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Inorganic/organic heterojunctions show promising applications as high-performance sensing platforms for photoelectrochemical (PEC) immunosensors. This work reports constructing a PEC biosensor for CA15-3 based on a self-assembled perylene diimide (PDI) nanowire sensitized In 2 O 3 @MgIn 2 S 4 S-scheme heterojunction platform. P-type semiconductor Cu 2 O nanoparticles were designed as a signal burst source and were used as immunoassay labels. The carboxyl group on self-assembled PDI nanowires eliminates the step of additional surface functionalization for covalent immobilization of the capture elements. The π-π stacking of PDI enhances electron generation efficiency, while the carboxylic acid groups on PDI promote electron transfer. The performance of the constructed sensor was validated using CA15-3 as a model. The experimental results showed that the sensor based on In 2 O 3 @MgIn 2 S 4 /PDI has excellent selectivity, stability, and reproducibility, and can sensitively detect CA15-3 in the range of 0.001-100 U·mL -1 with the detection limit of 0.00056 U·mL -1 . The sensor has a broad application prospect. It is hoped that this research work based on the unique advantages of the organic compound PDI will inspire other researchers to design light-responsive materials and promote the development of the field of photoelectrochemical sensing.

Metal nanoclusters (NCs) as a new kind of luminophore have acquired sufficient interest, but their widespread application is restricted on account of their relatively low electrochemiluminescence (ECL) efficiency. Then, aqueous metal NCs with high ECL efficiency were strongly anticipated, especially for the ultrasensitive analysis of biomarkers. Herein, a near-infrared (NIR) ECL biosensing strategy for the test of neuron-specific enolase (NSE) was proposed by utilizing N -acetyl-l-cysteine (NAC)- and cysteamine (Cys)-stabilized gold NCs (NAC/Cys-AuNCs) as ECL emitters with the NIR ECL emission around 860 nm and a metal-organic framework/palladium nanocubes (ZIF-67/PdNCs) hybrid as the coreaction accelerator through their admirable electrocatalytic activity. The NIR emission would reduce photochemical injury to the samples and even realize nondestructive analysis with highly strong susceptibility and suitability. Furthermore, the utilization of ZIF-67/PdNCs could improve the ECL response of NAC/Cys-AuNCs by facilitating the oxidation of the coreactant triethylamine (TEA), leading to the production of a larger quantity of reducing intermediate radical TEA •+ . Consequently, NAC/Cys-AuNCs with ZIF-67/PdNCs displayed 2.7 fold enhanced ECL emission compared with the single NAC/Cys-AuNCs using TEA as the coreactant. In addition, HWRGWVC (HWR), a heptapeptide, was introduced to immobilize antibodies for the specially binding Fc fragment of the antibodies, which improved the binding efficiency and sensitivity. As a result, a "signal-on" immunosensor for NSE analysis was obtained with an extensive linear range of 0.1 to 5 ng/mL and a low limit of detection (0.033 fg/mL) (S/N = 3). This study provides a wonderful method for the development of an efficient nondestructive immunoassay.

The low electrochemiluminescence (ECL) efficiency issue of zirconia (ZrO 2 ) has been a pressing problem since its discovery. In this study, a bandgap-regulated ECL enhancement strategy was developed to improve the ECL efficiency of ZrO 2 . Specifically, through the calcination of metal-organic frameworks (MOFs), the MOF-derived bimetallic oxide ZrCuO 3 was synthesized. Compared to ZrO 2 , the synthesized ZrCuO 3 exhibited a narrower bandgap and higher electron transfer efficiency, leading to enhanced ECL efficiency. Further investigation of the ECL emitter revealed that ZrCuO 3 exhibited multimodal ECL emission: annihilation ECL and co-reactant participation ECL (including anodic ECL with tripropylamine as a co-reactant and cathodic ECL with K 2 S 2 O 8 as a co-reactant). The anodic ECL with the highest efficiency was selected as the main mode for detecting the target in the aptasensor. Annihilation ECL and cathodic ECL served as alternative modes to ensure stability and continuity of the sensing system. Based on the bandgap-regulated strategy of ZrCuO 3 , a sensing chip with ITO as the working electrode was designed for the sensitive detection of florfenicol (FF). The constructed signal "off-on-off" aptasensor exhibited excellent detection performance for FF in the range of 0.0005-200 ng/mL. The proposed method provided a novel strategy for the analysis of other antibiotics or biomolecules.

Herein, a high-efficiency biosensor based on ternary electrochemiluminescence (ECL) system was constructed for procalcitonin (PCT) detection. Specifically, silver nanoclusters (Ag NCs) with stable luminescence properties were prepared with small-molecule lipoic acid (LA) as the ligand, and its ECL emission in persulfate (S 2 O 8 2- ) was first reported. Meanwhile, the prepared Ag NCs possessed ligand-to-metal charge-transfer characteristics, thus transferring energy from LA to Ag + for luminescence. Based on the small particle size, good biocompatibility, and molecular binding ability, Ag NCs-LA was used as an ideal luminescent probe. In addition, α-Fe 2 O 3 -Pt was introduced to facilitate the activation of S 2 O 8 2- , thereby generating more sulfate radicals to react with the free radicals of Ag NCs to enhance ECL emission. The synergistic effect of the variable valence state of transition metals and high catalytic activity of noble metals endows α-Fe 2 O 3 -Pt with excellent catalytic ability for S 2 O 8 2- . Importantly, the sensing mechanism was systematically demonstrated by UV-vis, fluorescence, and ECL analysis, as well as density functional theory calculations. At last, NKFRGKYKC was designed for specific immobilization of antibodies, thus releasing the antigen binding sites to improve the antigen recognition efficiency. Based on this, the developed biosensor showed high sensitivity for PCT detection, with a wide linear range (10 fg/mL-100 ng/mL) and a low detection limit (3.56 fg/mL), which could be extended to clinical detection of multiple biomarkers.

Herein, a novel dual mode detection system of split-type photoelectrochemical (PEC) and visual immunoassay was developed to detect neuron specific enolase (NSE), which achieved simultaneous and reliable NSE detection due to the completely different signal readouts and transduction mechanism. Specifically, specific reactions of antigens and antibodies were performed in 96-microwell plates. Gold nanoparticle (Au NP)-loaded Fe 3 O 4 (Au@Fe 3 O 4 ) NPs were used as secondary antibody markers and signal regulators, which could produce a blue-colored solution in the presence of 3,3',5,5'-tetramethylbenzidine (TMB) and H 2 O 2 because of its peroxidase-like activity. Therefore, the visual detection of NSE was realized, making the results more intuitive. Meanwhile, the above biological process could also be used as part of the split-type PEC sensing platform. Oxidized TMB and Fe 3+ were consumptive agents of the electron donor, which both realized the double quenching of PEC signal generated by the SnO 2 /MgIn 2 S 4 /Zn 0.1 Cd 0.9 S composites. Owing to the waterfall band structure, SnO 2 /MgIn 2 S 4 /Zn 0.1 Cd 0.9 S composites partially absorb visible light and effectively inhibit the electron-hole recombination, thereby providing significantly enhanced and stable initial signal. On the basis of the multiple signal amplification strategy and the split-type mode, NSE could be sensitively detected with a low detection limit of 14.0 fg·mL -1 (S/N = 3) and a wide linear range from 50.0 fg·mL -1 to 50.0 ng·mL -1 .

Nanoarrays (NAs) with stable signal output have become the most promising photoelectrochemical (PEC) biosensing substrate. However, a general issue is that interfacial charge-carrier recombination in a single-component semiconductor cannot be easily prevented, resulting in a low photocurrent density. Herein, a biosensor utilizing a Ag-embedded TiO 2 -Ag 2 S nanojunction (TiO 2 -Ag-Ag 2 S) as a signal converter was developed for the detection of CD44 protein─a transmembrane glycoprotein highly expressed in breast cancer cells. The ternary Z-scheme heterojunction was prepared by a distinctive scheme in which the Ag layer is introduced onto the surface of rutile TiO 2 NAs by magnetron sputtering, whereas the Ag 2 S is rooted in the local sulfuration of Ag. With a sufficient density of oriented nanorods, TiO 2 -Ag-Ag 2 S exhibits a smooth photocurrent output and minimal variation among different batches; it is undoubtedly a satisfactory PEC sensing carrier, which enables highly specific identification of target CD44 on the surface of MDA-MB-231 cells due to DNA strand displacement reactions (SDRs) and host-guest recognition between hyaluronic acid (HA) and CD44. The biosensor shows a sensitive PEC response to CD44 over a wide range of 37 to 5.0 × 10 5 cells/mL. We can conclude that this approach will provide an alternative solution to breast cancer diagnosis.

Dynamic self-assembly of iridium complexes in water-soluble nanocontainers is an important bottom-up process for fabricating electrochemiluminescence (ECL) bioprobes. PEGylated apoferritin (PEG-apoHSF) as the host offers a confined space to alter and modify the self-assembly of trans -bis(2-phenylpyridine)(acetylacetonate)iridium(III) [Ir(ppy) 2 (acac)] based on a pH-dependent depolymerization/reassembly pathway, allowing the formation of ECL-active iridium cores in PEG-apoHSF cavities (Ir@PEG-apoHSF). With an improved encapsulation ratio in PEG-apoHSF, the coreactant ECL behavior of the fabricated Ir@PEG-apoHSF nanodots with tri- n -propylamine (TPrA) was further demonstrated, exhibiting maximum ECL emission at 530 nm that was theoretically dominated by the band gap transition. The application of Ir@PEG-apoHSF as a bioprobe in a "signal-on" ECL immunosensing system was developed based on electroactive Ti 3 C 2 T x MXenes/TiO 2 nanosheet (Ti 3 C 2 T x /TiO 2 ) hybrids. Combining with the efficiently catalyzed electro-oxidation of TPrA and Ir(ppy) 2 (acac) by Ti 3 C 2 T x /TiO 2 hybrids, the developed immunosensor showed dramatically amplified ECL responses toward the target analyte of neuron-specific enolase (NSE). Under experimental conditions, linear quantification of NSE from 100 fg/mL to 50 ng/mL was well established by this assay, achieving a limit of detection (LOD) of 35 fg/mL. The results showcased the capability of PEGylated apoHSF to host and stabilize water-insoluble iridium complexes as ECL emitters for aqueous biosensing and immunoassays.

Nowadays, the electrochemiluminescence (ECL) immunosensor with the unique superiority of tunable luminescence and ultrahigh sensitivity has become one of the most promising immunoassay techniques, especially for low-abundance biomarkers analysis. However, the use of signal probes with high excited potential and applied emitters which owned good intensity but biotoxicity limited its application. Herein, an ECL resonance energy transfer strategy was developed based on protein bioactivity protection utilizing europium-doped phosphoric acid gadolinium (GdPO 4 :Eu) as novel low-potential luminophor (donor) and Pd@Cu 2 O as the quenching probe (acceptor). Specifically, GdPO 4 :Eu was first prepared by using the hydrothermal synthesis method to apply in ECL, and when it coexisted with K 2 S 2 O 8 , cathode, a strong ECL signal would be generated at a low potential of -1.15 V (vs Ag/AgCl), where the immunocompetence of antigens and antibodies can be maintained well. Electrical pair Eu 3+ /Eu 2+ , as the coreactant promoter, produced by potential excitation could produce more SO 4 •- to accelerate the oxidation process of GdPO 4 :Eu. Meanwhile, Cu 2 O coated onto Pd (Pd@Cu 2 O), as a dual-quencher, enhanced the quenching effect of Pd alone and controlled the ECL intensity of the "signal on" state within a reasonable range. As a result, the proposed biosensor for detection of trace procalcitonin, a biomarker of systemic inflammatory response syndrome, exhibited a far low detection limit, 0.402 fg/mL (S/N = 3). Importantly, this work not only utilized a promising ECL emitter for biosensing platform construction but also had momentous potential in biomarker detection of disease diagnosis and clinical analysis.

The expansion of electrochemiluminescence (ECL) technology to immunoassay at the core of care emphasizes all immune molecules will not be inactivated in the analysis process. That poses a major challenge to ECL-based biosensors due to the deoxynucleotide sequences of an antigen or antibody could be oxidized through a route of excessive cyclic potential. Herein, an ultrasensitive ECL biosensor was developed based on a novel bioactivity-protected sensing strategy utilizing Au nanoclusters (Au NCs) as low-potential luminophor for detection of procalcitonin (PCT). Bovine serum albumin (BSA)-templated Au NCs exhibited a low-potential anodic ECL signal in triethylamine (TEA) solution at 0.87 V, where it is suitable for the survival of immune molecules. Taking advantage of good conductivity and high surface area, a Cu 2 S snowflake not only functions as a satisfying substrate for connecting immune molecules but also acts as co-reaction accelerator to produce more cationic radicals TEA •+ , which could improve the ECL intensity needed to meet the requirements of trace analysis. Otherwise, HWRGWVC (HC-7) heptapeptide as specific antibody immobilizer for site-oriented fixation was introduced to further maintain the bioactivity of an antibody. In view of the preceding discussion, the obtained biosensor exhibited ultrahigh immune recognition to targets so that the detection limit was as low as an unprecedented value of 2.36 fg/mL, which will be of great significance to the application and development of a biosensor in the future.