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PubMed2002

Synthesis and surface properties of environmentally responsive segmented polyurethanes.

Polyurethanes, containing well-defined assemblies of perfluoro-polyether (PFPE or hexafluoropropene oxide oligomer), polydimethylsiloxane (PDMS), and polyethylene glycol (PEG) segments, exhibit oleophobic, hydrophobic, and hydrophilic properties in response to the polarity of the contacting medium. These polymers were prepared by reacting hydroxy(polyethyleneoxy)-propylether-terminated PDMS block copolymer (HO-PEG-PDMS-PEG-OH) with 4,4'-methylene-bis(phenylene isocyanate) (MDI) in the presence of dibutyltin dilaurate catalyst, followed by reaction with 1,2-diol functional PFPE and chain extension with 2,2,3,3-tetrafluoro-1,4-butanediol (FB). The oleophobic and hydrophobic properties of the segmented polyurethanes (SPU) are due to the segregation of PFPE segments at the polymer-air interface. Wettability studies revealed that the same surface becomes hydrophilic, presumably due to the segregation of the PEG segments at the polymer-water interface. This hydrophobic-to-hydrophilic transformation of the surface prevails not only when the polymer is in contact with liquid water but with water vapor as well. The understanding of the reconstruction mechanism of this novel family of SPU surfaces would furnish valuable information for various applications where dynamic transformation of surface activity is desired.

Journal Article↗

PubMed2001

Molybdenum determination in iron matrices by ICP-AES after separation and preconcentration using polyurethane foam.

A procedure is proposed for the separation and determination of molybdenum in iron matrices by a batch process. It is based on the solid-phase extraction of the molybdenum(V) ion as thiocyanate complex on polyurethane (PU) foam. The extraction parameters were optimized. Using 0.20 mol L-1 hydrochloric acid, a thiocyanate concentration of 0.10 mol L-1, 100 mg of polyurethane foam and shaking time of 10 min, molybdenum (5-400 micrograms) can be separated and preconcentrated from large amounts of iron (10 mg). Desorption was carried out instantaneously by conc. nitric acid or acetone. Distribution coefficients, sorption capacity of the PU foam and coefficients of variation were also evaluated. The effect of some ions on the separation procedure was assessed. Iron(III) should be reduced to iron(II). The proposed procedure was used to determine molybdenum in standard iron matrices such as steel and pure iron. The achieved results did not show significant differences with certified values.

Journal Article↗

PubMed2002

Polyurethane-covered dacron mesh versus polytetrafluoroethylene DualMesh for intraperitoneal hernia repair in rats.

PURPOSE: Abdominal hernia repair using the intraperitoneal implantation of a prosthesis requires mesh with impervious properties, such as expanded polytetrafluoroethylene (ePTFE). A newly developed polyurethane-covered polyester mesh with impervious properties has recently been introduced as a less expensive alternative to PTFE, and we compare these materials herein. METHODS: The adhesion formation and stability of intraperitoneal abdominal hernia repairs with DualMesh (macroporous ePTFE mesh with a microporous component) and PolyesterComposite (the newly developed polyurethane-covered Dacron mesh) were compared in a rat model. Forty rats were randomly divided into two groups; ten animals from each group were killed after 14 days, and the other ten after 90 days. RESULTS: The number and intensity of adhesions were comparable in the PolyesterComposite and PTFE groups. Loose adhesions were seen in 13 animals and appeared only selectively at the fixation sutures. Both PolyesterComposite and PTFE induced the formation of a smooth neoperitoneum on the intraperitoneal surface and showed a complete ingrowing of the prosthesis in the surrounding tissue. There were no significant differences between the prostheses in terms of clinical herniation pressure and hydroxyproline concentration. CONCLUSIONS: PolyesterComposite and PTFE are both suitable prostheses for intrapertoneal implantation, but PolyesterComposite is less expensive, which is an important advantage for clinical use.

Animals↗

PubMed1992

In vivo fragmentation of microporous polyurethane- and copolyesterether elastomer-based vascular prostheses.

A previous study showed that microporous, compliant and (bio)degradable vascular prostheses prepared from a polyurethane/poly(L-lactic acid) mixture can function as a temporary scaffold for the regeneration of small-calibre arteries. In this study the mechanism of fragmentation of vascular prostheses made of polyurethane, copolyesterether and blends of either polyurethane or copolyesterether with polymers differing in biodegradability, crystallinity and glass transition temperature is investigated. Animal studies revealed that after 6 wk of implantation only the prostheses made of blends containing a second polymer which was non-elastic at 37 degrees C were fragmented extensively, whether the second polymer was (bio)degradable or not. It is concluded that fragmentation of the prostheses is mainly caused by alternating stresses induced by the arterial pulsations and that (bio)degradation plays a minor role.

Animals↗

PubMed2006

Synthesis, characterization, antibacterial and corrosion protective properties of epoxies, epoxy-polyols and epoxy-polyurethane coatings from linseed and Pongamia glabra seed oils.

The aim of this paper is to investigate the structures and properties of epoxidized linseed and Pongamia glabra oils (LOE/POE), their derived products-epoxy-polyols (HLOE/HPOE), epoxy-polyurethanes (EU=LOPU/POPU) and EU coatings. Changes in epoxy equivalent, iodine value, hydroxyl value and percent saturation of oil backbone in due course of epoxidation and hydroxylation reactions, were plotted as a function of time. Spectral (IR, (1)H NMR and (13)C NMR), physico-chemical and thermal (TGA and DSC) analyses of aforementioned resins were performed by standard methods. Physico-mechanical and chemical resistance tests reveal that coatings of LOPUs perform better than those of POPUs. It was found that properties of oil epoxy-polyurethane coatings are mainly governed by: (i) fatty acid composition and nature of starting oils, (ii) extent of epoxidation, (iii) number and location of hydroxyls and residual double bonds in the final product and (iv) the presence of long dangling chains. PO, HLOE and LOPUs exhibit good antibacterial activity against Escherichia coli at very small MIC. These EU systems can be safely employed unto 220 degrees C.

Anti-Bacterial Agents↗

PubMed2000

Characterization of polyether and polyester polyurethane soft blocks using MALDI mass spectrometry

Selective degradation reactions combined with MALDI analysis have been applied for molecular weight (MW) determination of polyether and polyester polyurethane (PUR) soft blocks. Selective degradation allows recovery of the polyols, and direct observation of the soft block oligomer distribution is possible for the first time by using MALDI. Ethanolamine is applied for polyether PUR degradation. MALDI analysis indicates that the recovered polytetrahydrofuran (pTHF) MW distribution is nearly identical to the unreacted pTHF material. Reduction in the ethanolamine reaction time allows observation of oligomer ions containing the diisocyanate linkage, which provide identification of the diisocyanate. Ethanolamine is not used for polyester PUR's degradation because the ester bonds will be cleaved. Therefore, phenylisocyanate is applied for polyester PUR degradation. Polybutylene adipate (pBA) oligomers were directly observed in the MALDI spectra of the degraded pBA-PUR samples. Comparison of the degraded pBA-PUR oligomer distribution with the unreacted pBA material indicates that low-mass oligomers are less abundant in the degraded pBA-PURs. Oligomer ions containing the diisocyanate linkage are also observed in the spectrum, providing a means for identifying the diisocyanate used for PUR syntheses. Size-exclusion chromatography (SEC) was combined with MALDI to provide accurate MW determination. Narrow MW fractions of the degraded and unreacted polyols were collected and analyzed by MALDI. This method allows precise calibration of the SEC chromatogram. The SEC-MALDI results provide significantly larger Mw and PD values than MALDI alone. Using SEC-MALDI, it was determined that the PD indexes of the pTHF and pBA samples are larger than the assumed values, which are based on the polyol synthesis reactions. The combination of selective degradation with SEC-MALDI, using either ethanolamine or phenylisocyanate, is a viable method for polyurethane polyol characterization.

Journal Article↗

PubMed2006

Synthesis, swelling behavior, and biocompatibility of novel physically cross-linked polyurethane-block-poly(glycerol methacrylate) hydrogels.

Physically cross-linked novel block copolymer hydrogels with tunable hydrophilic properties for biomedical applications were synthesized by controlled radical polymerization of polyurethane macroiniferter and (2,2-dimethyl-1,3-dioxolane) methyl methacrylate. The block copolymers were converted to hydrogels by the selective hydrolysis of poly[(2,2-dimethyl-1,3-dioxolane) methyl methacrylate] block to poly(glycerol methacrylate). The block copolymerization has been monitored by monomer conversion and molecular weight increase as a function of time. It was observed that the polymerization proceeded with a characteristic "living" behavior where both monomer conversion and molecular weight increased linearly, with increasing reaction time. The resulting hydrogels were investigated for their equilibrium water content (EWC), dynamic water contact angles, swelling kinetics, thermodynamic interaction parameters, plasma protein adsorption, and platelet adhesion. Similar to our previous mechanically responsive hydrogels (Mequanint, K.; Sheardown, H. J. Biomater. Sci. Polym. Ed. 2005, 10, 1303-1318), the present results indicated that block copolymer hydrogels have excellent hydrophilicity and swelling behavior with improved modulus of elasticity. The equilibrium swelling was affected by the hydrolysis time, block length of poly(glycerol methacrylate), temperature, and the presence of soluble salts. Fibrinogen adsorption and platelet adhesion were significantly lower for the hydrogels than for the control polyurethane, whereas albumin adsorption increased for the hydrogels in proportion to the contents of poly(glycerol methacrylate). These hydrogels have potential in a number of biomedical applications such as drug delivery and scaffolds for tissue engineering.

Adsorption↗

PubMed1998

A new biomedical polyurethane with a high modulus based on 1,4-butanediisocyanate and epsilon-caprolactone.

A new approach to the synthesis of biomedical polyurethanes based on epsilon-caprolactone and 1,4-butanediisocyanate with a high modulus, has been developed. By chain extending an epsilon-caprolactone prepolymer with a long uniform-size diisocyanate block, a segmented polyurethane with uniform-size hard segments was obtained. It shows excellent mechanical properties; an extremely high modulus of 105 MPa and a tensile strength of 35 MPa. The polymer is soluble at high concentrations in various volatile solvents such as chloroform and 1,4-dioxane. By a combination of salt-leaching and freeze-drying, porous materials have been obtained in which macropores ranging in size from 150-300 microm are highly interconnected by micropores. The material shows a sufficiently high compression modulus of 200 kPa and appears to be suitable for biomedical applications such as meniscal prostheses.

Journal Article↗

PubMed1999

Polyurethane-maleamides for cardiovascular applications: synthesis and properties.

Several polyurethane-maleamides (PUMAs) containing polyether or polycarbonate soft segments, and aromatic or aliphatic hard segments were synthesized by solution or bulk polymerization, using maleic acid (MA) or a mixture of MA and butanediol as chain extenders. Using this process, activated double bonds are introduced into the polymer chains and the base polyurethanes may undergo further modification via specific grafting, thus improving their tissue compatibility. PUMAs chemicophysical properties were evaluated by gel permeation chromatography (GPC), intrinsic viscosity analyses, differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR) and tensile mechanical tests. Polycarbonate diol (PCU)-based PUMAs showed higher molecular weights than polyether diol (PEU)-based ones. The use of butanediol in mixture with maleic acid led to an increase of molecular weights. FT-IR confirmed the presence of the bands related to the amide groups and to the conjugated double bond, yet more evident for the polymer obtained in solution. The higher crystallinity shown by this polymer was also indicative of a better phase separation. All the PCU-PUMAs exhibited similar tensile properties with a higher stiffness than PEU-PUMAs. Among the PEU-PUMAs, the highest tensile properties were shown by the polymer obtained in solution, and by the one derived from a mixture of maleic acid and butanediol.

Journal Article↗

PubMed1997

Conditioning fluid influences on the surface properties of silicone and polyurethane peritoneal catheters: implications for infection.

Catheter-related infection remains a considerable problem in continuous ambulatory peritoneal dialysis (CAPD). This study examined the adherence of clinical isolates of Staphylococcus epidermidis to commercially available polyurethane and silicone peritoneal catheters in the presence and absence of a proteinaceous conditioning film. In addition, the effects of the conditioning film on the surface properties (advancing and receding contact angles, and surface rugosity) of these biomaterials were investigated. Bacterial adherence to polyurethane and silicone catheters, pre-treated with phosphate-buffered saline (PBS) or artificial spent peritoneal dialysate (ASD) for 1 h at 37 degrees C, was examined using a radiometric (2-3H-adenine) adherence assay. The advancing and receding contact angles and the surface rugosity of ASD- and PBS-treated biomaterials were examined using a dynamic contact angle analyser and an atomic force microscope, respectively. The bacterial isolates were selected to represent high and low cell surface hydrophobicity. The hydrophobic isolate exhibited both a significantly greater rate and a significantly greater extent of adherence than the hydrophilic isolate to both catheter materials, independent of pre-treatment. In general, pre-treatment of the catheter materials with ASD significantly decreased the subsequent adherence of both isolates owing to the deposition of a conditioning film on the surface of the biomaterial. ASD treatment also decreased both the advancing and receding contact angles and the surface rugosity of both catheter materials. This study highlights the influence of both bacterial cell surface hydrophobicity and biomaterial surface conditioning films on bacterial adherence to CAPD catheters. In addition, it is recommended that the effects of proteinaceous conditioning films on biomaterial surface properties should be considered when assessing materials for medical devices and products.

Journal Article↗

PubMed2002

Oxygen plasma modification of polyurethane membranes.

Polyurethane membranes were prepared under nitrogen atmosphere by using various proportions of toluene diisocyanates (TDI) and polypropylene-ethylene glycol (P) with addition of no other ingredients such as catalysts, initiator or solvent in order to achieve medical purity. Effects of composition on mechanical properties were examined. In general, modulus and UTS values demonstrated an increase and PSBR demonstrated a decrease as the TDI/Polyol ratio of the polymer increased. Elastic modulus, ultimate tensile strength (UTS) and per cent strain before rupture (PSBR) values were found to be in the range of 1.4-5.4 MPa, 0.9-1.9 MPa, and 60.4-99.7%, respectively. Surfaces of the membranes were modified by oxygen plasma applying glow-discharge technique and the effect of applied plasma power (10 W or 100 W, 15 min) on surface hydrophilicity and on the attachment of Vero cells were studied. Water contact angle values of the plasma modified surfaces varied between 67 degrees and 46 degrees, demonstrating a decrease as the applied plasma power was increased. The unmodified material had 42-45 cells attached per cm(2). It was observed that as the applied power increased the number of attached cells first increased (60-70 cells/cm(2) at 10 W) and then decreased (27-40 cells/cm(2) at 100 W). These demonstrated that surface properties of polyurethanes can be modified by plasma-glow discharge technique to achieve the optimum levels of cell attachment.

Journal Article↗

PubMed2000

Micro-SAXS and force/strain measurements during the tensile deformation of single struts of an elastomeric polyurethane foam.

A microdeformation stage based on a piezoelectric crystal actuator capable of measuring the force applied to micrometre-sized polymeric samples is described. Laboratory force/strain measurements on a single strut of an elastomeric polyurethane foam have been conducted for the first time. The device has also been used on the microfocus beamline at the European Synchrotron Radiation Facility to collect microbeam small-angle X-ray scattering data simultaneously with strain and force measurements during the time-resolved tensile deformation of a single strut of elastomeric polyurethane foam.

Journal Article↗

PubMed2005

Abomasal cannulation in the milk-fed calf using a 7 mm polyurethane tube.

The main objective of this study was to develop a simple and effective surgical technique for abomasal cannulation in neonatal calves. General anaesthesia was induced in 12, 3-day-old male dairy calves and a polyurethane cannula surgically implanted in the abomasal body (n = 12) and pyloric antrum (n = 6) through a right paracostal incision. Fifteen cannulae remained in situ from day 3 to 34 of life (mean: 29 days), and three cannulae were extruded 13-14 days after placement. Calves were clinically healthy and gained weight during the study. Cannulae were well tolerated by the calves and abomasal contents did not leak from the cannula sites. Necropsy examination revealed firm adhesions between the abomasum and parietal peritoneum at the cannula sites with no evidence of leakage or peritonitis. We conclude that surgical placement of polyurethane tubes designed for percutaneous endoscopic gastrostomy provided a useful method for cannulation of the abomasum of neonatal calves. The cannulation technique can be used for experimental studies, as well as for nutritional and fluid support of sick calves that cannot be managed by oral treatment.

Abomasum↗

PubMed1986

Five-year performance of the Medtronic 6971 polyurethane endocardial electrode.

There is a considerable debate over the long-term performance of polyurethane electrodes. Observation to date has demonstrated surface cracking and some clinical failures in patients. Since 1978 we have implanted about 82 6971 Unipolar Medtronic electrodes in the ventricle. In 33 patients, lead integrity was assessed by chronic thresholds determined by decreasing pulse width and pulse amplitude. Sensing functions were assessed by electrocardiographic rhythm analysis. At a follow-up between 7 and 67 months, chronic thresholds at 2.50 volts were 0.08 +/- 0.04 milliseconds in 26 patients with Medtronic Pulse generators (Models 8423, 5985, and 7000). In two patients with similar units, no loss of capture was seen even at 0.05 milliseconds. Three patients, one with Cordis Unit (233F) showed loss of capture at 0.20 milliseconds at 2.00 MA, the other with a Pacesetter unit (255-6) showed loss of capture at 0.20 milliseconds, at 2.50 volts. One patient with Intermedics unit (283) lost capture at 0.07 milliseconds at 2.70 volts. Insulation breaks seen in two patients were demonstrated by pectoral stimulation and pacemaker oversensing. In addition, 24-hour long-term electrocardiographic monitoring was performed in 22 patients between 23 to 70 months. Appropriate pacemaker function was seen except in one patient who demonstrated oversensing. Interruption in insulation was demonstrated at the ligature site at exploration. Thus, in this series of patients who were paced in the ventricle by the 6971 Medtronic electrode, only two patients have demonstrated insulation failure. The incidence of insulation break in this polyurethane unipolar electrode is uncommon and occurs at further stress points.

Electrodes, Implanted↗

PubMed1968

Effects of jet-fuel microbial isolates on a polyurethane foam.

Jet-fuel microbial isolates were studied for effects on a polyurethane foam material that has been proposed as a baffling material for use in aircraft fuel tanks. Evidence was found that a polyesterurethane foam gave increased cell counts and oxygen uptake with a bacterial isolate, and extensive matting with fragmentation and decreases in tensile strength of the foam with a fungal isolate. The polyurethane foam was affected by activity of the jet-fuel microbial isolates to an extent that would cause serious microbiological problems in the fuel tanks of jet aircraft.

Journal Article↗

PubMed1969

Effects of polyurethane foams on microbial growth in fuel-water systems.

Four, open-cell, ester-base polyurethane foams were examined for their effect on growth of fuel-utilizing organisms in jet fuel-water systems. Three foams contained a potential biocide, tetraethylthiuram E (0.66%), sodium omadine (0.07%), or zinc omadine (0.07%), all w/v. These were compared with a control foam which did not contain an additive. Each foam was examined in fuel-water systems containing JP-4 fuel, JP-4 fuel plus 0.1% anti-icing additive (AIA), or JP-5 fuel. Pure cultures of a fuel-grown bacterium, Pseudomonas aeruginosa, and of a fuel-grown fungus, Hormodendrum (Cladosporium) sp., served as test organisms. In control cultures without foam and in cultures containing control foam, P. aeruginosa achieved maximum stationary-phase populations of approximately 10 viable cells per ml, and Hormodendrum sp. produced an extensive mycelial mat. In the three fuel systems examined, tetraethylthiuram E- and sodium omadine-containing foams had little effect on growth of the bacterium; foam with zinc omadine decreased the rate of bacterial growth but had little effect on total populations. Tetraethylthiuram E decreased the rate of fungal growth and showed its greatest effect in JP-4 plus AIA. Foam with sodium omadine or zinc omadine markedly decreased fungal growth in all three fuel systems. The data suggest that either sodium omadine or zinc omadine in polyurethane foam may be a useful antifungal agent; and that tetraethylthiuram E and AIA could exert a synergistic effect, particularly at AIA concentrations which have been reported to occur in some field situations.

Journal Article↗

PubMed1993

Cancer incidence and mortality in the Swedish polyurethane foam manufacturing industry.

Toluene diisocyanate (TDI) and methylene diphenyldiisocyanate (MDI) are used in large quantities in the polyurethane foam manufacturing industry. Both substances are mutagenic and at least TDI is carcinogenic to animals, but the occupational hazard with respect to cancer is not known. Cancer incidence and mortality patterns were therefore investigated in a cohort of 4154 workers from nine Swedish plants manufacturing polyurethane foam, employed for at least one year. Each workplace and job task in the nine plants was categorically assessed for each calendar year by an experienced occupational hygienist, for "no exposure", "low or intermittent exposure", or "apparent exposure" to TDI and MDI. The observed deficit for all cause mortality (standardised mortality ratio (SMR) 0.78, (95% confidence interval (95% CI) 0.66-0.93) became smaller (SMR 0.92) excluding the first 10 years since the start of exposure and was ascribed to a healthy worker effect. No increased risk for death from bronchial obstructive diseases was found. An almost statistically significant deficit occurred for all malignant neoplasms (standardised incidence ratio (SIR) 0.81, 95% CI 0.63-1.02); slight (not significant) increased risks were found for rectal cancer (SIR 1.66) and non-Hodgkin's lymphoma (SIR 1.53). The SIR for non-Hodgkin's lymphoma increased to 2.80 (95% CI 0.76-7.16) when the first 10 years since first exposure were excluded from the observation period. The corresponding figure for rectal cancer was 1.92 (95% CI 0.52-4.92). Further restricting the analysis to those who had experienced an apparent exposure to TDI or MDI increased the SIR for both rectal cancer (3.19, 95% CI 0.66-9.33), and non-Hodgkin's lymphoma (3.03, 95% CI 0.37-10.9). These estimates were based, however, on few incident cases. As the cohort is still young and little time has elapsed since the start of exposure, future follow ups will enable a more conclusive evaluation.

Adult↗

PubMed1996

Mortality of workers exposed to toluene diisocyanate in the polyurethane foam industry.

OBJECTIVE: To evaluate cancer mortality among United States workers exposed to toluene diisocyanate (TDI) in the manufacture of polyurethane foam. METHODS: This cohort mortality study included 4611 men and women employed in four polyurethane foam plants for at least three months between the late 1950s and 1987. The mortality experience of the cohort was then compared with that of the general United States population. RESULTS: Current and past industrial hygiene data indicated that air concentrations in 1984-5 were below the current United States standard of 0.04 mg/m3 but exceeded the standard before 1980. Mortality ratio (SMR) 2.78, 95% confidence interval (95% CI) 0.57-8.13) and non-Hodgkin's lymphoma (SMR 1.54, 95% CI 0.42-3.95) were increased, but not significantly. There was one male breast cancer. However, breast cancer was not increased in women (SMR 0.74). No other cancer category had an increased number of deaths compared with the general population. Only non-Hodgkin's lymphoma and Hodgkin's disease showed a possible relation with time since first employment and no cancer death category showed a strong relation with duration of employment. Mortality from non-malignant respiratory disease was not increased (SMR 0.86). CONCLUSIONS: This young cohort has few deaths and short follow up. The findings are therefore not conclusive. Further years of follow up will enable better evaluation of mortality.

Air Pollutants, Occupational↗