铱催化不对称氢化反应的研究进展

铱催化不对称氢化反应是形成碳碳、碳氮和碳氧键的重要合成方法. 综述了近年来铱催化碳碳双键、碳氧双键、碳氮双键不对称氢化反应的最新研究进展.     

铜催化交叉偶联反应研究的新进展

对Cu催化交叉偶联反应的最新研究进展作了综述 .该反应涉及碳—碳、碳—氮、碳—氧、碳—硫、碳—硒、以及碳—卤的成键 .反应的类型包括Ullmann反应、Suzuki反应、Stille反应以及Heck反应等 .还详细地介绍了Cu催化交叉偶联反应中选用不同的铜盐、配体以及溶剂时所产生的效果     

碳硼烷和碳硼炔金属配合物中金属-碳键的化学性质

碳硼烷和碳硼炔金属配合物中的金属-碳键具有不同于经典金属-碳键的化学性质.一方面,二十面体碳硼烷独特的电子和空间效应使得碳硼烷金属配合物中的金属-碳键不参与和不饱和分子的反应 另一方面,在一定条件下具有大空间位阻的碳硼笼可以诱导某些碳-碳偶联反应.然而,碳硼炔金属配合物中的金属-碳键能与多种不饱和分子发生反应,其反应模式取决于中心金属离子的电子构型.本文简要总结了我们近期在这方面的研究进展.     

通过金属有机化合物的β-消除切断化学键

金属有机化合物的β-原子或基团的消除反应是实现选择性切断非活性化学键(包括碳-氢键、碳-碳键和碳-杂原子键)的有效方法之一.介绍了近年来金属有机化合物的β-原子或基团消除反应研究进展以及该反应在有机合成中的应用.     

弱碱柔能克刚:动力学去质子官能化反应

碳氢键的去质子官能化反应是碳碳键构建最常用的方法,是一种重要的碳氢键活化方式.近年来,碱催化碳碳键形成反应在含弱酸性碳氢键化合物作为亲核试剂的底物拓展方面取得了重要进展.强碱性试剂或催化剂是实现这些弱酸性碳氢键官能化反应的关键.根据酸碱平衡理论,相对较强的碱才能够对弱酸性碳氢键发生去质子化反应,形成较大浓度的碳负离子中间体,进而发生亲核反应.相对较弱的碱不足以对弱酸性碳氢键进行去质子化反应,然而尽管碳负离子中间体可能浓度很低,但应该仍然存在于反应体系中.如果可以选择性地进行热力学有利的化学转化,碳负离子中间体的浓度将会下降并引起去质子化平衡的重新构建.结合碳负离子中间体不可逆的转化和去质子平衡的重新构建,弱酸性碳氢键就可以在弱碱条件下实现缓慢却持续不断的去质子官能化反应.为区别于强碱条件下、通过热力学稳定碳负离子中间体的传统碳氢键去质子官能化反应,我们将这种在弱碱条件下、通过热力学不利的碳负离子中间体转化和酸碱平衡重新构建实现的弱酸性碳氢键的官能化反应称为动力学去质子官能化反应.本文总结了碳氢键去质子官能化反应研究现状和本研究团队近年来在弱碱条件下的动力学去质子官能化反应研究进展.     

硫酸催化的炔丙醇快速亲核取代反应（英文）

硫酸有效地催化炔丙醇和一系列碳和氧亲核试剂的直接亲核取代反应以形成碳-碳键和碳-氧键.反应可以在未除水溶剂中和空气条件下进行并获得良好的产率.室温下大多数底物的反应能在1 min内完成.     

Lewis酸促进的钯催化碳—碳叁键氧化断裂反应

碳—碳叁键的氧化断裂反应是有机合成中的重要反应之一. 一般情况下, 进行炔键断裂反应使用的化学试剂有:高锰酸钾、碱性双氧水、臭氧、四氧化锇和四氧化钌, 而以环境友好的氧气(O2)作为氧化剂的炔键氧化断裂反应却未见报道. 华南理工大学江焕峰等使用O2作为氧化剂, 在Lewis酸的促进下, 实现了钯催化碳—碳叁键的氧化断裂反应. 炔化合物在不同的醇溶液中可以氧化断裂成不同的羧酸酯, 分离收率最高可达90%. 该催化反应体系为钯催化碳—碳叁键的断裂提供了重要的参考.     

聚乙二醇:绿色有机合成的新媒介

聚乙二醇(PEG)可以溶解多种有机物和金属配合物,具有良好的热稳定性、难挥发、无毒、能生物降解、廉价易得,易于回收和循环使用. PEG作为绿色介质已经成功地应用到许多有机反应中,如碳-碳偶联反应、碳-杂偶联反应、多组分反应、缩合反应、加成反应、取代反应、氧化反应、还原反应等.总结了近年来PEG作为反应介质在不同有机反应中的应用情况.     

基于糖烯的碳苷合成方法研究进展

碳苷是一类具有多种生物活性的糖类天然产物,其独特的C—C糖苷键构筑是糖化学研究中的热点和难点.通过双键官能团构建新的C—C键是有机化学中的常用策略.随着烯化学的飞速发展,含1,2-位双键的糖烯供体在碳苷合成中也取得了显著进步.从FerrierI型碳苷化反应、Heck偶联型碳苷化反应、1-取代糖烯的过渡金属催化偶联碳苷化反应、2-取代糖烯的Michael加成型和自由基加成型碳苷化反应等方面,总结近年来基于糖烯的碳苷合成方法.     

Mitsunobu反应在构建化学键中的研究进展

Mitsunobu反应是醇与酸性化合物偶联形成新化学键的一种有效方法,可以用来构建碳-氧、碳-氮、碳-硫及碳-碳等化学键,在天然产物和功能有机分子的合成中已得到了非常广泛的应用.对Mitsunobu反应的机理及其在构建化学键中的应用进行了介绍,并对该反应的区域选择性进行了较为系统的总结.     

Polymer-surfactant and protein-surfactant interactions

The phase behavior and some physicochemical properties of homopolymers (HP) and hydrophobically modified (HMP) polymers, as well as of polyelectrolytes (PE) and proteins (PR), in the presence of aqueous surfactants, or their mixtures, are discussed. Mixing the above components gives rise to the formation of organized phases, whose properties are controlled by polymer and/or surfactant content, temperature, pH, and ionic strength. Depending on the nature, concentration, and net charge of both solutes, molecular solutions, polymer-surfactant complexes, adsorption onto micelles and vesicles, gels, liquid crystalline phases, and precipitates are observed. Such rich polymorphic behavior is the result of a complex balance between electrostatic, excluded volume, van der Waals, and other contributions to overall system stability. It is also modulated by the molecular details and architecture of both the polymer and the surfactant. Different experimental methods allow investigation of the above systems and getting information on the nature of polymer-surfactant interactions (PSI). Surface adsorption and thermodynamic methods, together with investigation of the phase diagrams, give information on the forces controlling PSI and on the existence of different phases. Conductivity, QELS and viscosity allow estimating the size and shape of polymer-surfactant (protein-surfactant) complexes. Optical microscopy, cryo-TEM, AFM, NMR, fluorescence, and relaxation methods give more information on the above systems. Use of the above mixtures in controlling gelation, surface covering, preparing dielectric layers, and drug release is suggested.     

丝素蛋白纤维及功能化材料的设计与构筑

随着环境污染、资源枯竭和医疗健康等问题的加剧,研发同时满足特定使用性能、安全性及可再生性的新型材料成为当前的发展趋势.而丝素蛋白材料正是以天然蚕丝为基本原材料,经一定的加工和功能化而形成的具有特殊结构、独特性能和广泛应用的生物质材料,近年来在生物医药、生物电子、智能传感等领域展现出巨大的应用潜力.本专论总结了丝素蛋白纤维及功能化材料的最新成果,结合本课题组相关工作,重点阐述了再生丝素蛋白纤维的仿生制备、生物医用支架的构筑与功能化、智能电子材料的设计以及天然多功能蚕丝及其构筑基元制备的研究进展,以期为高性能丝素蛋白材料的设计与构筑提供指导和借鉴.     

Overall connectivities/topological complexities: a new powerful tool for QSPR/QSAR

Earlier attempts to assess the complexity of molecules are analyzed and summarized in a number of definitions of general and topological complexity. A concept which specifies topological complexity as overall connectivity, and generalizes the idea of molecular connectivities of Randic, Kier, and Hall, is presented. Two overall connectivity indices, TC and TC1, are defined as the connectivity (the sum of the vertex degrees) of all connected subgraphs in the molecular graph. The contributions to TC and TC1, which originate from all subgraphs having the same number of edges e, form two sets of eth-order overall connectivities, eTC and eTC1. The total number of subgraphs K is also analyzed as a complexity measure, and the vector of its eth-order components, eK, is examined as well. The TC, TC1, and K indices match very well the increase in molecular complexity with the increase in the number of atoms and, at a constant number of atoms, with the increased degree of branching and cyclicity of the molecular skeleton, as well as with the multiplicity of bonds and the presence of heteroatoms. The potential of the three sets of eth-order complexities for applications to QSPR was tested by the modeling of 10 alkane properties (boiling point, critical temperature, critical pressure, critical volume, molar volume, molecular refraction, heat of formation, heat of vaporization, heat of atomization, and surface tension), in parallel with Kier and Hall's molecular connectivity indices (k)chi. The topological complexity indices were shown to outperform molecular connectivity indices in 44 out of the 50 pairs of models compared, including all models with four and five parameters.     

Effect of Cr(VI) anions on adsorption and desorption behavior of Cu(II) in the colloidal systems of two authentic variable charge soils

Heavy metals in wastes exist as multiple pollutants. The study of the interactions between multiple pollutants and soils should be of significance in practice. In the present study, the effect of chromate on adsorption and desorption behavior of Cu(II) in two variable charge soils was investigated, with the emphasis on the adsorption and desorption equilibria of Cu(II). The results showed that chromate can affect adsorption and desorption of Cu(II) in the colloidal systems of two variable charge soils. The extent of the effect was related to the initial concentrations of chromate and Cu(II), the system pH, and the nature of the soils. The presence of chromate led to an increase in the adsorption of Cu(II). For example, in the presence of 0.5, 0.8, 1.0, and 1.5 mmol L(-1) of chromate, for the rhodic ferralsol the adsorption of Cu(II) increased by 15.3, 18.0, 19.0, and 20.2%, respectively. For the hyperrhodic ferrasol, the corresponding figures were 11.9, 17.0, 20.3, and 26.1%, respectively. The presence of chromate also caused an increase in the desorption of Cu(II). For instance, in the presence of 0.5, 1.0, and 1.5 mmol L(-1) of chromate, the desorption for the rhodic ferralsol increased by 16.9, 27.5, and 34.1%, respectively. For the hyperrhodic ferralsol, the corresponding figures were 18.1, 35.6, and 51.4%, respectively. The increments of the adsorption and desorption increased with the increase in equilibrium concentration of Cu(II) in the solution. For instance, when the equilibrium concentrations were 0.5, 1.0, 1.5, and 2.0 mmol L(-1), the increments for the rhodic ferralsol were 2.5, 3.2, 3.3, and 3.0 mmol kg(-1), respectively. For the hyperrhodic ferralsol, the corresponding figures were 2.9, 3.5, 4.0, and 4.2 mmol kg(-1), respectively. The effect of chromate for the hyperrhodic ferralsol was greater than that for the rhodic ferralsol. This is caused by the difference in the content of iron oxides for the two soils. The increments of the adsorption and the desorption of Cu(II) increased with the rise in pH, reaching a maximum value, and then decreased. It can be assumed that the increment of the adsorption was caused by the change in surface charge of the soils induced by the adsorption of chromate and the cooperative adsorption of chromate adsorbed and Cu(II). The increase of electrostatically adsorbed Cu(II) was responsible for the increase in the desorption of Cu(II).     

类水滑石材料主客体插层结构的构筑及特性的理论研究

因主体层板和层间客体具有丰富的可调性,类水滑石材料(LDHs)在催化、吸附、生物医药及光、电、磁等方面展现出了广阔的应用前景.近年来理论研究已成为揭示LDHs微观结构和性质的重要手段,本文系统综述了LDHs材料主体结构、客体结构以及主客体相互作用3个方面的理论研究工作进展,及其在作为光驱动催化剂方面应用的理论研究.从主体元素构成、元素比例、电荷分布、拓扑结构转变、能带结构、态密度、层间阴离子组成、离子交换性能、主客体作用力、能量性质及光催化性能等方面,在原子、电子尺度上揭示了LDHs材料结构-性能之间的构效关系,为以其为材料平台构筑一系列基于超分子插层结构主客体间相互作用的新型功能材料、扩展材料的功能性提供了丰富的理论信息和有益指导.     

自组装方法与三维光子晶体制作

光子晶体,特别是三维光子晶体,可能成为信息处理和通信等领域的新型功能材料.光子晶体的制作方法可分为"自上而下"的物理方法和"自下而上"的化学自组装方法.化学自组装方法是制作三维光子晶体最为经济有效的方法.本文在阐述自组装方法的种类、一般过程、优点和不足等内容的基础上,分别分析和总结了带有各种功能缺陷的三维光子晶体的制作,这些缺陷主要包括线缺陷、面缺陷和点缺陷.从研究中可以看出,化学自组装方法通常需要结合其他方法才能实现缺陷的嵌入.近些年,三维光子晶体制作在材料选取、结构设计和方法改进等方面都有一些最新进展,本文对此进行了较为详尽的评述,并对我们课题组的研究进行了总结.最后对光子晶体的研究和制作方向进行了展望.     

Theoretical ONIOM2 study on pyridine adsorption in the channels and intersection of ZSM-5

The structures of the acid sites in the channels and intersections of H-, Li-, and Na-ZSM-5 (ZSM = zeolite socony mobil) and their interactions with pyridine molecule have been computed by using three corresponding models containing 22 tetrahedral sites. The calculated adsorption energies of pyridine in the intersection regions of H-, Li-, and Na-ZSM-5 are 197.0, 172.5, and 122.3 kJ/mol, respectively, in good agreement with the respective experimental values of 200 +/- 5, 155-195, and 120 kJ/mol, while those in the straight and sinusoidal channels are much smaller (157.9 and 127.6, 152.2 and 149.4, and 150.4 and 109.9 kJ/mol, respectively). These indicate that the most probable adsorption site for pyridine in ZSM-5 is the acidic site located in the intersection region. The structural parameters of the adsorption complexes show that the acidic proton in the three models of H-ZSM-5 has been transferred to the nitrogen of pyridine, while in alkali cation-exchanged ZSM-5, the coordination of the alkali cation to the nitrogen atom of pyridine dominates the overall interaction. In addition, the adsorption complexes were further stabilized by the long-range electrostatic interaction between the positively charged pyridine hydrogen atoms and the negatively charged lattice oxygen atoms of the zeolite framework. In the intersection regions of H-, Li-, and Na-ZSM-5, the coordination energy of the charge-compensating cation to the pyridine nitrogen amounts to 58, 60, and 68% of the total adsorption energy, respectively, while another 42, 40, and 32%, respectively, is due to long-range electrostatic interactions. This indicates that the zeolite lattice framework surrounding the adsorption site has important contributions to the adsorption energy of the pyridine molecule.     

低温等离子体在锂离子电池材料中的应用

综合评述了低温等离子体技术的基本原理、 常用方法及其在锂离子电池材料领域中的研究进展, 重点评述了等离子体技术在锂离子电池正极、 负极、 隔膜及固态电解质等重要组分中的材料制备与表面改性方面的主要研究结果和应用优势, 并对其所面临的挑战和未来的应用方向进行了展望.     

纳米粒子的精准组装

纳米材料由于其独特的光、电、磁、力学等性质,成为了构建功能材料与器件的理想基元。实现纳米粒子的精确组装,是探究粒子之间的耦合聚集性质和制备宏观功能器件的基础。但是由于纳米粒子的小尺寸以及在溶液中运动的随机性与复杂性,精准控制纳米粒子组装体的形貌以及在空间中的相对位置仍存在巨大挑战。为了将纳米粒子组装成理想的有序结构,许多控制粒子组装的策略与方法得到发展。本文首先概述了纳米粒子自组装的控制方法与典型形貌,着重分析了影响粒子精准排布的因素与控制方法,并对纳米粒子及其组装体的光学性质与器件应用的最新研究进展进行了讨论,最后对目前纳米粒子精准组装所面临的挑战以及未来发展的方向进行了展望。