高效液相色谱法测定重氮反应中6-溴-2,4-二甲基苯胺盐酸盐

通过采用高效液相色谱法测定6-溴-2,4-二甲基苯胺重氮反应液中6-溴-2,4-二甲基苯胺盐酸盐的含量,提出了高效液相色谱法监测6-溴-2,4-二甲基苯胺重氮反应进程的方法。以Hypersil BDS-C18色谱柱(4.6 mm×200 mm,5μm)为固定相,以乙腈-水(60+40)溶液为流动相,检测波长为210 nm。在此检测条件下,胺盐的质量浓度在5.0～200.0 mg.L-1范围与其峰面积呈线性关系,测得回收率在96.6%～103.0%之间。     

二元含胺聚合引发体系

一、引言近年来发现了以过氧化苯甲酰与 N,N-二甲基苯胺的混合物作为乙烯型单体聚合的引发剂,被称之为有机的氧化-还原引发体系,并在此基础上有了进一步的新发现。此等新发现的引发剂皆有二个组分,并且当二个组分单独存在时都无引发能力,也很难划分为氧化剂与还原剂二个部分,故暂称为复合引发剂。本文将先介绍过氧化苯甲酰-N,N-二甲基苯胺引发剂,随后是以 N,N-二甲基苯胺为基础的新引发剂。     

2,4-二甲基苯胺印迹电极的零流电位法制备与应用

以电聚合方式,在石墨烯修饰的铅笔芯电极表面制备出2,4-二甲基苯胺的分子印迹聚合物,以零流电位变化的最大差值为指标获得最佳电聚合参数。磷酸缓冲溶液的pH为6.47,功能单体与模板分子的配比为1∶8,电位范围为–0.8～0.8 V,聚合圈数为26,洗脱时间为5 min。与2,4-二甲基苯胺结构相近的物质如4-氯苯胺、4-氨基联苯、联苯胺、邻甲苯胺等均不干扰测定。2,4-二甲基苯胺质量浓度的对数在0.121 2～605.908μg/L范围内与零流电位线性关系良好,相关系数为0.991,检出限为0.040 6μg/L。测定结果的相对标准偏差为0.84%(n=5),平均回收率为95.59%～101.70%。该电极制备简单,灵敏度高,选择性和稳定性好,适用于实际废水中2,4-二甲基苯胺的检测。     

用L-脯氨酸衍生物作为手性流动相添加剂拆分对映异构体

用自制的N-十二酰基-L-脯氨酸和N-十二酰基-L-脯氨酸-3,5-二甲基苯胺两种L-脯氨酸衍生物作手性流动相添加剂,在氨丙基硅烷化硅胶柱上,用正己烷/异丙醇作流动相,对多种手性化合物进行了高效液相色谱拆分.实验结果表明用N-十二酰基-L-脯氨酸作添加剂拆分的12种手性化合物,有8种手性化合物能得到拆分,具有较好的手性选择性.虽然用N-十二酰基-L-脯氨酸-3,5-二甲基苯胺作添加剂,手性选择性也较好,但由于含有苯环,紫外吸收增强,基线波动严重.     

对-氨基二甲基苯胺缩PMBP席夫碱及其配合物的合成、表征和抑菌活性

对-氨基二甲基苯胺缩PMBP席夫碱及其配合物的合成、表征和抑菌活性     

酚醛型吸附树脂在非水体系中对吡啶和N,N-二甲基苯胺的吸附性能研究

研究了酚醛型吸附树脂JDW 2在非水体系中对吡啶和N ,N 二甲基苯胺的静态吸附 .由实验结果推论正己烷中树脂对吡啶和N ,N 二甲基苯胺的吸附是以氢键吸附机理为主进行的 ,JDW 2酚醛型吸附树脂在正己烷中 ,等温吸附吡啶和N ,N 二甲基苯胺的平衡吸附数据符合Langmuir方程 ,相关系数在 0 99以上 ,因此 ,酚醛型吸附树脂在正己烷中吸附吡啶和N ,N 二甲基苯胺属单分子层吸附 ;同时对非水体系中乙醇或乙酸乙酯的含量对树脂吸附吡啶和N ,N 二甲基苯胺的影响进行了研究     

对-(二甲氨基)苯基锗倍半氧化物的合成、结构及其对体外培养癌细胞的作用

在常压下,由N,N′-二甲基苯胺和GeCl_4合成了对-(二甲氨基)苯基锗倍半氧化物,研究了它的红外光谱、光电子能谱及热分析性质,讨论了化合物的结构.用体外细胞培养法,观察了它对人乳腺癌细胞分裂的抑制作用。     

超高效液相色谱-四极杆飞行时间质谱法测定血液与尿液中赛拉嗪及代谢产物2,6-二甲基苯胺

建立了一种超高效液相色谱-串联四极杆飞行时间质谱同时测定血液和尿液中赛拉嗪及2,6-二甲基苯胺的分析方法。样品经乙酸乙酯-正己烷(1∶1,体积比)提取,C18色谱柱分离,电喷雾正电离条件下进行全离子扫描模式检测。借助分析软件,通过对化合物离子精确质荷比、同位素轮廓丰度、特征二级质谱以及保留时间的比对,对目标物进行验证。方法的回收率为72.5%~87.8%,相对标准偏差为6.8%~9.7%。赛拉嗪在血液和尿液中的检出限分别为0.2,0.1μg/L,定量下限分别为0.6,0.3μg/L;2,6-二甲基苯胺在血液和尿液中的检出限分别为0.5,0.3μg/L,定量下限分别为1.5,1.0μg/L。方法快速、灵敏度高、重现性好,适用于中毒人体的血液和尿液中赛拉嗪及2,6-二甲基苯胺的检测。     

梳型接枝共聚物的合成 (Ⅲ)氯代乙酸 (降冰片烯基) 甲酯的制备

从双环戊二烯与烯丙醇进行Diels-Alder反应合成了5-羟甲基2-降冰片烯2,后者在N.N-二甲基苯胺存在下与a-氯代乙酰氯反应,首次合成出了氯乙酸降冰片烯甲酯2,考察了反应条件 (温度、反应物摩尔比等) 对各步反应收率的影响.并对各步反应产物结构进行表征.     

新型多齿手性氨基醇的合成和结构表征

以L-苯甘氨酸和N,N-二甲基苯胺为原料,合成了2种新型多齿手性氨基醇S-1,1,2-三苯基-2-[(2-二甲氨基-5-溴-1-苯基)甲氨基]-1-乙醇和S-2-苯基-2-[(2-二甲氨基-5-溴-1-苯基)甲氨基]-1-乙醇;利用红外光谱仪、核磁共振谱仪及质谱仪表征了合成产物的结构.     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.