Stereocomplexed Functional and Statistical Poly(lactide-carbonate)s via a Simple Organocatalytic System.

The stereocomplexation of polylactide (PLA) has been widely relied upon to develop degradable, sustainable materials with increased strength and improved material properties in comparison to stereopure PLA. However, forming functionalized copolymers of PLA while retaining high crystallinity remains elusive. Herein, the controlled ring-opening copolymerization (ROCOP) of lactide (LA) and functionalized cyclic carbonate monomers is undertaken.

Enhancing Dual-State Emission in Maleimide Fluorophores through Fluorocarbon Functionalisation.

Herein, a library of trifluoroethyl substituted aminomaleimide derivatives are reported with small size and enhanced emissions in both solution and solid-state. A diCH CF substituted aminochloromaleimide exhibits the most efficient dual-state emission (Φ >50 % in solution and solid-state), with reduced quenching from protic solvents. This is attributed to the reduction of electron density on the maleimide ring and suppressed π-π stacking in the solid-state.

Rigidochromism by imide functionalisation of an aminomaleimide fluorophore.

Fluorescent dyes that exhibit high solid state quantum yields and sensitivity to the mechanical properties of their local environment are useful for a wide variety of applications, but are limited in chemical diversity. We report a trityl-functionalised maleimide that displays rigidochromic behaviour, becoming highly fluorescent when immobilised in a solid matrix, while displaying negligible fluorescence in solution. Furthermore, the dye's quantum yield is shown to be sensitive to the nature of the surrounding matrix.

DNA-polymer conjugates the graft-through polymerisation of native DNA in water.

The direct, graft-through, ring-opening metathesis polymerisation (ROMP) of unprotected DNA macromonomers is reported. By tuning the polymerisation conditions, good control is achieved, enabling the rapid and efficient synthesis of DNA-containing bottlebrush copolymers, without the need for protection of the DNA bases.

Manipulating the fluorescence lifetime at the sub-cellular scale via photo-switchable barcoding.

Fluorescent barcoding is a pivotal technique for the investigation of the microscale world, from information storage to the monitoring of dynamic biochemical processes. Using fluorescence lifetime as the readout modality offers more reproducible and quantitative outputs compared to conventional fluorescent barcoding, being independent of sample concentration and measurement methods. However, the use of fluorescence lifetime in this area has been limited by the lack of strategies that provide spatiotemporal manipulation of the coding process.

Tuning the membrane permeability of polymersome nanoreactors developed by aqueous emulsion polymerization-induced self-assembly.

Polymeric vesicles (or polymersomes) are hollow bilayer structures consisting of an inner aqueous compartment enclosed by a hydrophobic membrane. Vesicular constructs are ubiquitous in nature and perform a variety of functions by compartmentalizing molecules into disparate environments. For polymer chemists, the synthesis of vesicles can be readily accomplished using polymerization-induced self-assembly (PISA), whereby pure vesicle morphologies can be easily accessed by tuning initial reaction parameters.

Rational design of substituted maleimide dyes with tunable fluorescence and solvafluorochromism.

A series of maleimide derivatives were systematically designed and synthesized with tunable fluorescent properties. The facile modifications herein provide a simple methodology to expand the scope of maleimide-based dyes and also provide insight into the relationship between substitution pattern and optical properties.

Poly(oligo(ethylene glycol) vinyl acetate)s: A Versatile Class of Thermoresponsive and Biocompatible Polymers.

Polymers with a thermally triggered phase transition are important in the design of materials for biological applications, where their behavior can be used to trigger release or (dis)assembly events. Despite their advantages, a system with tunable thermal response, end-group reactive sites, low toxicity, and controlled main-chain degradability has not been realized, yet this would be a significant advance. The versatile new poly(oligo(ethylene glycol) vinyl acetate)s are presented with excellent control over their molecular properties obtained through RAFT/MADIX polymerization.

Catalytic reduction of dioxygen with modified Thermus thermophilus cytochrome c552.

Efficient catalysis of the oxygen reduction reaction (ORR) is of central importance to function in fuel cells. Metalloproteins, such as laccase (Cu) or cytochrome c oxidase (Cu/Fe-heme) carry out the 4H(+)/4e(-) reduction quite efficiently, but using large, complex protein frameworks. Smaller heme proteins also can carry out ORR, but less efficiently.