Skip to Main content Skip to Navigation
Journal articles

Self-Assembly of Stimuli-Responsive Biohybrid Synthetic-b-Recombinant Block Copolypeptides

Gaëlle Le Fer 1, 2 Anne-Laure Wirotius 1, 3 Annie Brûlet 4 Elisabeth Garanger 1, 2 Sébastien Lecommandoux 1, 2, *
* Corresponding author
2 Team 3 LCPO : Polymer Self-Assembly & Life Sciences
LCPO - Laboratoire de Chimie des Polymères Organiques
3 Team 1 LCPO : Polymerization Catalyses & Engineering
LCPO - Laboratoire de Chimie des Polymères Organiques
4 GDPA - Groupe Diffusion petits angles
LLB - UMR 12 - Laboratoire Léon Brillouin : DRF/IRAMIS/LLB, IRAMIS - Institut Rayonnement Matière de Saclay : DRF/IRAMIS/LLB
Abstract : The synthesis and original thermoresponsive behavior of hybrid diblock copolypeptides composed of synthetic and recombinant polypeptides are herein reported. A thermoresponsive recombinant elastin-like polypeptide was used as a macroinitiator to synthesize a range of poly(L-glutamic acid)-block-elastin-like polypeptide (PGlu-b-ELP) diblock copoly-peptides with variable PGlu block lengths. Their temperature-triggered self-assembly in water and in phosphate-buffered saline (PBS) was investigated at the macroscopic scale using complementary techniques such as turbidimetry, dynamic and static light scattering, small-angle neutron scattering, and at the molecular scale by 1 H NMR and circular dichroism (CD). In deionized water, PGlu-b-ELP copolypeptides showed one transition from free soluble chains below the transition temperature (Tt) of the ELP block to macroscopic aggregates above the Tt. In contrast, in PBS, four successive regimes were observed upon increasing temperature: below the Tt , copolypeptides were soluble, above the Tt , large aggregates appeared and fell apart into discrete and defined spherical nanoparticles at a temperature named critical micellization temperature (CMT), before finally reaching an equilibrium. During the last regime, neutron scattering experiments revealed that the micelle-like structures underwent a densification step and expelled water from their core. In addition, 1H NMR and CD experiments revealed, in deionized water, the formation of type II β-turns into the ELP block upon temperature increase. These β-turns are known to participate in the intrinsic thermoresponsive behavior of the ELPs. In contrast, in PBS, circular dichroism measurements showed an attenuation of folded structure during the self-assembly phase, leading to less cohesive aggregates able to reorganize into nanoparticles at the CMT.
Complete list of metadata

Cited literature [102 references]  Display  Hide  Download
Contributor : Olivier Sandre Connect in order to contact the contributor
Submitted on : Monday, July 8, 2019 - 8:54:01 AM
Last modification on : Thursday, July 8, 2021 - 3:52:22 AM


Article PGlu-b-ELPM40-reviewed...
Files produced by the author(s)



Gaëlle Le Fer, Anne-Laure Wirotius, Annie Brûlet, Elisabeth Garanger, Sébastien Lecommandoux. Self-Assembly of Stimuli-Responsive Biohybrid Synthetic-b-Recombinant Block Copolypeptides. Biomacromolecules, American Chemical Society, 2019, 20 (1), pp.254-272. ⟨10.1021/acs.biomac.8b01390⟩. ⟨hal-01948441⟩



Record views


Files downloads