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Sample records for zintl phase precursors

  1. A Versatile Low Temperature Synthetic Route to Zintl Phase Precursors: Na4Si4, Na4Ge4 and K4Ge4 as Examples

    PubMed Central

    Ma, Xuchu; Xu, Fen; Atkins, Tonya; Goforth, Andrea M.; Neiner, Doinita; Navrotsky, Alexandra; Kauzlarich, Susan M.

    2010-01-01

    Na4Si4 and Na4Ge4 are ideal chemical precursors for inorganic clathrate structures, clusters, and nanocrystals. The monoclinic Zintl phases, Na4Si4 and Na4Ge4, contain isolated homo-tetrahedranide [Si4]4− and [Ge4]4− clusters surrounded by alkali metal cations. In this study, a simple scalable route has been applied to prepare Zintl phases of composition Na4Si4 and Na4Ge4 using the reaction between NaH and Si or Ge at low temperature (420 °C for Na4Si4 and 270 °C for Na4Ge4). The method was also applied to K4Ge4, using KH and Ge as raw materials, to show the versatility of this approach. The influence of specific reaction conditions on the purity of these Zintl phases has been studied by controlling five factors: the method of reagent mixing (manual or ball milled), the stoichiometry between raw materials, the reaction temperature, the heating time and the gas flow rate. Moderate ball-milling and excess NaH or KH facilitate the formation of pure Na4Si4, Na4Ge4 or K4Ge4 at 420 °C (Na4Si4) or 270 °C (both M4Ge4 compounds, M = Na, K). TG/DSC analysis of the reaction of NaH and Ge indicates that ball milling reduces the temperature for reaction and confirms the formation temperature. This method provides large quantities of high quality Na4Si4 and Na4Ge4 without the need for specialized laboratory equipment, such as Schlenk lines, niobium/tantalum containers, or an arc welder, thereby expanding the accessibility and chemical utility of these phases by making them more convenient to prepare. This new synthetic method may also be extended to lithium-containing Zintl phases (LiH is commercially available) as well as to alkali metal-tetrel Zintl compounds of other compositions, e.g. K4Ge9. PMID:19921060

  2. Zintl Phases for Thermoelectric Applications

    NASA Technical Reports Server (NTRS)

    Snyder, G. Jeffrey (Inventor); Toberer, Eric (Inventor); Zevalkink, Alex (Inventor)

    2014-01-01

    The inventors demonstrate herein that various Zintl compounds can be useful as thermoelectric materials for a variety of applications. Specifically, the utility of Ca3AlSb3, Ca5Al2Sb6, Ca5In2Sb6, Ca5Ga2Sb6, is described herein. Carrier concentration control via doping has also been demonstrated, resulting in considerably improved thermoelectric performance in the various systems described herein.

  3. Thermoelectric Properties of Complex Zintl Phases

    NASA Astrophysics Data System (ADS)

    Snyder, G. Jeffrey

    2008-03-01

    Complex Zintl phases make ideal thermoelectric materials because they can exhibit the necessary ``electron-crystal, phonon-glass'' properties required for high thermoelectric efficiency. Complex crystal structures can lead to high thermoelectric figure of merit (zT) by having extraordinarily low lattice thermal conductivity. A recent example is the discovery that Yb14MnSb11, a complex Zintl compound, has twice the zT as the SiGe based material currently in use at NASA. The high temperature (300K - 1300K) electronic properties of Yb14MnSb11 can be understood using models for heavily doped semiconductors. The free hole concentration, confirmed by Hall effect measurements, is set by the electron counting rules of Zintl and the valence of the transition metal (Mn^+2). Substitution of nonmagnetic Zn^+2 for the magnetic Mn^+2 reduces the spin-disorder scattering and leads to increased zT (10%). The reduction of spin-disorder scattering is consistent with the picture of Yb14MnSb11 as an underscreened Kondo lattice as derived from low temperature measurements. The hole concentration can be reduced by the substitution of Al^+3 for Mn^+2, which leads to an increase in the Seebeck coefficient and electrical resistivity consistent with models for degenerate semiconductors. This leads to further improvements (about 25%) in zT and a reduction in the temperature where the zT peaks. The peak in zT is due to the onset of minority carrier conduction and can be correlated with reduction in Seebeck coefficient, increase in electrical conductivity and increase in thermal conductivity due to bipolar thermal conduction.

  4. Hydrogenation properties of KSi and NaSi Zintl phases.

    PubMed

    Tang, Wan Si; Chotard, Jean-Noël; Raybaud, Pascal; Janot, Raphaël

    2012-10-14

    The recently reported KSi-KSiH(3) system can store 4.3 wt% of hydrogen reversibly with slow kinetics of several hours for complete absorption at 373 K and complete desorption at 473 K. From the kinetics measured at different temperatures, the Arrhenius plots give activation energies (E(a)) of 56.0 ± 5.7 kJ mol(-1) and 121 ± 17 kJ mol(-1) for the absorption and desorption processes, respectively. Ball-milling with 10 wt% of carbon strongly improves the kinetics of the system, i.e. specifically the initial rate of absorption becomes about one order of magnitude faster than that of pristine KSi. However, this fast absorption causes a disproportionation into KH and K(8)Si(46), instead of forming the KSiH(3) hydride from a slow absorption. This disproportionation, due to the formation of stable KH, leads to a total loss of reversibility. In a similar situation, when the pristine Zintl NaSi phase absorbs hydrogen, it likewise disproportionates into NaH and Na(8)Si(46), indicating a very poorly reversible reaction.

  5. Zintl Clusters as Wet-Chemical Precursors for Germanium Nanomorphologies with Tunable Composition.

    PubMed

    Bentlohner, Manuel M; Waibel, Markus; Zeller, Patrick; Sarkar, Kuhu; Müller-Buschbaum, Peter; Fattakhova-Rohlfing, Dina; Fässler, Thomas F

    2016-02-12

    [Ge9](4-) Zintl clusters are used as soluble germanium source for a bottom-up fabrication of Ge nanomorphologies such as inverse opal structures with tunable composition. The method is based on the assembly and oxidation of [Ge9 ](4-) clusters in a template mold using SiCl4 , GeCl4 , and PCl3 leading to Si and P-containing Ge phases as shown by X-ray diffraction, Raman spectroscopy, and energy-dispersive X-ray analysis. [Ge9](4-) clusters are retained using ethylenediamine (en) as a transfer medium to a mold after removal of the solvent if water is thoroughly excluded, but are oxidized to amorphous Ge in presence of water traces. (1)H NMR spectroscopy reveals the oxidative deprotonation of en by [Ge9](4-). Subsequent annealing leads to crystalline Ge. As an example for wet-chemical synthesis of complex Ge nanomorphologies, we describe the fabrication of undoped and P-doped inverse opal-structured Ge films with a rather low oxygen contents. The morphology of the films with regular volume porosity is characterized by SEM, TEM, and grazing incidence small-angle X-ray scattering. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Bonding in Some Zintl Phases: A Study by Tin-119 Mössbauer Spectroscopy

    NASA Astrophysics Data System (ADS)

    Asbrand, M.; Berry, F. J.; Eisenmann, B.; Kniep, R.; Smart, L. E.; Thied, R. C.

    1995-09-01

    The 119Sn Mössbauer parameters for a range of Zintl phase compounds are reported. The compounds containing tetrahedrally coordinated tin of composition M5SnX3 (M = Na, K; X = P, As, Sb) have chemical isomer shifts close to that of grey-tin and can be considered to be covalently bonded species. The layer structures of composition KSnX (X = As, Sb) and double-layer compounds M Sn2X2 (M = Na, Sr; X = As, Sb) have tin in a distorted octahedral environment. The chemical isomer shifts are closer to that of white-tin and can be interpreted in terms of metallic bonding.

  7. Hydrides of Alkaline Earth–Tetrel (AeTt) Zintl Phases: Covalent Tt–H Bonds from Silicon to Tin

    SciT

    Auer, Henry; Guehne, Robin; Bertmer, Marko

    Zintl phases form hydrides either by incorporating hydride anions (interstitial hydrides) or by covalent bonding of H to the polyanion (polyanionic hydrides), which yields a variety of different compositions and bonding situations. Hydrides (deuterides) of SrGe, BaSi, and BaSn were prepared by hydrogenation (deuteration) of the CrB-type Zintl phases AeTt and characterized by laboratory X-ray, synchrotron, and neutron diffraction, NMR spectroscopy, and quantum-chemical calculations. SrGeD4/3–x and BaSnD4/3–x show condensed boatlike six-membered rings of Tt atoms, formed by joining three of the zigzag chains contained in the Zintl phase. These new polyanionic motifs are terminated by covalently bound H atoms withmore » d(Ge–D) = 1.521(9) Å and d(Sn–D) = 1.858(8) Å. Additional hydride anions are located in Ae4 tetrahedra; thus, the features of both interstitial hydrides and polyanionic hydrides are represented. BaSiD2–x retains the zigzag Si chain as in the parent Zintl phase, but in the hydride (deuteride), it is terminated by H (D) atoms, thus forming a linear (SiD) chain with d(Si–D) = 1.641(5) Å.« less

  8. Structural and thermoelectric properties of zintl-phase CaLiPn (Pn=As, Sb, Bi)

    SciT

    Chandran, Anoop K.; Gudelli, Vijay Kumar; Sreeparvathy, P.C.

    First-principles calculations were carried out to study the structural, mechanical, dynamical and transport properties of zintl phase materials CaLiPn (Pn=As, Sb and Bi). We have used two different approaches to solve the system based on density functional theory. The plane wave pseudopotential approach has been used to study the structural and dynamical properties whereas, full potential linear augment plane wave method is used to examine the electronic structure, mechanical and thermoelectric properties. The calculated ground-state properties agree quite well with experimental values. The computed electronic structure shows the investigated compounds to be direct band gap semiconductors. Further, we have calculatedmore » the thermoelectric properties of all the investigated compounds for both the carriers at various temperatures. We found a high thermopower for both the carriers, especially n-type doping to be more favourable, which enabled us to predict that CaLiPn might have promising applications as a good thermoelectric material. Further, the phonon dispersion curves of the investigated compounds showed flat phonon modes and we also find lower optical and acoustic modes to cut each other at the lower frequency range, which further indicate the investigated compounds to possess reasonably low thermal conductivity. We have also analysed the low value of the thermal conductivity through the empirical relations and discussions are presented here. - Highlights: • Electronic band structure and chemical bonding. • Single crystalline elastic constants and poly crystalline elastic moduli. • Thermoelectric properties of zintl phase. • Lattice dynamics and phonon density of states.« less

  9. Higher thermoelectric performance of Zintl phases (Eu0.5Yb0.5)1-xCaxMg2Bi2 by band engineering and strain fluctuation.

    PubMed

    Shuai, Jing; Geng, Huiyuan; Lan, Yucheng; Zhu, Zhuan; Wang, Chao; Liu, Zihang; Bao, Jiming; Chu, Ching-Wu; Sui, Jiehe; Ren, Zhifeng

    2016-07-19

    Complex Zintl phases, especially antimony (Sb)-based YbZn0.4Cd1.6Sb2 with figure-of-merit (ZT) of ∼1.2 at 700 K, are good candidates as thermoelectric materials because of their intrinsic "electron-crystal, phonon-glass" nature. Here, we report the rarely studied p-type bismuth (Bi)-based Zintl phases (Ca,Yb,Eu)Mg2Bi2 with a record thermoelectric performance. Phase-pure EuMg2Bi2 is successfully prepared with suppressed bipolar effect to reach ZT ∼ 1. Further partial substitution of Eu by Ca and Yb enhanced ZT to ∼1.3 for Eu0.2Yb0.2Ca0.6Mg2Bi2 at 873 K. Density-functional theory (DFT) simulation indicates the alloying has no effect on the valence band, but does affect the conduction band. Such band engineering results in good p-type thermoelectric properties with high carrier mobility. Using transmission electron microscopy, various types of strains are observed and are believed to be due to atomic mass and size fluctuations. Point defects, strain, dislocations, and nanostructures jointly contribute to phonon scattering, confirmed by the semiclassical theoretical calculations based on a modified Debye-Callaway model of lattice thermal conductivity. This work indicates Bi-based (Ca,Yb,Eu)Mg2Bi2 is better than the Sb-based Zintl phases.

  10. Structural and thermoelectric properties of zintl-phase CaLiPn (Pn=As, Sb, Bi)

    NASA Astrophysics Data System (ADS)

    Chandran, Anoop K.; Gudelli, Vijay Kumar; Sreeparvathy, P. C.; Kanchana, V.

    2016-11-01

    First-principles calculations were carried out to study the structural, mechanical, dynamical and transport properties of zintl phase materials CaLiPn (Pn=As, Sb and Bi). We have used two different approaches to solve the system based on density functional theory. The plane wave pseudopotential approach has been used to study the structural and dynamical properties whereas, full potential linear augment plane wave method is used to examine the electronic structure, mechanical and thermoelectric properties. The calculated ground-state properties agree quite well with experimental values. The computed electronic structure shows the investigated compounds to be direct band gap semiconductors. Further, we have calculated the thermoelectric properties of all the investigated compounds for both the carriers at various temperatures. We found a high thermopower for both the carriers, especially n-type doping to be more favourable, which enabled us to predict that CaLiPn might have promising applications as a good thermoelectric material. Further, the phonon dispersion curves of the investigated compounds showed flat phonon modes and we also find lower optical and acoustic modes to cut each other at the lower frequency range, which further indicate the investigated compounds to possess reasonably low thermal conductivity. We have also analysed the low value of the thermal conductivity through the empirical relations and discussions are presented here.

  11. Synthesis and isolation of [Fe@Ge(10)](3-): a pentagonal prismatic Zintl ion cage encapsulating an interstitial iron atom.

    PubMed

    Zhou, Binbin; Denning, Mark S; Kays, Deborah L; Goicoechea, Jose M

    2009-03-04

    Reaction of an ethylenediamine (en) solution of the Zintl phase precursor K(4)Ge(9) with FeAr(2) (Ar = 2,6-Mes(2)C(6)H(3)) in the presence of 2,2,2-crypt (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) yielded the endohedral Zintl ion [Fe@Ge(10)](3-) (1) which was crystallographically characterized as a [K(2,2,2-crypt)](+) salt in [K(2,2,2-crypt)](3)[Fe@Ge(10)]*2en. This unprecedented Zintl ion exhibits a pentagonal prismatic 10-atom germanium cage with an interstitial iron atom in the central cavity. Confirmation of the existence of the cluster anion in solution was corroborated by positive and negative ion mode electrospray mass spectrometry.

  12. Pressure-induced structural transformations of the Zintl phase sodium silicide

    NASA Astrophysics Data System (ADS)

    Cabrera, Raúl Quesada; Salamat, Ashkan; Barkalov, Oleg I.; Leynaud, Olivier; Hutchins, Peter; Daisenberger, Dominik; Machon, Denis; Sella, Andrea; Lewis, Dewi W.; McMillan, Paul F.

    2009-09-01

    The high-pressure behaviour of NaSi has been studied using Raman spectroscopy and angle-dispersive synchrotron X-ray diffraction to observe the onset of structural phase transformations and potential oligomerisation into anionic Si nanoclusters with extended dimensionality. Our studies reveal a first structural transformation occurring at 8-10 GPa, followed by irreversible amorphisation above 15 GPa, suggesting the formation of Si-Si bonds with oxidation of the Si - species and reduction of Na + to metallic sodium. We have combined our experimental studies with DFT calculations to assist in the analysis of the structural behaviour of NaSi at high pressure.

  13. Pressure-induced structural transformations of the Zintl phase sodium silicide

    SciT

    Cabrera, Raul Quesada; Salamat, Ashkan; Barkalov, Oleg I.

    The high-pressure behaviour of NaSi has been studied using Raman spectroscopy and angle-dispersive synchrotron X-ray diffraction to observe the onset of structural phase transformations and potential oligomerisation into anionic Si nanoclusters with extended dimensionality. Our studies reveal a first structural transformation occurring at 8-10 GPa, followed by irreversible amorphisation above 15 GPa, suggesting the formation of Si-Si bonds with oxidation of the Si{sup -} species and reduction of Na{sup +} to metallic sodium. We have combined our experimental studies with DFT calculations to assist in the analysis of the structural behaviour of NaSi at high pressure. - Abstract: The high-pressuremore » behaviour of NaSi has been studied using Raman spectroscopy and angle-dispersive synchrotron X-ray diffraction. Our studies reveal a first structural transformation occurring at 8-10 GPa, followed by irreversible amorphisation, suggesting the formation of Si-Si bonds with oxidation of the Si{sup -} species and reduction of Na{sup +} to metallic sodium. We have combined our experimental studies with DFT calculations to assist in the analysis of the structural behaviour of NaSi at high pressure. Display Omitted« less

  14. The unusual chemical bonding and thermoelectric properties of a new type Zintl phase compounds Ba3Al2As4

    NASA Astrophysics Data System (ADS)

    Yang, Gui; Zhang, Guangbiao; Wang, Chao; Wang, Yuanxu

    2016-07-01

    Ba3Al2As4 exhibits an unusual anisotropic electrical conductivity, that is, the electrical conductivity along the chain is smaller than those along other two directions. The results is conflict with previous conclusion for Ca5M2Pn6. Earlier studies on Ca5M2Pn6 showed that a higher electrical conductivity could be obtained along the chain. The band decomposed charge density is used to explain such unusual behavior. Our calculations indicate the existence of a conductive pathway near the Fermi level is responsible for the electrons transport. Further, the Ba-As bonding of Ba3Al2As4 has some degree covalency which is novel for the Zintl compounds.

  15. Roles of cations, electronegativity difference, and anionic interlayer interactions in the metallic versus nonmetallic character of Zintl phases related to arsenic.

    PubMed

    Alemany, Pere; Llunell, Miquel; Canadell, Enric

    2008-10-01

    A first-principles Density Functional Theory study of several layered solids structurally related to rhombohedral arsenic has been carried out. The electronic structures of rhombohedral arsenic, CaSi(2), CaAl(2)Si(2), KSnSb, and SrSn(2)As(2) are discussed in detail, emphasizing on the origins of their metallic or nonmetallic behaviours. It is found that all of these systems are metallic except KSnSb. Electronegativity differences between the elements in the anionic sublattice and/or direct interlayer interactions play the main role in controlling the conductivity behavior. CaSi(2) exhibits a peculiar feature since the cation directly influences the conductivity but is not essential for its appearance. Cation-anion interactions are shown to have an important covalent contribution, but despite this fact and the metallic character found for most of these phases, the Zintl approach still provides a valid approximation to their electronic structure. (c) 2008 Wiley Periodicals, Inc.

  16. Structural, elastic, electronic, optical and thermoelectric properties of the Zintl-phase Ae3AlAs3 (Ae = Sr, Ba)

    NASA Astrophysics Data System (ADS)

    Benahmed, A.; Bouhemadou, A.; Alqarni, B.; Guechi, N.; Al-Douri, Y.; Khenata, R.; Bin-Omran, S.

    2018-05-01

    First-principles calculations were performed to investigate the structural, elastic, electronic, optical and thermoelectric properties of the Zintl-phase Ae3AlAs3 (Ae = Sr, Ba) using two complementary approaches based on density functional theory. The pseudopotential plane-wave method was used to explore the structural and elastic properties whereas the full-potential linearised augmented plane wave approach was used to study the structural, electronic, optical and thermoelectric properties. The calculated structural parameters are in good consistency with the corresponding measured ones. The single-crystal and polycrystalline elastic constants and related properties were examined in details. The electronic properties, including energy band dispersions, density of states and charge-carrier effective masses, were computed using Tran-Blaha modified Becke-Johnson functional for the exchange-correlation potential. It is found that both studied compounds are direct band gap semiconductors. Frequency-dependence of the linear optical functions were predicted for a wide photon energy range up to 15 eV. Charge carrier concentration and temperature dependences of the basic parameters of the thermoelectric properties were explored using the semi-classical Boltzmann transport model. Our calculations unveil that the studied compounds are characterised by a high thermopower for both carriers, especially the p-type conduction is more favourable.

  17. The new Zintl phases Eu{sub 21}Cd{sub 4}Sb{sub 18} and Eu{sub 21}Mn{sub 4}Sb{sub 18}

    SciT

    Wang, Yi; Darone, Gregory M.; Bobev, Svilen, E-mail: bobev@udel.edu

    Crystals of two new Zintl compounds, Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} have been synthesized using the molten metal flux method, and their structures have been established by single-crystal X-ray diffraction. Both compounds are isotypic and crystallize in the monoclinic space group C2/m (No. 12, Z=4). The structures are based on edge- and corner-shared MnSb{sub 4} or CdSb{sub 4} tetrahedra, which make octameric [Mn{sub 8}Sb{sub 22}] or [Cd{sub 8}Sb{sub 22}] polyanions. Homoatomic Sb–Sb bonds are present in both structures. The Eu atoms take the role of Eu{sup 2+}cations with seven unpaired 4f electrons, as suggested by themore » temperature-dependent magnetization measurements. The magnetic susceptibilities of Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} indicate that both phases order anti-ferromagnetically with Néel temperatures of ca. 7 K and ca. 10 K, respectively. The unpaired 3d electrons of the Mn atoms in Eu{sub 21}Mn{sub 4}Sb{sub 18} do contribute to the magnetic response, however, the bulk magnetization measurements do not provide evidence for long-range ordering of the Mn spins down to 5 K. Electrical resistivity measurements suggest that both compounds are narrow band gap semiconductors. - Graphical abstract: Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} have complex monoclinic structures, based on MnSb{sub 4} and CdSb{sub 4} tetrahedra, both edge- and corner-shared. A perspective of the crystal structure is shown, as viewed along the b axis. Display Omitted - Highlights: • Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} are novel compounds in the respective ternary phase diagrams. • For both structures, the Zintl-Klemm rules are followed, and both are small gap semiconductors. • Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} are air-stable Zintl phases and could be new thermoelectric materials.« less

  18. High efficiency thermoelectric power generation using Zintl-type materials

    NASA Technical Reports Server (NTRS)

    Brown, Shawna (Inventor); Snyder, G. Jeffrey (Inventor); Gascoin, Franck (Inventor); Kauzlarich, Susan (Inventor)

    2010-01-01

    The invention disclosed herein relates to thermoelectrically-active p-type Zintl phase materials as well as devices utilizing such compounds. Such thermoelectric materials and devices may be used to convert thermal energy into electrical energy, or use electrical energy to produce heat or refrigeration. Embodiments of the invention relate to p-type thermoelectric materials related to the compound Yb.sub.14MnSb.sub.11.

  19. Semiconducting Ba 3Sn 3Sb 4 and Metallic Ba 7–xSn 11Sb 15–y ( x = 0.4, y = 0.6) Zintl Phases

    DOE PAGES

    Chen, Haijie; Narayan, Awadhesh; Stoumpos, Constantinos C.; ...

    2017-11-08

    In this paper, we report the discovery of two ternary Zintl phases Ba 3Sn 3Sb 4 and Ba 7-xSn 11Sb 15-y, (x = 0.4, y = 0.6). Ba 3Sn 3Sb 4 adopts the monoclinic space group P2 1/c with a = 14.669(3) Å, b = 6.9649(14) Å, c = 13.629(3) Å, and β = 104.98(3)°. It features a unique corrugated two-dimensional (2D) structure consisting of [Sn 3Sb 4] 6- layers extending along the ab plane with Ba 2+ atoms sandwiched between them. The non-stoichiometric Ba 6.6Sn 11Sb 14.4 has a complex one-dimensional (1D) structure adopting the orthorhombic space group Pnma,more » with unit cell parameters a = 37.964(8) Å, b = 4.4090(9) Å and c = 24.682(5) Å. It consists of large double Sn-Sb ribbons separated by Ba 2+ atoms. Ba3Sn3Sb4 is an n-type semiconductor which has a narrow energy gap of ~0.18 eV and a room temperature carrier concentration of ~4.2 × 10 18 cm -3. Lastly, Ba 6.6Sn 11Sb 14.4 is determined to be a metal with electrons being the dominant carriers.« less

  20. Semiconducting Ba 3Sn 3Sb 4 and Metallic Ba 7–xSn 11Sb 15–y ( x = 0.4, y = 0.6) Zintl Phases

    SciT

    Chen, Haijie; Narayan, Awadhesh; Stoumpos, Constantinos C.

    In this paper, we report the discovery of two ternary Zintl phases Ba 3Sn 3Sb 4 and Ba 7-xSn 11Sb 15-y, (x = 0.4, y = 0.6). Ba 3Sn 3Sb 4 adopts the monoclinic space group P2 1/c with a = 14.669(3) Å, b = 6.9649(14) Å, c = 13.629(3) Å, and β = 104.98(3)°. It features a unique corrugated two-dimensional (2D) structure consisting of [Sn 3Sb 4] 6- layers extending along the ab plane with Ba 2+ atoms sandwiched between them. The non-stoichiometric Ba 6.6Sn 11Sb 14.4 has a complex one-dimensional (1D) structure adopting the orthorhombic space group Pnma,more » with unit cell parameters a = 37.964(8) Å, b = 4.4090(9) Å and c = 24.682(5) Å. It consists of large double Sn-Sb ribbons separated by Ba 2+ atoms. Ba3Sn3Sb4 is an n-type semiconductor which has a narrow energy gap of ~0.18 eV and a room temperature carrier concentration of ~4.2 × 10 18 cm -3. Lastly, Ba 6.6Sn 11Sb 14.4 is determined to be a metal with electrons being the dominant carriers.« less

  1. Structurally complex Zintl compounds for high temperature thermoelectric power generation

    NASA Astrophysics Data System (ADS)

    Zevalkink, Alexandra; Pomrehn, Gregory; Gibbs, Zachary; Snyder, Jeffrey

    2014-03-01

    Zintl phases, characterized by covalently-bonded substructures surrounded by highly electropositive cations, exhibit many of the characteristics desired for thermoelectric applications. Recently, we demonstrated promising thermoelectric performance (zT values between 0.4 and 0.9) in a class of Zintl antimonides that share a common structural motif: anionic moieties resembling infinite chains of linked tetrahedra. These compounds (A5M2 Sb6 and A3 M Sb3 compounds where A = Ca or Sr and M = Al, Ga and In) crystallize as four distinct, but closely related chain-forming structure types. Their large unit cells lead to exceptionally low lattice thermal conductivity due to the containment of heat in low velocity optical phonon modes. Here, we show that chemical substitutions on the A and M sites can be used to control the electronic and thermal transport properties and optimize the thermoelectric figure of merit. Doping with alio-valent elements allows for rational control of the carrier concentration, while isoelectronic substitutions can be used to fine-tune the intrinsic properties. A combination of Density Functional calculations and classical transport models was used to explain the experimentally observed transport properties of these compounds.

  2. Aromaticity and Antiaromaticity in Zintl Clusters

    SciT

    Sun, Zhong -Ming; Liu, Chao; Popov, Ivan Aleksandrovich

    Originally, the concepts of aromaticity and antiaromaticity were introduced to explain the stability and reactivity of unsaturated organic compounds. Since then, they have been extended to other species with delocalized electrons including various saturated systems, organometallic compounds, and even inorganic clusters and molecules. In this study, we focus on the most recent progress of using these concepts to guide experimental synthesis and rationalize geometrical and electronic structures of a particular family of polyanions composed of Group 14 and 15 elements, namely Zintl clusters.

  3. Aromaticity and Antiaromaticity in Zintl Clusters

    DOE PAGES

    Sun, Zhong -Ming; Liu, Chao; Popov, Ivan Aleksandrovich; ...

    2018-05-18

    Originally, the concepts of aromaticity and antiaromaticity were introduced to explain the stability and reactivity of unsaturated organic compounds. Since then, they have been extended to other species with delocalized electrons including various saturated systems, organometallic compounds, and even inorganic clusters and molecules. In this study, we focus on the most recent progress of using these concepts to guide experimental synthesis and rationalize geometrical and electronic structures of a particular family of polyanions composed of Group 14 and 15 elements, namely Zintl clusters.

  4. Structural comparison of nickel electrodes and precursor phases

    NASA Technical Reports Server (NTRS)

    Cornilsen, Bahne C.; Shan, Xiaoyin; Loyselle, Patricia

    1989-01-01

    Researchers summarize previous Raman spectroscopic results and discuss important structural differences in the various phases of active mass and active mass precursors. Raman spectra provide unique signatures for these phases, and allow one to distinguish each phase, even when the compound is amorphous to x rays (i.e., does not scatter x rays because of a lack of order and/or small particle size). The structural changes incurred during formation, charge and discharge, cobalt addition, and aging are discussed. The oxidation states and dopant contents are explained in terms of the nonstoichiometric structures.

  5. Synthesis and characterization of the divalent samarium Zintl-phases SmMg 2Bi 2 and SmMg 2Sb 2

    DOE PAGES

    Ramirez, D.; Gallagher, A.; Baumbach, R.; ...

    2015-08-29

    Here, single crystals of LnMg 2Bi 2 (Ln = Yb, Eu, Sm) and SmMg 2Sb 2 were synthesized using Mg-Bi metal and Mg-Sb metal fluxes, respectively. The crystal structures are of the CaAl 2Si 2 type with space group P3 m1 (#164, Z = 1): SmMg 2Bi 2 ( a = 4.7745(1)Å, c = 7.8490(2)Å), EuMg 2Bi 2 ( a = 4.7702(1)Å, c = 7.8457(2) Å), YbMg 2Bi 2 ( a = 4.7317(2)Å, c = 7.6524(3) Å), and SmMg 2Sb 2 ( a = 4.6861(1) Å, c = 7.7192(2) Å). Heat capacity, electrical transport, and magnetization of all bismuth containingmore » phases were measured. The materials behave as “poor metals” with resistivity between 2 and 10 mΩ·cm. Temperature independent Van Vleck paramagnetism is observed in SmMg 2Bi 2 indicative of divalent samarium (Sm 2+) ions.« less

  6. Overview of the amorphous precursor phase strategy in biomineralization

    NASA Astrophysics Data System (ADS)

    Weiner, Steve; Mahamid, Julia; Politi, Yael; Ma, Yurong; Addadi, Lia

    2009-06-01

    It was assumed for a long time that organisms produce minerals directly from a saturated solution. A few exceptions were known, including the well documented mineralized teeth of the chiton. In 1997 it was demon-strated that sea urchin larvae form their calcitic spicules by first depositing a highly unstable mineral phase called amorphous calcium carbonate. This strategy has since been shown to be used by animals from other phyla and for both aragonite and calcite. Recent evidence shows that vertebrate bone mineral may also be formed via a precursor phase of amorphous calcium carbonate. This strategy thus appears to be widespread. The challenge now is to understand the mechanisms by which these unstable phases are initially formed, how they are temporarily stabilized and how they are destabilized and transform into a crystalline mature product.

  7. Eu9Cd4-xCM2+x-y□ySb9: Ca9Mn4Bi9-type structure stuffed with coinage metals (Cu, Ag, and Au) and the challenges with classical valence theory in describing these possible zintl phases.

    PubMed

    Kazem, Nasrin; Hurtado, Antonio; Klobes, Benedikt; Hermann, Raphaël P; Kauzlarich, Susan M

    2015-02-02

    The synthesis, crystal structure, magnetic properties, and europium Mössbauer spectroscopy of the new members of the 9-4-9 Zintl family of Eu(9)Cd(4-x)CM(2+x-y)□(y)Sb(9) (CM = coinage metal: Au, Ag, and Cu) are reported. These compounds crystallize in the Ca(9)Mn(4)Bi(9) structure type (9-4-9) with the 4g interstitial site almost half-occupied by coinage metals; these are the first members in the 9-4-9 family where the interstitial positions are occupied by a monovalent metal. All previously known compounds with this structure type include divalent interstitials where these interstitials are typically the same as the transition metals in the anionic framework. Single-crystal magnetic susceptibility data indicate paramagnetic behavior for all three compounds with antiferromagnetic ordering below 10 K (at 100 Oe) that shifts to lower temperature (<7 K) by applying a 3 T magnetic field. (151)Eu Mössbauer spectra were collected on polycrystalline powder samples of Eu(9)Cd(4-x)CM(2+x-y)□(y)Sb(9) at 50 and 6.5 K in order to evaluate the valence of Eu cations. Although the Zintl formalism states that the five crystallographically distinct Eu sites in Eu(9)Cd(4-x)CM(2+x-y)□(y)Sb9 should bear Eu(2+), the Mössbauer spectral isomer shifts are clearly indicative of both 2+ and 3+ valence of the Eu cations with the Cu- and Au-containing compounds showing higher amounts of Eu(3+). This electronic configuration leads to an excess of negative charge in these compounds that contradicts the expected valence-precise requirement of Zintl phases. The spectra obtained at 6.5 K reveal magnetic ordering for both Eu(2+) and Eu(3+). The field dependence of Eu(2+) indicates two distinct magnetic sublattices, with higher and lower fields, and of a small field for Eu(3+). The site symmetry of the five Eu sites is not distinguishable from the Mössbauer data.

  8. Amorphous Calcium Carbonate in Biomineralization: Stable and Precursor Phases

    NASA Astrophysics Data System (ADS)

    Weiner, S.

    2003-12-01

    The biological formation of the crystalline polymorphs of calcium carbonate, aragonite and calcite, is widespread. The less stable polymorphs, vaterite and monohydrocalcite are also formed by some organisms. Surprisingly, the highly unstable phase, amorphous calcium carbonate (ACC), is formed by a variety of organisms from different phyla. Most of these are stable at least within the lifetime of the organism. The stable forms all have a stoichiometry of CaCO3.H2O. Despite the fact that they do not diffract X-rays. Studies of their short range order by EXAFS, reveal species specific variations in the number and distances of atoms that surround the calcium ion. Proteins extracted from stable biogenic ACC are able to stabilize the phase in vitro. ACC has also been identified as a transient precursor phase during the formation of the calcitic larval spicule of the sea urchin and the formation of the larval shell of a bivalve. The transient form has little or no water associated with the CaCO3. Preliminary EXAFS data suggest that the short range order of the sea urchin spicule transient ACC resembles calcite. Proteins extracted from these spicules are able to stabilize ACC provided Mg is present in the solution. As the mollusks and the echinoderms are on two different branches of the animal phylogenetic tree, it is conceivable that the strategy of using ACC as a precursor phase at least for larval mineralization may be widespread. It has yet to be shown that it is used by adults of either phylum. The manner in which organisms precipitate, stabilize and destabilize if necessary, this highly metastable phase of calcium carbonate presents many fascinating and enigmatic questions, whose solutions could well contribute to a better understanding of basic processes in biomineralization. For more details and references, see Addadi, L., Raz, S. and Weiner, S. (2003). Taking advantage of disorder: Amorphous calcium carbonate and its roles in biomineralization. Adv. Mat.15, 959-970.

  9. Structural comparison of nickel electrodes and precursor phases

    NASA Technical Reports Server (NTRS)

    Cornilsen, Bahne C.; Shan, Xiaoyin; Loyselle, Patricia

    1989-01-01

    A summary of previous Raman spectroscopic results and a discussion of important structural differences in the various phases of active mass and active mass precurors are presented. Raman spectra provide unique signatures for these phases, and allow one to distinguish each phase, even when the compound is amorphous to X-rays (i.e., does not scatter X-rays because of a lack of order and/or small particle size). The structural changes incurred during formation, charge and discharge, cobalt addition, and aging will be discussed and related to electrode properties. Important structural differences include NiO2 layer stacking, nonstoichiometry (especially cation-deficit nonstoichiometry), disorder, dopant content, and water content. The results indicate that optimal nickel active mass is non-close packed and nonstoichiometric. The formation process transforms precursor phases into this structure. Therefore, the precursor disorder, or lack thereof, influences this final active mass structure and the rate of formation. Aging processes induce structural change which is believed to be detrimental. The role of cobalt addition can be appreciated in terms of structures favored or stabilized by the dopant. In recent work, the in situ Raman technique to characterize the critical structural parameters was developed. An in situ method relates structure, electrochemistry, and preparation. In situ Raman spectra of cells during charge and discharge, either during cyclic voltammetry or under constant current conditions were collected. With the structure-preparation knowledge and the in situ Raman tool, it will be possible to define the structure-property-preparation relations in more detail. This instrumentation has application to a variety of electrode systems.

  10. Potential for high thermoelectric performance in n-type Zintl compounds: A case study of Ba doped KAlSb 4

    DOE PAGES

    Ortiz, Brenden R.; Gorai, Prashun; Krishna, Lakshmi; ...

    2017-01-11

    High-throughput calculations (first-principles density functional theory and semi-empirical transport models) have the potential to guide the discovery of new thermoelectric materials. Herein we have computationally assessed the potential for thermoelectric performance of 145 complex Zintl pnictides. Of the 145 Zintl compounds assessed, 17% show promising n-type transport properties, compared with only 6% showing promising p-type transport. We predict that n-type Zintl compounds should exhibit high mobility μ n while maintaining the low thermal conductivity κ L typical of Zintl phases. Thus, not only do candidate n-type Zintls outnumber their p-type counterparts, but they may also exhibit improved thermoelectric performance. Frommore » the computational search, we have selected n-type KAlSb 4 as a promising thermoelectric material. Synthesis and characterization of polycrystalline KAlSb 4 reveals non-degenerate n-type transport. With Ba substitution, the carrier concentration is tuned between 10 18 and 10 19 e – cm –3 with a maximum Ba solubility of 0.7% on the K site. High temperature transport measurements confirm a high μ n (50 cm 2 V –1 s –1) coupled with a near minimum κ L (0.5 W m –1 K –1) at 370 °C. Together, these properties yield a zT of 0.7 at 370 °C for the composition K 0.99Ba 0.01AlSb 4. As a result, based on the theoretical predictions and subsequent experimental validation, we find significant motivation for the exploration of n-type thermoelectric performance in other Zintl pnictides.« less

  11. Potential for high thermoelectric performance in n-type Zintl compounds: A case study of Ba doped KAlSb 4

    SciT

    Ortiz, Brenden R.; Gorai, Prashun; Krishna, Lakshmi

    High-throughput calculations (first-principles density functional theory and semi-empirical transport models) have the potential to guide the discovery of new thermoelectric materials. Herein we have computationally assessed the potential for thermoelectric performance of 145 complex Zintl pnictides. Of the 145 Zintl compounds assessed, 17% show promising n-type transport properties, compared with only 6% showing promising p-type transport. We predict that n-type Zintl compounds should exhibit high mobility μ n while maintaining the low thermal conductivity κ L typical of Zintl phases. Thus, not only do candidate n-type Zintls outnumber their p-type counterparts, but they may also exhibit improved thermoelectric performance. Frommore » the computational search, we have selected n-type KAlSb 4 as a promising thermoelectric material. Synthesis and characterization of polycrystalline KAlSb 4 reveals non-degenerate n-type transport. With Ba substitution, the carrier concentration is tuned between 10 18 and 10 19 e – cm –3 with a maximum Ba solubility of 0.7% on the K site. High temperature transport measurements confirm a high μ n (50 cm 2 V –1 s –1) coupled with a near minimum κ L (0.5 W m –1 K –1) at 370 °C. Together, these properties yield a zT of 0.7 at 370 °C for the composition K 0.99Ba 0.01AlSb 4. As a result, based on the theoretical predictions and subsequent experimental validation, we find significant motivation for the exploration of n-type thermoelectric performance in other Zintl pnictides.« less

  12. Formation of titanosilicate precursors of an active adsorption phase

    NASA Astrophysics Data System (ADS)

    Kuznetsova, T. F.; Ivanets, A. I.; Katsoshvili, L. L.

    2017-04-01

    Micro-mesoporous titanosilicate precursors of the active absorption phase of a composite ceramic membrane are synthesized, and their textural and adsorption properties are investigated by means of low-temperature nitrogen adsorption/desorption. Low-temperature isotherms of nitrogen adsorption/desorption are analyzed using the BET, Langmuir, comparative t-plot, Barrett-Joyner-Halenda, and density functional theory methods. It is found that at high contents of silicon(IV) oxide, the resulting xerogels have surface areas of 656 and 890 m2/g according to the BET and Langmuir approaches, respectively, while the micropores' inner and outer surfaces are 453 and 466 m2/g, respectively, according to the t-plot. According to the DFT distributions, the mesopore diameters of a sample can be adjusted in the range of 3-9 nm. By analyzing the type of capillary condensation hysteresis in the adsorption/desorption isotherms, it is shown that the pores in the samples are very bottle-like, even though their shape may be different in reality. It is found that in samples with high contents of titanium(IV) oxide, the pore throats are blocked during adsorbate desorption, due to the percolation effect. It is assumed that the stabilization of particles of titanium(IV) oxide by amorphous layers of silica protects the texture of titanosilicate xerogels from full contraction and the coalescence of particles during heat treatment ranging from 393 to 923 K.

  13. Effect of charge and composition on the structural fluxionality and stability of nine atom tin-bismuth Zintl analogues.

    PubMed

    Gupta, Ujjwal; Reber, Arthur C; Clayborne, Penee A; Melko, Joshua J; Khanna, Shiv N; Castleman, A W

    2008-12-01

    Synergistic studies of bismuth doped tin clusters combining photoelectron spectra with first principles theoretical investigations establish that highly charged Zintl ions, observed in the condensed phase, can be stabilized as isolated gas phase clusters through atomic substitution that preserves the overall electron count but reduces the net charge and thereby avoids instability because of coulomb repulsion. Mass spectrometry studies reveal that Sn(8)Bi(-), Sn(7)Bi(2)(-), and Sn(6)Bi(3)(-) exhibit higher abundances than neighboring species, and photoelectron spectroscopy show that all of these heteroatomic gas phase Zintl analogues (GPZAs) have high adiabatic electron detachment energies. Sn(6)Bi(3)(-) is found to be a particularly stable cluster, having a large highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap. Theoretical calculations demonstrate that the Sn(6)Bi(3)(-) cluster is isoelectronic with the well know Sn(9)(-4) Zintl ion; however, the fluxionality reported for Sn(9)(-4) is suppressed by substituting Sn atoms with Bi atoms. Thus, while the electronic stability of the clusters is dominated by electron count, the size and position of the atoms affects the dynamics of the cluster as well. Substitution with Bi enlarges the cage compared with Sn(9)(-4) making it favorable for endohedral doping, findings which suggest that these cages may find use for building blocks of cluster assembled materials.

  14. Revealing the optoelectronic and thermoelectric properties of the Zintl quaternary arsenides ACdGeAs{sub 2} (A = K, Rb)

    SciT

    Azam, Sikander; Khan, Saleem Ayaz; Goumri-Said, Souraya, E-mail: Souraya.Goumri-Said@chemistry.gatech.edu

    Highlights: • Zintl tetragonal phase ACdGeAs{sub 2} (A = K, Rb) are chalcopyrite and semiconductors. • Their direct band gap is suitable for PV, optolectronic and thermoelectric applications. • Combination of DFT and Boltzmann transport theory is employed. • The present arsenides are found to be covalent materials. - Abstract: Chalcopyrite semiconductors have attracted much attention due to their potential implications in photovoltaic and thermoelectric applications. First principle calculations were performed to investigate the electronic, optical and thermoelectric properties of the Zintl tetragonal phase ACdGeAs{sub 2} (A = K, Rb) using the full potential linear augmented plane wave method andmore » the Engle–Vosko GGA (EV–GGA) approximation. The present compounds are found semiconductors with direct band gap and covalent bonding character. The optical transitions are investigated via the dielectric function (real and imaginary parts) along with other related optical constants including refractive index, reflectivity and energy-loss spectrum. Combining results from DFT and Boltzmann transport theory, we reported the thermoelectric properties such as the Seebeck’s coefficient, electrical and thermal conductivity, figure of merit and power factor as function of temperatures. The present chalcopyrite Zintl quaternary arsenides deserve to be explored for their potential applications as thermoelectric materials and for photovoltaic devices.« less

  15. Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups

    PubMed Central

    Gillett-Kunnath, Miriam M.; Sevov, Slavi C.

    2012-01-01

    Although the first studies of Zintl ions date between the late 1890's and early 1930's they were not structurally characterized until many years later.1,2 Their redox chemistry is even younger, just about ten years old, but despite this short history these deltahedral clusters ions E9n- (E = Si, Ge, Sn, Pb; n = 2, 3, 4) have already shown interesting and diverse reactivity and have been at the forefront of rapidly developing and exciting new chemistry.3-6 Notable milestones are the oxidative coupling of Ge94- clusters to oligomers and infinite chains,7-19 their metallation,14-16,20-25 capping by transition-metal organometallic fragments,26-34 insertion of a transition-metal atom at the center of the cluster which is sometimes combined with capping and oligomerization,35-47 addition of main-group organometallic fragments as exo-bonded substituents,48-50 and functionalization with various organic residues by reactions with organic halides and alkynes.51-58 This latter development of attaching organic fragments directly to the clusters has opened up a new field, namely organo-Zintl chemistry, that is potentially fertile for further synthetic explorations, and it is the step-by-step procedure for the synthesis of germanium-divinyl clusters described herein. The initial steps outline the synthesis of an intermetallic precursor of K4Ge9 from which the Ge94- clusters are extracted later in solution. This involves fused-silica glass blowing, arc-welding of niobium containers, and handling of highly air-sensitive materials in a glove box. The air-sensitive K4Ge9 is then dissolved in ethylenediamine in the box and then alkenylated by a reaction with Me3SiC≡CSiMe3. The reaction is followed by electrospray mass spectrometry while the resulting solution is used for obtaining single crystals containing the functionalized clusters [H2C=CH-Ge9-CH=CH2]2-. For this purpose the solution is centrifuged, filtered, and carefully layered with a toluene solution of 18-crown-6. Left

  16. Synthesis, crystal structures, and physical properties of the new Zintl phases A{sub 21}Zn{sub 4}Pn{sub 18} (A=Ca, Eu; Pn=As, Sb)—Versatile arrangements of [ZnPn{sub 4}] tetrahedra

    SciT

    Suen, Nian-Tzu; Wang, Yi; Bobev, Svilen, E-mail: bobev@udel.edu

    Four new Zintl phases, Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18} and Eu{sub 21}Zn{sub 4}Sb{sub 18} have been synthesized by metal flux reactions. Their structures have been established from single-crystal X-ray diffraction. Despite the similar chemical makeup and the identical formulae, the structures of the four compounds are not the same—Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18} and Eu{sub 21}Zn{sub 4}As{sub 18} crystallize in the monoclinic space group C2/m (No. 12, Z=4) with the β-Ca{sub 21}Mn{sub 4}Sb{sub 18} structure type, while Eu{sub 21}Zn{sub 4}Sb{sub 18} adopts the Ba{sub 21}Cd{sub 4}Sb{sub 18} structure type withmore » the orthorhombic space group Cmce (No. 64, Z=8). Both structures are based on ZnAs{sub 4} or ZnSb{sub 4} tetrahedra, linked in slightly different ways, and Ca{sup 2+} and Eu{sup 2+} cations that fill the space between them. The structural relationships between the title compounds and other known ternary phases with intricate structures are discussed. Electrical resistivity measurement on single-crystalline Eu{sub 21}Zn{sub 4}Sb{sub 18} suggests an intrinsic semiconductor behavior with a band gap of ca. 0.2 eV. The temperature dependent DC magnetization measurement on the same material indicates Curie–Weiss paramagnetism in the high-temperature regime, and a spontaneous antiferromagnetic ordering below 8 K. The calculated effective moments of Eu confirm the divalent Eu{sup 2+} ground state, as expected from the Zintl–Klemm concept. - Graphical abstract: The four new Zintl phases—Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18}, and Eu{sub 21}Zn{sub 4}Sb{sub 18}—crystallize in two structure types, showing the versatility in the arrangements of ZnAs{sub 4} and ZnSb{sub 4} tetrahedra. - Highlights: • Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18}, and Eu{sub 21}Zn{sub 4}Sb

  17. Synthesis and structural characterization of the Zintl phases Na{sub 3}Ca{sub 3}TrPn{sub 4}, Na{sub 3}Sr{sub 3}TrPn{sub 4}, and Na{sub 3}Eu{sub 3}TrPn{sub 4} (Tr=Al, Ga, In; Pn=P, As, Sb)

    SciT

    Wang, Yi; Suen, Nian-Tzu; College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002

    15 new quaternary Zintl phases have been synthesized by solid-state reactions from the respective elements, and their structures have been determined by single-crystal X-ray diffraction. Na{sub 3}E{sub 3}TrPn{sub 4} (E=Ca, Sr, Eu; Tr=Al, Ga, In; Pn=P, As, Sb) crystallize in the hexagonal crystal system with the non-centrosymmetric space group P6{sub 3}mc (No. 186). The structure represents a variant of the K{sub 6}HgS{sub 4} structure type (Pearson index hP22) and features [TrPn{sub 4}]{sup 9–} tetrahedral units, surrounded by Na{sup +} and Ca{sup 2+}, Sr{sup 2+}, Eu{sup 2+} cations. The nominal formula rationalization [Na{sup +}]{sub 3}[E{sup 2+}]{sub 3}[TrPn{sub 4}]{sup 9–} follows themore » octet rule, suggesting closed-shell configurations for all atoms and intrinsic semiconducting behavior. However, structure refinements for several members hint at disorder and mixing of cations that potentially counteract the optimal valence electron count. - Graphical abstract: The hexagonal, non-centrosymmetric structure of Na{sub 3}E{sub 3}TrPn{sub 4} (E=Ca, Sr, Eu; Tr=Al, Ga, In; Pn=P, As, Sb) features [TrPn{sub 4}]{sup 9–} tetrahedral units, surrounded by Na{sup +} and Ca{sup 2+}, Sr{sup 2+}, Eu{sup 2+} cations. - Highlights: • 15 quaternary phosphides, arsenides, and antimonides are synthesized and structurally characterized. • The structure is a variant of the hexagonal K{sub 6}HgS{sub 4}-type, with distinctive pattern for the cations. • Occupational and/or positional disorder of yet unknown origin exists for some members of the series.« less

  18. Nonequilibrium Phase Precursors during a Photoexcited Insulator-to-Metal Transition in V2O3

    NASA Astrophysics Data System (ADS)

    Singer, Andrej; Ramirez, Juan Gabriel; Valmianski, Ilya; Cela, Devin; Hua, Nelson; Kukreja, Roopali; Wingert, James; Kovalchuk, Olesya; Glownia, James M.; Sikorski, Marcin; Chollet, Matthieu; Holt, Martin; Schuller, Ivan K.; Shpyrko, Oleg G.

    2018-05-01

    Here, we photoinduce and directly observe with x-ray scattering an ultrafast enhancement of the structural long-range order in the archetypal Mott system V2O3 . Despite the ultrafast increase in crystal symmetry, the change of unit cell volume occurs an order of magnitude slower and coincides with the insulator-to-metal transition. The decoupling between the two structural responses in the time domain highlights the existence of a transient photoinduced precursor phase, which is distinct from the two structural phases present in equilibrium. X-ray nanoscopy reveals that acoustic phonons trapped in nanoscale twin domains govern the dynamics of the ultrafast transition into the precursor phase, while nucleation and growth of metallic domains dictate the duration of the slower transition into the metallic phase. The enhancement of the long-range order before completion of the electronic transition demonstrates the critical role the nonequilibrium structural phases play during electronic phase transitions in correlated electrons systems.

  19. OBSERVATIONS OF MAGNETIC FLUX-ROPE OSCILLATION DURING THE PRECURSOR PHASE OF A SOLAR ERUPTION

    SciT

    Zhou, G. P.; Wang, J. X.; Zhang, J., E-mail: gpzhou@nao.cas.cn, E-mail: wangjx@nao.cas.cn, E-mail: jzhang7@gmu.edu

    2016-05-20

    Based on combined observations from the Interface Region Imaging Spectrograph (IRIS) spectrometer with the coronal emission line of Fe xxi at 1354.08 Å and SDO /AIA images in multiple passbands, we report the finding of the precursor activity manifested as the transverse oscillation of a sigmoid, which is likely a pre-existing magnetic flux rope (MFR), that led to the onset of an X class flare and a fast halo coronal mass ejection (CME) on 2014 September 10. The IRIS slit is situated at a fixed position that is almost vertical to the main axis of the sigmoid structure that hasmore » a length of about 1.8 × 10{sup 5} km. This precursor oscillation lasts for about 13 minutes in the MFR and has velocities in the range of [−9, 11] km s{sup −1} and a period of ∼280 s. Our analysis, which is based on the temperature, density, length, and magnetic field strength of the observed sigmoid, indicates that the nature of the oscillation is a standing wave of fast magnetoacoustic kink mode. We further find that the precursor oscillation is excited by the energy released through an external magnetic reconnection between the unstable MFR and the ambient magnetic field. It is proposed that this precursor activity leads to the dynamic formation of a current sheet underneath the MFR that subsequently reconnects to trigger the onset of the main phase of the flare and the CME.« less

  20. Engineering half-Heusler thermoelectric materials using Zintl chemistry

    NASA Astrophysics Data System (ADS)

    Zeier, Wolfgang G.; Schmitt, Jennifer; Hautier, Geoffroy; Aydemir, Umut; Gibbs, Zachary M.; Felser, Claudia; Snyder, G. Jeffrey

    2016-06-01

    Half-Heusler compounds based on XNiSn and XCoSb (X = Ti, Zr or Hf) have rapidly become important thermoelectric materials for converting waste heat into electricity. In this Review, we provide an overview on the electronic properties of half-Heusler compounds in an attempt to understand their basic structural chemistry and physical properties, and to guide their further development. Half-Heusler compounds can exhibit semiconducting transport behaviour even though they are described as ‘intermetallic’ compounds. Therefore, it is most useful to consider these systems as rigid-band semiconductors within the framework of Zintl (or valence-precise) compounds. These considerations aid our understanding of their properties, such as the bandgap and low hole mobility because of interstitial Ni defects in XNiSn. Understanding the structural and bonding characteristics, including the presence of defects, will help to develop different strategies to improve and design better half-Heusler thermoelectric materials.

  1. Nucleation and Epitaxy-Mediated Phase Transformation of a Precursor Cadmium Carbonate Phase at the Calcite/Water Interface

    SciT

    Riechers, Shawn L.; Rosso, Kevin M.; Kerisit, Sebastien N.

    Mineral nucleation can be catalyzed by the presence of mineral substrates; however, the mechanisms of heterogeneous nucleation remain poorly understood. A combination of in situ time-sequenced measurements and nano-manipulation experiments were performed using atomic force microscopy (AFM) to probe the mechanisms of heteroepitaxial nucleation of otavite (CdCO3) on calcite (CaCO3) single crystals that exposed the (10-14) surface. Otavite and calcite are isostructural carbonates that display a 4% lattice mismatch, based on their (10-14) surface areas. AFM observations revealed a two-stage process in the nucleation of cadmium carbonate surface precipitates. As evidenced by changes in height, shape, growth behavior, and frictionmore » signal of the precipitates, a precursor phase was observed to initially form on the surface and subsequently undergo an epitaxy-mediated phase transformation to otavite, which then grew epitaxially. Nano-manipulation experiments, in which the applied force was increased progressively until precipitates were removed from the surface, showed that adhesion of the precursor phase to the substrate was distinctively weaker than that of the epitaxial phase, consistent with that of an amorphous phase. These findings demonstrate for the first time that heterogeneous mineral nucleation can follow a non-classical pathway like that found in homogenous aqueous conditions.« less

  2. Template-assisted mineral formation via an amorphous liquid phase precursor route

    NASA Astrophysics Data System (ADS)

    Amos, Fairland F.

    The search for alternative routes to synthesize inorganic materials has led to the biomimetic route of producing ceramics. In this method, materials are manufactured at ambient temperatures and in aqueous solutions with soluble additives and insoluble matrix, similar to the biological strategy for the formation of minerals by living organisms. Using this approach, an anionic polypeptide additive was used to induce an amorphous liquid-phase precursor to either calcium carbonate or calcium phosphate. This precursor was then templated on either organic or inorganic substrates. Non-equilibrium morphologies, such as two-dimensional calcium carbonate films, one-dimensional calcium carbonate mesostructures and "molten" calcium phosphate spherulites were produced, which are not typical of the traditional (additive-free) solution grown crystals in the laboratory. In the study of calcium carbonate, the amorphous calcium carbonate mineral formed via the liquid-phase precursor, either underwent a dissolution-recrystallization event or a pseudo-solid-state transformation to produce different morphologies and polymorphs of the mineral. Discrete or aggregate calcite crystals were formed via the dissolution of the amorphous phase to allow the reprecipitation of the stable crystal. Non-equilibrium morphologies, e.g., films, mesotubules and mesowires were templated using organic and inorganic substrates and compartments. These structures were generated via an amorphous solid to crystalline solid transformation. Single crystalline tablets and mesowires of aragonite, which are reported to be found only in nature as skeletal structures of marine organisms, such as mollusk nacre and echinoderm teeth, were successfully synthesized. These biomimetic structures were grown via the polymer-induced liquid-phase precursor route in the presence of magnesium. Only low magnesium-bearing calcite was formed in the absence of the polymer. A similar approach of using a polymeric additive was

  3. Electron beam induced deposition of silicon nanostructures from a liquid phase precursor.

    PubMed

    Liu, Yin; Chen, Xin; Noh, Kyong Wook; Dillon, Shen J

    2012-09-28

    This work demonstrates electron beam induced deposition of silicon from a SiCl(4) liquid precursor in a transmission electron microscope and a scanning electron microscope. Silicon nanodots of tunable size are reproducibly grown in controlled geometries. The volume of these features increases linearly with deposition time. The results indicate that secondary electrons generated at the substrate surface serve as the primary source of silicon reduction. However, at high current densities the influence of the primary electrons is observed to retard growth. The results demonstrate a new approach to fabricating silicon nanostructures and provide fundamental insights into the mechanism for liquid phase electron beam induced deposition.

  4. Electron beam induced deposition of silicon nanostructures from a liquid phase precursor

    NASA Astrophysics Data System (ADS)

    Liu, Yin; Chen, Xin; Noh, Kyong Wook; Dillon, Shen J.

    2012-09-01

    This work demonstrates electron beam induced deposition of silicon from a SiCl4 liquid precursor in a transmission electron microscope and a scanning electron microscope. Silicon nanodots of tunable size are reproducibly grown in controlled geometries. The volume of these features increases linearly with deposition time. The results indicate that secondary electrons generated at the substrate surface serve as the primary source of silicon reduction. However, at high current densities the influence of the primary electrons is observed to retard growth. The results demonstrate a new approach to fabricating silicon nanostructures and provide fundamental insights into the mechanism for liquid phase electron beam induced deposition.

  5. Multiwavelength Diagnostics of the Precursor and Main Phases of an M1.8 Flare on 2011 April 22

    NASA Technical Reports Server (NTRS)

    Awasthi, A. K.; Jain, R.; Gadhiya, P. D.; Aschwanden, M. J.; Uddin, W.; Srivastava, A. K.; Chandra, R.; Gopalswamy, N.; Nitta, N. V.; Yashiro, S.; hide

    2013-01-01

    We study the temporal, spatial and spectral evolution of the M1.8 flare, which occurred in the active region 11195 (S17E31) on 2011 April 22, and explore the underlying physical processes during the precursor phase and their relation to the main phase. The study of the source morphology using the composite images in 131Å wavelength observed by the Solar Dynamics Observatory/Atmospheric Imaging Assembly and 6-14 kiloelectronvolts [from the Reuven Ramaty High Energy Solar Spectroscopic Imager (RHESSI)] revealed a multi-loop system that destabilized systematically during the precursor and main phases. In contrast, hard X-ray emission (20-50 kiloelectronvolts) was absent during the precursor phase, appearing only from the onset of the impulsive phase in the form of foot-points of emitting loops. This study also revealed the heated loop-top prior to the loop emission, although no accompanying foot-point sources were observed during the precursor phase. We estimate the flare plasma parameters, namely temperature (T), emission measure (EM), power-law index (gamma) and photon turn-over energy (to), and found them to be varying in the ranges 12.4-23.4 megakelvins, 0.0003-0.6 x 10 (sup 49) per cubic centimeter, 5-9 and 14-18 kiloelectronvolts, respectively, by forward fitting RHESSI spectral observations. The energy released in the precursor phase was thermal and constituted approximately 1 percent of the total energy released during the flare. The study of morphological evolution of the filament in conjunction with synthesized T and EM maps was carried out, which reveals (a) partial filament eruption prior to the onset of the precursor emission and (b) heated dense plasma over the polarity inversion line and in the vicinity of the slowly rising filament during the precursor phase. Based on the implications from multiwavelength observations, we propose a scheme to unify the energy release during the precursor and main phase emissions in which the precursor phase emission

  6. Chromospheric Response during the Precursor and the Main Phase of a B6.4 Flare on 2005 August 20

    NASA Astrophysics Data System (ADS)

    Awasthi, Arun Kumar; Rudawy, Pawel; Falewicz, Robert; Berlicki, Arkadiusz; Liu, Rui

    2018-05-01

    Solar flare precursors depict a constrained rate of energy release, in contrast to the imminent rapid energy release, which calls for a different regime of plasma processes to be at play. Due to the subtle emission during the precursor phase, its diagnostics remain delusive, revealing either nonthermal electrons (NTEs) or thermal conduction to be the driver. In this regard, we investigate the chromospheric response during various phases of a B6.4 flare on 2005 August 20. Spatiotemporal investigation of flare ribbon enhancement during the precursor phase, carried out using spectra images recorded in several wavelength positions on the Hα line profile, revealed its delayed response (180 s) compared to the X-ray emission, as well as a sequential increment in the width of the line profile, which are indicative of a slow heating process. However, the energy contained in the Hα emission during the precursor phase can reach as high as 80% of that estimated during the main phase. Additionally, the plasma hydrodynamics during the precursor phase, resulting from the application of a single-loop one-dimensional model, revealed the presence of a power-law extension in the model-generated X-ray spectra, with a flux lower than the RHESSI background. Therefore, our multiwavelength diagnostics and hydrodynamical modeling of the precursor emission indicates the role of a two-stage process. First, reconnection-triggered NTEs, although too small in flux to overcome the observational constraints, thermalize in the upper chromosphere. This leads to the generation of a slow conduction front, which causes plasma heating during the precursor phase.

  7. Organo-Zintl-based superatoms: [Ge9(CHO)3] and [Ge9(CHO)

    NASA Astrophysics Data System (ADS)

    Reddy, G. Naaresh; Jena, Puru; Giri, Santanab

    2017-10-01

    A systematic study, based on density functional theory and different hybrid functionals for exchange-correlation potential, shows that the electron affinities of organo-zintl clusters [Ge9(R)n] [R = CHO; n = 1, 3] are close to that of chlorine (3.6 eV) and iodine (3.0 eV). A detailed study of the molecular orbitals of these complexes, when compared to those of Al13-, Cl- and I-, confirm that they behave as superatoms, mimicking the chemistry of halogens. This study expands the scope of superatoms by including a new class of pseudo-halogens based on ligated organo-Zintl ions.

  8. Amorphous calcium carbonate: A precursor phase for aragonite in shell disease of the pearl oyster.

    PubMed

    Huang, Jingliang; Liu, Chuang; Xie, Liping; Zhang, Rongqing

    2018-02-26

    Amorphous calcium carbonate (ACC) has long been shown to act as an important constituent or precursor phase for crystalline material in mollusks. However, the presence and the role of ACC in bivalve shell formation are not fully studied. In this study, we found that brown deposits containing heterogeneous calcium carbonates were precipitated when a shell disease occurred in the pearl oyster Pinctada fucata. Calcein-staining of the brown deposits indicated that numerous amorphous calcium deposits were present, which was further confirmed by Fourier-transform infrared spectroscopy (FTIR), Raman spectrum and X-ray difraction (XRD) analyses. So we speculate that ACC plays an important role in rapid calcium carbonate precipitation during shell repair process in diseased oysters. Copyright © 2018 Elsevier Inc. All rights reserved.

  9. Thermoelectric Performance and Defect Chemistry in n-Type Zintl KGaSb 4

    DOE PAGES

    Ortiz, Brenden R.; Gorai, Prashun; Stevanovic, Vladan; ...

    2017-05-08

    The rise of high-throughput calculations has accelerated the discovery of promising classes of thermoelectric materials. In prior work, we identified the n-type Zintl pnictides as one such material class. To date, however, a lack of detailed defect calculations and chemical intuition has led the community to investigate p-type Zintls almost exclusively. Here, we investigate the synthesis, thermoelectric properties, and defect structure of the complex Zintl KGaSb 4. We find that KGaSb 4 is successfully doped n-type with Ba and has the potential for p-type doping with Zn. Our calculations reveal the fundamental defect structure in KGaSb 4 that enables n-typemore » and p-type doping. We find that Ba doped KGaSb4 exhibits high electronic mobility (~50 cm 2V -1s -1) and near minimum lattice thermal conductivity (<0.5 Wm -1K -1) at 400 °C. Samples doped with 1.5% Ba achieve zT > 0.9 at 400 °C, promising for a previously unstudied material. Here, we also briefly investigate the series of alloys between KGaSb 4 and KAlSb 4, finding that a full solid solution exists. Altogether our work reinforces motivation for the exploration of n-type Zintl materials, especially in tandem with high-throughput defect calculations to inform selection of effective dopants and systems amenable to n-type transport.« less

  10. Thermoelectric Performance and Defect Chemistry in n-Type Zintl KGaSb 4

    SciT

    Ortiz, Brenden R.; Gorai, Prashun; Stevanovic, Vladan

    The rise of high-throughput calculations has accelerated the discovery of promising classes of thermoelectric materials. In prior work, we identified the n-type Zintl pnictides as one such material class. To date, however, a lack of detailed defect calculations and chemical intuition has led the community to investigate p-type Zintls almost exclusively. Here, we investigate the synthesis, thermoelectric properties, and defect structure of the complex Zintl KGaSb 4. We find that KGaSb 4 is successfully doped n-type with Ba and has the potential for p-type doping with Zn. Our calculations reveal the fundamental defect structure in KGaSb 4 that enables n-typemore » and p-type doping. We find that Ba doped KGaSb4 exhibits high electronic mobility (~50 cm 2V -1s -1) and near minimum lattice thermal conductivity (<0.5 Wm -1K -1) at 400 °C. Samples doped with 1.5% Ba achieve zT > 0.9 at 400 °C, promising for a previously unstudied material. Here, we also briefly investigate the series of alloys between KGaSb 4 and KAlSb 4, finding that a full solid solution exists. Altogether our work reinforces motivation for the exploration of n-type Zintl materials, especially in tandem with high-throughput defect calculations to inform selection of effective dopants and systems amenable to n-type transport.« less

  11. The gas phase origin of complex organic molecules precursors in prestellar cores

    NASA Astrophysics Data System (ADS)

    Bacmann, A.; Faure, A.

    2015-05-01

    Complex organic molecules (COMs) have long been observed in the warm regions surrounding nascent protostars. The recent discovery of oxygen-bearing COMs like methyl formate or dimethyl ether in prestellar cores (Bacmann et al. [2]), where gas and dust temperatures rarely exceed 10-15 K, has challenged the previously accepted models according to which COM formation relied on the diffusion of heavy radicals on warm (˜30 K) grains. Following these detections, new questions have arisen: do non-thermal processes play a role in increasing radical mobility or should new gas-phase routes be explored? The radicals involved in the formation of the aforementioned COMs, HCO and CH3O represent intermediate species in the grain-surface synthesis of methanol which proceeds via successive hydrogenations of CO molecules in the ice. We present here observations of methanol and its grain-surface precursors HCO, H2CO, CH3O in a sample of prestellar cores and derive their relative abundances. We find that the relative abundances HCO:H2CO:CH3O:CH3OH are constant across the core sample, close to 10:100:1:100. Our results also show that the amounts of HCO and CH3O are consistent with a gas-phase synthesis of these species from H2CO and CH3OH via radical-neutral or ion-molecule reactions followed by dissociative recombinations. Thus, while grain chemistry is necessary to explain the abundances of the parent volatile CH3OH, and possibly H2CO, the reactive species HCO and CH3O might be daughter molecules directly produced in the gas-phase.

  12. Phase control during the synthesis of nickel sulfide nanoparticles from dithiocarbamate precursors

    NASA Astrophysics Data System (ADS)

    Roffey, Anna; Hollingsworth, Nathan; Islam, Husn-Ubayda; Mercy, Maxime; Sankar, Gopinathan; Catlow, C. Richard A.; Hogarth, Graeme; de Leeuw, Nora H.

    2016-05-01

    Square-planar nickel bis(dithiocarbamate) complexes, [Ni(S2CNR2)2], have been prepared and utilised as single source precursors to nanoparticulate nickel sulfides. While they are stable in the solid-state to around 300 °C, heating in oleylamine at 230 °C, 5 mM solutions afford pure α-NiS, where the outcome is independent of the substituents. DFT calculations show an electronic effect rather than steric hindrance influences the resulting particle size. Decomposition of the iso-butyl derivative, [Ni(S2CNiBu2)2], has been studied in detail. There is a temperature-dependence of the phase of the nickel sulfide formed. At low temperatures (150 °C), pure α-NiS is formed. Upon raising the temperature, increasing amounts of β-NiS are produced and at 280 °C this is formed in pure form. A range of concentrations (from 5-50 mM) was also investigated at 180 °C and while in all cases pure α-NiS was formed, particle sizes varied significantly. Thus at low concentrations average particle sizes were ca. 100 nm, but at higher concentrations they increased to ca. 150 nm. The addition of two equivalents of tetra-iso-butyl thiuram disulfide, (iBu2NCS2)2, to the decomposition mixture was found to influence the material formed. At 230 °C and above, α-NiS was generated, in contrast to the results found without added thiuram disulfide, suggesting that addition of (iBu2NCS2)2 stabilises the metastable α-NiS phase. At low temperatures (150-180 °C) and concentrations (5 mM), mixtures of α-NiS and Ni3S4, result. A growing proportion of Ni3S4 is noted upon increasing precursor concentration to 10 mM. At 20 mM a metastable phase of nickel sulfide, NiS2 is formed and as the concentration is increased, α-NiS appears alongside NiS2. Reasons for these variations are discussed.Square-planar nickel bis(dithiocarbamate) complexes, [Ni(S2CNR2)2], have been prepared and utilised as single source precursors to nanoparticulate nickel sulfides. While they are stable in the solid-state to

  13. Effect of temperature on the reaction pathway of calcium carbonate formation via precursor phases

    NASA Astrophysics Data System (ADS)

    Purgstaller, Bettina; Mavromatis, Vasileios; Konrad, Florian; Dietzel, Martin

    2016-04-01

    It has been earlier postulated that some biogenic and sedimentary calcium carbonate (CaCO3) minerals (e.g. calcite and aragonite) are secondary in origin and have originally formed via a metastable calcium carbonate precursor phase (e.g. amorphous CaCO3, [1-2]). Such formation pathways are likely affected by various physicochemical parameters including aqueous Mg and temperature. In an effort to improve our understanding on the formation mechanism of CaCO3 minerals, precipitation experiments were carried out by the addition of a 0.6 M (Ca,Mg)Cl2 solution at distinct Mg/Ca ratios (1/4 and 1/8) into a 1 M NaHCO3 solution under constant pH conditions(8.3 ±0.1). The formation of CaCO3 was systematically examined as a function of temperature (6, 12, 18 and 25 ±0.3° C). During the experimental runs mineral precipitation was monitored by in situ Raman spectroscopy as well as by continuous sampling and analyzing of precipitates and reactive solutions. The results revealed two pathways of CaCO3 formation depending on the initial Mg/Ca ratio and temperature: (i) In experiments with a Mg/Ca ratio of 1/4 at ≤ 12° C as well as in experiments with a Mg/Ca ratio of 1/8 at ≤ 18° C, ikaite (CaCO3 6H2O) acts as a precursor phase for aragonite formation. (ii) In contrast higher temperatures induced the formation of Mg-rich amorphous CaCO3 (Mg-ACC) which was subsequently transformed to Mg-rich calcite. In situ Raman spectra showed that the transformation of Mg-ACC to Mg-calcite occurs at a higher rate (˜ 8 min) compared to that of ikaite to aragonite (> 2 h). Thus, the formation of aragonite rather than of Mg-calcite occurs due to the slower release of Ca2+and CO32- ions into the Mg-rich reactive solution during retarded ikaite dissolution. This behavior is generally consistent with the observation that calcite precipitation is inhibited at elevated aqueous Mg/Ca ratios. [1] Addadi L., Raz S. and Weiner S. (2003) Advanced Materials 15, 959-970. [2] Rodriguez-Blanco J. D

  14. Role of Precursor-Conversion Chemistry in the Crystal-Phase Control of Catalytically Grown Colloidal Semiconductor Quantum Wires.

    PubMed

    Wang, Fudong; Buhro, William E

    2017-12-26

    Crystal-phase control is one of the most challenging problems in nanowire growth. We demonstrate that, in the solution-phase catalyzed growth of colloidal cadmium telluride (CdTe) quantum wires (QWs), the crystal phase can be controlled by manipulating the reaction chemistry of the Cd precursors and tri-n-octylphosphine telluride (TOPTe) to favor the production of either a CdTe solute or Te, which consequently determines the composition and (liquid or solid) state of the Bi x Cd y Te z catalyst nanoparticles. Growth of single-phase (e.g., wurtzite) QWs is achieved only from solid catalysts (y ≪ z) that enable the solution-solid-solid growth of the QWs, whereas the liquid catalysts (y ≈ z) fulfill the solution-liquid-solid growth of the polytypic QWs. Factors that affect the precursor-conversion chemistry are systematically accounted for, which are correlated with a kinetic study of the composition and state of the catalyst nanoparticles to understand the mechanism. This work reveals the role of the precursor-reaction chemistry in the crystal-phase control of catalytically grown colloidal QWs, opening the possibility of growing phase-pure QWs of other compositions.

  15. Different Topological Quantum States in Ternary Zintl compounds: BaCaX (X = Si, Ge, Sn and Pb)

    SciT

    Wang, Lin-Lin; Kaminski, Adam; Canfield, Paul C.

    Topological quantum states require stringent combination of crystal symmetry and spin–orbit coupling (SOC) strength. Here in this paper, we report that the ternary Zintl compound series BaCaX (X = Si, Ge, Sn and Pb, Group IV) in the same crystal structure having eight valence electrons per formula unit can host two different topological quantum phases, controlled by atomic size and SOC strength. BaCaSi is a nodal-line semimetal (NLSM) with band inversion protected by mirror symmetry and hosts a strong topological insulator (TI) state when SOC is turned on, thus, a NLSM-TI phase. Moving to larger atomic sizes and heavier atoms,more » BaCaGe and BaCaSn are normal insulators (NIs); then, with the strongest SOC in BaCaPb, a different band inversion is induced, giving a strong TI phase without the need of NLSM. Thus, we also predict two types of topological transitions in a phase diagram for BaCaX: (1) NLSM-TI to NI, then to TI by tuning atomic size and SOC strength via alloying, and (2) NI or TI to NLSM-TI via pressure.« less

  16. Different Topological Quantum States in Ternary Zintl compounds: BaCaX (X = Si, Ge, Sn and Pb)

    DOE PAGES

    Wang, Lin-Lin; Kaminski, Adam; Canfield, Paul C.; ...

    2017-12-14

    Topological quantum states require stringent combination of crystal symmetry and spin–orbit coupling (SOC) strength. Here in this paper, we report that the ternary Zintl compound series BaCaX (X = Si, Ge, Sn and Pb, Group IV) in the same crystal structure having eight valence electrons per formula unit can host two different topological quantum phases, controlled by atomic size and SOC strength. BaCaSi is a nodal-line semimetal (NLSM) with band inversion protected by mirror symmetry and hosts a strong topological insulator (TI) state when SOC is turned on, thus, a NLSM-TI phase. Moving to larger atomic sizes and heavier atoms,more » BaCaGe and BaCaSn are normal insulators (NIs); then, with the strongest SOC in BaCaPb, a different band inversion is induced, giving a strong TI phase without the need of NLSM. Thus, we also predict two types of topological transitions in a phase diagram for BaCaX: (1) NLSM-TI to NI, then to TI by tuning atomic size and SOC strength via alloying, and (2) NI or TI to NLSM-TI via pressure.« less

  17. Oral citrulline as arginine precursor may be beneficial in sickle cell disease: early phase two results.

    PubMed Central

    Waugh, W. H.; Daeschner, C. W.; Files, B. A.; McConnell, M. E.; Strandjord, S. E.

    2001-01-01

    L-Arginine may be a conditionally essential amino acid in children and adolescents with sickle cell disease, particularly as required substrate in the arginine-nitric oxide pathway for endogenous nitrovasodilation and vasoprotection. Vasoprotection by arginine is mediated partly by nitric oxide-induced inhibition of endothelial damage and inhibition of adhesion and activation of leukocytes. Activated leukocytes may trigger many of the complications, including vasoocclusive events and intimal hyperplasias. High blood leukocyte counts during steady states in the absence of infection are significant laboratory risk factors for adverse complications. L-Citrulline as precursor amino acid was given orally twice daily in daily doses of approximately 0.1 g/kg in a pilot Phase II clinical trial during steady states in four homozygous sickle cell disease subjects and one sickle cell-hemoglobin C disease patient (ages 10-18). There soon resulted dramatic improvements in symptoms of well-being, raised plasma arginine levels, and reductions in high total leukocyte and high segmented neutrophil counts toward or to within normal limits. Continued L-citrulline supplementation in compliant subjects continued to lessen symptomatology, to maintain plasma arginine concentrations greater than control levels, and to maintain nearly normal total leukocyte and neutrophil counts. Side effects or toxicity from citrulline were not experienced. Oral L-citrulline may portend very useful for palliative therapy in sickle cell disease. Placebo-controlled, long-term trials are now indicated. PMID:11688916

  18. Oral citrulline as arginine precursor may be beneficial in sickle cell disease: early phase two results.

    PubMed

    Waugh, W H; Daeschner, C W; Files, B A; McConnell, M E; Strandjord, S E

    2001-10-01

    L-Arginine may be a conditionally essential amino acid in children and adolescents with sickle cell disease, particularly as required substrate in the arginine-nitric oxide pathway for endogenous nitrovasodilation and vasoprotection. Vasoprotection by arginine is mediated partly by nitric oxide-induced inhibition of endothelial damage and inhibition of adhesion and activation of leukocytes. Activated leukocytes may trigger many of the complications, including vasoocclusive events and intimal hyperplasias. High blood leukocyte counts during steady states in the absence of infection are significant laboratory risk factors for adverse complications. L-Citrulline as precursor amino acid was given orally twice daily in daily doses of approximately 0.1 g/kg in a pilot Phase II clinical trial during steady states in four homozygous sickle cell disease subjects and one sickle cell-hemoglobin C disease patient (ages 10-18). There soon resulted dramatic improvements in symptoms of well-being, raised plasma arginine levels, and reductions in high total leukocyte and high segmented neutrophil counts toward or to within normal limits. Continued L-citrulline supplementation in compliant subjects continued to lessen symptomatology, to maintain plasma arginine concentrations greater than control levels, and to maintain nearly normal total leukocyte and neutrophil counts. Side effects or toxicity from citrulline were not experienced. Oral L-citrulline may portend very useful for palliative therapy in sickle cell disease. Placebo-controlled, long-term trials are now indicated.

  19. Role of precursors and coating polymers in sol-gel chemistry toward enhanced selectivity and efficiency in solid phase microextraction.

    PubMed

    Bagheri, Habib; Piri-Moghadam, Hamed; Ahdi, Tayebeh

    2012-09-12

    To evaluate the selectivity and efficiency of solid phase microextraction (SPME) fiber coatings, synthesized by sol-gel technology, roles of precursors and coating polymers were extensively investigated. An on-line combination of capillary microextraction (CME) technique and high performance liquid chromatography (HPLC) was set up to perform the investigation. Ten different fiber coatings were synthesized in which five of them contained only the precursor and the rests were prepared using both the precursor and coating polymer. All the coatings were chemically bonded to the inner surface of copper tubes, intended to be used as the CME device and already functionalized by self-assembly monolayers of 3-(mercaptopropyl)trimethoxysilane (3MPTMOS). The selected precursors included tetramethoxysilane (TMOS), 3-(trimethoxysilyl)propylmethacrylate (TMSPMA), 3-(triethoxysilyl)-propylamine (TMSPA), 3MPTMOS, [3-(2,3-epoxypropoxy)-propyl]-trimethoxysilane (EPPTMOS) while poly(ethyleneglycol) (PEG) was chosen as the coating polymer. The effects of different precursors on the extraction efficiency and selectivity, was studied by selecting a list of compounds ranging from non-polar to polar ones, i.e. polycyclic aromatic hydrocarbon, herbicides, estrogens and triazines. The results from CME-HPLC analysis revealed that there is no significant difference between precursors, except TMOS, in which has the lowest extraction efficiency. Most of the selected precursors have rather similar interactions toward the selected analytes which include Van der Walls, dipole-dipole and hydrogen bond while TMOS has only dipole-dipole interaction and therefore the least efficiency. TMOS is silica but the other sorbents are organically modified silica (ORMOSIL). Our investigation revealed that it is rather impossible to prepare a selective coating using conventional sol-gel methodologies. The comparison study performed among the fiber coatings contained only a precursor and those synthesized by a

  20. On-fiber furan formation from volatile precursors: a critical example of artefact formation during Solid-Phase Microextraction.

    PubMed

    Adams, An; Van Lancker, Fien; De Meulenaer, Bruno; Owczarek-Fendor, Agnieszka; De Kimpe, Norbert

    2012-05-15

    For the analysis of furan, a possible carcinogen formed during thermal treatment of food, Solid-Phase Microextraction (SPME) is a preferred and validated sampling method. However, when volatile furan precursors are adsorbed on the carboxen/PDMS fiber, additional amounts of furan can be formed on the fiber during thermal desorption, as shown here for 2-butenal and furfural. No significant increase in furan amounts was found upon heating the furan precursor 2-butenal, indicating that the furan amounts formed during precursor heating experiments are negligible as compared to the additional amounts of furan formed during fiber desorption. This artefactual furan formation increased with increasing desorption time, but especially with increasing desorption temperature. Although this effect was most pronounced on the Carboxen/PDMS SPME-fiber, it was also noted on two other SPME-fibers tested (PDMS and DVB/Carboxen/PDMS). The general impact on furan data from food and model systems in literature will depend on the amounts of volatile precursors present, but will probably remain limited. However, considering the importance of this worldwide food contaminant, special care has to be taken during SPME-analysis of furan. Especially when performing precursor studies, static headspace sampling should preferably be applied for furan analysis. Copyright © 2012 Elsevier B.V. All rights reserved.

  1. Deformation and failure of single- and multi-phase silicate liquids: seismic precursors and mechanical work

    NASA Astrophysics Data System (ADS)

    Vasseur, Jeremie; Lavallée, Yan; Hess, Kai-Uwe; Wassermann, Joachim; Dingwell, Donald B.

    2013-04-01

    Along with many others, volcanic unrest is regarded as a catastrophic material failure phenomenon and is often preceded by diverse precursory signals. Although a volcanic system intrinsically behave in a non-linear and stochastic way, these precursors display systematic evolutionary trends to upcoming eruptions. Seismic signals in particular are in general dramatically increasing prior to an eruption and have been extensively reported to show accelerating rates through time, as well as in the laboratory before failure of rock samples. At the lab-scale, acoustic emissions (AE) are high frequency transient stress waves used to track fracture initiation and propagation inside a rock sample. Synthesized glass samples featuring a range of porosities (0 - 30%) and natural rock samples from volcán de Colima, Mexico, have been failed under high temperature uniaxial compression experiments at constant stresses and strain rates. Using the monitored AEs and the generated mechanical work during deformation, we investigated the evolutionary trends of energy patterns associated to different degrees of heterogeneity. We observed that the failure of dense, poorly porous glasses is achieved by exceeding elevated strength and thus requires a significant accumulation of strain, meaning only pervasive small-scale cracking is occurring. More porous glasses as well as volcanic samples need much lower applied stress and deformation to fail, as fractures are nucleating, propagating and coalescing into localized large-scale cracks, taking the advantage of the existence of numerous defects (voids for glasses, voids and crystals for volcanic rocks). These observations demonstrate that the mechanical work generated through cracking is efficiently distributed inside denser and more homogeneous samples, as underlined by the overall lower AE energy released during experiments. In contrast, the quicker and larger AE energy released during the loading of heterogeneous samples shows that the

  2. Magnetic Fluctuations, Precursor Phenomena, and Phase Transition in MnSi under a Magnetic Field

    NASA Astrophysics Data System (ADS)

    Pappas, C.; Bannenberg, L. J.; Lelièvre-Berna, E.; Qian, F.; Dewhurst, C. D.; Dalgliesh, R. M.; Schlagel, D. L.; Lograsso, T. A.; Falus, P.

    2017-07-01

    The reference chiral helimagnet MnSi is the first system where Skyrmion lattice correlations have been reported. At a zero magnetic field the transition at TC to the helimagnetic state is of first order. Above TC, in a region dominated by precursor phenomena, neutron scattering shows the buildup of strong chiral fluctuating correlations over the surface of a sphere with radius 2 π /ℓ, where ℓ is the pitch of the helix. It has been suggested that these fluctuating correlations drive the helical transition to first order following a scenario proposed by Brazovskii for liquid crystals. We present a comprehensive neutron scattering study under magnetic fields, which provides evidence that this is not the case. The sharp first order transition persists for magnetic fields up to 0.4 T whereas the fluctuating correlations weaken and start to concentrate along the field direction already above 0.2 T. Our results thus disconnect the first order nature of the transition from the precursor fluctuating correlations. They also show no indication for a tricritical point, where the first order transition crosses over to second order with increasing magnetic field. In this light, the nature of the first order helical transition and the precursor phenomena above TC, both of general relevance to chiral magnetism, remain an open question.

  3. A Dual-Phase Ceramic Membrane with Extremely High H2 Permeation Flux Prepared by Autoseparation of a Ceramic Precursor.

    PubMed

    Cheng, Shunfan; Wang, Yanjie; Zhuang, Libin; Xue, Jian; Wei, Yanying; Feldhoff, Armin; Caro, Jürgen; Wang, Haihui

    2016-08-26

    A novel concept for the preparation of multiphase composite ceramics based on demixing of a single ceramic precursor has been developed and used for the synthesis of a dual-phase H2 -permeable ceramic membrane. The precursor BaCe0.5 Fe0.5 O3-δ decomposes on calcination at 1370 °C for 10 h into two thermodynamically stable oxides with perovskite structures: the cerium-rich oxide BaCe0.85 Fe0.15 O3-δ (BCF8515) and the iron-rich oxide BaCe0.15 Fe0.85 O3-δ (BCF1585), 50 mol % each. In the resulting dual-phase material, the orthorhombic perovskite BCF8515 acts as the main proton conductor and the cubic perovskite BCF1585 as the main electron conductor. The dual-phase membrane shows an extremely high H2 permeation flux of 0.76 mL min(-1)  cm(-2) at 950 °C with 1.0 mm thickness. This auto-demixing concept should be applicable to the synthesis of other ionic-electronic conducting ceramics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Amorphous surface layer versus transient amorphous precursor phase in bone - A case study investigated by solid-state NMR spectroscopy.

    PubMed

    Von Euw, Stanislas; Ajili, Widad; Chan-Chang, Tsou-Hsi-Camille; Delices, Annette; Laurent, Guillaume; Babonneau, Florence; Nassif, Nadine; Azaïs, Thierry

    2017-09-01

    The presence of an amorphous surface layer that coats a crystalline core has been proposed for many biominerals, including bone mineral. In parallel, transient amorphous precursor phases have been proposed in various biomineralization processes, including bone biomineralization. Here we propose a methodology to investigate the origin of these amorphous environments taking the bone tissue as a key example. This study relies on the investigation of a bone tissue sample and its comparison with synthetic calcium phosphate samples, including a stoichiometric apatite, an amorphous calcium phosphate sample, and two different biomimetic apatites. To reveal if the amorphous environments in bone originate from an amorphous surface layer or a transient amorphous precursor phase, a combined solid-state nuclear magnetic resonance (NMR) experiment has been used. The latter consists of a double cross polarization 1 H→ 31 P→ 1 H pulse sequence followed by a 1 H magnetization exchange pulse sequence. The presence of an amorphous surface layer has been investigated through the study of the biomimetic apatites; while the presence of a transient amorphous precursor phase in the form of amorphous calcium phosphate particles has been mimicked with the help of a physical mixture of stoichiometric apatite and amorphous calcium phosphate. The NMR results show that the amorphous and the crystalline environments detected in our bone tissue sample belong to the same particle. The presence of an amorphous surface layer that coats the apatitic core of bone apatite particles has been unambiguously confirmed, and it is certain that this amorphous surface layer has strong implication on bone tissue biogenesis and regeneration. Questions still persist on the structural organization of bone and biomimetic apatites. The existing model proposes a core/shell structure, with an amorphous surface layer coating a crystalline bulk. The accuracy of this model is still debated because amorphous calcium

  5. Strategies to indium nitride and gallium nitride nanoparticles: Low-temperature, solution-phase and precursor routes

    NASA Astrophysics Data System (ADS)

    Dingman, Sean Douglas

    I present new strategies to low-temperature solution-phase synthesis of indium and gallium nitride (InN and GaN) ceramic materials. The strategies include: direct conversion of precursor molecules to InN by pyrolysis, solution-phase synthesis of nanostructured InN fibers via molecular precursors and co-reactants, and synthesis of powders through reactions derived from molten-salt chemistry. Indium nitride powders are prepared by pyrolysis of the precursors R 2InN3 (R = t-Bu (1), i-Amyl(2), Et(3), i-Pr( 4)). The precursors are synthesized via azide-alkoxide exchange of R2InOMe with Me3SiN3. The precursors are coordination polymers containing five-coordinate indium centers. Pyrolysis of 1 and 2 under N2 at 400°C yields powders consisting primarily of InN with average crystal sizes of 15--35 nm. 1 yields nanocrystalline InN with average particle sizes of 7 nm at 250°C. 3 and 4 yield primarily In metal from pyrolysis. Refluxing 1 in diisopropylbenzene (203°C) in the presence of primary amines yields InN nanofibers 10--100 nm in length. InN nanofibers of up to 1 mum can be synthesized by treating 1 with 1,1-dimethylhydrazine (DMHy) The DMHy appears to control the fiber length by acting as a secondary source of active nitrogen in order to sustain fiber growth. The resulting fibers are attached to droplets of indium metal implying a solution-liquid-solid growth mechanism. Precursor 4 yields crystalline InN whiskers when reacted with DMHy. Reactions of 4 with reducing agents such as HSnBu3, yield InN nanoparticles with an average crystallite size of 16 nm. Gallium precursors R2GaN3 (R = t-Bu( 5), Me3SiCH2(6) and i-Pr( 7)), synthesized by azide-alkoxide exchange, are found to be inert toward solution decomposition and do not yield GaN. These compounds are molecular dimers and trimers unlike the indium analogs. Compound 6 displays a monomer-dimer equilibrium in benzene solution, but exists as a solid-state trimer. InN powders are also synthesized by reactions of InCl3 and

  6. Effect of Precursor Selection on the Photocatalytic Performance of Indium Oxide Nanomaterials for Gas-Phase CO 2 Reduction

    DOE PAGES

    Hoch, Laura B.; He, Le; Qiao, Qiao; ...

    2016-06-01

    Nonstoichiometric indium oxide nanoparticles, In 2O 3–x(OH)y, have been shown to function as active photocatalysts for gas-phase CO 2 reduction under simulated solar irradiation. We demonstrate that the choice of starting material has a strong effect on the photocatalytic activity of indium oxide nanoparticles. We also examine three indium oxide materials prepared via the thermal decomposition of either indium(III) hydroxide or indium(III) nitrate and correlate their stability and photocatalytic activity to the number and type of defect present in the material. Furthermore, we use 13CO 2 isotope-tracing experiments to clearly identify the origins of the observed carbon-containing products. Significantly, wemore » find that the oxidizing nature of the precursor anion has a substantial impact on the defect formation within the sample. Our study demonstrates the importance of surface defects in designing an active heterogeneous photocatalyst and provides valuable insight into key parameters for the precursor design, selection, and performance optimization of materials for gas-phase CO 2 reduction.« less

  7. Precursor dynamics in the ferroelectric phase transition of barium titanate single crystals studied by Brillouin light scattering

    NASA Astrophysics Data System (ADS)

    Ko, Jae-Hyeon; Kim, Tae Hyun; Roleder, K.; Rytz, D.; Kojima, Seiji

    2011-09-01

    The acoustic anomalies and precursor dynamics of high-quality barium titanate single crystals were investigated by Brillouin light scattering and the birefringence measurements in the paraelectric phase above the cubic-to-tetragonal ferroelectric phase transition temperature (Tc). Two elastic stiffness coefficients C11 and C44, the related sound velocities, and their absorption coefficients were determined from Tc to 400∘C for the first time. The longitudinal acoustic (LA) mode showed a substantial softening over a wide temperature range above Tc which was accompanied by a remarkable increase in the acoustic damping as well as growth of central peaks. The broad central peak (CP) exhibited a two-mode and one-mode behavior in the paraelectric and ferroelectric phase, respectively, which was consistent with recent far-infrared reflectivity measurements and first-principle-based calculations [Ponomareva , Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.77.012102 77, 012102 (2008)]. The acoustic anomalies and CP behavior were correlated with the anomalous birefringence, piezoelectric effect, and the deviation of the Curie-Weiss law observed from the same crystal. This strongly indicates similarity between the dynamics of polar clusters in typical ferroelectrics and the dynamics of polar nanoregions in relaxors, consistent with recent acoustic emission measurements [Dul’kin , Appl. Phys. Lett.APPLAB0003-695110.1063/1.3464968 97, 032903 (2010)]. The relaxation times estimated from the central peak and the LA mode anomalies exhibited similar temperature dependences with comparable orders of magnitude, indicating that the polarization fluctuations due to the precursor polar clusters couples to the LA mode through density fluctuations. All these anomalies share common microscopic origin, correlated Ti off-centered motions forming polar clusters having local symmetry breaking in the paraelectric phase. The existence of the polar clusters were directly evidenced by the

  8. Structural and spectroscopic characterization of irreversible phase changes in rapidly heated precursors of europium-doped titania nanoparticles

    NASA Astrophysics Data System (ADS)

    Gunawidjaja, Ray; Anderson, Benjamin R.; Eilers, Hergen

    2018-02-01

    We observe temperature-dependent phase changes in a precursor of europium-doped titania (p-Eu:TiO2) that is prepared via precipitation and is laser-heated to temperatures between 473 K and 1246 K within sub-second heating durations. The phase changes are characterized using X-ray diffraction and site-selective photoluminescence spectroscopy. We find that upon heating, the initially amorphous p-Eu:TiO2 first transforms into the anatase phase and then into a mixed anatase/rutile phase. These phase transformations change the local environment of the dopant Eu3+ ions resulting in modifications to the Eu3+ ions spectroscopic properties, with the modifications occurring for calcination temperatures above approximately 573 K following sub-second durations. These results demonstrate the temperature sensing ability of p-Eu:TiO2 nanoparticles for use in sub-second heating events. Moreover, at 573 K this temperature is lower than other host materials that we have evaluated (i.e., La2O3, ZrO2 and Y2O3).

  9. Preparation of niobium based oxynitride nanosheets by exfoliation of Ruddlesden-Popper phase precursor

    NASA Astrophysics Data System (ADS)

    da Silva Maia, Ary; Cheviré, François; Demange, Valérie; Bouquet, Valérie; Pasturel, Mathieu; Députier, Stéphanie; Lebullenger, Ronan; Guilloux-Viry, Marylline; Tessier, Franck

    2016-04-01

    A new oxynitride Ruddlesden-Popper phase K1.6Ca2Nb3O9.4N0.6.1.1H2O was synthesized by the topochemical ammonolysis reaction at 700 °C from the oxide Dion-Jacobson phase KCa2Nb3O10 in the presence of K2CO3. The oxynitride showed good stability with a little loss of nitrogen, even after a few months of exposure to air. Its crystal structure was solved by Rietveld refinement of X-ray powder diffraction data in space group P4/mmm and considering a two-phase mixture, due to the difference in the degree of hydration, with a = 3.894(2) Å and c = 17.90(8) Å for the most hydrated phase and a = 3.927(6) Å and c = 17.09(2) Å for the less one. Optical band gaps were measured by diffuse reflectance in the UV-Visible range indicating a red shift of Eg to the visible region. The oxynitride layered perovskite was then protonated and exfoliated into nanosheets. TEM images and SAED patterns of the nanosheets proved that exfoliation was successful, showing lattice parameters quite compatible with the Rietveld refinement.

  10. Viral Infection Induces Expression of Novel Phased MicroRNAs from Conserved Cellular MicroRNA Precursors

    PubMed Central

    Zhang, Jiayao; Zhao, Shuqi; Zheng, Hong; Gao, Ge; Wei, Liping; Li, Yi

    2011-01-01

    RNA silencing, mediated by small RNAs including microRNAs (miRNAs) and small interfering RNAs (siRNAs), is a potent antiviral or antibacterial mechanism, besides regulating normal cellular gene expression critical for development and physiology. To gain insights into host small RNA metabolism under infections by different viruses, we used Solexa/Illumina deep sequencing to characterize the small RNA profiles of rice plants infected by two distinct viruses, Rice dwarf virus (RDV, dsRNA virus) and Rice stripe virus (RSV, a negative sense and ambisense RNA virus), respectively, as compared with those from non-infected plants. Our analyses showed that RSV infection enhanced the accumulation of some rice miRNA*s, but not their corresponding miRNAs, as well as accumulation of phased siRNAs from a particular precursor. Furthermore, RSV infection also induced the expression of novel miRNAs in a phased pattern from several conserved miRNA precursors. In comparison, no such changes in host small RNA expression was observed in RDV-infected rice plants. Significantly RSV infection elevated the expression levels of selective OsDCLs and OsAGOs, whereas RDV infection only affected the expression of certain OsRDRs. Our results provide a comparative analysis, via deep sequencing, of changes in the small RNA profiles and in the genes of RNA silencing machinery induced by different viruses in a natural and economically important crop host plant. They uncover new mechanisms and complexity of virus-host interactions that may have important implications for further studies on the evolution of cellular small RNA biogenesis that impact pathogen infection, pathogenesis, as well as organismal development. PMID:21901091

  11. Comparison of three solid phase extraction sorbents for the isolation of THM precursors from manitoban surface waters.

    PubMed

    Goss, C D; Wiens, R; Gorczyca, B; Gough, K M

    2017-02-01

    Three prepackaged solid phase extraction (SPE) cartridges: two modified styrene divinylbenzene, Bond Elut ENV and Bond Elut PPL (Varian), and one N-vinylpyrrolidone (Strata-X, Phenomenex), were assessed for isolation of THM precursors from three surface waters in Manitoba, Canada. The dissolved organic matter (DOM) from the La Salle River (LR), Lake Winnipegosis (LW) and the Waterhen River (WR) were fractionated into hydrophobic (HPO) and hydrophilic (HPI) parts. ENV isolated less DOM (LR = 46.6 ± 1.5%; LW = 36.2 ± 1.4%; WR = 28.6 ± 2.2%) compared to PPL (LR = 50.2 ± 4.4%; LW = 47.9 ± 2.2%; WR = 37.3 ± 2.8%) and Strata (LR = 46.4% ± 1.0; LW = 51.6 ± 0.3%; WR = 31.9 ± 3.9%). The HPO fraction isolated by each SPE was characterized using Fourier Transform Infrared (FTIR) spectrochemical imaging. The FTIR spectra confirmed the HPO fractions were typical of humic-material and largely resembled fulvic acids; however, the PPL and Strata HPO isolates contained slightly more polysaccharides. The THM formation potential (THMFP) confirmed that the HPO fraction formed more THMs than the HPI. The HPO fraction isolated using ENV was found to have the lowest THMFP of all three SPEs in each waterbody; however, the specific THMFP (μgTHM/mgDOM) results indicated that ENV isolated THM precursors more effectively, as the Strata and PPL isolated a greater amount of non-THM forming material. All three SPE showed significant potential for implementation at water treatment plants as a simple tool to monitor THM precursors in source waters, enabling operators to adapt processes to improve drinking water quality. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Ab initio 27Al NMR chemical shifts and quadrupolar parameters for Al2O3 phases and their precursors

    NASA Astrophysics Data System (ADS)

    Ferreira, Ary R.; Küçükbenli, Emine; Leitão, Alexandre A.; de Gironcoli, Stefano

    2011-12-01

    The gauge-including projector augmented wave (GIPAW) method, within the density functional theory (DFT) generalized gradient approximation (GGA) framework, is applied to compute solid state NMR parameters for 27Al in the α, θ, and κ aluminium oxide phases and their gibbsite and boehmite precursors. The results for well established crystalline phases compare very well with available experimental data and provide confidence in the accuracy of the method. For γ-alumina, four structural models proposed in the literature are discussed in terms of their ability to reproduce the experimental spectra also reported in the literature. Among the considered models, the Fd3¯m structure proposed by Paglia [Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.71.224115 71, 224115 (2005)] shows the best agreement. We attempt to link the theoretical NMR parameters to the local geometry. Chemical shifts depend on coordination number but no further correlation is found with geometrical parameters. Instead, our calculations reveal that, within a given coordination number, a linear correlation exists between chemical shifts and Born effective charges.

  13. Evidence for negative thermal expansion in the superconducting precursor phase SmFeAsO

    NASA Astrophysics Data System (ADS)

    Zhou, H. D.; Sarte, P. M.; Conner, B. S.; Balicas, L.; Wiebe, C. R.; Chen, X. H.; Wu, T.; Wu, G.; Liu, R. H.; Chen, H.; Fang, D. F.

    2018-03-01

    The fluorine-doped rare-earth iron oxypnictide series SmFeAsO1-x F x (0 ≤slant x ≤slant 0.10) was investigated with high resolution powder x-ray scattering. In agreement with previous studies (Margadonna et al 2009 Phys. Rev. B. 79 014503), the parent compound SmFeAsO exhibits a tetragonal-to-orthorhombic structural distortion at T{S}   =  130 K which is rapidly suppressed by x ≃ 0.10 deep within the superconducting dome. The change in unit cell symmetry is followed by a previously unreported magnetoelastic distortion at 120 K. The temperature dependence of the thermal expansion coefficient αV reveals a rich phase diagram for SmFeAsO: (i) a global minimum at 125 K corresponds to the opening of a spin-density wave instability as measured by pump-probe femtosecond spectroscopy (Mertelj et al 2010 Phys. Rev. B 81 224504) whilst (ii) a global maximum at 110 K corresponds to magnetic ordering of the Sm and Fe sublattices as measured by magnetic x-ray scattering (Nandi et al 2011 Phys. Rev. B 84 055419). At much lower temperatures than T{N} , SmFeAsO exhibits a significant negative thermal expansion on the order of  -40 ppm · K-1 in contrast to the behaviour of other rare-earth oxypnictides such as PrFeAsO (Kimber et al 2008 Phys. Rev. B 78 140503) and the actinide oxypnictide NpFeAsO (Klimczuk et al 2012 Phys. Rev. B 85 174506) where the onset of αV < 0 only appears in the vicinity of magnetic ordering. Correlating this feature with the temperature and doping dependence of the resistivity and the unit cell parameters, we interpret the negative thermal expansion as being indicative of the possible condensation of itinerant electrons accompanying the opening of a SDW gap, consistent with transport measurements (Tropeano et al 2009 Supercond. Sci. Technol. 22 034004).

  14. Gas-phase Precursors to Anthropogenic SOA: Using the MCM to Probe Detailed Observations of Aromatic Photo-oxidation

    NASA Astrophysics Data System (ADS)

    Rickard, A. R.; Wyche, K. P.; Metzger, A.; Monks, P. S.; Ellis, A. M.; Baltensperger, U.; Pilling, M. J.; Jenkin, M. E.

    2008-12-01

    The formation of photochemical ozone and particulate matter are major priorities in the determination of European air quality policies. Predictions of the future state of the atmosphere and the development of appropriate mitigation strategies rely on models, which necessarily incorporate chemistry. The Master Chemical Mechanism (MCM, http://mcm.leeds.ac.uk/MCM) is a near-explicit chemical mechanism originally conceived to model ozone formation in Europe but now also employed as a benchmark mechanism in a wide variety of applications where chemical detail is required. The MCM currently describes the detailed gas- phase tropospheric degradation of a 135 primary emitted volatile organic compounds (VOCs) leading to a mechanism containing ca. 5900 species and 13500 reactions. In order that the MCM continues to be a state-of-the-art resource for the atmospheric science community it resides under a constant regime of evaluation, development and improvement. Individual VOC photochemical mechanisms are evaluated using data obtained, under a variety of atmospheric conditions, from highly instrumented smog chambers. Smog chamber experiments are crucial, not only for mechanism evaluation, but also for mechanism development. Findings obtained from combined model and chamber studies can additionally provide key insight for guiding the directions of future laboratory experiments. Recently, the MCM was updated to MCMv3.1 in order to take into account recent advancements in the understanding of aromatic photo-oxidation, an important class of anthropogenic VOCs. As well as constituting precursors to secondary organic aerosol (SOA), aromatics generally have high photochemical ozone creation potentials (POCPs) and hence contribute significantly towards tropospheric ozone formation. In the work presented, a detailed gas-phase photochemical chamber box model, incorporating the MCMv3.1 degradation mechanism for 1,3,5-trimethylbenzene (TMB), has been used to simulate data measured during

  15. Formation of crystalline InGaO₃(ZnO)n nanowires via the solid-phase diffusion process using a solution-based precursor.

    PubMed

    Guo, Yujie; Van Bilzen, Bart; Locquet, Jean Pierre; Seo, Jin Won

    2015-12-11

    One-dimensional single crystalline InGaO3(ZnO)n (IGZO) nanostructures have great potential for various electrical and optical applications. This paper demonstrates for the first time, to our knowledge, a non-vacuum route for the synthesis of IGZO nanowires by annealing ZnO nanowires covered with solution-based IGZO precursor. This method results in nanowires with highly periodic IGZO superlattice structure. The phase transition of IGZO precursor during thermal treatment was systematically studied. Transmission electron microscopy studies reveal that the formation of the IGZO structure is driven by anisotropic inter-diffusion of In, Ga, and Zn atoms, and also by the crystallization of the IGZO precursor. Optical measurements using cathodoluminescence and UV-vis spectroscopy confirm that the nanowires consist of the IGZO compound with wide optical band gap and suppressed luminescence.

  16. Effect of phase assemblage of precursor on the fabrication process and properties of Bi2223 tape sheathed with Ag-alloy

    NASA Astrophysics Data System (ADS)

    Nakamura, Y.; Shioiri, T.; Kurihara, C.; Machida, T.; Inada, R.; Oota, A.

    2008-09-01

    The use of alloy sheath is effective to increase the strength of Ag-sheathed Bi2223 tapes. However, the Jc value of alloy sheathed tapes was not high enough since the undesired reaction to form impurity phases and the change in formation rate of Bi2223 were disturbed by the microstructure of the filaments . In this study, the effect of 2223 contents in precursor on the formation and property of Bi2223 tapes sheathed with Ag-Mg alloy was investigated. The conversion rate of Bi2223 from Bi2212 was increased by the addition of Bi2223 phase in precursor but the conversion rate in Ag-Mg alloy sheathed tapes was slower than that in the Ag-Cu alloy sheathed tapes. This reduction of conversion speed of Bi2223 may be attributed to the decrease in the growth rate of Bi2223 crystals in Ag-Mg alloy sheath. Since the tapes with small Bi2223 crystals after first sintering showed many outgrowths after final sintering, the formation of outgrowth would be caused in the case of small crystal size. The Jc value of 2.2 × 10 4 A/cm 2 was achieved in the samples using the precursor with 10 wt.% 2223. The high Jc value can be achieved by the proper control of precursor condition including the contents of Bi2223 and corresponding heat treatment pattern in Ag-Mg alloy sheathed tapes.

  17. ­­Secondary organic aerosol formation from photo-oxidation of wood combustion emissions: Characterization of gas phase precursors and their link to SOA budget

    NASA Astrophysics Data System (ADS)

    Bhattu, D.; Stefenelli, G.; Zotter, P.; Zhou, J.; Nussbaumer, T.; Bertrand, A.; Marchand, N.; Termine-Roussel, B.; Baltensperger, U.; Slowik, J.; Prevot, A. S.; El-Haddad, I.; Dommen, J.

    2016-12-01

    Current legislation limits the emission of particulate matter, but does not regulate the precursors potentially forming secondary organic aerosol (SOA). Recent literature has shown that only 22 non-traditional SOA precursors from residential wood combustion explains 84-116% of the observed SOA mass whereas traditional precursors in the models account for only 3-27% of the SOA mass (Bruns et al., 2016). Investigation of gas phase emissions from wood combustion and their SOA formation potential have largely focused on single combustion devices with limited operating conditions. As, both primary emissions and SOA formation is a strong function of device type, load, fuel and operating conditions, we have performed a detailed chamber study investigating the gas-phase precursors from beech wood using three combustion devices namely a pellet boiler (combustion conditions: optimum, lack and excess of oxygen), an industrial wood chip grate boiler (30% and 100% power), and a log wood stove (varying fuel load and moisture content) using a potential aerosol mass reactor (PAM) with varying OH exposure. The short residence time in the reactor allowed a time resolved picture of SOA production potential and reduced wall losses. The main aim of this study is to characterize the primary and aged gaseous emissions and investigate their SOA formation potential depending on their mass yield, molecular structures, functional groups and OH reactivity in order to ascertain the contribution of residential wood burning in total carbonaceous OA budget. The physical and chemical effects of different OA aging conditions were monitored using an SMPS, an Aethalometer, an HR-ToF-AMS, as well as a PTR-ToF-MS and other gas monitors. In pellet boiler, significant SOA mass enhancement is observed in excess oxygen conditions compared to optimum and oxygen deprived conditions. Highest gas phase emissions from wood stove are observed at cold start (start of each burn cycle) and lowest in burn out phase

  18. Fabrication of Lanthanum Telluride 14-1-11 Zintl High-Temperature Thermoelectric Couple

    NASA Technical Reports Server (NTRS)

    Ravi, Vilupanur A.; Li, Billy Chun-Yip; Fleurial, Pierre; Star, Kurt

    2010-01-01

    The development of more efficient thermoelectric couple technology capable of operating with high-grade heat sources up to 1,275 K is key to improving the performance of radioisotope thermoelectric generators. Lanthanum telluride La3-xTe4 and 14-1-11 Zintls (Yb14MnSb11) have been identified as very promising materials. The fabrication of advanced high-temperature thermoelectric couples requires the joining of several dissimilar materials, typically including a number of diffusion bonding and brazing steps, to achieve a device capable of operating at elevated temperatures across a large temperature differential (up to 900 K). A thermoelectric couple typically comprises a heat collector/ exchanger, metallic interconnects on both hot and cold sides, n-type and ptype conductivity thermoelectric elements, and cold-side hardware to connect to the cold-side heat rejection and provide electrical connections. Differences in the physical, mechanical, and chemical properties of the materials that make up the thermoelectric couple, especially differences in the coefficients of thermal expansion (CTE), result in undesirable interfacial stresses that can lead to mechanical failure of the device. The problem is further complicated by the fact that the thermoelectric materials under consideration have large CTE values, are brittle, and cracks can propagate through them with minimal resistance. The inherent challenge of bonding brittle, high-thermal-expansion thermoelectric materials to a hot shoe material that is thick enough to carry the requisite electrical current was overcome. A critical advantage over prior art is that this device was constructed using all diffusion bonds and a minimum number of assembly steps. The fabrication process and the materials used are described in the following steps: (1) Applying a thin refractory metal foil to both sides of lanthanum telluride. To fabricate the n-type leg of the advanced thermoelectric couple, the pre-synthesized lanthanum

  19. [Simultaneous determination of nine perfluorinated compound precursors in atmospheric precipitation by solid phase extraction and ultra performance liquid chromatography with tandem mass spectrometry].

    PubMed

    Zhang, Ming; Tang, Fangliang; Xu, Jianfen; Yu, Bo; Zhang, Wei; Yao, Jianliang; Hu, Minhua

    2017-10-08

    A high-throughput detection method has been developed for the determination of nine perfluorinated compound precursors (PFCPs) in atmospheric precipitation by solid phase extraction-ultra performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (SPE-UPLC-ESI-MS/MS). The atmospheric precipitation samples were concentrated and purified with HLB solid phase extraction cartridges. The UPLC separation was performed on an HSS T 3 column (100 mm×2.1 mm, 1.7 μm) utilizing a gradient elution program of methanol and water as the mobile phases at a flow rate of 0.2 mL/min. The MS/MS detection was performed under negative electrospray ionization (ESI - ) in multiple reaction monitoring (MRM) mode. Good linearity was observed in the range of 0.05-5.00 μg/L, 0.50-50.0 μg/L or 5.00-500 μg/L with correlation coefficients from 0.9921 to 0.9995. The limits of detection (LODs) for the nine perfluorinated compound precursors were in the ranges of 0.05-7.9 ng/L. The recoveries ranged from 76.0% to 106% with the relative standard deviations between 0.72% and 13.7%. This method is characterized by high sensitivity and precision, extensive analytical range and quick analytical rate, and can be applied for the analysis of perfluorinated compound precursors in atmospheric precipitation.

  20. Combining single source chemical vapour deposition precursors to explore the phase space of titanium oxynitride thin films.

    PubMed

    Rees, Kelly; Lorusso, Emanuela; Cosham, Samuel D; Kulak, Alexander N; Hyett, Geoffrey

    2018-02-14

    In this paper we report on a novel chemical vapour deposition approach to the formation and control of composition of mixed anion materials, as applied to titanium oxynitride thin films. The method used is the aerosol assisted chemical vapour deposition (AACVD) of a mixture of single source precursors. To explore the titanium-oxygen-nitrogen system the single source precursors selected were tetrakis(dimethylamido) titanium and titanium tetraisopropoxide which individually are precursors to thin films of titanium nitride and titanium dioxide respectively. However, by combining these precursors in specific ratios in a series of AACVD reactions at 400 °C, we are able to deposit thin films of titanium oxynitride with three different structure types and a wide range of compositions. Using this precursor system we can observe films of nitrogen doped anatase, with 25% anion doping of nitrogen; a new composition of pseudobrookite titanium oxynitride with a composition of Ti 3 O 3.5 N 1.5 , identified as being a UV photocatalyst; and rock-salt titanium oxynitride in the range TiO 0.41 N 0.59 to TiO 0.05 N 0.95 . The films were characterised using GIXRD, WDX and UV-vis spectroscopy, and in the case of the pseudobrookite films, assessed for photocatalytic activity. This work shows that a so-called dual single-source CVD approach is an effective method for the deposition of ternary mixed anion ceramic films through simple control of the ratio of the precursors, while keeping all other experimental parameters constant.

  1. Phase formation of V{sub 2}O{sub 5}.xNb{sub 2}O{sub 5} compounds via gels and freeze-dried precursors

    SciT

    Langbein, Hubert; Mayer-Uhma, Tobias

    2009-03-05

    An X-ray powder diffraction study of the phase formation in the system V{sub 2}O{sub 5}/Nb{sub 2}O{sub 5} is performed. Freeze-dried ammonium vanadate and ammonium oxalato niobate, alkoxide-derived xerogels and a mixture of active oxides are used as precursors to compare the resulting phase composition. Thermal decomposition of the freeze-dried precursor is monitored with DTA/TG and mass spectrometry. In the quasi-binary system V{sub 2}O{sub 5}-Nb{sub 2}O{sub 5} metastable VNbO{sub 5}, V{sub 4}Nb{sub 18}O{sub 55}, VNb{sub 9}O{sub 25} and solid solutions of V{sub 2}O{sub 5} in TT-Nb{sub 2}O{sub 5} as also thermodynamically stable VNb{sub 9}O{sub 25} exist. The thermal decomposition of freeze-driedmore » vanadate-oxalatoniobate solution allows the synthesis of all these phases in a relative simple manner. Structural relationships between an intermediate phase and the product, or, in the case of solid-state reactions, between one of the starting oxide and the product, favour the desired reaction. Therefore, the structure of a former phase influences or directs the structure of the product similar to a topotactic reaction.« less

  2. ACBC to Balcite: Bioinspired Synthesis of a Highly Substituted High-Temperature Phase from an Amorphous Precursor

    SciT

    Whittaker, Michael L.; Joester, Derk

    2017-04-28

    Energy-efficient synthesis of materials locked in compositional and structural states far from equilibrium remains a challenging goal, yet biomineralizing organisms routinely assemble such materials with sophisticated designs and advanced functional properties, often using amorphous precursors. However, incorporation of organics limits the useful temperature range of these materials. Herein, the bioinspired synthesis of a highly supersaturated calcite (Ca0.5Ba0.5CO3) called balcite is reported, at mild conditions and using an amorphous calcium–barium carbonate (ACBC) (Ca1- x Ba x CO3·1.2H2O) precursor. Balcite not only contains 50 times more barium than the solubility limit in calcite but also displays the rotational disorder on carbonate sitesmore » that is typical for high-temperature calcite. It is significantly harder (30%) and less stiff than calcite, and retains these properties after heating to elevated temperatures. Analysis of balcite local order suggests that it may require the formation of the ACBC precursor and could therefore be an example of nonclassical nucleation. These findings demonstrate that amorphous precursor pathways are powerfully enabling and provide unprecedented access to materials far from equilibrium, including high-temperature modifications by room-temperature synthesis.« less

  3. Tuning the morphology, luminescence and magnetic properties of hexagonal-phase NaGdF4: Yb, Er nanocrystals via altering the addition sequence of the precursors

    NASA Astrophysics Data System (ADS)

    Zhao, Shuwen; Xia, Donglin; Zhao, Ruimin; Zhu, Hao; Zhu, Yiru; Xiong, Yuda; Wang, Youfa

    2017-01-01

    Hexagonal-phase NaGdF4: Yb, Er upconversion nanocrystals (UCNCs) with tunable morphology and properties were successfully prepared via a thermal decomposition method. The influences of the adding sequence of the precursors on the morphology, chemical composition, luminescence and magnetic properties were investigated by transmission electron microscopy (TEM), inductively coupled plasma-atomic emission spectrometry (ICP-AES), upconversion (UC) spectroscopy, and a vibrating sample magnetometer (VSM). It was found that the resulting nanocrystals, with different sizes ranging from 24 to 224 nm, are in the shape of spheres, hexagonal plates and flakes; moreover, the composition percentage of Yb3+-Er3+ and Gd3+ ions was found to vary in a regular pattern with the adding sequence. Furthermore, the intensity ratios of emission colors (f g/r, f g/p), and the magnetic mass susceptibility of hexagonal-phase NaGdF4: Yb, Er nanocrystals change along with the composition of the nanocrystals. A positive correlation between the susceptibility and f g/r of NaGdF4: Yb, Er was proposed. The decomposition processes of the precursors were investigated by a thermogravimetric (TG) analyzer. The result indicated that the decomposition of the resolved lanthanide trifluoroacetate is greatly different from lanthanide trifluoroacetate powder. It is of tremendous help to recognize the decomposition process of the precursors and to understand the related reaction mechanism.

  4. Zintl phase with a layered network structure, KSi/sub 3/As/sub 3/

    SciT

    Hurng, W.M.; Corbett, J.D.; Wang, S.L.

    The title compound is obtained in high yield from a two-step reaction of K with Si in sealed tantalum and then of that product with As in silica at 800-900/sup 0/C. Ion exchange with NaI at 500 /sup 0/C gives the sodium derivative. The structure of the purple KSi/sub 3/A/sub 3/ crystals has been established by x-ray diffraction means at room temperature (orthorhombic, space group Pbam, Z = 4, a = 10.010 (4) A, b = 19.139 (8) A, c = 3.664 (1) A, R = 0.044 for 674 reflections, 2theta < 55/sup 0/). The infinity /sup 2/(Si/sub 3/As/sub 3/)/supmore » -/ anion layers may be generated by Si-Si bonding between puckered Si/sub 3/As/sub 3/(As) rings to form chains followed by side-by-side condensation of these to sheets. The structure may be derived from the layered structure of SiAs in a concerted way through reductive ring opening and Si-Si bond formation. Comparisons are also made with more reduced Si-As anion chains and clusters and with the closely related Li/sub 3/NaSi/sub 6/. K/sub 2/SiAs/sub 2/ has also been synthesized and shown to be isostructural with K/sub 2/SiP/sub 2/. 20 references, 4 figures, 4 tables.« less

  5. Influence of Boehmite Precursor on Aluminosilicate Aerogel Pore Structure, Phase Stability and Resistance to Densification at High Temperatures

    NASA Technical Reports Server (NTRS)

    Hurwitz, Frances I.; Guo, Haiquan; Newlin, Katy N.

    2011-01-01

    Aluminosilicate aerogels are of interest as constituents of thermal insulation systems for use at temperatures higher than those attainable with silica aerogels. It is anticipated that their effectiveness as thermal insulators will be influenced by their morphology, pore size distribution, physical and skeletal densities. The present study focuses on the synthesis of aluminosilicate aerogel from a variety of Boehmite (precursors as the Al source, and tetraethylorthosilicate (TEOS) as the Si source, and the influence of starting powder on pore structure and thermal stability.

  6. V6O13 films by control of the oxidation state from aqueous precursor to crystalline phase.

    PubMed

    Peys, Nick; Ling, Yun; Dewulf, Daan; Gielis, Sven; De Dobbelaere, Christopher; Cuypers, Daniel; Adriaensens, Peter; Van Doorslaer, Sabine; De Gendt, Stefan; Hardy, An; Van Bael, Marlies K

    2013-01-28

    An aqueous deposition process for V(6)O(13) films is developed whereby the vanadium oxidation state is continuously controlled throughout the entire process. In the precursor stage, a controlled wet chemical reduction of the vanadium(V) source with oxalic acid is achieved and monitored by (51)Vanadium Nuclear Magnetic Resonance ((51)V-NMR) and Ultraviolet-Visible (UV-Vis) spectroscopy. The resulting vanadium(IV) species in the aqueous solution are identified as mononuclear citrato-oxovanadate(IV) complexes by Electron Paramagnetic Resonance (EPR) and Fourier Transform Infra-Red (FTIR) spectroscopy. This precursor is successfully employed for the deposition of uniform, thin films. The optimal deposition and annealing conditions for the formation of crystalline V(6)O(13), including the control of the vanadium oxidation state, are determined through an elaborate study of processing temperature and O(2) partial pressure. To ensure a sub 100 nm adjustable film thickness, a non-oxidative intermediate thermal treatment is carried out at the end of each deposition cycle, allowing maximal precursor decomposition while still avoiding V(IV) oxidation. The resulting surface hydrophilicity, indispensable for the homogeneous deposition of the next layer, is explained by an increased surface roughness and the increased availability of surface vanadyl groups. Crystalline V(6)O(13) with a preferential (002) orientation is obtained after a post deposition annealing in a 0.1% O(2) ambient for thin films with a thickness of 20 nm.

  7. New precursors for direct synthesis of single phase Na- and K-{beta}{double_prime}-aluminas for use in AMTEC systems

    SciT

    Cook, R.L.; MacQueen, D.B.; Bader, K.E.

    1997-12-31

    Alkali Metal Thermoelectric Converters (AMTEC) are efficient direct energy conversion devices that depend on the use of highly conductive beta-alumina membranes for their operation. The key component of the AMTEC system is a highly conductive Na-{beta}{double_prime}-alumina solid electrolyte which conducts sodium ions from the high to low temperature zone, thereby generating electricity. AMTEC cells convert thermal to electrical energy by using heat to produce and maintain an alkali metal concentration gradient across the ion transporting BASE membrane. They have developed a method for producing pure phase Na-{beta}{double_prime}-alumina and K-{beta}{double_prime}-alumina powders from single phase nano-sized carboxylato-alumoxanes precursors. Sodium or potassium ionsmore » (the mobile ions) and either Mg{sup 2+} or Li{sup +} ions (which stabilize the {beta}{double_prime}-alumina structure) can be atomically dispersed into the carboxylato-alumoxane lattice at low (< 100 C) temperature. Calculation of the carboxylato-alumoxane precursors at 1,200--1,500 C produces pure phase {beta}{double_prime}-alumina powders.« less

  8. Precursor Ion Scan Mode-Based Strategy for Fast Screening of Polyether Ionophores by Copper-Induced Gas-Phase Radical Fragmentation Reactions.

    PubMed

    Crevelin, Eduardo J; Possato, Bruna; Lopes, João L C; Lopes, Norberto P; Crotti, Antônio E M

    2017-04-04

    The potential of copper(II) to induce gas-phase fragmentation reactions in macrotetrolides, a class of polyether ionophores produced by Streptomyces species, was investigated by accurate-mass electrospray tandem mass spectrometry (ESI-MS/MS). Copper(II)/copper(I) transition directly induced production of diagnostic acylium ions with m/z 199, 185, 181, and 167 from α-cleavages of [macrotetrolides + Cu] 2+ . A UPLC-ESI-MS/MS methodology based on the precursor ion scan of these acylium ions was developed and successfully used to identify isodinactin (1), trinactin (2), and tetranactin (3) in a crude extract of Streptomyces sp. AMC 23 in the precursor ion scan mode. In addition, copper(II) was also used to induce radical fragmentation reactions in the carboxylic acid polyether ionophore nigericin. The resulting product ions with m/z 755 and 585 helped to identify nigericin in a crude extract of Streptomyces sp. Eucal-26 by means of precursor ion scan experiments, demonstrating that copper-induced fragmentation reactions can potentially identify different classes of polyether ionophores rapidly and selectively.

  9. Thermoelectric properties of AMg 2X 2, AZn 2Sb 2 (A = Ca, Sr, Ba; X = Sb, Bi), and Ba 2ZnX 2 (X = Sb, Bi) Zintl compounds

    DOE PAGES

    Sun, Jifeng; Singh, David J.

    2017-04-03

    In this paper, we report a theoretical investigation of the electronic structure and transport properties of eleven Zintl compounds including nine 122 phases (AMg 2X 2, AZn 2Sb 2 (A = Ca, Sr, Ba; X = Sb, Bi)) and two 212 phases (Ba 2ZnX 2 (X = Sb, Bi)). The electronic structures and electrical transport properties are studied using ab initio calculations and semi-classical Boltzmann theory within the constant relaxation time approximation. All the compounds are semiconducting. We find that the n-type 122 phases with the CaAl 2Si 2 structure type show better performance than p-type materials due to themore » multi-valley degeneracy with anisotropic carrier pockets at and near the conduction band minimum. The pocket anisotropy is beneficial in achieving high conductivity and Seebeck coefficient simultaneously. This mechanism yields substantial improvement in the power factor. Finally, the general performance of 212 phases is inferior to that of the 122 phases, with the Ba 2ZnSb 2 compound showing better performance.« less

  10. Single-phase ceramics with La 1- xSr xGa 1- yMg yO 3- δ composition from precursors obtained by mechanosynthesis

    NASA Astrophysics Data System (ADS)

    Moure, A.; Castro, A.; Tartaj, J.; Moure, C.

    Dense ceramics with La 0.80Sr 0.20Ga 0.85Mg 0.15O 2.825 and La 0.80Sr 0.15Ga 0.85Mg 0.20O 2.825 compositions have been prepared by sintering of mechanosynthesized precursors. The perovskite is synthesized after 85 h of milling in a planetary mill. Single phases have been obtained at conditions that are not possible if traditional solid-state reaction (SSR) method is used. The influence of milling time and composition in the reactivity of the precursors is studied. Highest purity is obtained in Sr = 0.15 and Mg = 0.20 composition, with relative density higher than 97%. The total elimination of typical secondary phases for these compositions, as SrLaGaO 4 and SrLaGa 3O 7, allows the total conductivity of the ceramics to be improved. The influence of the grain size and the nature of the grain boundaries on the electrical characteristic of the ceramics are also discussed.

  11. Structural and optical characterization of Eu3+ doped beta-Ga2O3 nanoparticles using a liquid-phase precursor method.

    PubMed

    Kim, Moung-O; Kang, Bongkyun; Yoon, Daeho

    2013-08-01

    Eu3+ doped beta-Ga2O3 and non-doped beta-Ga2O3 nanoparticles were synthesized at 800 degrees C using a liquid-phase precursor (LPP) method, with different annealing times and Eu3+ ion concentrations. Eu3+ doped beta-Ga2O3 nanoparticles showed broad XRD peaks, revealing a second phase compared with the non-doped beta-Ga2O3 nanoparticles. The cathode luminescence (CL) spectra of beta-Ga2O3 and Eu3+ doped beta-Ga2O3 nanoparticles showed a broad band emission (300-500 nm) of imperfection and two component emissions. The luminescence quenching properties of Eu3+ dopant ion concentration appeared gradually beyond 5 mol% in our investigation.

  12. Na(23)K(9)Tl(15.3): An Unusual Zintl Compound Containing Apparent Tl(5)(7)(-), Tl(4)(8)(-), Tl(3)(7)(-), and Tl(5)(-) Anions.

    PubMed

    Dong, Zhen-Chao; Corbett, John D.

    1996-05-22

    Reaction of the neat elements in tantalum containers at 400 degrees C and then 150 degrees C gives the pure title phase. X-ray crystallography shows that the hexagonal structure (P6(3)/mmc, Z = 2, a = 11.235(1) Å, b = 30.133(5) Å) contains relatively high symmetry clusters Tl(5)(7)(-) (D(3)(h)()), Tl(4)(8)(-) (C(3)(v)(), approximately T(d)), and the new Tl(3)(7)(-) (D(infinity)(h)()) plus Tl(5)(-), the last two disordered over the same elongated site in 1:2 proportions. Cation solvation of these anions is tight and specific, providing good Coulombic trapping of weakly bound electrons on the isolated cluster anions. The observed disorder makes the compound structurally a Zintl phase with a closed shell electron count. EHMO calculations on the novel Tl(3)(7)(-) reveal some bonding similarities with the isoelectronic CO(2), with two good sigma(s,p) bonding and two weakly bonding pi MO's. The Tl-Tl bond lengths therein (3.14 Å) are evidently consistent with multiple bonding. The weak temperature-independent paramagnetism and metallic conductivity (rho(293) approximately 90 &mgr;Omega.cm) of the phase are discussed.

  13. The Abundance of SiC2 in Carbon Star Envelopes⋆: Evidence that SiC2 is a gas-phase precursor of SiC dust

    PubMed Central

    Massalkhi, Sarah; Agúndez, M.; Cernicharo, J.; Velilla Prieto, L.; Goicoechea, J. R.; Quintana-Lacaci, G.; Fonfría, J. P.; Alcolea, J.; Bujarrabal, V.

    2017-01-01

    Context Silicon carbide dust is ubiquitous in circumstellar envelopes around C-rich AGB stars. However, the main gas-phase precursors leading to the formation of SiC dust have not yet been identified. The most obvious candidates among the molecules containing an Si–C bond detected in C-rich AGB stars are SiC2, SiC, and Si2C. To date, the ring molecule SiC2 has been observed in a handful of evolved stars, while SiC and Si2C have only been detected in the C-star envelope IRC +10216. Aims We aim to study how widespread and abundant SiC2, SiC, and Si2C are in envelopes around C-rich AGB stars and whether or not these species play an active role as gas-phase precursors of silicon carbide dust in the ejecta of carbon stars. Methods We carried out sensitive observations with the IRAM 30m telescope of a sample of 25 C-rich AGB stars to search for emission lines of SiC2, SiC, and Si2C in the λ 2 mm band. We performed non-LTE excitation and radiative transfer calculations based on the LVG method to model the observed lines of SiC2 and to derive SiC2 fractional abundances in the observed envelopes. Results We detect SiC2 in most of the sources, SiC in about half of them, and do not detect Si2C in any source, at the exception of IRC +10216. Most of these detections are reported for the first time in this work. We find a positive correlation between the SiC and SiC2 line emission, which suggests that both species are chemically linked, the SiC radical probably being the photodissociation product of SiC2 in the external layer of the envelope. We find a clear trend in which the denser the envelope, the less abundant SiC2 is. The observed trend is interpreted as an evidence of efficient incorporation of SiC2 onto dust grains, a process which is favored at high densities owing to the higher rate at which collisions between particles take place. Conclusions The observed behavior of a decline in the SiC2 abundance with increasing density strongly suggests that SiC2 is an important

  14. The Abundance of SiC2 in Carbon Star Envelopes: Evidence that SiC2 is a gas-phase precursor of SiC dust.

    PubMed

    Massalkhi, Sarah; Agúndez, M; Cernicharo, J; Velilla Prieto, L; Goicoechea, J R; Quintana-Lacaci, G; Fonfría, J P; Alcolea, J; Bujarrabal, V

    2018-03-01

    Silicon carbide dust is ubiquitous in circumstellar envelopes around C-rich AGB stars. However, the main gas-phase precursors leading to the formation of SiC dust have not yet been identified. The most obvious candidates among the molecules containing an Si-C bond detected in C-rich AGB stars are SiC 2 , SiC, and Si 2 C. To date, the ring molecule SiC 2 has been observed in a handful of evolved stars, while SiC and Si 2 C have only been detected in the C-star envelope IRC +10216. We aim to study how widespread and abundant SiC 2 , SiC, and Si 2 C are in envelopes around C-rich AGB stars and whether or not these species play an active role as gas-phase precursors of silicon carbide dust in the ejecta of carbon stars. We carried out sensitive observations with the IRAM 30m telescope of a sample of 25 C-rich AGB stars to search for emission lines of SiC 2 , SiC, and Si 2 C in the λ 2 mm band. We performed non-LTE excitation and radiative transfer calculations based on the LVG method to model the observed lines of SiC 2 and to derive SiC 2 fractional abundances in the observed envelopes. We detect SiC 2 in most of the sources, SiC in about half of them, and do not detect Si 2 C in any source, at the exception of IRC +10216. Most of these detections are reported for the first time in this work. We find a positive correlation between the SiC and SiC 2 line emission, which suggests that both species are chemically linked, the SiC radical probably being the photodissociation product of SiC 2 in the external layer of the envelope. We find a clear trend in which the denser the envelope, the less abundant SiC 2 is. The observed trend is interpreted as an evidence of efficient incorporation of SiC 2 onto dust grains, a process which is favored at high densities owing to the higher rate at which collisions between particles take place. The observed behavior of a decline in the SiC 2 abundance with increasing density strongly suggests that SiC 2 is an important gas-phase

  15. In Vivo Formation of Cubic Phase in Situ after Oral Administration of Cubic Phase Precursor Formulation Provides Long Duration Gastric Retention and Absorption for Poorly Water-Soluble Drugs.

    PubMed

    Pham, Anna C; Hong, Linda; Montagnat, Oliver; Nowell, Cameron J; Nguyen, Tri-Hung; Boyd, Ben J

    2016-01-04

    Lipid-based liquid crystalline systems based on the combination of digestible and nondigestible lipids have been proposed as potential sustained release delivery systems for oral delivery of poorly water-soluble drugs. The potential for cubic phase liquid crystal formation to induce dramatically extended gastric retention in vivo has been shown previously to strongly influence the resulting pharmacokinetics of incorporated drug. In vitro studies showing the in situ formation of cubic phase from a disordered precursor comprising a mixture of digestible and nondigestible lipids under enzymatic digestion have also recently been reported. Combining both concepts, here we show the potential for such systems to form in vivo, increasing gastric retention, and providing a sustained release effect for a model poorly water-soluble drug cinnarizine. A mixture of phytantriol and tributyrin at an 85:15 mass ratio, shown previously to form cubic phase under the influence of digestion, induced a similar pharmacokinetic profile to that in the absence of tributyrin, but completely different from tributyrin alone. The gastric retention of the formulation, assessed using micro-X-ray CT imaging, was also consistent with the pharmacokinetic behavior, where phytantriol alone and with 15% tributyrin was greater than that of tributyrin in the absence of phytantriol. Thus, the concept of precursor lipid systems that form cubic phase in situ during digestion in vivo has been demonstrated and opens new opportunities for sustained release of poorly water-soluble drugs.

  16. Addition of a thallium vertex to empty and centered nine-atom deltahedral zintl ions of germanium and tin.

    PubMed

    Rios, Daniel; Gillett-Kunnath, Miriam M; Taylor, Jacob D; Oliver, Allen G; Sevov, Slavi C

    2011-03-21

    Nickel atoms were inserted into nine-atom deltahedral Zintl ions of E(9)(4-) (E = Ge, Sn) via reactions with Ni(cod)(2) (cod = cyclooctadiene), and [Ni@Sn(9)](3-) was structurally characterized. Both the empty and the Ni-centered clusters react with TlCp (Cp = cyclopentadienyl anion) and add a thallium vertex to form the deltahedral ten-atom closo-species [E(9)Tl](3-) and [Ni@E(9)Tl](3-), respectively. The structures of [Ge(9)Tl](3-) and [Ni@Sn(9)Tl](3-) showed that, as expected, the geometry of the ten-atom clusters is that of a bicapped square antiprism where the Tl-atom occupies one of the two capping vertices. This illustrates that centering a nine-atom cluster with a nickel atom does not change its reactivity toward TlCp. All compounds were characterized by electrospray mass spectrometry.

  17. Motion of the guest ion as precursor to the first-order phase transition in the cage system GdB6

    NASA Astrophysics Data System (ADS)

    Iwasa, Kazuaki; Igarashi, Ryosuke; Saito, Kotaro; Laulhé, Claire; Orihara, Toshihiko; Kunii, Satoru; Kuwahara, Keitaro; Nakao, Hironori; Murakami, Youichi; Iga, Fumitoshi; Sera, Masafumi; Tsutsui, Satoshi; Uchiyama, Hiroshi; Baron, Alfred Q. R.

    2011-12-01

    The motion of guest Gd ions in oversized boron cages in GdB6 was investigated from phonon spectra measurements obtained by inelastic x-ray scattering. The measured phonon modes soften by about 10% from 300 K down to TN=16 K, in particular, the longitudinal phonon for the propagation vector q1=(1/2,0,0) that characterizes the distorted structure below TN. Besides, the dispersion relation curves show kinklike anomalies at qk=(0.38,0.38,0). The observed results imply that the motion of the guest Gd ion interplays with the f electrons magnetoelastically and with carriers via Fermi surface nesting. The anomalous properties previously reported for this material far above TN originate from the strong electron-phonon coupling, which causes the motion of guest ions as precursors to the first-order phase transition.

  18. Enhanced Photocatalytic Activity of Bismuth Precursor by Rapid Phase and Surface Transformation Using Structure-Guided Combustion Waves.

    PubMed

    Lee, Kang Yeol; Hwang, Hayoung; Kim, Tae Ho; Choi, Wonjoon

    2016-02-10

    The development of an efficient method for manipulating phase and surface transformations would facilitate the improvement of catalytic materials for use in a diverse range of applications. Herein, we present the first instance of a submicrosecond time frame direct phase and surface transformation of Bi(NO3)3 rods to nanoporous β-Bi2O3 rods via structure-guided combustion waves. Hybrid composites of the prepared Bi(NO3)3·H2O rods and organic fuel were fabricated by a facile preparation method. The anisotropic propagation of combustion waves along the interfacial boundaries of Bi(NO3)3·H2O rods induced direct phase transformation to β-Bi2O3 rods in the original structure due to the rapid pyrolysis, while the release of gas molecules enabled the formation of nanoporous structures on the surfaces of rods. The developed β-Bi2O3 rods showed improved photocatalytic activity for the photodegradation of rhodamine B in comparison with Bi(NO3)3·H2O rods and α-Bi2O3 rods due to the more suitable interdistance and the large contact areas of the porous surfaces. This new method of using structure-guided combustion waves for phase and surface transformation may contribute to the development of new catalysts as well as the precise manipulation of diverse micronanostructured materials.

  19. Heterometallic molecular precursors for a lithium-iron oxide material: synthesis, solid state structure, solution and gas-phase behaviour, and thermal decomposition.

    PubMed

    Han, Haixiang; Wei, Zheng; Barry, Matthew C; Filatov, Alexander S; Dikarev, Evgeny V

    2017-05-02

    Three heterometallic single-source precursors with a Li : Fe = 1 : 1 ratio for a LiFeO 2 oxide material are reported. Heterometallic compounds LiFeL 3 (L = tbaoac (1), ptac (2), and acac(3)) have been obtained on a large scale, in nearly quantitative yields by one-step reactions that employ readily available reagents. The heterometallic precursor LiFe(acac) 3 (3) with small, symmetric substituents on the ligand (acac = pentane-2,4-dionate), maintains a 1D polymeric structure in the solid state that limits its volatility and prevents solubility in non-coordinating solvents. The application of the unsymmetrical ligands, tbaoac (tert-butyl acetoacetate) and ptac (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate), that exhibit different bridging properties at the two ends of the ligand, allowed us to change the connectivity pattern within the heterometallic assembly. The latter was demonstrated by structural characterization of heterometallic complexes LiFe(tbaoac) 3 (1) and LiFe(ptac) 3 (2) that consist of discrete heterocyclic tetranuclear molecules Li 2 Fe 2 L 6 . The compounds are highly volatile and exhibit a congruent sublimation character. DART mass spectrometric investigation revealed the presence of heterometallic molecules in the gas phase. The positive mode spectra are dominated by the presence of [M - L] + peaks (M = Li 2 Fe 2 L 6 ). In accord with their discrete molecular structure, complexes 1 and 2 are highly soluble in nearly all common solvents. In order to test the retention of the heterometallic structure in solution, the diamagnetic analog of 1, LiMg(tbaoac) 3 (4), has been isolated. Its tetranuclear molecular structure was found to be isomorphous to that of the iron counterpart. 1 H and 7 Li NMR spectroscopy unambiguously confirmed the presence of heterometallic molecules in solutions of non-coordinating solvents. The heterometallic precursor 1 was shown to exhibit clean thermal decomposition in air that results in phase-pure

  20. Acoustic measurements of the 1999 basaltic eruption of Shishaldin volcano, Alaska 2. Precursor to the Subplinian phase

    Vergniolle, S.; Caplan-Auerbach, J.

    2004-01-01

    The 1999 eruption of Shishaldin volcano (Alaska, USA) displayed both Strombolian and Subplinian basaltic activity. The Subplinian phase was preceded by a signal of low amplitude and constant frequency (??? 2 Hz) lasting 13 h. This "humming signal" is interpreted as the coalescence of the very shallow part of a foam building up in the conduit, which produces large gas bubbles before bursting. The acoustic waveform of the hum event is modelled by a Helmholtz resonator: gas is trapped into a rigid cavity and can only escape through a tiny upper hole producing sound waves. At Shishaldin, the radius of the hole (??? 5 m) is close to that of the conduit (??? 6 m), the cavity has a length of ??? 60 m, and gas presents only a small overpressure between (??? 1.2 ?? 10-3 and 4.5 ?? 10-3 MPa). Such an overpressure is obtained by the partial coalescence of a foam formed by bubbles with a diameter from ??? 2.3 mm at the beginning of the episode towards ??? 0.64 mm very close to the end of the phase. The intermittency between hum events is explained by the ripening of the foam induced by the H2O diffusion through the liquid films. The two extreme values, from 600 to 10 s, correspond to a bubble diameter from 2.2 to 0.3 mm at the beginning and end of the pre-Subplinian phase, respectively. The extremely good agreement between two independent estimates of bubble diameters in the shallow foam reinforces the validity of such an interpretation. The total gas volume lost at the surface during the humming events is at most 5.9 ?? 106 m3. At the very end of the pre-Subplinian phase, there is a single large bubble with an overpressure of ???0.42 MPa. The large overpressure suggests that it comes from significant depth, unlike other bubbles in the pre-Subplinian phase. This deep bubble may be responsible for the entire foam collapse, resulting in the Subplinian phase. ?? 2004 Elsevier B.V. All rights reserved.

  1. Eu2P7X and Ba2As7X (X = Br, I): Chiral double-Zintl salts containing heptapnictotricyclane clusters

    NASA Astrophysics Data System (ADS)

    Dolyniuk, Juli-Anna; Lee, Shannon; Tran, Nhon; Wang, Jian; Wang, Lin-Lin; Kovnir, Kirill

    2018-07-01

    Chiral double Zintl salts present tunable crystal structures with enhanced structural flexibilities and potential for applications requiring chiral control and enantioselectivity. To accompany the chiral Sr2P7I and Sr2P7Br double Zintl salts reported by us previously, six new chiral Zintl salts of the form Ba2-ySryAs7I (y = 0, 0.23, 2), Eu2P7I, Eu2P7Br, and Eu1.3Ba0.7P7Br have been synthesized and characterized by single crystal X-ray diffraction and SEM-EDS analyses. All new compounds crystallize in the Sohncke space group P213 (No. 198) with variations of P73- (heptaphosphanortricyclane) or As73- (heptaarsanortricyclane) clusters surrounded by alkaline-earth or Eu cations and halogen anions. Band structure calculations predict semiconducting properties for all synthesized compounds. Diffuse reflectance UV-vis spectroscopy indicates that Eu2P7I is a direct bandgap semiconductor with Eg of 1.7 eV.

  2. About the Shape of the Melting Line as a Possible Precursor of a Liquid-Liquid Phase Transition

    NASA Astrophysics Data System (ADS)

    Imre, Attila R.; Rzoska, Sylwester J.

    Several simple, non-mesogenic liquids can exists in two or more different liquid forms. When the liquid-liquid line, separating two liquid forms, meets the melting line, one can expect some kind of break on the melting line, caused by the different freezing/melting behaviour of the two liquid forms. Unfortunately recently several researchers are using this vein of thinking in reverse; seeing some irregularity on the melting line, they will expect a break and the appearance of a liquid-liquid line. In this short paper, we are going to show, that in the case of the high-pressure nitrogen studied recently by Mukherjee and Boehler, the high-pressure data can be easily described by a smooth, break-free function, the modified Simon-Glatzel equation. In this way, the break, suggested by them and consequently the suggested appearance of a new liquid phase of the nitrogen might be artefacts.

  3. The Formation of Solid Particles from their Gas-Phase Molecular Precursors in Cosmic Environments with NASA Ames' COSmIC Facility

    NASA Technical Reports Server (NTRS)

    Salama, Farid

    2014-01-01

    We present and discuss the unique characteristics and capabilities of the laboratory facility, COSmIC, that was developed at NASA Ames to generate, process and analyze interstellar, circumstellar and planetary analogs in the laboratory. COSmIC stands for Cosmic Simulation Chamber and is dedicated to the study of molecules and ions under the low temperature and high vacuum conditions that are required to simulate interstellar, circumstellar and planetary physical environments in space. COSmIC integrates a variety of state-of-the-art instruments that allow forming, processing and monitoring simulated space conditions for planetary, circumstellar and interstellar materials in the laboratory. COSmIC is composed of a Pulsed Discharge Nozzle (PDN) expansion that generates a free jet supersonic expansion coupled to two ultrahigh-sensitivity, complementary in situ diagnostics: a Cavity Ring Down Spectroscopy (CRDS) system for photonic detection and a Reflectron Time-Of-Flight Mass Spectrometer (ReTOF-MS) for mass detection. Recent, unique, laboratory astrophysics results that were obtained using the capabilities of COSmIC will be discussed, in particular the progress that have been achieved in monitoring in the laboratory the formation of solid gains from their gas-phase molecular precursors in environments as varied as stellar/circumstellar outflow and planetary atmospheres. Plans for future, next generation, laboratory experiments on cosmic molecules and grains in the growing field of laboratory astrophysics will also be addressed as well as the implications of these studies for current and upcoming space missions.

  4. Safety and activity of blinatumomab for adult patients with relapsed or refractory B-precursor acute lymphoblastic leukaemia: a multicentre, single-arm, phase 2 study.

    PubMed

    Topp, Max S; Gökbuget, Nicola; Stein, Anthony S; Zugmaier, Gerhard; O'Brien, Susan; Bargou, Ralf C; Dombret, Hervé; Fielding, Adele K; Heffner, Leonard; Larson, Richard A; Neumann, Svenja; Foà, Robin; Litzow, Mark; Ribera, Josep-Maria; Rambaldi, Alessandro; Schiller, Gary; Brüggemann, Monika; Horst, Heinz A; Holland, Chris; Jia, Catherine; Maniar, Tapan; Huber, Birgit; Nagorsen, Dirk; Forman, Stephen J; Kantarjian, Hagop M

    2015-01-01

    Adults with relapsed or refractory B-precursor acute lymphoblastic leukaemia have an unfavourable prognosis. Blinatumomab is a bispecific T-cell engager antibody construct targeting CD19, an antigen consistently expressed on B-lineage acute lymphoblastic leukaemia cells. We aimed to confirm the activity and safety profile of blinatumomab for acute lymphoblastic leukaemia. In a multicentre, single-arm, open-label phase 2 study, we enrolled adult patients with Philadelphia-chromosome-negative, primary refractory or relapsed (first relapse within 12 months of first remission, relapse within 12 months after allogeneic haemopoietic stem-cell transplantation [HSCT], or no response to or relapse after first salvage therapy or beyond) leukaemia. Patients received blinatumomab (9 μg/day for the first 7 days and 28 μg/day thereafter) by continuous intravenous infusion over 4 weeks every 6 weeks (up to five cycles), per protocol. The primary endpoint was complete remission (CR) or CR with partial haematological recovery of peripheral blood counts (CRh) within the first two cycles. Analysis was by intention to treat. This trial is registered at ClinicalTrials.gov, number NCT01466179. Between Jan 13, 2012, and Oct 10, 2013, 189 patients were enrolled and treated with blinatumomab. After two cycles, 81 (43%, 95% CI 36-50) patients had achieved a CR or CRh: 63 (33%) patients had a CR and 18 (10%) patients had a CRh. 32 (40%) of patients who achieved CR/CRh underwent subsequent allogeneic HSCT. The most frequent grade 3 or worse adverse events were febrile neutropenia (48 patients, 25%), neutropenia (30 patients, 16%), and anaemia (27 patients, 14%). Three (2%) patients had grade 3 cytokine release syndrome. Neurologic events of worst grade 3 or 4 occurred in 20 (11%) and four (2%) patients, respectively. Three deaths (due to sepsis, Escherichia coli sepsis, and Candida infection) were thought to be treatment-related by the investigators. Single-agent blinatumomab showed

  5. Irreversible phase transitions due to laser-based T-jump heating of precursor Eu:ZrO{sub 2}/Tb:Y{sub 2}O{sub 3} core/shell nanoparticles

    SciT

    Gunawidjaja, Ray; Diez-y-Riega, Helena; Eilers, Hergen, E-mail: eilers@wsu.edu

    2015-09-15

    Amorphous precursors of Eu-doped-ZrO{sub 2}/Tb-doped-Y{sub 2}O{sub 3} (p-Eu:ZrO{sub 2}/p-Tb:Y{sub 2}O{sub 3}) core/shell nanoparticles are rapidly heated to temperatures between 200 °C and 950 °C for periods between 2 s and 60 s using a CO{sub 2} laser. During this heating process the nanoparticles undergo irreversible phase changes. The fluorescence spectra due to Eu{sup 3+} dopants in the core and Tb{sup 3+} dopants in the shell are used to identify distinct phases within the material and to generate time/temperature phase diagrams. Such phase diagrams can potentially help to determine unknown time/temperature histories in thermosensor applications. - Graphical abstract: A CO{sub 2}more » laser is used for rapid heating of p-Eu:ZrO{sub 2}/p-Tb:Y{sub 2}O{sub 3} core/shell nanoparticles. Optical spectra are used to identify distinct phases and to determine its thermal history. - Highlights: • Synthesized oxide precursors of lanthanide doped core/shell nanoparticles. • Heated core/shell nanoparticles via laser-based T-jump technique. • Observed time- and temperature-dependent irreversible phase transition.« less

  6. Ab initio computational study on the lattice thermal conductivity of Zintl clathrates [Si19P4] Cl4 and Na4[Al4Si19

    NASA Astrophysics Data System (ADS)

    Härkönen, Ville J.; Karttunen, Antti J.

    2016-08-01

    The lattice thermal conductivity of silicon clathrate framework Si23 and two Zintl clathrates, [Si19P4] Cl4 and Na4[Al4Si19] , is investigated by using an iterative solution of the linearized Boltzmann transport equation in conjunction with ab initio lattice dynamical techniques. At 300 K, the lattice thermal conductivities for Si23, [Si19P4] Cl4 , and Na4[Al4Si19] were found to be 43 W/(m K), 25 W/(m K), and 2 W/(m K), respectively. In the case of Na4[Al4Si19] , the order-of-magnitude reduction in the lattice thermal conductivity was found to be mostly due to relaxation times and group velocities differing from Si23 and [Si19P4] Cl4 . The difference in the relaxation times and group velocities arises primarily due to the phonon spectrum at low frequencies, resulting eventually from the differences in the second-order interatomic force constants (IFCs). The obtained third-order IFCs were rather similar for all materials considered here. The present findings are similar to those obtained earlier for some skutterudites. The predicted lattice thermal conductivity of Na4[Al4Si19] is in line with the experimentally measured thermal conductivity of recently synthesized type-I Zintl clathrate Na8[Al8Si38] (polycrystalline samples).

  7. Lithiation-induced zinc clustering of Zn 3, Zn 12, and Zn 18 units in Zintl-like Ca ~30Li 3+xZn 60-x (x=0.44-1.38)

    SciT

    Lin, Qisheng

    2014-11-14

    Zinc clusters are not common for binary intermetallics with relatively low zinc content, but this work shows that zinc clustering can be triggered by lithiation, as exemplified by Ca ~30Li 3+xZn 60-x, P6/mmm, Z = 1, which can be directly converted from CaZn 2. Two end members of the solid solution (x = 0.44 and 1.38) were established and structurally characterized by single-crystal X-ray diffraction analyses: Ca 30Li 3.44(6)Zn59.56(6), a = 15.4651(9) Å, c = 9.3898(3) Å; Ca 30.45(2)Li 4.38(6)Zn 58.62(6), a = 15.524(3) Å, c = 9.413(2) Å. The structures of Ca ~30Li 3+xZn 60-x feature a condensed anionicmore » network of Zn3 triangles, lithium-centered Zn12 icosahedra, and arachno-(Zn,Li)18 tubular clusters that are surrounded respectively by Ca 14, Ca 20, and Ca 30 polyhedra. These polyhedra share faces and form a clathrate-like cationic framework. The specific occupation of lithium in the structure is consistent with theoretical “coloring” analyses. Analysis by the linear muffin-tin orbital (LMTO) method within the atomic sphere approximation reveals that Ca ~30Li 3+xZn 60-x is a metallic, Zintl-like phase with an open-shell electronic structure. The contribution of Ca–Zn polar covalent interactions is about 41%.« less

  8. Peeling without precursors

    NASA Astrophysics Data System (ADS)

    Lister, John; Skinner, Dominic; Large, Tim

    2017-11-01

    The peeling by fluid injection of an elastic sheet away from a substrate is often regularised by invoking a thin prewetting film or a low-viscosity phase in the tip. Here we analyse fluid-driven peeling without such precursors, and consider an elastic sheet either bonded to, or simply laid on, an elastic substrate. To resolve the `elastic contact-line problem' that arises from viscous flow and beam theory, we determine the near-tip behaviour from lubrication theory coupled to the full equations of elasticity and fracture. The result is a law for the tip propagation speed in terms of the remote loading and the toughness of the sheet-substrate bonding (which might be zero). There are distinct modes of failure, according to whether there is slip ahead of the fluid front. The propagation-speed law gives rise to new similarity solutions for the spread of a fluid-filled blister in different regimes.

  9. Magnéli phases Ti{sub 4}O{sub 7} and Ti{sub 8}O{sub 15} and their carbon nanocomposites via the thermal decomposition-precursor route

    SciT

    Conze, S., E-mail: susan.conze@ikts.fraunhofer.de; Veremchuk, I.; Reibold, M.

    2015-09-15

    A new synthetic approach for producing nano-powders of the Magnéli phases Ti{sub 4}O{sub 7}, Ti{sub 8}O{sub 15} and their carbon nanocomposites by thermal decomposition-precursor route is proposed. The formation mechanism of the single-phase carbon nanocomposites (Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C) from metal–organic precursors is studied using FT-IR, elemental analysis, TG, STA-MS and others. The synthesis parameters and conditions were optimized to prepare the target oxides with the desired microstructure and physical properties. The electrical and transport properties of Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C are investigated. These nano-materials are n-type semiconductors with relatively low thermal conductivity inmore » contrast to the bulk species. The nanostructured carbon nanocomposites of Magnéli phases achieve a low thermal conductivity close to 1 W/m K at RT. The maximum ZT{sub 570} {sub °C} values are 0.04 for Ti{sub 4}O{sub 7}/C powder nanocomposite and 0.01 for Ti{sub 8}O{sub 15}/C bulk nanocomposite. - Graphical abstract: From the precursor to the produced titanium oxide pellet and its microstructure (SEM, TEM micrographs) as well as results of phase and thermoelectric analyses. - Highlights: • Magnéli phases Ti{sub 4}O{sub 7}/Ti{sub 8}O{sub 15} via thermal decomposition-precursor route is proposed. • The formation mechanism of the nanocomposites Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C are investigated. • Microstructure of Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C are examined. • The electrical and transport properties of Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C are investigated. • The maximum figure of mertit ZT{sub 570} {sub °C} of Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C are 0.01 and 0.04.« less

  10. Structural and electronic properties of Genm- and KGen- Zintl anions (n=3-10;m=2-4) from density functional theory

    NASA Astrophysics Data System (ADS)

    Li, Si-Dian; Guo, Qiao-Ling; Zhao, Xiu-Feng; Wu, Hai-Shun; Jin, Zhi-Hao

    2002-07-01

    Structural optimizations and frequency analyses have been performed on free Genm- and KGen- (n=3-10, m=2-4) Zintl anions and ionization potentials and electron affinities calculated for KGen using the density functional theory (DFT) of Becke's three-parameter hybrid functional with the Perdew/Wang 91 expression. The DFT results obtained for small clusters (n=3-5) are further checked with both the second-order Moller-Plesset perturbation theory (MP2) and the configuration interaction calculations with all single and double substitutions from the Hartree-Fock reference determinant (CISD). Free Gen2- anions are found to share the same geometries as naked Zintl anions observed in solids with a systematical expansion in bond lengths within about 5%. Intensive searches indicate that two isomers, a tricapped trigonal prism (D3h) and a slightly distorted tricapped trigonal prism (C2v), exist for Ge92- and Ge93-, while nido-Ge94- clearly favors the monocapped antisquare prism (C4v) structure. HOMO-LUMO energy gaps >2.23 eV are obtained for Genm- series at the DFT level, except Ge93- which has a much narrower energy gap of 1.16 eV. The calculated Gibbs free energy change of Ge92-+Ge94-=2 Ge93- conversion reaction involving nonagermanides has the value of Delta]G[deg=-2.91 x105 J mol-1, providing the first quantum chemistry evidence that the geometrically deduced mixed valent couple of Ge92- and Ge94- in a previous study is thermodynamically unstable compared to two Ge93- anions. The calculated stabilization energies of Gen2-, Gen-, and Gen exhibit similar variation trends, clearly indicating a maximum at n=7, a minimum at n=8, and an obvious recovery at n=9 and 10. The calculated normal vibrational frequencies reproduce the six observed Raman peaks of naked Ge52- with an averaged discrepancy of 11 cm-1. Face-capped or edge-capped deltahedral structures are predicted for binary KGen- anions and KGen and K2Gen neutrals. The magic numbers at n=5, 9, and 10 obtained in both

  11. Detailed Visualization of Phase Evolution during Rapid Formation of Cu(InGa)Se2 Photovoltaic Absorber from Mo/CuGa/In/Se Precursors.

    PubMed

    Koo, Jaseok; Kim, Sammi; Cheon, Taehoon; Kim, Soo-Hyun; Kim, Woo Kyoung

    2018-03-02

    Amongst several processes which have been developed for the production of reliable chalcopyrite Cu(InGa)Se 2 photovoltaic absorbers, the 2-step metallization-selenization process is widely accepted as being suitable for industrial-scale application. Here we visualize the detailed thermal behavior and reaction pathways of constituent elements during commercially attractive rapid thermal processing of glass/Mo/CuGa/In/Se precursors on the basis of the results of systematic characterization of samples obtained from a series of quenching experiments with set-temperatures between 25 and 550 °C. It was confirmed that the Se layer crystallized and then melted between 250 and 350 °C, completely disappearing at 500 °C. The formation of CuInSe 2 and Cu(InGa)Se 2 was initiated at around 450 °C and 550 °C, respectively. It is suggested that pre-heat treatment to control crystallization of Se layer should be designed at 250-350 °C and Cu(InGa)Se 2 formation from CuGa/In/Se precursors can be completed within a timeframe of 6 min.

  12. Determination of 15 N-nitrosodimethylamine precursors in different water matrices by automated on-line solid-phase extraction ultra-high-performance-liquid chromatography tandem mass spectrometry.

    PubMed

    Farré, Maria José; Insa, Sara; Mamo, Julian; Barceló, Damià

    2016-08-05

    A new methodology based on on-line solid-phase extraction (SPE) ultra-high-performance-liquid chromatography coupled to a triple quadrupole mass spectrometer (UHPLC-MS-MS) for the determination of 15 individual anthropogenic N-nitrosodimethylamine (NDMA) precursors was developed. On-line SPE was performed by passing 2mL of the water sample through a Hypersil GOLD aQ column and chromatographic separation was done using a Kinetex Biphenyl column using methanol and 0.1% formic acid aqueous solution as a mobile phase. For unequivocal identification and confirmation, two selected reaction monitoring (SRM) transitions were monitored per compound. Quantification was performed by internal standard approach and matrix match calibration. The main advantages of the developed method are high sensitivity (limits of detection in the sub ng/L range), selectivity due to the use of tandem mass spectrometry, precision and minimum sample manipulation as well as fast analytical response. Process efficiency and recovery were also evaluated for all the target compounds. As part of the validation procedure, the method was applied in a sampling campaign for the analysis of influent and secondary effluent of a wastewater treatment plant (WWTP) in Girona, Spain. Additionally, the effluent from a nanofiltration (NF) membrane system used for water recycling was monitored. The percentage of NDMA formation explained by the measured precursors was also quantified. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Identified EM Earthquake Precursors

    NASA Astrophysics Data System (ADS)

    Jones, Kenneth, II; Saxton, Patrick

    2014-05-01

    Many attempts have been made to determine a sound forecasting method regarding earthquakes and warn the public in turn. Presently, the animal kingdom leads the precursor list alluding to a transmission related source. By applying the animal-based model to an electromagnetic (EM) wave model, various hypotheses were formed, but the most interesting one required the use of a magnetometer with a differing design and geometry. To date, numerous, high-end magnetometers have been in use in close proximity to fault zones for potential earthquake forecasting; however, something is still amiss. The problem still resides with what exactly is forecastable and the investigating direction of EM. After a number of custom rock experiments, two hypotheses were formed which could answer the EM wave model. The first hypothesis concerned a sufficient and continuous electron movement either by surface or penetrative flow, and the second regarded a novel approach to radio transmission. Electron flow along fracture surfaces was determined to be inadequate in creating strong EM fields, because rock has a very high electrical resistance making it a high quality insulator. Penetrative flow could not be corroborated as well, because it was discovered that rock was absorbing and confining electrons to a very thin skin depth. Radio wave transmission and detection worked with every single test administered. This hypothesis was reviewed for propagating, long-wave generation with sufficient amplitude, and the capability of penetrating solid rock. Additionally, fracture spaces, either air or ion-filled, can facilitate this concept from great depths and allow for surficial detection. A few propagating precursor signals have been detected in the field occurring with associated phases using custom-built loop antennae. Field testing was conducted in Southern California from 2006-2011, and outside the NE Texas town of Timpson in February, 2013. The antennae have mobility and observations were noted for

  14. On the difficulties of detecting PP precursors

    NASA Astrophysics Data System (ADS)

    Lessing, Stephan; Thomas, Christine; Saki, Morvarid; Schmerr, Nicholas; Vanacore, Elizabeth

    2015-06-01

    The PP precursors are seismic waves that form from underside reflections of P waves off discontinuities in the upper mantle transition zone (MTZ). These seismic phases are used to map discontinuity topography, sharpness, and impedance contrasts; the resulting structural variations are then often interpreted as evidence for temperature and/or mineralogy variations within the mantle. The PP precursors as well as other seismic phases have been used to establish the global presence of seismic discontinuities at 410 and 660 km depth. Intriguingly, in more than 80 per cent of PP precursor observations the seismic wave amplitudes are significantly weaker than the amplitudes predicted by seismic reference models. Even more perplexing is the observation that 1-5 per cent of all earthquakes (which are 20-25 per cent of earthquakes with clear PP waveforms) do not show any evidence for the PP precursors from the discontinuities even in the presence of well-developed PP waveforms. Non-detections are found in six different data sets consisting of tens to hundreds of events. We use synthetic modelling to examine a suite of factors that could be responsible for the absence of the PP precursors. The take-off angles for PP and the precursors differ by only 1.2-1.5°; thus source-related complexity would affect PP and the precursors. A PP wave attenuated in the upper mantle would increase the relative amplitude of the PP precursors. Attenuation within the transition zone could reduce precursor amplitudes, but this would be a regional phenomenon restricted to particular source receiver geometries. We also find little evidence for deviations from the theoretical travel path of seismic rays expected for scattered arrivals. Factors that have a strong influence include the stacking procedures used in seismic array techniques in the presence of large, interfering phases, the presence of topography on the discontinuities on the order of tens of kilometres, and 3-D lateral heterogeneity in

  15. Polyimide Precursor Solid Residuum

    NASA Technical Reports Server (NTRS)

    Weiser, Erik S. (Inventor); St.Clair, Terry L. (Inventor); Echigo, Yoshiaki (Inventor); Kaneshiro, Hisayasu (Inventor)

    2001-01-01

    A polyimide precursor solid residuum is an admixture of an aromatic dianhydride or derivative thereof and an aromatic diamine or derivative thereof plus a complexing agent, which is complexed with the admixture by hydrogen bonding. The polyimide precursor solid residuum is effectively employed in the preparation of polyimide foam and the fabrication of polyimide foam structures.

  16. Patterning at the 10 nanometer length scale using a strongly segregating block copolymer thin film and vapor phase infiltration of inorganic precursors

    NASA Astrophysics Data System (ADS)

    Choi, Jonathan W.; Li, Zhaodong; Black, Charles T.; Sweat, Daniel P.; Wang, Xudong; Gopalan, Padma

    2016-06-01

    In this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order-disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns and registers sub-12 nm diameter nanowires to larger-scale rectangular, curved, and circular features patterned by optical lithography. The alumina nanowires function as a robust hard mask to withstand the conditions required for patterning the underlying silicon by plasma etching. We conclude with a discussion of some of the challenges that arise with using block copolymers for patterning at sub-10 nm feature sizes.In this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order-disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns and

  17. Electron interactions with the heteronuclear carbonyl precursor H2FeRu3(CO)13 and comparison with HFeCo3(CO)12: from fundamental gas phase and surface science studies to focused electron beam induced deposition

    PubMed Central

    P, Ragesh Kumar T; Weirich, Paul; Hrachowina, Lukas; Hanefeld, Marc; Bjornsson, Ragnar; Hrodmarsson, Helgi Rafn; Barth, Sven; Fairbrother, D Howard; Huth, Michael

    2018-01-01

    In the current contribution we present a comprehensive study on the heteronuclear carbonyl complex H2FeRu3(CO)13 covering its low energy electron induced fragmentation in the gas phase through dissociative electron attachment (DEA) and dissociative ionization (DI), its decomposition when adsorbed on a surface under controlled ultrahigh vacuum (UHV) conditions and exposed to irradiation with 500 eV electrons, and its performance in focused electron beam induced deposition (FEBID) at room temperature under HV conditions. The performance of this precursor in FEBID is poor, resulting in maximum metal content of 26 atom % under optimized conditions. Furthermore, the Ru/Fe ratio in the FEBID deposit (≈3.5) is higher than the 3:1 ratio predicted. This is somewhat surprising as in recent FEBID studies on a structurally similar bimetallic precursor, HFeCo3(CO)12, metal contents of about 80 atom % is achievable on a routine basis and the deposits are found to maintain the initial Co/Fe ratio. Low temperature (≈213 K) surface science studies on thin films of H2FeRu3(CO)13 demonstrate that electron stimulated decomposition leads to significant CO desorption (average of 8–9 CO groups per molecule) to form partially decarbonylated intermediates. However, once formed these intermediates are largely unaffected by either further electron irradiation or annealing to room temperature, with a predicted metal content similar to what is observed in FEBID. Furthermore, gas phase experiments indicate formation of Fe(CO)4 from H2FeRu3(CO)13 upon low energy electron interaction. This fragment could desorb at room temperature under high vacuum conditions, which may explain the slight increase in the Ru/Fe ratio of deposits in FEBID. With the combination of gas phase experiments, surface science studies and actual FEBID experiments, we can offer new insights into the low energy electron induced decomposition of this precursor and how this is reflected in the relatively poor performance

  18. Electron interactions with the heteronuclear carbonyl precursor H2FeRu3(CO)13 and comparison with HFeCo3(CO)12: from fundamental gas phase and surface science studies to focused electron beam induced deposition.

    PubMed

    P, Ragesh Kumar T; Weirich, Paul; Hrachowina, Lukas; Hanefeld, Marc; Bjornsson, Ragnar; Hrodmarsson, Helgi Rafn; Barth, Sven; Fairbrother, D Howard; Huth, Michael; Ingólfsson, Oddur

    2018-01-01

    In the current contribution we present a comprehensive study on the heteronuclear carbonyl complex H 2 FeRu 3 (CO) 13 covering its low energy electron induced fragmentation in the gas phase through dissociative electron attachment (DEA) and dissociative ionization (DI), its decomposition when adsorbed on a surface under controlled ultrahigh vacuum (UHV) conditions and exposed to irradiation with 500 eV electrons, and its performance in focused electron beam induced deposition (FEBID) at room temperature under HV conditions. The performance of this precursor in FEBID is poor, resulting in maximum metal content of 26 atom % under optimized conditions. Furthermore, the Ru/Fe ratio in the FEBID deposit (≈3.5) is higher than the 3:1 ratio predicted. This is somewhat surprising as in recent FEBID studies on a structurally similar bimetallic precursor, HFeCo 3 (CO) 12 , metal contents of about 80 atom % is achievable on a routine basis and the deposits are found to maintain the initial Co/Fe ratio. Low temperature (≈213 K) surface science studies on thin films of H 2 FeRu 3 (CO) 13 demonstrate that electron stimulated decomposition leads to significant CO desorption (average of 8-9 CO groups per molecule) to form partially decarbonylated intermediates. However, once formed these intermediates are largely unaffected by either further electron irradiation or annealing to room temperature, with a predicted metal content similar to what is observed in FEBID. Furthermore, gas phase experiments indicate formation of Fe(CO) 4 from H 2 FeRu 3 (CO) 13 upon low energy electron interaction. This fragment could desorb at room temperature under high vacuum conditions, which may explain the slight increase in the Ru/Fe ratio of deposits in FEBID. With the combination of gas phase experiments, surface science studies and actual FEBID experiments, we can offer new insights into the low energy electron induced decomposition of this precursor and how this is reflected in the relatively

  19. Patterning at the 10 nanometer length scale using a strongly segregating block copolymer thin film and vapor phase infiltration of inorganic precursors

    DOE PAGES

    Choi, Jonathan W.; Li, Zhaodong; Black, Charles T.; ...

    2016-05-04

    Here in this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order–disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns andmore » registers sub-12 nm diameter nanowires to larger-scale rectangular, curved, and circular features patterned by optical lithography. The alumina nanowires function as a robust hard mask to withstand the conditions required for patterning the underlying silicon by plasma etching. Lastly, we conclude with a discussion of some of the challenges that arise with using block copolymers for patterning at sub-10 nm feature sizes.« less

  20. Patterning at the 10 nanometer length scale using a strongly segregating block copolymer thin film and vapor phase infiltration of inorganic precursors

    SciT

    Choi, Jonathan W.; Li, Zhaodong; Black, Charles T.

    Here in this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order–disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns andmore » registers sub-12 nm diameter nanowires to larger-scale rectangular, curved, and circular features patterned by optical lithography. The alumina nanowires function as a robust hard mask to withstand the conditions required for patterning the underlying silicon by plasma etching. Lastly, we conclude with a discussion of some of the challenges that arise with using block copolymers for patterning at sub-10 nm feature sizes.« less

  1. GAS-PHASE SYNTHESIS OF PRECURSORS OF INTERSTELLAR GLYCINE: A COMPUTATIONAL STUDY OF THE REACTIONS OF ACETIC ACID WITH HYDROXYLAMINE AND ITS IONIZED AND PROTONATED DERIVATIVES

    SciT

    Barrientos, Carmen; Redondo, Pilar; Largo, Laura

    2012-04-01

    A computational study of the reactions of hydroxylamine and its ionized and protonated derivatives with acetic acid is provided. The reaction of neutral hydroxylamine with acetic acid, despite being clearly exothermic, involves a very large energy barrier. The reaction of ionized hydroxylamine with acetic acid is also clearly exothermic, but again a significant energy barrier is found (around 24 kcal mol{sup -1} at the CCSD(T) level). The reaction of the most stable protonated isomer of hydroxylamine, NH{sub 3}OH{sup +}, with acetic acid also involves a high barrier (more than 27 kcal mol{sup -1} at the CCSD(T) level). Only the highermore » energy isomer, NH{sub 2}OH{sup +}{sub 2}, leads to a sensibly lower energy barrier (about 2.3 kcal mol{sup -1} at the CCSD(T) level). Nevertheless, an estimate of the reaction coefficient at low temperatures such as those reigning in the interstellar medium gives very low values. Therefore, it seems that precursors of interstellar glycine could not be efficiently produced from the reactions of hydroxylamine-derived ions with acetic acid.« less

  2. Earthquakes: hydrogeochemical precursors

    Ingebritsen, Steven E.; Manga, Michael

    2014-01-01

    Earthquake prediction is a long-sought goal. Changes in groundwater chemistry before earthquakes in Iceland highlight a potential hydrogeochemical precursor, but such signals must be evaluated in the context of long-term, multiparametric data sets.

  3. Achieving phase transformation and structure control of crystalline anatase TiO2@C hybrids from titanium glycolate precursor and glucose molecules.

    PubMed

    Cheng, Gang; Stadler, Florian J

    2015-01-15

    Considerable efforts have focused on functional TiO2@carbonaceous hybrid nanostructured materials (TiO2@C) to satisfy the future requirements of environmental photocatalysis and energy storage using these advanced materials. In this study, we developed a two-step solution-phase reaction to prepare hybrid TiO2@C with tuneable structure and composition from the hydrothermal carbonization (HTC) of glucose. X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA) were used to determine the crystallite size, composition, and phase purity. The results of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high resolution TEM (HRTEM) showed that the morphology of the as-synthesized TiO2@C hybrids could be controlled by varying the amount of glucose, also acting as the carbon source. Based on the observations made with different glucose concentrations, a formation mechanism of nanoparticulate and nanoporous TiO2@C hybrids was proposed. In addition, the as-synthesized TiO2@C hybrids with different compositions and structures showed enhanced adsorption of visible light and improved dye-adsorption capacity, which supported their potential use as photocatalysts with good activity. This new synthetic approach, using a nanoprecursor, provides a simple and versatile way to prepare TiO2@C hybrids with tuneable composition, structures, and properties, and is expected to lead to a family of composites with designed properties. Copyright © 2014 Elsevier Inc. All rights reserved.

  4. The relationship between the electronic structure and thermoelectric properties of Zintl compounds M2Zn5As4 (M = K, Rb).

    PubMed

    Yang, Gui; Yang, Jueming; Yan, Yuli; Wang, Yuanxu

    2014-03-28

    The electronic structure and the thermoelectric properties of M2Zn5As4 (M = K, Rb) are studied by the first principles and the semiclassical BoltzTraP theory. It is determined that they are semiconductors with an indirect band gap of about 1 eV, which is much larger than that of Ca5Al2Sb6 (0.50 eV). The calculated electronic localization function indicates that they are typical Zintl bonding compounds. The combination of heavy and light bands near the valence band maximum may improve their thermoelectric performance. Rb2Zn5As4 exhibits relatively large Seebeck coefficients, high electrical conductivities, and the large "maximum" thermoelectric figures of merit (ZeT). Compared with Ca5Al2Sb6, the highest ZeT of Rb2Zn5As4 appears at relatively low carrier concentration. For Rb2Zn4As5, the p-type doping may achieve a higher thermoelectric performance than n-type doping. The thermoelectric properties of Rb2Zn5As4 are possibly superior to those of Ca5Al2Sb6.

  5. Crystallization Experiments in the MgO-CO2-H2O system: Role of Amorphous Magnesium Carbonate Precursors in Magnesium Carbonate Hydrated Phases and Morphologies in Low Temperature Hydrothermal Fluids

    NASA Astrophysics Data System (ADS)

    Giampouras, Manolis; Garcia-Ruiz, Juan Manuel; Garrido, Carlos J.

    2017-04-01

    Numerous forms of hydrated or basic magnesium carbonates occur in the complex MgO-CO2-H2O system. Mineral saturation states from low temperature hydrothermal fluids in Semail Ophiolite (Oman), Prony Bay (New Caledonia) and Lost City hydrothermal field (mid-Atlantic ridge) strongly indicate the presence of magnesium hydroxy-carbonate hydrates (e.g. hydromagnesite) and magnesium hydroxides (brucite). Study of formation mechanisms and morphological features of minerals forming in the MgO-CO2-H2O system could give insights into serpentinization-driven, hydrothermal, alkaline environments, which are related to early Earth conditions. Temperature, hydration degree, pH and fluid composition are crucial factors regarding the formation, coexistence and transformation of such mineral phases. The rate of supersaturation, on the other hand, is a fundamental parameter to understand nucleation and crystal growth processes. All these parameters can be examined in a solution using different crystallization techniques. In the present study, we applied different crystallization techniques to synthesize and monitor the crystallization of Mg-bearing carbonates and hydroxides under abiotic conditions. Various crystallization techniques (counter-diffusion, vapor diffusion and unseeded solution mixing) were used to screen the formation conditions of each phase, transformation processes and structural development. Mineral and textural characterization of the different synthesized phases were carried out by X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy coupled to dispersive energy spectroscopy (FE-SEM-EDS). Experimental investigation of the effect of pH level and silica content under variable reactant concentrations revealed the importance of Amorphous Magnesium Carbonate (AMC) in the formation of hydroxy-carbonate phases (hydromagnesite and dypingite). Micro-structural resemblance between AMC precursors and later stage crystalline phases highlights the

  6. Density functional theory (DFT) study of the gas-phase decomposition of the Cd[((i)Pr)2PSSe] 2 single-source precursor for the CVD of binary and ternary cadmium chalcogenides.

    PubMed

    Opoku, Francis; Asare-Donkor, Noah Kyame; Adimado, Anthony A

    2014-11-01

    The chemistry of group II-VI semiconductors has spurred considerable interest in decomposition reaction mechanisms and has been exploited for various technological applications. In this work, computational chemistry was employed to investigate the possible gas-phase decomposition pathways of the mixed Cd[((i)Pr)2PSSe]2 single-source precursor for the chemical vapour deposition of cadmium chalcogenides as thin films. The geometries of the species involved were optimised by employing density functional theory at the MO6/LACVP* level. The results indicate that the steps that lead to CdS formation on the singlet potential energy surface are favoured kinetically over those that lead to CdSe and ternary CdSe(x)S(1-x) formation. On the doublet PES, the steps that lead to CdSe formation are favoured kinetically over those that lead to CdS and CdSe(x)S(1-x) formation. However, thermodynamically, the steps that lead to ternary CdSe(x)S(1-x) formation are more favourable than those that lead to CdSe and CdS formation on both the singlet and the doublet PESs. Density functional theory calculations revealed that the first steps exhibit huge activation barriers, meaning that the thermodynamically favourable process takes a very long time to initiate.

  7. Facile and green synthesis of (La0.95Eu0.05)2O2S red phosphors with sulfate-ion pillared layered hydroxides as a new type of precursor: controlled hydrothermal processing, phase evolution and photoluminescence

    PubMed Central

    Wang, Xuejiao; Li, Ji-Guang; Zhu, Qi; Li, Xiaodong; Sun, Xudong; Sakka, Yoshio

    2014-01-01

    This study presents a facile and green route for the synthesis of (La0.95Eu0.05)2O2S red phosphors of controllable morphologies, with the sulfate-type layered hydroxides of Ln2(OH)4SO4·2H2O (Ln = La and Eu) as a new type of precursor. The technique takes advantage of the fact that the precursor has had the exact Ln:S molar ratio of the targeted phosphor, thus saving the hazardous sulfurization reagents indispensable to traditional synthesis. Controlled hydrothermal processing at 120 °C yielded phase-pure Ln2(OH)4SO4·2H2O crystallites in the form of either nanoplates or microprisms, which can both be converted into Ln2O2S phosphor via a Ln2O2SO4 intermediate upon annealing in flowing H2 at a minimum temperature of ∼ 700 °C. The nanoplates collapse into relatively rounded Ln2O2S particles while the microprisms retain well their initial morphologies at 1 200 °C, thus yielding two types of red phosphors. Photoluminescence excitation (PLE) studies found two distinct charge transfer (CT) excitation bands of O2− → Eu3+ at ∼ 270 nm and S2− → Eu3+ at ∼ 340 nm for the Ln2O2S phosphors, with the latter being stronger and both significantly stronger than the intrinsic intra-f transitions of Eu3+. The two types of phosphors share high similarities in the positions of PLE/PL (photoluminescence) bands and both show the strongest red emission at 627 nm (5D0 → 7F2 transition of Eu3+) under S2− → Eu3+ CT excitation at 340 nm. The PLE/PL intensities show clear dependence on particle morphology and calcination temperature, which were investigated in detail. Fluorescence decay analysis reveals that the 627 nm red emission has a lifetime of ∼ 0.5 ms for both types of the phosphors. PMID:27877631

  8. The EM Earthquake Precursor

    NASA Astrophysics Data System (ADS)

    Jones, K. B., II; Saxton, P. T.

    2013-12-01

    Many attempts have been made to determine a sound forecasting method regarding earthquakes and warn the public in turn. Presently, the animal kingdom leads the precursor list alluding to a transmission related source. By applying the animal-based model to an electromagnetic (EM) wave model, various hypotheses were formed, but the most interesting one required the use of a magnetometer with a differing design and geometry. To date, numerous, high-end magnetometers have been in use in close proximity to fault zones for potential earthquake forecasting; however, something is still amiss. The problem still resides with what exactly is forecastable and the investigating direction of EM. After the 1989 Loma Prieta Earthquake, American earthquake investigators predetermined magnetometer use and a minimum earthquake magnitude necessary for EM detection. This action was set in motion, due to the extensive damage incurred and public outrage concerning earthquake forecasting; however, the magnetometers employed, grounded or buried, are completely subject to static and electric fields and have yet to correlate to an identifiable precursor. Secondly, there is neither a networked array for finding any epicentral locations, nor have there been any attempts to find even one. This methodology needs dismissal, because it is overly complicated, subject to continuous change, and provides no response time. As for the minimum magnitude threshold, which was set at M5, this is simply higher than what modern technological advances have gained. Detection can now be achieved at approximately M1, which greatly improves forecasting chances. A propagating precursor has now been detected in both the field and laboratory. Field antenna testing conducted outside the NE Texas town of Timpson in February, 2013, detected three strong EM sources along with numerous weaker signals. The antenna had mobility, and observations were noted for recurrence, duration, and frequency response. Next, two

  9. Precursor composites for oxygen dispersion hardened silver sheathed superconductor composites

    DOEpatents

    Podtburg, E.R.

    1999-06-22

    An oxide superconductor composite having improved texture and durability is disclosed. The oxide superconductor composite includes an oxide superconductor phase substantially surrounded with/by a noble metal matrix, the noble metal matrix comprising a metal oxide in an amount effective to form metal oxide domains that increase hardness of the composite. The composite is characterized by a degree of texture at least 10% greater than a comparable oxide superconductor composite lacking metal oxide domains. An oxide superconducting composite may be prepared by oxidizing the precursor composite under conditions effective to form solute metal oxide domains within the silver matrix and to form a precursor oxide in the precursor alloy phase; subjecting the oxidized composite to a softening anneal under conditions effective to relieve stress within the noble metal phase; and converting the oxide precursor into an oxide superconductor. 1 fig.

  10. Precursor composites for oxygen dispersion hardened silver sheathed superconductor composites

    DOEpatents

    Podtburg, Eric R.

    1999-01-01

    An oxide superconductor composite having improved texture and durability. The oxide superconductor composite includes an oxide superconductor phase substantially surrounded with/by a noble metal matrix, the noble metal matrix comprising a metal oxide in an amount effective to form metal oxide domains that increase hardness of the composite. The composite is characterized by a degree of texture at least 10% greater than a comparable oxide superconductor composite lacking metal oxide domains. An oxide superconducting composite may be prepared by oxidizing the precursor composite under conditions effective to form solute metal oxide domains within the silver matrix and to form a precursor oxide in the precursor alloy phase; subjecting the oxidized composite to a softening anneal under conditions effective to relieve stress within the noble metal phase; and converting the oxide precursor into an oxide superconductor.

  11. Theoretical investigation of M@Pb122- and M@Sn122- Zintl clusters (M = Lrn+, Lun+, La3+, Ac3+ and n = 0, 1, 2, 3).

    PubMed

    Joshi, Meenakshi; Chandrasekar, Aditi; Ghanty, Tapan K

    2018-06-06

    The positions of lawrencium (Lr), lutetium (Lu), actinium (Ac) and lanthanum (La) in the periodic table have been a controversial topic for quite some time. According to studies carried out by different groups with their justifications, these elements may potentially be placed in the d-block, p-block or all four in a 15 element f-block. The present work looks into this issue from a new perspective, which involves encapsulation of these four elements into Zintl ion clusters, Pb122- and Sn122-, followed by the determination of the structural, thermodynamic and electronic properties of these endohedral M@Pb122- and M@Sn122- clusters (M = Lrn+, Lun+ with n = 0, 1, 2, 3) using first principles based density functional theory (DFT). These parameters are compared with similar clusters encapsulated La3+ and Ac3+ ions in order to seek out similarities and differences to draw conclusions about their placement in the periodic table. For the first time the structural, energetic, and electronic properties of these metal atom/ion encapsulated Pb122- and Sn122- clusters have been investigated thoroughly. Structural parameters such as bond distances, geometry and symmetry, electronic properties viz. the density of states, the molecular orbital ordering, the electron localization function, bond critical point properties and charge distributions have been analyzed. Additionally, the thermodynamic property of the binding energy during the encapsulation process has also been calculated. All M@Pb12+ and M@Sn12+ (M = Lr and Lu) clusters form stable 18 bonding electron magic number systems with shell closing. They show negative values of binding energy and relatively large HOMO-LUMO energy gaps indicating the stability of such clusters. All the calculated parameters for Lr encapsulated clusters closely match with the corresponding calculated parameters of Lu encapsulated clusters, confirming the similarity between Lr and Lu metal atoms in various oxidation states, though their atomic

  12. Alternative group V precursors for CVD applications

    NASA Astrophysics Data System (ADS)

    Lum, R. M.; Klingert, J. K.

    1991-01-01

    The chemical vapor deposition (CVD) techniques used to grow III/V semiconductors films, such as metalorganic vapor phase epitaxy (MOVPE), hydride VPE, chemical beam epitaxy (CBE) and gas source molecular beam epitaxy (GS-MBE), all use hydrides (AsH 3 and PH 3) as the Group V source. However, the hydrides are extremely toxic gases which are stored under high pressure (200-2000 psi). To reduce the safety hazards associated with these gases, alternative Group V precursors have been investigated. Organoarsenic and phosphorous compounds have received the most attention as replacements for AsH 3 and PH 3 because they are typically low vapor pressure liquids, and thus present significantly lower exposure risks than the hydrides. For AsH 3 these have included the methyl, ethyl and butyl-based derivatives RnAsH 3- n, with varying degrees ( n = 1-3) of hydrogen atom substitution. In this paper the growth properties, thermochemistry and toxicity of the various alkylarsine precursors are compared with arsine. Data are presented on the impact of the thermochemistry of these compounds on film electrical properties, and on the effects of precursor composition and purity on overall film quality. The suitability of alternative As-precursors for device applications is demonstrated, and selection criteria are presented for the most effective alkylarsine compound for a particular CVD growth process.

  13. An interstellar precursor mission

    NASA Technical Reports Server (NTRS)

    Jaffe, L. D.; Ivie, C.; Lewis, J. C.; Lipes, R. G.; Norton, H. N.; Stearns, J. W.; Stimpson, L.; Weissman, P.

    1977-01-01

    A mission out of the planetary system, with launch about the year 2000, could provide valuable scientific data as well as test some of the technology for a later mission to another star. Primary scientific objectives for the precursor mission concern characteristics of the heliopause, the interstellar medium, stellar distances (by parallax measurements), low energy cosmic rays, interplanetary gas distribution, and mass of the solar system. Secondary objectives include investigation of Pluto. Candidate science instruments are suggested. Individual spacecraft systems for the mission were considered, technology requirements and problem areas noted, and a number of recommendations made for technology study and advanced development. The most critical technology needs include attainment of 50-yr spacecraft lifetime and development of a long-life NEP system.

  14. Insight into the optoelectronic and thermoelectric properties of Ca-based Zintl phase CaCd2X2 (X = P, As) from first principles calculation

    NASA Astrophysics Data System (ADS)

    Belfarh, T.; Batouche, M.; Seddik, T.; Uğur, G.; Omran, S. Bin; Bouhemadou, A.; Sandeep; Wang, Xiaotian; Sun, Xiao-Wei; Khenata, R.

    2018-06-01

    We have studied the structural, optical, electronic and thermoelectric properties of the CaCd2X2 (X = P, As) compounds by using the full-potential augmented plane wave plus local orbitals method (FP-APW + lo). The exchange-correlation potential was treated using both the gradient generalized approximation (WC-GGA) and local density approximation (LDA). The estimated structural parameters, including the lattice parameters and internal coordinates agree well with the available experimental data. Our computed band structure shows that both studied compounds are semiconductors, with direct band gaps (Γ-Γ) of approximately 1.78 eV and 1.2 eV for CaCd2P2 and CaCd2As2, respectively, using GGA-TB-mBJ approach. The calculated optical spectra reveal a strong response of these materials in the energy range between the visible light and extreme UV regions, making them a good candidate for optoelectronic devices. Thermoelectric parameters, such as thermal conductivity, electrical conductivity, Seebeck coefficient, power factor and figure of merit were calculated. We note that both the CaCd2P2 and CaCd2As2 compounds show promising thermoelectric properties.

  15. High Tc superconducting films from metallo-organic precursors

    NASA Astrophysics Data System (ADS)

    Davison, W. W.; Shyu, S. G.; Buchanan, R. C.

    High Tc superconducting films of heavy metal soaps (derived from carboxylic acid precursors) have been prepared on Si and other substrates. The precursors were synthesized and mixed in appropriate molar ratios to form the high Tc compound YBa2Cu3O(7-x), using a high boiling point common solvent base. The precursor solution was deposited by a spin casting technique on the substrates. Film thicknesses of 0.1-1.0 micron were achieved after heat treatment at 550-850 C at not longer than 4 hours. Films were analyzed as to orientation, appropriate phase, interfacial reaction, and superconducting properties.

  16. New insights into the application of the valence rules in Zintl phases—Crystal and electronic structures of Ba{sub 7}Ga{sub 4}P{sub 9}, Ba{sub 7}Ga{sub 4}As{sub 9}, Ba{sub 7}Al{sub 4}Sb{sub 9}, Ba{sub 6}CaAl{sub 4}Sb{sub 9}, and Ba{sub 6}CaGa{sub 4}Sb{sub 9}

    SciT

    He, Hua; Stoyko, Stanislav; Bobev, Svilen, E-mail: bobev@udel.edu

    Crystals of three new ternary pnictides—Ba{sub 7}Al{sub 4}Sb{sub 9}, Ba{sub 7}Ga{sub 4}P{sub 9}, and Ba{sub 7}Ga{sub 4}As{sub 9} have been prepared by reactions of the respective elements in molten Al or Pb fluxes. Single-crystal X-ray diffraction studies reveal that the three phases are isotypic, crystallizing in the orthorhombic Ba{sub 7}Ga{sub 4}Sb{sub 9}-type structure (space group Pmmn, Pearson symbol oP40, Z=2), for which only the prototype is known. The structure is based on TrPn{sub 4} tetrahedra (Tr=Al, Ga; Pn=P, As, Sb), connected in an intricate scheme into 1D-ribbons. Long interchain Pn–Pn bonds (d{sub P–P}>3.0 Å; d{sub As–As}>3.1 Å; d{sub Sb–Sb}>3.3 Å)more » account for the realization of 2D-layers, separated by Ba{sup 2+} cations. Applying the classic valance rules to rationalize the bonding apparently fails, and Ba{sub 7}Ga{sub 4}Sb{sub 9} has long been known as a metallic Zintl phase. Earlier theoretical calculations, both empirical and ab-initio, suggest that the possible metallic properties originate from filled anti-bonding Pn–Pn states, and the special roles of the “cations” in this crystal structure. To experimentally probe this hypothesis, we sought to synthesize the ordered quaternary phases Ba{sub 6}CaTr{sub 4}Sb{sub 9} (Tr=Al, Ga). Single-crystal X-ray diffraction work confirms Ba{sub 6.145(3)}Ca{sub 0.855}Al{sub 4}Sb{sub 9} and Ba{sub 6.235(3)}Ca{sub 0.765}Ga{sub 4}Sb{sub 9}, with Ca atoms preferably substituting Ba on one of the three available sites. The nuances of the five crystal structures are discussed, and the chemical bonding in Ba{sub 7}Ga{sub 4}As{sub 9} is interrogated by tight-binding linear muffin-tin orbital calculations. - Graphical abstract: The new Zintl phases—Ba{sub 7}Al{sub 4}Sb{sub 9}, Ba{sub 7}Ga{sub 4}P{sub 9}, and Ba{sub 7}Ga{sub 4}As{sub 9}, and their quaternary variants Ba{sub 6}CaTr{sub 4}Sb{sub 9} (Tr=Al, Ga)—crystallize in the Ba{sub 7}Ga{sub 4}Sb{sub 9} structure type. The structures

  17. Electromagnetic Whistler Precursors at Supercritical Interplanetary Shocks

    NASA Technical Reports Server (NTRS)

    Wilson, L. B., III

    2012-01-01

    We present observations of electromagnetic precursor waves, identified as whistler mode waves, at supercritical interplanetary shocks using the Wind search coil magnetometer. The precursors propagate obliquely with respect to the local magnetic field, shock normal vector, solar wind velocity, and they are not phase standing structures. All are right-hand polarized with respect to the magnetic field (spacecraft frame), and all but one are right-hand polarized with respect to the shock normal vector in the normal incidence frame. Particle distributions show signatures of specularly reflected gyrating ions, which may be a source of free energy for the observed modes. In one event, we simultaneously observe perpendicular ion heating and parallel electron acceleration, consistent with wave heating/acceleration due to these waves.

  18. Precursor Mediated Synthesis of Nanostructured Silicas: From Precursor-Surfactant Ion Pairs to Structured Materials.

    PubMed

    Hesemann, Peter; Nguyen, Thy Phung; Hankari, Samir El

    2014-04-11

    The synthesis of nanostructured anionic-surfactant-templated mesoporous silica (AMS) recently appeared as a new strategy for the formation of nanostructured silica based materials. This method is based on the use of anionic surfactants together with a co-structure-directing agent (CSDA), mostly a silylated ammonium precursor. The presence of this CSDA is necessary in order to create ionic interactions between template and silica forming phases and to ensure sufficient affinity between the two phases. This synthetic strategy was for the first time applied in view of the synthesis of surface functionalized silica bearing ammonium groups and was then extended on the formation of materials functionalized with anionic carboxylate and bifunctional amine-carboxylate groups. In the field of silica hybrid materials, the "anionic templating" strategy has recently been applied for the synthesis of silica hybrid materials from cationic precursors. Starting from di- or oligosilylated imidazolium and ammonium precursors, only template directed hydrolysis-polycondensation reactions involving complementary anionic surfactants allowed accessing structured ionosilica hybrid materials. The mechanistic particularity of this approach resides in the formation of precursor-surfactant ion pairs in the hydrolysis-polycondensation mixture. This review gives a systematic overview over the various types of materials accessed from this cooperative ionic templating approach and highlights the high potential of this original strategy for the formation of nanostructured silica based materials which appears as a complementary strategy to conventional soft templating approaches.

  19. Precursor Mediated Synthesis of Nanostructured Silicas: From Precursor-Surfactant Ion Pairs to Structured Materials

    PubMed Central

    Hesemann, Peter; Nguyen, Thy Phung; Hankari, Samir El

    2014-01-01

    The synthesis of nanostructured anionic-surfactant-templated mesoporous silica (AMS) recently appeared as a new strategy for the formation of nanostructured silica based materials. This method is based on the use of anionic surfactants together with a co-structure-directing agent (CSDA), mostly a silylated ammonium precursor. The presence of this CSDA is necessary in order to create ionic interactions between template and silica forming phases and to ensure sufficient affinity between the two phases. This synthetic strategy was for the first time applied in view of the synthesis of surface functionalized silica bearing ammonium groups and was then extended on the formation of materials functionalized with anionic carboxylate and bifunctional amine-carboxylate groups. In the field of silica hybrid materials, the “anionic templating” strategy has recently been applied for the synthesis of silica hybrid materials from cationic precursors. Starting from di- or oligosilylated imidazolium and ammonium precursors, only template directed hydrolysis-polycondensation reactions involving complementary anionic surfactants allowed accessing structured ionosilica hybrid materials. The mechanistic particularity of this approach resides in the formation of precursor-surfactant ion pairs in the hydrolysis-polycondensation mixture. This review gives a systematic overview over the various types of materials accessed from this cooperative ionic templating approach and highlights the high potential of this original strategy for the formation of nanostructured silica based materials which appears as a complementary strategy to conventional soft templating approaches. PMID:28788602

  20. Preparation of superconductor precursor powders

    DOEpatents

    Bhattacharya, Raghunath

    1998-01-01

    A process for the preparation of a precursor metallic powder composition for use in the subsequent formation of a superconductor. The process comprises the steps of providing an electrodeposition bath comprising an electrolyte medium and a cathode substrate electrode, and providing to the bath one or more soluble salts of one or more respective metals which are capable of exhibiting superconductor properties upon subsequent appropriate treatment. The bath is continually energized to cause the metallic and/or reduced particles formed at the electrode to drop as a powder from the electrode into the bath, and this powder, which is a precursor powder for superconductor production, is recovered from the bath for subsequent treatment. The process permits direct inclusion of all metals in the preparation of the precursor powder, and yields an amorphous product mixed on an atomic scale to thereby impart inherent high reactivity. Superconductors which can be formed from the precursor powder include pellet and powder-in-tube products.

  1. A low temperature solution phases synthesis for silicon quantum dots

    SciT

    Bley, R.A.; Yang, Chung-Sung; Kauzlarich, S.M.

    Silicon nanoparticles are of interest because of their optoelectronic properties. This warrants finding new methods for making these clusters which are more economical and allow for greater versatility in their mechanical and chemical manipulation. We have produced silicon nanoclusters using a low temperature solution phase method. Our approach uses the Zintl salts KSi, NaSi or Mg{sub 2}Si as the source of silicon anion, This is reacted with tetrachlorosilane, the silicon cation source, in appropriate solvents. These nanoclusters have been terminated with various organic groups via reaction with alkyl-Li or alkylgrignard reagents. High resolution TEM, FTIR, and Raman spectroscopy have beenmore » used to establish the size, structure and surface composition of the particles. UV-vis and photoluminescence have been used to investigate their optical properties. The effect of termination on the photoluminescence will be discussed in detail.« less

  2. Supramolecular Assembly of Single-Source Metal-Chalcogenide Nanocrystal Precursors.

    PubMed

    Smith, Stephanie C; Bryks, Whitney; Tao, Andrea R

    2018-05-28

    In this Feature Article, we discuss our recent work in the synthesis of novel supramolecular precursors for semiconductor nanocrystals. Metal chalcogenolates that adopt liquid crystalline phases are employed as single-source precursors that template the growth of shaped solid-state nanocrystals. Supramolecular assembly is programmed by both precursor chemical composition and molecular parameters such alkyl chain length, steric bulk, and the intercalation of halide ions. Here, we explore the various design principles that enable the rational synthesis of these single-source precursors, their liquid crystalline phases, and the various semiconductor nanocrystal products that can be generated by thermolysis, ranging from highly anisotropic two-dimensional nanosheets and nanodisks to spheres.

  3. Observations of Electron-driven Evaporation in a Flare Precursor

    NASA Astrophysics Data System (ADS)

    Li, Dong; Li, Ying; Su, Wei; Huang, Yu; Ning, Zongjun

    2018-02-01

    We investigate the relationship between the blueshifts of a hot emission line and the nonthermal emissions in microwave and hard X-ray (HXR) wavelengths in the precursor of a solar flare on 2014 October 27. The flare precursor is identified as a small but well-developed peak in the soft X-ray and extreme-ultraviolet passbands before the GOES flare onset, which is accompanied by a pronounced burst in microwave 17 and 34 GHz and in HXR 25–50 keV. The slit of the Interface Region Imaging Spectrograph (IRIS) stays on one ribbon-like transient during the flare precursor phase, which shows visible nonthermal emissions in Nobeyama Radioheliograph and RHESSI images. The IRIS spectroscopic observations show that the hot line of Fe XXI 1354.09 Å (log T ∼ 7.05) displays blueshifts, while the cool line of Si IV 1402.77 Å (log T ∼ 4.8) exhibits redshifts. The blueshifts and redshifts are well correlated with each other, indicative of an explosive chromospheric evaporation during the flare precursor phase combining a high nonthermal energy flux with a short characteristic timescale. In addition, the blueshifts of Fe XXI 1354.09 Å are well correlated with the microwave and HXR emissions, implying that the explosive chromospheric evaporation during the flare precursor phase is driven by nonthermal electrons.

  4. Brillouin precursors in Debye media

    NASA Astrophysics Data System (ADS)

    Macke, Bruno; Ségard, Bernard

    2015-05-01

    We theoretically study the formation of Brillouin precursors in Debye media. We point out that the precursors are visible only at propagation distances such that the impulse response of the medium is essentially determined by the frequency dependence of its absorption and is practically Gaussian. By simple convolution, we then obtain explicit analytical expressions of the transmitted waves generated by reference incident waves, distinguishing precursor and main signal by a simple examination of the long-time behavior of the overall signal. These expressions are in good agreement with the signals obtained in numerical or real experiments performed on water in the radio-frequency domain and explain in particular some observed shapes of the precursor. Results are obtained for other remarkable incident waves. In addition, we show quite generally that the shape of the Brillouin precursor appearing alone at sufficiently large propagation distance and the law giving its amplitude as a function of this distance do not depend on the precise form of the incident wave but only on its integral properties. The incidence of a static conductivity of the medium is also examined and explicit analytical results are again given in the limit of weak and strong conductivities.

  5. Phase behavior and crystal structure of 3-(1-naphthyloxy)- and 3-(4-indolyloxy)-propane-1,2-diol, synthetic precursors of chiral drugs propranolol and pindolol

    NASA Astrophysics Data System (ADS)

    Bredikhin, Alexander A.; Gubaidullin, Aidar T.; Bredikhina, Zemfira A.; Fayzullin, Robert R.; Samigullina, Aida I.; Zakharychev, Dmitry V.

    2013-08-01

    Valuable precursors of popular chiral drugs propranolol and pindolol, 3-(1-naphthyloxy)-propane-1,2-diol 3 and 3-(4-indolyloxy)-propane-1,2-diol 4 were investigated by IR spectroscopy, DSC, and X-ray diffraction methods. Both compounds, crystallizing from enantiopure feed material, form "guaifenesin-like" crystal packing in which the classic H-bonded bilayers, framed in both sides by hydrophobic fragments of the molecules, acts as the basic crystal-forming motif. Diol 4 prone to spontaneous resolution and conserves its packing pattern crystallizing from racemate. Under the same conditions, diol 3 forms weakly stable solid racemic compound. Some reasons for such a behavior are identified and discussed.

  6. Preparation of superconductor precursor powders

    DOEpatents

    Bhattacharya, R.

    1998-08-04

    A process for the preparation of a precursor metallic powder composition for use in the subsequent formation of a superconductor. The process comprises the steps of providing an electrodeposition bath comprising an electrolyte medium and a cathode substrate electrode, and providing to the bath one or more soluble salts of one or more respective metals which are capable of exhibiting superconductor properties upon subsequent appropriate treatment. The bath is continually energized to cause the metallic and/or reduced particles formed at the electrode to drop as a powder from the electrode into the bath, and this powder, which is a precursor powder for superconductor production, is recovered from the bath for subsequent treatment. The process permits direct inclusion of all metals in the preparation of the precursor powder, and yields an amorphous product mixed on an atomic scale to thereby impart inherent high reactivity. Superconductors which can be formed from the precursor powder include pellet and powder-in-tube products. 7 figs.

  7. Preparation of superconductor precursor powders

    DOEpatents

    Bhattacharya, Raghunath; Blaugher, Richard D.

    1995-01-01

    A process for the preparation of a precursor metallic powder composition for use in the subsequent formation of a superconductor. The process comprises the steps of providing an electrodeposition bath comprising an electrolyte medium and a cathode substrate electrode, and providing to the bath one or more soluble salts of one or more respective metals, such as nitrate salts of thallium, barium, calcium, and copper, which are capable of exhibiting superconductor properties upon subsequent appropriate treatment. The bath is continually energized to cause the metallic particles formed at the electrode to drop as a powder from the electrode into the bath, and this powder, which is a precursor powder for superconductor production, is recovered from the bath for subsequent treatment. The process permits direct inclusion of thallium in the preparation of the precursor powder, and yields an amorphous product mixed on an atomic scale to thereby impart inherent high reactivity. Superconductors which can be formed from the precursor powder include pellet and powder-in-tube products.

  8. Bound Volatile Precursors in Genotypes in the Pedigree of 'Marion' Blackberry (Rubus Sp.)

    Glycosidically bound volatiles and precursors in genotypes representing the pedigree for 'Marion' blackberry were investigated over two growing seasons. The volatile precursors were isolated using a C18 solid-phase extraction column. After enzymatic hydrolysis, the released volatiles were analyzed u...

  9. Vaporization of a mixed precursors in chemical vapor deposition for YBCO films

    NASA Technical Reports Server (NTRS)

    Zhou, Gang; Meng, Guangyao; Schneider, Roger L.; Sarma, Bimal K.; Levy, Moises

    1995-01-01

    Single phase YBa2Cu3O7-delta thin films with T(c) values around 90 K are readily obtained by using a single source chemical vapor deposition technique with a normal precursor mass transport. The quality of the films is controlled by adjusting the carrier gas flow rate and the precursor feed rate.

  10. Transition Metal Dichalcogenide Growth via Close Proximity Precursor Supply

    NASA Astrophysics Data System (ADS)

    O'Brien, Maria; McEvoy, Niall; Hallam, Toby; Kim, Hye-Young; Berner, Nina C.; Hanlon, Damien; Lee, Kangho; Coleman, Jonathan N.; Duesberg, Georg S.

    2014-12-01

    Reliable chemical vapour deposition (CVD) of transition metal dichalcogenides (TMDs) is currently a highly pressing research field, as numerous potential applications rely on the production of high quality films on a macroscopic scale. Here, we show the use of liquid phase exfoliated nanosheets and patterned sputter deposited layers as solid precursors for chemical vapour deposition. TMD monolayers were realized using a close proximity precursor supply in a CVD microreactor setup. A model describing the growth mechanism, which is capable of producing TMD monolayers on arbitrary substrates, is presented. Raman spectroscopy, photoluminescence, X-ray photoelectron spectroscopy, atomic force microscopy, transmission electron microscopy, scanning electron microscopy and electrical transport measurements reveal the high quality of the TMD samples produced. Furthermore, through patterning of the precursor supply, we achieve patterned growth of monolayer TMDs in defined locations, which could be adapted for the facile production of electronic device components.

  11. Comparative examination of titania nanocrystals synthesized by peroxo titanic acid approach from different precursors.

    PubMed

    Liu, Yong-Jun; Aizawa, Mami; Wang, Zheng-Ming; Hatori, Hiroaki; Uekawa, Naofumi; Kanoh, Hirofumi

    2008-06-15

    Titanium dioxide nanocrystalline particles were synthesized by peroxo titanium acid (PTA) approach from titanium alkoxide and inorganic salt precursors, and their structural and surface properties, porosities, and photocatalytic activities were comparatively examined by XRD, TG/DTA, DRIFT, UV-vis, low temperature N(2) adsorption, and methyl orange (MO) degradation. It was found that nanoparticles with single anatase phase can be obtained from alkoxide precursor even near room temperature if synthesis conditions are appropriately controlled. PTA-derived anatase nanoparticles from titanium alkoxide precursor have smaller crystalline sizes and better porosities, and contain less amount of peroxo group and no organic impurities as compared to those from TiCl(4) precursor. The advantages in structural property, porosity, and surface properties (few deficiencies) lead to a much better photocatalytic activity for TiO(2) nanoparticles from titanium alkoxide precursor in comparison with those from TiCl(4) precursor.

  12. Precursor polymer compositions comprising polybenzimidazole

    DOEpatents

    Klaehn, John R.; Peterson, Eric S.; Orme, Christopher J.

    2015-07-14

    Stable, high performance polymer compositions including polybenzimidazole (PBI) and a melamine-formaldehyde polymer, such as methylated, poly(melamine-co-formaldehyde), for forming structures such as films, fibers and bulky structures. The polymer compositions may be formed by combining polybenzimidazole with the melamine-formaldehyde polymer to form a precursor. The polybenzimidazole may be reacted and/or intertwined with the melamine-formaldehyde polymer to form the polymer composition. For example, a stable, free-standing film having a thickness of, for example, between about 5 .mu.m and about 30 .mu.m may be formed from the polymer composition. Such films may be used as gas separation membranes and may be submerged into water for extended periods without crazing and cracking. The polymer composition may also be used as a coating on substrates, such as metal and ceramics, or may be used for spinning fibers. Precursors for forming such polymer compositions are also disclosed.

  13. The Innate Lymphoid Cell Precursor.

    PubMed

    Ishizuka, Isabel E; Constantinides, Michael G; Gudjonson, Herman; Bendelac, Albert

    2016-05-20

    The discovery of tissue-resident innate lymphoid cell populations effecting different forms of type 1, 2, and 3 immunity; tissue repair; and immune regulation has transformed our understanding of mucosal immunity and allergy. The emerging complexity of these populations along with compounding issues of redundancy and plasticity raise intriguing questions about their precise lineage relationship. Here we review advances in mapping the emergence of these lineages from early lymphoid precursors. We discuss the identification of a common innate lymphoid cell precursor characterized by transient expression of the transcription factor PLZF, and the lineage relationships of innate lymphoid cells with conventional natural killer cells and lymphoid tissue inducer cells. We also review the rapidly growing understanding of the network of transcription factors that direct the development of these lineages.

  14. Vapor pressure of germanium precursors

    NASA Astrophysics Data System (ADS)

    Pangrác, J.; Fulem, M.; Hulicius, E.; Melichar, K.; Šimeček, T.; Růžička, K.; Morávek, P.; Růžička, V.; Rushworth, S. A.

    2008-11-01

    The vapor pressure of two germanium precursors tetrakis(methoxy)germanium (Ge(OCH 3) 4, CASRN 992-91-6) and tetrakis(ethoxy)germanium (Ge(OC 2H 5) 4, CASRN 14165-55-0) was determined using a static method in the temperature range 259-303 K. The experimental vapor pressure data were fit with the Antoine equation. The mass spectra before and after degassing by vacuum distillation at low temperature are also reported and discussed.

  15. Precursor Lesions of Urologic Malignancies.

    PubMed

    Khani, Francesca; Robinson, Brian D

    2017-12-01

    - Precursor lesions of urologic malignancies are established histopathologic entities, which are important not only to recognize for clinical purposes, but also to further investigate at the molecular level in order to gain a better understanding of the pathogenesis of these malignancies. - To provide a brief overview of precursor lesions to the most common malignancies that develop within the genitourinary tract with a focus on their clinical implications, histologic features, and molecular characteristics. - Literature review from PubMed, urologic pathology textbooks, and the 4th edition of the World Health Organization Classification of Tumours of the Urinary System and Male Genital Organs. All photomicrographs were taken from cases seen at Weill Cornell Medicine or from the authors' personal slide collections. - The clinical importance and histologic criteria are well established for the known precursor lesions of the most common malignancies throughout the genitourinary tract, but further investigation is warranted at the molecular level to better understand the pathogenesis of these lesions. Such investigation may lead to better risk stratification of patients and potentially novel treatments.

  16. Simultaneous constraint and phase conversion processing of oxide superconductors

    DOEpatents

    Li, Qi; Thompson, Elliott D.; Riley, Jr., Gilbert N.; Hellstrom, Eric E.; Larbalestier, David C.; DeMoranville, Kenneth L.; Parrell, Jeffrey A.; Reeves, Jodi L.

    2003-04-29

    A method of making an oxide superconductor article includes subjecting an oxide superconductor precursor to a texturing operation to orient grains of the oxide superconductor precursor to obtain a highly textured precursor; and converting the textured oxide superconducting precursor into an oxide superconductor, while simultaneously applying a force to the precursor which at least matches the expansion force experienced by the precursor during phase conversion to the oxide superconductor. The density and the degree of texture of the oxide superconductor precursor are retained during phase conversion. The constraining force may be applied isostatically.

  17. Increased KPI containing amyloid precursor protein in experimental autoimmune encephalomyelitis brains.

    PubMed

    Beilin, Orit; Karussis, Dimitrios M; Korczyn, Amos D; Gurwitz, David; Aronovich, Ramona; Mizrachi-Kol, Rachel; Chapman, Joab

    2007-04-16

    Amyloid precursor protein can be translated from three alternatively spliced mRNAs. We measured levels of amyloid precursor protein isoforms containing the Kunitz protease inhibitor domain (KPIAPP), and amyloid precursor protein without the Kunitz protease inhibitor domain (KPIAPP) in brain homogenates of acute experimental autoimmune encephalomyelitis mice. At the preclinical phase of the disease, both KPIAPP and KPIAPP levels were significantly higher in homogenates from brains of autoimmune encephalomyelitis mice, whereas at the acute phase of the disease only KPIAPP remained significantly elevated compared with controls. At the recovery phase, no differences were observed between the groups. The early and isoform-specific elevation of KPIAPP in autoimmune encephalomyelitis mice suggests a possible role for amyloid precursor protein in the immune response mediating the disease.

  18. Annealing of aromatic polyimide precursors

    NASA Technical Reports Server (NTRS)

    Wakelyn, N. T.

    1975-01-01

    A study has been made of the thermal behavior of polyimide precursors: an isomeric pair of crystals of the complex formed by p-phenylenediamine with the separated isomers of the di-isopropyl ester of pyromellitic acid. Specimens of this material were isothermally annealed in the temperature range 120 C to 170 C for periods of time up to 1 week. Although this temperature range is well below that customarily used for imidizations, the working hypothesis was that it would be more likely that a polymer embodying at least part of the precursor structure could be formed if the molecular motion was minimized to that actually required for the formation of the imide linkage. The progress of the annealing was followed by: infrared spectroscopy, differential thermal analysis, powder X-ray diffraction, and thermal gravimetric analysis. Single crystal X-ray analysis of the meta monomer yields a structure of chains of alternating acid and base and suggests that this monomer is amenable to polymerization with a minimum of geometrical disruption.

  19. Functional Analyses and Treatment of Precursor Behavior

    PubMed Central

    Najdowski, Adel C; Wallace, Michele D; Ellsworth, Carrie L; MacAleese, Alicia N; Cleveland, Jackie M

    2008-01-01

    Functional analysis has been demonstrated to be an effective method to identify environmental variables that maintain problem behavior. However, there are cases when conducting functional analyses of severe problem behavior may be contraindicated. The current study applied functional analysis procedures to a class of behavior that preceded severe problem behavior (precursor behavior) and evaluated treatments based on the outcomes of the functional analyses of precursor behavior. Responding for all participants was differentiated during the functional analyses, and individualized treatments eliminated precursor behavior. These results suggest that functional analysis of precursor behavior may offer an alternative, indirect method to assess the operant function of severe problem behavior. PMID:18468282

  20. Mars MetNet Precursor Mission Status

    NASA Astrophysics Data System (ADS)

    Harri, Ari-Matti; Aleksashkin, Sergey; Guerrero, Héctor; Schmidt, Walter; Genzer, Maria; Vazquez, Luis; Haukka, Harri

    2013-04-01

    A new kind of planetary exploration mission for Mars is being developed in collaboration between the Finnish Meteorological Institute (FMI), Lavochkin Association (LA), Space Research Institute (IKI) and Institutio Nacional de Tecnica Aerospacial (INTA). The Mars MetNet mission is based on a new semi-hard landing vehicle called MetNet Lander (MNL), using an inflatable entry and descent system instead of rigid heat shields and parachutes as earlier semi-hard landing devices have used. This way the ratio of the payload mass to the overall mass is optimized. The landing impact will burrow the payload container into the Martian soil providing a more favorable thermal environment for the electronics and a suitable orientation of the telescopic boom with external sensors and the radio link antenna. It is planned to deploy several tens of MNLs on the Martian surface operating at least partly at the same time to allow meteorological network science. For the precursor mission (MMPM) intended to verify the landing concept and key technology during a real Mars mission all qualification activities are completed and the payload and system flight model components are being manufactured. The descent processes dynamic properties are monitored by a special 3-axis accelerometer combined with a 3-axis gyrometer. The data will be sent via auxiliary beacon antenna throughout the descent phase starting shortly after separation from the spacecraft. Details of the current MMPM system and payload configuration and their performance parameters will be shown.

  1. New Polymeric Precursors of Silicon Carbide

    NASA Technical Reports Server (NTRS)

    Litt, M.; Kumar, K.

    1987-01-01

    Silicon carbide made by pyrolizing polymers. Method conceived for preparation of poly(decamethylcyclohexasilanes) as precursors for preparation of silicon carbide at high yield. Technical potential of polysilanes as precursors of SiC ceramics being explored. Potential limited by intractability of some polysilanes; formation of small, cyclic polycarbosilane fragments during pyrolysis; and overall low char yield and large shrinkage in conversion to ceramics.

  2. The Interrelationships of Mathematical Precursors in Kindergarten

    ERIC Educational Resources Information Center

    Cirino, Paul T.

    2011-01-01

    This study evaluated the interrelations among cognitive precursors across quantitative, linguistic, and spatial attention domains that have been implicated for math achievement in young children. The dimensionality of the quantity precursors was evaluated in 286 kindergarteners via latent variable techniques, and the contribution of precursors…

  3. Precursors and adjuncts of a lunar base

    NASA Technical Reports Server (NTRS)

    Burke, J. D.

    1988-01-01

    The automated, teleoperated, robotic and human-tended subsystems which will precede and accompany a lunar base program are discussed. The information about lunar conditions that can be provided by such precursors and adjuncts is addressed. The use of precursors and adjuncts for communications and navigation, for safety and survival, for lunar archives, and for entertainment and leisure is examined.

  4. Glass precursor approach to high-temperature superconductors

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.

    1992-01-01

    The available studies on the synthesis of high T sub c superconductors (HTS) via the glass precursor approach were reviewed. Melts of the Bi-Sr-Ca-Cu-O system as well as those doped with oxides of some other elements (Pb, Al, V, Te, Nb, etc.) could be quenched into glasses which, on further heat treatments under appropriate conditions, crystallized into the superconducting phase(s). The nature of the HTS phase(s) formed depends on the annealing temperature, time, atmosphere, and the cooling rate and also on the glass composition. Long term annealing was needed to obtain a large fraction of the 110 K phase. The high T sub c phase did not crystallize out directly from the glass matrix, but was preceded by the precipitation of other phases. The 110 K HTS was produced at high temperatures by reaction between the phases formed at lower temperatures resulting in multiphase material. The presence of a glass former such as B2O3 was necessary for the Y-Ba-Cu-O melt to form a glass on fast cooling. A discontinuous YBa2Cu3O(7-delta) HTS phase crystallized out on heat treatment of this glass. Attempts to prepare Tl-Ba-Ca-Cu-O system in the glassy state were not successful.

  5. The Interrelationships of Mathematical Precursors in Kindergarten

    PubMed Central

    Cirino, Paul T.

    2011-01-01

    This study evaluated the interrelations among cognitive precursors across quantitative, linguistic, and spatial attention domains that have been implicated for math achievement in young children. The dimensionality of the quantity precursors was evaluated in 286 Kindergarteners via latent variable techniques, and the contribution of precursors from each domain was established for small sums addition. Results showed a five factor structure for the quantity precursors with the major distinction between nonsymbolic and symbolic tasks. The overall model demonstrated good fit, and strong predictive power (R2 = 55%) for addition number combinations. Linguistic and spatial attention domains showed indirect relationships with outcomes, with their effects mediated by symbolic quantity measures. These results have implications for the measurement of mathematical precursors, and yield promise for predicting future math performance. PMID:21194711

  6. Method of texturing a superconductive oxide precursor

    DOEpatents

    DeMoranville, Kenneth L.; Li, Qi; Antaya, Peter D.; Christopherson, Craig J.; Riley, Jr., Gilbert N.; Seuntjens, Jeffrey M.

    1999-01-01

    A method of forming a textured superconductor wire includes constraining an elongated superconductor precursor between two constraining elongated members placed in contact therewith on opposite sides of the superconductor precursor, and passing the superconductor precursor with the two constraining members through flat rolls to form the textured superconductor wire. The method includes selecting desired cross-sectional shape and size constraining members to control the width of the formed superconductor wire. A textured superconductor wire formed by the method of the invention has regular-shaped, curved sides and is free of flashing. A rolling assembly for single-pass rolling of the elongated precursor superconductor includes two rolls, two constraining members, and a fixture for feeding the precursor superconductor and the constraining members between the rolls. In alternate embodiments of the invention, the rolls can have machined regions which will contact only the elongated constraining members and affect the lateral deformation and movement of those members during the rolling process.

  7. Ionospheric parameters as the precursors of disturbed geomagnetic conditions

    NASA Astrophysics Data System (ADS)

    Blagoveshchensky, D. V.; Sergeeva, M. A.; Kozlovsky, A.

    2017-12-01

    Geomagnetic storms and substorms are the principal elements of the disturbed Space Weather conditions. The aim of the study was to reveal the ionospheric precursors that can be used to forecast geomagnetic disturbance beginning. To study the ionospheric processes before, during and after magnetic storms and substorms data from Sodankylä Geophysical Observatory was used (geomagnetic coordinates: 64.1oN, 119.2oE). In earlier works the Main Effect (ME) was revealed for substorms. It consists of the following steps: (a) the increase of critical frequency foF2 from its quiet median before and during the substorm growth phase, four-five hours before To moment that is the moment of the expansion phase onset, (b) the foF2 decrease to the level lower than its median just after To and until Te that is the moment of the end of the expansion phase, (c) the issue ;a; repeated during the recovery phase (d) two bell-shape spikes in the cutoff frequency values foEs: first spike occurs three hours before To, second spike - during the expansion phase within the interval between To and Te. In the present work it is shown that ME manifestations can be used as precursors of magnetic substorms at high-latitudes (geomagnetic latitudes 50oN-65oN). In particular, the foF2 growth some hours before To can be used as a precursor of substorm development. The first foEs bell-shaped spike also can be used for short-term forecasting, two-three hours in advance of a substorm. Furthermore, the storms between 2008 and 2012 were studied. It was revealed that the similar ME also takes place in the case of magnetic storms but within the different time scale. More specifically, the first ME maximum in foF2 values occurs one-two days before the storm beginning and can be used as its precursor. In addition, the foEs spike takes place approximately ten hours before a storm and also can be used for the prediction of the storm beginning.

  8. Synthesis and structures of metal chalcogenide precursors

    NASA Technical Reports Server (NTRS)

    Hepp, Aloysius F.; Duraj, Stan A.; Eckles, William E.; Andras, Maria T.

    1990-01-01

    The reactivity of early transition metal sandwich complexes with sulfur-rich molecules such as dithiocarboxylic acids was studied. Researchers recently initiated work on precursors to CuInSe2 and related chalcopyrite semiconductors. Th every high radiation tolerance and the high absorption coefficient of CuInSe2 makes this material extremely attractive for lightweight space solar cells. Their general approach in early transition metal chemistry, the reaction of low-valent metal complexes or metal powders with sulfur and selenium rich compounds, was extended to the synthesis of chalcopyrite precursors. Here, the researchers describe synthesis, structures, and and routes to single molecule precursors to metal chalcogenides.

  9. Observations of Electromagnetic Whistler Precursors at Supercritical Interplanetary Shocks

    NASA Technical Reports Server (NTRS)

    Wilson, L. B., III; Koval, A.; Szabo, Adam; Breneman, A.; Cattell, C. A.; Goetz, K.; Kellogg, P. J.; Kersten, K.; Kasper, J. C.; Maruca, B. A.; hide

    2012-01-01

    We present observations of electromagnetic precursor waves, identified as whistler mode waves, at supercritical interplanetary shocks using the Wind search coil magnetometer. The precursors propagate obliquely with respect to the local magnetic field, shock normal vector, solar wind velocity, and they are not phase standing structures. All are right-hand polarized with respect to the magnetic field (spacecraft frame), and all but one are right-hand polarized with respect to the shock normal vector in the normal incidence frame. They have rest frame frequencies f(sub ci) < f much < f(sub ce) and wave numbers 0.02 approx < k rho (sub ce) approx <. 5.0. Particle distributions show signatures of specularly reflected gyrating ions, which may be a source of free energy for the observed modes. In one event, we simultaneously observe perpendicular ion heating and parallel electron acceleration, consistent with wave heating/acceleration due to these waves. Al though the precursors can have delta B/B(sub o) as large as 2, fluxgate magnetometer measurements show relatively laminar shock transitions in three of the four events.

  10. On important precursor of singular optics (tutorial)

    NASA Astrophysics Data System (ADS)

    Polyanskii, Peter V.; Felde, Christina V.; Bogatyryova, Halina V.; Konovchuk, Alexey V.

    2018-01-01

    The rise of singular optics is usually associated with the seminal paper by J. F. Nye and M. V. Berry [Proc. R. Soc. Lond. A, 336, 165-189 (1974)]. Intense development of this area of modern photonics has started since the early eighties of the XX century due to invention of the interfrence technique for detection and diagnostics of phase singularities, such as optical vortices in complex speckle-structured light fields. The next powerful incentive for formation of singular optics into separate area of the science on light was connectected with discovering of very practical technique for creation of singular optical beams of various kinds on the base of computer-generated holograms. In the eghties and ninetieth of the XX century, singular optics evolved, almost entirely, under the approximation of complete coherency of light field. Only at the threshold of the XXI century, it has been comprehended that the singular-optics approaches can be fruitfully expanded onto partially spatially coherent, partially polarized and polychromatic light fields supporting singularities of new kinds, that has been resulted in establishing of correlation singular optics. Here we show that correlation singular optics has much deeper roots, ascending to "pre-singular" and even pre-laser epoch and associated with the concept of partial coherence and polarization. It is remarcable that correlation singular optics in its present interpretation has forestalled the standard coherent singular optics. This paper is timed to the sixtieth anniversary of the most profound precursor of modern correlation singular optics [J. Opt. Soc. Am., 47, 895-902 (1957)].

  11. Molecular precursor routes to transition metal sulfides

    NASA Astrophysics Data System (ADS)

    Dinnage, Christopher Walker

    This thesis is primarily concerned with the synthesis of homoleptic early transition meta thiolates and the subsequent preparation of bulk and thin-film metal disulfides from these compounds. Chapter 1 gives an introduction into the properties, preparation procedures and uses of bulk and thin-film transition metal disulfides as well as giving an overview of early transition metal thiolates synthesied so far in the literature (for titanium, zirconium, tantalum and niobium). Chapter 2 is concerned with the synthesis of a number of ionic and neutral transition metal thiolates. The main synthetic methodologies discussed in this chapter include substitution reactions of transition metal amides and alkyls with thiols, salt metathesis reactions of transition metal chlorides with alkali metal thiolates or with a base / thiol and the use of Grignard reagents. Chapter 3 discusses the preparation of bulk transition metal disulfides using the thiolates prepared in the previous chapter via a thio "sol-gel" route. The preparation of a range of bulk metal and mixed-metal disulfides using transition metal chlorides and hexamethyldisilathiane is also discussed in this chapter. Finally, chapter 4 is concerned with the attempted preparation of thin-films of some transition metal disulfides. Decomposition studies of some of the thiolates prepared in chapter 2 are discussed using thermal gravimetric analysis. Vapour-phase deposition studies are also explored in order to test the potential of the transition metal thiolates as precursors to the disulfides. Experiments using low-pressure chemical vapour deposition and aerosol-assisted chemical vapour deposition are also described.

  12. 1994 Accident sequence precursor program results

    SciT

    Belles, R.J.; Cletcher, J.W.; Copinger, D.A.

    1996-01-01

    The Accident Sequence Precursor (ASP) Program involves the systematic review and evaluation of operational events that have occurred at light-water reactors to identify and categorize precursors to potential severe core damage accident sequences. The results of the ASP Program are published in an annual report. The most recent report, which contains the analyses of the precursors for 1994, is NUREG/CR-4674, Vols. 21 and 22, Precursors to Potential Severe Core Damage Accidents: 1994, A Status Report, published in December 1995. This article provides an overview of the ASP review and evaluation process and a summary of the results for 1994. 12more » refs., 2 figs., 4 tabs.« less

  13. Thin Film CuInS2 Prepared by Spray Pyrolysis with Single-Source Precursors

    NASA Technical Reports Server (NTRS)

    Jin, Michael H.; Banger, Kulinder K.; Harris, Jerry D.; Cowen, Jonathan E.; Hepp, Aloysius F.; Lyons, Valerie (Technical Monitor)

    2002-01-01

    Both horizontal hot-wall and vertical cold-wall atmospheric chemical spray pyrolysis processes deposited near single-phase stoichiometric CuInS2 thin films. Single-source precursors developed for ternary chalcopyrite materials were used for this study, and a new liquid phase single-source precursor was tested with a vertical cold-wall reactor. The depositions were carried out under an argon atmosphere, and the substrate temperature was kept at 400 C. Columnar grain structure was obtained with vapor deposition, and the granular structure was obtained with (liquid) droplet deposition. Conductive films were deposited with planar electrical resistivities ranging from 1 to 30 Omega x cm.

  14. Hydridosiloxanes as precursors to ceramic products

    DOEpatents

    Blum, Yigal D.; Johnson, Sylvia M.; Gusman, Michael I.

    1997-01-01

    A method is provided for preparing ceramic precursors from hydridosiloxane starting materials and then pyrolyzing these precursors to give rise to silicious ceramic materials. Si--H bonds present in the hydridosiloxane starting materials are catalytically activated, and the activated hydrogen atoms may then be replaced with nonhydrogen substituents. These preceramic materials are pyrolyzed in a selected atmosphere to give the desired ceramic product. Ceramic products which may be prepared by this technique include silica, silicon oxynitride, silicon carbide, metal silicates, and mullite.

  15. Hydridosiloxanes as precursors to ceramic products

    DOEpatents

    Blum, Y.D.; Johnson, S.M.; Gusman, M.I.

    1997-06-03

    A method is provided for preparing ceramic precursors from hydridosiloxane starting materials and then pyrolyzing these precursors to give rise to silicious ceramic materials. Si-H bonds present in the hydridosiloxane starting materials are catalytically activated, and the activated hydrogen atoms may then be replaced with nonhydrogen substituents. These preceramic materials are pyrolyzed in a selected atmosphere to give the desired ceramic product. Ceramic products which may be prepared by this technique include silica, silicon oxynitride, silicon carbide, metal silicates, and mullite.

  16. A systematic review of methamphetamine precursor regulations.

    PubMed

    McKetin, Rebecca; Sutherland, Rachel; Bright, David A; Norberg, Melissa M

    2011-11-01

    To assess the effectiveness of methamphetamine precursor regulations in reducing illicit methamphetamine supply and use. A systematic review of 12 databases was used to identify studies that had evaluated the impact of methamphetamine precursor regulations on methamphetamine supply and/or use. The guidelines of the Effective Practice and Organization of Care Group (EPOC) of The Cochrane Collaboration were used to determine which study designs were included and assess their quality. Ten studies met the inclusion criteria. These studies evaluated 15 interventions (13 regulations and two related interdiction efforts), all of which were located in North America. Interventions had consistent impacts across various indicators of methamphetamine supply and use. Seven of the 15 interventions produced reductions in methamphetamine indicators (ranging from 12% to 77%). Two of the largest impacts were seen following interdiction efforts, involving the closure of rogue pharmaceutical companies. There was no evidence of a shift into other types of drug use, or injecting use, although the impact on the synthetic drug market was not examined. Null effects were related largely to the existence of alternative sources of precursor chemicals or the availability of imported methamphetamine. Methamphetamine precursor regulations can reduce indicators of methamphetamine supply and use. Further research is needed to determine whether regulations can be effective outside North America, particularly in developing countries, and what impact they have on the broader synthetic drug market. Improved data on precursor diversion are needed to facilitate the evaluation of precursor regulations. © 2011 The Authors, Addiction © 2011 Society for the Study of Addiction.

  17. Structural Evolution of Iron Antimonides from Amorphous Precursors to Crystalline Products Studied by Total Scattering Techniques.

    PubMed

    Bauers, Sage R; Wood, Suzannah R; Jensen, Kirsten M Ø; Blichfeld, Anders B; Iversen, Bo B; Billinge, Simon J L; Johnson, David C

    2015-08-05

    Homogeneous reaction precursors may be used to form several solid-state compounds inaccessible by traditional synthetic routes, but there has been little development of techniques that allow for a priori prediction of what may crystallize in a given material system. Here, the local structures of FeSbx designed precursors are determined and compared with the structural motifs of their crystalline products. X-ray total scattering and atomic pair distribution function (PDF) analysis are used to show that precursors that first nucleate a metastable FeSb3 compound share similar local structure to the product. Interestingly, precursors that directly crystallize to thermodynamically stable FeSb2 products also contain local structural motifs of the metastable phase, despite their compositional disagreement. While both crystalline phases consist of distorted FeSb6 octahedra with Sb shared between either two or three octahedra as required for stoichiometry, a corner-sharing arrangement indicative of AX3-type structures is the only motif apparent in the PDF of either precursor. Prior speculation was that local composition controlled which compounds nucleate from amorphous intermediates, with different compositions favoring different local arrangements and hence different products. This data suggests that local environments in these amorphous intermediates may not be very sensitive to overall composition. This can provide insight into potential metastable phases which may form in a material system, even with a precursor that does not crystallize to the kinetically stabilized product. Determination of local structure in homogeneous amorphous reaction intermediates from techniques such as PDF can be a valuable asset in the development of systematic methods to prepare targeted solid-state compounds from designed precursors.

  18. Geoelectric precursors to strong earthquakes in China

    NASA Astrophysics Data System (ADS)

    Yulin, Zhao; Fuye, Qian

    1994-05-01

    The main results of searching for electrical precursors to strong earthquakes in China for the last 25 yr are presented. This comprises: the continuous twenty-year resistivity record before and after the great Tangshan earthquake of 1976; spatial and temporal variations in resistivity anomalies observed at more than 6 stations within 150 km of the Tangshan earthquake epicenter; the travel-time curve for the front of the resistivity precursor; and a method of intersection for predicting the epicenter location. These results reveal a number of interesting facts: (1) Resistivity measurements with accuracies of 0.5% or better for over 20 yr show that resistivity decreases of several percent, which began approximately 3 yr prior to the Tangshan earthquake, were larger than the background fluctuations and hence statistically significant. An outstanding example of an intermediate-term resistivity precursor is given. (2) The intermediate-term resistivity precursor decrease before Tangshan earthquake is such a pervasive phenomenon that the mean decrease, in percent, can be contoured on a map of the Beijing-Tianjin-Tangshan region. This shows the maximum decrease centered over the epicenter. (3) The anomalies in resistivity and self-potential, which began 2-0.5 months before the Tangshan main shock, had periods equal to that of the tidal waves M 2 and MS f, respectively, so that the associated anomalies can be identified as impending-earthquake precursors and a modal related to stress-displacement weakening is proposed.

  19. JAK/Stat signaling regulates heart precursor diversification in Drosophila

    PubMed Central

    Johnson, Aaron N.; Mokalled, Mayssa H.; Haden, Tom N.; Olson, Eric N.

    2011-01-01

    Intercellular signal transduction pathways regulate the NK-2 family of transcription factors in a conserved gene regulatory network that directs cardiogenesis in both flies and mammals. The Drosophila NK-2 protein Tinman (Tin) was recently shown to regulate Stat92E, the Janus kinase (JAK) and Signal transducer and activator of transcription (Stat) pathway effector, in the developing mesoderm. To understand whether the JAK/Stat pathway also regulates cardiogenesis, we performed a systematic characterization of JAK/Stat signaling during mesoderm development. Drosophila embryos with mutations in the JAK/Stat ligand upd or in Stat92E have non-functional hearts with luminal defects and inappropriate cell aggregations. Using strong Stat92E loss-of-function alleles, we show that the JAK/Stat pathway regulates tin expression prior to heart precursor cell diversification. tin expression can be subdivided into four phases and, in Stat92E mutant embryos, the broad phase 2 expression pattern in the dorsal mesoderm does not restrict to the constrained phase 3 pattern. These embryos also have an expanded pericardial cell domain. We show the E(spl)-C gene HLHm5 is expressed in a pattern complementary to tin during phase 3 and that this expression is JAK/Stat dependent. In addition, E(spl)-C mutant embryos phenocopy the cardiac defects of Stat92E embryos. Mechanistically, JAK/Stat signals activate E(spl)-C genes to restrict Tin expression and the subsequent expression of the T-box transcription factor H15 to direct heart precursor diversification. This study is the first to characterize a role for the JAK/Stat pathway during cardiogenesis and identifies an autoregulatory circuit in which tin limits its own expression domain. PMID:21965617

  20. Lu2O3-SiO2-ZrO2 Coatings for Environmental Barrier Application by Solution Precursor Plasma Spraying and Influence of Precursor Chemistry

    NASA Astrophysics Data System (ADS)

    Darthout, Émilien; Quet, Aurélie; Braidy, Nadi; Gitzhofer, François

    2014-02-01

    As environmental barrier coatings are subjected to thermal stress in gas turbine engines, the introduction of a secondary phase as zircon (ZrSiO4) is likely to increase the stress resistance of Lu2Si2O7 coatings generated by induction plasma spraying using liquid precursors. In a first step, precursor chemistry effect is investigated by the synthesis of ZrO2-SiO2 nanopowders by induction plasma nanopowder synthesis technique. Tetraethyl orthosilicate (TEOS) as silicon precursor and zirconium oxynitrate and zirconium ethoxide as zirconium precursors are mixed in ethanol and produce a mixture of tetragonal zirconia and amorphous silica nanoparticles. The use of zirconium ethoxide precursor results in zirconia particles with diameter below 50 nm because of exothermic thermal decomposition of the ethoxide and its high boiling point with respect to solvent, while larger particles are formed when zirconium oxynitrate is employed. The formation temperature of zircon from zirconia and silica oxides is found at 1425 °C. Second, coatings are synthesized in Lu2O3-ZrO2-SiO2 system. After heat treatment, the doping effect of lutetium on zirconia grains totally inhibits the zircon formation. Dense coatings are obtained with the use of zirconium ethoxide because denser particles with a homogeneous diameter distribution constitute the coating.

  1. Materials Design Through Chemical Control of Precursors

    DTIC Science & Technology

    2008-08-22

    Ligand Sets,” H. M. El-Kaderi, M.J. Heeg, and C.H. Winter, Polyhedron 2006, 25, 224-234. 7. “Atomic Layer Deposition of Ga2O3 Films from a...poster presentation. 4. “Atomic Layer Deposition (ALD) of High Quality Ga2O3 Thin Films from a Dimeric Dialkylamido-Bridged Gallium Complex,” C. L...growth of Ga2O3 films from a new metalorganic precursor (“Atomic Layer Deposition of Ga2O3 Films from a 4 Dialkylamido-Based Precursor,” C. L

  2. High-Solids Polyimide Precursor Solutions

    NASA Technical Reports Server (NTRS)

    Chuang, Chun-Hua (Inventor)

    2004-01-01

    The invention is a highly concentrated stable solution of polymide precursors (monometers) having a solids content ranging from about 80 to 98 percent by weight in lower aliphatic alcohols i.e. methyl and/or ethylalcohol. the concentrated polyimide precursos solution comparisons effective amounts of at least one aromatic diamine, at least one aromatic dianhydride, and a monofunctional endcap including monoamines, monoanhydrides and lower alkyl esters of said monoanhydrides. These concentrated polyimide precursor solutions are particularly useful for the preparation of fibrous prepregs and composites for use in structural materials for military and civil applications.

  3. Applying polarity rapid assessment method and ultrafiltration to characterize NDMA precursors in wastewater effluents.

    PubMed

    Chen, Chao; Leavey, Shannon; Krasner, Stuart W; Mel Suffet, I H

    2014-06-15

    Certain nitrosamines in water are disinfection byproducts that are probable human carcinogens. Nitrosamines have diverse and complex precursors that include effluent organic matter, some anthropogenic chemicals, and natural (likely non-humic) substances. An easy and selective tool was first developed to characterize nitrosamine precursors in treated wastewaters, including different process effluents. This tool takes advantages of the polarity rapid assessment method (PRAM) and ultrafiltration (UF) (molecular weight distribution) to locate the fractions with the strongest contributions to the nitrosamine precursor pool in the effluent organic matter. Strong cation exchange (SCX) and C18 solid-phase extraction cartridges were used for their high selectivity for nitrosamine precursors. The details of PRAM operation, such as cartridge clean-up, capacity, pH influence, and quality control were included in this paper, as well as the main parameters of UF operation. Preliminary testing of the PRAM/UF method with effluents from one wastewater treatment plant gave very informative results. SCX retained 45-90% of the N-nitrosodimethylamine (NDMA) formation potential (FP)-a measure of the precursors-in secondary and tertiary wastewater effluents. These results are consistent with NDMA precursors likely having a positively charged amine group. C18 adsorbed 30-45% of the NDMAFP, which indicates that a substantial portion of these precursors were non-polar. The small molecular weight (MW) (<1 kDa) and large MW (>10 kDa) fractions obtained from UF were the primary contributors to NDMAFP. The combination of PRAM and UF brings important information on the characteristics of nitrosamine precursors in water with easy operation. Copyright © 2014 Elsevier Ltd. All rights reserved.

  4. Tannins and terpenoids as major precursors of Suwannee River fulvic acid

    Leenheer, Jerry A.; Rostad, Colleen E.

    2004-01-01

    Suwannee River fulvic acid (SRFA) was fractionated into 7 fractions by normal-phase chromatography on silica gel followed by reverse-phase fractionation on XAD-8 resin that produced 18 subfractions. Selected major subfractions were characterized by 13C-nuclear magnetic resonance (NMR), infrared spectrometry, and elemental analyses. 13C-NMR spectra of the subfractions were more indicative of precursor structures than unfractionated SRFA, and gave spectral profiles that indicated SRFA mass was about equally split between tannin precursors and terpenoid precursors. Lignin precursors were minor components. Synthesis of 13C-NMR data with elemental data for subfractions derived from both tannin and terpenoid precursors revealed high ring contents and low numbers of carbon per rings which is indicative of fused ring structures that are extensively substituted with carboxyl and methyl groups. These results ruled out extended chain structures for SRFA. This information is useful for determining sources and properties of fulvic acid in drinking water supplies as tannins are more reactive with chlorine to produce undesirable disinfection by-products than are terpenoids.

  5. Valence State Driven Site Preference in the Quaternary Compound Ca5MgAgGe5: An Electron-Deficient Phase with Optimized Bonding

    SciT

    Ponou, Simeon; Lidin, Sven; Zhang, Yuemei

    The quaternary phase Ca5Mg0.95Ag1.05(1)Ge5 (3) was synthesized by high-temperature solid-state techniques, and its crystal structure was determined by single-crystal diffraction methods in the orthorhombic space group Pnma – Wyckoff sequence c12 with a = 23.1481(4) Å, b = 4.4736(1) Å, c = 11.0128(2) Å, V = 1140.43(4) Å3, Z = 4. The crystal structure can be described as linear intergrowths of slabs cut from the CaGe (CrB-type) and the CaMGe (TiNiSi-type; M = Mg, Ag) structures. Hence, 3 is a hettotype of the hitherto missing n = 3 member of the structure series with the general formula R2+nT2X2+n, previously describedmore » with n = 1, 2, and 4. The member with n = 3 was predicted in the space group Cmcm – Wyckoff sequence f5c2. The experimental space group Pnma (in the nonstandard setting Pmcn) corresponds to a klassengleiche symmetry reduction of index two of the predicted space group Cmcm. This transition originates from the switching of one Ge and one Ag position in the TiNiSi-related slab, a process that triggers an uncoupling of each of the five 8f sites in Cmcm into two 4c sites in Pnma. The Mg/Ag site preference was investigated using VASP calculations and revealed a remarkable example of an intermetallic compound for which the electrostatic valency principle is a critical structure-directing force. The compound is deficient by one valence electron according to the Zintl concept, but LMTO electronic structure calculations indicate electronic stabilization and overall bonding optimization in the polyanionic network. Other stability factors beyond the Zintl concept that may account for the electronic stabilization are discussed.« less

  6. Precursor to the TRICARE Next Generation Program

    DTIC Science & Technology

    2004-06-01

    Precursor to T-NEX 6 Appendix A - Maps of Interest 84 Appendix B - International Classification of Diseases Codes 86...utilization management, and disease management (Lupo, 2003). Health management will be demonstrated by measurable quality improvements, population...National Association of County and City Health Officials and the Center for Disease Control and Prevention that helps key officials review community

  7. Sol-gel precursors and products thereof

    DOEpatents

    Warren, Scott C.; DiSalvo, Jr., Francis J.; Weisner, Ulrich B.

    2017-02-14

    The present invention provides a generalizable single-source sol-gel precursor capable of introducing a wide range of functionalities to metal oxides such as silica. The sol-gel precursor facilitates a one-molecule, one-step approach to the synthesis of metal-silica hybrids with combinations of biological, catalytic, magnetic, and optical functionalities. The single-source precursor also provides a flexible route for simultaneously incorporating functional species of many different types. The ligands employed for functionalizing the metal oxides are derived from a library of amino acids, hydroxy acids, or peptides and a silicon alkoxide, allowing many biological functionalities to be built into silica hybrids. The ligands can coordinate with a wide range of metals via a carboxylic acid, thereby allowing direct incorporation of inorganic functionalities from across the periodic table. Using the single-source precursor a wide range of functionalized nanostructures such as monolith structures, mesostructures, multiple metal gradient mesostructures and Stober-type nanoparticles can be synthesized. ##STR00001##

  8. Superconductor precursor mixtures made by precipitation method

    DOEpatents

    Bunker, Bruce C.; Lamppa, Diana L.; Voigt, James A.

    1989-01-01

    Method and apparatus for preparing highly pure homogeneous precursor powder mixtures for metal oxide superconductive ceramics. The mixes are prepared by instantaneous precipitation from stoichiometric solutions of metal salts such as nitrates at controlled pH's within the 9 to 12 range, by addition of solutions of non-complexing pyrolyzable cations, such as alkyammonium and carbonate ions.

  9. School Violence: Prevalence, Precursors, and Prevention.

    ERIC Educational Resources Information Center

    Juvonen, Jaanna

    2002-01-01

    Reviews types of school violence students confront, including a frequent precursor thereto: bullying. Discusses positive and negative aspects of current approach to school violence prevention such as surveillance, zero-tolerance policies, anti-bullying programs. Describes components of model school violence-prevention program. (Contains 38…

  10. Detection of Chemical Precursors of Explosives

    NASA Technical Reports Server (NTRS)

    Li, Jing

    2012-01-01

    Certain selected chemicals associated with terrorist activities are too unstable to be prepared in final form. These chemicals are often prepared as precursor components, to be combined at a time immediately preceding the detonation. One example is a liquid explosive, which usually requires an oxidizer, an energy source, and a chemical or physical mechanism to combine the other components. Detection of the oxidizer (e.g. H2O2) or the energy source (e.g., nitromethane) is often possible, but must be performed in a short time interval (e.g., 5 15 seconds) and in an environment with a very small concentration (e.g.,1 100 ppm), because the target chemical(s) is carried in a sealed container. These needs are met by this invention, which provides a system and associated method for detecting one or more chemical precursors (components) of a multi-component explosive compound. Different carbon nanotubes (CNTs) are loaded (by doping, impregnation, coating, or other functionalization process) for detecting of different chemical substances that are the chemical precursors, respectively, if these precursors are present in a gas to which the CNTs are exposed. After exposure to the gas, a measured electrical parameter (e.g. voltage or current that correlate to impedance, conductivity, capacitance, inductance, etc.) changes with time and concentration in a predictable manner if a selected chemical precursor is present, and will approach an asymptotic value promptly after exposure to the precursor. The measured voltage or current are compared with one or more sequences of their reference values for one or more known target precursor molecules, and a most probable concentration value is estimated for each one, two, or more target molecules. An error value is computed, based on differences of voltage or current for the measured and reference values, using the most probable concentration values. Where the error value is less than a threshold, the system concludes that the target

  11. Precursor preparation for Ca-Al layered double hydroxide to remove hexavalent chromium coexisting with calcium and magnesium chlorides

    NASA Astrophysics Data System (ADS)

    Zhong, Lihua; He, Xiaoman; Qu, Jun; Li, Xuewei; Lei, Zhiwu; Zhang, Qiwu; Liu, Xinzhong

    2017-01-01

    Al(OH)3 and Ca(OH)2 powders are co-ground to prepare a precursor which hydrates into a layered double hydroxide (LDH) phase by agitation in aqueous solution with target hexavalent chromium (Cr(VI)) at room temperature, to achieve an obvious improvement in removal efficiency of Cr(VI) through an easy incorporation into the structure. Although the prepared precursor transforms into LDH phases also when agitated in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist. The adsorption isotherm and kinetic studies show that the phenomena occurring on the Al-Ca precursor fit a pseudo-second-order kinetics with a Langmuir adsorption capacity of 59.45 mg/g. Besides, characterizations of the prepared precursor and the samples after adsorption are also performed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Transmission electron microscope (TEM) to understand the reason of the preferential incorporation of Cr(VI) to the coexisting chloride salts during the LDH phase formation. Ca-Al precursor (C3A) was agitated in a hexavalent chromium (Cr(VI)) solution to form Al-Ca-CrO4 LDH product. Ca-Al-CrO4 LDH phase occurred preferentially to Ca-Al-MCl2 LDH phases in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist.

  12. Preparation of plutonium-bearing ceramics via mechanically activated precursor

    NASA Astrophysics Data System (ADS)

    Chizhevskaya, S. V.; Stefanovsky, S. V.

    2000-07-01

    The problem of excess weapons plutonium disposition is suggested to be solved by means of its incorporation in stable ceramics with high chemical durability and radiation resistivity. The most promising host phases for plutonium as well as uranium and neutron poisons (gadolinium, hafnium) are zirconolite, pyrochlore, zircon, zirconia [1,2], and murataite [3]. Their production requires high temperatures and a fine-grained homogeneous precursor to reach final waste form with high quality and low leachability. Currently various routes to homogeneous products preparation such as sol-gel technology, wet-milling, and grinding in a ball or planetary mill are used. The best result demonstrates sol-gel technology but this route is very complicated. An alternative technology for preparation of ceramic precursors is the treatment of the oxide batch with high mechanical energy [4]. Such a treatment produces combination of mechanical (fine milling with formation of various defects, homogenization) and chemical (split bonds with formation of active centers—free radicals, ion-radicals, etc.) effects resulting in higher reactivity of the activated batch.

  13. Subeutectic Synthesis of Epitaxial Si-NWs with Diverse Catalysts Using a Novel Si Precursor

    PubMed Central

    2010-01-01

    The applicability of a novel silicon precursor with respect to reasonable nanowire (NW) growth rates, feasibility of epitaxial NW growth and versatility with respect to diverse catalysts was investigated. Epitaxial growth of Si-NWs was achieved using octochlorotrisilane (OCTS) as Si precursor and Au as catalyst. In contrast to the synthesis approach with SiCl4 as precursor, OCTS provides Si without the addition of H2. By optimizing the growth conditions, effective NW synthesis is shown for alternative catalysts, in particular, Cu, Ag, Ni, and Pt with the latter two being compatible to complementary metal-oxide-semiconductor technology. As for these catalysts, the growth temperatures are lower than the lowest liquid eutectic; we suggest that the catalyst particle is in the solid state during NW growth and that a solid-phase diffusion process, either in the bulk, on the surface, or both, must be responsible for NW nucleation. PMID:20843058

  14. MicroRNA-like RNAs from the same miRNA precursors play a role in cassava chilling responses.

    PubMed

    Zeng, Changying; Xia, Jing; Chen, Xin; Zhou, Yufei; Peng, Ming; Zhang, Weixiong

    2017-12-07

    MicroRNAs (miRNAs) are known to play important roles in various cellular processes and stress responses. MiRNAs can be identified by analyzing reads from high-throughput deep sequencing. The reads realigned to miRNA precursors besides canonical miRNAs were initially considered as sequencing noise and ignored from further analysis. Here we reported a small-RNA species of phased and half-phased miRNA-like RNAs different from canonical miRNAs from cassava miRNA precursors detected under four distinct chilling conditions. They can form abundant multiple small RNAs arranged along precursors in a tandem and phased or half-phased fashion. Some of these miRNA-like RNAs were experimentally confirmed by re-amplification and re-sequencing, and have a similar qRT-PCR detection ratio as their cognate canonical miRNAs. The target genes of those phased and half-phased miRNA-like RNAs function in process of cell growth metabolism and play roles in protein kinase. Half-phased miR171d.3 was confirmed to have cleavage activities on its target gene P-glycoprotein 11, a broad substrate efflux pump across cellular membranes, which is thought to provide protection for tropical cassava during sharp temperature decease. Our results showed that the RNAs from miRNA precursors are miRNA-like small RNAs that are viable negative gene regulators and may have potential functions in cassava chilling responses.

  15. Molecular characterization of an ependymin precursor from goldfish brain.

    PubMed

    Königstorfer, A; Sterrer, S; Eckerskorn, C; Lottspeich, F; Schmidt, R; Hoffmann, W

    1989-01-01

    Ependymins are thought to be implicated in fundamental processes involved in plasticity of the goldfish CNS. Gas-phase sequencing of purified ependymins beta and gamma revealed that they share the same N-terminal sequence. Each sequence displays microheterogeneities at several positions. Based on the protein sequences obtained, we constructed synthetic oligonucleotides and used them as hybridization probes for screening cDNA libraries of goldfish brain. In this article we describe the full-length sequence of a mRNA encoding a precursor of ependymins. A cleavable signal sequence characteristic of secretory proteins is located at the N-terminal end, followed directly by the ependymin sequence. Also, two potential N-glycosylation sites were detected. A computer search revealed that ependymins form a novel family of unique proteins.

  16. Investigations on precursor measures for aeroelastic flutter

    NASA Astrophysics Data System (ADS)

    Venkatramani, J.; Sarkar, Sunetra; Gupta, Sayan

    2018-04-01

    Wind tunnel experiments carried out on a pitch-plunge aeroelastic system in the presence of fluctuating flows reveal that flutter instability is presaged by a regime of intermittency. It is observed that as the flow speed gradually increases towards the flutter speed, there appears intermittent bursts of periodic oscillations which become more frequent as the wind speed increases and eventually the dynamics transition into fully developed limit cycle oscillations, marking the onset of flutter. The signature from these intermittent oscillations are exploited to develop measures that forewarn a transition to flutter and can serve as precursors. This study investigates a suite of measures that are obtained directly from the time history of measurements and are hence model independent. The dependence of these precursors on the size of the measured data set and the time required for their computation is investigated. These measures can be useful in structural health monitoring of aeroelastic structures.

  17. Metabolic Precursors to Amphetamine and Methamphetamine.

    PubMed

    Cody, J D

    1993-12-01

    Analysis and interpretation of amphetamine results is a challenging process made difficult by a number of factors. One of the complications comes from determination of the origin of amphetamine or methamphetamine in a sample. Given the relatively rare occasions that either of these two drugs are prescribed, legal prescription of one of these drugs is seldom a reason for positive findings. A number of other precursor compounds are metabolized by the body to amphetamine or methamphetamine, many of which could be used for legitimate reasons. Fourteen different metabolic precursors of amphetamine or methamphetamine are included in this review. They are amphetaminil, benzphetamine, clobenzorex, deprenyl, dimethylamphetamine, ethylamphetamine, famprofazone, fencamine, fenethylline, fenproporex, furfenorex, mefenorex, mesocarb, and prenylamine. Medical use, metabolism, analysis, and interpretation are described to afford sufficient information to evaluate the possible involvement of these drugs in positive amphetamine or methamphetamine results. Copyright © 1993 Central Police University.

  18. DNA Precursor Metabolism and Mitochondrial Genome Stability

    DTIC Science & Technology

    2003-04-01

    mitochondrial DNA replication , to learn how the pool sizes are regulated, and to understand how perturbations of normal dNTP metabolism within the...mitochondria raises the possibility, however unlikely, that it is serving a function in addition to its role in DNA replication . The literature on non-DNA...is below since many authors do not follow the 200 word limit 14. SUBJECT TERMS Mitochondria, Genome stability, DNA precursors, Mitochondrial DNA

  19. Precursors to radiopharmaceutical agents for tissue imaging

    DOEpatents

    Srivastava, Prem C.; Knapp, Jr., Furn F.

    1988-01-01

    A class of radiolabeled compounds to be used in tissue imaging that exhibits rapid brain uptake, good brain:blood radioactivity ratios, and long retention times. The imaging agents are more specifically radioiodinated aromatic amines attached to dihydropyridine carriers, that exhibit heart as well as brain specificity. In addition to the radiolabeled compounds, classes of compounds are also described that are used as precursors and intermediates in the preparation of the imaging agents.

  20. Scalar model for frictional precursors dynamics

    PubMed Central

    Taloni, Alessandro; Benassi, Andrea; Sandfeld, Stefan; Zapperi, Stefano

    2015-01-01

    Recent experiments indicate that frictional sliding occurs by nucleation of detachment fronts at the contact interface that may appear well before the onset of global sliding. This intriguing precursory activity is not accounted for by traditional friction theories but is extremely important for friction dominated geophysical phenomena as earthquakes, landslides or avalanches. Here we simulate the onset of slip of a three dimensional elastic body resting on a surface and show that experimentally observed frictional precursors depend in a complex non-universal way on the sample geometry and loading conditions. Our model satisfies Archard's law and Amontons' first and second laws, reproducing with remarkable precision the real contact area dynamics, the precursors' envelope dynamics prior to sliding, and the normal and shear internal stress distributions close to the interfacial surface. Moreover, it allows to assess which features can be attributed to the elastic equilibrium, and which are attributed to the out-of-equilibrium dynamics, suggesting that precursory activity is an intrinsically quasi-static physical process. A direct calculation of the evolution of the Coulomb stress before and during precursors nucleation shows large variations across the sample, explaining why earthquake forecasting methods based only on accumulated slip and Coulomb stress monitoring are often ineffective. PMID:25640079

  1. Scalar model for frictional precursors dynamics.

    PubMed

    Taloni, Alessandro; Benassi, Andrea; Sandfeld, Stefan; Zapperi, Stefano

    2015-02-02

    Recent experiments indicate that frictional sliding occurs by nucleation of detachment fronts at the contact interface that may appear well before the onset of global sliding. This intriguing precursory activity is not accounted for by traditional friction theories but is extremely important for friction dominated geophysical phenomena as earthquakes, landslides or avalanches. Here we simulate the onset of slip of a three dimensional elastic body resting on a surface and show that experimentally observed frictional precursors depend in a complex non-universal way on the sample geometry and loading conditions. Our model satisfies Archard's law and Amontons' first and second laws, reproducing with remarkable precision the real contact area dynamics, the precursors' envelope dynamics prior to sliding, and the normal and shear internal stress distributions close to the interfacial surface. Moreover, it allows to assess which features can be attributed to the elastic equilibrium, and which are attributed to the out-of-equilibrium dynamics, suggesting that precursory activity is an intrinsically quasi-static physical process. A direct calculation of the evolution of the Coulomb stress before and during precursors nucleation shows large variations across the sample, explaining why earthquake forecasting methods based only on accumulated slip and Coulomb stress monitoring are often ineffective.

  2. Formulating Precursors for Coating Metals and Ceramics

    NASA Technical Reports Server (NTRS)

    Morales, Wilfredo; Gatica, Jorge E.; Reye, John T.

    2005-01-01

    A protocol has been devised for formulating low-vapor-pressure precursors for protective and conversion coatings on metallic and ceramic substrates. The ingredients of a precursor to which the protocol applies include additives with phosphate esters, or aryl phosphate esters in solution. Additives can include iron, chromium, and/or other transition metals. Alternative or additional additives can include magnesium compounds to facilitate growth of films on substrates that do not contain magnesium. Formulation of a precursor begins with mixing of the ingredients into a high-vapor-pressure solvent to form a homogeneous solution. Then the solvent is extracted from the solution by evaporation - aided, if necessary, by vacuum and/or slight heating. The solvent is deemed to be completely extracted when the viscosity of the remaining solution closely resembles the viscosity of the phosphate ester or aryl phosphate ester. In addition, satisfactory removal of the solvent can be verified by means of a differential scanning calorimetry essay: the absence of endothermic processes for temperatures below 150 C would indicate that the residual solvent has been eliminated from the solution beyond a detectable dilution level.

  3. Optical Synchrotron Precursors of Radio Hypernovae

    NASA Astrophysics Data System (ADS)

    Nakauchi, Daisuke; Kashiyama, Kazumi; Nagakura, Hiroki; Suwa, Yudai; Nakamura, Takashi

    2015-06-01

    We examine the bright radio synchrotron counterparts of low-luminosity gamma-ray bursts and relativistic supernovae (SNe) and find that they can be powered by spherical hypernova (HN) explosions. Our results imply that radio-bright HNe are driven by relativistic jets that are choked deep inside the progenitor stars or quasi-spherical magnetized winds from fast-rotating magnetars. We also consider the optical synchrotron counterparts of radio-bright HNe and show that they can be observed as precursors several days before the SN peak with an r-band absolute magnitude of {{M}r}∼ -14 mag. While previous studies suggested that additional trans-relativistic components are required to power the bright radio emission, we find that they overestimated the energy budget of the trans-relativistic component by overlooking some factors related to the minimum energy of non-thermal electrons. If an additional trans-relativistic component exists, then a much brighter optical precursor with {{M}r}∼ -20 mag can be expected. Thus, the scenarios of radio-bright HNe can be distinguished by using optical precursors, which can be detectable from ≲ 100 Mpc by current SN surveys like the Kiso SN Survey, Palomar Transient Factory, and Panoramic Survey Telescope & Rapid Response System.

  4. Spinel formation for stabilizing simulated nickel-laden sludge with aluminum-rich ceramic precursors.

    PubMed

    Shih, Kaimin; White, Tim; Leckie, James O

    2006-08-15

    The feasibility of stabilizing nickel-laden sludge from commonly available Al-rich ceramic precursors was investigated and accomplished with high nickel incorporation efficiency. To simulate the process, nickel oxide was mixed alternatively with gamma-alumina, corundum, kaolinite, and mullite and was sintered from 800 to 1480 degrees C. The nickel aluminate spinel (NiAl2O4) was confirmed as the stabilization phase for nickel and crystallized with efficiencies greater than 90% for all precursors above 1250 degrees C and 3-h sintering. The nickel-incorporation reaction pathways with these precursors were identified, and the microstructure and spinel yield were investigated as a function of sintering temperature with fixed sintering time. This study has demonstrated a promising process for forming nickel spinel to stabilize nickel-laden sludge from a wide range of inexpensive ceramic precursors, which may provide an avenue for economically blending waste metal sludges via the building industry processes to reduce the environmental hazards of toxic metals. The correlation of product textures and nickel incorporation efficiencies through selection of different precursors also provides the option of tailoring property-specific products.

  5. Consideration of formation process for the nuclei on precursor

    NASA Astrophysics Data System (ADS)

    Nagata, J.; Okamoto, M.

    2003-12-01

    The very isotropic microwave background and the Hubble expansion indicate that the universe has evolved from an earlier state of high temperature and density that can be reasonably well described by Friedman-Lemaitre-Robertson-Walker cosmological models. The nuclear evolution of non-degenerate matter expanding from very high temperature was studied in detail for various values of the expansion rate and of the proton-neutron abundance difference and baryon density[1,2,3]. In this calculation, many nuclear reactions were included, and its results suggested important reaction process for the evolution of nuclear abundances. 3He and 4He are very important elements in these nuclear reactions as the primordial nucleosynthesis. Microscopic study for few body system is one main topic in nuclear theoretical physics. In this field, very accurate calculations are available by using the Faddeev equations[4]. Recently, many data for pd, p-3He and d-3He have been obtained including polarized observables. Model calculations for systems including 3He and 4He (for example, d + 3He -> p + 4He) are carried out using the Faddeev equations based on the meson exchange models[4]. This model reproduces well the empirical phase shifts which are determined by so-called phase-shift analyses using all of available scattering data measured at various laboratories around the world[5,6,7]. Constructions of models for the nuclear reactions including 3He and 4He will give important information for calculations of the primordial nucleosynthesis after big-ban. The calculations are carried out until the sum of the abundances at each mass number ceases to change. Various different set of initial conditions for the baryon mass density, the expansion rate and the neutron-proton ratio are used. Dusts kept in precursor asteroid nebular form precursor asteroid, then, formations of planet start [8]. Possible values of parameters in the initial conditions for theoretical calculations will be searched

  6. MetNet Precursor - Network Mission to Mars

    NASA Astrophysics Data System (ADS)

    Harri, Arri-Matti

    2010-05-01

    We are developing a new kind of planetary exploration mission for Mars - MetNet in situ observation network based on a new semi-hard landing vehicle called the Met-Net Lander (MNL). The first MetNet vehicle, MetNet Precursor, slated for launch in 2011. The MetNet development work started already in 2001. The actual practical Precursor Mission development work started in January 2009 with participation from various space research institutes and agencies. The scientific rationale and goals as well as key mission solutions will be discussed. The eventual scope of the MetNet Mission is to deploy some 20 MNLs on the Martian surface using inflatable descent system structures, which will be supported by observations from the orbit around Mars. Currently we are working on the MetNet Mars Precursor Mission (MMPM) to deploy one MetNet Lander to Mars in the 2011 launch window as a technology and science demonstration mission. The MNL will have a versatile science payload focused on the atmospheric science of Mars. Time-resolved in situ Martian meteorological measurements acquired by the Viking, Mars Pathfinder and Phoenix landers and remote sensing observations by the Mariner 9, Viking, Mars Global Surveyor, Mars Odyssey and the Mars Express orbiters have provided the basis for our current understanding of the behavior of weather and climate on Mars. However, the available amount of data is still scarce and a wealth of additional in situ observations are needed on varying types of Martian orography, terrain and altitude spanning all latitudes and longitudes to address microscale and mesoscale atmospheric phenomena. Detailed characterization of the Martian atmospheric circulation patterns and climatological cycles requires simultaneous in situ atmospheric observations. The scientific payload of the MetNet Mission encompasses separate instrument packages for the atmospheric entry and descent phase and for the surface operation phase. The MetNet mission concept and key probe

  7. 40 CFR 766.38 - Reporting on precursor chemical substances.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reporting on precursor chemical... SUBSTANCES CONTROL ACT DIBENZO-PARA-DIOXINS/DIBENZOFURANS Specific Chemical Testing/Reporting Requirements § 766.38 Reporting on precursor chemical substances. (a) Identification of precursor chemical substances...

  8. 40 CFR 766.38 - Reporting on precursor chemical substances.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reporting on precursor chemical... SUBSTANCES CONTROL ACT DIBENZO-PARA-DIOXINS/DIBENZOFURANS Specific Chemical Testing/Reporting Requirements § 766.38 Reporting on precursor chemical substances. (a) Identification of precursor chemical substances...

  9. 40 CFR 766.38 - Reporting on precursor chemical substances.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reporting on precursor chemical... SUBSTANCES CONTROL ACT DIBENZO-PARA-DIOXINS/DIBENZOFURANS Specific Chemical Testing/Reporting Requirements § 766.38 Reporting on precursor chemical substances. (a) Identification of precursor chemical substances...

  10. 40 CFR 766.38 - Reporting on precursor chemical substances.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reporting on precursor chemical... SUBSTANCES CONTROL ACT DIBENZO-PARA-DIOXINS/DIBENZOFURANS Specific Chemical Testing/Reporting Requirements § 766.38 Reporting on precursor chemical substances. (a) Identification of precursor chemical substances...

  11. 40 CFR 766.38 - Reporting on precursor chemical substances.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reporting on precursor chemical... SUBSTANCES CONTROL ACT DIBENZO-PARA-DIOXINS/DIBENZOFURANS Specific Chemical Testing/Reporting Requirements § 766.38 Reporting on precursor chemical substances. (a) Identification of precursor chemical substances...

  12. Material State Awareness for Composites Part I: Precursor Damage Analysis Using Ultrasonic Guided Coda Wave Interferometry (CWI).

    PubMed

    Patra, Subir; Banerjee, Sourav

    2017-12-16

    Detection of precursor damage followed by the quantification of the degraded material properties could lead to more accurate progressive failure models for composite materials. However, such information is not readily available. In composite materials, the precursor damages-for example matrix cracking, microcracks, voids, interlaminar pre-delamination crack joining matrix cracks, fiber micro-buckling, local fiber breakage, local debonding, etc.-are insensitive to the low-frequency ultrasonic guided-wave-based online nondestructive evaluation (NDE) or Structural Health Monitoring (SHM) (~100-~500 kHz) systems. Overcoming this barrier, in this article, an online ultrasonic technique is proposed using the coda part of the guided wave signal, which is often neglected. Although the first-arrival wave packets that contain the fundamental guided Lamb wave modes are unaltered, the coda wave packets however carry significant information about the precursor events with predictable phase shifts. The Taylor-series-based modified Coda Wave Interferometry (CWI) technique is proposed to quantify the stretch parameter to compensate the phase shifts in the coda wave as a result of precursor damage in composites. The CWI analysis was performed on five woven composite-fiber-reinforced-laminate specimens, and the precursor events were identified. Next, the precursor damage states were verified using high-frequency Scanning Acoustic Microscopy (SAM) and optical microscopy imaging.

  13. Systems and methods for detection of blowout precursors in combustors

    DOEpatents

    Lieuwen, Tim C.; Nair, Suraj

    2006-08-15

    The present invention comprises systems and methods for detecting flame blowout precursors in combustors. The blowout precursor detection system comprises a combustor, a pressure measuring device, and blowout precursor detection unit. A combustion controller may also be used to control combustor parameters. The methods of the present invention comprise receiving pressure data measured by an acoustic pressure measuring device, performing one or a combination of spectral analysis, statistical analysis, and wavelet analysis on received pressure data, and determining the existence of a blowout precursor based on such analyses. The spectral analysis, statistical analysis, and wavelet analysis further comprise their respective sub-methods to determine the existence of blowout precursors.

  14. Preparation of boron nitride fiber by organic precursor method

    NASA Astrophysics Data System (ADS)

    Zhou, Yingying; Sun, Runjun; Zhang, Zhaohuan; Fan, Wei; Zhou, Dan; Sheng, Cuihong

    In this paper, boron nitride polymer precursor was made by boric acid, melamine, twelve sodium alkyl sulfate as raw materials and pure water as medium which is heated to 70 °C. Boron nitride precursor polymer was soluble in formic acid solution. The boron nitride precursor can be electrostatically spun at the voltage in 23 kV and the distance between the positive and negative poles is 15 cm. The formed fiber is very uniform. The properties of the precursors were analyzed through electron microscope, infrared spectrum, X-ray and ultraviolet spectrum. The aim of the job is to got the precursor of BN and spun it.

  15. Meat flavor precursors and factors influencing flavor precursors--A systematic review.

    PubMed

    Khan, Muhammad Issa; Jo, Cheorun; Tariq, Muhammad Rizwan

    2015-12-01

    Flavor is the sensory impression sensed by taste and smell buds and is a leading factor determining the meat quality and purchasing decision of the consumer. Meat flavor is characteristic of volatiles produced as a result of reactions of non-volatile components that are induced thermally. The water soluble compounds having low molecular weight and meat lipids are important precursors of cooked meat flavor. The Maillard reaction, lipid oxidation, and vitamin degradation are leading reactions during cooking which develop meat flavor from uncooked meat with little aroma and bloody taste. The pre-slaughter and postmortem factors like animal breed, sex, age, feed, aging and cooking conditions contribute to flavor development of cooked meat. The objective of this review is to highlight the flavor chemistry, meat flavor precursors and factors affecting meat flavor precursors. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. Y2O3-MgO Nano-Composite Synthesized by Plasma Spraying and Thermal Decomposition of Solution Precursors

    NASA Astrophysics Data System (ADS)

    Muoto, Chigozie Kenechukwu

    This research aims to identify the key feedstock characteristics and processing conditions to produce Y2O3-MgO composite coatings with high density and hardness using solution precursor plasma spray (SPPS) and suspension plasma spray (SPS) processes, and also, to explore the phenomena involved in the production of homogenized nano-composite powders of this material system by thermal decomposition of solution precursor mixtures. The material system would find potential application in the fabrication of components for optical applications such as transparent windows. It was shown that a lack of major endothermic events during precursor decomposition and the resultant formation of highly dense particles upon pyrolysis are critical precursor characteristics for the deposition of dense and hard Y2O3-MgO coatings by SPPS. Using these principles, a new Y2O3-MgO precursor solution was developed, which yielded a coating with Vickers hardness of 560 Hv. This was a considerable improvement over the hardness of the coatings obtained using conventional solution precursors, which was as low as 110 Hv. In the thermal decomposition synthesis process, binary solution precursor mixtures of: yttrium nitrate (Y[n]) or yttrium acetate (Y[a]), with magnesium nitrate (Mg[n]) or magnesium acetate (Mg[a]) were used in order to study the effects of precursor chemistry on the structural characteristics of the resultant Y2O3-MgO powders. The phase domains were coarse and distributed rather inhomogeneously in the materials obtained from the Y[n]Mg[n] and Y[a]Mg[a] mixtures; finer and more homogeneously-distributed phase domains were obtained for ceramics produced from the Y[a]Mg[n] and Y[n]Mg[a] mixtures. It was established that these phenomena were related to the thermal characteristics for the decomposition of the precursors and their effect on phase separation during oxide crystallization. Addition of ammonium acetate to the Y[n[Mg[n] mixture changed the endothermic process to exothermic

  17. Neutron-powered precursors of kilonovae

    NASA Astrophysics Data System (ADS)

    Metzger, Brian D.; Bauswein, Andreas; Goriely, Stephane; Kasen, Daniel

    2015-01-01

    The merger of binary neutron stars (NSs) ejects a small quantity of neutron-rich matter, the radioactive decay of which powers a day to week long thermal transient known as a kilonova. Most of the ejecta remains sufficiently dense during its expansion that all neutrons are captured into nuclei during the r-process. However, recent general relativistic merger simulations by Bauswein and collaborators show that a small fraction of the ejected mass (a few per cent, or ˜10-4 M⊙) expands sufficiently rapidly for most neutrons to avoid capture. This matter originates from the shocked-heated interface between the merging NSs. Here, we show that the β-decay of these free neutrons in the outermost ejecta powers a `precursor' to the main kilonova emission, which peaks on a time-scale of ˜ few hours following merger at U-band magnitude ˜22 (for an assumed distance of 200 Mpc). The high luminosity and blue colours of the neutron precursor render it a potentially important counterpart to the gravitational wave source, that may encode valuable information on the properties of the merging binary (e.g. NS-NS versus NS-black hole) and the NS equation of state. Future work is necessary to assess the robustness of the fast-moving ejecta and the survival of free neutrons in the face of neutrino absorptions, although the precursor properties are robust to a moderate amount of leptonization. Our results provide additional motivation for short latency gravitational wave triggers and rapid follow-up searches with sensitive ground-based telescopes.

  18. The Search for Precursor Redline Auroral Events

    NASA Astrophysics Data System (ADS)

    Sobel, E. I.; Kepko, L.; Angelopoulos, V.; Donovan, E.; Spanswick, E.

    2013-12-01

    A popular theory of geomagnetic substorms postulates that substorms begin in the downtail region of the magnetosphere and propagate Earthward. This should result in a visible auroral precursor; however, observations have not shown such formations. This poster presents the results of our project to examine the little-studied redline data in search of these early-cycle auroral phenomena. We reviewed daily ground-based redline auroral observations for relevant months of 2008-2013 using software developed in IDL and created an event database with the observation stations, onset timestamp, available satellites, and notes. After narrowing the initial list of nearly 350 events to the best 5, we analyzed the redline events alongside white light and green light observations from the same stations, as well as in situ measurements from THEMIS and geomagnetic readings from ground-based stations. Preliminary results from 36 suspected cases and 5 confirmed cases show some instances of clear redline formations that precede visual onsets. These phenomena form above the equatorward auroral arc, descend over several minutes, and then appear to trigger onset within minutes of reaching the arc boundary. We also found evidence that these precursors are created by earthward plasma flows. This research helps answer the long-standing question of why there has been no visible precursor, despite strong evidence of pre-onset earthward flows. It is one of the first ventures into the lower spectra of the aurora, opening the door for future work on the longer-lasting, lower-energy, and more sensitive red wavelengths.

  19. Effects of detergents on ribosomal precursor subunits of Bacillus megaterium.

    PubMed

    Body, A; Brownstein, B H

    1978-01-01

    Cell extracts prepared by osmotic lysis of protoplasts were analyzed by sucrose gradient sedimentation. In the absence of detergents, ribosomal precursor particles were found in a gradient fraction which sedimented faster than mature 50S subunits and in two other fractions coincident with mature 50S and 30S ribosomal subunits. Phospholipid, an indicator of membrane, was shown to be associated with only the fastest-sedimenting ribosomal precursor particle fraction. After the extracts were treated with detergents, all phospholipid was found at the top of the gradients. Brij 58, Triton X-100, and Nonidet P-40 did not cause a change in the sedimentation values of precursors; however, the detergents deoxycholate or LOC (Amway Corp.) disrupted the fastest-sedimenting precursor and converted the ribosomal precursor subunits which sedimented at the 50S and 30S positions to five different classes of more slowly sedimenting particles. Earlier reports on the in vivo assembly of ribosomal subunits have shown that several stages of ribosomal precursor subunits exist, and, in the presence of the detergents deoxycholate and LOC, which had been used to prepare cell extracts, the precursors sedimented more slowly. Our data are consistent with the hypothesis that those detergents selectively modify the structure of ribosomal precursors and lend further support to the hypothesis that the in vivo ribosomal precursor subunits have 50S and 30S sedimentation values. In addition, these data support the idea that the ribosomal precursor particles found in the fast-sedimenting fraction may constitute a unique precursor fraction.

  20. Effects of Detergents on Ribosomal Precursor Subunits of Bacillus megaterium

    PubMed Central

    Body, Barbara A.; Brownstein, Bernard H.

    1978-01-01

    Cell extracts prepared by osmotic lysis of protoplasts were analyzed by sucrose gradient sedimentation. In the absence of detergents, ribosomal precursor particles were found in a gradient fraction which sedimented faster than mature 50S subunits and in two other fractions coincident with mature 50S and 30S ribosomal subunits. Phospholipid, an indicator of membrane, was shown to be associated with only the fastest-sedimenting ribosomal precursor particle fraction. After the extracts were treated with detergents, all phospholipid was found at the top of the gradients. Brij 58, Triton X-100, and Nonidet P-40 did not cause a change in the sedimentation values of precursors; however, the detergents deoxycholate or LOC (Amway Corp.) disrupted the fastest-sedimenting precursor and converted the ribosomal precursor subunits which sedimented at the 50S and 30S positions to five different classes of more slowly sedimenting particles. Earlier reports on the in vivo assembly of ribosomal subunits have shown that several stages of ribosomal precursor subunits exist, and, in the presence of the detergents deoxycholate and LOC, which had been used to prepare cell extracts, the precursors sedimented more slowly. Our data are consistent with the hypothesis that those detergents selectively modify the structure of ribosomal precursors and lend further support to the hypothesis that the in vivo ribosomal precursor subunits have 50S and 30S sedimentation values. In addition, these data support the idea that the ribosomal precursor particles found in the fast-sedimenting fraction may constitute a unique precursor fraction. PMID:412833

  1. Conformal dynamics of precursors to fracture

    NASA Astrophysics Data System (ADS)

    Barra, F.; Herrera, M.; Procaccia, I.

    2003-09-01

    An exact integro-differential equation for the conformal map from the unit circle to the boundary of an evolving cavity in a stressed 2-dimensional solid is derived. This equation provides an accurate description of the dynamics of precursors to fracture when surface diffusion is important. The solution predicts the creation of sharp grooves that eventually lead to material failure via rapid fracture. Solutions of the new equation are demonstrated for the dynamics of an elliptical cavity and the stability of a circular cavity under biaxial stress, including the effects of surface stress.

  2. Near-infrared–driven decomposition of metal precursors yields amorphous electrocatalytic films

    PubMed Central

    Salvatore, Danielle A.; Dettelbach, Kevan E.; Hudkins, Jesse R.; Berlinguette, Curtis P.

    2015-01-01

    Amorphous metal-based films lacking long-range atomic order have found utility in applications ranging from electronics applications to heterogeneous catalysis. Notwithstanding, there is a limited set of fabrication methods available for making amorphous films, particularly in the absence of a conducting substrate. We introduce herein a scalable preparative method for accessing oxidized and reduced phases of amorphous films that involves the efficient decomposition of molecular precursors, including simple metal salts, by exposure to near-infrared (NIR) radiation. The NIR-driven decomposition process provides sufficient localized heating to trigger the liberation of the ligand from solution-deposited precursors on substrates, but insufficient thermal energy to form crystalline phases. This method provides access to state-of-the-art electrocatalyst films, as demonstrated herein for the electrolysis of water, and extends the scope of usable substrates to include nonconducting and temperature-sensitive platforms. PMID:26601148

  3. The elusive indigo precursors in woad (Isatis tinctoria L.)--identification of the major indigo precursor, isatan A, and a structure revision of isatan B.

    PubMed

    Oberthür, Christine; Schneider, Bernd; Graf, Heidemarie; Hamburger, Matthias

    2004-01-01

    A metabolite-profiling study of shock-frozen leaves of Isatis tinctoria L., an old indigo dye plant and medicinal herb, revealed a complex pattern of indigo-forming compounds with higher polarities than the known indigo precursors isatan B and indican. These highly unstable compounds underwent rapid post-harvest transformation and were not detected in air-dried leaves. The major indigo precursor, named isatan A (4), was isolated by rapid normal-phase and gel chromatography, along with isatan B (3). A full spectral data set of 3 showed that the previous structure assignment as 'indoxyl-5-ketogluconate' has to be revised to 1H-indol-3-yl beta-D-ribohex-3-ulopyranoside. Isatan A (4) was identified as 1H-indol-3-yl 6'-O-(carboxyacetyl)-beta-D-ribohex-3'-ulopyranoside. In aqueous solution, glycosides 3 and 4 occur as hydrates and undergo rapid hydrolysis under very mild acidic or basic conditions.

  4. Activated microporous materials through polymerization of microemulsion precursors

    NASA Astrophysics Data System (ADS)

    Venkatesan, Arunkumar

    Microemulsions have been well studied for their unique characteristics. They are isotropic, thermodynamically stable and microstructured mixtures of oil and water stabilized by one or more surfactant species. They are formed spontaneously and are thermodynamically stable. Microemulsion precursors can be polymerized to make microporous solids with controlled pore structure and sizes. These polymeric solids have been studied extensively in the past. Although the fundamental properties of the microporous solids have been studied in depth, the development of specific applications that will utilize the unique properties of these solids has not been exhaustively researched. The current work establishes the feasibility of making activated microporous solids from microemulsion precursors, by the use of a ligand that chelates metals and also attaches itself to the polymer monolith. It also uses a novel 'in-situ' incorporation by combining the formulation and incorporation steps into one. The research objectives are, to formulate a microemulsion system that can yield useful microporous solids upon polymerization and activation, to characterize these solids using existing techniques available for analysis of similar microporous solids, to identify and understand the effect of the variables in the system and to study the influence of these variables on the performance characteristics of this material. Characterization techniques like Differential Scanning Calorimetry, Thermogravimetric Analysis and Scanning Electron Microscopy were used. A hydroxyethylmethylmethacrylate/methylmethacrylate/aqueous phase containing 10% SDS' system was chosen as the precursor microemulsion and the corresponding microporous solids were made. A metal chelating ligand, Congo Red, was incorporated onto the microporous polymer using NaOH as a binding agent. The ability of the resultant 'activated' microporous solid to remove metal ions from solution, was evaluated. The metal ion chosen was chromium

  5. Effect of chain length on thermal conversion of alkoxy-substituted copper phthalocyanine precursors.

    PubMed

    Fukuda, Takamitsu; Kikukawa, Yuu; Tsuruya, Ryota; Fuyuhiro, Akira; Ishikawa, Naoto; Kobayashi, Nagao

    2011-11-21

    A series of dialkoxy-substituted copper phthalocyanine (CuPc) precursors (4a-4d) have been prepared by treating phthalonitrile with the corresponding lithium alkoxide under mild conditions. The precursors exhibited high solubilities in common organic solvents, including acetone, toluene, tetrahydrofuran (THF), CH(2)Cl(2), and CHCl(3). Elongation of the alkoxy chains improved the solubilities of the precursors effectively, and accordingly, the butoxy-substituted derivative (4d) showed the highest solubility among 4a-4d. X-ray crystallography clarified that the conjugated skeletons of 4a-4d are all isostructural, and have two alkoxy groups in a syn-conformation fashion, leading to highly bent structures. Thermal conversions of the precursors examined by thermogravimetry (TG) and differential thermal analysis (DTA) demonstrate that 4a was converted into CuPc via two distinct exothermic processes in the 200-250 °C temperature range, while 4d exhibits only one exothermic signal in the DTA. In the field emission scanning electron microscopy (FESEM) images of 4a, the presence of two types of distinct crystal morphology (prismatic and plate-like crystals) can be recognized, implying that the two observed exothermic processes in the DTA can be attributed to the different crystal morphologies of the samples rather than the step-by-step elimination of the alkoxy groups. The thermal formation of CuPc from the precursors has been unambiguously confirmed by X-ray powder diffraction, UV-vis spectroscopy, and elemental analysis. The precursors were converted into CuPc at lower temperature with increasing chain length, presumably because of the increased void volume in the crystals. Thermal conversion performed in the solution phase results in a bright blue-colored solution with prominent absorption bands in the 650-700 nm region, strongly supporting the formation of CuPc.

  6. First results on GlioLab/GlioSat Precursors Missions

    NASA Astrophysics Data System (ADS)

    Cappelletti, Chantal; Notarangelo, Angelo; Demoss, Darrin; Carella, Massimo

    2012-07-01

    Since 2009 GAUSS group is involved in a joint collaboration with Morehead State University (MSU) Space Science Center and IRCCS Casa Sollievo della Sofferenza (CSS) research labs with the aim to design a biomedical project in order to investigate if the combined effects of microgravity conditions and ionizing radiation increase or decrease the survival rate of cancer cells. The biological sample consists of Glioblastoma cancer cell line ANGM-CSS. Glioblastoma is a kind of cancer that can be treated after surgery only by radiotherapy using ionizing radiation. This treatment, anyway, results in a very low survival rate. This project uses different university space platforms: a CubeLab, named GlioLab, on board the International Space Station and the university microsatellite UniSat-5 designed by GAUSS. In addition a GlioLab/GlioSat precursor experiment has already flown two times with the Space Shuttle during the missions STS-134 and STS-135. The phase 0 or the precursor of GlioLab uses a COTS system, named Liquid Mixing Apparatus (LMA), to board the biological samples inside the Space Shuttle for thirty day . The LMA allows to board liquids inside a vial but is not equipped with environment control system. After landing the samples were investigated by researchers at CSS in Italy and at MSU in Kentucky. This paper deals with the experimental set up and the results obtained during the STS-134 and STS-135 missions and with the new evidences on the behavior of this kind of cancer. In particular the results obtained on the DNA analysis give a confirmation of the original idea of GLioLab/Gliosat project justifying the development of the two systems.

  7. The role of amorphous precursors in the crystallization of La and Nd carbonates

    NASA Astrophysics Data System (ADS)

    Vallina, Beatriz; Rodriguez-Blanco, Juan Diego; Brown, Andrew P.; Blanco, Jesus A.; Benning, Liane G.

    2015-07-01

    Crystalline La and Nd carbonates can be formed from poorly-ordered nanoparticulate precursors, termed amorphous lanthanum carbonate (ALC) and amorphous neodymium carbonate (ANC). When reacted in air or in aqueous solutions these precursors show highly variable lifetimes and crystallization pathways. We have characterized these precursors and the crystallization pathways and products with solid-state, spectroscopic and microscopic techniques to explain the differences in crystallization mechanisms between the La and Nd systems. ALC and ANC consist of highly hydrated, 10-20 nm spherical nanoparticles with a general formula of REE2(CO3)3.5H2O (REE = La, Nd). The stabilities differ by ~2 orders of magnitude, with ANC being far more stable than ALC. This difference is due to the Nd3+ ion having a far higher hydration energy compared to the La3+ ion. This, together with temperature and reaction times, leads to clear differences not only in the kinetics and mechanisms of crystallization of the amorphous precursor La- and Nd-carbonate phases but also in the resulting crystallite sizes and morphologies of the end products. All crystalline La and Nd carbonates developed spherulitic morphologies when crystallization occurred from hydrous phases in solution at temperatures above 60 °C (La system) and 95 °C (Nd system). We suggest that spherulitic growth occurs due to a rapid breakdown of the amorphous precursors and a concurrent rapid increase in supersaturation levels in the aqueous solution. The kinetic data show that the crystallization pathway for both La and Nd carbonate systems is dependent on the reaction temperature and the ionic potential of the REE3+ ion.Crystalline La and Nd carbonates can be formed from poorly-ordered nanoparticulate precursors, termed amorphous lanthanum carbonate (ALC) and amorphous neodymium carbonate (ANC). When reacted in air or in aqueous solutions these precursors show highly variable lifetimes and crystallization pathways. We have

  8. Utilization of Mineral Wools as Alkali-Activated Material Precursor

    PubMed Central

    Yliniemi, Juho; Kinnunen, Paivo; Karinkanta, Pasi; Illikainen, Mirja

    2016-01-01

    Mineral wools are the most common insulation materials in buildings worldwide. However, mineral wool waste is often considered unrecyclable because of its fibrous nature and low density. In this paper, rock wool (RW) and glass wool (GW) were studied as alkali-activated material precursors without any additional co-binders. Both mineral wools were pulverized by a vibratory disc mill in order to remove the fibrous nature of the material. The pulverized mineral wools were then alkali-activated with a sodium aluminate solution. Compressive strengths of up to 30.0 MPa and 48.7 MPa were measured for RW and GW, respectively, with high flexural strengths measured for both (20.1 MPa for RW and 13.2 MPa for GW). The resulting alkali-activated matrix was a composite-type in which partly-dissolved fibers were dispersed. In addition to the amorphous material, sodium aluminate silicate hydroxide hydrate and magnesium aluminum hydroxide carbonate phases were identified in the alkali-activated RW samples. The only crystalline phase in the GW samples was sodium aluminum silicate. The results of this study show that mineral wool is a very promising raw material for alkali activation. PMID:28773435

  9. High-fraction brookite films from amorphous precursors

    SciT

    Haggerty, James E. S.; Schelhas, Laura T.; Kitchaev, Daniil A.

    2017-11-09

    Structure-specific synthesis processes are of key importance to the growth of polymorphic functional compounds such as TiO 2, where material properties strongly depend on structure as well as chemistry. The robust growth of the brookite polymorph of TiO 2, a promising photocatalyst, has been difficult in both powder and thin-film forms due to the disparity of reported synthesis techniques, their highly specific nature, and lack of mechanistic understanding. In this work, we report the growth of high-fraction (~95%) brookite thin films prepared by annealing amorphous titania precursor films deposited by pulsed laser deposition. We characterize the crystallization process, eliminating themore » previously suggested roles of substrate templating and Na helper ions in driving brookite formation. Instead, we link phase selection directly to film thickness, offering a novel, generalizable route to brookite growth that does not rely on the presence of extraneous elements or particular lattice-matched substrates. In addition to providing a new synthesis route to brookite thin films, our results take a step towards resolving the problem of phase selection in TiO 2 growth, contributing to the further development of this promising functional material.« less

  10. High-fraction brookite films from amorphous precursors.

    PubMed

    Haggerty, James E S; Schelhas, Laura T; Kitchaev, Daniil A; Mangum, John S; Garten, Lauren M; Sun, Wenhao; Stone, Kevin H; Perkins, John D; Toney, Michael F; Ceder, Gerbrand; Ginley, David S; Gorman, Brian P; Tate, Janet

    2017-11-09

    Structure-specific synthesis processes are of key importance to the growth of polymorphic functional compounds such as TiO 2 , where material properties strongly depend on structure as well as chemistry. The robust growth of the brookite polymorph of TiO 2 , a promising photocatalyst, has been difficult in both powder and thin-film forms due to the disparity of reported synthesis techniques, their highly specific nature, and lack of mechanistic understanding. In this work, we report the growth of high-fraction (~95%) brookite thin films prepared by annealing amorphous titania precursor films deposited by pulsed laser deposition. We characterize the crystallization process, eliminating the previously suggested roles of substrate templating and Na helper ions in driving brookite formation. Instead, we link phase selection directly to film thickness, offering a novel, generalizable route to brookite growth that does not rely on the presence of extraneous elements or particular lattice-matched substrates. In addition to providing a new synthesis route to brookite thin films, our results take a step towards resolving the problem of phase selection in TiO 2 growth, contributing to the further development of this promising functional material.

  11. Vinpocetine inhibits oligodendroglial precursor cell differentiation.

    PubMed

    Torres, Klintsy Julieta; Göttle, Peter; Kremer, David; Rivera, Jose Flores; Aguirre-Cruz, Lucinda; Corona, Teresa; Hartung, Hans-Peter; Küry, Patrick

    2012-01-01

    In multiple sclerosis during periods of remission a limited degree of myelin repair can be observed mediated by oligodendroglial precursor cells. Phosphodiesterase inhibitors act as anti-inflammatory agents and might hold promise for future multiple sclerosis treatment. To investigate whether phosphodiesterase inhibitors could also influence myelin repair. We stimulated primary oligodendroglial precursor cells with cilostazol, rolipram and vinpocetine and assessed their effects on repair related cellular processes. We found that vinpocetine exerted a strong negative effect on myelin expression while cilostazol and rolipram did not show such effects. In addition, vinpocetine decreased morphological complexities suggesting an overall negative impact on oligodendroglial cell maturation. We provide evidence that this is not mediated via a blockade of phosphodiesterase-1 but rather by inhibition of IĸB kinase. These findings suggest that vinpocetine via IĸB inhibition exerts a strong negative impact on oligodendroglial cell maturation and may therefore provide the rationale to restrict its application during periods of remission in multiple sclerosis patients. This is of particular interest since vinpocetine is widely used as a health supplement thought to act as a cognitive and memory enhancer for healthy people and patients with neurological or muscle diseases. Copyright © 2012 S. Karger AG, Basel.

  12. Ascorbate as a Biosynthetic Precursor in Plants

    PubMed Central

    Debolt, Seth; Melino, Vanessa; Ford, Christopher M.

    2007-01-01

    Background and Aims l-Ascorbate (vitamin C) has well-documented roles in many aspects of redox control and anti-oxidant activity in plant cells. This Botanical Briefing highlights recent developments in another aspect of l-ascorbate metabolism: its function as a precursor for specific processes in the biosynthesis of organic acids. Scope The Briefing provides a summary of recent advances in our understanding of l-ascorbate metabolism, covering biosynthesis, translocation and functional aspects. The role of l-ascorbate as a biosynthetic precursor in the formation of oxalic acid, l-threonic acid and l-tartaric acid is described, and progress in elaborating the mechanisms of the formation of these acids is reviewed. The potential conflict between the two roles of l-ascorbate in plant cells, functional and biosynthetic, is highlighted. Conclusions Recent advances in the understanding of l-ascorbate catabolism and the formation of oxalic and l-tartaric acids provide compelling evidence for a major role of l-ascorbate in plant metabolism. Combined experimental approaches, using classic biochemical and emerging ‘omics’ technologies, have provided recent insight to previously under-investigated areas. PMID:17098753

  13. Nanoceramic -Metal Matrix Composites by In-Situ Pyrolysis of Organic Precursors in a Liquid Melt

    NASA Astrophysics Data System (ADS)

    Sudarshan; Surappa, M. K.; Ahn, Dongjoon; Raj, Rishi

    2008-12-01

    We show the feasibility of introducing a dispersion of a refractory ceramic phase into metals by stirring a powder of an organic polymer into a magnesium melt and having it convert into a ceramic within the melt by in-situ pyrolysis of the polymer. The pyrolysis is a highly reactive process, accompanied by the evolution of hydrogen, which disperses the ceramic phase into nanoscale constituents. In the present experiments, a polysilazane-based precursor, which is known to yield an amorphous ceramic constituted from silicon, carbon, and nitrogen, was used. Five weight percent of the precursor (which has a nominal ceramic yield of 75 to 85 wt pct) produced a twofold increase in the room-temperature yield strength and reduced the steady-state strain rate at 450 °C by one to two orders of magnitude, relative to pure magnesium. This polymer-based in-situ process (PIP) for processing metal-matrix composites (MMCs) is likely to have great generality, because many different kinds of organic precursors, for producing oxide, carbides, nitrides, and borides, are commercially available. Also, the process would permit the addition of large volume fractions of the ceramic, enabling the nanostructural design, and production of MMCs with a wide range of mechanical properties, meant especially for high-temperature applications. An important and noteworthy feature of the present process, which distinguishes it from other methods, is that all the constituents of the ceramic phase are built into the organic molecules of the precursor ( e.g., polysilazanes contain silicon, carbon, and nitrogen); therefore, a reaction between the polymer and the host metal is not required to produce the dispersion of the refractory phase.

  14. Life Cycle Assessment of III-V Precursors for Photovoltaic and Semiconductor Applications

    SciT

    Horowitz, Kelsey A; Smith, Brittany L.; Babbitt, Callie W.

    This study provides detailed information on the manufacture of III-V metal organic vapor phase epitaxy precursors through extensive literature and patent research. This data informed a cradle-to-gate life cycle assessment of these chemicals. Reported impacts include cumulative energy demand and greenhouse gas emissions. The results were interpreted to identify sources of environmental burden within the life cycle and were compared to energy demand reported in previous studies.

  15. The role of low-energy electrons in focused electron beam induced deposition: four case studies of representative precursors.

    PubMed

    Thorman, Rachel M; Kumar T P, Ragesh; Fairbrother, D Howard; Ingólfsson, Oddur

    2015-01-01

    Focused electron beam induced deposition (FEBID) is a single-step, direct-write nanofabrication technique capable of writing three-dimensional metal-containing nanoscale structures on surfaces using electron-induced reactions of organometallic precursors. Currently FEBID is, however, limited in resolution due to deposition outside the area of the primary electron beam and in metal purity due to incomplete precursor decomposition. Both limitations are likely in part caused by reactions of precursor molecules with low-energy (<100 eV) secondary electrons generated by interactions of the primary beam with the substrate. These low-energy electrons are abundant both inside and outside the area of the primary electron beam and are associated with reactions causing incomplete ligand dissociation from FEBID precursors. As it is not possible to directly study the effects of secondary electrons in situ in FEBID, other means must be used to elucidate their role. In this context, gas phase studies can obtain well-resolved information on low-energy electron-induced reactions with FEBID precursors by studying isolated molecules interacting with single electrons of well-defined energy. In contrast, ultra-high vacuum surface studies on adsorbed precursor molecules can provide information on surface speciation and identify species desorbing from a substrate during electron irradiation under conditions more representative of FEBID. Comparing gas phase and surface science studies allows for insight into the primary deposition mechanisms for individual precursors; ideally, this information can be used to design future FEBID precursors and optimize deposition conditions. In this review, we give a summary of different low-energy electron-induced fragmentation processes that can be initiated by the secondary electrons generated in FEBID, specifically, dissociative electron attachment, dissociative ionization, neutral dissociation, and dipolar dissociation, emphasizing the different

  16. The role of low-energy electrons in focused electron beam induced deposition: four case studies of representative precursors

    PubMed Central

    Thorman, Rachel M; Kumar T. P., Ragesh; Fairbrother, D Howard

    2015-01-01

    Summary Focused electron beam induced deposition (FEBID) is a single-step, direct-write nanofabrication technique capable of writing three-dimensional metal-containing nanoscale structures on surfaces using electron-induced reactions of organometallic precursors. Currently FEBID is, however, limited in resolution due to deposition outside the area of the primary electron beam and in metal purity due to incomplete precursor decomposition. Both limitations are likely in part caused by reactions of precursor molecules with low-energy (<100 eV) secondary electrons generated by interactions of the primary beam with the substrate. These low-energy electrons are abundant both inside and outside the area of the primary electron beam and are associated with reactions causing incomplete ligand dissociation from FEBID precursors. As it is not possible to directly study the effects of secondary electrons in situ in FEBID, other means must be used to elucidate their role. In this context, gas phase studies can obtain well-resolved information on low-energy electron-induced reactions with FEBID precursors by studying isolated molecules interacting with single electrons of well-defined energy. In contrast, ultra-high vacuum surface studies on adsorbed precursor molecules can provide information on surface speciation and identify species desorbing from a substrate during electron irradiation under conditions more representative of FEBID. Comparing gas phase and surface science studies allows for insight into the primary deposition mechanisms for individual precursors; ideally, this information can be used to design future FEBID precursors and optimize deposition conditions. In this review, we give a summary of different low-energy electron-induced fragmentation processes that can be initiated by the secondary electrons generated in FEBID, specifically, dissociative electron attachment, dissociative ionization, neutral dissociation, and dipolar dissociation, emphasizing the

  17. Formation of complex precursors of amino acids by irradiation of simulated interstellar media with heavy ions

    NASA Astrophysics Data System (ADS)

    Kobayashi, K.; Suzuki, N.; Taniuchi, T.; Kaneko, T.; Yoshida, S.

    A wide variety of organic compounds have been detected in such extraterrestrial bodies as meteorites and comets Amino acids were identified in the extracts from Murchison meteorite and other carbonaceous chondrites It is hypothesized that these compounds are originally formed in ice mantles of interstellar dusts ISDs in molecular clouds by cosmic rays and ultraviolet light UV Formation of amino acid precursors by high energy protons or UV irradiation of simulated ISDs was reported by several groups The amino acid precursors were however not well-characterized We irradiated a frozen mixture of methanol ammonia and water with heavy ions to study possible organic compounds abiotically formed in molecular clouds by cosmic rays A mixture of methanol ammonia and water was irradiated with carbon beams 290 MeV u from a heavy ion accelerator HIMAC of National Institute of Radiological Sciences Japan Irradiation was performed either at room temperature liquid phase or at 77 K solid phase The products were characterized by gel filtration chromatography GFC FT-IR pyrolysis PY -GC MS etc Amino acids were analyzed by HPLC and GC MS after acid hydrolysis or the products Amino acids such as glycine and alanine were identified in the products in both the cases of liquid phase and solid phase irradiation Energy yields G-values of glycine were 0 014 liquid phase and 0 007 solid phase respectively Average molecular weights of the products were estimated as to 2300 in both the case Aromatic hydrocarbons N-containing heterocyclic

  18. Identifying precursors and aqueous organic aerosol formation pathways during the SOAS campaign

    NASA Astrophysics Data System (ADS)

    Sareen, Neha; Carlton, Annmarie G.; Surratt, Jason D.; Gold, Avram; Lee, Ben; Lopez-Hilfiker, Felipe D.; Mohr, Claudia; Thornton, Joel A.; Zhang, Zhenfa; Lim, Yong B.; Turpin, Barbara J.

    2016-11-01

    Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized, low-volatility organic aerosol and, in some cases, light-absorbing (brown) carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, and health. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented, forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols), leading to the formation of secondary organic aerosol (SOAAQ). Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOAAQ. The goal of this work is to identify additional precursors and products that may be atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere into water at Brent, Alabama, during the 2013 Southern Oxidant and Aerosol Study (SOAS). Hydroxyl (OH⚫) radical oxidation experiments were conducted with the aqueous mixtures collected from SOAS to better understand the formation of SOA through gas-phase followed by aqueous-phase chemistry. Total aqueous-phase organic carbon concentrations for these mixtures ranged from 92 to 179 µM-C, relevant for cloud and fog waters. Aqueous OH-reactive compounds were primarily observed as odd ions in the positive ion mode by electrospray ionization mass spectrometry (ESI-MS). Ultra high-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) spectra and tandem MS (MS-MS) fragmentation of these ions were consistent with the presence of carbonyls and tetrols. Products were observed in the negative ion mode and included pyruvate and oxalate, which were confirmed by ion chromatography. Pyruvate and oxalate have been found in the particle phase in many locations (as salts and complexes). Thus

  19. HI-SCALE Nanoparticle Composition and Precursors Field Campaign Report

    SciT

    Smith, James; Stark, Harald; Browne, Eleanor

    From 21 August to 27 September, 2016, during the second Intensive Operational Period (IOP) of the Holistic Interactions of Shallow Clouds, Aerosols, and Land-Ecoystems (HI-SCALE) field campaign, a suite of instruments were placed in the Guest Instrument Facility (GIF) at the Central Facility of the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility’s Southern Great Plains (SGP) site in Lamont, Oklahoma. The goal of these measurements was to fully characterize the formation and evolution of atmospheric aerosol particles through measurements of gas-phase precursor and ambient nanoparticle composition. Specifically, we sought to: 1. investigate the role ofmore » acid-base chemistry in new-particle growth through measurements of ammonia and amines as well as organic and inorganic acids in both atmospheric nanoparticles and the gas phase; 2. investigate the contribution of other surface-area or volume-controlled processes to nanoparticle formation and growth, such as the uptake of extremely low volatility organic compounds (ELVOCs); 3. evaluate the performance of a new instrument being developed with funding from the DOE Small Business Innovation Research (SBIR) program for measuring gas-phase amines and related compounds; and 4. together with colleagues measuring on the ground and onboard the ARM Gulfstream-1 (G-1) aircraft during HI-SCALE, create a comprehensive data set related to new particle formation and growth that can be used in modeling efforts by the research team as well as DOE collaborators.« less

  20. An effective approach to synthesize monolayer tungsten disulphide crystals using tungsten halide precursor

    NASA Astrophysics Data System (ADS)

    Thangaraja, Amutha; Shinde, Sachin M.; Kalita, Golap; Tanemura, Masaki

    2016-02-01

    The synthesis of large-area monolayer tungsten disulphide (WS2) single crystal is critical for realistic application in electronic and optical devices. Here, we demonstrate an effective approach to synthesize monolayer WS2 crystals using tungsten hexachloride (WCl6) as a solid precursor in atmospheric chemical vapor deposition process. In this technique, 0.05M solution of WCl6 in ethanol was drop-casted on SiO2/Si substrate to create an even distribution of the precursor, which was reduced and sulfurized at 750 °C in Ar atmosphere. We observed growth of triangular, star-shaped, as well as dendritic WS2 crystals on the substrate. The crystal geometry evolves with the shape and size of the nuclei as observed from the dendritic structures. These results show that controlling the initial nucleation and growth process, large WS2 single crystalline monolayer can be grown using the WCl6 precursor. Our finding shows an easier and effective approach to grow WS2 monolayer using tungsten halide solution-casting, rather than evaporating the precursor for gas phase reaction.

  1. A Review of Single Source Precursors for the Deposition of Ternary Chalcopyrite Materials

    NASA Technical Reports Server (NTRS)

    Banger, K. K.; Cowen, J.; Harris, J.; McClarnon, R.; Hehemann, D. G.; Duraj, S. A.; Scheiman, D.; Hepp, A. F.

    2002-01-01

    The development of thin-film solar cells on flexible, lightweight, space-qualified durable substrates (i.e. Kapton) provides an attractive solution to fabricating solar arrays with high specific power, (W/kg). The syntheses and thermal modulation of ternary single source precursors, based on the [{LR}2Cu(SR')2In(SR')2] architecture in good yields are described. Thermogravimetric analyses (TGA) and Low temperature Differential Scanning Caloriometry, (DSC) demonstrate that controlled manipulation of the steric and electronic properties of either the group five-donor and/or chalcogenide moiety permits directed adjustment of the thermal stability and physical properties of the precursors. TGA-Evolved Gas Analysis, confirms that single precursors decompose by the initial extrusion of the sulphide moiety, followed by the loss of the neutral donor group, (L) to release the ternary chalcopyrite matrix. X-ray diffraction studies, EDS and SEM on the non-volatile pyrolized material demonstrate that these derivatives afford single-phase CuInS2/CuInSe2 materials at low temperature. Thin-film fabrication studies demonstrate that these single source precursors can be used in a spray chemical vapor deposition process, for depositing CuInS2 onto flexible polymer substrates at temperatures less than 400 C.

  2. The rational design of a Au(I) precursor for focused electron beam induced deposition

    PubMed Central

    Marashdeh, Ali; Tiesma, Thiadrik; van Velzen, Niels J C; Harder, Sjoerd; Havenith, Remco W A; De Hosson, Jeff T M

    2017-01-01

    Au(I) complexes are studied as precursors for focused electron beam induced processing (FEBIP). FEBIP is an advanced direct-write technique for nanometer-scale chemical synthesis. The stability and volatility of the complexes are characterized to design an improved precursor for pure Au deposition. Aurophilic interactions are found to play a key role. The short lifetime of ClAuCO in vacuum is explained by strong, destabilizing Au–Au interactions in the solid phase. While aurophilic interactions do not affect the stability of ClAuPMe3, they leave the complex non-volatile. Comparison of crystal structures of ClAuPMe3 and MeAuPMe3 shows that Au–Au interactions are much weaker or partially even absent for the latter structure. This explains its high volatility. However, MeAuPMe3 dissociates unfavorably during FEBIP, making it an unsuitable precursor. The study shows that Me groups reduce aurophilic interactions, compared to Cl groups, which we attribute to electronic rather than steric effects. Therefore we propose MeAuCO as a potential FEBIP precursor. It is expected to have weak Au–Au interactions, making it volatile. It is stable enough to act as a volatile source for Au deposition, being stabilized by 6.5 kcal/mol. Finally, MeAuCO is likely to dissociate in a single step to pure Au. PMID:29354346

  3. Ultrasmall Zeolite L Crystals Prepared from Highly-Interdispersed Alkali-Silicate Precursors.

    PubMed

    Li, Rui; Linares, Noemi; Sutjianto, James G; Chawla, Aseem; Garcia Martinez, Javier; Rimer, Jeffrey D

    2018-06-19

    The preparation of nanosized zeolites is critical for applications where mass transport limitations within microporous networks hinder their performance. Oftentimes the ability to generate ultrasmall zeolite crystals is dependent upon the use of expensive organics with limited commercial relevance. Here, we report the generation of zeolite L crystals with uniform sizes less than 30 nm using a facile, organic-free method. Time-resolved analysis of precursor assembly and evolution during nonclassical crystallization highlights key differences among silicon sources. Our findings reveal that a homogenous dispersion of potassium ions throughout silicate precursors is critical to enhancing the rate of nucleation and facilitating the formation of ultrasmall crystals. Intimate contact between the inorganic structure-directing agent and silica leads to the formation of a metastable nonporous phase, identified as KAlSi2O6, which undergoes an intercrystalline transformation to zeolite L. The presence of highly-interdispersed alkali-silicate precursors is seemingly integral to a reduced zeolite induction time and may facilitate the development of ultrasmall crystals. Given the general difficulty of achieving nanosized crystals in zeolite synthesis, it is likely that using well-dispersed precursors does not have the same effect on all framework types; however, in select cases it may provide an alternative strategy for optimizing zeolite synthesis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. An effective approach to synthesize monolayer tungsten disulphide crystals using tungsten halide precursor

    SciT

    Thangaraja, Amutha; Shinde, Sachin M.; Kalita, Golap, E-mail: kalita.golap@nitech.ac.jp

    2016-02-01

    The synthesis of large-area monolayer tungsten disulphide (WS{sub 2}) single crystal is critical for realistic application in electronic and optical devices. Here, we demonstrate an effective approach to synthesize monolayer WS{sub 2} crystals using tungsten hexachloride (WCl{sub 6}) as a solid precursor in atmospheric chemical vapor deposition process. In this technique, 0.05M solution of WCl{sub 6} in ethanol was drop-casted on SiO{sub 2}/Si substrate to create an even distribution of the precursor, which was reduced and sulfurized at 750 °C in Ar atmosphere. We observed growth of triangular, star-shaped, as well as dendritic WS{sub 2} crystals on the substrate. The crystalmore » geometry evolves with the shape and size of the nuclei as observed from the dendritic structures. These results show that controlling the initial nucleation and growth process, large WS{sub 2} single crystalline monolayer can be grown using the WCl{sub 6} precursor. Our finding shows an easier and effective approach to grow WS{sub 2} monolayer using tungsten halide solution-casting, rather than evaporating the precursor for gas phase reaction.« less

  5. The rational design of a Au(I) precursor for focused electron beam induced deposition.

    PubMed

    Marashdeh, Ali; Tiesma, Thiadrik; van Velzen, Niels J C; Harder, Sjoerd; Havenith, Remco W A; De Hosson, Jeff T M; van Dorp, Willem F

    2017-01-01

    Au(I) complexes are studied as precursors for focused electron beam induced processing (FEBIP). FEBIP is an advanced direct-write technique for nanometer-scale chemical synthesis. The stability and volatility of the complexes are characterized to design an improved precursor for pure Au deposition. Aurophilic interactions are found to play a key role. The short lifetime of ClAuCO in vacuum is explained by strong, destabilizing Au-Au interactions in the solid phase. While aurophilic interactions do not affect the stability of ClAuPMe 3 , they leave the complex non-volatile. Comparison of crystal structures of ClAuPMe 3 and MeAuPMe 3 shows that Au-Au interactions are much weaker or partially even absent for the latter structure. This explains its high volatility. However, MeAuPMe 3 dissociates unfavorably during FEBIP, making it an unsuitable precursor. The study shows that Me groups reduce aurophilic interactions, compared to Cl groups, which we attribute to electronic rather than steric effects. Therefore we propose MeAuCO as a potential FEBIP precursor. It is expected to have weak Au-Au interactions, making it volatile. It is stable enough to act as a volatile source for Au deposition, being stabilized by 6.5 kcal/mol. Finally, MeAuCO is likely to dissociate in a single step to pure Au.

  6. Filler/ Polycarbosilane Systems as CMC Matrix Precursors

    NASA Technical Reports Server (NTRS)

    Hurwitz, Frances I.

    1998-01-01

    Pyrolytic conversion of polymeric precursors to ceramics is accompanied by loss of volatiles and large volume changes. Infiltration of a low viscosity polymer into a fiber preform will fill small spaces within fiber tows by capillary forces, but create large matrix cracks within large, intertow areas. One approach to minimizing shrinkage and reducing the number of required infiltration cycles is to use particulate fillers. In this study, Starfire allylhydridopolycarbosilane (AHPCS) was blended with a silicon carbide powder, with and without dispersant, using shear mixing. The polymer and polymer/particle interactions were characterized using nuclear magnetic resonance, differential scanning calorimetry, thermogravimetric analysis and rheometry. Polymer/particulate slurries and suspensions were used to infiltrate a figidized preform of an eight ply five harness satin CG Nicalon fiber having a dual layer BN/SiC interface coating, and the resulting composites characterized by optical and scanning electron microscopy.

  7. Silsesquioxanes as precursors to ceramic composites

    NASA Technical Reports Server (NTRS)

    Hurwitz, Frances I.; Hyatt, Lizbeth H.; Gorecki, Joy; Damore, Lisa

    1987-01-01

    Silsesquioxanes having the general structure RSiO sub 1.5, where R = methyl, propyl, or phenyl, melt flow at 70 to 100 C. Above 100 C, free -OH groups condense. At 225 C further crosslinking occurs, and the materials form thermosets. Pyrolysis, with accompanying loss of volatiles, takes place at nominally 525 C. At higher temperatures, the R group serves as an internal carbon soruce for carbo-thermal reduction to SiC accompanied by the evolution of CO. By blending silsesquioxanes with varying R groups, both the melt rheology and composition of the fired ceramic can be controlled. Fibers can be spun from the melt which are stable in argon in 1400 C. The silsesquioxanes also were used as matrix precursors for Nicalon and alpha-SiC platelet reinforced composites.

  8. Design of Aerosol Coating Reactors: Precursor Injection

    PubMed Central

    Buesser, Beat; Pratsinis, Sotiris E.

    2013-01-01

    Particles are coated with thin shells to facilitate their processing and incorporation into liquid or solid matrixes without altering core particle properties (coloristic, magnetic, etc.). Here, computational fluid and particle dynamics are combined to investigate the geometry of an aerosol reactor for continuous coating of freshly-made titanium dioxide core nanoparticles with nanothin silica shells by injection of hexamethyldisiloxane (HMDSO) vapor downstream of TiO2 particle formation. The focus is on the influence of HMDSO vapor jet number and direction in terms of azimuth and inclination jet angles on process temperature and coated particle characteristics (shell thickness and fraction of uncoated particles). Rapid and homogeneous mixing of core particle aerosol and coating precursor vapor facilitates synthesis of core-shell nanoparticles with uniform shell thickness and high coating efficiency (minimal uncoated core and free coating particles). PMID:23658471

  9. Mars MetNet Precursor Mission Status

    NASA Astrophysics Data System (ADS)

    Harri, A.-M.; Aleksashkin, S.; Guerrero, H.; Schmidt, W.; Genzer, M.; Vazquez, L.; Haukka, H.

    2013-09-01

    We are developing a new kind of planetary exploration mission for Mars in collaboration between the Finnish Meteorological Institute (FMI), Lavochkin Association (LA), Space Research Institute (IKI) and Institutio Nacional de Tecnica Aerospacial (INTA). The Mars MetNet mission is based on a new semi-hard landing vehicle called MetNet Lander (MNL). The scientific payload of the Mars MetNet Precursor [1] mission is divided into three categories: Atmospheric instruments, Optical devices and Composition and structure devices. Each of the payload instruments will provide significant insights in to the Martian atmospheric behavior. The key technologies of the MetNet Lander have been qualified and the electrical qualification model (EQM) of the payload bay has been built and successfully tested.

  10. Mechanical mixtures of metal oxides and phosphorus pentoxide as novel precursors for the synthesis of transition-metal phosphides.

    PubMed

    Guo, Lijuan; Zhao, Yu; Yao, Zhiwei

    2016-01-21

    This study presents a new type of precursor, mechanical mixtures of metal oxides (MOs) and phosphorus pentoxide (P2O5) are used to synthesize Ni2P, Co2P and MoP phosphides by the H2 reduction method. In addition, this is first report of common solid-state P2O5 being used as a P source for the synthesis of metal phosphides. The traditional precursors are usually prepared via a complicated preparation procedure involving dissolution, drying and calcination steps. However, these novel MOs/P2O5 precursors can be obtained only by simple mechanical mixing of the starting materials. Furthermore, unlike the direct transformation from amorphous phases to phosphides, various specific intermediates were involved in the transformation from MOs/P2O5 to phosphides. It is worthy to note that the dispersions of Ni2P, Co2P and MoP obtained from MOs/P2O5 precursors were superior to those of the corresponding phosphides prepared from the abovementioned traditional precursors. It is suggested that the morphology of the as-prepared metal phosphides might be inherited from the corresponding MOs. Based on the results of XRD, XPS, SEM and TEM, the formation pathway of phosphides can be defined as MOs/P2O5 precursors → complex intermediates (metals, metal phosphates and metal oxide-phosphates) → metal phosphides.

  11. Precursor conditions related to Zimbabwe's summer droughts

    NASA Astrophysics Data System (ADS)

    Nangombe, Shingirai; Madyiwa, Simon; Wang, Jianhong

    2018-01-01

    Despite the increasing severity of droughts and their effects on Zimbabwe's agriculture, there are few tools available for predicting these droughts in advance. Consequently, communities and farmers are more exposed, and policy makers are always ill prepared for such. This study sought to investigate possible cycles and precursor meteorological conditions prior to drought seasons that could be used to predict impending droughts in Zimbabwe. The Single Z-Index was used to identify and grade drought years between 1951 and 2010 according to rainfall severity. Spectral analysis was used to reveal the cycles of droughts for possible use of these cycles for drought prediction. Composite analysis was used to investigate circulation and temperature anomalies associated with severe and extreme drought years. Results indicate that severe droughts are more highly correlated with circulation patterns and embedded weather systems in the Indian Ocean and equatorial Pacific Ocean than any other area. This study identified sea surface temperatures in the average period June to August, geopotential height and wind vector in July to September period, and air temperature in September to November period as precursors that can be used to predict a drought occurrence several months in advance. Therefore, in addition to sea surface temperature, which was identified through previous research for predicting Zimbabwean droughts, the other parameters identified in this study can aid in drought prediction. Drought cycles were established at 20-, 12.5-, 3.2-, and 2.7-year cycles. The spectral peaks, 12.5, 3.2, and 2.7, had a similar timescale with the luni-solar tide, El Niño Southern Oscillation and Quasi Biennial Oscillation, respectively, and hence, occurrence of these phenomena have a possibility of indicating when the next drought might be.

  12. Polymer precursors for ceramic matrix composites

    NASA Technical Reports Server (NTRS)

    Litt, M. H.; Kumar, K.

    1986-01-01

    The synthesis and characterization of a polycyclohexasilane is reported. Because of its cyclic structure, it is anticipated that this polymer might serve as a precursor to SIC having a high char yield with little rearrangement to form small, volatile cyclic silanes, and, as such, would be of interest as a precursor to SiC composite matrices and fibers, or as a binder in ceramic processing. Several approaches to the synthesis of a bifunctional cyclic monomer were attempted; the most successful of these was metal coupling of PhMeSiCl2 and Me2SiCl2. The procedure gives six-membered ring compounds with all degrees of phenyl substitution, from none to hexaphenyl. The compounds with from 0-2 groups were isolated and characterized. The fraction with degree of phenyl substitution equal to 2, a mixture of cis and trans 1,2-; 1,3-; and 1,4 isomers, was isolated in 32 percent yield. Pure 1,4 diphenyldecamethylcyclohexasilane was isolated from the mixed diphenyl compounds and characterized. Diphenyldecamethylcyclohexasilanes were dephenylated to dichlorodecamethylcyclohexasilanes by treating with H2SO4.NH4Cl in benzene. The latter were purified and polymerized by reacting with sodium in toluene. The polymers were characterized by HPGPC, elemental analysis, proton NMR, and IR. Thermogravimetric analyses were carried out on the polymers. As the yield of residual SiC was low, polymers were heat treated to increase the residual char yield. As high as 51.52 percent residual char yield was obtained in one case.

  13. Thermal Stability of Jet Fuels: Kinetics of Forming Deposit Precursors

    NASA Technical Reports Server (NTRS)

    Naegeli, David W.

    1997-01-01

    The focus of this study was on the autoxidation kinetics of deposit precursor formation in jet fuels. The objectives were: (1) to demonstrate that laser-induced fluorescence is a viable kinetic tool for measuring rates of deposit precursor formation in jet fuels; (2) to determine global rate expressions for the formation of thermal deposit precursors in jet fuels; and (3) to better understand the chemical mechanism of thermal stability. The fuels were isothermally stressed in small glass ampules in the 120 to 180 C range. Concentrations of deposit precursor, hydroperoxide and oxygen consumption were measured over time in the thermally stressed fuels. Deposit precursors were measured using laser-induced fluorescence (LIF), hydroperoxides using a spectrophotometric technique, and oxygen consumption by the pressure loss in the ampule. The expressions, I.P. = 1.278 x 10(exp -11)exp(28,517.9/RT) and R(sub dp) = 2.382 x 10(exp 17)exp(-34,369.2/RT) for the induction period, I.P. and rate of deposit precursor formation R(sub dp), were determined for Jet A fuel. The results of the study support a new theory of deposit formation in jet fuels, which suggest that acid catalyzed ionic reactions compete with free radical reactions to form deposit precursors. The results indicate that deposit precursors form only when aromatics are present in the fuel. Traces of sulfur reduce the rate of autoxidation but increase the yield of deposit precursor. Free radical chemistry is responsible for hydroperoxide formation and the oxidation of sulfur compounds to sulfonic acids. Phenols are then formed by the acid catalyzed decomposition of benzylic hydroperoxides, and deposit precursors are produced by the reaction of phenols with aldehydes, which forms a polymer similar to Bakelite. Deposit precursors appear to have a phenolic resin-like structure because the LIF spectra of the deposit precursors were similar to that of phenolic resin dissolved in TAM.

  14. Nazca-South America Subduction Zone Reflectivity from P'P' Precursors

    NASA Astrophysics Data System (ADS)

    Gu, Y. J.; Schultz, R.

    2012-12-01

    Much of what is known about mantle owes to the interpretation of its reflectivity structure. On the global scale mantle stratifications have been attributed to mineralogical phase changes of olivine; two widely observed examples are the 410 and 660 km discontinuities. Among the various seismological tools, results from longer-period SS/PP precursors and high frequency receiver functions are routinely compared to increase the confidence of the recovered mantle stratifications. The former are lower frequency approaches with complex Fresnel zones, while constraints on receiver distribution hinder analysis in oceanic regions for the latter. P'P' precursors are a promising high frequency alternative, capable of resolving small-scale structures (resolution of ~5 km vertically, 200 km laterally) in the mantle, owing to its short-period nature (~1Hz), shallow angle of incidence and nearly symmetric Fresnel zone. However, P'P' precursors are known for several complications: phase triplication (PKiKPPKiKP, PKIKPPKIKP, PKPPKPab and PKPPKPbc) and the maximum-phase Fresnel zones result in strong scattering and asymmetric arrivals. Much of these concerns are alleviated through revamped processing techniques involving stacking, deconvolution, Radon transform and migration. We utilize P'P' precursors to constrain the mantle structure and layering beneath the Nazca-South America subduction zone. Our migration profiles reveal both olivine (e.g., 410, 520, 660) and garnet related transitions in the mantle, with constraints on the sharpness of these transitions. Observations of a depressed 660 are attributed to thermal variations, showing the spatial extent of the impinging Nazca slab. Prominent 520 arrivals near subducted slab material suggest this transition is sharpened to a thickness resonant with P'P' (~10km). The possibility of chemical heterogeneity is evidenced near the top of the mantle transition zone through complicated 410 amplitudes. The existence, depth, sharpness and

  15. Thin HTSC films produced by a polymer metal precursor technique

    NASA Astrophysics Data System (ADS)

    Lampe, L. v.; Zygalsky, F.; Hinrichsen, G.

    In precursors the metal ions are combined with acid groups of polymethacrylic acid (PMAA), polyacrylic acid (PAA) or novolac. Compared to thermal degradation temperature of pure polymers those of precursors are low. Precursors films were patterned by UV lithography. Diffractometric investigations showed that the c-axis oriented epitaxial films of YBa 2Cu 3O x and Bi 2Sr 2CaCu 2O x originated from amorphous metal oxide films, which were received after thermal degradation of the precursor. Transition temperatures and current densities were determined by electric resistivity measurements.

  16. Descriptive and Experimental Analyses of Potential Precursors to Problem Behavior

    PubMed Central

    Borrero, Carrie S.W; Borrero, John C

    2008-01-01

    We conducted descriptive observations of severe problem behavior for 2 individuals with autism to identify precursors to problem behavior. Several comparative probability analyses were conducted in addition to lag-sequential analyses using the descriptive data. Results of the descriptive analyses showed that the probability of the potential precursor was greater given problem behavior compared to the unconditional probability of the potential precursor. Results of the lag-sequential analyses showed a marked increase in the probability of a potential precursor in the 1-s intervals immediately preceding an instance of problem behavior, and that the probability of problem behavior was highest in the 1-s intervals immediately following an instance of the precursor. We then conducted separate functional analyses of problem behavior and the precursor to identify respective operant functions. Results of the functional analyses showed that both problem behavior and the precursor served the same operant functions. These results replicate prior experimental analyses on the relation between problem behavior and precursors and extend prior research by illustrating a quantitative method to identify precursors to more severe problem behavior. PMID:18468281

  17. Applying the polarity rapid assessment method to characterize nitrosamine precursors and to understand their removal by drinking water treatment processes.

    PubMed

    Liao, Xiaobin; Bei, Er; Li, Shixiang; Ouyang, Yueying; Wang, Jun; Chen, Chao; Zhang, Xiaojian; Krasner, Stuart W; Suffet, I H Mel

    2015-12-15

    Some N-nitrosamines (NAs) have been identified as emerging disinfection by-products during water treatment. Thus, it is essential to understand the characteristics of the NA precursors. In this study, the polarity rapid assessment method (PRAM) and the classical resin fractionation method were studied as methods to fractionate the NA precursors during drinking water treatment. The results showed that PRAM has much higher selectivity for NA precursors than the resin approach. The normalized N-nitrosodimethylamine formation potential (NDMA FP) and N-nitrosodiethylamine (NDEA) FP of four resin fractions was at the same level as the average yield of the bulk organic matter whereas that of the cationic fraction by PRAM showed 50 times the average. Thus, the cationic fraction was shown to be the most important NDMA precursor contributor. The PRAM method also helped understand which portions of the NA precursor were removed by different water treatment processes. Activated carbon (AC) adsorption removed over 90% of the non-polar PRAM fraction (that sorbs onto the C18 solid phase extraction [SPE] cartridge) of NDMA and NDEA precursors. Bio-treatment removed 80-90% of the cationic fraction of PRAM (that is retained on the cation exchange SPE cartridge) and 40-60% of the non-cationic fractions. Ozonation removed 50-60% of the non-polar PRAM fraction of NA precursors and transformed part of them into the polar fraction. Coagulation and sedimentation had very limited removal of various PRAM fractions of NA precursors. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Precursors of chicken flavor. II. Identification of key flavor precursors using sensory methods.

    PubMed

    Aliani, Michel; Farmer, Linda J

    2005-08-10

    Sensory evaluation was used to identify flavor precursors that are critical for flavor development in cooked chicken. Among the potential flavor precursors studied (thiamin, inosine 5'-monophosphate, ribose, ribose-5-phosphate, glucose, and glucose-6-phosphate), ribose appears most important for chicken aroma. An elevated concentration (added or natural) of only 2-4-fold the natural concentration gives an increase in the selected aroma and flavor attributes of cooked chicken meat. Assessment of the volatile odor compounds by gas chromatography-odor assessment and gas chromatography-mass spectrometry showed that ribose increased odors described as "roasted" and "chicken" and that the changes in odor due to additional ribose are probably caused by elevated concentrations of compounds such as 2-furanmethanethiol, 2-methyl-3-furanthiol, and 3-methylthiopropanal.

  19. Synthesis, characterization, microstructure, optical and magnetic properties of strontium cobalt carbonate precursor and Sr2Co2O5 oxide material

    NASA Astrophysics Data System (ADS)

    Agilandeswari, K.; Ruban Kumar, A.

    2014-04-01

    Sr2Co2O5 ceramic synthesized by the coprecipitation of strontium cobalt carbonate method. XRD analysis shows the single phase strontianite precursor and decomposed oxide product as orthorhombic structure of Sr2Co2O5. Thermal analysis proves the Sr2Co2O5 phase formation temperature of 800 °C. SEM image indicates crystalline rod shaped carbonate precursor transformed to oxide as porous diffused sphere shape particles. Optical band gap it reveals the strontium cobalt carbonate precursor as insulating material and the Sr2Co2O5 as semiconducting nature. The room temperature magnetic study indicates the carbonate precursor as paramagnetic but its oxide Sr2Co2O5 as superparamagnetic behavior.

  20. Precursor directed synthesis - ``molecular'' mechanisms in the Soft Chemistry approaches and their use for template-free synthesis of metal, metal oxide and metal chalcogenide nanoparticles and nanostructures

    NASA Astrophysics Data System (ADS)

    Seisenbaeva, Gulaim A.; Kessler, Vadim G.

    2014-05-01

    This review provides an insight into the common reaction mechanisms in Soft Chemistry processes involved in nucleation, growth and aggregation of metal, metal oxide and chalcogenide nanoparticles starting from metal-organic precursors such as metal alkoxides, beta-diketonates, carboxylates and their chalcogene analogues and demonstrates how mastering the precursor chemistry permits us to control the chemical and phase composition, crystallinity, morphology, porosity and surface characteristics of produced nanomaterials.This review provides an insight into the common reaction mechanisms in Soft Chemistry processes involved in nucleation, growth and aggregation of metal, metal oxide and chalcogenide nanoparticles starting from metal-organic precursors such as metal alkoxides, beta-diketonates, carboxylates and their chalcogene analogues and demonstrates how mastering the precursor chemistry permits us to control the chemical and phase composition, crystallinity, morphology, porosity and surface characteristics of produced nanomaterials. To Professor David Avnir on his 65th birthday.

  1. Production of jet fuel precursor monoterpenoids from engineered Escherichia coli: Production of Jet Fuel Precursor Monoterpenoids

    SciT

    Mendez-Perez, Daniel; Alonso-Gutierrez, Jorge; Hu, Qijun

    Monoterpenes (C 10 isoprenoids) are the main components of essential oils and are possible precursors for many commodity chemicals and high energy density fuels. Monoterpenes are synthesized from geranyl diphosphate (GPP), which is also the precursor for the biosynthesis of farnesyl diphosphate (FPP). FPP biosynthesis diverts the carbon flux from monoterpene production to C 15 products and quinone biosynthesis. In this study, we tested a chromosomal mutation of Escherichia coli's native FPP synthase (IspA) to improve GPP availability for the production of monoterpenes using a heterologous mevalonate pathway. Monoterpene production at high levels required not only optimization of GPP productionmore » but also a basal level of FPP to maintain growth. The optimized strains produced two jet fuel precursor monoterpenoids 1,8-cineole and linalool at the titer of 653 mg/L and 505 mg/L, respectively, in batch cultures with 1% glucose. The engineered strains developed in this work provide useful resources for the production of high-value monoterpenes.« less

  2. Production of jet fuel precursor monoterpenoids from engineered Escherichia coli: Production of Jet Fuel Precursor Monoterpenoids

    DOE PAGES

    Mendez-Perez, Daniel; Alonso-Gutierrez, Jorge; Hu, Qijun; ...

    2017-05-18

    Monoterpenes (C 10 isoprenoids) are the main components of essential oils and are possible precursors for many commodity chemicals and high energy density fuels. Monoterpenes are synthesized from geranyl diphosphate (GPP), which is also the precursor for the biosynthesis of farnesyl diphosphate (FPP). FPP biosynthesis diverts the carbon flux from monoterpene production to C 15 products and quinone biosynthesis. In this study, we tested a chromosomal mutation of Escherichia coli's native FPP synthase (IspA) to improve GPP availability for the production of monoterpenes using a heterologous mevalonate pathway. Monoterpene production at high levels required not only optimization of GPP productionmore » but also a basal level of FPP to maintain growth. The optimized strains produced two jet fuel precursor monoterpenoids 1,8-cineole and linalool at the titer of 653 mg/L and 505 mg/L, respectively, in batch cultures with 1% glucose. The engineered strains developed in this work provide useful resources for the production of high-value monoterpenes.« less

  3. Investigation of phase evolution of CaCu3Ti4O12 (CCTO) by in situ synchrotron high-temperature powder diffraction

    NASA Astrophysics Data System (ADS)

    Ouyang, Xin; Huang, Saifang; Zhang, Weijun; Cao, Peng; Huang, Zhaohui; Gao, Wei

    2014-03-01

    In situ synchrotron X-ray powder diffraction was used to study the high-temperature phase evolution of CaCu3Ti4O12 (CCTO) precursors prepared via solid-state and sol-gel methods. After the precursors are heated to 1225 °C, the CCTO phase is the main phase observed in the calcined powder, with the presence of some minor impurities. Comparing the two precursors, we found that the onset temperature for the CCTO phase formation is 800 °C in the sol-gel precursor, lower than that in the solid-state precursor (875 °C). Intermediate phases were only observed in the sol-gel precursor. Both precursors are able to be calcined to sub-micrometric sized powders. Based on the synchrotron data along with differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA), the phase formation sequence and mechanism during calcination are proposed in this study.

  4. Frog Swarms: Earthquake Precursors or False Alarms?

    PubMed Central

    Grant, Rachel A.; Conlan, Hilary

    2013-01-01

    Simple Summary Media reports linking unusual animal behaviour with earthquakes can potentially create false alarms and unnecessary anxiety among people that live in earthquake risk zones. Recently large frog swarms in China and elsewhere have been reported as earthquake precursors in the media. By examining international media reports of frog swarms since 1850 in comparison to earthquake data, it was concluded that frog swarms are naturally occurring dispersal behaviour of juveniles and are not associated with earthquakes. However, the media in seismic risk areas may be more likely to report frog swarms, and more likely to disseminate reports on frog swarms after earthquakes have occurred, leading to an apparent link between frog swarms and earthquakes. Abstract In short-term earthquake risk forecasting, the avoidance of false alarms is of utmost importance to preclude the possibility of unnecessary panic among populations in seismic hazard areas. Unusual animal behaviour prior to earthquakes has been reported for millennia but has rarely been scientifically documented. Recently large migrations or unusual behaviour of amphibians have been linked to large earthquakes, and media reports of large frog and toad migrations in areas of high seismic risk such as Greece and China have led to fears of a subsequent large earthquake. However, at certain times of year large migrations are part of the normal behavioural repertoire of amphibians. News reports of “frog swarms” from 1850 to the present day were examined for evidence that this behaviour is a precursor to large earthquakes. It was found that only two of 28 reported frog swarms preceded large earthquakes (Sichuan province, China in 2008 and 2010). All of the reported mass migrations of amphibians occurred in late spring, summer and autumn and appeared to relate to small juvenile anurans (frogs and toads). It was concluded that most reported “frog swarms” are actually normal behaviour, probably caused by

  5. Eruption precursors: Manifestations and strategies for detection

    NASA Astrophysics Data System (ADS)

    Poland, Michael; Pritchard, Matthew

    2017-04-01

    The past several decades have seen a rapid increase in volcano monitoring and modeling capabilities. Diverse arrays of instrument networks can detect a variety of pre-, co-, and post-eruptive phenomena, and remote sensing observations are available across a range of spatial, temporal, and spectral resolutions. A growing class of models, based on the physics of magmatic systems, are making use of these expanding datastreams, providing probabilistic assessments of such parameters as magma supply, volatile content, and eruption duration. To what extent, however, do these developments heighten our ability to identify eruption precursors? The advent of better data and new models provides an opportunity to reexamine our understanding of pre-eruption unrest, as well as our ability to detect and recognize it as such. An idealized model of the buildup to a volcanic eruption might include magma ascent from a deep source region and accumulation in the mid- to upper crust in the preceding months to years. The process might be manifested by surface inflation and deep long-period earthquakes, and accompanied by an increase in CO2 emissions. As magma continues to accumulate, distal volcano-tectonic earthquakes may result as stress builds on nearby faults, H2S emissions may increase as sulfur in a shallow reservoir is hydrolyzed by groundwater, and fumarole and spring temperatures may increase and show changes in chemistry. In the days to hours before an eruption, sudden changes in the rate and style of earthquakes (including repeating earthquakes and tremor) and deformation may occur as the magma reservoir ruptures and magma moves laterally or vertically. Phreatic eruptions might result as ascending magma comes into contact with groundwater, and SO2 emissions might increase as the path between the magma and surface dries out. How often does such a sequence actually occur? Relatively few volcanoes are comprehensively monitored prior to obvious expressions of unrest, so this is not

  6. Role of Elemental Sulfur in Forming Latent Precursors of H2S in Wine.

    PubMed

    Jastrzembski, Jillian A; Allison, Rachel B; Friedberg, Elle; Sacks, Gavin L

    2017-12-06

    The level of hydrogen sulfide (H 2 S) can increase during abiotic storage of wines, and potential latent sources of H 2 S are still under investigation. We demonstrate that elemental sulfur (S 0 ) residues on grapes not only can produce H 2 S during fermentation but also can form precursors capable of generating additional H 2 S after bottle storage for 3 months. H 2 S could be released from S 0 -derived precursors by addition of a reducing agent (TCEP), but not by addition of strong brine to induce release of H 2 S from metal sulfide complexes. The size of the TCEP-releasable pool varied among yeast strains. Using the TCEP assay, multiple polar S 0 -derived precursors were detected following normal-phase preparative chromatography. Using reversed-phase liquid chromatography and high-resolution mass spectrometry, we detected an increase in the levels of diglutathione trisulfane (GSSSG) and glutathione disulfide (GSSG) in S 0 -fermented red wine and an increase in the levels of glutathione S-sulfonate (GSSO 3 - ) and tetrathionate (S 4 O 6 2- ) in S 0 -fermented white wine as compared to controls. GSSSG, but not S 4 O 6 2- , was shown to evolve H 2 S in the presence of TCEP. Pathways for the formation of GSSSG, GSSG, GSSO 3 - , and S 4 O 6 2- from S 0 are proposed.

  7. Synthesis and optical properties of Mg-Al layered double hydroxides precursor powders

    NASA Astrophysics Data System (ADS)

    Lin, Chia-Hsuan; Chu, Hsueh-Liang; Hwang, Weng-Sing; Wang, Moo-Chin; Ko, Horng-Huey

    2017-12-01

    The synthesis and optical properties of Mg-Al layered double hydroxide (LDH) precursor powders were investigated using X-ray diffraction (XRD), Fourier transform-infrared (FT-IR) spectroscopy, transmission electron microscopy (TEM), selected area electron diffraction (SAED), high-resolution TEM (HRTEM), UV-transmission spectrometer, and fluorescence spectrophotometer. The FT-IR results show that the intense absorption at around 1363-1377 cm-1 can be assigned to the antisymmetric ν3 mode of interlayer carbonate anions because the LDH phase contains some CO32-. The XRD results show that all of the Mg-Al LDH precursor powders contain only a single phase of [Mg0.833Al0.167(OH)2](CO3)0.083.(H2O)0.75 but have broad and weak intensities of peaks. All of Mg-Al LDHs precursor powders before calcination have the same photoluminescence (PL) spectra. Moreover, these spectra were excited at λex = 235 nm, and the broad emission band was in the range 325-650 nm. In the range, there were relatively strong intensity at around 360, 407 and 510 nm, respectively.

  8. Sentinel-5 Precursor: First Copernicus Atmospheric Mission Ready for Launch

    NASA Astrophysics Data System (ADS)

    McMullan, Kevin; Nett, Herbert; Fehr, Thorsten; Ingmann, Paul

    2016-08-01

    Sentinel-5 Precursor (S-5P) will be the first of a series of atmospheric missions to be launched within the European Commission's Copernicus (former GMES) Programme. With the current launch window mid October - mid November 2016 and a nominal lifetime of 7 years S-5P is expected to provide continuity in the availability of global atmospheric data products between its predecessor missions SCIAMACHY (Envisat) and OMI (AURA) and the future Sentinel-4 and -5 series.S-5P will deliver unique data regarding the sources and sinks of trace gases with a focus on the lower Troposphere including the planet boundary layer. Due to its enhanced spatial, temporal and spectral sampling capabilities, as compared to its predecessors.The S-5P satellite will carry a single payload, TROPOMI (TROPOspheric Monitoring Instrument) which is jointly developed by The Netherlands and ESA. Covering spectral channels in the UV, visible, near- and short-wave infrared it will measure various key species including tropospheric/stratospheric ozone, NO2, SO2, CO, CH4, CH2O as well as cloud and aerosol parameters.The S-5P Project has successfully passed the Ground Segment Acceptance Review (GS-AR) and the satellite level Qualification Acceptance Review (QAR) in March and April 2016, respectively. Remaining pre-launch tasks focus on the detailed planning of Phase E1 activities and the training of the operations teams.

  9. Hydrodeoxygenation of coal using organometallic catalyst precursors

    NASA Astrophysics Data System (ADS)

    Kirby, Stephen R.

    2002-04-01

    coals. Trends within the data were similar to those reported by other authors. Based on the conclusions from both the model compound studies and the coal analysis, predictions were made of the catalyst precursors' performance in the HDO of the three selected coals. It was concluded that CoMo-T2 is a desirable catalyst precursor for the HDO of coals (particularly low-rank coals), but that an optimum set of conditions must be determined to take full advantage of its HDO ability. (Abstract shortened by UMI.)

  10. Mixed-ligand approach to design of heterometallic single-source precursors with discrete molecular structure.

    PubMed

    Lieberman, Craig M; Navulla, Anantharamulu; Zhang, Haitao; Filatov, Alexander S; Dikarev, Evgeny V

    2014-05-05

    Heterometallic single-source precursors for the Pb/Fe = 1:1 oxide materials, PbFe(β-dik)4 (β-dik = hexafluoroacetylacetonate (hfac, 1), acetylacetonate (acac, 2), and trifluoroacetylacetonate (tfac, 4)), have been isolated by three different solid-state synthetic methods. The crystal structures of heterometallic diketonates 1, 2, and 4 were found to contain polymeric chains built on alternating [Fe(β-dik)2] and [Pb(β-dik)2] units that are held together by bridging M-O interactions. Heterometallic precursors are highly volatile, but soluble only in coordinating solvents, in which they dissociate into solvated homometallic fragments. In order to design the heterometallic precursor with a proper metal/metal ratio and with a discrete molecular structure, we used a combination of two different diketonate ligands. Heteroleptic complex Pb2Fe2(hfac)6(acac)2 (5) has been obtained by optimized stoichiometric reaction of an addition of homo-Fe(acac)2 to heterometallic Pb2Fe(hfac)6 (3) diketonate that can be run in solution on a high scale. The combination of two ligands with electron-withdrawing and electron-donating groups allows changing the connectivity pattern within the heterometallic assembly and yields the precursor with a discrete tetranuclear structure. In accord with its molecular structure, heteroleptic complex 5 is soluble even in noncoordinating solvents and was found to retain its heterometallic structure in solution. Thermal decomposition of heterometallic precursors in air at 750 °C resulted in the target Pb2Fe2O5 oxide, a prospective multiferroic material. Prolonging the annealing time or increasing the decomposition temperature leads to another phase-pure lead-iron oxide PbFe12O19 that is a representative of the important family of magnetic hexaferrites.

  11. Essential elucidation for preparation of supported nickel phosphide upon nickel phosphate precursor

    SciT

    Liu, Xuguang, E-mail: liuxuguang@qust.edu.cn; Xu, Lei; Zhang, Baoquan

    2014-04-01

    Preparation of supported nickel phosphide (Ni{sub 2}P) depends on nickel phosphate precursor, generally related to its chemical composition and supports. Study of this dependence is essential and meaningful for the preparation of supported Ni{sub 2}P with excellent catalytic activity. The chemical nature of nickel phosphate precursor is revealed by Raman and UV–vis spectra. It is found that initial P/Ni mole ratio ≥0.8 prohibits the Ni-O-Ni bridge bonding (i.e., nickel oxide). This chemical bonding will not result in Ni{sub 2}P structure, verified by XRD characterization results. The alumina (namely, γ-Al{sub 2}O{sub 3}, θ-Al{sub 2}O{sub 3}, or α-Al{sub 2}O{sub 3}) with distinctmore » physiochemical properties also results in diverse chemical nature of nickel phosphate, and then different nickel phosphides. The influence of alumina support on producing Ni{sub 2}P was explained by the theory of surface energy heterogeneity, calculated by the NLDFT method based on N{sub 2}-sorption isotherm. The uniform surface energy of α-Al{sub 2}O{sub 3} results only in the nickel phosphosate precursor and thus the Ni{sub 2}P phase. - Graphical abstract: Surface energy heterogeneity in alumina (namely α-Al{sub 2}O{sub 3}, θ-Al{sub 2}O{sub 3}, and γ-Al{sub 2}O{sub 3}) supported multi-oxidic precursors with different reducibilities and thus diverse nickel phosphides (i.e., Ni{sub 3}P, Ni{sub 12}P{sub 5}, Ni{sub 2}P). - Highlights: • Preparing pure Ni{sub 2}P. • Elucidating nickel phosphate precursor. • Associating with surface energy.« less

  12. MMPM - Mission implementation of Mars MetNet Precursor

    NASA Astrophysics Data System (ADS)

    Harri, A.-M.

    2009-04-01

    We are developing a new kind of planetary exploration mission for Mars - MetNet in situ observation network based on a new semi-hard landing vehicle called the Met-Net Lander (MNL). The key technical aspects and solutions of the mission will be discussed. The eventual scope of the MetNet Mission is to deploy some 20 MNLs on the Martian surface using inflatable descent system structures, which will be supported by observations from the orbit around Mars. Currently we are working on the MetNet Mars Precursor Mission (MMPM) to deploy one MetNet Lander to Mars in the 2009/2011 launch window as a technology and science demonstration mission. The MNL will have a versatile science payload focused on the atmospheric science of Mars. Detailed characterization of the Martian atmospheric circulation patterns, boundary layer phenomena, and climatology cycles, require simultaneous in-situ measurements by a network of observation posts on the Martian surface. The scientific payload of the MetNet Mission encompasses separate instrument packages for the atmospheric entry and descent phase and for the surface operation phase. The MetNet mission concept and key probe technologies have been developed and the critical subsystems have been qualified to meet the Martian environmental and functional conditions. This development effort has been fulfilled in collaboration between the Finnish Meteorological Institute (FMI), the Russian Lavoschkin Association (LA) and the Russian Space Research Institute (IKI) since August 2001. Currently the INTA (Instituto Nacional de Técnica Aeroespacial) from Spain is also participating in the MetNet payload development.

  13. An Evaluation of Strengthening Precursors to Increase Preschooler Compliance

    ERIC Educational Resources Information Center

    Kraus, Aaron J.; Hanley, Gregory P.; Cesana, Lori L.; Eisenberg, Danielle; Jarvie, Adam C.

    2012-01-01

    We evaluated the strategy of increasing precursors to compliance on the compliance of 2 preschool boys. Modeling and differential reinforcement were used to increase specific responses to his name being called prior to the opportunity to comply with an instruction. The precursors were stopping the ongoing activity and orienting to, making eye…

  14. Assimilation of NAD(+) precursors in Candida glabrata.

    PubMed

    Ma, Biao; Pan, Shih-Jung; Zupancic, Margaret L; Cormack, Brendan P

    2007-10-01

    The yeast pathogen Candida glabrata is a nicotinamide adenine dinucleotide (NAD(+)) auxotroph and its growth depends on the environmental supply of vitamin precursors of NAD(+). C. glabrata salvage pathways defined in this article allow NAD(+) to be synthesized from three compounds - nicotinic acid (NA), nicotinamide (NAM) and nicotinamide riboside (NR). NA is salvaged through a functional Preiss-Handler pathway. NAM is first converted to NA by nicotinamidase and then salvaged by the Preiss-Handler pathway. Salvage of NR in C. glabrata occurs via two routes. The first, in which NR is phosphorylated by the NR kinase Nrk1, is independent of the Preiss-Handler pathway. The second is a novel pathway in which NR is degraded by the nucleosidases Pnp1 and Urh1, with a minor role for Meu1, and ultimately converted to NAD(+) via the nicotinamidase Pnc1 and the Preiss-Handler pathway. Using C. glabrata mutants whose growth depends exclusively on the external NA or NR supply, we also show that C. glabrata utilizes NR and to a lesser extent NA as NAD(+) sources during disseminated infection.

  15. Defining pancreatic endocrine precursors and their descendants.

    PubMed

    White, Peter; May, Catherine Lee; Lamounier, Rodrigo N; Brestelli, John E; Kaestner, Klaus H

    2008-03-01

    The global incidence of diabetes continues to increase. Cell replacement therapy and islet transplantation offer hope, especially for severely affected patients. Efforts to differentiate insulin-producing beta-cells from progenitor or stem cells require knowledge of the transcriptional programs that regulate the development of the endocrine pancreas. Differentiation toward the endocrine lineage is dependent on the transcription factor Neurogenin 3 (Neurog3, Ngn3). We utilize a Neurog3-enhanced green fluorescent protein knock-in mouse model to isolate endocrine progenitor cells from embryonic pancreata (embryonic day [E]13.5 through E17.5). Using advanced genomic approaches, we generate a comprehensive gene expression profile of these progenitors and their immediate descendants. A total of 1,029 genes were identified as being temporally regulated in the endocrine lineage during fetal development, 237 of which are transcriptional regulators. Through pathway analysis, we have modeled regulatory networks involving these proteins that highlight the complex transcriptional hierarchy governing endocrine differentiation. We have been able to accurately capture the gene expression profile of the pancreatic endocrine progenitors and their descendants. The list of temporally regulated genes identified in fetal endocrine precursors and their immediate descendants provides a novel and important resource for developmental biologists and diabetes researchers alike.

  16. Robotic Precursor Missions for Mars Habitats

    NASA Technical Reports Server (NTRS)

    Huntsberger, Terry; Pirjanian, Paolo; Schenker, Paul S.; Trebi-Ollennu, Ashitey; Das, Hari; Joshi, Sajay

    2000-01-01

    Infrastructure support for robotic colonies, manned Mars habitat, and/or robotic exploration of planetary surfaces will need to rely on the field deployment of multiple robust robots. This support includes such tasks as the deployment and servicing of power systems and ISRU generators, construction of beaconed roadways, and the site preparation and deployment of manned habitat modules. The current level of autonomy of planetary rovers such as Sojourner will need to be greatly enhanced for these types of operations. In addition, single robotic platforms will not be capable of complicated construction scenarios. Precursor robotic missions to Mars that involve teams of multiple cooperating robots to accomplish some of these tasks is a cost effective solution to the possible long timeline necessary for the deployment of a manned habitat. Ongoing work at JPL under the Mars Outpost Program in the area of robot colonies is investigating many of the technology developments necessary for such an ambitious undertaking. Some of the issues that are being addressed include behavior-based control systems for multiple cooperating robots (CAMPOUT), development of autonomous robotic systems for the rescue/repair of trapped or disabled robots, and the design and development of robotic platforms for construction tasks such as material transport and surface clearing.

  17. Bacterial Cellular Materials as Precursors of Chloroform

    NASA Astrophysics Data System (ADS)

    Wang, J.; Ng, T.; Zhang, Q.; Chow, A. T.; Wong, P.

    2011-12-01

    The environmental sources of chloroform and other halocarbons have been intensively investigated because their effects of stratospheric ozone destruction and environmental toxicity. It has been demonstrated that microorganisms could facilitate the biotic generation of chloroform from natural organic matters in soil, but whether the cellular materials itself also serves as an important precursor due to photo-disinfection is poorly known. Herein, seven common pure bacterial cultures (Acinetobacter junii, Aeromonas hydrophila, Bacillus cereus, Bacillus substilis, Escherichia coli, Shigella sonnei, Staphylococcus sciuri) were chlorinated to evaluate the yields of chloroform, dibromochloromethane, dichlorobromomethane, and bromoform. The effects of bromide on these chemical productions and speciations were also investigated. Results showed that, on average, 5.64-36.42 μg-chloroform /mg-C were generated during the bacterial chlorination, in similar order of magnitude to that generated by humic acid (previously reported as 78 μg-chloroform/mg-C). However, unlike humic acid in water chlorination, chloroform concentration did not simply increase with the total organic carbon in water mixture. In the presence of bromide, the yield of brominated species responded linearly to the bromide concentration. This study provides useful information to understand the contributions of chloroform from photodisinfection processes in coastal environments.

  18. Cystic precursors to invasive pancreatic cancer

    PubMed Central

    Matthaei, Hanno; Schulick, Richard D.; Hruban, Ralph H.; Maitra, Anirban

    2011-01-01

    Improvements in the sensitivity and quality of cross-sectional imaging have led to increasing numbers of patients being diagnosed with cystic lesions of the pancreas. In parallel, clinical, radiological, pathological and molecular studies have improved the systems for classifying these cysts. Patients with asymptomatic serous cystic neoplasms can be managed conservatively with regular monitoring; however, the clinical management of patients with intraductal papillary mucinous neoplasms and mucinous cystic neoplasms is far more challenging, as it is difficult to determine whether these lesions will progress to malignancy. Fortunately, prospective studies have helped to establish that proposed clinical and radiological criteria (the Sendai guidelines) can be used to guide the care of patients with cystic lesions of the pancreas. Despite this progress in imaging and clinical guidelines, sensitive and specific tests have not yet been developed that can reliably predict the histology and biological properties of a cystic lesion. Such biomarkers are urgently needed, as noninvasive precursors of pancreatic cancer are curable, while the vast majority of invasive pancreatic adenocarcinomas are not. PMID:21383670

  19. Innate lymphoid cells, precursors and plasticity.

    PubMed

    Gronke, Konrad; Kofoed-Nielsen, Michael; Diefenbach, Andreas

    2016-11-01

    Innate lymphoid cells (ILC) have only recently been recognized as a separate entity of the lymphoid lineage. Their subpopulations share common characteristics in terms of early development and major transcriptional circuitry with their related cousins of the T cell world. It is currently hypothesized that ILCs constitute an evolutionary older version of the lymphoid immune system. They are found at all primary entry points for pathogens such as mucosal surfaces of the lung and gastrointestinal system, the skin and the liver, which is the central contact point for pathogens that breach the intestinal barrier and enter the circulation. There, ILC contribute to the first line defense as well as to organ homeostasis. However, ILC are not only involved in classical defense tasks, but also contribute to the organogenesis of lymphoid organs as well as tissue remodeling and even stem cell regeneration. ILC may, therefore, implement different functions according to their emergence in ontogeny, their development and their final tissue location. We will review here their early development from precursors of the fetal liver and the adult bone marrow as well as their late plasticity in adaptation to their environment. Copyright © 2016 European Federation of Immunological Societies. Published by Elsevier B.V. All rights reserved.

  20. Review on hydroxylamine, a precursor to amino-acids

    NASA Astrophysics Data System (ADS)

    Lemaire, Jean Louis

    2015-08-01

    Does life on earth come from interstellar space (IS)?It has been recently demonstrated that part of the terrestrial water is of IS origin [Cleeves et al. Science 2014]. This raises the question whether materials like amino-acids or their pre-biotic molecular precursors could have been formed and brought to earth in the same way than water. Another question is whether these molecules were formed in the gas phase or through reactions on the surface/volume of ice-covered grains. This may then have occurred in the vicinity of proto-stellar cores or deep into a pristine dense molecular clouds at very low temperatures.As far as bio-related molecules are concerned, chemistry with nitrogen-bearing molecules (like NH3 and NO) is involved. I review recent experimental work showing that hydroxylamine (NH2OH) could be formed either by surface or by volume reactions in conditions close to those prevailing in dense media. They use either electron-UV irradiation of water-ammonia ices [Zheng & Kaiser JCPA 2010] or successive hydrogenation of solid nitric oxide[Congiu, Fedoseev & al. ApJL.2012] or the simple oxidation of ammonia [He, Vidali, Lemaire & Garrod, ApJ, 2015] or the reaction of ammonia with hydroxyl radicals in a rare gas matrix [Zins & Krim, 2014, 69th ISMS]. A step further, the synthesis of the simplest amino-acids, glycine (NH2CH2COOH) and L- or D-alanine (NH2CH3CHCOOH) has already been obtained via reactions in the gas phase involving NH2OH+ [Blagojevic & al. MNRAS 2003].In addition to several earlier models demonstrating that the formation of all these molecules is possible in the gas phase, a new recent three-phase gas-grain chemical kinetics model of hot cores [Garrod ApJ 2013] shows that the results of ammonia oxidation we obtain are plausible by surface/volume reactions.Although none of the aforementioned molecules (except glycine in a sample of cometary origin) has been yet detected in the IS, they all are considered by many observers and modelers as likely

  1. Influence of thermal treatment on the formation of zirconia nanostructured powder by thermal decomposition of different precursors

    NASA Astrophysics Data System (ADS)

    Stoia, Marcela; Barvinschi, Paul; Barbu-Tudoran, Lucian; Negrea, Adina; Barvinschi, Floricica

    2013-10-01

    The paper presents some results concerning the preparation of zirconia powders starting from ZrOCl2·8H2O by using two synthesis methods: (a) precipitation with NH3, at 90 °C, and (b) thermal decomposition of carboxylate precursors, obtained in the reaction of zirconium nitrate and two different alcohols, 1,3-propanediol (PD) and poly(vinyl alcohol) (PVA), at 150 °C. The precursors obtained at different temperatures have been characterized by thermal analysis (TG, DTA) and FT-IR spectroscopy. DTA analysis evidenced very clearly the transition temperatures between zirconia crystalline phases. The precursors have been annealed at different temperatures in order to obtain zirconia powders and the as obtained powders have been characterized by means of X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), and Scanning Electron Microscopy (SEM). In case of precipitation method the presence of the tetragonal phase was observed at 400 °C, while the monoclinic phase appears at temperatures higher than 400 °C, becoming major crystalline phase starting with 700 °C. In case of the powders prepared by thermal decomposition of carboxylate precursors, the tetragonal phase was formed at temperatures below 700 °C, when the monoclinic phase begin to crystallize as secondary phase, in a higher proportion for the samples synthesized with 1,3-propanediol. All powders annealed at 1200 °C are pure monoclinic zirconia. SEM images have evidenced for the zirconia powders annealed at 1000 °C particles with diameters up to 150 nm, agglomerated in micrometer-sized aggregates, more individualized and homogenous than that obtained in the case of zirconia powder synthesized with poly(vinyl alcohol).

  2. Solid State Chemistry of Clathrate Phases: Crystal Structure, Chemical Bonding and Preparation Routes

    NASA Astrophysics Data System (ADS)

    Baitinger, Michael; Böhme, Bodo; Ormeci, Alim; Grin, Yuri

    Clathrates represent a family of inorganic materials called cage compounds. The key feature of their crystal structures is a three-dimensional (host) framework bearing large cavities (cages) with 20-28 vertices. These polyhedral cages bear—as a rule—guest species. Depending on the formal charge of the framework, clathrates are grouped in anionic, cationic and neutral. While the bonding in the framework is of (polar) covalent nature, the guest-host interaction can be ionic, covalent or even van-der Waals, depending on the chemical composition of the clathrates. The chemical composition and structural features of the cationic clathrates can be described by the enhanced Zintl concept, whereas the composition of the anionic clathrates deviates often from the Zintl counts, indicating additional atomic interactions in comparison with the ionic-covalent Zintl model. These interactions can be visualized and studied by applying modern quantum chemical approaches such as electron localizability.

  3. From iron(III) precursor to magnetite and vice versa

    SciT

    Gotic, M., E-mail: gotic@irb.hr; Jurkin, T.; Music, S.

    2009-10-15

    The syntheses of nanosize magnetite particles by wet-chemical oxidation of Fe{sup 2+} have been extensively investigated. In the present investigation the nanosize magnetite particles were synthesised without using the Fe(II) precursor. This was achieved by {gamma}-irradiation of water-in-oil microemulsion containing only the Fe(III) precursor. The corresponding phase transformations were monitored. Microemulsions (pH {approx} 12.5) were {gamma}-irradiated at a relatively high dose rate of {approx}22 kGy/h. Upon 1 h of {gamma}-irradiation the XRD pattern of the precipitate showed goethite and unidentified low-intensity peaks. Upon 6 h of {gamma}-irradiation, reductive conditions were achieved and substoichiometric magnetite ({approx}Fe{sub 2.71}O{sub 4}) particles with insignificantmore » amount of goethite particles found in the precipitate. Hydrated electrons (e{sub aq}{sup -}), organic radicals and hydrogen gas as radiolytic products were responsible for the reductive dissolution of iron oxide in the microemulsion and the reduction Fe{sup 3+} {yields} Fe{sup 2+}. Upon 18 h of {gamma}-irradiation the precipitate exhibited dual behaviour, it was a more oxidised product than the precipitate obtained after 6 h of {gamma}-irradiation, but it contained magnetite particles in a more reduced form ({approx}Fe{sub 2.93}O{sub 4}). It was presumed that the reduction and oxidation processes existed as concurrent competitive processes in the microemulsion. After 18 h of {gamma}-irradiation the pH of the medium shifted from the alkaline to the acidic range. The high dose rate of {approx}22 kGy/h was directly responsible for this shift to the acidic range. At a slightly acidic pH a further reduction of Fe{sup 3+} {yields} Fe{sup 2+} resulted in the formation of more stoichiometric magnetite particles, whereas the oxidation conditions in the acidic medium permitted the oxidation Fe{sup 2+} {yields} Fe{sup 3+}. The Fe{sup 3+} was much less soluble in the acidic medium and it

  4. Lanthanide-Substituted Magnetite Nanoparticles Using a New Mixed Precursor Method by Thermoanaerobacter ethanolicus

    NASA Astrophysics Data System (ADS)

    Moon, J.; Roh, Y.; Yeary, L. W.; Lauf, R. J.; Phelps, T. J.

    2006-12-01

    A metal reducing bacterium, Thermoanaerobacter ethanolicus successfully converted the precursor of L (lanthanide)-mixed akaganeite (LxFe1-xOOH) phase to L-substituted magnetite (LyFe3-yO4) while avoiding the potentially toxic effects of soluble L-ions. Antibiotic elements, lanthanide (Nd, Gd, Tb, Ho, and Er)-substituted magnetites were produced by microbial fermentation using LxFe1-xOOH, where x was up to 0.02 which is equivalent to 0.72 mM. Combining lanthanides into the akaganeite precursor phase mitigated some of the toxicity when compared to the traditional method by using pure akaganeite and the dissolved L-salt form. This new technique showed that an upper limit of L-concentrations between 0.02 and 0.1 mM might suppress bacterial activity. At the equivalent L-cation mole fraction, the traditional method increased the concentration of soluble toxic L ions in the final media. The precursor method enabled production of microbially synthesized L- substituted magnetite with an L-concentration 36-fold greater than could be obtained when the lanthanides were added as soluble salts. These results were confirmed by protein assay. The increase of L-concentration in the magnetite evidently manipulates its physical properties such as decreasing Curie temperature and decreasing saturation magnetism of L-substituted magnetite. This mixed precursor method can therefore be used to extend the application for nanofermentation and other bacterial synthesis fields where there is a need for economically low-energy consumable microbial production of nanoscale materials that should involve toxic or inhibitory elements to bacterial growth.

  5. Molding mineral within microporous hydrogels by a polymer-induced liquid-precursor (PILP) process.

    PubMed

    Cheng, Xingguo; Gower, Laurie B

    2006-01-01

    Natural biominerals often have exquisite morphologies, where the cells exercise a high degree of crystallographic control through secretion of biological macromolecules and regulation of ion transport. One important example is the sea urchin spine. It has recently been shown to be formed through deposition of a transient amorphous calcium carbonate (ACC) precursor phase that later transforms to single-crystalline calcite, ultimately forming an elaborate three-dimensional microporous calcium carbonate structure with interconnected pores. Macromolecules associated with the mineral phase are thought to play a key role in regulating this transformation. The work described here mimics this type of morphological control by "molding" an amorphous calcium carbonate precursor within a porous poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogel that has been prepared as a negative replica from the void space of an urchin spine. Using an acidic biomimetic polymer as a process-directing agent, we show that polyaspartic acid induces amorphous calcium carbonate (ACC) nanoparticles, which have fluidic character and therefore are able to infiltrate the PHEMA hydrogel replica and coalesce into the convoluted morphology that replicates the original microporous structure of the sea urchin spine. By "molding" calcium carbonate into a complex morphology at room temperature, using a precursor process that is induced by a biomimetic acidic macromolecule, the PILP process is a useful in vitro model for examining different aspects of the amorphous-to-crystalline transformation process that is apparently used by a variety of biomineralizing organisms. For example, although we were able to replicate the overall morphology of the spine, it had polycrystalline texture; further studies with this system will focus on controlling the nucleation event, which may help to elucidate how such a convoluted structure can be prepared with single-crystalline texture via an amorphous precursor. Through a

  6. Templating Influence of Molecular Precursors on Pr(OH)3 Nanostructures.

    PubMed

    Hemmer, Eva; Cavelius, Christian; Huch, Volker; Mathur, Sanjay

    2015-07-06

    Four new praseodymium alkoxo and amido compounds ([Pr3(μ3-OtBu)2(μ2-OtBu)3(OtBu)4(HOtBu)2] (1), [Pr{OC(tBu)3}3(THF)] (2), [PrCl{N(SiMe3)2}2(THF)]2 (3), and [PrCl{OC(tBu)3}2(THF)]2 (4)) were synthesized and structurally characterized by single-crystal X-ray diffraction analysis. Application of these compounds in solvothermal synthesis of praseodymium oxide/hydroxide nanostructures showed their templating influence on the morphology and phase composition of the resulting solid-state materials. Differential reactivity of the chosen alkoxide ligands toward water and the different arrangements of metal-oxygen units in the studied precursor compounds strongly influenced the kinetics of hydrolysis and cross-condensation reactions as manifested in the morphological changes and phase composition of the final products. Thermal decomposition studies of 1-4 confirmed their conversion into the corresponding oxide phases. Activation of compounds 1, 2, and 4 by either a base or a stoichiometric amount of water showed the distinct influence of their chemical configuration on the obtained nanopowders: whereas 1 solely produced nanorods of Pr(OH)3, 2 predominantly formed a mixture of rod-shaped and spherical particles. The solvothermal decomposition of 4 resulted in Pr(OH)2Cl or PrOCl due to the presence of Cl ligands in the molecular precursor. The resultant materials were thoroughly characterized to demonstrate the relationship between precursor chemistry and the processing parameters that are clearly manifested in the morphology and phase of the final ceramics.

  7. Investigation of phase evolution of CaCu{sub 3}Ti{sub 4}O{sub 12} (CCTO) by in situ synchrotron high-temperature powder diffraction

    SciT

    Ouyang, Xin; Huang, Saifang; School of Materials Science and Technology, China University of Geosciences

    2014-03-15

    In situ synchrotron X-ray powder diffraction was used to study the high-temperature phase evolution of CaCu{sub 3}Ti{sub 4}O{sub 12} (CCTO) precursors prepared via solid-state and sol–gel methods. After the precursors are heated to 1225 °C, the CCTO phase is the main phase observed in the calcined powder, with the presence of some minor impurities. Comparing the two precursors, we found that the onset temperature for the CCTO phase formation is 800 °C in the sol–gel precursor, lower than that in the solid-state precursor (875 °C). Intermediate phases were only observed in the sol–gel precursor. Both precursors are able to bemore » calcined to sub-micrometric sized powders. Based on the synchrotron data along with differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA), the phase formation sequence and mechanism during calcination are proposed in this study. -- Graphical abstract: The in situ synchrotron HT-XRD patterns of CCTO sol–gel and solid-state precursor. Highlights: • Phase formation sequence/mechanism in two CCTO precursors has been established. • Formation temperature of CCTO via sol–gel method is lower than solid-state method. • Intermediate phases are only observed in the sol–gel precursor. • Both precursors are able to be calcined into sub-micrometric sized powders.« less

  8. Synthesis, Dielectric, Electrical and Optical characterization of ZnO synthesized by chemical route using polymer precursors

    NASA Astrophysics Data System (ADS)

    Mishra, Raman; Bajpai, P. K.

    2011-11-01

    Nano-size ZnO (particle size 7.8 nm) have been prepared from a versatile, efficient and technically simple polymer matrix based precursor solution. The precursor solution constituted of zinc nitrates with polymer PVA in presence of mono-/disaccharides. Annealing the precursor mass at 900 °C single phase zinc oxide nano-particles are obtained. X-ray diffraction analysis confirms hexagonal crystal structure with lattice parameter a = b = 3.261 A0, c = 5.220 A0. The estimated average particle size obtained from XRD data is ≈7.8 nm. The impedance analysis reveals that the grain resistance decreases with increase in temperature as expected for a semi-conducting material. The relaxation is polydispersive and conduction is mainly through grains. Optical properties and AC/DC conduction activation energies are estimated from Arrhenius plots and conduction mechanism is discussed.

  9. Biosynthesis and characterization of silver nanoparticles prepared from two novel natural precursors by facile thermal decomposition methods

    NASA Astrophysics Data System (ADS)

    Goudarzi, Mojgan; Mir, Noshin; Mousavi-Kamazani, Mehdi; Bagheri, Samira; Salavati-Niasari, Masoud

    2016-09-01

    In this work, two natural sources, including pomegranate peel extract and cochineal dye were employed for the synthesis of silver nanoparticles. The natural silver complex from pomegranate peel extract resulted in nano-sized structures through solution-phase method, but this method was not efficient for cochineal dye-silver precursor and the as-formed products were highly agglomerated. Therefore, an alternative facile solid-state approach was investigated as for both natural precursors and the results showed successful production of well-dispersed nanoparticles with narrow size distribution for cochineal dye-silver precursor. The products were characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Energy dispersive X-ray microanalysis (EDX), and Transmission Electron Microscopy (TEM).

  10. The influence of the precursor compositional ratio on Cu2ZnSnS4 films prepared by using sulfurization of the metallic precursor

    NASA Astrophysics Data System (ADS)

    Amal, Muhamad I.; Kim, Kyoo Ho

    2013-12-01

    Cu2ZnSnS4 (CZTS) films were prepared by using the sulfurization of sputtered metallic precursors. The compositional ratio of the CZTS films was slightly different compared to their initial metallic precursors due to elemental loss during annealing. The Cu/(Zn+Sn) ratio for the CZTS-1, CZTS-2 and CZTS-3 films were 0.91, 1.06 and 1.21, respectively. In addition, all films had a compositional ratio of Zn/Sn >1. The grain sizes of the CZTS films increased with increasing Cu ratio. X-ray diffraction and Raman spectroscopy showed that the CZTS films with an excess of copper and zinc had secondary phases of Cu2SnS3 and ZnS. The optical band gap and absorption coefficient for all CZTS films in the range of the experimental compositions were calculated to be 1.5 eV and >104 cm-1, respectively. The presence of secondary phases related to compositional ratio in the CZTS films influenced the electrical properties. The CZTS-1 film with a Cu-poor and Zn-rich composition whose a carrier concentration, an electrical mobility, and a resistivity values were 2.29 × 1018 cm-3, 10.29 cm2 V-1 s-1, 3.16 Ω cm, is the most suitable for solar-cell applications.

  11. Precursor Science for the Terrestrial Planet Finder

    NASA Technical Reports Server (NTRS)

    Lawson, P. R. (Editor); Unwin, S. C. (Editor); Beichman, C. A. (Editor)

    2004-01-01

    This document outlines a path for the development of the field of extrasolar planet research, with a particular emphasis on the goals of the Terrestrial Planet Finder (TPF). Over the past decade, a new field of research has developed, the study of extrasolar planetary systems, driven by the discovery of massive planets around nearby stars. The planet count now stands at over 130. Are there Earth-like planets around nearby stars? Might any of those planets be conducive to the formation and maintenance of life? These arc the questions that TPF seeks to answer. TPF will be implemented as a suite of two space observatories, a 6-m class optical coronagraph, to be launched around 20 14, and a formation flying mid-infrared interferometer, to be launched sometime prior to 2020. These facilities will survey up to 165 or more nearby stars and detect planets like Earth should they be present in the 'habitable zone' around each star. With observations over a broad wavelength range, TPF will provide a robust determination of the atmospheric composition of planets to assess habitability and the presence of life. At this early stage of TPF's development, precursor observational and theoretical programs are essential to help define the mission, to aid our understanding of the planets that TPF could discover, and to characterize the stars that TPF will eventually study. This document is necessarily broad in scope because the significance of individual discoveries is greatly enhanced when viewed in thc context of the field as a whole. This document has the ambitious goal of taking us from our limited knowledge today, in 2004, to the era of TPF observations in the middle of the next decade. We must use the intervening years wisely. This document will be reviewed annually and updated as needed. The most recent edition is available online at http://tpf.jpl.nasa.gov/ or by email request to lawson@hucy.jpl.nasa.gov

  12. High crystalline Cu2ZnSnS4 semiconductor prepared from low toxicity ethanol-based precursors

    NASA Astrophysics Data System (ADS)

    Munir, Badrul; Prastyo, Bayu Eko; Nurjaya, Dwi Marta; Muslih, Ersan Yudhapratama; Alfauzan, Sahri Karim

    2017-01-01

    At this moment, we present a new, cost-effective, and environmentally friendly method of preparing a high crystalline Cu2ZnSnS4 (CZTS) absorber layer for thin film solar cells using ethanol-based solutions. Ethanolamine (ETA) and 2-mercaptopropionic acid (MPA) were studied as a stabilizer and to improve wetting ability of the precursors during the deposition process. Cu2ZnSnS4 precursors are deposited onto soda lime glass using spin coater in different molar of cations in the precursor. The effects of a precursor system, ethanol-ETA-MPA, and ethanol-MPA, on the structure, morphology, composition and optical properties of CZTS thin films have been investigated in details. X-ray diffraction and energy-dispersive X-ray spectroscopy analyses confirmed the successful fabrication of high crystalline Cu2ZnSnS4 kesterite phase. The crystallinity of CZTS is continue increasing before reaching 2.2 molar cations of the ethanol-MPA precursors. The crystallinity of ethanol-ETA-MPA precursors remains similar in the experiment using 1.2 molar and 1.6 molars. The highest crystallinity was achieved using 2 molar cations of the ethanol-MPA precursor. Its band gap energy is found to be around 1.4 eV. The SEM micrographs of CZTS film shows the average grain size around 1.5 µm and some porosity which indicated the room of improvement. The high-crystallinity CZTS achieved in the present study brings a low-cost absorber semiconductor one step closer to practical use.

  13. Metal Precursors and Reduction in Renazzo Chondrules

    NASA Astrophysics Data System (ADS)

    Zanda, B.; Hewins, R. H.; Bourot-Denise, M.

    1993-07-01

    The positive Co-Ni correlation and Cr, P contents of metal in CR chondrites have generally been taken to indicate their primitive nature, probably inherited from condensation [1,2]. Si in the metal of primitive chondrites has also been reported and interpreted as a condensation heritage [3,4]. However, Cr, P, and Si (dissolved or in the form of inclusions) in metal of any CR chondrule generally fall within a +-10% range, though large interchondrule variations exist [5]. We have shown that Cr and Si in metal are in equilibrium with Fo and En in silicates, due to the reducing conditions that prevailed during chondrule formation [6]. In the present paper, we show that the Co-Ni trend was also established during chondrule formation out of heterogeneous precursor material with a variable Co/Ni ratio. Chondrules in Renazzo are classified as highly molten (HM), in which metal has been expelled to form a mantle outside the chondrule, medium molten (MM), with metal inside and at the periphery, and with evidence for grain coalescence, and little melted (LM), in which metal is only present in the form of small blebs dispersed among the silicates. In HM chondrules, Ni and Co concentrations are extremely homogeneous, comparatively low and in the cosmic ratio. In LM chondrules, quite the opposite: Ni and Co spread over a large range and the amount of scatter increases with decreasing degree of melting of the chondrule. In addition, they do not correlate along the cosmic ratio, but show a negative correlation if any. This heterogeneity is present not only from grain to grain in these chondrules, but also in individual metal grains. Such a heterogeneity is also exhibited in Cr and P abundances that span a much larger range than the +-10% found in the other chondrules. These results indicate that chondrule formation is responsible for the homogenization of Co and Ni contents of metal grains through coalescence and mixing. The less melted objects give an idea of the nature of metal

  14. Hydrothermal synthesis and characterization of Si and Sr co-substituted hydroxyapatite nanowires using strontium containing calcium silicate as precursors.

    PubMed

    Zhang, Na; Zhai, Dong; Chen, Lei; Zou, Zhaoyong; Lin, Kaili; Chang, Jiang

    2014-04-01

    In the absence of any organic surfactants and solvents, the silicon (Si) and strontium (Sr) co-substituted hydroxyapatite [Ca10(PO4)6(OH)2, Si/Sr-HAp] nanowires were synthesized via hydrothermal treatment of the Sr-containing calcium silicate (Sr-CS) powders as the precursors in trisodium phosphate (Na3PO4) aqueous solution. The morphology, phase, chemical compositions, lattice constants and the degradability of the products were characterized. The Si/Sr-HAp nanowires with diameter of about 60nm and up to 2μm in length were obtained after hydrothermal treatment of the Sr-CS precursors. The Sr and Si substitution amount of the HAp nanowires could be well regulated by facile tailoring the Sr substitution level of the precursors and the reaction ratio of the precursor/solution, respectively. The SiO4 tetrahedra and Sr(2+) ions occupied the crystal sites of the HAp, and the lattice constants increased apparently with the increase of the substitution amount. EDS mapping also suggested the uniform distribution of Si and Sr in the synthetic nanowires. Moreover, the Si/Sr-substitution apparently improved the degradability of the HAp materials. Our study suggested that the precursor transformation method provided a facile approach to synthesize the Si/Sr co-substituted HAp nanowires with controllable substitution amount, and the synthetic Si/Sr-HAp nanowires might be used as bioactive materials for hard tissue regeneration applications. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Tuning the optical properties of ZnO nanorods by variation of precursor concentration through hydrothermal method

    NASA Astrophysics Data System (ADS)

    Kumari, Lakshmi; Kar, Asit Kumar

    2018-05-01

    ZnO nanorods with varying precursor concentration have been successfully synthesized by the hydrothermal method. The effect of the precursor concentration on the structural, morphological and optical properties of the resulting nanorods was investigated by means of X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), UV-Vis spectroscopy and photoluminescence (PL) spectroscopy. The crystalline structural characterization demonstrated that the synthesized materials crystallize in pure ZnO wurtzite structure without any other secondary phase. SEM micrographs demonstrate nanorod type features in all the samples. In addition, they show that increase of precursor concentration changes the length and diameter of nanorods. The UV-Vis studies show a strong absorption band in UV region at 373 nm attributed to the band-edge absorption of wurtzite hexagonal ZnO, blue shifted relative to its bulk form (380 nm). The PL spectra of obtained nanorods excited at 360 nm present broad visible emission. Moreover, as the visible region (from 510 to 550 nm) is concerned, it is speculated that the increase of the precursor concentration affects strongly the kind of interstitial defects (Oi, Zni and Vo) formed in ZnO nanorods. The luminescence intensity decreases with the increase of precursor concentration.

  16. Methods for forming particles from single source precursors

    DOEpatents

    Fox, Robert V [Idaho Falls, ID; Rodriguez, Rene G [Pocatello, ID; Pak, Joshua [Pocatello, ID

    2011-08-23

    Single source precursors are subjected to carbon dioxide to form particles of material. The carbon dioxide may be in a supercritical state. Single source precursors also may be subjected to supercritical fluids other than supercritical carbon dioxide to form particles of material. The methods may be used to form nanoparticles. In some embodiments, the methods are used to form chalcopyrite materials. Devices such as, for example, semiconductor devices may be fabricated that include such particles. Methods of forming semiconductor devices include subjecting single source precursors to carbon dioxide to form particles of semiconductor material, and establishing electrical contact between the particles and an electrode.

  17. Molybdenum nitride fibers or tubes via ammonolysis of polysulfide precursor

    NASA Astrophysics Data System (ADS)

    Wang, Shutao; Zhang, Zude; Zhang, Yange; Qian, Yitai

    2004-08-01

    Millimeter-sized molybdenum nitride (MoN), in the forms of fiber-like prisms or hollow tubes, has been successfully synthesized via thermal ammonolysis of molybdenum polysulfide precursor. The initial morphology of the precursor is well preserved in the final product. This method could be expanded to preparation of other fiber-like nonmetal ceramics without addition of template. The polysulfide precursor (abbreviated to PS), hydrothermally prepared at 30°C (PS1) or 150°C (PS2), was characterized by various methods for better comprehension of the sulfide-nitride topotactic conversion model.

  18. Supplementation with tocotrienol-rich fraction alters the plasma levels of Apolipoprotein A-I precursor, Apolipoprotein E precursor, and C-reactive protein precursor from young and old individuals.

    PubMed

    Heng, Eng Chee; Karsani, Saiful Anuar; Abdul Rahman, Mariati; Abdul Hamid, Noor Aini; Hamid, Zalina; Wan Ngah, Wan Zurinah

    2013-10-01

    Tocotrienol possess beneficial effects not exhibited by tocopherol. In vitro studies using animal models have suggested that these effects are caused via modulation of gene and protein expression. However, human supplementation studies using tocotrienol-rich isomers are limited. This study aims to identify plasma proteins that changed in expression following tocotrienol-rich fraction (TRF) supplementation within two different age groups. Subjects were divided into two age groups-32 ± 2 (young) and 52 ± 2 (old) years old. Four subjects from each group were assigned with TRF (78% tocotrienol and 22% tocopherol, 150 mg/day) or placebo capsules for 6 months. Fasting plasma were obtained at 0, 3, and 6 months. Plasma tocopherol and tocotrienol levels were determined. Plasma proteome was resolved by 2DE, and differentially expressed proteins identified by MS. The expressions of three proteins were validated by Western blotting. Six months of TRF supplementation significantly increased plasma levels of tocopherols and tocotrienols. Proteins identified as being differentially expressed were related to cholesterol homeostasis, acute-phase response, protease inhibitor, and immune response. The expressions of Apolipoprotein A-I precursor, Apolipoprotein E precursor, and C-reactive protein precursor were validated. The old groups showed more proteins changing in expression. TRF appears to not only affect plasma levels of tocopherols and tocotrienols, but also the levels of plasma proteins. The identity of these proteins may provide insights into how TRF exerts its beneficial effects. They may also be potentially developed into biomarkers for the study of the effects and effectiveness of TRF supplementation.

  19. Large scale synthesis of nanostructured zirconia-based compounds from freeze-dried precursors

    NASA Astrophysics Data System (ADS)

    Gómez, A.; Villanueva, R.; Vie, D.; Murcia-Mascaros, S.; Martínez, E.; Beltrán, A.; Sapiña, F.; Vicent, M.; Sánchez, E.

    2013-01-01

    Nanocrystalline zirconia powders have been obtained at the multigram scale by thermal decomposition of precursors resulting from the freeze-drying of aqueous acetic solutions. This technique has equally made possible to synthesize a variety of nanostructured yttria or scandia doped zirconia compositions. SEM images, as well as the analysis of the XRD patterns, show the nanoparticulated character of those solids obtained at low temperature, with typical particle size in the 10-15 nm range when prepared at 673 K. The presence of the monoclinic, the tetragonal or both phases depends on the temperature of the thermal treatment, the doping concentration and the nature of the dopant. In addition, Rietveld refinement of the XRD profiles of selected samples allows detecting the coexistence of the tetragonal and the cubic phases for high doping concentration and high thermal treatment temperatures. Raman experiments suggest the presence of both phases also at relatively low treatment temperatures.

  20. Ceramics Derived from Organo-Metallic Precursors

    DTIC Science & Technology

    1991-10-01

    spraying, and roller-coating may also be used to good effect . The films deposited by any of these techniques are ready to be fired immediately...films. The wet chemical route offers great potential for highly cost- effective processing; and the critical issue for its wide-scale implementation is...glasses and subsequently to crystallize single phase HTSC materials. The fourth composition, 4223, was made in order to test the effect of Bi on glass

  1. Biological Indicators in Studies of Earthquake Precursors

    NASA Astrophysics Data System (ADS)

    Sidorin, A. Ya.; Deshcherevskii, A. V.

    2012-04-01

    Time series of data on variations in the electric activity (EA) of four species of weakly electric fish Gnathonemus leopoldianus and moving activity (MA) of two cat-fishes Hoplosternum thoracatum and two groups of Columbian cockroaches Blaberus craniifer were analyzed. The observations were carried out in the Garm region of Tajikistan within the frameworks of the experiments aimed at searching for earthquake precursors. An automatic recording system continuously recorded EA and DA over a period of several years. Hourly means EA and MA values were processed. Approximately 100 different parameters were calculated on the basis of six initial EA and MA time series, which characterize different variations in the EA and DA structure: amplitude of the signal and fluctuations of activity, parameters of diurnal rhythms, correlated changes in the activity of various biological indicators, and others. A detailed analysis of the statistical structure of the total array of parametric time series obtained in the experiment showed that the behavior of all animals shows a strong temporal variability. All calculated parameters are unstable and subject to frequent changes. A comparison of the data obtained with seismicity allow us to make the following conclusions: (1) The structure of variations in the studied parameters is represented by flicker noise or even a more complex process with permanent changes in its characteristics. Significant statistics are required to prove the cause-and-effect relationship of the specific features of such time series with seismicity. (2) The calculation of the reconstruction statistics in the EA and MA series structure demonstrated an increase in their frequency in the last hours or a few days before the earthquake if the hypocenter distance is comparable to the source size. Sufficiently dramatic anomalies in the behavior of catfishes and cockroaches (changes in the amplitude of activity variation, distortions of diurnal rhythms, increase in the

  2. Large scale synthesis of nanostructured zirconia-based compounds from freeze-dried precursors

    SciT

    Gomez, A.; Villanueva, R.; Vie, D.

    2013-01-15

    Nanocrystalline zirconia powders have been obtained at the multigram scale by thermal decomposition of precursors resulting from the freeze-drying of aqueous acetic solutions. This technique has equally made possible to synthesize a variety of nanostructured yttria or scandia doped zirconia compositions. SEM images, as well as the analysis of the XRD patterns, show the nanoparticulated character of those solids obtained at low temperature, with typical particle size in the 10-15 nm range when prepared at 673 K. The presence of the monoclinic, the tetragonal or both phases depends on the temperature of the thermal treatment, the doping concentration and themore » nature of the dopant. In addition, Rietveld refinement of the XRD profiles of selected samples allows detecting the coexistence of the tetragonal and the cubic phases for high doping concentration and high thermal treatment temperatures. Raman experiments suggest the presence of both phases also at relatively low treatment temperatures. - Graphical abstract: Zr{sub 1-x}A{sub x}O{sub 2-x/2} (A=Y, Sc; 0{<=}x{<=}0.12) solid solutions have been prepared as nanostructured powders by thermal decomposition of precursors obtained by freeze-drying, and this synthetic procedure has been scaled up to the 100 g scale. Highlights: Black-Right-Pointing-Pointer Zr{sub 1-x}A{sub x}O{sub 2-x/2} (A=Y, Sc; 0{<=}x{<=}0.12) solid solutions have been prepared as nanostructured powders. Black-Right-Pointing-Pointer The synthetic method involves the thermal decomposition of precursors obtained by freeze-drying. Black-Right-Pointing-Pointer The temperature of the thermal treatment controls particle sizes. Black-Right-Pointing-Pointer The preparation procedure has been scaled up to the 100 g scale. Black-Right-Pointing-Pointer This method is appropriate for the large-scale industrial preparation of multimetallic systems.« less

  3. Cross influences of ozone and sulfate precursor emissions changes on air quality and climate

    PubMed Central

    Unger, Nadine; Shindell, Drew T.; Koch, Dorothy M.; Streets, David G.

    2006-01-01

    Tropospheric O3 and sulfate both contribute to air pollution and climate forcing. There is a growing realization that air quality and climate change issues are strongly connected. To date, the importance of the coupling between O3 and sulfate has not been fully appreciated, and thus regulations treat each pollutant separately. We show that emissions of O3 precursors can dramatically affect regional sulfate air quality and climate forcing. At 2030 in an A1B future, increased O3 precursor emissions enhance surface sulfate over India and China by up to 20% because of increased levels of OH and gas-phase SO2 oxidation rates and add up to 20% to the direct sulfate forcing for that region relative to the present day. Hence, O3 precursors impose an indirect forcing via sulfate, which is more than twice the direct O3 forcing itself (compare −0.61 vs. +0.35 W/m2). Regulatory policy should consider both air quality and climate and should address O3 and sulfate simultaneously because of the strong interaction between these species. PMID:16537360

  4. Production and application of synthetic precursors labeled with carbon-11 and fluorine-18

    SciT

    Ferrieri, R.A.

    2001-04-02

    It is evident from this chapter that there is enormous flexibility both in the selection of the nature of the radioisotope and ways to generate it, as well as in the selection of the labeling precursor to appropriately attach that radioisotope to some larger biomolecule of interest. The arsenal of radiolabeling precursors now available to the chemist is quite extensive, and without a doubt will continue to grow as chemists develop new ones. However, the upcoming years will perhaps reflect a greater effort in refining existing methods for preparing some of those precursors that are already available to us. Formore » example, the use of solid-phase reactions to accomplish in a single step what would normally take several using conventional solvent-based reactions has already been shown to work in many occasions. The obvious advantage here is that processes become more amenable to system automation thus affording greater reliability in day-to-day operations. There are perhaps other technologies in science that have yet to be realized by the chemist in the PET laboratory that could provide a similar or even a greater benefit. One only needs to be open to new ideas, and imaginative enough to apply them to the problems at hand.« less

  5. CVD of SiC and AlN using cyclic organometallic precursors

    NASA Technical Reports Server (NTRS)

    Interrante, L. V.; Larkin, D. J.; Amato, C.

    1992-01-01

    The use of cyclic organometallic molecules as single-source MOCVD precursors is illustrated by means of examples taken from our recent work on AlN and SiC deposition, with particular focus on SiC. Molecules containing (AlN)3 and (SiC)2 rings as the 'core structure' were employed as the source materials for these studies. The organoaluminum amide, (Me2AlNH2)3, was used as the AlN source and has been studied in a molecular beam sampling apparatus in order to determine the gas phase species present in a hot-wall CVD reactor environment. In the case of SiC CVD, a series of disilacyclobutanes (Si(XX')CH2)2 (with X and X' = H, CH3, and CH2SiH2CH3), were examined in a cold-wall, hot-stage CVD reactor in order to compare their relative reactivities and prospective utility as single-source CVD precursors. The parent compound, disilacyclobutane, (SiH2CH2)2, was found to exhibit the lowest deposition temperature (ca. 670 C) and to yield the highest purity SiC films. This precursor gave a highly textured, polycrystalline film on the Si(100) substrates.

  6. The union of somatic gonad precursors and primordial germ cells during C. elegans embryogenesis

    PubMed Central

    Rohrschneider, Monica R.; Nance, Jeremy

    2013-01-01

    Somatic gonadal niche cells control the survival, differentiation, and proliferation of germline stem cells. The establishment of this niche-stem cell relationship is critical, and yet the precursors to these two cell types are often born at a distance from one another. The simple C. elegans gonadal primordium, which contains two somatic gonad precursors (SGPs) and two primordial germ cells (PGCs), provides an accessible model for determining how stem cell and niche cell precursors first assemble during development. To visualize the morphogenetic events that lead to formation of the gonadal primordium, we generated transgenic strains to label the cell membranes of the SGPs and PGCs and captured time-lapse movies as the gonadal primordium formed. We identify three distinct phases of SGP behavior: posterior migration along the endoderm towards the PGCs, extension of a single long projection around the adjacent PGC, and a dramatic wrapping over the PGC surfaces. We show that the endoderm and PGCs are dispensable for SGP posterior migration and initiation of projections. However, both tissues are required for the final positioning of the SGPs and the morphology of their projections, and PGCs are absolutely required for SGP wrapping behaviors. Finally, we demonstrate that the basement membrane component laminin, which localizes adjacent to the developing gonadal primordium, is required to prevent the SGPs from over-extending past the PGCs. Our findings provide a foundation for understanding the cellular and molecular regulation of the establishment of a niche-stem cell relationship. PMID:23562590

  7. Liquid precursor for deposition of copper selenide and method of preparing the same

    DOEpatents

    Curtis, Calvin J.; Miedaner, Alexander; Franciscus Antonius Maria Van Hest, Marinus; Ginley, David S.; Hersh, Peter A.; Eldada, Louay; Stanbery, Billy J.

    2015-09-08

    Liquid precursors containing copper and selenium suitable for deposition on a substrate to form thin films suitable for semiconductor applications are disclosed. Methods of preparing such liquid precursors and methods of depositing a precursor on a substrate are also disclosed.

  8. Alteration of synaptic connectivity of oligodendrocyte precursor cells following demyelination

    PubMed Central

    Sahel, Aurélia; Ortiz, Fernando C.; Kerninon, Christophe; Maldonado, Paloma P.; Angulo, María Cecilia; Nait-Oumesmar, Brahim

    2015-01-01

    Oligodendrocyte precursor cells (OPCs) are a major source of remyelinating oligodendrocytes in demyelinating diseases such as Multiple Sclerosis (MS). While OPCs are innervated by unmyelinated axons in the normal brain, the fate of such synaptic contacts after demyelination is still unclear. By combining electrophysiology and immunostainings in different transgenic mice expressing fluorescent reporters, we studied the synaptic innervation of OPCs in the model of lysolecithin (LPC)-induced demyelination of corpus callosum. Synaptic innervation of reactivated OPCs in the lesion was revealed by the presence of AMPA receptor-mediated synaptic currents, VGluT1+ axon-OPC contacts in 3D confocal reconstructions and synaptic junctions observed by electron microscopy. Moreover, 3D confocal reconstructions of VGluT1 and NG2 immunolabeling showed the existence of glutamatergic axon-OPC contacts in post-mortem MS lesions. Interestingly, patch-clamp recordings in LPC-induced lesions demonstrated a drastic decrease in spontaneous synaptic activity of OPCs early after demyelination that was not caused by an impaired conduction of compound action potentials. A reduction in synaptic connectivity was confirmed by the lack of VGluT1+ axon-OPC contacts in virtually all rapidly proliferating OPCs stained with EdU (50-ethynyl-20-deoxyuridine). At the end of the massive proliferation phase in lesions, the proportion of innervated OPCs rapidly recovers, although the frequency of spontaneous synaptic currents did not reach control levels. In conclusion, our results demonstrate that newly-generated OPCs do not receive synaptic inputs during their active proliferation after demyelination, but gain synapses during the remyelination process. Hence, glutamatergic synaptic inputs may contribute to inhibit OPC proliferation and might have a physiopathological relevance in demyelinating disorders. PMID:25852473

  9. The human gastrin precursor. Characterization of phosphorylated forms and fragments.

    PubMed Central

    Varro, A; Desmond, H; Pauwels, S; Gregory, H; Young, J; Dockray, G J

    1988-01-01

    There is a potential phosphorylation site in the C-terminal region of the precursor for the acid-stimulating hormone gastrin, which is immediately adjacent to an important cleavage point. In the present study we have sought to identify, separate, quantify and characterize phosphorylated and unphosphorylated forms of human progastrin and its fragments. Identification was made by two radioimmunoassays: (a) a novel assay employing an antibody raised to intact human progastrin; and (b) an assay using antibody reacting with the C-terminal tryptic fragment of human progastrin, as well as progastrin itself. Two forms of human progastrin isolated from a gastrinoma were separated by ion-exchange h.p.l.c., and had similar elution positions on reverse-phase h.p.l.c. and on gel filtration. The more acidic peptide contained close to equimolar amounts of phosphate. On trypsinization, peptides were released that co-eluted on ion-exchange h.p.l.c. with, and had the immunochemical properties of, naturally occurring C-terminal fragments of progastrin. One of the latter was isolated and shown by Edman degradation after derivatization with ethanethiol to have the sequence Ser (P)-Ala-Glu-Asp-Glu-Asn. Similar peptides occur in antral mucosa resected from ulcer patients. The unphosphorylated forms of progastrin predominated, whereas the phosphorylated forms of the C-terminal fragments were predominant. This distribution could be explained by preferential cleavage of phosphorylated progastrin. We conclude that in human progastrin, Ser-96 can occur in the phosphorylated form; this residue immediately follows a pair of basic residues (Arg-Arg) that are cleaved during synthesis of the biologically active product. PMID:3223964

  10. MULTIPOLLUTANT METHODS - METHODS FOR OZONE AND OZONE PRECURSORS

    EPA Science Inventory

    This task involves the development and testing of methods for monitoring ozone and compounds associated with the atmospheric chemistry of ozone production both as precursors and reaction products. Although atmospheric gases are the primary interest, separation of gas and particl...

  11. Quarternary Amines as Nitrosamine Precursors: A Role for Consumer Products?

    Nitrosamine formation is associated with wastewater-impacted water supplies, but the specific precursors within municipal wastewater effluents have not been identified. Quaternary amines are significant constituents of consumer products, including shampoos, detergents and fabric softeners. Experimen...

  12. A high yield reverse micelle synthesis of catalysts and catalyst precursors

    SciT

    Linehan, J.C.; Matson, D.W.; Darab, J.G.

    1995-04-01

    Reverse micelles or water-in-oil microemulsions have been prepared using a mixed AOT/SDS surfactant to increase the stability of the microemulsion and thereby allow a high loading of particle-forming precursors in the aqueous cores. The Modified Reverse Micelles (MRM), as these new binary surfactant microemulsions are called, have proven useful for the laboratory-scale synthesis of nanoscale metals, metal oxides, metal sulfides, and mixed metal materials. The system allows control over the phase and size of the precipitated crystallites and is ideal for producing nanocrystalline powders and suspensions.

  13. Shape-programmed nanofabrication: understanding the reactivity of dichalcogenide precursors.

    PubMed

    Guo, Yijun; Alvarado, Samuel R; Barclay, Joshua D; Vela, Javier

    2013-04-23

    Dialkyl and diaryl dichalcogenides are highly versatile and modular precursors for the synthesis of colloidal chalcogenide nanocrystals. We have used a series of commercially available dichalcogenide precursors to unveil the molecular basis for the outcome of nanocrystal preparations, more specifically, how precursor molecular structure and reactivity affect the final shape and size of II-VI semiconductor nanocrystals. Dichalcogenide precursors used were diallyl, dibenzyl, di-tert-butyl, diisopropyl, diethyl, dimethyl, and diphenyl disulfides and diethyl, dimethyl, and diphenyl diselenides. We find that the presence of two distinctively reactive C-E and E-E bonds makes the chemistry of these precursors much richer and interesting than that of other conventional precursors such as the more common phosphine chalcogenides. Computational studies (DFT) reveal that the dissociation energy of carbon-chalcogen (C-E) bonds in dichalcogenide precursors (R-E-E-R, E=S or Se) increases in the order (R): diallylprecursor reactivity, leading to progressively slower nucleation and higher selectivity for anisotropic growth, all the way from dots to pods to tetrapods. Under identical experimental conditions, we obtain CdS and CdSe nanocrystals with spherical, elongated, or tetrapodal morphology by simply varying the identity and reactivity of the dichalcogenide precursor. Interestingly, we find that precursors with strong C-E and weak E-E bond dissociation energies such as Ph-S-S-Ph serve as a ready source of thiol radicals that appear to stabilize small CdE nuclei, facilitating anisotropic growth. These CdS and CdSe nanocrystals have been

  14. Synthesis and Characterization of the First Liquid Single Source Precursors for the Deposition of Ternary Chalcopyrite (CuInS2) Thin Film Materials

    NASA Technical Reports Server (NTRS)

    Banger, Kulbinder K.; Cowen, Jonathan; Hepp, Aloysius

    2002-01-01

    Molecular engineering of ternary single source precursors based on the [{PBu3}2Cu(SR')2In(SR')2] architecture have afforded the first liquid CIS ternary single source precursors (when R = Et, n-Pr), which are suitable for low temperature deposition (< 350 C). Thermogravimetric analyses (TGA) and modulated-differential scanning calorimetry (DSC) confirm their liquid phase and reduced stability. X-ray diffraction studies, energy dispersive analyzer (EDS), and scanning electron microscopy (SEM) support the formation of the single-phase chalcopyrite CuInS2 at low temperatures.

  15. Improved Single-Source Precursors for Solar-Cell Absorbers

    NASA Technical Reports Server (NTRS)

    Banger, Kulbinder K.; Harris, Jerry; Hepp, Aloysius

    2007-01-01

    Improved single-source precursor compounds have been invented for use in spray chemical vapor deposition (spray CVD) of chalcopyrite semiconductor absorber layers of thin-film cells. A "single-source precursor compound" is a single molecular compound that contains all the required elements, which when used under the spray CVD conditions, thermally decomposes to form CuIn(x)Ga(1-x)S(y)Se(2-y).

  16. SEARCH FOR PRECURSOR ERUPTIONS AMONG TYPE IIB SUPERNOVAE

    SciT

    Strotjohann, Nora L.; Ofek, Eran O.; Gal-Yam, Avishay

    2015-10-01

    The progenitor stars of several Type IIb supernovae (SNe) show indications of extended hydrogen envelopes. These envelopes might be the outcome of luminous energetic pre-explosion events, so-called precursor eruptions. We use the Palomar Transient Factory (PTF) pre-explosion observations of a sample of 27 nearby SNe IIb to look for such precursors during the final years prior to the SN explosion. No precursors are found when combining the observations in 15-day bins, and we calculate the absolute-magnitude-dependent upper limit on the precursor rate. At the 90% confidence level, SNe IIb have on average <0.86 precursors as bright as an absolute R-bandmore » magnitude of −14 in the final 3.5 years before the explosion and <0.56 events over the final year. In contrast, precursors among SNe IIn have a ≳5 times higher rate. The kinetic energy required to unbind a low-mass stellar envelope is comparable to the radiated energy of a few-weeks-long precursor that would be detectable for the closest SNe in our sample. Therefore, mass ejections, if they are common in such SNe, are radiatively inefficient or have durations longer than months. Indeed, when using 60-day bins, a faint precursor candidate is detected prior to SN 2012cs (∼2% false-alarm probability). We also report the detection of the progenitor of SN 2011dh that does not show detectable variability over the final two years before the explosion. The suggested progenitor of SN 2012P is still present, and hence is likely a compact star cluster or an unrelated object.« less

  17. Precursors for the polymer-assisted deposition of films

    DOEpatents

    McCleskey, Thomas M.; Burrell, Anthony K.; Jia, Quanxi; Lin, Yuan

    2013-09-10

    A polymer assisted deposition process for deposition of metal oxide films is presented. The process includes solutions of one or more metal precursor and soluble polymers having binding properties for the one or more metal precursor. After a coating operation, the resultant coating is heated at high temperatures to yield metal oxide films. Such films can be epitaxial in structure and can be of optical quality. The process can be organic solvent-free.

  18. Mexico's methamphetamine precursor chemical interventions: impacts on drug treatment admissions.

    PubMed

    Cunningham, James K; Bojorquez, Ietza; Campollo, Octavio; Liu, Lon-Mu; Maxwell, Jane Carlisle

    2010-11-01

    To help counter problems related to methamphetamine, Mexico has implemented interventions targeting pseudoephedrine and ephedrine, the precursor chemicals commonly used in the drug's synthesis. This study examines whether the interventions impacted methamphetamine treatment admissions-an indicator of methamphetamine consequences. Quasi-experiment: autoregressive integrated moving average (ARIMA)-based intervention time-series analysis. precursor chemical restrictions implemented beginning November 2005; major rogue precursor chemical company closed (including possibly the largest single drug-cash seizure in history) March 2007; precursor chemicals banned from Mexico (North America's first precursor ban) August 2008. Mexico and Texas (1996-2008). Monthly treatment admissions for methamphetamine (intervention series) and cocaine, heroin and alcohol (quasi-control series). The precursor restriction was associated with temporary methamphetamine admissions decreases of 12% in Mexico and 11% in Texas. The company closure was associated with decreases of 56% in Mexico and 48% in Texas; these decreases generally remained to the end of the study period. Neither intervention was associated with significant changes in the Mexico or Texas quasi-control series. The analysis of Mexico's ban was indeterminate due largely to a short post-ban series. This study, one of the first quasi-experimental analyses of an illicit-drug policy in Mexico, indicates that the country's precursor interventions were associated with positive impacts domestically and in one of the Unites States' most populous states--Texas. These interventions, coupled with previous US and Canadian interventions, amount to a new, relatively cohesive level of methamphetamine precursor control across North America's largest nations, raising the possibility that the impacts found here could continue for an extended period. © 2010 The Authors. Journal compilation © 2010 Society for the Study of Addiction.

  19. A New Ferroelectric Varactor from Water Based Inorganic Precursors

    DTIC Science & Technology

    2003-04-03

    See Equation 2). 0 0 4 OH +-)4T H13< Equation 2. Idealized Reaction of Titanium Isopropoxide with 2-ethylhexanoic acid. Inconsistent results with the...Equation 3). Equation 3. Reaction of 2-ethylhexanoic anhydride with Titanium Isopropoxide We have made over one hundred batches of both BST and SBTN MOD...aliphatic acids used in the more common MOD precursors. Equation 4 shows a comparison of the decomposition products of Titanium MOD precursors made from 2

  20. Elements of the tsunami precursors' detection physics

    NASA Astrophysics Data System (ADS)

    Novik, Oleg; Ruzhin, Yuri; Ershov, Sergey; Volgin, Max; Smirnov, Fedor

    ionosphere from the buoy, balloon and satellite complexes. The balloon and buoy complexes will transmit data to a shore station over satellite link. The frequency ranges and sensitivity thresholds of all of the sensors of the LOAMS will be adapted to the characteristics of expected seismic signals according to the numerical research above. Computational methods and statistical analysis (e.g. seismic changes of coherence of spatially distributed sensors of different nature) of the recorded multidimensional time series will be used for prognostic interpretation. The multilevel recordings will provide a stable noise (e.g. ionosphere Pc pulsations, hard sea, industry) and seismic event detection. An intensive heat flow typical for tectonically active lithosphere zones may be considered as an energy source for advanced modifications of the LOAMS. The latter may be used as a warning system for continental and marine technologies, e.g. a sea bottom geothermal energy production. Indeed, seismic distraction of the nuclear power station Fukushima I demonstrates that similar technology hardly is able to solve the energy problems in seismically active regions. On the other hand, the LOAMS may be considered as a scientific observatory for development of the seaquake/tsunami precursor physics, i.e. seismo-hydro-electromagnetics.

  1. Are neutrons precursors of solar flares?

    NASA Astrophysics Data System (ADS)

    Martirosyan, H.

    2001-08-01

    The analysis of data of a worldwide network of neutron monitors (NM) shows, that at local noon and during approximately 4 hours after, the NM sometimes register statistically significant excess. Enhancement of count rate is approxi-mately ≈ 1.5÷2%. Depending on the geographical coordinates the time slice is determined, during which the global increase of a registered ux (characteristic time of the order of tens of hours) is observed. These data are correlated with data from space-borne sensors, proving significant increase ( ≈ 5 ÷ 10 times) of the low energy protons and electrons in near-earth space. In both cases the ux enhancement during tenths of hours is proceeding by an impulse phase of the next solar are. The analysis of data allows to put forward a hypothesis that the enhancement of the protons and electrons ux is stipulated by decay of solar neutrons with energies 10 ÷ 30 MeV . These neutrons during tenths of hours before an impulse phase of a are are born in active areas of the Sun, as a product of thermonuclear reactions (D + d → He3 + n, T + d → He4 + n). The part of neutrons are decaying in the interplanetary space, and part of high en-ergy neutrons (En > 20 V ) penetrate through terrestrial atmosphere (with probability ≈ 10-7 and are registered by neutron monitors.

  2. Predicting Solar Cycle 24 Using a Geomagnetic Precursor Pair

    NASA Technical Reports Server (NTRS)

    Pesnell, W. Dean

    2014-01-01

    We describe using Ap and F(10.7) as a geomagnetic-precursor pair to predict the amplitude of Solar Cycle 24. The precursor is created by using F(10.7) to remove the direct solar-activity component of Ap. Four peaks are seen in the precursor function during the decline of Solar Cycle 23. A recurrence index that is generated by a local correlation of Ap is then used to determine which peak is the correct precursor. The earliest peak is the most prominent but coincides with high levels of non-recurrent solar activity associated with the intense solar activity of October and November 2003. The second and third peaks coincide with some recurrent activity on the Sun and show that a weak cycle precursor closely following a period of strong solar activity may be difficult to resolve. A fourth peak, which appears in early 2008 and has recurrent activity similar to precursors of earlier solar cycles, appears to be the "true" precursor peak for Solar Cycle 24 and predicts the smallest amplitude for Solar Cycle 24. To determine the timing of peak activity it is noted that the average time between the precursor peak and the following maximum is approximately equal to 6.4 years. Hence, Solar Cycle 24 would peak during 2014. Several effects contribute to the smaller prediction when compared with other geomagnetic-precursor predictions. During Solar Cycle 23 the correlation between sunspot number and F(10.7) shows that F(10.7) is higher than the equivalent sunspot number over most of the cycle, implying that the sunspot number underestimates the solar-activity component described by F(10.7). During 2003 the correlation between aa and Ap shows that aa is 10 % higher than the value predicted from Ap, leading to an overestimate of the aa precursor for that year. However, the most important difference is the lack of recurrent activity in the first three peaks and the presence of significant recurrent activity in the fourth. While the prediction is for an amplitude of Solar Cycle 24 of

  3. Precursor preparation for Ca-Al layered double hydroxide to remove hexavalent chromium coexisting with calcium and magnesium chlorides

    SciT

    Zhong, Lihua; He, Xiaoman; Qu, Jun

    Al(OH){sub 3} and Ca(OH){sub 2} powders are co-ground to prepare a precursor which hydrates into a layered double hydroxide (LDH) phase by agitation in aqueous solution with target hexavalent chromium (Cr(VI)) at room temperature, to achieve an obvious improvement in removal efficiency of Cr(VI) through an easy incorporation into the structure. Although the prepared precursor transforms into LDH phases also when agitated in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist. The adsorption isotherm and kinetic studies show that the phenomena occurring on the Al-Ca precursor fit a pseudo-second-order kineticsmore » with a Langmuir adsorption capacity of 59.45 mg/g. Besides, characterizations of the prepared precursor and the samples after adsorption are also performed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Transmission electron microscope (TEM) to understand the reason of the preferential incorporation of Cr(VI) to the coexisting chloride salts during the LDH phase formation. - Graphical abstract: Activated Ca-Al hydroxides (C{sub 3}A) transformed into Ca-Al-OH compound when agitated in water. Ca-Al precursor (C{sub 3}A) was agitated in a hexavalent chromium (Cr(VI)) solution to form Al-Ca-CrO{sub 4} LDH product. Ca-Al-CrO{sub 4} LDH phase occurred preferentially to Ca-Al-MCl{sub 2} LDH phases in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist. - Highlights: • Activated Ca-Al hydroxides transformed into LDH when agitated in water with some inorganic substances. • Hexavalent Cr was incorporated in the LDH structure at high adsorption capacity. • Ca-Al-Cr LDH phase occurred preferentially to Ca-Al-MCl{sub 2} LDH phases with coexistence. • The prepared Ca-Al hydroxides had high performance as adsorbent even with high salinity of the solution.« less

  4. Automated electrochemical assembly of the protected potential TMG-chitotriomycin precursor based on rational optimization of the carbohydrate building block.

    PubMed

    Nokami, Toshiki; Isoda, Yuta; Sasaki, Norihiko; Takaiso, Aki; Hayase, Shuichi; Itoh, Toshiyuki; Hayashi, Ryutaro; Shimizu, Akihiro; Yoshida, Jun-ichi

    2015-03-20

    The anomeric arylthio group and the hydroxyl-protecting groups of thioglycosides were optimized to construct carbohydrate building blocks for automated electrochemical solution-phase synthesis of oligoglucosamines having 1,4-β-glycosidic linkages. The optimization study included density functional theory calculations, measurements of the oxidation potentials, and the trial synthesis of the chitotriose trisaccharide. The automated synthesis of the protected potential N,N,N-trimethyl-d-glucosaminylchitotriomycin precursor was accomplished by using the optimized building block.

  5. THE ARECIBO L-BAND FEED ARRAY ZONE OF AVOIDANCE SURVEY. I. PRECURSOR OBSERVATIONS THROUGH THE INNER AND OUTER GALAXY

    SciT

    Henning, P. A.; McIntyre, T.; Day, F.

    The Arecibo L-band Feed Array (ALFA) is being used to conduct a low-Galactic latitude survey, to map the distribution of galaxies and large-scale structures behind the Milky Way through detection of galaxies' neutral hydrogen (H I) 21 cm emission. This Zone of Avoidance (ZOA) survey finds new H I galaxies which lie hidden behind the Milky Way, and also provides redshifts for partially obscured galaxies known at other wavelengths. Before the commencement of the full survey, two low-latitude precursor regions were observed, totaling 138 deg{sup 2}, with 72 H I galaxies detected. Detections through the inner Galaxy generally have nomore » cataloged counterparts in any other waveband, due to the heavy extinction and stellar confusion. Detections through the outer Galaxy are more likely to have Two Micron All Sky Survey counterparts. We present the results of these precursor observations, including a catalog of the detected galaxies, with their H I parameters. The survey sensitivity is well described by a flux- and linewidth-dependent signal-to-noise ratio of 6.5. ALFA ZOA galaxies, which also have H I measurements in the literature, show good agreement between our measurements and previous work. The inner Galaxy precursor region was chosen to overlap the H I Parkes Zone of Avoidance Survey, so ALFA performance could be quickly assessed. The outer Galaxy precursor region lies north of the Parkes sky. Low-latitude large-scale structure in this region is revealed, including an overdensity of galaxies near l = 183{sup 0} and between 5000-6000 km s{sup -1} in the ZOA. The full ALFA ZOA survey will be conducted in two phases: a shallow survey using the observing techniques of the precursor observations, and also a deep phase with much longer integration time, with thousands of galaxies predicted for the final catalog.« less

  6. Controlled synthesis of Co2C nanochains using cobalt laurate as precursor: Structure, growth mechanism and magnetic properties

    NASA Astrophysics Data System (ADS)

    Zhang, Yajing; Zhu, Yuan; Wang, Kangjun; Li, Da; Wang, Dongping; Ding, Fu; Meng, Dan; Wang, Xiaolei; Choi, Chuljin; Zhang, Zhidong

    2018-06-01

    Cobalt carbides (Co2C and Co3C) nanocomposites exhibit interesting hard magnetic property, controlled synthesis of individual phase facilitates to clarify the magnetism of each, but it is difficult to obtain the single phase. We present a new approach to address this issue via a polyol refluxing process, using cobalt laurate as the precursor. The single phase Co2C magnetic nanochains self-assembled by nanoparticles are synthesized. The precursor is the key factor for controlling the growth kinetics of the Co2C nanochains. Cobalt, instead of cobalt carbides, is produced if cobalt chloride, acetate and acetylacetonate replace cobalt laurate as the precursor, respectively. The evolution of the growth process has been studied. In the formation of Co2C, first fcc-Co produces, then it transforms into Co2C by carbon diffusion process, and the produced carbon first exists in disordered state and then a small amount of them transforms into graphite. Saturation magnetization (Ms) of Co2C nanochains obtained at 300 °C for 20, 60, and 180 min are 27.1, 18.9, and 10.9 emu g-1, respectively. The decrease of Ms caused by increasing carbon content, and the carbon content are much larger than the stoichiometric ratio value of Co2C (9.2 wt%). The Co2C nanochains have mesoporous pore of 3.8 nm and the specific surface area of 48.6 m2 g-1.

  7. Wet-chemical synthesis of different bismuth telluride nanoparticles using metal organic precursors - single source vs. dual source approach.

    PubMed

    Bendt, Georg; Weber, Anna; Heimann, Stefan; Assenmacher, Wilfried; Prymak, Oleg; Schulz, Stephan

    2015-08-28

    Thermolysis of the single source precursor (Et2Bi)2Te in DIPB at 80 °C yielded phase-pure Bi4Te3 nanoparticles, while mixtures of Bi4Te3 and elemental Bi were formed at higher temperatures. In contrast, cubic Bi2Te particles were obtained by thermal decomposition of Et2BiTeEt in DIPB. Moreover, a dual source approach (hot injection method) using the reaction of Te(SiEt3)2 and Bi(NMe2)3 was applied for the synthesis of different pure Bi-Te phases including Bi2Te, Bi4Te3 and Bi2Te3, which were characterized by PXRD, REM, TEM and EDX. The influence of reaction temperature, precursor molar ratio and thermolysis conditions on the resulting material phase was verified. Moreover, reactions of alternate bismuth precursors such as Bi(NEt2)3, Bi(NMeEt)3 and BiCl3 with Te(SiEt3)2 were investigated.

  8. Morphology and stability in a half-metallic ferromagnetic CrO 2 compound of nanoparticles synthesized via a polymer precursor

    NASA Astrophysics Data System (ADS)

    Biswas, S.; Ram, S.

    2004-11-01

    Nanoparticles of stable CrO2 of a half-metallic ferromagnet are synthesized with a novel chemical method involving a Cr4+-polymer composite precursor. A single phase CrO2 of D4h 14 : P42 / mnm tetragonal crystal structure (lattice parameters a = 0.4250 and c = 0.3190 nm) lies after firing the precursor at 350 °C for 1 h in air. Microstructure reveals single domain CrO2 particles of thin platelets (aspect ratio ∼1) of average 50 nm diameter and 35 nm thickness. In air, unless heating at temperatures above 500 °C, no due CrO2 → Cr2O3 phase transformation encounters. The results are presented in terms of X-ray diffraction and thermal or thermogravimetric analysis of precursor and derived CrO2 powder.

  9. Advanced transition metal phosphide materials from single-source molecular precursors

    NASA Astrophysics Data System (ADS)

    Colson, Adam Caleb

    In this thesis, the feasibility of employing organometallic single-source precursors in the preparation of advanced transition metal pnictide materials such as colloidal nanoparticles and films has been investigated. In particular, the ternary FeMnP phase was targeted as a model for preparing advanced heterobimetallic phosphide materials, and the iron-rich Fe3P phase was targeted due to its favorable ferromagnetic properties as well as the fact that the preparation of advanced Fe3P materials has been elusive by commonly used methods. Progress towards the synthesis of advanced Fe2--xMn xP nanomaterials and films was facilitated by the synthesis of the novel heterobimetallic complexes FeMn(CO)8(mu-PR1R 2) (R1 = H, R2 = H or R1 = H, R2 = Ph), which contain the relatively rare mu-PH2 and mu-PPhH functionalities. Iron rich Fe2--xMnxP nanoparticles were obtained by thermal decomposition of FeMn(CO)8(mu-PH 2) using solution-based synthetic methods, and empirical evidence suggested that oleic acid was responsible for manganese depletion. Films containing Fe, Mn, and P with the desired stoichiometric ratio of 1:1:1 were prepared using FeMn(CO)8(mu-PH2) in a simple low-pressure metal-organic chemical vapor deposition (MOCVD) apparatus. Although the elemental composition of the precursor was conserved in the deposited film material, spectroscopic evidence indicated that the films were not composed of pure-phase FeMnP, but were actually mixtures of crystalline FeMnP and amorphous FeP and Mn xOy. A new method for the preparation of phase-pure ferromagnetic Fe 3P films on quartz substrates has also been developed. This approach involved the thermal decomposition of the single-source precursors H 2Fe3(CO)9PR (R = tBu or Ph) at 400 °C. The films were deposited using a simple home-built MOCVD apparatus and were characterized using a variety of analytical methods. The films exhibited excellent phase purity, as evidenced by X-ray diffraction, X-ray photoelectron spectroscopy, and

  10. Subcellular Distribution of Glutathione Precursors in Arabidopsis thaliana

    PubMed Central

    Koffler, Barbara Eva; Maier, Romana; Zechmann, Bernd

    2011-01-01

    Abstract Glutathione is an important antioxidant and has many important functions in plant development, growth and defense. Glutathione synthesis and degradation is highly compartment-specific and relies on the subcellular availability of its precursors, cysteine, glutamate, glycine and γ-glutamylcysteine especially in plastids and the cytosol which are considered as the main centers for glutathione synthesis. The availability of glutathione precursors within these cell compartments is therefore of great importance for successful plant development and defense. The aim of this study was to investigate the compartment-specific importance of glutathione precursors in Arabidopsis thaliana. The subcellular distribution was compared between wild type plants (Col-0), plants with impaired glutathione synthesis (glutathione deficient pad2-1 mutant, wild type plants treated with buthionine sulfoximine), and one complemented line (OE3) with restored glutathione synthesis. Immunocytohistochemistry revealed that the inhibition of glutathione synthesis induced the accumulation of the glutathione precursors cysteine, glutamate and glycine in most cell compartments including plastids and the cytosol. A strong decrease could be observed in γ-glutamylcysteine (γ-EC) contents in these cell compartments. These experiments demonstrated that the inhibition of γ-glutamylcysteine synthetase (GSH1) – the first enzyme of glutathione synthesis – causes a reduction of γ-EC levels and an accumulation of all other glutathione precursors within the cells. PMID:22050910

  11. Gamma-Ray Burst Precursor Activity as Observed with BATSE

    NASA Technical Reports Server (NTRS)

    Koshut, Thomas M.; Kouveliotou, Chryssa; Paciesas, William S.; vanParadijs, Jan; Pendleton, Geoffrey N.; Briggs, Michael S.; Fishman, Gerald J.; Meegan, Charles A.

    1995-01-01

    Gamma-ray burst time histories often consist of multiple episodes of emission with the count rate dropping to the background level between adjacent episodes. We define precursor activity as any case in which the first episode (referred to as the precursor episode) has a lower peak intensity than that of the remaining emission (referred to as the main episode) and is separated from the remaining burst emission by a background interval that is at least as long as the remaining emission. We find that approx. 3% of the bursts observed with the Burst and Transient Source Experiment (BATSE) on Compton Gamma Ray Observatory (CGRO) satisfy this definition. We present the results of a study of the properties of these events. The spatial distribution of these sources is consistent with that of the larger set of all BATSE gamma-ray bursts: inhomogeneous and isotropic. A correlation between the duration of the precursor emission and the duration of the main episode emission is observed at about the 3 sigma confidence level. We find no meaningful significant correlations between or among any of the other characteristics of the precursor or main episode emission. It appears that the characteristics of the main episode emission are independent of the existence of the precursor emission.

  12. Experimental analysis of precursors to severe problem behavior.

    PubMed

    Fritz, Jennifer N; Iwata, Brian A; Hammond, Jennifer L; Bloom, Sarah E

    2013-01-01

    Some individuals engage in both mild and severe forms of problem behavior. Research has shown that when mild behaviors precede severe behaviors (i.e., the mild behaviors serve as precursors), they can (a) be maintained by the same source of reinforcement as severe behavior and (b) reduce rates of severe behavior observed during assessment. In Study 1, we developed an objective checklist to identify precursors via videotaped trials for 16 subjects who engaged in problem behavior and identified at least 1 precursor for every subject. In Study 2, we conducted separate functional analyses of precursor and severe problem behaviors for 8 subjects, and obtained correspondence between outcomes in 7 cases. In Study 3, we evaluated noncontingent reinforcement schedule thinning plus differential reinforcement of alternative behavior to reduce precursors, increase appropriate behavior, and maintain low rates of severe behavior during 3 treatment analyses for 2 subjects. Results showed that this treatment strategy was effective for behaviors maintained by positive and negative reinforcement. © Society for the Experimental Analysis of Behavior.

  13. Cryopreservation of GABAergic Neuronal Precursors for Cell-Based Therapy

    PubMed Central

    2017-01-01

    Cryopreservation protocols are essential for stem cells storage in order to apply them in the clinic. Here we describe a new standardized cryopreservation protocol for GABAergic neural precursors derived from the medial glanglionic eminence (MGE), a promising source of GABAergic neuronal progenitors for cell therapy against interneuron-related pathologies. We used 10% Me2SO as cryoprotectant and assessed the effects of cell culture amplification and cellular organization, as in toto explants, neurospheres, or individualized cells, on post-thaw cell viability and retrieval. We confirmed that in toto cryopreservation of MGE explants is an optimal preservation system to keep intact the interneuron precursor properties for cell transplantation, together with a high cell viability (>80%) and yield (>70%). Post-thaw proliferation and self-renewal of the cryopreserved precursors were tested in vitro. In addition, their migration capacity, acquisition of mature neuronal morphology, and potency to differentiate into multiple interneuron subtypes were also confirmed in vivo after transplantation. The results show that the cryopreserved precursor features remained intact and were similar to those immediately transplanted after their dissection from the MGE. We hope this protocol will facilitate the generation of biobanks to obtain a permanent and reliable source of GABAergic precursors for clinical application in cell-based therapies against interneuronopathies. PMID:28122047

  14. Isolation of pheromone precursor genes of Magnaporthe grisea.

    PubMed

    Shen, W C; Bobrowicz, P; Ebbole, D J

    1999-01-01

    In heterothallic ascomycetes one mating partner serves as the source of female tissue and is fertilized with spermatia from a partner of the opposite mating type. The role of pheromone signaling in mating is thought to involve recognition of cells of the opposite mating type. We have isolated two putative pheromone precursor genes of Magnaporthe grisea. The genes are present in both mating types of the fungus but they are expressed in a mating type-specific manner. The MF1-1 gene, expressed in Mat1-1 strains, is predicted to encode a 26-amino-acid polypeptide that is processed to produce a lipopeptide pheromone. The MF2-1 gene, expressed in Mat1-2 strains, is predicted to encode a precursor polypeptide that is processed by a Kex2-like protease to yield a pheromone with striking similarity to the predicted pheromone sequence of a close relative, Cryphonectria parasitica. Expression of the M. grisea putative pheromone precursor genes was observed under defined nutritional conditions and in field isolates. This suggests that the requirement for complex media for mating and the poor fertility of field isolates may not be due to limitation of pheromone precursor gene expression. Detection of putative pheromone precursor gene mRNA in conidia suggests that pheromones may be important for the fertility of conidia acting as spermatia. Copyright 1999 Academic Press.

  15. Thermal conversion of an iron nitride-silicon nitride precursor into a ferromagnetic nanocomposite

    NASA Astrophysics Data System (ADS)

    Maya, L.; Thompson, J. R.; Song, K. J.; Warmack, R. J.

    1998-01-01

    Iron nitride films, FeN, in a pure form and in the form of a nanocomposite in silicon nitride were prepared by reactive sputtering using iron or iron disilicide, respectively, as targets in a nitrogen plasma. Iron nitride decomposes into the elements by heating in vacuum to 800 °C. Intermediate phases such as Fe2N or Fe4N form at lower temperatures. The nanocomposites contain the iron phases as particles with an average size of ˜5 nm dispersed in the amorphous silicon nitride matrix. The magnetic properties of the nanocomposites were established. The precursor FeN-Si3N4 film is paramagnetic, while the Fe-Si3N4, obtained by heating in vacuum, is ferromagnetic and shows typical superparamagnetic behavior. These films are of interest as recording media with superior chemical and mechanical stability and may be encoded by localized heating.

  16. Role of precursor crystal structure on electrochemical performance of carbide-derived carbon electrodes

    NASA Astrophysics Data System (ADS)

    Palazzo, Benjamin; Norris, Zach; Taylor, Greg; Yu, Lei; Lofland, Samuel; Hettinger, Jeffrey

    2015-03-01

    Binary carbides with hexagonal and cubic crystal structures have been synthesized by reactive magnetron sputtering of vanadium and other transition metals in acetylene or methane gas mixed with argon. The binary carbides are converted to carbide-derived carbon (CDC) films using chlorine gas in a post-deposition process in an external vacuum reaction furnace. Residual chlorine has been removed using an annealing step in a hydrogen atmosphere. The CDC materials have been characterized by x-ray diffraction, x-ray fluorescence, and scanning electron microscopy. The performance of the CDC materials in electrochemical device applications has been measured with the hexagonal phase precursor demonstrating a significantly higher specific capacitance in comparison to that of the cubic phase. We report these results and pore-size distributions of these and similar materials.

  17. Development of molecular precursors for deposition of indium sulphide thin film electrodes for photoelectrochemical applications.

    PubMed

    Ehsan, Muhammad Ali; Peiris, T A Nirmal; Wijayantha, K G Upul; Olmstead, Marilyn M; Arifin, Zainudin; Mazhar, Muhammad; Lo, K M; McKee, Vickie

    2013-08-14

    Symmetrical and unsymmetrical dithiocarbamato pyridine solvated and non-solvated complexes of indium(III) with the general formula [In(S2CNRR')3]·n(py) [where py = pyridine; R,R' = Cy, n = 2 (1); R,R' = (i)Pr, n = 1.5 (2); NRR' = Pip, n = 0.5 (3) and R = Bz, R' = Me, n = 0 (4)] have been synthesized. The compositions, structures and properties of these complexes have been studied by means of microanalysis, IR and (1)H-NMR spectroscopy, X-ray single crystal and thermogravimetric (TG/DTG) analyses. The applicability of these complexes as single source precursors (SSPs) for the deposition of β-In2S3 thin films on fluorine-doped SnO2 (FTO) coated conducting glass substrates by aerosol-assisted chemical vapour deposition (AACVD) at temperatures of 300, 350 and 400 °C is studied. All films have been characterized by powder X-ray diffraction (PXRD) and energy dispersive X-ray analysis (EDX) for the detection of phase and stoichiometry of the deposit. Scanning electron microscopy (SEM) studies reveal that precursors (1)-(4), irrespective of different metal ligand design, generate comparable morphologies of β-In2S3 thin films at different temperatures. Direct band gap energies of 2.2 eV have been estimated from the UV-vis spectroscopy for the β-In2S3 films fabricated from precursors (1) and (4). The photoelectrochemical (PEC) properties of β-In2S3 were confirmed by recording the current-voltage plots under light and dark conditions. The plots showed anodic photocurrent densities of 1.25 and 0.65 mA cm(-2) at 0.23 V vs. Ag/AgCl for the β-In2S3 films made at 400 and 350 °C from the precursors (1) and (4), respectively. The photoelectrochemical performance indicates that the newly synthesised precursors are highly useful in fabricating β-In2S3 electrodes for solar energy harvesting and optoelectronic application.

  18. Chemical precursors to non-oxide ceramics: Macro to nanoscale materials

    NASA Astrophysics Data System (ADS)

    Forsthoefel, Kersten M.

    molecular precursor and porous alumina templating routes paired with solution-based methodologies are shown to generate non-oxide ceramic nanotubules of boron carbide, boron nitride and silicon carbide compositions. In the final phase of this work, a new metal-catalyzed route to poly(1-alkenyl- o-carborane) homopolymers and related copolymers was developed. Both homopolymers of 1-alkenyl-o-carboranes (1-vinyl-, 1-butenyl-, 1-hexenyl-) and copolymers of 1-hexenyl-o-carborane and allyltrimethylsilane or 1-hexenyl-o-carborane and 6-hexenyldecaborane were synthesized via the Cp2ZrMe2/B(C6F5) 3 catalyst system. A copolymer containing 1-hexenyl-o-carborane and the cross-linking agent, 6-hexenyldecaborane, was synthetically designed which exhibits initial cross-linking at ˜250°C and then converts in 75% yields to boron carbide at 1250°C.

  19. Thin film solar cells by selenization sulfurization using diethyl selenium as a selenium precursor

    DOEpatents

    Dhere, Neelkanth G.; Kadam, Ankur A.

    2009-12-15

    A method of forming a CIGSS absorber layer includes the steps of providing a metal precursor, and selenizing the metal precursor using diethyl selenium to form a selenized metal precursor layer (CIGSS absorber layer). A high efficiency solar cell includes a CIGSS absorber layer formed by a process including selenizing a metal precursor using diethyl selenium to form the CIGSS absorber layer.

  20. PARTITIONING TUNGSTEN BETWEEN MATRIX PRECURSORS AND CHONDRULE PRECURSORS THROUGH RELATIVE SETTLING

    SciT

    Hubbard, Alexander, E-mail: ahubbard@amnh.org

    2016-08-01

    Recent studies of chondrites have found a tungsten isotopic anomaly between chondrules and matrix. Given the refractory nature of tungsten, this implies that W was carried into the solar nebula by at least two distinct families of pre-solar grains. The observed chondrule/matrix split requires that the distinct families were kept separate during the dust coagulation process, and that the two families of grain interacted with the chondrule formation mechanism differently. We take the co-existence of different families of solids in the same general orbital region at the chondrule-precursor size as given, and explore the requirements for them to have interactedmore » with the chondrule formation process at significantly different rates. We show that this sorting of families of solids into chondrule- and matrix-destined dust had to have been at least as powerful a sorting mechanism as the relative settling of aerodynamically distinct grains at least two scale heights above the midplane. The requirement that the chondrule formation mechanism was correlated in some fashion with a dust-grain sorting mechanism argues strongly for spatially localized chondrule formation mechanisms such as turbulent dissipation in non-thermally ionized disk surface layers, and argues against volume-filling mechanisms such as planetesimal bow shocks.« less

  1. Partitioning Tungsten between Matrix Precursors and Chondrule Precursors through Relative Settling

    NASA Astrophysics Data System (ADS)

    Hubbard, Alexander

    2016-08-01

    Recent studies of chondrites have found a tungsten isotopic anomaly between chondrules and matrix. Given the refractory nature of tungsten, this implies that W was carried into the solar nebula by at least two distinct families of pre-solar grains. The observed chondrule/matrix split requires that the distinct families were kept separate during the dust coagulation process, and that the two families of grain interacted with the chondrule formation mechanism differently. We take the co-existence of different families of solids in the same general orbital region at the chondrule-precursor size as given, and explore the requirements for them to have interacted with the chondrule formation process at significantly different rates. We show that this sorting of families of solids into chondrule- and matrix-destined dust had to have been at least as powerful a sorting mechanism as the relative settling of aerodynamically distinct grains at least two scale heights above the midplane. The requirement that the chondrule formation mechanism was correlated in some fashion with a dust-grain sorting mechanism argues strongly for spatially localized chondrule formation mechanisms such as turbulent dissipation in non-thermally ionized disk surface layers, and argues against volume-filling mechanisms such as planetesimal bow shocks.

  2. The proteolytic processing site of the precursor of lysyl oxidase.

    PubMed Central

    Cronshaw, A D; Fothergill-Gilmore, L A; Hulmes, D J

    1995-01-01

    The precise cleavage site of the N-terminal propeptide region of the precursor of lysyl oxidase has not yet been established, due to N-terminal blocking of the mature protein. Using a combination of peptide fragmentation, amino acid sequencing, time-of-flight m.s. and partial chemical unblocking procedures, it is shown that the mature form of lysyl oxidase begins at residue Asp-169 of the precursor protein (numbered according to the human sequence). The cleavage site is 28 residues to the C-terminal side of the site previously suggested on the basis of apparant molecular mass by SDS/PAGE, with the consequence that the two putative, N-linked glycosylation sites and the position of the Arg/Gln sequence polymorphism are now all in the precursor region. PMID:7864821

  3. Obtaining aluminas from the thermal decomposition of their different precursors: An {sup 27}Al MAS NMR and X-ray powder diffraction studies

    SciT

    Chagas, L.H.; De Carvalho, G.S.G.; San Gil, R.A.S.

    2014-01-01

    Graphical abstract: - Highlights: • We synthesized three precursors of alumina from different methods. • The calcination of the precursors generated several alumina polymorphs. • XRD and NMR were used for structural investigation of the polymorphs. • The synthesis route determines the structural and textural properties of the solids. - Abstract: A commercial sample of Boehmite was used as precursor of alumina polymorphs. For comparison, three other precursors were synthesized from different methods. Particularly, the use of excess of urea promoted a very crystalline form of basic aluminum carbonate. The characteristics of the four precursors were investigated by thermal, vibrationalmore » and X-ray powder diffraction (XRD) analysis. Additionally, the nuclear magnetic resonance, with magic angle spinning ({sup 27}Al MAS NMR), was used to verify the coordination of aluminum cations. Each precursor was calcined at various temperatures generating alumina polymorphs, which were structurally analyzed by XRD and {sup 27}Al MAS NMR. Due to interest in catalysis supports, special attention was given to the γ-Al{sub 2}O{sub 3} phase, which in addition to structural investigation was subjected to textural analysis. The results showed that, from different synthesis procedures and common route of calcination, one can obtain materials with the same composition but with different structural and textural properties, which in turn can significantly influence the performance of a supported catalyst.« less

  4. Observation of a Hydrodynamically Driven, Radiative Precursor Shock

    NASA Astrophysics Data System (ADS)

    Keiter, P. A.; Drake, R. P.; Perry, T. S.; Robey, H.; Remington, B. A.; Iglesias, C. A.; Turner, N.; Stone, J.; Knauer, J.

    2001-10-01

    Many astrophysical systems, such as supernova remnants and jets, produce radiative-precursor shock waves. In a radiative-precursor shock, radiation from the shock ionizes and heats the medium ahead of it. The simulation of such systems requires that one treat both the emission and the absorption of the radiation. An important goal of this effort is to produce an experiment that can be modeled by astrophysical codes without implementing laser absorption physics into an astrophysical code. We report here the first measurements of a radiative-precursor shock in such an experiment. The experimental design is based on a past experiment[1,2] that used the Nova laser facility to simulate young supernova remnants. The target consists of a 60 νm CH plastic plug followed by a 150 νm vacuum gap and 2 mm of SiO2 aerogel foam. For the experiment, the density of the components and the laser-irradiation conditions are chosen so that the driven shock will produce an observable radiative precursor. We observed the radiative-precursor by using absorption spectroscopy. By backlighting the silicate aerogel foam with a thulium backlighter, we were able to observe both the 1s-2p and 1s-3p lines. These observations will allow us to determine the temperature profile in the precursor. 1. R.P. Drake, et al, Phys. Rev. Lett. 81, 2068 (1998). 2. R.P. Drake, et al., Phys. Plasmas, 7, 2142 (2000) Work supported by the U.S. Department of Energy both directly and through the Lawrence Livermore National Laboratory

  5. Fate of grape flavor precursors during storage on yeast lees.

    PubMed

    Loscos, Natalia; Hernández-Orte, Purificación; Cacho, Juan; Ferreira, Vicente

    2009-06-24

    The effect of the addition of a grape flavor precursor extract to a grape juice, before or after fermentation with three different Saccharomyces cerevisiae yeast strains, on the evolution of the wine aroma composition during a 9-month aging period on yeast lees has been studied. Wine aroma compounds were determined by gas chromatography-mass spectrometry after alcoholic fermentation and after 3 and 9 months of storage. The aging of wine on lees caused important changes in the aroma profiles of wines, making the concentrations of three terpenes, norisoprenoids (except beta-damascenone and beta-ionone), 4-allyl-2,6-dimethoxyphenol, ethyl vanillate, syringaldehyde, and ethyl cinnamate increase, whereas the concentrations of most of the rest of compounds tended to decrease. Lees are responsible for the observed increasing trends, except for linalool and alpha-terpineol, and also for a large part of the observed decrements. As expected, the addition of precursors brings about an increment in the levels of most terpenes, norisoprenoids, vanillins, and ethyl cinnamate, and it is after an aging time when differences linked to the level of precursors in the must become more evident. The timing of the addition of precursors has a minor influence, except for beta-damascenone, vanillin, and syringaldehyde, for which supplementation after fermentation is more effective. It has also been observed that the precursor fraction makes the levels of vinylphenols decrease. Finally, it has also been found that lees from different yeast strains may have a slightly different abilities to release volatile compounds derived from precursors.

  6. Isolation of Oct4-Expressing Extraembryonic Endoderm Precursor Cell Lines

    PubMed Central

    Debeb, Bisrat G.; Galat, Vasiliy; Epple-Farmer, Jessica; Iannaccone, Steve; Woodward, Wendy A.; Bader, Michael; Iannaccone, Philip; Binas, Bert

    2009-01-01

    Background The extraembryonic endoderm (ExEn) defines the yolk sac, a set of membranes that provide essential support for mammalian embryos. Recent findings suggest that the committed ExEn precursor is present already in the embryonic Inner Cell Mass (ICM) as a group of cells that intermingles with the closely related epiblast precursor. All ICM cells contain Oct4, a key transcription factor that is first expressed at the morula stage. In vitro, the epiblast precursor is most closely represented by the well-characterized embryonic stem (ES) cell lines that maintain the expression of Oct4, but analogous ExEn precursor cell lines are not known and it is unclear if they would express Oct4. Methodology/Principal Findings Here we report the isolation and characterization of permanently proliferating Oct4-expressing rat cell lines (“XEN-P cell lines”), which closely resemble the ExEn precursor. We isolated the XEN-P cell lines from blastocysts and characterized them by plating and gene expression assays as well as by injection into embryos. Like ES cells, the XEN-P cells express Oct4 and SSEA1 at high levels and their growth is stimulated by leukemia inhibitory factor, but instead of the epiblast determinant Nanog, they express the ExEn determinants Gata6 and Gata4. Further, they lack markers characteristic of the more differentiated primitive/visceral and parietal ExEn stages, but exclusively differentiate into these stages in vitro and contribute to them in vivo. Conclusions/Significance Our findings (i) suggest strongly that the ExEn precursor is a self-renewable entity, (ii) indicate that active Oct4 gene expression (transcription plus translation) is part of its molecular identity, and (iii) provide an in vitro model of early ExEn differentiation. PMID:19784378

  7. Innovative Strategies for Asteroid Precursor Exploration

    NASA Astrophysics Data System (ADS)

    Klaus, K.; Lawrence, S.; Elsperman, M. S.; Smith, D. B.

    2011-12-01

    initial mass gives a propellant loading of 200 kg. The solution for this case required 115.3 kg of propellant, leaving a 42% propellant margin. Science Instrumentation: Key objectives of this notional asteroid explorer would include: (1) high-resolution surface topography; (2) characterization surface composition and mineralogy; (3) quantification of the radiation environment near an NEO; and (4) mechanical properties of surface, if a touchdown takes place. Each nanosat would notionally contain a stereo camera for navigation, an alpha proton x-ray spectrometer to make measurements of the surface chemistry, and a microscopic imaging system to characterize the particle size distribution of asteroid regolith; multiple nanosats would provided redundancy for the in-situ surface characterization phase of the mission and enable a rudimentary gravity map through radio signal tracking.

  8. Learning from Cancer Precursors | Center for Cancer Research

    Cancer.gov

    Cancers that are preceded by distinct nonmalignant lesions provide an opportunity to study cancer progression and develop early detection and intervention strategies. Multiple myeloma—a cancer of the bone marrow that originates in a type of white blood cell called plasma cells—is consistently preceded by one of two nonmalignant precursor diseases: monoclonal gammopathy of undetermined significance (MGUS) or smoldering myeloma. Ola Landgren, M.D., Ph.D., and Adam Waxman, B.A., of the CCR Medical Oncology Branch recently published a case presentation and review in JAMA that discusses current understanding of myeloma precursor diseases and future opportunities for improving personalized management of patients with these conditions.

  9. Non-PGM cathode catalysts for fuel cell application derived from heat treated heteroatomic amines precursors

    DOEpatents

    Serov, Alexey; Halevi, Barr; Artyushkova, Kateryna; Atanassov, Plamen B; Martinez, Ulises A

    2017-04-25

    A method of preparing M-N--C catalysts utilizing a sacrificial support approach and inexpensive and readily available polymer precursors as the source of nitrogen and carbon is disclosed. Exemplary polymer precursors include non-porphyrin precursors with no initial catalytic activity. Examples of suitable non-catalytic non-porphyrin precursors include, but are not necessarily limited to low molecular weight precursors that form complexes with iron such as 4-aminoantipirine, phenylenediamine, hydroxysuccinimide, ethanolamine, and the like.

  10. Phase transitions in colloidal fluids: Kinetically or thermodynamically controlled?

    NASA Astrophysics Data System (ADS)

    Duran-Olivencia, Miguel A.; Yatsyshin, Peter; Lutsko, James F.; Kalliadasis, Serafim

    2017-11-01

    In recent years, a flurry of experimental observations suggests that most phase transitions occur in a multistage manner and via intermediate phases. These precursors to the final phase are commonly understood as the local minima of the free energy of the system. Inherently, the classical paradigm of nucleation has no capacity to describe neither the origin nor the role played by these precursors in the nucleation pathway. Here we present a systematic theoretical framework capable of describing the precursor phases in a self-consistent way. We demonstrate that nucleation precursors can appear even in situations involving a single free-energy barrier. This contradicts previous phenomenological approaches, which always characterise intermediate phases as the minima of a complex free-energy landscape. We show that a kinetically-induced mechanism temporarily stabilises an intermediate phase, which thus is not the result of a local minimum of the free energy but a consequence of the entropic cost of cluster formation. Moreover, the appearance of precursors does not seem to influence the overall nucleation time, which is governed by the free-energy barrier. The mechanism uncovered in this study can be used to explain recently reported experimental findings in crystallisation. European Research Council - Advanced Grant No. 247031; Engineering and Physical Sciences Research Council - Grant Nos. EP/L020564 and EP/L025159.

  11. Terminal Transient Phase of Chaotic Transients

    NASA Astrophysics Data System (ADS)

    Lilienkamp, Thomas; Parlitz, Ulrich

    2018-03-01

    Transient chaos in spatially extended systems can be characterized by the length of the transient phase, which typically grows quickly with the system size (supertransients). For a large class of these systems, the chaotic phase terminates abruptly, without any obvious precursors in commonly used observables. Here we investigate transient spatiotemporal chaos in two different models of this class. By probing the state space using perturbed trajectories we show the existence of a "terminal transient phase," which occurs prior to the abrupt collapse of chaotic dynamics. During this phase the impact of perturbations is significantly different from the earlier transient and particular patterns of (non)susceptible regions in state space occur close to the chaotic trajectories. We therefore hypothesize that even without perturbations proper precursors for the collapse of chaotic transients exist, which might be highly relevant for coping with spatiotemporal chaos in cardiac arrhythmias or brain functionality, for example.

  12. Process for producing ceramic nitrides anc carbonitrides and their precursors

    DOEpatents

    Brown, G.M.; Maya, L.

    1987-02-25

    A process for preparing ceramic nitrides and carbon nitrides in the form of very pure, fine particulate powder. Appropriate precursors is prepared by reaching a transition metal alkylamide with ammonia to produce a mixture of metal amide and metal imide in the form of an easily pyrolyzable precipitate.

  13. Glutamine: precursor or nitrogen donor for citrulline synthesis?

    Glutamine (Gln) is considered the main precursor for citrulline (Cit) synthesis, but no attempts have been made to differentiate the contribution of Gln carbon (Gln-C) skeleton vs. the nonspecific contribution through NH3 and CO2. To study the contribution of dietary Gln-N to the synthesis of Cit, t...

  14. Glutamine: Precursor or nitrogen donor for citrulline synthesis?

    Although glutamine is considered the main precursor for citrulline synthesis, the current literature does not differentiate between the contribution of glutamine carbon skeleton, versus nonspecific nitrogen (i.e., ammonia) and carbon derived from glutamine oxidation. To elucidate the role of glutami...

  15. Precursors for ornithine and citrulline synthesis in neonatal pigs

    Citrulline (CIT) is an amino acid synthesized by gut and utilized for the synthesis of the conditionally essential amino acid arginine (ARG). In turn, the immediate precursor for CIT synthesis, ornithine (ORN), can originate from proline (PRO) and glutamine (GLN) via ornithine aminotransferase (OAT,...

  16. TRIHALOMETHANE PRECURSOR REMOVAL BY THE MAGNESIUM CARBONATE PROCESS

    EPA Science Inventory

    A project was conducted to determine and improve the ability of the magnesium carbonate process to remove trihalomethane (THM) precursors in treated drinking water. The project was conducted at a drinking water treatment plant in Melbourne, FL, which had been developed and instal...

  17. RIVERBANK FILTRATION: FATE OF DBP PRECURSORS AND SELECTED MICROORGANISMS

    EPA Science Inventory

    The fate of disinfection by-product (DBP) precursors and selected microorganisms during riverbank filtration (RBF) was monitored at three different mid-Western drinking water utilities. At all three sites, filtration (RBF) was monitored at three different mid-Western drinking wa...

  18. College Student Stress: A Predictor of Eating Disorder Precursor Behaviors

    ERIC Educational Resources Information Center

    Shelton, Virginia L.; Valkyrie, Karena T.

    2010-01-01

    Eating disorders are compulsive behaviors that can consume a person's life to the point of becoming life threatening. Previous research found stress associated with eating disorders. College can be a stressful time. If stress predicted precursor behaviors to eating disorders, then counselors would have a better chance to help students sooner. This…

  19. Process for producing ceramic nitrides and carbonitrides and their precursors

    DOEpatents

    Brown, Gilbert M.; Maya, Leon

    1988-01-01

    A process for preparing ceramic nitrides and carbonitrides in the form of very pure, fine particulate powder. Appropriate precursor is prepared by reacting a transition metal alkylamide with ammonia to produce a mixture of metal amide and metal imide in the form of an easily pyrolyzable precipitate.

  20. Pure erythroid leukemia following precursor B-cell lymphoblastic leukemia.

    PubMed

    Xu, Min; Finn, Laura S; Tsuchiya, Karen D; Thomson, Blythe; Pollard, Jessica; Rutledge, Joe

    2012-01-01

    Therapy-related acute myeloid leukemia is an unfortunate sequel to current multimodal intensive chemotherapy. The patient described was diagnosed with pure erythroleukemia, AML-M6b, during therapy for precursor B-cell acute lymphoblastic leukemia. To the best of our knowledge, this is the first report of this unusual association.

  1. Methionine as a Precursor of Ethylene—Commentary

    Lieberman et al. showed in a 1966 publication of Plant Physiology that methionine is a precursor of ethylene. It was the first paper that showed ethylene carbons are derived from carbons 3 and 4 of methionine. This paper catalyzed remarkable interest among plant biologists to elucidate the biosynth...

  2. Technical Note: Methionine, a precursor of methane in living plants

    NASA Astrophysics Data System (ADS)

    Lenhart, K.; Althoff, F.; Greule, M.; Keppler, F.

    2015-03-01

    When terrestrial plants were identified as producers of the greenhouse gas methane, much discussion and debate ensued not only about their contribution to the global methane budget but also with regard to the validity of the observation itself. Although the phenomenon has now become more accepted for both living and dead plants, the mechanism of methane formation in living plants remains to be elucidated and its precursor compounds to be identified. We made use of stable isotope techniques to verify the in vivo formation of methane, and, in order to identify the carbon precursor, 13C positionally labeled organic compounds were employed. Here we show that the amino acid L-methionine acts as a methane precursor in living plants. Employing 13C-labeled methionine clearly identified the sulfur-bound methyl group of methionine as a carbon precursor of methane released from lavender (Lavandula angustifolia). Furthermore, when lavender plants were stressed physically, methane release rates and the stable carbon isotope values of the emitted methane greatly increased. Our results provide additional support that plants possess a mechanism for methane production and suggest that methionine might play an important role in the formation of methane in living plants, particularly under stress conditions.

  3. Technical note: Methionine, a precursor of methane in living plants

    NASA Astrophysics Data System (ADS)

    Lenhart, K.; Althoff, F.; Greule, M.; Keppler, F.

    2014-11-01

    When terrestrial plants were identified as producers of the greenhouse gas methane, much discussion and debate ensued, not only about their contribution to the global methane budget, but also with regard to the validity of the observation itself. Although the phenomenon has now become more accepted for both living and dead plants, the mechanism of methane formation in living plants remains to be elucidated and its precursor compounds identified. We made use of stable isotope techniques to verify in vivo formation of methane and, in order to identify the carbon precursor, 13C-positionally labelled organic compounds were employed. Here we show that the amino acid L-methionine acts as a methane precursor in living plants. Employing 13C-labelled methionine clearly identified the sulphur-bound methyl group of methionine as a carbon precursor of methane released from lavender (Lavandula angustifolia). Furthermore, when lavender plants were stressed physically, methane release rates and the stable carbon isotope values of the emitted methane greatly increased. Our results provide additional support that plants possess a mechanism for methane production and suggest that methionine might play an important role in the formation of methane in living plants, particularly under stress conditions.

  4. Manganite perovskite ceramics, their precursors and methods for forming

    DOEpatents

    Payne, David Alan; Clothier, Brent Allen

    2015-03-10

    Disclosed are a variety of ceramics having the formula Ln.sub.1-xM.sub.xMnO.sub.3, where 0.Itoreq.x.Itoreq.1 and where Ln is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or Y; M is Ca, Sr, Ba, Cd, or Pb; manganite precursors for preparing the ceramics; a method for preparing the precursors; and a method for transforming the precursors into uniform, defect-free ceramics having magnetoresistance properties. The manganite precursors contain a sol and are derived from the metal alkoxides: Ln(OR).sub.3, M(OR).sub.2 and Mn(OR).sub.2, where R is C.sub.2 to C.sub.6 alkyl or C.sub.3 to C.sub.9 alkoxyalkyl, or C.sub.6 to C.sub.9 aryl. The preferred ceramics are films prepared by a spin coating method and are particularly suited for incorporation into a device such as an integrated circuit device.

  5. Inflammatory arthritis increases mouse osteoclast precursors with myeloid suppressor function

    PubMed Central

    Charles, Julia F.; Hsu, Lih-Yun; Niemi, Erene C.; Weiss, Arthur; Aliprantis, Antonios O.; Nakamura, Mary C.

    2012-01-01

    Increased osteoclastic bone resorption leads to periarticular erosions and systemic osteoporosis in RA patients. Although a great deal is known about how osteoclasts differentiate from precursors and resorb bone, the identity of an osteoclast precursor (OCP) population in vivo and its regulatory role in RA remains elusive. Here, we report the identification of a CD11b–/loLy6Chi BM population with OCP activity in vitro and in vivo. These cells, which can be distinguished from previously characterized precursors in the myeloid lineage, display features of both M1 and M2 monocytes and expand in inflammatory arthritis models. Surprisingly, in one mouse model of RA (adoptive transfer of SKG arthritis), cotransfer of OCP with SKG CD4+ T cells diminished inflammatory arthritis. Similar to monocytic myeloid-derived suppressor cells (M-MDSCs), OCPs suppressed CD4+ and CD8+ T cell proliferation in vitro through the production of NO. This study identifies a BM myeloid precursor population with osteoclastic and T cell–suppressive activity that is expanded in inflammatory arthritis. Therapeutic strategies that prevent the development of OCPs into mature bone-resorbing cells could simultaneously prevent bone resorption and generate an antiinflammatory milieu in the RA joint. PMID:23114597

  6. Development of precursors recognition methods in vector signals

    NASA Astrophysics Data System (ADS)

    Kapralov, V. G.; Elagin, V. V.; Kaveeva, E. G.; Stankevich, L. A.; Dremin, M. M.; Krylov, S. V.; Borovov, A. E.; Harfush, H. A.; Sedov, K. S.

    2017-10-01

    Precursor recognition methods in vector signals of plasma diagnostics are presented. Their requirements and possible options for their development are considered. In particular, the variants of using symbolic regression for building a plasma disruption prediction system are discussed. The initial data preparation using correlation analysis and symbolic regression is discussed. Special attention is paid to the possibility of using algorithms in real time.

  7. NASA's Accident Precursor Analysis Process and the International Space Station

    NASA Technical Reports Server (NTRS)

    Groen, Frank; Lutomski, Michael

    2010-01-01

    This viewgraph presentation reviews the implementation of Accident Precursor Analysis (APA), as well as the evaluation of In-Flight Investigations (IFI) and Problem Reporting and Corrective Action (PRACA) data for the identification of unrecognized accident potentials on the International Space Station.

  8. Developmental Dyslexia: Early Precursors, Neurobehavioral Markers, and Biological Substrates

    ERIC Educational Resources Information Center

    Benasich, April A., Ed.; Fitch, R. Holly, Ed.

    2012-01-01

    Understanding the precursors and early indicators of dyslexia is key to early identification and effective intervention. Now there's a single research volume that brings together the very latest knowledge on the earliest stages of dyslexia and the diverse genetic, neurobiological, and cognitive factors that may contribute to it. Based on findings…

  9. Environment Conscious, Biomorphic Ceramics from Pine and Jelutong Wood Precursors

    NASA Technical Reports Server (NTRS)

    Singh, Mrityunjay; Yee, Bo-Moon; Gray, Hugh R. (Technical Monitor)

    2002-01-01

    Environment conscious, biomorphic ceramics have been fabricated from pine and jelutong wood precursors. A carbonaceous preform is produced through wood pyrolysis and subsequent infiltration with oxides (ZrO2 sols) and liquid silicon to form ceramics. These biomorphic ceramics show a wide variety of microstructures, densities, and hardness behavior that are determined by the type of wood and infiltrants selected.

  10. Deposition on disordered substrates with precursor layer diffusion

    NASA Astrophysics Data System (ADS)

    Filipe, J. A. N.; Rodgers, G. J.; Tavassoli, Z.

    1998-09-01

    Recently we introduced a one-dimensional accelerated random sequential adsorption process as a model for chemisorption with precursor layer diffusion. In this paper we consider this deposition process on disordered or impure substrates. The problem is solved exactly on both the lattice and continuum and for various impurity distributions. The results are compared with those from the standard random sequential adsorption model.

  11. [Endometrial carcinomas and precursor lesions--new aspects].

    PubMed

    Schmidt, D

    2009-07-01

    Endometrial carcinomas can be separated into two groups which are designated as type I and type II carcinomas today. Both groups of tumors are clearly different with regard to conventional light microscopy, immunohistochemistry, molecular pathology and clinical features. Only type I carcinomas are associated with hyperestrogenism. The group of type I carcinomas consists of endometrioid carcinoma and its variants, and mucinous carcinoma. The prototypes of type II carcinomas are serous and clear cell carcinoma. Not all carcinomas, however, can be assigned to one of the two groups, because there are hybrid tumors and mixed carcinomas, e.g. endometrioid carcinoma with a serous component. The precursor lesions of the endometrioid carcinoma and the serous carcinoma are well characterized morphologically and by molecular pathology. Atypical hyperplasia is the precursor lesion of endometrioid carcinoma, whereas endometrial intraepithelial carcinoma (EIC) is the precursor lesion of serous carcinoma. No precursor lesion has as yet been identified for clear cell carcinoma. Immunohistochemical markers for endometrial carcinoma are CK7 and vimentin, for serous carcinoma markers are p53 and p16. Correct typing is of essential prognostic necessity in endometrial carcinoma. Of utmost importance is the detection of a serous component, because serous carcinoma leads to early tumor spread with the necessity of radical surgery, chemotherapy and radiotherapy.

  12. Learning from Cancer Precursors | Center for Cancer Research

    Cancer.gov

    Cancers that are preceded by distinct nonmalignant lesions provide an opportunity to study cancer progression and develop early detection and intervention strategies. Multiple myeloma—a cancer of the bone marrow that originates in a type of white blood cell called plasma cells—is consistently preceded by one of two nonmalignant precursor diseases: monoclonal gammopathy of

  13. Characterization of electrochemically deposited films from aqueous and ionic liquid cobalt precursors toward hydrogen evolution reactions

    NASA Astrophysics Data System (ADS)

    Dushatinski, Thomas; Huff, Clay; Abdel-Fattah, Tarek M.

    2016-11-01

    Electrodepositions of cobalt films were achieved using an aqueous or an ethylene glycol based non-aqueous solution containing choline chloride (vitamin B4) with cobalt chloride hexahydrate precursor toward hydrogen evolution reactions from sodium borohydride (NaBH4) as solid hydrogen feedstock (SHF). The resulting cobalt films had reflectivity at 550 nm of 2.2% for aqueously deposited films (ACoF) and 1.3% for non-aqueously deposited films (NCoF). Surface morphology studied by scanning electron microscopy showed a positive correlation between particle size and thickness. The film thicknesses were tunable between >100 μm and <300 μm for each film. The roughness (Ra) value measurements by Dektak surface profiling showed that the NCoF (Ra = 165 nm) was smoother than the ACoF (Ra = 418 nm). The NCoFs and ACoFs contained only α phase (FCC) crystallites. The NCoFs were crystalline while the ACoFs were largely amorphous from X-ray diffraction analysis. The NCoF had an average Vickers hardness value of 84 MPa as compared to 176 MPa for ACoF. The aqueous precursor has a single absorption maximum at 510 nm and the non-aqueous precursor had three absorption maxima at 630, 670, and 695 nm. The hydrogen evolution reactions over a 1 cm2 catalytic surface with aqueous NaBH4 solutions generated rate constants (K) = equal to 4.9 × 10-3 min-1, 4.6 × 10-3 min-1, and 3.3 × 10-3 min-1 for ACoF, NCoF, and copper substrate respectively.

  14. Properties of NiO thin films deposited by chemical spray pyrolysis using different precursor solutions

    NASA Astrophysics Data System (ADS)

    Cattin, L.; Reguig, B. A.; Khelil, A.; Morsli, M.; Benchouk, K.; Bernède, J. C.

    2008-07-01

    NiO thin films have been deposited by chemical spray pyrolysis using a perfume atomizer to grow the aerosol. The influence of the precursor, nickel chloride hexahydrate (NiCl 2·6H 2O), nickel nitrate hexahydrate (Ni(NO 3) 2·6H 2O), nickel hydroxide hexahydrate (Ni(OH) 2·6H 2O), nickel sulfate tetrahydrate (NiSO 4·4H 2O), on the thin films properties has been studied. In the experimental conditions used (substrate temperature 350 °C, precursor concentration 0.2-0.3 M, etc.), pure NiO thin films crystallized in the cubic phase can be achieved only with NiCl 2 and Ni(NO 3) 2 precursors. These films have been post-annealed at 425 °C for 3 h either in room atmosphere or under vacuum. If all the films are p-type, it is shown that the NiO films conductivity and optical transmittance depend on annealing process. The properties of the NiO thin films annealed under room atmosphere are not significantly modified, which is attributed to the fact that the temperature and the environment of this annealing is not very different from the experimental conditions during spray deposition. The annealing under vacuum is more efficient. This annealing being proceeded in a vacuum no better than 10 -2 Pa, it is supposed that the modifications of the NiO thin film properties, mainly the conductivity and optical transmission, are related to some interaction between residual oxygen and the films.

  15. Synthesis and characterization of silver nanoparticles from (bis)alkylamine silver carboxylate precursors

    NASA Astrophysics Data System (ADS)

    Uznanski, Pawel; Zakrzewska, Joanna; Favier, Frederic; Kazmierski, Slawomir; Bryszewska, Ewa

    2017-03-01

    A comparative study of amine and silver carboxylate adducts [R1COOAg-2(R2NH2)] (R1 = 1, 7, 11; R2 = 8, 12) as a key intermediate in NPs synthesis is carried out via differential scanning calorimetry, solid-state FT-infrared spectroscopy, 13C CP MAS NMR, powder X-ray diffraction and X-ray photoelectron spectroscopy, and various solution NMR spectroscopies (1H and 13C NMR, pulsed field gradient spin-echo NMR, and ROESY). It is proposed that carboxyl moieties in the presence of amine ligands are bound to silver ions via chelating bidentate type of coordination as opposed to bridging bidentate coordination of pure silver carboxylates resulting from the formation of dimeric units. All complexes are packed as lamellar bilayer structures. Silver carboxylate/amine complexes show one first-order melting transition. The evidence presented in this study shows that phase behavior of monovalent metal carboxylates are controlled, mainly, by head group bonding. In solution, insoluble silver salt is stabilized by amine molecules which exist in dynamic equilibrium. Using (bis)amine-silver carboxylate complex as precursor, silver nanoparticles were fabricated. During high-temperature thermolysis, the (bis)amine-carboxylate adduct decomposes to produce silver nanoparticles of small size. NPs are stabilized by strongly interacting carboxylate and trace amounts of amine derived from the silver precursor interacting with carboxylic acid. A corresponding aliphatic amide obtained from silver precursor at high-temperature reaction conditions is not taking part in the stabilization. Combining NMR techniques with FTIR, it was possible to follow an original stabilization mechanism.

  16. Atmospheric new particle formation at the research station Melpitz, Germany: connection with gaseous precursors and meteorological parameters

    NASA Astrophysics Data System (ADS)

    Größ, Johannes; Hamed, Amar; Sonntag, André; Spindler, Gerald; Elina Manninen, Hanna; Nieminen, Tuomo; Kulmala, Markku; Hõrrak, Urmas; Plass-Dülmer, Christian; Wiedensohler, Alfred; Birmili, Wolfram

    2018-02-01

    This paper revisits the atmospheric new particle formation (NPF) process in the polluted Central European troposphere, focusing on the connection with gas-phase precursors and meteorological parameters. Observations were made at the research station Melpitz (former East Germany) between 2008 and 2011 involving a neutral cluster and air ion spectrometer (NAIS). Particle formation events were classified by a new automated method based on the convolution integral of particle number concentration in the diameter interval 2-20 nm. To study the relevance of gaseous sulfuric acid as a precursor for nucleation, a proxy was derived on the basis of direct measurements during a 1-month campaign in May 2008. As a major result, the number concentration of freshly produced particles correlated significantly with the concentration of sulfur dioxide as the main precursor of sulfuric acid. The condensation sink, a factor potentially inhibiting NPF events, played a subordinate role only. The same held for experimentally determined ammonia concentrations. The analysis of meteorological parameters confirmed the absolute need for solar radiation to induce NPF events and demonstrated the presence of significant turbulence during those events. Due to its tight correlation with solar radiation, however, an independent effect of turbulence for NPF could not be established. Based on the diurnal evolution of aerosol, gas-phase, and meteorological parameters near the ground, we further conclude that the particle formation process is likely to start in elevated parts of the boundary layer rather than near ground level.

  17. Cryptic color change in a crab spider (Misumena vatia): identification and quantification of precursors and ommochrome pigments by HPLC.

    PubMed

    Riou, Mickaël; Christidès, Jean-Philippe

    2010-04-01

    Mimicry is used widely by arthropods to survive in a hostile environment. Often mimicry is associated with the production of chemical compounds such as pigments. In crab spiders, the change of color is based on a complex physiological process that still is not understood. The aim of this study was to identify and quantify the ommochrome pigments and precursors responsible for the color change in the mimetic crab spider Misumena vatia (Thomisidae). A modified high performance reverse phase ion-pair chromatography technique enabled us to separate and quantify the ommochrome pigments, their precursors, and related metabolites in individual spiders. Compounds such as tryptophan, kynurenine, and kynurenic acid occurred only or mainly in white crab spiders. In contrast, compounds such as 3-hydroxy-kynurenine, xanthommatin, and ommatin D occurred only or mainly in yellow crab spiders. Factor analysis ranked the different color forms in accordance with their metabolites. The biochemical results enabled us to associate the different phases of formation of pigment granules with specific metabolites. Yellow crab spiders contain many unknown ommochrome-like compounds not present in white crab spiders. We also found large quantities of decarboxylated xanthommatin, whose role as precursor of new pathways in ommochrome synthesis needs to be assessed. The catabolism of ommochromes, a process occurring when spiders revert from yellow to white, warrants further study.

  18. Micro-structural evolution and biomineralization behavior of carbon nanofiber/bioactive glass composites induced by precursor aging time.

    PubMed

    Jia, Xiaolong; Tang, Tianhong; Cheng, Dan; Zhang, Cuihua; Zhang, Ran; Cai, Qing; Yang, Xiaoping

    2015-12-01

    Bioactive glass (BG)-containing carbon nanofibers (CNFs) are promising orthopaedic biomaterials. Herein, CNF composites were produced from electrospinning of polyacrylonitrile (PAN)/BG sol-gel precursor solution, followed by carbonization. Choosing 58S-type BG (mol%: 58.0% SiO2-26.3% CaO-15.7% P2O5) as the model, micro-structural evolution of CNF/BG composites was systematically evaluated in relating to aging times of BG precursor solution. With aging time prolonging, BG precursors underwent morphological changes from small sol clusters with loosely and randomly branched structure to highly crosslinked Si-network structure, showing continuous increase in solution viscosity. BG precursor solution with low viscosity could mix well with PAN solution, resulting in CNF composite with homogeneously distributed BG component. Whereas, BG precursor gel with densely crosslinked Si-network structure led to uneven distribution of BG component along final CNFs due to its significant phase separation from PAN component. Meanwhile, BG nanoparticles in CNFs demonstrated micro-structural evolution that they transited from weak to strong crystal state along with longer aging time. Biomineralization in simulated body fluid and in vitro osteoblasts proliferation were then applied to determine the bioactivity of CNF/BG composites. CNF/BG composites prepared from shorter aging time could induce both faster apatite deposition and cell proliferation rate. It was suggested weakly crystallized BG nanoparticles along CNFs dissolved fast and was able to provide numerous nucleation sites for apatite deposition, which also favored the proliferation of osteoblasts cells. Aging time could thus be a useful tool to regulate the biological features of CNF/BG composites. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Precursor directed synthesis--"molecular" mechanisms in the Soft Chemistry approaches and their use for template-free synthesis of metal, metal oxide and metal chalcogenide nanoparticles and nanostructures.

    PubMed

    Seisenbaeva, Gulaim A; Kessler, Vadim G

    2014-06-21

    This review provides an insight into the common reaction mechanisms in Soft Chemistry processes involved in nucleation, growth and aggregation of metal, metal oxide and chalcogenide nanoparticles starting from metal-organic precursors such as metal alkoxides, beta-diketonates, carboxylates and their chalcogene analogues and demonstrates how mastering the precursor chemistry permits us to control the chemical and phase composition, crystallinity, morphology, porosity and surface characteristics of produced nanomaterials.

  20. Precursor routes to quaternary intermetallics: Synthesis, crystal structure, and physical properties of clathrate-II Cs8Na16Al24Si112

    NASA Astrophysics Data System (ADS)

    Wei, Kaya; Dong, Yongkwan; Nolas, George S.

    2016-05-01

    A new quaternary clathrate-II composition, Cs8Na16Al24Si112, was synthesized by kinetically controlled thermal decomposition (KCTD) employing both NaSi and NaAlSi as the precursors and CsCl as a reactive flux. The crystal structure and composition of Cs8Na16Al24Si112 were investigated using both Rietveld refinement and elemental analysis, and the temperature dependent transport properties were investigated. Our results indicate that KCTD with multiple precursors is an effective method for the synthesis of multinary inorganic phases that are not easily accessible by traditional solid-state synthesis or crystal growth techniques.

  1. Early T-cell precursor acute lymphoblastic leukaemia in children treated in AIEOP centres with AIEOP-BFM protocols: a retrospective analysis.

    PubMed

    Conter, Valentino; Valsecchi, Maria Grazia; Buldini, Barbara; Parasole, Rosanna; Locatelli, Franco; Colombini, Antonella; Rizzari, Carmelo; Putti, Maria Caterina; Barisone, Elena; Lo Nigro, Luca; Santoro, Nicola; Ziino, Ottavio; Pession, Andrea; Testi, Anna Maria; Micalizzi, Concetta; Casale, Fiorina; Pierani, Paolo; Cesaro, Simone; Cellini, Monica; Silvestri, Daniela; Cazzaniga, Giovanni; Biondi, Andrea; Basso, Giuseppe

    2016-02-01

    Early T-cell precursor acute lymphoblastic leukaemia was recently recognised as a distinct leukaemia and reported as associated with poor outcomes. We aimed to assess the outcome of early T-cell precursor acute lymphoblastic leukaemia in patients from the Italian Association of Pediatric Hematology Oncology (AIEOP) centres treated with AIEOP-Berlin-Frankfurt-Münster (AIEOP-BFM) protocols. In this retrospective analysis, we included all children aged from 1 to less than 18 years with early T-cell precursor acute lymphoblastic leukaemia immunophenotype diagnosed between Jan 1, 2008, and Oct 31, 2014, from AIEOP centres. Early T-cell precursors were defined as being CD1a and CD8 negative, CD5 weak positive or negative, and positive for at least one of the following antigens: CD34, CD117, HLADR, CD13, CD33, CD11b, or CD65. Treatment was based on AIEOP-BFM acute lymphoblastic leukaemia 2000 (NCT00613457) or AIEOP-BFM acute lymphoblastic leukaemia 2009 protocols (European Clinical Trials Database 2007-004270-43). The main differences in treatment and stratification of T-cell acute lymphoblastic leukaemia between the two protocols were that in the 2009 protocol only, pegylated L-asparaginase was substituted for Escherichia coli L-asparaginase, patients with prednisone poor response received an additional dose of cyclophosphamide at day 10 of phase IA, and high minimal residual disease at day 15 assessed by flow cytometry was used as a high-risk criterion. Outcomes were assessed in terms of event-free survival, disease-free survival, and overall survival. Early T-cell precursor acute lymphoblastic leukaemia was diagnosed in 49 patients. Compared with overall T-cell acute lymphoblastic leukaemia, it was associated with absence of molecular markers for PCR detection of minimal residual disease in 25 (56%) of 45 patients; prednisone poor response in 27 (55%) of 49 patients; high minimal residual disease at day 15 after starting therapy in 25 (64%) of 39 patients (bone marrow

  2. Behaviour of mantle transition zone discontinuities beneath the Indian Ocean from PP and SS precursors

    NASA Astrophysics Data System (ADS)

    Reiss, Anne-Sophie; Thomas, Christine

    2015-04-01

    As part of the RHUM-RUM project we investigate the upwelling plume beneath the island La Réunion, located in the Indian Ocean 200 km east of Madagascar. This plume belongs to one of the most active hotspot regions in the world and is still active today. Understanding the depth origin and dimensions of such a plume helps to better understand mantle processes and the heat flux of the Earth. If the plume originates at the core-mantle boundary the Earth is cooled down differently compared with an indirect cooling of plumes originating in the upper mantle. Here we use underside reflections of PP and SS waves off the seismic discontinuities at 410 km and 660 km depth that arrive as precursors to the main phase in order to investigate the topography of these discontinuities that mark the top and bottom of the mantle transition zone. If hotter or colder material intersects the mantle transition zone, the discontinuities at 410 km and 660 km depth are deflected, hence the topography of the mantle transition zone can be an indicator for an upwelling plume. The 410 km discontinuity, which exists due to the phase change of olivine to spinel, should be depressed significantly in the presence of hot upwelling material. Because of the opposite Clapeyron slope of the phase change of spinel to magnesiowuestite and perovskite at 660 km depth, the topography of this discontinuity should be elevated. For this study we analyse over 200 events with Mw ≥ 5.8 and bounce points distributed over the entire Indian Ocean. Array seismology methods, such as vespagrams and slowness-backazimuth analysis, are used to enhance the signal-to-noise-ratio and detect and identify precursors. Using different source-receiver combinations enables us to get a dense coverage of bounce points of PP and SS waves in the Indian Ocean and especially around La Réunion, also with crossing ray paths. The differential travel times of PP and SS arrivals and their precursors of robust stacks are converted into

  3. Upper Mantle Discontinuity Structure Beneath the Western Atlantic Ocean and Eastern North America from SS Precursors

    NASA Astrophysics Data System (ADS)

    Schmerr, N. C.; Beghein, C.; Kostic, D.; Baldridge, A. M.; West, J. D.; Nittler, L. R.; Bull, A. L.; Montesi, L.; Byrne, P. K.; Hummer, D. R.; Plescia, J. B.; Elkins-Tanton, L. T.; Lekic, V.; Schmidt, B. E.; Elkins, L. J.; Cooper, C. M.; ten Kate, I. L.; Van Hinsbergen, D. J. J.; Parai, R.; Glass, J. B.; Ni, J.; Fuji, N.; McCubbin, F. M.; Michalski, J. R.; Zhao, C.; Arevalo, R. D., Jr.; Koelemeijer, P.; Courtier, A. M.; Dalton, H.; Waszek, L.; Bahamonde, J.; Schmerr, B.; Gilpin, N.; Rosenshein, E.; Mach, K.; Ostrach, L. R.; Caracas, R.; Craddock, R. A.; Moore-Driskell, M. M.; Du Frane, W. L.; Kellogg, L. H.

    2015-12-01

    Seismic discontinuities within the mantle arise from a wide range of mechanisms, including changes in mineralogy, major element composition, melt content, volatile abundance, anisotropy, or a combination of the above. In particular, the depth and sharpness of upper mantle discontinuities at 410 and 660 km depth are attributed to solid-state phase changes sensitive to both mantle temperature and composition, where regions of thermal heterogeneity produce topography and chemical heterogeneity changes the impedance contrast across the discontinuity. Seismic mapping of this topography and sharpness thus provides constraint on the thermal and compositional state of the mantle. The EarthScope USArray is providing unprecedented access to a wide variety of new regions previously undersampled by the SS precursors. This includes the boundary between the oceanic plate in the western Atlantic Ocean and continental margin of eastern North America. Here we use a seismic array approach to image the depth, sharpness, and topography of the upper mantle discontinuities, as well as other possible upper mantle reflectors beneath this region. This array approach utilizes seismic waves that reflect off the underside of a mantle discontinuity and arrive several hundred seconds prior to the SS seismic phase as precursory energy. In this study, we collected high-quality broadband data SS precursors data from shallow focus (< 30 km deep), mid-Atlantic ridge earthquakes recorded by USArray seismometers in Alaska. We generated 4th root vespagrams to enhance the SS precursors and determine how they sample the mantle. Our data show detection of localized structure on the discontinuity boundaries as well as additional horizons, such as the X-discontinuity and a potential reflection from a discontinuity near the depth of the lithosphere-asthenosphere boundary. These structures are related to the transition from predominantly old ocean lithosphere to underlying continental lithosphere, as while

  4. Analysis and identification of astaxanthin and its carotenoid precursors from Xanthophyllomyces dendrorhous by high-performance liquid chromatography.

    PubMed

    Lu, Mingbo; Zhang, Yang'e; Zhao, Chunfang; Zhou, Pengpeng; Yu, Longjiang

    2010-01-01

    This study presents an HPLC method for simultaneous analysis of astaxanthin and its carotenoid precursors from Xanthophyllomyces dendrorhous. The HPLC method is accomplished by employing a C18 column and the mobile phase methanol/water/acetonitrile/ dichloromethane (70:4:13:13, v/v/v/v). Astaxanthin is quantified by detection at 480 nm. The carotenoid precursors are identified by LC-APCI-MS and UV-vis absorption spectra. Peaks showed in the HPLC chromatogram are identified as carotenoids in the monocyclic biosynthetic pathway or their derivatives. In the monocyclic carotenoid pathway, 3,3'-dihydroxy-beta,psi-carotene-4,4'-dione (DCD) is produced through gamma-carotene and torulene.

  5. Effect of Group-III precursors on unintentional gallium incorporation during epitaxial growth of InAlN layers by metalorganic chemical vapor deposition

    SciT

    Kim, Jeomoh, E-mail: jkim610@gatech.edu; Ji, Mi-Hee; Detchprohm, Theeradetch

    2015-09-28

    Unintentional incorporation of gallium (Ga) in InAlN layers grown with different molar flow rates of Group-III precursors by metalorganic chemical vapor deposition has been experimentally investigated. The Ga mole fraction in the InAl(Ga)N layer was increased significantly with the trimethylindium (TMIn) flow rate, while the trimethylaluminum flow rate controls the Al mole fraction. The evaporation of metallic Ga from the liquid phase eutectic system between the pyrolized In from injected TMIn and pre-deposited metallic Ga was responsible for the Ga auto-incorporation into the InAl(Ga)N layer. The theoretical calculation on the equilibrium vapor pressure of liquid phase Ga and the effectivemore » partial pressure of Group-III precursors based on growth parameters used in this study confirms the influence of Group-III precursors on Ga auto-incorporation. More Ga atoms can be evaporated from the liquid phase Ga on the surrounding surfaces in the growth chamber and then significant Ga auto-incorporation can occur due to the high equilibrium vapor pressure of Ga comparable to effective partial pressure of input Group-III precursors during the growth of InAl(Ga)N layer.« less

  6. Effect of Group-III precursors on unintentional gallium incorporation during epitaxial growth of InAlN layers by metalorganic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Kim, Jeomoh; Ji, Mi-Hee; Detchprohm, Theeradetch; Dupuis, Russell D.; Fischer, Alec M.; Ponce, Fernando A.; Ryou, Jae-Hyun

    2015-09-01

    Unintentional incorporation of gallium (Ga) in InAlN layers grown with different molar flow rates of Group-III precursors by metalorganic chemical vapor deposition has been experimentally investigated. The Ga mole fraction in the InAl(Ga)N layer was increased significantly with the trimethylindium (TMIn) flow rate, while the trimethylaluminum flow rate controls the Al mole fraction. The evaporation of metallic Ga from the liquid phase eutectic system between the pyrolized In from injected TMIn and pre-deposited metallic Ga was responsible for the Ga auto-incorporation into the InAl(Ga)N layer. The theoretical calculation on the equilibrium vapor pressure of liquid phase Ga and the effective partial pressure of Group-III precursors based on growth parameters used in this study confirms the influence of Group-III precursors on Ga auto-incorporation. More Ga atoms can be evaporated from the liquid phase Ga on the surrounding surfaces in the growth chamber and then significant Ga auto-incorporation can occur due to the high equilibrium vapor pressure of Ga comparable to effective partial pressure of input Group-III precursors during the growth of InAl(Ga)N layer.

  7. Synthesis, Optical and Structural Properties of Copper Sulfide Nanocrystals from Single Molecule Precursors

    PubMed Central

    Ajibade, Peter A.; Botha, Nandipha L.

    2017-01-01

    We report the synthesis and structural studies of copper sulfide nanocrystals from copper (II) dithiocarbamate single molecule precursors. The precursors were thermolysed in hexadecylamine (HDA) to prepare HDA-capped CuS nanocrystals. The optical properties of the nanocrystals studied using UV–visible and photoluminescence spectroscopy showed absorption band edges at 287 nm that are blue shifted, and the photoluminescence spectra show emission curves that are red-shifted with respect to the absorption band edges. These shifts are as a result of the small crystallite sizes of the nanoparticles leading to quantum size effects. The structural studies were carried out using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and atomic force microscopy. The XRD patterns indicates that the CuS nanocrystals are in hexagonal covellite crystalline phases with estimated particles sizes of 17.3–18.6 nm. The TEM images showed particles with almost spherical or rod shapes, with average crystallite sizes of 3–9.8 nm. SEM images showed morphology with ball-like microspheres on the surfaces, and EDS spectra confirmed the presence of CuS nanoparticles. PMID:28336865

  8. Local Structure and Anisotropy in the Amorphous Precursor= to Ba-Hexaferrite Thin Films

    NASA Astrophysics Data System (ADS)

    Snyder, J. E.; Harris, V. G.; Koon, N. C.; Sui, X.; Kryder, M. H.

    1996-03-01

    Ba-hexaferrite thin-films for recording media applications are commonly fabricated by a two-step process: sputter-deposition of an amorphous precursor, followed by annealing to crystallize the BaFe_12O_19 phase. The magnetic anisotropy of the crystalline films can be either in-plane or perpendicular, depending on the sputtering process used in the first step. However, conventional characterization techniques (x-ray diffraction and TEM) have been unable to observe any structure in the amorphous precursor films. In this study, such films are investigated by PD-EXAFS (polarization-dependent extended x-ray absorption fine structure). An anisotropic local ordered structure is observed around both Fe and Ba atoms in the "amorphous" films. This anisotropic local structure appears to determine the orientation of the fast-growing basal plane directions during crystallization, and thus the directions of the c-axes and the magnetic anisotropy. Results suggest that the structure of the amorphous films consists of networks made up of units of Fe atoms surrounded by their O nearest neighbors, that are connected together. Ba atoms appear to fit into in-between spaces as network-modifiers.

  9. A Real-Time Earthquake Precursor Detection Technique Using TEC from a GPS Network

    NASA Astrophysics Data System (ADS)

    Alp Akyol, Ali; Arikan, Feza; Arikan, Orhan

    2016-07-01

    Anomalies have been observed in the ionospheric electron density distribution prior to strong earthquakes. However, most of the reported results are obtained by earthquake analysis. Therefore, their implementation in practice is highly problematic. Recently, a novel earthquake precursor detection technique based on spatio-temporal analysis of Total Electron Content (TEC) data obtained from Turkish National Permanent GPS Network (TNPGN) is developed by IONOLAB group (www.ionolab.org). In the present study, the developed detection technique is implemented in a causal setup over the available data set in test phase that enables the real time implementation. The performance of the developed earthquake prediction technique is evaluated by using 10 fold cross validation over the data obtained in 2011. Among the 23 earthquakes that have magnitudes higher than 5, the developed technique can detect precursors of 14 earthquakes while producing 8 false alarms. This study is supported by TUBITAK 115E915 and Joint TUBITAK 114E092 and AS CR 14/001 projects.

  10. The Engineering Development Array: A Low Frequency Radio Telescope Utilising SKA Precursor Technology

    NASA Astrophysics Data System (ADS)

    Wayth, Randall; Sokolowski, Marcin; Booler, Tom; Crosse, Brian; Emrich, David; Grootjans, Robert; Hall, Peter J.; Horsley, Luke; Juswardy, Budi; Kenney, David; Steele, Kim; Sutinjo, Adrian; Tingay, Steven J.; Ung, Daniel; Walker, Mia; Williams, Andrew; Beardsley, A.; Franzen, T. M. O.; Johnston-Hollitt, M.; Kaplan, D. L.; Morales, M. F.; Pallot, D.; Trott, C. M.; Wu, C.

    2017-08-01

    We describe the design and performance of the Engineering Development Array, which is a low-frequency radio telescope comprising 256 dual-polarisation dipole antennas working as a phased array. The Engineering Development Array was conceived of, developed, and deployed in just 18 months via re-use of Square Kilometre Array precursor technology and expertise, specifically from the Murchison Widefield Array radio telescope. Using drift scans and a model for the sky brightness temperature at low frequencies, we have derived the Engineering Development Array's receiver temperature as a function of frequency. The Engineering Development Array is shown to be sky-noise limited over most of the frequency range measured between 60 and 240 MHz. By using the Engineering Development Array in interferometric mode with the Murchison Widefield Array, we used calibrated visibilities to measure the absolute sensitivity of the array. The measured array sensitivity matches very well with a model based on the array layout and measured receiver temperature. The results demonstrate the practicality and feasibility of using Murchison Widefield Array-style precursor technology for Square Kilometre Array-scale stations. The modular architecture of the Engineering Development Array allows upgrades to the array to be rolled out in a staged approach. Future improvements to the Engineering Development Array include replacing the second stage beamformer with a fully digital system, and to transition to using RF-over-fibre for the signal output from first stage beamformers.

  11. Multi-Step Crystallization of Barium Carbonate: Rapid Interconversion of Amorphous and Crystalline Precursors.

    PubMed

    Whittaker, Michael L; Smeets, Paul J M; Asayesh-Ardakani, Hasti; Shahbazian-Yassar, Reza; Joester, Derk

    2017-12-11

    The direct observation of amorphous barium carbonate (ABC), which transforms into a previously unknown barium carbonate hydrate (herewith named gortatowskite) within a few hundred milliseconds of formation, is described. In situ X-ray scattering, cryo-, and low-dose electron microscopy were used to capture the transformation of nanoparticulate ABC into gortatowskite crystals, highly anisotropic sheets that are up to 1 μm in width, yet only about 10 nm in thickness. Recrystallization of gortatowskite to witherite starts within 30 seconds. We describe a bulk synthesis and report a first assessment of the composition, vibrational spectra, and structure of gortatowskite. Our findings indicate that transient amorphous and crystalline precursors can play a role in aqueous precipitation pathways that may often be overlooked owing to their extremely short lifetimes and small dimensions. However, such transient precursors may be integral to the formation of more stable phases. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Peroxyl radical reactions with carotenoids in microemulsions: Influence of microemulsion composition and the nature of peroxyl radical precursor.

    PubMed

    El-Agamey, Ali; McGarvey, David J

    2016-01-01

    The reactions of acetylperoxyl radicals with different carotenoids (7,7'-dihydro-β-carotene and ζ-carotene) in SDS and CTAC microemulsions of different compositions were investigated using laser flash photolysis (LFP) coupled with kinetic absorption spectroscopy. The primary objective of this study was to explore the influence of microemulsion composition and the type of surfactant used on the yields and kinetics of various transients formed from the reaction of acetylperoxyl radicals with carotenoids. Also, the influence of the site (hydrocarbon phases or aqueous phase) of generation of the peroxyl radical precursor was examined by using 4-acetyl-4-phenylpiperidine hydrochloride (APPHCl) and 1,1-diphenylacetone (11DPA) as water-soluble and lipid-soluble peroxyl radical precursors, respectively. LFP of peroxyl radical precursors with 7,7'-dihydro-β-carotene (77DH) in different microemulsions gives rise to the formation of three distinct transients namely addition radical (λmax=460 nm), near infrared transient1 (NIR, λmax=700 nm) and 7,7'-dihydro-β-carotene radical cation (77DH(•+), λmax=770 nm). In addition, for ζ-carotene (ZETA) two transients (near infrared transient1 (NIR1, λmax=660 nm) and ζ-carotene radical cation (ZETA(•+), λmax=730-740 nm)) are generated following LFP of peroxyl radical precursors in the presence of ζ-carotene (ZETA) in different microemulsions. The results show that the composition of the microemulsion strongly influences the observed yield and kinetics of the transients formed from the reactions of peroxyl radicals (acetylperoxyl radicals) with carotenoids (77DH and ZETA). Also, the type of surfactant used in the microemulsions influences the yield of the transients formed. The dependence of the transient yields and kinetics on microemulsion composition (or the type of surfactant used in the microemulsion) can be attributed to the change of the polarity of the microenvironment of the carotenoid. Furthermore, the nature of

  13. Fabrication and Characterization of CZTS Thin Films Prepared by the Sulfurization of RF-Sputtered Stacked Metal Precursors

    NASA Astrophysics Data System (ADS)

    Abusnina, Mohamed; Moutinho, Helio; Al-Jassim, Mowafak; DeHart, Clay; Matin, Mohammed

    2014-09-01

    In this work, Cu2ZnSnS4 (CZTS) thin films were prepared by the sulfurization of metal precursors deposited sequentially via radio frequency magnetron sputtering on Mo-coated soda-lime glass. The stack order of the precursors was Mo/Zn/Sn/Cu. Sputtered precursors were annealed in sulfur atmosphere with nine different conditions to study the impact of sulfurization time and substrate temperature on the structural, morphological, and optical properties of the final CZTS films. X-ray fluorescence was used to determine the elemental composition ratio of the metal precursors. Final CZTS films were characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS). XRD and EDS were combined to investigate the films' structure and to identify the presence of secondary phases. XRD analysis indicated an improvement in film crystallinity with an increase of the substrate temperature and annealing times. Also indicated was the minimization and/or elimination of secondary phases when the films experienced longer annealing time. EDS revealed slight Sn loss in films sulfurized at 550°C; however, an increase of the sulfurization temperature to 600°C did not confirm these results. SEM study showed that films treated with higher temperatures exhibited dense morphology, indicating the completion of the sulfurization process. The estimated absorption coefficient was on the order of 104 cm-1 for all CZTS films, and the values obtained for the optical bandgap energy of the films were between 1.33 eV and 1.52 eV.

  14. The escaping "pneuma" - gas of ancient earthquake concepts in relation to animal, atmospheric and thermal precursors

    NASA Astrophysics Data System (ADS)

    Helmut, Tributsch

    2013-04-01

    anomalies matches that of reported unusual animal behaviour. It may indeed be caused by the same geophysical phenomenon, a pressure-change induced liberation of "pneuma" -gas. The latter may simply be understood as the consequence of pressure dependent changes of the chemical equilibrium constants within the condensed phases of the underground. They will be proportional to the reaction molar volume of interfacial and bulk geochemical mechanisms and may lead to the desorption and emission of chemical species, which finally reach the earth surface. The nature of reported animal behaviour is supporting such conclusion. Straightforward experimental strategies will be required for characterization of the escaping gas in terms of chemical and nano- and micro- particle composition. Non-linear irreversible thermodynamic models may be invoked for understanding energy turnover during the geophysical precursor activity.

  15. Whole-cell fungal transformation of precursors into dyes

    PubMed Central

    2010-01-01

    Background Chemical methods of producing dyes involve extreme temperatures and unsafe toxic compounds. Application of oxidizing enzymes obtained from fungal species, for example laccase, is an alternative to chemical synthesis of dyes. Laccase can be replaced by fungal biomass acting as a whole-cell biocatalyst with properties comparable to the isolated form of the enzyme. The application of the whole-cell system simplifies the transformation process and reduces the time required for its completion. In the present work, four fungal strains with a well-known ability to produce laccase were tested for oxidation of 17 phenolic and non-phenolic precursors into stable and non-toxic dyes. Results An agar-plate screening test of the organic precursors was carried out using four fungal strains: Trametes versicolor, Fomes fomentarius, Abortiporus biennis, and Cerrena unicolor. Out of 17 precursors, nine were transformed into coloured substances in the presence of actively growing fungal mycelium. The immobilized fungal biomass catalyzed the transformation of 1 mM benzene and naphthalene derivatives in liquid cultures yielding stable and non-toxic products with good dyeing properties. The type of fungal strain had a large influence on the absorbance of the coloured products obtained after 48-hour transformation of the selected precursors, and the most effective was Fomes fomentarius (FF25). Whole-cell transformation of AHBS (3-amino-4-hydroxybenzenesulfonic acid) into a phenoxazinone dye was carried out in four different systems: in aqueous media comprising low amounts of carbon and nitrogen source, in buffer, and in distilled water. Conclusions This study demonstrated the ability of four fungal strains belonging to the ecological type of white rot fungi to transform precursors into dyes. This paper highlights the potential of fungal biomass for replacing isolated enzymes as a cheaper industrial-grade biocatalyst for the synthesis of dyes and other commercially important

  16. Making Single-Source Precursors of Ternary Semiconductors

    NASA Technical Reports Server (NTRS)

    Hepp, Aloysius; Banger, Kulbindre K.

    2007-01-01

    A synthesis route has been developed for the commercial manufacture of single- source precursors of chalcopyrite semiconductor absorber layers of thin-film solar photovoltaic cells. A closely related class of single-source precursors of these semiconductors, and their synthesis routes, were reported in "Improved Single-Source Precursors for Solar-Cell Absorbers" (LEW-17445-1), NASA Tech Briefs, Vol. 31, No. 6 (June 2007), page 56. The present synthesis route is better suited to commercialization because it is simpler and involves the use of commercially available agents, yet offers the flexibility needed for synthesis of a variety of precursors. A single-source precursor of the type of interest here is denoted by the general formula L2M'(mu-ER)2M(ER)2, where L signifies a Lewis base; M signifies Al, In, or Ga; M' signifies Ag or Cu; R signifies an alkyl, aryl, silyl, or perfluorocarbon group; E signifies O, S, Se, or Te; and mu signifies a bridging ligand. This compound can be synthesized in a "one-pot" procedure from ingredients that are readily available from almost any chemical supplier. In a demonstration, the following synthesis was performed: Under anaerobic conditions, InCl3 was reacted with sodium ethanethiolate in methanol in a 1:4 molar ratio to afford the ionic stable intermediate compound Na+[In(SEt)4]- (where Et signifies ethyl group). After approximately 15 minutes, a heterogeneous solution of CuCl and the Lewis base PPh3 (where Ph signifies phenyl) in a 1:2 ratio in a mixture of CH3CN and CH2Cl2 was added directly to the freshly prepared Na+[In(SEt)4]-. After 24 hours, the reaction was essentially complete. The methanolic solution was concentrated, then the product was extracted with CH2Cl2, then the product was washed with dry ether and pentane. The product in its final form was a creamy white solid. Spectroscopic and elemental analysis confirmed that the product was (PPh3)2Cu(mu-SEt)2In(mu-SEt)2, which is known to be a precursor of the ternary

  17. Thermal Studies of New Precursors to Indium-tin Oxides for Use as Sensor Materials in the Detection of NO(x)

    NASA Technical Reports Server (NTRS)

    Goldsby, J. C.; Kacik, T.; Hockensmith, C. M.

    1999-01-01

    Control of combustion product emissions in both sub and super-sonic jet engines can be facilitated by measurement of NO(x) levels with metal oxide sensors, In2O3, metal-doped SnO2, and SnO, (as well as other materials) show resistivity changes in the presence of NO(x), but often their sensitivity, stability, and selectivity are low. This study was designed to develop new synthetic pathways to precursors that produce high purity, two phase In2O3-SnO2. The precursors were formed by complexation of tin with any oxide ligands to give the ammonium salt (NH4). Thermal studies of these precursors were carried out by thermal gravimetry (TG) and differential scanning calorimetry (DSC). Further studies by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR) were also conducted.

  18. Single-Source Molecular Precursor for Synthesis of CdS Nanoparticles and Nanoflowers

    NASA Astrophysics Data System (ADS)

    Salavati-Niasari, Masoud; Sobhani, Azam

    2012-04-01

    CdS Semiconductor nanostructures were synthesized by using two different methods. Using triphenylphosphine (C18H15P) and oleylamine (C18H37N) as surfactant, CdS semiconductor nanocrystals with a size ranging from 30 to 90 nm can be synthesized by thermal decomposition of precursor [bis(thiosemicarbazide)cadmium(II)]. CdS nanoflowers were synthesized via hydrothermal decomposition of [bis(thiosemicarbazide) cadmium(II)] without any surfactant. X-ray diffraction (XRD) patterns confirm that the resulting samples were a pure hexagonal phase of CdS. The optical property test indicates that the absorption peak of the samples shifts towards short wavelength, and the blue shift phenomenon might be ascribed to the quantum effect.

  19. Titania-catalyzed radiofluorination of tosylated precursors in highly aqueous medium

    DOE PAGES

    Sergeev, Maxim E.; Morgia, Federica; Lazari, Mark; ...

    2015-04-10

    Nucleophilic radiofluorination is an efficient synthetic route to many positron-emission tomography (PET) probes, but removal of water to activate the cyclotron-produced [ 18F]fluoride has to be performed prior to reaction, which significantly increases overall radiolabeling time and causes radioactivity loss. In this paper, we demonstrate the possibility of 18F-radiofluorination in highly aqueous medium. The method utilizes titania nanoparticles, 1:1 (v/v) acetonitrile–thexyl alcohol solvent mixture, and tetra-n-butylammonium bicarbonate as a phase-transfer agent. Efficient radiolabeling is directly performed with aqueous [ 18F]fluoride without the need for a drying/azeotroping step to significantly reduce radiosynthesis time. High radiochemical purity of the target compound ismore » also achieved. Finally, the substrate scope of the synthetic strategy is demonstrated with a range of aromatic, aliphatic, and cycloaliphatic tosylated precursors.« less

  20. Characterization of the Sol-Gel Transition for Zirconia-Toughened Alumina Precursors

    NASA Technical Reports Server (NTRS)

    Moeti, I.; Karikari, E.; Chen, J.

    1998-01-01

    High purity ZTA ceramic powders with and without yttria were produced using metal alkoxide precursors. ZTA ceramic powders with varying volume percents of zirconia were prepared (7, 15, and 22%). Aluminum tri-sec butoxide, zirconium propoxide, and yttrium isopropoxide were the reagents used. Synthesis conditions were varied to control the hydrolysis and the aging conditions for the sol to gel transition. FTIR analysis and theological characterization were used to follow the structural evolution during the sol to gel transition. The greater extent of hydrolysis and the build-up of structure measured from viscoelastic properties were consistent. Heat treatment was conducted to produce submicron grain fully crystalline ZTA ceramic powders. In all experimental cases a-alumina and tetragonal zirconia phases were confirmed even in the absence of yttria.

  1. Nanostructured polymer-titanium composites and titanium oxide through polymer swelling in titania precursor.

    PubMed

    Kierys, A; Zaleski, R; Buda, W; Pikus, S; Dziadosz, M; Goworek, J

    2013-06-01

    Polymer (XAD7HP)/Ti 4+ nanocomposites were prepared through the swelling of polymer in titanium (IV) ethoxide as a titanium dioxide precursor. The nanocomposite beads exhibit relatively high porosity different than the porosity of the initial polymer. Thermal treatment of composite particles up to 200 °C in vacuum causes the change of their internal structure. At higher temperature, the components of composite become more tightly packed. Calcination at 600 °C and total removal of polymer produce spherically shaped TiO 2 condensed phase as determined by XRD. Thermally treated composites show the substantial change of pore dimensions within micro- and mesopores. The presence of micropores and their transformation during thermal processing was studied successfully by positron annihilation lifetime spectroscopy (PALS). The results derived from PALS experiment were compared with those obtaining from low-temperature nitrogen adsorption data.

  2. Antarctic new particle formation from continental biogenic precursors

    NASA Astrophysics Data System (ADS)

    Kyrö, E.-M.; Kerminen, V.-M.; Virkkula, A.; Dal Maso, M.; Parshintsev, J.; Ruíz-Jimenez, J.; Forsström, L.; Manninen, H. E.; Riekkola, M.-L.; Heinonen, P.; Kulmala, M.

    2012-12-01

    Over Antarctica, aerosol particles originate almost entirely from marine areas, with minor contribution from long-range transported dust or anthropogenic material. The Antarctic continent itself, unlike all other continental areas, has been thought to be practically free of aerosol sources. Here we present evidence of local aerosol production associated with melt-water ponds in the continental Antarctica. We show that in air masses passing such ponds, new aerosol particles are efficiently formed and these particles grow up to sizes where they may act as cloud condensation nuclei (CCN). The precursor vapours responsible for aerosol formation and growth originate very likely from highly abundant cyanobacteria Nostoc commune (Vaucher) communities of local ponds. This is the first time when freshwater vegetation has been identified as an aerosol precursor source. The influence of the new source on clouds and climate may increase in future Antarctica, and possibly elsewhere undergoing accelerating summer melting of semi-permanent snow cover.

  3. Antarctic new particle formation from continental biogenic precursors

    NASA Astrophysics Data System (ADS)

    Kyrö, E.-M.; Kerminen, V.-M.; Virkkula, A.; Dal Maso, M.; Parshintsev, J.; Ruíz-Jimenez, J.; Forsström, L.; Manninen, H. E.; Riekkola, M.-L.; Heinonen, P.; Kulmala, M.

    2013-04-01

    Over Antarctica, aerosol particles originate almost entirely from marine areas, with minor contribution from long-range transported dust or anthropogenic material. The Antarctic continent itself, unlike all other continental areas, has been thought to be practically free of aerosol sources. Here we present evidence of local aerosol production associated with melt-water ponds in continental Antarctica. We show that in air masses passing such ponds, new aerosol particles are efficiently formed and these particles grow up to sizes where they may act as cloud condensation nuclei (CCN). The precursor vapours responsible for aerosol formation and growth originate very likely from highly abundant cyanobacteria Nostoc commune (Vaucher) communities of local ponds. This is the first time freshwater vegetation has been identified as an aerosol precursor source. The influence of the new source on clouds and climate may increase in future Antarctica, and possibly elsewhere undergoing accelerating summer melting of semi-permanent snow cover.

  4. Derivation of Multipotent Mesenchymal Precursors from Human Embryonic Stem Cells

    PubMed Central

    Barberi, Tiziano; Willis, Lucy M; Socci, Nicholas D; Studer, Lorenz

    2005-01-01

    Background Human embryonic stem cells provide access to the earliest stages of human development and may serve as a source of specialized cells for regenerative medicine. Thus, it becomes crucial to develop protocols for the directed differentiation of embryonic stem cells into tissue-restricted precursors. Methods and Findings Here, we present culture conditions for the derivation of unlimited numbers of pure mesenchymal precursors from human embryonic stem cells and demonstrate multilineage differentiation into fat, cartilage, bone, and skeletal muscle cells. Conclusion Our findings will help to elucidate the mechanism of mesoderm specification during embryonic stem cell differentiation and provide a platform to efficiently generate specialized human mesenchymal cell types for future clinical applications. PMID:15971941

  5. Superconducting MgB2 films via precursor postprocessing approach

    NASA Astrophysics Data System (ADS)

    Paranthaman, M.; Cantoni, C.; Zhai, H. Y.; Christen, H. M.; Aytug, T.; Sathyamurthy, S.; Specht, E. D.; Thompson, J. R.; Lowndes, D. H.; Kerchner, H. R.; Christen, D. K.

    2001-06-01

    Superconducting MgB2 films with Tc=38.6 K were prepared using a precursor-deposition, ex situ postprocessing approach. Precursor films of boron, ˜0.5 μm thick, were deposited onto Al2O3 (102) substrates by electron-beam evaporation; a postanneal at 890 °C in the presence of bulk MgB2 and Mg metal produced highly crystalline MgB2 films. X-ray diffraction indicated that the films exhibit some degree of c-axis alignment, but are randomly oriented in plane. Transport current measurements of the superconducting properties show high values of the critical current density and yield an irreversibility line that exceeds that determined by magnetic measurements on bulk polycrystalline materials.

  6. Nuclear localization of foamy virus Gag precursor protein.

    PubMed Central

    Schliephake, A W; Rethwilm, A

    1994-01-01

    All foamy viruses give rise to a strong nuclear staining when infected cells are reacted with sera from infected hosts. This nuclear fluorescence distinguishes foamy viruses from all other retroviruses. The experiments reported here indicate that the foamy virus Gag precursor protein is transiently located in the nuclei of infected cells and this is the likely reason for the typical foamy virus nuclear fluorescence. By using the vaccinia virus expression system, a conserved basic sequence motif in the nucleocapsid domain of foamy virus Gag proteins was identified to be responsible for the nuclear transport of the gag precursor molecule. This motif was also found to be able to direct a heterologous protein, the Gag protein of human immunodeficiency virus, into the nucleus. Images PMID:8035493

  7. Structural basis for precursor protein-directed ribosomal peptide macrocyclization

    SciT

    Li, Kunhua; Condurso, Heather L.; Li, Gengnan

    Macrocyclization is a common feature of natural product biosynthetic pathways including the diverse family of ribosomal peptides. Microviridins are architecturally complex cyanobacterial ribosomal peptides that target proteases with potent reversible inhibition. The product structure is constructed via three macrocyclizations catalyzed sequentially by two members of the ATP-grasp family, a unique strategy for ribosomal peptide macrocyclization. Here we describe in detail the structural basis for the enzyme-catalyzed macrocyclizations in the microviridin J pathway of Microcystis aeruginosa. The macrocyclases MdnC and MdnB interact with a conserved α-helix of the precursor peptide using a novel precursor-peptide recognition mechanism. The results provide insight intomore » the unique protein–protein interactions that are key to the chemistry, suggest an origin for the natural combinatorial synthesis of microviridin peptides, and provide a framework for future engineering efforts to generate designed compounds.« less

  8. Possible precursors to the 2011 3/11 Japan earthquake:

    NASA Astrophysics Data System (ADS)

    Hayakawa, M.; Hobara, Y.; Schekotov, A.; Rozhnoi, A.; Solovieva, M.

    2012-04-01

    The purpose of this paper is to present a possible precursor to the 2011 March 11 Japan earthquake. First of all, we present the results on subionospheric VLF/LF propagation anomaly (ionospheric perturbation) by means of Japan-Russia VLF network. It is found that the ionospheric perturbation is clearly detected on March 4, 5 and 6 on the propagation paths of NLK (Seattle, USA) to Japanese stations and on a path of JJI (Miyazaki, Kyushu) to Kamchatka. Next, we present the results on the ULF depression (horizontal component) on the same days, which is interpreted in terms of the absorption in the disturbed lower ionosphere of the downgoing magnetospheric Alfve'n waves. These two precursors are considered to be due to the same effect of the lower ionospheric perturbation about one week before the earthquake.

  9. Amplitude of foreshocks as a possible seismic precursor to earthquakes

    Lindh, A.G.

    1978-01-01

    In recent years, we have made significant progress in being able to recognize the long-range pattern of events that precede large earthquakes. For example, in a recent issue of the Earthquake Information Bulletin, we saw how the pioneering work of S.A. Fedotov of the U.S.S.R in the Kamchatka-Kurile Islands region has been applied worldwide to forecast where large, shallow earthquakes might occur in the next decades. Indeed, such a "seismic gap" off the coast of Alaska was filled by the 1972 Sitka earthquake. Promising results are slowly accumulating from other techniques that suggest that intermediate-term precursors might also be seen: among these are tilt and geomagnetic anomalies and anomalous land uplift. But the crucial point remains that short-term precursors (days to hours) will be needed in many cases if there is to be a significant saving of lives. 

  10. Creep and slip: Seismic precursors to the Nuugaatsiaq landslide (Greenland)

    NASA Astrophysics Data System (ADS)

    Poli, Piero

    2017-09-01

    Precursory signals to material's failure are predicted by numerical models and observed in laboratory experiments or using field data. These precursory signals are a marker of slip acceleration on weak regions, such as crustal faults. Observation of these precursory signals of catastrophic natural events, such as earthquakes and landslides, is necessary for improving our knowledge about the physics of the nucleation process. Furthermore, observing such precursory signals may help to forecast these catastrophic events or reduce their hazard. I report here the observation of seismic precursors to the Nuugaatsiaq landslide in Greenland. Time evolution of the detected precursors implies that an aseismic slip event is taking place for hours before the landslide, with an exponential increase of slip velocity. Furthermore, time evolution of the precursory signals' amplitude sheds light on the evolution of the fault physics during the nucleation process.

  11. Ceramic fibers from Si-B-C polymer precursors

    NASA Technical Reports Server (NTRS)

    Riccitiello, S. R.; Hsu, M. S.; Chen, T. S.

    1993-01-01

    Non-oxide ceramics such as silicon carbide (SiC), silicon nitride (Si3N4), and silicon borides (SiB4, SiB6) have thermal stability, oxidation resistance, hardness, and varied electrical properties. All these materials can be prepared in a fiber form from a suitable polymer precursor. The above mentioned fibers, when tested over a temperature range from 25 to 1400 C, experience degradation at elevated temperatures. Past work in ceramic materials has shown that the strength of ceramics containing both carbides and borides is sustained at elevated temperatures, with minimum oxidation. The work presented here describes the formation of ceramic fibers containing both elements, boron and silicon, prepared via the polymer precursor route previously reported by the authors, and discusses the fiber mechanical properties that are retained over the temperature range studied.

  12. Boron/Carbon/Silicon/Nitrogen Ceramics And Precursors

    NASA Technical Reports Server (NTRS)

    Riccitiello, Salvatore; Hsu, Ming TA; Chen, Timothy S.

    1996-01-01

    Ceramics containing various amounts of boron, carbon, silicon, and nitrogen made from variety of polymeric precursors. Synthesized in high yield from readily available and relatively inexpensive starting materials. Stable at room temperature; when polymerized, converted to ceramics in high yield. Ceramics resist oxidation and other forms of degradation at high temperatures; used in bulk to form objects or to infiltrate other ceramics to obtain composites having greater resistance to oxidation and high temperatures.

  13. New Ir Bis-Carbonyl Precursor for Water Oxidation Catalysis

    SciT

    Huang, Daria L.; Beltrán-Suito, Rodrigo; Thomsen, Julianne M.

    2016-02-05

    This paper introduces IrI(CO)2(pyalc) (pyalc = (2-pyridyl)-2-propanoate) as an atom-efficient precursor for Ir-based homogeneous oxidation catalysis. This compound was chosen to simplify analysis of the water oxidation catalyst species formed by the previously reported Cp*IrIII(pyalc)OH water oxidation precatalyst. Here, we present a comparative study on the chemical and catalytic properties of these two precursors. Previous studies show that oxidative activation of Cp*Ir-based precursors with NaIO4 results in formation of a blue IrIV species. This activation is concomitant with the loss of the placeholder Cp* ligand which oxidatively degrades to form acetic acid, iodate, and other obligatory byproducts. The activation processmore » requires substantial amounts of primary oxidant, and the degradation products complicate analysis of the resulting IrIV species. The species formed from oxidation of the Ir(CO)2(pyalc) precursor, on the other hand, lacks these degradation products (the CO ligands are easily lost upon oxidation) which allows for more detailed examination of the resulting Ir(pyalc) active species both catalytically and spectroscopically, although complete structural analysis is still elusive. Once Ir(CO)2(pyalc) is activated, the system requires acetic acid or acetate to prevent the formation of nanoparticles. Investigation of the activated bis-carbonyl complex also suggests several Ir(pyalc) isomers may exist in solution. By 1H NMR, activated Ir(CO)2(pyalc) has fewer isomers than activated Cp*Ir complexes, allowing for advanced characterization. Future research in this direction is expected to contribute to a better structural understanding of the active species. A diol crystallization agent was needed for the structure determination of 3.« less

  14. Preparation of Sic/AIN Solid Solutions Using Organometallic Precursors

    DTIC Science & Technology

    1989-02-15

    pyrolysis of organoaluminum and organosilicon compounds was investigated as a potential source of SiC /AUI solid solutions. Using two different co... pyrolysis methods, homogeneous mixtures of organoaluminum amides and both a vinylic polysilane and a poly- carbosilane were convertec to a preceramic ...solid that transformed to crystalline SiC /AiN solid solutions at 򒸀 C. Moreover, the liquid, polymeric , form of these precursor mixtures provides a

  15. Viral repression of fungal pheromone precursor gene expression.

    PubMed

    Zhang, L; Baasiri, R A; Van Alfen, N K

    1998-02-01

    Biological control of chestnut blight caused by the filamentous ascomycete Cryphonectria parasitica can be achieved with a virus that infects this fungus. This hypovirus causes a perturbation of fungal development that results in low virulence (hypovirulence), poor asexual sporulation, and female infertility without affecting fungal growth in culture. At the molecular level, the virus is known to affect the transcription of a number of fungal genes. Two of these genes, Vir1 and Vir2, produce abundant transcripts in noninfected strains of the fungus, but the transcripts are not detectable in virus-infected strains. We report here that these two genes encode the pheromone precursors of the Mat-2 mating type of the fungus; consequently, these genes have been renamed Mf2/1 and Mf2/2. To determine if the virus affects the mating systems of both mating types of this fungus, the pheromone precursor gene, Mf1/1, of a Mat-1 strain was cloned and likewise was found to be repressed in virus-infected strains. The suppression of transcription of the pheromone precursor genes of this fungus could be the cause of the mating defect of infected strains of the fungus. Although published reports suggest that a G alpha(i) subunit may be involved in this regulation, our results do not support this hypothesis. The prepropheromone encoded by Mf1/1 is structurally similar to that of the prepro-p-factor of Schizosaccharomyces pombe. This is the first description of the complete set of pheromone precursor genes encoded by a filamentous ascomycete.

  16. Viral Repression of Fungal Pheromone Precursor Gene Expression

    PubMed Central

    Zhang, Lei; Baasiri, Rudeina A.; Van Alfen, Neal K.

    1998-01-01

    Biological control of chestnut blight caused by the filamentous ascomycete Cryphonectria parasitica can be achieved with a virus that infects this fungus. This hypovirus causes a perturbation of fungal development that results in low virulence (hypovirulence), poor asexual sporulation, and female infertility without affecting fungal growth in culture. At the molecular level, the virus is known to affect the transcription of a number of fungal genes. Two of these genes, Vir1 and Vir2, produce abundant transcripts in noninfected strains of the fungus, but the transcripts are not detectable in virus-infected strains. We report here that these two genes encode the pheromone precursors of the Mat-2 mating type of the fungus; consequently, these genes have been renamed Mf2/1 and Mf2/2. To determine if the virus affects the mating systems of both mating types of this fungus, the pheromone precursor gene, Mf1/1, of a Mat-1 strain was cloned and likewise was found to be repressed in virus-infected strains. The suppression of transcription of the pheromone precursor genes of this fungus could be the cause of the mating defect of infected strains of the fungus. Although published reports suggest that a Gαi subunit may be involved in this regulation, our results do not support this hypothesis. The prepropheromone encoded by Mf1/1 is structurally similar to that of the prepro-p-factor of Schizosaccharomyces pombe. This is the first description of the complete set of pheromone precursor genes encoded by a filamentous ascomycete. PMID:9447992

  17. Petrological and seismic precursors of the paroxysmal phase of the last Vesuvius eruption on March 1944

    PubMed Central

    Pappalardo, Lucia; D'Auria, Luca; Cavallo, Andrea; Fiore, Stefano

    2014-01-01

    Abrupt transitions in style and intensity are common during volcanic eruptions, with an immediate impact on the surrounding territory and its population. Defining the factors trigger such sudden shifts in the eruptive behavior as well as developing methods to predict such changes during volcanic crises are crucial goals in volcanology. In our research, the combined investigation of both petrological and seismic indicators has been applied for the first time to a Vesuvius eruption, that of March 1944 that caused the present dormant state of the volcano. Our results contribute to elucidate the evolution of the conduit dynamics that generated a drastic increase in the Volcanic Explosivity Index, associated to the ejection of huge amount of volcanic ash. Remarkably, our study shows that the main paroxysm was announced by robust changes in petrology consistent with seismology, thus suggesting that the development of monitoring methods to assess the nature of ejected juvenile material combined with conventional geophysical techniques can represent a powerful tool for forecasting the evolution of an eruption towards violent behavior. This in turn is a major goal in volcanology because this evidence can help decision-makers to implement an efficient safety strategy during the emergency (scale and pace of evacuation). PMID:25199537

  18. Nanostructured manganese oxides as highly active water oxidation catalysts: a boost from manganese precursor chemistry.

    PubMed

    Menezes, Prashanth W; Indra, Arindam; Littlewood, Patrick; Schwarze, Michael; Göbel, Caren; Schomäcker, Reinhard; Driess, Matthias

    2014-08-01

    We present a facile synthesis of bioinspired manganese oxides for chemical and photocatalytic water oxidation, starting from a reliable and versatile manganese(II) oxalate single-source precursor (SSP) accessible through an inverse micellar molecular approach. Strikingly, thermal decomposition of the latter precursor in various environments (air, nitrogen, and vacuum) led to the three different mineral phases of bixbyite (Mn2 O3 ), hausmannite (Mn3 O4 ), and manganosite (MnO). Initial chemical water oxidation experiments using ceric ammonium nitrate (CAN) gave the maximum catalytic activity for Mn2 O3 and MnO whereas Mn3 O4 had a limited activity. The substantial increase in the catalytic activity of MnO in chemical water oxidation was demonstrated by the fact that a phase transformation occurs at the surface from nanocrystalline MnO into an amorphous MnOx (1

  19. The determination of nonylphenol and its precursors in a trickling filter wastewater treatment process.

    PubMed

    Petrie, Bruce; McAdam, Ewan J; Whelan, Mick J; Lester, John N; Cartmell, Elise

    2013-04-01

    An ultra performance liquid chromatography method coupled to a triple quadrupole mass spectrometer was developed to determine nonylphenol and 15 of its possible precursors (nonylphenol ethoxylates and nonylphenol carboxylates) in aqueous and particulate wastewater matrices. Final effluent method detection limits for all compounds ranged from 1.4 to 17.4 ng l(-1) in aqueous phases and from 1.4 to 39.4 ng g(-1) in particulate phases of samples. The method was used to measure the performance of a trickling filter wastewater treatment works, which are not routinely monitored despite their extensive usage. Relatively good removals of nonylphenol were observed over the biological secondary treatment process, accounting for a 53 % reduction. However, only an 8 % reduction in total nonylphenolic compound load was observed. This was explained by a shortening in ethoxylate chain length which initiated production of shorter polyethoxylates ranging from 1 to 4 ethoxylate units in length in final effluents. Modelling the possible impact of trickling filter discharge demonstrated that the nonylphenol environmental quality standard may be exceeded in receiving waters with low dilution ratios. In addition, there is a possibility that the EQS can be exceeded several kilometres downstream of the mixing zone due to the biotransformation of readily degradable short-chained precursors. This accentuates the need to monitor 'non-priority' parent compounds in wastewater treatment works since monitoring nonylphenol alone can give a false indication of process performance. It is thus recommended that future process performance monitoring and optimisation is undertaken using the full suite of nonylphenolic moieties which this method can facilitate.

  20. Synthesis of t-Butyl (2R)-Hydroxyisovalerate, A Precursor of Aureobasidin B

    NASA Astrophysics Data System (ADS)

    Maharani, R.; Puspitasari, D.; Taufiqqurahman; Huspa, D. H. P.; Hidayat, A. T.; Sumiarsa, D.; Hidayat, I. W.

    2017-02-01

    Aureobasidins are a family of cyclodepsipeptides have antifungal properties. They were isolated from the black yeast Aureobasidium pullulans R106 and over 30 derivatives have been successfully characterized. There are few publications reporting the total synthesis of aureobasidins. The limited reports of the synthesis of the aureobasidin derivatives are due to the difficult access to the preparations of precursors. The aim of this research is to synthesise a precursor of aureobasidin B, t-butyl (2R)-hydroxyisovalerate (t-Bu-Hiv), that is prepared for the total synthesis of aureobasidin B. The synthesis of AbB is planned to be undertaken by using a solid phase method, so the ester formation between t-Bu-Hiv and the Fmoc-β-hydroxymethylvaline will be carried out in solution phase to form depsidipeptide. The t-butyl group was used as protecting agent that is due to the straightforward elimination of the protecting group from the Fmoc-depsidipeptide. The t-Bu-Hiv acid was prepared from D-valine through diazotisation to form (2R)-acetyloxyisovaleric acid in 62.7% yield. Product of the first step was then protected by t-butyl group by using Boc-anhydride in t-butanol to give t-butil (2R)-acetyloxyisovalerate in 44% yield. In the last step, the acetyloxy group was eliminated by using potassium carbonate in methanol/water to give the desired product, t-Bu-Hiv in 33.5% yield. The t-Bu-Hiv is ready to be combined with Fmoc-β-hydroxymethylvaline to result in depsidipeptide that will be attached to the resin in the total synthesis of AbB. Each stage of this synthesis was controlled by thin layer chromatography and all products were purified by open column chromatography. All the synthesized products were characterized by various spectroscopic techniques, including infrared spectrophotometer, mass spectroscopy (ESI-MS), 1H-NMR and 13C-NMR.

  1. Production of jet fuel precursor monoterpenoids from engineered Escherichia coli.

    PubMed

    Mendez-Perez, Daniel; Alonso-Gutierrez, Jorge; Hu, Qijun; Molinas, Margaux; Baidoo, Edward E K; Wang, George; Chan, Leanne J G; Adams, Paul D; Petzold, Christopher J; Keasling, Jay D; Lee, Taek S

    2017-08-01

    Monoterpenes (C 10 isoprenoids) are the main components of essential oils and are possible precursors for many commodity chemicals and high energy density fuels. Monoterpenes are synthesized from geranyl diphosphate (GPP), which is also the precursor for the biosynthesis of farnesyl diphosphate (FPP). FPP biosynthesis diverts the carbon flux from monoterpene production to C 15 products and quinone biosynthesis. In this study, we tested a chromosomal mutation of Escherichia coli's native FPP synthase (IspA) to improve GPP availability for the production of monoterpenes using a heterologous mevalonate pathway. Monoterpene production at high levels required not only optimization of GPP production but also a basal level of FPP to maintain growth. The optimized strains produced two jet fuel precursor monoterpenoids 1,8-cineole and linalool at the titer of 653 mg/L and 505 mg/L, respectively, in batch cultures with 1% glucose. The engineered strains developed in this work provide useful resources for the production of high-value monoterpenes. Biotechnol. Bioeng. 2017;114: 1703-1712. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  2. Phylogenetic appearance of Neuropeptide S precursor proteins in tetrapods

    PubMed Central

    Reinscheid, Rainer K.

    2007-01-01

    Sleep and emotional behavior are two hallmarks of vertebrate animal behavior, implying that specialized neuronal circuits and dedicated neurochemical messengers may have been developed during evolution to regulate such complex behaviors. Neuropeptide S (NPS) is a newly identified peptide transmitter that activates a typical G protein-coupled receptor. Central administration of NPS produces profound arousal, enhances wakefulness and suppresses all stages of sleep. In addition, NPS can alleviate behavioral responses to stress by producing anxiolytic-like effects. A bioinformatic analysis of current genome databases revealed that the NPS peptide precursor gene is present in all vertebrates with the exception of fish. A high level of sequence conservation, especially of aminoterminal structures was detected, indicating stringent requirements for agonist-induced receptor activation. Duplication of the NPS precursor gene was only found in one out of two marsupial species with sufficient genome coverage (Monodelphis domestica; opossum), indicating that the duplicated opossum NPS sequence might have arisen as an isolated event. Pharmacological analysis of both Monodelphis NPS peptides revealed that only the closely related NPS peptide retained agonistic activity at NPS receptors. The duplicated precursor might be either a pseudogene or could have evolved different receptor selectivity. Together, these data show that NPS is a relatively recent gene in vertebrate evolution whose appearance might coincide with its specialized physiological functions in terrestrial vertebrates. PMID:17293003

  3. Molecular pathogenesis of precursor lesions of pancreatic ductal adenocarcinoma.

    PubMed

    Biankin, Andrew V; Kench, James G; Dijkman, Floriaan P; Biankin, Sandra A; Henshall, Susan M

    2003-02-01

    Precursor lesions are assuming greater importance in the study of pancreatic ductal adenocarcinoma. As pancreatic cancer is almost universally fatal due to late clinical presentation and biological aggressiveness, characterisation of its precursor lesions may create scope for early diagnosis and improved outcome with conventional therapies as well as the development of novel therapeutic and preventative strategies. Pancreatic intraepithelial neoplasia (PanIN) and intraductal papillary mucinous tumours (IPMTs) are thought to be precursor lesions of ductal adenocarcinoma of the pancreas. Recent work has focused on the molecular aberrations associated with these lesions leading to the formulation of a progression model for pancreatic cancer. Progressive histopathological changes along the progression model are associated with aberrations of cell cycle regulatory and growth factor signalling molecules that occur in pancreatic cancer at high frequency and are common to many cancers. Characterisation of these molecular aberrations provides scope for the development of novel diagnostic and treatment strategies that will ultimately impact on the outcome for people who develop pancreatic cancer.

  4. LWIR hyperspectral imaging application and detection of chemical precursors

    NASA Astrophysics Data System (ADS)

    Lavoie, Hugo; Thériault, Jean-Marc; Bouffard, François; Puckrin, Eldon; Dubé, Denis

    2012-10-01

    Detection and identification of Toxic industrial chemicals (TICs) represent a major challenge to protect and sustain first responder and public security. In this context, passive Hyperspectral Imaging (HSI) is a promising technology for the standoff detection and identification of chemical vapors emanating from a distant location. To investigate this method, the Department of National Defense and Public Safety Canada have mandated Defense Research and Development Canada (DRDC) - Valcartier to develop and test Very Long Wave Infrared (VLWIR) HSI sensors for standoff detection. The initial effort was focused to address the standoff detection and identification of toxic industrial chemicals (TICs), surrogates and precursors. Sensors such as the Improved Compact ATmospheric Sounding Interferometer (iCATSI) and the Multi-option Differential Detection and Imaging Fourier Spectrometer (MoDDIFS) were developed for this application. This paper presents the sensor developments and preliminary results of standoff detection and identification of TICs and precursors. The iCATSI and MoDDIFS sensors are based on the optical differential Fourier-transform infrared (FTIR) radiometric technology and are able to detect, spectrally resolve and identify small leak at ranges in excess of 1 km. Results from a series of trials in asymmetric threat type scenarios are reported. These results serve to establish the potential of passive standoff HSI detection of TICs, precursors and surrogates.

  5. Prolactin Stimulates Precursor Cells in the Adult Mouse Hippocampus

    PubMed Central

    Walker, Tara L.; Vukovic, Jana; Koudijs, Margaretha M.; Blackmore, Daniel G.; Mackay, Eirinn W.; Sykes, Alex M.; Overall, Rupert W.; Hamlin, Adam S.; Bartlett, Perry F.

    2012-01-01

    In the search for ways to combat degenerative neurological disorders, neurogenesis-stimulating factors are proving to be a promising area of research. In this study, we show that the hormonal factor prolactin (PRL) can activate a pool of latent precursor cells in the adult mouse hippocampus. Using an in vitro neurosphere assay, we found that the addition of exogenous PRL to primary adult hippocampal cells resulted in an approximate 50% increase in neurosphere number. In addition, direct infusion of PRL into the adult dentate gyrus also resulted in a significant increase in neurosphere number. Together these data indicate that exogenous PRL can increase hippocampal precursor numbers both in vitro and in vivo. Conversely, PRL null mice showed a significant reduction (approximately 80%) in the number of hippocampal-derived neurospheres. Interestingly, no deficit in precursor proliferation was observed in vivo, indicating that in this situation other niche factors can compensate for a loss in PRL. The PRL loss resulted in learning and memory deficits in the PRL null mice, as indicated by significant deficits in the standard behavioral tests requiring input from the hippocampus. This behavioral deficit was rescued by direct infusion of recombinant PRL into the hippocampus, indicating that a lack of PRL in the adult mouse hippocampus can be correlated with impaired learning and memory. PMID:22973440

  6. Oxidation and formation of deposit precursors in hydrocarbon fuels

    NASA Technical Reports Server (NTRS)

    Mayo, F. R.; Lan, B.; Cotts, D. B.; Buttrill, S. E., Jr.; St.john, G. A.

    1983-01-01

    The oxidation of two jet turbine fuels and some pure hydrocarbons was studied at 130 C with and without the presence of small amounts of N-methyl pyrrole (NMP) or indene. Tendency to form solid-deposit precursors was studied by measuring soluble gum formation as well as dimer and trimer formation using field ionization mass spectrometry. Pure n-dodecane oxidized fastest and gave the smallest amount of procursors. An unstable fuel oil oxidized much slower but formed large amounts of precursors. Stable Jet A fuel oxidized slowest and gave little precursors. Indene either retarded or accelerated the oxidation of n-dodecane, depending on its concentration, but always caused more gum formation. The NMP greatly retarded n-dodecane oxidation but accelerated Jet A oxidation and greatly increased the latter's gum formation. In general, the additive reacted faster and formed most of the gum. Results are interpreted in terms of classical cooxidation theory. The effect of oxygen pressure on gum formation is also reported.

  7. Reduction of precursor decay anomaly in single crystal lithium fluoride

    NASA Astrophysics Data System (ADS)

    Sano, Yukio

    2000-08-01

    The purpose of this study is to reveal that the precursor decay anomaly in single crystal lithium fluoride is reduced by Sano's decay curve [Y. Sano, J. Appl. Phys. 85, 7616 (1999)], which is much smaller in slope than Asay's decay curve [J. R. Asay, G. R. Fowles, G. E. Duvall, M. H. Miles, and R. F. Tinder, J. Appl. Phys. 43, 2132 (1972)]. To this end, strain, particle, velocity, and stress in a precursor and near the leading edge of the follower changing with time along Sano's decay curve are first analyzed quantitatively. The analysis verified the existence of degenerate contraction waves I and II and a subrarefaction wave R', and the decay process [Y. Sano, J. Appl. Phys. 77, 3746 (1995)] caused in sequence by evolving followers C, I, II, R', Rb. Next, inequalities relating decay rates qualitatively to plastic strain rates at the leading edge of the follower, which are derived using the properties of the followers, are incorporated into the analysis. Calculation results showed that the plastic strain rates were reduced by low decay rates. This indicates that the precursor decay anomaly might be greatly reduced by Sano's decay curve.

  8. Precursor Wave Emission Enhanced by Weibel Instability in Relativistic Shocks

    NASA Astrophysics Data System (ADS)

    Iwamoto, Masanori; Amano, Takanobu; Hoshino, Masahiro; Matsumoto, Yosuke

    2018-05-01

    We investigated the precursor wave emission efficiency in magnetized purely perpendicular relativistic shocks in pair plasmas. We extended our previous study to include the dependence of upstream magnetic field orientations. We performed two-dimensional particle-in-cell simulations and focused on two magnetic field orientations: the magnetic field in the simulation plane (i.e., in-plane configuration) and that perpendicular to the simulation plane (i.e., out-of-plane configuration). Our simulations in the in-plane configuration demonstrated that not only extraordinary but also ordinary mode waves are excited. We quantified the emission efficiency as a function of the magnetization parameter σ e and found that the large-amplitude precursor waves are emitted for a wide range of σ e . We found that especially at low σ e , the magnetic field generated by Weibel instability amplifies the ordinary mode wave power. The amplitude is large enough to perturb the upstream plasma, and transverse density filaments are generated as in the case of the out-of-plane configuration investigated in the previous study. We confirmed that our previous conclusion holds regardless of upstream magnetic field orientations with respect to the two-dimensional simulation plane. We discuss the precursor wave emission in three dimensions and the feasibility of wakefield acceleration in relativistic shocks based on our results.

  9. A mobile precursor determines protein resistance on nanostructured surfaces.

    PubMed

    Wang, Kang; Chen, Ye; Gong, Xiangjun; Xia, Jianlong; Zhao, Junpeng; Shen, Lei

    2018-05-09

    Biomaterials are often engineered with nanostructured surfaces to control interactions with proteins and thus regulate their biofunctions. However, the mechanism of how nanostructured surfaces resist or attract proteins together with the underlying design rules remains poorly understood at a molecular level, greatly limiting attempts to develop high-performance biomaterials and devices through the rational design of nanostructures. Here, we study the dynamics of nonspecific protein adsorption on block copolymer nanostructures of varying adhesive domain areas in a resistant matrix. Using surface plasmon resonance and single molecule tracking techniques, we show that weakly adsorbed proteins with two-dimensional diffusivity are critical precursors to protein resistance on nanostructured surfaces. The adhesive domain areas must be more than tens or hundreds of times those of the protein footprints to slow down the 2D-mobility of the precursor proteins for their irreversible adsorption. This precursor model can be used to quantitatively analyze the kinetics of nonspecific protein adsorption on nanostructured surfaces. Our method is applicable to precisely manipulate protein adsorption and resistance on various nanostructured surfaces, e.g., amphiphilic, low-surface-energy, and charged nanostructures, for the design of protein-compatible materials.

  10. Accident sequence precursor events with age-related contributors

    SciT

    Murphy, G.A.; Kohn, W.E.

    1995-12-31

    The Accident Sequence Precursor (ASP) Program at ORNL analyzed about 14.000 Licensee Event Reports (LERs) filed by US nuclear power plants 1987--1993. There were 193 events identified as precursors to potential severe core accident sequences. These are reported in G/CR-4674. Volumes 7 through 20. Under the NRC Nuclear Plant Aging Research program, the authors evaluated these events to determine the extent to which component aging played a role. Events were selected that involved age-related equipment degradation that initiated an event or contributed to an event sequence. For the 7-year period, ORNL identified 36 events that involved aging degradation as amore » contributor to an ASP event. Except for 1992, the percentage of age-related events within the total number of ASP events over the 7-year period ({approximately}19%) appears fairly consistent up to 1991. No correlation between plant ape and number of precursor events was found. A summary list of the age-related events is presented in the report.« less

  11. Precursor Analysis for Flight- and Ground-Based Anomaly Risk Significance Determination

    NASA Technical Reports Server (NTRS)

    Groen, Frank

    2010-01-01

    This slide presentation reviews the precursor analysis for flight and ground based anomaly risk significance. It includes information on accident precursor analysis, real models vs. models, and probabilistic analysis.

  12. Precursors in the preparation of transition metal nitrides and transition metal carbonitrides and their reaction intermediates

    DOEpatents

    Maya, Leon

    1991-01-01

    A process for making ammonolytic precursors to nitride and carbonitride ceramics. Extreme reaction conditions are not required and the precursor is a powder-like substance that produces ceramics of improved purity and morphology upon pyrolysis.

  13. An empirical probability density distribution of planetary ionosphere storms with geomagnetic precursors

    NASA Astrophysics Data System (ADS)

    Gulyaeva, Tamara; Stanislawska, Iwona; Arikan, Feza; Arikan, Orhan

    The probability of occurrence of the positive and negative planetary ionosphere storms is evaluated using the W index maps produced from Global Ionospheric Maps of Total Electron Content, GIM-TEC, provided by Jet Propulsion Laboratory, and transformed from geographic coordinates to magnetic coordinates frame. The auroral electrojet AE index and the equatorial disturbance storm time Dst index are investigated as precursors of the global ionosphere storm. The superposed epoch analysis is performed for 77 intense storms (Dst≤-100 nT) and 227 moderate storms (-100phase pW+ (W = 3 and 4) and negative phase pW- (W = -3 and -4) of ionosphere storm, versus AE index and Dst index. It is found that AE index better suits to serve as a precursor of the ionosphere storm than Dst index with onset of the average auroral AE storm occurring 6 h before the equatorial Dst storm onset for intense storms and 3 h in advance of moderate Dst storm. The similar space zones advancement of the ionosphere storm is observed with W index (pW+ and pW-) depicting maximum localized in the polar magnetic zone and minimum at magnetic equator. An empirical relation for pW+ and pW- with AE storm precursor is derived which enables the probability of occurrence of the ionosphere storm to be predicted with leading time of 1-2 h for the positive ionosphere storm and 9-10 h for the negative ionosphere storm. The ionosphere storm probability model is validated using data for 2 intense and 20

  14. Ketonization of levulinic acid and γ-valerolactone to hydrocarbon fuel precursors

    DOE PAGES

    Lilga, Michael A.; Padmaperuma, Asanga B.; Auberry, Deanna L.; ...

    2017-06-21

    We studied a new process for direct conversion of either levulinic acid (LA) or γ-valerolactone (GVL) to hydrocarbon fuel precursors. The process involves passing an aqueous solution of LA or GVL containing a reducing agent, such as ethylene glycol or formic acid, over a ketonization catalyst at 380–400 °C and atmospheric pressure to form a biphasic liquid product. The organic phase is significantly oligomerized and deoxygenated and comprises a complex mixture of open-chain alkanes and olefins, aromatics, and low concentrations of ketones, alcohols, ethers, and carboxylates or lactones. Carbon content in the aqueous phase decreases with decreasing feed rate; themore » aqueous phase can be reprocessed through the same catalyst to form additional organic oils to improve carbon yield. Catalysts are readily regenerated to restore initial activity. Furthermore, the process might be valuable in converting cellulosics to biorenewable gasoline, jet, and diesel fuels as a means to decrease petroleum use and decrease greenhouse gas emissions.« less

  15. 40 CFR 93.164 - Inter-precursor mitigation measures and offsets.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Inter-precursor mitigation measures... § 93.164 Inter-precursor mitigation measures and offsets. Federal agencies must reduce the same type of... mitigation measures of different precursors of the same criteria pollutant, if such trades are allowed by a...

  16. 40 CFR 93.164 - Inter-precursor mitigation measures and offsets.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Inter-precursor mitigation measures... § 93.164 Inter-precursor mitigation measures and offsets. Federal agencies must reduce the same type of... mitigation measures of different precursors of the same criteria pollutant, if such trades are allowed by a...

  17. 40 CFR 93.164 - Inter-precursor mitigation measures and offsets.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 21 2012-07-01 2012-07-01 false Inter-precursor mitigation measures... § 93.164 Inter-precursor mitigation measures and offsets. Federal agencies must reduce the same type of... mitigation measures of different precursors of the same criteria pollutant, if such trades are allowed by a...

  18. 40 CFR 93.164 - Inter-precursor mitigation measures and offsets.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Inter-precursor mitigation measures... § 93.164 Inter-precursor mitigation measures and offsets. Federal agencies must reduce the same type of... mitigation measures of different precursors of the same criteria pollutant, if such trades are allowed by a...

  19. Liquid precursor for deposition of indium selenide and method of preparing the same

    DOEpatents

    Curtis, Calvin J.; Miedaner, Alexander; van Hest, Marinus Franciscus Antonius Maria; Ginley, David S.; Hersh, Peter A.; Eldada, Louay; Stanbery, Billy J.

    2015-09-22

    Liquid precursors containing indium and selenium suitable for deposition on a substrate to form thin films suitable for semiconductor applications are disclosed. Methods of preparing such liquid precursors and method of depositing a liquid precursor on a substrate are also disclosed.

  20. Preparation of Bi-Sr-Ca-Cu-O superconductors from oxide-glass precursors

    DOEpatents

    Hinks, David G.; Capone, II, Donald W.

    1992-01-01

    A superconductor and precursor therefor from oxide mixtures of Ca, Sr, Bi and Cu. Glass precursors quenched to elevated temperatures result in glass free of crystalline precipitates having enhanced mechanical properties. Superconductors are formed from the glass precursors by heating in the presence of oxygen to a temperature below the melting point of the glass.

  1. Functional Analysis of Precursors for Serious Problem Behavior and Related Intervention

    ERIC Educational Resources Information Center

    Langdon, Nancy A.; Carr, Edward G.; Owen-DeSchryver, Jamie S.

    2008-01-01

    Precursor behaviors are innocuous behaviors that reliably precede the occurrence of problem behavior. Intervention efforts applied to precursors might prevent the occurrence of severe problem behavior. We examined the relationship between precursor behavior and problem behavior in three individuals with developmental disabilities. First, a…

  2. Precursor Ion–Ion Aggregation in the Brust–Schiffrin Synthesis of Alkanethiol Nanoparticles

    SciT

    Graham, Trent R.; Renslow, Ryan; Govind, Niranjan

    Tetraoctylammonium bromide is used in the Brust-Schiffrin nanoparticle synthesis to phase-transfer chloroaurate ions from the aqueous phase to the organic phase. While it is established that the quaternary ammonium complex self-associates in the organic phase, the actual self-assembled structure is debated. We have confirmed the presence of ion-ion aggregates through quantitative 1H Nuclear Magnetic Resonance spectroscopy (NMR), pulsed field gradient, diffusion-ordered NMR (DOSY-NMR) and density functional theory (DFT) based NMR shift calculations. Tetraoctylammonium complexes (TOA-X, where X = Br, Cl, AuCl4-xBrx, AuBr4/Br and AuCl4-xBrx/Br) were investigated to measure the extraction of water into the organic phase. 1H NMR and DFTmore » based NMR shielding calculations indicated that deshielding of water is due to hydration of the anion and not the formation of the aqueous core of a reverse micelle. DOSYNMR results were consistent with the formation of small aggregates at typical Brust-Schiffrin synthesis concentrations. The extent of aggregation correlated with the size and electronegativity of the anion and was analyzed with a modified, isodesmic, indefinite aggregation model. The substitution of bromoauric acid for chlororoauric acid at conditions emulating the Brust-Schiffrin synthesis increased the aggregation of the quaternary ammonium complex. The increase in aggregation corresponded with an increase in the size of the produced nanoparticles from 4.3 to 4.6 nm. Understanding the selfassembly and supramolecular structure of precursors in the Brust-Schiffrin synthesis will enable further refinement of models that predict the growth of noble metal nanoparticles.« less

  3. CuInS2 Films Deposited by Aerosol-Assisted Chemical Vapor Deposition Using Ternary Single-Source Precursors

    NASA Technical Reports Server (NTRS)

    Jin, Michael; Banger, Kal; Harris, Jerry; Hepp, Aloysius

    2003-01-01

    Polycrystalline CuInS2 films were deposited by aerosol-assisted chemical vapor deposition using both solid and liquid ternary single-source precursors (SSPs) which were prepared in-house. Films with either (112) or (204/220) preferred orientation, had a chalcopyrite structure, and (112)-oriented films contained more copper than (204/220)-oriented films. The preferred orientation of the film is likely related to the decomposition and reaction kinetics associated with the molecular structure of the precursors at the substrate. Interestingly, the (204/220)-oriented films were always In-rich and were accompanied by a secondary phase. From the results of post-growth annealing, etching experiments, and Raman spectroscopic data, the secondary phase was identified as an In-rich compound. On the contrary, (112)-oriented films were always obtained with a minimal amount of the secondary phase, and had a maximum grain size of about 0.5 micron. Electrical and optical properties of all the films grown were characterized. They all showed p-type conduction with an electrical resistivity between 0.1 and 30 Omega-cm, and an optical band gap of approximately 1.46 eV +/- 0.02, as deposited. The material properties of deposited films revealed this methodology of using SSPs for fabricating chalcopyrite-based solar cells to be highly promising.

  4. Precursor wave structure, prereversal vertical drift, and their relative roles in the development of post sunset equatorial spread-F

    NASA Astrophysics Data System (ADS)

    Abdu, Mangalathayil; Sobral, José; alam Kherani, Esfhan; Batista, Inez S.; Souza, Jonas

    2016-07-01

    The characteristics of large-scale wave structure in the equatorial bottomside F region that are present during daytime as precursor to post sunset development of the spread F/plasma bubble irregularities are investigated in this paper. Digisonde data from three equatorial sites in Brazil (Fortaleza, Sao Luis and Cachimbo) for a period of few months at low to medium/high solar activity phases are analyzed. Small amplitude oscillations in the F layer true heights, representing wave structure in polarization electric field, are identified as upward propagating gravity waves having zonal scale of a few hundred kilometers. Their amplitudes undergo amplification towards sunset, and depending on the amplitude of the prereversal vertical drift (PRE) they may lead to post sunset generation of ESF/plasma bubble irregularities. On days of their larger amplitudes they appear to occur in phase coherence on all days, and correspondingly the PRE vertical drift velocities are larger than on days of the smaller amplitudes of the wave structure that appear at random phase on the different days. The sustenance of these precursor waves structures is supported by the relatively large ratio (approaching unity) of the F region-to- total field line integrated Pedersen conductivities as calculated using the SUPIM simulation of the low latitude ionosphere. This study examines the role of the wave structure relative to that of the prereversal vertical drift in the post sunset spread F irregularity development.

  5. Mesoporous Titania Powders: The Role of Precursors, Ligand Addition and Calcination Rate on Their Morphology, Crystalline Structure and Photocatalytic Activity

    PubMed Central

    Masolo, Elisabetta; Meloni, Manuela; Garroni, Sebastiano; Mulas, Gabriele; Enzo, Stefano; Baró, Maria Dolors; Rossinyol, Emma; Rzeszutek, Agnieszka; Herrmann-Geppert, Iris; Pilo, Maria

    2014-01-01

    We evaluate the influence of the use of different titania precursors, calcination rate, and ligand addition on the morphology, texture and phase content of synthesized mesoporous titania samples, parameters which, in turn, can play a key role in titania photocatalytic performances. The powders, obtained through the evaporation-induced self-assembly method, are characterized by means of ex situ X-Ray Powder Diffraction (XRPD) measurements, N2 physisorption isotherms and transmission electron microscopy. The precursors are selected basing on two different approaches: the acid-base pair, using TiCl4 and Ti(OBu)4, and a more classic route with Ti(OiPr)4 and HCl. For both precursors, different specimens were prepared by resorting to different calcination rates and with and without the addition of acetylacetone, that creates coordinated species with lower hydrolysis rates, and with different calcination rates. Each sample was employed as photoanode and tested in the water splitting reaction by recording I-V curves and comparing the results with commercial P25 powders. The complex data framework suggests that a narrow pore size distribution, due to the use of acetylacetone, plays a major role in the photoactivity, leading to a current density value higher than that of P25. PMID:28344237

  6. Bortezomib with chemotherapy is highly active in advanced B-precursor acute lymphoblastic leukemia: Therapeutic Advances in Childhood Leukemia & Lymphoma (TACL) Study.

    PubMed

    Messinger, Yoav H; Gaynon, Paul S; Sposto, Richard; van der Giessen, Jeannette; Eckroth, Elena; Malvar, Jemily; Bostrom, Bruce C

    2012-07-12

    Therapy of relapsed pediatric acute lymphoblastic leukemia (ALL) is hampered by low remission rates and high toxicity, especially in second and subsequent relapses. Our phase 1 study, T2005-003, showed that the combination of bortezomib with vincristine, dexamethasone, pegylated asparaginase, and doxorubicin had acceptable toxicity. We report the phase 2 expansion of this combination in patients with relapsed ALL who failed 2-3 previous regimens. Twenty-two patients with relapsed ALL were treated with bortezomib combined with this regimen; their ages ranged from 1 to 22 years, and they had either B-precursor ALL (n = 20) or T-cell ALL (n = 2). Grade 3 peripheral neuropathy developed in 2 (9%) patients. After 3 patients died from bacterial infections, treatment with vancomycin, levofloxacin, and voriconazole prophylaxis resulted in no further infectious mortality in the last 6 patients. Fourteen patients achieved complete remission (CR), and 2 achieved CR without platelet recovery, for an overall 73% response rate, meeting predefined criteria allowing for early closure. B-precursor patients faired best, with 16 of 20 (80%) CR + CR without platelet recovery, whereas the 2 patients with T-cell ALL did not respond. Thus, this combination of bortezomib with chemotherapy is active in B-precursor ALL, and prophylactic antibiotics may be useful in reducing mortality. Bortezomib merits further evaluation in combination therapy in pediatric B-precursor ALL. This study is registered at http://www.clinicaltrials.gov as NCT00440726.

  7. Emission of discrete vortex rings by a vibrating grid in superfluid 3He-B: a precursor to quantum turbulence.

    PubMed

    Bradley, D I; Clubb, D O; Fisher, S N; Guénault, A M; Haley, R P; Matthews, C J; Pickett, G R; Tsepelin, V; Zaki, K

    2005-07-15

    We report a transition in the vorticity generated by a grid moving in the B phase of superfluid 3He at Tprecursors to the developed turbulence. Furthermore we believe that this may be a feature of all quantum turbulence arising from repetitive mechanical agitation.

  8. Moon Phases

    ERIC Educational Resources Information Center

    Riddle, Bob

    2010-01-01

    When teaching Moon phases, the focus seems to be on the sequence of Moon phases and, in some grade levels, how Moon phases occur. Either focus can sometimes be a challenge, especially without the use of models and observations of the Moon. In this month's column, the author describes some of the lessons that he uses to teach the phases of the Moon…

  9. Monitoring of precursor landslide surface deformation using InSAR image in Kuchi-Sakamoto, Shizuoka Prefecture, Japan

    NASA Astrophysics Data System (ADS)

    Sato, H. P.; Nakajima, H.; Nakano, T.; Daimaru, H.

    2014-12-01

    Synthetic Aperture Radar (SAR) is the technique to obtain ground surface images using microwave that is emitted from and received on the antenna. The Kuchi-Sakamoto area, 2.2 km2 in precipitous mountains, central Japan, has suffered from frequent landslides, and slow landslide surface deformation has been monitored by on-site extensometer; however, such the monitoring method cannot detect the deformation in the whole area. Because satellite InSAR is effective tool to monitor slow landslide suface deformation, it is a promising tool for detecting precursor deformation and preparing effective measures against serious landslide disasters. In this study Advanced Land Observing Satellite (ALOS) / Phased Array type L-band SAR (PALSAR) data were used, and InSAR images were produced from the PALSAR data that were observed between 5 Sep 2008 and 21 Oct 2008 (from descending orbit) and between 20 Jul 2008 and 7 Sep 2009 (from ascending orbit). InSAR image from descending orbit was found to detect clear precursor landslide surface deformation on a slope; however, InSAR image on ascending orbit did not always detect clear precursor deformation. It is thought to be related with atmospheric moisture condition, length of observation baseline and so on. Furthermore, after phase unwrapping on InSAR images, 2.5-dimensional deformation was analized. This analysis needed both ascending and descending InSAR images and culculated quasi east-west deformation component (Figs. (a) and (b)) and quasi up-down deformation component (Figs. (c) and (d)). The resulting 2.5D calculation gave westward deformation and mixture of upward and downward deformations on the precursor landslide surface deformation slope (blue circles in Figs. (c) and (d)), where remarkable disrupted deep landslide occurred during Nov 2012 and 25 Jun 2013, judging from result of airborne LiDAR survey and field survey; the occurrence date is not precisely identified. The figure remains the issue that eliminating "real

  10. Copper stabilization via spinel formation during the sintering of simulated copper-laden sludge with aluminum-rich ceramic precursors.

    PubMed

    Tang, Yuanyuan; Chui, Stephen Sin-Yin; Shih, Kaimin; Zhang, Lingru

    2011-04-15

    The feasibility of incorporating copper-laden sludge into low-cost ceramic products, such as construction ceramics, was investigated by sintering simulated copper-laden sludge with four aluminum-rich ceramic precursors. The results indicated that all of these precursors (γ-Al(2)O(3), corundum, kaolinite, mullite) could crystallochemically stabilize the hazardous copper in the more durable copper aluminate spinel (CuAl(2)O(4)) structure. To simulate the process of copper transformation into a spinel structure, CuO was mixed with the four aluminum-rich precursors, and fired at 650-1150 °C for 3 h. The products were examined using powder X-ray diffraction (XRD) and scanning electron microscopic techniques. The efficiency of copper transformation among crystalline phases was quantitatively determined through Rietveld refinement analysis of the XRD data. The sintering experiment revealed that the optimal sintering temperature for CuAl(2)O(4) formation was around 1000 °C and that the efficiency of copper incorporation into the crystalline CuAl(2)O(4) structure after 3 h of sintering ranged from 40 to 95%, depending on the type of aluminum precursor used. Prolonged leaching tests were carried out by using acetic acid with an initial pH value of 2.9 to leach CuO and CuAl(2)O(4) samples for 22 d. The sample leachability analysis revealed that the CuAl(2)O(4) spinel structure was more superior to stabilize copper, and suggested a promising and reliable technique for incorporating copper-laden sludge or its incineration ash into usable ceramic products. Such results also demonstrated the potential of a waste-to-resource strategy by using waste materials as part of the raw materials with the attainable temperature range used in the production of ceramics.

  11. Possibility to study ionospheric earthquakes precursors using CubeSats

    NASA Astrophysics Data System (ADS)

    Korepanov, Valery; Lappas, Vaios

    It is generally accepted that the earthquakes (EQ) are the most dangerous natural phenomena leading to the multiple losses in human lives and economics. The space observations must be included into the global chain of the EQ precursors monitoring at least as the initial warning to pay greater attention to the ground segment data. As the common opinion agrees, only in combination of multiple observation sites and set of monitored parameters the further progress at the way to raise EQ precursors detection probability may be obtained. There is necessary to answer two important questions before to plan any experiment to study ionospheric precursors of EQ. First one - whether the variations in the ionosphere definitely connected with the EQ preparation process do exist, and the second one - if they do, whether using these signals the precursors of EQ can be reliably identified and used for, if not prediction, then for the warning that the EQ in the given area approaches. The first successful mission dedicated to this problem solution was DEMETER (in orbit during more than 6 years from June 2004 until December 2010). The statistics of this study is impressive: altogether, about 9000 EQs with magnitude larger than M = 5.0 and depth lower than 40 km occurred all over the world during the analyzed period. In the result, the conclusion made there suggests that, obviously, there are real perturbations in the ionosphere connected with the seismic activity, but they are rather weak and at the present stage of data processing may be revealed only with the help of statistical analysis. To realize the study of ionospheric precursors, first it is imperative to clarify the mechanism of energy transfer along the chain “lithosphere-atmosphere-ionosphere”. Many hypotheses of such a mechanism exist, from which the mostly supported are fair weather currents (FWC) and atmospheric gravity waves (AGW), both of which have their pros and contras. The following minimal set of physical

  12. Nanoscale Transforming Mineral Phases in Fresh Nacre

    DOE PAGES

    DeVol, Ross T.; Sun, Chang-Yu; Marcus, Matthew A.; ...

    2015-09-24

    Nacre, or mother-of-pearl, the iridescent inner layer of many mollusk shells, is a biomineral lamellar composite of aragonite (CaCO 3) and organic sheets. Biomineralization frequently occurs via transient amorphous precursor phases, crystallizing into the final stable biomineral. In nacre, despite extensive attempts, amorphous calcium carbonate (ACC) precursors have remained elusive. They were inferred from non-nacre-forming larval shells, or from a residue of amorphous material surrounding mature gastropod nacre tablets, and have only once been observed in bivalve nacre. Here we present the first direct observation of ACC precursors to nacre formation, obtained from the growth front of nacre in gastropodmore » shells from red abalone (Haliotis rufescens), using synchrotron spectromicroscopy. Surprisingly, the abalone nacre data show the same ACC phases that are precursors to calcite (CaCO 3) formation in sea urchin spicules, and not proto-aragonite or poorly crystalline aragonite (pAra), as expected for aragonitic nacre. In contrast, we find pAra in coral.« less

  13. Nanoscale Transforming Mineral Phases in Fresh Nacre.

    PubMed

    DeVol, Ross T; Sun, Chang-Yu; Marcus, Matthew A; Coppersmith, Susan N; Myneni, Satish C B; Gilbert, Pupa U P A

    2015-10-21

    Nacre, or mother-of-pearl, the iridescent inner layer of many mollusk shells, is a biomineral lamellar composite of aragonite (CaCO3) and organic sheets. Biomineralization frequently occurs via transient amorphous precursor phases, crystallizing into the final stable biomineral. In nacre, despite extensive attempts, amorphous calcium carbonate (ACC) precursors have remained elusive. They were inferred from non-nacre-forming larval shells, or from a residue of amorphous material surrounding mature gastropod nacre tablets, and have only once been observed in bivalve nacre. Here we present the first direct observation of ACC precursors to nacre formation, obtained from the growth front of nacre in gastropod shells from red abalone (Haliotis rufescens), using synchrotron spectromicroscopy. Surprisingly, the abalone nacre data show the same ACC phases that are precursors to calcite (CaCO3) formation in sea urchin spicules, and not proto-aragonite or poorly crystalline aragonite (pAra), as expected for aragonitic nacre. In contrast, we find pAra in coral.

  14. Selective Disparity of Ordinary Chondritic Precursors in Micrometeorite Flux

    NASA Astrophysics Data System (ADS)

    Rudraswami, N. G.; Fernandes, D.; Naik, A. K.; Shyam Prasad, M.; Carrillo-Sánchez, J. D.; Plane, J. M. C.; Feng, W.; Taylor, S.

    2018-01-01

    All known extraterrestrial dust (micrometeoroids) entering the Earth’s atmosphere is anticipated to have a significant contribution from ordinary chondritic precursors, as seen in meteorites, but this is an apparent contradiction that needs to be addressed. Ordinary chondrites represent a minor contribution to the overall meteor influx compared to carbonaceous chondrites, which are largely dominated by CI and/or CM chondrites. However, the near-Earth asteroid population presents a scenario with sufficient scope for generation of dust-sized debris from ordinary chondritic sources. The bulk chemical composition of 3255 micrometeorites (MMs) collected from Antarctica and deep-sea sediments has shown Mg/Si largely dominated by carbonaceous chondrites, and less than 10% having ordinary chondritic precursors. The chemical ablation model is combined with different initial chondritic compositions (CI, CV, L, LL, H), and the results clearly indicate that high-density (≥2.8 g cm‑3) precursors, such as CV and ordinary chondrites in the size range 100–700 μm and zenith angle 0°–70°, ablate at much faster rates and lose their identity even before reaching the Earth’s surface and hence are under-represented in our collections. Moreover, their ability to survive as MMs remains grim for high-velocity micrometeoroids (>16 km s‑1). The elemental ratio for CV and ordinary chondrites are also similar to each other irrespective of the difference in the initial chemical composition. In conclusion, MMs belonging to ordinary chondritic precursors’ concentrations may not be insignificant in thermosphere, as they are found on Earth’s surface.

  15. Accident Precursor Analysis and Management: Reducing Technological Risk Through Diligence

    NASA Technical Reports Server (NTRS)

    Phimister, James R. (Editor); Bier, Vicki M. (Editor); Kunreuther, Howard C. (Editor)

    2004-01-01

    Almost every year there is at least one technological disaster that highlights the challenge of managing technological risk. On February 1, 2003, the space shuttle Columbia and her crew were lost during reentry into the atmosphere. In the summer of 2003, there was a blackout that left millions of people in the northeast United States without electricity. Forensic analyses, congressional hearings, investigations by scientific boards and panels, and journalistic and academic research have yielded a wealth of information about the events that led up to each disaster, and questions have arisen. Why were the events that led to the accident not recognized as harbingers? Why were risk-reducing steps not taken? This line of questioning is based on the assumption that signals before an accident can and should be recognized. To examine the validity of this assumption, the National Academy of Engineering (NAE) undertook the Accident Precursors Project in February 2003. The project was overseen by a committee of experts from the safety and risk-sciences communities. Rather than examining a single accident or incident, the committee decided to investigate how different organizations anticipate and assess the likelihood of accidents from accident precursors. The project culminated in a workshop held in Washington, D.C., in July 2003. This report includes the papers presented at the workshop, as well as findings and recommendations based on the workshop results and committee discussions. The papers describe precursor strategies in aviation, the chemical industry, health care, nuclear power and security operations. In addition to current practices, they also address some areas for future research.

  16. Radiative precursors driven by converging blast waves in noble gases

    SciT

    Burdiak, G. C.; Lebedev, S. V.; Harvey-Thompson, A. J.

    2014-03-15

    A detailed study of the radiative precursor that develops ahead of converging blast waves in gas-filled cylindrical liner z-pinch experiments is presented. The experiment is capable of magnetically driving 20 km s{sup −1} blast waves through gases of densities of the order 10{sup −5} g cm{sup −3} (see Burdiak et al. [High Energy Density Phys. 9(1), 52–62 (2013)] for a thorough description). Data were collected for Ne, Ar, and Xe gas-fills. The geometry of the setup allows a determination of the plasma parameters both in the precursor and across the shock, along a nominally uniform line of sight that is perpendicularmore » to the propagation of the shock waves. Radiation from the shock was able to excite NeI, ArII, and XeII/XeIII precursor spectral features. It is shown that the combination of interferometry and optical spectroscopy data is inconsistent with upstream plasmas being in LTE. Specifically, electron density gradients do not correspond to any apparent temperature change in the emission spectra. Experimental data are compared to 1D radiation hydrodynamics HELIOS-CR simulations and to PrismSPECT atomic physics calculations to assist in a physical interpretation of the observations. We show that upstream plasma is likely in the process of being radiatively heated and that the emission from a small percentage of ionised atoms within a cool background plasma dominates the emission spectra. Experiments were carried out on the MAGPIE and COBRA pulsed-power facilities at Imperial College London and Cornell University, respectively.« less

  17. Proliferative and transcriptional identity of distinct classes of neural precursors in the mammalian olfactory epithelium.

    PubMed

    Tucker, Eric S; Lehtinen, Maria K; Maynard, Tom; Zirlinger, Mariela; Dulac, Catherine; Rawson, Nancy; Pevny, Larysa; Lamantia, Anthony-Samuel

    2010-08-01

    Neural precursors in the developing olfactory epithelium (OE) give rise to three major neuronal classes - olfactory receptor (ORNs), vomeronasal (VRNs) and gonadotropin releasing hormone (GnRH) neurons. Nevertheless, the molecular and proliferative identities of these precursors are largely unknown. We characterized two precursor classes in the olfactory epithelium (OE) shortly after it becomes a distinct tissue at midgestation in the mouse: slowly dividing self-renewing precursors that express Meis1/2 at high levels, and rapidly dividing neurogenic precursors that express high levels of Sox2 and Ascl1. Precursors expressing high levels of Meis genes primarily reside in the lateral OE, whereas precursors expressing high levels of Sox2 and Ascl1 primarily reside in the medial OE. Fgf8 maintains these expression signatures and proliferative identities. Using electroporation in the wild-type embryonic OE in vitro as well as Fgf8, Sox2 and Ascl1 mutant mice in vivo, we found that Sox2 dose and Meis1 - independent of Pbx co-factors - regulate Ascl1 expression and the transition from lateral to medial precursor state. Thus, we have identified proliferative characteristics and a dose-dependent transcriptional network that define distinct OE precursors: medial precursors that are most probably transit amplifying neurogenic progenitors for ORNs, VRNs and GnRH neurons, and lateral precursors that include multi-potent self-renewing OE neural stem cells.

  18. Proliferative and transcriptional identity of distinct classes of neural precursors in the mammalian olfactory epithelium

    PubMed Central

    Tucker, Eric S.; Lehtinen, Maria K.; Maynard, Tom; Zirlinger, Mariela; Dulac, Catherine; Rawson, Nancy; Pevny, Larysa; LaMantia, Anthony-Samuel

    2010-01-01

    Neural precursors in the developing olfactory epithelium (OE) give rise to three major neuronal classes – olfactory receptor (ORNs), vomeronasal (VRNs) and gonadotropin releasing hormone (GnRH) neurons. Nevertheless, the molecular and proliferative identities of these precursors are largely unknown. We characterized two precursor classes in the olfactory epithelium (OE) shortly after it becomes a distinct tissue at midgestation in the mouse: slowly dividing self-renewing precursors that express Meis1/2 at high levels, and rapidly dividing neurogenic precursors that express high levels of Sox2 and Ascl1. Precursors expressing high levels of Meis genes primarily reside in the lateral OE, whereas precursors expressing high levels of Sox2 and Ascl1 primarily reside in the medial OE. Fgf8 maintains these expression signatures and proliferative identities. Using electroporation in the wild-type embryonic OE in vitro as well as Fgf8, Sox2 and Ascl1 mutant mice in vivo, we found that Sox2 dose and Meis1 – independent of Pbx co-factors – regulate Ascl1 expression and the transition from lateral to medial precursor state. Thus, we have identified proliferative characteristics and a dose-dependent transcriptional network that define distinct OE precursors: medial precursors that are most probably transit amplifying neurogenic progenitors for ORNs, VRNs and GnRH neurons, and lateral precursors that include multi-potent self-renewing OE neural stem cells. PMID:20573694

  19. The wireless networking system of Earthquake precursor mobile field observation

    NASA Astrophysics Data System (ADS)

    Wang, C.; Teng, Y.; Wang, X.; Fan, X.; Wang, X.

    2012-12-01

    The mobile field observation network could be real-time, reliably record and transmit large amounts of data, strengthen the physical signal observations in specific regions and specific period, it can improve the monitoring capacity and abnormal tracking capability. According to the features of scatter everywhere, a large number of current earthquake precursor observation measuring points, networking technology is based on wireless broadband accessing McWILL system, the communication system of earthquake precursor mobile field observation would real-time, reliably transmit large amounts of data to the monitoring center from measuring points through the connection about equipment and wireless accessing system, broadband wireless access system and precursor mobile observation management center system, thereby implementing remote instrument monitoring and data transmition. At present, the earthquake precursor field mobile observation network technology has been applied to fluxgate magnetometer array geomagnetic observations of Tianzhu, Xichang,and Xinjiang, it can be real-time monitoring the working status of the observational instruments of large area laid after the last two or three years, large scale field operation. Therefore, it can get geomagnetic field data of the local refinement regions and provide high-quality observational data for impending earthquake tracking forecast. Although, wireless networking technology is very suitable for mobile field observation with the features of simple, flexible networking etc, it also has the phenomenon of packet loss etc when transmitting a large number of observational data due to the wireless relatively weak signal and narrow bandwidth. In view of high sampling rate instruments, this project uses data compression and effectively solves the problem of data transmission packet loss; Control commands, status data and observational data transmission use different priorities and means, which control the packet loss rate within

  20. Vortex multiplication in applied flow: A precursor to superfluid turbulence.

    PubMed

    Finne, A P; Eltsov, V B; Eska, G; Hänninen, R; Kopu, J; Krusius, M; Thuneberg, E V; Tsubota, M

    2006-03-03

    A surface-mediated process is identified in 3He-B which generates vortices at a roughly constant rate. It precedes a faster form of turbulence where intervortex interactions dominate. This precursor becomes observable when vortex loops are introduced in low-velocity rotating flow at sufficiently low mutual friction dissipation at temperatures below 0.5Tc. Our measurements indicate that the formation of new loops is associated with a single vortex interacting in the applied flow with the sample boundary. Numerical calculations show that the single-vortex instability arises when a helical Kelvin wave expands from a reconnection kink at the wall and then intersects again with the wall.

  1. Gelcasting polymeric precursors for producing net-shaped graphites

    DOEpatents

    Klett, James W.; Janney, Mark A.

    2002-01-01

    The present invention discloses a method for molding complex and intricately shaped high density monolithic carbon, carbon-carbon, graphite, and thermoplastic composites using gelcasting technology. The method comprising a polymeric carbon precursor, a solvent, a dispersant, an anti-foaming agent, a monomer system, and an initiator system. The components are combined to form a suspension which is poured into a mold and heat-treated to form a thermoplastic part. The thermoplastic part can then be further densified and heat-treated to produce a high density carbon or graphite composite. The present invention also discloses the products derived from this method.

  2. Cytoplasmic Incorporation of a Ribonucleic Acid Precursor in Amoeba proteus

    PubMed Central

    Plaut, Walter; Rustad, Ronald C.

    1957-01-01

    The question of RNA synthesis in enucleate cytoplasm of Amoeba has been approached experimentally by incubating enucleate amoebae in a labelled RNA precursor and determining the incorporation into RNA autoradiographically. The results indicate that there is a cytoplasmic incorporation mechanism which can operate in the absence of the nucleus. A comparison is made between Acetabularia and Amoeba with respect to the origins of cytoplasmic RNA. It is concluded that the existing data are consistent with the assumption that some cytoplasmic RNA is of nuclear origin in both organisms. PMID:13449107

  3. Cytoplasmic incorporation of a ribonucleic acid precursor in Amoeba proteus.

    PubMed

    PLAUT, W; RUSTAD, R C

    1957-07-25

    The question of RNA synthesis in enucleate cytoplasm of Amoeba has been approached experimentally by incubating enucleate amoebae in a labelled RNA precursor and determining the incorporation into RNA autoradiographically. The results indicate that there is a cytoplasmic incorporation mechanism which can operate in the absence of the nucleus. A comparison is made between Acetabularia and Amoeba with respect to the origins of cytoplasmic RNA. It is concluded that the existing data are consistent with the assumption that some cytoplasmic RNA is of nuclear origin in both organisms.

  4. Aroma Precursors in Grapes and Wine: Flavor Release during Wine Production and Consumption.

    PubMed

    Parker, Mango; Capone, Dimitra L; Francis, I Leigh; Herderich, Markus J

    2018-03-14

    Pioneering investigations into precursors of fruity and floral flavors established the importance of terpenoid and C 13 -norisoprenoid glycosides to the flavor of aromatic wines. Nowadays flavor precursors in grapes and wine are known to be structurally diverse, encompassing glycosides, amino acid conjugates, odorless volatiles, hydroxycinnamic acids, and many others. Flavor precursors mainly originate in the grape berry but also from oak or other materials involved in winemaking. Flavors are released from precursors during crushing and subsequent production steps by enzymatic and nonenzymatic transformations, via microbial glycosidases, esterases, C-S lyases, and decarboxylases, and through acid-catalyzed hydrolysis and chemical rearrangements. Flavors can also be liberated from glycosides and amino acid conjugates by oral microbiota. Hence, it is increasingly likely that flavor precursors contribute to retronasal aroma formation through in-mouth release during consumption, prompting a shift in focus from identifying aroma precursors in grapes to understanding aroma precursors present in bottled wine.

  5. Strain-induced dimensionality crossover of precursor modulations in Ni2MnGa

    SciT

    Nie, Zhihua; Wang, Yandong; Shang, Shunli

    2015-01-01

    Precursor modulations often occur in functional materials like magnetic shape memory alloys, ferroelectrics, and superconductors. In this letter, we have revealed the underlying mechanism of the precursor modulations in ferromagnetic shape memory alloys Ni2MnGa by combining synchrotron-based x-ray diffraction experiments and first-principles phonon calculations. We discovered the precursor modulations along [011] direction can be eliminated with [001] uniaxial loading, while the precursor modulations or premartensite can be totally suppressed by hydrostatic pressure condition. The TA2 phonon anomaly is sensitive to stress induced lattice strain, and the entire TA2 branch is stabilized along the directions where precursor modulations are eliminated bymore » external stress. Our discovery bridges precursor modulations and phonon anomalies, and sheds light on the microscopic mechanism of the two-step superelasticity in precursor martensite.« less

  6. Strain-induced dimensionality crossover of precursor modulations in Ni{sub 2}MnGa

    SciT

    Nie, Zhihua, E-mail: zhihua-nie@yahoo.com, E-mail: ydwang@neu.edu.cn; Wang, Yandong, E-mail: zhihua-nie@yahoo.com, E-mail: ydwang@neu.edu.cn; Shang, Shunli

    2015-01-12

    Precursor modulations often occur in functional materials like magnetic shape memory alloys, ferroelectrics, and superconductors. In this letter, we have revealed the underlying mechanism of the precursor modulations in ferromagnetic shape memory alloys Ni{sub 2}MnGa by combining synchrotron-based x-ray diffraction experiments and first-principles phonon calculations. We discovered the precursor modulations along [011] direction can be eliminated with [001] uniaxial loading, while the precursor modulations or premartensite can be totally suppressed by hydrostatic pressure condition. The TA{sub 2} phonon anomaly is sensitive to stress induced lattice strain, and the entire TA{sub 2} branch is stabilized along the directions where precursor modulationsmore » are eliminated by external stress. Our discovery bridges precursor modulations and phonon anomalies, and sheds light on the microscopic mechanism of the two-step superelasticity in precursor martensite.« less

  7. Late stage erythroid precursor production is impaired in mice with chronic inflammation.

    PubMed

    Prince, Olivier D; Langdon, Jacqueline M; Layman, Andrew J; Prince, Ian C; Sabogal, Miguel; Mak, Howard H; Berger, Alan E; Cheadle, Chris; Chrest, Francis J; Yu, Qilu; Andrews, Nancy C; Xue, Qian-Li; Civin, Curt I; Walston, Jeremy D; Roy, Cindy N

    2012-11-01

    We and others have shown previously that over-expression of hepcidin antimicrobial peptide, independently of inflammation, induces several features of anemia of inflammation and chronic disease, including hypoferremia, sequestration of iron stores and iron-restricted erythropoiesis. Because the iron-restricted erythropoiesis evident in hepcidin transgenic mice differs from the normocytic, normochromic anemia most often observed in anemia of inflammation, we tested the hypothesis that chronic inflammation may contribute additional features to anemia of inflammation which continue to impair erythropoiesis following the acute phase of inflammation in which hepcidin is active. We compared erythropoiesis and iron handling in mice with turpentine-induced sterile abscesses with erythropoiesis and iron handling in hepcidin transgenic mice. We compared erythrocyte indices, expression of genes in the hepcidin regulatory pathway, tissue iron distribution, expression of heme and iron transport genes in splenic macrophages, the phenotype of erythroid maturation and chloromethyl dichlorodihydrofluorescein diacetate, acetyl ester fluorescence. Mice with sterile abscesses exhibited an intense, acute inflammatory phase followed by a mild to moderate chronic inflammatory phase. We found that erythrocytes in mice with sterile abscesses were normocytic and normochromic in contrast to those in hepcidin transgenic mice. We also observed that although hypoferremia resolved in the late phases of inflammation, erythropoiesis remained suppressed, with evidence of inefficient maturation of erythroid precursors in the bone marrow of mice with sterile abscesses. Finally, we observed increased oxidative stress in erythroid progenitors and circulating erythrocytes of mice with sterile abscesses which was not evident in hepcidin transgenic mice. Our results suggest that chronic inflammation inhibits late stages of erythroid production in the turpentine-induced sterile abscess model and induces

  8. Late stage erythroid precursor production is impaired in mice with chronic inflammation

    PubMed Central

    Prince, Olivier D.; Langdon, Jacqueline M.; Layman, Andrew J.; Prince, Ian C.; Sabogal, Miguel; Mak, Howard H.; Berger, Alan E.; Cheadle, Chris; Chrest, Francis J.; Yu, Qilu; Andrews, Nancy C.; Xue, Qian-Li; Civin, Curt I.; Walston, Jeremy D.; Roy, Cindy N.

    2012-01-01

    Background We and others have shown previously that over-expression of hepcidin antimicrobial peptide, independently of inflammation, induces several features of anemia of inflammation and chronic disease, including hypoferremia, sequestration of iron stores and iron-restricted erythropoiesis. Because the iron-restricted erythropoiesis evident in hepcidin transgenic mice differs from the normocytic, normochromic anemia most often observed in anemia of inflammation, we tested the hypothesis that chronic inflammation may contribute additional features to anemia of inflammation which continue to impair erythropoiesis following the acute phase of inflammation in which hepcidin is active. Design and Methods We compared erythropoiesis and iron handling in mice with turpentine-induced sterile abscesses with erythropoiesis and iron handling in hepcidin transgenic mice. We compared erythrocyte indices, expression of genes in the hepcidin regulatory pathway, tissue iron distribution, expression of heme and iron transport genes in splenic macrophages, the phenotype of erythroid maturation and chloromethyl dichlorodihydrofluorescein diacetate, acetyl ester fluorescence. Results Mice with sterile abscesses exhibited an intense, acute inflammatory phase followed by a mild to moderate chronic inflammatory phase. We found that erythrocytes in mice with sterile abscesses were normocytic and normochromic in contrast to those in hepcidin transgenic mice. We also observed that although hypoferremia resolved in the late phases of inflammation, erythropoiesis remained suppressed, with evidence of inefficient maturation of erythroid precursors in the bone marrow of mice with sterile abscesses. Finally, we observed increased oxidative stress in erythroid progenitors and circulating erythrocytes of mice with sterile abscesses which was not evident in hepcidin transgenic mice. Conclusions Our results suggest that chronic inflammation inhibits late stages of erythroid production in the

  9. Persistence of perfluoroalkyl acid precursors in AFFF-impacted groundwater and soil.

    PubMed

    Houtz, Erika F; Higgins, Christopher P; Field, Jennifer A; Sedlak, David L

    2013-08-06

    Several classes of polyfluorinated chemicals that are potential precursors to the perfluorinated carboxylates and sulfonates are present in aqueous film-forming foams (AFFF). To assess the persistence of these AFFF-derived precursors, groundwater, soil, and aquifer solids were obtained in 2011 from an unlined firefighter training area at a U.S. Air Force Base where AFFF was regularly used between 1970 and 1990. To measure the total concentration of perfluorinated carboxylate and sulfonate precursors in archived AFFF formulations and AFFF-impacted environmental samples, a previously developed assay that uses hydroxyl radical to oxidize precursors to perfluorinated carboxylates was adapted for these media. This assay was employed along with direct measurement of 22 precursors found in AFFF and a suite of other poly- and perfluoroalkyl substances (PFASs). On a molar basis, precursors accounted for 41-100% of the total concentration of PFASs in archived AFFF formulations. In the training area, precursors measured by the oxidation assay accounted for an average of 23% and 28% of total PFASs (i.e., precursors and perfluorinated carboxylates and sulfonates) in groundwater and solids samples, respectively. One precursor in AFFF, perfluorohexane sulfonamide amine, was observed on several highly contaminated soil and aquifer solids samples, but no other precursors present in AFFF formulations were detected in any samples at this field site. Suspected intermediate transformation products of precursors in AFFF that were directly measured accounted for approximately half of the total precursor concentration in samples from the training site. The fraction of PFASs consisting of perfluorinated carboxylates and sulfonates was greater in groundwater and solid samples than in any archived AFFF formulations, suggesting that much of the mass of precursors released at the site was converted to perfluorinated carboxylates and sulfonates. The precursors that have persisted at this site

  10. Methods of making copper selenium precursor compositions with a targeted copper selenide content and precursor compositions and thin films resulting therefrom

    DOEpatents

    Curtis, Calvin J [Lakewood, CO; Miedaner, Alexander [Boulder, CO; van Hest, Marinus Franciscus Antonius Maria; Ginley, David S [Evergreen, CO; Leisch, Jennifer [Denver, CO; Taylor, Matthew [West Simsbury, CT; Stanbery, Billy J [Austin, TX

    2011-09-20

    Precursor compositions containing copper and selenium suitable for deposition on a substrate to form thin films suitable for semi-conductor applications. Methods of forming the precursor compositions using primary amine solvents and methods of forming the thin films wherein the selection of temperature and duration of heating controls the formation of a targeted species of copper selenide.

  11. Perfluoroalkyl Acids (PFAAs) and Selected Precursors in the Baltic Sea Environment: Do Precursors Play a Role in Food Web Accumulation of PFAAs?

    PubMed

    Gebbink, Wouter A; Bignert, Anders; Berger, Urs

    2016-06-21

    The present study examined the presence of perfluoroalkyl acids (PFAAs) and selected precursors in the Baltic Sea abiotic environment and guillemot food web, and investigated the relative importance of precursors in food web accumulation of PFAAs. Sediment, water, zooplankton, herring, sprat, and guillemot eggs were analyzed for perfluoroalkane sulfonic acids (PFSAs; C4,6,8,10) and perfluoroalkyl carboxylic acids (PFCAs; C6-15) along with six perfluoro-octane sulfonic acid (PFOS) precursors and 11 polyfluoroalkyl phosphoric acid diesters (diPAPs). FOSA, FOSAA and its methyl and ethyl derivatives (Me- and EtFOSAA), and 6:2/6:2 diPAP were detected in sediment and water. While FOSA and the three FOSAAs were detected in all biota, a total of nine diPAPs were only detected in zooplankton. Concentrations of PFOS precursors and diPAPs exceeded PFOS and PFCA concentrations, respectively, in zooplankton, but not in fish and guillemot eggs. Although PFOS precursors were present at all trophic levels, they appear to play a minor role in food web accumulation of PFOS based on PFOS precursor/PFOS ratios and PFOS and FOSA isomer patterns. The PFCA pattern in fish could not be explained by the intake pattern based on PFCAs and analyzed precursors, that is, diPAPs. Exposure to additional precursors might therefore be a dominant exposure pathway compared to direct PFCA exposure for fish.

  12. Synthesis and characterization of silver nanoparticles from (bis)alkylamine silver carboxylate precursors.

    PubMed

    Uznanski, Pawel; Zakrzewska, Joanna; Favier, Frederic; Kazmierski, Slawomir; Bryszewska, Ewa

    2017-01-01

    A comparative study of amine and silver carboxylate adducts [R 1 COOAg-2(R 2 NH 2 )] (R 1  = 1, 7, 11; R 2  = 8, 12) as a key intermediate in NPs synthesis is carried out via differential scanning calorimetry, solid-state FT-infrared spectroscopy, 13 C CP MAS NMR, powder X-ray diffraction and X-ray photoelectron spectroscopy, and various solution NMR spectroscopies ( 1 H and 13 C NMR, pulsed field gradient spin-echo NMR, and ROESY). It is proposed that carboxyl moieties in the presence of amine ligands are bound to silver ions via chelating bidentate type of coordination as opposed to bridging bidentate coordination of pure silver carboxylates resulting from the formation of dimeric units. All complexes are packed as lamellar bilayer structures. Silver carboxylate/amine complexes show one first-order melting transition. The evidence presented in this study shows that phase behavior of monovalent metal carboxylates are controlled, mainly, by head group bonding. In solution, insoluble silver salt is stabilized by amine molecules which exist in dynamic equilibrium. Using (bis)amine-silver carboxylate complex as precursor, silver nanoparticles were fabricated. During high-temperature thermolysis, the (bis)amine-carboxylate adduct decomposes to produce silver nanoparticles of small size. NPs are stabilized by strongly interacting carboxylate and trace amounts of amine derived from the silver precursor interacting with carboxylic acid. A corresponding aliphatic amide obtained from silver precursor at high-temperature reaction conditions is not taking part in the stabilization. Combining NMR techniques with FTIR, it was possible to follow an original stabilization mechanism. Graphical abstractThe synthesis of a series (bis)alkylamine silver(I) carboxylate complexes in nonpolar solvents were carried out and fully characterized both in the solid and solution. Carboxyl moieties in the presence of amine ligands are bound to silver ions via chelating bidentate type of

  13. Total N-nitrosamine Precursor Adsorption with Carbon Nanotubes: Elucidating Controlling Physiochemical Properties and Developing a Size-Resolved Precursor Surrogate

    NASA Astrophysics Data System (ADS)

    Needham, Erin Michelle

    As drinking water sources become increasingly impaired with nutrients and wastewater treatment plant (WWTP) effluent, formation of disinfection byproducts (DBPs)--such as trihalomethanes (THMs), dihaloacetonitriles (DHANs), and N-nitrosamines--during water treatment may also increase. N-nitrosamines may comprise the bulk of the chronic toxicity in treated drinking waters despite forming at low ng/L levels. This research seeks to elucidate physicochemical properties of carbon nanotubes (CNTs) for removal of DBP precursors, with an emphasis on total N-nitrosamines (TONO). Batch experiments with CNTs were completed to assess adsorption of THM, DHAN, and TONO precursors; physiochemical properties of CNTs were quantified through gas adsorption isotherms and x-ray photoelectron spectroscopy. Numerical modeling was used to elucidate characteristics of CNTs controlling DBP precursor adsorption. Multivariate models developed with unmodified CNTs revealed that surface carboxyl groups and, for TONO precursors, cumulative pore volume (CPV), controlled DBP precursor adsorption. Models developed with modified CNTs revealed that specific surface area controlled adsorption of THM and DHAN precursors while CPV and surface oxygen content were significant for adsorption of TONO precursors. While surrogates of THM and DHAN precursors leverage metrics from UV absorbance and fluorescence spectroscopy, a TONO precursor surrogate has proved elusive. This is important as measurements of TONO formation potential (TONOFP) require large sample volumes and long processing times, which impairs development of treatment processes. TONO precursor surrogates were developed using samples that had undergone oxidative or sorption treatments. Precursors were analyzed with asymmetric flow field-flow fractionation (AF4) with inline fluorescence detection (FLD) and whole water fluorescence excitation-emission matrices (EEMs). TONO precursor surrogates were discovered, capable of predicting changes in

  14. Study on Precursor Activity of the X1.6 Flare in the Great AR 12192 with SDO, IRIS, and Hinode

    NASA Astrophysics Data System (ADS)

    Bamba, Yumi; Lee, Kyoung-Sun; Imada, Shinsuke; Kusano, Kanya

    2017-05-01

    The physical properties and their contribution to the onset of a solar flare are still uncleare even though chromospheric brightening is considered a precursor phenomenon of a flare. Many studies suggested that photospheric magnetic field changes cause destabilization of large-scale coronal structure. We aim to understand how a small photospheric change contributes to a flare and to reveal how the intermediary chromosphere behaves in the precursor phase. We analyzed the precursor brightening of the X1.6 flare on 2014 October 22 in the AR 12192 using the Interface Region Imaging Spectrograph (IRIS) and Hinode/EUV Imaging Spectrometer (EIS) data. We investigated a localized jet with the strong precursor brightening, and compared the intensity, Doppler velocity, and line width in C II, Mg II k, and Si IV lines by IRIS and He II, Fe xii, and Fe xv lines by Hinode/EIS. We also analyzed the photospheric magnetic field and chromospheric/coronal structures using the Solar Dynamics Observatory (SDO)/Helioseismic and Magnetic Imager and Atmospheric Imaging Assembly. We found a significant blueshift (˜100 km s-1), which is related to the strong precursor brightening over a characteristic magnetic field structure, and the blueshift was observed at all of the temperatures. This might indicate that the flow is accelerated by Lorentz force. Moreover, the large-scale coronal loop that connects the foot points of the flare ribbons was destabilized just after the precursor brightening with the blueshift. It suggests that magnetic reconnection locally occurred in the lower chromosphere and it triggered magnetic reconnection of the X1.6 flare in the corona.

  15. Study on Precursor Activity of the X1.6 Flare in the Great AR 12192 with SDO , IRIS , and Hinode

    SciT

    Bamba, Yumi; Lee, Kyoung-Sun; Imada, Shinsuke

    The physical properties and their contribution to the onset of a solar flare are still uncleare even though chromospheric brightening is considered a precursor phenomenon of a flare. Many studies suggested that photospheric magnetic field changes cause destabilization of large-scale coronal structure. We aim to understand how a small photospheric change contributes to a flare and to reveal how the intermediary chromosphere behaves in the precursor phase. We analyzed the precursor brightening of the X1.6 flare on 2014 October 22 in the AR 12192 using the Interface Region Imaging Spectrograph ( IRIS ) and Hinode /EUV Imaging Spectrometer (EIS) data.more » We investigated a localized jet with the strong precursor brightening, and compared the intensity, Doppler velocity, and line width in C ii, Mg ii k, and Si iv lines by IRIS and He ii, Fe xii, and Fe xv lines by Hinode /EIS. We also analyzed the photospheric magnetic field and chromospheric/coronal structures using the Solar Dynamics Observatory ( SDO )/Helioseismic and Magnetic Imager and Atmospheric Imaging Assembly. We found a significant blueshift (∼100 km s{sup −1}), which is related to the strong precursor brightening over a characteristic magnetic field structure, and the blueshift was observed at all of the temperatures. This might indicate that the flow is accelerated by Lorentz force. Moreover, the large-scale coronal loop that connects the foot points of the flare ribbons was destabilized just after the precursor brightening with the blueshift. It suggests that magnetic reconnection locally occurred in the lower chromosphere and it triggered magnetic reconnection of the X1.6 flare in the corona.« less

  16. Detecting primary precursors of January surface air temperature anomalies in China

    NASA Astrophysics Data System (ADS)

    Tan, Guirong; Ren, Hong-Li; Chen, Haishan; You, Qinglong

    2017-12-01

    This study aims to detect the primary precursors and impact mechanisms for January surface temperature anomaly (JSTA) events in China against the background of global warming, by comparing the causes of two extreme JSTA events occurring in 2008 and 2011 with the common mechanisms inferred from all typical episodes during 1979-2008. The results show that these two extreme events exhibit atmospheric circulation patterns in the mid-high latitudes of Eurasia, with a positive anomaly center over the Ural Mountains and a negative one to the south of Lake Baikal (UMLB), which is a pattern quite similar to that for all the typical events. However, the Eurasian teleconnection patterns in the 2011 event, which are accompanied by a negative phase of the North Atlantic Oscillation, are different to those of the typical events and the 2008 event. We further find that a common anomalous signal appearing in early summer over the tropical Indian Ocean may be responsible for the following late-winter Eurasian teleconnections and the associated JSTA events in China. We show that sea surface temperature anomalies (SSTAs) in the preceding summer over the western Indian Ocean (WIO) are intimately related to the UMLB-like circulation pattern in the following January. Positive WIOSSTAs in early summer tend to induce strong UMLB-like circulation anomalies in January, which may result in anomalously or extremely cold events in China, which can also be successfully reproduced in model experiments. Our results suggest that the WIOSSTAs may be a useful precursor for predicting JSTA events in China.

  17. Mechanism of organic aerosol formation and aging: Role of the precursor carbon skeleton

    NASA Astrophysics Data System (ADS)

    Hunter, J. F.; Carrasquillo, A. J.; Daumit, K. E.; Cross, E. S.; Worsnop, D. R.; Kroll, J. H.

    2012-12-01

    Oxidative aging of organic aerosol consists of a complex set of reactions coupled with gas-particle partitioning processes. Functionalization reactions involve adding oxygen containing functional groups onto a molecule, leading to reduced vapor pressures and promoting aerosol formation. In fragmentation reactions carbon-carbon bonds are broken as oxygen containing functional groups are added, which generally splits the parent molecule into two smaller and more volatile products. The initial structure of an aerosol-forming precursor molecule may influence what chemistry will occur both by changing the branching between fragmentation and functionalization processes as well as changing the effects of those processes. The fate of early generation oxidation products upon further aging is dependent on this initial chemistry, leading to a persistent effect of the precursor carbon skeleton. Aging experiments have been conducted using a high NOx smog chamber based aging technique. Long residence times and modestly elevated OH concentrations lead to typical maximum OH exposure of 3e11 molecule*seconds/cc, approaching several days equivalent exposure to ambient OH concentrations. A broad set of linear, branched and cyclic aliphatic hydrocarbons has been oxidized to determine the effects of carbon skeleton on the relative importance of fragmentation and functionalization and impacts on aerosol formation chemistry. Relative degree of fragmentation and functionalization is constrained by mass spectrometry of both the gas and particle phase. Measurements of the aerosol oxygen content and mass yield are reported, and structural effects on these properties are determined. Degree of unsaturation is hypothesized to have a significant impact on the effect of fragmentation reactions and to promote additional aerosol formation, extended aging and more oxygenated aerosol.

  18. Role of reduced precursor and solvolytic reagent molar ratio on preparation and properties of ionogel

    SciT

    Gupta, Abhishek Kumar; Verma, Yogendra Lal; Singh, Manish Pratap

    In the present study, ionogels have been synthesized by immobilizing IL (1-ethyl-3-methylimidazolium tetrafluoroborate) in silica gel matrices using non-aqueous route. In this process, tetraethyl orho-silane (TEOS) as a precursor to silicon dioxide and formic acid as a solvolytic gelating reagent in reduced molar ratio 1:4 were used. We find that reduced molar concentration of formic acid results the formation of ionogels having less number of closed pores (totally isolated from their neighbours), larger density and stable monolithic form. TEM and SEM measurements are used to visualize the morphology of sample and closed pores present in the sample. N{sub 2}-sorption measurementmore » is used to measure the pore parameters of the silica matrices which shows the mesoporous structure. DSC and TGA results show the change in phase transition temperature and thermal stability of IL upon confinement in silica matrices. Moreover, ionic conductivity of bulk and confined IL is measured using impedance spectroscopy and it has been found that it increases with increasing the temperature as well as concentration of IL in ionogels. Apart from these characterization techniques, ionogels have been characterized using FTIR and fluorescence spectroscopy which exhibit the change in vibrational frequencies and fluorescence behaviour of confined IL. - Highlights: • Synthesis of stable ionogel using non-hydrolytic route with reduced precursor and solvolytic reagent molar ratio. • Ionogels are free from entrapped residual reaction product. • The ionogels synthesized with higher amount of ionic liquids show bulk liquid like electrical behaviour.« less

  19. Benzoyl Halides as Alternative Precursors for the Colloidal Synthesis of Lead-Based Halide Perovskite Nanocrystals

    PubMed Central

    2018-01-01

    We propose here a new colloidal approach for the synthesis of both all-inorganic and hybrid organic–inorganic lead halide perovskite nanocrystals (NCs). The main limitation of the protocols that are currently in use, such as the hot injection and the ligand-assisted reprecipitation routes, is that they employ PbX2 (X = Cl, Br, or I) salts as both lead and halide precursors. This imposes restrictions on being able to precisely tune the amount of reaction species and, consequently, on being able to regulate the composition of the final NCs. In order to overcome this issue, we show here that benzoyl halides can be efficiently used as halide sources to be injected in a solution of metal cations (mainly in the form of metal carboxylates) for the synthesis of APbX3 NCs (in which A = Cs+, CH3NH3+, or CH(NH2)2+). In this way, it is possible to independently tune the amount of both cations and halide precursors in the synthesis. The APbX3 NCs that were prepared with our protocol show excellent optical properties, such as high photoluminescence quantum yields, low amplified spontaneous emission thresholds, and enhanced stability in air. It is noteworthy that CsPbI3 NCs, which crystallize in the cubic α phase, are stable in air for weeks without any postsynthesis treatment. The improved properties of our CsPbX3 perovskite NCs can be ascribed to the formation of lead halide terminated surfaces, in which Cs cations are replaced by alkylammonium ions. PMID:29378131

  20. Benzoyl Halides as Alternative Precursors for the Colloidal Synthesis of Lead-Based Halide Perovskite Nanocrystals.

    PubMed

    Imran, Muhammad; Caligiuri, Vincenzo; Wang, Mengjiao; Goldoni, Luca; Prato, Mirko; Krahne, Roman; De Trizio, Luca; Manna, Liberato

    2018-02-21

    We propose here a new colloidal approach for the synthesis of both all-inorganic and hybrid organic-inorganic lead halide perovskite nanocrystals (NCs). The main limitation of the protocols that are currently in use, such as the hot injection and the ligand-assisted reprecipitation routes, is that they employ PbX 2 (X = Cl, Br, or I) salts as both lead and halide precursors. This imposes restrictions on being able to precisely tune the amount of reaction species and, consequently, on being able to regulate the composition of the final NCs. In order to overcome this issue, we show here that benzoyl halides can be efficiently used as halide sources to be injected in a solution of metal cations (mainly in the form of metal carboxylates) for the synthesis of APbX 3 NCs (in which A = Cs + , CH 3 NH 3 + , or CH(NH 2 ) 2 + ). In this way, it is possible to independently tune the amount of both cations and halide precursors in the synthesis. The APbX 3 NCs that were prepared with our protocol show excellent optical properties, such as high photoluminescence quantum yields, low amplified spontaneous emission thresholds, and enhanced stability in air. It is noteworthy that CsPbI 3 NCs, which crystallize in the cubic α phase, are stable in air for weeks without any postsynthesis treatment. The improved properties of our CsPbX 3 perovskite NCs can be ascribed to the formation of lead halide terminated surfaces, in which Cs cations are replaced by alkylammonium ions.

  1. Relict chondrules in primitive achondrites: Remnants from their precursor parent bodies

    NASA Astrophysics Data System (ADS)

    Schrader, Devin L.; McCoy, Timothy J.; Gardner-Vandy, Kathryn

    2017-05-01

    We studied the petrography, analyzed the chemical compositions, constrained the closure temperatures (via geothermometry), and determined the oxidation states of relict chondrules in Campo del Cielo (IAB iron meteorite), Graves Nunataks (GRA) 98028 (acapulcoite), and Netschaëvo (IIE iron meteorite) to constrain their formation conditions and investigate links to known meteorite groups. Despite having been thermally metamorphosed, mineral phases within relict chondrules retain information about their precursor compositions. The sizes and textures of relict chondrules, and silicate and chromite compositions indicate that Campo del Cielo, GRA 98028, and Netschaëvo had distinct parent bodies that were similar to, but different from, known chondrite groups. To determine the utility of relict chondrule sizes in thermally metamorphosed meteorites, we determined the chondrule size distributions in the LL chondrites Semarkona (LL3.00), Soko-Banja (LL4), Siena (LL5), and Saint-Séverin (LL6), and the H chondrites Clovis (No. 1) (H3.6), Kesen (H4), Arbol Solo (H5), and Estacado (H6). As expected, mean chondrule diameters increase with degree of thermal metamorphism. We find that Campo del Cielo and GRA 98028 were reduced during thermal metamorphism, consistent with previous studies, indicating that their precursors were initially more FeO-rich than their current compositions. In contrast to previous studies, we find no evidence for reduction of silicates in Netschaëvo. Normal zoning of olivine in Netschaëvo is consistent with crystallization and suggests its silicates are near their primary FeO-contents. The presence of elongated chromite grains along olivine grain boundaries in Netschaëvo indicates formation during thermal metamorphism under oxidizing conditions. Due to the absence of reduction and the composition of chromite being distinct from that of metamorphosed H chondrites, we conclude that Netschaëvo, and by extension the IIE iron meteorites, are not from the H

  2. High strength nanostructured Al-based alloys through optimized processing of rapidly quenched amorphous precursors.

    PubMed

    Kim, Song-Yi; Lee, Gwang-Yeob; Park, Gyu-Hyeon; Kim, Hyeon-Ah; Lee, A-Young; Scudino, Sergio; Prashanth, Konda Gokuldoss; Kim, Do-Hyang; Eckert, Jürgen; Lee, Min-Ha

    2018-01-18

    We report the methods increasing both strength and ductility of aluminum alloys transformed from amorphous precursor. The mechanical properties of bulk samples produced by spark-plasma sintering (SPS) of amorphous Al-Ni-Co-Dy powders at temperatures above 673 K are significantly enhanced by in-situ crystallization of nano-scale intermetallic compounds during the SPS process. The spark plasma sintered Al 84 Ni 7 Co 3 Dy 6 bulk specimens exhibit 1433 MPa compressive yield strength and 1773 MPa maximum strength together with 5.6% plastic strain, respectively. The addition of Dy enhances the thermal stability of primary fcc Al in the amorphous Al-TM -RE alloy. The precipitation of intermetallic phases by crystallization of the remaining amorphous matrix plays important role to restrict the growth of the fcc Al phase and contributes to the improvement of the mechanical properties. Such fully crystalline nano- or ultrafine-scale Al-Ni-Co-Dy systems are considered promising for industrial application because their superior mechanical properties in terms of a combination of very high room temperature strength combined with good ductility.

  3. Silicic central volcanoes as precursors to rift propagation: the Afar case

    NASA Astrophysics Data System (ADS)

    Lahitte, Pierre; Gillot, Pierre-Yves; Courtillot, Vincent

    2003-02-01

    The Afar depression is a triple junction characterised by thinned continental crust, where three rift systems meet (Red Sea, Gulf of Aden and East African Rift). About 100 recent K-Ar ages obtained on Plio-Pleistocene lavas [Lahitte et al., J. Geophys. Res. (2002) in press; Kidane et al., J. Geophys. Res. (2002) in press], complemented by new geomorphological interpretations, allow better understanding of the volcano-tectonic activity linked to rift propagation. In Central Afar, a significant spatial and temporal correlation is observed between the occurrence of silicic central volcanoes and the initiation of the successive phases of on-land propagation of the Red Sea and Aden rifts. Inside the Afar depression, at the scale of both a whole ridge and a small rift segment, silicic lavas are systematically erupted close to the location of a future rift segment and prior to the main extensive phase associated with fissural basaltic activity. Central silicic volcanoes therefore appear to be precursor features, and their locations underline the preferred direction of future rift propagation. Evolved volcanoes (and associated magma chambers) form zones of localised lithospheric weakness, which concentrate stress and guide the development of fractures in which fissural magmatism is next emplaced. Differentiated silicic lavas are erupted first. Then, as extension increases, basaltic magma directly erupts to the surface. This composite style of rifting, with volcanic and tectonic components, is a scaled-down equivalent of the continental break-up process at the largest scale.

  4. The Subaru Coronagraphic Extreme AO project: an XAO4ELT precursor

    NASA Astrophysics Data System (ADS)

    Martinache, F.

    2011-09-01

    A diffraction-limited 30-meter telescope theoretically provides a 10 mas resolution limit in the near infrared. Modern coronagraphs like the Vortex, the 8OPM and the PIAA offer the means to take full advantage of this angular resolution allowing to explore at high contrast, the innermost parts of nearby planetary systems to within a fraction of an astronomical unit: an unprecedented capability that will revolutionize our understanding of planet formation across the habitable zone. A precursor of such a system is the Subaru Coronagraphic Extreme AO project. SCExAO combines a high performance PIAA-based coronagraph downstream Subaru's AO188 AO system and a 1024-actuator MEMS DM. SCExAO employs advanced wavefront control schemes that make high contrast detection possible at 1 λ/D, providing for a few cases, the possibility to detect the light reflected by exoplanets. Moderate-high contrast detection in the super-resolution regime (<λ/D) is also possible using well calibrated closure quantities like closure-phase for a non-redundant (masked) aperture and its extension for to arbitrary apertures (Kernel-phase). Lessons learned from SCExAO's incremental deployment plan during its first 2011 engineering campaign provides insights that will guide future development of high contrast instrumentation on an ELT.

  5. The Murchison Widefield Array: solar science with the low frequency SKA Precursor

    NASA Astrophysics Data System (ADS)

    Tingay, S. J.; Oberoi, D.; Cairns, I.; Donea, A.; Duffin, R.; Arcus, W.; Bernardi, G.; Bowman, J. D.; Briggs, F.; Bunton, J. D.; Cappallo, R. J.; Corey, B. E.; Deshpande, A.; deSouza, L.; Emrich, D.; Gaensler, B. M.; R, Goeke; Greenhill, L. J.; Hazelton, B. J.; Herne, D.; Hewitt, J. N.; Johnston-Hollitt, M.; Kaplan, D. L.; Kasper, J. C.; Kennewell, J. A.; Kincaid, B. B.; Koenig, R.; Kratzenberg, E.; Lonsdale, C. J.; Lynch, M. J.; McWhirter, S. R.; Mitchell, D. A.; Morales, M. F.; Morgan, E.; Ord, S. M.; Pathikulangara, J.; Prabu, T.; Remillard, R. A.; Rogers, A. E. E.; Roshi, A.; Salah, J. E.; Sault, R. J.; Udaya-Shankar, N.; Srivani, K. S.; Stevens, J.; Subrahmanyan, R.; Waterson, M.; Wayth, R. B.; Webster, R. L.; Whitney, A. R.; Williams, A.; Williams, C. L.; Wyithe, J. S. B.

    2013-06-01

    The Murchison Widefield Array is a low frequency (80 - 300 MHz) SKA Precursor, comprising 128 aperture array elements (known as tiles) distributed over an area of 3 km diameter. The MWA is located at the extraordinarily radio quiet Murchison Radioastronomy Observatory in the mid-west of Western Australia, the selected home for the Phase 1 and Phase 2 SKA low frequency arrays. The MWA science goals include: 1) detection of fluctuations in the brightness temperature of the diffuse redshifted 21 cm line of neutral hydrogen from the epoch of reionisation; 2) studies of Galactic and extragalactic processes based on deep, confusion-limited surveys of the full sky visible to the array; 3) time domain astrophysics through exploration of the variable radio sky; and 4) solar imaging and characterisation of the heliosphere and ionosphere via propagation effects on background radio source emission. This paper concentrates on the capabilities of the MWA for solar science and summarises some of the solar science results to date, in advance of the initial operation of the final instrument in 2013.

  6. Ewing's sarcoma precursors are highly enriched in embryonic osteochondrogenic progenitors.

    PubMed

    Tanaka, Miwa; Yamazaki, Yukari; Kanno, Yohei; Igarashi, Katsuhide; Aisaki, Ken-ichi; Kanno, Jun; Nakamura, Takuro

    2014-07-01

    Ewing's sarcoma is a highly malignant bone tumor found in children and adolescents, and the origin of this malignancy is not well understood. Here, we introduced a Ewing's sarcoma-associated genetic fusion of the genes encoding the RNA-binding protein EWS and the transcription factor ETS (EWS-ETS) into a fraction of cells enriched for osteochondrogenic progenitors derived from the embryonic superficial zone (eSZ) of long bones collected from late gestational murine embryos. EWS-ETS fusions efficiently induced Ewing's sarcoma-like small round cell sarcoma formation by these cells. Analysis of the eSZ revealed a fraction of a precursor cells that express growth/differentiation factor 5 (Gdf5), the transcription factor Erg, and parathyroid hormone-like hormone (Pthlh), and selection of the Pthlh-positive fraction alone further enhanced EWS-ETS-dependent tumor induction. Genes downstream of the EWS-ETS fusion protein were quite transcriptionally active in eSZ cells, especially in regions in which the chromatin structure of the ETS-responsive locus was open. Inhibition of β-catenin, poly (ADP-ribose) polymerase 1 (PARP1), or enhancer of zeste homolog 2 (EZH2) suppressed cell growth in a murine model of Ewing's sarcoma, suggesting the utility of the current system as a preclinical model. These results indicate that eSZ cells are highly enriched in precursors to Ewing's sarcoma and provide clues to the histogenesis of Ewing's sarcoma in bone.

  7. Essential role of citron kinase in cytokinesis of spermatogenic precursors.

    PubMed

    Cunto, Ferdinando Di; Imarisio, Sara; Camera, Paola; Boitani, Carla; Altruda, Fiorella; Silengo, Lorenzo

    2002-12-15

    During spermatogenesis, the first morphological indication of spermatogonia differentiation is incomplete cytokinesis, followed by the assembly of stable intercellular cytoplasmic communications. This distinctive feature of differentiating male germ cells has been highly conserved during evolution, suggesting that regulation of the cytokinesis endgame is a crucial aspect of spermatogenesis. However, the molecular mechanisms underlying testis-specific regulation of cytokinesis are still largely unknown. Citron kinase is a myotonin-related protein acting downstream of the GTPase Rho in cytokinesis control. We previously reported that Citron kinase knockout mice are affected by a complex neurological syndrome caused by cytokinesis block and apoptosis of specific neuronal precursors. In this report we show that, in addition, these mice display a dramatic testicular impairment, with embryonic and postnatal loss of undifferentiated germ cells and complete absence of mature spermatocytes. By contrast, the ovaries of mutant females appear essentially normal. Developmental analysis revealed that the cellular depletion observed in mutant testes is caused by increased apoptosis of undifferentiated and differentiating precursors. The same cells display a severe cytokinesis defect, resulting in the production of multinucleated cells and apoptosis. Our data indicate that Citron kinase is specifically required for cytokinesis of the male germ line.

  8. A karyometric note on nucleoli in human early granulocytic precursors.

    PubMed

    Smetana, K; Mikulenková, D; Jirásková, I; Klamová, H

    2006-01-01

    The diameter of nucleoli was measured in human bone marrow early granulocytic precursors after visualization by a simple cytochemical method for demonstration of RNA. Such method facilitated to clearly see nucleolar bodies without perinucleolar chromatin, including those of micronucleoli. The bone marrow of patients suffering from chronic myeloid leukaemia (untreated with cytostatics) provided a satisfactory number of both myeloblasts and promyelocytes for nucleolar measurements because of prevailing granulopoiesis. The direct nucleolar measurement was carried out on digitized and processed images on the screen at magnification 4,300x. It seems to be likely that the nucleolar size is directly related to the number of nucleoli per cell. The largest nucleoli were present in both myeloblasts and promyelocytes that possessed a single nucleolus. In contrast, the nucleolar diameter was significantly smaller in cells with multiple nucleoli. However, in cells with small multiple nucleoli, one of them was always larger and dominant with a large number of AgNORs. Such large nucleoli are possibly visible in specimens stained with panoptic procedures or methods staining nuclear chromatin or DNA. It should also be mentioned that both myeloblasts and promyelocytes mostly possessed two nucleoli with the mean diameter close to 1.5 microm. The incidence of early granulocytic precursors classified according to the nucleolar number and size strongly suggested that the various nucleolar number and nucleolar size in these cells might be related to the different stage of the cell cycle and might also explain their heterogeneity.

  9. Application of Deep Learning to Detect Precursors of Tropical Cyclone

    NASA Astrophysics Data System (ADS)

    Matsuoka, D.; Nakano, M.; Sugiyama, D.; Uchida, S.

    2017-12-01

    Tropical cyclones (TCs) affect significant damage to human society. Predicting TC generation as soon as possible is important issue in both academic and social perspectives. In the present work, we investigate the probability of predicting TCs seven days prior using deep neural networks. The training data is produced from 30-year cloud resolving global atmospheric simulation (NICAM) with 14 km horizontal resolution (Kodama et al., 2015). We employed a TCs tracking algorithm (Sugi et al., 2002; Nakano et al., 2015) to NICAM simulation data in order to generate supervised cloud images (horizontal sizes are 800-1,000km). We generate approximately one million images of "TCs (include their precursors)" and "not TCs (low pressure clouds)". We generate ten types of image classifier based on 2-dimensional convolutional neural network, includes four convolutional layers, three pooling layers and two fully connected layers. The final predicted results are obtained by these ensemble mean values. Generated classifiers are applied to untrained global simulation data (four million test images). As a result, we succeeded in predicting the precursors of TCs seven and five days before their formation with a Recall of 88.6% and 89.6% (Precision is 11.4%), respectively.

  10. Redundancy and divergence in the amyloid precursor protein family.

    PubMed

    Shariati, S Ali M; De Strooper, Bart

    2013-06-27

    Gene duplication provides genetic material required for functional diversification. An interesting example is the amyloid precursor protein (APP) protein family. The APP gene family has experienced both expansion and contraction during evolution. The three mammalian members have been studied quite extensively in combined knock out models. The underlying assumption is that APP, amyloid precursor like protein 1 and 2 (APLP1, APLP2) are functionally redundant. This assumption is primarily supported by the similarities in biochemical processing of APP and APLPs and on the fact that the different APP genes appear to genetically interact at the level of the phenotype in combined knockout mice. However, unique features in each member of the APP family possibly contribute to specification of their function. In the current review, we discuss the evolution and the biology of the APP protein family with special attention to the distinct properties of each homologue. We propose that the functions of APP, APLP1 and APLP2 have diverged after duplication to contribute distinctly to different neuronal events. Our analysis reveals that APLP2 is significantly diverged from APP and APLP1. Copyright © 2013 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

  11. The NAD(+) precursor nicotinamide riboside decreases exercise performance in rats.

    PubMed

    Kourtzidis, Ioannis A; Stoupas, Andreas T; Gioris, Ioannis S; Veskoukis, Aristidis S; Margaritelis, Nikos V; Tsantarliotou, Maria; Taitzoglou, Ioannis; Vrabas, Ioannis S; Paschalis, Vassilis; Kyparos, Antonios; Nikolaidis, Michalis G

    2016-01-01

    Nicotinamide adenine dinucleotide (NAD(+)) and its phosphorylated form (NADP(+)) are key molecules in ubiquitous bioenergetic and cellular signaling pathways, regulating cellular metabolism and homeostasis. Thus, supplementation with NAD(+) and NADP(+) precursors emerged as a promising strategy to gain many and multifaceted health benefits. In this proof-of-concept study, we sought to investigate whether chronic nicotinamide riboside administration (an NAD(+) precursor) affects exercise performance. Eighteen Wistar rats were equally divided in two groups that received either saline vehicle or nicotinamide riboside at a dose of 300 mg/kg body weight/day for 21 days via gavage. At the end of the 21-day administration protocol, both groups performed an incremental swimming performance test. The nicotinamide riboside group showed a tendency towards worse physical performance by 35 % compared to the control group at the final 10 % load (94 ± 53 s for the nicotinamide riboside group and 145 ± 59 s for the control group; P = 0.071). Our results do not confirm the previously reported ergogenic effect of nicotinamide riboside. The potentially negative effect of nicotinamide riboside administration on physical performance may be attributed to the pleiotropic metabolic and redox properties of NAD(+) and NADP(+).

  12. An Accident Precursor Analysis Process Tailored for NASA Space Systems

    NASA Technical Reports Server (NTRS)

    Groen, Frank; Stamatelatos, Michael; Dezfuli, Homayoon; Maggio, Gaspare

    2010-01-01

    Accident Precursor Analysis (APA) serves as the bridge between existing risk modeling activities, which are often based on historical or generic failure statistics, and system anomalies, which provide crucial information about the failure mechanisms that are actually operative in the system and which may differ in frequency or type from those in the various models. These discrepancies between the models (perceived risk) and the system (actual risk) provide the leading indication of an underappreciated risk. This paper presents an APA process developed specifically for NASA Earth-to-Orbit space systems. The purpose of the process is to identify and characterize potential sources of system risk as evidenced by anomalous events which, although not necessarily presenting an immediate safety impact, may indicate that an unknown or insufficiently understood risk-significant condition exists in the system. Such anomalous events are considered accident precursors because they signal the potential for severe consequences that may occur in the future, due to causes that are discernible from their occurrence today. Their early identification allows them to be integrated into the overall system risk model used to intbrm decisions relating to safety.

  13. Radon anomaly in soil gas as an earthquake precursor.

    PubMed

    Miklavcić, I; Radolić, V; Vuković, B; Poje, M; Varga, M; Stanić, D; Planinić, J

    2008-10-01

    The mechanical processes of earthquake preparation are always accompanied by deformations; afterwards, the complex short- or long-term precursory phenomena can appear. Anomalies of radon concentrations in soil gas are registered a few weeks or months before many earthquakes. Radon concentrations in soil gas were continuously measured by the LR-115 nuclear track detectors at site A (Osijek) during a 4-year period, as well as by the Barasol semiconductor detector at site B (Kasina) during 2 years. We investigated the influence of t