This review explores the different synthetic methods by which dispersity and MWD shape can be tuned and discusses the different properties and applications where this variation is beneficial.

Dispersity significantly affects the properties of polymers. However, current methods for controlling the polymer dispersity are limited to bimodal molecular weight distributions, adulterated polymer chains, or low end‐group fidelity and rely on feeding reagents, flow‐based, or multicomponent systems. To overcome these limitations, we report a simple batch system whereby photoinduced atom transfer radical polymerisation is exploited as a convenient and versatile technique to control dispersity of both homopolymers and block copolymers. By varying the concentration of the copper complex, a wide range of monomodal molecular weight distributions can be obtained (Đ=1.05–1.75). In all cases, high end‐group fidelity was confirmed by MALDI‐ToF‐MS and exemplified by efficient block copolymer formation (monomodal, Đ=1.1–1.5). Importantly, our approach utilises ppm levels of copper (as low as 4 ppm), can be tolerant to oxygen and exhibits perfect temporal control, representing a major step forward in tuning polymer dispersity for various applications.

Reversible addition-fragmentation chain transfer (RAFT) polymerization has been widely utilized to produce low-dispersity (co)polymers by employing a single highactivity RAFT agent. Anastasaki and co-workers reported RAFT polymerization by mixing one high-activity and one low-activity RAFT agent to tune the dispersity for a wide range of polymer classes. In all cases, monomodal molecular weight distributions were obtained, and this method was further applied to the preparation of block co-polymers, where successful chain extension was observed, independent of initial dispersity.

The immense application potential of amphiphilic protein-polymer conjugates remains largely unexplored, as established "grafting from" synthetic protocols involve time-consuming, harsh and disruptive deoxygenation methods, while "grafting to" approaches result in low yields. Here we report an oxygen tolerant, photoinduced CRP approach which readily affords quantitative yields of protein-polymer conjugates within 2 h, avoiding damage to the secondary structure of the protein and providing easily accessible means to produce biomacromolecular assemblies. Importantly, our methodology is compatible with multiple proteins (e.g. BSA, HSA, GOx, beta-galactosidase) and monomer classes including acrylates, methacrylates, styrenics and acrylamides. The polymerizations are conveniently conducted in plastic syringes and in the absence of any additives or external deoxygenation procedures using low-organic content media and ppm levels of copper. The robustness of the protocol is further exemplified by its implementation under UV, blue light or even sunlight irradiation as well as in buffer, nanopure, tap or even sea water.

This manuscript is dedicated to Professor Mitsuo Sawamoto's outstanding achievements in polymer chemistry and recognizes his recent retirement from 40 years of exceptional service to Kyoto University.To address this challenge and provide insight into photo-CRP processes, a recently developed in situ NMR spectroscopy method is utilized to evaluate temporal control for a selection of widely studied photo-CRP processes (see Fig. 1 and Supplementary Information Figure S1 for a Additional supporting information may be found in the online version of this article.