用电子自旋共振谱研究我国一些煤的自由基

本文用电子自旋共振谱(ESR)研究了我国十种不同变质程度的煤。电子自旋共振最重要的参数是g值、自由基的浓度、线宽和线形。用这些参数与煤中的碳、氧等元素相关联,发现ESR参数与煤的变质程度有密切关系。     

脂族酰基过氧化物分解动力学的研究X: 过氧化酰热分解反应的自旋捕获ESR研究

用亚硝基丁烷(TNB)、亚硝基苯和C-苯基-N-叔丁基硝酮作为自旋捕获剂来捕获和检出一些二酰基过氧化物类化合物分解时形成的短命烷基自由基. 报导了烷基自由基对自旋捕获剂加成的氮氧化物自由基的电子自旋共振谱, 并观察到2,4,4-三甲基戊基自由基中α-CH2的氢是非对映和非等价的. 据此, 认为与这一类自由基的加合物产生的电子自旋共振谱与其它类型自由基是不同的.     

电子自旋共振在高分子聚合研究中的若干应用

近十几年来,电子自旋共振(Electron SpinResonance,以下简称 ESR)广泛应用于高分子聚合过程的研究。它可提供高分子聚合中自由基的产生、反应和消失的过程以及自由基和反     

新型含磷无机离子交换剂研究(Ⅶ)——金属离子在SSPP上交换机理及选择性

通过表面离子交换容量的测定和红外、反射光谱及电子自旋共振谱的分析,研究了金属离子与焦磷亚硒酸锡(SSPP)的离子交换反应机理及其特性,对选择性作了解释。     

自旋标记ESR波谱在聚合物研究中的应用

电子自旋共振(ESR)波谱用于聚合物的研究,已是人所共知。特别是研究自由基聚合、交联、光降解、氧化等反应,ESR方法更具有独特的优越性。但对不含未偶电子的样品,ESR     

杂原子ZSM-48型分子筛研究 III. 杂原子存在状态

X射线衍射、红外光谱、X射线光电子能谱、磁化率、电子自旋共振等研究结果表明, 杂原子以畸变四面体配位方式占据M-ZSM-48(M=B、Cr、Ge、V)型分子筛骨架, V、Cr分别以V(Ⅳ)和Cr(Ⅲ)形式存在。     

元宝枫黄酮提取物的抗氧化性能

制备了元宝枫黄酮的乙醇提取物.用电子自旋共振(ESR)法和光敏化合物微生物法检测了元宝枫黄酮提取物对芳香烃自由基、单线态氧自由基及混合氧自由基的抗氧化性能 结果显示,元宝枫黄酮提取物具有良好的综合抗氧化性.     

铜(Ⅱ)-羟肟络合物的电子自旋共振谱研究

本文报导芳香族羟肟铜(Ⅱ)络合物的电子自旋共振(ESR)谱的研究。讨论了这类配位体上取代基的电子效应对络合物中铜(Ⅱ)的超精细分裂常数A_(Cu)值的影响,以及A_(Cu)值与这些配位体萃取铜的分配系数的关系。     

微复相体系中光解二苯甲酮羰自由基的CIDEP的研究

用高时间分辨电子自旋共振(TRESR)波谱仪,研究了微复相体系中光解二苯甲酮羰自由基的化学诱导动态电子自旋极化(CIDEP). 实验结果指出,在十二醇聚氧乙烯醚(AEO9)/异丙醇/水/辛烷体系的溶致液晶中,观察到光解二苯甲酮羰自由基(Ph2OH)表现出自旋相关自由基对极化(SCRP). 在微乳液中,则表现出常规的RPM的极化谱. 还从自由基所处微环境性质出发,讨论了SCRP的形成机理和有关的物理学性质.     

正磷烷基(9-电子)自由基化学

正磷烷基自由基第一次被认为可能的反应中间体是在1957年。十四年之后,由电子自旋共振(ESR)光谱证实了Bu~tOP(OEt)_3自由基的存在。迄今已探察到了大量的正磷烷基自由基的ESR光谱,即使是过于不稳定的自由     

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.     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

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.