Novel well‐defined glycopolymers synthesized via the reversible addition fragmentation chain transfer process in aqueous media

Abstract

We describe here the direct synthesis of novel gluconamidoalkyl methacrylamides by reacting D‐gluconolactone with aminoalkyl methacrylamides. The glycomonomers were then successfully polymerized via the reversible addition‐fragmentation chain transfer process (RAFT) using 4‐cyanopentanoic acid dithiobenzoate (CTP) as chain transfer agent and 4,4′‐azobis(4‐cyanovaleric acid) (ACVA) as the initiator in aqueous media. Well‐defined polymers were obtained as revealed by gel permeation chromatography. Diblock copolymers were then synthesized by the macro‐CTA approach. The cationic glycopolymers were subsequently used in the formation of nanostructures via the complexation with plasmid DNA. As noted by dynamic light scattering, monodisperse nanoparticles were obtained via the electrostatic interaction of the cationic glycopolymer with DNA. The sizes of the nanoparticles formed were found to be stable and independent of pH. In vitro cell viability studies of the glycopolymers were carried out using HELA cell lines. The RAFT synthesized glycopolymers and cationic glyco‐copolymers revealed to be nontoxic. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 614–627, 2009

Living Radical Polymerization by the RAFT Process - A Second Update

“…Methacrylamide derivatives subjected to RAFT polymerization 325 [154] 326 [154] 327 [157] OH [278] 329 [140] HN Table 20. Amino acid-derived acrylamides subjected to RAFT polymerization (R )-2-acrylamidopropanoic acid 330 [318,457] (S )-2-acrylamidopropanoic acid 331 [159,318,401,457] O NH HO 2 C O NH HO 2 C 332 [221,457] O NH HO 2 C 333 [457] 334 [458] 335 [458] [221,458] 337 [458] 338 [221,235,401,457] O…”

“…BMA [139] MAA [140] MMA [64,141] AEMA [90,142] DEGMA [141] DMAEMA [143] DPAEMA [144] MAA [145] PEGMA [144,[146][147][148] 383 [149] DMAM [150] NIPAM [151] 274 [152,153] 325 [154] 326 [154] APMAM-b-NIPAM [89,152] AEMAM [153] St [155] 274 [153] 275 [153] 285 [156] 286 [156] 289 [157] 292 [158] 304 [140] 305 [140] 331 [159] 329 [140] 327 [157] 380 [160] 391 [161,162] 389 [104] (390) [104] 416 [163,164] MAA-b-280 [145] BMA-b-MPC [139] PEGMA/ 320 [165] PEGMA/344 [165] DEGMA-b-384 [141] MMA-b-384 …”

Well‐Defined Glycopolymers via RAFT Polymerization: Stabilization of Gold Nanoparticles

“…Overall, RAFT technique presents several advantages such as the absence of metal catalyst, which is crucial for biomedical uses and also its tolerance to wide variety of solvents and monomers. This versatile reaction method allows the polymerization of both protected and unprotected glycomonomers in organic and aqueous media, simplifying the synthetic procedure . Moreover, RAFT polymerization yields polymers with dithio‐ or trithio‐terminal groups, which can be readily converted into thiol moieties.…”

Synthesis of Glycopolymer Architectures by Reversible-Deactivation Radical Polymerization

“…Narain et al [165] described the polymerization of unprotected methacrylamide derivatives M69 and M70 in H 2 O/DMF mixtures (14%-20% DMF, 70 °C) in the presence of R1 as the RAFT agent (Entry 157-158, Table 3). After an induction period of 60 min, reactions proceeded with pseudo-first order kinetics and a linear evolution of M n with conversion.…”