水溶性卟啉及金属卟啉在DNA中的研究进展

近年来, 卟啉及金属卟啉与DNA的相互作用已成为研究的热点. 通过对卟啉及金属卟啉与DNA相互作用的研究将有助于更深地认识DNA本身的结构和功能, 有助于卟啉及金属卟啉在医学上的应用, 对认识很多疾病的治病机制和药物的设计也起到非常重要的作用. 本文阐述了卟啉及金属卟啉与DNA相互作用的方式和影响因素, 并将水溶性卟啉及金属卟啉分为三类: 具有吡啶基或铵基的阳离子型卟啉及金属卟啉, 具有磺酸基或羧基的阴离子型卟啉及金属卟啉, 以及非离子型的卟啉及金属卟啉. 重点论述了这三类水溶性卟啉及金属卟啉与DNA之间的相互作用, 以及这三类水溶性卟啉及金属卟啉在DNA中的应用研究进展.     

卟啉化合物的固载化及其应用的研究概况

卟啉是一类重要的大环化合物,广泛存在于自然界和生命体中,具有广泛的应用。 由于自由卟啉化合物的化学稳定性差,天然卟啉通常在特定的天然大分子(多肽)环境中发挥其特性,因此,人们研究开发了多种担体,固载化卟啉和金属卟啉,大大拓展了其应用范围。 本文综述了文献报道的卟啉及金属卟啉的常用固载载体、常用的固载方法、以及固载型卟啉化合物在催化和传感器等领域的最新应用进展,展望了卟啉的固载化和固载型卟啉的应用前景。     

卟啉化合物的固载化及其应用的研究概况

卟啉是一类重要的大环化合物,广泛存在于自然界和生命体中,具有广泛的应用。由于自由卟啉化合物的化学稳定性差,天然卟啉通常在特定的天然大分子(多肽)环境中发挥其特性,因此,人们研究开发了多种担体,固载化卟啉和金属卟啉,大大拓展了其应用范围。本文综述了文献报道的卟啉及金属卟啉的常用固载载体、常用的固载方法、以及固载型卟啉化合物在催化和传感器等领域的最新应用进展,展望了卟啉的固载化和固载型卟啉的应用前景。     

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。     

卟啉类化合物与人血清白蛋白相互作用的研究进展

卟啉类化合物与人血清白蛋白的相互作用研究可以为制备新型金属卟啉与蛋白质的结合体及卟啉类化合物的功能开发研究提供重要的理论基础,是当前仿生化学、生物有机、医药化学等领域中的热门研究课题。本文综述了近几年来具有不同结构特点的卟啉类化合物与人血清白蛋白间的相互作用,并展望了该研究方向的发展趋势和应用前景。     

手性金属卟啉配合物的性能研究

本文综述了近几年来手性金属卟啉配合物在主客体化学、立体催化及光电化学领域的性能研究成果。分析了在主客体化学中手性卟啉作为分子识别反应主体所具有的结构特征;介绍了模拟生物大分子的功能时手性卟啉所反映出的识别机制;评述了手性卟啉对苯乙烯及其衍生物的环丙烷化、羟基化及氨化等催化反应中所展示出的对映选择性和催化稳定性;概括了手性卟啉配合物在模拟植物光合成反应和制作新型光学材料方面所具有的光电性能。最后总结了手性卟啉研究成果的应用范围,并展望了手性卟啉在催化氧化方面的研究和发展方向。     

金属卟啉对杂环及DNA分子识别研究进展

介绍了近几年国内外关于组装金属卟啉对杂环分子、DNA碱基以及RNA的分子识别的研究进展, 并简述了本课题组对金属卟啉与杂环及药物分子复合物的理论研究工作. 金属卟啉广泛存在于自然界和生物体中, 此识别过程对研究和模拟生命体中各种细胞之间的相互作用具有重要意义. 组装后的金属卟啉可通过轴向配位、氢键及π-π堆积作用等识别杂环分子. 金属卟啉对DNA的识别主要有四种作用方式, 而金属卟啉对DNA以及RNA分子的识别主要靠疏水作用力、静电力以及自堆叠作用. 卟啉阳离子与DNA的结合位点受主体侧链取代基的空间结构影响. 金属卟啉对药物分子的识别靠配位键和氢键进行, 以配位键结合的复合物通常具有更高的结合能.     

基于芳香分子-糖类手性超分子组装体及功能

手性超分子组装体广泛存在于自然界中,因其在材料、化学和生物学等领域广阔的应用前景,引起了科学家们极大的兴趣。其中以糖类分子作为手性源,经分子自组装构筑手性超分子组装体的研究已成为超分子化学领域的研究热点之一。本文综述了基于糖类修饰的苝酰亚胺分子、偶氮苯分子、联苯类分子和卟啉类分子等芳香分子化合物经自组装构筑的手性超分子组装体,介绍了其在有机溶剂和水的混合溶剂、水中的凝胶性质,超分子手性特征和功能,糖分子类型与超分子组装体手性间的关系等,并对基于糖类的手性超分子组装体的前景进行了展望。     

金属卟啉催化烯烃环氧化及反应机理研究*

本文就铁卟啉及锰卟啉模拟酶体系近年来在催化烯烃环氧化反应机理方面的最新研究成果进行了详细阐述。均相催化剂固载化技术的应用,使金属卟啉配合物担载于无机载体上克服了卟啉的二聚、催化剂再生等难题,有力地推动了金属卟啉配合物应用研究的发展。     

非水介质中金属卟啉电化学

本文概述在非水介质中合成金属卟啉络合物的电化学。总结反应机理与金属卟啉的氧化和还原的关系,阐明半波电位及电子转移途径与一些因数的关系,如取代基效应,与氮基的轴向配位体配位,与卤素阴离子的轴向配位体配位,与二原子分子的轴向配位体配位,卟啉环体系的特性结构(即立栅式卟啉等),卟啉环的碱度,与溶剂的氢离子键合等。     

Progress of 3-aminopyridine-based amide,urea, imine and azo derivatives in supramolecular gelation

Supramolecular gels derived from low molecular weight gelators are considered to be fascinating soft and smart materials. Gelators of this class form gel networks involving noncovalent interactions and show various applications in many areas. The structural softness and the arrangement of the gelator molecules in the aggregated state have the collaborative effect to intensify the properties of the molecules for their potential applications in material chemistry. Of the various properties, stimulus responsibility is a desired property of supramolecular gel that finds profound application in sensing. In this review, a comprehensive summary of the work on 3-aminopyridine-based amide, urea, imine and azo gelators of different architectures indicating their different uses in supramolecular chemistry has been focused.     

The interdependence of defects, electronic structure and surface chemistry

In this article we present three diverse applications of first-principles simulations to problems of materials chemistry and chemical physics. Their common characteristic is that they are essentially problems of the relationships among atomic structures and the properties they promote in real materials and real applications. The studies are on transition-metal oxide surface chemistry, the reactivity and electronic structure of sp(2)-bonded carbon systems, and defects and electrochromic properties in WO(3). In these demanding applications we must have concern for how realistic our model systems are and how well current implementations of DFT perform, and we comment on both.     

Trends in the Synthesis of Polymer Nano- and Microscale Materials for Bio-Related Applications

Polymeric nano- and microscale materials bear significant potential in manifold applications related to biomedicine. This is owed not only to the large chemical diversity of the constituent polymers, but also to the various morphologies these materials can achieve, ranging from simple particles to intricate self-assembled structures. Modern synthetic polymer chemistry permits the tuning of many physicochemical parameters affecting the behavior of polymeric nano- and microscale materials in the biological context. In this Perspective, an overview of the synthetic principles underlying the modern preparation of these materials is provided, aiming to demonstrate how advances in and ingenious implementations of polymer chemistry fuel a range of applications, both present and prospective.     

Competition between Halogen,Hydrogen and Dihydrogen Bonding in Brominated Carboranes

Halogen bonds are a subset of noncovalent interactions with rapidly expanding applications in materials and medicinal chemistry. While halogen bonding is well known in organic compounds, it is new in the field of boron cluster chemistry. We have synthesized and crystallized carboranes containing Br atoms in two different positions, namely, bound to C‐ and B‐vertices. The Br atoms bound to the C‐vertices have been found to form halogen bonds in the crystal structures. In contrast, Br atoms bound to B‐vertices formed hydrogen bonds. Quantum chemical calculations have revealed that halogen bonding in carboranes can be much stronger than in organic architectures. These findings open new possibilities for applications of carboranes, both in materials and medicinal chemistry.     

Chirality Transfer and Memory of Chirality in Gold‐Catalyzed Reactions

Over the last few years, gold‐catalyzed reactions that involved chirality transfer and memory of chirality (MOC) have emerged as a powerful tool in enantioselective synthesis. This technique has allowed for the single‐step synthesis of enantioenriched compounds from readily available starting materials. This Focus Review discusses this emerging field with an emphasis on mechanistic aspects and their applications in synthetic organic chemistry.     

Coronenes,Benzocoronenes and Beyond: Modern Aspects of Their Syntheses,Properties, and Applications

In recent years, a variety of new designs of coronene-based polycyclic aromatic hydrocarbons (PAHs) with diverse functions have emerged to serve as complementary materials in organic chemistry and materials chemistry. In the present review, we highlight the modern aspects of syntheses related to or different from the strategies used in the early era of coronene research. Systematic extension and expansion of coronene backbones to wide categories of angular PAHs are covered. The substitution and extension of coronene architectures, by incorporating functional groups and by fusing small and large conjugated units, advatangeously enrich their photophysical, electrochemical, self-assembling, and other properties, of which are discussed to demostrate their impact in materials chemistry. While the highly symmetric coronenes, tribenzocoronenes and hexabenzocoronenes conceived wide potential in charge-transporting, electroluminescent, sensing, and other applications, other related derivatives such as dibenzo, tetrabenzo and pentabenzocoronenes also displayed their potentials as exemplified by their use as charge-conduction channel in transistor application.     

胶体与界面化学的研究进展

胶体与界面化学是研究胶体分散体系和界面现象的一门科学,在能源、材料、生物、化学制造和环境科学等领域具有广泛的应用。近年来,由于先进功能材料、仿生学和生物医药等学科的迅速发展,在纳米尺寸(胶体)的范围内进行分子组装和材料的制备已经引起了人们的高度关注。过去两年里,中国胶体与界面化学领域的科学家的创新性研究工作层出不穷,国际影响力日益提升,所获得的研究成果越来越受到国际同行的关注。这些成果可概括为:(1)系列新型有序分子组合体的构建及其在生物医药领域的应用,尤其是超分子组装、表面图案化有序组装材料的设计和应用;(2)胶体与界面化学方法在微纳米功能材料合成中的应用,包括形貌可控的无机材料、有机-无机复合功能材料、贵金属纳米材料以及小分子凝胶的合成及其应用;(3)胶体与界面化学在生物传感领域的新应用;(4)胶体与界面化学研究新方法。作为一门与实际应用密切结合的学科,现代经济社会为胶体与界面化学的发展提供了广阔的空间。可以预期,未来胶体与界面化学将更注重其基本的物理化学问题,如:新颖有序分子组合体的构建和理论认识;功能性微纳米材料界面结构与性能调控的理论指导。此外,新的手段和方法在胶体与界面体系的不断渗透,将不断产生新的学科交叉点,从而有力地促进胶体与界面化学的学科发展。共引用参考文献96篇。     

Applications of pillarenes,an emerging class of synthetic macrocycles

Synthetic macrocycles, a typical type of building block for molecular recognition and self-assembly, are crucial to supramolecular chemistry and materials science. Since 2008, a new generation of synthetic macrocyclic hosts, pillarenes and their abundant derivatives, which consist of hydroquinone units linked by methylene bridges at 2,5-positions, have been the focus of much research. Numerous studies on their host-guest properties and the fabrication of supramolecular assemblies have demonstrated that pillarenes and their derivatives possess many advantages that facilitate their applications in many research fields. Herein we summarize and classify the applications of pillarenes in terms of artificial transmembrane channels, controlled delivery systems, dispersion of carbon hybrid materials, extraction and absorption, liquid crystals, metal-organic frameworks, sensing and detection, stabilization of nanoparticles (Au/Ag/CdTe), and other typical biological applications. We also provide an overview of future developments in pillarene chemistry.     

铌多酸三维框架材料的研究进展

铌多酸三维框架材料是近年来无机合成化学与材料化学领域的研究热点. 该类材料不但可以将铌多酸的优异特性与框架结构的优点复合起来, 而且在光催化、 主客体化学、 能源转化等领域具有重要的应用前景. 本文总结了近10年来铌多酸三维框架材料的研究进展, 包括了该类材料的合成策略、 结构调控、 性质及应用探索. 此外, 还对当前该类材料的发展所面临的挑战进行了总结, 并对其发展前景进行了展望.