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Poly(amino acid)-grafted polymacrolactones. Synthesis, self-assembling and ionic coupling properties

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posted on 16.04.2021, 09:06 by E Tinajero-Díaz, A Martínez de Ilarduya, Brenton Cavanagh, Andreas Heise, S Muñoz-Guerra

Polyglobalide (PGl) with number average polymerization degree of ~20 was prepared by enzymatic ROP and then polyfunctionalized at 60% with aminothioethylene groups. The PGl20-(NH2)12 copolymer was used as macroinitiator for the ROP of NCAs of BLG (γ-benzyl L-glutamate) and ZLL (εN-carbobenzoxy-l-lysine) protected amino acids to produce neutral polypeptide-grafted polyglobalides poly[Gl20-graft-(AA)z] with z = 5 and 12, which upon deprotection, afforded anionic and cationic copolymers, respectively. Both protected and deprotected graft copolymers were characterized in full detail by NMR, and their thermal properties were evaluated by TGA and DSC. The structure of these copolymers in the solid-state was examined by FTIR and XRD using synchrotron radiation. All grafted polyglobalides were amorphous but the polypeptide side chains were arranged in either alpha-helix or beta-sheet conformation, and reliable indications on the occurrence of supramolecular structures were frequently found. The capacity of poly[Gl20-graft-(AA)z] copolymers to self-assemble in aqueous medium was evidenced by the preparation of well-shaped spheroidal nanoparticles with a diversity of sizes depending on copolymer composition and charge. Loading and release of doxorubicin (DOX) from nanoparticles made of negatively charged poly[Gl20-graft-(LGA)12] as well as DNA complexation with cationic poly[Gl20-graft-(LL)5] were explored to appraise the potential of these copolymers for building drug delivery systems.

Funding

MINECO (grant MAT-2016- 77345-CO3-01)

CONACYT (México)

L’Obra Social la Caixa (Spain) “Beca de Mobilitat Internacional” award

Science Foundation Ireland (SFI) Principle Investigator Award 13/IA/1840(T)

History

Comments

The original article is available at https://www.sciencedirect.com

Published Citation

Tinajero-Díaz E, Martínez de Ilarduya A, Cavanagh B, Heise A, Muñoz-Guerra S. Poly(amino acid)-grafted polymacrolactones. Synthesis, self-assembling and ionic coupling properties. Reactive and Functional Polymers. 2019;143:104316

Publication Date

4 July 2019

Department/Unit

  • Chemistry

Research Area

  • Chemistry and Pharmaceutical Sciences
  • Biomaterials and Regenerative Medicine

Publisher

Elsevier BV

Version

  • Accepted Version (Postprint)