The combination of controlled polymerization techniques and “click” reactions form an efficient platform for the preparation of polymers in various architectures. In this critical review, an update of our 2007 review in Chem. Soc. Rev., we focus on the “click” reactions that have been used widely in the last four years to create new polymer architectures. Not only block copolymers and star-shaped polymers but also cyclic and dendritic macromolecules could be synthesized using these robust “click” reactions (205 references).

“Clicking” on/with polymers: a rapidly expanding field for the straightforward preparation of novel macromolecular architectures

Owing to their low toxicity, biocompatibility and biodegradability, aliphatic poly(carbonate)s have been widely studied as materials for biomedical application. Furthermore, the synthetic versatility of the six-membered cyclic carbonates for the realization of functional degradable polymers by ring-opening polymerisation has driven wider interest in this area. In this review, the synthesis and ring-opening polymerisation of functional cyclic carbonates that have been reported in the literature in the past decade are discussed. Finally, the post-polymerisation modification methods that have been applied to the resulting homopolymers and copolymers and the application of the materials are also discussed.

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Synthesis and post-polymerisation modifications of aliphatic poly(carbonate)s prepared by ring-opening polymerisation.

Polymeric nanostructured materials for biomedical applications

Both function and use of nanoparticles (NPs) to a great extent are dominated by interfacial energies, which in turn can be addressed by chemical modifications. This article focuses exclusively on the use of ‘click’-chemistry for NP-surface modification, also putting a major focus on the application of the resulting NPs in bio- and nanoscience. As ‘click’-chemistry is a universal method to link reaction partners in high efficiency, solvent insensitivity and at moderate reaction conditions, its use for engineering NP surfaces has become widespread. The basic approach of Cu(I)-catalyzed azide/alkyne-‘click’ (CuAAC) chemistry for NP-science is elucidated in this article, together with the applications of the resulting surface modified NPs in medicine, nanotechnology and bioassay-science.

Click-chemistry for nanoparticle-modification

Single-chain polymer nanoparticles via reversible disulfide bridges

We present the synthesis of discrete functionalized polyester nanoparticles in selected nanoscale size dimensions via a controlled intermolecular chain cross-linking process facilitated via “click”-chemistry approaches such as the Cu(I)-catalyzed 1,3-dipolar cycloaddition of azides and thiol−ene reactions. Both “click” reactions led to the formation of well-defined nanoparticles with narrow size distribution and selected nanoscopic size dimensions. The controlled coupling involves the cross-linking of an alkyne functionalized polyester with a bisazide, 1,8-diazide-3,6-dioxaoctane, and an allyl functionalized polyester with 3,6-dioxa-1,8-octanedithiol. The linear functional polyester precursors were synthesized via ring-opening copolymerization of δ-valerolactone and α-propargyl-δ-valerolactone as well as with α-ally-δ-valerolactone, respectively. We found that the nanoparticle formation and the control over the nanoscopic dimension are primarily influenced by the degree of the alkyne or allyl entity imple...

Jared Katz

Papers

``Click'' Reactions: Novel Chemistries for Forming Well-defined Polyester Nanoparticles