On‐POM Ring‐Opening Polymerisation of N‐Carboxyanhydrides

Abstract

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.

Exploiting Interactions between Polyoxometalates and Proteins for Applications in (Bio)chemistry and Medicine

“…[89] Additionally, Mn-centered Anderson-Evans HPOMs have also been recently employed for the formation of novel "POMlymers" in which POMs are covalently conjugated with polypeptide chains. [90,91] In aqueous conditions the amphiphilic POMlymers self-assemble into nanoparticles, with the POM located deep within the hydrophobic core, ensuring that the catalytic activity is well preserved. [90] Moreover, the nanoparticles displayed enhanced antimicrobial activity with respect to the POM without the polypeptide and demonstrated better inhibition of bacterial biofilm formation than the corresponding ionic assembly of the POM with the polypeptide lacking any covalent linkage.…”

“…For example, the binding of a known DnaK‐binding peptide towards the bacterial DnaK protein was studied, with a 2.5‐fold increase in protein affinity following incorporation of a POM‐AA [89] . Additionally, Mn‐centered Anderson–Evans HPOMs have also been recently employed for the formation of novel “POMlymers” in which POMs are covalently conjugated with polypeptide chains [90, 91] . In aqueous conditions the amphiphilic POMlymers self‐assemble into nanoparticles, with the POM located deep within the hydrophobic core, ensuring that the catalytic activity is well preserved [90] .…”

Synthesis of metal‐containing Schiff based cyclomatrix polyphosphazene microspheres based on polyoxometalates and application in flame retardance for epoxy resin

“…17,18 Recently, POMs as catalyst or flame retardant have also been applied in polymer matrices. 19,20 As one of the six basic POM structures, Anderson clusters can be directly modified with the tris(hydroxymethyl)aminomethane (Tris). [Al(OH) 6 Mo 6 O 18 ] 3À , a typical Andersontype POM, can be decorated with Tris just on single-side to obtain [N(C 4 H 9 ) 4 ] 3 [AlMo 6 O 18 (OH) 3 {(OCH 2 ) 3 CNH 2 }] (NH 2 -AlMo 6 ), which provides a platform for the singleside functionalization of Anderson-type POMs.…”

“…Polyoxometalates (POMs) are a kind of early transition metal oxygen clusters with flexibility in adjustable composition and size, which promotes the studies of POMs in different fields such as catalysis, biomedicine, and materials 17,18 . Recently, POMs as catalyst or flame retardant have also been applied in polymer matrices 19,20 . As one of the six basic POM structures, Anderson clusters can be directly modified with the tris(hydroxymethyl)aminomethane (Tris).…”