This paper describes both well-established routes and recent advances in the end group modification of polymers synthesised by reversible addition–fragmentation chain transfer (RAFT) polymerisation. The lability of the thiocarbonylthio group, which facilitates the RAFT mechanism, allows for ready post-polymerisation functionalisation of RAFT polymers by a number of techniques. In particular, end group thermolysis, radical induced reduction, hetero-Diels–Alder reactions and reaction with nucleophiles are discussed as are the applications and limitations of each method. The versatility of RAFT as a polymerisation tool for the synthesis of polymers with functional end groups for a range of applications is demonstrated.

Polymer vesicles prepared by self-assembly techniques have attracted increasing scientific interest in recent years. This is as a result of their numerous potential applications such as tunable delivery vehicles, for the templating of biomineralization, as nanoreactors and as scaffolds for biological conjugation. Presented in this review are the recent advances in the preparation and application of ‘smart’ and functional block copolymer vesicles such as those which respond to external stimuli to afford a change in structure, morphology or controlled release event. In this Highlight, we first give an overview of the structure of polymer vesicles, followed by a summary of the methods used for their preparation. We then focus on recently developed intelligent polymer vesicles which can respond to the application of external stimuli such as a change in temperature, pH or redox to afford novel nanomaterials. The potential applications of these materials are explored with specific focus on the functionalization of various domains of the polymer vesicles. Finally, the current limitations in the preparation and application of polymer vesicles are explored as are the challenges facing the development of these nanostructures towards real-world applications.

Anisotropic particles, such as patchy, multicompartment and Janus particles, have attracted significant attention in recent years due to their novel morphologies and diverse potential applications. The non-centrosymmetric features of these particles make them a unique class of nano- or micro-colloidal materials. Patchy particles usually have different compositional patches in the corona, whereas multicompartment particles have a multi-phasic anisotropic architecture in the core domain. In contrast, Janus particles, named after the double-faced Roman god, have a strictly biphasic geometry of distinct compositions and properties in the core and/or corona. The term Janus particles, multicompartment particles and patchy particles frequently appears in the literature, however, they are sometimes misused due to their structural similarity. Therefore, in this critical review we classify the key features of these different anisotropic colloidal particles and compare structural properties as well as discuss their preparation and application. This review brings together and highlights the significant advances in the last 2 to 3 years in the fabrication and application of these novel patchy, multicompartment and Janus particles (98 references).

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The synthesis and self-assembly of poly(lactide)-b-poly(acrylic acid) and poly(lactide)-b-poly(dimethylaminoethylacrylate) block copolymers by a combination of ring-opening polymerization and reverse-addition fragmentation chain transfer (RAFT) polymerization is reported. Self-assembly of block copolymers containing enantiopure homochiral poly(lactide), PLA, by a simple direct dissolution methodology results in core-crystallization to afford micelles with a cylindrical morphology. Amorphous atactic PLA cores and conditions that did not promote crystallization resulted in spherical micelles. Cylindrical micelles were characterized by transmission electron microscopy (TEM) with cryo-TEM, small angle neutron scattering (SANS) and angular dependent dynamic light scattering (DLS) proving that the cylindrical morphology was persistent in solution. Manipulation of the assembly conditions enabled the length and dispersity of the resultant cylindrical micelles to be controlled.