BioInorganic Reaction Mechanisms最新文献

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Kinetics and Mechanism of Oxidation of β-Alanine by a Ag(III) Complex Ag(III)配合物氧化β-丙氨酸的动力学和机理

BioInorganic Reaction Mechanisms

Pub Date : 2007-01-01 DOI: 10.1515/IRM.2007.6.3.231

S. Huo, C. Song, J. Shan, S. Shen, Hanwen Sun

引用次数: 1

Kinetic and Mechanistic Studies of Uncatalysed Substitution of Coordinated Cyanide in Hexacyanoferrate(II) by Phenylhydrazine 苯基肼非催化取代六氰铁酸盐(II)中配位氰化物的动力学和机理研究

BioInorganic Reaction Mechanisms

Pub Date : 2007-01-01 DOI: 10.1515/IRM.2007.6.3.217

R. Naik, R. Tiwari, P. Singh, A. Verma

The kinetics of uncatalyzed reaction between hexacyanoferrate(II) and 2,2'-Bipyridine (further designated as Bipy) has been followed spectrophotometrically by monitoring the increase in absorbance at 400 nm, the λmax of cherry red complex, [Fe(CN)4Bipy] 2– as a function of pH, Ionic strength, temperature and concentration of reactants. In this reaction, the coordinated cyanide ion in hexacyanoferrate(II) get replaced by incoming ligand Bipy under the following specified reaction conditions. Temperature = 30+0.1 o C, pH = 3.8+0.02 and I = 0.10 M (KNO3). The uncatalyzed reaction between [Fe(CN)6] 4– and Bipy is very slow. The reaction follows first order dependence each in [Fe(CN)6] 4– and [Bipy]. It was found that the initial rate varies linearly with increasing concentration of hexacyanoferrate(II), keeping other variables fixed at an optimum value. The initial rate is also found to increase in the beginning with increasing concentration of [Bipy] up to [Bipy] < 1.5×10 -4 M, passes through a maximum and then finally falls. The effect of pH, ionic strength on initial rate have also been studied and explained. The activation parameters for reaction have been evaluated. A most plausible mechanistic scheme has been proposed based on the experimental observations.

用分光光度法研究了六氰高铁酸盐(II)与2,2′-联吡啶(简称Bipy)的非催化反应动力学，测定了400 nm处的吸光度、樱桃红配合物[Fe(CN)4Bipy] 2 -的λmax随pH、离子强度、温度和反应物浓度的变化规律。在该反应中，六氰高铁酸盐(II)中的配位氰化物离子在以下规定的反应条件下被进入的配体Bipy取代。温度= 30+0.1℃，pH = 3.8+0.02, I = 0.10 M (KNO3)。[Fe(CN)6] 4 -与Bipy的非催化反应非常缓慢。在[Fe(CN)6] 4 -和[Bipy]中，反应均遵循一阶依赖关系。发现初始速率随六氰高铁酸盐(II)浓度的增加呈线性变化，其他变量固定在一个最佳值。初始速率也随着[Bipy]浓度的增加而开始增加，直到[Bipy] < 1.5×10 -4 M，经过一个最大值后最终下降。研究并解释了pH、离子强度对初始速率的影响。对反应的活化参数进行了评价。根据实验观察，提出了一种最合理的机理方案。

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引用次数: 1

Mechanism of Interaction of DNA Bases with Pd(II)-azoimidazoles: The Cytosine Case DNA碱基与Pd(II)-偶氮咪唑的相互作用机制:胞嘧啶案例

BioInorganic Reaction Mechanisms

Pub Date : 2006-06-01 DOI: 10.1515/IRM.2006.6.1.19

S. Saha, Tapas Majumdar, Ambikesh Mahapatra

Cytosine is responsible for maintaining cytosineguanine triple hydrogen bonded bond pairing during coding information transfer of progeny [1,2]. There is a long-standing interest to explore the interaction of carcinogenic agents and anticancer drugs with DNA [3-12]. Inorganic Reaction Mechanisims, Vol. 6, pp. 19-29 © 2006 Old City Publishing, Inc. Reprints available directly from the publisher Published by license under the OCP Science imprint, Photocopying permitted by license only a member of the Old City Publishing Group.

引用次数: 5

Kinetics and Mechanism of Oxidation of Iminodiacetatochromium(III) by Periodate 高碘酸盐氧化亚氨基二乙酰铬(III)的动力学及机理

BioInorganic Reaction Mechanisms

Pub Date : 2006-01-01 DOI: 10.1515/IRM.2006.6.1.39

H. Ewais, Faris D. Al-Otaibi, A. ABDEL-KHALEK,

The oxidation of chromium from the trivalent to hexavalent states is an important environmental process because of the high mobility and toxicity of chromium(VI) [1]. Periodate oxidations have been reported to play an important role in biological determinants [2, 3]. They are used to degrade carbohydrate determinants in proteins without altering protein or lipid epitopes [2, 3]. The oxidation of hexacyanoferrate(II) by periodate has been investigated previously in weakly alkaline and neutral phosphate buffer solution and the kinetic were observed to be simple [4]. The oxidation kinetics of hexacyanoferrate(II) by periodate in acetate buffer was also studied [5]. It was reported that the mechanism of oxidation greatly differed on going from alkaline to acidic solution, whereas in acidic solutions the reaction rate was not only independent of periodate, but also inhibited by its increasing concentration. Symons [6] reported that the oxidation of iron(II) by periodate proceeds via a series of one electron-transfer steps. The polymerization of added acrylonitrile was taken as a criterion for the formation Inorganic Reaction Mechanisims, Vol. 6, pp.39-47 © 2006 Old City Publishing, Inc. Reprints available directly from the publisher Published by license under the OCP Science imprint, Photocopying permitted by license only a member of the Old City Publishing Group.

由于铬(VI)的高迁移率和高毒性，铬从三价态氧化为六价态是一个重要的环境过程[1]。据报道，高碘酸盐氧化在生物决定因素中起着重要作用[2,3]。它们被用来降解蛋白质中的碳水化合物决定因子而不改变蛋白质或脂质表位[2,3]。高碘酸盐在弱碱性和中性磷酸盐缓冲溶液中氧化六氰高铁酸盐(II)的研究已经进行过，观察到动力学很简单[4]。还研究了高碘酸盐在醋酸缓冲液中的氧化动力学[5]。从碱性溶液到酸性溶液的氧化机理差异较大，而在酸性溶液中，高碘酸盐不仅不影响氧化反应速率，而且还会受到高碘酸盐浓度增加的抑制。Symons[6]报道了高碘酸盐对铁(II)的氧化是通过一系列单电子转移步骤进行的。《无机反应机理》第6卷第39-47页©2006 Old City Publishing, Inc.。可直接从出版商处获得重印，在OCP科学印记下通过许可出版，仅允许旧城出版集团成员的许可复印。

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引用次数: 9

Micellar Effects on the Reactions of Chromium(VI) Oxidation of Lactic Acid and Malic Acid in the Presence and Absence of Picolinic Acid in Aqueous Acid Media 胶束效应对乳酸和苹果酸在有或无吡啶酸条件下氧化铬反应的影响

BioInorganic Reaction Mechanisms

Pub Date : 2006-01-01 DOI: 10.1515/IRM.2006.6.2.141

B. Saha, Monirul Islam, A. Das

Among the different chelating agents like 1,10phenanthroline, 2,2/-bipyridyl, ethylenediaminetetraacetic acid and oxalic acid acting as catalysts [1,2] in Cr(VI) oxidation of different substrates, the catalytic ability [2,3,4] of picolinic acid (PA) is unique and of considerable interest. Picolinic acid (PA) is never cooxInorganic Reaction Mechanisims, Vol. 6, pp. 141-149 © 2006 Old City Publishing, Inc. Reprints available directly from the publisher Published by license under the OCP Science imprint, Photocopying permitted by license only a member of the Old City Publishing Group.

引用次数: 18

Interaction Between Pd(RaaiR/)Cl2 and HQ: Reaction Dynamics and Mechanism (RaaiR/ = 1-alkyl-2-(arylazo)imidazole; HQ = 8-Quinolinol) Pd(RaaiR/)Cl2与HQ的相互作用:反应动力学及机理(RaaiR/ = 1-烷基-2-(芳基偶氮)咪唑)q = 8-喹啉

BioInorganic Reaction Mechanisms

Pub Date : 2006-01-01 DOI: 10.1515/IRM.2006.6.1.71

S. Saha, Ambikesh Mahapatra

引用次数: 7

Kinetics and Mechanism of Oxidation of Sodium Glycollate by Dihydroxyditelluratoargentate(III) in Alkaline Medium 二羟二苯丙酮酸钠(III)在碱性介质中氧化甘草酸钠的动力学及机理

BioInorganic Reaction Mechanisms

Pub Date : 2006-01-01 DOI: 10.1515/IRM.2006.6.2.113

S. Huo, J. Shan, S. Li, S. Shen, Hanwen Sun

The study of the highest accessible oxidation state of transition metals has intrigued many researchers. Transition metals in a higher oxidation state generally can be stabilized by chelation with suitable polydentate ligands. Metal complexes such as diperiodatoargentate(III) [1], ditelluratorargentate(III) [2], ditelluratocuprate(III) [3], and diperiodatonickelate(IV) [4] are good oxidants in a medium with an appropriate pH value. The use of complexes as good oxidizing agents in analytical chemistry has been well reported [5,6]. The oxidation of a number of organic compounds and metals in lower oxidation states by Ag(III) has also been performed, but no further information on the kinetics is available. In this Inorganic Reaction Mechanisims, Vol. 6, pp. 113-118 © 2006 Old City Publishing, Inc. Reprints available directly from the publisher Published by license under the OCP Science imprint, Photocopying permitted by license only a member of the Old City Publishing Group.

过渡金属最高可达氧化态的研究引起了许多研究者的兴趣。高氧化态的过渡金属通常可以通过与合适的多齿配体螯合来稳定。金属配合物如双盐酸盐(III)[1]、双盐酸盐(III)[2]、双盐酸盐(III)[3]和双盐酸盐(IV)[4]在适当pH值的介质中是良好的氧化剂。在分析化学中，配合物作为良好氧化剂的使用已经有很好的报道[5,6]。Ag(III)对一些低氧化态的有机化合物和金属的氧化也进行了研究，但没有进一步的动力学信息。《无机反应机理》第6卷，第113-118页©2006 Old City Publishing, Inc。可直接从出版商处获得重印，在OCP科学印记下通过许可出版，仅允许旧城出版集团成员的许可复印。

引用次数: 0

Inner-sphere Oxidation of a Ternary Complex Involving Iminodiacetatochromium(III) and DL-Aspartic acid by Periodate 含亚氨基二乙酰铬(III)和dl -天冬氨酸的三元配合物在高碘酸盐球内氧化的研究

BioInorganic Reaction Mechanisms

Pub Date : 2006-01-01 DOI: 10.1515/IRM.2006.6.1.31

A. ABDEL-KHALEK,, H. Ewais, Faris D. AL-OTAIBIF,

The oxidation of chromium from the trivalent to hexavalent states is an important environmental process because of the high mobility and toxicity of chromium(VI) [1]. Chromium(VI) compounds are well known to be potent toxic and carcinogenic agents. Because chromium(VI) is easily taken up by cells and is subsequently reduced to the trivalent form, the formation of chromium(III) or other Inorganic Reaction Mechanisims, Vol. 6, pp. 31-38 © 2006 Old City Publishing, Inc. Reprints available directly from the publisher Published by license under the OCP Science imprint, Photocopying permitted by license only a member of the Old City Publishing Group.

引用次数: 5

Effects of Inclusion of (Ferrocenylmethyl)trimethylammonium Complexes in Para-Sulfonated Calixarenes on the Kinetics of Their Electron Transfer Reactions 对磺化杯芳烃中(二茂铁甲基)三甲基铵配合物对其电子转移反应动力学的影响

BioInorganic Reaction Mechanisms

Pub Date : 2006-01-01 DOI: 10.1515/IRM.2006.6.2.161

J. A. Imonigie, D. Macartney

The guest-host inclusion of transition metal complexes in macrocyclic receptors can have a pronounced effect on the kinetics of their electron transfer1-12 reactions in solution. In addition to rendering an included complex less reactive or nonreactive by means of inhibiting their access to the other reactant(s) in the reaction process, the inclusion can also change other properties, such as their reduction potential,13 which will in turn affect the kinetics of their electron transfer reactions. The effects of guest-host interactions on the kinetics of electron-exchange and electron transfer reactions of transition metal complexes have been studied with cyclic host molecules such as the crown ethers,1-4 cyclodextrins,6-12 and calixarenes.5 The kinetic behaviour of the included transit ion metal Inorganic Reaction Mechanisims, Vol. 6, pp. 161-168 © 2006 Old City Publishing, Inc. Reprints available directly from the publisher Published by license under the OCP Science imprint, Photocopying permitted by license only a member of the Old City Publishing Group.

大环受体中过渡金属配合物的主客体包合对其在溶液中的电子转移动力学有显著影响。除了通过抑制其在反应过程中与其他反应物的接触而使所含配合物的反应性降低或不反应性外，所含配合物还可以改变其他性质，例如它们的还原电位13，这将反过来影响其电子转移反应的动力学。以冠醚、1-4环糊精、6-12和杯芳烃为环宿主分子，研究了主-主相互作用对过渡金属配合物电子交换和电子转移反应动力学的影响含过渡离子金属无机反应机理的动力学行为，Vol. 6, pp. 161-168©2006 Old City Publishing, Inc.。可直接从出版商处获得重印，在OCP科学印记下通过许可出版，仅允许旧城出版集团成员的许可复印。

引用次数: 1

Mono- and Dinuclear Copper(II) Complexes of Pendant-Arm Macrocyclic Polyamines: Synthesis, Characterization and Investigation as Hydrolytic Cleavage Agents for DNA 悬垂臂大环多胺单核和双核铜(II)配合物:作为DNA水解裂解剂的合成、表征和研究

BioInorganic Reaction Mechanisms

Pub Date : 2006-01-01 DOI: 10.1515/IRM.2006.6.2.91

Nichola Mccann, G. D. Iuliis, G. Lawrance, M. Maeder, K. Schrader, P. Moore

Based on the 10-methyl-1,4,8,12-tetraazacyclopentadecane-10-amine (1) parent, macrocycles 10-benzylamine-10-methyl-1,4,8,12-tetraazacyclopentadecane (2), 10-(2'-pyridinylmethanamino) -10-methyl-1,4,8,1 2-tetraazacyclopentadecane (3) and 5-(hydroxymethyl)-5'-(10 ''-methyl-1 '',4 '',8 '',12 ''-tetraazacyclopentadecane-10 ''-amino)-(2,2'-dipyridine) (4), as well as the p-xylene-linked dinucleating macrocycle 1,4-bis( 10'-methyl-1',4',8',12'-tetraazacyclopentacecane-10'-aminomethyl)benzene (5) and its o-xylene analogue (6), have been synthesized as free ligands and or copper(II) complexes and characterized spectroscopically. Cyclic voltammetry of the Cu(II) complexes of 2 - 6 are also reported, with involvement of the pendant groups in complexation influencing voltammetric behaviour. Potentionnetric titrations of 1, 2, 5 and 6 and their Cu(II) complexes yielded pK(a) values. Both dimers 5 and 6, as well as their mononuclear close analogues 1 and 2, have proven to be inefficient as hydrolytic cleavage agents for DNA, as was also the case for mononuclear Cu(II) complexes of N-4-macrocycles with a range of N-pendant groups based on the 3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),13,15-triene framework (7). Mononuclear triazamacrocyclic Cu(II) complexes show greater activity. Of other dinuclear systems examined, dicopper(II) complexes of the relatively rigid compartment ligands 3,13-dimethyl-3,13-dinitro-1,5,11,15-tetraazacycloeicosane-8,18-diol and -dithiol are also inactive. Whereas the 1:1 Cu(II):L complexes of cyclam and its N,N',N '',N '''-tetrakis(methylbenzyl) substituted analogue are inactive, the tetrakis(2-methylpyridine)-substituted analogue as a 2:1 Cu(II):L species mu-hydroxy {tetrakis(2'-methylpyridine)-1,4,8,11-tetraazacyclotetradecane} dicopper(II) is very efficient as a cleavage agent for plasmid DNA, with both single and double strand cleavage steps observed with rate constants (at pH 7.6, 37 degrees C, 0.8 mM complex, 0.12 mg/mL plasmid) of 1.2x10(-4) and 3.5x10(-6) s(-1) respectively. This is attributed to the capacity for concerted binding to the phosphodiester unit and nucleophilic attack by the coordinated hydroxide molecule that is activated by bridging between the two metal centres.

基于10-甲基-1,4,8,12-四氮杂环戊烷-10-胺(1)母体，大环10-苄胺-10-甲基-1,4,8,12-四氮杂环戊烷(2)，10-(2'-吡啶基甲氨基)- 10-甲基-1,4,8,1 -四氮杂环戊烷(3)和5-(羟甲基)-5'-(10 '-甲基-1,4,8 '，12 '-四氮杂环戊烷-10 '-氨基)-(2,2'-二吡啶)(4)，以及对二甲苯连接的二核大环1,4-二(10'-甲基-1'，4'，8'，12'-四氮杂环戊烷-10'-氨基甲基)苯(5)及其邻二甲苯类似物(6)作为游离配体和或铜(II)配合物被合成并进行了光谱表征。还报道了2 - 6的Cu(II)配合物的循环伏安法，其中参与络合的悬垂基团影响伏安行为。1、2、5和6及其Cu(II)配合物的电位滴定得到了pK(a)值。二聚体5和6，以及它们的单核类似物1和2，都被证明是低效的DNA水解裂解剂，同样的，基于3,7,11,17-四氮杂环[11.3.1]十六元-1(17)，13,15-三烯框架的n -4大环的单核Cu(II)配合物也是如此(7)。单核三氮杂环Cu(II)配合物表现出更大的活性。在研究的其他双核体系中，相对刚性的室室配体3,13-二甲基-3,13-二硝基-1,5,11,15-四氮杂环二糖烷-8,18-二醇和-二硫醇的二铜(II)配合物也是非活性的。环环酮的1:1 Cu(II):L配合物及其N,N'，N '，N ''-四元(甲基苄)取代类似物是无活性的，而四元(2-甲基吡啶)取代类似物作为2:1 Cu(II):L种多羟基四元(2'-甲基吡啶)-1,4,8,11-四氮杂环十四烷}铜(II)作为质粒DNA的切割剂是非常有效的，在速率常数(pH 7.6, 37℃，0.8 mM配合物)下观察到单链和双链切割步骤。0.12 mg/mL质粒)分别为1.2 × 10(-4)和3.5 × 10(-6) s(-1)。这是由于与磷酸二酯单元协同结合的能力，以及由两个金属中心之间的桥接激活的配位氢氧化物分子的亲核攻击。

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