An oligonucleotide-based electrochemically controlled gold-coated microcantilever biosensor that can transduce specific biomolecular interactions is reported. The derivatized microcantilever exhibits characteristic surface stress time course patterns in response to an externally applied periodic square wave potential. Experiments demonstrate that control of the surface charge density with an electrode potential is essential to producing a sensor that exhibits large, reproducible surface stress changes. The time course of surface stress changes are proposed to be linked to an electrochemically mediated competition between the adsorption of solution-based ions and the single- or double-stranded oligonucleotides tethered to the gold surface. A similar potential-actuated change in surface stress also results from the interaction between an oligonucleotide aptamer and its cognate ligand, demonstrating the broad applicability of this methodology.

The characterization of liposomes was undertaken using in-situ microfluidic transmission electron microscopy. Liposomes were imaged without contrast enhancement staining or cryogenic treatment, allowing for the observation of functional liposomes in an aqueous environment. The stability and quality of the liposome structures observed were found to be highly dependent on the surface and liposome chemistries within the liquid cell. The successful imaging of liposomes suggests the potential for the extension of in-situ microfluidic TEM to a wide variety of other biological and soft matter systems and processes.

In this study of drying water-based nanofluid droplets, we report the influence of surface functional groups and substrate surface energies on crack formation and dry-out shape. These two key parameters are investigated by allowing nanofluids with several functional groups grafted on polystyrene nanoparticle surfaces to dry on various substrates. These experiments result in a variety of regular crack patterns with identical nanoparticle diameter, material, concentration, and drying conditions. We demonstrate that, despite the various patterns observed, the crack spacing/deposit height ratio is constant for similar substrate surface energies and linearly increases with this parameter. Moreover, this study shows that the crack shape is strongly influenced by surface functional groups as a result of particle interactions (depending on the particle surface potentials) and compaction during solvent evaporation.

Phenothiazine (PTZ) crystals are grown by a physical vapor transport method in a horizontal tube furnace. The resulting disk-type PTZ single crystals have a layered structure, which can be mechanically exfoliated into stacked individual layers to exhibit various colors depending on the thickness. The PTZ single-crystal field-effect transistor (FET) devices exhibit a p-type semiconducting property with 3.03 × 10^–6 S/cm electrical conductivity, 1.15 × 10^–4 cm²/(V s) carrier mobility, and a 10⁴ on/off ratio.

We study the formation of porous polymer nanostructures fabricated by the surface-induced phase separation of polymer solutions in anodic aluminum oxide (AAO) templates. Poly(methyl methacrylate) (PMMA) and tetrahydrofuran (THF) are used to investigate the evolution process of the surface-induced phase separation. With the longer immersion time of the AAO template in the polymer solution, the size of the solvent-rich droplet is increased by the coarsening process, resulting in the formation of porous polymer nanostructures. The coarsening mechanism is further evaluated by changing the experimental parameters including the immersion time, the polymer concentration, the polymer molecular weight, and the solvent quality. Under conditions in which polymer solutions have higher viscosities, the coarsening process is slowed down and the formation of the porous nanostructures is prohibited. The prevention of the porous nanostructures can also be realized by adding water to the PMMA/THF solution before the immersion process.

The ethanol–water exchange process is one of the standard methods of generating nanobubbles at a solid–water interface. In this work, we examine whether the nanobubbles formed by the solvent exchange can initiate microbubble formation as the temperature increases, thus acting as nuclei. This, however, is not the case: the nanobubbles are stable and do not facilitate microbubble formation. Instead, the process of solvent exchange, which aids the formation of nanobubbles and even microbubbles on some hydrophobic substrates under ambient conditions, suppresses microbubble nucleation on graphite and hydrophilic micropit-decorated substrates at high temperature (i.e., deactivates the nucleation sites for microbubble formation). We ascribe this behavior to the prewetting of the surface by the alcohol and the stability of the nanobubbles to the temperature increase. The findings in this study have implications for the prevention of bubble formation for a range of applications.

Fluid transport through microporous carbon-based materials is inherent in numerous applications, ranging from gas separation by carbon molecular sieves to natural gas production from coal seams and gas shales. The present study investigates the steady-state permeation of supercritical methane in response to a constant cross-membrane pressure drop. We performed dual control volume grand canonical molecular dynamics (DCV-GCMD) simulations to mimic the conditions of actual permeation experiments. To overcome arbitrary assumptions regarding the investigated porous structures, the membranes were modeled after the CS1000a and CS1000 molecular models, which are representative of real microporous carbon materials. When adsorption-induced molecular trapping (AIMT) mechanisms are negligible, we show that the permeability of the microporous material, although not significantly sensitive to the pressure gradient, monotonically decreases with temperature and reservoir pressures, consistent with diffusion theory. However, when AIMT occurs, the permeability increases with temperature in agreement with experimental data found in the literature.

Using turbidity measurements, we quantified the interactions between PDMS-grafted silica nanoparticles (PDMS-g-silica) in pure solvents and a concentrated polymer solution with a focus on detecting the impact of solvent quality on graft layer stretching. This work is an extension of our previous work where we showed that interfacial wetting of the grafted polymer leads to depletion restabilization in semidilute and concentrated polymer solutions in good solvents (Dutta, N.; Green, D. Langmuir 2008, 24, 5260−5269). Subsequently, we showed that the criterion for depletion restabilization holds for both good and marginally poor solvents (Dutta, N.; Green, D. Langmuir 2010, 26, 16737−16744). In this work, we quantified nanoparticle interactions in terms of the second virial coefficient (B₂), which captures the stretching of the brush in a good solvent in comparison to compression in a poor solvent. The transition from stretching to compression of the graft layer as a function of solvent quality was also supported by self-consistent mean-field (SCF) calculations. The PDMS-g-silica nanoparticles in a concentrated polymer solution in a good solvent within the complete wetting region behaved as though they were in a good solvent rather than in a polymer melt where on the basis of the SCF calculations the graft layers were expected to behave ideally. Overall, our results indicate that turbidity measurements can be used to determine the second virial coefficients for polymer-grafted nanoparticles in solvents and concentrated polymer solutions, and the relative values of the coefficients correspond well to those from theoretical calculations.

A series of novel amphiphiles were designed for self-assembly into chiral morphologies, the amphiphiles consisting of a glutamic acid (Glu) headgroup connected through an 11-carbon alkoxy chain to a diphenyldiazenyl (Azo) group and terminated with a variable length alkyl chain (R-Azo-11-Glu, where R denotes the number of carbons in the distal chain). TEM imaging of amphiphile aggregates self-assembled from heated, methanolic, aqueous solution showed that chiral order, expressed as twisted ribbons, helical ribbons, and helically based nanotubes, increased progressively up to a distal chain length containing eight carbons, and then decreased with further increases in distal chain length. TEM and CD showed that the chiral aggregations of single enantiomers were influenced by the molecular chirality of the headgroup. However, the assembly of d,l-10-Azo-11-Glu into nanotubes demonstrated that chiral symmetry breaking effected by the azo group was also relevant to the chiral organization of the amphiphiles. The chiral order of aggregate morphologies was additionally affected by the temperature and solvent composition of assembly in a manner correlated to the mechanism driving assembly; i.e., d,l-10-Azo-11-Glu was sensitive to the temperature of assembly but less so to solvent composition, while l-14-Azo-11-Glu was sensitive to solvent composition and not to temperature. FTIR and UV–vis spectroscopic investigations into the organization of the head and azo groups, in chiral and achiral structures, illustrated that a balance of the influences of the hydrophilic and hydrophobic components on self-assembly was required for the optimization of the chiral organization of the self-assembled structures.

In this paper, lithographic methods are successfully employed to create growth templates for colloidal self-assembly, enabling the inclusion of crystallographic defects at predetermined positions. It is shown that through smart template design stacking faults can be grown predictably into face centered cubic structures. More interestingly, by precise guiding of the stacking faults hollow intergrowth channels can be grown at predetermined lateral and vertical positions. The mechanisms involved in defect growth are promising for extension of this technique to more complex crystal structures, such as the diamond structure, as well as to more complex faults, including corners and t-junctions.

We have developed a new class of bistable Pickering foams, which can remain intact for weeks at room temperature but can be destroyed rapidly and on-demand with the use of a magnetic field. Such responsive foam systems can find application in various industrial and environmental processes that require controlled defoaming. These foams are stabilized by particles of hypromellose phthalate (HP-55) and contain oleic acid-coated carbonyl iron particles embedded in the HP-55 matrix. The complex behavior of these foams arises from several factors: a robust anisotropic particle matrix, the capacity to retain a high amount of water, as well as an age-dependent response to an external field. We report how the structure and viscoelastic properties of the foams change with time and affect their collapse characteristics. The evolution of foam properties is quantified by measuring the rate of liquid drainage from the foam as well as the rate of bubble growth in the foam with respect to time elapsed (in the absence of a magnetic field). We also evaluate the time necessary for foam collapse in magnetic fields as a function of magnetic particle content. A decreasing liquid volume fraction in the foam during aging leads to an increase in the elasticity and rigidity of the foam structure. These data allow us to identify a transition time separating two distinct stages of foam development in the absence of field. We propose different mechanisms which control foam collapse for each stage in a magnetic field. The stiffening of foam films between air bubbles with age plays a key role in distinguishing between the two destabilization regimes.

The simultaneous spreading and evaporation of droplets of aqueous trisiloxane (superspreader) solutions onto a hydrophobic substrate has been studied both experimentally, using a video-microscopy technique, and theoretically. The experiments have been carried out over a wide range of surfactant concentration, temperature, and relative humidity. Similar to pure liquids, four different stages have been observed: the initial one corresponds to spreading until the contact angle, θ, reaches the value of the static advancing contact angle, θ_ad. Duration of this stage is rather short, and the evaporation during this stage can be neglected. The evaporation is essential during the next three stages. The next stage after the spreading, which is referred to herein as the first stage, takes place at constant perimeter and ends when θ reaches the static receding contact angle, θ_r. During the next, second stage, the perimeter decreases at constant contact angle θ = θ_r for surfactant concentration above the critical wetting concentration (CWC). The static receding contact angle decreases during the second stage for concentrations below CWC because the concentration increases due to the evaporation. During the final stage both the perimeter and the contact angle decrease. In what follows, we consider only the longest stages I and II. The developed theory predicts universal curves for the contact angle dependency on time during the first stage, and for the droplet perimeter on time during the second stage. A very good agreement between theory and experimental data has been found for the first stage of evaporation, and for the second stage for concentrations above CWC; however, some deviations were found for concentrations below CWC.

The properties of ionic micelles are affected by the nature of the counterion. Specific ion effects can be dramatic, inducing even shape and phase changes in micellar solutions, transitions apparently related to micellar hydration and counterion binding at the micellar interface. Thus, determining the hydration and dynamics of ions in micellar systems capable of undergoing such transitions is a crucial step in understanding shape and phase changes. For cationic micelles, such transitions are common with large organic anions as counterions. Interestingly, however, phase separation also occurs for dodecyltrimethylammonium triflate (DTATf) micelles in the presence of sodium triflate (NaTf). Specific ion effects for micellar solutions of dodecyltrimethylammonium chloride (DTAC), bromide (DTAB), methanesulfonate (DTAMs), and triflate (DTATf) were studied with dielectric relaxation spectroscopy (DRS), a technique capable of monitoring hydration and counterion dynamics of micellar aggregates. In comparison to DTAB, DTAC, and DTAMs, DTATf micelles were found to be considerably less hydrated and showed reduced counterion mobility at the micellar interface. The obtained DTATf and DTAMs data support the reported central role of the anion’s −CF₃ moiety with respect to the properties of DTATf micelles. The reduced hydration observed for DTATf micelles was rationalized in terms of the higher packing of this surfactant compared to that of other DTA-based systems. The decreased mobility of Tf^– anions condensed at the DTATf interface strongly suggests the insertion of Tf^– in the micellar interface, which is apparently driven by the strong hydrophobicity of −CF₃.

The amphiphilic properties of conjugated oligoelectrolytes (COE) and their sensitivity to the polarity of their microenvironment lead to interesting aggregation behavior, in particular in their interaction with surfactants. Photoluminescence (PL) spectroscopy, liquid-phase atomic force microscopy, small-angle neutron scattering, small-angle X-ray scattering, and grazing-incidence X-ray diffraction were used to examine interactions between cationic p-phenylene vinylene based oligoelectrolytes and surfactants. These techniques indicate the formation of COE/surfactant aggregates in aqueous solution, and changes in the photophysical properties are observed when compared to pure aqueous solutions. We evaluate the effect of the charge of the surfactant polar headgroup, the size of the hydrophobic chain, and the role of counterions. At low COE concentrations (micromolar), it was found that these COEs display larger emission quantum efficiencies upon incorporation into micelles, along with marked blue-shifts of the PL spectra. This effect is most pronounced in the series of anionic surfactants, and the degree of blue shifts as a function of surfactant charge is as follows: cationic < nonionic < anionic surfactants. In anionic surfactants, such as sodium dodecyl sulfate (SDS), the PL spectra show vibronic resolution above the critical micelle concentration of the surfactant, suggesting more rigid structures. Scattering data indicate that in aqueous solutions, trimers appear as essentially 3-dimensional particles, while tetra- and pentamers form larger, cylindrical particles. When the molar ratio of nonionic C₁₂E₅ surfactant to 1,4-bis(4-{N,N-bis-[(N,N,N-trimethylammonium)hexyl]amino}-styryl)benzene tetraiodide (DSBNI) is close to one, the size of the formed DSBNI-C₁₂E₅ particles corresponds to the full coverage of individual oligomers. When these particles are transferred into thin films, they organize into a cubic in-plane pattern. If anionic SDS is added, the formed DSBNI-SDS particles are larger than expected for full surfactant coverage, and particles may thus contain several oligomers. This tendency is attributed to the merging of DSBNI oligomers due to the charge screening and, thus, reduced water solubility.

We report a first application of vertical small-angle X-ray scattering to investigate the drying process of a colloidal suspension by overcoming gravity related restrictions. From the observation of the drying behavior of charge-stabilized colloidal silica in situ, we find the solidification of the colloidal particles exhibits an initial ordering, followed by a sudden aggregation when they overcome an electrostatic energy barrier. The aggregation can be driven not only by capillary pressure but also by thermal motion of the particles. The dominating contribution is determined by the magnitude of the energy barrier at the transition, which significantly decreases during drying due to an increased ionic strength.

The micelle–vesicle–micelle transition in aqueous mixtures of the cationic surfactant cetyl trimethyl ammonium bromide (CTAB) and the anionic surfactant-like ionic liquid 1-butyl-3-methylimidazolium octyl sulfate, [C₄mim][C₈SO₄] has been investigated by using dynamic light scattering (DLS), transmission electron microscopy (TEM), surface tension, conductivity, and fluorescence anisotropy at different volume fractions of surfactant. The surface tension value decreases sharply with increasing CTAB concentration up to ∼0.38 volume fraction and again increases up to ∼0.75 volume fraction of CTAB. Depending upon their relative amount, these surfactants either mixed together to form vesicles and/or micelles, or both of these structures were in equilibrium. Fluorescence anisotropy of 1,6-diphenyl-1,3,5-hexatriene (DPH), incorporated in this system at different composition of surfactant indicates the formation of micelle and vesicle structures. The apparent hydrodynamic diameter of these large multilamellar vesicles is about ∼200 nm–300 nm obtained by DLS measurement and finally confirmed by TEM micrographs. The large multilamellar vesicles are transformed into small unilamellar ones by sonication using a Lab-line instruments probe sonicator with a diameter of ∼90–125 nm. To investigate the heterogeneity, solvent, and rotational relaxation of coumarin-153 (C-153) have been investigated in these unilamellar vesicles by using picosecond time-resolved fluorescence spectroscopic technique. The solvation dynamics of C-153 in these vesicles is found to be biexponential with average time constant ∼580 ps. This indicates the slow relaxation of water molecules in the surfactant bilayer. In accordance with solvation dynamics, fluorescence anisotropy analysis of C-153 in unilamellar vesicles also indicates hindered rotation compared to bulk water.

In this article, the impact of different neutral polymers on the kinetic stability of charge-stabilized poly(diallyldimethylammonium chloride) (PDADMAC)/sodium dodecylsulfate (SDS) colloidal dispersions is analyzed using dynamic light scattering, electrophoretic mobility, turbidity, and coagulation kinetics measurements. Poly(ethyleneoxide) (PEO), poly(vinylpyrrolidone) (PVP), and dextran of comparable molecular masses as well as a higher-molecular-weight dextran sample were tested as nonionic additives. The light scattering and mobility data indicate that the PEO and PVP molecules may adsorb on the surface of the PDADMAC/SDS nanoparticles formed in the presence of excess surfactant. The primary effect of these additives is manifested in enhanced coagulation of the PDADMAC/SDS nanoparticles due to bridging at lower polymer concentrations and depletion flocculation at higher polymer concentrations. These findings are in sharp contrast to the earlier published effect of the same nonionic polymers on the poly(ethyleneimine) (PEI)/SDS colloidal dispersions, which can be sterically stabilized at appropriate PEO or PVP concentrations. However, the adsorption of the investigated dextran samples is negligible on the PDADMAC/SDS nanoparticles. Therefore, dextran molecules may cause only depletion flocculation in the PDADMAC/SDS system in the vicinity of the critical overlap concentration.

We describe a new antifouling surface coating, based on aggregation of a short amphiphilic four-armed PEG-dopamine polymer into particles and on surface binding by catechol chemistry. An unbroken and smooth polymeric coating layer with an average thickness of approximately 4 μm was formed on top of titanium oxide surfaces by a single step reaction. Coatings conferred excellent resistance to protein adhesion. Cell attachment was completely prevented for at least eight weeks, although the membranes themselves did not appear to be intrinsically cytotoxic. When linear PEG or four-armed PEG of higher molecular weight were used, the resulting coatings were inferior in thickness and in preventing protein adhesion. This coating method has potential applicability for biomedical devices susceptible to fouling after implantation.

Conformational changes of three cyclic β-helical peptides upon adsorption onto planar fused-quartz substrates were detected and analyzed by far-ultraviolet (UV) circular dichroism (CD) spectroscopy. In trifluoroethanol (TFE), hydrophobic peptides, Leu β and Val β, form left- and right-handed helices, respectively, and water-soluble peptide WS β forms a left-handed helix. Upon adsorption, CD spectra showed a mixture of folded and unfolded conformations for Leu β and Val β and predominantly unfolded conformations for WS β. X-ray photoelectron spectroscopy (XPS) provided insight about the molecular mechanisms governing the conformational changes, revealing that ca. 40% of backbone amides in Leu β and Val β were interacting with the hydrophilic substrate, while only ca. 15% of the amines/amides in WS β showed similar interactions. In their folded β-helical conformations, Leu β and Val β present only hydrophobic groups to their surroundings; hydrophilic surface groups can only interact with backbone amides if the peptides change their conformation. Conversely, as a β helix, WS β presents hydrophilic side chains to its surroundings that could, in principle, interact with hydrophilic surface groups, with the peptide retaining its folded structure. Instead, the observed unfolded surface conformation for WS β and the relatively small percentage of surface-bound amides (15 versus 40% for Leu β and Val β) suggest that hydrophilic surface groups induce unfolding. Upon this surface-induced unfolding, WS β interacts with the surface preferentially via hydrophilic side chains rather than backbone amides. In contrast, the unfolded β-hairpin-like form of WS β does not irreversibly adsorb on fused quartz from water, highlighting that solvation effects can be more important than initial conformation in governing peptide adsorption. Both label-free methods demonstrated in this work are, in general, applicable to structural analysis of a broad range of biomolecules adsorbed on transparent planar substrates, the surface properties of which could be customized.

This article describes single-molecule force spectroscopy measurements of the interaction between individual amino acid residues and inorganic surfaces in an aqueous solution. In each measurement, there is an amino acid residue, lysine, glutamate, phenylalanine, leucine, or glutamine, and each represents a class of amino acids (positively or negatively charged, aromatic, nonpolar, and polar). Force–distance curves measured the interaction of the individual amino acid bound to a silicon atomic force microscope (AFM) tip with a silcon substrate, cut from a single-crystal wafer, or mica. Using this method, we were able to measure low adhesion forces (below 300 pN) and could clearly determine the strength of interactions between the individual amino acid residues and the inorganic substrate. In addition, we observed how changes in the pH and ionic strength of the solution affected the adsorption of the residues to the substrates. Our results pinpoint the important role of hydrophobic interactions among the amino acids and the substrate, where hydrophobic phenylalanine exhibited the strongest adhesion to a silicon substrate. Additionally, electrostatic interactions also contributed to the adsorption of amino acid residues to inorganic substrates. A change in the pH or ionic strength values of the buffer altered the strength of interactions among the amino acids and the substrate. We concluded that the interplay between the hydrophobic forces and electrostatic interactions will determine the strength of adsorption among the amino acids and the surface. Overall, these results contribute to our understanding of the interaction at the organic–inorganic interface. These results may have implications for our perception of the specificity of peptide binding to inorganic surfaces. Consequently, it would possibly lead to a better design of composite materials and devices.

A new μ-oxo-bis(μ-acetato)diruthenium(III) complex bearing two pyridyl disulfide ligands {[Ru₂(μ-O)(μ-OAc)₂(bpy)₂(L_py-SS)₂](PF₆)₂ (OAc = CH₃CO₂^–, bpy = 2,2′-bipyridine, L_py-SS = (C₅H₄N)CH₂NHC(O)(CH₂)₄CH(CH₂)₂SS) (1)} has been synthesized to prepare self-assembled monolayers (SAMs) on the Au(111) electrode surface. The SAMs have been characterized by contact-angle measurements, reflection–absorption surface infrared spectroscopy, cyclic voltammetry, and reductive desorption experiments. The SAMs exhibited proton-coupled electron transfer (PCET) reactions when the electrochemistry was studied in aqueous electrolyte solution (0.1 M NaClO₄ with Britton–Robinson buffer to adjust the solution pH). The potential–pH plot (Pourbaix diagram) in the pH range from 1 to 12 has established that the dinuclear ruthenium moiety was involved in the interfacial PCET processes with four distinct redox states: Ru^IIIRu^III(μ-O), Ru^IIRu^III(μ-OH), Ru^IIRu^II(μ-OH), and Ru^IIRu^II(μ-OH₂). We also demonstrated that the interfacial redox processes were modulated by the addition of Lewis acids such as BF₃ or Al³⁺ to the electrolyte media, in which the externally added Lewis acids interacted with μ-O of the dinuclear moiety within the SAMs.

MnO_x–CeO_x mixed oxide systems exhibit interesting sulfur adsorption capacities and catalytic activity. We examined the electronic structure of Mn-doped fluorite CeO₂ bulk solid and surface using density functional theory (DFT) with the Hubbard U term or the Heyd–Scuseria–Ernzerhof (HSE06) hybrid functional. We specifically evaluate the reducibility and formation energies of Mn-doped CeO₂ surfaces. The use of a U value on the d-states of Mn is examined, and a value of 4 eV is chosen based upon results from DFT+U calculations on bulk MnO_x,1 XANES characterization of oxidation states in calcined and reduced Mn-doped CeO₂, and comparison with HSE06 hybrid functional results. Electronic structure impacts of the U inclusion are discussed. The concentration and orientation of Mn atoms doped into the surface of CeO₂ have a great influence on the reducibility of the surface. Based upon formation energies, Mn will not favor doping into the surface of CeO₂ in a fully oxidized system (Mn⁴⁺). Under reducing environments, Mn will dope into the surface with oxygen vacancies present (Mn³⁺ and Mn²⁺). The first oxygen vacancy is not likely catalytically important in fluorite MnO_x–CeO_x systems as formation of the fully oxidized surface is not stable. A greater degree of reduction would occur during a catalyzed redox reaction.

The molecular kinetic theory (MKT) of dynamic wetting, first proposed nearly 50 years ago, has since been refined to account explicitly for the effects of viscosity and solid–liquid interactions. The MKT asserts that the systematic deviation of the dynamic contact angle from its equilibrium value quantitatively reflects local energy dissipation (friction) at the moving contact line as it traverses sites of solid–liquid interaction. Specifically, it predicts that the coefficient of contact-line friction ζ will be proportional to the viscosity of the liquid η_L and exponentially dependent upon the strength of solid–liquid interactions as measured by the equilibrium work of adhesion Wa⁰. Here, we analyze a very large set of dynamic wetting data drawn from more than 20 publications and representative of a very wide range of systems, from molecular-dynamics-simulated Lenard–Jones liquids and substrates, through conventional liquids and solids, to molten glasses and liquid metals on refractory solids. The combined set spans 9 decades of viscosity and 11 decades of contact-line friction. Our analysis confirms the predicted dependence of ζ upon η_L and Wa⁰, although the data are scattered. In particular, a plot of ln(ζ/η_L) versus Wa⁰/n (i.e., the work of adhesion per solid–liquid interaction site) is broadly linear, with 85% of the data falling within a triangular envelope defined by Wa⁰ and 0.25Wa⁰. Various reasons for this divergence are explored, and a semi-empirical approach is proposed to predict ζ. We suggest that the broad agreement between the MKT and such a wide range of data is strong evidence that the local microscopic contact angle is directly dependent upon the velocity of the contact line.

Non-specific adsorption of the molecular components of biofluids is ubiquitous in the area of biosensing technologies, severely limiting the use of biosensors in real-world applications. The surface chemistries developed to prevent non-specific adsorption of crude serum are not necessarily suited for sensing in other biosamples. In particular, the diagnostic potential of differential expression of proteins in tissues makes cell lysate attractive for disease diagnostics using solid biopsies. However, crude cell lysate poses a significant challenge for surface chemistries because of a large concentration of highly adherent lipids. Contrary to the non-specific adsorption in crude serum being suppressed by hydrophilic surfaces, the surface plasmon resonance (SPR) analysis of serine-, aspartic-acid-, histidine-, leucine-, and phenylalanine-based peptide monolayers revealed that hydrophobic and positively charged peptides decreased non-specific adsorption when using lysate from HEK 293FT cells. A polyethylene glycol (PEG) monolayer resulted in 2-fold greater fouling than the best peptide [3-MPA–(His)₂(Leu)₂(Phe)₂–OH] under the same conditions. Matrix-assisted laser desorption ionization tandem time-of-flight mass spectrometry (MALDI–TOF/TOF MS) analysis of the adsorbate from cell lysate confirmed that lipids are the main source of non-specific adsorption. Importantly, the mass spectrometry (MS) study revealed that both the number of lipids identified and their intensity decreased with decreasing non-specific adsorption. A peptide monolayer thus provides an efficient mean to suppress non-specific adsorption from this human cell lysate.

Nanotribological properties of silica surfaces, with and without adsorbed, brushlike copolymers of poly(l-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG) and poly(l-lysine)-graft-dextran (PLL-g-dextran) have been investigated in aqueous viscous solvent mixtures by means of colloid-probe lateral force microscopy. Lateral forces for PEG/dextran brushes have been measured as a function of shear velocity in aqueous mixtures of glycerol and ethylene glycol (EG), which are highly miscible with water, but are poor solvents for hydrophilic PEG and dextran chains. Prior to the friction measurements on polymer brushes, a nanoscale Stribeck curve was obtained on a bare silica surface in the selected aqueous cosolvent mixtures. The Stribeck curve for bare surfaces indicates the existence of a surface-solvating thin film due to the adsorption of hydrated ions, preventing direct silica–silica contact in the boundary-lubrication regime. A clear transition to the hydrodynamic regime is seen at high speeds for solvents with higher viscosities. The polymer brushes, however, show a shear-thinning effect with increasing shear speed and a combined influence of polymer film and solvent viscosity on the measured friction forces. The formation of an interfacial fluid-film is shown to shift the hydrodynamic regime of hydrated brushes to a lower value of Uη. The correlation between the structural configuration and the corresponding frictional properties of the polymer brushes upon changing solvent quality is discussed.

Ionic liquids (ILs) are ionic compounds that are liquid at room temperature. We studied the spontaneous mixing behavior between two ILs, ethylammonium nitrate (EAN) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF₆]), and observed notable phenomena. Experimental studies showed that the interface between the two ILs was unusually long-lived, despite the ILs being miscible with one another. Molecular dynamics (MD) simulations supported these findings and provided insight into the micromixing behavior of the ILs. We found that not only did the ions experience slow diffusion as they mix but also exhibited significant ordering into distinct regions. We suspect that this ordering disrupted concentration gradients in the direction normal to the interface, thus hindering diffusion in this direction and allowing the macroscopic interface to remain for long periods of time. Intermolecular interactions responsible for this behavior included the O–NH interaction between the EAN ions and the carbon chain–carbon chain interactions between the [BMIM]⁺ cations, which associate more strongly in the mixed state than in the pure IL state.

Ionizing radiation, including γ rays and X-rays, are high-energy electromagnetic radiation with diverse applications in nuclear energy, astrophysics, and medicine. In this work, we describe the use of ionizing radiation and cysteine-containing elastin-like polypeptides (C_nELPs, where n = 2 or 12 cysteines in the polypeptide sequence) for the generation of gold nanoparticles. In the presence of C_nELPs, ionizing radiation doses higher than 175 Gy resulted in the formation of maroon-colored gold nanoparticle dispersions, with maximal absorbance at 520 nm, from colorless metal salts. Visible color changes were not observed in any of the control systems, indicating that ionizing radiation, gold salt solution, and C_nELPs were all required for nanoparticle formation. The hydrodynamic diameters of nanoparticles, determined using dynamic light scattering, were in the range of 80–150 nm, while TEM imaging indicated the formation of gold cores 10–20 nm in diameter. Interestingly, C₂ELPs formed 1–2 nm diameter gold nanoparticles in the absence of radiation. Our results describe a facile method of nanoparticle formation in which nanoparticle size can be tailored based on radiation dose and C_nELP type. Further improvements in these polypeptide-based systems can lead to colorimetric detection of ionizing radiation in a variety of applications.

Vesicles are dynamic supramolecular structures with a bilayer membrane consisting of lipids or synthetic amphiphiles enclosing an aqueous compartment. Lipid vesicles have often been considered as mimics for biological cells. In this paper, we present a novel strategy for the preparation of three-dimensional multilayered structures in which vesicles containing amphiphilic β-cyclodextrin are interconnected by proteins using cyclodextrin guests as bifunctional linker molecules. We compared two pairs of adhesion molecules for the immobilization of vesicles: mannose–concanavalin A and biotin–streptavidin. Microcontact printing and thiol–ene click chemistry were used to prepare suitable substrates for the vesicles. Successful immobilization of intact vesicles through the mannose–concanavalin A and biotin–streptavidin motifs was verified by fluorescence microscopy imaging and dynamic light scattering, while the vesicle adlayer was characterized by quartz crystal microbalance with dissipation monitoring. In the case of the biotin–streptavidin motif, up to six layers of intact vesicles could be immobilized in a layer-by-layer fashion using supramolecular interactions. The construction of vesicle multilayers guided by noncovalent vesicle–vesicle junctions can be taken as a minimal model for artificial biological tissue.

Stable biofouling resistance is significant for general filtration requirements, especially for the improvement of membrane lifetime. A systematic group of hyper-brush PEGylated diblock copolymers containing poly(ethylene glycol) methacrylate (PEGMA) and polystyrene (PS) was synthesized using an atom transfer radical polymerization (ATRP) method and varying PEGMA lengths. This study demonstrates the antibiofouling membrane surfaces by self-assembled anchoring PEGylated diblock copolymers of PS-b-PEGMA on the microporous poly(vinylidene fluoride) (PVDF) membrane. Two types of copolymers are used to modify the PVDF surface, one with different PS/PEGMA molar ratios in a range from 0.3 to 2.7 but the same PS molecular weights (MWs, ∼5.7 kDa), the other with different copolymer MWs (∼11.4, 19.9, and 34.1 kDa) but the similar PS/PEGMA ratio (∼1.7 ± 0.2). It was found that the adsorption capacities of diblock copolymers on PVDF membranes decreased as molar mass ratios of PS/PEGMA ratio reduced or molecular weights of PS-b-PEGMA increased because of steric hindrance. The increase in styrene content in copolymer enhanced the stability of polymer anchoring on the membrane, and the increase in PEGMA content enhanced the protein resistance of membranes. The optimum PS/PEGMA ratio was found to be in the range between 1.5 and 2.0 with copolymer MWs above 20.0 kDa for the ultrastable resistance of protein adsorption on the PEGylated PVDF membranes. The PVDF membrane coated with such a diblock copolymer owned excellent biofouling resistance to proteins of BSA and lysozyme as well as bacterium of Escherichia coli and Staphylococcus epidermidis and high stable microfiltration operated with domestic wastewater solution in a membrane bioreactor.

The study of adsorption of glycine and glycylglycine (or diglycine) on a copper surface is an important step for the comprehension of mechanisms that determine the stability of biological functionalizers on metal substrates. These two molecules can be considered as prototypes and essential models to investigate, theoretically and experimentally, the adaptability of flexible short peptide chains to a definite interface. In this work, we have improved and updated earlier molecular dynamics simulations by including reactivity of the various species and the comparison of ab initio calculated C, N, and O core photoelectron chemical shifts with the ones found in previous studies. New diglycine–copper bonding is predicted, and the results of the chemical shift analysis are, in all cases, fully compatible with structural information obtained through experimental measurements. Moreover, we have found that the process of proton transfer, which is fundamental in the dynamics of amino acids and peptides, occurs mainly by intermolecular interaction between the first and second layer of the adsorbate.

Microtubes obtained from the self-assembly of l-diphenylalanine (FF-MTs) were evaluated as potential vehicles for drug delivery. The biological marker Rhodamine B (RhB) was chosen as a model drug and conjugated to the peptide arrays during self-organization in the liquid phase. Microscopy and X-ray studies were performed to provide morphological and structural information. The data revealed that the cargo was distributed either in small aggregates at the hydrophobic surface of the FF-MTs or homogeneously embedded in the structure, presumably anchored at polar sites in the matrix. Raman spectroscopy revealed notable shifts of the characteristic RhB resonance peaks, demonstrating the successful conjugation of the fluorophore and peptide assemblies. In vitro assays were conducted in erythrocytes and fibroblast cells. Interestingly, FF-MTs were found to modulate the release of the load. The release of RhB from the FF-MTs followed first-order kinetics with a steady-state profile, demonstrating the potential of these carriers to deliver drugs at constant rates in the body. Cytotoxicity investigations revealed high cell viability up to concentrations of 5 mg mL^–1, demonstrating the low toxicity of the FF-MTs.

Many biomedical applications benefit from responsive polymer coatings. The properties of poly(dopamine) (PDA) films can be affected by codepositing dopamine (DA) with the temperature-responsive polymer poly(N-isopropylacrylamide) (pNiPAAm). We characterize the film assembly at 24 and 39 °C using DA and aminated or carboxylated pNiPAAm by a quartz crystal microbalance with dissipation monitoring (QCM-D), X-ray photoelectron spectroscopy, UV–vis, ellipsometry, and atomic force microscopy. It was found that pNiPAAm with both types of end groups are incorporated into the films. We then identified a temperature-dependent adsorption behavior of proteins and liposomes to these PDA and pNiPAAm containing coatings by QCM-D and optical microscopy. Finally, a difference in myoblast cell response was found when these cells were allowed to adhere to these coatings. Taken together, these fundamental findings considerably broaden the potential biomedical applications of PDA films due to the added temperature responsiveness.

We have prepared Fe₃O₄ nanocrystal-embedded polyaniline hybrids with well-defined cluster-like morphology through macromolecule-induced self-assembly. These magnetic and electrically conductive composite nanoclusters show flowability at room temperature in the absence of any solvent, which offers great potential in applications such as microwave absorbents and electromagnetic shielding coatings. This macromolecule-induced self-assembly strategy can be readily applied on the fabrication of other ion oxide/conjugated polymer composites to achieve robust multifunctional materials.

Thermo-sensitive gelling systems, like chitosan/polyol-phosphate, are candidates with a high potential for the design of biodegradable drug delivery systems, notably for in situ forming depots. They consist of stable and low viscosity aqueous solutions, liquid at room temperature, which turn into a gel state upon an increase of temperature (e.g., after subcutaneous administration). This technology enables a sustained release of potentially encapsulated active substances. Despite these thermo-gelling solutions being widely studied for the development of parenteral drug delivery systems, most commonly using β-glycerophosphate (β-GP) as gelling agent, the mechanism inducing the gelation and the role of the polyol part in this mechanism has not been clearly elucidated. To investigate the mechanism of the gelation process, comprehensive rheological studies were performed, comparing different chitosan/polyol-phosphate systems varying in the chemical structure of the polyol parts of the gelling agents. As reference, β-GP was compared to glucose-1-phosphate (G1-P) and glucose-6-phosphate (G6-P) and to a polyol-free phosphate salt, Na₂HPO₄, as well. Frequency sweep experiments at different temperatures or different gelling agent concentrations, temperature, and time sweep tests were performed as complementary experimental approaches. The results disclosed significant trends with widespread implications, establishing a relationship between the chemical structure of the polyol part and the macroscopic gelling behavior of the solutions, that is, transition temperature, gelation time, and gel strength. The new results presented in this study show that increasing the size of the polyol part prevents the interactions between the chitosan chains, strongly influencing the gelling process.

Trapping of organic molecules and dyes within nanoporous matrices is of great interest for the potential creation of new materials with tailored features and, thus, different possible applications ranging from nanomedicine to material science. The understanding of the physical basis of entrapment and the spectral properties of the guest molecules within the host matrix is an essential prerequisite for the design and control of the properties of these materials. In this work, we show that a mesoporous silica xerogel can efficiently trap the dye thioflavin T (ThT, a molecule used as a marker of amyloid fibrils and with potential drug benefits), sequestering it from an aqueous solution and producing a highly fluorescent material with a ThT quantum yield 1500 times greater than that of the free molecule. The study of spectroscopical properties of this system and the comparison with fluorescence of an uncharged analogue of ThT give indications about the mechanism responsible for the fluorescence switching-on of ThT molecules during their uptaking into the glass. Diffusion and nanocapillarity are responsible for ThT absorption, whereas electrostatic interaction between positive ThT molecules and negative dangling ≡SiO groups covering the pore surfaces causes the immobilization of ThT molecules inside the pores and the enhancement of its fluorescence, in line with the molecular rotor model proposed for this dye. We also show that entrapment efficiency and kinetics can be tuned by varying the electrostatic properties of the dye and/or the matrix.

This work reports an experimental study of the kinetics and mechanisms of gelation of carbon nanotubes (CNTs)–hyaluronic acid (HA) mixtures. These materials are of great interest as functional biogels for future medical applications and tissue engineering. We show that CNTs can induce the gelation of noncovalently modified HA in water. This gelation is associated with a dynamical arrest of a liquid crystal phase separation, as shown by small-angle light scattering and polarized optical microscopy. This phenomenon is reminiscent of arrested phase separations in other colloidal systems in the presence of attractive interactions. The gelation time is found to strongly vary with the concentrations of both HA and CNTs. Near-infrared photoluminescence reveals that the CNTs remain individualized both in fluid and in gel states. It is concluded that the attractive forces interplay are likely weak depletion interactions and not strong van der Waals interactions which could promote CNT rebundling, as observed in other biopolymer–CNT mixtures. The present results clarify the remarkable efficiency of CNT at inducing the gelation of HA, by considering that CNTs easily phase separate as liquid crystals because of their giant aspect ratio.

A well-known nonsteroidal anti-inflammatory drug (NSAID), namely, naproxen (Np), was conjugated with β-alanine and various combinations of amino alcohols and l-alanine. Quite a few bioconjugates, thus synthesized, were capable of gelling pure water, NaCl solution (0.9 wt %), and phosphate-buffered saline (PBS) (pH 7.4). The hydrogels were characterized by rheology and electron microscopy. Hydrogelation was probed by FT-IR and temperature-variable ¹H NMR studies. Single-crystal X-ray diffraction (SXRD) of a nonhydrogelator and a hydrogelator in the series established a useful structure–property (gelation) correlation. MTT assay of the hydrogelators in the mouse macrophage RAW 264.7 cell line showed excellent biocompatibility. The prostaglandin E₂ (PGE₂) assay of the hydrogelators revealed their anti-inflammatory response, which was comparable to that of the parent NSAID naproxen sodium (Ns).

Honeycomb-structured porous polymer films based on photosensitizer-grafted polystyrene are prepared through the breath figure process. Rose Bengal (RB) photosensitizer is first attached to a well-defined poly(styrene-stat-4-vinylbenzyl chloride) statistical copolymer, synthesized by nitroxide-mediated radical polymerization. The RB grafted poly(styrene-stat-4-vinylbenzyl chloride) (ca. 20 000 g mol^–1 molar mass, 1.2 dispersity) leads to porous polymer films, with a hexagonal pore pattern, while a simple mixture of poly(styrene-stat-4-vinylbenzyl chloride) and the insoluble RB photosensitizer produced unstructured, nonporous films. The RB-grafted honeycomb films, compared with the corresponding nonporous flat films, are more efficient for oxidation of organic molecules via singlet oxygen production at a liquid/solid interface. The oxidations of 1,5-dihydroxynaphthalene to juglone and α-terpinene to ascaridole are followed in ethanol in the presence of both types of films. Oxidation of the organic molecules is a factor 5 greater with honeycomb compared to the nonporous films. This gain is ascribed to two factors: the specific location of the polar photosensitizer at the film interface and the greater exchange surface, as revealed by fluorescence and scanning electron microscopies.

Electrochemical treatment of Au(111) in aqueous H₂SO₄ solution by repetitive application of oxide formation–reduction cycles (OFRC) generates nanopatterned surfaces with long-range order. The pattern development depends on the lower and upper potential limits (E_L, E_U), the number (n) of OFRCs, and the potential scan rate (s). Surface patterning of Au(111) initially (n = 1–2) generates small islands and holes that are one atomic step in height. As n increases to 5, the number of islands decreases and the holes become larger; after n = 10 OFRCs, the islands become inexistent and large, randomly distributed holes are observed. Increase of OFRCs to n = 20 generates surface structures that reside within three atomic layers and resemble phase separation through a spinodal decomposition mechanism. As the number of OFRCs rises to n = 50, a network of interconnected islands and holes emerges; the islands and holes are two-three atomic steps in height, and are located within topmost five monolayers. Further increase of the number of OFRCs to n = 100 creates a network of interconnected trigonal pyramids that are pointed in the same direction. The size of the pyramids depends on the electrolyte composition and the number of OFRCs. In the case of n = 100, the pyramids are 12–25 nm in base length and 0.4–1.6 nm in height in 0.1 M aqueous H₂SO₄, and 20–50 nm in base length and 0.8–1.6 nm in height in 0.1 M aqueous HNO₃. The number of OFRCs and scan rate play an important role in patterning of Au(111), and complete nanopattern development requires a large number of OFRCs and low scan rates.

The ability to observe interactions of drugs with cell membranes is an important area in pharmaceutical research. However, these processes are often difficult to understand due to the dynamic nature of cell membranes. Therefore, artificial systems composed of lipids have been used to study membrane properties and their interaction with drugs. Here, lipid vesicle adsorption, rupture, and formation of planar lipid bilayers induced by various antibiotics (surfactin, azithromycin, gramicidin, melittin and ciprofloxacin) and the detergent dodecyl-b-d-thiomaltoside (DOTM) was studied using reflective interferometric Fourier transform spectroscopy (RIFTS) on an oxidized porous silicon (pSi) surface as a transducer. The pSi transducer surfaces are prepared as thin films of 3 μm thickness with pore dimensions of a few nanometers in diameter by electrochemical etching of crystalline silicon followed by passivation with a thermal oxide layer. Furthermore, the sensitivity of RIFTS was investigated using three different concentrations of surfactin. Complementary techniques including atomic force microscopy, fluorescence recovery after photobleaching, and fluorescence microscopy were used to validate the RIFTS-based method and confirm adsorption and consequent rupture of vesicles to form a phospholipid bilayer upon the addition of antibiotics. The method provides a sensitive and real-time approach to monitor the antibiotic-induced transition of lipid vesicles to phospholipid bilayers.

Selective ion exclusion from charged nanopores in track-etched membranes allows separation of ions with different charges or mobilities. This study examines pressure-driven transport of dissolved ions through track-etched membranes modified by adsorption of poly(styrene sulfonate) (PSS)/protonated poly(allylamine) (PAH) films. For nominal 30 nm pores modified with a single layer of PSS, Br^–/SO₄^2– selectivities are ∼3.4 with SO₄^2– rejections around 85% due to selective electrostatic exclusion of the divalent anion from the negatively charged pore. Corresponding membranes containing an adsorbed PSS/PAH bilayer are positively charged and exhibit average K⁺/Mg²⁺ selectivities >10 at 8 mM ionic strength, and Mg²⁺ rejections are >97.5% at ionic strengths <5 mM. The high rejection of Mg²⁺ compared to SO₄^2– likely results from both a smaller pore size after deposition of the PAH layer and higher surface charge because of Mg²⁺ adsorption. Simultaneous modeling of K⁺ and Mg²⁺ rejections using the nonlinearized Poisson–Boltzmann equation gives an average modified pore diameter of 8.4 ± 2.1 nm, which does not vary significantly with ionic strength. This diameter is smaller than that calculated from hydraulic permeabilities and estimated pore densities, suggesting that narrow regions near the pore entrance control ion transport. In addition to simple electrostatic exclusion, streaming potentials lead to differing rejections of Br^– and acetate in PSS/PAH-modified pores, and of Li⁺ and Cs⁺ in PSS-modified pores. For these cases, electrical migration of ions toward the feed solution results in higher rejection of the more mobile ion.