title: Imprinting of molecular recognition sites combined with π-donor-acceptor interactions using bis-aniline-crosslinked Au-CdSe/ZnS nanoparticles array on electrodes: Development of electrochemiluminescence sensor for the ultrasensitive and selective detection of 2-methyl-4-chlorophenoxyacetic acid.
abstract: A novel strategy is reported for the fabrication of bis-aniline-crosslinked Au nanoparticles (NPs)-CdSe/ZnS quantum dots (QDs) array composite by facil one-step co-electropolymerization of thioaniline-functionalized AuNPs and thioaniline-functionalized CdSe/ZnS QDs onto thioaniline-functionalized Au elctrodes (AuE). Stable and enhanced cathodic electrochemiluminescence (ECL) of CdSe/ZnS QDs is observed on the modified electrode in neutral solution, suggesting promising applications in ECL sensing. An advanced ECL sensor is explored for detection of 2-methyl-4-chlorophenoxyacetic acid (MCPA) which quenches the ECL signal through electron-transfer pathway. The sensitive determination of MCPA with limit of detection (LOD) of 2.2 nmolL(-1) (S/N=3) is achieved by π-donor-acceptor interactions between MCPA and the bis-aniline bridging units. Impressively, the imprinting of molecular recognition sites into the bis-aniline-crosslinked AuNPs-CdSe/ZnS QDs array yields a functionalized electrode with an extremely sensitive response to MCPA in a linear range of 10 pmolL(-1)-50 μmolL(-1) with a LOD of 4.3 pmolL(-1 ()S/N=3). The proposed ECL sensor with high sensitivity, good selectivity, reproducibility and stability has been successfully applied for the determination of MCPA in real samples with satisfactory recoveries. In this study, ECL sensor combined the merits of QDs-ECL and molecularly imprinting technology is reported for the first time. The developed ECL sensor holds great promise for the fabrication of QDs-based ECL sensors with improved sensitivity and furthermore opens the door to wide applications of QDs-based ECL in food safety and environmental monitoring.
authors.affiliation: Key Laboratory of Food Nutrition and Safety, Ministry of Education of China, No. 29, 13th Avenue, Tianjin Economic and Technological Development Area (TEDA), Tianjin 300457, China; Tianjin Key Laboratory of Food Nutrition and Safety, No. 29, 13th Avenue, Tianjin Economic and Technological Development Area (TEDA), Tianjin 300457, China; Tianjin University of Science and Technology, No. 29, 13th Avenue, Tianjin Economic and Technological Development Area (TEDA), Tianjin 300457, China.
authors.forename: Yukun
authors.initials: Y
authors.lastname: Yang
authors.affiliation: Key Laboratory of Food Nutrition and Safety, Ministry of Education of China, No. 29, 13th Avenue, Tianjin Economic and Technological Development Area (TEDA), Tianjin 300457, China; Tianjin Key Laboratory of Food Nutrition and Safety, No. 29, 13th Avenue, Tianjin Economic and Technological Development Area (TEDA), Tianjin 300457, China; Tianjin University of Science and Technology, No. 29, 13th Avenue, Tianjin Economic and Technological Development Area (TEDA), Tianjin 300457, China. Electronic address: fangguozhen@tust.edu.cn.
authors.forename: Guozhen
authors.initials: G
authors.lastname: Fang
authors.affiliation: Key Laboratory of Food Nutrition and Safety, Ministry of Education of China, No. 29, 13th Avenue, Tianjin Economic and Technological Development Area (TEDA), Tianjin 300457, China; Tianjin Key Laboratory of Food Nutrition and Safety, No. 29, 13th Avenue, Tianjin Economic and Technological Development Area (TEDA), Tianjin 300457, China; Tianjin University of Science and Technology, No. 29, 13th Avenue, Tianjin Economic and Technological Development Area (TEDA), Tianjin 300457, China.
authors.forename: Xiaomin
authors.initials: X
authors.lastname: Wang
authors.affiliation: Key Laboratory of Food Nutrition and Safety, Ministry of Education of China, No. 29, 13th Avenue, Tianjin Economic and Technological Development Area (TEDA), Tianjin 300457, China; Tianjin Key Laboratory of Food Nutrition and Safety, No. 29, 13th Avenue, Tianjin Economic and Technological Development Area (TEDA), Tianjin 300457, China; Tianjin University of Science and Technology, No. 29, 13th Avenue, Tianjin Economic and Technological Development Area (TEDA), Tianjin 300457, China.
authors.forename: Guiyang
authors.initials: G
authors.lastname: Liu
authors.affiliation: Key Laboratory of Food Nutrition and Safety, Ministry of Education of China, No. 29, 13th Avenue, Tianjin Economic and Technological Development Area (TEDA), Tianjin 300457, China; Tianjin Key Laboratory of Food Nutrition and Safety, No. 29, 13th Avenue, Tianjin Economic and Technological Development Area (TEDA), Tianjin 300457, China; Tianjin University of Science and Technology, No. 29, 13th Avenue, Tianjin Economic and Technological Development Area (TEDA), Tianjin 300457, China. Electronic address: s.wang@tust.edu.cn.
authors.forename: Shuo
authors.initials: S
authors.lastname: Wang
mesh_terms: D008456:2-Methyl-4-chlorophenoxyacetic Acid / Q000032:analysis* / Q000737:chemistry; D000814:Aniline Compounds / Q000737:chemistry; D019187:Cadmium Compounds / Q000737:chemistry; D003432:Cross-Linking Reagents / Q000737:chemistry; D004563:Electrochemistry / Q000295:instrumentation*; D004784:Environmental Monitoring / Q000295:instrumentation; D004785:Environmental Pollutants / Q000032:analysis / Q000737:chemistry; D004867:Equipment Design; D019544:Equipment Failure Analysis; D006046:Gold / Q000737:chemistry; D006540:Herbicides / Q000032:analysis / Q000737:chemistry; D008163:Luminescent Measurements / Q000295:instrumentation*; D053768:Metal Nanoparticles / Q000737:chemistry* / Q000648:ultrastructure; D046228:Microarray Analysis / Q000295:instrumentation; D008839:Microelectrodes; D054802:Molecular Imprinting; D045663:Quantum Dots; D015203:Reproducibility of Results; D018036:Selenium Compounds / Q000737:chemistry; D012680:Sensitivity and Specificity; D017967:Zinc Compounds / Q000737:chemistry
chemical_list: D000814:Aniline Compounds; D019187:Cadmium Compounds; D003432:Cross-Linking Reagents; D004785:Environmental Pollutants; D006540:Herbicides; D018036:Selenium Compounds; D017967:Zinc Compounds; D006046:Gold; C058667:cadmium selenide; D008456:2-Methyl-4-chlorophenoxyacetic Acid; C044696:zinc selenide
keywords: 2-methyl-4-chlorophenoxyacetic acid; Au nanoparticles; Electrochemiluminescence sensor; Molecularly imprinted polymers; Quantum dots; π-donor–acceptor interactions