An all-in-one paper-based analytical device (PAD) was successfully developed for visual fluorescence detection of carcinoembryonic antigen (CEA) on CdTe/CdSe quantum dot (QD)-enzyme-impregnated paper by coupling with a bioresponsive controlled-release system from DNA-gated mesoporous silica nanocontainers (MSNs). The assay was carried out in a centrifuge tube by using glucose-loaded MSNs with a CEA aptamer and a QD-enzyme-paper attached on the lid. Initially, single-strand complementary DNA to a CEA aptamer was covalently conjugated to the aminated MSN, and then glucose (enzyme substrate) molecules were gated into the pore with the help of the aptamer. Glucose oxidase (GOD) and CdTe/CdSe QDs were coimmobilized on paper for the visual fluorescence signal output. Upon target CEA introduction in the detection cell, the analyte specifically reacted with the immobilized aptamer on the MSN to open the pore, thereby resulting in the glucose release. The released glucose was oxidized by the immobilized GOD on paper to produce gluconic acid and hydrogen peroxide, and the latter quenched the fluorescence of CdTe/CdSe QDs, which could be determined by the naked eye on a portable smartphone and a commercial fluorospectrometer. Under optimal conditions, the PAD-based sensing system enabled sensitive discrimination of target CEA against other biomarkers or proteins in a linear range of 0.05-20 ng mL with a limit of detection of 6.7 pg mL (ppt). In addition, our strategy displayed high specificity, good reproducibility, and acceptable accuracy for analyzing human serum specimens with a commercial human CEA ELISA kit. Importantly, this methodology offers promise for simple analysis of biological samples and is suitable for use in the mass production of miniaturized devices, thus opening new opportunities for protein diagnostics and biosecurity.

Titanium dioxide (TiO; as a potential photosensitizer) has good photocurrent performance and chemical stability but often exhibits low utilization efficiency under ultraviolet (UV) region excitation. Herein, we devised a near-infrared light-to-UV light-mediated photoelectrochemical (PEC) aptasensing platform for the sensitive detection of carcinoembryonic antigen (CEA) based on core-shell NaYF:Yb,Tm@TiO upconversion microrods by coupling with target-triggered rolling circle amplification (RCA). The upconversion microrods synthesized through the hydrothermal reaction could act as a photosensing platform to convert the near-infrared (near-IR) excitation into UV emission for generation of photoinduced electrons. The target analyte was determined on a functional magnetic bead by using the corresponding aptamers with a sandwich-type assay format. Upon target CEA introduction, a complex was first formed between capture aptamer-1-conjugated magnetic bead (Apt1-MB) and aptamer-2-primer DNA (Apt2-pDNA). Thereafter, the carried primer DNA by the aptamer-2 paired with linear padlock DNA to trigger the RCA reaction. The guanine (G)-rich product by RCA reaction was cleaved by exonuclease I and exonuclease III (Exos I/III), thereby resulting in the formation of numerous individual guanine bases to enhance the photocurrent of core-shell NaYF:Yb,Tm@TiO upconversion microrods under near-IR illumination (980 nm). Under optimal conditions, the near-IR light-mediated PEC aptasensing system could exhibit good photoelectrochemical response toward target CEA and allowed for the detection of target CEA as low as 3.6 pg mL. High reproducibility and good accuracy were achieved for analysis of human serum specimens. Importantly, the near-IR-activated PEC aptasensing scheme provides a promising platform for ultrasensitive detection of other biomolecules.

A near-infrared light-activated ratiometric photoelectrochemical aptasensor was fabricated for detection of carcinoembryonic antigen (CEA) coupling with upconversion nanoparticles (UCNPs)-semiconductor nanocrystals-based spatial-resolved technique on a homemade 3D printing device in which a self-regulating integrated electrode was designed for dual signal readout. The as-prepared NaYF4:Yb,Er UCNPs@CdTe nanocrystals were initially assembled on two adjacent photoelectrodes, then CEA aptamer 1 (A1) and capture DNA (CA) were modified onto two working photoelectrodes (WP1 and WP2) through covalent binding, respectively, and then gold nanoparticle-labeled CEA aptamer 2 (Au NP-A2) was immobilized on the surface of functional WP2 for the formation of double-stranded DNA. Upon target CEA introduction, the various concentrations of CEA were captured on the WP1, whereas the binding of the CEA with Au NP-A2 could be released from the WP2 thanks to the highly affinity of CEA toward A2. The dual signal readout with the “signal-off” of WP1 and “signal-on” of WP2 were employed for the spatial-resolved PEC (SR-PEC) strategy to detect CEA as an analytical model. Combining NaYF4:Yb,Er UCNPs@CdTe nanocrystals with spatial-resolved model on 3D printing device, the PEC ratiometric aptasensor based on steric hindrance effect and exciton–plasmon interactions (EPI) exhibited a linear range from 10.0 pg mL–1 to 5.0 ng mL–1 with a limit of detection of 4.8 pg mL–1 under 980 nm illumination. The SR-PEC ratiometric strategy showed acceptable stability and reproducibility with a superior anti-interference ability. This approach can provide the guidance for the design of ratiometric, multiplexed, and point-of-care biosensors.

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.

Herein a novel split-type photoelectrochemical (PEC) immunosensing platform was designed for sensitive detection of low-abundance biomarkers (prostate-specific antigen, PSA, used in this case) by coupling a peroxyoxalate chemiluminescence (PO-CL) self-illuminated system with digital multimeter (DMM) readout. The PEC detection device consisted of a capacitor/DMM-joined electronic circuit and a PO-CL-based self-illuminated cell. Initially, reduced graphene oxide-doped BiVO4 (BiVO4-rGO) photovoltaic materials with good photoelectric properties was integrated into the capacitor/DMM-joined circuit for photocurrent generation in the presence of hydrogen peroxide (H2O2, as the hole-trapping reagent). A sandwich-type immunoreaction with target PSA was carried out in capture antibody-coated microplates by using glucose oxidase/detection antibody-conjugating gold nanoparticle (pAb2-AuNP-GOx). Accompanying the sandwiched immunocomplex, the labeled GOx could oxidize glucose to produce H2O2. The as-generated H2O2 could act as the coreaction reagent to trigger the chemiluminescence of the peroxyoxalate system and the PEC reaction of the BiVO4-rGO. Meanwhile, the self-illuminated light could induce photovoltaic material (BiVO4-rGO) to produce a voltage that was utilized to charge an external capacitor. With the switch closed, the capacitor could discharge through the DMM and provide an instantaneous current. Different from conventional PEC immunoassays, the as-generated photoelectron was stored in the capacitor and released instantaneously to amplify the photocurrent. Under the optimal conditions, the transient current increased with the increasing target PSA concentration in the dynamic working range from 10 pg mL(-1) to 80 ng mL(-1) with a detection limit (LOD) of 3 pg mL(-1). This work demonstrated for the first time that the peroxyoxalate CL system could be used as a suitable substitute of physical light source to apply in PEC immunoassay. In addition, this methodology afforded good reproducibility, precision, and high specificity, and the method accuracy matched well with the commercial PSA ELISA kit. Importantly, the developed split-type photoelectrochemical immunoassay could not only avoid the interfering of the biomolecules relative to the photovoltaic materials but also eliminate the need of an exciting light source and expensive instrumentation, thus representing a user-friendly and low-cost assay protocol for practical utilization in quantitative low-abundance proteins.

An innovative near-infrared (NIR) light-driven photoelectrochemical (PEC) aptasensor was constructed for sensitive screening of carcinoembryonic antigen (CEA) on the basis of in situ formation of AgS nanoparticles on the NaYF:Yb,Er upconversion nanoparticles (UCNs), coupled with hybridization chain reaction (HCR) for the signal amplification. Utilization of UCN as the light nanotransducer could convert the NIR light into an applicable wavelength harvested by semiconductors. The multiemissions of NaYF:Yb,Er UCN could match well with the absorption characteristics of AgS. In the presence of target CEA, a sandwich-type reaction was carried out between capture CEA aptamer/NaYF:Yb,Er-modified electrode and trigger CEA aptamer, which underwent an unbiased strand-displacement reaction to open C-rich hairpin probes in sequence between two alternating hairpins with the assistance of C-Ag-C chelation reaction. Upon addition of sulfide, the chelated Ag ions in the long-nicked DNA poly strands by hybridization chain reaction reacted with sulfide to generate AgS nanoparticles. The formed AgS could utilize effectively the upconversion emissions to amplify the photocurrent. Under optimal conditions, NaYF:Yb,Er-based NIR light-responsive PEC aptasensing platform exhibited high sensitivity for the determination of CEA within a dynamic linear range of 0.005-5.0 ng mL. The limit of detection was 1.9 pg mL. Good precision and high specificity could be acquired in this system for the analysis of target CEA. Human serum samples containing target CEA were measured using our strategy and received well-matched results relative to human CEA enzyme-linked immunosorbent assay kits. Importantly, the NaYF:Yb,Er-based NIR light-responsive PEC aptasensing system provides a new ideal for the detection of disease-related biomarkers using a nucleic acid-based amplification strategy.

Photoelectrochemical (PEC) measurement has been developed rapidly for bioanalysis in recent years. However, the actual application for most existed PEC bioanalytical systems is still a challenge because the perfect solutions for sensing surface design, high-throughput detection, and portability are lacked. To successfully overcome these limitations and realize accurate, continuous screening and assessing on prognostic indicator of early stage cancer on the spot, an innovative and portable semiautomated support power-free photoelectrochemical (SP-PEC) immunosensing platform consisted with a miniature semiautomatic injection system and digital multimeter (DMM) readout is designed (prostate specific antigen, PSA, was used as the proof-of-concept analyte). Decahedral BiVO that decorated with Au nanocrystal on {010} facets (Au-BiVO) by photodeposition is used as the photoanode materials to produce photocurrent signal under irradiation of micro laser light (5.0 w, λ ≥ 380 nm). The monoclonal anti-PSA capture antibody (mAb)-functionalized FeO magnetic nanobeads (mAb-MN) and glucose oxidase (GOx)/monoclonal detection antibody (mAb)-conjugated gold nanoparticle (GOx-AuNP-mAb) are employed as immunosensing probe and signal probe, respectively. The HO as an excellent holes scavenger that in suit generated from GOx oxidization glucose substrate significantly amplifies the photocurrent. The variation of instantaneous current value that registered as the signal of the immunoassay increases linearly with the logarithm of target PSA concentration increasing in a wide range from 10 pg mL to 100 ng mL with a low detection limit (LOD) of 4.0 pg mL. The SP-PEC immunosensing platform not only simplifies the assay process, but also improves detecting efficiency. The semiautomatic and portable SP-PEC analysis device allows analysis on spot and high-throughput continuous detection. Additional, we also gain deep insight into the relations between the specific shape as well as Au nanocrystal decoration and PEC activity and speculate the possible enhancement mechanisms of Au-BiVO. Therefore, the present work not only develops a flexible SP-PEC biosensor platform for rapid and continuous detection, but also provides a possible route for designing high performance photoelectric materials.

The organic–inorganic nanohybrids are emerging as one of the most attractive sensing materials in the area of gas sensors and usually exhibit some advanced properties because of synergetic/complementary effects between organic molecules and inorganic components. This work demonstrates a novel class of organic–inorganic nanohybrids, Cu2+-doped SnO2 nanograin/poly pyrrole nanospheres, for the sensitive room-temperature H2S gas sensing. Doping Cu2+ in SnO2 nanograins remarkably enhances the surface potential barrier by tailoring surface defects. After polymerizing pyrrole surrounded nanograins in aqueous media to form the organic–inorganic nanohybrids, the resulting nanoheterojunctions further improve the sensitivity. Additionally, the nanohybrids-based sensor provides high surface area and abounding reaction sites to accelerate gas diffusion and adsorption as well as the electron transfer. Compare with pristine SnO2 nanograins alone, the sensitivity of using the nanohybrids increases 7 times for the detection of 50-ppm of H2S. The response and recovery rate can increase 27 and 22 times at room temperature, respectively. Significantly, this work provides an attractive material for the real-time monitoring of H2S, whereas the insights into organic–inorganic composite interactions within the sensing mechanism may pave the way for designing functional materials with tailored properties.