Structural effects of crosslinking a biopolymer hydrogel derived from marine mussel adhesive protein

In an effort to explore new biocompatible substrates for biomedical technologies, we present a structural study on a crosslinked gelatinous protein extracted from marine mussels. Prior studies have shown the importance of iron in protein crosslinking and mussel adhesive formation. Here, the structure and properties of an extracted material were examined both before and after crosslinking with iron. The structures of these protein hydrogels were studied by SEM, SANS, and SAXS. Viscoelasticity was tested by rheological means. The starting gel was found to have a heterogeneous porous structure on a micrometer scale and, surprisingly, a regular structure on the micron to nanometer scale. However disorder, or "no periodic structure", was deduced from scattering on nanometer length scales at very high q. Crosslinking with iron condensed the structure on a micrometer level. On nanometer length scales at high q, small angle neutron scattering showed no significant differences between the samples, possibly due to strong heterogeneity. X-ray scattering also confirmed the absence of any defined periodic structure. Partial crosslinking transformed the viscoelastic starting gel into one with more rigid and elastic properties.     

3D Mapping of Gas Physisorption for the Spatial Characterisation of Nanoporous Materials

Nanoporous materials used in industrial applications (e. g., catalysis and separations) draw their functionality from properties at the nanoscale (1–10 Å). When shaped into a technical form these solids reveal spatial variations in the same properties over much larger length scales (1 μm–1 cm). The multiscale characterization of these systems is impaired by the trade-off between sample size and image resolution that is bound to the use of most imaging techniques. We show here the application of X-ray computed tomography for the non-invasive spatial characterization of a zeolite/activated carbon adsorbent bed across three orders of magnitude in scale. Through the unique combination of gas adsorption isotherms measured locally and their interpretation by physisorption analysis, we determine three-dimensional maps of the specific surface area and micropore volume. We further use machine learning to identify and locate the materials within the packed bed. This novel ability to reveal the extent of heterogeneity in technical porous solids will enable a deeper understanding of their function in industrial reactors. Such developments are essential towards bridging the gap between material research and process design.     

Shear-Induced Restructuring of Colloidal Silica Gels

Continuous oscillatory experiments were used to investigate the viscoelastic properties and structural evolution of silica gels obtained from unsheared and presheared sols, at pH 8. The processes controlling structural evolution before, at and after the gel point are discussed. Although the viscoelastic properties of the aged gels are comparable (implying similar structures on length scales of several microns), their chemical properties and microstructures (<1 m) are significantly different. This is directly related to the different aggregate structures formed in the unsheared and presheared systems (50 and 700 nm, respectively) and the associated concentration of surface hydroxyls available for cross-linking and formation of stable siloxane bonds.     

多嵌段共聚物分子的组成不均一性

从不同结构层次角度说明了多嵌段共聚物的分子组成不均一性。提出了一种新的看法,即在讨论多嵌段共聚物的形态和性能时,除了链段间的微相分离外,还必须首先考虑不同平均链段长度的多嵌段大分子间的宏观相分离作用。如何表征与控制其组成不均一性是十分重要的课题。     

Structure and Properties of Poly(vinyl alcohol) Hydrogels Obtained by Freeze/Thaw Techniques

The relationships between the structure and the viscoelastic properties of freeze/thaw PVA hydrogels obtained by repeatedly freezing and thawing dilute solutions of PVA in D₂O(11% w/w PVA) in as-prepared and rehydrated states are investigated. Our results indicate that the PVA chains and solvent molecules are organized at different hierarchical length scales, which include the presence of micro- and macro-pores, into a network scaffolding. The porous network is ensured by the presence of crystallites, which act as knots interconnected by portions of PVA chains swollen by the solvent. X-ray diffraction and SANS techniques are used to obtain structural information at short (angstroms) and medium (nanometers) ranges of length scales, concerning the crystallinity, the size of small crystalline aggregates and the average distance between crystallites in PVA hydrogels. Indirect information concerning the structural organization on the large length scales (microns) are provided by viscoelastic measurements. The dynamic shear elastic moduli at low frequency and low strain amplitude, G′, are determined and related to the degree of crystallinity. These data indicate that a minimum crystallinity of 1% is required for these PVA samples to exhibit gel behaviour and have allowed obtaining the order of magnitude of the average mesh size in these gels. Finally, it is shown that the negative effect of aging, inducing worse physical and mechanical properties in these systems, may be prevented using a drying/re-hydration protocol able to keep the physical properties of the as-prepared PVA hydrogels.     

Time Scales in Polymer Modified Asphalts

Historically, Maxwell was probably the first one who recognized the importance of time scales for understanding the mechanical response of asphalt. In instantaneous response asphalt behaves as an elastic, solid-like material, on the other hand its long time response is that of a viscous, fluid-like material. In the linear viscoelastic region asphalt behaves as a low molecular weight polymer. However, in the nonlinear region of high strains or rates of strain the behavior of some asphaltic systems can be rather complicated. In asphalts, asphaltenes, resins and alkanes compose a complex colloidal system, in which alkanes act as a solvent, asphaltenes as micelles and the polar resins as stabilizers. In order to enhance the mechanical properties of asphalts they are frequently modified by blending them with appropriate polymers. Changes in the impermanent network that can be formed in some of these blends can lead to an unexpected behavior of the steady shear viscosity function. Several different time scales emerge from this behavior. A possible relation of these “nonlinear” time scales to the linear viscoelastic time scales is discussed and examples of anomalous behavior of polymer-modified asphalts are given.     

Communication: crystallite nucleation in supercooled glycerol near the glass transition

Heterogeneity and solid-like structures found near the glass transition provide a key to a better understanding of supercooled liquids and of the glass transition. However, the formation of solid-like structures and its effect on spatial heterogeneity in supercooled liquids is neither well documented nor well understood. In this work, we reveal the crystalline nature of the solid-like structures in supercooled glycerol by means of neutron scattering. The results indicate that inhomogeneous nucleation happens at temperatures near T(g). Nevertheless, the thermal history of the sample is essential for crystallization. This implies such structures in supercooled liquids strongly depend on thermal history. Our work suggests that different thermal histories may lead to different structures and therefore to different length and time scales of heterogeneity near the glass transition.     

Viscoelastic measurements of single molecules on a millisecond time scale by magnetically driven oscillation of an atomic force microscope cantilever

The dynamical nature of biomolecular systems means that knowledge of their viscoelastic behavior is important in fully understanding function. The linear viscoelastic response can be derived from an analysis of Brownian motion. However, this is a slow measurement and technically demanding for many molecular systems of interest. To address this issue, we have developed a simple method for measuring the full linear viscoelastic response of single molecules based on magnetically driven oscillations of an atomic force microscope cantilever. The cantilever oscillation frequency is periodically swept through the system resonance in less than 200 ms allowing the power spectrum to be obtained rapidly and analyzed with a suitable model. The technique has been evaluated using dextran, a polysaccharide commonly used as a test system for single molecule mechanical manipulation experiments. The monomer stiffness and friction constants were compared with those derived from other methods. Excellent agreement is obtained indicating that the new method accurately and, most importantly, rapidly provides the viscoelastic response of a single molecule between the tip and substrate. The method will be a useful tool for studying systems that change their structure and dynamic response on a time scale of 100-200 ms, such as protein folding and unfolding under applied force.     

Relaxation phenomena in PPG model networks near the glass-rubber transition

The viscoelastic and dielectric properties of polypropyleneglycol (PPG)-tris-(4-isocyanatophenyl)thiophosphate (Desmodur^®) model networks have been studied. Attention was focused on the relaxation behaviour near the glass transition. Two relaxation mechanisms were observed in the glass transition range, one due to the PPG chain segments and one due to the less mobile cross-link moieties, i.e. the networks show motional heterogeneity. Mechanically only the first mechanism was observed while dielectrically both mechanisms were found. This motional heterogeneity has a profound effect on the dependence of the glass transition temperature on the composition of these networks. The effect of the stage of cure on the temperature of maximum loss and the magnitude of these two relaxation mechanisms was studied dielectrically. Finally, the effect of exchanging the cross-linker molecules with chain extender molecules with similar structure, thus lowering the cross-link density, was studied.     

Photosynthetic Antenna–Reaction Center Mimicry by Using Boron Dipyrromethene Sensitizers

Various molecular and supramolecular systems have been synthesized and characterized recently to mimic the functions of photosynthesis, in which solar energy conversion is achieved. Artificial photosynthesis consists of light‐harvesting and charge‐separation processes together with catalytic units of water oxidation and reduction. Among the organic molecules, derivatives of BF₂‐chelated dipyrromethene (BODIPY), “porphyrin’s little sister”, have been widely used in constructing these artificial photosynthetic models due to their unique properties. In these photosynthetic models, BODIPYs act as not only excellent antenna molecules, but also as electron‐donor and ‐acceptor molecules in both the covalently linked molecular and supramolecular systems formed by axial coordination, hydrogen bonding, or crown ether complexation. The relationships between the structures and photochemical reactivities of these novel molecular and supramolecular systems are discussed in relation to the efficiency of charge separation and charge recombination. Femto‐ and nanosecond transient absorption and photoelectrochemical techniques have been employed in these studies to give clear evidence for the occurrence of energy‐ and electron‐transfer reactions and to determine their rates and efficiencies.     

Interactions of biomacromolecules with reverse hexagonal liquid crystals: drug delivery and crystallization applications

Recently, self-assembled lyotropic liquid crystals (LLCs) of lipids and water have attracted the attention of both scientific and applied research communities, due to their remarkable structural complexity and practical potential in diverse applications. The phase behavior of mixtures of glycerol monooleate (monoolein, GMO) was particularly well studied due to the potential utilization of these systems in drug delivery systems, food products, and encapsulation and crystallization of proteins. Among the studied lyotropic mesophases, reverse hexagonal LLC (H(II)) of monoolein/water were not widely subjected to practical applications since these were stable only at elevated temperatures. Lately, we obtained stable H(II) mesophases at room temperature by incorporating triacylglycerol (TAG) molecules into the GMO/water mixtures and explored the physical properties of these structures. The present feature article summarizes recent systematic efforts in our laboratory to utilize the H(II) mesophases for solubilization, and potential release and crystallization of biomacromolecules. Such a concept was demonstrated in the case of two therapeutic peptides-cyclosporin A (CSA) and desmopressin, as well as RALA peptide, which is a model skin penetration enhancer, and eventually a larger macromolecule-lysozyme (LSZ). In the course of the study we tried to elucidate relationships between the different levels of organization of LLCs (from the microstructural level, through mesoscale, to macroscopic level) and find feasible correlations between them. Since the structural properties of the mesophase systems are a key factor in drug release applications, we investigated the effects of these guest molecules on their conformations and the way these molecules partition within the domains of the mesophases. The examined H(II) mesophases exhibited great potential as transdermal delivery vehicles for bioactive peptides, enabling tuning the release properties according to their chemical composition and physical properties. Furthermore, we showed a promising opportunity for crystallization of CSA and LSZ in single crystal form as model biomacromolecules for crystallographic structure determination. The main outcomes of our research demonstrated that control of the physical properties of hexagonal LLC on different length scales is key for rational design of these systems as delivery vehicles and crystallization medium for biomacromolecules.     

Impact of Higher‐Order Structuralization on the Adsorptive Properties of Metal–Organic Frameworks

The structural processing of metal–organic frameworks (MOFs) over multiple length scales is critical for their successful use as adsorbents in a variety of emerging applications. Although significant advances in molecular‐scale design have provided strategies to boost the adsorptive capacities of MOFs, relatively little attention has been directed toward understanding the influence of higher‐order structuralization on the material performance. Herein, we present the main strategies that are currently available for the structural processing of MOFs and discuss the influence these processes can impart on the adsorptive properties of the materials. In all, this intriguing area of research is expected to provide significant opportunities to enhance the properties of MOFs further, which will ultimately aid in their optimization in the context of specific real‐world applications.     

Molecular dynamics studies of ionically conducting glasses and ionic liquids: wave number dependence of intermediate scattering function

Dynamical heterogeneity is a key feature to characterize both acceleration and slowing down of the dynamics in interacting disordered materials. In the present work, the heterogeneous ion dynamics in both ionically conducting glass and in room temperature ionic liquids are characterized by the combination of the concepts of Lévy distribution and multifractality. Molecular dynamics simulation data of both systems are analyzed to obtain the fractional power law of the k-dependence of the dynamics, which implies the Lévy distribution of length scale. The multifractality of the motion and structures makes the system more complex. Both contributions in the dynamics become separable by using g(k,t) derived from the intermediate scattering function, F(s)(k,t). When the Lévy index obtained from F(s)(k,t) is combined with fractal dimension analysis of random walks and multifractal analysis, all the spatial exponent controlling both fast and slow dynamics are clarified. This analysis is generally applicable to other complex interacting systems and is deemed beneficial for understanding their dynamics.     

Reporters in the nanoworld: diffusion of single molecules in mesoporous materials

Mesoporous materials have a high potential for a number of different applications in Materials Science such as in molecular sieving, as masks for the formation of nanometre-sized metallic wires, as novel drug-delivery systems or as advanced host systems for catalysis. For many of these applications a thorough understanding of the interaction of guest molecules within the host matrix is required. In this tutorial review, we cover recent single-molecule experiments that allow the investigation of host-guest dynamics with unprecedented detail. We will show how molecules diffusing in samples with (almost) perfect domain ordering still show a large heterogeneity in their mobility and interaction with the host. With the presented methodology it is now possible to dramatically improve our understanding of host-guest interactions and in return develop new nano-structured mesoporous materials with properties optimised for a certain application.     

Responsive self-assemblies based on fatty acids

Fatty acids are anionic surfactants under their deprotonated forms. They are surfactants with both biodegrability and low toxicity. Fatty acid molecules can self-assemble under various shapes in an aqueous solution. These self-assembled structures can respond to stimuli such as pH, CO₂ and temperature due to changes occurring at the molecular level. These specificities make them surfactants of special interest to tune the properties at a macroscopic scale. The aim of this article is to review the recent advances in the creation and in the understanding of responsive self-assemblies obtained from fatty acid molecules in an aqueous solution. The links between the microscopic, mesoscopic and macroscopic scales are described. The alkyl chain melting phenomenon triggered by temperature at the molecular level leading to thermoresponsive interfaces and foams at the macroscopic scale is highlighted.     

Tuning Achiral to Chiral Supramolecular Helical Superstructures

The design and synthesis of achiral organic functional molecules which can assemble into a chiral with selective handedness in the absence of chiral substances is an important in understanding the role chirality plays within these systems. In this review, we described general approaches towards supramolecular chiral molecules the synthesis and self‐assembly of achiral molecule to active chiral molecules to investigate controlled supramolecular chiral nanostructures with their photoluminescent properties for rapid, sensitive and selective detection of analytes of choice. Various small molecules have been discussed for achiral to chiral along with induction of chirality and controlled chiral helical structures in detail. We discussed few examples where stimuli used to control the chirality such as temperature, pH etc. Finally, we will also explore on the photo responsive helicity properties of the aggregation induced emission active molecule such as tetraphenylethene conjugates.     

The Potentials of Pulsed Field Gradient NMR for Investigation of Porous Media

PFG NMR self-diffusion studies provide information on the translational mobility of fluid molecules. Since in porous media the diffusion path of fluid molecules in the pore space is affected by interaction with the pore wall, PFG NMR measurements are sensitive to structural peculiarities of the confining porous medium. The pore space properties which can be investigated depend on length scales set by the PFG NMR experiment in respect to the typical size of the structural feature studied. Based upon these length scales, an interpretation pattern for PFG NMR self-diffusion studies in porous media is given. PFG NMR self-diffusion studies in macro- and microporous systems such as sedimentary rocks and zeolite crystallites, respectively, are reviewed.     

Strong optical nonlinearities of self-assembled polymorphic microstructures of phenylethynyl functionalized fluorenones

The polymorphs of a phenylethynyl functionalized fluorenone derivative, and their controlled self-assembly for microstructures with different morphologies have been studied. These polymorphic microcrystals exhibit very distinctive NLO properties, which are highly correlated to their electronic and supramolecular structures.     

Particle tracking microrheology of lyotropic liquid crystals

We present comprehensive results on the microrheological study of lyotropic liquid crystalline phases of various space groups constituted by water-monoglyceride (Dimodan) mixtures. In order to explore the viscoelastic properties of these systems, we use particle tracking of probe colloidal particles suitably dispersed in the liquid crystals and monitored by diffusing wave spectroscopy. The identification of the various liquid crystalline phases was separately carried out by small-angle X-ray scattering. The restricted motion of the particles was monitored and identified by the decay time of intensity autocorrelation function and the corresponding time-dependent mean square displacement (MSD), which revealed space group-dependent behavior. The characteristic time extracted by the intersection of the slopes of the MSD at short and long time scales, provided a characteristic time which could be directly compared with the relaxation time obtained by microrheology. Further direct comparison of microrheology and bulk rheology measurements was gained via the Laplace transform of the generalized time-dependent MSD, yielding the microrheology storage and loss moduli, G'(ω) and G'(ω), in the frequency domain ω. The general picture emerging from the microrheology data is that all liquid crystals exhibit viscoelastic properties in line with results from bulk rheology and the transition regime (elastic to viscous) differs according to the specific liquid crystal considered. In the case of the lamellar phase, a plastic fluid is measured by bulk rheology, while microrheology indicates viscoelastic behavior. Although we generally find good qualitative agreement between the two techniques, all liquid crystalline systems are found to relax faster when studied with microrheology. The most plausible explanation for this difference is due to the different length scales probed by the two techniques: that is, microscopical relaxation on these structured fluids, is likely to occur at shorter time scales which are more suitably probed by microrheology, whereas bulk, macroscopic relaxations occurring at longer time scales can only be probed by bulk rheology.     

Cross-linking of functionalised siloxanes with alumatrane: Reaction mechanisms and kinetics

Cross-linking of functionalised polysiloxanes is an important tool to adjust their viscoelastic properties and can be achieved by the reaction with alumatrane. The cross-linking reaction has been found to proceed only with hydrolyzed alumatrane species. Siloxane model compounds with different functional groups such as alkoxy, siloxy, and hydroxy groups were considered in order to optimise the rheological properties of the polymer. The activation energy barriers of the related reactions were analysed using the density functional theory under the assumption of the presence of Al-OH groups formed by the hydrolysis of alumatrane. The cross-linking involving hydroxy groups of siloxane and hydrolyzed alumatrane has been found to have the lowest activation energy (−14 kJ/mol). As the reaction of the Si-O-Si-polymer backbone with the hydroxy groups of the hydrolyzed alumatrane turned out to have the very low activation energy of +2 kJ/mol, this type of reaction is predicted to play a key role for the cross-linking of polysiloxanes with hydrolyzed alumatrane. The involved water molecules are formed back in the course of subsequent polycondensation reactions, therefore H₂O can be considered as a cross-linking catalyst in these systems.