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This Protocol introduces biomass-derived carbon nanodots as emerging photoinitiating materials in conventional radical polymerization (Type I and Type II systems) and as photocatalysts for atom transfer radical polymerization-based polymerization.

Polymer materials suffer mechano-oxidative deterioration or degradation in the presence of molecular oxygen and mechanical forces. Here the authors demonstrate a synthetic approach in which molecular oxygen and mechanical energy synergistically initiate polymerization and affords robustness in polymeric materials.

Therapeutic proteins are often conjugated with polymers, but separating the conjugate from unconjugated protein and free polymer is a major challenge. Here, the authors discover that proteins conjugated to charged or zwitterionic polymers maintain solubility in 100% ammonium sulfate, greatly simplifying purification.

Developing materials for uranium harvesting from seawater with high adsorption capacity remains challenging. Here, the authors develop a new protocol, by combining multi-scale computational simulations with the PET-RAFT polymerization, for rational design and precise synthesis of block copolymers with optimal architectures and atomic economy, achieving a capacity of 11.4 mg/g within 28 days.

Surface-active macromolecules that are chemically different can be mixed at fluid interfaces if the molecules attract each other, or if they have complementary shapes and a net attraction is induced by a depletant. Now, a strategy that eludes the need for complementarity between the molecules, where tethered molecular brushes induce an entropic net repulsion between like species, achieves long-range arrays of perfectly mixed macromolecules.

A polymer code based on a triplet of parameters—network strand length, side-chain length and grafting density—enables materials to be designed with specific combinations of mechanical properties to mimic biological materials.

The topology of polymers could be carefully controlled if the monomers were to be well-defined in sequence and regiochemical linkage. Here the authors present a method to synthesize oligomers of controlled sequence and regiochemistry, formed through iterative liquid-phase boronate-tagged syntheses, which are precursors to topologically distinct polymers.

Synthesis of protein-polymer conjugates typically relies on multi-step processes in solution and on challenging purification strategies. Here the authors show a robust synthesis approach which eliminates purification processes by immobilizing proteins reversibly on modified agarose beads before grafting from polymers via ATRP.

Generally cubosomes are formed by the self-assembly of surfactants such as lipids and are used as adsorbents or in host-guest applications. Here the authors have shown that an amphiphilic block copolymer can form nanoscale cuboidal particles with a bicontinuous cubic phase.

Conjugation of exendin-4 — a drug to treat type 2 diabetes — with a poly(ethylene glycol) (PEG)-based brush polymer reduces the conjugate's reactivity towards anti-PEG antibodies and leads to lower blood glucose levels in mice for up to 5 days after a single injection.

During free-radical polymerization of multivinyl monomers, the regulation of intermolecular crosslinking and intramolecular cyclization enables the construction of complex polymer architectures. This Review summarizes methods to achieve this control and techniques to analyse the sub-chain connections. Finally, it discusses exemplary biomedical applications of the complex polymer products.

Atom transfer radical polymerization (ATRP) is a technique that employs the transfer of a halogen or pseudohalogen group between a catalyst and a monomeric or polymeric radical to generate and elongate polymers, respectively. In this Primer, Harrisson et al. describe considerations for ATRP, its available initiators, catalysts and mechanisms, the range of structures that can be generated and techniques for assessing the ATRP product, concluding with an overview of upcoming developments in the field.

Eutectic Ga-In droplets can be functionalized with various polymers and co-polymers using atom transfer radical polymerization. The droplets are ready for direct solution processing to form liquid-metal nanocomposites for potential applications in soft robotics.

Solvent-free, supersoft and superelastic polymer melts and networks made from bottlebrush macromolecules can display low modulus, high strain at break, and extraordinary elasticity.

The polymer materials of the twenty-first century will be complex chemical systems that can respond and adapt to their environment. Such materials can be attained by synthesizing precision macromolecules with controlled architectures, and by mastering polymer interactions and self-organization.

The simplicity and broad applicabilty of atom transfer radical polymerization make it a rapidly developing area of synthetic polymer chemistry. Here, the fundamentals of the technique are discussed, along with how it can be used to synthesize macromolecules with controlled molecular architecture, and how their self-assembly can create nanostructured functional materials.