meso-四(4-N-取代吡啶基)卟啉铜(Ⅱ)配合物的合成及其对O-·2的清除作用

以Ｃｕ２（ＯＨ）２ＣＯ３为原料通过非均相金属插入反应合成ｍｅｓｏ－四（４－Ｎ－甲基吡啶基）卟啉合铜（Ⅱ）（ＣｕＴＭＰｙＰ）和ｍｅｓｏ－四（４－Ｎ－苄基吡啶基）卟啉合铜（Ⅱ）（ＣｕＴＢＰｙＰ）．方法操作方便，产率高．研究表明，在核黄素光照产生Ｏ－·２的体系中，ＣｕＴＭＰｙＰ和ＣｕＴＢＰｙＰ对Ｏ－·２具有明显的清除作用，对人红细胞内血红蛋白具有一定保护作用．     

邻菲罗啉-氨基酸铜(Ⅱ)配合物的合成及表征

合成了三种邻菲罗啉（Ｐｈｅｎ）－氨基酸酮（Ⅱ）的配合物：［Ｃｕ（Ｐｈｅｎ）（Ｌ－Ｈｉｓ）］·２ＣｌＯ４·Ｈ２Ｏ,［Ｃｕ（Ｐｈｅｎ）（Ｇｌｙ）］·ＣｌＯ４·Ｈ２Ｏ和［Ｃｕ（Ｐｈｅｎ）（Ｌ－Ｐｒｏ）］·ＣｌＯ４·０．５Ｃ２Ｈ５ＯＨ（Ｌ－Ｈｉｓ：组氨酸;Ｇｌｙ：甘氨酸：Ｌ－Ｐｒｏ：脯氨酸）。用元素分析、摩尔电导、ＩＲ和电子吸收光谱等手段对配合物进行了表征     

双四氮杂大环镍(Ⅱ)配合物催化的化学振荡反应

四氮杂大环配合物是生物体内一些金属酶结构单元的模拟物,四氮杂大环铜和镍的配合物可以催化化学振荡反应。近年来,此类反应被广泛地研究［１～４］。目前已报道的作为化学振荡反应催化剂的四氮杂大环配合物的配体都是单环。我们发现一种双四氮杂大环镍(Ⅱ)配合物Ｎｉ２Ｌ（ＣｌＯ４）４［Ｌ为双(１１,１３二甲基１,４,７,１０四氮杂１０,１３环十三二烯１２亚甲基)］可以作为化学振荡反应的催化剂,本文研究了Ｎｉ２Ｌ（ＣｌＯ４）４催化ＮａＢｒＯ３ＣＨ２（ＣＯＯＨ）２（ＭＡ）Ｈ３ＰＯ４体系的化学振荡反应。１实验部分实验试剂:丙二酸…     

钌(Ⅱ)联吡啶配合物cis-[Ru~Ⅱ(bpy)_2(L)_2]的配体取代效应(CNDO/2)

用ＣＮＤＯ／２方法经ＳＣＦ计算获得了钌（Ⅱ）联吡啶配合物ｃｉｓ－［ＲｕⅡ（ｂｐｙ）２（Ｌ）２］的电子结构（其中ｂｐｙ＝２，２′－二联吡啶；Ｌ＝Ｃｌ－，ＮＣＳ－，ＣＮ－，ＮＨ３，ＮＣＣＨ３）．计算结果表明，这些钌（Ⅱ）联吡啶配合物的ＬＵＭＯ均定域于配体ｂｐｙ的最低能π轨道，而其ＨＯＭＯ均定域于中心钌（Ⅱ）原子的ｄπ轨道．随着配体Ｌ的σ电子给予能力的增强，对应配合物的ＨＯＭＯ能级相应增大，ＬＵＭＯ能级亦有所增大，两者之差值则降低．这些钌（Ⅱ）联吡啶配合物的ＨＯＭＯ和ＬＵＭＯ能级变化趋势分别与相应的第一氧化和第一还原电势变化趋势相同，并且ＨＯＭＯ和ＬＵＭＯ能级与其光谱最低吸收能和第一氧化还原电势呈现出很好的线性相关性．计算结果与实验数据相吻合．     

二硫代草酰胺基或二环己酮草酰二腙作桥联基的新型双核Cu（Ⅱ）－Cu（Ⅱ）配合物的合成和磁性（Ⅱ）

合成和表征了四种新的以二硫代草酰胺基（ｄｔＯ２－）或二环己酮草酰二腙（ＢＣＯ）作桥基的双核金属配合物［Ｃｕ２（ｐｈｅｎ）２（ｄｔＯ）］（ＣｌＯ４）２（１）、［Ｃｕ２（ｄｉｅｎ）２（ｄｔＯ）］（ＣｌＯ４）２·２Ｈ２Ｏ（２）、［Ｎｉ２（ｄｉｅｎ）２（Ｈ２Ｏ）２（ｄｔＯ）］（ＣｌＯ４）２（３）及［Ｃｕ２（ｐｈｅｎ）２（ＣｌＯ４）２（ＢＣＯ）］（ＣｌＯ４）２（４），（ｐｈｅｎ：１，１０－邻菲咯啉，ｄｉｅｎ：二乙烯三胺）。测定了配合物１和４的变温磁化率，并求出交换积分Ｊ分别为－７．６７（１）和－０．９２（４）ｃｍ－１，表明双核配合物中铜离子间存在反铁磁性自旋交换相互作用。     

μ－4，4＇－联吡啶桥联三核Cu（Ⅱ）配合物的合成和磁性

合成了３种以４，４＇－联吡啶为桥联配体的三核环状Ｃｕ（Ⅱ）配合物［Ｃｕ＿３（４，４＇－ｂｐｙ）＿３·（ｐｈｅｎ）＿３］（ＣｌＯ＿４）＿６·２Ｈ＿２Ｏ（１）、［Ｃｕ＿３（４，４＇－ｂｐｙ）＿３］（ｂｐｙ）＿３］（ＣｌＯ＿４）＿６·Ｈ＿２Ｏ（２）和［Ｃｕ＿３（４，４＇－ｂｐｙ）＿３·（ＮＯ＿２－ｐｈｅｎ）＿３］（ＣｌＯ＿４）＿６·６Ｈ＿２Ｏ（３）。经元素分析、电导、ＩＲ、电子光谱、ＥＳＲ、磁化率等方法进行了表征，推定该配合物具有以４，４＇－联吡啶为扩展桥的结构。利用Ｈｅｉｓｅｎｂｅｒｇ模型求得交换参数Ｊ值为－０．２３ｃｍ－１（１）和－０．９０ｃｍ－１（３），表明配合物中金属离子间仅有很弱的反铁磁交换作用．     

茶叶、银杏叶中铅(Ⅱ)、镉(Ⅱ)、铜(Ⅱ)的测定

1　引　　言四 (4 磺酸苯基 )卟啉 (ＴＰＰＳ4)在最佳条件下可与Ｐｂ 、Ｃｄ 、Ｃｕ 形成稳定的络合物。但由于卟啉可与多种金属离子反应 ,因此 ,要将此络合物体系用于成分复杂的天然植物分析 ,则必须解决干扰问题。本文利用简便、易操作、不需使用大量有毒有机试剂及具有选择性吸附的巯基棉富集分离方法 ,实现了样品中干扰离子的分离以及痕量Ｐｂ 、Ｃｄ 、Ｃｕ 的富集和相互分离。此体系应用于茶叶、银杏叶中Ｐｂ 、Ｃｄ 、Ｃｕ 的测定 ,获得良好结果。2　实验部分2 .1　仪器和试剂　ＵＶ 2 4 0型紫外可见分光光度计 (日本岛津公司 …     

四（2─咪唑基）卟啉在水溶液中的性质及其在乙酸中与Co（Ⅱ）（OAc）_2的反应动力学研究

合成了水溶性四（２─咪唑基）卟啉（Ｈ２＿ＴＩｍＰ），研究了它在水溶液中的聚合性质．实验发现Ｈ２ＴＩｍＰ水溶液在ＰＨ＝０，６时遵守Ｂｅｅｒ定律，并呈单体形式存在．用光谱滴定法测定了Ｈ＿２ＴｌｍＰ加质于的平衡常数．用紫外可见分光光度计研究了在乙酸溶剂中Ｈ＿２ＴＩｍＰ与Ｃｏ（Ⅱ）（ＯＡｃ）２反应的动力学．提出与实验结果相吻合的反应机理，并求得预平衡步的Ｋ，　　以及速控步的Ｋ，讨论了溶剂化对标准摩尔熵及活化熵的影响．     

1，2－亚丙基双（草酰胺根）桥联的线性三核铜（Ⅱ）配合物的合成与磁性

本文合成和表征了四种新的三核铜（Ⅱ）配合物｛［Ｃｕ（Ｌ）］２［Ｃｕ（ＣＨ３－ｅｂｏ）］｝（ＣｌＯ４）２（ＣＨ３ｅｂｏ表示１，２－亚丙基双（草酰胺根），Ｌ表示１，１０－菲咯啉（ｐｈｅｎ）（１），５－硝基－１，１０－菲咯琳（ＮＯ２－ｐｈｅｍ）（２），２，２’－联吡啶（ｂｐｙ）（３）和４，４’－二甲基－２，２’－联吡啶（Ｍｅ２ｐｙ）（４））．测定了四种配合物的变温磁化率（７７－３００Ｋ），求得交换参数分别为Ｊ１＝－２１９．６ｃｍ－１，Ｊ２＝－１９１．７ｃｍ－１，Ｊ３＝－２００．８ｃｍ－１，Ｊ４＝－１８５．５ｃｍ－１，表明Ｃｕ（Ⅱ）－Ｃｕ（Ⅱ）离子间存在着强的反铁磁交换相互作用．     

铜(Ⅱ)与苯基羧酸(HPCA)和2,2''''-联吡啶衍生物(dpx)混配配合物的合成和表征

合成了铜（Ⅱ）与苯基羧酸根［ＰＣＡ－＝苯甲酸根（Ｂｚ－），２－苯乙酸根（ＰＡｃ－），３－苯丙酸根（ＰＰｒ－），４－苯丁酸根［ＰＢｕ－）］和２，２′－联吡啶衍生物（ｄｐｘ：２，２′－联吡啶胺ｄｐａ、２，２′－联吡啶酮ｄｐｋ、２，２′－联吡啶甲烷ｄｐｍ）三大系列１２种新的三元配合物。用元素分析、摩尔电导、红外光谱、１Ｈ核磁共振、差热分析等实验方法表征了它们的组成和性质。确定该系列配合物化学组成为Ｃｕ（ＰＣＡ）２（ｄｐａ）、Ｃｕ（ＰＣＡ）２（ｄｐｍ）、Ｃｕ（ＰＣＡ）２（ｄｐｋ）·ｎＨ２Ｏ（ｎ＝２－４）。它们具有相似的组成和配位方式。它们的可能结构为：二个ＰＣＡ－与Ｃｕ（Ⅱ）单齿配位，一个ｄｐｘ与Ｃｕ（Ⅱ）Ｎ，Ｎ二齿螯合配位。ｄｐｋ的羰基在金属离子Ｃｕ２＋的存在下发生水化作用成ｄｐｋ·Ｈ２Ｏ。用１ＨＮＭＲ法研究了Ｃｕ（Ｂｚ）２（ｄｐｘ）·ｎＨ２Ｏ和Ｃｕ（ＰＡｃ）２（ｄｐｘ）·ｎＨ２Ｏ二个体系其分子内或分子间可能存在的非共价键作用。     

CL-P204萃淋树脂分离铟(Ⅲ)镓(Ⅲ)锌(Ⅱ)

铟、镓作为重要的电子工业材料,在高技术领域有着广泛的应用．但是由于它们都是非常稀有而且分散的金属,至今以其为主要成份的主矿床尚未发现,它们通常是以微量的组分共生于锌矿等矿物中,因此,有关从锌矿中分离铟、镓的研究具有重要意义．由于铟、镓、锌３种离子的性...     

二甲胺基尾式卟啉铁与双原子小分子CO,NO配位性质的研究

本文报道了二甲胺基尾式卟啉铁{中位-[邻(4-二甲胺基丁酰胺基)苯基]三苯基卟啉合铁(II)}同双原子小分子CO, NO的配合物的UV, MCD, ESR光谱和电化学性质, 测定了它与CO轴向加合平衡常数为1.38x10^7M^-^1, 讨论了尾端配体对CO与中心离子铁的成键影响。NO配合物的ESR和循环伏安结果表明, NO的配位削弱了尾端N与中心离子铁的键强, 并用分子轨道理论解释了这一结果。     

Cyclic voltammetry and voltabsorptometry studies of redox proteins immobilised on nanocrystalline tin dioxide electrodes

Protein film cyclic voltammetry is a well-established technique for the study of redox proteins immobilised on electrode surfaces. In this paper, we use nanostructured SnO(2) electrodes to demonstrate that cyclic voltabsorptometry is an effective, complimentary approach to such studies of protein redox function. We exemplify this approach using two different redox systems: microperoxidase-11 (MP-11) and flavodoxin Desulfovibrio vulgaris Hildenborough (Fld). Both systems were immobilised on nanocrystalline SnO(2) electrodes and the resulting films investigated by simultaneous cyclic voltammetry and voltabsorptometry. We demonstrate that cyclic voltabsorptometry allows the unambiguous and background free observation of redox reactions for both systems studied.     

Fabrication and characterization of poly 2-napthol orange film modified electrode and its application to selective detection of dopamine

The present work is based on the use of a redox mediator containing an azo group for the selective determination of dopamine in the presence of uric acid and ascorbic acid by electrochemical method. A modified electrode was prepared by electrochemical polymerization of the poly 2-napthol orange film (P2NO) on the paraffin wax-impregnated graphite electrode (PIGE) by applying potential between ?0.6 and 0.8 V at scan rate of 50 mV s^?1 for 30 segments. The modified P2NO film electrode was characterized by ATR-IR spectroscopy, FE-SEM, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), differential pulse voltammetry (DPV), hydrodynamic voltammetry (HDV), and chronoamperometry (CA). The P2NO film modified electrode exhibited selective determination of dopamine in the presence of uric acid and ascorbic acid, and the electrocatalytic activity for oxidation of dopamine was excellent. The linear range for the determination of dopamine was 0.6 to 250 μM with a limit of detection of 0.13 μM. The modified P2NO electrode showed good stability and reproducibility. The modified electrode was used for real sample analysis such as human blood serum, rat blood serum, and pharmaceutical samples (dopamine hydrochloride injection). The results obtained were found to be satisfactory.     

Fiber-optic infrared reflectance spectroelectrochemical studies of osmium and ruthenium nitrosyl porphyrins containing alkoxide and thiolate ligands

We have examined the redox behavior of the osmium and ruthenium compounds (OEP)M(NO)(OEt) and (OEP)M(NO)(SEt) (OEP = octaethylporphyrinato dianion; M = Os, Ru) by cyclic voltammetry and infrared spectroelectrochemistry. The compound (OEP)Os(NO)(OEt) undergoes a single reversible oxidation process in dichloromethane. In contrast, the thiolate compound (OEP)Os(NO)(SEt) undergoes a net irreversible oxidation resulting in formal loss of the SEt ligand. Extended Hückel calculations on crystal structures of these two compounds provide insight into the nature of their HOMOs. In the case of the alkoxide compound, the HOMO is largely metal centered, with 70% of the charge located in the metal's orbital and approximately 25% on the porphyrin ring. However, the HOMO of the thiolate compound consists of a pi bonding interaction between the metal dxz orbital and the px orbital on the sulfur, and a pi antibonding interaction between the metal d orbital and a pi* orbital on NO. The redox behavior of the Ru analogues have been determined, and are compared with those of the Os compounds.     

Unprecedented 1,3-diaza[3]ferrocenophane scaffold as molecular probe for anions

The guanidine unit in the guise of 2-aminoimidazole in the new structural motif 2-arylamino-1,3-diaza[3]ferrocenophane 4 acts as a binding site for anions. The electrochemical behavior of this compound has been studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) and was found to exhibit a quasi reversible oxidation peak, associated to the Fe(II)/Fe(III) redox couple (Ep = 440 mV), and a non-reversible oxidation wave (Ep = 817 mV), probably associated to the oxidation of the C═N unit present in the guanidine bridge. Recognition of AcO(-), PhCO(2)(-), F(-), Cl(-), and Br(-) anions by the free receptor and the less basic anions Br(-), Cl(-), and NO(3)(-) by its monoprotonated form takes place by unusual redox-ratiometric measurements and spectroscopic ((1)H NMR and UV-vis) changes.     

Syntheses of copper(I)cis-1,3,5-tri-iminocyclohexane complexes

Copper(I) complexes of the ligand cis-1,3,5-tris(cinnamylideneamino)cyclohexane (L) have been prepared from a versatile precursor complex, [Cu(I)(L)NCMe]BF4, which incorporates a labile acetonitrile ligand that can be exchanged to give a range of new Cu(L)X complexes (where X = Cl, Br, NO2, SPh). 1H NMR spectra and X-ray structures of the Cl, Br and NO2 complexes show L coordinated in a symmetric fashion about the copper centre. The complexes have been further characterised using UV/Visible spectroscopy and cyclic voltammetry. CuLCl shows an electrochemically reversible Cu(I/II) redox couple at 0.51 V (vs. Ag/AgCl) while the CuLNO2 complex shows an analogous quasi-reversible wave at 0.41 V (vs. Ag/AgCl).     

Studies of electrochemical behaviour of RuO2-PVC film electrodes: dependence on oxide preparation temperature

Ruthenium dioxide electrodes, prepared on a Pt substrate using coatings of PVC-RuO₂ mixed in THF (designated as RuO₂-PVC film electrode) have been studied for their redox behaviour in 1 M NaOH using variable scan cyclic voltammetry. The various redox transitions in the oxidation state of the central metal ion are characterized using electrochemical parameters such as peak potential, peak current, and surface charge. The effect of oxide preparation temperature, in the range 300–700 °C, on the redox characteristics has also been studied and correlated with the electrochemically active surface area (as measured using small amplitude cyclic voltammetry) and the true surface area (by the BET method). Received: 12 August 1997 / Accepted: 18 October 1999     

First example of a di-cadmium tris-phthalocyanine triple-decker sandwich complex

An unprecedented M(II)2Pc3 (M = Cd) triple-decker sandwich complex has been synthesized and characterised by single crystal X-ray crystallography; cyclic voltammetry shows an unusually large range of redox states and EPR spectroscopy indicates that the material exists in at least two redox states, one having spin (1/2).     

Redox transformations of adsorbed NO molecules on a Pt(100) electrode

The electrochemical behavior of adsorbed NO molecules on a Pt(100) electrode has been studied in perchloric acid solutions by means of cyclic voltammetry. According to the literature data, a saturated NO adlayer with a coverage of ～0.5 monolayers (MLs) is formed under open circuit conditions in an acidic nitrite solution as a result of a disproportionation reaction. The saturated adlayer is stable in the potential range of 0.4–0.9 V vs. a reversible hydrogen electrode in 0.1 M HClO₄. NO molecules are oxidized at 0.9–1.1 V with the formation of adsorbed nitrite anions, and they can be reduced to ammonia at potentials less than 0.4 V. In this paper it has been shown that the adlayer stability depends on the surface coverage and extent of ordering. An unsaturated NO adlayer demonstrates NO ? NH₃ redox transformations at 0.5–0.8 V.