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Spontaneous Dipole Reorientation in Confined Water and Its Effect on Wetting/Dewetting of Hydrophobic Nanopores
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Functional Nanostructured Materials (including low-D carbon)

Spontaneous Dipole Reorientation in Confined Water and Its Effect on Wetting/Dewetting of Hydrophobic Nanopores
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Cite this: ACS Appl. Mater. Interfaces 2024, 16, 6, 7604–7616
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https://doi.org/10.1021/acsami.3c17272
Published February 1, 2024

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Abstract

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The properties of nanoconfined fluids are important for a broad range of natural and engineering systems. In particular, wetting/dewetting of hydrophobic nanoporous materials is crucial due to their broad applicability for molecular separation and liquid purification; energy storage, conversion, recuperation, and dissipation; for catalysis, chromatography, and so on. In this work, a rapid, orchestrated, and spontaneous dipole reorientation was observed in hydrophobic nanotubes of various pore sizes d (7.9–16.5 Å) via simulations. This phenomenon leads to the fragmentation of water clusters in the narrow nanopores (d = 7.9, 10 Å) and strongly affects dewetting through cluster repulsion. The cavitation in these pores has an electrostatic origin. The dependence of hydrogen-bonded network properties on the tube aperture is obtained and is used to explain wetting (intrusion)–dewetting (extrusion) hysteresis. Computer simulations and experimental data demonstrate that d equals ca. 12.5 Å is a threshold between a nonhysteretic (spring) behavior, where intrusion–extrusion is reversible, and a hysteretic one (shock absorber), where hysteresis is prominent. This work suggests that water clustering and the electrostatic nature of cavitation are important factors that can be effectively exploited for controlling the wetting/dewetting of nanoporous materials.

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Introduction

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Nanoconfinement brings unexpected and sometimes counterintuitive properties in liquids, with water being the most fascinating example. (1−3) Understanding nanoconfined liquids is of paramount importance for a broad range of technologies, including purification, nanolubrication, separation, and energy. In particular, heterogeneous lyophobic systems (HLSs) consisting of porous solids and nonwetting liquids have many applications, including chromatography, molecular separations, energy storage, energy conversion, recuperation, dissipation, and so on. (4−11) Zeolites, metal–organic and covalent organic frameworks (MOFs, COFs), carbon nanotubes (CNTs), mesoporous silica, and porous liquids are natural and synthetic porous materials that have been intensively studied and applied. (12−18) Heterogeneous hydrophobic systems (HHSs) involving hydrophobic porous matrices and water have attracted much attention due to their simplicity and abundance. Moreover, wetting/dewetting processes are vital in biology and nanoscience, where water usually interacts with hydrophobic materials and structures. (19−21)
The hydrophobicity, pore opening size, geometry, topology of a pore system, and pore morphology are key parameters that determine the wetting of porous materials. A plethora of studies was devoted to investigating moderately hydrophobic and wetted ambient-pressure CNTs. (16,22) A single-walled CNT is a 1D cylindrical tube with a circular cross section that makes it favorable for modeling and computer simulations of heterogeneous water–CNT systems. It was shown that water changes its properties under confinement, and many anomalies were found. For example, new phases of ice, not observed for bulk water, are formed at high pressures. (22,23)
For more hydrophobic materials, water can be intruded into pores only at an elevated pressure. Intrusion–extrusion isotherms, the P–V diagrams, characterize this process. Extrusion can be observed at the same or lower pressure or may not occur at all. These HLSs are called molecular spring, shock-absorber, and bumper, respectively. (7,10)
Pure silica zeolites (PSZs) have larger hydrophobicity compared to that of CNTs, and water cannot permeate into crystals at ambient pressure. Plenty of zeolite topologies, pore sizes, pore shapes, and mutual intersections of porous channels hinder the systematic investigation of their wetting/dewetting. The chemical instability of some PSZs makes the situation even more complicated. Silanol defects of frameworks can be formed after water intrusion. They significantly decrease the hydrophobicity of PSZs, influencing extrusion pressure and, thus, the system behavior. (7,24,25) Progressive degradation of materials during the cyclization of intrusion–extrusion processes prevents their applications in some technologies.
Mesoporous silica materials are amorphous and hydrophilic due to silanol groups covering internal pore surfaces. They receive considerable attention due to their simple production and applications for medical diagnostics or drug delivery systems. (26,27) Using the methods of silane chemistry, they can be easily functionalized and made hydrophobic. However, synthesis conditions and the procedure of functionalization affect the pore size and volume and introduce heterogeneities at the nanoscale. The water intrusion–extrusion isotherms were obtained for some grafted mesoporous materials with the 1D system of channels. (28−30)
The dimensionality of the pore system affects water intrusion–extrusion. It was shown that hydrophobicity is regulated not only by the chemical modification of internal pore surfaces but also by closing lateral pores. (31,32) Computer simulations and correlations of experimental intrusion pressures with the ratio of Connolly surface area to pore volume show that PSZs with 1D channels have larger intrusion pressure than zeolites with other topologies with the same pore-opening diameters.
Despite intensive investigations, (15,33−35) the peculiarities of intermolecular interactions, molecular mechanisms of processes, and the structure of liquids under nanoconfinement are not well established. Many natural factors affect the wetting/dewetting processes in HHSs. The main goal of this work is to systematically investigate the collective behavior, dynamical state, structure, and interactions of water under different nanoconfinements and their effect on the wetting/dewetting process. The observed kinetics of molecular populations of tubes and processes of dipole reorientations indicate new factors for controlling the wetting/dewetting hysteresis of hydrophobic nanopores.

Results

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Intrusion–extrusion isotherms are the main results of experimental investigations of wetting and dewetting for HHSs. The isotherms, calculated for five nanotubes and presented in Figure 1, demonstrate pore loading versus external hydrostatic pressure. Two types of data presentations are exploited in the present work. The number of molecules in the tubes, N(P), is proportional to the adsorbed water volume. Meanwhile, the fractional loadings F(P) = N(P)/Nmax highlight curve differences and allow determining intrusion–extrusion pressures (Pintr, Pextr), which correspond to F = 0.5 by definition. Depending on the pore aperture, the three behaviors of heterogeneous systems are detected in our study: bumper (Pextr < 0), shock-absorber (Pextr < Pintr), and spring (Pextr = Pintr).

Figure 1

Figure 1. Intrusion–extrusion isotherms demonstrate three types of behavior for systems with different pore apertures: (a) number of water molecules vs pressure; cross sections of the pores are presented in insets; (b) fractional loadings vs pressure. Pintr and Pextr correspond to the half-loading of the tubes by definition.

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Atomistic simulations allow the intrusion–extrusion process to be observed step by step. Small water clusters, the groups connected by hydrogen-bond molecules, enter the tube from both sides. With the increasing pressure, they propagate at larger distances and coalesce afterward if the pressure is larger than Pintr. However, as will be shown further, the dynamic behavior of water clusters after intrusion and during extrusion depends on the pore width.
Two slopes appear on the curves in Figure 1. The first region corresponds to growing clusters with pressure, which occupy more and more room in tubes. The fast transition from a partially to totally loaded state is due to the relatively short tubes (ca. 39 Å). In an actual experimental situation, the pore length is orders of magnitude longer than that in our cases, and the experimental isotherms are smooth functions of pressure. However, the isotherms calculated for the narrowest pore are shallow-sloped, and they correspond to specific processes and water structures in the tube described below.
Figure 2 demonstrates the correlations of intrusion–extrusion pressures with the reversed pore diameter, d–1. This correlation was chosen according to the Laplace–Washburn equation that defines the capillary pressure as
Pc=−4γlvcos⁡θd=4γsl−γsvd
(1)
where γlv, γsl, and γsv are liquid–vapor, solid–liquid, and solid–vapor surface tension, respectively; θ is the contact angle; and d is the pore diameter. In our cases, it is difficult to define surface tension due to the extreme nanoconfinement because several water molecules are on the tips of the propagating clusters. However, the linear correlations of intrusion–extrusion pressures with d–1 are observed for the investigated systems.

Figure 2

Figure 2. Intrusion–extrusion pressures vs reverse pore apertures for tubes, PSZs, and mesoporous silica. Estimated extrusion pressures are shown by gray circles.

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The computational results are compared with the experimental ones obtained for PSZs (36) and grafted amorphous mesoporous silica materials with the 1D system of channels. (28−30) This topology was selected because the intrusion pressures significantly depend on the dimension of a pore. (31) Table 1S contains all experimental data presented in Figure 2, whereas Figure S1 demonstrates the zeolite pore aperture measurement method.
The hydrophobicity of materials depends on their quality and grafting density as well as functional groups. Grafted MCM-41, HMS, and RPB are less hydrophobic than MTS materials because the intrusion pressure is smaller than that expected from the correlation line calculated for MTS data. We used the MTS data for the correlation because they were obtained for the same material and method of grafting. (28) The quality of materials, the grafting protocol, and the material’s morphology affect the pressures. (30)
The external surface of PSZs has a hydrophobicity that is very different from that of the internal surface. This difference is due to the presence of hydrophilic OH groups. (37,38) Estimating the hydrophobicity of the channels and pores of zeolites using standard experimental methods is not possible. (39) Intrusion pressure correlates with the hydrophobicity of materials. However, pore shapes and water–wall interactions depend on the material and grafting procedure. The data presented in Figure 2 show that the hydrophobicity of simulated tubes is higher than the hydrophobicity of PSZs but lower than that of grafted mesoporous silica. At the same pore aperture (for example, at 1/d = 0.82 Å–1), intrusion pressure increases in the order: PZS, tubes, mesoporous silica.
The data for the 1D PSZs are listed on the right side of Figure 2. Previously, it was shown that all PSZs can be divided into three groups depending on their topology and the ratio of the Connolly surface to the free volume of pores. (31) The dimension, the shape of pores, and chemical interactions of silica with water affect the pressures. (24,25) Some defects in the crystalline structure usually appear after water loading. Silanol groups, forming hydrophilic nests, decrease hydrophobicity and, as a result, extrusion pressure. Thus, small hysteresis is observed for PSZs with 1D channels, but generally, zeolites demonstrate a spring behavior. For PSZs, the correlation with d–1 is monotonic and follows a similar trend as for the tubes and grafted silica. However, it is noticeably poorer due to some uncertainties in d definition due to a noncircular shape of the pore’s cross sections. (40)
The difference between intrusion and extrusion pressures is hysteresis. For the tubes, after a certain threshold, hysteresis appears and increases with the size of the pore aperture. Extrapolation of intrusion/extrusion fitting lines obtained for the MTS shows their intersection in the region very close to the intersection of the lines obtained for the tubes. Consistently, zeolites are all located in the spring region of d. All of the materials have the 1D system of channels, but hydrophobicity is different. It explains the different slopes of the fitting lines. The hydrophobicity of tubes is higher than that of PSZs but smaller than that of grafted mesoporous silica. However, we highlight the geometrical effect here: the wider the pore aperture─the larger the hysteresis. The estimated spring or shock-absorber behavior threshold is ca. 12.5. Å.
The largest tube and two mesoporous silica materials (MTS-4g and RPB) demonstrate the bumper behavior, Pextr < 0. After intrusion, water stays in pores even at ambient pressure. The estimated extrusion pressures are shown by gray circles in Figure 2. Large negative pressures are unreachable in actual experiments.

Figure 3

Figure 3. Time evolution of the average cosine between dipole moments and the axial direction of the tube (d = 7.9 Å): (a) at different pressures; (b) at P = 380 MPa. (c) Water clusters in the tube corresponding to event no. 1. Arrows show the orientation of dipole moments.

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Thus, computer models and experiments show three behaviors of HHSs composed of porous materials with a 1D system of channels. The width of pores and the hydrophobicity of materials determine the behavior. In our simulations, two narrow tubes are molecular springs. The structure of confined water was investigated to understand the obtained trend of hysteresis with the tube size.

Tube with d = 7.9 Å

First, we discuss the water structure and its dynamic behavior for the tube with the narrowest pore. Hydrogen-bonded water molecules form a single-file structure─a 1D chain. (41) Molecular dipole moments in H-bonded chains can be collectively “left-” or “right-side” oriented. For each saved molecular configuration, we calculated the average cosine angle α between the dipole moment of the molecules in the tube and the axial axis. The results are presented in Figure 3a. Most of the time, all molecular dipoles are preferentially oriented toward one side of the tube. However, in nanosecond intervals at any pressure larger than Pintr, several events corresponding to the fast dipole reorientation are observed. The hops between states often occur during 40 ps, evidencing collective molecular reorientation.
To study the process in detail, we calculated at P = 380 MPa the average cosine concentration and the number of molecules in the tube for the configurations saved with a time step of 4 ps. Four reorientation events are visible in Figure 3b. The first one occurs near 12 ns, with a duration of about 180 ps. Here, the collective dipole reorientations are accompanied by a partial depletion of the tube. The corresponding molecular configurations of water in the tube are shown in Figure 3c. During 16 ps, the reorientation wave propagated along the tube at a speed of 100 m/s (1 Å/ps). After that, the cluster loses connectivity, and two separated clusters with the “head-to-head” orientation and empty space between them are formed. Finally, the initial single-file structure has been restored. The same process is observed in Figure 3b at 14.2 ns (event no. 3). However, event no. 4 is different. Reorientation of the dipole moments is not accompanied by dewetting of the tube. The snapshots of the corresponding molecular configurations are shown in Figure S2. Again, the speed of the reorientation wave is about 100 m/s. During event no. 2, all dipoles changed the initial orientation, and empty space formation was observed.
At a smaller pressure (P = 320 MPa), the partial and total dewetting of the tube was observed approximately at 2 and 4 ns, respectively, as presented in Figure S3. These events are synchronized with the changes in the average cosine, which are close to zero due to the oppositely directed dipoles in the two clusters. With decreased pressure, the empty space increases due to the rise in the distance between clusters. There are no water molecules in the empty spaces. Repulsive electrostatic interactions create an additional internal pressure that increases the probability of dewetting.
Thus, two water clusters, formed after dipole-reorientation-induced splitting, can shrink, grow, or merge, restoring the single-file structure. In computer simulations, the lengths of tubes are orders of magnitude shorter than those in materials used for actual experiments. For long channels, fragmentation of water is expected. Empty spaces are formed between oppositely oriented water clusters. Under a higher pressure, the dynamic equilibrium shifts toward the more filled state of the channel, making isotherms shallow-sloped. Fragmentation is the factor that provokes additional internal resistance to water penetration. Experiments support this speculation. Shallow-sloped isotherms are observed for PSZs with narrow 1D channels, having MTT, (42) MTW, and TON (43) topologies. This has great importance for intrusion-based porosimetry techniques, including water intrusion porosimetry. (44) Typically, shallow-sloped isotherms are attributed to porous materials with a broad pore size distribution. However, our results suggest that the slope of the intrusion isotherm has nothing to do with the pore size distribution; rather, it is related to an additional energetic penalty due to electrostatic interactions of oppositely oriented dipoles of water in the nanopore. (45)

Tube with d = 10 Å

The geometry of the pores affects the shape of the water cluster, as presented in Figure 4. Four molecules are visible in the cross section, and the partially disordered square ice structure with four-membered rings (MRs) elements is observed (Figure S4). The formation of ice phases with different structures is a well-known phenomenon of water nanoconfinement. (2,22) Cylindrical nanotubes, mostly CNTs, were the objects for investigations. Phase diagrams of water were calculated for CNTs with d = 11.1 and 12.5 Å. (23) Depending on the pressure and temperature, five ice phases were identified. Square ice is formed in the narrow tube.

Figure 4

Figure 4. Water clusters are formed in the tube with d = 10 Å. Green lines highlight the four-membered rings of H bonds.

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In contrast to CNTs, there are no straight cylindrical channels among the zeolite topologies. We observed a liquid behavior in the tube. The associated four MR fragments can be embryos of the solid phase. Near the solid–liquid coexistence line, nucleation can be a very slow process, taking time far exceeding the time for computer simulations. The phenomenon of ice–liquid oscillations observed at nanoconfinement is more probable. (2) Figure S4 demonstrates spontaneous ice formation in almost the whole tube, but the ice melts with time. The absence of wetting/dewetting (intrusion–extrusion) hysteresis in experiments indicates the liquid state of water in the PSZs. Otherwise, ice would clog channels.
The average cosine fluctuates in time with a smaller amplitude than in the case of the tube with d = 7.9 Å because several interconnected chains of water molecules with oppositely directed dipoles are formed (see Figure S5). However, a spontaneous splitting of water into two clusters is observed. Two events are presented in Figures 5 and S6. Again, electrostatic interactions between clusters prevent their coalescence over hundreds of picoseconds. However, we do not observe a complete depletion of the tube at P > Pintr.

Figure 5

Figure 5. Water clusters in the tube with d = 10 Å. Arrows show the preferential orientation of the dipole moments.

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We may imagine the water cluster as four interconnected rubber threads to simplify the picture and better understand the process of cluster splitting. Unlike in a single-file structure, dipole reorientation must occur in four chains simultaneously. The probability of this event is rather small. Figure S7 demonstrates clusters that are close to being split. One can see a break of two or three threads, but the elasticity of the remaining threads is enough to prevent the complete disconnection and partial depletion of the tube in these cases. It is expected that spontaneous dewetting at P > Pintr is a rare event, but water fragmentation occurs in long channels. Again, dipole–dipole repulsion is responsible for splitting.

Tubes with d > 12 Å

Intrusion–extrusion hysteresis is observed for these tubes, but at P > Pintr, there are no breaks of percolated clusters. Several extrusion events are presented in Figure 6 and S8–S10. Average cosines are closer to zero than that in previously discussed cases due to the summation of differently oriented dipoles. Meanwhile, note that the extrusion process has stages: a local decrease in molecular density; formation of chains bridging bulky domains with oppositely directed dipoles; splitting of the cluster; and fast expulsion of fragments. Dipole–dipole interactions force the depletion of tubes.

Figure 6

Figure 6. Extrusion of water from the tube with d = 14.3 Å at P = 10 MPa. Arrows show the preferential orientation of dipole moments, t is the time mark, and N is the number of water molecules in the tube.

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Spontaneous Dipole Reorientation as a Triggering Factor for Dewetting (Extrusion)

The collective dipole reorientation described above provides a molecular level of understanding of the dewetting process of hydrophobic nanopores. Spontaneous cavitation is observed in molecular configurations at P < Pextr, but molecules still form clusters. There is no vapor phase in tubes at the explored temperature. The formation of bridges between bulky fragments and the breaking of “rubber threads” testify to the spinodal decomposition mechanism when metastable water loses mechanical stability. Fast and orchestrated orientational jumps provoke the formation of mutually repulsive domains connected by bridges. However, the bridges are the fragments of water structures observed in narrower pores that expel water at a higher pressure. The threads suddenly lose elasticity due to dipole reorientation. Thus, fast spontaneous molecular reorientation is a governing factor for dewetting.
We have observed only one mechanism of tube dewetting. Some events are presented in Figures 6 and S8–S10. However, cluster splitting can occur due to large spontaneous density or energy fluctuations, but the probability of such events is small. In the ensemble of channels in actual materials, their main part is dewetted through the orchestrated dipole reorientation of water molecules.

Properties of H-Bonded Networks

How does microporous confinement affect the water structure? It is a challenging question. We performed a set of calculations to answer it. The ability to form hydrogen bonds is one of the crucial properties dictating the structure of water. Many definitions of H bonds are used to analyze computed molecular configurations. (46) In this work, we apply the threshold criterion, considering two molecules bonded if the energy of their interactions is less than −3.5 kcal/mol (EHB < −14.64 kJ/mol), a typical energy of the middle-strength H-bond. It was shown (47,48) that the uncertainty in the definition of H bonds does not principally influence the final qualitative results. Scanning the water H-bonded network’s properties using the different EHB values gives additional information about weak and strong H-bond distributions.
The topological properties of the H-bonded networks were analyzed: the statistics of molecules with different connectivities─the fractions of molecules forming i bonds with neighbors (i = 0–4) (47) and the statistics of closed rings of H bonds in the network. (48−50) We compared the properties of water in the tubes with the corresponding properties of bulk water and water in imaginary tubes─the bulk water in the cutoff spaces with the geometrical parameters of the actual tubes. Water in imaginary tubes is in ideal hydrophilic surroundings. Molecules form hydrogen bonds with other water molecules through imaginary borders. However, the topological properties of H-bonded networks differ from those of bulk water due to artificial confinement, which depends on the tube size. Thus, a comparison of water properties for water in actual and imaginary tubes and bulk water highlights the confinement and the hydrophobicity effects.
The first characteristic under consideration is the statistics of H bonds. If each bond forms with probability p and breaks with the probability (1 – p), then in the model of the random network, the fraction of molecules with i bonds is defined as (47)
fi=(ki)pi(1−p)k−i×100%
(2)
Here, we assume that a water molecule can form four bonds at the maximum; thus, k = 4. The probability is calculated as p = nHB/4, where nHB is the mean number of H bonds per molecule, which depends on the H-bond definition. Some molecules in a molecular ensemble form bifurcated H bonds. We counted molecules with more than four bonds as four-bonded to compare the calculated fractions with the theoretical distribution, eq 2.
The second characteristic is ring statistics. A closed ring consists of molecules connected by hydrogen bonds if the path along the bonds comes back to the starting molecule. We searched all rings for each molecule until six-membered rings (6 MRs), not only short-circuited as it is usually adopted. (51) Thus, the same molecule can belong to several rings, not only the primitive ones. Our method has been used previously to investigate the topology of H-bonded networks formed in several liquids. (48−50) The closed ring statistics are characteristic of the supramolecular structure. Crystalline structures contain a specific set of rings. Hexagonal rings (6 MRs) are the basis of ice Ih and Ic. Five and six MRs are the elements of the network in clathrate hydrates. All types of rings are found in bulk water, but we will discuss only 3–6 MRs for simplicity.
Bulk water is the reference system for comparison to the properties of confined water. Calculations show that the mean number of H bonds per molecule is 3.01, and it does not depend on the external pressure. The distribution of molecules versus the number of H bonds they participated and the ring statistics are presented in Figure 7. We conclude that pressure minimally affects these properties of the network at the accepted definitions of H bond and pressure range. The thermodynamic properties of water, such as volume or enthalpy, depend on pressure. We consider only relatively strong H bonds forming a skeleton of the network with high elasticity. Pressure deforms these H bonds but does not break them. Only small deviations from the theoretical predictions (eq 2) are observed in Figure 7a. Thus, H bonds are formed randomly and distorted only under pressure. It reminiscences the well-known and widely considered random network model of water. (52)

Figure 7

Figure 7. Statistics of H bonds (a) and rings (b) for bulk water at different pressures. Here, i is the number of hydrogen bonds in which a molecule participates.

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Water is Confined in Tubes

The mean number of H bonds per water molecule decreases with a decrease in the pore width, as presented in Figure 8, evidencing network disruption. A linear correlation with d –1 is observed for four tubes, but if the bulk water is not too far from the extrapolated value, water in the narrowest tube is out of the correlation. In the perfect single-file structure, each molecule participates in two H bonds. The calculated nHB < 2 corresponds to the formation of separated water clusters in this tube.

Figure 8

Figure 8. Mean number of H bonds in which a water molecule participated. Data for four tubes were linearly fitted (red line) and extrapolated (dashed black line).

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Statistics of fi for water molecules in tubes with d > 8 Å are presented in Figure 9a. The fraction of molecules with four bonds (i = 4) progressively decreases, but f2 progressively increases with the narrowing of pores. Fractions of other types of water molecules do not vary significantly. Two factors affect these changes: a decrease in nHB and the alteration of the water structure due to confinement. Molecules near tube surfaces cannot form some H bonds due to sterical obstacles. It leads to an increase in their potential energy. The network adopts a new configuration to minimize this effect. Interconnected chains and square ice structures are the typical fragments in the networks, especially at d = 10 Å.

Figure 9

Figure 9. Statistics of H bonds for water: (a) in tubes with d ≥ 10 Å; (b) in the tube with d = 7.9 Å, comparing with theoretical predictions at k = 2 and 4, eq 2; (c) in the tube with d = 16.5 Å, comparing with bulk water and water in the imaginary tube. (d) Statistics of closed rings for bulk water and water in tubes.

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Are H bonds formed randomly in the tubes? To answer this question, we compared the statistics of bonds with the theoretical prediction in eq 2. Histograms presented in Figure S11 demonstrate an increase in the fractions of molecules with two Hbonds (i = 2) and a decrease in f4. The changes progressively increase with the degree of confinement. The distribution drastically changes for the narrowest pore (d = 7.9 Å), as shown in Figure 9b, and far from the distribution predicted by eq 2 with k = 4, but if we assume that k = 2, fi will correspond to the theoretical values. It means water molecules predominately form two H bonds instead of four, but they again are formed randomly with the probability p = nHB/2. Thus, we see the smooth distortion of the water structure in a specific range of pore openings until the critical value d < 10 Å. After that, the structure changes abruptly. However, H bonds are formed randomly in all cases.
Finally, we calculated the statistics for water molecules occluded in imaginary tubes in bulk water (Figure 9c). Only molecules whose coordinates correspond to the geometrical parameters of the internal space of tubes were selected in bulk water molecular configurations. We consider some H bonds broken because they link molecules across imaginary boundaries. These are the molecules forming H bonds with “ideal hydrophilic walls”. Thus, the effect of hydrophobic walls is highlighted. One can see three different distributions in Figure 9c. Due to confinement, the fractions of molecules with three and four H bonds decrease while f0 – f2 increase. For really occluded water, fractions of molecules with two and three bonds increase with respect to “imaginary confined” water. Considering a reduction of f0 and f1, we may conclude that the network distortion in the hydrophobic tube tends to be minimal. If molecules cannot form hydrogen bonds with walls, they minimize potential energy, forming additional bonds with molecules in the tube.
Statistics of rings are listed in Figure 9d. Again, as in the case of H-bond statistics, the confined water structure is significantly distorted compared with bulk water. The numbers of 5 and 6 MRs decrease, while the numbers of topological elements corresponding to distorted water structures (3 and 4 MRs) increase. Square cross sections of tubes stimulate the formation of 4 MRs, but the number of 4 MRs progressively decreases with the tube diameter. There is no significant difference in the distributions for the large tubes (d = 14.3 and 16.5 Å), but they are still far from bulk water. Confinement suppresses the formation of 6 MRs in the networks, but for the tube with d = 10 Å, the increase in 4 MRs is accompanied by an increase in 6 MRs. This evidences the formation of a partially disordered square ice structure because 6 MRs can be represented as a couple of 4 MRs with a shared edge (see Figure 4).
Does the tube shape affect the formation of square ice? Computer simulations demonstrate that this ice is formed in cylindrical CNTs, (23) silicon carbide nanotubes, (53) and irregularly shaped cylindrical channels of AFI-type PSZ. (54) These investigations show that ice formation has a general character and that the type of ice depends on the width of the pore and, to a small extent, on the chemistry or pore shape.
The study of nucleation and crystallization demands long productive runs reaching a few microseconds. (23) This investigation was not our primary task. Each crystal structure has a specific set of topological elements of the network––the “fingerprints”. According to our calculations, water in tubes is in a disordered state. It does not contradict ice–liquid oscillations observed in molecular configurations (Figure S4). The spring behavior of water–PSZ systems with 1D channels provided compelling evidence of the liquid state of confined water. In all tubes, liquid water is observed, but its structure is significantly altered due to a decrease in the average number of H bonds with narrowing and specific confinement and hydrophobic effects.

Discussion

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Our results demonstrate a strong effect of spontaneous collective dipole reorientation of nanoconfined water on the wetting/dewetting of hydrophobic nanopores. In particular, we demonstrate that the contact of two formed water clusters with oppositely oriented dipoles triggers dewetting (extrusion) due to electrostatic repulsion.
For bulk water, it was shown (55) that groups of molecules spontaneously, abruptly, and collectively change their orientations during a subpicosecond time, in other words, in the THz time scale. The fast and orchestrated angular jumps are predominantly located in the patches of the H-bonded network with a lower density and many defects. Confinement provokes such a behavior. In the narrowest tube, molecules in the chain form two H bonds with neighbors. The spontaneously broken H bond due to the angular jump of one molecule induces orchestrated reorientations of dipole moments in large clusters and, as a result, increases the probability of dewetting of a hydrophobic nanopore. In particular, our simulations show that dipole reorientations in the tube of 39 Å length and diameter of 7.9 Å occur during 40–200 ps, corresponding to the GHz range. The partial reorientation stimulates chain splitting. At hydrophobic tubes under elevated pressure, electrostatic repulsion of formed clusters with oppositely directed dipole moments creates an additional internal pressure, hindering their coalescence that facilitates dewetting (extrusion).
Our simulations were performed for tubes whose lengths are shorter than the channels in zeolite crystals but more prolonged than the length of biological nanopores. (56) The size of continuous clusters with the unimodal orientation of dipole moments depends on the temperature, pressure, hydrophobicity, width, and length of channels. In micrometer-sized channels, we expect water to form clusters when groups of molecules are separated by voids, which is usually called the vapor phase. However, the volume fraction of the voids is small and decreases with pressure (see Figure 1). A dipole–dipole repulsion strongly depends on distance. Figures 3c and 5 demonstrate typical voids, whose lengths are approximately 4–7 Å.
Because of the state above, one may expect that the wetting (intrusion)/dewetting (extrusion) pressure depends on an external electric field, which inhibits spontaneous dipole reorientations and promotes wetting. An electrowetting effect was observed (56,57) in the computer simulations of short pores (ca. 10–30 Å) with lower hydrophobicity than the hydrophobicity of PSZs and grafted mesoporous silica. The voltage-gated ion channel mechanism is crucial in understanding the nature of biological membrane permeability. (56,58)
Charged particles on the outer and inner surfaces can influence porous materials’ wetting/dewetting properties. In this article, we discuss only PSZs that do not contain any extra-charged particles like aluminum atoms in the framework and extra-framework counterions. Even a small amount of Al decreases both pressures due to the strong interactions of water molecules with ions and the formation of water clusters. (55,59) The same effect was observed for the silanol defects. (60) The synthesis and methods of PSZs and mesoporous materials characterization are described in the literature. (28−30,61) Deionized and degassed water was used for intrusion–extrusion experiments. Thus, experimentally studied systems could contain only trace amounts of ions.
Intrusion–extrusion experiments with PSZs show that both pressures shift toward high values when aqueous salt solutions are used instead of water. (10) Ions, adsorbed on the outer surface of micrometer-sized crystals, cannot affect pressures due to charge screening at long distances from the surfaces where most pores are situated. Ions can affect the wetting/dewetting of porous materials if they penetrate pores. The increase in osmotic pressure and partial desolvation of hydrated ions can explain the increase in intrusion/extrusion pressures. The ion dehydration was detected experimentally. (62,63) It has been shown that intruded species are ions coordinated by a smaller number of water molecules than those in the bulk solution. On the other hand, PSZs are exploited to produce reverse osmosis membranes used for water desalination. (64)
Monte Carlo (65) and MD (66) simulations of narrow water-filled CNTs demonstrate that a static electric field of ca. 108 V/m decreases the diffusion coefficient of water in CNTs while increasing the average number of H bonds. For hydrophobic tubes with an aperture diameter of 20–30 Å, MD simulations showed that the same electric field does decrease the extrusion pressure. (67)
The main problem is the achievement of such a strong field in experiments. An isolated monovalent ion in a vacuum creates an electric field of ca. 108 V/m at a distance of less than 20 Å, and it decreases fast with the distance. The static dielectric permittivity of a liquid (ε) proportionally reduces the field. Electric screening effects manifest in nanotubes. (41,68) Meanwhile, the simulations of a single-file structure reaction on the isolated ion imposed in a vacuum near the CNT wall demonstrate the soliton-like propagation of dipole reorientation with the speed of 720 m/s. (69) It is 1 order of magnitude faster than in our case of spontaneous reorientation and defect diffusion through the hydrophobic tube under elevated pressure. Cavitation hinders soliton propagation over long distances. An electric field is expected to provoke the soliton mechanism and support proton transport along 1D chains (41) formed in pores under pressure.
The experimental evidence of the intrusion pressure decrease due to external electric field was obtained for ZSM-5 (MFI) zeolite. (70) This zeolite has a 3D network of narrow channels. Therefore, at any moment in the zeolite–water dispersion, only a small part of water molecules in micropores are oriented along the applied electric field. However, intrusion pressure decreased by 15% with the increase in strength of the electric field to 2400 V/m, which is 5 orders of magnitude weaker than the field used in computer simulations. This effect may be due to the inhibition of the spontaneous dipole reorientation of nanoconfined water.
Thus, experiments and computer simulations show that ions or static electric fields affect the wetting/dewetting of hydrophobic pores. Suppression of orchestrated dipole reorientation explains the electrowetting effect. Additional computer simulations are needed to investigate how a static electric field affects the frequency of reorientations, water cluster sizes, and the structure of water.
We hypothesize that a more effective control of wetting/dewetting can be obtained by applying microwave electromagnetic radiation. The main idea is that water in the tube is in an altered state. It differs from bulk water, and we may expect different frequencies of dipole reorientations. The oscillation of the electric field vector in resonance with collective dipole reorientation may provoke fast energy absorption and the transformation of energy into heat.
This hypothesis is supported by the previous computations of the effect of microwaves on water in narrow CNTs. (71) The maximum of the imaginary part of complex-frequency-dependent dielectric permittivity, responsible for dielectric losses and microwave absorption, is shifted toward the lower frequency range with respect to bulk water, where the maximum is at ca. 20 GHz. According to calculations, the maximum microwave absorption for (8,8) CNT with the single-file water structure is observed near 2.45 GHz, the frequency used in ordinary microwave ovens, where water is relatively transparent, and the reflection of waves from walls provides their deep penetration into a heating object and effective absorption.
Suppose a gap separates the microwave absorption bands for confined and bulk water. In that case, one can control intrusion–extrusion pressures and heat release in a porous material by applying microwave electromagnetic radiation. Additional pressure must be applied to suppress chain fragmentation and water boiling inside pores. Hence, intrusion–extrusion pressures can be controlled by the power or direction of radiation in the case of the anisotropic orientation of pores. The pores should be oriented along the electromagnetic wave propagation direction to maximize the effect of the electric field on the intrusion–extrusion pressure. Therefore, membranes with ordered pores are preferred for this strategy. On the contrary, powderous materials, where channels are randomly oriented, should have a lower effect of an electric field that is expected to result in shallow-sloped isotherms. The same can be stated about the 2D and 3D pore systems.

Heated Water in Micropores Expels from Hydrophobic Pores at a High Speed

It was proposed to exploit this effect for the engineering of nanorockets. (72) The possible construction of the nanorocket using water heating inside double-walled CNTs was demonstrated. One of the applications of nanorockets is drug delivery vehicles. (73) If our hypothesis is correct, the design of the nanorocket may be simple, and pulsating microwave radiation used as the energy source will help the cyclization of the process and permanent motion of nanoparticles. The new propulsion mechanism can be used widely. (73,74)
Thus, the observed effects for nanoconfined water under pressure stimulate new theoretical and experimental investigations that promise a broad range of prospective applications covering energy storage, liquid purification, the production of nanoparticles with unique properties, and many more.

Conclusions

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It was demonstrated that the collective dipole reorientation mechanism in liquid water is manifested under nanoconfinement and plays a crucial role in the system’s wetting/dewetting behavior. At elevated pressures, we found the instability of the single-file structure observed in the narrowest hydrophobic pore under investigation (d = 7.9 Å) due to the fast and orchestrated reorientation of molecular dipoles, followed by splitting and repulsion of formed water clusters. The wave of sequaciously jumping dipoles propagates the tube with a speed of ca. 100 m/s. As a result, the total dipole reorientation in a molecular chain occurs, or the chain splits into fragments, which increases the probability of dewetting (extrusion) due to the repulsive electrostatic interactions of oppositely oriented dipoles in separated molecular chains that create the internal pressure responsible for cavitation.
The proposed mechanism plays a significant role in wider tubes (d = 12.2–16.5 Å) during water expulsion. With a decrease in pressure (P < Pintr), water goes into the stretched and metastable state, followed by the loss of mechanical stability. A splitting water cluster is stabilized by chain bridging, while it is destabilized by electrostatic interactions and the spontaneous reorientation of dipoles.
By combining the simulation and experimental data for PSZs, grafted mesoporous silica, and tubes, we demonstrate that the wetting (intrusion)–dewetting (extrusion) hysteresis appears for pore apertures larger than ca. 12.5 Å and progressively increases with the width of the pore.
Statistics of H bonds and closed rings were analyzed to characterize the water structure under confinement. It was demonstrated that the bulk water structure is altered in pores. The mean number of H bonds per molecule decreases linearly with d–1 for all pores except the narrowest, manifesting progressive disruption of the H-bonded network. In the meantime, the H-bond statistics generally correspond to the theoretical predictions assuming random formation and breaking of bonds. The water structure is abruptly changed in the narrowest pore, where a single-file structure is observed. The analysis of statistics of closed rings of H bonds, which characterize the topological properties of networks, has shown that the square shape of the pore’s cross sections stimulates the formation of 4 MRs. Embryos of the square ice structure─the associated 4 MRs─are observed in the pore with d = 10 Å.
Tubes with pore openings of 7.9 and 10 Å demonstrate the molecular spring behavior. The water structure is the most distorted due to confinement in these tubes. With the increase in the tube diameter, the structure gets closer to the structure of bulk water, and water stays in tubes at a pressure lower than intrusion pressure due to its ability to be in the metastable state.
The obtained results are useful for designing heterogeneous systems for energy storage and absorption and explaining a broad range of phenomena where water interacts with porous hydrophobic materials, such as liquid purification, separation, catalysis, and so on. We expect that dipole reorientation jumps under confinement are sensitive to the electric field and microwave radiation, which can be used to regulate the wetting/dewetting of pores and to be among the dominant factors controlling the hydrophobicity of porous materials. Additional investigations must be performed to elucidate this hypothesis.

Methods

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We investigated simplified systems to highlight the role of the size of the pore openings. Porous materials were made from the face-centered cubic (fcc) crystal structure of gold. Five tubes of different widths and the same length were prepared. The tubes were excavated from the crystals so that the wall thickness was the same for all tubes; an example is presented in Figure S12.
In contrast with the cylindrical single-walled CNTs, the tailored tubes have square cross sections and thick walls that make them closer to real systems, such as zeolites. To generalize the results of computations, we modeled systems whose properties are close to those of both PSZs and some mesoporous silica materials for which experimental measurements were done.
We define the internal size of a tube d as the distance between the centers of atoms. It equals the edge of the square cross section. Otherwise, not well-defined distances may be assigned due to the “softness” of atoms. It is a source of additional uncertainties. Tubes were tailored from atoms with Lennard-Jones parameters of water oxygens; thus, the accessible size of a pore is about 2.8 Å less than d. Oxygens cover the zeolite pore surfaces. It is difficult to assign an average parameter for pore opening because of the irregular shape of pores in 1D channel systems (see Figure S1). (40) The definition of pore aperture for mesoporous silica materials is not as critical as in the case of microporous ones, and we took them from the original publications. (28)
In our models, the pore openings d were 7.9, 10, 12.2, 14.3, and 16.5 Å, whereas the length of the tubes was 39 Å. The tubes were immersed in orthorhombic boxes with 20,000 water molecules. Periodic boundary conditions were applied to eliminate surface effects. The Melchionna modification of the Nosé–Hoover algorithm was used for molecular dynamics simulations in the NPT ensemble at T = 300 K and P = 0–380 MPa by using the DL_POLY version 4.10 software. 0.5 and 1 ps relaxation times were employed for thermo- and barostat, respectively.
For simplicity, we used rigid tubes. Atoms were fixed in their crystallographic positions to save the tube structure during the simulations. Due to fluctuations in pressure, the sizes of the tubes vibrated during runs. They were also slightly different (less than 3%) at different external pressures due to the scaling of the atomistic coordinates, according to the barostat algorithm. This effect mimics the compressibility of the actual materials.
The SPC/Fw flexible water model was adopted for simulations with a recommended spherical cutoff radius of 9 Å. (75) The simulation results can, to some extent, be dependent on the choice of the force field. For example, using the TIP4P/2005 water model, Mochizuki (54) observed a spontaneous square ice formation in AFI-type PSZ at 300 K, but crystallization was absent at elevated temperatures. This force field provides a qualitatively correct description of the relative energies of ice for bulk water (76) but does not exclude artifacts for water under nanoconfinement. SPC-type force fields correspond well to experimental intrusion/extrusion pressures for PSZs, (24,32,77) and the short cutoff radius is optimal for accelerating calculations in the DL_POLY 4 program.
The interactions between tube atoms were neglected. The parameters of Lennard-Jones interactions for water and tube atoms are the same: ε = 0.1554 kcal/mol and σ = 3.1655 Å. The tubes are artificial objects whose hydrophobicity is regulated to a large extent by electrostatic interactions between water and tube atoms. In the present work, these electrostatic interactions are absent, providing a larger hydrophobicity of the tubes than the hydrophobicity of PSZs where silicon and oxygen atoms have partial electric charges. The roles of framework flexibility, partial electric charges, and water models were discussed in previous publications (see Supporting Information). (32,77) It was shown that the decrease of charges shifts intrusion–extrusion pressures toward higher values, thus making the material more hydrophobic.
The smooth particle mesh Ewald method was used to calculate the long-range part of the electrostatic interactions. Equations of motion were integrated numerically by the velocity Verlet method with a time step of 1 fs. The duration of the runs depended on the pressure and width of the tubes, reaching 20 ns in some cases. An example of DL_POLY files containing all information about the simulation method and force fields is presented in Supporting Information.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.3c17272.

  • DL_POLY input files (ZIP)

  • Characteristics of pure silica zeolites and grafted mesoporous silica materials with the 1D system of channels; pore openings in zeolites with the 1D system of channels; evolution of dipole orientations in the water cluster in the tube; time evolutions of the average cosine and the number of water molecules in the tube; fragments of square ice structure; evolution of average cosine between dipole moments and the axial direction of the tube; collection of snapshots of clusters in the tube; extrusion of water from the tube; and statistics of H bonds for water in tubes (PDF)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Author Information

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  • Corresponding Author
  • Authors
    • Yaroslav Grosu - Institute of Chemistry, University of Silesia in Katowice, Szkolna 9 Street, 40-006 Katowice, Poland;  Centre for Cooperative Research on Alternative Energies (CIC EnergiGUNE), Basque Research and Technology Alliance (BRTA), Alava Technology Park, Albert Einstein 48, Vitoria, Gasteiz 01510, Spain;  Orcidhttps://orcid.org/0000-0001-6523-1780
    • Mirosław Chorążewski - Institute of Chemistry, University of Silesia in Katowice, Szkolna 9 Street, 40-006 Katowice, Poland;  Orcidhttps://orcid.org/0000-0002-8912-9024
  • Author Contributions

    The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

  • Funding

    This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement no. 101017858 and from the Narodowe Centrum Nauki (National Science Centre, Poland) No. 2018/31/B/ST8/00599. This article is part of the grant RYC2021–032445-I funded by MICIN/AEI/10.13,039/501100011033 and by the European Union NextGenerationEU/PRTR.

  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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Y.B. acknowledges the University of Silesia in Katowice for access to the PAAD cluster.

References

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This article references 77 other publications.

  1. 1
    Zhang, S.; Zhang, J.; Zhang, Y.; Deng, Y. Nanoconfined Ionic Liquids. Chem. Rev. 2017, 117 (10), 6755– 6833,  DOI: 10.1021/acs.chemrev.6b00509
    Google Scholar
    1
    Nanoconfined Ionic Liquids
    Zhang, Shiguo; Zhang, Jiaheng; Zhang, Yan; Deng, Youquan
    Chemical Reviews (Washington, DC, United States) (2017), 117 (10), 6755-6833CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. Ionic liqs. (ILs) have been widely investigated as novel solvents, electrolytes, and soft functional materials. Nevertheless, the widespread applications of ILs in most cases have been hampered by their liq. state. The confinement of ILs into nanoporous hosts is a simple but versatile strategy to overcome this problem. Nanoconfined ILs constitute a new class of composites with the intrinsic chemistries of ILs and the original functions of solid matrixes. The interplay between these two components, particularly the confinement effect and the interactions between ILs and pore walls, further endows ILs with significantly distinct physicochem. properties in the restricted space compared to the corresponding bulk systems. The aim of this article is to provide a comprehensive review of nanoconfined ILs. After a brief introduction of bulk ILs, the synthetic strategies and investigation methods for nanoconfined ILs are documented. The local structure and physicochem. properties of ILs in diverse porous hosts are summarized in the next sections. The final section highlights the potential applications of nanoconfined ILs in diverse fields, including catalysis, gas capture and sepn., ionogels, supercapacitors, carbonization, and lubrication. Further research directions and perspectives on this topic are also provided in the conclusion.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XitFKksrnO&md5=651e867644b95e0294e99ef691ed6c74
  2. 2
    Kastelowitz, N.; Molinero, V. Ice-Liquid Oscillations in Nanoconfined Water. ACS Nano 2018, 12 (8), 8234– 8239,  DOI: 10.1021/acsnano.8b03403
    Google Scholar
    2
    Ice-Liquid Oscillations in Nanoconfined Water
    Kastelowitz, Noah; Molinero, Valeria
    ACS Nano (2018), 12 (8), 8234-8239CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
    Nanoscale confinement has a strong effect on the phase behavior of water. Studies in the last two decades have revealed a wealth of novel cryst. and quasicryst. structures for water confined in nanoslits. Less is known, however, about the nature of ice-liq. coexistence in extremely nanoconfined systems. Here, we use mol. simulations to investigate the ice-liq. equil. for water confined between two nanoscopic disks. We find that the nature of ice-liq. phase coexistence in nanoconfined water is different from coexistence in both bulk water and extended nanoslits. In highly nanoconfined systems, liq. water and ice do not coexist in space because the two-phase states are unstable. The confined ice and liq. phases coexist in time, through oscillations between all-liq. and all-cryst. states. The avoidance of spatial coexistence of ice and liq. originates on the non-negligible cost of the interface between confined ice and liq. in a small system. It is the result of the small no. of water mols. between the plates and has no analog in bulk water.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtlGit7jM&md5=5722fe0c65f2593a216643ab33ab709b
  3. 3
    Leoni, F.; Calero, C.; Franzese, G. Nanoconfined Fluids: Uniqueness of Water Compared to Other Liquids. ACS Nano 2021, 15 (12), 19864– 19876,  DOI: 10.1021/acsnano.1c07381
    Google Scholar
    3
    Nanoconfined Fluids: Uniqueness of Water Compared to Other Liquids
    Leoni, Fabio; Calero, Carles; Franzese, Giancarlo
    ACS Nano (2021), 15 (12), 19864-19876CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
    Nanoconfinement can drastically change the behavior of liqs., puzzling us with counterintuitive properties. It is relevant in applications, including decontamination and crystn. control. However, it still lacks a systematic anal. for fluids with different bulk properties. Here we address this gap. We compare, by mol. dynamics simulations, three different liqs. in a graphene slit pore: (A) A simple fluid, such as argon, described by a Lennard-Jones potential; (B) An anomalous fluid, such as a liq. metal, modeled with an isotropic core-softened potential; (C) Water, the prototypical anomalous liq., with directional hydrogen bonds. We study how the slit-pore width affects the structure, thermodn., and dynamics of the fluids. All the fluids show similar oscillating properties by changing the pore size. However, their free-energy min. are quite different in nature: (i) are energy-driven for the simple liq.; (ii) are entropy-driven for the isotropic core-softened potential; (iii) have a changing nature for water. Indeed, for water the monolayer min. is entropy-driven, at variance with the simple liq., while the bilayer min. is energy-driven, at variance with the other anomalous liq. Also, water has a large increase in diffusion for subnm slit pores, becoming faster than bulk. Instead, the other two fluids have diffusion oscillations much smaller than water, slowing down for decreasing slit-pore width. Our results, clarifying that water confined at the subnm scale behaves differently from other (simple or anomalous) fluids under similar confinement, are possibly relevant in nanopores applications, e.g., in water purifn. from contaminants. Longitudinal diffusion coeff. D‖, normalized to its large-δ value, for the three fluids in a slit-pore, as a function of the plate sepn. δ. Comparison of the TIP4P/2005-water (blue triangles) with (a) the LJ (black circles), and (b) the CSW (red squares). In both panels vertical lines mark, approx., maxima (dotted lines) and min. (dot-dashed lines) for the isotropic fluid (see text). The value of D‖ at δ = 17 Å is ≃23 nm2/ns for both the LJ and the CSW, and is ≃1.9 nm2/ns for the TIP4P/2005-water.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXisFemt77O&md5=95c7bc5417a3fddb061ebb3c1657ef64
  4. 4
    Giacomello, A. What Keeps Nanopores Boiling. J. Chem. Phys. 2023, 159 (11), 110902,  DOI: 10.1063/5.0167530
    Google Scholar
    4
    What keeps nanopores boiling
    Giacomello, Alberto
    Journal of Chemical Physics (2023), 159 (11), 110902CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
    A review. The liq.-to-vapor transition can occur under unexpected conditions in nanopores, opening the door to fundamental questions and new technologies. The physics of boiling in confinement is progressively introduced, starting from classical nucleation theory, passing through nanoscale effects, and terminating with the material and external parameters that affect the boiling conditions. The relevance of boiling in specific nanoconfined systems is discussed, focusing on heterogeneous lyophobic systems, chromatog. columns, and ion channels. The current level of control of boiling in nanopores enabled by microporous materials such as metal org. frameworks and biol. nanopores paves the way to thrilling theor. challenges and to new technol. opportunities in the fields of energy, neuromorphic computing, and sensing. (c) 2023 American Institute of Physics.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhvFKlu7fF&md5=00ad49946af56a3904a2184c1717a825
  5. 5
    Gritti, F.; Hlushkou, D.; Tallarek, U. Faster Dewetting of Water from C8- than from C18-Bonded Silica Particles Used in Reversed-Phase Liquid Chromatography: Solving the Paradox. J. Chromatogr. A 2019, 1602, 253– 265,  DOI: 10.1016/j.chroma.2019.05.041
    Google Scholar
    5
    Faster dewetting of water from C8- than from C18-bonded silica particles used in reversed-phase liquid chromatography: Solving the paradox
    Gritti, Fabrice; Hlushkou, Dzmitry; Tallarek, Ulrich
    Journal of Chromatography A (2019), 1602 (), 253-265CODEN: JCRAEY; ISSN:0021-9673. (Elsevier B.V.)
    For comparable surface coverage of alkyl-bonded chains (∼3μmol/m2), the dewetting of 100% aq. mobile phases from the mesopores of octyl(C8)-bonded silica particles is found 70 times faster than that from the same but octadecyl(C18)-bonded silica particles. This observation was made in this work for both fully porous (5μm Symmetry) and superficially porous (2.7μm CORTECS) particles. This exptl. result is paradoxical because (1) the av. pore size of C8-bonded materials is 10-15 Å larger than that of C18-bonded materials for the same unbounded silica gel and (2) the contact angle of water measured on smooth and planar C8-bonded surface is ∼6° smaller than that on the same but C18-bonded surface (104° vs. 110°). The equil. Laplace pressure is then expected to be smaller and the kinetics of water dewetting to be slower for silica-C8 than for silica-C18 stationary phases used in RPLC. The soln. to this riddle was studied based on (1) the calcn. of the dewetting time assuming that the pores are monosized and the process is driven by the Laplace pressure, (2) the measurement of the advancing and receding contact angles of three different C18- and C8-bonded silica gels (4μm NovaPak, 5μm Symmetry, and 2.7μm CORTECS) from the water porograms measured in a range of water pressure from normal pressure to 500 bar, and (3) on the calcn. of the pore connectivity for both C8 and C18-bonded silica. First, the obsd. dewetting times are of the order of minutes or even hours instead of millisecond as predicted by the dewetting model. Secondly, the advancing and receding contact angles of water onto the C8-bonded silicas are found larger (by an av. of +7° and +2°, resp.) than those measured for the same but C18-bonded silica (av. of 112° and 92°). Finally, the calcd. pore connectivity is decreasing by ∼30% for 90 Å unbounded silica materials from C8 to C18-bonded RPLC phases. Overall, the obsd. and much faster dewetting of water from C8 column than that from C18 column is primarily explained by a higher internal pore connectivity due to the thinner thickness of the alkyl-bonded layer (7 Å vs. 15 Å) and, to a lesser extent, by a higher extrusion Laplace pressure of water (≃+10 bar).
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtFClsbvM&md5=26ae05a35b2eec2aeebc7bf3f2cf3ace
  6. 6
    Eroshenko, V.; Regis, R. C.; Soulard, M.; Patarin, J. Energetics: A New Field of Applications for Hydrophobic Zeolites. J. Am. Chem. Soc. 2001, 123 (33), 8129– 8130,  DOI: 10.1021/ja011011a
    Google Scholar
    6
    Energetics. A new field of applications for hydrophobic zeolites
    Eroshenko, Valentin; Regis, Robert-Charles; Soulard, Michel; Patarin, Joeel
    Journal of the American Chemical Society (2001), 123 (33), 8129-8130CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    A thermodn. study was carried out for several hydrophobic zeolites in contact with H2O. The water-zeolite β, water silicalite-1 (OH-), and water silicalite-1 (F-) systems were examd. The compressibility of the systems was measured, and the pressure-vol. isotherms are depicted. The reciprocal transformation of mech. energy into interfacial energy in such a system is discussed together with possible energetic applications.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXlsFaqtbg%253D&md5=606031933801cc854c44d99f6bc3572c
  7. 7
    Fraux, G.; Coudert, F. X.; Boutin, A.; Fuchs, A. H. Forced Intrusion of Water and Aqueous Solutions in Microporous Materials: From Fundamental Thermodynamics to Energy Storage Devices. Chem. Soc. Rev. 2017, 46 (23), 7421– 7437,  DOI: 10.1039/C7CS00478H
    Google Scholar
    7
    Forced intrusion of water and aqueous solutions in microporous materials: from fundamental thermodynamics to energy storage devices
    Fraux, Guillaume; Coudert, Francois-Xavier; Boutin, Anne; Fuchs, Alain H.
    Chemical Society Reviews (2017), 46 (23), 7421-7437CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    We review the high pressure forced intrusion studies of water in hydrophobic microporous materials such as zeolites and MOFs, a field of research that has emerged some 15 years ago and is now very active. Many of these studies are aimed at investigating the possibility of using these systems as energy storage devices. A series of all-silica zeolites (zeosil) frameworks were found suitable for reversible energy storage because of their stability with respect to hydrolysis after several water intrusion-extrusion cycles. Several microporous hydrophobic zeolite imidazolate frameworks (ZIFs) also happen to be quite stable and resistant towards hydrolysis and thus seem very promising for energy storage applications. Replacing pure water by electrolyte aq. solns. enables to increase the stored energy by a factor close to 3, on account of the high pressure shift of the intrusion transition. In addn. to the fact that aq. solns. and microporous silica materials are environmental friendly, these systems are thus becoming increasingly interesting for the design of new energy storage devices. This review also addresses the theor. approaches and mol. simulations performed in order to better understand the exptl. behavior of nano-confined water. Mol. simulation studies showed that water condensation takes place through a genuine first-order phase transition, provided that the interconnected pores structure is 3-dimensional and sufficiently open. In an extreme confinement situations such as in ferrierite zeosil, condensation seem to take place through a continuous supercrit. crossing from a dild. to a dense fluid, on account of the fact that the first-order transition line is shifted to higher pressure, and the confined water crit. point is correlatively shifted to lower temp. These mol. simulation studies suggest that the most important features of the intrusion/extrusion process can be understood in terms of equil. thermodn. considerations.
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  8. 8
    Wu, L.; Li, Y.; Fu, Z.; Su, B. L. Hierarchically Structured Porous Materials: Synthesis Strategies and Applications in Energy Storage. Natl. Sci. Rev. 2020, 7 (11), 1667– 1701,  DOI: 10.1093/nsr/nwaa183
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    8
    Hierarchically structured porous materials: synthesis strategies and applications in energy storage
    Wu, Liang; Li, Yu; Fu, Zhengyi; Su, Bao-Lian
    National Science Review (2020), 7 (11), 1667-1701CODEN: NSRACI; ISSN:2053-714X. (Oxford University Press)
    To address the growing energy demands of sustainable development, it is crucial to develop new materials that can improve the efficiency of energy storage systems. Hierarchically structured porous materials have shown their great potential for energy storage applications owing to their large accessible space, high surface area, low d., excellent accommodation capability with vol. and thermal variation, variable chem. compns. and well controlled and interconnected hierarchical porosity at different length scales. Porous hierarchy benefits electron and ion transport, and mass diffusion and exchange. The electrochem. behavior of hierarchically structured porous materials varies with different pore parameters. Understanding their relationship can lead to the defined and accurate design of highly efficient hierarchically structured porous materials to enhance further their energy storage performance. In this review, we take the characteristic parameters of the hierarchical pores as the survey object to summarize the recent progress on hierarchically structured porous materials for energy storage. This is the first of this kind exclusively to survey the performance of hierarchically structured porous materials from different porous characteristics. For those who are not familiar with hierarchically structured porous materials, a series of very significant synthesis strategies of hierarchically structured porous materials are firstly and briefly reviewed.This will be beneficial for those who want to quickly obtain useful ref. information about the synthesis strategies of new hierarchically structured porousmaterials to improve their performance in energy storage. The effect of different organizational, structural and geometric parameters of porous hierarchy on their electrochem. behavior is then deeply discussed.We outline the existing problems and development challenges of hierarchically structured porous materials that need to be addressed in renewable energy applications.We hope that this review can stimulate strong intuition into the design and application of new hierarchically structured porous materials in energy storage and other fields.
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  9. 9
    Hashemi-Tilehnoee, M.; Tsirin, N.; Stoudenets, V.; Bushuev, Y. G.; Chorążewski, M.; Li, M.; Li, D.; Leão, J. B.; Bleuel, M.; Zajdel, P.; Del Barrio, E. P.; Grosu, Y. Liquid Piston Based on Molecular Springs for Energy Storage Applications. J. Energy Storage 2023, 68, 107697,  DOI: 10.1016/j.est.2023.107697
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    There is no corresponding record for this reference.
  10. 10
    Confalonieri, G.; Daou, T. J.; Nouali, H.; Arletti, R.; Ryzhikov, A. Energetic Performance of Pure Silica Zeolites under High-Pressure Intrusion of LiCl Aqueous Solutions: An Overview. Molecules 2020, 25 (9), 2145,  DOI: 10.3390/molecules25092145
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    10
    Energetic performance of pure silica zeolites under high-pressure intrusion of LiCl aqueous solutions: an overview
    Confalonieri, Giorgia; Daou, T. Jean; Nouali, Habiba; Arletti, Rossella; Ryzhikov, Andrey
    Molecules (2020), 25 (9), 2145CODEN: MOLEFW; ISSN:1420-3049. (MDPI AG)
    A review. An overview of all the studies on high-pressure intrusion-extrusion of LiCl aq. solns. in hydrophobic pure silica zeolites (zeosils) for absorption and storage of mech. energy is presented. Operational principles of heterogeneous lyophobic systems and their possible applications in the domains of mech. energy storage, absorption, and generation are described. The intrusion of LiCl aq. solns. instead of water allows to considerably increase energetic performance of zeosil-based systems by a strong rise of intrusion pressure. The intrusion pressure increases with the salt concn. and depends considerably on zeosil framework. In the case of channel-type zeosils, it rises with the decrease of pore opening diam., whereas for cage-type ones, no clear trend is obsd. A relative increase of intrusion pressure in comparison with water is particularly strong for the zeosils with narrow pore openings. The use of highly concd. LiCl aq. solns. instead of water can lead to a change of system behavior. This effect seems to be related to a lower formation of silanol defects under intrusion of solvated ions and a weaker interaction of the ions with silanol groups of zeosil framework. The influence of zeosil nanostructure on LiCl aq. solns. intrusion-extrusion is also discussed.
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  11. 11
    Grosu, Y.; Li, M.; Peng, Y. L.; Luo, D.; Li, D.; Faik, A.; Nedelec, J. M.; Grolier, J. P. A Highly Stable Nonhysteretic {Cu2(Tebpz) MOF+water} Molecular Spring. ChemPhysChem 2016, 17 (21), 3359– 3364,  DOI: 10.1002/cphc.201600567
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    11
    A Highly Stable Nonhysteretic {Cu2(tebpz) MOF + water} Molecular Spring
    Grosu, Yaroslav; Li, Mian; Peng, Yun-Lei; Luo, Dong; Li, Dan; Faik, Abdessamad; Nedelec, Jean-Marie; Grolier, Jean-Pierre
    ChemPhysChem (2016), 17 (21), 3359-3364CODEN: CPCHFT; ISSN:1439-4235. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A mol. spring formed by a hydrophobic metal-org. framework Cu2(tebpz) (tebpz = 3,3',5,5'-tetraethyl-4,4'-bipyrazolate) and water is presented. This nanoporous heterogeneous lyophobic system (HLS) has exceptional properties compared to numerous reported systems of such type in terms of stability, efficiency, and operating pressure. Mech. and thermal energetic characteristics as well as stability of the system are discussed and compared in detail with those of other previously reported HLS.
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  12. 12
    Bennett, T. D.; Coudert, F. X.; James, S. L.; Cooper, A. I. The Changing State of Porous Materials. Nat. Mater. 2021, 20 (9), 1179– 1187,  DOI: 10.1038/s41563-021-00957-w
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    12
    The changing state of porous materials
    Bennett, Thomas D.; Coudert, Francois-Xavier; James, Stuart L.; Cooper, Andrew I.
    Nature Materials (2021), 20 (9), 1179-1187CODEN: NMAACR; ISSN:1476-1122. (Nature Portfolio)
    A review. Porous materials contain regions of empty space into which guest mols. can be selectively adsorbed and sometimes chem. transformed. This has made them useful in both industrial and domestic applications, ranging from gas sepn., energy storage and ion exchange to heterogeneous catalysis and green chem. Porous materials are often ordered (cryst.) solids. Order-or uniformity-is frequently held to be advantageous, or even pivotal, to our ability to engineer useful properties in a rational way. Here we highlight the growing evidence that topol. disorder can be useful in creating alternative properties in porous materials. In particular, we highlight here several concepts for the creation of novel porous liqs., rationalize routes to porous glasses and provide perspectives on applications for porous liqs. and glasses.
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  13. 13
    Egleston, B. D.; Mroz, A.; Jelfs, K. E.; Greenaway, R. L. Porous Liquids - the Future Is Looking Emptier. Chem. Sci. 2022, 13, 5042– 5054,  DOI: 10.1039/D2SC00087C
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    13
    Porous liquids - the future is looking emptier
    Egleston, Benjamin D.; Mroz, Austin; Jelfs, Kim E.; Greenaway, Rebecca L.
    Chemical Science (2022), 13 (18), 5042-5054CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
    The development of microporosity in the liq. state is leading to an inherent change in the way we approach applications of functional porosity, potentially allowing access to new processes by exploiting the fluidity of these new materials. By engineering permanent porosity into a liq., over the transient intermol. porosity in all liqs., it is possible to design and form a porous liq. Since the concept was proposed in 2007, and the first examples realized in 2015, the field has seen rapid advances among the types and nos. of porous liqs. developed, our understanding of the structure and properties, as well as improvements in gas uptake and mol. sepns. However, despite these recent advances, the field is still young, and with only a few applications reported to date, the potential that porous liqs. have to transform the field of microporous materials remains largely untapped. In this review, we will explore the theory and conception of porous liqs. and cover major advances in the area, key exptl. characterization techniques and computational approaches that have been employed to understand these systems, and summarise the investigated applications of porous liqs. that have been presented to date. We also outline an emerging discovery workflow with recommendations for the characterization required at each stage to both confirm permanent porosity and fully understand the phys. properties of the porous liq.
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  14. 14
    Canivet, J.; Fateeva, A.; Guo, Y.; Coasne, B.; Farrusseng, D. Water Adsorption in MOFs: Fundamentals and Applications. Chem. Soc. Rev. 2014, 43 (16), 5594– 5617,  DOI: 10.1039/C4CS00078A
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    14
    Water adsorption in MOFs: fundamentals and applications
    Canivet, Jerome; Fateeva, Alexandra; Guo, Youmin; Coasne, Benoit; Farrusseng, David
    Chemical Society Reviews (2014), 43 (16), 5594-5617CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    A review. This review article presents the fundamental and practical aspects of water adsorption in Metal-Org. Frameworks (MOFs). The state of the art of MOF stability in water, a crucial issue to many applications in which MOFs are promising candidates, is discussed here. Stability in both gaseous (such as humid gases) and aq. media is considered. By considering a non-exhaustive yet representative set of MOFs, the different mechanisms of water adsorption in this class of materials are presented: reversible and continuous pore filling, irreversible and discontinuous pore filling through capillary condensation, and irreversibility arising from the flexibility and possible structural modifications of the host material. Water adsorption properties of more than 60 MOF samples are reported. The applications of MOFs as materials for heat-pumps and adsorbent-based chillers and proton conductors are also reviewed. Some directions for future work are suggested as concluding remarks.
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  15. 15
    Rangnekar, N.; Mittal, N.; Elyassi, B.; Caro, J.; Tsapatsis, M. Zeolite Membranes - a Review and Comparison with MOFs. Chem. Soc. Rev. 2015, 44 (20), 7128– 7154,  DOI: 10.1039/C5CS00292C
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    15
    Zeolite membranes - a review and comparison with MOFs
    Rangnekar, N.; Mittal, N.; Elyassi, B.; Caro, J.; Tsapatsis, M.
    Chemical Society Reviews (2015), 44 (20), 7128-7154CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    The latest developments in zeolite membranes are reviewed, with an emphasis on the synthesis techniques, including seed assembly and secondary growth methods. This review also discusses the current industrial applications of zeolite membranes, the feasibility of their use in membrane reactors and their hydrothermal stability. Finally, zeolite membranes are compared with metal-org. framework (MOF) membranes and the latest advancements in MOF and mixed matrix membranes are highlighted.
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  16. 16
    Alexiadis, A.; Kassinos, S. Molecular Simulation of Water in Carbon Nanotubes. Chem. Rev. 2008, 108 (12), 5014– 5034,  DOI: 10.1021/cr078140f
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    16
    Molecular Simulation of Water in Carbon Nanotubes
    Alexiadis, Alessio; Kassinos, Stavros
    Chemical Reviews (Washington, DC, United States) (2008), 108 (12), 5014-5034CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. The authors review the recent advances in the area of mol. dynamics of water in carbon nanotubes. It is shown that many properties of confined water differ from those of bulk water and depend on the nanotube size. Due to the effect of confinement, the phase diagram of water gains a new dimension (the nanotube diam.). All the water models available are parametrized for bulk water and it is not known how reliable they are in the case of confined water. Results obtained with different water models provide different pictures of the structure of the water layers. Ab initio calcns. can represent the optimal answer since they are based on first principles and do not require any parametrized force fields.
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  17. 17
    Barboiu, M. Artificial Water Channels. Angew. Chem., Int. Ed. 2012, 51 (47), 11674– 11676,  DOI: 10.1002/anie.201205819
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    17
    Artificial Water Channels
    Barboiu, Mihail
    Angewandte Chemie, International Edition (2012), 51 (47), 11674-11676CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. Water is fundamental to life, playing a variety of roles related to its complex dynamic behavior at the supramol. level. Most physiol. processes depend on the selective exchange of ions or mols. between a cell and its environment, with water serving a crucial function in these translocation events. Artificial ion channels have been extensively studied with the goal of facilitating ionic conduction in bilayer membranes; however, there has not been as much progress in the area of synthetic water channels. Several artificial water channel systems have been reported to date, and these include the following: (1) helical pores assembled from dendritic peptides; (2) a chiral supramol. imidazole (I)-quartet assembled from lipophilic ureidoimidazole; and (3) polyazide-substituted pillar[5]arenes assembled into tubular hydrogen-bonded superstructures.
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  18. 18
    Clayson, I. G.; Hewitt, D.; Hutereau, M.; Pope, T.; Slater, B. High Throughput Methods in the Synthesis, Characterization, and Optimization of Porous Materials. Adv. Mater. 2020, 32 (44), 1– 47,  DOI: 10.1002/adma.202002780
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    There is no corresponding record for this reference.
  19. 19
    Lynch, C. I.; Rao, S.; Sansom, M. S. P. Water in Nanopores and Biological Channels: A Molecular Simulation Perspective. Chem. Rev. 2020, 120 (18), 10298– 10335,  DOI: 10.1021/acs.chemrev.9b00830
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    19
    Water in Nanopores and Biological Channels: A Molecular Simulation Perspective
    Lynch, Charlotte I.; Rao, Shanlin; Sansom, Mark S. P.
    Chemical Reviews (Washington, DC, United States) (2020), 120 (18), 10298-10335CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. This Review explores the dynamic behavior of water within nanopores and biol. channels in lipid bilayer membranes. We focus on mol. simulation studies, alongside selected structural and other exptl. investigations. Structures of biol. nanopores and channels are reviewed, emphasizing those high-resoln. crystal structures, which reveal water mols. within the transmembrane pores, which can be used to aid the interpretation of simulation studies. Different levels of mol. simulations of water within nanopores are described, with a focus on mol. dynamics (MD). In particular, models of water for MD simulations are discussed in detail to provide an evaluation of their use in simulations of water in nanopores. Simulation studies of the behavior of water in idealized models of nanopores have revealed aspects of the organization and dynamics of nanoconfined water, including wetting/dewetting in narrow hydrophobic nanopores. A survey of simulation studies in a range of nonbiol. nanopores is presented, including carbon nanotubes, synthetic nanopores, model peptide nanopores, track-etched nanopores in polymer membranes, and hydroxylated and functionalized nanoporous silica. These reveal a complex relationship between pore size/geometry, the nature of the pore lining, and rates of water transport. Wider nanopores with hydrophobic linings favor water flow whereas narrower hydrophobic pores may show dewetting. Simulation studies over the past decade of the behavior of water in a range of biol. nanopores are described, including porins and β-barrel protein nanopores, aquaporins and related polar solute pores, and a no. of different classes of ion channels. Water is shown to play a key role in proton transport in biol. channels and in hydrophobic gating of ion channels. An overall picture emerges, whereby the behavior of water in a nanopore may be predicted as a function of its hydrophobicity and radius. This informs our understanding of the functions of diverse channel structures and will aid the design of novel nanopores. Thus, our current level of understanding allows for the design of a nanopore which promotes wetting over dewetting or vice versa. However, to design a novel nanopore, which enables fast, selective, and gated flow of water de novo would remain challenging, suggesting a need for further detailed simulations alongside exptl. evaluation of more complex nanopore systems.
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  20. 20
    Levy, Y.; Onuchic, J. N. Water Mediation in Protein Folding and Molecular Recognition. Annu. Rev. Biophys. Biomol. Struct. 2006, 35 (1), 389– 415,  DOI: 10.1146/annurev.biophys.35.040405.102134
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    20
    Water mediation in protein folding and molecular recognition
    Levy, Yaakov; Onuchic, Jose N.
    Annual Review of Biophysics and Biomolecular Structure (2006), 35 (), 389-415CODEN: ABBSE4; ISSN:1056-8700. (Annual Reviews Inc.)
    A review. Water is essential for life in many ways, and without it biomols. might no longer truly be biomols. In particular, water is important to the structure, stability, dynamics, and function of biol. macromols. In protein folding, water mediates the collapse of the chain and the search for the native topol. through a funneled energy landscape. Water actively participates in mol. recognition by mediating the interactions between binding partners and contributes to either enthalpic or entropic stabilization. Accordingly, water must be included in recognition and structure prediction codes to capture specificity. Thus, water should not be treated as an inert environment, but rather as an integral and active component of biomol. systems, where it has both dynamic and structural roles. Focusing on water sheds light on the physics and function of biol. machinery and self-assembly and may advance the understanding of the natural design of proteins and nucleic acids.
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  21. 21
    Yin, H.; Hummer, G.; Rasaiah, J. C. Metastable Water Clusters in the Nonpolar Cavities of the Thermostable Protein Tetrabrachion. J. Am. Chem. Soc. 2007, 129 (23), 7369– 7377,  DOI: 10.1021/ja070456h
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    21
    Metastable Water Clusters in the Nonpolar Cavities of the Thermostable Protein Tetrabrachion
    Yin, Hao; Hummer, Gerhard; Rasaiah, Jayendran C.
    Journal of the American Chemical Society (2007), 129 (23), 7369-7377CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Water expulsion from the protein core is a key step in protein folding. Nevertheless, unusually large water clusters confined into the nonpolar cavities have been obsd. in the x-ray crystal structures of tetrabrachion, a bacterial protein that is thermostable up to at least 403 K (130°). Here, we use mol. dynamics (MD) simulations to investigate the structure and thermodn. of water filling the largest cavity of the right-handed coiled-coil stalk of tetrabrachion at 365 K (92°), the temp. of optimal bacterial growth, and at room temp. (298 K). Hydrogen-bonded water clusters of seven to nine water mols. are found to be thermodynamically stable in this cavity at both temps., confirming the x-ray studies. Stability, as measured by the transfer free energy of the optimal size cluster, decreases with increasing temp. Water filling is thus driven by the energy of transfer and opposed by the transfer entropy, both depending only weakly on temp. Our calcns. suggest that cluster formation becomes unfavorable at ∼384 K (110°), signaling the onset of drying just slightly above the temp. of optimal growth. "Drying" thus precedes protein denaturation. At room temp., the second largest cavity in tetrabrachion accommodates a five water mol. cluster, as reported in the x-ray studies. However, the simulations show that at 365 K the cluster is unstable and breaks up. We suggest that the large hydrophobic cavities may act as binding sites for two proteases, possibly explaining the unusual thermostability of the resulting protease-stalk complexes (up to ∼393 K, 120°).
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  22. 22
    Chatzichristos, A.; Hassan, J. Current Understanding of Water Properties inside Carbon Nanotubes. Nanomaterials 2022, 12 (1), 174,  DOI: 10.3390/nano12010174
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    22
    Current Understanding of Water Properties inside Carbon Nanotubes
    Chatzichristos, Aris; Hassan, Jamal
    Nanomaterials (2022), 12 (1), 174CODEN: NANOKO; ISSN:2079-4991. (MDPI AG)
    A review. Confined water inside carbon nanotubes (CNTs) has attracted a lot of attention in recent years, amassing as a result a very large no. of dedicated studies, both theor. and exptl. This exceptional scientific interest can be understood in terms of the exotic properties of nanoconfined water, as well as the vast array of possible applications of CNTs in a wide range of fields stretching from geol. to medicine and biol. This review presents an overreaching narrative of the properties of water in CNTs, based mostly on results from systematic NMR (NMR) and mol. dynamics (MD) studies, which together allow the untangling and explanation of many seemingly contradictory results present in the literature. Further, we identify still-debatable issues and open problems, as well as avenues for future studies, both theor. and exptl.
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  23. 23
    Mochizuki, K.; Koga, K.; Sastry, S. Solid-Liquid Critical Behavior of Water in Nanopores. Proc. Natl. Acad. Sci. U.S.A. 2015, 112 (27), 8221– 8226,  DOI: 10.1073/pnas.1422829112
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    23
    Solid-liquid critical behavior of water in nanopores
    Mochizuki, Kenji; Koga, Kenichiro
    Proceedings of the National Academy of Sciences of the United States of America (2015), 112 (27), 8221-8226CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
    Nanoconfined liq. water can transform into low-dimensional ices whose cryst. structures are dissimilar to any bulk ices and whose m.p. may significantly rise with reducing the pore size, as revealed by computer simulation and confirmed by expt. One of the intriguing, and as yet unresolved, questions concerns the observation that the liq. water may transform into a low-dimensional ice either via a first-order phase change or without any discontinuity in thermodn. and dynamic properties, which suggests the existence of solid-liq. crit. points in this class of nanoconfined systems. Here we explore the phase behavior of a model of water in carbon nanotubes in the temp.-pressure-diam. space by mol. dynamics simulation and provide unambiguous evidence to support solid-liq. crit. phenomena of nanoconfined water. Solid-liq. first-order phase boundaries are detd. by tracing spontaneous phase sepn. at various temps. All of the boundaries eventually cease to exist at the crit. points and there appear loci of response function maxima, or the Widom lines, extending to the supercrit. region. The finite-size scaling anal. of the d. distribution supports the presence of both first-order and continuous phase changes between solid and liq. At around the Widom line, there are microscopic domains of two phases, and continuous solid-liq. phase changes occur in such a way that the domains of one phase grow and those of the other evanesce as the thermodn. state departs from the Widom line.
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  24. 24
    Bushuev, Y. G.; Sastre, G. Atomistic Simulation of Water Intrusion-Extrusion in ITQ-4 (IFR) and ZSM-22 (TON): The Role of Silanol Defects. J. Phys. Chem. C 2011, 115 (44), 21942– 21953,  DOI: 10.1021/jp207020w
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    24
    Atomistic Simulation of Water Intrusion-Extrusion in ITQ-4 (IFR) and ZSM-22 (TON): The Role of Silanol Defects
    Bushuev, Yuriy G.; Sastre, German
    Journal of Physical Chemistry C (2011), 115 (44), 21942-21953CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
    Water in pure silica zeolites (zeosils) may behave as a bumper by absorbing mech. energy of the intruded water, as a spring by restoring after extrusion of the energy spent in intrusion, or as shock absorber by dissipating the energy. The understanding of how the structure and topol. of the zeosils are responsible of such behavior has not yet been fully clarified. Mol. dynamics and mol. mechanics simulations of IFR- and TON-type zeosils were performed in an attempt to elucidate the energetics of these materials after water intrusion-extrusion. The authors aim the simulations to capture the exptl. obsd. bumper and spring water-zeosil behavior of IFR and TON, resp. The excess energy with respect to dry zeosil was calcd., and this relates to the energetic response of the zeosil after water intrusion. The excess energy of water-TON is larger than the energy of bulk water at any loading. The small opening of the TON channel prevents the formation of energetically stable bulky water clusters. The water content is stabilized on a certain loading range in water-IFR. Any silanol defects in IFR framework channels stabilize systems. Defect positions (silanol groups), which make the water-IFR system energetically stable, are found. Silanol groups increase the hydrophilicity of IFR-type zeosil, initially hydrophobic. There are two factors explaining the bumper behavior (under high pressure, water penetrates into the zeosil channels and remains there even after the pressure is released) of water-IFR systems: channel size and hydrolisis leading to framework breaking under large hydrostatic pressure. Silanol groups in channels are centers of water clusterization. The chem. stability of TON framework and its small channel size explain its spring behavior.
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  25. 25
    Karbowiak, T.; Saada, M. A.; Rigolet, S.; Ballandras, A.; Weber, G.; Bezverkhyy, I.; Soulard, M.; Patarin, J.; Bellat, J. P. New Insights in the Formation of Silanol Defects in Silicalite-1 by Water Intrusion under High Pressure. Phys. Chem. Chem. Phys. 2010, 12 (37), 11454– 11466,  DOI: 10.1039/c000931h
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    25
    New insights in the formation of silanol defects in silicalite-1 by water intrusion under high pressure
    Karbowiak, Thomas; Saada, Mohamed-Ali; Rigolet, Severinne; Ballandras, Anthony; Weber, Guy; Bezverkhyy, Igor; Soulard, Michel; Patarin, Joel; Bellat, Jean-Pierre
    Physical Chemistry Chemical Physics (2010), 12 (37), 11454-11466CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
    The water-silicalite-1" system is known to act as a mol. spring. The successive intrusion-extrusion cycles of liq. water in small crystallites (6 × 3 × 0.5 μm3) of hydrophobic silicalite-1 were studied by volumetric and calorimetric techniques. The expts. displayed a decrease of the intrusion pressure between the 1st intrusion-extrusion cycle and the consecutive ones, whereas the extrusion pressures remained unchanged. However, neither XRD studies nor SEM observations revealed any structural and morphol. modifications of silicalite-1 at the long-range order. Such a shift in the value of the intrusion pressure after the 1st water intrusion-extrusion cycle is attributed to the creation of silanol groups during the 1st water intrusion. Detailed FTIR and solid-state NMR spectroscopic characterizations provided a mol. evidence of chem. modification of zeolite framework with the formation of local silanol defects created by the breaking of siloxane bonds.
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  26. 26
    Narayan, R.; Nayak, U. Y.; Raichur, A. M.; Garg, S. Mesoporous Silica Nanoparticles: A Comprehensive Review on Synthesis and Recent Advances. Pharmaceutics 2018, 10 (3), 118– 149,  DOI: 10.3390/pharmaceutics10030118
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    26
    Mesoporous silica nanoparticles: a comprehensive review on synthesis and recent advances
    Narayan, Reema; Nayak, Usha Y.; Raichur, Ashok M.; Garg, Sanjay
    Pharmaceutics (2018), 10 (3), 118CODEN: PHARK5; ISSN:1999-4923. (MDPI AG)
    Recent advancements in drug delivery technologies utilizing a variety of carriers have resulted in a path-breaking revolution in the approach towards diagnosis and therapy alike in the current times. Need for materials with high thermal, chem. and mech. properties have led to the development of mesoporous silica nanoparticles (MSNs). These ordered porous materials have garnered immense attention as drug carriers owing to their distinctive features over the others. They can be synthesized using a relatively simple process, thus making it cost effective. Moreover, by controlling the parameters during the synthesis; the morphol., pore size and vol. and particle size can be transformed accordingly. Over the last few years, a rapid increase in research on MSNs as drug carriers for the treatment of various diseases has been obsd. indicating its potential benefits in drug delivery. Their widespread application for the loading of small mols. as well as macromols. such as proteins, siRNA and so forth, has made it a versatile carrier. In the recent times, researchers have sorted to several modifications in the framework of MSNs to explore its potential in drug resistant chemotherapy, antimicrobial therapy. In this review, we have discussed the synthesis of these multitalented nanoparticles and the factors influencing the size and morphol. of this wonder carrier. The second part of this review emphasizes on the applications and the advances made in the MSNs to broaden the spectrum of its use esp. in the field of biomedicine. We have also touched upon the lacunae in the thorough understanding of its interaction with a biol. system which poses a major hurdle in the passage of this carrier to the clin. level. In the final part of this review, we have discussed some of the major patents filed in the field of MSNs for therapeutic purpose.
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  27. 27
    Ahmadi, F.; Sodagar-Taleghani, A.; Ebrahimnejad, P.; Pouya Hadipour Moghaddam, S.; Ebrahimnejad, F.; Asare-Addo, K.; Nokhodchi, A. A Review on the Latest Developments of Mesoporous Silica Nanoparticles as a Promising Platform for Diagnosis and Treatment of Cancer. Int. J. Pharm. 2022, 625 (March), 122099,  DOI: 10.1016/j.ijpharm.2022.122099
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    27
    A review on the latest developments of mesoporous silica nanoparticles as a promising platform for diagnosis and treatment of cancer
    Ahmadi, Fatemeh; Sodagar-Taleghani, Arezoo; Ebrahimnejad, Pedram; Pouya Hadipour Moghaddam, Seyyed; Ebrahimnejad, Farzam; Asare-Addo, Kofi; Nokhodchi, Ali
    International Journal of Pharmaceutics (Amsterdam, Netherlands) (2022), 625 (), 122099CODEN: IJPHDE; ISSN:0378-5173. (Elsevier B.V.)
    A review. Cancer is the second cause of human mortality after cardiovascular disease around the globe. Conventional cancer therapies are chemotherapy, radiation, and surgery. In fact, due to the lack of abs. specificity and high drug concns., early recognition and treatment of cancer with conventional approaches have become challenging issues in the world. To mitigate against the limitations of conventional cancer chemotherapy, nanomaterials have been developed. Nanomaterials exhibit particular properties that can overcome the drawbacks of conventional therapies such as lack of specificity, high drug concns., and adverse drug reactions. Among nanocarriers, mesoporous silica nanoparticles (MSNs) have gained increasing attention due to their well-defined pore size and structure, high surface area, good biocompatibility and biodegradability, ease of surface modification, and stable aq. dispersions. This review highlights the current progress with the use of MSNs for the delivery of chemotherapeutic agents for the diagnosis and treatment of cancer. Various stimuli-responsive gatekeepers, which endow the MSNs with on-demand drug delivery, surface modification strategies for targeting purposes, and multifunctional MSNs utilized in drug delivery systems (DDSs) are also addressed. Also, the capability of MSNs as flexible imaging platforms is considered. In addn., physicochem. attributes of MSNs and their effects on cancer therapy with a particular focus on recent studies is emphasized. Moreover, major challenges to the use of MSNs for cancer therapy, biosafety and cytotoxicity aspects of MSNs are discussed.
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  28. 28
    Lefevre, B.; Saugey, A.; Barrat, J. L.; Bocquet, L.; Charlaix, E.; Gobin, P. F.; Vigier, G. Intrusion and Extrusion of Water in Hydrophobic Mesopores. J. Chem. Phys. 2004, 120 (10), 4927– 4938,  DOI: 10.1063/1.1643728
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    28
    Intrusion and extrusion of water in hydrophobic mesopores
    Lefevre, B.; Saugey, A.; Barrat, J. L.; Bocquet, L.; Charlaix, E.; Gobin, P. F.; Vigier, G.
    Journal of Chemical Physics (2004), 120 (10), 4927-4938CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
    We present exptl. and theor. results on intrusion-extrusion cycles of water in hydrophobic mesoporous materials, characterized by independent cylindrical pores. The intrusion, which takes place above the bulk satn. pressure, can be well described using a macroscopic capillary model. Once the material is satd. with water, extrusion takes place upon redn. of the externally applied pressure. Our results for the extrusion pressure can only be understood by assuming that the limiting extrusion mechanism is the nucleation of a vapor bubble inside the pores. A comparison of calcd. and exptl. nucleation pressures shows that a proper inclusion of line tension effects is necessary to account for the obsd. values of nucleation barriers. Neg. line tensions of order 10-11 J m-1 are found for our system, in reasonable agreement with other exptl. ests. of this quantity.
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  29. 29
    Guillemot, L.; Biben, T.; Galarneau, A.; Vigier, G.; Charlaix, É. Activated Drying in Hydrophobic Nanopores and the Line Tension of Water. Proc. Natl. Acad. Sci. U.S.A. 2012, 109 (48), 19557– 19562,  DOI: 10.1073/pnas.1207658109
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    29
    Activated drying in hydrophobic nanopores and the line tension of water
    Guillemot, Ludivine; Biben, Thierry; Galarneau, Anne; Vigier, Gerard; Charlaix, Elisabeth
    Proceedings of the National Academy of Sciences of the United States of America (2012), 109 (48), 19557-19562, S19557/1-S19557/5CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
    Slow dynamics of water evapn. out of hydrophobic cavities has been studied by using model porous silica materials grafted with octylsilanes. The cylindrical pores were monodisperse, with a radius in the range of 1-2 nm. Liq. water penetrated into the nanopores at high pressure and emptied the pores when the pressure was lowered. The drying pressure exhibited a logarithmic growth as a function of the driving rate over more than three decades, showing the thermally activated nucleation of vapor bubbles. The slow dynamics and the crit. vol. of the vapor nucleus were quant. described by the classical theory of capillarity without adjustable parameter. The classical capillarity overestimated the crit. bubble energy. Possible effect of surface heterogeneities, long-range interactions, and high-curvature effects is discussed, and it is shown that a classical theory can describe vapor nucleation provided that a neg. line tension is taken into account. The drying pressure then provides a detn. of this line tension with much higher precision than currently available methods. The authors found consistent values of the order of -30 pN in a variety of hydrophobic materials.
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  30. 30
    Amabili, M.; Grosu, Y.; Giacomello, A.; Meloni, S.; Zaki, A.; Bonilla, F.; Faik, A.; Casciola, C. M. Pore Morphology Determines Spontaneous Liquid Extrusion from Nanopores. ACS Nano 2019, 13 (2), 1728,  DOI: 10.1021/acsnano.8b07818
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    30
    Pore Morphology Determines Spontaneous Liquid Extrusion from Nanopores
    Amabili, Matteo; Grosu, Yaroslav; Giacomello, Alberto; Meloni, Simone; Zaki, Abdelali; Bonilla, Francisco; Faik, Abdessamad; Casciola, Carlo Massimo
    ACS Nano (2019), 13 (2), 1728-1738CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
    In this contribution we explore by means of expts., theory, and mol. dynamics the effect of pore morphol. on the spontaneous extrusion of nonwetting liqs. from nanopores. Understanding and controlling this phenomenon is central for manipulating nanoconfined liqs., e.g., in nanofluidic applications, drug delivery, and oil extn. Qual. different extrusion behaviors were obsd. in high-pressure water intrusion-extrusion expts. on porous materials with similar nominal diam. and hydrophobicity: macroscopic capillary models and mol. dynamics simulations revealed that the very presence or absence of extrusion is connected to the internal morphol. of the pores and, in particular, to the presence of small-scale roughness or pore interconnections. Addnl. expts. with mercury confirmed that this mechanism is generic for nonwetting liqs. and is rooted in the pore topol. The present results suggest a rational way to engineer heterogeneous systems for energy and nanofluidic applications in which the extrusion behavior can be controlled via the pore morphol.
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  31. 31
    Bushuev, Y. G.; Grosu, Y.; Chorążewski, M. A.; Meloni, S. Effect of the Topology on Wetting and Drying of Hydrophobic Porous Materials. ACS Appl. Mater. Interfaces 2022, 14 (26), 30067– 30079,  DOI: 10.1021/acsami.2c06039
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    31
    Effect of the Topology on Wetting and Drying of Hydrophobic Porous Materials
    Bushuev, Yuriy G.; Grosu, Yaroslav; Chorazewski, Miroslaw A.; Meloni, Simone
    ACS Applied Materials & Interfaces (2022), 14 (26), 30067-30079CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Establishing mol. mechanisms of wetting and drying of hydrophobic porous materials is a general problem for science and technol. within the subcategories of the theory of liqs., chromatog., nanofluidics, energy storage, recuperation, and dissipation. In this article, we demonstrate a new way to tackle this problem by exploring the effect of the topol. of pure silica nanoparticles, nanotubes, and zeolites. Using mol. dynamics simulations, we show how secondary porosity promotes the intrusion of water into micropores and affects the hydrophobicity of materials. It is demonstrated herein that for nano-objects, the hydrophobicity can be controlled by changing the ratio of open to closed nanometer-sized lateral pores. This effect can be exploited to produce new materials for practical applications when the hydrophobicity needs to be regulated without significantly changing the chem. or structure of the materials. Based on these simulations and theor. considerations, for pure silica zeolites, we examd. and then classified the exptl. database of intrusion pressures, thus leading to the prediction of any zeolite's intrusion pressure. We show a correlation between the intrusion pressure and the ratio of the accessible pore surface area to total pore vol. The correlation is valid for some zeolites and mesoporous materials. It can facilitate choosing prospective candidates for further investigation and possible exploitation, esp. for energy storage, recuperation, and dissipation.
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  32. 32
    Bushuev, Y. G.; Grosu, Y.; Chora̧żewski, M. A.; Meloni, S. Subnanometer Topological Tuning of the Liquid Intrusion/Extrusion Characteristics of Hydrophobic Micropores. Nano Lett. 2022, 22 (6), 2164– 2169,  DOI: 10.1021/acs.nanolett.1c02140
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    32
    Subnanometer Topological Tuning of the Liquid Intrusion/Extrusion Characteristics of Hydrophobic Micropores
    Bushuev, Yuriy G.; Grosu, Yaroslav; Chorazewski, Miroslaw A.; Meloni, Simone
    Nano Letters (2022), 22 (6), 2164-2169CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
    Intrusion(wetting)/extrusion(drying) of liqs. in/from lyophobic nanoporous systems is key in many fields, including chromatog., nanofluidics, biol. and energy materials. Here we demonstrate that secondary topol. features decorating main channels of porous systems dramatically affect the intrusion/extrusion cycle. These secondary features, allowing an unexpected bridging with liq. in the surrounding domains, stabilize the water stream intruding a micropore. This reduces the intrusion/extrusion barrier and the corresponding pressures without altering other properties of the system. Tuning the intrusion/extrusion pressures via subnanometric topol. features represent a yet unexplored strategy for designing hydrophobic micropores. Though energy is not the only field of application, here we show that the proposed tuning approach may bring 20-75 MPa of intrusion-extrusion pressure increase, expanding the applicability of hydrophobic microporous materials.
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  33. 33
    Huang, L. B.; Di Vincenzo, M.; Li, Y.; Barboiu, M. Artificial Water Channels: Towards Biomimetic Membranes for Desalination. Chem.─Eur. J. 2021, 27 (7), 2224– 2239,  DOI: 10.1002/chem.202003470
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    33
    Artificial Water Channels: Towards Biomimetic Membranes for Desalination
    Huang, Li-Bo; Di Vincenzo, Maria; Li, Yuhao; Barboiu, Mihail
    Chemistry - A European Journal (2021), 27 (7), 2224-2239CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. Natural Aquaporin (AQP) channels are efficient water translocating proteins, rejecting ions. Inspired by this masterpiece of nature, Artificial Water Channels (AWCs) with controlled functional structures, can be potentially used to mimic the AQPs to a certain extent, offering flexible avenues toward biomimetic membranes for water purifn. The objective of this paper is to trace the historical development and significant advancements of current reported AWCs. Meanwhile, we attempt to reveal important structural insights and supramol. self-assembly principles governing the selective water transport mechanisms, toward innovative AWC-based biomimetic membranes for desalination.
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  34. 34
    Berne, B. J.; Weeks, J. D.; Zhou, R. Dewetting and Hydrophobic Interaction in Physical and Biological Systems. Annu. Rev. Phys. Chem. 2009, 60, 85– 103,  DOI: 10.1146/annurev.physchem.58.032806.104445
    Google Scholar
    34
    Dewetting and hydrophobic interaction in physical and biological systems
    Berne, Bruce J.; Weeks, John D.; Zhou, Ruhong
    Annual Review of Physical Chemistry (2009), 60 (), 85-103CODEN: ARPLAP; ISSN:0066-426X. (Annual Reviews Inc.)
    A review. Hydrophobicity manifests itself differently on large and small length scales. This review focuses on large-length-scale hydrophobicity, particularly on dewetting at single hydrophobic surfaces and drying in regions bounded on two or more sides by hydrophobic surfaces. We review applicable theories, simulations, and expts. pertaining to large-scale hydrophobicity in phys. and biomol. systems and clarify some of the crit. issues pertaining to this subject. Given space constraints, we cannot review all the significant and interesting work in this active field.
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  35. 35
    Sen, S.; Risbud, S. H.; Bartl, M. H. Thermodynamic and Kinetic Transitions of Liquids in Nanoconfinement. Acc. Chem. Res. 2020, 53 (12), 2869– 2878,  DOI: 10.1021/acs.accounts.0c00502
    Google Scholar
    35
    Thermodynamic and Kinetic Transitions of Liquids in Nanoconfinement
    Sen, Sabyasachi; Risbud, Subhash H.; Bartl, Michael H.
    Accounts of Chemical Research (2020), 53 (12), 2869-2878CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
    Conspectus: Core principles of chem. are ubiquitously invoked to shed light on the nature of mol. level interactions in nanoconfined fluids, which play a pivotal role in a wide range of processes in geochem., biol., and engineering. A detailed understanding of the physicochem. processes involved in the flow, structural transitions, and freezing or melting behavior of fluids confined within nanometer-sized pores of solid materials is thus of enormous importance for both basic research and technol. applications. This Account provides a perspective on new insights into the thermodn. and kinetic transitions of nanoconfined fluids in their stable and metastable forms. After briefly introducing the unique properties of mesoporous silicas from the SBA, MCM, and FDU families that serve as the confinement matrixes, combining highly ordered single and bimodal mesopore architectures with tunable pore sizes in the ~ 2-15 nm range and narrow size distributions, recent studies on melting/freezing behavior of water confined in these host matrixes are reviewed. While differential scanning calorimetry (DSC) reveals a linear relationship between m.p. depression and pore size (independent of the pore shape), as predicted by the Gibbs-Thomson relation, variable temp. 2H wide-line NMR spectroscopy studies confirm the core-shell model of water and give evidence for a layer-by-layer freezing mechanism, which gives rise to an apparent fragile-to-strong transition in the solidification dynamics. In contrast to the freezing/melting behavior of water, the effect of nanoconfinement on the glass transition of supercooled liqs. is nonuniversal and the glass transition temp. Tg can either increase or decrease with the dimensionality and extent of confinement. This nonuniversal behavior is exemplified by the two glass-forming mol. liqs., glycerol and ortho-terphenyl (OTP). While glycerol shows an increase in Tg and a pronounced slowdown of the rotational dynamics of the constituent mols. due to a change in the mol. packing between the bulk and the confined liq., OTP displays a linear and confining-media-dependent depression of Tg with increased confinement that is strongly influenced by the pore-liq. interface characteristics. This Account concludes with a focus on recent exptl. evidence of extreme spatial and dynamical heterogeneity in both freezing and glass transition processes. This discovery was enabled by the unique mesoporous structures of SBA-16 and FDU-5, possessing bimodal architectures with two interconnected pore types of different size and shape (spherical and cylindrical). For the very first time, two m.ps. for water and two glass transitions for supercooled OTP, corresponding to a specific pore type, were obsd. Collectively, these observations strongly suggest a close mechanistic connection between the local fluctuations in the structure and dynamics of nanoconfined liqs. While the findings reviewed in this Account provide new insights into thermodn. and kinetic transitions of fluids, there remain many unanswered questions regarding the effects of nanoconfinement on the fundamental properties of fluids, which offer exciting future opportunities in chem. research.
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  36. 36
    Ronchi, L.; Patarin, J.; Nouali, H.; Daou, T. J.; Ryzhikov, A. Structure Influence on High-Pressure Water Intrusion in Pure Silica Zeolites. New J. Chem. 2024,  DOI: 10.1039/D3NJ03991A
    Google Scholar
    There is no corresponding record for this reference.
  37. 37
    Leung, K.; Nielsen, I. M. B.; Criscenti, L. J. Elucidating the Bimodal Acid-Base Behavior of the Water-Silica Interface from First Principles. J. Am. Chem. Soc. 2009, 131 (51), 18358– 18365,  DOI: 10.1021/ja906190t
    Google Scholar
    37
    Elucidating the Bimodal Acid-Base Behavior of the Water-Silica Interface from First Principles
    Leung, Kevin; Nielsen, Ida M. B.; Criscenti, Louise J.
    Journal of the American Chemical Society (2009), 131 (51), 18358-18365CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Understanding the acid-base behavior of silica surfaces is crit. for many nanoscience and bionano interface applications. Silanol groups (SiOH) on silica surfaces exhibit two acidity consts.-one as acidic as vinegar-but their structural basis remains controversial. The at. details of the more acidic silanol site govern not just the overall surface charge d. at near neutral soln. pH but also how ions and biomols. interact with and bind to silica immersed in water. Using ab initio mol. dynamics simulations and multiple representative cryst. silica surfaces, the authors det. the deprotonation free energies of silanol groups with different structural motifs. Previously proposed motifs related to chem. connectivity or intersilanol hydrogen bonds do not yield high acidity. Instead, a plausible candidate for pKa = 4.5 silanol groups may be found in locally strained or defected regions with sparse silanol coverage. In the process, irreversible ring-opening reactions of strained silica trimer rings in contact with liq. water are obsd.
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  38. 38
    Lopes, P. E. M.; Murashov, V.; Tazi, M.; Demchuk, E.; Mackerell, A. D. Development of an Empirical Force Field for Silica. Application to the Quartz-Water Interface. J. Phys. Chem. B 2006, 110 (6), 2782– 2792,  DOI: 10.1021/jp055341j
    Google Scholar
    38
    Development of an Empirical Force Field for Silica. Application to the Quartz-Water Interface
    Lopes, Pedro E. M.; Murashov, Vladimir; Tazi, Mouhsine; Demchuk, Eugene; MacKerell, Alexander D., Jr.
    Journal of Physical Chemistry B (2006), 110 (6), 2782-2792CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)
    Interactions of pulverized cryst. silica with biol. systems, including the lungs, cause cell damage, inflammation, and apoptosis. To allow computational atomistic modeling of these pathogenic processes, including interactions between silica surfaces and biol. mols., new parameters for quartz, compatible with the CHARMM empirical force field were developed. Parameters were optimized to reproduce the exptl. geometry of α-quartz, ab initio vibrational spectra, and interactions between model compds. and water. The newly developed force field was used to study interactions of water with two singular surfaces of α-quartz, (011) and (100). Properties monitored and analyzed include the variation of the d. of water mols. in the plane perpendicular to the surface, disruption of the water H-bond network upon adsorption, and space-time correlations of water oxygen atoms in terms of Van Hove self-correlation functions. The vibrational d. of states spectra of water in confined compartments were also computed and compared with exptl. neutron-scattering results. Both the attenuation and shifting to higher frequencies of the hindered translational peaks upon confinement are clearly reproduced by the model. However, an upshift of librational peaks under the conditions of model confinement still remains underrepresented at the current empirical level.
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  39. 39
    Law, K. Y. Definitions for Hydrophilicity, Hydrophobicity, and Superhydrophobicity: Getting the Basics Right. J. Phys. Chem. Lett. 2014, 5 (4), 686– 688,  DOI: 10.1021/jz402762h
    Google Scholar
    39
    Definitions for Hydrophilicity, Hydrophobicity, and Superhydrophobicity: Getting the Basics Right
    Law, Kock-Yee
    Journal of Physical Chemistry Letters (2014), 5 (4), 686-688CODEN: JPCLCD; ISSN:1948-7185. (American Chemical Society)
    There is no expanded citation for this reference.
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  40. 40
    Bermúdez, D.; Sastre, G. Calculation of Pore Diameters in Zeolites. Theor. Chem. Acc. 2017, 136 (10), 1– 11,  DOI: 10.1007/s00214-017-2143-6
    Google Scholar
    40
    Calculation of pore diameters in zeolites
    Bermudez, Diego; Sastre, German
    Theoretical Chemistry Accounts (2017), 136 (10), 1-11CODEN: TCACFW; ISSN:1432-2234. (Springer)
    Pore diams. of zeolites are calcd. using a new freely available software tool which identifies rings based on the crystallog. notation of atoms. In addn., an automated algorithm allows to ext. information from mol. dynamics outputs so that dynamic pore diams. are calcd. and compared to an exptl. ref. This is useful in order to identify different rings along a given channel as well as for the calcn. and anal. of ring deformations due to framework dynamics and sorbate diffusion.
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  41. 41
    Köfinger, J.; Hummer, G.; Dellago, C. Single-File Water in Nanopores. Phys. Chem. Chem. Phys. 2011, 13 (34), 15403– 15417,  DOI: 10.1039/c1cp21086f
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    41
    Single-file water in nanopores
    Kofinger Jurgen; Hummer Gerhard; Dellago Christoph
    Physical chemistry chemical physics : PCCP (2011), 13 (34), 15403-17 ISSN:.
    Water molecules confined to pores with sub-nanometre diameters form single-file hydrogen-bonded chains. In such nanoscale confinement, water has unusual physical properties that are exploited in biology and hold promise for a wide range of biomimetic and nanotechnological applications. The latter can be realized by carbon and boron nitride nanotubes which confine water in a relatively non-specific way and lend themselves to the study of intrinsic properties of single-file water. As a consequence of strong water-water hydrogen bonds, many characteristics of single-file water are conserved in biological and synthetic pores despite differences in their atomistic structures. Charge transport and orientational order in water chains depend sensitively on and are mainly determined by electrostatic effects. Thus, mimicking functions of biological pores with apolar pores and corresponding external fields gives insight into the structure-function relation of biological pores and allows the development of technical applications beyond the molecular devices found in living systems. In this Perspective, we revisit results for single-file water in apolar pores, and examine the similarities and the differences between these simple systems and water in more complex pores.
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  42. 42
    Ryzhikov, A.; Khay, I.; Nouali, H.; Daou, T. J.; Patarin, J. Energetic Performances of Pure Silica STF and MTT-Type Zeolites under High Pressure Water Intrusion. RSC Adv. 2014, 4 (71), 37655– 37661,  DOI: 10.1039/C4RA05519E
    Google Scholar
    42
    Energetic performances of pure silica STF and MTT-type zeolites under high pressure water intrusion
    Ryzhikov, A.; Khay, I.; Nouali, H.; Daou, T. J.; Patarin, J.
    RSC Advances (2014), 4 (71), 37655-37661CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
    Exptl. water intrusion-extrusion isotherms were performed at room temp.on two pure silica MTT- and STF-type hydrophobic zeolites (zeosils) with 1D channel and cage pore systems, resp. by applying or releasing a high hydraulic pressure. These zeosils were obtained by hydrothermal synthesis in fluoride medium and characterized by structural and physicochem. methods before and after water intrusion. The system "MTT-type zeosil-water" displays a spring behavior with an intrusion pressure of 176 MPa and a stored energy of 5.3 J g-1. No influence of water intrusion on the structure of MTT-type zeosil was found. The "STF-type zeosil-water" system shows a combination of shock-absorber and bumper behavior in the first cycle with an intrusion pressure of 51 MPa. Nevertheless in the following cycles the system demonstrates a spring behavior with an intrusion pressure of 38 MPa. Such behavior can be explained by the formation of silanol groups under intrusion in some pores confirmed by NMR spectroscopy and TG data.
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  43. 43
    Tzanis, L.; Trzpit, M.; Soulard, M.; Patarin, J. High Pressure Water Intrusion Investigation of Pure Silica 1D Channel AFI, MTW and TON-Type Zeolites. Microporous Mesoporous Mater. 2011, 146 (1–3), 119– 126,  DOI: 10.1016/j.micromeso.2011.03.043
    Google Scholar
    43
    High pressure water intrusion investigation of pure silica 1D channel AFI, MTW and TON-type zeolites
    Tzanis, Lydie; Trzpit, Mickael; Soulard, Michel; Patarin, Joel
    Microporous and Mesoporous Materials (2011), 146 (1-3), 119-126CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier Inc.)
    Exptl. water intrusion-extrusion isotherms were performed at room temp. on various 1-dimensional channel pure silica AFI, MTW and TON-type zeolites. The water intrusion is obtained by applying a high hydraulic pressure corresponding to the intrusion step. Whatever the zeosil, when the pressure is released, the water extrusion occurs at a similar pressure to that of the intrusion one. These zeosil-water systems behave like a spring and the phenomenon is reproducible over several cycles. Several characterizations were realized before and after water intrusion-extrusion expts. to reveal the presence or the absence of defects after such expts. For all samples, no structural modifications at the long range order are obsd. by XRD anal. However for the MTW-type zeosil, solid state NMR spectroscopy get evidence of the presence of Q2 and Q3 groups revealing the breaking of some siloxane bridges. Nevertheless, the amt. of defects is very low ( < 2%) and seems not to have an influence on the intrusion-extrusion data for numerous cycles. The stored energy is relatively important and close to 5.8, 15 and 14 J/g for AFI, MTW and TON-type zeosils, resp.
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  44. 44
    Fadeev, A.; Eroshenko, V. Study of Penetration of Water into Hydrophobized Porous Silicas. J. Colloid Interface Sci. 1997, 187 (2), 275– 282,  DOI: 10.1006/jcis.1996.4495
    Google Scholar
    44
    Study of penetration of water into hydrophobized porous silicas
    Fadeev, Alexander Y.; Eroshenko, Valentine A.
    Journal of Colloid and Interface Science (1997), 187 (2), 275-282CODEN: JCISA5; ISSN:0021-9797. (Academic)
    Intrusion of water into a pore space of silicas hydrophobized with alkylsilanes is studied. The water porosimetry technique is introduced and construction of a water porosimeter is described. The effects of bonded alkyl chain length, bonding d., structure of alkylsilane, and av. pore diam. of silica on the parameters of water intrusion are studied. Advancing and receding angles of water on chem. modified silica surfaces are estd. It is shown that contact angles increase as bonding d. and bonded chain length are increased. The correlation between the structure of a bonded alkylsilane monolayer and its hydrophobicity is discussed.
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  45. 45
    Beckstein, O.; Sansom, M. S. P. Liquid-Vapor Oscillations of Water in Hydrophobic Nanopores. Proc. Natl. Acad. Sci. U.S.A. 2003, 100 (12), 7063– 7068,  DOI: 10.1073/pnas.1136844100
    Google Scholar
    45
    Liquid-vapor oscillations of water in hydrophobic nanopores
    Beckstein, Oliver; Sansom, Mark S. P.
    Proceedings of the National Academy of Sciences of the United States of America (2003), 100 (12), 7063-7068CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
    Water plays a key role in biol. membrane transport. In ion channels and water-conducting pores (aquaporins), one-dimensional confinement in conjunction with strong surface effects changes the phys. behavior of water. In mol. dynamics simulations of water in short (0.8 nm) hydrophobic pores the water d. in the pore fluctuates on a nanosecond time scale. In long simulations (460 ns in total) at pore radii ranging from 0.35 to 1.0 nm we quantify the kinetics of oscillations between a liq.-filled and a vapor-filled pore. This behavior can be explained as capillary evapn. alternating with capillary condensation, driven by pressure fluctuations in the water outside the pore. The free-energy difference between the two states depends linearly on the radius. The free-energy landscape shows how a metastable liq. state gradually develops with increasing radius. For radii > ≈0.55 nm it becomes the globally stable state and the vapor state vanishes. One-dimensional confinement affects the dynamic behavior of the water mols. and increases the self diffusion by a factor of 2-3 compared with bulk water. Permeabilities for the narrow pores are of the same order of magnitude as for biol. water pores. Water flow is not continuous but occurs in bursts. Our results suggest that simulations aimed at collective phenomena such as hydrophobic effects may require simulation times >50 ns. For water in confined geometries, it is not possible to extrapolate from bulk or short time behavior to longer time scales.
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  46. 46
    Kumar, R.; Schmidt, J. R.; Skinner, J. L. Hydrogen Bonding Definitions and Dynamics in Liquid Water. J. Chem. Phys. 2007, 126 (20), 204107,  DOI: 10.1063/1.2742385
    Google Scholar
    46
    Hydrogen bonding definitions and dynamics in liquid water
    Kumar, R.; Schmidt, J. R.; Skinner, J. L.
    Journal of Chemical Physics (2007), 126 (20), 204107/1-204107/12CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
    X-ray and neutron diffractions, vibrational spectroscopy, and x-ray Raman scattering and absorption expts. on water are often interpreted in terms of hydrogen bonding. To this end a no. of geometric definitions of hydrogen bonding in water have been developed. While all definitions of hydrogen bonding are to some extent arbitrary, those involving one distance and one angle for a given water dimer are unnecessarily so. In this paper the authors develop a systematic procedure based on two-dimensional potentials of mean force for defining cutoffs for a given pair of distance and angular coordinates. They also develop an electronic structure-based definition of hydrogen bonding in liq. water, related to the electronic occupancy of the antibonding OH orbitals. This definition turns out to be reasonably compatible with one of the distance-angle geometric definitions. These two definitions lead to an est. of the no. of hydrogen bonds per mol. in liq. simple point charge/extended (SPC/E) water of between 3.2 and 3.4. They also used these and other hydrogen-bond definitions to examine the dynamics of local hydrogen-bond no. fluctuations, finding an approx. long-time decay const. for SPC/E water of between 0.8 and 0.9 ps, which corresponds to the time scale for local structural relaxation.
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  47. 47
    Stanley, H. E.; Teixeira, J. Interpretation of the Unusual Behavior of H2O and D2O at Low Temperatures: Tests of a Percolation Model. J. Chem. Phys. 1980, 73 (7), 3404– 3422,  DOI: 10.1063/1.440538
    Google Scholar
    47
    Interpretation of the unusual behavior of water and heavy water at low temperatures: tests of a percolation model
    Stanley, H. Eugene; Teixeira, J.
    Journal of Chemical Physics (1980), 73 (7), 3404-22CODEN: JCPSA6; ISSN:0021-9606.
    The unusual low-temp. behavior of liq. water is interpreted using a simple model based upon connectivity concepts from correlated-site percolation theory. Emphasis is placed on examg. the phys. implications of the continuous H-bonded network (or "gel") formed by water mols. Each water mol. A is assigned to 1 of 5 species based on the no. of "intact bonds" (the no. of other mols. whose interaction energy with A is stronger than some cutoff VHB). The spatial positions of the various species are not randomly distributed but rather are cor. In particular, it is seen that the infinite H-bonded network contains tiny "patches" of 4-bonded mols. Well-defined predictions based upon the putative presence of these tiny patches are developed. The detailed dependences are predicted on temp, diln. with the isotope D2O, hydrostatic pressure greater than atm., and "patch-breaking impurities"--for 4 sep. response functions.
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  48. 48
    Bushuev, Y. G. Properties of the Network of the Hydrogen Bonds of Water. Russ. Chem. Bull. 1997, 46 (5), 888– 891,  DOI: 10.1007/BF02496112
    Google Scholar
    48
    Properties of the network of the hydrogen bonds of water
    Bushuev, Yu. G.
    Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya) (1997), 46 (5), 888-891CODEN: RCBUEY; ISSN:1066-5285. (Consultants Bureau)
    Networks of the hydrogen bonds and those consisting of lines connecting nearby mols. were constructed using configurations of water mols. obtained by the Monte-Carlo method. The concns. of closed cycles of hydrogen bonds were established to be detd. only by the probability of hydrogen bond formation. Characteristics of a model ideal water network were detd. Topol. properties of the Polk model and those of the network of nearest neighbors differ substantially from the properties of the ideal network. The totality of the hydrogen bonds in pure water was proposed to be considered as a hierarchical system. Three topol. different structures of water assocs. were detd.
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  49. 49
    Bushuev, Y.; Davletbaeva, S.; Korolev, V. The Influence of Universal and Specific Interactions on Structural Properties of Liquid Formamide. Russ. Chem. Bull. 1999, 48 (12), 2200– 2210,  DOI: 10.1007/bf02498260
    Google Scholar
    49
    The influence of universal and specific interactions on structural properties of liquid formamide
    Bushuev, Yu. G.; Davletbaeva, S. V.; Korolev, V. P.
    Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya) (1999), 48 (12), 2200-2210CODEN: RCBUEY; ISSN:1066-5285. (Consultants Bureau)
    Monte Carlo simulation of the structure of liq. formamide at 298 K was carried out. Intermol. interactions were calcd. using five different potentials. No essential changes in the spatial structure and topol. properties of the network of hydrogen bonds of liq. formamide occur upon varying the electrostatic intermol. interactions, strength of H-bonds, and temp. Fragments of crystal structure are partly retained in liq. formamide. It was found that the network of H-bonds is structurally inhomogeneous and contains long-lived assocs. of closed cycles of H-bonds as well as tree-like and chain-like structures. The energy, topol., and statistical characteristics of closed cycles of H-bonds were detd.
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  50. 50
    Bushuev, Y. G.; Davletbaeva, S. V. Structural Properties of Liquid N-Methylformamide. Russ. Chem. Bull. 2000, 49 (2), 238– 250,  DOI: 10.1007/bf02494665
    Google Scholar
    50
    Structural properties of liquid N-methylformamide
    Bushuev, Yu. G.; Davletbaeva, S. V.
    Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya) (2000), 49 (2), 238-250CODEN: RCBUEY; ISSN:1066-5285. (Consultants Bureau)
    Monte Carlo simulation of liq. HCONHMe (I) was carried out at 298 K. The atom-atom spatial-distribution functions, concns. of closed cycles of H bonds, radial distribution functions of geometric centers of the cycles, and other characteristics of the system of H bonds and the network built of the lines connecting neighboring mols. were calcd. The effects of electrostatic and van der Waals interactions as well as mol. conformations on the regularities of mutual orientation of the mols. were studied. Open chains of H bonds dominate over closed cycles. The spatial structure of liq. I is detd. by packing of the mols. and steric factors, and is close to the structure of a random closely packed system of soft spheres.
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  51. 51
    Formanek, M.; Martelli, F. Probing the Network Topology in Network-Forming Materials: The Case of Water. AIP Adv. 2020, 10 (5), 055205,  DOI: 10.1063/5.0005332
    Google Scholar
    51
    Probing the network topology in network-forming materials: The case of water
    Formanek, Maud; Martelli, Fausto
    AIP Advances (2020), 10 (5), 055205CODEN: AAIDBI; ISSN:2158-3226. (American Institute of Physics)
    Rings statistic has been widely used to investigate the network topol. in numerically simulated network-forming materials in order to rationalize their phys. and mech. properties. However, different topologies arise depending on how rings are counted, leading to incomplete or even contrasting phys. interpretations. Solving this crit. ambiguity is of primary importance for the correct assessment of material properties. Here, we show how such differences emerge in water, a complex network-forming material endowed with polyamorphism and a directional network of hydrogen bonds whose topol. is correlated with the anomalous behavior of water. We probe the network in the liq. state at several thermodn. points under equil. conditions, as well as during the out-of-equil. first-order-like low d. to high d. amorphous transformation. We study three schemes for counting rings and show that each of them provides complementary insightful information about the network, suggesting that a single counting scheme may not be sufficient to properly describe network topologies and to assess material properties. Our results provide a mol. description of the rings in supercooled water and of the amorphous-to-amorphous transformation kinetics, hence shedding light on the complex nature of water. Nonetheless, our results expose how delicate the proper choice of method for counting rings is, an issue with important consequences for rationalizing the properties of network-forming materials at large. (c) 2020 American Institute of Physics.
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  52. 52
    Rice, S. A.; Sceats, M. G. A Random Network Model for Water. J. Phys. Chem. 1981, 85 (9), 1108– 1119,  DOI: 10.1021/j150609a009
    Google Scholar
    52
    A random network model for water
    Rice, Stuart A.; Sceats, Mark G.
    Journal of Physical Chemistry (1981), 85 (9), 1108-19CODEN: JPCHAX; ISSN:0022-3654.
    A random network model for liq. water is discussed. This model, which uses information derived from studies of cryst. ices, amorphous solid water, and liq. water, is based on two assumptions, one of which refers to structure and the other to the dynamics of the mol. motion. These assumptions are (i) there is a continuous, albeit distorted, network of H bonds in the liq., and (ii) it is meaningful to describe the mol. motion by using two distinct time scales. It is shown how adoption of these assumptions leads to the definition of a random network potential, and to rather good descriptions of the OO distribution function, the dielec. const., and the bulk thermodn. properties of liq. water. Despite its successes, the random network model fails to describe adequately some of the properties of liq. water; these discrepancies are discussed from the point of view of modifications needed to improve the model.
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  53. 53
    Cobeña-Reyes, J.; Sahimi, M. Universal Intrinsic Dynamics and Freezing of Water in Small Nanotubes. J. Phys. Chem. C 2021, 125 (1), 946– 956,  DOI: 10.1021/acs.jpcc.0c08494
    Google Scholar
    53
    Universal intrinsic dynamics and freezing of water in nanotubes
    Cobena-Reyes, Jose; Sahimi, Muhammad
    Journal of Physical Chemistry C (2021), 125 (1), 946-956CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
    Although it is well known that confinement alters the f.p. of water, the mechanism by which this occurs, particularly in small nanotubes, is still under active research. It was recently claimed that the f.p. of water in a carbon nanotube of a certain size may be as high as its b.p. under bulk conditions or even higher. A more recent paper reported that the change in the f.p. may not be as drastic as what was claimed by Agrawal et al., and may in fact be close to the bulk f.p. Thus, aside from the need to resolve the issue, an important question that arises is whether such a behavior is universal and may happen in any type of nanotube. In other words, can the interactions between water mols. and the wall atoms in other types of nanotube suppress this effect, or is this a universal feature occurring in every type of nanotube. In this paper, we address these issues by carrying out extensive mol. dynamics (MD) simulations and studying the dynamics of water in silicon carbide nanotubes. The results indicate that the m.p. can be as much as 100 K lower than the bulk value. A comparison between the hydrogen-bond networks formed in carbon and silicon carbon nanotubes indicates that weaker HB networks are the main cause of the depression of the f.p. Several types of ice, including those with trigonal, square, and pentagonal cross sections, are identified, each of which exhibits a different m.p. that depends on the nanotube's diam. The effect of the partial charges of the atoms of the nanotube's walls on the strength of the hydrogen-bond network was also studied. Larger partial charges lead to a more rapid decay of the hydrogen-bond correlation function, signaling a lower m.p.
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  54. 54
    Mochizuki, K. Absorption of Mechanical Energyviaformation of Ice Nanotubes in Zeolites. Phys. Chem. Chem. Phys. 2021, 23 (36), 20307– 20312,  DOI: 10.1039/D1CP01482J
    Google Scholar
    54
    Absorption of mechanical energy via formation of ice nanotubes in zeolites
    Mochizuki, Kenji
    Physical Chemistry Chemical Physics (2021), 23 (36), 20307-20312CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
    Mol. dynamics simulations are carried out for a heterogeneous system composed of bulk water and pure-silica zeolites of the AFI type. My simulations show, for the first time, the spontaneous crystn. of water in hydrophobic zeolite channels by compression, while the water outside remains liq. The formation of ice nanotubes results in a mol. bumper behavior in the absence of chem. reactions, although the mechanism has been explained by the appearance of silanol defects. In contrast, the same zeolite-water system exhibits a weak shock-absorber behavior at higher temps. My study shows that the phase transitions of confined water dramatically change its intrusion/extrusion behavior and alter the energetic performance by varying the temp. alone. The results offer a new perspective for a better design of hydrophobic nanoporous materials utilized with water.
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  55. 55
    Offei-Danso, A.; Morzan, U. N.; Rodriguez, A.; Hassanali, A.; Jelic, A. The Collective Burst Mechanism of Angular Jumps in Liquid Water. Nat. Commun. 2023, 14 (1), 1345– 1411,  DOI: 10.1038/s41467-023-37069-9
    Google Scholar
    55
    The collective burst mechanism of angular jumps in liquid water
    Offei-Danso, Adu; Morzan, Uriel N.; Rodriguez, Alex; Hassanali, Ali; Jelic, Asja
    Nature Communications (2023), 14 (1), 1345CODEN: NCAOBW; ISSN:2041-1723. (Nature Portfolio)
    Understanding the microscopic origins of collective reorientational motions in aq. systems requires techniques that allow us to reach beyond our chem. imagination. Herein, we elucidate a mechanism using a protocol that automatically detects abrupt motions in reorientational dynamics, showing that large angular jumps in liq. water involve highly cooperative orchestrated motions. Our automatized detection of angular fluctuations, unravels a heterogeneity in the type of angular jumps occurring concertedly in the system. We show that large orientational motions require a highly collective dynamical process involving correlated motion of many water mols. in the hydrogen-bond network that form spatially connected clusters going beyond the local angular jump mechanism. This phenomenon is rooted in the collective fluctuations of the network topol. which results in the creation of defects in waves on the THz timescale. The mechanism we propose involves a cascade of hydrogen-bond fluctuations underlying angular jumps and provides new insights into the current localized picture of angular jumps, and its wide use in the interpretations of numerous spectroscopies as well in reorientational dynamics of water near biol. and inorg. systems. The role of finite size effects, as well as of the chosen water model, on the collective reorientation is also elucidated.
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  56. 56
    Paulo, G.; Sun, K.; di Muccio, G.; Gubbiotti, A.; Morozzo della Rocca, B.; Geng, J.; Maglia, G.; Chinappi, M.; Giacomello, A. Hydrophobically gated memristive nanopores for neuromorphic applications. Nat. Commun. 2023, 14, 8390,  DOI: 10.1038/s41467-023-44019-y
    Google Scholar
    56
    Hydrophobically gated memristive nanopores for neuromorphic applications
    Paulo, Goncalo; Sun, Ke; Di Muccio, Giovanni; Gubbiotti, Alberto; Morozzo della Rocca, Blasco; Geng, Jia; Maglia, Giovanni; Chinappi, Mauro; Giacomello, Alberto
    Nature Communications (2023), 14 (1), 8390CODEN: NCAOBW; ISSN:2041-1723. (Nature Portfolio)
    Abstr.: Signal transmission in the brain relies on voltage-gated ion channels, which exhibit the elec. behavior of memristors, resistors with memory. State-of-the-art technologies currently employ semiconductor-based neuromorphic approaches, which have already demonstrated their efficacy in machine learning systems. However, these approaches still cannot match performance achieved by biol. neurons in terms of energy efficiency and size. In this study, we utilize mol. dynamics simulations, continuum models, and electrophysiol. expts. to propose and realize a bioinspired hydrophobically gated memristive nanopore. Our findings indicate that hydrophobic gating enables memory through an electrowetting mechanism, and we establish simple design rules accordingly. Through the engineering of a biol. nanopore, we successfully replicate the characteristic hysteresis cycles of a memristor and construct a synaptic device capable of learning and forgetting. This advancement offers a promising pathway for the realization of nanoscale, cost- and energy-effective, and adaptable bioinspired memristors.
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  57. 57
    Dzubiella, J.; Hansen, J. P. Electric-Field-Controlled Water and Ion Permeation of a Hydrophobic Nanopore. J. Chem. Phys. 2005, 122 (23), 234706,  DOI: 10.1063/1.1927514
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    57
    Electric-field-controlled water and ion permeation of a hydrophobic nanopore
    Dzubiella, J.; Hansen, J.-P.
    Journal of Chemical Physics (2005), 122 (23), 234706/1-234706/14CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
    The permeation of hydrophobic, cylindrical nanopores by water mols. and ions is investigated under equil. and out-of-equil. conditions by extensive mol.-dynamics simulations. Neglecting the chem. structure of the confining pore surface, we focus on the effects of pore radius and elec. field on permeation. The simulations confirm the intermittent filling of the pore by water, reported earlier under equil. conditions for pore radii larger than a crit. radius Rc. Below this radius, water can still permeate the pore under the action of a strong elec. field generated by an ion concn. imbalance at both ends of the pore embedded in a structureless membrane. The water driven into the channel undergoes considerable electrostriction characterized by a mean d. up to twice the bulk d. and by a dramatic drop in dielec. permittivity which can be traced back to a considerable distortion of the hydrogen-bond network inside the pore. The free-energy barrier to ion permeation is estd. by a variant of umbrella sampling for Na+, K+, Ca2+, and Cl- ions, and correlates well with known solvation free energies in bulk water. Starting from an initial imbalance in ion concn., equil. is gradually restored by successive ion passages through the water-filled pore. At each passage the elec. field across the pore drops, reducing the initial electrostriction, until the pore, of radius less than Rc, closes to water and hence to ion transport, thus providing a possible mechanism for voltage-dependent gating of hydrophobic pores.
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  58. 58
    Rasaiah, J. C.; Garde, S.; Hummer, G. Water in Nonpolar Confinement: From Nanotubes to Proteins and Beyond. Annu. Rev. Phys. Chem. 2008, 59, 713– 740,  DOI: 10.1146/annurev.physchem.59.032607.093815
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    58
    Water in nonpolar confinement: from nanotubes to proteins and beyond
    Rasaiah, Jayendran C.; Garde, Shekhar; Hummer, Gerhard
    Annual Review of Physical Chemistry (2008), 59 (), 713-740CODEN: ARPLAP; ISSN:0066-426X. (Annual Reviews Inc.)
    A review. Water mols. confined to nonpolar pores and cavities of nanoscopic dimensions exhibit highly unusual properties. Water filling is strongly cooperative, with the possible coexistence of filled and empty states and sensitivity to small perturbations of the pore polarity and solvent conditions. Confined water mols. form tightly hydrogen bonded wires or clusters. The weak attractions to the confining wall, combined with strong interactions between water mols., permit exceptionally rapid water flow, exceeding expectations from macroscopic hydrodynamics by several orders of magnitude. The proton mobility along 1D water wires also substantially exceeds that in the bulk. Proteins appear to exploit these unusual properties of confined water in their biol. function (e.g., to ensure rapid water flow in aquaporins or to gate proton flow in proton pumps and enzymes). The unusual properties of water in nonpolar confinement are also relevant to the design of novel nanofluidic and mol. sepn. devices or fuel cells.
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  59. 59
    Fasano, M.; Bevilacqua, A.; Chiavazzo, E.; Humplik, T.; Asinari, P. Mechanistic Correlation between Water Infiltration and Framework Hydrophilicity in MFI Zeolites. Sci. Rep. 2019, 9 (1), 18429– 18512,  DOI: 10.1038/s41598-019-54751-5
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    59
    Mechanistic correlation between water infiltration and framework hydrophilicity in MFI zeolites
    Fasano, Matteo; Bevilacqua, Alessio; Chiavazzo, Eliodoro; Humplik, Thomas; Asinari, Pietro
    Scientific Reports (2019), 9 (1), 18429CODEN: SRCEC3; ISSN:2045-2322. (Nature Research)
    Hydrophobic zeolites are nanoporous materials that are attracting an increasing interest, esp. for catalysis, desalination, energy storage and biomedical applications. Nevertheless, a more profound understanding and control of water infiltration in their nanopores is still desirable to rationally design zeolite-based materials with tailored properties. In this work, both atomistic simulations and previous exptl. data are employed to investigate water infiltration in hydrophobic MFI zeolites with different concn. of hydrophilic defects. Results show that limited concns. of defects (e.g. 1%) induce a change in the shape of infiltration isotherms (from type-V to type-I), which denotes a sharp passage from typical hydrophobic to hydrophilic behavior. A correlation parametrized on both energy and geometric characteristics of the zeolite (infiltration model) is then adopted to interpolate the infiltration isotherms data by means of a limited no. of phys.-meaningful parameters. Finally, the infiltration model is combined with the water-zeolite interaction energy computed by simulations to correlate the water intrusion mechanism with the atomistic details of the zeolite crystal, such as defects concn., distribution and hydrophilicity. The suggested methodol. may allow a faster (more than one order of magnitude) and more systematic preliminary computational screening of innovative zeolite-based materials for energy storage, desalination and biomedical purposes.
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  60. 60
    Trzpit, M.; Soulard, M.; Patarin, J.; Desbiens, N.; Cailliez, F.; Boutin, A.; Demachy, I.; Fuchs, a H. The Effect of Local Defects on Water Adsorption in Silicalite-1 Zeolite: A Joint Experimental and Molecular Simulation Study. Langmuir 2007, 23 (20), 10131– 10139,  DOI: 10.1021/la7011205
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    60
    The effect of local defects on water adsorption in silicalite-1 zeolite. A joint experimental and molecular simulation study
    Trzpit, M.; Soulard, M.; Patarin, J.; Desbiens, N.; Cailliez, F.; Boutin, A.; Demachy, I.; Fuchs, A. H.
    Langmuir (2007), 23 (20), 10131-10139CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
    We report a joint exptl. and mol. simulation study of water condensation in silicalite-1 zeolite. A sample was synthesized using the fluoride route and was found to contain essentially no defects. A second sample synthesized using the hydroxide route was found to contain a small amt. of silanol groups. The thermodn. of water condensation was studied in these 2 samples, as well as in a com. sample, to understand the effect of local defects on water adsorption. The mol. simulation study enabled us to qual. reproduce the exptl. obsd. condensation thermodn. features. A shift and a rounding of the condensation transition was obsd. with an increasing hydrophilicity of the local defect, but the condensation transition was still obsd. above the water satn. vapor pressure P0. Both expts. and simulations agree on the fact that a small water uptake can be obsd. at very low pressure, but that the bulk liq. does not form from the gas phase below P0. The picture that emerges from the obsd. water condensation mechanism is the existence of a heterogeneous internal surface that is overall hydrophobic, despite the existence of hydrophilic "patches". This heterogeneous surface configuration is thermodynamically stable in a wide range of reduced pressures (from P/P0 = 0.2 to a few thousands), until the condensation transition takes place.
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  61. 61
    Zones, S.; Hwang, S.; Elomari, S.; Ogino, I.; Davis, M.; Burton, A. The Fluoride-Based Route to All-Silica Molecular Sieves; a Strategy for Synthesis of New Materials Based upon Close-Packing of Guest-Host Products. C. R. Chim. 2005, 8 (3–4), 267– 282,  DOI: 10.1016/j.crci.2004.12.009
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    61
    The fluoride-based route to all-silica molecular sieves; a strategy for synthesis of new materials based upon close-packing of guest-host products
    Zones, Stacey I.; Hwang, Son-Jong; Elomari, Saleh; Ogino, Isao; Davis, Mark E.; Burton, Allen W.
    Comptes Rendus Chimie (2005), 8 (3-4), 267-282CODEN: CRCOCR; ISSN:1631-0748. (Editions Scientifiques et Medicales Elsevier)
    A review. This study surveys the use of a range of structure-directing agents (SDA) in zeolite synthesis expts. using HF. The studies involve systems contg. only silica as the inorg. component. Results from this study reinforce the concept that more open-framework host structures form when the reaction conditions include lower H2O/SiO2 ratios. Novel pure silica compns. are achieved using this methodol. Also explored using MAS NMR studies were whether the use of fluoride anions in synthesis leads to different nucleation selectivities as a function of diln. and whether guest mols. achieve tighter packing in the host structures using fluoride instead of hydroxide. The results indicated that some large organo-cations which produce no products in alk. media give interesting host structures in the fluoride reactions.
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  62. 62
    Arletti, R.; Ronchi, L.; Quartieri, S.; Vezzalini, G.; Ryzhikov, A.; Nouali, H.; Daou, T. J.; Patarin, J. Intrusion-Extrusion Experiments of MgCl2 Aqueous Solution in Pure Silica Ferrierite: Evidence of the Nature of Intruded Liquid by in Situ High Pressure Synchrotron X-Ray Powder Diffraction. Microporous Mesoporous Mater. 2016, 235, 253– 260,  DOI: 10.1016/j.micromeso.2016.08.024
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    62
    Intrusion-extrusion experiments of MgCl2 aqueous solution in pure silica ferrierite: Evidence of the nature of intruded liquid by in situ high pressure synchrotron X-ray powder diffraction
    Arletti, Rossella; Ronchi, Laura; Quartieri, Simona; Vezzalini, Giovanna; Ryzhikov, Andrey; Nouali, Habiba; Daou, T. Jean; Patarin, Joel
    Microporous and Mesoporous Materials (2016), 235 (), 253-260CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier B.V.)
    Exptl. intrusion-extrusion isotherms of MgCl2•21H2O soln. were recorded at room temp. on pure silica FER-type zeolite (Si-FER). The intrusion occurs at 195 MPa and the phenomenon is completely reversible with a slight hysteresis. The "Si-FER - MgCl2 aq. soln." system behaves like a spring. The material was deeply characterized before and after intrusion-extrusion expts. and no significant changes were obsd. The unit cell parameters were refined - on the basis of the in situ synchrotron X-ray powder diffraction data - up to 1.47 GPa and then at Pamb upon pressure release. The Rietveld refinement of the data collected at 0.28 GPa (280 MPa), a pressure close to the intrusion value, shows that both ions and water mols. present in the MgCl2 aq. soln. were intruded in the porosity. However, the solvation degree of the intruded ions differs from the initial soln., revealing a partial desolvation of both magnesium and chloride ions. As a whole, the nature and amt. of the intruded species correspond to a MgCl2•10H2O compn. Moreover, at a higher pressure (0.68 GPa), a phase transition from the orthorhombic Pmnn to the monoclinic P21/n s.g. is obsd. in Si-FER. At 1.47 GPa, the zeolite maintains this monoclinic symmetry, while another phase transition, to the monoclinic P21 s g., is argued from the anal. of the pattern of the sample compressed to 2.6 GPa and then collected upon pressure release to ambient conditions.
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  63. 63
    Confalonieri, G.; Ryzhikov, A.; Arletti, R.; Quartieri, S.; Vezzalini, G.; Isaac, C.; Paillaud, J. L.; Nouali, H.; Daou, T. J. Structural Interpretation of the Energetic Performances of a Pure Silica LTA-Type Zeolite. Phys. Chem. Chem. Phys. 2020, 22 (9), 5178– 5187,  DOI: 10.1039/C9CP06760D
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    63
    Structural interpretation of the energetic performances of a pure silica LTA-type zeolite
    Confalonieri, Giorgia; Ryzhikov, Andrey; Arletti, Rossella; Quartieri, Simona; Vezzalini, Giovanna; Isaac, Carole; Paillaud, Jean-Louis; Nouali, Habiba; Daou, T. Jean
    Physical Chemistry Chemical Physics (2020), 22 (9), 5178-5187CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
    The high pressure intrusion-extrusion process of different electrolyte aq. solns. (NaCl and CaCl2, 2 M and 3 M) in a hydrophobic pure-silica LTA zeolite was investigated for energetic purposes by means of in situ X-ray powder diffraction, porosimeter tests, thermogravimetric anal. and NMR spectroscopy. The intrusion pressure of the saline solns. was proved to be higher than that of pure water, with the highest value measured for CaCl2, thus increasing the energetic performance of the system. The intrusion of NaCl solns. was irreversible (bumper behavior), whereas that of CaCl2 solns. is partially reversible (shock absorber behavior). The structural investigation allowed interpreting these results on the basis of the different intrusion mechanisms, in turn induced by the different nature of the cations present in the electrolyte solns. When Si-LTA is intruded by NaCl soln., firstly H2O mols. penetrate the pores, leading to higher silanol defect formation followed by the solvated ions. With CaCl2, instead, due to a higher solvation enthalpy of Ca2+, a higher pressure is required for intrusion, and both H2O and ions penetrate at the same pressure. The structural refinements demonstrate (i) a different arrangement of the extraframework species in the two systems, (ii) the intrusion of the salt solns. occurs through strong desolvation of the ions and (iii) the salt/H2O ratios of the intruded species are higher than those of the starting electrolyte solns.
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  64. 64
    Hughes, Z. E.; Carrington, L. A.; Raiteri, P.; Gale, J. D. A Computational Investigation into the Suitability of Purely Siliceous Zeolites as Reverse Osmosis Membranes. J. Phys. Chem. C 2011, 115 (10), 4063– 4075,  DOI: 10.1021/jp109591f
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    64
    A Computational Investigation into the Suitability of Purely Siliceous Zeolites as Reverse Osmosis Membranes
    Hughes, Zak E.; Carrington, Louise A.; Raiteri, Paolo; Gale, Julian D.
    Journal of Physical Chemistry C (2011), 115 (10), 4063-4075CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
    Desalination by reverse osmosis is an increasingly important source of potable water in many countries. The interest in developing new, more effective membranes is, therefore, great. One set of materials that have been suggested as a possible new type of desalination membrane are nanoporous materials. In this work computational methods are used to investigate the behavior of water within five different zeolitic systems. Quantum mech. calcns. are used to construct a set of force-field parameters for two atomistic models. Mol. dynamics simulations of the zeolites show that water will diffuse through zeolites at a rate faster than that obtained with the composite membranes currently used in com. desalination. In addn., the thermodn. of salt rejection have been investigated using the free energy perturbation method. The results of these calcns. show that the chloride ion finds the zeolitic environment strongly unfavorable compared to the bulk soln. In the case of the sodium ion, the energetic difference between the zeolite environment and soln. is less significant, but charge sepn. prevents sodium from permeating the membrane.
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  65. 65
    Vaitheeswaran, S.; Rasaiah, J. C.; Hummer, G. Electric Field and Temperature Effects on Water in the Narrow Nonpolar Pores of Carbon Nanotubes. J. Chem. Phys. 2004, 121 (16), 7955– 7965,  DOI: 10.1063/1.1796271
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    65
    Electric field and temperature effects on water in the narrow nonpolar pores of carbon nanotubes
    Vaitheeswaran, Subramanian; Rasaiah, Jayendran C.; Hummer, Gerhard
    Journal of Chemical Physics (2004), 121 (16), 7955-7965CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
    Water mols. in the narrow cylindrical pore of a (6,6) carbon nanotube form single-file chains with their dipoles collectively oriented either up or down along the tube axis. We study the interaction of such water chains with homogeneous elec. fields for finite closed and infinite periodically replicated tubes. By evaluating the grand-canonical partition function term-by-term, we show that homogeneous elec. fields favor the filling of previously empty nanotubes with water from the bulk phase. A two-state description of the collective water dipole orientation in the nanotube provides an excellent approxn. for the dependence of the water-chain polarization and the filling equil. on the elec. field. The energy and entropy contributions to the free energy of filling the nanotube were detd. from the temp. dependence of the occupancy probabilities. We find that the energy of transfer depends sensitively on the water-tube interaction potential, and that the entropy of one-dimensionally ordered water chains is comparable to that of bulk water. We also discuss implications for proton transfer reactions in biol.
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  66. 66
    de Freitas, D. N.; Mendonça, B. H.; Köhler, M. H.; Barbosa, M. C.; Matos, M. J. S.; Batista, R. J. C.; de Oliveira, A. B. Water Diffusion in Carbon Nanotubes under Directional Electric Frields: Coupling between Mobility and Hydrogen Bonding. Chem. Phys. 2020, 537 (April), 110849,  DOI: 10.1016/j.chemphys.2020.110849
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    66
    Water diffusion in carbon nanotubes under directional electric frields: Coupling between mobility and hydrogen bonding
    de Freitas, Debora N.; Mendonca, Bruno H. S.; Kohler, Mateus H.; Barbosa, Marcia C.; Matos, Matheus J. S.; Batista, Ronaldo J. C.; de Oliveira, Alan B.
    Chemical Physics (2020), 537 (), 110849CODEN: CMPHC2; ISSN:0301-0104. (Elsevier B.V.)
    Mol. Dynamics simulations of water confined in carbon nanotubes subjected to external elec. fields show that water mobility strongly depends on the confining geometry, the intensity and directionality of the elec. field. While fields forming angles of 0° and 45° slow down the water dynamics by increasing organization, perpendicular fields can enhance water diffusion by decreasing hydrogen bond formation. For 1.2 diam. long nanotubes, the parallel field destroys the ice-like water structure increasing mobility. These results indicate that the structure and dynamics of confined water are extremely sensitive to external fields and can be used to facilitate filtration processes.
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  67. 67
    Gao, Y.; Yin, M.; Zhang, H.; Xu, B. Electrically Suppressed Outflow of Confined Liquid in Hydrophobic Nanopores. ACS Nano 2022, 16 (6), 9420– 9427,  DOI: 10.1021/acsnano.2c02240
    Google Scholar
    67
    Electrically Suppressed Outflow of Confined Liquid in Hydrophobic Nanopores
    Gao, Yuan; Yin, Mengtian; Zhang, Haozhe; Xu, Baoxing
    ACS Nano (2022), 16 (6), 9420-9427CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
    Confining liq. in a hydrophobic nanoenvironment has enabled a broad spectrum of applications in biomedical sensors, mech. actuators, and energy storage and converters, where the outflow of confined liq. is spontaneous and fast due to the intrinsic hydrophobic nature of nanopores with extremely low interfacial friction, challenging design capacity and control tolerance of structures and devices. Here, we present a facile approach of suppressing the outflow of water confined in hydrophobic nanopores with an elec. field. Extensive mol. dynamics simulations show that the presence of an elec. field could significantly strengthen hydrogen bonds and retard degrdns. of the assocd. networks during the outflow. The outflow deformation and strength are extd. to quant. characterize the elec. suppression to outflow and agree well with simulations. This study proposes a practical means of impeding the fast liq. outflow in hydrophobic nanopores, potentially useful for devising nanofluidics-based functional structures and devices with controllable performance.
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  68. 68
    Lu, D.; Li, Y.; Rotkin, S. V.; Ravaioli, U.; Schulten, K. Finite-Size Effect and Wall Polarization in a Carbon Nanotube Channel. Nano Lett. 2004, 4 (12), 2383– 2387,  DOI: 10.1021/nl0485511
    Google Scholar
    68
    Finite-Size Effect and Wall Polarization in a Carbon Nanotube Channel
    Lu, Deyu; Li, Yan; Rotkin, Slava V.; Ravaioli, Umberto; Schulten, Klaus
    Nano Letters (2004), 4 (12), 2383-2387CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
    The electronic structure and dielec. screening of finite-length armchair carbon nanotubes are studied in view of their tech. applications. For this purpose, a self-consistent tight-binding method, which captures the periodic oscillation pattern of the finite band gap as a function of tube length, is applied. We find the parallel screening const. ε‖ to grow nearly linearly with the length L and to show little dependence on the band gap. In contrast, the perpendicular screening const. ε.perp. is strongly related to the band gap and converges for L > 10R (radius) to its bulk value. Our description is employed to study the wall polarization in a short (6,6) nanotube filled with six water mols., a situation that arises with tech. uses of carbon nanotubes as channels.
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  69. 69
    Shen, C.; Qiu, H.; Guo, W. Soliton-like Propagation of Dipole Reorientation in Confined Single-File Water Chains. Nanoscale 2019, 11 (41), 19387– 19392,  DOI: 10.1039/C9NR03631H
    Google Scholar
    69
    Soliton-like propagation of dipole reorientation in confined single-file water chains
    Shen, Chun; Qiu, Hu; Guo, Wanlin
    Nanoscale (2019), 11 (41), 19387-19392CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)
    A review. Water mols. confined in a narrow nanotube channel orient themselves into a uniformly ordered single-file chain. Here, we report by means of comprehensive mol. dynamics simulations and soliton-model-based theor. anal. that the reorientation (i.e., rotation) of a single water mol. in this dipole chain, triggered for example by an external charge, can induce successive reorientation of the rest of the water mols., which propagates in a soliton-like manner. The resulting local potential energy peak sepg. the reoriented and the pending reorientation subsections moves with an unweakened peak intensity at a const. velocity in the ambient environment, and particularly, can penetrate or make a turn through a crossed nanotube junction. The propagation velocity depends on the strength of the external charge, in agreement with our sine-Gordon soliton-based theor. anal. We further show that this unidirectional propagation originates from the partially inhibited fluctuation in dipole orientation of reoriented water with respect to that of original ones. These findings may be helpful in the development of high-efficiency information transmitting, processing and storage devices and the understanding of functioning of biol. water channels.
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  70. 70
    Zhang, Y.; Zhang, J.; Luo, R.; Dou, Y. Experimental Study on the Effects of Applied Electric Field on Liquid Infiltration into Hydrophobic Zeolite. Energies 2023, 16 (13), 5065,  DOI: 10.3390/en16135065
    Google Scholar
    70
    Experimental Study on the Effects of Applied Electric Field on Liquid Infiltration into Hydrophobic Zeolite
    Zhang, Yafei; Zhang, Jiahua; Luo, Rui; Dou, Yihua
    Energies (Basel, Switzerland) (2023), 16 (13), 5065CODEN: ENERGA; ISSN:1996-1073. (MDPI AG)
    A nanofluidic energy absorption system (NEAS) is composed of nanoporous material and functional liq. with high energy absorption d. Applying an elec. field to adjust the energy absorption characteristics of a nanofluidic system will open broader prospects for its application. In the current work, ZSM-5 zeolite was adopted as the nanoporous material and water, a 25% KCl soln., and a satd. KCl soln. were adopted as functional liqs. to configure NEASs. Pressure-induced infiltration expts. were carried out to study the infiltration and defiltration characteristics of the NEASs under the action of an applied elec. field. The results show that the introduction of an applied elec. field can weaken the hydrogen bonds between mols., thus reducing the equiv. surface tension and contact angle, changing the infiltrability of liq. mols. into the nanopores, and reducing the infiltration pressure of the system. In an electrolyte soln./zeolite system, the anions and cations move close to the two plate electrodes under the action of an external elec. field, and the fluid properties in the central zone of the pressure chamber are close to the water/zeolite system. For both an ultra-low cond. liq. and an electrolyte soln./zeolite system, applying an elec. field can effectively improve the relative outflow rate of liq., thus improving the reusability of the system.
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  71. 71
    Lin, Y.; Shiomi, J.; Maruyama, S.; Amberg, G. Dielectric Relaxation of Water inside a Single-Walled Carbon Nanotube. Phys. Rev. B: Condens. Matter Mater. Phys. 2009, 80 (4), 045419– 45427,  DOI: 10.1103/PhysRevB.80.045419
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    71
    Dielectric relaxation of water inside a single-walled carbon nanotube
    Lin, Yuan; Shiomi, Junichiro; Maruyama, Shigeo; Amberg, Gustav
    Physical Review B: Condensed Matter and Materials Physics (2009), 80 (4), 045419/1-045419/7CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)
    We report a mol. dynamics study of anisotropic dynamics and dielec. properties of water confined inside a single-walled C nanotube (SWNT) at room temp. The model includes dynamics of an SWNT described by a realistic potential function. A comparison with simulations assuming a rigid nanotube demonstrates that the popular assumption severely overestimates the dielec. const. for small diam. SWNTs. Simulations of water inside flexible SWNTs with various diams. reveal strong directional dependence of the dynamic and dielec. properties due to the confinement effect. The obtained dielec. permittivity spectra (DPS) identify 2 different dipolar relaxation frequencies corresponding to the axial and the cross-sectional directions, which are significantly smaller and larger than the single relaxation frequency of bulk water, resp. The frequency variation increases as the SWNT diam. decreases. DPS can be used as a fingerprint of water inside SWNTs to monitor the water intrusion into SWNTs.
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  72. 72
    Fasano, M.; Crisafulli, A.; Cardellini, A.; Bergamasco, L.; Chiavazzo, E.; Asinari, P. Thermally Triggered Nanorocket from Double-Walled Carbon Nanotube in Water. Mol. Simul. 2019, 45 (4–5), 417– 424,  DOI: 10.1080/08927022.2018.1535180
    Google Scholar
    72
    Thermally triggered nanorocket from double-walled carbon nanotube in water
    Fasano, Matteo; Crisafulli, Alessandro; Cardellini, Annalisa; Bergamasco, Luca; Chiavazzo, Eliodoro; Asinari, Pietro
    Molecular Simulation (2019), 45 (4-5), 417-424CODEN: MOSIEA; ISSN:0892-7022. (Taylor & Francis Ltd.)
    In this work, we propose and investigate the use of double-walled carbon nanotubes (DWCNTs) as nanosized rockets. The nanotubes are immersed in water, and the propulsion of inner nanotube is achieved by heating the water encapsulated within the DWCNT. Considering a setup made of (5,5)(8,8) DWCNT, mol. dynamics simulations for different water temps. show that the trajectory can be divided into four phases: trigger, expulsion, damping and final equil. After analyzing the dynamics and the involved forces, we find out that the inner nanotube expulsion is mainly controlled by van der Waals interactions between the nanotubes; whereas, the damping role is predominantly played by the external aq. environment. Based on these results, we propose an anal. model able to predict both the triggering time for a given water temp. and the whole dynamics of nanorocket. The validity of such dynamical model can be extended also to a broader variety of DWCNT configurations, once the different forces acting on the inner nanotube are provided. The proposed model may contribute to assist the design of nanorockets in several nanotechnol. applications, such as triggered drug delivery, cell membrane piercing, or colloids with thermophoretic properties.
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  73. 73
    Li, J.; Rozen, I.; Wang, J. Rocket Science at the Nanoscale. ACS Nano 2016, 10, 5619– 5634,  DOI: 10.1021/acsnano.6b02518
    Google Scholar
    73
    Rocket Science at the Nanoscale
    Li, Jinxing; Rozen, Isaac; Wang, Joseph
    ACS Nano (2016), 10 (6), 5619-5634CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
    A review. Autonomous propulsion at the nanoscale represents one of the most challenging and demanding goals in nanotechnol. Over the past decade, numerous important advances in nanotechnol. and material science have contributed to the creation of powerful self-propelled micro/nanomotors. In particular, micro- and nanoscale rockets (MNRs) offer impressive capabilities, including remarkable speeds, large cargo-towing forces, precise motion controls, and dynamic self-assembly, which have paved the way for designing multifunctional and intelligent nanoscale machines. These multipurpose nanoscale shuttles can propel and function in complex real-life media, actively transporting and releasing therapeutic payloads and remediation agents for diverse biomedical and environmental applications. This review discusses the challenges of designing efficient MNRs and presents an overview of their propulsion behavior, fabrication methods, potential rocket fuels, navigation strategies, practical applications, and the future prospects of rocket science and technol. at the nanoscale.
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  74. 74
    Venugopalan, P. L.; Esteban-Fernández De Ávila, B.; Pal, M.; Ghosh, A.; Wang, J. Fantastic Voyage of Nanomotors into the Cell. ACS Nano 2020, 14, 9423– 9439,  DOI: 10.1021/acsnano.0c05217
    Google Scholar
    74
    Fantastic Voyage of Nanomotors into the Cell
    Venugopalan, Pooyath Lekshmy; Esteban-Fernandez de Avila, Berta; Pal, Malay; Ghosh, Ambarish; Wang, Joseph
    ACS Nano (2020), 14 (8), 9423-9439CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
    A review. Richard Feynman's 1959 vision of controlling devices at small scales and swallowing the surgeon has inspired the science-fiction Fantastic Voyage film and has played a crucial role in the rapid development of the microrobotics field. Sixty years later, the authors are currently witnessing a dramatic progress in this field, with artificial micro- and nanoscale robots moving within confined spaces, down to the cellular level, and performing a wide range of biomedical applications within the cellular interior while addressing the limitations of common passive nanosystems. In this review article, key recent advances in the field of micro/nanomotors toward important cellular applications are discussed. Specifically, the authors outline the distinct capabilities of nanoscale motors for such cellular applications and illustrate how the active movement of nanomotors leads to distinct advantages of rapid cell penetration, accelerated intracellular sensing, and effective intracellular delivery toward enhanced therapeutic efficiencies. The authors finalize by discussing the future prospects and key challenges that such micromotor technol. face toward implementing practical intracellular applications. By increasing the authors' knowledge of nanomotors' cell entry and of their behavior within the intracellular space, and by successfully addressing key challenges, the authors expect that next-generation nanomotors will lead to exciting advances toward cell-based diagnostics and therapy.
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  75. 75
    Wu, Y.; Tepper, H. L.; Voth, G. A. Flexible Simple Point-Charge Water Model with Improved Liquid-State Properties. J. Chem. Phys. 2006, 124 (2), 024503,  DOI: 10.1063/1.2136877
    Google Scholar
    75
    Flexible simple point-charge water model with improved liquid-state properties
    Wu, Yujie; Tepper, Harald L.; Voth, Gregory A.
    Journal of Chemical Physics (2006), 124 (2), 024503/1-024503/12CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
    In order to introduce flexibility into the simple point-charge (SPC) water model, the impact of the intramol. degrees of freedom on liq. properties was systematically studied in this work as a function of many possible parameter sets. It was found that the diffusion const. is extremely sensitive to the equil. bond length and that this effect is mainly due to the strength of intermol. hydrogen bonds. The static dielec. const. was found to be very sensitive to the equil. bond angle via the distribution of intermol. angles in the liq.: A larger bond angle will increase the angle formed by two mol. dipoles, which is particularly significant for the first solvation shell. This result is in agreement with the work of Hochtl et al. [J. Chem. Phys. 109, 4927 (1998)]. A new flexible simple point-charge water model was derived by optimizing bulk diffusion and dielec. consts. to the exptl. values via the equil. bond length and angle. Due to the large sensitivities, the parametrization only slightly perturbs the mol. geometry of the base SPC model. Extensive comparisons of thermodn., structural, and kinetic properties indicate that the new model is much improved over the std. SPC model and its overall performance is comparable to or even better than the extended SPC model.
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  76. 76
    Aragones, J. L.; Noya, E. G.; Abascal, J. L. F.; Vega, C. Properties of Ices at 0 K: A Test of Water Models. J. Chem. Phys. 2007, 127 (15), 154510– 154518,  DOI: 10.1063/1.2774986
    Google Scholar
    There is no corresponding record for this reference.
  77. 77
    Bushuev, Y. G.; Sastre, G.; de Julián-Ortiz, J. V.; Gálvez, J. Water-Hydrophobic Zeolite Systems. J. Phys. Chem. C 2012, 116 (47), 24916– 24929,  DOI: 10.1021/jp306188m
    Google Scholar
    77
    Water-Hydrophobic Zeolite Systems
    Bushuev, Yuriy G.; Sastre, German; de Julian-Ortiz, J. Vicente; Galvez, Jorge
    Journal of Physical Chemistry C (2012), 116 (47), 24916-24929CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
    Water intrusion-extrusion in hydrophobic microporous AFI, IFR, MTW and TON pure silica zeolites (zeosils) has been investigated through mol. dynamics (MD) simulations. It was found that intruded water vols. correlate with the free vol. of the zeosil unit cells. Calcd. adsorption isotherms allowed us to est. the amts. of water intruded, and deviations from expts. (lower exptl. with respect to calcd. intrusion pressures) have been explained in terms of connectivity defects in the synthesized materials. Water phase transitions in defectless zeosils occur in a narrow range at high pressure. On the basis of a simple model, we derived a thermodn. equation that allows one to est. the intrusion pressure with few parameters, which are easy to obtain, such as fractional free vol. of zeosil and the intrusion pressure of a ref. system. The structural properties of water clusters inside the zeosil micropores have been interpreted from the anal. of the MD simulations. Compact 'bulk-like' clusters form in large channels such as those in AFI and IFR zeosils. The smaller channels of MTW and TON promote the formation of chain-like clusters, which, interestingly, are commensurate with the zeolite channel topol. due to a coincidence between the distances of the crystallog. parameter, along the channel, and a max. in the O-O radial distribution function of bulk water.
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  1. Andrey Ryzhikov, Céline Dirand, Amir Astafan, Habiba Nouali, T. Jean Daou, Igor Bezverkhyy, Gérald Chaplais, Jean-Pierre Bellat. Calorimetric Heats of Intrusion of LiCl Aqueous Solutions in Hydrophobic MFI-Type Zeosil: Influence of the Concentration. Langmuir 2024, 40 (17) , 8827-8835. https://doi.org/10.1021/acs.langmuir.3c03931
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  • Abstract

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    Figure 1

    Figure 1. Intrusion–extrusion isotherms demonstrate three types of behavior for systems with different pore apertures: (a) number of water molecules vs pressure; cross sections of the pores are presented in insets; (b) fractional loadings vs pressure. Pintr and Pextr correspond to the half-loading of the tubes by definition.

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    Figure 2

    Figure 2. Intrusion–extrusion pressures vs reverse pore apertures for tubes, PSZs, and mesoporous silica. Estimated extrusion pressures are shown by gray circles.

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    Figure 3

    Figure 3. Time evolution of the average cosine between dipole moments and the axial direction of the tube (d = 7.9 Å): (a) at different pressures; (b) at P = 380 MPa. (c) Water clusters in the tube corresponding to event no. 1. Arrows show the orientation of dipole moments.

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    Figure 4

    Figure 4. Water clusters are formed in the tube with d = 10 Å. Green lines highlight the four-membered rings of H bonds.

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    Figure 5

    Figure 5. Water clusters in the tube with d = 10 Å. Arrows show the preferential orientation of the dipole moments.

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    Figure 6

    Figure 6. Extrusion of water from the tube with d = 14.3 Å at P = 10 MPa. Arrows show the preferential orientation of dipole moments, t is the time mark, and N is the number of water molecules in the tube.

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    Figure 7

    Figure 7. Statistics of H bonds (a) and rings (b) for bulk water at different pressures. Here, i is the number of hydrogen bonds in which a molecule participates.

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    Figure 8

    Figure 8. Mean number of H bonds in which a water molecule participated. Data for four tubes were linearly fitted (red line) and extrapolated (dashed black line).

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    Figure 9

    Figure 9. Statistics of H bonds for water: (a) in tubes with d ≥ 10 Å; (b) in the tube with d = 7.9 Å, comparing with theoretical predictions at k = 2 and 4, eq 2; (c) in the tube with d = 16.5 Å, comparing with bulk water and water in the imaginary tube. (d) Statistics of closed rings for bulk water and water in tubes.

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  • References

    This article references 77 other publications.

    1. 1
      Zhang, S.; Zhang, J.; Zhang, Y.; Deng, Y. Nanoconfined Ionic Liquids. Chem. Rev. 2017, 117 (10), 6755– 6833,  DOI: 10.1021/acs.chemrev.6b00509
      1
      Nanoconfined Ionic Liquids
      Zhang, Shiguo; Zhang, Jiaheng; Zhang, Yan; Deng, Youquan
      Chemical Reviews (Washington, DC, United States) (2017), 117 (10), 6755-6833CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. Ionic liqs. (ILs) have been widely investigated as novel solvents, electrolytes, and soft functional materials. Nevertheless, the widespread applications of ILs in most cases have been hampered by their liq. state. The confinement of ILs into nanoporous hosts is a simple but versatile strategy to overcome this problem. Nanoconfined ILs constitute a new class of composites with the intrinsic chemistries of ILs and the original functions of solid matrixes. The interplay between these two components, particularly the confinement effect and the interactions between ILs and pore walls, further endows ILs with significantly distinct physicochem. properties in the restricted space compared to the corresponding bulk systems. The aim of this article is to provide a comprehensive review of nanoconfined ILs. After a brief introduction of bulk ILs, the synthetic strategies and investigation methods for nanoconfined ILs are documented. The local structure and physicochem. properties of ILs in diverse porous hosts are summarized in the next sections. The final section highlights the potential applications of nanoconfined ILs in diverse fields, including catalysis, gas capture and sepn., ionogels, supercapacitors, carbonization, and lubrication. Further research directions and perspectives on this topic are also provided in the conclusion.
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    2. 2
      Kastelowitz, N.; Molinero, V. Ice-Liquid Oscillations in Nanoconfined Water. ACS Nano 2018, 12 (8), 8234– 8239,  DOI: 10.1021/acsnano.8b03403
      2
      Ice-Liquid Oscillations in Nanoconfined Water
      Kastelowitz, Noah; Molinero, Valeria
      ACS Nano (2018), 12 (8), 8234-8239CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
      Nanoscale confinement has a strong effect on the phase behavior of water. Studies in the last two decades have revealed a wealth of novel cryst. and quasicryst. structures for water confined in nanoslits. Less is known, however, about the nature of ice-liq. coexistence in extremely nanoconfined systems. Here, we use mol. simulations to investigate the ice-liq. equil. for water confined between two nanoscopic disks. We find that the nature of ice-liq. phase coexistence in nanoconfined water is different from coexistence in both bulk water and extended nanoslits. In highly nanoconfined systems, liq. water and ice do not coexist in space because the two-phase states are unstable. The confined ice and liq. phases coexist in time, through oscillations between all-liq. and all-cryst. states. The avoidance of spatial coexistence of ice and liq. originates on the non-negligible cost of the interface between confined ice and liq. in a small system. It is the result of the small no. of water mols. between the plates and has no analog in bulk water.
      >> More from SciFinder ®
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    3. 3
      Leoni, F.; Calero, C.; Franzese, G. Nanoconfined Fluids: Uniqueness of Water Compared to Other Liquids. ACS Nano 2021, 15 (12), 19864– 19876,  DOI: 10.1021/acsnano.1c07381
      3
      Nanoconfined Fluids: Uniqueness of Water Compared to Other Liquids
      Leoni, Fabio; Calero, Carles; Franzese, Giancarlo
      ACS Nano (2021), 15 (12), 19864-19876CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
      Nanoconfinement can drastically change the behavior of liqs., puzzling us with counterintuitive properties. It is relevant in applications, including decontamination and crystn. control. However, it still lacks a systematic anal. for fluids with different bulk properties. Here we address this gap. We compare, by mol. dynamics simulations, three different liqs. in a graphene slit pore: (A) A simple fluid, such as argon, described by a Lennard-Jones potential; (B) An anomalous fluid, such as a liq. metal, modeled with an isotropic core-softened potential; (C) Water, the prototypical anomalous liq., with directional hydrogen bonds. We study how the slit-pore width affects the structure, thermodn., and dynamics of the fluids. All the fluids show similar oscillating properties by changing the pore size. However, their free-energy min. are quite different in nature: (i) are energy-driven for the simple liq.; (ii) are entropy-driven for the isotropic core-softened potential; (iii) have a changing nature for water. Indeed, for water the monolayer min. is entropy-driven, at variance with the simple liq., while the bilayer min. is energy-driven, at variance with the other anomalous liq. Also, water has a large increase in diffusion for subnm slit pores, becoming faster than bulk. Instead, the other two fluids have diffusion oscillations much smaller than water, slowing down for decreasing slit-pore width. Our results, clarifying that water confined at the subnm scale behaves differently from other (simple or anomalous) fluids under similar confinement, are possibly relevant in nanopores applications, e.g., in water purifn. from contaminants. Longitudinal diffusion coeff. D‖, normalized to its large-δ value, for the three fluids in a slit-pore, as a function of the plate sepn. δ. Comparison of the TIP4P/2005-water (blue triangles) with (a) the LJ (black circles), and (b) the CSW (red squares). In both panels vertical lines mark, approx., maxima (dotted lines) and min. (dot-dashed lines) for the isotropic fluid (see text). The value of D‖ at δ = 17 Å is ≃23 nm2/ns for both the LJ and the CSW, and is ≃1.9 nm2/ns for the TIP4P/2005-water.
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    4. 4
      Giacomello, A. What Keeps Nanopores Boiling. J. Chem. Phys. 2023, 159 (11), 110902,  DOI: 10.1063/5.0167530
      4
      What keeps nanopores boiling
      Giacomello, Alberto
      Journal of Chemical Physics (2023), 159 (11), 110902CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
      A review. The liq.-to-vapor transition can occur under unexpected conditions in nanopores, opening the door to fundamental questions and new technologies. The physics of boiling in confinement is progressively introduced, starting from classical nucleation theory, passing through nanoscale effects, and terminating with the material and external parameters that affect the boiling conditions. The relevance of boiling in specific nanoconfined systems is discussed, focusing on heterogeneous lyophobic systems, chromatog. columns, and ion channels. The current level of control of boiling in nanopores enabled by microporous materials such as metal org. frameworks and biol. nanopores paves the way to thrilling theor. challenges and to new technol. opportunities in the fields of energy, neuromorphic computing, and sensing. (c) 2023 American Institute of Physics.
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    5. 5
      Gritti, F.; Hlushkou, D.; Tallarek, U. Faster Dewetting of Water from C8- than from C18-Bonded Silica Particles Used in Reversed-Phase Liquid Chromatography: Solving the Paradox. J. Chromatogr. A 2019, 1602, 253– 265,  DOI: 10.1016/j.chroma.2019.05.041
      5
      Faster dewetting of water from C8- than from C18-bonded silica particles used in reversed-phase liquid chromatography: Solving the paradox
      Gritti, Fabrice; Hlushkou, Dzmitry; Tallarek, Ulrich
      Journal of Chromatography A (2019), 1602 (), 253-265CODEN: JCRAEY; ISSN:0021-9673. (Elsevier B.V.)
      For comparable surface coverage of alkyl-bonded chains (∼3μmol/m2), the dewetting of 100% aq. mobile phases from the mesopores of octyl(C8)-bonded silica particles is found 70 times faster than that from the same but octadecyl(C18)-bonded silica particles. This observation was made in this work for both fully porous (5μm Symmetry) and superficially porous (2.7μm CORTECS) particles. This exptl. result is paradoxical because (1) the av. pore size of C8-bonded materials is 10-15 Å larger than that of C18-bonded materials for the same unbounded silica gel and (2) the contact angle of water measured on smooth and planar C8-bonded surface is ∼6° smaller than that on the same but C18-bonded surface (104° vs. 110°). The equil. Laplace pressure is then expected to be smaller and the kinetics of water dewetting to be slower for silica-C8 than for silica-C18 stationary phases used in RPLC. The soln. to this riddle was studied based on (1) the calcn. of the dewetting time assuming that the pores are monosized and the process is driven by the Laplace pressure, (2) the measurement of the advancing and receding contact angles of three different C18- and C8-bonded silica gels (4μm NovaPak, 5μm Symmetry, and 2.7μm CORTECS) from the water porograms measured in a range of water pressure from normal pressure to 500 bar, and (3) on the calcn. of the pore connectivity for both C8 and C18-bonded silica. First, the obsd. dewetting times are of the order of minutes or even hours instead of millisecond as predicted by the dewetting model. Secondly, the advancing and receding contact angles of water onto the C8-bonded silicas are found larger (by an av. of +7° and +2°, resp.) than those measured for the same but C18-bonded silica (av. of 112° and 92°). Finally, the calcd. pore connectivity is decreasing by ∼30% for 90 Å unbounded silica materials from C8 to C18-bonded RPLC phases. Overall, the obsd. and much faster dewetting of water from C8 column than that from C18 column is primarily explained by a higher internal pore connectivity due to the thinner thickness of the alkyl-bonded layer (7 Å vs. 15 Å) and, to a lesser extent, by a higher extrusion Laplace pressure of water (≃+10 bar).
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    6. 6
      Eroshenko, V.; Regis, R. C.; Soulard, M.; Patarin, J. Energetics: A New Field of Applications for Hydrophobic Zeolites. J. Am. Chem. Soc. 2001, 123 (33), 8129– 8130,  DOI: 10.1021/ja011011a
      6
      Energetics. A new field of applications for hydrophobic zeolites
      Eroshenko, Valentin; Regis, Robert-Charles; Soulard, Michel; Patarin, Joeel
      Journal of the American Chemical Society (2001), 123 (33), 8129-8130CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      A thermodn. study was carried out for several hydrophobic zeolites in contact with H2O. The water-zeolite β, water silicalite-1 (OH-), and water silicalite-1 (F-) systems were examd. The compressibility of the systems was measured, and the pressure-vol. isotherms are depicted. The reciprocal transformation of mech. energy into interfacial energy in such a system is discussed together with possible energetic applications.
      >> More from SciFinder ®
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    7. 7
      Fraux, G.; Coudert, F. X.; Boutin, A.; Fuchs, A. H. Forced Intrusion of Water and Aqueous Solutions in Microporous Materials: From Fundamental Thermodynamics to Energy Storage Devices. Chem. Soc. Rev. 2017, 46 (23), 7421– 7437,  DOI: 10.1039/C7CS00478H
      7
      Forced intrusion of water and aqueous solutions in microporous materials: from fundamental thermodynamics to energy storage devices
      Fraux, Guillaume; Coudert, Francois-Xavier; Boutin, Anne; Fuchs, Alain H.
      Chemical Society Reviews (2017), 46 (23), 7421-7437CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      We review the high pressure forced intrusion studies of water in hydrophobic microporous materials such as zeolites and MOFs, a field of research that has emerged some 15 years ago and is now very active. Many of these studies are aimed at investigating the possibility of using these systems as energy storage devices. A series of all-silica zeolites (zeosil) frameworks were found suitable for reversible energy storage because of their stability with respect to hydrolysis after several water intrusion-extrusion cycles. Several microporous hydrophobic zeolite imidazolate frameworks (ZIFs) also happen to be quite stable and resistant towards hydrolysis and thus seem very promising for energy storage applications. Replacing pure water by electrolyte aq. solns. enables to increase the stored energy by a factor close to 3, on account of the high pressure shift of the intrusion transition. In addn. to the fact that aq. solns. and microporous silica materials are environmental friendly, these systems are thus becoming increasingly interesting for the design of new energy storage devices. This review also addresses the theor. approaches and mol. simulations performed in order to better understand the exptl. behavior of nano-confined water. Mol. simulation studies showed that water condensation takes place through a genuine first-order phase transition, provided that the interconnected pores structure is 3-dimensional and sufficiently open. In an extreme confinement situations such as in ferrierite zeosil, condensation seem to take place through a continuous supercrit. crossing from a dild. to a dense fluid, on account of the fact that the first-order transition line is shifted to higher pressure, and the confined water crit. point is correlatively shifted to lower temp. These mol. simulation studies suggest that the most important features of the intrusion/extrusion process can be understood in terms of equil. thermodn. considerations.
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    8. 8
      Wu, L.; Li, Y.; Fu, Z.; Su, B. L. Hierarchically Structured Porous Materials: Synthesis Strategies and Applications in Energy Storage. Natl. Sci. Rev. 2020, 7 (11), 1667– 1701,  DOI: 10.1093/nsr/nwaa183
      8
      Hierarchically structured porous materials: synthesis strategies and applications in energy storage
      Wu, Liang; Li, Yu; Fu, Zhengyi; Su, Bao-Lian
      National Science Review (2020), 7 (11), 1667-1701CODEN: NSRACI; ISSN:2053-714X. (Oxford University Press)
      To address the growing energy demands of sustainable development, it is crucial to develop new materials that can improve the efficiency of energy storage systems. Hierarchically structured porous materials have shown their great potential for energy storage applications owing to their large accessible space, high surface area, low d., excellent accommodation capability with vol. and thermal variation, variable chem. compns. and well controlled and interconnected hierarchical porosity at different length scales. Porous hierarchy benefits electron and ion transport, and mass diffusion and exchange. The electrochem. behavior of hierarchically structured porous materials varies with different pore parameters. Understanding their relationship can lead to the defined and accurate design of highly efficient hierarchically structured porous materials to enhance further their energy storage performance. In this review, we take the characteristic parameters of the hierarchical pores as the survey object to summarize the recent progress on hierarchically structured porous materials for energy storage. This is the first of this kind exclusively to survey the performance of hierarchically structured porous materials from different porous characteristics. For those who are not familiar with hierarchically structured porous materials, a series of very significant synthesis strategies of hierarchically structured porous materials are firstly and briefly reviewed.This will be beneficial for those who want to quickly obtain useful ref. information about the synthesis strategies of new hierarchically structured porousmaterials to improve their performance in energy storage. The effect of different organizational, structural and geometric parameters of porous hierarchy on their electrochem. behavior is then deeply discussed.We outline the existing problems and development challenges of hierarchically structured porous materials that need to be addressed in renewable energy applications.We hope that this review can stimulate strong intuition into the design and application of new hierarchically structured porous materials in energy storage and other fields.
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    9. 9
      Hashemi-Tilehnoee, M.; Tsirin, N.; Stoudenets, V.; Bushuev, Y. G.; Chorążewski, M.; Li, M.; Li, D.; Leão, J. B.; Bleuel, M.; Zajdel, P.; Del Barrio, E. P.; Grosu, Y. Liquid Piston Based on Molecular Springs for Energy Storage Applications. J. Energy Storage 2023, 68, 107697,  DOI: 10.1016/j.est.2023.107697
      There is no corresponding record for this reference.
    10. 10
      Confalonieri, G.; Daou, T. J.; Nouali, H.; Arletti, R.; Ryzhikov, A. Energetic Performance of Pure Silica Zeolites under High-Pressure Intrusion of LiCl Aqueous Solutions: An Overview. Molecules 2020, 25 (9), 2145,  DOI: 10.3390/molecules25092145
      10
      Energetic performance of pure silica zeolites under high-pressure intrusion of LiCl aqueous solutions: an overview
      Confalonieri, Giorgia; Daou, T. Jean; Nouali, Habiba; Arletti, Rossella; Ryzhikov, Andrey
      Molecules (2020), 25 (9), 2145CODEN: MOLEFW; ISSN:1420-3049. (MDPI AG)
      A review. An overview of all the studies on high-pressure intrusion-extrusion of LiCl aq. solns. in hydrophobic pure silica zeolites (zeosils) for absorption and storage of mech. energy is presented. Operational principles of heterogeneous lyophobic systems and their possible applications in the domains of mech. energy storage, absorption, and generation are described. The intrusion of LiCl aq. solns. instead of water allows to considerably increase energetic performance of zeosil-based systems by a strong rise of intrusion pressure. The intrusion pressure increases with the salt concn. and depends considerably on zeosil framework. In the case of channel-type zeosils, it rises with the decrease of pore opening diam., whereas for cage-type ones, no clear trend is obsd. A relative increase of intrusion pressure in comparison with water is particularly strong for the zeosils with narrow pore openings. The use of highly concd. LiCl aq. solns. instead of water can lead to a change of system behavior. This effect seems to be related to a lower formation of silanol defects under intrusion of solvated ions and a weaker interaction of the ions with silanol groups of zeosil framework. The influence of zeosil nanostructure on LiCl aq. solns. intrusion-extrusion is also discussed.
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    11. 11
      Grosu, Y.; Li, M.; Peng, Y. L.; Luo, D.; Li, D.; Faik, A.; Nedelec, J. M.; Grolier, J. P. A Highly Stable Nonhysteretic {Cu2(Tebpz) MOF+water} Molecular Spring. ChemPhysChem 2016, 17 (21), 3359– 3364,  DOI: 10.1002/cphc.201600567
      11
      A Highly Stable Nonhysteretic {Cu2(tebpz) MOF + water} Molecular Spring
      Grosu, Yaroslav; Li, Mian; Peng, Yun-Lei; Luo, Dong; Li, Dan; Faik, Abdessamad; Nedelec, Jean-Marie; Grolier, Jean-Pierre
      ChemPhysChem (2016), 17 (21), 3359-3364CODEN: CPCHFT; ISSN:1439-4235. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A mol. spring formed by a hydrophobic metal-org. framework Cu2(tebpz) (tebpz = 3,3',5,5'-tetraethyl-4,4'-bipyrazolate) and water is presented. This nanoporous heterogeneous lyophobic system (HLS) has exceptional properties compared to numerous reported systems of such type in terms of stability, efficiency, and operating pressure. Mech. and thermal energetic characteristics as well as stability of the system are discussed and compared in detail with those of other previously reported HLS.
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    12. 12
      Bennett, T. D.; Coudert, F. X.; James, S. L.; Cooper, A. I. The Changing State of Porous Materials. Nat. Mater. 2021, 20 (9), 1179– 1187,  DOI: 10.1038/s41563-021-00957-w
      12
      The changing state of porous materials
      Bennett, Thomas D.; Coudert, Francois-Xavier; James, Stuart L.; Cooper, Andrew I.
      Nature Materials (2021), 20 (9), 1179-1187CODEN: NMAACR; ISSN:1476-1122. (Nature Portfolio)
      A review. Porous materials contain regions of empty space into which guest mols. can be selectively adsorbed and sometimes chem. transformed. This has made them useful in both industrial and domestic applications, ranging from gas sepn., energy storage and ion exchange to heterogeneous catalysis and green chem. Porous materials are often ordered (cryst.) solids. Order-or uniformity-is frequently held to be advantageous, or even pivotal, to our ability to engineer useful properties in a rational way. Here we highlight the growing evidence that topol. disorder can be useful in creating alternative properties in porous materials. In particular, we highlight here several concepts for the creation of novel porous liqs., rationalize routes to porous glasses and provide perspectives on applications for porous liqs. and glasses.
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    13. 13
      Egleston, B. D.; Mroz, A.; Jelfs, K. E.; Greenaway, R. L. Porous Liquids - the Future Is Looking Emptier. Chem. Sci. 2022, 13, 5042– 5054,  DOI: 10.1039/D2SC00087C
      13
      Porous liquids - the future is looking emptier
      Egleston, Benjamin D.; Mroz, Austin; Jelfs, Kim E.; Greenaway, Rebecca L.
      Chemical Science (2022), 13 (18), 5042-5054CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
      The development of microporosity in the liq. state is leading to an inherent change in the way we approach applications of functional porosity, potentially allowing access to new processes by exploiting the fluidity of these new materials. By engineering permanent porosity into a liq., over the transient intermol. porosity in all liqs., it is possible to design and form a porous liq. Since the concept was proposed in 2007, and the first examples realized in 2015, the field has seen rapid advances among the types and nos. of porous liqs. developed, our understanding of the structure and properties, as well as improvements in gas uptake and mol. sepns. However, despite these recent advances, the field is still young, and with only a few applications reported to date, the potential that porous liqs. have to transform the field of microporous materials remains largely untapped. In this review, we will explore the theory and conception of porous liqs. and cover major advances in the area, key exptl. characterization techniques and computational approaches that have been employed to understand these systems, and summarise the investigated applications of porous liqs. that have been presented to date. We also outline an emerging discovery workflow with recommendations for the characterization required at each stage to both confirm permanent porosity and fully understand the phys. properties of the porous liq.
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    14. 14
      Canivet, J.; Fateeva, A.; Guo, Y.; Coasne, B.; Farrusseng, D. Water Adsorption in MOFs: Fundamentals and Applications. Chem. Soc. Rev. 2014, 43 (16), 5594– 5617,  DOI: 10.1039/C4CS00078A
      14
      Water adsorption in MOFs: fundamentals and applications
      Canivet, Jerome; Fateeva, Alexandra; Guo, Youmin; Coasne, Benoit; Farrusseng, David
      Chemical Society Reviews (2014), 43 (16), 5594-5617CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review. This review article presents the fundamental and practical aspects of water adsorption in Metal-Org. Frameworks (MOFs). The state of the art of MOF stability in water, a crucial issue to many applications in which MOFs are promising candidates, is discussed here. Stability in both gaseous (such as humid gases) and aq. media is considered. By considering a non-exhaustive yet representative set of MOFs, the different mechanisms of water adsorption in this class of materials are presented: reversible and continuous pore filling, irreversible and discontinuous pore filling through capillary condensation, and irreversibility arising from the flexibility and possible structural modifications of the host material. Water adsorption properties of more than 60 MOF samples are reported. The applications of MOFs as materials for heat-pumps and adsorbent-based chillers and proton conductors are also reviewed. Some directions for future work are suggested as concluding remarks.
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    15. 15
      Rangnekar, N.; Mittal, N.; Elyassi, B.; Caro, J.; Tsapatsis, M. Zeolite Membranes - a Review and Comparison with MOFs. Chem. Soc. Rev. 2015, 44 (20), 7128– 7154,  DOI: 10.1039/C5CS00292C
      15
      Zeolite membranes - a review and comparison with MOFs
      Rangnekar, N.; Mittal, N.; Elyassi, B.; Caro, J.; Tsapatsis, M.
      Chemical Society Reviews (2015), 44 (20), 7128-7154CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      The latest developments in zeolite membranes are reviewed, with an emphasis on the synthesis techniques, including seed assembly and secondary growth methods. This review also discusses the current industrial applications of zeolite membranes, the feasibility of their use in membrane reactors and their hydrothermal stability. Finally, zeolite membranes are compared with metal-org. framework (MOF) membranes and the latest advancements in MOF and mixed matrix membranes are highlighted.
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    16. 16
      Alexiadis, A.; Kassinos, S. Molecular Simulation of Water in Carbon Nanotubes. Chem. Rev. 2008, 108 (12), 5014– 5034,  DOI: 10.1021/cr078140f
      16
      Molecular Simulation of Water in Carbon Nanotubes
      Alexiadis, Alessio; Kassinos, Stavros
      Chemical Reviews (Washington, DC, United States) (2008), 108 (12), 5014-5034CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. The authors review the recent advances in the area of mol. dynamics of water in carbon nanotubes. It is shown that many properties of confined water differ from those of bulk water and depend on the nanotube size. Due to the effect of confinement, the phase diagram of water gains a new dimension (the nanotube diam.). All the water models available are parametrized for bulk water and it is not known how reliable they are in the case of confined water. Results obtained with different water models provide different pictures of the structure of the water layers. Ab initio calcns. can represent the optimal answer since they are based on first principles and do not require any parametrized force fields.
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    17. 17
      Barboiu, M. Artificial Water Channels. Angew. Chem., Int. Ed. 2012, 51 (47), 11674– 11676,  DOI: 10.1002/anie.201205819
      17
      Artificial Water Channels
      Barboiu, Mihail
      Angewandte Chemie, International Edition (2012), 51 (47), 11674-11676CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. Water is fundamental to life, playing a variety of roles related to its complex dynamic behavior at the supramol. level. Most physiol. processes depend on the selective exchange of ions or mols. between a cell and its environment, with water serving a crucial function in these translocation events. Artificial ion channels have been extensively studied with the goal of facilitating ionic conduction in bilayer membranes; however, there has not been as much progress in the area of synthetic water channels. Several artificial water channel systems have been reported to date, and these include the following: (1) helical pores assembled from dendritic peptides; (2) a chiral supramol. imidazole (I)-quartet assembled from lipophilic ureidoimidazole; and (3) polyazide-substituted pillar[5]arenes assembled into tubular hydrogen-bonded superstructures.
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    18. 18
      Clayson, I. G.; Hewitt, D.; Hutereau, M.; Pope, T.; Slater, B. High Throughput Methods in the Synthesis, Characterization, and Optimization of Porous Materials. Adv. Mater. 2020, 32 (44), 1– 47,  DOI: 10.1002/adma.202002780
      There is no corresponding record for this reference.
    19. 19
      Lynch, C. I.; Rao, S.; Sansom, M. S. P. Water in Nanopores and Biological Channels: A Molecular Simulation Perspective. Chem. Rev. 2020, 120 (18), 10298– 10335,  DOI: 10.1021/acs.chemrev.9b00830
      19
      Water in Nanopores and Biological Channels: A Molecular Simulation Perspective
      Lynch, Charlotte I.; Rao, Shanlin; Sansom, Mark S. P.
      Chemical Reviews (Washington, DC, United States) (2020), 120 (18), 10298-10335CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. This Review explores the dynamic behavior of water within nanopores and biol. channels in lipid bilayer membranes. We focus on mol. simulation studies, alongside selected structural and other exptl. investigations. Structures of biol. nanopores and channels are reviewed, emphasizing those high-resoln. crystal structures, which reveal water mols. within the transmembrane pores, which can be used to aid the interpretation of simulation studies. Different levels of mol. simulations of water within nanopores are described, with a focus on mol. dynamics (MD). In particular, models of water for MD simulations are discussed in detail to provide an evaluation of their use in simulations of water in nanopores. Simulation studies of the behavior of water in idealized models of nanopores have revealed aspects of the organization and dynamics of nanoconfined water, including wetting/dewetting in narrow hydrophobic nanopores. A survey of simulation studies in a range of nonbiol. nanopores is presented, including carbon nanotubes, synthetic nanopores, model peptide nanopores, track-etched nanopores in polymer membranes, and hydroxylated and functionalized nanoporous silica. These reveal a complex relationship between pore size/geometry, the nature of the pore lining, and rates of water transport. Wider nanopores with hydrophobic linings favor water flow whereas narrower hydrophobic pores may show dewetting. Simulation studies over the past decade of the behavior of water in a range of biol. nanopores are described, including porins and β-barrel protein nanopores, aquaporins and related polar solute pores, and a no. of different classes of ion channels. Water is shown to play a key role in proton transport in biol. channels and in hydrophobic gating of ion channels. An overall picture emerges, whereby the behavior of water in a nanopore may be predicted as a function of its hydrophobicity and radius. This informs our understanding of the functions of diverse channel structures and will aid the design of novel nanopores. Thus, our current level of understanding allows for the design of a nanopore which promotes wetting over dewetting or vice versa. However, to design a novel nanopore, which enables fast, selective, and gated flow of water de novo would remain challenging, suggesting a need for further detailed simulations alongside exptl. evaluation of more complex nanopore systems.
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    20. 20
      Levy, Y.; Onuchic, J. N. Water Mediation in Protein Folding and Molecular Recognition. Annu. Rev. Biophys. Biomol. Struct. 2006, 35 (1), 389– 415,  DOI: 10.1146/annurev.biophys.35.040405.102134
      20
      Water mediation in protein folding and molecular recognition
      Levy, Yaakov; Onuchic, Jose N.
      Annual Review of Biophysics and Biomolecular Structure (2006), 35 (), 389-415CODEN: ABBSE4; ISSN:1056-8700. (Annual Reviews Inc.)
      A review. Water is essential for life in many ways, and without it biomols. might no longer truly be biomols. In particular, water is important to the structure, stability, dynamics, and function of biol. macromols. In protein folding, water mediates the collapse of the chain and the search for the native topol. through a funneled energy landscape. Water actively participates in mol. recognition by mediating the interactions between binding partners and contributes to either enthalpic or entropic stabilization. Accordingly, water must be included in recognition and structure prediction codes to capture specificity. Thus, water should not be treated as an inert environment, but rather as an integral and active component of biomol. systems, where it has both dynamic and structural roles. Focusing on water sheds light on the physics and function of biol. machinery and self-assembly and may advance the understanding of the natural design of proteins and nucleic acids.
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    21. 21
      Yin, H.; Hummer, G.; Rasaiah, J. C. Metastable Water Clusters in the Nonpolar Cavities of the Thermostable Protein Tetrabrachion. J. Am. Chem. Soc. 2007, 129 (23), 7369– 7377,  DOI: 10.1021/ja070456h
      21
      Metastable Water Clusters in the Nonpolar Cavities of the Thermostable Protein Tetrabrachion
      Yin, Hao; Hummer, Gerhard; Rasaiah, Jayendran C.
      Journal of the American Chemical Society (2007), 129 (23), 7369-7377CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Water expulsion from the protein core is a key step in protein folding. Nevertheless, unusually large water clusters confined into the nonpolar cavities have been obsd. in the x-ray crystal structures of tetrabrachion, a bacterial protein that is thermostable up to at least 403 K (130°). Here, we use mol. dynamics (MD) simulations to investigate the structure and thermodn. of water filling the largest cavity of the right-handed coiled-coil stalk of tetrabrachion at 365 K (92°), the temp. of optimal bacterial growth, and at room temp. (298 K). Hydrogen-bonded water clusters of seven to nine water mols. are found to be thermodynamically stable in this cavity at both temps., confirming the x-ray studies. Stability, as measured by the transfer free energy of the optimal size cluster, decreases with increasing temp. Water filling is thus driven by the energy of transfer and opposed by the transfer entropy, both depending only weakly on temp. Our calcns. suggest that cluster formation becomes unfavorable at ∼384 K (110°), signaling the onset of drying just slightly above the temp. of optimal growth. "Drying" thus precedes protein denaturation. At room temp., the second largest cavity in tetrabrachion accommodates a five water mol. cluster, as reported in the x-ray studies. However, the simulations show that at 365 K the cluster is unstable and breaks up. We suggest that the large hydrophobic cavities may act as binding sites for two proteases, possibly explaining the unusual thermostability of the resulting protease-stalk complexes (up to ∼393 K, 120°).
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    22. 22
      Chatzichristos, A.; Hassan, J. Current Understanding of Water Properties inside Carbon Nanotubes. Nanomaterials 2022, 12 (1), 174,  DOI: 10.3390/nano12010174
      22
      Current Understanding of Water Properties inside Carbon Nanotubes
      Chatzichristos, Aris; Hassan, Jamal
      Nanomaterials (2022), 12 (1), 174CODEN: NANOKO; ISSN:2079-4991. (MDPI AG)
      A review. Confined water inside carbon nanotubes (CNTs) has attracted a lot of attention in recent years, amassing as a result a very large no. of dedicated studies, both theor. and exptl. This exceptional scientific interest can be understood in terms of the exotic properties of nanoconfined water, as well as the vast array of possible applications of CNTs in a wide range of fields stretching from geol. to medicine and biol. This review presents an overreaching narrative of the properties of water in CNTs, based mostly on results from systematic NMR (NMR) and mol. dynamics (MD) studies, which together allow the untangling and explanation of many seemingly contradictory results present in the literature. Further, we identify still-debatable issues and open problems, as well as avenues for future studies, both theor. and exptl.
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    23. 23
      Mochizuki, K.; Koga, K.; Sastry, S. Solid-Liquid Critical Behavior of Water in Nanopores. Proc. Natl. Acad. Sci. U.S.A. 2015, 112 (27), 8221– 8226,  DOI: 10.1073/pnas.1422829112
      23
      Solid-liquid critical behavior of water in nanopores
      Mochizuki, Kenji; Koga, Kenichiro
      Proceedings of the National Academy of Sciences of the United States of America (2015), 112 (27), 8221-8226CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
      Nanoconfined liq. water can transform into low-dimensional ices whose cryst. structures are dissimilar to any bulk ices and whose m.p. may significantly rise with reducing the pore size, as revealed by computer simulation and confirmed by expt. One of the intriguing, and as yet unresolved, questions concerns the observation that the liq. water may transform into a low-dimensional ice either via a first-order phase change or without any discontinuity in thermodn. and dynamic properties, which suggests the existence of solid-liq. crit. points in this class of nanoconfined systems. Here we explore the phase behavior of a model of water in carbon nanotubes in the temp.-pressure-diam. space by mol. dynamics simulation and provide unambiguous evidence to support solid-liq. crit. phenomena of nanoconfined water. Solid-liq. first-order phase boundaries are detd. by tracing spontaneous phase sepn. at various temps. All of the boundaries eventually cease to exist at the crit. points and there appear loci of response function maxima, or the Widom lines, extending to the supercrit. region. The finite-size scaling anal. of the d. distribution supports the presence of both first-order and continuous phase changes between solid and liq. At around the Widom line, there are microscopic domains of two phases, and continuous solid-liq. phase changes occur in such a way that the domains of one phase grow and those of the other evanesce as the thermodn. state departs from the Widom line.
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    24. 24
      Bushuev, Y. G.; Sastre, G. Atomistic Simulation of Water Intrusion-Extrusion in ITQ-4 (IFR) and ZSM-22 (TON): The Role of Silanol Defects. J. Phys. Chem. C 2011, 115 (44), 21942– 21953,  DOI: 10.1021/jp207020w
      24
      Atomistic Simulation of Water Intrusion-Extrusion in ITQ-4 (IFR) and ZSM-22 (TON): The Role of Silanol Defects
      Bushuev, Yuriy G.; Sastre, German
      Journal of Physical Chemistry C (2011), 115 (44), 21942-21953CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      Water in pure silica zeolites (zeosils) may behave as a bumper by absorbing mech. energy of the intruded water, as a spring by restoring after extrusion of the energy spent in intrusion, or as shock absorber by dissipating the energy. The understanding of how the structure and topol. of the zeosils are responsible of such behavior has not yet been fully clarified. Mol. dynamics and mol. mechanics simulations of IFR- and TON-type zeosils were performed in an attempt to elucidate the energetics of these materials after water intrusion-extrusion. The authors aim the simulations to capture the exptl. obsd. bumper and spring water-zeosil behavior of IFR and TON, resp. The excess energy with respect to dry zeosil was calcd., and this relates to the energetic response of the zeosil after water intrusion. The excess energy of water-TON is larger than the energy of bulk water at any loading. The small opening of the TON channel prevents the formation of energetically stable bulky water clusters. The water content is stabilized on a certain loading range in water-IFR. Any silanol defects in IFR framework channels stabilize systems. Defect positions (silanol groups), which make the water-IFR system energetically stable, are found. Silanol groups increase the hydrophilicity of IFR-type zeosil, initially hydrophobic. There are two factors explaining the bumper behavior (under high pressure, water penetrates into the zeosil channels and remains there even after the pressure is released) of water-IFR systems: channel size and hydrolisis leading to framework breaking under large hydrostatic pressure. Silanol groups in channels are centers of water clusterization. The chem. stability of TON framework and its small channel size explain its spring behavior.
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    25. 25
      Karbowiak, T.; Saada, M. A.; Rigolet, S.; Ballandras, A.; Weber, G.; Bezverkhyy, I.; Soulard, M.; Patarin, J.; Bellat, J. P. New Insights in the Formation of Silanol Defects in Silicalite-1 by Water Intrusion under High Pressure. Phys. Chem. Chem. Phys. 2010, 12 (37), 11454– 11466,  DOI: 10.1039/c000931h
      25
      New insights in the formation of silanol defects in silicalite-1 by water intrusion under high pressure
      Karbowiak, Thomas; Saada, Mohamed-Ali; Rigolet, Severinne; Ballandras, Anthony; Weber, Guy; Bezverkhyy, Igor; Soulard, Michel; Patarin, Joel; Bellat, Jean-Pierre
      Physical Chemistry Chemical Physics (2010), 12 (37), 11454-11466CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
      The water-silicalite-1" system is known to act as a mol. spring. The successive intrusion-extrusion cycles of liq. water in small crystallites (6 × 3 × 0.5 μm3) of hydrophobic silicalite-1 were studied by volumetric and calorimetric techniques. The expts. displayed a decrease of the intrusion pressure between the 1st intrusion-extrusion cycle and the consecutive ones, whereas the extrusion pressures remained unchanged. However, neither XRD studies nor SEM observations revealed any structural and morphol. modifications of silicalite-1 at the long-range order. Such a shift in the value of the intrusion pressure after the 1st water intrusion-extrusion cycle is attributed to the creation of silanol groups during the 1st water intrusion. Detailed FTIR and solid-state NMR spectroscopic characterizations provided a mol. evidence of chem. modification of zeolite framework with the formation of local silanol defects created by the breaking of siloxane bonds.
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    26. 26
      Narayan, R.; Nayak, U. Y.; Raichur, A. M.; Garg, S. Mesoporous Silica Nanoparticles: A Comprehensive Review on Synthesis and Recent Advances. Pharmaceutics 2018, 10 (3), 118– 149,  DOI: 10.3390/pharmaceutics10030118
      26
      Mesoporous silica nanoparticles: a comprehensive review on synthesis and recent advances
      Narayan, Reema; Nayak, Usha Y.; Raichur, Ashok M.; Garg, Sanjay
      Pharmaceutics (2018), 10 (3), 118CODEN: PHARK5; ISSN:1999-4923. (MDPI AG)
      Recent advancements in drug delivery technologies utilizing a variety of carriers have resulted in a path-breaking revolution in the approach towards diagnosis and therapy alike in the current times. Need for materials with high thermal, chem. and mech. properties have led to the development of mesoporous silica nanoparticles (MSNs). These ordered porous materials have garnered immense attention as drug carriers owing to their distinctive features over the others. They can be synthesized using a relatively simple process, thus making it cost effective. Moreover, by controlling the parameters during the synthesis; the morphol., pore size and vol. and particle size can be transformed accordingly. Over the last few years, a rapid increase in research on MSNs as drug carriers for the treatment of various diseases has been obsd. indicating its potential benefits in drug delivery. Their widespread application for the loading of small mols. as well as macromols. such as proteins, siRNA and so forth, has made it a versatile carrier. In the recent times, researchers have sorted to several modifications in the framework of MSNs to explore its potential in drug resistant chemotherapy, antimicrobial therapy. In this review, we have discussed the synthesis of these multitalented nanoparticles and the factors influencing the size and morphol. of this wonder carrier. The second part of this review emphasizes on the applications and the advances made in the MSNs to broaden the spectrum of its use esp. in the field of biomedicine. We have also touched upon the lacunae in the thorough understanding of its interaction with a biol. system which poses a major hurdle in the passage of this carrier to the clin. level. In the final part of this review, we have discussed some of the major patents filed in the field of MSNs for therapeutic purpose.
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    27. 27
      Ahmadi, F.; Sodagar-Taleghani, A.; Ebrahimnejad, P.; Pouya Hadipour Moghaddam, S.; Ebrahimnejad, F.; Asare-Addo, K.; Nokhodchi, A. A Review on the Latest Developments of Mesoporous Silica Nanoparticles as a Promising Platform for Diagnosis and Treatment of Cancer. Int. J. Pharm. 2022, 625 (March), 122099,  DOI: 10.1016/j.ijpharm.2022.122099
      27
      A review on the latest developments of mesoporous silica nanoparticles as a promising platform for diagnosis and treatment of cancer
      Ahmadi, Fatemeh; Sodagar-Taleghani, Arezoo; Ebrahimnejad, Pedram; Pouya Hadipour Moghaddam, Seyyed; Ebrahimnejad, Farzam; Asare-Addo, Kofi; Nokhodchi, Ali
      International Journal of Pharmaceutics (Amsterdam, Netherlands) (2022), 625 (), 122099CODEN: IJPHDE; ISSN:0378-5173. (Elsevier B.V.)
      A review. Cancer is the second cause of human mortality after cardiovascular disease around the globe. Conventional cancer therapies are chemotherapy, radiation, and surgery. In fact, due to the lack of abs. specificity and high drug concns., early recognition and treatment of cancer with conventional approaches have become challenging issues in the world. To mitigate against the limitations of conventional cancer chemotherapy, nanomaterials have been developed. Nanomaterials exhibit particular properties that can overcome the drawbacks of conventional therapies such as lack of specificity, high drug concns., and adverse drug reactions. Among nanocarriers, mesoporous silica nanoparticles (MSNs) have gained increasing attention due to their well-defined pore size and structure, high surface area, good biocompatibility and biodegradability, ease of surface modification, and stable aq. dispersions. This review highlights the current progress with the use of MSNs for the delivery of chemotherapeutic agents for the diagnosis and treatment of cancer. Various stimuli-responsive gatekeepers, which endow the MSNs with on-demand drug delivery, surface modification strategies for targeting purposes, and multifunctional MSNs utilized in drug delivery systems (DDSs) are also addressed. Also, the capability of MSNs as flexible imaging platforms is considered. In addn., physicochem. attributes of MSNs and their effects on cancer therapy with a particular focus on recent studies is emphasized. Moreover, major challenges to the use of MSNs for cancer therapy, biosafety and cytotoxicity aspects of MSNs are discussed.
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    28. 28
      Lefevre, B.; Saugey, A.; Barrat, J. L.; Bocquet, L.; Charlaix, E.; Gobin, P. F.; Vigier, G. Intrusion and Extrusion of Water in Hydrophobic Mesopores. J. Chem. Phys. 2004, 120 (10), 4927– 4938,  DOI: 10.1063/1.1643728
      28
      Intrusion and extrusion of water in hydrophobic mesopores
      Lefevre, B.; Saugey, A.; Barrat, J. L.; Bocquet, L.; Charlaix, E.; Gobin, P. F.; Vigier, G.
      Journal of Chemical Physics (2004), 120 (10), 4927-4938CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
      We present exptl. and theor. results on intrusion-extrusion cycles of water in hydrophobic mesoporous materials, characterized by independent cylindrical pores. The intrusion, which takes place above the bulk satn. pressure, can be well described using a macroscopic capillary model. Once the material is satd. with water, extrusion takes place upon redn. of the externally applied pressure. Our results for the extrusion pressure can only be understood by assuming that the limiting extrusion mechanism is the nucleation of a vapor bubble inside the pores. A comparison of calcd. and exptl. nucleation pressures shows that a proper inclusion of line tension effects is necessary to account for the obsd. values of nucleation barriers. Neg. line tensions of order 10-11 J m-1 are found for our system, in reasonable agreement with other exptl. ests. of this quantity.
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    29. 29
      Guillemot, L.; Biben, T.; Galarneau, A.; Vigier, G.; Charlaix, É. Activated Drying in Hydrophobic Nanopores and the Line Tension of Water. Proc. Natl. Acad. Sci. U.S.A. 2012, 109 (48), 19557– 19562,  DOI: 10.1073/pnas.1207658109
      29
      Activated drying in hydrophobic nanopores and the line tension of water
      Guillemot, Ludivine; Biben, Thierry; Galarneau, Anne; Vigier, Gerard; Charlaix, Elisabeth
      Proceedings of the National Academy of Sciences of the United States of America (2012), 109 (48), 19557-19562, S19557/1-S19557/5CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
      Slow dynamics of water evapn. out of hydrophobic cavities has been studied by using model porous silica materials grafted with octylsilanes. The cylindrical pores were monodisperse, with a radius in the range of 1-2 nm. Liq. water penetrated into the nanopores at high pressure and emptied the pores when the pressure was lowered. The drying pressure exhibited a logarithmic growth as a function of the driving rate over more than three decades, showing the thermally activated nucleation of vapor bubbles. The slow dynamics and the crit. vol. of the vapor nucleus were quant. described by the classical theory of capillarity without adjustable parameter. The classical capillarity overestimated the crit. bubble energy. Possible effect of surface heterogeneities, long-range interactions, and high-curvature effects is discussed, and it is shown that a classical theory can describe vapor nucleation provided that a neg. line tension is taken into account. The drying pressure then provides a detn. of this line tension with much higher precision than currently available methods. The authors found consistent values of the order of -30 pN in a variety of hydrophobic materials.
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    30. 30
      Amabili, M.; Grosu, Y.; Giacomello, A.; Meloni, S.; Zaki, A.; Bonilla, F.; Faik, A.; Casciola, C. M. Pore Morphology Determines Spontaneous Liquid Extrusion from Nanopores. ACS Nano 2019, 13 (2), 1728,  DOI: 10.1021/acsnano.8b07818
      30
      Pore Morphology Determines Spontaneous Liquid Extrusion from Nanopores
      Amabili, Matteo; Grosu, Yaroslav; Giacomello, Alberto; Meloni, Simone; Zaki, Abdelali; Bonilla, Francisco; Faik, Abdessamad; Casciola, Carlo Massimo
      ACS Nano (2019), 13 (2), 1728-1738CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
      In this contribution we explore by means of expts., theory, and mol. dynamics the effect of pore morphol. on the spontaneous extrusion of nonwetting liqs. from nanopores. Understanding and controlling this phenomenon is central for manipulating nanoconfined liqs., e.g., in nanofluidic applications, drug delivery, and oil extn. Qual. different extrusion behaviors were obsd. in high-pressure water intrusion-extrusion expts. on porous materials with similar nominal diam. and hydrophobicity: macroscopic capillary models and mol. dynamics simulations revealed that the very presence or absence of extrusion is connected to the internal morphol. of the pores and, in particular, to the presence of small-scale roughness or pore interconnections. Addnl. expts. with mercury confirmed that this mechanism is generic for nonwetting liqs. and is rooted in the pore topol. The present results suggest a rational way to engineer heterogeneous systems for energy and nanofluidic applications in which the extrusion behavior can be controlled via the pore morphol.
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    31. 31
      Bushuev, Y. G.; Grosu, Y.; Chorążewski, M. A.; Meloni, S. Effect of the Topology on Wetting and Drying of Hydrophobic Porous Materials. ACS Appl. Mater. Interfaces 2022, 14 (26), 30067– 30079,  DOI: 10.1021/acsami.2c06039
      31
      Effect of the Topology on Wetting and Drying of Hydrophobic Porous Materials
      Bushuev, Yuriy G.; Grosu, Yaroslav; Chorazewski, Miroslaw A.; Meloni, Simone
      ACS Applied Materials & Interfaces (2022), 14 (26), 30067-30079CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Establishing mol. mechanisms of wetting and drying of hydrophobic porous materials is a general problem for science and technol. within the subcategories of the theory of liqs., chromatog., nanofluidics, energy storage, recuperation, and dissipation. In this article, we demonstrate a new way to tackle this problem by exploring the effect of the topol. of pure silica nanoparticles, nanotubes, and zeolites. Using mol. dynamics simulations, we show how secondary porosity promotes the intrusion of water into micropores and affects the hydrophobicity of materials. It is demonstrated herein that for nano-objects, the hydrophobicity can be controlled by changing the ratio of open to closed nanometer-sized lateral pores. This effect can be exploited to produce new materials for practical applications when the hydrophobicity needs to be regulated without significantly changing the chem. or structure of the materials. Based on these simulations and theor. considerations, for pure silica zeolites, we examd. and then classified the exptl. database of intrusion pressures, thus leading to the prediction of any zeolite's intrusion pressure. We show a correlation between the intrusion pressure and the ratio of the accessible pore surface area to total pore vol. The correlation is valid for some zeolites and mesoporous materials. It can facilitate choosing prospective candidates for further investigation and possible exploitation, esp. for energy storage, recuperation, and dissipation.
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    32. 32
      Bushuev, Y. G.; Grosu, Y.; Chora̧żewski, M. A.; Meloni, S. Subnanometer Topological Tuning of the Liquid Intrusion/Extrusion Characteristics of Hydrophobic Micropores. Nano Lett. 2022, 22 (6), 2164– 2169,  DOI: 10.1021/acs.nanolett.1c02140
      32
      Subnanometer Topological Tuning of the Liquid Intrusion/Extrusion Characteristics of Hydrophobic Micropores
      Bushuev, Yuriy G.; Grosu, Yaroslav; Chorazewski, Miroslaw A.; Meloni, Simone
      Nano Letters (2022), 22 (6), 2164-2169CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
      Intrusion(wetting)/extrusion(drying) of liqs. in/from lyophobic nanoporous systems is key in many fields, including chromatog., nanofluidics, biol. and energy materials. Here we demonstrate that secondary topol. features decorating main channels of porous systems dramatically affect the intrusion/extrusion cycle. These secondary features, allowing an unexpected bridging with liq. in the surrounding domains, stabilize the water stream intruding a micropore. This reduces the intrusion/extrusion barrier and the corresponding pressures without altering other properties of the system. Tuning the intrusion/extrusion pressures via subnanometric topol. features represent a yet unexplored strategy for designing hydrophobic micropores. Though energy is not the only field of application, here we show that the proposed tuning approach may bring 20-75 MPa of intrusion-extrusion pressure increase, expanding the applicability of hydrophobic microporous materials.
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    33. 33
      Huang, L. B.; Di Vincenzo, M.; Li, Y.; Barboiu, M. Artificial Water Channels: Towards Biomimetic Membranes for Desalination. Chem.─Eur. J. 2021, 27 (7), 2224– 2239,  DOI: 10.1002/chem.202003470
      33
      Artificial Water Channels: Towards Biomimetic Membranes for Desalination
      Huang, Li-Bo; Di Vincenzo, Maria; Li, Yuhao; Barboiu, Mihail
      Chemistry - A European Journal (2021), 27 (7), 2224-2239CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. Natural Aquaporin (AQP) channels are efficient water translocating proteins, rejecting ions. Inspired by this masterpiece of nature, Artificial Water Channels (AWCs) with controlled functional structures, can be potentially used to mimic the AQPs to a certain extent, offering flexible avenues toward biomimetic membranes for water purifn. The objective of this paper is to trace the historical development and significant advancements of current reported AWCs. Meanwhile, we attempt to reveal important structural insights and supramol. self-assembly principles governing the selective water transport mechanisms, toward innovative AWC-based biomimetic membranes for desalination.
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    34. 34
      Berne, B. J.; Weeks, J. D.; Zhou, R. Dewetting and Hydrophobic Interaction in Physical and Biological Systems. Annu. Rev. Phys. Chem. 2009, 60, 85– 103,  DOI: 10.1146/annurev.physchem.58.032806.104445
      34
      Dewetting and hydrophobic interaction in physical and biological systems
      Berne, Bruce J.; Weeks, John D.; Zhou, Ruhong
      Annual Review of Physical Chemistry (2009), 60 (), 85-103CODEN: ARPLAP; ISSN:0066-426X. (Annual Reviews Inc.)
      A review. Hydrophobicity manifests itself differently on large and small length scales. This review focuses on large-length-scale hydrophobicity, particularly on dewetting at single hydrophobic surfaces and drying in regions bounded on two or more sides by hydrophobic surfaces. We review applicable theories, simulations, and expts. pertaining to large-scale hydrophobicity in phys. and biomol. systems and clarify some of the crit. issues pertaining to this subject. Given space constraints, we cannot review all the significant and interesting work in this active field.
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    35. 35
      Sen, S.; Risbud, S. H.; Bartl, M. H. Thermodynamic and Kinetic Transitions of Liquids in Nanoconfinement. Acc. Chem. Res. 2020, 53 (12), 2869– 2878,  DOI: 10.1021/acs.accounts.0c00502
      35
      Thermodynamic and Kinetic Transitions of Liquids in Nanoconfinement
      Sen, Sabyasachi; Risbud, Subhash H.; Bartl, Michael H.
      Accounts of Chemical Research (2020), 53 (12), 2869-2878CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
      Conspectus: Core principles of chem. are ubiquitously invoked to shed light on the nature of mol. level interactions in nanoconfined fluids, which play a pivotal role in a wide range of processes in geochem., biol., and engineering. A detailed understanding of the physicochem. processes involved in the flow, structural transitions, and freezing or melting behavior of fluids confined within nanometer-sized pores of solid materials is thus of enormous importance for both basic research and technol. applications. This Account provides a perspective on new insights into the thermodn. and kinetic transitions of nanoconfined fluids in their stable and metastable forms. After briefly introducing the unique properties of mesoporous silicas from the SBA, MCM, and FDU families that serve as the confinement matrixes, combining highly ordered single and bimodal mesopore architectures with tunable pore sizes in the ~ 2-15 nm range and narrow size distributions, recent studies on melting/freezing behavior of water confined in these host matrixes are reviewed. While differential scanning calorimetry (DSC) reveals a linear relationship between m.p. depression and pore size (independent of the pore shape), as predicted by the Gibbs-Thomson relation, variable temp. 2H wide-line NMR spectroscopy studies confirm the core-shell model of water and give evidence for a layer-by-layer freezing mechanism, which gives rise to an apparent fragile-to-strong transition in the solidification dynamics. In contrast to the freezing/melting behavior of water, the effect of nanoconfinement on the glass transition of supercooled liqs. is nonuniversal and the glass transition temp. Tg can either increase or decrease with the dimensionality and extent of confinement. This nonuniversal behavior is exemplified by the two glass-forming mol. liqs., glycerol and ortho-terphenyl (OTP). While glycerol shows an increase in Tg and a pronounced slowdown of the rotational dynamics of the constituent mols. due to a change in the mol. packing between the bulk and the confined liq., OTP displays a linear and confining-media-dependent depression of Tg with increased confinement that is strongly influenced by the pore-liq. interface characteristics. This Account concludes with a focus on recent exptl. evidence of extreme spatial and dynamical heterogeneity in both freezing and glass transition processes. This discovery was enabled by the unique mesoporous structures of SBA-16 and FDU-5, possessing bimodal architectures with two interconnected pore types of different size and shape (spherical and cylindrical). For the very first time, two m.ps. for water and two glass transitions for supercooled OTP, corresponding to a specific pore type, were obsd. Collectively, these observations strongly suggest a close mechanistic connection between the local fluctuations in the structure and dynamics of nanoconfined liqs. While the findings reviewed in this Account provide new insights into thermodn. and kinetic transitions of fluids, there remain many unanswered questions regarding the effects of nanoconfinement on the fundamental properties of fluids, which offer exciting future opportunities in chem. research.
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    36. 36
      Ronchi, L.; Patarin, J.; Nouali, H.; Daou, T. J.; Ryzhikov, A. Structure Influence on High-Pressure Water Intrusion in Pure Silica Zeolites. New J. Chem. 2024,  DOI: 10.1039/D3NJ03991A
      There is no corresponding record for this reference.
    37. 37
      Leung, K.; Nielsen, I. M. B.; Criscenti, L. J. Elucidating the Bimodal Acid-Base Behavior of the Water-Silica Interface from First Principles. J. Am. Chem. Soc. 2009, 131 (51), 18358– 18365,  DOI: 10.1021/ja906190t
      37
      Elucidating the Bimodal Acid-Base Behavior of the Water-Silica Interface from First Principles
      Leung, Kevin; Nielsen, Ida M. B.; Criscenti, Louise J.
      Journal of the American Chemical Society (2009), 131 (51), 18358-18365CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Understanding the acid-base behavior of silica surfaces is crit. for many nanoscience and bionano interface applications. Silanol groups (SiOH) on silica surfaces exhibit two acidity consts.-one as acidic as vinegar-but their structural basis remains controversial. The at. details of the more acidic silanol site govern not just the overall surface charge d. at near neutral soln. pH but also how ions and biomols. interact with and bind to silica immersed in water. Using ab initio mol. dynamics simulations and multiple representative cryst. silica surfaces, the authors det. the deprotonation free energies of silanol groups with different structural motifs. Previously proposed motifs related to chem. connectivity or intersilanol hydrogen bonds do not yield high acidity. Instead, a plausible candidate for pKa = 4.5 silanol groups may be found in locally strained or defected regions with sparse silanol coverage. In the process, irreversible ring-opening reactions of strained silica trimer rings in contact with liq. water are obsd.
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    38. 38
      Lopes, P. E. M.; Murashov, V.; Tazi, M.; Demchuk, E.; Mackerell, A. D. Development of an Empirical Force Field for Silica. Application to the Quartz-Water Interface. J. Phys. Chem. B 2006, 110 (6), 2782– 2792,  DOI: 10.1021/jp055341j
      38
      Development of an Empirical Force Field for Silica. Application to the Quartz-Water Interface
      Lopes, Pedro E. M.; Murashov, Vladimir; Tazi, Mouhsine; Demchuk, Eugene; MacKerell, Alexander D., Jr.
      Journal of Physical Chemistry B (2006), 110 (6), 2782-2792CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)
      Interactions of pulverized cryst. silica with biol. systems, including the lungs, cause cell damage, inflammation, and apoptosis. To allow computational atomistic modeling of these pathogenic processes, including interactions between silica surfaces and biol. mols., new parameters for quartz, compatible with the CHARMM empirical force field were developed. Parameters were optimized to reproduce the exptl. geometry of α-quartz, ab initio vibrational spectra, and interactions between model compds. and water. The newly developed force field was used to study interactions of water with two singular surfaces of α-quartz, (011) and (100). Properties monitored and analyzed include the variation of the d. of water mols. in the plane perpendicular to the surface, disruption of the water H-bond network upon adsorption, and space-time correlations of water oxygen atoms in terms of Van Hove self-correlation functions. The vibrational d. of states spectra of water in confined compartments were also computed and compared with exptl. neutron-scattering results. Both the attenuation and shifting to higher frequencies of the hindered translational peaks upon confinement are clearly reproduced by the model. However, an upshift of librational peaks under the conditions of model confinement still remains underrepresented at the current empirical level.
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    39. 39
      Law, K. Y. Definitions for Hydrophilicity, Hydrophobicity, and Superhydrophobicity: Getting the Basics Right. J. Phys. Chem. Lett. 2014, 5 (4), 686– 688,  DOI: 10.1021/jz402762h
      39
      Definitions for Hydrophilicity, Hydrophobicity, and Superhydrophobicity: Getting the Basics Right
      Law, Kock-Yee
      Journal of Physical Chemistry Letters (2014), 5 (4), 686-688CODEN: JPCLCD; ISSN:1948-7185. (American Chemical Society)
      There is no expanded citation for this reference.
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    40. 40
      Bermúdez, D.; Sastre, G. Calculation of Pore Diameters in Zeolites. Theor. Chem. Acc. 2017, 136 (10), 1– 11,  DOI: 10.1007/s00214-017-2143-6
      40
      Calculation of pore diameters in zeolites
      Bermudez, Diego; Sastre, German
      Theoretical Chemistry Accounts (2017), 136 (10), 1-11CODEN: TCACFW; ISSN:1432-2234. (Springer)
      Pore diams. of zeolites are calcd. using a new freely available software tool which identifies rings based on the crystallog. notation of atoms. In addn., an automated algorithm allows to ext. information from mol. dynamics outputs so that dynamic pore diams. are calcd. and compared to an exptl. ref. This is useful in order to identify different rings along a given channel as well as for the calcn. and anal. of ring deformations due to framework dynamics and sorbate diffusion.
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    41. 41
      Köfinger, J.; Hummer, G.; Dellago, C. Single-File Water in Nanopores. Phys. Chem. Chem. Phys. 2011, 13 (34), 15403– 15417,  DOI: 10.1039/c1cp21086f
      41
      Single-file water in nanopores
      Kofinger Jurgen; Hummer Gerhard; Dellago Christoph
      Physical chemistry chemical physics : PCCP (2011), 13 (34), 15403-17 ISSN:.
      Water molecules confined to pores with sub-nanometre diameters form single-file hydrogen-bonded chains. In such nanoscale confinement, water has unusual physical properties that are exploited in biology and hold promise for a wide range of biomimetic and nanotechnological applications. The latter can be realized by carbon and boron nitride nanotubes which confine water in a relatively non-specific way and lend themselves to the study of intrinsic properties of single-file water. As a consequence of strong water-water hydrogen bonds, many characteristics of single-file water are conserved in biological and synthetic pores despite differences in their atomistic structures. Charge transport and orientational order in water chains depend sensitively on and are mainly determined by electrostatic effects. Thus, mimicking functions of biological pores with apolar pores and corresponding external fields gives insight into the structure-function relation of biological pores and allows the development of technical applications beyond the molecular devices found in living systems. In this Perspective, we revisit results for single-file water in apolar pores, and examine the similarities and the differences between these simple systems and water in more complex pores.
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    42. 42
      Ryzhikov, A.; Khay, I.; Nouali, H.; Daou, T. J.; Patarin, J. Energetic Performances of Pure Silica STF and MTT-Type Zeolites under High Pressure Water Intrusion. RSC Adv. 2014, 4 (71), 37655– 37661,  DOI: 10.1039/C4RA05519E
      42
      Energetic performances of pure silica STF and MTT-type zeolites under high pressure water intrusion
      Ryzhikov, A.; Khay, I.; Nouali, H.; Daou, T. J.; Patarin, J.
      RSC Advances (2014), 4 (71), 37655-37661CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
      Exptl. water intrusion-extrusion isotherms were performed at room temp.on two pure silica MTT- and STF-type hydrophobic zeolites (zeosils) with 1D channel and cage pore systems, resp. by applying or releasing a high hydraulic pressure. These zeosils were obtained by hydrothermal synthesis in fluoride medium and characterized by structural and physicochem. methods before and after water intrusion. The system "MTT-type zeosil-water" displays a spring behavior with an intrusion pressure of 176 MPa and a stored energy of 5.3 J g-1. No influence of water intrusion on the structure of MTT-type zeosil was found. The "STF-type zeosil-water" system shows a combination of shock-absorber and bumper behavior in the first cycle with an intrusion pressure of 51 MPa. Nevertheless in the following cycles the system demonstrates a spring behavior with an intrusion pressure of 38 MPa. Such behavior can be explained by the formation of silanol groups under intrusion in some pores confirmed by NMR spectroscopy and TG data.
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    43. 43
      Tzanis, L.; Trzpit, M.; Soulard, M.; Patarin, J. High Pressure Water Intrusion Investigation of Pure Silica 1D Channel AFI, MTW and TON-Type Zeolites. Microporous Mesoporous Mater. 2011, 146 (1–3), 119– 126,  DOI: 10.1016/j.micromeso.2011.03.043
      43
      High pressure water intrusion investigation of pure silica 1D channel AFI, MTW and TON-type zeolites
      Tzanis, Lydie; Trzpit, Mickael; Soulard, Michel; Patarin, Joel
      Microporous and Mesoporous Materials (2011), 146 (1-3), 119-126CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier Inc.)
      Exptl. water intrusion-extrusion isotherms were performed at room temp. on various 1-dimensional channel pure silica AFI, MTW and TON-type zeolites. The water intrusion is obtained by applying a high hydraulic pressure corresponding to the intrusion step. Whatever the zeosil, when the pressure is released, the water extrusion occurs at a similar pressure to that of the intrusion one. These zeosil-water systems behave like a spring and the phenomenon is reproducible over several cycles. Several characterizations were realized before and after water intrusion-extrusion expts. to reveal the presence or the absence of defects after such expts. For all samples, no structural modifications at the long range order are obsd. by XRD anal. However for the MTW-type zeosil, solid state NMR spectroscopy get evidence of the presence of Q2 and Q3 groups revealing the breaking of some siloxane bridges. Nevertheless, the amt. of defects is very low ( < 2%) and seems not to have an influence on the intrusion-extrusion data for numerous cycles. The stored energy is relatively important and close to 5.8, 15 and 14 J/g for AFI, MTW and TON-type zeosils, resp.
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    44. 44
      Fadeev, A.; Eroshenko, V. Study of Penetration of Water into Hydrophobized Porous Silicas. J. Colloid Interface Sci. 1997, 187 (2), 275– 282,  DOI: 10.1006/jcis.1996.4495
      44
      Study of penetration of water into hydrophobized porous silicas
      Fadeev, Alexander Y.; Eroshenko, Valentine A.
      Journal of Colloid and Interface Science (1997), 187 (2), 275-282CODEN: JCISA5; ISSN:0021-9797. (Academic)
      Intrusion of water into a pore space of silicas hydrophobized with alkylsilanes is studied. The water porosimetry technique is introduced and construction of a water porosimeter is described. The effects of bonded alkyl chain length, bonding d., structure of alkylsilane, and av. pore diam. of silica on the parameters of water intrusion are studied. Advancing and receding angles of water on chem. modified silica surfaces are estd. It is shown that contact angles increase as bonding d. and bonded chain length are increased. The correlation between the structure of a bonded alkylsilane monolayer and its hydrophobicity is discussed.
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    45. 45
      Beckstein, O.; Sansom, M. S. P. Liquid-Vapor Oscillations of Water in Hydrophobic Nanopores. Proc. Natl. Acad. Sci. U.S.A. 2003, 100 (12), 7063– 7068,  DOI: 10.1073/pnas.1136844100
      45
      Liquid-vapor oscillations of water in hydrophobic nanopores
      Beckstein, Oliver; Sansom, Mark S. P.
      Proceedings of the National Academy of Sciences of the United States of America (2003), 100 (12), 7063-7068CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
      Water plays a key role in biol. membrane transport. In ion channels and water-conducting pores (aquaporins), one-dimensional confinement in conjunction with strong surface effects changes the phys. behavior of water. In mol. dynamics simulations of water in short (0.8 nm) hydrophobic pores the water d. in the pore fluctuates on a nanosecond time scale. In long simulations (460 ns in total) at pore radii ranging from 0.35 to 1.0 nm we quantify the kinetics of oscillations between a liq.-filled and a vapor-filled pore. This behavior can be explained as capillary evapn. alternating with capillary condensation, driven by pressure fluctuations in the water outside the pore. The free-energy difference between the two states depends linearly on the radius. The free-energy landscape shows how a metastable liq. state gradually develops with increasing radius. For radii > ≈0.55 nm it becomes the globally stable state and the vapor state vanishes. One-dimensional confinement affects the dynamic behavior of the water mols. and increases the self diffusion by a factor of 2-3 compared with bulk water. Permeabilities for the narrow pores are of the same order of magnitude as for biol. water pores. Water flow is not continuous but occurs in bursts. Our results suggest that simulations aimed at collective phenomena such as hydrophobic effects may require simulation times >50 ns. For water in confined geometries, it is not possible to extrapolate from bulk or short time behavior to longer time scales.
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    46. 46
      Kumar, R.; Schmidt, J. R.; Skinner, J. L. Hydrogen Bonding Definitions and Dynamics in Liquid Water. J. Chem. Phys. 2007, 126 (20), 204107,  DOI: 10.1063/1.2742385
      46
      Hydrogen bonding definitions and dynamics in liquid water
      Kumar, R.; Schmidt, J. R.; Skinner, J. L.
      Journal of Chemical Physics (2007), 126 (20), 204107/1-204107/12CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
      X-ray and neutron diffractions, vibrational spectroscopy, and x-ray Raman scattering and absorption expts. on water are often interpreted in terms of hydrogen bonding. To this end a no. of geometric definitions of hydrogen bonding in water have been developed. While all definitions of hydrogen bonding are to some extent arbitrary, those involving one distance and one angle for a given water dimer are unnecessarily so. In this paper the authors develop a systematic procedure based on two-dimensional potentials of mean force for defining cutoffs for a given pair of distance and angular coordinates. They also develop an electronic structure-based definition of hydrogen bonding in liq. water, related to the electronic occupancy of the antibonding OH orbitals. This definition turns out to be reasonably compatible with one of the distance-angle geometric definitions. These two definitions lead to an est. of the no. of hydrogen bonds per mol. in liq. simple point charge/extended (SPC/E) water of between 3.2 and 3.4. They also used these and other hydrogen-bond definitions to examine the dynamics of local hydrogen-bond no. fluctuations, finding an approx. long-time decay const. for SPC/E water of between 0.8 and 0.9 ps, which corresponds to the time scale for local structural relaxation.
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    47. 47
      Stanley, H. E.; Teixeira, J. Interpretation of the Unusual Behavior of H2O and D2O at Low Temperatures: Tests of a Percolation Model. J. Chem. Phys. 1980, 73 (7), 3404– 3422,  DOI: 10.1063/1.440538
      47
      Interpretation of the unusual behavior of water and heavy water at low temperatures: tests of a percolation model
      Stanley, H. Eugene; Teixeira, J.
      Journal of Chemical Physics (1980), 73 (7), 3404-22CODEN: JCPSA6; ISSN:0021-9606.
      The unusual low-temp. behavior of liq. water is interpreted using a simple model based upon connectivity concepts from correlated-site percolation theory. Emphasis is placed on examg. the phys. implications of the continuous H-bonded network (or "gel") formed by water mols. Each water mol. A is assigned to 1 of 5 species based on the no. of "intact bonds" (the no. of other mols. whose interaction energy with A is stronger than some cutoff VHB). The spatial positions of the various species are not randomly distributed but rather are cor. In particular, it is seen that the infinite H-bonded network contains tiny "patches" of 4-bonded mols. Well-defined predictions based upon the putative presence of these tiny patches are developed. The detailed dependences are predicted on temp, diln. with the isotope D2O, hydrostatic pressure greater than atm., and "patch-breaking impurities"--for 4 sep. response functions.
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    48. 48
      Bushuev, Y. G. Properties of the Network of the Hydrogen Bonds of Water. Russ. Chem. Bull. 1997, 46 (5), 888– 891,  DOI: 10.1007/BF02496112
      48
      Properties of the network of the hydrogen bonds of water
      Bushuev, Yu. G.
      Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya) (1997), 46 (5), 888-891CODEN: RCBUEY; ISSN:1066-5285. (Consultants Bureau)
      Networks of the hydrogen bonds and those consisting of lines connecting nearby mols. were constructed using configurations of water mols. obtained by the Monte-Carlo method. The concns. of closed cycles of hydrogen bonds were established to be detd. only by the probability of hydrogen bond formation. Characteristics of a model ideal water network were detd. Topol. properties of the Polk model and those of the network of nearest neighbors differ substantially from the properties of the ideal network. The totality of the hydrogen bonds in pure water was proposed to be considered as a hierarchical system. Three topol. different structures of water assocs. were detd.
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    49. 49
      Bushuev, Y.; Davletbaeva, S.; Korolev, V. The Influence of Universal and Specific Interactions on Structural Properties of Liquid Formamide. Russ. Chem. Bull. 1999, 48 (12), 2200– 2210,  DOI: 10.1007/bf02498260
      49
      The influence of universal and specific interactions on structural properties of liquid formamide
      Bushuev, Yu. G.; Davletbaeva, S. V.; Korolev, V. P.
      Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya) (1999), 48 (12), 2200-2210CODEN: RCBUEY; ISSN:1066-5285. (Consultants Bureau)
      Monte Carlo simulation of the structure of liq. formamide at 298 K was carried out. Intermol. interactions were calcd. using five different potentials. No essential changes in the spatial structure and topol. properties of the network of hydrogen bonds of liq. formamide occur upon varying the electrostatic intermol. interactions, strength of H-bonds, and temp. Fragments of crystal structure are partly retained in liq. formamide. It was found that the network of H-bonds is structurally inhomogeneous and contains long-lived assocs. of closed cycles of H-bonds as well as tree-like and chain-like structures. The energy, topol., and statistical characteristics of closed cycles of H-bonds were detd.
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    50. 50
      Bushuev, Y. G.; Davletbaeva, S. V. Structural Properties of Liquid N-Methylformamide. Russ. Chem. Bull. 2000, 49 (2), 238– 250,  DOI: 10.1007/bf02494665
      50
      Structural properties of liquid N-methylformamide
      Bushuev, Yu. G.; Davletbaeva, S. V.
      Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya) (2000), 49 (2), 238-250CODEN: RCBUEY; ISSN:1066-5285. (Consultants Bureau)
      Monte Carlo simulation of liq. HCONHMe (I) was carried out at 298 K. The atom-atom spatial-distribution functions, concns. of closed cycles of H bonds, radial distribution functions of geometric centers of the cycles, and other characteristics of the system of H bonds and the network built of the lines connecting neighboring mols. were calcd. The effects of electrostatic and van der Waals interactions as well as mol. conformations on the regularities of mutual orientation of the mols. were studied. Open chains of H bonds dominate over closed cycles. The spatial structure of liq. I is detd. by packing of the mols. and steric factors, and is close to the structure of a random closely packed system of soft spheres.
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    51. 51
      Formanek, M.; Martelli, F. Probing the Network Topology in Network-Forming Materials: The Case of Water. AIP Adv. 2020, 10 (5), 055205,  DOI: 10.1063/5.0005332
      51
      Probing the network topology in network-forming materials: The case of water
      Formanek, Maud; Martelli, Fausto
      AIP Advances (2020), 10 (5), 055205CODEN: AAIDBI; ISSN:2158-3226. (American Institute of Physics)
      Rings statistic has been widely used to investigate the network topol. in numerically simulated network-forming materials in order to rationalize their phys. and mech. properties. However, different topologies arise depending on how rings are counted, leading to incomplete or even contrasting phys. interpretations. Solving this crit. ambiguity is of primary importance for the correct assessment of material properties. Here, we show how such differences emerge in water, a complex network-forming material endowed with polyamorphism and a directional network of hydrogen bonds whose topol. is correlated with the anomalous behavior of water. We probe the network in the liq. state at several thermodn. points under equil. conditions, as well as during the out-of-equil. first-order-like low d. to high d. amorphous transformation. We study three schemes for counting rings and show that each of them provides complementary insightful information about the network, suggesting that a single counting scheme may not be sufficient to properly describe network topologies and to assess material properties. Our results provide a mol. description of the rings in supercooled water and of the amorphous-to-amorphous transformation kinetics, hence shedding light on the complex nature of water. Nonetheless, our results expose how delicate the proper choice of method for counting rings is, an issue with important consequences for rationalizing the properties of network-forming materials at large. (c) 2020 American Institute of Physics.
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    52. 52
      Rice, S. A.; Sceats, M. G. A Random Network Model for Water. J. Phys. Chem. 1981, 85 (9), 1108– 1119,  DOI: 10.1021/j150609a009
      52
      A random network model for water
      Rice, Stuart A.; Sceats, Mark G.
      Journal of Physical Chemistry (1981), 85 (9), 1108-19CODEN: JPCHAX; ISSN:0022-3654.
      A random network model for liq. water is discussed. This model, which uses information derived from studies of cryst. ices, amorphous solid water, and liq. water, is based on two assumptions, one of which refers to structure and the other to the dynamics of the mol. motion. These assumptions are (i) there is a continuous, albeit distorted, network of H bonds in the liq., and (ii) it is meaningful to describe the mol. motion by using two distinct time scales. It is shown how adoption of these assumptions leads to the definition of a random network potential, and to rather good descriptions of the OO distribution function, the dielec. const., and the bulk thermodn. properties of liq. water. Despite its successes, the random network model fails to describe adequately some of the properties of liq. water; these discrepancies are discussed from the point of view of modifications needed to improve the model.
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    53. 53
      Cobeña-Reyes, J.; Sahimi, M. Universal Intrinsic Dynamics and Freezing of Water in Small Nanotubes. J. Phys. Chem. C 2021, 125 (1), 946– 956,  DOI: 10.1021/acs.jpcc.0c08494
      53
      Universal intrinsic dynamics and freezing of water in nanotubes
      Cobena-Reyes, Jose; Sahimi, Muhammad
      Journal of Physical Chemistry C (2021), 125 (1), 946-956CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      Although it is well known that confinement alters the f.p. of water, the mechanism by which this occurs, particularly in small nanotubes, is still under active research. It was recently claimed that the f.p. of water in a carbon nanotube of a certain size may be as high as its b.p. under bulk conditions or even higher. A more recent paper reported that the change in the f.p. may not be as drastic as what was claimed by Agrawal et al., and may in fact be close to the bulk f.p. Thus, aside from the need to resolve the issue, an important question that arises is whether such a behavior is universal and may happen in any type of nanotube. In other words, can the interactions between water mols. and the wall atoms in other types of nanotube suppress this effect, or is this a universal feature occurring in every type of nanotube. In this paper, we address these issues by carrying out extensive mol. dynamics (MD) simulations and studying the dynamics of water in silicon carbide nanotubes. The results indicate that the m.p. can be as much as 100 K lower than the bulk value. A comparison between the hydrogen-bond networks formed in carbon and silicon carbon nanotubes indicates that weaker HB networks are the main cause of the depression of the f.p. Several types of ice, including those with trigonal, square, and pentagonal cross sections, are identified, each of which exhibits a different m.p. that depends on the nanotube's diam. The effect of the partial charges of the atoms of the nanotube's walls on the strength of the hydrogen-bond network was also studied. Larger partial charges lead to a more rapid decay of the hydrogen-bond correlation function, signaling a lower m.p.
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    54. 54
      Mochizuki, K. Absorption of Mechanical Energyviaformation of Ice Nanotubes in Zeolites. Phys. Chem. Chem. Phys. 2021, 23 (36), 20307– 20312,  DOI: 10.1039/D1CP01482J
      54
      Absorption of mechanical energy via formation of ice nanotubes in zeolites
      Mochizuki, Kenji
      Physical Chemistry Chemical Physics (2021), 23 (36), 20307-20312CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
      Mol. dynamics simulations are carried out for a heterogeneous system composed of bulk water and pure-silica zeolites of the AFI type. My simulations show, for the first time, the spontaneous crystn. of water in hydrophobic zeolite channels by compression, while the water outside remains liq. The formation of ice nanotubes results in a mol. bumper behavior in the absence of chem. reactions, although the mechanism has been explained by the appearance of silanol defects. In contrast, the same zeolite-water system exhibits a weak shock-absorber behavior at higher temps. My study shows that the phase transitions of confined water dramatically change its intrusion/extrusion behavior and alter the energetic performance by varying the temp. alone. The results offer a new perspective for a better design of hydrophobic nanoporous materials utilized with water.
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    55. 55
      Offei-Danso, A.; Morzan, U. N.; Rodriguez, A.; Hassanali, A.; Jelic, A. The Collective Burst Mechanism of Angular Jumps in Liquid Water. Nat. Commun. 2023, 14 (1), 1345– 1411,  DOI: 10.1038/s41467-023-37069-9
      55
      The collective burst mechanism of angular jumps in liquid water
      Offei-Danso, Adu; Morzan, Uriel N.; Rodriguez, Alex; Hassanali, Ali; Jelic, Asja
      Nature Communications (2023), 14 (1), 1345CODEN: NCAOBW; ISSN:2041-1723. (Nature Portfolio)
      Understanding the microscopic origins of collective reorientational motions in aq. systems requires techniques that allow us to reach beyond our chem. imagination. Herein, we elucidate a mechanism using a protocol that automatically detects abrupt motions in reorientational dynamics, showing that large angular jumps in liq. water involve highly cooperative orchestrated motions. Our automatized detection of angular fluctuations, unravels a heterogeneity in the type of angular jumps occurring concertedly in the system. We show that large orientational motions require a highly collective dynamical process involving correlated motion of many water mols. in the hydrogen-bond network that form spatially connected clusters going beyond the local angular jump mechanism. This phenomenon is rooted in the collective fluctuations of the network topol. which results in the creation of defects in waves on the THz timescale. The mechanism we propose involves a cascade of hydrogen-bond fluctuations underlying angular jumps and provides new insights into the current localized picture of angular jumps, and its wide use in the interpretations of numerous spectroscopies as well in reorientational dynamics of water near biol. and inorg. systems. The role of finite size effects, as well as of the chosen water model, on the collective reorientation is also elucidated.
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    56. 56
      Paulo, G.; Sun, K.; di Muccio, G.; Gubbiotti, A.; Morozzo della Rocca, B.; Geng, J.; Maglia, G.; Chinappi, M.; Giacomello, A. Hydrophobically gated memristive nanopores for neuromorphic applications. Nat. Commun. 2023, 14, 8390,  DOI: 10.1038/s41467-023-44019-y
      56
      Hydrophobically gated memristive nanopores for neuromorphic applications
      Paulo, Goncalo; Sun, Ke; Di Muccio, Giovanni; Gubbiotti, Alberto; Morozzo della Rocca, Blasco; Geng, Jia; Maglia, Giovanni; Chinappi, Mauro; Giacomello, Alberto
      Nature Communications (2023), 14 (1), 8390CODEN: NCAOBW; ISSN:2041-1723. (Nature Portfolio)
      Abstr.: Signal transmission in the brain relies on voltage-gated ion channels, which exhibit the elec. behavior of memristors, resistors with memory. State-of-the-art technologies currently employ semiconductor-based neuromorphic approaches, which have already demonstrated their efficacy in machine learning systems. However, these approaches still cannot match performance achieved by biol. neurons in terms of energy efficiency and size. In this study, we utilize mol. dynamics simulations, continuum models, and electrophysiol. expts. to propose and realize a bioinspired hydrophobically gated memristive nanopore. Our findings indicate that hydrophobic gating enables memory through an electrowetting mechanism, and we establish simple design rules accordingly. Through the engineering of a biol. nanopore, we successfully replicate the characteristic hysteresis cycles of a memristor and construct a synaptic device capable of learning and forgetting. This advancement offers a promising pathway for the realization of nanoscale, cost- and energy-effective, and adaptable bioinspired memristors.
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    57. 57
      Dzubiella, J.; Hansen, J. P. Electric-Field-Controlled Water and Ion Permeation of a Hydrophobic Nanopore. J. Chem. Phys. 2005, 122 (23), 234706,  DOI: 10.1063/1.1927514
      57
      Electric-field-controlled water and ion permeation of a hydrophobic nanopore
      Dzubiella, J.; Hansen, J.-P.
      Journal of Chemical Physics (2005), 122 (23), 234706/1-234706/14CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
      The permeation of hydrophobic, cylindrical nanopores by water mols. and ions is investigated under equil. and out-of-equil. conditions by extensive mol.-dynamics simulations. Neglecting the chem. structure of the confining pore surface, we focus on the effects of pore radius and elec. field on permeation. The simulations confirm the intermittent filling of the pore by water, reported earlier under equil. conditions for pore radii larger than a crit. radius Rc. Below this radius, water can still permeate the pore under the action of a strong elec. field generated by an ion concn. imbalance at both ends of the pore embedded in a structureless membrane. The water driven into the channel undergoes considerable electrostriction characterized by a mean d. up to twice the bulk d. and by a dramatic drop in dielec. permittivity which can be traced back to a considerable distortion of the hydrogen-bond network inside the pore. The free-energy barrier to ion permeation is estd. by a variant of umbrella sampling for Na+, K+, Ca2+, and Cl- ions, and correlates well with known solvation free energies in bulk water. Starting from an initial imbalance in ion concn., equil. is gradually restored by successive ion passages through the water-filled pore. At each passage the elec. field across the pore drops, reducing the initial electrostriction, until the pore, of radius less than Rc, closes to water and hence to ion transport, thus providing a possible mechanism for voltage-dependent gating of hydrophobic pores.
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    58. 58
      Rasaiah, J. C.; Garde, S.; Hummer, G. Water in Nonpolar Confinement: From Nanotubes to Proteins and Beyond. Annu. Rev. Phys. Chem. 2008, 59, 713– 740,  DOI: 10.1146/annurev.physchem.59.032607.093815
      58
      Water in nonpolar confinement: from nanotubes to proteins and beyond
      Rasaiah, Jayendran C.; Garde, Shekhar; Hummer, Gerhard
      Annual Review of Physical Chemistry (2008), 59 (), 713-740CODEN: ARPLAP; ISSN:0066-426X. (Annual Reviews Inc.)
      A review. Water mols. confined to nonpolar pores and cavities of nanoscopic dimensions exhibit highly unusual properties. Water filling is strongly cooperative, with the possible coexistence of filled and empty states and sensitivity to small perturbations of the pore polarity and solvent conditions. Confined water mols. form tightly hydrogen bonded wires or clusters. The weak attractions to the confining wall, combined with strong interactions between water mols., permit exceptionally rapid water flow, exceeding expectations from macroscopic hydrodynamics by several orders of magnitude. The proton mobility along 1D water wires also substantially exceeds that in the bulk. Proteins appear to exploit these unusual properties of confined water in their biol. function (e.g., to ensure rapid water flow in aquaporins or to gate proton flow in proton pumps and enzymes). The unusual properties of water in nonpolar confinement are also relevant to the design of novel nanofluidic and mol. sepn. devices or fuel cells.
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    59. 59
      Fasano, M.; Bevilacqua, A.; Chiavazzo, E.; Humplik, T.; Asinari, P. Mechanistic Correlation between Water Infiltration and Framework Hydrophilicity in MFI Zeolites. Sci. Rep. 2019, 9 (1), 18429– 18512,  DOI: 10.1038/s41598-019-54751-5
      59
      Mechanistic correlation between water infiltration and framework hydrophilicity in MFI zeolites
      Fasano, Matteo; Bevilacqua, Alessio; Chiavazzo, Eliodoro; Humplik, Thomas; Asinari, Pietro
      Scientific Reports (2019), 9 (1), 18429CODEN: SRCEC3; ISSN:2045-2322. (Nature Research)
      Hydrophobic zeolites are nanoporous materials that are attracting an increasing interest, esp. for catalysis, desalination, energy storage and biomedical applications. Nevertheless, a more profound understanding and control of water infiltration in their nanopores is still desirable to rationally design zeolite-based materials with tailored properties. In this work, both atomistic simulations and previous exptl. data are employed to investigate water infiltration in hydrophobic MFI zeolites with different concn. of hydrophilic defects. Results show that limited concns. of defects (e.g. 1%) induce a change in the shape of infiltration isotherms (from type-V to type-I), which denotes a sharp passage from typical hydrophobic to hydrophilic behavior. A correlation parametrized on both energy and geometric characteristics of the zeolite (infiltration model) is then adopted to interpolate the infiltration isotherms data by means of a limited no. of phys.-meaningful parameters. Finally, the infiltration model is combined with the water-zeolite interaction energy computed by simulations to correlate the water intrusion mechanism with the atomistic details of the zeolite crystal, such as defects concn., distribution and hydrophilicity. The suggested methodol. may allow a faster (more than one order of magnitude) and more systematic preliminary computational screening of innovative zeolite-based materials for energy storage, desalination and biomedical purposes.
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    60. 60
      Trzpit, M.; Soulard, M.; Patarin, J.; Desbiens, N.; Cailliez, F.; Boutin, A.; Demachy, I.; Fuchs, a H. The Effect of Local Defects on Water Adsorption in Silicalite-1 Zeolite: A Joint Experimental and Molecular Simulation Study. Langmuir 2007, 23 (20), 10131– 10139,  DOI: 10.1021/la7011205
      60
      The effect of local defects on water adsorption in silicalite-1 zeolite. A joint experimental and molecular simulation study
      Trzpit, M.; Soulard, M.; Patarin, J.; Desbiens, N.; Cailliez, F.; Boutin, A.; Demachy, I.; Fuchs, A. H.
      Langmuir (2007), 23 (20), 10131-10139CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
      We report a joint exptl. and mol. simulation study of water condensation in silicalite-1 zeolite. A sample was synthesized using the fluoride route and was found to contain essentially no defects. A second sample synthesized using the hydroxide route was found to contain a small amt. of silanol groups. The thermodn. of water condensation was studied in these 2 samples, as well as in a com. sample, to understand the effect of local defects on water adsorption. The mol. simulation study enabled us to qual. reproduce the exptl. obsd. condensation thermodn. features. A shift and a rounding of the condensation transition was obsd. with an increasing hydrophilicity of the local defect, but the condensation transition was still obsd. above the water satn. vapor pressure P0. Both expts. and simulations agree on the fact that a small water uptake can be obsd. at very low pressure, but that the bulk liq. does not form from the gas phase below P0. The picture that emerges from the obsd. water condensation mechanism is the existence of a heterogeneous internal surface that is overall hydrophobic, despite the existence of hydrophilic "patches". This heterogeneous surface configuration is thermodynamically stable in a wide range of reduced pressures (from P/P0 = 0.2 to a few thousands), until the condensation transition takes place.
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    61. 61
      Zones, S.; Hwang, S.; Elomari, S.; Ogino, I.; Davis, M.; Burton, A. The Fluoride-Based Route to All-Silica Molecular Sieves; a Strategy for Synthesis of New Materials Based upon Close-Packing of Guest-Host Products. C. R. Chim. 2005, 8 (3–4), 267– 282,  DOI: 10.1016/j.crci.2004.12.009
      61
      The fluoride-based route to all-silica molecular sieves; a strategy for synthesis of new materials based upon close-packing of guest-host products
      Zones, Stacey I.; Hwang, Son-Jong; Elomari, Saleh; Ogino, Isao; Davis, Mark E.; Burton, Allen W.
      Comptes Rendus Chimie (2005), 8 (3-4), 267-282CODEN: CRCOCR; ISSN:1631-0748. (Editions Scientifiques et Medicales Elsevier)
      A review. This study surveys the use of a range of structure-directing agents (SDA) in zeolite synthesis expts. using HF. The studies involve systems contg. only silica as the inorg. component. Results from this study reinforce the concept that more open-framework host structures form when the reaction conditions include lower H2O/SiO2 ratios. Novel pure silica compns. are achieved using this methodol. Also explored using MAS NMR studies were whether the use of fluoride anions in synthesis leads to different nucleation selectivities as a function of diln. and whether guest mols. achieve tighter packing in the host structures using fluoride instead of hydroxide. The results indicated that some large organo-cations which produce no products in alk. media give interesting host structures in the fluoride reactions.
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    62. 62
      Arletti, R.; Ronchi, L.; Quartieri, S.; Vezzalini, G.; Ryzhikov, A.; Nouali, H.; Daou, T. J.; Patarin, J. Intrusion-Extrusion Experiments of MgCl2 Aqueous Solution in Pure Silica Ferrierite: Evidence of the Nature of Intruded Liquid by in Situ High Pressure Synchrotron X-Ray Powder Diffraction. Microporous Mesoporous Mater. 2016, 235, 253– 260,  DOI: 10.1016/j.micromeso.2016.08.024
      62
      Intrusion-extrusion experiments of MgCl2 aqueous solution in pure silica ferrierite: Evidence of the nature of intruded liquid by in situ high pressure synchrotron X-ray powder diffraction
      Arletti, Rossella; Ronchi, Laura; Quartieri, Simona; Vezzalini, Giovanna; Ryzhikov, Andrey; Nouali, Habiba; Daou, T. Jean; Patarin, Joel
      Microporous and Mesoporous Materials (2016), 235 (), 253-260CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier B.V.)
      Exptl. intrusion-extrusion isotherms of MgCl2•21H2O soln. were recorded at room temp. on pure silica FER-type zeolite (Si-FER). The intrusion occurs at 195 MPa and the phenomenon is completely reversible with a slight hysteresis. The "Si-FER - MgCl2 aq. soln." system behaves like a spring. The material was deeply characterized before and after intrusion-extrusion expts. and no significant changes were obsd. The unit cell parameters were refined - on the basis of the in situ synchrotron X-ray powder diffraction data - up to 1.47 GPa and then at Pamb upon pressure release. The Rietveld refinement of the data collected at 0.28 GPa (280 MPa), a pressure close to the intrusion value, shows that both ions and water mols. present in the MgCl2 aq. soln. were intruded in the porosity. However, the solvation degree of the intruded ions differs from the initial soln., revealing a partial desolvation of both magnesium and chloride ions. As a whole, the nature and amt. of the intruded species correspond to a MgCl2•10H2O compn. Moreover, at a higher pressure (0.68 GPa), a phase transition from the orthorhombic Pmnn to the monoclinic P21/n s.g. is obsd. in Si-FER. At 1.47 GPa, the zeolite maintains this monoclinic symmetry, while another phase transition, to the monoclinic P21 s g., is argued from the anal. of the pattern of the sample compressed to 2.6 GPa and then collected upon pressure release to ambient conditions.
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    63. 63
      Confalonieri, G.; Ryzhikov, A.; Arletti, R.; Quartieri, S.; Vezzalini, G.; Isaac, C.; Paillaud, J. L.; Nouali, H.; Daou, T. J. Structural Interpretation of the Energetic Performances of a Pure Silica LTA-Type Zeolite. Phys. Chem. Chem. Phys. 2020, 22 (9), 5178– 5187,  DOI: 10.1039/C9CP06760D
      63
      Structural interpretation of the energetic performances of a pure silica LTA-type zeolite
      Confalonieri, Giorgia; Ryzhikov, Andrey; Arletti, Rossella; Quartieri, Simona; Vezzalini, Giovanna; Isaac, Carole; Paillaud, Jean-Louis; Nouali, Habiba; Daou, T. Jean
      Physical Chemistry Chemical Physics (2020), 22 (9), 5178-5187CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
      The high pressure intrusion-extrusion process of different electrolyte aq. solns. (NaCl and CaCl2, 2 M and 3 M) in a hydrophobic pure-silica LTA zeolite was investigated for energetic purposes by means of in situ X-ray powder diffraction, porosimeter tests, thermogravimetric anal. and NMR spectroscopy. The intrusion pressure of the saline solns. was proved to be higher than that of pure water, with the highest value measured for CaCl2, thus increasing the energetic performance of the system. The intrusion of NaCl solns. was irreversible (bumper behavior), whereas that of CaCl2 solns. is partially reversible (shock absorber behavior). The structural investigation allowed interpreting these results on the basis of the different intrusion mechanisms, in turn induced by the different nature of the cations present in the electrolyte solns. When Si-LTA is intruded by NaCl soln., firstly H2O mols. penetrate the pores, leading to higher silanol defect formation followed by the solvated ions. With CaCl2, instead, due to a higher solvation enthalpy of Ca2+, a higher pressure is required for intrusion, and both H2O and ions penetrate at the same pressure. The structural refinements demonstrate (i) a different arrangement of the extraframework species in the two systems, (ii) the intrusion of the salt solns. occurs through strong desolvation of the ions and (iii) the salt/H2O ratios of the intruded species are higher than those of the starting electrolyte solns.
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    64. 64
      Hughes, Z. E.; Carrington, L. A.; Raiteri, P.; Gale, J. D. A Computational Investigation into the Suitability of Purely Siliceous Zeolites as Reverse Osmosis Membranes. J. Phys. Chem. C 2011, 115 (10), 4063– 4075,  DOI: 10.1021/jp109591f
      64
      A Computational Investigation into the Suitability of Purely Siliceous Zeolites as Reverse Osmosis Membranes
      Hughes, Zak E.; Carrington, Louise A.; Raiteri, Paolo; Gale, Julian D.
      Journal of Physical Chemistry C (2011), 115 (10), 4063-4075CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      Desalination by reverse osmosis is an increasingly important source of potable water in many countries. The interest in developing new, more effective membranes is, therefore, great. One set of materials that have been suggested as a possible new type of desalination membrane are nanoporous materials. In this work computational methods are used to investigate the behavior of water within five different zeolitic systems. Quantum mech. calcns. are used to construct a set of force-field parameters for two atomistic models. Mol. dynamics simulations of the zeolites show that water will diffuse through zeolites at a rate faster than that obtained with the composite membranes currently used in com. desalination. In addn., the thermodn. of salt rejection have been investigated using the free energy perturbation method. The results of these calcns. show that the chloride ion finds the zeolitic environment strongly unfavorable compared to the bulk soln. In the case of the sodium ion, the energetic difference between the zeolite environment and soln. is less significant, but charge sepn. prevents sodium from permeating the membrane.
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    65. 65
      Vaitheeswaran, S.; Rasaiah, J. C.; Hummer, G. Electric Field and Temperature Effects on Water in the Narrow Nonpolar Pores of Carbon Nanotubes. J. Chem. Phys. 2004, 121 (16), 7955– 7965,  DOI: 10.1063/1.1796271
      65
      Electric field and temperature effects on water in the narrow nonpolar pores of carbon nanotubes
      Vaitheeswaran, Subramanian; Rasaiah, Jayendran C.; Hummer, Gerhard
      Journal of Chemical Physics (2004), 121 (16), 7955-7965CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
      Water mols. in the narrow cylindrical pore of a (6,6) carbon nanotube form single-file chains with their dipoles collectively oriented either up or down along the tube axis. We study the interaction of such water chains with homogeneous elec. fields for finite closed and infinite periodically replicated tubes. By evaluating the grand-canonical partition function term-by-term, we show that homogeneous elec. fields favor the filling of previously empty nanotubes with water from the bulk phase. A two-state description of the collective water dipole orientation in the nanotube provides an excellent approxn. for the dependence of the water-chain polarization and the filling equil. on the elec. field. The energy and entropy contributions to the free energy of filling the nanotube were detd. from the temp. dependence of the occupancy probabilities. We find that the energy of transfer depends sensitively on the water-tube interaction potential, and that the entropy of one-dimensionally ordered water chains is comparable to that of bulk water. We also discuss implications for proton transfer reactions in biol.
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    66. 66
      de Freitas, D. N.; Mendonça, B. H.; Köhler, M. H.; Barbosa, M. C.; Matos, M. J. S.; Batista, R. J. C.; de Oliveira, A. B. Water Diffusion in Carbon Nanotubes under Directional Electric Frields: Coupling between Mobility and Hydrogen Bonding. Chem. Phys. 2020, 537 (April), 110849,  DOI: 10.1016/j.chemphys.2020.110849
      66
      Water diffusion in carbon nanotubes under directional electric frields: Coupling between mobility and hydrogen bonding
      de Freitas, Debora N.; Mendonca, Bruno H. S.; Kohler, Mateus H.; Barbosa, Marcia C.; Matos, Matheus J. S.; Batista, Ronaldo J. C.; de Oliveira, Alan B.
      Chemical Physics (2020), 537 (), 110849CODEN: CMPHC2; ISSN:0301-0104. (Elsevier B.V.)
      Mol. Dynamics simulations of water confined in carbon nanotubes subjected to external elec. fields show that water mobility strongly depends on the confining geometry, the intensity and directionality of the elec. field. While fields forming angles of 0° and 45° slow down the water dynamics by increasing organization, perpendicular fields can enhance water diffusion by decreasing hydrogen bond formation. For 1.2 diam. long nanotubes, the parallel field destroys the ice-like water structure increasing mobility. These results indicate that the structure and dynamics of confined water are extremely sensitive to external fields and can be used to facilitate filtration processes.
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    67. 67
      Gao, Y.; Yin, M.; Zhang, H.; Xu, B. Electrically Suppressed Outflow of Confined Liquid in Hydrophobic Nanopores. ACS Nano 2022, 16 (6), 9420– 9427,  DOI: 10.1021/acsnano.2c02240
      67
      Electrically Suppressed Outflow of Confined Liquid in Hydrophobic Nanopores
      Gao, Yuan; Yin, Mengtian; Zhang, Haozhe; Xu, Baoxing
      ACS Nano (2022), 16 (6), 9420-9427CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
      Confining liq. in a hydrophobic nanoenvironment has enabled a broad spectrum of applications in biomedical sensors, mech. actuators, and energy storage and converters, where the outflow of confined liq. is spontaneous and fast due to the intrinsic hydrophobic nature of nanopores with extremely low interfacial friction, challenging design capacity and control tolerance of structures and devices. Here, we present a facile approach of suppressing the outflow of water confined in hydrophobic nanopores with an elec. field. Extensive mol. dynamics simulations show that the presence of an elec. field could significantly strengthen hydrogen bonds and retard degrdns. of the assocd. networks during the outflow. The outflow deformation and strength are extd. to quant. characterize the elec. suppression to outflow and agree well with simulations. This study proposes a practical means of impeding the fast liq. outflow in hydrophobic nanopores, potentially useful for devising nanofluidics-based functional structures and devices with controllable performance.
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    68. 68
      Lu, D.; Li, Y.; Rotkin, S. V.; Ravaioli, U.; Schulten, K. Finite-Size Effect and Wall Polarization in a Carbon Nanotube Channel. Nano Lett. 2004, 4 (12), 2383– 2387,  DOI: 10.1021/nl0485511
      68
      Finite-Size Effect and Wall Polarization in a Carbon Nanotube Channel
      Lu, Deyu; Li, Yan; Rotkin, Slava V.; Ravaioli, Umberto; Schulten, Klaus
      Nano Letters (2004), 4 (12), 2383-2387CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
      The electronic structure and dielec. screening of finite-length armchair carbon nanotubes are studied in view of their tech. applications. For this purpose, a self-consistent tight-binding method, which captures the periodic oscillation pattern of the finite band gap as a function of tube length, is applied. We find the parallel screening const. ε‖ to grow nearly linearly with the length L and to show little dependence on the band gap. In contrast, the perpendicular screening const. ε.perp. is strongly related to the band gap and converges for L > 10R (radius) to its bulk value. Our description is employed to study the wall polarization in a short (6,6) nanotube filled with six water mols., a situation that arises with tech. uses of carbon nanotubes as channels.
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    69. 69
      Shen, C.; Qiu, H.; Guo, W. Soliton-like Propagation of Dipole Reorientation in Confined Single-File Water Chains. Nanoscale 2019, 11 (41), 19387– 19392,  DOI: 10.1039/C9NR03631H
      69
      Soliton-like propagation of dipole reorientation in confined single-file water chains
      Shen, Chun; Qiu, Hu; Guo, Wanlin
      Nanoscale (2019), 11 (41), 19387-19392CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)
      A review. Water mols. confined in a narrow nanotube channel orient themselves into a uniformly ordered single-file chain. Here, we report by means of comprehensive mol. dynamics simulations and soliton-model-based theor. anal. that the reorientation (i.e., rotation) of a single water mol. in this dipole chain, triggered for example by an external charge, can induce successive reorientation of the rest of the water mols., which propagates in a soliton-like manner. The resulting local potential energy peak sepg. the reoriented and the pending reorientation subsections moves with an unweakened peak intensity at a const. velocity in the ambient environment, and particularly, can penetrate or make a turn through a crossed nanotube junction. The propagation velocity depends on the strength of the external charge, in agreement with our sine-Gordon soliton-based theor. anal. We further show that this unidirectional propagation originates from the partially inhibited fluctuation in dipole orientation of reoriented water with respect to that of original ones. These findings may be helpful in the development of high-efficiency information transmitting, processing and storage devices and the understanding of functioning of biol. water channels.
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    70. 70
      Zhang, Y.; Zhang, J.; Luo, R.; Dou, Y. Experimental Study on the Effects of Applied Electric Field on Liquid Infiltration into Hydrophobic Zeolite. Energies 2023, 16 (13), 5065,  DOI: 10.3390/en16135065
      70
      Experimental Study on the Effects of Applied Electric Field on Liquid Infiltration into Hydrophobic Zeolite
      Zhang, Yafei; Zhang, Jiahua; Luo, Rui; Dou, Yihua
      Energies (Basel, Switzerland) (2023), 16 (13), 5065CODEN: ENERGA; ISSN:1996-1073. (MDPI AG)
      A nanofluidic energy absorption system (NEAS) is composed of nanoporous material and functional liq. with high energy absorption d. Applying an elec. field to adjust the energy absorption characteristics of a nanofluidic system will open broader prospects for its application. In the current work, ZSM-5 zeolite was adopted as the nanoporous material and water, a 25% KCl soln., and a satd. KCl soln. were adopted as functional liqs. to configure NEASs. Pressure-induced infiltration expts. were carried out to study the infiltration and defiltration characteristics of the NEASs under the action of an applied elec. field. The results show that the introduction of an applied elec. field can weaken the hydrogen bonds between mols., thus reducing the equiv. surface tension and contact angle, changing the infiltrability of liq. mols. into the nanopores, and reducing the infiltration pressure of the system. In an electrolyte soln./zeolite system, the anions and cations move close to the two plate electrodes under the action of an external elec. field, and the fluid properties in the central zone of the pressure chamber are close to the water/zeolite system. For both an ultra-low cond. liq. and an electrolyte soln./zeolite system, applying an elec. field can effectively improve the relative outflow rate of liq., thus improving the reusability of the system.
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    71. 71
      Lin, Y.; Shiomi, J.; Maruyama, S.; Amberg, G. Dielectric Relaxation of Water inside a Single-Walled Carbon Nanotube. Phys. Rev. B: Condens. Matter Mater. Phys. 2009, 80 (4), 045419– 45427,  DOI: 10.1103/PhysRevB.80.045419
      71
      Dielectric relaxation of water inside a single-walled carbon nanotube
      Lin, Yuan; Shiomi, Junichiro; Maruyama, Shigeo; Amberg, Gustav
      Physical Review B: Condensed Matter and Materials Physics (2009), 80 (4), 045419/1-045419/7CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)
      We report a mol. dynamics study of anisotropic dynamics and dielec. properties of water confined inside a single-walled C nanotube (SWNT) at room temp. The model includes dynamics of an SWNT described by a realistic potential function. A comparison with simulations assuming a rigid nanotube demonstrates that the popular assumption severely overestimates the dielec. const. for small diam. SWNTs. Simulations of water inside flexible SWNTs with various diams. reveal strong directional dependence of the dynamic and dielec. properties due to the confinement effect. The obtained dielec. permittivity spectra (DPS) identify 2 different dipolar relaxation frequencies corresponding to the axial and the cross-sectional directions, which are significantly smaller and larger than the single relaxation frequency of bulk water, resp. The frequency variation increases as the SWNT diam. decreases. DPS can be used as a fingerprint of water inside SWNTs to monitor the water intrusion into SWNTs.
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    72. 72
      Fasano, M.; Crisafulli, A.; Cardellini, A.; Bergamasco, L.; Chiavazzo, E.; Asinari, P. Thermally Triggered Nanorocket from Double-Walled Carbon Nanotube in Water. Mol. Simul. 2019, 45 (4–5), 417– 424,  DOI: 10.1080/08927022.2018.1535180
      72
      Thermally triggered nanorocket from double-walled carbon nanotube in water
      Fasano, Matteo; Crisafulli, Alessandro; Cardellini, Annalisa; Bergamasco, Luca; Chiavazzo, Eliodoro; Asinari, Pietro
      Molecular Simulation (2019), 45 (4-5), 417-424CODEN: MOSIEA; ISSN:0892-7022. (Taylor & Francis Ltd.)
      In this work, we propose and investigate the use of double-walled carbon nanotubes (DWCNTs) as nanosized rockets. The nanotubes are immersed in water, and the propulsion of inner nanotube is achieved by heating the water encapsulated within the DWCNT. Considering a setup made of (5,5)(8,8) DWCNT, mol. dynamics simulations for different water temps. show that the trajectory can be divided into four phases: trigger, expulsion, damping and final equil. After analyzing the dynamics and the involved forces, we find out that the inner nanotube expulsion is mainly controlled by van der Waals interactions between the nanotubes; whereas, the damping role is predominantly played by the external aq. environment. Based on these results, we propose an anal. model able to predict both the triggering time for a given water temp. and the whole dynamics of nanorocket. The validity of such dynamical model can be extended also to a broader variety of DWCNT configurations, once the different forces acting on the inner nanotube are provided. The proposed model may contribute to assist the design of nanorockets in several nanotechnol. applications, such as triggered drug delivery, cell membrane piercing, or colloids with thermophoretic properties.
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    73. 73
      Li, J.; Rozen, I.; Wang, J. Rocket Science at the Nanoscale. ACS Nano 2016, 10, 5619– 5634,  DOI: 10.1021/acsnano.6b02518
      73
      Rocket Science at the Nanoscale
      Li, Jinxing; Rozen, Isaac; Wang, Joseph
      ACS Nano (2016), 10 (6), 5619-5634CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
      A review. Autonomous propulsion at the nanoscale represents one of the most challenging and demanding goals in nanotechnol. Over the past decade, numerous important advances in nanotechnol. and material science have contributed to the creation of powerful self-propelled micro/nanomotors. In particular, micro- and nanoscale rockets (MNRs) offer impressive capabilities, including remarkable speeds, large cargo-towing forces, precise motion controls, and dynamic self-assembly, which have paved the way for designing multifunctional and intelligent nanoscale machines. These multipurpose nanoscale shuttles can propel and function in complex real-life media, actively transporting and releasing therapeutic payloads and remediation agents for diverse biomedical and environmental applications. This review discusses the challenges of designing efficient MNRs and presents an overview of their propulsion behavior, fabrication methods, potential rocket fuels, navigation strategies, practical applications, and the future prospects of rocket science and technol. at the nanoscale.
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    74. 74
      Venugopalan, P. L.; Esteban-Fernández De Ávila, B.; Pal, M.; Ghosh, A.; Wang, J. Fantastic Voyage of Nanomotors into the Cell. ACS Nano 2020, 14, 9423– 9439,  DOI: 10.1021/acsnano.0c05217
      74
      Fantastic Voyage of Nanomotors into the Cell
      Venugopalan, Pooyath Lekshmy; Esteban-Fernandez de Avila, Berta; Pal, Malay; Ghosh, Ambarish; Wang, Joseph
      ACS Nano (2020), 14 (8), 9423-9439CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
      A review. Richard Feynman's 1959 vision of controlling devices at small scales and swallowing the surgeon has inspired the science-fiction Fantastic Voyage film and has played a crucial role in the rapid development of the microrobotics field. Sixty years later, the authors are currently witnessing a dramatic progress in this field, with artificial micro- and nanoscale robots moving within confined spaces, down to the cellular level, and performing a wide range of biomedical applications within the cellular interior while addressing the limitations of common passive nanosystems. In this review article, key recent advances in the field of micro/nanomotors toward important cellular applications are discussed. Specifically, the authors outline the distinct capabilities of nanoscale motors for such cellular applications and illustrate how the active movement of nanomotors leads to distinct advantages of rapid cell penetration, accelerated intracellular sensing, and effective intracellular delivery toward enhanced therapeutic efficiencies. The authors finalize by discussing the future prospects and key challenges that such micromotor technol. face toward implementing practical intracellular applications. By increasing the authors' knowledge of nanomotors' cell entry and of their behavior within the intracellular space, and by successfully addressing key challenges, the authors expect that next-generation nanomotors will lead to exciting advances toward cell-based diagnostics and therapy.
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    75. 75
      Wu, Y.; Tepper, H. L.; Voth, G. A. Flexible Simple Point-Charge Water Model with Improved Liquid-State Properties. J. Chem. Phys. 2006, 124 (2), 024503,  DOI: 10.1063/1.2136877
      75
      Flexible simple point-charge water model with improved liquid-state properties
      Wu, Yujie; Tepper, Harald L.; Voth, Gregory A.
      Journal of Chemical Physics (2006), 124 (2), 024503/1-024503/12CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
      In order to introduce flexibility into the simple point-charge (SPC) water model, the impact of the intramol. degrees of freedom on liq. properties was systematically studied in this work as a function of many possible parameter sets. It was found that the diffusion const. is extremely sensitive to the equil. bond length and that this effect is mainly due to the strength of intermol. hydrogen bonds. The static dielec. const. was found to be very sensitive to the equil. bond angle via the distribution of intermol. angles in the liq.: A larger bond angle will increase the angle formed by two mol. dipoles, which is particularly significant for the first solvation shell. This result is in agreement with the work of Hochtl et al. [J. Chem. Phys. 109, 4927 (1998)]. A new flexible simple point-charge water model was derived by optimizing bulk diffusion and dielec. consts. to the exptl. values via the equil. bond length and angle. Due to the large sensitivities, the parametrization only slightly perturbs the mol. geometry of the base SPC model. Extensive comparisons of thermodn., structural, and kinetic properties indicate that the new model is much improved over the std. SPC model and its overall performance is comparable to or even better than the extended SPC model.
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    76. 76
      Aragones, J. L.; Noya, E. G.; Abascal, J. L. F.; Vega, C. Properties of Ices at 0 K: A Test of Water Models. J. Chem. Phys. 2007, 127 (15), 154510– 154518,  DOI: 10.1063/1.2774986
      There is no corresponding record for this reference.
    77. 77
      Bushuev, Y. G.; Sastre, G.; de Julián-Ortiz, J. V.; Gálvez, J. Water-Hydrophobic Zeolite Systems. J. Phys. Chem. C 2012, 116 (47), 24916– 24929,  DOI: 10.1021/jp306188m
      77
      Water-Hydrophobic Zeolite Systems
      Bushuev, Yuriy G.; Sastre, German; de Julian-Ortiz, J. Vicente; Galvez, Jorge
      Journal of Physical Chemistry C (2012), 116 (47), 24916-24929CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      Water intrusion-extrusion in hydrophobic microporous AFI, IFR, MTW and TON pure silica zeolites (zeosils) has been investigated through mol. dynamics (MD) simulations. It was found that intruded water vols. correlate with the free vol. of the zeosil unit cells. Calcd. adsorption isotherms allowed us to est. the amts. of water intruded, and deviations from expts. (lower exptl. with respect to calcd. intrusion pressures) have been explained in terms of connectivity defects in the synthesized materials. Water phase transitions in defectless zeosils occur in a narrow range at high pressure. On the basis of a simple model, we derived a thermodn. equation that allows one to est. the intrusion pressure with few parameters, which are easy to obtain, such as fractional free vol. of zeosil and the intrusion pressure of a ref. system. The structural properties of water clusters inside the zeosil micropores have been interpreted from the anal. of the MD simulations. Compact 'bulk-like' clusters form in large channels such as those in AFI and IFR zeosils. The smaller channels of MTW and TON promote the formation of chain-like clusters, which, interestingly, are commensurate with the zeolite channel topol. due to a coincidence between the distances of the crystallog. parameter, along the channel, and a max. in the O-O radial distribution function of bulk water.
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  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.3c17272.

    • DL_POLY input files (ZIP)

    • Characteristics of pure silica zeolites and grafted mesoporous silica materials with the 1D system of channels; pore openings in zeolites with the 1D system of channels; evolution of dipole orientations in the water cluster in the tube; time evolutions of the average cosine and the number of water molecules in the tube; fragments of square ice structure; evolution of average cosine between dipole moments and the axial direction of the tube; collection of snapshots of clusters in the tube; extrusion of water from the tube; and statistics of H bonds for water in tubes (PDF)


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