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Surface functionalization and grafting of heparin and/or RGD by an aqueous-based process to a poly(carbonate-urea)urethane cardiovascular graft for cellular engineering applications.

An aqueous-based process is reported for surface functionalization and grafting of anticoagulant and cell attachment moieties, such as heparin and/or arginine-glycine- aspartate (RGD) onto the lumenal surface of a prefabricated cardiovascular graft (5 mm i.d.) made of poly(carbonate- urea)urethane (MyoLink). It is a three-stage process, all aqueous: (1) hydroxylation using an azobis compound, particularly 2,2'-azobis(2-methylpropionamidine)dihydrochloride, which abstracts hydrogen via an electron transfer process from the polyurethane surface (strong oxygen purging); (2) grafting using the as-generated hydroxide groups to allow attachment of an acrylamide monomer using a conventional ceric ion technique (strong nitrogen purging); and (3) moiety attachment, preactivated with [1-ethyl-3-(3-dimethylaminopropyl)carbodiimide] in acidic solution. The technique was validated by attaching heparin and RGD/heparin to the MyoLink polymer. Following bonding, the graft segments were exposed to prolonged physiologic shear force in a flow circuit (10 h). The grafts first were analyzed by X-ray photoelectron spectroscopy (XPS) to determine the degree of attachment of the moieties and then by materials methods to assess whether any degradation of the graft material itself had occurred since polyurethanes with carbonate amorphous segments are readily susceptible to hydrolytic degradation following functionalization processes. XPS showed the moieties were present on the surface at a concentration of 10%. The S2p(3/2) states of sulfur indicated that there were high degrees of ionic covalent bonding, indicating high degrees of moiety bioactivity. Heparin was found to be present from the sulfur signal, namely NSO(3). RGD was found to be present from the nitrogen signal present at the binding energy of 399 eV. Macroscopic analysis and ESEM showed no signs of polyurethane degradation or small protuberances indicative of microgel formation. Quality control (QC) showed that the internal diameters and wall thicknesses of all the respective grafts postbonding remained within normal batch release limits (5 +/- 0.1mm, i.d.; 0.9 +/- 0.05 mm, wall thickness). Gel permeation chromatography (GPC) showed there were no statistical differences between the control, which was nonbonded (MN 45,300, MW 98,500, D 2.17) and all of the bonded samples, respectively (MN 41,800, MW 104,000, D 2.45). Radial tensile strength (RTS) analysis also showed that all of the respective samples postbonding (1.48N/mm) remained within batch release specifications (>1N/mm). A simple aqueous polymer surface functionalization and grafting technique has been developed for covalent bonding of anticoagulant and cell-attachment moieties onto poly(carbonate-urea)urethane(s) and has been validated by surface and materials analyses. The moieties were attached uniformly and were bioactive at a high surface density. No degradation in terms of a loss in mechanical properties was evident following bonding of the polyurethane.