doi:10.1039/d1nr08223jengSoria-Carrera, H.Atrián-Blasco, E.de la Fuente, J. M.Mitchell, S. G.Martín-Rapún, R.Polyoxometalate-polypeptide nanoassemblies as peroxidase surrogates with antibiofilm propertiesART-2022-128778Developing artificial metalloenzymes that possess a superior performance to their natural counterparts is an attractive concept. Polyoxometalates (POMs) are a class of anionic molecular metal-oxides with excellent redox properties and bioactivity. We have recently introduced “POMlymers” - covalently conjugated POM-peptide hybrid materials - where the polypeptide chain is obtained through a ring-opening polymerisation (ROP) of a-amino acid N-carboxyanhydrides (NCA) on an inorganic POM scaffold. Attracted by the idea of preparing artificial metalloenzymes, here we report the supramolecular self-assembly of POMlymer hybrids into nanoparticles where an optimal environment for catalysis is created. Our results demonstrate that the self-assembly of covalent POMlymers, enhances the peroxidase-like activity of the parent POM anion whereas, in contrast, the catalytic activity for nanoparticles obtained by ionic self-assembly of the same peptide and POM components practically disappears. Furthermore, POMlymer nanoparticles also present antimicrobial and antibiofilm activity against the skin bacterium Staphylococcus epidermidis; whereas, ionic POM-peptide hybrids significantly increase biofilm production and endogenous production of reactive oxygen species. In summary, we present the self-assembly of POMlymer hybrids into nanoparticles and a combination of peroxidase activity and microbiology assays that show that the POM-peptide covalent bond is essential for the stability of the self-assembled nanoparticles and therefore for their catalytic and biological activity. © 2022 The Royal Society of Chemistry.2022http://zaguan.unizar.es/record/11747210.1039/d1nr08223jhttp://zaguan.unizar.es/record/117472oai:zaguan.unizar.es:117472info:eu-repo/grantAgreement/ES/CSIC/i-Link+2019-LINK20270info:eu-repo/grantAgreement/ES/DGA/E15-20Rinfo:eu-repo/grantAgreement/EC/H2020/845427/EU/Peptide-functionalized POMs as biofilm disruption agents: searching for synergy in bactericidal materials/PePiPOMThis project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No H2020 845427-PePiPOMinfo:eu-repo/grantAgreement/ES/MEC/FPU2016-02456info:eu-repo/grantAgreement/ES/MICINN/PID2019-109333RB-I00Nanoscale 14, 16 (2022), 5999-6006byhttp://creativecommons.org/licenses/by/3.0/es/info:eu-repo/semantics/openAccess