Coating Methods of Carbon Nonwovens with Cross-Linked Hyaluronic Acid and Its Conjugates with BMP Fragments.

The cross-linking of polysaccharides is a universal approach to affect their structure and physical properties. Both physical and chemical methods are used for this purpose. Although chemical cross-linking provides good thermal and mechanical stability for the final products, the compounds used as stabilizers can affect the integrity of the cross-linked substances or have toxic properties that limit the applicability of the final products. These risks might be mitigated by using physically cross-linked gels. In the present study, we attempted to obtain hybrid materials based on carbon nonwovens with a layer of cross-linked hyaluronan and peptides that are fragments of bone morphogenetic proteins (BMPs). A variety of cross-linking procedures and cross-linking agents (1,4-butanediamine, citric acid, and BDDE) were tested to find the most optimal method to coat the hydrophobic carbon nonwovens with a hydrophilic hyaluronic acid (HA) layer. Both the use of hyaluronic acid chemically modified with BMP fragments and a physical modification approach (layer-by-layer method) were proposed. The obtained hybrid materials were tested with the spectrometric (MALDI-TOF MS) and spectroscopic methods (IR and 1H-NMR). It was found that the chemical cross-linking of polysaccharides is an effective method for the deposition of a polar active substance on the surface of a hydrophobic carbon nonwoven fabric and that the final material is highly biocompatible.

Chemical Modification as a Method of Improving Biocompatibility of Carbon Nonwovens.

It was shown that carbon nonwoven fabrics obtained from polyacrylonitrile fibers (PAN) by thermal conversion may be modified on the surface in order to improve their biological compatibility and cellular response, which is particularly important in the regeneration of bone or cartilage tissue. Surface functionalization of carbon nonwovens containing C-C double bonds was carried out using in situ generated diazonium salts derived from aromatic amines containing both electron-acceptor and electron-donor substituents. It was shown that the modification method characteristic for materials containing aromatic structures may be successfully applied to the functionalization of carbon materials. The effectiveness of the surface modification of carbon nonwoven fabrics was confirmed by the FTIR method using an ATR device. The proposed approach allows the incorporation of various functional groups on the nonwovens' surface, which affects the morphology of fibers as well as their physicochemical properties (wettability). The introduction of a carboxyl group on the surface of nonwoven fabrics, in a reaction with 4-aminobenzoic acid, became a starting point for further modifications necessary for the attachment of RGD-type peptides facilitating cell adhesion to the surface of materials. The surface modification reduced the wettability (θ) of the carbon nonwoven by about 50%. The surface free energy (SFE) in the chemically modified and reference nonwovens remained similar, with the surface modification causing an increase in the polar component (ɣp). The modification of the fiber surface was heterogeneous in nature; however, it provided an attractive site of cell-materials interaction by contacting them to the fiber surface, which supports the adhesion process.