MnO2纳米酶催化ABTS的显色反应及其在Fe2+和Pb2+检测中的应用
Chromogenic reaction of ABTS catalyzed by MnO2 nanozyae and its application in the visual detection of Fe2+ and Pb2+
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摘要:
本文探讨了纳米MnO2催化2,2'-联氮双(3-乙基苯并噻唑啉-6-磺酸)二铵盐(ABTS)显色反应的类氧化酶活性,系统地评估了单一金属离子Fe2+和Pb2+对MnO2纳米酶活性的影响及作用机理,揭示了MnO2纳米酶-ABTS反应体系在选择性检测实际水体中Fe2+和Pb2+的应用.在pH 3.8、25℃条件下,纳米MnO2能够催化ABTS单电子转移形成ABTS阳离子自由基(ABTS·+,绿色产物),其类氧化酶活性为0.0412 U·mL-1.酶剂量、底物浓度、pH和温度影响了MnO2纳米酶活性.在反应体系中添加0.01 mmol·L-1 Fe2+(或Pb2+)显著地抑制了MnO2纳米酶活性(P < 0.01),主要是由于Fe2+(或Pb2+)在静电引力作用下强烈吸附在纳米MnO2表面,导致MnO2纳米酶催化活性的钝化甚至失活.其中Fe2+吸附在MnO2纳米酶表面能够与多价锰发生氧化还原反应,而Pb2+特异性吸附在MnO2纳米酶表面形成络合物.加标回收试验结果表明,MnO2纳米酶能够用于选择性测定实际水样中单一污染的Fe2+和Pb2+.MnO2纳米酶-ABTS反应体系对天然水体中Fe2+和Pb2+的检测具有较高精确度(相对误差为3.4%-10.5%)和良好回收性能(回收率为96%-110%).研究结果提供了一种简单、快速、高灵敏的检测方法用于可视化分析环境水样中Fe2+和Pb2+浓度.
Abstract:Nanoscale metal oxide-based enzymatic detection system is an alluring way for versatile applications in the environmental fields. In this paper. The oxidase-mimicking activity of nano-MnO2 was investigated to catalyze the chromogenic reaction of 2,2'-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS) in citrate-phosphate buffer solution (C-PBS) at 25℃ and pH 3.8. Moreover, the effect and mechanism of single metal ion (i.e., Fe2+ or Pb2+) on MnO2 nanozyme activity was also systematically evaluated. Particularly, MnO2 nanozyme-ABTS as a detection system was respectively used for visual detection of Fe2+ and Pb2+ ions in the real water samples. Results showed that nano-MnO2 could catalyze the single-electron transfer of ABTS to form ABTS radical cations (ABTS·+, green product), suggesting that nano-MnO2 possessed owned the oxidase-like activity. The dosage of MnO2 nanozyme, substrate concentration, pH, and temperature exhibited evident influence on the catalytic activity of nano-MnO2. It is worth noting that the activity of MnO2 nanozyme was significantly inhibited in the presence of 0.01 mmol·L-1 Fe2+(或Pb2+) ion (P < 0.01), which was mainly due to the strong affinity of Fe2+(或Pb2+) ion toward the reactive sites of nano-MnO2 surface via electrostatic attractions, thereby leading to the passivation and inactivation of MnO2 nanozyme catalytic activity. Thereinto, Fe2+ was absorbed onto MnO2 nanozyme surface and reacted with multivalent Mn by oxidation-reduction, while Pb2+ was specifically adsorbed onto the surface of MnO2 nanozyme and formed complexes. Additionally, MnO2 nanozyme could also be used as a detection system for visual detection of Fe2+ and Pb2+ in real water samples. This detection system achieved high accuracy (relative errors:3.4%-10.5%) and recovery (recovery rate:96%-110%) for the detection of Fe2+ and Pb2+ in the real water samples. Such cost-effective detection system provided a simple, fast, and highly sensitive approach for visual detection of Fe2+ and Pb2+ ions in the environmental water samples.
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Key words:
- MnO2 nanozyme /
- ABTS /
- chromogenic reactions /
- metal ion /
- inhibition mechanism
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