Time-resolved photoelectron spectroscopy of polyatomic molecules using 42-nm vacuum ultraviolet laser based on high harmonics generation

NASA Astrophysics Data System (ADS)

Nishitani, Junichi; West, Christopher W.; Higashimura, Chika; Suzuki, Toshinori

2017-09-01

Time-resolved photoelectron spectroscopy (TRPES) of gaseous polyatomic molecules using 266-nm (4.7 eV) pump and 42-nm (29.5 eV) probe pulses is presented. A 1-kHz Ti:sapphire laser with a 35 fs pulse duration is employed to generate high harmonics in Kr gas, and the 19th harmonic (42-nm) was selected using two SiC/Mg mirrors. Clear observation of the ultrafast electronic dephasing in pyrazine and photoisomerization of 1,3-cyclohexadiene demonstrates the feasibility of TRPES with the UV pump and VUV probe pulses under weak excitation conditions in the perturbation regime.

Noble-Gas Difluoride Complexes of Mercury(II): The Syntheses and Structures of Hg(OTeF 5) 2·1.5NgF 2 (Ng = Xe, Kr) and Hg(OTeF 5) 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

DeBackere, John R.; Mercier, Helene P. A; Schrobilgen, Gary J.

2014-02-03

The synthesis of high-purity Hg(OTeF 5) 2 has resulted in its structural characterization in the solid state by Raman spectroscopy and single-crystal X-ray diffraction (XRD) and in solution by 19F NMR spectroscopy. The crystal structure of Hg(OTeF 5) 2 (-173 °C) consists of discrete Hg(OTeF 5) 2 units having gauche-conformations that interact through long Hg---O and Hg---F intramolecular contacts to give a chain structure. Furthermore, the Lewis acidity of Hg(OTeF 5) 2 toward NgF 2 (Ng = Xe, Kr) was investigated in SO 2ClF solvent and shown to form stable coordination complexes with NgF 2 at -78 °C. Both complexesmore » were characterized by low-temperature Raman spectroscopy (-155 °C) and single-crystal XRD. The complexes are isostructural and are formulated as Hg(OTeF 5) 2·1.5NgF 2. The Hg(OTeF 5) 2 units of Hg(OTeF 5) 2·1.5NgF 2 also have gauche-conformations and are linked through bridging NgF 2 molecules, also resulting in chain structures. The complexes represent the only examples of coordination compounds where NgF 2 coordinates to mercury in a neutral covalent compound and the only example of mercury coordinated to KrF 2. Moreover, the Hg(OTeF 5) 2·1.5KrF 2 complex is the only KrF 2 complex known to contain a bridging KrF 2 ligand. Energy-minimized gas-phase geometries and vibrational frequencies for the model compounds, [Hg(OTeF5) 2] 3 and [Hg(OTeF 5) 2] 3·2NgF 2, were obtained and provide good approximations of the local environments of Hg(OTeF 5) 2 and NgF 2 in the crystal structures of Hg(OTeF5)2 and Hg(OTeF 5) 2·1.5NgF 2. Assignments of the Raman spectra of Hg(OTeF 5) 2 and Hg(OTeF 5) 2·1.5NgF 2 are based on the calculated vibrational frequencies of the model compounds. Natural bond orbital analyses provided the associated bond orders, valencies, and natural population analysis charges.« less

Study of titania nanorod films deposited by matrix-assisted pulsed laser evaporation as a function of laser fluence

NASA Astrophysics Data System (ADS)

Caricato, A. P.; Belviso, M. R.; Catalano, M.; Cesaria, M.; Cozzoli, P. D.; Luches, A.; Manera, M. G.; Martino, M.; Rella, R.; Taurino, A.

2011-11-01

Chemically synthesized brookite titanium dioxide (TiO2) nanorods with average diameter and length dimensions of 3-4 nm and 35-50 nm, respectively, were deposited by the matrix-assisted pulsed laser evaporation technique. A toluene nanorod solution was frozen at the liquid-nitrogen temperature and irradiated with a KrF excimer laser ( λ=248 nm, τ=20 ns) at the repetition rate of 10 Hz, at different fluences (25 to 350 mJ/cm2). The deposited films were structurally characterized by high-resolution scanning and transmission electron microscopy. <100> single-crystal Si wafers and carbon-coated Cu grids were used as substrates. Structural analyses evidenced the occurrence of brookite-phase crystalline nanospheres coexisting with individually distinguishable TiO2 nanorods in the films deposited at fluences varying from 50 to 350 mJ/cm2. Nanostructured TiO2 films comprising only nanorods were deposited by lowering the laser fluence to 25 mJ/cm2. The observed shape and phase transitions of the nanorods are discussed taking into account the laser-induced heating effects, reduced melting temperature and size-dependent thermodynamic stability of nanoscale TiO2.

Radiation damage and nanocrystal formation in uranium-niobium titanates

NASA Astrophysics Data System (ADS)

Lian, J.; Wang, S. X.; Wang, L. M.; Ewing, R. C.

2001-07-01

Two uranium-niobium titanates, U 2.25Nb 1.90Ti 0.32O 9.8 and Nb 2.75U 1.20Ti 0.36O 10, formed during the synthesis of brannnerite (UTi 2O 6), a minor phase in titanate-based ceramics investigated for plutonium immobilization. These uranium titanates were subjected to 800 keV Kr 2+ irradiation from 30 to 973 K. The critical amorphization dose of the U-rich and Nb-rich titanates at room temperature were 4.72×10 17 and 5×10 17 ions/ m2, respectively. At elevated temperature, the critical amorphization dose increases due to dynamic thermal annealing. The critical amorphization temperature for both Nb-rich and U-rich titanates is ˜933 K under a 800 keV Kr 2+ irradiation. Above the critical amorphization temperature, nanocrystals with an average size of ˜15 nm were observed. The formation of nanocrystals is due to epitaxial recrystallization. At higher temperatures, an ion irradiation-induced nucleation-growth mechanism also contributes to the formation of nanocrystals.

Periodic structure with a periodicity of 2-3.5 μm on crystalline TiO2 induced by unpolarized KrF excimer lasers

NASA Astrophysics Data System (ADS)

He, Rong; Ma, Hongliang; Zheng, Jiahui; Han, Yongmei; Lu, Yuming; Cai, Chuanbing

2016-08-01

Laser-induced periodic surface structures (LIPSS) were processed on the TiO2 bulk surface under the irradiation of 248 nm unpolarized KrF excimer laser pulses in air. Spatial LIPSS periods ranging from 2 to 3.5 μm are ascribed to the capillary wave. These microstructures were analyzed at different laser pulse numbers with the laser energy from 192 to 164 mJ. The scanning electron microscopy results indicated eventually stripes that have been disrupted as the increase in the laser pulse numbers, which is reasonably explained by the energy accumulating effect. In addition, investigations were concentrated on the surface modifications at pre-focal plane, focal plane and post-focal plane in the same defocusing amount. Compared with condition at pre-focal plane, in addition to the plasma produced at target, the air was also breakdown for the situation of post-focal plane. So it was reasonable that stripes appeared at pre-focal plane but not at post-focal plane.

Ion-beam irradiation of lanthanum compounds in the systems La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} and La{sub 2}O{sub 3}-TiO{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Whittle, Karl R., E-mail: karl.whittle@ansto.gov.a; Lumpkin, Gregory R.; Blackford, Mark G.

2010-10-15

Thin crystals of La{sub 2}O{sub 3}, LaAlO{sub 3}, La{sub 2/3}TiO{sub 3}, La{sub 2}TiO{sub 5}, and La{sub 2}Ti{sub 2}O{sub 7} have been irradiated in situ using 1 MeV Kr{sup 2+} ions at the Intermediate Voltage Electron Microscope-Tandem User Facility (IVEM-Tandem), Argonne National Laboratory (ANL). We observed that La{sub 2}O{sub 3} remained crystalline to a fluence greater than 3.1x10{sup 16} ions cm{sup -2} at a temperature of 50 K. The four binary oxide compounds in the two systems were observed through the crystalline-amorphous transition as a function of ion fluence and temperature. Results from the ion irradiations give critical temperatures for amorphisationmore » (T{sub c}) of 647 K for LaAlO{sub 3}, 840 K for La{sub 2}Ti{sub 2}O{sub 7}, 865 K for La{sub 2/3}TiO{sub 3}, and 1027 K for La{sub 2}TiO{sub 5}. The T{sub c} values observed in this study, together with previous data for Al{sub 2}O{sub 3} and TiO{sub 2}, are discussed with reference to the melting points for the La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} and La{sub 2}O{sub 3}-TiO{sub 2} systems and the different local environments within the four crystal structures. Results suggest that there is an observable inverse correlation between T{sub c} and melting temperature (T{sub m}) in the two systems. More complex relationships exist between T{sub c} and crystal structure, with the stoichiometric perovskite LaAlO{sub 3} being the most resistant to amorphisation. - Graphical abstract: La{sub 2}TiO{sub 5} with atypical co-ordination for Ti, TiO{sub 5} is found to be different in radiation resistance to La{sub 2}Ti{sub 2}O{sub 7} and La{sub 2/3}TiO{sub 3}. Irradiation of La-Ti-O, and La-Al-O based systems has found that radiation damage resistance is related to the ability of the system to disorder.« less

Heavy ion irradiation-induced microstructural evolution in pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} at room temperature and 723 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Q.R.; Zhang, J., E-mail: zhangjian@xmu.edu.cn; Dong, X.N.

Polycrystalline pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated with 600 keV Kr{sup 3+} at room temperature and 723 K to a fluence of 4×10{sup 15} ions/cm{sup 2}, corresponding to an average ballistic damage dose of 10 displacements per atom in the peak damage region. Irradiation-induced microstructural evolution was examined by grazing incidence X-ray diffraction, and cross-sectional transmission electron microscopy. Incomplete amorphization was observed in the sample irradiated at room temperature due to the formation of nano-crystal which has the identical structure of pyrochlore, and the formation of nano-crystal is attributed to the mechanism of epitaxial recrystallization. However, an orderedmore » pyrochlore phase to a swelling disordered fluorite phase transformation is occurred for the Lu{sub 2}Ti{sub 2}O{sub 7} sample irradiated at 723 K, which is due to the disordering of metal cations and anion vacancies. - Graphical Abstract: Polycrystalline pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated with 600 keV Kr{sup 3+} to a fluence of 4×10{sup 15} ions/cm{sup 2} at room temperature and 723 K, Incomplete amorphization was observed in the sample irradiated at room temperature due to the formation of nano-crystal. However, an ordered pyrochlore phase to a swelling disordered fluorite phase transformation is occurred for the Lu{sub 2}Ti{sub 2}O{sub 7} sample irradiated at 723 K, which is due to the disordering of metal cations and anion vacancies. - Highlights: Pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated by heavy ions at RT and 723 K. At RT irradiation, ~75% of amorphization was achieved. The nano-crystals were formed in the damage layer at RT irradiation. The formed nano-crystals enhanced the radiation tolerance of Lu{sub 2}Ti{sub 2}O{sub 7}. A pyrochlore to fluorite phase transformation was observed at 723 K irradiation.« less

Excimer laser annealing of NiTi shape memory alloy thin film

NASA Astrophysics Data System (ADS)

Xie, Qiong; Huang, Weimin; Hong, Ming Hui; Song, Wendong; Chong, Tow Chong

2003-02-01

NiTi Shape Memory Alloy (SMA) is with great potential for actuation in microsystems. It is particularly suitable for medical applications due to its excellent biocompatibility. In MEMS, local annealing of SMA is required in the process of fabrication. In this paper, local annealing of Ni52Ti48 SMA with excimer laser is proposed for the first time. The Ni52Ti48 thin film in a thickness of 5 μm was deposited on Si (100) wafer by sputtering at room temperature. After that, the thin film was annealed by excimer laser (248nm KrF laser) for the first time. Field-Emission Scanning Electron Microscopy (FESEM) and Atomic Force Microscopy (AFM) were used to characterize the surface profile of the deposited film after laser annealing. The phase transformation was measured by Differential Scanning Calorimeter (DSC) test. It is concluded that NiTi film sputtering on Si(100) substrate at room temperature possesses phase transformation after local laser annealing but with cracks.

Plume dynamics from UV pulsed ablation of Al and Ti

NASA Astrophysics Data System (ADS)

Bauer, William; Perram, Glen; Haugan, Timothy

2016-12-01

Pulsed laser ablation of Al and Ti with a < 3.3 J/cm2 KrF laser and Ar background pressure of up to 1 Torr was performed to study the ablated plume. Mass loss experiments revealed the number of ablated atoms per pulse increases by 30% for Ti and 20% for Al as pressure decreases from 1 Torr to vacuum. Optical emission imaging performed using a gated ICCD revealed a strong dependence of shock front parameters, defined by the Sedov-Taylor blast and classical drag models, on background pressure. Spatially resolved optical emission spectroscopy from Al I, Al II, Ti I, and Ti II revealed ion temperatures of 104 K that decreased away from the target surface along the surface normal and neutral temperatures of 103 K independent of target distance. Comparison between kinetic energy in the shock and internal excitation energy reveals that nearly 100% of the energy is partitioned into shock front kinetic energy and 1% into internal excitation.

Noble Gas-Uranium Coordination and Intersystem Crossing for the CUO(Ne)x(Ng)n (Ng = Ar, Kr, Xe) Complexes in Solid Neon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andrews, Lester; Liang, Binyong; Li, Jun

2004-02-15

Atomic uranium excited by laser ablation reacts with CO in excess neon to produce the novel CUO molecule, which forms weak complexes CUO(Ne)m with neon and stronger complexes CUO(Ne)x(Ng)n (Ng = Ar, Kr, Xe) when the heavier noble gas atoms are present. The heavier CUO(Ne)m-1(Ng) complexes are identified through the effects of CO isotopic and Ng substitution on the neon matrix infrared spectra and by comparison to DFT frequency calculations on model complexes CUO(Ng) (Ng = Ne, Ar, Kr, Xe). The U-C and U-O stretching frequencies of CUO(Ne)m-1(Ng) complexes are slightly red shifted from 1047 and 872 cm-1 frequencies formore » the 1Sigma+ CUO ground state neon complex, which identifies singlet ground state CUO(Ne)m-1(Ng) complexes in solid neon. The next singlet CUO(Ne)x(Ng)2 complexes in excess neon follow in like manner. However, stretching modes and the isotopic shifts of the higher CUO(Ne)x(Ng)n complex approach those of the pure argon matrix CUO(Ar)n complex, which characterizes triple t ground state complexes by comparison to DFT frequency calculations.« less

Joint experimental-theoretical investigation of the lower bound states of the NO(X2Pi)-Kr complex.

PubMed

Wen, Bo; Meyer, Henning; Kłos, Jacek; Alexander, Millard H

2009-07-02

We describe the first measurement of the near IR spectrum of the NO-Kr van der Waals complex. A variant of IR-REMPI double-resonance spectroscopy is employed in which the IR and UV lasers are scanned simultaneously in such a way that throughout the scan the sum of the two photon energies is kept constant, matching a UV resonance of the system. In the region of the first overtone vibration of the NO monomer, we observe several rotationally resolved bands for the NO-Kr complex. In addition to the origin band located at 3723.046 cm(-1), we observe excited as well as hot bands involving the excitation of one or two quanta of z-axis rotation. Another band is assigned to the excitation of one quantum of bending vibration. The experimental spectra are compared with results of bound-state calculations for a new set of potential energy surfaces calculated at the spin-restricted coupled cluster level. For the average vibration-rotation energies, there is excellent agreement between the theoretical results based on the coupled states (CS) approximation and the full close-coupling (CC) treatment. Finer details like the electrostatic splitting and the P-type doubling of the rotational levels are accounted for only within the CC formalism. The comparison of the CC results with the measured spectra confirms the high quality of the PESs. However, the high resolution of the experiments is sufficient to identify some inaccuracies in the difference between the potential energy surfaces of A' and A'' reflection symmetry.

Spectral and raw quasi in-situ energy dispersive X-ray data captured via a TEM analysis of an ODS austenitic stainless steel sample under 1 MeV Kr2+ high temperature irradiation.

PubMed

Brooks, Adam J; Yao, Zhongwen

2017-10-01

The data presented in this article is related to the research experiment, titled: ' Quasi in-situ energy dispersive X-ray spectroscopy observation of matrix and solute interactions on Y-Ti-O oxide particles in an austenitic stainless steel under 1 MeV Kr 2+ high temperature irradiation' (Brooks et al., 2017) [1]. Quasi in-situ analysis during 1 MeV Kr 2+ 520 °C irradiation allowed the same microstructural area to be observed using a transmission electron microscope (TEM), on an oxide dispersion strengthened (ODS) austenitic stainless steel sample. The data presented contains two sets of energy dispersive X-ray spectroscopy (EDX) data collected before and after irradiation to 1.5 displacements-per-atom (~1.25×10 -3  dpa/s with 7.5×10 14  ions cm -2 ). The vendor software used to process and output the data is the Bruker Esprit v1.9 suite. The data includes the spectral (counts vs. keV energy) of the quasi in-situ scanned region (512×512 pixels at 56k magnification), along with the EDX scanning parameters. The.raw files from the Bruker Esprit v1.9 output are additionally included along with the.rpl data information files. Furthermore included are the two quasi in-situ HAADF images for visual comparison of the regions before and after irradiation. This in-situ experiment is deemed ' quasi' due to the thin foil irradiation taking place at an external TEM facility. We present this data for critical and/or extended analysis from the scientific community, with applications applying to: experimental data correlation, confirmation of results, and as computer based modeling inputs.

Infrared spectroscopy and density functional calculations on titanium-dinitrogen complexes

NASA Astrophysics Data System (ADS)

Yoo, Hae-Wook; Choi, Changhyeok; Cho, Soo Gyeong; Jung, Yousung; Choi, Myong Yong

2018-04-01

Titanium-nitrogen complexes were generated by laser ablated titanium (Ti) atoms and N2 gas molecules in this study. These complexes were isolated on the pre-deposited solid Ar matrix on the pre-cooled KBr window (T ∼ 5.4 K), allowing infrared spectra to be measured. Laser ablation experiments with 15N2 isotope provided distinct isotopic shifts in the infrared spectra that strongly implicated the formation of titanium-nitrogen complexes, Ti(NN)x. Density functional theory (DFT) calculations were employed to investigate the molecular structures, electronic ground state, relative energies, and IR frequencies of the anticipated Ti(NN)x complexes. Based on laser ablation experiments and DFT calculations, we were able to assign multiple Ti(NN)x (x = 1-6) species. Particularly, Ti(NN)5 and Ti(NN)6, which have high nitrogen content, may serve as good precursors in preparing polynitrogens.

Mechanical properties improvement of pulsed laser-deposited hydroxyapatite thin films by high energy ion-beam implantation

NASA Astrophysics Data System (ADS)

Nelea, V.; Pelletier, H.; Müller, D.; Broll, N.; Mille, P.; Ristoscu, C.; Mihailescu, I. N.

2002-01-01

Major problems in the hydroxyapatite (HA), Ca 5(PO 4) 3OH, thin films processing still keep the poor mechanical properties and the lack in density. We present a study on the feasibility of high energy ion-beam implantation technique to densify HA bioceramic films. Crystalline HA films were grown by pulsed laser deposition (PLD) method using an excimer KrF ∗ laser ( λ=248 nm, τ FWHM≥20 ns). The films were deposited on Ti-5Al-2.5Fe alloys substrates previously coated with a ceramic TiN buffer layer. After deposition the films were implanted with Ar + ions at high energy. Optical microscopy (OM), white light confocal microscopy (WLCM), grazing incidence X-ray diffraction (GIXRD) and Berkovich nanoindentation in normal and scratch options have been applied for the characterization of the obtained structures. We put into evidence an enhancement of the mechanical characteristics after implantation, while GIXRD measurements confirm that the crystalline structure of HA phase is preserved. The improvement in mechanical properties is an effect of a densification after ion treatment as a result of pores elimination and grains regrowth.

Quantitative evaluation method for nonlinear characteristics of piezoelectric transducers under high stress with complex nonlinear elastic constant

NASA Astrophysics Data System (ADS)

Miyake, Susumu; Kasashima, Takashi; Yamazaki, Masato; Okimura, Yasuyuki; Nagata, Hajime; Hosaka, Hiroshi; Morita, Takeshi

2018-07-01

The high power properties of piezoelectric transducers were evaluated considering a complex nonlinear elastic constant. The piezoelectric LCR equivalent circuit with nonlinear circuit parameters was utilized to measure them. The deformed admittance curve of piezoelectric transducers was measured under a high stress and the complex nonlinear elastic constant was calculated by curve fitting. Transducers with various piezoelectric materials, Pb(Zr,Ti)O3, (K,Na)NbO3, and Ba(Zr,Ti)O3–(Ba,Ca)TiO3, were investigated by the proposed method. The measured complex nonlinear elastic constant strongly depends on the linear elastic and piezoelectric constants. This relationship indicates that piezoelectric high power properties can be controlled by modifying the linear elastic and piezoelectric constants.

Temperature dependence of the radiation tolerance of nanocrystalline pyrochlores A 2Ti 2O 7 (A = Gd, Ho and Lu)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wen, J.; Sun, C.; Dholabhai, P. P.

A potentially enhanced radiation resistance of nanocrystalline materials, as a consequence of the high density of interfaces and surfaces, has attracted much attention both to understand the fundamental role of these defect sinks and to develop them for high-radiation environments. Here, irradiation response of nanocrystalline A 2Ti 2O 7 (A = Gd, Ho and Lu) pyrochlore powders with grain sizes of 20–30 nm was investigated by 1-MeV Kr 2+ ion bombardment. In situ transmission electron microscopy (TEM) revealed that the critical amorphization fluence for each nanocrystalline compound at room temperature was greater than that for their coarse-grained counterparts, indicating anmore » enhanced amorphization resistance. The effect of temperature on the irradiation response of one of these compounds, nanocrystalline Lu 2Ti 2O 7, was further examined by performing ion irradiation at an elevated temperature range of 480–600 K. The critical amorphization temperature (T c) was found to be noticeably higher in nanocrystalline Lu 2Ti 2O 7 (610 K) than its coarse-grained counterpart (480 K), revealing that nanocrystalline Lu 2Ti 2O 7 is less resistant to amorphization compared to its coarse-grained phase under high temperatures. We interpret these results with the aid of atomistic simulations. Molecular statics calculations find that cation antisite defects are less energetically costly to form near surfaces than in the bulk, suggesting that the nanocrystalline form of these materials is generally less susceptible to amorphization than coarse-grained counterparts at low temperatures where defect kinetics are negligible. In contrast, at high temperatures, the annealing efficiency of antisite defects by cation interstitials is significantly reduced due to the sink properties of the surfaces in the nanocrystalline pyrochlore, which contributes to the observed higher amorphization temperature in the nano-grained phase than in coarse-grained counterpart. Altogether, these results provide new insight into the behavior of nanocrystalline materials under irradiation.« less

Temperature dependence of the radiation tolerance of nanocrystalline pyrochlores A 2Ti 2O 7 (A = Gd, Ho and Lu)

DOE PAGES

Wen, J.; Sun, C.; Dholabhai, P. P.; ...

2016-03-21

A potentially enhanced radiation resistance of nanocrystalline materials, as a consequence of the high density of interfaces and surfaces, has attracted much attention both to understand the fundamental role of these defect sinks and to develop them for high-radiation environments. Here, irradiation response of nanocrystalline A 2Ti 2O 7 (A = Gd, Ho and Lu) pyrochlore powders with grain sizes of 20–30 nm was investigated by 1-MeV Kr 2+ ion bombardment. In situ transmission electron microscopy (TEM) revealed that the critical amorphization fluence for each nanocrystalline compound at room temperature was greater than that for their coarse-grained counterparts, indicating anmore » enhanced amorphization resistance. The effect of temperature on the irradiation response of one of these compounds, nanocrystalline Lu 2Ti 2O 7, was further examined by performing ion irradiation at an elevated temperature range of 480–600 K. The critical amorphization temperature (T c) was found to be noticeably higher in nanocrystalline Lu 2Ti 2O 7 (610 K) than its coarse-grained counterpart (480 K), revealing that nanocrystalline Lu 2Ti 2O 7 is less resistant to amorphization compared to its coarse-grained phase under high temperatures. We interpret these results with the aid of atomistic simulations. Molecular statics calculations find that cation antisite defects are less energetically costly to form near surfaces than in the bulk, suggesting that the nanocrystalline form of these materials is generally less susceptible to amorphization than coarse-grained counterparts at low temperatures where defect kinetics are negligible. In contrast, at high temperatures, the annealing efficiency of antisite defects by cation interstitials is significantly reduced due to the sink properties of the surfaces in the nanocrystalline pyrochlore, which contributes to the observed higher amorphization temperature in the nano-grained phase than in coarse-grained counterpart. Altogether, these results provide new insight into the behavior of nanocrystalline materials under irradiation.« less

Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du, Guodong

In this work, the first examples of group 4 metalloporphyrin 1,2-diolato complexes were synthesized through a number of strategies. In general, treatment of imido metalloporphyrin complexes, (TTP)M=NR, (M = Ti, Zr, Hf), with vicinal diols led to the formation of a series of diolato complexes. Alternatively, the chelating pinacolate complexes could be prepared by metathesis of (TTP)MCl 2 (M = Ti, Hf) with disodium pinacolate. These complexes were found to undergo C-C cleavage reactions to produce organic carbonyl compounds. For titanium porphyrins, treatment of a titanium(II) alkyne adduct, (TTP)Ti(η 2-PhC≡CPh), with aromatic aldehydes or aryl ketones resulted in reductive couplingmore » of the carbonyl groups to produce the corresponding diolato complexes. Aliphatic aldehydes or ketones were not reactive towards (TTP)Ti(η 2-PhC≡CPh). However, these carbonyl compounds could be incorporated into a diolato complex on reaction with a reactive precursor, (TTP)Ti[O(Ph) 2C(Ph) 2O] to provide unsymmetrical diolato complexes via cross coupling reactions. In addition, an enediolato complex (TTP)Ti(OCPhCPhO) was obtained from the reaction of (TTP)Ti(η 2-PhC≡CPh) with benzoin. Titanium porphyrin diolato complexes were found to be intermediates in the (TTP)Ti=O-catalyzed cleavage reactions of vicinal diols, in which atmospheric oxygen was the oxidant. Furthermore, (TTP)Ti=O was capable of catalyzing the oxidation of benzyl alcohol and α-hydroxy ketones to benzaldehyde and α-diketones, respectively. Other high valent metalloporphyrin complexes also can catalyze the oxidative diol cleavage and the benzyl alcohol oxidation reactions with dioxygen. A comparison of Ti(IV) and Sn(IV) porphyrin chemistry was undertaken. While chelated diolato complexes were invariably obtained for titanium porphyrins on treatment with 1,2-diols, the reaction of vicinal diols with tin porphyrins gave a number of products, including mono-, bis-alkoxo, and chelating diolato complexes, depending on the identity of diols and the stoichiometry employed. It was also found that tin porphyrin complexes promoted the oxidative cleavage of vicinal diols and the oxidation of α-ketols to α-diketones with dioxygen. In extending the chemistry of metalloporphyrins and analogous complexes, a series of chiral tetraaza macrocyclic ligands and metal complexes were designed and synthesized. Examination of iron(II) complexes showed that they were efficient catalysts for the cyclopropanation of styrene by diazo reagents. Good yields and high diastereoselectivity were obtained with modest enantioselectivity. A rationalization of the stereoselectivity was presented on the basis of structural factors in a carbene intermediate.« less

High-energy krypton fluoride lasers for inertial fusion.

PubMed

Obenschain, Stephen; Lehmberg, Robert; Kehne, David; Hegeler, Frank; Wolford, Matthew; Sethian, John; Weaver, James; Karasik, Max

2015-11-01

Laser fusion researchers have realized since the 1970s that the deep UV light from excimer lasers would be an advantage as a driver for robust high-performance capsule implosions for inertial confinement fusion (ICF). Most of this research has centered on the krypton-fluoride (KrF) laser. In this article we review the advantages of the KrF laser for direct-drive ICF, the history of high-energy KrF laser development, and the present state of the art and describe a development path to the performance needed for laser fusion and its energy application. We include descriptions of the architecture and performance of the multi-kilojoule Nike KrF laser-target facility and the 700 J Electra high-repetition-rate KrF laser that were developed at the U.S. Naval Research Laboratory. Nike and Electra are the most advanced KrF lasers for inertial fusion research and energy applications.

On the Noble-Gas Induced Intersystem Crossing for the CUO Molecule: Experimental and Theoretical investigations of CUO(Ng)n (Ng = Ar, Kr, Xe; n = 1, 2, 3, 4) Complexes in Solid Neon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang, Binyong; Andrews, Lester S.; Li, Jun

2004-02-09

Uranium atoms excited by laser ablation react with CO in excess neon to produce the novel CUO molecule, which forms distinct Ng complexes (Ng = Ar, Kr, Xe) when the heavier noble gases are added. The CUO(Ng) complexes are identified through CO isotopic and Ng substitution on the neon matrix infrared spectra and by comparison to DFT frequency calculations. The U-C and U-O stretching frequencies of CUO(Ng) complexes are slightly red shifted from frequencies for the 1S+ CUO ground state, which identifies singlet ground state CUO(Ng) complexes. In solid neon the CUO molecule is also a complex CUO(Ne)n, and themore » CUO(Ne)n-1(Ng) complexes are likewise specified. The next singlet CUO(Ne)x(Ng)2 complexes in excess neon follow in like manner. However, the higher CUO(Ne)x(Ng)n complex (n = 3, 4) stretching modes approach pure argon matrix CUO(Ar)n values and isotopic behavior, which are characterized as triplet ground state complexes by DFT frequency calculations. This work suggests that the singlet-triplet crossing occurs with 3 Ar, 3 Kr or 4 Xe and a balance of Ne atoms coordinated to CUO in the neon matrix host.« less

Mechanical properties of pulsed laser-deposited hydroxyapatite thin films implanted at high energy with N + and Ar + ions. Part II: nano-scratch tests with spherical tipped indenter

NASA Astrophysics Data System (ADS)

Pelletier, H.; Nelea, V.; Mille, P.; Muller, D.

2004-02-01

In this study we report a method to improve the adherence of hydroxyapatite (HA) thin films, using an ion beam implantation treatment. Crystalline HA films were grown by pulsed laser deposition technique (PLD), using an excimer KrF * laser. The films were deposited at room temperature in vacuum on Ti-5Al-2.5Fe alloy substrates previously coated with a ceramic TiN buffer layer and then annealed in ambient air at (500-600) °C. After deposition the films were implanted with N + and Ar + ions accelerated at high energy (1-1.5 MeV range) at a fixed dose of 10 16 cm -2. The intrinsic mechanical resistance and adherence to the TiN buffer layer of the implanted HA films have been evaluated by nano-scratch tests. We used for measurements a spherical indenter with a tip radius of 5 μm. Different scratch tests have been performed on implanted and unimplanted areas of films to put into evidence the effects of N + and Ar + ion implantation process on the films properties. Results show an enhancement of the dynamic mechanical properties in the implanted zones and influence of the nature of the implanted species. The best results are obtained for films implanted with nitrogen.

Influence of a TiN interlayer on the microstructure and mechanical properties of hydroxyapatite films grown by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Nelea, Valentin D.; Ristoscu, Carmen; Colis, Silviu; Arens, Simona; Pelletier, Herve; Mihailescu, Ion N.; Mille, Pierre

2001-04-01

Crystalline hydroxyapatite (HA) thin films grown on metallic substrates is the best choice for bone restoration. This is due to the good biological compatibility of the hydroxyapatite material combined with the good mechanical characteristics of the substrates. We deposit HA thin films by Pulsed Laser Deposition (PLD) in vacuum at room temperature using a KrF* excimer laser ((lambda) equals 248 nm, (tau) FWHM >= 20 ns). The depositions were performed directly on Ti-5Al-2.5Fe or on substrates previously coated with a TiN buffer layer. The HA deposited structures were characterized by complementary techniques: GIXRD, SEM, TEM, SAED, EDS and nanoindentation. Properties of the HA films grown with and without the TiN buffer were discussed in term of microstructure and mechanical behavior. The films with interlayer preserve the stoichiometry, are completely recrystallized and present better mechanical characteristics as compared with those without buffer.

In situ formation of heterobimetallic salen complexes containing titanium and/or vanadium ions.

PubMed

Belokon, Yuri N; Harrington, Ross W; North, Michael; Young, Carl

2008-05-05

A combination of high-resolution electrospray mass spectrometry and (1)H NMR spectroscopy has been used to prove that when a mixture of [(salen)TiO]2 complexes containing two different salen ligands (salen and salen') is formed, an equilibrium is established between the homodimers and the heterodimer [(salen)TiO2Ti(salen')]. Depending upon the structure and stereochemistry of the two salen ligands, the equilibrium may favor either the homodimers or the heterodimer. Extension of this process to mixtures of titanium(salen) complexes [(salen)TiO]2 and vanadium (V)(salen') complexes [(salen')VO] (+)Cl (-) allowed the in situ formation of the heterobimetallic complex [(salen)TiO2V(salen')] (+)X (-) to be confirmed for all combinations of salen ligands studied except when the salen ligand attached to titanium contained highly electron-withdrawing nitro-groups. The rate of equilibration between heterobimetallic complexes is faster than that between two titanium complexes as determined by line broadening in the (1)H NMR spectra. These structural results explain the strong rate-inhibiting effect of vanadium (V)(salen) complexes in asymmetric cyanohydrin synthesis catalyzed by [(salen)TiO]2 complexes. It has also been demonstrated for the first time that the titanium and vanadium complexes can undergo exchange of salen ligands and that this is catalyzed by protic solvents. However, the ligand exchange is relatively slow (occurring on a time scale of days at room temperature) and so does not complicate studies aimed at using heterobimetallic titanium and vanadium salen complexes as asymmetric catalysts. Attempts to obtain a crystal structure of a heterobimetallic salen complex led instead to the isolation of a trinuclear titanium(salen) complex, the formation of which is also consistent with the catalytic results obtained previously.

Petrogenesis and metallogenesis of the Wajilitag and Puchang Fe-Ti oxide-rich intrusive complexes, northwestern Tarim Large Igneous Province

NASA Astrophysics Data System (ADS)

Zhang, Dongyang; Zhang, Zhaochong; Huang, He; Cheng, Zhiguo; Charlier, Bernard

2018-04-01

The Wajilitag and Puchang intrusive complexes of the Tarim large igneous province (TLIP) are associated with significant resources of Fe-Ti oxide ores. These two mafic-ultramafic intrusions show differences in lithology and mineral chemistry. Clinopyroxenite and melagabbro are the dominant rock types in the Wajilitag complex, whereas the Puchang complex is generally gabbroic and anorthositic in composition with minor plagioclase-bearing clinopyroxenites in the marginal zone. Disseminated Fe-Ti oxide ores are found in the Wajilitag complex and closely associated with clinopyroxenites, whereas the Puchang complex hosts massive to disseminated Fe-Ti oxide ores mainly within its gabbroic rocks. The Wajilitag intrusive rocks are characterized by a restricted range of initial 87Sr/86Sr ratios (0.7038-0.7048) and positive εNd(t) (+0.04 - +3.01), indicating insignificant involvement of continental crustal contamination. The slightly higher initial 87Sr/86Sr ratios (0.7039-0.7059) and lower εNd(t) values (-1.05 - +2.35) of the Puchang intrusive rocks also suggest that the isotopic characteristics was controlled primarily by their mantle source, rather than by crustal contamination. Both complexes have Sr-Nd isotopic compositions close the neighboring kimberlitic rocks and their hosted mantle xenoliths in the TLIP. This indicates that the ferrobasaltic parental magmas were most probably originated from partial melting of a metasomatized subcontinental lithospheric mantle, modified recently with subduction-related materials by the impingement of the ascending mantle plume. The recycled subduction-related materials preserved in the lithospheric mantle could play a key role in the formation of the parental Fe-rich magmas in the context of an overall LIP system. The distinct variations in mineral assemblage for each complex and modeled results indicated that the Wajilitag and Puchang complexes experienced different crystallization path. Fe-Ti oxides in Wajilitag joined the liquidus earlier in the crystallization sequence, especially relative to the crystallization of plagioclase. This is attributed to the relatively high TFeO, TiO2 and initial H2O contents of the parental magma. In combination with definitive field and petrological evidence, the enrichment of highly incompatible elements (e.g., Zr, Hf, Nb and Ta) and the depletion of rare earth elements in the Fe-Ti oxide ores is consistent with the plausible interpretation that the ores could be formed by fractional crystallization and crystal accumulation of the Fe-Ti oxide crystals from the ferrobasaltic parental magmas. A considerable amount of the Fe-Ti oxides in the Puchang has transported and sunk from higher up in the chamber to the underlying unconsolidated silicate crystal pile. The highly dense Fe-Ti oxide crystal slurries further tended to effective accumulate Fe-Ti oxides to form high-grade Fe-Ti oxide ore bodies, and subsequent rapid collapse and intrusive into lower lithologies within the complex under a H2O-rich environment during the late-stage of magmatic differentiation. The development of massive Fe-Ti oxide ores in the case of the Puchang, could plausibly result from a combination of the protracted differentiation history of a Fe highly enriched parental magma and the later addition of external H2O from the country rocks (e.g., carbonates) to the slowly cooling magma chamber.

High energy KrCl electric discharge laser

DOEpatents

Sze, Robert C.; Scott, Peter B.

1981-01-01

A high energy KrCl laser for producing coherent radiation at 222 nm. Output energies on the order of 100 mJ per pulse are produced utilizing a discharge excitation source to minimize formation of molecular ions, thereby minimizing absorption of laser radiation by the active medium. Additionally, HCl is used as a halogen donor which undergoes a harpooning reaction with metastable Kr.sub.M * to form KrCl.

High energy KrCl electric discharge laser

DOEpatents

Sze, R.C.; Scott, P.B.

A high energy KrCl laser is presented for producing coherent radiation at 222 nm. Output energies on the order of 100 mJ per pulse are produced utilizing a discharge excitation source to minimize formation of molecular ions, thereby minimizing absorption of laser radiation by the active medium. Additionally, HCl is used as a halogen donor which undergoes a harpooning reaction with metastable Kr/sub M/ to form KrCl.

Inertial Fusion Target Physics Advantages with the Krypton Fluoride Laser

NASA Astrophysics Data System (ADS)

Obenschain, Stephen

2010-11-01

The krypton fluoride (KrF) laser's short wavelength, broad bandwidth and capability to provide extremely uniform target illumination are advantages towards obtaining high gain direct drive implosions. The short wavelength helps suppress deleterious laser-plasma instabilities, and allows one to employ higher ablation pressures. In addition, the KrF architecture allows one to zoom down the focal diameter to follow the size of the imploding pellet, thereby improving the coupling efficiency. The NRL researchers have been conducting theoretical and experimental studies to quantify the beneficial effects of utilizing KrF light. Experiments using the Nike facility have confirmed that KrF light significantly increases the threshold for laser-plasma instability. This presentation will discuss the observed target physics with KrF light and its effects towards facilitating the high gains needed for power production with inertial fusion. Simulations indicate that shock ignited designs can achieve gains above 200 with KrF energies as low a 1 megajoule. For fusion energy a laser driver must be capable of high repetition rates (5-10 Hz) along with adequate efficiency and durability. The Electra KrF 30-cm aperture electron-beam-pumped amplifier has demonstrated long duration continuous operation at high-repetition rates. This and other advances show that the KrF laser should be able to meet the requirements.

Preparation and self-sterilizing properties of Ag@TiO2-styrene-acrylic complex coatings.

PubMed

Zhou, Xiang-dong; Chen, Feng; Yang, Jin-tao; Yan, Xiao-hui; Zhong, Ming-qiang

2013-04-01

In this study, we report a simple and cost-effective method for self-sterilized complex coatings obtained by Ag@TiO2 particle incorporation into styrene-acrylic latex. The Ag@TiO2 particles were prepared via a coupling agent modification process. The composite latices characterized by transmission electron microscopy (TEM) study were highly homogeneous at the nanometric scale, and the Ag@TiO2 particles were well dispersed and exhibited an intimate contact between both the organic and inorganic components. The Ag@TiO2 nanoparticles significantly enhanced the absorption in the visible region and engendered a good heat-insulating effect of the complex coatings. Moreover, the Ag@TiO2 nanoparticle incorporation into this polymer matrix renders self-sterilized nanocomposite materials upon light excitation, which are tested against Escherichia coli and Staphylococcus aureus. The complex coatings display an impressive performance in the killing of all micro-organisms with a maximum for a Ag@TiO2 loading concentration of 2-5 wt.%. The weathering endurance of the complex coating was also measured. Copyright © 2012 Elsevier B.V. All rights reserved.

Modeling protein-small molecule interactions: structure and thermodynamics of noble gases binding in a cavity in mutant phage T4 lysozyme L99A.

PubMed

Mann, G; Hermans, J

2000-09-29

The complexes of phage T4 lysozyme L99A with noble gases have been studied by molecular dynamics simulation. In a long simulation of the complex with one Xe atom, the structure was found to undergo global conformation change involving a reversible opening and closing of the entrance to the substrate-binding site, during which the conformations of the N and C-terminal domains varied little. The distributions of Xe positions sampled in dynamics simulations were refined in terms of anisotropic Gaussian distributions via least-squares minimization of the difference between Fourier transforms. In addition, molecular transformation simulations have been applied in order to calculate the binding free energies of Xe, Kr and Ar relative to a standard state at a pressure of 1 bar. A single bound Xe is found to assume an equilibrium distribution over three adjacent preferred sites, while in a two-Xe complex, the two Xe atoms preferentially occupy two of these. The positions of the three sites agree closely with the positions of bound Xe determined in the refined crystal structure of a complex formed at a pressure of 8 bar Xe, and the calculated affinities agree well with the observed partial occupancies. At a pressure of 8 bar, a mixture of one-Xe and two-Xe complexes is present, and similarly for complexes with Kr and Ar, with single occupancy relatively more prevalent with Kr and Ar. (Binding of a third Xe atom is found to be quite unfavorable.) A comparison with simulation results for the binding of benzene to the same site leads to the conclusion that binding of Xe within cavities in proteins is common because of several favorable factors: (1) Xe has a large atomic polarizability; (2) Xe can be applied at a relatively high pressure, i.e. high chemical potential; (3) an unfavorable entropic term related to the need to orient the ligand in the binding site is absent. Finally, it is found that the model's binding energy of a water molecule in the cavity is insufficient to overcome the unfavorable binding entropy. Copyright 2000 Academic Press.

DFT studies on the ligand effect on electronic and optical properties of three series of functionalized Ir(III) complexes

NASA Astrophysics Data System (ADS)

Liu, Shujie; Li, Yangen; Hu, Xiaoying; Liu, Xiangdong; Guan, Bo

2018-01-01

With the help of DFT and TDDFT, a series of functionalized mononuclear iridium (III) complexes were systematically investigated to make clear the effect of auxiliary ligands on their electrionic and photophysical properties. It can be found that introducing electron withdrawing group (sbnd CF3) on benzene moiety can stabilize HOMO level, thus leading to wider HOMO-LUMO gap and blue shift in spectrum. More importantly, introducing sbnd CF3 on benzene moiety can also significantly improve the radiative decay rate (kr). On the other hand, the incorporation of electron donating groups (such as -Ph(CH3)3) into pyridine moiety on ligand reduce kr. The complexes 1c-3c and 1d-3d have improved charge balance ability and larger percentage of metal character. The results revealed the nature of the different substituents have a significant effect on the HOMO, LUMO energy levels and kr, resulting in the change of emission color and the quantum efficiency (Φp).

Defect Complex Effect in Nb Doped TiO2 Ceramics with Colossal Permittivity

NASA Astrophysics Data System (ADS)

Li, Fuchao; Shang, Baoqiang; Liang, Pengfei; Wei, Lingling; Yang, Zupei

2016-10-01

Donor-doped Nb x Ti1- x O2 ( x = 1%, 2%, 4%, 6%, and 8%) ceramics with giant permittivity (>104) and a very low dielectric loss (˜0.05) were sintered under flowing N2 at 1400°C for 10 h. By increasing Nb doping concentration, two different dielectric responses were evidenced in the frequency dependence of dielectric properties of Nb doped TiO2 ceramics, which corresponded to the space charge polarization and the electron-pinned defect-dipoles effect, respectively. Especially, combined with the x-ray photoelectron spectroscopy results, the electron-pinned defect-dipoles induced by the 2({Nb}^{5 + } )_{{Ti}}^{ bullet } to 4({Ti}^{3 + } )^'_{{Ti}} leftarrow {V}_{{o}}^{ bullet bullet } defect complex were further confirmed to give rise to both their high ɛr and low tan δ in the high frequency range for the Nb x Ti1- x O2 ceramics with x > 4%.

Intermolecular dissociation energies of dispersively bound complexes of aromatics with noble gases and nitrogen

NASA Astrophysics Data System (ADS)

Knochenmuss, Richard; Sinha, Rajeev K.; Leutwyler, Samuel

2018-04-01

We measured accurate intermolecular dissociation energies D0 of the supersonic jet-cooled complexes of 1-naphthol (1NpOH) with the noble gases Ne, Ar, Kr, and Xe and with N2, using the stimulated-emission pumping resonant two-photon ionization method. The ground-state values D0(S0) for the 1NpOHṡS complexes with S= Ar, Kr, Xe, and N2 were bracketed to be within ±3.5%; they are 5.67 ± 0.05 kJ/mol for S = Ar, 7.34 ± 0.07 kJ/mol for S = Kr, 10.8 ± 0.28 kJ/mol for S = Xe, 6.67 ± 0.08 kJ/mol for isomer 1 of the 1NpOHṡN2 complex, and 6.62 ± 0.22 kJ/mol for the corresponding isomer 2. For S = Ne, the upper limit is D0 < 3.36 kJ/mol. The dissociation energies increase by 1%-5% upon S0 → S1 excitation of the complexes. Three dispersion-corrected density functional theory (DFT-D) methods (B97-D3, B3LYP-D3, and ωB97X-D) predict that the most stable form of these complexes involves dispersive binding to the naphthalene "face." A more weakly bound edge isomer is predicted in which the S moiety is H-bonded to the OH group of 1NpOH; however, no edge isomers were observed experimentally. The B97-D3 calculated dissociation energies D0(S0) of the face complexes with Ar, Kr, and N2 agree with the experimental values within <5%, but the D0(S0) for Xe is 12% too low. The B3LYP-D3 and ωB97X-D calculated D0(S0) values exhibit larger deviations to both larger and smaller dissociation energies. For comparison to 1-naphthol, we calculated the D0(S0) of the carbazole complexes with S = Ne, Ar, Kr, Xe, and N2 using the same DFT-D methods. The respective experimental values have been previously determined to be within <2%. Again, the B97-D3 results are in the best overall agreement with experiment.

Post-KR Delay Intervals and Mental Practice: A Test of Adams' Closed Loop Theory

ERIC Educational Resources Information Center

Bole, Ronald

1976-01-01

The present study suggests that post-KR delay interval time or activity in the interval has little to do with learning on a self-paced positioning task, not ruling out that on ballistic tasks or more complex nonballistic tasks that a learner could make use of additional time or strategy. (MB)

Notes on lunar ilmenite

NASA Technical Reports Server (NTRS)

Hutson, M. L.

1989-01-01

Opaques (mostly ilmenite) make up 0 to 5 percent of highland rocks, 1 to 11 percent of low-Ti mare basalts, and 10 to 34 percent of high-Ti mare basalts (Carter 1988). Apollos 11 and 17 sampled high-Ti basalts. Apollos 12 and 14 sampled low-Ti basalts. Apollo 15 sampled a complex mixture of mare and highland material. Apollo 16 sampled mainly highland material (Taylor 1975).

Recovery TiO2 by leaching process of carbothermic reduced Kalimantan ilmenite

NASA Astrophysics Data System (ADS)

Wahyuningsih, S.; Sari, P. P.; Ramelan, A. H.

2018-05-01

Ilmenite naturally occurred in iron titanate (FeTiO3) minerals. The separation of natural ilmenite into TiO2 and Fe2O3 need to be explored to gain the high purity separation product. A new combination method named of carbothermic reduction, acidic-leaching and complexation by EDTA were proposed for separation TiO2 from Ilmenite. Roasting of ilmenite was carried out at 950 °C for 1 h by the addition of activated carbon with mass ratio of ilmenite : activated carbon =4:3. The carbothermic reduction was carried out to yield a high separation of initial content of ilmenite that will be easily to dissolve within hydrochloric acid solution in leaching process. The composition of ilmenite observed by X-Ray Fluoresences (XRF) changed after the carbothermic reduction process and the dominant content is TiO2 (57.56%). X-Ray Diffraction (XRD) of roasted ilmenite composed of decomposed product of ilmenite i.e. hematite (Fe2O3), TiO2 anatase, TiO2 rutile, and inorganic salt. The leaching of the roasted ilmenite has been done by sulphuric acid solution (6 M) to gain the titanyl sulphate solution. Separation of iron impurities of TiO2 gel from titanyl sulphate (TiOSO4) solution was conducted by complexation method using EDTA as a complexation agent. The characteristic of TiO2 obtained using XRD showed that TiO2 is anatase type and the percentage of TiO2 using XRF showed that TiO2 content of 86,03%.

Rapid estimation of the electron correlation energy for van der Waals complexes RgX (Rg = Kr, Xe, X = Br, I)

NASA Astrophysics Data System (ADS)

Xinying, Li; Yongfang, Zhao; Xiaogong, Jing; Fengli, Liu; Fengyou, Hao

2006-01-01

We present the rules of electron correlation energies for RgX (Rg = Kr, Xe, X = Br, I) van der Waals (vdW) complex systems at CCSD(T) theoretical level with SDB-cc-pVQZ basis set by the Gaussian 98 program. A new method to derive the dispersion coefficient C6 by fitting the intermonomer electron correlation energies to C6R-6 function is introduced. The present C6 values are compared with the corresponding theoretical ones.

Factors that Influence Physician Identification of Potential Opioid Misusers

DTIC Science & Technology

2013-05-30

Shawn M. FWI-l20120134E Mannina, Lisa M. Bebarta, Vikhyat S. oe. I ,o.;:,l\\ 1\\IUIVIUI:ti Ganem, Victoria J. Carey , Katherine R. or. VVUHI\\ Ul\\111 1...opioid misusers Lisa M. Manina, Shawn M. Varney, Vikhyat S. Bebarta, Katherine R. Carey , Victoria J. Ganem, Rosemarie G. Ramos Background...Varney SM, Bebarta VS, Carey KR, Ganem VJ, Ramos RG Department of Emergency Medicine, San Antonio Military Medical Center, San Antonio, TX

Inhibition Kinetics and Emodin Cocrystal Structure of a Type II Polyketide Ketoreductase†,‡

PubMed Central

Korman, Tyler Paz; Tan, Yuhong; Wong, Justin; Luo, Rui; Tsai, Shiou-Chuan

2008-01-01

Type II polyketides are a class of natural products that include pharmaceutically important aromatic compounds such as the antibiotic tetracycline and antitumor compound doxorubicin. The type II polyketide synthase (PKS) is a complex consisting of 5–10 standalone domains homologous to fatty acid synthase (FAS). Polyketide ketoreductase (KR) provides regio- and stereochemical diversity during the reduction. How the type II polyketide KR specifically reduces only the C9 carbonyl group is not well understood. The cocrystal structures of actinorhodin polyketide ketoreductase (actKR) bound with NADPH or NADP+ and the inhibitor emodin were solved with the wild type and P94L mutant of actKR, revealing the first observation of a bent p-quinone in an enzyme active site. Molecular dynamics simulation help explain the origin of the bent geometry. Extensive screening for in vitro substrates shows that unlike FAS KR, the actKR prefers bicyclic substrates. Inhibition kinetics indicate that actKR follows an ordered Bi Bi mechanism. Together with docking simulations that identified a potential phosphopantetheine binding groove, the structural and functional studies reveal that the C9 specificity is a result of active site geometry and substrate ring constraints. The results lay the foundation for the design of novel aromatic polyketide natural products with different reduction patterns. PMID:18205400

Inhibition Kinetics And Emodin Cocrystal Structure of a Type II Polyketide Ketoreductase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Korman, T.P.; Tan, Y.-H.; Wong, J.

Type II polyketides are a class of natural products that include pharmaceutically important aromatic compounds such as the antibiotic tetracycline and antitumor compound doxorubicin. The type II polyketide synthase (PKS) is a complex consisting of 5-10 standalone domains homologous to fatty acid synthase (FAS). Polyketide ketoreductase (KR) provides regio- and stereochemical diversity during the reduction. How the type II polyketide KR specifically reduces only the C9 carbonyl group is not well understood. The cocrystal structures of actinorhodin polyketide ketoreductase (actKR) bound with NADPH or NADP{sup +} and the inhibitor emodin were solved with the wild type and P94L mutant ofmore » actKR, revealing the first observation of a bent p-quinone in an enzyme active site. Molecular dynamics simulation help explain the origin of the bent geometry. Extensive screening for in vitro substrates shows that unlike FAS KR, the actKR prefers bicyclic substrates. Inhibition kinetics indicate that actKR follows an ordered Bi Bi mechanism. Together with docking simulations that identified a potential phosphopantetheine binding groove, the structural and functional studies reveal that the C9 specificity is a result of active site geometry and substrate ring constraints. The results lay the foundation for the design of novel aromatic polyketide natural products with different reduction patterns.« less

Kr/Xe Separation over a Chabazite Zeolite Membrane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Xuhui; Zong, Zhaowang; Elsaidi, Sameh K.

2016-08-10

Cryogenic distillation, the current conventional technology to separate Krypton and Xenon from air, and from nuclear reprocessing technologies, is an energy-intensive and expensive process. Membrane technology could potentially make this challenging industrial separation less energy intensive and economically viable. We demonstrate that chabazite zeolite SAPO-34 membranes effectively separated Kr/Xe gas mixtures at industrially relevant compositions. Control over membrane thickness and average crystal size led to industrial range permeances and high separation selectivities. Specifically, SAPO-34 membranes can separate Kr/Xe mixtures with Kr permeances as high as 361.4 GPU and separation selectivities of 34.8 for molar compositions close to typical concentrations ofmore » these two gases in air. In addition, SAPO-34 membranes separated Kr/Xe mixtures with Kr permeances as high as 525.7 GPU and separation selectivities up to 45.1 for molar compositions as might be encountered in nuclear reprocessing technologies. Molecular sieving and differences in diffusivities were identified as the dominant separation mechanisms.« less

Magnesiothermic reduction for direct synthesis of Ti-Nb alloy at 1073 K (800 °C)

NASA Astrophysics Data System (ADS)

Choi, Kyunsuk; Lee, Kwang Hee; Ali, Basit; Choi, Sang-Hoon; Park, Kyoung-Tae; Sohn, Il

2017-09-01

Direct fabrication of titanium (Ti) and niobium (Nb) alloys by direct magnesiothermic reduction from the respective initial metal oxides and complex oxides has been studied. TiO2, Nb2O5, and complex TiNb2O7 oxides were used as raw materials with Mg used as a reductant. To ensure a high chemical potential of the reactants to drive the spontaneous magnesiothermic reduction of the oxide mixtures, excess Mg five times higher than the required stoichiometric molar ratio was added. Samples were heated in a glove box under recycled and purified Ar atmosphere at 1073 K (800 °C) for 10 h. After the reduction of TiO2, intermediate oxide phases of Ti6O could still be observed, but reduction of Nb2O5 and TiNb2O7 showed metallic Nb and Ti-Nb to be present with negligible oxides according to the scanning electron microscope-energy dispersive spectroscopy and x ray diffraction analysis. This indicated that direct fabrication of Ti-Nb alloys through a complex TiNb2O7 oxide is possible and can be more efficient than alloying pure metallic elements of Ti and Nb.

Nanocrystalline ferroelectric BaTiO3/Pt/fused silica for implants synthetized by pulsed laser deposition method

NASA Astrophysics Data System (ADS)

Jelínek, Miroslav; Drahokoupil, Jan; Jurek, Karel; Kocourek, Tomáš; Vaněk, Přemysl

2017-09-01

The thin-films of BaTiO3 (BTO)/Pt were prepared to test their potential as coatings for titanium-alloy implants. The nanocrystalline BTO/Pt bi-layers were successfully synthesized using fused silica as substrates. The bi-layers were prepared using KrF excimer laser ablation at substrate temperatures (Ts) ranging from 650 °C to 750 °C. The microstructure and composition of the deposits were investigated by scanning electron microscope, x-ray diffraction and wavelength dispersive x-ray spectroscopy methods. The electrical characterization of the Pt/BTO/Pt capacitors indicated ferroelectric-type response in BTO films containing (40-140) nm-sized grains. The technology, microstructure, and functional response of the layers are presented in detail.

Comparison of plume dynamics for laser ablated metals: Al and Ti

NASA Astrophysics Data System (ADS)

Bauer, William; Perram, Glen P.; Haugan, Timothy

2018-03-01

Emissive plumes from pulsed laser ablation of bulk Ti and Al from KrF laser irradiation at laser fluence up to 3.5 J/cm2 and argon background pressures of 0-1 Torr have been observed using gated intensified charged-coupled device imagery. Mass loss for Ti increases from 0.1 to 0.8 μg/pulse as pulse energy increase from 174 to 282 mJ/pulse (35-170 photons/atom) and decreases by ˜30% as pressure increases from vacuum to 1 Torr. Early plume energies are described by the free expansion velocities of 1.57 ± 0.02 and of 1.81 ± 0.07 cm/μs for Ti and Al, respectively, and up to 90% of the incoming laser energy can be attributed to the Al shock front in the mid-field. The ablation thresholds of 90 ± 27 mJ (1.12 ± 0.34 J/cm2) for Ti and 126 ± 13 mJ (1.58 ± 0.16 J/cm2) for Al also represent 30%-70% of the incident laser energy. The decrease in mass loss at higher pressures is attributed to plasma shielding of the target surface.

Ab initio ground and excited state potential energy surfaces for NO-Kr complex and dynamics of Kr solids with NO impurity

NASA Astrophysics Data System (ADS)

Castro-Palacios, Juan Carlos; Rubayo-Soneira, Jesús; Ishii, Keisaku; Yamashita, Koichi

2007-04-01

The intermolecular potentials for the NO(XΠ2)-Kr and NO(AΣ+2)-Kr systems have been calculated using highly accurate ab initio calculations. The spin-restricted coupled cluster method for the ground 1A'2 state [NO(XΠ2)-Kr ] and the multireference singles and doubles configuration interaction method for the excited 2A'2 state [NO(AΣ+2)-Kr], respectively, were used. The potential energy surfaces (PESs) show two linear wells and one that is almost in the perpendicular position. An analytical representation of the PESs has been constructed for the triatomic systems and used to carry out molecular dynamics (MD) simulations of the NO-doped krypton matrix response after excitation of NO. MD results are shown comparatively for three sets of potentials: (1) anisotropic ab initio potentials [NO molecule direction fixed during the dynamics and considered as a point (its center of mass)], (2) isotropic ab initio potentials (isotropic part in a Legendre polynomial expansion of the PESs), and (3) fitted Kr-NO potentials to the spectroscopic data. An important finding of this work is that the anisotropic and isotropic ab initio potentials calculated for the Kr-NO triatomic system are not suitable for describing the dynamics of structural relaxation upon Rydberg excitation of a NO impurity in the crystal. However, the isotropic ab initio potential in the ground state almost overlaps the published experimental potential, being almost independent of the angle asymmetry. This fact is also manifested in the radial distribution function around NO. However, in the case of the excited state the isotropic ab initio potential differs from the fitted potentials, which indicates that the Kr-NO interaction in the matrix is quite different because of the presence of the surrounding Kr atoms acting on the NO molecule. MD simulations for isotropic potentials reasonably reproduce the experimental observables for the femtosecond response and the bubble size but do not match spectroscopic results. A general overall view of the results suggests that, when the Kr-NO interaction takes place inside the matrix, potentials are rather symmetric and less repulsive than those for the triatomic system. pectroscopy, yields a mean absolute deviation of about 5cm-1 over the 22 levels. The dissociation energy with respect to the lowest vibrational energy is calculated within 30cm-1 of the experimental value of 12953±8cm-1. The reported agreement of the theoretical spectrum and dissociation energy with experiment is contingent upon the inclusion of the effects of core-generated electron correlation, spin-orbit coupling, and scalar relativity. The Dunham analysis [Phys. Rev. 41, 721 (1932)] of the spectrum is found to be very accurate. New values are given for the spectroscopic constants.

The Occurrence of the Holometabolous Pupal Stage Requires the Interaction between E93, Krüppel-Homolog 1 and Broad-Complex

PubMed Central

Ureña, Enric; Chafino, Silvia; Manjón, Cristina; Franch-Marro, Xavier; Martín, David

2016-01-01

Complete metamorphosis (Holometaboly) is a key innovation that underlies the spectacular success of holometabolous insects. Phylogenetic analyses indicate that Holometabola form a monophyletic group that evolved from ancestors exhibiting hemimetabolous development (Hemimetaboly). However, the nature of the changes underlying this crucial transition, including the occurrence of the holometabolan-specific pupal stage, is poorly understood. Using the holometabolous beetle Tribolium castaneum as a model insect, here we show that the transient up-regulation of the anti-metamorphic Krüppel-homolog 1 (TcKr-h1) gene at the end of the last larval instar is critical in the formation of the pupa. We find that depletion of this specific TcKr-h1 peak leads to the precocious up-regulation of the adult-specifier factor TcE93 and, hence, to a direct transformation of the larva into the adult form, bypassing the pupal stage. Moreover, we also find that the TcKr-h1-dependent repression of TcE93 is critical to allow the strong up-regulation of Broad-complex (TcBr-C), a key transcription factor that regulates the correct formation of the pupa in holometabolous insects. Notably, we show that the genetic interaction between Kr-h1 and E93 is also present in the penultimate nymphal instar of the hemimetabolous insect Blattella germanica, suggesting that the evolution of the pupa has been facilitated by the co-option of regulatory mechanisms present in hemimetabolan metamorphosis. Our findings, therefore, contribute to the molecular understanding of insect metamorphosis, and indicate the evolutionary conservation of the genetic circuitry that controls hemimetabolan and holometabolan metamorphosis, thereby shedding light on the evolution of complete metamorphosis. PMID:27135810

Production of highly charged ion beams Kr32+, Xe44+, Au54+ with Electron String Ion Source (ESIS) Krion-2 and corresponding basic and applied studies

NASA Astrophysics Data System (ADS)

Donets, D. E.; Donets, E. D.; Donets, E. E.; Salnikov, V. V.; Shutov, V. B.

2010-09-01

Electron String Ion Source (ESIS) Krion-2 (JINR, Dubna) was used for basic and applied research in various aspects of multiply charged heavy ions production. Energy recuperation mode in ESIS has been proofed first and used for production of highly charged ions 84Kr28+÷84Kr32+, 124Xe40÷124Xe44 and Au51+÷ Au54+. Krion-2 ESIS was mounted on high voltage (HV) platform of LU-20 Linac and used as an injector of highly charged ions during Nuclotron run N° 41. Krion-2 ESIS has produced 3.0.107 124Xe42+ ions per pulse of 7 μs duration. This ion beam was injected into LU-20 and Nuclotron, accelerated up to energy of 186 GeV and the extracted Xe beam was used for physics experiments. Electron String Ion Source Krion-2 demonstrated the high reliability and stability running during 30 days on HV platform. We believe that it is due to an extremely low electron beam power, provided by using the electron string mode of operation: 50 W pulse power and about 10 W average power. Other possible application of ESIS could be its use in injection complexes of synchrotrons and cyclotrons for cancer therapy. Slow and fast extraction of C4+ and C6+ beams from Krion-2 ESIS were preliminary studied towards ESIS optimization for medical accelerators requirements.

Low temperature oxidative desulfurization with hierarchically mesoporous titaniumsilicate Ti-SBA-2 single crystals.

PubMed

Shi, Chengxiang; Wang, Wenxuan; Liu, Ni; Xu, Xueyan; Wang, Danhong; Zhang, Minghui; Sun, Pingchuan; Chen, Tiehong

2015-07-21

Hierarchically porous Ti-SBA-2 with high framework Ti content (up to 5 wt%) was firstly synthesized by employing organic mesomorphous complexes of a cationic surfactant (CTAB) and an anionic polyelectrolyte (PAA) as templates. The material exhibited excellent performance in oxidative desulfurization of diesel fuel at low temperature (40 °C or 25 °C) due to the unique hierarchically porous structure and high framework Ti content.

Molecular hydrogen and catalytic combustion in the production of hyperpolarized 83Kr and 129Xe MRI contrast agents

PubMed Central

Rogers, Nicola J.; Hill-Casey, Fraser; Stupic, Karl F.; Six, Joseph S.; Lesbats, Clémentine; Rigby, Sean P.; Fraissard, Jacques; Pavlovskaya, Galina E.; Meersmann, Thomas

2016-01-01

Hyperpolarized (hp) 83Kr is a promising MRI contrast agent for the diagnosis of pulmonary diseases affecting the surface of the respiratory zone. However, the distinct physical properties of 83Kr that enable unique MRI contrast also complicate the production of hp 83Kr. This work presents a previously unexplored approach in the generation of hp 83Kr that can likewise be used for the production of hp 129Xe. Molecular nitrogen, typically used as buffer gas in spin-exchange optical pumping (SEOP), was replaced by molecular hydrogen without penalty for the achievable hyperpolarization. In this particular study, the highest obtained nuclear spin polarizations were P = 29% for 83Kr and P = 63% for 129Xe. The results were reproduced over many SEOP cycles despite the laser-induced on-resonance formation of rubidium hydride (RbH). Following SEOP, the H2 was reactively removed via catalytic combustion without measurable losses in hyperpolarized spin state of either 83Kr or 129Xe. Highly spin-polarized 83Kr can now be purified for the first time, to our knowledge, to provide high signal intensity for the advancement of in vivo hp 83Kr MRI. More generally, a chemical reaction appears as a viable alternative to the cryogenic separation process, the primary purification method of hp 129Xe for the past 2 1/2 decades. The inherent simplicity of the combustion process will facilitate hp 129Xe production and should allow for on-demand continuous flow of purified and highly spin-polarized 129Xe. PMID:26961001

Molecular hydrogen and catalytic combustion in the production of hyperpolarized 83Kr and 129Xe MRI contrast agents

NASA Astrophysics Data System (ADS)

Rogers, Nicola J.; Hill-Casey, Fraser; Stupic, Karl F.; Six, Joseph S.; Lesbats, Clémentine; Rigby, Sean P.; Fraissard, Jacques; Pavlovskaya, Galina E.; Meersmann, Thomas

2016-03-01

Hyperpolarized (hp) 83Kr is a promising MRI contrast agent for the diagnosis of pulmonary diseases affecting the surface of the respiratory zone. However, the distinct physical properties of 83Kr that enable unique MRI contrast also complicate the production of hp 83Kr. This work presents a previously unexplored approach in the generation of hp 83Kr that can likewise be used for the production of hp 129Xe. Molecular nitrogen, typically used as buffer gas in spin-exchange optical pumping (SEOP), was replaced by molecular hydrogen without penalty for the achievable hyperpolarization. In this particular study, the highest obtained nuclear spin polarizations were P = 29% for 83Kr and P = 63% for 129Xe. The results were reproduced over many SEOP cycles despite the laser-induced on-resonance formation of rubidium hydride (RbH). Following SEOP, the H2 was reactively removed via catalytic combustion without measurable losses in hyperpolarized spin state of either 83Kr or 129Xe. Highly spin-polarized 83Kr can now be purified for the first time, to our knowledge, to provide high signal intensity for the advancement of in vivo hp 83Kr MRI. More generally, a chemical reaction appears as a viable alternative to the cryogenic separation process, the primary purification method of hp 129Xe for the past 2 1/2 decades. The inherent simplicity of the combustion process will facilitate hp 129Xe production and should allow for on-demand continuous flow of purified and highly spin-polarized 129Xe.

Halogen and trace element geochemistry in Mid-Ocean Ridge basalts from the Australian-Antarctic Ridge (AAR)

NASA Astrophysics Data System (ADS)

Yang, Y. S.; Seo, J. H.; Park, S. H.; Kim, T.

2015-12-01

Australian-Antarctic Ridge (AAR) is an extension of easternmost SE Indian Mid-Ocean Ridge (MOR).We collected volcanic glasses from the "in-axis" of the KR1 and KR2 MOR, and the overlapping zones of the KR1 MOR and the nearby seamounts ("KR1 mixing"). We determined trace and halogen elements in the glasses. Halogen concentrations and its ratios in the glasses are important to understand the mantle metasomatism and volatile recycling. 52 of the collected glasses are "primitive" (higher than 6 wt% MgO), while 3 of them have rather "evolved" composition (MgO wt% of 1.72, 2.95 and 4.15). K2O concentrations and Th/Sc ratios in the glasses show a negative correlation with its MgO concentration. Incompatible element ratios such as La/Sm are rather immobile during a magma differentiation so the ratios are important to understand mantle composition (Hofmann et al. 2003). La/Sm ratios in the glasses are 0.95 ~ 3.28 suggesting that the AAR basalts can be classified into T-MORB and E-MORB (Schilling et al., 1983). La/Sm ratios are well-correlated with incompatible elements such as U, Ba, Nb, and negatively correlated with compatible elements such as Sc, Eu2+, Mg. The AAR glasses contain detectable halogen elements. The "KR1 mixing" glasses in halogen elements are more abundant than "in-axis" the glasses. Cl is the least variable element compared to the other halogens such as Br and I in the AAR. The "KR1 mixing" glasses have the largest variations of Br/Cl ratios compared to the "in-axis" glasses. The Cl/Br and Th/Sc ratios in the "in-axis" glasses and in the "KR1 mixing" glasses show positive and negative correlations, respectively. The Br-rich glasses in the "KR1 mixing" zone might be explained by a recycled Br-rich oceanic slab of paleo-subduction or by a hydrothermal alteration in the AAR. I composition in the glasses does not show a correlation other trace elements. The K/Cl and K/Ti ratios in the AAR glasses are similar to the basalts from the Galapagos Spreading Center (Geldmacher et al., 2010) and Pacific MORB. The AAR region closely located with Balleny hotspot (Lanyon et al., 1993) and Pacific-Antarctic Ridge. K2O/Nb and Zr/Nb ratios are very low compared with near Pacific-Antarctic Ridge and Southeast Indian Ridge. The ratios are close to the Balleny hotspot.

Unique capabilities for ICF and HEDP research with the KrF laser

NASA Astrophysics Data System (ADS)

Obenschain, Stephen; Bates, Jason; Chan, Lop-Yung; Karasik, Max; Kehne, David; Sethian, John; Serlin, Victor; Weaver, James; Oh, Jaechul; Jenkins, Bruce; Lehmberg, Robert; Hegeler, Frank; Terrell, Stephen; Aglitskiy, Yefim; Schmitt, Andrew

2014-10-01

The krypton-fluoride (KrF) laser provides the shortest wavelength, broadest bandwidth and most uniform target illumination of all developed high-energy lasers. For directly driven targets these characteristics result in higher and more uniform ablation pressures as well as higher intensity thresholds for laser-plasma instability. The ISI beam smoothing scheme implemented on the NRL Nike KrF facility allows easy implementation of focal zooming where the laser radial profile is varied during the laser pulse. The capability for near continuous zooming with KrF would be valuable towards minimizing the effects of cross beam energy transport (CBET) in directly driven capsule implosions. The broad bandwidth ISI beam smoothing that is utilized with the Nike KrF facility may further inhibit certain laser plasma instability. In this presentation we will summarize our current understanding of laser target interaction with the KrF laser and the benefits it provides for ICF and certain HEDP experiments. Status and progress in high-energy KrF laser technology will also be discussed. Work supported by the Deparment of Energy, NNSA.

Molecular mechanism underlying juvenile hormone-mediated repression of precocious larval-adult metamorphosis.

PubMed

Kayukawa, Takumi; Jouraku, Akiya; Ito, Yuka; Shinoda, Tetsuro

2017-01-31

Juvenile hormone (JH) represses precocious metamorphosis of larval to pupal and adult transitions in holometabolous insects. The early JH-inducible gene Krüppel homolog 1 (Kr-h1) plays a key role in the repression of metamorphosis as a mediator of JH action. Previous studies demonstrated that Kr-h1 inhibits precocious larval-pupal transition in immature larva via direct transcriptional repression of the pupal specifier Broad-Complex (BR-C). JH was recently reported to repress the adult specifier gene Ecdysone-induced protein 93F (E93); however, its mechanism of action remains unclear. Here, we found that JH suppressed ecdysone-inducible E93 expression in the epidermis of the silkworm Bombyx mori and in a B. mori cell line. Reporter assays in the cell line revealed that the JH-dependent suppression was mediated by Kr-h1. Genome-wide ChIP-seq analysis identified a consensus Kr-h1 binding site (KBS, 14 bp) located in the E93 promoter region, and EMSA confirmed that Kr-h1 directly binds to the KBS. Moreover, we identified a C-terminal conserved domain in Kr-h1 essential for the transcriptional repression of E93 Based on these results, we propose a mechanism in which JH-inducible Kr-h1 directly binds to the KBS site upstream of the E93 locus to repress its transcription in a cell-autonomous manner, thereby preventing larva from bypassing the pupal stage and progressing to precocious adult development. These findings help to elucidate the molecular mechanisms regulating the metamorphic genetic network, including the functional significance of Kr-h1, BR-C, and E93 in holometabolous insect metamorphosis.

Effects of pulmonary inhalation on hyperpolarized krypton-83 magnetic resonance T1 relaxation

NASA Astrophysics Data System (ADS)

Stupic, K. F.; Elkins, N. D.; Pavlovskaya, G. E.; Repine, J. E.; Meersmann, T.

2011-07-01

The 83Kr magnetic resonance (MR) relaxation time T1 of krypton gas in contact with model surfaces was previously found to be highly sensitive to surface composition, surface-to-volume ratio, and surface temperature. The work presented here explored aspects of pulmonary 83Kr T1 relaxation measurements in excised lungs from healthy rats using hyperpolarized (hp) 83Kr with approximately 4.4% spin polarization. MR spectroscopy without spatial resolution was applied to the ex vivo lungs that actively inhale hp 83Kr through a custom designed ventilation system. Various inhalation schemes were devised to study the influence of anatomical dead space upon the measured 83Kr T1 relaxation times. The longitudinal 83Kr relaxation times in the distal airways and the respiratory zones were independent of the lung inhalation volume, with T1 = 1.3 s and T1 = 1.0 s, depending only on the applied inhalation scheme. The obtained data were highly reproducible between different specimens. Further, the 83Kr T1 relaxation times in excised lungs were unaffected by the presence of up to 40% oxygen in the hp gas mixture. The results support the possible importance of 83Kr as a biomarker for evaluating lung function.

Major impact of N-methylation on cytotoxicity and hydrolysis of salan Ti(IV) complexes: sterics and electronics are intertwined.

PubMed

Meker, Sigalit; Manna, Cesar M; Peri, Dani; Tshuva, Edit Y

2011-10-14

A series of Ti(IV) complexes containing diamino bis(phenolato) "salan" type ligands with NH coordination were prepared, and their hydrolysis and cytotoxicity were analyzed and compared to the N-methylated analogues. Substituting methyl groups on the coordinative nitrogen donor of highly active and stable Ti(IV) salan complexes with H atoms has two main consequences: the hydrolysis rate increases and the cytotoxic activity diminishes. In addition, the small modification of a single replacement of Me with H leads to a different major hydrolysis product, where a dinuclear Ti(IV) complex with two bridging oxo ligands is obtained, as characterized by X-ray crystallography, rather than a trinuclear cluster. A partial hydrolysis product containing a single oxo bridge was also crystallographically analyzed. Investigation of a series of complexes with NH donors of different steric and electronic effects revealed that cytotoxicity may be restored by fine tuning these parameters even for complexes of low stability.

C60 and U ion irradiation of Gd 2Ti xZr 2-xO 7 pyrochlore

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jiaming; Toulemonde, Marcel; Lang, Maik

2015-08-01

Gd 2Ti xZr 2-xO 7 (x = 0 to 2) pyrochlore was irradiated by 30 MeV C 60 clusters, which provide an extremely high ionizing energy density. Here, high-resolution transmission electron microscopy revealed a complex ion-track structure in Gd 2Ti 2O 7 and Gd 2TiZrO 7, consisting of an amorphous core and a shell of a disordered, defect-fluorite structure.

Production of extended plasma channels in atmospheric air by amplitude-modulated UV radiation of GARPUN-MTW Ti : sapphire—KrF laser. Part 2. Accumulation of plasma electrons and electric discharge control

NASA Astrophysics Data System (ADS)

Zvorykin, V. D.; Ionin, Andrei A.; Levchenko, A. O.; Mesyats, Gennadii A.; Seleznev, L. V.; Sinitsyn, D. V.; Smetanin, Igor V.; Sunchugasheva, E. S.; Ustinovskii, N. N.; Shutov, A. V.

2013-04-01

The problem of the production of extended (~1 m) plasma channels is studied in atmospheric air by amplitude-modulated laser pulses of UV radiation, which are a superposition of a subpicosecond USP train amplified in a regenerative KrF amplifier with an unstable confocal resonator and a quasi-stationary lasing pulse. The USPs possess a high (0.2-0.3 TW) peak power and efficiently ionise oxygen molecules due to multiphoton ionisation, and the quasi-stationary lasing pulse, which has a relatively long duration (~100 ns), maintains the electron density at a level ne = (3-5) × 1014 cm—3 by suppressing electron attachment to oxygen. Experiments in laser triggering of high-voltage electric discharges suggest that the use of combined pulses results in a significant lowering of the breakdown threshold and enables controlling the discharge trajectory with a higher efficiency in comparison with smooth pulses. It was shown that controlled breakdowns may develop with a delay of tens of microseconds relative to the laser pulse, which is many orders of magnitude greater than the lifetime of free electrons in the laser-induced plasma. We propose a mechanism for this breakdown, which involves speeding-up of the avalanche ionisation of the air by negative molecular oxygen ions with a low electron binding energy (~0.5 eV) and a long lifetime (~1 ms), which are produced upon cessation of the laser pulse.

Cryosolution infrared study of hydrogen bonded halothane acetylene complex

NASA Astrophysics Data System (ADS)

Melikova, S. M.; Rutkowski, K. S.; Rospenk, M.

2018-05-01

The interactions between halothane (2-bromo-2-chloro-1,1,1-trifluoroethane) and acetylene (C2H2) are studied by FTIR spectroscopy. Results obtained in liquid cryosolutions in Kr suggest weak complex formation stabilized by H - bond. The complexation enthalpy (∼11 kJ/mol) is evaluated in a series of temperature measurements (T ∼ 120-160 K) of integrated intensity of selected bands performed in liquefied Kr. The quantum chemical MP2/6-311++G(2d,2p) calculations predict four different structures of the complex. The most stable and populated (94% at T∼120 K) structure corresponds to the H - bond between H atom of halothane and pi-electron of triple bond between C atoms of acetylene. Wave numbers of vibrational bands of the most stable structure are calculated in anharmonic approximation implemented in Gaussian program.

Formation of solid Kr nanoclusters in MgO

NASA Astrophysics Data System (ADS)

van Huis, M. A.; van Veen, A.; Schut, H.; Kooi, B. J.; de Hosson, J. Th.

2003-06-01

The phenomenon of positron confinement enables us to investigate the electronic structure of nanoclusters embedded in host matrices. Solid Kr nanoclusters are a very interesting subject of investigation because of the very low predicted value of the positron affinity of bulk Kr. In this work, positron trapping in solid Kr nanoclusters embedded in MgO is investigated. The Kr nanoclusters were created by means of 280 keV Kr ion implantation in single crystals of MgO(100) and subsequent thermal annealing at a temperature of 1100 K. The nanoclusters were observed by cross-sectional transmission electron microscopy in high-resolution mode. The fcc Kr nanoclusters are rectangularly shaped with sizes of 2 to 5 nm and are in a cube-on-cube orientation relationship with the MgO host matrix. From the Moiré fringes in high-resolution recordings, the lattice parameter of the solid Kr was deduced and found to vary from 5.3 to 5.8 Å. The corresponding pressures are 0.6 2.5 GPa as found using the Ronchi equation of state. The relationship between lattice parameter and cluster size was investigated and it was found that the lattice parameter increases linearly with increasing nanocluster size. The defect evolution during annealing was monitored by means optical absorption spectroscopy and positron beam analysis. No evidence of positron trapping was found despite the very low positron affinity of solid Kr. Alternative definitions of the positron affinity are proposed for application to insulator materials.

Lifetime measurement of high spin states in (75) Kr

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sheikh, Javid; Trivedi, T.; Maurya, K.

2010-01-01

The lifetimes of high spin states of {sup 75}Kr have been determined via {sup 50}Cr ({sup 28}Si, 2pn) {sup 75}Kr reaction in positive parity band using the Doppler-shift attenuation method. The transition quadrupole moments Q deduced from lifetime measurements have been compared with {sup 75}Br. Experimental results obtained from lifetime measurement are interpreted in the framework of projected shell model.

Relationship between crystallographic structure of the Ti{sub 2}O{sub 3}/MnS complex inclusion and microstructure in the heat-affected zone (HAZ) in steel processed by oxide metallurgy route and impact toughness

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiong, Zhihui; Liu, Shilong; Wang, Xuemin, E-mail: wxm@mater.ustb.edu.cn

2015-08-15

A new method based on electron back scattered diffraction (EBSD) is proposed to determine the structure of titanium oxide/MnS complex inclusion which induced the formation of intragranular acicular ferrite (IAF) in heat-affected zone (HAZ) in steel processed by oxide metallurgy route. It was found that the complex inclusion was Ti{sub 2}O{sub 3}/MnS, the orientation relationship between Ti{sub 2}O{sub 3} and MnS was also examined, and the crystallographic orientation relationship among IAF, Ti{sub 2}O{sub 3}/MnS complex inclusion, austenite, bainite formed at lower temperature is researched systematically. It was observed that MnS precipitated on Ti{sub 2}O{sub 3} at specific habit plane andmore » direction and MnS had a specific orientation relationship ((0001) Ti{sub 2}O{sub 3}//(111) MnS), <10–10> Ti{sub 2}O{sub 3}//<110> MnS) with respect to Ti{sub 2}O{sub 3}. Intragranular acicular ferrite (IAF) nucleated on MnS part of the Ti{sub 2}O{sub 3}/MnS complex inclusion had no specific orientation relationship with MnS. IAF and the surrounding bainite had different Bain groups, so that there was an increase in high angle boundaries, which was beneficial for the toughness of HAZ. - Highlights: • The inclusion of TiO{sub x}/MnS that induced IAF formation is identified to be Ti{sub 2}O{sub 3}/MnS. • The inclusion is identified based on electron back scattered diffraction (EBSD). • MnS and Ti{sub 2}O{sub 3} had specific orientation relationship of Ti{sub 2}O{sub 3}/MnS complex inclusion. • The IAFs formed on the same inclusion tend to be in one Bain group. • IAF and the surrounding bainite tend to be in different Bain groups.« less

Photocatalytic and antibacterial properties of Au-TiO2 nanocomposite on monolayer graphene: From experiment to theory

NASA Astrophysics Data System (ADS)

He, Wangxiao; Huang, Hongen; Yan, Jin; Zhu, Jian

2013-11-01

The formation of the Au-TiO2 nanocomposite on monolayer Graphene (GTA) by sequentially depositing titanium dioxide particles and gold nanoparticles on graphene sheet was synthesized and analyzed in our work. The structural, morphological, and physicochemical properties of samples were thoroughly investigated by UV-Vis spectrophotometer, Raman spectroscopy, Fourier transform infrared spectroscopy, atomic force microscopy, scanning electron microscope, and transmission electron microscope. Photocatalytic performance of GTA, graphene (GR), TiO2, and TiO2 -graphene nanocomposite (GT) were comparatively studied for degradation of methyl orange, and it was found that GTA had highest performance among all samples. More importantly, antibacterial performance of this novel composite against Gram-positive bacteria, Gram-negative bacteria, and fungus was predominant compared to GR, TiO2, and GT. And the result of biomolecules oxidation tests suggested that antimicrobial actions were contributed by oxidation stress on both membrane and antioxidant systems. Besides, the rate of two decisive processes during photocatalytic reaction, the rate of the charge transfer (kCT) and the rate of the electron-hole recombination (kR) have been studied by Perturbation theory, Radiation theory, and Schottky barrier theory. Calculation and derivation results show that GTA possesses superior charge separation and transfer rate, which gives an explanation for the excellent oxidation properties of GTA.

Neutron capture cross sections of Kr

NASA Astrophysics Data System (ADS)

Fiebiger, Stefan; Baramsai, Bayarbadrakh; Couture, Aaron; Krtička, Milan; Mosby, Shea; Reifarth, René; O'Donnell, John; Rusev, Gencho; Ullmann, John; Weigand, Mario; Wolf, Clemens

2018-01-01

Neutron capture and β- -decay are competing branches of the s-process nucleosynthesis path at 85Kr [1], which makes it an important branching point. The knowledge of its neutron capture cross section is therefore essential to constrain stellar models of nucleosynthesis. Despite its importance for different fields, no direct measurement of the cross section of 85Kr in the keV-regime has been performed. The currently reported uncertainties are still in the order of 50% [2, 3]. Neutron capture cross section measurements on a 4% enriched 85Kr gas enclosed in a stainless steel cylinder were performed at Los Alamos National Laboratory (LANL) using the Detector for Advanced Neutron Capture Experiments (DANCE). 85Kr is radioactive isotope with a half life of 10.8 years. As this was a low-enrichment sample, the main contaminants, the stable krypton isotopes 83Kr and 86Kr, were also investigated. The material was highly enriched and contained in pressurized stainless steel spheres.

High temperature ethylene polymerization catalyzed by titanium(IV) complexes with tetradentate aminophenolate ligands in cis-O, N, N chelating mode.

PubMed

Zhao, Ruiguo; Liu, Taotao; Wang, Liying; Ma, Haiyan

2014-09-07

A series of titanium trichloride complexes , ligated with claw-type tetradentate aminophenolate ligands were synthesized from the direct reaction of TiCl4(THF)2 with 1 equiv. of the corresponding aminophenol in the presence of triethylamine. For comparison purposes, titanium isopropoxide complexes were also synthesized via the reaction of Ti(O(i)Pr)4 and 1 equiv. of the proligand. Similar reactions of ZrCl4(THF)2 with the corresponding aminophenol ligands in the presence of triethylamine only allowed the isolation of zirconium complex . The X-ray diffraction studies reveal that titanium trichloride complexes , and titanium triisopropoxide complex all possess a distorted octahedral geometry with the tetradentate aminophenolate ligand in cis-O, N, N chelating mode, where the methoxy group of the aryl unit does not coordinate with the metal center in the solid state. Upon activation with MMAO, these titanium and zirconium(iv) complexes exhibited moderate to high catalytic activities for ethylene polymerization at 30-120 °C, producing high-molecular-weight polyethylenes with broad distributions (Mw/Mn = 10.2-34.8). The activities of titanium trichloride complexes are significantly higher than those of titanium isopropoxide and zirconium trichloride complexes at high temperatures. The highest activity of 15 456 kg (mol-Ti h)(-1) could be achieved by titanium trichloride complex with bromo groups on both ortho- and para-positions of the phenolate ring of the ligand at 120 °C.

Acceleration to High Velocities and Heating by Impact Using Nike KrF Laser

DTIC Science & Technology

2010-01-01

Acceleration to high velocities and heating by impact using Nike KrF laser. Max Karasik,1, ∗ J. L. Weaver,1 Y. Aglitskiy,2 T. Watari,3 Y. Arikawa,3 T...Suita, Osaka 565-0871, Japan 4RSI, Lanham, MD 20706 The Nike krypton fluoride laser [S. P. Obenschain, S. E. Bodner, D. Colombant, K. Gerber, R. H...COVERED 00-00-2010 to 00-00-2010 4. TITLE AND SUBTITLE Acceleration to high velocities and heating by impact using Nike KrF laser. 5a. CONTRACT

Gene Expression Dynamics in Major Endocrine Regulatory Pathways along the Transition from Solitary to Social Life in a Bumblebee, Bombus terrestris.

PubMed

Jedlička, Pavel; Ernst, Ulrich R; Votavová, Alena; Hanus, Robert; Valterová, Irena

2016-01-01

Understanding the social evolution leading to insect eusociality requires, among other, a detailed insight into endocrine regulatory mechanisms that have been co-opted from solitary ancestors to play new roles in the complex life histories of eusocial species. Bumblebees represent well-suited models of a relatively primitive social organization standing on the mid-way to highly advanced eusociality and their queens undergo both, a solitary and a social phase, separated by winter diapause. In the present paper, we characterize the gene expression levels of major endocrine regulatory pathways across tissues, sexes, and life-stages of the buff-tailed bumblebee, Bombus terrestris , with special emphasis on critical stages of the queen's transition from solitary to social life. We focused on fundamental genes of three pathways: (1) Forkhead box protein O and insulin/insulin-like signaling, (2) Juvenile hormone (JH) signaling, and (3) Adipokinetic hormone signaling. Virgin queens were distinguished by higher expression of forkhead box protein O and downregulated insulin-like peptides and JH signaling, indicated by low expression of methyl farnesoate epoxidase ( MFE ) and transcription factor Krüppel homolog 1 ( Kr-h1 ). Diapausing queens showed the expected downregulation of JH signaling in terms of low MFE and vitellogenin ( Vg ) expressions, but an unexpectedly high expression of Kr-h1 . By contrast, reproducing queens revealed an upregulation of MFE and Vg together with insulin signaling. Surprisingly, the insulin growth factor 1 (IGF-1) turned out to be a queen-specific hormone. Workers exhibited an expression pattern of MFE and Vg similar to that of reproducing queens. Males were characterized by high Kr-h1 expression and low Vg level. The tissue comparison unveiled an unexpected resemblance between the fat body and hypopharyngeal glands across all investigated genes, sexes, and life stages.

High surface stability of magnetite on bi-layer Fe3O4/Fe/MgO(0 0 1) films under 1 MeV Kr+ ion irradiation

NASA Astrophysics Data System (ADS)

Kim-Ngan, N.-T. H.; Krupska, M.; Balogh, A. G.; Malinsky, P.; Mackova, A.

2017-12-01

We investigate the stability of the bi-layer Fe3O4/Fe(0 0 1) films grown epitaxially on MgO(0 0 1) substrates with the layer thickness in the range of 25-100 nm upon 1 MeV Kr+ ion irradiation. The layer structure and layer composition of the films before and after ion irradiation were studied by XRR, RBS and RBS-C techniques. The interdiffusion and intermixing was analyzed. No visible change in the RBS spectra was observed upon irradiation with ion fluence below 1015 Kr cm-2. The bi-layer structure and the stoichiometric Fe3O4 layer on the surface were well preserved after Kr+ ion irradiation at low damage levels, although the strong intermixing implied a large interfacial (Fe x O y ) and (Fe, Mg)O y layer respective at Fe3O4-Fe and Fe-MgO interface. The high ion fluence of 3.8  ×  1016 Kr cm-2 has induced a complete oxidization of the buffer Fe layer. Under such Kr fluence, the stoichiometry of the Fe3O4 surface layer was still preserved indicating its high stability. The entire film contains Fe x O y -type composition at ion fluence large than 5.0  ×  1016 Kr cm-2.

Vii. New Kr IV - VII Oscillator Strengths and an Improved Spectral Analysis of the Hot, Hydrogen-deficient Do-type White Dwarf RE 0503-289

NASA Technical Reports Server (NTRS)

Rauch, T.; Quinet, P.; Hoyer, D.; Werner, K.; Richter, P.; Kruk, J. W.; Demleitner, M.

2016-01-01

For the spectral analysis of high-resolution and high signal-to-noise (SN) spectra of hot stars, state-of-the-art non-local thermodynamic equilibrium (NLTE) model atmospheres are mandatory. These are strongly dependent on the reliability of the atomic data that is used for their calculation. Aims. New Krivvii oscillator strengths for a large number of lines enable us to construct more detailed model atoms for our NLTEmodel-atmosphere calculations. This enables us to search for additional Kr lines in observed spectra and to improve Kr abundance determinations. Methods. We calculated Krivvii oscillator strengths to consider radiative and collisional bound-bound transitions in detail in our NLTE stellar-atmosphere models for the analysis of Kr lines that are exhibited in high-resolution and high SN ultraviolet (UV)observations of the hot white dwarf RE 0503.

Fabrication of SLM NiTi Shape Memory Alloy via Repetitive Laser Scanning

NASA Astrophysics Data System (ADS)

Khoo, Zhong Xun; Liu, Yong; Low, Zhi Hong; An, Jia; Chua, Chee Kai; Leong, Kah Fai

2018-03-01

Additive manufacturing has the potential to overcome the poor machinability of NiTi shape-memory alloy in fabricating smart structures of complex geometry. In recent years, a number of research activities on selective laser melting (SLM) of NiTi have been carried out to explore the optimal parameters for producing SLM NiTi with the desired phase transformation characteristics and shape-memory properties. Different effects of energy density and processing parameters on the properties of SLM NiTi were reported. In this research, a new approach—repetitive laser scanning—is introduced to meet these objectives as well. The results suggested that the laser absorptivity and heat conductivity of materials before and after the first scan significantly influence the final properties of SLM NiTi. With carefully controlled repetitive scanning process, the fabricated samples have demonstrated shape-memory effect of as high as 5.11% (with an average value of 4.61%) and exhibited comparable transformation characteristics as the NiTi powder used. These results suggest the potential for fabricating complex NiTi structures with similar properties to that of the conventionally produced NiTi parts.

Fabrication of SLM NiTi Shape Memory Alloy via Repetitive Laser Scanning

NASA Astrophysics Data System (ADS)

Khoo, Zhong Xun; Liu, Yong; Low, Zhi Hong; An, Jia; Chua, Chee Kai; Leong, Kah Fai

2018-01-01

Additive manufacturing has the potential to overcome the poor machinability of NiTi shape-memory alloy in fabricating smart structures of complex geometry. In recent years, a number of research activities on selective laser melting (SLM) of NiTi have been carried out to explore the optimal parameters for producing SLM NiTi with the desired phase transformation characteristics and shape-memory properties. Different effects of energy density and processing parameters on the properties of SLM NiTi were reported. In this research, a new approach—repetitive laser scanning—is introduced to meet these objectives as well. The results suggested that the laser absorptivity and heat conductivity of materials before and after the first scan significantly influence the final properties of SLM NiTi. With carefully controlled repetitive scanning process, the fabricated samples have demonstrated shape-memory effect of as high as 5.11% (with an average value of 4.61%) and exhibited comparable transformation characteristics as the NiTi powder used. These results suggest the potential for fabricating complex NiTi structures with similar properties to that of the conventionally produced NiTi parts.

Analyzing non-LTE Kr plasmas produced in high energy density experiments: from the Z machine to the National Ignition Facility

NASA Astrophysics Data System (ADS)

Dasgupta, Arati

2015-11-01

Designing high fluence photon sources above 10 keV are a challenge for High Energy Density plasmas. This has motivated radiation source development investigations of Kr with K-shell energies around 13 keV. Recent pulsed power driven gas-puff experiments on the refurbished Z machine at Sandia have produced intense X-rays in the multi-keV photon energy range. K-shell radiative yields and efficiencies are very high for Ar, but rapidly decrease for higher atomic number (ZA) elements such as Kr. It has been suggested that an optimum exists corresponding to a trade-off between the increase of photon energy for higher ZA elements and the corresponding fall off in radiative power. However the conversion efficiency on NIF, where the drive, energy deposition process, and target dynamics are different, does not fall off with higher ZA as rapidly as on Z. We have developed detailed atomic structure and collisional data for the full K-, L- and partial M-shell of Kr using the Flexible Atomic Code (FAC). Our non-LTE atomic model includes all collisional and recombination processes, including state-specific dielectronic recombination (DR), that significantly affect ionization balance and spectra of Kr plasmas at the temperatures and densities of concern. The model couples ionization physics, radiation production and transport, and magnetohydrodynamics. In this talk, I will give a detailed description of the model and discuss 1D Kr simulations employing a multifrequency radiation transport scheme. Synthetic K- and L-shell spectra will be compared with available experimental data. This talk will analyze experimental data indicative of the differences between Z and NIF experimental data and discuss how they affect the K-shell radiative output of Kr plasma. Work supported by DOE/NNSA.

A human fatty acid synthase inhibitor binds β-ketoacyl reductase in the keto-substrate site.

PubMed

Hardwicke, Mary Ann; Rendina, Alan R; Williams, Shawn P; Moore, Michael L; Wang, Liping; Krueger, Julie A; Plant, Ramona N; Totoritis, Rachel D; Zhang, Guofeng; Briand, Jacques; Burkhart, William A; Brown, Kristin K; Parrish, Cynthia A

2014-09-01

Human fatty acid synthase (hFAS) is a complex, multifunctional enzyme that is solely responsible for the de novo synthesis of long chain fatty acids. hFAS is highly expressed in a number of cancers, with low expression observed in most normal tissues. Although normal tissues tend to obtain fatty acids from the diet, tumor tissues rely on de novo fatty acid synthesis, making hFAS an attractive metabolic target for the treatment of cancer. We describe here the identification of GSK2194069, a potent and specific inhibitor of the β-ketoacyl reductase (KR) activity of hFAS; the characterization of its enzymatic and cellular mechanism of action; and its inhibition of human tumor cell growth. We also present the design of a new protein construct suitable for crystallography, which resulted in what is to our knowledge the first co-crystal structure of the human KR domain and includes a bound inhibitor.

Selection of a novel peptide aptamer with high affinity for TiO2-nanoparticle through a direct electroporation with TiO2-binding phage complexes.

PubMed

Inoue, Ippei; Ishikawa, Yasuaki; Uraoka, Yukiharu; Yamashita, Ichiro; Yasueda, Hisashi

2016-11-01

We have developed an easy and rapid screening method of peptide aptamers with high affinity for a target material TiO 2 using M13 phage-display and panning procedure. In a selection step, the phage-substrate complexes and Escherichia coli cells were directly applied by electric pulse for electroporation, without separating the objective phages from the TiO 2 nanoparticles. Using this simple and rapid method, we obtained a novel peptide aptamer (named ST-1 with the sequence AYPQKFNNNFMS) with highly strong binding activity for TiO 2 . A cage-shaped protein fused with both ST-1 and an available carbon nanotube-affinity peptide was designed and produced in E. coli. The multi-functional supraprotein could efficiently mineralize a titanium-compound around the surface of single-wall carbon nanotubes (SWNTs), indicating that the ST-1 is valuable in the fabrication of nano-composite materials with titanium-compounds. The structural analysis of ST-1 variants indicated the importance of the N-terminal region (as a motif of AXPQKX 6 S) of the aptamer in the TiO 2 -binding activity. Copyright © 2016 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

KrF laser pumping by electron beam discharge

NASA Astrophysics Data System (ADS)

Bonnet, J.; Fournier, G.; Pigache, D.

1981-09-01

The pumping of excimer lasers used in nuclear fusion and isotope separation is considered. Homogeneous ionization with an electron beam permitted discharge pumping of a KrF laser with a discharge-energy/beam-energy ratio 5. This high value is obtained to the detriment of an energy density and an efficiency which are about half the best values obtained under other conditions. This result does not modify a recent conclusion indicating that an electron beam controlled discharge has no significant advantage over a pure electron beam as regards pumping high energy KrF lasers at high repetition rate.

The influence of crystal structure on ion-irradiation tolerance in the Sm(x)Yb(2-x)TiO5 series

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aughterson, R. D.; Lumpkin, G. R.; de los Reyes, M.

2016-04-01

his ion-irradiation study covers the four major crystal structure types in the Ln(2)TiO(5) series (Ln = lanthanide), namely orthorhombic Pnma, hexagonal P63/mmc, cubic (pyrochlore-like) Fd-3m and cubic (fluorite-like) Fm-3m. This is the first systematic examination of the complete Ln(2)TiO(5) crystal system and the first reported examination of the hexagonal structure. A series of samples, based on the stoichiometry Sm(x)Yb(2-x)TiO5 (where x = 2, 1.4, 1, 0.6, and 0) have been irradiated using 1 MeV Kr2+ ions and characterised in-situ using a transmission electron microscope. Two quantities are used to define ion-irradiation tolerance: critical dose of amorphisation (D-c), which is themore » irradiating ion dose required for a crystalline to amorphous transition, and the critical temperature (T-c), above which the sample cannot be rendered amorphous by ion irradiation. The structure type plus elements of bonding are correlated to ion-irradiation tolerance. The cubic phases, Yb2TiO5 and Sm0.6Yb1.4TiO5, were found to be the most radiation tolerant, with Tc values of 479 and 697 K respectively. The improved radiation tolerance with a change in symmetry to cubic is consistent with previous studies of similar compounds.« less

High spin states in {sup 151,153}Pr, {sup 157}Sm, and {sup 93}Kr

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hwang, J. K.; Ramayya, A. V.; Hamilton, J. H.

2010-09-15

High spin states are observed for the first time in the neutron-rich nuclei {sup 151,153}Pr, {sup 157}Sm, and {sup 93}Kr from the spontaneous fission of {sup 252}Cf. Twenty new transitions in {sup 151}Pr, twelve in {sup 153}Pr, five in {sup 157}Sm, and four in {sup 93}Kr were identified by using x-ray(Pr/Sm)-{gamma}-{gamma} and {gamma}-{gamma}-{gamma} triple coincidences. From the measured total internal conversion coefficients {alpha}{sub T} of four low-energy transitions in {sup 151,153}Pr, we determine that two bands in each nucleus have opposite parity. The interlacing E1 transitions between the bands suggest a form of parity doubling in {sup 151,153}Pr. New bandsmore » in {sup 157}Sm and {sup 93}Kr are reported. The half-life of the 354.8 keV state in {sup 93}Kr is measured to be 10(2) ns.« less

Cracking and Exfoliation of TiO2 Film Irradiated with Excimer Laser

NASA Astrophysics Data System (ADS)

Qian, H. X.; Zhou, W.; Zheng, H. Y.

TiO2 film deposited on glass was irradiated in air with single-shot KrF excimer laser pulse. The surface roughened as the result of the laser ablation. It is further noted that single-pulse irradiation with fluence ranging from 400 to 1200 mJ/cm2 gave rise to protrusion of the irradiated surface above the original surface, which is in contrast to usual expectation that irradiated surface is below the unirradiated surface. The surface protrusion is mainly attributed to the effect of surface tension. At the laser fluence of 1000 mJ/cm2, cracks were formed in the irradiated area and severe film exfoliation was observed at the periphery of the irradiated area due to the release of internal stress. With higher laser fluence above 1000 mJ/cm2, patches of film were observed to peel off within the irradiated areas. Hydrodynamic ablation is proposed to account for film exfoliation. The observed phenomenon is useful for further understanding how TiO2 film reacts to strong UV laser irradiation.

Analyses of surface coloration on TiO 2 film irradiated with excimer laser

NASA Astrophysics Data System (ADS)

Zheng, H. Y.; Qian, H. X.; Zhou, W.

2008-01-01

TiO 2 film of around 850 nm in thickness was deposited on a soda-lime glass by PVD sputtering and irradiated using one pulse of krypton-fluorine (KrF) excimer laser (wavelength of 248 nm and pulse duration of 25 ns) with varying fluence. The color of the irradiated area became darker with increasing laser fluence. Irradiated surfaces were characterized using optical microscopy, scanning electron microscopy, Raman spectroscopy and atomic force microscopy. Surface undergoes thermal annealing at low laser fluence of 400 and 590 mJ/cm 2. Microcracks at medium laser fluence of 1000 mJ/cm 2 are attributed to surface melting and solidification. Hydrodynamic ablation is proposed to explain the formation of micropores and networks at higher laser fluence of 1100 and 1200 mJ/cm 2. The darkening effect is explained in terms of trapping of light in the surface defects formed rather than anatase to rutile phase transformation as reported by others. Controlled darkening of TiO 2 film might be used for adjustable filters.

External Control of Knowledge of Results: Learner Involvement Enhances Motor Skill Transfer.

PubMed

Figueiredo, L S; Ugrinowitsch, H; Freire, A B; Shea, J B; Benda, R N

2018-04-01

Providing the learner control over aspects of practice has improved the process of motor skill acquisition, and self-controlled knowledge of results (KR) schedules have shown specific advantages over externally controlled ones. A possible explanation is that self-controlled KR schedules lead learners to more active task involvement, permitting deeper information processing. This study tested this explanatory hypothesis. Thirty undergraduate volunteers of both sexes, aged 18 to 35, all novices in the task, practiced transporting a tennis ball in a specified sequence within a time goal. We compared a high-involvement group (involvement yoked, IY), notified in advance about upcoming KR trials, to self-controlled KR (SC) and yoked KR (YK) groups. The experiment consisted of three phases: acquisition, retention, and transfer. We found both IY and SC groups to be superior to YK for transfer of learning. Postexperiment participant questionnaires confirmed a preference for receiving KR after learner-perceived good trials, even though performance on those trials did not differ from performance on trials without KR. Equivalent IY and SC performances provide support for the benefits of task involvement and deeper information processing when KR is self-controlled in motor skill acquisition.

High-spin lifetime measurements in the N=Z nucleus Kr72

NASA Astrophysics Data System (ADS)

Andreoiu, C.; Svensson, C. E.; Afanasjev, A. V.; Austin, R. A. E.; Carpenter, M. P.; Dashdorj, D.; Finlay, P.; Freeman, S. J.; Garrett, P. E.; Greene, J.; Grinyer, G. F.; Görgen, A.; Hyland, B.; Jenkins, D.; Johnston-Theasby, F.; Joshi, P.; Machiavelli, A. O.; Moore, F.; Mukherjee, G.; Phillips, A. A.; Reviol, W.; Sarantites, D. G.; Schumaker, M. A.; Seweryniak, D.; Smith, M. B.; Valiente-Dobón, J. J.; Wadsworth, R.

2007-04-01

High-spin states in the N=Z nucleus Kr72 have been populated in the Ca40(Ca40, 2α)Kr72 fusion-evaporation reaction at a beam energy of 165 MeV using the Gammasphere array for γ-ray detection coupled to the Microball array for charged particle detection. The previously observed bands in Kr72 were extended to an excitation energy of ˜24 MeV and angular momentum of 30ℏ. Using the Doppler shift attenuation method the lifetimes of high-spin states were measured for the first time. Excellent agreement between the results of calculations within the isovector mean field theory and experiment is observed both for rotational and deformation properties. No enhancement of quadrupole deformation expected in the presence of isoscalar t=0 np pairing is observed. Current data do not show any evidence for the existence of the isoscalar np pairing.

Kr-85m activity as burnup measurement indicator in a pebble bed reactor based on ORIGEN2.1 Computer Simulation

NASA Astrophysics Data System (ADS)

Husnayani, I.; Udiyani, P. M.; Bakhri, S.; Sunaryo, G. R.

2018-02-01

Pebble Bed Reactor (PBR) is a high temperature gas-cooled reactor which employs graphite as a moderator and helium as a coolant. In a multi-pass PBR, burnup of the fuel pebble must be measured in each cycle by online measurement in order to determine whether the fuel pebble should be reloaded into the core for another cycle or moved out of the core into spent fuel storage. One of the well-known methods for measuring burnup is based on the activity of radionuclide decay inside the fuel pebble. In this work, the activity and gamma emission of Kr-85m were studied in order to investigate the feasibility of Kr-85m as burnup measurement indicator in a PBR. The activity and gamma emission of Kr-85 were estimated using ORIGEN2.1 computer code. The parameters of HTR-10 were taken as a case study in performing ORIGEN2.1 simulation. The results show that the activity revolution of Kr-85m has a good relationship with the burnup of the pebble fuel in each cycle. The Kr-85m activity reduction in each burnup step,in the range of 12% to 4%, is considered sufficient to show the burnup level in each cycle. The gamma emission of Kr-85m is also sufficiently high which is in the order of 1010 photon/second. From these results, it can be concluded that Kr-85m is suitable to be used as burnup measurement indicator in a pebble bed reactor.

High efficiency Dual-Cycle Conversion System using Kr-85.

PubMed

Prelas, Mark A; Tchouaso, Modeste Tchakoua

2018-04-26

This paper discusses the use of one of the safest isotopes known isotopes, Kr-85, as a candidate fuel source for deep space missions. This isotope comes from 0.286% of fission events. There is a vast quantity of Kr-85 stored in spent fuel and it is continually being produced by nuclear reactors. In using Kr-85 with a novel Dual Cycle Conversion System (DCCS) it is feasible to boost the system efficiency from 26% to 45% over a single cycle device while only increasing the system mass by less than 1%. The Kr-85 isotope is the ideal fuel for a Photon Intermediate Direct Energy Conversion (PIDEC) system. PIDEC is an excellent choice for the top cycle in a DCCS. In the top cycle, ionization and excitation of the Kr-85:Cl gas mixture (99% Kr and 1% Cl) from beta particles creates KrCl* excimer photons which are efficiently absorbed by diamond photovoltaic cells on the walls of the pressure vessels. The benefit of using the DCCS is that Kr-85 is capable of operating at high temperatures in the primary cycle and the residual heat can then be converted into electrical power in the bottom cycle which uses a Stirling Engine. The design of the DCCS begins with a spherical pressure vessel of radius 13.7 cm with 3.7 cm thick walls and is filled with a Kr-85:Cl gas mixture. The inner wall has diamond photovoltaic cells attached to it and there is a sapphire window between the diamond photovoltaic cells and the Kr-85:Cl gas mixture which shields the photovoltaic cells from beta particles. The DCCS without a gamma ray shield has specific power of 6.49 W/kg. A removable 6 cm thick tungsten shield is used to safely limit the radiation exposure levels of personnel. A shadow shield remains in the payload to protect the radiation sensitive components in the flight package. The estimated specific power of the unoptimized system design in this paper is about 2.33 W/kg. The specific power of an optimized system should be higher. The Kr-85 isotope is relatively safe because it will disperse quickly in case of an accident and if it enters the lungs there is no significant biological half-life. Copyright © 2018 Elsevier Ltd. All rights reserved.

Krüppel homolog 1 and E93 mediate Juvenile hormone regulation of metamorphosis in the common bed bug, Cimex lectularius.

PubMed

Gujar, Hemant; Palli, Subba Reddy

2016-05-17

The common bed bug is an obligate hematophagous parasite of humans. We studied the regulation of molting and metamorphosis in bed bugs with a goal to identify key players involved. qRT-PCR studies on the expression of genes known to be involved in molting and metamorphosis showed high levels of Krüppel homolog 1 [Kr-h1, a transcription factor that plays key roles in juvenile hormone (JH) action] mRNA in the penultimate nymphal stage (N4). However, low levels of Kr-h1 mRNA were detected in the fifth and last nymphal stage (N5). Knockdown of Kr-h1 in N4 resulted in a precocious development of adult structures. Kr-h1 maintains the immature stage by suppressing E93 (early ecdysone response gene) in N4. E93 expression increases during the N5 in the absence of Kr-h1 and promotes the development of adult structures. Knockdown of E93 in N5 results in the formation of supernumerary nymphs. The role of JH in the suppression of adult structures through interaction with Kr-h1 and E93 was also studied by the topical application of JH analog, methoprene, to N5. Methoprene induced Kr-h1 and suppressed E93 and induced formation of the supernumerary nymph. These data show interactions between Kr-h1, E93 and JH in the regulation of metamorphosis in the bed bugs.

Krüppel homolog 1 and E93 mediate Juvenile hormone regulation of metamorphosis in the common bed bug, Cimex lectularius

PubMed Central

Gujar, Hemant; Palli, Subba Reddy

2016-01-01

The common bed bug is an obligate hematophagous parasite of humans. We studied the regulation of molting and metamorphosis in bed bugs with a goal to identify key players involved. qRT-PCR studies on the expression of genes known to be involved in molting and metamorphosis showed high levels of Krüppel homolog 1 [Kr-h1, a transcription factor that plays key roles in juvenile hormone (JH) action] mRNA in the penultimate nymphal stage (N4). However, low levels of Kr-h1 mRNA were detected in the fifth and last nymphal stage (N5). Knockdown of Kr-h1 in N4 resulted in a precocious development of adult structures. Kr-h1 maintains the immature stage by suppressing E93 (early ecdysone response gene) in N4. E93 expression increases during the N5 in the absence of Kr-h1 and promotes the development of adult structures. Knockdown of E93 in N5 results in the formation of supernumerary nymphs. The role of JH in the suppression of adult structures through interaction with Kr-h1 and E93 was also studied by the topical application of JH analog, methoprene, to N5. Methoprene induced Kr-h1 and suppressed E93 and induced formation of the supernumerary nymph. These data show interactions between Kr-h1, E93 and JH in the regulation of metamorphosis in the bed bugs. PMID:27185064

Stellar laboratories. VII. New Kr iv - vii oscillator strengths and an improved spectral analysis of the hot, hydrogen-deficient DO-type white dwarf RE 0503-289

NASA Astrophysics Data System (ADS)

Rauch, T.; Quinet, P.; Hoyer, D.; Werner, K.; Richter, P.; Kruk, J. W.; Demleitner, M.

2016-05-01

Context. For the spectral analysis of high-resolution and high signal-to-noise (S/N) spectra of hot stars, state-of-the-art non-local thermodynamic equilibrium (NLTE) model atmospheres are mandatory. These are strongly dependent on the reliability of the atomic data that is used for their calculation. Aims: New Kr iv-vii oscillator strengths for a large number of lines enable us to construct more detailed model atoms for our NLTE model-atmosphere calculations. This enables us to search for additional Kr lines in observed spectra and to improve Kr abundance determinations. Methods: We calculated Kr iv-vii oscillator strengths to consider radiative and collisional bound-bound transitions in detail in our NLTE stellar-atmosphere models for the analysis of Kr lines that are exhibited in high-resolution and high S/N ultraviolet (UV) observations of the hot white dwarf RE 0503-289. Results: We reanalyzed the effective temperature and surface gravity and determined Teff = 70000 ± 2000 K and log (g/ cm s-2) = 7.5 ± 0.1. We newly identified ten Kr v lines and one Kr vi line in the spectrum of RE 0503-289. We measured a Kr abundance of -3.3 ± 0.3 (logarithmic mass fraction). We discovered that the interstellar absorption toward RE 0503-289 has a multi-velocity structure within a radial-velocity interval of -40 km s-1

Electronic phase separation at the LaAlO₃/SrTiO₃ interface.

PubMed

Ariando; Wang, X; Baskaran, G; Liu, Z Q; Huijben, J; Yi, J B; Annadi, A; Barman, A Roy; Rusydi, A; Dhar, S; Feng, Y P; Ding, J; Hilgenkamp, H; Venkatesan, T

2011-02-08

There are many electronic and magnetic properties exhibited by complex oxides. Electronic phase separation (EPS) is one of those, the presence of which can be linked to exotic behaviours, such as colossal magnetoresistance, metal-insulator transition and high-temperature superconductivity. A variety of new and unusual electronic phases at the interfaces between complex oxides, in particular between two non-magnetic insulators LaAlO(3) and SrTiO(3), have stimulated the oxide community. However, no EPS has been observed in this system despite a theoretical prediction. Here, we report an EPS state at the LaAlO(3)/SrTiO(3) interface, where the interface charges are separated into regions of a quasi-two-dimensional electron gas, a ferromagnetic phase, which persists above room temperature, and a (superconductor like) diamagnetic/paramagnetic phase below 60 K. The EPS is due to the selective occupancy (in the form of 2D-nanoscopic metallic droplets) of interface sub-bands of the nearly degenerate Ti orbital in the SrTiO(3). The observation of this EPS demonstrates the electronic and magnetic phenomena that can emerge at the interface between complex oxides mediated by the Ti orbital.

Halogens, Barium and Uranium in Mantle Fluid Inclusions

NASA Astrophysics Data System (ADS)

Villa, I. M.; Peverelli, V.; Oglialoro, E.; Pettke, D. T.; Frezzotti, M. L.

2016-12-01

Halogens are an underexplored geochemical marker. A way to measure halogens at ng/g levels is measuring Ar, Kr and Xe in irradiated samples [1,2]. We derive absolute halogen amounts from rare gas amounts via scapolite monitor SY [2]. Kr-Xe systematics also yield Ba and U concentrations. We combined irradiation with stepheating on carbonate-sulfate-rich fluid inclusions (FI)-bearing xe­no­liths from El Hierro, Canarias: spinel harzburgite XML-7 and spinel dunite XML-1 [3]. Three components are recognized in the rare gas release. (1) Atmospheric surface contamination occurs up to 1000 °C. (2) FI decrepitation by laboratory heating occurs above 1200 °C [4], corresponding to the release of 80,82Kr and 128Xe in the 1200 and 1400 °C steps. Br whole-rock concentrations are 3-8 ng/g; the molar Br/Cl and I/Cl ratios in the harzburgite FI, 9 E-4 resp. 2 E-4, are identical to those in the dunite FI. This sets the halogens in our FI apart from MORB [2]. Halogen-derived rare gases are closely associated to artificial 131Xe from Ba; Ba has a high affinity of for CO2-rich fluids. Daughter minerals in multiphase FI were identified by Raman micro­spectroscopy [4]. The calculated Ba concentrations are 2-6 µg/g. (3) The third component is U-derived 134,136Xe and 86Kr released in a spike at 1000 °C, decoupled from FI. This requires a different carrier than FI, e.g. Ti oxides. As U concentrations are 10-20 pg/g, the U-bearing phase needs to be below a ppm, invisible by petro­graphy. The 136Xe/134Xe ratio > 1 suggests retention of radio­genic Xe. However, analysis of an unirradiated sample detected no radiogenic Xe. It is likely that Xe-U produced in the core of the McMaster reactor (thermal, epithermal and fast neutrons) has a different isotopic composition from that in textbooks, as proposed by [2].[1] Jeffery & Reynolds (1961) J.Geophys. Res. 66, 3582 [2] Kendrick (2012) Chem. Geol. 292, 116 [3] Oglialoro et al (2015) AGU Fall Meeting abstract V21C-3046 [4] Roedder (1965) Am. Min. 50, 1746

Quasi 2D Ultrahigh Carrier Density in a Complex Oxide Broken Gap Heterojunction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Peng; Droubay, Timothy C.; Jeong, Jong S.

2016-01-21

Two-dimensional (2D) ultra-high carrier densities at complex oxide interfaces are of considerable current research interest for novel plasmonic and high charge-gain devices. However, the highest 2D electron density obtained in oxide heterostructures is thus far limited to 3×1014 cm-2 (½ electron/unit cell/interface) at GdTiO3/SrTiO3 interfaces, and is typically an order of magnitude lower at LaAlO3/SrTiO3 interfaces. Here we show that carrier densities much higher than 3×1014 cm-2 can be achieved via band engineering. Transport measurements for 3 nm SrTiO3/t u.c. NdTiO3/3 nm SrTiO3/LSAT (001) show that charge transfer significantly in excess of the value expected from the polar discontinuity modelmore » occurs for higher t values. The carrier density remains unchanged, and equivalent to ½ electron/unit cell/interface for t < 6 unit cells. However, above a critical NdTiO3 thickness of 6 u.c., electrons from the valence band of NdTiO3 spill over into the SrTiO3 conduction band as a natural consequence of the band alignment. An atomistic model consistent with first-principle calculations and experimental results is proposed for the charge transfer mechanisms. These results may provide an exceptional route to the realization of the room-temperature oxide electronics.« less

The Liquid Krypton Hugoniot at Megabar Pressures

NASA Astrophysics Data System (ADS)

Root, Seth; Magyar, Rudy J.; Mattsson, Ann E.; Hanson, David L.; Mattsson, Thomas R.

2011-06-01

Krypton is an ideal candidate to study multi-Mbar pressure effects on elements with filled-shell electron configurations. Few experimental data on Kr at high pressures exist, however, with prior Hugoniot data limited to below 1 Mbar. Similar to liquid xenon, the current Kr equation of state (EOS) models agree with the data and each other below 1 Mbar, but diverge with increasing pressure. We examine the liquid Kr Hugoniot up to 8 Mbar by using density functional theory (DFT) methods and by performing shock compression experiments on the Sandia Z - accelerator. Our initial DFT Kr Hugoniot calculations indicated the standard PAW potential is inadequate at the high pressures and temperatures occurring under strong shock compression. A new Kr PAW potential was constructed giving improved scattering properties of the atom at high energies. The Z Hugoniot measurements above 1 Mbar validated the DFT results and the pseudo-potential. The DFT and Z results suggest that the current EOS models require some modifications. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, for the U. S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Forbidden line emission from highly ionized atoms in tokamak plasmas

NASA Technical Reports Server (NTRS)

Feldman, U.; Doschek, G. A.; Bhatia, A. K.

1982-01-01

Considerable interest in the observation of forbidden spectral lines from highly ionized atoms in tokamak plasmas is related to the significance of such observations for plasma diagnostic applications. Atomic data for the elements Ti Cr, Mn, Fe, Ni, and Kr have been published by Feldman et al. (1980) and Bhatia et al. (1980). The present investigation is concerned with collisional excitation rate coefficients and radiative decay rates, which are interpolated for ions of elements between calcium, and krypton and for levels of the 2s2 2pk, 2s 2p(k+1), and 2p(k+2) configurations, and for the O I, N I, C I, B I, and Be I isoelectronic sequences. The provided interpolated atomic data can be employed to calculate level populations and relative line intensities for ions of the considered sequences, taking into account levels of the stated configurations. Important plasma diagnostic information provided by the forbidden lines includes the ion temperature

Quenching of electron transfer reactions through coadsorption: A study of oxygen photodesorption from TiO 2(110)

DOE PAGES

Petrik, Nikolay G.; Kimmel, Greg A.; Shen, Mingmin; ...

2016-01-11

Using temperature programmed desorption (TPD) and photon-stimulated desorption (PSD), we show that coadsorbates of varying binding energies on the rutile TiO 2(110) surface exert a commensurate inhibiting influence on the hole-mediated photodesorption of adsorbed O 2. A variety of coadsorbates (Ar, Kr, Xe, N 2, CO, CO 2, CH 4, N 2O, acetone, methanol or water) were shown to quench O 2 photoactivity, with the extent correlating with the coadsorbate's gas phase basicity, which in turn determines the strength of the coadsorbate–Ti 4+ bond. Coadsorbed rare gases inhibited the photodesorption of O 2 by ~ 10–25%, whereas strongly bound speciesmore » (water, methanol, and acetone) nearly completely inhibited O 2 PSD. We suggest that coadsorption of these molecules inhibit the arrival probability of holes to the surface. Band-bending effects, which vary with the extent of charge transfer between the coadsorbate and the TiO 2(110) surface, are not expected to be significant in the cases of the rare gases and physisorbed species. Furthermore, these results indicate that neutral coadsorbates can exert a significant influence on charge transfer events by altering the interfacial dipole in the vicinity of the target molecule.« less

Positron annihilation studies on the behaviour of vacancies in LaAlO3/SrTiO3 heterostructures

NASA Astrophysics Data System (ADS)

Yuan, Guoliang; Li, Chen; Yin, Jiang; Liu, Zhiguo; Wu, Di; Uedono, Akira

2012-11-01

The formation and diffusion of vacancies are studied in LaAlO3/SrTiO3 heterostructures. Oxygen vacancies (VOS) appear easily in the SrTiO3 substrate during LaAlO3 film growth at 700 °C and 10-4 Pa oxygen pressure rather than at 10-3-10-1 Pa, thus the latter two-dimensional electron gas should come from the polarity discontinuity at the (LaO)+/(TiO2)0 interface. For SrTiO3-δ/LaAlO3/SrTiO3, high-density VOS of the SrTiO3-δ film can pass through the LaAlO3 film and then diffuse to 1.7 µm depth in the SrTiO3 substrate, suggesting that LaAlO3 has VOS at its middle-deep energy levels within the band gap. Moreover, high-density VOS may combine with a strontium/titanium vacancy (VSr/Ti) to form VSr/Ti-O complexes in the SrTiO3 substrate at 700 °C.

The effect of copper doping on martensite shear stress in porous TiNi(Mo,Fe,Cu) alloys

NASA Astrophysics Data System (ADS)

Khodorenko, V. N.; Kaftaranova, M. I.; Gunther, V. E.

2015-03-01

The properties of alloys based on porous nickel-titanium (TiNi) with copper additives have been studied. It is established that the copper doping of porous TiNi(Mo,Fe,Cu) alloys fabricated by the method of self-propagating high-temperature synthesis leads to a significant decrease in the martensite shear stress (below 30 MPa). Low values of the martensite shear stress (σmin) in copper-doped TiNi-based alloys allows medical implants of complex shapes to be manufactured for various purposes, including oral surgery. The optimum concentration of copper additives (within 3-6 at %) has been determined that ensures high performance characteristics of TiNi-based porous alloys for medical implants.

Structural and Biochemical Analyses of Regio- and Stereo-Specificities Observed in a Type II Polyketide Ketoreductase

PubMed Central

Javidpour, Pouya; Korman, Tyler Paz; Shakya, Gaurav; Tsai, Shiou-Chuan

2011-01-01

Type II polyketides include antibiotics such as tetracycline, and chemotherapeutics such as daunorubicin. Type II polyketides are biosynthesized by the type II polyketide synthase (PKS) that consists of 5 – 10 stand-alone domains. In many type II PKSs, the type II ketoreductase (KR) specifically reduce the C9-carbonyl group. How the type II KR achieves such a high regio-specificity, and the nature of stereo-specificity, are not well understood. Sequence alignment of KRs led to a hypothesis that a well-conserved 94-XGG-96 motif may be involved in controlling the stereochemistry. The stereo-specificity of single, double and triple mutant combinations of P94L, G95D and G96D were analyzed in vitro and in vivo for the actinorhodin KR (actKR). The P94L mutation is sufficient to change the stereospecificity of actKR. Binary and ternary crystal structures of both wild type and P94L actKR were solved. Together with assay results, docking simulations, and co-crystal structures, a model for stereochemical control is presented herein that elucidates how type II polyketides are introduced into the substrate pocket such that the C9-carbonyl can be reduced with high regio- and stereo-specificities. The molecular features of actKR important for regio- and stereo-specificities can potentially be applied to biosynthesize new polyketides via protein engineering that rationally controls polyketide ketoreduction. PMID:21506596

Signal intensity alteration within infrapatellar fat pad predicts knee replacement within 5 years: data from the Osteoarthritis Initiative.

PubMed

Wang, K; Ding, C; Hannon, M J; Chen, Z; Kwoh, C K; Lynch, J; Hunter, D J

2018-05-26

To investigate whether infrapatellar fat pad (IPFP) signal intensity (SI) alteration predicts the occurrence of knee replacement (KR) in knee osteoarthritis (OA) patients over 5 years. The subjects were selected from Osteoarthritis Initiative (OAI) study. Case knees (n = 127) were defined as those who received KR during 5 years follow-up visit. They were matched by gender, age and radiographic status with control knees (n = 127). We used T2-weighted MR images to measure IPFP SI alteration using a newly developed algorithm in MATLAB. The measurements were assessed at baseline (BL), T0 (the visit just before KR) and 1 year before T0 (T-1). Conditional logistic regression was used to analyse the associations between IPFP SI alterations and the risk of KR. Participants were mostly female (57%), with an average age of 63.7 years old and a mean body mass index (BMI) of 29.5 kg/m 2 . In multivariable analysis, the standard deviation (SD) of IPFP SI [sDev (IPFP)] and the ratio of high SI region volume to whole IPFP volume [Percentage (H)] measured at BL were significantly associated with increased risks of KR after adjustment for covariates. IPFP SI alterations measured at T-1 including sDev (IPFP), Percentage (H) and clustering effect of high SI [Clustering factor (H)] were significantly associated with higher risks of KR. All measurements were significantly associated with higher risks of KR at T0. IPFP SI is associated with the occurrence of KR suggesting it may play a role in end-stage knee OA. Copyright © 2018 Osteoarthritis Research Society International. Published by Elsevier Ltd. All rights reserved.

Spectroscopic abundance analyses of the 3He stars HD 185330 and 3 Cen A

NASA Astrophysics Data System (ADS)

Sadakane, Kozo; Nishimura, Masayoshi

2018-06-01

Abundances of 21 elements in two 3He stars, HD 185330 and 3 Cen A, have been analysed relative to the well-studied sharp-lined B3 V star ι Her. Six elements (P, Ti, Mn, Fe, Ni, and Br) are over-abundant in these two peculiar stars, while six elements (C, O, Mg, Al, S, and Cl) are under-abundant. Absorption lines of the two rarely observed heavy elements Br II and Kr II are detected in both stars and these elements are both over-abundant. The centroid wavelengths of the Ca II infrared triplet lines in these stars are redshifted relative to those lines in ι Her and the presence of heavy isotopes of Ca (mass number 44-46) in these two stars is confirmed. In spite of these similarities, there are several remarkable differences in abundance pattern between these two stars. N is under-abundant in HD 185330, as in many Hg-Mn stars, while it is significantly over-abundant in 3 Cen A. P and Ga are both over-abundant in 3 Cen A, while only P is over-abundant and no trace of absorption line of Ga II can be found in HD 185330. Large over-abundances of Kr and Xe are found in both stars, while the abundance ratio Kr/Xe is significantly different between them (-1.4 dex in HD 185330 and +1.2 dex in 3 Cen A). Some physical explanations are needed to account for these qualitative differences.

Spectroscopic abundance analyses of the 3He stars HD 185330 and 3 Cen A

NASA Astrophysics Data System (ADS)

Sadakane, Kozo; Nishimura, Masayoshi

2018-04-01

Abundances of 21 elements in two 3He stars, HD 185330 and 3 Cen A, have been analysed relative to the well-studied sharp-lined B3 V star ι Her. Six elements (P, Ti, Mn, Fe, Ni, and Br) are over-abundant in these two peculiar stars, while six elements (C, O, Mg, Al, S, and Cl) are under-abundant. Absorption lines of the two rarely observed heavy elements Br II and Kr II are detected in both stars and these elements are both over-abundant. The centroid wavelengths of the Ca II infrared triplet lines in these stars are redshifted relative to those lines in ι Her and the presence of heavy isotopes of Ca (mass number 44-46) in these two stars is confirmed. In spite of these similarities, there are several remarkable differences in abundance pattern between these two stars. N is under-abundant in HD 185330, as in many Hg-Mn stars, while it is significantly over-abundant in 3 Cen A. P and Ga are both over-abundant in 3 Cen A, while only P is over-abundant and no trace of absorption line of Ga II can be found in HD 185330. Large over-abundances of Kr and Xe are found in both stars, while the abundance ratio Kr/Xe is significantly different between them (-1.4 dex in HD 185330 and +1.2 dex in 3 Cen A). Some physical explanations are needed to account for these qualitative differences.

Defect types and room-temperature ferromagnetism in undoped rutile TiO2 single crystals

NASA Astrophysics Data System (ADS)

Li, Dong-Xiang; Qin, Xiu-Bo; Zheng, Li-Rong; Li, Yu-Xiao; Cao, Xing-Zhong; Li, Zhuo-Xin; Yang, Jing; Wang, Bao-Yi

2013-03-01

Room-temperature ferromagnetism has been experimentally observed in annealed rutile TiO2 single crystals when a magnetic field is applied parallel to the sample plane. By combining X-ray absorption near the edge structure spectrum and positron annihilation lifetime spectroscopy, Ti3+—VO defect complexes (or clusters) have been identified in annealed crystals at a high vacuum. We elucidate that the unpaired 3d electrons in Ti3+ ions provide the observed room-temperature ferromagnetism. In addition, excess oxygen ions in the TiO2 lattice could induce a number of Ti vacancies which obviously increase magnetic moments.

Enhanced photocurrent production by bio-dyes of photosynthetic macromolecules on designed TiO2 film

PubMed Central

Yu, Daoyong; Wang, Mengfei; Zhu, Guoliang; Ge, Baosheng; Liu, Shuang; Huang, Fang

2015-01-01

The macromolecular pigment-protein complex has the merit of high efficiency for light-energy capture and transfer after long-term photosynthetic evolution. Here bio-dyes of A. platensis photosystem I (PSI) and spinach light-harvesting complex II (LHCII) are spontaneously sensitized on three types of designed TiO2 films, to assess the effects of pigment-protein complex on the performance of bio-dye sensitized solar cells (SSC). Adsorption models of bio-dyes are proposed based on the 3D structures of PSI and LHCII, and the size of particles and inner pores in the TiO2 film. PSI shows its merit of high efficiency for captured energy transfer, charge separation and transfer in the electron transfer chain (ETC), and electron injection from FB to the TiO2 conducting band. After optimization, the best short current (JSC) and photoelectric conversion efficiency (η) of PSI-SSC and LHCII-SSC are 1.31 mA cm-2 and 0.47%, and 1.51 mA cm-2 and 0.52%, respectively. The potential for further improvement of this PSI based SSC is significant and could lead to better utilization of solar energy. PMID:25790735

KrF laser-induced OH fluorescence imaging in a supersonic combustion tunnel

NASA Technical Reports Server (NTRS)

Quagliaroli, T. M.; Laufer, G.; Hollo, S. D.; Krauss, R. H.; Whitehurst, R. B., III; Mcdaniel, J. C., Jr.

1992-01-01

Planar fluorescence images of OH in a continuous-flow, electrical-resistively heated, high enthalpy, hydrogen-air combustion tunnel, induced by a tunable KrF laser, were recorded. These images were compared to previously recorded fluorescence images induced by a doubled-dye laser under similar conditions. Images induced by the doubled-dye laser system demonstrated a severe distortion caused by absorption and fluorescence trapping. By contrast, images of the fluorescence induced by the tunable KrF laser retained the symmetry properties of the flow. Based on signal-to-noise ratio measurements the yield of the fluorescence induced by the doubled-dye laser is larger than the fluorescence yield induced by the KrF laser. The measurements in the present facility of OH fluorescence induced by the KrF laser were limited by the photon-statistical noise. Based 2 on this result, doubled-dye laser systems are recommended for OH imaging in small and OH lean (less than 10 exp 15/cu cm) facilities. KrF lasers should be selected otherwise.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shirkov, Leonid; Makarewicz, Jan, E-mail: jama@amu.edu.pl

An ab initio intermolecular potential energy surface (PES) has been constructed for the benzene-krypton (BKr) van der Waals (vdW) complex. The interaction energy has been calculated at the coupled cluster level of theory with single, double, and perturbatively included triple excitations using different basis sets. As a result, a few analytical PESs of the complex have been determined. They allowed a prediction of the complex structure and its vibrational vdW states. The vibrational energy level pattern exhibits a distinct polyad structure. Comparison of the equilibrium structure, the dipole moment, and vibrational levels of BKr with their experimental counterparts has allowedmore » us to design an optimal basis set composed of a small Dunning’s basis set for the benzene monomer, a larger effective core potential adapted basis set for Kr and additional midbond functions. Such a basis set yields vibrational energy levels that agree very well with the experimental ones as well as with those calculated from the available empirical PES derived from the microwave spectra of the BKr complex. The basis proposed can be applied to larger complexes including Kr because of a reasonable computational cost and accurate results.« less

Morphological and phase evolution of TiO 2 nanocrystals prepared from peroxotitanate complex aqueous solution: Influence of acetic acid

NASA Astrophysics Data System (ADS)

Chang, Jeong Ah; Vithal, Muga; Baek, In Chan; Seok, Sang Il

2009-04-01

Nanosized anatase and rutile TiO 2 having different shape, phase and size have been prepared from aqueous solutions of peroxo titanium complex starting from titanium(IV) isopropoxide (TTIP), acetic acid and hydrogen peroxide (H 2O 2) in water/isopropanol media by a facile sol-gel process. The TiO 2 nanocrystals are characterized by powder X-ray diffraction (XRD), Raman spectroscopy, FT-IR spectroscopy, TEM, high resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) techniques. The influence of pH and the sequence of addition of reaction contents on the phase and morphology of TiO 2 are studied. The reasons for the observation of only anatase and/or mixture of anatase and rutile are given.

Principal network analysis: identification of subnetworks representing major dynamics using gene expression data

PubMed Central

Kim, Yongsoo; Kim, Taek-Kyun; Kim, Yungu; Yoo, Jiho; You, Sungyong; Lee, Inyoul; Carlson, George; Hood, Leroy; Choi, Seungjin; Hwang, Daehee

2011-01-01

Motivation: Systems biology attempts to describe complex systems behaviors in terms of dynamic operations of biological networks. However, there is lack of tools that can effectively decode complex network dynamics over multiple conditions. Results: We present principal network analysis (PNA) that can automatically capture major dynamic activation patterns over multiple conditions and then generate protein and metabolic subnetworks for the captured patterns. We first demonstrated the utility of this method by applying it to a synthetic dataset. The results showed that PNA correctly captured the subnetworks representing dynamics in the data. We further applied PNA to two time-course gene expression profiles collected from (i) MCF7 cells after treatments of HRG at multiple doses and (ii) brain samples of four strains of mice infected with two prion strains. The resulting subnetworks and their interactions revealed network dynamics associated with HRG dose-dependent regulation of cell proliferation and differentiation and early PrPSc accumulation during prion infection. Availability: The web-based software is available at: http://sbm.postech.ac.kr/pna. Contact: dhhwang@postech.ac.kr; seungjin@postech.ac.kr Supplementary information: Supplementary data are available at Bioinformatics online. PMID:21193522

Coexistence of superfluid and rigid moments of inertia in 76,78Kr

NASA Astrophysics Data System (ADS)

Kaplan, M. S.; Saladin, J. X.; Faro, L.; Winchell, D. F.; Takai, H.; Knott, C. N.

1988-12-01

High spin states in 76,78Kr were populated via the 63Cu( 16O,n2p) 76Kr and 64Ni( 18O,4n) 78Kr reactions at 69 MeV and γγ coincidence data were collected. New band crossings and quasi-particle alignments are discussed. Moments of inertia of bands built on intrinsic excitations are found to be exceptionally constant with spin and equal to the rigid-body value, indicating strong suppression of coherent pairing correlations. The coexistence of such bands with bands of reduced, superfluid moments of inertia suggests the appearance of a new phenomenon: phase coexistence.

Influence of the interface layer on the adhesion of pulsed laser deposited hydroxyapatite coatings on titanium alloy

NASA Astrophysics Data System (ADS)

Fernández-Pradas, J. M.; García-Cuenca, M. V.; Clèries, L.; Sardin, G.; Morenza, J. L.

2002-07-01

Hydroxyapatite (HA) coatings were deposited on Ti-6Al-4V substrates by laser ablation with a KrF excimer laser. Depositions were performed at 45 Pa of water vapour and at a substrate temperature of 575 °C. After 7 min of deposition, coatings were left at this temperature for different times before cooling down. The samples morphology and structure were characterised by scanning electron microscopy, X-ray diffractometry and Raman spectroscopy. The mechanical performance of the coatings was evaluated through the scratch-test technique. The coatings do not present important differences between them. However, there is an interface layer between the coating and the substrate that indeed presents an evolution with the heating time. This interface layer is constituted by two different species: titanium oxide and Ti-6Al-4V with oxygen diffused in its lattice. Its thickness increases during the first minutes of heating after deposition. An evolution of the titanium oxide phases with the time of heating has been detected by Raman spectroscopy. The samples fail at lower loads in the scratch-test as longer is the time that they remained at high temperature. The mode of failure of the samples suggests that failure occurs at the interface.

Staged Z-pinch experiments on the Mega-Ampere current driver COBRA

NASA Astrophysics Data System (ADS)

Valenzuela, Julio; Banasek, Jacob; Byvank, Thomas; Conti, Fabio; Greenly, John; Hammer, David; Potter, William; Rocco, Sophia; Ross, Michael; Wessel, Frank; Narkis, Jeff; Rahman, Hafiz; Ruskov, Emil; Beg, Farhat

2017-10-01

Experiments were conducted on the Cornell's 1 MA, 100 ns current driver COBRA with the goal of better understanding the Staged Z-pinch physics and validating MHD codes. We used a gas injector composed of an annular (1.2 cm radius) high atomic number (e.g., Ar or Kr) gas-puff and an on-axis plasma gun that delivers the ionized hydrogen target. Liner implosion velocity and stability were studied using laser shadowgraphy and interferometry as well as XUV imaging. From the data, the signature of the MRT instability and zippering effect can be seen, but time integrated X-ray imaging show a stable target plasma. A key component of the experiment was the use of optical Thomson scattering (TS) diagnostics to characterize the liner and target plasmas. By fitting the experimental scattered spectra with synthetic data, electron and ion temperature as well as density can be obtained. Preliminary analysis shows significant scattered line broadening from the plasma on-axis ( 0.5 mm diameter) which can be explained by either a low temperature H plasma with Te =Ti =75eV, or by a hot plasma with Ti =3keV, Te =350eV if an Ar-H mixture is present with an Ar fraction higher than 10%. Funded by the Advanced Research Projects Agency - Energy, DE-AR0000569.

Effective surface passivation of multi-shelled InP quantum dots through a simple complexing with titanium species

NASA Astrophysics Data System (ADS)

Jo, Jung-Ho; Kim, Min-Seok; Han, Chang-Yeol; Jang, Eun-Pyo; Do, Young Rag; Yang, Heesun

2018-01-01

Fluorescent efficiency of various visible quantum dots (QDs) has been incessantly improved to meet industrially high standard mainly through the advance in core/shell heterostructural design, however, their stability against degradable environments appears still lacking. The most viable strategy to cope with this issue was to exploit chemically inert oxide phases to passivate QD surface in the form of either individual overcoating or matrix embedding. Herein, we report a simple but effective means to passivate QD surface by complexing its organic ligands with a metal alkoxide of titanium isopropoxide (Ti(i-PrO)4). For this, highly efficient red-emitting InP QDs with a multi-shell structure of ZnSeS intermediate plus ZnS outer shell are first synthesized and then the surface of resulting InP/ZnSeS/ZnS QDs is in-situ decorated with Ti(i-PrO)4. The presence of Tisbnd O species from Ti(i-PrO)4 on QD surface is verified by x-ray photoelectron and Fourier transform infrared spectroscopic analyses. Two comparative dispersions of pristine versus Ti(i-PrO)4-complexed QDs are exposed for certain periods of time to UV photon and heat and their temporal changes in photoluminescence are monitored, resulting in a huge improvement in QD stability from the latter ones through Ti(i-PrO)4-mediated better surface passivation.

Microstructure and property correlations in high-temperature superconductors

NASA Astrophysics Data System (ADS)

Kalyanaraman, Ramakrishnan

1998-11-01

The work in this dissertation is intended at developing high quality device gradefilms of the high temperature (high-Tsbc) superconductor, Yttrium Barium Copper Oxide (YBCO), on MgO(001) substrates. Three approaches have been used to achieve the above goal, (i) The use of a SrTiOsb3 buffer layer, (ii) The use of Ag to enhance the growth of YBCO films and (iii) Investigation of the atomic structure-property correlations of low-angle grain boundaries in these films. Thin film heterostructures of YBCO/MgO and YBCO/SrTiOsb3/MgO were fabricated by pulsed laser deposition (PLD), using a 248 nm KrF excimer laser. Analysis of the structure and measurement of superconducting properties of the films were carried out to optimize the suitable conditions under each approach. The key findings were, (i) Single crystal-like SrTiOsb3 buffer layers can be grown and they give the highest JsbcYBCO films, (ii) An in-depth study of the role of Ag showed that it enhanced film growth of YBCO thereby improving its quality, and (iii) Low-angle boundaries in YBCO/MgO occur with two probable habit planes and the Jsbcs across them differ slightly. A systematic investigation of the crystalline quality of the SrTiOsb3 films deposited by PLD was performed as a function of oxygen partial pressure (pOsb2) and substrate temperature (Tsbc). The highest quality films were grown in the pOsb2 range of 0.1-1 mTorr at 750sp°C. The films had as-deposited x-ray diffraction rocking curve (omega) values of {˜}0.70sp° and Rutherford backscattering channeling yields (chisbmin) of 5% as compared to omega˜1.40sp° and chisbmin˜14% for the film deposited in 100 mTorr of pOsb2. The x-ray phi-scans showed epitaxial cube-on-cube alignment of the SrTiOsb3 films on MgO(001) substrates. Thermal annealing of the SrTiOsb3 films further improved the quality, and the 1 mTorr films gave omega{˜}0.13sp° and chisbmin˜2.0%. Transmission electron microscopy investigations (TEM) of these films showed that the defects in films grown in the pOsb2 range of 0.5-1 mTorr consisted mainly of dislocations and sub-grain boundaries, while those grown in the higher pOsb2 contained numerous low-angle grain boundaries. YBCO films grown on the best SrTiOsb3 buffer layers showed reproducible Jsbcs of {˜}5.5× 10sp6 amps/cmsp2 at 77K and Tsbcs of 88-91K. The YBCO films was observed to grow epitaxially on SrTiOsb3 with (110) sbPYBCO//(110) sbSriTiO3 and (001) sbYBCO//(001) sbSrTiO3{*}chisbmin for the best YBCO film was ˜2.8%. The crystalline quality of the SrTiOsb3 and YBCO films developed are amongst the highest reported so far. Composite targets of Ag+YBCO were used to grow YBCO films using PLD. Using XRD and Tsbc measurements clear evidence for enhanced oxygenation of the YBCO films was shown. Detailed TEM investigation of grain boundaries in YBCO/MgO(001) showed that the low-angle grain boundaries in YBCO are equally likely to have (100) or (110) habit planes. (Abstract shortened by UMI.)

Growth of metal oxide thin films by laser-induced metalorganic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Tokita, Koji; Okada, Fumio

1996-12-01

The growth of metal oxide thin films by laser-induced metalorganic chemical vapor deposition was investigated by changing wavelength, power, repetition rate, and irradiation angle of the excimer laser. When O2 was used as an oxidizing gas with 193 or 248 nm irradiation, amorphous TiO2 and crystalline PbO films were obtained in the laser-irradiated area of Si substrates from the parent metalorganic compounds, Ti(O-iC3H7)4 and (C2H5)3PbOCH2C(CH3)3, respectively. In contrast, no ZrO2 film could be formed from Zr(O-tC4H9)4. One-photon formation of TiO2 films was confirmed from laser power dependence measurements. The maximum growth rate of 0.05 Å per laser pulse was compared with that estimated by a simple surface reaction model, according to which the slow growth rate is due to the small absorption cross section of Ti(O-iC3H7)4 and mild fluence of laser irradiation. In experiments of ozone gas excitation by KrF laser, a SiO2 film was obtained by gas-phase reactions of the oxygen radical, O(1D), with Si(O-C2H5)4. The direct patterning of TiO2 and PbO films as well as the possibility of producing patterned PbTiO3 film was demonstrated. The growth of the patterned SiO2 film was prevented by gas-phase diffusion of intermediates.

Background Information and User Guide for MIL-F-8785C, Military Specification - Flying Qualities of Piloted Airplanes

DTIC Science & Technology

1982-07-01

Design Military Specification 20. ABSTRACT (Co.itInue o., revorse.• de if ,lec0O.•,•dr’ 1 Id•ntnify’’ bY bI. rk ,CI•,ti lim r) ’This document is published...criteria to Insert into the basic requirements, verification proceduresand leason: learned from past experience. The Standkerd will thus be the framework ...equations with sketch: Each of the three paired quantities in the de - nominators of KS and KR should have a hir over them, as is done in the numerators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Ting; Feng, Xuhui; Elsaidi, Sameh K.

Herein, we demonstrate that a prototypical type of metal organic framework, zeolitic imidazolate framework-8 (ZIF-8), in membrane form, can effectively separate Kr/Xe gas mixtures at industrially relevant compositions. The best membranes separated Kr/Xe mixtures with average Kr permeances as high as 1.5 × 10 -8 ± 0.2 mol/m 2 s Pa and average separation selectivities of 14.2 ± 1.9 for molar feed compositions corresponding to Kr/Xe ratio encountered typically in air. Molecular sieving, competitive adsorption, and differences in diffusivities were identified as the prevailing separation mechanisms. These membranes potentially represent a less-energy-intensive alternative to cryogenic distillation, which is the benchmarkmore » technology used to separate this challenging gas mixture. To our best knowledge, this is the first example of any metal organic membrane composition displaying separation ability for Kr/Xe gas mixtures.« less

Transcription factor E93 specifies adult metamorphosis in hemimetabolous and holometabolous insects.

PubMed

Ureña, Enric; Manjón, Cristina; Franch-Marro, Xavier; Martín, David

2014-05-13

All immature animals undergo remarkable morphological and physiological changes to become mature adults. In winged insects, metamorphic changes either are limited to a few tissues (hemimetaboly) or involve a complete reorganization of most tissues and organs (holometaboly). Despite the differences, the genetic switch between immature and adult forms in both types of insects relies on the disappearance of the antimetamorphic juvenile hormone (JH) and the transcription factors Krüppel-homolog 1 (Kr-h1) and Broad-Complex (BR-C) during the last juvenile instar. Here, we show that the transcription factor E93 is the key determinant that promotes adult metamorphosis in both hemimetabolous and holometabolous insects, thus acting as the universal adult specifier. In the hemimetabolous insect Blattella germanica, BgE93 is highly expressed in metamorphic tissues, and RNA interference (RNAi)-mediated knockdown of BgE93 in the nymphal stage prevented the nymphal-adult transition, inducing endless reiteration of nymphal development, even in the absence of JH. We also find that BgE93 down-regulated BgKr-h1 and BgBR-C expression during the last nymphal instar of B. germanica, a key step necessary for proper adult differentiation. This essential role of E93 is conserved in holometabolous insects as TcE93 RNAi in Tribolium castaneum prevented pupal-adult transition and produced a supernumerary second pupa. In this beetle, TcE93 also represses expression of TcKr-h1 and TcBR-C during the pupal stage. Similar results were obtained in the more derived holometabolous insect Drosophila melanogaster, suggesting that winged insects use the same regulatory mechanism to promote adult metamorphosis. This study provides an important insight into the understanding of the molecular basis of adult metamorphosis.

DFT study of benzyl alcohol/TiO2 interfacial surface complex: reaction pathway and mechanism of visible light absorption.

PubMed

Zhao, Lei; Gu, Feng Long; Kim, Minjae; Miao, Maosheng; Zhang, Rui-Qin

2017-09-24

We propose a new pathway for the adsorption of benzyl alcohol on the surface of TiO 2 and the formation of interfacial surface complex (ISC). The reaction free energies and reaction kinetics were thoroughly investigated by density functional calculations. The TiO 2 surfaces were modeled by clusters consisting of 4 Ti atoms and 18 O atoms passivated by H, OH group and H 2 O molecules. Compared with solid-state calculations utilizing the periodicity of the materials, such cluster modeling allows inclusion of the high-order correlation effects that seem to be essential for the adsorption of organic molecules onto solid surfaces. The effects of both acidity and solvation are included in our calculations, which demonstrate that the new pathway is competitive with a previous pathway. The electronic structure calculations based on the relaxed ISC structures reveal that the chemisorption of benzyl alcohol on the TiO 2 surface greatly alters the nature of the frontier molecular orbitals. The resulted reduced energy gap in ISC matches the energy of visible light, showing how the adsorption of benzyl alcohol sensitizes the TiO 2 surface. Graphical Abstract The chemisorption of benzyl alcohol on TiO 2 surface greatly alters the nature of the frontier molecular orbitals and the formed interfacial surface complex can be sensitized by visible light.

Complexes with Tunable Intramolecular Ferrocene to Ti(IV) Electronic Transitions: Models for Solid State Fe(II) to Ti(IV) Charge Transfer.

PubMed

Turlington, Michael D; Pienkos, Jared A; Carlton, Elizabeth S; Wroblewski, Karlee N; Myers, Alexis R; Trindle, Carl O; Altun, Zikri; Rack, Jeffrey J; Wagenknecht, Paul S

2016-03-07

Iron(II)-to-titanium(IV) metal-to-metal-charge transfer (MMCT) is important in the photosensitization of TiO2 by ferrocyanide, charge transfer in solid-state metal-oxide photocatalysts, and has been invoked to explain the blue color of sapphire, blue kyanite, and some lunar material. Herein, a series of complexes with alkynyl linkages between ferrocene (Fc) and Ti(IV) has been prepared and characterized by UV-vis spectroscopy and electrochemistry. Complexes with two ferrocene substituents include Cp2Ti(C2Fc)2, Cp*2Ti(C2Fc)2, and Cp2Ti(C4Fc)2. Complexes with a single ferrocene utilize a titanocene with a trimethylsilyl derivatized Cp ring, (TMS)Cp, and comprise the complexes (TMS)Cp2Ti(C2Fc)(C2R), where R = C6H5, p-C6H4CF3, and CF3. The complexes are compared to Cp2Ti(C2Ph)2, which lacks the second metal. Cyclic voltammetry for all complexes reveals a reversible Ti(IV/III) reduction wave and an Fe(II/III) oxidation that is irreversible for all complexes except (TMS)Cp2Ti(C2Fc)(C2CF3). All of the complexes with both Fc and Ti show an intense absorption (4000 M(-1)cm(-1) < ε < 8000 M(-1)cm(-1)) between 540 and 630 nm that is absent in complexes lacking a ferrocene donor. The energy of the absorption tracks with the difference between the Ti(IV/III) and Fe(III/II) reduction potentials, shifting to lower energy as the difference in potentials decreases. Reorganization energies, λ, have been determined using band shape analysis (2600 cm(-1) < λ < 5300 cm(-1)) and are in the range observed for other donor-acceptor complexes that have a ferrocene donor. Marcus-Hush-type analysis of the electrochemical and spectroscopic data are consistent with the assignment of the low-energy absorption as a MMCT band. TD-DFT analysis also supports this assignment. Solvatochromism is apparent for the MMCT band of all complexes, there being a bathochromic shift upon increasing polarizability of the solvent. The magnitude of the shift is dependent on both the electron density at Ti(IV) and the identity of the linker between the titanocene and the Fc. Complexes with a MMCT are photochemically stable, whereas Cp2Ti(C2Ph)2 rapidly decomposes upon photolysis.

Silica-supported, single-site titanium catalysts for olefin epoxidation. A molecular precursor strategy for control of catalyst structure.

PubMed

Jarupatrakorn, Jonggol; Don Tilley, T

2002-07-17

A molecular precursor approach involving simple grafting procedures was used to produce site-isolated titanium-supported epoxidation catalysts of high activity and selectivity. The tris(tert-butoxy)siloxy titanium complexes Ti[OSi(O(t)Bu)(3)](4) (TiSi4), ((i)PrO)Ti[OSi(O(t)Bu)(3)](3) (TiSi3), and ((t)BuO)(3)TiOSi(O(t)Bu)(3) (TiSi) react with the hydroxyl groups of amorphous Aerosil, mesoporous MCM-41, and SBA-15 via loss of HO(t)Bu and/or HOSi(O(t)Bu)(3) and introduction of titanium species onto the silica surface. Powder X-ray diffraction, nitrogen adsorption/desorption, infrared, and diffuse reflectance ultraviolet spectroscopies were used to investigate the structures and chemical natures of the surface-bound titanium species. The titanium species exist mainly in isolated, tetrahedral coordination environments. Increasing the number of siloxide ligands in the molecular precursor decreases the amount of titanium that can be introduced this way, but also enhances the catalytic activity and selectivity for the epoxidation of cyclohexene with cumene hydroperoxide as oxidant. In addition, the high surface area mesoporous silicas (MCM-41 and SBA-15) are more effective than amorphous silica as supports for these catalysts. Supporting TiSi3 on the SBA-15 affords highly active cyclohexene epoxidation catalysts (0.25-1.77 wt % Ti loading) that provide turnover frequencies (TOFs) of 500-1500 h(-1) after 1 h (TOFs are reduced by about half after calcination). These results demonstrate that oxygen-rich siloxide complexes of titanium are useful as precursors to supported epoxidation catalysts.

Influence of impurities on the high temperature conductivity of SrTiO3

NASA Astrophysics Data System (ADS)

Bowes, Preston C.; Baker, Jonathon N.; Harris, Joshua S.; Behrhorst, Brian D.; Irving, Douglas L.

2018-01-01

In studies of high temperature electrical conductivity (HiTEC) of dielectrics, the impurity in the highest concentration is assumed to form a single defect that controls HiTEC. However, carrier concentrations are typically at or below the level of background impurities, and all impurities may complex with native defects. Canonical defect models ignore complex formation and lump defects from multiple impurities into a single effective defect to reduce the number of associated reactions. To evaluate the importance of background impurities and defect complexes on HiTEC, a grand canonical defect model was developed with input from density functional theory calculations using hybrid exchange correlation functionals. The influence of common background impurities and first nearest neighbor complexes with oxygen vacancies (vO) was studied for three doping cases: nominally undoped, donor doped, and acceptor doped SrTiO3. In each case, conductivity depended on the ensemble of impurity defects simulated with the extent of the dependence governed by the character of the dominant impurity and its tendency to complex with vO. Agreement between simulated and measured conductivity profiles as a function of temperature and oxygen partial pressure improved significantly when background impurities were included in the nominally undoped case. Effects of the impurities simulated were reduced in the Nb and Al doped cases as both elements did not form complexes and were present in concentrations well exceeding all other active impurities. The influence of individual impurities on HiTEC in SrTiO3 was isolated and discussed and motivates further experiments on singly doped SrTiO3.

Lifetime measurements in N=Z 72Kr

NASA Astrophysics Data System (ADS)

Andreoiu, C.; Svensson, C. E.; Austin, R. A. E.; Carpenter, M. P.; Dashdorj, D.; Finlay, P.; Freeman, S. J.; Garrett, P. E.; Görgen, A.; Greene, J.; Grinyer, G. F.; Hyland, B.; Jenkins, D.; Johnston-Theasby, F.; Joshi, P.; Machiavelli, A. O.; Moore, F.; Mukherjee, G.; Phillips, A. A.; Reviol, W.; Sarantites, D. G.; Schumaker, M. A.; Seweryniak, D.; Smith, M. B.; Valiente-Dobón, J. J.; Wadsworth, R.

2006-07-01

High-spin states in the N=Z nucleus 72Kr have been populated in the 40Ca(40Ca, 2α)72Kr fusion-evaporation reaction at a beam energy of 165 MeV and using a thin isotopically enriched 40Ca target. The experiment, performed at Argonne National Laboratory close to Chicago, USA, employed the Gammasphere array for γ-ray detection coupled to the Microball array for charged particle detection. The previously observed bands in 72Kr were extended to a higher excitation energy of ~24 MeV and higher angular momentum of 30planck. Using the Doppler-shift attenuation method, the lifetimes of high-spin states were measured for the first time in order to investigate deformation changes associated with the g9/2 proton and neutron alignments in this N=Z nucleus. An excellent agreement with theoretical calculations including only standard t=1 np pairing was observed.

Atom Trap Trace Analysis: Developments & Applications

NASA Astrophysics Data System (ADS)

Zappala, Jake Christopher

Atom Trap Trace Analysis (ATTA) is an efficient and selective laser-based atom counting technique that provides radiokrypton 81Kr and 85Kr dating to the earth science community. 81Kr (half-life = 230,000 yr) is an ideal tracer for old water and ice with mean residence times of 105-106 years, a range beyond the reach of 14C-dating. 85Kr (half-life = 10.7 yr) is an increasingly important tracer for young groundwater in the age range of 5-50 years. Over the past three years, we have implemented a number of developments that have improved the precision and efficiency of the ATTA technique. These developments have further allowed us to make new leaps in the analysis of both isotopes. For 81Kr, we have demonstrated measurements of 81Kr/Kr with relative one-sigma uncertainties of 1% and placed an improved limit on anthropogenic 81Kr in the atmosphere, removing a systematic constraint to high precision 81Kr-dating. For 85Kr, we have developed new methodologies that increase sample throughput from 1 sample every 48 hours to 6 samples in 24 hours. All the while, we have used the ATTA-3 system at Argonne National Laboratory to continue and provide sample measurements to the scientific community and have now completed over 230 measurements in more than 25 collaborative projects which together span all seven continents. Finally we have investigated options for further development of the ATTA technique given the growing demand and new applications present within the scientific community at large. Ultimately, we aspire, through ATTA, to make radiokrypton dating as readily and easily available as radiocarbon dating.

Titanium biomaterials with complex surfaces induced aberrant peripheral circadian rhythms in bone marrow mesenchymal stromal cells.

PubMed

Hassan, Nathaniel; McCarville, Kirstin; Morinaga, Kenzo; Mengatto, Cristiane M; Langfelder, Peter; Hokugo, Akishige; Tahara, Yu; Colwell, Christopher S; Nishimura, Ichiro

2017-01-01

Circadian rhythms maintain a high level of homeostasis through internal feed-forward and -backward regulation by core molecules. In this study, we report the highly unusual peripheral circadian rhythm of bone marrow mesenchymal stromal cells (BMSCs) induced by titanium-based biomaterials with complex surface modifications (Ti biomaterial) commonly used for dental and orthopedic implants. When cultured on Ti biomaterials, human BMSCs suppressed circadian PER1 expression patterns, while NPAS2 was uniquely upregulated. The Ti biomaterials, which reduced Per1 expression and upregulated Npas2, were further examined with BMSCs harvested from Per1::luc transgenic rats. Next, we addressed the regulatory relationship between Per1 and Npas2 using BMSCs from Npas2 knockout mice. The Npas2 knockout mutation did not rescue the Ti biomaterial-induced Per1 suppression and did not affect Per2, Per3, Bmal1 and Clock expression, suggesting that the Ti biomaterial-induced Npas2 overexpression was likely an independent phenomenon. Previously, vitamin D deficiency was reported to interfere with Ti biomaterial osseointegration. The present study demonstrated that vitamin D supplementation significantly increased Per1::luc expression in BMSCs, though the presence of Ti biomaterials only moderately affected the suppressed Per1::luc expression. Available in vivo microarray data from femurs exposed to Ti biomaterials in vitamin D-deficient rats were evaluated by weighted gene co-expression network analysis. A large co-expression network containing Npas2, Bmal1, and Vdr was observed to form with the Ti biomaterials, which was disintegrated by vitamin D deficiency. Thus, the aberrant BMSC peripheral circadian rhythm may be essential for the integration of Ti biomaterials into bone.

Defect evolution in a Nisbnd Mosbnd Crsbnd Fe alloy subjected to high-dose Kr ion irradiation at elevated temperature

NASA Astrophysics Data System (ADS)

de los Reyes, Massey; Voskoboinikov, Roman; Kirk, Marquis A.; Huang, Hefei; Lumpkin, Greg; Bhattacharyya, Dhriti

2016-06-01

A candidate Nisbnd Mosbnd Crsbnd Fe alloy (GH3535) for application as a structural material in a molten salt nuclear reactor was irradiated with 1 MeV Kr2+ ions (723 K, max dose of 100 dpa) at the IVEM-Tandem facility. The evolution of defects like dislocation loops and vacancy- and self-interstitial clusters was examined in-situ. For obtaining a deeper insight into the true nature of these defects, the irradiated sample was further analysed under a TEM post-facto. The results show that there is a range of different types of defects formed under irradiation. Interaction of radiation defects with each other and with pre-existing defects, e.g., linear dislocations, leads to the formation of complex microstructures. Molecular dynamics simulations used to obtain a greater understanding of these defect transformations showed that the interaction between linear dislocations and radiation induced dislocation loops could form faulted structures that explain the fringed contrast of these defects observed in TEM.

A study of the vacancy loop formation probability in Ni-Cu and Ag-Pd alloys. [50-keV Kr sup + ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smalinskas, K.; Chen, Gengsheng; Haworth, J.

1992-04-01

The molten-zone model of vacancy loop formation from a displacement cascade predicts that the loop formation probability should scale with the melting temperature. To investigate this possibility the vacancy loop formation probability has been determined in a series of Cu-Ni and Ag-Pd alloys. The irradiations were performed at room temperature with 50 keV Kr+ ions and the resulting damage structure was examined by using transmission electron microscopy. In the Cu-Ni alloy series, the change in loop formation probability with increasing Ni concentration was complex, and at low- and high- nickel concentrations, the defect yield did not change in the predictedmore » manner. The defect yield was higher in the Cu-rich alloys than in the Ni-rich alloys. In the Ag-Pd alloy the change in the loop formation probability followed more closely the change in melting temperature, but no simple relationship was determined.« less

Understanding Bright 13 keV Kr K-shell X-ray Sources at the NIF

NASA Astrophysics Data System (ADS)

May, M. J.; Colvin, J. D.; Kemp, G. E.; Fournier, K. B.; Scott, H.; Patel, M.; Barrios, Widmann; Widmann, K.

2015-11-01

High x-ray conversion efficiency (CE) K-shell Kr sources are being investigated for High Energy Density experiments. These sources are 4.1 mm in diameter 4.4 mm tall hollow epoxy tubes having a 40 μm thick wall holding either 1.2 or 1.5 atm of Kr gas. The CE of K-shell Kr is dependent upon the peak electron temperature in the radiating plasma. In the NIF experiments, the available energy heats the source to Te = 6-7 keV, well below the temperature of Te ~25 keV needed to optimize the Kr CE. The CE is a steep function of the peak electron temperature. A spatially averaged electron temperature can be estimated from measured He(α) and Ly(α) line ratios. Some disagreement has been observed in the simulated and measured line ratios for some of these K-shell sources. Disagreements have been observed between the simulated and measured line ratios for some of these K-shell sources. To help understand this issue, Kr gas pipes have been shot with 3 ω light at ?750 kJ at ~210, ~140 TW and ~120 TW power levels with 3.7, 5.2 and 6.7 ns pulses, respectively. The power and pulse length scaling of the measured CE and K-shell line ratios and their comparison to simulations will be discussed. This work was performed under the auspic

Atomic alignment effect on reactivity and on product alignment in the energy-transfer reaction of oriented Ar (3P2, 4s [3/2]2, M(J) = 2) + Kr (4p6, 1S0) → Ar (3p6, 1S0) + Kr (5p [3/2]2).

PubMed

Ohoyama, H

2015-03-12

Steric effect for the formation of Kr (5p [3/2]₂) in the energy transfer reaction of Ar (³P₂, 4s [3/2]₂) + Kr has been studied by using an oriented Ar (³P₂, 4s [3/2]₂, M(J) = 2) beam at a collision energy of ∼0.09 eV. The emission intensity of Kr (5p [3/2]₂) is ca. 2 times enhanced when the angular momentum (J(Ar)) of Ar (³P₂) is aligned perpendicular to the relative velocity vector (v(R)). In addition, the Kr (5p [3/2]₂) emission is highly polarized parallel to v(R) (I(∥)/I(⊥) ∼ 1.2) when JAr is aligned perpendicular to v(R). The observed polarization moments indicate that the alignment of the unpaired Ar (3p) orbital of Ar (³P₂) to v(R), (Σ (|L′| = 0), Π (|L′| = 1)), dominates the energy transfer probability (σ(Π)(∥): σ(Σ)(∥): σ(Π)(⊥): σ(Σ)(⊥) = 0.49:1.33:0.55:1.23) and also the alignment of the Kr (5p) orbital of Kr (5p [3/2]₂) to v(R): the Σ-configuration of the Ar (3p) orbital leads to the parallel alignment (Σ-configuration) of the Kr(5p) orbital to v(R), conversely, the Π-configuration of Ar (3p) orbital leads to the perpendicular alignment (Π-configuration) of the Kr(5p) orbital. In addition, the selectivity of the alignment of the Kr (5p) orbital turns out to vary from perpendicular to parallel as the collision energy increases after a threshold down to 0.03 eV.

Hierarchical TiO2/C nanocomposite monoliths with a robust scaffolding architecture, mesopore-macropore network and TiO2-C heterostructure for high-performance lithium ion batteries

NASA Astrophysics Data System (ADS)

Huang, Hai-Bo; Yang, Yue; Chen, Li-Hua; Wang, Yun; Huang, Shao-Zhuan; Tao, Jia-Wei; Ma, Xiao-Ting; Hasan, Tawfique; Li, Yu; Xu, Yan; Su, Bao-Lian

2016-05-01

Engineering hierarchical structures of electrode materials is a powerful strategy for optimizing the electrochemical performance of an anode material for lithium-ion batteries (LIBs). Herein, we report the fabrication of hierarchical TiO2/C nanocomposite monoliths by mediated mineralization and carbonization using bacterial cellulose (BC) as a scaffolding template as well as a carbon source. TiO2/C has a robust scaffolding architecture, a mesopore-macropore network and TiO2-C heterostructure. TiO2/C-500, obtained by calcination at 500 °C in nitrogen, contains an anatase TiO2-C heterostructure with a specific surface area of 66.5 m2 g-1. When evaluated as an anode material at 0.5 C, TiO2/C-500 exhibits a high and reversible lithium storage capacity of 188 mA h g-1, an excellent initial capacity of 283 mA h g-1, a long cycle life with a 94% coulombic efficiency preserved after 200 cycles, and a very low charge transfer resistance. The superior electrochemical performance of TiO2/C-500 is attributed to the synergistic effect of high electrical conductivity, anatase TiO2-C heterostructure, mesopore-macropore network and robust scaffolding architecture. The current material strategy affords a general approach for the design of complex inorganic nanocomposites with structural stability, and tunable and interconnected hierarchical porosity that may lead to the next generation of electrochemical supercapacitors with high energy efficiency and superior power density.Engineering hierarchical structures of electrode materials is a powerful strategy for optimizing the electrochemical performance of an anode material for lithium-ion batteries (LIBs). Herein, we report the fabrication of hierarchical TiO2/C nanocomposite monoliths by mediated mineralization and carbonization using bacterial cellulose (BC) as a scaffolding template as well as a carbon source. TiO2/C has a robust scaffolding architecture, a mesopore-macropore network and TiO2-C heterostructure. TiO2/C-500, obtained by calcination at 500 °C in nitrogen, contains an anatase TiO2-C heterostructure with a specific surface area of 66.5 m2 g-1. When evaluated as an anode material at 0.5 C, TiO2/C-500 exhibits a high and reversible lithium storage capacity of 188 mA h g-1, an excellent initial capacity of 283 mA h g-1, a long cycle life with a 94% coulombic efficiency preserved after 200 cycles, and a very low charge transfer resistance. The superior electrochemical performance of TiO2/C-500 is attributed to the synergistic effect of high electrical conductivity, anatase TiO2-C heterostructure, mesopore-macropore network and robust scaffolding architecture. The current material strategy affords a general approach for the design of complex inorganic nanocomposites with structural stability, and tunable and interconnected hierarchical porosity that may lead to the next generation of electrochemical supercapacitors with high energy efficiency and superior power density. Electronic supplementary information (ESI) available: Characterizing BC aerogel; TG/DTA curves of BC@TiO2; EDX spectrum of TiO2/C-500; photograph of BC@TiO2 and TiO2/C-500 monoliths; XRD patterns of TiO2/C-T monoliths under a nitrogen atmosphere; characterizing TiO2/C-T and TiO2-500; XPS of TiO2/C-500; cycling performance of TiO2/C-T; capacity retention plots, coulombic efficiency, EIS spectra after 10 cycles and the initial EIS spectra of TiO2/C-500; XRD patterns of TiO2/C-500 before and after 150 discharge-charge cycles at 0.5 C. See DOI: 10.1039/c5nr09149g

Geochemical stratigraphy and correlation within large igneous provinces: The final preserved stages of the Faroe Islands Basalt Group

NASA Astrophysics Data System (ADS)

Millett, J. M.; Hole, M. J.; Jolley, D. W.; Passey, S. R.

2017-08-01

The Faroe Islands Basalt Group (FIBG) comprises a gross stratigraphic thickness of over 6.5 km of dominantly extrusive basaltic facies erupted during the Late Palaeocene to Early Eocene. In this study we present 140 major and trace element analyses from flow by flow field and borehole sample profiles, through the Enni Formation, which comprises the final phase of volcanism preserved on the Faroe Islands. The sample profiles target geographically spaced and overlapping stratigraphic sequences tied relative to a 3D ArcGIS surface for the regionally extensive volcaniclastic Argir Beds marker unit. From these profiles five geochemical groups including one low TiO2 (Low-Ti < 1.5 wt%) and four high TiO2 (High-Ti > 1.5 wt%) groups differentiated by Nb, Zr, Y and V variations are identified in conjunction with previous studies. The spatial and stratigraphic distribution of these groups is mapped across the islands and demonstrates a complex inter-digitated flow field evolution. Within the finer scale variations, broad spatial and temporal development trends are identified demonstrating the potential for correlation within the volcanic succession at the local, tens of kilometers scale. Low-Ti lavas formed in association with lithospheric thinning and developed extensive flow fields between the Faroe Islands and East Greenland contemporaneous to the eruption of High-Ti smaller melt fraction lava flows in both locations. The progression of High-Ti lava groups preserved on either side of the developing rift zone is very similar, but is not, however, chronostratigraphic due to multiple inter-digitations of the chemical types. We tentatively suggest that a previously proposed rift-oblique transfer zone between the Faroe Islands and East Greenland enabled non-uniform lithospheric thinning and the preservation of a near-continuous High-Ti melting region between these areas beyond the onset of Low-Ti eruptions which were initially fed from the west. This study highlights the complex nature of late stage flood basalt plumbing systems and eruption dynamics in a rift proximal setting.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Kimmel, Greg A.; Shen, Mingmin

Using temperature programmed desorption (TPD) and photon-stimulated desorption (PSD), we show that coadsorbates of varying binding energies on the rutile TiO 2(110) surface exert a commensurate inhibiting influence on the hole-mediated photodesorption of adsorbed O 2. A variety of coadsorbates (Ar, Kr, Xe, N 2, CO, CO 2, CH 4, N 2O, acetone, methanol or water) were shown to quench O 2 photoactivity, with the extent correlating with the coadsorbate's gas phase basicity, which in turn determines the strength of the coadsorbate–Ti 4+ bond. Coadsorbed rare gases inhibited the photodesorption of O 2 by ~ 10–25%, whereas strongly bound speciesmore » (water, methanol, and acetone) nearly completely inhibited O 2 PSD. We suggest that coadsorption of these molecules inhibit the arrival probability of holes to the surface. Band-bending effects, which vary with the extent of charge transfer between the coadsorbate and the TiO 2(110) surface, are not expected to be significant in the cases of the rare gases and physisorbed species. Furthermore, these results indicate that neutral coadsorbates can exert a significant influence on charge transfer events by altering the interfacial dipole in the vicinity of the target molecule.« less

Dielectric relaxation study of amorphous TiTaO thin films in a large operating temperature range

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rouahi, A.; Kahouli, A.; Laboratoire Materiaux, Organisation et Proprietes

2012-11-01

Two relaxation processes have been identified in amorphous TiTaO thin films deposited by reactive magnetron sputtering. The parallel angle resolved x-ray photoelectron spectroscopy and field emission scanning electron microscopy analyses have shown that this material is composed of an agglomerates mixture of TiO{sub 2}, Ta{sub 2}O{sub 5}, and Ti-Ta bonds. The first relaxation process appears at low temperature with activation energy of about 0.26 eV and is related to the first ionisation of oxygen vacancies and/or the reduction of Ti{sup 4+} to Ti{sup 3+}. The second relaxation process occurs at high temperature with activation energy of 0.95 eV. This lastmore » peak is associated to the diffusion of the doubly ionized oxygen vacancies V{sub O}e. The dispersion phenomena observed at high temperature can be attributed to the development of complex defect such as (V{sub O}e - 2Ti{sup 3+}).« less

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor.

PubMed

von Rohr, Fabian; Winiarski, Michał J; Tao, Jing; Klimczuk, Tomasz; Cava, Robert Joseph

2016-11-15

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellent intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials.

The formation and study of titanium, zirconium, and hafnium complexes

NASA Technical Reports Server (NTRS)

Wilson, Bobby; Sarin, Sam; Smith, Laverne; Wilson, Melanie

1989-01-01

Research involves the preparation and characterization of a series of Ti, Zr, Hf, TiO, and HfO complexes using the poly(pyrazole) borates as ligands. The study will provide increased understanding of the decomposition of these coordination compounds which may lead to the production of molecular oxygen on the Moon from lunar materials such as ilmenite and rutile. The model compounds are investigated under reducing conditions of molecular hydrogen by use of a high temperature/pressure stainless steel autoclave reactor and by thermogravimetric analysis.

Three tier transition of Neoarchean TTG-sanukitoid magmatism in the Beit Bridge Complex, Southern Africa

NASA Astrophysics Data System (ADS)

Rajesh, H. M.; Belyanin, G. A.; Van Reenen, D. D.

2018-01-01

Neoarchean TTG-sanukitoid associations of contrasting scales occur within the Beit Bridge Complex terrane of the Limpopo Complex in southern Africa. These include the smaller 2.65-2.63 Ga Avoca granitoid and the voluminous 2.73-2.64 Ga Alldays granitoid. This study characterizes the wide compositional spectrum preserved in these two granitoids. The elliptical Avoca pluton consists of a biotite-amphibole-orthopyroxene ± clinopyroxene-bearing core that is dominantly trondhjemite with less dominant tonalite and granodiorite variants, and a thin amphibole-biotite-bearing granite rim, with local occurrence of two-pyroxene-bearing metabasite boudins. While both the core and rim rocks exhibit a linear fabric, the granite in addition preserves a penetrative foliation. Field relations of granite enclaves in the core rocks together with available ages indicate that the core rocks intruded the granite. The foliated biotite ± amphibole-bearing Alldays granitoid contains inclusions of older supracrustals and rocks of the Messina layered intrusion, and is widely distributed. Compositionally, it include tonalites and granodiorites and to a lesser extent trondhjemites. Both the Avoca core and rim rocks are characterized by difference in mineral chemistry, with the mafic minerals Mg-rich in the TTG core, while they are Fe-rich in the granite and metabasite. In comparison, biotite is Mg-rich and amphibole is Fe-rich in the Alldays granitoid. Two groups of Alldays TTG can be delineated in terms of whole-rock geochemical characteristics, and are comparable to the low- to medium-pressure TTG groups delineated by Moyen (2011), while the Avoca TTG is similar to the high-pressure TTG group. The lowest silica samples from each group of granitoid have geochemical characteristics comparable to Archean sanukitoids, with those from the Avoca granitoid similar to low-Ti sanukitoids, and those from the Alldays granitoid similar to low-Ti and high-Ti sanukitoids. Separate petrogenetic models are suggested for different phases of the Avoca core, with the trondhjemite-tonalites considered as high-pressure melts of metabasalt, while the granodiorite with lower SiO2 content, higher K2O and MgO contents, and higher incompatible element contents, than the trondhjemite-tonalites, is a product of hybridization of earlier TTG melts and peridodite. Granite from the Avoca rim are low-pressure melts of pre-existing crustal lithologies. The two groups of Alldays TTG with lower Sr/Y ratios than the Avoca TTG are considered as low- to medium-pressure melts of metabasalt, whose progressive interaction with peridotitic mantle at shallower angles account for the unique composition of Alldays low-Ti and high-Ti sanukitoids. Taken together with their spatial and temporal transition from southeastern ( 2.73-2.72 Ga; low-pressure TTG-low-Ti sanukitoid) to central ( 2.65-2.64 Ga; medium-pressure TTG-high-Ti sanukitoid) to northwestern ( 2.63 Ga; high-pressure TTG-low-Ti sanukitoid) parts of the Beit Bridge Complex, the three tier transition of TTG-sanukitoid magmatism argues for the southern margin of the Beit Bridge Complex to represent an active arc in the Neoarchean.

California GAMA Special Study. Development of a Capability for the Analysis of Krypton-85 in Groundwater Samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Visser, Ate; Bibby, Richard K.; Moran, Jean E.

A capability for the analysis of krypton-85 ( 85Kr) in groundwater samples was developed at LLNL. Samples are collected by extracting gas from 2000-4000 L of groundwater at the well, yielding approximately 0.2 cm 3 STP krypton. Sample collection takes 1 to 4 hours. Krypton is purified in the laboratory using a combination of molecular sieve and activated charcoal traps, and transferred to a liquid scintillation vial. The 85Kr activity is measured by liquid scintillation on a Quantulus 1220 liquid scintillation counter from PerkinElmer. The detection limit for a typical 0.2 cm 3Kr sample size is 11% of the presentmore » day activity in air, corresponding to the decay corrected activity in air in 1987. The typical measurement uncertainty is below 10% for recently recharged samples. Six groundwater samples were collected, purified and counted. 85Kr was not detected in any of the samples counted at LLNL. 85Kr was detected by the low level counting laboratory of Bern University in all samples between 1.5 and 6.6 decays per minute per cm 3 krypton, corresponding to decay corrected activities in air between 1971 and 1985. The new capability is an excellent complement to tritium-helium, expanding the existing suite of age dating tools available to the GAMA program ( 35S, 3H/ 3He, 14C and radiogenic helium). 85Kr can replace 3H/ 3He in settings where 3H/ 3He ages are impossible to determine (for example where terrigenic helium overwhelms tritiogenic helium) and provides additional insight into travel time distributions in complex mixed groundwater systems.« less

The sol-gel template synthesis of porous TiO2 for a high performance humidity sensor

NASA Astrophysics Data System (ADS)

Wang, Zhuyi; Shi, Liyi; Wu, Fengqing; Yuan, Shuai; Zhao, Yin; Zhang, Meihong

2011-07-01

This research develops a simple template assisted sol-gel process for preparing porous TiO2 for a high performance humidity sensor. Tetraethyl orthosilicate (TEOS) as a template was directly introduced into TiO2 sol formed by the hydrolysis and condensation of titanium alkoxide; the following calcination led to the formation of TiO2-SiO2 composite, and the selective removal of SiO2 by dilute HF solution led to the formation of porous structure in TiO2. The resulting porous TiO2-based sensor exhibits high sensitivity and linear response in the wide relative humidity (RH) range of 11%-95%, with an impedance variation of four orders of magnitude to humidity change. Moreover, it exhibits a rapid and highly reversible response characterized by a very small hysteresis of < 1% RH and a short response-recovery time (5 s for adsorption and 8 s for desorption), and a 30-day stability test also confirms its long-term stability. Compared with pure TiO2 prepared by the conventional sol-gel method, our product shows remarkably improved performance and good prospect for a high performance humidity sensor. The complex impedance spectra were used to elucidate its humidity sensing mechanism in detail.

Growth of highly textured PbTiO3 films on conductive substrate under hydrothermal conditions

NASA Astrophysics Data System (ADS)

Tang, Haixiong; Zhou, Zhi; Bowland, Christopher C.; Sodano, Henry A.

2015-08-01

Perovskite structure (ABO3) thin films have wide applications in electronic devices due to their unique properties, including high dielectric permittivity, ferroelectricity and piezoelectric coupling. Here, we report an approach to grow highly textured thick lead titanate (PbTiO3) films on conductive substrates by a two-step hydrothermal reaction. Initially, vertically aligned TiO2 nanowire arrays are grown on fluorine-doped tin oxide (FTO) coated glass, which act as template crystals for conversion to the perovskite structure. The PbTiO3 films are then converted from TiO2 NW arrays by diffusing Pb2+ ions into the template through a second hydrothermal reaction. The dielectric permittivity and piezoelectric coupling coefficient (d33) of the PbTiO3 films are as high as 795 at 1 kHz and 52 pm V-1, respectively. The reported process can also potentially be expanded for the assembly of other complex perovskite ATiO3 (A = Ba, Ca, Cd, etc) films by using the highly aligned TiO2 NW arrays as templates. Therefore, the approach introduced here opens up a new door to synthesize ferroelectric thin films on conductive substrates for application in sensors, actuators, and ultrasonic transducers that are important in various industrial and scientific areas.

Isotopologue-selective excitation studied via optical-optical double resonance using the E3 Σ1+(63S1) ←A3Π0+(53P1) ←X1Σ0+(51S0) transitions in CdAr and CdKr van der Waals complexes

NASA Astrophysics Data System (ADS)

Urbańczyk, T.; Dudek, J.; Koperski, J.

2018-06-01

A method of experimental selection of molecular isotopologues using optical-optical double resonance (OODR) scheme and supersonic beam source of van der Waals (vdW) complexes is presented. Due to an appropriately large isotopic shift, the proper choice of a wavenumber of a sufficiently narrowband laser in the first transition of OODR scheme can lead to a selective isotopologue excitation to the intermediate state. Thanks to this approach, it is possible to select some of the isotopologues which subsequently give a contribution to laser induced fluorescence (LIF) signal originated from the final state of OODR. In this article, results of tests of the proposed method that employs the E3 Σ1+ ←A3Π0+ ←X1Σ0+ transitions in two vdW complexes, CdKr and CdAr, are presented and analysed.

Electron-pinned defect-dipoles for high-performance colossal permittivity materials.

PubMed

Hu, Wanbiao; Liu, Yun; Withers, Ray L; Frankcombe, Terry J; Norén, Lasse; Snashall, Amanda; Kitchin, Melanie; Smith, Paul; Gong, Bill; Chen, Hua; Schiemer, Jason; Brink, Frank; Wong-Leung, Jennifer

2013-09-01

The immense potential of colossal permittivity (CP) materials for use in modern microelectronics as well as for high-energy-density storage applications has propelled much recent research and development. Despite the discovery of several new classes of CP materials, the development of such materials with the required high performance is still a highly challenging task. Here, we propose a new electron-pinned, defect-dipole route to ideal CP behaviour, where hopping electrons are localized by designated lattice defect states to generate giant defect-dipoles and result in high-performance CP materials. We present a concrete example, (Nb+In) co-doped TiO₂ rutile, that exhibits a largely temperature- and frequency-independent colossal permittivity (> 10(4)) as well as a low dielectric loss (mostly < 0.05) over a very broad temperature range from 80 to 450 K. A systematic defect analysis coupled with density functional theory modelling suggests that 'triangular' In₂(3+)Vo(••)Ti(3+) and 'diamond' shaped Nb₂(5+)Ti(3+)A(Ti) (A = Ti(3+)/In(3+)/Ti(4+)) defect complexes are strongly correlated, giving rise to large defect-dipole clusters containing highly localized electrons that are together responsible for the excellent CP properties observed in co-doped TiO₂. This combined experimental and theoretical work opens up a promising feasible route to the systematic development of new high-performance CP materials via defect engineering.

Channel-specific dielectronic recombination of Ge(XXXII), Se(XXXIV), and Kr(XXXVI)

NASA Astrophysics Data System (ADS)

El Machtoub, G.

2004-04-01

We present explicit calculations of channel-specific dielectronic recombination cross sections for hydrogen-like germanium, Ge(XXXII); selenium, Se(XXXIV); and krypton, Kr(XXXVI). The convoluted cross sections characterize K-shell emission spectra over a wide energy range where contributions from high-n (n = 2-10), satellite lines are included. The high-n contributions presented are important for better diagnostics in the domain of high-temperature plasmas.

Many-body interactions and high-pressure equations of state in rare-gas solids

NASA Astrophysics Data System (ADS)

Freiman, Yu. A.; Tretyak, S. M.

2007-06-01

The T =0K equations of state (EOS) of rare-gas solids (RGS) (He, Ne, Ar, Kr, and Xe) are calculated in the experimentally studied ranges of pressures with the two- and three-body interatomic forces taken into account. Solid-state corrections to the pure two-body Aziz et al. potentials included the long-range Axilrod-Teller three-body interaction and short-range three-body exchange interaction. The energy-scale and length-scale parameters of the latter were taken as adjustable parameters of theory. The calculated T =0K EOS for all RGS are in excellent agreement with experiment in the whole range of pressures. The calculated EOS for Ar, Kr, and Xe exhibit inflection points where the isothermal bulk moduli have non-physical maxima, indicating that account of only three-body forces becomes insufficient. These points lie at pressures 250, 200, and 175GPa (volume compressions of approximately 4.8, 4.1, and 3.6) for Ar, Kr, and Xe, respectively. No such points were found in the calculated EOS of He and Ne. The relative magnitude of the three-body contribution to the ground-state energy with respect to the two-body one as a function of the volume compression was found to be nonmonotonic in the sequence Ne-Ar-Kr-Xe. In a large range of compressions, Kr has the highest value of this ratio. This anomalously high three-body exchange force contributes to the EOS a negative pressure so large that the EOS for Kr and Ar as a function of compression nearly coincide. At compressions higher than approximately 3.5 the curves intersect, and further on, the EOS of Kr lies lower than that of Ar.

Increased response to β₂-adrenoreceptor stimulation augments inhibition of IKr in heart failure ventricular myocytes.

PubMed

Wang, Hegui; Chen, Yanhong; Zhu, Hongjun; Wang, Sen; Zhang, Xiwen; Xu, Dongjie; Cao, Kejiang; Zou, Jiangang

2012-01-01

Increasing evidence indicates that the rapid component of delayed rectifier potassium current (I(Kr)) is modulated by α- and β-adrenergic stimulation. However, the role and mechanism regulating I(Kr) through β(2)-adrenoreceptor (β-AR) stimulation in heart failure (HF) are unclear. In the present study, we investigated the effects of fenoterol, a highly selective β(2)-AR agonist, on I(Kr) in left ventricular myocytes obtained from control and guinea pigs with HF induced by descending aortic banding. I(Kr) was measured by using whole cell patch clamp technique. In control myocytes, superfusion of fenoterol (10 µM) caused a 17% decrease in I(Kr). In HF myocytes, the same concentration of fenoterol produced a significantly greater decrease (33%) in I(Kr). These effects were not modified by the incubation of myocytes with CGP-20712A, a β(1)-AR antagonist, but were abolished by pretreatment of myocytes with ICI-118551, a β(2)-AR antagonist. An inhibitory cAMP analog, Rp-cAMPS and PKA inhibitor significantly attenuated fenoterol-induced inhibition of I(Kr) in HF myocytes. Moreover, fenoterol markedly prolonged action potential durations at 90% (APD(90)) repolarization in HF ventricular myocytes. The results indicate that inhibition of I(Kr) induced by β(2)-AR stimulation is increased in HF. The inhibitory effect is likely to be mediated through a cAMP/PKA pathway in HF ventricular myocytes.

Development of Atmospheric Air 85Kr Monitoring Methodology on the Territory of the USSR

NASA Astrophysics Data System (ADS)

Pakhomov, Sergei; Dubasov, Yury

2014-05-01

Highly sensitive, low-background and high-performance method of beta-radioactivity measurements of the gas samples was developed in mid-eighties at Khlopin Radium institute. This method was based on the use of the serial automated installation for liquid scintillation measurements and special scintillating cells. Cells were equipped with the gas valve, and their internal surface were covered by a thin layer of organic scintillator. This method found was successfully was applied for 85Kr activity measurements in atmospheric krypton samples and for 85Kr concentration measurements in atmospheric air. For the first time, method developed for 85Kr activity measurements, was practically tested in May - June, 1986, while studying radioactive pollution characteristics in the air basin of Russia and Ukraine after the Chernobyl NPP accident. Thus for sampling of atmospheric krypton the industrial krypton-xenon mix manufactured at air-separating plants, located in the cities of Cherepovets, Lipetsk, Krivoi Rog and Enakiyevo was used. In the end of April and in the first half of May it was determined that 1,5-fold excess concentrations of 85Kr in atmospheric air were observed in atmospheric air of considerable part of the European territory of Russia and Ukraine During the period from 1987 to 1991 this method was used for monitoring of 85Kr on the territory of the former USSR in the air basin of Russia, Ukraine and Kazakhstan. Industrial krypton-xenon mix manufactured at 14 large air-separating plants was also used for sampling. Six of them were situated in Russia (Novomoskovsk, Lipetsk, Cherepovets, Chelyabinsk, Nizhni Tagil, Orsk). Seven - in Ukraine (Enakiyevo, Kommunarsk, Krivoi Rog, Makeyevka, Mariupol, Severodonetsk, Dneprodzerzhinsk). One plant was situated in Temirtau, in Kazakhstan. The analysis indicated that in Krivoi Rog; Dneprozhzerzhinsk; Severodonetsk; Makeyevka; Mariupol; Enakiyevo; Kommunarsk; Novomoskovsk and Cherepovets the average 85Kr concentration in atmospheric air was close to background level during monitoring. But in Lipetsk; Orsk; Nizhni Tagil and Temirtau 10-20% excess of background level was systematically observed. In Chelyabinsk concentration of 85Kr steadily exceeded this level by 2-3 times, and incidentally exceeded it for order. Generally, during this period about 1500 values of concentration 85Kr were obtained. Actually, the large-scale monitoring system of atmospheric 85Kr with a binding of sampling points to 14 air-separating plants covered the territory 1000 x 3000 km was created. The developed method of 85Kr activity measurement was successfully applied also when carrying out expedition works in Northern Atlantic during the period from 1987 to 1994 with use o ZIF-1000 cryogenic installation for sampling, which initially was intended for liquid nitrogen manufacturing at the ship. Generally, 80 measurements of 85Kr concentration were obtained using this method. It was determined, that the average concentration of 85Kr in atmospheric air in the open regions of the Atlantic Ocean, were close to background level during monitoring. The concentrations of 85Kr steadily exceeded this level by 2-3 times in English Channel, and incidentally exceeded it in tens times.

Amine-functionalized TiO₂ nanoparticles for highly selective enrichment of phosphopeptides.

PubMed

Liu, Hailong; Zhou, Jiahong; Huang, Heyong

2015-10-01

Specific enrichment of trace phosphoproteins or phosphopeptides from complex biological samples prior to mass spectrometry analysis is of profound significance for in-depth phosphoproteomics. In this work, an amine-functionalized TiO2 nano-material with N'[3-(trimethoxysilyl)-propyl] diethylenetriamine (TPDA) modified on the surface of nanoparticle TiO2 (TiO2@TPDA) was successfully designed and applied for the enrichment of phosphopeptides. Compared with pure TiO2, the novel prepared TiO2@TPDA possessed lower Lewis acidity, enhanced hydrophilicity and stronger affinity to phosphopeptides, and its performance for selective and effective enrichment of phosphopeptide was investigated by the standard protein digests and human serum. Copyright © 2015 Elsevier B.V. All rights reserved.

Theoretical characterization and design of highly efficient iridium (III) complexes bearing guanidinate ancillary ligand.

PubMed

Ren, Xin-Yao; Wu, Yong; Wang, Li; Zhao, Liang; Zhang, Min; Geng, Yun; Su, Zhong-Min

2014-06-01

A density functional theory/time-depended density functional theory was used to investigate the synthesized guanidinate-based iridium(III) complex [(ppy)2Ir{(N(i)Pr)2C(NPh2)}] (1) and two designed derivatives (2 and 3) to determine the influences of different cyclometalated ligands on photophysical properties. Except the conventional discussions on geometric relaxations, absorption and emission properties, many relevant parameters, including spin-orbital coupling (SOC) matrix elements, zero-field-splitting parameters, radiative rate constants (kr) and so on were quantitatively evaluated. The results reveal that the replacement of the pyridine ring in the 2-phenylpyridine ligand with different diazole rings cannot only enlarge the frontier molecular orbital energy gaps, resulting in a blue-shift of the absorption spectra for 2 and 3, but also enhance the absorption intensity of 3 in the lower-energy region. Furthermore, it is intriguing to note that the photoluminescence quantum efficiency (ΦPL) of 3 is significantly higher than that of 1. This can be explained by its large SOC value(n=3-4) and large transition electric dipole moment (μS3), which could significantly contribute to a larger kr. Besides, compared with 1, the higher emitting energy (ET1) and smaller (2) value for 3 may lead to a smaller non-radiative decay rate. Additionally, the detailed results also indicate that compared to 1 with pyridine ring, 3 with imidazole ring performs a better hole injection ability. Therefore, the designed complex 3 can be expected as a promising candidate for highly efficient guanidinate-based phosphorescence emitter for OLEDs applications. Copyright © 2014 Elsevier Inc. All rights reserved.

Plasma mirrors for short pulse KrF lasers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gilicze, Barnabás; Szatmári, Sándor; Barna, Angéla

2016-08-15

It is demonstrated for the first time that plasma mirrors can be successfully applied for KrF laser systems. High reflectivity up to 70% is achieved by optimization of the beam quality on the plasma mirror. The modest spectral shift and the good reflected beam quality allow its applicability for high power laser systems for which a new arrangement is suggested.

Direct diode pumped Ti:sapphire ultrafast regenerative amplifier system

DOE PAGES

Backus, Sterling; Durfee, Charles; Lemons, Randy; ...

2017-02-10

Here, we report on a direct diode-pumped Ti:sapphire ultrafast regenerative amplifier laser system producing multi-uJ energies with repetition rate from 50 to 250 kHz. By combining cryogenic cooling of Ti:sapphire with high brightness fiber-coupled 450nm laser diodes, we for the first time demonstrate a power-scalable CW-pumped architecture that can be directly applied to demanding ultrafast applications such as coherent high-harmonic EUV generation without any complex post-amplification pulse compression. Initial results promise a new era for Ti:sapphire amplifiers not only for ultrafast laser applications, but also for tunable CW sources. We discuss the unique challenges to implementation, as well as themore » solutions to these challenges.« less

Direct diode pumped Ti:sapphire ultrafast regenerative amplifier system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Backus, Sterling; Durfee, Charles; Lemons, Randy

Here, we report on a direct diode-pumped Ti:sapphire ultrafast regenerative amplifier laser system producing multi-uJ energies with repetition rate from 50 to 250 kHz. By combining cryogenic cooling of Ti:sapphire with high brightness fiber-coupled 450nm laser diodes, we for the first time demonstrate a power-scalable CW-pumped architecture that can be directly applied to demanding ultrafast applications such as coherent high-harmonic EUV generation without any complex post-amplification pulse compression. Initial results promise a new era for Ti:sapphire amplifiers not only for ultrafast laser applications, but also for tunable CW sources. We discuss the unique challenges to implementation, as well as themore » solutions to these challenges.« less

Rutile solubility and titanium coordination in silicate melts

NASA Astrophysics Data System (ADS)

Dickinson, James E., Jr.; Hess, Paul C.

1985-11-01

The solubility of rutile has been determined in a series of compositions in the K 2O-Al 2O 3-SiO 2 system ( K ∗ = K 2O /(K 2O + Al 2O 3) = 0.38-0.90), and the CaO-Al 2O 3-SiO 2 system ( C ∗ = CaO/(CaO + Al 2O 3) = 0.47-0.59 ). Isothermal results in the KAS system at 1325°C, 1400°C, and 1475°C show rutile solubility to be a strong function of the K ∗ ratio. For example, at 1475°C the amount of TiO 2 required for rutile saturation varies from 9.5 wt% ( K ∗ = 0.38 ) to 11.5 wt% ( K ∗ = 0.48 ) to 41.2 wt% ( K ∗ = 0.90 ). In the CAS system at 1475°C, rutile solubility is not a strong function of C ∗. The amount of TiO 2 required for saturation varies from 14 wt% ( C ∗ = 0.48 ) to 16.2 wt% ( C ∗ = 0.59 ). The solubility changes in KAS melts are interpreted to be due to the formation of strong complexes between Ti and K + in excess of that needed to charge balance Al 3+. The suggested stoichiometry of this complex is K 2Ti 2O 5 or K 2Ti 3O 7. In CAS melts, the data suggest that Ca 2+ in excess of A1 3+ is not as effective at complexing with Ti as is K +. The greater solubility of rutile in CAS melts when C ∗ is less than 0.54 compared to KAS melts of equal K ∗ ratio results primarily from competition between Ti and Al for complexing cations (Ca vs. K). TiK β x-ray emission spectra of KAS glasses ( K ∗ = 0.43-0.60 ) with 7 mole% added TiO 2, rutile, and Ba 2TiO 4, demonstrate that the average Ti-O bond length in these glasses is equal to that of rutile rather than Ba 2TiO 4, implying that Ti in these compositions is 6-fold rather than 4-fold coordinated. Re-examination of published spectroscopic data in light of these results and the solubility data, suggests that the 6-fold coordination polyhedron of Ti is highly distorted, with at least one Ti-O bond grossly undersatisfied in terms of Pauling's rules.

Motivation in vigilance - A test of the goal-setting hypothesis of the effectiveness of knowledge of results.

NASA Technical Reports Server (NTRS)

Warm, J. S.; Riechmann, S. W.; Grasha, A. F.; Seibel, B.

1973-01-01

This study tested the prediction, derived from the goal-setting hypothesis, that the facilitating effects of knowledge of results (KR) in a simple vigilance task should be related directly to the level of the performance standard used to regulate KR. Two groups of Ss received dichotomous KR in terms of whether Ss response times (RTs) to signal detections exceeded a high or low standard of performance. The aperiodic offset of a visual signal was the critical event for detection. The vigil was divided into a training phase followed by testing, during which KR was withdrawn. Knowledge of results enhanced performance in both phases. However, the two standards used to regulate feedback contributed little to these effects.

Heterobimetallic Ti/Co Complexes That Promote Catalytic N-N Bond Cleavage.

PubMed

Wu, Bing; Gramigna, Kathryn M; Bezpalko, Mark W; Foxman, Bruce M; Thomas, Christine M

2015-11-16

Treatment of the tris(phosphinoamide) titanium precursor ClTi(XylNP(i)Pr2)3 (1) with CoI2 leads to the heterobimetallic complex (η(2)-(i)Pr2PNXyl)Ti(XylNP(i)Pr2)2(μ-Cl)CoI (2). One-electron reduction of 2 affords (η(2)-(i)Pr2PNXyl)Ti(XylNP(i)Pr2)2CoI (3), which can be reduced by another electron under dinitrogen to generate the reduced diamagnetic complex (THF)Ti(XylNP(i)Pr2)3CoN2 (4). The removal of the dinitrogen ligand from 4 under vacuum affords (THF)Ti(XylNP(i)Pr2)3Co (5), which features a Ti-Co triple bond. Treatment of 4 with hydrazine or methyl hydrazine results in N-N bond cleavage and affords the new diamagnetic complexes (L)Ti(XylNP(i)Pr2)3CoN2 (L = NH3 (6), MeNH2 (7)). Complexes 4, 5, and 6 have been shown to catalyze the disproportionation of hydrazine into ammonia and dinitrogen gas through a mechanism involving a diazene intermediate.

KR Aur - extremely high variations in optical bands

NASA Astrophysics Data System (ADS)

Boeva, S.; Latev, G.; Nikolov, Y.; Nikolov, P.; Nikolov, G.; Spassov, B.; Petrov, B.; Damljanovic, G.; Sekulic, M.; Zamanov, R.

2017-03-01

Since 2008, the cataclysmic variable star KR Aur is in deep minimum state with a short brightening in 2010. We performed photometric monitoring in 12 nights during the period August 2016 - February 2017 with the telescopes of Rozhen (Bulgaria), Belogradchik (Bulgaria) and Vidojevica (Serbia).

Inhibition of Mdmx (Mdm4) in vivo induces anti-obesity effects.

PubMed

Kon, Ning; Wang, Donglai; Li, Tongyuan; Jiang, Le; Qiang, Li; Gu, Wei

2018-01-26

Although cell-cycle arrest, senescence and apoptosis remain as major canonical activities of p53 in tumor suppression, the emerging role of p53 in metabolism has been a topic of great interest. Nevertheless, it is not completely understood how p53-mediated metabolic activities are regulated in vivo and whether this part of the activities has an independent role beyond tumor suppression. Mdmx (also called Mdm4), like Mdm2, acts as a major suppressor of p53 but the embryonic lethality of mdmx-null mice creates difficulties to evaluate its physiological significance in metabolism. Here, we report that the embryonic lethality caused by the deficiency of mdmx , in contrast to the case for mdm2 , is fully rescued in the background of p53 3KR/3KR , an acetylation-defective mutant unable to induce cell-cycle arrest, senescence and apoptosis. p53 3KR/3KR /mdmx -/- mice are healthy but skinny without obvious developmental defects. p53 3KR/3KR /mdmx -/- mice are resistant to fat accumulation in adipose tissues upon high fat diet. Notably, the levels of p53 protein are only slightly increased and can be further induced upon DNA damage in p53 3KR/3KR /mdmx -/- mice, suggesting that Mdmx is only partially required for p53 degradation in vivo . Further analyses indicate that the anti-obesity phenotypes in p53 3KR/3KR /mdmx -/- mice are caused by activation of lipid oxidation and thermogenic programs in adipose tissues. These results demonstrate the specific effects of the p53/Mdmx axis in lipid metabolism and adipose tissue remodeling and reveal a surprising role of Mdmx inhibition in anti-obesity effects beyond, commonly expected, tumor suppression. Thus, our study has significant implications regarding Mdmx inhibitors in the treatment of obesity related diseases.

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor

DOE Office of Scientific and Technical Information (OSTI.GOV)

von Rohr, Fabian; Winiarski, Michał J.; Tao, Jing

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellentmore » intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials.« less

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor

PubMed Central

von Rohr, Fabian; Winiarski, Michał J.; Tao, Jing; Klimczuk, Tomasz; Cava, Robert Joseph

2016-01-01

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellent intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials. PMID:27803330

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor

DOE PAGES

von Rohr, Fabian; Winiarski, Michał J.; Tao, Jing; ...

2016-11-01

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellentmore » intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials.« less

Microstructure and Tribological Properties of AlCoCrFeNiTi0.5 High-Entropy Alloy in Hydrogen Peroxide Solution

NASA Astrophysics Data System (ADS)

Yu, Y.; Liu, W. M.; Zhang, T. B.; Li, J. S.; Wang, J.; Kou, H. C.; Li, J.

2014-01-01

Microstructure and tribological properties of an AlCoCrFeNiTi0.5 high-entropy alloy in high-concentration hydrogen peroxide solution were investigated in this work. The results show that the sigma phase precipitates and the content of bcc2 decrease during the annealing process. Meanwhile, the complex construction of the interdendrite region changes into simple isolated-island shape, and much more spherical precipitates are formed. Those changes of microstructure during the annealing process lead to the increase of hardness of this alloy. In the testing conditions, the AlCoCrFeNiTi0.5 alloy shows smoother worn surfaces and steadier coefficient of friction curves than does the 1Cr18Ni9Ti stainless steel, and SiC ceramic preserves better wear resistance than ZrO2 ceramic. After annealing, the wear resistance of the AlCoCrFeNiTi0.5 alloy increases coupled with SiC counterface but decreases with ZrO2 counterface.

Capability of Sputtered Micro-patterned NiTi Thick Films

NASA Astrophysics Data System (ADS)

Bechtold, Christoph; Lima de Miranda, Rodrigo; Quandt, Eckhard

2015-09-01

Today, most NiTi devices are manufactured by a combination of conventional metal fabrication steps, e.g., melting, extrusion, cold working, etc., and are subsequently structured by high accuracy laser cutting. This combination has been proven to be very successful; however, there are several limitations to this fabrication route, e.g., in respect to the fabrication of more complex device designs, device miniaturization or the combination of different materials for the integration of further functionality. These issues have to be addressed in order to develop new devices and applications. The fabrication of micro-patterned films using magnetron sputtering, UV lithography, and wet etching has great potential to overcome limitations of conventional device manufacturing. Due to its fabrication characteristics, this method allows the production of devices with complex designs, high structural accuracy, smooth edge profile, at layer thicknesses up to 75 µm. The aim of this study is to present recent developments in the field of NiTi thin film technology, its advantages and limitations, as well as new possible applications in the medical and in non-medical fields. These developments include among others NiTi scaffold structures covered with NiTi membranes for their potential use as filters, heart valve components or aneurysm treatments, as well as micro-actuators for consumable electronics or automotive applications.

Chalcogenide Aerogels as Sorbents for Noble Gases (Xe, Kr)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Subrahmanyam, Kota S.; Spanopoulos, Ioannis; Chun, Jaehun

High surface MoSx and SbSx chalcogels were studied for Xe/Kr gas separation. The intrinsic soft character of the chalcogel framework is a unique property among the large family of porous materials and offers a potential new approach towards the selective separation of Xe over Kr. Among these chalcogels, MoSx shows the highest Xe and Kr uptake, reaching 0.69 mmol g-1 (1.05 mmol cm-3) and 0.28 mmol g-1 (0.42 mmol cm-3) respectively, at 273 K and 1 bar. The corresponding isosteric heat of adsorption at zero coverage (Qst0) is 22.8 and 18.6 kJ mol-1 and both are the highest among themore » selected chalcogels. The IAST (10:90) Xe/Kr selectivity at 273 K for MoSx is 6.0 while for SbSx chalcogels varies in the range 2.0-2.8. The higher formal charge of molybdenum, Mo4+, in MoSx versus that of antimony, Sb3+, in SbSx coupled with its larger atomic size could induce higher polarizability in the MoSx framework and therefore higher Xe/Kr selectivity.« less

Cytological lesions in the midgut of Tribolium confusum larvae exposed to gamma radiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jafri, R.H.; Ismail, M.

1977-01-01

The major cytological lesions in Tribolium confusum after irradiation were displayed by the midgut epithelium. At 24 hr following exposure to 5.3 kR, the regenerative cells called nidi appeared numerous. They gradually disappeared with increases in dosage and time in accordance with Arndt-Schulze's Law. The columnar epithelial cells and their nuclei appeared swollen and vacuolated on the fifth and twelfth day following exposure to 5.3 kR. They appeared disorganized and shed into the lumen of the midgut on the twelfth and fifth day following 50- and 70-kR irradiation, respectively. The basement membrane and the muscularis appeared loose on the fifthmore » and twelfth day dollowing 70-kR irradiation. It was observed that once the catabolic activity, i.e., histolysis, was initiated in the midgut, it continued to accelerate with increasing dose and time. Thus, the last effects at low doses, 5.3 and 10 kR, appeared as immediate effects at high doses, 50 and 70 kR. The differentiated cells, i.e., columnar epithelial cells, appeared radioresistant as compared to undifferentiated cells, i.e., regenerative cells, which appeared radiosensitive in accordance with the principle of Bergonie and Tribondeau.« less

(Zr,Ti)O2 interface structure in ZrO2-TiO2 nanolaminates with ultrathin periodicity

NASA Astrophysics Data System (ADS)

Aita, C. R.; DeLoach, J. D.; Yakovlev, V. V.

2002-07-01

A mixed cation interfacial structure in ZrO2-TiO2 nanolaminate films with ultrathin bilayer periodicity grown by sputter deposition at 297 K was identified by x-ray diffraction and nonresonant Raman spectroscopy. This structure consists of an amorphous phase at a ZrO2-on-TiO2 bilayer interface, followed by an extensive crystalline monoclinic (Zr,Ti)O2 solid solution predicted by Vegard's law. Monoclinic (Zr,Ti)O2 has previously been reported only once, in bulk powder of a single composition (ZrTiO4) at high pressure. Its stabilization in the nanolaminates is explained by the Gibbs-Thomson effect. This complex interfacial structure is shown to be a means of accommodating chemical mixing in the absence of a driving force for heteroepitaxy.

Improvement in Titanium Complexes Bearing Schiff Base Ligands in the Ring-Opening Polymerization of L-Lactide: A Dinuclear System with Hydrazine-Bridging Schiff Base Ligands.

PubMed

Tseng, Hsi-Ching; Chen, Hsing-Yin; Huang, Yen-Tzu; Lu, Wei-Yi; Chang, Yu-Lun; Chiang, Michael Y; Lai, Yi-Chun; Chen, Hsuan-Ying

2016-02-15

A series of titanium (Ti) complexes bearing hydrazine-bridging Schiff base ligands were synthesized and investigated as catalysts for the ring-opening polymerization (ROP) of L-lactide (LA). Complexes with electron withdrawing or steric bulky groups reduced the catalytic activity. In addition, the steric bulky substituent on the imine groups reduced the space around the Ti atom and then reduced LA coordination with Ti atom, thereby reducing catalytic activity. All the dinuclear Ti complexes exhibited higher catalytic activity (approximately 10-60-fold) than mononuclear L(Cl-H)-TiOPr2 did. The strategy of bridging dinuclear Ti complexes with isopropoxide groups in the ROP of LA was successful, and adjusting the crowded heptacoordinated transition state by the bridging isopropoxide groups may be the key to our successful strategy.

Synthesis and Microstructure of Highly Oriented PbTiO3 Thin Films Prepared by a Sol-Gel Method

DTIC Science & Technology

1989-06-01

lead acetate with titanium isopropoxide * in 2-methoxyethanol,* in a method similar to that reported by Gurkovitch and Blum." The resulting yellow-gold...orientation by a sol-gel processing method. EXPERIMENTAL Precursor Solution Preparation Stock solutions of complex Pb-Ti alkoxide were prepared by reacting... solution had an equivalent PbTiO 3 concentration of approximately 66 wt%. The alkoxide solutions were handled as moisture-sensitive reagents and, as

Alternative to classic annealing treatments for fractally patterned TiO{sub 2} thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Overschelde, O. van; Wautelet, M.; Guisbiers, G.

2008-11-15

Titanium dioxide thin films have been deposited by reactive magnetron sputtering on glass and subsequently irradiated by UV radiation using a KrF excimer laser. The influence of the laser fluence (F) on the constitution and microstructure of the deposited films is studied for 0.05

Decomposition Theory in the Teaching of Elementary Linear Algebra.

ERIC Educational Resources Information Center

London, R. R.; Rogosinski, H. P.

1990-01-01

Described is a decomposition theory from which the Cayley-Hamilton theorem, the diagonalizability of complex square matrices, and functional calculus can be developed. The theory and its applications are based on elementary polynomial algebra. (KR)

High spin states of 72-74Kr

NASA Astrophysics Data System (ADS)

Kaushik, M.; Kumawat, M.; Singh, U. K.; Saxena, G.

2018-05-01

A theoretical investigation has made on the structure of high spin states of 72-74Kr within the framework of cranked Hartree-Fock-Bogoliubov (CHFB) theory employing a pairing + quadrupole + hexadecapole model interaction. Dependence of shape with the spin, excitation energy, alignment of proton as well as neutron 0g9/2 orbital along with backbending phenomenon are discussed upto a high spin J = 26. We found reasonable agreement with the experimental values and other theoretical calculations.

Geochemistry of lavas from the Australian-Antarctic Ridge, easternmost Southeast Indian Ridge

NASA Astrophysics Data System (ADS)

Park, S.; Langmuir, C. H.; Lin, J.; Kim, S.; Hahm, D.; Michael, P. J.; Baker, E. T.

2012-12-01

The intermediate spreading Australian-Antarctic Ridge (AAR), an easternmost extension of the South East Indian Ridge located in the south of Tasmania, is one of the largest unexplored regions of the global mid-ocean ridge system, owing to its remote location and a very limited workable weather window. In early and late 2011, the Korea Polar Research Institute (KOPRI) conducted two surveys of two segments at 160°E (KR1) and 152.5°E (KR2) using the icebreaker Araon, producing a multi-beam map, 48 rock core samples and a MAPR (Miniature Autonomous Plume Recorder) hydrothermal survey. The full spreading rate of the spreading center in this area is 68 mm/yr. The axial depth of KR1 is relatively shallow (~2,000m) and is a first-order segment bounded by two large offset transform faults. The axial morphology of KR1 varies substantially from an axial high plateau (Segment 1) in the west, to a small rift valley (Segment 2), to an axial high with graben (Segment 3), and to a substantial rift valley (Segment 4) in the east. These changes occur in the absence of marked offsets in the ridge, such as overlapping spreading centers. Even so, these segments can be divided still further into shorter scale segments based on small discontinuities in the linearity of the axis and variations in rock chemistry. Small offsets in bathymetry can be associated with large chemical changes, such as between Segments 2 and 3, where incompatible element abundances change by almost a factor of ten. Incompatible trace element ratios for basalts show a regular pattern that is nonetheless not a single gradient. Along Segments 1 and 2, an axial high changes to a modest rift, (La/Sm)N of basalts decreases from 0.9 to 0.5. Then there is an abrupt step in enrichment to (La/Sm)N of 1.5, associated with a shallower depths and the appearance of an off-axis seamount south of the axis. This enrichment persists eastwards and then declines progressively to values of (La/Sm)N of 0.7 in the pronounced rift valley of Segment 4. Plume signals indicating hydrothermal vents were found in the middle of KR1 where the most enriched basalts occur and the magma supply appears robust. The first- order segment KR2 can be divided into two segments -- an axial high western segment, and a rift valley eastern segment. Hydrothermal vent signals were mainly found in the western part of the segment. The KR2 samples are mostly depleted, but KR2 also contains enriched basalts, including an E-MORB with 0.65% K2O in the western segment. Enriched KR2 basalts have different ratios of alkalis to HFSE compared to KR1, suggesting they are not derived from the same enriched component. In general in this region, inflated axial morphology is associated with trace element enrichment, suggesting that magma flux is being influenced by changing mantle composition on the segment scale.

Tetrahedral silsesquioxane-C2H2Ti complex for hydrogen storage

NASA Astrophysics Data System (ADS)

Konda, Ravinder; Tavhare, Priyanka; Ingale, Nilesh; Chaudhari, Ajay

2018-04-01

The interaction of molecular hydrogen with tetrahedral silsesquioxane (T4)-C2H2Ti complex has been studied using Density Functional Theory with M06-2X functional and MP2 method with 6-311++G** basis set. T4-C2H2Ti complex can absorb maximum five hydrogen molecules with the gravimetric hydrogen storage capacity of 3.4 wt %. Adsorption energy calculations show that H2 adsorption on T4-C2H2Ti complex is favorable at room temperature by both the methods. We have studied the effect of temperature and pressure on Gibbs free energy corrected adsorption energies. Molecular dynamics simulations for H2 adsorbed T4-C2H2Ti complex have also been performed at 300K and show that loosely bonded H2 molecule flies away within 1fs. Various interaction energies within the complex are studied. Stability of a complex is predicted by means of a gap between Highest Occupied Molecular Orbital (HUMO) and Lowest Unoccupied Molecular Orbital (LUMO). The H2 desorption temperature for T4-C2H2Ti complex is calculated with Van't Hoff equation and it is found to be 229K.

Gaseous 83mKr generator for KATRIN

NASA Astrophysics Data System (ADS)

Sentkerestiová, J.; Dragoun, O.; Lebeda, O.; Ryšavý, M.; Sturm, M.; Vénos, D.

2018-04-01

Monoenergetic conversion electrons from the 83mKrKr isomeric state have been proven to be useful in the calibration of several tritium neutrino mass and dark matter experiments. In this paper the design and characteristics of the gaseous 83mKrKr generator, including the 83Rb/83mKrKr source behavior in tritium, for the KATRIN experiment are presented. Using Si(Li) and silicon drift detectors (SDD) detectors, the half-life of the 83mKrKr isomeric state was measured to be 1.8620 ± 0.0019 h.

Electron-pinned defect-dipoles for high-performance colossal permittivity materials

NASA Astrophysics Data System (ADS)

Hu, Wanbiao; Liu, Yun; Withers, Ray L.; Frankcombe, Terry J.; Norén, Lasse; Snashall, Amanda; Kitchin, Melanie; Smith, Paul; Gong, Bill; Chen, Hua; Schiemer, Jason; Brink, Frank; Wong-Leung, Jennifer

2013-09-01

The immense potential of colossal permittivity (CP) materials for use in modern microelectronics as well as for high-energy-density storage applications has propelled much recent research and development. Despite the discovery of several new classes of CP materials, the development of such materials with the required high performance is still a highly challenging task. Here, we propose a new electron-pinned, defect-dipole route to ideal CP behaviour, where hopping electrons are localized by designated lattice defect states to generate giant defect-dipoles and result in high-performance CP materials. We present a concrete example, (Nb+In) co-doped TiO2 rutile, that exhibits a largely temperature- and frequency-independent colossal permittivity (> 104) as well as a low dielectric loss (mostly < 0.05) over a very broad temperature range from 80 to 450 K. A systematic defect analysis coupled with density functional theory modelling suggests that ‘triangular’ In23+VO••Ti3+ and ‘diamond’ shaped Nb25+Ti3+ATi (A  =  Ti3+/In3+/Ti4+) defect complexes are strongly correlated, giving rise to large defect-dipole clusters containing highly localized electrons that are together responsible for the excellent CP properties observed in co-doped TiO2. This combined experimental and theoretical work opens up a promising feasible route to the systematic development of new high-performance CP materials via defect engineering.

Laser ablated high T(sub c) superconducting thin YBa2Cu3O(7-x) films on substrates suitable for microwave applications

NASA Astrophysics Data System (ADS)

Warner, J. D.; Meola, J. E.; Jenkins, K. A.; Bhasin, K. B.

1990-04-01

The development of high temperature superconducting YBa2Cu3O(7-x) thin films on substrates suitable for microwave applications is of great interest for evaluating their applications for space radar, communication, and sensor systems. Thin films of YBa2Cu3O(7-x) were formed on SrTiO3, ZrO2, MgO, and LaAlO3 substrates by laser ablation. The wavelength used was 248 nm from a KrF excimer laser. During deposition the films were heated to 600 C in a flowing oxygen environment, and required no post annealing. The low substrate temperature during deposition with no post annealing gave films which were smooth, which had their c-axis aligned to the substrates, and which had grains ranging from 0.2 to 0.5 microns in size. The films being c-axis aligned gave excellent surface resistance at 35 GHz which was lower than that of copper at 77 K. At present, LaAlO3 substrates with a dielectric constant of 22, appears suitable as a substrate for microwave and electronic applications. The films were characterized by resistance-temperature measurements, scanning electron microscopy, and x ray diffraction. The highest critical transition temperatures (T sub c) are above 89 K for films on SrTiO3 and LaAlO3, above 88 K for ZrO2, and above 86 K for MgO. The critical current density (J sub c) of the films on SrTiO3 is above 2 x 10(exp 6) amperes/sq cm at 77 K. The T(sub c) and J(sub c) are reported as a function of laser power, composition of the substrate, and temperature of the substrate during deposition.

Energy transfer of highly vibrationally excited naphthalene: collisions with CHF3, CF4, and Kr.

PubMed

Chen Hsu, Hsu; Tsai, Ming-Tsang; Dyakov, Yuri A; Ni, Chi-Kung

2011-08-07

Energy transfer of highly vibrationally excited naphthalene in the triplet state in collisions with CHF(3), CF(4), and Kr was studied using a crossed-beam apparatus along with time-sliced velocity map ion imaging techniques. Highly vibrationally excited naphthalene (2.0 eV vibrational energy) was formed via the rapid intersystem crossing of naphthalene initially excited to the S(2) state by 266 nm photons. The shapes of the collisional energy-transfer probability density functions were measured directly from the scattering results of highly vibrationally excited naphthalene. In comparison to Kr atoms, the energy transfer in collisions between CHF(3) and naphthalene shows more forward scatterings, larger cross section for vibrational to translational (V → T) energy transfer, smaller cross section for translational to vibrational and rotational (T → VR) energy transfer, and more energy transferred from vibration to translation, especially in the range -ΔE(d) = -100 to -800 cm(-1). On the other hand, the difference of energy transfer properties between collisional partners Kr and CF(4) is small. The enhancement of the V → T energy transfer in collisions with CHF(3) is attributed to the large attractive interaction between naphthalene and CHF(3) (1-3 kcal/mol).

Cross sections and rate coefficients for inner-shell excitation of Li-like ions with 6 < Z < 42

NASA Astrophysics Data System (ADS)

Safronova, U. I.; Safronova, M. S.; Kato, T.

1996-07-01

Excitation cross sections and rate coefficients by electron impact were calculated for the 1s22s-1s2s2p, 1s22s-1s2s2 and 1s22s-1s2p2 transitions of the Li-like ions (C IV, N V, O VI, Ne VIII, Mg X, Al XI, Si XII, S XIV, Ar XVI, Ca XVIII, Ti XX, Fe XXIV, Ni XXVI, Zn XXVIII, Ge XXX, Se XXXII, Kr XXXIV and Mo XXXX) in the Coulomb-Born approximation with exchange including relativistic effects and configuration interaction. Level energies, mixing coefficients and transition wavelengths and probabilities were also computed. Calculations performed by the 1/Z perturbation theory and Coulomb-Born approximation are compared with the R-matrix method and the distorted-wave approximation were Z is the nuclear charge. Formulae obtained for the angular factors of n-electron atomic system allow one to generalize this method to an arbitrary system of highly charged ions.

Structure and functional properties of TiNiZr surface layers obtained by high-velocity oxygen fuel spraying

NASA Astrophysics Data System (ADS)

Rusinov, P. O.; Blednova, Zh M.; Borovets, O. I.

2017-05-01

The authors studied a complex method of surface modification of steels for materials with shape memory effect (SME) Ti-Ni-Zr with a high-velocity oxygen-fuel spraying (HVOF) of mechanically activated (MA) powder in a protective medium. We assessed the functional properties and X-ray diffraction studies, which showed that the formation of surface layers according to the developed technology ensures the manifestation of the shape memory effect.

High-temperature solution growth and characterization of (1-x)PbTiO3-xBi(Zn2/3Nb1/3)O3 piezo-/ferroelectric single crystals

NASA Astrophysics Data System (ADS)

Paterson, Alisa R.; Zhao, Jinyan; Liu, Zenghui; Wu, Xiaoqing; Ren, Wei; Ye, Zuo-Guang

2018-03-01

Complex perovskite PbTiO3-Bi(Me‧Me″)O3 solid solutions represent new materials systems that possess a higher Curie temperature (TC) than the relaxor-PbTiO3 solid solutions, and are useful for potential applications. To this end, novel ferroelectric single crystals of the (1-x)PbTiO3-xBi(Zn2/3Nb1/3)O3 (PT-BZN) solid solution were successfully grown by the high-temperature solution growth (HTSG) method. Powder X-ray diffraction shows that the symmetry of the grown crystals is tetragonal. The dielectric permittivity and optical domain structures were characterized by dielectric measurements and polarized light microscopy, respectively, as a function of temperature, revealing a first-order ferroelectric-paraelectric phase transition at a TC of 436 ± 2 °C. Based on the TC, the average composition of the crystal platelet was estimated to be 0.58PT-0.42BZN. Piezoresponse force microscopy measurements of the phase and amplitude as a function of voltage reveal the complex polar domain structure and demonstrate the ferroelectric switching behaviour of these materials. These results suggest that the PT-BZN single crystals indeed form a new family of high TC piezo-/ferroelectric materials which are potentially useful for the fabrication of electromechanical transducers for high-temperature applications.

Computing Relative Free Energies of Solvation using Single Reference Thermodynamic Integration Augmented with Hamiltonian Replica Exchange.

PubMed

Khavrutskii, Ilja V; Wallqvist, Anders

2010-11-09

This paper introduces an efficient single-topology variant of Thermodynamic Integration (TI) for computing relative transformation free energies in a series of molecules with respect to a single reference state. The presented TI variant that we refer to as Single-Reference TI (SR-TI) combines well-established molecular simulation methodologies into a practical computational tool. Augmented with Hamiltonian Replica Exchange (HREX), the SR-TI variant can deliver enhanced sampling in select degrees of freedom. The utility of the SR-TI variant is demonstrated in calculations of relative solvation free energies for a series of benzene derivatives with increasing complexity. Noteworthy, the SR-TI variant with the HREX option provides converged results in a challenging case of an amide molecule with a high (13-15 kcal/mol) barrier for internal cis/trans interconversion using simulation times of only 1 to 4 ns.

The complex behavior of the Pd 7 cluster supported on TiO 2 (110) during CO oxidation: adsorbate-driven promoting effect

DOE PAGES

An, Wei; Liu, Ping

2016-09-07

When using the TiO 2(110)-supported Pd7 cluster as a model catalyst, we identified the dynamics of supported metal nanoparticles using density functional theory calculations, at the sub-nanometer scale and under reactive environments. Increasing the CO coverage can induce a structural transformation from Pd 7-3D/TiO 2(110) at low coverage to Pd 7-2D/TiO 2(110) at the saturation coverage wherein CO saturation-driven Pd7-2D/TiO 2(110) structure displays superior CO oxidation activity at the interfacial sites, which are highly active for catalyzing O 2 dissociation and CO oxidation via bifunctional synergy.

High-Speed Schlieren and 10-Hz Kr PLIF for the new AFRL Mach-6 Ludwieg Tube Hypersonic Wind Tunnel

DTIC Science & Technology

2017-11-01

STATES AIR FORCE AFRL-RQ-WP-TP-2017-0167 HIGH -SPEED SCHLIEREN AND 10-HZ KR PLIF FOR THE NEW AFRL MACH 6 LUDWIEG TUBE HYPERSONIC WIND TUNNEL Roger...L. Kimmel and Campbell D. Carter Hypersonic Sciences Branch High Speed Systems Division Joshua D. Pickles and Venkateswaran Narayanaswamy North...Public Affairs Office (PAO) and is available to the general public, including foreign nationals. Copies may be obtained from the Defense Technical

[Cr-Ti-Al-N complex coating on titanium to strengthen Ti/porcelain bonding].

PubMed

Zhang, Hui; Guo, Tian-wen; Li, Jun-ming; Pan, Jing-guang; Dang, Yong-gang; Tong, Yu

2006-02-01

To study the feasibility of magnetron sputtering Cr-Ti-Al-N complex coating as an interlayer on titanium to enhance the titanium-ceramic binding strength. With a three-point bending test according to ISO 9693, the binding strength of Duceratin (Degussa) to titanium substrate prepared with 4 different surface treatments (polishing, polishing and megnetron sputtering Cr, Ti, Al, and N complex coating, sandblasting, sandblasting and coating) was evaluated. Ti/porcelain interface and fractured Ti surface were examined using scanning electron microscopy with energy-dispersive spectrometry (EDS). The binding strength of polished and coated titanium/Duceratin was significantly higher than polished titanium group (P<0.05). The binding strength of sandblasted and coated titanium/Duceratin did not differ significantly from that of sandblasted titanium group (P>0.05), and the strength in the two sandblasted titanium groups was significantly higher than that in polished and coated titanium group (P<0.05). Megnetron sputtering Cr-Ti-Al-N complex on polished titanium can increase the titanium/porcelain binding strength. Megnetron sputtering coating is a promising Ti/porcelain interlayer.

Strain-induced phenomenon in complex oxide thin films

NASA Astrophysics Data System (ADS)

Haislmaier, Ryan

Complex oxide materials wield an immense spectrum of functional properties such as ferroelectricity, ferromagnetism, magnetoelectricity, optoelectricity, optomechanical, magnetoresistance, superconductivity, etc. The rich coupling between charge, spin, strain, and orbital degrees of freedom makes this material class extremely desirable and relevant for next generation electronic devices and technologies which are trending towards nanoscale dimensions. Development of complex oxide thin film materials is essential for realizing their integration into nanoscale electronic devices, where theoretically predicted multifunctional capabilities of oxides could add tremendous value. Employing thin film growth strategies such as epitaxial strain and heterostructure interface engineering can greatly enhance and even unlock novel material properties in complex oxides, which will be the main focus of this work. However, physically incorporating oxide materials into devices remains a challenge. While advancements in molecular beam epitaxy (MBE) of thin film oxide materials has led to the ability to grow oxide materials with atomic layer precision, there are still major limitations such as controlling stoichiometric compositions during growth as well as creating abrupt interfaces in multi-component layered oxide structures. The work done in this thesis addresses ways to overcome these limitations in order to harness intrinsic material phenomena. The development of adsorption-controlled stoichiometric growth windows of CaTiO3 and SrTiO3 thin film materials grown by hybrid MBE where Ti is supplied using metal-organic titanium tetraisopropoxide material is thoroughly outlined. These growth windows enable superior epitaxial strain-induced ferroelectric and dielectric properties to be accessed as demonstrated by chemical, structural, electrical, and optical characterization techniques. For tensile strained CaTiO3 and compressive strained SrTiO 3 films, the critical effects of nonstoichiometry on ferroelectric properties are investigated, where enhanced ferroelectric responses are only found for stoichiometric films grown inside of the growth windows, whereas outside of the optimal growth window conditions, ferroelectric properties are greatly deteriorated and eventually disappear for highly nonstoichiometric film compositions. Utilizing these stoichiometric growth windows, high temperature polar phase transitions are discovered for compressively strained CaTiO3 films with transition temperatures in excess of 700 K, rendering this material as a strong candidate for high temperature electronic applications. Beyond the synthesis of single phase materials using hybrid MBE, a methodology is presented for constructing layered (SrTiO3)n/(CaTiO 3)n superlattice structures, where precise control over the unit cell layering thickness (n) is demonstrated using in-situ reflection high energy electron diffraction. The effects of interface roughness and layering periodicity (n) on the strain-induced ferroelectric properties for a series of n=1-10 (SrTiO3)n/(CaTiO3) n superlattice films are investigated. It is found that the stabilization of a ferroelectric phase is independent of n, but is however strongly dominated by the degree of interface roughness which is quantified by measuring the highest nth order X-ray diffraction peak splitting of each superlattice film. A counter-intuitive realization is made whereby a critical amount of interface roughness is required in order to enable the formation of the predicted strain-stabilized ferroelectric phase, whereas sharp interfaces actually suppress this ferroelectric phase from manifesting. It is shown how high-quality complex oxide superlattices can be constructed using hybrid MBE technique, allowing the ability to control layered materials at the atomic scale. Furthermore, a detailed growth methodology is provided for constructing a layered n=4 SrO(SrTiO3)n Ruddlesden-Popper (RP) phase by hybrid MBE, where the ability to deposit single monolayers of SrO and TiO2 is utilized to build the RP film structure over a time period of 5 hours. This is the first time that a thin film RP phase has been grown using hybrid MBE, where an a stable control over the fluxes is demonstrated during relatively long time periods of growth, which advantageously facilitates the synthesis of high-quality RP materials with excellent structural and chemical homogeneity. Additionally, this work demonstrates some major advancements in optical second harmonic generation (SHG) characterization techniques of ferroelectric thin film materials. The SHG characterization techniques developed here proved to be the 'bread-and-butter' for most of the work performed in this thesis, providing a powerful tool for identifying the existence of strain-induced ferroelectric phases, including their temperature dependence and polar symmetry. The work presented in this dissertation will hopefully provide a preliminary road map for future hybrid MBE growers, scientists and researchers, to develop and investigate epitaxial strain and heterostructure layering induced phenomena in other complex oxide systems.

A novel urotensin II receptor antagonist, KR-36996, improved cardiac function and attenuated cardiac hypertrophy in experimental heart failure.

PubMed

Oh, Kwang-Seok; Lee, Jeong Hyun; Yi, Kyu Yang; Lim, Chae Jo; Park, Byung Kil; Seo, Ho Won; Lee, Byung Ho

2017-03-15

Urotensin II and its receptor are thought to be involved in various cardiovascular diseases such as heart failure, pulmonary hypertension and atherosclerosis. Since the regulation of the urotensin II/urotensin II receptor offers a great potential for therapeutic strategies related to the treatment of cardiovascular diseases, the study of selective and potent antagonists for urotensin II receptor is more fascinating. This study was designed to determine the potential therapeutic effects of a newly developed novel urotensin II receptor antagonist, N-(1-(3-bromo-4-(piperidin-4-yloxy)benzyl)piperidin-4-yl)benzo[b]thiophene-3-carboxamide (KR-36996), in experimental models of heart failure. KR-36996 displayed a high binding affinity (Ki=4.44±0.67nM) and selectivity for urotensin II receptor. In cell-based study, KR-36996 significantly inhibited urotensin II-induced stress fiber formation and cellular hypertrophy in H9c2 UT cells. In transverse aortic constriction-induced cardiac hypertrophy model in mice, the daily oral administration of KR-36996 (30mg/kg) for 14 days significantly decreased left ventricular weight by 40% (P<0.05). In myocardial infarction-induced chronic heart failure model in rats, repeated echocardiography and hemodynamic measurements demonstrated remarkable improvement of the cardiac performance by KR-36996 treatment (25 and 50mg/kg/day, p.o.) for 12 weeks. Moreover, KR-36996 decreased interstitial fibrosis and cardiomyocyte hypertrophy in the infarct border zone. These results suggest that potent and selective urotensin II receptor antagonist could efficiently attenuate both cardiac hypertrophy and dysfunction in experimental heart failure. KR-36996 may be useful as an effective urotensin II receptor antagonist for pharmaceutical or clinical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Different protein kinase C isoenzymes mediate inhibition of cardiac rapidly activating delayed rectifier K+ current by different G-protein coupled receptors.

PubMed

Liu, Xueli; Wang, Yuhong; Zhang, Hua; Shen, Li; Xu, Yanfang

2017-12-01

Elevated angiotensin II (Ang II) and sympathetic activity contributes to a high risk of ventricular arrhythmias in heart disease. The rapidly activating delayed rectifier K + current (I Kr ) carried by the hERG channels plays a critical role in cardiac repolarization, and decreased I Kr is involved in increased cardiac arrhythmogenicity. Stimulation of α 1A -adrenoreceptors or angiotensin II AT 1 receptors is known to inhibit I Kr via PKC. Here, we have identified the PKC isoenzymes mediating the inhibition of I Kr by activation of these two different GPCRs. The whole-cell patch-clamp technique was used to record I Kr in guinea pig cardiomyocytes and HEK293 cells co-transfected with hERG and α 1A -adrenoreceptor or AT 1 receptor genes. A broad spectrum PKC inhibitor Gö6983 (not inhibiting PKCε), a selective cPKC inhibitor Gö6976 and a PKCα-specific inhibitor peptide, blocked the inhibition of I Kr by the α 1A -adrenoreceptor agonist A61603. However, these inhibitors did not affect the reduction of I Kr by activation of AT 1 receptors, whereas the PKCε-selective inhibitor peptide did block the effect. The effects of angiotensin II and the PKCε activator peptide were inhibited in mutant hERG channels in which 17 of the 18 PKC phosphorylation sites were deleted, whereas a deletion of the N-terminus of the hERG channels selectively prevented the inhibition elicited by A61603 and the cPKC activator peptide. Our results indicated that inhibition of I Kr by activation of α 1A -adrenoreceptors or AT 1 receptors were mediated by PKCα and PKCε isoforms respectively, through different molecular mechanisms. © 2017 The British Pharmacological Society.

Cross-Section Measurements of the Kr86(γ,n) Reaction to Probe the s-Process Branching at Kr85

NASA Astrophysics Data System (ADS)

Raut, R.; Tonchev, A. P.; Rusev, G.; Tornow, W.; Iliadis, C.; Lugaro, M.; Buntain, J.; Goriely, S.; Kelley, J. H.; Schwengner, R.; Banu, A.; Tsoneva, N.

2013-09-01

We have carried out photodisintegration cross-section measurements on Kr86 using monoenergetic photon beams ranging from the neutron separation energy, Sn=9.86MeV, to 13 MeV. We combine our experimental Kr86(γ,n)Kr85 cross section with results from our recent Kr86(γ,γ') measurement below the neutron separation energy to obtain the complete nuclear dipole response of Kr86. The new experimental information is used to predict the neutron capture cross section of Kr85, an important branching point nucleus on the abundance flow path during s-process nucleosynthesis. Our new and more precise Kr85(n,γ)Kr86 cross section allows us to produce more precise predictions of the Kr86 abundance from s-process models. In particular, we find that the models of the s process in asymptotic giant branch stars of mass <1.5M⊙, where the C13 neutron source burns convectively rather than radiatively, represent a possible solution for the highest Kr86∶Kr82 ratios observed in meteoritic stardust SiC grains.

Cross-section measurements of the 86Kr(γ,n) reaction to probe the s-process branching at 85Kr.

PubMed

Raut, R; Tonchev, A P; Rusev, G; Tornow, W; Iliadis, C; Lugaro, M; Buntain, J; Goriely, S; Kelley, J H; Schwengner, R; Banu, A; Tsoneva, N

2013-09-13

We have carried out photodisintegration cross-section measurements on 86Kr using monoenergetic photon beams ranging from the neutron separation energy, S(n) = 9.86  MeV, to 13 MeV. We combine our experimental 86Kr(γ,n)85Kr cross section with results from our recent 86Kr(γ,γ') measurement below the neutron separation energy to obtain the complete nuclear dipole response of 86Kr. The new experimental information is used to predict the neutron capture cross section of 85Kr, an important branching point nucleus on the abundance flow path during s-process nucleosynthesis. Our new and more precise 85Kr(n,γ)86Kr cross section allows us to produce more precise predictions of the 86Kr abundance from s-process models. In particular, we find that the models of the s process in asymptotic giant branch stars of mass <1.5M⊙, where the 13C neutron source burns convectively rather than radiatively, represent a possible solution for the highest 86Kr:82Kr ratios observed in meteoritic stardust SiC grains.

Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane.

PubMed

Samantaray, Manoja K; Kavitake, Santosh; Morlanés, Natalia; Abou-Hamad, Edy; Hamieh, Ali; Dey, Raju; Basset, Jean-Marie

2017-03-08

Two compatible organometallic complexes, W(Me) 6 (1) and TiNp 4 (2), were successively anchored on a highly dehydroxylated single silica support (SiO 2-700 ) to synthesize the well-defined bimetallic precatalyst [(≡Si-O-)W(Me) 5 (≡Si-O-)Ti(Np) 3 ] (4). Precatalyst 4 was characterized at the molecular level using advanced surface organometallic chemistry (SOMC) characterization techniques. The strong autocorrelation observed between methyl of W and Ti in 1 H- 1 H multiple-quantum NMR spectra demonstrates that W and Ti species are in close proximity to each other. The bimetallic precatalyst 4, with a turnover number (TON) of 9784, proved to be significantly more efficient than the silica-supported monometallic catalyst [(≡Si-O-)W(Me) 5 ] (3), with a TON of 98, for propane metathesis at 150 °C in a flow reactor. The dramatic improvement in the activity signifies the cooperativity between Ti and W and indicates that the key step of alkane metathesis (C-H bond activation followed by β-H elimination) occurs on Ti, followed by olefin metathesis, which occurs on W. We have demonstrated the influence and importance of proximity of Ti to W for achieving such a significantly high activity. This is the first report demonstrating the considerably high activity (TON = 9784) in propane metathesis at moderate temperature (150 °C) using a well-defined bimetallic system prepared via the SOMC approach.

KrF laser amplifier with phase-conjugate Brillouin retroreflectors.

PubMed

Gower, M C

1982-09-01

We have demonstrated the use of phase-conjugate stimulated Brillouin scattering mirrors to produce high-quality, short-pulse KrF laser beams from angular multiplexed and regenerative amplifiers. The mirror was also shown to isolate systems optically from amplifier spontaneous emission. Automatic alignment of targets using this mirror as a retroreflector was also demonstrated.

Magnetoelectric coupling of multiferroic chromium doped barium titanate thin film probed by magneto-impedance spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shah, Jyoti, E-mail: shah.jyoti1@gmail.com; Kotnala, Ravinder K., E-mail: rkkotnala@nplindia.org, E-mail: rkkotnala@gmail.com

2014-04-07

Thin film of BaTiO{sub 3} doped with 0.1 at. % Cr (Cr:BTO) has been prepared by pulsed laser deposition technique. Film was deposited on Pt/SrTiO{sub 3} substrate at 500 °C in 50 mTorr Oxygen gas pressure using KrF (298 nm) laser. Polycrystalline growth of single phase Cr:BTO thin film has been confirmed by grazing angle X-ray diffraction. Cr:BTO film exhibited remnant polarization 6.4 μC/cm{sup 2} and 0.79 MV/cm coercivity. Magnetization measurement of Cr:BTO film showed magnetic moment 12 emu/cc. Formation of weakly magnetic domains has been captured by magnetic force microscopy. Theoretical impedance equation fitted to experimental data in Cole-Cole plot for thin film inmore » presence of transverse magnetic field resolved the increase in grain capacitance from 4.58 × 10{sup −12} to 5.4 × 10{sup −11} F. Film exhibited high value 137 mV/cm-Oe magneto-electric (ME) coupling coefficient at room temperature. The high value of ME coupling obtained can reduce the typical processing steps involved in multilayer deposition to obtain multiferrocity in thin film. Barium titanate being best ferroelectric material has been tailored to be multiferroic by non ferromagnetic element, Cr, doping in thin film form opens an avenue for more stable and reliable spintronic material for low power magnetoelectric random excess memory applications.« less

Structure of a Water Monolayer on the Anatase TiO2(101) Surface

NASA Astrophysics Data System (ADS)

Patrick, Christopher E.; Giustino, Feliciano

2014-07-01

Titanium dioxide (TiO2) plays a central role in the study of artificial photosynthesis, owing to its ability to perform photocatalytic water splitting. Despite over four decades of intense research efforts in this area, there is still some debate over the nature of the first water monolayer on the technologically relevant anatase TiO2(101) surface. In this work, we use first-principles calculations to reverse engineer the experimental high-resolution x-ray photoelectron spectra measured for this surface by Walle et al. [J. Phys. Chem. C 115, 9545 (2011)] and find evidence supporting the existence of a mix of dissociated and molecular water in the first monolayer. Using both semilocal and hybrid functional calculations, we revise the current understanding of the adsorption energetics by showing that the energetic cost of water dissociation is reduced via the formation of a hydrogen-bonded hydroxyl-water complex. We also show that such a complex can provide an explanation of an unusual superstructure observed in high-resolution scanning tunneling microscopy experiments.

Bubble evolution in Kr-irradiated UO2 during annealing

NASA Astrophysics Data System (ADS)

He, L.; Bai, X. M.; Pakarinen, J.; Jaques, B. J.; Gan, J.; Nelson, A. T.; El-Azab, A.; Allen, T. R.

2017-12-01

Transmission electron microscopy observation of Kr bubble evolution in polycrystalline UO2 annealed at high temperature was conducted in order to understand the inert gas behavior in oxide nuclear fuel. The average diameter of intragranular bubbles increased gradually from 0.8 nm in as-irradiated sample at room temperature to 2.6 nm at 1600 °C and the bubble size distribution changed from a uniform distribution to a bimodal distribution above 1300 °C. The size of intergranular bubbles increased more rapidly than intragranular ones and bubble denuded zones near grain boundaries formed in all the annealed samples. It was found that high-angle grain boundaries held bigger bubbles than low-angle grain boundaries. Complementary atomistic modeling was conducted to interpret the effects of grain boundary character on the Kr segregation. The area density of strong segregation sites in the high-angle grain boundaries is much higher than that in the low angle grain boundaries.

The Effect of TiO2 Doped Photocatalytic Nano-Additives on the Hydration and Microstructure of Portland and High Alumina Cements

PubMed Central

Pérez-Nicolás, María; Alvarez, José Ignacio

2017-01-01

Mortars with two different binders (Portland cement (PC) and high alumina cement (HAC)) were modified upon the bulk incorporation of nano-structured photocatalytic additives (bare TiO2, and TiO2 doped with either iron (Fe-TiO2) or vanadium (V-TiO2)). Plastic and hardened state properties of these mortars were assessed in order to study the influence of these nano-additives. Water demand was increased, slightly by bare TiO2 and Fe-TiO2, and strongly by V-TiO2, in agreement with the reduction of the particle size and the tendency to agglomerate. Isothermal calorimetry showed that hydration of the cementitious matrices was accelerated due to additional nucleation sites offered by the nano-additives. TiO2 and doped TiO2 did not show pozzolanic reactivity in the binding systems. Changes in the pore size distribution, mainly the filler effect of the nano-additives, accounted for the increase in compressive strengths measured for HAC mortars. A complex microstructure was seen in calcium aluminate cement mortars, strongly dependent on the curing conditions. Fe-TiO2 was found to be homogeneously distributed whereas the tendency of V-TiO2 to agglomerate was evidenced by elemental distribution maps. Water absorption capacity was not affected by the nano-additive incorporation in HAC mortars, which is a favourable feature for the application of these mortars. PMID:29036917

Thermoelectric Properties of Complex Oxide Heterostructures

NASA Astrophysics Data System (ADS)

Cain, Tyler Andrew

Thermoelectrics are a promising energy conversion technology for power generation and cooling systems. The thermal and electrical properties of the materials at the heart of thermoelectric devices dictate conversion efficiency and technological viability. Studying the fundamental properties of potentially new thermoelectric materials is of great importance for improving device performance and understanding the electronic structure of materials systems. In this dissertation, investigations on the thermoelectric properties of a prototypical complex oxide, SrTiO3, are discussed. Hybrid molecular beam epitaxy (MBE) is used to synthesize La-doped SrTiO3 thin films, which exhibit high electron mobilities and large Seebeck coefficients resulting in large thermoelectric power factors at low temperatures. Large interfacial electron densities have been observed in SrTiO3/RTiO 3 (R=Gd,Sm) heterostructures. The thermoelectric properties of such heterostructures are investigated, including the use of a modulation doping approach to control interfacial electron densities. Low-temperature Seebeck coefficients of extreme electron-density SrTiO3 quantum wells are shown to provide insight into their electronic structure.

Characterisation of phases in nanostructured, multilayered titanium alloys by analytical and high-resolution electron microscopy.

PubMed

Czyrska-Filemonowicz, A; Buffat, P A

2009-01-01

Surface processing of a Ti-6Al-4V alloy led to a complex multilayered microstructure containing several phases of the Ni-Ti-P-Al-O system, which improves the mechanical and tribological surface properties. The microstructure, chemical and phase compositions of the hard layer formed on the surface were investigated by LM, XRD, SEM as well as analytical/high-resolution TEM, STEM, EDS, electron diffraction and FIB. Phase identification based on electron diffraction, HRTEM and EDS microanalysis revealed the presence of several binary and ternary phases in the system Ti-Ni-P, sometimes with partial substitution of Ti by Al. However some phases, mainly nanoparticles, still remain not identified satisfactorily. Electron microscopy techniques used for identification of phases present in surface multilayers and some practical limits to their routine application are reminded here.

Risk factors for knee replacement due to primary osteoarthritis, a population based, prospective cohort study of 315,495 individuals.

PubMed

Apold, Hilde; Meyer, Haakon E; Nordsletten, Lars; Furnes, Ove; Baste, Valborg; Flugsrud, Gunnar B

2014-06-23

Osteoarthritis (OA) of the knee is a common and disabling condition. We wanted to investigate the modifiable risk factors Body Mass Index (BMI) and physical activity, using knee replacement (KR) as a marker for severely symptomatic disease, focusing on the interaction between these risk factors. 315,495 participants (mean age 43.0 years) from national health screenings were followed prospectively with respect to KR identified by linkage to the Norwegian Arthroplasty Register. Data were analysed by Cox proportional hazard regression. During 12 years of follow up 1,323 individuals received KR for primary OA. There was a dose-response relationship between BMI and heavy labour, and later KR. Comparing the highest versus the lowest quarter of BMI, the relative risk was 6.2 (95% CI: 4.2-9.0) in men and 11.1 (95% CI: 7.8-15.6) in women. Men reporting intensive physical activity at work had a relative risk of 2.4 (95% CI: 1.8-3.2) versus men reporting sedentary activity at work, the corresponding figure in women being 2.3 (95% CI: 1.7-3.2). The effect of BMI and physical activity at work was additive. The heaviest men with the most strenuous work had a RR of 11.7 (95% CI: 5.9-23.1) compared to the ones with the lowest BMI and most sedentary work. For women the corresponding RR was 15.8 (95% CI: 8.2-30.3). There was no association between physical activity during leisure and KR. We found that a high BMI and intensive physical activity at work both contribute strongly to the risk of having a KR. As the two risk factors seem to act independently, people with strenuous physical work with a high BMI are at particularly high risk for severely disabling OA of the knee, and should be targeted with effective preventive measures.

Enhancing the electron mobility of SrTiO3 with strain

NASA Astrophysics Data System (ADS)

Jalan, Bharat; Allen, S. James; Beltz, Glenn E.; Moetakef, Pouya; Stemmer, Susanne

2011-03-01

We demonstrate, using high-mobility SrTiO3 thin films grown by molecular beam epitaxy, that stress has a pronounced influence on the electron mobility in this prototype complex oxide. Moderate strains result in more than 300% increases in the electron mobilities with values exceeding 120 000 cm2/V s and no apparent saturation in the mobility gains. The results point to a range of opportunities to tailor high-mobility oxide heterostructure properties and open up ways to explore oxide physics.

SERS of semiconducting nanoparticles (TiO{sub 2} hybrid composites).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Musumeci, A.; Gosztola, D.; Schiller, T.

Raman scattering of molecules adsorbed on the surface of TiO{sub 2} nanoparticles was investigated. We find strong enhancement of Raman scattering in hybrid composites that exhibit charge transfer absorption with TiO{sub 2} nanoparticles. An enhancement factor up to {approx}10{sup 3} was observed in the solutions containing TiO{sub 2} nanoparticles and biomolecules, including the important class of neurotransmitters such as dopamine and dopac (3,4-dihydroxy-phenylacetic acid). Only selected vibrations are enhanced, indicating molecular specificity due to distinct binding and orientation of the biomolecules coupled to the TiO{sub 2} surface. All enhanced modes are associated with the asymmetric vibrations of attached molecules thatmore » lower the symmetry of the charge transfer complex. The intensity and the energy of selected vibrations are dependent on the size and shape of nanoparticle support. Moreover, we show that localization of the charge in quantized nanoparticles (2 nm), demonstrated as the blue shift of particle absorption, diminishes SERS enhancement. Importantly, the smallest concentration of adsorbed molecules shows the largest Raman enhancements suggesting the possibility for high sensitivity of this system in the detection of biomolecules that form a charge transfer complex with metal oxide nanoparticles. The wavelength-dependent properties of a hybrid composite suggest a Raman resonant state. Adsorbed molecules that do not show a charge transfer complex show weak enhancements probably due to the dielectric cavity effect.« less

The REM Sleep Behavior Disorder Screening Questionnaire: Validation Study of the Korean Version (RBDQ-KR).

PubMed

You, Sooyeoun; Moon, Hye-Jin; Do, So Young; Wing, Yun-Kwok; Sunwoo, Jun-Sang; Jung, Ki-Young; Cho, Yong Won

2017-12-15

REM sleep behavior disorder (RBD) is a parasomnia that is commonly associated with neurodegenerative disorders. We aimed to validate the Hong Kong version of the self-reported RBD questionnaire (RBDQ-HK) with the Korean version (RBDQ-KR) and to investigate its clinical usefulness. One-hundred five patients with RBD and 105 age- and sex-matched controls were enrolled. Thirty were randomly selected for a retest with the questionnaire after 2 to 4 weeks without any treatment. Receiver operating characteristic curve and exploratory factor analysis were used to evaluate the scale, which had a score ranging from 0 to 100. There was no difference in mean age and sex in patients with RBD and control subjects. Patients with RBD had a significantly higher total RBDQ-KR score than the control group ( P < .001). The RBDQ-KR demonstrated high sensitivity (93.3%), specificity (89.5%), positive predictive value (89.9%), and negative predictive value (93.1%). Cronbach α coefficient for internal consistency of the total score of the RBDQ-KR was 0.9, which shows high reliability. Exploratory factor analysis showed two components, dream-related and behavioral factors, consistent with the main clinical features of RBD. Based on the results, the best cutoff for the total score ranging from 0 to 100 was at 18/19 and for factor 2 ranging from 0 to 75 was at 11. This study showed RBDQ-KR is a valid and reliable questionnaire for RBD symptoms and severity in Korea. It serves as an effective tool to identify patients with RBD and to facilitate future clinical and research studies. © 2017 American Academy of Sleep Medicine

Energy levels and radiative rates for transitions in B-like to F-like Kr ions (Kr XXXII XXVIII)

NASA Astrophysics Data System (ADS)

Aggarwal, K. M.; Keenan, F. P.; Lawson, K. D.

2008-05-01

Energy levels, radiative rates, oscillator strengths, line strengths, and lifetimes have been calculated for transitions in B-like to F-like Kr ions, Kr XXXIII-XXVIII. For the calculations, the fully relativistic GRASP code has been adopted, and results are reported for all electric dipole (E1), electric quadrupole (E2), magnetic dipole (M1), and magnetic quadrupole (M2) transitions among the lowest 125, 236, 272, 226, and 113 levels of Kr XXXII, Kr XXXI, Kr XXX, Kr XXIX, and Kr XXVIII, respectively, belonging to the n ⩽ 3 configurations. Comparisons are made with earlier available theoretical and experimental results, and some discrepancies have been noted and explained.

Temperature dependence of the pressure broadening of spectral lines

NASA Astrophysics Data System (ADS)

Roston, G. D.; Helmi, M. S.

2012-12-01

The aim of this work is to obtain a formula relating the pressure broadening coefficient of the spectral line β with the temperature T, when the difference potential ΔV(R) between the upper and lower states of the emitting atom is represented by (Lennard - Jones) potential, The obtained formula is a power index law of β on T. This formula is applied for calculating β for different interactions of Ar, Ne, TI, Hg, Cd and Zn with the inert gases (Xe, Kr, Ar, Ne and He) at different temperatures. The results of these calculations are in good agreement with the corresponding values obtained before numerically. The obtained formula is considered very important in astrophysical problems.

Modeling, Simulation, Additive Manufacturing, and Experimental Evaluation of Solid and Porous NiTi

NASA Astrophysics Data System (ADS)

Taheri Andani, Mohsen

In recent years, shape memory alloys (SMAs) have entered a wide range of engineering applications in fields such as aerospace and medical applications. Nickel-titanium (NiTi) is the most commonly used SMAs due to its excellent functional characteristics (shape memory effect and superelasticity behavior). These properties are based on a solid-solid phase transformation between martensite and austenite. Beside these two characteristics, low stiffness, biocompatibility and corrosion properties of NiTi make it an attractive candidate for biomedical applications (e.g., bone plates, bone screws, and vascular stents). It is well know that manufacturing and processing of NiTi is very challenging. The functional properties of NiTi are significantly affected by the impurity level and due to the high titanium content, NiTi are highly reactive. Therefore, high temperature processed parts through methods such as melting and casting which result in increased impurity levels have inadequate structural and functional properties. Furthermore, high ductility and elasticity of NiTi, adhesion, work hardening and spring back effects make machining quite challenging. These unfavorable effects for machining cause significant tool wear along with decreasing the quality of work piece. Recently, additive manufacturing (AM) has gained significant attention for manufacturing NiTi. Since AM can create a part directly from CAD data, it is predicted that AM can overcome most of the manufacturing difficulties. This technique provides the possibility of fabricating highly complex parts, which cannot be processed by any other methods. Curved holes, designed porosity, and lattice like structures are some examples of mentioned complex parts. This work investigates manufacturing superelastic NiTi by selective laser melting (SLM) technique (using PXM by Phenix/3D Systems). An extended experimental study is conducted on the effect of subsequent heat treatments with different aging conditions on phase transformation temperatures of the manufactured parts. To this end both phase transformation and mechanical behavior of the AM parts are studied. Moreover, the application of additive manufacturing to develop NiTi components with desired stiffness by introducing engineered porosity is studied. To this end, a unit cell made of two interconnecting struts is used to generate the CAD files for a series of porous structures with six different levels of porosity in the range of 20% to 82%. Finite element analyses are conducted to examine the stress-strain behavior of the fabricated structures under loading. To validate the simulations, uniaxial compression tests are performed on three NiTi samples with three different levels of porosity (32%, 45%, and 58%). The experimental data closely match with the analytical results. The findings of this study indicate that introducing porosity to a NiTi structure results in a significant drop in the stiffness of the component. These results pave the way for designing porous NiTi structures with the desired level of stiffness.

TiO2 Nanotube Arrays: Fabricated by Soft-Hard Template and the Grain Size Dependence of Field Emission Performance

NASA Astrophysics Data System (ADS)

Yang, Xuxin; Ma, Pei; Qi, Hui; Zhao, Jingxin; Wu, Qiang; You, Jichun; Li, Yongjin

2017-11-01

Highly ordered TiO2 nanotube (TNT) arrays were successfully synthesized by the combination of soft and hard templates. In the fabrication of them, anodic aluminum oxide membranes act as the hard template while the self-assembly of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) complexed with titanium-tetraisopropoxide (TTIP, the precursor of TiO2) provides the soft template to control the grain size of TiO2 nanotubes. Our results indicate that the field emission (FE) performance depends crucially on the grain size of the calcinated TiO2 which is dominated by the PS-b-PEO and its blending ratio with TTIP. The optimized sample (with the TTIP/PEO ratio of 3.87) exhibits excellent FE performances involving both a low turn-on field of 3.3 V/um and a high current density of 7.6 mA/cm2 at 12.7 V/μm. The enhanced FE properties can be attributed to the low effective work function (1.2 eV) resulted from the smaller grain size of TiO2.

Interaction of water, alkyl hydroperoxide, and allylic alcohol with a single-site homogeneous Ti-Si epoxidation catalyst: A spectroscopic and computational study.

PubMed

Urakawa, Atsushi; Bürgi, Thomas; Skrabal, Peter; Bangerter, Felix; Baiker, Alfons

2005-02-17

Tetrakis(trimethylsiloxy)titanium (TTMST, Ti(OSiMe3)4) possesses an isolated Ti center and is a highly active homogeneous catalyst in epoxidation of various olefins. The structure of TTMST resembles that of the active sites in some heterogeneous Ti-Si epoxidation catalysts, especially silylated titania-silica mixed oxides. Water cleaves the Ti-O-Si bond and deactivates the catalyst. An alkyl hydroperoxide, TBHP (tert-butyl hydroperoxide), does not cleave the Ti-O-Si bond, but interacts via weak hydrogen-bonding as supported by NMR, DOSY, IR, and computational studies. ATR-IR spectroscopy combined with computational investigations shows that more than one, that is, up to four, TBHP can undergo hydrogen-bonding with TTMST, leading to the activation of the O-O bond of TBHP. The greater the number of TBHP molecules that form hydrogen bonds to TTMST, the more electrophilic the O-O bond becomes, and the more active the complex is for epoxidation. An allylic alcohol, 2-cyclohexen-1-ol, does not interact strongly with TTMST, but the interaction is prominent when it interacts with the TTMST-TBHP complex. On the basis of the experimental and theoretical findings, a hydrogen-bond-assisted epoxidation mechanism of TTMST is suggested.

A double Fe-Ti oxide and Fe-sulphide liquid immiscibility in the Itsindro Gabbro Complex, Madagascar

NASA Astrophysics Data System (ADS)

Augé, Thierry; Bailly, Laurent; Roig, Jean-Yves

2017-11-01

The petrology and mineralogy of the Itsindro complex in south-central Madagascar has been investigated through samples obtained from the 320.7 m-deep Lanjanina borehole. The section consists of a 254 m-thick pyroxenite unit with interbedded gabbro layers that overlies a gabbro unit and is itself overlain by a 19 m-thick granite unit. Most of the structures are sub-horizontal. A weak magmatic layering is locally observed but at the scale of the core, the intrusion does not appear to be a layered complex. Pyroxenite and gabbro show a systematic disseminated mineralization consisting of Fe-Ti-P oxides and Fe-(Cu-Ni) sulphides that takes the form of ilmenite-titanomagnetite ± apatite and pyrrhotite ± chalcopyrite ± pentlandite. In the upper zone, from 90 to 72 m, sub-massive centimetre-to decimetre-sized layers of oxides and sulphides comprise a total of 16 m of sub-massive sulphide (the main mineralized zone). In this mineralized zone the oxide/sulphide ratio is close to 1/1. The sulphide is strongly dominated by pyrrhotite, which may locally contain inclusions of molybdenite crystals with the Re sulphide rheniite (ReS2). Oxides are generally euhedral, included in or attached to the Fe-sulphide, and also locally form sub-massive centimetre-sized bands. Apatite as a cumulus phase is ubiquitous. Locally it may account for 30% of the ore-rich samples and some samples consist of apatite-Fe-Ti oxides-Fe-Cu-Ni sulphides with virtually no silicate. Apatite is the main REE carrier but the total REE content remains low (<90 ppm). Mineral compositions and whole rock geochemistry indicate that the rocks are highly differentiated, and in spite of a relatively limited thickness, the differentiation process is observed. Two zones can be distinguished: from the bottom to 162.8 m we see a decrease in the Mg number of olivine and pyroxene, and a drop in TiO2 and Al2O3 for the latter. A reverse trend is then observed within the pyroxenite unit from the 162.8 m level upwards. The main mineralized zone is located in the upper part of this unit, about 70 m above this discontinuity. The highly differentiated Fe-Ti-P facies of the Lanjanina series in the Itsindro Gabbro Complex have been interpreted as corresponding to the Fe-Ti-P rich, Si-poor member remaining after an immiscible segregation of an evolved mafic magma. The granite dykes and the overlying granite unit represent the second, Si-rich member of the immiscibility process. The presence of large amounts of sulphide is attributed to sulphur contamination of the Fe-Ti-rich liquid. Fe-Ti oxides will tend to crystallize on the sulphide droplets and the accumulation of dense Fe-sulphides (liquid) and associated Fe-Ti oxides (solid) will result in this complex and unusual association taking the form of a net texture.

Transcriptional Analysis and Subcellular Protein Localization Reveal Specific Features of the Essential WalKR System in Staphylococcus aureus

PubMed Central

Poupel, Olivier; Moyat, Mati; Groizeleau, Julie; Antunes, Luísa C. S.; Gribaldo, Simonetta; Msadek, Tarek; Dubrac, Sarah

2016-01-01

The WalKR two-component system, controlling cell wall metabolism, is highly conserved among Bacilli and essential for cell viability. In Staphylococcus aureus, walR and walK are followed by three genes of unknown function: walH, walI and walJ. Sequence analysis and transcript mapping revealed a unique genetic structure for this locus in S. aureus: the last gene of the locus, walJ, is transcribed independently, whereas transcription of the tetra-cistronic walRKHI operon occurred from two independent promoters located upstream from walR. Protein topology analysis and protein-protein interactions in E. coli as well as subcellular localization in S. aureus allowed us to show that WalH and WalI are membrane-bound proteins, which associate with WalK to form a complex at the cell division septum. While these interactions suggest that WalH and WalI play a role in activity of the WalKR regulatory pathway, deletion of walH and/or walI did not have a major effect on genes whose expression is strongly dependent on WalKR or on associated phenotypes. No effect of WalH or WalI was seen on tightly controlled WalKR regulon genes such as sle1 or saouhsc_00773, which encodes a CHAP-domain amidase. Of the genes encoding the two major S. aureus autolysins, AtlA and Sle1, only transcription of atlA was increased in the ΔwalH or ΔwalI mutants. Likewise, bacterial autolysis was not increased in the absence of WalH and/or WalI and biofilm formation was lowered rather than increased. Our results suggest that contrary to their major role as WalK inhibitors in B. subtilis, the WalH and WalI proteins have evolved a different function in S. aureus, where they are more accessory. A phylogenomic analysis shows a striking conservation of the 5 gene wal cluster along the evolutionary history of Bacilli, supporting the key importance of this signal transduction system, and indicating that the walH and walI genes were lost in the ancestor of Streptococcaceae, leading to their atypical 3 wal gene cluster, walRKJ. PMID:26999783

Transcriptional Analysis and Subcellular Protein Localization Reveal Specific Features of the Essential WalKR System in Staphylococcus aureus.

PubMed

Poupel, Olivier; Moyat, Mati; Groizeleau, Julie; Antunes, Luísa C S; Gribaldo, Simonetta; Msadek, Tarek; Dubrac, Sarah

2016-01-01

The WalKR two-component system, controlling cell wall metabolism, is highly conserved among Bacilli and essential for cell viability. In Staphylococcus aureus, walR and walK are followed by three genes of unknown function: walH, walI and walJ. Sequence analysis and transcript mapping revealed a unique genetic structure for this locus in S. aureus: the last gene of the locus, walJ, is transcribed independently, whereas transcription of the tetra-cistronic walRKHI operon occurred from two independent promoters located upstream from walR. Protein topology analysis and protein-protein interactions in E. coli as well as subcellular localization in S. aureus allowed us to show that WalH and WalI are membrane-bound proteins, which associate with WalK to form a complex at the cell division septum. While these interactions suggest that WalH and WalI play a role in activity of the WalKR regulatory pathway, deletion of walH and/or walI did not have a major effect on genes whose expression is strongly dependent on WalKR or on associated phenotypes. No effect of WalH or WalI was seen on tightly controlled WalKR regulon genes such as sle1 or saouhsc_00773, which encodes a CHAP-domain amidase. Of the genes encoding the two major S. aureus autolysins, AtlA and Sle1, only transcription of atlA was increased in the ΔwalH or ΔwalI mutants. Likewise, bacterial autolysis was not increased in the absence of WalH and/or WalI and biofilm formation was lowered rather than increased. Our results suggest that contrary to their major role as WalK inhibitors in B. subtilis, the WalH and WalI proteins have evolved a different function in S. aureus, where they are more accessory. A phylogenomic analysis shows a striking conservation of the 5 gene wal cluster along the evolutionary history of Bacilli, supporting the key importance of this signal transduction system, and indicating that the walH and walI genes were lost in the ancestor of Streptococcaceae, leading to their atypical 3 wal gene cluster, walRKJ.

Caught in the Act: 1.5 Å Resolution Crystal Structures of the HIV-1 Protease and the I54V Mutant Reveal a Tetrahedral Reaction Intermediate

PubMed Central

Kovalevsky, Andrey Y.; Chumanevich, Alexander A.; Liu, Fengling; Louis, John M.; Weber, Irene T.

2008-01-01

HIV-1 protease (PR) is the target for several important antiviral drugs used in AIDS therapy. The drugs bind inside the active-site cavity of PR where normally the viral poly-protein substrate is bound and hydrolyzed. We report two high resolution crystal structures of wild-type PR (PRWT) and the multi-drug resistant variant with the I54V mutation (PRI54V) in complex with a peptide at 1.46 Å and 1.50 Å resolution, respectively. The peptide forms a gem-diol tetrahedral reaction intermediate (TI) in the crystal structures. Distinctive interactions are observed for the TI binding in the active site cavity of PRWT and PRI54V. The mutant PRI54V /TI complex has lost water-mediated hydrogen bond interactions with the amides of Ile 50 and 50′ in the flap. Hence, the structures provide insight into the mechanism of drug resistance arising from this mutation. The structures also illustrate an intermediate state in the hydrolysis reaction. One of the gem-diol hydroxide groups in the PRWT complex forms a very short (2.3 Å) hydrogen bond with the outer carboxylate oxygen of Asp25. Quantum chemical calculations based on this TI structure are consistent with protonation of the inner carboxylate oxygen of Asp25′, in contrast to several theoretical studies. These TI complexes and quantum calculations are discussed in relation to the chemical mechanism of the peptide bond hydrolysis catalyzed by PR. PMID:18052235

Involvement of Met and Kr-h1 in JH-Mediated Reproduction of Female Bactrocera dorsalis (Hendel).

PubMed

Yue, Yong; Yang, Rui-Lin; Wang, Wei-Ping; Zhou, Qi-Hao; Chen, Er-Hu; Yuan, Guo-Rui; Wang, Jin-Jun; Dou, Wei

2018-01-01

Juvenile hormone (JH) prevents metamorphosis during insect larval stages and promotes adult reproductive processes. Krüppel-homolog 1 (Kr-h1), a zinc finger transcription factor assumed to be induced by JH via the JH receptor methoprene-tolerant (Met), mediates the antimetamorphic effect of JH in insects, but its function in JH-mediated reproductive processes has not been fully explored. In this study, Met and Kr-h1 involved in the JH signaling pathway were first cloned and identified from the oriental fruit fly, Bactrocera dorsalis , an important pest infesting fruit and vegetables worldwide. Subsequent spatiotemporal expression analysis revealed that Met and Kr-h1 were both highly expressed in 7-day-old adults and fat body of female adults, respectively. Treatment with a JH analog (methoprene) significantly induced the expression of JH signaling and vitellogenin ( Vg ) genes and accelerated ovary development. RNA interference (RNAi) further revealed that either Met or Kr-h1 depletion at the adult stage of B. dorsalis impeded ovary development, with significantly lower egg production noted as well. In addition, rescue through methoprene application after RNAi stimulated the expression of JH signaling and Vg genes. Although there were still differences in ovary phenotype between rescued insects and the pre-RNAi control, ovary redevelopment with a larger surface area was observed, consistent with the spatiotemporal expression and phenotypes recorded in the original methoprene experiment. Our data reveal the involvement of Met and Kr-h1 in insect vitellogenesis and egg production, thus indicating the crucial role of the JH signaling pathway in insect reproduction.

Monomeric Ti(IV) homopiperazine complexes and their exploitation for the ring opening polymerisation of rac-lactide

PubMed Central

2013-01-01

Background The area of biodegradable/sustainable polymers is one of increasing importance in the 21st Century due to their positive environmental characteristics. Lewis acidic metal centres are currently one of the most popular choices for the initiator for the polymerisation. Thus, in this paper we report the synthesis and characterisation of a series of monometallic homopiperazine Ti(IV) complexes where we have systematically varied the sterics of the phenol moieties. Results When the ortho substituent of the ligand is either a Me, tBu or amyl then the β-cis isomer is isolated exclusively in the solid-state. Nevertheless, in solution multiple isomers are clearly observed from analysis of the NMR spectra. However, when the ortho substituent is an H-atom then the trans-isomer is formed in the solid-state and solely in solution. The complexes have been screened for the polymerisation of rac-lactide in solution and under the industrially preferred melt conditions. Narrow molecular weight material (PDI 1.07 – 1.23) is formed under melt conditions with controlled molecular weights. Conclusions Six new Ti(IV) complexes are presented which are highly active for the polymerisation. In all cases atactic polymer is prepared with predictable molecular weight control. This shows the potential applicability of Ti(IV) to initiate the polymerisations. PMID:23915921

A new Ti-5Ag alloy for customized prostheses by three-dimensional printing (3DP).

PubMed

Hong, S B; Eliaz, N; Leisk, G G; Sach, E M; Latanision, R M; Allen, S M

2001-03-01

Three important considerations in the fabrication of customized cranio-maxillofacial prostheses are geometric precision, material strength, and biocompatibility. Three-dimensional printing (3DP) is a rapid part-fabrication process that can produce complex parts with high precision. The aim of this study was to design, synthesize by 3DP, and characterize a new Ti-5Ag (wt%) alloy. Silver nitrate was found to be an appropriate inorganic binder for the Ti powder-based skeleton, and the optimum sintering parameters for full densification were determined. The hardness of the Ti-5Ag alloy was shown to be much higher than that of a pure titanium sample. Potentiodynamic measurements, carried out in saline solution at body temperature, showed that the Ti-5Ag alloy had good passivation behavior, similar to that of pure titanium. It is concluded that the Ti-Ag system may be suitable for fabrication of customized prostheses by 3DP.

Identification of peptide features in precursor spectra using Hardklör and Krönik

PubMed Central

Hoopmann, Michael R.; MacCoss, Michael J.; Moritz, Robert L.

2013-01-01

Hardklör and Krönik are software tools for feature detection and data reduction of high resolution mass spectra. Hardklör is used to reduce peptide isotope distributions to a single monoisotopic mass and charge state, and can deconvolve overlapping peptide isotope distributions. Krönik filters, validates, and summarizes peptide features identified with Hardklör from data obtained during liquid chromatography mass spectrometry (LC-MS). Both software tools contain a simple user interface and can be run from nearly any desktop computer. These tools are freely available from http://proteome.gs.washington.edu/software/hardklor. PMID:22389013

The Pseudorabies Virus Glycoprotein gE/gI Complex Suppresses Type I Interferon Production by Plasmacytoid Dendritic Cells

PubMed Central

Lamote, Jochen A. S.; Kestens, Manon; Van Waesberghe, Cliff; Delva, Jonas; De Pelsmaeker, Steffi; Devriendt, Bert

2017-01-01

ABSTRACT Plasmacytoid dendritic cells (pDC) play a central role in the antiviral immune response, both in the innate response and in shaping the adaptive response, mainly because of their ability to produce massive amounts of type I interferon (TI-IFN). Here, we report that cells infected with the live attenuated Bartha vaccine strain of porcine alphaherpesvirus pseudorabies virus (PRV) trigger a dramatically increased TI-IFN response by porcine primary pDC compared to cells infected with wild-type PRV strains (Becker and Kaplan). Since Bartha is one of the relatively few examples of a highly successful alphaherpesvirus vaccine, identification of factors that may contribute to its efficacy may provide insights for the rational design of other alphaherpesvirus vaccines. The Bartha vaccine genome displays several mutations compared to the genome of wild-type PRV strains, including a large deletion in the unique short (US) region, encompassing the glycoprotein E (gE), gI, US9, and US2 genes. Using recombinant PRV Becker strains harboring the entire Bartha US deletion or single mutations in the four affected US genes, we demonstrate that the absence of the viral gE/gI complex contributes to the observed increased IFN-α response. Furthermore, we show that the absence of gE leads to an enhanced extracellular signal-regulated kinase 1/2 (ERK1/2) phosphorylation in pDC, which correlates with a higher TI-IFN production by pDC. In conclusion, the PRV Bartha vaccine strain triggers strongly increased TI-IFN production by porcine pDC. Our data further indicate that the gE/gI glycoprotein complex suppresses TI-IFN production by pDC, which represents the first alphaherpesvirus factor that suppresses pDC activity. IMPORTANCE Several alphaherpesviruses, including herpes simpex virus, still lack effective vaccines. However, the highly successful Bartha vaccine has contributed substantially to eradication of the porcine alphaherpesvirus pseudorabies virus (PRV) in several countries. The impact of Bartha on the immune response is still poorly understood. Type I interferon (TI-IFN)-producing plasmacytoid dendritic cells (pDC) may play an important role in vaccine development. Here, we show that Bartha elicits a dramatically increased type I interferon (TI-IFN) response in primary porcine pDC compared to wild-type strains. In addition, we found that the gE/gI complex, which is absent in Bartha, inhibits the pDC TI-IFN response. This is the first description of an immune cell type that is differentially affected by Bartha versus wild-type PRV and is the first report describing an alphaherpesvirus protein that inhibits the TI-IFN response by pDC. These data may therefore contribute to the rational design of other alphaherpesvirus vaccines. PMID:28122975

The Pseudorabies Virus Glycoprotein gE/gI Complex Suppresses Type I Interferon Production by Plasmacytoid Dendritic Cells.

PubMed

Lamote, Jochen A S; Kestens, Manon; Van Waesberghe, Cliff; Delva, Jonas; De Pelsmaeker, Steffi; Devriendt, Bert; Favoreel, Herman W

2017-04-01

Plasmacytoid dendritic cells (pDC) play a central role in the antiviral immune response, both in the innate response and in shaping the adaptive response, mainly because of their ability to produce massive amounts of type I interferon (TI-IFN). Here, we report that cells infected with the live attenuated Bartha vaccine strain of porcine alphaherpesvirus pseudorabies virus (PRV) trigger a dramatically increased TI-IFN response by porcine primary pDC compared to cells infected with wild-type PRV strains (Becker and Kaplan). Since Bartha is one of the relatively few examples of a highly successful alphaherpesvirus vaccine, identification of factors that may contribute to its efficacy may provide insights for the rational design of other alphaherpesvirus vaccines. The Bartha vaccine genome displays several mutations compared to the genome of wild-type PRV strains, including a large deletion in the unique short (US) region, encompassing the glycoprotein E (gE), gI, US9, and US2 genes. Using recombinant PRV Becker strains harboring the entire Bartha US deletion or single mutations in the four affected US genes, we demonstrate that the absence of the viral gE/gI complex contributes to the observed increased IFN-α response. Furthermore, we show that the absence of gE leads to an enhanced extracellular signal-regulated kinase 1/2 (ERK1/2) phosphorylation in pDC, which correlates with a higher TI-IFN production by pDC. In conclusion, the PRV Bartha vaccine strain triggers strongly increased TI-IFN production by porcine pDC. Our data further indicate that the gE/gI glycoprotein complex suppresses TI-IFN production by pDC, which represents the first alphaherpesvirus factor that suppresses pDC activity. IMPORTANCE Several alphaherpesviruses, including herpes simpex virus, still lack effective vaccines. However, the highly successful Bartha vaccine has contributed substantially to eradication of the porcine alphaherpesvirus pseudorabies virus (PRV) in several countries. The impact of Bartha on the immune response is still poorly understood. Type I interferon (TI-IFN)-producing plasmacytoid dendritic cells (pDC) may play an important role in vaccine development. Here, we show that Bartha elicits a dramatically increased type I interferon (TI-IFN) response in primary porcine pDC compared to wild-type strains. In addition, we found that the gE/gI complex, which is absent in Bartha, inhibits the pDC TI-IFN response. This is the first description of an immune cell type that is differentially affected by Bartha versus wild-type PRV and is the first report describing an alphaherpesvirus protein that inhibits the TI-IFN response by pDC. These data may therefore contribute to the rational design of other alphaherpesvirus vaccines. Copyright © 2017 American Society for Microbiology.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Razhev, A M; Kargapol'tsev, E S; Churkin, D S

Results of an experimental study of the influence of a gas mixture (laser active medium) composition on an output energy and total efficiency of gas-discharge excimer lasers on ArF* (193 nm), KrCl* (222 nm), KrF* (248 nm) and XeCl* (308 nm) molecules operating without a buffer gas are presented. The optimal ratios of gas components (from the viewpoint of a maximum output energy) of an active medium are found, which provide an efficient operation of laser sources. It is experimentally confirmed that for gas-discharge excimer lasers on halogenides of inert gases the presence of a buffer gas in an activemore » medium is not a necessary condition for efficient operation. For the first time, in two-component gas mixtures of repetitively pulsed gas-discharge excimer lasers on electron transitions of excimer molecules ArF*, KrCl*, KrF* and XeCl*, the pulsed energy of laser radiation obtained under pumping by a transverse volume electric discharge in a low-pressure gas mixture without a buffer gas reached up to 170 mJ and a high pulsed output power (of up to 24 MW) was obtained at a FWHM duration of the KrF-laser pulse of 7 ns. The maximal total efficiency obtained in the experiment with two-component gas mixtures of KrF and XeCl lasers was 0.8%. (lasers)« less

Generation and characterization of point defects in SrTiO3 and Y3Al5O12

NASA Astrophysics Data System (ADS)

Selim, F. A.; Winarski, D.; Varney, C. R.; Tarun, M. C.; Ji, Jianfeng; McCluskey, M. D.

Positron annihilation lifetime spectroscopy (PALS) was applied to characterize point defects in single crystals of Y3Al5O12 and SrTiO3 after populating different types of defects by relevant thermal treatments. In SrTiO3, PALS measurements identified Sr vacancy, Ti vacancy, vacancy complexes of Ti-O (vacancy) and hydrogen complex defects. In Y3Al5O12 single crystals the measurements showed the presence of Al-vacancy, (Al-O) vacancy and Al-vacancy passivated by hydrogen. These defects are shown to play the major role in defining the electronic and optical properties of these complex oxides.

Toward a comprehensive UV laser ablation modeling of multicomponent materials—A non-equilibrium investigation on titanium carbide

NASA Astrophysics Data System (ADS)

Ait Oumeziane, Amina; Parisse, Jean-Denis

2018-05-01

Titanium carbide (TiC) coatings of great quality can be produced using nanosecond pulsed laser deposition (PLD). Because the deposition rate and the transfer of the target stoichiometry depend strongly on the laser-target/laser-plasma interaction as well as the composition of the laser induced plume, investigating the ruling fundamental mechanisms behind the material ablation and the plasma evolution in the background environment under PLD conditions is essential. This work, which extends previous investigations dedicated to the study of nanosecond laser ablation of pure target materials, is a first step toward a comprehensive non-equilibrium model of multicomponent ones. A laser-material interaction model coupled to a laser-plasma interaction one is presented. A UV 20 ns KrF (248 nm) laser pulse is considered. Ablation depths, plasma ignition thresholds, and shielding rates have been calculated for a wide range of laser beam fluences. A comparison of TiC behavior with pure titanium material under the same conditions is made. Plasma characteristics such as temperature and composition have been investigated. An overall correlation between the various results is presented.

Microstructure and mechanical behavior of metal injection molded Ti-Nb binary alloys as biomedical material.

PubMed

Zhao, Dapeng; Chang, Keke; Ebel, Thomas; Qian, Ma; Willumeit, Regine; Yan, Ming; Pyczak, Florian

2013-12-01

The application of titanium (Ti) based biomedical materials which are widely used at present, such as commercially pure titanium (CP-Ti) and Ti-6Al-4V, are limited by the mismatch of Young's modulus between the implant and the bones, the high costs of products, and the difficulty of producing complex shapes of materials by conventional methods. Niobium (Nb) is a non-toxic element with strong β stabilizing effect in Ti alloys, which makes Ti-Nb based alloys attractive for implant application. Metal injection molding (MIM) is a cost-efficient near-net shape process. Thus, it attracts growing interest for the processing of Ti and Ti alloys as biomaterial. In this investigation, metal injection molding was applied to the fabrication of a series of Ti-Nb binary alloys with niobium content ranging from 10wt% to 22wt%, and CP-Ti for comparison. Specimens were characterized by melt extraction, optical microscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and transmission electron microscopy (TEM). Titanium carbide formation was observed in all the as-sintered Ti-Nb binary alloys but not in the as-sintered CP-Ti. Selected area electron diffraction (SAED) patterns revealed that the carbides are Ti2C. It was found that with increasing niobium content from 0% to 22%, the porosity increased from about 1.6% to 5.8%, and the carbide area fraction increased from 0% to about 1.8% in the as-sintered samples. The effects of niobium content, porosity and titanium carbides on mechanical properties have been discussed. The as-sintered Ti-Nb specimens exhibited an excellent combination of high tensile strength and low Young's modulus, but relatively low ductility. © 2013 Elsevier Ltd. All rights reserved.

Software-hardware complex for the input of telemetric information obtained from rocket studies of the radiation of the earth's upper atmosphere

NASA Astrophysics Data System (ADS)

Bazdrov, I. I.; Bortkevich, V. S.; Khokhlov, V. N.

2004-10-01

This paper describes a software-hardware complex for the input into a personal computer of telemetric information obtained by means of telemetry stations TRAL KR28, RTS-8, and TRAL K2N. Structural and functional diagrams are given of the input device and the hardware complex. Results that characterize the features of the input process and selective data of optical measurements of atmospheric radiation are given. © 2004

Recent advances in the deformation processing of titanium alloys

NASA Astrophysics Data System (ADS)

Tamirisakandala, S.; Bhat, R. B.; Vedam, B. V.

2003-12-01

Titanium (Ti) alloys are special-purpose materials used for several critical applications in aerospace as well as non-aerospace industries, and extensive deformation processing is necessary to shape-form these materials, which poses many challenges due to the microstructural complexities. Some of the recent developments in the deformation processing of Ti alloys and usefulness of integrating the material behavior information with simulation schemes while designing and optimizing manufacturing process schedules are discussed in this paper. Discussions are primarily focused on the most important alloy, Ti-6Al-4V and on developing a clear understanding on the influence of key parameters (e.g., oxygen content, starting microstructure, temperature, and strain rate) on the deformation behavior during hot working. These studies are very useful not only for obtaining controlled microstructures but also to design complex multi-step processing sequences to produce defect-free components. Strain-induced porosity (SIP) has been a serious problem during titanium alloy processing, and improved scientific understanding helps in seeking elegant solutions to avoid SIP. A novel high-speed processing technique for microstructural conversion in titanium has been described, which provides several benefits over the conventional slow-speed practices. The hot working behavior of some of the affordable α+β and β titanium alloys being developed recently—namely, Ti-5.5Al-1Fe, Ti-10V-2Fe-3Al, Ti-6.8Mo-4.5Fe-1.5Al, and Ti-10V-4.5Fe-1.5Al—has been analyzed, and the usefulness of the processing maps in optimizing the process parameters and design of hot working schedules in these alloys is demonstrated. Titanium alloys modified with small additions of boron are emerging as potential candidates for replacing structural components requiring high specific strength and stiffness. Efforts to understand the microstructural mechanisms during deformation processing of Ti-B alloys and the issues associated with their processing are discussed.

Conducting interface in oxide homojunction: Understanding of superior properties in black TiO 2

DOE PAGES

Lu, Xujie; Chen, Aiping; Luo, Yongkang; ...

2016-09-14

Black TiO 2 nanoparticles with a crystalline core and amorphous-shell structure exhibit superior optoelectronic properties in comparison with pristine TiO 2. The fundamental mechanisms underlying these enhancements, however, remain unclear, largely due to the inherent complexities and limitations of powder materials. Here, we fabricate TiO 2 homojunction films consisting of an oxygen-deficient amorphous layer on top of a highly crystalline layer, to simulate the structural/functional configuration of black TiO 2 nanoparticles. Metallic conduction is achieved at the crystalline–amorphous homointerface via electronic interface reconstruction, which we show to be the main reason for the enhanced electron transport of black TiO 2.more » As a result, this work not only achieves an unprecedented understanding of black TiO 2 but also provides a new perspective for investigating carrier generation and transport behavior at oxide interfaces, which are of tremendous fundamental and technological interest.« less

Probing the coordination environment of Ti(3+) ions coordinated to nitrogen-containing Lewis bases.

PubMed

Morra, E; Maurelli, S; Chiesa, M; Van Doorslaer, S

2015-08-28

Multi-frequency continuous-wave and pulsed EPR techniques are employed to investigate the coordination of nitrogen-containing ligands to Ti(3+)-chloro complexes. Frozen solutions of TiCl3 and TiCl3(Py)3 dissolved in nitrogen-containing solvents have been investigated together with the TiCl3(Py)3 solid-state complex. For these different systems, the hyperfine and nuclear quadrupole data of Ti(3+)-bound (14)N nuclei are reported and discussed in the light of DFT computations, allowing for a detailed description of the microscopic structure of these systems.

Ab initio calculation of Ti NMR shieldings for titanium oxides and halides

NASA Astrophysics Data System (ADS)

Tossell, J. A.

Titanium NMR shielding constants have been calculated using ab initio coupled Hartree-Fock perturbation theory and polarized double-zeta basis sets for TiF 4, TiF 62-, TiCI 4, Ti(OH) 4, Ti(OH 2) 64+, Ti(OH) 4O, and Ti(OH) 3O -. In all cases the calculations were performed at Hartree-Fuck energy-optimized geometries. For Ti(OH) 4 a S4-symmetry geometry with nonlinear ∠ TiOH was employed. Relative shieldings are in reasonable agreement with experiment for TiF 62-, TiCI 4, and Ti(OR) 4, where R = H or alkyl. Ti(OH 2) 64+ is predicted to be more highly shielded than Ti(OH) 4 by about 340 ppm. The five-coordinate complex Ti(OH) 4O, whose calculated structure matches well that measured by extended X-ray absorption fine structure in K 2O · TiO 2 · SiO 2 glass, is actually deshielded compared to Ti(OH) 4 by about 40 ppm. X-ray absorption-near-edge spectral energies have also been calculated for TiF 4, TiCI 4, Ti(OH) 4, and Ti(OH) 4O using an equivalent ionic core virtual-orbital method and the observed reduction in term energy for the five-coordinate species compared to Ti(OH) 4 has been reproduced. Replacement of the H atoms in Ti(OH) 4 by point charges has only a slight effect upon σTi, suggesting a possible means of incorporating second-neighbor effects in NMR calculations for condensed phases.

Q4 Titanium 6-4 Material Properties Development

NASA Technical Reports Server (NTRS)

Cooper, Kenneth; Nettles, Mindy

2015-01-01

This task involves development and characterization of selective laser melting (SLM) parameters for additive manufacturing of titanium-6%aluminum-4%vanadium (Ti-6Al-4V or Ti64). SLM is a relatively new manufacturing technology that fabricates complex metal components by fusing thin layers of powder with a high-powered laser beam, utilizing a 3D computer design to direct the energy and form the shape without traditional tools, dies, or molds. There are several metal SLM technologies and materials on the market today, and various efforts to quantify the mechanical properties, however, nothing consolidated or formal to date. Meanwhile, SLM material fatigue properties of Ti64 are currently highly sought after by NASA propulsion designers for rotating turbomachinery components.

Interatomic potentials for HeAr, HeKr, and HeXe from multiproperty fits

DOE Office of Scientific and Technical Information (OSTI.GOV)

Danielson, L.J.; Keil, M.

1988-01-15

Crossed molecular beam measurements of differential cross sections (DCS) are reported for elastic scattering of He by Ar, Kr, and Xe at high resolution. Interatomic potentials are determined by simultaneously fitting the DCS's, as well as mixture viscosity and interaction second virial data. Bias due to systematic and potential model errors are examined and are used to estimate the accuracy of the potential energy curves obtained. Attractive well depths are 2.59, 2.67, and 2.64 meV +- 3% for HeAr, HeKr, and HeXe, respectively, agreeing with the best available HeAr potential and a previously proposed HeKr potential, but significantly deeper thanmore » previously reported potentials for HeXe. The HeXe attractive well is also considerably broader than previously reported. Attractive minimum positions are 3.48, 3.70, and 4.00 A ( +- 0.03 A) for HeAr, HeKr, and HeXe, respectively. Including the accurate diffusion data of Dunlop and co-workers (Physica A 95, 561 (1979)) and the absolute integral cross sections of Pirani and Vecchiocattivi (J. Chem. Phys. 66, 372 (1977) and revisions thereto) verify the error bounds for all three potentials.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hancock, R.L.

Irradiation effects in the phylum Annelida are almost entirely unknown, nor is it know why the LD/sub 50/30// for amoebae is 100 kr, whereas mammals show LD/sub 50/ doses of approximates 0.5 kr. To shed more light on comparative radiosensitivity, Lumbricus terrestris was irradiated at a rate of 1 kr/min with 250-kr x rays to total doses of 10 to l00 kr. No lethal effect occurs at 45 kr or below in Lumbricus, whereas a definite mortality occurs with 75 kr. All worms died within 2 months after 100 kr. The LD/sub 50/35//and LD/sub 100/67// are approximates 100 kr. Thismore » is in contrast to the mollusk Radix which has a for lethal effects. The annelid Enchytraeus shows no apparent effect after 90 kr. It is suggested that some feature of biological organization, which has up to the present escaped discovery, may hold a clue to the fundamental nature of radiobiological action, and may explain the extremes of radiosensitivity present within a few selected invertebrate types. (BBB)« less

A Review of Selective Laser Melted NiTi Shape Memory Alloy

PubMed Central

Khoo, Zhong Xun; Shen, Yu Fang

2018-01-01

NiTi shape memory alloys (SMAs) have the best combination of properties among the different SMAs. However, the limitations of conventional manufacturing processes and the poor manufacturability of NiTi have critically limited its full potential applicability. Thus, additive manufacturing, commonly known as 3D printing, has the potential to be a solution in fabricating complex NiTi smart structures. Recently, a number of studies on Selective Laser Melting (SLM) of NiTi were conducted to explore the various aspects of SLM-produced NiTi. Compared to producing conventional metals through the SLM process, the fabrication of NiTi SMA is much more challenging. Not only do the produced parts require a high density that leads to good mechanical properties, strict composition control is needed as well for the SLM NiTi to possess suitable phase transformation characteristics. Additionally, obtaining a good shape memory effect from the SLM NiTi samples is another challenging task that requires further understanding. This paper presents the results of the effects of energy density and SLM process parameters on the properties of SLM NiTi. Its shape memory properties and potential applications were then reviewed and discussed. PMID:29596320

THE ABUNDANCES OF LIGHT NEUTRON-CAPTURE ELEMENTS IN PLANETARY NEBULAE. III. THE IMPACT OF NEW ATOMIC DATA ON NEBULAR SELENIUM AND KRYPTON ABUNDANCE DETERMINATIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sterling, N. C.; Porter, R. L.; Dinerstein, Harriet L., E-mail: nsterlin@westga.edu, E-mail: ryanlporter@gmail.com, E-mail: harriet@astro.as.utexas.edu

The detection of neutron(n)-capture elements in several planetary nebulae (PNe) has provided a new means of investigating s-process nucleosynthesis in low-mass stars. However, a lack of atomic data has inhibited accurate trans-iron element abundance determinations in astrophysical nebulae. Recently, photoionization (PI) and recombination data were determined for Se and Kr, the two most widely detected n-capture elements in nebular spectra. We have incorporated these new data into the photoionization code Cloudy. To test the atomic data, numerical models were computed for 15 PNe that exhibit emission lines from multiple Kr ions. We found systematic discrepancies between the predicted and observedmore » emission lines that are most likely caused by inaccurate PI and recombination data. These discrepancies were removed by adjusting the Kr{sup +}–Kr{sup 3+} PI cross sections within their cited uncertainties and the dielectronic recombination rate coefficients by slightly larger amounts. From grids of models spanning the physical conditions encountered in PNe, we derive new, broadly applicable ionization correction factor (ICF) formulae for calculating Se and Kr elemental abundances. The ICFs were applied to our previous survey of near-infrared [Kr iii] and [Se iv] emission lines in 120 PNe. The revised Se and Kr abundances are 0.1–0.3 dex lower than former estimates, with average values of [Se/(O, Ar)] = 0.12 ± 0.27 and [Kr/(O, Ar)] = 0.82 ± 0.29, but correlations previously found between their abundances and other nebular and stellar properties are unaffected. We also find a tendency for high-velocity PNe that can be associated with the Galactic thick disk to exhibit larger s-process enrichments than low-velocity PNe belonging to the thin-disk population.« less

Structural, spectral, NLO and MEP analysis of the [MgO2Ti2(OPri)6], [MgO2Ti2(OPri)2(acac)4] and [MgO2Ti2(OPri)2(bzac)4] by DFT method

NASA Astrophysics Data System (ADS)

Sayin, Koray; Karakaş, Duran

2015-06-01

Quantum chemical calculations are performed on [MgO2Ti2(OPri)6] and [MgO2Ti2(OPri)2(L)4] complexes. L is acetylacetonate (acac) and benzoylacetonate (bzac) anion. The crystal structures of these complexes have not been obtained as experimentally but optimized structures of these complexes are obtained as theoretically in this study. Universal force field (UFF) and DFT/B3LYP method are used to obtain optimized structures. Theoretical spectral analysis (IR, 1H and 13C NMR) is compared with their experimental values. A good agreement is found between experimental and theoretical spectral analysis. These results mean that the optimized structures of mentioned complexes are appropriate. Additionally, the active sites of mentioned complexes are determined by molecular electrostatic potential (MEP) diagrams and non-linear optical (NLO) properties are investigated.

Palladium-directed self-assembly of multi-titanium(IV)-porphyrin arrays on the substrate surface as sensitive ultrathin films for hydrogen peroxide sensing, photocurrent generation, and photochromism of viologen

NASA Astrophysics Data System (ADS)

He, Wen-Li; Fang, Fang; Ma, Dong-Mei; Chen, Meng; Qian, Dong-Jin; Liu, Minghua

2018-01-01

Multiporphyrin arrays are large, π-conjugated chromophores with high absorption efficiency and strong chemical stability that play an important role in supramolecular and advanced material sciences. Palladium-directed self-assembly of multiporphyrin array ultrathin films was achieved on substrate surfaces using oxo[5,10,15,20-tetra(4-pyridyl)porphyrinato]titanium (IV) complex [TiO(TPyP)] as a linker and sodium tetrachloropalladate (Na2PdCl4) as a connector. The Pd-TiOTPyP films as prepared were characterized by using UV-vis absorption and X-ray photoelectron spectroscopy, as well as by atomic force and scanning electron microscopy. The Soret absorption band of TiOTPyP was observed to red shift by 6 nm when the Pd-TiOTPyP multilayer-modified quartz substrate was immersed in an aqueous solution containing hydrogen peroxide. This was attributed to the formation of a TiO2TPyP monoperoxo complex. This oxidation reaction could be accelerated in an acidic solution. Furthermore, the immobilized Pd-TiOTPyP multilayers could act as light-harvesting units for photocurrent generation and photochromism of viologens, with strong stability, reproducibility, and recyclability. The photocurrent density could be enhanced in electrolyte solutions containing electron donors such as triethanolamine, or electron acceptors such as viologens. Finally, photoinduced reduction (photochromism) of viologens was investigated using the Pd-TiOTPyP multilayers as light sensitizers and EDTA as the electron donors.

The Role of Pictures in Learning Biology: Part 2, Picture-Text Processing.

ERIC Educational Resources Information Center

Reid, David

1990-01-01

The complex interactions between picture, text, and learner are examined, based on a 3-D model which describes the context of the learning task. The different strategies that children of various ability levels use in reading from illustrated texts are described. (KR)

Facile synthesis of titanium (IV) ion immobilized adenosine triphosphate functionalized silica nanoparticles for highly specific enrichment and analysis of intact phosphoproteins.

PubMed

Wang, Hao; Tian, Zhixin

2018-06-06

Analysis of phosphoproteins always faces the challenge of low stoichiometry, which demands highly selective and efficient enrichment in the initial sample preparation. Here we report our synthesis of the novel titanium (IV) ion immobilized adenosine triphosphate functionalized silica nanoparticles (Ti 4+ -ATP-NPs) for efficient enrichment of intact phosphoproteins. The average diameter of Ti 4+ -ATP-NPs was about 128 nm with good dispersibility and the saturated adsorption capacity for β-casein was 1046.5 mg/g. In addition, Ti 4+ -ATP-NPs exhibited high specificity and selectivity in enriching phosphoproteins from both standard protein mixtures and complex biological samples (non-fat milk, chicken egg white and mouse heart tissue extract) as demonstrated by SDS-PAGE. Copyright © 2018 Elsevier B.V. All rights reserved.

Temporal and spatial adaptations during the acquisition of a reversal movement.

PubMed

van Loon, E M; Buekers, M J; Helsen, W; Magill, R A

1998-03-01

Adjustments of the biphasic movement in a coincidence anticipation task were studied using an erroneous knowledge of results (KR) paradigm. Forty participants received either no KR, correct KR, erroneous (+100 ms) KR, or 100 trials of correct KR followed by 50 trials of erroneous KR. Kinematic analyses revealed that for this 100-50 KR group the extension part of the movement was temporally adjusted under the influence of erroneous KR. Although accompanied by a decrease in movement amplitude, this did not account for the temporal shift in movement outcome, because all groups showed a reduction in amplitude. It is argued that changing external time constraints mainly results in temporal adaptations. However, spatial adaptations do play a role in kinematic changes during acquisition.

Rapid processing of 85Kr/Kr ratios using Atom Trap Trace Analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zappala, J. C.; Bailey, K.; Mueller, P.

In this paper, we report a methodology for measuring 85Kr/Kr isotopic abundances using Atom Trap Trace Analysis (ATTA) that increases sample measurement throughput by over an order of magnitude to six samples per 24 h. The noble gas isotope 85Kr (half-life = 10.7 years) is a useful tracer for young groundwater in the age range of 5–50 years. ATTA, an efficient and selective laser-based atom counting method, has recently been applied to 85Kr/Kr isotopic abundance measurements, requiring 5–10 μL of krypton gas at STP extracted from 50 to 100 L of water. Previously, a single such measurement required 48 h.more » In conclusion, our new method demonstrates that we can measure 85Kr/Kr ratios with 3–5% relative uncertainty every 4 h, on average, with the same sample requirements.« less

Rapid processing of 85Kr/Kr ratios using Atom Trap Trace Analysis

DOE PAGES

Zappala, J. C.; Bailey, K.; Mueller, P.; ...

2017-03-11

In this paper, we report a methodology for measuring 85Kr/Kr isotopic abundances using Atom Trap Trace Analysis (ATTA) that increases sample measurement throughput by over an order of magnitude to six samples per 24 h. The noble gas isotope 85Kr (half-life = 10.7 years) is a useful tracer for young groundwater in the age range of 5–50 years. ATTA, an efficient and selective laser-based atom counting method, has recently been applied to 85Kr/Kr isotopic abundance measurements, requiring 5–10 μL of krypton gas at STP extracted from 50 to 100 L of water. Previously, a single such measurement required 48 h.more » In conclusion, our new method demonstrates that we can measure 85Kr/Kr ratios with 3–5% relative uncertainty every 4 h, on average, with the same sample requirements.« less

Setting a limit on anthropogenic sources of atmospheric 81Kr through Atom Trap Trace Analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zappala, J. C.; Bailey, K.; Jiang, W.

In this study, we place a 2.5% limit on the anthropogenic contribution to the modern abundance of 81Kr/Kr in the atmosphere at the 90% confidence level. Due to its simple production and transport in the terrestrial environment, 81Kr (half-life = 230,000 years) is an ideal tracer for old water and ice with mean residence times in the range of 105–106 years. In recent years, 81Kr-dating has been made available to the earth science community thanks to the development of Atom Trap Trace Analysis (ATTA), a laser-based atom counting technique. Further upgrades and improvements to the ATTA technique now allow usmore » to demonstrate 81Kr/Kr measurements with relative uncertainties of 1% and place this new limit on anthropogenic 81Kr. As a result of this limit, we have removed a potential systematic constraint for 81Kr-dating.« less

Setting a limit on anthropogenic sources of atmospheric 81Kr through Atom Trap Trace Analysis

DOE PAGES

Zappala, J. C.; Bailey, K.; Jiang, W.; ...

2017-02-09

In this study, we place a 2.5% limit on the anthropogenic contribution to the modern abundance of 81Kr/Kr in the atmosphere at the 90% confidence level. Due to its simple production and transport in the terrestrial environment, 81Kr (half-life = 230,000 years) is an ideal tracer for old water and ice with mean residence times in the range of 105–106 years. In recent years, 81Kr-dating has been made available to the earth science community thanks to the development of Atom Trap Trace Analysis (ATTA), a laser-based atom counting technique. Further upgrades and improvements to the ATTA technique now allow usmore » to demonstrate 81Kr/Kr measurements with relative uncertainties of 1% and place this new limit on anthropogenic 81Kr. As a result of this limit, we have removed a potential systematic constraint for 81Kr-dating.« less

Passage and rumination of inert particles varying in size and specific gravity as determined from analysis of faecal appearance using multicompartment models.

PubMed

Murphy, M R; Kennedy, P M; Welch, J G

1989-09-01

Plastic particles of defined length (2, 5 mm) and specific gravity (sp.gr. 1.10, 1.34, 1.77) were administered just before feeding into the reticulo-rumen of four cattle and four swamp buffaloes given a diet predominantly of rice straw ad lib. Simultaneously, doses of ground rice straw marked with Cr and Yb were likewise given. Plastic particles were recovered from faeces for 12 d after dosing, and divided into non-ruminated (NR) and ruminated (R) particles. Excretion data of plastic particles were interpreted using a four-pool model incorporating passage of NR (kp) and R from the reticulo-rumen, post-ruminal passage, rate of chewing (kr) and two lag times. An inverse relationship was found between kr and sp.gr. The kr was higher for 5 mm than that for 2 mm particles. In contrast, kp was greatest for particles of sp.gr. 1.34, with higher kp for 2 mm than for 5 mm particles. Rates of passage and rumination (kp, kr) were higher for buffaloes than for cattle. Rumination time was related to kr, most highly (r2 0.96) with kr of 2 mm, 1.10 sp.gr. particles. Fragmentation of 5 mm particles by rumination tended to increase the rate of passage from the rumen. Ruminal passage rates of Yb and Cr markers were poorly correlated with each other and with kp of any of the plastic markers. Reanalysis of published data from plastic particle studies supported the relationships between sp.gr., size, kp and kr.(ABSTRACT TRUNCATED AT 250 WORDS)

Validity of Alcohol Use Disorder Identification Test-Korean Revised Version for Screening Alcohol Use Disorder according to Diagnostic and Statistical Manual of Mental Disorders, Fifth Edition Criteria.

PubMed

Chang, Jung Wei; Kim, Jong Sung; Jung, Jin Gyu; Kim, Sung Soo; Yoon, Seok Joon; Jang, Hak Sun

2016-11-01

The Alcohol Use Disorder Identification Test (AUDIT) has been widely used to identify alcohol use disorder (AUD). This study evaluated the validity of the AUDIT-Korean revised version (AUDIT-KR) for screening AUD according to Diagnostic and Statistical Manual of Mental Disorders, fifth edition (DSM-5) criteria. This research was conducted with 443 subjects who visited the Chungnam National University Hospital for a comprehensive medical examination. All subjects completed the demographic questionnaire and AUDIT-KR without assistance. Subjects were divided into two groups according to DSM-5 criteria: an AUD group, which included patients that fit the criteria for AUD (120 males and 21 females), and a non-AUD group, which included 146 males and 156 females that did not meet AUD criteria. The appropriate cut-off values, sensitivity, specificity, and positive and negative predictive values of the AUDIT-KR were evaluated. The mean±standard deviation AUDIT-KR scores were 10.32±7.48 points in males and 3.23±4.42 points in females. The area under the receiver operating characteristic curve (95% confidence interval, CI) of the AUDIT-KR for identifying AUD was 0.884 (0.840-0.920) in males and 0.962 (0.923-0.985) in females. The optimal cut-off value of the AUDIT-KR was 10 points for males (sensitivity, 81.90%; specificity, 81.33%; positive predictive value, 77.2%; negative predictive value, 85.3%) and 5 points for females (sensitivity, 100.00%; specificity, 88.54%; positive predictive value, 52.6%; negative predictive value, 100.0%). The AUDIT-KR has high reliability and validity for identifying AUD according to DSM-5 criteria.

Rapid fabrication of TiO2@carboxymethyl cellulose coatings capable of shielding UV, antifog and delaying support aging.

PubMed

Li, Xiaozhou; Lv, Junping; Li, Dehuai; Wang, Lin

2017-08-01

Agricultural plastic films capable of shielding UV, filtering visible light and antifog are important to prolong their life and protect safeties of agriculturists and crops. In this work, high stable and small size TiO 2 @polymer nanoparticles (NPs) were prepared by an efficient one-pot microwave synthesis using titanic sulfate as Ti resource, carboxymethyl cellulose sodium (CMC) as complexing agent and stabilizer. The TiO 2 @CMC NPs obtained were then utilized to fabricate poly(ethylene imine) (PEI)/TiO 2 @CMC coatings on the surface of polypropylene films by a layer-by-layer assembly technique. The TiO 2 @CMC NPs show rapid deposition rate because small, spherical and anion-rich TiO 2 @CMC NPs possess large specific surface area and fast diffusion rate. More importantly, property experiments confirm that (PEI/TiO 2 @CMC)*15 coatings can not only effectively shield UV rays, filter visible light and prevent fogging but also delay the aging of their supports. Copyright © 2017 Elsevier Ltd. All rights reserved.

Phase inversion and frequency doubling of reflection high-energy electron diffraction intensity oscillations in the layer-by-layer growth of complex oxides

NASA Astrophysics Data System (ADS)

Mao, Zhangwen; Guo, Wei; Ji, Dianxiang; Zhang, Tianwei; Gu, Chenyi; Tang, Chao; Gu, Zhengbin; Nie*, Yuefeng; Pan, Xiaoqing

In situ reflection high-energy electron diffraction (RHEED) and its intensity oscillations are extremely important for the growth of epitaxial thin films with atomic precision. The RHEED intensity oscillations of complex oxides are, however, rather complicated and a general model is still lacking. Here, we report the unusual phase inversion and frequency doubling of RHEED intensity oscillations observed in the layer-by-layer growth of SrTiO3 using oxide molecular beam epitaxy. In contacts to the common understanding that the maximum(minimum) intensity occurs at SrO(TiO2) termination, respectively, we found that both maximum or minimum intensities can occur at SrO, TiO2, or even incomplete terminations depending on the incident angle of the electron beam, which raises a fundamental question if one can rely on the RHEED intensity oscillations to precisely control the growth of thin films. A general model including surface roughness and termination dependent mean inner potential qualitatively explains the observed phenomena, and provides the answer to the question how to prepare atomically and chemically precise surface/interfaces using RHEED oscillations for complex oxides. We thank National Basic Research Program of China (No. 11574135, 2015CB654901) and the National Thousand-Young-Talents Program.

Exploring Trends in Metal-Metal Bonding, Spectroscopic Properties, and Conformational Flexibility in a Series of Heterobimetallic Ti/M and V/M Complexes (M = Fe, Co, Ni, and Cu).

PubMed

Wu, Bing; Wilding, Matthew J T; Kuppuswamy, Subramaniam; Bezpalko, Mark W; Foxman, Bruce M; Thomas, Christine M

2016-12-05

To understand the metal-metal bonding and conformational flexibility of first-row transition metal heterobimetallic complexes, a series of heterobimetallic Ti/M and V/M complexes (M = Fe, Co, Ni, and Cu) have been investigated. The titanium tris(phosphinoamide) precursors ClTi(XylNP i Pr 2 ) 3 (1) and Ti(XylNP i Pr 2 ) 3 (2) have been used to synthesize Ti/Fe (3), Ti/Ni (4, 4 THF ), and Ti/Cu (5) heterobimetallic complexes. A series of V/M (M = Fe (7), Co (8), Ni (9), and Cu (10)) complexes have been generated starting from the vanadium tris(phosphinoamide) precursor V(XylNP i Pr 2 ) 3 (6). The new heterobimetallic complexes were characterized and studied by NMR spectroscopy, X-ray crystallography, electron paramagnetic resonance, and Mössbauer spectroscopy, where applicable, and computational methods (DFT). Compounds 3, 4 THF , 7, and 8 are C 3 -symmetric with three bridging phosphinoamide ligands, while compounds 9 and 10 adopt an asymmetric geometry with two bridging phosphinoamides and one phosphinoamide ligand bound η 2 to vanadium. Compounds 4 and 5, on the other hand, are asymmetric in the solid state but show evidence for fluxional behavior in solution. A correlation is established between conformational flexibility and metal-metal bond order, which has important implications for the future reactivity of these and other heterobimetallic molecules.

Does knee replacement surgery for osteoarthritis improve survival? The jury is still out.

PubMed

Misra, Devyani; Lu, Na; Felson, David; Choi, Hyon K; Seeger, John; Einhorn, Thomas; Neogi, Tuhina; Zhang, Yuqing

2017-01-01

The relation of knee replacement (KR) surgery to all-cause mortality has not been well established owing to potential biases in previous studies. Thus, we aimed to examine the relation of KR to mortality risk among patients with knee osteoarthritis (OA) focusing on identifying biases that may threaten the validity of prior studies. We included knee OA subjects (ages 50-89 years) from The Health Improvement Network, an electronic medical records database in the UK. Risk of mortality among KR subjects was compared with propensity score-matched non-KR subjects. To explore residual confounding bias, subgroup analyses stratified by age and propensity scores were performed. Subjects with KR had 28% lower risk of mortality than non-KR subjects (HR 0.72, 95% CI 0.66 to 0.78). However, when stratified by age, protective effect was noted only in older age groups (>63 years) but not in younger subjects (≤63 years). Further, the mortality rate among KR subjects decreased as candidacy (propensity score) for KR increased among subjects with KR, but no such consistent trend was noted among non-KR subjects. While a protective effect of KR on mortality cannot be ruled out, findings of lower mortality among older KR subjects and those with higher propensity scores suggest that prognosis-based selection for KR may lead to intractable confounding by indication; hence, the protective effect of KR on all-cause mortality may be overestimated. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/.

An interpolated activity during the knowledge-of-results delay interval eliminates the learning advantages of self-controlled feedback schedules.

PubMed

Carter, Michael J; Ste-Marie, Diane M

2017-03-01

The learning advantages of self-controlled knowledge-of-results (KR) schedules compared to yoked schedules have been linked to the optimization of the informational value of the KR received for the enhancement of one's error-detection capabilities. This suggests that information-processing activities that occur after motor execution, but prior to receiving KR (i.e., the KR-delay interval) may underlie self-controlled KR learning advantages. The present experiment investigated whether self-controlled KR learning benefits would be eliminated if an interpolated activity was performed during the KR-delay interval. Participants practiced a waveform matching task that required two rapid elbow extension-flexion reversals in one of four groups using a factorial combination of choice (self-controlled, yoked) and KR-delay interval (empty, interpolated). The waveform had specific spatial and temporal constraints, and an overall movement time goal. The results indicated that the self-controlled + empty group had superior retention and transfer scores compared to all other groups. Moreover, the self-controlled + interpolated and yoked + interpolated groups did not differ significantly in retention and transfer; thus, the interpolated activity eliminated the typically found learning benefits of self-controlled KR. No significant differences were found between the two yoked groups. We suggest the interpolated activity interfered with information-processing activities specific to self-controlled KR conditions that occur during the KR-delay interval and that these activities are vital for reaping the associated learning benefits. These findings add to the growing evidence that challenge the motivational account of self-controlled KR learning advantages and instead highlights informational factors associated with the KR-delay interval as an important variable for motor learning under self-controlled KR schedules.

Identification of genes differentially expressed in B16 murine melanoma sublines with different metastatic potentials.

PubMed

Ishiguro, T; Nakajima, M; Naito, M; Muto, T; Tsuruo, T

1996-02-15

B16-F10 and B16-BL6 are B16 mouse melanoma sublines that preferentially metastasize to the lung following i.v. and s.c. injections, respectively. To study molecular mechanisms underlying the different metastatic behaviors exhibited by the B16 melanoma sublines, we performed differential hybridization of the genes transcribed in these cells and compared their expression levels. We isolated four genes that were highly expressed in B16-F10 cells but not in B16-BL6 cells: TI-225 (polyubiquitin), TI-229 (pyruvate kinase), TI-241 (LRF-1 homologue), and TI-227 (novel gene). Triosephosphate isomerase, 10-formyltetrahydrofolate dehydrogenase, tyrosinase-related protein 2, cytochrome c oxidase, ATP synthetase alpha subunit, RNA helicase, and ribosomal protein (L37, J1, acidic phosphoprotein), however, showed higher expression in B16-BL6 cells than in B16-F10 cells. Among these clones, transfection of TI-241 into the low metastatic clone F1 converted the parental cells from low- into high-metastatic cells. TI-241 may regulate the expression of various genes as a transcription factor in the complex process of metastasis.

Kr photoionized plasma induced by intense extreme ultraviolet pulses

NASA Astrophysics Data System (ADS)

Bartnik, A.; Wachulak, P.; Fiedorowicz, H.; Skrzeczanowski, W.

2016-04-01

Irradiation of any gas with an intense EUV (extreme ultraviolet) radiation beam can result in creation of photoionized plasmas. The parameters of such plasmas can be significantly different when compared with those of the laser produced plasmas (LPP) or discharge plasmas. In this work, the photoionized plasmas were created in a krypton gas irradiated using an LPP EUV source operating at a 10 Hz repetition rate. The Kr gas was injected into the vacuum chamber synchronously with the EUV radiation pulses. The EUV beam was focused onto a Kr gas stream using an axisymmetrical ellipsoidal collector. The resulting low temperature Kr plasmas emitted electromagnetic radiation in the wide spectral range. The emission spectra were measured either in the EUV or an optical range. The EUV spectrum was dominated by emission lines originating from Kr III and Kr IV ions, and the UV/VIS spectra were composed from Kr II and Kr I lines. The spectral lines recorded in EUV, UV, and VIS ranges were used for the construction of Boltzmann plots to be used for the estimation of the electron temperature. It was shown that for the lowest Kr III and Kr IV levels, the local thermodynamic equilibrium (LTE) conditions were not fulfilled. The electron temperature was thus estimated based on Kr II and Kr I species where the partial LTE conditions could be expected.

Investigations of the Rg-BrCl (Rg = He, Ne, Ar, Kr, Xe) binary van der Waals complexes: ab initio intermolecular potential energy surfaces, vibrational states and predicted pure rotational transition frequencies

NASA Astrophysics Data System (ADS)

Li, Song; Zheng, Rui; Chen, Shan-Jun; Chen, Yan; Chen, Peng

2017-03-01

The intermolecular potential energy surfaces (PESs) of the ground electronic state for the Rg-BrCl (Rg = He, Ne, Ar, Kr, Xe) van der Waals complexes have been constructed by using the coupled-cluster method in combination with the augmented quadruple-zeta correlation-consistent basis sets supplemented with an additional set of bond functions. The features of the anisotropic PESs for these complexes are remarkably similar, which are characterized by three minima and two saddle points between them. The global minimum corresponds to a collinear Rg-Br-Cl configuration. Two local minima, correlate with an anti-linear Rg-Cl-Br geometry and a nearly T-shaped structure, can also be located on each PES. The quantum bound state calculations enable us to investigate intermolecular vibrational states and rotational energy levels of the complexes. The transition frequencies are predicted and are fitted to obtain their corresponding spectroscopic constants. In general, the periodic trends are observed for this complex family. Comparisons with available experimental data for the collinear isomer of Ar-BrCl demonstrate reliability of our theoretical predictions, and our results for the other two isomers of Ar-BrCl as well as for other members of the complex family are also anticipated to be trustable. Except for the collinear isomer of Ar-BrCl, the data presented in this paper would be beneficial to improve our knowledge for these experimentally unknown species.

Microstructure refinement and mechanical properties improvement by developing IAF on inclusions in Ti–Al complex deoxidized HSLA steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, M., E-mail: jiangmin@ustb.edu.cn; Wang, X.H.; Hu, Z.Y.

2015-10-15

The present study focused on microstructure refinement in Ti–Al complex deoxidized low alloy structural steel by developing IAF on inclusions. The goal was to establish more determined relation between Ti, Al in steel and the produced microstructures. In steel sample with Ti and Al contents of 0.0035% and 0.0004%, respectively, IAF was well developed by inclusions characterized by TiO{sub x}–MnO oxide cores enwrapped by (MnO–SiO{sub 2}–Al{sub 2}O{sub 3})–MnS or (MnO–SiO{sub 2})–MnS surface layers. With the rise of Ti and Al contents, IAF volume decreased greatly because of different inclusion chemistry, TiO{sub x} + MnS, TiO{sub x}–Al{sub 2}O{sub 3} or Al{submore » 2}O{sub 3}, which inhibit the formation of IAF. Thermodynamic calculations were carried out for optimal Ti and Al contents in steel to target inclusions with proper chemistry for nucleating IAF. These laboratorial findings were successfully applied and reproducibly observed in pilot trials. It was indicated that low temperature impact toughness at 0 °C and − 20 °C of the produced medium plate was effectively improved despite lower Ti contents than common process, which was very meaningful in saving the cost of high Ti content steels. - Highlights: • IAF volume showed close relationship to Ti or Al contents. • To target IAF, there is no need to add too many titanium alloys. • Optimal Ti and Al were about 0.0020–0.0060% and 0.0005–0.0020%, respectively. • Impact toughness of steel plate at 0 °C and − 20 °C was successfully improved.« less

Influence of Basicity on High-Chromium Vanadium-Titanium Magnetite Sinter Properties, Productivity, and Mineralogy

NASA Astrophysics Data System (ADS)

Zhou, Mi; Yang, Songtao; Jiang, Tao; Xue, Xiangxin

2015-05-01

The effect of basicity on high-chromium vanadium-titanium magnetite (V-Ti-Cr) sintering was studied via sintering pot tests. The sinter rate, yield, and productivity were calculated before determining sinter strength (TI) and reduction degradation index (RDI). Furthermore, the effect of basicity on V-Ti-Cr sinter mineralogy was clarified using metallographic microscopy, x-ray diffraction, and scanning electron microscopy-energy-dispersive x-ray spectroscopy. The results indicate that increasing basicity quickly increases the sintering rate from 25.4 mm min-1 to 28.9 mm min-1, yield from 75.3% to 87.2%, TI from 55.4% to 64.8%, and productivity from 1.83 t (m2 h)-1 to 1.94 t (m2 h)-1 before experiencing a slight drop. The V-Ti-Cr sinter shows complex mineral composition, with main mineral phases such as magnetite, hematite, silicate (dicalcium silicate, Ca-Fe olivine, glass), calcium and aluminum silico-ferrite (SFCA/SFCAI) and perovskite. Perovskite is notable because it lowers the V-Ti sinter strength and RDI. The well intergrowths between magnetite and SFCA/SFCAI, and the decrease in perovskite and secondary skeletal hematite are the key for improving TI and RDI. Finally, a comprehensive index was calculated, and the optimal V-Ti-Cr sinter basicity also for industrial application was 2.55.

Electrostatic analysis of n-doped SrTiO{sub 3} metal-insulator-semiconductor systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kamerbeek, A. M., E-mail: a.m.kamerbeek@rug.nl; Banerjee, T.; Hueting, R. J. E.

2015-12-14

Electron doped SrTiO{sub 3}, a complex-oxide semiconductor, possesses novel electronic properties due to its strong temperature and electric-field dependent permittivity. Due to the high permittivity, metal/n-SrTiO{sub 3} systems show reasonably strong rectification even when SrTiO{sub 3} is degenerately doped. Our experiments show that the insertion of a sub nanometer layer of AlO{sub x} in between the metal and n-SrTiO{sub 3} interface leads to a dramatic reduction of the Schottky barrier height (from around 0.90 V to 0.25 V). This reduces the interface resistivity by 4 orders of magnitude. The derived electrostatic analysis of the metal-insulator-semiconductor (n-SrTiO{sub 3}) system is consistent with thismore » trend. When compared with a Si based MIS system, the change is much larger and mainly governed by the high permittivity of SrTiO{sub 3}. The non-linear permittivity of n-SrTiO{sub 3} leads to unconventional properties such as a temperature dependent surface potential non-existent for semiconductors with linear permittivity such as Si. This allows tuning of the interfacial band alignment, and consequently the Schottky barrier height, in a much more drastic way than in conventional semiconductors.« less

Final Project Report (Oct 2014-Dec 2017): Zeolite Membranes for Krypton/Xenon Separation from Spent Nuclear Fuel Reprocessing Off-Gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kwon, Yeon Hye; Nair, Sankar; Bhave, Ramesh

The overall focus of this project is to develop and understand SAPO-34 zeolitic membranes that can separate mixtures of radioisotope krypton-85 and xenon released as off-gases during used nuclear fuel recycling. The primary advantage of separating 85Kr from Xe is to reduce the volume of radioactive waste for storage. The second advantage is the revenue generated from the sale of high-purity Xe. Zeolite membranes are attractive because of their much lower energy requirements relative to cryogenic distillation, and their high resistance to radiation degradation. We report the detailed study of silicoaluminophosphate zeolite SAPO-34 materials and membranes for this application, duemore » to hypothesized favorable molecular sieving properties. In the 3-year Mission Support project, we developed a novel, high-performance, low-energy intensity, lower-cost zeolite membrane process for Kr/Xe separation during SNF processing; and investigated the underlying molecular adsorption and transport processes in both ‘idealized’ and ‘realistic’ operating conditions to develop reliable synthesis-structure-property relationships for such membranes. Adsorption and diffusion measurements on SAPO-34 crystals indicate their potential for use in Kr-Xe separation membranes, but also highlight competing effects of adsorption and diffusion selectivity. SAPO-34 membranes synthesized on α-alumina substrates via steam-assisted conversion seeding and hydrothermal growth are characterized in detail, with Kr permeances 26 GPU and ideal Kr/Xe selectivities >20 at 298 K after thickness reduction. Post-synthesis cation exchange shows large (>50%) increases in selectivity at ambient or slight sub-ambient conditions. In addition, we confirm that SAPO-34 membrane is stable under radiation exposure and the impact of radiation exposure on membrane performance would not be substantial. We also successfully synthesized hollow-fiber SAPO-34 membranes with the same performance levels as the disk-type and tubular membranes. This important development will allow a very compact and low-cost Kr/Xe separation system. Finally, a detailed process calculation for techno-economic analysis was performed by integrating Maxwell-Stefan model into cross-flow membrane system, in order to estimate the required number of membrane stages and the total cost.« less

Kinetic and dynamic kinetic resolution of secondary alcohols with ionic-surfactant-coated Burkholderia cepacia lipase: substrate scope and enantioselectivity.

PubMed

Kim, Cheolwoo; Lee, Jusuk; Cho, Jeonghun; Oh, Yeonock; Choi, Yoon Kyung; Choi, Eunjeong; Park, Jaiwook; Kim, Mahn-Joo

2013-03-15

Forty-four different secondary alcohols, which can be classified into several types (II-IX), were tested as the substrates of ionic surfactant-coated Burkholderia cepacia lipase (ISCBCL) to see its substrate scope and enantioselectivity in kinetic and dynamic kinetic resolution (KR and DKR). They include 6 boron-containing alcohols, 24 chiral propargyl alcohols, and 14 diarylmethanols. The results from the studies on KR indicate that ISCBCL accepted most of them with high enantioselectivity at ambient temperature and with useful to high enantioselectivity at elevated temperatures. In particular, ISCBCL displayed high enantioselectivity toward sterically demanding secondary alcohols (types VIII and IX) which have two bulky substituents at the hydroxymethine center. DKR reactions were performed by the combination of ISCBCL with a ruthenium-based racemization catalyst at 25-60 °C. Forty-one secondary alcohols were tested for DKR. About half of them were transformed into their acetates of high enantiopurity (>90% ee) with good yields (>80%). It is concluded that ISCBCL appears to be a superb enzyme for the KR and DKR of secondary alcohols.

Remote sensing of potential lunar resources. 2: High spatial resolution mapping of spectral reflectance ratios and implications for nearside mare TiO2 content`

NASA Technical Reports Server (NTRS)

Melendrez, David E.; Johnson, Jeffrey R.; Larson, Stephen M.; Singer, Robert B.

1994-01-01

High spatial resolution maps illustrating variations in spectral reflectance 400/560 nm ratio values have been generated for the following mare regions: (1) the border between southern Mare Serenitatis and northern Mare Tranquillitatis (including the MS-2 standard area and Apollo 17 landing site), (2) central Mare Tranquillitatis, (3) Oceanus Procellarum near Seleucus, and (4) southern Oceanus Procellarum and Flamsteed. We have also obtained 320-1000 nm reflectance spectra of several sites relative to MS-2 to facilitate scaling of the images and provide additional information on surface composition. Inferred TiO2 abundances for these mare regions have been determined using an empirical calibration which relates the weight percent TiO2 in mature mare regolith to the observed 400/560 nm ratio. Mare areas with high TiO2 abundances are probably rich in ilmenite (FeTiO3) a potential lunar resource. The highest potential TiO2 concentrations we have identified in the nearside maria occur in central Mare Tranquillitatis. Inferred TiO2 contents for these areas are greater than 9 wt% and are spatially consistent with the highest-TiO2 regions mapped previously at lower spatial resolution. We note that the morphology of surface units with high 400/560 nm ratio values increases in complexity at higher spatial resolutions. Comparisons have been made with previously published geologic maps, Lunar Orbiter IV, and ground-based images, and some possible morphologic correlatins have been found between our mapped 400/560 nm ratio values and volcanic landforms such as lava flows, mare domes, and collapse pits.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aggarwal, K.M.; Keenan, F.P.; Lawson, K.D.

Energy levels, radiative rates, oscillator strengths, line strengths, and lifetimes have been calculated for transitions in B-like to F-like Kr ions, Kr XXXIII-XXVIII. For the calculations, the fully relativistic GRASP code has been adopted, and results are reported for all electric dipole (E1), electric quadrupole (E2), magnetic dipole (M1), and magnetic quadrupole (M2) transitions among the lowest 125, 236, 272, 226, and 113 levels of Kr XXXII, Kr XXXI, Kr XXX, Kr XXIX, and Kr XXVIII, respectively, belonging to the n {<=} 3 configurations. Comparisons are made with earlier available theoretical and experimental results, and some discrepancies have been notedmore » and explained.« less

Testing Room-Temperature Ionic Liquid Solutions for Depot Repair of Aluminum Coatings

DTIC Science & Technology

2011-05-01

Ne 3 Na Mg IIIB IVB VB VIB VIIB ------ VIIIB ------ IB IIB Al Si P S Cl Ar 4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 5 Rb Sr Y Zr Nb Mo Tc...Ru Rh Pd Ag Cd In Sn Sb Te I Xe 6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 7 Fr Ra Ac Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Th Pa U Np...Electroplating Bath Lid Arrangement ;:::::::::::=== Thermometer Purge gas vent Anode lead Cathode lead (Extractable from the lid) Purge feed gas

Cross sections and rate coefficients for excitation of Δn = 1 transitions in Li-like ions with 6 < Z < 42.

NASA Astrophysics Data System (ADS)

Safronova, U. I.; Safronova, M. S.; Kato, T.

Excitation cross sections and rate coefficients by electron impact were calculated for the 1s22s - 1s2s2p, 1s22s - 1s2s2 and 1s22s - 1s2p2 transitions of the Li-like ions (C IV, N V, O VI, Ne VIII, Mg X, Al XI, Si XII, S XIV, Ar XVI, Ca XVIII, Ti XX, Fe XXIV, Ni XXVI, Zn XXVIII, Ge XXX, Se XXXII, Kr XXXIIV and Mo XXXX) by a Coulomb-Born approximation with exchange and including relativistic effects and configuration interactions. Level energies, mixing coefficients and transition wavelengths and probabilities were also computed.

Investigation of anodic TiO2 nanotube composition with high spatial resolution AES and ToF SIMS

NASA Astrophysics Data System (ADS)

Dronov, Alexey; Gavrilin, Ilya; Kirilenko, Elena; Dronova, Daria; Gavrilov, Sergey

2018-03-01

High resolution Scanning Auger Electron Spectroscopy (AES) and Time-of-Flight Secondary Ion Mass-Spectrometry (ToF SIMS) were used to investigate structure and elemental composition variation of both across an array of TiO2 nanotubes (NTs) and single tube of an array. The TiO2 NT array was grown by anodic oxidation of Ti foil in fluorine-containing ethylene glycol electrolyte. It was found that the studied anodic TiO2 nanotubes have a layered structure with rather sharp interfaces. The differences in AES depth profiling results of a single tube with the focused primary electron beam (point analysis) and over an area of 75 μm in diameter of a nanotube array with the defocused primary electron beam are discussed. Depth profiling by ToF SIMS was carried out over approximately the same size of a nanotube array to determine possible ionic fragments in the structure. The analysis results show that the combination of both mentioned methods is useful for a detailed analysis of nanostructures with complex morphology and multi-layered nature.

Hybrid TiO2 -Ruthenium Nano-photosensitizer Synergistically Produces Reactive Oxygen Species in both Hypoxic and Normoxic Conditions.

PubMed

Gilson, Rebecca C; Black, Kvar C L; Lane, Daniel D; Achilefu, Samuel

2017-08-28

Photodynamic therapy (PDT) is widely used to treat diverse diseases, but its dependence on oxygen to produce cytotoxic reactive oxygen species (ROS) diminishes the therapeutic effect in a hypoxic environment, such as solid tumors. Herein, we developed a ROS-producing hybrid nanoparticle-based photosensitizer capable of maintaining high levels of ROS under both normoxic and hypoxic conditions. Conjugation of a ruthenium complex (N3) to a TiO 2 nanoparticle afforded TiO 2 -N3. Upon exposure of TiO 2 -N3 to light, the N3 injected electrons into TiO 2 to produce three- and four-fold more hydroxyl radicals and hydrogen peroxide, respectively, than TiO 2 at 160 mmHg. TiO 2 -N3 maintained three-fold higher hydroxyl radicals than TiO 2 under hypoxic conditions via N3-facilitated electron-hole reduction of adsorbed water molecules. The incorporation of N3 transformed TiO 2 from a dual type I and II PDT agent to a predominantly type I photosensitizer, irrespective of the oxygen content. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Groundwater residence time and paleohydrology in the Baltic Artesian basin:isotope geochemical data

NASA Astrophysics Data System (ADS)

Vaikmae, R.; Gerber, C.; Purtschert, R.; Aeschbach, W.; Raidla, V., Sr.; Lu, Z. T.; Zappala, J. C.; Mueller, P.; Mokrik, R., Sr.; Jiang, W.

2016-12-01

In this study of the Cambrian aquifer system(CAS) in the Baltic Artesian Basin(BAS) (, chemistry, stable isotopes, noble gas measurements, and dating tracers were combined for study the flow and recharge dynamics of the system over the last million years We find that the variability in chemical composition, stable isotopes and noble gas content in the basin is predominately controlled by mixing of three distinct water masses: Holocene and Pleistocene interglacial water, glacial meltwater, and brine. 81Kr is a nearly ideal dating tracer for such old systems. The radiogenic 4He and 40Ar provide additional information, but are more difficult to interpret in terms of groundwater age. In this study, we did not consider diffusive loss of 81Kr to stagnant water, which might result in an overestimation of groundwater ages ). However, the relatively high porosity and large thickness of the CAS, together with the presumed high salinity and low Kr content of the stagnant water all diminish the effect of diffusive 81Kr loss on age estimates. Our results confirm that under normal conditions, underground production of 81Kr is not affecting the dating results. 81Kr, 4He, and 40Ar all indicate a residence time of the brine of more than 1-3 Ma. Some uncertainty about the brine formation process remains, but the combination of chemical and stable isotope composition of the brine, noble gas concentrations and dating results favors evaporative enrichment of seawater. Tracer ages of interglacial water and glacial meltwater are on the order of several hundred thousand years, which means that several reversals of the flow direction in the CAS as a result of the paleoclimatology of the area have to be taken into account. Under such conditions, small vertical leakage, through fracture zones for example, might considerably impact the net flow pattern. Due to the cyclic flow direction reversals, the aquifer was probably in a transient state over most of the last 1 Ma period.

Rubidium D1 collision shift by heavy noble gases

NASA Astrophysics Data System (ADS)

Wells, N. P.; Driskell, T. U.; Camparo, J. C.

2015-10-01

Using an isoclinic-point technique, we measured the D1 collision shift by Xe, ∂ [δ ν ]/∂ P , and the exponent κ of the shift's temperature dependence (i.e., δ ν ˜Tκ ). As demonstrated in our examination of the Rb-Kr system [N. P. Wells et al., Phys. Rev. A 89, 052516 (2014), 10.1103/PhysRevA.89.052516], the isoclinic point provides (arguably) the only means of assessing κ unambiguously: κKr=0.36 ±0.06 and in the present work κXe=0.32 ±0.05 . With our estimate of κ for the Rb-Kr and Rb-Xe systems, we were able to combine our Kr and Xe collision shift measurements with those of Rotondaro and Perram [M. D. Rotondaro and G. P. Perram, J. Quant. Spectrosc. Radiat. Transfer 57, 497 (1997), 10.1016/S0022-4073(96)00147-1] (another set of high quality ∂ [δ ν ]/∂ P measurements) to obtain a highly accurate experimental estimate for the D1 collision shift resulting from Rb's interaction with the heavy noble gases: For the Rb-Kr interaction ∂ [δ ν ] /∂ P |T =323 K=-5.02 ±0.07 MHz /torr and for the Rb-Xe interaction ∂ [δ ν ] /∂ P |T =323 K=-5.46 ±0.09 MHz /torr . These measured values for the collision-shift coefficient are approximately 20 % smaller (in magnitude) than the best theoretical estimates, suggesting that there is room for theoretical improvement regarding our present understanding of how noble-gas collisions perturb the alkali-metal P1 /2 state.

Algae Tile Data: 2004-2007, BPA-51; Preliminary Report, October 28, 2008.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holderman, Charles

Multiple files containing 2004 through 2007 Tile Chlorophyll data for the Kootenai River sites designated as: KR1, KR2, KR3, KR4 (Downriver) and KR6, KR7, KR9, KR9.1, KR10, KR11, KR12, KR13, KR14 (Upriver) were received by SCS. For a complete description of the sites covered, please refer to http://ktoi.scsnetw.com. To maintain consistency with the previous SCS algae reports, all analyses were carried out separately for the Upriver and Downriver categories, as defined in the aforementioned paragraph. The Upriver designation, however, now includes three additional sites, KR11, KR12, and the nutrient addition site, KR9.1. Summary statistics and information on the four responses,more » chlorophyll a, chlorophyll a Accrual Rate, Total Chlorophyll, and Total Chlorophyll Accrual Rate are presented in Print Out 2. Computations were carried out separately for each river position (Upriver and Downriver) and year. For example, the Downriver position in 2004 showed an average Chlorophyll a level of 25.5 mg with a standard deviation of 21.4 and minimum and maximum values of 3.1 and 196 mg, respectively. The Upriver data in 2004 showed a lower overall average chlorophyll a level at 2.23 mg with a lower standard deviation (3.6) and minimum and maximum values of (0.13 and 28.7, respectively). A more comprehensive summary of each variable and position is given in Print Out 3. This lists the information above as well as other summary information such as the variance, standard error, various percentiles and extreme values. Using the 2004 Downriver Chlorophyll a as an example again, the variance of this data was 459.3 and the standard error of the mean was 1.55. The median value or 50th percentile was 21.3, meaning 50% of the data fell above and below this value. It should be noted that this value is somewhat different than the mean of 25.5. This is an indication that the frequency distribution of the data is not symmetrical (skewed). The skewness statistic, listed as part of the first section of each analysis, quantifies this. In a symmetric distribution, such as a Normal distribution, the skewness value would be 0. The tile chlorophyll data, however, shows larger values. Chlorophyll a, in the 2004 Downriver example, has a skewness statistic of 3.54, which is quite high. In the last section of the summary analysis, the stem and leaf plot graphically demonstrates the asymmetry, showing most of the data centered around 25 with a large value at 196. The final plot is referred to as a normal probability plot and graphically compares the data to a theoretical normal distribution. For chlorophyll a, the data (asterisks) deviate substantially from the theoretical normal distribution (diagonal reference line of pluses), indicating that the data is non-normal. Other response variables in both the Downriver and Upriver categories also indicated skewed distributions. Because the sample size and mean comparison procedures below require symmetrical, normally distributed data, each response in the data set was logarithmically transformed. The logarithmic transformation, in this case, can help mitigate skewness problems. The summary statistics for the four transformed responses (log-ChlorA, log-TotChlor, and log-accrual ) are given in Print Out 4. For the 2004 Downriver Chlorophyll a data, the logarithmic transformation reduced the skewness value to -0.36 and produced a more bell-shaped symmetric frequency distribution. Similar improvements are shown for the remaining variables and river categories. Hence, all subsequent analyses given below are based on logarithmic transformations of the original responses.« less

High- T c superconductivity at the interface between the CaCuO 2 and SrTiO 3 insulating oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Di Castro, D.; Cantoni, C.; Ridolfi, F.

2015-09-28

At interfaces between complex oxides it is possible to generate electronic systems with unusual electronic properties, which are not present in the isolated oxides. One important example is the appearance of superconductivity at the interface between insulating oxides, although, until now, with very low T c. We report the occurrence of high T c superconductivity in the bilayer CaCuO 2/SrTiO 3, where both the constituent oxides are insulating. In order to obtain a superconducting state, the CaCuO 2/SrTiO 3 interface must be realized between the Ca plane of CaCuO 2 and the TiO 2 plane of SrTiO 3. Only inmore » this case can oxygen ions be incorporated in the interface Ca plane, acting as apical oxygen for Cu and providing holes to the CuO 2 planes. In addition, a detailed hole doping spatial profile can be obtained by scanning transmission electron microscopy and electron-energy-loss spectroscopy at the O K edge, clearly showing that the (super)conductivity is confined to about 1–2 CaCuO 2 unit cells close to the interface with SrTiO 3. The results obtained for the CaCuO 2/SrTiO 3 interface can be extended to multilayered high T c cuprates, contributing to explaining the dependence of T c on the number of CuO 2 planes in these systems.« less

Photocatalytic and adsorption properties of TiO2-pillared montmorillonite obtained by hydrothermally activated intercalation of titanium polyhydroxo complexes

PubMed Central

Ovchinnikov, Nikolay L; Karasev, Nikita S; Kochkina, Nataliya E; Agafonov, Alexander V; Vinogradov, Alexandr V

2018-01-01

We report on a new approach for the synthesis of TiO2-pillared montmorillonite, where the pillars exhibit a high degree of crystallinity (nanocrystals) representing a mixture of anatase and rutile phases. The structures exhibit improved adsorption and photocatalytic activity as a result of hydrothermally activated intercalation of titanium polyhydroxo complexes (i.e., TiCl4 hydrolysis products) in a solution with a concentration close to the sol formation limit. The materials, produced at various annealing temperatures from the intercalated samples, were characterized by infrared spectroscopy, differential scanning calorimetry (DSC)/thermogravimetric analysis (TGA), X-ray diffraction, dynamic light scattering (DLS) measurements, and liquefied nitrogen adsorption/desorption. The photocatalytic activity of the TiO2-pillared materials was studied using the degradation of anionic (methyl orange, MO) and cationic (rhodamine B, RhB) dyes in water under UV irradiation. The combined effect of adsorption and photocatalysis resulted in removal of 100% MO and 97.5% RhB (with an initial concentration of 40 mg/L and a photocatalyst-sorbent concentration of 1 g/L) in about 100 minutes. The produced TiO2-pillared montmorillonite showed increased photocatalytic activity as compared to the commercially available photocatalyst Degussa P25. PMID:29515950

DOE Office of Scientific and Technical Information (OSTI.GOV)

Radchenko, Valery; Meyer, Catherine Anne Louise; Engle, Jonathan Ward

Scandium-44 g (half-life 3.97 h) shows promise for positron emission tomography (PET) imaging of longer biological processes than that of the current gold standard, 18F, due to its favorable decay parameters. One source of 44gSc is the long-lived parent nuclide 44Ti (half-life 60.0 a). A 44Ti/ 44gSc generator would have the ability to provide radionuclidically pure 44gSc on a daily basis. The production of 44Ti via the 45Sc(p,2n) reaction requires high proton beam currents and long irradiation times. Recovery and purification of no-carrier added (nca) 44Ti from scandium metal targets involves complex separation chemistry. In this study, separation systems basedmore » on solid phase extraction chromatography were investigated, including branched diglycolamide (BDGA) resin and hydroxamate based ZR resin. Lastly, results indicate that ZR resin in HCl media represents an effective 44Ti/ 44gSc separation system.« less

Origin of Fe-Ti Oxide Mineralization in the Middle Paleoproterozoic Elet'ozero Syenite-Gabbro Intrusive Complex (Northern Karelia, Russia)

NASA Astrophysics Data System (ADS)

Sharkov, E. V.; Chistyakov, A. V.; Shchiptsov, V. V.; Bogina, M. M.; Frolov, P. V.

2018-03-01

Magmatic oxide mineralization widely developed in syenite-gabbro intrusive complexes is an important Fe and Ti resource. However, its origin is hotly debatable. Some researchers believe that the oxide ores were formed through precipitation of dense Ti-magnetite in an initial ferrogabbroic magma (Bai et al., 2012), whereas others consider them as a product of immiscible splitting of Fe-rich liquid during crystallization of Fe-Ti basaltic magma (Zhou et al., 2013). We consider this problem with a study of the Middle Paleoproterozoic (2086 ± 30 Ma) Elet'ozero Ti-bearing layered intrusive complex in northern Karelia (Baltic Shield). The first ore-bearing phase of the complex is mainly made up of diverse ferrogabbros, with subordinate clinopyroxenites and peridotites. Fe-Ti oxides (magnetite, Ti-magnetite, and ilmenite) usually account for 10-15 vol %, reaching 30-70% in ore varieties. The second intrusive phase is formed by alkaline and nepheline syenites. Petrographical, mineralogical, and geochemical data indicate that the first phase of the intrusion was derived from a moderately alkaline Fe-Ti basaltic melt, while the parental melt of the second phase was close in composition to alkaline trachyte. The orebodies comprise disseminated and massive ores. The disseminated Fe-Ti oxide ores make up lenses and layers conformable to general layering. Massive ores occur in subordinate amounts as layers and lenses, as well as cross-cutting veins. Elevated Nb and Ta contents in Fe-Ti oxides makes it possible to consider them complex ores. It is shown that the Fe-Ti oxide mineralization is related to the formation of a residual (Fe,Ti)-rich liquid, which lasted for the entire solidification history of the first intrusive phase. The liquid originated through multiple enrichment of Fe and Ti in the crystallization zone of the intrusion owing to the following processes: (1) precipitation of silicate minerals in the crystallization zone with a corresponding increase in the Fe and Ti contents in an interstitial melt; and (2) periodic accumulation of the residual melt in front of this zone. Unlike liquid immiscibility leading to melt splitting into two phases, this liquid dissolved the residual components of the melt. Correspondingly, such an Fe-rich liquid has unusual properties and requires further study.

Molecular titanium nitrides: nucleophiles unleashed

DOE PAGES

Grant, Lauren N.; Pinter, Balazs; Kurogi, Takashi; ...

2017-01-30

In this contribution we present reactivity studies of a rare example of a titanium salt, in the form of [μ 2-K(OEt 2)] 2[(PN) 2Timore » $$\\equiv$$N] 2 (1) (PN - = N-(2-(diisopropylphosphino)-4-methylphenyl)-2,4,6-trimethylanilide) to produce a series of imide moieties including rare examples such as methylimido, borylimido, phosphonylimido, and a parent imido. For the latter, using various weak acids allowed us to narrow the pK a range of the NH group in (PN) 2Ti$$\\equiv$$NH to be between 26–36. Complex 1 could be produced by a reductively promoted elimination of N 2 from the azide precursor (PN) 2TiN 3, whereas reductive splitting of N 2 could not be achieved using the complex (PN) 2Ti$$\\equiv$$N$$\\equiv$$N$$\\equiv$$Ti(PN) 2 (2) and a strong reductant. Complete N-atom transfer reactions could also be observed when 1 was treated with ClC(O) tBu and OCCPh 2 to form NC tBu and KNCCPh 2, respectively, along with the terminal oxo complex (PN) 2Ti$$\\equiv$$O, which was also characterized. A combination of solid state 15N NMR (MAS) and theoretical studies allowed us to understand the shielding effect of the counter cation in dimer 1, the monomer [K(18-crown-6)][(PN) 2Ti$$\\equiv$$N], and the discrete salt [K(2,2,2-Kryptofix)][(PN) 2Ti$$\\equiv$$N] as well as the origin of the highly downfield 15N NMR resonance when shifting from dimer to monomer to a terminal nitride (discrete salt). The upfield shift of 15N nitride resonance in the 15N NMR spectrum was found to be linked to the K + induced electronic structural change of the titanium-nitride functionality by using a combination of MO analysis and quantum chemical analysis of the corresponding shielding tensors.« less

Synthesis and Characterization of LaTiO2N

NASA Astrophysics Data System (ADS)

Rugen, Evan E.

Photocatalysts offer an excellent opportunity to shift the global energy landscape from a fossil fuel-dependent paradigm to sustainable and carbon-neutral solar fuels. Oxynitride materials such as LaTiO2N are potential photocatalysts for the water splitting reaction due to their high oxidative stability and their narrow band gaps, which are suitable for visible light absorption. However, facile synthetic routes to metal oxynitrides with controlled morphologies are rare, and the local structures of these materials are under-characterized. Ultrasonic spray synthesis (USS) offers a facile method toward complex metal oxides which can potentially be converted to oxynitrides with preservation of the microsphere structures that typify the products from such aerosol routes. Here, La-Ti-O microspheres were facilely produced by USS and converted by ammonolysis to LaTiO2N microspheres with porous shells and hollow interiors. This particle architecture is accounted for by coupling suitable combustion chemistry with the aerosol technique, producing precursor particles where the La3+ and Ti4+ are well-mixed at small length scales; this feature enables preservation of the microsphere morphology during nitridation despite the crystallographic changes that occur. The LaTiO2N microspheres are comparable oxygen evolving photocatalysts to samples produced by conventional solid state methods. Pair distribution function (PDF) analysis is a local probe designed to examine the structure of disordered crystalline materials, and is an ideal technique for characterizing the ordering of anions in oxynitrides. Preliminary studies using PDF analysis to determine the presence of anion ordering and local structure in LaTiO2N produced by solid state methods are presented here. Future experiments are proposed that will grant detailed insight into the factors driving the degree of anion ordering in these types of materials. These results demonstrate the utility of USS as a facile, potentially scalable route to complex photocatalytic materials and their precursors, and the feasibility of PDF analysis for the determination of local structures in complex oxynitrides.

Determination of the reaction rate coefficient of sulphide mine tailings deposited under water.

PubMed

Awoh, Akué Sylvette; Mbonimpa, Mamert; Bussière, Bruno

2013-10-15

The efficiency of a water cover to limit dissolved oxygen (DO) availability to underlying acid-generating mine tailings can be assessed by calculating the DO flux at the tailings-water interface. Fick's equations, which are generally used to calculate this flux, require knowing the effective DO diffusion coefficient (Dw) and the reaction (consumption) rate coefficient (Kr) of the tailings, or the DO concentration profile. Whereas Dw can be accurately estimated, few studies have measured the parameter Kr for submerged sulphide tailings. The objective of this study was to determine Kr for underwater sulphide tailings in a laboratory experiment. Samples of sulphide mine tailings (an approximately 6 cm layer) were placed in a cell under a water cover (approximately 2 cm) maintained at constant DO concentration. Two tailings were studied: TA1 with high sulphide content (83% pyrite) and TA2 with low sulphide content (2.8% pyrite). DO concentration was measured with a microelectrode at various depths above and below the tailings-water interface at 1 mm intervals. Results indicate that steady-state condition was rapidly attained. As expected, a diffusive boundary layer (DBL) was observed in all cases. An iterative back-calculation process using the numerical code POLLUTEv6 and taking the DBL into account provided the Kr values used to match calculated and experimental concentration profiles. Kr obtained for tailings TA1 and TA2 was about 80 d(-1) and 6.5 d(-1), respectively. For comparison purposes, Kr obtained from cell tests on tailings TA1 was lower than Kr calculated from the sulphate production rate obtained from shake-flask tests. Steady-state DO flux at the water-tailings interface was then calculated with POLLUTEv6 using tailings characteristics Dw and Kr. For the tested conditions, DO flux ranged from 608 to 758 mg O2/m(2)/d for tailings TA1 and from 177 to 221 mg O2/m(2)/d for tailings TA2. The impact of placing a protective layer of inert material over the tailings was also investigated for tailings TA1 (with high sulphide content). A protective layer of only 5 cm reduced the DO flux into the tailings at about 5 mg/m(2)/d, compared to 608 mg O2/m(2)/d without a protective layer, or an approximately 99% reduction in flux. Copyright © 2013 Elsevier Ltd. All rights reserved.

Xe/Kr Selectivity Measurements using AgZ-PAN at Various Temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garn, Troy Gerry; Greenhalgh, Mitchell Randy; Watson, Tony Leroy

2015-05-01

In preparation for planned FY-15 Xe/Kr multi-column testing, a series of experiments were performed to determine the selectivity of Xe over Kr using the silver converted mordenite-polyacrylonitrile (AgZ-PAN) sorbent. Results from these experiments will be used for parameter selection guidelines to define test conditions for Kr gas capture purity evaluations later this year. The currently configured experimental test bed was modified by installing a new cooling apparatus to permit future multi-column testing with independent column temperature control. The modified test bed will allow for multi-column testing to facilitate a Xe separation followed by a Kr separation using engineered form sorbents.more » Selectivity experiments were run at temperatures of 295, 250 and 220 K. Two feed gas compositions of 1000 ppmv Xe, 150 ppmv Kr in either a He or an air balance were used. AgZ-PAN sorbent selectivity was calculated using Xe and Kr capacity determinations. AgZ-PAN sorbent selectivities for Xe over Kr of 72 were calculated at room temperature (295 K) using the feed gas with a He balance and 34 using the feed gas with an air balance. As the test temperatures were decreased the selectivity of Xe over Kr also decreased due to an increase in both Xe and Kr capacities. At 220 K, the sorbent selectivities for Xe over Kr were 22 using the feed gas with a He balance and 28 using the feed gas with an air balance. The selectivity results indicate that AgZ-PAN used in the first column of a multi-column configuration will provide adequate partitioning of Xe from Kr in the tested temperature range to produce a more pure Kr end product for collection.« less

A heterobimetallic complex featuring a Ti–Co multiple bond and its application to the reductive coupling of ketones to alkenes† †Electronic supplementary information (ESI) available: Experimental procedures, additional spectroscopic data for 1–4, and computational details of 2 and 3. CCDC 1037714–1037716. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc03772c Click here for additional data file. Click here for additional data file.

PubMed Central

Wu, Bing; Bezpalko, Mark W.; Foxman, Bruce M.

2015-01-01

To explore metal–metal multiple bonds between first row transition metals, Ti/Co complexes supported by two phosphinoamide ligands have been synthesized and characterized. The Ti metalloligand Cl2Ti(XylNPiPr2)2 (1) was treated with CoI2 under reducing conditions, permitting isolation of the Ti/Co complex [(μ-Cl)Ti(XylNPiPr2)2CoI]2 (2). One electron reduction of complex 2 affords ClTi(XylNPiPr2)2CoPMe3 (3), which features a metal–metal triple bond and an unprecedentedly short Ti–Co distance of 2.0236(9) Å. This complex is shown to promote the McMurry coupling reaction of aryl ketones into alkenes, with concomitant formation of the tetranuclear complex [Ti(μ3-O)(NXylPiPr2)2CoI]2 (4). A cooperative mechanism involving bimetallic C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 O bond activation and a cobalt carbene intermediate is proposed. PMID:29142672

The Transient Nature of Bunyamwera Orthobunyavirus NSs Protein Expression: Effects of Increased Stability of NSs Protein on Virus Replication

PubMed Central

van Knippenberg, Ingeborg; Fragkoudis, Rennos; Elliott, Richard M.

2013-01-01

The NSs proteins of bunyaviruses are the viral interferon antagonists, counteracting the host's antiviral response to infection. During high-multiplicity infection of cultured mammalian cells with Bunyamwera orthobunyavirus (BUNV), NSs is rapidly degraded after reaching peak levels of expression at 12hpi. Through the use of inhibitors this was shown to be the result of proteasomal degradation. A recombinant virus (rBUN4KR), in which all four lysine residues in NSs were replaced by arginine residues, expresses an NSs protein (NSs4KR) that is resistant to degradation, confirming that degradation is lysine-dependent. However, despite repeated attempts, no direct ubiquitylation of NSs in infected cells could be demonstrated. This suggests that degradation of NSs, although lysine-dependent, may be achieved through an indirect mechanism. Infection of cultured mammalian cells or mice indicated no disadvantage for the virus in having a non-degradable NSs protein: in fact rBUN4KR had a slight growth advantage over wtBUNV in interferon-competent cells, presumably due to the increased and prolonged presence of NSs. In cultured mosquito cells there was no difference in growth between wild-type BUNV and rBUN4KR, but surprisingly NSs4KR was not stabilised compared to the wild-type NSs protein. PMID:23667701

The transient nature of Bunyamwera orthobunyavirus NSs protein expression: effects of increased stability of NSs protein on virus replication.

PubMed

van Knippenberg, Ingeborg; Fragkoudis, Rennos; Elliott, Richard M

2013-01-01

The NSs proteins of bunyaviruses are the viral interferon antagonists, counteracting the host's antiviral response to infection. During high-multiplicity infection of cultured mammalian cells with Bunyamwera orthobunyavirus (BUNV), NSs is rapidly degraded after reaching peak levels of expression at 12hpi. Through the use of inhibitors this was shown to be the result of proteasomal degradation. A recombinant virus (rBUN4KR), in which all four lysine residues in NSs were replaced by arginine residues, expresses an NSs protein (NSs4KR) that is resistant to degradation, confirming that degradation is lysine-dependent. However, despite repeated attempts, no direct ubiquitylation of NSs in infected cells could be demonstrated. This suggests that degradation of NSs, although lysine-dependent, may be achieved through an indirect mechanism. Infection of cultured mammalian cells or mice indicated no disadvantage for the virus in having a non-degradable NSs protein: in fact rBUN4KR had a slight growth advantage over wtBUNV in interferon-competent cells, presumably due to the increased and prolonged presence of NSs. In cultured mosquito cells there was no difference in growth between wild-type BUNV and rBUN4KR, but surprisingly NSs4KR was not stabilised compared to the wild-type NSs protein.

Precipitation Behaviors of TiN Inclusion in GCr15 Bearing Steel Billet

NASA Astrophysics Data System (ADS)

Tian, Qianren; Wang, Guocheng; Zhao, Yang; Li, Jing; Wang, Qi

2018-06-01

There are many types of non-metallic TiN-based inclusions observed in GCr15 bearing steel, including single-particle TiN, multi-particle polymerized TiN, and complex inclusions like TiN-MnS, TiN-MgO-MgAl2O4 (TiN-MgO-MA), and TiN-MgAl2O4-MnS (TiN-MA-MnS). Thermodynamic calculations suggest that single-particle TiN precipitates dominate the mushy zone of GCr15 bearing steel. Kinetic calculations regarding TiN growth suggest that the final size of the single-particle TiN ranges between 1 and 6 μm in the initial concentration range of [pct Ti] = 0.0060 to 0.0079 and [pct N] = 0.0049 to 0.0070, at 1620 to 1640 K and a local cooling rate of 0.5 to 10 K/s. The multi-particle polymerized TiN are formed by single TiN particles in three stages: single-particle TiN inclusions approach each other drawn by the cavity bridge force (CBF), local active angles consolidate, and neck region sintering occurs. Based on the thermodynamic calculations of TiN, MnS, and MgO precipitation, the formation behaviors of complex inclusions of TiN-MnS, TiN-MgO-MA, and TiN-MA-MnS were investigated.

Metal–organic framework with optimally selective xenon adsorption and separation

DOE PAGES

Banerjee, Debasis; Simon, Cory M.; Plonka, Anna M.; ...

2016-06-13

Nuclear energy is considered among the most viable alternatives to our current fossil fuel based energy economy.1 The mass-deployment of nuclear energy as an emissions-free source requires the reprocessing of used nuclear fuel to mitigate the waste.2 One of the major concerns with reprocessing used nuclear fuel is the release of volatile radionuclides such as Xe and Kr. The most mature process for removing these radionuclides is energy- and capital-intensive cryogenic distillation. Alternatively, porous materials such as metal-organic frameworks (MOFs) have demonstrated the ability to selectively adsorb Xe and Kr at ambient conditions.3-8 High-throughput computational screening of large databases ofmore » porous materials has identified a calcium-based nanoporous MOF, SBMOF-1, as the most selective for Xe over Kr.9,10 Here, we affirm this prediction and report that SBMOF-1 exhibits by far the highest Xe adsorption capacity and a remarkable Xe/Kr selectivity under relevant nuclear reprocessing conditions. The exceptional selectivity of SBMOF-1 is attributed to its pore size tailored to Xe and its dense wall of atoms that constructs a binding site with a high affinity for Xe, as evident by single crystal X-ray diffraction and molecular simulation.« less

New high pressure experiments on sulfide saturation of high-FeO∗ basalts with variable TiO2 contents - Implications for the sulfur inventory of the lunar interior

NASA Astrophysics Data System (ADS)

Ding, Shuo; Hough, Taylor; Dasgupta, Rajdeep

2018-02-01

In order to constrain sulfur concentration in intermediate to high-Ti mare basalts at sulfide saturation (SCSS), we experimentally equilibrated FeS melt and basaltic melt using a piston cylinder at 1.0-2.5 GPa and 1400-1600 °C, with two silicate compositions similar to high-Ti (Apollo 11: A11, ∼11.1 wt.% TiO2, 19.1 wt.% FeO∗, and 39.6 wt.% SiO2) and intermediate-Ti (Luna 16, ∼5 wt.% TiO2, 18.7 wt.% FeO∗, and 43.8 wt.% SiO2) mare basalts. Our experimental results show that SCSS increases with increasing temperature, and decreases with increasing pressure, which are similar to the results from previous experimental studies. SCSS in the A11 melt is systematically higher than that in the Luna 16 melt, which is likely due to higher FeO∗, and lower SiO2 and Al2O3 concentration in the former. Compared to the previously constructed SCSS models, including those designed for high-FeO∗ basalts, the SCSS values determined in this study are generally lower than the predicted values, with overprediction increasing with increasing melt TiO2 content. We attribute this to the lower SiO2 and Al2O3 concentration of the lunar magmas, which is beyond the calibration range of previous SCSS models, and also more abundant FeTiO3 complexes in our experimental melts that have higher TiO2 contents than previous models' calibration range. The formation of FeTiO3 complexes lowers the activity of FeO∗, a FeO∗silicatemelt , and therefore causes SCSS to decrease. To accommodate the unique lunar compositions, we have fitted a new SCSS model for basaltic melts of >5 wt.% FeO∗ and variable TiO2 contents. Using previous chalcophile element partitioning experiments that contained more complex Fe-Ni-S sulfide melts, we also derived an empirical correction that allows SCSS calculation for basalts where the equilibrium sulfides contain variable Ni contents of 10-50 wt.%. At the pressures and temperatures of multiple saturation points, SCSS of lunar magmas with compositions from picritic glasses, mare basalts, to young lunar meteorites vary from 2600 to 4800 ppm for basalt equilibration with a pure FeS melt and from 1400 to 2600 ppm for basalt equilibration with a Fe-rich sulfide melt containing 30 wt.% Ni. The measured S contents in these proposed near-primary lunar magmas are lower than the predicted SCSS at the conditions of their last equilibration with the lunar mantle, indicating no sulfide retention in the lunar mantle source during partial melting. Sulfide exhaustion during partial melting in the lunar mantle also supports the notion that the bulk silicate moon is depleted in highly siderophile elements. Based on the measured S contents and the estimated degree of melting, the estimated S contents for the mantle source of A15 green glass and A15 mare basalts is 10-23 ppm; for A17 orange glass is 25-62 ppm, for A12 mare basalts is 27-92 ppm, and for A11 basalt is 35-120 ppm. Consideration of SCSS decrease due to the presence of Ni in the sulfide melt does not change these mantle S abundance estimates for <30 wt.% Ni in the sulfide. The inferred S contents suggest that the lunar mantle is heterogeneous in terms of S. Although variable among different groups, the inferred S abundance of up to 120 ppm in the lunar mantle falls near the lower end of the S content of the depleted terrestrial mantle such as the MORB source.

[TiO2-Induced Photodegradation of Levofloxacin by Visible Light and Its Mechanism].

PubMed

Guo, Hong-sheng; Liu, Ya-nan; Qiao, Qi; Wei, Hong; Dong, Cheng-xing; Xue, Jie; Li, Ke-bin

2015-05-01

Levofloxacin is an emerging pollutant. Single levofloxacin and TiO2 have no visible-light activity. However, photodegradation of levofloxacin dramatically enhanced in the presence of TiO2 under visible light irradiation. Considering this finding, he photodegradation of levofloxacin over TiO2 was investigated under visible light irradiation. Effects of TiO2 dosage, levofloxacin concentration, and solution pH on levofloxacin photodegradation were examined by monitoring its concentration decay with time. The results showed that levofloxacin photodegradation fitted the Langmuir-Hinshelwood kinetic model. Solution pH, TiO2 dose, and levofloxacin concentration had significant effects on the photodegradation rates. In addition, batch adsorption experiments revealed that adsorption of levofloxacin on TiO2 conformed to the pseudo-second-order kinetics and the Langmuir isotherm. DRS spectrum of levofloxacin-adsorbed TiO2 suggested that a surface complex was formed between levofloxacin and TiO2. Addition of radical scavengers and N2-degassing affecting levofloxacin photodegradation indicated that the superoxide ion radical was mainly active species. UV-Vis spectra of a deaerated TiO2 and levofloxacin suspensions further confirmed that the electron injection into TiO2 conduction band took place under visible light irradiation. Based on these results, a charge-transfer mechanism initiated by photoexcitation of TiO2/ levofloxacin surface complex was proposed for levofloxacin photocatalytic degradation over TiO2 under visible light. This study indicates that the charge-transfer-complex-mediated photocatalytic technique has promising applications in the removal of colorless organic pollutants.

Nanoscale Strontium Titanate Sheets and Crystals

NASA Astrophysics Data System (ADS)

Tilka, Jack Andrew

The physical properties of materials are dominated by their structure and composition. Insight into the structure of complex oxide materials has the potential to improve our understanding and eventually control of their physical properties. This PhD thesis reports the development of characterization and fabrication techniques relevant to improving the scientific understanding of complex oxide materials. The work presented here has two components. I report a way to use ideas that were originally developed in semiconductor processing to control the elastic strain state and crystallization process of the model complex oxide SrTiO3. An additional component is an important series of advances in the analysis of diffraction patterns acquired with focused x-ray nanobeams. The fabrication and characterization of nanoscale SrTiO3 has been experimentally shown to allow the introduction of elastic strain into SrTiO3. The creation of thin SrTiO3 crystals from (001)-oriented SrTiO3 bulk single crystals using focused ion beam milling techniques yields sheets with submicron thickness and arbitrary orientation within the (001) plane. Synchrotron x-ray nanodiffraction experiments show that the SrTiO 3 sheets have rocking curves with angular widths less than 0.02°. These widths are less than a factor of two larger than bulk SrTiO3, which shows that the sheets are suitable substrates for epitaxial thin film growth. A precisely selected elastic strain can be introduced into the SrTiO 3 sheets using a silicon nitride stressor layer. Synchrotron x-ray nanodiffraction studies show that the strain introduced in the SrTiO3 sheets is on the order of 10-4, matching the predictions of an elastic model. This approach to elastic strain sharing in complex oxides allows the strain to be selected within a wide and continuous range of values, an effect not achievable in heteroepitaxy on rigid substrates. An additional fabrication technique is also evaluated here based on the crystallization of SrTiO3 from initially amorphous thin films. This process is known as solid-phase epitaxy in two-dimensional samples but is just beginning to be explored in more complex geometries. I report experiments in both homoepitaxy and heteroepitaxy including measurements of crystal growth rates and the crystallographic orientations of crystals formed in this way. The lateral growth rates are consistent with previously measured vertical growth. This result indicated that previous work on vertical solid-phase epitaxy could be extended into lateral solid-phase epitaxy, which has the power to be applied to complicated non-planar geometries. The highly coherent and tightly focused x-ray beams produced by hard x-ray light sources enable the nanoscale structural characterization of materials but are accompanied by significant challenges in the interpretation of diffraction and scattering patterns. I report here a series of methods that expand the range of physical problems that can be accurately captured by coherent x-ray optical simulations. My approach has been to expand simulations methods to include arbitrary x-ray incident angles and arbitrary epitaxial heterostructures. I first applied these methods to extract the misorientation of lattice planes and the strain of individual layers of Si/SiGe heterostructures relevant to applications in quantum electronics. Further applications reported in this thesis are in probing defects created in the processing of SrTiO3 and in measuring the change in lattice parameter introduced into strained SrTiO3 sheets. The systematic interpretation of nanobeam diffraction patterns aids in the fabrication of SrTiO3 nanostructures.

Kr photoionized plasma induced by intense extreme ultraviolet pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bartnik, A., E-mail: andrzej.bartnik@wat.edu.pl; Wachulak, P.; Fiedorowicz, H.

Irradiation of any gas with an intense EUV (extreme ultraviolet) radiation beam can result in creation of photoionized plasmas. The parameters of such plasmas can be significantly different when compared with those of the laser produced plasmas (LPP) or discharge plasmas. In this work, the photoionized plasmas were created in a krypton gas irradiated using an LPP EUV source operating at a 10 Hz repetition rate. The Kr gas was injected into the vacuum chamber synchronously with the EUV radiation pulses. The EUV beam was focused onto a Kr gas stream using an axisymmetrical ellipsoidal collector. The resulting low temperature Krmore » plasmas emitted electromagnetic radiation in the wide spectral range. The emission spectra were measured either in the EUV or an optical range. The EUV spectrum was dominated by emission lines originating from Kr III and Kr IV ions, and the UV/VIS spectra were composed from Kr II and Kr I lines. The spectral lines recorded in EUV, UV, and VIS ranges were used for the construction of Boltzmann plots to be used for the estimation of the electron temperature. It was shown that for the lowest Kr III and Kr IV levels, the local thermodynamic equilibrium (LTE) conditions were not fulfilled. The electron temperature was thus estimated based on Kr II and Kr I species where the partial LTE conditions could be expected.« less

Synthesis of high performance ceramic fibers by chemical vapor deposition for advanced metallics reinforcing

NASA Technical Reports Server (NTRS)

Revankar, Vithal; Hlavacek, Vladimir

1991-01-01

The chemical vapor deposition (CVD) synthesis of fibers capable of effectively reinforcing intermetallic matrices at elevated temperatures which can be used for potential applications in high temperature composite materials is described. This process was used due to its advantage over other fiber synthesis processes. It is extremely important to produce these fibers with good reproducible and controlled growth rates. However, the complex interplay of mass and energy transfer, blended with the fluid dynamics makes this a formidable task. The design and development of CVD reactor assembly and system to synthesize TiB2, CrB, B4C, and TiC fibers was performed. Residual thermal analysis for estimating stresses arising form thermal expansion mismatch were determined. Various techniques to improve the mechanical properties were also performed. Various techniques for improving the fiber properties were elaborated. The crystal structure and its orientation for TiB2 fiber is discussed. An overall view of the CVD process to develop CrB2, TiB2, and other high performance ceramic fibers is presented.

Effects of ultrasonication and conventional mechanical homogenization processes on the structures and dielectric properties of BaTiO3 ceramics.

PubMed

Akbas, Hatice Zehra; Aydin, Zeki; Yilmaz, Onur; Turgut, Selvin

2017-01-01

The effects of the homogenization process on the structures and dielectric properties of pure and Nb-doped BaTiO 3 ceramics have been investigated using an ultrasonic homogenization and conventional mechanical methods. The reagents were homogenized using an ultrasonic processor with high-intensity ultrasonic waves and using a compact mixer-shaker. The components and crystal types of the powders were determined by Fourier-transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) analyses. The complex permittivity (ε ' , ε″) and AC conductivity (σ') of the samples were analyzed in a wide frequency range of 20Hz to 2MHz at room temperature. The structures and dielectric properties of pure and Nb-doped BaTiO 3 ceramics strongly depend on the homogenization process in a solid-state reaction method. Using an ultrasonic processor with high-intensity ultrasonic waves based on acoustic cavitation phenomena can make a significant improvement in producing high-purity BaTiO 3 ceramics without carbonate impurities with a small dielectric loss. Copyright © 2016 Elsevier B.V. All rights reserved.

Microwave properties of epitaxial (111)-oriented Ba{sub 0.6}Sr{sub 0.4}TiO{sub 3} thin films on Al{sub 2}O{sub 3}(0001) up to 40 GHz

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang Lihui; UMR CNRS 8520, IEMN-DOAE-MIMM Team, Bat. P3, Cite Scientifique, Villeneuve d'Ascq, 59655 Lille; Ponchel, Freddy

2010-10-18

Perovskite Ba{sub 0.6}Sr{sub 0.4}TiO{sub 3} (BST) thin films have been grown on Al{sub 2}O{sub 3}(0001) substrates without/with inserting an ultrathin TiO{sub x} seeding layer by rf magnetron sputtering. X-ray diffraction and pole figure studies reveal that the film with the TiO{sub x} layer (12-A-thick) is highly oriented along the (111) direction and exhibits a good in-plane relationship of BST(111)||Al{sub 2}O{sub 3}(0001). The high frequency dielectric measurements demonstrate that the complex permittivity ({epsilon}={epsilon}{sup '}-j{epsilon}{sup ''}) is well described by a Curie-von Scheidler dispersion with an exponent of 0.40. The resulting epitaxial BST films show high permittivity ({approx}428) and tunability ({approx}41%, atmore » 300 kV/cm and 40 GHz) and their microwave properties (1-40 GHz) potentially could be made suitable for tunable devices.« less

Separation of 44Ti from proton irradiated scandium by using solid-phase extraction chromatography and design of 44Ti/44Sc generator system.

PubMed

Radchenko, V; Meyer, C A L; Engle, J W; Naranjo, C M; Unc, G A; Mastren, T; Brugh, M; Birnbaum, E R; John, K D; Nortier, F M; Fassbender, M E

2016-12-16

Scandium-44g (half-life 3.97h [1]) shows promise for positron emission tomography (PET) imaging of longer biological processes than that of the current gold standard, 18 F, due to its favorable decay parameters. One source of 44g Sc is the long-lived parent nuclide 44 Ti (half-life 60.0 a). A 44 Ti/ 44g Sc generator would have the ability to provide radionuclidically pure 44g Sc on a daily basis. The production of 44 Ti via the 45 Sc(p,2n) reaction requires high proton beam currents and long irradiation times. Recovery and purification of no-carrier added (nca) 44 Ti from scandium metal targets involves complex separation chemistry. In this study, separation systems based on solid phase extraction chromatography were investigated, including branched diglycolamide (BDGA) resin and hydroxamate based ZR resin. Results indicate that ZR resin in HCl media represents an effective 44 Ti/ 44g Sc separation system. Copyright © 2016 Elsevier B.V. All rights reserved.

Imaging and tuning polarity at SrTiO3 domain walls

NASA Astrophysics Data System (ADS)

Frenkel, Yiftach; Haham, Noam; Shperber, Yishai; Bell, Christopher; Xie, Yanwu; Chen, Zhuoyu; Hikita, Yasuyuki; Hwang, Harold Y.; Salje, Ekhard K. H.; Kalisky, Beena

2017-12-01

Electrostatic fields tune the ground state of interfaces between complex oxide materials. Electronic properties, such as conductivity and superconductivity, can be tuned and then used to create and control circuit elements and gate-defined devices. Here we show that naturally occurring twin boundaries, with properties that are different from their surrounding bulk, can tune the LaAlO3/SrTiO3 interface 2DEG at the nanoscale. In particular, SrTiO3 domain boundaries have the unusual distinction of remaining highly mobile down to low temperatures, and were recently suggested to be polar. Here we apply localized pressure to an individual SrTiO3 twin boundary and detect a change in LaAlO3/SrTiO3 interface current distribution. Our data directly confirm the existence of polarity at the twin boundaries, and demonstrate that they can serve as effective tunable gates. As the location of SrTiO3 domain walls can be controlled using external field stimuli, our findings suggest a novel approach to manipulate SrTiO3-based devices on the nanoscale.

Scavenging of oxygen from SrTiO3 by metals and its implications for oxide thin film deposition

NASA Astrophysics Data System (ADS)

Posadas, Agham; Kormondy, Kristy; Guo, Wei; Ponath, Patrick; Kremer, Jacqueline; Hadamek, Tobias; Demkov, Alexander

SrTiO3 is a widely used substrate for the growth of other functional oxide thin films. However, SrTiO3 loses oxygen very easily during oxide thin film deposition even under relatively high oxygen pressures. In some cases, there will be an interfacial layer of oxygen-deficient SrTiO3 formed at the interface with the deposited oxide film, depending on the metals present in the film. By depositing a variety of metals layer by layer and measuring the evolution of the core level spectra of both the deposited metal and SrTiO3 using x-ray photoelectron spectroscopy, we show that there are three distinct types of behavior that occur for thin metal films on SrTiO3. We discuss the implications of these types of behavior for the growth of complex oxide thin films on SrTiO3, and which oxide thin films are expected to produce an interfacial oxygen-deficient layer depending on their elemental constituents.

Separation of 44Ti from proton irradiated scandium by using solid-phase extraction chromatography and design of 44Ti/ 44Sc generator system

DOE PAGES

Radchenko, Valery; Meyer, Catherine Anne Louise; Engle, Jonathan Ward; ...

2016-11-24

Scandium-44 g (half-life 3.97 h) shows promise for positron emission tomography (PET) imaging of longer biological processes than that of the current gold standard, 18F, due to its favorable decay parameters. One source of 44gSc is the long-lived parent nuclide 44Ti (half-life 60.0 a). A 44Ti/ 44gSc generator would have the ability to provide radionuclidically pure 44gSc on a daily basis. The production of 44Ti via the 45Sc(p,2n) reaction requires high proton beam currents and long irradiation times. Recovery and purification of no-carrier added (nca) 44Ti from scandium metal targets involves complex separation chemistry. In this study, separation systems basedmore » on solid phase extraction chromatography were investigated, including branched diglycolamide (BDGA) resin and hydroxamate based ZR resin. Lastly, results indicate that ZR resin in HCl media represents an effective 44Ti/ 44gSc separation system.« less

X-ray induced mutations in jute (Corchorus capsularis L. and Corchorus olitorius L.)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, D.P.; Sharma, B.K.; Banerjee, S.C.

1973-09-30

Dry dormant seeds of three varieties of jute (C. capsularis & b. olitorius), which yield commercial fibers, were irradiated with different doses of x-rays ranging from 10 kR to 100 kR at 10 kR intervals. The percentage of germination, survival rates, the resulting morphological abnormalities in different generations, the total abnormalities, the total mutation frequency including chlorophyll mutations, and the complete, mutation spectrum are described in detail. Mutations were classified into different groups and each mutant was briefly described. Several directly useful mutations were observed with emphasis on the fiber yield. Interesting results were obtained after crossing mutants, where themore » first high yielding hybrid was evolved by the senior author. (auth)« less

Scalable Synthesis of Triple-Core-Shell Nanostructures of TiO2 @MnO2 @C for High Performance Supercapacitors Using Structure-Guided Combustion Waves.

PubMed

Shin, Dongjoon; Shin, Jungho; Yeo, Taehan; Hwang, Hayoung; Park, Seonghyun; Choi, Wonjoon

2018-03-01

Core-shell nanostructures of metal oxides and carbon-based materials have emerged as outstanding electrode materials for supercapacitors and batteries. However, their synthesis requires complex procedures that incur high costs and long processing times. Herein, a new route is proposed for synthesizing triple-core-shell nanoparticles of TiO 2 @MnO 2 @C using structure-guided combustion waves (SGCWs), which originate from incomplete combustion inside chemical-fuel-wrapped nanostructures, and their application in supercapacitor electrodes. SGCWs transform TiO 2 to TiO 2 @C and TiO 2 @MnO 2 to TiO 2 @MnO 2 @C via the incompletely combusted carbonaceous fuels under an open-air atmosphere, in seconds. The synthesized carbon layers act as templates for MnO 2 shells in TiO 2 @C and organic shells of TiO 2 @MnO 2 @C. The TiO 2 @MnO 2 @C-based electrodes exhibit a greater specific capacitance (488 F g -1 at 5 mV s -1 ) and capacitance retention (97.4% after 10 000 cycles at 1.0 V s -1 ), while the absence of MnO 2 and carbon shells reveals a severe degradation in the specific capacitance and capacitance retention. Because the core-TiO 2 nanoparticles and carbon shell prevent the deformation of the inner and outer sides of the MnO 2 shell, the nanostructures of the TiO 2 @MnO 2 @C are preserved despite the long-term cycling, giving the superior performance. This SGCW-driven fabrication enables the scalable synthesis of multiple-core-shell structures applicable to diverse electrochemical applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of point defects on the amorphization of metallic alloys during ion implantation. [NiTi

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pedraza, D.F.; Mansur, L.K.

1985-01-01

A theoretical model of radiation-induced amorphization of ordered intermetallic compounds is developed. The mechanism is proposed to be the buildup of lattice defects to very high concentrations, which destabilizes the crystalline structure. Because simple point defects do not normally reach such levels during irradiation, a new defect complex containing a vacancy and an interstitial is hypothesized. Crucial properties of the complex are that the interstitial sees a local chemical environment similar to that of an atom in the ordered lattice, that the formation of the complex prevents mutual recombination and that the complex is immobile. The evolution of a disordermore » based on complexes is not accompanied by like point defect aggregation. The latter leads to the development of a sink microstructure in alloys that do not become amorphous. For electron irradiation, the complexes form by diffusional encounters. For ion irradiation, complexes are also formed directly in cascades. The possibility of direct amorphization in cascades is also included. Calculations for the compound NiTi show reasonable agreement with measured amorphization kinetics.« less

Functional aging impairs the role of feedback in motor learning.

PubMed

Liu, Yu; Cao, Chunmei; Yan, Jin H

2013-10-01

Optimal motor skill acquisition frequently requires augmented feedback or knowledge of results (KR). However, the effect of functional declines on the benefits of KR remains to be determined. The objective of this research was to examine how cognitive and motor deficits of older adults influence the use of KR for motor skill learning. A total of 57 older adults (mean 73.1 years; SD 4.2) received both cognitive and eye-hand coordination assessments, whereas 55 young controls (mean 25.8 years; SD 3.8) took only the eye-hand coordination test. All young and older participants learned a time-constrained arm movement through KR in three pre-KR and post-KR intervals. In the subsequent no-KR skill retests, absolute and variable time errors were not significantly reduced for the older learners who had KR during skill practice, especially for those with cognitive and motor dysfunctions. The finding suggests that KR results in no measureable improvement for older adults with cognitive and motor functional deficiencies. More importantly, for the older adults, longer post-KR intervals showed greater detrimental effects on feedback-based motor learning than shorter pauses after KR delivery. The findings support the hypothesis about the effects of cognitive and motor deficits on KR in motor skill learning of older adults. The dynamics of cognitive and motor aging, external feedback and internal control mechanisms collectively explain the deterioration in the sensory-motor learning of older adults. The theoretical implications and practical relevance of functional aging for motor skill learning are discussed. © 2013 Japan Geriatrics Society.

Hydride oxidation from a titanium–aluminum bimetallic complex: insertion, thermal and electrochemical reactivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, Alexandra C.; Altman, Alison B.; Lohrey, Trevor D.

We report the synthesis and reactivity of paramagnetic heterometallic complexes containing a Ti(III)-μ-H-Al(III) moiety. Combining different stoichiometries amounts of Cp 2TiCl and KH 3AlC(TMS) 3 (Cp = cyclopentadienyl, TMS = trimethylsilyl) resulted in the formation of either bimetallic Cp 2Ti(μ-H) 2(H)AlC(TMS) 3 (2) or trimetallic (Cp 2Ti) 2(μ-H) 3(H)AlC(TMS) 3 (3) via salt metathesis pathways. While these complexes were indefinitely stable at room temperature, the bridging hydrides were readily activated upon exposure to heteroallenes, heating, or electrochemical oxidation. In each case, formal hydride oxidation occurred, but the isolated product maintained the +3 oxidation state at both metal centers. The naturemore » of this reactivity was explored using deuterium labelling experiments and Density Functional Theory (DFT) calculations. It was found that while C–H activation from the Ti(III) bimetallic may occur through a σ-bond metathesis pathway, chemical oxidation to Ti(IV) promotes bimolecular reductive elimination of dihydrogen to form a Ti(III) product.« less

Hydride oxidation from a titanium–aluminum bimetallic complex: insertion, thermal and electrochemical reactivity

DOE PAGES

Brown, Alexandra C.; Altman, Alison B.; Lohrey, Trevor D.; ...

2017-05-31

We report the synthesis and reactivity of paramagnetic heterometallic complexes containing a Ti(III)-μ-H-Al(III) moiety. Combining different stoichiometries amounts of Cp 2TiCl and KH 3AlC(TMS) 3 (Cp = cyclopentadienyl, TMS = trimethylsilyl) resulted in the formation of either bimetallic Cp 2Ti(μ-H) 2(H)AlC(TMS) 3 (2) or trimetallic (Cp 2Ti) 2(μ-H) 3(H)AlC(TMS) 3 (3) via salt metathesis pathways. While these complexes were indefinitely stable at room temperature, the bridging hydrides were readily activated upon exposure to heteroallenes, heating, or electrochemical oxidation. In each case, formal hydride oxidation occurred, but the isolated product maintained the +3 oxidation state at both metal centers. The naturemore » of this reactivity was explored using deuterium labelling experiments and Density Functional Theory (DFT) calculations. It was found that while C–H activation from the Ti(III) bimetallic may occur through a σ-bond metathesis pathway, chemical oxidation to Ti(IV) promotes bimolecular reductive elimination of dihydrogen to form a Ti(III) product.« less

Characterization of a new TiF(4) and β-cyclodextrin inclusion complex and its in vitro evaluation on inhibiting enamel demineralization.

PubMed

Nassur, Camila; Alexandria, Adílis Kalina; Pomarico, Luciana; de Sousa, Valeria Pereira; Cabral, Lúcio Mendes; Maia, Lucianne Cople

2013-03-01

Titanium tetrafluoride (TiF(4)) is an effective but instable caries preventive agent. As the stability problems could be minimized through the use of drug carriers this study aimed to prepare and characterize a new TiF(4) nanoinclusion complex and to evaluate its potential in inhibiting enamel demineralization under pH cycling conditions. The TiF(4) nanosystems were prepared using β-cyclodextrin (βCD) and sodium montmorillonite (MMTNa). Bovine enamel blocks (n=48) with known surface microhardness (SMH), were randomly assigned to 4 groups (n=12) and submitted to one of the following treatments: distilled deionized water (as negative control) and solutions containing 1% βCD, 1% TiF(4) and TiF(4):βCD. The solutions were blinded applied once on the blocks with a microbrush(®) on the surface for 1min before pH-cycling. After that, samples were reavaluated by SMH, %SMH loss, cross-sectional microhardness (CSMH), scanning electron microscope (SEM) and energy dispersive spectrometry (EDX). The inclusion complex of TiF(4):βCD offered better protection against demineralization in the subsurface. The SEM analysis showed that TiF(4) and TiF(4):βCD samples presented the most intact enamel than the control. The EDX analysis identified titanium in TiF(4) and TiF(4):βCD groups. TiF(4):βCD has higher potential on inhibiting demineralization in the inner enamel. TiF(4):βCD is a new alternative to TiF(4) stabilization in order to reduce enamel subsurface demineralization. Copyright © 2012 Elsevier Ltd. All rights reserved.

SERS of semiconducting nanoparticles (TIO{sub 2} hybrid composites).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rajh, T.; Musumeci, A.; Gosztola, D.

Raman scattering of molecules adsorbed on the surface of TiO{sub 2} nanoparticles was investigated. We find strong enhancement of Raman scattering in hybrid composites that exhibit charge transfer absorption with TiO{sub 2} nanoparticles. An enhancement factor up to {approx}10{sup 3} was observed in the solutions containing TiO{sub 2} nanoparticles and biomolecules, including the important class of neurotransmitters such as dopamine and dopac (3,4-dihydroxy-phenylacetic acid). Only selected vibrations are enhanced, indicating molecular specificity due to distinct binding and orientation of the biomolecules coupled to the TiO{sub 2} surface. All enhanced modes are associated with the asymmetric vibrations of attached molecules thatmore » lower the symmetry of the charge transfer complex. The intensity and the energy of selected vibrations are dependent on the size and shape of nanoparticle support. Moreover, we show that localization of the charge in quantized nanoparticles (2 nm), demonstrated as the blue shift of particle absorption, diminishes SERS enhancement. Importantly, the smallest concentration of adsorbed molecules shows the largest Raman enhancements suggesting the possibility for high sensitivity of this system in the detection of biomolecules that form a charge transfer complex with metal oxide nanoparticles. The wavelength-dependent properties of a hybrid composite suggest a Raman resonant state. Adsorbed molecules that do not show a charge transfer complex show weak enhancements probably due to the dielectric cavity effect.« less

Photoionisation study of Xe.CF{sub 4} and Kr.CF{sub 4} van-der-Waals molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alekseev, V. A., E-mail: alekseev@va3474.spb.edu; Kevorkyants, R.; Garcia, G. A.

2016-05-14

We report on photoionization studies of Xe.CF{sub 4} and Kr.CF{sub 4} van-der-Waals complexes produced in a supersonic expansion and detected using synchrotron radiation and photoelectron-photoion coincidence techniques. The ionization potential of CF{sub 4} is larger than those of the Xe and Kr atoms and the ground state of the Rg.CF{sub 4}{sup +} ion correlates with Rg{sup +} ({sup 2}P{sub 3/2}) + CF{sub 4}. The onset of the Rg.CF{sub 4}{sup +} signals was found to be only ∼0.2 eV below the Rg ionization potential. In agreement with experiment, complementary ab initio calculations show that vertical transitions originating from the potential minimummore » of the ground state of Rg.CF{sub 4} terminate at a part of the potential energy surfaces of Rg.CF{sub 4}{sup +}, which are approximately 0.05 eV below the Rg{sup +} ({sup 2}P{sub 3/2}) + CF{sub 4} dissociation limit. In contrast to the neutral complexes, which are most stable in the face geometry, for the Rg.CF{sub 4}{sup +} ions, the calculations show that the minimum of the potential energy surface is in the vertex geometry. Experiments which have been performed only with Xe.CF{sub 4} revealed no Xe.CF{sub 4}{sup +} signal above the first ionization threshold of Xe, suggesting that the Rg.CF{sub 4}{sup +} ions are not stable above the first dissociation limit.« less

The environmental hypersensitivity symptom inventory: metric properties and normative data from a population-based study

PubMed Central

2013-01-01

Background High concomitant intolerance attributed to odorous/pungent chemicals, certain buildings, electromagnetic fields (EMF), and everyday sounds calls for a questionnaire instrument that can assess symptom prevalence in various environmental intolerances. The Environmental Hypersensitivity Symptom Inventory (EHSI) was therefore developed and metrically evaluated, and normative data were established. The EHSI consists of 34 symptom items, requires limited time to respond to, and provides a detailed and broad description of the individual’s symptomology. Methods Data from 3406 individuals who took part in the Västerbotten Environmental Health Study were used. The participants constitute a random sample of inhabitants in the county of Västerbotten in Sweden, aged 18 to 79 years, stratified for age and gender. Results Exploratory factor analysis identified five significant factors: airway symptoms (9 items; Kuder-Richardson Formula 20 coefficient, KR-20, of internal consistency = 0.74), skin and eye symptoms (6 items; KR-20 = 0.60), cardiac, dizziness and nausea symptoms (4 items; KR-20 = 0.55), head-related and gastrointestinal symptoms (5 items; KR-20 = 0.55), and cognitive and affective symptoms (10 items; KR-20 = 0.80). The KR-20 was 0.85 for the entire 34-item EHSI. Symptom prevalence rates in percentage for having the specific symptoms every week over the preceding three months constitute normative data. Conclusions The EHSI can be recommended for assessment of symptom prevalence in various types of environmental hypersensitivity, and with the advantage of comparing prevalence rates with normality. PMID:23837629

Reconstructing the Phylogenetic History of Long-Term Effective Population Size and Life-History Traits Using Patterns of Amino Acid Replacement in Mitochondrial Genomes of Mammals and Birds

PubMed Central

Nabholz, Benoit; Lartillot, Nicolas

2013-01-01

The nearly neutral theory, which proposes that most mutations are deleterious or close to neutral, predicts that the ratio of nonsynonymous over synonymous substitution rates (dN/dS), and potentially also the ratio of radical over conservative amino acid replacement rates (Kr/Kc), are negatively correlated with effective population size. Previous empirical tests, using life-history traits (LHT) such as body-size or generation-time as proxies for population size, have been consistent with these predictions. This suggests that large-scale phylogenetic reconstructions of dN/dS or Kr/Kc might reveal interesting macroevolutionary patterns in the variation in effective population size among lineages. In this work, we further develop an integrative probabilistic framework for phylogenetic covariance analysis introduced previously, so as to estimate the correlation patterns between dN/dS, Kr/Kc, and three LHT, in mitochondrial genomes of birds and mammals. Kr/Kc displays stronger and more stable correlations with LHT than does dN/dS, which we interpret as a greater robustness of Kr/Kc, compared with dN/dS, the latter being confounded by the high saturation of the synonymous substitution rate in mitochondrial genomes. The correlation of Kr/Kc with LHT was robust when controlling for the potentially confounding effects of nucleotide compositional variation between taxa. The positive correlation of the mitochondrial Kr/Kc with LHT is compatible with previous reports, and with a nearly neutral interpretation, although alternative explanations are also possible. The Kr/Kc model was finally used for reconstructing life-history evolution in birds and mammals. This analysis suggests a fairly large-bodied ancestor in both groups. In birds, life-history evolution seems to have occurred mainly through size reduction in Neoavian birds, whereas in placental mammals, body mass evolution shows disparate trends across subclades. Altogether, our work represents a further step toward a more comprehensive phylogenetic reconstruction of the evolution of life-history and of the population-genetics environment. PMID:23711670

Synthesis, characterization and antimicrobial investigation of some moxifloxacin metal complexes

NASA Astrophysics Data System (ADS)

Sadeek, Sadeek A.; El-Shwiniy, Walaa H.; El-Attar, Mohamed S.

2011-12-01

The new complexes of moxifloxacin (MOX), with Ti(IV), Y(III), Pd(II) and Ce(IV) have been synthesized. These complexes were then characterized by melting point, magnetic studies and spectroscopic techniques involving infrared spectra (IR), UV-Vis, 1H NMR. C, H, N and halogen elemental analysis and thermal behavior of complexes also investigated. The results suggested that the molar ratio for all complexes is M: MOX = 1:2 where moxifloxacin acts as a bidentate via one of the oxygen atoms of the carboxylate group and through the ring carbonyl group and the complexes have the following formula [Ti(MOX) 2](SO 4) 2·7H 2O, [Y(MOX) 2Cl 2]Cl·12H 2O, [Pd(MOX) 2(H 2O) 2]Cl 2·6H 2O and [Ce(MOX) 2](SO 4) 2·2H 2O. The activation energies, E*, enthalpies, Δ H*, entropies, Δ S* and Gibbs free energies, Δ G*, of the thermal decomposition reactions have been derived from thermogravimetric (TGA) and differential thermogravimetric (DrTG) curves, using Coats-Redfern (CR) and Horowitz-Metzger (HM) methods. The antimicrobial activity of these complexes has been evaluated against three Gram-positive and three Gram-negative bacteria and compared with the reference drug moxifloxacin. The antibacterial activity of Ti(IV) complex is significant for E. coli K32 and highly significant for S. aureus K1, B. subtilis K22, Br. otitidis K76, P. aeruginosa SW1 and K. oxytoca K42 compared with free moxifloxacin.

High-efficiency generation of pulsed Lyman-α radiation by resonant laser wave mixing in low pressure Kr-Ar mixture.

PubMed

Saito, Norihito; Oishi, Yu; Miyazaki, Koji; Okamura, Kotaro; Nakamura, Jumpei; Louchev, Oleg A; Iwasaki, Masahiko; Wada, Satoshi

2016-04-04

We report an experimental generation of ns pulsed 121.568 nm Lyman-α radiation by the resonant nonlinear four-wave mixing of 212.556 nm and 845.015 nm radiation pulses providing a high conversion efficiency 1.7x10^-3 with the output pulse energy 3.6 μJ achieved using a low pressure Kr-Ar mixture. Theoretical analysis shows that this efficiency is achieved due to the advantage of using (i) the high input laser intensities in combination with (ii) the low gas pressure allowing us to avoid the onset of full-scale discharge in the laser focus. In particular, under our experimental conditions the main mechanism of photoionization caused by the resonant 2-photon 212.556 nm radiation excitation of Kr atoms followed by the 1-photon ionization leads to ≈17% loss of Kr atoms and efficiency loss only by the end of the pulse. The energy of free electrons, generated by 212.556 nm radiation via (2 + 1)-photon ionization and accelerated mainly by 845.015 nm radiation, remains during the pulse below the level sufficient for the onset of full-scale discharge by the electron avalanche. Our analysis also suggests that ≈30-fold increase of 845.015 nm pulse energy can allow one to scale up the L-α radiation pulse energy towards the level of ≈100 μJ.

Characterization of two-phase flow regimes in horizontal tubes using 81mKr tracer experiments.

PubMed

Oriol, Jean; Leclerc, Jean Pierre; Berne, Philippe; Gousseau, Georges; Jallut, Christian; Tochon, Patrice; Clement, Patrice

2008-10-01

The diagnosis of heat exchangers on duty with respect to flow mal-distributions needs the development of non-intrusive inlet-outlet experimental techniques in order to perform an online fault diagnosis. Tracer experiments are an example of such techniques. They can be applied to mono-phase heat exchangers but also to multi-phase ones. In this case, the tracer experiments are more difficult to perform. In order to check for the capabilities of tracer experiments to be used for the flow mal-distribution diagnosis in the case of multi-phase heat exchangers, we present here a preliminary study on the simplest possible system: two-phase flows in a horizontal tube. (81m)Kr is used as gas tracer and properly collimated NaI (TI) crystal scintillators as detectors. The specific shape of the tracer response allows two-phase flow regimes to be characterized. Signal analysis allows the estimation of the gas phase real average velocity and consequently of the liquid phase real average velocity as well as of the volumetric void fraction. These results are compared successfully to those obtained with liquid phase tracer experiments previously presented by Oriol et al. 2007. Characterization of the two-phase flow regimes and liquid dispersion in horizontal and vertical tubes using coloured tracer and no intrusive optical detector. Chem. Eng. Sci. 63(1), 24-34, as well as to those given by correlations from literature.

Protein Structural Deformation Induced Lifetime Shortening of Photosynthetic Bacteria Light-Harvesting Complex LH2 Excited State

PubMed Central

Chen, Xing-Hai; Zhang, Lei; Weng, Yu-Xiang; Du, Lu-Chao; Ye, Man-Ping; Yang, Guo-Zhen; Fujii, Ritsuko; Rondonuwu, Ferdy S.; Koyama, Yasushi; Wu, Yi-Shi; Zhang, J. P.

2005-01-01

Photosynthetic bacterial light-harvesting antenna complex LH2 was immobilized on the surface of TiO2 nanoparticles in the colloidal solution. The LH2/TiO2 assembly was investigated by the time-resolved spectroscopic methods. The excited-state lifetimes for carotenoid-containing and carotenoidless LH2 have been measured, showing a decrease in the excited-state lifetime of B850 when LH2 was immobilized on TiO2. The possibility that the decrease of the LH2 excited-state lifetime being caused by an interfacial electron transfer reaction between B850 and the TiO2 nanoparticle was precluded experimentally. We proposed that the observed change in the photophysical properties of LH2 when assembled onto TiO2 nanoparticles is arising from the interfacial-interaction-induced structural deformation of the LH2 complex deviating from an ellipse of less eccentric to a more eccentric ellipse, and the observed phenomenon can be accounted by an elliptical exciton model. Experiment by using photoinactive SiO2 nanoparticle in place of TiO2 and core complex LH1 instead of LH2 provide further evidence to the proposed mechanism. PMID:15821161

Protein structural deformation induced lifetime shortening of photosynthetic bacteria light-harvesting complex LH2 excited state.

PubMed

Chen, Xing-Hai; Zhang, Lei; Weng, Yu-Xiang; Du, Lu-Chao; Ye, Man-Ping; Yang, Guo-Zhen; Fujii, Ritsuko; Rondonuwu, Ferdy S; Koyama, Yasushi; Wu, Yi-Shi; Zhang, J P

2005-06-01

Photosynthetic bacterial light-harvesting antenna complex LH2 was immobilized on the surface of TiO(2) nanoparticles in the colloidal solution. The LH2/TiO(2) assembly was investigated by the time-resolved spectroscopic methods. The excited-state lifetimes for carotenoid-containing and carotenoidless LH2 have been measured, showing a decrease in the excited-state lifetime of B850 when LH2 was immobilized on TiO(2). The possibility that the decrease of the LH2 excited-state lifetime being caused by an interfacial electron transfer reaction between B850 and the TiO(2) nanoparticle was precluded experimentally. We proposed that the observed change in the photophysical properties of LH2 when assembled onto TiO(2) nanoparticles is arising from the interfacial-interaction-induced structural deformation of the LH2 complex deviating from an ellipse of less eccentric to a more eccentric ellipse, and the observed phenomenon can be accounted by an elliptical exciton model. Experiment by using photoinactive SiO(2) nanoparticle in place of TiO(2) and core complex LH1 instead of LH2 provide further evidence to the proposed mechanism.

Hydration of Kr(aq) in dilute and concentrated solutions

DOE PAGES

Chaudhari, Mangesh I.; Sabo, Dubravko; Pratt, Lawrence R.; ...

2014-10-13

Molecular dynamics simulations of water with both multi-Kr and single Kr atomic solutes are carried out to implement quasi-chemical theory evaluation of the hydration free energy of Kr(aq). This approach obtains free energy differences reflecting Kr–Kr interactions at higher concentrations. Those differences are negative changes in hydration free energies with increasing concentrations at constant pressure. The changes are due to a slight reduction of packing contributions in the higher concentration case. The observed Kr–Kr distributions, analyzed with the extrapolation procedure of Krüger et al., yield a modestly attractive osmotic second virial coefficient, B2 ≈ -60 cm 3/mol. Moreover, the thermodynamicmore » analysis interconnecting these two approaches shows that they are closely consistent with each other, providing support for both approaches.« less

Heavy noble gases in solar wind delivered by Genesis mission.

PubMed

Meshik, Alex; Hohenberg, Charles; Pravdivtseva, Olga; Burnett, Donald

2014-02-15

One of the major goals of the Genesis Mission was to refine our knowledge of the isotopic composition of the heavy noble gases in solar wind and, by inference, the Sun, which represents the initial composition of the solar system. This has now been achieved with permil precision: 36 Ar/ 38 Ar = 5.5005 ± 0.0040, 86 Kr/ 84 Kr = .3012 ± .0004, 83 Kr/ 84 Kr = .2034 ± .0002, 82 Kr/ 84 Kr = .2054 ± .0002, 80 Kr/ 84 Kr = .0412 ± .0002, 78 Kr/ 84 Kr = .00642 ± .00005, 136 Xe/ 132 Xe = .3001 ± .0006, 134 Xe/ 132 Xe = .3691 ± .0007, 131 Xe/ 132 Xe = .8256 ± .0012, 130 Xe/ 132 Xe = .1650 ± .0004, 129 Xe/ 132 Xe = 1.0405 ± .0010, 128 Xe/ 132 Xe = .0842 ± .0003, 126 Xe/ 132 Xe = .00416 ± .00009, and 124 Xe/ 132 Xe = .00491 ± .00007 (error-weighted averages of all published data). The Kr and Xe ratios measured in the Genesis solar wind collectors generally agree with the less precise values obtained from lunar soils and breccias, which have accumulated solar wind over hundreds of millions of years, suggesting little if any temporal variability of the isotopic composition of solar wind krypton and xenon. The higher precision for the initial composition of the heavy noble gases in the solar system allows (1) to confirm that, exept 136 Xe and 134 Xe, the mathematically derived U-Xe is equivalent to Solar Wind Xe and (2) to provide an opportunity for better understanding the relationship between the starting composition and Xe-Q (and Q-Kr), the dominant current "planetary" component, and its host, the mysterious phase-Q.

Heavy noble gases in solar wind delivered by Genesis mission

PubMed Central

Meshik, Alex; Hohenberg, Charles; Pravdivtseva, Olga; Burnett, Donald

2017-01-01

One of the major goals of the Genesis Mission was to refine our knowledge of the isotopic composition of the heavy noble gases in solar wind and, by inference, the Sun, which represents the initial composition of the solar system. This has now been achieved with permil precision: 36Ar/38Ar = 5.5005 ± 0.0040, 86Kr/84Kr = .3012 ± .0004, 83Kr/84Kr = .2034 ± .0002, 82Kr/84Kr = .2054 ± .0002, 80Kr/84Kr = .0412 ± .0002, 78Kr/84Kr = .00642 ± .00005, 136Xe/132Xe = .3001 ± .0006, 134Xe/132Xe = .3691 ± .0007, 131Xe/132Xe = .8256 ± .0012, 130Xe/132Xe = .1650 ± .0004, 129Xe/132Xe = 1.0405 ± .0010, 128Xe/132Xe = .0842 ± .0003, 126Xe/132Xe = .00416 ± .00009, and 124Xe/132Xe = .00491 ± .00007 (error-weighted averages of all published data). The Kr and Xe ratios measured in the Genesis solar wind collectors generally agree with the less precise values obtained from lunar soils and breccias, which have accumulated solar wind over hundreds of millions of years, suggesting little if any temporal variability of the isotopic composition of solar wind krypton and xenon. The higher precision for the initial composition of the heavy noble gases in the solar system allows (1) to confirm that, exept 136Xe and 134Xe, the mathematically derived U–Xe is equivalent to Solar Wind Xe and (2) to provide an opportunity for better understanding the relationship between the starting composition and Xe-Q (and Q-Kr), the dominant current “planetary” component, and its host, the mysterious phase-Q. PMID:29151613

A new route for the synthesis of titanium silicalite-1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vasile, Aurelia, E-mail: aurelia_vasile@yahoo.com; Busuioc-Tomoiaga, Alina Maria; Catalysis Research Department, ChemPerformance SRL, Iasi 700337

2012-01-15

Graphical abstract: Well-prepared TS-1 was synthesized by an innovative procedure using inexpensive reagents such as fumed silica and TPABr as structure-directing agent. This is the first time when highly crystalline TS-1 is obtained in basic medium, using sodium hydroxide as HO{sup -} ion source required for the crystallization process. Hydrolysis of titanium source has been prevented by titanium complexation with acetylacetone before structuring gel. Highlights: Black-Right-Pointing-Pointer TS-1 was obtained using cheap reagents as fumed silica and tetrapropylammonium bromide. Black-Right-Pointing-Pointer First time NaOH was used as source of OH{sup -} ions required for crystallization process. Black-Right-Pointing-Pointer The hydrolysis Ti alkoxides wasmore » controlled by Ti complexation with 2,4-pentanedione. -- Abstract: A new and efficient route using inexpensive reagents such as fumed silica and tetrapropylammonium bromide is proposed for the synthesis of titanium silicalite-1. High crystalline titanium silicalite-1 was obtained in alkaline medium, using sodium hydroxide as HO{sup -} ion source required for the crystallization process. Hydrolysis of titanium source with formation of insoluble oxide species was prevented by titanium complexation with before structuring gel. The final solids were fully characterized by powder X-ray diffraction, scanning electron microscopy, Fourier transform infrared, ultraviolet-visible diffuse reflectance, Raman and atomic absorption spectroscopies, as well as nitrogen sorption analysis. It was found that a molar ratio Ti:Si of about 0.04 in the initial reaction mixture is the upper limit to which well formed titanium silicalite-1 with channels free of crystalline or amorphous material can be obtained. Above this value, solids with MFI type structure containing both Ti isomorphously substituted in the network and extralattice anatase nanoparticles inside of channels is formed.« less

Development of a High Resolution X-Ray Spectrometer for the National Ignition Facility (NIF)

NASA Astrophysics Data System (ADS)

Hill, K. W.; Bitter, M.; Delgado-Aparicio, L.; Efthimion, P. C.; Ellis, R.; Gao, L.; Maddox, J.; Pablant, N. A.; Schneider, M. B.; Chen, H.; Ayers, S.; Kauffman, R. L.; Macphee, A. G.; Beiersdorfer, P.; Ma, T.; Nora, R. C.; Scott, H. A.; Thorn, D. B.; Kilkenny, J. D.; Nelson, D.; Shoup, M., III; Maron, Y.

2016-10-01

A high resolution (E/ ΔE 2000) Bragg crystal x-ray spectrometer is being developed to measure plasma parameters in NIF experiments. The instrument will be a positioner insertable cassette designed to infer electron density in compressed capsules from Stark broadening of the helium- β (1s2-1s3p) lines of krypton, and electron temperature from the relative intensities of dielectronic satellites. Two conically shaped crystals will diffract and sagittally focus (1) the Kr He β complex and (2) the He α and Ly α complexes onto a streak camera photocathode for time resolved measurement. A third cylindrical crystal will focus the full He α to He β spectrum onto an image plate for a time integrated calibration spectrum. Performance estimates and design status will be presented. Performed under the auspices of the US DOE by PPPL under contract DE-AC02-09CH11466 and by LLNL under contract DE-AC52-07NA27344.

SEM and TEM characterization of microstructure of stainless steel composites reinforced with TiB{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sulima, Iwona, E-mail: isulima@up.krakow.pl

Steel-8TiB{sub 2} composites were produced by two new sintering techniques, i.e. Spark Plasma Sintering (SPS) and High Pressure-High Temperature (HP-HT) sintering. This study discusses the impact of these sintering methods on the microstructure of steel composites reinforced with TiB{sub 2} particles. Scanning electron microscopy (SEM), wavelength dispersive spectroscopy (WDS), X-ray diffraction, electron backscatter diffraction (EBSD) and transmission electron microscopy (TEM) were used to analyze the microstructure evolution in steel matrix composites. The results of microscopic examinations revealed a close relationship between the composite microstructure and the methods and conditions of sintering. Substantial differences were observed in the grain size ofmore » materials sintered by HP-HT and SPS. It has been demonstrated that the composites sintered by HP-HT tend to form a chromium-iron-nickel phase in the steel matrix. In contrast, the microstructure of the composites sintered by SPS is characterized by the presence of complex borides and chromium-iron phase. - Highlights: •The steel-8TiB{sub 2} composites were fabricated by Spark Plasma Sintering (SPS) and High Pressure-High Temperature (HP-HT). •Sintering techniques has an important effect on changes in the microstructure of steel-8TiB{sub 2} composites. •New phases of different size and morphology were identified.« less

Hormonal regulation and developmental role of Krüppel homolog 1, a repressor of metamorphosis, in the silkworm Bombyx mori.

PubMed

Kayukawa, Takumi; Murata, Mika; Kobayashi, Isao; Muramatsu, Daisuke; Okada, Chieko; Uchino, Keiro; Sezutsu, Hideki; Kiuchi, Makoto; Tamura, Toshiki; Hiruma, Kiyoshi; Ishikawa, Yukio; Shinoda, Tetsuro

2014-04-01

Juvenile hormone (JH) has an ability to repress the precocious metamorphosis of insects during their larval development. Krüppel homolog 1 (Kr-h1) is an early JH-inducible gene that mediates this action of JH; however, the fine hormonal regulation of Kr-h1 and the molecular mechanism underlying its antimetamorphic effect are little understood. In this study, we attempted to elucidate the hormonal regulation and developmental role of Kr-h1. We found that the expression of Kr-h1 in the epidermis of penultimate-instar larvae of the silkworm Bombyx mori was induced by JH secreted by the corpora allata (CA), whereas the CA were not involved in the transient induction of Kr-h1 at the prepupal stage. Tissue culture experiments suggested that the transient peak of Kr-h1 at the prepupal stage is likely to be induced cooperatively by JH derived from gland(s) other than the CA and the prepupal surge of ecdysteroid, although involvement of unknown factor(s) could not be ruled out. To elucidate the developmental role of Kr-h1, we generated transgenic silkworms overexpressing Kr-h1. The transgenic silkworms grew normally until the spinning stage, but their development was arrested at the prepupal stage. The transgenic silkworms from which the CA were removed in the penultimate instar did not undergo precocious pupation or larval-larval molt but fell into prepupal arrest. This result demonstrated that Kr-h1 is indeed involved in the repression of metamorphosis but that Kr-h1 alone is incapable of implementing normal larval molt. Moreover, the expression profiles and hormonal responses of early ecdysone-inducible genes (E74, E75, and Broad) in transgenic silkworms suggested that Kr-h1 is not involved in the JH-dependent modulation of these genes, which is associated with the control of metamorphosis. Copyright © 2014 Elsevier Inc. All rights reserved.

Investigations of the Rg-BrCl (Rg=He, Ne, Ar, Kr, Xe) binary van der Waals complexes: ab initio intermolecular potential energy surfaces, vibrational states and predicted pure rotational transition frequencies.

PubMed

Li, Song; Zheng, Rui; Chen, Shan-Jun; Chen, Yan; Chen, Peng

2017-03-05

The intermolecular potential energy surfaces (PESs) of the ground electronic state for the Rg-BrCl (Rg=He, Ne, Ar, Kr, Xe) van der Waals complexes have been constructed by using the coupled-cluster method in combination with the augmented quadruple-zeta correlation-consistent basis sets supplemented with an additional set of bond functions. The features of the anisotropic PESs for these complexes are remarkably similar, which are characterized by three minima and two saddle points between them. The global minimum corresponds to a collinear Rg-Br-Cl configuration. Two local minima, correlate with an anti-linear Rg-Cl-Br geometry and a nearly T-shaped structure, can also be located on each PES. The quantum bound state calculations enable us to investigate intermolecular vibrational states and rotational energy levels of the complexes. The transition frequencies are predicted and are fitted to obtain their corresponding spectroscopic constants. In general, the periodic trends are observed for this complex family. Comparisons with available experimental data for the collinear isomer of Ar-BrCl demonstrate reliability of our theoretical predictions, and our results for the other two isomers of Ar-BrCl as well as for other members of the complex family are also anticipated to be trustable. Except for the collinear isomer of Ar-BrCl, the data presented in this paper would be beneficial to improve our knowledge for these experimentally unknown species. Copyright © 2016 Elsevier B.V. All rights reserved.

On the size and structure of helium snowballs formed around charged atoms and clusters of noble gases.

PubMed

Bartl, Peter; Leidlmair, Christian; Denifl, Stephan; Scheier, Paul; Echt, Olof

2014-09-18

Helium nanodroplets doped with argon, krypton, or xenon are ionized by electrons and analyzed in a mass spectrometer. HenNgx(+) ions containing up to seven noble gas (Ng) atoms and dozens of helium atoms are identified; the high resolution of the mass spectrometer combined with advanced data analysis make it possible to unscramble contributions from isotopologues that have the same nominal mass but different numbers of helium or Ng atoms, such as the magic He20(84)Kr2(+) and the isobaric, nonmagic He41(84)Kr(+). Anomalies in these ion abundances reveal particularly stable ions; several intriguing patterns emerge. Perhaps most astounding are the results for HenAr(+), which show evidence for three distinct, solid-like solvation shells containing 12, 20, and 12 helium atoms. This observation runs counter to the common notion that only the first solvation shell is solid-like but agrees with calculations by Galli et al. for HenNa(+) [J. Phys. Chem. A 2011, 115, 7300] that reveal three shells of icosahedral symmetry. HenArx(+) (2 ≤ x ≤ 7) ions appear to be especially stable if they contain a total of n + x = 19 atoms. A sequence of anomalies in the abundance distribution of HenKrx(+) suggests that rings of six helium atoms are inserted into the solvation shell each time a krypton atom is added to the ionic core, from Kr(+) to Kr3(+). Previously reported strong anomalies at He12Kr2(+) and He12Kr3(+) [Kim , J. H.; et al. J. Chem. Phys. 2006, 124, 214301] are attributed to a contamination. Only minor local anomalies appear in the distributions of HenXex(+) (x ≤ 3). The distributions of HenKr(+) and HenXe(+) show strikingly similar, broad features that are absent from the distribution of HenAr(+); differences are tentatively ascribed to the very different fragmentation dynamics of these ions.

On the Size and Structure of Helium Snowballs Formed around Charged Atoms and Clusters of Noble Gases

PubMed Central

2013-01-01

Helium nanodroplets doped with argon, krypton, or xenon are ionized by electrons and analyzed in a mass spectrometer. HenNgx+ ions containing up to seven noble gas (Ng) atoms and dozens of helium atoms are identified; the high resolution of the mass spectrometer combined with advanced data analysis make it possible to unscramble contributions from isotopologues that have the same nominal mass but different numbers of helium or Ng atoms, such as the magic He2084Kr2+ and the isobaric, nonmagic He4184Kr+. Anomalies in these ion abundances reveal particularly stable ions; several intriguing patterns emerge. Perhaps most astounding are the results for HenAr+, which show evidence for three distinct, solid-like solvation shells containing 12, 20, and 12 helium atoms. This observation runs counter to the common notion that only the first solvation shell is solid-like but agrees with calculations by Galli et al. for HenNa+ [J. Phys. Chem. A2011, 115, 730021568337] that reveal three shells of icosahedral symmetry. HenArx+ (2 ≤ x ≤ 7) ions appear to be especially stable if they contain a total of n + x = 19 atoms. A sequence of anomalies in the abundance distribution of HenKrx+ suggests that rings of six helium atoms are inserted into the solvation shell each time a krypton atom is added to the ionic core, from Kr+ to Kr3+. Previously reported strong anomalies at He12Kr2+ and He12Kr3+ [KimJ. H.; et al. J. Chem. Phys.2006, 124, 21430116774401] are attributed to a contamination. Only minor local anomalies appear in the distributions of HenXex+ (x ≤ 3). The distributions of HenKr+ and HenXe+ show strikingly similar, broad features that are absent from the distribution of HenAr+; differences are tentatively ascribed to the very different fragmentation dynamics of these ions. PMID:24128371

Strong polarization enhancement in asymmetric three-component ferroelectric superlattices

NASA Astrophysics Data System (ADS)

Lee, Ho Nyung; Christen, Hans M.; Chisholm, Matthew F.; Rouleau, Christopher M.; Lowndes, Douglas H.

2005-01-01

Theoretical predictions-motivated by recent advances in epitaxial engineering-indicate a wealth of complex behaviour arising in superlattices of perovskite-type metal oxides. These include the enhancement of polarization by strain and the possibility of asymmetric properties in three-component superlattices. Here we fabricate superlattices consisting of barium titanate (BaTiO3), strontium titanate (SrTiO3) and calcium titanate (CaTiO3) with atomic-scale control by high-pressure pulsed laser deposition on conducting, atomically flat strontium ruthenate (SrRuO3) layers. The strain in BaTiO3 layers is fully maintained as long as the BaTiO3 thickness does not exceed the combined thicknesses of the CaTiO3 and SrTiO3 layers. By preserving full strain and combining heterointerfacial couplings, we find an overall 50% enhancement of the superlattice global polarization with respect to similarly grown pure BaTiO3, despite the fact that half the layers in the superlattice are nominally non-ferroelectric. We further show that even superlattices containing only single-unit-cell layers of BaTiO3 in a paraelectric matrix remain ferroelectric. Our data reveal that the specific interface structure and local asymmetries play an unexpected role in the polarization enhancement.

Effect of the carbon coating in Fe-C-TiO(2) photocatalyst on phenol decomposition under UV irradiation via photo-Fenton process.

PubMed

Tryba, Beata; Morawski, Antoni W; Inagaki, Michio; Toyoda, Masahiro

2006-08-01

Fe-C-TiO(2) photocatalysts which contained the residue carbon (0.2-3.3 mass%) were prepared from a mixture of TiO(2) and FeC(2)O(4) through the heating at 673-1173 K in Ar. These photocatalysts did not show a high adsorption of phenol, but they were active in photo-Fenton reactions during decomposition of phenol under UV irradiation with addition of H(2)O(2). It was proved that Fe(2+) governed the photoactivity of Fe-C-TiO(2) photocatalysts, it decreased with heat-treatment temperature above 773 K. For comparison, Fe-TiO(2) photocatalyst was prepared by heating TiO(2) and FeC(2)O(4) at 823 K in air for 3h. Phenol decomposition was going much slower on Fe-TiO(2) photocatalyst in comparison with Fe-C-TiO(2), of which mechanism was different, on the former phenol was decomposed by the radical reaction, on the latter through a complex reaction with iron and intermediates of phenol decomposition. Therefore carbon-coating TiO(2) was found to be advantageous for mounting iron and its application for the phenol decomposition via photo-Fenton process.

H and Au diffusion in high mobility a-InGaZnO thin-film transistors via low temperature KrF excimer laser annealing

NASA Astrophysics Data System (ADS)

Bermundo, Juan Paolo S.; Ishikawa, Yasuaki; Fujii, Mami N.; Ikenoue, Hiroshi; Uraoka, Yukiharu

2017-03-01

We report the fabrication of high mobility amorphous InGaZnO (a-IGZO) thin-film transistors (TFTs) irradiated by a single shot of a 248 nm KrF excimer laser. Very high mobilities (μ) of up to 43.5 cm2/V s were obtained after the low temperature excimer laser annealing (ELA) process. ELA induces high temperatures primarily in the upper layers and maintains very low temperatures of less than 50 °C in the substrate region. Scanning Transmission Electron micrographs show no laser induced damage and clear interfaces after the laser irradiation. In addition, several characterization studies were performed to determine the μ improvement mechanism. The analysis of Secondary Ion Mass Spectrometry and X-ray Photoelectron Spectroscopy suggests incorporation of H mainly from the hybrid passivation layer into the channel. Moreover, Energy-dispersive X-ray Spectroscopy results show that Au diffused into the channel after ELA. Both KrF ELA-induced H and Au diffusion contributed to the higher μ. These results demonstrate that ELA can greatly enhance the electrical properties of a-IGZO TFTs for promising applications in large area, transparent, and flexible electronics.

Spectroscopy of Photovoltaic Materials: Charge-Transfer Complexes and Titanium Dioxide

NASA Astrophysics Data System (ADS)

Dillon, Robert John

The successful function of photovoltaic (PV) and photocatalytic (PC) systems centers primarily on the creation and photophysics of charge separated electron-hole pairs. The pathway leading to separate carriers varies by material; organic materials typically require multiple events to charge separate, whereas inorganic semiconductors can directly produce free carriers. In this study, time-resolved spectroscopy is used to provide insight into two such systems: 1) organic charge-transfer (CT) complexes, where electrons and holes are tightly bound to each other, and 2) Au-TiO2 core-shell nanostructures, where free carriers are directly generated. 1) CT complexes are structurally well defined systems consisting of donor molecules, characterized by having low ionization potentials, and acceptor molecules, characterized by having high electron affinities. Charge-transfer is the excitation of an electron from the HOMO of a donor material directly into the LUMO of the acceptor material, leading to an electron and hole separated across the donor:acceptor interface. The energy of the CT transition is often less than that of the bandgaps of donor and acceptor materials individually, sparking much interest if PV systems can utilize the CT band to generate free carriers from low energy photons. In this work we examine the complexes formed between acceptors tetracyanobenzene (TCNB) and tetracyanoquinodimethane (TCNQ) with several aromatic donors. We find excitation of the charge-transfer band of these systems leads to strongly bound electron-hole pairs that exclusively undergo recombination to the ground state. In the case of the TCNB complexes, our initial studies were flummoxed by the samples' generally low threshold for photo and mechanical damage. As our results conflicted with previous literature, a significant portion of this study was spent quantifying the photodegradation process. 2) Unlike the previous system, free carriers are directly photogenerated in TiO2, and the prime consideration is avoiding loss due to recombination of the electron and hole. In this study, four samples of core-shell Au-TiO 2 nanostructures are analyzed for their photocatalytic activity and spectroscopic properties. The samples were made with increasingly crystalline TiO2 shells. The more crystalline samples had higher photocatalytic activities, attributed to longer carrier lifetimes. The observed photophysics of these samples vary with excitation wavelength and detection method used. We find the time-resolved photoluminescence correlates with the samples' photocatalytic activities only when high energy, excitation wavelength less than or equal to 300 nm is used, while transient absorption experiments show no correlation regardless of excitation source. The results imply that photoexcitation with high energy photons can generate both reactive surface sites and photoluminescent surface sites in parallel. Both types of sites then undergo similar electron-hole recombination processes that depend on the crystallinity of the TiO2 shell. Surface sites created by low energy photons, as well as bulk TiO2 carrier dynamics that are probed by transient absorption, do not appear to be sensitive to the same dynamics that determine chemical reactivity.

Beyond the structure-property relationship paradigm: influence of the crystal structure and microstructure on the Li+ conductivity of La2/3Li(x)Ti(1-x)Al(x)O3 Oxides.

PubMed

García-Martín, Susana; Morata-Orrantía, Ainhoa; Alario-Franco, Miguel A; Rodríguez-Carvajal, Juan; Amador, Ulises

2007-01-01

The crystal structures of several oxides of the La(2/3)Li(x)Ti(1-x)Al(x)O(3) system have been studied by selected-area electron diffraction, high-resolution transmission electron microscopy, and powder neutron diffraction, and their lithium conductivity has been by complex impedance spectroscopy. The compounds have a perovskite-related structure with a unit cell radical2 a(p)x2 a(p)x radical2 a(p) (a(p)=perovskite lattice parameter) due to the tilting of the (Ti/Al)O(6) octahedra and the ordering of lanthanum and lithium ions and vacancies along the 2 a(p) axis. The Li(+) ions present a distorted square-planar coordination and are located in interstitial positions of the structure, which could explain the very high ionic conductivity of this type of material. The lithium conductivity depends on the oxide composition and its crystal microstructure, which varies with the thermal treatment of the sample. The microstructure of these titanates is complex due to formation of domains of ordering and other defects such as strains and compositional fluctuations.

Three-dimensional nanometer scale analyses of precipitate structures and local compositions in titanium aluminide engineering alloys

NASA Astrophysics Data System (ADS)

Gerstl, Stephan S. A.

Titanium aluminide (TiAl) alloys are among the fastest developing class of materials for use in high temperature structural applications. Their low density and high strength make them excellent candidates for both engine and airframe applications. Creep properties of TiAl alloys, however, have been a limiting factor in applying the material to a larger commercial market. In this research, nanometer scale compositional and structural analyses of several TiAl alloys, ranging from model Ti-Al-C ternary alloys to putative commercial alloys with 10 components are investigated utilizing three dimensional atom probe (3DAP) and transmission electron microscopies. Nanometer sized borides, silicides, and carbide precipitates are involved in strengthening TiAl alloys, however, chemical partitioning measurements reveal oxygen concentrations up to 14 at. % within the precipitate phases, resulting in the realization of oxycarbide formation contributing to the precipitation strengthening of TiAl alloys. The local compositions of lamellar microstructures and a variety of precipitates in the TiAl system, including boride, silicide, binary carbides, and intermetallic carbides are investigated. Chemical partitioning of the microalloying elements between the alpha2/gamma lamellar phases, and the precipitate/gamma-matrix phases are determined. Both W and Hf have been shown to exhibit a near interfacial excess of 0.26 and 0.35 atoms nm-2 respectively within ca. 7 nm of lamellar interfaces in a complex TiAl alloy. In the case of needle-shaped perovskite Ti3AlC carbide precipitates, periodic domain boundaries are observed 5.3+/-0.8 nm apart along their growth axis parallel to the TiAl[001] crystallographic direction with concomitant composition variations after 24 hrs. at 800°C.

Adsorption and breakdown of penicillin antibiotic in the presence of titanium oxide nanoparticles in water.

PubMed

Peterson, Jonathan W; Petrasky, Laura J; Seymour, Michael D; Burkhart, Rachel S; Schuiling, Amanda B

2012-05-01

The fate and transport of antibiotics in natural water systems is controlled in part by interactions with nanometer (10(-9)m) metal oxide particles. Experiments were performed by mixing solutions of ampicillin (AMP), a common, penicillin-class human and veterinary antibiotic, with 25 nm-TiO(2) (anatase) nanoparticles at different pH conditions. Both sorption and degradation of AMP were observed in the AMP-nanoparticle solutions. For AMP concentrations from ~3 μM to 2.9 mM the overall AMP removal from solution can be described by linear isotherms with removal coefficients (K(r)) of 3028 (±267)L kg(-1) at pH 2, 11,533 (±823)L kg(-1) at pH 4, 12,712 (±672)L kg(-1) at pH 6, and 1941 (±342)L kg(-1) at pH 8. Mass spectral analysis of AMP solutions after removal of the solid nanoparticles yielded ions that indicate the presence of peniclloic acid, penilloic acid and related de-ammoniated by-products as possible compounds resulting from the degradation of AMP at the TiO(2) surface. Copyright © 2012 Elsevier Ltd. All rights reserved.

LL-37-derived short antimicrobial peptide KR-12-a5 and its d-amino acid substituted analogs with cell selectivity, anti-biofilm activity, synergistic effect with conventional antibiotics, and anti-inflammatory activity.

PubMed

Kim, Eun Young; Rajasekaran, Ganesan; Shin, Song Yub

2017-08-18

KR-12-a5 is a 12-meric α-helical antimicrobial peptide (AMP) with dual antimicrobial and anti-inflammatory activities designed from human cathelicidin LL-37. We designed and synthesized a series of d-amino acid-substituted analogs of KR-12-a5 with the aim of developing novel α-helical AMPs that possess higher cell selectivity than KR-12-a5, while maintaining the anti-inflammatory activity. d-amino acid incorporation into KR-12-a5 induced a significant improvement in the cell selectivity by 2.6- to 13.6-fold as compared to KR-12-a5, while maintaining the anti-inflammatory activity. Among the three analogs, KR-12-a5 (6- D L) with d-amino acid in the polar-nonpolar interface (Leu 6 ) showed the highest cell selectivity (therapeutic index: 61.2). Similar to LL-37, KR-12-a5 and its analogs significantly inhibited the expression and secretion of NO, TNF-α, IL-6 and MCP-1 from LPS-stimulated RAW264.7 cells. KR-12-a5 and its analogs showed a more potent antimicrobial activity against antibiotic-resistant bacteria, including clinically isolated MRSA, MDRPA, and VREF than LL-37 and melittin. Furthermore, compared to LL-37, KR-12-a5 and its analogs showed greater synergistic effects with conventional antibiotics, such as chloramphenicol, ciprofloxacin, and oxacillin against MDRPA; KR-12-a5 and its analogs had a FICI range between 0.25 and 0.5, and LL-37 had a range between 0.75 and 1.5. KR-12-a5 and its analogs were found to be more effective anti-biofilm agents against MDRPA than LL-37. In addition, KR-12-a5 and its analogs maintained antimicrobial activity in physiological salts and human serum. SYTOX Green uptake and membrane depolarization studies revealed that KR-12-a5 and its analogs kills microbial cells by permeabilizing the cell membrane and damaging membrane integrity. Taken together, our results suggest that KR-12-a5 and its analogs can be developed further as novel antimicrobial/anti-inflammatory agents to treat antibiotic-resistant infections. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Excitation mechanism in a hollow cathode He-Kr ion laser

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hazama, J.; Arai, T.; Goto, M.

1995-12-31

Pulsed laser operation in the afterglow of a positive column He-Kr discharge on the 469.4 nm (6s{sup 4}P{sub 5/2} {yields} 5p{sup 4}P{sub 5/2}) transition of Kr(II) was observed for the first time by Dana and Laure`s. It appears that the upper level of Kr(II) laser line is populated by the second kind collisions between He 2{sup 3}S metastable atoms and ground state Kr ions. CW oscillations on Kr(II) transitions have been obtained in a hollow cathode discharge. In this work, we have estimated the excitation mechanism for the upper state of 469.4 nm laser line from the measurements of themore » decay of endlight intensity in the hollow cathode He-Kr discharge.« less

Binding investigation on the interaction between Methylene Blue (MB)/TiO2 nanocomposites and bovine serum albumin by resonance light-scattering (RLS) technique and fluorescence spectroscopy.

PubMed

Li, Yuesheng; Zhang, Yue; Sun, Shaofa; Zhang, Aiqing; Liu, Yi

2013-11-05

The interaction between Methylene Blue (MB)/TiO2 nanocomposites and bovine serum albumin (BSA) was investigated by resonance light scattering (RLS), fluorescence, three-dimension spectra and UV-vis absorbance spectroscopy. Several factors which may influence the RLS intensity were also investigated before characterizing MB/TiO2-BSA complex. It was proved that the mechanism of MB/TiO2 nanocomposites binding to BSA was mainly a result of the formation of MB/TiO2-BSA complex. The binding constant of MB/TiO2-BSA is 0.762 × 10(-5) L mol(-1) at 298K. By calculating the binding constant at different temperature, the thermodynamic parameters ΔH, ΔG, and ΔS can be observed and deduced that the hydrophobic interactions played an important role to stabilize the complex. The distance r (3.73 nm) between donor (BSA) and acceptor (MB/TiO2) was obtained according to fluorescence resonance energy transfer (FRET). The binding site for MB/TiO2 on BSA was mainly located in sub-domain IIA. The UV-vis absorbance, circular dichroism and three dimension fluorescence have also been used to investigate the effect of MB/TiO2 on the conformation of BSA. Copyright © 2013 Elsevier B.V. All rights reserved.

Dielectric characteristics of Mn-doped LaTiO3+δ ceramics

NASA Astrophysics Data System (ADS)

Chen, Yan; Cui, Yimin

A series of ceramic composites of Mn-doped La1- x MnxTiO3+ δ and LaMnxTi1- x O3+ δ (x = 0.1, 0.2) were synthesized by conventional solid-state reaction method. The low-frequency complex dielectric properties of the composites were investigated as functions of temperature (77 K <= T <= 360 K) and frequency (100 Hz <= f <= 1 MHz), respectively. The dielectric constant of A-site doped samples is higher than that of B-site doped samples. The loss tangent of low doped samples is much less than that of high doped samples. The A-site doped composites exhibit intrinsic dielectric response with a dielectric constant of 40 in the temperature below 250 K. Interestingly, the dielectric constants of B-site doped ceramics increase slightly in the temperature range from 77 to 360 K. And it is clearly observed that extraordinarily high dielectric loss tangent ( 6) appear at low frequency (100 Hz) in LaMn0.2Ti0.8O3+ δ , which is 8 times larger than that of LaMn0.1Ti0.9O3+ δ , which indicates that the doped content can affect the intrinsic dielectric characteristics significantly.

Disorder engineering of undoped TiO2 nanotube arrays for highly efficient solar-driven oxygen evolution.

PubMed

Salari, M; Aboutalebi, S H; Aghassi, A; Wagner, P; Mozer, A J; Wallace, G G

2015-02-28

The trade-off between performance and complexity of the device manufacturing process should be balanced to enable the economic harvest of solar energy. Here, we demonstrate a conceptual, yet practical and well-regulated strategy to achieve efficient solar photocatalytic activity in TiO2 through controlled phase transformation and disorder engineering in the surface layers of TiO2 nanotubes. This approach enabled us to fine-tune the bandgap structure of undoped TiO2 according to our needs while simultaneously obtaining robust separation of photo-excited charge carriers. Introduction of specific surface defects also assisted in utilization of the visible part of sunlight to split water molecules for the production of oxygen. The strategy proposed here can serve as a guideline to overcome the practical limitation in the realization of efficient, non-toxic, chemically stable photoelectrochemical systems with high catalytic activity at neutral pH under visible illumination conditions. We also successfully incorporated TiO2 nanotube arrays (TNTAs) with free-based porphyrin affording a pathway with an overall 140% enhanced efficiency, an oxygen evolution rate of 436 μL h(-1) and faradic efficiencies over 100%.

Synthesis and Reactivity of Siloxide and Silamide Complexes Pertaining to Bond Breaking and Aggregation Phenomena

DTIC Science & Technology

1992-07-01

Dimeriza- tion of a Titanium Ketyl: (silox)3TiOCPh2. (silox) = tBu 3SiO’)." Covert, K.J.; Wolczanski, P.T. Inorg. Chem. 1989, 28, 4565-4567. "Ketyl...underwent subsequent reactivity. Acetone reacted with 14 to give isopropoxide and 2-propenoxide species, (silox)3Ti-(OCHMe2) (16) and (silox) 3Ti(OMeC...Activations by Tri-tert-butylsilylimido Complexes of Titanium . "Tri-tert-butylsilylimido Complexes of Titanium : Benzene C-H Activation and Struc- ture

Probing surface sites of TiO2: reactions with [HRe(CO)5] and [CH3Re(CO)5].

PubMed

Lobo-Lapidus, Rodrigo J; Gates, Bruce C

2010-10-04

Two carbonyl complexes of rhenium, [HRe(CO)(5)] and [CH(3)Re(CO)(5)], were used to probe surface sites of TiO(2) (anatase). These complexes were adsorbed from the gas phase onto anatase powder that had been treated in flowing O(2) or under vacuum to vary the density of surface OH sites. Infrared (IR) spectra demonstrate the variation in the number of sites, including Ti(+3)-OH and Ti(+4)-OH. IR and extended X-ray absorption fine structure (EXAFS) spectra show that chemisorption of the rhenium complexes led to their decarbonylation, with formation of surface-bound rhenium tricarbonyls, when [HRe(CO)(5)] was adsorbed, or rhenium tetracarbonyls, when [CH(3)Re(CO)(5)] was adsorbed. These reactions were accompanied by the formation of water and surface carbonates and removal of terminal hydroxyl groups associated with Ti(+3) and Ti(+4) ions on the anatase. Data characterizing the samples after adsorption of [HRe(CO)(5)] or [CH(3)Re(CO)(5)] determined a ranking of the reactivity of the surface OH sites, with the Ti(+3)-OH groups being the more reactive towards the rhenium complexes but the less likely to be dehydroxylated. The two rhenium pentacarbonyl probes provided complementary information, suggesting that the carbonate species originate from carbonyl ligands initially bonded to the rhenium and from hydroxyl groups of the titania surface, with the reaction leading to the formation of water and bridging hydroxyl groups on the titania. The results illustrate the value of using a family of organometallic complexes as probes of oxide surface sites.

Interfacial charge-transfer transitions in a TiO2-benzenedithiol complex with Ti-S-C linkages.

PubMed

Fujisawa, Jun-ichi; Muroga, Ryuki; Hanaya, Minoru

2015-11-28

Interfacial charge-transfer (ICT) transitions between organic materials and inorganic semiconductors are a new mechanism for light absorption at organic-semiconductor interfaces. ICT transitions cause one-step interfacial charge separation without loss of energy. This feature is potentially useful to realize efficient organic-inorganic hybrid solar cells. ICT transitions have been examined by employing titanium dioxide (TiO2) nanoparticles chemisorbed with π-conjugated molecules via Ti-O-C linkages. Here, we report ICT transitions in a TiO2 and 1,2-benzenedithiol (BDT) complex with Ti-S-C linkages. BDT adsorbs on TiO2 by the bridging bidentate coordination of the sulfur atoms to surface titanium atoms. The TiO2-BDT complex shows ICT transitions from the BDT moiety to the conduction band of TiO2 in the visible region. The ICT transitions occur by orbital overlaps between the d orbitals of the surface titanium atoms and the π orbitals of the benzene ring. Our density-functional-theory (DFT) analysis reveals that the 3p valence orbitals of the sulfur bridging atoms contribute to more than 50% of the highest occupied molecular orbital (HOMO) and the 3d-3p(sulfur)-π interaction via the Ti-S-C linkage enhances the electronic mixing between the titanium atoms and the benzene moiety as compared to the 3d-2p(oxygen)-πvia the Ti-O-C linkage. This result indicates the important role of the heavier-atom linkers for strong organic-inorganic electronic couplings.

Nature and geodynamic setting of the protoliths of the UHP metamorphic Complex and migmatites in Bixiling area, the Dabie Orogen, China

NASA Astrophysics Data System (ADS)

Li, H.; Jahn, B.; Wang, D.; Yu, H.; Liu, Z.; Hou, G.

2013-12-01

As the largest coesite-bearing mafic-ultramafic body in the Dabie-Sulu orogen, the Bixiling Complex is composed of meta-ultramafic rocks, MgAl-rich eclogites and FeTi-rich eclogites. The FeTi-rich eclogites are further divided into low-Si-high-Fe type (Type I) and high-Si-low-Fe type (Type II) according to their mineral assemblages and bulk chemical composition. Field, petrographic, petrological and geochemical characteristics of these rocks, although suffered an ultra-high pressure metamorphism, still show a magmatic differentiation process among the protoliths of the meta-ultramafic rocks, MgAl-rich eclogites and Type I FeTi-rich eclogites. A small degree of lower crustal contamination occurred during their magma chamber process. Amphibolite is widespread in the periphery of the complex. Non-foliation and fine-grained texture are their obvious characteristics. Geochemical and isotopic affinities suggest that the amphibolites represent a product of complete retrogression from type II FeTi-rich eclogites. The UHP complex is enclosed in granitic gneisses, which variably include two-mica plagioclase gneiss, epidote two-mica plagioclase gneiss, or white-mica plagioclase gneiss. They all show TTG, especially trondjhemitic composition. A migmatite outcrop was found near the northeastern end of the complex. The migmatites consist of dark colored, non-foliated amphibolites and light-colored, fine-grained trondhjemitic gneisses. Field occurrences, microstructures observed under optical microscope and SEM, Sr-Nd isotopic data suggest an origin of partial melting. Chemical composition of two stages of amphiboles occurred in both the amphibolites and the trondhjemitic gneisses also imply a partial melting process occurred. Trace element, Sr-Nd isotope and SHRIMP zircon U-Pb dating of MgAl-rich eclogite, amphibolites and trondhjemite suggest that the migmatites represent a partial melting of crustal materials at about 780Ma, possibly accompanied by the coeval emplacement of a differentiated mafic intrusive body. These rocks were deeply subducted into a mantle depth during the Triassic continental collision between the Yangtze Craton and North China Craton, and thereafter were exhumed to the surface. Their residual geochemical characteristics and spatial / temporal relationship could impose constraints on the tectonic evolution of the Dabieshan UHP terrane.

Phosphate-modified TiO2 nanoparticles for selective detection of dopamine, levodopa, adrenaline, and catechol based on fluorescence quenching.

PubMed

Wu, Hsin-Pin; Cheng, Tian-Lu; Tseng, Wei-Lung

2007-07-03

For the first time, an aqueous solution, comprising 6-nm phosphate-modified titanium dioxide (P-TiO2) nanoparticles (NPs) and fluorescein, has been used for sensing dopamine (DA), levodopa (L-DOPA), adrenaline, and catechol. The complexes obtained by means of chelation of surface Ti(IV) ions with an enediol group exhibit strong absorption at 428 nm; thus, they can be designed as efficient quenchers for fluorescein. The fluorescence of a fluorescein solution containing 1.4 mM P-TiO2 NPs at pH 8.0 decreases if the solution comprises DA, L-DOPA, adrenaline, and catechol, but not noradrenaline, ascorbic acid, and salicylic acid. We consider that P-TiO2 NPs have a number of advantages over bare TiO2 NPs, such as ease of preparation, high selectivity, and high stability. By measuring fluorescence quenching, the limits of detection at a signal-to-noise ratio of 3 are calculated as 33.5, 81.8, 20.3, and 92.1 nM for DA, L-DOPA, adrenaline, and catechol, respectively. In contrast, UV-vis absorption reveals the relatively poor sensitivity of these compounds. We have validated the applicability of our method by means of analyses of DA in urine samples. High-performance liquid chromatography in combination with an electrochemical cell has been used to further confirm our results. We believe that this approach has great potential for diagnostic purposes.

Comparison of hardness variation of ion irradiated borosilicate glasses with different projected ranges

NASA Astrophysics Data System (ADS)

Sun, M. L.; Peng, H. B.; Duan, B. H.; Liu, F. F.; Du, X.; Yuan, W.; Zhang, B. T.; Zhang, X. Y.; Wang, T. S.

2018-03-01

Borosilicate glass has potential application for vitrification of high-level radioactive waste, which attracts extensive interest in studying its radiation durability. In this study, sodium borosilicate glass samples were irradiated with 4 MeV Kr17+ ion, 5 MeV Xe26+ ion and 0.3 MeV P+ ion, respectively. The hardness of irradiated borosilicate glass samples was measured with nanoindentation in continuous stiffness mode and quasi continuous stiffness mode, separately. Extrapolation method, mean value method, squared extrapolation method and selected point method are used to obtain hardness of irradiated glass and a comparison among these four methods is conducted. The extrapolation method is suggested to analyze the hardness of ion irradiated glass. With increasing irradiation dose, the values of hardness for samples irradiated with Kr, Xe and P ions dropped and then saturated at 0.02 dpa. Besides, both the maximum variations and decay constants for three kinds of ions with different energies are similar indicates the similarity behind the hardness variation in glasses after irradiation. Furthermore, the hardness variation of low energy P ion irradiated samples whose range is much smaller than those of high energy Kr and Xe ions, has the same trend as that of Kr and Xe ions. It suggested that electronic energy loss did not play a significant role in hardness decrease for irradiation of low energy ions.

Caesalpinia bonduc serine proteinase inhibitor CbTI-2: Exploring the conformational features and antimalarial activity.

PubMed

Bhattacharyya, Arindam; Babu, C R

2017-10-01

Seeds of tropical legumes posses a repertoire of proteinase inhibitors (PI) and the current study highlights some structural/functional features of a strong serine PI from the seeds of Caesalpinia bonduc (CbTI-2). Following purification, N-terminal sequence of CbTI-2 revealed over 40% similarity with a few serine PIs of Caesalpinioideae subfamily. Upon exposure to metal ions and ionic/non ionic surfactants, CbTI-2 showed immense variation in the levels of antitryptic activity. Exposure of CbTI-2 to 1,4-Dithiothreitol, Guanidinium HCl, H 2 O 2 and Dimethyl sulfoxide led to a steady loss of inhibitory activity. Chemical modification of amino acids suggested an arginine as the active site residue. Circular Dichroism spectrum of native CbTI-2 revealed an unordered state. Secondary structure composition of CbTI-2 following exposure to extreme conditions (heat, acidic/alkaline environment, Guanidine hydrochloride and DTT) showed considerable perturbations that caused severe loss of antiproteolytic activity. DLS studies yielded a hydrodynamic radius of ∼2.2nm for CbTI-2 and also reconfirmed 1:1 stoichiometry for the trypsin-CbTI-2 complex. Initial studies indicated CbTI-2 to be a potent antiplasmodial agent by being highly toxic towards growth, schizont rupture process and erythrocytic invasion of Plasmodium falciparum. Copyright © 2017 Elsevier B.V. All rights reserved.

Structural and electrochemical studies of TiO2 complexes with (4,4'-((1E,1'E)-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethene-2,1-diyl))bis-(E)-N-(2,5-bis(octyloxy)benzylidene)) imine derivative bases towards organic devices.

PubMed

Rozycka, Anna; Iwan, Agnieszka; Bogdanowicz, Krzysztof Artur; Filapek, Michal; Górska, Natalia; Hreniak, Agnieszka; Marzec, Monika

2018-06-12

Three (4,4'-((1E,1'E)-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethene-2,1-diyl))bis-(E)-N-(2,5-bis(octyloxy)benzylidene)) imine derivatives were synthesized via a condensation reaction with p-toluenesulfonic acid as a catalyst. The effects of the end groups and vinylene (-HC[double bond, length as m-dash]CH-) moieties on the structural, thermal, optical, electrochemical and photovoltaic properties of imines were investigated to check the influence of TiO2 on the imine properties. The thermal behavior of imines and their complexes with TiO2 was widely investigated using FT-IR, XRD, DSC and POM methods in order to determine the order type in the imine structure. All imines present the highest occupied molecular orbital (HOMO) levels of about -5.39 eV (SAI1 and SAI2) and -5.27 eV (SAI3) and the lowest unoccupied molecular orbital (LUMO) levels at about -3.17 eV. The difference of the end groups in the imines in each case did not affect redox properties. Generally, both oxidation and reduction are easier after TiO2 addition and it also changes the HOMO-LUMO levels of imines. Moreover, changes in the characteristic bands for imines in the region 1500-1700 cm-1 observed as a drastic decrease of intensity or even disappearance of bands in the imine : TiO2 mixture suggest the formation of a complex (C[double bond, length as m-dash]N)-TiO2. Organic devices with the configuration of ITO/TiO2/SAIx (or SAIx : TiO2)/Au were fabricated and investigated in the presence and absence of visible light irradiation with an intensity of 93 mW cm-2. In all imines and complexes with TiO2, the generation of the photocurrent indicates their use as photodiodes and the best result was observed for SAI3 : TiO2 complexes.

Electromagnetically induced absorption and transparency in degenerate two level systems of metastable Kr atoms and measurement of Landé g-factor

NASA Astrophysics Data System (ADS)

Kale, Y. B.; Tiwari, V. B.; Mishra, S. R.; Singh, S.; Rawat, H. S.

2016-12-01

We report electromagnetically induced absorption (EIA) and transparency (EIT) resonances of sub-natural linewidth in degenerate two level systems (DTLSs) of metastable 84Kr (84Kr*) and 83Kr (83Kr*) atoms. Using the spectrally narrow EIA signals obtained corresponding to the closed hyperfine transition 4p55s[3/2]2(F=13/2) to 4p55p[5/2]3(F‧ = 15 / 2) in 83Kr* atom, we have measured the Landé g-factor (gF) for the lower hyperfine level involved in this transition by application of small values of magnetic field of few Gauss.

The informational role of knowledge of results in motor learning.

PubMed

Blackwell, J R; Newell, K M

1996-07-01

An experiment is reported that was set-up to examine the informational role of knowledge of results (KR) in the learning of a single-limb movement timing task. A group with KR practiced 200 trials a day for 5 days prior to receiving a sixth day of practice without KR. The performance of this group was contrasted to another group that practiced 200 trials without KR for one day. Traditional movement error and time series analyses revealed that KR serves to calibrate the movement outcome to the task demands and modulate the performance outcome relation between trials. The degree of systematic trial-to-trial modulation was strongly dependent upon the degree of error exhibited on any given trial, and was enhanced under no-KR conditions. Information in KR has both immediate and persistent influences on learning and performance that are dependent upon the task constraints and the skill level of the performer.

Development of Electron Beam Pumped KrF Lasers for Fusion Energy

DTIC Science & Technology

2008-01-01

Direct drive with krypton fluoride (KrF) lasers is an attractive approach to inertial fusion energy (IFE): KrF lasers have outstanding beam spatial...attractive power plant [3]. In view of these advances, several world-wide programs are underway to develop KrF lasers for fusion energy . These include

DOE Office of Scientific and Technical Information (OSTI.GOV)

Valderrama, Billy; He, Lingfeng; Henderson, Hunter B.

Fission products, such as krypton (Kr), are known to be insoluble within UO 2, segregating towards grain boundaries, eventually leading to a lowering of the thermal conductivity and fuel swelling. Recent computational studies have identified that differences in grain boundary structure have a significant effect on the segregation behavior of fission products. However, experimental work supporting these simulations is lacking. Atom probe tomography was used to measure the Kr distribution across grain boundaries in UO 2. Polycrystalline depleted-UO 2 samples was irradiated with 0.7 and 1.8 MeV Kr-ions and annealed to 1000ºC, 1300ºC, and 1600°C for 1 hour to producemore » a Kr-bubble dominated microstructure. The results of this work indicate a strong dependence of Kr concentration as a function of grain boundary structure. Temperature also influences grain boundary chemistry with greater Kr concentration evident at higher temperatures, resulting in a reduced Kr concentration in the bulk. While Kr migration is active at elevated temperatures, no changes in grain size or texture were observed in the irradiated UO 2 samples.« less

New method of 85Kr reduction in a noble gas based low-background detector

NASA Astrophysics Data System (ADS)

Akimov, D. Yu.; Bolozdynya, A. I.; Burenkov, A. A.; Hall, C.; Kovalenko, A. G.; Kuzminov, V. V.; Simakov, G. E.

2017-04-01

Krypton-85 is an anthropogenic beta-decaying isotope which produces low energy backgrounds in dark matter and neutrino experiments, especially those based upon liquid xenon. Several technologies have been developed to reduce the Kr concentration in such experiments. We propose to augment those separation technologies by first adding to the xenon an 85Kr-free sample of krypton in an amount much larger than the natural krypton that is already present. After the purification system reduces the total Kr concentration to the same level, the final 85Kr concentration will be reduced even further by the dilution factor. A test cell for measurement of the activity of various Kr samples has been assembled, and the activity of 25-year-old krypton has been measured. The measured activity agrees well with the expected activity accounting for the 85Kr abundance of the earth's atmosphere in 1990 and the half-life of the isotope. Additional tests with a Kr sample produced in the year 1944 (before the atomic era) have been done in order to demonstrate the sensitivity of the test cell.

Aqua complexes of 18—crown-6 with H 3PO 4, H 2TiF 6, and HNO 3: synthesis and vibrational spectra

NASA Astrophysics Data System (ADS)

Chénevert, R.; Rodrigue, A.; Chamberland, D.; Ouellet, J.; Savoie, R.

1985-11-01

Neutral-component complexes of 2:3:1 (acid:water:18-crown-6) stoichiometry have been obtained with H 3PO 4 and H 2TiF 6. These adducts have been studied by infrared and Raman spectroscopy, along with the corresponding (HNO 3-H 1O) 2-18-crown-6 complex, whose synthesis has already been reported. The spectra indicate that the crown ether has a highly regular conformation in these complexes. In those with H 3PO 4 and HNO 3, the binding of the acid molecule to the ether takes place through a H 2O linker, the strength of the XOH⋯OH 2 hydrogen bond being directly related to the p K a of the acid. With HNO 3, the acidic proton appears to be delocalized between the two oxygen atoms, giving a pseudo H 2O + ion whereas in the corresponding deuterocompound the D atom remains associated with the acid.

Tandem Reactions for Streamlining Synthesis

PubMed Central

HUSSAIN, MAHMUD M.; WALSH, PATRICK J.

2009-01-01

CONSPECTUS In 1980 Sharpless and Katsuki introduced the asymmetric epoxidation of prochiral allylic alcohols (the Sharpless-Katsuki Asymmetric Epoxidation), which enabled the rapid synthesis of highly enantioenriched epoxy alcohols. This reaction was a milestone in the development of asymmetric catalysis because it was the first highly enantioselective oxidation reaction. Furthermore, it provided access to enantioenriched allylic alcohols that are now standard starting materials in natural product synthesis. In 1981 Sharpless and coworkers made another seminal contribution by describing the kinetic resolution (KR) of racemic allylic alcohols. This work demonstrated that small-molecule catalysts could compete with enzymatic catalysts in KRs. For these pioneering works, Sharpless was awarded the 2001 Nobel Prize with Knowles and Noyori. Despite these achievements, the Sharpless KR is not an efficient method to prepare epoxy alcohols with high enantiomeric excess (ee). First, the racemic allylic alcohol must be prepared and purified. KR of the racemic allylic alcohol must be stopped at low conversion, because the ee of the product epoxy alcohol decreases as the KR progresses. Thus, better methods to prepare epoxy alcohols containing stereogenic carbinol carbons are needed. This Account summarizes our efforts to develop one-pot methods for the synthesis of various epoxy alcohols and allylic epoxy alcohols with high enantio-, diastereo-, and chemoselectivity. Our laboratory developed titanium-based catalysts for use in the synthesis of epoxy alcohols with tertiary carbinols. The catalysts are involved in the first step, which is an asymmetric alkyl or allyl addition to enones. The resulting intermediates are then subjected to a titanium-directed diastereoselective epoxidation to provide tertiary epoxy alcohols. Similarly, the synthesis of acyclic epoxy alcohols begins with asymmetric additions to enals and subsequent epoxidation. The methods described here enable the synthesis of skeletally diverse epoxy alcohols. PMID:18710197

Influence of inert gases on the reactive high power pulsed magnetron sputtering process of carbon-nitride thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schmidt, Susann; Czigany, Zsolt; Greczynski, Grzegorz

2013-01-15

The influence of inert gases (Ne, Ar, Kr) on the sputter process of carbon and carbon-nitride (CN{sub x}) thin films was studied using reactive high power pulsed magnetron sputtering (HiPIMS). Thin solid films were synthesized in an industrial deposition chamber from a graphite target. The peak target current during HiPIMS processing was found to decrease with increasing inert gas mass. Time averaged and time resolved ion mass spectroscopy showed that the addition of nitrogen, as reactive gas, resulted in less energetic ion species for processes employing Ne, whereas the opposite was noticed when Ar or Kr were employed as inertmore » gas. Processes in nonreactive ambient showed generally lower total ion fluxes for the three different inert gases. As soon as N{sub 2} was introduced into the process, the deposition rates for Ne and Ar-containing processes increased significantly. The reactive Kr-process, in contrast, showed slightly lower deposition rates than the nonreactive. The resulting thin films were characterized regarding their bonding and microstructure by x-ray photoelectron spectroscopy and transmission electron microscopy. Reactively deposited CN{sub x} thin films in Ar and Kr ambient exhibited an ordering toward a fullerene-like structure, whereas carbon and CN{sub x} films deposited in Ne atmosphere were found to be amorphous. This is attributed to an elevated amount of highly energetic particles observed during ion mass spectrometry and indicated by high peak target currents in Ne-containing processes. These results are discussed with respect to the current understanding of the structural evolution of a-C and CN{sub x} thin films.« less

Intrinsic Enhancement of Dielectric Permittivity in (Nb + In) co-doped TiO2 single crystals.

PubMed

Kawarasaki, Masaru; Tanabe, Kenji; Terasaki, Ichiro; Fujii, Yasuhiro; Taniguchi, Hiroki

2017-07-13

The development of dielectric materials with colossal permittivity is important for the miniaturization of electronic devices and fabrication of high-density energy-storage devices. The electron-pinned defect-dipoles has been recently proposed to boost the permittivity of (Nb + In) co-doped TiO 2 to 10 5 . However, the follow-up studies suggest an extrinsic contribution to the colossal permittivity from thermally excited carriers. Herein, we demonstrate a marked enhancement in the permittivity of (Nb + In) co-doped TiO 2 single crystals at sufficiently low temperatures such that the thermally excited carriers are frozen out and exert no influence on the dielectric response. The results indicate that the permittivity attains quadruple of that for pure TiO 2 . This finding suggests that the electron-pinned defect-dipoles add an extra dielectric response to that of the TiO 2 host matrix. The results offer a novel approach for the development of functional dielectric materials with large permittivity by engineering complex defects into bulk materials.

Training for vigilance: using predictive power to evaluate feedback effectiveness.

PubMed

Szalma, James L; Hancock, Peter A; Warm, Joel S; Dember, William N; Parsons, Kelley S

2006-01-01

We examined the effects of knowledge of results (KR) on vigilance accuracy and report the first use of positive and negative predictive power (PPP and NPP) to assess vigilance training effectiveness. Training individuals to detect infrequent signals among a plethora of nonsignals is critical to success in many failure-intolerant monitoring technologies. KR has been widely used for vigilance training, but the effect of the schedule of KR presentation on accuracy has been neglected. Previous research on training for vigilance has used signal detection metrics or hits and false alarms. In this study diagnosticity measures were applied to augment traditional analytic methods. We examined the effects of continuous KR and a partial-KR regimen versus a no-KR control on decision diagnosticity. Signal detection theory (SDT) analysis indicated that KR induced conservatism in responding but did not enhance sensitivity. However, KR in both forms equally enhanced PPP while selectively impairing NPP. There is a trade-off in the effectiveness of KR in reducing false alarms and misses. Together, SDT and PPP/NPP measures provide a more complete portrait of performance effects. PPP and NPP together provide another assessment technique for vigilance performance, and as additional diagnostic tools, these measures are potentially useful to the human factors community.

Study of Pair and many-body interactions in rare-gas halide atom clusters using negative ion zero electron kinetic energy (ZEKE) and threshold photodetachment spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yourshaw, Ivan

1998-07-09

The diatomic halogen atom-rare gas diatomic complexes KrBr -, XeBr -, and KrCl - are studied in this work by zero electron kinetic energy (ZEKE) spectroscopy in order to characterize the weak intermolecular diatomic potentials of these species. Also, the ZEKE and threshold photodetachment spectra of the polyatomic clusters Ar nBr - (n = 2-9) and Ar nI - (n = 2-19) are studied to obtain information about the non-additive effects on the interactions among the atoms. This work is part of an ongoing effort to characterize the pair and many-body potentials of the complete series of rare gas halidemore » clusters. In these studies we obtain information about both the anionic and neutral clusters.« less

Imaging and tuning polarity at SrTiO 3 domain walls

DOE PAGES

Frenkel, Yiftach; Haham, Noam; Shperber, Yishai; ...

2017-09-18

Electrostatic fields tune the ground state of interfaces between complex oxide materials. Electronic properties, such as conductivity and superconductivity, can be tuned and then used to create and control circuit elements and gate-defined devices. Here in this paper, we show that naturally occurring twin boundaries, with properties that are different from their surrounding bulk, can tune the LaAlO 3/SrTiO 3 interface 2DEG at the nanoscale. In particular, SrTiO 3 domain boundaries have the unusual distinction of remaining highly mobile down to low temperatures, and were recently suggested to be polar. Here we apply localized pressure to an individual SrTiO 3more » twin boundary and detect a change in LaAlO 3/SrTiO 3 interface current distribution. Our data directly confirm the existence of polarity at the twin boundaries, and demonstrate that they can serve as effective tunable gates. As the location of SrTiO 3 domain walls can be controlled using external field stimuli, our findings suggest a novel approach to manipulate SrTiO 3-based devices on the nanoscale.« less

First Report of Orange Rust of Sugarcane caused by Puccinia kuehnii in Ecuador

USDA-ARS?s Scientific Manuscript database

Orange rust, Puccinia kuehnii (W. Krüger) E.J. Butler, is an important disease of sugarcane (complex hybrid of Saccharum L. species) that causes yield losses, and impacts breeding programs. Initially confined to the Asia-Oceania region (5), P. kuehnii was reported in Florida in June 2007 (2) and lat...

Analysis of XeC1 Emission in a Hollow Cathode Discharge.

DTIC Science & Technology

1981-06-01

excited homopolar molecule, e.g., Xe2 , Hg2 The term exciplex refers to an electronically excited heteropolar complex, e.g., KrF , XeOH , XeCl , which...HCI Products, k9 = 5.4 x 10 cm /sec. (25) Figure 9 summarizes the main energy pathways for XeCI exciplex formation via three body recombination and

Complex damage distribution behaviour in cobalt implanted rutile TiO2 (1 1 0) lattice

NASA Astrophysics Data System (ADS)

Joshi, Shalik Ram; Padmanabhan, B.; Chanda, Anupama; Ojha, Sunil; Kanjilal, D.; Varma, Shikha

2017-11-01

The present work investigates the radiation damage, amorphization and structural modifications that are produced by ion-solid interactions in TiO2 crystals during 200 keV Cobalt ion implantation. RBS/C and GIXRD have been utilized to evaluate the damage in the host lattice as a function of ion fluence. Multiple scattering formalism has been applied to extract the depth dependent damage distributions in TiO2(1 1 0). The results have been compared with the MC simulations performed using SRIM-2013. RBS/C results delineate a buried amorphous layer at a low fluence. Surprisingly, ion induced dynamic activation produces a recovery in this damage at higher fluences. This improvement interestingly occurs only in deep regions (60-300 nm) where a systematic lowering in damage with fluence is observed. Formation of Co-Ti-O phases and generation of stress in TiO2 lattice can also be responsible for this improvement in deep regions. In contrast, surface region (0-60 nm) indicates a gradual increase in damage with fluence. Such a switch in the damage behavior creates a cross point in damage profiles at 60 nm. Surface region is a sink of vacancies whereas deep layers are interstitial rich. However, these regions are far separated from each other resulting in an intermediate (100-150 nm) region with a significant dip (valley) in damage which can be characterized by enhanced recombination of point defects. The damage profiles thus indicate a very complex behavior. MC simulations, however, present very different results. They depict a damage profile that extends to a depth of only 150 nm, which is only about half of the damage- width observed here via RBS/C. Moreover, MC simulations do not indicate presence of any valley like structure in the damage profile. The complex nature of damage distribution observed here via RBS/C may be related to the high ionic nature of the chemical bonds in the TiO2 lattice.

Lifetime of inner-shell hole states of Ar (2p) and Kr (3d) using equation-of-motion coupled cluster method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghosh, Aryya; Vaval, Nayana, E-mail: np.vaval@ncl.res.in; Pal, Sourav

2015-07-14

Auger decay is an efficient ultrafast relaxation process of core-shell or inner-shell excited atom or molecule. Generally, it occurs in femto-second or even atto-second time domain. Direct measurement of lifetimes of Auger process of single ionized and double ionized inner-shell state of an atom or molecule is an extremely difficult task. In this paper, we have applied the highly correlated complex absorbing potential-equation-of-motion coupled cluster (CAP-EOMCC) approach which is a combination of CAP and EOMCC approach to calculate the lifetime of the states arising from 2p inner-shell ionization of an Ar atom and 3d inner-shell ionization of Kr atom. Wemore » have also calculated the lifetime of Ar{sup 2+}(2p{sup −1}3p{sup −1}) {sup 1}D, Ar{sup 2+}(2p{sup −1}3p{sup −1}) {sup 1}S, and Ar{sup 2+}(2p{sup −1}3s{sup −1}) {sup 1}P double ionized states. The predicted results are compared with the other theoretical results as well as experimental results available in the literature.« less

Cosmogenic and fissiogenic noble gases and 81Kr-Kr exposure age clusters of eucrites

NASA Astrophysics Data System (ADS)

Shukolyukov, A.; Begemann, F.

1996-01-01

The isotopic composition and concentrations of noble gases were measured in the eucrites Bereba, Cachari, Caldera, Camel Donga, Chervony Kut, Ibitira, Jonzac, Juvinas, Millbillillie, Moore County, Padvarninkai, Pasamonte, Pomozdino, Serra de Magé, Sioux County, and Vetluga. The distribution of 81Kr-Kr exposure ages shows "clusters" at (7 ± 1) Ma, (10 ± 1) Ma, (14 ± 1) Ma, (22 ± 2) Ma, and (37 ± 1) Ma that agree with those for howardites, eucrites, and diogenites (HED) at (6 ± 1) Ma, (12 ± 2) Ma, (21 ± 4) Ma, and (38 ± 8) Ma. This most likely indicates a common origin of HED meteorites. Correlation equations for the shielding-sensitive cosmogenic ratios 78Kr/83Kr, 80Kr/83Kr, 82Kr/83Kr, and 124Xe/131Xe were obtained. Comparison with data from simulation experiments suggests that most eucrites were exposed to the cosmic radiation as somewhat large meteoroids with diameters of ˜1 m or more. The shielding-dependence of the 78Kr and 126Xe production rates was found to be small, with a few exceptions the variations aren <10%-15%. Concentrations of spallogenic 3He indicate diffusive losses of up to 70% that can be, in first approximation, described by a model of quasi-continuous losses during the exposure to the cosmic radiation with a loss rate of the order of ˜3 × 10-8 a-1. Radiogenic 4He shows additional substantial losses that occurred at the time of, or prior to, the separation of the meteoroids from their parent body. Typical 40Ar retention in eucrites is 50%-60% which corresponds to a 40Ar-K retention age of 3.4-3.6 Ga. In all analyzed unbrecciated eucrites, the retention is distinctly larger (70%-100%). The 244Pu fission ratio (86Kr/136Xe)Pu, was evaluated from the data on Pomozdino samples to be 0.039 ± 0.014.

Dye sensitized solar cell applications of CdTiO{sub 3}–TiO{sub 2} composite thin films deposited from single molecular complex

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ehsan, Muhammad Ali; Khaledi, Hamid; Pandikumar, Alagarsamy

2015-10-15

A heterobimetallic complex [Cd{sub 2}Ti{sub 4}(μ-O){sub 6}(TFA){sub 8}(THF){sub 6}]·1.5THF (1) (TFA=trifluoroacetato, THF=tetrahydrofuran) comprising of Cd:Ti (1:2) ratio was synthesized by a chemical reaction of cadmium (II) acetate with titanium (IV) isopropoxide and triflouroacetic acid in THF. The stoichiometry of (1) was recognized by single crystal X-ray diffraction, spectroscopic and elemental analyses. Thermal studies revealed that (1) neatly decomposes at 450 °C to furnish 1:1 ratio of cadmium titanate:titania composite oxides material. The thin films of CdTiO{sub 3}–TiO{sub 2} composite oxides were deposited at 550 °C on fluorine doped tin oxide coated conducting glass substrate in air ambient. The micro-structure, crystallinity,more » phase identification and chemical composition of microspherical architectured CdTiO{sub 3}–TiO{sub 2} composite thin film have been determined by scanning electron microscopy, X-ray diffraction, Raman spectroscopy and energy dispersive X-ray analysis. The scope of composite thin film having band gap of 3.1 eV was explored as photoanode for dye-sensitized solar cell application. - Graphical abstarct: Microspherical designed CdTiO{sub 3}–TiO{sub 2} composite oxides photoanode film has been fabricated from single source precursor [Cd{sub 2}Ti{sub 4}(μ-O){sub 6}(TFA){sub 8}(THF){sub 6}]·1.5THF via aerosol assisted chemical vapor deposition technique for dye sensitized solar cell application. - Highlights: • Synthesis and characterization of a heterobimetallic Cd–Ti complex. • Fabrication of CdTiO{sub 3}–TiO{sub 2} thin film photoelectrode. • Application as dye sensitized photoanode for solar application.« less

Formation Mechanism of Spherical TiC in Ni-Ti-C System during Combustion Synthesis.

PubMed

Zhu, Guoliang; Wang, Wei; Wang, Rui; Zhao, Chuanbao; Pan, Weitao; Huang, Haijun; Du, Dafan; Wang, Donghong; Shu, Da; Dong, Anping; Sun, Baode; Jiang, Sheng; Pu, Yilong

2017-08-29

The formation mechanism of TiC particles in a Ni-Ti-C system were revealed by using differential thermal analysis (DTA), XRD, and SEM to identify the reaction products in different temperature ranges. The results indicated that the synthesis mechanism of TiC in Ni-Ti-C system was complex; several reactions were involved in the combustion synthesis of TiC-Ni composite. The Ni-Ti intermediate phases play important roles during the formation of TiC. Moreover, the influence of heating rate on the size range of TiC was also discussed.

Formation Mechanism of Spherical TiC in Ni-Ti-C System during Combustion Synthesis

PubMed Central

Zhu, Guoliang; Wang, Wei; Wang, Rui; Zhao, Chuanbao; Pan, Weitao; Huang, Haijun; Du, Dafan; Wang, Donghong; Shu, Da; Dong, Anping; Sun, Baode; Jiang, Sheng; Pu, Yilong

2017-01-01

The formation mechanism of TiC particles in a Ni-Ti-C system were revealed by using differential thermal analysis (DTA), XRD, and SEM to identify the reaction products in different temperature ranges. The results indicated that the synthesis mechanism of TiC in Ni-Ti-C system was complex; several reactions were involved in the combustion synthesis of TiC-Ni composite. The Ni-Ti intermediate phases play important roles during the formation of TiC. Moreover, the influence of heating rate on the size range of TiC was also discussed. PMID:28850088

Microstructure and properties of Fe-based composite coating by laser cladding Fe-Ti-V-Cr-C-CeO2 powder

NASA Astrophysics Data System (ADS)

Zhang, Hui; Zou, Yong; Zou, Zengda; Wu, Dongting

2015-01-01

In situ TiC-VC reinforced Fe-based cladding layer was obtained on low carbon steel surface by laser cladding with Fe-Ti-V-Cr-C-CeO2 alloy powder. The microstructure, phases and properties of the cladding layer were investigated by X-ray diffractometry (XRD), scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), transmission electron microscopy (TEM), potentio-dynamic polarization and electro-chemical impedance spectroscopy (EIS). Results showed Fe-Ti-V-Cr-C-CeO2 alloy powder formed a good cladding layer without defects such as cracks and pores. The phases of the cladding layer were α-Fe, γ-Fe, TiC, VC and TiVC2. The microstructures of the cladding layer matrix were lath martensite and retained austenite. The carbides were polygonal blocks with a size of 0.5-2 μm and distributed uniformly in the cladding layer. High resolution transmission electron microscopy showed the carbide was a complex matter composed of nano TiC, VC and TiVC2. The cladding layer with a hardness of 1030 HV0.2 possessed good wear and corrosion resistance, which was about 16.85 and 9.06 times than that of the substrate respectively.

Dehydriding properties of Ti or/and Zr-doped sodium aluminum hydride prepared by ball-milling

NASA Astrophysics Data System (ADS)

Xiao, Xue-Zhang; Chen, Li-Xin; Wang, Xin-Hua; Li, Shou-Quan; Hang, Zhou-Ming; Chen, Chang-Pin; Wang, Qi-Dong

2007-12-01

The NaAlH4 complex is attracting great attention for its potential applications in hydrogen-powered fuel-cell vehicles due to its high hydrogen storage capacity and suitable thermodynamic properties. However, its practicable hydrogen storage capacity presently obtained is less than the theoretical capacity (5.6 wt.%). To improve the hydrogen capacity, we chose metallic Ti or/and Zr powder as catalyst dopants, and prepared the sodium aluminum hydride by hydrogenation of ball-milled NaH/Al mixture containing 10 mol% dopants with different proportions of Ti and Zr, and then investigated the effects on their hydrogen storage (dehydriding) properties. The results showed that different catalyst dopants affected the dehydriding properties greatly. The catalysis of metal Ti as a catalyst dopant alone on dehydriding kinetics for the entire dehydrogenation process of ball-milled (NaH/Al) composite was higher than that of adopting Zr alone. The synergistic catalytic effect of Ti and Zr together as co-dopants on the dehydrogenation process of (NaH/Al) composite was higher than that using only Ti or Zr as dopant individually. The composite doped with proper proportion of Ti and Zr together (8 mol% Ti+ 2 mol% Zr) as co-dopants exhibited the highest dehydriding kinetic property and desorption capacity.

High calcination of ferroelectric BaTiO₃ doped Fe nanoceramics prepared by a solid-state sintering method.

PubMed

Samuvel, K; Ramachandran, K

2015-07-05

This study examined the effects of the combination of starting materials on the properties of solid-state reacted BaTiO3 using two different types of BaCO3 and TiO2. In addition, the effect of mechanochemical activation by high energy milling and the Ba/Ti molar ratio on the reaction temperature, particle size and tetragonality were investigated. The TiO2 phase and size plays a major role in increasing the reaction temperature and particle size. With the optimum selection of starting materials and processing conditions, BaTiO3 with a particle size <200 nm (Scherrer's formula) and a tetragonality c/a of approximately 1.007 was obtained. Broadband dielectric spectroscopy is applied to investigate the electrical properties of disordered perovskite-like ceramics in a wide temperature range. From the X-ray diffraction analysis it was found that the newly obtained BaTi0.5Fe0.5O3 ceramics consist of two chemically different phases. The electric modulus M∗ formalism used in the analysis enabled us to distinguish and separate the relaxation processes, dominated by marked conductivity in the ε∗(ω) representation. Interfacial effects on the dielectric properties of the samples have been understood by Cole-Cole plots in complex impedance and modulus formalism. Modulus formalism has identified the effects of both grain and grain boundary microstructure on the dielectric properties, particularly in solid state routed samples. Copyright © 2015 Elsevier B.V. All rights reserved.

High calcination of ferroelectric BaTiO3 doped Fe nanoceramics prepared by a solid-state sintering method

NASA Astrophysics Data System (ADS)

Samuvel, K.; Ramachandran, K.

2015-07-01

This study examined the effects of the combination of starting materials on the properties of solid-state reacted BaTiO3 using two different types of BaCO3 and TiO2. In addition, the effect of mechanochemical activation by high energy milling and the Ba/Ti molar ratio on the reaction temperature, particle size and tetragonality were investigated. The TiO2 phase and size plays a major role in increasing the reaction temperature and particle size. With the optimum selection of starting materials and processing conditions, BaTiO3 with a particle size <200 nm (Scherrer's formula) and a tetragonality c/a of approximately 1.007 was obtained. Broadband dielectric spectroscopy is applied to investigate the electrical properties of disordered perovskite-like ceramics in a wide temperature range. From the X-ray diffraction analysis it was found that the newly obtained BaTi0.5Fe0.5O3 ceramics consist of two chemically different phases. The electric modulus M∗ formalism used in the analysis enabled us to distinguish and separate the relaxation processes, dominated by marked conductivity in the ε∗(ω) representation. Interfacial effects on the dielectric properties of the samples have been understood by Cole-Cole plots in complex impedance and modulus formalism. Modulus formalism has identified the effects of both grain and grain boundary microstructure on the dielectric properties, particularly in solid state routed samples.

Efficient photocatalytic degradation of gaseous N,N-dimethylformamide in tannery waste gas using doubly open-ended Ag/TiO2 nanotube array membranes

NASA Astrophysics Data System (ADS)

Zhao, Yang; Ma, Lin; Chang, Wenkai; Huang, Zhiding; Feng, Xugen; Qi, Xiaoxia; Li, Zenghe

2018-06-01

Gaseous N,N-dimethylformamide (DMF), typical volatile organic compound exhausted from manufacturing factories, may damage the health of workers under long-term exposure even at low levels. The defined geometry, porous surface and highly ordered channels make the free-standing anodic TiO2 nanotube (TiNT) arrays particularly suitable for applications of practical air purification by flow-through photocatalysis. In the present work, crystallized doubly open-ended Ag/TiNT array membranes were designed and prepared by employing a lift-off process based on an anodization-annealing-anodization-etching sequence, followed by uniform Ag nanoparticles decoration. For the photocatalytic degradation of gaseous DMF at low concentration levels close to that found in realistic pollutant air, an analytical methodology for the monitoring and determination of degradation process was developed based on the coupling of headspace sampling with gas chromatography mass spectrometry (HS-GC-MS). The doubly open-ended Ag/TiNT arrays exhibited higher removal efficiency of gaseous DMF from air compared with conventional bottom-closed Ag/TiNT arrays and pure bottomless TiNT arrays. These results indicated that the photocatalytic properties of TiNT arrays were improved with the open-bottom morphology and the Ag nanoparticles decoration. Based on the analysis with GC-MS and high performance ion chromatography (HPIC), it was found that demethylation is the main pathway of DMF degradation in photocatalytic reactions. Furthermore, decontamination of actual polluted tannery waste gas collected in leather factory proved that the photocatalysis on doubly open-ended Ag/TiNT array membrane is an efficient way and a promising application to treat air contaminated by DMF despite the complexity of various volatile organic compounds.

Evaluating Thermodynamic Integration Performance of the New Amber Molecular Dynamics Package and Assess Potential Halogen Bonds of Enoyl-ACP Reductase (FabI) Benzimidazole Inhibitors

PubMed Central

Su, Pin-Chih; Johnson, Michael E.

2015-01-01

Thermodynamic integration (TI) can provide accurate binding free energy insights in a lead optimization program, but its high computational expense has limited its usage. In the effort of developing an efficient and accurate TI protocol for FabI inhibitors lead optimization program, we carefully compared TI with different Amber molecular dynamics (MD) engines (sander and pmemd), MD simulation lengths, the number of intermediate states and transformation steps, and the Lennard-Jones and Coulomb Softcore potentials parameters in the one-step TI, using eleven benzimidazole inhibitors in complex with Francisella tularensis enoyl acyl reductase (FtFabI). To our knowledge, this is the first study to extensively test the new AMBER MD engine, pmemd, on TI and compare the parameters of the Softcore potentials in the one-step TI in a protein-ligand binding system. The best performing model, the one-step pmemd TI, using 6 intermediate states and 1 ns MD simulations, provides better agreement with experimental results (RMSD = 0.52 kcal/mol) than the best performing implicit solvent method, QM/MM-GBSA from our previous study (RMSD = 3.00 kcal/mol), while maintaining similar efficiency. Briefly, we show the optimized TI protocol to be highly accurate and affordable for the FtFabI system. This approach can be implemented in a larger scale benzimidazole scaffold lead optimization against FtFabI. Lastly, the TI results here also provide structure-activity relationship insights, and suggest the para-halogen in benzimidazole compounds might form a weak halogen bond with FabI, which is a well-known halogen bond favoring enzyme. PMID:26666582

Evaluating thermodynamic integration performance of the new amber molecular dynamics package and assess potential halogen bonds of enoyl-ACP reductase (FabI) benzimidazole inhibitors.

PubMed

Su, Pin-Chih; Johnson, Michael E

2016-04-05

Thermodynamic integration (TI) can provide accurate binding free energy insights in a lead optimization program, but its high computational expense has limited its usage. In the effort of developing an efficient and accurate TI protocol for FabI inhibitors lead optimization program, we carefully compared TI with different Amber molecular dynamics (MD) engines (sander and pmemd), MD simulation lengths, the number of intermediate states and transformation steps, and the Lennard-Jones and Coulomb Softcore potentials parameters in the one-step TI, using eleven benzimidazole inhibitors in complex with Francisella tularensis enoyl acyl reductase (FtFabI). To our knowledge, this is the first study to extensively test the new AMBER MD engine, pmemd, on TI and compare the parameters of the Softcore potentials in the one-step TI in a protein-ligand binding system. The best performing model, the one-step pmemd TI, using 6 intermediate states and 1 ns MD simulations, provides better agreement with experimental results (RMSD = 0.52 kcal/mol) than the best performing implicit solvent method, QM/MM-GBSA from our previous study (RMSD = 3.00 kcal/mol), while maintaining similar efficiency. Briefly, we show the optimized TI protocol to be highly accurate and affordable for the FtFabI system. This approach can be implemented in a larger scale benzimidazole scaffold lead optimization against FtFabI. Lastly, the TI results here also provide structure-activity relationship insights, and suggest the parahalogen in benzimidazole compounds might form a weak halogen bond with FabI, which is a well-known halogen bond favoring enzyme. © 2015 Wiley Periodicals, Inc.

Co2+Ti4+ substituted Z-type barium ferrite with enhanced imaginary permeability and resonance frequency

NASA Astrophysics Data System (ADS)

Li, Z. W.; Guoqing, Lin; Chen, Linfeng; Yuping, Wu; Ong, C. K.

2006-03-01

Co2+Ti4+ substitution for Fe3+ in Co2Z (Ba3Co2Fe24O41) has been prepared. The crystal structure and static and high-frequency magnetic properties have been studied for Ba3Co2+xTixFe24-2xO41 and the corresponding ferrite/polymer composites. As compared to the general Co2Z ferrite/polymer composite, the CoTi substituted ferrite/polymer composite with x=1.0 has a high natural resonance frequency (4.5 GHz), due to its large out-of-plane anisotropy fields Hθ. Furthermore, the maximum imaginary permeability μmax'' is increased by about 50%. The increase is attributed to a decreased damping coefficient, based on the curve-fitted results to the complex permeability spectra. The composites are good electromagnetic attenuation materials with low reflectivity and broad bandwidth at microwave frequencies.

Progress in the Science and Technology of Direct Drive Laser Fusion with the KrF Laser

DTIC Science & Technology

2010-12-01

important parameters KrF technology leads) Direct Laser Drive is a better choice for Energy Indirect Drive (initial path for NIF ) Laser Beams x-rays Hohlraum...Pellet Direct Drive (IFE) Laser Beams Pellet .. • ID Ignition being explored on NIF • Providing high enough gain for pure fusion energy is...challenging. • DD Ignition physics can be explored on NIF . • More efficient use of laser light, and greater flexibility in applying drive provides potential for

Electra: Repetitively Pulsed 700 J, 100 ns Electron Beam Pumped KrF Laser

DTIC Science & Technology

2006-05-01

the Inertial Fusion Energy (IFE) requirements for durability, efficiency, and cost. The technologies developed on Electra should be directly scalable...and S. Searles, "Electron beam pumped krypton fluoride lasers for fusion energy ," Proc. IEEE, vol. 92, pp. 1043-1056, July 2004. [2] M.C. Myers, J.D...34Repetitively pulsed, high energy KrF lasers for inertial fusion energy ," Nucl. Fusion, vol. 44, pp. S247-S253, November 2004. [3] J.D. Sethian, M

Optical properties of trinuclear metal chalcogenolate complexes - room temperature NIR fluorescence in [Cu2Ti(SPh)6(PPh3)2].

PubMed

Kühn, Michael; Lebedkin, Sergei; Weigend, Florian; Eichhöfer, Andreas

2017-01-31

The optical properties of four isostructural trinuclear chalcogenolato bridged metal complexes [Cu 2 Sn(SPh) 6 (PPh 3 ) 2 ], [Cu 2 Sn(SePh) 6 (PPh 3 ) 2 ], [Ag 2 Sn(SPh) 6 (PPh 3 ) 2 ] and [Cu 2 Ti(SPh) 6 (PPh 3 ) 2 ] have been investigated by absorption and photoluminescence spectroscopy and time-dependent density functional theory (TDDFT) calculations. All copper-tin compounds demonstrate near-infrared (NIR) phosphorescence at ∼900-1100 nm in the solid state at low temperature, which is nearly absent at ambient temperature. Stokes shifts of these emissions are found to be unusually large with values of about 1.5 eV. The copper-titanium complex [Cu 2 Ti(SPh) 6 (PPh 3 ) 2 ] also shows luminescence in the NIR at 1090 nm but with a much faster decay (τ ∼ 10 ns at 150 K) and a much smaller Stokes shift (ca. 0.3 eV). Even at 295 K this fluorescence is found to comprise a quantum yield as high as 9.5%. The experimental electronic absorption spectra well correspond to the spectra simulated from the calculated singlet transitions. In line with the large Stokes shifts of the emission spectra the calculations reveal for the copper-tin complexes strong structural relaxation of the excited triplet states whereas those effects are found to be much smaller in the case of the copper-titanium complex.

Si/Ti2O3/Reduced Graphene Oxide Nanocomposite Anodes for Lithium-Ion Batteries with Highly Enhanced Cyclic Stability.

PubMed

Park, A Reum; Son, Dae-Yong; Kim, Jung Sub; Lee, Jun Young; Park, Nam-Gyu; Park, Juhyun; Lee, Joong Kee; Yoo, Pil J

2015-08-26

Silicon (Si) has attracted tremendous attention as a high-capacity anode material for next generation Li-ion batteries (LIBs); unfortunately, it suffers from poor cyclic stability due to excessive volume expansion and reduced electrical conductivity after repeated cycles. To circumvent these issues, we propose that Si can be complexed with electrically conductive Ti2O3 to significantly enhance the reversible capacity and cyclic stability of Si-based anodes. We prepared a ternary nanocomposite of Si/Ti2O3/reduced graphene oxide (rGO) using mechanical blending and subsequent thermal reduction of the Si, TiO2 nanoparticles, and rGO nanosheets. As a result, the obtained ternary nanocomposite exhibited a specific capacity of 985 mAh/g and a Coulombic efficiency of 98.4% after 100 cycles at a current density of 100 mA/g. Furthermore, these ternary nanocomposite anodes exhibited outstanding rate capability characteristics, even with an increased current density of 10 A/g. This excellent electrochemical performance can be ascribed to the improved electron and ion transport provided by the Ti2O3 phase within the Si domains and the structurally reinforced conductive framework comprised of the rGO nanosheets. Therefore, it is expected that our approach can also be applied to other anode materials to enable large reversible capacity, excellent cyclic stability, and good rate capability for high-performance LIBs.

Evolution and Control of Electronic Structures near the Interface of Complex Oxide Heterostructure SmTiO3/SrTiO3

NASA Astrophysics Data System (ADS)

Mori, Ryo; Marshall, Patrick; Isaac, Brandon; Denlinger, Jonathan; Stemmer, Susanne; Lanzara, Alessandra

The confined electron system in the quantum well of the transition metal oxide, SrTiO3, embedded in the rare earth titanate, SmTiO3, shows unique properties, such as high carrier density, fermi liquid to non-fermi liquid transition, and pseudo-gap, which can be controlled by changing the shape of the quantum well. We will present a distinct difference in the electronic structures between the different quantum well structures obtained by angle-resolved photoemission spectroscopy (ARPES) measurements, suggesting the possibility to control the orbital character and the electron correlation near the interface as well as carrier density. The work was supported by the Quantum Materials Program at LBNL, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under Contract No. DE-AC02-05CH11231.

Flexible tensile strain sensor based on lead-free 0.5Ba (Ti0.8Zr0.2) O3-0.5(Ba0.7Ca0.3) TiO3 piezoelectric nanofibers

NASA Astrophysics Data System (ADS)

Xing, Lindong; Zhu, Ruijian; Wang, Zengmei; Wang, Fengxia; Kimura, Hideo

2017-09-01

Here, we report our study results of a flexible piezoelectric tensile strain sensor which is fabricated by synthesizing 0.5Ba (Zr0.2Ti0.8) O3-0.5(Ba0.7Ca0.3) TiO3 (0.5BZT-0.5BCT) nanofibers via an electrospinning process. Our nanofibers show an ultrahigh d33 of 275 pm V-1. 0.5BZT-0.5BCT nanofibers and MW-CNTs are dispersed in polydimethylsiloxane (PDMS) to fabricate a highly stretchable and flexible tensile sensor, and the multiple roles of the MW-CNTs are probed and demonstrated. This nanofiber-based piezoelectric tensile strain sensor shows great resolution and sensitivity under external mechanical deformation. It is suitable for applications in complex environments.

Anatase TiO2 as a Cheap and Sustainable Buffering Filler for Silicon Nanoparticles in Lithium-Ion Battery Anodes.

PubMed

Maroni, Fabio; Carbonari, Gilberto; Croce, Fausto; Tossici, Roberto; Nobili, Francesco

2017-12-08

The design of effective supporting matrices to efficiently cycle Si nanoparticles is often difficult to achieve and requires complex preparation strategies. In this work, we present a simple synthesis of low-cost and environmentally benign aAnatase TiO 2 nanoparticles as buffering filler for Si nanoparticles (Si@TiO 2 ). The average anatase TiO 2 crystallite size was approximately 5 nm. A complete structural, morphological, and electrochemical characterization was performed. Electrochemical test results show very good specific capacity values of up to 1000 mAh g -1 and cycling at several specific currents, ranging from 500 to 2000 mA g -1 , demonstrating a very good tolerance to high cycling rates. Postmortem morphological analysis shows very good electrode integrity after 100 cycles at 500 mA g -1 specific current. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Particle morphology influence on mechanical and biocompatibility properties of injection molded Ti alloy powder.

PubMed

Gülsoy, H Özkan; Gülsoy, Nagihan; Calışıcı, Rahmi

2014-01-01

Titanium and Titanium alloys exhibits properties that are excellent for various bio-applications. Metal injection molding is a processing route that offers reduction in costs, with the added advantage of near net-shape components. Different physical properties of Titanium alloy powders, shaped and processed via injection molding can achieve high complexity of part geometry with mechanical and bioactivity properties, similar or superior to wrought material. This study describes that the effect of particle morphology on the microstructural, mechanical and biocompatibility properties of injection molded Ti-6Al-4V (Ti64) alloy powder for biomaterials applications. Ti64 powders irregular and spherical in shape were injection molded with wax based binder. Binder debinding was performed in solvent and thermal method. After debinding the samples were sintered under high vacuum. Metallographic studies were determined to densification and the corresponding microstructural changes. Sintered samples were immersed in a simulated body fluid (SBF) with elemental concentrations that were comparable to those of human blood plasma for a total period of 15 days. Both materials were implanted in fibroblast culture for biocompatibility evaluations were carried out. The results show that spherical and irregular powder could be sintered to a maximum theoretical density. Maximum tensile strength was obtained for spherical shape powder sintered. The tensile strength of the irregular shape powder sintered at the same temperature was lower due to higher porosity. Finally, mechanical tests show that the irregular shape powder has lower mechanical properties than spherical shape powder. The sintered irregular Ti64 powder exhibited better biocompatibility than sintered spherical Ti64 powder. Results of study showed that sintered spherical and irregular Ti64 powders exhibited high mechanical properties and good biocompatibility properties.

Allylic aminations with hindered secondary amine nucleophiles catalyzed by heterobimetallic Pd-Ti complexes.

PubMed

Walker, Whitney K; Anderson, Diana L; Stokes, Ryjul W; Smith, Stacey J; Michaelis, David J

2015-02-06

Phosphinoamide-scaffolded heterobimetallic palladium-titanium complexes are highly effective catalysts for allylic aminations of allylic chlorides with hindered secondary amine nucleophiles. Three titanium-containing ligands are shown to assemble active catalysts in situ and enable catalysis at room temperature. A variety of sterically bulky secondary amines are efficiently allylated in high yields with as little as 1 mol % palladium catalyst. Piperidine and pyrrolidine products are also efficiently generated via intramolecular aminations with hindered amine nucleophiles.

Generation of TiII Alkyne Trimerization Catalysts in the Absence of Strong Metal Reductants

PubMed Central

See, Xin Yi; Beaumier, Evan P.; Davis-Gilbert, Zachary W.; Dunn, Peter L.; Larsen, Jacob A.; Pearce, Adam J.; Wheeler, T. Alex; Tonks, Ian A.

2017-01-01

Low-valent TiII species have typically been synthesized by the reaction of TiIV halides with strong metal reductants. Herein we report that TiII species can be generated simply by reacting TiIV imido complexes with 2 equiv of alkyne, yielding a metallacycle that can reductively eliminate pyrrole while liberating TiII. In order to probe the generality of this process, TiII-catalyzed alkyne trimerization reactions were carried out with a diverse range of TiIV precatalysts. PMID:28690352

Study on dissolution behavior of polymer-bound and polymer-blended photo-acid generator (PAG) resists

NASA Astrophysics Data System (ADS)

Yamamoto, Hiroki; Kozawa, Takahiro; Tagawa, Seiichi

2013-03-01

The requirements for the next generation resist materials are so challenging that it is indispensable for feasibility of EUV lithography to grasp basic chemistry of resist matrices in all stage of resist processes. Under such circumstances, it is very important to know dissolution characteristics of the resist film into alkaline developer though the dissolution of exposed area of resist films in alkaline developer to form a pattern is a complex reactive process. In this study, the influence of EUV and KrF exposure on the dissolution behavior of polymer bound PAG and polymer blended PAG was studied in detail using quartz crystal microbalance (QCM) methods. The difference in swelling formation between KrF and EUV exposure was observed. It is likely that difference of reaction mechanism induces the difference of these swelling. Also, it is observed that the swelling of polymer-bound PAG is less than that of polymer blended PAG in both KrF and EUV exposure. This result indicates that polymer-bound PAG suppresses swelling very well and showed an excellent performance. Actually, the developed polymer bound-PAG resist showed an excellent performance (half pitch 50 nm line and space pattern). Thus, polymer bound PAG is one of the promising candidate for 16 nm EUV resist.

Identification of Near-infrared [Se III] and [Kr VI] Emission Lines in Planetary Nebulae

NASA Astrophysics Data System (ADS)

Sterling, N. C.; Madonna, S.; Butler, K.; García-Rojas, J.; Mashburn, A. L.; Morisset, C.; Luridiana, V.; Roederer, I. U.

2017-05-01

We identify [Se III] 1.0994 μm in the planetary nebula (PN) NGC 5315 and [Kr VI] 1.2330 μm in three PNe from spectra obtained with the Folded-Port InfraRed Echellette (FIRE) spectrometer on the 6.5 m Baade Telescope. Se and Kr are the two most widely detected neutron-capture elements in astrophysical nebulae, and can be enriched by s-process nucleosynthesis in PN progenitor stars. The detection of [Se III] 1.0994 μm is particularly valuable when paired with observations of [Se IV] 2.2864 μm, as it can be used to improve the accuracy of nebular Se abundance determinations, and allows Se ionization correction factor (ICF) schemes to be empirically tested for the first time. We present new effective collision strength calculations for Se2+ and Kr5+, which we use to compute ionic abundances. In NGC 5315, we find that the Se abundance computed from Se3+/H+ is lower than that determined with ICFs that incorporate Se2+/H+. We compute new Kr ICFs that take Kr5+/H+ into account, by fitting correlations found in grids of Cloudy models between Kr ionic fractions and those of more abundant elements, and use these to derive Kr abundances in four PNe. Observations of [Se III] and [Kr VI] in a larger sample of PNe, with a range of excitation levels, are needed to rigorously test the ICF prescriptions for Se and our new Kr ICFs. This paper includes data obtained with the 6.5-m Magellan Telescopes at Las Campanas Observatory, Chile.

The Effect of Sequential Dependence on the Sampling Distributions of KR-20, KR-21, and Split-Halves Reliabilities.

ERIC Educational Resources Information Center

Sullins, Walter L.

Five-hundred dichotomously scored response patterns were generated with sequentially independent (SI) items and 500 with dependent (SD) items for each of thirty-six combinations of sampling parameters (i.e., three test lengths, three sample sizes, and four item difficulty distributions). KR-20, KR-21, and Split-Half (S-H) reliabilities were…

Development in understanding of Gauss-Krüger projection and its outcomes

NASA Astrophysics Data System (ADS)

Masaharu, Hiroshi

2018-05-01

The role of Gauss and Krüger is made clear in developing Gauss-Krüger projection. Gauss developed the projection and Krüger had brought Gauss's posthumous work into the open. From studying such historical issues, useful projection formula was found and this is now implemented for actual usage in surveying in Japan.

Kinetics of the iodine- and bromine-mediated transport of halide ions: demonstration of an interfacial complexation mechanism.

PubMed Central

Klotz, K H; Benz, R

1993-01-01

Stationary and kinetic experiments were performed on lipid bilayer membranes to study the mechanism of iodine- and bromine-mediated halide transport in detail. The stationary conductance data suggested that four different 1:1 complexes between I2 and Br2 and the halides I- and Br- were responsible for the observed conductance increase by iodine and bromine (I3-, I2Br-, Br2I-, and Br3-). Charge pulse experiments allowed the further elucidation of the transport mechanism. Only two of three exponential voltage relaxations predicted by the Läuger model could be resolved under all experimental conditions. This means that either the heterogeneous complexation reactions kR (association) and kD (dissociation) were too fast to be resolved or that the neutral carriers were always in equilibrium within the membrane. Experiments at different carrier and halide concentrations suggested that the translocation of the neutral carrier is much faster than the other processes involved in carrier-mediated ion transport. The model was modified accordingly. From the charge pulse data at different halide concentrations, the translocation rate constant of the complexed carriers, kAS, the dissociation constant, kD, and the total surface concentration of charged carriers, NAS, could be evaluated from one single charge pulse experiment. The association rate of the complex, kR, could be obtained in some cases from the plot of the stationary conductance data as a function of the halide concentration in the aqueous phase. The translocation rate constant, kAS, of the different complexes is a function of the image force and of the Born charging energy. It increases 5000-fold from Br3- to I3- because of an enlarged ion radius. PMID:8312500

Computational study of pristine and titanium-doped sodium alanates for hydrogen storage applications

NASA Astrophysics Data System (ADS)

Dathar, Gopi Krishna Phani

The emphasis of this research is to study and elucidate the underlying mechanisms of reversible hydrogen storage in pristine and Ti-doped sodium aluminum hydrides using molecular modeling techniques. An early breakthrough in using complex metal hydrides as hydrogen storage materials is from the research on sodium alanates by Bogdanovic et al., in 1997 reporting reversible hydrogen storage is possible at moderate temperatures and pressures in transition metal doped sodium alanates. Anton reported titanium salts as the best catalysts compared to all other transition metal salts from his further research on transition metal doped sodium alanates. However, a few questions remained unanswered regarding the role of Ti in reversible hydrogen storage of sodium alanates with improved thermodynamics and kinetics of hydrogen desorption. The first question is about the position of transition metal dopants in the sodium aluminum hydride lattice. The position is investigated by identifying the possible sites for titanium dopants in NaAlH4 lattice and studying the structure and dynamics of possible compounds resulting from titanium doping in sodium alanates. The second question is the role of titanium dopants in improved thermodynamics of hydrogen desorption in Ti-doped NaAlH4. Though it is accepted in the literature that formation of TiAl alloys (Ti-Al and TiAl3) is favorable, reaction pathways are not clearly established. Furthermore, the source of aluminum for Ti-Al alloy formation is not clearly understood. The third question in this area is the role of titanium dopants in improved kinetics of hydrogen absorption and desorption in Ti-doped sodium alanates. This study is directed towards addressing the three longstanding questions in this area. Thermodynamic and kinetic pathways for hydrogen desorption in pristine NaAlH4 and formation of Ti-Al alloys in Ti-doped NaAlH 4, are elucidated to understand the underlying mechanisms of hydrogen desorption. Density functional theory formalism as implemented in CASTEP (Cambridge Serial Total Energy Package) is used to study the structure and energetics of pristine and Ti-doped sodium alanates. From investigations of various models of sodium alanates with Ti dopants, it is shown that the difference between the energy required for Ti→SNa (Ti-substituted Na at the lattice site on the surface) and Ti→TI (Ti placed on top of the surface interstitial SI site) is 0.003 eV atom-1, and is minimal compared to other models. Since less energy is required for Ti→S Na and Ti→TI, these two sites (SNa and T I) would be preferred by the Ti dopants. In Ti→SNa model, Ti is coordinated to two aluminum and seven hydrogen atoms resulting in the possible formation of a TiAl2H7 complex. At elevated temperatures (423 and 448 K), the number of aluminum atoms coordinating with titanium in the complex increase from two (at distances in the 2.6-2.7 A range) to five (at distances in the 2.6-2.7 A range). Besides the formation of a Ti-Al-H complex, Al-Al association (with a 2.97 A bond length) is also seen from the DFT-MD results. In the case of Ti→TI, Ti is coordinated to two aluminum and two hydrogen atoms resulting in the possible formation of a TiAl2H2 complex. TiAl2 H2 complex becomes TiAl3H6 and TiAl 3H7 at elevated temperatures of 423 and 448 K, respectively. The investigation of thermodynamics pathways in Ti-doped sodium alanates illustrates a three step reaction pathway to the formation of TiAl3 (Ti and AlH3 after the first reaction, TiAl after the second and finally TiAl3). This investigation also suggests aluminum in its +3 oxidation state present in aluminum hydride species is responsible in the formation of Ti-Al alloys. From kinetics studies, the proposed mechanism is related to transition from AlH4- to AlH6 3-. The rate limiting step is determined to be associated with hydrogen evolution from association of AlH3 species nucleating aluminum phase. This step is 15 kJ/mol higher than the nearest highest barrier in the reaction path related to transition from AlH52- to AlH63-. From the DFT-MD simulations, it is observed that the titanium dopants are present on the surface during the entire simulation time and exhibit the role in catalytic splitting of hydrogen from surrounding AlH4 groups. Besides the catalytic role, Ti dopants also form bonds with Al, and we also see that the AlH4 groups on the surface and that are present in the sub-surface layers are drawn towards the Ti dopants. This association of Al around titanium indicates the initiation of Al nucleation site facilitated by Ti dopants residing on the surface.

Krypton-81 in groundwater of the Culebra Dolomite near the Waste Isolation Pilot Plant, New Mexico

NASA Astrophysics Data System (ADS)

Sturchio, Neil C.; Kuhlman, Kristopher L.; Yokochi, Reika; Probst, Peter C.; Jiang, Wei; Lu, Zheng-Tian; Mueller, Peter; Yang, Guo-Min

2014-05-01

The Waste Isolation Pilot Plant (WIPP) in New Mexico is the first geologic repository for disposal of transuranic nuclear waste from defense-related programs of the US Department of Energy. It is constructed within halite beds of the Permian-age Salado Formation. The Culebra Dolomite, confined within Rustler Formation evaporites overlying the Salado Formation, is a potential pathway for radionuclide transport from the repository to the accessible environment in the human-disturbed repository scenario. Although extensive subsurface characterization and numerical flow modeling of groundwater has been done in the vicinity of the WIPP, few studies have used natural isotopic tracers to validate the flow models and to better understand solute transport at this site. The advent of Atom-Trap Trace Analysis (ATTA) has enabled routine measurement of cosmogenic 81Kr (half-life 229,000 yr), a near-ideal tracer for long-term groundwater transport. We measured 81Kr in saline groundwater sampled from two Culebra Dolomite monitoring wells near the WIPP site, and compared 81Kr model ages with reverse particle-tracking results of well-calibrated flow models. The 81Kr model ages are ~ 130,000 and ~ 330,000 yr for high-transmissivity and low-transmissivity portions of the formation, respectively. Compared with flow model results which indicate a relatively young mean hydraulic age (~ 32,000 yr), the 81Kr model ages imply substantial physical attenuation of conservative solutes in the Culebra Dolomite and provide limits on the effective diffusivity of contaminants into the confining aquitards.

Metal-organic frameworks for Xe/Kr separation

DOEpatents

Ryan, Patrick J.; Farha, Omar K.; Broadbelt, Linda J.; Snurr, Randall Q.; Bae, Youn-Sang

2014-07-22

Metal-organic framework (MOF) materials are provided and are selectively adsorbent to xenon (Xe) over another noble gas such as krypton (Kr) and/or argon (Ar) as a result of having framework voids (pores) sized to this end. MOF materials having pores that are capable of accommodating a Xe atom but have a small enough pore size to receive no more than one Xe atom are desired to preferentially adsorb Xe over Kr in a multi-component (Xe--Kr mixture) adsorption method. The MOF material has 20% or more, preferably 40% or more, of the total pore volume in a pore size range of 0.45-0.75 nm which can selectively adsorb Xe over Kr in a multi-component Xe--Kr mixture over a pressure range of 0.01 to 1.0 MPa.

Metal-organic frameworks for Xe/Kr separation

DOEpatents

Ryan, Patrick J.; Farha, Omar K.; Broadbelt, Linda J.; Snurr, Randall Q.; Bae, Youn-Sang

2013-08-27

Metal-organic framework (MOF) materials are provided and are selectively adsorbent to xenon (Xe) over another noble gas such as krypton (Kr) and/or argon (Ar) as a result of having framework voids (pores) sized to this end. MOF materials having pores that are capable of accommodating a Xe atom but have a small enough pore size to receive no more than one Xe atom are desired to preferentially adsorb Xe over Kr in a multi-component (Xe--Kr mixture) adsorption method. The MOF material has 20% or more, preferably 40% or more, of the total pore volume in a pore size range of 0.45-0.75 nm which can selectively adsorb Xe over Kr in a multi-component Xe--Kr mixture over a pressure range of 0.01 to 1.0 MPa.

Research and Process-Optimization on Mixed Crystal Caused Uneven-Performance of High-strength Structural Car Steel QStE500TM

NASA Astrophysics Data System (ADS)

Jian-wen, Li; Hong-yan, Liu

Handan Iron and Steel production of high-strength structural car steel QStE500TM thin gauge products using Nb + Ti composite strengthening, with a small amount of Cr element to improve its hardenability, the process parameter control is inappropriate with Nb + Ti complex steel, it is easy to produce in the mixed crystal phenomenon, resulting in decreasing the toughness and uneven performance. In this paper, Gleeble 3500 thermal simulation testing machine for high-strength structural steel car QStE500TM product deformation austenite recrystallization behavior research, determined completely recrystallized, partial recrystallization and non-recrystallization region, provide theoretical basis and necessary data for reasonable controlled rolling process for production.

Kr ion irradiation study of the depleted-uranium alloys

NASA Astrophysics Data System (ADS)

Gan, J.; Keiser, D. D.; Miller, B. D.; Kirk, M. A.; Rest, J.; Allen, T. R.; Wachs, D. M.

2010-12-01

Fuel development for the reduced enrichment research and test reactor (RERTR) program is tasked with the development of new low enrichment uranium nuclear fuels that can be employed to replace existing high enrichment uranium fuels currently used in some research reactors throughout the world. For dispersion type fuels, radiation stability of the fuel-cladding interaction product has a strong impact on fuel performance. Three depleted-uranium alloys are cast for the radiation stability studies of the fuel-cladding interaction product using Kr ion irradiation to investigate radiation damage from fission products. SEM analysis indicates the presence of the phases of interest: U(Al, Si) 3, (U, Mo)(Al, Si) 3, UMo 2Al 20, U 6Mo 4Al 43 and UAl 4. Irradiations of TEM disc samples were conducted with 500 keV Kr ions at 200 °C to ion doses up to 2.5 × 10 19 ions/m 2 (˜10 dpa) with an Kr ion flux of 10 16 ions/m 2/s (˜4.0 × 10 -3 dpa/s). Microstructural evolution of the phases relevant to fuel-cladding interaction products was investigated using transmission electron microscopy.

Improving the optoelectronic properties of titanium-doped indium tin oxide thin films

NASA Astrophysics Data System (ADS)

Taha, Hatem; Jiang, Zhong-Tao; Henry, David J.; Amri, Amun; Yin, Chun-Yang; Mahbubur Rahman, M.

2017-06-01

The focus of this study is on a sol-gel method combined with spin-coating to prepare high-quality transparent conducting oxide (TCO) films. The structural, morphological, optical and electrical properties of sol-gel-derived pure and Ti-doped indium tin oxide (ITO) thin films were studied as a function of the concentration of the Ti (i.e. 0 at%, 2 at% and 4 at%) and annealing temperatures (150 °C-600 °C). FESEM measurements indicate that all the films are ˜350 nm thick. XRD analysis confirmed the cubic bixbyite structure of the polycrystalline indium oxide phase for all of the thin films. Increasing the Ti ratio, as well as the annealing temperature, improved the crystallinity of the films. Highly crystalline structures were obtained at 500 °C, with average grain sizes of about 50, 65 and 80 nm for Ti doping of 0 at%, 2 at% and 4 at%, respectively. The electrical and optical properties improved as the annealing temperature increased, with an enlarged electronic energy band gap and an optical absorption edge below 280 nm. In particular, the optical transmittance and electrical resistivity of the samples with a 4 at% Ti content improved from 87% and 7.10 × 10-4 Ω.cm to 92% and 1.6 × 10-4 Ω.cm, respectively. The conductivity, especially for the annealing temperature at 150 °C, is acceptable for many applications such as flexible electronics. These results demonstrate that unlike the more expensive and complex vacuum sputtering process, high-quality Ti-doped ITO films can be achieved by fast processing, simple wet-chemistry, and easy doping level control with the possibility of producing films with high scalability.

Influence of Europium Doping on Various Electrical Properties of Low-Temperature Sintered 0.5Ba0.90Ca0.10TiO3-0.5BaTi0.88Zr0.12O3-0.1%CuO- xEu Lead-Free Ceramics

NASA Astrophysics Data System (ADS)

Tian, Yongshang; Li, Shuiyun; Sun, Shulin; Gong, Yansheng; Li, Tiantian; Yu, Yongshang; Jing, Qiangshan

2018-01-01

0.5Ba0.90Ca0.10TiO3-0.5BaTi0.88Zr0.12O3-0.1%CuO- xEu (BCT-BZT-Cu- xEu; x = 0-0.90%) lead-free ceramics were sintered at 1220°C with as-synthesized nanoparticles by a modified Pechini method. The structural characteristics and electrical properties of the ceramics that were influenced by varying europium-doping were investigated. All the ceramics featured high densification (relative density: ˜ 96%). X-ray powder diffraction results indicated the samples possessed pure orthorhombic phase. The maximum relative permittivity ( ɛ r, 10869) was found at x around 0.30%. Europium ions could dope on different substitution sites in the ABO3 lattice, which evidently influenced electrical properties with various volumes of oxygen vacancy. Moreover, the formation mechanisms of oxygen vacancy and defect electron complexes were stated. The piezoelectric properties were impacted by defect electron complexes, internal stress, ionic electronegativity, etc. The optimal electrical properties, i.e., d 33 = 384 pC/N, Q m = 92, and k p = 0.36, were detected at x = 0.45%.

ATTA-3: a State-of-the-Art Instrument for Radio-Krypton Dating

NASA Astrophysics Data System (ADS)

Jiang, W.; Zappala, J. C.; Bailey, K.; Lu, Z.; Müller, P.; O'Connor, T. P.

2013-12-01

The ATTA-3 instrument at Argonne has recently enabled routine Kr-81 dating. The instrument is based on Atom Trap Trace Analysis (ATTA), a novel laser based atom counting technique that allows detection of long lived noble gas radioisotopes (Kr-81, Kr-85 and Ar-39) with extremely low abundance (1E-16 to 1E-10). At the center of the instrument is a magneto-optical trap (MOT), which traps and counts only the atoms of the desired isotope. This unique feature makes ATTA free of interference from any other isotopes or molecular species. For Kr-81 dating in the age range of 150 - 1,500 kyr, the required sample size is 5 - 10 micro-L STP of krypton gas, which can be extracted from approximately 100 - 200 kg of water or 40 - 80 kg of ice. Several recent developments in our lab may lead to further improvements to the current ATTA-3 apparatus: 1) The isotopic abundance ratio between the unknown, rare isotope (either Kr-81 or Kr-85) and the stable, abundant isotope (Kr-83) is measured. Here the stable isotope serves as a control isotope. A new method has been developed that allows more accurate measurements of the control isotope Kr-83. Combined with the ability to measure the rare Kr-81 and Kr-85 isotopes, this scheme allows ATTA-3 to directly determine 81Kr/Kr and 85Kr/Kr ratios without other supplemental measurements, to reduce the overall uncertainties of the measured isotope ratios, and also to improve the long term stability of the system. 2) The current capacity of the ATTA-3 instrument is about 120 samples per year. The throughput is mainly limited by the so called 'memory effect', which is caused by the residual samples trapped in the system after each measurement. These residual samples are gradually released in subsequent measurements, causing cross-sample contaminations. In order to mitigate this problem, we wash the system with a xenon discharge for about 36 hours between measurements. This practice limits the overall sample processing speed. Preliminary investigations of the memory effect indicate that it can be reduced and the wash time between measurements shortened. This will increase the number of samples that the ATTA-3 instrument can handle annually in the future. This work is supported by DOE, Office of Nuclear Physics, under contract DE-AC02-06CH11357.

The influence of different cucumariosides on immunogenicity of OmpF porin from Yersinia pseudotuberulosis as a model protein antigen of tubular immunostimulating complex

NASA Astrophysics Data System (ADS)

Sanina, N. M.; Chopenko, N. S.; Davydova, L. A.; Mazeika, A. N.; Portnyagina, O. Yu.; Kim, N. Yu.; Golotin, V. A.; Kostetsky, E. Y.; Shnyrov, V. L.

2017-09-01

Nanoparticulate tubular immunostimulating complex (TI-complex) is a novel promising adjuvant carrier of antigens allowing to create safe and effective vaccines of new generation. The adjuvant activity of TI-complexes based on monogalactosyldyacylglycerol (MGDG) from the sea alga Ulva lactuca and different triterpene glycosides cucumariosides (CDs) from marine invertebrate Cucumaria japonica and their fractions was studied to assess effects of different CDs on the immunogenicity of porin OmpF from Yersinia pseudotuberculosis (YOmpF). TI-complexes with cucumarioside A2-2 (CDA2-2) maximally stimulated anti-porin antibody production. Studies of protein intrinsic fluorescence showed that all CDs had a relaxing effect on the conformation of YOmpF, loosening peripheral region of protein and promoting exposure of the protein antigenic determinants to the water environment. The greatest immunostimulating effect of TI-complexes comprising CDA2-2 was accompanied by mild effect of this CD on the tertiary structure of protein antigen YOmpF, whereas cucumarioside E (CDE) and cucumarioside A2-4 (CDA2-4) caused especially sharp redistribution of spectral form of the YOmpF corresponding to the emission of an intrinsic protein fluorophore tryptophan.

Facile Synthesis and Superior Catalytic Activity of Nano-TiN@N-C for Hydrogen Storage in NaAlH4.

PubMed

Zhang, Xin; Ren, Zhuanghe; Lu, Yunhao; Yao, Jianhua; Gao, Mingxia; Liu, Yongfeng; Pan, Hongge

2018-05-09

Herein, we synthesize successfully ultrafine TiN nanoparticles (<3 nm in size) embedded in N-doped carbon nanorods (nano-TiN@N-C) by a facile one-step calcination process. The prepared nano-TiN@N-C exhibits superior catalytic activity for hydrogen storage in NaAlH 4 . Adding 7 wt % nano-TiN@N-C induces more than 100 °C reduction in the onset dehydrogenation temperature of NaAlH 4 . Approximately 4.9 wt % H 2 is rapidly released from the 7 wt % nano-TiN@N-C-containing NaAlH 4 at 140 °C within 60 min, and the dehydrogenation product is completely hydrogenated at 100 °C within 15 min under 100 bar of hydrogen, exhibiting significantly improved desorption/absorption kinetics. No capacity loss is observed for the nano-TiN@N-C-containing sample within 25 de-/hydrogenation cycles because nano-TiN functions as an active catalyst instead of a precursor. A severe structural distortion with extended bond lengths and reduced bond strengths for Al-H bonding when the [AlH 4 ] - group adsorbs on the TiN cluster is demonstrated for the first time by density functional theory calculations, which well-explains the reduced de-/hydrogenation temperatures of the nano-TiN@N-C-containing NaAlH 4 . These findings provide new insights into designing and synthesizing high-performance catalysts for hydrogen storage in complex hydrides.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Hang, E-mail: xhinbj@126.com; Li, Mei; Jun, Zhang

Graphical abstract: The micro morphological structure of the nano-TiO{sub 2} particles was also observed with TEM, as shown in figure. The TEM images clearly exhibited the homogeneous microstructure of particles with a size of around 10–15 nm. - Highlights: • Nano-TiO{sub 2} was prepared by complex techniques of sol–gel, micro-emulsion and solvent thermal. • The size of TiO{sub 2} was nano level and uniformity. • Nano-TiO{sub 2} exhibited high photo-catalytic activity at internal air lift circulating reactor. • The best nano-TiO{sub 2} dosage was obtained. - Abstract: Anatase nano-titania (TiO{sub 2}) powder was prepared by using a sol–gel process mediatedmore » in reverse microemulsion combined with a solvent thermal technique. The structures of the obtained TiO{sub 2} were characterized by TG-DSC, XRD, TEM. The photocatalytic decomposition of methylene blue (MB) on nano-TiO{sub 2} was studied by using an internal air lift circulating photocatalytic reactor. The results show that the anatase structure appears in the calcination temperature range of 400–510 °C, while the transformation of anatase into rutile takes place above 510 °C. The homogeneous microstructure of nano-TiO{sub 2} particles was obtained with a size of around 10–15 nm. In the photocatalytic performance, degradation process follows pseudo first order kinetics with different dosages of photocatalyst and initial MB concentrations and optimal TiO{sub 2} dosage is 0.1 g/L with neutral medium.« less

Comparison of the virulence of three H3N2 canine influenza virus isolates from Korea and China in mouse and Guinea pig models.

PubMed

Xie, Xing; Na, Woonsung; Kang, Aram; Yeom, Minjoo; Yuk, Heejun; Moon, Hyoungjoon; Kim, Sung-Jae; Kim, Hyun-Woo; Kim, Jeong-Ki; Pang, Maoda; Wang, Yongshan; Liu, Yongjie; Song, Daesub

2018-05-02

Avian-origin H3N2 canine influenza virus (CIV) has been the most common subtype in Korea and China since 2007. Here, we compared the pathogenicity and transmissibility of three H3N2 CIV strains [Chinese CIV (JS/10), Korean CIV (KR/07), and Korean recombinant CIV between the classic H3N2 CIV and the pandemic H1N1 virus (MV/12)] in BALB/c mouse and guinea pig models. The pandemic H1N1 (CA/09) strain served as the control. BALB/c mice infected with H1N1 had high mortality and obvious body weight loss, whereas no overt disease symptoms were observed in mice inoculated with H3N2 CIV strains. The viral titers were higher in the group MV/12 than those in groups JS/10 and KR/07, while the mice infected with JS/10 showed higher viral titers in all tissues (except for the lung) than the mice infected with KR/07. The data obtained in guinea pigs also demonstrated that group MV/12 presented the highest loads in most of the tissues, followed by group JS/10 and KR/07. Also, direct contact transmissions of all the three CIV strains could be observed in guinea pigs, and for the inoculated and the contact groups, the viral titer of group MV/12 and KR/07 was higher than that of group JS/10 in nasal swabs. These findings indicated that the matrix (M) gene obtained from the pandemic H1N1 may enhance viral replication of classic H3N2 CIV; JS/10 has stronger viral replication ability in tissues as compared to KR/07, whereas KR/07 infected guinea pigs have more viral shedding than JS/10 infected guinea pigs. There exists a discrepancy in pathobiology among CIV isolates. Reverse genetics regarding the genomes of CIV isolates will be helpful to further explain the virus characteristics.

Well-defined Ti 4 pre-catalysts for the ring-opening polymerisation of lactide

DOE PAGES

Cols, Jean-Marie E. P.; Taylor, Cameron E.; Gagnon, Kevin J.; ...

2016-10-17

Here, the synthesis and full characterisation of four discrete tetrametallic titanium complexes is reported. These well-defined compounds are isostructural in the solid state and share the same general formula: Ti 4(μ-O) 2L 4 (L = 1, 2, 3 or 4). Using a combination of NMR techniques the complexes are found to be stable in solution, even at elevated temperatures. Further studies show that the carboxylate moieties of the supporting amine bis(phenolate) ligands can be displaced by a more strongly coordinating solvent. This reversible process causes the coordinatively saturated Ti 4(μ-O) 2L 4 complexes to separate into two Ti 2(μ-O)L 2more » subunits which we envisaged would be catalytically active. Proof-of-concept experiments establish that all four of these complexes display catalytic activity in the ring-opening polymerisation of rac-lactide. These aggregates can therefore be viewed as air and moisture stable pre-catalysts for a range of reactions.« less

Photo-reduction of CO2 Using a Rhenium Complex Covalently Supported on a Graphene/TiO2 Composite.

PubMed

Cui, Shi-Cong; Sun, Xue-Zhong; Liu, Jin-Gang

2016-07-07

One of the promising solutions for decreasing atmospheric CO2 is artificial photosynthesis, in which CO2 can be photoconverted into solar fuels. In this study, a rhenium complex Re(PyBn)(CO)3 Cl (PyBn=1-(2-picolyl)-4-phenyl-1H-1,2,3-triazole) was covalently grafted onto the surface of reduced graphene oxide (rGO). This was further combined with TiO2 to fabricate a novel catalyst composite TiO2 -rGO-Re(PyBn)(CO)3 Cl for CO2 photo-reduction. This hybrid composite demonstrated high selectivity conversion of CO2 into CO under xenon-lamp irradiation. Compared with the unsupported homogeneous catalyst Re(PyBn)(CO)3 Cl, the covalent immobilized catalyst composite TiO2 -rGO-Re(PyBn)(CO)3 Cl enhanced the turnover number six times and significantly improved catalyst stability. During the process of CO2 photo-reduction, intermediate species with lifetimes longer than hundreds of microseconds were observed and the formation of CO products was revealed using timeresolved infrared spectroscopy. A plausible mechanism for CO2 photo-reduction by the TiO2 -rGO-Re(PyBn)(CO)3 Cl catalyst composite has been suggested. The obtained results have implications for the future design of efficient catalyst composites for CO2 photo-conversion. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluating the ototoxicity of an anti-MRSA peptide KR-12-a2.

PubMed

Sung, Chung Man; Kim, Hong Chan; Cho, Yong Beom; Shin, Song Yub; Jang, Chul Ho

2017-05-31

Methicillin-resistant staphylococcus aureus is an emerging problem for the treatment of chronic suppurative otitis media, and also for pediatric tympanostomy tube otorrhea. To date, there are no effective topical antibiotic drugs to treat methicillin-resistant staphylococcus aureus otorrhea. In this study, we evaluated the ototoxicity of topical KR-12-a2 solution on the cochlea when it is applied topically in the middle ear of guinea pigs. The antimicrobial activity of KR-12-a2 against methicillin-resistant staphylococcus aureus strains was examined by using the inhibition zone test. Topical application of KR-12-a2 solution, Gentamicin and Phosphate Buffered Saline were applied in the middle ear of the guinea pigs after inserting ventilation tubes. Ototoxicity was assessed by Auditory Brainstem Evoked Response and Scanning Electron Microscope examination. KR-12-a2 produced an inhibition zone against methicillin-resistant staphylococcus aureus from 6.25 μg. Hearing threshold in the KR-12-a2 and PBS groups were similar to that before ventilation tube insertion. However, the Gentamicin group showed elevation of the hearing threshold and there were statistically significant differences compared to the PBS or the KR-12-a2 group. In the SEM findings, the KR-12-a2 group showed intact outer hair cells. However, the GM group showed total loss of outer hair cells. In our experiment, topically applied KR-12-a2 solution did not cause hearing loss or cochlear damage in guinea pigs. In our experiment, topically applied KR-12-a2 solution did not cause hearing loss or cochlear damage in guinea pigs. The KR-12-a2 solution can be used as ototopical drops for treating methicillin-resistant staphylococcus aureus otorrhea; however, further evaluations, such as the definition of optimal concentration and combination, are necessary. Copyright © 2017 Associação Brasileira de Otorrinolaringologia e Cirurgia Cérvico-Facial. Published by Elsevier Editora Ltda. All rights reserved.

Mechanism and Stereochemistry of Polyketide Chain Elongation and Methyl Group Epimerization in Polyether Biosynthesis.

PubMed

Xie, Xinqiang; Garg, Ashish; Khosla, Chaitan; Cane, David E

2017-03-01

The polyketide synthases responsible for the biosynthesis of the polyether antibiotics nanchangmycin (1) and salinomycin (4) harbor a number of redox-inactive ketoreductase (KR 0 ) domains that are implicated in the generation of C2-epimerized (2S)-2-methyl-3-ketoacyl-ACP intermediates. Evidence that the natural substrate for the polyether KR 0 domains is, as predicted, a (2R)-2-methyl-3-ketoacyl-ACP intermediate, came from a newly developed coupled ketosynthase (KS)-ketoreductase (KR) assay that established that the decarboxylative condensation of methylmalonyl-CoA with S-propionyl-N-acetylcysteamine catalyzed by the Nan[KS1][AT1] didomain from module 1 of the nanchangmycin synthase generates exclusively the corresponding (2R)-2-methyl-3-ketopentanoyl-ACP (7a) product. In tandem equilibrium isotope exchange experiments, incubation of [2- 2 H]-(2R,3S)-2-methyl-3-hydroxypentanoyl-ACP (6a) with redox-active, epimerase-inactive EryKR6 from module 6 of the 6-deoxyerythronolide B synthase and catalytic quantities of NADP + in the presence of redox-inactive, recombinant NanKR1 0 or NanKR5 0 , from modules 1 and 5 of the nanchangmycin synthase, or recombinant SalKR7 0 from module 7 of the salinomycin synthase, resulted in first-order, time-dependent washout of deuterium from 6a. Control experiments confirmed that this washout was due to KR 0 -catalyzed isotope exchange of the reversibly generated, transiently formed oxidation product [2- 2 H]-(2R)-2-methyl-3-ketopentanoyl-ACP (7a), consistent with the proposed epimerase activity of each of the KR 0 domains. Although they belong to the superfamily of short chain dehydrogenase-reductases, the epimerase-active KR 0 domains from polyether synthases lack one or both residues of the conserved Tyr-Ser dyad that has previously been implicated in KR-catalyzed epimerizations.

Mechanism and Stereochemistry of Polyketide Chain Elongation and Methyl Group Epimerization in Polyether Biosynthesis

PubMed Central

Xie, Xinqiang; Garg, Ashish; Khosla, Chaitan; Cane, David E.

2017-01-01

The polyketide synthases responsible for the biosynthesis of the polyether antibiotics nanchangmycin (1) and salinomycin (4) harbor a number of redox-inactive ketoreductase (KR0) domains that are implicated in the generation of C2-epimerized (2S)-2-methyl-3-ketoacyl-ACP intermediates. Evidence that the natural substrate for the polyether KR0 domains is, as predicted, a (2R)-2-methyl-3-ketoacyl-ACP intermediate, came from a newly developed coupled ketosynthase (KS)-ketoreductase (KR) assay that established that the decarboxylative condensation of methylmalonyl-CoA with S-propionyl-N-acetylcysteamine catalyzed by the Nan[KS1][AT1] didomain from module 1 of the nanchangmycin synthase generates exclusively the corresponding (2R)-2-methyl-3-ketopentanoyl-ACP (7a) product. In tandem equilibrium isotope exchange experiments, incubation of [2-2H]-(2R,3S)-2-methyl-3-hydroxypentanoyl-ACP (6a) with redox-active, epimerase-inactive EryKR6 from module 6 of the 6-deoxyerythronolide B synthase and catalytic quantities of NADP+ in the presence of redox-inactive, recombinant NanKR10 or NanKR50, from modules 1 and 5 of the nanchangmycin synthase, or recombinant SalKR70 from module 7 of the salinomycin synthase, resulted in first-order, time-dependent washout of deuterium from 6a. Control experiments confirmed that this washout was due to KR0-catalyzed isotope exchange of the reversibly-generated, transiently-formed oxidation product [2-2H]-(2R)-2-methyl-3-ketopentanoyl-ACP (7a), consistent with the proposed epimerase activity of each of the KR0 domains. Although they belong to the superfamily of short chain dehydrogenase-reductases, the epimerase-active KR0 domains from polyether synthases lack one or both residues of the conserved Tyr-Ser dyad that has previously been implicated in KR-catalyzed epimerizations. PMID:28157306

Rosetting of Plasmodium falciparum-infected red blood cells with uninfected red blood cells enhances microvascular obstruction under flow conditions.

PubMed

Kaul, D K; Roth, E F; Nagel, R L; Howard, R J; Handunnetti, S M

1991-08-01

The occurrence of rosetting of Plasmodium falciparum-infected human red blood cells (IRBC) with uninfected red blood cells (RBC) and its potential pathophysiologic consequences were investigated under flow conditions using the perfused rat mesocecum vasculature. Perfusion experiments were performed using two knobby (K+) lines of P falciparum, ie, rosetting positive (K+R+) and rosetting negative (K+R-). The infusion of K+R+ IRBC resulted in higher peripheral resistance (PRU) than K+R- IRBC (P less than .0012). Video microscopy showed that under conditions of flow, in addition to cytoadherence of K+R+ IRBC to the venular endothelium, rosette formation was also restricted to venules, especially in the areas of slow flow. Rosettes were absent in arterioles and were presumably dissociated by higher wall shear rates. The presence of rosettes in the venules must therefore reflect their rapid reformation after disruption. Cytoadherence of K+R+ IRBC was characterized by formation of focal clusters along the venular wall. In addition, large aggregates of RBC were frequently observed at venular junctions, probably as a result of interaction between flowing rosettes, free IRBC, and uninfected RBC. In contrast, the infusion of K+R+ IRBC resulted in diffuse cytoadherence of these cells exclusively to the venular endothelium but not in rosetting or large aggregate formation. The cytoadherence of K+R+ IRBC showed strong inverse correlation with the venular diameter (r = -.856, P less than .00001). Incubation of K+R+ IRBC with heparin and with monoclonal antibodies to glycoprotein IV/CD36 abolished the rosette formation and resulted in decreased PRU and microvascular blockage. These findings demonstrate that rosetting of K+R+ IRBC with uninfected RBC enhances vasocclusion, suggesting an important in vivo role for rosetting in the microvascular sequestration of P falciparum-infected RBC.

Inhibitor of MYC identified in a Kröhnke pyridine library

PubMed Central

Hart, Jonathan R.; Garner, Amanda L.; Yu, Jing; Ito, Yoshihiro; Sun, Minghao; Ueno, Lynn; Rhee, Jin-Kyu; Baksh, Michael M.; Stefan, Eduard; Hartl, Markus; Bister, Klaus; Vogt, Peter K.; Janda, Kim D.

2014-01-01

In a fluorescence polarization screen for the MYC–MAX interaction, we have identified a novel small-molecule inhibitor of MYC, KJ-Pyr-9, from a Kröhnke pyridine library. The Kd of KJ-Pyr-9 for MYC in vitro is 6.5 ± 1.0 nM, as determined by backscattering interferometry; KJ-Pyr-9 also interferes with MYC–MAX complex formation in the cell, as shown in a protein fragment complementation assay. KJ-Pyr-9 specifically inhibits MYC-induced oncogenic transformation in cell culture; it has no or only weak effects on the oncogenic activity of several unrelated oncoproteins. KJ-Pyr-9 preferentially interferes with the proliferation of MYC-overexpressing human and avian cells and specifically reduces the MYC-driven transcriptional signature. In vivo, KJ-Pyr-9 effectively blocks the growth of a xenotransplant of MYC-amplified human cancer cells. PMID:25114221

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhatia, A.K.; Seely, J.F.; Feldman, U.

Oscillator strengths, radiative decay rates, and electron collision strengths have been calculated for the N-like ions Ar XII, Ti XVI, Fe XX, Zn XXIV, and Kr XXX. Included in the calculation are the 72 levels of the configurations 2s{sup 2}2p{sup 3}, 2s2p{sup 4}, 2p{sup 5}, 2s{sup 2}2p{sup 2}3s, 2s{sup 2}2p{sup 2}3p, and 2s{sup 2}2p{sup 2}3d. The level populations are calculated for the electron densities 10{sup 13}, 10{sup 14}, and 10{sup 15} cm{sup {minus}3}, and the spectral line intensities of the transitions from these levels are presented. The calculated intensities are in good agreement with the relative intensities observed in themore » spectra from the PLT tokamak.« less

10 CFR Appendix C to Part 835 - Derived Air Concentration (DAC) for Workers From External Exposure During Immersion in a Cloud of...

Code of Federal Regulations, 2013 CFR

2013-01-01

...-05 6E+05 Kr-81 2.1E+05 yr 7E-04 2E+07 Kr-83m 1.83 h 7E-02 2E+09 Kr-85 10.72 yr 7E-04 2E+07 Kr-85m 4.48 h 2E-05 1E+06 Kr-87 76.3 min 4E-06 1E+05 Kr-88 2.84 h 1E-06 7E+04 Xe-120 40.0 min 1E-05 4E+05 Xe-121 40.1 min 2E-06 8E+04 Xe-122 20.1 h 8E-05 3E+06 Xe-123 2.14 h 6E-06 2E+05 Xe-125 16.8 h 1E-05 6E+05...

10 CFR Appendix C to Part 835 - Derived Air Concentration (DAC) for Workers From External Exposure During Immersion in a Cloud of...

Code of Federal Regulations, 2014 CFR

2014-01-01

...-05 6E+05 Kr-81 2.1E+05 yr 7E-04 2E+07 Kr-83m 1.83 h 7E-02 2E+09 Kr-85 10.72 yr 7E-04 2E+07 Kr-85m 4.48 h 2E-05 1E+06 Kr-87 76.3 min 4E-06 1E+05 Kr-88 2.84 h 1E-06 7E+04 Xe-120 40.0 min 1E-05 4E+05 Xe-121 40.1 min 2E-06 8E+04 Xe-122 20.1 h 8E-05 3E+06 Xe-123 2.14 h 6E-06 2E+05 Xe-125 16.8 h 1E-05 6E+05...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sterling, N. C.; Mashburn, A. L.; Madonna, S.

We identify [Se iii] 1.0994 μ m in the planetary nebula (PN) NGC 5315 and [Kr vi] 1.2330 μ m in three PNe from spectra obtained with the Folded-Port InfraRed Echellette (FIRE) spectrometer on the 6.5 m Baade Telescope. Se and Kr are the two most widely detected neutron-capture elements in astrophysical nebulae, and can be enriched by s -process nucleosynthesis in PN progenitor stars. The detection of [Se iii] 1.0994 μ m is particularly valuable when paired with observations of [Se iv] 2.2864 μ m, as it can be used to improve the accuracy of nebular Se abundance determinations,more » and allows Se ionization correction factor (ICF) schemes to be empirically tested for the first time. We present new effective collision strength calculations for Se{sup 2+} and Kr{sup 5+}, which we use to compute ionic abundances. In NGC 5315, we find that the Se abundance computed from Se{sup 3+}/H{sup +} is lower than that determined with ICFs that incorporate Se{sup 2+}/H{sup +}. We compute new Kr ICFs that take Kr{sup 5+}/H{sup +} into account, by fitting correlations found in grids of Cloudy models between Kr ionic fractions and those of more abundant elements, and use these to derive Kr abundances in four PNe. Observations of [Se iii] and [Kr vi] in a larger sample of PNe, with a range of excitation levels, are needed to rigorously test the ICF prescriptions for Se and our new Kr ICFs.« less

Experimental studies of electron impact depopulation of excited states of atoms: applications to laser development for fusion and isotope separation. Final report, 1 January 1977-30 June 1979

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lubell, M.S.

1980-06-01

Motivated by the need for measurements of metastable depopulation mechanisms of Ar and Kr in the KrF rare-gas monohalide excimer laser, an ultra-high vacuum triple crossed-beams apparatus has been designed, fabricated, and assembled for the purpose of studying electron scattering from excited states of Ar and Kr atoms. A beam of metastable rare gas atoms, produced by near-resonant charge transfer of rare gas ions with alkali neutral atoms, is crossed by an electron beam and a far-red laser beam along mutually orthogonal axes. A hemispherical electron monochromator-spectrometer pair is used to measure the cross section for electron scattering from themore » 2p/sub 9/ excited state of the rare gas atom. Testing of parts of the assembled apparatus has been completed.« less

The Nike KrF laser facility: Performance and initial target experiments

NASA Astrophysics Data System (ADS)

Obenschain, S. P.; Bodner, S. E.; Colombant, D.; Gerber, K.; Lehmberg, R. H.; McLean, E. A.; Mostovych, A. N.; Pronko, M. S.; Pawley, C. J.; Schmitt, A. J.; Sethian, J. D.; Serlin, V.; Stamper, J. A.; Sullivan, C. A.; Dahlburg, J. P.; Gardner, J. H.; Chan, Y.; Deniz, A. V.; Hardgrove, J.; Lehecka, T.; Klapisch, M.

1996-05-01

Krypton-fluoride (KrF) lasers are of interest to laser fusion because they have both the large bandwidth capability (≳THz) desired for rapid beam smoothing and the short laser wavelength (1/4 μm) needed for good laser-target coupling. Nike is a recently completed 56-beam KrF laser and target facility at the Naval Research Laboratory. Because of its bandwidth of 1 THz FWHM (full width at half-maximum), Nike produces more uniform focal distributions than any other high-energy ultraviolet laser. Nike was designed to study the hydrodynamic instability of ablatively accelerated planar targets. First results show that Nike has spatially uniform ablation pressures (Δp/p<2%). Targets have been accelerated for distances sufficient to study hydrodynamic instability while maintaining good planarity. In this review we present the performance of the Nike laser in producing uniform illumination, and its performance in correspondingly uniform acceleration of targets.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dongil Chun; Dohyeon Kim; Kwangyong Eun

TiC-Ni-Mo cermet specimens were prepared by using a mixture of fine (1.5 [mu]m) and coarse (30 [mu]m) TiC powders. When the fraction of fine TiC particles was 80%, a (Ti,Mo,Ni)C complex carbide phase was observed deposited on the coarse TiC particles and resulted in a typical cored structure. As the fraction of fine TiC particles decreased, the coarse TiC particles exhibited a unique microstructural evolution with the development of a concave interface. This microstructural change of the coarse TiC grains can be explained in terms of the coherency strain energy.

Fluorimetric determination of proteins using 4-chloro-(2'-hydroxylophenylazo)rhodanine-Ti(IV) complex as a spectral probe.

PubMed

Sun, Shuting; Ma, Hongmin; Chen, Xin; Zhang, Nuo; Wu, Dan; Du, Bin; Wei, Qin

2008-01-01

A novel method for the determination of proteins was developed, based on the enhancement of fluorescence with 4-chloro-(2'-hydroxylophenylazo)rhodanine-Ti(IV) [ClHARP-Ti(IV)] complex as a fluorescence probe. The excitation and emission wavelengths of the system were 335 nm and 376 nm, respectively. The presence of bis(2-ethylhexyl)sulphosuccinate sodium salt (AOT) microemulsion greatly increased the sensitivity of the system. Under optimal conditions, four kinds of proteins, including bovine serum albumin (BSA), human serum albumin (HSA), egg albumin (Ova), and gamma-globin (gamma-G) were studied. The detection limits were 0.182 microg/mL for BSA, 0.0788 microg/mL for HSA, 0.216 microg/mL for Ova and 0.484 microg/mL for gamma-G. The linear ranges of the calibration were 0-12.0, 0-10.0, 0-18.0 and 0-18.0 microg/mL, respectively. The method possessed high sensitivity, good selectivity and was applied to the analysis of protein in milk powder and cornmeal with satisfactory results.

Self-controlled knowledge of results: age-related differences in motor learning, strategies, and error detection.

PubMed

Carter, Michael J; Patterson, Jae T

2012-12-01

Research has demonstrated that a self-controlled KR schedule is advantageous for motor learning; however, the usefulness of a self-controlled KR context in older adults remains unknown. To address this gap in knowledge, we examined whether (1) the learning benefits of a self-controlled KR schedule are modulated by the age of the learner; (2) practicing in a self-controlled KR context concurrently strengthens the learner's error detection mechanism, and (3) the KR strategy during acquisition changes as a function of practice trials completed and age. As a function of age, participants were quasirandomly assigned to either the self-control or yoked group resulting in four experimental groups (Self-Young, Yoked-Young, Self-Old, and Yoked-Old). The results revealed the Self-Young group: (1) demonstrated superior retention performance than all other groups (p<.05); (2) was more accurate in estimating motor performance than all other groups during retention (p<.05), and (3) self-reported a switch in their strategy for requesting KR during acquisition based on the number of practice trials completed. Collectively, our findings suggest that older adults do not demonstrate the same learning benefits of a self-controlled KR context as younger adults which may be attributed to differences in KR strategies. Copyright © 2012 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Negret, Alexandru; Singh, Balraj

The experimental nuclear spectroscopic data for known nuclides of mass number 75 (Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Kr, Rb, Sr) have been evaluated and presented together with Adopted properties for levels and γ rays. New high-spin data are available for {sup 75}Ga, and {sup 75}Rb; and lifetime data for high-spin states in {sup 75}Br and {sup 75}Kr. For ΔJ =1, M1+E2 transitions in two rotational bands in {sup 75}Kr, several B(E2)(W.u.) values are anomalously high, deviating by 2–3 σ values from currently accepted RUL(E2) = 300. In the opinion of the evaluators, there is needmore » to remeasure level lifetimes and multipole mixing ratios in {sup 75}Kr to resolve this serious discrepancy. New precise single-particle transfer cross section data are available for {sup 75}Ga, {sup 75}Ge, {sup 75}As and {sup 75}Se from several different reactions (2009Ka06,2008Sc03); these data give information for occupancy of valence neutron orbitals in the ground states of target nuclides: {sup 76}Ge, {sup 76}Se and {sup 78}Se. No significant new data since the 1999 NDS for A = 75 have been reported for {sup 75}As and {sup 75}Se. No data are yet available for excited states in {sup 75}Co, {sup 75}Ni and {sup 75}Sr. For {sup 75}Fe, only the isotopic identification is made with one observed event. The radioactive decay schemes of {sup 75}Co and {sup 75}Ni are unknown while those for {sup 75}Rb and {sup 75}Sr are incomplete. This work supersedes the data presented in the previous NDS evaluation of A = 75 published by 1999Fa05.« less

Sediment cores from kettle holes in NE Germany reveal recent impacts of agriculture.

PubMed

Kleeberg, Andreas; Neyen, Marielle; Schkade, Uwe-Karsten; Kalettka, Thomas; Lischeid, Gunnar

2016-04-01

Glacial kettle holes in young moraine regions receive abundant terrigenous material from their closed catchments. Core chronology and sediment accumulation were determined for two semi-permanent kettle holes, designated RG and KR, on arable land close to the villages of Rittgarten and Kraatz, respectively, in Uckermark, NE Germany. Core dating ((210)Pb, (137)Cs) revealed variable sediment accretion rates through time (RG 0.4-23.1 mm a(-1); KR 0.2-35.5 mm a(-1)), with periods of high accumulation corresponding to periods of intensive agricultural activity and consequent erosional inputs from catchments. Sediment composition (C, N, P, S, K, Ca, Fe, Mn, Zn, Cu, Mo, Pb, Cd, Zr) was used to determine sediment source and input processes. At RG, annual P input increased from 0.65 kg ha(-1) in the early nineteenth century to 1.67 kg ha(-1) by 2013. At KR, P input increased from 0.6 to 4.1 kg ha(-1) over the last century. There was a concurrent increase in Fe input in both water bodies. Thus, Fe/P ratios showed no temporal trend and did not differ between RG (18.5) and KR (18.4), indicating similar P mobility. At RG, the S/Fe ratio increased from 0.4 to 2.3, indicating more iron sulphides and thus higher P availability, coinciding with high coverage of duckweed (Spirodela polyrhiza (L.)) and soft hornwort (Ceratophyllum submersum L.). At KR, however, this ratio remained low and relatively unchanged (0.3 ± 0.4), indicating more efficient Fe-P binding and lower hydrophyte productivity. Trends in sediment composition indicate a shift towards eutrophication in both kettle holes, but with differences in timing and magnitude. Other morphologically similar kettle holes in NE Germany that are prone to erosion could have been similarly impacted but may differ in the extent of sediment infilling and degradation of their ecological functions.

Deliberate Design of TiO2 Nanostructures towards Superior Photovoltaic Cells.

PubMed

Sun, Ziqi; Liao, Ting; Sheng, Liyuan; Kou, Liangzhi; Kim, Jung Ho; Dou, Shi Xue

2016-08-01

TiO2 nanostructures are being sought after as flexibly utilizable building blocks for the fabrication of the mesoporous thin-film photoelectrodes that are the heart of the third-generation photovoltaic devices, such as dye-sensitized solar cells (DSSCs), quantum-dot-sensitized solar cells (QDSSCs), and the recently promoted perovskite-type solar cells. Here, we report deliberate tailoring of TiO2 nanostructures for superior photovoltaic cells. Morphology engineering of TiO2 nanostructures is realized by designing synthetic protocols in which the precursor hydrolysis, crystal growth, and oligomer self-organization are precisely controlled. TiO2 nanostructures in forms varying from isolated nanocubes, nanorods, and cross-linked nanorods to complex hierarchical structures and shape-defined mesoporous micro-/nanostructures were successfully synthesized. The photoanodes made from the shape-defined mesoporous TiO2 microspheres and nanospindles presented superior performances, owing to the well-defined overall shapes and the inner ordered nanochannels, which allow not only a high amount of dye uptake, but also improved visible-light absorption. This study provides a new way to seek an optimal synthetic protocol to meet the required functionality of the nanomaterials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of TiO2 Nanoparticles from Ilmenite Through the Mechanism of Vapor-Phase Reaction Process by Thermal Plasma Technology

NASA Astrophysics Data System (ADS)

Samal, Sneha

2017-11-01

Synthesis of nanoparticles of TiO2 was carried out by non-transferred arc thermal plasma reactor using ilmenite as the precursor material. The powder ilmenite was vaporized at high temperature in plasma flame and converted to a gaseous state of ions in the metastable phase. On cooling, chamber condensation process takes place on recombination of ions for the formation of nanoparticles. The top-to-bottom approach induces the disintegration of complex ilmenite phases into simpler compounds of iron oxide and titanium dioxide phases. The vapor-phase reaction mechanism was carried out in thermal plasma zone for the synthesis of nanoparticles from ilmenite compound in a plasma reactor. The easy separation of iron particles from TiO2 was taken place in the plasma chamber with deposition of light TiO2 particles at the top of the cooling chamber and iron particles at the bottom. The dissociation and combination process of mechanism and synthesis are studied briefly in this article. The product TiO2 nanoparticle shows the purity with a major phase of rutile content. TiO2 nanoparticles produced in vapor-phase reaction process shows more photo-induced capacity.

Strain Effects in Epitaxial VO2 Thin Films on Columnar Buffer-Layer TiO2/Al2O3 Virtual Substrates.

PubMed

Breckenfeld, Eric; Kim, Heungsoo; Burgess, Katherine; Charipar, Nicholas; Cheng, Shu-Fan; Stroud, Rhonda; Piqué, Alberto

2017-01-18

Epitaxial VO 2 /TiO 2 thin film heterostructures were grown on (100) (m-cut) Al 2 O 3 substrates via pulsed laser deposition. We have demonstrated the ability to reduce the semiconductor-metal transition (SMT) temperature of VO 2 to ∼44 °C while retaining a 4 order of magnitude SMT using the TiO 2 buffer layer. A combination of electrical transport and X-ray diffraction reciprocal space mapping studies help examine the specific strain states of VO 2 /TiO 2 /Al 2 O 3 heterostructures as a function of TiO 2 film growth temperatures. Atomic force microscopy and transmission electron microscopy analyses show that the columnar microstructure present in TiO 2 buffer films is responsible for the partially strained VO 2 film behavior and subsequently favorable transport characteristics with a lower SMT temperature. Such findings are of crucial importance for both the technological implementation of the VO 2 system, where reduction of its SMT temperature is widely sought, as well as the broader complex oxide community, where greater understanding of the evolution of microstructure, strain, and functional properties is a high priority.

Electrochemical Behaviour and Electrorefining of Cobalt in NaCl-KCl-K2TiF6 Melt

NASA Astrophysics Data System (ADS)

Kuznetsov, Sergey A.; Kazakova, Olga S.; Makarova, Olga V.

2009-08-01

The electrorefining of cobalt in NaCl-KCl-K2TiF6 (20 wt%) melt has been investigated. It was shown that complexes of Ti(III) and Co(II) appeared in the melt due to the reaction 2Ti(IV) + Co → 2Ti(III) + Co(II) and this reaction was entirely shifted to the right hand side. On the base of linear sweep voltammetry diagnostic criteria it was found that the discharge of Co(II) to Co metal is controlled by diffusion. The limiting current density of discharge Co(II) to metal in NaCl-KCl-K2TiF6 (20 wt%) melt was determined by steady-state voltammetry. The electrorefining of cobalt was carried out in hermetic electrolyser under argon atmosphere. Initial cathodic current density was changed from 0.2 Acm-2 up to 0.7 Acm-2, the electrolysis temperature varied within 973 - 1123 K. Behaviour of impurities during cobalt electrorefining was discussed. It was shown that electrorefining led to the elimination of most of the interstitial impurities (H2, N2, O2, C), with the result that the remaining impurity levels below 10 ppm impart high ductility to cobalt.

Expanding the Therapeutic Potential of the Iron Chelator Deferasirox in the Development of Aqueous Stable Ti(IV) Anticancer Complexes.

PubMed

Loza-Rosas, Sergio A; Vázquez-Salgado, Alexandra M; Rivero, Kennett I; Negrón, Lenny J; Delgado, Yamixa; Benjamín-Rivera, Josué A; Vázquez-Maldonado, Angel L; Parks, Timothy B; Munet-Colón, Charlene; Tinoco, Arthur D

2017-07-17

The recent X-ray structure of titanium(IV)-bound human serum transferrin (STf) exhibiting citrate as a synergistic anion reveals a difference in Ti(IV) coordination versus iron(III), the metal endogenously delivered by the protein to cells. This finding enriches our bioinspired drug design strategy for Ti(IV)-based anticancer therapeutics, which applies a family of Fe(III) chelators termed chemical transferrin mimetic (cTfm) ligands to inhibit Fe bioavailability in cancer cells. Deferasirox, a drug used for iron overload disease, is a cTfm ligand that models STf coordination to Fe(III), favoring Fe(III) binding versus Ti(IV). This metal affinity preference drives deferasirox to facilitate the release of cytotoxic Ti(IV) intracellularly in exchange for Fe(III). An aqueous speciation study performed by potentiometric titration from pH 4 to 8 with micromolar levels of Ti(IV) deferasirox at a 1:2 ratio reveals exclusively Ti(deferasirox) 2 in solution. The predominant complex at pH 7.4, [Ti(deferasirox) 2 ] 2- , exhibits the one of the highest aqueous stabilities observed for a potent cytotoxic Ti(IV) species, demonstrating little dissociation even after 1 month in cell culture media. UV-vis and 1 H NMR studies show that the stability is unaffected by the presence of biomolecular Ti(IV) binders such as citrate, STf, and albumin, which have been shown to induce dissociation or regulate cellular uptake and can alter the activity of other antiproliferative Ti(IV) complexes. Kinetic studies on [Ti(deferasirox) 2 ] 2- transmetalation with Fe(III) show that a labile Fe(III) source is required to induce this process. The initial step of this process occurs on the time scale of minutes, and equilibrium for the complete transmetalation is reached on a time scale of hours to a day. This work reveals a mechanism to deliver Ti(IV) compounds into cells and trigger Ti(IV) release by a labile Fe(III) species. Cellular studies including other cTfm ligands confirm the Fe(III) depletion mechanism of these compounds and show their ability to induce early and late apoptosis.

The CasKR Two-Component System Is Required for the Growth of Mesophilic and Psychrotolerant Bacillus cereus Strains at Low Temperatures

PubMed Central

Diomandé, Sara Esther; Chamot, Stéphanie; Antolinos, Vera; Vasai, Florian; Guinebretière, Marie-Hélène; Bornard, Isabelle; Nguyen-the, Christophe; Broussolle, Véronique

2014-01-01

The different strains of Bacillus cereus can grow at temperatures covering a very diverse range. Some B. cereus strains can grow in chilled food and consequently cause food poisoning. We have identified a new sensor/regulator mechanism involved in low-temperature B. cereus growth. Construction of a mutant of this two-component system enabled us to show that this system, called CasKR, is required for growth at the minimal temperature (Tmin). CasKR was also involved in optimal cold growth above Tmin and in cell survival below Tmin. Microscopic observation showed that CasKR plays a key role in cell shape during cold growth. Introducing the casKR genes in a ΔcasKR mutant restored its ability to grow at Tmin. Although it was first identified in the ATCC 14579 model strain, this mechanism has been conserved in most strains of the B. cereus group. We show that the role of CasKR in cold growth is similar in other B. cereus sensu lato strains with different growth temperature ranges, including psychrotolerant strains. PMID:24509924

ALMA observations of TiO2 around VY Canis Majoris

NASA Astrophysics Data System (ADS)

De Beck, E.; Vlemmings, W.; Muller, S.; Black, J. H.; O'Gorman, E.; Richards, A. M. S.; Baudry, A.; Maercker, M.; Decin, L.; Humphreys, E. M.

2015-08-01

Context. Titanium dioxide, TiO2, is a refractory species that could play a crucial role in the dust-condensation sequence around oxygen-rich evolved stars. To date, gas phase TiO2 has been detected only in the complex environment of the red supergiant VY CMa. Aims: We aim to constrain the distribution and excitation of TiO2 around VY CMa in order to clarify its role in dust formation. Methods: We analyse spectra and channel maps for TiO2 extracted from ALMA science verification data. Results: We detect 15 transitions of TiO2, and spatially resolve the emission for the first time. The maps demonstrate a highly clumpy, anisotropic outflow in which the TiO2 emission likely traces gas exposed to the stellar radiation field. An accelerating bipolar-like structure is found, oriented roughly east-west, of which the blue component runs into and breaks up around a solid continuum component. A distinct tail to the south-west is seen for some transitions, consistent with features seen in the optical and near-infrared. Conclusions: We find that a significant fraction of TiO2 remains in the gas phase outside the dust-formation zone and suggest that this species might play only a minor role in the dust-condensation process around extreme oxygen-rich evolved stars like VY CMa. Appendix A is available in electronic form at http://www.aanda.org

Comparison of TiO2 nanoparticle and graphene-TiO2 nanoparticle composite phototoxicity to Daphnia magna and Oryzias latipes

EPA Science Inventory

With a dramatic rise in complexity, needs of nanotoxicology research go beyond simple forms of nanomaterials. This study compared the phototoxicity of nano-TiO2and graphene-TiO2 nanocomposite (GNP). GNP was synthesized based on a hydrothermal method, which simultaneously performe...

Direct measurements of irradiation-induced creep in micropillars of amorphous Cu{sub 56}Ti{sub 38}Ag{sub 6}, Zr{sub 52}Ni{sub 48}, Si, and SiO{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Özerinç, Sezer; Kim, Hoe Joon; Averback, Robert S.

2015-01-14

We report in situ measurements of irradiation-induced creep on amorphous (a-) Cu{sub 56}Ti{sub 38}Ag{sub 6}, Zr{sub 52}Ni{sub 48}, Si, and SiO{sub 2}. Micropillars 1 μm in diameter and 2 μm in height were irradiated with ∼2 MeV heavy ions during uniaxial compression at room temperature. The creep measurements were performed using a custom mechanical testing apparatus utilizing a nanopositioner, a silicon beam transducer, and an interferometric laser displacement sensor. We observed Newtonian flow in all tested materials. For a-Cu{sub 56}Ti{sub 38}Ag{sub 6}, a-Zr{sub 52}Ni{sub 48}, a-Si, and Kr{sup +} irradiated a-SiO{sub 2} irradiation-induced fluidities were found to be nearly the same, ≈3 GPa{sup −1}more » dpa{sup −1}, whereas for Ne{sup +} irradiated a-SiO{sub 2} the fluidity was much higher, 83 GPa{sup −1} dpa{sup −1}. A fluidity of 3 GPa{sup −1} dpa{sup −1} can be explained by point-defect mediated plastic flow induced by nuclear collisions. The fluidity of a-SiO{sub 2} can also be explained by this model when nuclear stopping dominates the energy loss, but when the electronic stopping exceeds 1 keV/nm, stress relaxation in thermal spikes also contributes to the fluidity.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Kimmel, Greg A.; Shen, Mingmin

Using temperature programmed desorption (TPD) and photon stimulated desorption (PSD), we show that coadsorbates of varying binding energies on the rutile TiO2(110) surface exert a commensurate inhibiting influence on the hole-mediated photodesorption of adsorbed O2. A variety of coadsorbates (Ar, Kr, Xe, N2, CO, CO2, CH4, N2O, acetone, methanol or water) were shown to quench O2 photoactivity, with the extent correlating with the coadsorbate’s gas phase basicity, which in turn determines the strength of the coadsorbate-Ti4+ bond. Coadsorbed rare gases inhibited the photodesorption of O2 by ~10-25%, whereas strongly bound species (water, methanol and acetone) nearly completely inhibited O2 PSD.more » We suggest that coadsorption of these molecules inhibit the arrival probability of holes to the surface. Band bending effects, which vary with the extent of charge transfer between the coadsorbate and the TiO2(110) surface, are not expected to be significant in the cases of the rare gases and physisorbed species. These results indicate that neutral coadsorbates can exert a significant influence on charge transfer events by altering the interfacial dipole in the vicinity of the target molecule. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. The work was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle under Contract DE-AC05-76RL01830.« less

Effect of Cu(2+)-complexation on the scavenging ability of chrysin towards photogenerated singlet molecular oxygen (O2((1)Δg)). Possible biological implications.

PubMed

Muñoz, Vanesa A; Ferrari, Gabriela V; Montaña, M Paulina; Miskoski, Sandra; García, Norman A

2016-09-01

Visible-light irradiation of aqueous-ethanolic solutions of Riboflavin (Rf) in the individual presence of the flavone chrysin (Chr) and its complex with Cu(2+) ([Chr2Cu]; 2:1 L:M) generates singlet molecular oxygen O2((1)Δg), that concomitantly interact with both flavone derivatives. Overall (kt) and reactive (kr) rate constants in the order of 10(7)M(-1)s(-1) were determined for the process. Metal chelation greatly enhances the scavenging ability of [Chr2Cu] towards O2((1)Δg) through a mechanism dominated, in >80%, by the physical component. In this way, practically all O2((1)Δg) is deactivated by the complex without significant loss of the quencher. The isolated flavone quenches O2((1)Δg) in a prevailing reactive fashion. The very low value exhibited by [Chr2Cu] for the kr/kt ratio constitutes a positive quality for antioxidative protectors in biological media, where elevated local concentration and high reactivity of significant molecules make them initial targets for O2((1)Δg) aggression. Finally, two interesting properties in the field of free radicals scavenging by [Chr2Cu] must be mentioned. In first place metal chelation itself, in the obvious sense of free metal ion withdrawal from the oxidizable medium, prevents the initiation of a free radical-mediated oxidation processes through mechanisms of Fenton or lipid peroxidation. In addition, the incorporation of Cu adds to [Chr2Cu] the ability of a free radical scavenger, already described for similar Cu-chelate compounds. This collection of beneficial properties positions the complex as a remarkably promising bioprotector towards ROS-mediated oxidation. A quantification of the efficiency on the initial anti-oxidative effect exerted by Chr and [Chr2Cu] towards tryptophan was carried out. The amino acid is an archetypal molecular model, commonly employed to monitor oxidative degradation of proteinaceous media. It was efficiently photoprotected against O2((1)Δg)-mediated photooxidation by [Chr2Cu]. Copyright © 2016. Published by Elsevier B.V.

Parental styles in second generation effects of genocide stemming from the Khmer Rouge regime in Cambodia.

PubMed

Field, Nigel P; Om, Chariya; Kim, Thida; Vorn, Sin

2011-11-01

This study examined the impact of parental styles on second generation effects of trauma among adolescent offspring of survivors of the Khmer Rouge (KR) genocide in Cambodia. Two hundred high school students completed measures addressing their parents' trauma stemming from the KR regime, parental styles (role reversing, overprotective), depression and anxiety. Parents' role reversing parental style and mothers' overprotective parenting were shown to mediate the impact of their trauma symptoms on the child's depression and anxiety. The implications of the findings are discussed.

Simulations of High-Gain Shock-Ignited Inertial-Confinement-Fusion Implosions Using Less Than 1 MJ of Direct KrF Laser Energy

DTIC Science & Technology

2009-05-01

transport, and thermonuclear burn. Using FAST, three classes of shock-ignited targets were designed that achieve one-dimensional fusion - energy gains in the...MJ) G a in Figure 1: Results of one-dimensional simulations showing the fusion energy gain as a function of KrF laser energy for three classes of...rises smoothly (according to a double power (a) Spike width: 160 ps (b) Spike power: 1530 TW Figure 4: Examples of fusion - energy gain contours for a shock

Erroneous knowledge of results affects decision and memory processes on timing tasks.

PubMed

Ryan, Lawrence J; Fritz, Matthew S

2007-12-01

On mental timing tasks, erroneous knowledge of results (KR) leads to incorrect performance accompanied by the subjective judgment of accurate performance. Using the start-stop technique (an analogue of the peak interval procedure) with both reproduction and production timing tasks, the authors analyze what processes erroneous KR alters. KR provides guidance (performance error information) that lowers decision thresholds. Erroneous KR also provides targeting information that alters response durations proportionately to the magnitude of the feedback error. On the production task, this shift results from changes in the reference memory, whereas on the reproduction task this shift results from changes in the decision threshold for responding. The idea that erroneous KR can alter different cognitive processes on related tasks is supported by the authors' demonstration that the learned strategies can transfer from the reproduction task to the production task but not visa versa. Thus effects of KR are both task and context dependent.

B (e 2 ;21+→01+) value in 90Kr

NASA Astrophysics Data System (ADS)

Régis, J.-M.; Jolie, J.; Saed-Samii, N.; Warr, N.; Pfeiffer, M.; Blanc, A.; Jentschel, M.; Köster, U.; Mutti, P.; Soldner, T.; Simpson, G. S.; Drouet, F.; Vancraeyenest, A.; de France, G.; Clément, E.; Stezowski, O.; Ur, C. A.; Urban, W.; Regan, P. H.; Podolyák, Zs.; Larijani, C.; Townsley, C.; Carroll, R.; Wilson, E.; Fraile, L. M.; Mach, H.; Paziy, V.; Olaizola, B.; Vedia, V.; Bruce, A. M.; Roberts, O. J.; Smith, J. F.; Kröll, T.; Hartig, A.-L.; Ignatov, A.; Ilieva, S.; Thürauf, M.; Lalkovski, S.; Ivanova, D.; Kisyov, S.; Korten, W.; Salsac, M.-D.; Zielińska, M.; Mǎrginean, N.; Ghitǎ, D. G.; Licǎ, R.; Petrache, C. M.; Astier, A.; Leguillon, R.

2014-12-01

A smooth onset of collectivity in 88 ,92 ,94 ,96Kr has been determined from reported B (E 2 ;21+→01+) and E (21+) values. This is in contrast to the sudden onset in even-even Zr, Mo, and Sr isotopes. Our objective was to complete the systematics by determining the B (E 2 ;21+→01+) value in 90Kr, which was produced by cold-neutron-induced fission of 235U . The lifetime of the 21+ state in 90Kr was measured via the electronic γ -γ timing technique using the EXILL and FATIMA spectrometers. Based on the measured mean lifetime of τ = 15(10) ps, the B (E 2 ;21+→01+) value of 13 -5+26 W.u. in 90Kr is determined for the first time and the smooth onset of deformation in the even-even Kr isotopes beyond neutron number N =50 is confirmed.

Oxidation characteristics of Ti-25Al-10Nb-3V-1Mo intermetallic alloy

NASA Technical Reports Server (NTRS)

Wallace, Terryl A.; Clark, Ronald K.; Sankaran, Sankara N.; Wiedemann, Karl E.

1990-01-01

Static oxidation kinetics of the super-alpha 2 titanium-aluminide alloy Ti-25Al-10Nb-3V-1Mo (at. percent) were investigated in air over the temperature range of 650 to 1000 C using thermogravimetric analysis. The oxidation kinetics were complex at all exposure temperatures and displayed up to three distinct oxidation rates. Breakaway oxidation occurred after long exposure times at high temperatures. Oxidation products were determined using x ray diffraction techniques, electron microprobe analysis, and energy dispersive x ray analysis. Oxide scale morphology was examined by scanning electron microscopy of the surfaces and cross sections of oxidized specimens. The oxides during the parabolic stages were compact and multilayered, consisting primarily of TiO2 doped with Nb, a top layer of Al2O3, and a thin bottom layer of TiN. The transition between the second and third parabolic stage was found to be linked to the formation of a TiAl layer at the oxide-metal interface. Porosity was formed during the third stage, causing degradation of the oxide and the beginning of breakaway oxidation.

Mechanical intermixing of components in (CoMoNi)-based systems and the formation of (CoMoNi)/WC nanocomposite layers on Ti sheets under ball collisions

NASA Astrophysics Data System (ADS)

Romankov, S.; Park, Y. C.; Shchetinin, I. V.

2017-11-01

Cobalt (Co), molybdenum (Mo), and nickel (Ni) components were simultaneously introduced onto titanium (Ti) surfaces from a composed target using ball collisions. Tungsten carbide (WC) balls were selected for processing as the source of a cemented carbide reinforcement phase. During processing, ball collisions continuously introduced components from the target and the grinding media onto the Ti surface and induced mechanical intermixing of the elements, resulting in formation of a complex nanocomposite structure onto the Ti surface. The as-fabricated microstructure consisted of uniformly dispersed WC particles embedded within an integrated metallic matrix composed of an amorphous phase with nanocrystalline grains. The phase composition of the alloyed layers, atomic reactions, and the matrix grain sizes depended on the combination of components introduced onto the Ti surface during milling. The as-fabricated layer exhibited a very high hardness compared to industrial metallic alloys and tool steel materials. This approach could be used for the manufacture of both cemented carbides and amorphous matrix composite layers.

Surface modification of TiO{sub 2} nanoparticles with carotenoids. EPR study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Konovalova, T.A.; Kispert, L.D.; Konovalov, V.V.

1999-06-03

Among the semiconductors, titanium dioxide is the most suitable for many environmental applications. EPR measurements demonstrate efficient charge separation on carotenoid-modified titanium dioxide nanoparticles (7 nm). Strong complexation of carotenoids containing terminal carboxy groups ({minus}CO{sub 2}H) with the TiO{sub 2} surface leads to electron transfer from the adsorbed carotenoid molecule to the surface trapping site. For these systems, EPR signals of the carotenoid radical cations Car{sup {sm_bullet}+} and the electrons trapped on the TiO{sub 2} are observed before irradiation (77 K). Their UV-visible spectra show an absorption band with a maximum near 650 nm that is characteristic of the trappedmore » electrons. Surface modification of the TiO{sub 2} by other carotenoids results in the formation of a complex with an optical absorption band near 545 nm. These systems form charge-separated pairs [Car{sup {sm_bullet}+}{hor_ellipsis}TiO{sub 2}(e{sup {minus}}{sub tr}){sub surf}. TiO{sub 2}(e{sup {minus}}{sub tr}){sub latt}] only upon 365--600 nm illumination at 77 K. Complexation of the TiO{sub 2} colloids with carotenoids enhances spatial charge separation, shifts the absorption threshold into the visible region, and thus greatly improves the reducing ability of the semiconductor. Photoreduction of acceptor molecules such as 2,5-dichloro-1,4-benzoquinone, nitrobenzene, and oxygen is demonstrated.« less

Development of a high resolution x-ray spectrometer for the National Ignition Facility (NIF)

DOE PAGES

Hill, K. W.; Bitter, M.; Delgado-Aparicio, L.; ...

2016-09-28

A high resolution (E/ΔE = 1200-1800) Bragg crystal x-ray spectrometer is being developed to measure plasma parameters in National Ignition Facility experiments. The instrument will be a diagnostic instrument manipulator positioned cassette designed mainly to infer electron density in compressed capsules from Stark broadening of the helium-β (1s 2-1s3p) lines of krypton and electron temperature from the relative intensities of dielectronic satellites. Two conically shaped crystals will diffract and focus (1) the Kr Heβ complex and (2) the Heα (1s 2-1s2p) and Lyα (1s-2p) complexes onto a streak camera photocathode for time resolved measurement, and a third cylindrical or conicalmore » crystal will focus the full Heα to Heβ spectral range onto an image plate to provide a time integrated calibration spectrum. Calculations of source x-ray intensity, spectrometer throughput, and spectral resolution are presented. Furthermore, details of the conical-crystal focusing properties as well as the status of the instrumental design are also presented.« less

Development of a high resolution x-ray spectrometer for the National Ignition Facility (NIF).

PubMed

Hill, K W; Bitter, M; Delgado-Aparicio, L; Efthimion, P C; Ellis, R; Gao, L; Maddox, J; Pablant, N A; Schneider, M B; Chen, H; Ayers, S; Kauffman, R L; MacPhee, A G; Beiersdorfer, P; Bettencourt, R; Ma, T; Nora, R C; Scott, H A; Thorn, D B; Kilkenny, J D; Nelson, D; Shoup, M; Maron, Y

2016-11-01

A high resolution (E/ΔE = 1200-1800) Bragg crystal x-ray spectrometer is being developed to measure plasma parameters in National Ignition Facility experiments. The instrument will be a diagnostic instrument manipulator positioned cassette designed mainly to infer electron density in compressed capsules from Stark broadening of the helium-β (1s 2 -1s3p) lines of krypton and electron temperature from the relative intensities of dielectronic satellites. Two conically shaped crystals will diffract and focus (1) the Kr Heβ complex and (2) the Heα (1s 2 -1s2p) and Lyα (1s-2p) complexes onto a streak camera photocathode for time resolved measurement, and a third cylindrical or conical crystal will focus the full Heα to Heβ spectral range onto an image plate to provide a time integrated calibration spectrum. Calculations of source x-ray intensity, spectrometer throughput, and spectral resolution are presented. Details of the conical-crystal focusing properties as well as the status of the instrumental design are also presented.

Structural effects of TiO2 nanoparticles and doxorubicin on DNA and their antiproliferative roles in T47D and MCF7 cells.

PubMed

Hekmat, Azadeh; Saboury, Ali Akbar; Divsalar, Adeleh; Seyedarabi, Arefeh

2013-07-01

The structural changes in DNA caused by the combined effects of TiO2 nanoparticles (TiO2 NPs) and doxorubicin (DOX) were investigated along with their corresponding inhibitory roles in the growth of T47D and MCF7 cells. The UV-visible titration studies showed that DOX+ TiO2 NPs could form a novel complex with DNA. The data also reveal that the TiO2-DOX complex forms through a 1:4 stoichiometric ratio in solution. The values of binding constants reveal that DOX+TiO2 NPs interact more strongly with DNA as compared to TiO2 NPs or DOX alone. CD data show that DOX+TiO2 NPs can noticeably cause disturbance on DNA structure compared to TiO2 NPs or DOX alone, considering that DNA is relatively thermally stable in the condition used. The anticancer property of 0.3 µM DOX+ 60 µM TiO2 NPs and 0.4 µM DOX+ 670 µM TiO2 NPs by MTT assay and DAPI stain demonstrates that this combination can tremendously diminish proliferation of T47D and MCF7cells compared to DOX or TiO2 NPs alone. The UV-Vis absorption spectroscopy, flow cytometry and fluorescence microscopy experiments show much more enhancement of DOX uptake through the use of TiO2 NPs. These results reveal that DOX+TiO2 NPs could proffer a novel strategy for the development of promising and efficient chemotherapy agents.

Pulsed Laser Deposited Ferromagnetic Chromium Dioxide thin Films for Applications in Spintronics

NASA Astrophysics Data System (ADS)

Dwivedi, S.; Jadhav, J.; Sharma, H.; Biswas, S.

Stable rutile type tetragonal chromium dioxide (CrO2) thin films have been deposited on lattice-matched layers of TiO2 by KrF excimer laser based pulsed laser deposition (PLD) technique using Cr2O3 target. The TiO2 seed layer was deposited on oxidized Si substrates by the same PLD process followed by annealing at 1100 °C for 4 h. The lattice-matched interfacial layer is required for the stabilization of Cr (IV) phase in CrO2, since CrO2 behaves as a metastable compound under ambient conditions and readily converts into its stable phase of Cr (III) oxide, Cr2O3. Analyses with X-ray diffraction (XRD), Glancing-angle XRD (GIXRD), Raman spectroscopy and grazing-angle Fourier transform infra-red (FTIR) spectroscopy confirm the presence of tetragonal CrO2 phase in the as-deposited films. Microstructure and surface morphology in the films were studied with field emission scanning electron microscope (FESEM) and atomic force microscope (AFM). Electrical and magnetic characterizations of the films were performed at room temperature. Such type of stable half-metallic CrO2 thin films with low field magnetoresistive switching behaviour are in demand for applications as diverse as spin-FETs, magnetic sensors, and magneto-optical devices.

Carbon, nitrogen, magnesium, silicon, and titanium isotopic compositions of single interstellar silicon carbide grains from the Murchison carbonaceous chondrite

NASA Technical Reports Server (NTRS)

Hoppe, Peter; Amari, Sachiko; Zinner, Ernst; Ireland, Trevor; Lewis, Roy S.

1994-01-01

Seven hundred and twenty SiC grains from the Murchison CM2 chondrite, ranging in size from 1 to 10 micrometers, were analyzed by ion microprobe mass spectrometry for their C-isotopic compositions. Subsets of the grains were also analyzed for N (450 grains), Si (183 grains), Mg (179 grains), and Ti (28 grains) isotopes. These results are compared with previous measurements on 41 larger SiC grains (up to 15 x 26 micrometers) from a different sample of Murchison analyzed by Virag et al. (1992) and Ireland, Zinner, & Amari (1991a). All grains of the present study are isotopically anomalous with C-12/C-13 ratios ranging from 0.022 to 28.4 x solar, N-14/N-15 ratios from 0.046 to 30 x solar, Si-29/Si-28 from 0.54 to 1.20 x solar, Si-30/Si-28 from 0.42 to 1.14 x solar, Ti-49/Ti-48 from 0.96 to 1.95 x solar, and Ti-50/Ti-48 from 0.94 to 1.39 x solar. Many grains have large Mg-26 excesses from the decay of Al-26 with inferred Al-26/Al-27 ratios ranging up to 0.61, or 12,200 x the ratio of 5 x 10(exp -5) inferred for the early solar system. Several groups can be distinguished among the SiC grains. Most of the grains have C-13 and N-14 excesses, and their Si isotopic compositions (mostly excesses in Si-29 and Si-30) plot close to a slope 1.34 line on a Delta Si-29/Si-28 versus Delta Si-30/Si-28 three-isotope plot. Grains with small C-12/C-13 ratios (less than 10) tend to have smaller or no N-14 excesses and high Al-26/Al-27 ratios (up to 0.01). Grains with C-12/C-13 greater than 150 fall into two groups: grains X have N-15 excesses and Si-29 and Si-30 deficits and the highest (0.1 to 0.6) Al-26/Al-27 ratios; grains Y have N-14 excesses and plot on a slope 0.35 line on a Si three-isotope plot. In addition, large SiC grains of the Virag et al. (1992) study fall into three-distinct clusters according to their C-, Si-, and Ti-isotopic compositions. The isotopic diversity of the grains and the clustering of their isotopic compositions imply distinct and multiple stellar sources. The C- and N-isotopic compositions of most grains are consistent with H-burning in the CNO cycle. These and s-process Kr, Xe, Ba, and Nd suggest asymptotic giant branch (AGB) or Wolf-Rayet stars as likely sources for the grains, but existing models of nucleosynthesis in these stellar sites fail to account in detail for all the observed isotopic compositions. Special problems are posed by grains with C-12/C-13 less than 10 and almost normal and heavy N-isotopic compositions. Also the Si- and Ti-isotopic compositions, with excesses in Si-29 and Si-30 relative to Si-28 and excesses in all Ti isotopes relative to Ti-48, do not precisely conform with the compositions predicted for slow neutron capture. Additional theoretical efforts are needed to achieve an understanding of the isotopic composition of the SiC grains and their stellar sources.

Infrared and Microwave Spectra of Ne-WATER Complex

NASA Astrophysics Data System (ADS)

Liu, Xunchen; Thomas, Javix; Xu, Yunjie; Hou, Dan; Li, Hui

2016-06-01

The binary complex of rare gas atom and water is an ideal model to study the anisotropic potential energy surface of van der Waals interaction and the large amplitude motion. Although Xe-H_2O, Kr-H_2O, Ar-H_2O, Ar-D_2O and even Ne-D_2O complexes were studied by microwave or high resolution infrared spectroscopy, the lighter Ne-H_2O complex has remained unidentified. In this talk, we will present the theoretical and experimental investigation of the Ne-H_2O complex. A four-dimension PES for H_2O-Ne which only depended on the intramolecular (Q2) normal-mode coordinate of H2O monomer was calculated in this work to determine the rovibrational energy levels and mid-infrared transitions. Aided with the calculated transitions, we were able to assigned the high resolution mid-infrared spectra of both 20Ne-H_2O and 22Ne-H_2O complexes that are generated with a pulsed supersonic molecular beam in a multipass direct absorption spectrometer equiped with an external cavity quantum cascade laser at 6 μm. Several bands of both para and ortho Ne-H2O were assigned and fitted using the Hamiltonian with strong Coriolis and angular-radical coupling terms. The predicted groud state energy levels are then confirmed by the J=1-0 and J=2-1 transitions measurement using a cavity based Fourier transform microwave spectrometer.

Characterization, optical properties and laser ablation behavior of epoxy resin coatings reinforced with high reflectivity ceramic particles

NASA Astrophysics Data System (ADS)

Li, Wenzhi; Kong, Jing; Wu, Taotao; Gao, Lihong; Ma, Zhuang; Liu, Yanbo; Wang, Fuchi; Wei, Chenghua; Wang, Lijun

2018-04-01

Thermal damage induced by high power energy, especially high power laser, significantly affects the lifetime and performance of equipment. High-reflectance coating/film has attracted considerable attention due to its good performance in the damage protection. Preparing a high-reflectance coating with high reaction endothermal enthalpy will effectively consume a large amount of incident energy and in turn protect the substrate from thermal damage. In this study, a low temperature process was used to prepare coatings onto substrate with complex shape and avoid thermal effect during molding. An advanced high reflection ceramic powder, La1‑xSrxTiO3+δ , was added in the epoxy adhesive matrix to improve the reflectivity of coating. The optical properties and laser ablation behaviors of coatings with different ceramic additive ratio of La1‑xSrxTiO3+δ and modified epoxy-La1‑xSrxTiO3+δ with ammonium polyphosphate coatings were investigated, respectively. We found that the reflectivity of coatings is extremely high due to mixed high-reflection La1‑xSrxTiO3+δ particles, up to 96% at 1070 nm, which can significantly improve the laser resistance. In addition, the ammonium polyphosphate modifies the residual carbon structure of epoxy resin from discontinuous fine particles structure to continuous and porous structure, which greatly enhances the thermal-insulation property of coating. Furthermore, the laser ablation threshold is improved obviously, which is from 800 W cm‑2 to 1000 W cm‑2.

Enhanced simultaneous PEC eradication of bacteria and antibiotics by facilely fabricated high-activity {001} facets TiO2 mounted onto TiO2 nanotubular photoanode.

PubMed

Li, Guiying; Nie, Xin; Chen, Jiangyao; Wong, Po Keung; An, Taicheng; Yamashita, Hiromi; Zhao, Huijun

2016-09-15

Biohazards and coexisted antibiotics are two groups of emerging contaminants presented in various aquatic environments. They can pose serious threat to the ecosystem and human health. As a result, inactivation of biohazards, degradation of antibiotics, and simultaneous removal of them are highly desired. In this work, a novel photoanode with a hierarchical structured {001} facets exposed nano-size single crystals (NSC) TiO2 top layer and a perpendicularly aligned TiO2 nanotube array (NTA) bottom layer (NSC/NTA) was successfully fabricated. The morphology and facets of anatase TiO2 nanoparticles covered on the top of NTA layer could be controlled by adjusting precalcination temperature and heating rate as the pure NTA was clamped with glasses. Appropriate recalcination can timely remove surface F from {001} facets, and the photocatalytic activity of the resultant photoanode was subsequently activated. NSC/NTA photoanode fabricated under 500 °C precalcination with 20 °C min(-1) followed by 550 °C recalcination possessed highest photoelectrocatalytic efficiency to simultaneously remove bacteria and antibiotics. Results suggest that two-step calcination is necessary for fabrication of high photocatalytic activity NSC/NTA photoanode. The capability of simultaneous eradication of bacteria and antibiotics shows great potential for development of a versatile approach to effectively purify various wastewaters contaminated with complex pollutants. Copyright © 2016 Elsevier Ltd. All rights reserved.

Optically active bis(β-diketonate) complexes of titanium.

PubMed

Kongprakaiwoot, Natcharee; Armstrong, Jack B; Noll, Bruce C; Brown, Seth N

2010-11-14

The 2,2'-bis(methylene)biphenyl bridged bis(diketonate) (Tol(2)Bob)Ti(IV) fragment is resolved by reaction of the isopropoxide complex with (R)-1,1'-bi-2-naphthol, which selectively forms (S,Δ)-(Tol(2)Bob)Ti(R-BINOL). The binaphtholate ligand can be cleaved from titanium by careful treatment with trifluoromethanesulfonic acid to give (S,Δ)-(Tol(2)Bob)Ti(OTf)(2), which has a half-life toward racemization of at least 34 h at 51 °C. Racemization of the (Tol(2)Bob)Ti(IV) fragment is strongly accelerated under protic conditions, probably due to protonolysis of one of the diketonate ligands. Analogous optically active titanium bis(diketonates) can also be prepared by using an optically active 2,2'-bis(methylene)-1,1'-binaphthyl bridged bis(diketonate) ligand, Tol(2)Bobbinap, prepared from (R)-BINOLH2. Complexation of (R)-Tol(2)BobbinapH(2) with Ti(OiPr)(4) gives only a single diastereomer with the Λ configuration at titanium. The bis(diketonate)titanium(IV) fragment gives rise to characteristic signals in circular dichroism spectra which can be used to identify the configuration at the metal centre.

Krypton-81 in groundwater of the Culebra Dolomite near the Waste Isolation Pilot Plant, New Mexico.

PubMed

Sturchio, Neil C; Kuhlman, Kristopher L; Yokochi, Reika; Probst, Peter C; Jiang, Wei; Lu, Zheng-Tian; Mueller, Peter; Yang, Guo-Min

2014-05-01

The Waste Isolation Pilot Plant (WIPP) in New Mexico is the first geologic repository for disposal of transuranic nuclear waste from defense-related programs of the US Department of Energy. It is constructed within halite beds of the Permian-age Salado Formation. The Culebra Dolomite, confined within Rustler Formation evaporites overlying the Salado Formation, is a potential pathway for radionuclide transport from the repository to the accessible environment in the human-disturbed repository scenario. Although extensive subsurface characterization and numerical flow modeling of groundwater has been done in the vicinity of the WIPP, few studies have used natural isotopic tracers to validate the flow models and to better understand solute transport at this site. The advent of Atom-Trap Trace Analysis (ATTA) has enabled routine measurement of cosmogenic (81)Kr (half-life 229,000 yr), a near-ideal tracer for long-term groundwater transport. We measured (81)Kr in saline groundwater sampled from two Culebra Dolomite monitoring wells near the WIPP site, and compared (81)Kr model ages with reverse particle-tracking results of well-calibrated flow models. The (81)Kr model ages are ~130,000 and ~330,000 yr for high-transmissivity and low-transmissivity portions of the formation, respectively. Compared with flow model results which indicate a relatively young mean hydraulic age (~32,000 yr), the (81)Kr model ages imply substantial physical attenuation of conservative solutes in the Culebra Dolomite and provide limits on the effective diffusivity of contaminants into the confining aquitards. Copyright © 2014 Elsevier B.V. All rights reserved.

Strength and Deformation of Solid Krypton and Xenon to Mbar Pressures

NASA Astrophysics Data System (ADS)

Brugman, B. L.; Lv, M.; Liu, J.; Park, C.; Popov, D.; Prakapenka, V. B.; Dorfman, S.

2017-12-01

Studying phase equilibria and deformation of rare gas solids (RGS) under pressure provides insight into their behavior in planetary bodies. Their simple bonding properties make them useful analogs for materials with similar structures and other van der Waals bonded materials. He, Ne, and Ar are useful as pressure-transmitting media in diamond anvil cell (DAC) experiments due to their low strength and inert chemistry, and Xe has been proposed as a pressure medium as well, but relatively little is known about the strength of Kr and Xe. The strength of heavy RGS may be affected by a martensitic transition from fcc to hcp structure, which is observed at lower pressures with higher Z. The pressure ranges of this transition in Kr and Xe in previous experimental and computational studies vary from 5 to 29 GPa for Xe and as high as 130 GPa for Kr. The transition may be further complicated by kinetics and multiple transition mechanisms. Modeling of phase equilibria and evaluation of Kr and Xe as pressure media may be improved by examination of elastic and plastic properties at extreme pressure. We studied phase transitions and deformation of Kr and Xe using synchrotron x-ray diffraction at Advanced Photon Source beamlines 13-ID-D and 16-BM-D in the DAC at pressures up to 118 GPa. The martensitic fcc-hcp phase transition begins as peak asymmetry and weak peaks in both Kr and Xe at pressures as low as 5 GPa. Intensity of hcp peaks in Xe increases continuously to 118 GPa. Weak hcp peaks were evident in Kr alongside fcc peaks from 5 to 94 GPa, contrary to theoretical predictions that the hcp transition does not begin below 110-130 GPa. Strength and plasticity of Kr and Xe were obtained by complementary lattice strain and peak width analysis of diffraction patterns in both axial and radial geometries as well as observation of pressure gradients by ruby fluorescence. Xe is approximately hydrostatic with strength comparable to common pressure media at pressures up to 10-12 GPa. Differential stress in Xe increases quickly above 12 GPa and then levels off above 30-50 GPa. This apparent reduction in strength coincides with dramatic growth of hcp peaks, suggesting that weakening is associated with the fcc-hcp transition. Strength is systematically higher for higher-Z RGS below the fcc-hcp transition, but transformation to the hcp structure modifies this trend.

Shock-induced mechanochemistry in heterogeneous reactive powder mixtures

NASA Astrophysics Data System (ADS)

Gonzales, Manny; Gurumurthy, Ashok; Kennedy, Gregory; Neel, Christopher; Gokhale, Arun; Thadhani, Naresh

The bulk response of compacted powder mixtures subjected to high-strain-rate loading conditions in various configurations is manifested from behavior at the meso-scale. Simulations at the meso-scale can provide an additional confirmation of the possible origins of the observed response. This work investigates the bulk dynamic response of Ti +B +Al reactive powder mixtures under two extreme loading configurations - uniaxial stress and strain loading - leveraging highly-resolved in-situ measurements and meso-scale simulations. Modified rod-on-anvil impact tests on a reactive pellet demonstrate an optimized stoichiometry promoting reaction in Ti +B +Al. Encapsulated powders subjected to shock compression via flyer plate tests provide possible evidence of a shock-induced reaction at high pressures. Meso-scale simulations of the direct experimental configurations employing highly-resolved microstructural features of the Ti +B compacted mixture show complex inhomogeneous deformation responses and reveal the importance of meso-scale features such as particle size and morphology and their effects on the measured response. Funding is generously provided by DTRA through Grant No. HDTRA1-10-1-0038 (Dr. Su Peiris - Program Manager) and by the SMART (AFRL Wright Patterson AFB) and NDSEG fellowships (High Performance Computing and Modernization Office).

TiO2 Nanorods Preparation from Titanyl Sulphate Produced by Dissolution of Ilmenite

NASA Astrophysics Data System (ADS)

Wahyuningsih, S.; Rinawati, L.; Munifa, R. M. I.; Ramelan, A. H.; Sulistyono, Eko

2017-02-01

One-dimensional titanium oxides (TiO2) nanorods have substantial applications in photocatalytic, nanoelectronic, and photoelectrochemical solar cells. These applications require large quantities of materials and a production technique suitable for future industry fabrication. We demonstrate here a new method of TiO2 nanorods production from ilmenite sands (FeTiO3). In this process, the roasted ilmenite sand was separated from the iron content and dissolved in the sulphuric acid solution. Separation process of TiO2 from ilmenite has been carried out by roasting, leaching and precipitation processes. The roasting process was conducted by the addition of Na2S at a temperature of 800°C that had been deomposed ilmenite into hematite (Fe2O3), anatase TiO2, rutile TiO2, Na2SO4, NaFeS2 and NaFeO2. Separation TiO2 from titanyl sulfate (TiOSO4) after leaching in H2SO4 solution was conducted by hydrolysis-condensation step and complexation step of Fe2+ content. KCNS solution was used as a complexing agent. The xerogel synthesized TiO2 then was prepared to 1-D nanostructure of TiO2 nanorods by hydrothermal process under alkaline condition. By the two-step method, we finally gain the 1D nanorods TiO2 extracted from ilmenite sand. The characterization using the Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) obtained the nanorod morphology at a diameter about 9.6 nm.

Mechanism of generation of large (Ti,Nb,V)(C,N)-type precipitates in H13 + Nb tool steel

NASA Astrophysics Data System (ADS)

Xie, You; Cheng, Guo-guang; Chen, Lie; Zhang, Yan-dong; Yan, Qing-zhong

2016-11-01

The characteristics and generation mechanism of (Ti,Nb,V)(C,N) precipitates larger than 2 μm in Nb-containing H13 bar steel were studied. The results show that two types of (Ti,Nb,V)(C,N) phases exist—a Ti-V-rich one and an Nb-rich one—in the form of single or complex precipitates. The sizes of the single Ti-V-rich (Ti,Nb,V)(C,N) precipitates are mostly within 5 to 10 μm, whereas the sizes of the single Nb-rich precipitates are mostly 2-5 μm. The complex precipitates are larger and contain an inner Ti-V-rich layer and an outer Nb-rich layer. The compositional distribution of (Ti,Nb,V)(C,N) is concentrated. The average composition of the single Ti-V-rich phase is (Ti0.511V0.356Nb0.133)(C x N y ), whereas that for the single Nb-rich phase is (Ti0.061V0.263Nb0.676)(C x N y ). The calculation results based on the Scheil-Gulliver model in the Thermo-Calc software combining with the thermal stability experiments show that the large phases precipitate during the solidification process. With the development of solidification, the Ti-V-rich phase precipitates first and becomes homogeneous during the subsequent temperature reduction and heat treatment processes. The Nb-rich phase appears later.

Inert gases in Sea of Fertility regolith

NASA Technical Reports Server (NTRS)

Vinogradov, A. P.; Zadorozhnyy, I. K.

1974-01-01

The content and isotopic composition were studied of inert gases -- He, Ne, Ar, Kr, and Xe -- in samples of lunar regolith returned by the Luna 16 automatic station. The samples were taken from depths of about 12 and 30 cm. The high concentrations of inert gases exceed by several orders their concentrations observed in ordinary stony meteorites. The gases in lunar regolith were a complex mixture of gases of different origins: Solar, cosmogenic, radiogenic, and so on. Solar wind gases predominated, distributed in the thin surficial layer of the regolith grains. The concentrations of these gases in the surficial layer is several cubic centimeters per gram. The isotopic composition of the inert gases of solar origin approaches their composition measured in gas-rich meteorites.

Ab initio studies of the Rg–NO{sup +}(X{sup 1}Σ{sup +}) van der Waals complexes (Rg = He, Ne, Ar, Kr, and Xe)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Orek, Cahit; Bulut, Niyazi, E-mail: jklos@umd.edu, E-mail: francois.lique@univ-lehavre.fr, E-mail: bulut-niyazi@yahoo.com; Kłos, Jacek, E-mail: jklos@umd.edu, E-mail: francois.lique@univ-lehavre.fr, E-mail: bulut-niyazi@yahoo.com

2016-05-28

We used the explicitly correlated variant of the coupled clusters method with single, double, and noniterative triple excitations [CCSD(T)-F12] to compute two-dimensional potential energy surfaces of van der Waals complexes formed by rare gas atoms (Rg) and NO{sup +}(X{sup 1}Σ{sup +}) cations. We used the correlation-consistent, triple-zeta (cc-pVTZ-F12) atomic basis sets, and for Kr and Xe rare gases, we employed corresponding pseudopotential cc-pVTZ-PP-F12 atomic basis sets. These basis sets were additionally augmented with mid-bond functions. The complexes are all of skewed T-shape type with Rg atom being closer to the N-side. Using analytical representation of the potentials, we have estimatedmore » zero-point energy corrected dissociation energies from anharmonic calculations with BOUND program and also from the harmonic approximation. The binding energies increase with the polarization of the Rg atom in series from He to Xe and are 196 cm{sup −1}, 360 cm{sup −1}, 1024 cm{sup −1}, 1434 cm{sup −1}, and 2141 cm{sup −1}, respectively. Their corresponding dissociation energies are 132 cm{sup −1}, 300 cm{sup −1}, 927 cm{sup −1}, 1320 cm{sup −1}, and 1994 cm{sup −1} for the complexes with He to Xe, respectively. We find good agreement with previous theoretical and experimental results. The harmonic vibrational frequencies were calculated for the bending and stretching modes of the Rg–NO{sup +} complexes.« less

Photoelectron imaging of doped helium nanodroplets

NASA Astrophysics Data System (ADS)

Neumark, Daniel

2008-03-01

Photoelectron images of helium nanodroplets doped with Kr and Ne atoms are reported. The images and resulting photoelectron spectra were obtained using tunable synchrotron radiation to ionize the droplets. Droplets were excited at 21.6 eV, corresponding to a strong droplet electronic excitation. The rare gas dopant is then ionized via a Penning excitation transfer process. The electron kinetic energy distributions reflect complex ionization and electron escape dynamics.

Radiometric 81Kr dating identifies 120,000-year-old ice at Taylor Glacier, Antarctica

PubMed Central

Buizert, Christo; Baggenstos, Daniel; Jiang, Wei; Purtschert, Roland; Petrenko, Vasilii V.; Lu, Zheng-Tian; Müller, Peter; Kuhl, Tanner; Lee, James; Severinghaus, Jeffrey P.; Brook, Edward J.

2014-01-01

We present successful 81Kr-Kr radiometric dating of ancient polar ice. Krypton was extracted from the air bubbles in four ∼350-kg polar ice samples from Taylor Glacier in the McMurdo Dry Valleys, Antarctica, and dated using Atom Trap Trace Analysis (ATTA). The 81Kr radiometric ages agree with independent age estimates obtained from stratigraphic dating techniques with a mean absolute age offset of 6 ± 2.5 ka. Our experimental methods and sampling strategy are validated by (i) 85Kr and 39Ar analyses that show the samples to be free of modern air contamination and (ii) air content measurements that show the ice did not experience gas loss. We estimate the error in the 81Kr ages due to past geomagnetic variability to be below 3 ka. We show that ice from the previous interglacial period (Marine Isotope Stage 5e, 130–115 ka before present) can be found in abundance near the surface of Taylor Glacier. Our study paves the way for reliable radiometric dating of ancient ice in blue ice areas and margin sites where large samples are available, greatly enhancing their scientific value as archives of old ice and meteorites. At present, ATTA 81Kr analysis requires a 40–80-kg ice sample; as sample requirements continue to decrease, 81Kr dating of ice cores is a future possibility. PMID:24753606

Radiometric 81Kr dating identifies 120,000-year-old ice at Taylor Glacier, Antarctica.

PubMed

Buizert, Christo; Baggenstos, Daniel; Jiang, Wei; Purtschert, Roland; Petrenko, Vasilii V; Lu, Zheng-Tian; Müller, Peter; Kuhl, Tanner; Lee, James; Severinghaus, Jeffrey P; Brook, Edward J

2014-05-13

We present successful (81)Kr-Kr radiometric dating of ancient polar ice. Krypton was extracted from the air bubbles in four ∼350-kg polar ice samples from Taylor Glacier in the McMurdo Dry Valleys, Antarctica, and dated using Atom Trap Trace Analysis (ATTA). The (81)Kr radiometric ages agree with independent age estimates obtained from stratigraphic dating techniques with a mean absolute age offset of 6 ± 2.5 ka. Our experimental methods and sampling strategy are validated by (i) (85)Kr and (39)Ar analyses that show the samples to be free of modern air contamination and (ii) air content measurements that show the ice did not experience gas loss. We estimate the error in the (81)Kr ages due to past geomagnetic variability to be below 3 ka. We show that ice from the previous interglacial period (Marine Isotope Stage 5e, 130-115 ka before present) can be found in abundance near the surface of Taylor Glacier. Our study paves the way for reliable radiometric dating of ancient ice in blue ice areas and margin sites where large samples are available, greatly enhancing their scientific value as archives of old ice and meteorites. At present, ATTA (81)Kr analysis requires a 40-80-kg ice sample; as sample requirements continue to decrease, (81)Kr dating of ice cores is a future possibility.

Energy-Transfer Kinetics for Xe (6p[1/2]0) Atoms in Kr, Ar, Ne, and He.

PubMed

He, Shan; Liu, Dong; Li, Xueyang; Chu, Junzhi; Guo, Jingwei; Liu, Jinbo; Hu, Shu; Sang, Fengting; Jin, Yuqi

2018-06-11

The kinetic processes for the Xe (6p[1/2] 0 ) atoms in Kr, Ar, Ne, and He buffer gases were studied. We found that Kr, Ar, and Ne atoms can be used to switch the amplified spontaneous emission (ASE) channel from 3408 nm (6p[1/2] 0 -6s'[1/2] 1 ) to 3680 nm (5d[1/2] 1 -6p[1/2] 1 ), while Xe and He atoms do not show such a phenomenon. This ASE channel switch is mainly ascribed to the fast transfer of 6p[1/2] 0 → 5d[1/2] 1 . On the basis of the rate equations for two-state coupling (energy-transfer processes between the two states are very rapid), the reason why the ASE channel switch effect normally coincides with a double exponential decay of the spontaneous emission at 828 nm (6p[1/2] 0 -6s[3/2] 1 ) is explained. The actual situations in Xe, Ar, Ne, and He follow this rule. However, the strictly single exponential decay of the spontaneous emission at 828 nm and strong ASE channel switch effect simultaneously emerge in Kr. This indicates that the transfer of 6p[1/2] 0 → 5d[1/2] 1 in Kr does not occur via two-state coupling, but via two steps of near-resonance collision through the 5s[3/2] 2 (Kr) state as the intermediate state (6p[1/2] 0 → 5s[3/2] 2 (Kr) → 5d[1/2] 1 ). In addition, we found Xe (6p[1/2] 0 ) atoms strongly tend to reach the 6p[3/2] 2 , 6p[3/2] 1 , and 6p[5/2] 2 states through the 5s[3/2] 2 (Kr) state as the intermediate state in Kr. The 5s[3/2] 2 (Kr) state plays a very important role in the energy-transfer kinetics for the Xe (6p[1/2] 0 ) atoms. Kr is probably an excellent buffer gas for laser systems based on Xe.

Mechanical Properties of a Newly Additive Manufactured Implant Material Based on Ti-42Nb

PubMed Central

Schulze, Christian; Weinmann, Markus; Schweigel, Christoph; Keßler, Olaf; Bader, Rainer

2018-01-01

The application of Ti-6Al-4V alloy or commercially pure titanium for additive manufacturing enables the fabrication of complex structural implants and patient-specific implant geometries. However, the difference in Young’s modulus of α + β-phase Ti alloys compared to the human bone promotes stress-shielding effects in the implant–bone interphase. The aim of the present study is the mechanical characterization of a new pre-alloyed β-phase Ti-42Nb alloy for application in additive manufacturing. The present investigation focuses on the mechanical properties of SLM-printed Ti-42Nb alloy in tensile and compression tests. In addition, the raw Ti-42Nb powder, the microstructure of the specimens prior to and after compression tests, as well as the fracture occurring in tensile tests are characterized by means of the SEM/EDX analysis. The Ti-42Nb raw powder exhibits a dendrite-like Ti-structure, which is melted layer-by-layer into a microstructure with a very homogeneous distribution of Nb and Ti during the SLM process. Tensile tests display Young’s modulus of 60.51 ± 3.92 GPa and an ultimate tensile strength of 683.17 ± 16.67 MPa, whereas, under a compressive load, a compressive strength of 1330.74 ± 53.45 MPa is observed. The combination of high mechanical strength and low elastic modulus makes Ti-42Nb an interesting material for orthopedic and dental implants. The spherical shape of the pre-alloyed material additionally allows for application in metal 3D printing, enabling the fabrication of patient-specific structural implants. PMID:29342864

Mechanical Properties of a Newly Additive Manufactured Implant Material Based on Ti-42Nb.

PubMed

Schulze, Christian; Weinmann, Markus; Schweigel, Christoph; Keßler, Olaf; Bader, Rainer

2018-01-13

The application of Ti-6Al-4V alloy or commercially pure titanium for additive manufacturing enables the fabrication of complex structural implants and patient-specific implant geometries. However, the difference in Young's modulus of α + β-phase Ti alloys compared to the human bone promotes stress-shielding effects in the implant-bone interphase. The aim of the present study is the mechanical characterization of a new pre-alloyed β-phase Ti-42Nb alloy for application in additive manufacturing. The present investigation focuses on the mechanical properties of SLM-printed Ti-42Nb alloy in tensile and compression tests. In addition, the raw Ti-42Nb powder, the microstructure of the specimens prior to and after compression tests, as well as the fracture occurring in tensile tests are characterized by means of the SEM/EDX analysis. The Ti-42Nb raw powder exhibits a dendrite-like Ti-structure, which is melted layer-by-layer into a microstructure with a very homogeneous distribution of Nb and Ti during the SLM process. Tensile tests display Young's modulus of 60.51 ± 3.92 GPa and an ultimate tensile strength of 683.17 ± 16.67 MPa, whereas, under a compressive load, a compressive strength of 1330.74 ± 53.45 MPa is observed. The combination of high mechanical strength and low elastic modulus makes Ti-42Nb an interesting material for orthopedic and dental implants. The spherical shape of the pre-alloyed material additionally allows for application in metal 3D printing, enabling the fabrication of patient-specific structural implants.

Tio2-dopamine complex implanted unilaterally in the caudate nucleus improves motor activity and behavior function of rats with induced hemiparkinsonism.

PubMed

Vergara-Aragón, Patricia; Domínguez-Marrufo, Leonardo Eduardo; Ibarra-Guerrero, Patricia; Hernandez-Ramírez, Heidi; Hernández-Téllez, Beatriz; López-Martínez, Irma Elena; Sánchez-Cervantes, Ivonne; Santiago-Jacinto, Patricia; García-Macedo, Jorge Alberto; Valverde-Aguilar, Guadalupe; Santiago, Julio

2011-01-01

Parkinson's disease (PD) is characterized by malfunction of dopaminergic systems, and the current symptomatic treatment is to replace lost dopamine. For investigating mechanisms of pathogenesis and alternative treatments to compensate lack of dopamine (DA) activity in PD, the 6-hydroxydopamine (6-OHDA)-lesioned rat model of PD has been useful, these animals display apomorphine-induced contralateral rotational behavior, when they are examined after lesion. The purpose of this study was to assess Titania-dopamine (TiO2-DA) complexes implanted on the caudate nucleus for diminishing motor behavior alterations of the 6-OHDA rat model. Rats with 6-OHDA unilateral lesions received TiO2 alone or TiO2-DA implants, and were tested for open field (OF) gross motor crossing and rearing behaviors, and apomorphine-induced rotation (G) behavior. TiO2 complex have no effects on rearing OF and G behaviors, and a significant reducing effect on crossing motor behavior of normal rats compared to control non-treated rats throughout 56 days of observation. Interestingly, TiO2-DA treatment significant recovered motor crossing and rearing behaviors in 6-OHDA-lesioned rats, and diminished the G behaviors during 56 days of examination. Additionally, in the 6-OHDA-lesioned rats TiO2 treatment had a moderate recovering effect only on crossing behavior compared to lesioned non treated rats. Our results suggest that continuous release of dopamine in the caudate nucleus from TiO2-DA complex is capable of reversing gross motor deficits observed in the 6-OHDA-lesioned rat model of PD. Thistype of delivery system of DA represents a promising therapy for PD in humans.

Stabilization of nanosized titanium dioxide by cyclodextrin polymers and its photocatalytic effect on the degradation of wastewater pollutants

PubMed Central

Agócs, Tamás Zoltán; Puskás, István; Varga, Erzsébet; Molnár, Mónika

2016-01-01

Advanced oxidation processes (AOPs) are considered highly competitive water treatment technologies for the removal of organic pollutants. Among AOP techniques, photocatalysis has recently been the most widely studied. Our aims were to investigate how the dispersion of nanosized titanium dioxide (nanoTiO2) applied in photodegradation-based procedures can be stabilized with cyclodextrins in order to obtain a new, more efficient photocatalyst for the purification of waters polluted by xenobiotics applying UV irradiation. During our work, on the one hand, we studied the behavior and stability of nanoTiO2 in cyclodextrin solutions. On the other hand, we used various monomer and polymer cyclodextrin derivatives, and assessed the options for nanoTiO2 stabilization in the presence of various salts and tap water on the basis of turbidity tests. The physical stability of nanoTiO2 dispersions is diminished in the presence of the salts found in tap water (and occurring also in surface waters and ground water) and they are precipitated immediately. This colloidal instability can be improved by cyclodextrin derivatives. Based on the results of our studies we have selected carboxymethyl β-cyclodextrin polymer (CMBCD-P) for stabilization of nanoTiO2 dispersions. The photocatalytic degradation of methylene blue and ibuprofen as model organic pollutants in various media (distilled water, NaCl solution and tap water) has been studied using nanoTiO2 as catalyst stabilized by CMBCD-P. CMBCD-P itself showed a catalytic effect on the UV degradation of methylene blue. In addition to enhancing the colloid stability of nanoTiO2 CMBCD-P showed also synergistic effects in catalyzing the photodecomposition process of the dye. On the other hand, ibuprofen as a model pharmaceutical, a pollutant of emerging concern (EP), was protected by CMBCD-P against the photocatalytic degradation showing that inclusion complex formation can result in opposite effects depending on the structure of the host–guest complex. PMID:28144360

Stabilization of nanosized titanium dioxide by cyclodextrin polymers and its photocatalytic effect on the degradation of wastewater pollutants.

PubMed

Agócs, Tamás Zoltán; Puskás, István; Varga, Erzsébet; Molnár, Mónika; Fenyvesi, Éva

2016-01-01

Advanced oxidation processes (AOPs) are considered highly competitive water treatment technologies for the removal of organic pollutants. Among AOP techniques, photocatalysis has recently been the most widely studied. Our aims were to investigate how the dispersion of nanosized titanium dioxide (nanoTiO 2 ) applied in photodegradation-based procedures can be stabilized with cyclodextrins in order to obtain a new, more efficient photocatalyst for the purification of waters polluted by xenobiotics applying UV irradiation. During our work, on the one hand, we studied the behavior and stability of nanoTiO 2 in cyclodextrin solutions. On the other hand, we used various monomer and polymer cyclodextrin derivatives, and assessed the options for nanoTiO 2 stabilization in the presence of various salts and tap water on the basis of turbidity tests. The physical stability of nanoTiO 2 dispersions is diminished in the presence of the salts found in tap water (and occurring also in surface waters and ground water) and they are precipitated immediately. This colloidal instability can be improved by cyclodextrin derivatives. Based on the results of our studies we have selected carboxymethyl β-cyclodextrin polymer (CMBCD-P) for stabilization of nanoTiO 2 dispersions. The photocatalytic degradation of methylene blue and ibuprofen as model organic pollutants in various media (distilled water, NaCl solution and tap water) has been studied using nanoTiO 2 as catalyst stabilized by CMBCD-P. CMBCD-P itself showed a catalytic effect on the UV degradation of methylene blue. In addition to enhancing the colloid stability of nanoTiO 2 CMBCD-P showed also synergistic effects in catalyzing the photodecomposition process of the dye. On the other hand, ibuprofen as a model pharmaceutical, a pollutant of emerging concern (EP), was protected by CMBCD-P against the photocatalytic degradation showing that inclusion complex formation can result in opposite effects depending on the structure of the host-guest complex.

Rapid and direct synthesis of complex perovskite oxides through a highly energetic planetary milling

PubMed Central

Lee, Gyoung-Ja; Park, Eun-Kwang; Yang, Sun-A; Park, Jin-Ju; Bu, Sang-Don; Lee, Min-Ku

2017-01-01

The search for a new and facile synthetic route that is simple, economical and environmentally safe is one of the most challenging issues related to the synthesis of functional complex oxides. Herein, we report the expeditious synthesis of single-phase perovskite oxides by a high-rate mechanochemical reaction, which is generally difficult through conventional milling methods. With the help of a highly energetic planetary ball mill, lead-free piezoelectric perovskite oxides of (Bi, Na)TiO3, (K, Na)NbO3 and their modified complex compositions were directly synthesized with low contamination. The reaction time necessary to fully convert the micron-sized reactant powder mixture into a single-phase perovskite structure was markedly short at only 30–40 min regardless of the chemical composition. The cumulative kinetic energy required to overtake the activation period necessary for predominant formation of perovskite products was ca. 387 kJ/g for (Bi, Na)TiO3 and ca. 580 kJ/g for (K, Na)NbO3. The mechanochemically derived powders, when sintered, showed piezoelectric performance capabilities comparable to those of powders obtained by conventional solid-state reaction processes. The observed mechanochemical synthetic route may lead to the realization of a rapid, one-step preparation method by which to create other promising functional oxides without time-consuming homogenization and high-temperature calcination powder procedures. PMID:28387324

Dye sensitized solar cell applications of CdTiO3-TiO2 composite thin films deposited from single molecular complex

NASA Astrophysics Data System (ADS)

Ehsan, Muhammad Ali; Khaledi, Hamid; Pandikumar, Alagarsamy; Huang, Nay Ming; Arifin, Zainudin; Mazhar, Muhammad

2015-10-01

A heterobimetallic complex [Cd2Ti4(μ-O)6(TFA)8(THF)6]·1.5THF (1) (TFA=trifluoroacetato, THF=tetrahydrofuran) comprising of Cd:Ti (1:2) ratio was synthesized by a chemical reaction of cadmium (II) acetate with titanium (IV) isopropoxide and triflouroacetic acid in THF. The stoichiometry of (1) was recognized by single crystal X-ray diffraction, spectroscopic and elemental analyses. Thermal studies revealed that (1) neatly decomposes at 450 °C to furnish 1:1 ratio of cadmium titanate:titania composite oxides material. The thin films of CdTiO3-TiO2 composite oxides were deposited at 550 °C on fluorine doped tin oxide coated conducting glass substrate in air ambient. The micro-structure, crystallinity, phase identification and chemical composition of microspherical architectured CdTiO3-TiO2 composite thin film have been determined by scanning electron microscopy, X-ray diffraction, Raman spectroscopy and energy dispersive X-ray analysis. The scope of composite thin film having band gap of 3.1 eV was explored as photoanode for dye-sensitized solar cell application.

Effects of humic acids on the aggregation and sorption of nano-TiO2.

PubMed

Li, Yanjie; Yang, Chen; Guo, Xuetao; Dang, Zhi; Li, Xiaoqin; Zhang, Qian

2015-01-01

In this study, humic acids (HAs) from three sources, peat, sediment and straw, used to coat nano-TiO2 were investigated. The results indicated that HAs isolated from peat were aromatic-rich, whereas those isolated from sediment and straw were aliphatic-rich. The nano-TiO2 sedimentation experiments indicated that the presence of aromatic-rich HAs was more capable of stabilizing nano-TiO2 particles than was the presence of aliphatic-rich HAs. This result is because the deionized phenolic groups in the HAs were preferentially adsorbed on the nano-TiO2 surfaces, which generated a higher charge density on the nano-TiO2 surfaces and caused stronger repulsive forces among particles. Furthermore, the aromatic-rich TiO2-HA complexes exhibited a greater sorption capacity than the aliphatic-rich TiO2-HAs complexes and nonlinear phenanthrene sorption because of their higher affinity and the condensed state of aromatic fractions. Note that natural organic matters, such as humic acids, in aquatic environments can not only increase the stability of nanoparticles but can also influence the mobility of hydrophobic organic compounds (HOCs). Copyright © 2014. Published by Elsevier Ltd.

Microstructural Influence on Mechanical Properties in Plasma Microwelding of Ti6Al4V Alloy

NASA Astrophysics Data System (ADS)

Baruah, M.; Bag, S.

2016-11-01

The complexity of joining Ti6Al4V alloy enhances with reduction in sheet thickness. The present work puts emphasis on microplasma arc welding (MPAW) of 500-μm-thick Ti6Al4V alloy in butt joint configuration. Using controlled and regulated arc current, the MPAW process is specifically designed to use in joining of thin sheet components over a wide range of process parameters. The weld quality is assessed by carefully controlling the process parameters and by reducing the formation of oxides. The combined effect of welding speed and current on the weld joint properties is evaluated for joining of Ti6Al4V alloy. The macro- and microstructural characterizations of the weldment by optical microscopy as well as the analysis of mechanical properties by microtensile and microhardness test have been performed. The weld joint quality is affected by specifically designed fixture that controls the oxidation of the joint and introduces high cooling rate. Hence, the solidified microstructure of welded specimen influences the mechanical properties of the joint. The butt joint of titanium alloy by MPAW at optimal process parameters is of very high quality, without any internal defects and with minimum residual distortion.

Effects of TiO2 crystal structure on the luminescence quenching of [Ru(bpy)2(dppz)]2 +-intercalated into DNA

NASA Astrophysics Data System (ADS)

Chen, Linlin; Wang, Yi; Huang, Minggao; Li, Xiaodan; Zhu, Licai; Li, Hong

2017-06-01

The intercalation of [Ru(bpy)2(dppz)]2 + labeled as Ru(II) (bpy = 2,2‧-bipyridine and dppz = dipyrido[3,2,-a:2‧,3‧-c]phenazine) into herring sperm DNA leads to the formation of emissive Ru(II)-DNA dyads, which can be quenched by TiO2 nanoparticles (NPs) and sol-gel silica matrices at heterogeneous interfaces. The calcinations temperature exhibits a remarkable influence on the luminescence quenching of the Ru(II)-DNA dyads by TiO2 NPs. With increasing calcinations temperature in the range from 200 to 850 °C, the anatase-to-rutile TiO2 crystal structure transformation increases the average particle size and hydrodynamic diameter of TiO2 and DNA@TiO2. The anatase TiO2 has the stronger ability to unbind the Ru(II)-DNA dyads than the rutile TiO2 at room temperature. The TiO2 NPs and sol-gel silica matrices can quench the luminescence of the Ru(II) complex intercalated into DNA by selectively capturing the negatively DNA and positively charged Ru(II) complex to unbind the dyads, respectively. This present results provide new insights into the luminescence quenching and competitive binding of dye-labeled DNA dyads by inorganic NPs.

Anodal transcranial direct current stimulation over the primary motor cortex does not enhance the learning benefits of self-controlled feedback schedules.

PubMed

Carter, Michael J; Smith, Victoria; Carlsen, Anthony N; Ste-Marie, Diane M

2018-05-01

A distinct learning advantage has been shown when participants control their knowledge of results (KR) scheduling during practice compared to when the same KR schedule is imposed on the learner without choice (i.e., yoked schedules). Although the learning advantages of self-controlled KR schedules are well-documented, the brain regions contributing to these advantages remain unknown. Identifying key brain regions would not only advance our theoretical understanding of the mechanisms underlying self-controlled learning advantages, but would also highlight regions that could be targeted in more applied settings to boost the already beneficial effects of self-controlled KR schedules. Here, we investigated whether applying anodal transcranial direct current stimulation (tDCS) to the primary motor cortex (M1) would enhance the typically found benefits of learning a novel motor skill with a self-controlled KR schedule. Participants practiced a spatiotemporal task in one of four groups using a factorial combination of KR schedule (self-controlled vs. yoked) and tDCS (anodal vs. sham). Testing occurred on two consecutive days with spatial and temporal accuracy measured on both days and learning was assessed using 24-h retention and transfer tests without KR. All groups improved their performance in practice and a significant effect for practicing with a self-controlled KR schedule compared to a yoked schedule was found for temporal accuracy in transfer, but a similar advantage was not evident in retention. There were no significant differences as a function of KR schedule or tDCS for spatial accuracy in retention or transfer. The lack of a significant tDCS effect suggests that M1 may not strongly contribute to self-controlled KR learning advantages; however, caution is advised with this interpretation as typical self-controlled learning benefits were not strongly replicated in the present experiment.

Comparisons of sets of electron-neutral scattering cross sections and calculated swarm parameters in Kr and Xe

NASA Astrophysics Data System (ADS)

Bordage, M. C.; Hagelaar, G. J. M.; Pitchford, L. C.; Biagi, S. F.; Puech, V.

2011-10-01

Xenon is used in a number of application areas ranging from light sources to x-ray detectors for imaging in medicine, border security and high-energy particle physics. There is a correspondingly large body of data available for electron scattering cross sections and swarm parameters in Xe, whereas data for Kr are more limited. In this communication we show intercomparisons of the cross section sets in Xe and Kr presently available on the LXCat site. Swarm parameters calculated using these cross sections sets are compared with experimental data, also available on the LXCat site. As was found for Ar, diffusion coefficients calculated using these cross section data in a 2-term Boltzmann solver are higher than Monte Carlo results by about 30% over a range of E/N from 1 to 100 Td. We find otherwise good agreement in Xe between 2-term and Monte Carlo results and between measured and calculated values of electron mobility, ionization rates and light emission (dimer) at atmospheric pressure. The available cross section data in Kr yield swarm parameters in agreement with the limited experimental data. The cross section compilations and measured swarm parameters used in this work are available on-line at www.lxcat.laplace. univ-tlse.fr.

Negligible fractionation of Kr and Xe isotopes by molecular diffusion in water

NASA Astrophysics Data System (ADS)

Tyroller, Lina; Brennwald, Matthias S.; Busemann, Henner; Maden, Colin; Baur, Heinrich; Kipfer, Rolf

2018-06-01

Molecular diffusion is a key transport process for noble gases in water. Such diffusive transport is often thought to cause a mass-dependent fractionation of noble gas isotopes that is inversely proportional to the square root of the ratio of their atomic mass, referred to as the square root relation. Previous studies, challenged the commonly held assumption that the square root relation adequately describes the behaviour of noble gas isotopes diffusing through water. However, the effect of diffusion on noble gas isotopes has only been determined experimentally for He, Ne and Ar to date, whereas the extent of fractionation of Kr and Xe has not been measured. In the present study the fractionation of Kr and Xe isotopes diffusing through water immobilised by adding agar was quantified through measuring the respective isotope ratio after diffusing through the immobilised water. No fractionation of Kr and Xe isotopes was observed, even using high-precision noble gas analytics. These results complement our current understanding on isotopic fractionation of noble gases diffusing through water. Therefore this complete data set builds a robust basis to describe molecular diffusion of noble gases in water in a physical sound manner which is fundamental to assess the physical aspects of gas dynamics in aquatic systems.

High-density Two-Dimensional Small Polaron Gas in a Delta-Doped Mott Insulator

PubMed Central

Ouellette, Daniel G.; Moetakef, Pouya; Cain, Tyler A.; Zhang, Jack Y.; Stemmer, Susanne; Emin, David; Allen, S. James

2013-01-01

Heterointerfaces in complex oxide systems open new arenas in which to test models of strongly correlated material, explore the role of dimensionality in metal-insulator-transitions (MITs) and small polaron formation. Close to the quantum critical point Mott MITs depend on band filling controlled by random disordered substitutional doping. Delta-doped Mott insulators are potentially free of random disorder and introduce a new arena in which to explore the effect of electron correlations and dimensionality. Epitaxial films of the prototypical Mott insulator GdTiO3 are delta-doped by substituting a single (GdO)+1 plane with a monolayer of charge neutral SrO to produce a two-dimensional system with high planar doping density. Unlike metallic SrTiO3 quantum wells in GdTiO3 the single SrO delta-doped layer exhibits thermally activated DC and optical conductivity that agree in a quantitative manner with predictions of small polaron transport but with an extremely high two-dimensional density of polarons, ~7 × 1014 cm−2. PMID:24257578

Imaging Local Polarization in Ferroelectric Thin Films by Coherent X-Ray Bragg Projection Ptychography

NASA Astrophysics Data System (ADS)

Hruszkewycz, S. O.; Highland, M. J.; Holt, M. V.; Kim, Dongjin; Folkman, C. M.; Thompson, Carol; Tripathi, A.; Stephenson, G. B.; Hong, Seungbum; Fuoss, P. H.

2013-04-01

We used x-ray Bragg projection ptychography (BPP) to map spatial variations of ferroelectric polarization in thin film PbTiO3, which exhibited a striped nanoscale domain pattern on a high-miscut (001) SrTiO3 substrate. By converting the reconstructed BPP phase image to picometer-scale ionic displacements in the polar unit cell, a quantitative polarization map was made that was consistent with other characterization. The spatial resolution of 5.7 nm demonstrated here establishes BPP as an important tool for nanoscale ferroelectric domain imaging, especially in complex environments accessible with hard x rays.

Estimation of 85Kr dispersion from the spent nuclear fuel reprocessing plant in Rokkasho, Japan, using an atmospheric dispersion model.

PubMed

Abe, K; Iyogi, T; Kawabata, H; Chiang, J H; Suwa, H; Hisamatsu, S

2015-11-01

The spent nuclear fuel reprocessing plant of Japan Nuclear Fuel Limited (JNFL) located in Rokkasho, Japan, discharged small amounts of (85)Kr into the atmosphere during final tests of the plant with actual spent fuel from 31 March 2006 to October 2008. During this period, the gamma-ray dose rates due to discharged (85)Kr were higher than the background rates measured at the Institute for Environmental Sciences and at seven monitoring stations of the Aomori prefectural government and JNFL. The dispersion of (85)Kr was simulated by means of the fifth-generation Penn State/NCAR Mesoscale Model and the CG-MATHEW/ADPIC models (ver. 5.0) with a vertical terrain-following height coordinate. Although the simulated gamma-ray dose rates due to discharged (85)Kr agreed fairly well with measured rates, the agreement between the estimated monthly mean (85)Kr concentrations and the observed concentrations was poor. Improvement of the vertical flow of air may lead to better estimation of (85)Kr dispersion. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

SEP-Kr and SEP-Xe in Lunar Ilmenite and the Ar/Kr/Xe Ratio in the Solar Wind

NASA Astrophysics Data System (ADS)

Wieler, R.; Baur, H.; Signer, P.

1992-07-01

We analyzed all five noble gases in an ilmenite sample from lunar soil 71501 by closed system stepped etching (CSSE), thus extending our CSSE studies of solar noble gases (Wieler et al., 1986; Benkert et al., 1988) to Kr and Xe. He, Ne, Ar isotopes: We observe the familiar presence of two solar noble gas components: step 1 shows ^4He/^3He = 2250, ^20Ne/^22Ne = 13.8, and ^36Ar/^38Ar=5.46. The first two ratios are essentially identical to modern solar wind values (SWC; Geiss, 1973), indicating an isotopically unfractionated SW noble gas reservoir in lunar ilmenite. The Ne data-points of later steps fall on a straight line and reach the SEP-Ne point (^20Ne/^22Ne = 11.3). The slope of this line indicates mass dependent fractionation between SW-Ne and SEP-Ne. SEP-He (^4He/^3He = 4650 +-100) and SEP-Ar (^36Ar/^38Ar = 4.89+-0.05) are also observed (latter two numbers slightly revised compared to Wieler et al., 1992). Kr, Xe isotopes: Kr in those two steps that release pure SW-Ne is very slightly lighter than atmospheric Kr (^86Kr/^84Kr = 0.3041; see also Wieler et al., 1992). We interpret this to be SW-Kr in soil 71501. Steps containing (isotopically heavier) SEP-Ne likewise release heavier Kr, interpreted accordingly as SEP-Kr (^86Kr/^84Kr = 0.323). Similarly, a light Xe component is released first (SW-Xe, ^136Xe/^132Xe = 0.3003), followed by heavier SEP-Xe (^136Xe/^132Xe = 0.319). The data are consistent with both Kr and Xe in SW and SEP components to be related by mass fractionation. The relation first proposed by Benkert et al. (1988) between a ratio R(m(sub)2,m(sub)1) of two isotopes with masses m(sub)2>m(sub)1 in SW and SEP now holds for all five noble gases: (R(sub)SW-R(sub)SEP)/R(sub)SW = (2+-0.13)*(m(sub)2- m(sub)1)/m(sub)2. Since m(sub)2~m(sub)1, this relation may also be written as: R(sub)SEP/R(sub)SW ~ (m(sub)1/m(sub)2)^2 (Geiss and Bochsler, 1991). Element ratios: ^4He/^36Ar and ^20Ne/^36Ar rise from values several times below SWC to essentially SWC ratios in the steps releasing nearly pure SEP gases, indicating element fractionation between SW-He/Ne, but essentially unfractionated SEP-He/Ne/Ar in lunar ilmenite. In contrast, Kr/Xe stays virtually constant (^84Kr/^132Xe = 8.4+-0.5), except in the first few steps. If the light three noble gases indeed are not fractionated in the SEP dominated steps, we would also expect no fractionation for Kr/Xe. The measured ^84Kr/^132Xe ratio is, however, about 2.4 times lower than the most recent "solar system" ratio (Anders and Grevesse, 1989), albeit only ~30% lower than the "solar" value preferred by Marti and Suess (1988). Kr/Xe ratios similar to those in ilmenites have been found earlier, e.g. in Peysanoe (Marti, 1969). They are often taken to indicate fractionated loss of solar noble gases. Based on the new CSSE results, we propose, instead, that lunar ilmenites retain a faithful record of ^84Kr/^132Xe in SW and SEP (and also ^36Ar/^84Kr(sub)SW = 1750+- 300). If so, this may indicate noble gas fractionation in the solar corpuscular radiation, perhaps depending on first ionization potential or a related parameter. Work supported by the Swiss National Science Foundation. References: Anders, E. and Grevesse, N. (1989) Geochim. Cosmochim. Acta. 53, 197-214. Benkert, J.-P. et al. (1988) Lunar Planet. Sci. (abstract) 19, 59-60. Geiss, J. (1973) Proc. 13th Int. Cosmic Ray Conf. 3375-3398. Geiss, J. and Bochsler, P. (1991) In The Sun in Time (eds. C. P. Sonett, M. S. Giampapa and M.S. Matthews), pp. 98-117. Univ. Arizona Press, Tucson, Arizona. Marti, K. (1969) Science. 166. 1263-1265. Marti, K. and Suess, H. E. (1988) Astrophys. Space Sci. 144. 507-517. Wieler, R. et al. (1986) Geochim. Cosmochim. Acta. 50. 1997-2017. Wieler, R. et al. (1992) Lunar Planet. Sci. (abstract) 23.

Evaluation of the tratment of metal-EDTA complexes using Ti0{sub 2} photocatalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Madden, T.; Datyte, A.K.; Prairie, M.R.

1996-03-01

This study has demonstrated the feasibility of TiO{sub 2} photocatalysis to treat EDTA and several metal-EDTA complexes that can be found in industrial wastewaters. For the EDTA complexes of metals capable of photodeposition, such as Cu and Pb, certain reaction conditions were shown to facilitate the simultaneous complex degradation and photodeposition of these metals onto the catalyst. With metals that do not easily photodeposit, such as Ni and Cd, it is shown that the complex degradation is still facilitated, and can enhance other metals removal processes after photocatalytic treatment. Because the treatment of these metal-EDTA complexes typically requires special measures,more » there may exist situations where TiO{sub 2} photocatalysis could actually be the preferred method of treatment. However, its use should be compared economically to other more established advanced oxidation technologies. This necessity is demonstrated in the economic comparison to ozone treatment for EDTA degradation alone, where ozone treatment appears to be the clear choice in this application.« less

Origin of colossal permittivity in (In1/2Nb1/2)TiO2via broadband dielectric spectroscopy.

PubMed

Zhao, Xiao-gang; Liu, Peng; Song, Yue-Chan; Zhang, An-ping; Chen, Xiao-ming; Zhou, Jian-ping

2015-09-21

(In1/2Nb1/2)TiO2 (IN-T) ceramics were prepared via a solid-state reaction route. X-ray diffraction (XRD) and Raman spectroscopy were used for the structural and compositional characterization of the synthesized compounds. The results indicated that the sintered ceramics have a single phase of rutile TiO2. Dielectric spectroscopy (frequency range from 20 Hz to 1 MHz and temperature range from 10 K to 270 K) was performed on these ceramics. The IN-T ceramics showed extremely high permittivities of up to ∼10(3), which can be referred to as colossal permittivity, with relatively low dielectric losses of ∼0.05. Most importantly, detailed impedance data analyses of IN-T demonstrated that electron-pinned defect-dipoles, interfacial polarization and polaron hopping polarization contribute to the colossal permittivity at high temperatures (270 K); however, only the complexes (pinned electron) and polaron hopping polarization are active at low temperatures (below 180 K), which is consistent with UDR analysis.

Properties of 83mKr conversion electrons and their use in the KATRIN experiment

NASA Astrophysics Data System (ADS)

Vénos, D.; Sentkerestiová, J.; Dragoun, O.; Slezák, M.; Ryšavý, M.; Špalek, A.

2018-02-01

The gaseous 83mKr will be used as a source of monoenergetic conversion electrons for systematic studies and calibration of the energy scale in the KArlsruhe TRItium Neutrino experiment (KATRIN). Using all existing experimental data the adopted values of the electron binding energies for free krypton were established and the basic conversion electron properties in 83mKr decay were compiled. Modes of the measurements with gaseous 83mKr were suggested for KATRIN.

Photocatalytic activity of low temperature oxidized Ti-6Al-4V.

PubMed

Unosson, Erik; Persson, Cecilia; Welch, Ken; Engqvist, Håkan

2012-05-01

Numerous advanced surface modification techniques exist to improve bone integration and antibacterial properties of titanium based implants and prostheses. A simple and straightforward method of obtaining uniform and controlled TiO(2) coatings of devices with complex shapes is H(2)O(2)-oxidation and hot water aging. Based on the photoactivated bactericidal properties of TiO(2), this study was aimed at optimizing the treatment to achieve high photocatalytic activity. Ti-6Al-4V samples were H(2)O(2)-oxidized and hot water aged for up to 24 and 72 h, respectively. Degradation measurements of rhodamine B during UV-A illumination of samples showed a near linear relationship between photocatalytic activity and total treatment time, and a nanoporous coating was observed by scanning electron microscopy. Grazing incidence X-ray diffraction showed a gradual decrease in crystallinity of the surface layer, suggesting that the increase in surface area rather than anatase formation was responsible for the increase in photocatalytic activity.

Origin of biotite-hornblende-garnet coronas between oxides and plagioclase in olivine metagabbros, Adirondack region, New York

USGS Publications Warehouse

Whitney, P.R.; McLelland, J.M.

1982-01-01

Complex multivariant reactions involving Fe-Ti oxide minerals, plagioclase and olivine have produced coronas of biotite, hornblende and garnet between ilmenite and plagioclase in Adirondack olivine metagabbros. Both the biotite (6-10% TiO2) and the hornblende (3-6% TiO2) are exceptionally Titanium-rich. The garnet is nearly identical in composition to the garnet in coronas around olivine in the same rocks. The coronas form in two stages: (a) Plagioclase+Fe-Ti Oxides+Olivine+water =Hornblende+Spinel+Orthopyroxene??Biotite +more-sodic Plagioclase (b) Hornblende+Orthopyroxene??Spinel+Plagioclase =Garnet+Clinopyroxene+more-sodic Plagioclase The Orthopyroxene and part of the clinopyroxene form adjacent to olivine. Both reactions are linked by exchange of Mg2+ and Fe2+ with the reactions forming pyroxene and garnet coronas around olivine in the same rocks. The reactions occur under granulite fades metamorphic conditions, either during isobaric cooling or with increasing pressure at high temperature. ?? 1983 Springer-Verlag.

Observation of a two-dimensional liquid of Fröhlich polarons at the bare SrTiO3 surface

PubMed Central

Chen, Chaoyu; Avila, José; Frantzeskakis, Emmanouil; Levy, Anna; Asensio, Maria C.

2015-01-01

The polaron is a quasi-particle formed by a conduction electron (or hole) together with its self-induced polarization in a polar semiconductor or an ionic crystal. Among various polarizable examples of complex oxides, strontium titanate (SrTiO3) is one of the most studied. Here we examine the carrier type and the interplay of inner degrees of freedom (for example, charge, lattice, orbital) in SrTiO3. We report the experimental observation of Fröhlich polarons, or large polarons, at the bare SrTiO3 surface prepared by vacuum annealing. Systematic analyses of angle-resolved photoemission spectroscopy and X-ray absorption spectra show that these Fröhlich polarons are two-dimensional and only exist with inversion symmetry breaking by two-dimensional oxygen vacancies. Our discovery provides a rare solvable field theoretical model, and suggests the relevance of large (bi)polarons for superconductivity in perovskite oxides, as well as in high-temperature superconductors. PMID:26489376

Transport Properties of La- doped SrTiO3 Ceramics Prepared Using Spark Plasma Sintering

NASA Astrophysics Data System (ADS)

Mehdizadeh Dehkordi, Arash; Bhattacharya, Sriparna; Tritt, Terry M.; Alshareef, Husam N.

2012-02-01

In this work, thermoelectric transport properties of La-doped SrTiO3 ceramics prepared using conventional solid state reaction and spark plasma sintering have been investigated. Room temperature power factor of single crystal strontium titanate (SrTiO3), comparable to that of Bi2Te3, has brought new attention to this perovskite-type transition metal-oxide as a potential n-type thermoelectric for high temperature applications. Electronic properties of this model complex oxide, SrTiO3 (ABO3), can be tuned in a wide range through different doping mechanisms. In addition to A site (La-doped) or B site (Nb-doped) substitutional doping, introducing oxygen vacancies plays an important role in electrical and thermal properties of these structures. Having multiple doping mechanisms makes the transport properties of these perovskites more dependent on preparation parameters. The effect of these synthesis parameters and consolidation conditions on the transport properties of these materials has been studied.

Structural crossover from nonmodulated to long-period modulated tetragonal phase and anomalous change in ferroelectric properties in the lead-free piezoelectric N a1 /2B i1 /2Ti O3-BaTi O3

NASA Astrophysics Data System (ADS)

Rao, Badari Narayana; Khatua, Dipak Kumar; Garg, Rohini; Senyshyn, Anatoliy; Ranjan, Rajeev

2015-06-01

The highly complex structure-property interrelationship in the lead-free piezoelectric (x )N a1 /2B i1 /2Ti O3- (1 -x ) BaTi O3 is a subject of considerable contemporary debate. Using comprehensive x-ray, neutron diffraction, dielectric, and ferroelectric studies, we have shown the existence of a new criticality in this system at x =0.80 , i.e., well within the conventional tetragonal phase field. This criticality manifests as a nonmonotonic variation of the tetragonality and coercivity and is shown to be associated with a crossover from a nonmodulated tetragonal phase (for x <0.8 ) to a long-period modulated tetragonal phase (for x >0.80 ). It is shown that the stabilization of long-period modulation introduces a characteristic depolarization temperature in the system. While differing qualitatively from the two-phase model often suggested for the critical compositions of this system, our results support the view with regard to the tendency in perovskites to stabilize long-period modulated structures as a result of complex interplay of antiferrodistortive modes [Bellaiche and Iniguez, Phys. Rev. B 88, 014104 (2013), 10.1103/PhysRevB.88.014104; Prosandeev, Wang, Ren, Iniguez, ands Bellaiche, Adv. Funct. Mater. 23, 234 (2013), 10.1002/adfm.201201467].

Suppressed carrier density for the patterned high mobility two-dimensional electron gas at γ-Al2O3/SrTiO3 heterointerfaces

NASA Astrophysics Data System (ADS)

Niu, Wei; Gan, Yulin; Zhang, Yu; Valbjørn Christensen, Dennis; von Soosten, Merlin; Wang, Xuefeng; Xu, Yongbing; Zhang, Rong; Pryds, Nini; Chen, Yunzhong

2017-07-01

The two-dimensional electron gas (2DEG) at the non-isostructural interface between spinel γ-Al2O3 and perovskite SrTiO3 is featured by a record electron mobility among complex oxide interfaces in addition to a high carrier density up to the order of 1015 cm-2. Herein, we report on the patterning of 2DEG at the γ-Al2O3/SrTiO3 interface grown at 650 °C by pulsed laser deposition using a hard mask of LaMnO3. The patterned 2DEG exhibits a critical thickness of 2 unit cells of γ-Al2O3 for the occurrence of interface conductivity, similar to the unpatterned sample. However, its maximum carrier density is found to be approximately 3 × 1013 cm-2, much lower than that of the unpatterned sample (˜1015 cm-2). Remarkably, a high electron mobility of approximately 3600 cm2 V-1 s-1 was obtained at low temperatures for the patterned 2DEG at a carrier density of ˜7 × 1012 cm-2, which exhibits clear Shubnikov-de Haas quantum oscillations. The patterned high-mobility 2DEG at the γ-Al2O3/SrTiO3 interface paves the way for the design and application of spinel/perovskite interfaces for high-mobility all-oxide electronic devices.

Milestone Report - M4FT-15OR03120218 - A Literature Search on the Effects of the Decay of 85Kr to 85Rb on Long-term Storage Options

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruffey, Stephanie H.; Strachan, Denis M.; Jubin, Robert Thomas

2015-10-01

Reprocessing of UNF that has been out of the reactor for less than about 50 y requires the removal of 85Kr from the process off-gas streams. This is needed despite the relatively small amount of that isotope in the combined Xe and Kr inventory (Table 1). The decay of 85Kr to 85Rb presents challenges to the materials that will potentially be used to remove and store the Kr recovered from the off-gas. To address some of these problems, a thorough literature survey was completed, and the results of that analysis are summarized in this document.

Effect of pressure of helium, argon, krypton, and xenon on the porosity, microstructure, and mechanical properties of commercially pure titanium castings.

PubMed

Zinelis, S

2000-11-01

Porosity is a frequently observed casting defect in dental titanium alloys. This study evaluated the effect of pressure of helium, argon, krypton, and xenon on the porosity, microstructure, and mechanical properties of commercially pure titanium (cp Ti) castings. Eight groups (A-H) of 16 rectangular wax patterns each (30 mm in length, 3 mm in width, and 1 mm in depth) were prepared. The wax patterns were invested with a magnesia-based material and cast with cp Ti (grade II). Groups A, C, E, and G were cast under a pressure of 1 atm, and groups B, D, F, and H were cast under a pressure of 0.5 atm of He, Ar, Kr, and Xe, respectively. The extent of the porosity of the cast specimens was determined radiographically and quantified by image analysis. Three specimens of each group and 3 cylinders of the as-received cp Ti used as a reference were embedded in resin and studied metallographically after grinding, polishing, and chemical etching. These surfaces were used for determination of the Vickers hardness (VHN) as well. Eight specimens from each group were fractured in the tensile mode, and the 0.2% yield strength, fracture stress, and percentage elongation were calculated. Porosity was analyzed with 2-way ANOVA and the Newman-Keuls multiple range test. VHN measurements and tensile properties for specimen groups were compared with 1-way ANOVA and the Newman-Keuls multiple range test (95% significance level). The porosity levels per group were (%): A = 5.50 +/- 4.34, B = 0.77 +/- 1.27, C = 2.44 +/- 3.68, D = 0.06 +/- 0.12, E-H = 0. Two-way ANOVA showed that there was no detectable interaction (P<.05) between gas type and applied pressure. Metallographic examination revealed no differences in microstructure among the groups studied. A finer grain size was observed in all cast groups compared with the original cp Ti. The VHN of the as-received cp Ti was significantly greater than all the cast groups tested. Groups cast under He showed the highest VHN, yield strength, and fracture stress. No significant differences were found in percentage elongation values among the groups. Porosity and mechanical properties of cp Ti castings are dependent on the gas type and pressure, whereas the microstructure remains unaffected.

Thermoelectric properties of in-situ plasma spray synthesized sub-stoichiometry TiO 2-x

DOE PAGES

Lee, Hwasoo; Han, Su Jung; Seshadri, Ramachandran Chidambaram; ...

2016-11-04

The thermoelectric properties of sub-stoichiometric TiO 2-x deposits produced by cascaded-plasma spray process are investigated from room-temperature to 750 K. Sub-stoichiometric TiO 2-x deposits are formed through in-situ reaction of the TiO 1.9 within the high temperature plasma flame and manipulated through introduction of varying amounts of hydrogen in the plasma. Although the TiO 2-x particles experience reduction within plasma, it can also re-oxidize through interaction with the surrounding ambient atmosphere, resulting in a complex interplay between process conditions and stoichiometry. The deposits predominantly contain rutile phase with presence of Magneli phases especially under significantly reducing plasma conditions. The resultantmore » deposits show sensitivity to thermoelectric properties and under certain optimal conditions repeatedly show Seebeck coefficients reaching values of -230 μV K -1 at temperatures of 750 K while providing an electrical conductivity of 5.48 × 10 3 S m -1, relatively low thermal conductivity in the range of 1.5 to 2 W m -1 K -1 resulting in power factor of 2.9 μW cm -1 K -2. The resultant maximum thermoelectric figure of merit value reached 0.132 under these optimal conditions. Lastly, the results point to a potential pathway for a large-scale fabrication of low-cost oxide based thermoelectric with potential applicability at moderate to high temperatures.« less

Thermoelectric properties of in-situ plasma spray synthesized sub-stoichiometry TiO 2-x

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Hwasoo; Han, Su Jung; Seshadri, Ramachandran Chidambaram

The thermoelectric properties of sub-stoichiometric TiO 2-x deposits produced by cascaded-plasma spray process are investigated from room-temperature to 750 K. Sub-stoichiometric TiO 2-x deposits are formed through in-situ reaction of the TiO 1.9 within the high temperature plasma flame and manipulated through introduction of varying amounts of hydrogen in the plasma. Although the TiO 2-x particles experience reduction within plasma, it can also re-oxidize through interaction with the surrounding ambient atmosphere, resulting in a complex interplay between process conditions and stoichiometry. The deposits predominantly contain rutile phase with presence of Magneli phases especially under significantly reducing plasma conditions. The resultantmore » deposits show sensitivity to thermoelectric properties and under certain optimal conditions repeatedly show Seebeck coefficients reaching values of -230 μV K -1 at temperatures of 750 K while providing an electrical conductivity of 5.48 × 10 3 S m -1, relatively low thermal conductivity in the range of 1.5 to 2 W m -1 K -1 resulting in power factor of 2.9 μW cm -1 K -2. The resultant maximum thermoelectric figure of merit value reached 0.132 under these optimal conditions. Lastly, the results point to a potential pathway for a large-scale fabrication of low-cost oxide based thermoelectric with potential applicability at moderate to high temperatures.« less

Monte Carlo simulations of ionization potential depression in dense plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stransky, M., E-mail: stransky@fzu.cz

A particle-particle grand canonical Monte Carlo model with Coulomb pair potential interaction was used to simulate modification of ionization potentials by electrostatic microfields. The Barnes-Hut tree algorithm [J. Barnes and P. Hut, Nature 324, 446 (1986)] was used to speed up calculations of electric potential. Atomic levels were approximated to be independent of the microfields as was assumed in the original paper by Ecker and Kröll [Phys. Fluids 6, 62 (1963)]; however, the available levels were limited by the corresponding mean inter-particle distance. The code was tested on hydrogen and dense aluminum plasmas. The amount of depression was up tomore » 50% higher in the Debye-Hückel regime for hydrogen plasmas, in the high density limit, reasonable agreement was found with the Ecker-Kröll model for hydrogen plasmas and with the Stewart-Pyatt model [J. Stewart and K. Pyatt, Jr., Astrophys. J. 144, 1203 (1966)] for aluminum plasmas. Our 3D code is an improvement over the spherically symmetric simplifications of the Ecker-Kröll and Stewart-Pyatt models and is also not limited to high atomic numbers as is the underlying Thomas-Fermi model used in the Stewart-Pyatt model.« less

Structural, thermal and electrical conductivity characteristics of Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln: La, Nd and Sm) complex perovskites as anode materials for solid oxide fuel cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jeong, Jihoon; Department of Mechanical Engineering, The University of Texas at Austin, Austin, TX 78712; Azad, Abul K.

2015-03-15

The Ti and Mn replaced complex perovskites, Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln: La, Nd and Sm), were reported as potential anode materials for high temperature-operating solid oxide fuel cells (HT-SOFCs). For the present research study, synthesis, crystallographic, thermal and electrical conductivity properties of Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} complex perovskites were investigated using X-ray diffraction (XRD), Rietveld method, thermogravimetric analysis (TGA) and electrical conductivity to apply these oxide materials for the HT-SOFC anode materials. XRD results showed that Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} oxide systems synthesized as single phases did not react with 8 mol% yttriamore » stabilized zirconia (8YSZ) and 10 mol% Gd-doped cerium oxide (CGO91) up to 1500 °C and did not decompose under dry 3.9% hydrogen at 850 °C. The crystal structures of La{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (LSTM), Nd{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (NSTM) and Sm{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (SSTM) showed orthorhombic symmetry with the space group Pbnm and SSTM showed a more distorted structure. Thermogravimetric analysis (TGA) proved weight gains in these three sample occurred under oxidizing conditions and weight loss under reducing conditions. Electrical conductivity values of NSTM were higher than those of LSTM and SSTM under oxidizing and reducing conditions. - Graphical abstract: The B-site cations (Ti/Mn) are surrounded by regular octahedra of oxygen in Nd{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d}(NSTM). These octahedra are linked together in a corner sharing three dimensional framework, while Nd/Sr ion occupies 12-coordinated A-site between these octahedra. The Ti/Mn–O{sub 6} octahedra are elongated along the c-axis. The crystal structure distortion was due to the smaller ionic radius of the A-site cations, which force the (Ti/Mn)–O{sub 6} octahedra to tilt in order to optimize the A–O bond distances. The same structural symmetry was found when the samples were reduced in 3.9% H{sub 2} in Ar at 900 °C for 12 h. - Highlights: • Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} oxide systems do not react with 8YSZ and CGO91. • LSTM, NSTM and SSTM show orthorhombic symmetry with the space group Pbnm. • LSTM shows relatively lower onset temperature in Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d}. • Electrical conductivity values of NSTM are higher than those of LSTM and SSTM.« less

Krypton-xenon separation properties of SAPO-34 zeolite materials and membranes

DOE PAGES

Hye Kwon, Yeon; Kiang, Christine; Benjamin, Emily; ...

2016-07-27

Separation of the radioisotope 85Kr from 136Xe is an important target during used nuclear fuel recycling. In this paper, we report a detailed study on the Kr and Xe adsorption, diffusion, and membrane permeation properties of the silicoaluminophosphate zeolite SAPO-34. Adsorption and diffusion measurements on SAPO-34 crystals indicate their potential for use in Kr-Xe separation membranes, but also highlight competing effects of adsorption and diffusion selectivity. SAPO-34 membranes are synthesized on α$-$alumina disk and tubular substrates via steam assisted conversion seeding and hydrothermal growth, and are characterized in detail. Membrane transport measurements reveal that SAPO-34 membranes can separate Kr frommore » Xe by molecular sieving, with Kr permeabilities around 50 Barrer and mixture selectivity of 25–30 for Kr at ambient or slight sub-ambient conditions. Finally, the membrane transport characteristics are modeled by the Maxwell-Stefan equations, whose predictions are in very good agreement with experiment and confirm the minimal competing effects of adsorption and diffusion.« less

Energy transfer of highly vibrationally excited biphenyl.

PubMed

Hsu, Hsu Chen; Dyakov, Yuri; Ni, Chi-Kung

2010-11-07

The energy transfer between Kr atoms and highly vibrationally excited, rotationally cold biphenyl in the triplet state was investigated using crossed-beam/time-of-flight mass spectrometer/time-sliced velocity map ion imaging techniques. Compared to the energy transfer of naphthalene, energy transfer of biphenyl shows more forward scattering, less complex formation, larger cross section for vibrational to translational (V→T) energy transfer, smaller cross section for translational to vibrational and rotational (T→VR) energy transfer, larger total collisional cross section, and more energy transferred from vibration to translation. Significant increase in the large V→T energy transfer probabilities, termed supercollisions, was observed. The difference in the energy transfer of highly vibrationally excited molecules between rotationally cold naphthalene and rotationally cold biphenyl is very similar to the difference in the energy transfer of highly vibrationally excited molecules between rotationally cold naphthalene and rotationally hot naphthalene. The low-frequency vibrational modes with out-of-plane motion and rotationlike wide-angle motion are attributed to make the energy transfer of biphenyl different from that of naphthalene.

Spectroscopic study of the charge-transfer complexes TiCl4/styrene and TiCl4/polystyrene

NASA Astrophysics Data System (ADS)

Gonçalves, Norberto S.; Noda, Lúcia. K.

2017-10-01

In this work, solutions of TiCl4/styrene and TiCl4/polystyrene charge-transfer complexes in CHCl3 or CDCl3 were investigated by UV-vis, resonance Raman and 1H NMR spectroscopies in order to study their molecular and electronic structures. Both show a yellow colour due to absorption in the 400 nm region, related to a charge-transfer transition. In Raman spectra, as the excitation approaches the resonance region, the primary enhancement of aromatic ring modes was mainly observed, rather than intensification of the vinylic double-bond stretch. Under the experimental conditions it was observed that formation of polystyrene takes place, as showed by 1H NMR spectra, and the most significant interaction occurs at the aromatic ring, as supported by the results from interaction of TiCl4 with polystyrene, as indicated by the charge-transfer band and resonant intensification of the aromatic ring modes.

Tailoring Selective Laser Melting Process Parameters for NiTi Implants

NASA Astrophysics Data System (ADS)

Bormann, Therese; Schumacher, Ralf; Müller, Bert; Mertmann, Matthias; de Wild, Michael

2012-12-01

Complex-shaped NiTi constructions become more and more essential for biomedical applications especially for dental or cranio-maxillofacial implants. The additive manufacturing method of selective laser melting allows realizing complex-shaped elements with predefined porosity and three-dimensional micro-architecture directly out of the design data. We demonstrate that the intentional modification of the applied energy during the SLM-process allows tailoring the transformation temperatures of NiTi entities within the entire construction. Differential scanning calorimetry, x-ray diffraction, and metallographic analysis were employed for the thermal and structural characterizations. In particular, the phase transformation temperatures, the related crystallographic phases, and the formed microstructures of SLM constructions were determined for a series of SLM-processing parameters. The SLM-NiTi exhibits pseudoelastic behavior. In this manner, the properties of NiTi implants can be tailored to build smart implants with pre-defined micro-architecture and advanced performance.

Pt deposited TiO2 catalyst fabricated by thermal decomposition of titanium complex for solar hydrogen production

NASA Astrophysics Data System (ADS)

Truong, Quang Duc; Le, Thanh Son; Ling, Yong-Chien

2014-12-01

C, N codoped TiO2 catalyst has been synthesized by thermal decomposition of a novel water-soluble titanium complex. The structure, morphology, and optical properties of the synthesized TiO2 catalyst were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and UV-vis diffuse reflectance spectroscopy. The photocatalytic activity of the Pt deposited TiO2 catalysts synthesized at different temperatures was evaluated by means of hydrogen evolution reaction under both UV-vis and visible light irradiation. The investigation results reveal that the photocatalytic H2 evolution rate strongly depended on the crystalline grain size as well as specific surface area of the synthesized catalyst. Our studies successfully demonstrate a simple method for the synthesis of visible-light responsive Pt deposited TiO2 catalyst for solar hydrogen production.

Functionally graded Ti6Al4V and Inconel 625 by Laser Metal Deposition

NASA Astrophysics Data System (ADS)

Pulugurtha, Syamala R.

The objective of the current work was to fabricate a crack-free functionally graded Ti6Al4V and Inconel 625 thin wall structure by Laser Metal Deposition (LMD). One potential application for the current material system is the ability to fabricate a functionally graded alloy that can be used in a space heat exchanger. The two alloys, Inconel 625 and Ti6Al4V are currently used for aerospace applications. They were chosen as candidates for grading because functionally grading those combines the properties of high strength/weight ratio of Ti6Al4V and high temperature oxidation resistance of Inconel 625 into one multifunctional material for the end application. However, there were challenges associated with the presence of Ni-Ti intermetallic phases (IMPs). The study focused on several critical areas such as (1) understanding microstructural evolution, (2) reducing macroscopic cracking, and (3) reducing mixing between graded layers. Finite element analysis (FEA) was performed to understand the effect of process conditions on multilayer claddings for simplified material systems such as SS316L and Inconel 625 where complex microstructures did not form. The thermo-mechanical models were developed using Abaqus(TM) (and some of them experimentally verified) to predict temperature-gradients; remelt layer depths and residual stresses. Microstructure evolution along the functionally graded Ti6Al4V and Inconel 625 was studied under different processing and grading conditions. Thermodynamic modeling using Factsage (v 6.1) was used to construct phase diagrams and predict the possible equilibrium major/minor phases (verified experimentally by XRD) that may be present along the functionally graded Ti6Al4V and Inconel 625 thin wall structures.

Anode catalysts for direct ethanol fuel cells utilizing directly solar light illumination.

PubMed

Chu, Daobao; Wang, Shuxi; Zheng, Peng; Wang, Jian; Zha, Longwu; Hou, Yuanyuan; He, Jianguo; Xiao, Ying; Lin, Huashui; Tian, Zhaowu

2009-01-01

Shine a light: A PtNiRu/TiO(2) anode catalyst for direct ethanol fuel cells shows photocatalytic activity. The peak current density for ethanol oxidation under solar light illumination is 2-3 times greater than that in the absence of solar light. Ethanol is oxidized by light-generated holes, and the electrons are collected by the TiO(2) support to generate the oxidation current.Novel PtNiRu/TiO(2) anode catalysts for direct ethanol fuel cells (DEFCs) were prepared from PtNiRu nanoparticles (1:1:1 atomic ratios) and a nanoporous TiO(2) film by a sol-gel and electrodeposition method. The performances of the catalysts for ethanol oxidation were investigated by cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. The results indicate a remarkable enhancement of activity for ethanol oxidation under solar light illumination. Under solar light illumination, the generated oxidation peak current density is 24.6 mA cm(-2), which is about 2.5 times higher than that observed without solar light (9.9 mA cm(-2)). The high catalytic activity of the PtNiRu/TiO(2) complex catalyst for the electrooxidation of ethanol may be attributed to the modified metal/nanoporous TiO(2) film, and the enhanced electrooxidation of ethanol under solar light may be due to the photogeneration of holes in the modified nanoporous TiO(2) film.

Quiet-Time Spectra and Abundances of Energetic Particles During the 1996 Solar Minimum

NASA Technical Reports Server (NTRS)

Reames, Donald V.

1999-01-01

We report the energy spectra and abundances of ions with atomic number, Z, in the interval Z is greater than or equal to 2 and Z is less than or equal to 36 and energies approximately 3-20 MeV/amu for solar and interplanetary quiet periods between 1994 November and 1998 April as measured by the large-geometry Low Energy Matrix Telescope (LEMT) telescope on the Wind spacecraft near Earth. The energy spectra show the presence of galactic (GCR) and "anomalous" cosmic ray (ACR) components, depending on the element. ACR components are reported for Mg and Si for the first time at 1 AU and the previous observation of S and Ar is confirmed. However, only GCR components are clearly apparent for the elements Ca, Ti, Cr, Fe, as well as for C. New limits are placed on a possible ACR contribution for other elements, including Kr.

Quiet-Time Spectra and Abundances of Energetic Particles During the 1996 Solar Minimum

NASA Technical Reports Server (NTRS)

Reames, Donald V.

1998-01-01

This report concerns the energy spectra and abundances of ions with atomic number, Z, in the interval 2 greater than or equal to Z and Z less than or equal to 36 and energies approximately 3-20 MeV/amu for solar and interplanetary quiet periods between November 1994 and April 1998 as measured by the large-geometry LEMT telescope on the Wind spacecraft near Earth. The energy spectra show the presence of galactic (GCR) and 'anomalous' cosmic ray (ACR) components, depending on the element. ACR components are reported for Mg and Si for the first time at 1 AU and the previous observation of S and Ar is confirmed. However, only GCR components are clearly apparent for the elements Ca, Ti, Cr, Fe, as well as for C. New limits are placed on a possible ACR contribution for other elements, including Kr.

Unprecedented H-atom transfer from water to ketyl radicals mediated by Cp(2)TiCl.

PubMed

Paradas, Miguel; Campaña, Araceli G; Marcos, Maria Luisa; Justicia, Jose; Haidour, Ali; Robles, Rafael; Cárdenas, Diego J; Oltra, J Enrique; Cuerva, Juan M

2010-10-07

The H-atom transfer (HAT) from water to ketyl radicals, mediated by titanocene(iii) aqua-complexes, can explain the Ti(III)-promoted reduction of ketones in aqueous medium better than the conventional House mechanism. Moreover, we also report novel evidences supporting the existence of these titanocene(iii) aqua-complexes.

Modulation-Doped SrTiO3/SrTi1-xZrxO3 Heterostructures

NASA Astrophysics Data System (ADS)

Kajdos, Adam Paul

Two-dimensional electron gases (2DEGs) in SrTiO3 have attracted considerable attention for exhibiting a variety of interesting physical phenomena, such as superconductivity and magnetism. So far, most of the literature has focused on interfaces between nonpolar SrTiO3 and polar perovskite oxides (e.g. LaAlO3 or rare-earth titanates), where high carrier density 2DEGs (˜3 x 1014 cm-2) are generated by polar discontinuity. Modulation doping is an alternative approach to generating a 2DEG that has been explored extensively in III-V semiconductors but has not heretofore been explored in complex oxides. This approach involves interfacing an undoped semiconductor with a doped semiconductor whose conduction band edge lies at a higher energy, which results in electrons diffusing into the undoped semiconductor transport channel, where scattering from ionized dopants is minimized. Realizing a high-mobility modulation-doped structure with a SrTiO3 transport channel therefore requires both the optimization of the transport channel by minimizing native defects as well as the development of a perovskite oxide which has a suitable band offset with SrTiO3 and can be electron-doped. The growth of high electron mobility SrTiO3 as a suitable transport channel material was previously demonstrated using the hybrid molecular beam epitaxy (MBE) approach, where Sr is delivered via a solid source and Ti is delivered using a metal-organic precursor, titanium (IV) tetra-isopropoxide (TTIP). Expanding on this, in-situ reflection high-energy electron diffraction (RHEED) is used to track the surface and resulting film cation stoichiometry of homoepitaxial SrTiO3 (001) thin films grown by hybrid MBE. It is shown that films with lattice parameters identical to bulk single-crystal substrates within the detection limit of high-resolution X-ray diffraction (XRD) measurements exhibit an evolution in surface reconstruction with increasing TTIP beam-equivalent pressure. The change in the observed surface reconstruction from (1x1) to (2x1) to c(4x4) is correlated with a change from mixed SrO/TiO2 to pure TiO2 surface termination. It is argued that optimal cation stoichiometry is achieved for growth conditions within the XRD-defined growth window that result in a c(4x4) surface lattice. The development of a doped perovskite oxide semiconductor with a suitable conduction band offset is then discussed as the next necessary step towards realizing modulation-doped heterostructures. The SrTixZr1-x O3 solid solution is investigated for this purpose, with a focus on optimizing cation stoichiometry to allow for controlled doping. In particular, the hybrid MBE growth of SrTixZr1-xO3 thin films is explored using a metal-organic precursor for Zr, zirconium tert-butoxide (ZTB). The successful generation of 2DEGs by modulation doping of SrTiO3 is then demonstrated in SrTiO3/La:SrTi0.95Zr0.05O 3 heterostructures, and the electronic structure is studied by Shubnikov-de Haas analysis using multiple-subband models.

Probing the N˜Z line via β decay

NASA Astrophysics Data System (ADS)

Oinonen, Markku

1999-11-01

This contribution reports several beta-decay studies performed at ISOLDE On-line Mass Separator at CERN recently for nuclei close to N=Z line. Beta decay of 58Zn provides a possibility to compare Gamow-Teller strength extracted from complementary beta-decay studies and charge-exchange reactions. Measurement on beta-decay half-life of 70Kr shows importance of experimental information in modelling the path of the astrophysical rp process. Decay of 71Kr is an example of a mirror beta decay and extends the systematics of these particular decays towards highly deformed region close to A=80.

Pyrrole-regulated precipitation of titania nanorods on polymer fabrics for photocatalytic degradation of trace toluene in air

NASA Astrophysics Data System (ADS)

Gu, Yi-Jie; Wen, Wei; Xu, Yang; Wu, Jin-Ming

2018-03-01

When compared with nanoparticulate counterparts, TiO2 thin films with vertically aligned one-dimensional (1D) nanostructures exhibit enhanced photocatalytic activity because of the highly accessible surface area. The perpendicular of the 1D nanostructure reduces the charge migration path and hence the carrier recombination rate, which also contributes to the photocatalytic activity. Furthermore, TiO2 thin films on flexible substrates are more suitable to degrade pollutants in either water or air because of its easy recovery and free-bending shape. In this study, flexible polyethylene fabrics were firstly coated with a sol-gel nanoparticulate TiO2 seed layer. Quasi-aligned TiO2 nanorods were then precipitated homogeneously under an atmospheric pressure and a low temperature not exceeding 80 °C, using a peroxy-titanium complex precursor with the additive of pyrrole. It is found that the density of TiO2 nanorods increased with the increasing amount of pyrrole monomers. The resultant TiO2 film on polyethylene fabrics exhibited a much reduced band gap of ca. 2.86 eV, which can be attributed to the surface oxygen deficiencies. When utilized to assist photocatalytic degradation of trace toluene in air under the UV light illumination, the TiO2 film exhibited a gradually increased photocatalytic activity upon the increasing cycles for up to six, because of the gradual removal of trace organics on the TiO2 surface. The highest photocatalytic efficiency is recorded to be 5 times that of TiO2 nanotube arrays, which are regarded as an excellent photocatalyst for air cleaning.