卟啉类化合物分子光电器件研究进展

分子电子器件是未来分子电路的微电子元件,已成为有机功能纳米材料研究的热点。 卟啉类化合物的π共轭体系表现出的独特光电性能和良好的热稳定性,使其作为光电器件、模拟生物酶、分子识别和传感材料在材料化学、医学、生物化学和分析化学等领域展现出良好的应用前景,由于卟啉分子平面结构的易修饰性,常用卟啉化合物组装单元来构建功能化的卟啉光电器件。 本文综述了卟啉类化合物的特点及其在光电器件中的应用进展。     

卟啉纳米材料制备及在可视化传感器中的应用

在水/油体系中,利用表面活性剂辅助自组装制备出5,10,15,20-四苯基卟啉锌(ZnTPP)和5,10,15,20-四苯基卟啉钴(CoTPP)纳米材料,改变陈化时间制备多种形貌卟啉纳米材料,如纳米球、纳米棒和纳米片等。利用紫外-可见光谱和荧光光谱分析两种卟啉纳米材料的光学性质,ZnTPP纳米材料的荧光强度是其单体的4.5倍,具有良好光敏性。基于两种卟啉纳米材料构建可视化阵列芯片对挥发性气体己醛检测,卟啉纳米的响应度是它们单体的2倍。     

有机微纳米材料的设计策略、加工及应用

有机微纳米材料是一类新型的材料体系,具备了传统体相有机材料诸多特点,同时由于尺寸效应表现出独特的物理化学特性,因而在最近几年引起了广泛的关注。相比传统的无机微纳米材料体系,有机微纳米材料构筑单元选择广泛、可调控性强、加工成本低以及易于大规模加工,目前已被应用在有机场效应晶体管、有机光伏太阳能电池等方面。本文总结了有机微纳米材料的加工方法,利用超分子化学的概念探讨了有机微纳米材料的分子设计思路,以及有机微纳米材料的生长机理,并介绍了其相关应用。     

卟啉修饰碳纳米管研究进展

碳纳米管作为一类新型纳米材料具有许多独特的物理、化学性质,卟啉在可见光区具有广泛吸收.并可作为构筑分子体系的光捕捉单元.卟啉修饰的碳纳米管有望在生命、信息、材料科学等许多相关学科得到应用.本文综述了卟啉修饰碳纳米管的方法、影响因素,展望了其在光电领域的应用前景.     

水热微乳法合成La(OH)3纳米棒的形貌控制研究

自1991年Iijima发现碳纳米管以来,一维纳米材料如纳米管、纳米线、纳米棒和纳米纤维等由于其具有独特的光、电、磁等性质及其潜在的应用前景而引起全世界的广泛关注,一维纳米材料的制备方法有化学气相沉积法、溶胶一凝胶法、催化剂辅助法、固相化学反应法、模板法、溶剂热法、微乳法和水热,微乳法等,其中水热,微乳法是近年来兴起的一种很有发展前途的制备一维纳米材料的方法。     

卟啉纳米组装与生物传感

卟啉是一类重要的有机共轭分子,可以模拟许多酶的活性中心。一系列卟啉仿生酶已被合成,并用于模拟生物蛋白酶的催化活性,包括平面卟啉、栅栏卟啉、扩展环卟啉和三元环卟啉。在生物体内,许多金属蛋白酶经常自组装成纳米尺度的超分子结构来实现其基本的生物催化作用。卟啉可以通过共价或者非共价作用有序组装在纳米材料上,实现其模拟金属蛋白酶的功能。金属卟啉是良好的电子媒介体,对生命过程相关小分子的氧化还原具有较好的电催化活性。因此,金属卟啉纳米组装形成的纳米材料复合物可用于新型电化学生物传感器的构建。基于卟啉纳米材料复合物的光物理和光化学性质构建的新型光电化学生物传感平台已用于生物分子的检测。本文主要从卟啉仿生酶的合成、有序纳米组装和卟啉纳米复合物的生物传感进行评述,为构建新型电化学和光电化学传感器提供有用信息。     

卟啉衍生物及其高分子材料

卟啉是一类由4个吡咯环通过次甲基相连而形成的共轭大环化合物.卟啉及其衍生物广泛存在于生物体内,参与催化、氧的输运和能量转移等重要生理过程.因其独特的生理功能和物理化学特性,卟啉衍生物及其高分子材料的制备和合成引起了广泛关注.本文介绍了卟啉及其衍生物在生命系统中的功能及其合成方法,回顾了含卟啉的高分子材料和超分子组装体的设计和制备方法,总结了近年来基于卟啉的高分子和超分子功能材料的研究动态.     

卟啉单晶微纳米棒的合成及光电性能研究

通过相界面反应制备了一维卟啉微纳米棒,并通过紫外、红外和X衍射仪等多种表征方法对其进行了表征.结果表明,在无机酸的作用下,卟啉分子通过-,氢键和静电作用等多种相互作用聚集成有序的J-聚集体.将此一维卟啉微纳米棒构筑为微纳米器件,并测试其光电性能.该纳米器件在可见光照射下的光电流很大,关闭光源,电流在40 s内降到最低,再次打开光源,电流又在120 s内升到了最大.经过多次＂开＂、＂关＂光源,电导的光响应依旧没有降低.这种具有光电响应的卟啉微纳米棒有望成为微纳电子器件的光电元件.     

纤维素模板可控制备功能纳米材料的研究进展

作为自然界中最丰富的天然高分子材料,纤维素具备无毒无害、可再生、价格低廉和多层次空间结构等优点,被广泛应用在纺织、化学、可降解材料等领域。其中,纤维素特有的分子排列和多层次的空间结构,使其被广泛用作生物模板,进行可控制备功能纳米材料,纳米材料可以实现最大程度地复制出纤维素模板的纳米结构。本文综述了应用纤维素为模板,可控制备多种功能纳米材料(氧化物纳米材料、金属纳米材料、无机非金属复合纳米材料和其他无机纳米材料等)的最新进展,并展望了以纤维素模板可控制备功能纳米材料的未来研究方向。     

形貌可控卟啉材料的合成及光电性质

通过自组装方法制备了一种卟啉材料,并通过调节溶液pH值实现了对其形貌的可控。 当pH值较低时形成卟啉棒状结构;当pH值较高时形成卟啉叶片状结构。 利用紫外、红外和X衍射仪等多种表征方法对其结构和性质进行了表征。 结果表明,在无机酸的作用下,卟啉分子通过π-π、静电作用形成一维结构的J-聚集体;当pH值增加时,氢键的作用占主要作用形成二维片状结构。 将此卟啉棒状材料构筑微纳米器件,测试其光电性能,表明对可见光有很好的响应。 这种具有光电响应的卟啉材料有望成为微纳电子器件的光电元件。     

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.     

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.     

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.     

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.