title: Microfluidic paper-based analytical device for photoelectrochemical immunoassay with multiplex signal amplification using multibranched hybridization chain reaction and PdAu enzyme mimetics.
abstract: Combining multibranched hybridization chain reaction (mHCR), the photoelectrochemical (PEC) immunosensor was fabricated with a microfluidic paper-based analytical devices using different sizes of CdTe quantum dots (QDs) sensitized flower-like 3D ZnO superstructures as photoactive materials. Firstly, 4-aminothiophenol (PATP) functioned ZnO was anchored on gold-paper working electrode. With the aid of PATP, large-sized CdTe-COOH QDs (QDs1) were conjugated onto the ZnO surface because of the formation of a strong bond (Zn-S) between the thiol of PATP molecule and the ZnO, and the remaining amino group formed an amide bond with carboxylic acid group capping CdTe. Then the small-sized CdTe-NH2 QDs (QDs2) were modified on the QDs1 by forming amide bond, which leaded to a very strong photocurrent response because of the formation of cosensitized structure. The designed mHCR produced long products with multiple branched arms, which could attached multiple PdAu nanoparticles and catalyze the oxidation of hydroquinone (HQ) using H2O2 as anoxidant. Double strands DNA with multiple branched arms (mdsDNA) was formed by mHCR. In the presence of carcinoembryonic antigen (CEA), PdAu-mdsDNA conjugates-labeled CEA antibody was captured. The concentrations of CEA were measured through the decrease in photocurrent intensity resulting from the increase in steric hindrance of the immunocomplex and the polymeric oxidation product of HQ. In addition, the oxidation product of HQ deposited on the as-obtained electrode, which could efficiently inhibit the photoinduced electron transfer. Under optimal conditions, the PEC immunosensor exhibited excellent analytical performance: the detection range of CEA was from 0.001 to 90 ng mL(-1) with low detection limit of 0.33 pg mL(-1). The as-obtained immunosensor exhibited excellent precision, prominent specificity, acceptable stability and reproducibility, and could be used for the detection of CEA in real samples. The proposed assay opens a promising platform of clinical immunoassay for other biomolecules.
authors.affiliation: School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, PR China.
authors.forename: Feifei
authors.initials: F
authors.lastname: Lan
authors.affiliation: School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, PR China.
authors.forename: Guoqiang
authors.initials: G
authors.lastname: Sun
authors.affiliation: School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, PR China.
authors.forename: Linlin
authors.initials: L
authors.lastname: Liang
authors.affiliation: School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, PR China; Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, PR China. Electronic address: chm_gesg@163.com.
authors.forename: Shenguang
authors.initials: S
authors.lastname: Ge
authors.affiliation: School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, PR China.
authors.forename: Mei
authors.initials: M
authors.lastname: Yan
authors.affiliation: School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, PR China.
authors.forename: Jinghua
authors.initials: J
authors.lastname: Yu
mesh_terms: D015374:Biosensing Techniques / Q000379:methods*; D002272:Carcinoembryonic Antigen / Q000302:isolation & purification*; D004247:DNA / Q000737:chemistry; D055664:Electrochemical Techniques / Q000379:methods*; D006046:Gold / Q000737:chemistry; D006801:Humans; D007118:Immunoassay / Q000379:methods*; D044085:Microfluidics / Q000379:methods; D053758:Nanoparticles / Q000737:chemistry; D009693:Nucleic Acid Hybridization; D010209:Paper; D045663:Quantum Dots; D013440:Sulfides / Q000737:chemistry
chemical_list: D002272:Carcinoembryonic Antigen; D013440:Sulfides; D006046:Gold; D004247:DNA
keywords: Microfluidic paper-based analytical device; Multibranched hybridization chain reaction; PdAu enzyme mimetics; Photoelectrochemical immunoassay