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.

A new double photosystems-based 'Z-scheme' photoelectrochemical (PEC) sensing platform is designed for ultrasensitive detection of prostate-specific antigen (PSA) by coupling with a three-dimensional (3D) DNA walker. Two photosystems consist of CdS quantum dots (photosystem I; PS I) and BiVO photoactive materials (photosystem II; PS II), whereas gold nanoparticles (AuNPs) photodeposited on high-active {010} facets of BiVO are used as the electron mediators to promote electron transfer from conduction band of PS II to valence band of PS I. 3D DNA walker-based amplification strategy is carried out between hairpin DNA1 conjugated onto the AuNP, hairpin DNA2 labeled with CdS quantum dot (QD-H2), and DNA walker complementary with the PSA aptamer modified to a magnetic bead (Apt-MB). Upon addition of target, DNA walker strand is displaced from DNA walker/Apt-MB to open hairpin DNA1 on AuNP@BiVO. In the presence of QD-H2, DNA walker induces the hybridization of DNA1 with DNA2 on the gold nanoparticles step by step, thereby resulting in the assembly of CdS QDs on the AuNP@BiVO to form Z-scheme double photosystems with strong photocurrent. Under optimum conditions, the Z-scheme PEC sensing system exhibits good photocurrent responses toward target PSA within the working range of 0.01-50 ng mL at a low detection limit of 1.5 pg mL. Good reproducibility and accuracy are acquired for analysis of target PSA and human serum specimens relative to the commercial PSA ELISA kit. Importantly, our strategy provides a new horizon for photoelectrochemical in vitro diagnostics.

This work demonstrates that the photoelectric response of defect-engineered TiO modified with Au nanoparticles can be modulated by oxygen vacancy concentration and excitation wavelength. When strongly plasmonic Au nanoparticles are anchored to defect-engineered TiO by DNA hybridization, several times plasmonic enhancement of photocurrent occurs under 585 nm excitation, and it is employed as a novel signaling mode for developing an improved photoelectrochemical sensing platform. This signaling mode combined with exonuclease III-assisted target recycling amplification exhibits excellent analytical performance, which provides a novel photoelectrochemical detection protocol.

This work has looked to explore an innovative and powerful visible fluorescence immunoassay method through wet NH 3triggered structural change of NH 2 -MIL-125(Ti) impregnated on paper for the detection of carcinoembryonic antigen (CEA). Gold nanoparticles heavily functionalized with glutamate dehydrogenase (GDH) and secondary antibody were used for generation of wet NH 3 with a sandwiched immunoassay format. Paper-based analytical device (PAD) coated with NH 2 -MIL-125(Ti) exhibited good visible fluorescence intensity through wet NH 3 -triggeried structural change with high accuracy and reproducibility. Moreover, NH 2 -MIL-125(Ti)-based PAD displayed two visual modes of fluorescence color and physical color with the naked eye and allowed the detection of CEA at a concentration as low as 0.041 ng mL −1 . Importantly, the PAD-based assay provides promise for use in the mass production of miniaturized devices and opens new opportunities for protein diagnostics and biosecurity.

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chem.9b03177. Measurement with AFP ELISA kit for human serum samples, calculation method for t-test statistics, statistical analysis, and Figures S1−S5 (PDF) ■ AUTHOR INFORMATION

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