Jerzy Kubacki

Photofunctionalization of Titanium: An Alternative Explanation of Its Chemical-Physical Mechanism.

Objectives To demonstrate that titanium implant surfaces as little as 4 weeks from production are contaminated by atmospheric hydrocarbons. This phenomenon, also known as biological ageing can be reversed by UVC irradiation technically known as photofunctionalization. To propose a new model from our experimental evidence to explain how the changes in chemical structure of the surface will affect the adsorption of amino acids on the titanium surface enhancing osteointegration. Methods In our study XPS and AES were used to analyze the effects of UVC irradiation (photofunctionalization) in reversing biological ageing of titanium. SEM was used to analyze any possible effects on the topography of the surface. Results UVC irradiation was able to reverse biological ageing of titanium by greatly reducing the amount of carbon contamination present on the implant surface by up to 4 times, while the topography of the surface was not affected. UVC photon energy reduces surface H2O and increases TiOH with many –OH groups being produced. These groups explain the super-hydrophilic effect from photofunctionalization when these groups come into contact with water. Significance Photofunctionalization has proven to be a valid method to reduce the amount of hydrocarbon contamination on titanium dental implants and improve biological results. The chemisorption mechanisms of amino acids, in our study, are dictated by the chemical structure and electric state present on the surface, but only in the presence of an also favourable geometrical composition at the atomical level.

Synthesis and characterisation of PEG-peptide surfaces for proteolytic enzyme detection.

AbstractPeptide surfaces were obtained by the covalent immobilisation of fluorescently labelled pentapeptides carboxyfluorescein–glycine–arginine–methionine–leucine–glycine, either directly or through a poly(ethylene glycol) (PEG) linker on modified silicon wafers. Each step during the preparation of the peptide surfaces was confirmed by several surface characterisation techniques. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy were used to determine the surface composition, the wafers philicity was measured by contact angle and atomic force microscopy was used to investigate the surface morphology. Exposure of the peptide surfaces to trypsin resulted in the release of a fluorescently labelled peptide product, which allowed the kinetics of the enzymatic reaction to be followed with the aid of fluorescence spectroscopy. The electrospray ionisation mass spectrometry analysis of the post-digestion solution confirmed that the pentapeptides attached to the solid support undergo specific trypsin hydrolysis at the C-terminus of the arginine residues. Detailed surface analyses before and after the enzyme action was performed using ToF-SIMS. Because of the limited accessibility of the short peptide directly attached to the surface, a quantitative yield of enzymatic hydrolysis was observed only in case when the peptide was bound through the PEG linker. The insertion of the PEG linker increased the number of immobilised peptides and the rate of enzymatic digestion which consequently improved the quality of the enzyme assays. The described approach may be used for different peptide sequences designed for other proteases. FigureMonitoring of trypsin hydrolysis on PEG-peptide surface

Temperature-Driven Changes of Electronic Structure Through the Phase Transition in Magnetocaloric Compound Mn 1.1 Fe 0.9 P 0.55 As 0.45

The electronic structure of magnetocaloric compound Mn1.1Fe0.9P0.55As0.45, prepared via solid-state sintering was studied. Adiabatic temperature change of 3.6 K was observed through the phase transition found at 273 K. The X-ray diffraction and time-of-flight secondary ion mass spectroscopy were applied to verify the purity and homogeneity of the sample. The X-ray photoemission spectroscopy was used to study electronic structure at room temperature and below the phase transition at 180 K. The existence of local magnetic moment was deduced from the exchange splitting effect found for 2p states of manganese. This effect was also studied below the phase transition at low temperature. It was reflected in the shape of the valence band. A shift of 0.15 eV was detected on the onset of the valence band at low temperature. The splitting of the 3s core lines of manganese and iron were investigated. The values of these splitting were obtained. No influence of phase transition was found on the photoemission spectra from iron 2p, phosphorus 2p, and arsenic 3d states.

Photofunctionalization of dental zirconia oxide: Surface modification to improve bio-integration preserving crystal stability

The use of zirconium oxide in dental implantology is rapidly increasing as it is regarded as being more aesthetical and biologically friendly than titanium oxide. The interaction of titanium oxide with cells and proteins has proven to be significantly affected by the inevitable atmospheric hydrocarbon contamination, defined as biological ageing. The latter has proven to be effectively reversed by UVC irradiation. Crystal structures of both Zr and Ti oxides are very similar, thus also ZrO2 is prone to contamination by hydrocarbons. In the present study we have characterized the chemical-physical changes occurring to ZrO2 after UVC irradiation. Firstly a reduction by 3-fold of carbon present on its surface. XRD analysis has indicated that UVC irradiation treatment does not affect the crystalline structure of ZrO2, suggesting that it is possible to improve cell attachment on the surface without sacrificing the mechanical strength of the material. In addition a chemical model of interaction of cell surface proteins with the almost carbon free ZrO2 surface obtainable after UVC irradiation is proposed, pointing to the important role likely played by integrins and RGD sequences originating in soluble proteins adsorbed at the cell/ZrO2 interface. Hence in clinical practice UVC photofunctionalization could improve the soft tissue seal around dental implants functioning as a valid barrier between implant and peri-implant bone, thereby improving the long-term success of implants.