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Gradient Functionalization of Poly(lactic acid)-Based Materials with Polylysine for Spatially Controlled Cell
Viktor Korzhikov-Vlakh1,2, Aleksandra Mikhailova1,3, Ekaterina Sinitsyna1
1Institute of Chemistry, St. Petersburg, St. Petersburg State University, 198504 St. Petersburg, Russia.
Abstract:
The development of biomaterials with gradient surface modification capable of spatially controlled cell adhesion and migration is of great importance for tissue engineering and regeneration. In this study, we proposed a method for the covalent modification of PLA-based materials with a cationic polypeptide (polylysine, PLys) via a thiol-ene click reaction carried out under a light gradient. With this aim, PLA-based films were fabricated and modified with 2-aminoethyl methacrylate (AEMA) as a double bond source. The latter was introduced by reacting pre-formed and activated surface carboxyl groups with the amino group of AEMA. The success of the modification was confirmed by 1H NMR, Raman and X-ray photoelectron spectroscopy data. A further photoinduced thiol-ene click reaction in the presence of a photosensitive initiator as a radical source was further optimized using cysteine. For grafting of PLys via the thiol-ene click reaction, PLys with a terminal thiol group was synthesized by ring-opening polymerization using Cys(Acm) as an amine initiator. Deprotection of the polypeptide resulted in the formation of free thiol groups of Cys-PLys. Successful gradient grafting of Cys-PLys was evidenced by covalent staining with the fluorescent dye Cy3-NHS. In addition, PLys gradient-dependent adhesion and migration of HEK 293 cells on PLys-PLA-based surfaces was confirmed.
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