In recent years, extensive studies have been continuously undertaken on the design of bioactive and biomimetic dental implant surfaces due to the need for improvement of the implant–bone interface properties. In this paper, the titanium dental implant surface was modified by bioactive vitamin D3 molecules by a self-assembly process in order to form an improved anticorrosion coating. Surface characterization of the modified implant was performed by field emission scanning electron microscopy (FE-SEM), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and contact angle measurements (CA). The implant’s electrochemical stability during exposure to an artificial saliva solution was monitored in situ by electrochemical impedance spectroscopy (EIS). The experimental results obtained were corroborated by means of quantum chemical calculations at the density functional theory level (DFT). The formation mechanism of the coating onto the titanium implant surface was proposed. During a prolonged immersion period, the bioactive coating effectively prevented a corrosive attack on the underlying titanium (polarization resistance in order of 107 Ω cm2) with ~95% protection effectiveness.
One of the most common crystal habits of the thermodynamically stable polymorph of calcium carbonate, calcite, is the rhombohedral one, which exposes {10.4} faces. When calcite is precipitated in the presence of Li+ ions, dominantly {00.1} faces appear together with the {10.4}, thus generating truncated rhombohedrons. This well-known phenomenon is explored in this work, with the aim of obtaining calcite crystals with smooth {00.1} faces. In order to achieve this objective, the formation of calcite was examined in precipitation systems with different c(Ca2+)/c(Li+) ratios and by performing an initial high-power sonication. At the optimal conditions, a precipitate consisting of thin, tabular {001} calcite crystals and very low content of incorporated Li+ has been obtained. The adsorption properties of the tabular crystals, in which the energetically unstable {00.1} faces represent almost all of the exposed surface, were tested with model dye molecules, calcein and crystal violet, and compared to predominantly rhombohedral crystals. It was found that the {00.1} crystals showed a lower adsorption capability when compared to the {10.4} crystals for calcein, while the adsorption of crystal violet was similar for both crystal morphologies. The obtained results open new routes for the usage of calcite as adsorbing substrates and are relevant for the understanding of biomineralization processes in which the {00.1} faces often interact with organic macromolecules.
Self-assembled molecules (SAMs) form layers on copper that have an advantage compared to traditional corrosion inhibitors because of the significant decrease of chemical application. The protective properties of such films can be improved by different procedures of application of the SAM layer. In this work, a SAM layer of elaidic acid, a monounsaturated long-chain fatty acid with trans geometrical configuration, was applied on copper surface. Gamma irradiation was used to improve the protective properties of the SAM layer toward corrosion in 3% NaCl. Influence of gamma irradiation on such layer's properties was studied by different electrochemical techniques (polarization measurements, EIS), contact angle measurements and FTIR analysis. The results have shown that gamma irradiation at doses 0.5-5 kGy improves the protective properties of the SAM. The surface film became thinner due to stronger adsorption and resulted in better ordering of molecules on the surface of the oxide film although the polymerization involving the participation of oxygen molecules has been initiated by irradiation.
Background: Nowadays investigations in the field of dental implants engineering are focused on bioactivity and osseointegration properties. Objective: In this study, the oxide-covered titanium was functionalized by vitamin D3 molecules via a simple self-assembly method with the aim to design more corrosion resistant and at the same time more bioactive surface. Methods: Surface properties of the D3-coated titanium were examined by scanning electron microscopy, attenuated total reflectance Fourier transform infrared spectroscopy, and contact angle measurements, while a long-term corrosion stability during immersion in an artificial saliva solution was investigated in situ by electrochemical impedance spectroscopy. Results: Results of all techniques confirmed a successful formation of the D3 vitamin layer on the oxide-covered titanium. Besides very good corrosion resistivity (~5 MΩcm2 ) the D3-modified titanium surface induced spontaneous formation of biocompatible bone-like calcium phosphates (CaP). Conclusion: Observed in vitro CaP-forming ability as a result of D3-modified titanium/artificial saliva interactions could serve as a promising predictor of in vivo bioactivity of implant materials.
Amino acids (AAs) attract attention for elucidating the role of proteins in biomineralization and the preparation of functionalized biomaterials. The influence that AAs exert on calcium phosphate (CaP) mineralization is still not completely understood, as contradictory results have been reported. In this paper, the influence of the addition of different classes of AAs, charged (L-aspartic acid, Asp; L-lysine, Lys), polar (L-asparagine, Asn; L-serine, Ser; L-tyrosine, Tyr), and non-polar (L-phenylalanine, Phe), on CaP growth in the presence of octacalcium phosphate (OCP) and calcium hydrogenphosphate dihydrate (DCPD) seeds was investigated. In control systems (without AAs), a calcium-deficient apatite (CaDHA) layer was formed on the surface of OCP, while a mixture of CaDHA and OCP in the form of spherical aggregates was formed on the surface of DCPD crystals. Charged and non-polar promoted, while polar AAs inhibited CaDHA formation on the OCP seeds. In the case of DCPD, Lys, Asp, and Phe promoted CaP formation, while the influence of other AAs was negligible. The most efficient promotor of precipitation in both cases was non-polar Phe. No significant influence of AAs on the composition and morphology of precipitates was observed. The obtained results are of interest for understanding biomineralization processes and additive controlled material synthesis.
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