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Dual signal amplification coupling dual inhibition effect for fabricating photoelectrochemical chlorpyrifos biosensor

Year: 2017

Journal: Sens. Actuator B-Chem., Volume 238, FEB, page 239–248

Authors: Mao, Hanping; Yan, Yuting; Hao, Nan; Liu, Qian; Qian, Jing; Chen, Saibo; Wang, Kun

Organizations: National Natural Science Foundation of China [21175061, 21375050]; National Key Technology Research and Development Program of the Ministry of Science and Technology of the People's Republic of China [2014BAD08B03]; Innovation Project of Science and Technology for College Graduates of Jiangsu Province [KYLX15_1085]; Priority Academic Program Development of Jiangsu Higher Education Institutions [PAPD-2014-37]; China Postdoctoral Science Foundation Funded Project [2015T80517]; Qing Lan Project; Key Laboratory of Modern Agriculture Equipment and Technology [NZ201109]

Keywords: Chlorpyrifos; CuFe2O4; Graphene quantum dot; Dual signal amplification; Dual inhibition; Photoelectrochemical biosensor

Photoelectrochemical (PEC) detection is an attractive analytical tool as it allows for an elegant and sensitive assay. However, designing a novel detection strategy to achieve an excellent PEC analytical performance is still highly challenging. Herein we design a novel photoelectrochemical (PEC) chlorpyrifos biosensor based on dual signal amplification strategy coupling dual inhibition effect. Dual signal amplification strategy was achieved by coupling the graphene quantum dots sensitized CuFe2O4 magnetic nanocrystal clusters (GQDsCuFe(2)O(4) MNCs) with the amplification of enzymolysis products. In this biosensing architecture, the GQDsCuFe(2)O(4) MNCs prepared by electrostatic adsorption showed nearly 4-fold and 30-fold enhancement photocurrent compared with the pure CuFe2O4 MNCs and GQDs, respectively. And the contact angle measurement demonstrated that the GQDsCuFe(2)O(4) MNCs exhibited good biocompatibility. Based on all these above advantages, the GQDsCuFe(2)O(4) MNCs were immobilized on the magnetic electrode surface by a fast and simple magnetism-assisted assembly, and the acetylcholinesterase (AChE) was further coated on the surface of the as-prepared multifunctional electrode. Due to thiocholine (enzymolysis products) acts as a sacrificial electron donor to scavenge the holes, compared with the GQDsCuFe(2)O(4) MNCs modified electrode in the acetylthiocholine chloride solution, the photocurrent of the resulting AChE-based biosensor was further significantly enhanced. Based on the dual inhibition of AChE activity by chlorpyrifos and the formation of Cu-chlorpyrifos complex hindered the electron transfer of CuFe2O4 MNCs toward the electrode surface, the proposed AChE-based biosensor can be applied to the quantification of chlorpyrifos with a linear range from 0.001 mu g mL(-1) to 1 mu g mL(-1) and a detection limit of 0.3 ng mL(-1) (S/N = 3). This novel dual signal amplification strategy opens up a new avenue for achieving high sensitivity in the field of PEC biosensing. (C) 2016 Elsevier B.V. All rights reserved.