Attractive Intermolecular Interactions Research Articles

A van der Waals Model of Solvation Thermodynamics.

Exploiting the van der Waals model of liquids, it is possible to derive analytical formulas for the thermodynamic functions governing solvation, the transfer of a solute molecule from a fixed position in the ideal gas phase to a fixed position in the liquid phase. The solvation Gibbs free energy change consists of two contributions: (a) the high number density of all liquids and the repulsive interactions due to the basic fact that each molecule has its own body leading to the need to spend free energy to produce an appropriate cavity to contain the solute molecule; (b) the ubiquitous intermolecular attractive interactions lead to a gain in free energy for switching-on attractions between the solute molecule and neighboring liquid molecules. Also the solvation entropy change consists of two contributions: (a) there is an entropy loss in all liquids because the cavity presence limits the space accessible to liquid molecules during their continuous translations; (b) there is an entropy gain in all liquids, at room temperature, due to the liquid structural reorganization as a response to the perturbation represented by solute addition. The latter entropy contribution is balanced by a corresponding enthalpy term. The scenario that emerged from the van der Waals model is in qualitative agreement with experimental results.

Thin Film Formation of HSA in the Presence of CTAB-Capped Gold Nanorods through Phase Separation.

Phase behavior in protein-nanoparticle systems in light of protein corona formation has been investigated. We report the formation of HSA thin films following the addition of a solid protein to a solution of CTAB-capped gold nanorods (AuNRs) via phase separation. The phase separation behavior was observed through UV-vis spectroscopy, turbidity assays, and DLS studies. UV-vis spectra for the protein-AuNR solution indicated a possible self-assembly formation by CTAB-HSA complexes and AuNR-HSA conjugates. The turbidity was found to increase linearly up to 30-50% v/v for each component. The growth phase slope is proportional to the concentration of the components, AuNRs, and HSA, with no lag phase. Dynamic light scattering (DLS) shows the formation of larger aggregates with time, implying a segregated phase of AuNR-HSA and a CTAB-HSA-AuNR network. ζ-potential values confirm surface modification, implying protein corona formation on nanorods. The thin films were also characterized using SEM, AFM, SAXS, XPS, FTIR, and TGA studies. SEM images show a smooth surface with a reduced number of pores, indicating the compactness of the deposited structure. AFM shows two different structural pattern formations with the deposition, indicating possible self-assembly of the protein-conjugated nanoparticles. FTIR studies indicate a change in the hydrogen bonding network and confirm the CTAB-HSA-AuNR complex network formation. The XPS studies indicate Au-S bond formation, along with Au-S-S-Au interactions. SAXS studies indicate the formation of aggregates (oligomers), as well as the presence of dominant attractive intermolecular interactions in the thin films.

Charge induced frustration in C60 monolayers on h-BN/Ni(111)

Frustration in a system occurs when all interacting components cannot reach their minimum energy simultaneously. We report on the development of a frustrated adsorption configuration of a C60 monolayer on epitaxial hexagonal boron nitride (h-BN) grown on Ni(111). In the low-temperature adsorption configuration, we discover non-periodic patterns with striped and zigzag elements, which are characteristic of frustrated systems, formed by molceules with different orientational alignement. Using scanning probe techniques, we investigate these complex patterns' structural and electronic properties. We find two distinct C60 species, one of which is neutral, and the other is charged due to a locally preferred energy level alignment that favors an electron transfer from the Ni(111). Discharging single or multiple intrinsically charged C60 molecules creates local changes in the electrostatic potential, shifting the energy of surrounding molecular orbitals. This allows us to measure the inter-fullerene Coulomb interactions, which plays a crucial role in the formation of the frustrated structure. Monte Carlo simulations derived from the antiferromagnetic Ising model replicate the experimentally observed frustration pattern by considering competing attractive and repulsive intermolecular interactions. As such, the C60 h-BN/Ni(111) system opens a window for essential insights into charge-induced frustration and intermolecular interactions.

Synthesis of Topological Gels by Penetrating Polymerization Using a Molecular Net

AbstractTopological gels possess structures that are cross‐linked only via physical constraints; ideally, no attractive intermolecular interactions act between their components, which yields interesting physical properties. However, most reported previous topological gels were synthesized based on supramolecular interlocked structures such as polyrotaxane, for which attractive intermolecular interactions are essential. Here, we synthesize a water‐soluble “molecular net” (MN) with a large molecular weight and three‐dimensional network structure using poly(ethylene glycol). When a water‐soluble monomer (N‐isopropylacrylamide) is polymerized in the presence of the MNs, the extending polymer chains penetrates the MNs to form an ideal topological MN gel with no specific attractive interactions between its components. The MN gels show unique physical properties as well a significantly high degree of swelling and high extensibility due to slipping of the physical cross‐linking. We postulate this method to yield a new paradigm in gel science with unprecedented physical properties.

Phenyl- versus cyclohexyl-terminated substituents: comparative study on aggregated structures and electron-transport properties in n-type organic semiconductors

This paper reports that specific attractive intermolecular interactions between side-chain substituents can be useful for enhancing charge-carrier mobility in organic semiconductors owing to the suppression of molecular motions.

Intramolecular Repulsion Visible Through the Electrostatic Potential in Disulfides: Analysis via Varying Iso-density Envelopes.

For a series of diethyl disulfide conformations, the nearly touching contours of the electrostatic potential plotted on iso-density molecular surfaces allow the assessment of intramolecular repulsion. The electrostatic potential is plotted on varying iso-density envelopes to find the nearly touching contours for which (a) the surface electrostatic potential does not show overlap between atoms or functional groups and (b) the typical features are visible (σ-hole, lone pair, hydrogen VS,max). When these nearly touching contours X are closer to the nuclei, the more electron density is excluded from the iso-density envelopes and the smaller are the volumes corresponding to these envelopes. Both the contours X and the corresponding volumes are found to correlate with relative conformational energy, reflecting the degree of intramolecular repulsion present in the various diethyl disulfides. Quantitative estimates of intramolecular repulsion can be made based on relationships between the nearly touching contour X vs relative energy and volume (of the nearly touching contour X) vs relative energy, obtained for series of diethyl disulfide conformers. These relations were used to analyze intramolecular repulsion in a set of disulfides broader than diethyl disulfide conformers. We have shown that the approach of varying electronic density contours can be used in the study of repulsive intramolecular interactions, hereby extending earlier work involving attractive intermolecular interactions.

The role of intermolecular interactions on monoclonal antibody filtration through virus removal membranes.

The removal of viruses by filtration is a critical unit operation to ensure the overall safety of monoclonal antibody (mAb) products. Many mAbs show very low filtrate flux during virus removal filtration, although there are still significant uncertainties regarding both the mechanisms and antibody properties that determine the filtration behavior. Experiments were performed with three highly purified mAbs through 3 different commercial virus filters (Viresolve ® Pro, Viresolve® NFP, and Pegasus™ SV4) with different pore structures and chemistries. The flux decline observed during mAb filtration was largely reversible, even under conditions where the filtrate flux with the mAb was more than 100-fold smaller than the corresponding buffer flux. The extent of flux decline was highly correlated with the hydrodynamic diameter of the mAb as determined by dynamic light scattering. The mAb with the lowest filtrate flux for all 3 membranes showed the largest attractive intermolecular interactions and the greatest hydrophobicity, with the latter determined by binding to a butyl resin in an analytical hydrophobic interaction chromatography column. These results strongly suggest that the flux behavior is dominated by reversible self-association of the mAbs, providing important insights into the design of more effective virus filtration processes and in the early identification of problematic mAbs / solution conditions. This article is protected by copyright. All rights reserved.

Concerted Intramolecular and Intermolecular Charge Transfer for High‐Efficiency Near‐Infrared Thermally Activated Delayed Fluorescent Materials Approaching 900 nm

AbstractHindered by the energy gap law, the development of high‐efficiency near‐infrared (NIR) thermally activated delayed fluorescence (TADF) emitters with emission peaks over 800 nm remains challenging. The conventional strategy of enhancing intramolecular charge transfer for bathochromic shift commonly results in low radiative decay rates (kr) and emission efficiency. Herein, a superior strategy of concerted intramolecular CT (intra‐CT) and intermolecular CT (inter‐CT) for high‐efficiency NIR‐TADF materials is demonstrated. As a proof‐of‐concept, two novel emitters DTPZ and DtBuTPZ are developed based on a new acceptor phenazine‐2,3‐dicarbonitrile (PZ). High kr is achieved by large oscillator strength from appropriate intra‐CT property in monomers and effective electronic couplings between inter‐CT and intra‐CT states in aggregates. Suppressed nonradiative decay processes are realized through strong inter‐CT properties, abundant intermolecular attractive interactions, and negligible π∙∙∙π stacking. Consequently, organic light‐emitting diodes based on those emitters showed record‐high maximum external quantum efficiencies and radiances of 2.28%, 24.18 W Sr−1 m−2 at 817 nm, 0.57%, 14.38 W Sr−1 m−2 at 877 nm for DTPZ, and 2.34%, 23.55 W Sr−1 m−2 at 807 nm for DtBuTPZ, respectively.

Domain-specific modulatory effects of phosphomimetic substitutions on liquid-liquid phase separation of tau protein

Aggregation of tau is one of the major pathogenic events in Alzheimer's disease and several other neurodegenerative disorders. Recent reports demonstrated that tau can condense into liquid droplets that undergo time-dependent transition to a solid-like state, suggesting that liquid condensates may be on the pathway to pathological aggregation of tau. While hyperphosphorylation is a key feature of tau isolated from brains of patients with Alzheimer's disease and other tauopathies, the mechanistic role of phosphorylation in tau liquid-liquid phase separation (LLPS) remains largely unexplored. In an attempt to bridge this gap, here we performed systematic studies by introducing phosphomimetic substitutions of Ser/Thr residues with negatively charged Asp/Glu residues in different regions of the protein. Our data indicate that the phosphorylation patterns that increase the polarization of charge distribution in full-length tau (tau441) promote protein LLPS, whereas those that decrease charge polarization have an opposite effect. Overall, this study further supports the notion that tau LLPS is driven by attractive intermolecular electrostatic interactions between the oppositely charged domains. We also show that the phosphomimetic tau variants with low intrinsic propensity for LLPS can be efficiently recruited to droplets formed by the variants with high LLPS propensity. Furthermore, the present data demonstrate that phosphomimetic substitutions have a major effect on time-dependent material properties of tau droplets, generally slowing down their aging. The latter effect is most dramatic for the tau variant with substitutions within the repeat domain, which correlates with the decreased fibrillation rate of this variant.

Synthesis of Stereoregular Uniform Oligomers Possessing a Dense 1,2,3-Triazole Backbone

Recent remarkable progress of precision polymerization techniques has allowed researchers to synthesize polymers of controlled molecular weight, tacticity, and monomer sequence with narrow distributions. However, it is still a challenging subject to synthesize uniform polymers and oligomers, which possess specific molecular weight, tacticity, and monomer sequence. Utilizing the advantages of t-butyl 4-azido-5-hexynoate (tBuAH), which we designed recently, for the synthesis of uniform polymers and oligomers, uniform oligomers of different stereoregularities possessing a dense 1,2,3-triazole backbone were synthesized using optically active tBuAH precursors by iterative procedures containing azidation, deprotection of the protecting group, and copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC). The stereoregular uniform oligomers were characterized in the solid state by powder X-ray diffraction (PXRD) and in the solution state by pulse-field-gradient spin-echo (PGSE) NMR, ultraviolet (UV) absorption, and circular dichroism (CD) spectroscopic techniques. While the solubility of stereoregular uniform oligomers was investigated using common organic solvents, gelation was observed for solutions of two octamers of different stereoregularities in some solvents, e.g., toluene, tetrahydrofuran (THF), acetone, and methanol. It is noteworthy that the intermolecular attractive interaction depended on the stereoregularity in aprotic polar solvents, i.e., THF and acetone, presumably because of the different polarities of octamers.

Theory and Applications of Nitroxide-based Paramagnetic Cosolutes for Probing Intermolecular and Electrostatic Interactions on Protein Surfaces.

Solvent paramagnetic relaxation enhancement (sPRE) arising from nitroxide-based cosolutes has recently been used to provide an atomic view of cosolute-induced protein denaturation and to characterize residue-specific effective near-surface electrostatic potentials (ϕENS). Here, we explore distinct properties of the sPRE arising from nitroxide-based cosolutes and provide new insights into the interpretation of the sPRE and sPRE-derived ϕENS. We show that: (a) the longitudinal sPRE rate Γ1 is heavily dependent on spectrometer field and viscosity, while the transverse sPRE rate Γ2 is much less so; (b) the spectral density J(0) is proportional to the inverse of the relative translational diffusion constant and is related to the quantity ⟨r-4⟩norm, a concentration-normalized equilibrium average of the electron-proton interspin separation; and (c) attractive intermolecular interactions result in a shortening of the residue-specific effective correlation time for the electron-proton vector. We discuss four different approaches for evaluating ϕENS based on Γ2, J(0), Γ1, or ⟨r-6⟩norm. The latter is evaluated from the magnetic field dependence of Γ1 in conjunction with Γ2. Long-range interactions dominate J(0) and Γ2, while, at high magnetic fields, the contribution of short-range interactions becomes significant for J(ω) and hence Γ1; the four ϕENS quantities enable one to probe both long- and short-range electrostatic interactions. The experimental ϕENS potentials were evaluated using three model protein systems, two folded (ubiquitin and native drkN SH3) and one intrinsically disordered (unfolded state of drkN SH3), in relation to theoretical ϕENS potentials calculated from atomic coordinates using the Poisson-Boltzmann theory with either a r-6 or r-4 dependence.

Zn(II) halide coordination compounds with imidazole and 2-methylimidazole. Structural and computational characterization of intermolecular interactions and disorder

Novel zinc(II) coordination compounds with imidazole (Im) and 2-methylimidazole (2-MeIm) were prepared and characterized: [ZnX2(Im)2] (X = Cl (1a), Br (1b), I (1c)) and [ZnX2(2-MeIm)2] (X = Cl (2a), Br (2b), I (2c)). Coordination compounds 1a–c were prepared mechanochemically by neat grinding while 2a–c were prepared by solution synthesis. The complexes were characterized by FT-IR and NMR spectroscopy and by powder X-ray diffraction. Crystal and molecular structures were determined by the single crystal X-ray diffraction. The characteristic of all structures is a distorted tetrahedral coordination of zinc consisting of two halide atoms and two nitrogen atoms from the imidazole (or 2-methylimidazole) ligand. Molecules in 1a–c are interconnected by hydrogen bonds into 3D structures. Structures of 1b and 1c were found to have similar unit cells and similar crystal packing and hydrogen bonding. Introduction of the 2-methylimidazole substituent introduced disorder in the crystal structures of 2a–c. Because of the very small size of the crystals data were collected by synchrotron radiation. For the disordered 2a,2b and 2c fixed geometry was used in refining of the structures. Crystal structures of 2a–c are characterized by chains of molecules connected by hydrogen bonds of the type N–H⋅⋅⋅X, with weak π⋅⋅⋅π and van der Waals interactions between the chains. The QTAIM, RDG and NCI computational analysis of 1a and 2a–c confirmed the presence of weak attractive intermolecular interactions that can be attributed to weak N–H⋅⋅⋅X and van der Waals interactions.

A structural and computational comparison of close contacts and related intermolecular energies of interaction in the structures of 1,3-diiodo-5-nitrobenzene, 1,3-dibromo-5-nitrobenzene, and 1,3-dichloro-5-nitrobenzene.

1,3-Diiodo-5-nitrobenzene, C6H3I2NO2, and 1,3-dibromo-5-nitrobenzene, C6H3Br2NO2, crystallize in the centrosymmetric space group P21/m, and are isostructural with 1,3-dichloro-5-nitrobenzene, C6H3Cl2NO2, that has been redetermined at 100 K for consistency. While the three-dimensional packing in all three structures is similar, the size of the halogen atom affects the nonbonded close contacts observed between molecules. Thus, the structure of 1,3-diiodo-5-nitrobenzene features a close Type 1 I...I contact, the structure of 1,3-dibromo-5-nitrobenzene features a self-complementary nitro-O...Br close contact, while the structure of 1,3-dichloro-5-nitrobenzene also has a self-complementary nitro-O...Cl interaction, as well as a bifurcated C-H...O(nitro) close contact. Notably, the major energetically attractive intermolecular interaction between adjacent molecules in each of the three structures corresponds to a π-stacked interaction. The self-complementary halogen...O(nitro) and C-H...O(nitro) interactions correspond to significant cohesive attraction between molecules in each structure, while the Type 1 halogen-halogen contact is weakly cohesive.

Water adsorption behavior of Mg and Fe substituted microporous AlPO4-5

Isomorphic substitution of zeolite and zeotype materials plays a dominant role in tuning the performance of the materials in adsorption and catalysis. Here, aluminophosphate AlPO4-5 crystals (AFI-type) with variable content of incorporated iron or magnesium were hydrothermally synthesized, characterized, and tested for water adsorption. The metal incorporation altered the growth direction and thus morphology of the resulting crystals, while the Al/P ratio decreased below unity with increasing Fe/Al2O3 or Mg/Al2O3, confirming selective substitution of aluminum. Moreover, the unit cell experienced shrinkage when Fe substituted Al, whereas the MgAPO-5 lattice refinement results revealed minor variation in the lattice parameters. Water vapor adsorption studies revealed that the materials exhibit non-typical, type-V adsorption behavior with initial low uptake, indicating hydrophobicity, followed by a steep capacity increase indicating capillary-like adsorption at higher relative pressures. Metal substitution could tune the behavior, i.e. by increasing hydrophilicity at the lower range of relative pressures, with the onset of the inflection point being shifted to lower P/P0 values with increasing metal content. An Fe-based AlPO4-5 yielded the highest absorption capacity among all adsorbents tested (13 mmol/g at 43 °C). Fowler-Guggenheim calculations showed that the interaction energy (ω) between the adsorbed water molecules was positive for both MgAPO-5 and FeAPO-5 indicating attractive intermolecular interactions, yet a decrease of ω with increasing Me/Al2O3 ratio in the synthesis mixture revealed suppression of intermolecular interactions with metal loading. The reported results and the tailoring of water adsorption behavior by metal substitution can be promising for water sorption/separation applications such as atmospheric water harvesting.

Thermodynamic properties (excess and partial molar volume, Gibbs free energy of activation for viscous flow, enthalpy, and entropy) of propylammonium nitrate/water mixtures

The purpose of this study is to use thermodynamic functions to clarify the change in the solution structure and interaction of the propylammonium nitrate (PAN)/water system in response to changes in the temperature and water concentration. Specifically, the viscosity and density of the PAN/water system were measured over the entire water concentration range and over the temperature range from 278.15 to 323.15 K. The molar free Gibbs energy of activation for viscous flow (ΔGm‡,E), entropy (ΔSm‡,E), and entropy (ΔHm‡,E) and their PAN (ΔGm,PAN‡,E, TΔSm,PAN‡,E, ΔHm,PAN‡,E) and water (ΔGm,H2O‡,E, ΔHm,H2O‡,E and TΔSm,H2O‡,E) partial quantities were calculated, and we investigated the validity of the unique interpretation that water might be accommodated in the cavities of the liquid structure of PAN. In the water concentration dependence, TΔSm‡,E and ΔHm‡,E were consistently negative andTΔSm‡,E < ΔHm‡,E. Therefore, the results suggest that PAN forms a more ordered structure when mixed with water even though the attractive intermolecular interaction decreases. However, the increase of ΔHm‡,E and TΔSm‡,E in the temperature range 278–323 K was 2.35 kJ mol−1 and 1.60 kJ mol−1, respectively, indicating that ΔHm‡,E > TΔSm‡,E. That is, the attractive intermolecular interaction increases with increasing temperature, suggesting that the ordered structure changes toward disorder. In addition, at a water mole fraction of 0.1, which was the lowest concentration of water investigated in this study, the partial molar volume of water is 16% lower than that of pure water and both ΔHm,H2O‡,E and TΔSm,H2O‡,E are reduced, suggesting that the attractive interaction of water is weaker in PAN than in bulk water and that the structure of PAN is closer to that of a pure liquid in this concentration range. Water is speculated to be accommodated into the cavities of the PAN structure.

Azide–Alkyne Interactions: A Crucial Attractive Force for Their Preorganization for Topochemical Cycloaddition Reaction

A new class of attractive intermolecular interaction between azide and ethynyl structural entities in a wide range of molecular crystals is reported. This interaction was systematically evaluated by using 11 geometrically different structural motifs that are preorganized to direct a solid-state topochemical azide-alkyne cycloaddition (TAAC) reaction. The supramolecular features of the azide-alkyne interaction were mapped by various crystallographic and quantum chemical approaches. Topological analysis shows the noticeable participation of electron density in the azide⋅⋅⋅alkyne interactions. Interestingly, reorientation of the atomic polarizabilities in vicinal azide and alkyne groups upon interaction in crystals favors soft orbital-guided TAAC reactions. Moreover, various solid-state and gas-phase energy decomposition methods of individual azide⋅⋅⋅alkyne interactions summarize that the strength (varies from -5.7 to -30.1 kJ mol-1 ) is primarily guided by the dispersion forces with a influencing contribution from the electrostatics.

Nitrogen-Containing Perylene Diimides: Molecular Design, Robust Aggregated Structures, and Advances in n-Type Organic Semiconductors.

ConspectusOrganic semiconductors (OSCs) have attracted much attention because of their potential applications for flexible and printed electronic devices and thus have been extensively investigated in a variety of research fields, such as organic chemistry, solid-state physics, and device physics and engineering. Organic thin-film transistors (OTFTs), a class of OSC-based devices, have been expected to be an alternative of silicon-based metal oxide semiconductor field-effect transistors (MOSFETs), which is the indispensable element for most of the current electronic devices. However, the noncovalently aggregated, van der Waals solid nature of the OSCs, by contrast to covalently bound silicon, conventionally exhibits lower carrier mobilities, limiting the practical applications of OTFTs. In particular, electron-transporting (i.e., n-type) OSCs lag behind their hole-transporting (p-type) counterparts in carrier mobility and ambient stability as OTFTs. This is primarily because of the difficulty in achieving compatibility between the aggregated structure exhibiting excellent carrier mobility and that with enough electron affinity. Recent understandings of carrier transport in OSCs explain that large and two-dimensionally isotropic transfer integrals coupled with small fluctuations are crucial for high carrier mobilities. In addition, from a practical point of view, the compatibility with practical device processes is highly required. Rational molecular design principles, therefore, are still demanded for developing OSCs and OTFTs toward high-end device applications.Herein, we will show our recent progress in the development of n-type OSCs with the key π-electron core (π-core) of benzo[de]isoquinolino[1,8-gh]quinolinetetracarboxylic diimide (BQQDI) on the basis of single-crystal OTFT technologies and the band-transport model enabled by two-dimensional molecular packing arrangements. The critical point is the introduction of electronegative nitrogen atoms into the π-core: the nitrogen atoms in BQQDI not only deepen the molecular orbital energies but also allow hydrogen-bonding-like attractive intermolecular interactions to control the aggregated structures, unlike the conventional role of the nitrogen introduced into OSCs only for the former role. Hence, the BQQDI analogues exhibit air-stable OTFT behavior and two-dimensional brickwork packing structures. Specifically, phenethyl-substituted analogue (PhC2-BQQDI) has been shown as the first principal BQQDI-based material, demonstrating solution-processable thin-film single crystals, fewer anisotropic transfer integrals, and an effective suppression of molecular motions, leading to band-like electron-transport properties and stress-durable n-channel OTFT performances, in conjunction with the support of computational calculations. Insights into more fundamental points of view have been found by side-chain derivatization and OTFT studies on polycrystalline and single-crystal films. We hope that this Account provides readers with new strategies for designing high-performance OSCs by two-dimensional control of the aggregated structures.

Investigating protein diffusivities in diluted hyaluronic acid solutions using dynamic light scattering.

This study aimed to investigate the diffusivities of lysozyme (LYS), ovalbumin (OVA), and hyaluronic acid (HA) in buffered solvents using dynamic light scattering (DLS). For protein/solvent and HA/solvent binary systems, the diffusion coefficients of protein or HA were obtained from autocorrelation function (ACF) curve fitting. Whereas, for protein/HA/solvent ternary systems, the two eigenvalues of the mutual diffusion coefficient matrix were obtained from ACF curve fitting. The results of binary systems showed that at low ionic strength, the diffusion coefficients of protein and HA increased linearly with concentration; at high ionic strength, the diffusion coefficients of OVA and LYS were independent on protein concentration; for HA, the positive linear relationship between diffusion coefficient and concentration existed at high and low ionic strengths, but the slope at high ionic strength was smaller compared to that at low ionic strength. For OVA/HA/solvent ternary systems, the sum of two eigenvalues (D1DLS + D2DLS) was slightly smaller compared to (DOVA + DHA), where DOVA and DHA were the diffusion coefficients in their binary systems. On the contrary, for LYS/HA/solvent ternary systems, (D1DLS + D2DLS) were significantly smaller than (DLYS + DHA) and the diffusion coefficients in binary and ternary systems exhibited an opposite trend with respect to ionic strength change. The DLS and MD simulation results indicated strong attractive intermolecular interaction existed between LYS and HA molecules, especially at low ionic strength. By using DLS, it was possible to characterize the diffusion coefficients of diluted protein/HA binary and ternary systems.

Coacervate-Based Instant and Repeatable Underwater Adhesive with Anticancer and Antibacterial Properties.

Underwater adhesion is a great challenge for the development of adhesives as the attractive interfacial intermolecular interactions are usually weakened by the surface hydration layer. The coacervation process of sessile organisms like marine mussels and sandcastle worms has inspired substantial research interest in the fabrication of long-lasting underwater adhesives, but they generally suffer from time-consuming curing triggered by surrounding environmental changes and cannot reserve the adhesiveness once damaged. Herein, an instant and repeatable underwater adhesive was developed based on the coacervation of tannic acid (TA) and poly(ethylene glycol)77-b-poly(propylene glycol)29-b-poly(ethylene glycol)77 (PEG-PPG-PEG, F68), which was driven by hydrogen-bonding interaction, and the hydrophobic cores of F68 micelles offered an additional cross-linking to enhance the mechanical properties. The TA-F68 coacervates could be facilely painted on different substrates, exhibiting robust and instant underwater adhesion (with adhesion strength up to 1.1 MPa on porcine skin) and excellent repeatability (at least 1000 cycles), superior to the previously reported coacervates. Due to the biological activities of TA, the underwater adhesive displayed innate anticancer and antibacterial properties against different types of cancer cells and bacteria, showing great potential for diverse biomedical applications, such as injectable drug carriers, tissue glues, and wound dressings.

Synthesis and characterization of alkylthio-attached azobenzene-based liquid crystal polymers: Roles of the alkylthio bond and polymer chain in phase behavior and liquid crystal formation

We demonstrate for the first time that the alkylthio (or thioether) bonds in the side-chains of liquid crystal (LC) polymers considerably influence the phase-transition behavior, mesomorphic properties, and nanostructures of the LC and crystal (Cr) phases. We synthesized three alkylthio-attached azobenzene-based polymethacrylates; namely, P–OS, P–SO, and P–SS, in which alkylthio bonds were introduced at an outer (terminal) 4-position, at an inner (polymer-chain side) 4-position, and at both the outer and inner 4-positions, respectively, of the azobenzene side chains. In marked contrast to the corresponding pre-monomers and methacrylate monomers, the P–OS, P–SO, and P–SS polymers form well-defined enantiotropic LC phases. Notably, while an outer terminal alkylthio bond renders azobenzene-based polymers (P–OS and P–SS) predominantly smectogenic, a sole inner alkylthio bond renders the P–SO polymer nematogenic. In addition, the outer and inner alkylthio bonds contribute to increasing and decreasing the phase-transition temperatures, respectively. The presence of the alkylthio bonds potentially provides LC polymers with crystallizability. Furthermore, X-ray diffractometry results reveal that the P–OS, P–SO, and P–SS polymers form deeply interdigitated bilayer structures in their SmA, highly ordered, and Cr phases. The specific packing mechanism is discussed in terms of intermolecular attractive interactions involving the sulfur atoms.