Smart hydrogels based on self-assembled amphiphilic copolymers

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