Department of Analytical Chemistry, College of Chemistry, Jilin University, Changchun 130012, China.
Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 230022, China.
Biosens Bioelectron. 2014 Apr 15;54:617-22. doi: 10.1016/j.bios.2013.11.050. Epub 2013 Nov 25.
In this work, a novel fluorescence "turn off-on" nanosensor for the determination of heparin and heparinase based on CuInS2 quantum dots (QDs) was established. CuInS2 QDs (modified by l-cysteine) featuring amino groups were directly prepared in aqueous solution via a hydrothermal synthesis method. The amino groups on the surface of CuInS2 QDs can interact with sulfate and carboxylate groups in heparin via electrostatic interactions and hydrogen bonding, which led the fluorescence of CuInS2 QDs to "turn-off". However, the heparin could be hydrolyzed into small fragments in the presence of heparinase, which resulted in the fluorescence of CuInS2 QDs being recovered. Therefore, the addition of heparinase to the heparin/CuInS2 QDs system activated the fluorescence of CuInS2 QDs to "turn-on" state. Thus, the determination of heparin and heparinase could be achieved by monitoring the fluorescence "turn off-on". Under the optimum conditions, there was a good linear relationship between I/I0 (I and I0 were the fluorescence intensity of CuInS2 QDs in the presence and absence of heparin, respectively) and heparin concentration in the range of 0.05-15 μmol L(-1) with the detection limit of 12.46 nmol L(-1). The linear detection for heparinase was in the range of 0.2-5 μg mL(-1) with the detection limit of 0.07 μg mL(-1). The proposed nanosensor was employed for the detection of heparin in fetal bovine serum samples with satisfactory results.
在这项工作中,建立了一种基于 CuInS2 量子点 (QDs) 的新型荧光“关闭-开启”纳米传感器,用于测定肝素和肝素酶。CuInS2 QDs(通过 l-半胱氨酸修饰)具有氨基,可通过水热合成方法直接在水溶液中制备。CuInS2 QDs 表面的氨基可通过静电相互作用和氢键与肝素中的硫酸根和羧基相互作用,导致 CuInS2 QDs 的荧光“关闭”。然而,在肝素酶的存在下,肝素可被水解成小片段,导致 CuInS2 QDs 的荧光恢复。因此,向肝素/CuInS2 QDs 体系中加入肝素酶可激活 CuInS2 QDs 的荧光“开启”状态。因此,通过监测荧光“关闭-开启”,可以实现对肝素和肝素酶的测定。在最佳条件下,CuInS2 QDs 的荧光强度 (I) 在存在和不存在肝素时的比值 (I/I0) 与肝素浓度在 0.05-15 μmol L(-1) 范围内呈良好线性关系,检测限为 12.46 nmol L(-1)。肝素酶的线性检测范围为 0.2-5 μg mL(-1),检测限为 0.07 μg mL(-1)。该纳米传感器用于检测胎牛血清样品中的肝素,结果令人满意。