金属配位化合物溶液的电化学研究

在已有的研究基础上,综述了近年来金属配位化合物溶液的电化学研究．内容包括：采用多种电化学方法研究金属配合物、簇状化合物溶液的电化学,配合物氧化还原电对的标准电极电位及有关的平衡常数,配合物的电极反应动力学及其与结构性能的关系,配合物的电催化作用,配合物的电合成．探讨配合物电极反应机理,测定多种电化学参数,提供了许多关于配合物性质、结构和功能的重要信息     

稀土发光配合物在水溶液中的组装及生物成像研究

稀土配合物具有较窄的f-f跃迁光谱带、较长的荧光寿命及较大的Stokes位移等独特的发光性质,同时其优异的顺磁性,赋予其在生物检测、疾病诊断及生物学活动研究中的重要应用价值.然而,稀土配合物大多水溶解性差,且荧光容易被环境中水分子O-H键的热振动淬灭等,极大地限制了其在水溶液及生物体系中的应用.近年来有研究表明,将稀土...     

金属配位化合物中的反位影响和反位效应

自1926年Черняев在总结前人工作的基础上提出金属配合物中的反位效应后,至今已有半个多世纪,有关它的实验现象和对它的理论解释已有评述.起初提出反位效应这一概念时是泛指在平面正方形和八面体的金属配合物内界彼此处于反位的配体之间的相互作用,即配体有使处于其反位的另一配体不稳定的效应.对于这种相互作用,由于从热力学和动力学方面考虑角度的不同,对该效应的概念也不同.1966年,A.Pideock和L.M.Venanzi等建议把从热力学角度考虑的称为“反位影响”(trans-influence),把从动力学方面考虑的称为“反位效应”(trans-effect).     

以三乙烯二胺为配体的过渡金属配位化合物合成、晶体结构及荧光性质研究

采用混合溶剂热法合成出一系列以三乙烯二胺（简写dabco）为配体的新型过渡金属配位化合物[CdCl₃H（dabco）₂]（1）、[CoCl₃Hdabco]（2）、[NiCl₂（H₂O）₃Hdabco]Cl（3）和[CuCl₃H（dabco）₂]Cl·H₂O（4）。对该系列化合物进行了元素分析、红外光谱以及热重分析表征,并通过X射线单晶衍射分析确定出晶体结构。结构解析表明：化合物1具有一维直链状分子结构;化合物2具有一维左螺旋状分子结构,化合物3具有一维右螺旋链状分子结构;化合物4具有二维平面网格状分子结构。对该系列化合物的荧光光谱研究结果表明,化合物1~4均具有较好的荧光性质。     

以三乙烯二胺为配体的过渡金属配位化合物合成、晶体结构及荧光性质研究

采用混合溶剂热法合成出一系列以三乙烯二胺(简写dabco)为配体的新型过渡金属配位化合物[CdCl3H(dabco)2](1)、[CoCl3Hdabco](2)、[NiCl2(H2O)3Hdabco]Cl(3)和[CuCl3H(dabco)2]Cl·H2O(4)。对该系列化合物进行了元素分析、红外光谱以及热重分析表征,并通过X射线单晶衍射分析确定出晶体结构。结构解析表明:化合物1具有一维直链状分子结构;化合物2具有一维左螺旋状分子结构,化合物3具有一维右螺旋链状分子结构;化合物4具有二维平面网格状分子结构。对该系列化合物的荧光光谱研究结果表明,化合物1~4均具有较好的荧光性质。     

荧光碳点探针的合成、性质及其在生物成像中的应用

荧光碳点探针是近几年来发展起来的一种新型荧光探针，具有传统有机染料、荧光染色蛋白及一般荧光纳米材料无法比拟的独特优势，如具有良好的水溶性、化学惰性、低毒性、易于功能化、抗光漂白性、可调谐和生物相容性等优异性能，因而引起研究者的广泛关注。目前已发展水热法等近十种较为经济便捷的方法，可进行大规模的荧光碳点制备，在细胞功能研究及细胞表面和内部功能分子的探测、组织的成像、病菌的定位等方面得到了较为广泛的应用。笔者对近年来荧光碳点的合成方法、依赖于碳点尺寸和波长等性质的发光性能，以及荧光碳点在生物成像等方面的应用作一简要综述，并对其在药用植物病理方面的应用提出展望，期望为丰富荧光碳点在生物成像领域的应用提供一定的借鉴和参考。     

核酸工具酶辅助的金属稳定同位素标记方法在生物分析中的应用

本文主要概述了近年来核酸工具酶辅助的基于金属稳定同位素标记的电感耦合等离子体质谱(ICP-MS)检测方法在生物分析中的发展和应用,简要介绍了该方法在蛋白质、核酸及一些生物小分子检测中的应用。最后对核酸工具酶辅助的基于金属稳定同位素标记的电感耦合等离子体质谱(ICP-MS)检测方法的发展前景做了展望。     

中药碳点的合成及其在生物成像和医学治疗方面的应用

碳点(Carbon dots, CDs)作为一类粒径小于10 nm新型零维光致发光纳米材料,具备可调荧光发射和激发波长,良好的光稳定性、水溶性和生物相容性、低毒性等显著优势,近年来得到了学者们广泛关注。以富含多种活性成分并可发挥多种药效作用的中药(Traditional Chinese Medicines, TCM)为碳源,制备出具有一些特殊功能的中药CDs(TCM-CDs),进而有望发挥出更大的药用价值。本文详细介绍了中药CDs的合成方法及每种合成方法的优缺点,全面综述了中药碳点在生物成像和医学治疗方面的最新研究进展,并对中药CDs研究的重要性及面临的主要问题及挑战和未来的发展方向进行了展望。     

水溶性糖基铱配合物的合成、表征及成像分析

设计、合成了3种水溶性糖基金属铱配合物[（dfppy）₂Ir（bpy-sugar）]Cl（1）、[（tpy-COOH）₂Ir（bpy-sugar）]Cl（2）和[（mpbq）₂Ir（bpy-sugar）]Cl（3）（dfppy=2-（2,4-二氟苯基）吡啶,tpy-COOH=4-（2''-吡啶基）苯甲酸,mpbq=2-甲基-3-苯基苯并[g]喹喔啉,bpy-sugar=4,4''-二（1-硫代-β-D-葡萄糖甲基）-2,2''-联吡啶）,利用核磁共振波谱、高分辨质谱、红外光谱和元素分析对其进行结构表征,并研究其光物理性质及其在细胞成像中的应用。通过辅助配体的调控,可以实现配合物从黄色到近红外的不同波长发光。配合物1和2在水溶液中表现出黄色发光,发射波长分别为546和584 nm,配合物3在水和二甲基亚砜的混合溶液（39：1,V/V）中表现出近红外发光,发射波长为780 nm。配合物1和2具有相对较高的量子产率（16.9%和3.1%）和较长的发光寿命（0.22和0.10 μs）。在配体上修饰不同的基团可以增大配合物的细胞穿透性和水溶性,实现配合物在细胞内的成像分析。从细胞成像结果可以看出,金属铱配合物能够穿过细胞膜进入到细胞,且与4,6-联脒-2-苯基吲哚（DAPI）染色的细胞核部分有所重合,说明进入到了细胞核。同时配合物的发光情况良好,说明在细胞所在的生物环境中,这种配合物仍是稳定的。     

金属配合物和原子簇化合物的电致化学发光及其应用

评述了金属配合物和原子簇化合物电致化学发光研究及应用的现状与进展,引用文献５０篇。     

Protein Staining Agents from Cationic and Neutral Luminescent Iridium(III) Complexes

Seven luminescent iridium(III) complexes were prepared to investigate the relationships between chemical structures and properties of protein staining. For the first time, the effect of the main ligand, the π conjugation effect of the ancillary ligand, and the charge effect of organometallic complexes on protein staining has been revealed. Most importantly, this study gives the first experimental evidence of the potential applications of charge‐neutral organometallic complexes in protein staining, which could open an avenue of exploiting novel protein staining agents in the future.     

Protein Labelling with Versatile Phosphorescent Metal Complexes for Live Cell Luminescence Imaging

To take advantage of the luminescent properties of d⁶ transition metal complexes to label proteins, versatile bifunctional ligands were prepared. Ligands that contain a 1,2,3‐triazole heterocycle were synthesised using Cu^I catalysed azide–alkyne cycloaddition “click” chemistry and were used to form phosphorescent Ir^III and Ru^II complexes. Their emission properties were readily tuned, by changing either the metal ion or the co‐ligands. The complexes were tethered to the metalloprotein transferrin using several conjugation strategies. The Ir^III/Ru^II–protein conjugates could be visualised in cancer cells using live cell imaging for extended periods without significant photobleaching. These versatile phosphorescent protein‐labelling agents could be widely applied to other proteins and biomolecules and are useful alternatives to conventional organic fluorophores for several applications.     

富氮唑类金属配合物的设计合成及应用

含能材料是一种特殊的能源材料,在国防和民用领域均具有特殊而重要的地位.富氮唑类合能金属配合物及其聚合物是含能材料的一个重要分支,它们在含能材料的起爆药、高能炸药、火箭推进剂和烟花等诸多领域均具有重要的研究价值和广阔的应用前景.本文从咪唑、吡唑、三唑、四唑和五唑等氮唑类含能金属配合物的理论设计、实验合成、性能评估和应用领...     

基于四齿配体的蓝光d8金属配合物及其OLED应用的研究进展

用于有机发光二极管(OLED)的红光和绿光磷光金属配合物材料在稳定性和发光效率方面均已达到了目前产业化应用的要求,而蓝光磷光配合物则在稳定性方面无法达到应用条件。高能量的激发态以及d-d态引起的配合物分解是造成蓝光磷光OLED器件稳定性差的原因之一。采用四齿配体开发d⁸金属配合物是同时提升配合物发光效率和稳定性的途径之一,有望在蓝光磷光材料和器件应用方面取得突破。本文总结了基于四齿配体的蓝光铂(Ⅱ)和钯(Ⅱ)配合物的研究进展,通过探讨配体结构对配合物光物理性质和稳定性的影响,为继续开发具有应用前景的蓝光金属配合物材料提供了指导性方向。     

手性pybox-金属络合物及其在不对称催化反应中的应用

具有C2对称性的双噁唑啉型吡啶(pybox)是一类有效的手性配体,能与许多金属离子配位,其手性催化性能已得到越来越多的关注。本文综述了手性配体pybox和pybox-金属络合物的合成方法,特别是近年来pybox-金属络合物在不对称催化反应如不对称环丙烷化反应、不对称Diels-Alder反应、1,3-偶极环加成反应、不对称aldol反应等中应用的最新进展。     

Bioactive Luminescent Transition‐Metal Complexes for Biomedical Applications

The serendipitous discovery of the anticancer drug cisplatin cemented medicinal inorganic chemistry as an independent discipline in the 1960s. Luminescent metal complexes have subsequently been widely applied for sensing, bio‐imaging, and in organic light‐emitting diode applications. Transition‐metal complexes possess a variety of advantages that make them suitable as therapeutics and as luminescent probes for biomolecules. It is thus highly desirable to develop new luminescent metal complexes that either interact with DNA through different binding modes or target alternative cellular machinery such as proteins as well as to provide a more effective means of monitoring disease progression. In this Review, we highlight recent examples of biologically active luminescent metal complexes that can target and probe a specific biomolecule, and offer insights into the future potential of these compounds for the investigation and treatment of human diseases.     

Organotellurium Ligands & Their Metal Complexes: Recent Developments

Abstract

The ligand chemistry of telluroethers, halotellurium ligands, and polytellurides has received good attention in the last decade. Tellurium-containing species have been used to design clusters. In the recent past the ligation of di and tri-telluroethers (including bis(4-methoxyphenyltelluro)methane) has been studied. Hybrid organotellurium ligands, N-[2-(4-methoxyphenyltelluro)propyl]phthalimid (L ¹ ), 2-(4-ethoxyphenyltelluromethyl)-tetrahydro-2H-pyran (L ² ), 2-(2-{4-ethoxyphenyl} telluroethyl)-1,3-dioxane (L ³ ), N-{2-(4-methoxyphenyltelluro)ethyl}morpholine (L ⁴ ), N-{2-(4-methoxyphenyltelluro)ethyl}-pyrrolidine (L ⁵ ), bis{2-(pyrrolidine-N-yl)ethyl}telluride (L ⁶ ), 1-(4-methoxyphenyltelluro)-2-[3-(6-methyl-2-pyridyl) propoxy]ethane (L ⁷ ), and 2-[2-(4-methoxyphenyltelluro)ethyl]thiophene (L ⁸ ) have been designed recently and studied for their complexation reactions. The (Te, N) and (N, Te, N) ligands, L ⁵ and L ⁶ , coordinate with Hg(II) through Te and N both, but the bonding with N is some what weak. The morpholine nitrogen of L ⁴ does not coordinate with Pd(II) or Pt(II) along with Te. The L ⁷ behaving as a (Te, N) ligand has formed 20-membered metallomacrocycle ring with Pt(II). Tellurated Schiff bases 4-MeOC₆H₄TeCH₂CH₂N═C(CH₃)C₆H₄-2-OH (L ⁹ ) and 2-HO-C₆H₄-(CH₃)C═NCH₂CH₂TeCH₂CH₂N═C(CH₃)C₆H₄-2-OH (L ¹⁰ ) and their reduction products 4-MeOC₆H₄TeCH₂CH₂NHCH(CH₃)C₆H₄-2-OH (L ¹¹ ) and 2-HO-C₆H₄-(CH₃)CHNHCH₂CH₂TeCH₂CH₂NHCH(CH₃)C₆H₄-2-OH (L ¹² ) respectively have been synthesized and studied for ligation behaviour. The L ⁹ on reaction with the [Ru(p-cymene)Cl₂]₂ results in [Ru(p-cymene)(4-MeOC₆H₄TeCH₂CH₂NH₂)Cl]Cl · H₂O whereas in the reaction of L ¹⁰ with [Ru(p-cymene) Cl₂]₂, p-cymene ligand is lost resulting in [RuCl(L ¹⁰ -H)]. The recent developments, particularly designing of L ¹ to L ¹² and their ligand chemistry, are reviewed in the present paper.     

苯并咪唑取代胺类及其金属配合物的研究与应用

概述了双苯并咪唑取代胺类、三苯并咪唑取代胺类及四苯并咪唑取代胺类配体及其金属配合物的研究和应用。研究报道,这些配体与人体必需的微量元素铜、锌、钴、镍、锰等金属形成的配合物能较好地模拟SOD分子中与金属离子配位的组氨酸的结构,且具有较好的拟SOD生物活性。     

Thermal Decomposition Kinetics of Some Metal Complexes of N,N-diethyl-n '-benzoylthiourea

Thermogravimetry (TG) and differential thermal analysis (DTA) were performed on the complexes with general formula (M(DEBT)_n (where M =Fe, Co, Ni, Cu or Ru; n =2, or 3 and DEBT=N,N-diethyl-N'-benzoylthiourea). Derivative thermogravimetric (DTG) curves were also recorded in order to obtain decomposition data on the complexes. The complexes of Fe(III), Co(II), Ni(II), Cu(II) and Ru(III) displayed two- or three-stage decomposition patterns when heated in a dynamic nitrogen atmosphere. Mass loss considerations relating to the decomposition stages indicated the conversion of the complexes to the sulfides or to the corresponding metal alone (Cu, Ru, NiS, CoS or FeS). Mathematical analysis of the TG and DTG data showed that the order of reaction varied between 0.395 and 0.973. Kinetic parameters such as the decomposition energy, the entropy of activation and the pre-exponential factor are reported. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis of Functionalized Aza-macrocycles and the Application of Their Metal Complexes in Binding Processes

Although aza-macrocycles have beenthoroughly investigated ever since their discoverybecause of their interesting binding properties,recent applications of their metal complexes inmedical concepts or as binding sites for recognitionin water have increased the demand for efficientsyntheses of functionalized derivatives. We presenthere two approaches to functionalized aza-macrocycles:substituted cyclams have been obtained byheterogeneous hydrogenation of unsaturatedheterocycles, and with established coupling methodsfrom peptide chemistry the selective introduction offunctional groups and tethering of cyclens wasachieved. The ability of Lewis-acidic complexes ofsuch substituted aza-macrocycles to reversibly formdefined aggregates even in neutral aqueous solutionwas demonstrated with the synthesis of an electrondonor – electron acceptor dyad, which is capable ofundergoing a very efficient intramolecular photoinducedelectron transfer.