两种β－环糊精衍生物手性石英毛细管柱拆分对映体

合成了全戊基化（Ⅰ）和部分戊基化三氟乙酰化（Ⅱ）的两种“环糊精手性固定相。将它们分别与ＯＶ－７混合制备出柱效大于４１００塔片／ｍ，热稳定性可达２１０℃的手性石英毛细管住。对映体拆分结果表明，固定相Ⅰ对醇、二醇、胺、γ－内酯等对映体比Ⅰ有更高的选择性。     

二阶导数差示脉冲极谱法用于醋酸氟氢可的松的定量研究

用二阶导数差示脉冲极谱法对醋酸氟氢可的松进行了定量分析。在０．００１ｍｏｌ／Ｌ硫酸＋乙醇＋水（１＋２５＋２４）的底液中，醋酸氟氢可的松于－０．３４０Ｖ（ｖｓＡｇ／ＡｇＣｌ）处出现一良好的二阶导数差示脉冲极谱峰，在５～１４０μｇ／ｍＬ范围内，醋酸氟氢可的松的浓度与其二阶导数差示脉冲极谱峰幅值呈线性关系，检测限为０．４ｎｇ／ｍＬ。本法操作简便、快速、灵敏、结果准确。     

A fluorescent chemical sensor for Fe based on blocking of intramolecular proton transfer of a quinazolinone derivative

In this paper, 2-(2′-hydroxy-phenyl)-4(3H)-quinazolinone (HPQ), a typical compound that exhibits excited state intramolecular proton transfer (ESIPT) reaction and possesses good photophysical properties, is synthesized and used as fluoroionophore for Fe³⁺ sensitive optochemical sensor. The decrease of fluorescence intensity of HPQ membrane upon the addition of Fe³⁺ was attributed to the blocking of ESIPT reactions of HPQ and quenching its fluorescence. The effect of the composition of the sensing membrane was studied, and experimental conditions were optimized. The sensor shows a linear response toward Fe³⁺ in the concentration range of 7.1 × 10⁻⁷ M to 1.4 × 10⁻⁴ M with a limit of detection of 8.0 × 10⁻⁸ M, and a working pH range from 2.5 to 4.5. It shows excellent selectivity for Fe³⁺ over a large number of cations such as alkali, alkaline earth and transitional metal ions. The proposed sensor is applied to the determination of the content of iron ions in pharmaceutical preparations samples with satisfactory results.     

Design and Synthesis of Glycosylated Aromatic Nitrogen Mustard Derivatives

Antibody-directed enzyme prodrug therapy(ADEPT) is a new strategy for the treatment of cancer that has arisen in recent twenty years, the main merits of which are that it can improve the selectivity of anticancer drugs and reduce the side effects in remote tissue. In the present study, two prodrugs-glycosylated aromatic nitrogen mustard derivatives were synthesized. Glucose and lactose were converted into glycosyl donors-trichloroacetimidate; the obtained glycosyl donors were glycosylated with p-nitrophenol(glycosyl donors) to form β-glucosyl p-nitrobenzene and β-lactosyl p-nitrobenzene that were protected by acetyl in a stereoselective manner; the two products were reduced by zinc dust and then treated with ethylene oxide, afforded two glycosylated nitrogen mustard derivatives that were protected by acetyl; the last step was to deacetylate and then afforded the two target compounds that could be used as prodrugs of ADEPT for further Anti-tumor research.     

多氟烷基取代的环丙烷衍生物的合成

以连二亚硫酸钠为引发剂, 烯丙基丙二酸二乙酯与多氟烷基碘代烷在温和反应条件下反应, 方便地得到一系列多氟烷基取代的环丙烷衍生物, 产率45%～55%. 在相同条件下, 烯丙基乙酰乙酸乙酯与多氟烷基碘代烷反应得到相应的加成物, 加成物随后用碱处理也得到环合的产物.     

Studies of surface properties of Na- and La-montmorillonites

This paper presents possible applications of thermal analysis, sorptometry and porosimetry to study physico-chemical properties of Na- and La-montmorillonite samples, especially for determination of total surface heterogeneity. The quasi-isothermal thermogravimetric (Q-TG) mass loss and its first derivative (Q-DTG) curves with respect to temperature and time obtained during programmed liquid thermodesorption under quasi-isothermal conditions have been used to study adsorbed layers and heterogeneous properties of the Na- and La-montmorillonites. Calculations of the desorption energy distribution functions by analytical procedure using mass loss Q-TG and differential mass loss Q-DTG curves of thermodesorption under quasi-isothermal conditions of polar and non-polar liquid vapours preadsorbed on a material surface are presented. Parameters relating to porosity of samples were determined by sorptometry, mercury porosimetry and atomic force microscopy (AFM). From nitrogen sorption isotherms from sorptometry and porosimetry methods, the fractal dimensions of montmorillonites have been calculated. Moreover, a new approach is proposed to calculate fractal dimensions of materials obtained from Q-TG curve; this is compared with values obtained by the above methods. The total heterogeneous properties (energy distribution function and pore-size distribution functions) of samples studied were estimated. The radius and pore volume of the tested samples calculated on the basis of thermogravimetry, sorptometry and porosimetry techniques were compared and good correlations obtained.     

三阶导数分光光度法同时测定铜,钴与镉

采用三阶导数光谱技术，以ｍｅｓｏ－四（４－三甲铵基苯基）卟啉作显色剂分光光度法同时测定了微量的铜、钴与镉。方法中以铅离子掩蔽过剩试剂的吸收峰，然后进行三级微分求导，可以使铜、钴、镉吸收峰完全分开，于４１５ｎｍ、４３４ｎｍ及４３８ｎｍ处同时测定３元素含量，由三阶导数光谱的吸光值可求算出配合物的三阶导数摩尔吸光系数分别为：１．１１×１０６、３．９５×１０５及６．４７×１０５Ｌ·ｍｏｌ－１·ｃｍ－１。     

Enantioseparation in capillary electrophoresis using 2-O-(2-hydroxybutyl)-beta-CD as a chiral selector

The resolving ability of 2-O-(2-hydroxybutyl)-beta-CD (HB-beta-CD) with different degrees of substitution (DS = 2.9 and 4.0) as a chiral selector in CZE is reported in this work. Fourteen chiral drugs belonging to different classes of compounds of pharmaceutical interest such as beta-agonists, antifungal agents, ageneric agents, etc., were resolved. The effects of the DS of HB-beta-CD on separations were also investigated. The chiral resolution (R(s)) was strongly influenced by the concentrations of the CD derivative, the BGE, and the pH of the BGE. Under the conditions of 50 mmol/L Tris-phosphate buffer at pH 2.5 containing 5 mmol/L HB-beta-CD, all 14 analytes were separated. The very low concentration necessary to obtain separation was particularly impressive. The DS had a significant effect on the resolution of the chiral drugs and the ionic strength of the separation media; hence, the use of a well-characterized CD derivative is crucial.     

普鲁士兰修饰碳黑微电极同时微分伏安法测定多巴胺和抗坏血酸

将含有1.0%普鲁士蓝的碳黑与固体石蜡按2.5∶1(质量比)混合后装入φ0.2mm的石英毛细管中,在其上端插入一铂丝并抛光后即制成普鲁士蓝修饰碳黑微电极.对多巴胺(DA)及抗坏血酸(VC)在此电极上的电化学行为及应用此电极测定两组分的最佳条件进行了研究,在定量测定中采用二次微分线性扫描伏安法.在最佳条件下,DA与VC的峰电流(i″p)分别与各自的浓度保持如下线性关系DA为4.0×10-6～8.0×10-4mol·L-1,VC为6.0×10-5～1.0×10-3mol·L-1;检出限(3σ)依次为2.0×10-6mol·L-1及1.0×10-5mol·L-1.应用此方法分析了3种含DA及VC的混合溶液,测得结果的相对标准偏差(n=8)依次小于2.0%及3.0%,回收率范围依次为96.5%～101.0%及95.0%～102.5%.