Download Hi-Res ImageDownload to MS-PowerPointCite This:Acc. Chem. Res. 2017, 50, 5, 1212-1221

Liquefaction of Biopolymers: Solvent-free Liquids and Liquid Crystals from Nucleic Acids and Proteins

Kai Liu^†
,
Chao Ma^§
,
Robert Göstl^*^‡
,
Lei Zhang^§
, and
Andreas Herrmann^*^§

View Author Information

† State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 130022 Changchun, China

§ Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands

‡ DWI−Leibniz Institute for Interactive Materials, Forckenbeckstr. 50, 52056 Aachen, Germany

*E-mail: [email protected]

Cite this: Acc. Chem. Res. 2017, 50, 5, 1212–1221

Publication Date (Web):May 5, 2017

https://doi.org/10.1021/acs.accounts.7b00030

Article Views

2746

Altmetric

Citations

LEARN ABOUT THESE METRICS

Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.

PDF (10 MB)

Get e-Alerts

SUBJECTS:

Get e-Alerts

Abstract

Conspectus

Biomacromolecules, such as nucleic acids, proteins, and virus particles, are persistent molecular entities with dimensions that exceed the range of their intermolecular forces hence undergoing degradation by thermally induced bond-scission upon heating. Consequently, for this type of molecule, the absence of a liquid phase can be regarded as a general phenomenon. However, certain advantageous properties usually associated with the liquid state of matter, such as processability, flowability, or molecular mobility, are highly sought-after features for biomacromolecules in a solvent-free environment. Here, we provide an overview over the design principles and synthetic pathways to obtain solvent-free liquids of biomacromolecular architectures approaching the topic from our own perspective of research. We will highlight the milestones in synthesis, including a recently developed general surfactant complexation method applicable to a large variety of biomacromolecules as well as other synthetic principles granting access to electrostatically complexed proteins and DNA.

These synthetic pathways retain the function and structure of the biomacromolecules even under extreme, nonphysiological conditions at high temperatures in water-free melts challenging the existing paradigm on the role of hydration in structural biology. Under these conditions, the resulting complexes reveal their true potential for previously unthinkable applications. Moreover, these protocols open a pathway toward the assembly of anisotropic architectures, enabling the formation of solvent-free biomacromolecular thermotropic liquid crystals. These ordered biomaterials exhibit vastly different mechanical properties when compared to the individual building blocks. Beyond the preparative aspects, we will shine light on the unique potential applications and technologies resulting from solvent-free biomacromolecular fluids: From charge transport in dehydrated liquids to DNA electrochromism to biocatalysis in the absence of a protein hydration shell. Moreover, solvent-free biological liquids containing viruses can be used as novel storage and process media serving as a formulation technology for the delivery of highly concentrated bioactive compounds. We are confident that this new class of hybrid biomaterials will fuel further studies and applications of biomacromolecules beyond water and other solvents and in a much broader context than just the traditional physiological conditions.

Introduction

ARTICLE SECTIONS

Jump To

Modern manufacturing of chemical products heavily relies on the tailor-making of molecules to combine desirable and discard undesirable material properties. Some of these properties, however, are almost exclusively associated with the molecules’ state of matter. While, for example, porosity and crystallinity are generally attributed to the solid state, molecular mobility and flowability are characteristics mostly associated with liquids. Solvent-free liquids surpass this intrinsic limitation and combine advantageous and even create completely new properties from multiple aggregate states. Exciting examples are solvent-free liquids that enhance the performance of dyes, (1) create permanent liquid porosity, (2) or increase reaction yields by unprecedentedly high concentrations. (3)

Concerning biomacromolecules, the production of solvent-free liquids is a particularly challenging task as the basic requirement for self-organization and activity of DNA, RNA, and proteins is the presence of water. (4, 5) Though biomacromolecular components are of increasing interest for the integration into artificial materials and devices, (6-10) their processability is currently limited to methods primarily involving the aqueous phase due to their insolubility and structural (hence functional) destabilization in organic solvents. Concomitantly, solid state processing of freeze-dried powders obtained from aqueous biomacromolecular solutions suffers from safety issues in storage and manipulation. Consequently, also considering solvent-incompatible high- and low-temperature applications, the investigation of biomacromolecular liquids in a solvent-free environment expands their value beyond the traditional modus operandi of biology. The preparation of solvent-free liquids with high concentrations of intact biomacromolecules will have a significant impact on advancing the design and processing of biologically derived nanostructures and even might replace conventional polymeric ionic liquids (11) in applications requiring biocompatibility or degradability. Their use as injectable depots for drug delivery of highly concentrated bioactive compounds, for example, barrier dressings for wound healing or artificial skin, (12, 13) is also a promising prospect that may spawn development toward flexible, printable bioelectronics where water hampers device performance. Moreover and from a fundamental perspective, biomacromolecular liquids allow insights into the (vastly different) structural stability and functionality of biomacromolecules in the absence of any solvent.

This Account provides insight into the conceptual understanding of the formation of solvent-free biomacromolecular liquids whose popularity has been fast-tracked by the recent finding that they can be prepared conveniently through electrostatic complexation with surfactants containing flexible alkyl tails followed by dehydration. (14-17) We will briefly outline design, preparation, and application of solvent-free liquids ranging from nucleic acids (14-16) to proteins (17-19) to whole viruses (20, 21) that have become accessible employing this simple and general protocol. In addition, this protocol has yielded access to solvent-free liquid crystals (LCs) (21-24) introducing ordering and fluidity by ionic self-assembly while retaining biological function (25) for biocatalysis, (26) bioelectronics, (27, 28) and potentially biomedicine.

Concept and Mechanism of Formation of Biomacromolecular Liquids

ARTICLE SECTIONS

Jump To

Many small molecules exhibit limited intermolecular interaction and hence can exist in all three common physical states of matter, that is, solid, liquid, and gas. However, with increasing molecular weight and presence of functional groups, forces, such as van der Waals (vdW), ionic interactions, or hydrogen bonds, restrict thermal motion limiting the adoption of different physical states in most pressure regimes. (29-31) This is particularly true for biomacromolecules or large biological complexes with sizes on the nanoscale as they strongly interact in the absence of solvent. Additionally, their phase behavior is limited as the size of the biomacromolecular features exceeds the range of the intermolecular force fields. (32) Consequently, once a biopolymer powder obtained by freeze-drying is heated above a critical temperature, the material will not melt but degrade due to thermally induced bond scission. As this is a general feature, until recently biopolymeric properties and functions have almost exclusively been investigated in aqueous solution.

The implicit question arising is how folded biomacromolecules or even larger biopolymer complexes can be transformed to show a richer phase behavior. One way to approach this task is to sterically shield strong intermolecular forces by introduction of a surfactant or polymer surface layer physically separating the individual biomacromolecules. Though this method initially appears similar to solvation, the surfactants or polymers specifically bind via distinct electrostatic interactions forming well-defined hybrid structures.

The surfactants or polymers assemble into a defined corona around the biomacromolecule’s surface and lower the intermolecular interactions twofold: First, they induce repulsion between the biomacromolecule–surfactant hybrids through the entropically unfavorable compression of surfactant or polymer chains. (32) Second, vdW interactions are reduced due to similar electric moments (expressed in similar refractive indices) of the biomacromolecule and the surfactant. (32, 33) Heating these complexes overcomes their solid state positional order increasing volume and allows transition into the liquid state. Additionally to these effects, during the formation of biomacromolecular liquid crystals, the surfactants can also contribute to induce positional order of the included biopolymers. (22, 34)

Design, Preparation, and Application of Biomacromolecular Liquids

ARTICLE SECTIONS

Jump To

Nucleic Acid Liquids and Liquid Crystals

Nucleic acid liquids can be prepared by the complexation of an oligonucleotide with a cationic surfactant. The groups of Thorp and Murray as well as Bourlinos pioneered this method and employed poly(ethylene glycol) (PEG) tail-containing quaternary ammonium surfactants (Figure 1a,b), which are electrostatically complexed in a simple procedure including a final dehydration step. (14, 15) The integrity of the double stranded DNA is verifiable by a variety of methods including Fourier transform infrared (FTIR), UV/vis, and circular dichroism (CD) spectroscopy. Mechanical analysis confirms the DNA’s liquid-like character as the loss modulus G″ is higher than the storage modulus G′.

Figure 1. Surfactants containing PEG tails for solvent-free DNA liquids. (a, b) Cationic quaternary ammonium surfactants. (14, 15) (c) Amine surfactant to complex acidified DNA by proton exchange. (15) (d) Polypyridyl complex of Co decorated with polyether chains as cationic surfactants. (14)

Besides relying on the exchange of the counterions, alternative pathways either make use of direct neutralization of acidified (i.e. protonated) high-molecular-weight DNA (>2000 bp) by tertiary amines (Figure 1c) (15) or employ metal coordinated cationic complexes as surfactants (Figure 1d). (14) Further functionality can be reached by blending hydrophobic molecules, such as the dyes coumarin or rhodamine 6G, into these DNA liquids yielding samples that may find application in DNA-based photonics. (15)

Inspired by previous work on electrostatic self-assembly of nucleic acid, (35-39) we recently found that combining DNA or RNA with cationic surfactants can be exploited for the production of a series of liquid crystalline DNA or RNA fluids (Figure 2). (16, 21) Instead of PEG residues, we employed ammonium surfactants substituted with aliphatic alkyl chains yielding either DNA–surfactant liquids or mesophases. For the analysis of the DNA LCs, polarized optical microscopy (POM) can be used revealing the characteristic focal-conic textures of lamellar structures (Figure 2a,b). Typically, the DNA LCs transition into the disordered liquid state after heating above the clearing temperature (Figure 2c) losing their birefringence (Figure 2d). Long range ordering of the alternatingly intercalating lamellar layer structure can be confirmed by small-angle X-ray scattering (SAXS) measurements, while its topography is visualized directly employing freeze-fracture transmission electron microscopy (FF-TEM). The DNA-surfactant melts are thermally stable, and phase transition temperatures can be adjusted via the surfactant’s alkyl chains (Figure 2e). These DNA thermotropic LCs are formed by virtue of their molecular shape, flexibility, and weak intermolecular interactions. This is in contrast to water-rich DNA LCs, (40-42) in which the amphiphilic character of DNA molecules and the rigidity of Au nanorods stabilize the mesophases.

Figure 2. Solvent-free liquid crystals and liquids of DNA–surfactant complexes. (16) (a) Lamellar structure in the LC phase. (b) POM image of the DNA–surfactant mesophases. (c) Schematic of disordered DNA-surfactant complex in the isotropic liquid phase, and (d) POM image of the isotropic liquid. The scale bar is 100 μm. (e) Phase-transition temperatures of DNA–surfactant complexes from crystalline (Cr) to liquid crystalline (LC) to isotropic liquid. Adapted with permission from ref 16. Copyright 2015 John Wiley & Sons, Inc.

The anhydrous character, negligible volatility, high DNA content, and thermal stability of these DNA liquids render them ideal materials for the incorporation into microelectronic circuits utilizing DNA for both self-assembly and electronic connections. (14, 43) For example, the Co^II-containing DNA liquid (Figure 1d) can be oxidized electrochemically to Co^III while revealing a very low faradaic current as the rigid DNA helices impede transport of the metal surfactant complex to the electrode. Likewise, the electron transfer rate in the Co^II/Co^I couple is also strongly reduced due to the low mobility of the DNA counterion. (43) The introduction of Fe^II into this system allows additional oxidation of the guanine base in the DNA through electrochemically generated Fe^III, (14) as observed in the DNA-Ru(bpy)₃³⁺ system. (44)

Beyond acting as a scaffold, the nucleobases of DNA can be reversibly oxidized in pristine DNA–surfactant fluids giving rise to phase-dependent electrochromism (Figure 3). (28) While in the isotropic phase, the electric field-induced formation of highly colored nucleobase radicals (45, 46) vanishes in seconds (Figure 3a,b), a multiple hours long optical memory is observed in the smectic phase (Figure 3c,d). Cooling the DNA-LC material in the colored state to the crystalline phase extends this memory time (Figure 3e,f) implying that the memory volatility is controllable by changing the phase of the DNA–surfactant fluid.

Figure 3. Phase-dependent electrochromic device based on solvent-free DNA–surfactant complexes. (28) (a, b) Switchable electrochromism in the isotropic liquid phase. (c, d) Optical memory of the liquid crystal as a persistent colored state. (e, f) Cooling the colored state to the crystalline phase further increases the relaxation time. (g, h) The activated device functions as time and temperature indicator. Adapted from ref 28. Licensed under CC BY 2016 Springer Nature.

As the electrochromic switching time in the isotropic phase correlates with the DNA length, the rate of DNA oxidation is presumably limited by the rate of mass transport to the electrode. Concomitantly, the surfactant sublayers may act as insulating barrier preventing electron hopping thus slowing the reduction of the colored radical cations. As the clearing points of these materials can be tuned by employing different surfactant mixtures (Figure 3g,h), the temperature controlled decoloration is prospectively applicable in smart tags for packaging perishable food or medical products.

Protein Liquids and Liquid Crystals

The manufacturing of solvent-free liquids from proteins was pioneered by Mann and co-workers, (17, 18, 25) inspired by previous work on nanoparticle liquids, (47-49) and follows a three-step process (Figure 4). The resulting surfactant complexes melt around 25 °C (Figure 4f) and exhibit a typical water content corresponding to only 6 water molecules per complex. (25) This is drastically fewer than required to cover the solvent-accessible surface (526 H₂O per myoglogin (Mb)), (50) also fewer than the number of site-specific structural water molecules (36 H₂O per Mb) or those required for protein motion and function (60 H₂O per protein). (51-53)

Figure 4. Fabrication of solvent-free protein liquids. (a) General route for the preparation of protein liquids: (17) (i) EDC-initiated coupling of N,N-dimethyl-1,3-propanediamine to carboxylic acid surface residues of proteins; (ii) electrostatic complexation of cationized protein with anionic surfactants forming protein–surfactant hybrid. (b, c) Surfactants electrostatically bound to proteins. (d, e) Electrostatic binding of protein with surfactants. (18) (f) Gravity-induced flow of a solvent-free protein–surfactant liquid. Adapted with permission from ref 17, Copyright 2009 John Wiley & Sons, Inc., and ref 18, Copyright 2010 Macmillan Publishers Ltd.

Additionally to the liquid phase, viscoelastic and smectic LC behavior are also observed, the latter of which can be confirmed by POM and differential scanning calorimetry (DSC). (17) Interestingly, SAXS experiments on the LC phase indicate a lamellar structure with a layer spacing matching the external ferritin diameter. This is an unusual finding as ferritin is a spherical nanoparticle and hence not expected to assemble anisotropically implying that the cationization and subsequent complexation with surfactant may alter its shape to an ellipsoidal complex promoting LC formation. (17)

Conversely, Mb–surfactant liquids possess high structural integrity retaining their α-helical secondary structure with only minor perturbation, which is confirmed by attenuated total reflectance (ATR) FTIR and CD spectroscopy. (18) Binding experiments show that the Mb–surfactant complex’s affinity toward O₂ is comparable to results obtained for deoxy-Mb under physiological conditions underlining that structure and function of Mb are preserved even without solvent. Further study on this complex employing high-resolution synchrotron radiation as well as CD and UV/vis spectroscopy revealed that the surfactant-assisted solvent-free environment stabilizes the protein evidenced by an increase of the half denaturation temperature. (25) This preservation of the folded structure may stem from additional interactions (H-bonds, electrostatic, vdW) within the protein–surfactant complex caused by a decrease of the protein interior’s dielectric constant upon dehydration but also from restriction in translational mobility due to strong molecular crowding. Concomitantly, incoherent neutron scattering on deuterium labeled surfactants showed that the surfactant shell fulfills a similar function as the water hydration layer required for protein chain mobility and activity. (54)

Aside from ferritin and Mb, solvent-free lysozyme-surfactant liquids were prepared employing the three-step procedure. (55) Studying such a complex with synchrotron radiation and CD spectroscopy while exploiting its increased thermal stability allows trapping an otherwise unobservable β-sheet-enriched intermediate unfolding state leading to a greater understanding of this transient analogue in aqueous environment. Molecular dynamics simulations allow a yet deeper insight into the atomistic structure suggesting that the mobility of the surfactant molecules is impaired and thus responsible for the retention and observability of the intermediate unfolding state. (56) In addition, anisotropic glucose oxidase–surfactant complexes can be synthesized exhibiting liquid, LC, and solid phase features while retaining the secondary structure. (57) As the conformational transition temperature of the enzyme correlates with the LC to liquid transition, it is likely that the shape anisotropy of the protein–surfactant building blocks plays a pivotal role in the formation of ordered structures of the complex. Beyond globular proteins, rod-like polypeptides, such as poly(l-lysine) or H-shaped hexapeptides, were transformed into solvent-free liquids and LCs employing lecithin or dodecylbenzenesulfonic acid as surfactants. (23, 24, 58)

Only recently solvent-free liquids and LCs of unfolded polypeptides have been discovered in our laboratory. We produced supercharged polypeptides (SUPs) with the glutamic acid-containing pentapeptide repeat motif (VPGEG)_n by gene multimerization through recursive directional ligation. (59, 60) Expression in Escherichia coli yielded unfolded monodisperse polypeptide chains with a well-defined number of negative charges (Figure 5). (19, 21) These SUPs were then complexed with cationic surfactants generating anhydrous, thermally stable SUP-surfactant complexes after dehydration that exhibit non-Newtonian (smectic LC) and Newtonian (isotropic liquid) fluid behaviors. Mechanical analysis indicated that viscoelastic properties dominate in the LC phase while Newtonian behavior prevails in the isotropic liquid state. Notably, the elastic moduli of the SUP–surfactant LCs are in the megapascal-range uncovering their extraordinary elasticity (Figure 5). Moreover and in contrast to the sole components, that is, SUPs as well as cationic surfactants, the mechanical properties are recoverable even after multiple phase transitions indicating their origin in the spatially segregated lamellar structure. Variation of surfactant alkyl chain length and molecular weight of the SUP backbone fine-tunes the mechanical response in the LC phase.

Figure 5. Solvent-free fluids based on SUPs. (19) (a) Negatively charged SUPs combined with cationic surfactants. (b) POM image of SUP-surfactant smectic LC. (c) Lamellar bilayer structure of the LC phase. (d) Rheological investigation of the solvent-free SUP-surfactant fluids. Adapted with permission from ref 19. Copyright 2015 John Wiley & Sons, Inc.

The Mb liquids containing folded polypeptide backbones exhibit remarkable thermal stability and retain their biological function even at high concentrations. Therefore, they are well-suited for bioelectrochemical applications. Consequently, Mann and co-workers deposited Mb onto a highly oriented pyrolytic graphite (HOPG) electrode inserting Pt (counter) and Ag (pseudoreference) wires into the electrolyte-free, anhydrous protein droplet (Figure 6a,b). (61) Cyclic voltammetry in combination with diffuse reflectance UV/vis, SAXS, and rheology measurements reveal that charge transport occurs via electron hopping between heme cofactors. Since charge transport is considerably lower than that reported for Mb dispersed in hydrated polyelectrolytes, (62) LiPF₆ was added. (26) From this a field-effect transistor was constructed granting control over the redox state of the heme by tuning the gate potential difference between working and reference electrodes (Figure 6c). Two temperature-dependent charge transport mechanisms can be identified, one stemming from electron hopping between heme redox centers and the other from ion movement within the protein liquid (Figure 6d).

Figure 6. Electrochemical investigation of solvent-free Mb–surfactant liquids. (27) (a) Molecular model of the Mb–surfactant complex. (b) Diagram of the three electrode cell configuration. (c) Structure of electrochemical FET used for conductivity measurements. (d) Conductivity measurements for the Mb–surfactant melt blended with LiPF₆ (red) and pristine Mb–surfactant melt (black). Adapted with permission from ref 27. Copyright 2015 John Wiley & Sons, Inc.

Enzyme catalysis in solvent-free protein liquids is an exciting prospect yet a considerable challenge as water or other solvent molecules regulate mass transfer of substrates, nucleophilicity, and proton transfer and dictate catalytically active conformations. Nevertheless, Mann and co-workers fabricated solvent-free lipase–surfactant liquids from the mesophile Rhizomucor miehei (RML) and thermophile Thermomyces lanuginosus (TML). With both liquids, hydrolysis of fatty acid esters was demonstrated (Figure 7) and by synchrotron experiments as well as CD and ATR-FTIR spectroscopy the conservation of the lipases’ native states was shown. (26) Esterase activity was monitored hydrolyzing model substrates p-nitrophenyl palmitate (pNPPal) and p-nitrophenyl butyrate (pNPB) (Figure 7a,b). UV/vis spectroscopy reveals that lipase activity increases with temperature (Figure 7c,d) yet reaction rates are much lower compared to catalysis in water at physiological temperatures due to the high intrinsic viscosity and hence unfavorable mass transport properties. However, enzyme activity in the solvent-free liquid state was maintained up to 150 °C allowing the investigation of biocatalysis at extreme conditions possibly providing new directions for industrial catalysis.

Figure 7. Hydrolysis of fatty acid esters in solvent-free lipase–surfactant liquids. (26) (a) 3D model showing the Ser144-His257-Asp203 catalytic triad of the lipase and the helical lid motif. (b) Two-step mechanism for lipase-based hydrolysis of pNPPal and pNPB. Initial rate of *reactions* of pNPB (c) and pNPPal (d) within solvent-free lipase–surfactant liquids as a function of temperature (RML black; TML red). Adapted by permission from Macmillan Publishers Ltd.: ref 26, copyright 2014.

Virus Liquids and Liquid Crystals

Besides solvent-free liquids based on nucleic acids or protein building blocks, liquids from bacteriophages and plant viruses are of particular interest for the development of storage and transport media as well as nonaqueous virus based nanotechnology. Cowpea mosaic virus (CPMV) or tobacco mosaic virus liquids, for example, can be engineered via a procedure comparable to that used for protein liquids (Figure 8a) and characterized by DSC and ATR-FTIR spectroscopy. (20) These methods reveal that dehydration and melting neither impede the secondary structure of the coat proteins nor remove the genetic material from the virus interior. The virus melt can directly be applied on plant leaves as the surfactant chains do not influence host processing of the viral RNA (Figure 8b,c). CPMV-surfactant complexes are soluble in a variety of low-boiling point organic solvents rendering aerosol delivery a viable option.

Figure 8. Solvent-free virus–surfactant fluids. (a) General route toward CPMV melt. (20) Optical images of symptomatic *Vigna unguiculata* plants after infection with aqueous dispersions of wild-type CPMV (b) and solvent-free CPMV–surfactant droplet (c). Pairs of leaves either treated or untreated are shown. (d, e) Bacteriophages used for solvent-free virus liquid crystals and liquids. (21) Magnifications of FF-TEM images of the phage-surfactant LCs are shown. Adapted with permission from ref 20. Copyright 2012 John Wiley & Sons, Inc.

Moreover, our group recently prepared solvent-free liquids of even larger and anisotropic, monodisperse rod-like M13 bacteriophages. (21) The negatively charged major coat protein of M13 allows complexing with mixed aliphatic ammonium surfactants yielding solvent-free liquids and LCs that can be characterized employing POM and SAXS measurements. The observed long-range periodicity in the LC phase is confirmed by FF-TEM studies revealing individual phages globally aligned along a preferred direction (Figure 8d,e).

Conclusions and Future Directions

ARTICLE SECTIONS

Jump To

In this Account, we introduced the concept behind biomacromolecular solvent-free liquids and liquid crystals and highlighted the most important synthetic pathways toward these materials. Moreover, we gave an outlook of the potential applications of this new class of biomacromolecular architectures. The wrapping of nucleic acids, polypeptides, proteins, and multiprotein complexes in a well-defined shell by complexing a surfactant electrostatically with the biomacromolecular component yields thermally stable, easy-to-process liquids with dimensions from the nanometer to the micrometer range. Phase transitions and order of these fluidic materials can be controlled over a broad temperature range granting access to functional liquid crystalline phases. While DNA melts provide a hydrophobic environment in the absence of water allowing the fabrication of DNA-based electrochemical devices, for example, control over the volatility of an optoelectronic state, protein liquids can retain the natural form of the enzyme enabling catalytic applications far outside the range of physiological conditions. Concomitantly, virus liquids prove worthwhile as concentrated, temperature resilient nanocarriers to infect biological targets.

The presented findings show that structure and function of most biomacromolecules can be retained during complexation with surfactants and subsequent transformation to the anhydrous state unleashing formerly unthinkable properties, such as extremely stiff liquid crystals employing noncovalently assembled supercharged polypeptides or biologically inspired charge transporting media relying on tunable myoglobin conductivity. These milestones in synthesis and material fabrication certainly will fuel further efforts employing the presented protocols for the preparation of solvent-free biofluids based on an even wider range of biomacromolecules and offer great opportunities to fabricate stimuli-responsive biological soft materials, thus providing new directions in technological applications including biosensing, biocatalysis, biomedicine, and the construction of bioelectronic devices.

Author Information

ARTICLE SECTIONS

Jump To

Corresponding Authors
- Robert Göstl - DWI−Leibniz Institute for Interactive Materials, Forckenbeckstr. 50, 52056 Aachen, Germany; Email: [email protected]
- Andreas Herrmann - Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands; http://orcid.org/0000-0002-8886-0894; Email: [email protected]
Authors
- Kai Liu - State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 130022 Changchun, China
- Chao Ma - Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands
- Lei Zhang - Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands
Funding
This research was supported by the European Union (European Research Council Advanced Grant and STREP project MICREAGENTS), the Netherlands Organization for Scientific Research (NWO-Vici, NWO-Echo), the Zernike Institute for Advanced Materials, the start-up supports from Changchun Institute of Applied Chemistry, and the National Thousand Talents Program for Distinguished Young Scholars.
Notes
The authors declare no competing financial interest.

Biographies

ARTICLE SECTIONS

Jump To

Kai Liu

Download MS PowerPoint Slide

Kai Liu studied chemistry at the University of Chinese Academy of Sciences and gained his master’s degree in inorganic chemistry in 2010. He then pursued Ph.D. and postdoctoral studies at the University of Groningen in Netherlands under the supervision of Prof. Andreas Herrmann. From March of 2017, he has been working as a principle investigator at Changchun Institute of Applied Chemistry of Chinese Academy of Sciences and heading a laboratory with research on functional biomaterials.

Chao Ma

Download MS PowerPoint Slide

Chao Ma received his master’s degree in chemical biology in 2013 from the China Pharmaceutical University in Nanjing. He then joined the group of Prof. Andreas Herrmann at the University of Groningen to earn his Ph.D. degree. His research is dedicated to genetically engineered supercharged polypeptides and proteins.

Robert Göstl

Download MS PowerPoint Slide

Robert Göstl studied chemistry at the Humboldt-Universität zu Berlin, Germany, and has been researching organic photoswitches in the group of Prof. Stefan Hecht since 2009 where he obtained his diploma in 2011 and his doctoral degree in 2014. After his postdoctoral stay in the group of Prof. Rint Sijbesma at the Eindhoven University of Technology in the Netherlands, he took up a position as project leader working on mechanoresponsive (bio)materials at DWI–Leibniz Institute for Interactive Materials.

Lei Zhang

Download MS PowerPoint Slide

Lei Zhang received her master’s degree in chemistry in 2010 from the University of Science and Technology of China in Hefei. In 2012, she started her Ph.D. studies in the group of Prof. Andreas Herrmann at the University of Groningen. Her research deals with peptide sledding on DNA.

Andreas Herrmann

Download MS PowerPoint Slide

Andreas Herrmann holds a chair for Polymer Chemistry and Bioengineering at the Zernike Institute for Advanced Materials, University of Groningen, The Netherlands. He studied chemistry at the University of Mainz (Germany). In 2000, he completed his graduate studies on dendritic macromolecules at the Max Planck Institute for Polymer Research in Mainz. After a short stay as a management consultant at Roland Berger, he returned to academia and worked as a postdoctoral researcher at the Swiss Federal Institute of Technology in Zurich on protein engineering. From 2004 to 2006, he was head of a junior research group at the Max Planck Institute for Polymer Research. Since 2007, he is full professor at the University of Groningen and his group is interested in nanobiomaterials with a focus on nucleic acid hybrids and supercharged polypeptides.

References

ARTICLE SECTIONS

Jump To

This article references 62 other publications.

1
Babu, S. S.; Hollamby, M. J.; Aimi, J.; Ozawa, H.; Saeki, A.; Seki, S.; Kobayashi, K.; Hagiwara, K.; Yoshizawa, M.; Möhwald, H.; Nakanishi, T. Nonvolatile Liquid Anthracenes for Facile Full-Colour Luminescence Tuning at Single Blue-Light Excitation Nat. Commun. 2013, 4, 1969 DOI: 10.1038/ncomms2969
[Crossref], [PubMed], [CAS], Google Scholar
1
Nonvolatile liquid anthracenes for facile full-colour luminescence tuning at single blue-light excitation
Babu Sukumaran Santhosh; Hollamby Martin J; Aimi Junko; Ozawa Hiroaki; Saeki Akinori; Seki Shu; Kobayashi Kenji; Hagiwara Keita; Yoshizawa Michito; Mohwald Helmuth; Nakanishi Takashi
Nature communications (2013), 4 (), 1969 ISSN:.
Nonvolatile room-temperature luminescent molecular liquids are a new generation of organic soft materials. They possess high stability, versatile optical properties, solvent-free fluid behaviour and can effectively accommodate dopant dye molecules. Here we introduce an approach to optimize anthracene-based liquid materials, focussing on enhanced stability, fluorescence quantum yield, colour tunability and processability, with a view to flexible electronic applications. Enveloping the anthracene core in low-viscosity branched aliphatic chains results in stable, nonvolatile, emissive liquid materials. Up to 96% efficient energy-transfer-assisted tunable emission is achieved by doping a minute amount of acceptor dye in the solvent-free state. Furthermore, we use a thermoresponsive dopant to impart thermally controllable luminescence colours. The introduced strategy leading to diverse luminescence colours at a single blue-light excitation can be an innovative replacement for currently used luminescent materials, providing useful continuous emissive layers in developing foldable devices.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC3snps1Cjsg%253D%253D&md5=a412f3040a22122303ee7c2a77199033
2
Giri, N.; Del Pópolo, M. G.; Melaugh, G.; Greenaway, R. L.; Rätzke, K.; Koschine, T.; Pison, L.; Gomes, M. F. C.; Cooper, A. I.; James, S. L. Liquids with Permanent Porosity Nature 2015, 527, 216– 220 DOI: 10.1038/nature16072
[Crossref], [PubMed], [CAS], Google Scholar
2
Liquids with permanent porosity
Giri, Nicola; Del Popolo, Mario G.; Melaugh, Gavin; Greenaway, Rebecca L.; Ratzke, Klaus; Koschine, Tonjes; Pison, Laure; Gomes, Margarida F. Costa; Cooper, Andrew I.; James, Stuart L.
Nature (London, United Kingdom) (2015), 527 (7577), 216-220CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
Porous solids such as zeolites and metal-org. frameworks are useful in mol. sepn. and in catalysis, but their solid nature can impose limitations. For example, liq. solvents, rather than porous solids, are the most mature technol. for post-combustion capture of carbon dioxide because liq. circulation systems are more easily retrofitted to existing plants. Solid porous adsorbents offer major benefits, such as lower energy penalties in adsorption-desorption cycles, but they are difficult to implement in conventional flow processes. Materials that combine the properties of fluidity and permanent porosity could therefore offer technol. advantages, but permanent porosity is not assocd. with conventional liqs. Here we report free-flowing liqs. whose bulk properties are detd. by their permanent porosity. To achieve this, we designed cage mols. that provide a well-defined pore space and that are highly sol. in solvents whose mols. are too large to enter the pores. The concn. of unoccupied cages can thus be around 500 times greater than in other mol. solns. that contain cavities, resulting in a marked change in bulk properties, such as an eightfold increase in the soly. of methane gas. Our results provide the basis for development of a new class of functional porous materials for chem. processes, and we present a one-step, multigram scale-up route for highly sol. 'scrambled' porous cages prepd. from a mixt. of com. available reagents. The unifying design principle for these materials is the avoidance of functional groups that can penetrate into the mol. cage cavities.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXitVSiu7nN&md5=6334a97707c4112dff7b44d5b72b001d
3
Ogoshi, T.; Aoki, T.; Shiga, R.; Iizuka, R.; Ueda, S.; Demachi, K.; Yamafuji, D.; Kayama, H.; Yamagishi, T. Cyclic Host Liquids for Facile and High-Yield Synthesis of [2]Rotaxanes J. Am. Chem. Soc. 2012, 134, 20322– 20325 DOI: 10.1021/ja310757p
[ACS Full Text ], [CAS], Google Scholar
3
Cyclic Host Liquids for Facile and High-Yield Synthesis of [2]Rotaxanes
Ogoshi, Tomoki; Aoki, Takamichi; Shiga, Ryohei; Iizuka, Ryo; Ueda, Seita; Demachi, Kazuki; Yamafuji, Daiki; Kayama, Hitoshi; Yamagishi, Tada-aki
Journal of the American Chemical Society (2012), 134 (50), 20322-20325CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
We developed "cyclic host liqs. (CHLs)" as a new type of solvent. The CHLs are a nonvolatile liq. over a wide temp. range, are biocompatible and recyclable, have high thermal stability, and are miscible with many org. solvents. Compared with typical complexation systems, the CHL system is extremely efficient for maintaining host-guest complexation because an addnl. solvent is not required. Based on the efficient host-guest complexation in the CHL system, we demonstrated synthesis of [2]rotaxanes in pillar[5]arene-based CHL. High yields were obtained for [2]rotaxanes capped by cationization (yield 91%) and Huisgen reaction (yield 88%) between the axle and the stopper components in the CHL system, while the assocn. consts. between the axles and wheels were quite low (10-15 M-1) in CDCl3. The CHL system provides a new powerful approach for synthesis of mech. interlocked mols. (MIMs) even with unfavorable statistical combinations of host-guest complexes.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhslOmu7nE&md5=d8b4a0aee89178a184bb94f672b1c4c5
4
Bellissent-Funel, M.-C.; Hassanali, A.; Havenith, M.; Henchman, R.; Pohl, P.; Sterpone, F.; van der Spoel, D.; Xu, Y.; Garcia, A. E. Water Determines the Structure and Dynamics of Proteins Chem. Rev. 2016, 116, 7673– 7697 DOI: 10.1021/acs.chemrev.5b00664
[ACS Full Text ], [CAS], Google Scholar
4
Water Determines the Structure and Dynamics of Proteins
Bellissent-Funel, Marie-Claire; Hassanali, Ali; Havenith, Martina; Henchman, Richard; Pohl, Peter; Sterpone, Fabio; van der Spoel, David; Xu, Yao; Garcia, Angel E.
Chemical Reviews (Washington, DC, United States) (2016), 116 (13), 7673-7697CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
Water is an essential participant in the stability, structure, dynamics, and function of proteins and other biomols. Thermodynamically, changes in the aq. environment affect the stability of biomols. Structurally, water participates chem. in the catalytic function of proteins and nucleic acids and phys. in the collapse of the protein chain during folding through hydrophobic collapse and mediates binding through the hydrogen bond in complex formation. Water is a partner that slaves the dynamics of proteins, and water interaction with proteins affect their dynamics. Here we provide a review of the exptl. and computational advances over the past decade in understanding the role of water in the dynamics, structure, and function of proteins. We focus on the combination of X-ray and neutron crystallog., NMR, terahertz spectroscopy, mass spectroscopy, thermodn., and computer simulations to reveal how water assist proteins in their function. The recent advances in computer simulations and the enhanced sensitivity of exptl. tools promise major advances in the understanding of protein dynamics, and water surely will be a protagonist.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XnvFeqsrw%253D&md5=365764ba66b0f0b2f94d1d401ee4d691
5
Bloomfield, V. A. DNA Condensation Curr. Opin. Struct. Biol. 1996, 6, 334– 341 DOI: 10.1016/S0959-440X(96)80052-2
[Crossref], [PubMed], [CAS], Google Scholar
5
DNA condensation
Bloomfield, Victor A.
Current Opinion in Structural Biology (1996), 6 (3), 334-341CODEN: COSBEF; ISSN:0959-440X. (Current Biology)
A review with 73 refs. is presented on recent progress in our understanding of DNA condensation. Topics discussed include the observation of the collapse of single DNA mols., greater insights into the intermol. forces driving condensation, the recognition of helix-structure perturbation in condensed DNA, and the increasing recognition of the likely biol. consequences of condensation. DNA condensed with cationic liposomes is an efficient agent for the transfection of eukaryotic cells, with considerable potential interest for gene therapy.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK28XjvFSgsL4%253D&md5=36b884b9e5f4af3e42f7f6d1d4f24a0e
6
Kim, W.; Conticello, V. P. Protein Engineering Methods for Investigation of Structure-Function Relationships in Protein-Based Elastomeric Materials Polym. Rev. 2007, 47, 93– 119 DOI: 10.1080/15583720601109586
[Crossref], Google Scholar
There is no corresponding record for this reference.
7
Kyle, S.; Aggeli, A.; Ingham, E.; McPherson, M. J. Production of Self-Assembling Biomaterials for Tissue Engineering Trends Biotechnol. 2009, 27, 423– 433 DOI: 10.1016/j.tibtech.2009.04.002
[Crossref], [PubMed], [CAS], Google Scholar
7
Production of self-assembling biomaterials for tissue engineering
Kyle, Stuart; Aggeli, Amalia; Ingham, Eileen; McPherson, Michael J.
Trends in Biotechnology (2009), 27 (7), 423-433CODEN: TRBIDM; ISSN:0167-7799. (Elsevier B.V.)
A review. Self-assembling peptide-based biomaterials are being developed for use as 3D tissue engineering scaffolds and for therapeutic drug-release applications. Chem. synthesis provides custom-made peptides in small quantities, but prodn. approaches based upon transgenic organisms might be more cost-effective for large-scale peptide prodn. Long lead times for developing appropriate animal clones or plant lines and potential neg. public opinion are obstacles to these routes. Microbes, particularly safe organisms used in the food industry, offer a more rapid route to the large-scale prodn. of recombinant self-assembling biomaterials. In this review, recent advances and challenges in the recombinant prodn. of collagen, elastin and de novo designed self-assembling peptides are discussed.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXnslymsbc%253D&md5=9321e7bd50eea7bdcacb4049bf13b439
8
Gordiichuk, P. I.; Wetzelaer, G.-J. A. H.; Rimmerman, D.; Gruszka, A.; de Vries, J. W.; Saller, M.; Gautier, D. A.; Catarci, S.; Pesce, D.; Richter, S.; Blom, P. W. M.; Herrmann, A. Solid-State Biophotovoltaic Cells Containing Photosystem I Adv. Mater. 2014, 26, 4863– 4869 DOI: 10.1002/adma.201401135
[Crossref], [PubMed], [CAS], Google Scholar
8
Solid-state biophotovoltaic cells containing Photosystem I
Gordiichuk, Pavlo I.; Wetzelaer, Gert-Jan A. H.; Rimmerman, Dolev; Gruszka, Agnieszka; Willem de Vries, Jan X.; Saller, Manfred; Gautier, Daniel A.; Catarci, Stefano; Pesce, Diego; Richter, Shachar; Blom, Paul W. M.; Herrmann, Andreas
Advanced Materials (Weinheim, Germany) (2014), 26 (28), 4863-4869CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
Processes occurring during photosynthesis, such as dynamic self-repair, light harvesting and quantum effects can be integrated into man-made photovoltaic devices. One of the most frequently used photoactive building blocks for that purpose is the multiprotein complex photosystem I (PSI). Biophotovoltaic devices similar to DSSCs were fabricated by self-assembly of PSI on 3D nanostructured semiconductor electrodes using a liq. electrolyte as redox mediator. Here, we introduce the implementation of PSI in org. electronic devices that combine the ease of processing of org. semiconductors with the biophotovoltaic activity of PSI.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXos1CjtL0%253D&md5=2ca7ed4b6f064ba7a6480e00fc62f364
9
Kwiat, M.; Elnathan, R.; Kwak, M.; de Vries, J. W.; Pevzner, A.; Engel, Y.; Burstein, L.; Khatchtourints, A.; Lichtenstein, A.; Flaxer, E.; Herrmann, A.; Patolsky, F. Non-Covalent Monolayer-Piercing Anchoring of Lipophilic Nucleic Acids: Preparation, Characterization, and Sensing Applications J. Am. Chem. Soc. 2012, 134, 280– 292 DOI: 10.1021/ja206639d
[ACS Full Text ], [CAS], Google Scholar
9
Non-covalent Monolayer-Piercing Anchoring of Lipophilic Nucleic Acids: Preparation, Characterization, and Sensing Applications
Kwiat, Moria; Elnathan, Roey; Kwak, Minseok; de Vries, Jan Willem; Pevzner, Alexander; Engel, Yoni; Burstein, Larisa; Khatchtourints, Artium; Lichtenstein, Amir; Flaxer, Eli; Herrmann, Andreas; Patolsky, Fernando
Journal of the American Chemical Society (2012), 134 (1), 280-292CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
Functional interfaces of biomols. and inorg. substrates like semiconductor materials are of utmost importance for the development of highly sensitive biosensors and microarray technol. However, there is still a lot of room for improving the techniques for immobilization of biomols., in particular nucleic acids and proteins. Conventional anchoring strategies rely on attaching biomacromols. via complementary functional groups, appropriate bifunctional linker mols., or non-covalent immobilization via electrostatic interactions. In this work, we demonstrate a facile, new, and general method for the reversible non-covalent attachment of amphiphilic DNA probes contg. hydrophobic units attached to the nucleobases (lipid-DNA) onto SAM-modified gold electrodes, silicon semiconductor surfaces, and glass substrates. We show the anchoring of well-defined amts. of lipid-DNA onto the surface by insertion of their lipid tails into the hydrophobic monolayer structure. The surface coverage of DNA mols. can be conveniently controlled by modulating the initial concn. and incubation time. Further control over the DNA layer is afforded by the addnl. external stimulus of temp. Heating the DNA-modified surfaces at temps. >80 °C leads to the release of the lipid-DNA structures from the surface without harming the integrity of the hydrophobic SAMs. These supramol. DNA layers can be further tuned by anchoring onto a mixed SAM contg. hydrophobic mols. of different lengths, rather than a homogeneous SAM. Immobilization of lipid-DNA on such SAMs has revealed that the surface d. of DNA probes is highly dependent on the compn. of the surface layer and the structure of the lipid-DNA. The formation of the lipid-DNA sensing layers was monitored and characterized by numerous techniques including XPS, quartz crystal microbalance, ellipsometry, contact angle measurements, at. force microscopy, and confocal fluorescence imaging. Finally, this new DNA modification strategy was applied for the sensing of target DNAs using silicon-nanowire field-effect transistor device arrays, showing a high degree of specificity toward the complementary DNA target, as well as single-base mismatch selectivity.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhsVOlt7zF&md5=3bed556154faf58f826dd10e32e57e3f
10
Kwak, M.; Gao, J.; Prusty, D. K.; Musser, A. J.; Markov, V. A.; Tombros, N.; Stuart, M. C. A.; Browne, W. R.; Boekema, E. J.; ten Brinke, G.; Jonkman, H. T.; van Wees, B. J.; Loi, M. A.; Herrmann, A. DNA Block Copolymer Doing It All: From Selection to Self-Assembly of Semiconducting Carbon Nanotubes Angew. Chem., Int. Ed. 2011, 50, 3206– 3210 DOI: 10.1002/anie.201007098
[Crossref], [CAS], Google Scholar
10
DNA Block Copolymer Doing It All: From Selection to Self-Assembly of Semiconducting Carbon Nanotubes
Kwak, Minseok; Gao, Jia; Prusty, Deepak K.; Musser, Andrew J.; Markov, Vladimir A.; Tombros, Nikolaos; Stuart, Marc C. A.; Browne, Wesley R.; Boekema, Egbert J.; ten Brinke, Gerrit; Jonkman, Harry T.; van Wees, Bart J.; Loi, Maria A.; Herrmann, Andreas
Angewandte Chemie, International Edition (2011), 50 (14), 3206-3210, S3206/1-S3206/32CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
The article presents a strait-forward soln. to many of the key concerns that face SWNT technol. (nondestructive dispersion of individual nanotubes, enrichment of semiconducting species, and precise supramol. addressability) by using amphiphilic DNA block copolymers (DBCs).
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXjsFyqs7g%253D&md5=4a245f8f385b141ab03d65386321bf40
11
Yuan, J.; Mecerreyes, D.; Antonietti, M. Poly(ionic Liquid)s: An Update Prog. Polym. Sci. 2013, 38, 1009– 1036 DOI: 10.1016/j.progpolymsci.2013.04.002
[Crossref], [CAS], Google Scholar
11
Poly(ionic liquid)s: An update
Yuan, Jiayin; Mecerreyes, David; Antonietti, Markus
Progress in Polymer Science (2013), 38 (7), 1009-1036CODEN: PRPSB8; ISSN:0079-6700. (Elsevier Ltd.)
This review presents a literature survey of recent work on poly(ionic liq.)s or polymd. ionic liqs. (PILs), a class of polyelectrolytes that has attracted rapidly increasing interest over the past few years. The review begins with a short explanation of the interconnection as well as the intrinsic differences between PILs and ionic liqs. Recently reported PIL homopolymers with new chem. structures and synthetic trends are introduced as a complement to the overall PIL synthesis schemes reported previously. In addn., block copolymers and colloidal particles of PILs are described, followed by a discussion of the limitations of PILs due to structural instability under certain conditions and the efforts to understand PIL physics. Examples of recent applications of PILs across a multitude of fields, such as thermoresponsive materials, carbon materials, catalysis, porous polymers, sepn. and absorption materials, and energy harvesting/generation as well as several biol. applications are described in detail.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXmvFymtbY%253D&md5=a348dd9a3b02001d968a37c919426f0e
12
Wang, R.; Li, J.; Chen, W.; Xu, T.; Yun, S.; Xu, Z.; Xu, Z.; Sato, T.; Chi, B.; Xu, H. A Biomimetic Mussel-Inspired ε-Poly-l-lysine Hydrogel with Robust Tissue-Anchor and Anti-Infection Capacity Adv. Funct. Mater. 2017, 27, 1604894 DOI: 10.1002/adfm.201604894
[Crossref], Google Scholar
There is no corresponding record for this reference.
13
Benight, S. J.; Tok, J. B. H.; Bao, Z.; Wang, C. Stretchable and Self-healing Polymers and Devices for Electronic Skin Prog. Polym. Sci. 2013, 38, 1961– 1977 DOI: 10.1016/j.progpolymsci.2013.08.001
[Crossref], [CAS], Google Scholar
13
Stretchable and self-healing polymers and devices for electronic skin
Benight, Stephanie J.; Wang, Chao; Tok, Jeffrey B. H.; Bao, Zhenan
Progress in Polymer Science (2013), 38 (12), 1961-1977CODEN: PRPSB8; ISSN:0079-6700. (Elsevier Ltd.)
A review. This review covers some of the most recent advances in stretchable and self-healing polymers and devices for Electronic skin (E-skin) applications. Applications for both stretchable and self-healing materials include, but are not limited to, electronics, displays, energy, the environment, and medicine. While the majority of org. materials can generally be rendered flexible, such materials are not stretchable, which is a key mech. property necessary to realize applications of E-skin for prosthetics, artificial intelligence, systems for robotics, personal health monitoring, biocompatibility, and communication devices. In our effort to survey materials utilized in various components of an electronic device, we report herein recent advances in stretchable and self-healing conductors, semiconductors, and substrates. We highlight some key technologies recently developed in stretchable org.-based sensors, solar cells, light-emitting diodes, and self-healing electronic devices.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhtlShsrbM&md5=e50109f11999be38fed58025cbfffb06
14
Leone, A. M.; Weatherly, S. C.; Williams, M. E.; Thorp, H. H.; Murray, R. W. An Ionic Liquid Form of DNA: Redox-Active Molten Salts of Nucleic Acids J. Am. Chem. Soc. 2001, 123, 218– 222 DOI: 10.1021/ja003332c
[ACS Full Text ], [CAS], Google Scholar
14
An Ionic Liquid Form of DNA: Redox-Active Molten Salts of Nucleic Acids
Leone, Anthony M.; Weatherly, Stephanie C.; Williams, Mary Elizabeth; Thorp, H. Holden; Murray, Royce W.
Journal of the American Chemical Society (2001), 123 (2), 218-222CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
Ionic liqs. are described that contain duplex DNA as the anion and polyether-decorated transition metal complexes based on M(MePEG-bpy)32+ as (M = Fe, Co; MePEG-bpy = 4,4'-(CH3(OCH2CH2)7OCO)2-2,2'-bipyridine). When the undiluted liq. DNA-or molten salt-is interrogated electrochem. by a microelectrode, the molten salts exhibit cyclic voltammograms due to the phys. diffusion (DPHYS) of the polyether-transition metal complex. When M = Co(II), the cyclic voltammogram of the melt shows an oxidative wave due to the Co(III/II) couple at E1/2 = 0.40 V (vs. Ag/AgCl) and a DPHYS of 6 × 10-12 cm2/s, which is significantly lower than that for Co(MePEG-bpy)3(ClO4)2 (DPHYS = 2.6 × 10-10 cm2/s) due to greater viscosity provoked by the DNA polymer. When a 1:1 mixt. is made of the Co(MePEG-bpy)3·DNA and Fe(MePEG-bpy)3(ClO4)2 melts, two redox waves are obsd. The 1st is due to the Co(III/II) couple, and the 2nd is a catalytic wave due to oxidn. of guanine in DNA by electrogenerated Fe(III) in the undiluted melt. Independent expts. show that the Fe(III) form of the complex selectively oxidizes guanine in duplex DNA. These DNA molten salts constitute a new class of materials whose properties can be controlled by nucleic acid sequence and that can be interrogated in undiluted form on microelectrode arrays.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXovVCisrs%253D&md5=3c6ed25ed2f9af71116cb1131b561d54
15
Bourlinos, A. B.; Ray Chowdhury, S.; Herrera, R.; Jiang, D. D.; Zhang, Q.; Archer, L. A.; Giannelis, E. P. Functionalized Nanostructures with Liquid-Like Behavior: Expanding the Gallery of Available Nanostructures Adv. Funct. Mater. 2005, 15, 1285– 1290 DOI: 10.1002/adfm.200500076
[Crossref], [CAS], Google Scholar
15
Functionalized nanostructures with liquid-like behavior: Expanding the gallery of available nanostructures
Bourlinos, Athanasios B.; Chowdhury, Subhendu Ray; Herrera, Rafael; Jiang, David D.; Zhang, Qiang; Archer, Lynden A.; Giannelis, Emmanuel P.
Advanced Functional Materials (2005), 15 (8), 1285-1290CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
Recently, the authors have developed a novel family of functionalized nanostructures that exhibit liq.-like behavior in the absence of solvents and preserve their nanostructure in the liq. state. The gallery of nanostructures developed so far includes functionalized SiO2 and magnetic Fe oxide nanoparticles, layer-like organosilicate nanoparticles, polyoxometalate clusters, and org.-inorg. hybrid networks. In an effort to demonstrate the wider applicability of this concept and to provide a deeper insight into this class of materials, the present work cites addnl. paradigms of functionalized nanostructures with similar behavior as above. In one case, surface functionalization of anatase nanoparticles (TiO2, an inorg. nanostructure) with a quaternary ammonium organosilane leads to ionically modified nanoparticles that, when electrostatically combined with a poly(ethylene glycol) (PEG)-tailed sulfonate anion, exhibit liq.-like behavior in the absence of solvents. In a different but quite interesting case of a bionanostructure, ion-exchange functionalization of a DNA oligonucleotide with a PEG-tailed quaternary ammonium cation leads to an easily separable liq. deriv. with attractive features. These examples show the versatility of this concept over a range of nanostructures.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXoslGms78%253D&md5=8aa63387e37005ebb049267b94291a35
16
Liu, K.; Shuai, M.; Chen, D.; Tuchband, M.; Gerasimov, J. Y.; Su, J.; Liu, Q.; Zajaczkowski, W.; Pisula, W.; Müllen, K.; Clark, N. A.; Herrmann, A. Solvent-free Liquid Crystals and Liquids from DNA Chem. - Eur. J. 2015, 21, 4898– 4903 DOI: 10.1002/chem.201500159
[Crossref], [PubMed], [CAS], Google Scholar
16
Solvent-free Liquid Crystals and Liquids from DNA
Liu, Kai; Shuai, Min; Chen, Dong; Tuchband, Michael; Gerasimov, Jennifer Y.; Su, Juanjuan; Liu, Qing; Zajaczkowski, Wojciech; Pisula, Wojciech; Muellen, Klaus; Clark, Noel A.; Herrmann, Andreas
Chemistry - A European Journal (2015), 21 (13), 4898-4903CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
As DNA exhibits persistent structures with dimensions that exceed the range of their intermol. forces, solid-state DNA undergoes thermal degrdn. at elevated temps. Therefore, the realization of solvent-free DNA fluids, including liq. crystals and liqs., still remains a significant challenge. To address this intriguing issue, we demonstrate that combining DNA with suitable cationic surfactants, followed by dehydration, can be a simple generic scheme for producing these solvent-free DNA fluid systems. In the anhyd. smectic liq. cryst. phase, DNA sublayers are intercalated between aliph. hydrocarbon sublayers. The lengths of the DNA and surfactant are found to be extremely important in tuning the phys. properties of the fluids. Stable liq.-cryst. and liq. phases are obtained in the -20 °C to 200 °C temp. range without thermal degrdn. of the DNA. Thus, a new type of DNA-based soft biomaterial has been achieved, which will promote the study and application of DNA in a much broader context.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXmsl2qs7w%253D&md5=fc971ffbf240d228432b19b819e608a6
17
Perriman, A. W.; Cölfen, H.; Hughes, R. W.; Barrie, C. L.; Mann, S. Solvent-Free Protein Liquids and Liquid Crystals Angew. Chem., Int. Ed. 2009, 48, 6242– 6246 DOI: 10.1002/anie.200903100
[Crossref], [CAS], Google Scholar
17
Solvent-Free Protein Liquids and Liquid Crystals
Perriman, Adam W.; Coelfen, Helmut; Hughes, Roy W.; Barrie, Claire L.; Mann, Stephen
Angewandte Chemie, International Edition (2009), 48 (34), 6242-6246, S6242/1-S6242/14CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
Herein, we report, to our knowledge, the first example of a solvent-free liq. protein. Specifically, we report the prepn. and properties of a protein melt based on a stoichiometric ferritin-polymer nanoscale construct with surface modifications that extend the range of intermol. interactions to a length scale that is commensurate with fluidity in the absence of water. Moreover, we show that these spherically shaped nanoconstructs undergo anisotropic ordering during melting at 30° to produce a viscoelastic protein liq. that exhibits thermotropic liq.-cryst. behavior, and which subsequently transforms to a Newtonian fluid at temps. above 40° and is stable up to a temp. of 405°. The method, which utilizes the site-specificity of surface amino acid residues and high degree of uniformity in ferritin mol. architecture to produce discrete single-component ferritin-polymer constructs, should be readily accessible to exploitation as a facile route to solvent-free liq. proteins and enzymes in general.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXpvFyhur4%253D&md5=7409c2035810bb79e89ce19e5bd62487
18
Perriman, A. W.; Brogan, A. P. S.; Cölfen, H.; Tsoureas, N.; Owen, G. R.; Mann, S. Reversible Dioxygen Binding in Solvent-Free Liquid Myoglobin Nat. Chem. 2010, 2, 622– 626 DOI: 10.1038/nchem.700
[Crossref], [PubMed], [CAS], Google Scholar
18
Reversible dioxygen binding in solvent-free liquid myoglobin
Perriman, Adam W.; Brogan, Alex P. S.; Coelfen, Helmut; Tsoureas, Nikolaos; Owen, Gareth R.; Mann, Stephen
Nature Chemistry (2010), 2 (8), 622-626CODEN: NCAHBB; ISSN:1755-4330. (Nature Publishing Group)
The ensemble of forces that stabilize protein structure and facilitate biol. function are intimately linked with the ubiquitous aq. environment of living systems. As a consequence, biomol. activity is highly sensitive to the interplay of solvent-protein interactions, and deviation from the native conditions, for example by exposure to increased thermal energy or severe dehydration, results in denaturation and subsequent loss of function. Although certain enzymes can be extd. into non-aq. solvents without significant loss of activity, there are no known examples of solvent-less (molten) liqs. of functional metalloproteins. Here we describe the synthesis and properties of room-temp. solvent-free myoglobin liqs. with near-native structure and reversible dioxygen binding ability equiv. to the haem protein under physiol. conditions. The realization of room-temp. solvent-free myoglobin liqs. with retained function presents novel challenges to existing theories on the role of solvent mols. in structural biol., and should offer new opportunities in protein-based nanoscience and bionanotechnol.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXpt1aksbo%253D&md5=d4dd63a877cdfd44954db927e5740d56
19
Liu, K.; Pesce, D.; Ma, C.; Tuchband, M.; Shuai, M.; Chen, D.; Su, J.; Liu, Q.; Gerasimov, J. Y.; Kolbe, A.; Zajaczkowski, W.; Pisula, W.; Müllen, K.; Clark, N. A.; Herrmann, A. Solvent-Free Liquid Crystals and Liquids Based on Genetically Engineered Supercharged Polypeptides with High Elasticity Adv. Mater. 2015, 27, 2459– 2465 DOI: 10.1002/adma.201405182
[Crossref], [PubMed], [CAS], Google Scholar
19
Solvent-Free Liquid Crystals and Liquids Based on Genetically Engineered Supercharged Polypeptides with High Elasticity
Liu, Kai; Pesce, Diego; Ma, Chao; Tuchband, Michael; Shuai, Min; Chen, Dong; Su, Juanjuan; Liu, Qing; Gerasimov, Jennifer Y.; Kolbe, Anke; Zajaczkowski, Wojciech; Pisula, Wojciech; Muellen, Klaus; Clark, Noel A.; Herrmann, Andreas
Advanced Materials (Weinheim, Germany) (2015), 27 (15), 2459-2465CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
We developed a series of solvent free GFP functionalized elastin-like protein liq. crystals and liqs. by electrostatic complexation of SUPs with surfactants contg. flexible alkyl chains.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXkvVSiu7c%253D&md5=e1da0277c0a322fd59ce336448aedb7e
20
Patil, A. J.; McGrath, N.; Barclay, J. E.; Evans, D. J.; Cölfen, H.; Manners, I.; Perriman, A. W.; Mann, S. Liquid Viruses by Nanoscale Engineering of Capsid Surfaces Adv. Mater. 2012, 24, 4557– 4563 DOI: 10.1002/adma.201201032
[Crossref], Google Scholar
There is no corresponding record for this reference.
21
Liu, K.; Chen, D.; Marcozzi, A.; Zheng, L.; Su, J.; Pesce, D.; Zajaczkowski, W.; Kolbe, A.; Pisula, W.; Müllen, K.; Clark, N. A.; Herrmann, A. Thermotropic Liquid Crystals from Biomacromolecules Proc. Natl. Acad. Sci. U. S. A. 2014, 111, 18596– 18600 DOI: 10.1073/pnas.1421257111
[Crossref], [PubMed], [CAS], Google Scholar
21
Thermotropic liquid crystals from biomacromolecules
Liu, Kai; Chen, Dong; Marcozzi, Alessio; Zheng, Lifei; Su, Juanjuan; Pesce, Diego; Zajaczkowski, Wojciech; Kolbe, Anke; Pisula, Wojciech; Muellen, Klaus; Clark, Noel A.; Herrmann, Andreas
Proceedings of the National Academy of Sciences of the United States of America (2014), 111 (52), 18596-18600CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
Complexation of biomacromols. (e.g., nucleic acids, proteins, or viruses) with surfactants contg. flexible alkyl tails, followed by dehydration, is shown to be a simple generic method for the prodn. of thermotropic liq. crystals. The anhyd. smectic phases that result exhibit biomacromol. sublayers intercalated between aliph. hydrocarbon sublayers at or near room temp. Both this and low transition temps. to other phases enable the study and application of thermotropic liq. crystal phase behavior without thermal degrdn. of the biomol. components.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXitFCrt7rO&md5=5ad169c3e83a7d867a26f0502dd7217d
22
Faul, C. F. J.; Antonietti, M. Ionic Self-Assembly: Facile Synthesis of Supramolecular Materials Adv. Mater. 2003, 15, 673– 683 DOI: 10.1002/adma.200300379
[Crossref], [CAS], Google Scholar
22
Ionic self-assembly: Facile synthesis of supramolecular materials
Faul, Charl F. J.; Antonietti, Markus
Advanced Materials (Weinheim, Germany) (2003), 15 (9), 673-683CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
A review. The technique of ionic self-assembly, i.e., the coupling of structurally different building blocks by electrostatic interactions, a powerful tool to create new material nanostructures and chem. objects, is reviewed with 110 refs. The excellent availability of the starting products (charged tectonic units) and the simplicity of synthesis, by neat addn. and cooperative stoichiometric pptn. with high purity, allow the recombinatorial synthesis of a whole range of functional materials and hybrids with interesting and versatile functions. Diverse combinations between polyelectrolytes, surfactants, inorg. clusters, and extended rigid org. scaffolds are discussed in detail, and the underlying principles of nanostructure formation are illustrated.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXjvFOku7o%253D&md5=36e682555777a250cf508d9f35837821
23
Wenzel, A.; Antonietti, M. Superstructures of Lipid Bilayers by Complexation with Helical Biopolymers Adv. Mater. 1997, 9, 487– 490 DOI: 10.1002/adma.19970090607
[Crossref], Google Scholar
There is no corresponding record for this reference.
24
General, S.; Antonietti, M. Supramolecular Organization of Oligopeptides, through Complexation with Surfactants Angew. Chem., Int. Ed. 2002, 41, 2957– 2960 DOI: 10.1002/1521-3773(20020816)41:16<2957::AID-ANIE2957>3.0.CO;2-F
[Crossref], Google Scholar
There is no corresponding record for this reference.
25
Brogan, A. P. S.; Siligardi, G.; Hussain, R.; Perriman, A. W.; Mann, S. Hyper-Thermal Stability and Unprecedented Re-Folding of Solvent-Free Liquid Myoglobin Chem. Sci. 2012, 3, 1839– 1846 DOI: 10.1039/c2sc20143g
[Crossref], [CAS], Google Scholar
25
Hyper-thermal stability and unprecedented re-folding of solvent-free liquid myoglobin
Brogan, Alex P. S.; Siligardi, Giuliano; Hussain, Rohanah; Perriman, Adam W.; Mann, Stephen
Chemical Science (2012), 3 (6), 1839-1846CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
Isolating solvent effects by studying proteins in a liq. phase devoid of solvent has not been previously possible because freeze-dried protein solids do not melt but thermally degrade. Herein we circumvent this problem by modifying the interactions between myoglobin mols. via a polymer-surfactant coronal layer to produce a solvent-free liq. phase that is thermally stable over a wide temp. range. Using high-resoln. synchrotron radiation CD and UV-Vis spectroscopies the authors det. the temp.-dependent structure and re-folding behavior of cationized myoglobin under solvent-free conditions, and show that dehydration and subsequent melting of the nanoconstruct has no significant effect on the protein secondary structure at room temp. Significantly, the solvent-free liq. myoglobin mols. exhibit hyper-thermophilic behavior and can be reversibly re-folded by cooling from 155 °C. We attribute the abnormally high thermal stability and persistence of protein folding to entropic contributions assocd. with macromol. crowding and confinement, and propose that re-folding in the absence of a solvent shell is facilitated by the configurational flexibility and mol. interactivity of the polymer surfactant coronal layer.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xnt12qs7s%253D&md5=00d62a628b2267e6cd7ef3f428e56af7
26
Brogan, A. P. S.; Sharma, K. P.; Perriman, A. W.; Mann, S. Enzyme Activity in Liquid Lipase Melts as a Step towards Solvent-Free Biology at 150 °C Nat. Commun. 2014, 5, 5058 DOI: 10.1038/ncomms6058
[Crossref], [PubMed], [CAS], Google Scholar
26
Enzyme activity in liquid lipase melts as a step towards solvent-free biology at 150 °C
Brogan, Alex P. S.; Sharma, Kamendra P.; Perriman, Adam W.; Mann, Stephen
Nature Communications (2014), 5 (), 5058CODEN: NCAOBW; ISSN:2041-1723. (Nature Publishing Group)
Water mols. play a no. of crit. roles in enzyme catalysis, including mass transfer of substrates and products, nucleophilicity and proton transfer at the active site, and solvent shell-mediated dynamics for accessing catalytically competent conformations. The pervasiveness of water in enzymolysis therefore raises the question concerning whether biocatalysis can be undertaken in the absence of a protein hydration shell. Lipase-mediated catalysis has been undertaken with reagent-based solvents and lyophilized powders, but there are no examples of molecularly dispersed enzymes that catalyze reactions at sub-solvation levels within solvent-free melts. Here we describe the synthesis, properties and enzyme activity of self-contained reactive biofluids based on solvent-free melts of lipase-polymer surfactant nanoconjugates. Desiccated substrates in liq. (p-nitrophenyl butyrate) or solid (p-nitrophenyl palmitate) form can be mixed or solubilized, resp., into the enzyme biofluids, and hydrolyzed in the solvent-free state. Significantly, the efficiency of product formation increases as the temp. is raised to 150 °C.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXksVCitrs%253D&md5=843ed216df21037c70e57d5b0082f4c6
27
Sharma, K. P.; Risbridger, T.; Bradley, K.; Perriman, A. W.; Fermin, D. J.; Mann, S. High-Temperature Electrochemistry of a Solvent-Free Myoglobin Melt ChemElectroChem 2015, 2, 976– 981 DOI: 10.1002/celc.201500094
[Crossref], [CAS], Google Scholar
27
High-Temperature Electrochemistry of a Solvent-Free Myoglobin Melt
Sharma, Kamendra P.; Risbridger, Thomas; Bradley, Kieren; Perriman, Adam W.; Fermin, David J.; Mann, Stephen
ChemElectroChem (2015), 2 (7), 976-981CODEN: CHEMRA; ISSN:2196-0216. (Wiley-VCH Verlag GmbH & Co. KGaA)
The electrochem. responses from a hybrid biofluid comprising lithium hexafluorophosphate (LiPF6) dispersed in a solvent-free myoglobin melt are investigated over an extreme temp. range (30-150°C). Incorporation of LiPF6 resulted in an approx. 20-fold increase in the cond. of the biofluid across the entire temp. range. A polaron-type mechanism involving electron hopping from heme-to-heme centers of myoglobin, accompanied by extrinsic Li counter-ion movement, is proposed for the charge-transport kinetics in the solvent-free melt. Significantly, the redox signature of the heme prosthetic group varied systematically and reversibly with temp., which was consistent with hyperthermophilic unfolding/refolding of the protein structure.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtFCjsbzK&md5=ed325f1247b818528aef352037487665
28
Liu, K.; Varghese, J.; Gerasimov, J. Y.; Polyakov, A. O.; Shuai, M.; Su, J.; Chen, D.; Zajaczkowski, W.; Marcozzi, A.; Pisula, W.; Noheda, B.; Palstra, T. T. M.; Clark, N. A.; Herrmann, A. Controlling the Volatility of the Written Optical State in Electrochromic DNA Liquid Crystals Nat. Commun. 2016, 7, 11476 DOI: 10.1038/ncomms11476
[Crossref], [PubMed], [CAS], Google Scholar
28
Controlling the volatility of the written optical state in electrochromic DNA liquid crystals
Liu, Kai; Varghese, Justin; Gerasimov, Jennifer Y.; Polyakov, Alexey O.; Shuai, Min; Su, Juanjuan; Chen, Dong; Zajaczkowski, Wojciech; Marcozzi, Alessio; Pisula, Wojciech; Noheda, Beatriz; Palstra, Thomas T. M.; Clark, Noel A.; Herrmann, Andreas
Nature Communications (2016), 7 (), 11476CODEN: NCAOBW; ISSN:2041-1723. (Nature Publishing Group)
Liq. crystals are widely used in displays for portable electronic information display. To broaden their scope for other applications like smart windows and tags, new material properties such as polarizer-free operation and tunable memory of a written state become important. Here, we describe an anhyd. nanoDNA-surfactant thermotropic liq. crystal system, which exhibits distinctive elec. controlled optical absorption, and temp.-dependent memory. In the liq. crystal isotropic phase, elec. field-induced coloration and bleaching have a switching time of seconds. Upon transition to the smectic liq. crystal phase, optical memory of the written state is obsd. for many hours without applied voltage. The reorientation of the DNA-surfactant lamellar layers plays an important role in preventing color decay. Thereby, the volatility of optoelectronic state can be controlled simply by changing the phase of the material. This research may pave the way for developing a new generation of DNA-based, phase-modulated, photoelectronic devices.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XnslWktL4%253D&md5=e6a1c65c6ef7a1f61d4d776a94b6e2f1
29
Doye, J. P. K.; Wales, D. J. The Effect of the Range of the Potential on the Structure and Stability of Simple Liquids: From Clusters to Bulk, from Sodium to C-60 J. Phys. B: At., Mol. Opt. Phys. 1996, 29, 4859– 4894 DOI: 10.1088/0953-4075/29/21/002
[Crossref], [CAS], Google Scholar
29
The effect of the range of the potential on the structure and stability of simple liquids: from clusters to bulk, from sodium to C60
Doye, Jonathan P. K.; Wales, David J.
Journal of Physics B: Atomic, Molecular and Optical Physics (1996), 29 (21), 4859-4894CODEN: JPAPEH; ISSN:0953-4075. (Institute of Physics Publishing)
A review with 103 refs. For systems with sufficiently short-ranged interparticle forces, such as some colloidal systems and perhaps C60, the liq. phase can be thermodynamically unstable. By analyzing the effect of the range of the interat. forces on the multidimensional potential energy surfaces of bulk material and clusters, a microscopic view of this phenomenon is provided. Structural anal. of the min. on the potential energy surface provides evidence for the polytetrahedral character of the liq. phase, and allows us to examine the evolution of the phase-like forms of clusters to the bulk limit. We find that essentially bulk-like liq. structure can develop in clusters with as few as 55 atoms. The effect of the range of the potential on the thermodn. is illustrated by a series of simulations of 55-atom clusters. For small clusters bound by long-ranged potentials, the lowest energy min. has an amorphous structure typical of the liq.-like state. This suggests an explanation for the transition from electronic to geometric magic nos. obsd. in the mass spectra of sodium clusters.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXitVWmsA%253D%253D&md5=043ea300336e37b2072a6fbdb0dd28ab
30
Min, Y.; Akbulut, M.; Kristiansen, K.; Golan, Y.; Israelachvili, J. The Role of Interparticle and External Forces in Nanoparticle Assembly Nat. Mater. 2008, 7, 527– 538 DOI: 10.1038/nmat2206
[Crossref], [PubMed], [CAS], Google Scholar
30
The role of interparticle and external forces in nanoparticle assembly
Min, Younjin; Akbulut, Mustafa; Kristiansen, Kai; Golan, Yuval; Israelachvili, Jacob
Nature Materials (2008), 7 (7), 527-538CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
A review. The past 20 years have witnessed simultaneous multidisciplinary explosions in exptl. techniques for synthesizing new materials, measuring and manipulating nanoscale structures, understanding biol. processes at the nanoscale, and carrying out large-scale computations of many-atom and complex macromol. systems. These advances have led to the new disciplines of nanoscience and nanoengineering. For reasons that are discussed here, most nanoparticles do not 'self-assemble' into their thermodynamically lowest energy state, and require an input of energy or external forces to 'direct' them into particular structures or assemblies. We discuss why and how a combination of self- and directed-assembly processes, involving interparticle and externally applied forces, can be applied to produce desired nanostructured materials.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXnslKqsrc%253D&md5=53d6916315dccf43b9d72be033f6453a
31
Hagen, M. H. J.; Meijer, E. J.; Mooij, G. C. a. M.; Frenkel, D.; Lekkerkerker, H. N. W. Does C60 Have a Liquid Phase? Nature 1993, 365, 425– 426 DOI: 10.1038/365425a0
[Crossref], [CAS], Google Scholar
31
Does fullerene C60 have a liquid phase?
Hagen, M. H. J.; Meijer, E. J.; Mooij, G. C. A. M.; Frenkel, D.; Lekkerkerker, H. N. W.
Nature (London, United Kingdom) (1993), 365 (6445), 425-6CODEN: NATUAS; ISSN:0028-0836.
Results are presented which suggest that C60 has no liq. phase. The phase diagram was mapped out using computer simulations in which the C60 mols. are represented by spheres interacting via Lennard-Jones potentials summed over all 60 C atoms. The sublimation line passes above the metastable liq.-vapor coexistence curve. By drawing an analogy with the aggregation of colloidal particles, solid C60 formed by nucleation from the vapor phase will probably be amorphous rather than cryst.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3sXmsFKqtr4%253D&md5=d290ac7d28b2a01d52ed77fa6679d3cc
32
Perriman, A. W.; Mann, S. Liquid Proteins—A New Frontier for Biomolecule-Based Nanoscience ACS Nano 2011, 5, 6085– 6091 DOI: 10.1021/nn202290g
[ACS Full Text ], Google Scholar
There is no corresponding record for this reference.
33
Bishop, K. J. M.; Wilmer, C. E.; Soh, S.; Grzybowski, B. A. Nanoscale Forces and Their Uses in Self-Assembly Small 2009, 5, 1600– 1630 DOI: 10.1002/smll.200900358
[Crossref], [PubMed], [CAS], Google Scholar
33
Nanoscale forces and their uses in self-assembly
Bishop, Kyle J. M.; Wilmer, Christopher E.; Soh, Siowling; Grzybowski, Bartosz A.
Small (2009), 5 (14), 1600-1630CODEN: SMALBC; ISSN:1613-6810. (Wiley-VCH Verlag GmbH & Co. KGaA)
A review. The ability to assemble nanoscopic components into larger structures and materials depends crucially on the ability to understand in quant. detail and subsequently "engineer" the interparticle interactions. This Review provides a crit. examn. of the various interparticle forces (van der Waals, electrostatic, magnetic, mol., and entropic) that can be used in nanoscale self-assembly. For each type of interaction, the magnitude and the length scale are discussed, as well as the scaling with particle size and interparticle distance. In all cases, the discussion emphasizes characteristics unique to the nanoscale. These theor. considerations are accompanied by examples of recent exptl. systems, in which specific interaction types were used to drive nanoscopic self-assembly. Overall, this Review aims to provide a comprehensive yet easily accessible resource of nanoscale-specific interparticle forces that can be implemented in models or simulations of self-assembly processes at this scale.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXpsV2ltLg%253D&md5=6bf8d9f5c31d0769c351c72fd6d13099
34
Faul, C. F. J. Ionic Self-Assembly for Functional Hierarchical Nanostructured Materials Acc. Chem. Res. 2014, 47, 3428– 3438 DOI: 10.1021/ar500162a
[ACS Full Text ], [CAS], Google Scholar
34
Ionic Self-Assembly for Functional Hierarchical Nanostructured Materials
Faul, Charl F. J.
Accounts of Chemical Research (2014), 47 (12), 3428-3438CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
A review. The challenge of constructing soft functional materials over multiple length scales can be addressed by a no. of different routes based on the principles of self-assembly, with the judicious use of various noncovalent interactions providing the tools to control such self-assembly processes. It is within the context of this challenge that we have extensively explored the use of an important approach for materials construction over the past decade: exploiting electrostatic interactions in our ionic self-assembly (ISA) method. In this approach, cooperative assembly of carefully chosen charged surfactants and oppositely charged building blocks (or tectons) provides a facile noncovalent route for the rational design and prodn. of functional nanostructured materials. Generally, our research efforts have developed with an initial focus on establishing rules for the construction of novel noncovalent liq.-cryst. (LC) materials. We found that the use of double-tailed surfactant species (esp. branched double-tailed surfactants) led to the facile formation of thermotropic (and, in certain cases, lyotropic) phases, as demonstrated by extensive temp.-dependent X-ray and light microscopy investigations. From this core area of activity, research expanded to cover issues beyond simple construction of anisotropic materials, turning to the challenge of inclusion and exploitation of switchable functionality. The use of photoactive azobenzene-contg. ISA materials afforded opportunities to exploit both photo-orientation and surface relief grating formation. The prepn. of these anisotropic LC materials was of interest, as the aim was the facile prodn. of disposable and low-cost optical components for display applications and data storage. However, the prohibitive cost of the photo-orientation processes hampered further exploitation of these materials. We also expanded our activities to explore ISA of biol. relevant tectons, specifically deoxyguanosine monophosphate. This approach proved, in combination with block copolymer (BCP) self-assembly, very fruitful for the construction of complex and hierarchical functional materials across multiple length scales. Mol. frustration and incommensurability, which played a major role in structure formation in combination with nucleotide assembly, have now become important tools to tune supramol. structure formation. These concepts, i.e., the use of BCP assembly and incommensurability, in combination with metal-contg. polymeric materials, have provided access to novel supramol. morphologies and, more importantly, design rules to prep. such constructs. These design rules are now also being applied to the assembly of electroactive oligo(aniline)-based materials for the prepn. of highly ordered functional soft materials, and present an opportunity for materials development for applications in energy storage. In this Account, we therefore discuss investigations into (i) the inclusion and prepn. of supramol. photoactive and electroactive materials; (ii) the exploitation and control over multiple noncovalent interactions to fine-tune function, internal structure, and long-range order and (iii) exploration of construction over multiple length scales by combination of ISA with well-known BCP self-assembly. Combination of ISA with tuning of vol. fractions, mutual compatibility, and mol. frustration now provides a versatile tool kit to construct complex and hierarchical functional materials in a facile noncovalent way. A direct challenge for future ISA activities would certainly be the construction of functional mesoscale objects. However, within a broader scientific context, the challenge would be to exploit this powerful assembly tool for application in areas of research with societal impact, for example, energy storage and generation. The hope is that this Account will provide a platform for such future research activities and opportunities.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsFWjsbbN&md5=04fb1a815df13d4049a7b0e305e15a11
35
Radler, J. O.; Salditt, T.; Safinya, C. R.; Koltover, I. Structure of DNA-cationic Liposome Complexes: DNA Intercalation In Multilamellar Membranes in Distinct Interhelical Packing Regimes Science 1997, 275, 810– 814 DOI: 10.1126/science.275.5301.810
[Crossref], [PubMed], [CAS], Google Scholar
35
Structure of DNA-cationic liposome complexes: DNA intercalation in multilamellar membranes in distinct interhelical packing regimes
Radler J O; Koltover I; Salditt T; Safinya C R
Science (New York, N.Y.) (1997), 275 (5301), 810-4 ISSN:0036-8075.
Cationic liposomes complexed with DNA (CL-DNA) are promising synthetically based nonviral carriers of DNA vectors for gene therapy. The solution structure of CL-DNA complexes was probed on length scales from subnanometer to micrometer by synchrotron x-ray diffraction and optical microscopy. The addition of either linear lambda-phage or plasmid DNA to CLs resulted in an unexpected topological transition from liposomes to optically birefringent liquid-crystalline condensed globules. X-ray diffraction of the globules revealed a novel multilamellar structure with alternating lipid bilayer and DNA monolayers. The lambda-DNA chains form a one-dimensional lattice with distinct interhelical packing regimes. Remarkably, in the isoelectric point regime, the lambda-DNA interaxial spacing expands between 24.5 and 57.1 angstroms upon lipid dilution and is indicative of a long-range electrostatic-induced repulsion that is possibly enhanced by chain undulations.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADyaK2s7msFOlsw%253D%253D&md5=9f24e0a90b0ce561d0b164d1fb0bab71
36
Dias, R.; Mel'nikov, S.; Lindman, B.; Miguel, M. G. DNA Phase Behavior in the Presence of Oppositely Charged Surfactants Langmuir 2000, 16, 9577– 9583 DOI: 10.1021/la000640f
[ACS Full Text ], [CAS], Google Scholar
36
DNA phase behavior in the presence of oppositely charged surfactants
Dias, Rita; Mel'nikov, Sergey; Lindman, Bjoern; Miguel, Maria G.
Langmuir (2000), 16 (24), 9577-9583CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
The interaction between DNA and alkyltrimethylammonium bromides of various chain lengths has been investigated. It is known that these systems phase sep. with the formation of a ppt.; this important feature allows, for example, purifn. of nucleic acids. Phase maps were drawn for the aq. systems illustrating the associative phase sepn. The boundary of the 2-phase region for the dil. part of the phase diagram was evaluated by turbidimetry, in both the absence and presence of salt. The extension of the ppt. region increases strongly with the surfactant alkyl chain length, and no redissoln. with an excess of surfactant was obsd. The addn. of NaBr led to novel interesting findings. The phase diagram studies were correlated with the single mol. conformational behavior of the same systems as studied for very dild. solns. by fluorescence microscopy. DNA exhibits a discrete phase transition in the presence of cationic surfactants from coils to globules. Results demonstrate that the coil-globule coexistence interval is narrow for CTAB and becomes wider for the shorter-chained surfactant. The findings for flexible polyions of lower charge d. differ qual. from that found for DNA. For the first, large amts. of surfactant have to be added before phase sepn. occurs, and the change in the polyion extension is gradual, indicating an essentially uniform distribution of surfactant aggregates among the different polyions. For DNA, the very low values of surfactant concn. at which phase sepn. starts demonstrate a different binding interaction; as binding to a polyion starts, further binding is facilitated, and one DNA mol. is satd. before binding starts at another.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXnslSht78%253D&md5=04e97af6a5f9fb7e2182fa769feafe99
37
Neumann, T.; Gajria, S.; Tirrell, M.; Jaeger, L. Reversible Structural Switching of a DNA–DDAB Film J. Am. Chem. Soc. 2009, 131, 3440– 3441 DOI: 10.1021/ja809349m
[ACS Full Text ], Google Scholar
There is no corresponding record for this reference.
38
Liu, K.; Zheng, L.; Liu, Q.; de Vries, J. W.; Gerasimov, J. Y.; Herrmann, A. Nucleic Acid Chemistry in the Organic Phase: From Functionalized Oligonucleotides to DNA Side Chain Polymers J. Am. Chem. Soc. 2014, 136, 14255– 14262 DOI: 10.1021/ja5080486
[ACS Full Text ], [CAS], Google Scholar
38
Nucleic Acid Chemistry in the Organic Phase: From Functionalized Oligonucleotides to DNA Side Chain Polymers
Liu, Kai; Zheng, Lifei; Liu, Qing; de Vries, Jan Willem; Gerasimov, Jennifer Y.; Herrmann, Andreas
Journal of the American Chemical Society (2014), 136 (40), 14255-14262CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
DNA-incorporating hydrophobic moieties can be synthesized by either solid-phase or soln.-phase coupling. On a solid support the DNA is protected, and hydrophobic units are usually attached employing phosphoramidite chem. involving a DNA synthesizer. On the other hand, soln. coupling in aq. medium results in low yields due to the solvent incompatibility of DNA and hydrophobic compds. Hence, the development of a general coupling method for producing amphiphilic DNA conjugates with high yield in soln. remains a major challenge. Here, we report an org.-phase coupling strategy for nucleic acid modification and polymn. by introducing a hydrophobic DNA-surfactant complex as a reactive scaffold. A remarkable range of amphiphile-DNA structures (DNA-pyrene, DNA-triphenylphosphine, DNA-hydrocarbon, and DNA block copolymers) and a series of new brush-type DNA side-chain homopolymers with high DNA grafting d. are produced efficiently. We believe that this method is an important breakthrough in developing a generalized approach to synthesizing functional DNA mols. for self-assembly and related technol. applications.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhs1CnsrnJ&md5=9b1d1f81232b941dc831be813d991a13
39
Chen, W.; Gerasimov, J. Y.; Zhao, P.; Liu, K.; Herrmann, A. High-Density Noncovalent Functionalization of DNA by Electrostatic Interactions J. Am. Chem. Soc. 2015, 137, 12884– 12889 DOI: 10.1021/jacs.5b05432
[ACS Full Text ], [CAS], Google Scholar
39
High-Density Noncovalent Functionalization of DNA by Electrostatic Interactions
Chen, Wei; Gerasimov, Jennifer Y.; Zhao, Pei; Liu, Kai; Herrmann, Andreas
Journal of the American Chemical Society (2015), 137 (40), 12884-12889CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
Preserving DNA hybridization in org. solvents could someday serve to significantly extend the applicability of DNA-based technologies. Here, the authors present a method that can be used to solubilize double-stranded DNA at high concns. in org. media. This method requires first pptg. a DNA mol. from the aq. environment with an anilinium deriv. and subsequently exchanging this moiety with an amine-contg. surfactant in org. solvent. This method yields complete exchange of the surfactant and allows for the modification of DNA with hydrophobic primary, secondary, and tertiary alkylamines and ordered functional π-systems. Using this approach, the authors fabricate a multichromophoric light harvesting system that would be unattainable by traditional methods. Addnl., this method makes it possible to use small, hydrophilic mols. to solubilize DNA in org. solvents, which reduces the shielding around the DNA and makes the macromol. more accessible for further chem. modification. The authors believe that this approach will prove tremendously beneficial in expanding the scope of DNA-based nano- and biotechnologies.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhsFGltLfN&md5=9c61742e8a4f2f70f35c47ed80a87964
40
Strzelecka, T. E.; Davidson, M. W.; Rill, R. L. Multiple Liquid Crystal Phases of DNA at High Concentrations Nature 1988, 331, 457– 460 DOI: 10.1038/331457a0
[Crossref], [PubMed], [CAS], Google Scholar
40
Multiple liquid crystal phases of DNA at high concentrations
Strzelecka, Teresa E.; Davidson, Michael W.; Rill, Randolph L.
Nature (London, United Kingdom) (1988), 331 (6155), 457-60CODEN: NATUAS; ISSN:0028-0836.
DNA forms ≥3 distinct liq. cryst. phases at concns. comparable to those in vivo, with phase transitions occurring over relatively narrow ranges of DNA concn. A weakly birefringent, dynamic, precholesteric mesophase with microscopic textures intermediate between those of a nematic and a true cholesteric phase forms at the lowest concns. required for phase sepn. At slightly higher DNA concns., a 2nd mesophase forms which is a strongly birefringent, well-ordered cholesteric phase with a concn.-dependent pitch of 2-10 μm. At the highest DNA concns., a phase forms which is 2-dimensionally ordered and resembles smectic phases of thermotropic liq. crystals obsd. with small mols.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL1cXht1Kru74%253D&md5=6ef25005329d68876cdcfbf09907a9c4
41
Nakata, M.; Zanchetta, G.; Chapman, B. D.; Jones, C. D.; Cross, J. O.; Pindak, R.; Bellini, T.; Clark, N. A. End-to-end Stacking and Liquid Crystal Condensation of 6-to-20-base Pair DNA Duplexes Science 2007, 318, 1276– 1279 DOI: 10.1126/science.1143826
[Crossref], [PubMed], [CAS], Google Scholar
41
End-to-End Stacking and Liquid Crystal Condensation of 6-to 20-Base Pair DNA Duplexes
Nakata, Michi; Zanchetta, Giuliano; Chapman, Brandon D.; Jones, Christopher D.; Cross, Julie O.; Pindak, Ronald; Bellini, Tommaso; Clark, Noel A.
Science (Washington, DC, United States) (2007), 318 (5854), 1276-1279CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
Short complementary B-form DNA oligomers, 6 to 20 base pairs in length, are found to exhibit nematic and columnar liq. crystal phases, even though such duplexes lack the shape anisotropy required for liq. crystal ordering. Structural study shows that these phases are produced by the end-to-end adhesion and consequent stacking of the duplex oligomers into polydisperse anisotropic rod-shaped aggregates, which can order into liq. crystals. Upon cooling mixed solns. of short DNA oligomers, in which only a small fraction of the DNA present is complementary, the duplex-forming oligomers phase-sep. into liq. crystal droplets, leaving the unpaired single strands in isotropic soln. In a chem. environment where oligomer ligation is possible, such ordering and condensation would provide an autocatalytic link whereby complementarity promotes the extended polymn. of complementary oligomers.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXhtlGmtbfP&md5=ae96e38beb2cc91ec9799903c76bac7b
42
Brach, K.; Matczyszyn, K.; Olesiak-Banska, J.; Gordel, M.; Samoc, M. Stabilization of DNA Liquid Crystals on Doping with Gold Nanorods Phys. Chem. Chem. Phys. 2016, 18, 7278– 7283 DOI: 10.1039/C5CP07026K
[Crossref], Google Scholar
There is no corresponding record for this reference.
43
Leone, A. M.; Tibodeau, J. D.; Bull, S. H.; Feldberg, S. W.; Thorp, H. H.; Murray, R. W. Ion Atmosphere Relaxation and Percolative Electron Transfer in Co Bipyridine DNA Molten Salts J. Am. Chem. Soc. 2003, 125, 6784– 6790 DOI: 10.1021/ja0348795
[ACS Full Text ], Google Scholar
There is no corresponding record for this reference.
44
Szalai, V. A.; Thorp, H. H. Electron Transfer in Tetrads: Adjacent Guanines Are Not Hole Traps in G Quartets J. Am. Chem. Soc. 2000, 122, 4524– 4525 DOI: 10.1021/ja0001355
[ACS Full Text ], Google Scholar
There is no corresponding record for this reference.
45
Candeias, L. P.; Steenken, S. Structure and Acid-Base Properties of One-Electron-Oxidized Deoxyguanosine, Guanosine, and 1-Methylguanosine J. Am. Chem. Soc. 1989, 111, 1094– 1099 DOI: 10.1021/ja00185a046
[ACS Full Text ], [CAS], Google Scholar
45
Structure and acid-base properties of one-electron-oxidized deoxyguanosine, guanosine, and 1-methylguanosine
Candeias, L. P.; Steenken, S.
Journal of the American Chemical Society (1989), 111 (3), 1094-9CODEN: JACSAT; ISSN:0002-7863.
The oxidn. of deoxyguanosine and its derivs., guanosine and 1-methylguanosine, by the 1-electron oxidants SO4•- and B2•- was studied following pulsed radiolysis in aq. soln. All 3 compds. reacted with SO4•- with nearly diffusion controlled rates and with Br2•- at rates of ≈5 × 107 M-1 s-1. At pH 7, the 1-electron oxidn. products were neutral radicals, formed by deprotonation from N(1) for guanosine and deoxyguanosine and from exocyclic N2 for 1-methylguanosine. The deoxyguanosine and guanosine radicals further deprotonate to give radical anions with pKa values of 10.8 and 10.7, resp. The results indicate that in the radiation chem. of DNA, the radical cation formed upon ionization of the guanine moiety shifts a proton to its complementary base cytosine.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL1MXltlOktg%253D%253D&md5=44185c0ceb937fff0f44e17bfed53174
46
Rokhlenko, Y.; Cadet, J.; Geacintov, N. E.; Shafirovich, V. Mechanistic Aspects of Hydration of Guanine Radical Cations in DNA J. Am. Chem. Soc. 2014, 136, 5956– 5962 DOI: 10.1021/ja412471u
[ACS Full Text ], [CAS], Google Scholar
46
Mechanistic Aspects of Hydration of Guanine Radical Cations in DNA
Rokhlenko, Yekaterina; Cadet, Jean; Geacintov, Nicholas E.; Shafirovich, Vladimir
Journal of the American Chemical Society (2014), 136 (16), 5956-5962CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
The mechanistic aspects of hydration of guanine radical cations, G•+ in double- and single-stranded oligonucleotides were investigated by direct time-resolved spectroscopic monitoring methods. The G•+ radical one-electron oxidn. products were generated by SO4•- radical anions derived from the photolysis of S2O82- anions by 308 nm laser pulses. In neutral aq. solns. (pH 7.0), after the complete decay of SO4•- radicals (∼5 μs after the actinic laser flash) the transient absorbance of neutral guanine radicals, G(-H)• with max. at 312 nm, is dominant. The kinetics of decay of G(-H)• radicals depend strongly on the DNA secondary structure. In double-stranded DNA (dsDNA), the G(-H)• decay is biphasic with one component decaying with a lifetime of ∼2.2 ms and the other with a lifetime of ∼0.18 s. By contrast, in single-stranded DNA (ssDNA) the G(-H)• radicals decay monophasically with a ∼ 0.28 s lifetime. The ms decay component in double-stranded DNA is correlated with the enhancement of 8-oxo-7,8-dihydroguanine (8-oxoG) yields which are ∼7 greater than in single-stranded DNA. In double-stranded DNA, it is proposed that the G(-H)• radicals retain radical cation character by sharing the N1-proton with the N3-site of C in the [G•+:C] base pair. This [G(-H)•:H+C G•+:C] equil. allows for the hydration of G•+ followed by formation of 8-oxoG. By contrast, in single-stranded DNA, deprotonation of G•+ and the irreversible escape of the proton into the aq. phase competes more effectively with the hydration mechanism, thus diminishing the yield of 8-oxoG, as obsd. exptl.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXltF2lsr8%253D&md5=629da5e8fef8cf2f31f3fa774b80e544
47
Bourlinos, A. B.; Herrera, R.; Chalkias, N.; Jiang, D. D.; Zhang, Q.; Archer, L. A.; Giannelis, E. P. Surface-Functionalized Nanoparticles with Liquid-Like Behavior Adv. Mater. 2005, 17, 234– 237 DOI: 10.1002/adma.200401060
[Crossref], [CAS], Google Scholar
47
Surface-functionalized nanoparticles with liquid-like behavior
Bourlinos, Athanasios B.; Herrera, Rafael; Chalkias, Nikolaos; Jiang, David D.; Zhang, Qiang; Archer, Lynden A.; Giannelis, Emmanuel P.
Advanced Materials (Weinheim, Germany) (2005), 17 (2), 234-237CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
Surface functionalization of silica or maghemite (γ-Fe2O3) nanoparticles with a quaternary ammonium organosilane leads to ionically modified nanoparticles that, depending on the nature of the counterion, exhibit liq.-like behavior in the absence of solvents. Solvent-free nanosalts composed of modified silica nanoparticles can be used to dissolve and polymerize pyrrole, while nanosalts composed of maghemite nanoparticles can form solvent-free ferrofluids.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXht12lur4%253D&md5=655948161182337fe5683d018695030f
48
Rodriguez, R.; Herrera, R.; Archer, L. A.; Giannelis, E. P. Nanoscale Ionic Materials Adv. Mater. 2008, 20, 4353– 4358 DOI: 10.1002/adma.200801975
[Crossref], [CAS], Google Scholar
48
Nanoscale ionic materials
Rodriguez, Robert; Herrera, Rafael; Archer, Lynden A.; Giannelis, Emmanuel P.
Advanced Materials (Weinheim, Germany) (2008), 20 (22), 4353-4358CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
Polymer nanocomposites (nanoparticles dispersed in a polymer matrix) were the subject of intense research for almost two decades in both academic and industrial settings. This interest was fueled by the ability of nanocomposites to not only improve the performance of polymers, but also by their ability to introduce new properties. Yet, there are still challenges that polymer nanocomposites must overcome to reach their full potential. In this Research News article a new class of hybrids termed nanoparticle ionic materials (NIMS) are discussed. NIMS are org.-inorg. hybrid materials comprising a nanoparticle core functionalized with a covalently tethered ionic corona. They are facilely engineered to display flow properties that span the range from glassy solids to free flowing liqs. These new systems have unique properties that can overcome some of the challenges facing nanocomosite materials.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhsVOhu7vO&md5=b578d0e300c2f1bfce66ec55a17084b7
49
Fernandes, N. J.; Wallin, T. J.; Vaia, R. A.; Koerner, H.; Giannelis, E. P. Nanoscale Ionic Materials Chem. Mater. 2014, 26, 84– 96 DOI: 10.1021/cm402372q
[ACS Full Text ], [CAS], Google Scholar
49
Nanoscale Ionic Materials
Fernandes, Nikhil J.; Wallin, Thomas J.; Vaia, Richard A.; Koerner, Hilmar; Giannelis, Emmanuel P.
Chemistry of Materials (2014), 26 (1), 84-96CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
A review. Within the general field of polymer grafted or hairy nanoparticles, nanoscale ionic materials (NIMs), consisting of a soft polymeric canopy bound to a well-defined nanoparticle core by an ionic bond, occupy a growing niche. They are the first example of neat, self-suspended fluids of nanoparticles (i.e., in the absence of a suspending medium). As such, the perennial dispersion challenges assocd. with polymer nanocomposites are minimized while the dynamic nature of the ionic bonds provides opportunities for self-healing behavior. Combining the properties of ionic liqs., charged colloid suspensions, and well-dispersed nanocomposites, this new materials platform offers remarkable versatility for current and future applications. This perspective covers techniques and current challenges in synthesis, discusses the state of understanding of the theory behind their structure and properties, and examines successes and future prospects in application in a no. of areas, notably in energy-related technologies.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhsV2ltr3I&md5=2693f51d90a3b2927930a7dd0f936018
50
Cavallo, L.; Kleinjung, J.; Fraternali, F. POPS: A Fast Algorithm for Solvent Accessible Surface Areas at Atomic and Residue Level Nucleic Acids Res. 2003, 31, 3364– 3366 DOI: 10.1093/nar/gkg601
[Crossref], [PubMed], [CAS], Google Scholar
50
POPS: a fast algorithm for solvent accessible surface areas at atomic and residue level
Cavallo, Luigi; Kleinjung, Jens; Fraternali, Franca
Nucleic Acids Research (2003), 31 (13), 3364-3366CODEN: NARHAD; ISSN:0305-1048. (Oxford University Press)
POPS (Parameter Optimized Surfaces) is a new method to calc. solvent accessible surface areas, which is based on an empirically parameterizable anal. formula and fast to compute. At. and residue areas (the latter represented by a single sphere centered on the Cα atom of amino acids and at the P atom of nucleotides) have been optimized vs. accurate all-atom methods. The parameterization has been derived from a selected dataset of proteins and nucleic acids of different sizes and topologies. The residue based approach POPS-R, has been devised as a useful tool for the anal. of large macromol. assemblies like the ribosome and it is specially suited for the refinement of low resoln. structures. POPS-R also allows for ests. of the loss of free energy of solvation upon complex formation, which should be particularly useful for the design of new protein-protein and protein-nucleic acid complexes.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXltVWisrk%253D&md5=967b4a0f2a96a800d64e28624897b6bf
51
Costantino, H. R.; Curley, J. G.; Hsu, C. C. Determining the Water Sorption Monolayer of Lyophilized Pharmaceutical Proteins J. Pharm. Sci. 1997, 86, 1390– 1393 DOI: 10.1021/js9701566
[Crossref], [PubMed], [CAS], Google Scholar
51
Determining the Water Sorption Monolayer of Lyophilized Pharmaceutical Proteins
Costantino, Henry R.; Curley, Janet G.; Hsu, Chung C.
Journal of Pharmaceutical Sciences (1997), 86 (12), 1390-1393CODEN: JPMSAE; ISSN:0022-3549. (American Chemical Society)
The concept of monolayer water coverage is useful in the development of lyophilized protein formulations. Herein, the authors explored 3 different methodologies to det. the water monolayer for pharmaceutical proteins: (1) theor. prediction based on the amino acid compn. and their relative propensities to sorb water; (2) a traditional adsorption isotherm measurement by Karl Fisher water titrn. of samples held at various relative humidities (created by satd. salt solns.); and (3) an adsorption isotherm measurement with a gravimetric sorption analyzer (GSA), which consists of a microbalance within a computer-controlled humidified environment. Data from the latter two methods were analyzed with the Brunauer-Emmett-Teller (BET) gas adsorption equation to yield exptl. monolayers. The authors examd. 6 different therapeutic proteins and found that for each case all 3 approaches yielded similar results for the water monolayer. The authors also attempted to use the BET equation to det. the water monolayer for a model sugar (trehalose) and polyol (mannitol), which are potential excipients in pharmaceutical protein formulations. Calcns. from the data obtained by the traditional and GSA methods yielded consistent results for trehalose, which remained amorphous upon lyophilization. Mannitol tended to form anhyd. crystals upon freeze-drying, and was thus not amenable to anal. The utility of both traditional and GSA methods for detg. the water monolayer was extended to colyophilized protein:sugar systems as well.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXnsFSitrk%253D&md5=0d8c3234802423dfc0d5419f1ff35fa3
52
Pauling, L. The Adsorption of Water by Proteins J. Am. Chem. Soc. 1945, 67, 555– 557 DOI: 10.1021/ja01220a017
[ACS Full Text ], [CAS], Google Scholar
52
The adsorption of water by proteins
Pauling, Linus
Journal of the American Chemical Society (1945), 67 (), 555-7CODEN: JACSAT; ISSN:0002-7863.
The data published by Bull (C.A. 38, 6156.1) and Shaw (C.A. 38, 6153.3) on the adsorption of water by proteins are in considerable degree interpreted on the assumption that the initial process is the attachment of one water mol. to each polar amino acid side chain. The data also indicate that peptide carbonyl and imido groups usually do not bind water, because of their mutual interaction by H-bond formation, but that water is bound by carbonyl groups that are not coupled by H bonds with imido groups. In salmin, in which most of the amino-acid residues are polar, these polar residues co.ovrddot.operate to attach one water mol. jointly to 2 polar groups in the initial process of hydration.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaH2MXhsVCmtQ%253D%253D&md5=530cf9b926551d5879c6a50f988cc833
53
Rupley, J. A.; Gratton, E.; Careri, G. Water and Globular Proteins Trends Biochem. Sci. 1983, 8, 18– 22 DOI: 10.1016/0968-0004(83)90063-4
[Crossref], [CAS], Google Scholar
53
Water and globular proteins
Rupley, John A.; Gratton, Enrico; Careri, Giorgio
Trends in Biochemical Sciences (1983), 8 (1), 18-22CODEN: TBSCDB; ISSN:0968-0004.
A review with 27 refs., on the hydration of globular proteins. The thermodn. of hydration are considered, and the effects of hydration on protein function, e.g., mol. dynamics and enzyme activity, are discussed.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL3sXosV2htA%253D%253D&md5=1bcdf1fe915c7556327c45ed1d59736c
54
Gallat, F.-X.; Brogan, A. P. S.; Fichou, Y.; McGrath, N.; Moulin, M.; Härtlein, M.; Combet, J.; Wuttke, J.; Mann, S.; Zaccai, G.; Jackson, C. J.; Perriman, A. W.; Weik, M. A Polymer Surfactant Corona Dynamically Replaces Water in Solvent-Free Protein Liquids and Ensures Macromolecular Flexibility and Activity J. Am. Chem. Soc. 2012, 134, 13168– 13171 DOI: 10.1021/ja303894g
[ACS Full Text ], [CAS], Google Scholar
54
A Polymer Surfactant Corona Dynamically Replaces Water in Solvent-Free Protein Liquids and Ensures Macromolecular Flexibility and Activity
Gallat, Francois-Xavier; Brogan, Alex P. S.; Fichou, Yann; McGrath, Nina; Moulin, Martine; Hartlein, Michael; Combet, Jerome; Wuttke, Joachim; Mann, Stephen; Zaccai, Giuseppe; Jackson, Colin J.; Perriman, Adam W.; Weik, Martin
Journal of the American Chemical Society (2012), 134 (32), 13168-13171CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
The observation of biol. activity in solvent-free protein-polymer surfactant hybrids challenges the view of aq. and nonaq. solvents being unique promoters of protein dynamics linked to function. Here, we combine elastic incoherent neutron scattering (EINS) and specific deuterium labeling to sep. study protein and polymer motions in solvent-free hybrids. Myoglobin (Mb) motions within the hybrid are found to closely resemble those of a hydrated protein, and motions of the polymer surfactant coating are similar to those of the hydration water, leading to the conclusion that the polymer surfactant coating plasticizes protein structures in a way similar to hydration water.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhtFalu7zF&md5=f2870398633b3c8082486516e7951765
55
Brogan, A. P. S.; Sharma, K. P.; Perriman, A. W.; Mann, S. Isolation of a Highly Reactive β-Sheet-Rich Intermediate of Lysozyme in a Solvent-Free Liquid Phase J. Phys. Chem. B 2013, 117, 8400– 8407 DOI: 10.1021/jp4041524
[ACS Full Text ], [CAS], Google Scholar
55
Isolation of a highly reactive β-sheet-rich intermediate of lysozyme in a solvent-free liquid phase
Brogan, Alex P. S.; Sharma, Kamendra P.; Perriman, Adam W.; Mann, Stephen
Journal of Physical Chemistry B (2013), 117 (28), 8400-8407CODEN: JPCBFK; ISSN:1520-5207. (American Chemical Society)
The thermal denaturation of solvent-free liq. lysozyme at temps. in excess of 200° was studied by synchrotron radiation CD spectroscopy. Temp.-dependent changes in the secondary structure were used to map the equil. denaturation pathway and characterize a reactive β-sheet-rich unfolding intermediate that was stable in the solvent-free liq. phase under anhyd. conditions but which underwent irreversible aggregation in the presence of water. The unfolding intermediate had a transition temp. of 78° and was extremely stable to temp., eventually reaching the fully denatured state at 178°. The authors propose that the 3-stage denaturation pathway arises from the decreased stability of the native state due to the absence of any appreciable hydrophobic effect, along with an entropically derived stabilization of the reactive intermediate assocd. with mol. crowding in the solvent-free liq.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXpvFantbk%253D&md5=3f965a145b653301ae3c0efdc23285ac
56
Brogan, A. P. S.; Sessions, R. B.; Perriman, A. W.; Mann, S. Molecular Dynamics Simulations Reveal a Dielectric-Responsive Coronal Structure in Protein–Polymer Surfactant Hybrid Nanoconstructs J. Am. Chem. Soc. 2014, 136, 16824– 16831 DOI: 10.1021/ja507592b
[ACS Full Text ], Google Scholar
There is no corresponding record for this reference.
57
Sharma, K. P.; Zhang, Y.; Thomas, M. R.; Brogan, A. P. S.; Perriman, A. W.; Mann, S. Self-Organization of Glucose Oxidase–Polymer Surfactant Nanoconstructs in Solvent-Free Soft Solids and Liquids J. Phys. Chem. B 2014, 118, 11573– 11580 DOI: 10.1021/jp507566u
[ACS Full Text ], [CAS], Google Scholar
57
Self-Organization of Glucose Oxidase-Polymer Surfactant Nanoconstructs in Solvent-Free Soft Solids and Liquids
Sharma, Kamendra P.; Zhang, Yixiong; Thomas, Michael R.; Brogan, Alex P. S.; Perriman, Adam W.; Mann, Stephen
Journal of Physical Chemistry B (2014), 118 (39), 11573-11580CODEN: JPCBFK; ISSN:1520-5207. (American Chemical Society)
An anisotropic glucose oxidase-polymer surfactant nanoconjugate is synthesized and shown to exhibit complex temp.-dependent phase behavior in the solvent-free state. At close to room temp., the nanoconjugate crystallizes as a mesolamellar soft solid with an expanded interlayer spacing of ca. 12 nm and interchain correlation lengths consistent with alkyl tail-tail and PEO-PEO ordering. The soft solid displays a birefringent spherulitic texture and melts at 40 °C to produce a solvent-free liq. protein without loss of enzyme secondary structure. The nanoconjugate melt exhibits a birefringent dendritic texture below the conformation transition temp. (Tc) of glucose oxidase (58 °C) and retains interchain PEO-PEO ordering. Our results indicate that the shape anisotropy of the protein-polymer surfactant globular building block plays a key role in directing mesolamellar formation in the solvent-free solid and suggests that the microstructure obsd. in the solvent-free liq. protein below Tc is assocd. with restrictions in the intramol. motions of the protein core of the nanoconjugate.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsFWjsrvJ&md5=0fda67f11c72f9fb5a1f90097c8f90b6
58
Hanski, S.; Junnila, S.; Almásy, L.; Ruokolainen, J.; Ikkala, O. Structural and Conformational Transformations in Self-Assembled Polypeptide–Surfactant Complexes Macromolecules 2008, 41, 866– 872 DOI: 10.1021/ma7019495
[ACS Full Text ], Google Scholar
There is no corresponding record for this reference.
59
Kolbe, A.; del Mercato, L. L.; Abbasi, A. Z.; Rivera Gil, P.; Gorzini, S. J.; Huibers, W. H. C.; Poolman, B.; Parak, W. J.; Herrmann, A. De Novo Design of Supercharged, Unfolded Protein Polymers, and Their Assembly into Supramolecular Aggregates Macromol. Rapid Commun. 2011, 32, 186– 190 DOI: 10.1002/marc.201000491
[Crossref], [PubMed], [CAS], Google Scholar
59
De Novo Design of Supercharged, Unfolded Protein Polymers, and Their Assembly into Supramolecular Aggregates
Kolbe, Anke; del Mercato, Loretta L.; Abbasi, Azhar Z.; Rivera Gil, Pilar; Gorzini, Sekineh J.; Huibers, Wim H. C.; Poolman, Bert; Parak, Wolfgang J.; Herrmann, Andreas
Macromolecular Rapid Communications (2011), 32 (2), 186-190CODEN: MRCOE3; ISSN:1022-1336. (Wiley-VCH Verlag GmbH & Co. KGaA)
Here we report for the first time the design and expression of highly charged, unfolded protein polymers based on elastin-like peptides (ELPs). Pos. and neg. charged variants were achieved by introducing lysine and glutamic acid residues, resp., within the repetitive pentapeptide units. Subsequently it was demonstrated that the monodisperse protein polyelectrolytes with precisely defined amino acid compns., sequences, and stereochemistries can be transferred into superstructures exploiting their electrostatic interactions. Hollow capsules were assembled from oppositely charged protein chains by using the layer-by-layer technique. The structures of the capsules were analyzed by various microscopy techniques revealing the fabrication of multilayer containers. Due to their low toxicity in comparison to other polyelectrolytes, supercharged ELPs are appealing candidates for the construction of electrostatically induced scaffolds in biomedicine.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXlsVyqug%253D%253D&md5=ac50c27ffe5f1cc8450cb5b7ced9d8a3
60
Yang, H.; Ma, C.; Li, K.; Liu, K.; Loznik, M.; Teeuwen, R.; van Hest, J. C. M.; Zhou, X.; Herrmann, A.; Wang, J. Tuning Ice Nucleation with Supercharged Polypeptides Adv. Mater. 2016, 28, 5008– 5012 DOI: 10.1002/adma.201600496
[Crossref], [PubMed], [CAS], Google Scholar
60
Tuning Ice Nucleation with Supercharged Polypeptides
Yang, Huige; Ma, Chao; Li, Kaiyong; Liu, Kai; Loznik, Mark; Teeuwen, Rosalie; van Hest, Jan C. M.; Zhou, Xin; Herrmann, Andreas; Wang, Jianjun
Advanced Materials (Weinheim, Germany) (2016), 28 (25), 5008-5012CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
The authors reported the tuning of ice nucleation through systematic control of both surface charge and charge d., which is achieved via modifying solid surfaces with supercharged unfolded polypeptides (SUPs). Compared to their chem. synthesized counterparts, SUPs are of low toxicity and are biodegradable. Moreover, the fabrication procedure based on genetic engineering allows abs. control over nature of charges, chain length, and charge d., combined with a monodisperse character. These structural attributes of SUPs open up new possibilities for the study of ice nucleation.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XmvFart78%253D&md5=5b3da396d9d9c2cca7bbeffd8e381e7a
61
Sharma, K. P.; Bradley, K.; Brogan, A. P. S.; Mann, S.; Perriman, A. W.; Fermin, D. J. Redox Transitions in an Electrolyte-Free Myoglobin Fluid J. Am. Chem. Soc. 2013, 135, 18311– 18314 DOI: 10.1021/ja4104606
[ACS Full Text ], [CAS], Google Scholar
61
Redox Transitions in an Electrolyte-Free Myoglobin Fluid
Sharma, Kamendra P.; Bradley, Kieren; Brogan, Alex P. S.; Mann, Stephen; Perriman, Adam W.; Fermin, David J.
Journal of the American Chemical Society (2013), 135 (49), 18311-18314CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
Redox responses assocd. with the heme prosthetic group in a myoglobin-polymer surfactant solvent-free liq. are investigated for the first time in the absence of an electrolyte soln. Cyclic voltammograms from the biofluid exhibit responses that are consistent with planar diffusion of mobile charges in the melt. Temp.-dependent dynamic electrochem. and rheol. responses are rationalized in terms of the effective electron hopping rate between heme centers and the transport of intrinsic ionic species in the viscous protein liq.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhvVShsL7L&md5=a7434c2da24494a9fac820cefdca1dbe
62
Rusling, J. F.; Nassar, A. E. F. Enhanced Electron Transfer for Myoglobin in Surfactant Films on Electrodes J. Am. Chem. Soc. 1993, 115, 11891– 11897 DOI: 10.1021/ja00078a030
[ACS Full Text ], [CAS], Google Scholar
62
Enhanced electron transfer for myoglobin in surfactant films on electrodes
Rusling, James F.; Nassar, Alaa Eldin F.
Journal of the American Chemical Society (1993), 115 (25), 11891-7CODEN: JACSAT; ISSN:0002-7863.
The Fe(III)/Fe(II) redox couple of the heme protein myoglobin (Mb) gave std. electron-transfer rate consts. about 1000-fold larger in liq. crystal films of didodecyldimethyl ammonium bromide (DDAB) on pyrolytic graphite (PG) electrodes than in aq. solns. Electron-transfer rates of Mb were also enhanced in films of sol. cationic and anionic surfactants absorbed on PG. Results suggest a role for strongly adsorbed surfactant at electrode-film interfaces, which may prevent adsorption of macromol. impurities which can block electron transfer. Mb-DDAB films were prepd. by spontaneous insertion of Mb from soln. into water-insol. cast films of DDAB. The resulting films were stable for a month in pH 5.5-7.5 buffers contg. 50 mM NaBr. Spectroscopic, thermal, and electrochem. characterizations suggest that the films consist of lamellar liq. crystal DDAB contg. preferentially oriented Mb with the iron heme in a high spin state. Mb-DDAB films showed good charge-transport rates, which allowed Mb to be used as a redox catalyst. Redns. of the organohalide pollutants trichloroacetic acid and ethylene dibromide were catalyzed by Mb-DDAB films on PG electrodes at voltages 1.0-1.3 V less neg. than direct redns.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXjvVyk&md5=d8b2faf9cb5410f53d44f7488a5945c5

Cited By

This article is cited by 27 publications.

Yusai Zhou, Kai Liu, Hongjie Zhang. Biomimetic Mineralization: From Microscopic to Macroscopic Materials and Their Biomedical Applications. ACS Applied Bio Materials 2023, 6 (9) , 3516-3531. https://doi.org/10.1021/acsabm.3c00109
Mengjiao Yi, Zhaohui Huang, Ping Qi, Qi Fan, Jingcheng Hao. K+, Sr2+-Triggered Phase Transitions from Chiral Thermotropic Liquid Crystalline to G-Quadruplex CTLC with Circularly Polarized Luminescence. The Journal of Physical Chemistry C 2021, 125 (35) , 19570-19579. https://doi.org/10.1021/acs.jpcc.1c06178
Lei Zhang, Yun Liu, Kang Wang, Guoqiang Zhang, Qianyao Du, Qikai Liang, Zhongtao Wu. Azobenzene-containing surfactant directs small features of DNA thermotropic liquid crystals via bottom-up and top-down strategies. Acta Biomaterialia 2023, 166 , 147-154. https://doi.org/10.1016/j.actbio.2023.05.023
Sudarshan Behera, Sundaram Balasubramanian. Molecular simulations explain the exceptional thermal stability, solvent tolerance and solubility of protein–polymer surfactant bioconjugates in ionic liquids. Physical Chemistry Chemical Physics 2022, 24 (36) , 21904-21915. https://doi.org/10.1039/D2CP02636H
Lei Zhang, Chenghao Zhang, Kang Wang, Jishuai Liu, Congxia Xie, Zhongtao Wu. Fluorescent solvent-free lignin ionic complexes with thermostability toward a luminescent hydrophobic coating material. Materials Chemistry Frontiers 2022, 6 (15) , 2122-2127. https://doi.org/10.1039/D2QM00449F
Chenghao Zhang, Lei Zhang, Zheng Cao, Changshuo Lian, Shengjie Gao, Di Zhang, Xue Shi, Wenjing Du, Congxia Xie, Zhongtao Wu. Fluorescent DNA thermotropic liquid crystal showing thermostability and water-resistance. Dyes and Pigments 2022, 52 , 110449. https://doi.org/10.1016/j.dyepig.2022.110449
Hua Yuan, Shiwen Yang, Hao Yan, Jiayi Guo, Wenchao Zhang, Qiao Yu, Xianze Yin, Yeqiang Tan. Liquefied Polysaccharides‐Based Polymer with Tunable Condensed State Structure for Antimicrobial Shield by Multiple Processing Methods. Small Methods 2022, 6 (5) https://doi.org/10.1002/smtd.202200129
Sudarshan Behera, Sundaram Balasubramanian. Insights into substrate behavior in a solvent-free protein liquid to rationalize its reduced catalytic rate. RSC Advances 2022, 12 (19) , 11896-11905. https://doi.org/10.1039/D2RA00666A
Joseph M. Slocik, Patrick B. Dennis, Zhifeng Kuang, Anthony Pelton, Rajesh R. Naik. Creation of stable water-free antibody based protein liquids. Communications Materials 2021, 2 (1) https://doi.org/10.1038/s43246-021-00222-2
L. Zhang, Y. Qu, J. Gu, Y. Liu, Z. Tang, C. Zhang, H. Liu, J. Liu, Z. Wu, X. Luo. Photoswitchable solvent-free DNA thermotropic liquid crystals toward self-erasable shape information recording biomaterials. Materials Today Bio 2021, 12 , 100140. https://doi.org/10.1016/j.mtbio.2021.100140
Lei Zhang, Yang Qu, Jingjing Gu, Han Liu, Zhongtao Wu, Xiliang Luo. Powerful tailoring effects of counterions of ammonium surfactants on the phase transitions of solvent-free DNA thermotropic liquid crystals. Journal of Molecular Liquids 2021, 337 , 116480. https://doi.org/10.1016/j.molliq.2021.116480
Lei Zhang, Yang Qu, Jingjing Gu, Zhenyu Tang, Zhongtao Wu, Xiliang Luo. Photoliquefiable DNA-surfactant ionic crystals: Anhydrous self-healing biomaterials at room temperature. Acta Biomaterialia 2021, 128 , 143-149. https://doi.org/10.1016/j.actbio.2021.04.039
Lei Zhang, Yang Qu, Yun Liu, Yawen Deng, Jingjing Gu, Zhongtao Wu, Jiehua Lin, Xiliang Luo. Visible Light Responsive DNA Thermotropic Liquid Crystals Based on a Photothermal Effect of Gold Nanoparticles. Journal of Analysis and Testing 2021, 5 (2) , 181-187. https://doi.org/10.1007/s41664-020-00150-z
Sikang Wan, Wei Cong, Baiqi Shao, Baiheng Wu, Qingbin He, Quan Chen, Jianlei Shen, Dong Chen, Hong-Gang Hu, Fangfu Ye, Chunhai Fan, Hongjie Zhang, Kai Liu. A library of thermotropic liquid crystals of inorganic nanoparticles and extraordinary performances based on their collective ordering. Nano Today 2021, 38 , 101115. https://doi.org/10.1016/j.nantod.2021.101115
Lei Zhang, Yawen Deng, Yubao Tang, Congxia Xie, Zhongtao Wu. Solid-state spiropyrans exhibiting photochromic properties based on molecular flexibility. Materials Chemistry Frontiers 2021, 5 (7) , 3119-3124. https://doi.org/10.1039/D0QM01086C
Yang Qu, Zhongtao Wu, Yun Liu, Jiehua Lin, Lei Zhang, Xiliang Luo. Impact of double-chain surfactant stabilizer on the free active surface sites of gold nanoparticles. Molecular Catalysis 2021, 501 , 111377. https://doi.org/10.1016/j.mcat.2020.111377
Sudarshan Behera, Sudip Das, Sundaram Balasubramanian. An atomistic view of solvent-free protein liquids: the case of Lipase A. Physical Chemistry Chemical Physics 2021, 5 https://doi.org/10.1039/D0CP05964A
Baiqi Shao, Sikang Wan, Chenjing Yang, Jianlei Shen, Yiwen Li, Hongpeng You, Dong Chen, Chunhai Fan, Kai Liu, Hongjie Zhang. Engineered Anisotropic Fluids of Rare‐Earth Nanomaterials. Angewandte Chemie 2020, 132 (41) , 18370-18374. https://doi.org/10.1002/ange.202007676
Baiqi Shao, Sikang Wan, Chenjing Yang, Jianlei Shen, Yiwen Li, Hongpeng You, Dong Chen, Chunhai Fan, Kai Liu, Hongjie Zhang. Engineered Anisotropic Fluids of Rare‐Earth Nanomaterials. Angewandte Chemie International Edition 2020, 59 (41) , 18213-18217. https://doi.org/10.1002/anie.202007676
Jun Ma, Chao Ma, Jingjing Li, Yao Sun, Fangfu Ye, Kai Liu, Hongjie Zhang. Extracellular Matrix Proteins Involved in Alzheimer's Disease. Chemistry – A European Journal 2020, 26 (53) , 12101-12110. https://doi.org/10.1002/chem.202000782
Chao Ma, Anke Malessa, Arnold J. Boersma, Kai Liu, Andreas Herrmann. Supercharged Proteins and Polypeptides. Advanced Materials 2020, 32 (20) https://doi.org/10.1002/adma.201905309
Huizhong Liu, Ling Wang, Yuanyuan Hu, Ziang Huang, Ying Sun, Shuli Dong, Jingcheng Hao. DNA thermotropic liquid crystals controlled by positively charged catanionic bilayer vesicles. Chemical Communications 2020, 56 (24) , 3484-3487. https://doi.org/10.1039/D0CC00980F
Zhaohui Huang, Xueyuan Li, Mengjun Chen, Yihan Liu, Xiuping Sun, Aixin Song, Jingcheng Hao. Guanosine-based thermotropic liquid crystals with tunable phase structures and ion-responsive properties. Journal of Colloid and Interface Science 2019, 553 , 269-279. https://doi.org/10.1016/j.jcis.2019.06.041
Zhaohui Huang, Ping Qi, Yihan Liu, Chunxiao Chai, Yitong Wang, Aixin Song, Jingcheng Hao. Ionic-surfactants-based thermotropic liquid crystals. Physical Chemistry Chemical Physics 2019, 21 (28) , 15256-15281. https://doi.org/10.1039/C9CP02697E
Kai Liu, Chao Ma, Andreas Herrmann. Solvent‐Free Liquids and Liquid Crystals from Biomacromolecules. 2019, 211-233. https://doi.org/10.1002/9783527804948.ch11
Caitlin Howell, Alison Grinthal, Steffi Sunny, Michael Aizenberg, Joanna Aizenberg. Designing Liquid‐Infused Surfaces for Medical Applications: A Review. Advanced Materials 2018, 30 (50) https://doi.org/10.1002/adma.201802724
Junjie Wu, Dongdong Li, Huifang Zeng, Zhou Zhou, Shijia Yang, Ning Zhao, Jian Xu. TiO2 nanoscale ionic materials using mussel adhesive proteins inspired ligand. Applied Surface Science 2018, 459 , 606-611. https://doi.org/10.1016/j.apsusc.2018.08.039

Download PDF

Abstract
High Resolution Image
Download MS PowerPoint Slide
Figure 1
Figure 1. Surfactants containing PEG tails for solvent-free DNA liquids. (a, b) Cationic quaternary ammonium surfactants. (14, 15) (c) Amine surfactant to complex acidified DNA by proton exchange. (15) (d) Polypyridyl complex of Co decorated with polyether chains as cationic surfactants. (14)
High Resolution Image
Download MS PowerPoint Slide
Figure 2
Figure 2. Solvent-free liquid crystals and liquids of DNA–surfactant complexes. (16) (a) Lamellar structure in the LC phase. (b) POM image of the DNA–surfactant mesophases. (c) Schematic of disordered DNA-surfactant complex in the isotropic liquid phase, and (d) POM image of the isotropic liquid. The scale bar is 100 μm. (e) Phase-transition temperatures of DNA–surfactant complexes from crystalline (Cr) to liquid crystalline (LC) to isotropic liquid. Adapted with permission from ref 16. Copyright 2015 John Wiley & Sons, Inc.
High Resolution Image
Download MS PowerPoint Slide
Figure 3
Figure 3. Phase-dependent electrochromic device based on solvent-free DNA–surfactant complexes. (28) (a, b) Switchable electrochromism in the isotropic liquid phase. (c, d) Optical memory of the liquid crystal as a persistent colored state. (e, f) Cooling the colored state to the crystalline phase further increases the relaxation time. (g, h) The activated device functions as time and temperature indicator. Adapted from ref 28. Licensed under CC BY 2016 Springer Nature.
High Resolution Image
Download MS PowerPoint Slide
Figure 4
Figure 4. Fabrication of solvent-free protein liquids. (a) General route for the preparation of protein liquids: (17) (i) EDC-initiated coupling of N,N-dimethyl-1,3-propanediamine to carboxylic acid surface residues of proteins; (ii) electrostatic complexation of cationized protein with anionic surfactants forming protein–surfactant hybrid. (b, c) Surfactants electrostatically bound to proteins. (d, e) Electrostatic binding of protein with surfactants. (18) (f) Gravity-induced flow of a solvent-free protein–surfactant liquid. Adapted with permission from ref 17, Copyright 2009 John Wiley & Sons, Inc., and ref 18, Copyright 2010 Macmillan Publishers Ltd.
High Resolution Image
Download MS PowerPoint Slide
Figure 5
Figure 5. Solvent-free fluids based on SUPs. (19) (a) Negatively charged SUPs combined with cationic surfactants. (b) POM image of SUP-surfactant smectic LC. (c) Lamellar bilayer structure of the LC phase. (d) Rheological investigation of the solvent-free SUP-surfactant fluids. Adapted with permission from ref 19. Copyright 2015 John Wiley & Sons, Inc.
High Resolution Image
Download MS PowerPoint Slide
Figure 6
Figure 6. Electrochemical investigation of solvent-free Mb–surfactant liquids. (27) (a) Molecular model of the Mb–surfactant complex. (b) Diagram of the three electrode cell configuration. (c) Structure of electrochemical FET used for conductivity measurements. (d) Conductivity measurements for the Mb–surfactant melt blended with LiPF₆ (red) and pristine Mb–surfactant melt (black). Adapted with permission from ref 27. Copyright 2015 John Wiley & Sons, Inc.
High Resolution Image
Download MS PowerPoint Slide
Figure 7
Figure 7. Hydrolysis of fatty acid esters in solvent-free lipase–surfactant liquids. (26) (a) 3D model showing the Ser144-His257-Asp203 catalytic triad of the lipase and the helical lid motif. (b) Two-step mechanism for lipase-based hydrolysis of pNPPal and pNPB. Initial rate of reactions of pNPB (c) and pNPPal (d) within solvent-free lipase–surfactant liquids as a function of temperature (RML black; TML red). Adapted by permission from Macmillan Publishers Ltd.: ref 26, copyright 2014.
High Resolution Image
Download MS PowerPoint Slide
Figure 8
Figure 8. Solvent-free virus–surfactant fluids. (a) General route toward CPMV melt. (20) Optical images of symptomatic Vigna unguiculata plants after infection with aqueous dispersions of wild-type CPMV (b) and solvent-free CPMV–surfactant droplet (c). Pairs of leaves either treated or untreated are shown. (d, e) Bacteriophages used for solvent-free virus liquid crystals and liquids. (21) Magnifications of FF-TEM images of the phage-surfactant LCs are shown. Adapted with permission from ref 20. Copyright 2012 John Wiley & Sons, Inc.
High Resolution Image
Download MS PowerPoint Slide
References
ARTICLE SECTIONS
Jump To
This article references 62 other publications.
1. 1
  Babu, S. S.; Hollamby, M. J.; Aimi, J.; Ozawa, H.; Saeki, A.; Seki, S.; Kobayashi, K.; Hagiwara, K.; Yoshizawa, M.; Möhwald, H.; Nakanishi, T. Nonvolatile Liquid Anthracenes for Facile Full-Colour Luminescence Tuning at Single Blue-Light Excitation Nat. Commun. 2013, 4, 1969 DOI: 10.1038/ncomms2969
  [Crossref], [PubMed], [CAS], Google Scholar
  1
  Nonvolatile liquid anthracenes for facile full-colour luminescence tuning at single blue-light excitation
  Babu Sukumaran Santhosh; Hollamby Martin J; Aimi Junko; Ozawa Hiroaki; Saeki Akinori; Seki Shu; Kobayashi Kenji; Hagiwara Keita; Yoshizawa Michito; Mohwald Helmuth; Nakanishi Takashi
  Nature communications (2013), 4 (), 1969 ISSN:.
  Nonvolatile room-temperature luminescent molecular liquids are a new generation of organic soft materials. They possess high stability, versatile optical properties, solvent-free fluid behaviour and can effectively accommodate dopant dye molecules. Here we introduce an approach to optimize anthracene-based liquid materials, focussing on enhanced stability, fluorescence quantum yield, colour tunability and processability, with a view to flexible electronic applications. Enveloping the anthracene core in low-viscosity branched aliphatic chains results in stable, nonvolatile, emissive liquid materials. Up to 96% efficient energy-transfer-assisted tunable emission is achieved by doping a minute amount of acceptor dye in the solvent-free state. Furthermore, we use a thermoresponsive dopant to impart thermally controllable luminescence colours. The introduced strategy leading to diverse luminescence colours at a single blue-light excitation can be an innovative replacement for currently used luminescent materials, providing useful continuous emissive layers in developing foldable devices.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC3snps1Cjsg%253D%253D&md5=a412f3040a22122303ee7c2a77199033
2. 2
  Giri, N.; Del Pópolo, M. G.; Melaugh, G.; Greenaway, R. L.; Rätzke, K.; Koschine, T.; Pison, L.; Gomes, M. F. C.; Cooper, A. I.; James, S. L. Liquids with Permanent Porosity Nature 2015, 527, 216– 220 DOI: 10.1038/nature16072
  [Crossref], [PubMed], [CAS], Google Scholar
  2
  Liquids with permanent porosity
  Giri, Nicola; Del Popolo, Mario G.; Melaugh, Gavin; Greenaway, Rebecca L.; Ratzke, Klaus; Koschine, Tonjes; Pison, Laure; Gomes, Margarida F. Costa; Cooper, Andrew I.; James, Stuart L.
  Nature (London, United Kingdom) (2015), 527 (7577), 216-220CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
  Porous solids such as zeolites and metal-org. frameworks are useful in mol. sepn. and in catalysis, but their solid nature can impose limitations. For example, liq. solvents, rather than porous solids, are the most mature technol. for post-combustion capture of carbon dioxide because liq. circulation systems are more easily retrofitted to existing plants. Solid porous adsorbents offer major benefits, such as lower energy penalties in adsorption-desorption cycles, but they are difficult to implement in conventional flow processes. Materials that combine the properties of fluidity and permanent porosity could therefore offer technol. advantages, but permanent porosity is not assocd. with conventional liqs. Here we report free-flowing liqs. whose bulk properties are detd. by their permanent porosity. To achieve this, we designed cage mols. that provide a well-defined pore space and that are highly sol. in solvents whose mols. are too large to enter the pores. The concn. of unoccupied cages can thus be around 500 times greater than in other mol. solns. that contain cavities, resulting in a marked change in bulk properties, such as an eightfold increase in the soly. of methane gas. Our results provide the basis for development of a new class of functional porous materials for chem. processes, and we present a one-step, multigram scale-up route for highly sol. 'scrambled' porous cages prepd. from a mixt. of com. available reagents. The unifying design principle for these materials is the avoidance of functional groups that can penetrate into the mol. cage cavities.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXitVSiu7nN&md5=6334a97707c4112dff7b44d5b72b001d
3. 3
  Ogoshi, T.; Aoki, T.; Shiga, R.; Iizuka, R.; Ueda, S.; Demachi, K.; Yamafuji, D.; Kayama, H.; Yamagishi, T. Cyclic Host Liquids for Facile and High-Yield Synthesis of [2]Rotaxanes J. Am. Chem. Soc. 2012, 134, 20322– 20325 DOI: 10.1021/ja310757p
  [ACS Full Text ], [CAS], Google Scholar
  3
  Cyclic Host Liquids for Facile and High-Yield Synthesis of [2]Rotaxanes
  Ogoshi, Tomoki; Aoki, Takamichi; Shiga, Ryohei; Iizuka, Ryo; Ueda, Seita; Demachi, Kazuki; Yamafuji, Daiki; Kayama, Hitoshi; Yamagishi, Tada-aki
  Journal of the American Chemical Society (2012), 134 (50), 20322-20325CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
  We developed "cyclic host liqs. (CHLs)" as a new type of solvent. The CHLs are a nonvolatile liq. over a wide temp. range, are biocompatible and recyclable, have high thermal stability, and are miscible with many org. solvents. Compared with typical complexation systems, the CHL system is extremely efficient for maintaining host-guest complexation because an addnl. solvent is not required. Based on the efficient host-guest complexation in the CHL system, we demonstrated synthesis of [2]rotaxanes in pillar[5]arene-based CHL. High yields were obtained for [2]rotaxanes capped by cationization (yield 91%) and Huisgen reaction (yield 88%) between the axle and the stopper components in the CHL system, while the assocn. consts. between the axles and wheels were quite low (10-15 M-1) in CDCl3. The CHL system provides a new powerful approach for synthesis of mech. interlocked mols. (MIMs) even with unfavorable statistical combinations of host-guest complexes.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhslOmu7nE&md5=d8b4a0aee89178a184bb94f672b1c4c5
4. 4
  Bellissent-Funel, M.-C.; Hassanali, A.; Havenith, M.; Henchman, R.; Pohl, P.; Sterpone, F.; van der Spoel, D.; Xu, Y.; Garcia, A. E. Water Determines the Structure and Dynamics of Proteins Chem. Rev. 2016, 116, 7673– 7697 DOI: 10.1021/acs.chemrev.5b00664
  [ACS Full Text ], [CAS], Google Scholar
  4
  Water Determines the Structure and Dynamics of Proteins
  Bellissent-Funel, Marie-Claire; Hassanali, Ali; Havenith, Martina; Henchman, Richard; Pohl, Peter; Sterpone, Fabio; van der Spoel, David; Xu, Yao; Garcia, Angel E.
  Chemical Reviews (Washington, DC, United States) (2016), 116 (13), 7673-7697CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
  Water is an essential participant in the stability, structure, dynamics, and function of proteins and other biomols. Thermodynamically, changes in the aq. environment affect the stability of biomols. Structurally, water participates chem. in the catalytic function of proteins and nucleic acids and phys. in the collapse of the protein chain during folding through hydrophobic collapse and mediates binding through the hydrogen bond in complex formation. Water is a partner that slaves the dynamics of proteins, and water interaction with proteins affect their dynamics. Here we provide a review of the exptl. and computational advances over the past decade in understanding the role of water in the dynamics, structure, and function of proteins. We focus on the combination of X-ray and neutron crystallog., NMR, terahertz spectroscopy, mass spectroscopy, thermodn., and computer simulations to reveal how water assist proteins in their function. The recent advances in computer simulations and the enhanced sensitivity of exptl. tools promise major advances in the understanding of protein dynamics, and water surely will be a protagonist.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XnvFeqsrw%253D&md5=365764ba66b0f0b2f94d1d401ee4d691
5. 5
  Bloomfield, V. A. DNA Condensation Curr. Opin. Struct. Biol. 1996, 6, 334– 341 DOI: 10.1016/S0959-440X(96)80052-2
  [Crossref], [PubMed], [CAS], Google Scholar
  5
  DNA condensation
  Bloomfield, Victor A.
  Current Opinion in Structural Biology (1996), 6 (3), 334-341CODEN: COSBEF; ISSN:0959-440X. (Current Biology)
  A review with 73 refs. is presented on recent progress in our understanding of DNA condensation. Topics discussed include the observation of the collapse of single DNA mols., greater insights into the intermol. forces driving condensation, the recognition of helix-structure perturbation in condensed DNA, and the increasing recognition of the likely biol. consequences of condensation. DNA condensed with cationic liposomes is an efficient agent for the transfection of eukaryotic cells, with considerable potential interest for gene therapy.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK28XjvFSgsL4%253D&md5=36b884b9e5f4af3e42f7f6d1d4f24a0e
6. 6
  Kim, W.; Conticello, V. P. Protein Engineering Methods for Investigation of Structure-Function Relationships in Protein-Based Elastomeric Materials Polym. Rev. 2007, 47, 93– 119 DOI: 10.1080/15583720601109586
  [Crossref], Google Scholar
  There is no corresponding record for this reference.
7. 7
  Kyle, S.; Aggeli, A.; Ingham, E.; McPherson, M. J. Production of Self-Assembling Biomaterials for Tissue Engineering Trends Biotechnol. 2009, 27, 423– 433 DOI: 10.1016/j.tibtech.2009.04.002
  [Crossref], [PubMed], [CAS], Google Scholar
  7
  Production of self-assembling biomaterials for tissue engineering
  Kyle, Stuart; Aggeli, Amalia; Ingham, Eileen; McPherson, Michael J.
  Trends in Biotechnology (2009), 27 (7), 423-433CODEN: TRBIDM; ISSN:0167-7799. (Elsevier B.V.)
  A review. Self-assembling peptide-based biomaterials are being developed for use as 3D tissue engineering scaffolds and for therapeutic drug-release applications. Chem. synthesis provides custom-made peptides in small quantities, but prodn. approaches based upon transgenic organisms might be more cost-effective for large-scale peptide prodn. Long lead times for developing appropriate animal clones or plant lines and potential neg. public opinion are obstacles to these routes. Microbes, particularly safe organisms used in the food industry, offer a more rapid route to the large-scale prodn. of recombinant self-assembling biomaterials. In this review, recent advances and challenges in the recombinant prodn. of collagen, elastin and de novo designed self-assembling peptides are discussed.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXnslymsbc%253D&md5=9321e7bd50eea7bdcacb4049bf13b439
8. 8
  Gordiichuk, P. I.; Wetzelaer, G.-J. A. H.; Rimmerman, D.; Gruszka, A.; de Vries, J. W.; Saller, M.; Gautier, D. A.; Catarci, S.; Pesce, D.; Richter, S.; Blom, P. W. M.; Herrmann, A. Solid-State Biophotovoltaic Cells Containing Photosystem I Adv. Mater. 2014, 26, 4863– 4869 DOI: 10.1002/adma.201401135
  [Crossref], [PubMed], [CAS], Google Scholar
  8
  Solid-state biophotovoltaic cells containing Photosystem I
  Gordiichuk, Pavlo I.; Wetzelaer, Gert-Jan A. H.; Rimmerman, Dolev; Gruszka, Agnieszka; Willem de Vries, Jan X.; Saller, Manfred; Gautier, Daniel A.; Catarci, Stefano; Pesce, Diego; Richter, Shachar; Blom, Paul W. M.; Herrmann, Andreas
  Advanced Materials (Weinheim, Germany) (2014), 26 (28), 4863-4869CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
  Processes occurring during photosynthesis, such as dynamic self-repair, light harvesting and quantum effects can be integrated into man-made photovoltaic devices. One of the most frequently used photoactive building blocks for that purpose is the multiprotein complex photosystem I (PSI). Biophotovoltaic devices similar to DSSCs were fabricated by self-assembly of PSI on 3D nanostructured semiconductor electrodes using a liq. electrolyte as redox mediator. Here, we introduce the implementation of PSI in org. electronic devices that combine the ease of processing of org. semiconductors with the biophotovoltaic activity of PSI.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXos1CjtL0%253D&md5=2ca7ed4b6f064ba7a6480e00fc62f364
9. 9
  Kwiat, M.; Elnathan, R.; Kwak, M.; de Vries, J. W.; Pevzner, A.; Engel, Y.; Burstein, L.; Khatchtourints, A.; Lichtenstein, A.; Flaxer, E.; Herrmann, A.; Patolsky, F. Non-Covalent Monolayer-Piercing Anchoring of Lipophilic Nucleic Acids: Preparation, Characterization, and Sensing Applications J. Am. Chem. Soc. 2012, 134, 280– 292 DOI: 10.1021/ja206639d
  [ACS Full Text ], [CAS], Google Scholar
  9
  Non-covalent Monolayer-Piercing Anchoring of Lipophilic Nucleic Acids: Preparation, Characterization, and Sensing Applications
  Kwiat, Moria; Elnathan, Roey; Kwak, Minseok; de Vries, Jan Willem; Pevzner, Alexander; Engel, Yoni; Burstein, Larisa; Khatchtourints, Artium; Lichtenstein, Amir; Flaxer, Eli; Herrmann, Andreas; Patolsky, Fernando
  Journal of the American Chemical Society (2012), 134 (1), 280-292CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
  Functional interfaces of biomols. and inorg. substrates like semiconductor materials are of utmost importance for the development of highly sensitive biosensors and microarray technol. However, there is still a lot of room for improving the techniques for immobilization of biomols., in particular nucleic acids and proteins. Conventional anchoring strategies rely on attaching biomacromols. via complementary functional groups, appropriate bifunctional linker mols., or non-covalent immobilization via electrostatic interactions. In this work, we demonstrate a facile, new, and general method for the reversible non-covalent attachment of amphiphilic DNA probes contg. hydrophobic units attached to the nucleobases (lipid-DNA) onto SAM-modified gold electrodes, silicon semiconductor surfaces, and glass substrates. We show the anchoring of well-defined amts. of lipid-DNA onto the surface by insertion of their lipid tails into the hydrophobic monolayer structure. The surface coverage of DNA mols. can be conveniently controlled by modulating the initial concn. and incubation time. Further control over the DNA layer is afforded by the addnl. external stimulus of temp. Heating the DNA-modified surfaces at temps. >80 °C leads to the release of the lipid-DNA structures from the surface without harming the integrity of the hydrophobic SAMs. These supramol. DNA layers can be further tuned by anchoring onto a mixed SAM contg. hydrophobic mols. of different lengths, rather than a homogeneous SAM. Immobilization of lipid-DNA on such SAMs has revealed that the surface d. of DNA probes is highly dependent on the compn. of the surface layer and the structure of the lipid-DNA. The formation of the lipid-DNA sensing layers was monitored and characterized by numerous techniques including XPS, quartz crystal microbalance, ellipsometry, contact angle measurements, at. force microscopy, and confocal fluorescence imaging. Finally, this new DNA modification strategy was applied for the sensing of target DNAs using silicon-nanowire field-effect transistor device arrays, showing a high degree of specificity toward the complementary DNA target, as well as single-base mismatch selectivity.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhsVOlt7zF&md5=3bed556154faf58f826dd10e32e57e3f
10. 10
  Kwak, M.; Gao, J.; Prusty, D. K.; Musser, A. J.; Markov, V. A.; Tombros, N.; Stuart, M. C. A.; Browne, W. R.; Boekema, E. J.; ten Brinke, G.; Jonkman, H. T.; van Wees, B. J.; Loi, M. A.; Herrmann, A. DNA Block Copolymer Doing It All: From Selection to Self-Assembly of Semiconducting Carbon Nanotubes Angew. Chem., Int. Ed. 2011, 50, 3206– 3210 DOI: 10.1002/anie.201007098
  [Crossref], [CAS], Google Scholar
  10
  DNA Block Copolymer Doing It All: From Selection to Self-Assembly of Semiconducting Carbon Nanotubes
  Kwak, Minseok; Gao, Jia; Prusty, Deepak K.; Musser, Andrew J.; Markov, Vladimir A.; Tombros, Nikolaos; Stuart, Marc C. A.; Browne, Wesley R.; Boekema, Egbert J.; ten Brinke, Gerrit; Jonkman, Harry T.; van Wees, Bart J.; Loi, Maria A.; Herrmann, Andreas
  Angewandte Chemie, International Edition (2011), 50 (14), 3206-3210, S3206/1-S3206/32CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
  The article presents a strait-forward soln. to many of the key concerns that face SWNT technol. (nondestructive dispersion of individual nanotubes, enrichment of semiconducting species, and precise supramol. addressability) by using amphiphilic DNA block copolymers (DBCs).
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXjsFyqs7g%253D&md5=4a245f8f385b141ab03d65386321bf40
11. 11
  Yuan, J.; Mecerreyes, D.; Antonietti, M. Poly(ionic Liquid)s: An Update Prog. Polym. Sci. 2013, 38, 1009– 1036 DOI: 10.1016/j.progpolymsci.2013.04.002
  [Crossref], [CAS], Google Scholar
  11
  Poly(ionic liquid)s: An update
  Yuan, Jiayin; Mecerreyes, David; Antonietti, Markus
  Progress in Polymer Science (2013), 38 (7), 1009-1036CODEN: PRPSB8; ISSN:0079-6700. (Elsevier Ltd.)
  This review presents a literature survey of recent work on poly(ionic liq.)s or polymd. ionic liqs. (PILs), a class of polyelectrolytes that has attracted rapidly increasing interest over the past few years. The review begins with a short explanation of the interconnection as well as the intrinsic differences between PILs and ionic liqs. Recently reported PIL homopolymers with new chem. structures and synthetic trends are introduced as a complement to the overall PIL synthesis schemes reported previously. In addn., block copolymers and colloidal particles of PILs are described, followed by a discussion of the limitations of PILs due to structural instability under certain conditions and the efforts to understand PIL physics. Examples of recent applications of PILs across a multitude of fields, such as thermoresponsive materials, carbon materials, catalysis, porous polymers, sepn. and absorption materials, and energy harvesting/generation as well as several biol. applications are described in detail.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXmvFymtbY%253D&md5=a348dd9a3b02001d968a37c919426f0e
12. 12
  Wang, R.; Li, J.; Chen, W.; Xu, T.; Yun, S.; Xu, Z.; Xu, Z.; Sato, T.; Chi, B.; Xu, H. A Biomimetic Mussel-Inspired ε-Poly-l-lysine Hydrogel with Robust Tissue-Anchor and Anti-Infection Capacity Adv. Funct. Mater. 2017, 27, 1604894 DOI: 10.1002/adfm.201604894
  [Crossref], Google Scholar
  There is no corresponding record for this reference.
13. 13
  Benight, S. J.; Tok, J. B. H.; Bao, Z.; Wang, C. Stretchable and Self-healing Polymers and Devices for Electronic Skin Prog. Polym. Sci. 2013, 38, 1961– 1977 DOI: 10.1016/j.progpolymsci.2013.08.001
  [Crossref], [CAS], Google Scholar
  13
  Stretchable and self-healing polymers and devices for electronic skin
  Benight, Stephanie J.; Wang, Chao; Tok, Jeffrey B. H.; Bao, Zhenan
  Progress in Polymer Science (2013), 38 (12), 1961-1977CODEN: PRPSB8; ISSN:0079-6700. (Elsevier Ltd.)
  A review. This review covers some of the most recent advances in stretchable and self-healing polymers and devices for Electronic skin (E-skin) applications. Applications for both stretchable and self-healing materials include, but are not limited to, electronics, displays, energy, the environment, and medicine. While the majority of org. materials can generally be rendered flexible, such materials are not stretchable, which is a key mech. property necessary to realize applications of E-skin for prosthetics, artificial intelligence, systems for robotics, personal health monitoring, biocompatibility, and communication devices. In our effort to survey materials utilized in various components of an electronic device, we report herein recent advances in stretchable and self-healing conductors, semiconductors, and substrates. We highlight some key technologies recently developed in stretchable org.-based sensors, solar cells, light-emitting diodes, and self-healing electronic devices.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhtlShsrbM&md5=e50109f11999be38fed58025cbfffb06
14. 14
  Leone, A. M.; Weatherly, S. C.; Williams, M. E.; Thorp, H. H.; Murray, R. W. An Ionic Liquid Form of DNA: Redox-Active Molten Salts of Nucleic Acids J. Am. Chem. Soc. 2001, 123, 218– 222 DOI: 10.1021/ja003332c
  [ACS Full Text ], [CAS], Google Scholar
  14
  An Ionic Liquid Form of DNA: Redox-Active Molten Salts of Nucleic Acids
  Leone, Anthony M.; Weatherly, Stephanie C.; Williams, Mary Elizabeth; Thorp, H. Holden; Murray, Royce W.
  Journal of the American Chemical Society (2001), 123 (2), 218-222CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
  Ionic liqs. are described that contain duplex DNA as the anion and polyether-decorated transition metal complexes based on M(MePEG-bpy)32+ as (M = Fe, Co; MePEG-bpy = 4,4'-(CH3(OCH2CH2)7OCO)2-2,2'-bipyridine). When the undiluted liq. DNA-or molten salt-is interrogated electrochem. by a microelectrode, the molten salts exhibit cyclic voltammograms due to the phys. diffusion (DPHYS) of the polyether-transition metal complex. When M = Co(II), the cyclic voltammogram of the melt shows an oxidative wave due to the Co(III/II) couple at E1/2 = 0.40 V (vs. Ag/AgCl) and a DPHYS of 6 × 10-12 cm2/s, which is significantly lower than that for Co(MePEG-bpy)3(ClO4)2 (DPHYS = 2.6 × 10-10 cm2/s) due to greater viscosity provoked by the DNA polymer. When a 1:1 mixt. is made of the Co(MePEG-bpy)3·DNA and Fe(MePEG-bpy)3(ClO4)2 melts, two redox waves are obsd. The 1st is due to the Co(III/II) couple, and the 2nd is a catalytic wave due to oxidn. of guanine in DNA by electrogenerated Fe(III) in the undiluted melt. Independent expts. show that the Fe(III) form of the complex selectively oxidizes guanine in duplex DNA. These DNA molten salts constitute a new class of materials whose properties can be controlled by nucleic acid sequence and that can be interrogated in undiluted form on microelectrode arrays.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXovVCisrs%253D&md5=3c6ed25ed2f9af71116cb1131b561d54
15. 15
  Bourlinos, A. B.; Ray Chowdhury, S.; Herrera, R.; Jiang, D. D.; Zhang, Q.; Archer, L. A.; Giannelis, E. P. Functionalized Nanostructures with Liquid-Like Behavior: Expanding the Gallery of Available Nanostructures Adv. Funct. Mater. 2005, 15, 1285– 1290 DOI: 10.1002/adfm.200500076
  [Crossref], [CAS], Google Scholar
  15
  Functionalized nanostructures with liquid-like behavior: Expanding the gallery of available nanostructures
  Bourlinos, Athanasios B.; Chowdhury, Subhendu Ray; Herrera, Rafael; Jiang, David D.; Zhang, Qiang; Archer, Lynden A.; Giannelis, Emmanuel P.
  Advanced Functional Materials (2005), 15 (8), 1285-1290CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
  Recently, the authors have developed a novel family of functionalized nanostructures that exhibit liq.-like behavior in the absence of solvents and preserve their nanostructure in the liq. state. The gallery of nanostructures developed so far includes functionalized SiO2 and magnetic Fe oxide nanoparticles, layer-like organosilicate nanoparticles, polyoxometalate clusters, and org.-inorg. hybrid networks. In an effort to demonstrate the wider applicability of this concept and to provide a deeper insight into this class of materials, the present work cites addnl. paradigms of functionalized nanostructures with similar behavior as above. In one case, surface functionalization of anatase nanoparticles (TiO2, an inorg. nanostructure) with a quaternary ammonium organosilane leads to ionically modified nanoparticles that, when electrostatically combined with a poly(ethylene glycol) (PEG)-tailed sulfonate anion, exhibit liq.-like behavior in the absence of solvents. In a different but quite interesting case of a bionanostructure, ion-exchange functionalization of a DNA oligonucleotide with a PEG-tailed quaternary ammonium cation leads to an easily separable liq. deriv. with attractive features. These examples show the versatility of this concept over a range of nanostructures.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXoslGms78%253D&md5=8aa63387e37005ebb049267b94291a35
16. 16
  Liu, K.; Shuai, M.; Chen, D.; Tuchband, M.; Gerasimov, J. Y.; Su, J.; Liu, Q.; Zajaczkowski, W.; Pisula, W.; Müllen, K.; Clark, N. A.; Herrmann, A. Solvent-free Liquid Crystals and Liquids from DNA Chem. - Eur. J. 2015, 21, 4898– 4903 DOI: 10.1002/chem.201500159
  [Crossref], [PubMed], [CAS], Google Scholar
  16
  Solvent-free Liquid Crystals and Liquids from DNA
  Liu, Kai; Shuai, Min; Chen, Dong; Tuchband, Michael; Gerasimov, Jennifer Y.; Su, Juanjuan; Liu, Qing; Zajaczkowski, Wojciech; Pisula, Wojciech; Muellen, Klaus; Clark, Noel A.; Herrmann, Andreas
  Chemistry - A European Journal (2015), 21 (13), 4898-4903CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
  As DNA exhibits persistent structures with dimensions that exceed the range of their intermol. forces, solid-state DNA undergoes thermal degrdn. at elevated temps. Therefore, the realization of solvent-free DNA fluids, including liq. crystals and liqs., still remains a significant challenge. To address this intriguing issue, we demonstrate that combining DNA with suitable cationic surfactants, followed by dehydration, can be a simple generic scheme for producing these solvent-free DNA fluid systems. In the anhyd. smectic liq. cryst. phase, DNA sublayers are intercalated between aliph. hydrocarbon sublayers. The lengths of the DNA and surfactant are found to be extremely important in tuning the phys. properties of the fluids. Stable liq.-cryst. and liq. phases are obtained in the -20 °C to 200 °C temp. range without thermal degrdn. of the DNA. Thus, a new type of DNA-based soft biomaterial has been achieved, which will promote the study and application of DNA in a much broader context.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXmsl2qs7w%253D&md5=fc971ffbf240d228432b19b819e608a6
17. 17
  Perriman, A. W.; Cölfen, H.; Hughes, R. W.; Barrie, C. L.; Mann, S. Solvent-Free Protein Liquids and Liquid Crystals Angew. Chem., Int. Ed. 2009, 48, 6242– 6246 DOI: 10.1002/anie.200903100
  [Crossref], [CAS], Google Scholar
  17
  Solvent-Free Protein Liquids and Liquid Crystals
  Perriman, Adam W.; Coelfen, Helmut; Hughes, Roy W.; Barrie, Claire L.; Mann, Stephen
  Angewandte Chemie, International Edition (2009), 48 (34), 6242-6246, S6242/1-S6242/14CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
  Herein, we report, to our knowledge, the first example of a solvent-free liq. protein. Specifically, we report the prepn. and properties of a protein melt based on a stoichiometric ferritin-polymer nanoscale construct with surface modifications that extend the range of intermol. interactions to a length scale that is commensurate with fluidity in the absence of water. Moreover, we show that these spherically shaped nanoconstructs undergo anisotropic ordering during melting at 30° to produce a viscoelastic protein liq. that exhibits thermotropic liq.-cryst. behavior, and which subsequently transforms to a Newtonian fluid at temps. above 40° and is stable up to a temp. of 405°. The method, which utilizes the site-specificity of surface amino acid residues and high degree of uniformity in ferritin mol. architecture to produce discrete single-component ferritin-polymer constructs, should be readily accessible to exploitation as a facile route to solvent-free liq. proteins and enzymes in general.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXpvFyhur4%253D&md5=7409c2035810bb79e89ce19e5bd62487
18. 18
  Perriman, A. W.; Brogan, A. P. S.; Cölfen, H.; Tsoureas, N.; Owen, G. R.; Mann, S. Reversible Dioxygen Binding in Solvent-Free Liquid Myoglobin Nat. Chem. 2010, 2, 622– 626 DOI: 10.1038/nchem.700
  [Crossref], [PubMed], [CAS], Google Scholar
  18
  Reversible dioxygen binding in solvent-free liquid myoglobin
  Perriman, Adam W.; Brogan, Alex P. S.; Coelfen, Helmut; Tsoureas, Nikolaos; Owen, Gareth R.; Mann, Stephen
  Nature Chemistry (2010), 2 (8), 622-626CODEN: NCAHBB; ISSN:1755-4330. (Nature Publishing Group)
  The ensemble of forces that stabilize protein structure and facilitate biol. function are intimately linked with the ubiquitous aq. environment of living systems. As a consequence, biomol. activity is highly sensitive to the interplay of solvent-protein interactions, and deviation from the native conditions, for example by exposure to increased thermal energy or severe dehydration, results in denaturation and subsequent loss of function. Although certain enzymes can be extd. into non-aq. solvents without significant loss of activity, there are no known examples of solvent-less (molten) liqs. of functional metalloproteins. Here we describe the synthesis and properties of room-temp. solvent-free myoglobin liqs. with near-native structure and reversible dioxygen binding ability equiv. to the haem protein under physiol. conditions. The realization of room-temp. solvent-free myoglobin liqs. with retained function presents novel challenges to existing theories on the role of solvent mols. in structural biol., and should offer new opportunities in protein-based nanoscience and bionanotechnol.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXpt1aksbo%253D&md5=d4dd63a877cdfd44954db927e5740d56
19. 19
  Liu, K.; Pesce, D.; Ma, C.; Tuchband, M.; Shuai, M.; Chen, D.; Su, J.; Liu, Q.; Gerasimov, J. Y.; Kolbe, A.; Zajaczkowski, W.; Pisula, W.; Müllen, K.; Clark, N. A.; Herrmann, A. Solvent-Free Liquid Crystals and Liquids Based on Genetically Engineered Supercharged Polypeptides with High Elasticity Adv. Mater. 2015, 27, 2459– 2465 DOI: 10.1002/adma.201405182
  [Crossref], [PubMed], [CAS], Google Scholar
  19
  Solvent-Free Liquid Crystals and Liquids Based on Genetically Engineered Supercharged Polypeptides with High Elasticity
  Liu, Kai; Pesce, Diego; Ma, Chao; Tuchband, Michael; Shuai, Min; Chen, Dong; Su, Juanjuan; Liu, Qing; Gerasimov, Jennifer Y.; Kolbe, Anke; Zajaczkowski, Wojciech; Pisula, Wojciech; Muellen, Klaus; Clark, Noel A.; Herrmann, Andreas
  Advanced Materials (Weinheim, Germany) (2015), 27 (15), 2459-2465CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
  We developed a series of solvent free GFP functionalized elastin-like protein liq. crystals and liqs. by electrostatic complexation of SUPs with surfactants contg. flexible alkyl chains.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXkvVSiu7c%253D&md5=e1da0277c0a322fd59ce336448aedb7e
20. 20
  Patil, A. J.; McGrath, N.; Barclay, J. E.; Evans, D. J.; Cölfen, H.; Manners, I.; Perriman, A. W.; Mann, S. Liquid Viruses by Nanoscale Engineering of Capsid Surfaces Adv. Mater. 2012, 24, 4557– 4563 DOI: 10.1002/adma.201201032
  [Crossref], Google Scholar
  There is no corresponding record for this reference.
21. 21
  Liu, K.; Chen, D.; Marcozzi, A.; Zheng, L.; Su, J.; Pesce, D.; Zajaczkowski, W.; Kolbe, A.; Pisula, W.; Müllen, K.; Clark, N. A.; Herrmann, A. Thermotropic Liquid Crystals from Biomacromolecules Proc. Natl. Acad. Sci. U. S. A. 2014, 111, 18596– 18600 DOI: 10.1073/pnas.1421257111
  [Crossref], [PubMed], [CAS], Google Scholar
  21
  Thermotropic liquid crystals from biomacromolecules
  Liu, Kai; Chen, Dong; Marcozzi, Alessio; Zheng, Lifei; Su, Juanjuan; Pesce, Diego; Zajaczkowski, Wojciech; Kolbe, Anke; Pisula, Wojciech; Muellen, Klaus; Clark, Noel A.; Herrmann, Andreas
  Proceedings of the National Academy of Sciences of the United States of America (2014), 111 (52), 18596-18600CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
  Complexation of biomacromols. (e.g., nucleic acids, proteins, or viruses) with surfactants contg. flexible alkyl tails, followed by dehydration, is shown to be a simple generic method for the prodn. of thermotropic liq. crystals. The anhyd. smectic phases that result exhibit biomacromol. sublayers intercalated between aliph. hydrocarbon sublayers at or near room temp. Both this and low transition temps. to other phases enable the study and application of thermotropic liq. crystal phase behavior without thermal degrdn. of the biomol. components.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXitFCrt7rO&md5=5ad169c3e83a7d867a26f0502dd7217d
22. 22
  Faul, C. F. J.; Antonietti, M. Ionic Self-Assembly: Facile Synthesis of Supramolecular Materials Adv. Mater. 2003, 15, 673– 683 DOI: 10.1002/adma.200300379
  [Crossref], [CAS], Google Scholar
  22
  Ionic self-assembly: Facile synthesis of supramolecular materials
  Faul, Charl F. J.; Antonietti, Markus
  Advanced Materials (Weinheim, Germany) (2003), 15 (9), 673-683CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
  A review. The technique of ionic self-assembly, i.e., the coupling of structurally different building blocks by electrostatic interactions, a powerful tool to create new material nanostructures and chem. objects, is reviewed with 110 refs. The excellent availability of the starting products (charged tectonic units) and the simplicity of synthesis, by neat addn. and cooperative stoichiometric pptn. with high purity, allow the recombinatorial synthesis of a whole range of functional materials and hybrids with interesting and versatile functions. Diverse combinations between polyelectrolytes, surfactants, inorg. clusters, and extended rigid org. scaffolds are discussed in detail, and the underlying principles of nanostructure formation are illustrated.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXjvFOku7o%253D&md5=36e682555777a250cf508d9f35837821
23. 23
  Wenzel, A.; Antonietti, M. Superstructures of Lipid Bilayers by Complexation with Helical Biopolymers Adv. Mater. 1997, 9, 487– 490 DOI: 10.1002/adma.19970090607
  [Crossref], Google Scholar
  There is no corresponding record for this reference.
24. 24
  General, S.; Antonietti, M. Supramolecular Organization of Oligopeptides, through Complexation with Surfactants Angew. Chem., Int. Ed. 2002, 41, 2957– 2960 DOI: 10.1002/1521-3773(20020816)41:16<2957::AID-ANIE2957>3.0.CO;2-F
  [Crossref], Google Scholar
  There is no corresponding record for this reference.
25. 25
  Brogan, A. P. S.; Siligardi, G.; Hussain, R.; Perriman, A. W.; Mann, S. Hyper-Thermal Stability and Unprecedented Re-Folding of Solvent-Free Liquid Myoglobin Chem. Sci. 2012, 3, 1839– 1846 DOI: 10.1039/c2sc20143g
  [Crossref], [CAS], Google Scholar
  25
  Hyper-thermal stability and unprecedented re-folding of solvent-free liquid myoglobin
  Brogan, Alex P. S.; Siligardi, Giuliano; Hussain, Rohanah; Perriman, Adam W.; Mann, Stephen
  Chemical Science (2012), 3 (6), 1839-1846CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
  Isolating solvent effects by studying proteins in a liq. phase devoid of solvent has not been previously possible because freeze-dried protein solids do not melt but thermally degrade. Herein we circumvent this problem by modifying the interactions between myoglobin mols. via a polymer-surfactant coronal layer to produce a solvent-free liq. phase that is thermally stable over a wide temp. range. Using high-resoln. synchrotron radiation CD and UV-Vis spectroscopies the authors det. the temp.-dependent structure and re-folding behavior of cationized myoglobin under solvent-free conditions, and show that dehydration and subsequent melting of the nanoconstruct has no significant effect on the protein secondary structure at room temp. Significantly, the solvent-free liq. myoglobin mols. exhibit hyper-thermophilic behavior and can be reversibly re-folded by cooling from 155 °C. We attribute the abnormally high thermal stability and persistence of protein folding to entropic contributions assocd. with macromol. crowding and confinement, and propose that re-folding in the absence of a solvent shell is facilitated by the configurational flexibility and mol. interactivity of the polymer surfactant coronal layer.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xnt12qs7s%253D&md5=00d62a628b2267e6cd7ef3f428e56af7
26. 26
  Brogan, A. P. S.; Sharma, K. P.; Perriman, A. W.; Mann, S. Enzyme Activity in Liquid Lipase Melts as a Step towards Solvent-Free Biology at 150 °C Nat. Commun. 2014, 5, 5058 DOI: 10.1038/ncomms6058
  [Crossref], [PubMed], [CAS], Google Scholar
  26
  Enzyme activity in liquid lipase melts as a step towards solvent-free biology at 150 °C
  Brogan, Alex P. S.; Sharma, Kamendra P.; Perriman, Adam W.; Mann, Stephen
  Nature Communications (2014), 5 (), 5058CODEN: NCAOBW; ISSN:2041-1723. (Nature Publishing Group)
  Water mols. play a no. of crit. roles in enzyme catalysis, including mass transfer of substrates and products, nucleophilicity and proton transfer at the active site, and solvent shell-mediated dynamics for accessing catalytically competent conformations. The pervasiveness of water in enzymolysis therefore raises the question concerning whether biocatalysis can be undertaken in the absence of a protein hydration shell. Lipase-mediated catalysis has been undertaken with reagent-based solvents and lyophilized powders, but there are no examples of molecularly dispersed enzymes that catalyze reactions at sub-solvation levels within solvent-free melts. Here we describe the synthesis, properties and enzyme activity of self-contained reactive biofluids based on solvent-free melts of lipase-polymer surfactant nanoconjugates. Desiccated substrates in liq. (p-nitrophenyl butyrate) or solid (p-nitrophenyl palmitate) form can be mixed or solubilized, resp., into the enzyme biofluids, and hydrolyzed in the solvent-free state. Significantly, the efficiency of product formation increases as the temp. is raised to 150 °C.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXksVCitrs%253D&md5=843ed216df21037c70e57d5b0082f4c6
27. 27
  Sharma, K. P.; Risbridger, T.; Bradley, K.; Perriman, A. W.; Fermin, D. J.; Mann, S. High-Temperature Electrochemistry of a Solvent-Free Myoglobin Melt ChemElectroChem 2015, 2, 976– 981 DOI: 10.1002/celc.201500094
  [Crossref], [CAS], Google Scholar
  27
  High-Temperature Electrochemistry of a Solvent-Free Myoglobin Melt
  Sharma, Kamendra P.; Risbridger, Thomas; Bradley, Kieren; Perriman, Adam W.; Fermin, David J.; Mann, Stephen
  ChemElectroChem (2015), 2 (7), 976-981CODEN: CHEMRA; ISSN:2196-0216. (Wiley-VCH Verlag GmbH & Co. KGaA)
  The electrochem. responses from a hybrid biofluid comprising lithium hexafluorophosphate (LiPF6) dispersed in a solvent-free myoglobin melt are investigated over an extreme temp. range (30-150°C). Incorporation of LiPF6 resulted in an approx. 20-fold increase in the cond. of the biofluid across the entire temp. range. A polaron-type mechanism involving electron hopping from heme-to-heme centers of myoglobin, accompanied by extrinsic Li counter-ion movement, is proposed for the charge-transport kinetics in the solvent-free melt. Significantly, the redox signature of the heme prosthetic group varied systematically and reversibly with temp., which was consistent with hyperthermophilic unfolding/refolding of the protein structure.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtFCjsbzK&md5=ed325f1247b818528aef352037487665
28. 28
  Liu, K.; Varghese, J.; Gerasimov, J. Y.; Polyakov, A. O.; Shuai, M.; Su, J.; Chen, D.; Zajaczkowski, W.; Marcozzi, A.; Pisula, W.; Noheda, B.; Palstra, T. T. M.; Clark, N. A.; Herrmann, A. Controlling the Volatility of the Written Optical State in Electrochromic DNA Liquid Crystals Nat. Commun. 2016, 7, 11476 DOI: 10.1038/ncomms11476
  [Crossref], [PubMed], [CAS], Google Scholar
  28
  Controlling the volatility of the written optical state in electrochromic DNA liquid crystals
  Liu, Kai; Varghese, Justin; Gerasimov, Jennifer Y.; Polyakov, Alexey O.; Shuai, Min; Su, Juanjuan; Chen, Dong; Zajaczkowski, Wojciech; Marcozzi, Alessio; Pisula, Wojciech; Noheda, Beatriz; Palstra, Thomas T. M.; Clark, Noel A.; Herrmann, Andreas
  Nature Communications (2016), 7 (), 11476CODEN: NCAOBW; ISSN:2041-1723. (Nature Publishing Group)
  Liq. crystals are widely used in displays for portable electronic information display. To broaden their scope for other applications like smart windows and tags, new material properties such as polarizer-free operation and tunable memory of a written state become important. Here, we describe an anhyd. nanoDNA-surfactant thermotropic liq. crystal system, which exhibits distinctive elec. controlled optical absorption, and temp.-dependent memory. In the liq. crystal isotropic phase, elec. field-induced coloration and bleaching have a switching time of seconds. Upon transition to the smectic liq. crystal phase, optical memory of the written state is obsd. for many hours without applied voltage. The reorientation of the DNA-surfactant lamellar layers plays an important role in preventing color decay. Thereby, the volatility of optoelectronic state can be controlled simply by changing the phase of the material. This research may pave the way for developing a new generation of DNA-based, phase-modulated, photoelectronic devices.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XnslWktL4%253D&md5=e6a1c65c6ef7a1f61d4d776a94b6e2f1
29. 29
  Doye, J. P. K.; Wales, D. J. The Effect of the Range of the Potential on the Structure and Stability of Simple Liquids: From Clusters to Bulk, from Sodium to C-60 J. Phys. B: At., Mol. Opt. Phys. 1996, 29, 4859– 4894 DOI: 10.1088/0953-4075/29/21/002
  [Crossref], [CAS], Google Scholar
  29
  The effect of the range of the potential on the structure and stability of simple liquids: from clusters to bulk, from sodium to C60
  Doye, Jonathan P. K.; Wales, David J.
  Journal of Physics B: Atomic, Molecular and Optical Physics (1996), 29 (21), 4859-4894CODEN: JPAPEH; ISSN:0953-4075. (Institute of Physics Publishing)
  A review with 103 refs. For systems with sufficiently short-ranged interparticle forces, such as some colloidal systems and perhaps C60, the liq. phase can be thermodynamically unstable. By analyzing the effect of the range of the interat. forces on the multidimensional potential energy surfaces of bulk material and clusters, a microscopic view of this phenomenon is provided. Structural anal. of the min. on the potential energy surface provides evidence for the polytetrahedral character of the liq. phase, and allows us to examine the evolution of the phase-like forms of clusters to the bulk limit. We find that essentially bulk-like liq. structure can develop in clusters with as few as 55 atoms. The effect of the range of the potential on the thermodn. is illustrated by a series of simulations of 55-atom clusters. For small clusters bound by long-ranged potentials, the lowest energy min. has an amorphous structure typical of the liq.-like state. This suggests an explanation for the transition from electronic to geometric magic nos. obsd. in the mass spectra of sodium clusters.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXitVWmsA%253D%253D&md5=043ea300336e37b2072a6fbdb0dd28ab
30. 30
  Min, Y.; Akbulut, M.; Kristiansen, K.; Golan, Y.; Israelachvili, J. The Role of Interparticle and External Forces in Nanoparticle Assembly Nat. Mater. 2008, 7, 527– 538 DOI: 10.1038/nmat2206
  [Crossref], [PubMed], [CAS], Google Scholar
  30
  The role of interparticle and external forces in nanoparticle assembly
  Min, Younjin; Akbulut, Mustafa; Kristiansen, Kai; Golan, Yuval; Israelachvili, Jacob
  Nature Materials (2008), 7 (7), 527-538CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
  A review. The past 20 years have witnessed simultaneous multidisciplinary explosions in exptl. techniques for synthesizing new materials, measuring and manipulating nanoscale structures, understanding biol. processes at the nanoscale, and carrying out large-scale computations of many-atom and complex macromol. systems. These advances have led to the new disciplines of nanoscience and nanoengineering. For reasons that are discussed here, most nanoparticles do not 'self-assemble' into their thermodynamically lowest energy state, and require an input of energy or external forces to 'direct' them into particular structures or assemblies. We discuss why and how a combination of self- and directed-assembly processes, involving interparticle and externally applied forces, can be applied to produce desired nanostructured materials.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXnslKqsrc%253D&md5=53d6916315dccf43b9d72be033f6453a
31. 31
  Hagen, M. H. J.; Meijer, E. J.; Mooij, G. C. a. M.; Frenkel, D.; Lekkerkerker, H. N. W. Does C60 Have a Liquid Phase? Nature 1993, 365, 425– 426 DOI: 10.1038/365425a0
  [Crossref], [CAS], Google Scholar
  31
  Does fullerene C60 have a liquid phase?
  Hagen, M. H. J.; Meijer, E. J.; Mooij, G. C. A. M.; Frenkel, D.; Lekkerkerker, H. N. W.
  Nature (London, United Kingdom) (1993), 365 (6445), 425-6CODEN: NATUAS; ISSN:0028-0836.
  Results are presented which suggest that C60 has no liq. phase. The phase diagram was mapped out using computer simulations in which the C60 mols. are represented by spheres interacting via Lennard-Jones potentials summed over all 60 C atoms. The sublimation line passes above the metastable liq.-vapor coexistence curve. By drawing an analogy with the aggregation of colloidal particles, solid C60 formed by nucleation from the vapor phase will probably be amorphous rather than cryst.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3sXmsFKqtr4%253D&md5=d290ac7d28b2a01d52ed77fa6679d3cc
32. 32
  Perriman, A. W.; Mann, S. Liquid Proteins—A New Frontier for Biomolecule-Based Nanoscience ACS Nano 2011, 5, 6085– 6091 DOI: 10.1021/nn202290g
  [ACS Full Text ], Google Scholar
  There is no corresponding record for this reference.
33. 33
  Bishop, K. J. M.; Wilmer, C. E.; Soh, S.; Grzybowski, B. A. Nanoscale Forces and Their Uses in Self-Assembly Small 2009, 5, 1600– 1630 DOI: 10.1002/smll.200900358
  [Crossref], [PubMed], [CAS], Google Scholar
  33
  Nanoscale forces and their uses in self-assembly
  Bishop, Kyle J. M.; Wilmer, Christopher E.; Soh, Siowling; Grzybowski, Bartosz A.
  Small (2009), 5 (14), 1600-1630CODEN: SMALBC; ISSN:1613-6810. (Wiley-VCH Verlag GmbH & Co. KGaA)
  A review. The ability to assemble nanoscopic components into larger structures and materials depends crucially on the ability to understand in quant. detail and subsequently "engineer" the interparticle interactions. This Review provides a crit. examn. of the various interparticle forces (van der Waals, electrostatic, magnetic, mol., and entropic) that can be used in nanoscale self-assembly. For each type of interaction, the magnitude and the length scale are discussed, as well as the scaling with particle size and interparticle distance. In all cases, the discussion emphasizes characteristics unique to the nanoscale. These theor. considerations are accompanied by examples of recent exptl. systems, in which specific interaction types were used to drive nanoscopic self-assembly. Overall, this Review aims to provide a comprehensive yet easily accessible resource of nanoscale-specific interparticle forces that can be implemented in models or simulations of self-assembly processes at this scale.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXpsV2ltLg%253D&md5=6bf8d9f5c31d0769c351c72fd6d13099
34. 34
  Faul, C. F. J. Ionic Self-Assembly for Functional Hierarchical Nanostructured Materials Acc. Chem. Res. 2014, 47, 3428– 3438 DOI: 10.1021/ar500162a
  [ACS Full Text ], [CAS], Google Scholar
  34
  Ionic Self-Assembly for Functional Hierarchical Nanostructured Materials
  Faul, Charl F. J.
  Accounts of Chemical Research (2014), 47 (12), 3428-3438CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
  A review. The challenge of constructing soft functional materials over multiple length scales can be addressed by a no. of different routes based on the principles of self-assembly, with the judicious use of various noncovalent interactions providing the tools to control such self-assembly processes. It is within the context of this challenge that we have extensively explored the use of an important approach for materials construction over the past decade: exploiting electrostatic interactions in our ionic self-assembly (ISA) method. In this approach, cooperative assembly of carefully chosen charged surfactants and oppositely charged building blocks (or tectons) provides a facile noncovalent route for the rational design and prodn. of functional nanostructured materials. Generally, our research efforts have developed with an initial focus on establishing rules for the construction of novel noncovalent liq.-cryst. (LC) materials. We found that the use of double-tailed surfactant species (esp. branched double-tailed surfactants) led to the facile formation of thermotropic (and, in certain cases, lyotropic) phases, as demonstrated by extensive temp.-dependent X-ray and light microscopy investigations. From this core area of activity, research expanded to cover issues beyond simple construction of anisotropic materials, turning to the challenge of inclusion and exploitation of switchable functionality. The use of photoactive azobenzene-contg. ISA materials afforded opportunities to exploit both photo-orientation and surface relief grating formation. The prepn. of these anisotropic LC materials was of interest, as the aim was the facile prodn. of disposable and low-cost optical components for display applications and data storage. However, the prohibitive cost of the photo-orientation processes hampered further exploitation of these materials. We also expanded our activities to explore ISA of biol. relevant tectons, specifically deoxyguanosine monophosphate. This approach proved, in combination with block copolymer (BCP) self-assembly, very fruitful for the construction of complex and hierarchical functional materials across multiple length scales. Mol. frustration and incommensurability, which played a major role in structure formation in combination with nucleotide assembly, have now become important tools to tune supramol. structure formation. These concepts, i.e., the use of BCP assembly and incommensurability, in combination with metal-contg. polymeric materials, have provided access to novel supramol. morphologies and, more importantly, design rules to prep. such constructs. These design rules are now also being applied to the assembly of electroactive oligo(aniline)-based materials for the prepn. of highly ordered functional soft materials, and present an opportunity for materials development for applications in energy storage. In this Account, we therefore discuss investigations into (i) the inclusion and prepn. of supramol. photoactive and electroactive materials; (ii) the exploitation and control over multiple noncovalent interactions to fine-tune function, internal structure, and long-range order and (iii) exploration of construction over multiple length scales by combination of ISA with well-known BCP self-assembly. Combination of ISA with tuning of vol. fractions, mutual compatibility, and mol. frustration now provides a versatile tool kit to construct complex and hierarchical functional materials in a facile noncovalent way. A direct challenge for future ISA activities would certainly be the construction of functional mesoscale objects. However, within a broader scientific context, the challenge would be to exploit this powerful assembly tool for application in areas of research with societal impact, for example, energy storage and generation. The hope is that this Account will provide a platform for such future research activities and opportunities.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsFWjsbbN&md5=04fb1a815df13d4049a7b0e305e15a11
35. 35
  Radler, J. O.; Salditt, T.; Safinya, C. R.; Koltover, I. Structure of DNA-cationic Liposome Complexes: DNA Intercalation In Multilamellar Membranes in Distinct Interhelical Packing Regimes Science 1997, 275, 810– 814 DOI: 10.1126/science.275.5301.810
  [Crossref], [PubMed], [CAS], Google Scholar
  35
  Structure of DNA-cationic liposome complexes: DNA intercalation in multilamellar membranes in distinct interhelical packing regimes
  Radler J O; Koltover I; Salditt T; Safinya C R
  Science (New York, N.Y.) (1997), 275 (5301), 810-4 ISSN:0036-8075.
  Cationic liposomes complexed with DNA (CL-DNA) are promising synthetically based nonviral carriers of DNA vectors for gene therapy. The solution structure of CL-DNA complexes was probed on length scales from subnanometer to micrometer by synchrotron x-ray diffraction and optical microscopy. The addition of either linear lambda-phage or plasmid DNA to CLs resulted in an unexpected topological transition from liposomes to optically birefringent liquid-crystalline condensed globules. X-ray diffraction of the globules revealed a novel multilamellar structure with alternating lipid bilayer and DNA monolayers. The lambda-DNA chains form a one-dimensional lattice with distinct interhelical packing regimes. Remarkably, in the isoelectric point regime, the lambda-DNA interaxial spacing expands between 24.5 and 57.1 angstroms upon lipid dilution and is indicative of a long-range electrostatic-induced repulsion that is possibly enhanced by chain undulations.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADyaK2s7msFOlsw%253D%253D&md5=9f24e0a90b0ce561d0b164d1fb0bab71
36. 36
  Dias, R.; Mel'nikov, S.; Lindman, B.; Miguel, M. G. DNA Phase Behavior in the Presence of Oppositely Charged Surfactants Langmuir 2000, 16, 9577– 9583 DOI: 10.1021/la000640f
  [ACS Full Text ], [CAS], Google Scholar
  36
  DNA phase behavior in the presence of oppositely charged surfactants
  Dias, Rita; Mel'nikov, Sergey; Lindman, Bjoern; Miguel, Maria G.
  Langmuir (2000), 16 (24), 9577-9583CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
  The interaction between DNA and alkyltrimethylammonium bromides of various chain lengths has been investigated. It is known that these systems phase sep. with the formation of a ppt.; this important feature allows, for example, purifn. of nucleic acids. Phase maps were drawn for the aq. systems illustrating the associative phase sepn. The boundary of the 2-phase region for the dil. part of the phase diagram was evaluated by turbidimetry, in both the absence and presence of salt. The extension of the ppt. region increases strongly with the surfactant alkyl chain length, and no redissoln. with an excess of surfactant was obsd. The addn. of NaBr led to novel interesting findings. The phase diagram studies were correlated with the single mol. conformational behavior of the same systems as studied for very dild. solns. by fluorescence microscopy. DNA exhibits a discrete phase transition in the presence of cationic surfactants from coils to globules. Results demonstrate that the coil-globule coexistence interval is narrow for CTAB and becomes wider for the shorter-chained surfactant. The findings for flexible polyions of lower charge d. differ qual. from that found for DNA. For the first, large amts. of surfactant have to be added before phase sepn. occurs, and the change in the polyion extension is gradual, indicating an essentially uniform distribution of surfactant aggregates among the different polyions. For DNA, the very low values of surfactant concn. at which phase sepn. starts demonstrate a different binding interaction; as binding to a polyion starts, further binding is facilitated, and one DNA mol. is satd. before binding starts at another.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXnslSht78%253D&md5=04e97af6a5f9fb7e2182fa769feafe99
37. 37
  Neumann, T.; Gajria, S.; Tirrell, M.; Jaeger, L. Reversible Structural Switching of a DNA–DDAB Film J. Am. Chem. Soc. 2009, 131, 3440– 3441 DOI: 10.1021/ja809349m
  [ACS Full Text ], Google Scholar
  There is no corresponding record for this reference.
38. 38
  Liu, K.; Zheng, L.; Liu, Q.; de Vries, J. W.; Gerasimov, J. Y.; Herrmann, A. Nucleic Acid Chemistry in the Organic Phase: From Functionalized Oligonucleotides to DNA Side Chain Polymers J. Am. Chem. Soc. 2014, 136, 14255– 14262 DOI: 10.1021/ja5080486
  [ACS Full Text ], [CAS], Google Scholar
  38
  Nucleic Acid Chemistry in the Organic Phase: From Functionalized Oligonucleotides to DNA Side Chain Polymers
  Liu, Kai; Zheng, Lifei; Liu, Qing; de Vries, Jan Willem; Gerasimov, Jennifer Y.; Herrmann, Andreas
  Journal of the American Chemical Society (2014), 136 (40), 14255-14262CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
  DNA-incorporating hydrophobic moieties can be synthesized by either solid-phase or soln.-phase coupling. On a solid support the DNA is protected, and hydrophobic units are usually attached employing phosphoramidite chem. involving a DNA synthesizer. On the other hand, soln. coupling in aq. medium results in low yields due to the solvent incompatibility of DNA and hydrophobic compds. Hence, the development of a general coupling method for producing amphiphilic DNA conjugates with high yield in soln. remains a major challenge. Here, we report an org.-phase coupling strategy for nucleic acid modification and polymn. by introducing a hydrophobic DNA-surfactant complex as a reactive scaffold. A remarkable range of amphiphile-DNA structures (DNA-pyrene, DNA-triphenylphosphine, DNA-hydrocarbon, and DNA block copolymers) and a series of new brush-type DNA side-chain homopolymers with high DNA grafting d. are produced efficiently. We believe that this method is an important breakthrough in developing a generalized approach to synthesizing functional DNA mols. for self-assembly and related technol. applications.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhs1CnsrnJ&md5=9b1d1f81232b941dc831be813d991a13
39. 39
  Chen, W.; Gerasimov, J. Y.; Zhao, P.; Liu, K.; Herrmann, A. High-Density Noncovalent Functionalization of DNA by Electrostatic Interactions J. Am. Chem. Soc. 2015, 137, 12884– 12889 DOI: 10.1021/jacs.5b05432
  [ACS Full Text ], [CAS], Google Scholar
  39
  High-Density Noncovalent Functionalization of DNA by Electrostatic Interactions
  Chen, Wei; Gerasimov, Jennifer Y.; Zhao, Pei; Liu, Kai; Herrmann, Andreas
  Journal of the American Chemical Society (2015), 137 (40), 12884-12889CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
  Preserving DNA hybridization in org. solvents could someday serve to significantly extend the applicability of DNA-based technologies. Here, the authors present a method that can be used to solubilize double-stranded DNA at high concns. in org. media. This method requires first pptg. a DNA mol. from the aq. environment with an anilinium deriv. and subsequently exchanging this moiety with an amine-contg. surfactant in org. solvent. This method yields complete exchange of the surfactant and allows for the modification of DNA with hydrophobic primary, secondary, and tertiary alkylamines and ordered functional π-systems. Using this approach, the authors fabricate a multichromophoric light harvesting system that would be unattainable by traditional methods. Addnl., this method makes it possible to use small, hydrophilic mols. to solubilize DNA in org. solvents, which reduces the shielding around the DNA and makes the macromol. more accessible for further chem. modification. The authors believe that this approach will prove tremendously beneficial in expanding the scope of DNA-based nano- and biotechnologies.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhsFGltLfN&md5=9c61742e8a4f2f70f35c47ed80a87964
40. 40
  Strzelecka, T. E.; Davidson, M. W.; Rill, R. L. Multiple Liquid Crystal Phases of DNA at High Concentrations Nature 1988, 331, 457– 460 DOI: 10.1038/331457a0
  [Crossref], [PubMed], [CAS], Google Scholar
  40
  Multiple liquid crystal phases of DNA at high concentrations
  Strzelecka, Teresa E.; Davidson, Michael W.; Rill, Randolph L.
  Nature (London, United Kingdom) (1988), 331 (6155), 457-60CODEN: NATUAS; ISSN:0028-0836.
  DNA forms ≥3 distinct liq. cryst. phases at concns. comparable to those in vivo, with phase transitions occurring over relatively narrow ranges of DNA concn. A weakly birefringent, dynamic, precholesteric mesophase with microscopic textures intermediate between those of a nematic and a true cholesteric phase forms at the lowest concns. required for phase sepn. At slightly higher DNA concns., a 2nd mesophase forms which is a strongly birefringent, well-ordered cholesteric phase with a concn.-dependent pitch of 2-10 μm. At the highest DNA concns., a phase forms which is 2-dimensionally ordered and resembles smectic phases of thermotropic liq. crystals obsd. with small mols.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL1cXht1Kru74%253D&md5=6ef25005329d68876cdcfbf09907a9c4
41. 41
  Nakata, M.; Zanchetta, G.; Chapman, B. D.; Jones, C. D.; Cross, J. O.; Pindak, R.; Bellini, T.; Clark, N. A. End-to-end Stacking and Liquid Crystal Condensation of 6-to-20-base Pair DNA Duplexes Science 2007, 318, 1276– 1279 DOI: 10.1126/science.1143826
  [Crossref], [PubMed], [CAS], Google Scholar
  41
  End-to-End Stacking and Liquid Crystal Condensation of 6-to 20-Base Pair DNA Duplexes
  Nakata, Michi; Zanchetta, Giuliano; Chapman, Brandon D.; Jones, Christopher D.; Cross, Julie O.; Pindak, Ronald; Bellini, Tommaso; Clark, Noel A.
  Science (Washington, DC, United States) (2007), 318 (5854), 1276-1279CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
  Short complementary B-form DNA oligomers, 6 to 20 base pairs in length, are found to exhibit nematic and columnar liq. crystal phases, even though such duplexes lack the shape anisotropy required for liq. crystal ordering. Structural study shows that these phases are produced by the end-to-end adhesion and consequent stacking of the duplex oligomers into polydisperse anisotropic rod-shaped aggregates, which can order into liq. crystals. Upon cooling mixed solns. of short DNA oligomers, in which only a small fraction of the DNA present is complementary, the duplex-forming oligomers phase-sep. into liq. crystal droplets, leaving the unpaired single strands in isotropic soln. In a chem. environment where oligomer ligation is possible, such ordering and condensation would provide an autocatalytic link whereby complementarity promotes the extended polymn. of complementary oligomers.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXhtlGmtbfP&md5=ae96e38beb2cc91ec9799903c76bac7b
42. 42
  Brach, K.; Matczyszyn, K.; Olesiak-Banska, J.; Gordel, M.; Samoc, M. Stabilization of DNA Liquid Crystals on Doping with Gold Nanorods Phys. Chem. Chem. Phys. 2016, 18, 7278– 7283 DOI: 10.1039/C5CP07026K
  [Crossref], Google Scholar
  There is no corresponding record for this reference.
43. 43
  Leone, A. M.; Tibodeau, J. D.; Bull, S. H.; Feldberg, S. W.; Thorp, H. H.; Murray, R. W. Ion Atmosphere Relaxation and Percolative Electron Transfer in Co Bipyridine DNA Molten Salts J. Am. Chem. Soc. 2003, 125, 6784– 6790 DOI: 10.1021/ja0348795
  [ACS Full Text ], Google Scholar
  There is no corresponding record for this reference.
44. 44
  Szalai, V. A.; Thorp, H. H. Electron Transfer in Tetrads: Adjacent Guanines Are Not Hole Traps in G Quartets J. Am. Chem. Soc. 2000, 122, 4524– 4525 DOI: 10.1021/ja0001355
  [ACS Full Text ], Google Scholar
  There is no corresponding record for this reference.
45. 45
  Candeias, L. P.; Steenken, S. Structure and Acid-Base Properties of One-Electron-Oxidized Deoxyguanosine, Guanosine, and 1-Methylguanosine J. Am. Chem. Soc. 1989, 111, 1094– 1099 DOI: 10.1021/ja00185a046
  [ACS Full Text ], [CAS], Google Scholar
  45
  Structure and acid-base properties of one-electron-oxidized deoxyguanosine, guanosine, and 1-methylguanosine
  Candeias, L. P.; Steenken, S.
  Journal of the American Chemical Society (1989), 111 (3), 1094-9CODEN: JACSAT; ISSN:0002-7863.
  The oxidn. of deoxyguanosine and its derivs., guanosine and 1-methylguanosine, by the 1-electron oxidants SO4•- and B2•- was studied following pulsed radiolysis in aq. soln. All 3 compds. reacted with SO4•- with nearly diffusion controlled rates and with Br2•- at rates of ≈5 × 107 M-1 s-1. At pH 7, the 1-electron oxidn. products were neutral radicals, formed by deprotonation from N(1) for guanosine and deoxyguanosine and from exocyclic N2 for 1-methylguanosine. The deoxyguanosine and guanosine radicals further deprotonate to give radical anions with pKa values of 10.8 and 10.7, resp. The results indicate that in the radiation chem. of DNA, the radical cation formed upon ionization of the guanine moiety shifts a proton to its complementary base cytosine.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL1MXltlOktg%253D%253D&md5=44185c0ceb937fff0f44e17bfed53174
46. 46
  Rokhlenko, Y.; Cadet, J.; Geacintov, N. E.; Shafirovich, V. Mechanistic Aspects of Hydration of Guanine Radical Cations in DNA J. Am. Chem. Soc. 2014, 136, 5956– 5962 DOI: 10.1021/ja412471u
  [ACS Full Text ], [CAS], Google Scholar
  46
  Mechanistic Aspects of Hydration of Guanine Radical Cations in DNA
  Rokhlenko, Yekaterina; Cadet, Jean; Geacintov, Nicholas E.; Shafirovich, Vladimir
  Journal of the American Chemical Society (2014), 136 (16), 5956-5962CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
  The mechanistic aspects of hydration of guanine radical cations, G•+ in double- and single-stranded oligonucleotides were investigated by direct time-resolved spectroscopic monitoring methods. The G•+ radical one-electron oxidn. products were generated by SO4•- radical anions derived from the photolysis of S2O82- anions by 308 nm laser pulses. In neutral aq. solns. (pH 7.0), after the complete decay of SO4•- radicals (∼5 μs after the actinic laser flash) the transient absorbance of neutral guanine radicals, G(-H)• with max. at 312 nm, is dominant. The kinetics of decay of G(-H)• radicals depend strongly on the DNA secondary structure. In double-stranded DNA (dsDNA), the G(-H)• decay is biphasic with one component decaying with a lifetime of ∼2.2 ms and the other with a lifetime of ∼0.18 s. By contrast, in single-stranded DNA (ssDNA) the G(-H)• radicals decay monophasically with a ∼ 0.28 s lifetime. The ms decay component in double-stranded DNA is correlated with the enhancement of 8-oxo-7,8-dihydroguanine (8-oxoG) yields which are ∼7 greater than in single-stranded DNA. In double-stranded DNA, it is proposed that the G(-H)• radicals retain radical cation character by sharing the N1-proton with the N3-site of C in the [G•+:C] base pair. This [G(-H)•:H+C G•+:C] equil. allows for the hydration of G•+ followed by formation of 8-oxoG. By contrast, in single-stranded DNA, deprotonation of G•+ and the irreversible escape of the proton into the aq. phase competes more effectively with the hydration mechanism, thus diminishing the yield of 8-oxoG, as obsd. exptl.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXltF2lsr8%253D&md5=629da5e8fef8cf2f31f3fa774b80e544
47. 47
  Bourlinos, A. B.; Herrera, R.; Chalkias, N.; Jiang, D. D.; Zhang, Q.; Archer, L. A.; Giannelis, E. P. Surface-Functionalized Nanoparticles with Liquid-Like Behavior Adv. Mater. 2005, 17, 234– 237 DOI: 10.1002/adma.200401060
  [Crossref], [CAS], Google Scholar
  47
  Surface-functionalized nanoparticles with liquid-like behavior
  Bourlinos, Athanasios B.; Herrera, Rafael; Chalkias, Nikolaos; Jiang, David D.; Zhang, Qiang; Archer, Lynden A.; Giannelis, Emmanuel P.
  Advanced Materials (Weinheim, Germany) (2005), 17 (2), 234-237CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
  Surface functionalization of silica or maghemite (γ-Fe2O3) nanoparticles with a quaternary ammonium organosilane leads to ionically modified nanoparticles that, depending on the nature of the counterion, exhibit liq.-like behavior in the absence of solvents. Solvent-free nanosalts composed of modified silica nanoparticles can be used to dissolve and polymerize pyrrole, while nanosalts composed of maghemite nanoparticles can form solvent-free ferrofluids.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXht12lur4%253D&md5=655948161182337fe5683d018695030f
48. 48
  Rodriguez, R.; Herrera, R.; Archer, L. A.; Giannelis, E. P. Nanoscale Ionic Materials Adv. Mater. 2008, 20, 4353– 4358 DOI: 10.1002/adma.200801975
  [Crossref], [CAS], Google Scholar
  48
  Nanoscale ionic materials
  Rodriguez, Robert; Herrera, Rafael; Archer, Lynden A.; Giannelis, Emmanuel P.
  Advanced Materials (Weinheim, Germany) (2008), 20 (22), 4353-4358CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
  Polymer nanocomposites (nanoparticles dispersed in a polymer matrix) were the subject of intense research for almost two decades in both academic and industrial settings. This interest was fueled by the ability of nanocomposites to not only improve the performance of polymers, but also by their ability to introduce new properties. Yet, there are still challenges that polymer nanocomposites must overcome to reach their full potential. In this Research News article a new class of hybrids termed nanoparticle ionic materials (NIMS) are discussed. NIMS are org.-inorg. hybrid materials comprising a nanoparticle core functionalized with a covalently tethered ionic corona. They are facilely engineered to display flow properties that span the range from glassy solids to free flowing liqs. These new systems have unique properties that can overcome some of the challenges facing nanocomosite materials.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhsVOhu7vO&md5=b578d0e300c2f1bfce66ec55a17084b7
49. 49
  Fernandes, N. J.; Wallin, T. J.; Vaia, R. A.; Koerner, H.; Giannelis, E. P. Nanoscale Ionic Materials Chem. Mater. 2014, 26, 84– 96 DOI: 10.1021/cm402372q
  [ACS Full Text ], [CAS], Google Scholar
  49
  Nanoscale Ionic Materials
  Fernandes, Nikhil J.; Wallin, Thomas J.; Vaia, Richard A.; Koerner, Hilmar; Giannelis, Emmanuel P.
  Chemistry of Materials (2014), 26 (1), 84-96CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
  A review. Within the general field of polymer grafted or hairy nanoparticles, nanoscale ionic materials (NIMs), consisting of a soft polymeric canopy bound to a well-defined nanoparticle core by an ionic bond, occupy a growing niche. They are the first example of neat, self-suspended fluids of nanoparticles (i.e., in the absence of a suspending medium). As such, the perennial dispersion challenges assocd. with polymer nanocomposites are minimized while the dynamic nature of the ionic bonds provides opportunities for self-healing behavior. Combining the properties of ionic liqs., charged colloid suspensions, and well-dispersed nanocomposites, this new materials platform offers remarkable versatility for current and future applications. This perspective covers techniques and current challenges in synthesis, discusses the state of understanding of the theory behind their structure and properties, and examines successes and future prospects in application in a no. of areas, notably in energy-related technologies.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhsV2ltr3I&md5=2693f51d90a3b2927930a7dd0f936018
50. 50
  Cavallo, L.; Kleinjung, J.; Fraternali, F. POPS: A Fast Algorithm for Solvent Accessible Surface Areas at Atomic and Residue Level Nucleic Acids Res. 2003, 31, 3364– 3366 DOI: 10.1093/nar/gkg601
  [Crossref], [PubMed], [CAS], Google Scholar
  50
  POPS: a fast algorithm for solvent accessible surface areas at atomic and residue level
  Cavallo, Luigi; Kleinjung, Jens; Fraternali, Franca
  Nucleic Acids Research (2003), 31 (13), 3364-3366CODEN: NARHAD; ISSN:0305-1048. (Oxford University Press)
  POPS (Parameter Optimized Surfaces) is a new method to calc. solvent accessible surface areas, which is based on an empirically parameterizable anal. formula and fast to compute. At. and residue areas (the latter represented by a single sphere centered on the Cα atom of amino acids and at the P atom of nucleotides) have been optimized vs. accurate all-atom methods. The parameterization has been derived from a selected dataset of proteins and nucleic acids of different sizes and topologies. The residue based approach POPS-R, has been devised as a useful tool for the anal. of large macromol. assemblies like the ribosome and it is specially suited for the refinement of low resoln. structures. POPS-R also allows for ests. of the loss of free energy of solvation upon complex formation, which should be particularly useful for the design of new protein-protein and protein-nucleic acid complexes.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXltVWisrk%253D&md5=967b4a0f2a96a800d64e28624897b6bf
51. 51
  Costantino, H. R.; Curley, J. G.; Hsu, C. C. Determining the Water Sorption Monolayer of Lyophilized Pharmaceutical Proteins J. Pharm. Sci. 1997, 86, 1390– 1393 DOI: 10.1021/js9701566
  [Crossref], [PubMed], [CAS], Google Scholar
  51
  Determining the Water Sorption Monolayer of Lyophilized Pharmaceutical Proteins
  Costantino, Henry R.; Curley, Janet G.; Hsu, Chung C.
  Journal of Pharmaceutical Sciences (1997), 86 (12), 1390-1393CODEN: JPMSAE; ISSN:0022-3549. (American Chemical Society)
  The concept of monolayer water coverage is useful in the development of lyophilized protein formulations. Herein, the authors explored 3 different methodologies to det. the water monolayer for pharmaceutical proteins: (1) theor. prediction based on the amino acid compn. and their relative propensities to sorb water; (2) a traditional adsorption isotherm measurement by Karl Fisher water titrn. of samples held at various relative humidities (created by satd. salt solns.); and (3) an adsorption isotherm measurement with a gravimetric sorption analyzer (GSA), which consists of a microbalance within a computer-controlled humidified environment. Data from the latter two methods were analyzed with the Brunauer-Emmett-Teller (BET) gas adsorption equation to yield exptl. monolayers. The authors examd. 6 different therapeutic proteins and found that for each case all 3 approaches yielded similar results for the water monolayer. The authors also attempted to use the BET equation to det. the water monolayer for a model sugar (trehalose) and polyol (mannitol), which are potential excipients in pharmaceutical protein formulations. Calcns. from the data obtained by the traditional and GSA methods yielded consistent results for trehalose, which remained amorphous upon lyophilization. Mannitol tended to form anhyd. crystals upon freeze-drying, and was thus not amenable to anal. The utility of both traditional and GSA methods for detg. the water monolayer was extended to colyophilized protein:sugar systems as well.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXnsFSitrk%253D&md5=0d8c3234802423dfc0d5419f1ff35fa3
52. 52
  Pauling, L. The Adsorption of Water by Proteins J. Am. Chem. Soc. 1945, 67, 555– 557 DOI: 10.1021/ja01220a017
  [ACS Full Text ], [CAS], Google Scholar
  52
  The adsorption of water by proteins
  Pauling, Linus
  Journal of the American Chemical Society (1945), 67 (), 555-7CODEN: JACSAT; ISSN:0002-7863.
  The data published by Bull (C.A. 38, 6156.1) and Shaw (C.A. 38, 6153.3) on the adsorption of water by proteins are in considerable degree interpreted on the assumption that the initial process is the attachment of one water mol. to each polar amino acid side chain. The data also indicate that peptide carbonyl and imido groups usually do not bind water, because of their mutual interaction by H-bond formation, but that water is bound by carbonyl groups that are not coupled by H bonds with imido groups. In salmin, in which most of the amino-acid residues are polar, these polar residues co.ovrddot.operate to attach one water mol. jointly to 2 polar groups in the initial process of hydration.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaH2MXhsVCmtQ%253D%253D&md5=530cf9b926551d5879c6a50f988cc833
53. 53
  Rupley, J. A.; Gratton, E.; Careri, G. Water and Globular Proteins Trends Biochem. Sci. 1983, 8, 18– 22 DOI: 10.1016/0968-0004(83)90063-4
  [Crossref], [CAS], Google Scholar
  53
  Water and globular proteins
  Rupley, John A.; Gratton, Enrico; Careri, Giorgio
  Trends in Biochemical Sciences (1983), 8 (1), 18-22CODEN: TBSCDB; ISSN:0968-0004.
  A review with 27 refs., on the hydration of globular proteins. The thermodn. of hydration are considered, and the effects of hydration on protein function, e.g., mol. dynamics and enzyme activity, are discussed.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL3sXosV2htA%253D%253D&md5=1bcdf1fe915c7556327c45ed1d59736c
54. 54
  Gallat, F.-X.; Brogan, A. P. S.; Fichou, Y.; McGrath, N.; Moulin, M.; Härtlein, M.; Combet, J.; Wuttke, J.; Mann, S.; Zaccai, G.; Jackson, C. J.; Perriman, A. W.; Weik, M. A Polymer Surfactant Corona Dynamically Replaces Water in Solvent-Free Protein Liquids and Ensures Macromolecular Flexibility and Activity J. Am. Chem. Soc. 2012, 134, 13168– 13171 DOI: 10.1021/ja303894g
  [ACS Full Text ], [CAS], Google Scholar
  54
  A Polymer Surfactant Corona Dynamically Replaces Water in Solvent-Free Protein Liquids and Ensures Macromolecular Flexibility and Activity
  Gallat, Francois-Xavier; Brogan, Alex P. S.; Fichou, Yann; McGrath, Nina; Moulin, Martine; Hartlein, Michael; Combet, Jerome; Wuttke, Joachim; Mann, Stephen; Zaccai, Giuseppe; Jackson, Colin J.; Perriman, Adam W.; Weik, Martin
  Journal of the American Chemical Society (2012), 134 (32), 13168-13171CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
  The observation of biol. activity in solvent-free protein-polymer surfactant hybrids challenges the view of aq. and nonaq. solvents being unique promoters of protein dynamics linked to function. Here, we combine elastic incoherent neutron scattering (EINS) and specific deuterium labeling to sep. study protein and polymer motions in solvent-free hybrids. Myoglobin (Mb) motions within the hybrid are found to closely resemble those of a hydrated protein, and motions of the polymer surfactant coating are similar to those of the hydration water, leading to the conclusion that the polymer surfactant coating plasticizes protein structures in a way similar to hydration water.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhtFalu7zF&md5=f2870398633b3c8082486516e7951765
55. 55
  Brogan, A. P. S.; Sharma, K. P.; Perriman, A. W.; Mann, S. Isolation of a Highly Reactive β-Sheet-Rich Intermediate of Lysozyme in a Solvent-Free Liquid Phase J. Phys. Chem. B 2013, 117, 8400– 8407 DOI: 10.1021/jp4041524
  [ACS Full Text ], [CAS], Google Scholar
  55
  Isolation of a highly reactive β-sheet-rich intermediate of lysozyme in a solvent-free liquid phase
  Brogan, Alex P. S.; Sharma, Kamendra P.; Perriman, Adam W.; Mann, Stephen
  Journal of Physical Chemistry B (2013), 117 (28), 8400-8407CODEN: JPCBFK; ISSN:1520-5207. (American Chemical Society)
  The thermal denaturation of solvent-free liq. lysozyme at temps. in excess of 200° was studied by synchrotron radiation CD spectroscopy. Temp.-dependent changes in the secondary structure were used to map the equil. denaturation pathway and characterize a reactive β-sheet-rich unfolding intermediate that was stable in the solvent-free liq. phase under anhyd. conditions but which underwent irreversible aggregation in the presence of water. The unfolding intermediate had a transition temp. of 78° and was extremely stable to temp., eventually reaching the fully denatured state at 178°. The authors propose that the 3-stage denaturation pathway arises from the decreased stability of the native state due to the absence of any appreciable hydrophobic effect, along with an entropically derived stabilization of the reactive intermediate assocd. with mol. crowding in the solvent-free liq.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXpvFantbk%253D&md5=3f965a145b653301ae3c0efdc23285ac
56. 56
  Brogan, A. P. S.; Sessions, R. B.; Perriman, A. W.; Mann, S. Molecular Dynamics Simulations Reveal a Dielectric-Responsive Coronal Structure in Protein–Polymer Surfactant Hybrid Nanoconstructs J. Am. Chem. Soc. 2014, 136, 16824– 16831 DOI: 10.1021/ja507592b
  [ACS Full Text ], Google Scholar
  There is no corresponding record for this reference.
57. 57
  Sharma, K. P.; Zhang, Y.; Thomas, M. R.; Brogan, A. P. S.; Perriman, A. W.; Mann, S. Self-Organization of Glucose Oxidase–Polymer Surfactant Nanoconstructs in Solvent-Free Soft Solids and Liquids J. Phys. Chem. B 2014, 118, 11573– 11580 DOI: 10.1021/jp507566u
  [ACS Full Text ], [CAS], Google Scholar
  57
  Self-Organization of Glucose Oxidase-Polymer Surfactant Nanoconstructs in Solvent-Free Soft Solids and Liquids
  Sharma, Kamendra P.; Zhang, Yixiong; Thomas, Michael R.; Brogan, Alex P. S.; Perriman, Adam W.; Mann, Stephen
  Journal of Physical Chemistry B (2014), 118 (39), 11573-11580CODEN: JPCBFK; ISSN:1520-5207. (American Chemical Society)
  An anisotropic glucose oxidase-polymer surfactant nanoconjugate is synthesized and shown to exhibit complex temp.-dependent phase behavior in the solvent-free state. At close to room temp., the nanoconjugate crystallizes as a mesolamellar soft solid with an expanded interlayer spacing of ca. 12 nm and interchain correlation lengths consistent with alkyl tail-tail and PEO-PEO ordering. The soft solid displays a birefringent spherulitic texture and melts at 40 °C to produce a solvent-free liq. protein without loss of enzyme secondary structure. The nanoconjugate melt exhibits a birefringent dendritic texture below the conformation transition temp. (Tc) of glucose oxidase (58 °C) and retains interchain PEO-PEO ordering. Our results indicate that the shape anisotropy of the protein-polymer surfactant globular building block plays a key role in directing mesolamellar formation in the solvent-free solid and suggests that the microstructure obsd. in the solvent-free liq. protein below Tc is assocd. with restrictions in the intramol. motions of the protein core of the nanoconjugate.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsFWjsrvJ&md5=0fda67f11c72f9fb5a1f90097c8f90b6
58. 58
  Hanski, S.; Junnila, S.; Almásy, L.; Ruokolainen, J.; Ikkala, O. Structural and Conformational Transformations in Self-Assembled Polypeptide–Surfactant Complexes Macromolecules 2008, 41, 866– 872 DOI: 10.1021/ma7019495
  [ACS Full Text ], Google Scholar
  There is no corresponding record for this reference.
59. 59
  Kolbe, A.; del Mercato, L. L.; Abbasi, A. Z.; Rivera Gil, P.; Gorzini, S. J.; Huibers, W. H. C.; Poolman, B.; Parak, W. J.; Herrmann, A. De Novo Design of Supercharged, Unfolded Protein Polymers, and Their Assembly into Supramolecular Aggregates Macromol. Rapid Commun. 2011, 32, 186– 190 DOI: 10.1002/marc.201000491
  [Crossref], [PubMed], [CAS], Google Scholar
  59
  De Novo Design of Supercharged, Unfolded Protein Polymers, and Their Assembly into Supramolecular Aggregates
  Kolbe, Anke; del Mercato, Loretta L.; Abbasi, Azhar Z.; Rivera Gil, Pilar; Gorzini, Sekineh J.; Huibers, Wim H. C.; Poolman, Bert; Parak, Wolfgang J.; Herrmann, Andreas
  Macromolecular Rapid Communications (2011), 32 (2), 186-190CODEN: MRCOE3; ISSN:1022-1336. (Wiley-VCH Verlag GmbH & Co. KGaA)
  Here we report for the first time the design and expression of highly charged, unfolded protein polymers based on elastin-like peptides (ELPs). Pos. and neg. charged variants were achieved by introducing lysine and glutamic acid residues, resp., within the repetitive pentapeptide units. Subsequently it was demonstrated that the monodisperse protein polyelectrolytes with precisely defined amino acid compns., sequences, and stereochemistries can be transferred into superstructures exploiting their electrostatic interactions. Hollow capsules were assembled from oppositely charged protein chains by using the layer-by-layer technique. The structures of the capsules were analyzed by various microscopy techniques revealing the fabrication of multilayer containers. Due to their low toxicity in comparison to other polyelectrolytes, supercharged ELPs are appealing candidates for the construction of electrostatically induced scaffolds in biomedicine.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXlsVyqug%253D%253D&md5=ac50c27ffe5f1cc8450cb5b7ced9d8a3
60. 60
  Yang, H.; Ma, C.; Li, K.; Liu, K.; Loznik, M.; Teeuwen, R.; van Hest, J. C. M.; Zhou, X.; Herrmann, A.; Wang, J. Tuning Ice Nucleation with Supercharged Polypeptides Adv. Mater. 2016, 28, 5008– 5012 DOI: 10.1002/adma.201600496
  [Crossref], [PubMed], [CAS], Google Scholar
  60
  Tuning Ice Nucleation with Supercharged Polypeptides
  Yang, Huige; Ma, Chao; Li, Kaiyong; Liu, Kai; Loznik, Mark; Teeuwen, Rosalie; van Hest, Jan C. M.; Zhou, Xin; Herrmann, Andreas; Wang, Jianjun
  Advanced Materials (Weinheim, Germany) (2016), 28 (25), 5008-5012CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
  The authors reported the tuning of ice nucleation through systematic control of both surface charge and charge d., which is achieved via modifying solid surfaces with supercharged unfolded polypeptides (SUPs). Compared to their chem. synthesized counterparts, SUPs are of low toxicity and are biodegradable. Moreover, the fabrication procedure based on genetic engineering allows abs. control over nature of charges, chain length, and charge d., combined with a monodisperse character. These structural attributes of SUPs open up new possibilities for the study of ice nucleation.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XmvFart78%253D&md5=5b3da396d9d9c2cca7bbeffd8e381e7a
61. 61
  Sharma, K. P.; Bradley, K.; Brogan, A. P. S.; Mann, S.; Perriman, A. W.; Fermin, D. J. Redox Transitions in an Electrolyte-Free Myoglobin Fluid J. Am. Chem. Soc. 2013, 135, 18311– 18314 DOI: 10.1021/ja4104606
  [ACS Full Text ], [CAS], Google Scholar
  61
  Redox Transitions in an Electrolyte-Free Myoglobin Fluid
  Sharma, Kamendra P.; Bradley, Kieren; Brogan, Alex P. S.; Mann, Stephen; Perriman, Adam W.; Fermin, David J.
  Journal of the American Chemical Society (2013), 135 (49), 18311-18314CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
  Redox responses assocd. with the heme prosthetic group in a myoglobin-polymer surfactant solvent-free liq. are investigated for the first time in the absence of an electrolyte soln. Cyclic voltammograms from the biofluid exhibit responses that are consistent with planar diffusion of mobile charges in the melt. Temp.-dependent dynamic electrochem. and rheol. responses are rationalized in terms of the effective electron hopping rate between heme centers and the transport of intrinsic ionic species in the viscous protein liq.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhvVShsL7L&md5=a7434c2da24494a9fac820cefdca1dbe
62. 62
  Rusling, J. F.; Nassar, A. E. F. Enhanced Electron Transfer for Myoglobin in Surfactant Films on Electrodes J. Am. Chem. Soc. 1993, 115, 11891– 11897 DOI: 10.1021/ja00078a030
  [ACS Full Text ], [CAS], Google Scholar
  62
  Enhanced electron transfer for myoglobin in surfactant films on electrodes
  Rusling, James F.; Nassar, Alaa Eldin F.
  Journal of the American Chemical Society (1993), 115 (25), 11891-7CODEN: JACSAT; ISSN:0002-7863.
  The Fe(III)/Fe(II) redox couple of the heme protein myoglobin (Mb) gave std. electron-transfer rate consts. about 1000-fold larger in liq. crystal films of didodecyldimethyl ammonium bromide (DDAB) on pyrolytic graphite (PG) electrodes than in aq. solns. Electron-transfer rates of Mb were also enhanced in films of sol. cationic and anionic surfactants absorbed on PG. Results suggest a role for strongly adsorbed surfactant at electrode-film interfaces, which may prevent adsorption of macromol. impurities which can block electron transfer. Mb-DDAB films were prepd. by spontaneous insertion of Mb from soln. into water-insol. cast films of DDAB. The resulting films were stable for a month in pH 5.5-7.5 buffers contg. 50 mM NaBr. Spectroscopic, thermal, and electrochem. characterizations suggest that the films consist of lamellar liq. crystal DDAB contg. preferentially oriented Mb with the iron heme in a high spin state. Mb-DDAB films showed good charge-transport rates, which allowed Mb to be used as a redox catalyst. Redns. of the organohalide pollutants trichloroacetic acid and ethylene dibromide were catalyzed by Mb-DDAB films on PG electrodes at voltages 1.0-1.3 V less neg. than direct redns.
  >> More from SciFinder ^®
  https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXjvVyk&md5=d8b2faf9cb5410f53d44f7488a5945c5

PDF [ 10MB]

All Types

Liquefaction of Biopolymers: Solvent-free Liquids and Liquid Crystals from Nucleic Acids and Proteins

Article Views

Altmetric

Citations

Abstract

Conspectus

Introduction

Concept and Mechanism of Formation of Biomacromolecular Liquids

Design, Preparation, and Application of Biomacromolecular Liquids

Nucleic Acid Liquids and Liquid Crystals

Figure 1

Figure 2

Figure 3

Protein Liquids and Liquid Crystals

Figure 4

Figure 5

Figure 6

Figure 7

Virus Liquids and Liquid Crystals

Figure 8

Conclusions and Future Directions

Author Information

Biographies

Kai Liu

Chao Ma

Robert Göstl

Lei Zhang

Andreas Herrmann

References

Cited By

Abstract

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

References

STEP 1:

STEP 2: