Liquid crystalline side-chain polysiloxanes containing mesogenic groups attached by esterification

Summary Liquid crystalline side-chain polysiloxanes were prepared without metal complex catalyst. Mesogenic groups such as cholesteryl, 4-cyano-4-biphenyl and 4-methoxy-4-biphenyl group were introduced into polysiloxane by esterification and from DSC measurements they were compatible with other liquid crystalline polysiloxanes reported previously.     

Ozonization of amides

Ozonization of various amides was carried out as a model reaction for the degradation of polyamides with ozone. N-alkylamides and N,N-dialkylamides were found to be reactive compared with those amides which have no alkyl group on the nitrogen atom, and it was suggested that ozone attacks preferentially N-methylene or N-methyl group of amides in the first step of ozonization.     

Coal liquefaction by in-situ hydrogen generation.: 2. Zinc-water model compound reactions

Model compound studies were carried out to elucidate the reaction mechanisms taking place during the liquefaction of coal with the hydrogen produced from the reaction of zinc and water. In compounds of the type Ph-(CH₂)_n-Ph the splitting of the aliphatic bridge was easier with higher n values. Ether type compounds such as diphenylether were unreactive although the C-O bond in dibenzylether was easily cleaved. Condensed ring aromatic compounds gave low conversion with hydrogenation being facilitated by an increase in ring number. Phenolic compounds such as phenol did not react well, but the reactivity increased with increase in aromatic ring size. The cleavage of the aliphatic bridge was accelerated by the OH group, for example, in the case of 4-hydroxydiphenylmethane bond scission was about 15 times higher than that of diphenylmethane. Heterocyclic compounds were unreactive.     

The steric effect of exfoliation agent for fabrication of layer niobium oxide nanosheet

In this research, the steric effect of an exfoliation agent between n-ethylamine and triethylamine for the fabrication of Ca₂Nb₃O₁₀⁻ nanosheet was investigated. The experimental results revealed that the different structures of the exfoliation agent have affected to fabrication of Ca₂Nb₃O₁₀⁻ nanosheet. The use of n-ethylamine as an exfoliation agent gave a maximum exfoliation efficiency of 10 wt.% while the maximum exfoliation efficiency of triethylamine was 90 wt.%. The result showed that the difference in exfoliation efficiency was caused by the steric effect of exfoliation agents. The image of transmission electron microscopy exhibited Ca₂Nb₃O₁₀⁻ nanosheets which were formed by exfoliation of HCa₂Nb₃O₁₀. Furthermore, the reaction time for liquid exfoliation was studied in this work. The reaction time at 4 h gave a maximum of exfoliation efficiency. The Ca₂Nb₃O₁₀⁻ suspension was tested capability to remove hazardous ions. After the experiment, we found the white precipitate which was the formation of CsCa₂Nb₃O₁₀. The result showed that the Ca₂Nb₃O₁₀⁻ nanosheet was efficient for the removal of Cs⁺ ions in the wastewater.     

Effect of direct ovarian injection of vascular endothelial growth factor gene fragments on follicular development in immature female rats

Vascular endothelial growth factor (VEGF) expression in granulosa cells is associated with the thecal vasculature growth during ovarian follicular development. We hypothesized that injection of VEGF gene fragments directly into the rat ovary would induce production of a large number of ovulatory follicles and that these follicles would ovulate. To test this hypothesis, we treated immature female rats with combinations of hormones and VEGF gene fragments. The animals were divided into two groups: one group received solution containing transfection reagents as a control (n = 5), while the other group received direct ovarian injection of VEGF gene fragments at 19 (n = 5), 21 (n = 5), 23 (n = 5), or 25 (n = 5) days after birth followed by i.p. administration of 20 IU equine chorionic gonadotropin (eCG) at the age of 26 days. Forty-eight hours after eCG injection, animals were given 20 IU human chorionic gonadotropin (hCG) i.p. and then the oocytes in both groups were counted. The maximum number of ovulated oocytes was obtained when the VEGF gene fragments were injected into the rat ovary at 21 days after birth. Histological examination revealed that the injection of VEGF gene fragments markedly increased the vascular density around the preovulatory follicles and also the number of these follicles. Our data provide the first reported evidence that most ovulatory follicles generated by injection of VEGF gene fragments are able to ovulate upon hCG treatment. These results demonstrate that injection of VEGF gene fragments directly into the ovary stimulates the development of antral follicles by inducing the formation of thecal vasculature in immature female rats.     

125th Anniversary Review: Microbiological Instability of Beer Caused by Spoilage Bacteria

Beer has been generally recognized as a microbiologically stable beverage. However, microbiological incidents occasionally occur in the brewing industry. The microbiological instability of beer is often caused by bacteria consisting of four genera, Lactobacillus, Pediococcus, Pectinatus and Megasphaera. Lactobacillus and Pediococcus belong to the lactic acid bacteria (LAB), whereas Pectinatus and Megasphaera form a group of strict anaerobes that are known as intermediates between Gram‐positive and Gram‐negative bacteria. The frequencies of beer spoilage incidents caused by these four genera have been reported to exceed 90% in Europe and therefore Lactobacillus, Pediococcus, Pectinatus and Megasphaera are considered to be the principal spoilage agents in the brewing industry. Thus, this review consists of three parts involving these four genera. The first part describes spoilage LAB in alcoholic beverages with some emphasis on beer spoilage LAB. In this part, the emergence and evolution of these spoilage LAB is discussed, the insight of which is useful for developing quality control methods for these beverages. The second part is devoted to the hop resistance in beer spoilage LAB. This area of research is evolving rapidly and recent progress in this field is summarized. The third part concerns Pectinatus and Megasphaera. Although this group of beer spoilage bacteria has been described relatively recently, the incident reports in Europe increased in the early 1990s, reaching around 30% of spoilage incidents. Various aspects of Pectinatus and Megasphaera, ranging from their taxonomy and beer spoilage ability to detection and eradication methods are described.     

A novel method for determining vitamin B1 in a wide variety of foodstuffs with or without polyphenols

Certain foodstuffs exhibit matrix interference effects on the vitamin B₁ analysis prescribed in the official methods of the European Union, AOAC International, and Japan. In this study, we demonstrated that one of the problematic polyphenols in green tea or cocoa was tannin. For these matrices, thiamine was found to interact with tannin in the extraction step and was thus removed by filtration as a residue. To resolve the matrix interference, we proposed lowering the pH of the extraction solution by adding hydrochloric acid after the enzyme reaction. High precision (2–3% RSDr) and good recovery (98.3–103%) were obtained with reference materials using the proposed method. We also confirmed the equivalence of the obtained data from the proposed method and the Japanese official method for nutritional labeling. From these results, the method was found to be effective for vitamin B₁ analysis regardless of the presence of interference matrices.     

Phase separation and dewetting in polystyrene/poly(vinyl methyl ether) blend thin films in a wide thickness range

Phase separation and dewetting processes of blend thin films of polystyrene (PS) and poly(vinyl methyl ether) (PVME) in two phase region have been studied in a wide film thickness range from 65 μm to 42 nm (∼2.5R_g, R_g being radius of gyration of a polymer) using optical microscope (OM), atomic force microscope (AFM) and small-angle light scattering (LS). It was found that both phase separation and dewetting processes depend on the film thickness and were classified into four thickness regions. In the first region above ∼15 μm the spinodal decomposition (SD) type phase separation occurs in a similar manner to bulk and no dewetting is observed. This region can be regarded as bulk. In the second region between ∼15 and ∼1 μm, the SD type phase separation proceeds in the early stage while the characteristic wavelength of the SD decreases with the film thickness. In the late stage dewetting is induced by the phase separation. In the third region between ∼1 μm and ∼200 nm the dewetting is observed even in the early stage. The dewetting morphology is very irregular and no definite characteristic wavelength is observed. It is expected that the irregular morphology is induced by mixing up the characteristic wavelengths of the phase separation and the dewetting. In the fourth region below ∼200 nm the dewetting occurs after a long incubation time with a characteristic wavelength, which decreases with the film thickness. It is considered that the layered structure is formed in the thin film during the incubation period and triggers the dewetting through the capillary fluctuation mechanism or the composition fluctuation one.     

Novel synthesis of poly(methyl methacrylate) brush encapsulated silica particles

Silica (SiO₂)‐crosslinked polystyrene (PS) particles possessing photofunctional N,N‐diethyldithiocarbamate (DC) groups on their surface were prepared by the free‐radical emulsion copolymerization of a mixture of SiO₂ (diameter = 20 nm), styrene, divinyl benzene, 4‐vinylbenzyl N,N‐diethyldithiocarbamate (VBDC), and 2‐hydroxyethyl methacrylate with a radical initiator under UV irradiation. In this copolymerization, the inimer VBDC had the formation of a hyperbranched structure by a living radical mechanism. The particle sizes of such core–shell structures [number‐average particle diameter (D_n) = 35–40 nm] were controlled by the variation of the feed amounts of the monomers and surfactant, or emulsion system. The size distributions were relatively narrow (weight‐average particle diameter/D_n ≈ 1.05). These particles had DC groups on their surface. Subsequently, poly(methyl methacrylate) brush encapsulated SiO₂ particles were synthesized by the grafting from a photoinduced atom transfer radical polymerization approach of methyl methacrylate initiated by SiO₂‐crosslinked PS particles as a macroinitiator. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Relative reactivity of phenylboronic acid to phenylboronate ion toward L-lactate and mandelate at physiological pH

Kinetic studies were performed on the reactions of phenylboronic acid with L-lactic acid and mandelic acid in acidic aqueous and alkaline solutions in order to specify reactive species in these reactions. It was confirmed that the diprotonated ligand (H₂L: L-lactic acid or mandelic acid) is less reactive than the monoprotonated ligand (HL^?: L-lactate ion or mandelate ion), which made possible direct determination of the rate constants of phenylboronic acid (PhB(OH)₂) and its conjugate base, phenylboronate ion (PhB(OH)₃^?). It was found that PhB(OH)₂ is more reactive than PhB(OH)₃^?. On the basis of kinetic results, it was concluded that the most reactive species are PhB(OH)₂ and HL^? at physiological pH 7.4, so the reaction in the boronic acid-based sensor for L-lactate mainly would occur between these species.