Precise Tuning of the D-Band Center of Dual-Atomic Enzymes for Catalytic Therapy.

Single-atom nanozyme-based catalytic therapy is of great interest in the field of tumor catalytic therapy; however, their development suffers from the low affinity of nanozymes to the substrates (H2O2 or O2), leading to deficient catalytic activity in the tumor microenvironment. Herein, we report a new strategy for precisely tuning the d-band center of dual-atomic sites to enhance the affinity of metal atomic sites and substrates on a class of edge-rich N-doped porous carbon dual-atomic sites Fe-Mn (Fe1Mn1-NCe) for greatly boosting multiple-enzyme-like catalytic activities. The as-made Fe1Mn1-NCe achieved a much higher catalytic efficiency (Kcat/Km = 4.01 × 105 S-1·M-1) than Fe1-NCe (Kcat/Km = 2.41 × 104 S-1·M-1) with an outstanding stability of over 90% activity retention after 1 year, which is the best among the reported dual-atom nanozymes. Theoretical calculations reveal that the synergetic effect of Mn upshifts the d-band center of Fe from -1.113 to -0.564 eV and enhances the adsorption capacity for the substrate, thus accelerating the dissociation of H2O2 and weakening the O-O bond on O2. We further demonstrated that the superior enzyme-like catalytic activity of Fe1Mn1-NCe combined with photothermal therapy could effectively inhibit tumor growth in vivo, with an inhibition rate of up to 95.74%, which is the highest value among the dual-atom artificial enzyme therapies reported so far.

Cation Exchange Reaction-Mediated Photothermal and Polarity-Switchable Photoelectrochemical Dual-Readout Biosensor.

Cation exchange (CE) is a burgeoning method for controlled crystal synthesis; however, its applications in bioanalysis are still in their infancy. Herein, we explored the transformation of ZnIn2S4 in properties after the CE reaction with Cu2+ ions; furthermore, the discrepancy was employed to design a dual-readout detection system of photothermal and polarity-switchable photoelectrochemical (PEC) immunoassays to realize reliable detection of carcinoembryonic antigen (CEA). In the presence of CEA, the CuO nanoparticles (CuO NPs) employed as dual-signal response probes would bond to the microplates and be acidolyzed by HCl to release Cu2+, which could replace Zn2+ and In3+ via the CE reaction. After the CE reaction is completed, the photocurrent would switch from a weak anodic photocurrent to a cathode one by using a 635 nm laser as a signal amplifier, while the photothermal signal would be enhanced with 808 nm laser illumination. On the basis of the polarity-switchable PEC strategy, CEA could be accurately detected from 0.1 to 50 ng mL-1 with a limit of detection (LOD) of 48 pg mL-1 (S/N = 3). Moreover, the photothermal assay for CEA detection possesses a linear range from 0.5 to 100 ng mL-1 with a LOD of 0.21 ng mL-1. In addition, the designed sensing platform only relies on devices with portability that are permitted for point-of-care detection.

High-entropy effect with hollow (ZnCdFeMnCu)xS nanocubes for photoelectrochemical immunoassay.

High entropy (HE) compounds with chemically disordered multi-cation structures have become a hot research topic because of their fascinating "cocktail effect". However, high entropy effect with the efficient photoelectric response has not been reported for photoelectrochemical (PEC) immunoassays. Herein, an innovative PEC immunoassay for the sensitive detection of prostate-specific antigen (PSA) was ingeniously constructed using hollow nanocubic (ZnCdFeMnCu)xS photoactive matrices with high entropic effect via the cation exchange. Initially, a sandwich-type immunoreaction has behaved using dopamine-loaded liposome labeled with anti-PSA secondary antibodies. In the presence of PSA, addition of Triton X-100 caused the liposomal cleavage to release dopamine, which was then detected as a reduced photocurrent on (ZnCdFeMnCu)xS-based photoelectrode. Under optimal condition, the PEC immunoassay showed good photocurrent responses toward target PSA with the dynamic linear range of 0.1-50 ng mL-1 with a limit of detection of 34.1 pg mL-1. Significantly, this system can provide a new platform for the development of PEC immunoassays by coupling with high-entropy photoactive materials.

Atomically Site Synergistic Effects of Dual-Atom Nanozyme Enhances Peroxidase-like Properties.

Pursuing effective and generalized strategies for modulating the electronic structures of atomically dispersed nanozymes with remarkable catalytic performance is exceptionally attractive yet challenging. Herein, we developed a facile "formamide condensation and carbonization" strategy to fabricate a library of single-atom (M1-NC; 6 types) and dual-atom (M1/M2-NC; 13 types) metal-nitrogen-carbon nanozymes (M = Fe, Co, Ni, Mn, Ru, Cu) to reveal peroxidase- (POD-) like activities. The Fe1Co1-NC dual-atom nanozyme with Fe1-N4/Co1-N4 coordination displayed the highest POD-like activity. Density functional theory (DFT) calculations revealed that the Co atom site synergistically affects the d-band center position of the Fe atom site and served as the second reaction center, which contributes to better POD-like activity. Finally, Fe1Co1 NC was shown to be effective in inhibiting tumor growth both in vitro and in vivo, suggesting that diatomic synergy is an effective strategy for developing artificial nanozymes as novel nanocatalytic therapeutics.

Ag/MoO3-Pd-mediated gasochromic reaction: An efficient dual-mode photoelectrochemical and photothermal immunoassay.

Herein, we presented a dual-readout gasochromic immunosensing platform for accurate and sensitive detection of carcinoembryonic antigen (CEA) based on Ag-doped/Pd nanoparticles loaded MoO3 nanorods (Ag/MoO3-Pd). Initially, the presence of analyte CEA would prompt the formation of sandwich-type immunoreaction, accompanied by the introduction of Pt NPs labeled on detection antibody. Upon the addition of NH3BH3, the product hydrogen (H2) will interact with Ag/MoO3-Pd as a bridge between the sensing interface and the biological assembly platform. Both photocurrent and temperature signals can serve as readouts due to the significantly increased PEC performance and enhanced photothermal conversion capability of H-Ag/MoO3-Pd (the product of Ag/MoO3-Pd react with H2) compared to Ag/MoO3-Pd. In addition, the DFT results show that the band gap of Ag/MoO3-Pd becomes narrower after the reaction with H2, thus improving the utilization of light, which theoretically explains the internal mechanism of gas sensing reaction. Under optimal conditions, the designed immunosensing platform showed good sensitivity for CEA detection with the limit of detection (LOD) of 26 pg mL-1 (photoelectrochemical mode) and 98 pg mL-1 (photothermal mode). This work not only presents the possible reaction mechanism of Ag/MoO3-Pd and H2, but also creatively applicate it in photothermal biosensors that give a new path for devising dual-readout immunosensor.

Point-of-Care Immunoassay Based on a Multipixel Dual-Channel Pressure Sensor Array with Visual Sensing Capability of Full-Color Switching and Reliable Electrical Signals.

The point-of-care (POC) method with affordability and portability for the sensitive detection of biological substances is an emerging topic in rapid disease screening and personalized medicine. In this work, we demonstrated a diverse responsive platform based on a dual-channel pressure sensor (DCPS). The DCPS had a multilayer flexible architecture consisting of a photonic hydrogel with chromatic transitions and a piezoresistive pressure sensor as the electrical data transmission unit, both of which had the property of pressure-induced mechanical stimulus feedback. By incorporating a platinum nanoparticles-labeled detection antibody (PtNPs-dAb) into the sandwich-type immunoreaction for the target carcinoembryonic antigen (CEA, as a model analyte), gas decomposition could be triggered by the addition of hydrogen peroxide (H2O2) to induce a significant increase under pressure in a closed chamber. Meanwhile, the DCPS enabled an accurate electrical signal output, and the photonic hydrogel converted spatiotemporal stimuli into eye-readable colorations with string brilliance. In this way, the target concentration could be quantificationally related to the electrical response and intuitively perceived through visible color alterations. Under optimal conditions, a sensitive determination of CEA was performed in a detectable range of 0.3-60 ng/mL with a limit of detection (LOD) of 0.13 ng/mL. In addition, the proposed protocol had satisfactory selectivity, accuracy, and reproducibility. Furthermore, an array-based immunoassay device was fabricated to conceptually validate its application potential in high-throughput biomedical detection and inspire a dual-signal POC diagnostic platform in a friendly way for resource-limited settings.

Smartphone-Based Photoelectrochemical Immunoassay with Co9S8@ZnIn2S4 for Point-of-Care Diagnosis of Breast Cancer Biomarker.

Photoelectrochemical immunoassays incorporating specific antigen-antibody recognition reactions with the photon-electron conversion capabilities of photocatalysts have been developed for biomarker detection, but most involve bulky and expensive equipment and are unsuitable for point-of-care testing. Herein, a portable smartphone-based photoelectrochemical immunoassay was innovatively designed for the on-site detection of breast cancer biomarkers (human epidermal growth factor receptor 2; HER2). The system consists of a split-type immunoassay mode, disposable screen-printed electrode covered with hierarchical Co9S8@ZnIn2S4 heterostructures, an integrated circuit board, and a Bluetooth smartphone equipped with a specially designed app. Using alkaline phosphatase (ALP) catalytic strategy to in situ generate ascorbic acid (AA) for electron-donating toward Co9S8@ZnIn2S4 heterostructures, an immunoreaction was successfully constructed for the HER2 detection in the real sample due to the positive correlation of the photocurrent signal to electron donor concentration. Differential charge density indicates that the formation of Co9S8@ZnIn2S4 heterojunction can facilitate the flow of charges in the interface and enhance the photocurrent of the composite. More importantly, the measured photocurrent signal can be wirelessly transmitted to the software and displayed on the smartphone screen to obtain the corresponding HER2 concentration value. The photocurrent values linearly with the logarithm of HER2 concentrations range spanned from 0.01 ng/mL to 10 ng/mL with a detection limit of 3.5 pg/mL. Impressively, the clinical serum specimen results obtained by the proposed method and the wireless sensing device are in good agreement with the enzyme-linked immunosorbent assay (ELISA).

Dual-Signaling Photoelectrochemical Biosensor Based on Biocatalysis-Induced Vulcanization of Bi2MoO6 Nanosheets.

A magnetic-assisted photoelectrochemical (PEC) and colorimetric (CL) dual-modal biosensing platform with high precision was established to monitor prostate-specific antigen (PSA) based on Bi2MoO6 nanosheets (BMO) by coupling the aptamer-guided hybridization chain reaction (HCR) with the hydrolysate-induced vulcanization reaction of Bi2MoO6 nanosheets. Upon addition of PSA, trigger DNA (tDNA) was released by the interaction between the target analyte and the aptamer and then further hybridized with anchor DNA (aDNA) conjugated on magnetic beads (MBs). The as-released tDNA initiated the target-assisted HCR in the presence of two alternating hairpin sequences (Bio-H1 and Bio-H2) to produce nicked long double-stranded DNA on the surface of MBs, where numerous alkaline phosphatase (ALP) enzymes could assemble with MBs through the biotin-avidin reaction, resulting in the hydrolysis of sodium thiophosphate (TP) to H2S. The as-produced H2S reacted with BMO to form vulcanized BMO (BMO-S), thus leading to obvious enhanced PEC performance under visible light with the color change from light yellow to brown. Having optimized the test conditions, the magnetic-assisted biosensing system holds a good quantitative diagnosis sensitivity area in a range of 5.0 pg mL-1-100 ng mL-1 with a calculated detection limit down to 3.5 pg mL-1. Meanwhile, a visual colorimetric assay on basis of the change in the color of the materials was also realized. Given the exceptional performance of the constructed biosensor, it may possess great promise as an advanced bioanalytical tool for practical applications.

Contactless Photoelectrochemical Biosensor Based on the Ultraviolet-Assisted Gas Sensing Interface of Three-Dimensional SnS2 Nanosheets: From Mechanism Reveal to Practical Application.

This work reports a contactless photoelectrochemical biosensor based on an ultraviolet-assisted gas sensor (UV-AGS) with a homemade three-dimensional (3D)-SnS2 nanosheet-functionalized interdigitated electrode. After rigorous examination, it was found that the gas responsiveness accelerated and the sensitivity increased using the UV irradiation strategy. The effects of the interlayer structure and the Schottky heterojunction on the gas-sensitive response of O2 and NH3 under UV irradiation were further investigated theoretically by 3D electrostatic field simulations and first-principles density functional theory to reveal the mechanism. Finally, a UV-AGS device was developed to quantify the blood ammonia bioassay in a small-volume whole blood sample by alkalizing blood to release gas-phase ammonia with a linear range of 25-5000 µM with a limit of detection (LOD) of 29.5 µM. The device also enables a rapid immunoassay of human cardiac troponin I (cTnI) with a linear range of 0.4-25.6 ng/mL and an LOD of 0.37 ng/mL using a urease-labeled antibody as the immune recognition molecule. Both analyses showed satisfying specificity and stability, suggesting that the device can be applied to practical assays and is of great potential to increase the value of gas-sensitive sensors in chemical biosensing.

Size-Controlled Engineering Photoelectrochemical Biosensor for Human Papillomavirus-16 Based on CRISPR-Cas12a-Induced Disassembly of Z-Scheme Heterojunctions.

Photoelectrochemical (PEC) biosensors incorporating biomolecular recognition with photon-to-electron conversion capabilities of the photoactive species have been developed for molecular diagnosis, but most involve difficulty in adjusting band gap positions and are unsuitable for PEC biodetection. In this work, an innovative PEC biosensor combined with quantum size-controlled engineering based on quantum confinement by controlling the quantum size was designed for the detection of human papillomavirus-16 (HPV-16) through CRISPR-Cas12a (Cpf1)-induced disassembly of Z-scheme heterojunction. To the best of our knowledge, quantum size-controlled engineering that precisely tunes the properties of photoactive materials is first utilized in the PEC bioanalysis. Based on the quantum size effect, the light absorption efficiency and charge-transfer rate were tuned to suitable levels to obtain the best PEC performance. After incubation with target HPV-16, the binding of Cas12a-crRNA to the target double-stranded DNA (dsDNA) stimulated the activity of indiscriminate cleavage toward single-stranded DNA (ssDNA), resulting in a decrease in photocurrent due to the blocking of electron transfer through the heterojunction. By optimizing experimental conditions, the Z-scheme sensing system exhibited incredible photocurrent response to HPV-16 in the range from 3.0 pM to 600 nM with a detection limit of 1.0 pM. Impressively, the application of the quantum size effect could stimulate more interest in the precise design of band gap structure to improve PEC performance.

CRISPR-Cas12a-Derived Photoelectrochemical Biosensor for Point-Of-Care Diagnosis of Nucleic Acid.

This work presented a point-of-care (POC) photoelectrochemical (PEC) biosensing for the detection of human papillomavirus-16 (HPV-16) on a portable electrochemical detection system by using CRISPR-Cas12a trans-cleaving the G-quadruplex for the biorecognition/amplification and a hollow In2O3-In2S3-modified screen-printed electrode (In2O3-In2S3/SPE) as the photoactive material. G-quadruplexes were capable of biocatalytic precipitation (H2O2-mediated 4-chloro-1-naphthol oxidation) on the In2O3-In2S3/SPE surface, resulting in a weakened photocurrent, but suffered from trans-cleavage when the CRISPR-Cas12a system specifically recognized the analyte. The photocurrent results could be directly observed with the card-sized electrochemical device via a smartphone, which displayed a high-value photocurrent for these positive samples, while a low-value photocurrent for the target-free samples. Such a system exhibited satisfying photocurrent responses toward HPV-16 within a wide working range from 5.0 to 5000 pM and allowed for detection of HPV-16 at a concentration as low as 1.2 pM. The proposed assay provided a smartphone signal readout to enable the rapid screening PEC determination of HPV-16 concentration without sophisticated instruments, thus meeting the requirements of remote areas and resource-limited settings. We envision that combining an efficient biometric PEC sensing platform with a wireless card-sized electrochemical device will enable high-throughput POC diagnostic analysis.

CRISPR/Cas12a-mediated liposome-amplified strategy for the photoelectrochemical detection of nucleic acid.

This study reports a photoelectrochemical biosensor for dopamine-loaded liposome-encoded magnetic beads cleaved by clustered regularly interspaced short palindromic repeats (CRISPR)/Cas 12a system for the quantification of human papilloma virus (HPV)-related DNA using neodymium-doped BiOBr nanosheets (Nd-BiOBr) as a photoactive matrix. Magnetic beads and dopamine-loaded liposomes are covalently attached to the both ends of ssDNA to construct dumbbell-shaped dopamine-loaded liposome-encoded magnetic bead (DLL-MB) probes. When the guide RNA binds to the target HPV-16, the ssDNA will be cleaved by Cas12a, thereby degrading the double dumbbell probes. After magnetic separation, the dissolved DLLs are treated with Triton X-100 to release the dopamine (as an electron donor), which was then detected by an amplified photocurrent using the Nd-BiOBr-based photoelectrode.

An ultrasensitive homogeneous electrochemical biosensor based on CRISPR-Cas12a.

Taking advantage of the high-efficiency indiscriminate ssDNA cleavage activity of Cas12a in combination with the diffusivity difference of methylene blue (MB)-labeled probes (short oligonucleotides/mononucleotides) toward the negatively-charged indium tin oxide (ITO) electrode, a simple, immobilization-free, highly sensitive, and homogeneous electrochemical biosensor for the detection of human papillomavirus (HPV-16) has been fabricated. At the core of the detection process, Cas12a employed ssDNA trans-cleavage capability to achieve short-strand nucleotide cleavage, while MB-labeled probes served as high-efficiency homogeneous electrochemical emitters to achieve differential pulse voltammetric (DPV) signal. Specifically, due to strong electrostatic repulsion, MB-labeled short oligonucleotides (reporter) cannot diffuse freely to the surface of the negatively charged ITO electrode, and only weak electrochemical signals can be detected. The presence of the target HPV-16 can activate the Cas12a complex to perform indiscriminate ssDNA cleavage of the reporter to produce MB-labeled mononucleotides. The MB-labeled mononucleotides with a smaller size have almost no negative charge, so they very easily diffuse to the surface of the ITO electrode and result in an enhanced electrochemical signal response. Different electrochemical responses (DPV peak intensity) of the CRISPR-Cas12a-assisted amplification strategy can be obtained through the diffusion rate of different MB-labeled DNA on the electrode, which is also positively correlated with the input HPV-16 concentration. Given the unique combination of the CRISPR-Cas12a system with the homogeneous electrochemical solution phase, the detection limit is determined to be 3.22 pM (wide dynamic working range from 0.01 nM to 100 nM) and the two-step detection workflow could be completed within 50 min at ambient temperature, which is superior to that of the HPV-based biosensors previously reported.

Horseradish peroxidase-encapsulated DNA nanoflowers: An innovative signal-generation tag for colorimetric biosensor.

Herein a versatile colorimetric biosensing platform was designed for sensitive, specific, and rapid screening of cancer-derived exosomes (HepG2 cell-derived) by introducing horseradish peroxidase -encapsulated DNA nanoflowers (HRP-DF) as the biorecognition elements and signal-generation tags. HRP was concurrently associated with the growing ultralong-chain DNA and the magnesium pyrophosphate crystals (Mg2PPi) during the rolling circle amplification (RCA), thereby ultimately leading to the direct fixation of HRP in DFs. For demonstration, a linear DNA circular molecule encoding the complementary sequence of CD63 aptamer (a nucleic acid sequence that can highly bind to exosomes) was used as a starting amplification template to obtain HRP-DF with the high biorecognition ability of exosomes. Upon addition of target exosomes, a sandwiched reaction was carried out between the cholesterol-modified DNA probes-conjugated magnetic bead (MB) and the HRP-DFs, accompanying formation of ternary complexes (MB-exosomes-HRP-DF). After simple magnetic separation, the HRP carried on the ternary complexes (MB-exosomes-HRP-DF) initiated oxidation of 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS, nearly colorless) into green-colored oxidized ABTS in the presence of hydrogen peroxide (H2O2). The obvious color change (from nearly colorless to dark green) of ABTS-H2O2 system can be easily observed with the naked eye and accurately monitored by UV-visible spectrometry, which was also proportional to the concentration of exosomes. Impressively, HRP-DF-based biosensing platform exhibited satisfactory colorimetric responses toward target exosomes within the working range from 5.0 × 103 to 5.0 × 106 particles/µL at a low detection limit of 3.32 × 103 particles/µL. Combined with a one-step sandwich reaction, magnetic separation and HRP-DF-based color-changing, this system had the advantages of acceptable accuracy, strong anti-interference ability and good reproducibility.

Magnetic bead-based photoelectrochemical immunoassay for sensitive detection of carcinoembryonic antigen using hollow cadmium sulfide.

Herein a versatile photoelectrochemical (PEC) immunoassay platform for sensitive and specific screening of tumor biomarkers (carcinoembryonic antigen; CEA) was innovatively designed using hollow cadmium sulfide (H-CdS) as photoactive matrix based on immunomagnetic separation. Experimental results reveal that the hollow-structure prepared by template hydrothermal-etching method endowed the CdS with better photocurrent intensity compared to the traditional CdS nanoparticles. Upon addition of target CEA, a sandwiched immunoreaction was carried out between anti-CEA capture antibody-conjugated immunomagnetic bead (IMB) and horseradish peroxidase (HRP)-labeled anti-CEA detection antibody, accompanying the immunocomplex formation of the IMB-antibody/CEA/HRP-labeled antibody (IMB-CEA-HRP). Followed by magnetic separation, the carried HRP on the sandwich structure triggers enzymatic bioetching of H-CdS, thus resulting in decreasing photocurrent intensity. The H-CdS-based PEC sensing system exhibited satisfying photocurrent responses toward target CEA within the working range from 0.02 ng mL-1 to 50 ng mL-1 at a low detection limit of 6.12 pg mL-1. Combined with magnetic immunoassay, this sensing platform has the advantages of high precision, great anti-interference ability, and acceptable accuracy. Overall, this research not only provides an efficient strategy for the activity of CdS with a well-defined hollow-nanostructures but also sheds light on the development of enzyme-triggered bioetching technology for traditional PEC immunoassay.

Palindromic Fragment-Mediated Single-Chain Amplification: An Innovative Mode for Photoelectrochemical Bioassay.

This work reports a strategy for glutathione-loaded liposome-encoded magnetic beads initiated by palindromic fragment-mediated single-chain amplification (PFMSCA) for high-precision quantification of a low-abundance aminoglycoside antibiotic (kanamycin; Kana) by using In2O3-ZnIn2S4 (IO-ZIS) as a photoactive matrix. In this strategy, a Kana-recognition region, primer-like palindromic fragment, and polymerization/nicking template are reasonably integrated into one oligonucleotide (hairpin HP1) for target recognition, magnetic separation, and target amplification. Upon target Kana introduction, the Kana-aptamer region in HP1 specifically recognizes the Kana and triggers the palindromic tails intramolecular self-hybridization, amplifying a large number of short fragments in the presence of Klenow fragment polymerase and Nt.BbvCI. The as-generated nick fragments act as a linker to introduce the free hairpin HP2-functionalized glutathione-loaded liposomes (HP2-GLL) onto the surface of the hairpin HP3-modified magnetic beads (HP3-MB), constructing liposome-encoded magnetic beads (HP3-MB-nick-HP2-GLL). Following magnetic separation, the detached glutathione-loaded liposomes (GLL) are lysed by treatment with 1% Triton X-100 to release the glutathione within it, which were then detected as an amplified photocurrent at the IO-ZIS-based photoelectrode. Importantly, this method can be readily carried out by using one oligonucleotide to achieve an exponential amplification effect and open new opportunities for advanced development of robust biodetection systems.

All-solid-state metal-mediated Z-scheme photoelectrochemical immunoassay with enhanced photoexcited charge-separation for monitoring of prostate-specific antigen.

An all-solid-state metal-mediated Z-scheme photoelectrochemical (PEC) immunoassay was designed for sensitive detection of prostate-specific antigen (PSA) by using WO3-Au-CdS nanocomposite as photoactive material and copper ion (Cu2+) as an inhibitor. The Z-scheme PEC system comprising of CdS nanoparticle (photosystem I; PS I), WO3 nanorod (photosystem II; PS II) and gold nanoparticle (Au NP; solid electron mediator) was reasonably established by a simple and green synthetic method. As an important part of Z-scheme system, the sandwiched gold nanoparticles between electron donor materials and hole provider materials could accelerate electron transfer from positive conduction band (CB) of WO3 to negative valence band (VB) of CdS, thus resulting in high-efficient separation of the carriers. In the presence of target PSA, a sandwiched immunoreaction was executed between capture antibody-coated microplate and CuO nanoparticle-labeled detection antibody. Thereafter, CuO nano labels were dissolved into Cu2+ ions under acidic condition to decrease the photocurrent of Z-scheme WO3-Au-CdS thanks to the formation of exciton trapping center of CuxS (x = 1,2) on the surface. Under optimum conditions, Z-scheme PEC immunoassay exhibited good photocurrents toward target PSA within a linear range of 0.01-50 ng mL-1 at a limit of detection of 1.8 pg mL-1. Moreover, the Z-scheme PEC immunoassay had high selectivity and accuracy. Importantly, this method provides a new horizon for detection of disease-related biomarkers with high sensitivity.

Photoelectrochemical bioanalysis of antibiotics on rGO-Bi2WO6-Au based on branched hybridization chain reaction.

Herein a versatile photoelectrochemical (PEC) bioanalysis platform for sensitive and specific screening of low-abundance antibiotics (kanamycin, Kana, used in this case) was innovatively designed using rGO-Bi2WO6-Au as photoactive matrix and target-induced branched hybridization chain reaction (t-bHCR) for efficient signal amplification. To realize the high-performance of our PEC bioanalysis system, rational introduction of reduced graphene oxide (rGO) and Au nanoparticles (Au NPs) greatly accelerated the electron transfer and enhances photoactivity. As expected, the ternary nanocomposite (i.e., rGO-Bi2WO6-Au) system with cascade energy level exhibited intense PEC signal responses thanks to multistep electron-transfer (MET) mechanism. Upon sensing the target Kana, t-bHCR is readily implemented, thus resulting in the assembly of numerous CuS nanoparticle (CuS NP). As a result, the loading CuS NPs from hyper-branched structure boosted the electron donors (ascorbic acid) consumption and enhanced the steric hindrance, synergistically decrease the photoelectric response. Under the optimized testing conditions, the t-bHCR-based PEC bioanalysis exhibited superior analytical performance with a linear range of 1 pM to 5 nM target Kana and limit of detection down to 0.78 pM. Additionally, favorable stability, great anti-interference ability and satisfactory accuracy for the analysis of actual samples were acquired. Impressively, the concept of t-bHCR-mediated provides an alternative to construct PEC bioanalysis and inspire more interest in the design of advanced PEC bioanalysis through nucleic acid-related signal amplification.

Platinum Nanozyme-Catalyzed Gas Generation for Pressure-Based Bioassay Using Polyaniline Nanowires-Functionalized Graphene Oxide Framework.

Pressure-based bioassays incorporating biomolecular recognition with a catalyzed gas-generation reaction have been developed for gas biosensors, but most involve poor sensitivity and are unsuitable for routine use. Herein we design an innovative gas pressure-based biosensing platform for the detection of Kanamycin (Kana) on polyaniline nanowires-functionalized reduced graphene oxide (PANI/rGO) framework by using platinum nanozyme-catalyzed gas generation. The signal was amplified by coupling with catalytic hairpin assembly (CHA) and strand-displacement amplification (SDA). Upon target Kana introduction, the analyte initially triggered a SDA reaction between hairpin DNA1 and hairpin DNA2, and then induced CHA conjugation between magnetic bead-labeled hairpin DNA3 (MB-H3) and platinum nanoparticle-labeled hairpin DNA4 (Pt-H4) to form a three-dimensional network. Numerous platinum nanoparticles (peroxidase-like nanozymes) were carried over with magnetic beads to reduce hydrogen peroxide into oxygen. The as-produced gas compressed PANI/rGO frameworks (modified to polyurethane sponge, used as the piezoelectric materials) in a homemade pressure-tight device, thus causing the increasing current of PANI/rGO sponge thanks to its deformation. The change in the current caused by the as-generated gas pressure was determined on an electrochemical workstation. Under optimum conditions, PANI/rGO sponge exhibited outstanding compressibility, stable signal-waveform output, fast response and recovery time (≈109 ms), and the current increased with the increasing Kana concentration within a dynamic working range of 0.2-50 pM at a detection limit of 0.063 pM. Good reproducibility, specificity, and acceptable precision were acquired for Kana analysis. In addition, the accuracy of this method was monitored to evaluate real milk samples with the well-matched results obtained by using the referenced Kana ELISA kit.

Near-Infrared Light-Excited Core-Core-Shell UCNP@Au@CdS Upconversion Nanospheres for Ultrasensitive Photoelectrochemical Enzyme Immunoassay.

A novel photoelectrochemical (PEC) enzyme immunoassay was designed for the ultrasensitive detection of alpha-fetoprotein (AFP) based on near-infrared (NIR) light-excited core-core-shell UCNP@Au@CdS upconversion nanospheres. Plasmonic gold (Au) between the sandwiched layers was not only utilized as an energy harvester for the collection of the incident light but also acted as an energy conveyor to transfer the energy from upconversion NaYF4:Yb3+,Er3+ (UCNP) to semiconductor CdS, thus exciting the efficient separation of electron-hole pairs by the generated H2O2 of enzyme immunoreaction under the irradiation of a 980 nm laser. By virtue of high catalytic activity of natural enzymes, gold nanoparticles heavily functionalized with glucose oxidase (GOx) and polyclonal anti-AFP antibody were utilized to generate H2O2. A sandwiched immunoreaction was first carried out in a monoclonal anti-AFP antibody-coated microplate by using an antibody-labeled gold nanoparticle as secondary antibody. Accompanying the gold nanoparticle, the carried GOx oxidized glucose in H2O2, thereby resulting in the enhanced photocurrent via capturing holes on the valence band of CdS to promote the separation of electron-hole pairs. Under optimum conditions, the NIR light-based PEC immunosensing system exhibited good photocurrent responses toward target AFP within the dynamic working range of 0.01-40 ng mL-1 at a detection limit of 5.3 pg mL-1. Moreover, the NIR light-based sensing platform had good reproducibility and high selectivity. Importantly, good well-matched results obtained from NIR light-based PEC immunoassay were acquired for the analysis of human serum specimens by using AFP ELISA kit as the reference.