Microwave-accelerated derivatization processes for the determination of phenolic acids by gas chromatography-mass spectrometry

A rapid method for the derivatization of phenolic antioxidants using microwave irradiation has been developed. Six antioxidatively active phenolic components of wines and fruits, namely gallic acid, gentisic acid, vanillic acid, caffeic acid, ferulic acid and p-coumaric acid were used in the model study. The solution of phenolic acids was evaporated to dryness on a rotary evaporator followed by further drying under microwave irradiation (600 W, 30 s). The resultant residue was dissolved in pyridene and treated with bis(trimethylsilyl)acetamide while irradiated by microwave using high power for 30 s. Controlled reaction was carried out employing bis(trimethylsilyl)trifluoroacetamide under conventional heating for 30 min. The trimethylsilyl derivatives were identified and quantified on a gas chromatography/mass selective detector. The mass spectral fragmentation patterns of the derivatives obtained by microwave irradiation were identical to those prepared by heating. The yields of microwave-assisted silylation were comparable to those from conventional heating. The rsd were less than 8% for six replicates. The linearity in wine matrix was nearly perfect. This method is a useful protocol to examine the phenolic constituents in wines and agricultural products.     

环己硅烷类液晶化合物的量子化学研究

运用AM1和PM3两种SCF-MO方法，通过能量梯度全优化计算，给出20种环己硅烷类（苯基乙烷系）液晶化合物的稳定几何构型、电子结构和基本性质．联系有机电子结构理论进行了细致的讨论．     

甲烷部分氧化制合成气：Ⅲ.镍系催化剂物性及与催化性能间的关联

使用ＴＰＲ和Ｈ２－ＴＰＤ技术对镍铝系催化剂的还原和氢脱附性能进行了研究，并与其催化性能相关联。结果发现，镍铝系催化剂的氢脱附能力与其催化性能之间有一定联系，脱附氢能力越强，催化剂的甲烷部分氧化反应性能就越好，但催化性能与还原性能无直接关联。     

磷酰化与非磷酰化蛋氨酸水溶液的脉冲辐解研究

蛋氨酸能快速清除导致辐射损伤的·OH自由基，在放射生物学上是一类很重要的辐射保护剂，因此，引起了人们的广泛关注［l一到．生物大分子的磷酸化作用亦越来越受到重视，特别是近年来基因调控研究发现，许多蛋白质和生物酶只有被磷酸化氧化才具有生理活性，文献［4－6］报导蛋     

The complexation of apo-metallothionein with cadmium ion and its conformation study

The circular dichroism was used to study the complexation of two isoforms of rabbit liver apo-metallothioneins (apo-MT1 and apo-MT2) with Cd²⁺ ion and the influence of Cd²⁺ ion on the conformation of reconstituted MTs. The stability of sulfhydryls of apo-MT has been investigated at the room temperature in the presence of air. The reconstitutions of apo-MT1 with Cd²⁺ ion were carried out atpH 4.71 (stable state) andpH 7.9 (with 90% sulfhydryls oxidated) respectively. it was found that the characteristic CD band at 257 nm(+), 238 nm(?), 226 nm(+) of reconstituted MT with Cd²⁺ ion was the same as native MT atpH 4.71, however only one peak at 243 nm(+) appeared on the CD spectra atpH 7.9 which arose from mononuclear complexes with four separated thiolate ligands per Cd²⁺ ion. The CD spectra of apo-MTs+7 eq Cd²⁺ system were measured at variouspH values. It was found that the peak at 256 nm of apo-MT1 binding Cd²⁺ ion split into two small peaks atpH between 2.42 and 3.02, and became one peak atpH 3.32, while the shapes of Cd peaks of apo-MT2 binding Cd²⁺ ion did not change withpH, indicating that the binding sites and pathway of apo-MT1 binding Cd²⁺ ion were different from those of apo-MT2. A possible mechanism was suggested.     

Aerobic oxidation assisted by ligand-free palladium catalysts

Aerobic oxidation of electron-rich benzylic and phenyl allylic alcohols was achieved with high yields with only 0.1 mol.% of Pd(OAc)2 catalyst in the absence of any ligand. This procedure was expected to be valuable for realistic industrial-scale applications from both economic as well as environmental points of view.     

Analysis of flavonoids in <Emphasis Type="Italic">Ginkgo biloba</Emphasis> L. and its phytopharmaceuticals by capillary electrophoresis with electrochemical detection

A high-performance capillary electrophoretic (CE) method with electrochemical detection (ED) has been developed for determination of the pharmacologically active flavonoids in Ginkgo biloba L. and phytopharmaceuticals containing its extract. Epicatechin, catechin, rutin, apigenin, luteolin, and quercetin are important flavonoids in this plant. Operated in a wall-jet configuration, a 300 micro m diameter carbon-disk electrode was used as working electrode with good response to the six analytes at +1000 mV (relative to the SCE). Under the optimum conditions, the analytes were separated within 22 min in a borax buffer (pH 9.0). Excellent linearity was obtained over two orders of magnitude and detection limits (S/N=3) ranged from 1.4 x 10(-7) to 5.0 x 10(-7) g mL(-1) for all six analytes. The method was successfully used for assay of Ginkgo biloba L. and its phytopharmaceuticals after a relatively simple extraction procedure; the results obtained were satisfactory.     

Carbon-13 spectra of some tetrahydropyridines. The structure of the tetrahydropyridines from 3,5-lutidine 1-oxide and mercaptans in acetic anhydride

The reaction of 3,5-lutidine 1-oxide ( 1 ) with t-butyl mereaptan in acetic anhydride, with or without triethylamine, was reinvestigated. There was obtained 2-t-butylthio-3,.5-lutidine as the major product, a small quantity of 3-(t-bulylthio)methyl-5-picoline, 1-acetyl-2,3-diacetoxy-3,5-dirnethyl-6-t-butylthio-1,2,3,6-tetrahydropyridine (which represents a structure revision) and l-acetyl-2,6-dihydroxy-3-t-butylthio-3,5-dimethyl-1,2,3,6-tetrahydropyridine. A similar reaction of 1 with 1-adamantyl mercaptan furnished 2-(l-adamantylthio)-3,5-lutidine and 1-acetyl-2,3-diacetoxy-3,5-dimethyl-6-(1-adamantylthio)-1,2,3,6-tetrahydropyridine. The structures of these new tetrahydropyridines were established primarily by carbon-13 nmr spectra.