二阶校正法与三维荧光光谱相结合直接测定人体血浆中的水杨酸

水杨酸、萘普生及血浆背景干扰组分,这三者荧光光谱重叠严重,如果不经分离,无法用常规方法定量分析水杨酸.本文利用二阶校正的优势,将三维激发发射荧光光谱与平行因子分析算法和交替三线性分解算法相结合,快速分析测定血浆中的水杨酸.当因子数选为4时,用两种算法获得的回收率分别为(103.8±3.5)%和(98.4±1.4)%.实验结果表明,此方法可用于干扰组分共存下,快速定量测定血浆中的水杨酸,从而可用于研究阿斯匹林的代谢过程.     

The enantioselective hydrolysis of racemic naproxen methyl ester in supercritical CO2 using Candida rugosa lipase

The enantioselective hydrolysis of racemic naproxen methyl ester by Candida rugosa lipase (CRL) was studied in aqueous buffer solution/isooctane reaction system in the presence of supercritical CO₂. The effects pressure (75–160 bar), temperature (32–42 °C) and reaction time (0.5–12 h) on the enantiomeric excesses of the product (ee_p) and the substrate (ee_s), enantiomeric ratio (E), conversion (x) and enzyme activity were investigated in a batch reactor system. The highest enantiomeric ratio achieved at 120 bar of pressure, 37 °C of temperature and 2 h of reaction time was E = 193 with x = 41.3%, ee_p = 97.9% and ee_s = 68.8%. CRL remained active at least for 12 h at 37 °C and 120 bar in supercritical CO₂ medium. Furthermore, enantiomeric ratio increased with increasing reaction time and reached the value of E = 236 with ee_p = 98.2%, ee_s = 70.0% and x = 41.6% after 12 h of hydrolysis.     

6-甲氧基-2-丙酰萘生产工艺改进

以 β 萘酚为原料 ,以 1,2 二氯乙烷及硝基甲烷代替剧毒物质硝基苯作为丙酰化反应中的溶剂 ,经甲醇、硫酸甲基化 ,丙酰氯、无水三氯化铝丙酰化制备 6 甲氧基 2 丙酰萘 ,总收率达73 8%。     

Highly efficient catalyst system for the synthesis of 2‐arylpropionic acids by carbonylation

Carbonylation of 1‐(4‐isobutylphenyl)ethanol has been studied using a homogeneous catalyst system consisting of PdCl₂(PPh₃)₂/ TsOH/ LiCl. Higher reaction rates with TOF up to 1200 h⁻¹ and ibuprofen selectivity >95% have been achieved at 388 K under a CO partial pressure of 5.4 MPa. The reaction proceeds through the formation of 4‐isobutylstyrene and 1‐(4‐isobutylphenyl)ethyl chloride as intermediates. The same catalyst system is shown to be effective for carbonylation of various α-arylethanols, vinyl aromatics and corresponding chloro derivatives. This revised version was published online in July 2006 with corrections to the Cover Date.     

Penicillium expansum脂肪酶选择性拆分外消旋萘普生

为了实现固定化扩展青霉TS414(Penicillium expansum TS414)脂肪酶在有机相中对外消旋萘普生的高效拆分,实验考察了水分、温度、有机溶剂、酶浓度、醇结构和醇浓度对酶促拆分反应的影响,确立了优化的酯化反应条件为：异辛烷为溶剂,外消旋萘普生2.15 mmol/L,正丙醇34.3 mmol/L,固定化酶量12 g/L,水0.05%(j), 40℃恒温摇床中200 r/min反应100 h. 在此条件下,酯化拆分反应的转化率为48.3%. 结果表明,固定化Penicillium expansum脂肪酶是一种较为理想的用于外消旋萘普生拆分的工具酶.     

Novel Use of Similarity Factors f2 and Sd for the Development of Diltiazem HCl Modified-Release Tablets Using a 32 Factorial Design

ABSTRACT

The objective of this study was to develop modified-release tablets of diltiazem HCl using a direct compression technique. A 3² factorial design was employed using the amount of alkali-treated guar gum and cetyl alcohol as independent variables. This article proposes the use of a novel approach—f₂and S_d values as dependent variables—to evaluate the effect of selected independent variables along with other dependent variables (i.e., percentage drug released in x min, Y_x; time required for z% drug release, t_z; and mean dissolution time (MDT)). It is concluded that when a decision is to be made for the selection of a best batch, it is perhaps more realistic to use the f₂ or S_d value which takes into account the dissolution profile as a whole, as opposed to Y_x and t_z values which use just one point from the dissolution plot. The batch showing the f₂ value nearest to 100 or the S_d value nearest to zero is ranked as the best batch (diltiazem HCl 90 mg, alkali-treated guar gum 80 mg and cetyl alcohol 15 mg). The gel strength and matrix erosion of the formulated tablets were dependent on the type and amount of the adjuvants. The drug release rate is well correlated with matrix erosion. The kinetics of drug release fitted best to the Korsmeyer and Peppas model. It is concluded that by using a proper combination of the hydrophilic polymer and cetyl alcohol one can achieve a desirable drug release pattern.     

聚苯乙烯二醋酸碘苯在萘普生合成中的应用

2-萘甲醚(1)在无水AlCl3催化下与丙酰氯反应得6-甲氧基-2-丙酰萘(2),(2)在原甲酸三乙酯、硫酸下采用聚苯乙烯二醋酸碘苯催化进行1,2-芳基迁移重排得2-(2-(6-甲氧基萘基))丙酸乙酯(3),(3)在氢氧化钠水溶液中水解、酸化得萘普生(4)。总收率约47.4%(以2-萘甲醚计)。试验研究了影响合成2-(2-(6-甲氧基萘基))丙酸乙酯(3)的多种因素,如:硫酸的用量、原甲酸三酯的用量以及聚苯乙烯碘苯的回收利用。     

S-萘普生的不对称合成

研究了以 6 甲氧基 2 丙酰基萘和 ( 2R ,3R) 酒石酸二甲酯为原料 ,用分子筛代替甲磺酸作催化剂合成了缩酮 2 乙基 2 ( 6 甲氧基 2 萘基 ) 1 ,3 二氧杂环戊烷 ( 4R ,5R ) 二羧酸二甲酯 ,此缩酮经过不对称溴化、水解、重排、脱溴反应后 ,得到了S -( ) 萘普生 ,总产率达 4 2 .5% .本合成路线具有反应条件温和 ,操作方便 ,三废少等优点 .