The mechanisms of HSA@PDA/Fe nanocomposites with enhanced nanozyme activity and their application in intracellular H2O2 detection.

Nanozymes have drawn increasing attention with their broad applications but most nanozymes lack enzyme-like molecular structures, resulting in weak selectivity and low activity. Bioinspired molecular assembly provides an extremely promising strategy to mimic natural enzyme processes and develop function enhanced architectures. Herein, a new bioinspired molecular assembly strategy based on human serum albumin@polydopamine/Fe nanocomposites (HSA@PDA/Fe NCs) was proposed, in which Fe(iii)/Fe(ii) were anchored on HSA supported on PDA. HSA@PDA/Fe NCs with iron as the active center and HSA@PDA as the skeleton showed excellent peroxidase-like activity, which was nearly 1000 times higher than that of free Fe(iii). This may be attributed to the phenomenon that the cycle of quinones and the hydroxyl group on the nanocomposite surface greatly accelerate the conversion of Fe(iii)/Fe(ii) in acidic microenvironments. Systematic experimental studies illustrated that its activity was mainly affected by the metal active center, followed by the polymeric ligand, while the protein framework has little effect on its activity. Meanwhile, even after freeze-thaw and thermal cycle tests, it also showed excellent catalytic stability. Besides, a colorimetric assay based on HSA@PDA/Fe NCs was developed for detection of H2O2 in vitro and in situ detection of H2O2 generated from live cells. This work will facilitate the developments on theoretical analysis, rational design and practical applications of nanozymes based on bioinspired molecular assemblies.