Plasma Modification of Carbon Coating Produced by RF CVD on Oxidized NiTi Shape Memory Alloy under Glow-Discharge Conditions.

Our previous work has shown that for cardiac applications, combining low-temperature plasma oxidation with an amorphous carbon coating (a-C:N:H type) constitutes a prospective solution. In this study, a short-term modification by low-temperature oxygen plasma is proposed as an example and a method for shaping the topography and surface energy of the outer amorphous carbon coating, produced via the Radio-Frequency Chemical Vapour Deposition (RFCVD) method on NiTi alloy oxidized under glow-discharge conditions. This treatment alters the chemical composition of the outer zone of the surface layer. A slight increase is also noted in the surface roughness at the nanoscale. The contact angles were shown to increase by about 20% for water and 30% for diiodomethane, while the surface free energy decreased by ca. 11%. The obtained results indicate that even short-term contact with low-temperature plasma can shape the surface properties of the carbon coating, an outcome which shows potential in terms of its use in medical applications.

Photofunctionalization effect and biological ageing of PEEK, TiO2 and ZrO2 abutments material.

The aim of this study was to evaluate the effectiveness of UVC photofunctionalization in removing the surface carbon contamination compounds from the most used surfaces utilized in dental implantology: TiO2, ZrO2 and PEEK. Machined samples were treated by UVC light in an Ushio Therabeam SuperOsseo® device for 12 min each. Non-treated disks were set as controls. X-Ray photoelectron spectroscopy was used to monitor the changes in surface chemical composition. Photofunctionalization of the PEEK material has been analyzed here for the first time. The removal of hydrocarbons allowed by UVC irradiation was nearly twofold, and irradiation simultaneously led to an increase of H-O-C=O bonds. For TiO2 and ZrO2 surfaces, the loss of hydrocarbons detected after UVC irradiation was threefold. The chemical stability of surfaces when left at atmospheric conditions after UVC irradiation was monitored during 10 weeks. After 6 weeks the carbon contamination on TiO2 surfaces returned to the level before UVC treatment, while for ZrO2 and PEEK it was 75% and 60% of its initial value, respectively. None of the materials tested displayed any toxicity towards human fibroblasts cultured in direct contact with them, confirming their potential employment for manufacturing of implant abutments. UVC photofunctionalization can be thus regarded as a valid method in order to reverse the detrimental effects of biological ageing of implant surfaces.

Europium Doping Impact on the Properties of MBE Grown Bi2Te3 Thin Film.

The impact of europium doping on the electronic and structural properties of the topological insulator Bi2Te3 is studied in this paper. The crystallographic structure studied by electron diffraction and transmission microscopy confirms that grown by Molecular Beam Epitaxy (MBE) system film with the Eu content of about 3% has a trigonal structure with relatively large monocrystalline grains. The X-ray photoemission spectroscopy indicates that europium in Bi2Te3 matrix remains divalent and substitutes bismuth in a Bi2Te3 matrix. An exceptional ratio of the photoemission 4d multiplet components in Eu doped film was observed. However, some spatial inhomogeneity at the nanometer scale is revealed. Firstly, local conductivity measurements indicate that the surface conductivity is inhomogeneous and is correlated with a topographic image revealing possible coexistence of conducting surface states with insulating regions. Secondly, Time of Flight Secondary Ion Mass Spectrometry (TOF-SIMS) depth-profiling also shows partial chemical segregation. Such in-depth inhomogeneity has an impact on the lattice dynamics (phonon lifetime) evaluated by femtosecond spectroscopy. This unprecedented set of experimental investigations provides important insights for optimizing the process of growth of high-quality Eu-doped thin films of a Bi2Te3 topological insulator. Understanding such complex behaviors at the nanoscale level is a necessary step before considering topological insulator thin films as a component of innovative devices.

A Study of Catalytic Oxidation of a Library of C2 to C4 Alcohols in the Presence of Nanogold.

The classical stoichiometric oxidation of alcohols is an important tool in contemporary organic chemistry. However, it still requires huge modifications in order to comply with the principles of green chemistry. The use of toxic chemicals, hazardous organic solvents, and the large amounts of toxic wastes that result from the reactions are a few examples of the problems that must be solved. Nanogold alone or conjugated with palladium were supported on different carriers (SiO2, C) and investigated in order to evaluate their catalytic potential for environmentally friendly alcohol oxidation under solvent-free and base-free conditions in the presence H2O2 as a clean oxidant. We tested different levels of Au loading (0.1⁻1.2% wt.) and different active catalytic site forms (monometallic Au or bimetallic Au⁻Pd sites). This provided new insights on how the structure of the Au-dispersions affected their catalytic performance. Importantly, the examination of the catalytic performance of the resulting catalysts was oriented toward a broad scope of alcohols, including those that are the most resistant to oxidation-the primary aliphatic alcohols. Surprisingly, the studies proved that Au/SiO2 at a level of Au loading as low as 0.1% wt. appeared to be efficient and prospective catalytic system for the green oxidation of alcohol. Most importantly, the results revealed that 0.1% Au/SiO2 might be the catalyst of choice with a wide scope of utility in the green oxidation of various structurally different alcohols as well as the non-activated aliphatic ones.

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.

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.

Spectroscopic Studies on Organic Matter from Triassic Reptile Bones, Upper Silesia, Poland.

Fossil biomolecules from an endogenous source were previously identified in Cretaceous to Pleistocene fossilized bones, the evidence coming from molecular analyses. These findings, however, were called into question and an alternative hypothesis of the invasion of the bone by bacterial biofilm was proposed. Herewith we report a new finding of morphologically preserved blood-vessel-like structures enclosing organic molecules preserved in iron-oxide-mineralized vessel walls from the cortical region of nothosaurid and tanystropheid (aquatic and terrestrial diapsid reptiles) bones. These findings are from the Early/Middle Triassic boundary (Upper Roetian/Lowermost Muschelkalk) strata of Upper Silesia, Poland. Multiple spectroscopic analyses (FTIR, ToF-SIMS, and XPS) of the extracted "blood vessels" showed the presence of organic compounds, including fragments of various amino acids such as hydroxyproline and hydroxylysine as well as amides, that may suggest the presence of collagen protein residues. Because these amino acids are absent from most proteins other than collagen, we infer that the proteinaceous molecules may originate from endogenous collagen. The preservation of molecular signals of proteins within the "blood vessels" was most likely made possible through the process of early diagenetic iron oxide mineralization. This discovery provides the oldest evidence of in situ preservation of complex organic molecules in vertebrate remains in a marine environment.

Catalytic Gas-Phase Glycerol Processing over SiO2-, Cu-, Ni- and Fe- Supported Au Nanoparticles.

In this study, we investigated different metal pairings of Au nanoparticles (NPs) as potential catalysts for glycerol dehydration for the first time. All of the systems preferred the formation of hydroxyacetone (HYNE). Although the bimetallics that were tested, i.e., Au NPs supported on Ni, Fe and Cu appeared to be more active than the Au/SiO2 system, only Cu supported Au NPs gave high conversion (ca. 63%) and selectivity (ca. 70%) to HYNE.

Processes of Removing Zinc from Water using Zero-Valent Iron.

Zero-valent iron has received considerable attention for its potential application in the removal of heavy metals from water. This paper considers the possibility of removal of zinc ions from water by causing precipitates to form on the surface of iron. The chemical states and the atomic concentrations of solids which have formed on the surface of zero-valent iron as well as the type of the deposited polycrystalline substances have been analyzed with the use of X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), respectively. The BET surface area, the pH at point of zero charge (pHPZC), the ORP of the solutions, and the pH and chemical concentrations in the solutions have also been measured. Furthermore, the paper also considers the possibility of release of zinc from the precipitates to demineralised water in changing physicochemical and chemical conditions. In a wide range of pH values, Zn x Fe3 - x O4 (where x ≤ 1) was the main compound resulting from the removal of zinc in ionic form from water. In neutral and alkaline conditions, the adsorption occurred as an additional process.

Ni-Supported Pd Nanoparticles with Ca Promoter: A New Catalyst for Low-Temperature Ammonia Cracking.

In this paper we report a new nanometallic, self-activating catalyst, namely, Ni-supported Pd nanoparticles (PdNPs/Ni) for low temperature ammonia cracking, which was prepared using a novel approach involving the transfer of nanoparticles from the intermediate carrier, i.e. nano-spherical SiO2, to the target carrier technical grade Ni (t-Ni) or high purity Ni (p-Ni) grains. The method that was developed allows a uniform nanoparticle size distribution (4,4±0.8 nm) to be obtained. Unexpectedly, the t-Ni-supported Pd NPs, which seemed to have a surface Ca impurity, appeared to be more active than the Ca-free (p-Ni) system. A comparison of the novel PdNPs/Ni catalyst with these reported in the literature clearly indicates the much better hydrogen productivity of the new system, which seems to be a highly efficient, flexible and durable catalyst for gas-phase heterogeneous ammonia cracking in which the TOF reaches a value of 2615 mmolH2/gPd min (10,570 molNH3/molPd(NP) h) at 600°C under a flow of 12 dm3/h (t-Ni).

Conversion of Natural Tannin to Hydrothermal and Graphene-Like Carbons Studied by Wide-Angle X-ray Scattering.

The atomic structure of carbon materials prepared from natural tannin by two different techniques, high-temperature pyrolysis and low-temperature hydrothermal carbonization, was studied by wide-angle X-ray scattering. The obtained diffraction data were converted to the real space representation in the form of pair distribution functions. The X-ray photoelectron spectroscopy measurements provided information about the chemical state of carbon in tannin-based materials that was used to construct final structural models of the investigated samples. The results of the experimental data in both reciprocal and real spaces were compared with computer simulations based on the PM7 semiempirical quantum chemical method. Using the collected detailed information, structural models of the tannin-based carbons were proposed. The characteristics of the investigated materials at the atomic level were discussed in relation to their preparation method. The rearrangement of the tannin molecular structure and its transformation to graphene-like structure was described. The structure of tannin-based carbons pyrolyzed at 900 °C exhibited coherently scattering domains about 20 Å in size, consisting of two defected atomic layers and resembling a graphene-like arrangement.

Relevance of the poly(ethylene glycol) linkers in peptide surfaces for proteases assays.

Poly(ethylene glycol)s (PEGs) with different lengths were used as linkers during the preparation of peptide surfaces for protease detection. In the first approach, the PEG monolayers were prepared using a "grafting to" method on 3-aminopropyltrietoxysilane (APTES)-modified silicon wafers. Protected peptides with a fluorescent marker were synthesized by Fmoc solid phase synthesis. The protected peptide structures enabled their site-specific immobilization onto the PEG surfaces. Alternatively, the PEG-peptide surface was obtained by immobilizing a PEG-peptide conjugate directly onto the modified silicon wafer. The surfaces (composition, grafting density, hydrophilicity, and roughness) were characterized by time-of-flight-secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), contact angle (CA), and atomic force microscopy (AFM). Introducing the PEG linker between the peptide and surface increased their resistance toward nonspecific protein adsorption. The peptide surfaces were examined as analytical platforms to study the action of trypsin as a representative protease. The products of the enzymatic hydrolysis were analyzed by fluorescence spectroscopy, electrospray ionization-mass spectrometry (ESI-MS), and ToF-SIMS. Conclusions about the optimal length of the PEG linker for the analytical application of PEG-peptide surfaces were drawn. This work demonstrates an effective synthetic procedure to obtain PEG-peptide surfaces as attractive platforms for the development of peptide microarrays.

Detection of Fe2+ valence states in Fe doped SrTiO3 epitaxial thin films grown by pulsed laser deposition.

We present an X-ray absorption spectroscopy study on Fe-doped SrTiO3 thin films grown by pulsed laser deposition. The Fe L2,3 edge spectra are recorded for doping concentrations from 0-5% after several annealing steps at moderate temperatures. The Fe valence state is determined by comparison with an ilmenite reference sample and calculations according to the charge transfer multiplet model. We found clear evidence of Fe(2+) and Fe(3+) oxidation states independently of the doping concentration. The Fe(2+) signal is enhanced at the surface and increases after annealing. The Fe(2+) configuration is in contrast to the mixed Fe(3+)/Fe(4+) valence state in bulk material and must be explained by the specific defect structure of the thin films due to the kinetically limited growth which induces a high concentration of oxygen vacancies.

Chemical, corrosion and topographical analysis of stainless steel implants after different implantation periods.

The aim of this work is to examine the corrosion properties, chemical composition, and material-implant interaction after different periods of implantation of plates used to correct funnel chest. The implants are made of 316L stainless steel. Examinations are carried out on three implants: new (nonimplanted) and two implanted for 29 and 35 months. The corrosion study reveals that in the potential range that could occur in the physiological condition the new bar has the lowest current density and the highest corrosion potential. This indicates that the new plate has the highest corrosion resistance and the corrosion resistance could be reduced during implantation by the instruments used during the operation. XPS analysis reveals changes in the surface chemistry. The longer the implantation time the more carbon and oxygen are observed and only trace of elements such as Cr, Mo are detected indicating that surface is covered by an organic layer. On some parts of the implants whitish tissue is observed: the thickness of which increased with the time of implantation. This tissue was identified as an organic layer; mainly attached to the surface on the areas close to where the implant was bent to attain anatomical fit and thus where the implant has higher surface roughness. The study indicates that the chest plates are impaired by the implantation procedure and contact with biological environment. The organic layer on the surface shows that the implant did not stay passive but some reactions at the tissue-implant interface occurred. These reactions should be seen as positive, as it indicates that the implants were accepted by the tissues. Nevertheless, if the implants react, they may continue to release chromium, nickel, and other harmful ions long term as indicated by lower corrosion resistance of the implants following implantation.