植物生物分子的电分析化学研究Ⅷ.秋水仙碱的微分脉冲极谱行为及分析应用

秋水仙碱是近年来新发现的有前途的抗癌植物有效成分。秋水仙碱的测定方法,如容量滴定法^[1]、电位滴定法^[2]、紫外分光光度法^[3]、荧光分析法^[4]和高效液相色谱法^[5]等,手续均不太简便。电化学分析研究秋水仙碱主要有阳极伏安法^[6]和交流极谱法^[7],前者因使用固态电极,重现性较差。后者用非水溶剂作介质,灵敏度不高。     

溴甲酚紫的极谱研究

溴甲酚紫是一应用广泛的有机式剂^[1-4]。关于羟基三苯甲烷类染料的极谱研究报导不多^[5]。Ghoneim^[6]曾报导溴甲酚紫在pH<7时产生一个2电子还原波,当pH大于10时,可产生两个1电子还原波。Goel^[7]只研究了第一波的还原机理。本文用普通极谱、脉冲极谱、循环伏安等方法较详细地研究了溴甲酚紫的电还原。提出一电还原机理,解释了半波电位随pH变化的特殊规律。     

悬汞电极阳极溶出伏安法——Ⅳ.纯镓中微量铟、镉、铅的测定

镓中某些杂质可用方波^[1]或示波^[2]极谱法测定。本文用悬汞电极阳极溶出伏安法在经典极谱仪上在溴化钾介质中测定纯镓中的铟、镉、铅。为消除溴化钾浓度小时镉对铟的干扰^[3],使用纯度较高的溴化钾,并提高其浓度四倍。铊对铟的严重干扰,则用EDTA掩蔽铟波,以差减法克服。     

光度法测定镉-邻二氮菲-溴苯三酚红混合配体络合物的平衡常数

混合配体络合物是络合物溶液化学研究中一个十分活跃的领域,有关镉的混合配体有色络合物见诸文献者不多^[1]。作者曾以光度法研究了镉(Ⅱ)-邻二氮菲(phen)-溴苯三酚红(BPR)三元体系中形成络合物的组成及有关光学特性^[2]。     

极谱法研究金属络合物时滴汞电极表面络合剂浓度的表达式

在极谱学中,各作者得到的从半波电位E_1/2求络合物稳定常数的公式中,都要用到半波电位E_1/2和汞滴表面络合剂X^b-的平衡浓度[X]₀这两个最基本的量^[1-11].其中,E_1/2这个量不但可以从实验上直接测定,而且它与标准电极电位、稳定常数、活度系数、扩散系数以及汞滴表面络合剂的平衡浓度等的关系式已由许多学者^[1-6]从理论上进行了推导.     

微波消解-微波等离子体炬原子发射光谱法测定无铅汽油中痕量铅的研究

四乙基铅作为一种良好的抗爆添加剂,曾广泛用于汽油生产中,但由于四乙基铅有很强的毒性,目前国际上已停止生产和使用车用含铅汽油,因此在生产车用无铅汽油时严格控制和准确测定铅的含量十分必要.迄今,测定汽油中铅含量的常用方法是铬酸盐容量法^[1]、一氯化碘法^[2]、X射线光谱法^[3]、分光光度法^[4,5]、原子吸收光谱法^[6]和等离子体光谱法^[7].这些方法或操作烦琐,测定时间较长^[4],或灵敏度低^[1～3],或测定误差较大,且在测试中需使用毒性较大的四乙基铅^[5],或所需的氯化甲基三辛基铵不易购买^[6],或处理过程繁琐,且仪器设备昂贵^[7].因此,建立一种简便、快速、灵敏、准确和无毒副作用的测定无铅汽油中痕量铅的方法已显得十分迫切.近年来发展的微波等离子体炬原子发射光谱法^[8]已有商品化仪器问世^[9].本文利用微波等离子体炬原子发射光谱仪研究了无铅汽油中痕量铅的测定方法,并提出用微波消解法预处理无铅汽油样品,将微波消解技术与微波等离子体炬原子发射光谱法相结合,建立了简便、快速、灵敏、准确和无污染的测定无铅汽油中痕量铅的新方法.     

一系列Ru(II)配合物电致化学发光性质的比较研究

比较研究了以C₂O₄^2－为共反应物时5个结构相关的Ru(II)配合物[Ru(bpy)₂L¹]^2＋, [Ru(bpy)₂L²]^2＋, [Ru(bpy)₂L³]^2＋, [Ru(phen)₂L¹]^2＋和[Ru(phen)₂L²]^2＋(其中bpy＝2,2′-联吡啶, phen＝1,10-邻菲啰啉, L¹＝4-羧基苯基咪唑[4,5-f][1,10]邻菲啰啉, L²＝3-羧基-4-羟基苯基咪唑[4,5-f][1,10]邻菲啰啉, L³＝3,4-二羟基苯基咪唑[4,5-f][1,10]邻菲啰啉)的电致化学发光(ECL)性质. 结果表明, 酚羟基的存在能有效地淬灭Ru(II)配合物[Ru(bpy)₂L²]^2＋, [Ru(bpy)₂L³]^2＋和[Ru(phen)₂L²]^2＋的ECL, 其它Ru(II)配合物的ECL量子效率与[Ru(bpy)₃]^2＋相差不大.     

零电流示波电位滴定盐酸异丙嗪

盐酸异丙嗪是一种较重要的抗组胺药,现行的分析标准为非水滴定法^[1],此外尚有分光光度法^[2]、伏安法^[3]、电极法^[4]、液相色谱法^[5]和流动注射分析法^[6]等。本文将高鸿提出的零电流示波电位滴定法^[7]中的铂片电极修饰一层含四苯基硼酸-异丙嗪电活性物质的PVC膜,使电极对异丙嗪产生响应,可用于四苯基硼酸钠直接滴定异丙嗪的终点指示。     

有机卤化合物中卤素的离子选择性电极的快速微量分析

近年来,离子选择性电极已应用于有机氯、溴^[1-3]及碘^[4]的微量分析。但在电位滴定中,水介质的终点不明显^[5-6],非水介质用的乙酸^[1,2]有刺激性,而1,4-二氧环^[3]已烷则价太贵。     

吸收液采样-高效液相色谱法测定室内空气中甲醛的含量

<正>甲醛是一种无色有刺激性气味的气体，被世界卫生组织(WHO)定为致畸和致癌的物质之一^[1]。我国规定室内空气甲醛的限值为0.10 mg·m-3^[2]。目前监测环境中甲醛的国家标准测定方法很多^[3],常用的有4-氨基-3-联氨-5-巯基-1,2,4-三氮杂茂(Ⅰ)(AHMT)分光光度法^[4]、3-甲基-2-苯并噻唑啉酮腙盐酸盐水合物(MBTH)酚试剂分光光度法^[5]、乙酰丙酮分光光度法^[6]、气相色谱法(GC)^[7]、     

A study of the conformational states of cyclopeptide systems

Summary 1. An empirical method for the quantitative determination of the number of NH groups of different types in peptides based on measurements of the integral intensity of the amide A bands in the IR spectra has been developed.2. The IR spectra of the diastereomeric cyclohexaalanyls in CHCl₃ solutions have been studied; they indicate the participation of an average of four NH groups in IMBHs.3. On the basis of a theoretical conformational analysis and of dipole-moment measurements, the system of IMHBs and the type of dominant conformation of the cyclohexapeptides in nonpolar solvents have been established.M. M. Shemyakin Institute of the Chemistry of Natural Compounds of the Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 347–357, May–June, 1971.     

Lipids of the oils of the fruit and leaves ofHoppopha? rhamnoides

The analysis of some lipids of four forms of the common sea buckthorn has shown that they all differ with respect to the composition of the fatty acids of the triacylglycerols of the leaves. One of the forms is characterized by an infringement of the specificity of the composition of the fatty acids in positions 2 of the triacylglycerols of the oils of the seeds and the leaves.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. V. L. Komarov Institute of Botany, Academy of Sciences of the Azerbaidzhan SSR, Baku. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 710–715, November–December, 1981.     

Spectral moments of phenylenes

In a series of publications Estrada (Estrada, E. J. Chem. Inf. Comput. Sci. 1996, 36, 844-849; 1997 37, 320-328; 1998, 38, 23-27) employed spectral moments of line graphs in QSPR and QSAR relationship studies of various classes of compounds. A recent paper (Markovi?, S.; Gutman, I. J. Chem. Inf Comput. Sci. 1999, 39, 289-293) reported that in QSPR and QSAR investigations of benzenoid hydrocarbons based on linear combination of spectral moments, it made no difference whether one used spectral moments of the molecular graph or those of the line graph. In the present work spectral moments of molecular graphs (Mk) and line graphs (muk) of phenylenes are considered. The first few Mk's and muk'S of phenylenes are dependent on identical structural parameters. It is proved that the two sets of moments of phenylenes are linearly dependent. It is also shown that in the case of the heat of formation of phenylenes there is no advantage in using lower spectral moments of line graphs instead of lower spectral moments of molecular graphs. In this way the redundancy observed in the case of benzenoid hydrocarbons is also shown to exist in the class of phenylenes.     

USE OF A pH-STAT DILUTION TO DETERMINE CRITICAL MICELLE CONCENTRATIONS AND COUNTERION CONCENTRATIONS OF IONIC MICELLES1

The use of a pH-stat to determine the critical micelle concentration (c.m.c.) of ionic micellar solutions is described. Counterion is released with the dilution of an ionic micellar solution at all concentrations above the c.m.c. The titration of the released counterion permits the evaluation of the c.m.c. and the associated amount of counterion for any concentration above the c.m.c. The diluent is the same medium in which the micelle is dissolved. Thus any ionic strength, ion composition, or pH may be used. Examples of the method to determine the c.m.c. of promethazine hydrochloride in water and of tetracaine hydrochloride in 0.128 N NaCl as a function of pH are given. Also the c.m.c of promethazine hydrochloride - Tween 80 mixtures was examined as a function of mole fraction.     

Äquidensitometrie: Eine Methode zur Beurteilung der Struktur von Plasmen—Qualitative Beurteilung des Lanthan-Gleichstrombogens durch Äquidensitometrie von monochromatischen Bogenphotographien

A new method has been developed for the experimental characterization of d.c. arc plasmas. The method consists of the combination of the spectral photography of d.c. arc plasmas with a slitless, stigmatic plane-grating spectrograph and the characterization of the photographs with the aid of photographic equidensitometry. The principles of the method are described. The method is used for the investigation of a lanthanum d.c. arc plasma. The qualitative results of the measurements of the axial distributions of the light emission and lanthanum and calcium particle concentrations in the arc are discussed. The limitations and shortcomings of the method are pointed out.     

Theoretical conformational analysis of the methylamide of N-acetyl-L-alanyl-L-prolyl-L-alanine. II

Summary 1. Spatial forms of Ac-L-Ala-L-Pro-L-Ala-NHMe with trans peptide bonds are the most preferred. Elongation of the peptide chain promotes the stabilization of the trans configuration of the tertiary amide group.2. In the structure of the compound investigated, the dominating role is played by the interaction of the neighboring residues.3. Of the six types of conformations of X-Pro-Y observed in proteins, the first four belong to the preferred forms of the Ac-L-Ala-L-Pro-L-Ala-NHMe molecule.M. M. Shemyakin Institute of Bioorganic Chemistry, Academy of Science of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 626–630, September–October, 1975.     

An investigation of the structure of the phospholipids of the cotton plant of variety Tashkent-2

Summary 1. The fatty-acid compositions of the total phospholipids of the seed kernels of the cotton plant of variety Tashkent-2, after the elimination of carbohydrates, and of their main components have been studied.2. It has been found that at 37–38°C the time of enzymatic hydrolysis is considerably shortened.3. A study of the products of acid and enzymatic hydrolysis has shown the structure of the individual phospholipids.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 145–148, March–April, 1976.     

Reaction of xylan with aqueous solutions of alkali

Conclusions 1. The action of an aqueous solution of caustic soda on xylan leads to the formation of both a molecular and an alkoxide form of this polysaccharide. The composition and amount of the alkoxide formed depend on the conditions of treating the xylan with alkali.2. In the reaction of an aqueous solution of caustic soda with xylan, the hydrogen of the alcohol grouping on the second carbon atom exhibits the greatest reactivity.3. The result of IR spectroscopy confirm the existence of a chemical interaction of the xylan with caustic soda.4. According to X-ray analysis, the action of a solution of caustic soda on xylan leads to a decrease in intermolecular interaction, to a more ordered supermolecular structure, and to the appearance of crystallinity.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 4, pp. 206–210, 1969     

Micellization of Cetylpyridinium Chloride Using Conductometric Technique

Abstract

Conductometric technique has been used to investigate the equilibrium properties of cetylpyridinium chloride (CPC) in the presence of a series of aliphatic alcohols. The dependence of conductivity of surfactant solution in the presence of particular amount of alcohol has been studied. According to the experimental results, ethanol cause to decrease the dielectric constant and conductivity of micellar solution. Alcohols with longer chain may change the conductivity of solution depend on concentration of surfactant. At low concentration of CPC near critical micelle concentration (cmc) region, the minimum value of conductivity can be observed. This minimum value can be controiled by decreasing of free monomer concentration and also increasing degree of dissociation of micelle because of penetration of alcohols in micellar core. Using Conductometric technique cmc and α (degree of dissociation of counterion) of CPC were evaluated. The micelle formation of CPC has been considered in ethylene glycol (E.G)/ water and glycerol/water mixtures. It has been shown, the logarithm of cmc is directly depended on the ratio of E.G/water or glycerol/water.     

Interaction of carbamazepine and promethazine in rabbits

The interaction of carbamazepine and promethazine in rabbits has been investigated. The influence of this interaction on the processes of biotransformation in the liver was revealed. The drugs were administered as single oral doses (100 mg of each drug) as well as simultaneously with an interval of 15 min. The sequence of administration of the drugs was varied. The influence of promethazine on the pharmacokinetics of carbamazepine is expressed by: (a) strong suppression of carbamazepine's level in plasma and appearance of multiple peaks of carbamazepine; (b) suppression of biotransformation of carbamazepine into carbamazepine-10,11-epoxide at the initial stages and its increase in the intermediate stages. These data are explained by the active capture of carbamazepine by liver at its primary transferal through the liver and sufficient presystem elimination of carbamazepine in the presence of promethazine. The character of kinetic curves of promethazine varies substantially under the influence of carbamazepine. However, this change is not as strong as in case of carbamazepine. The concentration of promethazine in plasma varies slightly and multiple peaks are not observed. The rate of terminal elimination of promethazine varies and abrupt prolonged segments of elimination appear at the initial and terminal stages of the process in return. These data perhaps indicate the induction of biotransformation of promethazine in the presence of carbamazepine-an inductor of microsomal liver enzymes. The changes of kinetics of promethazine and carbamazepine by simultaneous administration as compared with their administration separately, as well as a comparative consideration of pharmacokinetics of promethazine and carbamazepine by simultaneous administration show the existence of competition in the elimination between these drugs and the periodic saturation of liver for their biotransformation.