Jul 2026· Small· pp.
e74501
· 0 citations· 38 references
Medicine
TL;DR
This study reported the interface self-assembly of Au10 nanoclusters for the first time, and ultimately formed a fibrous structure with a high aspect ratio, Au10-Fiber, which is an innovative approach that significantly enhances the ECL activity of Au10 NCs.
Abstract
Atomically precise metal nanoclusters (NCs), as ultrasmall materials with well-defined composition and structure, exceptional biocompatibility, and unique optical properties, position them as strong candidates in the field of electrochemiluminescence (ECL). However, the ECL efficiency of NCs is relatively low, which dramatically constrained their applications due to the demands of detection sensitivity and brightness. In this study, we report the interface self-assembly of Au10 nanoclusters for the first time, and ultimately formed a fibrous structure with a high aspect ratio, Au10-Fiber, which is an innovative approach that significantly enhances the ECL activity of Au10 NCs. By employing time-dependent and in situ spectroscopic techniques, we visually monitored the dynamic assembly process, and elucidated the interface self-assembly mechanism mediated by aurophilic interaction and π-π stacking. The increase in local electronic density, enhanced conductivity of the ordered structure, and accelerated electron transfer within the π-conjugated system collectively contributed to the significant enhancement of the ECL performance, thereby revealing the key structural factors responsible for ECL enhancement. As a proof of concept, we successfully constructed an ECL immunosensor based on Au10-Fiber for the detection of Alzheimer's disease biomarker Aβ1-42, achieving a detection limit below 3.33 fg/mL.
Atomically Precise Gold Nanoclusters (AP-AuNCs) have emerged as cutting-edge nanomaterials in the electrochemiluminescence (ECL) realm due to their atomically precise structures, quantum confinement effect, and superior biocompatibility. This review systematically summarizes the recent advancements of AP-AuNCs in ECL. First, the fundamental ECL mechanisms are elucidated from a molecular orbital perspective, rooted in the “core-ligand shell” hierarchical structure and superatomic electronic nature of AP-AuNCs. Subsequently, precision modulation strategies for tuning their ECL performances, such as gold core structural regulation, bimetallic doping, ligand engineering, valence state engineering, aggregation-induced ECL, and system energy level matching, are comprehensively presented. Furthermore, the current application landscape in biomedicine, environmental monitoring, and food safety is evaluated. Finally, the future challenges and developmental prospects of this field are also discussed. This review aims to provide a systematic theoretical reference and innovative insights for the atomic-level design of high-performance AP-AuNCs-based ECL systems, facilitating their transitions toward practical application scenarios.
Bimetallic nanoclusters possess tunable physicochemical properties, improved performance, and enhanced stability for versatile applications. Among them, atomically precise AuAg nanoclusters have an important position in the series of bimetallic nanoclusters thanks to the easy preparation and crystallization, unique electronic structure, and robust stability. In this review, the general introduction of bimetallic nanoclusters and the uniqueness of AuAg nanoclusters are first explained. Then, the main strategies for the controlled synthesis of AuAg nanoclusters are summarized, with examples to illustrate the workflow and potential limitations. Following this, atomically precise AuAg nanoclusters for electrocatalytic applications, including overall water splitting, CO2 reduction reaction, and urea electrosynthesis, are discussed. In this major part, carefully chosen examples are analyzed to reveal the atomic-level structure-performance relationship and to understand the fundamental reaction mechanism. Finally, the current challenges and future outlooks in this field are discussed critically.
Jingwen Yang, Liang Qiao, Tao Wu et al.· Chemical Synthesis· 0 citations
While single thiolate-stabilized silver nanoclusters (NCs) are well studied, multiligand-protected analogues remain rare. Herein, we report a luminescent Ag24 nanocluster, co-stabilized by two distinct heterocyclic thiols, 2-mercapto-5-n-propylpyrimidine and 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol, together with triphenylphosphine, whose composition was confirmed by high resolution electrospray ionization (HR-ESI) mass spectrometry. It shows aggregation-caused quenching as it self-assembles into nonemissive sheets, but the emission reappears after mechanical grinding, demonstrating mechanoresponsive luminescence. Interestingly, individual ligands form nonluminescent clusters exhibiting no aggregation behavior. Femtosecond transient absorption measurements indicate that aggregation alters the excited-state dynamics, reflecting the effect of multiligand stabilization on structural rigidity and photophysical behavior in the NCs.
Deepak Kumar Patel, Ankit Sharma, Arijit Jana et al.· Inorganic Chemistry· 0 citations
As a blood biomarker associated with cerebral infarction (CI), the ultrasensitive detection of S100 calcium-binding protein B (S100B) is of great significance for the early warning of CI. Electrochemiluminescence (ECL) technology holds tremendous application potential due to its high sensitivity and low background noise. However, the further expansion of ECL applications is often limited by low efficiency. In particular, gold nanoclusters (NCs) typically undergo significant nonradiative decay due to the vibrational and rotational motion of their ligands. Regulating the metal-organic frameworks structure and synergistically enhancing it with coreactant accelerators is an effective strategy to overcome this performance bottleneck. In this study, we constructed an ECL system with dual enhancement effects of emitter and coreactant sides. At the emitter side, bovine serum albumin (BSA)-stabilized AuNCs (BSA-AuNCs) were loaded onto pleated Ce-MOF (B-AuNCs/Ce-MOF), and nonradiative decay was suppressed through the rigidification effect, resulting in 1.73 times the ECL efficiency of BSA-AuNCs. At the coreactant side, NiFe-PBA nanomaterials (Ni/Fe precursor molar ratio of 3:2) were engineered to serve as coreactant accelerators. Density functional theory (DFT) calculations indicated that the model constructed with a Ni/Fe precursor ratio of 3:2 exhibited the most favorable adsorption energy of TEA, with an adsorption energy of -0.432 eV. Consequently, the B-AuNCs/Ce-MOF+NiFe-PBA system exhibited 2.12 times the ECL efficiency of BSA-AuNCs. Based on this synergistically enhanced system, ultrasensitive detection of the CI biomarker S100B was achieved, with a linear range of 0.1 pg/mL-100 ng/mL and a detection limit of 0.03 pg/mL (S/N = 3). The method also demonstrated excellent stability, reproducibility and selectivity. This strategy provides a new approach for the early diagnosis and precise detection of acute CI.
Na Li, Jing Chen, Dehao Jia et al.· Analytical Chemistry· 0 citations
Achieving high-efficiency electrochemiluminescence (ECL) with an ultralong lifetime and a large Stokes shift in a single emitter is highly desirable yet challenging. Herein, we report the supramolecular assembly of gold nanoclusters (Au NCs) protected by a custom-designed ligand, 1-(4-carboxyphenyl)-5-mercapto-1H-tetrazole (CPMT), which achieved the aforementioned outstanding performance. The CPMT ligand not only stabilized the Au NCs through bidentate Au-S/Au-N coordination, but also induced supramolecular assembly via intermolecular π-π interactions and hydrogen bonding. The obtained self-assembled CPMT-Au NCs exhibited an exceptionally long ECL lifetime of 60.48 μs, since their rigid spherical superstructure effectively minimized interfacial nonradiative decay, leading to an intrinsically prolonged excited-state lifetime, and passivated the emissive cores against oxygen quenching, preserving the long-lived emission under ambient conditions. Concurrently, the assembly showcased a remarkably large Stokes shift of 490 nm, which virtually eliminated self-absorption even in the solid state. The assembled CPMT-Au NCs displayed dramatically enhanced ECL efficiency of 353.37%, a 15-fold enhancement over their nonassembled counterparts, attributable to the synergistic suppression of interfacial energy dissipation and self-absorption as well as the improved electrochemical excitation. Additionally, a sensitive sensing platform for carboxylesterase (CE) activity related to early hepatocellular carcinoma was developed with a detection limit of 1.98 × 10-7 U/L. Therefore, this work establishes supramolecular assembly driven by ligand engineering as a rational platform for regulating the excited-state properties of metal nanoclusters, opening new avenues for high-performance ECL emitters in lifetime-based sensing, high-brightness devices, and multiplexed bioassays.
In this work, red-fluorescent silver nanoclusters (MMTA@Ag NCs) with aggregation-induced emission (AIE) properties were synthesized via a facile one-pot strategy at room temperature using 2-mercapto-4-methyl-5-thiazoleacetic acid (MMTA) as the capping ligand. The as-prepared Ag NCs initially exhibited weak fluorescence in aqueous solution with a quantum yield of only 0.0037. Upon the introduction of Mn2+, the metal ions acted as electrostatic bridges by coordinating with the carboxylate groups (-COO-) on the NCs surface, triggering significant aggregation of the nanoclusters. This aggregation effectively restricted intramolecular motion, leading to a remarkable "turn-on" fluorescence enhancement with a 100-fold increase in quantum yield to 0.38. Based on this AIE mechanism, a novel fluorescent sensing platform for Mn2+ detection was established. The method exhibited a satisfactory linear response over the Mn2+ concentration range of 0.01-0.50 µmol L-1 with a low detection limit of 9.79 nmol L-1 and excellent selectivity over other interfering ions. The proposed method was successfully applied to the determination of Mn2+ in milk samples, with satisfactory recoveries ranging from 99.0% to 106.2% and RSD below 2.7%. Furthermore, a highly luminescent PVA composite film was fabricated using the MMTA@Ag NCs-Mn2+ system, demonstrating promising potential in anti-counterfeiting applications.
