TY - JOUR

T1 - Synthesis and characterization of well-defined poly(2-deoxy-2-methacrylamido-D-glucose) and its biopotential block copolymers via RAFT and ROP polymerization

AU - Levit, Mariia

AU - Zashikhina, Natalia

AU - Dobrodumov, Anatoliy

AU - Kashina, Anna

AU - Tarasenko, Irina

AU - Panarin, Evgeniy

AU - Fiorucci, Stefano

AU - Korzhikova-Vlakh, Evgenia

AU - Tennikova, Tatiana

PY - 2018/8/1

Y1 - 2018/8/1

N2 - Well-defined homopolymers of 2-deoxy-2-methacrylamido-D-glucose (MAG) were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization using 4-cyanopentanoic acid-4-dithiobenzoate as chain transfer agent (CTA) and 2,2′-azobisisobutyronitrile (AIBN) as initiator. The effect of polymerization conditions such as molar ratio of RAFT agent to initiator and monomer to RAFT agent on conversion and molecular mass characteristics of prepared polymers was estimated. Kinetics of the polymerization under various reaction conditions was studied as a function of time and conversion using in situ 1H NMR spectroscopy. The living character of polymerization was demonstrated by carriyng out the further chain extension experiments using isolated PMAG-CTA as a macroRAFT agent. For that, the PMAG with higher molecular weight, as well as block copolymer with acrylic acid were synthesized and characterized using 1H NMR and SEC analysis. A novel amphiphilic copolymer representing a hybrid of glycopolymer and polypeptide fragments was synthesized using RAFT and ring-opening polymerization (ROP). In this case, dithiobenzoate end-group of PMAG was transformed via simultaneous reduction and in situ thiol capping reaction by cysteamine hydrochloride into amino functionality suitable for polymerization of N-carboxyanhydrides (NCA). Two block copolymers of MAG with poly-L-phenylalanine (PPhe) differed with hydrophobic block length were synthesized, characterized and used for preparation of particles via copolymer self-assembly. The hydrodynamic diameter, morphology and cytotoxicity of polymer particles based on PMAG-b-PPhe were evaluated using DLS, TEM and MTT-assay, respectively. Moreover, the encapsulation of model compound (fluorescent dye rhodamine 6G) inside PMAG-b-PPhe micelles, as well as its release, were also tested.

AB - Well-defined homopolymers of 2-deoxy-2-methacrylamido-D-glucose (MAG) were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization using 4-cyanopentanoic acid-4-dithiobenzoate as chain transfer agent (CTA) and 2,2′-azobisisobutyronitrile (AIBN) as initiator. The effect of polymerization conditions such as molar ratio of RAFT agent to initiator and monomer to RAFT agent on conversion and molecular mass characteristics of prepared polymers was estimated. Kinetics of the polymerization under various reaction conditions was studied as a function of time and conversion using in situ 1H NMR spectroscopy. The living character of polymerization was demonstrated by carriyng out the further chain extension experiments using isolated PMAG-CTA as a macroRAFT agent. For that, the PMAG with higher molecular weight, as well as block copolymer with acrylic acid were synthesized and characterized using 1H NMR and SEC analysis. A novel amphiphilic copolymer representing a hybrid of glycopolymer and polypeptide fragments was synthesized using RAFT and ring-opening polymerization (ROP). In this case, dithiobenzoate end-group of PMAG was transformed via simultaneous reduction and in situ thiol capping reaction by cysteamine hydrochloride into amino functionality suitable for polymerization of N-carboxyanhydrides (NCA). Two block copolymers of MAG with poly-L-phenylalanine (PPhe) differed with hydrophobic block length were synthesized, characterized and used for preparation of particles via copolymer self-assembly. The hydrodynamic diameter, morphology and cytotoxicity of polymer particles based on PMAG-b-PPhe were evaluated using DLS, TEM and MTT-assay, respectively. Moreover, the encapsulation of model compound (fluorescent dye rhodamine 6G) inside PMAG-b-PPhe micelles, as well as its release, were also tested.

KW - Amphiphilic block copolymers

KW - Biomaterials

KW - Biopotential polymers

KW - Hybrid block copolymers

KW - Polymer micelles

KW - RAFT polymerization

KW - ROP NCA

KW - Self-assembly

KW - Well-defined glycopolymers

UR - http://www.scopus.com/inward/record.url?scp=85047603386&partnerID=8YFLogxK

U2 - 10.1016/j.eurpolymj.2018.05.018

DO - 10.1016/j.eurpolymj.2018.05.018

M3 - Article

AN - SCOPUS:85047603386

VL - 105

SP - 26

EP - 37

JO - European Polymer Journal

JF - European Polymer Journal

SN - 0014-3057

ER -