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Helical structures were confirmed for both the SmA b and SmBlue phases of banana-shaped molecular systems from observations of the microscopic fringe pattern and the selective reflection of blue color, respectively. X-ray and optical microscopy indicate that the helical axes in the SmA b and SmBlue phases are normal and parallel to the smectic layer, respectively. In these two helical phases, 13C NMR spectra show two C=O peaks, suggesting two different configurations of ester group, whereas only one C=O peak appears in the isotropic and crystal phases. This indicates that the two C=O groups in the mesogenic core are not in the same plane but are twisted. The addition of chiral dopant makes the dichroic ratio of the right- and left-circularly polarized scattered light positive or negative in the SmBlue phase, although the wavelength (∼430 nm) of the scattering peak does not change significantly. The origin of the helix will be discussed in view of the twisted molecular conformation (conformational chirality) and the escape from macroscopic polarization.

No abstract

We found that the frustration, i.e., unusual density modulation, is induced on ferroelectric SmAb and HexBb phases composed of achiral banana-shaped molecules. The frustration takes place along the bent direction of molecules, with four or five molecules included in each inversion unit. Such an unusual frustrated structure may be explained as a result of a two-dimensional escape from spontaneous polarization in the ferroelectric phases.

A series of platelet sericite particles coated to different extents with a fluorinating agent has been characterised and their behaviour in mixtures with air and oil studied. The material which forms by vigorous shaking depends on both the surface tension of the oil and the surface energy of the particles which control their degree of wetting. Oil dispersions are formed in liquids of relatively low tension (<22 mN m(-1)), e.g. hexane and cyclomethicone, for all particles. Particle-stabilised air-in-oil foams form in liquids of higher tension, e.g. dodecane and phenyl silicone, where the advancing three-phase contact angle θ, measured on a planar substrate composed of the particles into the liquid, lies between ca. 65° and 120°. For oils of tension above 27 mN m(-1) like squalane and liquid paraffin with particles for which θ > 70°, we have discovered that dry oil powders in which oil drops stabilised by particles dispersed in air (oil-in-air) can be prepared by gentle mixing up to a critical oil : particle ratio (COPR) and do not leak oil. These powders, containing up to 80 wt% oil, release the encapsulated oil when sheared on a substrate. For many of the systems forming oil powders, stable liquid oil marbles can also be prepared. Above the COPR, catastrophic phase inversion occurs yielding an ultra-stable air-in-oil foam. We thus demonstrate the ability to disperse oil drops or air bubbles coated with particles within novel materials.

In response to osmotic stress, proline is accumulated in many bacterial and plant cells as an osmoprotectant. The yeast Saccharomyces cerevisiae induces trehalose or glycerol synthesis but does not increase intracellular proline levels during various stresses. Using a proline-accumulating mutant, we previously found that proline protects yeast cells from damage by freezing, oxidative, or ethanol stress. This mutant was recently shown to carry an allele of PRO1 which encodes the Asp154Asn mutant ␥-glutamyl kinase (GK), the first enzyme of the proline biosynthetic pathway. Here, enzymatic analysis of recombinant proteins revealed that the GK activity of S. cerevisiae is subject to feedback inhibition by proline. The Asp154Asn mutant was less sensitive to feedback inhibition than wild-type GK, leading to proline accumulation. To improve the enzymatic properties of GK, PCR random mutagenesis in PRO1 was employed. The mutagenized plasmid library was introduced into an S. cerevisiae non-proline-utilizing strain, and proline-overproducing mutants were selected on minimal medium containing the toxic proline analogue azetidine-2-carboxylic acid. We successfully isolated several mutant GKs that, due to extreme desensitization to inhibition, enhanced the ability to synthesize proline better than the Asp154Asn mutant. The amino acid changes were localized at the region between positions 142 and 154, probably on the molecular surface, suggesting that this region is involved in allosteric regulation. Furthermore, we found that yeast cells expressing Ile150Thr and Asn142Asp/Ile166Val mutant GKs were more tolerant to freezing stress than cells expressing the Asp154Asn mutant.

Double-stranded DNA-grafted nanoparticles (dsDNA-NPs) exhibit a unique dispersion behavior under high-salt conditions depending on the pairing status of their outermost base pairs (pairing or unpairing). The dsDNA-NPs having complementary (i.e., pairing) outermost base pairs spontaneously aggregate under high-salt conditions, but not when their outermost base pairs are mismatched (unpairing). In this study, we used colloidal probe atomic force microscopy to examine how the outermost base pairs affect the interaction between the dsDNA-grafted layers (dsDNA layers). To precisely assess the subtle structural differences in the dsDNA layers, we developed a method for the formation of a homogenous dsDNA layer on gold surfaces using hairpin-shaped DNAs. Homogenous dsDNA layers having complementary (G-C) or mismatched (C-C) outermost base pairs were grafted onto the surfaces of colloidal probes and gold substrates. Force-distance curves measured in an aqueous medium under high-salt conditions revealed that the surface forces between the dsDNA layers were bilateral in nature and were governed by the outermost base pairs. Between complementary outermost dsDNA layers, the surface force changed from repulsive to attractive with an increase in the NaCl concentration (10-1000 mM). The attraction observed under high-salt conditions was attributed to the site-specific interaction proceeded only between complementary dsDNA terminals, the so-called blunt-end stacking. In fact, between mismatched outermost dsDNA layers, the repulsive force was mostly dominant within the same NaCl concentration range. Our results clearly revealed that the pairing status of the outermost base pairs has significant implications for the surface forces between dsDNA layers, leading to the unique dispersion behavior of dsDNA-NPs.

The type of material stabilized by four kinds of fluorinated particles (sericite and bentonite platelet clays and spherical zinc oxide) in air-oil mixtures has been investigated. It depends on the particle wettability and the degree of shear. Upon vigorous agitation, oil dispersions are formed in all the oils containing relatively large bentonite particles and in oils of relatively low surface tension (γla < 26 mN m(-1)) like dodecane, 20 cS silicone, and cyclomethicone containing the other fluorinated particles. Particle-stabilized oil foams were obtained in oils having γla > 26 mN m(-1) where the advancing air-oil-solid contact angle θ lies between ca. 90° and 120°. Gentle shaking, however, gives oil-in-air liquid marbles with all the oil-particle systems except for cases where θ is <60°. For oils of tension >24 mN m(-1) with omniphobic zinc oxide and sericite particles for which advancing θ ≥ 90°, dry oil powders consisting of oil drops in air which do not leak oil could be made upon gentle agitation up to a critical oil:particle ratio (COPR). Above the COPR, catastrophic phase inversion of the dry oil powders to air-in-oil foams was observed. When sheared on a substrate, the dry oil powders containing at least 60 wt % of oil release the encapsulated oil, making these materials attractive formulations in the cosmetic and food industries.