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Analysis and evaluation of a biomedical polycarbonate urethane tested in an in vitro study and an ovine arthroplasty model. Part I: materials selection and evaluation.

The polyurethane elastomer (PU) Corethane 80A (Corvita) is being considered as the acetabular bearing material in a novel total replacement hip joint. The biostability of Corethane 80A was investigated in vitro (this work) and in vivo (reported separately) in a fully functioning ovine total hip arthroplasty (THA) model, with the PU as the bearing layer in a prototype compliant layer acetabular cup. The in vitro studies assessed the resistance of Corethane 80A to the main degradation mechanisms observed in PUs: hydrolysis, environmental stress cracking (ESC), metal ion oxidation (MIO) and calcification. The performance of the polycarbonate PU Corethane 80A was assessed alongside three other commercially available biomedical PUs: polyether PUs Pellethane 2363-80A (DOW Chemical) and PHMO-PU (CSIRO, not supplied as a commercial material) as well as polycarbonate PU ChronoFlex AL-80A (CardioTech). Chemical and structural variables that affect the properties of the materials were analysed with particular attention to the nature of the material's hard and soft segments. PU degradation was probed using a range of analytical tools and physical-testing methods, including mechanical testing, differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and environmental scanning microscopy (ESEM). Corethane 80A displayed the best overall resistance to hydrolysis, ESC, MIO and calcification, followed by ChronoFlex 80A and PHMO-PU. Pellethane 80A was the least stable. This study provides compelling evidence for the biostability and effectiveness of Corethane 80A and points to its suitability for use as a compliant bearing layer in hip arthroplasty, and possibly also other joints.

Arthroplasty, Replacement, Hip↗

Glycocalyx-mimetic dextran-modified poly(vinyl amine) surfactant coating reduces platelet adhesion on medical-grade polycarbonate surface.

A dextran-modified poly(vinyl amine) comb-like surfactant polymer, poly(N-vinyl dextran aldonamide-co-N-vinyl hexanamide), that can surface-adsorb on hydrophobic polymeric substrates, was designed to improve the interfacial blood-compatibility of polymeric biomaterials. Medical-grade polycarbonate was selected as a model substrate because of its extensive use in blood-contacting biomedical devices like hemodialyzers, blood pumps and oxygenators. The surfactant polymer was physisorbed from aqueous solution onto the polycarbonate substrate. The surfactant coating was stable under dynamic shear conditions in whole blood, as confirmed by fluorescence microscopy and total internal reflection fluorescence (TIRF) experiments with fluorescein-labeled surfactant polymer. The coated disks and uncoated control disks were exposed to platelet-rich plasma (PRP) and whole human blood in a rotating disk system (RDS) to study platelet-adhesion under dynamic shear stress environments. Adhered platelets were stained with fluorescein isothiocyante (FITC)-tagged anti-CD41a monoclonal antibody and imaged by epifluorescence microscopy. Complimentary images were obtained by phase-contrast microscopy. Platelet adhesion on the surfactant-coated disks was reduced by approximately 90%, compared with uncoated disks. The images also showed a concomitant reduction in platelet-derived microparticles on surfactant-coated disks, compared with uncoated disks. The results suggest potential application of carbohydrate-modified surfactant polymers as a glycocalyx-mimetic non-thrombogenic interfacial coating for blood-contacting biomaterials.

Adult↗

Effect of metal chlorides on thermal degradation of (waste) polycarbonate.

In this study, we investigated how to treat (waste) polycarbonate efficiently to reduce its degraded residue. The study was carried out in an isothermal reactor under continuous nitrogen flow at atmospheric pressure to pyrolyze polycarbonate (PC) alone and in the presence of metal chloride. Some metal chlorides were shown to be catalytic active for the degradation of PC at 400 degrees C, which increased degradation conversion from 8.5% to more than 58.3%. Among those active metal chlorides, ZnCl2 and SnCl2 can produce higher liquid product yields. Effects such as particle size of PC, temperature, the weight ratio of metal chloride/PC, and degradation time on the degradation conversion of PC without and with these two most active metal chlorides were studied. Results of the liquid product analysis by GC/MS demonstrated the product composition of PC degradation over the metal chlorides is much simpler than that of degradation alone. The main liquid product is phenol, p-isopropylphenol, diphenyl carbonate, and bisphenol A for all cases.

Catalysis↗

Chemotaxis of polymorphonuclear leukocytes in whole blood in the 'sparse-pore' polycarbonate (Nuclepore) membrane/Boyden chamber assay.

Chemotaxis of polymorphonuclear leukocytes (PMN) in 100%, 50% and 25% whole blood as well as in separated preparations were compared using both N-formyl peptide and interleukin-8 as chemoattractants and Boyden-type chambers with 'sparse-pore' polycarbonate (Nucleopore, California) membranes. In addition, attachment, spreading and 'drop-off' of cells from the 'sparse-pore' membrane were documented. In whole blood, fewer PMN attached to the membrane, but these showed greater chemotactic activity and exhibited more spreading and more 'drop-off' than separated PMN. Despite these differences, the 'sparse-pore' polycarbonate membrane system may be used to assay chemotaxis with whole blood as the source of PMN.

Cell Adhesion↗

Prevention of ocular gunshot injuries using polycarbonate lenses.

Two patients lost three eyes, and one his life, secondary to ocular gunshot wounds. In both patients, the pellets gained entry into the central nervous system through the eye and orbital bones despite only superficial wounds to other areas of the body. These tragic injuries prompted a study of polycarbonate lenses to determine their effectiveness in preventing small caliber ocular gunshot wounds. This investigation determined that 3.0 mm and the 2.2 mm polycarbonate lenses could prevent such injuries at distances greater than 15 yards. In comparing the two lenses, it was found that the 3.0 mm lens sustained less damage at 70 degrees F, but the 2.2 mm lens was more resistant to penetration at 32 degrees F. Since most hunting is done in the fall and winter months, the brittle nature of the thicker lens is significant. Polyamide sports frames with a posterior rim were also tested and found to prevent posterior lenticular expulsion at 15 yards. Standard acetate frames were shown to be ineffective in this regard at 30 yards.

Adult↗

Polymers derived from the amino acid L-tyrosine: polycarbonates, polyarylates and copolymers with poly(ethylene glycol).

The natural amino acid L-tyrosine is a major nutrient having a phenolic hydroxyl group. This feature makes it possible to use derivatives of tyrosine dipeptide as a motif to generate diphenolic monomers, which are important building blocks for the design of biodegradable polymers. Particularly useful monomers are desaminotyrosyl-tyrosine alkyl esters (abbreviated as DTR, where R stands for the specific alkyl ester used). Using this approach, a wide variety of polymers have been synthesized. Here, tyrosine-derived polycarbonates, polyarylates, and polyethers are reviewed with special emphasis on recent developments relating to cellular and in vivo responses, sterilization techniques, surface characterization, drug delivery, and processing and fabrication techniques. The commercial development of tyrosine-derived polycarbonates is most advanced, with one polymer, poly(DTE carbonate) (E=ethyl), being under review by the USA Federal Drug Administration.

Animals↗

Two-dimensional transferred-echo double resonance study of molecular motion in a fluorinated polycarbonate.

A two-dimensional version of the transferred-echo double resonance (TEDOR) experiment is introduced to measure strong heteronuclear magnetic dipolar interactions between rare spins. A quantitative description of this 2D-TEDOR experiment is given for an I-S pair of spins undergoing relative motion. 2D-TEDOR calculations are consistent with data for a calibration model: the directly bound 13C-31P pair in [3-13C]glyphosate, HO31(3)P13CH2NHCH2COOH. Analysis shows that the indirect spin-spin interaction and the dipole-dipole interaction have opposite signs in this system. The 2D-TEDOR experiment is then used to measure heteronuclear 13C-19F interactions in a fluorinated polycarbonate in which an aromatic proton is replaced by a fluorine on every fourth ring. Results from the 2D-TEDOR experiment show that the aromatic ring flips that occur in ordinary polycarbonate are blocked for a fluorinated ring.

Carbon Isotopes↗

Porous and nonporous polycarbonate urethane stent-grafts for TIPS formation: biologic responses.

PURPOSE: To evaluate the biologic response to transjugular intrahepatic portosystemic shunts (TIPS) lined with polycarbonate urethane endografts and the effects of different porosity formulations. MATERIALS AND METHODS: Seventeen TIPS were created in non-modified portal hypertensive miniswine with use of porous (n = 6), nonporous (n = 7) polycarbonate urethane stent-grafts, and control Wallstents TIPS (n = 4). Eight-week venography, histology, scanning electron microscopy, and immunohistochemical analyses were performed. RESULTS: The mean 8-week percent parenchymal tract shunt stenosis was 75%, 46%, and 26% in the control, porous, and nonporous groups, respectively. Occlusions developed in one control, one porous, and two nonporous shunts. The biologic response to porous grafts included marked inflammation and encapsulation and permeation of the grafts by a thick fibrous pseudointima. Nonporous grafts evoked little inflammation or pseudointima. Mature thrombus lined the occluded shunts (under which little luminal pseudointima or endothelium was present). The control group showed typical pseudointimal hyperplasia enveloping the intraparenchymal portions of the stents. CONCLUSIONS: The healing response of the porous and nonporous grafts markedly differed. Unlike the porous grafts and control stents, the nonporous endografts elicited little inflammation or luminal pseudointimal hyperplasia, although sporadic thrombosis was problematic in this normotensive model. Graft use in high-flow situations (ie, human TIPS, possibly in concert with antiplatelet agents) may allow desired shunt patency prolongation.

Animals↗

Microfabricated polycarbonate CE devices for DNA analysis.

The microchip capillary electrophoresis (CE) devices were fabricated in polycarbonate (PC) plastic material by compression molding. The molded devices were enclosed utilizing thermal bonding to another PC wafer. These thermal bonds do not yield up to an applied force equivalent to 150 psi. Aqueous fluid transport inside the plastic CE devices was enhanced by UV irradiation treatment of the hydrophobic polycarbonate plastic surfaces prior to thermal bonding. In comparison to glass microchannels, electroosmotic flow (EOF) in native PC channels is low and is independent of buffer pH at pH 7 and 9. UV irradiation of PC surfaces increases surface hydrophilicity and increases EOF. CE DNA separation was demonstrated in these PC CE devices with good resolution and run-to-run reproducibility. The on-chip PCR/CE analysis of a 500-bp region of bacteriophage lambda DNA was also demonstrated.

DNA↗

High-throughput determination of quantitative structure-property relationships using a resonant multisensor system: solvent resistance of bisphenol a polycarbonate copolymers.

Polymers are important materials for sensor, microfluidic, and other demanding applications. High-throughput screening methodology has been applied for the evaluation of the solvent resistance of a family of polycarbonate copolymers prepared from the reaction of bisphenol A (BPA), hydroquinone (HQ), and resorcinol (RS) in different solvents of practical importance, such as chloroform, tetrahydrofuran (THF), and methyl ethyl ketone (MEK). We employed a 24-channel acoustic-wave sensor system that provided previously unavailable capabilities for parallel evaluation of polymer solvent resistance. This high-throughput polymer evaluation approach assisted in construction of detailed solvent-resistance maps of polycarbonate copolymers and in determination of quantitative structure-property relationships. The best absolute solvent resistance of all studied copolymers was achieved in MEK, followed by chloroform and THF. A D-optimal mixture design was employed to explore the relationship between the copolymer compositions and their solvent resistance. The applied special cubic model for each solvent took into account the primary mixture terms such as BPA, HQ, and RS; binary interaction terms such as BPA-HQ, BPA-RS, and HQ-RS; and a ternary interaction term BPA-HQ-RS. A combination of the normal distribution of the model residuals and the very high values of adjusted R2 (0.97-0.99) demonstrated a good quality of the model. At a HQ concentration of 40 mol %, the solvent resistance was the highest for all tested solvents, and different concentrations of BPA (40 and 60 mol %) and RS (0 and 20 mol %) did not affect the solvent resistance. Without HQ, solvent resistance was decreasing with an increase of RS and decrease of BPA. Overall, with an increase of HQ concentration from 0 to 40 mol %, the solvent resistance of BPA-HQ-RS copolymers was improved by up to 3 times in THF, by 21 times in chloroform, and by 32 times in MEK.

Journal Article↗

Carbon dioxide/epoxide coupling reactions utilizing Lewis base adducts of zinc halides as catalysts. Cyclic carbonate versus polycarbonate production.

The reactions of zinc halides with 2,6-di-methoxypyridine or 3-trifluoromethylpyridine in dichloromethane have led to the formation of quite different complexes. Specifically, reactions involving pyridine containing electron donating methoxy substitutents have provided salts of the type [Zn(2,6-dimethoxypyridine)4][Zn2X6], as revealed by elemental analysis and X-ray crystallography. On the other hand, simple bis-pyridine adducts of zinc halides were isolated from the reactions involving the pyridine ligand with electron withdrawing substituents and characterized by X-ray crystallography, for example, Zn(3-trifluoromethylpyridine)2Br2. These zinc complexes were shown to be catalytically active for the coupling of carbon dioxide and epoxides to provide high molecular weight polycarbonates and cyclic carbonates, with the order of reactivity being Cl > or = Br > I, and 2,6-di-methoxypyridine > 3-trifluoromethylpyridine. Polycarbonate production from carbon dioxide and cyclohexene oxide was shown to be first-order in both metal precursor complex and cyclohexene oxide, as monitored by in situ infrared spectroscopy at 80 degrees C and 55 bar pressure. For reactions carried out in CO2 swollen epoxide solutions in the absence of added quantities of pyridine, the copolymer produced contained significant polyether linkages. Alternatively, reactions performed in the presence of excess pyridine or in hydrocarbon solvent, although slower in rate, afforded completely alternating copolymers. For comparative purposes, zinc chloride was a very effective homopolymerization catalyst for polyethers. Additionally, zinc chloride afforded copolymers with 60% carbonate linkages in the presence of high carbon dioxide pressures. In the case of cyclohexene oxide, the copolymer back-biting reaction led exclusively to the production of the trans cyclic carbonate as shown by infrared spectroscopy in v(C=O) region and X-ray crystallography. The unique feature of these catalyst systems is their simplicity.

Journal Article↗

pH-induced hysteretic gating of track-etched polycarbonate membranes: swelling/deswelling behavior of polyelectrolyte multilayers in confined geometry.

pH-induced hysteretic gating of track-etched polycarbonate membranes (TEPC) has been achieved by depositing layer-by-layer assembled polyelectrolyte multilayers comprising poly(allylamine hydrochloride) (PAH) and poly(sodium 4-styrenesulfonate) (PSS) at a high pH condition (pH > 9.0). Scanning electron microscopy and transmission electron microscopy showed that the average bilayer thickness of multilayers was greater within the cylindrical pores of track-etched polycarbonate membranes compared to the multilayers on planar substrates (e.g., Si wafers and the face of TEPC membranes). Swelling/deswelling properties of multilayers and gating properties of the multilayer-modified TEPC membranes were studied by measuring the flux of pH-adjusted deionized water. Large discontinuous changes in the transmembrane flux were observed, indicating that the multilayers within the cylindrical pores of TEPC membranes exhibit the discontinuous swelling/deswelling behavior observed previously for planar systems. The degree of swelling as estimated by simple models, however, showed that (PAH/PSS) multilayers in the confined geometry swelled to smaller extents compared to the same multilayers on planar substrates under the same conditions. Multilayer-modified membranes showed reversible gating properties as the pH condition of feed solution was alternated between pH 2.5 and 10.5. In situ atomic force microscopy (AFM) was used to visualize the closing of the pores as a function of time. The hysteretic gating property of the multilayer-modified TEPC membrane was utilized to achieve either a "closed" or "open" state at one pH condition depending on the pretreatment history, thereby enabling either the retention or passage of high-molecular weight polymers by varying the membrane pretreatment condition.

Journal Article↗

Determination of potential migrants in polycarbonate containers used for microwave ovens by high-performance liquid chromatography with ultraviolet and fluorescence detection.

The determination of several compounds present in a commercial polycarbonate container intended to be used in microwave ovens which could be considered as potential migrants has been carried out by reversed-phase high-performance liquid chromatography (HPLC) with both ultraviolet (UV) and fluorescence detectors. Total dissolution with dichloromethane and polymer reprecipitation with methanol have been used to evaluate 100% potential migration as the worst case. The extract consisted of a complex mixture containing monomers, oligomers, UV stabilizers, antioxidants, degradation products, and other additives. Phenol, Bisphenol A, 2,4-di-tert-butylphenol, Cyasorb UV5411, bis(2-ethylhexylphthalate), Irganox 1076, and Irgafos 168 were identified by both retention times and fluorescence-to-UV ratios. Additional confirmation was achieved by HPLC with diode array detection and gas chromatography-mass spectrometry. Recovery percentages were in the range of 73.8-94.4%, the lowest one being for the antioxidant Irgafos 168 due to its transformation into the phosphate form and 2,4-di-tert-butylphenol. The concentrations of the studied analytes present in the polycarbonate container ranged between 0.9 and 240 microg.g(-)(1). The total dissolution conditions that may affect the final concentration of analytes, mainly Bisphenol A, are discussed.

Chromatography, High Pressure Liquid↗

Self-supported particle-track-etched polycarbonate membranes as templates for cylindrical polypyrrole nanotubes and nanowires: an X-ray scattering and scanning force microscopy investigation.

Self-supported particle-track-etched polycarbonate membranes with nearly perfect cylindrical pores are used for the preparation of similarly perfect cylindrical polypyrrole nanowires and nanotubes. A complete investigation of the structural properties that result at different stages of the preparation route of polypyrrole nanowires and nanotubes is based on a combination of real and reciprocal space techniques. Nanoporous membranes with nominal pore size ranging from 5 to 150 nm and pore density up to 10(9) pores/cm(2) made from 21-microm-thick polycarbonate films are used. Polypyrrole nanotubes or nanowires are synthesized inside the pores. A real-space picture of the nanomaterial results from scanning force microscopy (SFM) on ultrathin sections made in two directions to obtain structures in the sample surface as well as perpendicular to the surface. From a model-based fit to the small-angle and ultra-small-angle X-ray scattering (SAXS/USAXS) data, the geometric pore structure is obtained and compared to values determined with scanning electron microscopy (SEM). Nanopores, nanowires, and nanotubes are described by uniform solid cylinders or hollow tubes, which are oriented highly parallel to each other and exhibit a small size distribution. Below a critical pore diameter, solid nanowires are produced whereas above this limit hollow nanotubes result.

Microscopy, Atomic Force↗

Automated absorption assessment using Caco-2 cells cultured on both sides of polycarbonate membranes.

PURPOSE: To increase the capacity of in vitro absorption assessment and to decrease the amount of substance needed to perform early mechanistic investigations. METHODS: A liquid handling system, combined with a shaker and heating plates, was used to automate the Caco-2 cell based in vitro absorption assessment assay. In order to decrease the amount of substance needed for early mechanistic studies, a method for culturing Caco-2 cells on the lower side of polycarbonate membranes was also developed. RESULTS: Similar results were obtained with the automated assay as compared to manually performed assays. Data presented suggest that active transport and efflux were decreased in cells cultured on the lower side of the membranes as compared to ordinary seeded cells. CONCLUSIONS: Implementation of a liquid handling system for in vitro absorption assessment as reported here decrease the manual workload and increases the capacity of this in vitro assay substantially. Caco-2 cells cultured on the lower side of polycarbonate membranes, as described in this article, can not be used for analysis of transport mechanisms.

Absorption↗

The effect of pH and culture system on the attachment of plasmid-bearing and plasmid-cured Yersinia enterocolitica to a polycarbonate membrane in a surface adhesion immunofluorescent technique.

A rapid surface adhesion based immunofluorescence technique was used to isolate and detect Yersinia enterocolitica from inoculated enriched culture systems. The pathogen was isolated by surface adhesion to a polycarbonate membrane which was mounted on a glass slide and immersed in the enriched culture for 15 min. The pathogen was detected using a fluorescent labelled (FITC) monoclonal antibody which was specific for Y. enterocolitica serotype O:3 and then viewed using fluorescent microscopy. The effect of culture type (broth, meat homogenate and minced meat) and pH (5.00, 7.00, 9.00 and 11.00) on the adhesion of plasmid-bearing and plasmid-cured Y. enterocolitica to the polycarbonate membrane in this technique was determined. The pH had a significant effect (P < 0.05) in broth and meat homogenate cultures, with enhanced attachment of Y. enterocolitica (P+ and P-) at pH 9.00 than at pH 5, 7 or 11. Culture type was also important, with differences observed in the numbers of Yersinia adhering to membranes immersed in broth, meat homogenate and minced beef. Differences in attachment were noted between plasmid-bearing and plasmid-cured Y. enterocolitica isolated from similar cultural environments. The reasons for these observed differences, and their implications for the surface adhesion immunofluorescent rapid method, are discussed.

Bacterial Adhesion↗

Migration of 2-butoxyethyl acetate from polycarbonate infant feeding bottles.

An enforcement campaign was carried out to assess the migration of 2-butoxyethyl acetate (2-BEA) from polycarbonate infant feeding bottles intended for repeated use. Migration was measured by three successive migration tests into two of the European Union official food simulants: distilled water and 3% acetic acid testing at 40 degrees C for 10 days. The Danish Veterinary and Food Administration (DVFA) has assessed that a migration above 0.33 mg for 2-BEA and a group of eight related substances kg(-1) foodstuff from plastics articles used exclusively for infants is unacceptable. Migration of 2-BEA was found from eight of 12 bottles. However, migration above the target value of 0.33 mg kg(-1) was not observed in the third decisive test from any of the 12 different brands of polycarbonate feeding bottles. A migration of between 0.05 and 0.26 mg kg(-1) from seven of 12 bottles was measured to 3% acetic acid in the third test, whereas no migration to distilled water was observed in the third test. The average recovery of 2-BEA after the 10-day exposure at the target value of 0.33 mg kg(-1) was 77% into distilled water and 36% into 3% acetic acid. The limited recovery was understandable as 2-BEA was partly hydrolysed in the aqueous food simulants and 2-butoxyethanol, a hydrolysis product and one of the related substances was identified. Quantification was carried out using gas chromatography after liquid/liquid extraction of the food simulant.

Acetates↗

Purification and preconcentration of genomic DNA from whole cell lysates using photoactivated polycarbonate (PPC) microfluidic chips.

We discuss the use of a photoactivated polycarbonate (PPC) microfluidic chip for the solid-phase, reversible immobilization (SPRI) and purification of genomic DNA (gDNA) from whole cell lysates. The surface of polycarbonate was activated by UV radiation resulting in a photo-oxidation reaction, which produced a channel surface containing carboxylate groups. The gDNA was selectively captured on this photoactivated surface in an immobilization buffer, which consisted of 3% polyethylene glycol, 0.4 M NaCl and 70% ethanol. The methodology reported herein is similar to conventional SPRI in that surface-confined carboxylate groups are used for the selective immobilization of DNA; however, no magnetic beads or a magnetic field are required. As observed by UV spectroscopy, a load of approximately 7.6 +/- 1.6 microg/ml of gDNA was immobilized onto the PPC bed. The recovery of DNA following purification was estimated to be 85 +/- 5%. The immobilization and purification assay using this PPC microchip could be performed within approximately 25 min as follows: (i) DNA immobilization approximately 6 min, (ii) chip washout with ethanol 10 min, and (iii) drying and gDNA desorption approximately 6 min. The PPC microchip could also be used for subsequent assays with no substantial loss in recovery, no observable carryover and no need for 'reactivation' of the PC surface with UV light.

Buffers↗