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氨基酸席夫碱金属(II)配合物的光谱表征、循环伏安法、形态学、生物活性及DNA裂解研究

Spectral characterization, cyclic voltammetry, morphology, biological activities and DNA cleaving studies of amino acid Schiff base metal(II) complexes.

作者信息

Neelakantan M A, Rusalraj F, Dharmaraja J, Johnsonraja S, Jeyakumar T, Sankaranarayana Pillai M

机构信息

Chemistry Research Centre, National Engineering College, K.R. Nagar, Kovilpatti 628 503, Thoothukudi District, Tamil Nadu, India.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2008 Dec 15;71(4):1599-609. doi: 10.1016/j.saa.2008.06.008. Epub 2008 Jun 22.

Abstract

Metal complexes are synthesized with Schiff bases derived from o-phthalaldehyde (opa) and amino acids viz., glycine (gly) l-alanine (ala), l-phenylalanine (pal). Metal ions coordinate in a tetradentate or hexadentate manner with these N(2)O(2) donor ligands, which are characterized by elemental analysis, molar conductance, magnetic moments, IR, electronic, (1)H NMR and EPR spectral studies. The elemental analysis suggests the stoichiometry to be 1:1 (metal:ligand). Based on EPR studies, spin-Hamiltonian and bonding parameters have been calculated. The g-values calculated for copper complexes at 300K and in frozen DMSO (77K) indicate the presence of the unpaired electron in the dx2-y2 orbital. The evaluated metal-ligand bonding parameters showed strong in-plane sigma- and pi-bonding. X-ray diffraction (XRD) and scanning electron micrography (SEM) analysis provide the crystalline nature and the morphology of the metal complexes. The cyclic voltammograms of the Cu(II)/Mn(II)/VO(II) complexes investigated in DMSO solution exhibit metal centered electroactivity in the potential range -1.5 to +1.5V. The electrochemical data obtained for Cu(II) complexes explains the change of structural arrangement of the ligand around Cu(II) ions. The biological activity of the complexes has been tested on eight bacteria and three fungi. Cu(II) and Ni(II) complexes show an increased activity in comparison to the controls. The metal complexes of opapal Schiff base were evaluated for their DNA cleaving activities with calf-thymus DNA (CT DNA) under aerobic conditions. Cu(II) and VO(II) complexes show more pronounced activity in presence of the oxidant.

摘要

金属配合物是由邻苯二甲醛(opa)与氨基酸(即甘氨酸(gly)、L-丙氨酸(ala)、L-苯丙氨酸(pal))衍生的席夫碱合成的。金属离子以四齿或六齿方式与这些N(2)O(2)供体配体配位,通过元素分析、摩尔电导率、磁矩、红外光谱、电子光谱、(1)H核磁共振和电子顺磁共振光谱研究对其进行表征。元素分析表明化学计量比为1:1(金属:配体)。基于电子顺磁共振研究,计算了自旋哈密顿量和键合参数。在300K和冷冻二甲基亚砜(77K)中计算得到的铜配合物的g值表明在dx2 - y2轨道中存在未成对电子。评估的金属 - 配体键合参数显示出强的面内σ键和π键。X射线衍射(XRD)和扫描电子显微镜(SEM)分析提供了金属配合物的晶体性质和形态。在二甲基亚砜溶液中研究的Cu(II)/Mn(II)/VO(II)配合物的循环伏安图在 - 1.5至 + 1.5V的电位范围内表现出以金属为中心的电活性。从Cu(II)配合物获得的电化学数据解释了配体围绕Cu(II)离子的结构排列变化。已对八种细菌和三种真菌测试了配合物的生物活性。与对照相比,Cu(II)和Ni(II)配合物显示出增强的活性。在有氧条件下,评估了opa - pal席夫碱的金属配合物对小牛胸腺DNA(CT DNA)的DNA切割活性。在氧化剂存在下,Cu(II)和VO(II)配合物显示出更明显的活性。

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