Two novel aliphatic polyurethaneurea anionomers were synthesized based on polydimethylsiloxane (PDMS)-polytetramethylene oxide (PTMO) soft segments. The hard segments consisted of either 4,4'-methylene dicyclohexyl diisocyanate (H12MDI), sulfonic acid-containing diol and 1,4-butandiol (BD) or H12MDI, carboxylic acid-containing diol and BD. The nonionic counterpart chain extended with BD was prepared. In addition, the base nonionic polyurethaneurea containing a pure PDMS soft segment, which is denote H-D-BD, was also studied for comparison. The effects of soft segment type and ion incorporation on the physical properties, surface properties, and plateled adhesion are discussed. The ionic polyurethaneureas exhibited poor phase separation, a smaller fraction of PTMO present at the surface, and a smaller contact angle. On the other hand, it also showed a larger fraction of PDMS present at the surface and a higher water absorption value than its nonionic counterpart. H-D-BD had more phase-separated structure, a larger fraction of PDMS present at the surface, and larger contact angle but lower water absorption value than the PTMO-containing polyurethaneureas. The in vitro platelet adhesion experiments indicated that the ionic groups, especially for carboxylate, and surface enrichment PDMS soft segment could effectively inhibit platelet adhesion.
A simple procedure for surface modification of polyurethane by the Langmuir-Blodgett (LB) method using the amphiphile 1,2-distearoyl-sn-glycero-3-phosphocholine dihydrate (DSPC) was developed. The polyurethane containing the fluorinated moiety was prepared via the perfluoro-containing chain extender 2,2,3,3-tetrafluoro-1,4-butanediol. The fluorinated polyurethane (FPU) films were prepared by spin coating and dipping methods. The spin-coated FPU films exhibited hydrophobic characteristic and, thus, enhanced the transferability of DSPC. Held at constant pressure of 45 mN/m, the DSPC monolayer was transferred successfully to FPU films with a near-unity transfer ratio. The in vitro platelet adhesion assay revealed that the FPU modified with DSPC monolayer was more platelet compatible than the unmodified FPU substrates with no pseudopods and flattening of adherent platelets as well as lower platelet adhesion density. Moreover, the DSPC monolayer remained intact after platelet adhesion testing. In addition, the platelet compatibility of the unmodified FPU was affected by the film preparation methods. This might be attributed to the distinctive surface micromorphology formed. This simple DSPC deposition scheme by a LB technique would be very useful to further enhance the platelet compatibility of hydrophobic substrate and can be utilized for biomedical application in which the flow shear rate is not too high.
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