ABSTRACT
Herein, we introduce a photobiocidal surface activated by white light. The photobiocidal surface was produced through thermocompressing a mixture of titanium dioxide (TiO2), ultra-high-molecular-weight polyethylene (UHMWPE), and reduced graphene oxide (rGO) powders. A photobiocidal activity was not observed on UHMWPE-TiO2. However, UHMWPE-TiO2@rGO exhibited potent photobiocidal activity (>3-log reduction) against Staphylococcus epidermidis and Escherichia coli bacteria after a 12 h exposure to white light. The activity was even more potent against the phage phi 6 virus, a SARS-CoV-2 surrogate, with a >5-log reduction after 6 h exposure to white light. Our mechanistic studies showed that the UHMWPE-TiO2@rGO was activated only by UV light, which accounts for 0.31% of the light emitted by the white LED lamp, producing reactive oxygen species that are lethal to microbes. This indicates that adding rGO to UHMWPE-TiO2 triggered intense photobiocidal activity even at shallow UV flux levels.
Subject(s)
Escherichia coli , Graphite , Light , Polyethylenes , Staphylococcus epidermidis , Titanium , Graphite/chemistry , Graphite/pharmacology , Graphite/radiation effects , Titanium/chemistry , Titanium/pharmacology , Polyethylenes/chemistry , Polyethylenes/radiation effects , Polyethylenes/pharmacology , Staphylococcus epidermidis/drug effects , Escherichia coli/drug effects , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Reactive Oxygen Species/metabolism , Ultraviolet RaysABSTRACT
Rapid volumetric in vivo visualization of circulating microparticles can facilitate new biomedical applications, such as blood flow characterization or targeted drug delivery. However, existing imaging modalities generally lack the sensitivity to detect the weak signals generated by individual micrometer-sized particles distributed across millimeter- to centimeter-scale depths in living mammalian tissues. Also, the temporal resolution is typically insufficient to track the particles in an entire three-dimensional region. Herein, we introduce a new type of monodisperse (4 µm) silica-core microparticle coated with a shell formed by a multilayered structure of carbon nanotubes (CNT) and gold nanoparticles (AuNP) to provide strong optoacoustic (OA) absorption-based contrast. We capitalize on the unique advantages of a state-of-the-art high-frame-rate OA tomography system to visualize and track the motion of these core-shell particles individually and volumetrically as they flow throughout the mouse brain vasculature. The feasibility of localizing individual solid particles smaller than red blood cells opens new opportunities for mapping the blood flow velocity, enhancing the resolution and visibility of OA images, and developing new biosensing assays.
Subject(s)
Contrast Media/chemistry , Metal Nanoparticles/chemistry , Microplastics/chemistry , Nanotubes, Carbon/chemistry , Animals , Brain/diagnostic imaging , Contrast Media/radiation effects , Female , Gold/chemistry , Gold/radiation effects , Infrared Rays , Metal Nanoparticles/radiation effects , Mice, Nude , Microplastics/radiation effects , Nanotubes, Carbon/radiation effects , Photoacoustic Techniques/methods , Polyethylenes/chemistry , Polyethylenes/radiation effects , Quaternary Ammonium Compounds/chemistry , Quaternary Ammonium Compounds/radiation effects , Tomography, X-Ray Computed/methodsABSTRACT
BACKGROUND: Synovial fluid components, especially lipids, can trigger oxidation of ultrahigh-molecular-weight polyethylene (UHMWPE) artificial joint components in vivo. The use of antioxidants such as vitamin E effectively diminishes the oxidative cascade by capturing free radicals and reducing the oxidation potential of UHMWPE implants. Using a thermo-oxidative aging method, we recently found that tea polyphenols can enhance the oxidation resistance of irradiated UHMWPE in comparison with commercial vitamin E. However, it is yet unknown whether tea polyphenols can reduce lipid-induced oxidation. QUESTIONS/PURPOSES: We explored whether tea polyphenol-stabilized UHMWPE would exhibit (1) lower squalene absorption; (2) stronger oxidation resistance; and (3) lower content of free radicals than vitamin E-stabilized UHMWPE under a physiologically-motivated in vitro accelerated-aging model. METHODS: Tea polyphenol (lipid-soluble epigallocatechin gallate [lsEGCG]) and vitamin E were blended with UHMWPE powders followed by compression molding and electron beam irradiation at 100 and 150 kGy. Small cubes (n = 3, 60 mg, 4 × 4 × 4 mm) cut from the blocks were doped in squalene at 60°, 80°, 100°, and 120° C for 2 hours. Gravimetric change of the cubes after squalene immersion was measured to assess absorption. Thin films (n = 3, â¼60 µm) were also microtomed from the blocks and were doped at 120° C for 24 hours. Oxidation induction time (n = 3, 5 mg of material from the cubes) and incipient oxidation temperature (n = 3, thin films) were obtained to determine the oxidation stability. Signal intensity of the free radicals, obtained by electron spin resonance spectroscopy, was used to qualitatively rank the antioxidant ability of vitamin E and lsEGCG. RESULTS: Squalene absorption was comparable between lsEGCG/UHMWPE and vitamin E/UHMWPE at a given temperature and radiation dose. The oxidation induction time of 100 kGy-irradiated UHMWPE was increased with lsEGCG compared with vitamin E except at 120° C. For example, the oxidation induction time value of 100 kGy-irradiated lsEGCG/UHMWPE immersed at 60 C was 25.3 minutes (24.2-27.8 minutes), which was 8.3 minutes longer than that of 100 kGy-irradiated vitamin E/UHMWPE which was 17.0 minutes (15.0-17.1 minutes) (p = 0.040). After squalene immersion at 120° C, the incipient oxidation temperature of 100 and 150 kGy irradiated lsEGCG/UHMWPE was 234° C (227-240° C) and 227° C (225-229° C), which was higher than vitamin E-stabilized counterparts with value of 217° C (214-229° C; p = 0.095) and 216° C (207-218° C; p = 0.040), respectively. The electron spin resonance signal of 150 kGy irradiated lsEGCG/UHMWPE was qualitatively weaker than that of 150 kGy irradiated vitamin E/UHMWPE. CONCLUSIONS: lsEGCG-stabilized UHMWPE demonstrated higher oxidation resistance than vitamin E-stabilized UHMWPE after squalene immersion, likely because lsEGCG donates more protons to eliminate macroradicals than vitamin E. CLINICAL RELEVANCE: Our in vitro findings provide support that lsEGCG may be effective in protecting against oxidation that may be associated with synovial fluid-associated oxidation of highly crosslinked UHMWPE joint replacement components.
Subject(s)
Antioxidants/chemistry , Catechin/analogs & derivatives , Joint Prosthesis , Plant Extracts/chemistry , Polyethylenes/chemistry , Vitamin E/chemistry , Antioxidants/isolation & purification , Camellia sinensis/chemistry , Catechin/chemistry , Catechin/isolation & purification , Free Radicals/chemistry , Oxidation-Reduction , Plant Extracts/isolation & purification , Polyethylenes/radiation effects , Prosthesis Failure , Squalene/chemistry , Time FactorsABSTRACT
Vitamin E stabilization successfully improved long-term oxidation resistance of wear-resistant ultra-high-molecular-weight polyethylene (UHMWPE) used for joint implants. Stabilization can be achieved by blending an antioxidant into the UHMWPE resin powder before consolidation and irradiation. Balancing the wear resistance and vitamin E content in the blend is the current challenge with this approach, because vitamin E hinders crosslinking of UHMWPE during irradiation, which decreases wear resistance. The vitamin E concentration in the blend is generally limited to less than 0.3 wt%. Wear- and oxidation-resistant UHMWPE has been obtained previously by consolidating blends of pre-irradiated UHMWPE powders (XPE) into an unmodified polyethylene matrix (PE), where the improvement in wear rate depended on the radiation dose and fraction of XPE. We hypothesized that increasing the vitamin E content in the unirradiated matrix would not compromise wear and would further improve the oxidative stability of XPE/PE blends. Pin-on-disk wear testing showed that the XPE/PE blends containing 0.1-1.0 wt% vitamin E in the matrix had comparable wear rates. We used an aggressive accelerated aging test in the presence of the pro-oxidant squalene and oxidation induction time (OIT) test and found that higher amounts of vitamin E resulted in stronger oxidation resistance for XPE/PE blends. The mechanical strength and toughness of the blends were not affected by changing the vitamin E content in the matrix. Stabilizing UHMWPE with higher vitamin E content may extend the service life of UHMWPE implants. © 2017 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 36:1860-1867, 2018.
Subject(s)
Joint Prosthesis , Materials Testing , Polyethylenes/chemistry , Polyethylenes/radiation effects , Prosthesis Design , Vitamin E/chemistry , Antioxidants/chemistry , Biocompatible Materials , Calorimetry, Differential Scanning , Oxidation-Reduction , Oxidative Stress , Oxygen/chemistry , Powders , Stress, Mechanical , Tensile StrengthABSTRACT
The articulating components of artificial joints consist mainly of metals, ceramics, or polymers. Resulting abrasive wear particles can promote osteolysis and aseptic loosening of the endo-prosthetic implants. Ultra-high-molecular-weight-polyethylene is the material used most for bearing couples in total hip replacement. In the present study, three types of polyethylene (PE) liners varying in material composition, i.e., (1) conventional PE (C-PE), (2) sequentially cross-linked PE (SX-PE), (3) cross-linked PE blended with vitamin E (EX-PE) articulating with two types of femoral heads were used. After ultrasound treatment of each simulator lubricant, different concentrations (0.1/0.25/0.5/1.0 mL) were taken and dissolved in hydrochloric acid (37%) in a similar manner. The aim was to analyze the characteristics of wear particles generated in a hip simulator, with respect to different volumes of the lubricant. Within the scope of particle analysis, distinct alterations for particle characteristics were determined in the lubricant volumes and types of PE material used. A significant decrease in particle number for SX-PE liners, compared to the C-PE inserts and even more for EX-PE inserts, was detected at each lubricant volume. Particle morphologies varied depending on PE material. Alterations in particle size and other morphologic parameters between the four tested volumes, could be proven for each PE type. In general, particle sizes and parameters (e.g., length and width) increased with increasing serum volumes. In conclusion, the chosen volume of the simulator lubricant used for particle analysis has a crucial influence on detected particle number, size distribution, and morphologic parameters. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1299-1306, 2018.
Subject(s)
Hip Prosthesis , Lubricants , Polyethylenes/chemistry , Algorithms , Cross-Linking Reagents , Humans , Particle Size , Particulate Matter , Polyethylenes/radiation effects , Prosthesis Failure , UltrasonicsABSTRACT
Morphology and design of ultra-high molecular weight polyethylene (UHMWPE or simply PE) acetabular components used in total hip arthroplasty (THA) have been evolving for more than half a century. Since the late-1990s, there were two major technological innovations in PE emerged from necessity to overcome the wear-induced periprosthetic osteolysis, i.e., the development of highly crosslinked PEs (HXLPEs). There are many literature reporting that radiation crosslinked and remelted/annealed (first-generation) HXLPEs markedly reduced the incidence of osteolysis and aseptic loosening. Regardless of such clinical success in the first-generation technologies, there were some recent shifts in Japan toward the use of new second-generation HXLPEs subjected to sequential irradiation/annealing or antioxidant vitamin E (α-tocopherol) incorporation. Although the selection rate of first-generation liners still account for more than half of all the PE THAs (â¼58% in 2015), the use of vitamin E-stabilized liners has been steadily growing each year since their clinical introduction in 2010. In these contexts, it is of great importance to evaluate and understand the real clinical benefits of using the new second-generation liners as compared to the first generation. This article first summarizes structural evolution and characteristic features of first-generation HXLPEs, and then provides a detailed description of second-generation antioxidant HXLPEs in regard to the role of vitamin E incorporation on their chemical and mechanical performances in THA.
Subject(s)
Arthroplasty, Replacement, Hip/methods , Cross-Linking Reagents/pharmacology , Forecasting , Osteolysis/prevention & control , Polyethylenes/chemistry , Postoperative Complications/prevention & control , Vitamin E/pharmacology , Antioxidants/pharmacology , Cross-Linking Reagents/radiation effects , Diffusion/radiation effects , Hip Prosthesis , Humans , Materials Testing , Polyethylenes/radiation effects , Prosthesis Design , Radiation, IonizingABSTRACT
Diffusion of vitamin E into radiation cross-linked ultrahigh molecular weight polyethylene (UHMWPE) is used to increase stability against oxidation of total joint implant components. The dispersion of vitamin E throughout implant preforms has been optimized by a two-step process of doping and homogenization. Both of these steps are performed below the peak melting point of the cross-linked polymer (<140°C) to avoid loss of crystallinity and strength. Recently, it was discovered that the exposure of UHMWPE to elevated temperatures, around 300°C, for a limited amount of time in nitrogen, could improve the toughness without sacrificing wear resistance. We hypothesized that high temperature homogenization of antioxidant-doped, radiation cross-linked UHMWPE could improve its toughness. We found that homogenization at 300°C for 8 h resulted in an increase in the impact toughness (74 kJ/m2 compared to 67 kJ/m2 ), the ultimate tensile strength (50 MPa compared to 43 MPa) and elongation at break (271% compared to 236%). The high temperature treatment did not compromise the wear resistance or the oxidative stability as measured by oxidation induction time. In addition, the desired homogeneity was achieved at a much shorter duration (8 h compared to >240 h) by using high temperature homogenization. © 2016 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 35:1343-1347, 2017.
Subject(s)
Polyethylenes/chemistry , Vitamin E/analysis , Gamma Rays , Hot Temperature , Joint Prosthesis , Polyethylenes/radiation effectsABSTRACT
Radiation crosslinking of ultra-high molecular weight polyethylene (UHMWPE) increases its wear resistance in total joint replacement prostheses. Unfortunately, it is accompanied by a dose-dependent decrease in several mechanical properties. In this study, the tensile properties and fracture behavior of radiation crosslinked, Vitamin E stabilized UHMWPE was studied as a function of radiation dose. The Rice and Sorensen model, applicable to elastic-plastic materials, was utilized to obtain the initial crack driving force, J1c, steady state J-integral fracture toughness, Jss and the Tearing modulus. Tensile tests showed the dependence of tensile properties on radiation dose. Jss of non-crosslinked UHMWPE was higher than for crosslinked UHMWPE׳s but there was no dose dependent change in Jss whereas there was almost no change in J1c over the entire dose range. Finally, a monotonic decrease in Tearing modulus was observed with radiation dose.
Subject(s)
Biocompatible Materials/chemistry , Biocompatible Materials/radiation effects , Polyethylenes/chemistry , Polyethylenes/radiation effects , Vitamin E/chemistry , Biomechanical Phenomena , Joint Prosthesis , Materials Testing , Tensile StrengthABSTRACT
Polymers with functionalized surfaces have attracted a lot of attention in the last few years. Due to the progress in the techniques of polymer micro-patterning, miniaturized bioanalytical assays and biocompatible devices can be developed. In the presented work, we performed surface modification of polyethylene naphthalate (PEN) foil by an excimer laser beam through a photolithographic contact mask. The aim was to fabricate micro-patterned areas with surface functional groups available for localized covalent immobilization of biotin. It was found out that depending on the properties of the laser scans, a polymer surface exhibits different degrees of modification and as a consequence, different degrees of surface biotinylation can be achieved. Several affinity tests with optical detection of fluorescently labeled streptavidin were successfully performed on biotinylated micro-patterns of a PEN foil. The polymer surface properties were also evaluated by electrokinetic analysis, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The results have shown that PEN foils can be considered suitable substrates for construction of micro-patterned bioanalytical affinity assays.
Subject(s)
Biotin/chemistry , Naphthalenes/chemistry , Polyethylenes/chemistry , Streptavidin/chemistry , Biotinylation , Lab-On-A-Chip Devices , Lasers, Excimer , Microtechnology , Naphthalenes/radiation effects , Photochemical Processes , Polyethylenes/radiation effects , Surface PropertiesABSTRACT
This investigation analyzed retrieved sequentially crosslinked and annealed (SXL) ultra-high molecular weight polyethylene bearings to determine whether the material is chemically stable in vivo. A series of retrieved tibial and acetabular components were analyzed for changes in ketone oxidation, crosslink density, and free radical concentration. Oxidation was observed to increase with in vivo duration, and the rate of oxidation in tibial inserts was significantly greater than in acetabular liners. SXL acetabular bearings oxidized at a rate comparable to gamma-sterilized liners, while SXL tibial inserts oxidized at a significantly faster rate than their gamma-sterilized counterparts. A significant decrease in crosslink density with increased mean ketone oxidation index was observed, suggesting that in vivo oxidation may be causing material degradation. Furthermore, a subsurface whitened damage region was also found in a subset of the bearings, indicating the possibility of a clinically relevant decrease in mechanical properties of these components.
Subject(s)
Acetabulum/surgery , Arthroplasty, Replacement, Hip/instrumentation , Hip Prosthesis , Knee Prosthesis , Polyethylenes/chemistry , Tibia/surgery , Device Removal , Equipment Failure Analysis , Free Radicals/analysis , Gamma Rays , Hip Prosthesis/adverse effects , Humans , Ketones/analysis , Knee Prosthesis/adverse effects , Materials Testing , Oxidation-Reduction , Polyethylenes/radiation effects , Prosthesis-Related Infections , Retrospective Studies , Spectroscopy, Fourier Transform Infrared , Sterilization , Surface Properties , Time FactorsABSTRACT
Antioxidant stabilization of radiation cross-linked ultrahigh molecular weight polyethylene (UHMWPE) has been introduced to improve the oxidative stability of total joint implant bearing surfaces. Blending of an antioxidant with UHMWPE resin powder followed by consolidation and radiation cross-linking has been cleared by the FDA for use in both total hips and total knees for designs incorporating two antioxidants, namely vitamin E and Covernox™ (a medical grade version of Irganox™ 1010). The antioxidants in the polymer are expected to protect the polymer during consolidation, during radiation cross-linking, on the shelf before implantation, and in vivo after implantation. To maximize the protection of the polymer afforded by the antioxidant in vivo, a novel approach may be the use of multiple antioxidants, especially to protect the primary antioxidant for a longer period of time. We hypothesized that the addition of a phosphite stabilizer (Irgafos 168™) commonly used in conjunction with hindered phenolic antioxidants in polymer processing could improve the oxidative stability of radiation cross-linked blends of vitamin E. To test our hypothesis, we prepared UHMWPE blends with 0.05 wt% Irgafos and 0.05 wt% vitamin E and compared its cross-link density, wear resistance, tensile properties, and impact strength to control blends containing only vitamin E. Our hypothesis was not supported; the cross-link density of UHMWPE was significantly decreased by the additive without additional benefit to oxidative stability. To our knowledge, this was the first attempt at using multiple stabilizers in medical grade UHMWPE.
Subject(s)
Antioxidants/administration & dosage , Materials Testing , Phosphites/chemistry , Polyethylenes/chemistry , Vitamin E/administration & dosage , Cross-Linking Reagents , Electrons , Joint Prosthesis/standards , Materials Testing/methods , Phosphites/administration & dosage , Polyethylenes/radiation effects , Stress, Mechanical , Tensile StrengthABSTRACT
UNLABELLED: Despite of well-known advantages of high molecular weight polyethylene (Medpor, Synpore) in orbital reconstructions, the thickness of those implants significantly exceeds 0.5 mm and precise modification of thickness is limited. The aim of this study was to present the application of a self-developed method of treatment orbital wall fracture by custom implant made of ultrahigh molecular weight polyethylene (UHMW-PE). MATERIAL AND METHOD: First, the test of influence of sterilization process upon implant deformation was performed (autoclaving, ethylene oxide, gas plasma, irradiation). Next, ten cases for delayed surgical treatment of orbital fracture were included into this study (7 males, 3 females). Based on CT scan and mirrored technique, a CAD model of virtual implant for repairing orbital wall was made. Then, an implant was manufactured with a computer numerical controlled milling machine from UHMW-PE block, sterilized and used during a surgical procedure. Clinically used implants had thickness from 0.2 to 4.0 mm. RESULTS: The best method of sterilization is ethylene oxide process, and the worst is autoclaving. In this series of delayed surgical cases, functional results of orbital surgery are worse than in simpler, early treated cases, but long-term subsidence of diplopia is noticeable [10% poor results]. The results of the treatment depend on the initial level of diplopia where severe initial diplopia to be corrected requires thicker implants (p < 0.01). It also leads to longer surgical procedures (p < 0.01), but prolongation of the surgery had no negative influence upon results of any investigated follow-up examinations. Obviously, the orbital destruction intensity is related to injury-evoked initial diplopia but it also influences whole results of treatment up to 12 months post-op. Interesting result is presented by the relation of maximal implant thickness to 12-month diplopia evaluation. Thicker implants used result in lower residual diplopia (p < 0.05). This is important because of the correlation between the higher orbital destruction intensity with a thicker UHMW-PE implant (p < 0.05) applied in this series. CONCLUSION: Patient-specific ultrahigh molecular weight polyethylene implants enable precise reconstructions of orbital wall. One should not be afraid of a significant eye globe reposition caused by these thickness modulated implants, as such repositioning is essential for an efficient correction of enophthalmos.
Subject(s)
Biocompatible Materials/chemistry , Computer-Aided Design , Orbital Fractures/surgery , Polyethylenes/chemistry , Prosthesis Design , Adult , Biocompatible Materials/radiation effects , Diplopia/surgery , Disinfectants/therapeutic use , Enophthalmos/surgery , Ethylene Oxide/therapeutic use , Female , Follow-Up Studies , Humans , Male , Multidetector Computed Tomography/methods , Operative Time , Orbital Fractures/diagnostic imaging , Plasma Gases/therapeutic use , Polyethylenes/radiation effects , Prosthesis Implantation/methods , Plastic Surgery Procedures/instrumentation , Sterilization/methods , Surface Properties , User-Computer Interface , Young AdultABSTRACT
Structural modifications were studied at the molecular scale in two highly crosslinked UHMWPE materials for hip-joint acetabular components, as induced upon application of (uniaxial) compressive strain to the as-manufactured microstructures. The two materials, quite different in their starting resins and belonging to different manufacturing generations, were a single-step irradiated and a sequentially irradiated polyethylene. The latter material represents the most recently launched gamma-ray-irradiated polyethylene material in the global hip implant market. Confocal/polarized Raman spectroscopy was systematically applied to characterize the initial microstructures and the microstructural response of the materials to plastic deformation. Crystallinity fractions and preferential orientation of molecular chains have been followed up during in vitro deformation tests on unused cups and correlated to plastic strain magnitude and to the recovery capacity of the material. Moreover, analyses of the in vivo deformation behavior of two short-term retrieved hip cups are also presented. Trends of preferential orientation of molecular chains as a function of residual strain were similar for both materials, but distinctly different in their extents. The sequentially irradiated material was more resistant to plastic deformation and, for the same magnitude of residual plastic strain, possessed a higher capacity of recovery as compared to the single-step irradiated one.
Subject(s)
Hip Prosthesis , Polyethylenes/chemistry , Spectrum Analysis, Raman/methods , Compressive Strength/radiation effects , Elastic Modulus/radiation effects , Equipment Failure Analysis , Gamma Rays , Hardness/drug effects , Materials Testing , Molecular Conformation/radiation effects , Polyethylenes/radiation effects , Radiation Dosage , Surface Properties/radiation effectsABSTRACT
AIM OF THE STUDY: The introduction ofphotodegradable polymers raises doubts among the natural profession. Photodegradation is a process of destruction of polymer, that is the entirety of physical and chemical change within the plastic, leading to irreversible changes in structure and deterioration of processing parameters. The prospect of release of products of degradation, possessing unknown capabilities is unsettling, as is the possibility of accumulation of compounds that could potentially be toxic, mutagenic and allergenic. Despite this, the use of photodegradable polymers is unavoidable in some cases. The applicability of degradable materials is easily visible in agriculture, horticulture and fruit-growing and medicine. The aim of the study is to asses the influence of selected additives over the process of accelerated aging of polyethylene. The aging was conducted in laboratory environment using lamps simulating the effect of natural sunlight in conditions similar to natural. MATERIAL AND METHODS: Preparation of polyethylene samples with sensitizers (TiO2-anatase, acacFe (II), acacFe (III)) added, aging of the sample in a UV chamber, estimating the surface changes in polyethylene after irradiation by measuring contact angle, spectroscopic analysis of polyethylene photodegradation, assessing endurance characteristics. The results of study show the highest degradation occurs if Ferrous (Iron (II)) acetylacetonate is used, with Ferric (Iron (III)) acetylacetonate showing slightly less effectiveness. TiO2-anatase indicates little influence over the process of degradation, on the contrary--a protective activity can be noticed, connected with white colour of this additive reflecting UV radiation. CONCLUSIONS: The results of the study clearly signify an interrelation between aging process and endurance characteristics of the material. The conducted analysis shows correlation between the number of carbonyl groups and endurance characteristics which, in turn, points to clear structural changes in polyethylene.
Subject(s)
Equipment Failure Analysis , Photolysis , Polyethylenes/chemistry , Polyethylenes/radiation effects , Photochemistry , Sunlight , Ultraviolet RaysABSTRACT
Property degradation of the medical grade polymers after gamma irradiation is the primary concern that limits longevity of them. Though the conventional antioxidant material helps to reduce the degradation but it limits the degree of crosslinking of the polymer. The objective of the present work is to study the influence of multi walled carbon nanotubes (MWCNTs) on restricting the degradation of mechanical properties of medical grade ultra high molecular weight polyethylene (UHMWPE) after its irradiation. UHMWPE was reinforced by chemically treated MWCNTs at different concentrations such as 0.5, 1.0, 1.5, and 2.0 wt%. The test samples were then subjected to Co6° gamma irradiation with an integral dose of 25, 50, 75 and 100 kGy in air. The mechanical properties of irradiated samples were evaluated within 10 days, 60 and 120 days after irradiation. It was observed that the mechanical properties of virgin UHMWPE and nanocomposites were enhanced immediately after irradiation but they were found to be reduced at later stages. It was also observed that the presence of MWCNTs limited the ageing degradation of the mechanical properties of UHMWPE. Raman spectroscopic and TEM studies confirmed the formation of irradiation induced defects on the MWCNTs. Electron spin resonance studies showed that the relative radical intensity of virgin UHWMPE was reduced significantly with an increase of MWCNTs concentration confirming the radical scavenging ability of them. It is concluded that MWCNTs restricted the ageing degradation of irradiated UHMWPE.
Subject(s)
Biocompatible Materials/chemistry , Biocompatible Materials/radiation effects , Nanotubes, Carbon/chemistry , Nanotubes, Carbon/radiation effects , Polyethylenes/chemistry , Polyethylenes/radiation effects , Dose-Response Relationship, Radiation , Gamma Rays , Hardness/radiation effects , Materials Testing , Nanotubes, Carbon/ultrastructure , Radiation Dosage , Surface Properties/radiation effects , Tensile Strength/radiation effectsABSTRACT
Limiting cross-linking to the articular surfaces of ultrahigh molecular weight polyethylene (UHMWPE) to increase wear resistance while preventing detrimental effects of cross-linking on mechanical strength has been a desirable goal. A surface cross-linked UHMWPE can be achieved by blending UHMWPE with a free radical scavenger, such as vitamin E, consolidating the blend into an implant shape, extracting the vitamin E from the surface, and radiation cross-linking the surface extracted blend. This process results in high cross-link density in the vitamin E-depleted surface region because vitamin E hinders cross-linking during irradiation. In this study, we described the properties of successful extraction media and the manipulation of the wear and mechanical properties of extracted, irradiated blends. We showed that these formulations could have similar wear and significantly improved mechanical properties compared to currently available highly cross-linked UHMWPEs. We believe that these materials can enable thinner implant forms and more anatomical designs in joint arthroplasty and may provide a feasible alternative to metal-on-metal implants.
Subject(s)
Femur Head/surgery , Hip Prosthesis , Polyethylenes/chemistry , Prosthesis Design/methods , Vitamin E/chemistry , Antioxidants/chemistry , Cross-Linking Reagents/chemistry , Cross-Linking Reagents/radiation effects , Emulsifying Agents/chemistry , Feasibility Studies , Femur Head/anatomy & histology , Femur Head/physiology , Gamma Rays , Humans , Materials Testing , Polyethylenes/radiation effects , Prosthesis Failure , Stress, Mechanical , Tensile StrengthABSTRACT
Ultrahigh molecular weight polyethylene (UHMWPE) is the most frequently used bearing surface in currently used total joint replacements (TJR). According to the literature available, UHMWPE is the best polymer material, in terms of biocompatibility, mechanical properties and wear resistance, for this application. In spite of this fact, UHMWPE wear (i.e., release of microscopic particles from the polymer surface) remains one of the main reasons of TJR failures. Consequently, the wear of UHMWPE is a subject of intensive study by both materials scientists and orthopaedic surgeons. The structure and properties of UHMWPE strongly depend on the way of processing and post-processing modifications. The processing includes polymer resin preparation (microparticles about 100 em in size) and resin consolidation (forming bulk material). Post-processing modifications aim at increasing wear resistance and oxidation stability which are regarded as major factors involved in TJR failure. In order to maintain high purity materials for medical application, it is not allowed to use additional chemicals during the modification processes. The only exception is the use of vitamin E, a natural stabilizer and antioxidant. Considering all the above mentioned facts, the modifications can be based on (I) ionizing radiation such as gamma rays or accelerated electrons, (II) thermal modification, (III) additional stabilization with vitamin E, and (IV) sterilization. According to the modifications, we usually differentiate three generations of UHMWPE. The 1st generation UHMWPE is not modified except for obligatory sterilization. The sterilization procedures based on chemical procedures (formaldehyde vapours, hot water) have lately been forbidden, abandoned and replaced by gamma-irradiation with doses of 25-45 kGy. In the course of time, sterilization by means of gamma-irradiation showed to be unsuitable due to oxidative degradation of UHMWPE, which resulted in lower wear resistance, worse material properties and a decrease in longevity of joint replacements. The 2nd generation UHMWPE or highly cross-linked UHMWPE is material treated with ionizing radiation (gamma-rays or accelerated electrons) at higher doses (usually 50-100 kGy). The irradiation is followed by thermal treatment in order to eliminate residual radicals and limit oxidative degradation that occurs in the 1st generation UHMWPE types. Finally, the material is sterilized usually by modern procedures using ethylene oxide or gas plasma neither of which causes oxidative degradation (as opposed to gamma-irradiation sterilization). The 3rd generation UHMWPE is basically the same as that of the 2nd generation. The main difference consists in slightly better mechanical properties (strength, fatigue) and further stabilization to oxidative degradation. This is achieved by special procedures, some of which are either controversial (sequential irradiation) or well-accepted by a great majority of the orthopaedic community (vitamin E stabilization). Only the future will show whether the difference between the 2nd and 3rd generations of UHMWPE will play any role in increasing TJR longevity and therefore the quality of its performance. The final objective of all of UHMWPE modifications is, as already mentioned, to increase wear resistance, oxidative resistance and mechanical performance of the polymer. These changes, especially an increase in wear resistance, have been confirmed to prolong the longevity of total joint replacements based on UHMWPE.
Subject(s)
Arthroplasty, Replacement , Joint Prosthesis , Polyethylenes , Biocompatible Materials , Biomechanical Phenomena , Humans , Polyethylenes/chemistry , Polyethylenes/radiation effects , SterilizationABSTRACT
BACKGROUND: In the mid to late 1990 s, to sterilize UHMWPE bearings, manufacturers changed from gamma-irradiation-in-air (gamma-air) sterilization, which initiated oxidation leading to bearing fatigue, to gamma-irradiation sterilization in an inert environment (gamma-inert). The change to gamma-inert sterilization reportedly prevented shelf oxidation before implantation but not in vivo oxidation. QUESTIONS/PURPOSES: We asked: (1) Has the change to gamma-inert sterilization prevented shelf oxidation that led to early in vivo fatigue damage in gamma-air-sterilized tibial inserts? And (2) has the change to gamma-inert sterilization prevented the occurrence of fatigue secondary to in vivo oxidation? METHODS: We rated 183 retrieved gamma-air- and 175 retrieved gamma-inert-sterilized tibial inserts for clinical fatigue damage and analyzed 132 gamma-air- and 174 gamma-inert-sterilized tibial inserts for oxidation by Fourier transform infrared spectroscopy. RESULTS: Oxidation led to decreased mechanical properties in shelf-aged gamma-air-sterilized tibial inserts. Barrier packaging prevented shelf oxidation in gamma-inert-sterilized tibial inserts. Gamma-air- and gamma-inert-sterilized inserts oxidized in vivo. Fatigue damage (delamination) occurred more frequently in inserts retrieved after longer time in vivo. Longer in vivo time correlated with higher oxidation and more accumulated cycles of use. CONCLUSIONS: Published oxidation projections suggest gamma-inert-sterilized tibial inserts would reach the critical oxidation for the onset of fatigue after 11 to 14 years in vivo. These retrievals appear to follow the projected oxidation trends. Frequency of fatigue damage increased with increasing oxidation. CLINICAL RELEVANCE: Fatigue of tibial inserts becomes more likely, especially in active patients, after more than a decade of good clinical performance.
Subject(s)
Arthroplasty, Replacement, Knee/instrumentation , Device Removal , Gamma Rays , Knee Prosthesis , Polyethylenes/radiation effects , Prosthesis Failure , Sterilization/methods , Arthroplasty, Replacement, Knee/adverse effects , Biomechanical Phenomena , Equipment Failure Analysis , Humans , Minnesota , Oxidation-Reduction , Polyethylenes/adverse effects , Polyethylenes/chemistry , Product Packaging , Prosthesis Design , Reoperation , Spectroscopy, Fourier Transform Infrared , Stress, Mechanical , Tensile Strength , Time FactorsABSTRACT
Submicron sized particles are frequently observed in retrieved total hip and knee periprosthetic tissues and appear to be critical in the activation of the phagocytic inflammatory response. In this paper the concentration, size and shape of ultra-high molecular weight polyethylene (UHMWPE) wear particles between 0.05 and 2.00µm were determined after isolation from periprosthetic tissues from retrieved lumbar SB Charité III total disc replacements (TDR) using scanning electron microscopy (SEM). For comparison, UHMWPE wear particles were isolated from γ-radiation-air sterilized total hip arthroplasty (THA) revision tissues. The mean concentration of UHMWPE particles in TDR tissues was 1.6×10(9)g(-1)tissue (range 1.3-2.0), which was significantly lower than the concentration of 2.3×10(9)g(-1) THA revision tissue (range 1.8-3.2) (P=0.03). The mean particle size (equivalent circular diameter: TDR, 0.46µm; THA 0.53µm, P=0.60) and mean shape were comparable between TDR and THA (aspect ratio: TDR, 1.89; THA, 1.99, P=0.35; roundness: TDR, 0.58; THA, 0.56, P=0.35). However, the TDR particles tended to be smaller and more round. Although no correlations were found between visible damage to the UHMWPE core and the concentration or shape of the UHMWPE particles, a positive correlation was found between increasing particle size and increasing rim penetration of the TDR core (P=0.04). The presence of UHMWPE particles of similar size and shape in TDR tissue, albeit lower in concentration, might explain why, unlike THA, pain rather than osteolysis is the major reason for revision surgery.
Subject(s)
Arthroplasty, Replacement, Hip , Hip Prosthesis , Polyethylenes/chemistry , Total Disc Replacement , Humans , Microscopy, Electron, Scanning , Particle Size , Polyethylenes/radiation effects , ReoperationABSTRACT
Vitamin E (α-tocopherol) is a free-radical stabilizing antioxidant used to maintain oxidative stability in radiation cross-linked ultra-high molecular weight polyethylene (UHMWPE) used in total joint replacements. We investigated the oxidative resistance of vitamin E-stabilized UHMWPE in (i) postirradiation vitamin E-diffused UHMWPE, (ii) vitamin E blended and irradiated UHMWPE, and (iii) unstabilized, irradiated UHMWPE after accelerated aging and real-time aging in an aqueous environment at 40°C for 36 months. Unstabilized samples exhibited substantial oxidation throughout the surface and bulk with both types of aging. While vitamin E-stabilized, radiation cross-linked UHMWPEs were all superior to unstabilized samples, irradiated blends showed surface oxidation and subsurface oxidation potential beginning at ten months in real-time aging. In contrast, postirradiation vitamin E-diffused UHMWPEs showed no detectable oxidation and no increase in oxidation potential despite elution of some vitamin E. We also showed that current thermal accelerated aging methods were unable to differentiate among the oxidative stability of vitamin E-stabilized, radiation cross-linked UHMWPEs prepared by different processes.