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Water as foaming agent for open cell polyurethane structures.

The problem of moisture in polymer processing is known to any polymer engineer, as air bubbles may be formed. Hence granulates are generally dried prior to manufacturing. This study tried to develop a novel processing methods for scaffolds with controlled moisture content in thermoplastic polyurethane. The common foaming agents for polyurethane are organic solvents, whose residues remaining in the scaffold may be harmful to adherent cells, protein growth factors or nearby tissues. Water was used as a foaming agent and NaCl was used as porogens to achieve an open-cell structure. The polyether-polyurethane samples were processed in a heated press, and achieved a porosity of 64%. The pore size ranged between 50 and 500 microm. Human fibroblasts adhered and proliferate in the scaffold. A non-toxic production process was developed to manufacture a porous structure with a thermoplastic polyether-polyurethane. The process enables a mass-production of samples with adjustable pore size and porosity. In contrast to an existing method (solvent casting), the processing of the samples was not limited by its thickness. The process parameters, which attribute mostly to the pore building, were filling volume, temperature, NaCl-concentration and water-uptake rate.

Air↗

Polyurethane II catheter as long-indwelling intravenous catheter in patients with cancer.

BACKGROUND: Silicone has been the standard material for indwelling devices to date. Polyurethane II exhibits properties that makes it suitable as a component of long-indwelling vascular access, with the added advantage of low cost. OBJECTIVE: To describe the experience of an intravenous therapy team with 206 polyurethane II catheters used as long-indwelling vascular access in patients with cancer. MATERIALS AND METHODS: All polyurethane II single- and double-lumen catheters implanted between January 1, 1994, and March 15, 1995, were analyzed, including time of stay and type and rate of infectious and noninfectious complications. RESULTS: A total of 206 catheters were placed--164 single-lumen and 42 double-lumen catheters--in 190 patients; average stay was 101 days (range, 1-445 days). The infection incidence rate was 0.66 per 1000 catheter-days for single-lumen catheters and 1.6 per 1000 catheter-days for double-lumen catheters. Noninfectious complications included 1 thrombosis (incidence rate, 0.06 per 1000 catheter-days for single-lumen and none for double-lumen catheters), 5 catheter ruptures (2.4%), and 1 pneumothorax (0.48%). Twelve catheters (8.3%) were removed because of complications; only 1 was infectious. The remaining 17 infectious episodes (94.4%) were resolved without catheter removal. Our complication rate with single-lumen catheters in this series was similar to our previous experience with a nontunneled silicone catheter. CONCLUSIONS: Our findings indicate that polyurethane II catheters have proven useful and safe as long-indwelling vascular access in patients with cancer at our hospital at a considerably lower cost.

Adolescent↗

Calcified matrix production by SAOS-2 cells inside a polyurethane porous scaffold, using a perfusion bioreactor.

The repair and regeneration of damaged or resected bone are problematic. Bone autografts show optimal skeletal incorporation, but often bring about complications. Hence, there is increasing interest in designing new biomaterials that could potentially be used in the form of scaffolds as bone substitutes. In this study we used a hydrophobic cross-linked polyurethane in a typical tissue-engineering approach, that is, the seeding and in vitro culturing of cells within a porous scaffold. The polyurethane porous scaffold had an average pore diameter of 624 microm. Using a perfusion bioreactor, we investigated the effect of shear stress on SAOS-2 human osteoblast proliferation and calcified matrix production. The physical, morphological, and compressive properties of the polyurethane foam were characterized. At a scaffold perfusion rate of 3 mL/min, in comparison with static conditions without perfusion, we observed 33% higher cell proliferation; higher secretion of osteopontin, osteocalcin, decorin, and type I collagen (9.16-fold, 71.9-fold, 30.6-fold, and 18.12-fold, respectively); and 10-fold increased calcium deposition. The design of the bioreactor and the design of the polyurethane foam aimed at obtaining cell colonization and calcified matrix deposition. This cultured biomaterial could be used, in clinical applications, as an osteoinductive implant for bone repair.

Biocompatible Materials↗

Permeability of nitrile rubber, latex, polyurethane, and neoprene gloves to 18 antineoplastic drugs.

The permeability of four glove materials to various antineoplastic drugs was studied. Eighteen antineoplastic drugs posing potential health hazards to handlers were prepared at the highest concentrations normally encountered by hospital personnel. Four glove materials-nitrile rubber, latex, polyurethane, and neoprene-were exposed to the drugs for 30, 60, 90, and 120 minutes. Glove thickness was measured with an electronic digital caliper. Random samples of material were selected from the glove fingertips, and triplicate samples were tested for each drug at each interval. For a majority of the drugs, a bacterial mutagenicity assay was used to measure the amount of drug (if any) that permeated the material. High-performance liquid chromatography was used for drugs not tested with the bacterial assay. The nitrile gloves were the thinnest (0.12 mm), and the latex gloves were the thickest (0.18 mm). The four materials were generally impermeable to each drug. One sample of the nitrile gloves appeared to have a defect, allowing >5% of the drug solution to pass through at 30 minutes. One sample each of the latex, polyurethane, and neoprene gloves demonstrated minimal permeability (< or =1%): One latex glove sample was permeated by carmustine, and paclitaxel permeated one sample each of the polyurethane and neoprene materials. Nitrile rubber, latex, polyurethane, and neoprene gloves were impermeable to 18 antineoplastic drugs in most, but not all, cases.

Antineoplastic Agents↗

Epicardial administration of ibutilide from polyurethane matrices: effects on defibrillation threshold and electrophysiologic parameters.

Polymer-drug composites known as controlled-release systems have been used effectively to prevent and treat ventricular arrhythmias in experimental studies. We wished to determine if such systems could be useful in reducing ventricular defibrillation energy requirements in an acute canine model without producing undesirable electrophysiologic effects. Ibutilide-polyurethane monolithic controlled-release matrices were formulated with ibutilide fumarate and a polyether polyurethane. In vitro drug-release characteristics of the drug matrices were determined. Two formulations were investigated: (a) 20% ibutilide by weight in polyether polyurethane, and (b) 4% ibutilide/16% dimethyl tartrate in polyurethane. Based on in vitro release studies, 20% ibutilide matrices (25 mg) would provide a 25-kg dog with a dose of 25 micrograms/kg ibutilide in a 2-h acute experimental period, and 4% ibutilide matrices were estimated to provide 3.5 micrograms/kg. We used each of these types of matrices in acute open-chest dog studies to assess electrophysiologic effects and the influence of epicardial controlled-release ibutilide, as compared with intravenous (i.v.) administration, on defibrillation energy thresholds (DFTs), using epicardial defibrillation electrodes. In monophasic defibrillation waveform studies, 20% matrices significantly decreased DFT as compared with a predrug control period [2.54 +/- 0.59 (mean +/- SEM) vs. 7.23 +/- 1.73 J, respectively, p = 0.038]. Administration of the same dose i.v. did not cause significant reduction in energy requirement. With a biphasic defibrillation waveform, 4% ibutilide matrices significantly decreased DFT as compared with control (2.53 +/- 0.34 vs. 3.42 +/- 0.46 J, respectively, p = 0.003). Administration of an equivalent i.v. dose did not cause a significant reduction in biphasic energy requirement. Both types of controlled-release systems significantly prolonged refractoriness and conduction times of ventricular extrastimuli as compared with vehicle. No proarrhythmia events were observed. Epicardial polymeric controlled-release ibutilide significantly prolonged ventricular refractoriness and conduction and thus may enhance antiarrhythmia activity. In addition, controlled-release ibutilide formulations significantly decreased DFT requirements. Thus, ibutilide-polymeric controlled-release matrix systems may be useful in conjunction with implantable defibrillators in preventing ventricular arrhythmias and reducing defibrillation energy requirements.

Animals↗

Natural-Y Même polyurethane versus smooth silicone: analysis of the soft-tissue interaction from 3 days to 1 year in the rat animal model.

The polyurethane foam-covered breast prosthesis is experiencing increased clinical use. The polyurethane is felt to be responsible for altering capsule formation and reducing the contracture rate. This study characterizes the soft-tissue response to the Natural-Y Même polyurethane foam versus smooth silicone in a rat model. Implants were fashioned from an unbacked polyurethane foam specimen used to cover the Natural-Y prosthesis, a silicone shell covered with the Natural-Y foam, and a smooth silicone control. Materials were placed subcutaneously into the backs of male Lew/SsN rats (n = 81) for 3, 7, 14, and 28 days and 3, 6, and 12 months. Implants were then harvested with their soft-tissue response and evaluated histologically. Analysis demonstrates that microstructuring of a surface, as opposed to a smooth material, will dramatically alter the early, intermediate, and late wound-healing events. The soft-tissue response was observed to be dependent on implant site, material chemistry, and morphology as characterized by exudate formation, macrophage invasion, multinucleated giant cell formation, collagen deposition, foam degradation, and angiogenesis.

Animals↗

Comparative experience with smooth and polyurethane breast implants using the Kaplan-Meier method of survival analysis.

Smooth-walled silicone implants have been widely used in breast surgery. Capsular contracture, causing undesirable firmness and spherical deformity, has been a common problem. Recent studies suggest that polyurethane-covered breast implants are associated with a lower incidence of capsular contracture. The statistical methodology employed in some of these studies, however, may be subject to criticism. Between July of 1984 and June of 1990 (72 months), 427 polyurethane breast implants were used in 279 patients and 439 smooth prostheses were used in 250 patients for a variety of aesthetic and reconstructive procedures. The occurrence of capsular contracture was carefully monitored and then analyzed using the Kaplan-Meier method of survival analysis. This method is particularly well suited to analysis of these types of clinical data because it allows for the fact that contractures occur at varying intervals after surgery and that follow-up of patients is incomplete. The probability of capsular contracture with smooth-walled prostheses was found to be significantly greater than with polyurethane-covered implants in each group of patients studied (p less than 0.05). Other complications occurred at a similar rate regardless of prosthesis type. This study supports the belief that polyurethane breast implants have a lower contracture rate; furthermore, it introduces the Kaplan-Meier method for analyzing the outcome of alternative plastic surgical therapies.

Breast↗

The biomechanical and histopathologic effects of surface texturing with silicone and polyurethane in tissue implantation and expansion.

There has been considerable interest in determining the effect of morphologic alterations of prosthetic surfaces on capsule response in breast surgery. The purpose of this study was to provide a precise, three-dimensional evaluation of soft-tissue response to surface modifications in both implantation and expansion. Expandable 100-cc prostheses were designed with one of three surfaces: textured silicone (Biocell), standard smooth silicone, or polyurethane (Natural-Y, Meme). A new submuscular implantation site in the rabbit was developed. Each animal randomly received a smooth-surface device on one side and either a textured silicone or polyurethane device on the other. In one group of animals, the prostheses were expanded monthly. Capsular response was evaluated monthly in vivo using standardized techniques as well as biomechanical methods for up to 6 months in the expander group (n = 7 to 16) and 8 months in the implant group (n = 7 to 15). Analysis of biomechanical and histologic data revealed that prosthetic surface morphology can specifically alter capsular response. Polyurethane was the only effective surface in preventing capsular contracture in implantation. In expansion, both textured silicone and polyurethane surfaces resulted in significantly less capsular contracture and less resistance to expansion than comparable smooth-surfaced controls. Statistical comparisons reveal that the biomechanical methods utilized in this study provide the most precise and objective method of defining overall soft-tissue contracture around implanted biomaterials.

Animals↗

Use of polyurethane minisponges to collect human tear fluid.

PURPOSE: To characterize a method of tear collection based on the use of amphiphilic polyurethane absorbing minisponges. METHODS: Tear fluid was collected from 17 healthy volunteers. A preweighed polyurethane dry minisponge was laid on the margin of the lower eyelid. Once wet (5-10 minutes), the fluid was transferred to a preweighed Eppendorf tube after squeezing the sponge by centrifugation. The amount of fluid absorbed and fluid recovered were determined by reweighing the sponge and the tube after absorption and centrifugation steps, respectively. The fluid was qualitatively characterized by electrophoretic polypeptide profiling in Coomassie blue-stained SDS-polyacrylamide gels. RESULTS: Per eye, 14.6 +/- 5.3 microL tear fluid was collected. That volume was about 90% of the fluid absorbed by polyurethane minisponges, almost doubling the fraction recovered from other more hydrophilic absorbing polymers. Major bands characterizing the electrophoretic profile of this fluid were those of 79, 66, 27, 18, and 14 kd. This profile was indistinguishable from that of tear fluid aspirated into glass microcapillaries. Tear fluid collected simultaneously from both eyes displayed the same profiles. Successive tear samples from a single eye showed the same profile except for the 66-kd band, which increased steadily as collection proceeded. Tear donors rarely complained of discomfort. CONCLUSIONS: Tear collection by absorbing polyurethane minisponges is highly advantageous in efficiency (recovery) and reproducibility (invariant electrophoretic polypeptide profiles). Tear donor comfort, simultaneous bilateral collection, and collections from several donors at once are additional major advantages of this collection method in studies involving single subjects and populations in health and disease.

Adolescent↗

Clinical biodurability of aliphatic polyether based polyurethanes as peritoneal dialysis catheters.

Thermoplastic polyurethane elastomers are the most important implantable grade polyurethanes in medical applications. An aliphatic polyether based polyurethane, Tecoflex (TF; Thermedics, Inc., Woburn, MA), is used in the construction of a proprietary peritoneal dialysis (PD) catheter. Information is limited regarding the biostability of the TF polymer in the clinical environment as a PD catheter. This report presents the clinical experience regarding the biodurability of 104 catheter implants. The extracorporeal tubing segments of all TF catheters eventually developed aesthetically offensive discoloration, opaqueness, and surface tackiness. Catheter breaks in the external segment occurred in 27% of devices that survived longer than 28 months. Mupirocin ointment at the catheter skin exit site caused swelling and deformity of the TF in one case. Three catheters extruded as a result of Dacron cuffs separating from the tubing wall. Catheters removed for other reasons were frequently found to have loose cuffs, especially if the devices were implanted for several years. Causes and possible mechanisms for observed failures are discussed. The durability of biomaterials used in construction of PD catheters is of vital importance for successful long-term functioning. The TF polymer embodied as a PD catheter represents a mismatch of the material and its mission. Fabrication of PD catheters from higher grade polyurethanes possessing greater biostability should be explored. Silicone rubber appears to remain the most durable material to date for PD catheter construction.

Biocompatible Materials↗

In vitro function and durability assessment of a novel polyurethane heart valve prosthesis.

While flexible-leaflet, central-flow prosthetic heart valves promise relief from anticoagulation therapy, they continue to be restricted by inadequate durability. In consequence, a novel trileaflet valve, made entirely from polyurethane, has been developed. A batch of 6 consecutively manufactured polyurethane valves was subjected to hydrodynamic function and accelerated fatigue testing. Computerized data acquisition and control systems have been introduced to improve valve testing methodologies. In terms of hydrodynamic function, the polyurethane valve demonstrates transvalvular pressure gradients similar to those for a bioprosthetic valve (Carpentier-Edwards) and levels of retrograde flow significantly less than those for either the bioprosthetic valve or a bileaflet mechanical valve (St Jude Medical). The equivalent of 10 years of cycling without failure has been exceeded by all 6 polyurethane valves in accelerated fatigue tests with 2 valves remaining intact after 674 million cycles (equivalent to approximately 17 years) in continuing tests. Highspeed photography revealed considerable differences in leaflet motion between valves cycled at accelerated and physiological rates.

Biocompatible Materials↗

Thermoplastic polyurethanes as insulating materials for long-life cardiac pacing leads.

Historically, the material most widely used for permanent cardiac pacing lead insulation has been silicone elastomer. We have recently evaluated a variety of polyether polyurethanes and found them also to be suitable as insulating materials for cardiac pacing leads. Test results showed that these polyurethanes are extremely tough, hydrolytically very stable, non-toxic, non-carcinogenic, and very inert in a biological environment. In addition, because polyurethane has a higher tensile strength than silicone elastomer, a thinner insulating layer can be used to construct smaller diameter leads. This facilitates the introduction of one or two leads through small veins or split sheath introducers. The smooth polyurethane material is also very easy to advance through the venous circulation, thus improving the handling characteristics of the lead or leads.

Animals↗

Long-term performance of polyurethane pacing leads: mechanisms of design-related failures.

Environmental stress cracking has been identified as a crack propagating mechanism in polyurethane-insulated, heart pacemaker leads, which is directly related to specific lead design parameters. Lead designs imposing excessive stress on the polyurethane insulation through an interference fit between the coil and polymer have demonstrated insulation failures. Conversely, low-stress designs have shown virtually no insulation problems. The higher-stress designs have used organic solvents to facilitate coil placement during manufacturing, which may result in lowering the polymer's ability to resist the higher stress. In addition, a specific silver-containing coil wire composition has been found to galvanically corrode upon body fluid intrusion into the lead, ionizing the silver. These ions interact with the polyurethane polymer resulting in the loss of polymer strength. All polyurethane lead failures to date have been specific to high stress and/or chemical interaction. Leads using low-stress designs and nonreactive coil wire compositions continue to demonstrate a positive clinical experience.

Animals↗

Preparation and characterization of polyurethane optical phantoms.

We describe a method for the preparation of a polyurethane phantom to simulate the optical properties of biologic tissues at two wavelengths in the visible and near-infrared spectral range. We characterize the addition of added molecular absorbers with relatively narrow absorption bands [full width at half maximum (FWHM) 32 and 76 nm for Epolight 6084 and 4148, respectively] for independent absorption at 690 nm for absorption up to 5 cm(-1), and 830 nm for absorptions up to 3 cm(-1). Absorption by both dyes is linear with concentration in these respective regions and is consistent in polyurethane both before and after curing. The dyes are stable over long durations with no more than 4% change. The absorption of visible light by polyurethane decreases with time and is stable by one year with a drop of 0.03+/-0.003 cm(-1) from 500 to 830 nm. The scattering properties are selected by the addition of TiO2 particles to the polyurethane, which we functionally describe for the 690- and 830-nm wavelengths as related to the weight per volume. We demonstrate that the variation in absorption and scattering properties for large batch fabrication (12 samples) is +/-3%. The optical properties of the phantoms have not significantly changed in a period of exceeding one year, which makes them suitable for use as a reference standard.

Biomimetic Materials↗

Cancer incidence and mortality of isocyanate exposed workers from the Swedish polyurethane foam industry: updated findings 1959-98.

AIMS: To assess whether cancer incidence and mortality in chronic obstructive lung diseases were increased in the Swedish polyurethane foam industry cohort, updated with 11 more years of follow up. METHODS: The mortality and cancer incidence (1959-98) experienced by a cohort of 4175 male and female employees employed for at least one year in the period 1959-87 at one of nine Swedish polyurethane foaming plants were investigated. Comparisons were based on calendar year, sex, and five-year age group specific mortality and incidence rates for Sweden. Workplaces and job tasks were categorically assessed for exposure to toluene diisocyanate (TDI) and methylene diphenyldiisocyanate (MDI) by occupational hygienists. RESULTS: Fewer cancer cases than expected were observed, but the lung cancer incidence was enhanced in women. Women with "apparent exposure" to TDI or MDI did not, however, have a higher lung cancer incidence than those with "no or low exposure". Moreover, a nested case referent study did not find that polyurethane dust exposure had been more prevalent among the female lung cancer cases than among referents. No increased mortality in chronic obstructive lung diseases was observed in the cohort. CONCLUSIONS: Results support the findings from two other cohort studies of an increased lung cancer risk among female workers in the polyurethane foam manufacturing industry. Chance or confounding from smoking are not obvious explanations for the coherent findings. However, the study was not able to link isocyanate exposed employment with lung cancer risk.

Adult↗

Obstruction of the lacrimal system: treatment with a covered, retrievable, expandable nitinol stent versus a lacrimal polyurethane stent.

PURPOSE: To compare the clinical effectiveness of a covered nitinol stent with that of a polyurethane stent for treatment of lacrimal system obstructions. MATERIALS AND METHODS: A nitinol stent was knit from a single thread of 0.1-mm nitinol wire in a tubular configuration and was covered by dipping the stent into a polyurethane solution. The stent was 4 mm in diameter and 30 or 35 mm long. With fluoroscopic guidance, a covered nitinol stent (n = 33, group A) or a polyurethane stent (n = 35, group B) was placed in 68 patients. The following items were evaluated retrospectively: technical success, procedure time, cumulative patency rate, and complications. An unpaired Student t test was used to analyze the difference between the procedure times. Kaplan-Meier survival curves and a log-rank test were used to compare the cumulative patency rates. RESULTS: Stent placement was technically successful in 31 (94%) of 33 patients in group A and in all 35 (100%) patients in group B. After stent placement, all patients showed resolution of epiphora. Average procedure time was 400 seconds (range, 270-900 seconds) in group A and 260 seconds (range, 150-900 seconds) in group B. The difference between the procedure times was statistically significant (P =.0003). During the mean follow-up period of 40 months, there was recurrence of epiphora in 30 of 31 patients in group A and 26 of 35 patients in group B. The difference of the cumulative patency rates was statistically insignificant (P =.2). CONCLUSION: Although the polyurethane stent used for treatment seemed to be more effective than the nitinol stent, selection of these stents for placement should be made with caution, because the long-term patency rates are not encouraging.

Adolescent↗

Compression-induced changes on physical structures and calcification of the aromatic polyether polyurethane composite.

It is generally accepted that stress causes calcification in both bio-prosthetic and polyurethane heart valves. However, simple uni-axially- and bi-axially-stretched samples did not yield a feasible model for the elaboration of the stress-induced calcification. In this study, heat compaction combined with the incorporation of polyethylene has been explored. Specimens of polyurethane were solution cast onto a porous bi-axially-drawn ultra-high-molecular-weight polyethylene film and then heat compacted under a pressure of 18 MPa at a chosen temperature for 1.5 h. The heat-compaction-induced calcification and physical changes of the polyurethane composite were evaluated using a 28-day in vitro calcification model and Attenuated Total Reflection-Fourier Transform-Infrared (ATR-FT-IR) spectroscopy. The calcification results indicated that heat-compaction-induced calcification was double that achieved without heat compaction. Heat-compacted polyurethane composite showed higher affinity to calcium ions than the non-heat compacted sample. The ATR-FT-IR results showed that the heat-compaction-induced physical changes include distortions of polymeric molecules and permanent changes of microstructures. The distortions of polymeric molecules could be deteriorated in contact with different media. The relaxation of the stressed structures of the polyether moiety might serve as a calcium trap and a heterogeneous nucleation site for calcification. The permanent changes of microstructures resulted from high distortions also served as affinity sites attracting calcification.

Biocompatible Materials↗

A new method for continual quantitation of viable cells on endothelialized polyurethanes.

Many of the segmented polyurethanes currently used in cardiovascular prostheses undergo either modification of their surface structure or are lined with a confluent monolayer of endothelial cells to improve their hemocompatibility. During the establishment of an endothelial cell lining on these biopolymers it is necessary to continually monitor the number of viable cells that are covering the substrate. Yet, not all of the conventional cell enumeration techniques are suitable for assessing the growth of endothelial cells on polyurethanes. Methods, such as direct cell counting, dye uptake, or DNA or protein staining require either a transparent scaffold or lead to termination of the culturing process prior to measurement. In addition, some of the spectroscopic assays are often hampered by interaction of the dyes and/or solubilizers with the various constituents (e.g., catalyzers, antioxidants) and/or functional groups in the polyurethane formulations. In addressing these problems, we adapted a novel, highly reproducible fluorescent assay which is based on reduction by viable cells of an electrochemically sensitive compound, Alamar Blue. The bioreduced product is soluble and stable in culture media and noncytotoxic. In addition, the assay is independent of the geometry or physicochemical properties of the polymeric surfaces. In the present study we focus on the implementation of this assay to monitoring attachment and growth of various endothelial cell types on segmented polyurethanes.

Analysis of Variance↗