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Thermoresponsive P(HEMA-co-OEGMA) copolymers: synthesis, characteristics and solution behavior.

ABSTRACT: Random, thermoresponsive copolymers of 2-hydroxyethyl methacrylate (HEMA) and oligo(ethylene glycol) methyl ether methacrylate M _n = 300 (OEGMA) were synthesized via atom transfer radical polymerization (ATRP) in a DMSO/H₂O solvent mixture. Reactivity ratios were determined by the extended Kelen-Tudos method and found to be close to 1. Studies confirmed the randomness of the obtained copolymers. The thermoresponsiveness in water and in phosphate buffer (PBS) solutions and the influence of copolymer composition and solution concentration on the cloud point temperature (T _cp) were investigated. Phase transitions in water solutions were reversible and narrow. The response of P(HEMA-co-OEGMA) to temperature could be adjusted in the range from 66.5 °C to 21.5 °C by changing the HEMA content. In PBS solutions, significant differences in the heating/cooling cycle were observed for all investigated concentrations. The presence of kosmotropic salts in PBS decreased the T _cp value and caused thermal aggregation of chains to form a macroscopic aggregate at temperatures above the T _cp.

SUBMITTER: Kasprow M

PROVIDER: S-EPMC9076357 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature

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Thermoresponsive P(HEMA-co-OEGMA) copolymers: synthesis, characteristics and solution behavior.

Kasprów Maciej M Machnik Justyna J Otulakowski Łukasz Ł Dworak Andrzej A Trzebicka Barbara B

RSC advances 20191211 70

Random, thermoresponsive copolymers of 2-hydroxyethyl methacrylate (HEMA) and oligo(ethylene glycol) methyl ether methacrylate M n = 300 (OEGMA) were synthesized via atom transfer radical polymerization (ATRP) in a DMSO/H2O solvent mixture. Reactivity ratios were determined by the extended Kelen-Tudos method and found to be close to 1. Studies confirmed the randomness of the obtained copolymers. The thermoresponsiveness in water and in phosphate buffer (PBS) s ...[more]

PMID: 35540067

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Project description:The fabrication of multifunctional, thermoresponsive platforms for regenerative medicine based on polymers that can be easily functionalized is one of the most important challenges in modern biomaterials science. In this study, we utilized atom transfer radical polymerization (ATRP) to produce two series of novel smart copolymer brush coatings. These coatings were based on copolymerizing 2-hydroxyethyl methacrylate (HEMA) with either oligo(ethylene glycol) methyl ether methacrylate (OEGMA) or N-isopropylacrylamide (NIPAM). The chemical compositions of the resulting brush coatings, namely, poly(oligo(ethylene glycol) methyl ether methacrylate-co-2-hydroxyethyl methacrylate) (P(OEGMA-co-HEMA)) and poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) (P(NIPAM-co-HEMA)), were predicted using reactive ratios of the monomers. These predictions were then verified using time-of-flight-secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). The thermoresponsiveness of the coatings was examined through water contact angle (CA) measurements at different temperatures, revealing a transition driven by lower critical solution temperature (LCST) or upper critical solution temperature (UCST) or a vanishing transition. The type of transition observed depended on the chemical composition of the coatings. Furthermore, it was demonstrated that the transition temperature of the coatings could be easily adjusted by modifying their composition. The topography of the coatings was characterized using atomic force microscopy (AFM). To assess the biocompatibility of the coatings, dermal fibroblast cultures were employed, and the results indicated that none of the coatings exhibited cytotoxicity. However, the shape and arrangement of the cells were significantly influenced by the chemical structure of the coating. Additionally, the viability of the cells was correlated with the wettability and roughness of the coatings, which determined the initial adhesion of the cells. Lastly, the temperature-induced changes in the properties of the fabricated copolymer coatings effectively controlled cell morphology, adhesion, and spontaneous detachment in a noninvasive, enzyme-free manner that was confirmed using optical microscopy.

Project description:Reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion polymerization of 2-hydroxypropyl methacrylate was used to prepare three poly(glycerol monomethacrylate) x -poly(2-hydroxypropyl methacrylate) y (denoted G x -H y or PGMA-PHPMA) diblock copolymers, namely G37-H80, G54-H140, and G71-H200. A master phase diagram was used to select each copolymer composition to ensure that a pure worm phase was obtained in each case, as confirmed by transmission electron microscopy (TEM) and small-angle x-ray scattering (SAXS) studies. The latter technique indicated a mean worm cross-sectional diameter (or worm width) ranging from 11 to 20 nm as the mean degree of polymerization (DP) of the hydrophobic PHPMA block was increased from 80 to 200. These copolymer worms form soft hydrogels at 20 °C that undergo degelation on cooling. This thermoresponsive behavior was examined using variable temperature DLS, oscillatory rheology, and SAXS. A 10% w/w G37-H80 worm dispersion dissociated to afford an aqueous solution of molecularly dissolved copolymer chains at 2 °C; on returning to ambient temperature, these chains aggregated to form first spheres and then worms, with the original gel strength being recovered. In contrast, the G54-H140 and G71-H200 worms each only formed spheres on cooling to 2 °C, with thermoreversible (de)gelation being observed in the former case. The sphere-to-worm transition for G54-H140 was monitored by variable temperature SAXS: these experiments indicated the gradual formation of longer worms at higher temperature, with a concomitant reduction in the number of spheres, suggesting worm growth via multiple 1D sphere-sphere fusion events. DLS studies indicated that a 0.1% w/w aqueous dispersion of G71-H200 worms underwent an irreversible worm-to-sphere transition on cooling to 2 °C. Furthermore, irreversible degelation over the time scale of the experiment was also observed during rheological studies of a 10% w/w G71-H200 worm dispersion. Shear-induced polarized light imaging (SIPLI) studies revealed qualitatively different thermoreversible behavior for these three copolymer worm dispersions, although worm alignment was observed at a shear rate of 10 s-1 in each case. Subsequently conducting this technique at a lower shear rate of 1 s-1 combined with ultra small-angle x-ray scattering (USAXS) also indicated that worm branching occurred at a certain critical temperature since an upturn in viscosity, distortion in the birefringence, and a characteristic feature in the USAXS pattern were observed. Finally, SIPLI studies indicated that the characteristic relaxation times required for loss of worm alignment after cessation of shear depended markedly on the copolymer molecular weight.

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Thermoresponsive P(HEMA-co-OEGMA) copolymers: synthesis, characteristics and solution behavior.

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Thermoresponsive P(HEMA-<i>co</i>-OEGMA) copolymers: synthesis, characteristics and solution behavior.

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