Adhesivos óseos basados en cianoacrilatos / Bone adhesives based on cyanoacrylates

Los adhesivos biocompatibles de curado rápido son una alternativa promisoria para sustituir los dispositivos metálicos empleados en la inmovilización de fracturas de pequeños fragmentos óseos y en algunos procedimientos de cirugía máxilo-facial. Ellos tienen la capacidad de servir de soporte en el proceso de curación, aportan ventajas respecto a los métodos convencionales de fijación mediante placas y tornillos, tales como: su facilidad de aplicación y la biodegradabilidad del material. El objetivo del presente trabajo es analizar la literatura relacionada con los adhesivos óseos basados en cianoacrilatos, exponiendo las características de estos biomateriales, sus ventajas y desventajas para la fijación de pequeños fragmentos óseos en cirugía máxilo facial y ortopedia. Los estudios realizados de bioactividad, degradabilidad, citotoxicidad in vitro, implantación in vivo y adhesividad han demostrado que los materiales evaluados son biocompatibles y capaces de unir el tejido óseo.

Fast curing biocompatible adhesives are a promising alternative to the metallic devices used for immobilization of fractures of small bone fragments as well as for some maxillofacial surgical procedures. They may serve as supports during the curing process, and present some advantages with respect to conventional fixation methods by plates and screws, such as their ease of application and the biodegradability of the material. The objective of the present study is to analyze the literature about bone adhesives based on cyanoacrylates, presenting the characteristics of these biomaterials, as well as their advantages and disadvantages for the fixation of small bone fragments in maxillofacial surgery and orthopedics. Study of the bioactivity, degradability, in vitro cytotoxicity, in vivo implantation and adhesiveness of the materials evaluated reveal their biocompatibility and their capacity to bind bone tissue.

Synthesis of magnesium- and manganese-doped hydroxyapatite structures assisted by the simultaneous incorporation of strontium.

Samples of crystalline hydroxyapatite (HA) with and without the addition of individual Mg(2+), Mn(2+) and Sr(2+) ions and samples with the addition of all three ions simultaneously were prepared using the precipitation method in an aqueous medium. Chemical, structural, spectroscopic and thermophysical analyses of the synthesized samples were conducted. The obtained results indicate that Sr(2+) ions were easily incorporated into the HA crystal structure, whereas it was difficult to incorporate Mg(2+) and Mn(2+) ions into the HA lattice when these ions were individually introduced into the samples. The synthesis of HA with Mg(2+) or Mn(2+) ions is characterized by the formation of HA with a low concentration of doping elements that is outweighed by the amount of these atoms present in less biocompatible phases that formed simultaneously. However, the incorporation of Sr(2+) along with Mg(2+) and Mn(2+) ions into the samples allowed for the synthesis of HA with considerably higher concentrations of Mg(2+) and Mn(2+) in the crystal lattice.

Interlaboratory studies on in vitro test methods for estimating in vivo resorption of calcium phosphate ceramics.

A potential standard method for measuring the relative dissolution rate to estimate the resorbability of calcium-phosphate-based ceramics is proposed. Tricalcium phosphate (TCP), magnesium-substituted TCP (MgTCP) and zinc-substituted TCP (ZnTCP) were dissolved in a buffer solution free of calcium and phosphate ions at pH 4.0, 5.5 or 7.3 at nine research centers. Relative values of the initial dissolution rate (relative dissolution rates) were in good agreement among the centers. The relative dissolution rate coincided with the relative volume of resorption pits of ZnTCP in vitro. The relative dissolution rate coincided with the relative resorbed volume in vivo in the case of comparison between microporous MgTCPs with different Mg contents and similar porosity. However, the relative dissolution rate was in poor agreement with the relative resorbed volume in vivo in the case of comparison between microporous TCP and MgTCP due to the superimposition of the Mg-mediated decrease in TCP solubility on the Mg-mediated increase in the amount of resorption. An unambiguous conclusion could not be made as to whether the relative dissolution rate is predictive of the relative resorbed volume in vivo in the case of comparison between TCPs with different porosity. The relative dissolution rate may be useful for predicting the relative amount of resorption for calcium-phosphate-based ceramics having different solubility under the condition that the differences in the materials compared have little impact on the resorption process such as the number and activity of resorbing cells. STATEMENT OF SIGNIFICANCE: The evaluation and subsequent optimization of the resorbability of calcium phosphate are crucial in the use of resorbable calcium phosphates. Although the resorbability of calcium phosphates has usually been evaluated in vivo, establishment of a standard in vitro method that can predict in vivo resorption is beneficial for accelerating development and commercialization of new resorbable calcium phosphate materials as well as reducing use of animals. However, there are only a few studies to propose such an in vitro method within which direct comparison was carried out between in vitro and in vivo resorption. We propose here an in vitro method based on measuring dissolution rate. The efficacy and limitations of the method were evaluated by international round-robin tests as well as comparison with in vivo resorption studies for future standardization. This study was carried out as one of Versailles Projects on Advanced Materials and Standards (VAMAS).

A study of the physical, chemical and biological properties of TiO2 coatings produced by micro-arc oxidation in a Ca-P-based electrolyte.

In this work, a porous and homogeneous titanium dioxide layer was grown on commercially pure titanium substrate using a micro-arc oxidation (MAO) process and Ca-P-based electrolyte. The structure and morphology of the TiO2 coatings were characterized by X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy, and profilometry. The chemical properties were studied using electron dispersive X-ray spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy. The wettability of the coating was evaluated using contact angle measurements. During the MAO process, Ca and P ions were incorporated into the oxide layer. The TiO2 coating was composed of a mixture of crystalline and amorphous structures. The crystalline part of the sample consisted of a major anatase phase and a minor rutile phase. A cross-sectional image of the coating-substrate interface reveals the presence of voids elongated along the interface. An osteoblast culture was performed to verify the cytocompatibility of the anodized surface. The results of the cytotoxicity tests show satisfactory cell viability of the titanium dioxide films produced in this study.

Biocompatibility of wollastonite-poly(N-butyl-2-cyanoacrylate) composites.

Wollastonite-poly(n-butyl-2-cyanoacrylate) composite (W-BCA) has been proposed to immobilize anatomically bone fragments in order to achieve an optimal healing process. The present study evaluated the in vitro and in vivo behavior of three types of fillers: powdered natural wollastonite (Wn), synthetic pseudowollastonite powder (Ws), and synthetic pseudowollastonite powder coated with 5% acetyl tributyl citrate (Wst). The Wst-BCA composite underwent a higher degradability in the real-time degradation test and a superior cytotoxic effect; whereas the Wn-BCA composite showed a higher degradability in the accelerated test with no cytotoxicity. The formation of an extracellular collagenous matrix deposit on its surface and the most favorable new bone formation on Wn-BCA indicate its potential for bone adhesive use in unstable orthopedic traumas.

Surface-enhanced Raman scattering study of the redox adsorption of p-phenylenediamine on gold or copper surfaces.

The adsorption of the p-phenylenediamine (PPD(+)) radical cation on gold or copper nanoparticle (NP) surfaces was studied through surface-enhanced Raman scattering (SERS) spectroscopy, excited at 1064 nm. The SERS spectra were obtained from gold or copper NPs after exposure to non-oxidized p-phenylenediamine (PPD) aqueous solution, in millimolar concentration. The gold NPs were synthesized as nanoshells involving silica cores (SiO(2)@Au) and the copper NPs were obtained in aqueous medium, undergoing surface oxidation with the formation of Cu(II) oxide nanoshell (Cu@CuO). In the latter, the oxidative adsorption of PPD(+) led to the reduction of the copper oxide, present on NP surface, allowing obtaining the PPD(+) SERS spectrum. The vibrational assignments of the SERS spectra of the adsorbate were performed using the results of Density Functional Theory calculations of the Raman frequencies, which together with the SERS surface selection rules, allowed to infer the adsorption geometry of PPD(+) radical cation on both metallic surfaces. This work stress the investigation of redox processes involved in the molecular adsorption is imperative for the interpretation of the SERS results, which is even more important when copper surfaces are studied.

Understanding the impact of divalent cation substitution on hydroxyapatite: an in vitro multiparametric study on biocompatibility.

Hydroxyapatite (HA), a stable and biocompatible material for bone tissue therapy, may present a variable stoichiometry and accept a large number of cationic substitutions. Such substitutions may modify the chemical activity of HA surface, with possible impact on biocompatibility. In this work, we assessed the effects of calcium substitution with diverse divalent cations (Pb(2+), Sr(2+), Co(2+), Zn(2+), Fe(2+), Cu(2+), or Mg(2+)) on the biological behavior of HA. Physicochemical analyses revealed that apatite characteristics related to crystallinity and calcium dissolution/uptake rates are very sensitive to the nature of cationic substitution. Cytocompatibility was evaluated by mitochondrial activity, membrane integrity, cell density, proapoptotic potential, and adhesion tests. With the exception of Zn-HA, all the substituted HAs induced some level of apoptosis. The highest apoptosis levels were observed for Mg-HA and Co-HA. Cu-HA was the only material to impair simultaneously mitochondrial activity, membrane integrity, and cell density. The highest relative cell densities after exposure to the modified HAs were observed for Mg-HA and Zn-HA, while Co-HA significantly improved cell adhesion onto HA surface. These results show that changes on surface dissolution caused by cationic substitution, as well as the increase of metal species released to biological media, were the main responsible factors related to alterations on HA biocompatibility.

Surface characterization of dental implants coated with hydroxyapatite by plasma spray and biomimetic process.

PURPOSE: The aim of this study was to characterize implants coated with hydroxyapatite (HA) using 2 different processes. MATERIALS AND METHODS: Commercially pure titanium implants were coated with HA using a modified biomimetic process and the plasma spray process. These implants were characterized by scanning electron microscopy, Fourier-transformed infrared spectroscopy, and x-ray photoelectron spectroscopy. RESULTS: The plasma spray process generates a typical rough topography mainly consisting of HA. The HA coating produced by biomimetic process was partially dissolved in water and only a very thin layer of calcium titanate plus calcium phosphate and probably beta-tricalcium phosphate remained. In vitro test showed that both coatings can be considered bioactive. CONCLUSION: The modified biomimetic process seems to be a simple and low-cost alternative to coat titanium with a high potential of In vitro application.

Physicochemical characterization of two deproteinized bovine xenografts.

Calcium phosphate salts, or more specifically hydroxyapatite, are products of great interest in the fields of medical and dental science due to their biocompatibility and osteoconduction property. Deproteinized xenografts are primarily constituted of natural apatites, sintered or not. Variations in the industrial process may affect physicochemical properties and, therefore, the biological outcome. The purpose of this work was to characterize the physical and chemical properties of deproteinized xenogenic biomaterials, Bio-Oss (Geistlich Biomaterials, Wolhuser, Switzerland) and Gen-Ox (Baumer S.A., Brazil), widely used as bone grafts. Scanning electron microscopy, infrared region spectroscopy, X-ray diffraction, thermogravimetry and degradation analysis were conducted. The results show that both materials presented porous granules, composed of crystalline hydroxyapatite without apparent presence of other phases. Bio-Oss presented greater dissolution in Tris-HCl than Gen-Ox in the degradation test, possibly due to the low crystallinity and the presence of organic residues. In conclusion, both commercial materials are hydroxyapatite compounds, Bio-Oss being less crystalline than Gen-Ox and, therefore, more prone to degradation.

Physicochemical characterization of two deproteinized bovine xenografts

Calcium phosphate salts, or more specifically hydroxyapatite, are products of great interest in the fields of medical and dental science due to their biocompatibility and osteoconduction property. Deproteinized xenografts are primarily constituted of natural apatites, sintered or not. Variations in the industrial process may affect physicochemical properties and, therefore, the biological outcome. The purpose of this work was to characterize the physical and chemical properties of deproteinized xenogenic biomaterials, Bio-Oss (Geistlich Biomaterials, Wolhuser, Switzerland) and Gen-Ox (Baumer S.A., Brazil), widely used as bone grafts. Scanning electron microscopy, infrared region spectroscopy, X-ray diffraction, thermogravimetry and degradation analysis were conducted. The results show that both materials presented porous granules, composed of crystalline hydroxyapatite without apparent presence of other phases. Bio-Oss presented greater dissolution in Tris-HCl than Gen-Ox in the degradation test, possibly due to the low crystallinity and the presence of organic residues. In conclusion, both commercial materials are hydroxyapatite compounds, Bio-Oss being less crystalline than Gen-Ox and, therefore, more prone to degradation.

In vivo characterization of titanium implants coated with synthetic hydroxyapatite by electrophoresis.

This study compared in vivo the performances of commercially pure titanium (cp Ti) screw dental implants either uncoated or coated with synthetic hydroxyapatite (HA) by electrophoresis. The HA coating was characterized by scanning electron microscopy, energy dispersive spectroscopy (EDS) and Fourier-transform infrared (FT-IR) spectroscopy. Well-adhered carbonated-hydroxyapatite layers (4- to-8-microm-thick) were obtained. In vivo tests were carried out by insertion of both uncoated and HA-coated implants into rabbit tibiae for 8 or 12 weeks. Histomorphometric analysis was performed by scanning electron microscopy with the aid of image-processing software. Results showed significantly greater bone-implant contact for HA-coated implants (p<0.05) than cp Ti implants. Comparison of bone content inside the screw implants showed no significant differences (p>0.05) between both types of implants, although cp Ti had numerically higher percentage of bone content than HA-coated implants. In conclusion, the HA-coated implants had better performance regarding the bone-implant contact area than the uncoated implants; coating by electrophoresis proved to be a valuable process to coat metallic implants with an osteoconductive material such as hydroxyapatite.

In Vivo Characterization of Titanium Implants Coated with Synthetic Hydroxyapatite by Electrophoresis

Este estudo comparou in vivo a performance de implantes orais rosqueáveis fabricados em titânio comercialmente puro (Ti cp) e implantes recobertos com hidroxiapatita (HA) estequiométrica pelo processo de eletroforese. A camada recoberta foi caracterizada por microscopia eletrônica de varredura, espectroscopia de energia dispersiva e espectroscopia de infravermelho com transformada de Fourier. Foram obtidas camadas de carbonato-apatita bem aderidas ao substrato metálico, com espessura variando de 4 a 8 µm. Testes in vivo foram realizados por meio da inserção de implantes em tíbias de coelho por períodos de 8 ou 12 semanas. A análise histomorfométrica foi realizada quantificando-se imagens obtidas em microscopia eletrônica de varredura e com o auxílio de um software de processamento de imagens. Os resultados mostraram que a porcentagem de contato direto osso-implante foi significativamente maior para os implantes recobertos (p<0,05) do que para os implantes de titânio cp. A comparação da quantidade de osso no interior das roscas não mostrou diferença significativa para os dois tipos de implantes (p>0,05), embora os implantes de titânio cp tenham apresentado valores de porcentagem numericamente maiores que os implantes recobertos. Concluiu-se que os implantes recobertos com hidroxiapatita tiveram melhor performance em relação à área de contato osso-implante que os implantes de titânio cp. O processo de eletroforese parece ser uma alternativa simples e viável para se recobrir implantes de titânio com material osteocondutivo, como a hidroxiapatita.

Avaliação da adesão de hodroxi-apatia sobre implantes metálicos utilizando jato com suspensão de bicarbonato de cálcio / Evaluation of hydroxyapatite adhesion to metallic titanium by using sodium bicarbonate suspension spray

Matériais cerâmicos à base de fosfatos de cálcio como a hidroxiapatita (HA) são empregados no recobrimento de implantes metálicos para aplicações biomédicas. Esses recobrimentos possuem propriedades osteocondutoras, ou seja, favorecem a migração de células precursoras de osteoblastos, visando a minimizar o tempo de formação de novo osso e, consequentemente, acelerar a integração do implante. A adesão desses recobrimentos ao substrato metálico é de fundamental importância. Neste trabalho são apresentados e discutidos os métodos comumente empregados para medir ou avaliar a adesão, com suas vantagens e limitações. Propõe-se, então, um método de avaliação qualitativa em que chapas de titânio recobertas com hidroxiapatita por eletroforese são submetidas a um fluxo sob alta pressão contendo suspensão de bicarbonato de sódio. Esse método apresenta algumas vantagens, quando comparado aos testes que empregam fitas auto-adesivas, podendo ser empregado durante as etapas de desenvolvimento de processos de recobrimento.