Recently, reactive oxygen species (ROS)-independent mimetics of oxidase with Au nanoclusters (NCs) as the catalysts and MnO₂ as electron acceptor have gained attention. In this study, we aim to explore the oxidase-mimicking potential of bovine serum albumin (BSA)-templated metal nanoclusters (BSA-M NCs, where M = Ag, Pt, Cu, or Cd) beyond Au NCs in boosting the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by MnO₂, denoted as BM@Metal. The oxidase-mimetic activity of BM@Metal is independent of ROS and generally enhanced by the incorporation of metal nanoclusters. Notably, this enhancement varies with the metal species, with BSA-Cd exhibiting the highest activity. The X-ray photoelectron spectroscopy (XPS) analysis confirms mixed valence states (Mn(IV)/Mn(II)) in BM@Cd. Given that the catalytic activity is closely linked to the substrate adsorption, the label-free isothermal titration calorimetry was employed to probe the affinity between TMB and BSA-M NCs, which provides a robust approach for probing the interface adsorption. The results reveal that the superior catalytic performance of BSA-Cd correlates with enhanced TMB adsorption, likely facilitated by coordination and hydrophobic interactions. Finally, the superior catalytic performance of BSA-M NCs on the oxidation of TMB by MnO₂ has inspired us to fabricate the assay for analyzing α-glucosidase’s activity. This work not only demonstrates the versatility of metal NCs in constructing ROS-independent oxidase mimetics but also provides interfacial adsorption engineered strategy for the rational design of superior ROS independent mimetics of natural oxidase.

Gold nanoclusters (AuNCs) have garnered significant attention due to their unique photoluminescent, catalytic, and therapeutic properties. Since the discovery of their ability to enhance emission through aggregation, researchers have extensively studied hybrid nanomaterials formed by combining AuNCs with various components through assembly. Assembly can significantly improve the original performance of AuNCs and confer additional properties such as responsiveness and targeting. These assembly strategies greatly expand the potential applications of AuNCs and are regarded as essential means to improve the detection, imaging, and therapeutic capabilities. This review categorizes recent advancements in AuNC assembly methods, including self-assembly and co-assembly of AuNCs. In addition, the emerging directions in the in vivo assembly and disassembly of AuNCs are also being addressed. We also discuss the applications of AuNC assemblies in in vitro biodetection, in vivo bioimaging, and therapeutic platforms. Finally, we offer prospects for the future development of AuNC assemblies. With further exploration of assembly strategies, mechanisms, and application designs, AuNC assemblies are expected to play a more significant role in more fields.

The immunomodulatory efficacy of current psoriasis biological therapies is hindered by their limited ability to scavenge multiple cytokines, inefficient delivery to specific inflamed skin regions, and potential side effects. Upon analyzing samples from both patients and mice, we identify a significant increase in type IV collagen within the extracellular matrix (ECM) of psoriatic skin. Thus, we report the microneedle (MN) delivery of type IV collagen targeting peptide-modified dual-cell membrane biomimetic nanodecoys (CRHM@lip) with multiple cytokines scavenging ability for treating psoriasis. The CRHM@lip can scavenge both tumor necrosis factor-α (TNF-α) and interleukin (IL)-17. Upon MN delivery, the nanodecoys target ECM and exhibit skin retention for over 120 h. The treatment by CRHM@lip-integrated MNs reduces skin thickness in mice by 57.9% and shows decreased levels of TNF-α, IL-17, IL-23, and interferon (IFN)-γ in skin sections compared to the psoriasis group. Additionally, the CRHM@lip treatment reduces the CD4⁺ T cells, M1 macrophages, and dendritic cells in the spleen, and suppresses various inflammatory mediators in serum, significantly demonstrating immunological microenvironmental suppression. Compared to systemic administration routes, MN delivery improves treatment outcomes. No noticeable adverse effects on hepatic and renal functions are observed in mice after treatment. This approach enhances the effectiveness of biological therapies and has the potential for translation.