Front Cover: This work represents the RAFT copolymerization of the phosphine-functional styrenic monomer, 4-(diphenylphosphino)styrene, with styrene. Copolymerization behaviour is explored to establish the statistical distribution of the phosphine functionality within the copolymer. There is a strong tendency for the phosphine-bearing monomer to homopolymerize whilst styrene prefers to copolymerize. This results in the polymer possessing gradient-microstructure from preferential incorporation of phosphine-based functionality. Further details can be found in the article by Kyle J. Sykes, Simon Harrisson, and Daniel J. Keddie* on page 2310.

Molecular polymer brushes present an emerging class of polymer nanostructures with the potential to address persevering problems in nanomedicine. Recent improvements in the synthesis of these polymeric architectures allowed the tailoring of sophisticated nanomaterials for applications in drug and gene delivery, as well as the design of new imaging probes and prototype nanomaterials.

Polymeric drift control adjuvants (DCAs) increase the droplet size produced during agricultural spraying which minimizes drift of agrichemicals. Current DCAs are reviewed, highlighting key weaknesses and the mechanism through which they increase droplet size. A discussion on the applicability of new polymer chemistries and architectures to drift control then follows.

A study of the thermally triggered antibiotic release from poly(diethylene glycol methylether methacrylate) brush modified bottle-neck porous silicon shows a ninefold increase in release rate when the temperature is switched above the lower critical solution temperature.

A two-step synthetic technique is employed to grow hyperbranched polyglycerols (HPGs) within a previously unreported size range for these polymers. Successive precipitation of crude alkyne functional HPGs results in the isolation of a range of molecular weight polymers each with low polydispersity.

Novel hybrid star polymers with a polyhedral oligomeric silsesquioxane core and eight partly fluorinated copolymer arms are synthesized through R-group approach by reversible addition–fragmentation chain transfer (RAFT) polymerization. The ¹⁹F magnetic resonance imaging (MRI) capability is preliminarily confirmed by a single and strong ¹⁹F resonance in ¹⁹F nuclear magnetic resonance (NMR), and the imaging intensity is also calculated for a spin-echo pulse sequence.

This article presents the results obtained from advanced ¹H, ¹³C, and ¹⁹F NMR spectroscopy experiments using decoupling strategies, to ascertain unequivocally the microstructure of PVDF synthesized via RAFT polymerization. An uncommon NMR heteronuclear coupling between the proton of the stereocenter of the CTA R-group and the fluorine atoms of the CF₂ moiety of the first added VDF unit is highlighted.

¹H DOSY NMR provides a simple and convenient way to determine both the weight-average molecular weight M_w and the Flory exponent of poly(N-acryloylmorpholine) (PNAM) in various organic and aqueous solvents. Determination of the average diffusion coefficients D_PNAM of PNAM samples synthesized by reversible addition fragmentation chain transfer polymerization with various molecular weights leads to highly linear relationship between Log D_PNAM and Log M_w.

This study presents control of PMMA particle size over an unprecedented range (0.3–5.3 μm) using only a single stabilizer by free radical dispersion polymerization in scCO₂. This study explores also delayed monomer addition to considerably reduce batch-to-batch variability and reduced agglomeration between particles.

Conjugation of agmatine to poly(methacrylic acid) can enhance the cellular uptake of the polymer by cancer cells. It is observed that only small amounts of guanidinium are required to achieve a visibly increased cellular uptake. These nontoxic polymers with zwitterionic structure can be useful for polymer–drug conjugates to assist the efficient delivery of drugs into cells.

RAFT copolymerization of styrene and 4-(diphenylphosphino)styrene is explored to establish the statistical distribution of the phosphine-functional monomer within the copolymer. RAFT copolymerization provides phosphine-functional copolymers of low dispersity. Estimation of reactivity ratios indicates DPPS has a strong tendency to homopolymerize while St preferentially copolymerizes with DPPS. Block copolymers as well as polymeric phosphine oxides and phosphonium salts are also prepared.

Intensively investigated as photocatalysts for the photodegradation of persistent organic contaminants, TiO₂ nanomaterials can be tamed to enable miniemulsion photopolymerization. In particular, colloidal and supported titania offer many advantages compared to conventional molecular photoinitiator: facile addition to the monomer dispersion, high surface-to-volume ratio, nonmigrating, no byproducts, simple and low cost process, and possible recovery/reuse.

Profluorescent nitroxides (PFNs) are an important class of imaging agents for monitoring intracellular redox status and oxidative stress levels. The preparation of nitroxide-containing polymers of different chain length coupled to a fluorophore and their reduction with pentafluorophenylhydrazine are reported. The fluorescence switch-on kinetics and radical concentrations are monitored by fluorescence and EPR spectroscopy and compared to a conventional single-nitroxide PFN.