氨基磺酸均相催化合成柠檬酸三丁酯

以氨基磺酸为均相催化剂催化合成柠檬酸三丁酯,确定了酯化优化条件。试验结果表明:在催化剂6.0%(以柠檬酸为基数的质量百分数),柠檬酸0.1mol,丁醇0.55mol,反应温度100～150℃,反应时间90min的条件下,柠檬酸的酯化率达到98.6%以上。     

Interpretation of inorganic arsenic metabolism in humans in the light of observations made in vitro and in vivo in the rat

The toxicity of inorganic trivalent arsenic for living organisms is reduced by in vivo methylation of the element. In man, this biotransformation leads to the synthesis of monomethylarsonic (MMA) and dimethylarsinic (DMA) acids, which are efficiently eliminated in urine along with the unchanged form (As_i). In order to document the methylation process in humans, the kinetics of As_i, MMA and DMA elimination were studied in volunteers given a single dose of one of these three arsenicals or repeated doses of As_i. The arsenic methylation efficiency was also assessed in subjects acutely intoxicated with arsenic trioxide (As₂O₃) and in patients with liver diseases. Several observations in humans can be explained by the properties of the enzymic systems involved in the methylation process which we have characterized in vitro and in vivo in rats as follows: (1) production of As_i metabolites is catalyzed by an enzymic system whose activity is highest in liver cytosol; (2) different enzymic activities, using the same methyl group donor (S-adenosylmethionine), lead to the production of mono- and di-methylated derivatives which are excreted in urine as MMA and DMA; (3) dimethylating activity is highly sensitive to inhibition by excess of inorganic arsenic; (4) reduced glutathione concentration in liver moderates the arsenic methylation process through several mechanisms, e.g. stimulation of the first methylation reaction leading to MMA, facilitation of As_i uptake by hepatocytes, stimulation of the biliary excretion of the element, reduction of pentavalent forms before methylation, and protection of a reducing environment in the cells necessary to maintain the activity of the enzymic systems.     

Reaction of pentafluorobenzoylpyruvic acid with amines

Reactions of pentafluorobenzoylpyruvic acid with amines afford the respective enamines. The intramolecular cyclization of the latter results inN-substituted 4-quinolone-2-carboxylic acids. Ammonia and triethylamine favor the cyclization of pentafluorobenzoylpyruvic acid to 2-carboxychromone.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 299–302, February, 1994.     

Cubane derivatives 1. Synthesis and molecular structures of the esters of 1,4-cubanedicarboxylic acid

An effective method of esterification of 1,4-cubanedicarboxylic acid with alkylsulfuric acids is proposed. The derivatives of alkanols with substantially different pK_a Valus are obtained in high yields. Molecular structures of the esters obtained are confirmed by various methods. The X-ray study showed a remarkable effect of the nature of an alkyl radical on the geometry of the cubane core.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp.668–672, April, 1994.The authors thank Dr. G. V. Lagodzinskaya for analyzing the NMR spectra and for useful discussions.     

Electrochemical co-oxidation of C-H acids and methanol as a new route to functionalized cyclopropanes

Electrolysis of dimethyl malonate or methyl cyanoacetate in methanol in the presence of LiCl in an undivided cell leads to formation of 1,1,2,2-cyclopropanetetracarboxylic derivatives.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1835–1836, October, 1994.This work was supported by the International Science Foundation (Grant No MHY 000).     

《有机化学实验》教材中己二酸制备的改进

目前实验室制备己二酸的方法大部分采用环己醇经高锰酸钾氧化来制得,这种方法所耗用的氧化剂用量大,而且所制备出的已二酸实际产率不高。我们采用环己酮为原料来制己二酸,此方法可达到较理想的效果。改进后同样能使学生掌握实验技能,达到实验教学的目的,而且也节省了资金和时间。     

Synthesis and characterization of novel thermoresponsive‐co‐biodegradable hydrogels composed of N‐isopropylacrylamide,poly(L‐lactic acid), and dextran

A series of novel multifunctional hydrogels that combined the merits of both thermoresponsive and biodegradable polymeric materials were designed, synthesized, and characterized. The hydrogels were copolymeric networks composed of N‐isopropylacrylamide (NIPAAM) as a thermoresponsive component, poly(L‐lactic acid) (PLLA) as a hydrolytically degradable and hydrophobic component, and dextran as an enzymatically degradable and hydrophilic component. The chemical structures of the hydrogels were characterized by an attenuated total reflection–Fourier transform infrared spectroscopy (ATR–FTIR) technique. The hydrogels were thermoresponsive, showing a lower critical solution temperature (LCST) at approximately 32 °C, and their swelling properties strongly depended on temperature changes, the balance of the hydrophilic/hydrophobic components, and the degradation of the PLLA component. The degradation of the hydrogels caused by hydrolytic cleavage of ester bonds in the PLLA component was faster at 25 °C below the LCST than at 37 °C above the LCST, determined by the ATR–FTIR technique. Due to their multifunctional properties, the designed hydrogels show great potential for biomedical applications, including drug delivery and tissue engineering. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5054–5066, 2004     

INFLUENCE OF POLYMER CHARACTERISTICS AND MELT-SPINNING CONDITIONS ON THE PRODUCTION OF HIGH RANDOMNESS 60PHB/PET THERMOTROPIC LIQUID CRYSTAL COPOLYESTER FIBER

Six samples of linear high randomness 60PHB/ PET thermotropic liquid crystal copolyesters are made by melt copolymerization at 290℃ , whose randomness about 0.955 is measured by the discernible 'H-NMR spectrometer. High tenacity, high module fiber is prepared by melt spinning in liquid crystal phase. The effect of molecular weight, shear rate, temperature as well as spinning drawn ratio on the mechanical behavior of 60PHB / PET copolyester fiber are shown that, lower shear rate (2~ 10 s~(-1)), higher temperature melting (300℃ ), lower temperature spinning (280℃ ) and higher molecular weight are favourable to the increase of the fiber mechanical properties. With the variance of drawn ratio, fiber mechanical property has a transition point due to traversion from shear-orientation to drawn-orientation. The copolyester fiber has high crystallinity, high orientation at the crystalline region, high chain orientation and high regular fibrillar structure.     

Influence of poly(aminoquinone) on corrosion inhibition of iron in acid media

The inhibitor performance of chemically synthesized water soluble poly(aminoquinone) (PAQ) on iron corrosion in 0.5 M sulphuric acid was studied in relation to inhibitor concentration using potentiodynamic polarization and electrochemical impedance spectroscopy measurements. On comparing the inhibition performance of PAQ with that of the monomer o-phenylenediamine (OPD), the OPD gave an efficiency of 80% for 1000 ppm while it was 90% for 100 ppm of PAQ. PAQ was found to be a mixed inhibitor. Besides, PAQ was able to improve the passivation tendency of iron in 0.5 M H₂SO₄ markedly.