{"title":"Kinetics and Mechanism of Oxidation of β-Alanine by a Ag(III) Complex","authors":"S. Huo, C. Song, J. Shan, S. Shen, Hanwen Sun","doi":"10.1515/IRM.2007.6.3.231","DOIUrl":"https://doi.org/10.1515/IRM.2007.6.3.231","url":null,"abstract":"","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"97 1","pages":"231 - 238"},"PeriodicalIF":0.0,"publicationDate":"2007-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83500653","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Kinetic and Mechanistic Studies of Uncatalysed Substitution of Coordinated Cyanide in Hexacyanoferrate(II) by Phenylhydrazine","authors":"R. Naik, R. Tiwari, P. Singh, A. Verma","doi":"10.1515/IRM.2007.6.3.217","DOIUrl":"https://doi.org/10.1515/IRM.2007.6.3.217","url":null,"abstract":"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.","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"96 1","pages":"217 - 224"},"PeriodicalIF":0.0,"publicationDate":"2007-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78764747","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nichola Mccann, G. D. Iuliis, G. Lawrance, M. Maeder, K. Schrader, P. Moore
{"title":"Mono- and Dinuclear Copper(II) Complexes of Pendant-Arm Macrocyclic Polyamines: Synthesis, Characterization and Investigation as Hydrolytic Cleavage Agents for DNA","authors":"Nichola Mccann, G. D. Iuliis, G. Lawrance, M. Maeder, K. Schrader, P. Moore","doi":"10.1515/IRM.2006.6.2.91","DOIUrl":"https://doi.org/10.1515/IRM.2006.6.2.91","url":null,"abstract":"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.","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"24 1","pages":"112 - 91"},"PeriodicalIF":0.0,"publicationDate":"2006-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77774432","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}