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MnO2纳米酶催化ABTS的显色反应及其在Fe2+和Pb2+检测中的应用

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谢道月, 刘琦, 汪珺, 张锡涛, 顾凯业, 孙凯. MnO2纳米酶催化ABTS的显色反应及其在Fe2+和Pb2+检测中的应用[J]. 环境化学, 2019, (12): 2843-2850. doi: 10.7524/j.issn.0254-6108.2019010404
引用本文: 谢道月, 刘琦, 汪珺, 张锡涛, 顾凯业, 孙凯.

MnO2纳米酶催化ABTS的显色反应及其在Fe2+和Pb2+检测中的应用

[J]. 环境化学, 2019, (12): 2843-2850. doi: 10.7524/j.issn.0254-6108.2019010404
shu
XIE Daoyue, LIU Qi, WANG Jun, ZHANG Xitao, GU Kaiye, SUN Kai. Chromogenic reaction of ABTS catalyzed by MnO2 nanozyae and its application in the visual detection of Fe2+ and Pb2+[J]. Environmental Chemistry, 2019, (12): 2843-2850. doi: 10.7524/j.issn.0254-6108.2019010404
Citation: XIE Daoyue, LIU Qi, WANG Jun, ZHANG Xitao, GU Kaiye, SUN Kai.

Chromogenic reaction of ABTS catalyzed by MnO2 nanozyae and its application in the visual detection of Fe2+ and Pb2+

[J]. Environmental Chemistry, 2019, (12): 2843-2850. doi: 10.7524/j.issn.0254-6108.2019010404
shu

MnO2纳米酶催化ABTS的显色反应及其在Fe2+和Pb2+检测中的应用

  • 农田生态保育与污染防控安徽省重点实验室, 安徽农业大学资源与环境学院, 合肥, 230036

    • 通讯作者: 孙凯, E-mail: sunkai@ahau.edu.cn
  • 基金项目:

    国家自然科学基金（41471405），安徽省自然科学基金（1808085QD104），安徽农业大学稳定和引进人才项目（yj2018-31）资助.

Chromogenic reaction of ABTS catalyzed by MnO2 nanozyae and its application in the visual detection of Fe2+ and Pb2+

  • Anhui Province Key Laboratory of Farmland Ecological Conservation and Pollution Prevention, School of Resources and Environment, Anhui Agricultural University, Hefei, 230036, China

    • Corresponding author: SUN Kai, sunkai@ahau.edu.cn
  • Fund Project: Supported by the National Natural Science Foundation of China (41471405), the Natural Science Foundation of Anhui Province (1808085QD104), and the Stabilized and Introduced Talent Foundation of Anhui Agricultural University (yj2018-31).

  • 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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  • 收稿日期:  2019-01-04
  • 刊出日期:  2019-12-10

MnO2纳米酶催化ABTS的显色反应及其在Fe2+和Pb2+检测中的应用

    通讯作者: 孙凯, E-mail: sunkai@ahau.edu.cn
  • 农田生态保育与污染防控安徽省重点实验室, 安徽农业大学资源与环境学院, 合肥, 230036
  • 收稿日期:  2019-01-04
  • 网络出版日期:  2019-12-10
基金项目:

国家自然科学基金（41471405），安徽省自然科学基金（1808085QD104），安徽农业大学稳定和引进人才项目（yj2018-31）资助.

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.

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