Exploring a monothiolated β-cyclodextrin as the template to synthesize copper nanoclusters with exceptionally increased peroxidase-like activity

Exploring a monothiolated β-cyclodextrin as the template to synthesize copper nanoclusters with exceptionally increased peroxidase-like activity
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DOI:
10.1007/s00604-016-1915-3
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发表时间:
2016-08
期刊:
影响因子:
5.7
通讯作者:
Y. Zhong;Chun Deng;Yu He;Y. Ge;G. Song
Y. Zhong;Chun Deng;Yu He;Y. Ge;G. Song
中科院分区:
化学2区
文献类型:
--
作者:
Y. Zhong;Chun Deng;Yu He;Y. Ge;G. Song

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作者描述了一种用于增加用于非酶测定的铜纳米团簇(Cu-NC)的过氧化物酶样催化性质的方法。通过利用6-硫代-β-环糊精作为模板和有效的调节剂来制备Cu-NC,以增加Cu-NC的过氧化物酶样性质。β-CD包被的Cu-NC的平均直径为2 nm,在水溶液中是稳定的,显示出强的荧光,激发/发射峰波长为360/450 nm,并且具有过氧化物酶样催化活性,这使得它们成为有用的酶模拟物。我们已将这些发现应用于非酶光度测定(在650 nm处):(a)使用β-CD/Cu-NC辅助的H2 O2氧化四甲基联苯胺,在0.02至10 mM的浓度范围内测定H2 O2;以及(B)在加入葡萄糖氧化酶并形成H2 O2后,在0.04至20 mM的浓度范围内测定葡萄糖。检出限(S/N = 3):H_2O_2为0.2 μM,葡萄糖为0.4 μM。结果表明,β-CD包被后,反应速率明显加快,这可能是由于β-CD的空腔对底物的识别和催化起了口袋的作用。因此,结合特异性变得类似于天然酶。图形摘要在非酶传感器中,通过利用单6-硫代-β-环糊精(mono-6-SH-β-CD)作为模板分子和有效的速率调节剂,强烈增强了Cu-NC的过氧化物酶样催化活性。
The authors describe a method for increasing the peroxidase-like catalytic properties of copper nanoclusters (Cu-NCs) that are used in non-enzymatic assays. The Cu-NCs were prepared by utilizing 6-thio-β-cyclodextrin as both the template and as effective modulators for increasing the peroxidase-like properties of the Cu-NCs. The β-CD-coated Cu-NCs have an average diameter of 2 nm, are stable in aqueous solutions, display strong fluorescence with excitation/emission peak wavelengths of 360/450 nm, and possess peroxidase-like catalytic activity which makes them a useful enzyme mimic. We have applied the findings to non-enzymatic photometric determination (at 650 nm) of (a) H2O2in the concentration range of 0.02 to 10 mM using the β-CD/Cu-NC assisted oxidation of tetramethylbenzidine by H2O2, and (b) glucose in the concentration range of 0.04 to 20 mM after addition of glucose oxidase and formation of H2O2. The detection limits (at an S/N ratio of 3) are 0.2 μM for H2O2and 0.4 μM for glucose. The β-CD coating is found to result in a strong increase in the reaction rate, probably because the cavity of β-CD acts as a pocket for the recognition and catalysis of substrate. Hence, the binding specificity becomes similar to that of natural enzymes.Graphical AbstractThe peroxidase-like catalytic activity of Cu-NCs in non-enzymatic sensors is strongly enhanced by utilizing mono-6-thio-β-cyclodextrin (mono-6-SH-β-CD) as both the template molecule and the effective rate modulator.