铱配合物在磷光化学传感器中的应用

由于在生物领域和物联网领域的广泛应用,化学传感器在近期发展迅速.相比于纯有机分子的荧光化学传感器,基于重金属配合物的磷光化学传感器由于发光寿命长,斯托克斯位移大等优点越来越引起人们的广泛关注.重金属铱配合物三线态寿命短,发光效率高而且配合物的发射波长容易受配体的改变而发生变化,因此成为最好的磷光传感器材料之一.本文介绍了铱配合物在磷光化学传感器领域中的应用,具体包括:阳离子传感器、阴离子传感器、氧分子传感器、氨基酸传感器、pH传感器等,并指出了相比于其它磷光化学传感器,基于铱配合物的磷光化学传感器的优势以及目前所存在的问题,最后,对基于铱配合物的磷光化学传感器的研究和发展方向进行了展望.     

[Cr(III)(4-ASA)(en)2]Cl配合物的光化学活性

通过吸收光谱、荧光光谱、电导率和ESI-MS质谱等方法讨论了铬配合物[Cr(III)(4-ASA)(en)2]Cl (4-ASA: 4-aminosalicylic acid dianion, en: ethylenediamine)在不同温度、不同pH溶液中的稳定性及光化学稳定性. 实验表明, 该配合物的溶液(pH 7.4)在日光照射下发生了光化学取代反应, 取代产物为[Cr(4-ASA)(en)(H2O)2]＋. 同时研究了配合物及其光照产物对EDTA的动力学反应和对DNA的切割反应. 琼脂糖凝胶电泳实验表明, 配合物的光化学产物[Cr(4-ASA)(en)(H2O)2]＋能有效切割pBR 322 DNA.     

铜(Ⅱ)--二肽配合物的配位形式、结构和稳定性研究进展

本文概述了近几十年来铜(Ⅱ)—二肽配合物的研究进展,介绍了铜(Ⅱ)—二肽体系几种常见的配位方式,以及溶液和晶体中的二肽铜配合物的结构。对配合物的稳定性进行了讨论,着重介绍了二肽的光学异构对配合物稳定性的影响。     

三苯基膦铜(Ⅰ)配合物的合成与结构

概述了三苯基膦铜(Ⅰ)配合物的研究进展,包括三苯基膦铜(Ⅰ)配合物的四种合成方法:置换法、还原法、电化学法和直接加成法,以及单核、双核、多核和异核铜(Ⅰ)配合物的结构特征.参考文献36篇.     

二（1,8—萘啶氮氧化物）合硝酸铜（Ⅱ）的晶体结构

1,8-萘啶氮氧化物(简写napyo)是一种配位能力较强的中性配体,关于它与金属离子形成的配合物已有报道.但工作主要集中在配合物的合成及性质的研究,它与金属离子形成的配合物的晶体结构至今未见报道.本工作旨在探讨1,8-萘啶氮氧化物与铜(Ⅱ)的配合物中配体与金属离子的配位情况以及铜(Ⅱ)的配位构型.     

电化学诱导咪唑铜配合物断裂DNA的研究

二价咪唑铜配合物可以在电极表面发生氧化还原反应,该过程对应于单电子准可逆过程.荧光光谱电化学结果表明,还原产物一价咪唑铜配合物可以被空气中的O₂氧化为二价.在中性的Tris-HCl缓冲溶液中,配合物与DNA之间存在弱相互作用,其键合常数仅为2.7×10²L/mol.荧光光谱及电化学结果表明为嵌入式作用.据此建立了一种电化学诱导咪唑铜配合物对DNA断裂的新方法,并采用差示扫描量热(DSC)法检验了断裂结果.     

超分子体系中的分子识别研究(Ⅻ)──环糊精及环糊精双核铜配合物对4-取代苯酚的分子识别

用分光光度滴定法在25.0℃时测定了不同pH值下α-,β-,γ-环糊精以及1mol/LNaOH水溶液中α-和β-环糊精双核铜配合物与4-取代苯酚形成超分子配合物的稳定常数.化学计量法表明,主体环糊精及环糊精双核铜配合物与客体4-取代苯酚形成了1：1的超分子配合物.从主-客体间的尺寸关系、pH值、多点识别和诱导契合作用等因素讨论了环糊精及环糊精双核铜配合物对客体4-取代苯酚的分子识别机制.结果表明,β-环糊精双核铜配合物对4-取代苯酚具有特殊的键合能力和分子选择性。     

新型多吡啶配体的设计及其对配合物与DNA作用机制的影响

近年来 ,以钌 ( )多吡啶配合物为探针研究 DNA的结构已成为生物无机化学领域中的一个热点[1,2 ] .这些配合物由于热力学稳定性好 ,光化学和光物理信息丰富 ,在研究 DNA内部的电子转移和Fig.1　 Structures of the ligandsDNA的结构识别等方面均有重要的作用[3～ 7] .在配合物与 DNA的相互作用中 ,配合物的形状、大小以及中心离子电荷等都有一定的影响[8] ,其中 ,配合物的形状起着至关重要的作用 ,与 DNA的形状匹配的配合物与DNA的结合较强 .这些配合物中通常含有平面性较大的芳香环配体 ,可插入到 DNA的碱基对之间 ,并与 DNA具有…     

桥联双核铜席夫碱配合物的合成和晶体结构

利用1-苯基-3-甲基-5-吡唑啉酮和水杨酰胺制备了PMP缩水杨酰胺席夫碱及其铜(Ⅱ ) 配合物,根据红外和紫外光谱数据表征了它的结构.利用X射线衍射方法研究了配合物的晶体结构,结果表明配合物为桥联双核铜结构,铜原子为五配位的四方锥构型,每个铜原子与一个配体中吡唑啉酮上的氧原子、席夫碱上的N原子、水杨酰的酚氧原子和溶剂DMF中的氧原子配位,而相邻配体中水杨酰的酚氧原子也参加配位并将两个铜原子连接起来形成桥联双核铜配合物,两个Cu(Ⅱ )原子间的距离为0.3268 nm.芳环堆积作用和分子内及分子间氢键的存在增强了配合物分子的稳定性.     

对甲苯磺酸铜及其配合物电化学行为研究(英文)

本文合成了对甲苯磺酸铜,并应用热重(TG)和差示扫描量热法(DSC)进行分析.该铜盐容易脱除全部结晶水,且在空气中不潮解,如与乙醇胺形成等摩尔配合物,则在DMSO和DMF溶剂中能催化1,1′ 联 2 萘酚的氧化,但在H2O或CH3OH溶剂中则不发生反应.此外,还分别研究了该铜盐及其它铜盐与乙醇胺(1∶1)的配合物在DMSO、DMF、CH3OH和H2O中的电化学行为和催化活性.实验表明,铜胺配合物的两步单电子还原过程对催化氧化1,1′ 联 2 萘酚是必要的条件.     

Determination of trace metal complexes by natural organic and inorganic ligands in coastal seawater.

It is well-documented that organic compounds form strong complexes with most metals in aquatic systems, and that seawater is a complex medium which contains a large variety of organic and inorganic ligands, including colloidal matter. We suggest that most trace metals are complexed in seawater and that some inorganic metals complexes are either labile or not stable. In contrast, metal-organic complexes are often stable and need various and specific treatments to be dissociated. In this paper we try to illustrate a good tendency of some trace metals to be complexed by organic ligands in seawater. A solid-phase extraction method was applied using a C18 column as a resin that is able to separate metals complexed by neutral organic ligands, and the chelamine resin to separate metal species that are present as labile inorganic complexes. The determination of total dissolved metal concentrations was achieved by formatting a metal-8-hydroxyquinoline complex, followed by adsorption on C18 columns and ICP-AES analysis.     

Complexes of Copper in Unstable Oxidation States

The review covers methods of synthesis, structures, and stabilities of copper(IV), copper(III), and copper(I) complexes with inorganic and organic ligands.     

Reactive ligands in radical processes catalyzed by copper complexes

The effect of the reactivity of donor ligands on the catalytic properties of copper complexes in the oxidative dimerization of mercaptans is considered. Catalytic compositions containing metal complexes in an excess of organic reagent ligands, which can show pronounced reductive properties (aromatic amines) or, on the contrary, oxidative properties (dimethyl sulfoxide) toward substrates, exhibit the greatest activity. In the course of the oxidation of mercaptans catalyzed by copper complexes, redox reactions accompanied by not only a change in the oxidation state of the metal but also the direct interaction of a substrate with an organic donor occur. In the presence of aromatic amines, the coupled oxidation of thiols and amines occurs, whereas dimethyl sulfoxide participates in the reaction as an oxidizing agent.     

Copper complexes for fluorescence-based NO detection in aqueous solution

Two copper(II) complexes containing dansylated ligands were investigated as turn-on fluorescence-based nitric oxide (NO) sensors. Upon addition of NO (g), the quenched fluorescence of both complexes was restored in both organic and buffered aqueous solutions, which is caused by the formation of a diamagnetic Cu(I) species and protonation of the sulfonamide functionality of the ligands. The NO detection limit of these Cu(II) complexes is 10 nM.     

Oxidation of metallic copper with complexones in organic media

Direct oxidation of copper in organic media with complexones (sterically hindered o-quinones; acetylacetone and pyridine as stabilizing ligands) was studied. From the complexes obtained, the initial components can be regenerated.     

铁配合物的环境光化学及其参与的环境化学过程

铁是地壳中含量最为丰富的金属元素之一,而自然界中存在的绝大多数溶解性铁都是以有机络合形式存在的。环境中的铁配合物在光照下会发生直接光解和次级的(光)化学反应过程,生成还原性的Fe(Ⅱ)和有机自由基以及衍生的活性氧物种。铁配合物的环境光化学反应将深刻影响着氧自由基的生成与衰减、有机物降解和其他元素的环境化学循环过程,因此,成为近年来国际环境科学领域的研究热点。本文介绍了铁配合物光还原反应的类型和原理,分析了Fe(Ⅱ)(光)化学氧化的可能机理和影响因素,并对国内外关于铁参与的环境化学过程所开展的研究进行了评述。在此基础上,通过分析目前研究中所存在的问题,对今后的研究方向和趋势作了展望。     

Trace metal speciation measurements in waters by the liquid binding phase DGT device

The speciation measurements of trace metals by the diffusive gradients in thin-films technique (DGT) using a poly(4-styrenesulfonate) (PSS) aqueous solution as a binding phase and a cellulose dialysis membrane (CDM) as a diffusive layer, CDM-PSS DGT, were investigated and showed good agreement with computer modelling calculations. The diffusion coefficients of ethylenediaminetetraacetic acid (EDTA) complexes with Cd²⁺ and Cu²⁺ were measured and compared with those of the inorganic metal ions. CDM-PSS DGT device was tested for speciation measurement in sample solutions containing EDTA, tannic acid (TA), glucose (GL), dodecylbenzenesulfonic acid (DBS) and humic acid (HA) as complexing ligands forming organic complexes with varying stability constants. Lower percentages of DGT labile copper concentrations over total filterable copper concentrations obtained from the deployments in freshwater sites indicated that copper complexes with organic matter were basically not measured by the devices.     

Tetradentate nitrogen-containing ligands bis-5-(2-pyridylmethylidene)-3,5-dihydro-4<Emphasis Type="Italic">H</Emphasis>-imidazol-4-ones and their coordination compounds with Cu<Superscript>I</Superscript> and Cu<Superscript>II</Superscript>

Tetradentate N₄-type organic ligands containing two 5-(2-pyridylmethylidene)-2-thio-3,5-dihydro-4H-imidazol-4-one fragments linked by two-, four-, or six-carbon polymethylene bridges between the sulfur atoms were synthesized. Mono- and dinuclear complexes of these ligands with copper(II) chloride, as well as with copper(I) and copper(II) perchlorates, were prepared. The structure of the coordination compound (5Z,5′Z)-2,2′-(butane-1,2-diyl-disulfanyldiyl)bis-5-(2-pyridylmethylidene)-3-phenyl-3,5-dihydro-4H-imidazol-4-one with copper(I) perchlorate was established by X-ray diffraction. The copper atom in this complex is in a distorted tetrahedral coordination formed by four nitrogen atoms of two imidazole and two pyridine rings. The perchlorate anion is located in the outer sphere of the complex and is not involved in the coordination with the copper ion. The electrochemical study of the ligands and the complexes was carried out by cyclic voltammetry and rotating disk electrode voltammetry. The initial reduction of the complexes under study occurs at the metal atom. The length of the polymethylene bridge in the ligand has only a slight effect on the redox properties of the ligands and the complexes.     

The Structure and Properties of TiO(2)-Cu(II)-EDTA Ternary Surface Complexes

The formation, composition, structure, and electrochemical properties of ternary surface complexes between copper(II) and ethylenediaminetetraacetate adsorbed on TiO(2) xerogels and on thin-film TiO(2) electrodes from solutions of varying pH have been studied by potentiometry, EPR spectroscopy, and electrochemical methods. The results strongly indicate that, in contrast to other organic ligands, B-type ternary surface complexes are formed in this system. The organic ligand forms an isolating layer between the surface of the TiO(2) electrode and the redox-active copper ions. Copyright 2001 Academic Press.     

Tangential-flow ultrafiltration: a versatile methodology for determination of complexation parameters in refractory organic matter from Brazilian water and soil samples

In this work the copper(II) complexation parameters of aquatic organic matter, aquatic and soil humic substances from Brazilian were determined using a new versatile approach based on a single-stage tangential-flow ultrafiltration (TF-UF) technique (cut-off 1 kDa) and sensitive atomic spectrometry methods. The results regarding the copper(II) complexation capacity and conditional stability constants obtained for humic materials were compared with those obtained using direct potentiometry with a copper-ion-selective electrode. The analytical procedure based on ultrafiltration is a good alternative to determine the complexation parameters in natural organic material from aquatic and soil systems. This approach presents additional advantages such as better sensibility, applicability for multi-element capability, and its possible to be used under natural conditions when compared with the traditional ion-selective electrode.