Hyperbranched Copolymers Based on Glycidol and Amino Glycidyl Ether: Highly Biocompatible Polyamines Sheathed in Polyglycerols

Abstract

Functional hyperbranched polyglycerols (PGs) have recently garnered considerable interest due to their potential in biomedical applications. Here, we present a one-pot synthesis of hyperbranched PGs possessing amine functionality using a novel amino glycidyl ether monomer. A Boc-protected butanolamine glycidyl ether (BBAG) monomer was designed and polymerized with glycidol (G) through anionic ring-opening multibranching polymerization to yield a series of hyperbranched P(G-co-BBAG) with controlled molecular weights (4800-16700 g/mol) and relatively low molecular weight distributions (1.2-1.6). The copolymerization and subsequent deprotection chemistry allow the incorporation of an adjustable fraction of primary amine moieties (typically, 5-20% monomer ratio) within the hyperbranched PG backbones, thus providing potentials for varying charge densities and functionality in PGs. The copolymerization kinetics of G and BBAG was also evaluated using a quantitative in situ C NMR spectroscopic analysis, which revealed gradient copolymerization between the comonomers. The free amine groups within the deprotected P(G-co-BAG) copolymer were further utilized for a facile conjugation chemistry with a model molecule in a quantitative manner. Furthermore, the superior biocompatibility of the prepared P(G-co-BAG) polymers was demonstrated via cell viability assays, outperforming many existing polyamines possessing relatively high cytotoxicity. Taken together, the biocompatibility with facile conjugation chemistry of free amine groups sheathed within the framework of hyperbranched PGs holds the prospect of advancing biological and biomedical applications.

Anionic Polymerization of Azidoalkyl Glycidyl Ethers and Post-Polymerization Modification

“…Inspired by the advent of click chemistry, the azide functionality is regarded as a good candidate for the post-polymerization modification of polyethers due to its potential to undergo further modification by Cu-catalyzed azide–alkyne cycloaddition (CuAAC) or Staudinger reduction. As a part of our ongoing effort in the development of novel functional glycidyl ether monomer library, − herein, we introduce a series of new azide-functional glycidyl ether monomers, azidoethyl glycidyl ether (AEGE), azidobutyl glycidyl ether (ABGE), and azidohexyl glycidyl ether (AHGE) that can be polymerizable under organic superbase-catalyzed AROP conditions. The homopolymerization of each monomer was compared using in situ 1 H NMR kinetic study.…”

Highly Branched Polycaprolactone/Glycidol Copolymeric Green Plasticizer by One-Pot Solvent-Free Polymerization

“…Glycidol, one of the most versatile derivatives of renewable glycerol, has been widely used as a raw material in the chemical synthesis of polyglycerols, glycidyl ethers, and polyurethanes, as well as in perfumes, cosmetics, surface coatings, detergents, and paints. − In particular, since glycidol is converted to the glycerol branching unit after anionic/cationic ring-opening polymerization, a number of studies have demonstrated the availability of glycidol to produce highly branched polymers via copolymerization with other monomers. − From this perspective, we hypothesized that glycidol would be a suitable branching monomer for PCL, if it can be ring-opened under the typical conditions used for synthesizing PCL, i.e., a one-pot, solvent-free, and Sn­(Oct) 2 -catalyzed polymerization. However, to date, there have been only a few reports describing the ring-opening of glycidol in the presence of Sn­(Oct) 2 . , Furthermore, to the best of our knowledge, there are no reports on the ring-opening multibranching copolymerization of CL with glycidol.…”

Anionic ring‐opening polymerization of N‐glycidylphthalimide: Combination of phosphazene base and activated monomer mechanism

“…There are a few epoxide monomers functionalized with protected amino groups reported to be polymerized by AROP: N,Ndibenzylglycidylamine (DBGA), 12,13 N,Ndiallyglycidylamine (DAGA), 14 Boc-protected butanolamine glycidyl ether (BBAG). 15 Moreover, glycidyl phthalimide is an interesting protected-amine-containing monomer which has been used to functionalize hyperbranched polyglycerols with amine groups. 16,17 However, ABSTRACT : Anionic ring-opening polymerization of glycidyl phthalimide, initiated with alcoholphosphazene base systems and based on monomer activation with a Lewis acid (iBu3Al), has been studied.…”