Formation of OTS self-assembled monolayers at chemically treated titanium surfaces

Enhanced biocompatibility of titanium implants highly depends on the possibility of achieving high degrees of surface functionalization for a low immune response and/or enhanced mineralization of bioactive minerals, such as hydroxyapatite. In this respect, surface modification with Self Assembled Monolayers (SAMs) has a great potential in delivering artificial surfaces of improved biocompatibility. Herein, the effectiveness of common chemical pre-treatments, i.e. hydrogen peroxide (H₂O₂) and Piranha (H₂SO₄ + H₂O₂), in facilitating surface decontamination and hydroxylation of titanium surfaces to promote further surface functionalization by SAMs is investigated. The quality of the octadecyltrichlorosilane (OTS) based SAM appeared to strongly depend upon the surface morphology, the density and nature of surface hydroxyl sites resulting from the oxidative pre-treatments. Contrary to common belief, no further hydroxylation of the titanium substrate was observed after the selected chemical pre-treatments, but the number of hydroxyl groups available on the surface was decreased as a result of the formation of a titanium oxide layer with a gel-type structure. Further examinations by atomic force microscopy, infrared spectroscopy and X-ray photoelectron spectroscopy also revealed that mild oxidizing conditions were sufficient to remove surface contamination without detrimental effects on surface hydroxylation state and surface roughness. Furthermore, the adsorption of the alkylsiloxane molecules forming the SAM film is believed to proceed through hydrolysis at surface acidic hydroxyl groups rather than randomly. This site dependent adsorption process has significant implications for further functionalization of titanium based implants. It also highlights the difficulty of achieving an OTS based SAM at the surface of titanium and question the quality of SAMs reported at titanium surfaces so far.     

Characterization of the chemically deposited hydroxyapatite coating on a titanium substrate

Bioactive hydroxyapatite (HA) coating on titanium (Ti) implant can be used as a drug delivery device. A controlled release of drug around the implant requires the incorporation of drug into the coating material during the coating process. HA coating was prepared using a two-step procedure in conditions suitable for simultaneous incorporation of the protein-based drug into the coating material. Monetite coating was deposited on Ti substrate in acidic condition followed by the transformation of the monetite coating to HA. X-ray diffraction (XRD) confirmed the formation of the monetite phase at the first step of the coating preparation, which was transformed into HA at the second step. Fourier transform infrared spectroscopy demonstrated typical bands of a crystallized carbonated HA with A- and B-type substitution, which was confirmed by the XRD refinement of the structural parameters. Scanning electron microscope was used to observe the morphology of monetite and HA coatings. Adhesion of the coatings was measured using a scratch tester. The critical shearing stress was found to be 84.20 ± 1.27 MPa for the monetite coating, and 44.40 ± 2.39 MPa for the HA coating.     

Characterization of plasma nitrided pure titanium by X-ray absorption spectroscopy

To date, the exact nature of the plasma nitriding mechanism and the role of energetic particle bombardment are not well understood. The purpose of this work has been to obtain a more detailed knowledge about the evolution of the plasma nitrided surface layer as a function of the energy of the bombarding particles. Nitrided layers were produced at the surface of pure titanium specimens at various flux energies by Intensified Plasma-Assisted Processing (IPAP), a triode plasma technique developed in our laboratory. X-ray Absorption Near Edge Structure (XANES) spectroscopy and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy were used to characterize the local structure of the titanium nitride layers. Cross sections of the processed specimens were studied by Auger electron spectroscopy and electron microscopy. The results showed that increasing flux energy promotes the formation of a well-ordered TiN layer at the surface. Low flux energies produce significantly lower fractions of the TiN phase at the surface, as well as thinner nitrided layers. A structural model was suggested and quantitatively tested based on the XANES and EXAFS measurements.     

Characterization of Mo/Si soft X-ray multilayer mirrors by grazing-incidence small-angle X-ray scattering

The morphology of buried interfaces plays a key role in high performing Mo/Si soft X-ray mirrors. We show that grazing-incidence small-angle X-ray scattering is a highly effective and non-destructive diagnostic technique for analysis of buried interfaces. The parameters of average interface autocorrelation function can be determined unambiguously. Additionally period thickness, roughness of interfaces and an effective number of vertically correlated periods can be extracted. The multilayer mirrors were prepared by e-beam evaporation on heated and unheated substrates, ion beam assisted e-beam evaporation, ion beam sputtering and RF magnetron sputtering. The latter three techniques produce multilayer mirrors with comparable interface roughness. The differences in lateral correlation length and Hurst parameter are found.     

Characterization of chiral interactions using fluorescence anisotropy

This work details a study whereby the characterization of chiral selectors and identification of optimal separation conditions is evaluated by steady-state fluorescence anisotropy measurements. Earlier studies in our laboratory have shown fluorescence anisotropy to be an effective tool in evaluating chiral recognition, and in this study, the feasibility of characterizing chiral separation systems by the technique is evaluated. Four chiral selectors were examined under various conditions to explore correlation between chiral separation ability and differences in the steady-state fluorescence anisotropy of the enantiomers measured under similar conditions. A good correlation between the fluorescence anisotropy data and separation data was observed with R2 values ranging from 0.9279 to 0.9959. The fluorescence anisotropy measurements were examined under conditions that mimicked chiral separation conditions and the feasibility of a priori optimization of chiral separations is discussed.     

Element-specific detection in capillary electrophoresis using X-ray fluorescence spectroscopy

X-ray fluorescence spectroscopy is demonstrated here as a novel, element-specific detector for capillary electrophoresis. Monochromatic 10 keV X-rays from a synchrotron light source are used to excite core electrons, causing emission of characteristic Kalpha X-ray fluorescence (XRF) lines. Using this technique, XRF energies provide elemental identification, while XRF intensities can be used to quantitate the metal composition of each eluent. An X-ray transparent polymer coupling is used to create a window for the on-line, X-ray detection. This coupling contributes no measurable extra-column variance, and electrophoretic mobilities for the metal complexes used as model solutes are highly reproducible. The combination of XRF detection with capillary electrophoresis (CE-XRF) creates the first on-line detection system that is element-specific, nondestructive, and directly applicable to a broad range of applications including nonelectroactive species. CE-XRF is successfully demonstrated here for high binding-constant complexes of Fe(III), Co(II), Cu(II), and Zn(II). Within a single injection, electropherograms are obtained for each element of interest, with the element identity obtained directly from the emission energy. In contrast with ICPMS, this detection technique is directly on-line and does not require volatilization of the eluent. As a result, element-specific detection is not limited by the sample or the buffer volatility or atomization efficiency. Simultaneous XRF and UV absorbance detection can be used to provide an on-line determination of metal/chelate ratios. Although XRF detection limits are presently only in the 0.1 mM (0.5 ng) range, both collection geometry and incident intensity have yet to be optimized. Further optimization is expected to enhance this detection limit by another 2-3 orders of magnitude. As a result, the advent of XRF detection combined with the separating power of CE presents new possibilities for on-line, element-specific analysis.     

Characterization of filled rubbers using small-angle X-ray scattering

It is demonstrated how small-angle X-ray scattering (SAXS) can be used to characterize the structure of fillers such as carbon black and silica both before and after their incorporation into natural rubber. It is found that SAXS has significant advantages over conventional techniques such as gas adsorption or electron microscopy in determining both the size and distribution of sizes of the filler particles. The results are shown to be in good agreement with those obtained using conventional techniques. In addition it is demonstrated that SAXS can be used to characterize the filler particlesin situ enabling the volume fraction, particle size and particle surface area to be determined for a filled rubber and factors such as aggregation to be examined.     

Three-dimensional imaging of human stem cells using soft X-ray tomography

Three-dimensional imaging of human stem cells using transmission soft X-ray tomography (SXT) is presented for the first time. Major organelle types—nuclei, nucleoli, mitochondria, lysosomes and vesicles—were discriminated at approximately 50 nm spatial resolution without the use of contrast agents, on the basis of measured linear X-ray absorption coefficients and comparison of the size and shape of structures to transmission electron microscopy (TEM) images. In addition, SXT was used to visualize the distribution of a cell surface protein using gold-labelled antibody staining. We present the strengths of SXT, which include excellent spatial resolution (intermediate between that of TEM and light microscopy), the lack of the requirement for fixative or contrast agent that might perturb cellular morphology or produce imaging artefacts, and the ability to produce three-dimensional images of cells without microtome sectioning. Possible applications to studying the differentiation of human stem cells are discussed.     

Characterization of hydrothermally treated anodic oxides containing Ca and P on titanium

In this study, the formation of hydroxyapatite (HA) by a series of hydrothermal treatment and properties of the anodic oxide films and HA composite coatings were investigated. Based on the observations using EPMA, SEM, and X-ray diffraction, these needles were suggested to have a HA-like structure and were formed on the anodic oxide surfaces. The formation of these apatite-like needles were either oriented at an angle or formed on porous anodic oxide films. The concentration of Ca and P were enriched in apatite-like needles after hydrothermal treatments, whereas lower concentration of Ca and P were observed on anodic oxide film, particularly around the needles. In conclusion, HA-like needles were formed after hydrothermal treatment at 200 and 300 °C.     

A micro X-ray fluorescence analysis method using polycapillary X-ray optics and grazing exit geometry

Grazing exit X-ray fluorescence (GE-XRF), which has unique advantages in surface and film analysis, is a development of XRF related to total reflection XRF. The combination of polycapillary X-ray optics with total reflection geometry in the detection path allows micro analysis in thin layer characterization. This technique was applied to analyze a series of titanium and iron layers which were deposited on GaAs single crystal by metal vapor vacuum arc ion sources. Thickness and density of the layers result from fitting the experimental data to model calculations, and the information of layer uniformity can be acquired by two-dimensional scan analysis. The GE-XRF method has application for complete layer characterization and process control during the layer deposition.     

Characterization of sintered titanium/hydroxyapatite biocomposite using FTIR spectroscopy

Fourier transform infrared (FTIR) spectroscopy was employed to characterize the phase changes of hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂, HA) in a titanium/HA biocomposite during sintering. The effects of sintering temperature and the presence of Ti on the decomposition of HA were examined. It was observed that pure HA was stable in argon atmosphere at temperatures up to 1,200°C, although the dehydroxylation of pure HA was promoted by the increase in sintering temperature. In the Ti/HA system, on the other hand, the presence of Ti accelerated dehydroxylation and the decomposition of HA was detected at a temperature as low as 800°C. Tetracalcium phosphate (Ca₄P₂O₉, TTCP) and calcium oxide (CaO) were the dominant products of the decomposition, but no tricalcium phosphate (Ca₃(PO₄)₂, TCP) was detected due to phosphorus diffusion and possible reactions during the thermal process. The main decomposed constituents of HA in Ti/HA system at high temperatures (≥1,200°C) would be CaO and amorphous phases.     

Dielectric properties of chemically treated wood

Dielectric properties along the grain for absolutely dried untreated and seven kinds of chemically treated Sitka spruce (Picea sitchensis Carr.) woods were measured. Cole-Cole's circular arc law was applied to the results of the relaxation due to the motions of methylol groups. The following changes were caused by chemical treatments. In polyethylene glycol (PEG) impregnation, the distribution of relaxation times became very narrow, the generalized relaxation time (_m) was considerably decreased, and the relaxation magnitude (₀ – ) was slightly increased. In acetylation, the distribution of relaxation times became very broad, _m was considerably increased, and (₀ – ) was remarkably decreased. In propylene oxide treatment, the distribution of relaxation times became slightly narrow and _m was decreased. _m was slightly decreased in formalization, phenol-formaldehyde (PF) resin treatment and wood methyl methacrylate (MMA) composite. (₀ – ) was decreased in formalization and PF-resin treatment and was hardly changed in wood-MMA composite and heat treatment. The distribution of relaxation times was almost unchanged in formalization, PF-resin treatment, wood-MMA composite and heat treatment.     

Thickness determination of ultrathin metal films using the X-ray fluorescence technique

The X-ray fluorescence technique was used to determine the thickness of single-layered, double-layered and triple-layered films of copper, bismuth and gold on mylar substrates. An annular ¹⁰⁹Cd X-ray source of 5 mCi was used to excite hte characteristic X-rays. The background was much lower as well as flat in the present study in comparison with our earlier results an ²⁴¹Am exciter source. This resulted in a downward extension of the lower limit of thickness measurement of thin films coupled with an improved accuracy.     

Characterization of reinforced chemically bonded ceramics

Two different approaches were taken to increase the flexural strength of a chemically bonded ceramic (CBC) composite material. In the first method, poly-(p-phenylene terephthalamide) (Kevlar 29) fibers were subjected to surface modification by alkaline hydrolysis, and these surface-modified fibers were used as a reinforcing agent for the CBC composite, at a level of 0·2% (w/w). In the second approach, up to 5% (dry wt) of poly(acrylic acid) was added as a water-reducing plasticizer to the mixture, in an effort to decrease the void volume of the cementitious composite. Several variations on each of these two methods were also tested, including the use of different high-modulus fibers and other water-soluble polymers. Test bars made from the different compositions were subjected to mechanical testing, and the microstructure of the fracture surfaces was examined by scanning electron microscopy. Improvements in flexural behavior were found for both cases.     

Defining the nanostructured morphology of triblock copolymers using resonant soft X-ray scattering

The morphologies of a poly(1,4-isoprene)-block-polystyrene-block-poly(2-vinyl pyridine) (IS2VP) copolymer were investigated using resonant soft X-ray scattering (RSoXS) together with scanning force microscopy, small-angle X-ray scattering, and electron microscopy. Differences in the nanoscopic morphologies in the bulk and thin film samples were observed arising from the competition between segmental interactions between the blocks and the substrate and the surface energies of each block. Using soft X-rays at selected photon energies to isolate the scattering contribution from different polymer blocks, RSoXS unambiguously defined the complex morphology of the triblock copolymer. In the bulk sample, two nested, hexagonal arrays of P2VP and PI cylindrical microdomains residing in the PS matrix were observed. The cylindrical microdomains of one component were found to be located at the interstitial sites of the hexagonal array of the other component that has the larger d spacing. In solvent-annealed thin films with 40 nm in thickness, a hexagonal array of core-shell microdomains of P2VP cores with PS shells that reside in a PI matrix were observed.     

Biosorption of Cr(III) using in natura and chemically treated tropical peats

The physicochemical characteristics of three Brazilian peats were investigated using elemental analysis, scanning electron microscopy (SEM), X-ray diffractometry (XRD) and studies of Cr(III) biosorption based on adsorption isotherms. Adsorption of Cr(III) by in natura peat from Santo Amaro das Brotas (Sergipe State) was much greater than by peats from either Ribeir?o Preto (S?o Paulo State) or Itabaiana (Sergipe State), with adsorption capacities (q) of 4.90+/-0.01, 1.70+/-0.01 and 1.40+/-0.01 mg g(-1), respectively. Pre-treatments with HCl and NaOH+HCl reduced adsorption by the Santo Amaro das Brotas peat, showing that adsorption efficiency was associated with the amount of organic matter present. Conversely, increase in the mineral content following pre-treatment increased adsorption of Cr(III) by the Ribeir?o Preto and Itabaiana peats. Highest adsorption (retention >95.0%) was achieved at equilibrium pH 4.0 using the Santo Amaro das Brotas peat. Experimental data for the adsorption of Cr(III) from aqueous solution onto this peat were fitted to the Langmuir equation, from which an equilibrium adsorption capacity, q(max), of 5.60 mg g(-1) was obtained, which was close to the experimentally determined value.