Interaction of blood components with heparin-immobilized polyurethanes prepared by plasma glow discharge

The blood compatibility of poly(ethylene oxide) (PEO)-grafted and heparin (Hep) immobilized polyurethanes was investigated using in vitro plasma recalcification time (PRT), activated partial thromboplastin time (APTT), platelet adhesion and activation, and peripheral blood mononuclear cell (PBMC) adhesion and activation. In the experiment with plasma proteins, the PRT of the polyurethane (PU) surface was prolonged by PEO grafting and further prolonged by heparin immobilization. The APTT was prolonged on PU-Hep, suggesting the binding of immobilized heparin to antithrombin III. The percentage of platelet adhesion on PU was not much different from that on acrylic acid- and PEO-grafted PUs (PU-C, PU-6, PU-33), yet was substantially decreased by heparin immobilization (PU-6-Hep, PU-33-Hep). The release of serotonin from adhering platelets was slightly suppressed on PEO-grafted PUs yet significantly suppressed on heparin-immobilized PUs. In the PBMC experiments, the adhesion and activation of the cells were significantly suppressed on heparin-immobilized PUs, and the amount of interleukin-6 (IL-6) released from PBMCs stimulated with surface-modified PUs decreased with a decrease in PBMC adhesion.     

Surface characterization and in vitro blood compatibility of poly(ethylene terephthalate) immobilized with insulin and/or heparin using plasma glow discharge

Poly(ethylene terephthalate)(PET) film was exposed to oxygen plasma glow discharge to produce peroxides on its surfaces. These peroxides were then used as catalysts for the polymerization of acrylic acid (AA) in order to prepare a carboxylic acid group-introduced PET (PET-AA). Insulin and heparin co-immobilized PET (PET-I-H) was prepared by the grafting of poly(ethylene oxide) (PEO) on to PET-AA, followed by reaction first with insulin and then heparin. These surface-modified PETs were characterized by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, electron spectroscopy for chemical analysis (ESCA), and a contact angle goniometer. The concentration of the heparin (1.23 microg/cm2) bound to the PEO-grafted PET (PET-PEO) was higher than that (0.77 microg/cm2) on the insulin-immobilized PET (PET-In). The blood compatibilities of the surface-modified PETs were examined using in vitro thrombus formation, plasma recalcification time (PRT), activated partial thromboplastin time (APTT), and platelet adhesion and activation. In the experiment with plasma proteins, the PRT and APTT were significantly prolonged for both the heparin-immobilized PET (PET-He) and the PET-I-H, suggesting the binding of immobilized heparin to antithrombin III. The percentage of platelet adhesion slightly increased with the introduction of AA on the PET surfaces, decreased with the introduction of PEO and insulin, and decreased further with the immobilization of heparin. The release of serotonin was highly suppressed on PET-He and PET-I-H, and on surface-modified PETs the percentage of its release increased with an increase in platelet adhesion.     

Synthesis and characterization of heparinized polyurethanes using plasma glow discharge

Polyurethanes (PU) were synthesized from 4,4'-diphenylmethane diisocyanate and polytetramethylene glycol, and subsequently with ethylene diamine as a chain extender. The PU film was exposed to oxygen plasma glow discharge to produce peroxides on the surfaces. These peroxides were then used as catalysts for the copolymerization of acrylic acid (AA) and methyl acrylate (MA) in order to prepare carboxyl group-introduced PU (PU-C). Heparin-immobilized PU was prepared using the coupling reaction of PU-C with polyethylene oxide (PEO) followed by the reaction of grafted PEO with heparin. The surface-modified PUs were then characterized by attenuated total reflection Fourier transform infrared spectroscopy, electron spectroscopy for chemical analysis (ESCA), and a contact angle goniometer. The concentration of carboxylic acid groups on the PU surfaces could be controlled within the range of 0.47-1.68 micromol cm(-2) by the copolymerization of AA and MA. The amounts of heparin coupled to terminus amino groups on PU-6 and PU-33 were 1.30 and 1.16 microg cm(-2), respectively. The water contact angle of the PU was decreased by AA grafting, and further decreased by PEO grafting and heparin immobilization, showing an increased hydrophilicity of the modified PUs. A 3% loss from the originally bound heparin appeared within several hours and thereafter almost no heparin was released when heparin-immobilized PUs were immersed in a physiological solution for 100 h, indicating the covalent immobilization of heparin on the surfaces.     

Heparin immobilization onto segmented polyurethane-urea surfaces--effect of hydrophilic spacers

Heparin was immobilized onto segmented polyurethane-urea surfaces (Biomer) using hydrophilic poly(ethylene oxide) spacers of different chain lengths. The use of the hydrophilic spacer, poly(ethylene oxide), reduces protein adsorption and subsequent platelet adhesion on the surface. In addition, the bioactivity of the immobilized heparin is enhanced by the incorporation of these spacers. Immobilized heparin bioactivity is shown to be a function of PEO spacer length. Use of hydrophilic PEO spacers demonstrates that immobilized heparin's bioactivity is consistently higher than that of the C6 alkyl spacer, but heparin-immobilized surfaces demonstrate no chain length effect on platelet adhesion, even though they show less platelet adhesion compared to Biomer controls. In the case of PEO-grafted surfaces, platelet adhesion is decreased compared to Biomer controls, and C6 alkyl spacer-grafted surfaces, and exhibits a minimum at PEO 1000. In ex vivo A-A shunt experiments under low flow and low shear conditions, all heparinized surfaces exhibit significant prolongation of occlusion times compared to Biomer controls, indicating an ability of immobilized heparin to inhibit thrombosis in whole blood.     

Negative cilia concept for thromboresistance: synergistic effect of PEO and sulfonate groups grafted onto polyurethanes

In order to investigate the interaction between various sulfonated polyurethanes (PUs) and blood, a commercial PU surface was chemically modified by poly(ethylene oxide) (PEO), dodecanediol(DDO), and propane sultone to give hydrophilic, hydrophobic, and negative sulfonated surfaces, respectively. The blood compatibility of modified PUs was evaluated by an in vitro platelet adhesion test, activated partial thromboplastin time (APTT), and prothrombin time (PT) measurements as well as an ex vivo rabbit A-A shunt method. In the platelet adhesion test, the hydrophilic PEO grafted PUs showed less platelet adhesion than untreated PU and hydrophobic DDO grafted PU. Sulfonated PU-PEO exhibited a lower degree of adhesion and shape change of platelet. The APTT and PT, especially APTT, of the sulfonated PUs were extended, whereas those of PU-PEO and PU-DDO did not show any significant change compared with untreated PU. Meanwhile, in the ex vivo experiment, hydrophilic PEO grafted PUs showed longer occlusion times than untreated PU or hydrophobic DDO grafted PU. In addition, the incorporation of SO3 groups at the end of PU-DDO and PU-PEO, particularly PU-PEO-SO3, exhibited an enormous prolongation in occlusion time, indicating a synergistic effect of the hydrophilic PEO and the negative SO3 groups on thromboresistance. These occlusion times corresponded well to in vitro evaluation results: the less adhesion and shape change of platelet and the longer APTT and PT, the more extended the ex vivo occlusion time.     

Effect of synthesis temperature of PEO-grafted PU/PS IPNs on surface morphology and in vitro blood compatibility

When hydrophilic/hydrophobic polymers have a microdomain structure, platelet adhesion and activation are effectively suppressed by prohibition of the excessive assembly of glycoproteins and adenosine triphosphate (ATP) consumption of the platelets on the surface. In this study, poly(ethylene oxide)-grafted hydrophilic polyurethane (PU)/hydrophobic polystyrene (PS) interpenetrating polymer networks (IPNs) were synthesized by varying the synthesis temperature to control the phase separation and the microdomain surface structure, and the effect of the degree of phase separation on the in vitro blood compatibility. The size of the dispersed PS-rich domains in the PU-rich matrix decreased, and the hydrophilicity also decreased as the synthesis temperature of the PS network during the IPN synthesis was decreased, as the phase separation was suppressed during the synthesis. The amount of the adsorbed bovine plasma fibrinogens (BPF) on the PEO-grafted PU/PS IPNs decreased as the synthesis temperature was decreased, and the in vitro adhesion of the platelets was also suppressed on the PEO-grafted PU/PS IPNs prepared at lower temperature. The microdomain structure on the surface affected the adhesion and the activation of the adhered platelets, and the suppression of the phase separation resulted in the decrease of the domain size, which also enhanced the blood compatibility of the PEO-grafted PU/PS IPNs.     

Effect of synthesis temperature of PEO-grafted PU/PS IPNs on surface morphology and in vitro blood compatibility

When hydrophilic/hydrophobic polymers have a microdomain structure, platelet adhesion and activation are effectively suppressed by prohibition of the excessive assembly of glycoproteins and adenosine triphosphate (ATP) consumption of the platelets on the surface. In this study, poly(ethylene oxide)-grafted hydrophilic polyurethane (PU)/hydrophobic polystyrene (PS) interpenetrating polymer networks (IPNs) were synthesized by varying the synthesis temperature to control the phase separation and the microdomain surface structure, and the effect of the degree of phase separation on the in vitro blood compatibility. The size of the dispersed PS-rich domains in the PU-rich matrix decreased, and the hydrophilicity also decreased as the synthesis temperature of the PS network during the IPN synthesis was decreased, as the phase separation was suppressed during the synthesis. The amount of the adsorbed bovine plasma fibrinogens (BPF) on the PEO-grafted PU/PS IPNs decreased as the synthesis temperature was decreased, and the in vitro adhesion of the platelets was also suppressed on the PEO-grafted PU/PS IPNs prepared at lower temperature. The microdomain structure on the surface affected the adhesion and the activation of the adhered platelets, and the suppression of the phase separation resulted in the decrease of the domain size, which also enhanced the blood compatibility of the PEO-grafted PU/PS IPNs.     

PEO-grafting on PU/PS IPNs for enhanced blood compatibility--effect of pendant length and grafting density

Polyurethane (PU) homopolymers and PU/polystyrene (PS) interpenetrating polymer networks (IPNs) were successfully synthesized changing the length of the pendant poly(ethylene oxide) (PEO) chains and the grafting density of PEO chains. All the PU/PS IPNs had the microphase-separated structures in which the PS-rich phase domains were dispersed in the matrix of the PU-rich phase. The domain size decreased a little, as the degree of grafting with PEO chains was increased. The water swelling ratio increased, and the interfacial energy decreased, as the length of the pendant PEO chains, and the grafting density of PEO chains of the PEO-grafted PU/PS IPNs were increased, since the mobile hydrophilic pendant PEO chains effectively induced and absorbed the water, when they were contacted with water. The hydrophilic and highly concentrated pendant PEO chains could easily prohibit the adhesion of the fibrinogens and the platelets on the surface, and the blood compatibility of IPNs was enhanced by increasing of grafting with PEO chains. The adsorption of the fibrinogens and the platelets was suppressed, as the length of pendant PEO chains, and the grafting density were increased.     

Surface characteristics and blood compatibility of polyurethanes grafted by perfluoroalkyl chains

Polyurethane (PU) surface was chemically modified by grafting of perfluorodecanoic acid (PFDA) to produce a highly hydrophobic surface to compare the blood compatability with hydrophilic poly(ethylene oxide) (PEO) grafted PUs. The advancing contact angle of modified PU-PFDA was increased up to 115 deg, while that of untreated PU was 86 deg. The PFDA grafted PU exhibited less adhesion and shape change of platelets than untreated PU, and the activated partial thromboplastin time (APTT) of PU-PFDA was considerably extended. The ex vivo occlusion time of untreated PU was only 50 min, but that of PFDA grafted PU was extended to 130 min, indicating that this hydrophobic surface is significantly blood compatible. It is interesting to find that the enhanced blood compatibility of very hydrophobic PU-PFDA was equivalent to hydrophilic PU-PEO.     

Surface characteristics and blood compatibility of polyurethanes grafted by perfluoroalkyl chains.

Polyurethane (PU) surface was chemically modified by grafting of perfluorodecanoic acid (PFDA) to produce a highly hydrophobic surface to compare the blood compatability with hydrophilic poly(ethylene oxide) (PEO) grafted PUs. The advancing contact angle of modified PU-PFDA was increased up to 115 deg, while that of untreated PU was 86 deg. The PFDA grafted PU exhibited less adhesion and shape change of platelets than untreated PU, and the activated partial thromboplastin time (APTT) of PU-PFDA was considerably extended. The ex vivo occlusion time of untreated PU was only 50 min, but that of PFDA grafted PU was extended to 130 min, indicating that this hydrophobic surface is significantly blood compatible. It is interesting to find that the enhanced blood compatibility of very hydrophobic PU-PFDA was equivalent to hydrophilic PU-PEO.     

Synthesis and antithrombogenicity of heparinized polyurethanes with intervening spacer chains of various kinds

Heparin was immobilized to polyetherurethaneurea membrane by covalent or ionic bondings with intervening spacer chains having different lengths and different terminal functional groups. The amount of immobilization of heparin and the release rate of immobilized heparin were controlled by the nature and the mode of bonding of spacer chains. The heparinized polyetherurethaneurea membranes became more in vitro antithrombogenic and suppressed more strongly the adhesion and activation of platelets, as the amount of immobilization increased. It was also shown that the membrane to which the low-molecular-weight fraction of heparin was immobilized was less stimulating to platelets.     

In vitro and in vivo studies of PEO-grafted blood-contacting cardiovascular prostheses

The initial step of thrombus formation on blood-contacting biomaterials is known to be adsorption of blood proteins followed by platelet adhesion. Poly(ethylene oxide) (PEO) has been frequently used to modify biomaterial surfaces to minimize or prevent protein adsorption and cell adhesion. PEO was grafted onto a number of biomaterials in our laboratory. Nitinol stents and glass tubes were grafted with PEO by priming the metal surface with trichlorovinylsilane (TCVS) followed by adsorption of Pluronic and γ-irradiation. Nitinol stents were also coated with Carbothane® for PEO grafting. Chemically inert polymeric biomaterials, such as Carbothane, polyethylene, silicone rubber, and expanded polytetrafluoroethylene (e-PTFE), were first adsorbed with PEO-polybutadiene-PEO (PEO-PB-PEO) triblock copolymers and then exposed to γ-irradiation for covalent grafting. For PEO grafting to Dacron® (polyethylene terephthalate), the surface was sequentially treated with PEO-PB-PEO and Pluronics® followed by γ-irradiation. In vitro studies showed substantial reduction in fibrinogen adsorption and platelet adhesion to the PEO-grafted surfaces compared with control surfaces. Fibrinogen adsorption was reduced by 70-95% by PEO grafting on all surfaces, except for e-PTFE. The platelet adhesion corresponded to the fibrinogen adsorption. When the PEO-grafted surfaces were tested ex vivo/in vivo, however, the expected beneficial effect of PEO grafting was inconsistent. The beneficial effect of the PEO grafting was most pronounced on the PEO-grafted nitinol stents. Thrombus formation was reduced by more than 85% by PEO grafting on metallic stents. Only moderate improvement (i.e. 35% decrease in platelet deposition) was observed with PEO-grafted tubes of polyethylene, silicone rubber, and glass. For PEO-grafted heart valves made of Dacron, however, no effect of PEO grafting was observed at all. It appears that the extent of thrombus formation on PEO-grafted biomaterials was directly related to the extent of tissue damage during implantation surgery. Platelets can be activated and form aggregates in the bulk blood, and the formed platelet aggregates may be able to deposit on the PEO monolayer overcoming its repulsive property. Our studies indicate that the testing of in vitro platelet adhesion should include adhesion of large platelet aggregates, in addition to adhesion of individual platelets. Furthermore, the surface modification methods should be improved over the current monolayer grafting concept so that the repulsive force by the grafted PEO layers is large enough to prevent adhesion of platelet aggregates formed in the bulk blood before arriving at the biomaterial surface.     

In vitro and in vivo studies of PEO-grafted blood-contacting cardiovascular prostheses

The initial step of thrombus formation on blood-contacting biomaterials is known to be adsorption of blood proteins followed by platelet adhesion. Poly(ethylene oxide) (PEO) has been frequently used to modify biomaterial surfaces to minimize or prevent protein adsorption and cell adhesion. PEO was grafted onto a number of biomaterials in our laboratory. Nitinol stents and glass tubes were grafted with PEO by priming the metal surface with trichlorovinylsilane (TCVS) followed by adsorption of Pluronic and y-irradiation. Nitinol stents were also coated with Carbothane for PEO grafting. Chemically inert polymeric biomaterials, such as Carbothane, polyethylene, silicone rubber, and expanded polytetrafluoroethylene (e-PTFE), were first adsorbed with PEO-polybutadiene-PEO (PEO-PB-PEO) triblock copolymers and then exposed to gamma-irradiation for covalent grafting. For PEO grafting to Dacron (polyethylene terephthalate), the surface was sequentially treated with PEO-PB-PEO and Pluronics followed by gamma-irradiation. In vitro studies showed substantial reduction in fibrinogen adsorption and platelet adhesion to the PEO-grafted surfaces compared with control surfaces. Fibrinogen adsorption was reduced by 70-95% by PEO grafting on all surfaces, except for e-PTFE. The platelet adhesion corresponded to the fibrinogen adsorption. When the PEO-grafted surfaces were tested ex vivo/in vivo, however, the expected beneficial effect of PEO grafting was inconsistent. The beneficial effect of the PEO grafting was most pronounced on the PEO-grafted nitinol stents. Thrombus formation was reduced by more than 85% by PEO grafting on metallic stents. Only moderate improvement (i.e. 35% decrease in platelet deposition) was observed with PEO-grafted tubes of polyethylene, silicone rubber, and glass. For PEO-grafted heart valves made of Dacron, however, no effect of PEO grafting was observed at all. It appears that the extent of thrombus formation on PEO-grafted biomaterials was directly related to the extent of tissue damage during implantation surgery. Platelets can be activated and form aggregates in the bulk blood, and the formed platelet aggregates may be able to deposit on the PEO monolayer overcoming its repulsive property. Our studies indicate that the testing of in vitro platelet adhesion should include adhesion of large platelet aggregates, in addition to adhesion of individual platelets. Furthermore, the surface modification methods should be improved over the current monolayer grafting concept so that the repulsive force by the grafted PEO layers is large enough to prevent adhesion of platelet aggregates formed in the bulk blood before arriving at the biomaterial surface.     

Anticoagulant activity of immobilized heparin on the polypropylene nonwoven fabric surface depending upon the pH of processing environment

Antenna coupling microwave plasma enables a highly oxidative treatment of the outmost surface of polypropylene (PP) nonwoven fabric within a short time period. Subsequently, grafting copolymerization with acrylic acid (AAc) makes the plasma-treated fabric durably hydrophilic and excellent in water absorbency. With high grafting density and strong water affinity, the pAAc-grafted support greatly becomes feasible as an intensive absorbent and as a support to promote heparin immobilization through amide bonds. For heparin immobilized in acidic condition, the carbonate groups of the molecule tend to dissolve and passive encapsulation of the molecule prevents its functional groups from bonding with the carboxylic acid of pAAc. This effect leads to inhibit the immobilization process and consequently reduces the quantity as well as the bioactivity of the immobilized heparin. In alkaline processing environment, the oxidized uronic acid residues in heparin-related glycans are presumably cleaved and the removal of some oxidized residuals before immobilization process is likely to reduce the chain length of heparin. In the latter case, anticoagulant Factors X and XII, but not thrombin, are unaffected. Anticoagulant activity test using activated partial thromboplastin time (aPTT) is more sensitive in assessing heparin-immobilized surfaces, since it corresponds to Factor X and initiates the inhibition of Factor XII and thrombin. Likewise, platelets adhesion on the surfaces decreases as the process shifted from acidic to alkaline condition, whereas the hydrophilic character of the grafted pAAc markedly contributes to extend physical insertion of platelets. The immobilized heparin has a great part of original bioactivity, depending on the pH of the processing environment and the immobilized quantity. Relative bioactivity based upon aPTT tests is partially held longer than 90 days for the sample prepared in the alkaline or neutral environment.     

Gradient micropattern immobilization of heparin and its interaction with cells.

Heparin was immobilized on a polystyrene plate in a graded micropattern by photolithography. The micropattern was confirmed by staining with brilliant green. In the presence of basic fibroblast growth factor (bFGF), the growth of NIH3T3 cells was enhanced only in the heparin-immobilized regions. This result indicated that gradient-micropattern-immobilized heparin activated bFGF for cell growth. In addition, the growth of cells was found to be affected by the surface density of immobilized heparin. The surface density was regulated by a gap length of 2 microm-width stripes immobilized with heparin. Although a high density (a region having short gap length) of immobilized heparin suppressed the cell growth in the absence of bFGF, it enhanced cell growth in the presence of bFGF. The dependence of cell function on the density of immobilized heparin was visualized by gradient-micropattern-immobilization.     

Surface modification with PEO-containing triblock copolymer for improved biocompatibility: in vitro and ex vivo studies

Poly(ethylene oxide) (PEO) has been frequently used to modify biomaterial surfaces for improved biocompatibility. We have used PEO-polybutadiene-PEO triblock copolymer to graft PEO to biomaterials by gamma-irradiation for a total radiation dose of 1 Mrad. The molecular weight of PEO in the block copolymer was 5000. In vitro study showed that fibrinogen adsorption to Silastic, polyethylene, and glass was reduced by 70 to approximately 95% by PEO grafting. On the other hand, the reduction of fibrinogen adsorption was only 30% on expanded polytetrafluoroethylene (e-PTFE). In vitro platelet adhesion study showed that almost no platelets could adhere to PEO-coated Silastic, polyethylene, and glass, while numerous platelet aggregates were found on the ePTFE. The platelet adhesion in vitro corresponded to the fibrinogen adsorption. When the PEO-grafted surfaces were tested ex vivo using a series shunt in a canine model, the effect of the grafted PEO was not noticeable. Platelet deposition on ePTFE was reduced by PEO grafting from 8170 +/- 1030 to 5100 +/- 460 platelets 10(-3) microm2, but numerous thrombi were still present on the PEO-grafted surface. The numbers of platelets cumulated on Silastic, polyethylene, and glass were 100 +/- 80, 169 +/- 35, and 24 +/- 22 platelets 10(-3) microm2, respectively. This is about 35% reduction in platelet deposition by PEO grafting. While the numbers of deposited platelets were small, the decreases were not as large as those expected from the in vitro study. This may be due to a number of reasons which have to be clarified in future studies, but it appears that in vitro platelet adhesion and fibrinogen adsorption studies may not be a valuable predictor for the in vivo or ex vivo behavior of the PEO-grafted surfaces.     

Heparinized polyurethanes: in vitro and in vivo studies

Heparin immobilization chemistry using alkyl spacer arms was adapted to optimize yield on polyurethane (PU) surfaces. The resultant biological activity of immobilized heparin (HI) was examined in vitro and in vivo, and compared with a heparin releasing (HR) system. Immobilized heparin retained its ability to bind and inactivate thrombin and Factor Xa; nonspecific coagulation factor binding was insignificant. Such activity cannot be attributed to the leakage of improperly bound heparin. Immobilized heparin-polyurethane catheters implanted in canine femoral and jugular veins for 1 h periods exhibited significant reduction in thrombus formation compared with untreated PU contralateral controls. Polyurethane catheters coated with a 9% heparin dispersion in PU (HR) system provided even greater improvement in antithrombogenicity.     

The in vitro blood compatibility of poly(ethylene oxide)-grafted polyurethane/polystyrene interpenetrating polymer networks

Poly(ethylene oxide) (PEO)-grafted polyurethane (PU)/polystyrene (PS) interpenetrating polymer networks (IPNs) were synthesized. The effects of the mobile pendant PEO chains with their microphase separated structure on blood-compatibility were investigated. The morphology of both the fracture surface as well as the top surface indicate that the size of the dispersed domains of the PS-rich phase decreased as the grafting with the PEO was increased. The swelling ratio also decreased as the grafting with the PEO was increased. However, the dynamic contact angle and the interfacial energy between IPN surface and water decreased, due to the structural reorganization of the pendant PEO chains. PU/PS IPNs have an excellent mechanical property as compared with PU homopolymers. The adsorption of bovine plasma fibrinogen (BPF) onto the PU/PS IPNs and PU homopolymers was effectively suppressed by the PEO-grafting. In the platelet adhesion test, the amount of platelets adsorbed, activated, and/or coagulated upon the PEO-grafted PU/PS IPNs were reduced when compared to the ungrafted PU homopolymers.     

The in vitro blood compatibility of poly(ethylene oxide)-grafted polyurethane/polystyrene interpenetrating polymer networks

Poly(ethylene oxide) (PEO)-grafted polyurethane (PU)/polystyrene (PS) interpenetrating polymer networks (IPNs) were synthesized. The effects of the mobile pendant PEO chains with their microphase separated structure on blood-compatibility were investigated. The morphology of both the fracture surface as well as the top surface indicate that the size of the dispersed domains of the PS-rich phase decreased as the grafting with the PEO was increased. The swelling ratio also decreased as the grafting with the PEO was increased. However, the dynamic contact angle and the interfacial energy between IPN surface and water decreased, due to the structural reorganization of the pendant PEO chains. PU/PS IPNs have an excellent mechanical property as compared with PU homopolymers. The adsorption of bovine plasma fibrinogen (BPF) onto the PU/PS IPNs and PU homopolymers was effectively suppressed by the PEO-grafting. In the platelet adhesion test, the amount of platelets adsorbed, activated, and/or coagulated upon the PEO-grafted PU/PS IPNs were reduced when compared to the ungrafted PU homopolymers.     

Preparation and surface properties of PEO-sulfonate grafted polyurethanes for enhanced blood compatibility

In order to improve the thromboresistance of the commercial polyurethane(PU), its surface modification was accomplished by three new different methods and their surface characteristics were investigated using ATR-FTIR, ESCA, SEM, and dynamic contact angle measurements. Sulfonations using propane sultone were performed directly onto PU or onto hydrophobic dodecanediol (DDO) grafted PU or onto hydrophilic poly(ethyleneoxide) (PEO) grafted PU. ESCA data coincided well with ATR-IR results, as more 0 at. % for PEO grafted PUs and the presence of S for the sulfonated PUs were revealed. At SEM observation the surfaces of PU-DDO and PU-PEO were relatively smooth, whereas all the sulfonated PU surfaces showed excellent smoothness and homogeneity. The hydrophilicity of the surfaces was considerably increased after PEO grafting or sulfonation. In addition, all the sulfonated PU surfaces, particularly PU-PEO-SO₃, which has further hydrophilicity, exhibited complete wetting behavior due to the negatively charged SO₃ groups.