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PubMed2000

Exposure biomarkers and risk from gluing and heating of polyurethane: a cross sectional study of respiratory symptoms.

OBJECTIVES: To define the relation between exposure to polyurethane (PUR) glue, biomarkers of exposure and effect, and work related symptoms that occur at least once a week. METHODS: In a cross sectional study, 152 workers and 14 clerks in a factory with exposure to sprayed and heated PUR glue containing 4, 4'-diphenylmethane (MDI) or 1,6-hexamethylene (HDI) di-isocyanate were examined with gas chromatography-mass spectrometry (GC-MS) for metabolites of MDI in plasma (P-MDX) and urine (U-MDX), 2,4- and 2, 6-toluene di-isocyanate (TDI; P-TDX, U-TDX) and HDI in plasma and urine, specific serum IgG (S-IgG-MDI, S-IgG-HDI, and S-IgG-TDI, respectively) and IgE (S-IgE-MDI). Work related symptoms of the eyes and airways (nose or lower airways, or both), and lung function were also evaluated. RESULTS: P-MDX was detected in 65% of the workers, U-TDX in 47%, HDX in none. Three per cent were positive for S-IgE-MDI, 33% for S-IgG-MDI, 32% for S-IgG-TDI, and 12% for S-IgG-HDI. A few clerks had metabolites, and some had antibodies. Most metabolites and immunoglobulins were slightly correlated-for example, P-MDX v S-IgG-MDI: r(s)=0.21. Workers who heated glue had increased P-MDX (odds ratio (OR)=12 for a value above the median) and S-IgG-MDI (OR=3.7), sprayers P-2,4-TDX (OR=6.2) and P-2,6-TDX (OR=16). Twenty six per cent of the workers had work related symptoms of the airways, 21% from the nose, 11% from the lower airways. Spraying of glue increased the risk of work related symptoms and slightly decreased lung function. U-MDX was associated with work related symptoms from the airways (OR=3.7) and P-2,6-TDX with work related symptoms from the lower airways (OR=6.6). S-IgG-MDI was related to work related symptoms from the airways (OR=2.6). CONCLUSIONS: There were relations between exposures to sprayed and heated PUR glue based on MDI and HDI, concentrations of metabolites of MDI and TDI in plasma and urine, specific IgG serum antibodies against MDI, TDI, and HDI, and work related symptoms.

Adhesives↗

PubMed1996

Lacrimal canaliculus obstruction: nonsurgical treatment with a newly designed polyurethane stent.

A newly designed polyurethane stent was used to successfully treat 30 eyes (in 28 patients) with epiphora resulting from obstruction of the lacrimal canaliculus. After stent placement, epiphora resolved in all eyes. During follow-up, epiphora recurred in 20 eyes, but epiphora did not recur and the lacrimal canaliculus was patent in 12 eyes after the stent was removed. The stent appears to be valuable for nonsurgical treatment of obstruction of the lacrimal canaliculus.

Equipment Design↗

PubMed1998

Lacrimal system obstruction treated with lacrimal polyurethane stents: outcome of removal of occluded stents.

PURPOSE: To describe the short- and long-term outcomes of the removal of occluded stents. MATERIALS AND METHODS: With fluoroscopic guidance, 571 lacrimal polyurethane stents were placed in 502 patients with epiphora due to obstruction of the lacrimal system. Of the 571 stents, 142 were removed 2 weeks to 42 months (mean, 7 months) after placement because of recurrent epiphora, and the lacrimal system was irrigated with saline solution through the lacrimal point. RESULTS: Stent removal was well tolerated. Mild epistaxis occurred in one patient and was controlled with a nasal pack. Recurrent epiphora was due to obstruction of the stent with mucoid material in 49 (35%) of 142 systems and granulation tissue in 93 (65%) systems. After stent removal, 73 (51%) of the 142 lacrimal systems showed improvement of epiphora, with a patent lacrimal system at 7-day follow-up dacryocystography. During the follow-up of 2 weeks to 49 months (mean, 22 months) after stent removal, patency was maintained in 24 (33%) of the 73 lacrimal systems. CONCLUSION: Removal of an occluded lacrimal plastic stent was easy and safe. Recurrent epiphora after placement of lacrimal plastic stents can be treated with removal of the occluded stents an irrigation with saline solution through the lacrimal point, which resulted in a patent lacrimal system in 33% of cases in this study.

Adult↗

PubMed1999

Tracheobronchial strictures: treatment with a polyurethane-covered retrievable expandable nitinol stent--initial experience.

A polyurethane-covered retrievable expandable stent was placed in 13 patients with tracheobronchial strictures. In four patients with benign strictures, the stent was removed with use of a retrieval hook 2-6 months after placement. After stent removal, three of the four patients did not need further treatment. The retrievable stent warrants further investigation in the treatment of tracheobronchial strictures.

Adult↗

PubMed1976

Stimulation of human platelet aggregation by phospholipase-A and a saline "extract" of a polyurethane.

A saline extract of polyurethane (SPU) induces enzymatic conversion of arachidonic acid (either exogenous or released through the action of exogenous phospholipase-A) by activating a hitherto undiscovered labile enzyme, synthetase-alpha which is not blocked by aspirin. Addition of SPU, plus arachidonic acid or SPU plus phospholipase-A to platelet-rich plasma (PRP) triggers a biphasic platelet aggregation. Incubation of SPU with PRP results in activation and exhaustion of synthetase-alpha; this renders platelets refractory to the various aggregating agents.

Aspirin↗

PubMed1997

Double-J ureteric stent encrustations: clinical study on crystal formation on polyurethane stents.

OBJECTIVE: To evaluate the crystalline composition of encrustations on double-J ureteric stents in order to prevent their formation on the base of urolithiasis prophylaxis. PATIENTS: 40 patients had a polyurethane double-J ureteric stent inserted between June 1994 and March 1995. Group 1 comprised 22 stone formers whose stents were placed in support of endourological treatment or extracorporeal shock wave lithotripsy of renal or ureteric calculi. Group 2 comprised 18 patients whose stents were inserted for advanced and obstructive malignancy (n = 8) or as an adjunct to reconstructive surgery or endourological techniques (n = 10). After removal, stents were examined for encrustation and obstruction. A biochemical semiquantitative analysis was performed for deposits > 5 mg, and smaller sediments were examined with a polarizing optical microscope. RESULTS: The incidence of encrustation was significantly higher (p = 0.009) for stone formers. In addition, in this group indwelling times of encrusted and obstructed stents were significantly shorter (p = 0.03 and 0.02, respectively). No particular relationship was found between the incidence of encrustation and indwelling times for stone formers. Conversely, for patients without urolithiasis, indwelling times were significantly longer for encrusted or obstructed stents than for unaffected ones (p = 0.05 and 0.02, respectively). Biochemical and optical analyses of encrustations mainly revealed calcium oxalate, calcium phosphate and ammonium magnesium phosphate. Calcium oxalate was the main crystalline phase, especially in the absence of urinary infection. CONCLUSION: Calcium oxalate represents the principal component of double-J ureteric stent encrustations. Thus, prophylaxis of encrustation may consist of preventive measures usually applied in cases of recurrent idiopathic calcium oxalate urolithiasis.

Calcium Oxalate↗

PubMed2000

Surface photo-grafting of polyurethane with 2-hydroxyethyl acrylate for promotion of human endothelial cell adhesion and growth.

Cytocompatible polyurethane (PU) surface was prepared by photo-grafting 2-hydroxyethyl acrylate (HEA) onto the membrane surface. Graft polymerization was conducted by combining the use of the photo-oxidation and irradiation grafting. PU membrane was photo-oxidized to introduce the hydroperoxide groups onto the surface, then the membrane, immersed previously in monomer solution, was irradiated under UV light. The ATR-FTIR spectra, element spectroscopy for chemical analysis (ESCA), scanning electron microscopy (SEM) and water contact angle characterized the grafted copolymers and verified the occurrence of graft polymerization. The results showed that UV irradiation could realize the graft polymerization effectively and the grafting was confined within the surface layer. The grafted membrane showed minimal surface morphology. Human umbilical vein endothelial (HUVE) cells were seeded on the grafted surface. The performance of the surface in cell attachment and growth correlated with the oxygen content and mainly the carbonyl content on the surface. Cells were spread more extensively and grew faster on the surface with a higher oxygen content.

Acrylates↗

PubMed2000

Antithrombogenic polymer alloy composed of 2-methacryloyloxyethyl phosphorylcholine polymer and segmented polyurethane.

To evaluate the antithrombogenicity of a new polymeric biomaterial in vivo, a polymer alloy tube composed of poly[2-methacryloyloxyethyl phosphorylcholine(MPC)-co-2-ethylhexyl methacrylate](PMEH) polymer and a segmented polyurethane (SPU) was prepared by a solvent evaporation method on a Teflon rod from a homogeneous solution containing both the PMHE and SPU. The composition of the PMEH vs the SPU was 10 wt%. The inner and outer surfaces of the polymer alloy tubing were characterized by X-ray electron spectroscopic (XPS) measurements. The MPC units were located on the inner surface of the polymer alloy tubing rather than the outer surface. After immersion in aqueous media, a higher concentration of the MPC units was observed on both surfaces. Selective staining of the MPC units with osmium tetraoxide was carried out to observe the morphology of the PMEH domain on the surface of the polymer alloy. There were large-sized PMEH domains on the inner surface of the tubing but small-sized domains were found on the outer surface. This result was in good agreement with the XPS results. Blood compatibility of the polymer alloy was evaluated by observation of fibrinogen adsorption and platelet adhesion from human plasma. A lot of fibrinogen was adsorbed and many platelets adhered to the inner surface of the original SPU tubing. On the other hand, the PHEH/SPU polymer alloy tubing suppressed these adsorptions and adhesions. When the PMEH/SPU polymer alloy tubing was implanted into a rabbit's artery, thrombus could not be observed even after a 7-day implantation but the original SPU tubing was almost totally occluded only after a 90-min implantation due to serious thrombus deposition on the surface. These results clearly indicated that the PMEH in the SPU matrix acted as an antithrombus reagent by suppression of protein adsorption and platelet adhesion and activation. Particularly, the MPC units played a significant role in this function.

Adsorption↗

PubMed2001

PDMS-based polyurethanes with MPEG grafts: mechanical properties, bacterial repellency, and release behavior of rifampicin.

PDMS-based polyurethanes (PUs) grafted with monomethoxy poly(ethylene glycol) (MPEG) were synthesized to develop a coating material for urinary catheters with a silicone surface for minimizing urinary tract infections. MPEG was grafted on PDMS-based PUs by two methods depending on the PU synthetic routes: esterification and allophanate reactions. It was confirmed from mechanical characterization that an increase of the hard segment amount enhanced the ultimate strength and Young's modulus, while reducing elongation at the end-points. The incorporation of MPEG in PDMS-based PUs induced a decrease in tensile strength and Young's modulus, and increased elongation at the break point due to its high flexibility. When hydrated in distilled water, mechanical properties of all PUs synthesized in this study deteriorated due to water absorption. It was evident from the bacterial adhesion test that PDMS-based PUs showed moderate resistance to adhesion of E. coli on their surfaces compared to Pellethane, while the incorporation of MPEG significantly enhanced repellency to bacteria, including E. coli and S. epidermidis. We also studied the release behavior of an antibiotic drug, rifampicin, from the polymeric devices fabricated by solvent evaporation. Although rifampicin is hydrophilic and soluble in pH 7.4 phosphate buffer, it showed a sustained release over 45 days from PDMS-based PUs with MPEG that were grafted on ethylene glycol residues by allophanate reaction. This release characteristic was predominantly influenced by a hydrogen bond interaction between the polymers and rifampicin, which was confirmed through an ATR-IR study. This may imply that the specific interaction is responsible for the delayed release. Considering the mechanical properties, morphologies of drug-incorporated polymeric matrices, and drug release behaviors, PDMS-based PU with MPEG that were grafted on ethylene glycol (a chain extender) residues by allophanate reaction showed better material properties for uretharal catheter coating pusposes in order to minimize urinary tract infections.

Anti-Bacterial Agents↗

PubMed2002

Cytotoxic reaction and TNF-alpha response of macrophages to polyurethane particles.

Their unique mechanical and biological properties make polyurethanes (PUs) ideal materials for many implantable devices. However, uncertain long-term biostability in the human physiological environment limits their extensive clinical applications. Chronic inflammatory response associated with macrophage activation has been suggested as a prime factor; although the mechanism of macrophage activation in response to biomaterial surfaces and debris is still unknown. The overall objective of this work was to study the response of macrophages to PU materials in vitro by measuring cell viability and activity. The studies were carried out using phagocytozable-size PU particles from three types of commercially-available PUs: Pellethane 2363 80ABA (PL); Tecothane TT2065 (TC65); and Tecothane TT2085 (TC85). These polymers posess the same generic composition but differ in the length of hard and soft segments, as revealed by the FTIR and NMR studies. The results showed that PU particles affected both viability and activity of J774 macrophages. The percentage of mortality ranged from 1 to 15% with 10-100 microg ml(-1) of particles after 24 and 48 h incubation. These three types of particles induced different mortality on the macrophages. Specifically, the mortality with PL particles was 1-4% (p > 0.05), while the mortality with TC85 particles was 2-10% (p < 0.05) and 4-15% with TC65 (p < 0.05). Conversely, these particles also affected cell proliferation. Cell numbers increased by 132 and 167% after 24 and 48 h incubation, respectively, without particles, whereas the cell numbers increased only 46 and 78% with TC65, 66 and 105% with TC85, and 67 and 110% with PL in the presence of 100 microg ml(-1) of particles for the respective incubation times. PU particles also increased TNF-alpha release from macrophage. After having been incubated for 24 h with 100 microg ml(-1) particles of TC65, TC85, and PL, macrophages release TNF-alpha 7.4, 5.2, and 4.1 times more than the control. In conclusion, PU particles had cytotoxic effects on J774 macrophage at high concentrations. The order of macrophage response for three types of particles was TC65 > TC85 > PL. PU particles' effect on macrophage viability and activity depends on the concentration of particles and their chemical composition, especially on the ratio of hard to soft segments.

Animals↗

PubMed2002

Physicochemical properties and in vitro biocompatibility of PEO/PTMO multiblock copolymer/segmented polyurethane blends.

A multiblock copolymer composed of poly(ethylene oxide) (PEO) and poly(tetramethylene oxide) (PTMO) and which forms a physical hydrogel was blended with Pellethane, a commercial segmented polyurethane (SPU) developed for various biomedical devices, to provide a PEO-rich surface with improved stability. The effect of the copolymer blending was evaluated with respect to surface hydrophilicity, long-term stability, mechanical properties, in vitro protein adsorption, and platelet adhesion. A small amount of the copolymer additive (5 wt%) significantly improved surface hydrophilicity, which was then gradually enhanced by increasing the amount of the copolymer in the blends. The blend films exhibited minimal extraction of the copolymer additive when exposed to a buffer solution for 2 months at 37 degrees C, resulting in less than 1 wt% weight loss of the films even with 30 wt% content of the copolymer in the blends. Although a certain degree of alteration in the mechanical properties was observed by increasing the copolymer content, the mechanical properties were well maintained for up to 10 wt% addition of the copolymer, when compared with the bare SPU. Protein adsorption was significantly reduced with a small amount of copolymer additive as low as 5 wt%. Fibrinogen, an adhesive protein for further cellular adhesion and activation, was effectively repelled by increasing the amount of copolymer additive. The platelet adhesion test revealed that the blend film surface reduced platelet adhesion and the degree of inhibition was proportional to the content of the additive, up to 30 wt%. The high molecular weight (Mw = 66,000) and compatible chemical structure of the copolymer with SPU made the surfaces PEO-rich and stable in an aqueous environment, resulting in an enhancement of the resistance to protein adsorption and platelet adhesion without a significant deterioration in physical properties.

Adsorption↗

PubMed2003

Photografting of poly(hydroxylethyl acrylate) onto porous polyurethane scaffolds to improve their endothelial cell compatibility.

In order to improve the cytocompatibility of polyurethane (PU) porous scaffolds obtained by thermally-induced phase separation, poly(hydroxylethyl acrylate) (PHEA) was covalently immobilized by grafting copolymerization of HEA by photo-oxidation of the scaffolds and initiation of UV light. FT-IR-ATR spectroscopy and X-ray photoelectron spectroscopy (XPS) characterizations confirmed the occurrence of the grafting co-polymerization of HEA on the porous PU scaffolds. The measurement of water absorption demonstrated the improvement of the hydrophilicity after grafting with PHEA. The results obtained in a human umbilical vein endothelial cell (HUVEC) culture proved that the porous PU scaffold modified with the hydrophilic PHEA had better cytocompatibility than the control. The influence of surface pore size on the HUVEC growth behavior was assessed regarding cell anchorage, proliferation and viability, as well as morphology. An overall increase of cell number and viability with the decrease of the surface pore size was found.

Absorption↗

PubMed2003

Corrosion resistance of polyurethane-coated nitinol cardiovascular stents.

Corrosion of metal stents implanted inside an artery can have two adverse effects: (1) tissue reaction and possible toxic effects from the metal ions leaching out of the stent, and (2) loss of mechanical strength of the stent caused by corrosion. The corrosion resistance of Nitinol (Nickel-Titanium) stents and its modulation with different film thickness of polymer coating was studied against an artificial physiological solution using a Potentiostat/Galvanostat and an electrochemical corrosion cell. The corrosion rate decreased rapidly from 275 microm/year for an uncoated surface down to less than 13 microm/year for a 30 microm thick polyurethane coating. Stainless steel (316L) and Nitinol both contain potentially toxic elements, and both are subject to stress corrosion. Minimization of corrosion can significantly reduce both tissue reaction and structural degradation.

Alloys↗

PubMed2003

Safety issue of re-sterilization of polyurethane electrophysiology catheters: a cytotoxicity study.

The reuse of electrophysiology catheters could result in significant cost savings. However, re-sterilization of catheters could lead to several adverse consequences, including toxicity related to potential chemical reactions that occur during sterilization due to toxic residues remaining on the surface of catheters. The objective of this study was to investigate in vitro cytotoxicity of polyurethane (PU)-based catheter extracts on macrophages after their re-sterilization. We have compared three sterilization methods: steam autoclave, ethylene oxide (EtO) and hydrogen peroxide plasma (Sterrad system). Our results showed that the viability of cells varied from 90% to 99% as a function of incubation time and number of sterilization cycle. While there was no statistical difference based on the sterilization procedure, the number of sterilization cycles (up to 10 cycles) presents a statistically significant effect on the viability of J774 macrophages. However, extract obtained after resterilization of PU-based catheters had a low cytotoxic effect on J774 macrophages, since the overall cell mortality remained under 10%. An inhibitory effect on cell growth was also observed, which was not significant either as a function of incubation time, sterilization technique or the number of sterilization cycles. Finally, extracts of PU-based catheters had no statistically significant effect on TNF-alpha release by J774 macrophage. Even though there were some statistically significant differences between the control and processed samples, and among processed samples, our data suggest that one single reprocessing of PU-based catheters may not induce clinically significant changes in their cytotoxicity behaviour.

Animals↗

PubMed2004

Synthesis and characterization of novel polyurethane cationomers with dipeptide sequences and alkylammonium groups.

A synthetic approach to polyurethane cationomers containing S-pyroglutamyl-S-glutamic acid dipeptide (S-PyGlu-S-Glu) and alkylammonium groups is presented. Two segmented polycations, based on polycaprolactone diol, isophorone diisocyanate and dipeptide together with N-methyldiethanolamine, subsequently quaternized with dodecylbromide, were synthesized and characterized by IR spectroscopy, GPC, DSC and reduced viscosity measurements. Such polycations exhibited excellent film forming properties and their soft elastomeric nature provides adequate physical properties. Optical rotation varying from +10 (monomer) to -15 (polycation) could be associated with a configuration pertubation through the asymmetric carbon atoms of glutamic residues. Susceptibility of the cationic surface to heparinization and then to blood-polymer interaction suggested an anticoagulant activity of the heparinized polymeric films.

Anticoagulants↗

PubMed2005

In vitro thrombogenicity investigation of new water-dispersible polyurethane anionomers bearing carboxylate groups.

New segmented polyurethane (PU) anionomers based on hydroxytelechelic polybutadiene were synthesized via an aqueous dispersion process. Incorporation of carboxylic groups was achieved using thioacids of different length. Surface properties were investigated by mean of water absorption analysis and static contact-angle measurements using water, diiodomethane, formamide and ethylene glycol. Blood compatibility of the PUs was evaluated by in vitro adhesion assays using 111In-radiolabeled platelet-rich plasma and [125I]fibrinogen. Morphology of the adhered platelets was examined by scanning electron microscopy (SEM). Results were compared to two biomedical-grade PUs, namely Pellethane and Tecoflex. Insertion of carboxylic groups increased surface hydrophilicity and limited water uptake ( < 8% for an ion content of 5% by weight). Surface energy of all synthesized PUs was between 40 and 45 mJ/m2. Platelet adhesion and fibrinogen adsorption on the PU anionomer surfaces were affected as a function to the increase of graft length; thiopropionic was the most haemocompatible, followed by thiosuccinic and then thioglycolic acid. SEM analyses of all ionic PU samples exhibited low platelet adhesion to surfaces with no morphological modification. In conclusion, increased hydrophily, dynamic mobility and charge repulsion are synergistic key factors for enhanced haemocompatibility.

Absorption↗

PubMed1992

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.

Biocompatible Materials↗

PubMed1993

Adsorption behavior of fibrinogen to sulfonated polyethyleneoxide-grafted polyurethane surfaces.

Fibrinogen adsorptions to surface modified polyurethanes (PU, PU-PEO, and PU-PEO-SO3) were studied from plasma in vitro. PU and PU-PEO surfaces demonstrated that initial adsorption increases with increasing plasma concentration in kinetic profiles and adsorption time in adsorption profiles as a function of plasma concentration, but after the plateau is reached, its adsorption amount decreases as plasma concentration (0.2-2.0%) and adsorption time (1-120 min) increase, respectively. In contrast, PU-PEO-SO3 showed that initial adsorption is almost same regardless of plasma concentration and adsorption time, which is due to the high affinity of surface sulfonate group to fibrinogen. All the surfaces indicated the Vroman effect at about 0.6% plasma concentration; however, the displacement was relatively low. Adsorbed amount of fibrinogen at steady state decreased in the order: PU > PU-PEO-SO3 > PU-PEO, regardless of adsorption time and plasma concentration. The adsorption behavior of PU-PEO-SO3 is attributed to both effect of low binding affinity of PEO chain and high affinity of pendant sulfonate group toward fibrinogen.

Adsorption↗