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Synergistic effect of sandwich polyoxometalates and copper-imidazole complexes for enhancing the peroxidase-like activity

机译:夹心多金属氧酸盐和咪唑铜配合物的协同作用增强过氧化物酶样活性

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Two inorganic-organic hybrids based on copper(II)-imidazole complex modified sandwich-type tungstobismuthate Or tungstoantimonite, Na4H2[Cu-4(H(4)im)(12)(H(3)im)(2)][Cu-3(H2O)(3)(XW9O33)(2)]center dot nH(2)O (H(4)im = imidazole, H(3)im = deprotonated imidazole, X = Bi (1), n = 28 or X = Sb (2), n = 25), have been synthesized and structurally characterized by single crystal X-ray diffraction and FTIR. The sandwich polyoxoanion [CU3(H2O)(3)(XW9O33)(2)](12-) is modified by two copper(m)-imidazole complexes to form 1 or 2, in which an anionic imidazole is rarely observed as a linker to coordinate to two neighboring copper ions. As compared to other Keggin-type polyoxametalate-based peroxidase-like mimics, 1 and 2 both demonstrate higher peroxidase-like activity using 3,3',5,5'-tetramethylbenzidine (TMB) as a peroxidase substrate in the presence of H2O2 around physiological pH values in a heterogeneous phase. The maximized synergistic effects of sandwich-type POMs and copper(m)-imidazole complexes are responsible for the enhancement of the peroxidase- like activity. The negatively charged POMs and non-covalent interactions between imidazole ligands and TMB are beneficial to increase the affinity of TMB substrate, and thus lead to higher sensitivity towards H2O2. Considering the dependence of TMB colour on H2O2 concentrations, compound 1 can be used as an effective probe to detect H2O2 through a facile calorimetric method in a linear range from 1 mu M to 50 mu M with a low detection limit of 0.12 mu M.
机译:Na4H2 [Cu-4(H(4)im)(12)(H(3)im)(2)] [Cu]的两种基于铜(II)-咪唑配合物修饰的夹心型钨铋铋酸盐或钨锑锑酸盐的无机-有机杂化物-3(H2O)(3)(XW9O33)(2)]中心点nH(2)O(H(4)im =咪唑,H(3)im =去质子化的咪唑,X = Bi(1),n = 28或X = Sb(2),n = 25),已经合成并通过单晶X射线衍射和FTIR对其结构进行了表征。夹心多氧阴离子[CU3(H2O)(3)(XW9O33)(2)](12-)被两个铜(m)-咪唑配合物改性以形成1或2,其中很少见到阴离子咪唑为连接基与两个相邻的铜离子配合。与其他基于Keggin型多金属氧酸盐的过氧化物酶样模拟物相比,使用3,3',5,5'-四甲基联苯胺(TMB)作为过氧化物酶底物,且周围存在H2O2时,1和2均显示出较高的过氧化物酶样活性。异相中的生理pH值。夹心型POM和铜(m)-咪唑复合物的最大协同作用是增强过氧化物酶样活性的原因。带负电荷的POM和咪唑配体与TMB之间的非共价相互作用有利于增加TMB底物的亲和力,从而导致对H2O2的更高敏感性。考虑到TMB颜色对H2O2浓度的依赖性,化合物1可以用作简便的量热法,在1μM至50μM的线性范围内以0.12μM的低检测限通过线性量热法检测H2O2。

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