Ligand‐protected gold nanoclusters (AuNCs) have emerged as a new class of electrochemiluminescence (ECL) luminophores for their interesting catalytic and emission properties, although their quantum yield (ΦECL) in aqueous medium is low with a poor mechanistic understanding of the ECL process. Now it is shown that drying AuNCs on electrodes enabled both enhanced electrochemical excitation by an electrocatalytic effect, and enhanced emission by aggregation‐induced ECL (AIECL) for 6‐aza‐2‐thiothymine (ATT) protected AuNCs with triethylamine (TEA) as a coreactant. The dried ATT‐AuNCs/TEA system resulted in highly stable visual ECL with a ΦECL of 78 %, and a similar enhancement was also achieved with methionine‐capped AuNCs. The drying enabled dual‐enhancement mechanism has solved a challenging mechanistic problem for AuNC ECL probes, and can guide further rational design of ECL emitters.

This work elucidated the valence states effect on the electrogenerated chemiluminescence (ECL) performance of gold nanocluster (AuNC). The N-acetyl-l-cysteine-AuNCs (NAC-AuNCs) and the electrochemical reduction method for reducing the AuNCs were first employed to this study. Results demonstrate that the electrochemical reduction degree of the AuNCs depended on the reduction potential, and the enhancement of the ECL signals was positively correlated with the reduction degree of AuNCs, which indicated that the valence state of Au plays a vital role in the ECL performance of AuNCs. Furthermore, the proposed method has been successfully extended to the chemical reduction technique and other nanoclusters. Therefore, an excellent AuNC-based ECL method with various advantages, such as simple preparation, lower toxicity, high sensitivity, and Φ, and excellent stability, has been proposed. This approach not only opens up a new avenue for designing and developing ECL device from other functional-metal based NCs, but also extends the huge potential application in the ECL sensing.

Donor−linker−acceptor (D-L-A)-based photoinduced electron transfer (PET) has been frequently used for the construction of versatile fluorescent chemo/biosensors. However, sophisticated and tedious processes are generally required for the synthesis of these probes, which leads to poor design flexibility. In this work, by exploiting a Schiff base as a linker unit, a covalently bound D-L-A system was established and subsequently utilized for the development of a PET sensor. Cysteamine (Cys) and N-acetyl-L-cysteine (NAC) costabilized gold nanoclusters (Cys/ NAC-AuNCs) were synthesized and adopted as an electron acceptor, and pyridoxal phosphate (PLP) was selected as an electron donor. PLP can form a Schiff base (an aldimine) with the primary amino group of Cys/NAC-AuNC through its aldehyde group and thereby suppresses the fluorescence of Cys/NAC-AuNC. The Rehm−Weller formula results and a HOMO−LUMO orbital study revealed that a reductive PET mechanism is responsible for the observed fluorescence quenching. Since the pyridoxal (PL) produced by the acid phosphatase (ACP)-catalyzed cleavage of PLP has a weak interaction with Cys/NAC-AuNC, a novel turn-on fluorescent method for selective detection of ACP was successfully realized. To the best of our knowledge, this is the first example of the development of a covalently bound D-L-A system for fluorescent PET sensing of enzyme activity based on AuNC nanoprobes using a Schiff base.

Metal nanoclusters (NCs) have been developed as a new class of luminescent nanomaterials with potential applications in various fields. However, for most of the metal NCs reported so far, the relatively low photoluminescence quantum yield (QY) in aqueous solution hinders their applications. Here, we describe the utilization of bis-Schiff base linkages to restrict intramolecular motion of surface motifs at the single-cluster level. Based on Au22(SG)18 (SG: glutathione) NCs, an intracluster cross-linking system was constructed with 2,6-pyridinedicarboxaldehyde (PDA), and water-soluble gold NCs with luminescence QY up to 48% were obtained. The proposed approach for achieving high emission efficiency can be extended to other luminescent gold NCs with core-shell structure. Our results also show that the content of surface-bound Au(I)-SG complexes has a significant impact on the PDA-induced luminescence enhancement, and a high ratio of Au(I)-SG will be beneficial to increasing the photoluminescence intensity of gold NCs.

This report outlines a versatile high-performance electrochemiluminescence (ECL) enzyme-linked immunosorbent assay (ELISA) platform, which combines the merits of high-quantum-yield Au nanocluster (AuNC) probe-based ECL technology, the efficient ECLresonance energy-transfer (ECL-RET) strategy, and highly sensitive and specific ELISA technology. The ECL detection procedure was performed on a recyclable MnO 2 /AuNC-modified glassy carbon electrode interface by taking advantage of the ECL-RET between the AuNC probe and MnO 2 nanomaterials (NMs) to quench the ECL intensity. The etching of MnO 2 NMs by the product of ALP-based ELISA recovers the ECL signal. Notably, the ELISA process and the ECL detection procedure in this system are independent. Thus, the ECL-ELISA system can effectively avoid the influence of complex biological samples, and the ECL efficiency of the AuNC probe can be used readily. As demonstrated on TNF-α, because of the abovementioned characteristics, the ECL-ELISA platform presented an extremely wide dynamic range, with a detection limit of 2 orders lower than ELISA. Moreover, the system was also applicable for ultrahigh sensitive detection of various disease-related proteins and able to detect trace biomarkers in real serum samples. Therefore, this multifunctional ECL assay platform is versatile, facile, ultrasensitive, recyclable, and sufficiently straightforward for trace biomarker detection in complex biological samples. This approach not only enriches the foundational study of ECL devices but also greatly expands the potential application of ECL sensors in biological testing and clinical high-throughput diagnosis.

In this study, on the basis of the biomineralization capability of urease, a facile, one-step, and green synthetic method has been proposed for the fabrication of gold nanoclusters (AuNCs). The prepared urease-encapsulated AuNCs (U-AuNCs) exhibited strong red fluorescence emission (λ em = 630 nm) with a quantum yield as high as 17%. Interestingly, at a low concentration, the U-AuNC solution was found to be a dual-emissive system with the blue emission of the dityrosine (diTyr) residues of urease and the red emission of the embedded AuNCs. Further experiments demonstrated that p-nitrophenol (PNP) can selectively suppress the 410 nm emission of the diTyr residues of U-AuNCs without affecting the red emission of the U-AuNCs. The fluorescence quenching mechanism between U-AuNCs and PNP was systematically studied, and the leading role of the inner filter effect (IFE) was identified. Additionally, based on the sulfatase-catalyzed hydrolysis of p-nitrophenyl sulfate (PNPS) to release PNP, a self-referenced ratiometric detection method for sulfatase, which plays a crucial role in sulfur cycling, degradation of sulfated glycosaminoglycans and glycolipids, and extracellular remodeling of sulfated glycosaminoglycans, was developed by using dual-emissive U-AuNCs as the signal readout, in which the diTyr residues served as the probe and the AuNCs functioned as the internal reference. This IFEbased ratiometric sensing strategy showed a good linear relationship over the range of 0.01−1 U/mL (R 2 = 0.997). The detection limit for sulfatase activity was 0.01 U/mL. The developed protocol was successfully used to detect sulfatase activity in human serum samples. The simplicity, rapidity, low cost, high credibility, good reproducibility, and excellent selectivity of the detection platform serve as an inspiration for further applications of fluorescent AuNCs in chemo/biosensing.

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The use of metal ions to bridge the fluorescent materials to target analytes has been demonstrated to be a promising way to sensor design. Herein, the effect of rare-earth ions on the fluorescence of L-methioninestabilized gold nanoclusters (Met-AuNCs) was investigated. It was found that europium (Eu 3+ ) can significantly suppress the emission of Met-AuNCs, while other rare-earth ions showed a negligible impact. The mechanism on the observed fluorescence quenching of Met-AuNCs triggered by Eu 3+ was systematically explored, with results revealing the dominant role of photoinduced electron transfer (PET). Eu 3+ can bind to the surface of Met-AuNCs by the coordination effect and accepts the electron from the excited Met-AuNCs, which results in Met-AuNC fluorescence suppression. After introducing dipicolinic acid (DPA), an excellent biomarker for spore-forming pathogens, Eu 3+ was removed from the surface of Met-AuNCs owing to the higher binding affinity between Eu 3+ and DPA. Consequently, an immediate fluorescence recovery occurred when DPA was present in the system. Based on the Met-AuNC/Eu 3+ ensemble, we then established a simple and sensitive fluorescence strategy for turn-on determination of biomarker DPA, with a linear range of 0.2−4 μM and a low limit of detection of 110 nM. The feasibility of the proposed method was further validated by the quantitative detection of DPA in the soil samples. We believe that this study would significantly facilitate the construction of metal-ion-mediated PET sensors for the measurement of various interested analytes by applying fluorescent AuNCs as detection probes.