聚碳酸亚丙亚乙酯的合成和生物降解

由ＣＯ２和环氧丙烷的催化共聚制备了聚碳酸亚雨酯（ＰＰＣ），向ＰＰＣ引入环氧乙烷结构单元得到聚碳酸亚西亚乙酯（ＰＰＥＣ），用１ＨＮＭＲ等进行了结构表征，并用土埋法进行了生物降解性能的测定，结果表明ＰＰＣ仅在分子量很低时才具备显著的生物降解性能；而ＰＰＥＣ的生物降解速度高于分子量相近的ＰＰＣ．此外，土埋三月后共聚物的组成和分子量都保持基本不变，表明实验条件下生物降解主要在聚合物的表面进行．     

多孔β—TCP生物降解陶瓷的红外光谱研究

本文报道了多孔β－ＴＣＰ（β－Ｃａ３（ＰＯ４）２）生物降解陶瓷的红外光谱，研究了实验条件对生物降解陶瓷结构与性能的影响，结果表明，生物降解陶瓷以βＣａ３＊ＰＯ４）２米晶相，同时含有Ｃａ２Ｐ２Ｏ７，Ｃａ４Ｐ２Ｏ９晶相和其他非晶相，并呈现多孔的网络结构。     

多孔β－TCP生物降解陶瓷的拉曼光谱

求文研究了多孔Ｂ－ＴＣＰ生物降解陶瓷及其粘结剂的拉王光谱。参照各种磷酸盐及磷酸盐玻璃的拉曼光谱，对生物降解陶瓷的拉曼特征频率进行了经验式的归属和指认。实验结果表明，生物降解陶瓷以β－Ｃａ３（ＰＯ４）２（β－ＴＣＰ）为主晶相，当粘结剂含量增加时，生物降解陶瓷中出现明显的Ｃａ４Ｐ２Ｏ９９和Ｃａ２Ｐ２Ｏ７，晶相和其他非晶相，其含量随粘结剂量增加而增加，并呈现一种多孔的网络结构。     

N-芳基-5-芳基-2-呋喃甲酰胺和N-5-芳基-2-呋喃甲酰基-N′-芳氧基乙酰基肼的合成及生物活性的研究

５－芳基－２－呋喃甲酸及其衍生物具有调节植物生长等作用［４］．我们通过大量的实验，选用ＰＴＣ法，利用５－芳基－２－呋喃甲酰氯与芳胺和芳氧基乙酰肼反应，合成了新化合物Ⅱ和Ⅳ：ＲＣＯＣｌＯ（Ⅰ）ＡｒＮＨ２／ＰＥＧ－４００→ＲＣＯＮＨＡｒ（Ⅱ）ＯＮａＯＨ／...     

聚合物-锂改性蒙脱石复合材料离子迁移

以聚合物（ＰＥＯ,ＰＥＯ－ＰＭＭＡ）和锂改性蒙脱石作为主要原料,采用聚合物粉末直接熔融嵌入的方法,制备聚合物－蒙脱石复合材料．利用ＮＭＲ、ＡＣ阻抗等分析方法探讨了复合材料中聚合物链对 Ｌｉ＋离子迁移的影响．结果表明,聚合物（ＰＥＯ）嵌入蒙脱石层间,层间聚合物链的无序度增大,有利于Ｌｉ＋离子迁移．ＰＭＭＡ引入对ＰＥＯ链的改性,进一步加大聚合物链的无序度,更易于层间Ｌｉ＋离子迁移;复合材料的常温离子电导率接近１０－２Ｓ·ｃｍ－１,且具有良好的温度稳定性．     

二苯醚—对苯二甲酰氯—4,4‘—二苯氧基二苯砜三元共聚物的合成与性能

以无水ＡｌＣｌ３／ＣｌＣＨ２ＣＨ２Ｃｌ／ＮＭＰ为催化剂／溶剂体系，通过缩聚反应，由二苯醚，对苯二甲酰氯和４，４－二苯氧基二苯砜合成了聚醚酮酮和聚醚砜醚酮酮共聚物（ＰＥＫＫ／ＰＥＳＥＫＫ）．考察了单体浓度、反应时间对聚合物分子量的影响，并对其进行了ＩＲ、ＤＳＣ、ＷＡＸＤ等分析表征．结果表明，共聚物具有优异的耐热性，随着共聚物中ＰＥＳＥＫＫ单元含量的增加，其玻璃化温度逐渐升高，而熔融温度和结晶度逐渐降低．与聚醚酮酮（ＰＥＫＫ）相比，共聚物的断裂伸长率明显提高，而拉伸强度和拉伸模量却有所下降，但仍具有良好的力学性能．     

铜（Ⅱ）－聚丙烯酰胺和铜（Ⅱ）－聚乙烯醇配位聚合物的配位数

配位聚合物ＰＡＡｍ－ＣｕＣｌ＿２和ｃｕＣｌ＿２·２Ｈ＿２Ｏ的Ｃｕ￣（２＋）２ｐＸＰＳ谱上都有Ｓｈａｋｅ－ｕｐ峰，其与各自的Ｃｕ￣（２＋）２ｐ３／２肩峰或主峰距离ΔＥｓ２或ΔＥｓ分别为８．７和８．６ｅＶ；但配位聚合物Ｃｕ（Ⅱ）－ＰＶＡ却无此峰．由此推定，前者的Ｃｕ￣（２＋）是以ｓｐ￣３杂化轨道接受ＰＡＡｍ４个链节单元Ｃ－Ｎ上Ｎ的孤对电子部分转移形成配位键；而Ｃｕ（Ⅱ）－ＰＶＡ配位聚合物中的Ｃｕ￣（２＋）却以ｄｓｐ￣２杂化轨道接受ＰＶＡ４个链节单元侧基Ｏ的孤对电子部分转移，产生配位键，即Ｃｕ￣（２＋）与ＰＡＡｍ或ＰＶＡ的链节单元配位比均是１：４，此结果与电导率法测定ＰＡＡｍ－ＣｕＣｌ＿２的配位比相同．     

双醚二酐型聚醚酰亚胺的透气性能与分子结构之间关系的研究Ⅰ

合成了一系列双醚二酐型聚醚酰亚胺（ＰＥＩ），研究了它们对Ｈ２、ＣＯ２、Ｏ２、Ｎ２和ＣＨ４五种气体的透过性能与分子结构的关系．结果表明，这类聚醚酰亚胺的分子结构对其透气性和透气选择性有很大的影响，聚合物的自由体积和链段活动性是控制透气性和透气选择性的主要因素。三种带有酰亚胺键邻位取代基的聚醚酰亚胺（ＨＱＤＥＡ—ＤＭｏＢＤＡ、ＨＱＤＥＡ—ＤＭＭＤＡ和ＨＱＤＥＡ—ＤＭｏＭＤＡ）具有较大的自由体积和较小的链段活动性、很高的透气性和透气选择性。     

THE REACTION OF 2,2-DIHYDROPOLYFLUOROALKANOATES WITH C-NUCLEOPHILES

ＴＨＥ　ＲＥＡＣＴＩＯＮ　ＯＦ　２，２－ＤＩＨＹＤＲＯＰＯＬＹＦＬＵＯＲＯＡＬＫＡＮＯＡＴＥＳ　ＷＩＴＨ　Ｃ－ＮＵＣＬＥＯＰＨＩＬＥＳＴＨＥＲＥＡＣＴＩＯＮＯＦ２，２－ＤＩＨＹＤＲＯＰＯＬＹＦＬＵＯＲＯＡＬＫＡＮＯＡＴＥＳＷＩＴＨＣ－ＮＵＣＬＥＯＰＨ...     

环氧乙烷和环氧丙烷共聚物及其LiClO4复合物的热性能

用ＤＳＣ研究了环氧乙烷和环氧丙烷共聚物（ＥＯ／ＰＯ）及其ＬｉＣｌＯ＿４复合物的组成与热性能的关系，结果表明，结晶熔融热溶随ＰＯ的增加而减少，同时，结晶度下降，电导率上升；Ｏ／Ｌｉ＝２０的试样在２次升温中产生冷结晶；热历史影响聚合物的热性能。     

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。     

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.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.     

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.     

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.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

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。     

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.     

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。