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黑磷量子点可用作比色法测定生物硫醇的氧化酶模拟物。

Black phosphorus quantum dots are useful oxidase mimics for colorimetric determination of biothiols.

机构信息

Key Laboratory of Analytical Chemistry for Life Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China.

出版信息

Mikrochim Acta. 2020 Mar 13;187(4):229. doi: 10.1007/s00604-020-4222-y.

Abstract

Black phosphorus quantum dots (BP QDs) with small size are synthesized using an easy to operate thermal method. It was found that BP QDs possess oxidase-mimicking activity. They can catalyze the oxidation of the substrate 3,3',5,5'-tetramethylbenzidine to produce a blue-colored product even in the absence of hydrogen peroxide. Active oxygen species are proved to be involved in the reaction through the experiments of radical scavenging and electron spin resonance. Biothiols including reduced glutathione and cysteine inactivate the oxidase-mimicking activity of BP QDs, concomitant to the fading of the blue solution. This provides the  base for a colorimetric method for the determination of glutathione and cysteine. The decreased absorbance at 652 nm displays linear response to the concentrations of glutathione ranging from 0.1 to 5.0 μmol L, and cysteine from 0.1 to 10.0 μmol L. The detection limits are 0.02 μmol L and 0.03 μmol L for glutathione and cysteine, respectively. Successive determinations of 1.0 μmol L glutathione and 5.0 μmol L cysteine solution give relative standard deviations of 0.8% and 1.7% (n = 11), respectively. As a preliminary application, the practicability of the method was evaluated by the determination of glutathione in pharmaceutical preparations. This work not only discovers a useful oxidase mimics but also sets up a reliable platform based on BP QDs in colorimetric detection. Graphical abstract Schematic representation of colorimetric determination for biothiols through inactivating oxidase mimetic-like catalytic activity of black phosphorus quantum dots (BP QDs) on the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) with dissolved oxygen to produce its blue oxidized product (oxTMB).

摘要

采用一种易于操作的热法合成了具有小尺寸的黑磷量子点(BP QDs)。研究发现,BP QDs 具有氧化酶模拟活性。即使在没有过氧化氢的情况下,它们也可以催化底物 3,3',5,5'-四甲基联苯胺的氧化,产生蓝色产物。通过自由基清除和电子顺磁共振实验证明活性氧物种参与了反应。生物硫醇,包括还原型谷胱甘肽和半胱氨酸,使 BP QDs 的氧化酶模拟活性失活,同时蓝色溶液褪色。这为基于比色法测定谷胱甘肽和半胱氨酸提供了依据。在 652nm 处的吸光度降低与谷胱甘肽浓度在 0.1 至 5.0μmol/L 范围内呈线性响应,与半胱氨酸在 0.1 至 10.0μmol/L 范围内呈线性响应。谷胱甘肽和半胱氨酸的检测限分别为 0.02μmol/L 和 0.03μmol/L。对 1.0μmol/L 谷胱甘肽和 5.0μmol/L 半胱氨酸溶液进行连续 11 次测定,相对标准偏差分别为 0.8%和 1.7%(n=11)。作为初步应用,通过测定药物制剂中的谷胱甘肽评估了该方法的实用性。这项工作不仅发现了一种有用的氧化酶模拟物,而且还在比色检测中建立了一个基于黑磷量子点的可靠平台。

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