Thermal and chemical modification of titanium-aluminum-vanadium implant materials: effects on surface properties, glycoprotein adsorption, and MG63 cell attachment.

The microstructure, chemical composition and wettability of thermally and chemically modified Ti-6Al-4V alloy disks were characterized and correlated with the degree of radiolabeled fibronectin-alloy surface adsorption and subsequent adhesion of osteoblast-like cells. Heating either in pure oxygen or atmosphere (atm) resulted in an enrichment of Al and V within the surface oxide. Heating (oxygen/atm) and peroxide treatment both followed by butanol treatment resulted in a reduction in content of V, but not in Al. Heating (oxygen/atm) or peroxide treatment resulted in a thicker oxide layer and a more hydrophilic surface when compared with passivated controls. Post-treatment with butanol, however, resulted in less hydrophilic surfaces than heating or peroxide treatment alone. The greatest increases in the adsorption of radiolabeled fibronectin following treatment were observed with peroxide/butanol-treated samples followed by peroxide/butanol and heat/butanol, although binding was only increased by 20-40% compared to untreated controls. These experiments with radiolabeled fibronectin indicate that enhanced adsorption of the glycoprotein was more highly correlated with changes in chemical composition, reflected in a reduction in V content and decrease in the V/Al ratio, than with changes in wettability. Despite promoting only a modest elevation in fibronectin adsorption, the treatment of disks with heat or heat/butanol induced a several-fold increase in the attachment of MG63 cells promoted by a nonadhesive concentration of fibronectin that was used to coat the pretreated disks compared to uncoated disks. Therefore, results obtained with these modifications of surface properties indicate that an increase in the absolute content of Al and/or V (heat), and/or in the Al/V ratio (with little change in hydrophilicity; heat+butanol) is correlated with an increase in the fibronectin-promoted adhesion of an osteoblast-like cell line. It would also appear that the thermal treatment-induced enhancement of cell adhesion in the presence of this integrin-binding protein is due to its increased biological activity, rather than a mass effect alone, that appear to be associated with changes in chemical composition of the metallic surface. Future studies will investigate the influence of the surface chemical composition of various implantable alloys on protein adsorption and receptor-mediated cell adhesion. In addition, by altering the properties of bound osteogenic protein enhancing exposure to cell integrin binding domains, it may be possible to develop implant surfaces which enhance the attachment, adhesion and developmental response of osteoblast precursors leading to accelerated osseointegration.

Adsorption and dissolution behavior of human plasma fibronectin on thermally and chemically modified titanium dioxide particles.

Titanium is known for its biocompatibility and is widely used in dental and orthopedic reconstructive surgery. There are reports that osteointegration of these implants is not optimal. The objective of this study was to modify titanium dioxide particles and examine the resultant effects on protein adsorption to these altered surfaces using a model cell binding protein, human plasma fibronectin (HPF). HPF is an important matrix glycoprotein that plays a major role in cell and protein attachment, Titanium dioxide surfaces were modified by heating the titanium dioxide powder at 800 degrees C for 1 h or treating with an oxidizing agent: peroxide in ammonium hydroxide followed by peroxide in hydrochloric acid. Oxidized and control samples were further treated with 9:1 butanol:water for 30 min. Brunauer-Emmett-Teller showed no change in particle surface area as a result of thermal or chemical treatment. Hydrophobicity increased with butanol treatment of titanium dioxide. Diffuse reflectance Fourier transform infrared spectroscopy showed the presence of -CH2 and -CH3 vibrations in the region of 2850-3000 cm(-1) for both the heated, butanol and peroxide/butanol-treated samples. The absence of increased C-O and O-C=O features as determined by electron spectroscopy for chemical analysis indicates that butanol adsorption is not occurring via an esterification mechanism. The interaction between butanol and pre-heated or peroxide-treated titanium dioxide may be one of association (weak electrostatic and/or Van der Waals forces) rather than direct ionic bonding. Maximum HPF adsorption on modified or unmodified titanium dioxide occurred within 30 min, with greater protein adsorption occurring on butanol-treated samples. Desorption was minimal with all modifications. Zeta potential measurements showed that HPF adsorption caused an increase in the negative zeta potential with the greatest change noted for the butanol-treated samples. These findings suggest that wettability and surface charge both play an important role in protein adsorption to titanium dioxide. Thus, by modifying the physico-chemical properties of titanium dioxide surfaces, it may be possible to alter protein adsorption and hence optimize cell attachment.

Development of an enhanced anticaries efficacy dual component dentifrice containing sodium fluoride and dicalcium phosphate dihydrate.

A dual-chamber dentifrice, which contains sodium fluoride (NaF) in one component and dicalcium phosphate dihydrate (dical) in the other, has been developed. The dentifrice is packaged in a dual-chamber tube and is formulated to deliver 1100 ppm F. A series of studies consisting of in vitro fluoride uptake, in vivo calcium labeling, intraoral remineralization-demineralization, and animal caries studies were performed to support the improved anticaries efficacy of this product in comparison to a sodium fluoride/silica dentifrice (NaF/silica). An in vitro fluoride uptake study comparing 1100 ppm F NaF/dical dentifrice to 1100 ppm F NaF/silica showed that NaF/dical delivered significantly more fluoride than NaF/silica, 3.72 +/- 0.36 micrograms/cm2 versus 2.41 +/- 0.10 micrograms/cm2. A 6-day in vivo brushing study with a 44Ca labeled NaF/dical dentifrice showed that calcium from dical penetrated demineralized enamel and was present in plaque up to 18 hrs since the last brushing. An intra-oral remineralization-demineralization study was performed to evaluate NaF/dical's ability to promote remineralization in comparison to three silica-based dentifrices containing 0, 250, and 1100 ppm F as NaF. The percent mineral changes after treatment were +20.44 +/- 17.14 for NaF/dical, +9.27 +/- 19.53 for 1100 ppm NaF/silica, -1.43 +/- 20.57 for 250 ppm NaF/silica, and -12.36 +/- 32.76 for 0 ppm F/silica. A statistical analysis showed that the dual-chamber NaF/dical dentifrice was significantly more effective than the 1100 ppm NaF/silica dentifrice at promoting remineralization. A rat caries study was performed to evaluate NaF/dical ability to prevent caries in comparison to 1100 ppm F NaF/silica, 250 ppm F NaF/silica, silica, and dical dentifrices. The mean smooth surface caries scores were 1.6 +/- 2.8 for NaF/dical, 5.5 +/- 6.2 for 1100 ppm F NaF/silica, 10.6 +/- 6.2 for 250 ppm F NaF/silica, 13.7 +/- 4.7 for 0 ppm F/silica, and 9.5 +/- 7.8 0 ppm F/dical. A statistical analysis showed that the the dual-chamber NaF/dical dentifrice was superior to all other treatments tested in preventing caries in rats. The dical dentifrice was significantly superior to the silica dentifrice in preventing caries, which indicates that dical alone exhibits anticaries efficacy. In conclusion, individual and cumulative results from the fluoride uptake, intra-oral remineralization-demineralization, and rat caries studies from the dual chamber NaF/dical dentifrice support the improved anticaries efficacy of this product.

Physicochemical study of plasma-sprayed hydroxyapatite-coated implants in humans.

This study represents the first report of the physical and chemical changes occurring in coatings of failed hydroxyapatite (HA)-coated titanium implants obtained from a comprehensive, multicenter human dental implant study. A total of 53 retrieved samples were obtained and compared with unimplanted controls with the same manufacturer and similar manufacture dates. Forty-five retrieved implants were examined for surface characteristics and bulk composition. Implants were staged based on implantation history: stage 1 (implants retrieved between surgical placement and surgical uncovering), stage 2 (implants retrieved at surgical uncovering and evaluation), stage 3 (implants retrieved between surgical uncovering evaluation and occlusal loading), and stage 4 (implants retrieved after occlusal loading). Scanning electron microscopy showed progressive coating thinning with implantation time. At later stages, bare Ti metal was detected by energy-dispersive X-ray analysis and electron spectroscopy for chemical analysis. Increases in Ti and Al (2-7.5 atm % each) were detected at the apical ends of all stage 4 samples. In unimplanted coatings, X-ray diffraction analysis demonstrated the presence of amorphous calcium phosphate, beta-tricalcium phosphate, tetracalcium phosphate, and calcium oxide in addition to large hydroxyapatite crystals (c axis size, D002 = 429 +/- 13 A; a axis size, D300 = 402 +/- 11 A, a/c aspect ratio 0.92). The nonapatitic phases disappeared with increased implantation time, although there was a persistence of amorphous calcium phosphate. Bulk coating chemical analysis showed that Ca/P ratios for implant controls (1.81 +/- 0.01) were greater than stoichiometric HA (1.67) and decreased for implant stages 3 and 4 (1.69 +/- 0.09 and 1.67 +/- 0.09, respectively), explained by the dissolution of the non apatitic phases. Crystal sizes also changed with implantation times, being smaller than the control at all but stage 4. Fourier transform infrared analyses agreed with these results, and also indicated the accumulation of bone (protein and carbonate-apatite) in the retrieved coatings. The accumulation of bone was not stage dependent. These findings indicate that there was some biointegration with the surrounding bone, but the greatest changes occurred with the HA coating materials, their loss, and chemical change.

Elemental and molecular imaging of human hair using secondary ion mass spectrometry.

Secondary ion mass spectrometry (SIMS) is used to image the spatial distribution of elemental and molecular species on the surface and in cross sections of doped human hair using a magnetic sector SIMS instrument operated as an ion microprobe. Analysis of electrically insulating, non-planar hair samples requires one of two different methods of charge compensation to be used depending on the polarity of the sputtered secondary ions. For detection of positive secondary ions, the hair is imaged using a approximately 0.5 micron diameter, 19.5 keV impact energy, O- microbeam with no auxiliary electron bombardment. For detection of negative secondary ions, a approximately 0.2 micron diameter, 14.5 keV impact energy Cs+ microbeam is used in conjunction with normal incidence, low-energy electron bombardment. Both of these methods allow submicrometer spatial resolution elemental and molecular secondary ion images to be obtained from hair samples without metallic coating of the sample surface prior to analysis. Several examples are presented that reflect potential application areas for these analytical methods.

Recent advances in stannous fluoride technology: antibacterial efficacy and mechanism of action towards hypersensitivity.

Stannous fluoride (SnF2) is highly susceptible to oxidation and hydrolysis but both anhydrous and aqueous preparations can be well established by proper formulation. When stability in aqueous preparations is achieved by the use of certain strong complexing agents, reduced antibacterial activity is observed which may be attributed to reduced bioavailability of the stannous ion. In contrast, an anhydrous SnF2 preparation maintains stannous ion in a stable but, uncomplexed form. This preparation displays antibacterial activity in saliva and delivers stannous ion which is absorbed onto surfaces making them less susceptible to plaque formation for an extended period of time (hours). When this anhydrous preparation is brushed onto dentine in vitro or in situ, one observes a nearly complete coverage of the dentine surface and occlusion of tubules by a tin-rich surface deposit. This finding indicates that the observed clinical efficacy of this preparation at relieving hypersensitivity is due to occlusion of tubules by a mixture of low solubility complexes of tin. A water-based SnF2 preparation containing strongly complexed stannous ions does not form a surface coating on dentine in vitro suggesting that this preparation may not be optimal for treating hypersensitivity. Overall, the findings indicate that the stannous ions in a SnF2 preparation must be maintained in a stable, bioavailable form for optimal efficacy against plaque and hypersensitivity to be obtained. The results suggest that these properties are provided by stable anhydrous preparations but are difficult to achieve simultaneously in aqueous preparations. When properly formulated, stannous fluoride preparations can provide multiple oral therapeutic benefits.

Evaluation of a new dentifrice for the treatment of sensitive teeth.

A dentifrice containing 5% potassium nitrate, 1.3% soluble pyrophosphate, 1.5% polyvinylmethyl ether and maleic acid (PVM/MA) copolymer and 0.243% sodium fluoride in a silica base (Sensitive/Tartar Control) has been developed to concomitantly control tartar, caries and dentinal hypersensitivity. In vitro and animal studies show that the fluoride in this product effectively inhibits formation of enamel and dentine caries. In vitro studies also demonstrate that this dentifrice effectively reduces hydraulic conductance by occluding dentine tubules with a mixed surface deposit of copolymer and silica. Using an in vitro model that simulates in vivo conditions, this dentifrice also allows a rapid penetration of potassium nitrate through the dentine matrix. These findings demonstrate a correlation under in vivo conditions between the occlusion of dentine and the ability to deliver topically applied agents to target sites within or below dentine. The results indicate that this new dentifrice should provide multiple clinical therapeutic benefits including controlling tooth decay and tartar formation, and reducing and preventing dentinal hypersensitivity.