Bio-inspired nanozyme with ultra-thin Fe–Bi2O2S nanosheets for in-situ amplified photoelectrochemical immunoassay of cancer-related protein

This work reports a ZIF-8 (ZIF: Zeolitic Imidazolate Framework)-assisted NaYF4:Yb,Tm@ZnO upconverter for the photoelectrochemical (PEC) biosensing of carcinoembryonic antigen (CEA) under near-infrared (NIR) irradiation on a homemade 3D-printed device with DNA walker-based amplification strategy. The composite photosensitive material NaYF4:Yb,Tm@ZnO, as converter to transfer NIR import to photocurrent output, was driven from annealed NaYF4:Yb,Tm@ZIF-8. Yb3+ and Tm3+-codoped NaYF4 (NaYF4:Yb,Tm) converted NIR excitation into UV emission, matching with the absorption of ZnO for in situ excitation to generate the photocurrent. Upon target CEA introduction, the swing arm of DNA walker including the sequence of CEA aptamer carried out the sandwiched bioassembly with CEA capture aptamer on the G-rich anchorage DNA tracks-functionalized magnetic beads. Thereafter, DNA walker was triggered, and the swing arm DNA was captured by the G-rich anchorage DNA according to partly complementary pairing and Exonuclease III (Exo III) consumed anchorage DNA by a burnt-bridge mechanism to go into the next cycle. The released guanine (G) bases from DNA walker enhanced the photocurrent response on a miniature homemade 3D-printed device consisting of the detection cell, dark box, and light platform. Under optimal conditions, NaYF4:Yb,Tm@ZnO-based NIR light-driven PEC biosensor presented high sensitivity and selectivity for CEA sensing with a detection limit of 0.032 ng mL-1. Importantly, our strategy provides a new horizon for the development of NIR-based PEC biosensors in the aspect of developing MOF-derived photoelectric materials, flexible design of a 3D-printed device, and effective signal amplification mode.

Methods based on the photothermal effect (a common phenomenon in nature) have been widely applied in different fields; however, their application in bioanalysis has lagged behind. Herein, we designed a near-infrared (NIR) photothermal immunoassay for the qualitative or quantitative detection of prostate-specific antigen (PSA) using titanium carbide (Ti3C2) MXene quantum dot (QD)-encapsulated liposomes with high photothermal efficiency. This system involves a sandwich-type immunoreaction and photothermal measurements. Ti3C2 MXene QDs were utilized as innovative photothermal signal beacons and were encapsulated in liposomes for the labeling of the secondary antibody. The assay was carried out by coupling a low-cost microplate with a homemade 3D printed device. Under NIR-laser irradiation, the Ti3C2 MXene QDs converted the light energy into heat, and a shift in temperature corresponding with the analyte concentration was obtained on a handheld thermometer. Under optimal conditions, the Ti3C2 MXene QD-based photothermal immunoassay exhibited a dynamic linear range from 1.0 ng mL-1 to 50 ng mL-1 with a limit of detection of 0.4 ng mL-1 for PSA detection. Also, we constructed portable equipment using a portable near-infrared imaging camera to collect visual thermal data for the semi-quantitative analysis of the target PSA within 3 min. The specificity, reproducibility and accuracy of the photothermal immunoassay were acceptable. Importantly, our strategy opens new opportunities for protein point-of-care (POC) testing and biosecurity diagnostics.