The synthesis of novel well-defined alkyne side chain functional polymers featuring narrow molecular weight distributions (PDI = 1.09−1.17) by living radical polymerization is described. Grafting of protected and unprotected carbohydrates is achieved via either a C-6 or an anomeric azide (α or β) onto these polymers by Cu(I)-catalyzed “click chemistry”, providing a simple and efficient route to synthetic glycopolymers. The strategy provides an extremely powerful tool for the synthesis of libraries of materials that differ only in the nature of the sugar moiety presented on a well-defined polymer scaffold. A library of multivalent ligands were then prepared following a “coclicking” synthetic protocol, and the reactivity of these glycopolymers in the presence of concanavalin A and Ricinus communis agglutinin, model lectins able to selectively bind appropriate mannose and galactose derivatives, respectively, was assessed.

A series of alpha-functional maleimide polymethacrylates (M(n) = 4.1-35.4 kDa, PDi = 1.06-1.27) have been prepared via copper-catalyzed living radical polymerization (LRP). Two independent synthetic protocols have been successfully developed and the polymers obtained in multigram scale, with an 80-100% content of maleimide reactive chain ends, depending on the method employed. A method for the synthesis of amino-terminated polymers, starting from Boc-protected amino initiators, has also been developed, as these derivatives are key intermediates in one of the two processes studied in the present work. The alternative synthetic pathway involves an initiator containing a maleimide unit "protected" as a Diels-Alder adduct. After the polymerization step, the maleimide functionality has been reintroduced by retro-Diels-Alder reaction, by simply refluxing those polymers in toluene for 7 h. These maleimido-terminated materials, poly(methoxyPEG((475))) methacrylates and poly(glycerol) methacrylates, differ for both the nature and size of the polymer side branches and showed an excellent solubility in water, a property that made them an ideal candidate for the synthesis of new polymer-(poly)peptide biomaterials. These functional polymers have been successfully employed in conjugation reactions in the presence of thiol-containing model substrates, namely, reduced glutathione (gamma-Glu-Cys-Gly) and the carrier protein, bovine serum albumin (BSA), in 100 mM phosphate buffer (pH 6.8-7.4) and ambient temperature.

Combinations of synthetic and natural macromolecules offer a route to new functional materials. While biological and polymer chemistry may not be natural bedfellows, many researchers are focusing their attention on the benefits of combining these fields. Recent advances in living radical polymerization have provided methods to build tailor‐made macromolecular moieties using relatively simple processes. This has led to a plethora of block copolymers, end‐functional polymers and polymers with a whole range of biological recognition abilities. This review covers work carried out until late 2006 combining living radical polymerization with proteins and peptides in the rapidly‐expanding field of bioconjugation.magnified image