Search

Hyaluronan (HA) is a hydrophilic biopolymer that has been explored as a wetting agent in contact lens applications. In this study, HA was modified with siloxy or polyethylene glycol moieties using click chemistry to make it more soluble in monomer solutions used to synthesize model contact lens materials; unmodified HA was not soluble in the same monomer solutions. The water contents of the silicone hydrogels were not increased by the presence of modified HA, nor was there a decrease in the surface contact angle. However, modified HA did lead to a reduction in lysozyme adsorption in some cases. The leaching rate of HA modified with polyethylene glycol from a 78:22 DMA:TRIS(OH) hydrogel was significantly slower than for unmodified HA.

A collagenase-cleavable peptide-based crosslinking agent was synthesized and was incorporated into PHEMA sponges, and P[HEMA-co-MeO-PEGMA] gels and sponges [HEMA 2-hydroxyethyl methacrylate, PHEMA = poly(2-hydroxyethyl methacrylate), MeO-PEGMA = poly(ethylene glycol) monomethyl ether methacrylate]. PHEMA and P[HEMA-co-MeO-PEGMA] sponges had polymer droplet morphologies where the dimensions of the morphological features were three to five times larger compared to sponges that were crosslinked with tetraethylene glycol dimethacrylate (TEGDMA), while the P[HEMA-co-MeO-PEGMA] gels had similar morphologies regardless of the crosslinking agent. The differences in the dimensions of the morphologies of the sponges were attributed to differences in hydrophilicities of the crosslinking agent. When incubated in a collagenase solution, PHEMA sponges did not degrade, but P[HEMA-co-MeO-PEGMA] gels took 28 days to degrade and the P[HEMA-co-MeO-PEGMA] sponges took 101 days to degrade to 8% dry weight remaining. A cytotoxicity assay showed that the hydrogels do not elicit any cytotoxic response in vitro.

The internal morphologies for a series of heterogeneous PHEMA and P[HEMA-co-MeO-PEGMA] [PHEMA = poly(2-hydroxyethyl methacrylate), MeO-PEGMA = poly(ethylene glycol) methyl ether methacrylate] hydrogels were characterized by scanning electron microscopy (SEM) in conjunction with a sample drying procedure, and by laser scanning confocal microscopy (LSCM) without prior drying. Compared to SEM, LSCM was far simpler and more rapid technique for imaging hydrogels. LSCM also allowed the native hydrated morphology of the hydrogels to be characterized, whereas SEM could only characterize the morphology of samples in their dehydrated state. No dehydration method used in this study preserved the true native morphology, but plunge freezing/freeze drying was the most suitable method that best preserved the native morphology for all hydrogel compositions. Refrigerated freezing/freeze-drying and critical point drying introduced significant morphological artifacts, the severity of the artifacts being dependant on the sample's composition and Tg. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

A bis(methacrylamido) derivative of glucose has been used as a crosslinking agent for PHEMA sponges formed by polymerization-induced phase separation.

A nonapeptide, which is sensitive to enzymatic digestion by collagenase, was modified by the covalent attachment of an acrylamido group at the terminal positions. The functionalized peptide was used as a crosslinking agent during polymerization of 2-hydroxyethyl methacrylate (HEMA). Reversible addition-fragmentation chain transfer (RAFT) method was used to obtain a polymer (PHEMA) with an average theoretical molecular weight of 4000 Da, containing enzymatically labile peptide crosslinks. The functionalized peptide was analyzed in detail by 1H and 13C nuclear magnetic resonance (NMR) spectrometry. The polymerization reaction was monitored by near infrared spectrometry, while the resulting polymer was analyzed by size exclusion chromatography and solid NMR spectrometry. The peptide-crosslinked PHEMA was subjected to an in-vitro degradation assay in the presence of collagenase. At the highest concentration of enzyme used in the study, a weight loss of 35% was recorded after 60 days of incubation in the collagenolytic medium. This suggests that crosslinking with enzymatically degradable peptides is a valid method for inducing biodegradability in polymers that otherwise are not degradable.

2-Hydroxyethyl methacrylate has been polymerized in methanol using activators regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP), to produce water-soluble poly(2-hydroxyethyl methacrylate) (PHEMA). The various parameters that determine control of the living polymerization have been explored. Using the Cu(II)/TPMA catalyst system (TPMA = tris(2-pyridylmethyl)amine), controlled polymerization was achieved with Cu concentrations as low as 50 ppm relative to HEMA, with a [TPMA]/[Cu(II)] ratio of 5. Use of hydrazine as the reducing agent generally gave better control of polymerization than use of ascorbic acid. The polymerization conditions were tolerant of small amounts of air, and colorless polymers were easily isolated by simple precipitation and washing steps. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4084–4092, 2010

Hyaluronan (HA) is a hydrophilic biopolymer that has been explored as a wetting agent in contact lens applications. In this study, HA was modified with siloxy or polyethylene glycol moieties using click chemistry to make it more soluble in monomer solutions used to synthesize model contact lens materials; unmodified HA was not soluble in the same monomer solutions. The water contents of the silicone hydrogels were not increased by the presence of modified HA, nor was there a decrease in the surface contact angle. However, modified HA did lead to a reduction in lysozyme adsorption in some cases. The leaching rate of HA modified with polyethylene glycol from a 78:22 DMA:TRIS(OH) hydrogel was significantly slower than for unmodified HA.