The ring-opening polymerisation of α-amino acid N-carboxyanhydrides (NCAs) offers a simple and scalable route to polypeptides with predicted and narrow molecular weight distributions. Here we show how polyoxometalates (POMs)—redox-active molecular metal-oxide anions—can serve as inorganic scaffold initiators for such NCA polymerisations. This “On-POM polymerisation” strategy serves as an innovative platform to design hybrid materials with additive or synergistic properties stemming from the inorganic and polypeptide component parts. We have used this synthetic approach to synthesise a library of bactericidal poly(lysine)–POM hybrid derivatives that can be used to prevent biofilm formation. This versatile “On-POM polymerisation” method provides a flexible synthetic approach for combining inorganic scaffolds with amino acids, and the potential to tailor and improve the specificity and performance of hybrid antimicrobial materials.
Financial support from Ministerio de Ciencia Innovación y Universidades (Spain) through a Ramón y Cajal fellowship (RMR, RYC-2013-12570) and Proyectos I+D+i (PID2019-109333RB-I00, PGC2018-097583-B-I00, and PID2019-105881RB-I00) and CSIC i-Link+2019 project (LINK20270). HSC and IFC are grateful for predoctoral fellowships from Ministerio de Educación Cultura y Deporte (FPU program) and Gobierno de Aragón, respectively. Further financial support from Fondo Social Europeo-Gobierno de Aragón (E15_20R, E47_20R and E31_17R) and CIBER-BBN is gratefully acknowledged. The authors would like to acknowledge the Laboratorio de Microscopías Avanzadas (LMA) at Universidad de Zaragoza for offering access to their instruments and expertise, especially Guillermo Antorrena for the XPS measurements; the use of the Unidad de Apoyo a la Investigación del CEQMA (CSIC-Universidad de Zaragoza).