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Controlled release of EGF and bFGF from dextran hydrogels in vitro and in vivo
Dogan, A. K., M. Gumusderelioglu, et al. (2005), J Biomed Mater Res B Appl Biomater 74(1): 504-10.
Abstract: In the present study, dextran-epichlorohydrin hydrogels were employed as carriers for the controlled release of epidermal growth factor (EGF) and basic fibroblast growth factor (bFGF). The hydrogels were synthesized from 50% (by weight) monomeric cross-linker, epichlorohydrin, containing dextran mixtures by intermolecular side-chain reaction of dextran-hydroxyl groups with epichlorohydrin-epoxy groups. The hydrogel disks of 3-mm diameter and 1.5-mm thickness have a high swelling capacity (EWC = 650%) and enough mechanical stability for the studies in vivo. Impregnation of EGF and bFGF into the dried hydrogels was carried out by use of phosphate buffered saline solution (PBS, pH = 7.4) containing 0.5 microg mL(-1) EGF and 0.1 microg mL(-1) bFGF, respectively. The in vitro release of growth factors was detected by fluorescence spectroscopy. The prolonged release of EGF is continued up to the 14th day, in comparison with a 26-day release of bFGF. The in vivo studies were realized with subcutaneously implanted hydrogels in Wistar albino rats. The rate of neovascularization was analyzed statistically using one-way analysis of significance with EGF and bFGF incorporated hydrogels. In conclusion, dextran-epichlorohydrin hydrogels were shown to be an alternative delivery system for the release of growth factors.

Controlled release of heparin from polypyrrole-poly(vinyl alcohol) assembly by electrical stimulation
Li, Y., K. G. Neoh, et al. (2005), J Biomed Mater Res A 73(2): 171-81.
Abstract: A surface modification technique was developed for the covalent immobilization of poly(vinyl alcohol) (PVA)-heparin hydrogel onto electrically conductive polypyrrole (PPY) film with the objective of achieving controlled release of heparin. First, aldehyde groups were introduced onto PPY film through poly(ethylene glycol) monomethacrylate graft copolymerization and subsequent oxidation in acetic anhydride and dimethyl sulfoxide mixture. Then, the prepared PVA-heparin hydrogel was cast onto the PPY film and covalently immobilized to the film through the reaction between the aldehyde groups on the PPY film and the hydroxyl groups of PVA. X-ray photoelectron spectroscopy was used to characterize the surface-modified film after each stage. The strong attachment of the PVA-heparin layer on the PPY film was confirmed by peel test and scanning electron microscopy. The release behavior of heparin from the substrate with and without electrical stimulation was studied and the experimental results showed that the heparin release rate from the prepared substrate using an electric current of 3.5 mA is twofold higher than that without current.

Controlling algal growth in photo-dependent decolorant sludge by photocatalysis
Hong, J., H. Ma, et al. (2005), J Biosci Bioeng 99(6): 592-7.
Abstract: In the treatment of synthetic dye wastewater by photosynthetic bacteria under optical irradiation, excessive algal growth and adhesion on the walls of the reactor are serious problems. The adverse effects of excessive algal growth on photosynthetic bacterial activity are significantly greater than those of the decreased optical irradiation of the solution. In this report, we investigated the effects of photocatalysis on the growth of algae (Chroococcus sp.) and photosynthetic bacteria. The different sensitivities of Chroococcus sp. and photosynthetic bacteria to photocatalysis were observed by an ATP assay. Moreover, from microscopy findings, some algae were damaged by TiO2 with UV. We suggested that some algae suffered from membrane damage and consequently cell substances were released, resulting in the increase of dissolved material following treatment using TiO2 with UV.

Controlling cell adhesion and degradation of chitosan films by N-acetylation
Freier, T., H. S. Koh, et al. (2005), Biomaterials 26(29): 5872-8.
Abstract: As part of our ongoing effort to develop a biodegradable nerve guidance channel based on chitin/chitosan, we conducted a systematic in vitro study on the biodegradation and neural cell compatibility of chitosan and N-acetylated chitosan. The in vitro degradation (pH 7.4, 37 degrees C) in the presence of 1.5 microg/ml lysozyme showed a progressive mass loss to greater than 50% within 4 weeks for films with 30-70% acetylation. In contrast, the degradation of samples with very low or high acetylation was minimal over the 4-week period. Neural cell compatibility of chitosan and N-acetylated chitosan was tested using primary chick dorsal root ganglion (DRG) neurons. All chitosan-based films showed DRG cell adhesion after 2 days of culture. However, cell viability decreased with increasing acetylation. Chitosan that was 0.5% acetylated had the greatest cell viability, which was approximately 8 times higher than that of chitosan that was 11% acetylated. Chitosan with 0.5% and 11% acetylation showed more and longer neurites than the other samples studied. Thus chitosan amine content can be tuned for optimal biodegradation and cell compatibility, which are important for tissue engineering in the nervous system.

Controlling drug release from imprinted hydrogels by modifying the characteristics of the imprinted cavities
Hiratani, H., Y. Mizutani, et al. (2005), Macromol Biosci 5(8): 728-33.
Abstract: The aim of this study was to analyse the influence of the template/functional monomer proportion on the achievement of molecularly imprinted hydrogels with cavities with a high enough affinity for the drug to sustain drug release. Imprinted hydrogels were prepared from N,N-dimethylacrylamide and tris(trimethylsiloxy)sililpropyl methacrylate (DMAA and TRIS; main components), methacrylic acid (MAA; functional monomer), ethylene glycol dimethacrylate (EGDMA; cross-linker), and timolol (template drug). Photo-polymerization of the monomer solutions was carried out in poly(propylene) molds (0.3 mm thickness) to obtain contact lens-like devices. Non-imprinted control hydrogels were also prepared in the same way but without the addition of timolol. The imprinted hydrogels showed a higher affinity for timolol and a slower release rate than the non-imprinted hydrogels. The release rate decreased by increasing the MAA/timolol ratio in the gel recipe. Hydrogels prepared with 400 x 10(-3) M MAA, 600 x 10(-3) M EGDMA, and a timolol/MAA mole ratio of 1:16-1:32 had drug diffusion coefficients two orders of magnitude below those of non-imprinted hydrogels. The results obtained clearly indicate that the timolol release rate is critically affected by the conditions under which the hydrogels were synthesized. These effects are discussed on the basis of the influence of drug proportion on the conformation of the imprinted cavities.

Controlling osteopontin orientation on surfaces to modulate endothelial cell adhesion
Liu, L., S. Chen, et al. (2005), J Biomed Mater Res A 74(1): 23-31.
Abstract: Osteopontin (OPN) is an important extracellular matrix protein that has been shown to impact wound healing, inflammation, and the foreign body reaction, and has been identified as a potential surface component for engineered biomaterials. OPN contains the arginine-glycine-aspartic acid (RGD) moiety that has been shown to mediate cell adhesion through interactions with integrins. In its preferred orientation and conformation on a surface, the functional domains of OPN will be presented to cells to the greatest extent. However, control of protein orientation and conformation is still challenging. In this work, we investigated OPN adsorption and cell adhesion to the OPN layer on self-assembled monolayers (SAMs) of alkanethiols terminated with various functional groups and on a gold surface. The four SAM terminal groups studied were --CH3, --OH, --NH2, and --COOH, representing hydrophobic, hydrophilic but neutral, positively charged, and negatively charged surfaces, respectively. Surface plasmon resonance biosensor and atomic force microscopy were used to characterize the adsorption of OPN on these surfaces. An in vitro cell adhesion assay of bovine aortic endothelial cells was performed to test the functionality of OPN on various SAMs. Surface plasmon resonance results showed that the amount of protein adsorbed on the --NH2 surface is close to a monolayer and similar to that on the --COOH surface, consistent with the atomic force microscopy results. However, based on cell adhesion experiments, both cell count and average cell spreading area on the --NH2 surface are much higher than those on the --COOH surface. From these results, it is suggested that the orientation and conformation of OPN on a positively charged --NH2 surface is more favorable for cell adhesion and spreading than on a negatively charged --COOH surface. The surface coverage of bovine aortic endothelial cells on the surfaces studied decreased in the following order: --NH2 > Au > --CH3 > --COOH > --OH whereas the mean cell spreading area decreased in the following order: --NH2 > Au > --CH3 > --COOH. Our studies show that surface properties will alter OPN behavior on surfaces, thus influencing cell interactions.

Controlling the phenotype and function of mesenchymal stem cells in vitro by adhesion to silane-modified clean glass surfaces
Curran, J. M., R. Chen, et al. (2005), Biomaterials 26(34): 7057-67.
Abstract: The behaviour of human mesenchymal stem cells (hMSC) when cultured in contact with a range of silane-modified surfaces was examined to determine if changing the surface chemistry affected the early differentiation potential of mesenchymal stem cells in vitro over a 7-day period. Cells were cultured for 1 and 7 days in direct contact with glass which had been functionalized by surface treatment to provide a range of different surfaces: -CH(3), -NH(2), -SH, -OH, and -COOH modified surfaces and a clean glass reference (TAAB). Viable cell adhesion was quantified by Lactate Dehydrogenase assay, and morphology and viability was qualitatively evaluated using calcein AM, ethidium homodimer, cytoskeletal (F Actin), extra-cellular matrix (fibronectin and vitronectin) and Hoechst staining (nucleus). The expression of selected differentiation markers, Collagen II (chondrocytes), CBFA1 (bone transcription factor), Collagen I (MSC marker) and TGF-beta3 (extra-cellular matrix production) was determined using real time polymerase chain reaction. The expression of ornithine decarboxylase was evaluated as a marker of proliferation. Surfaces of the -NH(2) group demonstrated the greatest level of cell adhesion by the 7-day period, and mRNA expression profiles indicated osteogenic differentiation, increased CBFA1 and decreased Collagen II expression. Cells cultured in contact with the -COOH surfaces displayed different cell morphologies, fibronectin and vitronectin spatial distributions compared with the cells in contact with the -NH(2) surfaces, in addition to an increase in Collagen II expression, indicative of chondrogenic differentiation. The modifications to the surface chemistry of glass did affect cell behaviour, both in terms of viable cell adhesion, morphology and profiles of mRNA expression, providing the means to alter the differentiation potential of the MSCs.

Conversion and temperature profiles during the photoinitiated polymerization of thick orthopaedic biomaterials
Burdick, J. A., A. J. Peterson, et al. (2001), Biomaterials 22(13): 1779-86.
Abstract: Polymerization of a tetrafunctional monomer was investigated under a variety of photoinitiation conditions to assess the ability to form thick materials in situ for orthopaedic applications. The major biological concerns include local cell and tissue necrosis due to the polymerization exotherm and low conversions at greater depths due to light attenuation through thick samples. Experimental results indicate that depth of cure and temperature rises are controllable by altering the photoinitiator concentration, initiating light intensity, and type of photoinitiator. For example, no measurable conversion was detected at a 1.0 cm depth when polymerization was initiated with 1.0 wt% DMPA and 100 mW/cm2 ultraviolet light, whereas approximately 40% conversion was obtained when the initiator concentration was lowered to 0.1 wt%. This conversion was further increased to approximately 55% when a photobleaching initiator system was employed. At the highest rate of initiation studied (i.e., 1.0 wt% DMPA irradiated with 100 mW/cm2 ultraviolet light), a maximum temperature of approximately 49 degrees C was reached at the sample surface; however, this temperature dramatically decreased to approximately 33 degrees C when the light intensity was decreased to 25 mW/cm2. Finally, dual initiating systems that synergistically combine the advantages of photoinitiation and thermal initiation were investigated.

Coordinated design of cofactor and active site structures in development of new protein catalysts
Ueno, T., T. Koshiyama, et al. (2005), J Am Chem Soc 127(18): 6556-62.
Abstract: New methods for the synthesis of artificial metalloenzymes are important for the construction of novel biocatalysts and biomaterials. Recently, we reported new methodology for the synthesis of artificial metalloenzymes by reconstituting apo-myoglobin with metal complexes (Ohashi, M. et al., Angew Chem., Int. Ed. 2003, 42, 1005-1008). However, it has been difficult to improve their reactivity, since their crystal structures were not available. In this article, we report the crystal structures of M(III)(Schiff base).apo-A71GMbs (M = Cr and Mn). The structures suggest that the position of the metal complex in apo-Mb is regulated by (i) noncovalent interaction between the ligand and surrounding peptides and (ii) the ligation of the metal ion to proximal histidine (His93). In addition, it is proposed that specific interactions of Ile107 with 3- and 3'-substituent groups on the salen ligand control the location of the Schiff base ligand in the active site. On the basis of these results, we have successfully controlled the enantioselectivity in the sulfoxidation of thioanisole by changing the size of substituents at the 3 and 3' positions. This is the first example of an enantioselective enzymatic reaction regulated by the design of metal complex in the protein active site.

Copolymers of 2-methacryloyloxyethyl phosphorylcholine (MPC) as biomaterials
Nakabayashi, N. and Y. Iwasaki (2004), Biomed Mater Eng 14(4): 345-54.
Abstract: Copolymers of 2-methacryloyloxyethyl phosphorylcholine (MPC) showed good hemocompatibility as hypothesized. The hypothesis was surfaces having phosphorylcholine groups by polymerization of MPC could accumulate phospholipids from blood stream and show good blood compatibility. We designed and prepared a methacylate having a phosphorylcholine group. While it was possible to introduce them by polymer reactions, polymer reaction is not always good method to prepare the desired pure surface. This must be very important point to consider biomaterials, as we have to apply them in our body without any adverse effects.The hypothesis was confirmed by changing copolymer composition. The adsorption amount of phospholipids on the surfaces increased with increasing the MPC units in the copolymers. On the other hand, increasing MPC units in MPC copolymers decreased adsorption amount of peptides. There is limitation in blood compatibility tests in vitro due to unstable characteristics of blood itself. We evaluated them with series of blood compatibility tests, in vitro, ex vivo and in vivo, on coated PMMA beads, modified hollow fibers for hemodialysis and 2 mm small diameter blood vessels, respectively. These data suggested MPC is a promising methacrylate to develop good blood contacting devises, which may not require systemic anticoagulation. Conventional blood compatible biomaterials were not suitable to make permeable membranes. But MPC is soluble in water and we could prepare permeable membranes to various solutes by the copolymerization. Introduction of MPC copolymers on cellulose and polysulfone hollow fiber membranes gave them nonthrombogenicity but it did not give adverse effect on their permeability. These data suggested that it is possible to apply them to hemodialyzers, oxygenators and percutaneous glucose sensors to keep diabetic patients easier. MPC surfaces are good hydrogel to minimize damage on tissues by lubricating between organs and the coated devices. They do not induce denaturation of peptides, which is beneficial to keep activities of enzymes longer. And poly-MPC dissolved is applicable to stabilize several bioactive peptides in aqueous phase. So MPC polymers are useful to minimize fouling by inhibiting the adsorption of bioactive proteins. MPC has high potential to develop many varieties of new biomaterials useful in so-called biotechnology. MPC and their copolymers are commercially available from NOF (Tokyo, Japan) and Biocompatibles (UK, as PC technology).

Copper-binding efficacy of water-soluble chitosans: characterization by aqueous binding isotherms
Ben-Shalom, N., N. Kudabaeva, et al. (2005), Chemosphere 59(9): 1309-15.
Abstract: The major objective of the study is to measure directly the isotherms of copper binding onto soluble chitosan preparations, using ion-selective electrode technique. Copper uptake is found to decrease strongly when chitosan acetylation degree or chitosan concentration increased. When relating the bound copper concentrations to content of non-acetylated amine groups in a chitosan, differences between copper uptake on different chitosan preparations become reduced but not disappear. Other effects, in addition to the contents of non-acetylated amine groups, can involve differences in the copper binding by different chitosans. Due to isotherm non-linearity, the distribution coefficient K(d) of copper between a water-soluble chitosan and an aqueous solution may vary by two orders of magnitude as the free copper concentration C(free) varied. Linear relation between logK(d) normalized by free amine group content of chitosans and logC(free) may help in preliminary estimating of the copper binding by water-soluble chitosans at a certain pH.

Cora rotary pump for implantable left ventricular assist device: biomaterial aspects
Monties, J. R., I. Dion, et al. (1997), Artif Organs 21(7): 730-4.
Abstract: Our group is developing a left ventricular assist device based on the principle of the Maillard-Wankel rotative compressor: it is a rotary, not centrifugal, pump that produces a pulsatile flow. Stringent requirements have been defined for construction materials. They must be light, yet sufficiently hard and rigid, and able to be machined with high precision. The friction coefficient must be low and the wear resistance high. The materials must be chemically inert and not deformable. Also, the materials must be biocompatible, and the blood contacting surface must be hemocompatible. We assessed the materials in terms of physiochemistry, mechanics, and tribology to select the best for hemocompatibility (determined by studies of protein adsorption; platelet, leukocyte, and red cell retention; and hemolysis, among other measurements) and biocompatibility (determined by measurement of complement activation and toxicity, among other criteria). Of the materials tested, for short- and middle-term assistance, we chose titanium alloy (Ti6Al4V) and alumina ceramic (Al2O3) and for long-term and permanent use, composite materials (TiN coating on graphite). We saw that the polishing process of the substrate must be improved. For the future, the best coating material would be diamond-like carbon (DLC) or crystalline diamond coating.

Coralline hydroxyapatite and laminectomy-derived bone as adjuvant graft material for lumbar posterolateral fusion
Hsu, C. J., W. Y. Chou, et al. (2005), J Neurosurg Spine 3(4): 271-5.
Abstract: OBJECT: The purpose of this study was to evaluate the effectiveness of coralline hydroxyapatite (CHA) and laminectomy-derived bone as an adjuvant graft material when combined with autogenous iliac bone graft (AIBG) in posterolateral fusion (PLF). METHODS: This prospective, case-control study involved 58 patients who underwent lumbar instrumentation-augmented PLF for degenerative spinal stenosis-induced segmental instability between July 2000 and June 2001. The patients were divided into three groups. Laminectomy bone and AIBG were placed in the right intertransverse process space in Group 1 (20 patients), CHA and AIBG were placed in Group 2 (19 patients), and laminectomy bone and CHA were placed in Group 3 (19 patients). Pure autogenous iliac cancellous bone graft was placed in the left intertransverse process space in all three groups of patients. Successful fusion was determined by two spine surgeons after examining the plain, anteroposterior, bilateral oblique, and lateral flexion-extension radiographs. If the examiners did not agree on fusion status, fine-cut computerized tomography scans of the fusion mass were used to make the final decision. The chi-square test was used to compare the fusion rate at different time intervals among the three groups. CONCLUSIONS: Pure AIBG placed in left intertransverse process space was associated with the best fusion rate. After 6 months, CHA produced a comparable result to laminectomy-derived bone when combined with AIBG. When laminectomy bone was mixed with CHA, the combination failed to yield a satisfactory fusion rate (57.9%) even 1 year after surgery if no AIBG was added.

Coronally positioned flap procedures with or without a biodegradable membrane in the treatment of human gingival recession. A 6-year follow-up study
Leknes, K. N., E. S. Amarante, et al. (2005), J Clin Periodontol 32(5): 518-29.
Abstract: BACKGROUND: Short-term data have indicated that treatment of gingival recession type defects by coronally positioned flap procedures with or without biodegradable membranes may result in similar treatment outcome. The aim of this study was to compare 12-month and 6-year follow-up results for these two treatment approaches. METHODS: Twenty patients with buccal bilateral Miller Class I or Class II gingival recession defects in cuspids or bicuspids were treated randomly by coronally positioned flap alone (20 sites) or in combination with a biodegradable membrane (20 sites). Clinical measurements at baseline, 6, 12 months and 6 years included apical extent of gingival recession, width of the defect at the cemento-enamel junction (CEJ), width of keratinized tissue, as well as attachment level and probing depth. Eleven patients were available for the 6-year evaluation. RESULTS: At 12 months (20 sites), both treatments resulted in significant gain of root coverage (p<0.001), stable probing depth, and increased attachment level (p<0.001). The 6-year evaluation (11 sites) showed a significant gain of root coverage for the non-membrane group only (p<0.05). No significant between-group differences were detected for any other treatment variable regardless of smoking status (p>0.05). Compared with baseline, the 6-year results showed that seven membrane sites gained root coverage, three were unchanged and one lost root coverage. For the 11 non-membrane sites, eight gained root coverage, and three were unchanged. The five membrane and the 10 non-membrane sites exhibiting complete root coverage at 6 months were reduced to two and one, respectively, at the 6-year evaluation. CONCLUSIONS: The coronally positioned flap procedure offers a simple and reliable treatment alternative as a root coverage procedure in Class I and Class II recession type defects. Placement of a biodegradable membrane underneath the flap does not seem to improve neither the short- nor the long-term results. Long-term outcome stability seems to be critically dependent on a continuous follow-up program with re-instruction in non-traumatic brushing habits.

Coronary stents: in these days of climate change should all stents wear coats?
Lowe, R., I. B. Menown, et al. (2005), Heart 91 Suppl 3: iii20-3.

Correlative radiological, self-assessment and clinical analysis of evolution in instrumented dorsal and lateral fusion for degenerative lumbar spine disease. Autograft versus coralline hydroxyapatite
Korovessis, P., G. Koureas, et al. (2005), Eur Spine J 14(7): 630-8.
Abstract: This prospective longitudinal randomized clinical and radiological study compared the evolution of instrumented posterolateral lumbar and lumbosacral fusion using either coralline hydroxyapatite (CH), or iliac bone graft (IBG) or both in three comparable groups, A, B and C, which included 19, 18 and 20 patients, respectively, who suffered from symptomatic degenerative lumbar spinal stenosis and underwent decompression and fusion. The patients were divided randomly according to the graft used and the side that it was applied. The spines of group A received autologous IBG bilaterally; group B, IBG on the left side and hydroxyapatite mixed with local bone and bone marrow on the right side; group C, hydroxyapatite mixed with local bone and bone marrow bilaterally. The age of the patients in the groups A, B and C was 61+/-11 years, 64+/-8 years and 58+/-8 years, respectively. The SF-36, Oswestry Disability Index (ODI), and Roland-Morris (R-M) surveys were used for subjective evaluation of the result of the surgery and the Visual Analogue Scale (VAS) for pain severity. Plain roentgenograms including anteroposterior, lateral and oblique views, and lateral plus frontal bending views of the instrumented spine and CT scan were used to evaluate the evolution of the posterolateral fusion in all groups and sides. Two independent senior orthopaedic radiologists were asked to evaluate first the evolution of the dorsolateral bony fusion 3-48 months postoperatively with the Christiansen's radiologic method, and secondly the hydroxyapatite resorption course in the spines of groups B and C. The diagnosis of solid spinal fusion was definitively confirmed with the addition of the bending views, CT scans and self-assessment scores. The intraobserver and interobserver agreement (r) for radiological fusion was 0.71 and 0.69, respectively, and 0.83 and 0.76 for evaluation of CH resorption. T(12)-S(1) lordosis and segmental angulation did not change postoperatively. There was no radiological evidence for non-union on the plain roentgenograms and CT scans. Radiological fusion was achieved 1 year postoperatively and was observed in all groups and vertebral segments. Six months postoperatively there was an obvious resorption of hydroxyapatite granules at the intertransverse intersegmental spaces in the right side of the spines of group B and both sides of group C. The resorption of hydroxyapatite was completed 1 year postoperatively. Bone bridging started in the third month postoperatively in all instrumented spines and all levels posteriorly as well as between the transverse processes in the spines of the group A and on the left side of the spines of group B where IBG was applied. SF-36, ODI, and R-M score improved postoperatively in a similar way in all groups. There was one pedicle screw breakage at the lowermost instrumented level in group A and two in group C without radiologically visible pseudarthrosis, which were considered as having non-union. Operative time and blood loss were less in the patients of group C, while donor site complaints were observed in the patients of the groups A and B only. This study showed that autologous IBG remains the "gold standard" for achieving solid posterior instrumented lumbar fusion, to which each new graft should be compared. The incorporation of coralline hydroxyapatite mixed with local bone and bone marrow needs adequate bleeding bone surface. Subsequently, hydroxyapatite was proven in this series to not be appropriate for intertransverse posterolateral fusion, because the host bone in this area is little. However, the use of hydroxyapatite over the decorticated laminae that represents a wide host area was followed by solid dorsal fusion within the expected time.

Corrosion and other electrochemical aspects of biomaterials
Bundy, K. J. (1994), Crit Rev Biomed Eng 22(3-4): 139-251.
Abstract: Metallic materials are used extensively as orthopedic implants, dental materials, sensing elements of bioelectrodes, and other applications. The electrochemical behavior of these biomaterials is of interest for a variety of reasons. The corrosion resistance of an implant material influences its functional performance and durability and is a primary factor governing biocompatibility. Among the aspects affecting biocompatibility are the amounts and forms of released corrosion products and their disposition in the body after release. Electrochemical principles are very useful for understanding the factors affecting corrosion resistance and also form the foundation for many biosensors that measure the concentration of various chemical entities (including released corrosion products and naturally occurring substances). Many electrochemical measurement techniques have been used to study biomaterials for years (e.g., polarization curve measurement), while others (such as polarography and AC impedance methods) have been applied more recently. This work focuses on four main topics. The first is the nature of the body's environment as it affects in vivo electrochemical phenomena, that is, the chemical, mechanical, biological, and bioelectrical phenomena that affect the behavior and performance of biomaterials. The second deals with methodology--the techniques used for corrosion measurement and concentration determination, the appropriate environment (laboratory, cell culture, in vivo, etc.), and experimental problems encountered. The third topic treated is the knowledge accumulated regarding the performance of implant alloys in various applications, for example, the forms of corrosion to which they are susceptible, etc. Finally, improvements that may come about in the future regarding both materials and testing methodology are considered.

Corrosion behavior of titanium in the presence of calcium phosphate and serum proteins
Cheng, X. and S. G. Roscoe (2005), Biomaterials 26(35): 7350-6.
Abstract: The effect of calcium phosphate surface deposit and the surface adsorption of the serum proteins, bovine serum albumin (BSA) and fibrinogen, on the corrosion resistance and electrochemical behavior of (cp)titanium in phosphate buffer saline solution (pH 7.4) was investigated at physiological temperature, 37 degrees C, using electrochemical impedance spectroscopy and dc electrochemical polarization techniques. The formation of calcium phosphate deposit on the Ti surface decreased both the corrosion rate at the open circuit potential (OCP) and the anodic reaction current in the high anodic potential range (>2.6 V). Addition of BSA significantly moved the OCP towards a more negative (cathodic) potential and inhibited the cathodic corrosion reaction, but did not significantly change the corrosion resistance at the OCP. Addition of fibrinogen showed a similar, but less pronounced effect than BSA. The possible mechanisms leading to these observed effects are discussed.

Corrosion resistance for biomaterial applications of TiO2 films deposited on titanium and stainless steel by ion-beam-assisted sputtering
Pan, J., C. Leygraf, et al. (1997), J Biomed Mater Res 35(3): 309-18.
Abstract: The high corrosion resistance and good biocompatibility of titanium and its alloys are due to a thin passive film that consists essentially of titanium dioxide. There is increasing evidence, however, that under certain conditions extensive titanium release may occur in vivo. An ion-beam-assisted sputtering deposition technique has been used to deposit thick and dense TiO2 films on titanium and stainless steel surfaces. In this study, using the following measurements these TiO2 films have been investigated in a phosphate-buffered saline solution: (1) open-circuit potential versus time of exposure, (2) electrochemical impedance spectroscopy, (3) potentiodynamic polarization, and (4) Mott-Schottky plot. A higher electrical film resistance, lower passive current density, and lower donor density (in the order of 10(15) cm-3) have been measured for the sputter-deposited oxide film on titanium in contrast to the naturally formed passive oxide film on titanium (donor density in the order of 10(20) cm-3). The improved corrosion protection of the sputter-deposited oxide film can be explained by a low defect concentration and, consequently, by a slow mass transport process across the film. As opposed to TiO2 on titanium, a deviation from normal n-type semiconducting Mott-Schottky behavior was observed for TiO2 on stainless steel.

Corrosion resistance, surface mechanical properties, and cytocompatibility of plasma immersion ion implantation-treated nickel-titanium shape memory alloys
Yeung, K. W., R. W. Poon, et al. (2005), J Biomed Mater Res A 75(2): 256-67.
Abstract: Nickel-titanium shape memory alloys are promising materials in orthopedic applications because of their unique properties. However, for prolonged use in a human body, deterioration of the corrosion resistance of the materials becomes a critical issue because of the increasing possibility of deleterious ions released from the substrate to living tissues. We have investigated the use of nitrogen, acetylene, and oxygen plasma immersion ion implantation (PIII) to improve the corrosion resistance and mechanical properties of the materials. Our results reveal that the corrosion resistance and mechanical properties such as hardness and elastic modulus are significantly enhanced after surface treatment. The release of nickel is drastically reduced as compared with the untreated control. In addition, our in vitro tests show that the plasma-treated surfaces are well tolerated by osteoblasts. Among the three types of samples, the best biological effects are observed on the nitrogen PIII samples.


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