Properties of acyl modified poly(glycerol-adipate) comb-like polymers and their self-assembly into nanoparticles

Abstract

There is an increasing need to develop bio‐compatible polymers with an increased range of different physicochemical properties. Poly(glycerol‐adipate) (PGA) is a biocompatible, biodegradable amphiphilic polyester routinely produced from divinyl adipate and unprotected glycerol by an enzymatic route, bearing a hydroxyl group that can be further functionalized. Polymers with an average Mn of ∼13 kDa can be synthesized without any post‐polymerization deprotection reactions. Acylated polymers with fatty acid chain length of C4, C8, and C18 (PGAB, PGAO, and PGAS, respectively) at different degrees of substitution were prepared. These modifications yield comb‐like polymers that modulate the amphiphilic characteristics of PGA. This novel class of biocompatible polymers has been characterized through various techniques such as FT‐IR, 1H NMR, surface, thermal analysis, and their ability to self‐assemble into colloidal structures was evaluated by using DLS. The highly tunable properties of PGA reported herein demonstrate a biodegradable polymer platform, ideal for engineering solid dispersions, nanoemulsions, or nanoparticles for healthcare applications. © 2016 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3267–3278

Exploring the enzymatic degradation of poly(glycerol adipate)

“…Generally, aliphatic polyesters with a short chain between ester groups, such as PGA, are found to undergo hydrolysis in a biologically relevant time frame [9]. The use of lipase in the synthesis of the polymer shows it is a viable substrate and so suggests PGA will be degradable by this enzyme.…”

“…Unmodified PGA and PGA with a range of amino acid modifications have also been shown to have negligible lytic activity in a haemolytic assay [8]. The presence of the pendant eOH group in the polymer backbone allows for the conjugation of molecules with a variety of functional groups through simple coupling reactions, influencing the physicochemical properties of PGA and its ability to encapsulate a variety of drugs [6,[8][9][10]. These changes to the polymer as a result of the modifications suggest the enzymatic degradation will be affected due to the enhanced stability, altered hydrophobicity and increased steric hindrance, leading to a potential for tunable breakdown and release in vivo.…”

Polyglycerol Hyperbranched Polyesters: Synthesis, Properties and Pharmaceutical and Biomedical Applications

“…So, these polymers are expected to self-assemble into nanoparticles in the absence of surfactant. Such acylated PGAd copolymers with different chain lengths (C 4 , C 6 , C 8 , C 12 , C 18 , C 22 ) have been reported in literature [47,48,50,63,64]. For the acylation, typically linear PGAd was dissolved in THF and the appropriate acid chloride was added (with pyridine to neutralize the eliminated HCl) [64].…”

Synthesis and Characterization of Linear Polyisoprene Supramolecular Elastomers Based on Quadruple Hydrogen Bonding

“…These polymers combine supramolecular chemistry and polymer science, and they possess many unique characteristics. They have potential applications in many fields, such as self-healing materials [3,4], degradable drug nanocarriers [5,6], heterogeneous catalysis [7,8], molecular muscles [9,10], and stimuli-responsive supramolecular gels [11,12]. Among them, supramolecular elastomers, which require good processing properties at elevated temperatures, attracted great attention worldwide [13,14].…”