环氧丙烯酸酯的紫外光固化

制备了适于配制紫外光固化涂料的环氧丙烯酸酯，研究了反应温度、阻聚剂、催化剂等因素对环氧树脂与丙烯酸反应的影响；讨论了反应机理和动力学；并利用红外光谱观察了产物的紫外光固化行为。季铵盐能有效地催化环氧树脂和丙烯酸的反应，当其用量为０．６％～１．２％时，在９０～１１０℃反应４．５～８小时后，环氧基转化率大于９７％。由此配制的光固化涂料经紫外光辐照能快速固化。     

Silicon clusters: chemistry and structure

The chemical reactions of size selected silicon cluster ions (containing up to 70 atoms) have been studied with a number of different reagents using injected ion drift tube techniques. Both kinetic and equilibrium measurements have been performed as a function of temperature, and the influence of cluster annealing on chemical reactivity explored. Unlike metal clusters, where bulk behavior appears to be approached with around 30 atoms, large silicon clusters (n up to 70) are much less reactive than bulk silicon surfaces. These results suggest that the clusters in the size range examined here are not small crystals of bulk silicon, but have compact, high coordination number structures with few dangling bonds.     

13C nuclear magnetic resonance studies of cellulose acetate

¹³C-NMR spectra of ring carbons and O-acetyl carbonyl carbons of cellulose acetate (CA) in dimethyl sulfoxide-d₆ were analyzed. The CA samples with the degree of substitution (DS) ranging from 0.84 and 1.91 were prepared by homogeneous acetylation of cellulose with acetic anhydride in a 10% LiCl/dimethyl acetamide solvent. It was found that the use of these low DS samples permitted easier assignments not only of the ring carbon but also of the O-acetyl carbonyl carbon signals. The assignments were confirmed by comparing with the ¹H-NMR spectra of the samples obtained by complete acetylation of the corresponding CA samples with acetyl-d₃ chloride. Two methods for determining the distribution of O-acetyl groups of CA, i.e., the relative DS at the three different types of hydroxyl groups, were developed. One is based on the measurements of the relative intensities of the signals for the ring carbons and the other is based on the measurements of the relative intensities of the signals for the O-acetyl carbonyl carbons.     

Influence of the three-dimensional heterogeneous roughness on electrokinetic transport in microchannels

Surface roughness has been considered as a passive means of enhancing species mixing in electroosmotic flow through microfluidic systems. It is highly desirable to understand the synergetic effect of three-dimensional (3D) roughness and surface heterogeneity on the electrokinetic flow through microchannels. In this study, we developed a three-dimensional finite-volume-based numerical model to simulate electroosmotic transport in a slit microchannel (formed between two parallel plates) with numerous heterogeneous prismatic roughness elements arranged symmetrically and asymmetrically on the microchannel walls. We consider that all 3D prismatic rough elements have the same surface charge or zeta potential, the substrate (the microchannel wall) surface has a different zeta potential. The results showed that the rough channel's geometry and the electroosmotic mobility ratio of the roughness elements' surface to that of the substrate, epsilon(mu), have a dramatic influence on the induced-pressure field, the electroosmotic flow patterns, and the electroosmotic flow rate in the heterogeneous rough microchannels. The associated sample-species transport presents a tidal-wave-like concentration field at the intersection between four neighboring rough elements under low epsilon(mu) values and has a concentration field similar to that of the smooth channels under high epsilon(mu) values.     

Facile chemoselective synthesis of dehydroalanine-containing peptides

Useful methodology is described for the synthesis of dehydroalanine residues (II) within peptides. The unnatural amino acid (Se)-phenylselenocysteine (I) can be incorporated into growing peptide chains via standard peptide synthesis procedures. Subsequent oxidative elimination affords a dehydroalanine at the desired position. The oxidation conditions are mild and tolerate functionalities commonly found in peptides, including variously protected cysteine residues. To illustrate its utility, cyclic lanthionines have been synthesized by this method.     

Bactericidal effects of photoactivated porphyrins--an alternative approach to antimicrobial drugs

Photoactivated porphyrins display a potent cytotoxic activity towards a variety of Gram positive bacteria, mycoplasma and yeasts, but not Gram negative cells. The prerequisite for photosensitization of a microbial cell is the binding of porphyrin to the cytoplasmic membrane in a pH-dependent manner. On illumination, the membrane bound, and possibly, cytoplasmic porphyrin molecules generate singlet oxygen and radicals which sensitize biomolecules and lead to cell death. The immediate inhibition of cell growth on photodynamic treatment is accompanied by alterations in cell wall and membrane synthesis, leading to the formation of large mesosomes adjacent to the unaccomplished septa. Hemin bound to microbial cells exerts cytotoxic activity by peroxidative and oxidative reactions independent of light. Future research in the field may enhance the possibility of using porphyrin photosensitization for treatment of microbial infections. Such clinical use will be unrelated to the antibiotic resistance of the pathogen. Resistance of Gram negative bacteria to porphyrin photosensitization is the main impediment to its use as a broad spectrum antibacterial method.     

Structure of an anti-plasmin inhibitor, eckol, isolated from the brown alga Ecklonia kurome Okamura and inhibitory activities of its derivatives on plasma plasmin inhibitors

Eckol (1), a novel phlorotannin with a dibenzo-1,4-dioxin skeleton, has been isolated from the brown alga Ecklonia kurome Okamura as a potent and specific anti-plasmin inhibitor. Its structure has been elucidated based on the spectral data, in particular, by means of negative nuclear Overhauser effect (NOE), and finally established as 1-(3,5-dihydroxyphenoxy)-2,4,7,9-tetrahydroxydibenzo-1,4-dio xin by X-ray analysis. Some partially methoxylated derivatives of eckol were prepared by methylation with diazomethane and also by selective dimethylation of eckol permethylate (1b) to establish the structural requirements for inhibitory activities on alpha 2-macroglobulin and alpha 2-plasmin inhibitor, the main plasmin inhibitors in plasma.     

Singlet-triplet interconversion of diphenylmethylene. Energetics,dynamics and reactivities of different spin states

A combination of picosecond and nanosecond laser spectroscopy measurements, chemical quenching experiments and triplet sensitization experiments has allowed the determination of the rapid singlet to triplet and slower triplet to singlet intersystem crossing rates for diphenylmethylene in fluid solution at room temperature. It is shown that under the conditions of the kinetic measurements, singlet and triplet diphenylmethylene (¹DPM and ³DPM, respectively) are in rapid equilibrium relative to reactions, so that knowledge of the values of k_ST and k_TS allows determination of the equilibrium constant and change in free energy for the ¹DPM 〈 ³DPM process. The absolute reactivity of ¹DPM toward a series of alcohols has been determined and is discussed in terms of other current investigations of carbene reactivity.     

Effect of methotrexate treatment on the onset of autoimmune kidney disease in lupus mice.

In the present study, we examined the effects of methotrexate (MTX) on the development of autoimmune kidney disease in three kinds of autoimmune prone mice, NZB/NZW F1 (BWF1) mice, MRL/Mp-lpr/lpr (MRL/lpr) mice and NZW/BXSB F1 (WBF1) mice. The results showed that MTX delayed the appearance of proteinuria and prolonged survival of both BWF1 and MRL/lpr mice and inhibited the elevation of blood urea nitrogen (BUN) levels which accompanies the development of lupus nephritis. However, MTX treatment did not affect these in WBF1 mice. Furthermore, MTX could not suppress immunoglobulin G (IgG) class anti-deoxyribonucleic acid (DNA) and anti-trinitrophenol (TNP) antibody production in any variety of mice. These suggest that the therapeutic effect of MTX on BWF1 and MRL/lpr mice does not result in the suppression of IgG autoantibody production.