新型不对称四硫代富瓦烯导电LB膜的研究

新型不对称四硫代富瓦烯导电ＬＢ膜的研究李洪启姚钟麒刘丹谭干祖俞贤达（中国科学院兰州化学物理研究所７３００００）Ｌａｎｇｍｕｉｒ－Ｂｌｏｄｇｅｔ（ＬＢ）技术已成为制备分子厚度的有序导电薄膜的有力工具，该领域中四硫代富瓦烯（ＴＴＦ）衍生物是导电ＬＢ膜的研...     

含光功能基团聚合物LB膜的研究进展

本文在简要介绍含光功能基团聚合物ＬＢ膜之后，详细回顾了功能化ＬＢ膜体系光物理过程的研究，总结了含非线性光学基团聚合物ＬＢ膜的研究现状。最后，简要介绍了它们的应用前景。     

不同羧酯化的聚马来酸十八醇酯齐聚物的镉盐LB膜成膜特…

由聚马来酸酐和十八醇合成了一系列不同羧酯比的聚马来酸十八醇酯，并以其为成膜材料，ＣｄＣｌ２水溶液为亚相制备了一系列聚马来酸十八醇酯镉盐ＬＢ膜，借助小角Ｘ射线衍射和红外吸收光谱表征了成膜条件及羧酯比对ＣｄＰＭＡ膜有序结构的影响。在较高膜压和快速提拉条件下，低羧酯比的ＣｄＰＭＡ可得到有序性很高的Ｙ－型ＬＢ多层膜；高羧酯比的ＣｄＰＭＡ得不到高有序性的ＬＢ多层膜。     

可交联LB膜的研究（Ⅰ）：聚—L—谷氨酸—5—（6′—己二醇肉桂酸酯）酯的合成,表面

合成了一种新的聚合物聚Ｌ－谷氨酸－５－（６′－己二醇肉桂酸酯基），研究了它在空气／水界面的行为，形成ＬＢ膜能力，液晶性质及光交联反应。     

倒浮萍聚合物LB膜的有序－无序相变研究

倒浮萍聚合物ＬＢ膜的有序－无序相变研究李宏斌，张希，张瑞丰，赵冰，徐尉青，沈家骢，高忠民（吉林大学分子光谱与分子结构开放实验室、化学系，分析测试中心，长春，１３００２３）关键词聚合物ＬＢ膜，有序－无序相变，变温红外光谱，变温小角Ｘ光衍射ＬＢ膜的有序－...     

用自组装法制备聚合物纳米复合膜

文章比较了自组装法（ｓｅｌｆ－ａｓｓｅｍｂｌｙ,ＳＡ）与Ｌａｎｇｍｕｉｒ－Ｂｌｏｄｇｅｔｔ技术（ＬＢ）及其它方法在制备聚合物纳米复合膜时的优劣。ＳＡ法由于操作简单、膜的结构稳定性较高,因此较ＬＢ技术等具有更大的实用价值。利用ＳＡ法,可以制备各种有机聚电解质与其带相反电荷的有机聚电解质、粘土化合物及无机纳米颗粒等组成的聚合纳米复合膜。     

酸碱型磺化聚芳醚腈酮质子交换膜材料的性能研究

以合成的一系列不同磺化度的碘化聚芳醚腈酮(SPPENKs)为acidic聚合物,以聚芳醚酰亚胺(PEI)为basic聚合物,并将其溶解在N-甲基-2-吡咯烷酮(NMP)中配成质量分数为10%的成膜液,60℃下刮制成膜,制得acid-base型磺化聚芳醚腈酮质子导电了聚合物膜.用红外(FT-IR)谱图表征了acid-base型质子导电聚合物的结构,并测试了acid-base型质子导电聚合物膜的溶胀率、含水率、水解、氧化和热稳定性以及膜材料的离子交换容量IEC(IEC=meqSO3H/gdrymembrane)值等.测试结果初步表明新型质子导电聚合物膜具有良好的物化性能和较高的质子导电性,在80℃下acid-base型质子导电聚合物膜的水解断裂时间除SPPENK-40/PEI外,都超过2000h;SPPENK-60/PEI和SPPENK-80/PEI膜(IEC分别为1·08mmol/g、1·32mmol/g)与Nafion117相比,在具有较高质子交换能力的同时具有较低的溶胀率。     

多功能性聚吡咯复合膜

聚吡咯具有较高的电导率与良好的环境稳定性,被视为继聚苯胺之后最有工业化应用前景的导电高分子材料之一。聚吡咯与常规聚合物基体如聚乙烯醇、聚氯乙烯等形成的复合膜不仅可以综合聚吡咯奇异的多功能性与常规聚合物的易成膜性和低成本性于一体,而且可望发挥两者的协同效应,从而大大拓宽其应用领域。该研究已经成为导电聚合物研究领域中的又一新热点。作者系统论述了制备这类功能复合膜的两种典型制备方法,并在分析各自特点的基础上提出了改进与发展方向,指出聚吡咯复合膜具有广泛可调的电导率、快速的电学响应性以及稳定的电致变色性等多种功能,在透明导电膜、化学传感器、生物分离膜、电致变色膜领域具有诱人的应用前景。     

PAN/PMMA凝胶聚合物电解质膜导电动力学分析

采用静电纺丝法制备PAN/PMMA(聚丙烯腈/聚甲基丙烯酸甲酯)凝胶聚合物电解质膜,用交流阻抗法测试其在不同温度下的电导率,研究温度对凝胶聚合物电解质膜离子传输性能的影响规律;并与溶液浇铸法制得的平滑膜进行对比,分析两种不同形式凝胶聚合物电解质膜的导电动力学规律,探索其导电机理与微观形貌的关系.结果发现,两种薄膜的导电机理符合Arrhenius公式,其中纺丝薄膜的离子导电活化能较低.     

双亲性邻苯二甲酸正十八醇单酯稀土配合物的合成、发光、能量传递及成膜性能

自从ＶｏｎＨａｎｓＫｕｈｎ［１］首次发表了关于稀土配合物ＬＢ膜的研究以来,随着材料科学的不断发展,功能稀土配合物ＬＢ膜以其在导电［２,３］、非线性光学［４,５］、磁学［６,７］和光学［８,９］等领域中的优异性能愈来愈引起人们的注意,并取得了可喜的进展...     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.