Highly Stable Cesium Molybdenum Chloride Perovskite Nanocrystals for Photothermal Semihydrogenation Applications.

Metal halide perovskite materials with excellent carrier transport properties have been regarded as a new class of catalysts with great application potential. However, their development is hampered by their instability in polar solvents and high temperatures. Herein, we report a solution-processed Cs2MoCl6 perovskite nanocrystals (NCs) capped with the Mo6+, showing high thermostability in polar solvents. Furthermore, the Pd single atoms (PdSA) can be anchored on the surface of Cs2MoCl6 NCs through the unique coordination structure of Pd-Cl sites, which exhibit excellent semihydrogenation of different alkyne derivatives with high selectivity at full conversion at room temperature. Moreover, the activity could be improved greatly under Xe lamp irradiation. Detailed experimental characterization and DFT calculations indicate the improved activity under light illumination is due to the synergistic effect of photo-to-heat conversion and photoinduced electron transfer from Cs2MoCl6 to PdSA, which facilitates the activation of the C≡C group. This work not only provides a new catalyst for high selective semihydrogenation of alkyne derivatives but also opens a new avenue for metal halides as photothermal catalysts.

Controlling Photoluminescence and Photocatalysis Activities in Lead-Free Cs2 Ptx Sn1-x Cl6 Perovskites via Ion Substitution.

Lead-free halide perovskites have triggered interest in the field of optoelectronics and photocatalysis because of their low toxicity, and tunable optical and charge-carrier properties. From an application point of view, it is desirable to develop stable multifunctional lead-free halide perovskites. We have developed a series of Cs2 Ptx Sn1-x Cl6 perovskites (0≤x≤1) with high stability, which show switchable photoluminescence and photocatalytic functions by varying the amount of Pt4+ substitution. A Cs2 Ptx Sn1-x Cl6 solid solution with a dominant proportion of Pt4+ shows broadband photoluminescence with a lifetime on the microsecond timescale. A Cs2 Ptx Sn1-x Cl6 solid solution with a small amount of Pt4+ substitution exhibits photocatalytic hydrogen evolution activity. An optical spectroscopy study reveals that the switch between photoluminescence and photocatalysis functions is controlled by sub-band gap states. Our finding provides a new way to develop lead-free multifunctional halide perovskites with high stability.

Phase Engineering of Cesium Manganese Bromides Nanocrystals with Color-Tunable Emission.

For display applications, it is highly desirable to obtain tunable red/green/blue emission. However, lead-free perovskite nanocrystals (NCs) generally exhibit broadband emission with poor color purity. Herein, we developed a unique phase transition strategy to engineer the emission color of lead-free cesium manganese bromides NCs and we can achieve a tunable red/green/blue emission with high color purity in these NCs. Such phase transition can be triggered by isopropanol: from one dimensional (1D) CsMnBr3 NCs (red-color emission) to zero dimensional (0D) Cs3 MnBr5 NCs (green-color emission). Furthermore, in a humid environment both 1D CsMnBr3 NCs and 0D Cs3 MnBr5 NCs can be transformed into 0D Cs2 MnBr4 ⋅2 H2 O NCs (blue-color emission). Cs2 MnBr4 ⋅2 H2 O NCs could inversely transform into the mixture of CsMnBr3 and Cs3 MnBr5 phase during the thermal annealing dehydration step. Our work highlights the tunable optical properties in single component NCs via phase engineering and provides a new avenue for future endeavors in light-emitting devices.

Direct-readout photoelectrochemical lab-on-paper biosensing platform based on coupled electricity generating system and paper supercapacitors.

A direct-readout photoelectrochemical (PEC) lab-on-paper device based on coupled an electricity generating system and paper supercapacitors was established for highly sensitive detection of adenosine triphosphate (ATP). Concretely, CdSe quantum dots (QDs) decorated ZnO networks assembled sensing surface provided outstanding photoelectric properties, on which glucose oxidase (GOx) labeled aptamer was subsequently immobilized via the hybridization chain reaction. With analytes present, specific recognition was stimulated by aptamer, resulting in labeled GOx released. Such released GOx could flow to electrochemical cell to conduct electrochemical redox reactions, which could effectively produce electricity that was stored by capacitor I. Sequentially, photoactive material produced an outstanding voltage due to the decrease of steric hindrance on the sensing interface, which was utilized for charging an external capacitor II. The two instantaneous current was acquired along with the discharge of capacitor I and II by digital multimeter (DMM) readout, respectively. The summational current values performed an increment in pace with the addition of target ATP concentration with the dynamic working range from 10 nM to 3 µM and a detection limit of 6.3 nM attained. Significantly, the signal amplified strategy utilizing as-generated electricity from electrochemical redox reactions were isolated from the photoelectrodes, which was beneficial for amplifying the signal response in the PEC matrices and the development of more efficient signal performance.

Efficient Thermally Activated Delayed Fluorescence from All-Inorganic Cesium Zirconium Halide Perovskite Nanocrystals.

Thermally activated delayed fluorescence (TADF) is generally observed in solid-state organic molecules or metal-organic complexes. However, TADF in all-inorganic colloidal nanocrystals (NCs) is rare. Herein, we report the first colloidal synthesis of an air-stable all-inorganic lead-free Cs2 ZrCl6 perovskite NCs. The Cs2 ZrCl6 NCs exhibit long-lived triplet excited state (138.2 µs), and feature high photoluminescence (PL) quantum efficiency (QY=60.37 %) due to TADF mechanism. The emission color can be easily tuned from blue to green by synthesizing the mixed-halide Cs2 ZrBrx Cl6-x (0≤x≤1.5) NCs. Femtosecond transient absorption and temperature dependent PL measurements are performed to clarify the emission mechanism. In addition, Bi3+ ions are successfully doped into Cs2 ZrCl6 NCs, which further extends the PL properties. This work not only develops a new lead-free halide perovskite NCs for potential optoelectronic applications, but also offers unique strategies for developing new inorganic phosphors.

A self-powered origami paper analytical device with a pop-up structure for dual-mode electrochemical sensing of ATP assisted by glucose oxidase-triggered reaction.

A self-powered origami paper-based analytical device (oPAD), being with a pop-up structure as mechanical valve to first realize dual-mode of differential pulse voltammery (DPV)/supercapacitor amplified signal read out systems, was designed for detecting adenosine 5'-triphosphate (ATP) assisted by glucose oxidase (GOx)-triggered reaction. In order to accommodate the alternative step for dual-mode detection, a pop-up structure inspired by pop-up greeting cards was developed, making it possible to change the fluidic path with good registration and repeatability. To realize supercapacitor detection mode, a sandwich structure of a DNA sequence (DNA1), aptamer and a DNA sequence modified with GOx (GOx-DNA2) was formed on detection zone by hybridization reaction. With the addition of ATP, the GOx-DNA2 could be released with the specific binding between ATP and aptamer, and flowed into the reaction zone to catalyze the oxidation of glucose. Due to the difference in concentrations of [Fe(CN)6]3- and [Fe(CN)6]4- caused by the GOx-triggered reaction, a voltage could be produced to charge a paper supercapacitor which could provide a high instantaneous current with a digital multimeter to transduce the result of the assay, and realize the self-generation of an amplified electrical signal. By simply varying the direction of pop-up structure, the electrochemical signal from DPV read out mode could be achieved through catalytic oxidation of glucose by the remaining GOx-DNA2 on the detection zone. The proposed self-powered oPAD enabled the sensitive diagnosis of ATP in a linear range of 10-5000 nM with a limit of detection of 3 nM and 1.4 nM, respectively.

Mimic peroxidase-transfer enhancement of photoelectrochemical aptasensing via CuO nanoflowers functionalized lab-on-paper device with a controllable fluid separator.

Inspired by the design of folding greeting cards and tissue drawing covers, a photoelectrochemical (PEC) lab-on-paper device with a controllable fluid separator, producing both reaction zone and detection zone, was explored for ultrasensitive detection of adenosine 5'-triphosphate (ATP) via mimic peroxidase-transfer enhancement of photocurrent response. To realize it, the DNA1, aptamer, and DNA2 as well as the mimic peroxidase of G-quadruplex/hemin modified Au nanocubes were linked on the graphene oxide-functionalized reaction zone via the DNA hybridization. Meanwhile, three-dimensional CuO nanoflowers (CuO NFs) as a photoactive material with outstanding electron transfer ability and absorption of light were grown in situ on the detection zone, providing a PEC active interface. Besides, an innovative fluid separator was elaborately designed by assembling a strip of paper with a hydrophilic channel, providing an effective way to bridge the gap between the two zones with a controllable drawing way, which could successfully avoid the signal interference caused by modifying biomolecules layer by layer on photosensitive materials. In the presence of ATP, the G-quadruplex/hemin modified in the reaction zone was dissociated due to the specific recognition of ATP with aptamer and released into the detection zone with the assistance of controllable fluid separator. The free G-quadruplex/hemin could catalyze hydrogen peroxide to generate oxygen for the consumption of photo-induced electrons from CuO NFs, which could further promote the electron-hole carriers separation efficiency, and eventually resulting in the enhancement of PEC signal. The proposed PEC lab-on-paper device could be employed for specific detection of ATP in the range from 5.0 to 3.0 × 103 nM with a detection limit of 2.1 nM.

Time-resolution addressable photoelectrochemical strategy based on hollow-channel paper analytical devices.

The construction of a photoelectrochemical (PEC) strategy for multi-component detection represents a great challenge in the field of sensing. To address these challenges, herein we presented a hollow-channel paper-based PEC analytical platform based on chemiluminescence (CL) addressable strategies excited PEC strategy for multiplexed sensing application. Sandwich-structured CdS quantum dots (QDs)/reduced graphene oxide (RGO)/ZnO nanorods arrays (NRAs) heterostructure where CdS serves as visible light sensitizers, RGO acts as an electron relay between ZnO NRAs and CdS QDs, were simply assembled on the gold nanoparticles modified paper working photoelectrode (Au-PWE). The PEC performance of the CdS/RGO/ZnO can be greatly improved benefiting from the formation of type II band alignment between CdS QDs and ZnO NR as well as the super charge collection and shuttling property of RGO. Multiplexed CL emission could be achieved through controlling the CL co-reagents transport. By the virtue of CL addressable technique and the excellent PEC activity of CdS/RGO/ZnO, a highly sensitive, and selective multiple microRNAs (miRNAs) quantification method was achieved. Such a tailored strategy would break the bottleneck of the current PEC detection techniques in multiplex tracing, as well as serve as a novel concept for designing multi-channel PEC sensing method.

"On-Off-On" Photoelectrochemical/Visual Lab-on-Paper Sensing via Signal Amplification of CdS Quantum Dots@Leaf-Shape ZnO and Quenching of Au-Modified Prism-Anchored Octahedral CeO2 Nanoparticles.

An effective "on-off-on" photoelectrochemical (PEC)/visual sensing system based on cleaning-switchable lab-on-paper device was designed to achieve ultrasensitive detection of analytes. The first amplified "signal-on" PEC state was gained by CdS quantum dots sensitized leaf-shape ZnO (CdS QDs/leaf-shape ZnO) structure, which was assembled on reduced graphene oxide (rGO) modified paper electrode. Then Au-modified prism-anchored octahedral CeO2 nanoparticles (Au@PO-CeO2 NPs), as an efficient signal quencher, were immobilized on the CdS QDs/leaf-shape ZnO with the assistance of DNA hybridization, resulting in a noticeable photocurrent response decrement with the "signal-off" PEC state. With the addition of analytes, the quencher Au@PO-CeO2 NPs were immediately released from the sensing surface and robust PEC response was recovered to the signal-on state again. Meanwhile, the disengaged quencher in electrolyte solution flowed to the colorimetric detection area of lab-on-paper device and catalyzed oxidation of the chromogenic substrate 3,3',5,5'-tetramethylbenzidine in the presence of H2O2 to form the colored product, making the analytes detection more convincing with the visual discrimination. Under optimal conditions, the proposed PEC/visual lab-on-paper device possessed the detection limits toward adenosine and potassium ion as low as 0.15 and 0.06 nM, respectively. With ingenious design of actuating conversion process between hydrophilicity and hydrophobicity by slipping paper tab to solve cleaning issue in the assay procedures, the cleaning-switchable lab-on-paper device was constructed for high-performance biosensing applications. It provides an unambiguous simplicity and portable operation for exploring high reliability and sensitivity of novel point-of-care diagnostic tool with dual-signal readout.

Polyhedral-AuPd nanoparticles-based dual-mode cytosensor with turn on enable signal for highly sensitive cell evalution on lab-on-paper device.

A novel dual-mode cytosensor based on polyhedral AuPd alloy nanoparticles (PH-AuPd NPs) and three-dimentional reduced graphene oxide (3D-rGO) was constructed for highly sensitive detection of MCF-7 cells. The 3D-rGO was in situ synthesized on the paper working electrode (PWE) by a pollution-free hydrothermal method, increasing the specific surface area and further facilitating the modification of Au nanoparticles (AuNPs). After modified with AuNPs, the Au@ 3D-rGO/PWE was then functionalized by aptamer H1 to trap MCF-7 cells. To construct the cytosensor, PH-AuPd NPs was prepared as a novel catalytic material, and further modified with aptamer H2 for recognizing MCF-7 cells. With the occurrence of efficient recognition of MCF-7 cells, PH-AuPd NPs were bound onto the surface of the cells, and could catalyze H2O2 to generate •OH, leading to an amplified electrochemical signal. Meanwhile, as the electrolyte solution flowed, the •OH are transferred outward to the colorimetric detection zone, and catalyzed a chromogenic substrate TMB forms a colored product. The electrical signal measurement and colorimetric detection were carried out on a compatibly designed lab-on-paper device (LPD), realizing a dual-mode signal readout. This paper-based dual-mode cytosensor provided a relatively low detection limit of 20 cells mL-1 and a sensitive detection from 50 cells mL-1 to 107 cells mL-1 for MCF-7 cells, providing a reliable pathway of sensitively detecting cancer cells in clinical applications.

Highly sensitive microfluidic paper-based photoelectrochemical sensing platform based on reversible photo-oxidation products and morphology-preferable multi-plate ZnO nanoflowers.

A microfluidic paper-based analytical device (µPAD) was simply constructed for highly sensitive detection of L-glutamic acid and L-cysteine. The µPAD featured with two functional zones on one strip of paper achieved by preferable multi-plate ZnO nanoflowers (ZnO NFs) and molecularly imprinting polymer (MIP) membranes. The as-designed µPAD was established based on the inherent relation between the photo-oxidation products and photoelectrochemical (PEC) performance with the highly sensitive detection of biomolecules. The ZnO NFs were utilized to produce photo-oxidation products by driving the reaction between ferrocenemethanol and photogenerated holes under ultraviolet light. The photo-oxidation products easily flowed to MIP membranes along the hydrophilic channel via capillary action. MIP membranes as the receptors specifically recognized the analytes as well as decreased the electron loss by blocking the reduction reaction between electrons and photo-oxidation products. The PEC response was obtained in the processes of electrons transfer and exhibited the direct relationships corresponding to the concentrations of target analytes. The µPAD showed the detection limits toward L-glutamic acid and L-cysteine as low as 9.6 pM and 24 pM, respectively. Moreover, it is interesting to point out that ZnO NFs nanostructure shows superior PEC signal compared with those of ZnO nanospheres, nanosheets, and nanorod arrays. In current work, photo-oxidation products are utilized to achieve highly sensitive PEC detection for biomolecules under ultraviolet light as well as avoid the effects of multiple modifications in the same region on the reproducibility, which is beneficial for opening up rich possibility for designing more efficient analytical strategy.

Colorimetric and Electrochemiluminescence Dual-Mode Sensing of Lead Ion Based on Integrated Lab-on-Paper Device.

A highly selective two-point separation strategy was designed based on a cross-like all-in-one lab-on-paper analytical device. The stable and cleavable enzyme-coated reduced graphene oxide (rGO)-PdAu probe was fabricated as the signal reporter to enable the visualization and electrochemiluminescence (ECL) dual-mode sensing of Pb2+. Concretely, the experimental workflow consists of the following process: (i) fabrication of the lab-on-paper device and growth of Au nanoparticles on ECL detection zone, (ii) immobilization of Pb2+-specific DNAzyme, and (iii) hybridization between DNAzyme and rGO-PdAu-glucose oxidase (GOx) labeled oligonucleotide to form the double-stranded DNA. Upon addition of Pb2+ into the prepared system, the double-helix structure of the DNA was destroyed, resulting in the release of cleaved rGO-PdAu-GOx probe to visualization bar to promote the effective oxidation and color change of 3,3',5,5'-tetramethylbenzidine. As a consequence, the color change can be recognized by naked eye, meanwhile GOx on an uncleaved signal probe can oxidize glucose along with the H2O2 production. As a co-reaction reagent for luminol ECL system, the concentration of H2O2 is proportional to the ECL intensity, which constitutes a new mechanism for colorimetric and ECL dual mode to detect Pb2+. With the method developed here, the concentration of Pb2+ could be easily determined by the naked eye within a linear range from 5 to 2000 nM, as well as by monitoring the decreased ECL intensity of luminol in a linear range of 0.5-2000 nM. This work not only constructs a simple and versatile platform for on-site visible monitoring of Pb2+ in tap water and river water but also furnishes a strategy for designing a dual-mode sensing toward different heavy metal ions based on specific DNAzyme in the fields of environmental monitoring-related technologies.

Electrochemiluminescence of graphitic carbon nitride and its application in ultrasensitive detection of lead(II) ions.

Graphitic carbon nitride (g-C3N4) materials with a layered structure have unusual physicochemical properties. Herein it was shown that g-C3N4 quantum dots (QDs) obtained through a thermal-chemical etching route exhibited attractive upconversion and electrochemiluminescence (ECL) properties. After modification on nanoporous gold (NPG) with a sponge-like porous structure, g-C3N4 QDs were employed to fabricate an ECL sensor for the determination of Pb(2+) using target - dependent DNAzyme as the recognition unit. Moreover, magnetic reduced graphene oxide nanosheets (rGO) attached with Fe3O4 nanoparticles (rGO-Fe3O4) were obtained via a one-pot in situ reduction approach, and used as carriers of DNAzyme. To make full use of the unique magnetic property the prepared rGO-Fe3O4, a flow injection ECL detecting cell was designed using indium tin oxide (ITO) glass as working electrode. Due to the unique separation and enrichment properties of magnetic Fe3O4-rGO materials as well as wire-like conductivity of NPG, high sensitivity and selectivity for the determination of Pb(2+) in real water samples were achieved. This indicates that g-C3N4 has excellent anodic ECL performance in the presence of triethanolamine, and could be applied in real environmental samples analyses. Graphical Abstract Graphitic carbon nitride based electrochemiluminescence sensor for the sensitive monitor of lead(II) ions in real samples was constructed.

A 3D electrochemical immunodevice based on a porous Pt-paper electrode and metal ion functionalized flower-like Au nanoparticles.

A 3D microfluidic paper-based electrochemical immunodevice (µ-PEID) for simultaneous sensitive detection of two tumor biomarkers was fabricated. A nanoporous Pt particle modified paper working electrode (NPPt-PWE) was used as the matrix and metal ions loaded on the l-cysteine capped flower-like Au nanoparticles (Au-Cys) were used as a signal amplification label. The NPPt-PWE was constructed through the growth of a NPPt layer on the back of the paper working electrode to improve electron conduction. Besides, the prepared flower-like Au-Cys could significantly enhance the amount of loaded metal ions and played an important role in connecting the signal antibodies. The metal ion labels could be detected directly through differential pulse voltammetry without metal pre-concentration, and the distinct voltammetric peaks had a close relationship with each sandwich-type immunoreaction. Therefore, a novel 3D µ-PEID for simultaneously detecting carcinoembryonic antigen (CEA) and alpha-fetoprotein (AFP) with wider linear ranges was developed. The linear range was from 0.004 to 200 ng mL-1 and the limits of detection for AFP and CEA were 1.0 pg mL-1 and 1.3 pg mL-1 (S/N = 3), respectively. The good stability, reproducibility, and accuracy of the µ-PEID indicate that it has great potential application in clinical diagnostics.

Cyto-sensing in electrochemical lab-on-paper cyto-device for in-situ evaluation of multi-glycan expressions on cancer cells.

A novel electrochemical lab-on-paper cyto-device (ELPCD) was fabricated to demonstrate sensitive and specific cancer cell detection as well as in-situ monitoring of multi-glycans on living cancer cells. In this ELPCD, aptamers modified three-dimensional macroporous Au-paper electrode (Au-PE) was employed as the working electrode for specific and efficient cancer cell capture. Using a sandwich format, sensitive and reproducible cell detection was achieved in this ELPCD on the basis of the electrochemical signal amplification of the Au-PE and the horseradish peroxidase-lectin electrochemical probe. The ELPCD displayed excellent analytical performance for the detection of four K562 cells with a wide linear calibration range from 550 to 2.0×10(7) cells mL(-1). Then, this ELPCD was successfully applied to determine cell-surface multi-glycans in parallel and in-situ monitor multi-glycans expression on living cells in response to drug treatment through in-electrode 3D cell culture. The proposed method provides promising application in decipherment of the glycomic codes as well as clinical diagnosis and treatment in early process of cancer.

3D origami electrochemical immunodevice for sensitive point-of-care testing based on dual-signal amplification strategy.

A dual signal amplification immunosensing strategy that offers high sensitivity and specificity for the detection of low-abundance biomarkers was designed on a 3D origami electrochemical device. High sensitivity was achieved by using novel Au nanorods modified paper working electrode (AuNRs-PWE) as sensor platform and metal ion-coated Au/bovine serum albumin (Au/BSA) nanospheres as tracing tags. High specificity was further obtained by the simultaneous measurement of two cancer markers on AuNRs-PWE surface using different metal ion-coated Au/BSA tracers. The metal ions could be detected directly through differential pulse voltammetry (DPV) without metal preconcentration, and the distinct voltammetric peaks had a close relationship with each sandwich-type immunoreaction. The position and size of the peaks reflected the identity and level of the corresponding antigen. Integrating the dual-signal amplification strategy, a novel 3D origami electrochemical immunodevice for simultaneous detecting carcinoembryonic antigen (CEA) and cancer antigen 125 (CA125) with linear ranges of over 4 orders of magnitude with detection limits down to 0.08 pg mL(-1) and 0.06 mU mL(-1) was successfully developed. This strategy exhibits high sensitivity and specificity with excellent performance in real human serum assay. The AuNRs-PWE and the designed tracer on this immunodevice provided a new platform for low-cost, high-throughput and multiplex immunoassay and point-of-care testing in remote regions, developing or developed countries.

Ultrasensitive detection of lead ion sensor based on gold nanodendrites modified electrode and electrochemiluminescent quenching of quantum dots by electrocatalytic silver/zinc oxide coupled structures.

A signal-off electrochemiluminescence (ECL) DNA sensor based on gold nanodendrites (Au NDs) modified indium tin oxide (ITO) electrode for the detection of lead ion (Pb(2+)) was developed. Well-defined Au NDs were prepared on ITO electrode using low-potential synthesis, assisted by ethylenediamine. Based on Pb(2+)-specific deoxyribozyme, the silver/zinc oxide (Ag/ZnO) with coupled structure, prepared by one-pot method, was close to the surface of the electrode to catalyze the reduction of part of H2O2, the coreactant for cathodic ECL emission, leading to a decrease of ECL intensity. In addition, taking advantage of the larger surface area to capture a large amount of capture probe as well as excellent conductivity of Au NDs, the sensor could detect Pb(2+) quantitatively in a wider range, and performed excellent selectivity. Furthermore, such simple and sensitive DNA sensor was successfully applied for the detection of Pb(2+) in lake water and human serum samples, respectively.

Paper-based electrochemiluminescence origami cyto-device for multiple cancer cells detection using porous AuPd alloy as catalytically promoted nanolabels.

The detection of cancer cells is important and fundamental for cancer diagnosis and therapy, which has attracted considerable interest recently. Although traditional cyto-sensors have been widely explored due to their high sensitivity and selectivity, it is still a challenge to develop a low-cost, portable, disposable, fast, and easy-to-use cancer cell detection method for applying in the field of cancer diagnosis and therapy. Herein, to address these challenges, we developed a microfluidic paper-based electrochemiluminescence origami cyto-device (µ-PECLOC), in which aptamers modified 3D macroporous Au-paper electrodes were employed as the working electrodes and efficient platforms for the specific cancer cells capture. Owing to the effective disproportionation of hydrogen peroxide and specific recognition of mannose on cell surface, concanavalin-A conjugated porous AuPd alloy nanoparticles were introduced into this µ-PECLOC as the catalytically promoted nanolabels for peroxydisulfate ECL system. Under the optimal conditions, the proposed µ-PECLOC exhibited excellent analytical performance with good stability, reproducibility, and accuracy, towards the cyto-sensing of four types of cancer cells indicating the potential applications to facilitate effective and multiple early cancer diagnosis and clinical treatment.

CuO-induced signal amplification strategy for multiplexed photoelectrochemical immunosensing using CdS sensitized ZnO nanotubes arrays as photoactive material and AuPd alloy nanoparticles as electron sink.

In this work, multiplexed photoelectrochemical (PEC) immunoassays are introduced into an indium tin oxide (ITO) device. Firstly, the ITO device is fabricated using a simple acid etch treatment method. Secondly, AuPd alloy nanoparticles are electro-deposited on ITO working electrodes as electron sink to construct the immunosensor platform. After that, ZnO nanotubes (ZNTs) arrays are synthesized via chemical etching of ZnO nanorods that are grown on AuPd surface by electrochemical deposition method. Subsequently, CdS is electro-deposited on ZNTs arrays and used as photoactive material. Then, CuO nanoseeds are labeled with signal antibodies and firstly used as PEC signal amplification label. The introduction of CuO brings signal amplification because of the conduction band (CB) of both CuO and ZnO are lower than that of CdS, CuO will compete the photo-induced electrons in CB of CdS with ZnO, leading to the decrease of the photocurrent intensity. Using cancer antigen 125, prostate specific antigen and α-fetoprotein as model analytes, the proposed immunoassay exhibits excellent precision and sensitivity. Meanwhile, this work provides a promising, addressable and simple strategy for the multi-detection of tumor markers.