Thermo-mechanical analysis of a compliant poly(carbonate-urea)urethane after exposure to hydrolytic, oxidative, peroxidative and biological solutions

AIMS: To date, there is still a great need for a fully viable small diameter (< 6 mm) polymeric vascular graft. Currently in such low flow locations, non-elastic expanded polytetrafluoroethylene (ePTFE) is the best available but it is quite inferior to autologous saphenous vein since it fails due to intimal hyperplasia caused by compliance mismatch between the graft and elastic host artery. Recently, a novel compliant poly(carbonate-urea)urethane vascular graft whose trade name is MyoLink has been developed. In this article, we report the findings of a thermo-mechanical analysis of the polymers chemistry postexposure to in vitro solutions comprised of hydrolytic, oxidative, peroxidative and biological media. METHODS AND MATERIALS: The following degradative solutions were used in vitro: plasma fractions I-IV; phospholipase A2 (PLA); cholesterol esterase (CE) and solutions of H2O2/CoCl2, t-butyl peroxide/CoCl2 (t-but/CoCl2) and glutathione/t-butyl peroxide/ CoCl2 (glut/t-but/CoCl2). The MyoLink graft was compared against a conventional poly(ether)urethane (Pulse-Tec). All the graft specimens were 100 mm in length (5.0 mm ID) and were incubated in the latter solutions at 37 degrees C for 70 days in total. The following thermo-mechanical methods were used to analyse both graft types: thermo-mechanical analysis (TMA) and dynamic mechanical thermal analysis (DMTA). RESULTS: Incubation of Pulse-Tec in plasma fractions I-IV, PLA and CE reveals only one observable modification: an increase in the size of the low temperature, melting phase. But incubation in H2O2/CoCl2, and t-but/CoCl2 leads to an increase in the polymeric phase separation coupled with an enlargement in the size of the low temperature melting crystalline phase in Pulse-Tec. The glut/t-but/CoCl2 solution leads to a phase separation between the hard and soft segment domains, coupled with an increase of the internal order within the hard segment domains in Pulse-Tec. The only system in which MyoLink degraded was glut/t-but/CoCl2. In this system, an increase of the phase separation coupled with a simultaneous increase of the crystal size of the low-temperature melting crystalline phase occurred. CONCLUSION: This study shows dramatic changes in the chemistry of the soft and hard segments occurred in the case of the conventional poly(ether)urethane Pulse-Tec graft material. Such changes were not manifested in the majority of solutions in the case of MyoLink but a hydrolytic-led degradation of the carbonate soft segment was evidenced only in the glut/t-but/CoCl2 system.     

A new generation of polyurethane vascular prostheses: rara avis or ignis fatuus?

Three polyurethane (PU) vascular grafts with novel designs were investigated and compared in terms of the microporous structure, reinforcement technology, polymer chemistry, microphase separation, and mechanical properties. The Corvita graft, composed of a poly(carbonate urethane) polymer, displayed a helically wound filament structure with communicating inter-fiber spaces. The reinforced model contained an external PET mesh impregnated with a protein sealant, and displayed good microphase separation, the highest Young's modulus in the longitudinal direction, and the second highest in the radial direction. The Thoratec graft was made of a polyetherurethaneurea with an average micropore size of 15 microns. Silicone was observed on both surfaces of the graft. The Thoratec device displayed a low degree of hydrogen-bonding among the urethane groups and had no well-organized hard-segment domains. Its mechanical strength was superior to that of the Pulse-Tec graft. A solid PU layer underneath the luminal surface precluded any communication between the luminal and adventitial sides. The Pulse-Tec prosthesis was composed of polyetherurethane, with an average micropore size of 28 microns. It offered the highest radial compliance, a high degree of hydrogen-bonding, a narrow molecular weight distribution, and a certain degree of microphase separation. Its tensile strength and hysteresis loss were inferior to those of the other two grafts.     

Introducing a selectively biodegradable filament wound arterial prosthesis: a short-term implantation study.

This article introduces a new compliant and selectively biodegradable filament wound vascular graft and reports the findings of a short-term implantation study. A basic feature of filament winding is its ability to tailor and better control the mechanical properties of the prosthesis, so that a closer match with the anisotropic properties of native arteries is achieved. The elastomeric vascular grafts comprise poly(ether urethane urea) fibers (Lycra) embedded in a two-component matrix consisting of poly(ether urethane) (Pellethane) and a highly flexible poly(ethylene glycol)/poly(lactic acid) biodegradable segmented copolymer (PELA). Typical tensile modulus values fall in the few megapascals (MPa) range, this being comparable to that of natural arteries. The wound graft exhibits excellent handling and suturability characteristics as well as enhanced burst strength. Furthermore, due to its biodegradable constituent, the prosthesis combines minimal intraoperative blood loss and high healing porosity. The graft displays initially negligible in vitro water permeation, which increases gradually with time. In this short-term study, the prostheses were implanted in the canine carotid, and their biological performance was compared to that of expanded Gore-Tex. The luminal surface of the wound grafts was coated with a thin layer of pseudointima, strongly adhered to the prosthesis surface. Contrasting with the very stiff Gore-Tex grafts, the filament wound prostheses retained their high compliance, being highly pulsatile upon explanation. Histological studies fully corroborated these findings, underscoring the healing properties of these new filament wound vascular prostheses.     

Five Types of Polyurethane Vascular Grafts in Dogs: The Importance of Structural Design and Material Selection

Five polyurethane vascular grafts with three different chemistries were investigated in terms of device function, healing characteristics and material stability in a canine abdominal aorta model for prescheduled periods of 1 and 6 months. Corvita^®-reinforced grafts, with walls made of poly(carbonate urethane) (PCU) filaments, displayed a relatively thin, uniform and partially endothelialized inner capsule with good tissue in-growth. The external polyester mesh separated from the underlying PCU wall due to the degradation of the melt adhesive between these two layers. Three types of Thoratec^® access graft exhibited a high degree of thrombus and little tissue in-growth, and were non-adhesive to both the inner and external capsules as the solid layer beneath their lumens completely blocked any transmural communication. The microporous poly(ether urethane urea) degraded extensively. Pulse-Tec^® grafts at one month also demonstrated non-adhesive properties because the external skin served as a barrier to tissue in-growth. At 6 months, its poly(ether urethane) wall displayed the most severe degradation, damaging graft structural integrity and causing significant tissue deposition in the degradation areas. This study shows the importance of multiple factors in vascular prosthesis design and demonstrates that collective and comprehensive thinking will be key in the future development of creative and novel approaches.     

Enzymatic degradation of poly(ether urethane) and poly(carbonate urethane) by cholesterol esterase

This study examined the effect of cholesterol esterase (CE) on the degradation of commercial poly(ether urethane) (PEU) and poly(carbonate urethane) (PCU). Unstrained PEU and PCU films were incubated in 400 U/mL CE solution or a buffer control for 36 days. The study used a concentration of cholesterol esterase that was considerably higher than the estimated physiological level in order to accelerate degradation. However, characterization of treated polyurethane films with SEM, attenuated total reflectance Fourier transform infrared (ATR-FTIR) and GPC analysis revealed only a small loss in surface soft segment content. Comparison with implanted PEU and PCU films led to the conclusion that any effect of enzymatic hydrolysis was confined to the immediate surface, and the magnitude of the effect was too small to contribute significantly to in vivo degradation. The study confirmed that oxidation, rather than enzymatic hydrolysis, is the primary mechanism responsible for the observed biodegradation of PEU and PCU. The oxidative H(2)O(2)/CoCl(2) treatment continues to accurately predict the long-term biostability of polyurethanes.     

An assessment of covalent grafting of RGD peptides to the surface of a compliant poly(carbonate-urea)urethane vascular conduit versus conventional biological coatings: its role in enhancing cellular retention

The aim of sodding prosthetic grafts with endothelial cells (EC) is to establish a functioning antithrombogenic monolayer of EC. Application of basement membrane proteins improves EC adherence on ePTFE grafts. Their addition to a biodurable compliant poly(carbonate-urea)urethane graft (CPU) was studied with respect to EC adherence. Preclot, fibronectin, gelatin, and collagen were coated onto CPU. RGD peptide, heparin, and both RGD and heparin were chemically bonded to CPU. Human umbilical vein EC (HUVEC) labeled with 111-Indium oxine were sodded (1.8 x 10(6) EC/cm(2)) onto native and the modified CPU. The grafts were washed after 90 min and EC retention determined. The experiments were repeated six times. EC retention on native CPU was 1.0 +/- 0.2 x 10(5) EC/cm(2). The application of preclot, fibronectin, gelatin, and collagen did not improve EC retention, which was 0.8 +/- 0.1, 0.4 +/- 0.1, 0.3 +/- 0.08, and 0.5 +/- 0.2 x 10(5) EC/cm(2), respectively. Bonding RGD, heparin, and both RGD and heparin significantly improved EC retention to 1.9 +/- 0.6, 1.7 +/- 0.5, and 2.6 +/- 0.6 x 10(5) EC/cm(2), respectively (p < 0.01). Bonding of RGD, heparin, and both RGD and heparin accelerates and enhances EC retention onto CPU. Simple coating of basement membrane proteins confers no advantage over native CPU.     

Oxidative mechanisms of poly(carbonate urethane) and poly(ether urethane) biodegradation: in vivo and in vitro correlations

This study used an in vitro environment that simulated the microenvironment at the adherent cell-material interface to reproduce and accelerate the biodegradation of poly(ether urethane) (PEU) and poly(carbonate urethane) (PCU). Polyurethane films were treated in vitro for 24 days in 20% hydrogen peroxide/0.1 M cobalt chloride solution at 37 degrees C. Characterization with ATR-FTIR and SEM showed soft segment and hard segment degradation consistent with the chemical changes observed after long-term in vivo treatment. Overall, the PCU underwent less degradation and the degraded surface layer was much thinner than PEU. Nevertheless, the results supported a common oxidation mechanism for biodegradation of these polymers. The observed in vitro degradation was inhibited by adding an antioxidant to the polyurethane film. Our findings further support the use of the in vitro H(2)O(2)/CoCl(2) system in evaluating the biostability of polyurethanes under accelerated conditions.     

Arterial replacement with compliant hierarchic hybrid vascular graft: biomechanical adaptation and failure

Two types of hybrid vascular grafts were hierarchically structured with an autologous smooth muscle cell (SMC)-inoculated collagen gel layer and an endothelial cell (EC) monolayer, and wrapped with different elasomeric scaffolds. Type A graft was wrapped with poly(urethane)-nylon mesh, and type B graft was wrapped with an excimer laser-directed microporous segmented polyurethane (SPU) film as the scaffold. Type A graft was more compliant than canine carotid arteries, whereas compliance of type B graft was close to that of native arteries. After implantation into canine carotid arteries for 1 month, all type A grafts were dilated due to loosening of the mesh, resulting in loss of prelined ECs and thrombus formation. In contrast, type B grafts developed a well-organized neoarterial wall composed of a confluent EC monolayer and SMC-resided medial tissue, resulting in only slightly appreciable thrombus and minimal tissue ingrowth 6 months after implantation. Compliance of type B graft was reduced at 6 month's implantation, which is mostly due to encapsulated connective tissue formed around the graft.     

In vivo biostability of a poly(carbonate-urea)urethane graft

In peripheral and coronary bypass surgery, the patency of prosthetic grafts is inferior to autologous vein, mainly due to intimal hyperplasia caused in part by compliance mismatch between rigid graft and elastic host artery. We have developed a compliant poly(carbonate-urea)urethane vascular graft "MyoLink" which was biostable in vitro degradation studies. To further investigate the biostability of this material, we report a long-term in vivo study on 8 beagle dogs (15+/-3 kg) implanted with this graft (ID 5mm) in the aorta-iliac position; three grafts were harvested at 18 months to assess short-term biodegradation, with one animal having died from an unrelated infection. The 4 remaining grafts were harvested at 36 months for analysis by: (1) histology, (2) compliance measurements and (3) environmental scanning electron microscopy (ESEM); gel permeation chromatography (GPC); attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and radial tensile strength analysis.There was no infection or inflammation of the grafts or surrounding tissues. Histological analysis showed a well-developed neointima but only at the distal anastomosis. There were no significant differences in compliance pre- and post-implantation and no evidence of material curvature, radial expansion or chemical breakdown, ESEM and GPC showed no signs of degradation. Peak height analysis with ATR-FTIR of the 1740 cm(-1) (C=O of carbonate) and 1253 cm(-1) bands (C-O-C of CO-O-C) showed a loss of carbonate carbonyl but was not statistically significant. Radial tensile strength remained within batch release specifications.This polyurethane graft retains its compliance post-implantation, whilst exhibiting only a minor hydrolysis of the amorphous segment, confirming its biostability in vivo up to 3 years.     

Hydrolytic degradation and protein release studies of thermogelling polyurethane copolymers consisting of poly[(R)-3-hydroxybutyrate], poly(ethylene glycol), and poly(propylene glycol)

This paper reports the hydrolytic degradation and protein release studies for a series of newly synthesized thermogelling tri-component multi-block poly(ether ester urethane)s consisting of poly[(R)-3-hydroxybutyrate] (PHB), poly(propylene glycol) (PPG), and poly(ethylene glycol) (PEG). The poly(PEG/PPG/PHB urethane) copolymer hydrogels were hydrolytically degraded in phosphate buffer at pH 7.4 and 37 degrees C for a period of up to 6 months. The mass loss profiles of the copolymer hydrogels were obtained. The hydrogel residues at different time periods of hydrolysis were visualized by scanning electron microscopy, which exhibited increasing porosity with time of hydrolysis. The degradation products in the buffer were characterized by GPC, (1)H NMR, MALDI-TOF, and TGA. The results showed that the ester backbone bonds of the PHB segments were broken by random chain scission, resulting in a decrease in the molecular weight. In addition, the constituents of degradation products were found to be 3-hydroxybutyric acid monomer and oligomers of various lengths (n=1-5). The protein release profiles of the copolymer hydrogels were obtained using BSA as model protein. The results showed that the release rate was controllable by varying the composition of the poly(ether ester urethane)s or by adjusting the concentration of the copolymer in the hydrogels. Finally, we studied the correlation between the protein release characteristics of the hydrogels and their hydrolytic degradation. This is the first example that such a correlation has been attempted for a biodegradable thermogelling copolymer system.     

Biodegradable thermogelling poly(ester urethane)s consisting of poly(lactic acid)--thermodynamics of micellization and hydrolytic degradation

Multiblock poly(ether ester urethane)s comprising of poly(lactic acid) (PLA), poly(ethylene glycol) (PEG), and poly(propylene glycol) (PPG) segments were synthesized, and their aqueous solutions exhibited thermogelling behavior at critical gelation concentrations (CGC) ranging from 7 to 9 wt%. The chemical structures and molecular characteristics of the copolymers were studied by GPC, 1H NMR, 13C NMR and FTIR. The thermal stability of the poly(PEG/PPG/PLA urethane)s was studied by thermogravimetry analysis (TGA), and the PLA contents were calculated based on the thermal degradation profile. The results were in good agreement with those obtained from the 1H NMR measurements. The critical micellization concentration (CMC) of these water-soluble poly(ether ester urethane)s was determined at different temperatures using a dye solubilization method. The thermodynamic parameters for micelle formation were calculated, indicating that the process is largely entropy-driven. Interestingly, it appears that there exists a requirement for the system to possess a minimum gain in entropy before the thermogelling effect can be observed. Dilute copolymer solutions showed a lower critical solution temperature (LCST) behavior similar to pNIPAM dissolved in aqueous solutions. The thermogels hydrolytically degraded to polymer fragments corresponding to the constituent segment blocks within 3 months.     

Oxidative and hydrolytic stability of a novel acrylic terpolymer for biomedical applications

Oxidative and hydrolytic biostability assessment was carried out on a novel acrylic material made of hexamethyl methacrylate (HMA), methyl methacrylate (MMA), and methacrylic acid (MAA). To simulate the in vivo microenvironment, solutions of H2O2/CoCl2 and buffered solutions of cholesterol esterase (CE) and phospholipase A2 (PLA) were used. As controls, film specimens were incubated in deionized water. Samples were incubated in these solutions at 37 degrees C for 10 weeks before physical and mechanical properties were evaluated by size exclusion chromatography (SEC), 1H- nuclear magnetic resonance (1H-NMR), acid-base titration, and Instron tensile testing. The results from this study indicate excellent biostability of HMA-MMA-MAA terpolymers and thus their potential for use in biomedical devices for long-term implantation.     

聚碳酸酯型聚氨酯的体外降解研究

本研究聚碳酸酯型聚氨酯(PCU),在预氧化处理后(5%H2O2/0.05M CoCl2溶液),再用酶(番木瓜蛋白酶,20U/ml的溶液)水解处理后的表面形态及分子结构变化,同时与聚醚聚氨酯(PEU)和氟碳化合物封端的聚碳酸酯型聚氨酯(PCUF)材料作对比。通过扫描电镜(SEM),光电子能谱(XPS)和分子量(GPC)表征材料表面降解情况和分子结构变化。结果证实了材料的抗氧化性能直接影响材料的整体降解情况,结果显示PCU抗氧化性能优良,所以它的整体抗降解能力比抗氧化能力较低的PEU强,而且在PCU中引入氟碳化合物,其抗降解能力会更强。     

Fluorocarbon chain end-capped poly(carbonate urethane)s as biomaterials: blood compatibility and chemical stability assessments

Previous work has shown the synthesis of fluorocarbon chain (CF(3)(CF(2))(6)CH(2)O-) end-capped poly(carbonate urethane)s (FPCUs) and confirmed the presence of a novel bilayered surface structure in FPCUs, that is, the top fluorocarbon and subsurface hard segment layers (Xie et al., J Biomed Mater Res Part A 2008; 84:30-43). In this work, the effects of such surface structure on blood compatibility were investigated using hemolytic test and platelet adhesion analysis. The chemical stability of the polymers was also determined by Zhao's glass wool-H(2)O(2)/CoCl(2) test and phosphate-buffered saline (PBS, pH = 3.1-3.3) treatment. One of the FPCUs, FPCU-A, and two control materials, a poly(ether urethane) (PEU) and a poly(carbonate urethane) (PCU), were investigated. No significant difference in hemolytic indices was observed among the three materials, whereas the adherent density and deformation of platelets were much lower on FPCU-A compared with on PCU and PEU. Severe surface cracking and surface buckling developed in prestressed PEU and PCU films after H(2)O(2)/CoCl(2) treatment, respectively, whereas smooth surface was observed for the FPCU-A. PBS incubation resulted in parallel ridge-like morphology in PCU whereas PEU and FPCU-A retained their smooth surfaces. Under relatively high stress conditions, all the materials developed well-oriented strip-like surface patterns. Results from ATR-FTIR spectra revealed a surface oxidation mechanism as described in literature. However, observations of universal decrease of molecular weights under stress conditions further suggested the presence of another bulk stress oxidation mechanism. Regardless the degradation mechanisms involved, the unique bilayered surface structure really improved the blood compatibility and chemical stability of FPCU-A, indicating that further in vivo investigations are worthwhile.     

Long-term in vitro stability assessment of polycarbonate urethane micro catheters: resistance to oxidation and stress cracking

Micro catheter tubes were prepared from poly (carbonate urethane) (PCU, Bionate) and poly (ether urethane) (PEU, Pellethane) and their stability was investigated in vitro under applied strain. The tubes were stretched to an elongation of 200% or 300% and exposed to hydrogen peroxide/cobalt chloride (H(2)O(2)/CoCl(2)) solution for specific periods of time (up to 10 months). The samples were observed for surface degradation via scanning electron microscopy, the bulk erosion via the weight difference, and the changes in molecular weight using gel permeation chromatography. The 200% and 300% strained Pellethane tubes kept in H(2)O(2)/CoCl(2) solution for 1 month showed substantial cracking of the surface layer with pitting and have degraded completely within 45 to 60 days (from scanning electron microscopy). Bionate tubes treated in similar conditions for a 10-month period exhibited minute surface erosion in the depth of 0.25-1 microm and showed no evidence of major cracking or pitting. The gel permeation chromatography analysis of 300% strained catheters indicated that the degradation of Bionate tubes was negligible. The 10-month samples had shown approximately 18% reduction in their number average molecular weight (M(n)) and about 8% reduction in weight average molecular weight (M(w)). The Pellethane studied in similar conditions had indicated approximately 72% reduction in M(n) and about approximately 50% reduction in M(w) for 1 month. Overall, the Bionate underwent less degradation and the degradated surface layer was much thinner than Pellethane. These in vitro results are valuable in designing the in vivo studies for using Bionate tube as a long-term implant.     

Biodegradable polyurethanes for implants. II. In vitro degradation and calcification of materials from poly(epsilon-caprolactone)-poly(ethylene oxide) diols and various chain extenders

Linear, biodegradable, aliphatic polyurethanes with various degrees of hydrophilicity were synthesized in bulk at 50-100 degrees C. The ratios between the hydrophilic and hydrophobic segments were 0:100, 30:70, 40:60, 50:50, and 70:30, respectively. The hydrophilic segment consisted of poly(ethylene oxide) (PEO) diol (molecular weight = 600 or 2000) or the poly(ethylene-propylene-ethylene oxide) (PEO-PPO-PEO) diol Pluronic F-68 (molecular weight = 8000). The hydrophobic segment was made of poly(epsilon-caprolactone) diol (molecular weight = 530, 1250, or 2000). The chain extenders were 1,4-butane diol and 2-amino-1-butanol. The diisocyanate was aliphatic hexamethylene diisocyanate. The polymers absorbed water in an amount that increased with the increasing content of the PEO segment in the polymer chain. The total amount of absorbed water did not exceed 2% for the poly(ester urethane)s and was as high as 212% for some poly(ester ether urethane)s that behaved in water like hydrogels. The polymers were subjected to in vitro degradation at 37 +/- 0.1 degrees C in phosphate buffer solutions for up to 76 weeks. The poly(ester urethane)s showed 1-2% mass loss at 48 weeks and 1.1-3.8% mass loss at 76 weeks. The poly(ester ether urethane)s manifested 1.6-76% mass loss at 48 weeks and 1.6-96% mass loss at 76 weeks. The increasing content and molecular weight of the PEO segment enhanced the rate of mass loss. Similar relations were also observed for polyurethanes from PEO-PPO-PEO (Pluronic) diols. Materials obtained with 2-amino-1-butanol as the chain extender degraded at a slower rate than similar materials synthesized with 1,4-butane diol. All the materials already manifested a progressive decrease in the molecular weight in the first month of in vitro aging. The rate of molecular weight loss was higher for poly(ester ether urethane)s than for poly(ester urethane)s. For poly(ester ether urethane)s, the rate of molecular weight loss was higher for materials containing Pluronic than for those containing PEO segments. All polymers calcified in vitro. The susceptibility to calcification increased with material hydrophilicity. The progressive deposition of calcium salt on the film surfaces resulted in the formation of large crystal aggregates, the structure of which depended on the chemical composition of the calcified material. Needle-like aggregates, resembling brushite, formed on the hydrophobic polyurethane, and plate-like crystals formed on the highly hydrophilic material. The calcium-to-phosphorus atomic ratio of the crystals growing on the samples was dependent on the chemical composition of the material and varied from 0.94 to 1.55.     

Degradative changes in whole enamel homogenates incubated in vitro in the presence of low calcium ion concentrations

The purpose of this study was to investigate overall degradative changes occurring to enamel matrix proteins in small, freeze-dried pieces of rat incisor enamel homogenized and incubated directly for 0-48 hours in a synthetic enamel fluid solution (165 mM total ionic strength with 0.153 mM calcium chloride) versus other samples homogenized and incubated for the same time intervals in distilled water. The results indicated that many alterations in the apparent molecular weights of enamel matrix proteins took place under both conditions although the rates for many degradative changes over a 48 hour period were often slower in distilled water than in synthetic enamel fluid. Freeze-dried enamel samples homogenized and incubated in 165 mM Tris-HCl buffer at pH 8.0 showed changes comparable to those seen with distilled water. This suggested that differences observed between samples incubated in enamel fluid versus distilled water were unrelated to pH or ionic strength of the solutions and may be the result of a requirement by some enamel proteinases for small amounts of free calcium ions in incubation media. Of interest were findings that some enamel matrix proteins, especially those in strips taken from the first half of the secretory stage of amelogenesis, were degraded much faster in distilled water than in synthetic enamel fluid. The reasons for this effect are unclear although, in this case, calcium ions could be inhibitory to hydrolysis of certain matrix proteins by the enamel proteinases.     

Degradative Changes in Whole Enamel Homogenates Incubated In Vitro in the Presence of Low Calcium Ion Concentrations

The purpose of this study was to investigate overall degradative changes occurring to enamel matrix proteins in small, freeze-dried pieces of rat incisor enamel homogenized and incubated directly for 0–48 hours in a synthetic enamel fluid solution (165 mM total ionic strength with 0.153 mM calcium chloride) versus other samples homogenized and incubated for the same time intervals in distilled water. The results indicated that many alterations in the apparent molecular weights of enamel matrix proteins took place under both conditions although the rates for many degradative changes over a 48 hour period were often slower in distilled water than in synthetic enamel fluid. Freeze-dried enamel samples homogenized and incubated in 165 mM Tris-HCl buffer at pH 8.0 showed changes comparable to those seen with distilled water. This suggested that differences observed between samples incubated in enamel fluid versus distilled water were unrelated to pH or ionic strength of the solutions and may be the result of a requirement by some enamel proteinases for small amounts of free calcium ions in incubation media. Of interest were findings that some enamel matrix proteins, especially those in strips taken from the first half of the secretory stage of amelogenesis, were degraded much faster in distilled water than in synthetic enamel fluid. The reasons for this effect are unclear although, in this case, calcium ions could be inhibitory to hydrolysis of certain matrix proteins by the enamel proteinases.     

The degradative resistance of polyhedral oligomeric silsesquioxane nanocore integrated polyurethanes: an in vitro study

Polymer biostability is one of the critical parameters by which these materials are selected for use as biomedical devices. This is the major rationale for the use of polymers which are highly crystalline and stiff namely expanded polytetrafluoroethylene (ePTFE) and Dacron in particular, as arterial bypass grafts. While this is immaterial in high-flow states, it becomes critically important at lower flows with a greater need for more compliant vessels. Polyurethanes being one of the most compliant polymers known are as such, the natural choice to build such constructs. However, concerns regarding their resistance to degradation have limited their use as vascular prostheses and in order to augment their strength, herein a novel polyhedral oligomeric silsesquioxane integrated poly(carbonate-urea)urethane (POSS-PCU) nanocomposite was synthesised by our group. In the following series of experiments, the POSS-PCU nanocomposite samples were exposed to accelerated degradative solutions, in an 'in-house' established model in vitro for up to 70 days before being subjected to infra-red spectroscopy, scanning electron microscopy, stress-strain studies and differential scanning calorimetry. Our results demonstrate that these silsesquioxane nanocores shield the soft segment(s) of the polyurethane, responsible for its compliance and elasticity from all forms of degradation, principally oxidation and hydrolysis. These nanocomposites hence provide an optimal method by which these polymers may be strengthened whilst maintaining their elasticity, making them ideal as vascular prostheses particularly at low flow states.     

Effect of soft-segment chemistry on polyurethane biostability during in vitro fatigue loading

The effect of soft-segment chemistry on biostability of polyurethane elastomers was studied with a diaphragm-type film specimen under conditions of static and dynamic loading. During testing, the films were exposed to an H(2)O(2)/CoCl(2) solution, which simulated the oxidative component of the in vivo environment. Films treated for up to 24 days were evaluated by IR spectroscopy and by optical and scanning electron microscopy. Biostability of a poly(ether urethane) (PEU), which is known to undergo oxidative degradation, was compared with biostability of a poly(carbonate urethane) (PCU), which is thought to be more resistant to oxidation than PEU. Materials similar to PEU and PCU, in which the polyether or polycarbonate soft segment was partially replaced with poly(dimethylsiloxane) (PDMS), were also tested with the expectation that PDMS would improve soft-segment biostability. Oxidative degradation of the polyether soft segment of PEU was manifest chemically as chain scission and cross-linking and physically as surface pitting. Biaxial fatigue accelerated chemical degradation of PEU and eventually caused brittle stress cracking. In comparison, the polycarbonate soft segment was more stable to oxidation; there was minimal chemical or physical degradation of PCU, even in biaxial fatigue. Partial substitution of the polyether soft segment with PDMS enhanced oxidative stability of PEU. Although both strategies for modifying soft-segment chemistry improved the resistance to oxidative degradation, the outstanding mechanical properties of PEU were compromised to some extent.