SYNTHESIS AND REACTIONS OF SOME 2-THIENYL- AND 2-THENOYL-DERIVATIVES OF THIAZOLE AND THIADIAZOLINE AND THEIR SELENIUM ANALOGS

Abstract

2-(Thiocyanatoacetyl)thiophene 2 and its selenium analog 3 couple with diazotized anilines and yield 3-aryl-2-imino-5-(2-thenoyl)-2,3-dihydro-1,3,4-thiadiazoles 6 and 3-aryl-2-imino-5-(2-thenoyl)-2,3-dihydro-1,3,4-selenadiazoles 7 respectively. The reactions of both 6 and 7 with nitrous acid, acetic anhydride and benzoyl chloride are described. Azo coupling of 2-amino-4-(2-thienyl)thiazole 17 and its selenazole analog 18 with diazotized anilines yielded the arylazo derivatives 19 and 20 respectively. Reaction of the hydrazidoyl bromide 16 with potassium thiocyanate, potassium selenocyanate, thiourea and selenourea yields 6, 7, 19, and 20 respectively.     

温度及pH敏感N-异丙基丙烯酰胺/β-环糊精水凝胶的合成与性能研究

用顺丁烯二酸酐 (MAH)对具有分子包结能力的 β 环糊精 (β CD)进行化学改性 ,合成出了丁烯二酸单酯化 β CD单体 (MAH β CD) .通过氧化还原自由基引发MAH β CD与N 异丙基丙烯酰胺 (NIPA)聚合 ,合成出含 β CD结构单元的新型水凝胶 .用核磁共振、红外光谱及元素分析对MAH β CD单体及共聚物的结构和组成进行了表征 .溶胀研究结果表明 ,该水凝胶具有较好的pH、温度及离子强度敏感性 ;并且水凝胶在较高羧基(—COOH)含量和弱碱环境中 ,仍能表现出明显的温敏性     

生物质热解、加氢热解及其与煤共热解的热重研究

在加压热天平上用非等温热重法进行生物质（锯末、稻壳）在Ｎ２气氛下的热解和加氢热解研究。考察了升温速率（５～２５℃／ｍｉｎ）和压力（０．１～７ＭＰａ）的影响，求取了热解动力学参数，并研究了生物质与煤在常压Ｎ２气下的共热解过程。研究结果表明：生物质在４００℃左右即完成热解反应，总失重率大于７０％（Ｗ％，ｄａｆ．），热解时仅一个峰位于３００℃左右；与煤热解行为相同，随升温速率及压力的升高，转化率下降，ＤＴＧ峰移向高温，但由于热解反应在较低温度下进行，氧气的存在对生物质热解ＴＧ和ＤＴＧ的影响远小于煤热解。证明生物质热解以其内部氢对自由基的饱和及分子重排反应为主。生物质热解可用一级反应动力学处理，主要热解阶段及表现活化能分别为：锯末，２６７～３１４℃，６９．６６ｋＪ／ｍｏｌ；稻壳，２８３～３１０℃，５３．４５ｋＪ／ｍｏｌ；生物质由于与煤的热分解温度相差很大，因而在其共热解过程中无协同作用。     

PHOTOLYSIS AND RADIOLYSIS OF NITROMETHANE AND NITROETHANE

Abstract— Prolonged photolysis of nitromethane and nitroethane in liquid and vapour phases, with simultaneous photolysis of the nitrogen dioxide formed, was studied in the absence and presence of cupric oxide. A high-pressure quartz immersion lamp providing the full range of visible and u.v. spectrum, with a high output of radiation at 366 and 313 mμ, was employed as source of light. The products of photolysis were detected by microanalytical methods, infrared-absorption spectrum analysis and gas chromatography. Photolysis of liquid nitro-alkanes resulted in formation of many compounds; saturated hydrocarbons, and in the case of nitroethane, ethylene, were submitted to detailed examination. Photolysis in the vapour phase was carried out in a specially designed glass apparatus. The main products were nitrogen dioxide, aldehydes and polyaldehydes; hydrocarbons were not estimated.
Liquid nitromethane and nitroethane were also irradiated with γ-rays from a ⁶⁰Co source. The radiolysis products were similiar to those obtained on photolysis. The mechanism of photolytic decomposition of nitroalkanes is proposed and discussed.     

聚壬酰胺的制备纺丝及结构与性能测定

9-氨基壬酸系从癸二酸经单酯化、氨化和Hofmann重排制得。该单体以10克规模在玻璃管中和以4公斤量在15升聚合釜中,于260℃聚合成聚壬酰胺。聚合物在288℃纺丝,120℃牵伸,得到尼龙-9纤维。测定了聚合物和纤维的结构和多种性能。     

MECHANICS AND THE EVOLUTION AND FUNCTIONAL MORPHOLOGY OF CONCHOSTRACAN CARAPACE MECHANICS AND THE EVOLUTION AND FUNCTIONAL MORPHOLOGY OF CONCHOSTRACAN CARAPACE

Conchostracans, with a laterally compressed body enclosed between two symmetric valves, live swimming in fresh or brackish water. The carapace valve has a number of growth bands with various sculptures. The general trend of sculptural evolution is from smooth to punctate-minute polygon-medium reticulation-large reticulation, while these punctate, polygonal and various reticulate patterns may separately develop into various radial ridges. The development of sculpture can be well explained by mechanical principle. Functional morphology of carapace is discussed in the light of mechanics in this paper.     

四个酰基硫脲衍生物及其配合物的合成与表征

本文报道了四个Ｎ－酰基硫脲衍生物及其Ｃｕ＾２＋，Ｎｉ＾２＋，Ｃｄ＾２＋，Ｓｎ＾４＋配合物的合成。用质谱、红外光谱、紫外光谱对它们进行了结构、性质表征。配体与金属离子配位主要是通过硫原子进行，配合物都是非离子型的。     

N-苯基马来酰亚胺与环己烯共聚物的制备和表征

Ｎ苯基马来酰亚胺（ＰＨＭＩ）是一种很有应用价值的共聚单体,它能赋予共聚物很好的耐热性．有关ＰＨＭＩ与甲基丙烯酸甲酯、苯乙烯及乙烯基醚的二元共聚合反应已有文献报道［１～３］．而有关ＰＨＭＩ与环烯烃特别是环己烯的共聚合研究除我们所做的工作外［４］,报道甚少．作者研究了ＰＨＭＩ与环己烯在溶液中的二元共聚合反应,并对所得的共聚物进行了表征．１　原料ＰＨＭＩ,自制,ｍ．ｐ．８８－７℃;元素分析Ｃ,６９－３３;Ｈ,４－０７;Ｎ,８－１０;理论值Ｃ,６９－３６;Ｈ,４－０７;Ｎ,８－０９,１ＨＮＭＲ（δ）…     

A RAPID AND FACILE CONVERSION OF PRIMARY AMIDES AND ALDOXIMES TO NITRILES AND KETOXIMES TO AMIDES WITH TRIPHENYLPHOSPHINE AND N-CHLOROSUCCINIMIDE

ABSTRACT

Primary amides and aldoximes are easily converted to their corresponding nitriles using a mixture of triphenylphosphine and N-chlorosuccinimide in dichloromethane at room temperature. The reaction of aldoximes occurs almost immediately and primary amides in 0.5?h by this method. By this procedure secondary amides are produced by Beckmann rearrangement of ketoximes.     

CHLOROPHYLL a AND CAROTENOID AGGREGATES AND ENERGY MIGRATION IN MONOLAYERS AND THIN FILMS

Abstract— The spectra of absorption, fluorescence and excitation of monolayers and thin films containing chlorophyll a together with a carotenoid (cis-β-carotene, trans-β-carotene, fucoxanthin, or zeaxanthin), were measured at — 196°C. The concentration ratios used, (Chl)/(Car), were 6:1, 4:1, 3:1, 2:1, 1:1 and 1:3, and the area densities, 3·70, 2·55, 1·76, 0·71, 0·37 and 0·17 nm²/pigment molecule. In dilute monolayers, (3·70 nm²/molecule), with a constant concentration ratio (Chl)/(Car) = 3:1, evidence of three β-carotene forms, with absorption bands at 460, 500 and 520 nm (C₄₆₀, C₅₀₀ and C₅₂₀), and of a chlorophyll a form with an absorption band at 669–672 (Chl_669–672) was found. On increasing the density to 0·2–0·3 nm²/molecule, a conversion of C₄₆₀ and C₅₂₀ into C₅₀₀, was observed, and several more additional (probably more strongly aggregated) chlorophyll a forms appeared, with absorption bands at 672–733 nm. With excess carotene [(Chi)/(Car) = 1:3] the forms C₄₆₀, C₅₀₀, C₅₂₀ and Chl_669–672 were present even in the most dense films (0·2–0·3 nm²/molecule). The same was found with other carotenoids: if one of the pigments was in excess, aggregated forms of the other tended to disappear. In the transfer of energy from carotenoids to chlorophyll a, C₅₀₀ was found to be the main donor. In layers with a concentration ratio (Chl)/(Car) = 3:1, the efficiency of transfer was less than 10 per cent at the lowest density used (3·70 nm²/molecule); it increased to 50 per cent, as the density was increased to 0·20 nm²/molecule. When the relative concentration of the carotenoid was increased to (Chl)/(Car) = 1:1, the efficiency of energy transfer dropped to 25 per cent even at 0·20 nm²/molecule. It seems that the efficiency of energy transfer between carotene molecules (prior to its transfer to chlorophyll a) is low, and effective transfer occurs only between β-carotene and immediately adjacent chlorophyll a molecules.     

SURFACE ENTHALPY AND ENTROPY AND THE PHYSICO-CHEMICAL NATURE OF HYDROPHOBIC AND HYDROPHILIC INTERACTIONS

The attractive Interactions between typically hydrophobic molecules such as hexane or CCl₄, and the repulsive Interactions between extremely hydrophilic molecules such as poly(ethylene oxide) (PEO), when immersed in water, as well as the interactions between these molecules and water, have been examined from a surface thermodynamic viewpoint, taking the changes in surface free energy into account, as a function of temperature. It was found that attractive hydrophobic Interactions are not, as vas generally believed up to now, invariably entropic. Hydrophobic Interactions can be mainly enthalpic or mainly entropic, or more or less equal mixtures of both, depending on each individual case; however, all hydrophobic interactions are polar (in the sense of Lewis acid-base) in nature. Repulsive hydrophilic interactions are enthalpic, and also polar in nature. The interaction between hydrophobic solutes and water is mainly enthalpic, and is apolar in nature.     

用于基因和药物传递的多肽及聚多肽材料

多肽和聚多肽作为一类新型的生物医用材料,由于其具有良好的生物活性、生物可降解性以及生物相容性而备受瞩目.将具有特殊生理功能的多肽作为基因或药物载体、或用于药物修饰等,可以提高基因转染效率,增强药物的靶向治疗效果,降低药物的毒副作用.本文综述了近年来多肽及聚多肽材料在这些生物医学领域的应用及进展,对部分活性肽的作用机制和...     

乙基纤维素三甲硅基衍生物膜的结构表征与氧氮渗透行为

气体分离膜是近年发展起来的应用前途广阔的一个领域。近年来由于非对称膜技术的开发,美国和日本已开始用硅橡胶涂复在多孔聚砜上制成PDMS-PS复合膜。PDMS是透气量最高而稳定的膜材料,但氧氮分离系数仅为2。 乙基纤维素(EC)具有机械强度高、抗热、耐寒和稳定性好等优点,是一种具有潜力的优秀膜材料。其中取代基的位置和含量对膜的性能有较大的影响。日、美等国科学家利用EC对氧氮的良好分离系数制成了中孔纤维材料富氧器、EC涂复在聚二甲基硅氧     

多孔PVA水凝胶的组成、形貌及泊松比等力学性能研究

制备了不同含量的纯聚乙烯醇(PVA)水凝胶和不同表面活性剂含量的多孔PVA水凝胶,采用数字散斑测量其泊松比,并使用电镜和显微镜观察其微观结构,探讨了纯PVA水凝胶与多孔PVA水凝胶组成、微观结构、泊松比、压缩模量和体积模量的变化及相互关系.研究发现,采用表面活性剂成孔,反复冷冻成型制备的闭孔结构水凝胶,其泊松比随应力应变增加而减小;随PVA含量增加而泊松比值减小;随表面活性剂含量增加,孔径变大,泊松比值减小.PVA水凝胶泊松比值与压缩模量和体积模量的比值成正比.     

HYDROXYSTILBAZOLES AND HYDROXYAZAPHENANTHRENES: PHOTOCYCLIZATION AND FLUORESCENCE STUDIES

Abstract— As models for novel fluorescent probes, we have synthesized three isomeric hydroxystilbazole systems (4′-hydroxy-substituted 2-, 3-, and 4-stiIbazoles), examined their photocyclization-oxi-dation to four hydroxyazaphenanthrene systems, and made a preliminary study of their absorption and fluorescence spectra. All three stilbazoles can be prepared easily by addition of the isomeric picoline anions to 4-methoxybenzaldehyde, followed by dehydration and deprotection. Photocyclization proceeds efficiently, furnishing a single product isomer from each of the 2- and 4-stilbazole systems, and two isomeric azaphenanthrenes from the 3-stilbazole. The stilbazoles all have intense UV absorbance bands whose maxima depend upon solvent and pH; all three isomers have relatively similar spectra under neutral conditions and all three show a large red shift in base; in acid, however, the 2-and 4-stilbazole isomers show a greater red shift than the 3-stilbazole. The fluorescence of the stilbazoles is also solvent dependent, shifting to the red in more polar medium; red shifts are also observed in acid and base, but in acid, the 3-stilbazole shows a larger shift. The azaphenanthrene photocyclization products show absorbance spectra typical for quinolines and isoquinolines; their absorptivities are less than the stilbazoles, but their fluorescence is more intense. In general, the benzoquinolines have longer wavelength but weaker fluorescence than the benzoisoquinolines. Also, those isomers in which the resonance effects of the hydroxy and nitrogen groups can reinforce one another show longer wavelength emissions of greater intensity. All seven systems show dual fluorescence in water under neutral conditions, suggesting the emission from both non-ionized and ionized species in the excited state. In one case, the benzoisoquinoline system derived from 4′-hydroxy-4-stilbazole, an emission at 640 nm, observed in water over a wide pH range, is ascribed to a zwitterionic phototautomer. These stilbazoles, benzoquinolines and benzoisoquinolines may prove to be useful spectroscopic probes.     

乙基纤维素三甲硅基衍生物膜的结构表征与氧氮渗透行为

Characterization of ethyl cellulose and its derivative membranes EC-SiMe3 was studied by ¹H-NMR, ¹³C-NMR, solids-state ¹³C-NMR(CPMAS) and IR spectra. The permselectivity for oxygen and nitrogen of EC-SiMe3 membranes was determined.     

NMR,PE AND MASS SPECTROSCOPY OF 2-ALKYL- AND 2-ARYL-CARBAMYL- AND THIOCARBAMYL-CYCLOHEXANONES

Abstract

The following β-ketoamides and β-ketothioamides were prepared through Stork reaction.^3–6     

PE AND UV SPECTRA OF LINEAR AND CYCLIC POLYSILANES AND ASSIGNMENT BY AB INITIO CALCULATIONS

Abstract

Ab initio calculations have been performed on linear and cyclic polysilanes including permethylsubstituted compounds. Koopmans' approximation was used for assigning experimentally obtained PE and UV spectra. The PE spectrum of octamethylcyclotetrasilane and the UV spectra of cyclopenta and cyclohexasilane are presented for the first time.     

实验室的认可和质量管理体系的建立与运行

简要介绍了实验室认可的发展情况，开展实验室认可的必要性，实验室的质量管理体系的建立、运行及认证认可。