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At least 19 recordsLinked to original sources
PubMedDate not supplied

Linear poly(ethylene oxide)-based polyurethane hydrogels: polyurethane-ureas and polyurethane-amides.

Over the last 30 years, water-swellable and water-insoluble hydrogels have been extensively investigated and developed, leading to a large family of materials which have found uses in a wide range of biomedical applications. While hydrogels usually present a crosslinked structure, linear polyurethane-ureas (PUUs) based on poly(ethylene oxide) have been shown to be able to absorb and swell with aqueous media without dissolving. This behavior is due to the phase separated domain morphology, where hydrogen bonded urethane/urea hard segment domains are dispersed in a PEO soft segment domain. This work investigates the possibility of obtaining linear poly(ethylene oxide)-based polyurethane-amide (PUA) hydrogels using two amide diols as chain extenders, a mono amide diol (AD) and a diamide diol (DD), and a dicarboxylic acid (maleic acid, MA). Poly(ethylene oxide) based PUAs were obtained using a "one-shot" bulk polymerization technique. The chemicophysical characterization and water-solubility tests showed that these materials, while having molecular weights similar to the PUUs, do not possess sufficient phase separation, hydrogen bonding and hydrophobicity of the hard segment domains to exhibit hydrogel behavior. Crosslinked PUAs using maleic acid as chain extender show interesting hydrogel properties.

Journal Article↗
PubMed1999

Microbial degradation of polyurethane, polyester polyurethanes and polyether polyurethanes.

Polyurethane (PUR) is a polymer derived from the condensation of polyisocyanate and polyol and it is widely used as a base material in various industries. PUR, in particular, polyester PUR, is known to be vulnerable to microbial attack. Recently, environmental pollution by plastic wastes has become a serious issue and polyester PUR had attracted attention because of its biodegradability. There are many reports on the degradation of polyester PUR by microorganisms, especially by fungi. Microbial degradation of polyester PUR is thought to be mainly due to the hydrolysis of ester bonds by esterases. Recently, polyester-PUR-degrading enzymes have been purified and their characteristics reported. Among them, a solid-polyester-PUR-degrading enzyme (PUR esterase) derived from Comamonas acidovorans TB-35 had unique characteristics. This enzyme has a hydrophobic PUR-surface-binding domain and a catalytic domain, and the surface-binding domain was considered as being essential for PUR degradation. This hydrophobic surface-binding domain is also observed in other solid-polyester-degrading enzymes such as poly(hydroxyalkanoate) (PHA) depolymerases. There was no significant homology between the amino acid sequence of PUR esterase and that of PHA depolymerases, except in the hydrophobic surface-binding region. Thus, PUR esterase and PHA depolymerase are probably different in terms of their evolutionary origin and it is possible that PUR esterases come to be classified as a new solid-polyester-degrading enzyme family.

Bacteria↗
PubMed1988

Degradation of explanted polyurethane cardiac pacing leads and of polyurethane.

Polyurethane cardiac pacing leads explanted at autopsy and from reoperated patients were examined for degradation in the insulation. Scanning electron microscopy (SEM) analysis showed cracks on the polyurethane surface which were both parallel and perpendicular to the longitudinal axis of the lead. Surface analyses of leads were performed using Fourier-Transform Infra-red (FT-IR) spectrophotometry in the attenuated total reflectance mode. The FT-IR spectra of visibly deteriorated polyurethane from explanted lead sheaths were compared with that of unused polyurethane tubing used for such sheaths. Changes were most evident in the regions of 3000-2800, 1730 and 1368 cm-1. The observed alterations in the FT-IR spectra were consistent with a degradation mechanism involving oxidative chain cleavage in the polyurethane amorphous regions. New polyurethane tubing (Pellethane-Type 80A) was exposed to sodium hypochlorite to simulate a possible in-vivo process and generate reference material. Degradation with associated decreases in tensile strength and molecular weight was recorded. This study showed that polyurethane insulation used in pacing leads is susceptible to oxidative degradation.

Biocompatible Materials↗
PubMed1994

A review of the biostability and carcinogenicity of polyurethanes in medicine and the new generation of 'biostable' polyurethanes.

Polyurethanes are very versatile materials which have been used in the body for over 20 years. In fact, there are probably more scientific papers describing these materials and modifications of these materials for medical use than any other material to date. Unfortunately, some formulations of these polymers are subject to biodegradation and have limited their application in the body. Extensive investigation of the biodegradation mechanisms of these polymers by many researchers in the field has led to the development of a new generation of what are now called 'biostable' polyurethanes. This article reviews the history of polyurethane in medicine, polyurethane nomenclature, the biodegradation of these materials, the proposed mechanisms of its degradation as well as the carcinogenicity associated with these materials. Included in the discussion are the polyurethanes used as pacemaker lead insulators as well as those used to coat breast implants. The article concludes with a review of the new generation of 'biostable' polyurethanes and their proposed formulations.

Animals↗
PubMed1995

Adhesion of staphylococci to polyurethane and hydrogel-coated polyurethane catheters assayed by an improved radiolabelling technique.

Adhesion of Staphylococcus epidermidis NCTC 11047 to the external surface of polyurethane catheters was quantified by a radiolabelling assay. Maximum adhesion was achieved with an initial cell concentration of 3 x 10(8)/ml after incubation for 120 min. The assay was tested for reproducibility by analysis of variance. Adhesion of clinical strains of S. epidermidis and S. aureus to uncoated polyurethane and hydrogel (Hydromer)-coated polyurethane catheters was compared. Hydrogel coating significantly reduced adhesion for both S. epidermidis and S. aureus (mean percentage reduction 71% for S. epidermidis, 69% for S. aureus). Clinical isolates were also tested for adhesion to polystyrene by a modified microtitration well adhesion assay; there was no correlation between staphylococcal adhesion to polyurethane catheters and adhesion to polystyrene. Cell surface hydrophobicity values varied widely for both species. Positive correlations were found between cell surface hydrophobicity and adhesion to polystyrene and uncoated polyurethane catheters for S. epidermidis but not for S. aureus.

Analysis of Variance↗
PubMed2000

Solvent-free fabrication of micro-porous polyurethane amide and polyurethane-urea scaffolds for repair and replacement of the knee-joint meniscus.

New porous polyurethane urea and polyurethane amide scaffolds for meniscal reconstruction have been developed in a solvent-free process. As soft segments, copolymers of 50/50 L-lactide/epsilon-caprolactone have been used. After terminating the soft segment with diisocyanates, chain extension was performed with adipic acid and water. Reaction between the isocyanate groups and adipic acid or water provides carbon dioxide and results in a porous polymer. Extra hydroxyl-terminated prepolymer was added in order to regulate the amount of carbon dioxide formed in the foaming reaction. Furthermore, salt crystals ranging in size from 150 to 355 microm were added in order to induce macroporosity. The pore size was regulated by addition of surfactant and by the use of ultrasonic waves. The resulting porous polymer scaffolds exhibit good mechanical properties like a high-compression modulus of 150 kPa. Chain extension with adipic acid results in better mechanical properties due to better defined hard segments. This results from the lower nucleophilicity of carboxylic acids compared to water and alcohols. By adjusting the reaction conditions, materials in which macropores are interconnected by micropores can be obtained. On degradation only non-toxic products will be released; importantly, the materials were obtained by a simple, reproducible and solvent-free procedure.

Knee Injuries↗
PubMed1997

Polyurethane heart valves: fatigue failure, calcification, and polyurethane structure.

Six flexible-leaflet prosthetic heart valves, fabricated from a polyetherurethaneurea (PEUE), underwent long-term fatigue and calcification testing. Three valves exceeded 800 million cycles without failure. Three valves failed at 775, 460, and 544 million cycles, respectively. Calcification was observed with and without associated failure in regions of high strain. Comparison with similar valves fabricated from a polyetherurethane (PEU) suggests that the PEU is likely to fail sooner as a valve leaflet. Localized calcification developed in PEUE leaflets at the primary failure site of PEU leaflets, close to the coaptation region of the three leaflets. The failure mode in PEU valves had the appearance of abrasion wear associated with calcification. High strains in the same area may render the PEUE leaflets vulnerable to calcification. Intrinsic calcification of this type, however, is a long-term phenomenon unlikely to cause early valve failure. Both polymers performed similarly during static in vitro and in vivo calcification testing and demonstrated a much lesser degree of calcification than bioprosthetic types of valve materials. Polyurethane valves can achieve the durabilities required of an implantable prosthetic valve, equaling the fatigue life of currently available bioprosthetic valves.

Animals↗
PubMed1986

Synthesis and antithrombogenicity of anionic polyurethanes and heparin-bound polyurethanes.

Two kinds of novel antithrombogenic polyurethane materials were synthesized. One of them is a polyetherurethane with anionic charges on the film surface, and the other is a polyetherurethaneurea to which heparin was covalently bound. The mechanism of their antithrombogenicity was investigated. The anionic polyetherurethane selectively adsorbed albumin, did not cause a conformational change of plasma proteins adsorbed, and suppressed the adherence and deformation of platelets but did not deactivate the blood-clotting system, thus leading to a moderate antithrombogenicity. The heparin-bound polyetherurethaneurea was not favorable for the selective adsorption of albumin, caused the denaturation of plasma proteins adsorbed, and induced the adherence and deformation of platelets but deactivated the blood-clotting system, leading to excellent antithrombogenicity. For the investigation of blood-material interaction, the importance of a multiparameter estimation of the activation of platelets and the blood-clotting system was indicated.

Adsorption↗
PubMed1990

Blood plasma proteins on polyurethane and alkylsiloxane plasma-treated polyurethane surfaces. Dynamic approach by stimulus-response technique. Part 2. Evaluation of adsorption data by moment technique.

In this study, interactions of blood proteins (i.e. albumin and fibrinogen) with polyurethane biomaterial surfaces were investigated in an in vitro bead column test circuit using a stimulus-response technique. The dynamic sorption process of radiolabelled proteins on the surfaces was followed by detecting the radioactivity at the exit stream of the column, which was the response of a pulse stimulus at the inlet. The mathematical model was described and solved using 'parameter estimation by cybernetic moment technique', and the adsorption rate constants of plasma proteins on different biomaterial surfaces were calculated. By evaluation of the response curves with standard and cybernetic moment techniques, the following results were obtained. Albumin and fibrinogen adsorption is competitive, and the competition is strongly dependent upon the surface characteristics of the biomaterial. Preadsorption or preferential adsorption of albumin decreases the fibrinogen adsorption, and therefore increases the biocompatibility of material surface. Adsorption of blood plasma proteins are irreversible. The moment technique can also be used for the evaluation of stimulus-response data of biological systems, to determine the process parameters.

Adsorption↗
PubMed1997

In-vivo degradation of polyurethanes: transmission-FTIR microscopic characterization of polyurethanes sectioned by cryomicrotomy.

A combination of cryomicrotomy and transmission Fourier transform infrared (FTIR) microscopy was used to investigate chemical changes in unstrained sheets of Pellethane 2363-80A, Tecoflex EG80A and Biomer caused by biodegradation (18 month subcutaneous ovine implant). Cryomicrotomy was used to obtain thin sections (ca. 2.5 microm) from the surface into the bulk, parallel to the plane of the surface. FTIR microscopy was then used to obtain infrared absorbance spectra in the range 4000-600 cm(-1). Comparisons between the infrared spectra (by spectral subtraction) from implant surface, implant interior and non-implanted controls were used to detect chemical changes. Scanning electron microscopy was used to assess microstructural changes owing to biodegradation. Biodegradation in Biomer was observed as uniform pitting and superficial fissuring (<2.0 microm depth) over the implant surface. Biodegradation in Pellethane 2363-80A and Tecoflex EG 80A was observed as severe localized embrittlement of the surface with fissures infiltrating up to 40 microm into the bulk. The chemical changes associated with biodegradation were observed as localized oxidation of the soft segment and hydrolysis of the urethane bonds joining hard and soft segments. Tecoflex EG80A was also found to be susceptible to localized hydrolysis of the urethane bond within the aliphatic hard segment. Biomer showed evidence of a significant non-specific degradation in the non-implanted wet control (37 degrees C phosphate buffered saline at pH 7.3) samples and in the implant bulk.

Animals↗
PubMed1995

FT-IR spectroscopic studies of polyurethanes: IV. Studies of the effect of the presence of processing aids on the hemocompatibility of polyurethanes.

Many types of proprietary processing aids are used by the manufacturers of polymer medical devices, which are difficult to completely eliminate from the end product. In such cases, it is important to investigate how such processing aids affect the properties of the materials. One such material is Pellethane and a most commonly found processing aid is wax. We investigated the effect of the presence of such wax on hecompatibility properties, particularly on the adhesion and activation of human platelets, on a group of Pellethane samples with varying amounts of wax. The effectiveness of cleaning agents, like Freon, was examined for wax removal. The type and quantity of wax present within the near-surface regions of the Pellethane tubings was estimated by using the FT-IR-ATR technique. The presence of bis amide processing wax was found to affect the hemocompatibility properties of the Pellethane samples. Correlation between hemocompatibility and the amount of wax was made; platelet activation, as well as amount and density of fibrin formation, showed a linear correlation.

Biocompatible Materials↗
PubMed2000

A tribological study of UHMWPE acetabular cups and polyurethane compliant layer acetabular cups.

A novel design of polyurethane compliant layer acetabular cup has been developed through a series of friction, creep and wear tests. Friction tests were initially conducted on ABG standard form, polyurethane acetabular cups and an ABG standard form, UHMWPE acetabular cup for comparison. The polyurethane cups showed lower friction than the UHMWPE cup with maximum friction factors between 0. 008 and 0.02 compared with 0.035 for the UHMWPE cup. This indicated that, in the polyurethane cups, more of the load across the joint was carried by the fluid entrapped in the joint space rather than with asperity contact, compared with the UHMWPE cup. The inherent compliance of the polyurethane is used to promote elasto-hydrodynamic lubrication. However, this compliance raised concerns over excessive creep, which may in turn adversely affect tribological performance. Therefore, creep tests were undertaken on the ABG standard form, polyurethane acetabular cups followed by further friction tests. Small amounts of creep occurred in the polyurethane cups at ambient temperature, which reduced the friction slightly (maximum friction factors of 0.009) due to increased conformity between the head and the cup. However, at 37 degrees C, greater creep occurred causing pinching of the femoral head by the acetabular cup resulting in lubricant starvation and higher friction (maximum friction factors of 0.035). The design of the polyurethane cups was subsequently modified to incorporate a flared rim to eliminate the possibility of fluid starvation through pinching. Creep in polyurethane acetabular cups is also affected by the method of fixation of the cups, due to the conformity with and the stiffness of the cup backing. Hence, a one-million-cycle wear test was performed on five ABG flared form, polyurethane acetabular cups on the Mk. I Durham Hip Joint Wear Simulator to evaluate the best method of fixation for the polyurethane cups. The smallest amount of penetration, due to creep and wear, was found with cement fixation (0.30 mm penetration with cement fixation, 0.44 mm with polyethylene holder mounting, and 0.52 mm with metal shell mounting). A 4. 25-million-cycle wear test was then conducted on a further five ABG flared form, polyurethane acetabular cups with cement fixation. Five ABG standard form, UHMWPE acetabular cups were also wear-tested to 5. 0-million cycles. The mean and standard error of the wear rate for the polyurethane cups were 14.1 +/- 4.3 mg/10(6) (12.0 +/- 3.6 mm(3)/10(6)), cycles compared with 44.8 +/- 3.4 mg/10(6) (48.2 +/- 3. 7 mm(3)/10(6)), cycles for the UHMWPE cups. This study showed that the novel polyurethane-compliant layer acetabular cup with cement fixation was tribologically superior to the ABG standard form UHMWPE design currently being used clinically.

Biocompatible Materials↗
PubMed2000

Bacterial colonization of functionalized polyurethanes.

A protocol was developed for studying the growth of bacteria upon polyurethanes subsequent to the establishment of an adherent bacterial population. An inocula of approximately 10(5) cfu S. aureus were spread on functionalized polyurethanes which included Pellethane, sulfonated Pellethane, phosphonated Pellethane, quaternized amine polyurethanes, and a zwitterionic phosphonated polyurethane. After 24 h incubation, Pellethane, sulfonated Pellethane, and phosphonated Pellethane showed bacterial growth by at least a factor of 10. In contrast, the zwitterionic phosphonated polyurethane showed a factor of 10 decrease in bacteria after 24 h and the quaternized amine polyurethanes reduced the bacteria to only a few hundred after only 1 h. When treated with bovine serum albumin, Pellethane, sulfonated Pellethane, and phosphonated Pellethane again showed bacterial growth by as much as a factor of 10 over 24 h. The quaternized amine polyurethanes and the zwitterionic phosphonated polyurethane still exhibited bactericidal abilities even when coated with bovine serum albumin, with the zwitterionic material reducing bacteria by more than a factor of 10 over 24 h and the quaternized amine polyurethane reducing the bacteria to only a few hundred after only 1 h. A zone of inhibition study suggested that the bactericidal activity of the zwitterionic phosphonated polyurethane was due to the leaching of cadmium ions. A quaternized amine polyurethane which contained chloride instead of iodide as the counterion to the amine moiety was less bactericidal than the iodide-containing polymer when treated with albumin. Thus, bacteria were able to colonize Pellethane, phosphonated sulfonated Pellethane, and phosphonated Pellethane, but the iodide-containing quaternized amine polyurethane and the zwitterionic polyurethane prevented colonization.

Albumins↗
PubMed2005

Cholesterol-derivatized polyurethane: characterization and endothelial cell adhesion.

Endothelialization of synthetic surfaces has been challenging with limited success thus far. We investigated the hypothesis that covalent attachment of cholesterol to polyurethane via the urethane nitrogen groups would create a high-affinity surface for attachment and adhesion of endothelial cells. Cholesterol was covalently bound to the polyether polyurethane, Tecothane, by first derivatizing the polyurethane nitrogen groups with bromoalkyl side chains, followed by reacting mercapto-cholesterol to the bromoalkyl sites. Cholesterol-modified polyurethane demonstrated a qualitatively smoother surface per atomic force microscopy than nonmodified and increased surface energy (contact angle measurements) compared with unmodified polyurethane. Cell attachment assays showed a significantly greater number of attached bovine arterial endothelial cells (p = 0.0003) after 45 min of seeding on cholesterol-modified polyurethane versus unmodified polyurethane. Bovine arterial endothelial cells cultivated on cholesterol-modified Tecothane showed significantly greater levels of cell retention compared with unmodified Tecothane when exposed to arterial level shear stress for 2 h (25 dynes/cm2) with 90.0 +/- 6.23% cells remaining adherent compared with unmodified polyurethane, 41.4 +/- 11.7%, p = 0.0070. Furthermore, ovine endothelial precursors, obtained as blood outgrowth endothelial cells, were seeded on cholesterol-modified polyurethane and exposed to 25 dynes/cm2 shear conditions for 2 h, with the retention of 90.30 +/- 3.25% of seeded cells versus unmodified polyurethane, which retained only 4.56 +/- 0.85% (p < 0.001). It is concluded that covalently linking cholesterol to polyurethane results in improved material properties that permit increased endothelial cell retention compared with unmodified polyurethane.

Animals↗
PubMed1998

Synthesis and characterization of degradable polyurethane elastomers containing and amino acid-based chain extender.

Degradable polyurethane elastomers were synthesized using a diester chain extender. The chain extender was synthesized by a diesterification reaction between L-phenylalanine and 1,4-cyclohexane dimethanol to yield a diester, diamine. Soft segment chemistry (polycaprolactone diol, PCL and polyethylene oxide, PEO) and molecular weight were varied and the impact on polyurethane physicochemical and degradation characteristics was evaluated. It was found that the PEO containing polyurethanes absorbed large amounts of water while the PCL containing ones did not, indicating a large difference in bulk hydrophilicity. The rate of water vapor permeance (WVP) through the polyurethane films generally followed the water absorption trends. However, soft segment crystallinity, noted by DSC, for the PCL containing polyurethanes served to reduce WVP values with increasing PCL molecular weight. Polyurethane surface characterization was carried out by water contact angles and XPS. The PEO containing polyurethanes exhibited low contact angles in comparison with the PCL ones. In addition, angle-resolved XPS demonstrated soft segment surface enrichment in all cases typical for phase segregated materials. Significant variation in the physicochemical properties of the experimental polyurethanes was observed indicating potential use in a variety of biomaterials applications. An in vitro degradation study was carried out by incubating the polymers in 0.1 M TBS at 37 degrees C, pH 8.0 for up to 56 days. Degradation was followed by measuring mass loss, change in molecular weight by GPC and surface alteration by scanning electron microscopy. The polyurethane containing PEO was found to exhibit substantial mass and molecular weight loss over 56 days resulting in a porous material of little strength. In contrast, the PCL containing polyurethane displayed modest mass and molecular weight loss after 56 days. This polyurethane retained its strength and displayed little surface alteration after 56 days in buffer. It was hypothesized that differences in polyurethane hydrophilicity as well as initial molecular weight may have been responsible for the dramatic difference in degradation rate observed here.

Absorption↗