多重点击反应制备拓扑结构聚合物

点击反应由Sharpless提出,是一类具有高效、可靠、高选择性等特点的反应,被广泛用于各种拓扑结构聚合物的制备.目前,应用较为广泛的点击反应主要有Cu(I)催化的叠氮/炔环加成反应(CuAAC)、Diels-Alder(D-A)反应、巯基-烯及巯基-炔点击反应和氮氧自由基偶合反应.近年来,将多种点击反应结合起来,为高效合成拓扑结构聚合物提供了新的思路.本文综述了近几年来采用多重点击反应策略联用制备拓扑结构聚合物的研究进展,并对其发展趋势进行展望.     

合成不同拓扑结构聚合物的一个简便策略

随着高分子化学的进步, 特别是可控自由基聚合反应的发现, 不同拓扑结构聚合物的合成己获得了巨大的进展. 为合成这些复杂结构的聚合物, 人们成功地研究了不同的聚合方法. 其中, 不同功能团引发剂方法是较为方便和可行的方法之一, 并且已广泛用于不同结构聚合物的合成. 本文综述了用该方法合成不同拓扑结构聚合物, 包括嵌段、杂臂星形、H-形、π-形、接枝和环状聚合物所取得的进展, 特别强调的是这篇论文没有覆盖这方面的所有研究工作. 这一合成方法的思路是基于将不同聚合反应, 尤其是不同可控聚合反应相结合, 或者将可控聚合与不同的偶合反应, 例如与点击反应、Diel-Alder反应和活性酯反应等相结合. 所讨论的多功能引发剂不仅包括小分子化合物, 也包括带有两个和两个以上引发基团或链转移基团的聚合物. 后者称为大分子多功能团引发剂, 可以独立引发不同的聚合反应.     

不同拓扑结构的POSS/聚合物的合成及热稳定性的研究

以单官能团笼状倍半硅氧烷(POSS)、八官能团笼状倍半硅氧烷(POSS)分别为引发剂,CuCl/2,2联吡啶为催化剂,采用原子转移自由基聚合方法制备了"蝌蚪"形、星形POSS/PMMA和POSS/PMMA-b-PS复合材料。研究结果表明:通过ATRP法,能成功制备具有特定结构的POSS/PMMA和POSS/PMMA-b-PS复合材料。相比于纯的聚合物基体,星形POSS/PMMA复合材料的热稳定性降低,"蝌蚪"形POSS/PMMA复合材料的热稳定性提高。"蝌蚪"形POSS/PMMA-b-PS比星形POSS/PMMA-b-PS的热稳定性好。     

点击化学在拓扑结构聚合物合成中的应用

首先对点击化学进行简述,介绍了点击化学的概况、特征及主要反应类型;随后,重点介绍点击化学在拓扑结构聚合物(包括线形、刷形、星形、环状及树枝状大分子等)合成中的应用,并对这一领域的研究进展进行综述;最后,提出目前点击化学存在的一些问题,并对其发展前景进行展望.     

聚合物拓扑学的拓扑等价概念

聚合物拓扑学研究聚合物单体单元在大分子链的空间排布,尤其是研究常规线性以外的环形、支化、树枝、超分子组装以及含机械互锁结构的聚轮烷、聚索烃等拓扑聚合物的情况。引入拓扑等价概念可以简化具有多样性和复杂性聚合物链结构的分类。若把单体、金属离子或颗粒视为点,线性链视为线,环链视为环,则拓扑聚合物的链结构就涉及点、线、环之间的变换关系。本文介绍Tezuka提出的拓扑分类体系并阐述其在拓扑聚合物的应用。     

光诱导ATRP/Click技术在合成拓扑结构聚合物中的应用

随着绿色合成理念的不断提升,操作简便的光化学逐渐引起研究者的广泛关注.光化学与活性/可控原子转移自由基聚合(ATRP)或高活性、高选择性的点击化学(Click)相结合,能够为准确构建各种拓扑结构的聚合物提供一种行之有效的方法.近年来,光诱导ATRP/Click技术在高分子的制备中得到越来越多的应用,众多具有复杂结构和特...     

具有kgd拓扑结构的二维铅配位聚合物的合成、结构及性质研究(英文)

醋酸铅(Pb(Ac)2·3H2O)和咪唑乙酸(Hima)通过溶胶凝胶扩散合成二维配位聚合物[Pb(ima)2]n(1)的单晶。X-射线单晶衍射分析表明,晶体属于单斜晶系,P21/n空间群,晶胞参数为:a=0.8750(2)nm,b=5.1226(12)nm,c=13.292(3)nm,β=93.570(4)°,V=594.6(2)nm3,Z=2。配合物[Pb(ima)2]n是一个具有二维kgd拓扑结构的配位聚合物,二维层间又通过C-H…O氢键连接形成三维超分子结构。对配合物的红外、元素、热重及荧光等性质进行了研究。     

聚合物纳米复合体系中聚合物结构及动力学研究进展

从计算模拟及实验角度系统总结了聚合物结构、聚合物构象、聚合物扩散及聚合物多尺度动力学的研究进展,阐述了各影响因素及其变化规律,并对聚合物动力学的未来研究进行了展望.     

吡咯等离子体聚合及聚合物结构的研究

本文应用外部电容耦合式聚合装置,研究了吡咯等离子体聚合规律,找到了较好的聚合条件。通过元素分析、红外光谱等研究了聚合物的结构,电导率测定表明等离子体聚吡咯具有半导体性质。     

新型缠绕结构配位聚合物的合成及结构的研究

以2,6-H2ndc（2,6-H2ndc=naphthalene-2,6-dicarboxylic acid）,bipe[bipe=bis（4-imidazolphenoxy）ethane]为配体,在水热反应条件下,生成了1个新型缠绕配位聚合物[Co（2,6-ndc）（bipe）],并对其进行了元素分析、红外光谱（IR）、热重（TG）、粉末X射线衍射和X射线单晶衍射等表征.结构表征结果表明,该配位聚合物（4,4）-连接的sql网络,通过2D→2D平行→3D平行互穿的方式形成了三维的结构.     

Topologies of capillary condensation

Calculations are presented to illustrate the dependence of capillary adsorption upon the interactions present in model pores. The sequence of phase transitions at zero temperature is determined for a Lennard-Jones lattice gas in a pore consisting of 4 × 4 × sites. The dependence of the specific filling sequence upon the comparative strength of the gas-pore wall and the gas-gas interaction well-depths is determined. Grand canonical Monte Carlo simulations of sorption at finite temperature in the continuum version of the same model pore are also reported. Both the theory and the simulations were performed with variable gas-solid and gas-gas energy well-depths. At a temperature of 90 K, the gas-solid heterogeneity associated with atoms adsorbed in the corners, on the walls and in the interior pore volume gives rise to sequential adsorption similar to that observed in the lattice gas calculation at 0 K. A gradual approach to non-wetting behavior is observed as the gas-solid well-depth decreases. Values of the gas-solid well-depth needed to produce pore filling at saturation (i.e., pore-wetting) are discussed.     

Morphology Terminology

Following the conclusion of the Characterization Section on Tuesday, at the request of the Chairman, Prof. P. H. Geil, approximately 25 symposium attendees remained to discuss the general problem of morphology terminology for PVC. As a result the list of terms given in Table 1 was developed. It is strongly recommended that future papers discussing PVC use these terms to permit common understanding of the morphological units being described.     

不同拓扑构型嵌段液晶分子的合成与相变行为

本文对近来报道的三类嵌段液晶分子：多羟基1－苯甲酰胺－2,3－丙二醇两亲性分子I,星状季戊四醇苯甲酸酯II及带侧链的波拉化合物III的合成及自组装行为作了综述。这些分子由各向异性嵌段、两亲性嵌段和烷基链（或全氟链）以不同的拓扑形式组合而成,其合成的关键步骤是Pd(0)催化下碘代全氟烷烃对双键的自由基加成反应以及Pd(0)催化的偶合反应。通过调节亲水部分和亲脂部分的比例, 在I和II-F中观察到了从近晶层相（Sm）到柱相（Col）再到三维立方相（Cub）的液晶相序列;在波拉分子III-F中通过改变侧链的长度, 获得了一系列柱相及新型层相。这些研究表明, 利用多元化竞争组合理念,将分子中不相容的部分以不同的拓扑形式结合在一起,通过它们的微观相分离, 形成不同的微观区域, 获得不同的界面, 产生不同的界面曲率, 可设计合成具有不同微观结构的超分子体系, 从而在分子水平上控制分子的自组装行为; 同时全氟链的引入所带来的氟效应能促进微观分离,稳定液晶相,并有利于复杂超分子体系的产生。     

Nomenclature and Terminology Problems of Modern Coordination Chemistry

Russian Journal of General Chemistry - A brief analysis of the existing definitions of the term “coordination compound” has been carried out and a definition that takes into account the...     

关于摩尔吸光率术语

1 摩尔吸光率术语的演变经过 摩尔吸光率术语因吸光光度法的诞生而出现,最初称molar extinction coeffient,我国译成"克分子消光系数"[1].其后,随着人们认识的深化,发现不是"消光",而是"吸光"(absorption)作用,因而改称"克分子吸光系数"(molar absorption coeffi-cient).1983年国际纯粹与应用化学联合会分析化学部分析反应与试剂委员会明确指出:"系数"一词存在滥用的倾向,应限于在比例式中数字应用[2].     

The Effect of Topologies and Refilling Short-chain PEG on Protein Adsorption

PEGylation is the gold standard for constructing protein resistance surfaces. Herein, grafting mPEG-SH and SH-PEG-SH with varied molecular weights(Mw=5K, 10K, and 20K) on a gold chip, and the subsequent lysozyme adsorptions of the PEG layers are evaluated using quartzcrystal microbalance based on dissipation(QCM-D). The lysozyme resistance depends on the features of grafting density and chain conformation,i.e., linear and looped conformation. However, long-chain PEG(Mw≥10K) is insufficient to fo...     

对单原子催化术语的讨论

单原子催化,是由我国化学家提出的一个新概念,近年来在多相催化领域引领了一波研究热潮。单原子气体,是中学化学教育中的重要知识点。单原子催化这一术语,在文字上与单原子气体非常相似,但又有着完全不同的意义,存在一定的误导性,值得商榷。     

Highly Selective Zeolite Topologies for Flue Gas Separation

The separation of carbon dioxide from flue gas is essential for the reduction of greenhouse gas emissions. In adsorptive methods, the challenge lies in the choice of suitable porous materials. Among all zeolite topologies, a number of adsorbents with pore dimensions in the range of the guest molecules were identified to allow an excellent separation by diffusion, and MRE and AFO zeolite topologies appear to be the best candidates based on equilibrium adsorption. Also, it was found that the behavior of this gas mixture in DFT and APD zeolites differed from the normal behavior.     

Accurate mass measurement: Terminology and treatment of data

High-resolution mass spectrometry has become ever more accessible with improvements in instrumentation, such as modern FT-ICR and Orbitrap mass spectrometers. This has resulted in an increase in the number of articles submitted for publication quoting accurate mass data. There is a plethora of terms related to accurate mass analysis that are in current usage, many employed incorrectly or inconsistently. This article is based on a set of notes prepared by the authors for research students and staff in our laboratories as a guide to the correct terminology and basic statistical procedures to apply in relation to mass measurement, particularly for accurate mass measurement. It elaborates on the editorial by Gross in 1994 regarding the use of accurate masses for structure confirmation [1]. We have presented and defined the main terms in use with reference to the International Union of Pure and Applied Chemistry (IUPAC) recommendations for nomenclature and symbolism for mass spectrometry. The correct use of statistics and treatment of data is illustrated as a guide to new and existing mass spectrometry users with a series of examples as well as statistical methods to compare different experimental methods and datasets.