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[钴(II,III)与二硫代氨基甲酸衍生物的配合物——苏云金芽孢杆菌肽酶及红麴青霉和白色隐球菌α-L-鼠李糖苷酶的效应物]

[Complexes of cobalt (II, III) with derivatives of dithiocarbamic acid--effectors of peptidases of Bacillus thuringiensis and alpha-L-rhamnozidase of Eupenicillium erubescens and Cryptococcus albidus].

作者信息

Varbanets L D, Matseliukh E V, Seĭfullina I I, Khitrich N V, Nidialkova N A, Hudzenko E V

出版信息

Ukr Biochem J. 2014 May-Jun;86(3):49-60.

PMID:25033554
Abstract

The influence of cobalt (II, III) coordinative compounds with derivatives of dithiocarbamic acid on Bacillus thuringiensis IMV B-7324 peptidases with elastase and fibrinolytic activity and Eupenicillium erubescens and Cryptococcus albidus alpha-L-rhamnosidases have been studied. Tested coordinative compounds of cobalt (II, III) on the basis of their composition and structure are presented by 6 groups: 1) tetrachlorocobaltates (II) of 3,6-di(R,R')-iminio-1,2,4,5-tetratiane--(RR')2Ditt[CoCl4]; 2) tetrabromocobaltates (II) of 3,6-di(R,R')-iminio-1,2,4,5-tetratiane--(RR')2Ditt[CoBr4]; 3) isothiocyanates of tetra((R,R')-dithiocarbamatoisothiocyanate)cobalt (II)--Co(RR'Ditc)42]; 4) dithiocarbamates of cobalt (II)--[Co(S2CNRR')2]; 5) dithiocarbamates of cobalt (III)--[Co(S2CNRR')3]; 6) molecular complexes of dithiocarbamates of cobalt (III) with iodine--[Co(S2CNRR')3] x 2I(2). These groups (1-6) are combined by the presence of the same complexing agent (cobalt) and a fragment S2CNRR' in their molecules. Investigated complexes differ by a charge of intrinsic coordination sphere: anionic (1-2), cationic (3) and neutral (4-6). The nature of substituents at nitrogen atoms varies in each group of complexes. It is stated that the studied coordination compounds render both activating and inhibiting effect on enzyme activity, depending on composition, structure, charge of complex, coordination number of complex former and also on the enzyme and strain producer. Maximum effect is achieved by activating of peptidases B. thuringiensis IMV B-7324 with elastase and fibrinolytic activity. So, in order to improve the catalytic properties of peptidase 1, depending on the type of exhibited activity, it is possible to recommend the following compounds: for elastase--coordinately nonsaturated complexes of cobalt (II) (1-4) containing short aliphatic or alicyclic substituents at atoms of nitrogen and increasing activity by 17-100% at an average; for fibrinolytic--neutral dithiocarbamates of cobalt (II, III) (4-5) (by 29-199%). For increasing the fibrinolytic activity of peptidase it is better to use dibenzyl- or ethylphenyldithiocarbamates of cobalt (III), which increase activity by 15-40% at an average. The same complexes, and also compound {(CH2)6}2Ditt[CoCl4] make an activating impact on alpha-L-rhamnosidase C. albidus (by 10-20%).

摘要

研究了钴(II,III)与二硫代氨基甲酸衍生物的配位化合物对苏云金芽孢杆菌IMV B - 7324具有弹性蛋白酶和纤维蛋白溶解活性的肽酶以及红麴霉和白色隐球菌α - L - 鼠李糖苷酶的影响。基于其组成和结构,测试的钴(II,III)配位化合物分为6组:1)3,6 - 二(R,R') - 亚氨基 - 1,2,4,5 - 四氮杂环乙烷的四氯钴酸盐(II) - (RR')2Ditt[CoCl4];2)3,6 -二(R,R') - 亚氨基 - 1,2,4,5 - 四氮杂环乙烷的四溴钴酸盐(II) - (RR')2Ditt[CoBr4];3)四((R,R') - 二硫代氨基甲酰异硫氰酸酯)钴(II)的异硫氰酸盐 - [Co(RR'Ditc)4](NCS)2];4)钴(II)的二硫代氨基甲酸盐 - [Co(S2CNRR')2];5)钴(III)的二硫代氨基甲酸盐 - [Co(S2CNRR')3];6)钴(III)的二硫代氨基甲酸盐与碘的分子配合物 - [Co(S2CNRR')3]×2I(2)。这些组(1 - 6)因分子中存在相同的络合剂(钴)和片段S2CNRR'而组合在一起。所研究的配合物因内配位球的电荷不同而有所差异:阴离子型(1 - 2)、阳离子型(3)和中性型(4 - 6)。每组配合物中氮原子上取代基的性质各不相同。研究表明,所研究的配位化合物对酶活性具有激活和抑制作用,这取决于其组成、结构、配合物的电荷、配合物形成体的配位数以及酶和产生菌株。对具有弹性蛋白酶和纤维蛋白溶解活性的苏云金芽孢杆菌IMV B - 7324肽酶的激活可达到最大效果。因此,为了根据所表现出的活性类型改善肽酶1的催化特性,可推荐以下化合物:对于弹性蛋白酶活性 - 钴(II)的配位不饱和配合物(1 - 4),其氮原子上含有短脂肪族或脂环族取代基,平均活性提高17 - 100%;对于纤维蛋白溶解活性 - 钴(II,III)的中性二硫代氨基甲酸盐(4 - 5)(提高29 - 199%)。为了提高肽酶的纤维蛋白溶解活性,最好使用钴(III)的二苄基或乙基苯基二硫代氨基甲酸盐,其平均活性提高15 - 40%。相同的配合物以及化合物{(CH2)6}2Ditt[CoCl4]对白色隐球菌α - L - 鼠李糖苷酶具有激活作用(提高10 - 20%)。

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