BioInorganic Reaction Mechanisms最新文献

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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

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 in vivo, 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.

Texaphyrins最早是由Sessler和他的同事在20世纪80年代制备的，是早期的扩展卟啉的例子。这类五杂、低聚吡啶类大环具有优异的肿瘤定位和金属螯合性能。在生物环境中，texaphyrins作为氧化还原介质，能够产生活性氧。此外，texaphyrins已被证明在体内上调锌，这是一个重要的特征，启发我们开发新的锌离子载体，可能允许通过更简单的化学手段激发相同的功能。在这篇综述中，我们将讨论texaphyrins的基本性质和它们帮助生成的锌离子载体，以期开发出一种新的、具有氧化还原活性的抗癌药物。

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

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.

采用停流法研究了银(III)配合物双碲二氢银辉钼矿(III)对ε-氨基己酸的氧化作用。Ag(III)配合物和ε-氨基己酸均为一级反应。从动力学研究中提出了Ag(III)配合物与ε-氨基己酸之间形成预平衡加合物的合理机理。由该机理导出的速率定律可以解释一切实验现象。计算了活化参数和速率常数。

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

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.

(Bu 4N)2[ReBr6]在暴露于空气中的乙基溴中的溶液在254或313 nm处照射可使六溴间酚酸盐(IV)完全转化为过氢酸盐离子。反应速率线性依赖于入射光强度和铼络合物吸收的光的比例与溴乙基吸收的光的比例的组合。实验结果与溶剂引发和金属引发两种途径产生的过氧自由基CH 3CH(Br)OO通过电子转移氧化[ReBr 6]2−的机理一致。

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

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.

用分光光度法研究了l -半胱氨酸和n -乙酰半胱氨酸与cs [Pt(en)(OH2)2]2+的反应动力学，作为[Pt(en)(OH2)2]2+ T、[l -半胱氨酸]T/[n -乙酰半胱氨酸]T和pH(4.0)温度的函数，其中Pt(II)络合物主要以双水系存在，l -半胱氨酸和n -乙酰半胱氨酸为两性离子。取代反应呈现两个连续的过程;第一步是配体辅助阳离子化，第二步是螯合。n -乙酰半胱氨酸的氨化速率常数大于l -半胱氨酸。l -半胱氨酸的H1(61.6±1.8 kJ mol−1)、H2(47.5±2.0 kJ mol−1)、S1(- 54.4±5.3 kJ mol−1)和S2(- 164.8±6.5 jk−1 mol−1)和n -乙酰半胱氨酸的H1(23.2±0.8 kJ mol−1)、H2(61.5±0.6 kJ mol−1)和S1(- 178.6±2.6 jk−1 mol−1)、S2(- 115.6±2.0 jk−1 mol−1)表明，在连续的两个步骤中，配体取代过程具有联合激活模式。

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

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.

用分光光度法研究了双periodatocuate (III) (DPC)在298.2 K - 313.2 K的碱性水介质中氧化3-氨基-1-丙醇(3-AP)的动力学。DPC和1 < nap < 2 ~ 3-AP均为准一级反应。在伪一阶条件下([3-AP] 0 [DPC]0)，不同浓度的[OH−]对反应速率常数的影响是不同的。在低[OH−]时，kobs随[OH−]的增加而降低，而在高[OH−]时，kobs随[OH−]的增加而增加，高碘酸盐对反应速率有延缓作用。存在微弱的负盐效应。通过现场试验对主要产品进行了鉴定。根据实验结果，提出了一种可能的氧化反应机理。由该机理导出的速率方程可以解释所有的实验现象。测定了反应的活化参数和速率决定步骤的速率常数。

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

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.

实验研究了硅酸盐离子与氢铝酸盐离子(硅铝摩尔比2:1)在KOH水溶液中反应的化学状态和动力学。假设氢氧根与硅和铝的缩合反应形成交联聚合物;这个反应代表了从铝硅酸盐矿物合成所谓地聚合物的本质。将溶液转变为凝胶所需的时间作为反应速率标准进行测量。测定的凝胶点时间对反应溶液中KOH浓度的依赖性呈线性趋势。凝胶点时间随着温度的升高而缩短。在反应过程中，溶液的pH值出现可测量的增加。对不同Si/Al摩尔比的凝胶点时间的测量证实了2:1的选择比例是最优的。为了定量描述反应过程和解释所观察到的现象，应用了缩聚反应和原水解平衡的理论。理论计算的凝胶点时间对KOH浓度的依赖关系与实验测定值一致，证实了所研究反应的预期缩聚机理。

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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

,(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

合成并表征了(en=乙二胺，pyip =(pyip = 2-(1-芘基)- 1h -咪唑[4,5-f][1,10]菲罗啉)，(aip = 2-(9-蒽基)- 1h -咪唑[4,5，-f][1,10]菲罗啉)。利用吸收(紫外/可见)和发射光谱、粘度测量以及DNA熔化和质粒DNA切割研究，研究了这些复合物与小牛胸腺DNA的相互作用。实验结果表明，这四种复合物都能以嵌入模式与DNA结合。复合物的dna结合亲和力

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

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.

用分光光度法研究了l -天冬酰胺与顺式-[Ru(bipy)2(H2O)2]2+的相互作用动力学，并将其作为[Ru(bipy)2(H2O)2+ 2]、[天冬酰胺]和温度在特定pH值4.8下的函数进行了研究，其中底物络合物主要以双水系存在，而l -天冬酰胺主要以两性离子存在。该反应经过两个连续的步骤进行。第一步涉及配体辅助阳离子化，第二步涉及当第二个水配体移位时的螯合。计算了速率常数和活化参数。低的激活焓和负值较大的激活熵表明这两个步骤的激活模式是相关联的。

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

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.

实验研究了硅酸盐水溶液与Al(III)、Sn(IV)、Zn(II)和Ga(III)氢氧配合物的反应。所有研究的反应都在整个体积的反应混合物中产生凝胶，根据我们的假设，这些反应的本质是硅酸盐阴离子与给定两性元素的羟基络合物阴离子之间的缩聚，形成交联的无机聚合物。研究反应过程的标准是反应混合物的凝胶点时间。记录了凝胶点时间与温度、KOH浓度和反应混合物中硅酸盐/两性元素的摩尔比的关系。用x射线荧光光谱法对所研究的反应产物进行了分析。所得结果均符合硅酸盐与羟基配合物缩聚反应的假设，表明硅酸盐与羟基铝酸盐之间的反应只是一般化学反应的一个例子。

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

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.

采用分光光度法研究了2，' -联吡啶(bpy)在酸性水溶液中催化铬(VI)氧化1,2 -丙二醇的动力学和机理。该反应对Cr(VI)为准一级反应，对1,2 -丙二醇为分数级反应。观察到的速率常数(kobs)随[H +]和[bpy]的增加而增加。离子强度的变化对反应速率没有明显影响，也没有检测到自由基。因此，假设hcro4是Cr(VI)的主要存在种类。根据实验结果，提出了一种可能的氧化反应机理。由该机理导出的速率方程可以解释所有的实验现象。计算了反应的活化参数和速率常数。

引用次数: 0

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