Ring-opening metathesis polymerization of N-methylpyridinium-fused norbornenes to access antibacterial main-chain cationic polymers.

Cationic polymers have been identified as a promising type of antibacterial molecules, whose bioactivity can be tuned through structural modulation. Recent studies suggest that the placement of the cationic groups close to the core of the polymeric architecture rather than on appended side chains might improve both their bioactivity and selectivity for bacterial cells over mammalian cells. However, antibacterial main-chain cationic polymers are typically synthesized via polycondensations, which do not afford precise and uniform molecular design. Therefore, accessing main-chain cationic polymers with high degrees of molecular tunability hinges upon the development of controlled polymerizations tolerating cationic motifs (or cation progenitors) near the propagating species. Herein, we report the synthesis and ring-opening metathesis polymerization (ROMP) of N-methylpyridinium-fused norbornene monomers. The identification of reaction conditions leading to a well-controlled ROMP enabled structural diversification of the main-chain cationic polymers and a study of their bioactivity. This family of polyelectrolytes was found to be active against both Gram-negative (Escherichia coli) and Gram-positive (Methicillin-resistant Staphylococcus aureus) bacteria with minimal inhibitory concentrations as low as 25 µg/mL. Additionally, the molar mass of the polymers was found to impact their hemolytic activity with cationic polymers of smaller degrees of polymerization showing increased selectivity for bacteria over human red blood cells.

Expedient Synthesis and Ring-Opening Metathesis Polymerization of Pyridinonorbornenes.

Pyridine-containing polymers are promising materials for a variety of applications from the capture of contaminants to the self-assembly of block copolymers. However, the innate Lewis basicity of the pyridine motif often hampers living polymerization catalyzed by transition-metal complexes. Herein, we report the expedient synthesis of pyridinonorbornene monomers via a [4+2] cycloaddition between 2,3-pyridynes and cyclopentadiene. Well-controlled ring-opening metathesis polymerization was enabled by careful structural design of the monomer. Polypyridinonorbornenes exhibited high Tg and Td, a promising feature for high-temperature applications. Investigation of the polymerization kinetics and of the reactivity of the chain ends shed light on the influence of nitrogen coordination on the chain-growth mechanism.

Switchable Polymerization Catalysis Using a Tin(II) Catalyst and Commercial Monomers to Toughen Poly(l-lactide).

Sustainable plastics sourced without virgin petrochemicals, that are easily recyclable and with potential for degradation at end of life, are urgently needed. Here, copolymersand blends meeting these criteria are efficiently prepared using a single catalyst and existing commercial monomers l-lactide, propylene oxide, and maleic anhydride. The selective, one-reactor polymerization applies an industry-relevant tin(II) catalyst. Tapered, miscible block polyesters are formed with alkene groups which are postfunctionalized to modulate the polymer glass transition temperature. The polymers are blended at desirable low weight fractions (2 wt %) with commercial poly(l-lactide) (PLLA), increasing toughness, and elongation at break without compromising the elastic modulus, tensile strength, or thermal properties. The selective polymerization catalysis, using commercial monomers and catalyst, provides a straightforward means to improve bioplastics performances.

Isoselective Lactide Ring Opening Polymerisation using [2]Rotaxane Catalysts.

Polylactide (PLA) is a fully biodegradable and recyclable plastic, produced from a bio-derived monomer: it is a circular economy plastic. Its properties depend upon its stereochemistry and isotactic PLA shows superior thermal-mechanical performances. Here, a new means to control tacticity by exploiting rotaxane conformational dynamism is described. Dynamic achiral [2]rotaxanes can show high isoselectivity (Pi =0.8, 298 K) without requiring any chiral additives and enchain by a chain end control mechanism. The organocatalytic dynamic stereoselectivity is likely applicable to other small-molecule and polymerization catalyses.