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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Interaction of Triapine and related thiosemicarbazones with iron(III)/(II) and gallium(III): A comparative solution equilibrium study
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Interaction of Triapine and related thiosemicarbazones with iron(III)/(II) and gallium(III): A comparative solution equilibrium study

机译:Triapine和相关的硫代半脲与铁(III)/(II)和镓(III)的相互作用:溶液平衡比较研究

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摘要

Stoichiometry and stability of Ga~(III), Fe~(III), Fe ~(II) complexes of Triapine and five related α-N heterocyclic thiosemicarbazones with potential antitumor activity have been determined by pH-potentiometry, UV-vis spectrophotometry, ~1H NMR spectroscopy, and spectrofluorimetry in aqueous solution (with 30% DMSO), together with the characterization of the proton dissociation processes. Additionally, the redox properties of the iron complexes were studied by cyclic voltammetry at various pH values. Formation of high stability bis-ligand complexes was found in all cases, which are predominant at physiological pH with Fe~(III)/Fe ~(II), whilst only at the acidic pH range with Ga~(III). The results show that among the thiosemicarbazones with various substituents the N-terminal dimethylation does not exert a measurable effect on the redox potential, but has the highest impact on the stability of the complexes as well as the cytotoxicity, especially in the absence of a pyridine-NH_2 group in the molecule. In addition the fluorescence properties of the ligands in aqueous solution and their changes caused by Ga~(III) were studied.
机译:已通过pH电位法,紫外可见分光光度法测定了Triapine的Ga〜(III),Fe〜(III),Fe〜(II)配合物和5种具有潜在抗肿瘤活性的相关α-N杂环硫代半缩氮唑的化学计量和稳定性1H NMR光谱和水溶液(含30%DMSO)中的荧光光谱,以及质子解离过程的特征。另外,通过循环伏安法在各种pH值下研究了铁络合物的氧化还原性质。在所有情况下都发现形成高稳定性的双配体配合物,它们在生理pH下以Fe〜(III)/ Fe〜(II)为主,而仅在酸性pH下以Ga〜(III)为主。结果表明,在具有各种取代基的硫半脲中,N端二甲基化对氧化还原电位没有可测量的影响,但对配合物的稳定性和细胞毒性的影响最大,尤其是在没有吡啶的情况下分子中的-NH_2基团。此外,研究了配体在水溶液中的荧光性质及其由Ga〜(III)引起的变化。

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