Lithium-induced supramolecular hydrogel

We describe a novel anisotropic supramolecular gel made of cyclodextrin-dye, in which physical gelation is completed by lithium salt. Rheological experiment reveals the elastic behaviors of the hydrogel, and high ionic conductivity represents a good mobility of ions inside the gel matrix.     

Smart nanocomposite polymer gels

The combination of polymers with nanomaterials displays novel and often enhanced properties compared to the traditional materials. They can open up possibilities for new technological applications. The magnetic polymer gel represents a new type of composites consisting of small magnetic particles, usually from the nanometer range to the micron range, dispersed in a highly elastic polymeric gel matrix. Combination of magnetic and elastic properties leads to a number of striking phenomena that are exhibited in response to impressed magnetic fields. Giant deformational effects, high elasticity, anisotropic properties, temporary reinforcement and quick response to magnetic field open new opportunities for using such materials for various applications.     

The influence of anisotropic membrane inclusions on curvature elastic properties of lipid membranes

A membrane inclusion can be defined as a complex of protein or peptide and the surrounding significantly distorted lipids. We suggest a theoretical model that allows for the estimation of the influence of membrane inclusions on the curvature elastic properties of lipid membranes. Our treatment includes anisotropic inclusions whose energetics depends on their in-plane orientation within the membrane. On the basis of continuum elasticity theory, we calculate the inclusion-membrane interaction energy that reflects the protein or peptide-induced short-ranged elastic deformation of a bent lipid layer. A numerical estimate of the corresponding interaction constants indicates the ability of inclusions to sense membrane bending and to accumulate at regions of favorable curvature, matching the effective shape of the inclusions. Strongly anisotropic inclusions interact favorably with lipid layers that adopt saddlelike curvature; such structures may be stabilized energetically. We explore this possibility for the case of vesicle budding where we consider a shape sequence of closed, axisymmetric vesicles that form a (saddle-curvature adopting) membrane neck. It appears that not only isotropic but also strongly anisotropic inclusions can significantly contribute to the budding energetics, a finding that we discuss in terms of recent experiments.     

A QM/MM approach to interpreting 67Zn solid-state NMR data in zinc proteins

We present here a (67)Zn solid-state NMR investigation of Zn(2+) substituted rubredoxin. The sample has been prepared as both a dry powder and a frozen solution to determine the effects of static disorder on the NMR line shape. Low-temperature experiments have been performed at multiple fields to determine the relative contributions to the NMR line shape from the electric field gradient and the anisotropic shielding tensors. Finally we present the theoretical interpretation of the experimental results utilizing a combined quantum mechanical molecular mechanics (QM/MM) approach. Theory predicts a sizable contribution from anisotropic shielding as compared with previously examined model systems. This is in good agreement with the experimental data.     

Laterally attached liquid-crystalline polymers as stationary phases in reversed-phase high-performance liquid chromatography. III. Effect of the local anisotropic order on the separation of polycyclic aromatic hydrocarbons

Specific stationary phases based upon non-liquid-crystalline polymers, liquid-crystalline molecules and side-on fixed liquid-crystalline polymers (SO-LCP) have been synthesized for use as silica modified stationary phases in high-performance liquid chromatography (HPLC). The mesogenic side group of the SO-LCP was composed of three phenyl ring benzoate type with terminal alkoxy chains and was laterally linked to a polysiloxane backbone via an alkyl ester spacer arm. This study demonstrated that the shape recognition of stationary phases based upon SO-LCP towards the length-to-breath ratio (L/B) was strongly connected to the existence of a local liquid-crystalline order into the pores of silica gel, warranting the interest of the collective organization of mesomorphic materials in liquid chromatography. Furthermore, the chromatographic performances depended on the kind of anisotropic order and it was more advantageous to use smectic side-on liquid-crystalline polymer than nematic and obviously non-liquid-crystalline ones. Finally, for a series of polymers having the same mesomorphism, the larger the temperature stability range of the mesophase, the more pronounced the local order effect and the higher the shape recognition.     

P NMR investigation of a ringing gel phase and adjacent phases

The temperature-surfactant concentration phase diagram was examined for the dodecyltrimethylammonium dimethylphosphate/3-methyl-3-methoxybutanol/water ternary system. The phase diagram contained a highly elastic gel phase which is known as a “ringing gel phase”. The ringing gel phase and adjacent phases in the ternary system were investigated by polarized optical microscopy, freeze-fracture transmission electron microscopy, and ³¹P NMR. Globular textures were observed in an optically isotropic gel phase. Since the globules were larger than those found in an isotropic solution, the texture consists of domains of aggregated units in the cubic (I₁) phase. Structure units of domains are equivalent to microemulsions which are constructed by surfactant molecules and swollen by alcohol in the isotropic (L₁) phase. Characteristic polarized microscopic textures were visualized in two phases with higher surfactant concentrations. These phases were identified as being hexagonal (H₁) and lamellar (L) liquid crystals which was confirmed by transmission electron microscopy. The ³¹P NMR signal of the ringing gel showed a sharp singlet the same as that of the L₁ phase, indicating the fully averaged anisotropic interaction of the aggregates. The characteristic NMR signals of the anisotropic hexagonal and lamellar liquid crystal phases displayed chemical shielding with an asymmetric lineshape.     

Morphological control of particles

The objective of this review is to highlight the theoretical and practical aspects of particle morphological control. Materials with directional properties are opening new horizons in material science. Structural, optical, and electrical properties can be greatly augmented by the fabrication of composite materials with anisotropic microstructures or with anisotropic particles uniformly dispersed in an isotropic matrix. Examples include structural composites, magnetic and optical recording media, photographic film, and certain metal and ceramic alloys. The new applications and the need for model particles in scientific investigations are rapidly outdistancing the ability to synthesize anisotropic particles with specific chemistries and narrowly distributed physical characteristics (e.g. size distribution, shape, and aspect ratio). Anisotropic particles of many compositions have been produced but only a few (γ-Fe₂O₃ and AgI) are produced with any degree of chemical and physical control. These two examples are the result of literally decades of study. Unfortunately, the science and technology (mainly the technology) that have evolved are maintained as proprietary information. Thus, while we generally know what systems yield single crystal, anisotropic-shaped particles, we do not know how to make powders of these crystals with the desired control of shape uniformity, aspect ratio and phase composition. Particle shape control is a complex process requiring a fundamental understanding of the interactions between solid state chemistry, interfacial reactions and kinetics, and solution (or vapor) chemistry. During synthesis of other than a large single crystal the parameters controlling crystal growth must be balanced with the requirements for anisotropic powder nucleation and growth. Although there has been considerable progress in large single crystal growth and the synthesis of powders composed of monodispersed, spherical particles, these efforts have not often been transferred to the synthesis of anisotropic particles.     

Highly Stable Triangular Single-Layer 2D Assemblies: Synthesis and Their Stimuli-Responsive Elastic and Anisotropic Curling

Synthesis of highly stable two-dimensional single-layer assemblies (SLAs) is a key challenge in supramolecular science, especially those with long-range molecular order and well-defined morphology. Here, thin (thickness <2 nm) triangular Au^I-thiolate SLAs with high thermo-, solvato- and mechano- stability have been synthesized via a double-ligand co-assembly strategy. Furthermore, the SLAs show assembly-level elastic and anisotropic deformation responses to external stimuli as a result of the long-range anisotropic molecular packing, which provides SLAs with new application potentials in bio-mimic nanomechanics.     

Phase behavior and rheology of oil-swollen micellar cubic phase and gel emulsions in nonionic surfactant systems

We have studied the phase behavior and rheological property of the cubic phase and related gel emulsions in water/nonionic/dodecane systems. In the phase behavior study, it is pointed out that the formation of the discontinuous cubic phase (I₁) is not common in all nonionic surfactant systems; however, a cubic phase (I₁) with oil-swollen micelles or a cubic phase microemulsion is found in the water/C₁₆EO₆/dodecane system, which can solubilize large amount of oil. It was also observed that water/C₁₆EO₆/dodecane system forms stable gel emulsion. In the rheological study we have found an anomalous behavior of the I₁ phase in the water/C₁₂EO₆/dodecane and the water/C₁₆EO₆/dodecane systems. In the water/C₁₂EO₆/dodecane system, the viscoelastic nature of the I₁ phase has been observed, which is shifted to the elastic nature with the addition of dodecane, whereas, highly elastic nature was observed in the water/C₁₆EO₆/dodecane system. In both the cases shear-thinning behavior were seen. The elastic modulus, G′ and complex viscosity, |η1| of the I₁ phase increase with the dodecane concentration in the water/C₁₂EO₆/dodecane system, whereas, decreasing trend have been observed in the water/C₁₆EO₆/dodecane system. This anomalous behavior is suggested due to the nonspherical shape of micelles or polydispersity of the micelles in the water/C₁₆EO₆/dodecane system. The rheological behavior of the O/I₁ gel emulsion was also studied in both the systems.     

Characterization of inhomogeneous polyacrylamide hydrogels

The physical and structural properties of acrylamide gels have been characterized by osmotic deswelling, mechanical compression, and x-ray scattering. These properties vary considerably with the concentration of the crosslinking agent bisacrylamide, at fixed total monomers concentration (10% wt/wt water). In particular, changes in the properties appear more prominent at a crosslinking level of about 5-6% (wt bisacrylamide/wt monomers). The compression modulus of as-prepared and swollen gels passes through a maximum at this level of crosslinking. The swelling pressure curves can be separated into osmotic and elastic contributions of the gel network. The elastic part exhibits similar behavior to the compression modulus. The scaling of the osmotic part with the gel concentration varies with the degree of crosslinking, changing from 2.33 to 3.09. This indicates that the solvent power of water decreases with increasing crosslinking level, towards Φ conditions. The scattering patterns from the gels have been analyzed as arising from additive contributions from a homogeneous gel matrix, and embedded heterogeneities having a higher crosslinking density. These heterogeneities become much more prominent at the same level of crosslinking about 5-6%. Hysteresis observed in the sorption/desorption behavior of polyacrylamide gel suggests that further irreversible structural changes may occur at water activities lower than probed by osmotic deswelling. © 1992 John Wiley & Sons, Inc.     

A New System of Multiple Emulsions with Lamellar Gel Phases from Vegetable Oil

Emulsions are excellent pharmaceutical vehicles used in both the pharmacy and cosmetic industries. Vegetable oils have several effects/benefits on skin and can be used in emulsions to release principal active components for cosmetic purposes. Herein, multiple W/O/W emulsions were formulated in a one-step emulsification method, and the resulting anisotropic structures were characterized by x-ray diffraction measurements. The multiple emulsions obtained were stable and maintained their anisotropic structures over 2 years. WAXS (wide-angle x-ray scattering) measurements of these emulsions suggested that the carbon chains of the surfactant around the globules are disposed in a gel network phase. Furthermore, SAXS (small-angle x-ray scattering) measurements indicated that the surfactant is organized in lamellar layers around the globules. Thus, for the first time, we demonstrated that stable lamellar gel phase multiple emulsions can be made from vegetable oils. In addition to having the advantage of being prepared in one step, these emulsions have desirable characteristics that can be used in the cosmetic industry as natural active principles with low surfactant concentration and the unique features of multiple emulsions with gel phases.     

Globular protein gelation

In this paper, significant advances in the structure and rheological properties of globular protein gels have been described. The achievements of scattering methods, which have provided information over a range of distances from the monomer to the micron scale, are reviewed. The kinetics of gelation measured by rheological methods have also been discussed, including currently applied models for the gelation time, the gel elastic modulus and the critical gel concentration.     

Creep study of high-esterified pectin gels.

Summary A creep study has been made of pectin gels concentrated to 0.5–2.5% in the temperature interval 25 to 50°C. In the region of linear viscoelasticity the pectin gels are capable of being strained both reversibly and irreversibly. The shape of the reversible strain relaxation curves corresponds to the transition region between the glassy and highly elastic states. The temperature dependence of the largest Newtonian viscosity is described by de Guzmán-Arrhenius equation. The break-down enthalpy of the gel cross-links is between 51 and 74 kJ/mole, showing an increase with concentration.With 10 figures and 1 table     

关于A_（a_i）－B_（b_j）型缩聚物网络结构的研究 Ⅱ．网络结构参数的计算

利用作者在文［７］中得到的溶胶凝胶分配方程推导了Ａａｉ－Ｂｂｊ型缩聚物有效交联点，有效弹性链和悬吊链及相应平均链长的计算公式．由有效弹性链密度推算的丁羟聚氨酯平衡态弹性模量和实验结果有着相同的变化趋势，但有一系统偏差．初步探讨了损耗模量与悬吊链节分数间的定量关系．     

Strain-induced large fluctuations during stress relaxation in polymer melts observed by small-angle neutron scattering. “Lozenges”, “butterflies”, and related theory

We discuss the neutron scattering features of melts containing a fraction of labeled chains, and of rubbers containing a fraction of deuterated paths along several successive elementary chains. Both types of material are studied during relaxation after a fast deformation in very similar conditions. An unusual feature is the shape of the anisotropic scattering as visualized on a bidimensional detector: the isointensity lines have the shape of lozenges. A detailed review of various cases makes this appear as a general feature in SANS scattering from melts and rubbers in a state of partially relaxed deformation. We then describe results for mixtures of small labeled chains inside matrices of large entangled chains or crosslinked matrices: we find another unusual shape of the isointensity levels, called butterfly. We propose the lozenges to be a combination of the classical elliptical scattering with a butterfly scattering, which has a main axis orthogonal to the main axis of the ellipses. We discuss in more details the origin of the butterfly effect, by following two tracks: the first is several theories about demixing under strain, including influence of the strain on the enthalpic, elastic, and conformational terms of the free energy of mixing. The second track is the influence of heterogeneities in crosslinked materials. An explanation which would be common to the case of crosslinked and uncrosslinked material remains to be established.     

Oscillatory shear response of moisture barrier coatings containing clay of different shape factor

Oscillatory shear rheology of barrier coatings based on dispersed styrene-butadiene latex and clay of various shape factors or aspect ratio has been explored. Barrier performance of these coatings when applied to paperboard has been assessed in terms of water vapour transmission rates and the results related to shape factor, dewatering and critical strain. It has been shown that a system based on clay with high shape factor gives a lower critical strain, dewatering and water vapour transmission rate compared with clays of lower shape factor. The dissipated energy, as calculated from an amplitude sweep, indicated no attractive interaction between clay and latex implying a critical strain that appears to be solely dependent on the shape factor at a constant volume fraction. Particle size distribution was shown to have no effect on the critical strain while coatings of high elasticity exhibited high yield strains as expected. The loss modulus demonstrated strain hardening before the elastic to viscous transition. The loss modulus peak was identified by a maximum strain which was significantly lower for a coating based on clay with a high shape factor. The characteristic elastic time was found to vary between 0.6 and 1.3s. The zero shear viscosity of barrier dispersion coatings were estimated from the characteristic elastic time and the characteristic modulus to be of the order of 25-100 Pa s.     

First principles study of structural,electronic, elastic and thermal properties of YX (X = Cd,In, Au,Hg and Tl) intermetallics

The structural, electronic, elastic and thermal properties of YX (X = Cd, In, Au, Hg and Tl) intermetallic compounds crystallizing in B₂-type structure have been studied using first principles density functional theory within generalized gradient approximation (GGA) for the exchange correlation potential. Amongst all the YX compounds, YIn is stable in distorted tetragonal (P4/mmm) CuAu-type structure at ambient pressure with very small energy difference of 0.00681 Ry. but it undergoes to CsCl-type (B₂ phase) structure at 23.3 GPa. Rest of the compounds are stable in B₂ structure at ambient condition. The values of elastic moduli as a function of pressure are also reported. The ductility of these compounds has been analyzed using the Pugh rule. Our calculated results indicate that YTl is the most ductile amongst all the B₂-YX compounds. YAu is the hardest and less compressible compound due to the largest bulk modulus. The elastic properties such as Young's modulus (E), Poisson's ratio (σ) and anisotropic ratio (A) are also predicted. The anisotropic factor is found to be unity for YHg which shows that this compound is isotropic.     

Synthesis of Chemically Asymmetric Silica Nanobottles and Their Application for Cargo Loading and as Nanoreactors and Nanomotors

We report the synthesis of chemically asymmetric silica nanobottles (NBs) with a hydrophobic exterior surface (capped with 3‐chloropropyl groups) and a hydrophilic interior surface for spatially selective cargo loading, and for application as nanoreactors and nanomotors. The silica NBs, which have a “flask bottle” shape with an average diameter of 350 nm and an opening of ca. 100 nm, are prepared by anisotropic sol–gel growth in a water/n‐pentanol emulsion. Due to their chemically asymmetric properties, nanoparticles (NPs) with hydrophilic or hydrophobic surface properties can be selectively loaded inside the NBs or on the outside of the NBs, respectively. A high‐performance nanomotor is constructed by selectively loading catalytically active hydrophilic Pt NPs inside the NBs. It is also demonstrated that these NBs can be used as vessels for various reactions, such as the in situ synthesis of Au NPs, and using Au NP‐loaded NBs as nanoreactors for catalytic reactions.     

Relaxation of a viscoelastic gel bar: I. theory

When a rod of gel is deflected in 3-point bending, two types of relaxation process occur: hydrodynamic relaxation caused by flow of liquid within the gel network, and viscoelastic relaxation of the network itself. The kinetics of load relaxation have previously been analyzed for the case of hydrodynamic relaxation within a perfectly elastic network. That analysis describes, for example, the behavior of silica gel in a nonreactive solvent, such as acetone. When the liquid can attack the gel network, then true viscoelastic relaxation is superimposed on hydrodynamic relaxation, and that situation is examined in the present paper. To a very good degree of approximation, the total relaxation is equal to the product of the hydrodynamic and viscoelastic relaxation functions. In Part II, it will be shown that the present analysis describes the behavior of silica gel in an aqueous solvent and in an alcohol/amine solution.     

Effect of particle shape at finite concentration on the elastic moduli of filled polymers

The elegant approach of Eshelby, developed for dilute dispersions, is generalized to include the interaction of filler with filler. It is then utilized to determine the five elastic moduli of filled polymer containing aligned ellipsoidal particles at finite concentrations φ. The anisotropic particle shape is characterized by an aspect ratio ρ of an ellipsoid. The present theory compares well with available experiments in the literature. The experimentally verified Kerner equation for spherical particles and rule of mixtures for the longitudinal Young's modulus at ρ → ∞ are special cases of our new results.