Controlling enzyme hydrolysis of branched polymers synthesised using transfer-dominated branching radical telomerisation via telogen and taxogen selection.

With the ever-growing reliance on polymeric materials for numerous applications, new avenues to induce, design and control degradation are clearly important. Here, we describe a previously unreported approach to controlling enzymatic hydrolysis of high molecular weight branched polymers formed from the new free-radical polymer synthesis strategy transfer-dominated branching radical telomerisation (TBRT). Modifying the chemical nature of TBRT polymers may be accomplished through telogen selection and multi-vinyl taxogen (MVT) design, and we show telogen-driven control of enzyme-catalysed hydrolysis and the impact of careful placement of hydrolytically susceptible groups within readily synthesised MVTs.

Sustainable formulation polymers for home, beauty and personal care: challenges and opportunities.

As society moves towards a net-zero future, the need to adopt more sustainable polymers is well understood, and as well as plastics, less visible formulation polymers should also be included within this shift. As researchers, industries and consumers move towards more sustainable products there is a clear need to define what sustainability means in fast moving consumer goods and how it can be considered at the design stage. In this perspective key challenges in achieving sustainable formulation polymers are highlighted, and opportunities to overcome them are presented.

Model Diels-Alder Studies for the Creation of Amphiphilic Cross-Linked Networks as Healable, Antibiofouling Coatings.

Diels-Alder (DA) chemistry was used in the construction of amphiphilic cross-linked polymer networks comprised of furan-functionalized hyperbranched fluoropolymers and maleimide-functionalized linear poly(ethylene glycol)s, which were designed as antibiofouling coatings capable of repair. Discrete molecules and a linear polymer analog were studied as model systems to understand the nature of the thermally reversible [4 + 2] cycloaddition reaction involving a tetrafluorobenzylfuranyl ether unit, which was part of the structure for the incorporation of the DA functionalities into the composite network materials. Atomic force microscopy confirmed the complex, nanoscopically resolved topography needed for antibiofouling.

Antibiofouling hybrid dendritic Boltorn/star PEG thiol-ene cross-linked networks.

A series of thiol-ene generated amphiphilic cross-linked networks was prepared by reaction of alkene-modified Boltorn polyesters (Boltorn-ene) with varying weight percent of 4-armed poly(ethylene glycol) (PEG) tetrathiol (0-25 wt%) and varying equivalents of pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) (0-64 wt%). These materials were designed to present complex surface topographies and morphologies, with heterogeneity of surface composition and properties and robust mechanical properties, to serve as nontoxic antibiofouling coatings that are amenable to large-scale production for application in the marine environment. Therefore, a two-dimensional matrix of materials compositions was prepared to study the physical and mechanical properties, over which the compositions spanned from 0 to 25 wt% PEG tetrathiol and 0-64 wt% PETMP (the overall thiol/alkene (SH/ene) ratios ranged from 0.

Evaluation of Isoprene Chain Extension from PEO Macromolecular Chain Transfer Agents for the Preparation of Dual, Invertible Block Copolymer Nanoassemblies.

Two RAFT-capable PEO macro-CTAs, 2 and 5 kDa, were prepared and used for the polymerization of isoprene which yielded well-defined block copolymers of varied lengths and compositions. GPC analysis of the PEO macro-CTAs and block copolymers showed remaining unreacted PEO macro-CTA. Mathematical deconvolution of the GPC chromatograms allowed for the estimation of the blocking efficiency, about 50% for the 5 kDa PEO macro-CTA and 64% for the 2 kDa CTA.