像“折纸”一样操控双层二硫化钼电子态

<正>复旦大学物理系吴施伟、刘韡韬课题组与龚新高的计算组合作,通过"折纸"方式,研究与天然结构截然不同的二硫化钼双层材料,实现了对二硫化钼能带结构、能谷、自旋电子态等物理特性的操控。相关研究成果8月31日在线发表于《自然—纳米技术》。以二硫化钼为典型的过渡金属二硫属化物是近年来国际上最受关注的二维量子功能材料之一。二硫化钼具有与单原子厚度的"神奇材料"石墨烯类似的二维层状结构,是一种层状的晶体矿物。深入理解其内在机制,对能带结构、能谷等物理特性进行量子操控,对凝聚态物理学与未来新型的电子学、     

特种功能材料实验室简介

<正>河南大学特种功能材料重点实验室是以材料的制备、性能与结构表征、应用开发为主要研究内容的跨学科综合实验室,是进行科学研究和研究生教育的研究教学实体.1998年,在党鸿辛院士的带领下,依托于凝聚态物理和高分子化学与物理重点学科,在朱自强教授和张举贤教授80年代建立的"固体表面实验室"和"高分子化学研究室"的基础上组建了河南省高等学校"润滑与功能材料"     

特种功能材料实验室简介

<正>河南大学特种功能材料重点实验室是以材料的制备、性能与结构表征、应用开发为主要研究内容的跨学科综合实验室,是进行科学研究和研究生教育的研究教学实体.1998年,在党鸿辛院士的带领下,依托于凝聚态物理和高分子化学与物理重点学科,在朱自强教授和张举贤教授80年代建立的"固体表面实验室"和"高分子化学研究室"的基础上组建了河南省高等学校"润滑与功能材料"     

特种功能材料实验室简介

<正>河南大学特种功能材料重点实验室是以材料的制备、性能与结构表征、应用开发为主要研究内容的跨学科综合实验室,是进行科学研究和研究生教育的研究教学实体.1998年,在党鸿辛院士的带领下,依托于凝聚态物理和高分子化学与物理重点学科,在朱自强教授和张举贤教授80年代建立的"固体表面实验室"和"高分子化学研究室"的基础     

生物矿化中的凝聚态化学

不同于研究体相或分子与分子之间的常规化学,凝聚态化学重点关注的是多层次结构的凝聚态物质,主要研究凝聚态物质的化学性质与功能、构筑机制、凝聚态物质之间的反应以及结构与功能间的关系,也是生物矿化研究中特别感兴趣的科学问题。生物矿化是通过有机基质调控无机矿物的生成,构筑具有多层次结构和特殊功能(如保护、传感和运动等)的生物凝聚态物质。研究生物矿化中的化学构筑与结构-功能关系,通过仿生矿化可以设计并制备具有类生物矿物结构和先进功能的仿生凝聚态材料。本文从凝聚态化学的角度介绍生物矿化和仿生矿化领域的概况以及取得的重要成果和新认识,重点综述了本课题组近年来受生物矿化启发,基于无机离子寡聚体的仿生新材料构筑和功能方面的研究成果。相信生物矿化将为新兴凝聚态化学的研究和发展提供良好参考,同时从凝聚态化学的新高度看待和指导生物矿化,也将促进生物矿化研究走向新的台阶。     

高分子间相互作用的特点及意义

高分子间的相互作用与小分子间的相互作用有着显著的区别，导致高分子物质在凝聚态结构和诸多性能上明显地有别于小分子物质。本文就如下七个方面：特别强的高分子间相互作用、特殊的高聚物溶解过程、马克三角形原理、特征温度、特有的单链凝聚态、凝聚缠结和超分子体系来讨论高分子间相互作用的重要性及其对高聚物的结构和性能的影响。     

在"高聚物的结构与性能"课程中应该引入的几个新概念

在“高聚物的结构与性能”课程教学中，很有必要向学生介绍高分子科学近十几年来的发展，尤其是在高分子凝聚态基本物理问题上的研究成果以及相关的新概念、新知识，特别是我国学者的贡献。本文较为详细地讨论了近年来作者在教学中介绍的几个新概念，如：动态接触浓度、单链凝聚态、凝聚缠结等。     

“高分子物理”及“高分子物理实验”2门精品课程的建设

"高分子物理"(在中国科学技术大学叫"高聚物的结构与性能")和"高分子物理实验"课是该校高分子科学与工程系本科生的必修课。为了讲好和全面建设这两门课,作者倡导并积极开展教学研究,发表39篇教学研究论文,作者把这些研究心得和成果及时引入教学中,先后编写和出版了十几本教材及教学参考书,教学质量不断提高,并逐步形成了有鲜明特色的教学,在国内高校产生了很好的影响。通过多方面的建设,2005年"高聚物的结构与性能"被评为国家级精品课程,2006年"高分子物理实验"被评为安徽省精品课程。     

高分子多尺度结构与动力学的固体NMR研究

高分子材料中的微观结构和动力学特征决定了材料的最终物理化学性能,并具有典型的时间和空间上的多尺度特性。在不同时空尺度上表征凝聚态下高分子中多尺度的结构、动力学及其动态演变等问题,进而阐明其结构-性能间的关系一直是高分子科学研究中的挑战性课题。目前,固体NMR技术已成为从原子至100nm的空间和10-9～10s的时间尺度上研究固态高聚物体系中多层次结构和复杂运动并阐明其结构与性能关系的有力工具。本文将综述我们近年来系统构建的多尺度固体NMR实验技术,及其在阐明高分子链结构、链间相容性和相互作用、界面相结构及相区尺寸、以及从高频到超慢链运动等问题中的应用。     

《功能高分子材料》课堂教学方法的探索

功能高分子材料课堂教学过程涉及到大量高分子化学与高分子物理的基础知识,具有相辅相成的关系。在教学中如果能将高分子化学与物理知识与功能高分子材料的核心问题即"分子设计、结构与性能的关系",巧妙地衔接,紧密地结合,并有效地加以利用,不仅可以提高学生对该课程的重视度与学习兴趣,还可以加强教学效果,提升学生对专业知识的深层次理解与综合运用能力。本文结合这几年的教学实践,就如何利用功能高分子材料与高分子化学、高分子物理之间的联系以及后者对前者的辅助教学作用进行了阐述。     

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.