Photodynamic-Assisted Electrochemiluminescence Enhancement toward Advanced BODIPY for Precision Diagnosis of Parkinson.

Nowadays, signal enhancement is imperative to increase sensitivity of advanced ECL devices for expediting their promising applications in clinic. In this work, photodynamic-assisted electrochemiluminescence (PDECL) device was constructed for precision diagnosis of Parkinson, where an advanced emitter was prepared by electrostatically linking 2,6-dimethyl-8-(3-carboxyphenyl)4,4'-difluoroboradiazene (BET) with 1-butyl-3-methylimidazole tetrafluoroborate ([BMIm][BF4]). Specifically, protoporphyrin IX (PPIX) can trigger the photodynamic reaction under light irradiation with a wavelength of 450 nm to generate lots of singlet oxygen (1O2), showing a 2.43-fold magnification in the ECL responses. Then, the aptamer (Apt) was assembled on the functional BET-[BMIm] for constructing a "signal off" ECL biosensor. Later on, the PPIX was embedded into the G-quadruplex (G4) of the Apt to magnify the ECL signals for bioanalysis of α-synuclein (α-syn) under light excitation. In the optimized surroundings, the resulting PDECL sensor has a broad linear range of 100.0 aM ∼ 10.0 fM and a low limit of detection (LOD) of 63 aM, coupled by differentiating Parkinson patients from normal individuals according to the receiver operating characteristic (ROC) curve analysis of actual blood samples. Such research holds great promise for synthesis of other advanced luminophores, combined with achieving an early clinical diagnosis.

Pt─O Bond Accelerated Cu0/Cu+ Activity for Boosting Low-Energy Bipolar Hydrogen Production.

To address the imperative challenge of producing hydrogen in a low-energy consumption electrocatalytic system, this study emphasizes the utilization of thermodynamically favorable biomass oxidation for achieving energy-efficient hydrogen generation. This research integrates ultralow PtO2-loaded flower-like nanosheets (denoted as PtO2@Cu2O/Cu FNs) with Cu0/Cu+ pairs and Pt─O bonds, thereby yielding substantial enhancement in both hydrogen evolution reaction (HER, -0.042 VRHE at 10 mA cm-2) and furfural oxidation reaction (FFOR, 0.09 VRHE at 10 mA cm-2). As validated by DFT calculations, the dual built-in electric field (BIEF) is elucidated as the driving force behind the enhanced activities, in which Pt─O bonds expedite the HER, while Cu+/Cu0 promotes low-potential FFOR. By coupling the FFOR and HER together, the resulting bipolar-hydrogen production system requires a low power input (0.5072 kWh per m3) for producing H2. The system can generate bipolar hydrogen and high value-added furoic acid, significantly enhancing hydrogen production efficiency and concurrently mitigating energy consumption.

Palladium nanospheres-embedded metal-organic frameworks to enhance the ECL efficiency of 2,6-dimethyl-8-(3-carboxyphenyl)4,4'-difluoroboradiazene in aqueous solution for ultrasensitive Cu2+ detection.

Nowadays, organic emitters suffer from insufficient electrochemiluminescence (ECL) efficiency in aqueous solutions, and their practical applications are severely restricted in the bio-sensing field. In this work, palladium nanospheres-embedded metal-organic frameworks (Pd@MOFs) were exploited to enhance the ECL efficiency of 2,6-dimethyl-8-(3-carboxyphenyl)4,4'-difluoroboradiazene (BET) prepared by a one-pot method in aqueous environment. First, the Pd@MOFs were generated via in situ reduction of Pd nanospheres anchored onto the MOFs, and fabricated by orderly coordination of palladium chloride (PdCl2) with 1,2,4,5-benzenetetramine (BTA) tetrahydrochloride. Then, the influence of protons on the ECL response of BET was studied in detail to obtain stronger ECL emission using potassium persulfate (K2S2O8) as co-reactant in aqueous environment. As a result, a 1.47-fold ECL efficiency enlargement of BET/K2S2O8 was harvested at the Pd@MOFs/GCE, where Ru(bpy)32+ behaved as a standard. Based on the fact that the ECL signals of the BET-covered Pd@MOFs modified glassy carbon electrode (simplified as BET/Pd@MOFs/GCE) can be quenched by Cu2+, the as-built ECL sensor showed a wide linear range (1.0-100.0 pM) and a limit of detection (LOD) as low as 0.12 pM. Hence, such research offers huge potential to promote the development of organic emitters in ECL biosensors and environmental monitoring.

Porous poly(bismaleimide-co-divinylbenzene) microspheres as dispersive solid-phase extraction adsorbent coupled to high-performance liquid chromatography for the determination of triazine herbicide residues in vegetable samples.

In this work, monodisperse and nano-porous poly(bismaleimide-co-divinylbenzene) microspheres with large specific surface area (427.6 m2 /g) and rich pore structure were prepared by one-pot self-stable precipitation polymerization of 2,2'-bis[4-(4-maleimidophenoxy) phenyl] propane and divinylbenzene. The prepared poly(bismaleimide-co-divinylbenzene) microspheres were employed as dispersive solid-phase extraction (DSPE) adsorbent for the extraction of triazine herbicides. Under optimized conditions, good linearities were obtained between the peak area and the concentration of triazine herbicides in the range of 1-400 µg/L (R2 ≥ 0.9987) with the limits of detection of 0.12-0.31 µg/L. Triazine herbicides were detected using the described approach in vegetable samples (i.e., cucumber, tomato, and maize) with recoveries of 93.6%-117.3% and relative standard deviations of 0.4%-3.5%. In addition, the recoveries of triazine herbicides remained above 80.7% after being used for nine DSPE cycles, showing excellent reusability of poly(bismaleimide-co-divinylbenzene) microspheres. The adsorption of poly(bismaleimide-co-divinylbenzene) microspheres toward triazine herbicides was a monolayer and chemical adsorption. The adsorption mechanism between triazine herbicides and adsorbents might be a combination of hydrogen bonding, electrostatic interaction, and π-π conjugation. The results confirmed the potential use of the poly(bismaleimide-co-divinylbenzene) microspheres-based DSPE coupled to the high-performance liquid chromatography method for the detection of triazine herbicide residues in vegetable samples.

Target-regulated photoactivities of CdS/Ni-MOF heterojunction with [Ru(bpy)2dppz]2+ intercalator: a bisphenol A photoelectrochemical aptasensor.

Bisphenol A (BPA), an important endocrine disrupting compound, has infiltrated human daily lives through electronic devices, food containers, and children's toys. Developing of novel BPA assay methods with high sensitivity holds tremendous importance in valuing the pollution state. Here, we constructed an ultrasensitive photoelectrochemical (PEC) aptasensor for BPA determination by regulating photoactivities of CdS/Ni-based metal-organic framework (CdS/Ni-MOF) with [Ru(bpy)2dppz]2+ sensitizer. CdS/Ni-MOF spheres exhibited excellent photocatalytic performance, serving as a potential sensing platform for the construction of target recognition process. [Ru(bpy)2dppz]2+ were embedded into DNA double-stranded structure, functioning as sensitizer for modulating the signal response of the developed PEC aptasensor. The proposed PEC sensor exhibited outstanding analytical performances, including a wide linear range (0.1 to 1000.0 nM), low detection limit (0.026 nM, at 3σ/m), excellent selectivity, and high stability. This work provides a perspective for the design of ideal photosensitive materials and signal amplification strategies and extends their application in environment analysis.

Selective Increase in CO2 Electroreduction to Ethanol Activity at Nanograin-Boundary-Rich Mixed Cu(I)/Cu(0) Sites via Enriching Co-Adsorbed CO and Hydroxyl Species.

Selective producing ethanol from CO2 electroreduction is highly demanded, yet the competing ethylene generation route is commonly more thermodynamically preferred. Herein, we reported an efficient CO2-to-ethanol conversion (53.5% faradaic efficiency at -0.75 V versus reversible hydrogen electrode (vs. RHE)) over an oxide-derived nanocubic catalyst featured with abundant "embossment-like" structured grain-boundaries. The catalyst also attains a 23.2% energy efficiency to ethanol within a flow cell reactor. In situ spectroscopy and electrochemical analysis identified that these dualphase Cu(I) and Cu(0) sites stabilized by grain-boundaries are very robust over the operating potential window, which maintains a high concentration of co-adsorbed *CO and hydroxyl (*OH) species. Theoretical calculations revealed that the presence of *OHad not only promote the easier dimerization of *CO to form *OCCO (ΔG ~ 0.20 eV) at low overpotentials but also preferentially favor the key *CHCOH intermediate hydrogenation to *CHCHOH (ethanol pathway) while suppressing its dehydration to *CCH (ethylene pathway), which is believed to determine the remarkable ethanol selectivity. Such imperative intermediates associated with the bifurcation pathway were directly distinguished by isotope labelling in situ infrared spectroscopy. Our work promotes the understanding of bifurcating mechanism of CO2ER-to-hydrocarbons more deeply, providing a feasible strategy for the design of efficient ethanol-targeted catalysts.

Self-enhanced Electrochemiluminescence Luminophore Based on Pd Nanocluster-Anchored Metal Organic Frameworks via Ion Annihilation for Sensitive Cell Assay of Human Lung Cancer.

Electrochemiluminescence (ECL) has attracted significant interest in the analysis of cancer cells, where the ruthenium(II)-based emitter demonstrates urgency and feasibility to improve the ECL efficiency. In this work, the self-enhanced ECL luminophore was prepared by covalent anchoring of Pd nanoclusters on aminated metal organic frameworks (Pd NCs@MOFs), followed by linkage with bis(2,2'-bipyridine)-5-amino-1,10-phenanthroline ruthenium(II) (RuP). The resultant luminophore showed 214-fold self-magnification in the ECL efficiency over RuP alone, combined by promoting the interfacial photoelectron transfer. The enhanced mechanism through ion annihilation was critically proved by controlled experiments and density functional theory (DFT) calculations. Based on the above, a "signal off" ECL biosensor was built by assembly of tyrosine kinase 7 (PTK-7) aptamer (Apt) on the established sensing platform for analysis of human lung cancer cells (A549). The built sensor showed a lower detection limit of 8 cells mL-1, achieving the single-cell detection. This work reported a self-enhanced strategy for synthesis of advanced ECL emitters, combined by exploring the ECL biosensing devices in the single-cell analysis of cancers.

Hydrogen Bond Organic Frameworks as Radical Reactors for Enhancement in ECL Efficiency and Their Ultrasensitive Biosensing.

Nowadays, electrochemiluminescence (ECL) efficiency of an organic emitter is closely related with its potential applications in food safety and environmental monitoring fields. In this work, 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (TATB) was self-assembled to form hydrogen bond organic frameworks (HOFs), which worked as ideal reactors to generate highly active oxygen-containing radicals, followed by linking with isoluminol (ILu) via amide bond (termed ILu-HOFs). After covalent assembly with aminated indium-tin oxide electrode (labeled NH2-ITO), the ECL efficiency of the ILu-HOFs NH2-ITO showed about a 23.4-time increase over that of ILu itself in the presence of H2O2. Meanwhile, the enhanced ECL mechanism was mainly studied by electron paramagnetic resonance, theoretical calculation, and electrochemistry. On the above foundation, an aptamer "sandwich" ECL biosensor was constructed for detecting isocarbophos (ICP) via in situ elimination of H2O2 with catalase-linked palladium nanocubes (CAT-Pd NCs). The as-built sensor showed a broad linear range (1 pM to 100 nM) and a low limit of detection (LOD) down to 0.4 pM, coupled with efficient assays of ICP in lake water and cucumber juice samples. This strategy provides an effective way for the synthesis of advanced ECL emitter, coupled by showing promising applications in environmental and food analysis.

N-Doped Carbon Nanotubes Supported Fe-Mn Dual-Single-Atoms Nanozyme with Synergistically Enhanced Peroxidase Activity for Sensitive Colorimetric Detection of Acetylcholinesterase and Its Inhibitor.

Monitoring acetylcholinesterase (AChE) and its inhibitors is of importance for early diagnosis and therapy of neurological diseases. Herein, N-doped carbon nanotubes supported Fe-Mn dual-single-atoms (FeMn DSAs/N-CNTs) were fabricated by a simple pyrolysis, as thoroughly figured out by a series of the characterization techniques. The peroxidase-like activity of FeMn DSAs/N-CNTs was investigated by catalytic oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to generate rich hydroxyl radicals (·OH) in the H2O2 system, which effectively catalyzed colorless TMB oxidation to blue oxidized TMB (ox-TMB). Besides, the peroxidase-like activity was greatly weakened by thiocholine (derived from AChE), accompanied by making blue ox-TMB fade. Impressively, the highly improved peroxidase-like property is further evidenced by density functional theory (DFT) calculations, where the dual-single atoms show a lower energy barrier (0.079 eV) and their interactions with the N-CNTs played critical roles for producing the oxygen radicals. By virtue of the nanozyme, a low-cost, specific, and sensitive colorimetric sensor was built for detection of AChE with a broader linear range of 0.1-30 U L-1 and a lower limit of detection (LOD, 0.066 U L-1), combined with its feasible analysis in human serum samples. Also, this platform was applied for measuring huperzine A inhibitor with a wide linear scope of 5-500 nM and a LOD down to 4.17 nM. This strategy provides a low-cost and convenient approach for early clinical diagnosis and drug development.

High-Activity Fe3 C as pH-Universal Electrocatalyst for Boosting Oxygen Reduction Reaction and Zinc-Air Battery.

Transition metal catalysts are regarded as one of promising alternatives to replace traditional Pt-based catalysts for oxygen reduction reaction (ORR). In this work, an efficient ORR catalyst is synthesized by confining Fe3 C nanoparticles into N, S co-doped porous carbon nanosheets (Fe3 C/N,S-CNS) via high-temperature pyrolysis, in which 5-sulfosalicylic acid (SSA) demonstrates as an ideal complexing agent for iron (ΙΙΙ) acetylacetonate while g-C3 N4 behaves as a nitrogen source. The influence of the pyrolysis temperature on the ORR performance is strictly examined in the controlled experiments. The obtained catalyst exhibits excellent ORR performance (E1/2  = 0.86 V; Eonset  = 0.98 V) in alkaline electrolyte, coupled by exhibiting the superior catalytic activity and stability (E1/2  = 0.83 V, Eonset  = 0.95 V) to Pt/C in acidic media. In parallel, its ORR mechanism is carefully illustrated by the density functional theory (DFT) calculations, especially the role of the incorporated Fe3 C played in the catalytic process. The catalyst-assembled Zn-air battery also exhibits a much higher power density (163 mW cm-2 ) and ultralong cyclic stability in the charge-discharge test for 750 h with a gap increase down to 20 mV. This study provides some constructive insights for preparation of advanced ORR catalysts in green energy conversion units correlated systems.

One-pot wet-chemical fabrication of 3D urchin-like core-shell Au@PdCu nanocrystals for electrochemical breast cancer immunoassay.

Carbohydrate antigen 15-3 (CA15-3) is an important biomarker for early diagnosis of breast cancer. Herein, a label-free electrochemical immunosensor was built based on three-dimensional (3D) urchin-like core-shell Au@PdCu nanocrystals (labeled Au@PdCu NCs) for highly sensitive detection of CA15-3, where K3[Fe(CN)6] behaved as an electroactive probe. The Au@PdCu NCs were synthesized by a simple one-pot wet-chemical approach and the morphology, structures, and electrocatalytic property were investigated by several techniques. The Au@PdCu NCs prepared worked as electrode material to anchor more antibodies and as signal magnification material by virtue of its exceptional catalytic property. The developed biosensor exhibited a wide linear detection range from 0.1 to 300 U mL-1 and a low limit of detection (0.011 U mL-1, S/N = 3) for determination of CA15-3 under the optimal conditions. The established biosensing platform exhibits some insights for detecting other tumor biomarkers in clinical assays and early diagnosis.

Simple pyrolysis of graphene-wrapped PtNi nanoparticles supported on hierarchically N-doped porous carbon for sensitive detection of carbendazim.

A novel electrochemical sensor was established based on graphene-wrapped PtNi nanoparticles supported on three-dimensional (3D) N-doped porous carbon (G-PtNi/3D-NPC) for the highly sensitive and selective detection of carbendazim (CBZ). In this sensing system, the encapsulation of PtNi nanoparticles (NPs) by graphene can effectively prevent the aggregation tendency and enhance the structural stability. The hierarchically porous nanostructures have a large specific surface area to expose a large number of active sites and the resulting enhanced electrical conductivity ultimate improves the electrocatalytic activity towards CBZ. Under the optimal conditions, the prepared sensor showed excellent electrochemical responses for the determination of CBZ with a linear range of 0.5-30 µM and lower limit of detection (LOD) of 0.04 µM (S/N = 3). It also shows excellent anti-interference ability at a working potential of 0.74 V. The feasibility of the senor is demonstrated for its practical assays in diluted peach and vegetable samples with acceptable recovery (95.8-97.3 %, peach; 97.2-97.6 %, vegetable) and a relative standard deviation (RSD) below 2.3%.

Mulberry-like porous-hollow AuPtAg nanorods for electrochemical immunosensing of biomarker myoglobin.

Mulberry-like AuPtAg porous hollow nanorods (PHNR) were facilely synthesized for the first time via a wet chemical method, where Au nanorods (Au NR) behaved as sacrificed template. The anisotropic oriented growth and etching process are involved in this synthesis. Their structural and electronic characteristics were scrutinously examined by TEM, EDS, XPS, and electrochemical techniques. The AuPtAg PHNR provided a large specific surface area and exposed a large number of active sites, showing highly enhanced catalytic activity. On this foundation, a label-free electrochemical immunosensor was developed for myoglobin (Myo) assay based on the AuPtAg PHNR. Further, the built sensor exhibited fast and ultrasensitive responses in a linear range of 0.0001 ~ 1000 ng mL-1 with a low limit of detection (LOD = 0.46 pg mL-1, S/N = 3), and enabled efficient application to human serum samples with acceptable results. Consequently, the developed AuPtAg PHNR-based platform has a broad prospect in practically monitoring Myo and other biomarkers in clinics.

Bimetallic AuPt alloy/rod-like CeO2 nanojunctions with high peroxidase-like activity for colorimetric sensing of organophosphorus pesticides.

Organophosphorus pesticides (OP) have extensive applications in agriculture, while their overuse causes inevitable residues in food, soil, and water, ultimately being harmful to human health and even causing diverse dysfunctions. Herein, a novel colorimetric platform was established for quantitative determination of malathion based on peroxidase mimic AuPt alloy decorated on CeO2 nanorods (CeO2@AuPt NRs). The synthesized nanozyme oxidized colorless 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2. Besides, the oxidized TMB was inversely reduced by ascorbic acid (AA), which were originated from hydrolysis of L-ascorbic acid-2-phosphate (AA2P) with the assistance of acid phosphatase (ACP). Based upon this observation ACP analysis was explored by colorimetry, showing a wid linear range of 0.2 ~ 3.5 U L-1 and a low limit of detection (LOD = 0.085 U L-1, S/N = 3). Furthermore, malathion present in the colorimetric system inhibited the activity of ACP and simultaneously affected the generation of AA, in turn promoting the recovery of the chromogenic reaction. Based on this, the LOD was decreased to 1.5 nM (S/N = 3) for the assay of malathion with a wide linear range of 6 ~ 100 nM. This simple colorimetric platform provides some informative guidelines for determination of other pesticides and disease markers.

Bifunctional photoelectrochemical aptasensor based on heterostructured Ag3PO4/Ag/TiO2 nanorod array for determination of two tumor markers.

Constructing of heterostructures can significantly improve the photoelectrical (PEC) response signal by promoting the migration and suppressing the recombination of photogenerated carries. A bifunctional PEC sensing platform was designed for simultaneous high-performance detection of mucin-1 (MUC1) and carcinoembryonic antigen (CEA), which was based on generated Z-scheme heterostructured Ag3PO4/Ag/TiO2 nanorod arrays (NAs) and enzyme-mediated catalytic precipitation by alkaline phosphatase (ALP) and Au/hollow Co3O4 polyhedron. The proposed aptasensor displayed linear ranges of 1.0-100 ng mL-1 and 0.1-50 ng mL-1 for MUC1 and CEA with limit of detections of 0.430 and 0.058 ng mL-1, respectively. This strategy offers potential applications for early diagnosis, monitoring progression, and even evaluating the prognosis of breast cancer in practice.

Label-free "signal-off" PEC aptasensor for determination of kanamycin based on 3D nanoflower-like FeIn2S4/CdS Z-scheme heterostructures.

Highly photoactive 3D nanoflower-like FeIn2S4/CdS heterostructures were synthesized by hydrothermal treatment and low-temperature cation exchange. The FeIn2S4/CdS displayed 14.5 times signal amplification in contrast to FeIn2S4 alone. It was applied as a photoactive substrate to construct a label-free photoelectrochemical (PEC) aptasensor for ultrasensitive determination of kanamycin (KAN). Under the optimal conditions, the constructed PEC aptasensor displayed a wide linear range (5.0 × 10-4 ~ 5.0 × 101 ng mL-1) and a low detection limit (S/N = 3) of 40.01 fg mL-1. This study provides some constructive insights for preparation of advanced photoactive materials and exhibits great potential for quantitative determination of antibiotics in foods and environmental samples.

Magnetic-assisted exciton-plasmon interactions modulated Bi2S3 nanorods@MoS2 nanosheets heterojunction: towards a split-type photoelectrochemical sensing of profenofos.

A split-type photoelectrochemical (PEC) sensor was designed for the detection of profenofos (PFF) depending on the magnetic-assisted exciton-plasmon interactions (EPI) between the semiconductor substrate and Au NPs. The core-shell Bi2S3 nanorods@MoS2 nanosheets (Bi2S3 NRs@MoS2 NSs) heterostructure nanomaterial with fascinating performance was synthesized and used as the photovoltaic conversion substrate and signal molecules absorption platform. The PEC sensor is operated by co-incubating with the released Au NPs-cDNA from the surface of magnetic beads, originating from the target-triggered DNA double-stranded structure opening event. Due to the strong EPI effects, the photocurrent of Bi2S3 NRs@MoS2 NSs decreased and varied with the PFF concentrations. The proposed PEC sensor exhibited outstanding analytical performances, including a wide linear range (1.0 pg mL-1~1.0 µg mL-1), low detection limitation (0.23 pg mL-1, at 3 σ/m), excellent specificity, high stability, and applicability. Overall, this work provides a new signal strategy for PEC biosensors and extends its application in environmental analysis.

Novel Aggregation-Enhanced PEC Photosensitizer Based on Electrostatic Linkage of Ionic Liquid with Protoporphyrin IX for Ultrasensitive Detection of Molt-4 Cells.

Nowadays, aggregation quenching of most organic photosensitizers in aqueous media seriously restricts analytical and biomedical applications of photoelectrochemical (PEC) sensors. In this work, an aggregation-enhanced PEC photosensitizer was prepared by electrostatically bonding protoporphyrin IX (PPIX) with an ionic liquid of 1-butyl-3-methylimidazole tetrafluoroborate ([BMIm][BF4]), termed as PPIX-[BMIm] for clarity. The resultant PPIX-[BMIm] showed weak photocurrent in pure dimethyl sulfoxide (DMSO, good solvent), while the PEC signals displayed a 44.1-fold enhancement in a water (poor solvent)/DMSO binary solvent with a water fraction (fw) of 90%. Such PEC-enhanced mechanism was critically studied by electrochemistry and density functional theory (DFT) calculation in some detail. Afterward, a label-free PEC cytosensor was built for ultrasensitive bioassay of acute lymphoblastic leukemia (molt-4) cells by electrodepositing Au nanoparticles (Au NPs) on the PPIX-[BMIm] aggregates and sequential assembly of protein tyrosine kinase (PTK) aptamer DNA (aptDNA). The resultant cytosensor showed a wide linear range (300 to 3 × 105 cells mL-1) with a limit of detection (LOD) as low as 63 cells mL-1. The aggregation-enhanced PEC performance offers a valuable and practical pathway for synthesis of advanced organic photosensitizer to explore its PEC applications in early diagnosis of tumors.

Novel Ultrasensitive Photoelectrochemical Cytosensor Based on Hollow CdIn2S4/In2S3 Heterostructured Microspheres for HepG2 Cells Detection and Inhibitor Screening.

Hepatocellular carcinoma is a life-threatening malignant tumor found around the world for its high morbidity and mortality. Therefore, it is of great importance for sensitive analysis of liver cancer cells (HepG2 cells) in clinical diagnosis and biomedical research. To fulfill this demand, hollow CdIn2S4/In2S3 heterostructured microspheres (termed CdIn2S4/In2S3 for clarity) were prepared by a two-step hydrothermal strategy and applied for building a novel photoelectrochemical (PEC) cytosensor for ultrasensitive and accurate detection of HepG2 cells through specific recognition of CD133 protein on the cell surface with the respective aptamer. The optical properties of CdIn2S4/In2S3 were investigated by UV-vis diffuse reflectance spectroscopy (DRS) and PEC technology. By virtue of their appealing PEC characteristics, the resultant PEC sensor exhibited a wider dynamic linear range from 1 × 102 to 2 × 105 cells mL-1 with a lower limit of detection (LOD, 23 cells mL-1), combined by evaluating the expression level of CD133 protein stimulated by metformin as a benchmarked inhibitor. This work opens a valuable and feasible avenue for sensitive detection of diverse tumor cells, holding great potential in early clinical diagnosis and treatment coupled by screening inhibitors.

Electronic Regulation of ZnCo Dual-Atomic Active Sites Entrapped in 1D@2D Hierarchical N-Doped Carbon for Efficient Synergistic Catalysis of Oxygen Reduction in Zn-Air Battery.

Transition metal-based nitrogen-doped carbon (M-Nx -C) is considered as a promising catalyst for the oxygen reduction reaction (ORR) in clean energy storage and conversion devices. Herein, ZnCo dual-atomic sites are incorporated in hierarchical N-doped carbon (HNC), with 1D nanotubes wrapped in 2D nanosheets structure (termed as 1D@2D ZnCo-HNC), via a one-step bio-inspired pyrolysis. The feeding ratio of Zn to Co precursor and pyrolytic temperature are critically modulated to achieve well-defined morphologies of the products, endowing them with the integrated merits of nanotubes and nanosheets as efficient ORR catalysts. Benefiting from the particular structure and electronic regulation of Zn on Co, the ZnCo-Nx dual-atomic system exhibits excellent ORR catalytic characteristics with an onset potential of 1.05 V and a half-wave potential of 0.82 V. Density functional theory calculations further explain the regulating role of Zn, such that the adjusted Co in ZnCo-Nx sites significantly reduces the energy cost to ultimately facilitate the ORR. Moreover, the Zn-air battery assembled with ZnCo-HNC is capable of delivering the maximum power density of 123.7 mW cm-2 and robust stability for 110 h (330 cycles). This method provides a promising strategy for fabricating efficient transition metal-based carbon catalysts for green energy devices.