Phase Behavior of NR/PMMA Semi-IPNs and Development of Porous Structures.

In this research, the porous polymer structures (IPN) were made from natural isoprene rubber (NR) and poly(methyl methacrylate) (PMMA). The effects of molecular weight and crosslink density of polyisoprene on the morphology and miscibility with PMMA were determined. Sequential semi-IPNs were prepared. Viscoelastic, thermal and mechanical properties of semi-IPN were studied. The results showed that the key factor influencing the miscibility in semi-IPN was the crosslinking density of the natural rubber. The degree of compatibility was increased by doubling the crosslinking level. The degree of miscibility at two different compositions was compared by simulations of the electron spin resonance spectra. Compatibility of semi-IPNs was found to be more efficient when the PMMA content was less than 40 wt.%. A nanometer-sized morphology was obtained for a NR/PMMA ratio of 50/50. Highly crosslinked elastic semi-IPN followed the storage modulus of PMMA after the glass transition as a result of certain degree of phase mixing and interlocked structure. It was shown that the morphology of the porous polymer network could be easily controlled by the proper choice of concentration and composition of crosslinking agent. A dual phase morphology resulted from the higher concentration and the lower crosslinking level. This was used for developing porous structures from the elastic semi-IPN. The mechanical performance was correlated with morphology, and the thermal stability was comparable with respect to pure NR. Investigated materials might be interesting for use as potential carriers of bioactive molecules aimed for innovative applications such as in food packaging.

pH-Modulating Poly(ethylene glycol)/Alginate Hydrogel Dressings for the Treatment of Chronic Wounds.

The development of chronic wounds has been frequently associated with alkaline pH values. The application of pH-modulating wound dressings can, therefore, be a promising treatment option to promote normal wound healing. This study reports on the development and characterization of acidic hydrogel dressings based on interpenetrating poly(ethylene glycol) diacrylate/acrylic acid/alginate networks. The incorporation of ionizable carboxylic acid groups results in high liquid uptake up to 500%. The combination of two separate polymer networks significantly improves the tensile and compressive stability. In a 2D cell migration assay, the application of hydrogels (0% to 1.5% acrylic acid) results in complete "wound" closure; hydrogels with 0.25% acrylic acid significantly increase the cell migration velocity to 19.8 ± 1.9 µm h-1 . The most promising formulation (hydrogels with 0.25% acrylic acid) is tested on 3D human skin constructs, increasing keratinocyte ingrowth into the wound by 164%.

Scaffolds of Hyaluronic Acid-Poly(Ethyl Acrylate) Interpenetrating Networks: Characterization and In Vitro Studies.

Hyaluronic acid (HA) provides many advantages to regenerative implants through its bioactive properties, but it also has many limitations as a biomaterial if it is not chemically modified. In order to overcome some of these limitations, HA has been combined with poly(ethyl acrylate) in the form of interpenetrating polymeric networks (IPNs), in which the HA network is crosslinked with divinyl sulfone. Scaffolds of this IPN have been produced through a template-leaching methodology, and their properties have been compared with those of single-network scaffolds made of either PEA or crosslinked HA. A fibroblast cell line has been used to assess the in vitro performance of the scaffolds, revealing good cell response and a differentiated behavior on the IPN surface when compared to the individual polymers. Altogether, the results confirm that this type of material offers an interesting microenvironment for cells, which can be further improved toward its potential use in medical implants.

The bioactivity of agarose-PEGDA interpenetrating network hydrogels with covalently immobilized RGD peptides and physically entrapped aggrecan.

Our previous reports of interpenetrating networks (IPNs) have demonstrated drastic improvements in mechanical performance relative to individual constituent networks while maintaining viability of encapsulated cells. The current study investigated whether covalent linkage of RGD to the poly(ethylene glycol) diacrylate (PEGDA) network could improve upon cell viability and performance of agarose-PEGDA IPNs compared to unmodified IPNs (control) and to IPNs with different concentrations of physically entrapped aggrecan, providing a point of comparison to previous work. The inclusion of RGD or aggrecan generally did not adversely affect mechanical performance, and significantly improved chondrocyte viability and performance. Although both 4 and 100 µg/mL of aggrecan improved cell viability, only 100 µg/mL aggrecan was clearly beneficial to improving biosynthesis, whereas 100 µg/mL of RGD was beneficial to both chondrocyte viability and biosynthesis. Interestingly, clustering of cells within the IPNs with RGD and the higher aggrecan concentration were observed, likely indicating cell migration and/or preferred regional proliferation. This clustering resulted in a clearly visible enhancement of matrix production compared to the other IPNs. With this cell migration, we also observed significant cell proliferation and matrix synthesis beyond the periphery of the IPN, which could have important implications in facilitating integration with surrounding cartilage in vivo. With RGD and aggrecan (at its higher concentration) providing substantial and comparable improvements in cell performance, RGD would be the recommended bioactive signal for this particular IPN formulation and cell source given the significant cost savings and potentially more straightforward regulatory pathway in commercialization.