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The performance of antimicrobial polymers depends sensitively on the type of cationic species, charge density, and spatial arrangement of cations. Here we report antimicrobial polymers bearing unusually bulky tetraaminophosphonium groups as the source of highly delocalized cationic charge. The bulky cations drastically enhanced the biocidal activity of amphiphilic polymers, leading to remarkably potent activity in the submicromolar range. The cationic polynorbornenes with pendent tetraaminophosphonium groups killed over 98% E. coli at a concentration of 0.1 μg/mL and caused a 4-log reduction of E. coli within 2 h at a concentration of 2 μg/mL, showing very rapid and potent bactericidal activity. The polymers are also highly hemolytic at similar concentrations, indicating a biocidal activity profile. Polymers of a similar chemical structure but with more flexible backbones were made to examine the effects of the flexibility of polymer chains on their activity, which turned out to be marginal. We also explore variants with different spacer arm groups separating the cations from the backbone main chain. The antibacterial activity was comparably potent in all cases, but the polymers with shorter spacer arm groups showed more rapid bactericidal kinetics. Interestingly, pronounced counterion effects were observed. Tightly bound PF6– counteranions showed poor activity at high concentrations due to gross aggregate formation and precipitation from the assay media, whereas loosely bound Cl– counterions resulted in very potent activity that monotonically increased with increasing concentration. In this paper, we reveal that bulky phosphonium cations are associated with markedly enhanced biocidal activity, which provides an innovative strategy to develop more effective self-disinfecting materials. 

Model poly(n-butyl acrylate) (PBA) networks were prepared by photoinduced atom transfer radical polymerization (photoATRP), followed by curing of polymer stars via atom transfer radical coupling (ATRC) with a nitrosobenzene radical trap. The resulting nitroxyl radical installed thermally labile alkoxyamine functional groups at the junctions of the network. The alkoxyamine crosslinks of the network were degraded back to star-like products upon exposure to temperatures above 135 °C. Characterization of the degraded products via gel permeation chromatography (GPC) confirmed the inversion of polymer topology after thermal treatment.