Corrosion inhibition of powder metallurgy Mg by fluoride treatments

Pure Mg has been proposed as a potential degradable biomaterial to avoid both the disadvantages of non-degradable internal fixation implants and the use of alloying elements that may be toxic. However, it shows excessively high corrosion rate and insufficient yield strength. The effects of reinforcing Mg by a powder metallurgy (PM) route and the application of biocompatible corrosion inhibitors (immersion in 0.1 and 1 M KF solution treatments, 0.1 M FST and 1 M FST, respectively) were analyzed in order to improve Mg mechanical and corrosion resistance, respectively. Open circuit potential measurements, polarization techniques (PT), scanning electrochemical microscopy (SECM) and electrochemical impedance spectroscopy (EIS) were performed to evaluate its corrosion behavior. SECM showed that the local current of attacked areas decreased during the F^? treatments. The corrosion inhibitory action of 0.1 M FST and 1 M FST in phosphate buffered solution was assessed by PT and EIS. Under the experimental conditions assayed, 0.1 M FST revealed better performance. X-ray photoelectron spectroscopy, energy dispersive X-ray and X-ray diffraction analyses of Mg(PM) with 0.1 M FST showed the presence of KMgF₃ crystals on the surface while a MgF₂ film was detected for 1 M FST. After fluoride inhibition treatments, promising results were observed for Mg(PM) as degradable metallic biomaterial due to its higher yield strength and lower initial corrosion rate than untreated Mg, as well as a progressive loss of the protective characteristics of the F^?-containing film which ensures the gradual degradation process.     

Correlations between the in vitro and in vivo bioactivity of the Ti/HA composites fabricated by a powder metallurgy method

Ti/HA composites were successfully prepared by a powder metallurgy method and the effect of phase composition on the in vitro and in vivo bioactivity of the Ti/HA composites was investigated in the present study. The correlations between the in vitro and in vivo biological behaviors were highlighted. The results showed that the in vitro and in vivo bioactivity of the Ti/HA composites was dependent on their phase composition. The in vitro bioactivity of the Ti/HA composites was evaluated in simulated body fluid with ion concentrations similar to those of human plasma. After immersion in the simulated body fluid for a certain time, apatite precipitations formed on the surface of the composites with an initial titanium content of 50 and 70 wt.%, and no apatite was found on the surface of the composite with 30% titanium. Ti(2)O was responsible for the apatite formation on the surfaces of the composites. For in vivo analysis, Ti/HA cylinders were implanted in the metaphases of the rabbit femur. At the early stage of implantation, the new bone formed on the surface of the composite with 30% titanium was much less than that on the surfaces of the composites with 50% and 70% titanium. All the Ti/HA composites formed a chemical bone-bonding interface with the host bone by 6 months after implantation. The Ti/HA composites formed the bone-bonding interface with the surrounding bone through an apatite layer. The results in the present study suggested that the in vivo results agreed well with the in vitro results.     

In vitro bioactivity of a biocomposite fabricated from HA and Ti powders by powder metallurgy method

Traditionally, hydroxyapatite was used as a coating material on titanium substrate by various techniques. In the present work, a biocomposite was successfully fabricated from hydroxyapatite and titanium powders by powder metallurgy method. Bioactivity of the composite in a simulated body fluid (SBF) was investigated. Main crystal phases of the as-fabricated composite are found to be Ti2O, CaTiO3, CaO, alpha-Ti and a TiP-like phase. When the composite is immersed in the simulated body fluid for a certain time, a poor-crystallized, calcium-deficient, carbonate-containing apatite film will form on the surface of the composite. The time required to induce apatite nucleation is within 2 h. In addition, the apatite is also incorporated with a little magnesium and chlorine element. It is found that Ti2O has the ability to induce the formation of bone-like apatite in the SBF. And a dissolve of the CaO phase could also provide favorable conditions for the apatite formation, by forming open pores on the surface of the composite and increasing the degree of supersaturation of the SBF with respect to the apatite.     

In vitro bioactivity and degradation of polycaprolactone composites containing silicate fillers

In spite of numerous publications on the potential use of combinations of polycaprolactone (PCL)/bioactive fillers for bone regeneration, little information exists on the assessment of solid, nonporous composites prepared via solventless routes and consisting of unmodified, slowly degrading homopolymer with relatively low amounts of reactive fillers such as bioglass or calcium silicate (CS). Thus, composites of PCL with commercial CS and a bioactive glass (BG45S5) at 30wt.% were produced by melt mixing in a twin screw extruder. Neat fillers, PCL and their composites were immersed in simulated body fluid (SBF) and phosphate buffer saline and tested for in vitro bioactivity and degradation, respectively, over a 4 month period. Testing methods included scanning electron microscopy with energy dispersive X-ray analysis, X-ray diffraction (XRD), elemental analysis and weight and pH changes before and after immersion. Experiments with neat fillers indicated fast growth of calcium phosphate minerals having different textures; they included clusters and globules of mineral precipitates as well as needle-shaped nanosized crystallites and possibly other calcium phosphate structures with varying Ca/P ratio. The bioactive glass composite initially showed fast growth of the precipitated minerals and partial surface coverage after 1 week, whereas in the CS composite, growth and surface coverage increased as a function of immersion time (over a period of 4 weeks) in the SBF solution. XRD results showed early appearance (1 week) of hydroxyapatite for both types of composites with differences attributed to different dissolution rates and different surface reactions of the fillers. Both fillers appeared to enhance the hydrolytic degradation of the matrix. Overall, the limited observed bioactivity of both composites within the test period may be related to the hydrophobicity of the matrix, insufficient ionic activity since SBF was not replenished and the relatively low content of the low surface areas fillers. Optimization of filler properties, such as surface/volume ratio, surface chemistry and size range, appears as a most important factor that would provide, at the required high filler volume fractions, a balance of melt processability and bioactivity.     

In vitro cytotoxicity of dental composites based on new and traditional polymerization chemistries

The biological response to dental restorative polymer composites is mediated by the release of unpolymerized residual monomers. Several new composite formulations claim to reduce unpolymerized residual mass. The current study assessed the cytotoxic responses to several of these new formations and compared them with more traditional formulations. Our hypothesis predicted that if these new polymerization chemistries reduce unpolymerized residual mass, the cytotoxicity of these materials also should be reduced relative to traditional formulations. METHODS: Materials (HerculiteXRV, Premise, Filtek Supreme, CeramxDuo, Hermes, and Quixfil) were tested in vitro in direct contact with Balb mouse fibroblasts, initially, then after aging in artificial saliva for 0, 1, 3, 5, or 8 weeks. The toxicity was determined by using the MTT assay to the estimate SDH activity. Knoop hardness of the materials also was measured at 0 and 8 weeks to determine whether surface breakdown of the materials in artificial saliva contributed to cytotoxic responses. RESULTS: Materials with traditional methacrylate chemistries (Herculite, Premise, Filtek Supreme) were severely (>50%) cytotoxic throughout the 8-week interval, but materials with newer chemistries or filling strategies (Hermes, CeramXDuo, and Quixfil) improved over time of aging in artificial saliva. Hermes showed the least cytotoxicity at 8 weeks, and was statistically equivalent to Teflon negative controls. Hardness of the materials was unaffected by exposure to artificial saliva. CONCLUSIONS: Newer polymerization and filling strategies for dental composites show promise for reducing the release of unpolymerized components and cytotoxicity.     

Resorbable composites with bioresorbable glass fibers for load-bearing applications. In vitro degradation and degradation mechanism

An in vitro degradation study of three bioresorbable glass fiber-reinforced poly(l-lactide-co-dl-lactide) (PLDLA) composites was carried out in simulated body fluid (SBF), to simulate body conditions, and deionized water, to evaluate the nature of the degradation products. The changes in mechanical and chemical properties were systematically characterized over 52 weeks dissolution time to determine the degradation mechanism and investigate strength retention by the bioresorbable glass fiber-reinforced PLDLA composite. The degradation mechanism was found to be a combination of surface and bulk erosion and does not follow the typical core-accelerated degradation mechanism of poly(α-hydroxyacids). Strength retention by bioresorbable glass fiber-reinforced PLDLA composites can be tailored by changing the oxide composition of the glass fibers, but the structure–property relationship of the glass fibers has to be understood and controlled so that the phenomenon of ion leaching can be utilized to control the degradation rate. Therefore, these high performance composites are likely to open up several new possibilities for utilizing resorbable materials in clinical applications which could not be realized in the past.     

In vitro evaluation of degradation and cytotoxicity of a novel composite as a bone substitute

The purpose of this study was to prepare and evaluate in vitro the feasibility and cytocompatibility of a novel composite (GGT) as a large defect bone substitute. The composite is tricalcium phosphate ceramic particles combined with genipin crosslinked gelatin. After soaking the GGT composites in Ringer solutions at 37 degrees C for 7, 14, 28, 42, 56, and 84 days, the in vitro biologic degradation rate and biocompatibility were determined. Substances released from soaked GGT composites were analyzed with an ultraviolet visible light spectrophotometer. In addition, the solution soaking the GGT was co-cultured with osteoblasts to determine whether or not the released substances from GGT could facilitate the growth of bone cells. After they had been cultured for 2 days, the osteoblasts were tested for differentiation and proliferation by alkaline phosphatase (ALP) activity and a MTT assay. Results indicate that the concentration of the genipin solution is a critical factor in deciding the crosslinking degree of the GGT composite. Complete crosslinking reaction in the GGT composite occurred when 0.5 wt % of genipin had been added. Cytotoxic testing revealed that 80 ppm of the genipin in the culture medium served as the level over which cytotoxicity to osteoblasts could be produced. In addition, we found that gelatin and calcium continuously were released from the GGT composite in the soaking solution, which promoted differentiation and proliferation of the osteoblasts.     

In vitro evaluation of the effectiveness and cytotoxicity of meglumine antimoniate microspheres produced by spray drying against Leishmania infantum

The aim of the present study was to evaluate the in vitro activity and cytotoxicity of meglumine antimoniate microspheres produced by spray drying on Leishmania infantum and the effect of the excipients used in them. The parasite strain shows sensitivity to the meglumine antimoniate microspheres prepared. All the antimony IC₅₀ values from encapsulated meglumine antimoniate (3.80 ± 0.34 to 9.53 ± 0.70 μg SbV/ml for promastigotes assay) are considerably lower compared to the mean value of IC₅₀ in Glucantime solution (112 ± 12.74 μg SbV/ml). Interesting IC₅₀ values for the excipient chitosan (112.64 ± 0.53 mg/ml for promastigotes and 100.81 ± 26.45 mg/ml for amastigotes) were obtained (without cytotoxic activity), whereas the rest of the excipients did not show any activity. This new delivery system could offer a new pharmacological tool for the treatment of leishmaniosis that reduces the doses required, lowering toxic side effects because of meglumine antimoniate.     

In vitro degradation of glycine/DL-lactic acid copolymers

The in vitro degradation of glycine-DL-lactic acid copolymers was studied as a function of the composition. These polydepsipeptides were prepared by ring-opening copolymerization of 6-methyl-2,5-morpholinedione and DL-lactide. The degradation of discs of the copolymers was performed in a phosphate buffer at pH 7.4 and 37 degrees C. The decrease in molecular weight and weight was determined until complete weight loss had occurred. Poly(DL-lactide) was used as a reference material. All (co)-polymers show an immediate decrease in molecular weight, whereas the weight remains almost unchanged during a longer period of time. Decrease in weight started earlier as the glycine content of the co-polymer increased. The lactic acid content of the residual material increased during the weight loss showing a higher solubility of polymer fragments with a relatively high content of glycine residues. From the hydrolysis constants it was concluded that the degradation was best described by hydrolysis of ester bonds via a bulk erosion process, autocatalyzed by the generated carboxylic acid end groups. The rate constants varied from 4-7 X 10(-2) (day-1) for all (co)polymers. All (co)polymers show an increase in the molecular weight distribution upon weight loss.     

In vitro cytotoxicity of single-walled carbon nanotube/biodegradable polymer nanocomposites

Injectable nanocomposites made of biodegradable poly(propylene fumarate) and the crosslinking agent propylene fumarate-diacrylate as well as each of three forms of single-walled carbon nanotubes (SWNTs) were evaluated for their in vitro cytotoxicity. Unreacted components, crosslinked networks, and degradation products of the nanocomposites were investigated for their effects on cell viability using a fibroblast cell line in vitro. The results did not reveal any in vitro cytotoxicity for purified SWNTs, SWNTs functionalized with 4-tert-butylphenylene, and ultra-short SWNTs at 1- 100 microg/mL concentrations. Moreover, nearly 100% cell viability was observed on all crosslinked nanocomposites and cell attachment on their surfaces was comparable with that on tissue culture polystyrene. The degradation products of the nanocomposites displayed a dose-dependent adverse effect on cells, which was partially due to increased osmolarity by the conditions of accelerated degradation and could be overcome at diluted concentrations. These results demonstrate that all three tested nanocomposites have favorable cytocompatibility for potential use as scaffolds for bone tissue engineering applications.     

In vitro cytotoxicity of five glass-ionomer cements

To evaluate the cytotoxic effects of five glass-ionomer cements (GICs) on an odontoblast cell line (MDPC-23), disks of every material were prepared and divided into Group 1: Vitrebond, Group 2: Vitremer, Group 3: Fuji II LC, Group 4: Fuji IX GP, Group 5: Ketac-Molar, Group 6: Z-100 (positive control). In Group 7, phosphate-buffered saline solution (negative control) was applied on filter paper. After placing the samples in the bottom of wells, the cells (30,000cells/cm(2)) were plated and incubated for 72h. The cell number was counted, the cell morphology was assessed by scanning electron microscopy and the cell metabolism was evaluated using methyltetrazolium assay. The statistical analysis of Kruskal-Wallis was used to determine if the scores obtained for the cell metabolism and number of cells were different at the 95% confidence level. In groups 1, 2, 3, 4, 5, and 6 the materials decreased the cell number by 74.5%, 75.5%, 45.5%, 29.5%, 32.5%, and 88.5%, respectively. In groups 1, 2, 3, 4, and 5, the experimental GICs reduced the cell metabolism by 79%, 84%, 54%, 40%, and 42.5%, respectively. Despite the fact that all experimental materials were cytotoxic to the MDPC-23 cells, the GICs were the least cytotoxic. On the other hand, the RMGICs caused the highest cytophatic effects.     

In vitro cytotoxicity of Ag-Pd-Cu-based casting alloys

The cytotoxicity and its correlation to alloy composition, structure, corrosion, as well as galvanic coupling was studied with 12 Ag-Pd-Cu-type alloys, one conventional type III gold alloy and pure Ag, Cu, and Pd. The agar overlay cell culture technique was used. Single phase binary CuPd alloys were only slightly cytotoxic below a Cu content of 30 wt%. The tested multiphase alloys were all toxic, but no correlation between toxicity and Cu content could be observed. Solid solution annealing increased the cytotoxicity of a multiphase alloy. Exposure of a single phase alloy to an artificial saliva for 1 week prior to the test decreased its cytotoxicity significantly. Galvanic coupling of the alloys through an outer copper wire decreased their cytotoxicity.     

In vitro cytotoxicity of amorphous carbon films

Amorphous carbon (a-C), carbon nitride (a-CN) and titanium films were deposited on stainless steel substrates (SS) using a dc magnetron sputtering system attached to a high vacuum chamber. Films were deposited using a base pressure of 1.3x10(-4) Pa. For the carbon films a pure graphite target was eroded in an Argon plasma. For the case of the a-CN films, the Ar flux was substituted by 100% N2 gas. Titanium films were deposited in a different chamber, using a pure Ti target and an argon plasma. In vitro studies were carried out on the coated samples using human osteoblasts cells. Cytotoxicity of carbon films was assessed by cellular adhesion and proliferation, as determined by direct cellular counting using a spectroscopic technique and a well-defined standard curve. Osteoblasts cells were also grown on uncoated steel and prepared Petri dishes for comparison. The percentage of osteoblasts adhesion measured at 24 hrs attained maximum values for the a-C films. Similarly, cellular proliferation evaluated at three, five and seven days showed an outstanding increase of osteoblasts cells for the a-C and Ti coatings in contrast to the uncoated steel. The cell functionality was evaluated by the MTT test after incubation periods of 3, 5 and 7 days. The absorbance values obtained for a-C, a-CN and Ti surfaces resulted significantly higher with respect to the positive control, indicating that the surface did not induce any toxic effect. Preliminary bio-mineralization was evaluated by measuring the elemental composition of the mineral grown on the substrates after periods up to 14 days.     

β-磷酸三钙/聚-L-乳酸复合材料的骨内降解

背景：调控聚乳酸类可吸收材料的降解速率,使材料降解与新生骨爬行替代速度更同步,加入羟基磷灰石或β-磷酸三钙等无机粒子是目前的主流选择。 目的：对比观察β-磷酸三钙/聚-L-乳酸复合材料和聚-L-乳酸在松质骨内的降解速度及诱导成骨能力。 方法：将β-磷酸三钙/聚-L-乳酸复合材料及聚-L-乳酸材料分别植入12只新西兰大白兔双侧股骨内髁及外髁后,于术后6,12,24周3个时间点取材,测定其各个时间点的生物吸收率,扫描电镜和光学显微镜观察其在松质骨内的形态学变化,周围新骨爬行替代及异物反应情况。 结果与结论：各个时间点β-磷酸三钙/聚-L-乳酸与周围骨质贴合比聚-L-乳酸材料更紧密,未见明显异物反应。6周时β-磷酸三钙/聚-L-乳酸材料生物吸收率小于聚-L-乳酸材料,12周后生物吸收率增速加快,同时材料表面出现均匀分布的微孔及裂隙;术后24周内两种材料均未见新生骨爬行替代。结果表明β-磷酸三钙/聚-L-乳酸复合材料早期降解较聚-L-乳酸材料慢,有利于移植物植入早期的坚强固定;6周后降解加快,24周内未见诱导成骨现象。     

Ca/P ratio effects on the degradation of hydroxyapatite in vitro

Phase purity is a well-recognized but not well-understood variable affecting the biological integration of hydroxyapatite (HA)-based biomaterials. Minor amounts of specific, relevant impurities--calcium oxide (CaO) and tricalcium phosphate (TCP)--may often be present either as deliberate additions or as a result of decomposition during sintering. We investigated the influence of these two impurities in terms of their effects on surface morphology, weight loss/gain, and microstructural-level degradation. Phase purity variations were deliberately introduced into an otherwise-standardized HA matrix--the parent HA grain size and bulk density were relatively constant--produced using identical fabrication conditions. Stability varied markedly during exposure to mildly acidic, neutral, and pH 7.4 phosphate-buffered saline. Equivalent molar variations in the Ca/P ratio (1.62 vs 1.72) on either side of the stoichiometric ratio produce relatively small volumetric amounts of CaO (1.6 vol%) versus TCP (27 vol%) in HA. However, the relatively small amounts of CaO render the bulk more susceptible to degradation and more likely to have negative effects on a biological milieu. Interestingly, the presence of CaO is also a potent nucleating agent for the precipitation of new surface phases and detectable weight gain. The TCP-containing ceramic, in contrast, paradoxically exhibited slightly greater resistance to degradation than HA.     

In vitro generation of osteochondral composites

Osteochondral repair involves the regeneration of articular cartilage and underlying bone, and the development of a well-defined tissue-to-tissue interface. We investigated tissue engineering of three-dimensional cartilage/bone composites based on biodegradable polymer scaffolds, chondrogenic and osteogenic cells. Cartilage constructs were created by cultivating primary bovine calf articular chondrocytes on polyglycolic acid meshes; bone-like constructs were created by cultivating expanded bovine calf periosteal cells on foams made of a blend of poly-lactic-co-glycolic acid and polyethylene glycol. Pairs of constructs were sutured together after 1 or 4 weeks of isolated culture, and the resulting composites were cultured for an additional 4 weeks. All composites were structurally stable and consisted of well-defined cartilaginous and bone-like tissues. The fraction of glycosaminoglycan in the cartilaginous regions increased with time, both in isolated and composite cultures. In contrast, the mineralization in bone-like regions increased during isolated culture, but remained approximately constant during the subsequent composite culture. The integration at the cartilage/bone interface was generally better for composites consisting of immature (1-week) than mature (4-week) constructs. This study demonstrates that osteochondral tissue composites for potential use in osteochondral repair can be engineered in vitro by culturing mammalian chondrocytes and periosteal cells on appropriate polymer scaffolds.     

In vitro and in vivo characterization of synthetic polymer/biopolymer composites

Collagen, extracted from rat tail tendons using dilute acetic acid, was fabricated into films for subsequent characterization and biocompatibility testing. The reconstituted collagen was characterized with infrared spectroscopy, solution viscosity, contact angle, and tensile testing techniques and was found to be pure with molecular and physical properties consistent with findings of previous researchers. Composites composed of collagen coated on urethane and Silastic Rubber films were fabricated to give improved tear resistance. The biocompatibility of the composites and individual polymers was evaluated by discs implanted in the paravertebral muscle of rabbits. After four weeks none of the materials induced any gross changes in the muscle. Histopathological evaluation revealed a fibrous capsule around all of the materials. Collagen and collagen composites exhibited a stronger reaction as evidenced by a larger fibroblast layer and a variety of inflammatory cells, lymphocytes, eosinophils, and macrophages. The urethane was rated with a response index of 1.5 versus 3.25 for the urethane/collagen composite; Silastic Rubber rated a response index of 1.67 versus 3.12 for the Silastic Rubber/collagen composite; collagen rated a response index of 3.3. The polyester sutures also induced a reaction with a larger fibrous capsule but fewer inflammatory cells as compared to collagen and collagen composites.     

In vitro degradation of silk fibroin

A significant need exists for long-term degradable biomaterials which can slowly and predictably transfer a load-bearing burden to developing biological tissue. In this study Bombyx mori silk fibroin yarns were incubated in 1mg/ml Protease XIV at 37 degrees C to create an in vitro model system of proteolytic degradation. Samples were harvested at designated time points up to 12 weeks and (1) prepared for scanning electron microscopy (SEM), (2) lyophilized and weighed, (3) mechanical properties determined using a servohydraulic Instron 8511, (4) dissolved and run on a SDS-PAGE gel, and (5) characterized with Fourier transform infrared spectroscopy. Control samples were incubated in phosphate-buffered saline. Fibroin was shown to proteolytically degrade with predictable rates of change in fibroin diameter, failure strength, cycles to failure, and mass. SEM indicated increasing fragmentation of individual fibroin filaments from protease-digested samples with time of exposure to the enzyme; particulate debris was present within 7 days of incubation. Gel electrophoresis indicated a decreasing amount of the silk 25 kDa light chain and a shift in the molecular weight of the heavy chain with increasing incubation time in protease. Results support that silk is a mechanically robust biomaterial with predictable long-term degradation characteristics.     

In vivo and in vitro degradation of glycine/DL-lactic acid copolymers

A series of copolymers of glycine and DL-lactic acid with various compositions was synthesized and their in vivo and in vitro degradation behavior was studied. For the in vivo examination, discs of the copolymer films were subcutaneously implanted in rats. The in vitro studies were carried out in phosphate buffer at pH = 7.4 and 37 degrees C. The decrease in molecular weight, the loss of weight, and the tissue reactions of the different copolymers were determined after 2, 5, and 10 weeks. Poly(DL-lactic acid) was used as reference material. The in vivo and in vitro degradation behavior of the polymers was comparable. The decrease of molecular weight of the copolymers and poly(DL-lactic acid) in time was similar. The weight loss for copolymers with a higher mole fraction of glycine units started earlier. The copolymer with the highest content of glycine units disappeared completely within 10 weeks both in vivo and in vitro. The poly(DL-lactic acid) implant lost only 25% weight over the same period. Tissue reactions against all materials started with an acute inflammatory reaction caused by the trauma of implantation, followed by wound-healing processes, ending in a very mild foreign body reaction for the poly(DL-lactic acid) and a more excessive macrophage mediated foreign body reaction for the glycine/DL-lactic acid copolymers. The tissue reaction was more severe for polymers having a higher rate of degradation.