Glycopolymers are synthetic polymers possessing a non-carbohydrate main chain but featuring pendant and/or terminal carbohydrate moieties. Since the pioneering work of Horejsi et al., glycopolymers have raised an ever-increasing interest as artificial materials for a number of biological and biomedical uses. This is due to the expectation that polymers displaying carbohydrate functionalities similar to those of natural glycoconjugates might be able to mimic, or even exceed, their performance in specific applications (biomimetic approach). The presence of an appropriate carbohydrate in a glycolpolymer though, is per se insufficient to bestow it with the biological and physicochemical properties required, while control of the macromolecular architecture and composition has proven essential to enable sophisticated functions and to allow a precise correlation between these functions and the polymer structure.

In this seminar I will present a few examples of the design and synthesis of glycopolymers drawn from my personal experience. In particular, the opportunities offered by Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization for glycopolymer synthesis directly in water will be discussed [1], as well as its application to the preparation of statistical [2], di-block [3] and tri-block copolymers [4], some of them capable to self-assembly in a selective solvent. Finally, the use of (1→4)-α-L-guluronan oligomers extracted from alginate as building blocks in the synthesis of biohybrid glycopolymers and chimeric polysaccharides with original gelation properties will be detailed [5].

References [1] – (a) Ghadban, A. ; Albertin, L. Synthesis of Glycopolymer Architectures by Reversible-Deactivation Radical Polymerization. Polymers 2013, 5, 431-526. (b) 1. Albertin, L. ; Cameron, N.R. RAFT Polymerization of Methyl 6-O-Methacryloyl-α-D-glucoside in Homogeneous Aqueous Medium. A Detailed Kinetic Study at the Low Molecular Weight Limit of the Process. Macromolecules (Washington, DC, U. S.) 2007, 40, 6082-6093. (b) Albertin, L. ; Stenzel, M. ; Barner-Kowollik, C. ; Foster, L.J.R. ; Davis, T.P. Well-defined glycopolymers from RAFT polymerization : poly(methyl 6-O-methacryloyl-α-D-glucoside) and its block copolymer with 2-hydroxyethyl methacrylate. Macromolecules (Washington, DC, U. S.) 2004, 37, 7530-7537. (c) Albertin, L. ; Kohlert, C. ; Stenzel, M. ; Foster, L.J.R. ; Davis, T.P. Chemoenzymatic Synthesis of Narrow-Polydispersity Glycopolymers : Poly(6-O-vinyladipoyl-D-glucopyranose). Biomacromolecules 2004, 5, 255-260. [2] – Albertin, L. ; Charreyre, M.-T. ; Delair, T. ; Komurian-Pradel, F. In Preliminary studies on the synthesis of well defined multivalent glycoligands for exploring the influenza virus-host cell binding mechanism, HFSP Sixth Awardees Annual Meeting, Paris, July 3-5, 2006 ; Paris, 2006. [3] - (a) Cameron, N.R. ; Spain, S.G. ; Kingham, J.A. ; Weck, S. ; Albertin, L. ; Barker, C.A. ; Battaglia, G. ; Smart, T. ; Blanazsc, A. Synthesis of well-defined glycopolymers and some studies of their aqueous solution behaviour. Faraday Discussions 2008, 139, 359-368. (b) Albertin, L. ; Stenzel, M.H. ; Barner-Kowollik, C. ; Foster, L.J.R. ; Davis, T.P. Well-Defined Diblock Glycopolymers from RAFT Polymerization in Homogeneous Aqueous Medium. Macromolecules (Washington, DC, U. S.) 2005, 38, 9075-9084. [4] - Albertin, L. ; Wolnik, A. ; Ghadban, A. ; Dubreuil, F. Aqueous RAFT polymerization of N-acryloylmorpholine, synthesis of an ABA triblock glycopolymer and study of its self-association behavior Macromol. Chem. Phys. 2012, 213, 1768−1782. [5] – (a) Ghadban, A. ; Reynaud, E. ; Rinaudo, M. ; Albertin, L. RAFT copolymerization of alginate-derived macromonomers - Synthesis of a well-defined poly(HEMAm)-graft-(1→4)-α-L-guluronan copolymer capable of ionotropic gelation. Polym. Chem. 2013, 4, 4578-4583. [b] Ghadban, A. ; Albertin, L. ; Rinaudo, M. ; Heyraud, A. Biohybrid glycopolymer capable of ionotropic gelation. Biomacromolecules 2012, 13, 3108–3119.

Contact : lionel.bureau@ujf-grenoble.fr