特种氧化铝负载氧化钛作为异丙醇还原肉桂醛的高性能催化剂

肉桂醇在香料、香精以及医药等诸多高端领域有着重要应用,常通过肉桂醛加氢法制备.由于热力学上肉桂醛中C=C–C=O官能团的C=C双键加氢比C=O双键更有优势,因此不管是从学术角度还是工业生产角度来看,高选择性还原C=O基团都是一项极具挑战的任务.肉桂醛加氢反应的副产物苯丙醛以及苯丙醇的生成不仅导致肉桂醇收率降低,而且大大增加分离纯化成本,因此设计并制备出有利于C=O官能团高选择性氢化的高效催化剂具有重要意义.Meer-wein-Ponndorf-Verley(MPV)反应以异丙醇为氢供体,是一种可选择加氢C=C–C=O中C=O官能团的反应.目前用于MPV还原的催化剂(均相或多相)在实际应用中通常选择性不高,使得目标产物得率低且分离成本高.本文报道了负载于一种特殊氧化铝表面的氧化钛催化剂(记为TiOx/γ-Al2O3-nt),其催化肉桂醛经MPV还原为肉桂醇的催化性能优异,表征结果发现该特殊氧化铝可导致表面氧化钛呈较高比例的低价钛物种高度分散状态,从而成为一种高效的肉桂醛MPV还原催化剂.TEM结果表明,这种特殊氧化铝和普通氧化铝在形貌上有很大差别,具有比较规整的一维纳米粒子形貌.综合XRD,TEM,Raman以及H/D同位素交换表征结果,可得到氧化钛高度分散在氧化铝表面的结论.原位XPS结果表明,Ti-Ox/γ-Al2O3-nt催化剂表面具有较高浓度的Ti(III)物种,而以普通氧化铝为载体的催化剂TiOx/γ-Al2O3-c在相同的还原条件下其表面Ti(Ⅲ)物种浓度较低,这种差异的来源是具有规整形貌的一维纳米氧化铝提供了更加均匀的表面位点使得表面高度分散的氧化钛容易被还原为低价态.NH3-TPD结果表明,TiOx/γ-Al2O3-nt催化剂具有高的L酸酸量.肉桂醛MPV还原反应结果显示,表面负载氧化钛的特殊氧化铝(TiOx/γ-Al2O3-nt)是一种非常高效的催化剂,具有很高的目标产物肉桂醇的选择性,几乎观察不到副产物的生成,多次套用实验结果也证实该催化剂具有良好的稳定性.该催化剂的高性能可归纳为以下两个方面的原因:一方面,L酸是MPV还原反应的活性中心,该催化剂具有高的L酸酸量,因此转化率高;另一方面,其表面较高浓度的Ti(III)物种可以使肉桂醛以垂直吸附模式(吸附终端为C=O)在催化剂表面吸附,这种吸附模式可以高选择性地还原为目标产物肉桂醇,因此同时具有很高的选择性.     

Plasma polymerized allylamine coated quartz particles for humic acid removal

Nowadays, titanium is a very commonly used biomaterial for the preparation of orthopedic and dental implants. Its excellent mechanical and biochemical bulk properties are nevertheless counterbalanced by its propensity to long term degradation in physiological conditions and its weak osseointegrative capacities. In this context, surface modifications can significantly hinder titanium weaknesses. The approach considered in this work relies on the preparation of thin composite coatings based on tantalum oxide and carbon nanotubes by sol-gel process. Tantalum is particularly interesting for its high biocompatibility and bioactivity, as well as its strong resistance to bio-corrosion. Carbon nanotubes are exploited to reinforce the compactness and homogeneity of the coatings, and can act as a favorable factor to strengthen the interaction with bone components by biomimicry. The composite layers are further modified with specific organophosphonic acid molecular films, able to chemically bind the tantalum oxide surface and improve the hydroxyapatite formation process. The characteristics and the qualities of these hybrid inorganic/organic coatings are evaluated by XPS, SEM, TEM, peeling tests, contact angle measurements, and electrochemical characterizations (free potential, polarization curves).     

Organic pigment particles coated with titania via sol-gel process

This paper presented a novel method for the organic pigment coated with titania to improve the weatherability and dispersion ability in waterborne system. The organic pigment was first orderly adsorbed by two kinds of electrolyte: poly(sodium 4-styrenesulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC), then coated by titania via sol-gel process from titanium n-butoxide (TBOT). The effects of the numbers of polyelectrolyte layer, water content, and TBOT content on the morphology, particle size, surface element composition, porosity and pore size, thermal stability, and UV shielding property of the organic pigment were systematically investigated. It was found that only two layers of electrolyte adsorption and one-step coating of titania could obviously enhance the UV shielding property even thermal stability of the organic pigment. The thickness of the titania layer could be easily tailored by TBOT content.     

Development of dextran-derivative arrays to identify physicochemical properties involved in biofouling from serum

To control protein adsorption on surfaces, low-fouling polymer coatings such as poly(ethylene oxide) (PEG or PEO) and polysaccharides are used. Their ability to resist protein adsorption is related to the layer structure, hence the immobilization mode. A polymer array technology was developed to study the structural diversity of carboxymethyl dextran (CMD) layers, whose immobilization conditions were varied. CMD arrays were analyzed by X-ray photoelectron spectroscopy (XPS) and by atomic force microscopy (AFM) colloidal probe force measurements. Serum protein adsorption was studied directly on the CMD arrays using surface plasmon resonance (SPR) microscopy. Physicochemical characterization revealed that pinning density regulates surface coverage and the amount of adsorbed molecules, and that salt concentration influences the surface structure of the charged polymer, forming extended or short layers. Protein adsorption experiments from serum showed that repulsive CMD layers are dense, with extended flexible chains. The present study underlines the usefulness of polymer arrays to study structural diversity of thin graft layers and to relate their physicochemical properties to their resistance to nonspecific protein adsorption.     

Agarose template for the fabrication of macroporous metal oxide structures

Agarose gels have been applied as templates for the formation of macroporous metal oxide structures. The preparation of the agarose template is extremely simple, and with variation of the agarose content, control over morphology is demonstrated: The average pore size decreases from 180 to 55 nm and the surface area increases from 238 to 271 m2 g(-1) with increasing agarose content in the gel. The gelling temperature was also found to influence the final template morphology. Conducting sol-gel chemistry within the template structure followed by removal of the template by heating to 450 degrees C gives porous inorganic oxides. The technique has been demonstrated for the oxides of titanium, zirconium, niobium, and tin. The final morphology of the metal oxide is homogeneous and results from a coating of the agarose structure. The pore diameter decreased and the specific surface area of the titanium dioxide materials increased from 28 to 66 m2 g(-1) as the agarose content in the template is increased from 0.5 to 5.0 wt%. The overall pore size and surface area are lower than the original gel due to shrinkage occurring with the sol-gel process, as well as crystallization and a loss of microporosity in the final material.     

Comparative analysis of the composition, structure, and catalytic activity of the NiO-CuO-TiO2 on Titanium and NiO-CuO-Al2O3 on aluminum composites

The catalytically active oxide structures based on Al and Ti prepared by plasma-electrolytic oxidation (PEO) and additionally modified by impregnation with an aqueous solution of nickel and copper nitrates followed by annealing were studied. The oxide film-metal composites were studied using X-ray diffraction and X-ray spectroscopic analysis, X-ray electron spectroscopy, and electron microscopy. The catalytic activity of the composites in the reaction of CO oxidation was studied. In spite of differences in the elemental composition and morphology, the initial oxide layers on Al and Ti were comparable in terms of activity. Microgranules of size ～ 1 µm and formations from tens to hundreds of nanometers in size were detected on the surface of PEO layers. The modified layers contained crystalline CuO, NiO, and Al₂O₃ or TiO₂ phases. The surface layers of the modified structures about 3 nm in thickness on AMg5 aluminum alloy and VT1-0 titanium had the same elemental composition but exhibited different activity in the reaction of CO oxidation to CO₂.     

A spin-coated TiOx/Pt nanolayered anodic catalyst for the direct formic acid fuel cells

The CO poisoning of the platinum anodic catalyst which typically functions the catalytic deterioration of the direct formic acid fuel cells could be minimized with a simple modification for Pt with titanium oxide. The fabrication scheme involved the spin-coating of a Ti precursor onto a Pt thin layer that was physically sputtered onto a Si substrate. The whole assembly was subjected to a post-annealing processing to produce the TiOx layer (60 nm) in a porous structure (mostly Anatase) atop of the Pt surface. The porous nature of the TiOx layer permitted the participation of Pt in the electrocatalysis of the formic acid electro–oxidation (FAO). The annealing temperature was critical in identifying the catalytic efficiency and durability of the catalyst toward the FAO. Interestingly, if compared to bare-Pt substrates, the TiOx-modified catalysts could successfully steer the FAO toward the direct dehydrogenation (favorable and less energetic) pathway with more than an order of magnitude increase in the catalytic activity. It also provided a great opportunity for the mitigation of poisoning CO; concurrently with a lowering (~0.3 V) in the onset potential of the FAO. The scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction spectroscopy (XRD), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques were all combined to evaluate, respectively, the catalyst’s morphology, composition, crystal structure and activity and further to understand the role of the TiOx in the catalytic enhancement.     

One-pot preparation of silica-supported hybrid immobilized metal affinity adsorbent with macroporous surface based on surface imprinting coating technique combined with polysaccharide incorporated sol--gel process

A simple and reliable one-pot approach using surface imprinting coating technique combined with polysaccharide incorporated sol-gel process was established to synthesize a new organic-inorganic hybrid matrix possessing macroporous surface and functional ligand. Using mesoporous silica gel being a support, immobilized metal affinity adsorbent with a macroporous shell/mesoporous core structure was obtained after metal ion loading. In the prepared matrix, covalently bonded coating and morphology manipulation on silica gel was achieved by using one-pot sol-gel process starting from an inorganic precursor, -glycidoxypropyltrimethoxysiloxane (GPTMS), and a functional biopolymer, chitosan (CS) at the atmosphere of imprinting polyethylene glycol (PEG). Self-hydrolysis of GPTMS, self-condensation, and co-condensation of silanol groups (Si-OH) from siloxane and silica gel surface, and in situ covalent cross-linking of CS created an orderly coating on silica gel surface. PEG extraction using hot ammonium hydroxide solution gave a chemically and mechanically stabilized pore structure and deactivated residual epoxy groups. The prepared matrix was characterized by using X-ray energy dispersion spectroscopy (EDX), scanning electron microscopy (SEM) and mercury intrusion porosimetry. The matrix possessed a high capacity for copper ion loading. Protein adsorption performance of the new immobilized metal affinity adsorbent was evaluated by batch adsorption and column chromatographic experiment using bovine serum albumin (BSA) as a simple model protein. Under the optimized coating conditions, the obtained macroporous surface resulted in a fast kinetics and high capability for protein adsorption, while the matrix non-charged with metal ions offered a low non-specific adsorption.     

Electron microscopic characterization of SrTiO3 films obtained by anodic spark deposition

Crystalline strontium titanate layers were deposited on titanium anodes from Sr(OH)₂ aqueous electrolyte solutions by a plasmachemical-electrochemical process of anodic spark deposition. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) have been used to study the properties of the polycrystalline material. Strontium titanate was deposited on the titanium anode surface as a ceramic layer from an aqueous electrolyte. The typical pore structure morphology of the anodic spark deposit (ASD) was characterized by SEM as well as fractures which provide an intimate contact between layer and substrate. XRD-study showed that the layers are composed of a mixture of SrTiO₃ and TiO₂.     

Nickel- and copper-containing oxide films on titanium

We have studied the composition and structure of films 20–30 μm thick prepared by plasmaassisted electrochemical oxidation (PEO) and additionally modified by impregnation in aqueous solutions of nickel and copper nitrates and then annealed. The investigative tools used were powder X-ray diffraction, electron probe microanalysis (EPMA), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy. Unmodified film/titanium composites have a certain catalytic activity in CO oxidation to CO₂ at temperatures above 300°C; for modified layers, these temperatures are noticeably higher. Modification influences the surface structure, relief, and elemental composition. Relations between the composition and catalytic properties of the oxide layers are discussed.     

Characterization of oxide layers on Ti6Al4V and titanium by streaming potential and streaming current measurements

Titanium and titanium alloys (e.g. Ti6Al4V) are increasingly used as medical implant materials in a wide variety of applications. So far, many surface properties of the passive layer considered to explain interactions with biological tissues are deduced from those of the crystalline phases of titanium dioxide (anatase, rutile, brookite), but do not necessarily correspond to those of naturally formed amorphous passive layers. We report on streaming potential and streaming current measurements on oxide layers on Ti6Al4V and Ti, carried out using a microslit electrokinetic set-up (MES) and a commercial electrokinetic analyzer (EKA, PAAR). Passive and anodic oxide layers on Ti6Al4V, as well as passive layers on titanium sputtered on glass, were investigated in this study. Isoelectric points (IEP) of ≈4.4 were found for all oxide layers. The IEP of the air-formed passive layer on Ti6Al4V did not depend on the KCl concentration. Hence, it was concluded that IEP is here identical to the point of zero charge (pzc). Controversially, the charge formation process seems to depend on the chloride ion concentration in the neutral and basic pH region.     

One-pot preparation and uranyl adsorption properties of hierarchically porous zirconium titanium oxide beads using phase separation processes to vary macropore morphology

A simple and engineering friendly one-step process has been used to prepare zirconium titanium mixed oxide beads with porosity on multiple length scales. In this facile synthesis, the bead diameter and the macroporosity can be conveniently controlled through minor alterations in the synthesis conditions. The precursor solution consisted of poly(acrylonitrile) dissolved in dimethyl sulfoxide to which was added block copolymer Pluronic F127 and metal alkoxides. The millimeter-sized spheres were fabricated with differing macropore dimensions and morphology through dropwise addition of the precursor solution into a gelation bath consisting of water (H(2)O beads) or liquid nitrogen (LN(2) beads). The inorganic beads obtained after calcination (550 °C in air) had surface areas of 140 and 128 m(2) g(-1), respectively, and had varied pore architectures. The H(2)O-derived beads had much larger macropores (5.7 μm) and smaller mesopores (6.3 nm) compared with the LN(2)-derived beads (0.8 μm and 24 nm, respectively). Pluronic F127 was an important addition to the precursor solution, as it resulted in increased surface area, pore volume, and compressive yield point. From nonambient XRD analysis, it was concluded that the zirconium and titanium were homogeneously mixed within the oxide. The beads were analyzed for surface accessibility and adsorption rate by monitoring the uptake of uranyl species from solution. The macropore diameter and morphology greatly impacted surface accessibility. Beads with larger macropores reached adsorption equilibrium much faster than the beads with a more tortuous macropore network.     

In-situ investigation of the adsorption of globular model proteins on stimuli-responsive binary polyelectrolyte brushes

Binary brushes constituted from two incompatible polymers can be used in the form of ultrathin polymeric layers as a versatile tool for surface engineering to tune physicochemical surface characteristics such as wettability, surface charge, chemical composition, and morphology and furthermore to create responsive surface properties. Mixed brushes of oppositely charged weak polyelectrolytes represent a special case of responding surfaces that are sensitive to changes in the pH value of the aqueous environment and therefore represent interesting tools for biosurface engineering. The polyelectrolyte brushes used for this study were composed of two oppositely charged polyelelctrolytes poly(2-vinylpyridine) (P2VP) and poly(acrylic acid) (PAA). The in-situ properties and surface characteristics such as as surface charge, surface tension, and extent of swelling of these brush layers are functions of the pH value of the surrounding aqueous solution. To test the behavior of the mixed polylelctrolyte brushes in contact with biosystems, protein adsorption experiments with globular model proteins were performed at different pH values and salt concentrations (confinement of counterions) of the buffer solutions. The influence of the pH value, buffer salt concentration, and isoelectric points (IEP) of the brush and protein on the adsorbed amount and the interfacial tension during protein adsorption as well as the protein adsorption mechanism postulated in reference to recently developed theories of protein adsorption on polyelectrolyte brushes is discussed. In the salted regime, protein adsorption was found to be similar to the often-described adsorption at hydrophobic surfaces. However, in the osmotic regime the balance of electrostatic repulsion and a strong entropic driving force, "counterion release", was found to be the main influence on protein adsorption.     

Creation of high-refractive-index amorphous titanium oxide thin films from low-fractal-dimension polymeric precursors synthesized by a sol-gel technique with a hydrazine monohydrochloride catalyst

Amorphous titanium dioxide (TiO(2)) thin films exhibiting high refractive indices (n ≈ 2.1) and high transparency were fabricated by spin-coating titanium oxide liquid precursors having a weakly branched polymeric structure. The precursor solution was prepared from titanium tetra-n-butoxide (TTBO) via the catalytic sol-gel process with hydrazine monohydrochloride used as a salt catalyst, which serves as a conjugate acid-base pair catalyst. Our unique catalytic sol-gel technique accelerated the overall polycondensation reaction of partially hydrolyzed alkoxides, which facilitated the formation of liner polymer-like titanium oxide aggregates having a low fractal dimension of ca. (5)/(3), known as a characteristic of the so-called "expanded polymer chain". Such linear polymeric features are essential to the production of highly dense amorphous TiO(2) thin films; mutual interpenetration of the linear polymeric aggregates avoided the creation of void space that is often generated by the densification of high-fractal-dimension (particle-like) aggregates produced in a conventional sol-gel process. The mesh size of the titanium oxide polymers can be tuned either by water concentration or the reaction time, and the smaller mesh size in the liquid precursor led to a higher n value of the solid thin film, thanks to its higher local electron density. The reaction that required no addition of organic ligand to stabilize titanium alkoxides was advantageous to overcoming issues from organic residues such as coloration. The dense amorphous film structure suppressed light scattering loss owing to its extremely smooth surface and the absence of inhomogeneous grains or particles. Furthermore, the fabrication can be accomplished at a low heating temperature of <80 °C. Indeed, we successfully obtained a transparent film with a high refractive index of n = 2.064 (at λ = 633 nm) on a low-heat-resistance plastic, poly(methyl methacrylate), at 60 °C. The result offers an efficient route to high-refractive-index amorphous TiO(2) films as well as base materials for a wider range of applications.     

Surface functionalized titanium thin films: zeta-potential, protein adsorption and cell proliferation

The relationship between electric charge at a material surface and protein adsorption is essential to understand the mechanism of biological integration of materials with tissues. This study investigated the influence of titanium thin films' surface chemistry and surface electric charge (zeta-potential) properties on protein adsorption and cell proliferation. Titanium thin films were surface functionalized with different functional end groups, such as -CH=CH2, -NH2 and -COOH groups in order to produce surfaces with a variety of electric charge properties. The chemical compositions, electric charges and wettability were investigated by using X-ray photoelectron spectroscopy (XPS), zeta-potential measurements and water contact angle measurements, respectively. XPS revealed the surface functionalization of titanium films with -CH=CH2, -NH2, and -COOH groups, which were converted from -CH=CH2 groups. Ti-COOH samples showed the lowest water contact angles and zeta-potential compared to all other samples investigated in this study. NH2-terminated titanium films displayed intermediate contact angles of 70.3+/-2.5 degrees . Fibrinogen adsorption on titanium films and surface functionalized titanium films were investigated in this study. Ti-COOH samples displayed a lower protein adsorption than all other groups, such as NH2-, -CH=CH2-terminated titanium thin films. A tendency that the lower zeta-potential of the samples, the lower the protein adsorption at their surfaces was observed. In vitro cell proliferation tests were also performed on the different surface functionalized titanium films. NH2-terminated titanium films displayed good cell proliferation and cell viability tendency. However, a lower cell proliferation on COOH-terminated titanium films was observed compared with NH2-terminated titanium films. This effect was attributed to the difference in protein adsorption of these samples.     

Effects of the grain boundary on phase structure and surface morphology of TiO2 films prepared by MAO technology

Some porous titanium dioxide (TiO₂) films were prepared on flexible substrates by the method of micro‐arc oxidation (MAO) combined with magnetron sputtering (MS). The original material of MAO was Ti films prepared by MS, which was composed of columnar crystals with a diameter of less than 150 nm. The results indicated that the phase of the oxide films was mainly anatase structure, and the pore diameter of the films was about 100–300 nm. However, the phases of the oxide films prepared on Ti plates, which composed of equiaxed crystals with a diameter of 2–5 µm, were anatase and rutile structure. The pore diameter of those films was about 4–10 µm. It was suggested that the changes of the grain boundary structure of the original material could have a significant impact on the phase structure and surface morphology of the resultant TiOx films. Copyright © 2011 John Wiley & Sons, Ltd.     

Adsorption complexes ‘zeolite–cationic surfactant’: properties and surface activity in a polymer composite material based on ultra-high-molecular-weight polyethylene

We investigated the adsorption of the cationic surfactant cetyltrimethylammonium bromide (CTAB) to zeolite from premicellar and micellar solutions, as well as some properties of the organically modified zeolite surface and the nature of its interfacial interaction with ultra-high-molecular-weight polyethylene (UHMWPE) in a UHMWPE-based polymer composite material (PCM). The formation mechanism of mono- and bimolecular adsorption layers of cetyltrimethylammonium cation and bromide anion to the clinoptilolite (Cli) surface was proposed, and the thermodynamic and kinetic characteristics of adsorption were determined. The surface texture of organically modified zeolite was studied by instrumental methods; the thermal stability limits of CTAB adsorption layers to zeolite surface and their decomposition behavior in inert and oxidizing media were established. The evaluation of the deformation and strength properties, the study of the supramolecular structure, and the calculation of the thermodynamic and kinetic parameters of the PCM crystallization process revealed that the filing with organically modified Cli increases the UHMWPE surface activity and improves their compatibility.     

Cracking and Decohesion of Sol-Gel Hybrid Coatings on Metallic Substrates

Thin film coatings based on organically modified silanes were synthesized using sol-gel technology. Various mixtures of tetraethoxysilane and glycidoxypropyltrimethoxysilane precursors were used to produce sol-gel coatings on as-received and thermally oxidised copper, aluminium and titanium substrates. The mechanical properties and adhesion behaviour of the coatings were assessed using nano-indentation and microtensile testing, respectively. The relationship between the film structure and its mechanical response is examined. It is shown that the mechanical properties (hardness and Young's modulus) of the coatings are influenced dramatically by the organic substituent and the presence of an oxide layer thermally grown on the substrate material prior to deposition plays an important role on the film/substrate adhesion behaviour.     

Physicochemical and electrorheological properties of titanium dioxide modified with metal oxides

The properties of electrorheological fluids containing dispersed phase of titanium dioxide nanoparticles prepared via the sol-gel method and modified with metal oxides have been studied. Titanium dioxide has the anatase structure with crystallite sizes of 8–10 nm and a specific surface area of 90–140 m²/g. It has been found that the magnitude of the electrorheological response of the filler is determined by the specific surface area and the content of a modifying component. The strongest electrorheological response has been revealed for titanium dioxide modified with aluminum oxide at an Al content of 6.5–7.0 mol % relative to TiO₂.     

Photocatalytic,phosphorus-doped,anatase oxide layers applicable to titanium implant alloys

Titanium alloys provide excellent corrosion resistance and favorable mechanical properties well suited for a variety of biomaterial applications. The native oxide surface on titanium alloys has been shown to be less than ideal and surface modification is often needed. Previously, an optimized anodization process was shown to form a porous phosphorus-enhanced anatase oxide layer on commercially pure Ti grade 4. The anodized layer was shown to improve osseointegration and to reduce bacteria attachment when photocatalytically activated with UVA preillumination. The primary objective of the present study was to create a similar phosphorus-enhanced anatase oxide layer on series of titanium alloys including commercially pure Ti grade 4, Ti-6Al-7Nb, Ti-6Al-4V ELI, alpha + beta Ti-15Mo, beta Ti-15Mo, and Ti-35Nb-7Zr-5Ta. Phosphorus-enhanced anatase oxide layers were formed on each titanium substrate. Anatase formation was shown to generally increase with oxide thickness, except on substrate alloys containing niobium. Phosphorus uptake was shown to be dependent on the titanium alloy chemistry or microstructure. Anodized layers formed on beta-structured titanium alloys revealed the lowest phosphorus uptake and the most nanosized surface porosity. A methylene blue degradation assay showed anodized layers on commercially pure Ti and both Ti-15Mo alloys to exhibit the highest levels of photocatalytic activity. Given the range of mechanical properties available with the commercially pure Ti and Ti-15Mo alloys, the results of this study indicate the benefits of phosphorus-enhanced anatase oxide coatings may be applicable to a wide variety of biomaterial applications.