The importance of stereochemistry to the function of molecules is generally well understood. However, to date, control over stereochemistry and its potential to influence properties of the resulting polymers are, as yet, not fully realised. This review focuses on the state-of-the-art with respect to how stereochemistry in polymers has been used to influence and control their physical and mechanical properties as well as begin to control their function. A brief overview of the synthetic methodology by which to access these materials is included, with the main focus directed towards stereochemical control over properties such as mechanical, biodegradation and conductivity. Additionally, the advances being made towards enantioseparation, enantioselective catalyst supports and stereo-directed transitions are discussed. Finally, we also consider the opportunities that the rich stereochemistry of sustainably-sourced monomers could offer in this field. Where possible, parallels and general design principles are drawn together to identify opportunities and limitations that these approaches may present in their effects on materials properties, performance and function.

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The physical properties of cyclic and linear polymers are markedly different; however, there are few examples which exploit these differences in clinical applications. In this study, we demonstrate that self-assemblies comprised of cyclic-linear graft copolymers are significantly more stable than the equivalent linear-linear graft copolymer assemblies. This difference in stability can be exploited to allow for triggered disassembly by cleavage of just a single bond within the cyclic polymer backbone, via disulfide reduction, in the presence of intracellular levels of l-glutathione. This topological effect was exploited to demonstrate the first example of topology-controlled particle disassembly for the controlled release of an anti-cancer drug in vitro. This approach represents a markedly different strategy for controlled release from polymer nanoparticles and highlights for the first time that a change in polymer topology can be used as a trigger in the design of delivery vehicles. We propose such constructs, which demonstrate disassembly behavior upon a change in polymer topology, could find application in the targeted delivery of therapeutic agents.

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The controlled ring-opening polymerisation (ROP) of α-bromo-ε-caprolactone (αBrCL), a derivative of ε-caprolactone (εCL), and its copolymerisation with εCL is reported.

The synthesis of well‐defined propargyl‐functional aliphatic polycarbonates is achieved via the organocatalytic ring‐opening polymerization of prop‐2‐yn‐1‐yl 2‐oxo‐1,3,6‐dioxazocane‐6‐carboxylate (P‐8NC) using a wide variety of commercially available or readily made, shelf‐stable organocatalysts. The resulting homopolymers show low dispersities and end‐group fidelity, with the versatility of the system being demonstrated by the synthesis of telechelic copolymers and block copolymers with molar mass up to 40 kDa.

Hyperbranched, biodegradable PCL-based polymers are obtained through a random but invasive migration of an in-situ generated carbene end group which is unmasked via the thermolysis of its precursor diazirine moiety....