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Dinuclear copper(II) complexes with derivative triazine ligands as biomimetic models for catechol oxidases and nucleases
Journal of Inorganic Biochemistry ( IF 3.8 ) Pub Date : 2020-09-17 , DOI: 10.1016/j.jinorgbio.2020.111249
Marcos P Silva 1 , Cristine Saibert 2 , Tiago Bortolotto 2 , Adailton J Bortoluzzi 1 , Gerhard Schenk 3 , Rosely A Peralta 1 , Hernán Terenzi 2 , Ademir Neves 1
Affiliation  

The research reported herein focuses on the synthesis of two new Cu(II) complexes {[Cu2(2-X-4,6-bis(di-2-picolylamino)-1,3,5-triazine], with X = butane-1,4-diamine (2) or N-methylpyrenylbutane-1,4-diamine (3)}, the latter with a pyrene group as a possible DNA intercalating agent. The structure of complex (3) was determined by X-ray crystallography and shows the dinuclear {CuII(μ-OCH3)2CuII} unit in which the CuII···CuII distance of 3.040 Å is similar to that of 2.97 Å previously found for 1, which contains a {CuII(μ-OH)2CuII} structural unit. Complexes (2) and (3) were also characterized in spectroscopic and electrochemical studies, and catecholase-like activity were performed for both complexes. The kinetic parameters obtained for the oxidation of the model substrate 3,5-di-tert-butylcatechol revealed that the insertion of the spacer butane-1,4-diamine and the pyrene group strongly contributes to increasing the catalytic efficiency of these systems. In fact, Kass becomes significantly higher, indicating that these groups influence the interaction between the complex and the substrate. These complexes also show DNA cleavage under mild conditions with moderate reaction times. The rate of cleavage (kcat) indicated that the presence of butane-1,4-diamine and pyrene increased the activity of both complexes. The reaction mechanism seems to have oxidative and hydrolytic features and the effect of DNA groove binding compounds and circular dichroism indicate that all complexes interact with plasmid DNA through the minor groove. High-resolution DNA cleavage assays provide information on the interaction mechanism and for complex (2) a specificity for the unpaired hairpin region containing thymine bases was observed, in contrast to (3).



中文翻译:

双核铜(II)与衍生物三嗪配体的络合物作为儿茶酚氧化酶和核酸酶的仿生模型

本文报道的研究重点在于合成两种新的Cu(II)配合物{[Cu 2(2-X-4,6-bis(di-2-picolylamino)-1,3,5-triazine],其中X =丁烷-1,4-二胺(2)N-甲基吡啶基丁烷-1,4-二胺(3) },后者可能带有pyr基作为DNA嵌入剂,配合物(3)的结构由X-射线晶体学和示出了双核铜{ II(μ-OCH 32的Cu II }单元,其中在Cu II ...的Cu II 3.040埃的距离类似于2.97先前发现的1,它包含一个{铜II(μ-OH)2 Cu II }结构单元。配合物(2)(3)也在光谱和电化学研究中得到表征,并且对两种配合物都进行了儿茶酚酶样活性。为氧化模型底物3,5-二叔丁基邻苯二酚而获得的动力学参数表明,间隔基1,4-丁二胺和the基的插入极大地有助于提高这些系统的催化效率。其实K屁股变得更高,表明这些基团影响复合物与底物之间的相互作用。这些复合物还在温和条件下以中等反应时间显示出DNA裂解。裂解速率(k cat)表明,-1,4-丁二胺和pyr的存在增加了两种配合物的活性。反应机理似乎具有氧化和水解特性,DNA沟结合化合物和圆二色性的影响表明所有复合物均通过小沟与质粒DNA相互作用。高分辨率的DNA裂解检测提供了有关相互作用机理的信息,而对于复合物(2),观察到了对未配对的含有胸腺嘧啶碱基的发夹区域的特异性,与(3)

更新日期:2020-10-02
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