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Texaphyrins and water-soluble zinc(II) ionophores: development, mechanism of anticancer activity, and synergistic effects. Texaphyrins和水溶性锌离子载体:发展、抗癌活性机制和协同效应。
BioInorganic Reaction Mechanisms Pub Date : 2013-12-01 DOI: 10.1515/irm-2013-0001
Christian Preihs, Darren J Magda, Jonathan L Sessler
{"title":"Texaphyrins and water-soluble zinc(II) ionophores: development, mechanism of anticancer activity, and synergistic effects.","authors":"Christian Preihs,&nbsp;Darren J Magda,&nbsp;Jonathan L Sessler","doi":"10.1515/irm-2013-0001","DOIUrl":"https://doi.org/10.1515/irm-2013-0001","url":null,"abstract":"<p><p>Texaphyrins, first prepared by Sessler and coworkers in the 1980s, represent early examples of expanded porphyrins. This class of pentaaza, oligopyrrolic macrocycles demonstrates excellent tumor localization and metal-chelating properties. In biological milieus, texaphyrins act as redox mediators and are able to produce reactive oxygen species. Furthermore, texaphyrins have been shown to upregulate zinc <i>in vivo</i>, an important feature that inspired us to develop new zinc ionophores that might allow the same function to be elicited but via a simpler chemical means. In this review, the basic properties of texaphyrins and the zinc ionophores they helped spawn will be discussed in the cadre of developing an understanding that could lead to the preparation of new, redox-active anticancer agents.</p>","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"9 1-4","pages":"3-14"},"PeriodicalIF":0.0,"publicationDate":"2013-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1515/irm-2013-0001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"32730060","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 3
Oxidation of ε-Aminocaproic Acid by Bis(dihydrogentellurato)argentite(III): A Kinetics and Mechanism Study 双氢辉银矿氧化ε-氨基己酸(III)动力学及机理研究
BioInorganic Reaction Mechanisms Pub Date : 2008-12-01 DOI: 10.1515/IRM.2008.6.4.313
S. Huo, C. Song
{"title":"Oxidation of ε-Aminocaproic Acid by Bis(dihydrogentellurato)argentite(III): A Kinetics and Mechanism Study","authors":"S. Huo, C. Song","doi":"10.1515/IRM.2008.6.4.313","DOIUrl":"https://doi.org/10.1515/IRM.2008.6.4.313","url":null,"abstract":"The oxidation ofε-aminocaproic acid by the Ag(III) complex, bis(dihydrogen tellurato)argentite(III) was studied by the stopped-flow method. It was both first order with respect to Ag(III) complex and ε-aminocaproic acid. A plausible mechanism involving a pre-equilibrium adduct formation between the Ag(III) complex and ε-aminocaproic acid was proposed from the kinetics study. The rate law derived from the mechanism can explain all experimental phenomena. The activation parameters along with rate constants were calculated.","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"207 1","pages":"313 - 320"},"PeriodicalIF":0.0,"publicationDate":"2008-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78176178","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}
引用次数: 0
The Photooxidation of Hexabromorhenate(IV) in Ethyl Bromide 六溴庚酸酯(IV)在溴乙基中的光氧化反应
BioInorganic Reaction Mechanisms Pub Date : 2008-12-01 DOI: 10.1515/IRM.2008.6.4.293
Jessica L. Cohen, P. Hoggard
{"title":"The Photooxidation of Hexabromorhenate(IV) in Ethyl Bromide","authors":"Jessica L. Cohen, P. Hoggard","doi":"10.1515/IRM.2008.6.4.293","DOIUrl":"https://doi.org/10.1515/IRM.2008.6.4.293","url":null,"abstract":"Irradiation at 254 or 313 nm of solutions of (Bu 4N)2[ReBr6] in ethyl bromide exposed to air causes complete conversion of the hexabromorhenate(IV) to perrhenate ion. The rate of the reaction is linearly dependent on the incident light intensity and on a combination of the fraction of light absorbed by the rhenium complex and the fraction absorbed by the ethyl bromide. The experimental results are consistent with a mechanism in which the peroxy radical CH 3CH(Br)OO, produced in both the solvent-initiated and metal-initiated pathways, oxidizes [ReBr 6]2− by electron transfer.","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"6 1","pages":"293 - 300"},"PeriodicalIF":0.0,"publicationDate":"2008-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75654280","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}
引用次数: 1
Kinetic and Mechanistic Study of the Interaction of L-cysteine and N-acetylcysteine with cis-[Pt(en)(H2O)2](ClO4)2 in Aqueous Medium l -半胱氨酸和n -乙酰半胱氨酸与顺式[Pt(en)(H2O)2](ClO4)2相互作用的动力学和机理研究
BioInorganic Reaction Mechanisms Pub Date : 2008-12-01 DOI: 10.1515/IRM.2008.6.4.321
D. K. Baral, A. Dash, A. Pattanaik, P. Mohanty, M. Nanda
{"title":"Kinetic and Mechanistic Study of the Interaction of L-cysteine and N-acetylcysteine with cis-[Pt(en)(H2O)2](ClO4)2 in Aqueous Medium","authors":"D. K. Baral, A. Dash, A. Pattanaik, P. Mohanty, M. Nanda","doi":"10.1515/IRM.2008.6.4.321","DOIUrl":"https://doi.org/10.1515/IRM.2008.6.4.321","url":null,"abstract":"The kinetics of the reactions of L-cysteine and N-acetylcysteine with c s[Pt(en)(OH2)2]2+ have been studied spectrophotometrically as a function of [Pt(en) (OH2)2] 2+ T , [L-cysteine]T/[N-acetylcysteine] T and temperature at pH (4.0) where the Pt(II) complex exists predominantly as a diaqua species and L-cysteine and N-acetylcysteine as zwitterions. The substitution reaction shows two consecutive processes; the first step is the ligand assisted anation and the second one is the chelation step. The anation rate constants for N-acetylcysteine were found to be greater than that for L-cysteine. H1 (61.6 ± 1.8 kJ mol −1) H2 (47.5 ± 2.0 kJ mol −1), S1 (−54.4 ± 5.3 J.K−1 mol−1) and S2 (−164.8 ± 6.5 J.K−1 mol−1) for L-cysteine and H1 (23.2 ± 0.8 kJ mol −1), H2 (61.5 ± 0.6 kJ mol −1) and S1 (−178.6±2.6 J.K−1 mol−1), S2 (−115.6±2.0 J.K−1 mol−1) for N-acetylcysteine indicate an associative mode of activation for both the ligand substitution processes in the two consecutive steps.","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"60 1","pages":"321 - 326"},"PeriodicalIF":0.0,"publicationDate":"2008-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85180623","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}
引用次数: 2
Kinetics and Mechanism of Oxidation of 3-Amino-1-propanol by Diperiodatocuprate(III) in Alkaline Medium 双periodatocuate (III)在碱性介质中氧化3-氨基-1-丙醇的动力学及机理
BioInorganic Reaction Mechanisms Pub Date : 2008-01-01 DOI: 10.1515/IRM.2008.6.4.275
J. Shan, C. Han, S. Huo, L. Fan
{"title":"Kinetics and Mechanism of Oxidation of 3-Amino-1-propanol by Diperiodatocuprate(III) in Alkaline Medium","authors":"J. Shan, C. Han, S. Huo, L. Fan","doi":"10.1515/IRM.2008.6.4.275","DOIUrl":"https://doi.org/10.1515/IRM.2008.6.4.275","url":null,"abstract":"The kinetics of oxidation of 3-amino-1-propanol (3-AP) by diperiodatocuprate(III) (DPC) in aqueous alkaline medium have been studied by spectrophotometry in the temperature range 298.2 K–313.2 K. The reaction was found to be pseudo-first order with respect to DPC and 1 < nap < 2 to 3-AP. It was found that under pseudo-first order conditions ([3-AP] 0 [DPC]0), the observed rate constant kobschanged differently under different concentration of [OH −]. At low [OH−], kobsdecreased with increase in [OH−], but at higher [OH−], kobs increase with increase in [OH −], and periodate had a retarding effect on the reaction rate. There is a weak negative salt effect. The main products were identified by spot tests. Based on the experimental results, a probable reaction mechanism of oxidation is proposed. The rate equation derived from the mechanism can explain all the experimental phenomena. The activation parameters, along with the rate constants of the rate-determining step, were determined.","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"11 1","pages":"275 - 280"},"PeriodicalIF":0.0,"publicationDate":"2008-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84487248","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}
引用次数: 1
Reaction between Silicate and Hydroxoaluminate Ions in Aqueous Solution 水溶液中硅酸盐与氢铝酸盐离子的反应
BioInorganic Reaction Mechanisms Pub Date : 2008-01-01 DOI: 10.1515/IRM.2008.6.4.265
V. Bednařík, M. Vondruška, R. Slavík
{"title":"Reaction between Silicate and Hydroxoaluminate Ions in Aqueous Solution","authors":"V. Bednařík, M. Vondruška, R. Slavík","doi":"10.1515/IRM.2008.6.4.265","DOIUrl":"https://doi.org/10.1515/IRM.2008.6.4.265","url":null,"abstract":"The chemical status and kinetics of the reaction between silicate ions and hydroxoaluminate ions (at Si/Al molar ratio 2:1) in KOH aqueous solution has been experimentally studied. It is assumed that condensation of OH groups bonded to silicon and aluminum occurs in this reaction forming a cross-linked polymer; and that the reaction represents the essence of synthesis of so-called geopolymer from alumino-silicate minerals. Time required for the change of the solution to a gel was measured as the reaction rate criterion. Measured dependences of the gel-point time on KOH concentration in the reaction solution exhibit a linear trend. The gel-point time decreases with increasing temperature. A measurable increase in pH value of the solution appears during the reaction. Measurement of the gel-point time for different Si/Al molar ratios has confirmed that the selected ratio 2:1 has been optimal. For a quantitative description of the reaction course and for explanation of the observed phenomena, the theories of polycondensation reactions and protolytic equilibria have been applied. Theoretically calculated dependences of the gel-point time on KOH concentration are in accord with experimentally determined values, which confirms anticipated polycondensation mechanism of the reaction under study.","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"148 1","pages":"265 - 274"},"PeriodicalIF":0.0,"publicationDate":"2008-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87571314","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}
引用次数: 2
DNA-binding and Photocleavage Studies of Ethylenediamine Cobalt(III) and Ruthenium(II) Mixed Ligand Complexes 乙二胺钴(III)和钌(II)混合配体配合物的dna结合和光裂解研究
BioInorganic Reaction Mechanisms Pub Date : 2008-01-01 DOI: 10.1515/IRM.2008.6.4.301
P. Nagababu, M. Shilpa, Md. B. Mustafa, P. Ramjee, S. Satyanarayana
{"title":"DNA-binding and Photocleavage Studies of Ethylenediamine Cobalt(III) and Ruthenium(II) Mixed Ligand Complexes","authors":"P. Nagababu, M. Shilpa, Md. B. Mustafa, P. Ramjee, S. Satyanarayana","doi":"10.1515/IRM.2008.6.4.301","DOIUrl":"https://doi.org/10.1515/IRM.2008.6.4.301","url":null,"abstract":",(en=ethylene-diamine, pyip =(pyip = 2-(1-pyrenyl)-1H-imidazo[4,5-f][1,10]phenanthroline),(aip = 2-(9-anthryl)-1H-imidazo[4,5,-f][1,10] phenanthroline) have been synthe-sized and characterized. The interaction of these complexes with calf thymus DNAwas investigated using absorption (UV/vis) and emission spectroscopy, viscositymeasurements as well as DNA melting and plasmid DNA cleavage studies. Theexperimental results show that the four complexes can bind to DNA in an intercala-tion mode. The DNA-binding affinity of complex","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"55 1","pages":"301 - 312"},"PeriodicalIF":0.0,"publicationDate":"2008-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83904725","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}
引用次数: 4
Kinetic and Mechanistic Studies on the Interaction between L-Asparagine and cis-Diaquabis(bipyridine)ruthenium(II) Complex in Aqueous Medium l -天冬酰胺与顺式双胍(联吡啶)钌(II)配合物在水溶液中相互作用的动力学和机理研究
BioInorganic Reaction Mechanisms Pub Date : 2008-01-01 DOI: 10.1515/IRM.2008.6.4.257
Aishwarya MUKHERJEE (GOSWAMI),, K. De
{"title":"Kinetic and Mechanistic Studies on the Interaction between L-Asparagine and cis-Diaquabis(bipyridine)ruthenium(II) Complex in Aqueous Medium","authors":"Aishwarya MUKHERJEE (GOSWAMI),, K. De","doi":"10.1515/IRM.2008.6.4.257","DOIUrl":"https://doi.org/10.1515/IRM.2008.6.4.257","url":null,"abstract":"The kinetics of interaction between L-asparagine and cis-[Ru(bipy)2(H2O)2]2+ have been studied spectrophotometrically as a function of [Ru(bipy)2(H2O)2+ 2 ], [Lasparagine] and temperature at a particular pH 4.8 where the substrate complex exists predominantly as a diaqua species and L-asparagine as a zwitterion. The reaction has been found to proceed through two consecutive steps. The first step involves the ligand assisted anation while the second step involves chelation when the second aqua ligand is displaced. Rate constants have been evaluated and activation parameters are calculated. The low enthalpy of activation and large negative value of entropy of activation indicate an associative mode of activation for both the steps.","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"122 3","pages":"257 - 264"},"PeriodicalIF":0.0,"publicationDate":"2008-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91493537","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}
引用次数: 0
Polycondensation of Silicate with Hydroxocomplexes of Some Amphoteric Elements in Aqueous Solution 水溶液中硅酸盐与某些两性元素羟基配合物的缩聚反应
BioInorganic Reaction Mechanisms Pub Date : 2008-01-01 DOI: 10.1515/IRM.2008.6.4.327
V. Bednařík, M. Vondruška, R. Slavík, J. Mellar
{"title":"Polycondensation of Silicate with Hydroxocomplexes of Some Amphoteric Elements in Aqueous Solution","authors":"V. Bednařík, M. Vondruška, R. Slavík, J. Mellar","doi":"10.1515/IRM.2008.6.4.327","DOIUrl":"https://doi.org/10.1515/IRM.2008.6.4.327","url":null,"abstract":"Reactions of aqueous solution of silicate with hydroxocomplexes of Al(III), Sn(IV), Zn(II) and Ga(III) have been experimentally studied. All studied reactions have produced gel in the whole volume of reaction mixture, and according to our hypothesis the essence of these reactions is polycondensation between silicate anions and anions of hydroxocomplex of the given amphoteric element, with formation of crosslinked inorganic polymer. Criterion for studying the course of the tested reactions has been the gel-point time of the reaction mixture. Dependences of the gel-point time on temperature, on KOH concentration and on molar ratios of silicate/amphoteric element in reaction mixture have been recorded. Products of the studied reactions have been analyzed by means of X-ray fluorescent spectrometry. All obtained results are in accord with the hypothesis of polycondensation reaction between silicate and hydroxocomplexes, and indicate that the reaction between silicate and hydroxoaluminate is merely one case of a more general chemical reaction.","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"16 1","pages":"327 - 336"},"PeriodicalIF":0.0,"publicationDate":"2008-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73205944","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}
引用次数: 2
2, 2'-Bipyridyl Catalysis of the Chromium (VI) Oxidation of 1, 2-propanediol: a Kinetic and Mechanistic Study 2,2′-联吡啶基催化铬(VI)氧化1,2 -丙二醇的动力学和机理研究
BioInorganic Reaction Mechanisms Pub Date : 2008-01-01 DOI: 10.1515/IRM.2008.6.4.281
J. Shan, L. Fan, S. Huo, C. Han, S. Shen
{"title":"2, 2'-Bipyridyl Catalysis of the Chromium (VI) Oxidation of 1, 2-propanediol: a Kinetic and Mechanistic Study","authors":"J. Shan, L. Fan, S. Huo, C. Han, S. Shen","doi":"10.1515/IRM.2008.6.4.281","DOIUrl":"https://doi.org/10.1515/IRM.2008.6.4.281","url":null,"abstract":"The kinetics and mechanism of 2 , ′-bipyridyl (bpy) catalysis of the chromium(VI) oxidation of 1, 2-propanediol in aqueous acidic medium has been studied spectrophotometrically. The reaction shows pseudo-first order with respect to Cr(VI) and fractional order with respect to 1 , 2-propanediol. The observed rate constant ( kobs) increases with the increase in [H +] and [bpy]. Change in ionic strength does not influence the rate obviously and no free radicals are detected. Thus, HCrO 4 is assumed the main existing species of Cr(VI). Based on the experimental results, a probable reaction mechanism of oxidation is proposed. The rate equation derived from the mechanism can explain all the experimental phenomena. The activation parameters along with rate constants of the rate-determining step have been calculated.","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"9 1","pages":"281 - 286"},"PeriodicalIF":0.0,"publicationDate":"2008-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83496432","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}
引用次数: 0
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