Biofunctionalization strategies on tantalum-based materials for osseointegrative applications.

The use of tantalum as biomaterial for orthopedic applications is gaining considerable attention in the clinical practice because it presents an excellent chemical stability, body fluid resistance, biocompatibility, and it is more osteoconductive than titanium or cobalt-chromium alloys. Nonetheless, metallic biomaterials are commonly bioinert and may not provide fast and long-lasting interactions with surrounding tissues. The use of short cell adhesive peptides derived from the extracellular matrix has shown to improve cell adhesion and accelerate the implant's biointegration in vivo. However, this strategy has been rarely applied to tantalum materials. In this work, we have studied two immobilization strategies (physical adsorption and covalent binding via silanization) to functionalize tantalum surfaces with a cell adhesive RGD peptide. Surfaces were used untreated or activated with either HNO3 or UV/ozone treatments. The process of biofunctionalization was characterized by means of physicochemical and biological methods. Physisorption of the RGD peptide on control and HNO3-treated tantalum surfaces significantly enhanced the attachment and spreading of osteoblast-like cells; however, no effect on cell adhesion was observed in ozone-treated samples. This effect was attributed to the inefficient binding of the peptide on these highly hydrophilic surfaces, as evidenced by contact angle measurements and X-ray photoelectron spectroscopy. In contrast, activation of tantalum with UV/ozone proved to be the most efficient method to support silanization and subsequent peptide attachment, displaying the highest values of cell adhesion. This study demonstrates that both physical adsorption and silanization are feasible methods to immobilize peptides onto tantalum-based materials, providing them with superior bioactivity.

Quasi-phase-matched second-harmonic Talbot self-imaging in a 2D periodically-poled LiTaO3 crystal.

We demonstrate the improved second-harmonic Talbot self-imaging through the quasi-phase-matching technique in a 2D periodically-poled LiTaO(3) crystal. The domain structure not only composes a nonlinear optical grating which is necessary to realize nonlinear Talbot self-imaging, but also provides reciprocal vectors to satisfy the phase-matching condition for second-harmonic generation. Our experimental results show that quasi-phase-matching can improve the intensity of the second-harmonic Talbot self-imaging by a factor of 21.

Features of randomized electric-field assisted domain inversion in lithium tantalate.

We report on bulk and guided-wave second-harmonic generation via random Quasi-Phase-Matching in Lithium Tantalate. By acquiring the far-field profiles at several wavelengths, we extract statistical information on the distribution of the quadratic nonlinearity as well as its average period, both at the surface and in the bulk of the sample. By investigating the distribution in the two regions we demonstrate a non-invasive approach to the study of poling dynamics.

Ta3N5 nanotube arrays for visible light water photoelectrolysis.

Tantalum nitride (Ta3N5) has a band gap of approximately 2.07 eV, suitable for collecting more than 45% of the incident solar spectrum energy. We describe a simple method for scale fabrication of highly oriented Ta3N5 nanotube array films, by anodization of tantalum foil to achieve vertically oriented tantalum oxide nanotube arrays followed by a 700 degrees C ammonia anneal for sample crystallization and nitridation. The thin walled amorphous nanotube array structure enables transformation from tantalum oxide to Ta3N5 to occur at relatively low temperatures, while high-temperature annealing related structural aggregation that commonly occurs in particle films is avoided. In 1 M KOH solution, under AM 1.5 illumination with 0.5 V dc bias typical sample (nanotube length approximately 240 nm, wall thickness approximately 7 nm) visible light incident photon conversion efficiencies (IPCE) as high as 5.3% were obtained. The enhanced visible light activity in combination with the ordered one-dimensional nanoarchitecture makes Ta3N5 nanotube arrays films a promising candidate for visible light water photoelectrolysis.

Cavity-enhanced generation of 6 W cw second-harmonic power at 532 nm in periodically-poled MgO:LiTaO3.

We report on efficient cw high-power second harmonic generation in a periodically poled LiTaO3 crystal placed in a resonant enhancement cavity. We tested three configurations, differing in the coupling mirror reflectivity, and a maximum conversion efficiency of about 76%, corresponding to 6.1 W of green light with 8.0 W of fundamental power, was achieved. This is, to the best of our knowledge, the highest cw power ever reported using a periodically-poled crystal in an external cavity. We observed photo-thermal effect induced by photon absorption at the mirrors and in the crystal, which however does not affect stable operation of the cavity. A further effect arises for two out of the three configurations, at higher values of the input power, which degrades the performance of the locked cavity. We suggest this effect is due to the onset of competing nonlinearities in the same crystal.

High energy quasi-phase matched optical parametric oscillation using Mg-doped congruent LiTaO(3) crystal.

We report on high energy optical parametric oscillation of 118 mJ output with ~70% slope efficiency in 10 ns duration of 30 Hz operation by using Mg-doped congruent composition LiTaO(3) (MgLT). The periodically poled MgLT device with ~30 microm period for quasi-phase matching (QPM) in 5-mm-thick crystal are prepared. MgLT crystal could become a candidate for high-energy and higher durability material of QPM device, compared to conventional Mg-doped congruent composition LiNbO(3).

Compact high-power red-green-blue laser light source generation from a single lithium tantalate with cascaded domain modulation.

1W quasi-white-light source has been generated from a single lithium tantalate with cascaded domain modulation. The quasi-white-light is combined by proper proportion of the red, green and blue laser light. The red and the blue result from a compact self-sum frequency optical parametric oscillation when pumped by a single green laser. The efficiency of quasi-white-light from the green pump reaches 27%. This compact design can be employed not only as a stable and powerful RGB light source but also an effective blue laser generator.

A Novel High-Visibility Radiopaque Tantalum Marker for Biliary Self-Expandable Metal Stents.

Background/Aims: Radiopaque metal markers are required to improve X-ray absorption by self-expandable metal stents (SEMSs) to enable precise stent placement. A new tantalum radiopaque marker was recently developed using an ultrasonic spray technique. The aim of the present study was to evaluate the safety and visibility of tantalum markers. Methods: A total of three beagle dogs were used for a gastrointestinal tract absorption test. Five tantalum markers were placed in the stomach of each dog endoscopically. Excreted tantalum markers were collected, and their weights were compared to the original weights. In radiopacity tests, marker radiopacities on X-ray images were quantified using ImageJ software and compared with those of commercially available metal markers. Finally, the radiographic images of six patients who underwent biliary SEMS placement using tantalum marker Nitinol SEMSs (n=3) or gold marker Nitinol SEMSs (n=3) were compared with respect to marker brightness on fluoroscopic images. Results: Absorption testing showed that the marker structures and weights were unaffected. Radiopacity tests showed that the mean brightness and total brightness scores were greater for tantalum markers (226.22 and 757, respectively) than for gold (A, 209 and 355, respectively; B, 204.96 and 394, respectively; C, 194.34 and 281, respectively) or platinum markers (D, 203.6 and 98, respectively). On fluoroscopic images, tantalum markers had higher brightness and total brightness scores (41.47 and 497.67, respectively) in human bile ducts than gold markers (28.37 and 227, respectively). Conclusions: Tantalum markers were found to be more visible than other commercially available markers in X-ray images and to be resistant to gastrointestinal absorption.

Activation of natural Hf and Ta in relation to the production of 177Lu.

The isotope (177)Lu is used in nuclear medicine and biology for in vivo applications as a radioactive label of various targeting agents. To extend the availability of no-carrier added (177)Lu, we investigated the feasibility of its production in a proton accelerator. Tantalum and Hf targets were irradiated and chemically processed to determine the radioisotope yield and cross-sections. The largest cross-sections (approximately 20 mb) were found for the Hf target at 195 MeV; however, the presence of co-produced Lu isotopes may limit the product applications. The results are in good agreement with theoretical data calculated using computer codes MCNPX and ORIGEN2S. Production of relevant medical isotopes such as (167)Tm and (169)Yb from the above targets is discussed as well.

Enhanced tunable characteristics of the Na0.5Bi0.5TiO3-NaTaO3 relaxor-type system.

We have investigated the voltage-tunable characteristics of the Na(0.5)Bi(0.5)TiO(3)-NaTaO(3) homogeneity region, for which samples were prepared using a conventional solid-state reaction. The highest value of the relative tunability (n(r)) was obtained for the sample with 5 mol% of NaTaO(3), i.e., 47% at 1 MHz and a 70 kV/cm dc bias field. This sample also showed the highest value of the dielectric losses (tan delta) and temperature coefficient of the dielectric constant (tau(epsilon)), i.e., 0.05 and 4478 ppm/K, respectively. As the concentration of NaTaO(3) increased up to 90 mol% n(r), tan delta, and tau(epsilon) gradually decreased toward 22%, 0.0002 and -899 ppm/K, respectively. The dielectric constant of the samples varied in a similar manner between 662 and 130. At microwave frequencies, the dielectric losses of the samples substantially increased due to their relaxor-type nature. The lowest value was obtained for the samples with 90 mol% of NaTaO(3), i.e., 0.002. The tunable characteristics of the samples are related to the ferroelectric and dielectric properties, and it appears that the dielectric tunability of the Na(0.5)Bi(0.5)TiO(3)-NaTaO(3) system originates from its relaxor-type behavior.

Enhanced DNA damage induced by secondary electron emission from a tantalum surface exposed to soft x rays.

Both thick and thin films of pGEMR-3Zf- plasmid DNA deposited on a tantalum foil were exposed to soft X rays (effective energy of 14.8 keV) for various times in air under a relative humidity of 45% (Gamma approximately 6, where Gamma is the number of water molecules per nucleotide) and 84% (Gamma approximately 21), respectively. For a thick film, the DNA damage was induced chiefly by X-ray photons. For a thin film of DNA, X-ray-induced secondary electrons emitted from the tantalum result in a substantial increase in DNA damages. Different forms of plasmid DNA were separated and quantified by agarose gel electrophoresis and laser scanning. The exposure curves for the formation of nicked circular (single-strand break, SSB), linear (double-strand break, DSB), and interduplex crosslink forms 1 and 2 were obtained for both thick and thin films of DNA. The secondary electron enhancement factor for SSBs, DSBs and crosslinks of the thin film of DNA were derived to be 3.8 +/- 0.5, 2.9 +/- 0.7 and 7 +/- 3 at Gamma approximately 6 and 6.0 +/- 0.8, 7 +/- 1 and 3.9 +/- 0.9 at Gamma approximately 21, respectively. This study provides a molecular basis for understanding the enhanced biological effects at interfaces during diagnostic X-ray examination and radiotherapy.

Enhanced Charge Transport in Tantalum Nitride Nanotube Photoanodes for Solar Water Splitting.

In the present work we grow anodic self-organized Ta2O5 nanotube layers, which are converted by ammonolysis to Ta3 N5 nanotubes, and then are used as photoanodes for photoanalytic water splitting. We introduce a two-step anodization process that not only improves order (reduced growth defects) and overall light absorption in the nanotube layers, but also provides a significantly reduced interface charge resistance at the nitride/metal interface due to subnitride (TaNx ) formation. As a result, such nanotube anodes afford a 15-fold increase of the photocurrent compared with conventional nanotubular Ta3 N5 electrodes under AM 1.5 G simulated sunlight (100 mW cm(-2)) conditions.

Dosimetric measurements of an n-butyl cyanoacrylate embolization material for arteriovenous malformations.

PURPOSE: The therapeutic regimen for cranial arteriovenous malformations often involves both stereotactic radiosurgery and endovascular embolization. Embolization agents may contain tantalum or other contrast agents to assist the neurointerventionalists, leading to concerns regarding the dosimetric effects of these agents. This study investigated dosimetric properties of n-butyl cyanoacrylate (n-BCA) plus lipiodol with and without tantalum powder. METHODS: The embolization agents were provided cured from the manufacturer with and without added tantalum. Attenuation measurements were made for the samples and compared to the attenuation of a solid water substitute using a 6 MV photon beam. Effective linear attenuation coefficients (ELAC) were derived from attenuation measurements made using a portal imager and derived sample thickness maps projected in an identical geometry. Probable dosimetric errors for calculations in which the embolized regions are overridden with the properties of water were calculated using the ELAC values. Interface effects were investigated using a parallel plate ion chamber placed at set distances below fixed samples. Finally, Hounsfield units (HU) were measured using a stereotactic radiosurgery CT protocol, and more appropriate HU values were derived from the ELAC results and the CT scanner's HU calibration curve. RESULTS: The ELAC was 0.0516 ± 0.0063 cm(-1) and 0.0580 ± 0.0091 cm(-1) for n-BCA without and with tantalum, respectively, compared to 0.0487 ± 0.0009 cm(-1) for the water substitute. Dose calculations with the embolized region set to be water equivalent in the treatment planning system would result in errors of -0.29% and -0.93% per cm thickness of n-BCA without and with tantalum, respectively. Interface effects compared to water were small in magnitude and limited in distance for both embolization materials. CT values at 120 kVp were 2082 and 2358 HU for n-BCA without and with tantalum, respectively; dosimetrically appropriate HU values were estimated to be 79 and 199 HU, respectively. CONCLUSIONS: The dosimetric properties of the embolization agents are very close to those of water for a 6 MV beam. Therefore, treating the entire intracranial space as uniform in composition will result in less than 1% dosimetric error for n-BCA emboli smaller than 3.4 cm without added tantalum and n-BCA emboli smaller than 1.1 cm with added tantalum. Furthermore, when effective embolization can be achieved by the neurointerventionalist using n-BCA without tantalum, the dosimetric impact of overriding material properties will be lessened. However, due to the high attenuation of embolization agents with and without added tantalum for diagnostic energies, artifacts may occur that necessitate additional imaging to accurately identify the spatial extent of the region to be treated.

Improving radiochromic film's sensitivity by wrapping it with UV phosphor.

The main advantage of radiochromic-film dosimeters is the coupling of rapid full planar-acquisition, high-spatial resolution and dose linearity. Their main limitation, however, is their low radiation sensitivity. This precludes their application to measuring doses below a few Gy. Radiochromic films are sensitive to ultraviolet radiation. In this note the results of exposing radiochromic films to x rays through an UV imaging cassette, which converts and amplifies x rays to UV radiation, are presented. These results indicate a clear increase (around 50%) in radiochromic film's sensitivity to MV x rays (6, 10, and 18 MV) when exposed through the UV phosphor.

X-ray attenuation coefficients of high-atomic-number, hexanuclear transition metal cluster compounds: a new paradigm for radiographic contrast agents.

RATIONALE AND OBJECTIVES: The purpose of this study was to examine the radiologic attenuation properties of the parent cluster compounds, particularly attenuation as a function of discrete photon energy, before investigating ligand substitutions, which are necessary to improve cluster biocompatibility and to impart desirable physicochemical properties. MATERIALS AND METHODS: The linear attenuation coefficients for solutions of the cluster compounds Ta6Br14, K8Ta6O19, and (H3O)2W6Cl14 were determined at 60, 80, 103, 122, and 140 keV from gamma-ray transmission measurements with americium-241, xenon-133, gadolinium-153, cobalt-57, and technetium-99m radioactive sources. Transmission measurements were obtained for a fixed time interval that ensured a statistically accurate count distribution exceeding 20,000 counts through the sample for each trial. RESULTS: On a strictly mole per liter basis, a 0.075 mol/L aqueous solution of K8Ta6O19 showed 1.08 times the attenuation of 0.063 mol/L aqueous iohexol at 60 keV and 3.30 times the attenuation at 80 keV. Similarly, a 0.05 mol/L methanolic solution of (H3O)2W6Cl4 showed 0.96 times (96%) the attenuation of 0.063 mol/L aqueous iohexol at 60 keV but 3.09 times the attenuation of the iohexol solution at 80 keV. Attenuations of 0.063 mol/L aqueous iohexol and 0.0125 mol/L Ta6Br14 (ie, at approximately one-fifth the iohexol concentration) were comparable at greater than 60 keV. CONCLUSION: These results confirm the theoretic potential for use of early transition metal cluster compounds as radiographic contrast agents. At higher x-ray energies, cluster compounds demonstrate multiplied x-ray attenuation relative to iodinated contrast agents.

Compton profile study and electronic properties of tantalum diboride.

We have reported the first-ever experimental Compton profile (CP) of TaB2 using 20 Ci(137)Cs Compton spectrometer. To compare the experimental data, we have also computed the theoretical CPs using density functional theory (DFT) and hybridization of DFT and Hartree-Fock (HF) within linear combination of the atomic orbitals (LCAO) method. In addition, we have reported energy bands and density of states of TaB2 using LCAO and full potential-linearized augmented plane wave (FP-LAPW) methods. A real space analysis of CP of TaB2 confirms its metallic character which is in tune with the cross-overs of Fermi level by energy bands and Fermi surface topology. A comparison of equal-valence-electron-density (EVED) experimental profiles of isoelectronic TaB2 and NbB2 show more covalent (or less ionic) character of TaB2 than that of NbB2 which is in agreement with available ionicity data.

Thermal performance of batch boiling water targets for 18F production.

Batch boiling targets are commonly used in cyclotrons to produce Fluorine-18 by proton bombardment of Oxygen-18 enriched water. Computational models have been developed to predict the thermal performance of bottom-pressurized batch boiling production targets. The models have been validated with experimental test data from the Duke University Medical Cyclotron and the Wisconsin Medical Cyclotron. Good agreement has been observed between experimental measurements and model predictions of average target vapor fraction as a function of beam current and energy.

Dynamics of the hysteretic voltage-induced torsional strain in tantalum trisulfide.

We have studied how the hysteretic voltage-induced torsional strain, associated with charge-density-wave (CDW) depinning, in orthorhombic tantalum trisulfide depends on square-wave and triangle-wave voltages of different frequencies and amplitudes. The strains are measured by placing the sample, with a wire glued to the center as a transducer, in a radio frequency cavity and measuring the modulated response of the cavity. From the triangle waves, we map out the time dependence of the hysteresis loops, and find that the hysteresis loops broaden for waves with periods less than 30 s. The square-wave response shows that the dynamic responses to positive and negative voltages can be quite different. The overall frequency dependence is relaxational, but with multiple relaxation times which typically decrease with increasing voltage. The detailed dynamic response is very sample dependent, suggesting that it depends in detail on interactions of the CDW with sample defects.

Direct laser processing of a tantalum coating on titanium for bone replacement structures.

Recently tantalum is gaining more attention as a new metallic biomaterial as it has been shown to be bioactive and biologically bonds to bone. However, the relatively high cost of manufacture and an inability to produce a modular all Ta implant has limited its widespread acceptance. In this study we have successfully deposited a Ta coating on Ti using laser engineered net shaping (LENS) to enhance the osseointegration properties. In vitro biocompatibility study, using human osteoblast cell line hFOB, showed excellent cellular adherence and growth with abundant extracellular matrix formation on the Ta coating surface compared with the Ti surface. A six times higher living cell density was observed on the Ta coating than on the Ti control surface by MMT assay. A high surface energy and wettability of the Ta surface were observed to contribute to its significantly better cell-material interactions. Also, these dense Ta coatings do not suffer from low fatigue resistance due to the absence of porosity and a sharp interface between the coating and the substrate, which is a major concern for porous coatings used for enhanced/early biological fixation.

Optical multilayers for LED-based surface plasmon resonance sensors.

We address a structure for surface plasmon resonance (SPR) sensing supporting a symmetric bound surface plasmon, which results in a SPR feature narrower by a factor of 2 compared with that for the conventional configuration. We demonstrate that it enables a low-cost and low-power-consumption LED to be used as a polychromatic light source, which leads to a decrease in the sensor cost and an increase in the sensor miniaturization potential. Further, we show that these advancements are not at the expense of sensor performance in terms of its sensitivity and resolution. We show that the sensor can be designed to have similar sensitivity and even better resolution compared with those for a conventional configuration.