(Bio)Hydrogels

By tempering the hydrophobic blocks of block and grafted amphiphilic copolymers (that is by incorporating hydrophilic subunits inside them), we have been able to obtain self-assemblies and hydrogels at thermodynamic equilibrium whereas non tempered amphiphilic block copolymers display mostly the formation of frozen self-assemblies. When the hydrophilic subunits are pH sensitive, the dynamics of the resulting hydrogels can be tuned in a reversible way with pH over 11 orders of magnitude. Dynamic self-assemblies can be blended easily to achieve mixed micelles and hydrogels of controlled properties through the stoechiometry of the blends. We can also achieve interpenetrated self-assembled networks responsive to various stimuli when mixing appropriate block copolymers. This approach has been exemplified with a great variety of amphiphilic copolymers.

Researchers

• Lazhar Benyahia
• Christophe Chasseneiux
• Olivier Colombani
• Erwan Nicol
• Taco Nicolaï

Related papers

• Tsitsilianis, C.; Serras, G.; Ko, C.-H.; Jung, F.; Papadakis, C. M.; Rikkou-Kalourkoti, M.; Patricicios, C. S.; Schweins, R.; Chassenieux, C. Thermoresponsive Hydrogels Based on Telechelic Polyelectrolytes: From Dynamic to "Frozen" Networks. Macromolecules 2018, 51, (6), 2169-2179. doi: 10.1021/acs.macromol.8b00193.
• Nicol, E.; Nicolai, T.; Zhao, J.; Narita, T. Photo-Cross-Linked Self-Assembled Poly(ethylene oxide)-Based Hydrogels Containing Hybrid Junctions with Dynamic and Permanent Cross-Links. Acs Macro Letters 2018, 7, 683-687. doi: DOI: 10.1021/acsmacrolett.8b00317.
• Lauber, L.; Santarelli, J.; Boyron, O.; Chassenieux, C.; Colombani, O.; Nicolai, T. pH- and Thermoresponsive Self-Assembly of Cationic Triblock Copolymers with Controlled Dynamics. Macromolecules 2017, 50, (1), 416-423. doi: 10.1021/acs.macromol.6b02201.
• Lauber, L.; Depoorter, J.; Nicolai, T.; Chassenieux, C.; Colombani, O. Viscoelastic Properties of Hydrogels Based on Self-Assembled Multisticker Polymers Grafted with pH-Responsive Grafts. Macromolecules 2017, 50, (20), 8178-8184. doi: 10.1021/acs.macromol.7b01585.
• Wright, D. B.; Patterson, J. P.; Gianneschi, N. C.; Chassenieux, C.; Colombani, O.; O'Reilly, R. K. Blending block copolymer micelles in solution; obstacles of blending. Polymer Chemistry 2016, 7, (8), 1577-1583. doi: 10.1039/c5py02006a.
• Lauber, L.; Colombani, O.; Nicolai, T.; Chassenieux, C. pH-Controlled Rheological Properties of Mixed Amphiphilic Triblock Copolymers. Macromolecules 2016, 49, (19), 7469-7477. doi: 10.1021/acs.macromol.6b01600.
• Chassenieux, C.; Tsitsilianis, C. Recent trends in pH/thermo-responsive self-assembling hydrogels: from polyions to peptide-based polymeric gelators. Soft Matter 2016, 12, (5), 1344-1359. doi: 10.1039/c5sm02710a.
• Wright, D. B.; Patterson, J. P.; Pitto-Barry, A.; Lu, A.; Kirby, N.; Gianneschi, N. C.; Chassenieux, C.; Colombani, O.; O'Reilly, R. K. The Copolymer Blending Method: A New Approach for Targeted Assembly of Micellar Nanoparticles. Macromolecules 2015, 48, (18), 6516-6522. doi: 10.1021/acs.macromol.5b01426.
• Wright, D. B.; Patterson, J. P.; Pitto-Barry, A.; Cotanda, P.; Chassenieux, C.; Colombani, O.; O'Reilly, R. K. Tuning the aggregation behavior of pH-responsive micelles by copolymerization. Polymer Chemistry 2015, 6, (14), 2761-2768. doi: 10.1039/c4py01782j.
• Lauber, L.; Chassenieux, C.; Nicolai, T.; Colombani, O. Highlighting the Role of the Random Associating Block in the Self-Assembly of Amphiphilic Block-Random Copolymers. Macromolecules 2015, 48, (20), 7613-7619. doi: 10.1021/acs.macromol.5b01626.
• Klymenko, A.; Nicolai, T.; Benyahia, L.; Chassenieux, C.; Colombani, O.; Nicol, E. Multiresponsive Hydrogels Formed by Interpenetrated Self-Assembled Polymer Networks. Macromolecules 2014, 47, (23), 8386-8393. doi: 10.1021/ma501990r.

Projects

• ANR GELLIGHT
• ANR FOGEL
• ANR MACAOs
• ANR DYNAMIC PISA

Fine-tuning of thermo-induced assembly and rheological behavior of hydrogels based on well-defined bis-hydrophilic block copolymer bearing a terpyridine entity by successive RAFT aqueous dispersion polymerization via metal ions equivalent and mixture.

Researchers

• Sagrario Pascual
• Sandie Piogé
• Lazhar Benyahia
• Laurent Fontaine

Related papers

• M. Le Bohec, M. Banère, S. Piogé, S. Pascual, L. Benyahia, L. Fontaine, Polym. Chem., 2016, 7, 6834
• A. Gutierres, S. Pascual, L. Fontaine, S. Piogé, L. Benyahia, Polym. Chem., 2018, 9, 2494

Azlactone-based heterobifunctional linkers that proceed in orthogonal click-like reactions for chemical ligations in biologically relevant medium without releasing any by-product.

Researchers

• Sagrario Pascual
• Véronique Montembault
• Laurent Fontaine

Related papers

• Fontaine, H. T. Ho, S. Pascual, V. Montembault, PCT WO2014060357; US 20150285811A1; Japanese Patent n° 6262746 (2017)
• T. Ho, A. Bénard, G. Forcher, M. Le Bohec, V. Montembault, S. Pascual, L. Fontaine, Org. Biomol. Chem. 2018, 16, 7124-7128.

Azlactone-derived polymers synthesized by controlled RAFT polymerization are able to react with amines according to the “click” chemistry concept: with full atom economy, quantitatively and with total chemoselectivity. Such feature leads to thermosensitive lysozyme bioconjugates, thermosensitive metallo-supramolecular flower-like micelles and antibody-functionalized magnetic nanoparticles.

Researchers

• Sagrario Pascual
• Sandie Piogé
• Véronique Montembault
• Lazhar Benyahia
• Laurent Fontaine

Related papers

• T.H. Ho, M.E. Levere, S. Pascual, V. Montembault, N. Casse, A. Caruso, L. Fontaine, Polym. Chem. 2013, 4, 675-685
• Delplace, S. Harrisson, H. T. Ho, J. A. Tardy, Y. Guillaneuf, S. Pascual, L. Fontaine, J. Nicolas, Macromolecules 2015, 48, 2087-2097
• Pray-In, C. Boonthip, B. Rutnakornpituk, U. Wichai, V. Montembault, S. Pascual, L. Fontaine, M. Rutnakornpituk, Materials Science & Engineering, C: Materials for Biological Applications 2016, 67, 285-293
• M. Le Bohec, M. Banère, S. Piogé, S. Pascual, L. Benyahia, L. Fontaine, Polym. Chem. 2016, 7, 6834