Sample records for ac gly3 h2o3

  1. Synthesis, properties and crystal structure of (Gly) 2H 4SiW 12O 40·5.5H 2O

    NASA Astrophysics Data System (ADS)

    Lihua, Bi; Qizhuang, He; Qiong, Jia; Enbo, Wang

    2001-10-01

    A novel polyoxometalate containing Glycine (Gly), (Gly)2H4SiW12O40·5.5H2O (I), has been synthesized and characterized by single-crystal X-ray diffraction, elemental analyzes, IR spectrum, cyclic voltammograms and thermogravimetric analysis. The compound crystallizes in the monoclinic space group C2/C with a=40.362 (8) Å, b=12.478 (3) Å, c=19.879 (4) Å, β=96.22 (3)°, V=9953 (4) Å3, Z=8 and R1 (wR2)=0.0699 (0.1609). The crystal structure consists of [SiW12O40]4- units linked together with Gly molecules through hydrogen bonding. The electrochemical properties of I showed that the electrode reaction is surface-controlled. The compound has photosensitivity under irradiation of sunlight to result in charge transfer by oxidation of Gly and the reduction of SiW12O404-. We also found that the compound exhibited effectiveness in preventing cucumber mosaic virus (CMV).

  2. Pharmacology and expression analysis of glycine transporter GlyT1 with [3H]-(N-[3-(4'-fluorophenyl)-3-(4'phenylphenoxy)propyl])sarcosine.

    PubMed

    Mallorga, Pierre J; Williams, Jacinta B; Jacobson, Marlene; Marques, Rosemary; Chaudhary, Ashok; Conn, P Jeffrey; Pettibone, Douglas J; Sur, Cyrille

    2003-10-01

    In the central nervous system, re-uptake of the neurotransmitter glycine is mediated by two different glycine transporters, GlyT1 and GlyT2. GlyT2 is found in brainstem and spinal cord, whereas GlyT1 is expressed in rat forebrain regions where it is responsible for most glycine transport activity. Initially, GlyT1 and GlyT2 were pharmacologically differentiated by sarcosine, a weak selective inhibitor of GlyT1. The recently described selective and potent GlyT1 antagonist, NFPS/ALX-5407 provided an important additional tool to further characterize GlyT1 pharmacology. In the present study, we have radiolabeled the racemic form of NFPS (N-[3-(4'-fluorophenyl)-3-(4'-phenylphenoxy)propyl])sarcosine (also known as ALX-5407) to investigate its interaction with GlyT1, as well as define GlyT1 expression in the rat central nervous system. Kinetic studies indicated that [3H]NFPS binds rapidly to rat forebrain membranes and dissociates with a t(1/2) of 28 +/- 5 min. [3H]NFPS labeled a saturable population of sites in rat forebrain with a Kd of 7.1+/-1.3 nM and a B(max) of 3.14 +/- 0.26 pmol/mg protein. Bound [3H]NFPS was fully and potently displaced by unlabeled NFPS, whereas glycine and sarcosine were weak, Na+-dependent inhibitors with IC50 of 1,008 and 190 microM, respectively. Additional saturation experiments indicated that glycine and sarcosine were non-competitive antagonists of [3H]NFPS binding. Functional studies revealed that NFPS was a non-competitive inhibitor of [3H]glycine uptake and does not interact with Na+ and Cl- binding sites of GlyT1. Overall, this work shows that [3H]NFPS is a valuable tool in studying GlyT1 expression and pharmacology and that NFPS interacts with GlyT1 at a site different from the transporter translocation and ion binding sites.

  3. Differential requirements for Gli2 and Gli3 in the regional specification of the mouse hypothalamus

    PubMed Central

    Haddad-Tóvolli, Roberta; Paul, Fabian A.; Zhang, Yuanfeng; Zhou, Xunlei; Theil, Thomas; Puelles, Luis; Blaess, Sandra; Alvarez-Bolado, Gonzalo

    2015-01-01

    Secreted protein Sonic hedgehog (Shh) ventralizes the neural tube by modulating the crucial balance between activating and repressing functions (GliA, GliR) of transcription factors Gli2 and Gli3. This balance—the Shh-Gli code—is species- and context-dependent and has been elucidated for the mouse spinal cord. The hypothalamus, a forebrain region regulating vital functions like homeostasis and hormone secretion, shows dynamic and intricate Shh expression as well as complex regional differentiation. Here we asked if particular combinations of Gli2 and Gli3 and of GliA and GliR functions contribute to the variety of hypothalamic regions, i.e., we wanted to approach the question of a possible hypothalamic version of the Shh-Gli code. Based on mouse mutant analysis, we show that: (1) hypothalamic regional heterogeneity is based in part on differentially stringent requirements for Gli2 or Gli3; (2) another source of diversity are differential requirements for Shh of neural vs. non-neural origin; (3) the medial progenitor domain known to depend on Gli2 for its development generates several essential hypothalamic nuclei plus the pituitary and median eminence; (4) the suppression of Gli3R by neural and non-neural Shh is essential for hypothalamic specification. Finally, we have mapped our results on a recent model which considers the hypothalamus as a transverse region with alar and basal portions. Our data confirm the model and are explained by it. PMID:25859185

  4. Luminescence Spectroscopy and Crystal Field Simulations of Europium Propylenediphosphonate EuH[O 3P(CH 2) 3PO 3] and Europium Glutarate [Eu(H 2O)] 2[O 2C(CH 2) 3CO 2] 3·4H 2O

    NASA Astrophysics Data System (ADS)

    Serpaggi, F.; Férey, G.; Antic-Fidancev, E.

    1999-12-01

    The results of investigations on the photoluminescence of two europium hybrid compounds, EuH[O3P(CH2)3PO3] (Eu[diph]) and [Eu(H2O)]2[O2C(CH2)3CO2]3·4H2O (Eu[glut]), are presented. In both compounds one local environment is found for the rare earth (Re) ion and the symmetry of the Re polyhedron is low (Cs) as evidenced by the Eu3+ luminescence studies. The electrostatic crystal field (cf) parameters of the 7F multiplet are obtained by the application of the phenomenological cf theory. The simulations using C2v symmetry for the rare earth ion give good agreement between the calculated and the experimental 7F0-4 energy level schemes. The observed optical data are discussed in relation to the crystal structure of the compounds.

  5. Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 ­(H 2 O)]·7H 2 O and (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 (H 2 O)]·4H 2 O, and a Uranyl Selenate-Selenite [C 5 H 6 N][(UO 2 )(SeO 4 )(HSeO 3 )

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

    Jouffret, Laurent J.; Wylie, Ernest M.; Burns, Peter C.

    2012-08-08

    Two uranyl sulfate hydrates, (H3O)2[(UO2)2(SO4)3(H2O)]·7H2O (NDUS) and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O (NDUS1), and one uranyl selenate-selenite [C5H6N][(UO2)(SeO4)(HSeO3)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L-cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P21/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4)more » Å, β = 112.778(1)°, V = 2153.52(9) Å3,Z = 4, the tetragonal space group P43212, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) Å3, Z = 8, and in the monoclinic space group P21/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) Å3, Z = 4, respectively.The structural units of NDUS and NDUS1 are two-dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two-dimensional uranyl selenate-selenite sheets with a U/Se ratio of 1/2. In-situ reaction of the L-cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H3O+ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C5H6N+ cations result from the cyclization of the carboxyl groups of L-cystine, balancing the charge of the sheets.« less

  6. Synthesis of Nanoscale CaO-Al2O3-SiO2-H2O and Na2O-Al2O3-SiO2-H2O Using the Hydrothermal Method and Their Characterization

    PubMed Central

    Yang, Jingbin; Li, Dongxu; Fang, Yuan

    2017-01-01

    C-A-S-H (CaO-Al2O3-SiO2-H2O) and N-A-S-H (Na2O-Al2O3-SiO2-H2O) have a wide range of chemical compositions and structures and are difficult to separate from alkali-activated materials. Therefore, it is difficult to analyze their microscopic properties directly. This paper reports research on the synthesis of C-A-S-H and N-A-S-H particles with an average particle size smaller than 300 nm by applying the hydrothermal method. The composition and microstructure of the products with different CaO(Na2O)/SiO2 ratios and curing conditions were characterized using XRD, the RIR method, FTIR, SEM, TEM, and laser particle size analysis. The results showed that the C-A-S-H system products with a low CaO/SiO2 ratio were mainly amorphous C-A-S-H gels. With an increase in the CaO/SiO2 ratio, an excess of Ca(OH)2 was observed at room temperature, while in a high-temperature reaction system, katoite, C4AcH11, and other crystallized products were observed. The katoite content was related to the curing temperature and the content of Ca(OH)2 and it tended to form at a high-temperature and high-calcium environment, and an increase in the temperature renders the C-A-S-H gels more compact. The main products of the N-A-S-H system at room temperature were amorphous N-A-S-H gels and a small amount of sodalite. An increase in the curing temperature promoted the formation of the crystalline products faujasite and zeolite-P. The crystallization products consisted of only zeolite-P in the high-temperature N-A-S-H system and its content were stable above 70%. An increase in the Na2O/SiO2 ratio resulted in more non-bridging oxygen and the TO4 was more isolated in the N-A-S-H structure. The composition and microstructure of the C-A-S-H and N-A-S-H system products synthesized by the hydrothermal method were closely related to the ratio of the raw materials and the curing conditions. The results of this study increase our understanding of the hydration products of alkali-activated materials. PMID

  7. Glycine transporters GlyT1 and GlyT2 are differentially modulated by glycogen synthase kinase 3β.

    PubMed

    Jiménez, Esperanza; Núñez, Enrique; Ibáñez, Ignacio; Zafra, Francisco; Aragón, Carmen; Giménez, Cecilio

    2015-02-01

    Inhibitory glycinergic neurotransmission is terminated by the specific glycine transporters GlyT1 and GlyT2 which actively reuptake glycine from the synaptic cleft. GlyT1 is associated with both glycinergic and glutamatergic pathways, and is the main regulator of the glycine levels in the synapses. GlyT2 is the main supplier of glycine for vesicle refilling, a process that is vital to preserve the quantal glycine content in synaptic vesicles. Therefore, to control glycinergic neurotransmission efficiently, GlyT1 and GlyT2 activity must be regulated by diverse neuronal and glial signaling pathways. In this work, we have investigated the possible functional modulation of GlyT1 and GlyT2 by glycogen synthase kinase 3 (GSK3β). This kinase is involved in mood stabilization, neurodegeneration and plasticity at excitatory and inhibitory synapses. The co-expression of GSK3β with GlyT1 or GlyT2 in COS-7 cells and Xenopus laevis oocytes, leads to inhibition and stimulation of GlyT1 and GlyT2 activities, respectively, with a decrease of GlyT1, and an increase in GlyT2 levels at the plasma membrane. The specificity of these changes is supported by the antagonism exerted by a catalytically inactive form of the kinase and through inhibitors of GSK3β such as lithium chloride and TDZD-8. GSK3β also increases the incorporation of 32Pi into GlyT1 and decreases that of GlyT2. The pharmacological inhibition of the endogenous GSK3β in neuron cultures of brainstem and spinal cord leads to an opposite modulation of GlyT1 and GlyT2.Our results suggest that GSK3β is important for stabilizing and/or controlling the expression of functional GlyTs on the neural cell surface. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. Kinetic removal of haloacetonitrile precursors by photo-based advanced oxidation processes (UV/H2O2, UV/O3, and UV/H2O2/O3).

    PubMed

    Srithep, Sirinthip; Phattarapattamawong, Songkeart

    2017-06-01

    The objective of the study is to evaluate the performance of conventional treatment process (i.e., coagulation, flocculation, sedimentation and sand filtration) on the removals of haloacetonitrile (HAN) precursors. In addition, the removals of HAN precursors by photo-based advanced oxidation processes (Photo-AOPs) (i.e., UV/H 2 O 2 , UV/O 3 , and UV/H 2 O 2 /O 3 ) are investigated. The conventional treatment process was ineffective to remove HAN precursors. Among Photo-AOPs, the UV/H 2 O 2 /O 3 was the most effective process for removing HAN precursors, followed by UV/H 2 O 2 , and UV/O 3 , respectively. For 20min contact time, the UV/H 2 O 2 /O 3 , UV/H 2 O 2 , and UV/O 3 suppressed the HAN formations by 54, 42, and 27% reduction. Increasing ozone doses from 1 to 5 mgL -1 in UV/O 3 systems slightly improved the removals of HAN precursors. Changes in pH (6-8) were unaffected most of processes (i.e., UV, UV/H 2 O 2 , and UV/H 2 O 2 /O 3 ), except for the UV/O 3 system that its efficiency was low in the weak acid condition. The pseudo first-order kinetic constant for removals of dichloroacetonitrile precursors (k' DCANFP ) by the UV/H 2 O 2 /O 3 , UV/H 2 O 2 and standalone UV systems were 1.4-2.8 orders magnitude higher than the UV/O 3 process. The kinetic degradation of dissolved organic nitrogen (DON) tended to be higher than the k' DCANFP value. This study firstly differentiates the kinetic degradation between DON and HAN precursors. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Gibbs energies of transferring triglycine from water into H2O-DMSO solvent

    NASA Astrophysics Data System (ADS)

    Usacheva, T. R.; Kuz'mina, K. I.; Lan, Pham Thi; Kuz'mina, I. A.; Sharnin, V. A.

    2014-08-01

    The Gibbs energies of transferring triglycine (3Gly, glycyl-glycyl-glycine) from water into mixtures of water with dimethyl sulfoxide (χDMSO = 0.05, 0.10, and 0.15 mole fractions) at 298.15 K are determined from the interphase distribution. An increased dimethyl sulfoxide (DMSO) concentration in the solvent slightly raises the positive values of Δtr G ○(3Gly), possibly indicating the formation of more stable 3Gly-H2O solvated complexes than ones of 3Gly-DMSO. It is shown that the change in the Gibbs energy of transfer of 3Gly is determined by the enthalpy component. The relationship of 3Gly and 18-crown-6 ether (18C6) solvation's contributions to the change in the Gibbs energy of [3Gly18C6] molecular complex formation in H2O-DMSO solvents is analyzed, and the key role of 3Gly solvation's contribution to the change in the stability of [3Gly18C6] upon moving from H2O to mixtures with DMSO is revealed.

  10. Expansion of antimonato polyoxovanadates with transition metal complexes: (Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)]·8H2O.

    PubMed

    Antonova, Elena; Näther, Christian; Kögerler, Paul; Bensch, Wolfgang

    2012-02-20

    Two new polyoxovanadates (Co(N(3)C(5)H(15))(2))(2)[{Co(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·5H(2)O (1) and (Ni(N(3)C(5)H(15))(2))(2)[{Ni(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·8H(2)O (2) (N(3)C(5)H(15) = N-(2-aminoethyl)-1,3-propanediamine) were synthesized under solvothermal conditions and structurally characterized. In both structures the [V(15)Sb(6)O(42)(H(2)O)](6-) shell displays the main structural motif, which is strongly related to the {V(18)O(42)} archetype cluster. Both compounds crystallize in the triclinic space group P1 with a = 14.3438(4), b = 16.6471(6), c = 18.9186(6) Å, α = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°, and V = 4401.4(2) Å(3) (1) and a = 14.5697(13), b = 15.8523(16), c = 20.2411(18) Å, α = 86.702(11)°, β = 84.957(11)°, γ = 76.941(11)°, and V = 4533.0(7) Å(3) (2). In the structure of 1 the [V(15)Sb(6)O(42)(H(2)O)](6-) cluster anion is bound to a [Co(N(3)C(5)H(15))(2)](2+) complex via a terminal oxygen atom. In the Co(2+)-centered complex, one of the amine ligands coordinates in tridentate mode and the second one in bidentate mode to form a strongly distorted CoN(5)O octahedron. Similarly, in compound 2 an analogous NiN(5)O complex is joined to the [V(15)Sb(6)O(42)(H(2)O)](6-) anion via the same attachment mode. A remarkable difference between the two compounds is the orientation of the noncoordinated propylamine group leading to intermolecular Sb···O contacts in 1 and to Sb···N interactions in 2. In the solid-state lattices of 1 and 2, two additional [M(N(3)C(5)H(15))(2)](2+) complexes act as countercations and are located between the [{M(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)](4-) anions. Between the anions and cations strong N-H···O hydrogen bonds are observed. In both compounds the clusters are stacked along the b axis in an ABAB fashion with cations and water molecules occupying the space between the clusters. Magnetic characterization demonstrates that the Ni(2+) and Co(2+) cations do not

  11. Ground and excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters: Insight into the electronic structure of the [Fe(H2O)6]2+ – [Fe(H2O)6]3+ complex

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

    Miliordos, Evangelos; Xantheas, Sotiris S.

    We report the ground and low lying electronically excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters using multi-configuration electronic structure theory. In particular, we have constructed the Potential Energy Curves (PECs) with respect to the iron-oxygen distance when removing all water ligands at the same time from the cluster minima and established their correlation to the long range dissociation channels. Due to the fact that both the second and third ionization potentials of iron are larger than the one for water, the ground state products asymptotically correlate with dissociation channels that are repulsive in nature at large separations as theymore » contain at least one H2O+ fragment and a positive metal center. The most stable equilibrium structures emanate – via intersections and/or avoided crossings – from the channels consisting of the lowest electronic states of Fe2+(5D; 3d6) or Fe3+(6S; 3d5) and six neutral water molecules. Upon hydration, the ground state of Fe2+(H2O)6 is a triply (5Tg) degenerate one with the doubly (5Eg) degenerate state lying slightly higher in energy. Similarly, Fe3+(H2O)6 has a ground state of 6Ag symmetry under Th symmetry. We furthermore examine a multitude of electronically excited states of many possible spin multiplicities, and report the optimized geometries for several selected states. The PECs for those cases are characterized by a high density of states. Focusing on the ground and the first few excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters, we studied their mutual interaction in the gas phase. We obtained the optimal geometries of the Fe2+(H2O)6 – Fe3+(H2O)6 gas phase complex for different Fe–Fe distances. For distances shorter than 6.0 Å, the water molecules in the respective first solvation shells located between the two metal centers were found to interact via weak hydrogen bonds. We examined a total of ten electronic states for this complex, including those corresponding to the

  12. Synthesis, biological evaluation, and automated docking of constrained analogues of the opioid peptide H-Dmt-D-Ala-Phe-Gly-NH₂ using the 4- or 5-methyl substituted 4-amino-1,2,4,5-tetrahydro-2-benzazepin-3-one scaffold.

    PubMed

    De Wachter, Rien; de Graaf, Chris; Keresztes, Atilla; Vandormael, Bart; Ballet, Steven; Tóth, Géza; Rognan, Didier; Tourwé, Dirk

    2011-10-13

    The Phe(3) residue of the N-terminal tetrapeptide of dermorphin (H-Dmt-d-Ala-Phe-Gly-NH(2)) was conformationally constrained using 4- or 5-methyl-substituted 4-amino-1,2,4,5-tetrahydro-2-benzazepin-3-one (Aba) stereoisomeric scaffolds. Several of the synthesized peptides were determined to be high affinity agonists for the μ opioid receptor (OPRM) with selectivity over the δ opioid receptor (OPRD). Interesting effects of the Aba configuration on ligand binding affinity were observed. H-Dmt-d-Ala-erythro-(4S,5S)-5-Me-Aba-Gly-NH(2)9 and H-Dmt-threo-(4R,5S)-5-Me-Aba-Gly-NH(2)12 exhibited subnanomolar affinity for OPRM, while they possess an opposite absolute configuration at position 4 of the Aba ring. However, in the 4-methyl substituted analogues, H-Dmt-d-Ala-(4R)-Me-Aba-Gly-NH(2)14 was significantly more potent than the (4S)-derivative 13. These unexpected results were rationalized using the binding poses predicted by molecular docking simulations. Interestingly, H-Dmt-d-Ala-(4R)-Me-Aba-Gly-NH(2)14 is proposed to bind in a different mode compared with the other analogues. Moreover, in contrast to Ac-4-Me-Aba-NH-Me, which adopts a β-turn in solution and in the crystal structure, the binding mode of this analogue suggests an alternative receptor-bound conformation.

  13. Two mixed-ligand lanthanide–hydrazone complexes: [Pr(NCS)3(pbh)2H2O and [Nd(NCS)(NO3)(pbh)2(H2O)]NO3·2.33H2O [pbh is N′-(pyridin-2-ylmethylidene)benzo­hydrazide, C13H11N3O

    PubMed Central

    Paschalidis, Damianos G.; Harrison, William T. A.

    2016-01-01

    The gel-mediated syntheses and crystal structures of [N′-(pyridin-2-ylmethylidene-κN)benzohydrazide-κ2 N′,O]tris(thiocyanato-κN)praseodymium(III) mono­hydrate, [Pr(NCS)3(C13H11N3O)2H2O, (I), and aqua(nitrato-κ2 O,O′)[N′-(pyri­din-2-ylmethylidene-κN)benzohydrazide-κ2 N′,O](thiocyanato-κN)neo­dym­ium(III) nitrate 2.33-hydrate, [Nd(NCS)(NO3)(C13H11N3O)2(H2O)]NO3·2.33H2O, (II), are reported. The Pr3+ ion in (I) is coordinated by two N,N,O-tridentate N′-(pyridin-2-ylmethylidene)benzohydrazide (pbh) ligands and three N-bonded thio­cyanate ions to generate an irregular PrN7O2 coordination polyhedron. The Nd3+ ion in (II) is coordinated by two N,N,O-tridentate pbh ligands, an N-bonded thio­cyanate ion, a bidentate nitrate ion and a water mol­ecule to generate a distorted NdN5O5 bicapped square anti­prism. The crystal structures of (I) and (II) feature numerous hydrogen bonds, which lead to the formation of three-dimensional networks in each case. PMID:26958385

  14. hPEPT1 is responsible for uptake and transport of Gly-Sar in the human bronchial airway epithelial cell-line Calu-3.

    PubMed

    Søndergaard, Helle Bach; Brodin, Birger; Nielsen, Carsten Uhd

    2008-06-01

    The purpose of this work was to investigate the apical uptake and transepithelial transport of Gly-Sar along with the expression of the di-/tripeptide transporters hPEPT1 and hPEPT2 in human Calu-3 bronchial epithelial cells. The apical Gly-Sar uptake rate in Calu-3 cells followed Michaelis-Menten kinetics with a Km value of 1.3 +/- 0.3 mM and a Vmax value of 0.60 +/- 0.06 nmol cm(-2) min(-1). Transepithelial apical to basolateral transport of 50 microM [3H]-labelled Gly-Sar across the Calu-3 cell monolayer was pH-dependent. The Gly-Sar flux was significantly reduced in the presence of delta-aminolevulinic acid (2.5 mM), cephalexin (25 mM), and captopril (25 mM; p < 0.05, n = 3). Reverse transcriptase polymerase chain reaction (RT-PCR) revealed the presence of both hPEPT1 and hPEPT2 mRNA in the Calu-3 cells. These findings were confirmed in healthy human bronchial cDNA. Restriction-endonuclease analysis identified hPEPT2 in Calu-3 cells to be the hPEPT2*1 haplotype. Western blotting demonstrated expression of the hPEPT1 protein (approximately 80 kDa), and the immunolabel was mainly localized in the apical membrane as judged by immunolocalization studies using confocal laser scanning microscopy (CLSM). This work presents for the first time hPEPT1 and hPEPT2*1 expression in human Calu-3 cells. Surprisingly, the results indicate that Gly-Sar uptake and transport in Calu-3 cells are hPEPT1-mediated rather than hPEPT2-mediated.

  15. Nucleosome eviction along with H3K9ac deposition enhances Sox2 binding during human neuroectodermal commitment

    PubMed Central

    Du, Yanhua; Liu, Zhenping; Cao, Xinkai; Chen, Xiaolong; Chen, Zhenyu; Zhang, Xiaobai; Zhang, Xiaoqing; Jiang, Cizhong

    2017-01-01

    Neuroectoderm is an important neural precursor. However, chromatin remodeling and its epigenetic regulatory roles during the differentiation of human neuroectodermal cells (hNECs) from human embryonic stem cells (hESCs) remain largely unexplored. Here, we obtained hNECs through directed differentiation from hESCs, and determined chromatin states in the two cell types. Upon differentiation, H2A.Z-mediated nucleosome depletion leads to an open chromatin structure in promoters and upregulates expression of neuroectodermal genes. Increase in H3K9ac signals and decrease in H3K27me3 signals in promoters result in an active chromatin state and activate neuroectodermal genes. Conversely, decrease in H3K9ac signals and increase in H3K27me3 signals in promoters repress pluripotency genes. Moreover, H3K9ac signals facilitate the pluripotency factor Sox2 binding to target sites unique to hNECs. Knockdown of the acetyltransferase Kat2b erases H3K9ac signals, disrupts Sox2 binding, and fails the differentiation. Our results demonstrate a hierarchy of epigenetic regulation of gene expression during the differentiation of hNECs from hESCs through chromatin remodeling. PMID:28475175

  16. Cell cycle-dependent changes in H3K56ac in human cells

    PubMed Central

    Stejskal, Stanislav; Stepka, Karel; Tesarova, Lenka; Stejskal, Karel; Matejkova, Martina; Simara, Pavel; Zdrahal, Zbynek; Koutna, Irena

    2015-01-01

    The incorporation of histone H3 with an acetylated lysine 56 (H3K56ac) into the nucleosome is important for chromatin remodeling and serves as a marker of new nucleosomes during DNA replication and repair in yeast. However, in human cells, the level of H3K56ac is greatly reduced, and its role during the cell cycle is controversial. Our aim was to determine the potential of H3K56ac to regulate cell cycle progression in different human cell lines. A significant increase in the number of H3K56ac foci, but not in H3K56ac protein levels, was observed during the S and G2 phases in cancer cell lines, but was not observed in embryonic stem cell lines. Despite this increase, the H3K56ac signal was not present in late replication chromatin, and H3K56ac protein levels did not decrease after the inhibition of DNA replication. H3K56ac was not tightly associated with the chromatin and was primarily localized to active chromatin regions. Our results support the role of H3K56ac in transcriptionally active chromatin areas but do not confirm H3K56ac as a marker of newly synthetized nucleosomes in DNA replication. PMID:26645646

  17. Pincer phosphine complexes of ruthenium: formation of Ru(P-O-P)(PPh3)HCl (P-O-P = xantphos, DPEphos, (Ph2PCH2CH2)2O) and Ru(dppf)(PPh3)HCl and characterization of cationic dioxygen, dihydrogen, dinitrogen, and arene coordinated phosphine products.

    PubMed

    Ledger, Araminta E W; Moreno, Aitor; Ellul, Charles E; Mahon, Mary F; Pregosin, Paul S; Whittlesey, Michael K; Williams, Jonathan M J

    2010-08-16

    Treatment of Ru(PPh(3))(3)HCl with the pincer phosphines 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (xantphos), bis(2-diphenylphosphinophenyl)ether (DPEphos), or (Ph(2)PCH(2)CH(2))(2)O affords Ru(P-O-P)(PPh(3))HCl (xantphos, 1a; DPEphos, 1b; (Ph(2)PCH(2)CH(2))(2)O, 1c). The X-ray crystal structures of 1a-c show that all three P-O-P ligands coordinate in a tridentate manner through phosphorus and oxygen. Abstraction of the chloride ligand from 1a-c by NaBAr(4)(F) (BAr(4)(F) = B(3,5-C(6)H(3)(CF(3))(2))(4)) gives the cationic aqua complexes [Ru(P-O-P)(PPh(3))(H(2)O)H]BAr(4)(F) (3a-c). Removal of chloride from 1a by AgOTf yields Ru(xantphos)(PPh(3))H(OTf) (2a), which reacts with water to form [Ru(xantphos)(PPh(3))(H(2)O)H](OTf). The aqua complexes 3a-b react with O(2) to generate [Ru(xantphos)(PPh(3))(eta(2)-O(2))H]BAr(4)(F) (5a) and [Ru(DPEphos)(PPh(3))(eta(2)-O(2))H]BAr(4)(F) (5b). Addition of H(2) or N(2) to 3a-c yields the thermally unstable dihydrogen and dinitrogen species [Ru(P-O-P)(PPh(3))(eta(2)-H(2))H]BAr(4)(F) (6a-c) and [Ru(P-O-P)(PPh(3))(N(2))H]BAr(4)(F) (7a-c), which have been characterized by multinuclear NMR spectroscopy at low temperature. Ru(PPh(3))(3)HCl reacts with 1,1'-bis(diphenylphosphino)ferrocene (dppf) to give the 16-electron complex Ru(dppf)(PPh(3))HCl (1d), which upon treatment with NaBAr(4)(F), affords [Ru(dppf){(eta(6)-C(6)H(5))PPh(2)}H]BAr(4)(F) (8), in which the PPh(3) ligand binds eta(6) through one of the PPh(3) phenyl rings. Reaction of 8 with CO or PMe(3) at elevated temperatures yields the 18-electron products [Ru(dppf)(PPh(3))(CO)(2)H]BAr(F)(4) (9) and [Ru(PMe(3))(5)H]BAr(4)(F) (10).

  18. Reactions of CH3SH and CH3SSCH3 with gas-phase hydrated radical anions (H2O)n(•-), CO2(•-)(H2O)n, and O2(•-)(H2O)n.

    PubMed

    Höckendorf, Robert F; Hao, Qiang; Sun, Zheng; Fox-Beyer, Brigitte S; Cao, Yali; Balaj, O Petru; Bondybey, Vladimir E; Siu, Chi-Kit; Beyer, Martin K

    2012-04-19

    The chemistry of (H(2)O)(n)(•-), CO(2)(•-)(H(2)O)(n), and O(2)(•-)(H(2)O)(n) with small sulfur-containing molecules was studied in the gas phase by Fourier transform ion cyclotron resonance mass spectrometry. With hydrated electrons and hydrated carbon dioxide radical anions, two reactions with relevance for biological radiation damage were observed, cleavage of the disulfide bond of CH(3)SSCH(3) and activation of the thiol group of CH(3)SH. No reactions were observed with CH(3)SCH(3). The hydrated superoxide radical anion, usually viewed as major source of oxidative stress, did not react with any of the compounds. Nanocalorimetry and quantum chemical calculations give a consistent picture of the reaction mechanism. The results indicate that the conversion of e(-) and CO(2)(•-) to O(2)(•-) deactivates highly reactive species and may actually reduce oxidative stress. For reactions of (H(2)O)(n)(•-) with CH(3)SH as well as CO(2)(•-)(H(2)O)(n) with CH(3)SSCH(3), the reaction products in the gas phase are different from those reported in the literature from pulse radiolysis studies. This observation is rationalized with the reduced cage effect in reactions of gas-phase clusters. © 2012 American Chemical Society

  19. A three-dimensional coordination polymer based on 1,2,3-triazole-4,5-dicarboxylic acid (H{sub 3}tda): ([Cd{sub 12}(tda){sub 8}(H{sub 2}O){sub 11}] · (H{sub 2}O)6.25){sub n}

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

    Zhou, Xin-Hui, E-mail: iamxhzhou@njupt.edu.cn; Chen, Qiang

    The title coordination polymer ([Cd{sub 12}(tda){sub 8}(H{sub 2}O){sub 11}] · (H{sub 2}O){sub 6.25}){sub n} (H{sub 3}tda = 1,2,3-triazole-4,5-dicarboxylic acid), has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Complex crystallizes in orthorhombic sp. gr. Pmn2{sub 1} with Z = 4. The Cd{sub 2} unit doublebridged by one carboxylate oxygen atom and two neighboring nitrogen atoms from the tda{sup 3–} ligands are linked by the tda{sup 3–}ligands to lead to the 2D (4,4) network in the ac plane. The almost coplanar Cd{sub 2}(μ{sub 5}-tda){sub 2} unit comprised of two Cd ions double-bridged by two tda{sup 3–} ligands through themore » neighboring nitrogen atoms is connected with the other four Cd{sub 2}(μ{sub 5}-tda){sub 2} units form the undulating 2D network in the ac plane. The (4,4) networks and undulating 2D networks are alternatively connected along the b axis by the tda{sup 3–} ligands coordinating to the Cd ions to form the 3D framework.« less

  20. Normal exon copy number of the GLI2 and GLI3 genes in patients with esophageal atresia.

    PubMed

    Bednarczyk, D; Smigiel, R; Patkowski, D; Laczmanska, I; Lebioda, A; Laczmanski, L; Sasiadek, M M

    2013-01-01

    Esophageal atresia (EA) is a congenital developmental defect of the alimentary tract concerning the interruption of the esophagus with or without connection to the trachea. The incidence of EA is 1 in 3000-3500 of live-born infants, and occurs in both isolated and syndromic (in combination with abnormalities in other organ systems) forms. The molecular mechanisms underlying the development of EA are poorly understood. Knockout studies in mice indicate that genes like Sonic hedgehog, Gli2, and Gli3 play a role in the etiology of EA. These facts led us to hypothesize that Sonic hedgehog-GLI gene rearrangements are associated with EA in humans. To test this hypothesis, we screened patients with isolated and syndromic EA for GLI2 and/or GLI3 microrearrangements using methods to estimate the copy number (Multiplex Ligation-dependent Probe Amplification, real-time polymerase chain reaction). To our best knowledge this is the first study assessing copy number of GLI2 and GLI3 genes in patients with EA. © 2013 Wiley Periodicals, Inc. and the International Society for Diseases of the Esophagus.

  1. Pharmacological characterization of the inhibitory activity of beta h-endorphin (beta h-EP), [Arg9,19,24,28,29]-beta h-EP, [Gln8,Gly31]-beta h-EP-Gly-Gly-NH2, in the neuroeffector junction of the mouse vas deferens.

    PubMed

    Valenzuela, R; Li, C H; Huidobro-Toro, J P

    1991-08-01

    The inhibitory opioid activities of beta h-endorphin (beta h-EP), its structurally related peptide analogues [Gln8,Gly31]-beta h-EP-Gly-Gly-NH2 (Gly-Gly-beta h-EP), [Arg9,19,24,28,29]-beta h-EP (Arg-beta h-EP) and methionine enkephalin have been examined in the electrically stimulated mouse vas deferens bioassay. All four peptides behaved as full agonists; methionine enkephalin was the most potent followed by Arg-beta h-EP, beta h-EP and Gly-Gly-beta h-EP. Neither Gly-Gly-beta h-EP nor Arg-beta h-EP antagonized the inhibitory action of beta h-EP or methionine enkephalin. An hour of tissue exposure to 30 nM beta-funaltrexamine followed by thorough washing, displaced to the right, in a parallel fashion, the concentration-response curves of beta h-EP and analogues. Whereas the displacement of the concentration response curves was 8 to 10-fold for beta h-EP and Arg-beta h-EP, it was only about 3-fold for Gly-Gly-beta h-EP and methionine enkephalin. Naltrindole was the most potent antagonist of methionine enkephalin with an apparent pA2 of 9.4; its potency as an antagonist of beta h-EP and related analogues was approximately one-tenth of this with pA2 values approximately 8.5. Norbinaltorphimine also antagonized the action of the opioid peptides with pA2 values close to 7.8.

  2. Nqrs Data for H6I3InO12 [I3InO3(H2O)] (Subst. No. 2289)

    NASA Astrophysics Data System (ADS)

    Chihara, H.; Nakamura, N.

    This document is part of Subvolume B 'Substances Containing C10H16 … Zn' of Volume 48 'Nuclear Quadrupole Resonance Spectroscopy Data' of Landolt-Börnstein - Group III 'Condensed Matter'. It contains an extract of Section '3.2 Data tables' of the Chapter '3 Nuclear quadrupole resonance data' providing the NQRS data for H6I3InO12 [I3InO3(H2O)] (Subst. No. 2289)

  3. Interhemispheric differences in polar stratospheric HNO3, H2O, ClO, and O3

    NASA Technical Reports Server (NTRS)

    Santee, M. L.; Read, W. G.; Waters, J. W.; Froidevaux, L.; Manney, G. L.; Flower, D. A.; Jarnot, R. F.; Harwood, R. S.; Peckham, G. E.

    1995-01-01

    Simultaneous global measurements of nitric acid (HNO3), water (H2O), chlorine monoxide (ClO), and ozone (O3) in the stratosphere have been obtained over complete annual cycles in both hemispheres by the Microwave Limb Sounder on the Upper Atmosphere Research Satellite. A sizeable decrease in gas-phase HNO3 was evident in the lower stratospheric vortex over Antarctica by early June 1992, followed by a significant reduction in gas-phase H2O after mid-July. By mid-August, near the time of peak ClO, abundances of gas-phase HNO3 and H2O were extremely low. The concentrations of HNO3 and H2O over Antarctica remained depressed into November, well after temperatures in the lower stratosphere had risen above the evaporation threshold for polar stratospheric clouds, implying that denitrification and dehydration had occurred. No large decreases in either gas-phase HNO3 or H2O were observed in the 1992-1993 Arctic winter vortex. Although ClO was enhanced over the Arctic as it was over the Antarctic, Arctic O3 depletion was substantially smaller than that over Antarctica. A major factor currently limiting the formation of an Arctic ozone 'hole' is the lack of denitrification in the northern polar vortex, but future cooling of the lower stratosphere could lead to more intense denitrification and consequently larger losses of Arctic ozone.

  4. Selective photocatalytic reduction of CO2 by H2O/H2 to CH4 and CH3OH over Cu-promoted In2O3/TiO2 nanocatalyst

    NASA Astrophysics Data System (ADS)

    Tahir, Muhammad; Tahir, Beenish; Saidina Amin, Nor Aishah; Alias, Hajar

    2016-12-01

    Photocatalytic CO2 reduction by H2O and/or H2 reductant to selective fuels over Cu-promoted In2O3/TiO2 photocatalyst has been investigated. The samples, prepared via a simple and direct sol-gel method, were characterized by XRD, SEM, TEM, XPS, N2 adsorption-desorption, UV-vis diffuse reflectance, Raman and PL spectroscopy. Cu and In loaded into TiO2, oxidized as Cu2+ and In3+, promoted efficient separation of photo-generated electron/hole pairs (e-/h+). The results indicate that the reduction rate of CO2 by H2O to CH4 approached to 181 μmol g-1 h-1 using 0.5% Cu-3% In2O3/TiO2 catalyst, a 1.53 fold higher than the production rate over the 3% In2O3/TiO2 and 5 times the amount produced over the pure TiO2. In addition, Cu was found to promote efficient production of CH3OH and yield rate reached to 68 μmol g-1 h-1 over 1% Cu-3% In2O3/TiO2 catalyst. This improvement was attributed to charge transfer property and suppressed recombination rate by Cu-metal. More importantly, H2 reductant was less favorable for CH4 production, yet a significant amount of CH4 and CH3OH were obtained using a mixture of H2O/H2 reductant. Therefore, Cu-loaded In2O3/TiO2 catalyst has shown to be capable for methanol production, whereas product selectivity was greatly depending on the amount of Cu-loading and the type of reductant. A photocatalytic reaction mechanism was proposed to understand the experimental results over the Cu-loaded In2O3/TiO2 catalyst.

  5. Insertion of bentonite with Organometallic [Fe3O(OOC6H5)6(H2O)3(NO3).nH2O] as Adsorbent of Congo Red

    NASA Astrophysics Data System (ADS)

    Said, Muhammad; Paluta Utami, Hasja; Hayati, Ferlina

    2018-01-01

    The adsorption of Congo red using bentonite inserted organometallic has been investigated. The insertion bentonite was characterized using FT-IR Spectrophotometer, XRD and XRF analysis. The FT-IR characterization showed the higher intensity of peak wavenumber at 470.6 cm-1 for Fe3O on the ratio 1:3. While the XRD characterization showed the shift of diffraction angle of 2θ was 5.2° and has a basal spacing of 16.8 Å. In the XRF characterization, the insertion process of organometallic occurred optimally with the percentage of metal oxide reached 71.75 %. The adsorption process of bentonite inserted organometallic compound [Fe3O(OOC6H5)6(H2O)3(NO3)·nH2O] showed the adsorption rate (k) is 0.050 min-1, the largest adsorption capacity (b) at 70°C is 4.48 mol/g, the largest adsorption energy at temperature 30°C which is 6.4 kJ/mol Organometallic compounds. The value of the enthalpy (ΔH) and entropy (ΔS) decreased with increasing concentrations of the Congo red. Effect of pH on the adsorption on at pH 3 shows the biggest of number Congo red absorbed is 19.52 mg/L for insertion of bentonite.

  6. [Mechanism and performance of styrene oxidation by O3/H2O2].

    PubMed

    He, Jue-Cong; Huang, Qian-Ru; Ye, Qi-Hong; Luo, Yu-Wei; Zhang, Zai-Li; Fan, Qing-Juan; Wei, Zai-Shan

    2013-10-01

    It can produce a large number of free radicals in O3/H2O2, system, ozone and free radical coupling oxidation can improve the styrene removal efficiency. Styrene oxidation by O3/H2O2 was investigated. Ozone dosage, residence time, H2o2 volume fraction, spray density and molar ratio of O3/C8H8 on styrene removal were evaluated. The experimental results showed that styrene removal efficiency achieved 85.7%. The optimal residence time, H2O2, volume fraction, spray density and O3/C8H8 molar ratio were 20. 6 s, 10% , 1.72 m3.(m2.h)-1 and 0.46, respectively. The gas-phase degradation intermediate products were benzaldehyde(C6H5CHO) and benzoic acid (C6H5 COOH) , which were identified by means of gas chromatography-mass spectrometry(GC-MS). The degradation mechanism of styrene is presented.

  7. Pressure dependence of backbone chemical shifts in the model peptides Ac-Gly-Gly-Xxx-Ala-NH2.

    PubMed

    Erlach, Markus Beck; Koehler, Joerg; Crusca, Edson; Kremer, Werner; Munte, Claudia E; Kalbitzer, Hans Robert

    2016-06-01

    For a better understanding of nuclear magnetic resonance (NMR) detected pressure responses of folded as well as unstructured proteins the availability of data from well-defined model systems are indispensable. In this work we report the pressure dependence of chemical shifts of the backbone atoms (1)H(α), (13)C(α) and (13)C' in the protected tetrapeptides Ac-Gly-Gly-Xxx-Ala-NH2 (Xxx one of the 20 canonical amino acids). Contrary to expectation the chemical shifts of these nuclei have a nonlinear dependence on pressure in the range from 0.1 to 200 MPa. The polynomial pressure coefficients B 1 and B 2 are dependent on the type of amino acid studied. The coefficients of a given nucleus show significant linear correlations suggesting that the NMR observable pressure effects in the different amino acids have at least partly the same physical cause. In line with this observation the magnitude of the second order coefficients of nuclei being direct neighbors in the chemical structure are also weakly correlated.

  8. Synthesis and structure of heptaaqua(nitrilotris(methylenephosphonato))(dibarium)sodium monohydrate [Na(H{sub 2}O){sub 3}(μ{sup 6}-NH(CH{sub 2}PO{sub 3}){sub 3})(μ-H{sub 2}O){sub 3}Ba{sub 2}(H{sub 2}O)] · H{sub 2}O

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

    Somov, N. V., E-mail: somov@phys.unn.ru; Chausov, F. F., E-mail: xps@ftiudm.ru; Zakirova, R. M., E-mail: ftt@udsu.ru

    Crystals of the monohydrate form of heptaaqua(nitrilotris(methylenephosphonato))(dibarium) sodium [Na(H{sub 2}O{sub )3}(µ{sup 6}-NH(CH{sub 2}PO{sub 3}){sub 3})(µ-H{sub 2}O){sub 3}Ba{sub 2}(H{sub 2}O)] · H{sub 2}O are obtained; space group P2{sub 1}/c, Z = 4; a = 13.9117(10) Å, b = 11.54030(10) Å, and c = 24.1784(17) Å, ß = 148.785(18)°. The Na atom is coordinated octahedrally by one oxygen atom of a phosphonate group and five water molecules, including two bridging molecules. Ba atoms occupy two inequivalent crystallographic positions with coordination number eight and nine. The coordination spheres of both Ba atoms include two water molecules. Each ligand is bound to one Namore » atom and five Ba atoms forming three Ba–O–P–O and five Ba–O–P–C–N–C–P–O chelate cycles. In addition to the coordination bonds, molecules, including the solvate water molecule, are involved in hydrogen bonds in the crystal packing.« less

  9. Ilyukhinite (H3O,Na)14Ca6Mn2Zr3Si26O72(OH)23H2O, a New Mineral of the Eudialyte Group

    NASA Astrophysics Data System (ADS)

    Chukanov, N. V.; Rastsvetaeva, R. K.; Rozenberg, K. A.; Aksenov, S. M.; Pekov, I. V.; Belakovsky, D. I.; Kristiansen, R.; Van, K. V.

    2017-12-01

    A new eudialyte-group mineral, ilyukhinite, ideally (H3O,Na)14Ca6Mn2Zr3Si26O72(OH)2 · 3H2O, has been found in peralkaline pegmatite at Mt. Kukisvumchorr, Khibiny alkaline pluton, Kola Peninsula, Russia. It occurs as brownish orange, with vitreous luster anhedral grains up to 1 mm across in hydrothermally altered peralkaline rock, in association with aegirine, murmanite, albite, microcline, rhabdophane-(Ce), fluorite, sphalerite and molybdenite. The Mohs hardness is 5; cleavage is not observed. D meas 2.67(2), D calc 2.703 g/cm3. Ilyukhinite is optically uniaxial (-): ω = 1.585(2), ɛ = 1.584(2). The IR spectrum is given. The average chemical composition of ilyukhinite (wt %; electron microprobe, ranges given in parentheses; H2O determined by gas chromatography) is as follows: 3.07 (3.63-4.43) Na2O, 0.32 (0.28-0.52) K2O, 10.63 (10.26-10.90) CaO, 3.06 (2.74-3.22) MnO, 1.15 (0.93-1.37) FeO, 0.79 (0.51-0.89) La2O3, 1.21 (0.97-1.44) Ce2O3, 0.41 (0.30-0.56) Nd2O3, 0.90 (0.77-1.12) TiO2, 10.94 (10.15-11.21) ZrO2, 1.40 (0.76-1.68) Nb2O5, 51.24 (49.98-52.28) SiO2, 1.14 (0.89-1.37) SO3, 0.27 (0.19—0.38) Cl, 10.9(5 )H2O,-0.06-O = C1, total is 98.27. The empirical formula is H36.04(Na3.82K0.20)(Ca5.65Ce0.22La0.14Nd0.07)(Mn1.285Fe0.48)(Zr2.645Ti0.34)Nb0.31Si25.41S0.42Cl0.23O86.82. The crystal structure has been solved ( R = 0.046). Ilyukhinite is trigonal, R3 m; a = 14.1695(6) Å, b = 31.026(1) Å, V = 5394.7(7) Å3, Z = 3. The strongest XRD reflections [ d, Å (I, %) ( hkl)] are 11.44 (82) (101), 7.09 (70) (110), 6.02 (44) (021), 4.371 (89) 205), 3.805 (47) (303, 033), 3.376 (41) (131), 2.985 (100) (315, 128), 2.852 (92) (404). Ilyukhinite was named in memory of Vladimir V. Ilyukhin (1934-1982), an outstanding Soviet crystallographer. The type specimen of ilyukhinite has been deposited in the collection of the Natural History Museum, University of Oslo, Norway.

  10. 3-Methyl-7-(2-thienyl)pyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione: pi-stacked bilayers built from N-H...O, C-H...O and C-H...pi hydrogen bonds.

    PubMed

    Trilleras, Jorge; Quiroga, Jairo; Cobo, Justo; Glidewell, Christopher

    2009-06-01

    In the title compound, C(12)H(9)N(3)O(2)S, the thienyl substituent is disordered over two sets of sites with occupancies of 0.749 (3) and 0.251 (3). A combination of N-H...O, C-H...O and C-H...pi hydrogen bonds links the molecules into bilayers and these bilayers are themselves linked into a continuous structure by pi-pi stacking interactions.

  11. Mg shallow doping effects on the ac magnetic self-heating characteristics of γ-Fe2O3 superparamagnetic nanoparticles for highly efficient hyperthermia

    NASA Astrophysics Data System (ADS)

    Jang, Jung-tak; Bae, Seongtae

    2017-10-01

    The effects of Mg doping on the magnetic and AC self-heating temperature rising characteristics of γ-Fe2O3 superparamagnetic nanoparticles (SPNPs) were investigated for hyperthermia applications in biomedicine. The doping concentration of nonmagnetic Mg2+ cation was systematically controlled from 0 to 0.15 at. % in Mgx-γFe2O3 SPNPs during chemically and thermally modified one-pot thermal decomposition synthesis under bubbling O2/Ar gas mixture. It was empirically observed that the saturation magnetization (Ms) and the out-of-phase magnetic susceptibility ( χm″)of Mgx-γFe2O3 SPNPs were increased by increasing the Mg2+ cation doping concentration from 0.05 to 0.13 at. %. Correspondingly, the AC magnetically induced self-heating temperature (Tac,max) in solid state and the intrinsic loss power in water were increased up to 184 °C and 14.2 nH m2 kg-1 (Mgx-γFe2O3, x = 0.13), respectively, at the biologically and physiologically safe range of AC magnetic field (Happl × fappl = 1.2 × 109 A m-1 s-1). All the chemically and physically analyzed results confirmed that the dramatically improved AC magnetic induction heating characteristics and the magnetic properties of Mgx-γFe2O3 SPNPs (x = 0.13) are primarily due to the significantly enhanced magnetic susceptibility (particularly, χm″) and the improved AC/DC magnetic softness (lower AC/DC magnetic anisotropy) resulting from the systematically controlled nonmagnetic Mg2+ cation concentrations and distributions (occupation ratio) in the Fe vacancy sites of γ-Fe2O3 (approximately 12% vacancy), instead of typically well-known Fe3O4 (no vacancy) SPNPs. The cell viability and biocompatibility with U87 MG cell lines demonstrated that Mgx-γFe2O3 SPNPs (x = 0.13) has promising bio-feasibility for hyperthermia agent applications.

  12. Spectroscopic properties of morin in various CH3OH-H2O and CH3CN-H2O mixed solvents.

    PubMed

    Park, Hyoung-Ryun; Im, Seo-Eun; Seo, Jung-Ja; Kim, Bong-Gon; Yoon, Jin Ah; Bark, Ki-Min

    2015-01-01

    The specific fluorescence properties of morin (3,2',4',5,7-pentahydroxyflavone) were studied in various CH3OH-H2O and CH3CN-H2O mixed solvents. Although the dihedral angle is large in the S0 state, morin has an almost planar molecular structure in the S1 state owing to the very low rotational energy barrier around the interring bond between B and the A, C ring. The excited state intramolecular proton transfer (ESIPT) at the S1 state cannot occur immediately after excitation, S1 → S0 fluorescence can be observed. Two conformers, Morin A and B have been known. At the CH3OH-H2O, Morin B will be the principal species but at the CH3CN-H2O, Morin A is the principal species. At the CH3OH-H2O, owing to the large Franck-Condon (FC) factor for S2 → S1 internal convernal (IC) and flexible molecular structure, only S1 → S0 fluorescence was exhibited. At the CH3CN-H2O, as the FC factor for S2 → S1 IC is small and molecular structure is rigid, S2 → S0 and S1 → S0 dual fluorescence was observed. This abnormal fluorescence property was further supported by the small pK1 value, effective delocalization of the lone pair electrons of C(2')-OH to the A, C ring, and a theoretical calculation. © 2014 The American Society of Photobiology.

  13. Magnetocaloric effect in gadolinium-oxalate framework Gd{sub 2}(C{sub 2}O{sub 4}){sub 3}(H{sub 2}O){sub 6}⋅(0{sub ⋅}6H{sub 2}O)

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

    Sibille, Romain, E-mail: rom.sibille@gmail.com; Didelot, Emilie; Mazet, Thomas

    2014-12-01

    Magnetic refrigerants incorporating Gd{sup 3+} ions and light organic ligands offer a good balance between isolation of the magnetic centers and their density. We synthesized the framework material Gd{sub 2}(C{sub 2}O{sub 4}){sub 3}(H{sub 2}O){sub 6}⋅0.6H{sub 2}O by a hydrothermal route and characterized its structure. The honeycomb lattice of Gd{sup 3+} ions interlinked by oxalate ligands in the (a,c) plane ensures their decoupling in terms of magnetic exchange interactions. This is corroborated by magnetic measurements indicating negligible interactions between the Gd{sup 3+} ions in this material. The magnetocaloric effect was evaluated from isothermal magnetization measurements. The maximum entropy change −ΔS{sub M}{supmore » max} reaches 75.9 mJ cm{sup −3} K{sup −1} (around 2 K) for a moderate field change (2 T)« less

  14. The catalytic effects of H2CO3, CH3COOH, HCOOH and H2O on the addition reaction of CH2OO + H2O → CH2(OH)OOH

    NASA Astrophysics Data System (ADS)

    Zhang, Tianlei; Lan, Xinguang; Wang, Rui; Roy, Soumendra; Qiao, Zhangyu; Lu, Yousong; Wang, Zhuqing

    2018-07-01

    The addition reaction of CH2OO + H2O → CH2(OH)OOH without and with X (X = H2CO3, CH3COOH and HCOOH) and H2O was studied at CCSD(T)/6-311+ G(3df,2dp)//B3LYP/6-311+G(2d,2p) level of theory. Our results show that X can catalyse CH2OO + H2O → CH2(OH)OOH reaction both by increasing the number of rings, and by adding the size of the ring in which ring enlargement by COOH moiety of X inserting into CH2OO...H2O is favourable one. Water-assisted CH2OO + H2O → CH2(OH)OOH can occur by H2O moiety of (H2O)2 or the whole (H2O)2 forming cyclic structure with CH2OO, where the latter form is more favourable. Because the concentration of H2CO3 is unknown, the influence of CH3COOH, HCOOH and H2O were calculated within 0-30 km altitude of the Earth's atmosphere. The results calculated within 0-5 km altitude show that H2O and HCOOH have obvious effect on enhancing the rate with the enhancement factors are, respectively, 62.47%-77.26% and 0.04%-1.76%. Within 5-30 km altitude, HCOOH has obvious effect on enhancing the title rate with the enhancement factor of 2.69%-98.28%. However, compared with the reaction of CH2OO + HCOOH, the rate of CH2OO...H2O + HCOOH is much slower.

  15. Two new three-dimensional zinc phosphites templated by piperazine: [H2pip][Zn3(HPO3)4(H2O)2] and K[H2pip]0.5[Zn3(HPO3)4

    NASA Astrophysics Data System (ADS)

    Zhang, Xiao; Wang, Guo-Ming; Wang, Zong-Hua; Wang, Ying-Xia; Lin, Jian-Hua

    2014-01-01

    Two three-dimensional open-framework zinc phosphites with the same organically templated, [H2pip][Zn3(HPO3)4(H2O)2] (1) and K[H2pip]0.5[Zn3(HPO3)4] (2) (pip = piperazine), have been solvothermally synthesized and structurally characterized by IR, elemental analysis, thermogravimetric analysis, powder and single-crystal X-ray diffractions. Compound 1 consists of ZnO4 tetrahedra, [HPO3] pseudopyramids and [ZnO4(H2O)2] octahedra, which are linked through their vertexes to generate three-dimensional architecture with intersecting 8-membered channels along the [1 0 0], [0 0 1] and [1 0 1] directions. Compound 2 is constructed from strictly alternating ZnO4 tetrahedra and [HPO3] pseudopyramids, and exhibits (3,4)-connected inorganic framework with 8-, and 12-membered channels, in which the K+ and diprotonated H2pip2+ extra-framework cations reside, respectively. The coexistence of inorganic K+ and organic piperazine mixed templates in the structure is unique and, to the best of our knowledge, firstly observed in metal-phosphite materials. In addition, the participation of left-handed and right-handed helical chains in construction of the puckered 4.82 sheet structure in 2 is also noteworthy.

  16. Fe{sub 2}O{sub 3}-Bi{sub 2}O{sub 3}-B{sub 2}O{sub 3} glasses as lithium-free nonsilicate pH responsive glasses – Compatibility between pH responsivity and hydrophobicity

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

    Hashimoto, Tadanori, E-mail: hasimoto@chem.mie-u.ac.jp; Hamajima, Mitsuaki; Ohta, Honami

    Highlights: • Fe{sub 2}O{sub 3}-rich FeBiB glasses show high pH sensitivity and short pH response time. • Bi{sub 2}O{sub 3}-rich FeBiB glasses show relatively high contact angle for water. • FeBiB glasses are lithium-free nonsilicate pH responsive ones. • pH responsivity and hydrophobicity are obtained for optimum glass compositions. - Abstract: Lithium silicate-based glasses have widely been used as commercially available pH glass electrodes. It was revealed that Ti{sup 3+}-containing titanophosphate (TiO{sub 2}-P{sub 2}O{sub 5}, TP) glasses are pH responsive as lithium-free nonsilicate glasses for the first time. TP glasses with the compatibility between pH responsivity and self-cleaning property weremore » obtained by the sequential post-annealing (oxidation and reduction) of as-prepared glasses. Bi{sub 2}O{sub 3}-B{sub 2}O{sub 3} (BiB) glasses are relatively hydrophobic and are expected to show anti-fouling effect. They are unsuitable for pH responsive glasses, because they have high electrical resistivity. In the present study, xFe{sub 2}O{sub 3}·yBi{sub 2}O{sub 3}·(100 − x − y)B{sub 2}O{sub 3} glasses (xFeyBiB, x = 0–20 mol%, y = 20–80 mol%) glasses were selected as new pH responsive glasses with hydrophobicity, because Fe{sub 2}O{sub 3} is a representative component for causing hopping conduction to the glasses. BiB glass did not show pH responsivity, whereas xFeyBiB glasses showed good pH responsivity. xFeyBiB glasses are lithium-free nonsilicate pH responsive ones as well as TP glasses. The electrical resistivity and pH response time decreased with increasing Fe{sub 2}O{sub 3} content. The pH repeatability for standard solutions increased with increasing Bi{sub 2}O{sub 3} content. Silicate glass (20Fe70BiSi) showed better pH responsivity but lower contact angle than those of borate glass (20Fe70BiB). pH sensitivity increased in order of TP glasses (about 80%), xFeyBiB glasses (about 90%) and commercial pH responsive glass (about 100

  17. Lanthanite-(Nd), Nd2(CO3)3·8H2O

    PubMed Central

    Morrison, Shaunna M.; Andrade, Marcelo B.; Wenz, Michelle D.; Domanik, Kenneth J.; Downs, Robert T.

    2013-01-01

    Lanthanite-(Nd), ideally Nd2(CO3)3·8H2O [dineodymium(III) tricarbonate octa­hydrate], is a member of the lanthanite mineral group characterized by the general formula REE 2(CO3)3·8H2O, where REE is a 10-coordinated rare earth element. Based on single-crystal X-ray diffraction of a natural sample from Mitsukoshi, Hizen-cho, Karatsu City, Saga Prefecture, Japan, this study presents the first structure determination of lanthanite-(Nd). Its structure is very similar to that of other members of the lanthanite group. It is composed of infinite sheets made up of corner- and edge-sharing of two NdO10-polyhedra (both with site symmetry ..2) and two carbonate triangles (site symmetries ..2 and 1) parallel to the ab plane, and stacked perpendicular to c. These layers are linked to one another only through hydrogen bonding involving the water mol­ecules. PMID:23476479

  18. Anionic ordering and thermal properties of FeF3·3H2O.

    PubMed

    Burbano, Mario; Duttine, Mathieu; Borkiewicz, Olaf; Wattiaux, Alain; Demourgues, Alain; Salanne, Mathieu; Groult, Henri; Dambournet, Damien

    2015-10-05

    Iron fluoride trihydrate can be used to prepare iron hydroxyfluoride with the hexagonal-tungsten-bronze (HTB) type structure, a potential cathode material for batteries. To understand this phase transformation, a structural description of β-FeF3·3H2O is first performed by means of DFT calculations and Mössbauer spectroscopy. The structure of this compound consists of infinite chains of [FeF6]n and [FeF2(H2O)4]n. The decomposition of FeF3·3H2O induces a collapse and condensation of these chains, which lead to the stabilization, under specific conditions, of a hydroxyfluoride network FeF3-x(OH)x with the HTB structure. The release of H2O and HF was monitored by thermal analysis and physical characterizations during the decomposition of FeF3·3H2O. An average distribution of FeF4(OH)2 distorted octahedra in HTB-FeF3-x(OH)x was obtained subsequent to the thermal hydrolysis/olation of equatorial anionic positions involving F(-) and H2O. This study provides a clear understanding of the structure and thermal properties of FeF3·3H2O, a material that can potentially bridge the recycling of pickling sludge from the steel industry by preparing battery electrodes.

  19. Human CRL4DDB2 ubiquitin ligase preferentially regulates post-repair chromatin restoration of H3K56Ac through recruitment of histone chaperon CAF-1

    PubMed Central

    Zhu, Qianzheng; Wei, Shengcai; Sharma, Nidhi; Wani, Gulzar; He, Jinshan; Wani, Altaf A.

    2017-01-01

    Acetylated histone H3 lysine 56 (H3K56Ac) diminishes in response to DNA damage but is restored following DNA repair. Here, we report that CRL4DDB2 ubiquitin ligase preferentially regulates post-repair chromatin restoration of H3K56Ac through recruitment of histone chaperon CAF-1. We show that H3K56Ac accumulates at DNA damage sites. The restoration of H3K56Ac but not H3K27Ac, H3K18Ac and H3K14Ac depends on CAF-1 function, whereas all these acetylations are mediated by CBP/p300. The CRL4DDB2 components, DDB1, DDB2 and CUL4A, are also required for maintaining the H3K56Ac and H3K9Ac level in chromatin, and for restoring H3K56Ac following induction of DNA photolesions and strand breaks. Depletion of CUL4A decreases the recruitment of CAF-1 p60 and p150 to ultraviolet radiation- and phleomycin-induced DNA damage. Neddylation inhibition renders CRL4DDB2 inactive, decreases H3K56Ac level, diminishes CAF-1 recruitment and prevents H3K56Ac restoration. Mutation in the PIP box of DDB2 compromises its capability to elevate the H3K56Ac level but does not affect XPC ubiquitination. These results demonstrated a function of CRL4DDB2 in differential regulation of histone acetylation in response to DNA damage, suggesting a novel role of CRL4DDB2 in repair-driven chromatin assembly. PMID:29262658

  20. Urchin-Like Ni1/3Co2/3(CO3)1/2(OH)·0.11H2O for Ultrahigh-Rate Electrochemical Supercapacitors: Structural Evolution from Solid to Hollow.

    PubMed

    Wei, Wutao; Cui, Shizhong; Ding, Luoyi; Mi, Liwei; Chen, Weihua; Hu, Xianluo

    2017-11-22

    Portable electronics and electric or hybrid electric vehicles are developing in the trend of fast charge and long electric mileage, which ask us to design a novel electrode with sufficient electronic and ionic transport channels at the same time. Herein, we fabricate a uniform hollow-urchin-like Ni 1/3 Co 2/3 (CO 3 ) 1/2 (OH)·0.11H 2 O electrode material through an easy self-generated and resacrificial template method. The one-dimensional chain-like crystal structure unit containing the metallic bonding and the intercalated OH - and H 2 O endow this electrode material with abundant electronic and ionic transport channels. The hollow-urchin-like structure built by nanorods contributes to the large electrode-electrolyte contact area ensuring the supply of ions at high current. CNTs are employed to transport electrons between electrode material and current collector. The as-assembled NC-CNT-2//AC supercapacitor device exhibits a high specific capacitance of 108.3 F g -1 at 20 A g -1 , a capacitance retention ratio of 96.2% from 0.2 to 20 A g -1 , and long cycle life. Comprehensive investigations unambiguously highlight that the unique hollow-urchin-like Ni 1/3 Co 2/3 (CO 3 ) 1/2 (OH)·0.11H 2 O electrode material would be the right candidate for advanced next-generation supercapacitors.

  1. Anionic ordering and thermal properties of FeF 3·3H 2O

    DOE PAGES

    Burbano, Mario; Duttine, Mathieu; Borkiewicz, Olaf; ...

    2015-09-17

    In this study, iron fluoride tri-hydrate can be used to prepare iron hydroxyfluoride with the Hexagonal-Tungsten-Bronze (HTB) type structure, a potential cathode material for batteries. To understand this phase transformation, a structural description of β-FeF 3·3H 2O is first performed by means of DFT calculations and Mössbauer spectroscopy. The structure of this compound consists of infinite chains of [FeF 6]n and [FeF 2(H2O) 4] n. The decomposition of FeF 3·3H 2O induces a collapse and condensation of these chains, which lead to the stabilization, under specific conditions, of a hydroxyfluoride network FeF 3-x(OH) x with the HTB structure. The releasemore » of H 2O and HF was monitored by thermal analysis and physical characterizations during the decomposition of FeF 3·3H 2O. An average distribution of FeF 4(OH) 2 distorted octahedra in HTB-FeF 3-x(OH) x was obtained subsequent to the thermal hydrolysis/olation of equatorial anionic positions involving F- and H 2O. This study provides a clear understanding of the structure and thermal properties of FeF 3·3H 2O, a material that can potentially bridge the recycling of pickling sludge from the steel industry by preparing battery electrodes.« less

  2. Design and syntheses of hybrid metal-organic materials based on K3[M(C2O4)33H2O [M(III)=Fe, Al, Cr] metallotectons

    NASA Astrophysics Data System (ADS)

    Sun, Yayong; Zong, Yingxia; Ma, Haoran; Zhang, Ao; Liu, Kang; Wang, Debao; Wang, Wenqiang; Wang, Lei

    2016-05-01

    By using K3[M(C2O4)33H2O [M(III)=Fe, Al, Cr] (C2O42-=oxalate) metallotectons as the starting material, we have synthesized eight novel complexes with formulas [{Fe(C2O4)2(H2O)2}2]·(H-L1)2·H2O 1, [Fe(C2O4)Cl2]·(H2-L2)0.5·(L2)0.5·H2O 2, [{Fe(C2O4)1.5Cl2}2]·(H-L3)43, [Fe2(C2O4)Cl8]·(H2-L4)2·2H2O 4, K[Al(C2O4)3]·(H2-L5)·2H2O 5, K[Al(C2O4)3]·(H-L6)2·2H2O 6, K[Cr(C2O4)32H2O 7, Na[Fe(C2O4)3]·(H-L6)2·2H2O 8 (with L1=4-dimethylaminopyridine, L2=2,3,5,6-tetramethylpyrazine, L3=2-aminobenzimidazole, L4=1,4-bis-(1H-imidazol-1-yl)benzene, L5=1,4-bis((2-methylimidazol-1-yl)methyl)benzene, L6=2-methylbenzimidazole). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra and thermogravimetric analyses. Compound 3 is a 2D H-bonded supramolecular architecture. Others are 3D supramolecular structures. Compound 1 shows a [Fe(C2O4)2(H2O)2]- unit and 3D antionic H-bonded framework. Compound 2 features a [Fe(C2O4)Cl2]- anion and 1D iron-oxalate-iron chain. Compound 3 features a [Fe2(C2O4)3Cl4]4- unit. Compound 4 features distinct [Fe2(C2O4)Cl8]4- units, which are mutual linked by water molecules to generated a 2D H-bonded network. Compound 5 features infinite ladder-like chains constructed by [Al(C2O4)3]3- units and K+ cations. The 1D chains are further extended into 3D antionic H-bonded framework through O-H···O H-bonds. Compounds 6-8 show 2D [KAl(C2O4)3]2- layer, [KCr(C2O4)3]2- layer and [NaFe(C2O4)3]2- layer, respectively.

  3. Gli3 is a negative regulator of Tas1r3-expressing taste cells

    PubMed Central

    Jyotaki, Masafumi; Redding, Kevin; Jiang, Peihua

    2018-01-01

    Mouse taste receptor cells survive from 3–24 days, necessitating their regeneration throughout adulthood. In anterior tongue, sonic hedgehog (SHH), released by a subpopulation of basal taste cells, regulates transcription factors Gli2 and Gli3 in stem cells to control taste cell regeneration. Using single-cell RNA-Seq we found that Gli3 is highly expressed in Tas1r3-expressing taste receptor cells and Lgr5+ taste stem cells in posterior tongue. By PCR and immunohistochemistry we found that Gli3 was expressed in taste buds in all taste fields. Conditional knockout mice lacking Gli3 in the posterior tongue (Gli3CKO) had larger taste buds containing more taste cells than did control wild-type (Gli3WT) mice. In comparison to wild-type mice, Gli3CKO mice had more Lgr5+ and Tas1r3+ cells, but fewer type III cells. Similar changes were observed ex vivo in Gli3CKO taste organoids cultured from Lgr5+ taste stem cells. Further, the expression of several taste marker and Gli3 target genes was altered in Gli3CKO mice and/or organoids. Mirroring these changes, Gli3CKO mice had increased lick responses to sweet and umami stimuli, decreased lick responses to bitter and sour taste stimuli, and increased glossopharyngeal taste nerve responses to sweet and bitter compounds. Our results indicate that Gli3 is a suppressor of stem cell proliferation that affects the number and function of mature taste cells, especially Tas1r3+ cells, in adult posterior tongue. Our findings shed light on the role of the Shh pathway in adult taste cell regeneration and may help devise strategies for treating taste distortions from chemotherapy and aging. PMID:29415007

  4. Synthesis, structure, and properties of nickel complexes with nitrilotris(methylenephosphonic acid) [Ni(H{sub 2}O)3N(CH2PO{sub 3}H){sub 3}] and Na{sub 4}[Ni(H{sub 2}O)N(CH{sub 2}PO{sub 3}){sub 3}] ∙ 11H{sub 2}O

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

    Somov, N. V., E-mail: somov@phys.unn.ru; Chausov, F. F., E-mail: chaus@yandex.ru; Zakirova, R. M.

    2016-03-15

    Nitrilotris(methylenephosphonato)triaquanickel and tetrasodium nitrilotris(methylenephosphonato) aquanickelate undecahydrate were synthesized and characterized. The crystal of [Ni(H{sub 2}O){sub 3}N(CH{sub 2}PO{sub 3}H){sub 3}] is composed of linear coordination polymers and belongs to sp. gr. P2{sub 1}/c, Z = 4, a = 9.17120(10) Å, b = 16.05700(10) Å, c = 9.70890(10) Å, β = 115.830(2)°. The Ni atom is in an octahedral coordination formed by two oxygen atoms of one phosphonate ligand, one oxygen atom of another ligand molecule, and three water molecules in a meridional configuration. The crystal of Na{sub 4}[Ni(H{sub 2}O)N(CH{sub 2}PO{sub 3}){sub 3}] ∙ 11H{sub 2}O has an island dimeric chelate structuremore » and belongs to sp. gr. C2/c, Z = 8, a = 18.7152(2) Å, b = 12.05510(10) Å, c = 21.1266(2) Å, β = 104.4960(10)°. The Ni atom has a slightly distorted octahedral coordination involving one nitrogen atom and closes three five-membered N–C–P–O–Ni rings sharing the Ni–N bond.« less

  5. N-Doped Dual Carbon-Confined 3D Architecture rGO/Fe3O4/AC Nanocomposite for High-Performance Lithium-Ion Batteries.

    PubMed

    Ding, Ranran; Zhang, Jie; Qi, Jie; Li, Zhenhua; Wang, Chengyang; Chen, Mingming

    2018-04-25

    To address the issues of low electrical conductivity, sluggish lithiation kinetics and dramatic volume variation in Fe 3 O 4 anodes of lithium ion battery, herein, a double carbon-confined three-dimensional (3D) nanocomposite architecture was synthesized by an electrostatically assisted self-assembly strategy. In the constructed architecture, the ultrafine Fe 3 O 4 subunits (∼10 nm) self-organize to form nanospheres (NSs) that are fully coated by amorphous carbon (AC), formatting core-shell structural Fe 3 O 4 /AC NSs. By further encapsulation by reduced graphene oxide (rGO) layers, a constructed 3D architecture was built as dual carbon-confined rGO/Fe 3 O 4 /AC. Such structure restrains the adverse reaction of the electrolyte, improves the electronic conductivity and buffers the mechanical stress of the entire electrode, thus performing excellent long-term cycling stability (99.4% capacity retention after 465 cycles relevant to the second cycle at 5 A g -1 ). Kinetic analysis reveals that a dual lithium storage mechanism including a diffusion reaction mechanism and a surface capacitive behavior mechanism coexists in the composites. Consequently, the resulting rGO/Fe 3 O 4 /AC nanocomposite delivers a high reversible capacity (835.8 mA h g -1 for 300 cycles at 1 A g -1 ), as well as remarkable rate capability (436.7 mA h g -1 at 10 A g -1 ).

  6. Lack of mixed agonist-antagonist properties of [Gln8-Gly31]-beta h-EP-Gly-Gly-NH2 and [Arg9,19,24,28,29]-beta h-EP in the rat vas deferens neuroeffector junction: studies with naloxone, beta-funaltrexamine and ICI 174,864.

    PubMed

    Valenzuela, R; Li, C H; Huidobro-Toro, J P

    1989-02-01

    The 1-27 truncated fragment of beta h-endorphin (beta h-EP) as well as [Gln8,Gly31]-beta h-EP-Gly-Gly-NH2 or [Arg9,19,24,28,29]-beta h-EP exhibited opiate agonist activity in the rat vas deferens bioassay; the potency of these peptides was 3 to 6 times less than that of beta h-EP. None of these compounds exhibited any degree of antagonism towards the inhibitory action of beta h-EP. Naloxone antagonized and reversed the inhibitory action of beta h-EP and its analogues though with varying potencies. The apparent naloxone-pA2 value for beta h-EP was 8.94; that for [Gln8-Gly31]-beta h-EP-Gly-Gly-NH2 was 8.08 and that for [Arg9,19,24,28,29]-beta h-EP was 8.38. beta-Funaltrexamine (beta-FNA) potently antagonized the inhibitory action of beta h-EP following non-equilibrium kinetics. Tissue preincubation with 10 nM beta-FNA for 60 min followed by extensive washing caused a 10-fold increase in the beta h-EP IC50. However, 10 nM beta-FNA caused only a 1.2 increase in the IC50 of [Gln8,Gly31]-beta h-EP-Gly-Gly-NH2 and a 4.1-fold increase in the IC50 of [Arg9,19,24,28,29]-beta h-EP. In contrast, preincubation of the tissue with 3 microM ICI 174,864 did not modify the potency of beta h-EP or its structural analogues. However, a 60 min pretreatment with 10 microM beta-FNA followed by the addition of 3 microM ICI 174,864 revealed a further decrease in the potency of the opiopeptins compared with tissues exposed to beta-FNA alone or ICI 174,864 alone. In conclusion, the inhibitory action of these peptides is remarkably sensitive to beta-FNA antagonism; in addition the peptides act as pure opiate agonists in marked contrast with the agonist-antagonist properties described in the CNS.

  7. H3K9ac and HDAC2 Activity Are Involved in the Expression of Monocarboxylate Transporter 1 in Oligodendrocyte

    PubMed Central

    Lai, Qingwei; Du, Wantong; Wu, Jian; Wang, Xiao; Li, Xinyu; Qu, Xuebin; Wu, Xiuxiang; Dong, Fuxing; Yao, Ruiqin; Fan, Hongbin

    2017-01-01

    Recently, it is reported that monocarboxylate transporter 1 (MCT1) plays crucial role in oligodendrocyte differentiation and myelination. We found that MCT1 is strongly expressed in oligodendrocyte but weakly expressed in oligodendrocyte precursors (OPCs), and the underlying mechanisms remain elusive. Histone deacetylases (HDACs) activity is required for induction of oligodendrocyte differentiation and maturation. We asked whether HDACs are involved in the regulation of MCT1 expression. This work revealed that the acetylation level of histone H3K9 (H3K9ac) was much higher in mct1 gene (Slc16a1) promoter in OPCs than that in oligodendrocyte. H3K9ac regulates MCT1 expression was confirmed by HDAC acetyltransferase inhibitors trichostatin A and curcumin. Of note, there was a negative correlation between H3K9ac and MCT1 expression in oligodendrocyte. Further, we found that the levels of HDAC1, 2, and 3 protein in oligodendrocyte were obviously higher than those in OPCs. However, specific knockdown of HDAC2 but not HDAC1 and HDAC3 significantly decreased the expression of MCT1 in oligodendrocyte. Conversely, overexpression of HDAC2 remarkably enhanced the expression of MCT1. The results imply that HDAC2 is involved in H3K9ac modification which regulates the expression of MCT1 during the development of oligodendrocyte. PMID:29184483

  8. Syntheses and characterization of phosphonates and diphosphonates of molybdenum, A4[(MoO3)5(O3PR)2]·xH2O, A2[Mo2O5(O3PR)2] and A2[Mo2O5(O3P-R-PO3)] (A = K, Rb, Cs, Tl, NH4).

    PubMed

    Elias Jesu Packiam, D; Vidyasagar, Kanamaluru

    2017-11-28

    Twenty new molybdenum phosphonates and diphosphonates have been synthesized and structurally characterized by single crystal and powder X-ray diffraction, CHN analyses, spectroscopic and thermal studies. Four of them are molecular phenyl- and benzyl-phosphonates containing discrete [(MoO 3 ) 5 (O 3 PR) 2 ] 4- (R = Ph or CH 2 Ph) cyclic anions. The sixteen non-molecular compounds are layered isostructural phenylphosphonates, A 2 [Mo 2 O 5 (O 3 PPh) 2 ] (A = NH 4 , Tl, Rb, Cs) and K 1.5 (H 3 O) 0.5 [Mo 2 O 5 (O 3 PPh) 2 ] and the corresponding diphosphonate compounds with pillared anionic layers, A 2 [Mo 2 O 5 (O 3 P(CH 2 ) 3 PO 3 )], A 2 [Mo 2 O 5 (O 3 P(CH 2 ) 4 PO 3 )] and A 2 [Mo 2 O 5 (O 3 P(C 6 H 4 )PO 3 )]. The A + ions reside in the interlayer region as well as in the cavities within the anionic layers.

  9. Etude des mécanismes d'ionisation de H{2}O par interaction He^{*}(2 ^1S, 2 ^3S)/Ne^{*}(^3P{0}, ^3P{2})+H{2}O

    NASA Astrophysics Data System (ADS)

    Le Nadan, André; Sinou, Guillaume; Tuffin, Firmin

    1993-06-01

    Experimental observations of Penning ionisation of H{2}O by the helium metastables 21S and 23S and by the neon metastables ^3P{0} and ^3P{2} are reported. The kinetic energies of the ions created during the collision process (both parent and fragment) are analysed. Certain particularities of the experimental results are explained by involving the hypothesis of transfers of vibrational energy to kinetic energy. Furthermore, the forms of the energy distributions of the fragment ions are explained by th predissociation of the ^2B{2} state of H{2}O+. Nous avons étudié l'ionisation Penning de H{2}O par des métastables 21S et 23S de l'hélium, ainsi que ^3P{0} et ^3P{2} du néon. Nous avons analysé l'énergie cinétique des ions créés au cours de la collision (parents et fragments). Afin d'interpréter certaines particularités expérimentales, l'hypothèse de transferts d'énergie de vibration en énergie cinétique est proposées. Par ailleurs, les caractéristiques des distributions en énergie des ions fragments sont expliquées par la prédissociation de l'état ^2B{2} de H{2}O+.

  10. Metabolism of D-[1-3H]glucose, D-[2-3H]glucose, D-[5-3H]glucose, D-[6-3H]glucose and D-[U-14C]glucose by rat and human erythrocytes incubated in the presence of H2O or D2O.

    PubMed

    Conget, I; Malaisse, W J

    1995-02-01

    The present study investigates whether heavy water affects the efficiency of 3HOH production from D-[1-3H]glucose, D-[2-3H]glucose, D-[5-3H]glucose and D-[6-3H]glucose relative to the total generation of tritiated metabolites produced by either rat or human erythrocytes. The relative 3HOH yield was close to 95% with D-[5-3H]glucose, 72% with D-[2-3H]glucose, 22-32% with D-[1-3H]glucose, and only 12% with D-[6-3H]glucose. In the latter case, the comparison of the specific radioactivity of intracellular and extracellular acidic metabolites, expressed relative to that of 14C-labelled metabolites produced from D-[U-14C]glucose, indicated that the generation of 3HOH from D-[6-3H]glucose occurs at distal metabolic steps, such as the partial reversion of the pyruvate kinase reaction or the interconversion of pyruvate and L-alanine in the reaction catalysed by glutamate-pyruvate transaminase. As a rule, the substitution of H2O by D2O only caused minor to negligible changes in the relative 3HOH yield. This implies that the unexpectedly high deuteration of 13C-labelled D-glucose metabolites recently documented in erythrocytes exposed to D2O cannot be attributed to any major interference of heavy water with factors regulating both the deuteration and detritiation efficiency, such as the enzyme-to-enzyme tunnelling of specific glycolytic intermediates.

  11. Abatement of Polychoro-1,3-butadienes in Aqueous Solution by Ozone, UV Photolysis, and Advanced Oxidation Processes (O3/H2O2 and UV/H2O2).

    PubMed

    Lee, Minju; Merle, Tony; Rentsch, Daniel; Canonica, Silvio; von Gunten, Urs

    2017-01-03

    The abatement of 9 polychloro-1,3-butadienes (CBDs) in aqueous solution by ozone, UV-C(254 nm) photolysis, and the corresponding advanced oxidation processes (AOPs) (i.e., O 3 /H 2 O 2 and UV/H 2 O 2 ) was investigated. The following parameters were determined for 9 CBDs: second-order rate constants for the reactions of CBDs with ozone (k O 3 ) (<0.1-7.9 × 10 3 M -1 s -1 ) or with hydroxyl radicals (k • OH ) (0.9 × 10 9 - 6.5 × 10 9 M -1 s -1 ), photon fluence-based rate constants (k') (210-2730 m 2 einstein -1 ), and quantum yields (Φ) (0.03-0.95 mol einstein -1 ). During ozonation of CBDs in a natural groundwater, appreciable abatements (>50% at specific ozone doses of 0.5 gO 3 /gDOC to ∼100% at ≥1.0 gO 3 /gDOC) were achieved for tetra-CBDs followed by (Z)-1,1,2,3,4-penta-CBD and hexa-CBD. This is consistent with the magnitude of the determined k O 3 and k • OH . The formation of bromate, a potentially carcinogenic ozonation byproduct, could be significantly reduced by addition of H 2 O 2 . For a typical UV disinfection dose (400 J/m 2 ), various extents of phototransformations (10-90%) could be achieved. However, the efficient formation of photoisomers from CBDs with E/Z configuration must be taken into account because of their potential residual toxicity. Under UV-C(254 nm) photolysis conditions, no significant effect of H 2 O 2 addition on CBDs abatement was observed due to an efficient direct phototransformation of CBDs.

  12. Kamarizaite, Fe{3/3+}(AsO4)2(OH)3 · 3H2O, a new mineral species, arsenate analogue of tinticite

    NASA Astrophysics Data System (ADS)

    Chukanov, N. V.; Pekov, I. V.; Möckel, S.; Mukhanova, A. A.; Belakovsky, D. I.; Levitskaya, L. A.; Bekenova, G. K.

    2010-12-01

    Kamarizaite, a new mineral species, has been identified in the dump of the Kamariza Mine, Lavrion mining district, Attica Region, Greece, in association with goethite, scorodite, and jarosite. It was named after type locality. Kamarizaite occurs as fine-grained monomineralic aggregates (up to 3 cm across) composed of platy crystals up to 1 μm in size and submicron kidney-shaped segregations. The new mineral is yellow to beige, with light yellow streak. The Mohs hardness is about 3. No cleavage is observed. The density measured by hydrostatic weighing is 3.16(1) g/cm3, and the calculated density is 3.12 g/cm3. The wavenumbers of absorption bands in the IR spectrum of kamarizaite are (cm-1; s is strong band, w is weak band): 3552, 3315s, 3115, 1650w, 1620w, 1089, 911s, 888s, 870, 835s, 808s, 614w, 540, 500, 478, 429. According to TG and IR data, complete dehydration and dehydroxylation in vacuum (with a weight loss of 15.3(1)%) occurs in the temperature range 110-420°C. Mössbauer data indicate that all iron in kamarizaite is octahedrally coordinated Fe3+. Kamarizaite is optically biaxial, positive: n min = 1.825, n max = 1.835, n mean = 1.83(1) (for a fine-grained aggregate). The chemical composition of kamarizaite (electron microprobe, average of four point analyses) is as follows, wt %: 0.35 CaO, 41.78 Fe2O3, 39.89 As2O5, 1.49 SO3, 15.3 H2O (from TG data); the total is 98.81. The empirical formula calculated on the basis of (AsO4,SO4)2 is Ca0.03Fe{2.86/3+} (AsO4)1.90(SO4)0.10(OH)2.74 · 3.27H2O. The idealized formula is Fe{3/3+}(AsO4)2(OH)3 · 3H2O. Kamarizaite is an arsenate analogue of orthorhombic tinticite, space group Pccm, Pcc2, Pcmm, Pcm21, or Pc2 m; a = 21.32(1), b = 13.666(6), c =15.80(1) Å, V= 4603.29(5) Å3, Z= 16. The strongest reflections of the X-ray powder diffraction pattern [ bar d , Å ( I, %) ( hkl)] are: 6.61 (37) (112, 120), 5.85 (52) (311), 3.947 (100) (004, 032, 511), 3.396 (37) (133, 431), 3.332 (60) (314), 3.085 (58) (621, 414, 324

  13. Reversible Sialylation: Synthesis of CMP-NeuAc from 5′-CMP using α2,3-sialyl O-glycan, glycolipid and macromolecule based donors allow for the synthesis of diverse sialylated products

    PubMed Central

    Chandrasekaran, E.V.; Xue, Jun; Xia, Jie; Locke, Robert D.; Matta, Khushi L.; Neelamegham, Sriram

    2008-01-01

    Sialyltransferases transfer sialic acid from CMP-NeuAc to an acceptor molecule. Trans-sialidases of parasites transfer α2,3 linked sialic acid from one molecule to another without the involvement of CMP-NeuAc. Here, we report another type of sialylation termed reverse sialylation catalyzed by mammalian sialyltransferase ST3Gal-II. This enzyme synthesizes CMP-NeuAc by transferring NeuAc from the NeuAcα2,3Galβ1,3GalNAcα-unit of O-glycans, 3-sialyl globo unit of glycolipids and sialylated macromolecules to 5′-CMP. CMP-NeuAc produced in situ is utilized by the same enzyme to sialylate other O-glycans and by other sialyltransferases such as ST6Gal-I and ST6GalNAc-I forming α2,6 sialylated compounds. ST3Gal-II also catalyzed the conversion of 5′-UMP to UMP-NeuAc, which was found to be an inactive sialyl donor. Reverse sialylation proceeded without the need for free sialic acid, divalent metal ions or energy. The direct sialylation using CMP-NeuAc as well as the formation of CMP-NeuAc from 5′-CMP had a wide optimum range (pH 5.2–7.2 and 4.8–6.4 respectively) whereas the entire reaction comprising in situ production of CMP-NeuAc and sialylation of acceptor had a sharp optimum at pH 5.6 (the activity level 50% at pH 5.2 & 6.8 and 25% at pH 4.8 & 7.2). Several properties distinguish forward/conventional vs. reverse sialylation: i. Sodium citrate inhibited forward sialylation but not reverse sialylation. ii. 5′-CDP, a potent forward sialyltransferase inhibitor, did not inhibit the conversion of 5′-CMP to CMP-NeuAc. iii. The mucin core 2 compound 3-O-sulfoα2,3Galβ1,4GlcNAcβ1,6(Galβ1,3)GalNAcα-O-Bn, an efficient acceptor for ST3Gal-II, inhibited the conversion of 5′-CMP to CMP-NeuAc. A significant level of reverse sialylation activity is noted in human prostate cancer cell lines LNCaP and PC3. Overall, the study demonstrates that the sialyltransferase reaction is readily reversible in the case of ST3Gal-II and can be exploited for the enzymatic

  14. Expanding the remarkable structural diversity of uranyl tellurites: hydrothermal preparation and structures of K[UO(2)Te(2)O(5)(OH)], Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O, beta-Tl(2)[UO(2)(TeO(3))(2)], and Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2).

    PubMed

    Almond, Philip M; Albrecht-Schmitt, Thomas E

    2002-10-21

    The reactions of UO(2)(C(2)H(3)O(2))(2).2H(2)O with K(2)TeO(3).H(2)O, Na(2)TeO(3) and TlCl, or Na(2)TeO(3) and Sr(OH)(2).8H(2)O under mild hydrothermal conditions yield K[UO(2)Te(2)O(5)(OH)] (1), Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O (2) and beta-Tl(2)[UO(2)(TeO(3))(2)] (3), or Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2) (4), respectively. The structure of 1 consists of tetragonal bipyramidal U(VI) centers that are bound by terminal oxo groups and tellurite anions. These UO(6) units span between one-dimensional chains of corner-sharing, square pyramidal TeO(4) polyhedra to create two-dimensional layers. Alternating corner-shared oxygen atoms in the tellurium oxide chains are protonated to create short/long bonding patterns. The one-dimensional chains of corner-sharing TeO(4) units found in 1 are also present in 2. However, in 2 there are two distinct chains present, one where alternating corner-shared oxygen atoms are protonated, and one where the chains are unprotonated. The uranyl moieties in 2 are bound by five oxygen atoms from the tellurite chains to create seven-coordinate pentagonal bipyramidal U(VI). The structures of 3 and 4 both contain one-dimensional [UO(2)(TeO(3))(2)](2-) chains constructed from tetragonal bipyramidal U(VI) centers that are bridged by tellurite anions. The chains differ between 3 and 4 in that all of the pyramidal tellurite anions in 3 have the same orientation, whereas the tellurite anions in 4 have opposite orientations on each side of the chain. In 4, there are also additional isolated TeO(3)(2-) anions present. Crystallographic data: 1, orthorhombic, space group Cmcm, a = 7.9993(5) A, b = 8.7416(6) A, c = 11.4413(8) A, Z = 4; 2, orthorhombic, space group Pbam, a = 10.0623(8) A, b = 23.024(2) A, c = 7.9389(6) A, Z = 4; 3, monoclinic, space group P2(1)/n, a = 5.4766(4) A, b = 8.2348(6) A, c = 20.849(3) A, beta = 92.329(1) degrees, Z = 4; 4, monoclinic, space group C2/c, a = 20.546(1) A, b = 5.6571(3) A, c = 13.0979(8) A, beta

  15. Effect of substituent groups (R= sbnd CH3, sbnd Br and sbnd CF3) on the structure, stability and redox property of [Cr(R-pic)2(H2O)2]NO3·H2O complexes

    NASA Astrophysics Data System (ADS)

    Chai, Jie; Liu, Yanfei; Liu, Bin; Yang, Binsheng

    2017-12-01

    Complexes [Cr(3-CH3-pic)2(H2O)2]NO3·H2O (1), [Cr(5-Br-pic)2(H2O)2]NO3·H2O (2) and [Cr(5-CF3-pic)2(H2O)2]NO3·H2O (3) were synthesized (pic = pyridine-2-carboxylic acid) and characterized by X-ray crystal diffraction. Crystal structure indicates that two bidentate ligands occupy equatorial position and two H2O occupy axial positions in trans-configuration. (i) Decomposition of complexes 1, 2 and 3 in different medium (phosphate buffered saline (PBS), apo-ovotransferrin (apootf) and EDTA) indicates that decomposition rate constants of these complexes follow the sequence of 1 < 2 < 3. (ii) The redox potential of Cr(III)/Cr(II) by cyclic voltammetry follows the sequence of 1 (-1.20 V) > 3 (-1.29 V) > 2 (-1.31 V). (iii) In addition, ·OH-generation of the new synthesized complexes was determined by Fenton-like reaction in comparison with Cr(pic)3, and it may be related to the reduction potential of the complexes. (iv) Moreover, Hammett substituent constants σp (inductive) and σm (resonance) (R = 3-CH3, 5-Br, 5-CF3) were introduced to evaluate the impact of substituent groups on the bond length and decomposition kinetics. The substituent group on the ligand has great effect on the properties of the complexes.

  16. Identification of a 3rd Na+ Binding Site of the Glycine Transporter, GlyT2.

    PubMed

    Subramanian, Nandhitha; Scopelitti, Amanda J; Carland, Jane E; Ryan, Renae M; O'Mara, Megan L; Vandenberg, Robert J

    2016-01-01

    The Na+/Cl- dependent glycine transporters GlyT1 and GlyT2 regulate synaptic glycine concentrations. Glycine transport by GlyT2 is coupled to the co-transport of three Na+ ions, whereas transport by GlyT1 is coupled to the co-transport of only two Na+ ions. These differences in ion-flux coupling determine their respective concentrating capacities and have a direct bearing on their functional roles in synaptic transmission. The crystal structures of the closely related bacterial Na+-dependent leucine transporter, LeuTAa, and the Drosophila dopamine transporter, dDAT, have allowed prediction of two Na+ binding sites in GlyT2, but the physical location of the third Na+ site in GlyT2 is unknown. A bacterial betaine transporter, BetP, has also been crystallized and shows structural similarity to LeuTAa. Although betaine transport by BetP is coupled to the co-transport of two Na+ ions, the first Na+ site is not conserved between BetP and LeuTAa, the so called Na1' site. We hypothesized that the third Na+ binding site (Na3 site) of GlyT2 corresponds to the BetP Na1' binding site. To identify the Na3 binding site of GlyT2, we performed molecular dynamics (MD) simulations. Surprisingly, a Na+ placed at the location consistent with the Na1' site of BetP spontaneously dissociated from its initial location and bound instead to a novel Na3 site. Using a combination of MD simulations of a comparative model of GlyT2 together with an analysis of the functional properties of wild type and mutant GlyTs we have identified an electrostatically favorable novel third Na+ binding site in GlyT2 formed by Trp263 and Met276 in TM3, Ala481 in TM6 and Glu648 in TM10.

  17. Excision of uranium oxide chains and ribbons in the novel one-dimensional uranyl iodates K(2)[(UO(2))3(IO(3))(4)O(2)] and Ba[(UO(2)2(IO(3))(2)O(2)](H(2)O).

    PubMed

    Bean, A C; Ruf, M; Albrecht-Schmitt, T E

    2001-07-30

    The alkali metal and alkaline-earth metal uranyl iodates K(2)[(UO(2))(3)(IO(3))(4)O(2)] and Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O) have been prepared from the hydrothermal reactions of KCl or BaCl(2) with UO(3) and I(2)O(5) at 425 and 180 degrees C, respectively. While K(2)[(UO(2))(3)(IO(3))(4)O(2)] can be synthesized under both mild and supercritical conditions, the yield increases from <5% to 73% as the temperature is raised from 180 to 425 degrees C. Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O), however, has only been isolated from reactions performed in the mild temperature regime. Thermal measurements (DSC) indicate that K(2)[(UO(2))(3)(IO(3))(4)O(2)] is more stable than Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O) and that both compounds decompose through thermal disproportionation at 579 and 575 degrees C, respectively. The difference in the thermal behavior of these compounds provides a basis for the divergence of their preparation temperatures. The structure of K(2)[(UO(2))(3)(IO(3))(4)O(2)] is composed of [(UO(2))(3)(IO(3))(4)O(2)](2)(-) chains built from the edge-sharing UO(7) pentagonal bipyramids and UO(6) octahedra. Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O) consists of one-dimensional [(UO(2))(2)(IO(3))(2)O(2)](2)(-) ribbons formed from the edge sharing of distorted UO(7) pentagonal bipyramids. In both compounds the iodate groups occur in both bridging and monodentate binding modes and further serve to terminate the edges of the uranium oxide chains. The K(+) or Ba(2+) cations separate the chains or ribbons in these compounds forming bonds with terminal oxygen atoms from the iodate ligands. Crystallographic data: K(2)[(UO(2))(3)(IO(3))(4)O(2)], triclinic, space group P_1, a = 7.0372(5) A, b = 7.7727(5) A, c = 8.9851(6) A, alpha = 93.386(1) degrees, beta = 105.668(1) degrees, gamma = 91.339(1) degrees, Z = 1; Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O), monoclinic, space group P2(1)/c, a = 8.062(4) A, b = 6.940(3) A, c = 21.67(1), beta= 98.05(1) degrees, Z = 4.

  18. New functional materials AC3B4O12 (Review)

    NASA Astrophysics Data System (ADS)

    Vasil'ev, A. N.; Volkova, O. S.

    2007-11-01

    The physical properties of perovskites of the type AC3B4O12, whose structure derives from simple perovskites ABO3, are reviewed. The A position is subject to strong structural distortions and splits into two new positions A and C. In the structure of AC3B4O12 vacancies and any cations with a large radius, irrespective of their charge state, can be present in the icosahedral environment of A: Na +, Cd2+, Ca2+, Sr2+, Y3+, Ln3+, and Nd4+. The C position in the square environment of oxygen can be occupied only by the Jahn-Teller cations Cu2+ and Mn3+. Transition and nontransition metal ions—Mn3+, Fe3+, Al3+, Cr3+, Ti4+, Mn4+, Ge4+, Ru4+, Ir4+, Ta5+, Nb5+, Ta5+, Sb5+—can occupy the B position in an octahedral environment. Some members of the family of complex perovskites possess properties which are characteristic for systems with heavy fermions; collinear and noncollinear magnetic structures with high ordering temperatures occur in these materials; tunneling magnetoresistance and high permittivity are observed. The diversity and unique properties make these materials attractive for practical applications.

  19. Characterization of supramolecular (H2O)18 water morphology and water-methanol (H2O)15(CH3OH)3 clusters in a novel phosphorus functionalized trimeric amino acid host.

    PubMed

    Raghuraman, Kannan; Katti, Kavita K; Barbour, Leonard J; Pillarsetty, Nagavarakishore; Barnes, Charles L; Katti, Kattesh V

    2003-06-11

    Phosphorus functionalized trimeric alanine compounds (l)- and (d)-P(CH(2)NHCH(CH(3))COOH)(3) 2 are prepared in 90% yields by the Mannich reaction of Tris(hydroxymethyl)phosphine 1 with (l)- or (d)- Alanine in aqueous media. The hydration properties of (l)-2 and (d)-2 in water and water-methanol mixtures are described. The crystal structure analysis of (l)-2.4H(2)O, reveals that the alanine molecules pack to form two-dimensional bilayers running parallel to (001). The layered structural motif depicts two closely packed monolayers of 2 each oriented with its phosphorus atoms projected at the center of the bilayer and adjacent monolayers are held together by hydrogen bonds between amine and carboxylate groups. The water bilayers are juxtaposed with the H-bonded alanine trimers leading to 18-membered (H(2)O)(18) water rings. Exposure of aqueous solution of (l)-2 and (d)-2 to methanol vapors resulted in closely packed (l)-2 and (d)-2 solvated with mixed water-methanol (H(2)O)(15)(CH(3)OH)(3) clusters. The O-O distances in the mixed methanol-water clusters of (l)-2.3H(2)O.CH(3)OH and (d)-2.3H(2)O.CH(3)OH (O-O(average) = 2.857 A) are nearly identical to the O-O distance observed in the supramolecular (H(2)O)(18) water structure (O-O(average) = 2.859 A) implying the retention of the hydrogen bonded structure in water despite the accommodation of hydrophobic methanol groups within the supramolecular (H(2)O)(15)(CH(3)OH)(3) framework. The O-O distances in (l)-2.3H(2)O.CH(3)OH and (d)-2.3H(2)O.CH(3)OH and in (H(2)O)(18) are very close to the O-O distance reported for liquid water (2.85 A).

  20. AC losses in (Bi,Pb) 2Sr 2Ca 2Cu 3O x tapes

    NASA Astrophysics Data System (ADS)

    D'Anna, G.; Indenbom, M. V.; André, M.-O.; Benoit, W.; Grivel, J.-C.; Hensel, B.; Flükiger, R.

    1994-05-01

    A double peak structure is observed in the AC losses of (Bi,Pb) 2Sr 2Ca 2Cu 3O x silver-sheathed tapes using a torsion-pendulum oscillator. The low-temperature peak is associated to the intragrain flux expulsion, while the high-temperature peak results from a macroscopic current path around the whole sample due to a well-coupled fraction of the grains. The flux pinning by the dislocations forming small-angle grain boundaries is suggested to control the transport current.

  1. Incorporation of μ3-CO3 into an MnIII/MnIV Mn12 cluster: {[(cyclam)MnIV(μ-O)2MnIII(H2O)(μ-OH)]6(μ3-CO3)2}Cl8·24H2O

    PubMed Central

    Levaton, Ben B.; Olmstead, Marilyn M.

    2010-01-01

    The centrosymmetric title cluster, hexa­aquadi-μ3-carbonato-hexa­cyclamhexa-μ2-hydroxido-dodeca-μ2-oxido-hexa­mang­an­ese(IV)hexa­manganese(III) octa­chloride tetra­cosa­hydrate, [Mn12(CO3)2O12(OH)6(C10H24N4)6(H2O)6]Cl8·24H2O, has two μ3-CO3 groups that not only bridge octahedrally coordinated MnIII ions but also act as acceptors to two different kinds of hydrogen bonds. The carbonate anion is planar within experimental error and has an average C—O distance of 1.294 (4) Å. The crystal packing is stabilized by O—H⋯Cl, O—H⋯O, N—H⋯Cl and N—H⋯O hydrogen bonds. Two of the four independent chloride ions are disordered over five positions, and eight of the 12 independent water mol­ecules are disordered over 21 positions. PMID:21587382

  2. Proton transfer reactions and dynamics in CH(3)OH-H(3)O(+)-H(2)O complexes.

    PubMed

    Sagarik, Kritsana; Chaiwongwattana, Sermsiri; Vchirawongkwin, Viwat; Prueksaaroon, Supakit

    2010-01-28

    Proton transfer reactions and dynamics in hydrated complexes formed from CH(3)OH, H(3)O(+) and H(2)O were studied using theoretical methods. The investigations began with searching for equilibrium structures at low hydration levels using the DFT method, from which active H-bonds in the gas phase and continuum aqueous solution were characterized and analyzed. Based on the asymmetric stretching coordinates (Deltad(DA)), four H-bond complexes were identified as potential transition states, in which the most active unit is represented by an excess proton nearly equally shared between CH(3)OH and H(2)O. These cannot be definitive due to the lack of asymmetric O-H stretching frequencies (nu(OH)) which are spectral signatures of transferring protons. Born-Oppenheimer molecular dynamics (BOMD) simulations revealed that, when the thermal energy fluctuations and dynamics were included in the model calculations, the spectral signatures at nu(OH) approximately 1000 cm(-1) appeared. In continuum aqueous solution, the H-bond complex with incomplete water coordination at charged species turned out to be the only active transition state. Based on the assumption that the thermal energy fluctuations and dynamics could temporarily break the H-bonds linking the transition state complex and water molecules in the second hydration shell, elementary reactions of proton transfer were proposed. The present study showed that, due to the coupling among various vibrational modes, the discussions on proton transfer reactions cannot be made based solely on static proton transfer potentials. Inclusion of thermal energy fluctuations and dynamics in the model calculations, as in the case of BOMD simulations, together with systematic IR spectral analyses, have been proved to be the most appropriate theoretical approaches.

  3. Crystal structures of hydrates of simple inorganic salts. III. Water-rich aluminium halide hydrates: AlCl3 · 15H2O, AlBr3 · 15H2O, AlI3 · 15H2O, AlI3 · 17H2O and AlBr3 · 9H2O.

    PubMed

    Schmidt, Horst; Hennings, Erik; Voigt, Wolfgang

    2014-09-01

    Water-rich aluminium halide hydrate structures are not known in the literature. The highest known water content per Al atom is nine for the perchlorate and fluoride. The nonahydrate of aluminium bromide, stable pentadecahydrates of aluminium chloride, bromide and iodide, and a metastable heptadecahydrate of the iodide have now been crystallized from low-temperature solutions. The structures of these hydrates were determined and are discussed in terms of the development of cation hydration spheres. The pentadecahydrate of the chloride and bromide are isostructural. In AlI(3) · 15H2O, half of the Al(3+) cations are surrounded by two complete hydration spheres, with six H2O in the primary and 12 in the secondary. For the heptadecahydrate of aluminium iodide, this hydration was found for every Al(3+).

  4. Co3(PO4)2·4H2O

    PubMed Central

    Lee, Young Hoon; Clegg, Jack K.; Lindoy, Leonard F.; Lu, G. Q. Max; Park, Yu-Chul; Kim, Yang

    2008-01-01

    Single crystals of Co3(PO4)2·4H2O, tricobalt(II) bis­[ortho­phosphate(V)] tetra­hydrate, were obtained under hydro­thermal conditions. The title compound is isotypic with its zinc analogue Zn3(PO4)2·4H2O (mineral name hopeite) and contains two independent Co2+ cations. One Co2+ cation exhibits a slightly distorted tetra­hedral coordination, while the second, located on a mirror plane, has a distorted octa­hedral coordination environment. The tetra­hedrally coordinated Co2+ is bonded to four O atoms of four PO4 3− anions, whereas the six-coordinate Co2+ is cis-bonded to two phosphate groups and to four O atoms of four water mol­ecules (two of which are located on mirror planes), forming a framework structure. In addition, hydrogen bonds of the type O—H⋯O are present throughout the crystal structure. PMID:21200978

  5. Nqrs Data for H4I3Li2NO9 [H4INO3·2(ILiO3)] (Subst. No. 2278)

    NASA Astrophysics Data System (ADS)

    Chihara, H.; Nakamura, N.

    This document is part of Subvolume B 'Substances Containing C10H16 … Zn' of Volume 48 'Nuclear Quadrupole Resonance Spectroscopy Data' of Landolt-Börnstein - Group III 'Condensed Matter'. It contains an extract of Section '3.2 Data tables' of the Chapter '3 Nuclear quadrupole resonance data' providing the NQRS data for H4I3Li2NO9 [H4INO3·2(ILiO3)] (Subst. No. 2278)

  6. Methanesulfonates of high-valent metals: syntheses and structural features of MoO2(CH3SO3)2, UO2(CH3SO3)2, ReO3(CH3SO3), VO(CH3SO3)2, and V2O3(CH3SO3)4 and their thermal decomposition under N2 and O2 atmosphere.

    PubMed

    Betke, Ulf; Neuschulz, Kai; Wickleder, Mathias S

    2011-11-04

    Oxide methanesulfonates of Mo, U, Re, and V have been prepared by reaction of MoO(3), UO(2)(CH(3)COO)(22H(2)O, Re(2)O(7)(H(2)O)(2), and V(2)O(5) with CH(3)SO(3)H or mixtures thereof with its anhydride. These compounds are the first examples of solvent-free oxide methanesulfonates of these elements. MoO(2)(CH(3)SO(3))(2) (Pbca, a=1487.05(4), b=752.55(2), c=1549.61(5) pm, V=1.73414(9) nm(3), Z=8) contains [MoO(2)] moieties connected by [CH(3)SO(3)] ions to form layers parallel to (100). UO(2)(CH(3)SO(3))(2) (P2(1)/c, a=1320.4(1), b=1014.41(6), c=1533.7(1) pm, β=112.80(1)°, V=1.8937(3) nm(3), Z=8) consists of linear UO(2)(2+) ions coordinated by five [CH(3)SO(3)] ions, forming a layer structure. VO(CH(3)SO(3))(2) (P2(1)/c, a=1136.5(1), b=869.87(7), c=915.5(1) pm, β=113.66(1)°, V=0.8290(2) nm(3), Z=4) contains [VO] units connected by methanesulfonate anions to form corrugated layers parallel to (100). In ReO(3)(CH(3)SO(3)) (P1, a=574.0(1), b=1279.6(3), c=1641.9(3) pm, α=102.08(2), β=96.11(2), γ=99.04(2)°, V=1.1523(4) nm(3), Z=8) a chain structure exhibiting infinite O-[ReO(2)]-O-[ReO(2)]-O chains is formed. Each [ReO(2)]-O-[ReO(2)] unit is coordinated by two bidentate [CH(3)SO(3)] ions. V(2)O(3)(CH(3)SO(3))(4) (I2/a, a=1645.2(3), b=583.1(1), c=1670.2(3) pm, β=102.58(3), V=1.5637(5) pm(3), Z=4) adopts a chain structure, too, but contains discrete [VO]-O-[VO] moieties, each coordinated by two bidentate [CH(3)SO(3)] ligands. Additional methanesulfonate ions connect the [V(2)O(3)] groups along [001]. Thermal decomposition of the compounds was monitored under N(2) and O(2) atmosphere by thermogravimetric/differential thermal analysis and XRD measurements. Under N(2) the decomposition proceeds with reduction of the metal leading to the oxides MoO(2), U(3)O(7), V(4)O(7), and VO(2); for MoO(2)(CH(3)SO(3))(2), a small amount of MoS(2) is formed. If the thermal decomposition is carried out in a atmosphere of O(2) the oxides MoO(3) and V(2)O(5) are formed. Copyright

  7. Slow spin relaxation induced by magnetic field in [NdCo(bpdo)(H2O)4(CN)6]⋅3H2O.

    PubMed

    Vrábel, P; Orendáč, M; Orendáčová, A; Čižmár, E; Tarasenko, R; Zvyagin, S; Wosnitza, J; Prokleška, J; Sechovský, V; Pavlík, V; Gao, S

    2013-05-08

    We report on a comprehensive investigation of the magnetic properties of [NdCo(bpdo)(H2O)4(CN)6]⋅3H2O (bpdo=4, 4'-bipyridine-N,N'-dioxide) by use of electron paramagnetic resonance, magnetization, specific heat and susceptibility measurements. The studied material was identified as a magnet with an effective spin S = 1/2 and a weak exchange interaction J/kB = 25 mK. The ac susceptibility studies conducted at audio frequencies and at temperatures from 1.8 to 9 K revealed that the application of a static magnetic field induces a slow spin relaxation. It is suggested that the relaxation in the magnetic field appears due to an Orbach-like process between the two lowest doublet energy states of the magnetic Nd(3+) ion. The appearance of the slow relaxation in a magnetic field cannot be associated with a resonant phonon trapping. The obtained results suggest that the relaxation is influenced by nuclear spin driven quantum tunnelling which is suppressed by external magnetic field.

  8. Identification of a 3rd Na+ Binding Site of the Glycine Transporter, GlyT2

    PubMed Central

    Subramanian, Nandhitha; Scopelitti, Amanda J.; Carland, Jane E.; Ryan, Renae M.; O’Mara, Megan L.; Vandenberg, Robert J.

    2016-01-01

    The Na+/Cl- dependent glycine transporters GlyT1 and GlyT2 regulate synaptic glycine concentrations. Glycine transport by GlyT2 is coupled to the co-transport of three Na+ ions, whereas transport by GlyT1 is coupled to the co-transport of only two Na+ ions. These differences in ion-flux coupling determine their respective concentrating capacities and have a direct bearing on their functional roles in synaptic transmission. The crystal structures of the closely related bacterial Na+-dependent leucine transporter, LeuTAa, and the Drosophila dopamine transporter, dDAT, have allowed prediction of two Na+ binding sites in GlyT2, but the physical location of the third Na+ site in GlyT2 is unknown. A bacterial betaine transporter, BetP, has also been crystallized and shows structural similarity to LeuTAa. Although betaine transport by BetP is coupled to the co-transport of two Na+ ions, the first Na+ site is not conserved between BetP and LeuTAa, the so called Na1' site. We hypothesized that the third Na+ binding site (Na3 site) of GlyT2 corresponds to the BetP Na1' binding site. To identify the Na3 binding site of GlyT2, we performed molecular dynamics (MD) simulations. Surprisingly, a Na+ placed at the location consistent with the Na1' site of BetP spontaneously dissociated from its initial location and bound instead to a novel Na3 site. Using a combination of MD simulations of a comparative model of GlyT2 together with an analysis of the functional properties of wild type and mutant GlyTs we have identified an electrostatically favorable novel third Na+ binding site in GlyT2 formed by Trp263 and Met276 in TM3, Ala481 in TM6 and Glu648 in TM10. PMID:27337045

  9. Structurally characterized 1,1,3,3-tetramethylguanidine solvated magnesium aryloxide complexes: [Mg(mu-OEt)(DBP)(H-TMG)]2, [Mg(mu-OBc)(DBP)(H-TMG)]2, [Mg(mu-TMBA)(DBP)(H-TMG)]2, [Mg(mu-DPP)(DBP)(H-TMG)]2, [Mg(BMP)2(H-TMG)2], [Mg(O-2,6-Ph2C6H3)2 (H-TMG)2].

    PubMed

    Monegan, Jessie D; Bunge, Scott D

    2009-04-06

    The synthesis and structural characterization of several 1,1,3,3-tetramethylguanidine (H-TMG) solvated magnesium aryloxide complexes are reported. Bu(2)Mg was successfully reacted with H-TMG, HOC(6)H(3)(CMe(3))(2)-2,6 (H-DBP), and either ethanol, a carboxylic acid, or diphenyl phosphate in a 1:1 ratio to yield the corresponding [Mg(mu-L)(DBP)(H-TMG)](2) where L = OCH(2)CH(3) (OEt, 1), O(2)CC(CH(3))(3) (OBc, 2), O(2)C(C(6)H(2)-2,4,6-(CH(3))(3)) (TMBA, 3), or O(2)P(OC(6)H(5))(2) (DPP, 4). Bu(2)Mg was also reacted with two equivalents of H-TMG and HOC(6)H(3)(CMe(3))-2-(CH(3))-6 (BMP) or HO-2,6-Ph(2)C(6)H(3) to yield [Mg(BMP)(2)(H-TMG)(2)] (5) and [Mg(O-2,6-Ph(2)C(6)H(3))(2)(H-TMG)(2)] (6). Compounds 1-6 were characterized by single-crystal X-ray diffraction. Polymerization of l- and rac-lactide with 1 was found to generate polylactide (PLA). A discussion concerning the relevance of compounds 2 - 4 to the structure of Mg-activated phosphatase enzymes is also provided. The bulk powders for all complexes were found to be in agreement with the crystal structures based on elemental analyses, FT-IR spectroscopy, and (1)H, (13)C and (31)P NMR studies.

  10. A novel amido-pyrophosphate Mn(II) chelate complex with the synthetic ligand O{P(O)[NHC(CH3)3]2}2 (L): [Mn(L)2{OC(H)N(CH3)2}2]Cl2·2H2O.

    PubMed

    Tarahhomi, Atekeh; Pourayoubi, Mehrdad; Fejfarová, Karla; Dušek, Michal

    2013-03-01

    The title complex, trans-bis(dimethylformamide-κO)bis{N,N'-N'',N'''-tetra-tert-butyl[oxybis(phosphonic diamide-κO)]}manganese(II) dichloride dihydrate, [Mn(C16H40N4O3P2)2(C3H7NO)2]Cl2·2H2O, is the first example of a bis-chelate amido-pyrophosphate (pyrophosphoramide) complex containing an O[P(O)(NH)2]2 fragment. Its asymmetric unit contains half of the complex dication, one chloride anion and one water molecule. The Mn(II) atom, located on an inversion centre, is octahedrally coordinated, with a slight elongation towards the monodentate dimethylformamide ligand. Structural features of the title complex, such as the P=O bond lengths and the planarity of the chelate ring, are compared with those of previously reported complexes with six-membered chelates involving the fragments C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)2 and P(O)] and O[P(O)(N)2]2. This analysis shows that the six-membered chelate rings are less puckered in pyrophosphoramide complexes containing a P(O)OP(O) skeleton, such as the title compound. The extended structure of the title complex involves a linear aggregate mediated by N-H...O and N-H...Cl hydrogen bonds, in which the chloride anion is an acceptor in two additional O-H...Cl hydrogen bonds.

  11. Topology-energy relationships and lowest energy configurations for pentagonal dodecahedral (H2O)20X clusters, X=empty, H2O, NH3, H3O+: The importance of O-topology

    NASA Astrophysics Data System (ADS)

    Anick, David J.

    2010-04-01

    For (H2O)20X water clusters consisting of X enclosed by the 512 dodecahedral cage, X=empty, H2O, NH3, and H3O+, databases are made consisting of 55-82 isomers optimized via B3LYP/6-311++G∗∗. Correlations are explored between ground state electronic energy (Ee) or electronic energy plus zero point energy (Ee+ZPE) and the clusters' topology, defined as the set of directed H-bonds. Linear regression is done to identify topological features that correlate with cluster energy. For each X, variables are found that account for 99% of the variance in Ee and predict it with a rms error under 0.2 kcal/mol. The method of analysis emphasizes the importance of an intermediate level of structure, the "O-topology," consisting of O-types and a list of O pairs that are bonded but omitting H-bond directions, as a device to organize the databases and reduce the number of structures one needs to consider. Relevant variables include three parameters, which count the number of H-bonds having particular donor and acceptor types; |M|2, where M is the cluster's vector dipole moment; and the projection of M onto the symmetry axis of X. Scatter diagrams for Ee or Ee+ZPE versus |M| show that clusters fall naturally into "families" defined by the values of certain discrete parameters, the "major parameters," for each X. Combining "family" analysis and O-topologies, a small group of clusters is identified for each X that are candidates to be the global minimum, and the minimum is determined. For X=H3O+, one cluster with central hydronium lies just 2.08 kcal/mol above the lowest isomer with surface hydronium. Implications of the methodology for dodecahedral (H2O)20(NH4+) and (H2O)20(NH4+)(OH-) are discussed, and new lower energy isomers are found. For MP2/TZVP, the lowest-energy (H2O)20(NH4+) isomer features a trifurcated H-bond. The results suggest a much more efficient and comprehensive way of seeking low-energy water cluster geometries that may have wide applicability.

  12. Topology-energy relationships and lowest energy configurations for pentagonal dodecahedral (H2O)20X clusters, X = empty, H2O, NH3, H3O+: the importance of O-topology.

    PubMed

    Anick, David J

    2010-04-28

    For (H(2)O)(20)X water clusters consisting of X enclosed by the 5(12) dodecahedral cage, X = empty, H(2)O, NH(3), and H(3)O(+), databases are made consisting of 55-82 isomers optimized via B3LYP/6-311++G(**). Correlations are explored between ground state electronic energy (Ee) or electronic energy plus zero point energy (Ee+ZPE) and the clusters' topology, defined as the set of directed H-bonds. Linear regression is done to identify topological features that correlate with cluster energy. For each X, variables are found that account for 99% of the variance in Ee and predict it with a rms error under 0.2 kcal/mol. The method of analysis emphasizes the importance of an intermediate level of structure, the "O-topology," consisting of O-types and a list of O pairs that are bonded but omitting H-bond directions, as a device to organize the databases and reduce the number of structures one needs to consider. Relevant variables include three parameters, which count the number of H-bonds having particular donor and acceptor types; absolute value(M)(2), where M is the cluster's vector dipole moment; and the projection of M onto the symmetry axis of X. Scatter diagrams for Ee or Ee+ZPE versus absolute value(M) show that clusters fall naturally into "families" defined by the values of certain discrete parameters, the "major parameters," for each X. Combining "family" analysis and O-topologies, a small group of clusters is identified for each X that are candidates to be the global minimum, and the minimum is determined. For X = H(3)O(+), one cluster with central hydronium lies just 2.08 kcal/mol above the lowest isomer with surface hydronium. Implications of the methodology for dodecahedral (H(2)O)(20)(NH(4)(+)) and (H(2)O)(20)(NH(4)(+))(OH(-)) are discussed, and new lower energy isomers are found. For MP2/TZVP, the lowest-energy (H(2)O)(20)(NH(4)(+)) isomer features a trifurcated H-bond. The results suggest a much more efficient and comprehensive way of seeking low

  13. Synthesis of cationic iridium(I) complexes of water-soluble phosphine ligands, [Ir(CO)(TPPMS){sub 3}]CF{sub 3}SO{sub 3}, [Ir(CO)(H{sub 2}O)(TPPTS){sub 2}]CF{sub 3}SO{sub 3}, and [Ir(CO){sub 2}(TPPMS){sub 3}]ClO{sub 4} (TPPMS = PPh{sub 2}(m-C{sub 6}H{sub 4}SO{sub 3}K), TPPTS = P(m-C{sub 6}H{sub 4}SO{sub 3}Na){sub 3})

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

    Paterniti, D.P.; Francisco, L.W.; Atwood, J.D.

    Several new water-soluble iridium(I) complexes were synthesized and their reactivities with small molecules (H{sub 2} or CO) in polar solvents (DMSO or H{sub 2}O) examined. Reaction of H{sub 2} with [Ir(CO)(TPPMS){sub 3}]CF{sub 3}SO{sub 3} (TPPMS = P(C{sub 6}H{sub 5}){sub 2}(m-C{sub 6}H{sub 4}SO{sub 3}K)) in DMSO or H{sub 2}O produces [cis,mer-Ir(CO)(H){sub 2}(TPPMS){sub 3}]CF{sub 3}SO{sub 3}, while the reaction of CO with [Ir(CO)(TPPMS){sub 3}]-CF{sub 3}SO{sub 3} in water yields [Ir(CO){sub 2}(TPPMS){sub 3}]CF{sub 3}SO{sub 3}. Carbonylation of [Ir(CO){sub 2}(TPPMS){sub 3}]ClO{sub 4} in DMSO produces [Ir(CO){sub 3}(TPPMS){sub 2}]ClO{sub 4} and TPPMS; no reaction is observed in H{sub 2}O. Hydrogenation of [Ir(CO){sub 2}(TPPMS){sub 3}]ClO{sub 4}more » in DMSO or H{sub 2}O yields [cis,mer-Ir(CO)(H){sub 2}(TPPMS){sub 3}]ClO{sub 4}, while reaction of H{sub 2} with an aqueous solution of [Ir(CO)(H{sub 2}O)(TPPTS){sub 2}]CF{sub 3}SO{sub 3} produces [Ir(CO)(H{sub 2}O)(H){sub 2}(TPPTS){sub 2}]CF{sub 3}SO{sub 3}. Reaction of trans-Ir(CO)ClL{sub 2} (L = TPPMS or TPPTS) with excess L in H{sub 2}O produces [Ir(CO)L{sub 3}]Cl, while no reaction occurs in DMSO, [Ir(CO){sub 3}(TPPMS){sub 2}]Cl reacts irreversibly with TPPMS in H{sub 2}O to produce [Ir(CO){sub 2}-(TPPMS){sub 3}]Cl.« less

  14. Gli3 Regulation of Myogenesis Is Necessary for Ischemia-Induced Angiogenesis

    PubMed Central

    Renault, Marie-Ange; Vandierdonck, Soizic; Chapouly, Candice; Yu, Yang; Qin, Gangjian; Metras, Alexandre; Couffinhal, Thierry; Losordo, Douglas W.; Yao, Qinyu; Reynaud, Annabel; Jaspard-Vinassa, Béatrice; Belloc, Isabelle; Desgranges, Claude; Gadeau, Alain-Pierre

    2015-01-01

    Rationale A better understanding of the mechanism underlying skeletal muscle repair is required to develop therapies that promote tissue regeneration in adults. Hedgehog signaling has been shown previously to be involved in myogenesis and angiogenesis: 2 crucial processes for muscle development and regeneration. Objective The objective of this study was to identify the role of the hedgehog transcription factor Gli3 in the crosstalk between angiogenesis and myogenesis in adults. Methods and Results Using conditional knockout mice, we found that Gli3 deficiency in endothelial cells did not affect ischemic muscle repair, whereas in myocytes, Gli3 deficiency resulted in severely delayed ischemia-induced myogenesis. Moreover, angiogenesis was also significantly impaired in HSA-CreERT2; Gli3Flox/Flox mice, demonstrating that impaired myogenesis indirectly affects ischemia-induced angiogenesis. The role of Gli3 in myocytes was then further investigated. We found that Gli3 promotes myoblast differentiation through myogenic factor 5 regulation. In addition, we found that Gli3 regulates several proangiogenic factors, including thymidine phosphorylase and angiopoietin-1 both in vitro and in vivo, which indirectly promote endothelial cell proliferation and arteriole formation. In addition, we found that Gli3 is upregulated in proliferating myoblasts by the cell cycle–associated transcription factor E2F1. Conclusions This study shows for the first time that Gli3-regulated postnatal myogenesis is necessary for muscle repair–associated angiogenesis. Most importantly, it implies that myogenesis drives angiogenesis in the setting of skeletal muscle repair and identifies Gli3 as a potential target for regenerative medicine. PMID:24044950

  15. A neodymium(III)-ammonium complex involving oxalate and carbonate ligands: (NH4)2[Nd2(C2O4)3(CO3)(H2O)].H2O.

    PubMed

    Trombe, Jean-Christian; Galy, Jean; Enjalbert, Renée

    2002-10-01

    The title compound, diammonium aqua-mu-carbonato-tri-mu-oxalato-dineodymium(III) hydrate, (NH(4))(2)[Nd(2)(CO(3))(C(2)O(4))(3)(H(2)O)].H(2)O, involving the two ligands oxalate and carbonate, has been prepared hydrothermally as single crystals. The Nd atoms form a tetranuclear unit across the inversion centre at (1/2, 1/2, 1/2). Starting from this tetranuclear unit, the oxalate ligands serve to develop a three-dimensional network. The carbonate group acts as a bis-chelating ligand to two Nd atoms, and is monodentate to a third Nd atom. The oxalate groups are all bis-chelating. The two independent Nd atoms are ninefold coordinated and the coordination polyhedron of these atoms is a distorted monocapped antiprism.

  16. Thermal, Structural, AC Conductivity, and Dielectric Properties of Ethyl-2-amino-6-ethyl-5-oxo-4-(3-phenoxyphenyl)-5,6-dihydro-4H-pyrano[3,2-c]quinoline-3-carboxylate Thin Films

    NASA Astrophysics Data System (ADS)

    El-Shabaan, M. M.

    2018-05-01

    Thermal, structural, alternating-current (AC) conductivity (σ AC), and dielectric properties of ethyl-2-amino-6-ethyl-5-oxo-4-(3-phenoxyphenyl)-5,6-dihydro-4H-pyrano[3,2-c]quinoline-3-carboxylate (HPQC) thin films have been studied. Thermogravimetry analysis and differential scanning calorimetry confirmed the thermal stability of HPQC over a wide temperature range. Fourier-transform infrared spectroscopy and x-ray diffraction analysis were carried out on HPQC in powder form and as-deposited thin film. The crystal system and space group type were determined for HPQC in powder form. The AC conductivity and dielectric properties were determined in the frequency range from 0.5 kHz to 5 MHz and temperature range from 296 K to 443 K. The AC electrical conduction of HPQC thin film was found to be governed by the small-polaron tunneling mechanism. The polaron hopping energy (W H), tunneling distance (R), and density of states (N) near the Fermi level were determined as functions of temperature and frequency. The dielectric properties of HPQC thin film were studied by analysis of Nyquist diagrams, the dissipation factor (tan δ), and real (ɛ') and imaginary (ɛ″) parts of the dielectric constant.

  17. High-throughput and in situ EDXRD investigation on the formation of two new metal aminoethylphosphonates - Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}) and Ca(OH)(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3}){center_dot}2H{sub 2}O

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

    Schmidt, Corinna; Feyand, Mark; Rothkirch, Andre

    2012-04-15

    The system Ca{sup 2+}/2-aminoethylphosphonic acid/H{sub 2}O/NaOH was systematically investigated using high-throughput methods. The experiments led to one new compound Ca(O{sub 3}PC{sub 2} H{sub 4}NH{sub 2}) (1) and the crystal structure was determined using in house X-ray powder diffraction data (monoclinic, P2{sub 1}/c, a=9.7753(3), b=6.4931(2), c=8.4473(2) A, {beta}=106.46(2) Degree-Sign , V=514.20(2) A{sup 3}, Z=4). The formation of 1 was investigated by in situ energy dispersive X-ray diffraction measurements (EDXRD) at beamline F3 at HASYLAB (light source DORIS III), DESY, Hamburg. An intermediate, Ca(OH)(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3}){center_dot}2H{sub 2}O (2), was observed and could be isolated from the reaction mixture at ambientmore » temperatures by quenching the reaction. The crystal structure of 2 was determined from XRPD data using synchrotron radiation (monoclinic, P2{sub 1}/m, a=11.2193(7), b=7.1488(3), c=5.0635(2) A, {beta}=100.13(4) Degree-Sign , V=399.78(3) A{sup 3}, Z=2). - Graphical abstarct: The detailed in situ energy dispersive X-ray diffraction (EDXRD) investigation on the formation of the new inorganic-organic hybrid compound Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}) leads to the discovery of a new crystalline intermediate phase. Both crystal structures were elucidated using X-ray powder diffraction data. Highlights: Black-Right-Pointing-Pointer High-throughput investigation led to new metal aminoethylphosphonate Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}). Black-Right-Pointing-Pointer The formation of Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}) was followed by in situ EDXRD measurements. Black-Right-Pointing-Pointer The crystalline intermediate Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3})(OH){center_dot}2H{sub 2}O was discovered. Black-Right-Pointing-Pointer Isolation of Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3})(OH){center_dot}2H{sub 2}O was accomplished by quenching experiments. Black-Right-Pointing-Pointer The structures were determined using X

  18. Description and crystal structure of albrechtschraufite, MgCa4F2[UO2(CO3)3]2ṡ17-18H2O

    NASA Astrophysics Data System (ADS)

    Mereiter, Kurt

    2013-04-01

    Albrechtschraufite, MgCa4F2[UO2(CO3)3]2ṡ17-18H2O, triclinic, space group Pī, a = 13.569(2), b = 13.419(2), c = 11.622(2) Å, α = 115.82(1), β = 107.61(1), γ = 92.84(1)° (structural unit cell, not reduced), V = 1774.6(5) Å3, Z = 2, D c = 2.69 g/cm3 (for 17.5 H2O), is a mineral that was found in small amounts with schröckingerite, NaCa3F[UO2(CO3)3](SO4)ṡ10H2O, on a museum specimen of uranium ore from Joachimsthal (Jáchymov), Czech Republic. The mineral forms small grain-like subhedral crystals (≤ 0.2 mm) that resemble in appearance liebigite, Ca2[UO2(CO3)3]ṡ ~ 11H2O. Colour pale yellow-green, luster vitreous, transparent, pale bluish green fluorescence under ultraviolet light. Optical data: Biaxial negative, nX = 1.511(2), nY = 1.550(2), nZ = 1.566(2), 2 V = 65(1)° ( λ = 589 nm), r < v weak. After qualitative tests had shown the presence of Ca, U, Mg, CO2 and H2O, the chemical formula was determined by a crystal structure analysis based on X-ray four-circle diffractometer data. The structure was later on refined with data from a CCD diffractometer to R1 = 0.0206 and wR2 = 0.0429 for 9,236 independent observed reflections. The crystal structure contains two independent [UO2(CO3)3]4- anions of which one is bonded to two Mg and six Ca while the second is bonded to only one Mg and three Ca. Magnesium forms a MgF2(Ocarbonate)3(H2O) octahedron that is linked via the F atoms with three Ca atoms so as to provide each F atom with a flat pyramidal coordination by one Mg and two Ca. Calcium is 7- and 8-coordinate forming CaFO6, CaF2O2(H2O)4, CaFO3(H2O)4 and CaO2(H2O)6 coordination polyhedra. The crystal structure is built up from MgCa3F2[UO2(CO3)3]ṡ8H2O layers parallel to (001) which are linked by Ca[UO2(CO3)3]ṡ5H2O moieties into a framework of the composition MgCa4F2[UO2(CO3)3]ṡ13H2O. Five additional water molecules are located in voids of the framework and show large displacement parameters. One of the water positions is partly vacant, leading to a

  19. Synthesis, structure, and characterization of a new sandwich-type arsenotungstocerate, [As 2W 18Ce 3O 71(H 2O) 3] 12-

    NASA Astrophysics Data System (ADS)

    Alizadeh, M. H.; Eshtiagh-Hosseini, H.; Khoshnavazi, R.

    2004-01-01

    The rational synthesis of the new sandwich-type arsenotungstocerate [As 2W 18Ce 3O 71(H 2O) 3] 12- is reported for the first time by reaction of the trivacant lacunary species A-α-[AsW 9O 34] 9- with appropriate Ce IV. The single crystal structure analysis was carried out on K 7(H 3O) 5[As 2W 18Ce 3O 71(H 2O) 3]·9H 2O; H 39As 2Ce 3K 7O 88W 18; ( 2) which crystallizes in triclinic system, space group P overline1 with a=11.615(5) Å, b=17.638(7) Å, c=19.448(8) Å, α=73.643(7)°, β=88.799(7)°, γ=88.078(7)° and Z=2. The anion consists on two lacunary A-α-[AsW 9O 34] 9- Keggin moieties linked via a (H 2OCeO) 3 belt leading to a sandwich-type structure. Each cerium atom adopts tri-capped trigonal-prismatic coordination achieved by two terminal oxygen of an edge shared paired of WO 6 octahedra to each A-α-AsW 9O 349- moiety and two oxygen from the belt and the cap by one μ 3-O (As, W 2) to each A-α-AsW 9O 349- moiety and one external water ligand. The Ce-O bond lengths average in CeO 6 group, Ce-O(As, W 2) and Ce-O(nW) are 2.300(9), 2.887(3) and 2.682(5) Å, respectively. The acid/base titration curve reveals that the anion has two different titrable protons.

  20. Energetics of the O-H bond and of intramolecular hydrogen bonding in HOC6H4C(O)Y (Y = H, CH3, CH2CH=CH2, C[triple bond]CH, CH2F, NH2, NHCH3, NO2, OH, OCH3, OCN, CN, F, Cl, SH, and SCH3) compounds.

    PubMed

    Bernardes, Carlos E S; Minas da Piedade, Manuel E

    2008-10-09

    The energetics of the phenolic O-H bond in a series of 2- and 4-HOC 6H 4C(O)Y (Y = H, CH3, CH 2CH=CH2, C[triple bond]CH, CH2F, NH2, NHCH 3, NO2, OH, OCH3, OCN, CN, F, Cl, SH, and SCH3) compounds and of the intramolecular O...H hydrogen bond in 2-HOC 6H 4C(O)Y, was investigated by using a combination of experimental and theoretical methods. The standard molar enthalpies of formation of 2-hydroxybenzaldehyde (2HBA), 4-hydroxybenzaldehyde (4HBA), 2'-hydroxyacetophenone (2HAP), 2-hydroxybenzamide (2HBM), and 4-hydroxybenzamide (4HBM), at 298.15 K, were determined by micro- or macrocombustion calorimetry. The corresponding enthalpies of vaporization or sublimation were also measured by Calvet drop-calorimetry and Knudsen effusion measurements. The combination of the obtained experimental data led to Delta f H m (o)(2HBA, g) = -238.3 +/- 2.5 kJ.mol (-1), DeltafHm(o)(4HBA, g) = -220.3 +/- 2.0 kJ.mol(-1), Delta f H m (o)(2HAP, g) = -291.8 +/- 2.1 kJ.mol(-1), DeltafHm(o)(2HBM, g) = -304.8 +/- 1.5 kJ.mol (-1), and DeltafHm(o) (4HBM, g) = -278.4 +/- 2.4 kJ.mol (-1). These values, were used to assess the predictions of the B3LYP/6-31G(d,p), B3LYP/6-311+G(d,p), B3LYP/aug-cc-pVDZ, B3P86/6-31G(d,p), B3P86/6-311+G(d,p), B3P86/aug-cc-pVDZ, and CBS-QB3 methods, for the enthalpies of a series of isodesmic gas phase reactions. In general, the CBS-QB3 method was able to reproduce the experimental enthalpies of reaction within their uncertainties. The B3LYP/6-311+G(d,p) method, with a slightly poorer accuracy than the CBS-QB3 approach, achieved the best performance of the tested DFT models. It was further used to analyze the trends of the intramolecular O...H hydrogen bond in 2-HOC 6H 4C(O)Y evaluated by the ortho-para method and to compare the energetics of the phenolic O-H bond in 2- and 4-HOC 6H 4C(O)Y compounds. It was concluded that the O-H bond "strength" is systematically larger for 2-hydroxybenzoyl than for the corresponding 4-hydroxybenzoyl isomers mainly due to the presence of

  1. Radical-molecule reaction C3H+H2O: a mechanistic study.

    PubMed

    Dong, Hao; Ding, Yi-Hong; Sun, Chia-Chung

    2005-02-08

    Despite the importance of the C(3)H radical in both combustion and interstellar space, the reactions of C(3)H toward stable molecules have never been studied. In this paper, we report our detailed mechanistic study on the radical-molecule reaction C(3)H+H(2)O at the Becke's three parameter Lee-Yang-Parr-B3LYP6-311G(d,p) and coupled cluster with single, double, and triple excitations-CCSD(T)6-311G(2d,p) (single-point) levels. It is shown that the C(3)H+H(2)O reaction initially favors formation of the carbene-insertion intermediates HCCCHOH (1a,1b) rather than the direct H- or OH-abstraction process. Subsequently, the isomers (1a,1b) can undergo a direct H- extrusion to form the well-known product propynal HCCCHO (P(5)). Highly competitively, (1a,1b) can take the successive 1,4- and 1,2-H-shift interconversion to isomer H(2)CCCHO(2a,2b) and then to isomer H(2)CCHCO(3a,3b), which can finally take a direct C-C bond cleavage to give product C(2)H(3) and CO (P(1)). The other products are kinetically much less feasible. With the overall entrance barrier 10.6 kcal/mol, the title reaction can be important in postburning processes. Particularly, our calculations suggest that the title reaction may play a role in the formation of the intriguing interstellar molecule, propynal HCCCHO. The calculated results will also be useful for the analogous C(3)H reactions such as with ammonia and alkanes.

  2. Ag incorporated Mn3O4/AC nanocomposite based supercapacitor devices with high energy density and power density.

    PubMed

    Nagamuthu, S; Vijayakumar, S; Muralidharan, G

    2014-12-14

    Silver incorporated Mn3O4/amorphous carbon (AC) nanocomposites are synthesized by a green chemistry method. X-ray diffraction studies revealed the structural changes in Mn3O4/AC nanocomposites attributable to the addition of silver. Cyclic voltammetry, charge-discharge and ac-impedance studies indicated that the Ag-Mn3O4/AC-5 electrode was the most suitable candidate for supercapacitor applications. From the galvanostatic charge-discharge studies, a higher specific capacitance of 981 F g(-1) at a specific current of 1 A g(-1) was obtained. An Ag-Mn3O4/AC-symmetric supercapacitor consisting of an Ag-incorporated Mn3O4/AC composite as an anode as well as a cathode, and an asymmetric supercapacitor consisting of an Ag-incorporated Mn3O4/AC composite as a cathode and an activated carbon as an anode have been fabricated. The symmetric device exhibits a specific cell capacitance of 72 F g(-1) at a specific current of 1 A g(-1) whereas the asymmetric device delivers a specific cell capacitance of 180 F g(-1) at a high current rate of 10 A g(-1). The asymmetric supercapacitor device yields a high energy density of 81 W h kg(-1). This is higher than that of lead acid batteries and comparable with that of nickel hydride batteries.

  3. Degradation mechanism of alachlor during direct ozonation and O(3)/H(2)O(2) advanced oxidation process.

    PubMed

    Qiang, Zhimin; Liu, Chao; Dong, Bingzhi; Zhang, Yalei

    2010-01-01

    The degradation of alachlor by direct ozonation and advanced oxidation process O(3)/H(2)O(2) was investigated in this study with focus on identification of degradation byproducts. The second-order reaction rate constant between ozone and alachlor was determined to be 2.5+/-0.1M(-1)s(-1) at pH 7.0 and 20 degrees C. Twelve and eight high-molecular-weight byproducts (with the benzene ring intact) from alachlor degradation were identified during direct ozonation and O(3)/H(2)O(2), respectively. The common degradation byproducts included N-(2,6-diethylphenyl)-methyleneamine, 8-ethyl-3,4-dihydro-quinoline, 8-ethyl-quinoline, 1-chloroacetyl-2-hydro-3-ketone-7-acetyl-indole, 2-chloro-2',6'-diacetyl-N-(methoxymethyl)acetanilide, 2-chloro-2'-acetyl-6'-ethyl-N-(methoxymethyl)-acetanilide, and two hydroxylated alachlor isomers. In direct ozonation, four more byproducts were also identified including 1-chloroacetyl-2,3-dihydro-7-ethyl-indole, 2-chloro-2',6'-ethyl-acetanilide, 2-chloro-2',6'-acetyl-acetanilide and 2-chloro-2'-ethyl-6'-acetyl-N-(methoxymethyl)-acetanilide. Degradation of alachlor by O(3) and O(3)/H(2)O(2) also led to the formation of low-molecular-weight byproducts including formic, acetic, propionic, monochloroacetic and oxalic acids as well as chloride ion (only detected in O(3)/H(2)O(2)). Nitrite and nitrate formation was negligible. Alachlor degradation occurred via oxidation of the arylethyl group, N-dealkylation, cyclization and cleavage of benzene ring. After O(3) or O(3)/H(2)O(2) treatment, the toxicity of alachlor solution examined by the Daphnia magna bioassay was slightly reduced. 2009 Elsevier Ltd. All rights reserved.

  4. Vibrational spectroscopy of NO + (H2O)n: Evidence for the intracluster reaction NO + (H2O)n --> H3O + (H2O)n - 2 (HONO) at n => 4

    NASA Astrophysics Data System (ADS)

    Choi, Jong-Ho; Kuwata, Keith T.; Haas, Bernd-Michael; Cao, Yibin; Johnson, Matthew S.; Okumura, Mitchio

    1994-05-01

    Infrared spectra of mass-selected clusters NO+(H2O)n for n=1 to 5 were recorded from 2700 to 3800 cm-1 by vibrational predissociation spectroscopy. Vibrational frequencies and intensities were also calculated for n=1 and 2 at the second-order Møller-Plesset (MP2) level, to aid in the interpretation of the spectra, and at the singles and doubles coupled cluster (CCSD) level energies of n=1 isomers were computed at the MP2 geometries. The smaller clusters (n=1 to 3) were complexes of H2O ligands bound to a nitrosonium ion NO+ core. They possessed perturbed H2O stretch bands and dissociated by loss of H2O. The H2O antisymmetric stretch was absent in n=1 and gradually increased in intensity with n. In the n=4 clusters, we found evidence for the beginning of a second solvation shell as well as the onset of an intracluster reaction that formed HONO. These clusters exhibited additional weak, broad bands between 3200 and 3400 cm-1 and two new minor photodissociation channels, loss of HONO and loss of two H2O molecules. The reaction appeared to go to completion within the n=5 clusters. The primary dissociation channel was loss of HONO, and seven vibrational bands were observed. From an analysis of the spectrum, we concluded that the n=5 cluster rearranged to form H3O+(H2O)3(HONO), i.e., an adduct of the reaction products.

  5. Synthesis and antiviral evaluation of novel 2,3-dihydroxypropyl nucleosides from 2- and 4-thiouracils.

    PubMed

    Abdel-Rahman, Adel A-H; El-Etrawy, Abd-Allah Sh; Abdel-Megied, Ahmed E-S; Zeid, Ibrahim F; El Ashry, El Sayed H

    2008-12-01

    Regioselective alkylation of 2-thiouracils 1a-c and 4-thiouracils 7a,b with 2,3-O-isopropylidene-2,3-dihydroxypropyl chloride (2) afforded 2-[[(2,2-Dimethyl-1,3-dioxolan-4-yl) methyl]thio]pyrimidin-4(1H)-ones 3a-c and 4-[[(2,2-Dimethyl-1,3-dioxolan-4-yl)methyl]thio] pyrimidin-2(1H)-ones 8a,b, respectively. Further alkylation with 2 and/or 2,3-O-isopropylidine-1-O-(4-toluenesulfonyl)-glycerol (4) gave the acyclo N-nucleosides 5a-c and 9a,b whose deprotection afforded 6a-c and 10a,b. 2-(Methylthio)pyrimidin-4(1H)-ones 11a-c and 4-(methylthio)pyrimidin-2(1H)-ones 14a,b were treated with 2 and/or 4 to give 12a-c and 15a,b which were deprotected to give 13a-c and 16a,b. Pyrimidine-2,4(1H,3H)-dithiones 17a-c were treated with two equivalents of 2 to give 2,4-bis[[(2,2-dimethyl-1,3-dioxolan-4-yl)methyl]thio] pyrimidines 18a-c. Deprotection of compounds 18a-c gave 2,4-bis[(2,3-dihydroxypropyl)thio]pyrimidines 19a-c. The activity of the deprotected nucleosides against Hepatitis B virus was evaluated and showed moderate inhibition activity against HBV with mild cytotoxicity.

  6. 40 CFR 721.10356 - Zinc, bis[3-(acetyl-.kappa.O)-6-methyl-2H-pyran-2,4(3H)-dionato-.kappa.O4]diaqua-.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Zinc, bis[3-(acetyl-.kappa.O)-6-methyl-2H-pyran-2,4(3H)-dionato-.kappa.O4]diaqua-. 721.10356 Section 721.10356 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific...

  7. 40 CFR 721.10356 - Zinc, bis[3-(acetyl-.kappa.O)-6-methyl-2H-pyran-2,4(3H)-dionato-.kappa.O4]diaqua-.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Zinc, bis[3-(acetyl-.kappa.O)-6-methyl-2H-pyran-2,4(3H)-dionato-.kappa.O4]diaqua-. 721.10356 Section 721.10356 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific...

  8. 40 CFR 721.10356 - Zinc, bis[3-(acetyl-.kappa.O)-6-methyl-2H-pyran-2,4(3H)-dionato-.kappa.O4]diaqua-.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Zinc, bis[3-(acetyl-.kappa.O)-6-methyl-2H-pyran-2,4(3H)-dionato-.kappa.O4]diaqua-. 721.10356 Section 721.10356 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific...

  9. Understanding Complex Tribofilms by Means of H3BO3-B2O3 Model Glasses.

    PubMed

    Spadaro, F; Rossi, A; Ramakrishna, Shivaprakash N; Lainé, E; Woodward, P; Spencer, N D

    2018-02-13

    The discovery of the spontaneous reaction of boric oxides with moisture in the air to form lubricious H 3 BO 3 films has led to great interest in the tribology of boron compounds in general. Despite this, a study of the growth kinetics of H 3 BO 3 on a B 2 O 3 substrate under controlled relative humidity (RH) has not yet been reported in the literature. Here, we describe the tribological properties of H 3 BO 3 -B 2 O 3 glass systems after aging under controlled RH over different lengths of time. A series of tribological tests has been performed applying a normal load of 15 N, at both room temperature and 100 °C in YUBASE 4 oil. In addition, the cause of H 3 BO 3 film failure under high-pressure and high-temperature conditions has been studied to find out whether the temperature, the tribostress, or both influence the removal of the lubricious film from the contact points. The following techniques were exploited: confocal Raman spectroscopy to characterize the structure and chemical nature of the glass systems, environmental scanning electron microscopy to examine the morphology of the H 3 BO 3 films developed, atomic force microscopy to monitor changes in roughness as a consequence of the air exposure, focused-ion-beam scanning electron microscopy to measure the average thickness of the H 3 BO 3 films grown over various times on B 2 O 3 glass substrates and to reveal the morphology of the sample in the vertical section, tribological tests to shed light on the system's lubricating properties, and finally small-area X-ray photoelectron spectroscopy to investigate the composition of the transfer film formed on the steel ball while tribotesting.

  10. SMA observations of the W3(OH) complex: Dynamical differentiation between W3(H2O) and W3(OH)

    NASA Astrophysics Data System (ADS)

    Qin, Sheng-Li; Schilke, Peter; Wu, Jingwen; Liu, Tie; Wu, Yuefang; Sánchez-Monge, Álvaro; Liu, Ying

    2016-03-01

    We present Submillimeter Array observations of the HCN (3-2) and HCO+ (3-2) molecular lines towards the W3(H2O) and W3(OH) star-forming complexes. Infall and outflow motions in the W3(H2O) have been characterized by observing HCN and HCO+ transitions. High-velocity blue/red-shifted emission, tracing the outflow, show multiple knots, which might originate in episodic and precessing outflows. `Blue-peaked' line profiles indicate that gas is infalling on to the W3(H2O) dust core. The measured large mass accretion rate, 2.3 × 10-3 M⊙ yr-1, together with the small free-fall time-scale, 5 × 103 yr, suggest W3(H2O) is in an early evolutionary stage of the process of formation of high-mass stars. For the W3(OH), a two-layer model fit to the HCN and HCO+ spectral lines and Spizter/Infrared Array Camera (IRAC) images support that the W3(OH) H II region is expanding and interacting with the ambient gas, with the shocked neutral gas being expanding with an expansion time-scale of 6.4 × 103 yr. The observations suggest different kinematical time-scales and dynamical states for the W3(H2O) and W3(OH).

  11. Variable dimensionality and framework found in a series of quaternary zinc selenites, A{sub 2}Zn{sub 3}(SeO{sub 3}){sub 4}·xH{sub 2}O (A = Na, Rb, and Cs; 0≤x≤1) and Cs{sub 2}Zn{sub 2}(SeO{sub 3}){sub 32H{sub 2}O

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

    Lü, Minfeng; Jo, Hongil; Oh, Seung-Jin

    Five new alkali metal zinc selenites, A{sub 2}Zn{sub 3}(SeO{sub 3}){sub 4}·xH{sub 2}O (A = Na, Rb, and Cs; 0≤x≤1) and Cs{sub 2}Zn{sub 2}(SeO{sub 3}){sub 32H{sub 2}O have been synthesized by heating a mixture of ZnO, SeO{sub 2} and A{sub 2}CO{sub 3} (A = Na, Rb, and Cs), and characterized by X-ray diffraction (XRD) and spectroscopic analyses techniques. All of the reported materials revealed a rich structural chemistry with different frameworks and connection modes of Zn{sup 2+}. While Rb{sub 2}Zn{sub 3}(SeO{sub 3}){sub 4} and Cs{sub 2}Zn{sub 3}(SeO{sub 3}){sub 4}·H{sub 2}O revealed three-dimensional frameworks consisting of isolated ZnO{sub 4} tetrahedra and SeO{submore » 3} polyhedra, Na{sub 2}Zn{sub 3}(SeO{sub 3}){sub 4}, Cs{sub 2}Zn{sub 3}(SeO{sub 3}){sub 4}, and Cs{sub 2}Zn{sub 2}(SeO{sub 3}){sub 32H{sub 2}O contained two-dimensional [Zn{sub 3}(SeO{sub 3}){sub 4}]{sup 2-} layers. Specifically, whereas isolated ZnO{sub 4} tetrahedra and SeO{sub 3} polyhedra are arranged into two-dimensional [Zn{sub 3}(SeO{sub 3}){sub 4}]{sup 2-} layers in two cesium compounds, circular [Zn{sub 3}O{sub 10}]{sup 14-} chains and SeO{sub 3} linkers are formed in two-dimensional [Zn{sub 3}(SeO{sub 3}){sub 4}]{sup 2-} layers in Na{sub 2}Zn{sub 3}(SeO{sub 3}){sub 4}. Close structural examinations suggest that the size of alkali metal is significant in determining the framework geometry as well as connection modes of transition metal cations. - Graphical abstract: Variable dimensions and frameworks were found in a series of quaternary zinc selenites, A{sub 2}Zn{sub 3}(SeO{sub 3}){sub 4} (A = Na, Rb and Cs). - Highlights: • Five novel quaternary zinc selenites are synthesized. • All the selenites with different structures contain polarizable d{sup 10} and lone pair cations. • The size of alkali metal cations is significant in determining the framework geometry.« less

  12. Hydrothermal Syntheses and Structures of Three-Dimensional Oxo-fluorovanadium Phosphates: [H 2N(C 2H 4) 2NH 2] 0.5[(VO) 4V(HPO 4) 2(PO 4) 2F 2(H 2O) 4] · 2H 2O and K 2[(VO) 3(PO 4) 2F 2(H 2O)] · H 2O

    NASA Astrophysics Data System (ADS)

    Bonavia, Grant; Haushalter, R. C.; Zubieta, Jon

    1996-11-01

    The hydrothermal reactions of FPO3H2with vanadium oxides result in the incorporation of fluoride into V-P-O frameworks as a consequence of metal-mediated hydrolysis of the fluorophosphoric acid to produce F-and PO3-4. By exploiting this convenient source of F-, two 3-dimensional oxo-fluorovanadium phosphate phases were isolated, [H2N(C2H4)2NH2]0.5[(VO)4V(HOP4)2(PO4)2F2(H2O)4) · 2H2O (1 · 2H2O) and K2[(VO)3(PO4)2F2(H2O)] · H2O (2 · H2O). Both anionic frameworks contain (VIVO)-F--phosphate layers, with confacial bioctahedral {(VIVO)2FO6} units as the fundamental motif. In the case of 1, the layers are linked through {VIIIO6} octahedra, while for 2 the interlayer connectivity is provided by edge-sharing {(VIVO)2F2O6} units. Crystal data are 1 · 2H2O, CH10FN0.5O13P2V2.5, monoclinicC2/m,a= 18.425(4) Å,c= 8.954(2) Å, β = 93.69(2)0,V= 1221.1(4) Å3,Z= 4,Dcalc= 2.423 g cm-3; 2 · H2O, H4F2K2O13P2V3, triclinicPoverline1,a= 7.298(1) Å,b= 8.929(2) Å,c = 10.090(2) Å, α = 104.50(2)0, β = 100.39(2)0, δ = 92.13(2)0,V= 623.8(3) Å3,Z= 2,Dcalc= 2.891 g cm-3.

  13. Two basic bismuth nitrates: [Bi6O6(OH)2](NO3)4 · 2H2O with superior photodegradation activity for rhodamine B and [Bi6O5(OH)3](NO3)5 · 3H2O with ultrahigh adsorption capacity for methyl orange

    NASA Astrophysics Data System (ADS)

    Pang, Jiawei; Han, Qiaofeng; Liu, Weiqi; Shen, Zichen; Wang, Xin; Zhu, Junwu

    2017-11-01

    A novel basic bismuth nitrate, [Bi6O6(OH)2](NO3)4·2H2O (denoted as BiON-4N), was easily obtained at room temperature in the existence of 2-methoxyethanol (CH3OCH2CH2OH; 2ME) with a pH value ranging from 4.5 to 7.0. The morphology of BiON-4N could be easily tailored by changing the variety and amount of bases like urea, hexamethylenetetramine (HMTA), NaOH and NH3·H2O. When the solution pH was decreased lower than 4.5, another basic bismuth nitrate, [Bi6O5(OH)3](NO3)5·3H2O (denoted as BiON-5N), could be synthesized. Among those, BiON-4N nanoparticles obtained with 40 mmol of HMTA exhibited superior photocatalytic activity for rhodamine B (RhB) degradation with an efficiency of 100% within 4 min of UV light irradiation, which was much higher than that of commercial TiO2 (P25). The excellent photocatalytic performance of BiON-4N was mainly attributed to higher surface area (13.1 m2 g-1) in comparison with other basic bismuth nitrates. Furthermore, the as-prepared BiON-5N revealed excellent adsorption performance for the anions like methyl orange (MO) and K2Cr2O7, and especially for MO, the maximum adsorption capacity arrived up to 730 mg g-1, which should be relevant to highly positively charged surface. This work provides a new strategy for developing bismuth-based nanomaterials in the big bismuth family as potential photocatalyst and adsorbent for the removal of dyes and contaminants.

  14. Graphene assisted effective hole-extraction on In2O3:H/CH3NH3PbI3 interface: Studied by modulated surface spectroscopy

    NASA Astrophysics Data System (ADS)

    Vinoth Kumar, Sri Hari Bharath; Muydinov, Ruslan; Kol'tsova, Tat‘yana; Erfurt, Darja; Steigert, Alexander; Tolochko, Oleg; Szyszka, Bernd

    2018-01-01

    Charge separation in CH3NH3PbI3 (MAPbI3) films deposited on a hydrogen doped indium oxide (In2O3:H) photoelectrode was investigated by modulated surface photovoltage (SPV) spectroscopy in a fixed capacitor arrangement. It was found that In2O3:H reproducibly extracts photogenerated-holes from MAPbI3 films. The oxygen-plasma treatment of the In2O3:H surface is suggested to be a reason for this phenomenon. Introducing graphene interlayer increased charge separation nearly 6 times as compared to that on the In2O3:H/MAPbI3 interface. Furthermore, it is confirmed by SPV spectroscopy that the defects of the MAPbI3 interface are passivated by graphene.

  15. VAPOR PRESSURES, LIQUID MOLAR VOLUMES, VAPOR NON- IDEALITIES, AND CRITICAL PROPERTIES OF SOME FLUORINATED ETHERS: CF3OCF2OCF3, CF3OCF2 CF2H, c-CF2CF2CF2O, CF3OCF2H, AND CF3OCH3; AND OF CCl3F AND CF2ClH

    EPA Science Inventory

    Vapor pressures, compressibilities, expansivities, and molar volumes of the liquid phase have been measured between room temperature and the critical temperature for a series of fluorinated ethers: CF3OCF2OCF3, CF3OCF2CF2H, c-CF2CF2CF2O, CF3OCF2H, and CF3OCH3. Vapor-phase non-ide...

  16. A novel synthesis method for TiO2 particles with magnetic Fe3O4 cores.

    PubMed

    Dong, Qi; Zhang, Keqiang; An, Yi

    2014-01-01

    TiO2@(AC/Fe3O4) (AC is activated carbon) was prepared by using AC and Fe3O4 as joint support. The morphological features, crystal structure, and magnetism of the final product were characterized. The results indicate that TiO2 particles formed on the surface of AC and Fe3O4; the sizes of TiO2 and Fe3O4 were 0.5 and 0.7 μm respectively, and that of AC fell within a wide range. The highly crystalline cubic structures of the TiO2 particles was in accord with the standard X-ray diffractometry spectrum of magnetite and anatase. The maximum saturation magnetization of TiO2@(AC/Fe3O4) was 75 emu g(-1), which was enough to support magnetic recovery. The rate of methylene blue (MB) removal photocatalyzed by TiO2@(AC/Fe3O4) was higher by 50% than that achieved with AC/Fe3O4 photocatalysis, and similar to that achieved with TiO2@AC. The removal rate (kobs) decreased drastically from 1.77 × 10(-2) to 9.36 × 10(-3)min(-1) when the initial concentration of MB solution increased from 2.0 to 5.0 mg L(-1). The kobs value increased from 9.41 × 10(-3) to 1.34 × 10(-2)min(-1) with increasing photocatalyst dosage from 0.2 to 1.0 g, then slightly decreased to 1.33 × 10(-2)min(-1) at 2.0 g dosage.

  17. Chanabayaite, Cu2(N3C2H2)Cl(NH3,Cl,H2O,□)4, a new mineral containing triazolate anion

    NASA Astrophysics Data System (ADS)

    Chukanov, N. V.; Zubkova, N. V.; Möhn, G.; Pekov, I. V.; Pushcharovsky, D. Yu.; Zadov, A. E.

    2015-12-01

    A new mineral, chanabayaite, has been discovered at a guano deposit located at Mt. Pabellón de Pica near the village of Chanabaya, Iquique Province, Tarapacá region, Chile. It is associated with salammoniac, halite, joanneumite, nitratine and earlier chalcopyrite. Chanabayaite occurs as blue translucent imperfect prismatic crystals, up to 0.05 × 0.1 × 0.5 mm in size, and their radial aggregates. Chanabayaite is brittle, with a Mohs' hardness of 2. The cleavage is perfect on (001) and imperfect on (100) and (010). D meas = 1.48(2) g/cm3, D calc = 1.464 g/cm3. The mineral is optically biaxial (-), α = 1.561(2), β = 1.615(3), γ = 1.620(2), 2 V meas = 25(10)°, 2 V calc = 33°. Pleochroism is strong, Z ≈ Y (deep blue) ≫ X (pale blue with gray tint). IR spectrum is given. The chemical composition (electron microprobe data for Cu, Fe and Cl; gas chromatography data for H, N, C and O) is as follows (wt %): 32.23 Cu, 1.14 Fe, 16.13 Cl, 3.1 H, 29.9 N, 12.2 C, 3.4 O, total is 98.1. The empirical formula is ( Z = 4): Cu1.92Fe0.08Cl1.72N8.09C3.85H11.66O0.81. The structural model was based on the single-crystal X-ray diffraction data ( R = 0.1627). Chanabayaite is orthorhombic, space group Imma, a = 19.484(3), b = 7.2136(10), c = 11.999(4) Å, V = 1686.5(7) Å3, Z = 2. In chanabayaite, chains of the corner-sharing Cu(l)-centered octahedra and single Cu(2)-centered octahedra are linked via 1,2,4-triazolate anions C2N3H2 -. NH3 and Cl- are additional ligands coordinating Cu2+. Chanabayaite is a transformational mineral species formed by leaching of Na and one third of Cl and partial dehydration of the protophase Na2Cu2Cl3(N3C2H2)2(NH3)2 • 4H2O. The strongest reflections in the powder X-ray diffraction pattern [ d, Å ( I, %) ( hkl)] are detected: 10.19 (100) (101), 6.189 (40) (011), 5.729 (23) (301), 5.216 (75) (211, 202), 4.964 (20) (400), 2.830 (20) (602, 413, 503), 2.611 (24) (123, 422, 404).

  18. Stibiconite (Sb3O6OH), senarmontite (Sb2O3) and valentinite (Sb2O3): Dissolution rates at pH 2-11 and isoelectric points

    NASA Astrophysics Data System (ADS)

    Biver, M.; Shotyk, W.

    2013-05-01

    Batch reactor experiments were carried out in order to derive rate laws for the proton promoted dissolution of the main natural antimony oxide phases, namely stibiconite (idealized composition SbSb2O6OH), senarmontite (cubic Sb2O3) and (metastable) valentinite (orthorhombic Sb2O3) over the range 2 ⩽ pH ⩽ 11, under standard conditions and ionic strength I = 0.01 mol l-1. The rates of antimony release by stibiconite were r = (2.2 ± 0.2) × 10-9 a(H+)0.11±0.01 mol m-2 s-1 for 2.00 ⩽ pH ⩽ 4.74 and r = (4.3 ± 0.2) × 10-10 a(H+)-0.030±0.003 mol m-2 s-1 for 4.74 ⩽ pH ⩽ 10.54. The rates of dissolution of senarmontite were r = (5.3 ± 2.2) × 10-7 a(H+)0.54±0.05 mol m-2 s-1 for 2.00 ⩽ pH ⩽ 6.93 and r = (1.4 ± 0.3) × 10-14 a(H+)-0.53±0.07 mol m-2 s-1 for 6.93 ⩽ pH ⩽ 10.83. The rates of dissolution of valentinite were r = (6.3 ± 0.2) × 10-8 a(H+)0.052±0.003 mol m-2 s-1 for 1.97 ⩽ pH ⩽ 6.85. Above pH = 6.85, valentinite was found to dissolve at a constant rate of r = (2.79 ± 0.05) × 10-8 mol m-2 s-1. Activation energies were determined at selected pH values in the acidic and basic domain, over the temperature range 25-50 °C. The values for stibiconite are -10.6 ± 1.9 kJ mol-1 (pH = 2.00) and 53 ± 14 kJ mol-1 (pH = 8.7). For senarmontite, we found 46.6 ± 4.7 kJ mol-1 (pH = 3.0) and 68.1 ± 6.1 kJ mol-1 (pH = 9.9) and for valentinite 41.9 ± 1.1 kJ mol-1 (pH = 3.0) and 39.0 ± 4.6 kJ mol-1 (pH = 9.9). These activation energies are interpreted in the text. The solubility of stibiconite at 25 °C in the pH domain from 2 to 10 was determined; solubilities decrease from 452.0 μg l-1 (as Sb) at pH = 2.00 to 153.2 μg l-1 at pH = 7.55 and increase again in the basic region, up to 176.6 μg l-1 at pH = 9.92. A graphical synopsis of all the kinetic results, including those of stibnite (Sb2S3) from earlier work, is presented. This allows an easy comparison between the dissolution rates of stibnite and the minerals examined in the present work

  19. Identification of the gene transcription repressor domain of Gli3.

    PubMed

    Tsanev, Robert; Tiigimägi, Piret; Michelson, Piret; Metsis, Madis; Østerlund, Torben; Kogerman, Priit

    2009-01-05

    Gli transcription factors are downstream targets of the Hedgehog signaling pathway. Two of the three Gli proteins harbor gene transcription repressor function in the N-terminal half. We have analyzed the sequences and identified a potential repressor domain in Gli2 and Gli3 and have tested this experimentally. Overexpression studies confirm that the N-terminal parts harbor gene repression activity and we mapped the minimal repressor to residues 106 till 236 in Gli3. Unlike other mechanisms that inhibit Gli induced gene transcription, the repressor domain identified here does not utilize Histone deacetylases (HDACs) to achieve repression, as confirmed by HDAC inhibition studies and pull-down assays. This distinguishes the identified domain from other regulatory parts with negative influence on transcription.

  20. Synthesis, crystal structure, and spectroscopic characterization of trans-bis[(mu-1,3-bis(4-pyridyl)propane)(mu-(3-thiopheneacetate-O))(3-thiopheneacetate-O)]dicopper(II), [[Cu2(O2CCH2C4H3S)4mu-(BPP)2

    PubMed

    Marinho, Maria Vanda; Yoshida, Maria Irene; Guedes, Kassilio J; Krambrock, Klaus; Bortoluzzi, Adailton J; Hörner, Manfredo; Machado, Flávia C; Teles, Wagner M

    2004-02-23

    From the reaction between a dinuclear paddle-wheel carboxylate, namely [Cu2mu-(O2CCH2C4H3S)4] (1), and the flexible ligand 1,3-bis(4-pyridyl)propane (BPP) a neutral 2-D coordination polymer [[Cu2(O2CCH2C4H3S)4mu-(BPP)2

  1. Effect of pressure on the magnetic properties of TM3[Cr(CN)6]2·12H2O

    NASA Astrophysics Data System (ADS)

    Zentková, M.; Arnold, Z.; Kamarád, J.; Kavecanský, V.; Lukácová, M.; Mat'aš, S.; Mihalik, M.; Mitróová, Z.; Zentko, A.

    2007-07-01

    We present the results of magnetization and AC susceptibility measurements performed on ferrimagnetic Mn32+[CrIII(CN)6]2·12H2O and ferromagnetic Ni32+[CrIII(CN)6]2·12H2O systems under pressures up to 0.9 GPa in a commercial SQUID magnetometer. The magnetization process is affected by pressure: magnetization saturates at higher magnetic field, saturated magnetization μs of Ni3[Cr(CN)6]2 is reduced and almost unaffected for Mn3[Cr(CN)6]2 at low temperatures. The Curie temperature TC of Mn3[Cr(CN)6]2 increases with the applied pressure, ΔTC/Δp = 25.5 K GPa-1, due to a strengthened super-exchange antiferromagnetic interaction JAF, but it is not affected significantly in the case of Ni3[Cr(CN)6]2 with a dominant ferromagnetic JF super-exchange interaction. The increase in the JAF interaction is attributed to the enhanced value of the single electron overlapping integral S and the energy gap Δ of the mixed molecular orbitals t2g (Mn2+) and t2g (CrIII) induced by pressure.

  2. Synthesis and characterization of two layered aluminophosphates, ( T) 2HAl 2P 3O 12 ( T=2-BuNH 3+) and ( T)H 2Al 2P 3O 12 ( T=pyH +)

    NASA Astrophysics Data System (ADS)

    Chippindale, Ann M.; Powell, Anthony V.; Bull, Lucy M.; Jones, Richard H.; Cheetham, Anthony K.; Thomas, John M.; Xu, Ruren

    1992-01-01

    Two new aluminophosphates, ( T) 2HAl 2P 3O 12 ( T=2-BuNH 3+) ( I) and ( T)H 2Al 2P 3O 12 ( T=pyH +) ( II) with the same framework stoichiometry but different layer structures have been prepared under nonaqueous conditions and the structures determined by single-crystal X-ray diffraction. Compound ( I) crystallizes in the monoclinic space group P2 1/ c ( Z=4), with lattice parameters a=9.261(1) b=8.365(6), c=27.119(4) Å, β=91.50(1)δ, and V=2100.1 Å 3 ( R=0.072 and R w=0.090). The structure consists of Al-and P-centered tetrahedra linked to form layers. Protonated 2-butylamine molecules are located in the interlayer spaces and hydrogen bonded to the layers through NH 3+ groups. Weak hydrophobic van der Waals' interactions between alkyl groups of the 2-BuNH 3+ cations hold the layers together. Compound ( II) crystallizes in the triclinic space group P-1 ( Z=2), with a=8.574(2), b=8.631(3), c=10.371(2) Å, α=81.84(3), β=87.53(2), γ=69.07(2)δ, and V=709.49Å 3 ( R=0.039 and R w=0.052). The structure contains tetrahedrally coordinated P atoms and both tetrahedral and trigonal pyramidal Al atoms linked to form layers which are held together through hydrogen bonding, creating cavities in which pyH + cations reside.

  3. Design and syntheses of hybrid metal–organic materials based on K{sub 3}[M(C{sub 2}O{sub 4}){sub 3}]·3H{sub 2}O [M(III)=Fe, Al, Cr] metallotectons

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

    Sun, Yayong; Zong, Yingxia; Ma, Haoran

    2016-05-15

    By using K{sub 3}[M(C{sub 2}O{sub 4}){sub 3}]·3H{sub 2}O [M(III)=Fe, Al, Cr] (C{sub 2}O{sub 4}{sup 2−}=oxalate) metallotectons as the starting material, we have synthesized eight novel complexes with formulas [{Fe(C_2O_4)_2(H_2O)_2}{sub 2}]·(H–L{sub 1}){sub 2H{sub 2}O 1, [Fe(C{sub 2}O{sub 4})Cl{sub 2}]·(H{sub 2}–L{sub 2}){sub 0.5}·(L{sub 2}){sub 0.5}·H{sub 2}O 2, [{Fe(C_2O_4)_1_._5Cl_2}{sub 2}]·(H–L{sub 3}){sub 4}3, [Fe{sub 2}(C{sub 2}O{sub 4})Cl{sub 8}]·(H{sub 2}–L{sub 4}){sub 22H{sub 2}O 4, K[Al(C{sub 2}O{sub 4}){sub 3}]·(H{sub 2}–L{sub 5})·2H{sub 2}O 5, K[Al(C{sub 2}O{sub 4}){sub 3}]·(H–L{sub 6}){sub 22H{sub 2}O 6, K[Cr(C{sub 2}O{sub 4}){sub 3}]·2H{sub 2}O 7, Na[Fe(C{sub 2}O{sub 4}){sub 3}]·(H–L{sub 6}){sub 22H{sub 2}O 8 (with L{sub 1}=4-dimethylaminopyridine, L{sub 2}=2,3,5,6-tetramethylpyrazine, L{sub 3}=2-aminobenzimidazole, L{sub 4}=1,4-bis-(1H-imidazol-1-yl)benzene, L{sub 5}=1,4-bis((2-methylimidazol-1-yl)methyl)benzene,more » L{sub 6}=2-methylbenzimidazole). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra and thermogravimetric analyses. Compound 3 is a 2D H-bonded supramolecular architecture. Others are 3D supramolecular structures. Compound 1 shows a [Fe(C{sub 2}O{sub 4}){sub 2}(H{sub 2}O){sub 2}]{sup −} unit and 3D antionic H-bonded framework. Compound 2 features a [Fe(C{sub 2}O{sub 4})Cl{sub 2}]{sup -} anion and 1D iron-oxalate-iron chain. Compound 3 features a [Fe{sub 2}(C{sub 2}O{sub 4}){sub 3}Cl{sub 4}]{sup 4−} unit. Compound 4 features distinct [Fe{sub 2}(C{sub 2}O{sub 4})Cl{sub 8}]{sup 4−} units, which are mutual linked by water molecules to generated a 2D H-bonded network. Compound 5 features infinite ladder-like chains constructed by [Al(C{sub 2}O{sub 4}){sub 3}]{sup 3−} units and K{sup +} cations. The 1D chains are further extended into 3D antionic H-bonded framework through O–H···O H-bonds. Compounds 6–8 show 2D [KAl

  4. Photocatalytic self-cleaning transparent 2Bi2O3-B2O3 glass ceramics

    NASA Astrophysics Data System (ADS)

    Sharma, Sumeet Kumar; Singh, V. P.; Chauhan, Vishal S.; Kushwaha, H. S.; Vaish, Rahul

    2017-09-01

    Photocatalytic response of as-quenched and heat-treated 2Bi2O3-B2O3 glasses was studied. X ray diffraction reveals that the controlled heat treatment of glasses at 380 °C for 1 h, 2 h, and 3 h shows the formation of Bi4B2O9 crystals embedded in 2Bi2O3-B2O3 the host glass matrix. Scanning electron microscopic images reveal the presence of nanocrystallization in as-quenched glass. Significant photocatalytic activities were observed in as-quenched transparent glass. Photocatalytic activities were studied using the degradation of Resazurin as well as pharmaceutical 17 β-Estradiol under UV irradiation. Measurement of contact angle shows enhanced hydrophilicity with the increase in crystallization of the samples. Further, for as quenched 2Bi2O3-B2O3 glass ceramic, under UV irradiation, the water contact angle decreased from 92.7° to 39.5° and the sample surface transformed from hydrophobic to hydrophilic. Effective photocatalytic performance along with photoinduced hydrophilicity promotes 2Bi2O3-B2O3 glass ceramics in self-cleaning applications.

  5. Interstellar H3O(+) and its relation to the O2 and H2O abundances

    NASA Astrophysics Data System (ADS)

    Phillips, T. G.; van Dishoeck, Ewine F.; Keene, Jocelyn

    1992-11-01

    An interstellar medium study of the three reasonably accessible low-lying submillimeter lines of the H3O(+) molecular ion at 396, 364, and 307 GHz is presented. An analysis of the H3O(+) line ratios shows that under high density (about 10 exp 6 - 10 exp 7/cu cm) and high-temperature (greater than about 50 K), the 396 GHz line is about a factor of two stronger than the 364 GHz line, with the 307 GHz line much weaker. For lower densities, the excitation of the 364 GHz line can be very sensitive to dust radiation pumping, and it is shown that this is the case in Sgr B2, resulting in the 364 GHz line being a factor of 2-3 stronger than the 396 GHz line. Under almost all conditions, the 307 GHz line is weak, the exception being for densities greater than about 10 exp 7/cu cm.

  6. Controlled precipitation of nesquehonite (MgCO 3·3H 2O) by the reaction of MgCl 2 with (NH 4) 2CO 3

    NASA Astrophysics Data System (ADS)

    Wang, Yong; Li, Zhibao; Demopoulos, George P.

    2008-03-01

    In this study, homogeneous (unseeded) precipitation of nesquehonite (MgCO 3·3H 2O) by the reaction of MgCl 2 with (NH 4) 2CO 3 in supersaturated solutions was investigated. Factors that influence the precipitation of MgCO 3·3H 2O, such as reaction temperature, initial concentration, stirring speed, titration speed, equilibration time, have been studied. SEM images and particle size distribution show that the temperature, initial concentration and titration speed have significant effect on nesquehonite's crystal morphology and particle size. In addition, stirring speed and equilibration time also have some influence on its properties. X-ray powder diffraction (XRD) results show that the obtained crystals compositions are greatly affected by the reaction temperature. With the morphological transformation, their corresponding composition also change from MgCO 3· xH 2O to Mg 5(CO 3) 4(OH) 2·4H 2O in the interval of 288-333 K. With the optimization of operating conditions, the crystals can grow up to a length of about 40 μm and a width of 5 μm, indicating good filtration properties. High-purity nesquehonite obtained in this study was calcined to produce highly pure MgO at 1073 K as shown by XRD results.

  7. Syntheses, crystal structures and optical spectroscopy of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O

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

    Kazmierczak, Karolina; Hoeppe, Henning A., E-mail: henning@ak-hoeppe.d

    2011-05-15

    The lanthanide sulphate octahydrates Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and the respective tetrahydrate Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O were obtained by evaporation of aqueous reaction mixtures of trivalent rare earth oxides and sulphuric acid at 300 K. Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) crystallise in space group C2/c (Z=4, a{sub Ho}=13.4421(4) A, b{sub Ho}=6.6745(2) A, c{sub Ho}=18.1642(5) A, {beta}{sub Ho}=102.006(1) A{sup 3} and a{sub Tm}=13.4118(14) A, b{sub Tm}=6.6402(6) A, c{sub Tm}=18.1040(16) A, {beta}{sub Tm}=101.980(8) A{sup 3}), Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O adopts space group P2{sub 1}/n (a=13.051(3) A, b=7.2047(14) A, c=13.316(3) A, {beta}=92.55(3) A{sup 3}). The vibrationalmore » and optical spectra of Ho{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O are also reported. -- Graphical abstract: In the lanthanide sulphate octahydrates the cations form slightly undulated layers. Between the layers are voids in which sulphate tetrahedra and water molecules are located. The holmium compound exhibits an Alexandrite effect. Display Omitted Highlights: {yields} Determination of the optimum conditions for the growth of single-crystals of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O. {yields} Single-crystal structure elucidation of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) including hydrogen bonds. {yields} Single-crystal structure determination of Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O including hydrogen bonds. {yields} UV-vis spectra of Ho{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O recorded and interpreted: Assignation of bands and clarification of the Alexandrite effect of the Ho compound. {yields} IR and Raman spectra of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O recorded and interpreted.« less

  8. AC conduction of Ba1-xCaxTiO3 and BZT-BCTx

    NASA Astrophysics Data System (ADS)

    Khien, Nguyen Van; Huy, Than Trong; Hong, Le Van

    2018-03-01

    Ba1-xCaxTiO3 (BCTx), (x =0.0-0.3) and Ba0.8Zr0.2TiO3-Ba1-xCaxTiO3 (BZT-BCTx), (x=0.15-0.35) were fabricated by the solid state reaction method. Phase structure of the material samples was identified by X-ray diffraction. The impedance versus frequency in a range of 100 Hz to 2.5 MHz was measured for all the samples at room temperature. AC conductivity versus frequency of the BCTx and BZT-BCTx was evaluated and fitted by using the extended Universal Dielectric Response (UDR) equations. The fitting results were discussed in detail and shown that the localized reorientation polarization-based mechanism is most contributed in BCTx matrial samples. Basically both two the hopping polaron and polarization mechanisms play roles in BZT-BCTx material samples. In contrary the short-range polaron hopping is dominated in ac conductivity of BZT-BCTx material samples in low frequency range.

  9. Dehydration of glucose to 5-hydroxymethylfurfural by a core-shell Fe3O4@SiO2-SO3H magnetic nanoparticle catalyst

    USDA-ARS?s Scientific Manuscript database

    This paper discusses the potential use of (Fe3O4@SiO2-SO3H) nanoparticle catalyst for the dehydration of glucose into 5-hydroxymethylfurfural (HMF). A magnetically recoverable (Fe3O4@SiO2-SO3H) nanoparticle catalyst was successfully prepared by supporting sulfonic acid groups (SO3H) on the surface o...

  10. Influence of temperature on AC conductivity of nanocrystalline CuAlO2

    NASA Astrophysics Data System (ADS)

    Prakash, T.

    2012-07-01

    Nanocrystalline CuAlO2 was synthesized by mechanical alloying of Cu2O and α-Al2O3 powders in the molar ratio of 1:1 for 20 h in toluene medium with tungsten carbide balls and vials using planetary ball mill. The ball milling was carried out at 300 rpm with a ball to powder weight ratio of 10:1 and then annealed at 1373 K in a platinum crucible for 20 h to get CuAlO2 phase with average crystallite size 45 nm. Complex impedance spectroscopic measurement in the frequency region 1 Hz to 10 MHz between the temperatures 333 to 473 K was carried out for nanocrystalline CuAlO2 sample. The obtained complex impedance data was analyzed for AC conductivities, DC and AC conductivities correlations and crossover frequencies ( f co ). The BNN (Barton, Nakajima and Namikawa) relation was applied to understand the correlation between DC and AC conductivities. The observed experimental results were discussed in the paper.

  11. Hydrothermal synthesis of 4ZnO·B2O3·H2O:Ln3 + (Ln = Eu, Tb) phosphors: Morphology-tunable and luminescence properties

    NASA Astrophysics Data System (ADS)

    Cao, Shiwei; Jiao, Yang; Han, Weifang; Ge, Chunhua; Song, Bo; Wang, Jie; Zhang, Xiangdong

    2018-02-01

    4ZnO·B2O3·H2O:Ln3 + (Ln = Eu, Tb) phosphors with different morphologies have been successfully synthesized via one-step hydrothermal method through regulating the molar amount of Eu3 + and Tb3 +. Comprehensive scanning electron microscopy (SEM), X-ray diffraction (XRD) Fourier transform infrared spectrum (FT-IR) and inductively coupled plasma atomic emission spectrometer (ICP-AES) characterizations all confirm that obtained products are 4ZnO·B2O3·H2O:Ln3 + (Ln = Eu, Tb). The experimental results displayed that the morphology and photoluminescence of compounds is regularly changed with increased the molar amount of rare earth ions. For the Eu3 +-doped, Tb3 +-doped and Eu3 +/Tb3 + co-doped 4ZnO·B2O3·H2O phosphors of morphologies, the rod-like structures gradually changed to flower-like structures, fine wire-like structure and hybrid structure, respectively. To their photoluminescence, the Eu3 + shows a red emission (615 nm); the Tb3 + shows a green emission (545 nm); for the Eu3 +/Tb3 + co-doped 4ZnO·B2O3·H2O phosphors, a combination of blue (5d-4f of Eu2 +), green (5D4-7F5 of Tb3 +) and red (5D0-7F2 of Eu3 +) emissions emerges to achieve white emission. In addition, the energy transfer among Eu3 +, Eu2 + and Tb3 + ions was also discussed.

  12. Hydrothermal synthesis of 4ZnO·B2O3·H2O:Ln3+ (Ln=Eu, Tb) phosphors: Morphology-tunable and luminescence properties.

    PubMed

    Cao, Shiwei; Jiao, Yang; Han, Weifang; Ge, Chunhua; Song, Bo; Wang, Jie; Zhang, Xiangdong

    2018-02-05

    4ZnO·B 2 O 3 ·H 2 O:Ln 3+ (Ln=Eu, Tb) phosphors with different morphologies have been successfully synthesized via one-step hydrothermal method through regulating the molar amount of Eu 3+ and Tb 3+ . Comprehensive scanning electron microscopy (SEM), X-ray diffraction (XRD) Fourier transform infrared spectrum (FT-IR) and inductively coupled plasma atomic emission spectrometer (ICP-AES) characterizations all confirm that obtained products are 4ZnO·B 2 O 3 ·H 2 O:Ln 3+ (Ln=Eu, Tb). The experimental results displayed that the morphology and photoluminescence of compounds is regularly changed with increased the molar amount of rare earth ions. For the Eu 3+ -doped, Tb 3+ -doped and Eu 3+ /Tb 3+ co-doped 4ZnO·B 2 O 3 ·H 2 O phosphors of morphologies, the rod-like structures gradually changed to flower-like structures, fine wire-like structure and hybrid structure, respectively. To their photoluminescence, the Eu 3+ shows a red emission (615nm); the Tb 3+ shows a green emission (545nm); for the Eu 3+ /Tb 3+ co-doped 4ZnO·B 2 O 3 ·H 2 O phosphors, a combination of blue (5d-4f of Eu 2+ ), green ( 5 D 4 - 7 F 5 of Tb 3+ ) and red ( 5 D 0 - 7 F 2 of Eu 3+ ) emissions emerges to achieve white emission. In addition, the energy transfer among Eu 3+ , Eu 2+ and Tb 3+ ions was also discussed. Copyright © 2017. Published by Elsevier B.V.

  13. The interstellar chemistry of H2C3O isomers

    PubMed Central

    Loison, Jean-Christophe; Agúndez, Marcelino; Marcelino, Núria; Wakelam, Valentine; Hickson, Kevin M.; Cernicharo, José; Gerin, Maryvonne; Roueff, Evelyne; Guélin, Michel

    2016-01-01

    We present the detection of two H2C3O isomers, propynal and cyclopropenone, toward various starless cores and molecular clouds, together with upper limits for the third isomer propadienone. We review the processes controlling the abundances of H2C3O isomers in interstellar media showing that the reactions involved are gas-phase ones. We show that the abundances of these species are controlled by kinetic rather than thermodynamic effects. PMID:27013768

  14. Electric conductivity analysis and dielectric relaxation behavior of the hybrid polyvanadate (H{sub 3}N(CH{sub 2}){sub 3}NH{sub 3})[V{sub 4}O{sub 10}

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

    Nefzi, H.; Sediri, F., E-mail: faouzi.sediri@ipeit.rnu.tn; Faculté des Sciences de Tunis, Université Tunis El Manar, 2092 El Manar, Tunis

    2013-05-15

    Highlights: ► Plate-like crystals (H{sub 3}N(CH{sub 2}){sub 3}NH{sub 3})[V{sub 4}O{sub 10}] were synthesized. ► Frequency and temperature dependence of AC conductivity indicate CBH model. ► The temperature dependence of DC conductivity exhibits two conduction mechanisms. - Abstract: Layered hybrid compound (H{sub 3}N(CH{sub 2}){sub 3}NH{sub 3})[V{sub 4}O{sub 10}] has been synthesized via hydrothermal method. Techniques X-ray powder diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and impedance spectroscopy have been used to characterize the hybrid material. Electrical and dielectric properties dependence on both temperature and frequency of the compound have been reported. The direct current conductivity process is thermally activated andmore » it is found to be 12.67 × 10{sup −4} Ω{sup −1} m{sup −1} at 523 K. The spectra follow the Arrhenius law with two activation energy 0.25 eV for T < 455 K and 0.5 eV for T > 455 K.« less

  15. H+, O2+, O3+ and high resolution PIXE spectra of Yb2O3

    NASA Astrophysics Data System (ADS)

    Chaves, P. C.; Reis, M. A.

    2017-11-01

    The number of X-ray spectrometry systems having energy resolution of the order of 10 eV, or less, has increasing recently, included already energy dispersive systems (EDS). Access to previous unseen spectra details and enhanced information including speciation, becomes more common and available. Analysis of high resolution EDS PIXE spectra is, nevertheless a complex task due to the need to carefully account for contributions from minor and satellite transitions. In this work, a pure Yb2O3 sample was irradiated at the HRHE-PIXE setup of C2TN, and simultaneous CdTe and X-ray Microcalorimeter Spectrometer (XMS) spectra were collected. The L-shell spectrum of Yb emitted during irradiations using H+ , O2+ and O3+ ions in the energy range from 1.0 to 6.5 MeV was studied. Measured L X-ray spectra were analysed taking into account the effects of the multiple ionization in the L and M shells. All spectra were analysed using the DT2 code, which allows to include in the fitting model diagram lines as well as multi-ionization satellites and any other contributions. In this communication we present the results and discuss details and problems related to the transition energies, intensity, line width data, and multiple ionization satellites.

  16. Structural, thermal, optical and dielectric studies of Dy3+: B2O3-ZnO-PbO-Na2O-CaO glasses for white LEDs application

    NASA Astrophysics Data System (ADS)

    Mohammed, Al-B. F. A.; Lakshminarayana, G.; Baki, S. O.; Halimah, M. K.; Kityk, I. V.; Mahdi, M. A.

    2017-11-01

    Dy3+-doped borate glasses with nominal composition (60-x) B2O3-10 ZnO-10 PbO-10 Na2O-10 CaO-(x) Dy2O3 (x = 0, 0.1, 0.2, 0.5, 0.75, 1.0, 1.5 and 2.0 mol%) were prepared by the melt quenching technique. The XRD and SEM confirm the amorphous nature of the glasses and through EDAX, all the related elements were found in the synthesized glasses. The vibrations of metal cations such as Pb2+ and Zn2+, B-O-B bond bending vibrations from pentaborate groups, bending vibrations of BO3 triangles, and stretching vibrations of tetrahedral BO4- units etc. are identified from the respective FTIR and Raman spectra including the non-hygroscopic nature of the synthesized glasses. The TGA and DSC measurements were performed to study thermal properties, where ΔT >100 °C (ΔT = Tx - Tg) for all the glasses. Among all the Dy3+-doped glasses, the 0.75 mol% Dy3+-doped glass shows the highest PL intensity with four emissions, where the two transitions corresponding to 4F9/2 → 6H15/2 (blue) and 4F9/2 → 6H13/2 (yellow) are observed more intense than the others. The CIE chromaticity (x,y) coordinates for BZPNCDy 0.1 mol% glass are (0.398, 0.430), close to the white light region in the CIE 1931 chromaticity diagram. The dielectric properties of the 0.75 mol% Dy3+-doped glass such as dielectric constant, dielectric loss and AC conductivity were studied in the various frequencies and temperature.

  17. Crystal and molecular structure of Sr{sub 2}(Edta) . 5H{sub 2}O, Sr{sub 2}(H{sub 2}Edta)(HCO{sub 3}){sub 2} . 4H{sub 2}O, and Sr{sub 2}(H{sub 2}Edta)Cl{sub 2} . 5H{sub 2}O strontium ethylenediaminetetraacetates

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

    Polyakova, I. N., E-mail: polyakova@igic.ras.ru; Poznyak, A. L.; Sergienko, V. S.

    2009-03-15

    Three Sr{sup 2+} compounds with the Edta{sup 4-} and H{sub 2}Edta{sup 2-} ligands-Sr{sub 2}(Edta) . 5H{sub 2}O (I), Sr{sub 2}(H{sub 2}Edta)(HCO{sub 3}){sub 2} . 4H{sub 2}O (II), and Sr{sub 2}(H{sub 2}Edta)Cl{sub 2} . 5H{sub 2}O (III)-are synthesized, and their crystal structures are studied. In I, the Sr(1) atom is coordinated by the hexadentate Edta{sup 4-} ligand following the 2N + 4O pattern and by two O atoms of the neighboring ligands, which affords the formation of zigzag chains. The Sr(2) atom forms bonds with O atoms of five water molecules and attaches itself to a chain via bonds with threemore » O atoms of the Edta{sup 4-} ligands. The Sr(1)-O and Sr(2)-O bond lengths fall in the ranges 2.520(2)-2.656(3) and 2.527(3)-2.683(2) A, respectively. The Sr(1)-N bonds are 2.702(3) and 2.743(3) A long. In II and III, the H{sub 2}Edta{sup 2-} anions have a centrosymmetric structure with the trans configuration of the planar ethylenediamine fragment. The N atoms are blocked by acid protons. In II, the environment of the Sr atom is formed by six O atoms of three H{sub 2}Edta ligands, two O atoms of water molecules, and an O atom of the bicarbonate ion, which is disordered over two positions. In III, the environment of the Sr atom includes six O atoms of four H{sub 2}Edta{sup 2-} ligands and three O atoms of water molecules. The coordination number of the Sr atoms is equal to 8 + 1. In II and III, the main bonds fall in the ranges 2.534(3)-2.732(2) and 2.482(2)-2.746(3) A, whereas the ninth bond is elongated to 2.937(3) and 3.055(3) A, respectively. In II, all the structural elements are linked into wavy layers. The O-H-O interactions contribute to the stabilization of the layer and link neighboring layers. In III, hydrated Sr{sup 2+} cations and H{sub 2}Edta{sup -} anions form a three-dimensional [Sr{sub 2}(H{sub 2}Edta)(H{sub 2}O){sub 3}]{sub n}{sup 2n+} framework. The Cl{sup -} anions are fixed in channels of the framework by hydrogen bonds with four water

  18. Cell cycle- and chaperone-mediated regulation of H3K56ac incorporation in yeast.

    PubMed

    Kaplan, Tommy; Liu, Chih Long; Erkmann, Judith A; Holik, John; Grunstein, Michael; Kaufman, Paul D; Friedman, Nir; Rando, Oliver J

    2008-11-01

    Acetylation of histone H3 lysine 56 is a covalent modification best known as a mark of newly replicated chromatin, but it has also been linked to replication-independent histone replacement. Here, we measured H3K56ac levels at single-nucleosome resolution in asynchronously growing yeast cultures, as well as in yeast proceeding synchronously through the cell cycle. We developed a quantitative model of H3K56ac kinetics, which shows that H3K56ac is largely explained by the genomic replication timing and the turnover rate of each nucleosome, suggesting that cell cycle profiles of H3K56ac should reveal most first-time nucleosome incorporation events. However, since the deacetylases Hst3/4 prevent use of H3K56ac as a marker for histone deposition during M phase, we also directly measured M phase histone replacement rates. We report a global decrease in turnover rates during M phase and a further specific decrease in turnover at several early origins of replication, which switch from rapidly replaced in G1 phase to stably bound during M phase. Finally, by measuring H3 replacement in yeast deleted for the H3K56 acetyltransferase Rtt109 and its two co-chaperones Asf1 and Vps75, we find evidence that Rtt109 and Asf1 preferentially enhance histone replacement at rapidly replaced nucleosomes, whereas Vps75 appears to inhibit histone turnover at those loci. These results provide a broad perspective on histone replacement/incorporation throughout the cell cycle and suggest that H3K56 acetylation provides a positive-feedback loop by which replacement of a nucleosome enhances subsequent replacement at the same location.

  19. Low-Lying Energy Isomers and Global Minima of Aqueous Nanoclusters: Structures and Spectroscopic Features of the Pentagonal Dodecahedron (H2O)20 and (H3O)+(H2O)20

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

    Xantheas, Sotiris S.

    We rely on a hierarchy of methods to identify the low-lying isomers for the pentagonal dodecahedron (H2O)20 and the H3O+(H2O)20 clusters. Initial screening of isomers was performed with classical potentials [TIP4P, TTM2-F, TTM2.1-F for (H2O)20 and ASP for H3O+(H2O)20] and the networks obtained with those potentials were subsequently reoptimized at the DFT (B3LYP) and MP2 levels of theory. For the pentagonal dodecahedron (H2O)20 it was found that DFT (B3LYP) and MP2 produced the same global minimum. However, this was not the case for the H3O+(H2O)20 cluster, for which MP2 produced a different network for the global minimum when compared tomore » DFT (B3LYP). All low-lying minima of H3O+(H2O)20 correspond to hydrogen bonding networks having 9 ''free'' OH bonds and the hydronium ion on the surface of the cluster. The fact that DFT (B3LYP) and MP2 produce different results and issues related to the use of a smaller basis set, explains the discrepancy between the current results and the structure previously suggested [Science 304, 1137 (2004)] for the global minimum of the H3O+(H2O)20 cluster. Additionally, the IR spectra of the MP2 global minimum are closer to the experimentally measured ones than the spectra of the previously suggested DFT global minimum. The latter exhibit additional bands in the most red-shifted region of the OH stretching vibrations (corresponding to the ''fingerprint'' of the underlying hydrogen bonding network), which are absent from both the experimental as well as the spectra of the new structure suggested for the global minimum of this cluster.« less

  20. Three new d10 transition metal selenites containing PO4 tetrahedron: Cd7(HPO4)2(PO4)2(SeO3)2, Cd6(PO4)1.34(SeO3)4.66 and Zn3(HPO4)(SeO3)2(H2O)

    NASA Astrophysics Data System (ADS)

    Ma, Yun-Xiang; Gong, Ya-Ping; Hu, Chun-li; Mao, Jiang-Gao; Kong, Fang

    2018-06-01

    Three new d10 transition metal selenites containing PO4 tetrahedron, namely, Cd7(HPO4)2(PO4)2(SeO3)2 (1), Cd6(PO4)1.34(SeO3)4.66 (2) and Zn3(HPO4)(SeO3)2(H2O) (3), have been synthesized by hydrothermal reaction. They feature three different structural types. Compound 1 exhibits a novel 3D network composed of 3D cadmium selenite open framework with phosphate groups filled in the 1D helical tunnels. The structure of compound 2 displays a new 3D framework consisted of 2D cadmium oxide layers bridged by SeO3 and PO4 groups. Compound 3 is isostructural with the reported solids of Co3(SeO3)3-x(PO3OH)x(H2O) when x is equal to 1.0. Its structure could be viewed as a 3D zinc oxide open skeleton with SeO3 and HPO4 polyhedra attached on the wall of the tunnels. They represent the only examples in metal selenite phosphates in addition to the above cobalt compounds. Optical diffuse reflectance spectra revealed that these solids are insulators, which are consistent with the results of band structure computations based on DFT algorithm.

  1. SMA OBSERVATIONS OF THE W3(OH) COMPLEX: PHYSICAL AND CHEMICAL DIFFERENTIATION BETWEEN W3(H{sub 2}O) AND W3(OH)

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

    Qin, Sheng-Li; Schilke, Peter; Sánchez-Monge, Álvaro

    2015-04-10

    We report on the Submillimeter Array (SMA) observations of molecular lines at 270 GHz toward the W3(OH) and W3(H{sub 2}O) complex. Although previous observations already resolved the W3(H{sub 2}O) into two or three sub-components, the physical and chemical properties of the two sources are not well constrained. Our SMA observations clearly resolved the W3(OH) and W3(H{sub 2}O) continuum cores. Taking advantage of the line fitting tool XCLASS, we identified and modeled a rich molecular spectrum in this complex, including multiple CH{sub 3}CN and CH{sub 3}OH transitions in both cores. HDO, C{sub 2}H{sub 5}CN, O{sup 13}CS, and vibrationally excited lines ofmore » HCN, CH{sub 3}CN, and CH{sub 3}OCHO were only detected in W3(H{sub 2}O). We calculate gas temperatures and column densities for both cores. The results show that W3(H{sub 2}O) has higher gas temperatures and larger column densities than W3(OH) as previously observed, suggesting physical and chemical differences between the two cores. We compare the molecular abundances in W3(H{sub 2}O) to those in the Sgr B2(N) hot core, the Orion KL hot core, and the Orion Compact Ridge, and discuss the chemical origin of specific species. An east–west velocity gradient is seen in W3(H{sub 2}O), and the extension is consistent with the bipolar outflow orientation traced by water masers and radio jets. A north–south velocity gradient across W3(OH) is also observed. However, with current observations we cannot be assured whether the velocity gradients are caused by rotation, outflow, or radial velocity differences of the sub-components of W3(OH)« less

  2. Syntheses, crystal structures, and magnetic properties of the oxalato-bridged mixed-valence complexes (FeII(bpm)3]2[FeIII2(ox)5].8H2O and FeII(bpm)3Na(H2O)2Fe(ox)(3).4H2O (bpm = 2,2'-bipyrimidine).

    PubMed

    Armentano, D; De Munno, G; Faus, J; Lloret, F; Julve, M

    2001-02-12

    The preparation and crystal structures of two oxalato-bridged FeII-FeIII mixed-valence compounds, [FeII(bpm)3]2[FeIII2(ox)5].8H2O (1) and FeII(bpm)3Na(H2O)2FeIII(ox)(3).4H2O (2) (bpm = 2,2'-bipyrimidine; ox = oxalate dianion) are reported here. Complex 1 crystallizes in the triclinic system, space group P1, with a = 10.998(2) A, b = 13.073(3) A, c = 13.308(3) A, alpha = 101.95(2) degrees, beta = 109.20(2) degrees, gamma = 99.89(2) degrees, and Z = 1. Complex 2 crystallizes in the monoclinic system, space group P2(1)/c, with a = 12.609(2) A, b = 19.670(5) A, c = 15.843(3) A, beta = 99.46(1) degrees, and Z = 4. The structure of complex 1 consists of centrosymmetric oxalato-bridged dinuclear high-spin iron(III) [Fe2(ox)5]2- anions, tris-chelated low-spin iron(II) [Fe(bpm)3]2+ cations, and lattice water molecules. The iron atoms are hexacoordinated: six oxygen atoms (iron(III)) from two bidentate and one bisbidentate oxalato ligands and six nitrogen atoms (iron(II)) from three bidentate bpm groups. The Fe(III)-O(ox) and Fe(II)-N(bpm) bond distances vary in the ranges 1.967(3)-2.099(3) and 1.967(4)-1.995(3) A, respectively. The iron(III)-iron(III) separation across the bridging oxalato is 5.449(2) A, whereas the shortest intermolecular iron(III)-iron(II) distance is 6.841(2) A. The structure of complex 2 consists of neutral heterotrinuclear Fe(bpm)2Na(H2O)2Fe(ox)3 units and water molecules of crystallization. The tris-chelated low-spin iron(II) ([Fe(bpm)3]2+) and high-spin iron(III) ([Fe(ox)3]3-) entities act as bidentate ligands (through two bpm-nitrogen and two oxalato-oxygen atoms, respectively) toward the univalent sodium cation, yielding the trinuclear (bpm)2Fe(II)-bpm-Na(I)-ox-Fe(III)(ox)2 complex. Two cis-coordinated water molecules complete the distorted octahedral surrounding of the sodium atom. The ranges of the Fe(II)-N(bpm) and Fe(III)-O(ox) bond distances [1.968(6)-1.993(5) and 1.992(6)-2.024(6) A, respectively] compare well with those observed in 1. The Na

  3. Synthesis and X-ray Crystallography of [Mg(H2O)6][AnO2(C2H5COO)3]2 (An = U, Np, or Pu).

    PubMed

    Serezhkin, Viktor N; Grigoriev, Mikhail S; Abdulmyanov, Aleksey R; Fedoseev, Aleksandr M; Savchenkov, Anton V; Serezhkina, Larisa B

    2016-08-01

    Synthesis and X-ray crystallography of single crystals of [Mg(H2O)6][AnO2(C2H5COO)3]2, where An = U (I), Np (II), or Pu (III), are reported. Compounds I-III are isostructural and crystallize in the trigonal crystal system. The structures of I-III are built of hydrated magnesium cations [Mg(H2O)6](2+) and mononuclear [AnO2(C2H5COO)3](-) complexes, which belong to the AB(01)3 crystallochemical group of uranyl complexes (A = AnO2(2+), B(01) = C2H5COO(-)). Peculiarities of intermolecular interactions in the structures of [Mg(H2O)6][UO2(L)3]2 complexes depending on the carboxylate ion L (acetate, propionate, or n-butyrate) are investigated using the method of molecular Voronoi-Dirichlet polyhedra. Actinide contraction in the series of U(VI)-Np(VI)-Pu(VI) in compounds I-III is reflected in a decrease in the mean An═O bond lengths and in the volume and sphericity degree of Voronoi-Dirichlet polyhedra of An atoms.

  4. Adsorption of H2O, H2, O2, CO, NO, and CO2 on graphene/g-C3N4 nanocomposite investigated by density functional theory

    NASA Astrophysics Data System (ADS)

    Wu, Hong-Zhang; Bandaru, Sateesh; Liu, Jin; Li, Li-Li; Wang, Zhenling

    2018-02-01

    Motivated by the photocatalytic reactions of small molecules on g-C3N4 by these insights, we sought to explore the adsorption of H2O and CO2 molecules on the graphene side and H2O, H2, O2, CO, NO, and CO2 molecules on the g-C3N4 side of hybrid g-C3N4/graphene nanocomposite using first-principles calculations. The atomic structure and electronic properties of hybrid g-C3N4/graphene nanocomposite is explored. The adsorption of small molecules on graphene/g-C3N4 nanocomposite is thoroughly investigated. The computational studies revels that all small molecules on graphene/g-C3N4 nanocomposite are the physisorption. The adsorption characteristics of H2O and CO2 molecules on the graphene side are similar to that on graphene. The adsorption of H2O, H2, O2, CO, NO, and CO2 molecules on the g-C3N4 side always leads to a buckle structure of graphene/g-C3N4 nanocomposite. Graphene as a substrate can significantly relax the buckle degree of g-C3N4 in g-C3N4/graphene nanocomposite.

  5. Synthesis and structure of cesium complexes of nitrilotris(methylenephosphonic) acid [Cs-μ6-NH(CH2PO3)3H4] and [Cs2-μ10-NH(CH2PO3H)3] · H2O

    NASA Astrophysics Data System (ADS)

    Somov, N. V.; Chausov, F. F.; Zakirov, R. M.

    2017-07-01

    3D coordination polymers cesium nitrilotris(methylenephosphonate) and dicesium nitrilotris( methylenephosphonate) are synthesized and their crystal structure is determined. In the crystal of [Cs-μ6-NH(CH2PO3)3H4] (space group P, Z = 2), cesium atoms occupy two crystallographically inequivalent positions with c.n. = 10 and c.n. = 14. The phosphonate ligand plays the bridging function; its denticity is nine. The crystal packing consists of alternating layers of Cs atoms in different environments with layers of ligand molecules between them. A ligand is bound to three Cs atoms of one layer and three Cs atoms of another layer. In the crystal of [Cs2-μ10-NH(CH2PO3H)3] · H2O (space group P, Z = 2), the complex has a dimeric structure: the bridging phosphonate ligand coordinates Cs to form a three-dimensional Cs4O6 cluster. The denticity of the ligand is equal to nine; the coordination numbers of cesium atoms are seven and nine. Two-dimensional corrugated layers of Cs4O6 clusters lie in the (002) plane, and layers of ligand molecules are located between them. Each ligand molecule coordinates eight Cs atoms of one layer and two Cs atoms of the neighboring layer.

  6. Fabrication and Characterization of Luminescent Magnetic Bifunctional Nanocomposite Based on TbPO4·H2O Nanowires and Fe3O4 Nanoparticles

    NASA Astrophysics Data System (ADS)

    Huong, Nguyen Thanh; Hung, Nguyen Manh; Lien, Pham Thi; Van, Nguyen Duc; Nam, Pham Hong; Binh, Nguyen Thanh; Minh, Le Quoc

    2016-07-01

    The fabrication and properties of luminescent magnetic bifunctional nanocomposites comprised of TbPO4·H2O nanowires as a core and magnetite nanoparticles as a shell are presented. TbPO4·H2O nanowires were synthesized by a microwave-assisted method while the grafting process of freshly-formed superparamagnetic magnetite nanoparticles on the surface of luminescent nanowires was carried out by a co-precipitate method. The effects of the Fe3O4/TbPO4·H2O mass ratio on the luminescent and magnetic properties of the obtained nanocomposite were also investigated. The results showed that, for the optimized bifunctional nanocomposites, green luminescent emissions at 488 nm, 542 nm, 585 nm, 620 nm and superparamagnetic behavior with saturation magnetization M s of 6 emu/g were achieved. With a hyperthermia temperature of ~43.5°C under an alternating current (AC) magnetic field, the obtained TbPO4·H2O/Fe3O4 nanocomposite was expected to be used for both optical probing and hyperthermia cancer treatments in biomedical applications.

  7. Syntheses, structures, and vibrational spectroscopy of the two-dimensional iodates Ln(IO 3) 3 and Ln(IO 3) 3(H 2O) ( Lndbnd Yb, Lu)

    NASA Astrophysics Data System (ADS)

    Assefa, Zerihun; Ling, Jie; Haire, Richard G.; Albrecht-Schmitt, Thomas E.; Sykora, Richard E.

    2006-12-01

    The reaction of Lu 3+ or Yb 3+ and H 5IO 6 in aqueous media at 180 °C leads to the formation of Yb(IO 3) 3(H 2O) or Lu(IO 3) 3(H 2O), respectively, while the reaction of Yb metal with H 5IO 6 under similar reaction conditions gives rise to the anhydrous iodate, Yb(IO 3) 3. Under supercritical conditions Lu 3+ reacts with HIO 3 and KIO 4 to yield the isostructural Lu(IO 3) 3. The structures have been determined by single-crystal X-ray diffraction. Crystallographic data are (Mo Kα, λ=0.71073 Å): Yb(IO 3) 3, monoclinic, space group P2 1/ n, a=8.6664(9) Å, b=5.9904(6) Å, c=14.8826(15) Å, β=96.931(2)°, V=766.99(13), Z=4, R( F)=4.23% for 114 parameters with 1880 reflections with I>2 σ( I); Lu(IO 3) 3, monoclinic, space group P2 1/ n, a=8.6410(9), b=5.9961(6), c=14.8782(16) Å, β=97.028(2)°, V=765.08(14), Z=4, R( F)=2.65% for 119 parameters with 1756 reflections with I>2 σ( I); Yb(IO 3) 3(H 2O), monoclinic, space group C2/ c, a=27.2476(15), b=5.6296(3), c=12.0157(7) Å, β=98.636(1)°, V=1822.2(2), Z=8, R( F)=1.51% for 128 parameters with 2250 reflections with I>2 σ( I); Lu(IO 3) 3(H 2O), monoclinic, space group C2/ c, a=27.258(4), b=5.6251(7), c=12.0006(16) Å, β=98.704(2)°, V=1818.8(4), Z=8, R( F)=1.98% for 128 parameters with 2242 reflections with I>2 σ( I). The f elements in all of the compounds are found in seven-coordinate environments and bridged with monodentate, bidentate, or tridentate iodate anions. Both Lu(IO 3) 3(H 2O) and Yb(IO 3) 3(H 2O) display distinctively different vibrational profiles from their respective anhydrous analogs. Hence, the Raman profile can be used as a complementary diagnostic tool to discern the different structural motifs of the compounds.

  8. Polytherm of the CO(NH2)2-KNO3-H2O phase diagram

    NASA Astrophysics Data System (ADS)

    Yulina, I. V.; Trunin, A. S.

    2017-05-01

    The crystallization polytherm of the ternary CO(NH2)2-KNO3-H2O system is plotted for the first time via visual polythermal analysis and calculating ternary eutonics characteristics from data on the boundary elements of two-component systems. The ternary eutonics modeling error does not exceed 3.5%. In addition to the crystallization fields of individual components, the field of the redox reaction that occurs in the system between potassium nitrate and carbamide is shown in the CO(NH2)2-KNO3-H2O diagram by a dashed outline.

  9. Dielectric properties and electrical conductivity of the hybrid organic-inorganic polyvanadates (H{sub 3}N(CH{sub 2}){sub 4}NH{sub 3})[V{sub 6}O{sub 14}

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

    Nefzi, H.; Sediri, F., E-mail: faouzi.sediri@ipeit.rnu.tn; Faculte des Sciences de Tunis, Universite Tunis El Manar, 2092 El Manar, BP 94 CEDEX 1068, Cite Rommana Tunis

    2012-06-15

    Plate-like crystals of the polyvanadate (H{sub 3}N(CH{sub 2}){sub 4}NH{sub 3})[V{sub 6}O{sub 14}] have been synthesized via an hydrothermal treatment. X-ray powder diffraction, scanning electron microscope, Fourier transform infrared spectroscopy, electron spin resonance and complex impedance spectroscopy were used to analyze the hybrid material. The frequency dependence of AC conductivity at different temperatures indicates that the CBH model is the probable mechanism for the AC conduction behavior. The conductivity was measured by complex impedance spectroscopy which is equal to 31.10{sup -3} {Omega}{sup -1} m{sup -1} at 443 K. The Arrhenius diagram is not linear, it presents a rupture situated at 357more » K and the activation energies' average values are 0.22 eV and 0.14 eV, deduced from the Arrhenius relation. - Graphical abstract: At high temperature {epsilon} Double-Prime increases more rapidly which is due to the increasing conduction loss which rises with the increment in the DC conductivity. Highlights: Black-Right-Pointing-Pointer Rectangular plate-like crystals (H{sub 3}N(CH{sub 2}){sub 4}NH{sub 3})[V{sub 6}O{sub 14}] were synthesized. Black-Right-Pointing-Pointer frequency and temperature dependence of AC conductivity indicate CBH model. Black-Right-Pointing-Pointer The temperature dependence of DC conductivity exhibits two conduction mechanisms.« less

  10. Field induced 4f5d [Re(salen)]2O3[Dy(hfac)3(H2O)]2 single molecule magnet.

    PubMed

    Pointillart, Fabrice; Bernot, K; Sessoli, R; Gatteschi, D

    2010-05-03

    The reaction between the mononuclear [ReO(salen)(OMe)] (salen(2-) = N,N'-ethan-1,2-diylbis(salicylidenamine) dianion) and Dy(hfac)(3).2H(2)O (hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate anion) complexes lead to the formation of a compound with the formula {[Re(salen)](2)O(3)[Dy(hfac)(3)(H(2)O)](2)}(CHCl(3))(2)(CH(2)Cl(2))(2) noted (Dy(2)Re(2)). This compound has been characterized by single crystal and powder X-ray diffraction and has been found isostructural to the Y(III) derivative (Y(2)Re(2)) that we previously reported. The cyclic voltammetry demonstrates the redox activity of the system. The characterization of both static and dynamic magnetic properties is reported. Static magnetic data has been analyzed after the cancellation of the crystal field contribution by two different methods. Weak ferromagnetic exchange interactions between the Dy(III) ions are highlighted. The compound Dy(2)Re(2) displays slow relaxation of the magnetization when an external magnetic field is applied. Alternating current susceptibility shows a thermally activated behavior with pre-exponential factors of 7.13 (+/-0.10) x 10(-6) and 5.76 (+/-0.27) x 10(-7) s, and energy barriers of 4.19 (+/-0.02) and 8.52 (+/-0.55) K respectively for low and high temperature regimes.

  11. Polarization Rotation in Ferroelectric Tricolor PbTiO3/SrTiO3/PbZr0.2Ti0.8O3 Superlattices.

    PubMed

    Lemée, Nathalie; Infante, Ingrid C; Hubault, Cécile; Boulle, Alexandre; Blanc, Nils; Boudet, Nathalie; Demange, Valérie; Karkut, Michael G

    2015-09-16

    In ferroelectric thin films, controlling the orientation of the polarization is a key element to controlling their physical properties. We use laboratory and synchrotron X-ray diffraction to investigate ferroelectric bicolor PbTiO3/PbZr0.2Ti0.8O3 and tricolor PbTiO3/SrTiO3/PbZr0.2Ti0.8O3 superlattices and to study the role of the SrTiO3 layers on the domain structure. In the tricolor superlattices, we demonstrate the existence of 180° ferroelectric stripe nanodomains, induced by the depolarization field produced by the SrTiO3 layers. Each ultrathin SrTiO3 layer modifies the electrostatic boundary conditions between the ferroelectric layers compared to the corresponding bicolor structures, leading to the suppression of the a/c polydomain states. Combined with the electrostatic effect, the tensile strain induced by PbZr0.2Ti0.8O3 in the PbTiO3 layers leads to polarization rotation in the system as evidenced by grazing incidence X-ray measurements. This polarization rotation is associated with the monoclinic Mc phase as revealed by the splitting of the (HHL) and (H0L) reciprocal lattice points. This work demonstrates that the tricolor paraelectric/ferroelectric superlattices constitute a tunable system to investigate the concomitant effects of strains and depolarizing fields. Our studies provide a pathway to stabilize a monoclinic symmetry in ferroelectric layers, which is of particular interest for the enhancement of the piezoelectric properties.

  12. The reaction of O(1 D) with H2O and the reaction of OH with C3H6

    NASA Technical Reports Server (NTRS)

    Simonaitis, R.; Heicklen, J.

    1972-01-01

    The N2O was photolyzed at 2139 A to produce O(1 D) atoms in the presence of H2O and CO. The O(1 D) atoms react with H2O to produce HO radicals, as measured by CO2 production from the reaction of OH with CO. The relative rate constant for O(1 D) removal by H2O compared to that by N2O is 2.1. In the presence of C3H6, the OH can be removed by reaction with either CO or C3H6.

  13. Physical-chemical examination of the N2O3-SO3-H2O system

    NASA Technical Reports Server (NTRS)

    Linstroem, C.; Malyska, G.

    1977-01-01

    It was found that when (NO)HSO4 is added to absolute H2SO4, specific conductivity rises sharply, possibly due to an increase in mutual interionic effects and viscosity as the (NO)HSO4 concentration rises. The addition of SO3 to the solution yielded a precipitate; a combination of analysis, IR spectroscopy and X-ray diffraction techniques indicated that this precipitate was (NO)HS2O7.

  14. Decomposition of 3,5-dinitrobenzamide in aqueous solution during UV/H2O2 and UV/TiO2 oxidation processes.

    PubMed

    Yan, Yingjie; Liao, Qi-Nan; Ji, Feng; Wang, Wei; Yuan, Shoujun; Hu, Zhen-Hu

    2017-02-01

    3,5-Dinitrobenzamide has been widely used as a feed additive to control coccidiosis in poultry, and part of the added 3,5-dinitrobenzamide is excreted into wastewater and surface water. The removal of 3,5-dinitrobenzamide from wastewater and surface water has not been reported in previous studies. Highly reactive hydroxyl radicals from UV/hydrogen peroxide (H 2 O 2 ) and UV/titanium dioxide (TiO 2 ) advanced oxidation processes (AOPs) can decompose organic contaminants efficiently. In this study, the decomposition of 3,5-dinitrobenzamide in aqueous solution during UV/H 2 O 2 and UV/TiO 2 oxidation processes was investigated. The decomposition of 3,5-dinitrobenzamide fits well with a fluence-based pseudo-first-order kinetics model. The decomposition in both two oxidation processes was affected by solution pH, and was inhibited under alkaline conditions. Inorganic anions such as NO 3 - , Cl - , SO 4 2- , HCO 3 - , and CO 3 2- inhibited the degradation of 3,5-dinitrobenzamide during the UV/H 2 O 2 and UV/TiO 2 oxidation processes. After complete decomposition in both oxidation processes, approximately 50% of 3,5-dinitrobenzamide was decomposed into organic intermediates, and the rest was mineralized to CO 2 , H 2 O, and other inorganic anions. Ions such as NH 4 + , NO 3 - , and NO 2 - were released into aqueous solution during the degradation. The primary decomposition products of 3,5-dinitrobenzamide were identified using time-of-flight mass spectrometry (LCMS-IT-TOF). Based on these products and ions release, a possible decomposition pathway of 3,5-dinitrobenzamide in both UV/H 2 O 2 and UV/TiO 2 processes was proposed.

  15. Pressure dependence of side chain 13C chemical shifts in model peptides Ac-Gly-Gly-Xxx-Ala-NH2.

    PubMed

    Beck Erlach, Markus; Koehler, Joerg; Crusca, Edson; Munte, Claudia E; Kainosho, Masatsune; Kremer, Werner; Kalbitzer, Hans Robert

    2017-10-01

    For evaluating the pressure responses of folded as well as intrinsically unfolded proteins detectable by NMR spectroscopy the availability of data from well-defined model systems is indispensable. In this work we report the pressure dependence of 13 C chemical shifts of the side chain atoms in the protected tetrapeptides Ac-Gly-Gly-Xxx-Ala-NH 2 (Xxx, one of the 20 canonical amino acids). Contrary to expectation the chemical shifts of a number of nuclei have a nonlinear dependence on pressure in the range from 0.1 to 200 MPa. The size of the polynomial pressure coefficients B 1 and B 2 is dependent on the type of atom and amino acid studied. For H N , N and C α the first order pressure coefficient B 1 is also correlated to the chemical shift at atmospheric pressure. The first and second order pressure coefficients of a given type of carbon atom show significant linear correlations suggesting that the NMR observable pressure effects in the different amino acids have at least partly the same physical cause. In line with this observation the magnitude of the second order coefficients of nuclei being direct neighbors in the chemical structure also are weakly correlated. The downfield shifts of the methyl resonances suggest that gauche conformers of the side chains are not preferred with pressure. The valine and leucine methyl groups in the model peptides were assigned using stereospecifically 13 C enriched amino acids with the pro-R carbons downfield shifted relative to the pro-S carbons.

  16. Electrocatalytic activity of LaNiO3 toward H2O2 reduction reaction: Minimization of oxygen evolution

    NASA Astrophysics Data System (ADS)

    Amirfakhri, Seyed Javad; Meunier, Jean-Luc; Berk, Dimitrios

    2014-12-01

    The catalytic activity of LaNiO3 toward H2O2 reduction reaction (HPRR), with a potential application in the cathode side of fuel cells, is studied in alkaline, neutral and acidic solutions by rotating disk electrode. The LaNiO3 particles synthesised by citrate-based sol-gel method have sizes between 30 and 70 nm with an active specific surface area of 1.26 ± 0.05 m2 g-1. LaNiO3 shows high catalytic activity toward HPRR in 0.1 M KOH solution with an exchange current density based on the active surface area (j0A) of (7.4 ± 1) × 10-6 A cm-2 which is noticeably higher than the j0A of N-doped graphene. The analysis of kinetic parameters suggests that the direct reduction of H2O2, H2O2 decomposition, O2 reduction and O2 desorption occur through HPRR on this catalyst. In order to control and minimize oxygen evolution from the electrode surface, the effects of catalyst loading, bulk concentration of H2O2, and using a mixture of LaNiO3 and N-doped graphene are studied. Although the mechanism of HPRR is independent of the aforementioned operating conditions, gas evolution decreases by increasing the catalyst loading, decreasing the bulk concentration of H2O2, and addition of N-doped graphene to LaNiO3.

  17. Oxidative degradation of endotoxin by advanced oxidation process (O3/H2O2 & UV/H2O2).

    PubMed

    Oh, Byung-Taek; Seo, Young-Suk; Sudhakar, Dega; Choe, Ji-Hyun; Lee, Sang-Myeong; Park, Youn-Jong; Cho, Min

    2014-08-30

    The presence of endotoxin in water environments may pose a serious public health hazard. We investigated the effectiveness of advanced oxidative processes (AOP: O3/H2O2 and UV/H2O2) in the oxidative degradation of endotoxin. In addition, we measured the release of endotoxin from Escherichia coli following typical disinfection methods, such as chlorine, ozone alone and UV, and compared it with the use of AOPs. Finally, we tested the AOP-treated samples in their ability to induce tumor necrosis factor alpha (TNF-α) in mouse peritoneal macrophages. The production of hydroxyl radical in AOPs showed superior ability to degrade endotoxin in buffered solution, as well as water samples from Korean water treatment facilities, with the ozone/H2O2 being more efficient compared to UV/H2O2. In addition, the AOPs proved effective not only in eliminating E. coli in the samples, but also in endotoxin degradation, while the standard disinfection methods lead to the release of endotoxin following the bacteria destruction. Furthermore, in the experiments with macrophages, the AOPs-deactivated endotoxin lead to the smallest induction of TNF-α, which shows the loss of inflammation activity, compared to ozone treatment alone. In conclusion, these results suggest that AOPs offer an effective and mild method for endotoxin degradation in the water systems. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Oxidant effect of La(NO3)3·6H2O solution on the crystalline characteristics of nanocrystalline ZrO2 films grown by atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Oh, Nam Khen; Kim, Jin-Tae; Kang, Goru; An, Jong-Ki; Nam, Minwoo; Kim, So Yeon; Park, In-Sung; Yun, Ju-Young

    2017-02-01

    Nanocrystalline ZrO2 films were synthesized by atomic layer deposition method using CpZr[N(CH3)2]3 (Cp = C5H5) as the metal precursor and La(NO3)3·6H2O solution as the oxygen source. La element in the deposited ZrO2 films could not be detected as its content was below the resolution limit of the X-ray photoelectron spectroscopy. The alternative introduction of La(NO3)3·6H2O solution to conventionally used H2O as the oxidant effectively altered the crystalline structure, grain size, and surface roughness of the grown ZrO2 films. Specifically, the crystalline structure of the ZrO2 film changed from a mixture of tetragonal and monoclinic phases to monoclinic phase. The average grain size also increased, and the resulting film surface became rougher. The average grain sizes of the ZrO2 films prepared from La(NO3)3·6H2O solution at concentrations of 10, 20, 30, and 40% were 280, 256, 208, and 200 nm, respectively, whereas that prepared using H2O oxidant was 142 nm. However, the concentration of La(NO3)3·6H2O solution minimally influenced the crystalline characteristics of the nanocrystalline ZrO2 films i.e., the crystalline structure, grain size, and surface roughness except for crystallite size.

  19. Reactivity of Cyclopentadienyl Molybdenum Compounds towards Formic Acid: Structural Characterization of CpMo(PMe3)(CO)2H, CpMo(PMe3)2(CO)H, [CpMo(μ-O)(μ-O2CH)]2, and [Cp*Mo(μ-O)(μ-O2CH)]2.

    PubMed

    Neary, Michelle C; Parkin, Gerard

    2017-02-06

    The molecular structures of CpMo(PMe 3 )(CO) 2 H and CpMo(PMe 3 ) 2 (CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3 )(CO) 2 H and CpMo(PMe 3 ) 2 (CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H-Mo-CO moiety are displaced towards the hydride ligand. While Cp R Mo(PMe 3 ) 3-x (CO) x H (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts for the release of H 2 from formic acid, the carbonyl derivatives, Cp R Mo(CO) 3 H, are also observed to form dinuclear formate compounds, namely, [Cp R Mo(μ-O)(μ-O 2 CH)] 2 . The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2 CH)] 2 and [Cp*Mo(μ-O)(μ-O 2 CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2 CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO-1) orbitals. The σ 2 δ* 2 configuration thus corresponds to a formal direct Mo-Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo-Mo bond, whereas a Mo═Mo double bond is required in the absence of lone-pair donation.

  20. Ab Initio Reaction Kinetics of CH 3 O$$\\dot{C}$$(=O) and $$\\dot{C}$$H 2 OC(=O)H Radicals

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

    Tan, Ting; Yang, Xueliang; Ju, Yiguang

    The dissociation and isomerization kinetics of the methyl ester combustion intermediates methoxycarbonyl radical (CH3Omore » $$\\dot{C}$$(=O)) and (formyloxy)methyl radical ($$\\dot{C}$$H2OC(=O)H) are investigated theoretically using high-level ab initio methods and Rice–Ramsperger–Kassel–Marcus (RRKM)/master equation (ME) theory. Geometries obtained at the hybrid density functional theory (DFT) and coupled cluster singles and doubles with perturbative triples correction (CCSD(T)) levels of theory are found to be similar. We employ high-level ab initio wave function methods to refine the potential energy surface: CCSD(T), multireference singles and doubles configuration interaction (MRSDCI) with the Davidson–Silver (DS) correction, and multireference averaged coupled-pair functional (MRACPF2) theory. MRSDCI+DS and MRACPF2 capture the multiconfigurational character of transition states (TSs) and predict lower barrier heights than CCSD(T). The temperature- and pressure-dependent rate coefficients are computed using RRKM/ME theory in the temperature range 300–2500 K and a pressure range of 0.01 atm to the high-pressure limit, which are then fitted to modified Arrhenius expressions. Dissociation of CH3O$$\\dot{C}$$(=O) to $$\\dot{C}$$H3 and CO2 is predicted to be much faster than dissociating to CH3$$\\dot{O}$$ and CO, consistent with its greater exothermicity. Isomerization between CH3O$$\\dot{C}$$(=O) and $$\\dot{C}$$H2OC(=O)H is predicted to be the slowest among the studied reactions and rarely happens even at high temperature and high pressure, suggesting the decomposition pathways of the two radicals are not strongly coupled. The predicted rate coefficients and branching fractions at finite pressures differ significantly from the corresponding high-pressure-limit results, especially at relatively high temperatures. Finally, because it is one of the most important CH3$$\\dot{O}$$ removal mechanisms under atmospheric conditions, the reaction kinetics of

  1. A variable Ag-Cr-Oxalate channel lattice: [M(x)Ag(0.5)(-)(x)(H(2)O)(3)]@[Ag(2.5)Cr(C(2)O(4))(3)], M = K, Cs, Ag.

    PubMed

    Dean, Philip A W; Craig, Don; Dance, Ian; Russell, Vanessa; Scudder, Marcia

    2004-01-26

    Reaction of aqueous AgNO(3) with aqueous M(3)[Cr(ox)(3)] in >or=3:1 molar ratio causes the rapid growth of large, cherry-black, light-stable crystals which are not Ag(3)[Cr(ox)(3)], but [M(0.5)(H(2)O)(3)]@[Ag(2.5)Cr(ox)(3)] (ox(2)(-) = oxalate, C(2)O(4)(2)(-); M = Na, K, Cs, Ag, or mixtures of Ag and a group 1 element). The structure of these crystals contains an invariant channeled framework, with composition [[Ag(2.5)Cr(ox)(3)](-)(0.5)]( infinity ), constructed with [Cr(ox)(3)] coordination units linked by Ag atoms through centrosymmetric [Cr-O(2)C(2)O(2)-Ag](2) double bridges. The framework composition [Ag(2.5)Cr(ox)(3)](-)(0.5) occurs because one Ag is located on a 2-fold axis. Within the channels there is a well-defined and ordered set of six water molecules, strongly hydrogen bonded to each other and some of the oxalate O atoms. This invariant channel plus water structure accommodates group 1 cations, and/or Ag cations, in different locations and in variable proportions, but always coordinated by channel water and some oxalate O atoms. The general formulation of these crystals is therefore [M(x)Ag(0.5-x)(H(2)O)(3)]@[Ag(2.5)Cr(ox)(3)]. Five different crystals with this structure are reported, with compositions 1 Ag(0.5)[Ag(2.5)Cr(ox)(3)](H(2)O)(3), 2 Cs(0.19)Ag(0.31)[Ag(2.5)Cr(ox)(3)](H(2)O)(3), 3 K(0.28)Ag(0.22)[Ag(2.5)Cr(ox)(3)](H(2)O)(3), 4 Cs(0.41)Ag(0.09)[Ag(2.5)Cr(ox)(3)](H(2)O)(3), and 5 Cs(0.43)Ag(0.07) [Ag(2.5)Cr(ox)(3)](H(2)O)(3). All crystallize in space group C2/c, with a approximately 18.4, b approximately 14.6, c approximately 12.3 A, beta approximately 113 degrees. Pure Ag(3)[Cr(ox)(3)](H(2)O)(3), which has the same crystal structure (1), was obtained from water by treating Li(3)[Cr(ox)(3)] with excess AgNO(3). Complete dehydration of all of these compounds occurs between 30 and 100 degrees C, with loss of diffraction, but rehydration by exposure to H(2)O(g) at ambient temperature leads to recovery of the original diffraction pattern. In single

  2. New insights into genotype–phenotype correlation for GLI3 mutations

    PubMed Central

    Démurger, Florence; Ichkou, Amale; Mougou-Zerelli, Soumaya; Le Merrer, Martine; Goudefroye, Géraldine; Delezoide, Anne-Lise; Quélin, Chloé; Manouvrier, Sylvie; Baujat, Geneviève; Fradin, Mélanie; Pasquier, Laurent; Megarbané, André; Faivre, Laurence; Baumann, Clarisse; Nampoothiri, Sheela; Roume, Joëlle; Isidor, Bertrand; Lacombe, Didier; Delrue, Marie-Ange; Mercier, Sandra; Philip, Nicole; Schaefer, Elise; Holder, Muriel; Krause, Amanda; Laffargue, Fanny; Sinico, Martine; Amram, Daniel; André, Gwenaelle; Liquier, Alain; Rossi, Massimiliano; Amiel, Jeanne; Giuliano, Fabienne; Boute, Odile; Dieux-Coeslier, Anne; Jacquemont, Marie-Line; Afenjar, Alexandra; Van Maldergem, Lionel; Lackmy-Port-Lis, Marylin; Vincent- Delorme, Catherine; Chauvet, Marie-Liesse; Cormier-Daire, Valérie; Devisme, Louise; Geneviève, David; Munnich, Arnold; Viot, Géraldine; Raoul, Odile; Romana, Serge; Gonzales, Marie; Encha-Razavi, Ferechte; Odent, Sylvie; Vekemans, Michel; Attie-Bitach, Tania

    2015-01-01

    The phenotypic spectrum of GLI3 mutations includes autosomal dominant Greig cephalopolysyndactyly syndrome (GCPS) and Pallister–Hall syndrome (PHS). PHS was first described as a lethal condition associating hypothalamic hamartoma, postaxial or central polydactyly, anal atresia and bifid epiglottis. Typical GCPS combines polysyndactyly of hands and feet and craniofacial features. Genotype–phenotype correlations have been found both for the location and the nature of GLI3 mutations, highlighting the bifunctional nature of GLI3 during development. Here we report on the molecular and clinical study of 76 cases from 55 families with either a GLI3 mutation (49 GCPS and 21 PHS), or a large deletion encompassing the GLI3 gene (6 GCPS cases). Most of mutations are novel and consistent with the previously reported genotype–phenotype correlation. Our results also show a correlation between the location of the mutation and abnormal corpus callosum observed in some patients with GCPS. Fetal PHS observations emphasize on the possible lethality of GLI3 mutations and extend the phenotypic spectrum of malformations such as agnathia and reductional limbs defects. GLI3 expression studied by in situ hybridization during human development confirms its early expression in target tissues. PMID:24736735

  3. New insights into genotype-phenotype correlation for GLI3 mutations.

    PubMed

    Démurger, Florence; Ichkou, Amale; Mougou-Zerelli, Soumaya; Le Merrer, Martine; Goudefroye, Géraldine; Delezoide, Anne-Lise; Quélin, Chloé; Manouvrier, Sylvie; Baujat, Geneviève; Fradin, Mélanie; Pasquier, Laurent; Megarbané, André; Faivre, Laurence; Baumann, Clarisse; Nampoothiri, Sheela; Roume, Joëlle; Isidor, Bertrand; Lacombe, Didier; Delrue, Marie-Ange; Mercier, Sandra; Philip, Nicole; Schaefer, Elise; Holder, Muriel; Krause, Amanda; Laffargue, Fanny; Sinico, Martine; Amram, Daniel; André, Gwenaelle; Liquier, Alain; Rossi, Massimiliano; Amiel, Jeanne; Giuliano, Fabienne; Boute, Odile; Dieux-Coeslier, Anne; Jacquemont, Marie-Line; Afenjar, Alexandra; Van Maldergem, Lionel; Lackmy-Port-Lis, Marylin; Vincent-Delorme, Catherine; Chauvet, Marie-Liesse; Cormier-Daire, Valérie; Devisme, Louise; Geneviève, David; Munnich, Arnold; Viot, Géraldine; Raoul, Odile; Romana, Serge; Gonzales, Marie; Encha-Razavi, Ferechte; Odent, Sylvie; Vekemans, Michel; Attie-Bitach, Tania

    2015-01-01

    The phenotypic spectrum of GLI3 mutations includes autosomal dominant Greig cephalopolysyndactyly syndrome (GCPS) and Pallister-Hall syndrome (PHS). PHS was first described as a lethal condition associating hypothalamic hamartoma, postaxial or central polydactyly, anal atresia and bifid epiglottis. Typical GCPS combines polysyndactyly of hands and feet and craniofacial features. Genotype-phenotype correlations have been found both for the location and the nature of GLI3 mutations, highlighting the bifunctional nature of GLI3 during development. Here we report on the molecular and clinical study of 76 cases from 55 families with either a GLI3 mutation (49 GCPS and 21 PHS), or a large deletion encompassing the GLI3 gene (6 GCPS cases). Most of mutations are novel and consistent with the previously reported genotype-phenotype correlation. Our results also show a correlation between the location of the mutation and abnormal corpus callosum observed in some patients with GCPS. Fetal PHS observations emphasize on the possible lethality of GLI3 mutations and extend the phenotypic spectrum of malformations such as agnathia and reductional limbs defects. GLI3 expression studied by in situ hybridization during human development confirms its early expression in target tissues.

  4. Synthesis, Structures, and Vibrational Spectroscopy of the Two-Dimensional Iodates Ln(IO) 3 and Ln(IO 3) 3(H 2O) ( Ln-Yb,Lu)

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

    Assefa, Zerihun; Ling, Jie; Haire, Richard

    2006-01-01

    The reaction of Lu3+ or Yb3+ and H5IO6 in aqueous media at 180 C leads to the formation of Yb(IO3)3(H2O) or Lu(IO3)3(H2O), respectively, while the reaction of Yb metal with H5IO6 under similar reaction conditions gives rise to the anhydrous iodate, Yb(IO3)3. Under supercritical conditions Lu3+ reacts with HIO3 and KIO4 to yield the isostructural Lu(IO3)3. The structures have been determined by single-crystal X-ray diffraction. Crystallographic data are (MoKa, {lambda}=0.71073 {angstrom}): Yb(IO3)3, monoclinic, space group P21/n, a=8.6664(9) {angstrom}, b=5.9904(6) {angstrom}, c=14.8826(15) {angstrom}, {beta}=96.931(2){sup o}, V=766.99(13), Z=4, R(F)=4.23% for 114 parameters with 1880 reflections with I>2s(I); Lu(IO3)3, monoclinic, space group P21/n,more » a=8.6410(9), b=5.9961(6), c=14.8782(16) {angstrom}, {beta}=97.028(2){sup o}, V=765.08(14), Z=4, R(F)=2.65% for 119 parameters with 1756 reflections with I>2s(I); Yb(IO3)3(H2O), monoclinic, space group C2/c, a=27.2476(15), b=5.6296(3), c=12.0157(7) {angstrom}, {beta}=98.636(1){sup o}, V=1822.2(2), Z=8, R(F)=1.51% for 128 parameters with 2250 reflections with I>2s(I); Lu(IO3)3(H2O), monoclinic, space group C2/c, a=27.258(4), b=5.6251(7), c=12.0006(16) {angstrom}, {beta}=98.704(2){sup o}, V=1818.8(4), Z=8, R(F)=1.98% for 128 parameters with 2242 reflections with I>2s(I). The f elements in all of the compounds are found in seven-coordinate environments and bridged with monodentate, bidentate, or tridentate iodate anions. Both Lu(IO3)3(H2O) and Yb(IO3)3(H2O) display distinctively different vibrational profiles from their respective anhydrous analogs. Hence, the Raman profile can be used as a complementary diagnostic tool to discern the different structural motifs of the compounds.« less

  5. A simple hydrogen-bonded chain in (3Z)-3-{1-[(5-phenyl-1H-pyrazol-3-yl)amino]ethylidene}-4,5-dihydrofuran-2(3H)-one, and a hydrogen-bonded ribbon of centrosymmetric rings in the self-assembled adduct (3Z)-3-{1-[(5-methyl-1H-pyrazol-3-yl)amino]ethylidene}-4,5-dihydrofuran-2(3H)-one-6-(2-hydroxyethyl)-2,5-dimethylpyrazolo[1,5-a]pyrimidin-7(4H)-one (1/1).

    PubMed

    Quiroga, Jairo; Portilla, Jaime; Cobo, Justo; Glidewell, Christopher

    2010-01-01

    (3Z)-3-{1-[(5-Phenyl-1H-pyrazol-3-yl)amino]ethylidene}-4,5-dihydrofuran-2(3H)-one, C(15)H(15)N(3)O(2), (I), and the stoichiometric adduct (3Z)-3-{1-[(5-methyl-1H-pyrazol-3-yl)amino]ethylidene}-4,5-dihydrofuran-2(3H)-one-6-(2-hydroxyethyl)-2,5-dimethylpyrazolo[1,5-a]pyrimidin-7(4H)-one (1/1), C(10)H(13)N(3)O(2).C(10)H(13)N(3)O(2), (II), in which the two components have the same composition but different constitutions, are formed in the reactions of 2-acetyl-4-butyrolactone with 5-amino-3-phenyl-1H-pyrazole and 5-amino-3-methyl-1H-pyrazole, respectively. In each compound, the furanone component contains an intramolecular N-H...O hydrogen bond. The molecules of (I) are linked into a chain by a single intermolecular N-H...O hydrogen bond, while in (II), a combination of one O-H...N hydrogen bond, within the selected asymmetric unit, and two N-H...O hydrogen bonds link the molecular components into a ribbon containing alternating centrosymmetric R(4)(4)(20) and R(6)(6)(22) rings.

  6. Density functional theory study of 3R- and 2H-CuAlO2 under pressure

    NASA Astrophysics Data System (ADS)

    Liu, Qi-Jun; Liu, Zheng-Tang; Feng, Li-Ping; Tian, Hao; Liu, Wen-Ting; Yan, Feng

    2010-10-01

    We present a first-principles density-functional theory based study of the impact of pressure on the structural and elastic properties of bulk 3R- and 2H-CuAlO2. The ground state properties of 3R- and 2H-CuAlO2 are obtained, which are in good agreement with previous experimental and theoretical data. The analysis of enthalpy variation with pressure indicates the phase transition pressure between 3R and 2H is 15.4 GPa. The independent elastic constants of 3R- and 2H-CuAlO2 are calculated. As the applied pressure increases, the calculations show the presences of mechanical instability at 26.2 and 27.8 GPa for 3R- and 2H-CuAlO2, which are possibly related with the phase transitions.

  7. Phase Equilibria and Transport Properties in the Systems AgNO3/RCN/H2O. R = CH3, C2H5, C3H7, C4H,, C6H5, and C6H5CH2

    NASA Astrophysics Data System (ADS)

    Das, Surjya P.; Wittekopf, Burghard; Weil, Konrad G.

    1988-11-01

    Silver nitrate can form homogeneous liquid phases with some organic nitriles and water, even when there is no miscibility between the pure liquid components. We determined the shapes of the single phase regions in the ternary phase diagram for the following systems: silver nitrate /RCN /H2O with R =CH3, C3H7, C6H5, and C6H5CH2 at room temperature and for R =C6H5 also at 60 °C and O °C. Furthermore we studied kinematic viscosities, electrical conductivities, and densities of mixtures containing silver nitrate, RCN, and water with the mole ratios X /4 /1 (0.2≦ X ≦S 3.4). In these cases also R = C2H5 and C4H9 were studied. The organic nitriles show different dependences of viscosity and conductivity on the silver nitrate content from the aliphatic ones.

  8. Heat-Storage Modules Containing LiNO3-3H2O and Graphite Foam

    NASA Technical Reports Server (NTRS)

    Bootle, John

    2008-01-01

    A heat-storage module based on a commercial open-cell graphite foam (Poco-Foam or equivalent) imbued with lithium nitrate trihydrate (LiNO3-3H2O) has been developed as a prototype of other such modules for use as short-term heat sources or heat sinks in the temperature range of approximately 28 to 30 C. In this module, the LiNO3-3H2O serves as a phase-change heat-storage material and the graphite foam as thermally conductive filler for transferring heat to or from the phase-change material. In comparison with typical prior heat-storage modules in which paraffins are the phase-change materials and aluminum fins are the thermally conductive fillers, this module has more than twice the heat-storage capacity per unit volume.

  9. Synthesis, spectral and antifungal analysis of diaryldithiophosphates of mono- and dibutyltin(IV): x-ray structure of [{(3,5-CH3)2C6H3O)2PS2}2Sn(nBu)2].

    PubMed

    Syed, Atiya; Khajuria, Ruchi; Kumar, Sandeep; Jassal, Amanpreet Kaur; Hundal, Maninder S; Pandey, Sushil K

    2014-01-01

    Diaryldithiophosphate complexes of mono- and dibutyltin(IV) corresponding to [(ArO)(2)PS(2)(n)Sn(nBu)xCl(4-x-n)] (Ar = o-CH(3)C(6)H(4), m-CH(3)C(6)H(4), p-CH(3)C(6)H(4), 4-Cl-3-CH(3)C(6)H(3), (3,5-CH(3))(2)C(6)H(3); n = 1, 2 for x = 1 and n = 2 for x = 2) were successfully isolated and characterized by elemental analyses, IR, multinuclear NMR ((1)H, (13)C, (31)P and (119)Sn) spectroscopy and X-ray analysis. The thermal properties of the complex [(3,5-CH(3))(2)C(6)H(3)O(2)PS(2)](2)Sn(nBu)(2) (12) have been examined by combined DTA/ DTG thermal analyses. Single crystal X-ray analysis of [(3,5-CH(3))(2)C(6)H(3)O(2)PS(2)](2)S(n)(nBu)(2) (12) revealed that two diaryldithiophosphate ions are coordinated to tin atom in an anisobidentate fashion through the sulfur atoms of each dithiophosphate moiety leading to distorted skew-trapezoidal bipyramidal geometry. The antifungal activity depicts that these complexes are active against fungus Penicillium chrysogenium.

  10. Reactivity of cyclopentadienyl molybdenum compounds towards formic acid: Structural characterization of CpMo(PMe 3)(CO) 2H, CpMo(PMe 3) 2(CO)H, [CpMo(μ-O)(μ-O 2CH)] 2, and [Cp*Mo(μ-O)(μ-O 2CH)] 2

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

    Neary, Michelle C.; Parkin, Gerard

    Here, the molecular structures of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H–Mo–CO moiety are displaced towards the hydride ligand. While CpRMo(PMe 3) 3–x(CO) xH (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts formore » the release of H 2 from formic acid, the carbonyl derivatives, CpRMo(CO)3H, are also observed to form dinuclear formate compounds, namely, [Cp RMo(μ-O)(μ-O 2CH)] 2. The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2CH)] 2 and [Cp*Mo(μ-O)(μ-O 2CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO–1) orbitals. The σ 2δ *2 configuration thus corresponds to a formal direct Mo–Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo–Mo bond, whereas a Mo=Mo double bond is required in the absence of lone-pair donation.« less

  11. Reactivity of cyclopentadienyl molybdenum compounds towards formic acid: Structural characterization of CpMo(PMe 3)(CO) 2H, CpMo(PMe 3) 2(CO)H, [CpMo(μ-O)(μ-O 2CH)] 2, and [Cp*Mo(μ-O)(μ-O 2CH)] 2

    DOE PAGES

    Neary, Michelle C.; Parkin, Gerard

    2017-01-19

    Here, the molecular structures of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H–Mo–CO moiety are displaced towards the hydride ligand. While CpRMo(PMe 3) 3–x(CO) xH (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts formore » the release of H 2 from formic acid, the carbonyl derivatives, CpRMo(CO)3H, are also observed to form dinuclear formate compounds, namely, [Cp RMo(μ-O)(μ-O 2CH)] 2. The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2CH)] 2 and [Cp*Mo(μ-O)(μ-O 2CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO–1) orbitals. The σ 2δ *2 configuration thus corresponds to a formal direct Mo–Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo–Mo bond, whereas a Mo=Mo double bond is required in the absence of lone-pair donation.« less

  12. Dielectric behavior and AC conductivity of Cr doped α-Mn2O3

    NASA Astrophysics Data System (ADS)

    Chandra, Mohit; Yadav, Satish; Singh, K.

    2018-05-01

    The complex dielectric behavior of polycrystalline α-Mn2-xCrxO3 (x = 0.10) has been investigated isothermally at wide frequency range (4Hz-1 MHz) at different temperatures (300-390K). The dielectric spectroscopy results have been discussed in different formulism like dielectric constant, impedance and ac conductivity. The frequency dependent dielectric loss (tanδ) exhibit a clear relaxation behavior in the studied temperature range. The relaxation frequency increases with increasing temperature. These results are fitted using Arrhenius equation which suggest thermally activated process and the activation energy is 0.173±0.0024 eV. The normalized tanδ curves at different temperatures merge as a single master curve which indicate that the relaxation process follow the similar relaxation dynamics in the studied temperature range. Further, the dielectric relaxation follows non-Debye behavior. The impedance results inference that the grain boundary contribution dominate at lower frequency whereas grain contribution appeared at higher frequencies and exhibit strong temperature dependence. The ac conductivity data shows that the ac conductivity increases with increasing temperature which corroborate the semiconducting nature of the studied sample.

  13. Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

    2016-01-01

    Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C-O-H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred.

  14. Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature.

    PubMed

    Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

    2016-01-27

    Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C-O-H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred.

  15. Oxidation precursor dependence of atomic layer deposited Al2O3 films in a-Si:H(i)/Al2O3 surface passivation stacks.

    PubMed

    Xiang, Yuren; Zhou, Chunlan; Jia, Endong; Wang, Wenjing

    2015-01-01

    In order to obtain a good passivation of a silicon surface, more and more stack passivation schemes have been used in high-efficiency silicon solar cell fabrication. In this work, we prepared a-Si:H(i)/Al2O3 stacks on KOH solution-polished n-type solar grade mono-silicon(100) wafers. For the Al2O3 film deposition, both thermal atomic layer deposition (T-ALD) and plasma enhanced atomic layer deposition (PE-ALD) were used. Interface trap density spectra were obtained for Si passivation with a-Si films and a-Si:H(i)/Al2O3 stacks by a non-contact corona C-V technique. After the fabrication of a-Si:H(i)/Al2O3 stacks, the minimum interface trap density was reduced from original 3 × 10(12) to 1 × 10(12) cm(-2) eV(-1), the surface total charge density increased by nearly one order of magnitude for PE-ALD samples and about 0.4 × 10(12) cm(-2) for a T-ALD sample, and the carrier lifetimes increased by a factor of three (from about 10 μs to about 30 μs). Combining these results with an X-ray photoelectron spectroscopy analysis, we discussed the influence of an oxidation precursor for ALD Al2O3 deposition on Al2O3 single layers and a-Si:H(i)/Al2O3 stack surface passivation from field-effect passivation and chemical passivation perspectives. In addition, the influence of the stack fabrication process on the a-Si film structure was also discussed in this study.

  16. Optical characterization of Tm(3+) doped Bi2O3-GeO2-Ga2O3 glasses in absence and presence of BaF2.

    PubMed

    Han, Kexuan; Zhang, Peng; Wang, Shunbin; Guo, Yanyan; Zhou, Dechun; Yu, Fengxia

    2016-08-10

    In this paper, Two new Bi2O3-GeO2-Ga2O3 glasses (one presence of BaF2) doped with 1mol% Tm2O3 were prepared by melt-quenching technique. Differential thermal analysis (DTA), the absorption, Raman, IR spectra and fluorescence spectra were measured. The Judd-Ofelt intensity parameters, emission cross section, absorption cross section, and gain coefficient of Tm(3+) ions were comparatively investigated. After the BaF2 introduced, the glass showed a better thermal stability, lower phonon energy and weaker OH(-) absorption coefficient, meanwhile, a larger ~1.8 μm emission cross section σem (7.56 × 10(-21) cm(2)) and a longer fluorescence lifetime τmea (2.25 ms) corresponding to the Tm(3+): (4)F3 → (3)H6 transition were obtained, which is due to the addition of fluoride in glass could reduce the quenching rate of hydroxyls and raise the cross-relaxation ((3)H6 + (3)H4 → (3)F4 + (3)F4) rate. Our results suggest that the Tm(3+) doped Bi2O3-GeO2-Ga2O3 glass with BaF2 might be potential to the application in efficient ~1.8 μm lasers system.

  17. Optical characterization of Tm3+ doped Bi2O3-GeO2-Ga2O3 glasses in absence and presence of BaF2

    PubMed Central

    Han, Kexuan; Zhang, Peng; Wang, Shunbin; Guo, Yanyan; Zhou, Dechun; Yu, Fengxia

    2016-01-01

    In this paper, Two new Bi2O3-GeO2-Ga2O3 glasses (one presence of BaF2) doped with 1mol% Tm2O3 were prepared by melt-quenching technique. Differential thermal analysis (DTA), the absorption, Raman, IR spectra and fluorescence spectra were measured. The Judd–Ofelt intensity parameters, emission cross section, absorption cross section, and gain coefficient of Tm3+ ions were comparatively investigated. After the BaF2 introduced, the glass showed a better thermal stability, lower phonon energy and weaker OH− absorption coefficient, meanwhile, a larger ~1.8 μm emission cross section σem (7.56 × 10−21 cm2) and a longer fluorescence lifetime τmea (2.25 ms) corresponding to the Tm3+: 4F3 → 3H6 transition were obtained, which is due to the addition of fluoride in glass could reduce the quenching rate of hydroxyls and raise the cross-relaxation (3H6 + 3H4 → 3F4 + 3F4) rate. Our results suggest that the Tm3+ doped Bi2O3-GeO2-Ga2O3 glass with BaF2 might be potential to the application in efficient ~1.8 μm lasers system. PMID:27506152

  18. Synthesis, DFT calculations of structure, vibrational and thermal decomposition studies of the metal complex Pb[Mn(C3H2O4)2(H2O)2].

    PubMed

    Gil, Diego M; Carbonio, Raúl E; Gómez, María Inés

    2015-04-15

    The metallo-organic complex Pb[Mn(C3H2O4)2(H2O)2] was synthesized and characterized by IR and Raman spectroscopy and powder X-ray diffraction methods. The cell parameters for the complex were determined from powder X-ray diffraction using the autoindexing program TREOR, and refined by the Le Bail method with the Fullprof program. A hexagonal unit cell was determined with a=b=13.8366(7)Å, c=9.1454(1)Å, γ=120°. The DFT calculated geometry of the complex anion [Mn(C3H2O4)2(H2O)2](2-) is very close to the experimental data reported for similar systems. The IR and Raman spectra and the thermal analysis of the complex indicate that only one type of water molecules is present in the structure. The thermal decomposition of Pb[Mn(C3H2O4)2(H2O)2] at 700 °C in air produces PbO and Pb2MnO4 as final products. The crystal structure of the mixed oxide is very similar to that reported for Pb3O4. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. [{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20]36-: a molecular quantum spin icosidodecahedron.

    PubMed

    Botar, Bogdan; Kögerler, Paul; Hill, Craig L

    2005-07-07

    Self-assembly of aqueous solutions of molybdate and vanadate under reducing, mildly acidic conditions results in a polyoxomolybdate-based {Mo72V30} cluster compound Na8K16(VO)(H2O)5[K10 subset{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20].150H2O, 1, a quantum spin-based Keplerate structure.

  20. First identification and thermodynamic characterization of the ternary U(VI) species, UO2(O2)(CO3)2(4-), in UO2-H2O2-K2CO3 solutions.

    PubMed

    Goff, George S; Brodnax, Lia F; Cisneros, Michael R; Peper, Shane M; Field, Stephanie E; Scott, Brian L; Runde, Wolfgang H

    2008-03-17

    In alkaline carbonate solutions, hydrogen peroxide can selectively replace one of the carbonate ligands in UO2(CO3)3(4-) to form the ternary mixed U(VI) peroxo-carbonato species UO2(O2)(CO3)2(4-). Orange rectangular plates of K4[UO2(CO3)2(O2)].H2O were isolated and characterized by single crystal X-ray diffraction studies. Crystallographic data: monoclinic, space group P2(1)/ n, a = 6.9670(14) A, b = 9.2158(10) A, c = 18.052(4) A, Z = 4. Spectrophotometric titrations with H 2O 2 were performed in 0.5 M K 2CO 3, with UO2(O2)(CO3)2(4-) concentrations ranging from 0.1 to 0.55 mM. The molar absorptivities (M(-1) cm(-1)) for UO2(CO3)3(4-) and UO2(O2)(CO3)2(4-) were determined to be 23.3 +/- 0.3 at 448.5 nm and 1022.7 +/- 19.0 at 347.5 nm, respectively. Stoichiometric analyses coupled with spectroscopic comparisons between solution and solid state indicate that the stable solution species is UO2(O2)(CO3)2(4-), which has an apparent formation constant of log K' = 4.70 +/- 0.02 relative to the tris-carbonato complex.

  1. Reactions of the linear tetranuclear complex Ru sub 4 (CO) sub 10 (CH sub 3 C double bond C(H)C(H) double bond N-i-Pr) sub 2 with oxidizing reagents. Syntheses of halide-bridged (Ru(CO) sub 2 X(CH sub 3 C double bond C(H)C(H) double bond N-i-Pr)) sub 2 and fac-Ru(CO) sub 3 X(CH sub 3 C double bond C(H)C(H) double bond N-i-Pr)

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

    Mul, W.P.; Elsevier, C.J.; van Leijen, M.

    1991-01-01

    The linear tetranuclear complex Ru{sub 4}(CO){sub 10}(CH{sub 3}C{double bond}C(H)C(H){double bond}N-i-Pr){sub 2} (1), containing two {eta}{sup 5}-azaruthenacyclopentadienyl systems, reacts with oxidizing reagents (I{sub 2}, Br{sub 2}, NBS, CCl{sub 4}) at elevated temperatures (40-90C) in heptane or benzene to give the new dimeric halide-bridged organoruthenium(II) complexes (Ru(CO){sub 2}X(CH{sub 3}C{double bond}C(H)C(H){double bond}N-i-Pr)){sub 2} (X = I (3a), X = Br (3b), Cl (3c); yield 30-80%) together with (Ru(CO){sub 3}X{sub 2}){sub 2}. The reactions of 1 with CX{sub 4} (X = I, Br, Cl) are accelerated by CO, probably because Ru{sub 4}(CO){sub 12}(CH{sub 3}C{double bond}C(H)C(H){double bond}N-i-Pr){sub 2} (5), which contains two unbridged metal-metal bonds,more » is formed prior to oxidation. The halide-bridged dimers 3a-c are obtained as mixtures of four isomers, the configurations of which are discussed. Splitting of the halide bridges takes place when a solution of 3a-c is saturated with CO, whereby mononuclear fac-Ru(CO){sub 3}X(CH{sub 3}C{double bond}C(H)C(H){double bond}N-i-Pr) (4a-c) is obtained. This process is reversible; ie., passing a stream of nitrogen through a solution of 4a-c or removal of the solvent under vacuum causes the reverse reaction with reformation of 3a-c. Compounds 3a-c and 4a-c have been characterized by IR (3, 4), FD mass (3), {sup 1}H (3, 4), and {sup 13}C{l brace}H{r brace} NMR (4) spectroscopy and satisfactory elemental analyses have been obtained for 3a-c. Compounds 3 and 4 are suitable precursors for the preparation of new homo- and heteronuclear transition-metal complexes.« less

  2. Synthesis and characterization of two novel inorganic/organic hybrid materials based on polyoxomolybdate clusters: (C5H5N5)2(C5H6N5)4[(HAsO4)2Mo6O18]·11H2O and Na2(Himi)3[SeMo6O21(CH3COO)3]·6H2O

    NASA Astrophysics Data System (ADS)

    Ayed, Meriem; Mestiri, Imen; Ayed, Brahim; Haddad, Amor

    2017-01-01

    Two new organic-inorganic hybrid compound, (C5H5N5)2(C5H6N5)4[(HAsO4)2Mo6O18]·11H2O (I) and Na2(Himi)3[SeMo6O21(CH3COO)3]·6H2O (II) were synthesized and structurally characterized by scanning electron microscopy (SEM), elemental analyses, FTIR, UV spectroscopy, thermal stability analysis, XRD and single crystal X-ray diffraction. Crystal data: (I) triclinic system, space group P-1, a = 11,217 (9) Å, b = 11,637 (8) Å, c = 14,919 (8) Å, α = 70,90 (5)°, β = 70,83 (2)°, γ = 62,00(1)° and Z = 1; (II) triclinic system, space group P-1, a = 10.6740(1) Å, b = 10.6740(1) Å, c = 20.0570(1) Å, α = 76.285(1)°, β = 82.198(2)°, γ = 87.075(1)°, Z = 1. The crystal structure of (I) can be described by infinite polyanions [(HAsO4)2Mo6O18]4- organized with water molecules in layers parallel to the c-direction; adjacent layers are further joined up by hydrogen bonding interactions with organic groups which were associated in chains spreading along the b-direction. The structure of (II) consists of functionalized selenomolybdate clusters [SeMo6O21(CH3COO)3]5-, protonated imidazole cations, sodium ions and lattice water molecules, which are held together to generate a three-dimensional supramolecular network via hydrogen-bonding interaction. Furthermore, the electrochemical properties of these compounds have been studied.

  3. Crystal chemistry of hydrous phases in the Al2O3-Fe2O3-H2O system: implications for water cycle in the deep lower mantle

    NASA Astrophysics Data System (ADS)

    Zhang, L.

    2016-12-01

    Hydrous minerals play an important role in the transportation and storage of water in the Earth's interior. Recently a pyrite-structured iron oxide (FeO2) (P-phase) was found stable at 76 GPa and 1800 K [1] and this discovery has brought new insights into the H2-O2 cycles in the deep mantle. In this study, we perform in situ synchrotron X-ray experiments in the Al2O3-Fe2O3-H2O system in a laser-heated diamond anvil cell (DAC) at P-T conditions in the deep lower mantle. The new results added more complexity to the H2-O2/H2O cycles in the deep lower mantle. The symmetry and unit-cell parameters of each phase in the run products were determined using the multigrain approach [2]. On the other hand, the d-H solid solution AlOOH-MgSiO2(OH)2 is the stable hydrous phase coexisting with bridgmanite or post-perovskite under equilibrium P-T conditions to the deepest lower mantle [3]. The detailed crystal chemistry of the newly found hydrous phases and its relations to the d-H phase have been investigated using both first-principles calculations and experiments, providing new understanding to the hydration mechanism and water storage in the deep mantle. It is worth mentioning that recent development in high pressure multigrain method has realized separation of each individual phase in a multiphase assemblage and even allowed in situ crystal structure determination of a minor phase in the assemblage contained in a DAC [4]. [1] Q. Hu, D. Y. Kim, W. Yang, L. Yang, Y. Meng, L. Zhang, and H. K. Mao, Nature 534, 241 (2016). [2] H. O. Sørensen et al., Zeitschrift für Kristallographie 227, 63 (2012). [3] I. Ohira, E. Ohtani, T. Sakai, M. Miyahara, N. Hirao, Y. Ohishi, and M. Nishijima, Earth and Planetary Science Letters 401, 12 (2014). [4] L. Zhang, D. Popov, Y. Meng, J. Wang, C. Ji, B. Li, and H.-k. Mao, American Mineralogist 101, 231 (2016).

  4. Aqueous organometallic chemistry. 2. {sup 1}H NMR spectroscopic, synthetic, and structural study of the chemo- and diastereoselective reactions of [Cp{sup *}Rh(H{sub 2}O){sub 3}]{sup 2+} with nitrogen ligands as a function of pH

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

    Ogo, Seiji; Chen, H.; Fish, R.H.

    The reactions of a new Cp{sup *}Rh aqua synthon, [Cp{sup *}Rh(H{sub 2}O){sub 3}]{sup 2+} (1), at acidic pH values (2-6) with aniline (2), pyridine (3), and L-phenylalanine (4) have provided interesting chemo- and diastereoselectivities as studied by {sup 1}H NMR, FAB/MS, and single-crystal X-ray crystallography. The reaction of 2 and aqua complex 1, at pH values from 4 to 6, quantitatively provided [Cp{sup *}Rh({eta}{sup 6}-aniline)]{sup 2+} (5); the structure of 5 was unequivocally determined by a single-crystal X-ray analysis, which also showed an approximate 25% {eta}{sup 5} component. Compound 3 reacted with 1, at pH 2-6, to selectively provide [Cp{supmore » *}Rh({eta}{sup 1}-pyridine){sub n} (H{sub 2}O){sub 3-n}]{sup 2+} (n = 1-3) complexes 6a-c as a function of pH. Surprisingly, complex 1 reacted with 4, from pH 4 to 6, to provide only one diastereomer of the known cyclic trimer [(Cp{sup *}Rh)({mu}-{eta}{sup 1}-(OCO):{eta}{sup 2}-(N,OCO)-L-phe nylalanine)]{sub 3}{sup 3+} (7; S{sub C},S{sub C},S{sub C},S{sub Rh},S{sub Rh},S{sub Rh},) an example of a one-step, highly diastereoselective reaction in H{sub 2}O. 8 refs., 4 figs., 2 tabs.« less

  5. Degradation of nitrobenzene wastewater in an acidic environment by Ti(IV)/H2O2/O3 in a rotating packed bed.

    PubMed

    Yang, Peizhen; Luo, Shuai; Liu, Youzhi; Jiao, Weizhou

    2018-06-23

    The rotating packed bed (RPB) as a continuous flow reactor performs very well in degradation of nitrobenzene wastewater. In this study, acidic nitrobenzene wastewater was degraded using ozone (O 3 ) combined with hydrogen peroxide and titanium ions (Ti(IV)/H 2 O 2 /O 3 ) or using only H 2 O 2 /O 3 in a RPB. The degradation efficiency of nitrobenzene by Ti(IV)/H 2 O 2 /O 3 is roughly 16.84% higher than that by H 2 O 2 /O 3 , and it reaches as high as 94.64% in 30 min at a H 2 O 2 /O 3 molar ratio of 0.48. It is also found that the degradation efficiency of nitrobenzene is significantly affected by the high gravity factor, H 2 O 2 /O 3 molar ratio, and Ti(IV) concentration, and it reaches a maximum at a high gravity factor of 40, a Ti(IV) concentration of 0.50 mmol/L, a pH of 4.0, a H 2 O 2 /O 3 molar ratio of 0.48, a liquid flow rate of 120 L/h, and an initial nitrobenzene concentration of 1.22 mmol/L. Both direct ozonation and indirect ozonation are involved in the reaction of O 3 with organic pollutants. The indirect ozonation due to the addition of different amounts of tert-butanol (·OH scavenger) in the system accounts for 84.31% of the degradation efficiency of nitrobenzene, indicating that the nitrobenzene is dominantly oxidized by ·OH generated in the RPB-Ti(IV)/H 2 O 2 /O 3 process. Furthermore, the possible oxidative degradation mechanisms are also proposed to better understand the role of RPB in the removal of pollutants. Graphical abstract ᅟ.

  6. Cross sections for Scattering and Mobility of OH- and H3 O+ ions in H2 O

    NASA Astrophysics Data System (ADS)

    Petrovic, Zoran; Stojanovic, Vladimir; Maric, Dragana; Jovanovic, Jasmina

    2016-05-01

    Modelling of plasmas in liquids and in biological and medical applications requires data for scattering of all charged and energetic particles in water vapour. We present swarm parameters for OH- and H3 O+, as representatives of principal negative and positive ions at low pressures in an attempt to provide the data that are not yet available. We applied Denpoh-Nanbu procedure to calculate cross section sets for collisions of OH- and H3 O+ ions with H2 O molecule. Swarm parameters for OH- and H3 O+ ions in H2 O are calculated by using a well tested Monte Carlo code for a range of E / N(E -electric field, N-gas density) at temperature T = 295 K, in the low pressure limit. Non-conservative processes were shown to strongly influence the transport properties even for OH- ions above the average energy of 0.2 eV(E / N >200 Td). The data are valid for low pressure water vapour or small amounts in mixtures. They will provide a basis for calculating properties of ion-water molecule clusters that are most commonly found at higher pressures and for modelling of discharges in liquids. Acknowledgment to Ministry of Education, Science and Technology of Serbia.

  7. Evaluation of the solubility constants of the hydrated solid phases in the H2O-Al2O3-SO3 ternary system

    NASA Astrophysics Data System (ADS)

    Teyssier, A.; Lagneau, V.; Schmitt, J. M.; Counioux, J. J.; Goutaudier, C.

    2017-04-01

    During the acid processing of aluminosilicate ores, the precipitation of a solid phase principally consisting of hydrated aluminium hydroxysulfates may be observed. The experimental study of the H2O-Al2O3-SO3 ternary system at 25 ∘C and 101 kPa enabled to describe the solid-liquid equilibra and to identify the nature, the composition and the solubility of the solid phases which may form during the acid leaching. To predict the appearance of these aluminium hydroxysulfates in more complex systems, their solubility constants were calculated by modelling the experimental solubility results, using a geochemical reaction modelling software, CHESS. A model for non-ideality correction, based on the B-dot equation, was used as it was suitable for the considered ion concentration range. The solubility constants of three out of four solid phases were calculated: 104.08 for jurbanite (Al(SO4)(OH).5H2O), 1028.09 for the solid T (Al8(SO4)5(OH)14.34H2O) and 1027.28 for the solid V (Al10(SO4)3(OH)24.20H2O). However the activity correction model was not suitable to determine the solubility constant of alunogen (Al2(SO4)3.15.8H2O), as the ion concentrations of the mixtures were too high and beyond the allowable limits of the model. Another ionic activity correction model, based on the Pitzer equation for example, must be applied to calculate the solubility constant of alunogen.

  8. Structural, electronic properties and stability of metatitanic acid (H 2TiO 3) nanotubes

    NASA Astrophysics Data System (ADS)

    Enyashin, A. N.; Denisova, T. A.; Ivanovskii, A. L.

    2009-12-01

    Quite recently, metatitanic acid (H 2TiO 3) has been successfully prepared, which extended the family of known titanic acids H 2Ti nO 2n+1 ( n = 2, 3 and 4). Here the atomic models for nanotubes (NTs) of metatitanic acid are designed and their cohesive and electronic properties are considered depending on their chirality and radii by means of density-functional theory-tight-binding (DFTB) method. Our main findings are that the proposed H 2TiO 3 tubes are stable and that all these NTs will be the insulators (independently from their chirality and the diameters) with forbidden gaps at about ˜4.6 eV. We have found also that aforementioned properties of predicted H 2TiO 3 NTs are very similar with those of recently prepared fabricated nanotubes of polytitanic acids; thus, it is possible to expect that the proposed H 2TiO 3 tubular materials may be fabricated.

  9. Thermoluminescence and optically stimulated luminescence properties of Dy3+-doped CaO-Al2O3-B2O3-based glasses

    NASA Astrophysics Data System (ADS)

    Yahaba, T.; Fujimoto, Y.; Yanagida, T.; Koshimizu, M.; Tanaka, H.; Saeki, K.; Asai, K.

    2017-02-01

    We developed Dy3+-doped CaO-Al2O3-B2O3 based glasses with Dy concentrations of 0.5, 1.0, and 2.0 mol% using a melt-quenching technique. The as-synthesized glasses were applicable as materials exhibiting thermoluminescence (TL) and optically stimulated luminescence (OSL). The optical and radiation response properties of the glasses were characterized. In the photoluminescence (PL) spectra, two emission bands due to the 4F9/2 → 6H15/2 and 4F9/2 → 6H13/2 transitions of Dy3+ were observed at 480 and 580 nm. In the OSL spectra, the emission band due to the 4F9/2 → 6H15/2 transition of Dy3+ was observed. Excellent TL and OSL responses were observed for dose ranges of 0.1-90 Gy. In addition, TL fading behavior was better than that of OSL in term of the long-time storage. These results indicate that the Dy3+-doped CaO-Al2O3-B2O3-based glasses are applicable as TL materials.

  10. The crystal structure of galgenbergite-(Ce), CaCe2(CO3)4•H2O

    NASA Astrophysics Data System (ADS)

    Walter, Franz; Bojar, Hans-Peter; Hollerer, Christine E.; Mereiter, Kurt

    2013-04-01

    Galgenbergite-(Ce) from the type locality, the railroad tunnel Galgenberg between Leoben and St. Michael, Styria, Austria, was investigated. There it occurs in small fissures of an albite-chlorite schist as very thin tabular crystals building rosette-shaped aggregates associated with siderite, ancylite-(Ce), pyrite and calcite. Electron microprobe analyses gave CaO 9.49, Ce2O3 28.95, La2O3 11.70, Nd2O3 11.86, Pr2O3 3.48, CO2 30.00, H2O 3.07, total 98.55 wt.%. CO2 and H2O calculated by stoichiometry. The empirical formula (based on Ca + REE ∑3.0) is C{{a}_{1.00 }}{{( {C{{e}_{1.04 }}L{{a}_{0.42 }}N{{d}_{0.42 }}P{{r}_{0.12 }}} )}_{2.00 }}{{( {C{{O}_3}} )}_4}\\cdot {{H}_2}O , and the simplified formula is CaC{{e}_2}{{( {C{{O}_3}} )}_4}\\cdot {{H}_2}O . According to X-ray single crystal diffraction galgenbergite-(Ce) is triclinic, space group Poverline{1},a=6.3916(5) , b = 6.4005(4), c = 12.3898(9) Å, α = 100.884(4), β = 96.525(4), γ = 100.492(4)°, V = 483.64(6) Å3, Z = 2. The eight strongest lines in the powder X-ray diffraction pattern are [ d calc in Å/( I)/ hkl]: 5.052/(100)/011; 3.011/(70)/0-22; 3.006/(66)/004; 5.899/(59)/-101; 3.900/(51)/1-12; 3.125/(46)/-201; 2.526/(42)/022; 4.694/(38)/-102. The infrared absorption spectrum reveals H2O (OH-stretching mode at 3,489 cm-1, HOH bending mode at 1,607 cm-1) and indicates the presence of distinctly non-equivalent CO3-groups by double and quadruple peaks of their ν1, ν2, ν3 and ν4 modes. The crystal structure of galgenbergite-(Ce) was refined with X-ray single crystal data to R1 = 0.019 for 2,448 unique reflections ( I > 2 σ( I)) and 193 parameters. The three cation sites of the structure Ca(1), Ce(2) and Ce(3) have a modest mixed site occupation by Ca and small amount of REE (Ce, La, Pr, Nd) and vice versa. The structure is based on double layers parallel to (001), which are composed of Ca(1)Ce(2)(CO3)2 single layers with an ordered chessboard like arrangement of Ca and Ce, and with a roof tile

  11. DFT study of uranyl peroxo complexes with H2O, F-, OH-, CO3(2-), and NO3(-).

    PubMed

    Odoh, Samuel O; Schreckenbach, Georg

    2013-05-06

    The structural and electronic properties of monoperoxo and diperoxo uranyl complexes with aquo, fluoride, hydroxo, carbonate, and nitrate ligands have been studied using scalar relativistic density functional theory (DFT). Only the complexes in which the peroxo ligands are coordinated to the uranyl moiety in a bidentate mode were considered. The calculated binding energies confirm that the affinity of the peroxo ligand for the uranyl group far exceeds that of the F(-), OH(-), CO3(2-), NO3(-), and H2O ligands. The formation of the monoperoxo complexes from UO2(H2O)5(2+) and HO2(-) were found to be exothermic in solution. In contrast, the formation of the monouranyl-diperoxo, UO2(O2)2X2(4-) or UO2(O2)2X(4-/3-) (where X is any of F(-), OH(-), CO3(2-), or NO3(-)), complexes were all found to be endothermic in aqueous solution. This suggests that the monoperoxo species are the terminal monouranyl peroxo complexes in solution, in agreement with recent experimental work. Overall, we find that the properties of the uranyl-peroxo complexes conform to well-known trends: the coordination of the peroxo ligand weakens the U-O(yl) bonds, stabilizes the σ(d) orbitals and causes a mixing between the uranyl π- and peroxo σ- and π-orbitals. The weakening of the U-O(yl) bonds upon peroxide coordination results in uranyl stretching vibrational frequencies that are much lower than those obtained after the coordination of carbonato or hydroxo ligands.

  12. Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature

    PubMed Central

    Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

    2016-01-01

    Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C–O–H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred. PMID:26813580

  13. Fixation of CO2 in bi-layered coordination networks of zinc tetra(4-carboxyphenyl)porphyrin with multi-component [Pr2Na3(NO3)(H2O)3] connectors.

    PubMed

    Nandi, Goutam; Goldberg, Israel

    2014-11-14

    CO2 is fixed in a rare μ2-η bridging mode by bi-layered coordination networks of ZnTCPP tessellated along the four equatorial directions by [Pr2Na3(NO3)(H2O)3](8+) connecting clusters in a 2 : 1 ratio (1), but not in the isomorphous free-base porphyrin analogue [(TCPPH2)2(Pr2Na3(NO3)(H2O)3)]n (2), revealing the crucial role of the zinc metal in this process.

  14. A First Principles Study of H2 Adsorption on LaNiO3(001) Surfaces

    PubMed Central

    Pan, Changchang; Chen, Yuhong; Wu, Na; Zhang, Meiling; Yuan, Lihua; Zhang, Cairong

    2017-01-01

    The adsorption of H2 on LaNiO3 was investigated using density functional theory (DFT) calculations. The adsorption sites, adsorption energy, and electronic structure of LaNiO3(001)/H2 systems were calculated and indicated through the calculated surface energy that the (001) surface was the most stable surface. By looking at optimized structure, adsorption energy and dissociation energy, we found that there were three types of adsorption on the surface. First, H2 molecules completely dissociate and then tend to bind with the O atoms, forming two –OH bonds. Second, H2 molecules partially dissociate with the H atoms bonding to the same O atom to form one H2O molecule. These two types are chemical adsorption modes; however, the physical adsorption of H2 molecules can also occur. When analyzing the electron structure of the H2O molecule formed by the partial dissociation of the H2 molecule and the surface O atom, we found that the interaction between H2O and the (001) surface was weaker, thus, H2O was easier to separate from the surface to create an O vacancy. On the (001) surface, a supercell was constructed to accurately study the most stable adsorption site. The results from analyses of the charge population; electron localization function; and density of the states indicated that the dissociated H and O atoms form a typical covalent bond and that the interaction between the H2 molecule and surface is mainly due to the overlap-hybridization among the H 1s, O 2s, and O 2p states. Therefore, the conductivity of LaNiO3(001)/H2 is stronger after adsorption and furthermore, the conductivity of the LaNiO3 surface is better than that of the LaFeO3 surface. PMID:28772396

  15. Reflected shock tube studies of high-temperature rate constants for OH + CH4 --> CH3 + H2O and CH3 + NO2 --> CH3O + NO.

    PubMed

    Srinivasan, N K; Su, M-C; Sutherland, J W; Michael, J V

    2005-03-10

    The reflected shock tube technique with multipass absorption spectrometric detection of OH radicals at 308 nm has been used to study the reactions OH + CH(4) --> CH(3) + H(2)O and CH(3) + NO(2) --> CH(3)O + NO. Over the temperature range 840-2025 K, the rate constants for the first reaction can be represented by the Arrhenius expression k = (9.52 +/- 1.62) x 10(-11) exp[(-4134 +/- 222 K)/T] cm(3) molecule(-1) s(-1). Since this reaction is important in both combustion and atmospheric chemistry, there have been many prior investigations with a variety of techniques. The present results extend the temperature range by 500 K and have been combined with the most accurate earlier studies to derive an evaluation over the extended temperature range 195-2025 K. A three-parameter expression describes the rate behavior over this temperature range, k = (1.66 x 10(-18))T(2.182) exp[(-1231 K)/T] cm(3) molecule(-1) s(-1). Previous theoretical studies are discussed, and the present evaluation is compared to earlier theoretical estimates. Since CH(3) radicals are a product of the reaction and could cause secondary perturbations in rate constant determinations, the second reaction was studied by OH radical production from the fast reactions CH(3)O --> CH(2)O + H and H + NO(2) --> OH + NO. The measured rate constant is 2.26 x 10(-11) cm(3) molecule(-1) s(-1) and is not dependent on temperature from 233 to 1700 K within experimental error.

  16. Structural basis for recognition of H3K56-acetylated histone H3-H4 by the chaperone Rtt106

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

    Su, Dan; Hu, Qi; Li, Qing

    2013-04-08

    Dynamic variations in the structure of chromatin influence virtually all DNA-related processes in eukaryotes and are controlled in part by post-translational modifications of histones. One such modification, the acetylation of lysine 56 (H3K56ac) in the amino-terminal α-helix (αN) of histone H3, has been implicated in the regulation of nucleosome assembly during DNA replication and repair, and nucleosome disassembly during gene transcription. In Saccharomyces cerevisiae, the histone chaperone Rtt106 contributes to the deposition of newly synthesized H3K56ac-carrying H3-H4 complex on replicating DNA, but it is unclear how Rtt106 binds H3-H4 and specifically recognizes H3K56ac as there is no apparent acetylated lysinemore » reader domain in Rtt106. Here, we show that two domains of Rtt106 are involved in a combinatorial recognition of H3-H4. An N-terminal domain homodimerizes and interacts with H3-H4 independently of acetylation while a double pleckstrin-homology (PH) domain binds the K56-containing region of H3. Affinity is markedly enhanced upon acetylation of K56, an effect that is probably due to increased conformational entropy of the αN helix of H3. Our data support a mode of interaction where the N-terminal homodimeric domain of Rtt106 intercalates between the two H3-H4 components of the (H3-H4) 2 tetramer while two double PH domains in the Rtt106 dimer interact with each of the two H3K56ac sites in (H3-H4) 2. We show that the Rtt106-(H3-H4) 2 interaction is important for gene silencing and the DNA damage response.« less

  17. The diphtheria toxin transmembrane domain as a pH sensitive membrane anchor for human interleukin-2 and murine interleukin-3.

    PubMed

    Liger, D; Nizard, P; Gaillard, C; vanderSpek, J C; Murphy, J R; Pitard, B; Gillet, D

    1998-11-01

    We have constructed two fusion proteins T-hIL-2 and T-mIL-3 in which human interleukin-2 (hIL-2) or murine interleukin-3 (mIL-3) are fused to the C-terminus of the diphtheria toxin transmembrane domain (T domain). Two additional fusion proteins, T-(Gly4-Ser)2-hIL-2 and T-(Gly4-Ser)2-mIL-3, were derived by introduction of the (Gly4-Ser)2 spacer between the T domain and cytokine components. Recognition of the hIL-2 receptor or the mIL-3 receptor by the corresponding recombinant proteins was demonstrated by their capacity to stimulate cytokine-dependent cell lines. All proteins retained the capacity of the T domain to insert into phospholipid membranes at acidic pH. Finally, anchoring of both cytokines to the membrane of lipid vesicles or living cells was assessed by specific antibody recognition. Our results show that the T domain fused to the N-terminus of a given protein can function as a pH sensitive membrane anchor for that protein.

  18. Ab-initio study of the energetics and thermodynamics of the reaction CH3H + O( 3P) → CF3HO → CF3 + OH

    NASA Astrophysics Data System (ADS)

    Kreye, W. C.

    1996-07-01

    Ab-initio computations at 298.15 K were made of the activation quantities ΔH ‡, ΔS ‡, and ΔG ‡ and of the reaction quantities ΔHr and ΔSr for CF3H + O( 3P) → CF3HO → .CF3.OH. CF 3HO is the transition state (TS). GAUSSIAN92 was used and energies computed at a slightly modified Gaussian-2 level. Two potential surfaces for the TS had symmetries 3A' and 3A″. The two rate constants included a semi-classical, quantum-mechanical-tunneling transmission coefficient. The ab-initio ΔH ‡and ΔH r values were in excellent agreement (± 1 kcal/mol) with experiment; but the ΔS ‡, ΔG ‡, and ΔS r values yielded somewhat poorer agreement. Experimental and ab-initio structures were in excellent agreement.

  19. High pressure Raman spectroscopy of H2O-CH3OH mixtures.

    PubMed

    Hsieh, Wen-Pin; Chien, Yu-Hsiang

    2015-02-23

    Complex intra-molecular interactions and the hydrogen-bonding network in H2O-volatile mixtures play critical roles in many dynamics processes in physical chemistry, biology, and Earth and planetary sciences. We used high pressure Raman spectroscopy to study the pressure evolution of vibrational frequencies and bonding behavior in H2O-CH3OH mixtures. We found that the presence of low CH3OH content in H2O increases the transition pressure where water crystallizes to ice VI, but does not significantly change the pressure where ice VI transforms to ice VII. Furthermore, the stiffening rates of C-H stretching frequencies dω/dP in CH3OH significantly decrease upon the crystallization of water, and the softening rates of the O-H stretching frequencies of ice VII are suppressed over a narrow pressure range, after which the frequencies of these modes shift with pressure in ways similar to pure CH3OH and ice VII, respectively. Such complex pressure evolution of Raman frequencies along with pronounced variations in Raman intensities of CH3OH within the sample, and the hysteresis of the water-ice VI phase transition suggest pressure-induced segregation of low content CH3OH from ice VII. These findings indicate the significant influence of volatiles on the crystallization of sub-surface ocean and thermal evolution within large icy planets and satellites.

  20. One-pot chemoselective synthesis of novel pyrrole-substituted pyrido [2,3-d]pyrimidines using [γ-Fe2O3@HAp-SO3H] as an efficient nanocatalyst

    NASA Astrophysics Data System (ADS)

    Jahanshahi, Parivash; Mamaghani, Manouchehr; Haghbin, Fereshteh; Nia, Roghayeh Hossein; Rassa, Mehdi

    2018-03-01

    Novel (1-methyl-1H-pyrrol-2-yl)-[2,3-d]pyrimidine derivatives were synthesized chemoselectively in good to high yields (81-90%) and short reaction times (7-14 min) by hydroxyapatite-encapsulated-γ-Fe2O3 supported sulfonic acid ([γ-Fe2O3@HAp-SO3H]) catalyzed condensation of 3-(1-methyl-1H-pyrrol-2-yl)-3-oxopropanenitrile, 6-amino-2-(alkylthio)pyrimidin-4(3H)-one and various aromatic aldehydes. The easy work-up of the products, rapidity, high efficiency and recyclability of the catalyst are advantages of this protocol. The antibacterial activity of the newly synthesized products was investigated. Some of the products showed encouraging activity.

  1. Enhancement of a-Si:H solar cell efficiency by Y2O3 : Yb3+, Er3+ near infrared spectral upconverter

    NASA Astrophysics Data System (ADS)

    Markose, Kurias K.; Anjana, R.; Subha, P. P.; Antony, Aldrin; Jayaraj, M. K.

    2016-09-01

    The optical properties of Yb3+/Er3+ doped Y2O3 upconversion phosphor and the enhancement of efficiency of a-Si:H solar cell on incorporation of upconverter are investigated. The Y2O3 host material has high corrosion resistance, thermal stability, chemical stability, low toxicity and relatively low phonon energy (≈ 500 cm-1). Y2O3:Yb3+ (x %): Er3+ (y %) upconversion nanophosphors with different dopant concentrations were synthesized via simple hydrothermal method followed by a heat treatment at 1200°C for 12 hrs. Highly crystalline, quasi-spherical, body centered cubic Y2O3 structure was obtained. The structure, phase and morphology of the nanocrystals were determined using x-ray diffraction and SEM. Following pumping at 980 nm two dominant emission bands were observed at about 550 nm(green) and 660 nm(red), corresponding to 2H11/2, 4S3/2 -> 4I15/2 and 4F9/2 -> 4I15/2 transitions respectively. The dependence of emission intensity on pump power shows that the mechanism involved is two photon absorption. The upconversion phosphor along with a binder is coupled behind the a-Si:H solar cell which absorbs transmitted sub-band-gap photons and emits back the upconverted visible light which can be absorbed by the solar cell. Under suitable intensity of illumination the solar cell short circuit current is found to be increased on adding the upconversion layer.

  2. Siudaite, Na8(Mn2+ 2Na)Ca6Fe3+ 3Zr3NbSi25O74(OH)2Cl·5H2O: a new eudialyte-group mineral from the Khibiny alkaline massif, Kola Peninsula

    NASA Astrophysics Data System (ADS)

    Chukanov, Nikita V.; Rastsvetaeva, Ramiza K.; Kruszewski, Łukasz; Aksenov, Sergey M.; Rusakov, Vyacheslav S.; Britvin, Sergey N.; Vozchikova, Svetlana A.

    2018-03-01

    The new eudialyte-group mineral siudaite, ideally Na8(Mn2+ 2Na)Ca6Fe3+ 3Zr3NbSi25O74(OH)2Cl·5H2O, was discovered in a peralkaline pegmatite situated at the Eveslogchorr Mt., Khibiny alkaline massif, Kola Peninsula, Russia. The associated minerals are aegirine, albite, microcline, nepheline, astrophyllite, and loparite-(Ce). Siudaite forms yellow to brownish-yellow equant anhedral grains up to 1.5 cm across. Its lustre is vitreous, and the streak is white. Cleavage is none observed. The Mohs' hardness is 4½. Density measured by hydrostatic weighing is 2.96(1) g/cm3. Density calculated using the empirical formula is equal to 2.973 g/cm3. Siudaite is nonpleochroic, optically uniaxial, negative, with ω = 1.635(1) and ɛ = 1.626(1) (λ = 589 nm). The IR spectrum is given. The chemical composition of siudaite is (wt%; electron microprobe, H2O determined by HCN analysis): Na2O 8.40, K2O 0.62, CaO 9.81, La2O3 1.03, Ce2O3 1.62, Pr2O3 0.21, Nd2O3 0.29, MnO 6.45, Fe2O3 4.51. TiO2 0.54, ZrO2 11.67, HfO2 0.29, Nb2O5 2.76, SiO2 47.20, Cl 0.54, H2O 3.5, -O = Cl - 0.12, total 99.32. According to Mössbauer spectroscopy data, all iron is trivalent. The empirical formula (based on 24.5 Si atoms pfu, in accordance with structural data) is [Na7.57(H2O)1.43]Σ9(Mn1.11Na0.88Ce0.31La0.20Nd0.05Pr0.04K0.41)Σ3(H2O)1.8(Ca5.46Mn0.54)Σ6(Fe3+ 1.76Mn2+ 1.19)Σ2.95Nb0.65(Ti0.20Si0.50)Σ0.71(Zr2.95Hf0.04Ti0.01)Σ3Si24.00Cl0.47O70(OH)2Cl0.47·1.82H2O. The crystal structure was determined using single-crystal X-ray diffraction data. The new mineral is trigonal, space group R3m, with a = 14.1885(26) Å, c = 29.831(7) Å, V = 5200.8(23) Å3 and Z = 3. Siudaite is chemically related to georgbarsanovite and is its analogue with Fe3+-dominant M2 site. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 6.38 (60) (-114), 4.29 (55) (-225), 3.389 (47) (131), 3.191 (63) (-228). 2.963 (100) (4-15), 2.843 (99) (-444), 2.577 (49) (3-39). Siudaite is named after the Polish

  3. Cesium and strontium ion exchange on the framework titanium silicate M2Ti2O3SiO4.nH2O (M = H, Na).

    PubMed

    Solbrå, S; Allison, N; Waite, S; Mikhalovsky, S V; Bortun, A I; Bortun, L N; Clearfield, A

    2001-02-01

    The ion exchange properties of the titanium silicate, M2Ti2O3SiO4.nH2O (M = H, Na), toward stable and radioactive 137Cs+ and 89Sr2+, have been examined. By studying the cesium and strontium uptake in the presence of NaNO3, CaCl2, NaOH, and HNO3 (in the range of 0.01-6 M) the sodium titanium silicate was found to be an efficient Cs+ ion exchanger in acid, neutral, and alkaline media and an efficient Sr2+ ion exchanger in neutral and alkaline media, which makes it promising for treatment of contaminated environmental media and biological systems.

  4. Gold(I) Complexes with N-Donor Ligands. 2.(1) Reactions of Ammonium Salts with [Au(acac-kappaC(2))(PR(3))] To Give [Au(NH(3))L](+), [(AuL)(2)(&mgr;(2)-NH(2))](+), [(AuL)(4)(&mgr;(4)-N)](+), or [(AuL)(3)(&mgr;(3)-O)](+). A New and Facile Synthesis of [Au(NH(3))(2)](+) Salts. Crystal Structure of [{AuP(C(6)H(4)OMe-4)(3)}(3)(&mgr;(3)-O)]CF(3)SO(3).

    PubMed

    Vicente, José; Chicote, María-Teresa; Guerrero, Rita; Jones, Peter G.; Ramírez De Arellano, M. Carmen

    1997-09-24

    The complexes [Au(acac-kappaC(2))(PR(3))] (acac = acetylacetonate, R = Ph, C(6)H(4)OMe-4) react with (NH(4))ClO(4) to give amminegold(I), [Au(NH(3))(PR(3))]ClO(4), amidogold(I), [(AuPR(3))(2)(&mgr;(2)-NH(2))]ClO(4), or nitridogold(I), [(AuPR(3))(4)(&mgr;(4)-N)]ClO(4), complexes, depending on the reaction conditions. Similarly, [Au(acac-kappaC(2))(PPh(3))] reacts with (NH(3)R')OTf (OTf = CF(3)SO(3)) (1:1) or with [H(3)N(CH(2))(2)NH(2)]OTf (1:1) to give (amine)gold(I) complexes [Au(NH(2)R')(PPh(3))]OTf (R' = Me, C(6)H(4)NO(2)-4) or [(AuPPh(3))(2){&mgr;(2)-H(2)N(CH(2))(2)NH(2)}](OTf)(2), respectively. The ammonium salts (NH(2)R'(2))OTf (R' = Et, Ph) react with [Au(acac-kappaC(2))(PR(3))] (R = Ph, C(6)H(4)OMe-4) (1:2) to give, after hydrolysis, the oxonium salts [(AuPR(3))(3)(&mgr;(3)-O)]OTf (R = Ph, C(6)H(4)OMe-4). When NH(3) is bubbled through a solution of [AuCl(tht)] (tht = tetrahydrothiophene), the complex [Au(NH(3))(2)]Cl precipitates. Addition of [Au(NH(3))(2)]Cl to a solution of AgClO(4) or TlOTf leads to the isolation of [Au(NH(3))(2)]ClO(4) or [Au(NH(3))(2)]OTf, respectively. The crystal structure of [(AuPR(3))(3)(&mgr;(3)-O)]OTf.Me(2)CO (R = C(6)H(4)OMe-4) has been determined: triclinic, space group P&onemacr;, a = 14.884(3) Å, b = 15.828(3) Å, c = 16.061(3) Å, alpha = 83.39(3) degrees, beta = 86.28(3) degrees, gamma = 65.54(3) degrees, R1 (wR2) = 0.0370 (0.0788). The [(AuPR(3))(3)(&mgr;(3)-O)](+) cation shows an essentially trigonal pyramidal array of three gold atoms and one oxygen atom with O-Au-P bond angles of ca. 175 degrees and Au.Au contacts in the range 2.9585(7)-3.0505(14) Å. These cations are linked into centrosymmetric dimers through two short Au.Au [2.9585(7), 3.0919(9) Å] contacts. The gold atoms of the dimer form a six-membered ring with a chair conformation.

  5. Copper(II) ion catalytic oxidation of o-phenylenediamine and characterization, X-ray crystal structure and solution studies of the final product [DAPH][H3O][Cu(dipic)23H2O

    NASA Astrophysics Data System (ADS)

    Ghasemi, Khaled; Rezvani, Ali Reza; Shokrollahi, Ardeshir; Abdul Razak, Ibrahim; Refahi, Masoud; Moghimi, Abolghasem; Rosli, Mohd Mustaqim

    2015-09-01

    The complex [DAPH][H3O][Cu(dipic)23H2O, (1) (dipicH2 = 2,6-pyridinedicarboxylic acid and DAP = 2,3-diaminophenazine) was prepared from the reaction of Cu(NO3)2·2H2O with mixture of o-phenylenediamine (OPD) and 2,6-pyridinedicarboxylic acid in water. The complex was characterized by FTIR, elemental analysis, UV-Vis and the single-crystal X-ray diffraction. The crystal system is monoclinic with the space group P21/c. This complex is stabilized in the solid state by an extensive network of hydrogen bonds between crystallized water, anionic and cationic fragments, which form a three-dimensional network. Furthermore, hydrogen bonds, π⋯π and Csbnd O⋯π stacking interactions seem to be effective in stabilizing the crystal structures. The protonation constants of dipic (L) and DAP (Q), the equilibrium constants for the dipic-DAP proton transfer system and the stoichiometry and stability constants of binary complexes including each of ligands (dipic, DAP) in presence Cu2+ ion, ternary complexes including, both of ligands (dipic-DAP) in presence of metal ion were calculated in aqueous solutions by potentiometric pH titration method using the Hyperquad2008 program. The stoichiometry of the most complexes species in solution was found to be very similar to the solid-state of cited metal ion complex.

  6. Emission analysis of RE3+ (RE = Sm, Dy):B2O3-TeO2-Li2O-AlF3 glasses.

    PubMed

    Raju, C Nageswara; Sailaja, S; Kumari, S Pavan; Dhoble, S J; Kumar, V Ramesh; Ramanaiah, M V; Reddy, B Sudhakar

    2013-01-01

    This article reports on the optical properties of 0.5% mol of Sm(3+), Dy(3+) ion-doped B2O3-TeO2-Li2O-AlF3 (LiAlFBT) glasses. The glass samples were characterized by optical absorption and emission spectra. Judd-Ofelt theory was applied to analyze the optical absorption spectra and calculate the intensity parameters and radiative properties of the emission transitions. The emission spectra of Sm(3+) and Dy(3+):LiAlFBT glasses showed a bright reddish-orange emission at 598 nm ((4)G5/2 → (6)H7/2) and an intense yellow emission at 574 nm ((4)F9/2 → (6)H13/2), respectively. Full width at half maximum (FWHM), stimulated emission cross section, gain bandwidth and optical gain values were also calculated to extend the applications of the Sm(3+) and Dy(3+):LiAlFBT glasses. Copyright © 2012 John Wiley & Sons, Ltd.

  7. THE GREEN PHOSPHOR SrAl2O4:Eu2+, R3+ (R=Y, Dy) AND ITS APPLICATION IN ALTERNATING CURRENT LIGHT-EMITTING DIODES

    NASA Astrophysics Data System (ADS)

    Chen, Lei; Zhang, Yao; Xue, Shaochan; Deng, Xiaorong; Anqi; Luo; Liu, Fayong; Jiang, Yang; Chen, Shifu; Bahader, Ali

    2013-07-01

    The aim of the present investigation was to develop a phosphor to solve the flickering luminescence of alternating current (AC) light-emitting diodes (LED) by compensating the dark duration with appropriately persistent luminescence. The phosphor SrAl2O4:Eu2+ co-doped with Y3+ or Dy3+ was synthesized via solid-state reaction with H3BO3 as flux. The crystal structure and morphology were characterized by using X-ray diffraction (XRD) and Scanning Electron Microscope (SEM), respectively. The photoluminescence spectra were collected with a fluorescence spectrometer. The results demonstrated that appropriate amount of Y3+ or DY3+ doped was beneficial to suppress the by-product of Sr4Al14O25 which easily co-existed with the SrAl2O4 phase brought by the flux of H3BO3. However, too much Y3+ or DY3+ doped resulted in the formation of another impurity phase, i.e., the yttrium aluminum garnet of Y3Al5O12 and Dy3Al5O12. Comparatively, the doped DY3+ was more helpful in prolonging the persistent luminescence, while Y3+ was more efficient in enhancing luminescence intensity. To demonstrate the feasibility of the phosphor applied in AC LEDs, a nearly white AC LED was fabricated by coating the phosphor on a blue AC LED chip. The persistent luminescence was radiated from the AC LED device after turning power off. Moreover, the effect of the phosphor on compensating the AC LED dark duration through persistent luminescence was revealed by using the Keyence VW-9000 High-speed Microscope for the first time.

  8. Effect of solution combusted TiO2 nanopowder within commercial BaTiO3 dielectric layer on the photoelectric properties for AC powder electroluminescence devices.

    PubMed

    Park, Sung; Choi, Gil Rak; Kim, Youn Cheol; Lee, Jae Chun; Lee, Ju Hyeon

    2013-05-01

    A unique synthesis method was developed, which is called solution combustion method (SCM). TiO2 nanopowder was synthesized by this method. This SCM TiO2 nanopowder (-35 nm) was added to the dielectric layer of AC powder electroluminescence (EL) device. The dielectric layer was made of commercial BaTiO3 powder (-1.2 microm) and binding polymer. 0, 5, 10 and 15 wt% of SCM TiO2 nanopowder was added to the dielectric layer during fabrication of AC powder EL device respectively. Dielectric constant of these four kinds of dielectric layers was measured. The brightness and current density of AC powder EL device were also measured. When 10 wt% of SCM TiO2 nanopowder was added, dielectric constant and brightness were increased by 30% and 101% respectively. Furthermore, the current density was decreased by 71%. This means that the brightness was double and the power consumption was one third.

  9. Tris(5,6-dimethyl-1H-benzimidazole-κN(3))(pyridine-2,6-dicarboxyl-ato-κ(3)O(2),N,O(6))nickel(II).

    PubMed

    Li, Yue-Hua; Li, Feng-Feng; Liu, Xin-Hua; Zhao, Ling-Yan

    2012-06-01

    The title mononuclear complex, [Ni(C(7)H(3)NO(4))(C(9)H(10)N(2))(3)], shows a central Ni(II) atom which is coordinated by two carboxyl-ate O atoms and the N atom from a pyridine-2,6-dicarboxyl-ate ligand and by three N atoms from different 5,6-dimethyl-1H--benzimidazole ligands in a distorted octa-hedral geometry. The crystal structure shows intermolecular N-H⋯O hydrogen bonds.

  10. Axial zero-field splitting in mononuclear Co(ii) 2-N substituted N-confused porphyrin: Co(2-NC3H5-21-Y-CH2C6H4CH3-NCTPP)Cl (Y = o, m, p) and Co(2-NC3H5-21-CH2C6H5-NCTPP)Cl.

    PubMed

    Lai, Ya-Yuan; Chang, Yu-Chang; Chen, Jyh-Horung; Wang, Shin-Shin; Tung, Jo-Yu

    2016-03-21

    The inner C-benzyl- and C-o-xylyl (or m-xylyl, p-xylyl)-substituted cobalt(ii) complexes of a 2-N-substituted N-confused porphyrin were synthesized from the reaction of 2-NC3H5NCTPPH (1) and CoCl2·6H2O in toluene (or o-xylene, m-xylene, p-xylene). The crystal structures of diamagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-hydrogen-21-carbaporphyrinato-N,N',N'')zinc(ii) [Zn(2-NC3H5-21-H-NCTPP)Cl; 3 ] and paramagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-benzyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-CH2C6H5NCTPP)Cl; 7], and chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-Y-xylyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-Y-CH2C6H4CH3NCTPP)Cl] [Y = o (8), m (9), p (10)] were determined. The coordination sphere around the Zn(2+) (or Co(2+)) ion in 3 (or 7-10) is a distorted tetrahedron (DT). The free energy of activation at the coalescence temperature Tc for the exchange of phenyl ortho protons o-H (26) with o-H (22) in 3 in a CDCl3 solvent is found to be ΔG = 61.4 kJ mol(-1) through (1)H NMR temperature-dependent measurements. The axial zero-field splitting parameter |D| was found to vary from 35.6 cm(-1) in 7 (or 30.7 cm(-1) in 8) to 42.0 cm(-1) in 9 and 46.9 cm(-1) in 10 through paramagnetic susceptibility measurements. The magnitude of |D| can be related to the coordination sphere at the cobalt sites.

  11. Attikaite, Ca3Cu2Al2(AsO4)4(OH)4 · 2H2O, a new mineral species

    NASA Astrophysics Data System (ADS)

    Chukanov, N. V.; Pekov, I. V.; Zadov, A. E.

    2007-12-01

    Attikaite, a new mineral species, has been found together with arsenocrandalite, arsenogoyazite, conichalcite, olivenite, philipsbornite, azurite, malachite, carminite, beudantite, goethite, quartz, and allophane at the Christina Mine No. 132, Kamareza, Lavrion District, Attiki Prefecture (Attika), Greece. The mineral is named after the type locality. It forms spheroidal segregations (up to 0.3 mm in diameter) consisting of thin flexible crystals up to 3 × 20 × 80 μm in size. Its color is light blue to greenish blue, with a pale blue streak. The Mohs’ hardness is 2 to 2.5. The cleavage is eminent mica-like parallel to {001}. The density is 3.2(2) g/cm3 (measured in heavy liquids) and 3.356 g/cm3 (calculated). The wave numbers of the absorption bands in the infrared spectrum of attikaite are (cm-1; sh is shoulder; w is a weak band): 3525 sh, 3425, 3180, 1642, 1120 w, 1070 w, 1035 w, 900 sh, 874, 833, 820, 690 w, 645 w, 600 sh, 555, 486, 458, and 397. Attikaite is optically biaxial, negative, α = 1.642(2), β = γ = 1.644(2) ( X = c) 2 V means = 10(8)°, and 2 V calc = 0°. The new mineral is microscopically colorless and nonpleochroic. The chemical composition (electron microprobe, average over 4 point analyses, wt %) is: 0.17 MgO, 17.48 CaO, 0.12 FeO, 16.28 CuO, 10.61 Al2O3, 0.89 P2O5, 45.45 As2O5, 1.39 SO3, and H2O (by difference) 7.61, where the total is 100.00. The empirical formula calculated on the basis of (O,OH,H2O)22 is: Ca2.94Cu{1.93/2+} Al1.97Mg0.04Fe{0.02/2+} [(As3.74S0.16P0.12)Σ4.02O16.08](OH)3.87 · 2.05H2 O. The simplified formula is Ca3Cu2Al2(AsO4)4(OH)4 · 2H2O. Attikaite is orthorhombic, space group Pban, Pbam or Pba2; the unit-cell dimensions are a = 10.01(1), b = 8.199(5), c = 22.78(1) Å, V = 1870(3) Å3, and Z = 4. In the result of the ignition of attikaite for 30 to 35 min at 128 140°, the H2O bands in the IR spectrum disappear, while the OH-group band is not modified; the weight loss is 4.3%, which approximately corresponds to two H2O

  12. Hydrothermal synthesis and photoluminescent properties of hierarchical GdPO4·H2O:Ln3+ (Ln3+ = Eu3+, Ce3+, Tb3+) flower-like clusters

    NASA Astrophysics Data System (ADS)

    Amurisana, Bao.; Zhiqiang, Song.; Haschaolu, O.; Yi, Chen; Tegus, O.

    2018-02-01

    3D hierarchical GdPO4·H2O:Ln3+ (Ln3+ = Eu3+, Ce3+, Tb3+) flower clusters were successfully prepared on glass slide substrate by a simple, economical hydrothermal process with the assistance of disodium ethylenediaminetetraacetic acid (Na2H2L, where L4- = (CH2COO)2N(CH2)2N(CH2COO)24-). In this process, Na2H2L was used as both a chelating agent and a structure-director. The hierarchical flower clusters have an average diameter of 7-12 μm and are composed of well-aligned microrods. The influence of the molar ratio of Na2H2L/Gd3+ and reaction time on the morphology was systematically studied. A possible crystal growth and formation mechanism of hierarchical flower clusters is proposed based on the evolution of morphology as a function of reaction time. The self-assembled GdPO4·H2O:Ln3+ superstructures exhibit strong orange-red (Eu3+, 5D0 → 7F1), green (Tb3+, 5D4 → 7F5) and near ultraviolet emissions (Ce3+, 5d → 7F5/2) under ultraviolet excitation, respectively. This study may provide a new channel for building hierarchically superstructued oxide micro/nanomaterials with optical and new properties.

  13. Magnetic field tunable ac electrical transport of LaFeO3-wax nanocomposites

    NASA Astrophysics Data System (ADS)

    Roy, Supratim; Mandal, S. K.; Debnath, Rajesh; Nath, Debajyoti; Dey, P.

    2018-04-01

    Single phase perovskite LaFeO3 nanoparticles have been prepared through chemical pyrophoric reaction process. It is further grinded with paraffin wax of quantity 0.5 wt% of total composition to obtain an organic composite 99.5%LaFeO3-0.5%Wax. Studies of ac electrical properties viz. complex impedance, dielectric response, loss coefficient have been done in presence of external dc magnetic field, which reveals a good magnetoimpedance (˜221%) and a negative magnetodielectric (˜ 64%). The value of impedance, its real and imaginary part is observed to increase with dc field. The composite exhibits high dielectric constant (˜4760). The ac conductivity is found to decrease with applied field and increase with ac frequency.

  14. Speciated Monitoring of Gas-Phase Organic Peroxy Radicals by Chemical Ionization Mass Spectrometry: Cross-Reactions between CH3O2, CH3(CO)O2, (CH3)3CO2, and c-C6H11O2.

    PubMed

    Nozière, Barbara; Hanson, David R

    2017-11-09

    Organic peroxy radicals ("RO 2 ", with R organic) are key intermediates in most oxygen-rich systems, where organic compounds are oxidized (natural environment, flames, combustion engines, living organisms, etc). But, until recently, techniques able to monitor simultaneously and distinguish between RO 2 species ("speciated" detection) have been scarce, which has limited the understanding of complex systems containing these radicals. Mass spectrometry using proton transfer ionization has been shown previously to detect individual gas-phase RO 2 separately. In this work, we illustrate its ability to speciate and monitor several RO 2 simultaneously by investigating reactions involving CH 3 O 2 , CH 3 C(O)O 2 , c-C 6 H 11 O 2 , and (CH 3 ) 3 CO 2 . The detection sensitivity of each of these radicals was estimated by titration with NO to between 50 and 1000 Hz/ppb, with a factor from 3 to 5 of uncertainties, mostly due to the uncertainties in knowing the amounts of added NO. With this, the RO 2 concentration in the reactor was estimated between 1 × 10 10 and 1 × 10 12 molecules cm -3 . When adding a second radical species to the reactor, the kinetics of the cross-reaction could be studied directly from the decay of the first radical. The time-evolution of two and sometimes three different RO 2 was followed simultaneously, as the CH 3 O 2 produced in further reaction steps was also detected in some systems. The rate coefficients obtained are (in molecule -1 cm 3 s -1 ): k CH3O2+CH3C(O)O2 = 1.2 × 10 -11 , k CH3O2+t-butylO2 = 3.0 × 10 -15 , k c-hexylO2+CH3O2 = 1.2 × 10 -13 , k t-butylO2+CH3C(O)O2 = 3.7 × 10 -14 , and k c-hexylO2+t-butylO2 = 1.5 × 10 -15 . In spite of their good comparison with the literature and good reproducibility, large uncertainties (×5/5) are recommended on these results because of those in the detection sensitivities. This work is a first illustration of the potential applications of this technique for the investigation of organic radicals in

  15. High-resolution photoelectron spectroscopy of TiO3H2-: Probing the TiO2- + H2O dissociative adduct

    NASA Astrophysics Data System (ADS)

    DeVine, Jessalyn A.; Abou Taka, Ali; Babin, Mark C.; Weichman, Marissa L.; Hratchian, Hrant P.; Neumark, Daniel M.

    2018-06-01

    Slow electron velocity-map imaging spectroscopy of cryogenically cooled TiO3H2- anions is used to probe the simplest titania/water reaction, TiO20/- + H2O. The resultant spectra show vibrationally resolved structure assigned to detachment from the cis-dihydroxide TiO(OH)2- geometry based on density functional theory calculations, demonstrating that for the reaction of the anionic TiO2- monomer with a single water molecule, the dissociative adduct (where the water is split) is energetically preferred over a molecularly adsorbed geometry. This work represents a significant improvement in resolution over previous measurements, yielding an electron affinity of 1.2529(4) eV as well as several vibrational frequencies for neutral TiO(OH)2. The energy resolution of the current results combined with photoelectron angular distributions reveals Herzberg-Teller coupling-induced transitions to Franck-Condon forbidden vibrational levels of the neutral ground state. A comparison to the previously measured spectrum of bare TiO2- indicates that reaction with water stabilizes neutral TiO2 more than the anion, providing insight into the fundamental chemical interactions between titania and water.

  16. Live imaging of H3K9 acetylation in plant cells

    PubMed Central

    Kurita, Kazuki; Sakamoto, Takuya; Yagi, Noriyoshi; Sakamoto, Yuki; Ito, Akihiro; Nishino, Norikazu; Sako, Kaori; Yoshida, Minoru; Kimura, Hiroshi; Seki, Motoaki; Matsunaga, Sachihiro

    2017-01-01

    Proper regulation of histone acetylation is important in development and cellular responses to environmental stimuli. However, the dynamics of histone acetylation at the single-cell level remains poorly understood. Here we established a transgenic plant cell line to track histone H3 lysine 9 acetylation (H3K9ac) with a modification-specific intracellular antibody (mintbody). The H3K9ac-specific mintbody fused to the enhanced green fluorescent protein (H3K9ac-mintbody-GFP) was introduced into tobacco BY-2 cells. We successfully demonstrated that H3K9ac-mintbody-GFP interacted with H3K9ac in vivo. The ratio of nuclear/cytoplasmic H3K9ac-mintbody-GFP detected in quantitative analysis reflected the endogenous H3K9ac levels. Under chemically induced hyperacetylation conditions with histone deacetylase inhibitors including trichostatin A, Ky-2 and Ky-14, significant enhancement of H3K9ac was detected by H3K9ac-mintbody-GFP dependent on the strength of inhibitors. Conversely, treatment with a histone acetyltransferase inhibitor, C646 caused a reduction in the nuclear to cytoplasmic ratio of H3K9ac-mintbody-GFP. Using this system, we assessed the environmental responses of H3K9ac and found that cold and salt stresses enhanced H3K9ac in tobacco BY-2 cells. In addition, a combination of H3K9ac-mintbody-GFP with 5-ethynyl-2′-deoxyuridine labelling confirmed that H3K9ac level is constant during interphase. PMID:28418019

  17. 1-(2-Cyano­ethyl)-2-(2-pyrid­yl)-1H,3H-benzimidazol-3-ium perchlorate

    PubMed Central

    Li, Yan; Tang, Xiaoliang; Chen, Jiayu; Wu, Daxiang; Liu, Weisheng

    2010-01-01

    The title compound, C15H13N4 +·ClO4 −, comprises a nonplanar 1-(2-cyano­ethyl)-2-(2-pyrid­yl)-1H,3H-benzimidazol-3-ium cation [dihedral angle between the imidazole and pyridine rings = 22.5 (8)°] and a perchlorate anion. The cation is formed by protonation of the N atom of the benzimidazole ring. A charged N—H⋯O hydrogen bond connects the anion and cation, and inter­molecular C—H⋯O and C—H⋯N inter­actions contribute to the crystal packing. PMID:21579831

  18. Experimental Determination of Solubilities of Tri-calcium Di-Citrate Tetrahydrate [Ca 3[C 3H 5O(COO) 3] 2•4H 2O] Earlandite in NaCl and MgCl 2 Solutions to High Ionic Strengths and Its Pitzer Model: Applications to Nuclear Waste Isolation and Other Low Temperature Environments

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

    Xiong, Yongliang; Kirkes, Leslie Dawn; Westfall, Terry

    In this study, solubility measurements on tri-calcium di-citrate tetrahydrate [Ca 3[C 3H 5O(COO) 3]2•4H 2O, abbreviated as Ca 3[Citrate] 2•4H 2O] as a function of ionic strength are conducted in NaCl solutions up to I = 5.0 mol•kg –1 and in MgCl 2 solutions up to I = 7.5 mol•kg –1, at room temperature (22.5 ± 0.5°C). The solubility constant (log Kmore » $$0\\atop{sp}$$) for Ca 3[Citrate] 2•4H 2O and formation constant (logβ$$0\\atop{1}$$) for Ca[C 3H 5O(COO) 3] –Ca 3[C 3H 5O(COO) 3] 2•4H 2O (earlandite) = 3Ca 2+ + 2[C 3H 5O(COO) 3] 3– + 4H 2O (1) Ca 2+ + [C 3H 5O(COO) 3] 3– = Ca[C 3H 5O(COO) 3] – (2) are determined as –18.11 ± 0.05 and 4.97 ± 0.05, respectively, based on the Pitzer model with a set of Pitzer parameters describing the specific interactions in NaCl and M gCl 2 media.« less

  19. Thermodynamic properties and crystal structure refinement of ferricopiapite, coquimbite, rhomboclase, and Fe2(SO4)3(H2O)5

    USGS Publications Warehouse

    Majzlan, J.; Navrotsky, A.; McCleskey, R. Blaine; Alpers, Charles N.

    2006-01-01

    Enthalpies of formation of ferricopiapite [nominally Fe4.67(SO4)6(OH)2 (H2O)20]. coquimbite [Fe2(SO4)3(H2O)9], rhomboclase [(H3O)Fe(SO4)2 (H2O)3], and Fe2(SO4)3(H2O)5 were measured by acid (5 N HCl) solution calorimetry. The samples were characterized by wet chemical analyses and synchrotron powder X-ray diffraction (XRD). The refinement of XRD patterns gave lattice parameters, atomic positions, thermal factors, and occupancies of the sites. The calculated formulae differ slightly from the nominal compositions: Fe4.78(SO4)6 (OH)2.34(H2O)20.71 (ferricopiapite), (Fe1.47Al0.53)(SO4)3 (H2O)9.65 (coquimbite), (H3O)1.34Fe(SO4)2.17 (H2O)3.06 (rhomboclase), and Fe2(SO4)3 (H2O)5.03. All thermodynamic data are given per mole of these formulae. The measured standard enthalpies (in kJ/mol) of formation from the elements (crystalline Fe, Al, S, and ideal gases O2 and H2) at T = 298.15 K are -4115.8??4.1 [Fe2(SO4)3 (H2O)5.03], -12045.1??9.2 (ferricopiapite), -5738.4??3.3 (coquimbite), and -3201.1??2.6 (rhomboclase). Standard entropy (S??) was estimated as a sum of entropies of oxide, hydroxide, and sulfate components. The estimated S?? (in J/mol.K) values for the iron sulfates are 488.2 [Fe2(SO4)3 (H2O)5.03], 1449.2 (ferricopiapite), 638.3 (coquimbite), and 380.1 (rhomboclase). The calculated Gibbs free energies of formation (in kJ/mol) are -3499.7??4.2 [Fe2(SO4)3 (H2O)5.03], -10089.8??9.3 (ferricopiapite), -4845.6??3.3 (coquimbite), and -2688.0??2.7 (rhomboclase). These results combined with other available thermodynamic data allow construction of mineral stability diagrams in the FeIII2(SO4)3-FeII SO4-H2O system. One such diagram is provided, indicating that the order of stability of ferric sulfate minerals with decreasing pH in the range of 1.5 to -0.5 is: hydronium jarosite, ferricopiapite, and rhomboclase. ?? 2006 E. Schweizerbart'sche Verlagsbuchhandlung.

  20. Effect of H2O on the morphological changes of KNO3 formed on K2O/Al2O3 NOx storage materials: Fourier transform infra-red (FTIR) and time-resolved x-ray diffraction (TR-XRD) studies

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

    Kim, Do Heui; Mudiyanselage, Kumudu K.; Szanyi, Janos

    Based on combined FTIR and XRD studies, we report here that H2O induces a morphological change of KNO3 species formed on model K2O/Al2O3 NOx storage-reduction catalysts. Specifically as evidenced by FTIR, the contact of H2O with NO2 pre-adsorbed on K2O/Al2O3 promotes the transformation from bidentate (surface-like) KNO3 species to ionic (bulk-like) ones irrespective of K loadings. Once H2O is removed from the sample, a reversible transformation into bidentate KNO3 is observed, demonstrating a significant dependence of H2O on such morphological changes. TR-XRD results show the formation of two different types of bulk KNO3 phases (orthorhomobic and rhombohedral) in an as-impregnatedmore » sample. Once H2O begins to desorb above 400 K, the former is transformed into the latter, resulting in the existence of only the rhombohedral KNO3 phase. On the basis of consistent FTIR and TR-XRD results, we propose a model for the morphological changes of KNO3 species with respect to NO2 adsorption/desorption, H2O and/or heat treatments. Compared with the BaO/Al2O3 system, K2O/Al2O3 shows some similarities with respect to the formation of bulk nitrates upon H2O contact. However, there are significant differences that originate from the lower melting temperature of KNO3 relative to Ba(NO3)2.« less

  1. Infrared absorption of CH3OSO and CD3OSO radicals produced upon photolysis of CH3OS(O)Cl and CD3OS(O)Cl in p-H2 matrices.

    PubMed

    Lee, Yu-Fang; Kong, Lin-Jun; Lee, Yuan-Pern

    2012-03-28

    Irradiation at 239 ± 20 nm of a p-H(2) matrix containing methoxysulfinyl chloride, CH(3)OS(O)Cl, at 3.2 K with filtered light from a medium-pressure mercury lamp produced infrared (IR) absorption lines at 3028.4 (attributable to ν(1), CH(2) antisymmetric stretching), 2999.5 (ν(2), CH(3) antisymmetric stretching), 2950.4 (ν(3), CH(3) symmetric stretching), 1465.2 (ν(4), CH(2) scissoring), 1452.0 (ν(5), CH(3) deformation), 1417.8 (ν(6), CH(3) umbrella), 1165.2 (ν(7), CH(3) wagging), 1152.1 (ν(8), S=O stretching mixed with CH(3) rocking), 1147.8 (ν(9), S=O stretching mixed with CH(3) wagging), 989.7 (ν(10), C-O stretching), and 714.5 cm(-1) (ν(11), S-O stretching) modes of syn-CH(3)OSO. When CD(3)OS(O)Cl in a p-H(2) matrix was used, lines at 2275.9 (ν(1)), 2251.9 (ν(2)), 2083.3 (ν(3)), 1070.3 (ν(4)), 1056.0 (ν(5)), 1085.5 (ν(6)), 1159.7 (ν(7)), 920.1 (ν(8)), 889.0 (ν(9)), 976.9 (ν(10)), and 688.9 (ν(11)) cm(-1) appeared and are assigned to syn-CD(3)OSO; the mode numbers correspond to those used for syn-CH(3)OSO. The assignments are based on the photolytic behavior and a comparison of observed vibrational wavenumbers, infrared intensities, and deuterium isotopic shifts with those predicted with the B3P86∕aug-cc-pVTZ method. Our results extend the previously reported four transient IR absorption bands of gaseous syn-CH(3)OSO near 2991, 2956, 1152, and 994 cm(-1) to 11 lines, including those associated with C-O, O-S, and S=O stretching modes. Vibrational wavenumbers of syn-CD(3)OSO are new. These results demonstrate the advantage of a diminished cage effect of solid p-H(2) such that the Cl atom, produced via UV photodissociation of CH(3)OS(O)Cl in situ, might escape from the original cage to yield isolated CH(3)OSO radicals.

  2. Syntheses, structures, and vibrational spectroscopy of the two-dimensional iodates Ln(IO{sub 3}){sub 3} and Ln(IO{sub 3}){sub 3}(H{sub 2}O) (Ln =Yb, Lu)

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

    Assefa, Zerihun; Ling Jie; Haire, Richard G.

    2006-12-15

    The reaction of Lu{sup 3+} or Yb{sup 3+} and H{sub 5}IO{sub 6} in aqueous media at 180 {sup o}C leads to the formation of Yb(IO{sub 3}){sub 3}(H{sub 2}O) or Lu(IO{sub 3}){sub 3}(H{sub 2}O), respectively, while the reaction of Yb metal with H{sub 5}IO{sub 6} under similar reaction conditions gives rise to the anhydrous iodate, Yb(IO{sub 3}){sub 3}. Under supercritical conditions Lu{sup 3+} reacts with HIO{sub 3} and KIO{sub 4} to yield the isostructural Lu(IO{sub 3}){sub 3}. The structures have been determined by single-crystal X-ray diffraction. Crystallographic data are (MoK{alpha}, {lambda}=0.71073 A): Yb(IO{sub 3}){sub 3}, monoclinic, space group P2{sub 1}/n, a=8.6664(9)more » A, b=5.9904(6) A, c=14.8826(15) A, {beta}=96.931(2){sup o}, V=766.99(13), Z=4, R(F)=4.23% for 114 parameters with 1880 reflections with I>2{sigma}(I); Lu(IO{sub 3}){sub 3}, monoclinic, space group P2{sub 1}/n, a=8.6410(9), b=5.9961(6), c=14.8782(16) A, {beta}=97.028(2){sup o}, V=765.08(14), Z=4, R(F)=2.65% for 119 parameters with 1756 reflections with I>2{sigma}(I); Yb(IO{sub 3}){sub 3}(H{sub 2}O), monoclinic, space group C2/c, a=27.2476(15), b=5.6296(3), c=12.0157(7) A, {beta}=98.636(1){sup o}, V=1822.2(2), Z=8, R(F)=1.51% for 128 parameters with 2250 reflections with I>2{sigma}(I); Lu(IO{sub 3}){sub 3}(H{sub 2}O), monoclinic, space group C2/c, a=27.258(4), b=5.6251(7), c=12.0006(16) A, {beta}=98.704(2){sup o}, V=1818.8(4), Z=8, R(F)=1.98% for 128 parameters with 2242 reflections with I>2{sigma}(I). The f elements in all of the compounds are found in seven-coordinate environments and bridged with monodentate, bidentate, or tridentate iodate anions. Both Lu(IO{sub 3}){sub 3}(H and Yb(IO{sub 3}){sub 3}(H{sub 2}O) display distinctively different vibrational profiles from their respective anhydrous analogs. Hence, the Raman profile can be used as a complementary diagnostic tool to discern the different structural motifs of the compounds. - Graphical abstract: Four new metal iodates, Yb

  3. 1H,1H,5H-Perfluoropentyl-1,1,2,2-tetrafluoroethylether as a co-solvent for high voltage LiNi1/3Co1/3Mn1/3O2/graphite cells

    NASA Astrophysics Data System (ADS)

    Wang, Chengyun; Zuo, Xiaoxi; Zhao, Minkai; Xiao, Xin; Yu, Le; Nan, Junmin

    2016-03-01

    1H,1H,5H-Perfluoropentyl-1,1,2,2-tetrafluoroethylether (F-EAE) mixed with ethylene carbonate (EC), diethyl carbonate (DEC), and lithium hexafluorophosphate (LiPF6) is evaluated as a co-solvent high-potential electrolyte of LiNi1/3Co1/3Mn1/3O2/graphite batteries. Linear sweep voltammetry (LSV) and cyclic voltammetry (CV) indicate that the EC/DEC-based electrolyte with F-EAE possesses a high oxidation potential (>5.2 V vs. Li/Li+) and excellent film-forming characteristics. With 40 wt% F-EAE in the electrolyte, the capacity retention of the LiNi1/3Co1/3Mn1/3O2/graphite pouch cells that are cycled between 3.0 and 4.5 V is significantly improved from 28.8% to 86.8% after 100 cycles. In addition, electrochemical impedance spectroscopy (EIS) of three-electrode pouch cells, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) are used to characterize the effects of F-EAE on the enhanced capacity retention. It is demonstrated that F-EAE facilitates the formation of a stable surface electrolyte interface (SEI) layer with low impedance on the anode and effectively suppresses an increase in the charge-transfer resistance on the cathode. These results suggest that F-EAE can serve as an alternative electrolyte solvent for 4.5 V high voltage rechargeable lithium-ion batteries.

  4. Synthesis, structure, and catalytic performance in cyclooctene epoxidation of a molybdenum oxide/bipyridine hybrid material: {[MoO3(bipy)][MoO3(H2O)]}n.

    PubMed

    Abrantes, Marta; Amarante, Tatiana R; Antunes, Margarida M; Gago, Sandra; Paz, Filipe A Almeida; Margiolaki, Irene; Rodrigues, Alírio E; Pillinger, Martyn; Valente, Anabela A; Gonçalves, Isabel S

    2010-08-02

    The reaction of [MoO(2)Cl(2)(bipy)] (1) (bipy = 2,2'-bipyridine) with water in a Teflon-lined stainless steel autoclave (100 degrees C, 19 h), in an open reflux system with oil bath heating (12 h) or in a microwave synthesis system (120 degrees C, 4 h), gave the molybdenum oxide/bipyridine hybrid material {[MoO(3)(bipy)][MoO(3)(H(2)O)]}(n) (2) as a microcrystalline powder in yields of 72-92%. The crystal structure of 2 determined from synchrotron X-ray powder diffraction data is composed of two distinct neutral one-dimensional polymers: an organic-inorganic polymer, [MoO(3)(bipy)](n), and a purely inorganic chain, [MoO(3)(H(2)O)](n), which are interconnected by O-H...O hydrogen bonding interactions. Compound 2 is a moderately active, stable, and selective catalyst for the epoxidation of cis-cyclooctene at 55 degrees C with tert-butylhydroperoxide (tBuOOH, 5.5 M in decane or 70% aqueous) as the oxidant. Biphasic solid-liquid or triphasic solid-organic-aqueous mixtures are formed, and 1,2-epoxycyclooctane is the only reaction product. When n-hexane is employed as a cosolvent and tBuOOH(decane) is the oxidant, the catalytic reaction is heterogeneous in nature, and the solid catalyst can be recycled and reused without a loss of activity. For comparison, the catalytic performance of the precursor 1 was also investigated. The IR spectra of solids recovered after catalysis indicate that 1 transforms into the organic-inorganic polymer [MoO(3)(bipy)] when the oxidant is tBuOOH(decane) and compound 2 when the oxidant is 70% aqueous tBuOOH.

  5. Reaction paths in the system Al 2O 3-hBN-Y

    NASA Astrophysics Data System (ADS)

    Reichert, K.; Oreshina, O.; Cremer, R.; Neuschütz, D.

    2001-07-01

    As part of the investigations on the suitability of a new concept for a tailored fiber-matrix interface in sapphire fiber reinforced NiAl matrix composites for application as a high-temperature structural material, the interfacial reactions in the system alumina-hexagonal boron nitride-yttrium (Al 2O 3-hBN-Y) have been examined in the temperature range of 1100-1300°C. For this, alumina substrates were coated with hBN by means of CVD and subsequently with sputter deposited yttrium. Afterwards the samples were annealed for up to 16 h under inert atmosphere. Grazing incidence X-ray diffraction (GIXRD) served to analyze the phases formed by diffusion processes in the reaction zone. The peak intensities in these diffraction patterns were used to evaluate the sequence of phases formed due to diffusion and reaction. After the initial formation of YN and YB 2, the phases Y 2O 3, Al 2Y, and YB 4 were observed. Even longer annealing times or higher temperatures, respectively, led to the formation of the ternary oxides YAlO 3 and Y 3Al 5O 12 as well as metallic aluminum.

  6. [Ph(3)PCH(2)Ph](2)[Zn(3)(tp)(3)Cl(2)] and Ni(3)(tma)(2)(H(2)O)(8): two unusual claylike frameworks of metal-polycarboxylate coordination polymers (tp = terephthalate, tma = trimesate).

    PubMed

    Yang, Guo-Dong; Dai, Jing-Cao; Lian, Yun-Xia; Wu, Wen-Shi; Lin, Jian-Ming; Hu, Sheng-Min; Sheng, Tian-Lu; Fu, Zhi-Yong; Wu, Xin-Tao

    2007-09-17

    Two new compounds, [Ph3PCH2Ph]2[Zn3(tp)3Cl2] (1) and Ni3(tma)2(H2O)8 (2) (tp = terephthalate, tma = trimesate), are metal-polycarboxylate coordination polymers prepared by similar hydrothermal synthesis techniques. X-ray single-crystal structural analysis shows that both compounds crystallize in the 2D claylike lamellar architectures, in which 1 possesses the interlayer [Ph3PCH2Ph]+ exchangeable cation and has been confirmed by PXRD patterns. 1 (C74H56Cl2O12P2Zn3) belongs to monoclinic P21/c, Z = 2 (a = 18.956(1) A, b = 10.2697(5) A, c = 17.067(1) A, beta = 99.486(4) degrees ). 2 (C18H22O20Ni3) is attributed to triclinic P, Z = 1 (a = 6.6643(8) A, b = 9.622(1) A, c = 10.089(1) A, alpha = 112.675(2) degrees , beta = 94.007(1) degrees, gamma = 106.411(2) degrees ). Linear metal trinuclear clusters bridged by rigid linear tp ligands for 1 and trigonal tma ligands for 2 give rise to a novel 2D 6-linked (3,6) topological anionic network in 1 and an interesting 2D 3,6-linked molybdenite topological neutral network in 2, respectively. Both compounds exhibit intense fluorescent emission bands at 410 nm (lambda(exc) = 355 nm) for 1 and 398 nm (lambda(exc) = 300 nm) for 2 in the solid state at room temperature.

  7. Comparison of O2 and H2O as oxygen source for homoepitaxial growth of β-Ga2O3 layers by halide vapor phase epitaxy

    NASA Astrophysics Data System (ADS)

    Konishi, Keita; Goto, Ken; Togashi, Rie; Murakami, Hisashi; Higashiwaki, Masataka; Kuramata, Akito; Yamakoshi, Shigenobu; Monemar, Bo; Kumagai, Yoshinao

    2018-06-01

    Homoepitaxial growth of β-Ga2O3 layers by halide vapor phase epitaxy (HVPE) using O2 or H2O as an oxygen source was investigated by thermodynamic analysis, and compared with measured properties after growth. The thermodynamic analysis revealed that Ga2O3 growth is expected even at 1000 °C using both oxygen sources due to positive driving forces for Ga2O3 deposition. The experimental results for homoepitaxial growth on (0 0 1) β-Ga2O3 substrates showed that the surfaces of the layers grown with H2O were smoother than those grown with O2, although the growth rate with H2O was approximately half that with O2. However, in the homoepitaxial layer grown using H2O, incorporation of Si impurities with a concentration almost equal to the effective donor concentration (2 × 1016 cm-3) was confirmed, which was caused by decomposition of the quartz glass reactor due to the presence of hydrogen in the system.

  8. The Tick-Over Theory Revisited: Formation and Regulation of the Soluble Alternative Complement C3 Convertase (C3(H2O)Bb)

    PubMed Central

    Bexborn, Fredrik; Andersson, Per Ola; Chen, Hui; Nilsson, Bo; Ekdahl, Kristina N.

    2009-01-01

    The molecular interactions between the components of the C3 convertase of the alternative pathway (AP) of complement and its regulators, in both surface-bound and fluid-phase form, are still incompletely understood. The fact that the AP convertase is labile makes studies difficult to perform. According to the so called tick-over theory, hydrolyzed C3, called C3(H2O), forms the initial convertase in fluid phase together with factor B. In the present study, we have applied western blot analysis and ELISA together with fluorescence resonance energy transfer (FRET) to study the formation of the fluid-phase AP convertases C3(H2O)Bb and C3bBb and their regulation by factor H and factor I at specific time points and, with FRET, in real time. In our hands, factor B showed a higher affinity for C3(H2O) than for C3b, although in both cases it was readily activated to Bb. However, the convertase activity of C3bBb was approximately twice that of C3(H2O)Bb, as monitored by the generation of C3a. But in contrast, the C3(H2O)Bb convertase was more resistant to inactivation by factor H and factor I than was the C3bBb convertase. Under conditions that totally inactivated C3bBb, C3(H2O)Bb still retained approximately 25% of its initial activity. PMID:18096230

  9. The tick-over theory revisited: formation and regulation of the soluble alternative complement C3 convertase (C3(H2O)Bb).

    PubMed

    Bexborn, Fredrik; Andersson, Per Ola; Chen, Hui; Nilsson, Bo; Ekdahl, Kristina N

    2008-04-01

    The molecular interactions between the components of the C3 convertase of the alternative pathway (AP) of complement and its regulators, in both surface-bound and fluid-phase form, are still incompletely understood. The fact that the AP convertase is labile makes studies difficult to perform. According to the so called tick-over theory, hydrolyzed C3, called C3(H(2)O), forms the initial convertase in fluid phase together with factor B. In the present study, we have applied western blot analysis and ELISA together with fluorescence resonance energy transfer (FRET) to study the formation of the fluid-phase AP convertases C3(H(2)O)Bb and C3bBb and their regulation by factor H and factor I at specific time points and, with FRET, in real time. In our hands, factor B showed a higher affinity for C3(H(2)O) than for C3b, although in both cases it was readily activated to Bb. However, the convertase activity of C3bBb was approximately twice that of C3(H(2)O)Bb, as monitored by the generation of C3a. But in contrast, the C3(H(2)O)Bb convertase was more resistant to inactivation by factor H and factor I than was the C3bBb convertase. Under conditions that totally inactivated C3bBb, C3(H(2)O)Bb still retained approximately 25% of its initial activity.

  10. Engineering epitaxial γ-Al2O3 gate dielectric films on 4H-SiC

    NASA Astrophysics Data System (ADS)

    Tanner, Carey M.; Toney, Michael F.; Lu, Jun; Blom, Hans-Olof; Sawkar-Mathur, Monica; Tafesse, Melat A.; Chang, Jane P.

    2007-11-01

    The formation of epitaxial γ-Al2O3 thin films on 4H-SiC was found to be strongly dependent on the film thickness. An abrupt interface was observed in films up to 200 Å thick with an epitaxial relationship of γ-Al2O3(111)‖4H-SiC(0001) and γ-Al2O3(44¯0)‖4H-SiC(112¯0). The in-plane alignment between the film and the substrate is nearly complete for γ-Al2O3 films up to 115 Å thick, but quickly diminishes in thicker films. The films are found to be slightly strained laterally in tension; the strain increases with thickness and then decreases in films thicker than 200 Å, indicating strain relaxation which is accompanied by increased misorientation. By controlling the structure of ultrathin Al2O3 films, metal-oxide-semiconductor capacitors with Al2O3 gate dielectrics on 4H-SiC were found to have a very low leakage current density, suggesting suitability of Al2O3 for SiC device integration.

  11. Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O

    NASA Astrophysics Data System (ADS)

    Johannes, Wilhelm

    1980-09-01

    Beginning of melting and subsolidus relationships in the system K2O-CaO-Al2O3-SiO2-H2O have been experimentally investigated at pressures up to 20 kbars. The equilibria discussed involve the phases anorthite, sanidine, zoisite, muscovite, quartz, kyanite, gas, and melt and two invariant points: Point [Ky] with the phases An, Or, Zo, Ms, Qz, Vapor, and Melt; point [Or] with An, Zo, Ms, Ky, Qz, Vapor, and Melt. The invariant point [Ky] at 675° C and 8.7 kbars marks the lowest solidus temperature of the system investigated. At pressures above this point the hydrated phases zoisite and muscovite are liquidus phases and the solidus temperatures increase with increasing pressure. At 20 kbars beginning of melting occurs at 740 °C. The solidus temperatures of the quinary system K2O-CaO-Al2O3-SiO2-H2O are almost 60° C (at 20 kbars) and 170° C (at 2kbars) below those of the limiting quaternary system CaO-Al2O3-SiO2-H2O. The maximum water pressure at which anorthite is stable is lowered from 14 to 8.7 kbars in the presence of sanidine. The stability limits of anorthite+ vapor and anorthite+sanidine+vapor at temperatures below 700° C are almost parallel and do not intersect. In the wide temperature — pressure range at pressures above the reaction An+Or+Vapor = Zo+Ms+Qz and temperatures below the melting curve of Zo+Ms+Ky+Qz+Vapor, the feldspar assemblage anorthite+sanidine is replaced by the hydrated phases zoisite and muscovite plus quartz. CaO-Al2O3-SiO2-H2O. Knowledge of the melting relationships involving the minerals zoisite and muscovite contributes to our understanding of the melting processes occuring in the deeper parts of the crust. Beginning of melting in granites and granodiorites depends on the composition of plagioclase. The solidus temperatures of all granites and granodiorites containing plagioclases of intermediate composition are higher than those of the Ca-free alkali feldspar granite system and below those of the Na-free system discussed in this

  12. Syntheses and crystal structures of two new hydrated borates, Zn{sub 8}[(BO{sub 3}){sub 3}O{sub 2}(OH){sub 3}] and Pb[B{sub 5}O{sub 8}(OH)].1.5H{sub 2}O

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

    Chen Xuean; Zhao Yinghua; Chang Xinan

    Two new hydrated borates, Zn{sub 8}[(BO{sub 3}){sub 3}O{sub 2}(OH){sub 3}] and Pb[B{sub 5}O{sub 8}(OH)].1.5H{sub 2}O, have been prepared by hydrothermal reactions at 170 {sup o}C. Single-crystal X-ray structural analyses showed that Zn{sub 8}[(BO{sub 3}){sub 3}O{sub 2}(OH){sub 3}] crystallizes in a non-centrosymmetric space group R32 with a=8.006(2) A, c=17.751(2) A, Z=3 and Pb[B{sub 5}O{sub 8}(OH)].1.5H{sub 2}O in a triclinic space group P1-bar with a=6.656(2) A, b=6.714(2) A, c=10.701(2) A, {alpha}=99.07(2){sup o}, {beta}=93.67(2){sup o}, {gamma}=118.87(1){sup o}, Z=2. Zn{sub 8}[(BO{sub 3}){sub 3}O{sub 2}(OH){sub 3}] represents a new structure type in which Zn-centered tetrahedra are connected via common vertices leading to helical ribbons {submore » {infinity}} {sup 1}[Zn{sub 8}O{sub 15}(OH){sub 3}]{sup 17-} that pack side by side and are further condensed through sharing oxygen atoms to form a three-dimensional {sub {infinity}} {sup 3}[Zn{sub 8}O{sub 11}(OH){sub 3}]{sup 9-} framework. The boron atoms are incorporated into the channels in the framework to complete the final structure. Pb[B{sub 5}O{sub 8}(OH)].1.5H{sub 2}O is a layered compound containing double ring [B{sub 5}O{sub 8}(OH)]{sup 2-} building units that share exocyclic oxygen atoms to form a two-dimensional layer. Symmetry-center-related layers are stacked along the c-axis and held together by interlayer Pb{sup 2+} ions and water molecules via electrostatic and hydrogen bonding interactions. The IR spectra further confirmed the existence of both triangular BO{sub 3} and OH groups in Zn{sub 8}[(BO{sub 3}){sub 3}O{sub 2}(OH){sub 3}], and BO{sub 3}, BO{sub 4}, OH groups as well as guest water molecules in Pb[B{sub 5}O{sub 8}(OH)].1.5H{sub 2}O. -- Zn{sub 8}[(BO{sub 3}){sub 3}O{sub 2}(OH){sub 3}] represents a new structure type in which Zn-centered tetrahedra are connected via common vertices to form a three-dimensional framework. The boron atoms are incorporated into the channels in the framework to

  13. Simulating equilibrium processes in the Ga(NO3)3-H2O-NaOH system

    NASA Astrophysics Data System (ADS)

    Fedorova, E. A.; Bakhteev, S. A.; Maskaeva, L. N.; Yusupov, R. A.; Markov, V. F.

    2016-06-01

    Equilibrium processes in the Ga(NO3)3-H2O-NaOH system are simulated with allowance for the formation of precipitates of various compositions using experimental data from potentiometric titration and theoretical studies. The values of the instability constants are calculated along with the stoichiometric compositions of the resulting compounds. It is found that pH ranges of 1.0 to 4.3 and 12.0 to 14.0 are best for the deposition of gallium chalcogenide films.

  14. A second polymorph with composition Co3(PO4)2·H2O

    PubMed Central

    Lee, Young Hoon; Clegg, Jack K.; Lindoy, Leonard F.; Lu, G. Q. Max; Park, Yu-Chul; Kim, Yang

    2008-01-01

    Single crystals of Co3(PO4)2·H2O, tricobalt(II) bis­[ortho­phosphate(V)] monohydrate, were obtained under hydro­thermal conditions. The compound is the second polymorph of this composition and is isotypic with its zinc analogue, Zn3(PO4)2·H2O. Three independent Co2+ cations are bridged by two independent orthophosphate anions. Two of the metal cations exhibit a distorted tetra­hedral coordination while the third exhibits a considerably distorted [5 + 1] octa­hedral coordination environment with one very long Co—O distance of 2.416 (3) Å. The former cations are bonded to four different phosphate anions, and the latter cation is bonded to four anions (one of which is bidentate) and one water mol­ecule, leading to a framework structure. Additional hydrogen bonds of the type O—H⋯O stabilize this arrangement. PMID:21200979

  15. [Influences of R2O-Al2O3-B2O3-SiO2 system glass and superfine alpha-Al2O3 on the sintering and phase transition of hydroxyapatite ceramics].

    PubMed

    Wang, Zhiqiang; Chen, Xiaoxu; Cai, Yingji; Lü, Bingling

    2003-06-01

    The effects of R2O-Al2O3-B2O3-SiO2 system glass and superfine alpha-Al2O3 on the sintering and phase transition of hydroxyapatite (HAP) ceramics were assessed. The results showed that alpha-Al2O3 impeded the sintering of HAP and raised the sintering temperature. When glass and alpha-Al2O3 were used together to reinforce HAP ceramics, better results could be obtained; the bending strength of multiphase HAP ceramics approached 106 MPa when 10% (wt) alpha-Al2O3 and 20%(wt) glass were used and sintered at 1200 for 1 h.

  16. Polyoxometal cations within polyoxometalate anions. Seven-coordinate uranium and zirconium heteroatom groups in [(UO2)12(μ3-O)4(μ2-H2O)12(P2W15O56)4]32- and [Zr4(μ3-O)22-OH)2(H2O)4 (P2W16O59)2]14-

    NASA Astrophysics Data System (ADS)

    Gaunt, Andrew J.; May, Iain; Collison, David; Travis Holman, K.; Pope, Michael T.

    2003-08-01

    Two new composite polyoxotungstate anions with unprecedented structural features, [(UO2)12(μ3-O)4(μ2-H2O)12(P2W15O56)4]32- (1) and [Zr4(μ3-O)22-OH)2(H2O)4 (P2W16O59)2]14- (2) contain polyoxo-uranium and -zirconium clusters as bridging units. The anions are synthesized by reaction of Na12[P2W15O56] with solutions of UO2(NO3)2 and ZrCl4. The structure of 1 in the sodium salt contains four [P2W15O56]12- anions assembled into an overall tetrahedral cluster by means of trigonal bridging groups formed by three equatorial-edge-shared UO7 pentagonal bipyramids. The structure of anion 2 consists of a centrosymmetric assembly of two [P2W16O59]12- anions linked by a {Zr4O2(OH)2(H2O)4}10+ cluster. Both complexes in solution yield the expected two-line 31P-NMR spectra with chemical shifts of -2.95, -13.58 and -6.45, -13.69 ppm, respectively.

  17. Comparison of pharmaceutical abatement in various water matrices by conventional ozonation, peroxone (O3/H2O2), and an electro-peroxone process.

    PubMed

    Wang, Huijiao; Zhan, Juhong; Yao, Weikun; Wang, Bin; Deng, Shubo; Huang, Jun; Yu, Gang; Wang, Yujue

    2018-03-01

    Pharmaceutical abatement in a groundwater (GW), surface water (SW), and secondary effluent (SE) by conventional ozonation, the conventional peroxone (O 3 /H 2 O 2 ), and the electro-peroxone (E-peroxone) processes was compared in batch tests. SE had significantly more fast-reacting dissolved organic matter (DOM) moieties than GW and SW. Therefore, O 3 decomposed much faster in SE than in GW and SW. At specific ozone doses of 0.5-1.5 mg O 3 /mg dissolved organic carbon (DOC), the application of O 3 /H 2 O 2 and E-peroxone process (by adding external H 2 O 2 stocks or in-situ generating H 2 O 2 from cathodic O 2 reduction during ozonation) similarly enhanced the OH yield from O 3 decomposition by ∼5-12% and 5-7% in GW and SW, respectively, compared to conventional ozonation. In contrast, due to the slower reaction kinetics of O 3 with H 2 O 2 than O 3 with fast-reacting DOM moieties, the addition or electro-generation of H 2 O 2 hardly increased the OH yield (<4% increases) in SE. Corresponding to the changes in the OH yields, the abatement efficiencies of ozone-resistant pharmaceuticals (ibuprofen and clofibric acid) increased evidently in GW (up to ∼14-18% at a specific ozone dose of 1.5 mg O 3 /mg DOC), moderately in SW (up to 6-10% at 0.5 mg O 3 /mg DOC), and negligibly in SE during the O 3 /H 2 O 2 and E-peroxone treatment compared to conventional ozonation. These results indicate that similar to the conventional O 3 /H 2 O 2 process, the E-peroxone process can more pronouncedly enhance O 3 transformation to OH, and thus increase the abatement efficiency of ozone-resistant pharmaceuticals in water matrices exerting relatively high ozone stability (e.g., groundwater and surface water with low DOM contents). Therefore, by installing electrodes in existing ozone reactors, the E-peroxone process may provide a convenient way to enhance pharmaceutical abatement in drinking water applications, where groundwater and surface water with low DOM contents are used as

  18. Mixed-metal uranium(VI) iodates: hydrothermal syntheses, structures, and reactivity of Rb[UO(2)(CrO(4))(IO(3))(H(2)O)], A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K, Rb, Cs), and K(2)[UO(2)(MoO(4))(IO(3))(2)].

    PubMed

    Sykora, Richard E; McDaniel, Steven M; Wells, Daniel M; Albrecht-Schmitt, Thomas E

    2002-10-07

    The reactions of the molecular transition metal iodates A[CrO(3)(IO(3))] (A = K, Rb, Cs) with UO(3) under mild hydrothermal conditions provide access to four new, one-dimensional, uranyl chromatoiodates, Rb[UO(2)(CrO(4))(IO(3))(H(2)O)] (1) and A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K (2), Rb (3), Cs (4)). Under basic conditions, MoO(3), UO(3), and KIO(4) can be reacted to form K(2)[UO(2)(MoO(4))(IO(3))(2)] (5), which is isostructural with 2 and 3. The structure of 1 consists of one-dimensional[UO(2)(CrO(4))(IO(3))(H(2)O)](-) ribbons that contain uranyl moieties bound by bridging chromate and iodate anions as well as a terminal water molecule to create [UO(7)] pentagonal bipyramidal environments around the U(VI) centers. These ribbons are separated from one another by Rb(+) cations. When the iodate content is increased in the hydrothermal reactions, the terminal water molecule is replaced by a monodentate iodate anion to yield 2-4. These ribbons can be further modified by replacing tetrahedral chromate anions with MoO(4)(2)(-) anions to yield isostructural, one-dimensional [UO(2)(MoO(4))(IO(3))(2)](2)(-) ribbons. Crystallographic data: 1, triclinic, space group P(-)1, a = 7.3133(5) A, b = 8.0561(6) A, c = 8.4870(6) A, alpha = 88.740(1) degrees, beta = 87.075(1) degrees, gamma = 71.672(1) degrees, Z = 2; 2, monoclinic, space group P2(1)/c, a = 11.1337(5) A, b = 7.2884(4) A, c = 15.5661(7) A, beta = 107.977(1) degrees, Z = 4; 3, monoclinic, space group P2(1)/c, a = 11.3463(6) A, b = 7.3263(4) A, c = 15.9332(8) A, beta = 108.173(1) degrees, Z = 4; 4, monoclinic, space group P2(1)/n, a = 7.3929(5) A, b = 8.1346(6) A, c = 22.126(2) A, beta = 90.647(1) degrees, Z = 4; 5, monoclinic, space group P2(1)/c, a = 11.3717(6) A, b = 7.2903(4) A, c = 15.7122(8) A, beta = 108.167(1) degrees, Z = 4.

  19. Analysis of grain boundary phase devitrification of Y2O3- and Al2O3-doped Si3N4

    NASA Technical Reports Server (NTRS)

    Hench, L. L.; Vaidyanathan, P. N.

    1983-01-01

    The present study has the objective to show that a Fourier Transform IR (FTIR) spectrometer in a single-beam reflection mode can be used for direct comparison of fractured vs nonfractured Si3N4 surfaces. This can be done because the FTIR method permits a digital summation of nearly 1000 scans of the fracture surface. Commercial-grade Si3N4, Y2O3, and Al2O3 were used in the study. The samples were heat treated in a vacuum induction heating furnace at either 1000 C for 10 h or 1200 C for 10 h each. Use of Fourier transform IR reflection spectroscopic analysis and X-ray diffraction shows that 10 h at 1200 C is sufficient to devitrify the amorphous grain boundary phase of Si3N4 containing 15 percent Y2O3 + 2 percent Al2O3 densification aids.

  20. Impedance and AC conductivity studies of Sm3+ substituted 0.8Ba0.2(Bi0.5K0.5)TiO3 lead free ceramics

    NASA Astrophysics Data System (ADS)

    Sastry, C. V. S. S.; Ramesh, M. N. V.; Ramesh, K. V.

    2017-07-01

    Samarium substituted 0.8Ba0.2(Bi0.5K0.5)TiO3 (here after abbreviated as BTBKT-20) lead free ceramics with composition 0.8Ba0.2(Bi0.5(1-x)Sm0.5xK0.5)TiO3 (where x=0.01,0.03,0.05) lead free ceramics have been prepared by solid state reaction and followed by high energy ball milling process. The present paper focuses the impedance and ac conductivity studies of Sm substituted BTBKT-20 lead free ceramics. Impedance spectroscopic studies revealthat temperature dependent relaxation process. Single depressed semi circle was observed in Cole-Cole plots, indicates non-Debye kind of relaxation process. Maximum grain resistance was observed for x=0.03 Sm substituted BTBKT-20 sample. Frequency and temperature dependent AC conductivity was calculated and it found to obey the universal Jonscher's power law and the values of activation energies suggest that conduction is ionic in nature.

  1. Noteworthy performance of La(1-x)Ca(x)MnO3 perovskites in generating H2 and CO by the thermochemical splitting of H2O and CO2.

    PubMed

    Dey, Sunita; Naidu, B S; Govindaraj, A; Rao, C N R

    2015-01-07

    Perovskite oxides of the composition La1-xCaxMnO3 (LCM) have been investigated for the thermochemical splitting of H2O and CO2 to produce H2 and CO, respectively. The study was carried out in comparison with La1-xSrxMnO3, CeO2 and other oxides. The LCM system exhibits superior characteristics in high-temperature evolution of oxygen, and in reducing CO2 to CO and H2O to H2. The best results were obtained with La0.5Ca0.5MnO3 whose performance is noteworthy compared to that of other oxides including ceria. The orthorhombic structure of LCM seems to be a crucial factor.

  2. Electron-temperature dependence of the recombination of H3O+(H2O)n ions with electrons

    NASA Technical Reports Server (NTRS)

    Johnsen, R.

    1993-01-01

    The T(e) dependence of the recombination of H3O+(H2O)n cluster-ions with electrons has been measured in an afterglow experiment in which the electrons were heated by a radio-frequency electric field. The recombination coefficients were found to vary with T(e) as about T(e) exp -1/2 in better agreement with theoretical expectations than earlier results of microwave-afterglow measurements.

  3. Structure and vibrational properties of the dominant O-H center in β-Ga2O3

    NASA Astrophysics Data System (ADS)

    Weiser, Philip; Stavola, Michael; Fowler, W. Beall; Qin, Ying; Pearton, Stephen

    2018-06-01

    Hydrogen has a strong influence on the electrical properties of transparent conducting oxides where it can give rise to shallow donors and can passivate deep compensating defects. We have carried out infrared absorption experiments on H- and D-doped β-Ga2O3 that involve temperature- and polarization-dependent effects as well as relative H- and D-concentrations to probe the defect structures that hydrogen can form. The results of analysis of these data, coupled with detailed theoretical calculations, show that the dominant O-H vibrational line observed at 3437 cm-1 for hydrogenated Ga2O3 is due to a relaxed VGa-2H center.

  4. Structure–property relations of orthorhombic [(CH{sub 3}){sub 3}NCH{sub 2}COO]{sub 2}(CuCl{sub 2}){sub 32H{sub 2}O

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

    Haussühl, Eiken, E-mail: haussuehl@kristall.uni-frankfurt.de; Schreuer, Jürgen; Wiehl, Leonore

    2014-04-01

    Large single crystals of orthorhombic [(CH{sub 3}){sub 3}NCH{sub 2}COO]{sub 2}(CuCl{sub 2}){sub 32H{sub 2}O with dimensions up to 40×40×30 mm{sup 3} were grown from aqueous solutions. The elastic and piezoelastic coefficients were derived from ultrasonic resonance frequencies and their shifts upon variation of pressure, respectively, using the plate-resonance technique. Additionally, the coefficients of thermal expansion were determined between 95 K and 305 K by dilatometry. The elastic behaviour at ambient conditions is dominated by the 2-dimensional network of strong hydrogen bonds within the (001) plane leading to a corresponding pseudo-tetragonal anisotropy of the longitudinal elastic stiffness. The variation of elastic propertiesmore » with pressure, however, as well as the thermal expansion shows strong deviations from the pseudo-tetragonal symmetry. These deviations are probably correlated with tilts of the elongated tri-nuclear betaine–CuCl{sub 2}–water complexes. Neither the thermal expansion nor the specific heat capacity gives any hint on a phase transition in the investigated temperature range. - Graphical abstract: Single crystal of orthorhombic [(CH{sub 3}){sub 3}NCH{sub 2}COO]{sub 2}(CuCl{sub 2}){sub 32H{sub 2}O. - Highlights: • Large single crystals (40 ×40 ×30 mm{sup 3}) of [(CH{sub 3}){sub 3}NCH{sub 2}COO]{sub 2}(CuCl{sub 2}){sub 32H{sub 2}O were grown. • The elastic and piezoelastic coefficients were derived from ultrasonic resonance frequencies. • Thermal expansion (95 K–305 K) and heat capacity (113 K–323 K) were determined. • The orthorhombic structure shows pseudo-tetragonal elastic anisotropy at ambient conditions. • The crystal structure is stable in the investigated range (1–1600 bar, 95–303 K)« less

  5. Partial phase diagram for the system NH3-H2O - The water-rich region

    NASA Technical Reports Server (NTRS)

    Johnson, M. L.; Schwake, A.; Nicol, M.

    1984-01-01

    Phase boundaries of the H2O-NH3 system for (NH3)/x/(H2O)/1-x/ have been determined with diamond-anvil cells for mixtures in two composition ranges: (1) for x in the range from 0 to 0.3, at pressures up to 4 GPa at 21 C, and (2) for x in the range from 0.46 to 0.50, at pressures up to 5 GPa from 150 to 400 K. Phases were identified visually with a microscope and polarized optics. The NH3.2(H2O) phase is strongly anisotropic with a much smaller refractive index than that of ice VII and cracks in two nonperpendicular networks. NH3.H2O has a refractive index closer to that of Ice VII and does not appear to form cracks. Both phases are colorless. Phase boundaries were determined on both increasing and decreasing pressures, and compositions of the ammonia ices were determined by estimating relative amounts of water and ammonia ices at known overall compositions. For low-ammonia compositions (x equal to or less than 0.15), the following assemblages succedd one another as pressure increases: liquid; liquid and Ice VI (at 1.0 + GPa); liquid and Ice VII (at 2.1 GPa); Ice VII and NH3.H2O (at 3.5 GPa). For x in the range from 0.15 to 0.30, the water ice and liquid fields are replaced by the NH3.2(H2O) and liquid field at pressures down to 1.0 GPa and lower.

  6. Borate mineral assemblages in the system Na2OCaOMgOB2O3H2O

    USGS Publications Warehouse

    Christ, C.L.; Truesdell, A.H.; Erd, Richard C.

    1967-01-01

    he significant known hydrated borate mineral assemblages (principally of the western United States) in the system Na2OCaOz.sbnd;MgOB2O3H2O are expressible in three ternary composition diagrams. Phase rule interpretation of the diagrams is consistent with observation, if the activity of H2O is generally considered to be determined by the geologic environment. The absence of conflicting tie-lines on a diagram indicates that the several mineral assemblages of the diagram were formed under relatively narrow ranges of temperature and pressure. The known structural as well as empirical formulas for the minerals are listed, and the more recent (since 1960) crystal structure findings are discussed briefly. Schematic Gibbs free energy-composition diagrams based on known solubility-temperature relations in the systems Na2B4O7-H2O and Na2B4O7-NaCl-H2O, are highly useful in the interpretation and prediction of the stability relations in these systems; in particular these diagrams indicate clearly that tincalconite, although geologically important, is everywhere a metastable phase. Crystal-chemical considerations indicate that the same thermodynamic and kinetic behavior observed in the Na2B4O7-H2O system will hold in the Ca2B6O11-H2O system. This conclusion is confirmed by the petrologic evidence. The chemical relations among the mineral assemblages of a ternary diagram are expressed by a schematic "activity-activity" diagram. These activity-activity diagrams permit the tracing-out of the paragenetic sequences as a function of changing cation and H2O activities. ?? 1967.

  7. Site-specific vibrational spectral signatures of water molecules in the magic H3O+(H2O)20 and Cs+(H2O)20 clusters

    PubMed Central

    Fournier, Joseph A.; Wolke, Conrad T.; Johnson, Christopher J.; Johnson, Mark A.; Heine, Nadja; Gewinner, Sandy; Schöllkopf, Wieland; Esser, Tim K.; Fagiani, Matias R.; Knorke, Harald; Asmis, Knut R.

    2014-01-01

    Theoretical models of proton hydration with tens of water molecules indicate that the excess proton is embedded on the surface of clathrate-like cage structures with one or two water molecules in the interior. The evidence for these structures has been indirect, however, because the experimental spectra in the critical H-bonding region of the OH stretching vibrations have been too diffuse to provide band patterns that distinguish between candidate structures predicted theoretically. Here we exploit the slow cooling afforded by cryogenic ion trapping, along with isotopic substitution, to quench water clusters attached to the H3O+ and Cs+ ions into structures that yield well-resolved vibrational bands over the entire 215- to 3,800-cm−1 range. The magic H3O+(H2O)20 cluster yields particularly clear spectral signatures that can, with the aid of ab initio predictions, be traced to specific classes of network sites in the predicted pentagonal dodecahedron H-bonded cage with the hydronium ion residing on the surface. PMID:25489068

  8. Site-specific vibrational spectral signatures of water molecules in the magic H 3O +(H 2O) 20 and Cs +(H 2O) 20 clusters

    DOE PAGES

    Fournier, Joseph A.; Wolke, Conrad T.; Johnson, Christopher J.; ...

    2014-12-08

    Here, theoretical models of proton hydration with tens of water molecules indicate that the excess proton is embedded on the surface of clathrate-like cage structures with one or two water molecules in the interior. The evidence for these structures has been indirect, however, because the experimental spectra in the critical H-bonding region of the OH stretching vibrations have been too diffuse to provide band patterns that distinguish between candidate structures predicted theoretically. Here we exploit the slow cooling afforded by cryogenic ion trapping, along with isotopic substitution, to quench water clusters attached to the H 3O + and Cs +more » ions into structures that yield well-resolved vibrational bands over the entire 215- to 3,800-cm -1 range. The magic H 3O +(H 2O) 20 cluster yields particularly clear spectral signatures that can, with the aid of ab initio predictions, be traced to specific classes of network sites in the predicted pentagonal dodecahedron H-bonded cage with the hydronium ion residing on the surface.« less

  9. Orientational disorder in sodium cadmium trifluoride trihydrate, NaCdF{sub 3}.3H{sub 2}O

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

    Smith, Robert W.; Mar, Arthur; Liu Jianjun

    2006-03-09

    Attempts to synthesize the hypothetical anhydrous fluoroperovskite NaCdF{sub 3}, which has been predicted to be stable, resulted instead in a hydrated fluoride of nominal composition NaCdF{sub 3}.3H{sub 2}O. It decomposes to sodium fluoride, cadmium fluoride, and water at 60deg. C. Its structure has been determined by single-crystal X-ray diffraction. Na{sub 0.92(2)}Cd{sub 1.08}F{sub 3.08}.2.92H{sub 2}O crystallizes in the cubic space group Fm3-bar m with a=8.2369(4)A and Z=4. The structure is based on the NaSbF{sub 6}-type (an ordered variant of the ReO{sub 3}-type) and features tilted sodium- and cadmium-centred octahedra that are linked by shared vertices to form a three-dimensional network. Substitutionalmore » disorder occurs on the nonmetal site, which is occupied by both F and O atoms, and on one of the metal sites, which is occupied by 92% Na and 8% Cd. A four-fold orientational disorder of the tilted octahedra is manifested as partial occupancy (25%) of the nonmetal site. A scheme to synthesize the anhydrous fluoride is presented.« less

  10. Tris(5,6-dimethyl-1H-benzimidazole-κN 3)(pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)nickel(II)

    PubMed Central

    Li, Yue-Hua; Li, Feng-Feng; Liu, Xin-Hua; Zhao, Ling-Yan

    2012-01-01

    The title mononuclear complex, [Ni(C7H3NO4)(C9H10N2)3], shows a central NiII atom which is coordinated by two carboxyl­ate O atoms and the N atom from a pyridine-2,6-dicarboxyl­ate ligand and by three N atoms from different 5,6-dimethyl-1H-­benzimidazole ligands in a distorted octa­hedral geometry. The crystal structure shows intermolecular N—H⋯O hydrogen bonds. PMID:22719301

  11. Crystal structure, quantum mechanical investigation, IR and NMR spectroscopy of two new organic perchlorates: (C6H18N3)·(ClO4)3H2O (I) and (C9H11N2)·ClO4(II)

    NASA Astrophysics Data System (ADS)

    Bayar, I.; Khedhiri, L.; Soudani, S.; Lefebvre, F.; Ferretti, V.; Ben Nasr, C.

    2018-06-01

    The reaction of perchloric acid with 1-(2-aminoethyl)piperazine or 5,6-dimethyl-benzimidazole results in the formation of 1-(2-amonioethyl)piperazine-1,4-dium triperchlorate hydrate (C6H18N3)·(ClO4)3·H2O (I) or 5,6-dimethyl-benzylimidazolium perchlorate (C9H11N2)·ClO4(II). Both compounds were fully structurally characterized including single crystal X-ray diffraction analysis. Compound (I) crystallizes in the centrosymmetric triclinic space group P 1 bar with the lattice parameters a = 7.455 (2), b = 10.462 (2), c = 10.824 (2) Å, α = 80.832 (2), β = 88.243 (2), γ = 88.160 (2) °, Z = 2 and V = 832.77 (3) Å3. Compound (II) has been found to belong to the P21/c space group of the monoclinic system, with a = 7.590 (3), b = 9.266 (3), c = 16.503 (6) Å, β = 107.38 (2) °, V = 1107.69 (7) Å3 and Z = 4. The structures of (I) and (II) consist of slightly distorted [ClO4]- tetrahedra anions and 1-(2-amonioethyl)piperazine-1,4-dium trication (I) or 5,6-dimethyl-benzylimidazolium cations (II) and additionally a lattice water in (I). The crystal structures of (I) and (II) exhibit complex three-dimensional networks of H-bonds connecting all their components. In the atomic arrangement of (I), the ClO4- anions form corrugated chains, while in (II) the atomic arrangement exhibits wide pseudo-hexagonal channels of ClO4 tetrahedra including the organic entities. The lattice water serves as a link between pairs of cations and pairs of anions via several Osbnd H⋯O and N-H⋯O interactions in compound (I). The vibrational absorption bands were identified by infrared spectroscopy. These compounds were also investigated by solid-state 13C, 35Cl and 15N NMR spectroscopy. DFT calculations allowed the attribution of the IR and NMR bands. Intermolecular interactions were investigated by Hirshfeld surfaces. Electronic properties such as HOMO and LUMO energies were derived.

  12. Neuroligin-3 protects retinal cells from H2O2-induced cell death via activation of Nrf2 signaling.

    PubMed

    Li, Xiu-Miao; Huang, Dan; Yu, Qing; Yang, Jian; Yao, Jin

    2018-05-25

    Intensified oxidative stress can cause severe damage to human retinal pigment epithelium (RPE) cells and retinal ganglion cells (RGCs). The potential effect of neuroligin-3 (NLGN3) against the process is studied here. Our results show that NLGN3 efficiently inhibited hydrogen peroxide (H 2 O 2 )-induced death and apoptosis in human RPE cells and RGCs. H 2 O 2 -induced reactive oxygen species (ROS) production, lipid peroxidation and DNA damage in retinal cells were alleviated by NLGN3. NLGN3 activated nuclear-factor-E2-related factor 2 (Nrf2) signaling, enabling Nrf2 protein stabilization, nuclear translocation and expression of key anti-oxidant enzymes (HO1, NOQ1 and GCLC) in RPE cells and RGCs. Further results demonstrate that NLGN3 activated Akt-mTORC1 signaling in retinal cells. Conversely, Akt-mTORC1 inhibitors (RAD001 and LY294002) reduced NLGN3-induced HO1, NOQ1 and GCLC mRNA expression. Significantly, Nrf2 silencing by targeted shRNAs reversed NLGN3-induced retinal cytoprotection against H 2 O 2 . We conclude that NLGN3 activates Nrf2 signaling to protect human retinal cells from H 2 O 2 . NLGN3 could be further tested as a valuable retinal protection agent. Copyright © 2018 Elsevier Inc. All rights reserved.

  13. Crystal Structures and Thermal Properties of Two Transition-Metal Compounds {[Ni(DNI)2(H2O)3][Ni(DNI)2 (H2O)4]}·6H2O and Pb(DNI)2(H2O)4 (DNI = 2,4-Dinitroimidazolate)

    PubMed Central

    Zhang, Guo-Fang; Cai, Mei-Yu; Jing, Ping; He, Chong; Li, Ping; Zhao, Feng-Qi; Li, Ji-Zhen; Fan, Xue-Zhong; Ng, Seik Weng

    2010-01-01

    Two transition-metal compounds derived from 2,4-dinitroimidazole, {[Ni(DNI)2(H2O)3][Ni(DNI)2 (H2O)4]}·6H2O, 1, and Pb(DNI)2(H2O)4, 2, were characterized by elemental analysis, FT-IR, TG-DSC and X-ray single-crystal diffraction analysis. Crystal data for 1: monoclinic, space group C2/c, a = 26.826(3), b = 7.7199(10), c = 18.579(2) Å, β = 111.241(2)° and Z = 4; 2: monoclinic, space group C2/c, a = 6.5347(6), b = 17.1727(17), c = 14.1011(14) Å, β = 97.7248(10) and Z = 4. Compound 1 contains two isolated nickel centers in its structure, one being six-coordinate and another five-coordinate. The structure of 2 contains a lead (II) center surrounded by two chelating DNI ligands and four water molecules in distorted square-antiprism geometry. The abundant hydrogen bonds in two compounds link the molecules into three-dimensional network and stabilize the molecules. The TG-DSC analysis reveals that the first step is the loss of water molecules and the final residue is the corresponding metal oxides and carbon. PMID:20526419

  14. The Bean model and ac losses in Bi{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10}/Ag tapes

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

    Suenaga, M.; Chiba, T.; Wiesmann, H.J.

    The Bean model is almost solely used to interpret ac losses in the powder-in-tube processed composite conductor, Bi{sub 2}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10}/Ag. In order to examine the limits of the applicability of the model, a detailed comparison was made between the values of critical current density J{sub c} for Bi(2223)/Ag tapes which were determined by standard four-probe-dc measurement, and which were deduced from the field dependence of the ac losses utilizing the model. A significant inconsistency between these values of J{sub c} were found, particularly at high fields. Possible sources of the discrepancies are discussed.

  15. Impedance spectroscopy of V2O5-Bi2O3-BaTiO3 glass-ceramics

    NASA Astrophysics Data System (ADS)

    Al-syadi, Aref M.; Yousef, El Sayed; El-Desoky, M. M.; Al-Assiri, M. S.

    2013-12-01

    The glasses within composition as: (80 - x)V2O5/20Bi2O3/xBaTiO3 with x = 2.5, 5, 7.5 and 10 mol% have been prepared. The glass transition (Tg) increases with increasing BaTiO3 content. Synthesized glasses ceramic containing BaTi4O9, Ba3TiV4O15 nanoparticles of the order of 25-35 nm and 30-46 nm, respectively were estimated using XRD. The dielectric properties over wide ranges of frequencies and temperatures were investigated as a function of BaTiO3 content by impedance spectroscopy measurements. The hopping frequency, ωh, dielectric constant, ɛ', activation energies for the DC conduction, Eσ, the relaxation process, Ec, and stretched exponential parameter β of the glasses samples have been estimated. The, ωh,β, decrease from 51.63 to 0.31 × 106 (s-1), 0.84 to 0.79 with increasing BaTiO3 respectively. Otherwise, the Eσ, increase from 0.279 to 0.306 eV with increasing BaTiO3. The value of dielectric constant equal 9.5·103 for the 2.5BaTiO3/77.5V2O5/20Bi2O3 glasses-ceramic at 330 K for 1 KHz which is ten times larger than that of same glasses composition. Finally the relaxation properties of the investigated glasses are presented in the electric modulus formalism, where the relaxation time and the respective activation energy were determined.

  16. Structure-property relations of orthorhombic [(CH3)3NCH2COO]2(CuCl2)3 · 2H2 O

    NASA Astrophysics Data System (ADS)

    Haussühl, Eiken; Schreuer, Jürgen; Wiehl, Leonore; Paulsen, Natalia

    2014-04-01

    Large single crystals of orthorhombic [(CH3)3NCH2COO]2(CuCl2)3 · 2H2 O with dimensions up to 40×40×30 mm3 were grown from aqueous solutions. The elastic and piezoelastic coefficients were derived from ultrasonic resonance frequencies and their shifts upon variation of pressure, respectively, using the plate-resonance technique. Additionally, the coefficients of thermal expansion were determined between 95 K and 305 K by dilatometry. The elastic behaviour at ambient conditions is dominated by the 2-dimensional network of strong hydrogen bonds within the (001) plane leading to a corresponding pseudo-tetragonal anisotropy of the longitudinal elastic stiffness. The variation of elastic properties with pressure, however, as well as the thermal expansion shows strong deviations from the pseudo-tetragonal symmetry. These deviations are probably correlated with tilts of the elongated tri-nuclear betaine-CuCl2-water complexes. Neither the thermal expansion nor the specific heat capacity gives any hint on a phase transition in the investigated temperature range.

  17. Metastable α-AgVO3 microrods as peroxidase mimetics for colorimetric determination of H2O2.

    PubMed

    Wang, Yi; Zhang, Dun; Wang, Jin

    2017-12-01

    Single phase metastable α-AgVO 3 microrods with high crystallinity, tetragonal rod-like microstructure, uniform particle size distribution, and good dispersion were synthesized by direct coprecipitation at room temperature. They are shown to be viable peroxidase mimics that catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine in the presence of H 2 O 2 . Kinetic analysis indicated typical Michaelis-Menten catalytic behavior. The findings were used to design a colorimetric assay for H 2 O 2 , best measured at 652 nm. The method has a linear response in the 60 to 200 μM H 2 O 2 concentration range, with a 2 μM detection limit. Benefitting from the chemical stability of the microrods, the method is well reproducible. It also is easily performed and highly specific. Graphic abstract Single phase metastable α-AgVO 3 microrods with high crystallinity, tetragonal rod-like microstructure, uniform particle size distribution, and good dispersion can efficiently catalyze the oxidation reaction of peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H 2 O 2 to produce a blue color change.

  18. A new method for CH3O2 and C2H5O2 radical detection and kinetic studies of the CH3O2 self-reaction in HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry)

    NASA Astrophysics Data System (ADS)

    Onel, L. C.; Brennan, A.; Ingham, T.; Kirk, D.; Leggott, A.; Seakins, P. W.; Whalley, L.; Heard, D. E.

    2016-12-01

    Peroxy (RO2) radicals such as methylperoxy (CH3O2) and ethylperoxy (C2H5O2) are significant atmospheric species in the ozone formation in the presence of NO. At low concentrations of NO, the self-reaction of RO2 and RO2 + HO2 are important radical termination reactions. Despite their importance, at present typically only the sum of RO2 is measured in the atmosphere, making no distinction between different RO2 species.A new method has been developed for the direct detection of CH3O2 and C2H5O2 by FAGE (Fluorescence Assay by Gas Expansion) by titrating the peroxy radicals to RO (R = CH3 and C2H5) by reaction with NO and then detecting the resultant RO by laser induced fluorescence. The method has the potential to directly measure atmospheric levels of CH3O2 and potentially other RO2 species. The limit of detection is 3.8 × 108 molecule cm-3 for CH3O2 and 4.9 × 109 molecule cm-3 for C2H5O2 for a signal-to-noise ratio of 2 and a 4 min averaging time. The method has been used for time-resolved monitoring of CH3O2 during its self-reaction within HIRAC at 1 bar and at room temperature to determine a rate coefficient that is lower than the range of the previous results obtained by UV absorption measurements (http://iupac.pole-ether.fr/). A range of products of the CH3O2 self-reaction were also observed for the two reaction channels, (a) leading to formaldehyde and methanol and (b) forming methoxy (CH3O) radicals, over a range of temperatures from 296 - 340 K: CH3O and HO2 radicals (from reaction of CH3O + O2) were monitored by FAGE, formaldehyde was measured by FAGE and FTIR, and methanol was observed by FTIR. Good agreement was observed between the FTIR and FAGE measurements of formaldehyde. Using the concentrations of methanol and formaldehyde, the branching ratios at room temperature have been determined and are in very good agreement with the values recommended by IUPAC. Little temperature dependence of the branching ratios has been observed from 296 K to 340 K.

  19. Abrogation of Gli3 expression suppresses the growth of colon cancer cells via activation of p53

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

    Kang, Han Na; Oh, Sang Cheul; Kim, Jun Suk

    2012-03-10

    p53, the major human tumor suppressor, appears to be related to sonic hedgehog (Shh)-Gli-mediated tumorigenesis. However, the role of p53 in tumor progression by the Shh-Gli signaling pathway is poorly understood. Herein we investigated the critical regulation of Gli3-p53 in tumorigenesis of colon cancer cells and the molecular mechanisms underlying these effects. RT-PCR analysis indicated that the mRNA level of Shh and Gli3 in colon tumor tissues was significantly higher than corresponding normal tissues (P < 0.001). The inhibition of Gli3 by treatment with Gli3 siRNA resulted in a clear decrease in cell proliferation and enhanced the level of expressionmore » of p53 proteins compared to treatment with control siRNA. The half-life of p53 was dramatically increased by treatment with Gli3 siRNA. In addition, treatment with MG132 blocked MDM2-mediated p53 ubiquitination and degradation, and led to accumulation of p53 in Gli3 siRNA-overexpressing cells. Importantly, ectopic expression of p53 siRNA reduced the ability of Gli3 siRNA to suppress proliferation of those cells compared with the cells treated with Gli3 siRNA alone. Moreover, Gli3 siRNA sensitized colon cancer cells to treatment with anti-cancer agents (5-FU and bevacizumab). Taken together, our studies demonstrate that loss of Gli3 signaling leads to disruption of the MDM2-p53 interaction and strongly potentiate p53-dependent cell growth inhibition in colon cancer cells, indicating a basis for the rational use of Gli3 antagonists as a novel treatment option for colon cancer.« less

  20. Herschel Survey of Galactic OH+, H2O+, and H3O+: Probing the Molecular Hydrogen Fraction and Cosmic-Ray Ionization Rate

    NASA Astrophysics Data System (ADS)

    Indriolo, Nick; Neufeld, D. A.; Gerin, M.; Schilke, P.; Benz, A. O.; Winkel, B.; Menten, K. M.; Chambers, E. T.; Black, John H.; Bruderer, S.; Falgarone, E.; Godard, B.; Goicoechea, J. R.; Gupta, H.; Lis, D. C.; Ossenkopf, V.; Persson, C. M.; Sonnentrucker, P.; van der Tak, F. F. S.; van Dishoeck, E. F.; Wolfire, Mark G.; Wyrowski, F.

    2015-02-01

    In diffuse interstellar clouds the chemistry that leads to the formation of the oxygen-bearing ions OH+, H2O+, and H3O+ begins with the ionization of atomic hydrogen by cosmic rays, and continues through subsequent hydrogen abstraction reactions involving H2. Given these reaction pathways, the observed abundances of these molecules are useful in constraining both the total cosmic-ray ionization rate of atomic hydrogen (ζH) and molecular hydrogen fraction (f_H_2). We present observations targeting transitions of OH+, H2O+, and H3O+ made with the Herschel Space Observatory along 20 Galactic sight lines toward bright submillimeter continuum sources. Both OH+ and H2O+ are detected in absorption in multiple velocity components along every sight line, but H3O+ is only detected along 7 sight lines. From the molecular abundances we compute f_H_2 in multiple distinct components along each line of sight, and find a Gaussian distribution with mean and standard deviation 0.042 ± 0.018. This confirms previous findings that OH+ and H2O+ primarily reside in gas with low H2 fractions. We also infer ζH throughout our sample, and find a lognormal distribution with mean log (ζH) = -15.75 (ζH = 1.78 × 10-16 s-1) and standard deviation 0.29 for gas within the Galactic disk, but outside of the Galactic center. This is in good agreement with the mean and distribution of cosmic-ray ionization rates previously inferred from H_3^+ observations. Ionization rates in the Galactic center tend to be 10-100 times larger than found in the Galactic disk, also in accord with prior studies. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

  1. Hierachical Ni@Fe2O3 superparticles through epitaxial growth of γ-Fe2O3 nanorods on in situ formed Ni nanoplates

    NASA Astrophysics Data System (ADS)

    Tahir, Muhammad Nawaz; Herzberger, Jana; Natalio, Filipe; Köhler, Oskar; Branscheid, Robert; Mugnaioli, Enrico; Ksenofontov, Vadim; Panthöfer, Martin; Kolb, Ute; Frey, Holger; Tremel, Wolfgang

    2016-05-01

    One endeavour of nanochemistry is the bottom-up synthesis of functional mesoscale structures from basic building blocks. We report a one-pot wet chemical synthesis of Ni@γ-Fe2O3 superparticles containing Ni cores densely covered with highly oriented γ-Fe2O3 (maghemite) nanorods (NRs) by controlled reduction/decomposition of nickel acetate (Ni(ac)2) and Fe(CO)5. Automated diffraction tomography (ADT) of the Ni-Fe2O3 interface in combination with Mössbauer spectroscopy showed that selective and oriented growth of the γ-Fe2O3 nanorods on the Ni core is facilitated through the formation of a Fe0.05Ni0.95 alloy and the appearance of superstructure features that may reduce strain at the Ni-Fe2O3 interface. The common orientation of the maghemite nanorods on the Ni core of the superparticles leads to a greatly enhanced magnetization. After functionalization with a catechol-functional polyethylene glycol (C-PEG) ligand the Ni@γ-Fe2O3 superparticles were dispersible in water.One endeavour of nanochemistry is the bottom-up synthesis of functional mesoscale structures from basic building blocks. We report a one-pot wet chemical synthesis of Ni@γ-Fe2O3 superparticles containing Ni cores densely covered with highly oriented γ-Fe2O3 (maghemite) nanorods (NRs) by controlled reduction/decomposition of nickel acetate (Ni(ac)2) and Fe(CO)5. Automated diffraction tomography (ADT) of the Ni-Fe2O3 interface in combination with Mössbauer spectroscopy showed that selective and oriented growth of the γ-Fe2O3 nanorods on the Ni core is facilitated through the formation of a Fe0.05Ni0.95 alloy and the appearance of superstructure features that may reduce strain at the Ni-Fe2O3 interface. The common orientation of the maghemite nanorods on the Ni core of the superparticles leads to a greatly enhanced magnetization. After functionalization with a catechol-functional polyethylene glycol (C-PEG) ligand the Ni@γ-Fe2O3 superparticles were dispersible in water. Electronic supplementary

  2. Hydrothermal Synthesis, Crystal Structure, and Photoluminescent Properties of Li[UO2(CH3COO)3]3[Co(H2O)6

    NASA Astrophysics Data System (ADS)

    AlDamen, Murad A.; Juwhari, Hassan K.; Al-zuheiri, Aya M.; Alnazer, Louy A.

    2017-12-01

    Single crystal of Li[UO2(CH3COO)3]3[Co(H2O)6] was prepared and found to crystallize in the monoclinic crystal system in the sp. gr. C2/ c, with Z = 2, and unit cell parameters a = 22.1857(15) Å, b = 13.6477(8) Å, c = 15.6921(10) Å, β = 117.842(9)°, V = 4201.3(4) Å3. The crystal was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and differential scanning calorimetry. The single crystal X-ray diffraction analysis revealed that the crystal has a lamellar structure in which a cobalt hydrate is sandwiched within the Li[UO2(CH3COO)3]3 2- chains. Furthermore, the room temperature photoluminescence spectrum of the complex was investigated in the solid state.

  3. Oxygen isotope fractionation in the CaCO3-DIC-H2O system

    NASA Astrophysics Data System (ADS)

    Devriendt, Laurent S.; Watkins, James M.; McGregor, Helen V.

    2017-10-01

    The oxygen isotope ratio (δ18O) of inorganic and biogenic carbonates is widely used to reconstruct past environments. However, the oxygen isotope exchange between CaCO3 and H2O rarely reaches equilibrium and kinetic isotope effects (KIE) commonly complicate paleoclimate reconstructions. We present a comprehensive model of kinetic and equilibrium oxygen isotope fractionation between CaCO3 and water (αc/w) that accounts for fractionation between both (a) CaCO3 and the CO32- pool (α c / CO32-) , and (b) CO32- and water (α CO32- / w) , as a function of temperature, pH, salinity, calcite saturation state (Ω), the residence time of the dissolved inorganic carbon (DIC) in solution, and the activity of the enzyme carbonic anhydrase. The model results suggest that: (1) The equilibrium αc/w is only approached in solutions with low Ω (i.e. close to 1) and low ionic strength such as in the cave system of Devils Hole, Nevada. (2) The sensitivity of αc/w to the solution pH and/or the mineral growth rate depends on the level of isotopic equilibration between the CO32- pool and water. When the CO32- pool approaches isotopic equilibrium with water, small negative pH and/or growth rate effects on αc/w of about 1-2‰ occur where these parameters covary with Ω. In contrast, isotopic disequilibrium between CO32- and water leads to strong (>2‰) positive or negative pH and growth rate effects on α CO32-/ w (and αc/w) due to the isotopic imprint of oxygen atoms derived from HCO3-, CO2, H2O and/or OH-. (3) The temperature sensitivity of αc/w originates from the negative effect of temperature on α CO32-/ w and is expected to deviate from the commonly accepted value (-0.22 ± 0.02‰/°C between 0 and 30 °C; Kim and O'Neil, 1997) when the CO32- pool is not in isotopic equilibrium with water. (4) The model suggests that the δ18O of planktic and benthic foraminifers reflects a quantitative precipitation of DIC in isotopic equilibrium with a high-pH calcifying fluid, leading

  4. Crystal structures of ZnCl2·2.5H2O, ZnCl2·3H2O and ZnCl2·4.5H2O

    PubMed Central

    Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

    2014-01-01

    The formation of different complexes in aqueous solutions is an important step in understanding the behavior of zinc chloride in water. The structure of concentrated ZnCl2 solutions is governed by coordination competition of Cl− and H2O around Zn2+. According to the solid–liquid phase diagram, the title compounds were crystallized below room temperature. The structure of ZnCl2·2.5H2O contains Zn2+ both in a tetra­hedral coordination with Cl− and in an octa­hedral environment defined by five water mol­ecules and one Cl− shared with the [ZnCl4]2− unit. Thus, these two different types of Zn2+ cations form isolated units with composition [Zn2Cl4(H2O)5] (penta­aqua-μ-chlorido-tri­chlorido­di­zinc). The trihydrate {hexa­aqua­zinc tetra­chlorido­zinc, [Zn(H2O)6][ZnCl4]}, consists of three different Zn2+ cations, one of which is tetra­hedrally coordinated by four Cl− anions. The two other Zn2+ cations are each located on an inversion centre and are octa­hedrally surrounded by water mol­ecules. The [ZnCl4] tetra­hedra and [Zn(H2O)6] octa­hedra are arranged in alternating rows parallel to [001]. The structure of the 4.5-hydrate {hexa­aqua­zinc tetra­chlorido­zinc trihydrate, [Zn(H2O)6][ZnCl4]·3H2O}, consists of isolated octa­hedral [Zn(H2O)6] and tetra­hedral [ZnCl4] units, as well as additional lattice water mol­ecules. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ZnCl4 tetra­hedra and water mol­ecules as acceptor groups leads to the formation of a three-dimensional network in each of the three structures. PMID:25552980

  5. U3Si2 behavior in H2O: Part I, flowing steam and the effect of hydrogen

    NASA Astrophysics Data System (ADS)

    Wood, E. Sooby; White, J. T.; Grote, C. J.; Nelson, A. T.

    2018-04-01

    Recent interest in U3Si2 as an advanced light water reactor fuel has driven assessment of numerous properties, but characterization of its response to H2O environments is absent from the literature. The behavior of U3Si2 in H2O containing atmospheres is investigated and presented in a two-part series of articles aimed to understand the degradation mechanism of U3Si2 in H2O. Reported here are thermogravimetric data for U3Si2 exposed to flowing steam at 250-470 °C. Additionally the response of U3Si2 to flowing Ar-6% H2 from 350 to 400 °C is presented. Microstructural degradation is observed following hours of exposure at 350 °C in steam. U3Si2 undergoes pulverization on the timescale of minutes when temperatures are increased above 400 °C. This mechanism is accelerated in flowing Ar-H2 at the same temperatures.

  6. BEAN MODEL AND AC LOSSES IN Bi{sub 2}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10}/Ag TAPES

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

    SUENAGA,M.; CHIBA,T.; WIESMANN,H.J.

    The Bean model is almost solely used to interpret ac losses in the powder-in-tube processed composite conductor, Bi{sub 2}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10}/Ag. In order to examine the limits of the applicability of the model, a detailed comparison was made between the values of critical current density J{sub c} for Bi(2223)/Ag tapes which were determined by standard four-probe-dc measurement, and which were deduced from the field dependence of the ac losses utilizing the model. A significant inconsistency between these values of J{sub c} were found, particularly at high fields. Possible sources of the discrepancies are discussed.

  7. Characterization and receptor specific toxicity of two diphtheria toxin-related interleukin-3 fusion proteins DAB389-mIL-3 and DAB389-(Gly4Ser)2-mIL-3.

    PubMed

    Liger, D; vanderSpek, J C; Gaillard, C; Cansier, C; Murphy, J R; Leboulch, P; Gillet, D

    1997-04-07

    We have constructed two fusion proteins, DAB389-mIL-3 and DAB389-(Gly4Ser)2-mIL-3, in which the receptor-binding domain of diphtheria toxin is replaced by mouse interleukin-3 (IL-3). Cytotoxic activity of the fusion toxins was observed on three out of six cell lines assayed. This toxicity was mediated through binding to the IL-3 receptor as it was inhibited in a dose-dependent manner with murine IL-3 or anti-IL-3 neutralizing antibodies. DAB389-(Gly4Ser)2-mIL-3 was up to 5 times more toxic than DAB389-mIL-3, depending on the cell line (0.8 x 10(-10) M < IC50 < 3 x 10(-10) M). These proteins can be used for the detection of IL-3 receptors on mouse cells and should allow for the selective elimination of IL-3 receptor-positive pluripotent hematopoietic stem cells prior to bone marrow transplantation.

  8. Herschel/HIFI observations of CO, H2O and NH3 in Monoceros R2

    NASA Astrophysics Data System (ADS)

    Pilleri, P.; Fuente, A.; Cernicharo, J.; Ossenkopf, V.; Berné, O.; Gerin, M.; Pety, J.; Goicoechea, J. R.; Rizzo, J. R.; Montillaud, J.; González-García, M.; Joblin, C.; Le Bourlot, J.; Le Petit, F.; Kramer, C.

    2012-08-01

    Context. Mon R2, at a distance of 830 pc, is the only ultracompact H ii region (UCH ii) where the associated photon-dominated region (PDR) can be resolved with Herschel. Owing to its brightness and proximity, it is one of the best-suited sources for investigating the chemistry and physics of highly UV-irradiated PDRs. Aims: Our goal is to estimate the abundance of H2O and NH3 in this region and investigate their origin. Methods: We present new observations ([C ii], 12CO, 13CO, C18O, o-H2O, p-H2O, o-H_218O and o-NH3) obtained with the HIFI instrument onboard Herschel and the IRAM-30 m telescope. We investigated the physical conditions in which these lines arise by analyzing their velocity structure and spatial variations. Using a large velocity gradient approach, we modeled the line intensities and derived an average abundance of H2O and NH3 across the region. Finally, we modeled the line profiles with a non-local radiative transfer model and compared these results with the abundance predicted by the Meudon PDR code. Results: The variations of the line profiles and intensities indicate complex geometrical and kinematical patterns. In several tracers ([C ii], CO 9 → 8 and H2O) the line profiles vary significantly with position and have broader line widths toward the H ii region. The H2O lines present strong self-absorption at the ambient velocity and emission in high-velocity wings toward the H ii region. The emission in the o-H_218O ground state line reaches its maximum value around the H ii region, has smaller linewidths and peaks at the velocity of the ambient cloud. Its spatial distribution shows that the o-H_218O emission arises in the PDR surrounding the H ii region. By modeling the o-H_218O emission and assuming the standard [16O] / [18O] = 500, we derive a mean abundance of o-H2O of ~10-8 relative to H2. The ortho-H2O abundance, however, is larger (~1 × 10-7) in the high-velocity wings detected toward the H ii region. Possible explanations for this larger

  9. New family of lanthanide-based inorganic-organic hybrid frameworks: Ln2(OH)4[O3S(CH2)nSO32H2O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4) and their derivatives.

    PubMed

    Liang, Jianbo; Ma, Renzhi; Ebina, Yasuo; Geng, Fengxia; Sasaki, Takayoshi

    2013-02-18

    We report the synthesis and structure characterization of a new family of lanthanide-based inorganic-organic hybrid frameworks, Ln(2)(OH)(4)[O(3)S(CH(2))(n)SO(3)]·2H(2)O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4), and their oxide derivatives. Highly crystallized samples were synthesized by homogeneous precipitation of Ln(3+) ions from a solution containing α,ω-organodisulfonate salts promoted by slow hydrolysis of hexamethylenetetramine. The crystal structure solved from powder X-ray diffraction data revealed that this material comprises two-dimensional cationic lanthanide hydroxide {[Ln(OH)(2)(H(2)O)](+)}(∞) layers, which are cross-linked by α,ω-organodisulfonate ligands into a three-dimensional pillared framework. This hybrid framework can be regarded as a derivative of UCl(3)-type Ln(OH)(3) involving penetration of organic chains into two {LnO(9)} polyhedra. Substitutional modification of the lanthanide coordination promotes a 2D arrangement of the {LnO(9)} polyhedra. A new hybrid oxide, Ln(2)O(2)[O(3)S(CH(2))(n)SO(3)], which is supposed to consist of alternating {[Ln(2)O(2)](2+)}(∞) layers and α,ω-organodisulfonate ligands, can be derived from the hydroxide form upon dehydration/dehydroxylation. These hybrid frameworks provide new opportunities to engineer the interlayer chemistry of layered structures and achieve advanced functionalities coupled with the advantages of lanthanide elements.

  10. Conformation-Specific Spectroscopy of a Prototypical γ-PEPTIDE-WATER Complex: Ac2-hPhe-NHMe-(H2O)1

    NASA Astrophysics Data System (ADS)

    Buchanan, Evan G.; James, William H., III; Zwier, Timothy S.; Guo, Li; Gellman, Samuel H.

    2010-06-01

    The prototypical γ-peptide, Ac2-hPhe-NHMe, has been previously studied in a supersonic jet expansion, with three different conformers observed. Two of the monomers form nine atom, intramolecular hydrogen bonded rings, which differ by the position of the aromatic chromophore relative to the backbone. The third monomer conformer has no intramolecular H-bonds, but forms instead an intramolecular, amide-amide stacked structure unique to the γ-peptide backbone. This talk focuses attention on the conformation-specific IR spectra of the Ac2-hPhe-NHMe-(H2O)1 complex, which is observed to form six unique conformational isomers, all of which preserve the two distinct monomer structural motifs. Three conformers are assigned to the nine atom intramolecular hydrogen bond family with the water hydrogen bonded to it as donor in different locations. The other three belong to the amide-amide stacking family with the water forming a bridge between the two amide planes. Infrared photodissocation of the water molecule from the complex to form γ-peptide monomer conformations will also be discussed.

  11. 8-Chloro-6-iodo-2-phenyl­chromeno[4,3-c]pyrazol-4(2H)-one N,N-dimethyl­formamide monosolvate

    PubMed Central

    Lokhande, Pradeep; Hasanzadeh, Kamal; Khaledi, Hamid; Mohd Ali, Hapipah

    2011-01-01

    In the title compound, C16H8ClIN2O2·C3H7NO, the fused tricyclic pyrazolo­coumarin ring and the N-phenyl ring are almost coplanar, the dihedral angle between them being 1.86 (9)°. In the crystal, these rings stack on top of each other via π–π inter­actions [centroid–centroid distances = 3.489 (2), 3.637 (2), 3.505 (2) and 3.662 (2) Å], forming infinite chains along the a axis. The chains are connected into layers parallel to ac plane through I⋯O inter­actions [3.0011 (18) Å] between pairs of symmetry-related mol­ecules. The DMF solvent mol­ecules are C—H⋯O bonded to this network. PMID:21837089

  12. Catalytic dehydrofluorination of 1,1,1,3,3-pentafluoropropane to 1,3,3,3-tetrafluoropropene over fluorinated NiO/Cr2O3 catalysts

    NASA Astrophysics Data System (ADS)

    Luo, Jian-Wei; Song, Jian-Dong; Jia, Wen-Zhi; Pu, Zhi-Ying; Lu, Ji-Qing; Luo, Meng-Fei

    2018-03-01

    Catalytic dehydrofluorination of 1,1,1,3,3-pentafluoropropane to 1,3,3,3-tetrafluoropropene was performed on a series of fluorinated NiO/Cr2O3 catalysts. The NiO/Cr2O3 catalysts were more active than the Cr2O3 because the new acid sites provided by NiF2 had higher turnover frequencies (9.43 × 10-3 - 12.08 × 10-3 s-1) than those on the Cr2O3 (4.55 × 10-3 s-1). Also, the NiO/Cr2O3 was more stable than the Cr2O3 due to its lower density of surface acid sites, which alleviated the coke deposition on the catalyst as evidenced by the Raman spectroscopic results. The kinetic results revealed that the15NiO/Cr2O3 had much lower activation energy (63.6 ± 4.5 kJ mol-1) than the Cr2O3 (127.6 ± 3.8 kJ mol-1). Accordingly, different reaction pathways on the two catalysts were proposed, which involved the cleavage of the Csbnd F and Csbnd H bonds on the surface acid and base sites, respectively.

  13. Hilarionite, Fe{2/3+}(SO4)(AsO4)(OH) · 6H2O, a new supergene mineral from Lavrion, Greece

    NASA Astrophysics Data System (ADS)

    Pekov, I. V.; Chukanov, N. V.; Yapaskurt, V. O.; Rusakov, V. S.; Belakovsky, D. I.; Turchkova, A. G.; Voudouris, P.; Magganas, A.; Katerinopoulos, A.

    2014-12-01

    A new mineral, hilarionite, ideally Fe{2/3+} (SO4)(AsO4)(OH) · 6H2O, has been found in the Hilarion Mine, Agios Konstantinos, Kamariza, Lavrion district, Attiki Prefecture, Greece. It was formed in the oxidation zone of a sulfide-rich orebody in association with goethite, gypsum, bukovskyite, jarosite, melanterite, chalcanthite, allophane, and azurite. Hilarionite occurs as light green (typically with an olive or grayish tint) to light yellowish green spherulites (up to 1 mm in size) and bunches of prismatic to acicular "individuals" up to 0.5 mm long that are in fact near-parallel or divergent aggregates of very thin, curved fibers up to 0.3 mm long and usually lesser than 2 μm thick. The luster is silky to vitreous. The Mohs' hardness is ca. 2. Hilarionite is ductile, its "individuals" are flexible and inelastic; fracture is uneven or splintery. D(meas) = 2.40(5), D(calc) = 2.486 g/cm3. IR spectrum shows the presence of arsenate and sulfate groups and H2O molecules in significant amounts. The Mössbauer spectrum indicates the presence of Fe3+ at two six-fold coordinated sites and the absence of Fe2+. Hilarionite is optically biaxial (+), α = 1.575(2), γ = 1.64(2), 2 V is large. The chemical composition (electron microprobe, average of 7 point analyses; H2O determined by modified Penfield method) is as follows, wt %: 0.03 MnO, 0.18 CuO, 0.17 ZnO, 33.83 Fe2O3, 0.22 P2O5, 18.92 As2O5, 22.19 SO3, 26.3 H2O, total is 101.82%. The empirical formula calculated on the basis of 15 O is: (Fe{1.90/3+}Cu0.01Zn0.01)Σ1.92[(SO4)1.24(AsO4)0.74(PO4)0.01]Σ1.99(OH)1.01 · 6.03H2O. The X-ray powder diffraction data show close structural relationship of hilarionite and kaňkite, Fe{2/3+}(AsO4)2 · 7H2O. Hilarionite is monoclinic, space group C2/ m, Cm or C2, a = 18.53(4), b = 17.43(3), c = 7.56(1) Å, β = 94.06(15)°, V = 2436(3) Å3, Z = 8. The strongest reflections in the X-ray powder diffraction pattern ( d, Å- I[ hkl]) are: 12.66-100[110], , 5.00-10[22l], , 4

  14. Construction of Zeolite-Like Cluster Organic Frameworks from 3 d-4 d/3 d-3 d Heterometallic Supertetrahedral Secondary Building Units: Syntheses, Structures, and Properties.

    PubMed

    Lin, Li-Dan; Deng, Chu-Chu; Zhao, D; Li, Xin-Xiong; Zheng, Shou-Tian

    2018-01-02

    Two zeolite-like cluster organic frameworks based on Cd-Cu/Mn-Cu heterometallic supertetrahedral secondary building units have been successfully constructed under solvothermal conditions, namely, Cu[Cd 4 Cu 6 (L) 4 (H 2 O) 18 ](Ac) 9 ⋅DMA⋅3H 2 O (1), and Cu[Mn 4 Cu 6 (L) 4 (Ac) 3 (H 2 O) 12 ](Ac) 6 ⋅CH 3 CN⋅13 H 2 O (2), where H 3 L=2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol, Ac=CH 3 COO - , DMA=N,N'-dimethylacetamide. Single-crystal X-ray structural analysis reveals that both 1 and 2 exhibit 3-dimensional zeolite-like architectures with similar 4-connected components, but possess definitely different topologies of diamondoid (dia) and uncommon lonsdaleite (lon), respectively. 1 and 2 represent the first cases of zeolite-like cluster organic frameworks containing Cd-Cu/Mn-Cu heterometallic supertetrahedral secondary building units. Furthermore, the magnetic properties and porous nature of 1 and 2 were also studied. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. X-ray investigation of molten crystal hydrates H2SO4(nH2O) and HNO3(nH2O)

    NASA Technical Reports Server (NTRS)

    Romanova, A. V.; Skryshevskiy, A. F.

    1979-01-01

    Integral analysis of the intensity of the electron density distribution curve in molten crystal hydrates provided by X-ray analysis, permits the following conclusions on the structure of the complex SO and NO ions, and the short-range order in the structure of the solution. The SO4 ion in the solution has a tetrahedral structure with an S to O distance equal to 1.5 A. For the NO3 in the solution, a planar triangular shape is probable, with an N to O distance equal to 1.2 A. Preferential distances between each of the oxygens of the SO ion and the nearest molecules of water proved near to the corresponding distances in solid crystal hydrates. For an (H2SO4)(H2O) solution, the average number of water molecules surrounding each oxygen atom of the SO4 (--) ion was on the order of 1.3 molecules. Hence the preferential distances between the water molecules and the oxygen atoms of the SO ion, and the preference of their mutual position, correspond to the fixed position of these same elements of the structure in the solid crystal hydrate.

  16. Synthesis, characterization and biological study on Cr(3+), ZrO(2+), HfO(2+) and UO(2)(2+) complexes of oxalohydrazide and bis(3-hydroxyimino)butan-2-ylidene)-oxalohydrazide.

    PubMed

    El-Asmy, A A; El-Gammal, O A; Radwan, H A

    2010-09-01

    Cr(3+), ZrO(2+), HfO(2+) and UO(2)(2+) complexes of oxalohydrazide (H(2)L(1)) and oxalyl bis(diacetylmonoxime hydrazone) [its IUPAC name is oxalyl bis(3-hydroxyimino)butan-2-ylidene)oxalohydrazide] (H(4)L(2)) have been synthesized and characterized by partial elemental analysis, spectral (IR; electronic), thermal and magnetic measurements. [Cr(L(1))(H(2)O)(3)(Cl)].H(2)O, [ZrO(HL(1))(2)].C(2)H(5)OH, [UO(2)(L(1))(H(2)O)(2)] [ZrO(H(3)L(2))(Cl)](2).2H(2)O, [HfO(H(3)L(2))(Cl)](2).2H(2)O and [UO(2)(H(2)L(2))].2H(2)O have been suggested. H(2)L(1) behaves as a monobasic or dibasic bidentate ligand while H(4)L(2) acts as a tetrabasic octadentate with the two metal centers. The molecular modeling of the two ligands have been drawn and their molecular parameters were calculated. Examination of the DNA degradation of H(2)L(1) and H(4)L(2) as well as their complexes revealed that direct contact of [ZrO(H(3)L(2))(Cl)](2).2H(2)O or [HfO(H(3)L(2))(Cl)](2).2H(2)O degrading the DNA of Eukaryotic subject. The ligands and their metal complexes were tested against Gram's positive Bacillus thuringiensis (BT) and Gram's negative (Escherichia coli) bacteria. All compounds have small inhibitory effects. Copyright 2010 Elsevier B.V. All rights reserved.

  17. Crystal structures of Sr(ClO4)2·3H2O, Sr(ClO4)2·4H2O and Sr(ClO4)2·9H2O

    PubMed Central

    Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

    2014-01-01

    The title compounds, strontium perchlorate trihydrate {di-μ-aqua-aquadi-μ-perchlorato-strontium, [Sr(ClO4)2(H2O)3]n}, strontium perchlorate tetra­hydrate {di-μ-aqua-bis­(tri­aqua­diperchloratostrontium), [Sr2(ClO4)4(H2O)8]} and strontium perchlorate nona­hydrate {hepta­aqua­diperchloratostrontium dihydrate, [Sr(ClO4)2(H2O)7]·2H2O}, were crystallized at low temperatures according to the solid–liquid phase diagram. The structures of the tri- and tetra­hydrate consist of Sr2+ cations coordinated by five water mol­ecules and four O atoms of four perchlorate tetra­hedra in a distorted tricapped trigonal–prismatic coordination mode. The asymmetric unit of the trihydrate contains two formula units. Two [SrO9] polyhedra in the trihydrate are connected by sharing water mol­ecules and thus forming chains parallel to [100]. In the tetra­hydrate, dimers of two [SrO9] polyhedra connected by two sharing water mol­ecules are formed. The structure of the nona­hydrate contains one Sr2+ cation coordinated by seven water mol­ecules and by two O atoms of two perchlorate tetra­hedra (point group symmetry ..m), forming a tricapped trigonal prism (point group symmetry m2m). The structure contains additional non-coordinating water mol­ecules, which are located on twofold rotation axes. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ClO4 tetra­hedra and water mol­ecules as acceptor groups lead to the formation of a three-dimensional network in each of the three structures. PMID:25552979

  18. Infrared spectroscopy of solid normal hydrogen doped with CH3F and O2 at 4.2 K: CH3F:O2 complex and CH3F migration

    NASA Astrophysics Data System (ADS)

    Abouaf-Marguin, L.; Vasserot, A.-M.

    2011-04-01

    Double doping of solid normal hydrogen with CH3F and O2 at about 4.2 K gives evidence of (ortho-H2)n:CH3F clusters and of O2:CH3F complex formation. FTIR analysis of the time evolution of the spectra in the region of the v3 C-F stretching mode indicates that these clusters behave very differently from (ortho-H2)n:H2O clusters. The main point is the observed migration of CH3F molecules in solid para-H2 at 4.2 K which differs from that of H2O under identical experimental conditions. This is confirmed by an increase over time of the integrated intensity of the CH3F:O2 complex with a rate constant K = 2.7(2) . 10-4 s-1.

  19. Modeling Closed Equilibrium Systems of H2O-Dissolved CO2-Solid CaCO3.

    PubMed

    Tenno, Toomas; Uiga, Kalev; Mashirin, Alexsey; Zekker, Ivar; Rikmann, Ergo

    2017-04-27

    In many places in the world, including North Estonia, the bedrock is limestone, which consists mainly of CaCO 3 . Equilibrium processes in water involving dissolved CO 2 and solid CaCO 3 play a vital role in many biological and technological systems. The solubility of CaCO 3 in water is relatively low. Depending on the concentration of dissolved CO 2 , the solubility of CaCO 3 changes, which determines several important ground- and wastewater parameters, for example, Ca 2+ concentration and pH. The distribution of ions and molecules in the closed system solid H 2 O-dissolved CO 2 -solid CaCO 3 is described in terms of a structural scheme. Mathematical models were developed for the calculation of pH and concentrations of ions and molecules (Ca 2+ , CO 3 2- , HCO 3 - , H 2 CO 3 , CO 2 , H + , and OH - ) in the closed equilibrium system at different initial concentrations of CO 2 in the water phase using an iteration method. The developed models were then experimentally validated.

  20. Crystal structure of the tri-ethyl-ammonium salt of 3-[(4-hy-droxy-3-meth-oxy-phen-yl)(4-hy-droxy-2-oxo-2H-chromen-3-yl)meth-yl]-2-oxo-2H-chromen-4-olate.

    PubMed

    Ikram, Muhammad; Rehman, Sadia; Khan, Afzal; Schulzke, Carola

    2018-03-01

    The reaction between 3,3'-[(3-meth-oxy-4-hy-droxy-phen-yl)methanedi-yl]bis-(4-hy-droxy-2 H -chromen-2-one) and tri-ethyl-amine in methanol yielded the title compound tri-ethyl-ammonium 3-[(4-hy-droxy-3-meth-oxy-phen-yl)(4-hy-droxy-2-oxo-2 H -chromen-3-yl)meth-yl]-2-oxo-2 H -chromen-4-olate, C 6 H 16 N + ·C 26 H 17 O 8 - or (NHEt 3 ) + (C 26 H 17 O 8 ) - , which crystallized directly from its methano-lic mother liquor. The non-deprotonated coumarol substituent shares its H atom with the deprotonated coumarolate substituent in a short negative charge-assisted hydrogen bond in which the freely refined H atom is moved from its parent O atom towards the acceptor O atom, elongating the covalent O-H bond to 1.18 (3) Å. The respective H atom can therefore be described as being shared by two alcohol O atoms, culminating in the formation of an eight-membered ring.

  1. Preparation of epitaxial TlBa2Ca2Cu3O9 high Tc thin films on LaAlO3 (100) substrates

    NASA Astrophysics Data System (ADS)

    Piehler, A.; Reschauer, N.; Spreitzer, U.; Ströbel, J. P.; Schönberger, R.; Renk, K. F.; Saemann-Ischenko, G.

    1994-09-01

    Epitaxial TlBa2Ca2Cu3O9 high Tc thin films were prepared on LaAlO3 (100) substrates by a combination of laser ablation and thermal evaporation of thallium oxide. X-ray diffraction patterns of θ-2θ scans showed that the films consisted of highly c axis oriented TlBa2Ca2Cu3O9. φ scan measurements revealed an epitaxial growth of the TlBa2Ca2Cu3O9 thin films on the LaAlO3 (100) substrates. Ac inductive measurements indicated the onset of superconductivity at 110 K. At 6 K, the critical current density was 4×106 A/cm2 in zero magnetic field and 6×105 A/cm2 at a magnetic field of 3 T parallel to the c axis.

  2. Uptake of methanol on mixed HNO3/H2O clusters: An absolute pickup cross section

    NASA Astrophysics Data System (ADS)

    Pysanenko, A.; Lengyel, J.; Fárník, M.

    2018-04-01

    The uptake of atmospheric oxidized organics on acid clusters is relevant for atmospheric new particle formation. We investigate the pickup of methanol (CH3OH) on mixed nitric acid-water clusters (HNO3)M(H2O)N by a combination of mass spectrometry and cluster velocity measurements in a molecular beam. The mass spectra of the mixed clusters exhibit (HNO3)m(H2O)nH+ series with m = 0-3 and n = 0-12. In addition, CH3OH.(HNO3)m(H2O)nH+ series with very similar patterns appear in the spectra after the methanol pickup. The velocity measurements prove that the undoped (HNO3)m(H2O)nH+ mass peaks in the pickup spectra originate from the neutral (HNO3)M(H2O)N clusters which have not picked up any CH3OH molecule, i.e., methanol has not evaporated upon the ionization. Thus the fraction of the doped clusters can be determined and the mean pickup cross section can be estimated, yielding σs ¯ ≈ 20 Å2. This is compared to the lower estimate of the mean geometrical cross section σg ¯ ≈ 60 Å2 obtained from the theoretical cluster geometries. Thus the "size" of the cluster corresponding to the methanol pickup is at least 3-times smaller than its geometrical size. We have introduced a method which can yield the absolute pickup cross sections relevant to the generation and growth of atmospheric aerosols, as illustrated in the example of methanol and nitric acid clusters.

  3. Solid-State Synthesis and Structure of the Enigmatic Ammonium Octaborate: (NH4)2[B7O9(OH)5]·3/4B(OH)3·5/4H2O.

    PubMed

    Neiner, Doinita; Sevryugina, Yulia V; Schubert, David M

    2016-09-06

    The compound known since the 19th century as ammonium octaborate was structurally characterized revealing the ammonium salt of the ribbon isomer of the heptaborate anion, [B7O9(OH)5](2-), with boric acid and water molecules. Of composition (NH4)2B7.75O12.63·4.88H2O, it approximates the classical ammonium octaborate composition (NH4)2B8O13·6H2O and has the structural formula {(NH4)2[B7O9(OH)5]}4·3B(OH)3·5H2O. It spontaneously forms at room temperature in solid-state mixtures of ammonium tetraborate and ammonium pentaborate. It crystallizes in the monoclinic space group P21/c with a = 11.4137(2) Å, b = 11.8877(2) Å, c = 23.4459(3) Å, β = 90.092(1)°, V = 3181.19(8) Å(3), and Z = 2 and contains well-ordered ammonium cations and [B7O9(OH)5](2-) anions and disordered B(OH)3 and H2O molecules linked by extensive H bonding. Expeditious solid-state formation of the heptaborate anion under ambient conditions has important implications for development of practical syntheses of industrially useful borates.

  4. Molecular identification for epigallocatechin-3-gallate-mediated antioxidant intervention on the H2O2-induced oxidative stress in H9c2 rat cardiomyoblasts.

    PubMed

    Chen, Wei-Cheng; Hsieh, Shih-Rong; Chiu, Chun-Hwei; Hsu, Ban-Dar; Liou, Ying-Ming

    2014-06-09

    Epigallocatechin-3-gallate (EGCG) has been documented for its beneficial effects protecting oxidative stress to cardiac cells. Previously, we have shown the EGCG-mediated cardiac protection by attenuating reactive oxygen species and cytosolic Ca2+ in cardiac cells during oxidative stress and myocardial ischemia. Here, we aimed to seek a deeper elucidation of the molecular anti-oxidative capabilities of EGCG in an H2O2-induced oxidative stress model of myocardial ischemia injury using H9c2 rat cardiomyoblasts. Proteomics analysis was used to determine the differential expression of proteins in H9c2 cells cultured in the conditions of control, 400 μM H2O2 exposure for 30 min with and/or without 10 to 20 μM EGCG pre-treatment. In this model, eight proteins associated with energy metabolism, mitochondrial electron transfer, redox regulation, signal transduction, and RNA binding were identified to take part in EGCG-ameliorating H2O2-induced injury in H9c2 cells. H2O2 exposure increased oxidative stress evidenced by increases in reactive oxygen species and cytosolic Ca2+ overload, increases in glycolytic protein, α-enolase, decreases in antioxidant protein, peroxiredoxin-4, as well as decreases in mitochondrial proteins, including aldehyde dehydrogenase-2, ornithine aminotransferase, and succinate dehydrogenase ubiquinone flavoprotein subunit. All of these effects were reversed by EGCG pre-treatment. In addition, EGCG attenuated the H2O2-induced increases of Type II inositol 3, 4-bisphosphate 4-phosphatase and relieved its subsequent inhibition of the downstream signalling for Akt and glycogen synthase kinase-3β (GSK-3β)/cyclin D1 in H9c2 cells. Pre-treatment with EGCG or GSK-3β inhibitor (SB 216763) significantly improved the H2O2-induced suppression on cell viability, phosphorylation of pAkt (S473) and pGSK-3β (S9), and level of cyclin D1 in cells. Collectively, these findings suggest that EGCG blunts the H2O2-induced oxidative effect on the Akt activity

  5. Molecular identification for epigallocatechin-3-gallate-mediated antioxidant intervention on the H2O2-induced oxidative stress in H9c2 rat cardiomyoblasts

    PubMed Central

    2014-01-01

    Background Epigallocatechin-3-gallate (EGCG) has been documented for its beneficial effects protecting oxidative stress to cardiac cells. Previously, we have shown the EGCG-mediated cardiac protection by attenuating reactive oxygen species and cytosolic Ca2+ in cardiac cells during oxidative stress and myocardial ischemia. Here, we aimed to seek a deeper elucidation of the molecular anti-oxidative capabilities of EGCG in an H2O2-induced oxidative stress model of myocardial ischemia injury using H9c2 rat cardiomyoblasts. Results Proteomics analysis was used to determine the differential expression of proteins in H9c2 cells cultured in the conditions of control, 400 μM H2O2 exposure for 30 min with and/or without 10 to 20 μM EGCG pre-treatment. In this model, eight proteins associated with energy metabolism, mitochondrial electron transfer, redox regulation, signal transduction, and RNA binding were identified to take part in EGCG-ameliorating H2O2-induced injury in H9c2 cells. H2O2 exposure increased oxidative stress evidenced by increases in reactive oxygen species and cytosolic Ca2+ overload, increases in glycolytic protein, α-enolase, decreases in antioxidant protein, peroxiredoxin-4, as well as decreases in mitochondrial proteins, including aldehyde dehydrogenase-2, ornithine aminotransferase, and succinate dehydrogenase ubiquinone flavoprotein subunit. All of these effects were reversed by EGCG pre-treatment. In addition, EGCG attenuated the H2O2-induced increases of Type II inositol 3, 4-bisphosphate 4-phosphatase and relieved its subsequent inhibition of the downstream signalling for Akt and glycogen synthase kinase-3β (GSK-3β)/cyclin D1 in H9c2 cells. Pre-treatment with EGCG or GSK-3β inhibitor (SB 216763) significantly improved the H2O2-induced suppression on cell viability, phosphorylation of pAkt (S473) and pGSK-3β (S9), and level of cyclin D1 in cells. Conclusions Collectively, these findings suggest that EGCG blunts the H2O2-induced oxidative

  6. Ordered bimetallic ferromagnets of chromium(III): [Cr(NH 3) 6][Cr(CN) 6], [Cr(H 2O)(NH 3) 5][Cr(CN) 6], and trans-[Cr(en) 2(H 2O) 2]trans-[Cr(en) 2(OH)F] 2(CIO 4) 5·2H 2O

    NASA Astrophysics Data System (ADS)

    Burriel, Ramón; Casabó, Jaime; Pons, Josefina; Carnegie, David W.; Carlin, Richard L.

    1985-07-01

    The magnetic bahavior of the isomorphous compounds [Cr(NH 3) 6][Cr(CN) 6] and [Cr(H 2O)(NH 3) 5][Cr(CN) 6] has been studied by means of zero-field susceptibility measurements. The materials order ferromagnetically at 0.60 and 0.38K, respectively. The compounds behave as examples of the ferromagnetic ( S=3/2) Heisenberg body-center-cubic lattice. The susceptibilities have been analyzed and compared to the Padé approximants of the high-temperature series expansion for this model, a remarkably good fit being obtained with exchange constants 0.042 and 0.022 K, respectively. Another bimetallic substance, trans-[Cr(en) 2(H 2O) 2] trans-[Cr(en) 2(OH)F] 2(CIO 4) 5·2H 2O, with a dominant Heisenberg ferromagnetic interaction J/ kB=0.122 K in one dimension, orders antiferromagnetically at 0.14 K due to a weaker interchain interaction with exchange constant z‧ J‧/ kB=-0.019 K. The three sets of measurements have been carried out on powdered samples for which demagnetization effects are important. The exchange interactions are remarkably weak for such concentrated magnetic materials, yet they are stronger than those found in a number of other such Cr/Cr compounds.

  7. Luminescence and energy transfer of Tb3+-doped BaO-Gd2O3-Al2O3-B2O3-SiO2 glasses.

    PubMed

    Zuo, Chenggang; Huang, Jinze; Liu, Shaoyou; Xiao, Anguo; Shen, Youming; Zhang, Xiangyang; Zhou, Zhihua; Zhu, Ligang

    2017-12-05

    Transparent Tb 3+ -doped BaO-Gd 2 O 3 -Al 2 O 3 -B 2 O 3 -SiO 2 glasses with the greater than 4g/cm 3 were prepared by high temperature melting method and its luminescent properties have been investigated by measured UV-vis transmission, excitation, emission and luminescence decay spectra. The transmission spectrum shows there are three weak absorption bands locate at about 312, 378 and 484nm in the glasses and it has good transmittance in the visible spectrum region. Intense green emission can be observed under UV excitation. The effective energy transfer from Gd 3+ ion to Tb 3+ ion could occur and sensitize the luminescence of Tb 3+ ion. The green emission intensity of Tb 3+ ion could change with the increasing SiO 2 /B 2 O 3 ratio in the borosilicate glass matrix. With the increasing concentration of Tb 3+ ion, 5 D 4 → 7 F J transitions could be enhanced through the cross relaxation between the two nearby Tb 3+ ions. Luminescence decay time of 2.12ms from 546nm emission is obtained. The results indicate that Tb 3+ -doped BaO-Gd 2 O 3 -Al 2 O 3 -B 2 O 3 -SiO 2 glasses would be potential scintillating material for applications in X-ray imaging. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Frequency Comb Assisted IR Measurements of H_3^+, H_2D^+ and D_2H^+ Transitions

    NASA Astrophysics Data System (ADS)

    Jusko, Pavol; Asvany, Oskar; Schlemmer, Stephan

    2016-06-01

    We present recent measurements of the fundamental transitions of H_3^+, H_2D^+ and D_2H^+ in a 4 K 22-pole trap by action spectroscopic techniques. Either Laser Induced Inhibition of Cluster Growth (He attachment at T≈4 K), endothermic reaction of H_3^+ with O_2, or deuterium exchange has been used as measurement scheme. We used a 3 μm optical parametric oscillator coupled to a frequency comb in order to achieve accuracy generally below 1 MHz. Five transitions of H_3^+, eleven of H_2D^+ and ten of D_2H^+ were recorder in our spectral range. We compare our H_3^+ results with two previous frequency comb assisted works. Moreover, accurate determination of the frequency allows us to predict pure rotational transitions for H_2D^+ and D_2H^+ in the THz range. P. Jusko, C. Konietzko, S. Schlemmer, O. Asvany, J. Mol. Spec. 319 (2016) 55 O. Asvany, S. Brünken, L. Kluge, S. Schlemmer, Appl. Phys. B 114 (2014) 203 O. Asvany, J. Krieg, S. Schlemmer, Rev. Sci. Instr. 83 (2012) 093110 J.N. Hodges, A.J. Perry, P.A. Jenkins, B.M. Siller, B.J. McCall, J. Chem. Phys. 139 (2013) 164201 H.-C. Chen, C.-Y. Hsiao, J.-L. Peng, T. Amano, J.-T. Shy, Phys. Rev. Lett. 109 (2012) 263002

  9. U 3Si 2 behavior in H 2O: Part I, flowing steam and the effect of hydrogen

    DOE PAGES

    Wood, Elizabeth Sooby; White, Joshua Taylor; Grote, Christopher John; ...

    2018-01-17

    Recent interest in U 3Si 2 as an advanced light water reactor fuel has driven assessment of numerous properties, but characterization of its response to H 2O environments is absent from the literature. The behavior of U 3Si 2 in H 2O containing atmospheres is investigated and presented in a two-part series of articles aimed to understand the degradation mechanism of U 3Si 2 in H 2O. Reported here are thermogravimetric data for U 3Si 2 exposed to flowing steam at 250–470 °C. Additionally the response of U 3Si 2 to flowing Ar-6% H 2 from 350 to 400 °Cmore » is presented. Microstructural degradation is observed following hours of exposure at 350 °C in steam. U 3Si 2 undergoes pulverization on the timescale of minutes when temperatures are increased above 400 °C. In conclusion, this mechanism is accelerated in flowing Ar-H 2 at the same temperatures.« less

  10. U 3Si 2 behavior in H 2O: Part I, flowing steam and the effect of hydrogen

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

    Wood, Elizabeth Sooby; White, Joshua Taylor; Grote, Christopher John

    Recent interest in U 3Si 2 as an advanced light water reactor fuel has driven assessment of numerous properties, but characterization of its response to H 2O environments is absent from the literature. The behavior of U 3Si 2 in H 2O containing atmospheres is investigated and presented in a two-part series of articles aimed to understand the degradation mechanism of U 3Si 2 in H 2O. Reported here are thermogravimetric data for U 3Si 2 exposed to flowing steam at 250–470 °C. Additionally the response of U 3Si 2 to flowing Ar-6% H 2 from 350 to 400 °Cmore » is presented. Microstructural degradation is observed following hours of exposure at 350 °C in steam. U 3Si 2 undergoes pulverization on the timescale of minutes when temperatures are increased above 400 °C. In conclusion, this mechanism is accelerated in flowing Ar-H 2 at the same temperatures.« less

  11. Syntheses, characterization and antioxidant activity studies of mixed-ligand copper(II) complexes of 2,2‧-bipyridine and glycine: The X-ray crystal structure of [Cu(BPy)(Gly)]ClO4

    NASA Astrophysics Data System (ADS)

    Ibrahim, Mohamed M.; Ramadan, Abd El-Motaleb M.; Shaban, Shaban Y.; Mersal, Gaber A. M.; El-Shazly, Samir A.; Al-Juaid, Salih

    2017-04-01

    A series of mixed-ligand complexes, viz., [CuLL'X]Y {L = bipyridine; L' = glycine; X = 0, Y = ClO4- (1); X = Cl, Y = 2H2O (2); X = H2O, Y = NO3- (3); X = CH3COO-, Y = H2O (4)} and {[Cu(Gly)(BPy)]2-μ-(SO4)}(5)} have been synthesized and characterized by means of elemental analysis, spectroscopic (FT-IR, UV-Vis and ESR), and thermal analysis, as well as magnetic moment measurements. Spectral and X-ray structural features led to the conclusion that complexes 2-5 have square-pyramidal environments around copper(II) center with coordination chromophores CuN3OCl and CuN3O2, respectively. Whereas complex 1 displays square planar geometry. The quasi-reversible CuII/CuI redox couple slightly improves its reversibility with considerable decrease in current intensity. Additionally, the antioxidant (superoxide dismutase and catalase) biomimetic catalytic activities of the obtained complexes have been tested and found to be promising candidates as dual functional mimic enzyme to serve for complete reactive oxygen species (ROS) detoxification, both with respect to the superoxide radicals and the related peroxides.

  12. Cell-Cell Communication Between Fibroblast and 3T3-L1 Cells Under Co-culturing in Oxidative Stress Condition Induced by H2O2.

    PubMed

    Subramaniyan, Sivakumar Allur; Kim, Sidong; Hwang, Inho

    2016-10-01

    The present study was carried out to understand the interaction between fibroblast and 3T3-L1 preadipocyte cells under H 2 O 2 -induced oxidative stress condition. H 2 O 2 (40 μM) was added in co-culture and monoculture of fibroblast and 3T3-L1 cell. The cells in the lower well were harvested for analysis and the process was carried out for both cells. The cell growth, oxidative stress markers, and antioxidant enzymes were analyzed. Additionally, the mRNA expressions of caspase-3 and caspase-7 were selected for analysis of apoptotic pathways and TNF-α and NF-κB were analyzed for inflammatory pathways. The adipogenic marker such as adiponectin and PPAR-γ and collagen synthesis markers such as LOX and BMP-1 were analyzed in the co-culture of fibroblast and 3T3-L1 cells. Cell viability and antioxidant enzymes were significantly increased in the co-culture compared to the monoculture under stress condition. The apoptotic, inflammatory, adipogenic, and collagen-synthesized markers were significantly altered in H 2 O 2 -induced co-culture of fibroblast and 3T3-L1 cells when compared with the monoculture of H 2 O 2 -induced fibroblast and 3T3-L1 cells. In addition, the confocal microscopical investigation indicated that the co-culture of H 2 O 2 -induced 3T3-L1 and fibroblast cells increases collagen type I and type III expression. From our results, we suggested that co-culture of fat cell (3T3-L1) and fibroblast cells may influence/regulate each other and made the cells able to withstand against oxidative stress and aging. It is conceivable that the same mechanism might have been occurring from cell to cell while animals are stressed by various environmental conditions.

  13. Converse magnetoelectric coupling in NiFe/Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}–PbTiO{sub 3} nanocomposite thin films grown on Si substrates

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

    Feng, Ming; Key Laboratory of Functional Materials Physics and Chemistry of the Ministry of Education, Jilin Normal University, Siping 136000; Hu, Jiamian

    2013-11-04

    Multiferroic NiFe (∼30 nm)/Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}–PbTiO{sub 3}(PMN–PT, ∼220 nm) bilayered thin films were grown on common Pt/Ti/SiO{sub 2}/Si substrates by a combination of off-axis magnetron sputtering and sol-gel spin-coating technique. By using AC-mode magneto-optical Kerr effect technique, the change in the Kerr signal (magnetization) of the NiFe upon applying a low-frequency AC voltage to the PMN–PT film was in situ acquired at zero magnetic field. The obtained Kerr signal versus voltage loop essentially tracks the electromechanical strain curve of the PMN–PT thin film, clearly demonstrating a strain-mediated converse magnetoelectric coupling, i.e., voltage-modulated magnetization, in the NiFe/PMN–PT nanocomposite thin films.

  14. Effect of Er3+ concentration on the luminescence properties of Al2O3-ZrO2 powder

    NASA Astrophysics Data System (ADS)

    Clabel H., J. L.; Rivera, V. A. G.; Nogueira, I. C.; Leite, E. R.; Siu Li, M.; Marega, E.

    2016-12-01

    This manuscript reports on the effects of the luminescence properties of Er3+ on Al2O3-ZrO2 powder synthesized by the conventional solid-state method. The best conditions found for the calcinations were 1500 °C and 4 h. The structural dependence of the luminescence on Er3+:Al2O3-ZrO2 is associated with phase transformations of the Al2O3-ZrO2 host and presence of the OH group. Green and red emissions at room temperature from the 2H11/2, 4S3/2 → 4I15/2 and 4F9/2 → 4I15/2 levels of Er3+ ions were observed under 482 nm pumping. The green-to-red emission intensity ratios and CIE chromaticity coordinates were determined from emission spectra for the evaluation of light emitted as a function of the Er3+ concentration. The Er3+ luminescence quenching due to group OH and variation in the Er3+ concentration plays an important role in the definition of the luminescent response.

  15. Bi2O3 cocatalyst improving photocatalytic hydrogen evolution performance of TiO2

    NASA Astrophysics Data System (ADS)

    Xu, Difa; Hai, Yang; Zhang, Xiangchao; Zhang, Shiying; He, Rongan

    2017-04-01

    Photocatalytic hydrogen production using water splitting is of potential importance from the viewpoint of renewable energy development. Herein, Bi2O3-TiO2 composite photocatalysts presented as Bi-Bi2O3-anatase-rutile TiO2 multijunction were first fabricated by a simple impregnation-calcination method using Bi2O3 as H2-production cocatalysts. The obtained multijunction samples exhibit an obvious enhancement in photocatalytic H2 evolution activity in the presence of glycerol. The effect of Bi2O3 amount on H2-evolution activity of TiO2 was investigated and the optimal Bi2O3 content was found to be 0.89 mol%, achieving a H2-production rate of 920 μmol h-1, exceeding that of pure TiO2 by more than 73 times. The enhanced mechanism of photocatalytic H2-evolution activity is proposed. This study will provide new insight into the design and fabrication of TiO2-based hydrogen-production photocatalysts using low-cost Bi2O3 as cocatalyst.

  16. Crystal structure of triaquamaleatostrontium(II) monohydrate, [Sr(C{sub 4}H{sub 2}O{sub 4})(OH{sub 2}{sub 3}) {center_dot}] H{sub 2}O

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

    Diaz de Delgado, G.; Parra, P.P.; Briceno, A.

    1995-05-01

    (Sr(C{sub 4}H{sub 2}O{sub 4})(OH{sub 2}{sub 3}) {center_dot} H{sub 2}O is monoclinic, P2{sub 1}/n, with a = 11.476(2), b = 7.027(1), c = 12.344(2) {angstrom}, {beta} = 115.74(3){degrees}, V= 896.67 {angstrom}{sup 3}, Z = 4. The Sr atom is surrounded by nine oxygen atoms which come from four different maleate anions and three water molecules. The Sr-O distances range from 2.546(2) to 2.808(2) {angstrom}. The C-O distances are equal within the standard deviation 1.263(3) to 1.258(3) {angstrom}). In the maleate anion, the planes that contain the carboxylate groups form an angle of 74.44(9){degrees}. Both carboxylate groups deviate significantly from planarity. Themore » different coordination modes of the carboxylate group and the extensive hydrogen bonding present are responsible for the polymeric nature of the structure.« less

  17. The interface of SrTiO3 and H2O from density functional theory molecular dynamics

    PubMed Central

    Spijker, P.; Foster, A. S.

    2016-01-01

    We use dispersion-corrected density functional theory molecular dynamics simulations to predict the ionic, electronic and vibrational properties of the SrTiO3/H2O solid–liquid interface. Approximately 50% of surface oxygens on the planar SrO termination are hydroxylated at all studied levels of water coverage, the corresponding number being 15% for the planar TiO2 termination and 5% on the stepped TiO2-terminated surface. The lateral ordering of the hydration structure is largely controlled by covalent-like surface cation to H2O bonding and surface corrugation. We find a featureless electronic density of states in and around the band gap energy region at the solid–liquid interface. The vibrational spectrum indicates redshifting of the O–H stretching band due to surface-to-liquid hydrogen bonding and blueshifting due to high-frequency stretching vibrations of OH fragments within the liquid, as well as strong suppression of the OH stretching band on the stepped surface. We find highly varying rates of proton transfer above different SrTiO3 surfaces, owing to differences in hydrogen bond strength and the degree of dissociation of incident water. Trends in proton dynamics and the mode of H2O adsorption among studied surfaces can be explained by the differential ionicity of the Ti–O and Sr–O bonds in the SrTiO3 crystal. PMID:27713660

  18. Structures and chemical bonding of B{sub 3}O{sub 3}{sup −/0} and B{sub 3}O{sub 3}H{sup −/0}: A combined photoelectron spectroscopy and first-principles theory study

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

    Zhao, Li-Juan; Xu, Hong-Guang; Feng, Gang

    We present a combined photoelectron spectroscopy and first-principles theory study on the structural and electronic properties and chemical bonding of B{sub 3}O{sub 3}{sup −/0} and B{sub 3}O{sub 3}H{sup −/0} clusters. The concerted experimental and theoretical data show that the global-minimum structures of B{sub 3}O{sub 3} and B{sub 3}O{sub 3}H neutrals are very different from those of their anionic counterparts. The B{sub 3}O{sub 3}{sup −} anion is characterized to possess a V-shaped OB–B–BO chain with overall C{sub 2v} symmetry (1A), in which the central B atom interacts with two equivalent boronyl (B≡O) terminals via B–B single bonds as well as withmore » one O atom via a B=O double bond. The B{sub 3}O{sub 3}H{sup −} anion has a C{sub s} (2A) structure, containing an asymmetric OB–B–OBO zig-zag chain and a terminal H atom interacting with the central B atom. In contrast, the C{sub 2v} (1a) global minimum of B{sub 3}O{sub 3} neutral contains a rhombic B{sub 2}O{sub 2} ring with one B atom bonded to a BO terminal and that of neutral B{sub 3}O{sub 3}H (2a) is also of C{sub 2v} symmetry, which is readily constructed from C{sub 2v} (1a) by attaching a H atom to the opposite side of the BO group. The H atom in B{sub 3}O{sub 3}H{sup −/0} (2A and 2a) prefers to interact terminally with a B atom, rather than with O. Chemical bonding analyses reveal a three-center four-electron (3c-4e) π hyperbond in the B{sub 3}O{sub 3}H{sup −} (2A) cluster and a four-center four-electron (4c-4e) π bond (that is, the so-called o-bond) in B{sub 3}O{sub 3} (1a) and B{sub 3}O{sub 3}H (2a) neutral clusters.« less

  19. Influence of Background H2O on the Collision-Induced Dissociation Products Generated from [UO2NO3]+

    NASA Astrophysics Data System (ADS)

    Van Stipdonk, Michael J.; Iacovino, Anna; Tatosian, Irena

    2018-04-01

    Developing a comprehensive understanding of the reactivity of uranium-containing species remains an important goal in areas ranging from the development of nuclear fuel processing methods to studies of the migration and fate of the element in the environment. Electrospray ionization (ESI) is an effective way to generate gas-phase complexes containing uranium for subsequent studies of intrinsic structure and reactivity. Recent experiments by our group have demonstrated that the relatively low levels of residual H2O in a 2-D, linear ion trap (LIT) make it possible to examine fragmentation pathways and reactions not observed in earlier studies conducted with 3-D ion traps (Van Stipdonk et al. J. Am. Soc. Mass Spectrom. 14, 1205-1214, 2003). In the present study, we revisited the dissociation of complexes composed of uranyl nitrate cation [UVIO2(NO3)]+ coordinated by alcohol ligands (methanol and ethanol) using the 2-D LIT. With relatively low levels of background H2O, collision-induced dissociation (CID) of [UVIO2(NO3)]+ primarily creates [UO2(O2)]+ by the ejection of NO. However, CID (using He as collision gas) of [UVIO2(NO3)]+ creates [UO2(H2O)]+ and UO2 + when the 2-D LIT is used with higher levels of background H2O. Based on the results presented here, we propose that product ion spectrum in the previous experiments was the result of a two-step process: initial formation of [UVIO2(O2)]+ followed by rapid exchange of O2 for H2O by ion-molecule reaction. Our experiments illustrate the impact of residual H2O in ion trap instruments on the product ions generated by CID and provide a more accurate description of the intrinsic dissociation pathway for [UVIO2(NO3)]+. [Figure not available: see fulltext.

  20. Synthesis, characterization and AC conductivity studies of silver doped conducting polyaniline/graphene/SrTiO3 composites

    NASA Astrophysics Data System (ADS)

    Vinay, K.; Shivakumar, K.; Ravikiran, Y. T.; Revanasiddappa, M.

    2018-05-01

    The present work is an investigation of ac conduction behaviour and dielectric response of Polyaniline/Ag/Graphene/SrTiO3 (PAGS) composite prepared by in-situ chemical oxidative interfacial polymerization using (NH4)2S2O8 as an oxidising agent at 0-5°C. The structural characterization of the samples was examined using FT-IR and XRD techniques. The ac conductivity and dielectric response of synthesized polymer composites were investigated at room temperature in the frequency range varying from 5 × 101 - 5 × 106 Hz using HIOKI make 3532-50 LCR Hi-tester. The ac conductivity increases with increase in frequency and follows the regular trend, the real dielectric constant (ɛ') and imaginary dielectric constant (ɛ'') decreases with increase in frequency and exhibits almost zero dielectric loss at higher frequencies, which suggests that the composite is a lossless material at frequencies beyond 3Hz.

  1. Structure of complexes of nitrilo tris methylene phosphonic acid with copper, [CuN(CH{sub 2}PO{sub 3}){sub 3}(H{sub 2}O){sub 3}] and Na{sub 4}[CuN(CH{sub 2}PO{sub 3}){sub 3}]{sub 2} · 19H{sub 2}O, as bactericides and inhibitors of scaling and corrosion

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

    Somov, N. V., E-mail: somov@phys.unn.ru; Chausov, F. F., E-mail: chaus@uni.udm.ru

    2015-03-15

    Nitrilotris methylene phosphonate triaqua copper and octasodium bis(nitrilotris methylene phosphonate cuprate(II)) nonadecahydrate have been synthesized and investigated. [CuN(CH{sub 2}PO{sub 3}){sub 3}(H{sub 2}O){sub 3}] is crystallized in the sp. gr. P2{sub 1}/c, Z = 4, a = 9.2506(2) Å, b = 15.9815(2) Å, c = 9.5474(2) Å, β = 113.697(2)°. The copper atom is coordinated by oxygen atoms in the configuration of elongated octahedron; the ligand (of bridge type) links neighboring copper atoms. Na{sub 8}[CuN(CH{sub 2}PO{sub 3}){sub 3}]{sub 2} · 19H{sub 2}O is crystallized in the sp. gr. P2{sub 1}/c, Z = 2, a = 11.24550(10) Å, b = 17.38980(10) Å,more » c = 13.5852(2) Å, β = 127.8120(10)°. This complex is chelating; the copper atom closes three five-membered N-C-P-O-Cu cycles with a shared Cu-N bond. Copper is coordinated in a distorted trigonal-bipyramidal configuration.« less

  2. The Molybdenum(V) and Tungsten(VI) Oxoazides [MoO(N3 )3 ], [MoO(N3 )32 CH3 CN], [(bipy)MoO(N3 )3 ], [MoO(N3 )5 ](2-) , [WO(N3 )4 ], and [WO(N3 )4 ⋅CH3 CN].

    PubMed

    Haiges, Ralf; Skotnitzki, Juri; Fang, Zongtang; Dixon, David A; Christe, Karl O

    2015-12-14

    A series of novel molybdenum(V) and tungsten(VI) oxoazides was prepared starting from [MOF4 ] (M=Mo, W) and Me3 SiN3 . While [WO(N3 )4 ] was formed through fluoride-azide exchange in the reaction of Me3 SiN3 with WOF4 in SO2 solution, the reaction with MoOF4 resulted in a reduction of Mo(VI) to Mo(V) and formation of [MoO(N3 )3 ]. Carried out in acetonitrile solution, these reactions resulted in the isolation of the corresponding adducts [MoO(N3 )32 CH3 CN] and [WO(N3 )4 ⋅CH3 CN]. Subsequent reactions of [MoO(N3 )3 ] with 2,2'-bipyridine and [PPh4 ][N3 ] resulted in the formation and isolation of [(bipy)MoO(N3 )3 ] and [PPh4 ]2 [MoO(N3 )5 ], respectively. Most molybdenum(V) and tungsten(VI) oxoazides were fully characterized by their vibrational spectra, impact, friction and thermal sensitivity data and, in the case of [WO(N3 )4 ⋅CH3 CN], [(bipy)MoO(N3 )3 ], and [PPh4 ]2 [MoO(N3 )5 ], by their X-ray crystal structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Enhancement of CO Evolution by Modification of Ga2O3 with Rare-Earth Elements for the Photocatalytic Conversion of CO2 by H2O.

    PubMed

    Tatsumi, Hiroyuki; Teramura, Kentaro; Huang, Zeai; Wang, Zheng; Asakura, Hiroyuki; Hosokawa, Saburo; Tanaka, Tsunehiro

    2017-12-12

    Modification of the surface of Ga 2 O 3 with rare-earth elements enhanced the evolution of CO as a reduction product in the photocatalytic conversion of CO 2 using H 2 O as an electron donor under UV irradiation in aqueous NaHCO 3 as a pH buffer, with the rare-earth species functioning as a CO 2 capture and storage material. Isotope experiments using 13 CO 2 as a substrate clearly revealed that CO was generated from the introduced gaseous CO 2 . In the presence of the NaHCO 3 additive, the rare-earth (RE) species on the Ga 2 O 3 surface are transformed into carbonate hydrates (RE 2 (CO 3 ) 3 ·nH 2 O) and/or hydroxycarbonates (RE 2 (OH) 2(3-x) (CO 3 ) x ) which are decomposed upon photoirradiation. Consequently, Ag-loaded Yb-modified Ga 2 O 3 exhibits much higher activity (209 μmol h -1 of CO) than the pristine Ag-loaded Ga 2 O 3 . The further modification of the surface of the Yb-modified Ga 2 O 3 with Zn afforded a selectivity toward CO evolution of 80%. Thus, we successfully achieved an efficient Ag-loaded Yb- and Zn-modified Ga 2 O 3 photocatalyst with high activity and controllable selectivity, suitable for use in artificial photosynthesis.

  4. Infrared Spectroscopy of Mobility-Selected H+-Gly-Pro-Gly-Gly (GPGG)

    NASA Astrophysics Data System (ADS)

    Masson, Antoine; Kamrath, Michael Z.; Perez, Marta A. S.; Glover, Matthew S.; Rothlisberger, U.; Clemmer, David E.; Rizzo, Thomas R.

    2015-09-01

    We report the first results from a new instrument capable of acquiring infrared spectra of mobility-selected ions. This demonstration involves using ion mobility to first separate the protonated peptide Gly-Pro-Gly-Gly (GPGG) into two conformational families with collisional cross-sections of 93.8 and 96.8 Å2. After separation, each family is independently analyzed by acquiring the infrared predissociation spectrum of the H2-tagged molecules. The ion mobility and spectroscopic data combined with density functional theory (DFT) based molecular dynamics simulations confirm the presence of one major conformer per family, which arises from cis/ trans isomerization about the proline residue. We induce isomerization between the two conformers by using collisional activation in the drift tube and monitor the evolution of the ion distribution with ion mobility and infrared spectroscopy. While the cis-proline species is the preferred gas-phase structure, its relative population is smaller than that of the trans-proline species in the initial ion mobility drift distribution. This suggests that a portion of the trans-proline ion population is kinetically trapped as a higher energy conformer and may retain structural elements from solution.

  5. Observation of a second metastable spin-ordered state in ferrimagnet Cu2OSeO3

    NASA Astrophysics Data System (ADS)

    Huang, C. L.; Tseng, K. F.; Chou, C. C.; Mukherjee, S.; Her, J. L.; Matsuda, Y. H.; Kindo, K.; Berger, H.; Yang, H. D.

    2011-02-01

    dc and ac magnetization measurements were performed on single-crystal Cu2OSeO3 under magnetic field (H) and hydrostatic pressure (P) conditions. Increasing H shifts the ferrimagnetic transition observed at TC~60 K to a higher-temperature region. Moreover, the TC increases linearly and magnetization is enhanced with P. Features of the ladder in the M-vs-H curve or the peak in the dM/dH-vs-H curve are observed at HSF~0.5 kOe, suggesting a competing ordered state under magnetic fields below TC. Remarkably, a second shoulder is observed at ˜1 kOe in the dM/dH-vs-H curve, revealing another metastable spin-ordered state in Cu2OSeO3. This state is retained and enhanced by applying pressure. As H rises to 55 T, no further slope changes in the M-H curve are observed. These magnetic properties indicate a complex spin orientation in the geometrically spin-frustrated system Cu2OSeO3.

  6. Crystal structure of [NaZn(BTC)(H2O)4]·1.5H2O (BTC = benzene-1,3,5-tri-carb-oxy-l-ate): a heterometallic coordination compound.

    PubMed

    Ni, Min; Li, Quanle; Chen, Hao; Li, Shengqing

    2015-07-01

    The title coordination polymer, poly[[μ-aqua-tri-aqua-(μ3-benzene-1,3,5-tri-carboxyl-ato)sodiumzinc] sesquihydrate], {[NaZn(C9H3O6)(H2O)4]·1.5H2O} n , was obtained in ionic liquid microemulsion at room temperture by the reaction of benzene-1,3,5-tri-carb-oxy-lic acid (H3BTC) with Zn(NO3)2·6H2O in the presence of NaOH. The asymmetric unit comprises two Na(+) ions (each located on an inversion centre), one Zn(2+) ion, one BTC ligand, four coordinating water mol-ecules and two solvent water molecules, one of which is disordered about an inversion centre and shows half-occupation. The Zn(2+) cation is five-coordinated by two carboxyl-ate O atoms from two different BTC ligands and three coordinating H2O mol-ecules; the Zn-O bond lengths are in the range 1.975 (2)-2.058 (3) Å. The Na(+) cations are six-coordinated but have different arrangements of the ligands: one is bound to two carboxyl-ate O atoms of two BTC ligands and four O atoms from four coordinating H2O mol-ecules while the other is bound by four carboxyl-ate O atoms from four BTC linkers and two O atoms of coordinating H2O mol-ecules. The completely deprotonated BTC ligand acts as a bridging ligand binding the Zn(2+) atom and Na(+) ions, forming a layered structure extending parallel to (100). An intricate network of O-H⋯O hydrogen bonds is present within and between the layers.

  7. Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C15H9O5)3(H2O)3]n (Ln = Eu, Tb).

    PubMed

    Einkauf, Jeffrey D; Kelley, Tanya T; Chan, Benny C; de Lill, Daniel T

    2016-08-15

    A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.

  8. The effect of H2O on the adsorption of NO2 on γ-Al2O3: an in situ FTIR/MS study

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

    Szanyi, Janos; Kwak, Ja Hun; Chimentao, Ricardo J.

    2007-02-15

    The effect of water on the adsorption of NO2 onto a γ-Al2O3 catalyst support surface was investigated using Fourier transform infrared spectroscopy (FTIR) and mass spectrometry (MS). Upon room temperature exposure of the alumina surface to small amounts of NO2, nitrites and nitrates are formed, and at higher NO2 doses only nitrates are observed. The surface nitrates formed were of bridging monodentate, bridging bidentate, and monodentate configuration. At elevated NO2 pressures, the surface hydroxyls were consumed in their reaction with NO2 giving primarily bridge-bound nitrates. A significant amount of weakly adsorbed N2O3 was seen as well. Exposure of the NO2-saturatedmore » γ-Al2O3 surface to H2O resulted in the desorption of some NO2 + NO as H2O interacted with the weakly-held N2O3, while the bridging monodentate surface nitrates converted into monodentate nitrates. The conversion of these oxide-bound nitrates to water-solvated nitrates was observed at high water doses when the presence of liquid-like water is expected on the surface. The addition of H2O to the NO2-saturated γ-Al2O3 did not affect the amount of NOx strongly adsorbed on the support surface. In particular, no NOx desorption was observed when the NO2-saturated sample was heated to 573K prior to room temperature H2O exposure. The effect of water is completely reversible; i.e., during TPD experiments following NO2 and H2O coadsorption, the same IR spectra were observed at temperatures above that required for H2O desorption as seen for NO2 adsorption only experiments.« less

  9. A neutral molecular-based layered magnet [Fe(C2O4)(CH3OH)]n exhibiting magnetic ordering at TN approximately 23 K.

    PubMed

    Zhang, Bin; Zhang, Yan; Zhang, Jinbiao; Li, Junchao; Zhu, Daoben

    2008-10-07

    Solvothermal synthesis of FeCl(2).4H2O and H2C2O(4).2H2O in methanol at 120 degrees C yielded yellow plate-like crystals of [Fe(C2O4)(CH3OH)]n. Each iron atom is in a distorted octahedral environment, being bonded to four oxygen atoms from two bisbidentate oxalate anions, one O atom of a chelating oxalate anion and one O atom from a methanol molecule as an oxalate group bridging ligand in a five-coordination mode. The neutral layer of [Fe(C2O4)(CH3OH)]n with a [4,4] net along the ac plane. There is no interaction between layers. A long range magnetic ordering with spin canting at TN approximately 23 K was observed and confirmed by AC susceptibility measurements.

  10. A Computational Study of Chalcogen-containing H2 X…YF and (CH3 )2 X…YF (X=O, S, Se; Y=F, Cl, H) and Pnicogen-containing H3 X'…YF and (CH3 )3 X'…YF (X'=N, P, As) Complexes.

    PubMed

    McDowell, Sean A C; Buckingham, A David

    2018-04-20

    A computational study was undertaken for the model complexes H 2 X…YF and (CH 3 ) 2 X…YF (X=O, S, Se; Y=F, Cl, H), and H 3 X'…YF and (CH 3 ) 3 X'…YF (X'=N, P, As), at the MP2/6-311++G(d,p) level of theory. For H 2 X…YF and H 3 X'…YF, noncovalent interactions dominate the binding in order of increasing YF dipole moment, except for H 3 As…F 2 , and possibly H 3 As…ClF. However, for the methyl-substituted complexes (CH 3 ) 2 X…YF and (CH 3 ) 3 X'…YF the binding is especially strong for the complexes containing F 2 , implying significant chemical bonding between the interacting molecules. The relative stability of these complexes can be rationalized by the difference in the electronegativity of the X or X' and Y atoms. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Ac Conduction in Mixed Oxides Al-In2O3-SnO2-Al Structure Deposited by Co-Evaporation

    NASA Astrophysics Data System (ADS)

    Anwar, M.; Siddiqi, S. A.; Ghauri, I. M.

    Conductivity-frequency and capacitance-frequency characteristics of mixed oxides Al-In2O3-SnO2-Al structure are examined to elicit any correlation with the conduction mechanisms most often observed in thin film work. The existence of Schottky barriers is believed to be due to a strong donor band in the insulator established during the vacuum evaporation when a layer of mixed oxides In2O3-SnO2 system is sandwiched between two metal electrodes. Low values of activation energy at low temperatures indicate that the transport of the carriers between localized states is mainly due to electronic hopping over the barrier separating the two nearest neighbor sites. The increase in the formation of ionized donors with increase in temperature during electrical measurements indicates that electronic part of the conductivity is higher than the ionic part. The initial increase in conductivity with increase in Sn content in In2O3 lattice is caused by the Sn atom substitution of In atom, giving out one extra electron. The decrease in electrical conductivity above the critical Sn content (10 mol% SnO2) is caused by the defects formed by Sn atoms, which act as carrier traps rather than electron donors. The increase in electrical conductivity with film thickness is caused by the increase in free carriers density, which is generated by oxygen vacancy acting as two electron donor. The increase in conductivity with substrate and annealing temperatures is due to either the severe deficiency of oxygen, which deteriorates the film properties and reduces the mobility of the carriers or to the diffusion of Sn atoms from interstitial locations into the In cation sites and formation of indium species of lower oxidation state (In2+). Calculations of C and σac from tan δ measurements suggest that there is some kind of space-charge polarization in the material, caused by the storage of carriers at the electrodes. Capacitance decreases not only with the rise of frequency but also with the

  12. Laser-diode-excited blue upconversion in Tm3+/Yb3+ -codoped TeO2-Ga2O3-R2O (R=Li, Na, K) glasses.

    PubMed

    Zhao, Chun; Zhang, Qinyuan; Yang, Gangfeng; Jiang, Zhonghong

    2008-01-01

    This paper reports on intense blue upconversion in Tm(3+)/Yb(3+) codoped TeO(2)-Ga(2)O(3)-R(2)O(R=Li, Na, K) glasses upon excitation with commercial available laser diode (LD). Effects of alkali ions on the Raman spectra, thermal stability and spectroscopic properties of the tellurite-gallium glasses have also been investigated. Energy transfer and the involved upconversion mechanisms have been discussed. Intense blue upconversion emission centered at 476 nm along with a weak red emission at 650 nm has been observed upon excitation of 977 nm LD, assigned to the transitions of 1G4-->3H6, and 1G4-->3H4 and/or 3F(2,3)-->3H6 of Tm(3+), respectively. The blue upconversion intensity has a cubelike dependence on incident pump laser power, indicating a three-photon process. However, a quadratic dependence of the 476 nm upconversion intensity on the incident pump laser power has been observed when samples under excitation of 808 nm LD due to a two-photon absorption process. Enhanced upconversion luminescence have been observed with replacing K(+) for Na(+) and Li(+).

  13. VAPOR PRESSURES, LIQUID MOLAR VOLUMES, VAPOR NON- IDEALITY, AND CRITICAL PROPERTIES OF CF3OCF2CF2CF3, c-CF2CF2CF2CF2O, CF3OCF2OCF3, AND CF3OCF2CF2H

    EPA Science Inventory

    New measurements of the thermophysical properties of CF3OCF2CF2CF3 and c -CF2CF2CF2CF2O are reported from T ≈ 235 K to the critical region. Liquid-phase volumetric results for CF3OCF2OCF3 and CF3OCF2CF2H (235 < T/K < 303) are reported to supplement the information already availab...

  14. A second metastable spin-ordered state on ferrimagnetic single crystal Cu2 OSeO 3

    NASA Astrophysics Data System (ADS)

    Chou, Chih Chieh; Huang, C. L.; Tseng, K. F.; Mukherjee, S.; Her, J. L.; Matsuda, Y. H.; Kindo, K.; Berger, H.; Yang, H. D.

    2011-03-01

    DC and AC susceptibilities were executed on ferrimagnetic single crystal Cu 2 OSe O3 under magnetic field (H) and hydrostatic pressure (P) circumstance. With increasing H , the ferrimagnetic transition at TC ~ 60 K tends to a higher temperature. Furthermore, the TC rises with a linear slope and magnetization is enhanced with increasing P . Features of the ladder shown in the M vs. H curve or the peak observed in the d M / d H vs. H curve are noted at HSF ~ 0.5 kOe, exhibiting a competing ordered state in magnetic fields below TC . Remarkably, another shoulder is observed at ~ 1 kOe in the d M / d H vs. H curve, revealing a metastable spin ordered state in Cu 2 OSe O3 . In addition, the novel state is retained and enhanced by applied pressure. However, at H up to 55 T, there is no more observable slop change in magnetization. These magnetic properties suggest a complex spin orientation in the spin-frustrated system Cu 2 OSe O3 .

  15. Large hydrogen-bonded pre-nucleation (HSO4-)(H2SO4)m(H2O)k and (HSO4-)(NH3)(H2SO4)m(H2O)k clusters in the earth's atmosphere.

    PubMed

    Herb, Jason; Xu, Yisheng; Yu, Fangqun; Nadykto, A B

    2013-01-10

    The importance of pre-nucleation cluster stability as the key parameter controlling nucleation of atmospheric airborne ions is well-established. In this Article, large ternary ionic (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(H(2)O)(n) clusters have been studied using Density Functional Theory (DFT) and composite ab initio methods. Twenty classes of clusters have been investigated, and thermochemical properties of common atmospheric (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(0)(H(2)O)(k) and (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(1)(H(2)O)(n) clusters (with m, k, and n up to 3) have been obtained. A large amount of new themochemical and structural data ready-to-use for constraining kinetic nucleation models has been reported. We have performed a comprehensive thermochemical analysis of the obtained data and have investigated the impacts of ammonia and negatively charged bisulfate ion on stability of binary clusters in some detail. The comparison of theoretical predictions and experiments shows that the PW91PW91/6-311++G(3df,3pd) results are in very good agreement with both experimental data and high level ab initio CCSD(T)/CBS values and suggest that the PW91PW91/6-311++G(3df,3pd) method is a viable alternative to higher level ab initio methods in studying large pre-nucleation clusters, for which the higher level computations are prohibitively expensive. The uncertainties in both theory and experiments have been investigated, and possible ways of their reduction have been proposed.

  16. Suggestion for search of cyclopropenone (c-C3H2O) in a cosmic object

    NASA Astrophysics Data System (ADS)

    Sharma, M. K.; Sharma, M.; Chandra, S.

    2017-03-01

    Following Minimum Energy Principle, out of the three isomers of chemical formula C3H2O, the cyclopropenone (c-C3H2O) is the most stable and therefore may be the most abundant and easily detectable in a cosmic object. The cyclopropenone is detected in Sgr B2(N). Owing to half-spin of each of two hydrogen atoms, the c-C3H2O has two distinct ortho and para species. Using the rotational and centrifugal distortion constants along with the electric dipole moment, we have calculated energies of 100 rotational levels of each of the ortho and para species of c-C3H2O and the Einstein A-coefficients for radiative transitions between the levels. The values of Einstein A-coefficients along with the scaled values for collisional rate coefficients are used for solving a set of statistical equilibrium equations coupled with the equations of radiative transfer. Brightness temperatures of seven rotational transitions of each of the ortho and para species of c-C3H2O are investigated. Out of fourteen transitions, seven are found to show anomalous absorption and rest seven are found to show emission feature. We find that the transitions 110 -111 (1.544 GHz) may play important role in identification of cyclopropenone in a cosmic object.

  17. 4-O-Acetyl-sialic acid (Neu4,5Ac2) in acidic milk oligosaccharides of the platypus (Ornithorhynchus anatinus) and its evolutionary significance.

    PubMed

    Urashima, Tadasu; Inamori, Hiroaki; Fukuda, Kenji; Saito, Tadao; Messer, Michael; Oftedal, Olav T

    2015-06-01

    Monotremes (echidnas and platypus) retain an ancestral form of reproduction: egg-laying followed by secretion of milk onto skin and hair in a mammary patch, in the absence of nipples. Offspring are highly immature at hatching and depend on oligosaccharide-rich milk for many months. The primary saccharide in long-beaked echidna milk is an acidic trisaccharide Neu4,5Ac22-3)Gal(β1-4)Glc (4-O-acetyl 3'-sialyllactose), but acidic oligosaccharides have not been characterized in platypus milk. In this study, acidic oligosaccharides purified from the carbohydrate fraction of platypus milk were characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and (1)H-nuclear magnetic resonance spectroscopy. All identified structures, except Neu5Ac2-3)Gal(β1-4)Glc (3'-sialyllactose) contained Neu4,5Ac2 (4-O-acetyl-sialic acid). These include the trisaccharide 4-O-acetyl 3'-sialyllactose, the pentasaccharide Neu4,5Ac22-3)Gal(β1-4)GlcNAc(β1-3)Gal(β1-4)Glc (4-O-acetyl-3'-sialyllacto-N-tetraose d) and the hexasaccharide Neu4,5Ac22-3)Gal(β1-4)[Fuc(α1-3)]GlcNAc(β1-3)Gal(β1-4)Glc (4-O-acetyl-3'-sialyllacto-N-fucopentaose III). At least seven different octa- to deca-oligosaccharides each contained a lacto-N-neohexaose core (LNnH) and one or two Neu4,5Ac2 and one to three fucose residues. We conclude that platypus milk contains a diverse (≥ 20) array of neutral and acidic oligosaccharides based primarily on lactose, lacto-N-neotetraose (LNnT) and LNnH structural cores and shares with echidna milk the unique feature that all identified acidic oligosaccharides (other than 3'-sialyllactose) contain the 4-O-acetyl-sialic acid moiety. We propose that 4-O-acetylation of sialic acid moieties protects acidic milk oligosaccharides secreted onto integumental surfaces from bacterial hydrolysis via steric interference with bacterial sialidases. This may be of evolutionary significance since taxa ancestral to monotremes and other mammals are

  18. The performance and decolourization kinetics of O3/H2O2 oxidation of reactive green 19 dye in wastewater

    NASA Astrophysics Data System (ADS)

    Sabri, S. N.; Abidin, C. Z. A.; Fahmi; Kow, S. H.; Razali, N. A.

    2018-03-01

    The degradations characteristic of azo dye Reactive Green 19 (RG19) was investigated using advanced oxidation process (AOPs). It was evaluated based on colour and chemical oxygen demand (COD) removal. The effect of operational parameters such as initial dye concentration, initial dosage of hydrogen peroxide (H2O2), contact time, and pH was also being studied. The samples were treated by ozonation (O3) and peroxone O3/H2O2 process. Advanced oxidation processes (AOPs) involve two stages of oxidation; firstly is the formation of strong oxidant and secondly the reaction of organic contaminants in water. In addition, the term advanced oxidation is referring to the processes in which oxidation of organic contaminants occurs primarily through reactions with hydroxyl radicals. There are several analyses that use to determine the efficiency of the treatment process, which are UV-Vis absorption spectra, COD, Fourier Transform Infrared (FT-IR), and pH. The results demonstrated that the ozone oxidation was efficient in decolourization and good in mineralization, based on the reduction of colour and COD. Additionally, results indicate that H2O2 is able to perform better than ozonation in order to decolourize the dye wastewater with 0.5 mL H2O2/L dye dosage of H2O2 at different initial concentration, initial pH, with contact time.

  19. Probing the kinetic energy-release dynamics of H-atom products from the gas-phase reaction of O(3P) with vinyl radical C2H3.

    PubMed

    Jang, Su-Chan; Choi, Jong-Ho

    2014-11-21

    The gas-phase radical-radical reaction dynamics of ground-state atomic oxygen O((3)P) with vinyl radicals C2H3 has been studied by combining the results of vacuum-ultraviolet laser-induced fluorescence spectroscopy in a crossed beam configuration with ab initio calculations. The two radical reactants O((3)P) and C2H3 were produced by photolysis of NO2 and supersonic flash pyrolysis of C2H3I, respectively. Doppler profile analysis of the kinetic energy release of the nascent H-atom products from the title reaction O((3)P) + C2H3H((2)S) + CH2CO (ketene) revealed that the average translational energy of the products and the average fraction of the total available energy were 7.03 ± 0.30 kcal mol(-1) and 7.2%. The empirical data combined with CBS-QB3 level ab initio theory and statistical calculations demonstrated that the title oxygen-hydrogen exchange reaction is a major reaction channel, through an addition-elimination mechanism involving the formation of a short-lived, dynamical complex on the doublet potential energy surface. On the basis of systematic comparison with several exchange reactions of hydrocarbon radicals, the observed kinetic energy release can be explained in terms of the weak impulse at the moment of decomposition in the loose transition state with a product-like geometry and a small reverse barrier along the exit channel.

  20. Felix Spectroscopy of Likely Astronomical Molecular Ions: HC_3O^+, C_2H_3CNH^+, and C_2H_5CNH^+

    NASA Astrophysics Data System (ADS)

    Thorwirth, Sven; Asvany, Oskar; Brünken, Sandra; Jusko, Pavol; Schlemmer, Stephan; Martin-Drumel, Marie-Aline; McCarthy, Michael C.

    2017-06-01

    Infrared signatures of three molecular ions of relevance to the interstellar medium and planetary atmospheres have been detected at the Free Electron Laser for Infrared eXperiments, FELIX, at Radboud University (Nijmegen, The Netherlands) in combination with the 4K FELion 22-pole ion trap facility. Mid-infrared vibrational modes of protonated tricarbon monoxide, HC_3O^+, protonated vinyl cyanide, C_2H_3CNH^+, and protonated ethyl cyanide, C_2H_5CNH^+, were detected using resonant photodissociation of the respective Ne-complexes by monitoring the depletion of their cluster mass signal as a function of wavenumber. The infrared fingerprints compare very favorably with results from high-level quantum-chemical calculations performed at the CCSD(T) level of theory.

  1. Ab initio and transition state theory study of the OH + HO2H2O + O2(3Σg-)/O2(1Δg) reactions: yield and role of O2(1Δg) in H2O2 decomposition and in combustion of H2.

    PubMed

    Monge-Palacios, M; Sarathy, S Mani

    2018-02-07

    Reactions of hydroxyl (OH) and hydroperoxyl (HO 2 ) are important for governing the reactivity of combustion systems. We performed post-CCSD(T) ab initio calculations at the W3X-L//CCSD = FC/cc-pVTZ level to explore the triplet ground-state and singlet excited-state potential energy surfaces of the OH + HO 2H 2 O + O 2 ( 3 Σ g - )/O 2 ( 1 Δ g ) reactions. Using microcanonical and multistructural canonical transition state theories, we calculated the rate constant for the triplet and singlet channels over the temperature range 200-2500 K, represented by k(T) = 3.08 × 10 12 T 0.07  exp(1151/RT) + 8.00 × 10 12 T 0.32  exp(-6896/RT) and k(T) = 2.14 × 10 6 T 1.65  exp(-2180/RT) in cm 3 mol -1 s -1 , respectively. The branching ratios show that the yield of singlet excited oxygen is small (<0.5% below 1000 K). To ascertain the importance of singlet oxygen channel, our new kinetic information was implemented into the kinetic model for hydrogen combustion recently updated by Konnov (Combust. Flame, 2015, 162, 3755-3772). The updated kinetic model was used to perform H 2 O 2 thermal decomposition simulations for comparison against shock tube experiments performed by Hong et al. (Proc. Combust. Inst., 2013, 34, 565-571), and to estimate flame speeds and ignition delay times in H 2 mixtures. The simulation predicted a larger amount of O 2 ( 1 Δ g ) in H 2 O 2 decomposition than that predicted by Konnov's original model. These differences in the O 2 ( 1 Δ g ) yield are due to the use of a higher ab initio level and a more sophisticated methodology to compute the rate constant than those used in previous studies, thereby predicting a significantly larger rate constant. No effect was observed on the rate of the H 2 O 2 decomposition and on the flame speeds and ignition delay times of different H 2 -oxidizer mixtures. However, if the oxidizer is seeded with O 3 , small differences appear in the flame speed. Given that O 2 ( 1 Δ g ) is much more reactive than O

  2. A new Pu(iii) coordination geometry in (C5H5NBr)2[PuCl3(H2O)5]·2Cl·2H2O as obtained via supramolecular assembly in aqueous, high chloride media.

    PubMed

    Surbella, Robert G; Ducati, Lucas C; Pellegrini, Kristi L; McNamara, Bruce K; Autschbach, Jochen; Schwantes, Jon M; Cahill, Christopher L

    2017-09-28

    Crystals of a hydrated Pu(iii) chloride, (C 5 H 5 NBr) 2 [PuCl 3 (H 2 O) 5 ]·2Cl·2H 2 O, were grown via slow evaporation from acidic aqueous, high chloride media. X-ray diffraction data reveals the neutral [PuCl 3 (H 2 O) 5 ] tecton is assembled via charge assisted hydrogen and halogen bonds donated by 4-bromopyridinium cations and a series of inter-tecton hydrogen bonds.

  3. Carbonate mineral solubility at low temperatures in the Na-K-Mg-Ca-H-Cl-SO 4-OH-HCO 3-CO 3-CO 2-H 2O system

    NASA Astrophysics Data System (ADS)

    Marion, Giles M.

    2001-06-01

    Carbonate minerals have played an important role in the geochemical evolution of Earth, and may have also played an important role in the geochemical evolution of Mars and Europa. Several models have been published in recent years that describe chloride and sulfate mineral solubilities in concentrated brines using the Pitzer equations. Few of these models are parameterized for subzero temperatures, and those that are do not include carbonate chemistry. The objectives of this work are to estimate Pitzer-equation bicarbonate-carbonate parameters and carbonate mineral solubility products and to incorporate them into the FREZCHEM model to predict carbonate mineral solubilities in the Na-K-Mg-Ca-H-Cl-SO 4-OH-HCO 3-CO 3-CO 2-H 2O system at low temperatures (≤25°C) with a special focus on subzero temperatures. Most of the Pitzer-equation parameters and equilibrium constants are taken from the literature and extrapolated into the subzero temperature range. Solubility products for 14 sodium, potassium, magnesium, and calcium bicarbonate and carbonate minerals are included in the model. Most of the experimental data are at temperatures ≥ -8°C; only for the NaHCO 3-NaCl-H 2O and Na 2CO 3-NaCl-H 2O systems are there bicarbonate and carbonate data to temperatures as low as -21.6°C. In general, the fit of the model to the experimental data is good. For example, calculated eutectic temperatures and compositions for NaHCO 3, Na 2CO 3, and their mixtures with NaCl and Na 2SO 4 salts are in good agreement with experimental data to temperatures as low as -21.6°C. Application of the model to eight saline, alkaline carbonate waters give predicted pHs ranging from 9.2 to 10.2, in comparison with measured pHs that range from 8.7 to 10.2. The model suggests that the CaCO 3 mineral that precipitates during seawater freezing is probably calcite and not ikaite. The model demonstrates that a proposed salt assemblage for the icy surface of Europa consisting of highly hydrated MgSO 4

  4. VizieR Online Data Catalog: H3O+ and D3O+ rota

    NASA Astrophysics Data System (ADS)

    Owens, A.; Yurchenko, S. N.; Polyansky, O. L.; Ovsyannikov, R. I.; Thiel, W.; Spirko, V.

    2018-01-01

    Given the astronomical relevance of H3O+, and a good set of accurately measured experimental data (Uy, White & Oka 1997JMoSp.183..240U; Araki, Ozeki & Saito 1999, Mol. Phys., 97, 177); Tang & Oka 1999JMoSp.196..120T ; Furuya & Saito 2005A&A...441.1039F; Yu et al. 2009ApJS..180..119Y; Yu & Pearson 2014ApJ...786..133Y), we find it worthwhile to carry out a comprehensive study of hydronium, H316O+ (also referred to as H3O+), and its two symmetric top isotopologues, H318O+ and D316O+. To do this we employ a highly accurate variational approach, which was recently applied to ammonia (Owens et al. 2015MNRAS.450.3191O). Like NH3 (Jansen, Bethlem & Ubachs 2014JChPh.140a0901J; Spirko 2014, J. Phys. Chem. Lett., 5, 919; Owens et al. 2015MNRAS.450.3191O), there is a possibility to find transitions with strongly anomalous sensitivities caused by the Δk=+/-3 interactions (see Papousek et al. 1986JMoSt.141..361P), which have not yet been considered. (11 data files).

  5. X-ray diffraction analysis of 4- and 4'-substituted C n H2 n + 1O-C6H3(OH)-CH=N-C6H4-C m H2 m + 1 ( n/ m = 2/1 and 3/4) salicylideneanilines

    NASA Astrophysics Data System (ADS)

    Kuz'mina, L. G.; Navasardyan, M. A.; Mikhailov, A. A.

    2017-11-01

    X-ray diffraction study of two crystalline modifications of C2H5O-C6H3(OH)-CH=N-C6H4-CH3 ( 1a, sp. gr. P21/ n, and 1b, sp. gr. C2/c) and C3H7O-C6H3(OH)-CH=N-C6H4-C4H9 ( 2, sp. gr. P212121) has been performed. The 1a crystal structure contains two independent molecules. The molecules are conformationally nonrigid with respect to the mutual rotation of benzene rings; the dihedral angles between their planes are 29.19° and 26.00° in the independent molecules of 1a, 18.72° in the molecule of 1b, and 50.35° in the molecule of 2. The crystal packing of the compounds is discussed.

  6. Microwave dielectric properties of CaCu3Ti4O12-Al2O3 composite

    NASA Astrophysics Data System (ADS)

    Rahman, Mohd Fariz Ab; Abu, Mohamad Johari; Karim, Saniah Ab; Zaman, Rosyaini Afindi; Ain, Mohd Fadzil; Ahmad, Zainal Arifin; Mohamed, Julie Juliewatty

    2016-07-01

    (1-x)CaCu3Ti4O12 + (x)Al2O3 composite (0 ≤ x ≤0.25) was prepared via conventional solid-state reaction method. The fabrication of sample was started with synthesizing stoichiometric CCTO from CaCO3, CuO and TiO2 powders, then wet-mixed in deionized water for 24 h. The process was continued with calcined CCTO powder at 900 °C for 12 h before sintered at 1040 °C for 10 h. Next, the calcined CCTO powder with different amount of Al2O3 were mixed for 24 h, then palletized and sintered at 1040 °C for 10. X-ray diffraction analysis on the sintered samples showed that CCTO powder was in a single phase, meanwhile the trace of secondary peaks which belong to CaAl2O4 and Corundum (Al2O3) could be observed in the other samples Scanning electron microscopy analysis showed that the grain size of the sample is firstly increased with addition of Al2O3 (x = 0.01), then become smaller with the x > 0.01. Microwave dielectric properties showed that the addition of Al2O3 (x = 0.01) was remarkably reduced the dielectric loss while slightly increased the dielectric permittivity. However, further addition of Al2O3 was reduced both dielectric loss and permittivity at least for an order of magnitude.

  7. Removal of nitrate and phosphate using chitosan/Al2O3/Fe3O4 composite nanofibrous adsorbent: Comparison with chitosan/Al2O3/Fe3O4 beads.

    PubMed

    Bozorgpour, Farahnaz; Ramandi, Hossein Fasih; Jafari, Pooya; Samadi, Saman; Yazd, Shabnam Sharif; Aliabadi, Majid

    2016-12-01

    In the present study the chitosan/Al 2 O 3 /Fe 3 O 4 composite nanofibrous adsorbent was prepared by electrospinning process and its application for the removal of nitrate and phosphate were compared with chitosan/Al 2 O 3 /Fe 3 O 4 composite bead adsorbent. The influence of Al 2 O 3 /Fe 3 O 4 composite content, pH, contact time, nitrate and phosphate initial concentrations and temperature on the nitrate and phosphate sorption using synthesized bead and nanofibrous adsorbents was investigated in a single system. The reusability of chitosan/Al 2 O 3 /Fe 3 O 4 composite beads and nanofibers after five sorption-desorption cycles were carried out. The Box-Behnken design was used to investigate the interaction effects of adsorbent dosage, nitrate and phosphate initial concentrations on the nitrate and phosphate removal efficiency. The pseudo-second-order kinetic model and known Freundlich and Langmuir isotherm models were used to describe the kinetic and equilibrium data of nitrate and phosphate sorption using chitosan/Al 2 O 3 /Fe 3 O 4 composite beads and nanofibers. The influence of other anions including chloride, fluoride and sulphate on the sorption efficiency of nitrate and phosphate was examined. The obtained results revealed the higher potential of chitosan/Al 2 O 3 /Fe 3 O 4 composite nanofibers for nitrate and phosphate compared with chitosan/Al 2 O 3 /Fe 3 O 4 composite beads. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Porosity and thermal collapse measurements of H2O, CH3OH, CO2, and H2O:CO2 ices.

    PubMed

    Isokoski, K; Bossa, J-B; Triemstra, T; Linnartz, H

    2014-02-28

    The majority of astronomical and laboratory based studies of interstellar ices have been focusing on ice constituents. Ice structure is a much less studied topic. Particularly the amount of porosity is an ongoing point of discussion. A porous ice offers more surface area than a compact ice, for reactions that are fully surface driven. In this paper we discuss the amount of compaction for four different ices--H2O, CH3OH, CO2 and mixed H2O : CO2 = 2 : 1--upon heating over an astronomically relevant temperature regime. Laser interference and Fourier transform infrared spectroscopy are used to confirm that for amorphous solid water the full signal loss of dangling OH bonds is not a proof for full compaction. These data are compared with the first compaction results for pure CH3OH, pure CO2 and mixed H2O : CO2 = 2 : 1 ice. Here we find that thermal segregation benefits from a higher degree of porosity.

  9. 14-3-3ζ turns TGF-β's function from tumor suppressor to metastasis promoter in breast cancer by contextual changes of Smad partners from p53 to Gli2.

    PubMed

    Xu, Jia; Acharya, Sunil; Sahin, Ozgur; Zhang, Qingling; Saito, Yohei; Yao, Jun; Wang, Hai; Li, Ping; Zhang, Lin; Lowery, Frank J; Kuo, Wen-Ling; Xiao, Yi; Ensor, Joe; Sahin, Aysegul A; Zhang, Xiang H-F; Hung, Mien-Chie; Zhang, Jitao David; Yu, Dihua

    2015-02-09

    Transforming growth factor β (TGF-β) functions as a tumor suppressor in premalignant cells but as a metastasis promoter in cancer cells. The dichotomous functions of TGF-β are proposed to be dictated by different partners of its downstream effector Smads. However, the mechanism for the contextual changes of Smad partners remained undefined. Here, we demonstrate that 14-3-3ζ destabilizes p53, a Smad partner in premalignant mammary epithelial cells, by downregulating 14-3-3σ, thus turning off TGF-β's tumor suppression function. Conversely, 14-3-3ζ stabilizes Gli2 in breast cancer cells, and Gli2 partners with Smads to activate PTHrP and promote TGF-β-induced bone metastasis. The 14-3-3ζ-driven contextual changes of Smad partners from p53 to Gli2 may serve as biomarkers and therapeutic targets of TGF-β-mediated cancer progression. Copyright © 2015 Elsevier Inc. All rights reserved.

  10. The Influence of Layer Thickness-Ratio on Magnetoresistance in La2/3Ca1/3MnO3/La1/3Ca2/3MnO3 Exchange Biased System

    NASA Astrophysics Data System (ADS)

    Gomez, Maria Elena; Milena Diez, Sandra; Cuartas, Lina Maria; Marin, Lorena; Prieto, Pedro

    2012-02-01

    Isothermal magnetic field dependence of the resistance in La2/3Ca1/3MnO3 (F-LCMO)/ La1/3Ca2/3MnO3(AF-LCMO) bilayer and AF-LCMO/F-LCMO/AF-LCMO trilayer at temperatures below N'eel temperature of the antiferromagnetic layer were carried out to study the thickness layers influence on magneto transport properties. We grew multilayers using a high oxygen pressure sputtering technique. We systematically varied the thickness of the F-LCMO layer, tF, maintaining constant the thickness of the AF-LCMO layer, tAF. We studied the influence of the thickness ratio tF/tAF on the ZFC and FC magnetoresistance (MR) loops. HFC was varied from 100 Oe to 400 Oe. We found that MR has hysteretic behavior as observed in [La2/3Ca1/3MnO3/La1/3Ca2/3MnO3]N superlattices, where MR increases with the increasing field from H=0 to a maximum and then it decreases continuously. The position and magnitude of the maximum is not symmetric with respect to the axis H=0 for both FC and ZFC loops. We found that magnetoresistance behavior of the bilayer and trilayer is thickness-ratio dependent for both ZFC and FC loops.

  11. Thermal decomposition of europium sulfates Eu2(SO4)3·8H2O and EuSO4

    NASA Astrophysics Data System (ADS)

    Denisenko, Yu. G.; Khritokhin, N. A.; Andreev, O. V.; Basova, S. A.; Sal'nikova, E. I.; Polkovnikov, A. A.

    2017-11-01

    Reactions of europium sulfates Eu2(SO4)3·8H2O and EuSO4 complete decomposition were studied by Simultaneous Thermal Analysis. It was revealed that one-step dehydratation of Eu2(SO4)3·8H2O crystallohydrate is accompanied by the formation of amorphous anhydrous europium sulfate Eu2(SO4)3. Crystallization of amorphous europium (III) sulfate occurs at 381.1 °C (in argon) and 391.3 °C (in air). The average enthalpy values for dehydratation reaction of Eu2(SO4)3·8H2O (ΔH° = 141.1 kJ/mol), decomposition reactions of Eu2(SO4)3H = 463.1 kJ/mol), Eu2O2SO4 (ΔH = 378.4 kJ/mol) and EuSO4 (ΔH = 124.1 kJ/mol) were determined. The step process mechanisms of thermal decomposition of europium (III) sulfate in air and europium (II) sulfate in inert atmosphere were established and justified. The kinetic parameters of complete thermal decomposition of europium (III) sulfate octahydrate were calculated by Kissinger model. The standard enthalpies of compound formation were calculated using thermal effects and formation enthalpy data for binary compounds.

  12. Infrared photodissociation spectroscopy of H(+)(H2O)6·M(m) (M = Ne, Ar, Kr, Xe, H2, N2, and CH4): messenger-dependent balance between H3O(+) and H5O2(+) core isomers.

    PubMed

    Mizuse, Kenta; Fujii, Asuka

    2011-04-21

    Although messenger mediated spectroscopy is a widely-used technique to study gas phase ionic species, effects of messengers themselves are not necessarily clear. In this study, we report infrared photodissociation spectroscopy of H(+)(H(2)O)(6)·M(m) (M = Ne, Ar, Kr, Xe, H(2), N(2), and CH(4)) in the OH stretch region to investigate messenger(M)-dependent cluster structures of the H(+)(H(2)O)(6) moiety. The H(+)(H(2)O)(6), the protonated water hexamer, is the smallest system in which both the H(3)O(+) (Eigen) and H(5)O(2)(+) (Zundel) hydrated proton motifs coexist. All the spectra show narrower band widths reflecting reduced internal energy (lower vibrational temperature) in comparison with bare H(+)(H(2)O)(6). The Xe-, CH(4)-, and N(2)-mediated spectra show additional band features due to the relatively strong perturbation of the messenger. The observed band patterns in the Ar-, Kr-, Xe-, N(2)-, and CH(4)-mediated spectra are attributed mainly to the "Zundel" type isomer, which is more stable. On the other hand, the Ne- and H(2)-mediated spectra are accounted for by a mixture of the "Eigen" and "Zundel" types, like that of bare H(+)(H(2)O)(6). These results suggest that a messenger sometimes imposes unexpected isomer-selectivity even though it has been thought to be inert. Plausible origins of the isomer-selectivity are also discussed.

  13. Emission analysis of Tb3+ -and Sm3+ -ion-doped (Li2 O/Na2 O/K2 O) and (Li2 O + Na2 O/Li2 O + K2 O/K2 O + Na2 O)-modified borosilicate glasses.

    PubMed

    Naveen Kumar Reddy, B; Sailaja, S; Thyagarajan, K; Jho, Young Dahl; Sudhakar Reddy, B

    2018-05-01

    Four series of borosilicate glasses modified by alkali oxides and doped with Tb 3+ and Sm 3+ ions were prepared using the conventional melt quenching technique, with the chemical composition 74.5B 2 O 3 + 10SiO 2 + 5MgO + R + 0.5(Tb 2 O 3 /Sm 2 O 3 ) [where R = 10(Li 2 O /Na 2 O/K 2 O) for series A and C, and R = 5(Li 2 O + Na 2 O/Li 2 O + K 2 O/K 2 O + Na 2 O) for series B and D]. The X-ray diffraction (XRD) patterns of all the prepared glasses indicate their amorphous nature. The spectroscopic properties of the prepared glasses were studied by optical absorption analysis, photoluminescence excitation (PLE) and photoluminescence (PL) analysis. A green emission corresponding to the 5 D 4 → 7 F 5 (543 nm) transition of the Tb 3+ ions was registered under excitation at 379 nm for series A and B glasses. The emission spectra of the Sm 3+ ions with the series C and D glasses showed strong reddish-orange emission at 600 nm ( 4 G 5/2 → 6 H 7/2 ) with an excitation wavelength λ exci = 404 nm ( 6 H 5/2 → 4 F 7/2 ). Furthermore, the change in the luminescence intensity with the addition of an alkali oxide and combinations of these alkali oxides to borosilicate glasses doped with Tb 3+ and Sm 3+ ions was studied to optimize the potential alkali-oxide-modified borosilicate glass. Copyright © 2017 John Wiley & Sons, Ltd.

  14. Association studies to transporting proteins of fac-ReI(CO)3(pterin)(H2O) complex.

    PubMed

    Ragone, Fabricio; Saavedra, Héctor H Martínez; García, Pablo F; Wolcan, Ezequiel; Argüello, Gerardo A; Ruiz, Gustavo T

    2017-01-01

    A new synthetic route to acquire the water soluble complex fac-Re I (CO) 3 (pterin)(H 2 O) was carried out in aqueous solution. The complex has been obtained with success via the fac-[Re I (CO) 3 (H 2 O) 3 ]Cl precursor complex. Re I (CO) 3 (pterin)(H 2 O) has been found to bind strongly with bovine and human serum albumins (BSA and HSA) with intrinsic-binding constants, K b , of 6.5 × 10 5 M -1 and 5.6 × 10 5 M -1 at 310 K, respectively. The interactions of serum albumins with Re I (CO) 3 (pterin)(H 2 O) were evaluated employing UV-vis fluorescence and absorption spectroscopy and circular dichroism. The results suggest that the serum albumins-Re I (CO) 3 (pterin)(H 2 O) interactions occurred in the domain IIA-binding pocket without loss of helical stability of the proteins. The comparison of the fluorescence quenching of BSA and HSA due to the binding to the Re(I) complex suggested that local interaction around the Trp 214 residue had taken place. The analysis of the thermodynamic parameters ΔG 0 , ΔH 0 , and ΔS 0 indicated that the hydrophobic interactions played a major role in both HSA-Re(I) and BSA-Re(I) association processes. All these experimental results suggest that these proteins can be considered as good carriers for transportation of Re I (CO) 3 (pterin)(H 2 O) complex. This is of significant importance in relation to the use of this Re(I) complex in several biomedical fields, such as photodynamic therapy and radiopharmacy.

  15. Zincobotryogen, ZnFe3+(SO4)2(OH)ṡ7H2O: validation as a mineral species and new data

    NASA Astrophysics Data System (ADS)

    Yang, Zhuming; Giester, Gerald; Mao, Qian; Ma, Yuguang; Zhang, Di; Li, He

    2017-06-01

    Zincobotryogen occurs in the oxidation zone of the Xitieshan lead-zinc deposit, Qinghai, China. The mineral is associated with jarosite, copiapite, zincocopiapite, and quartz. The mineral forms prismatic crystals, 0.05 to 2 mm in size. It is optically positive (2Vcalc = 54.1°), with Z ‖ b and X ∧ c = 10°. The elongation is negative. The refractive indices are n α = 1.542(5), n β = 1.551(5), n γ = 1.587(5). The pleochroism scheme is X = colorless, Y = light yellow, Z = yellow. Microprobe analysis gave (in wt%): SO3 = 38.04, Al2O3 = 0.04, Fe2O3 = 18.46, ZnO = 13.75, MgO = 1.52, MnO = 1.23, H2O = 31.06 (by calculation), Total = 104.10. The simplified formula is (Zn,Mg)Fe3+(SO4)2(OH)ṡ7H2O. The mineral is monoclinic, P121/ n1, a = 10.504(2), b = 17.801(4), c = 7.1263(14) Å, and β = 100.08(3)°, V = 1311.9(5) Å3, Z = 4. The strongest lines in the powder X-ray diffraction pattern d(I)( hkl) are: 8.92 (100)(110), 6.32 (77)(-101), 5.56 (23)(021), 4.08 (22)(-221),3.21 (31)(231), 3.03 (34)(032), 2.77 (22)(042). The crystal structure was refined using 2816 unique reflections to R1( F) = 0.0355 and wR2( F 2) = 0.0651. The refined formula is (Zn0.84Mg0.16)Fe3+(SO4)2(OH)ṡ7H2O. The atomic arrangement is characterized by chains with composition [Fe3+(SO4)2(OH)(H2O)]2- and 7 Å repeat distance running parallel to the c-axis. The chain links to a [ MO(H2O)5] octahedron ( M = Zn, Mg) and an unshared H2O molecule, and forms a larger chain building module with composition [ M 2+Fe3+(SO4)2(OH)(H2O)6(H2O)]. The inter-chain module linkage involves only hydrogen bonding.

  16. Topologically identical, but geometrically isomeric layers in hydrous α-, β-Rb[UO2(AsO3OH)(AsO2(OH)2)]·H2O and anhydrous Rb[UO2(AsO3OH)(AsO2(OH)2)

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

    Yu, Na; Klepov, Vladislav V.; Villa, Eric M.

    The hydrothermal reaction of uranyl nitrate with rubidium nitrate and arsenic (III) oxide results in the formation of polymorphic α- and β-Rb[UO2(AsO3OH)(AsO2(OH)2)]·H2O (α-, β-RbUAs) and the anhydrous phase Rb[UO2(AsO3OH)(AsO2(OH)2)] (RbUAs). These phases were structurally, chemically and spectroscopically characterized. The structures of all three compounds are based upon topologically identical, but geometrically isomeric layers. The layers are linked with each other by means of the Rb cations and hydrogen bonding. Dehydration experiments demonstrate that water deintercalation from hydrous α- and β-RbUAs yields anhydrous RbUAs via topotactic reactions.

  17. Magneto-optical investigation of MgSO3·6H2O with polarized light

    NASA Astrophysics Data System (ADS)

    Petkova, P.

    2017-10-01

    The crystals of magnesium sulphite hexahydrate (MgSO3·6H2O) belong to point group C3 (no center of symmetry). They possess gyrotropy and nonlinear optical properties. The refractive index no and ne, the angle of Faraday rotation φ(λ), the Verdet constant V(λ), the magneto-optic anomaly factor γ(λ) and the density of oscillators N of MgSO3·6H2O single crystals have been studied in the present work. The investigations were carried out in the spectral range 300 - 800 nm with linear polarized light E ⃗ ⊥ c ̅ , E ⃗ | | c ̅ (c ̅ is the optical axis of MgSO3·6H2O) propagated in the direction (10 1 ̅ 0) .

  18. Facile synthesis of morphology-controlled Co3O4 nanostructures through solvothermal method with enhanced catalytic activity for H2O2 electroreduction

    NASA Astrophysics Data System (ADS)

    Cheng, Kui; Cao, Dianxue; Yang, Fan; Xu, Yang; Sun, Gaohui; Ye, Ke; Yin, Jinling; Wang, Guiling

    2014-05-01

    Hydrogen peroxide (H2O2) replaced oxygen (O2) as oxidant has been widely investigated due to its faster reduction kinetics, easier storage and handling than gaseous oxygen. The main challenge of using H2O2 as oxidant is the chemical decomposition. In this article, by using different C2H5OH/H2O volume ratio as the solvent, Co3O4 with different morphologies (nanosheet, nanowire, ultrafine nanowire net, nanobelts, and honeycomb-like) direct growth on Ni foam are synthesized via a simple solvothermal method for the first time. Results show that the introduction of ethanol could obviously improve the catalytic performance toward H2O2 electroreduction. The sample prepared in the solution with the C2H5OH/H2O volume ratio of 1:2 shows the best catalytic performance among the five samples and a current density of 0.214 A cm-2 is observed in 3.0 mol L-1 KOH + 0.5 mol L-1 H2O2 at -0.4 V (vs. Ag/AgCl KCl), which is much larger than that on the other metal oxides reported previously, almost comparable with the precious metals. This electrode of Co3O4 directly grown on Ni foam has superior mass transport property, which combining with its low-cost and facile preparation, make it a promising electrode for fuel cell using H2O2 as the oxidant.

  19. Geometry of α-Cr2O3(0001) as a Function of H2O Partial Pressure

    PubMed Central

    2015-01-01

    Surface X-ray diffraction has been employed to elucidate the surface structure of α-Cr2O3(0001) as a function of water partial pressure at room temperature. In ultra high vacuum, following exposure to ∼2000 Langmuir of H2O, the surface is found to be terminated by a partially occupied double layer of chromium atoms. No evidence of adsorbed OH/H2O is found, which is likely due to either adsorption at minority sites, or X-ray induced desorption. At a water partial pressure of ∼30 mbar, a single OH/H2O species is found to be bound atop each surface Cr atom. This adsorption geometry does not agree with that predicted by ab initio calculations, which may be a result of some differences between the experimental conditions and those modeled. PMID:26877825

  20. A Novel Coordination Polymer Constructed by Hetero-Metal Ions and 2,3-Pyridine Dicarboxylic Acid: Synthesis and Structure of [NiNa2(PDC)2(μ-H2O)(H2O)2] n

    NASA Astrophysics Data System (ADS)

    Dou, Ming-Yu; Lu, Jing

    2017-12-01

    A novel coordination polymer containing hetero-metal ions, [NiNa2(PDC)2(μ-H2O)(H2O)2] n , where PDC is 2,3-pyridine dicarboxylate ion, has been synthesized. In the structure, the PDC ligand chelates and bridges two Ni(II) and two Na(I) centers. Two kinds of metal centers are connected by μ4-PDC and μ2-H2O to form 2D coordination layers. Hydrogen bonds between coordination water molecules and carboxylate oxygen atoms further link these 2D coordination layers to form 3D supramolecular network.

  1. AC impedance spectroscopy of NASICON type Na3Fe2(PO4)3 ceramic

    NASA Astrophysics Data System (ADS)

    Mandal, Biswajit; Thakur, A. K.

    2018-05-01

    Super ionic conductors (e.g.; A3M2(XO4)3, A=Li, Na) have received attention in applied research due to their interesting electrochemical property and inherently high ionic conductivity [1]. However, structural and compatibility requirements for fast ion transport is stringent and it plays a crucial role. In A3M2(XO4)3, a suitable cage formation in the crystal framework due to corner sharing arrangement of XO4 tetrahedra and MO6 octahedra creates voids that acts as host/guest site for cation transport. In this work, we report Nasicon structure Na3Fe2(PO4)3 (NFP) prepared via sol-gel route mediated by citric acid. Structural analysis confirmed that NFP sample belongs to monoclinic crystal structure having Cc space group (S. G. No 9) with lattice parameters, a=15.106 Å, b=8.722 Å, c=8.775 Å and β=124.96°. Electrical properties of the prepared sample have been studied by AC impedance spectroscopy technique. The AC conductivity results indicated typical signature of ionically conducting system.

  2. Compressibility and thermal expansion of hydrous ringwoodite with 2.5(3) wt% H[subscript 2]O

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

    Ye, Yu; Brown, David A.; Smyth, Joseph R.

    Ringwoodite ({gamma}-Mg{sub 2}SiO{sub 4}) is the stable polymorph of olivine in the transition zone between 525-660 km depth, and can incorporate weight percent amounts of H{sub 2}O as hydroxyl, with charge compensated mainly by Mg vacancies (Mg{sup 2+} = 2H{sup +}), but also possibly as (Si{sup 4+} = 4H{sup +} and Mg{sup 2+} + 2H{sup +} = Si{sup 4+}). We synthesized pure Mg ringwoodite containing 2.5(3) wt% H{sub 2}O, measured by secondary ion mass spectrometry (SIMS), and determined its compressibility at 300 K by single-crystal and powder X-ray diffraction (XRD), as well as its thermal expansion behavior between 140 andmore » 740 K at room pressure. A third-order Birch-Murnaghan equation of state (BM3 EOS) fits values of the isothermal bulk modulus K{sub T0} = 159(7) GPa and (dK{sub T}/dP){sub P = 0} = K' = 6.7(7) for single-crystal XRD; K{sub T0} = 161(4) GPa and K' = 5.4(6) for powder XRD, with K{sub T0} = 160(2) GPa and K' = 6.2(3) for the combined data sets. At room pressure, hydrous ringwoodite breaks down by an irreversible unit-cell expansion above 586 K, which may be related to dehydration and changes in the disorder mechanisms. Single-crystal intensity data were collected at various temperatures up to 736 K, and show that the cell volume V(cell) has a mean thermal expansion coefficient {alpha}{sub V0} of 40(4) x 10{sup -6}/K (143-736 K), and 29(2) x 10{sup -6}/K (143-586 K before irreversible expansion). V(Mg) have {alpha}{sub 0} values of 41(3) x 10{sup -6}/K (143-736 K), and V(Si) has {alpha}{sub 0} values of 20(3) x 10{sup -6}/K (143-586 K) and 132(4) x 10{sup -6}K (586-736 K). Based on the experimental data and previous work from {sup 29}Si NMR, we propose that during the irreversible expansion, a small amount of H{sup +} cations in Mg sites transfer to Si sites without changing the cubic spinel structure of ringwoodite, and the substituted Si{sup 4+} cations move to the normally vacant octahedral site at (1/2, 1/2, 0). Including new SIMS data on

  3. Hyperekplexia mutation R271L of alpha1 glycine receptors potentiates allosteric interactions of nortropeines, propofol and glycine with [3H]strychnine binding.

    PubMed

    Maksay, Gábor; Bíró, Tímea; Laube, Bodo; Nemes, Péter

    2008-01-01

    Human alpha1 and hyperekplexia mutant alpha1(R271L) glycine receptors (GlyRs) were transiently expressed in human embryonic kidney 293 cells for [3H]strychnine binding. Binding parameters were determined using a ternary allosteric model. The hyperekplexia mutation increased the positive cooperativity of 0.3 mM propofol and glycine binding by about six times: the cooperativity factor beta was 0.26 for alpha1 GlyRs and 0.04 for alpha1(R271L) GlyRs. Thus, propofol restored the potency of glycine impaired by the mutation. Five nortropeines, i.e. substituted benzoates of nortropine and a new compound, nortropisetron were prepared and also examined on [3H]strychnine binding. They showed nanomolar displacing potencies amplified by the hyperekplexia mutation. The affinity of nor-O-zatosetron (2.6 nM) is one of the highest reported for GlyRs. This binding test offers an in vitro method to evaluate agents against neurological disorders associated with inherited mutations of GlyRs.

  4. Dynamic aggregation of the mid-sized gadolinium complex {Ph4[Gd(DTTA)(H2O)2](-)3}.

    PubMed

    Jaccard, Hugues; Miéville, Pascal; Cannizzo, Caroline; Mayer, Cédric R; Helm, Lothar

    2014-02-01

    A compound binding three Gd(3+) ions, {Ph4[Gd(DTTA)(H2O)2](-) 3} (where H5DTTA is diethylenetriaminetetraacetic acid), has been synthesized around a hydrophobic center made up of four phenyl rings. In aqueous solution the molecules start to self-aggregate at concentrations well below 1 mM as shown by the increase of rotational correlation times and by the decrease of the translational self-diffusion constant. NMR spectra recorded in aqueous solution of the diamagnetic analogue {Ph4[Y(DTTA)(H2O)2](-)3} show that the aggregation is dynamic and due to intermolecular π-stacking interactions between the hydrophobic aromatic centers. From estimations of effective radii, it can be concluded that the aggregates are composed of two to three monomers. The paramagnetic {Ph4[Gd(DTTA)(H2O)2](-)3} exhibits concentration-dependent (1)H NMR relaxivities with high values of approximately 50 mM(-1) s(-1) (30 MHz, 25 °C) at gadolinium concentrations above 20 mM. A combined analysis of (1)H NMR dispersion profiles measured at different concentrations of the compound and (17)O NMR data measured at various temperatures was performed using different theoretical approaches. The fitted parameters showed that the increase in relaxivity with increasing concentration of the compound is due to slower global rotational motion and an increase of the Lipari-Szabo order parameter S(2).

  5. Correlation between oxygen stoichiometry, structure, and opto-electrical properties in amorphous In2O3:H films

    NASA Astrophysics Data System (ADS)

    Koida, Takashi; Shibata, Hajime; Kondo, Michio; Tsutsumi, Koichi; Sakaguchi, Akio; Suzuki, Michio; Fujiwara, Hiroyuki

    2012-03-01

    We have characterized amorphous In2O3:H (H : ˜4 at.%) transparent conducting films by Rutherford backscattering spectrometry (RBS), thermal desorption spectroscopy, spectroscopic ellipsometry, and Hall measurements. The amorphous In2O3:H films have been fabricated at room temperature by sputtering of an In2O3 ceramic target under Ar, O2, and H2O vapor with variation of a flow ratio r(O2) = O2/(O2+Ar). We observe (i) signals originating from Ar in RBS spectra for all the films and (ii) desorption of H2O and Ar gases during post thermal annealing of the films. Furthermore, O2 desorption together with H2O and Ar is observed for the films grown at r(O2) > 0.375%, whereas In desorption together with H2O and Ar is observed for the films grown at r(O2) < 0.375%. These results suggest that the films have void and/or multi-vacancy rich structures inside the amorphous network, and the variety of atoms, such as Ar, H2O, and weakly bonded O and In, is present in the void structures for the films grown at O2-rich and O2-poor conditions, respectively. Corresponding to the structural changes, optical and electrical properties also change at r(O2) = 0.375%. For the films grown at r(O2) < 0.375%, we observe a broad absorption in the visible wavelengths that cannot be explained by free carrier absorption. In this film, the carrier mobility reduces rapidly with increasing carrier density. Analysis of spectroscopic ellipsometry and Hall measurements reveals that a large decrease in mobility is due to a large increase in carrier effective mass, in addition to the effect of ionized impurity scattering. In this article, we discuss the optical and transport properties with the variation of oxygen stoichiometry and microscopic structures in the amorphous In2O3:H films.

  6. The mid-IR Absorption Cross Sections of α- and β-NAT (HNO3 · 3H2O) in the range 170 to 185 K and of metastable NAD (HNO3 · 2H2O) in the range 172 to 182 K

    NASA Astrophysics Data System (ADS)

    Iannarelli, R.; Rossi, M. J.

    2015-11-01

    Growth and Fourier transform infrared (FTIR) absorption in transmission of the title nitric acid hydrates have been performed in a stirred flow reactor (SFR) under tight control of the H2O and HNO3 deposition conditions affording a closed mass balance of the binary mixture. The gas and condensed phases have been simultaneously monitored using residual gas mass spectrometry and FTIR absorption spectroscopy, respectively. Barrierless nucleation of the metastable phases of both α-NAT (nitric acid trihydrate) and NAD (nitric acid dihydrate) has been observed when HNO3 was admitted to the SFR in the presence of a macroscopic thin film of pure H2O ice of typically 1 µm thickness. The stable β-NAT phase was spontaneously formed from the precursor α-NAT phase through irreversible thermal rearrangement beginning at 185 K. This facile growth scheme of nitric acid hydrates requires the presence of H2O ice at thicknesses in excess of approximately hundred nanometers. Absolute absorption cross sections in the mid-IR spectral range (700-4000 cm-1) of all three title compounds have been obtained after spectral subtraction of excess pure ice at temperatures characteristic of the upper troposphere/lower stratosphere. Prominent IR absorption frequencies correspond to the antisymmetric nitrate stretch vibration (ν3(NO3-)) in the range 1300 to 1420 cm-1 and the bands of hydrated protons in the range 1670 to 1850 cm-1 in addition to the antisymmetric O-H stretch vibration of bound H2O in the range 3380 to 3430 cm-1 for NAT.

  7. The Cheshire-cat-like Behavior of 2nu(sub 3) Overtone of Co2 near 2.134 micron: NIR Lab Spectra of Solid CO2 in H2O and CH3OH

    NASA Technical Reports Server (NTRS)

    Bernstein, Max; Sandford, Scott; Cruikshank, Dale

    2005-01-01

    Infrared (IR) spectra have demonstrated that solid H2O is very common in the outer Solar System, and solid carbon dioxide (CO2) has been detected on icy satellites, comets, and planetismals throughout the outer Solar System. In such environments, CO2 and H2O must sometimes be mixed at a molecular level, changing their IR absorption features. In fact, the IR spectra of CO2-H2O mixtures are not equivalent to a linear combination of the spectra of the pure materials. Laboratory IR spectra of pure CO2 and H2O have been published but a lack of near-IR spectra of CO2-H2O mixtures has made the interpretation of outer Solar System spectra more difficult. We present near infrared (IR) spectra of CO2 in H2O and in CH3OH compared to that of pure solid CO2 and find significant differences. Peaks not present in either pure H2O or pure CO2 spectra become evident. First, the CO2 (2nu(sub 3)) overtone near 2.134 micron (4685/ cm) that is not seen in pure solid CO2 is prominent in the spectrum of a CO2/H2O = 25 mixture. Second, a 2.74 micron (3650/ cm) dangling OH feature of water (and a potentially related peak at 1.89 micron) appear in the spectra of CO2-H2O ice mixtures, but may not be specific to the presence of CO2. Other CO2 peaks display shifts in position and increased width because of intermolecular interactions with water. Changes in CO2 peak positions and profiles on warming of a CO2/H2O = 5 mixture are consistent with 'segregation' of the ice into nearly pure separate components. Absolute strengths for absorptions of CO2 in solid H2O are estimated. Similar results are observed for CO2 in solid CH3OH. Since the CO2 ( 2nu(sub 3)) overtone near 2.134 micron (4685/ cm) is not present in pure CO2 but prominent in mixtures it may be a good observational indicator of whether solid CO2 is a pure material or intimately mixed with other molecules. Significant changes in the near IR spectrum of solid CO2 in the presence of H2O and CH3OH means that the abundance of solid CO2 in the

  8. A Novel C2H2 Transcription Factor that Regulates gliA Expression Interdependently with GliZ in Aspergillus fumigatus

    PubMed Central

    Schoberle, Taylor J.; Nguyen-Coleman, C. Kim; Herold, Jennifer; Yang, Ally; Weirauch, Matt; Hughes, Timothy R.; McMurray, John S.; May, Gregory S.

    2014-01-01

    Secondary metabolites are produced by numerous organisms and can either be beneficial, benign, or harmful to humans. Genes involved in the synthesis and transport of these secondary metabolites are frequently found in gene clusters, which are often coordinately regulated, being almost exclusively dependent on transcription factors that are located within the clusters themselves. Gliotoxin, which is produced by a variety of Aspergillus species, Trichoderma species, and Penicillium species, exhibits immunosuppressive properties and has therefore been the subject of research for many laboratories. There have been a few proteins shown to regulate the gliotoxin cluster, most notably GliZ, a Zn2Cys6 binuclear finger transcription factor that lies within the cluster, and LaeA, a putative methyltransferase that globally regulates secondary metabolism clusters within numerous fungal species. Using a high-copy inducer screen in A. fumigatus, our lab has identified a novel C2H2 transcription factor, which plays an important role in regulating the gliotoxin biosynthetic cluster. This transcription factor, named GipA, induces gliotoxin production when present in extra copies. Furthermore, loss of gipA reduces gliotoxin production significantly. Through protein binding microarray and mutagenesis, we have identified a DNA binding site recognized by GipA that is in extremely close proximity to a potential GliZ DNA binding site in the 5′ untranslated region of gliA, which encodes an efflux pump within the gliotoxin cluster. Not surprisingly, GliZ and GipA appear to work in an interdependent fashion to positively control gliA expression. PMID:24784729

  9. Quantum chemical study of the mechanism of reaction between NH (X 3sigma-) and H2, H2O, and CO2 under combustion conditions.

    PubMed

    Mackie, John C; Bacskay, George B

    2005-12-29

    Reactions of ground-state NH (3sigma-) radicals with H2, H2O, and CO2 have been investigated quantum chemically, whereby the stationary points of the appropriate reaction potential energy surfaces, that is, reactants, products, intermediates, and transition states, have been identified at the G3//B3LYP level of theory. Reaction between NH and H2 takes place via a simple abstraction transition state, and the rate coefficient for this reaction as derived from the quantum chemical calculations, k(NH + H2) = (1.1 x 10(14)) exp(-20.9 kcal mol(-1)/RT) cm3 mol(-1) s(-1) between 1000 and 2000 K, is found to be in good agreement with experiment. For reaction between triplet NH and H2O, no stable intermediates were located on the triplet reaction surface although several stable species were found on the singlet surface. No intersystem crossing seam between triplet NH + H2O and singlet HNO + H2 (the products of lowest energy) was found; hence there is no evidence to support the existence of a low-energy pathway to these products. A rate coefficient of k(NH + H2O) = (6.1 x 10(13)) exp(-32.8 kcal mol(-1)/RT) cm3 mol(-1) s(-1) between 1000 and 2000 K for the reaction NH (3sigma-) + H2O --> NH2 (2B) + OH (2pi) was derived from the quantum chemical results. The reverse rate coefficient, calculated via the equilibrium constant, is in agreement with values used in modeling the thermal de-NO(x) process. For the reaction between triplet NH and CO2, several stable intermediates on both triplet and singlet reaction surfaces were located. Although a pathway from triplet NH + CO2 to singlet HNO + CO involving intersystem crossing in an HN-CO2 adduct was discovered, no pathway of sufficiently low activation energy was discovered to compare with that found in an earlier experiment [Rohrig, M.; Wagner, H. G. Proc. Combust. Inst. 1994, 25, 993.].

  10. Fine-structure relaxation of O(3P) induced by collisions with He, H and H2

    NASA Astrophysics Data System (ADS)

    Lique, F.; Kłos, J.; Alexander, M. H.; Le Picard, S. D.; Dagdigian, P. J.

    2018-02-01

    The excitation of fine-structure levels of O(3P) by collisions is an important cooling process in the interstellar medium (ISM). We investigate here spin-orbit (de-)excitation of O(3Pj, j = 0, 1, 2) induced by collisions with He, H and H2 based on quantum scattering calculations of the relevant rate coefficients in the 10-1000 K temperature range. The underlying potential energy surfaces are derived from highly correlated abinitio calculations. Significant differences were found with the rate coefficients currently used in astrophysical applications. In particular, our new rate coefficients for collisions with H are up to a factor of 5 lower. Radiative transfer computations allow the assessment of the astrophysical impact of these new rate coefficients. In the case of molecular clouds, the new data are found to increase slightly the flux of the 3P1 → 3P2, while decreasing the flux of the 3P0 → 3P1 line. In the case of atomic clouds, the flux of both lines is predicted to decrease. The new rate coefficients are expected to impact significantly the modelling of cooling in astrophysical environments while also allowing new insights into oxygen chemistry in the ISM.

  11. Hydrogen atom migration in the oxidation of aldehydes - O(3P) + H2CO

    NASA Technical Reports Server (NTRS)

    Dupuis, M.; Lester, W. A., Jr.

    1984-01-01

    An ab initio study of hydrogen atom migration in methylenebis(oxy)H2CO2(3B2) to form triplet formic acid HCOOH (3A1) is reported. From HF, MCHF, and CI calculated energy barriers, the activation energy is estimated to be no less than 30 kcal/mol. It is concluded that the hydrogen migration channel is not accessible in recent room temperature experiments on the O(3P) + H2CO reaction.

  12. 2,3-Dimethyl-6-nitro-2H-indazole

    PubMed Central

    Chen, Yan; Fang, Zheng; Wei, Ping

    2009-01-01

    In the mol­ecule of the title compound, C9H9N3O2, the indazole ring system is almost planar [maximum deviation = 0.019 (3) Å for the C atom bearing the nitro group]. In the crystal structure, inter­molecular C—H⋯O inter­actions link the mol­ecules into centrosymmetric dimers, forming R 2 2(18) ring motifs. Aromatic π–π contacts between indazole rings [centroid–centroid distances = 3.632 (1) and 3.705 (1) Å] may further stabilize the structure. PMID:21583483

  13. Crystal structures of [NEt3H]5[XCoIIW11O39]·3H2O (X = P or As)

    USGS Publications Warehouse

    Evans, H.T.; Weakley, T.J.R.; Jameson, G.B.

    1996-01-01

    The orthorhombic crystal structures of [NEt3H]5[XCoIIW11O39]·3H2O for X = P and As have been determined with data collected at room temperature, and for X = P at –100 °C, using Mo-Kα radiation. For the latter the space group is Pna21, a= 21.670(11), b= 14.805(4), c= 20.393(5)Å and Z= 4. The structure consists of chains of α-Keggin-type molecules joined by W–O–links aligned in the a-axis direction. The Co/W occupancy at the link is disordered, with 61% Co on one side and 39% on the other. Further probable disorder, by lamellar merohedral twinning on (001) and by misorientation of the triethylammonium ions, has obscured the ethyl groups and the water molecules. In polarized light the crystals are deep wine-red normal to the chains (in the b direction), but nearly colourless in the a and c directions. The structure of the arsenate is similar to that of the phosphate.

  14. Optical and dielectric properties of isothermally crystallized nano-KNbO3 in Er3+-doped K2O-Nb2O5-SiO2 glasses.

    PubMed

    Chaliha, Reenamoni Saikia; Annapurna, K; Tarafder, Anal; Tiwari, V S; Gupta, P K; Karmakar, Basudeb

    2010-01-01

    Precursor glass of composition 25K(2)O-25Nb(2)O(5)-50SiO(2) (mol%) doped with Er(2)O(3) (0.5 wt% in excess) was isothermally crystallized at 800 degrees C for 0-100 h to obtain transparent KNbO(3) nanostructured glass-ceramics. XRD, FESEM, TEM, FTIRRS, dielectric constant, refractive index, absorption and fluorescence measurements were carried out to analyze the morphology, dielectric, structure and optical properties of the glass-ceramics. The crystallite size of KNbO(3) estimated from XRD and TEM is found to vary in the range 7-23 nm. A steep rise in the dielectric constant of glass-ceramics with heat-treatment time reveals the formation of ferroelectric nanocrystalline KNbO(3) phase. The measured visible photoluminescence spectra have exhibited green emission transitions of (2)H(11/2), (4)S(3/2)-->(4)I(15/2) upon excitation at 377 nm ((4)I(15/2)-->(4)G(11/2)) absorption band of Er(3+) ions. The near infrared (NIR) emission transition (4)I(13/2)-->(4)I(15/2) is detected around 1550 nm on excitation at 980 nm ((4)I(15/2)-->(4)I(11/2)) of absorption bands of Er(3+) ions. It is observed that photoluminescent intensity at 526 nm ((2)H(11/2)-->(4)I(15/2)), 550 nm ((4)S(3/2)-->(4)I(15/2)) and 1550 nm ((4)I(13/2)-->(4)I(15/2)) initially decrease and then gradually increase with increase in heat-treatment time. The measured lifetime (tau(f)) of the (4)I(13/2)-->(4)I(15/2) transition also possesses a similar trend. The measured absorption and fluorescence spectra reveal that the Er(3+) ions gradually enter into the KNbO(3) nanocrystals. Copyright 2009 Elsevier B.V. All rights reserved.

  15. Investigation of radiation shielding properties for MeO-PbCl2-TeO2 (MeO = Bi2O3, MoO3, Sb2O3, WO3, ZnO) glasses

    NASA Astrophysics Data System (ADS)

    Sayyed, M. I.; Çelikbilek Ersundu, M.; Ersundu, A. E.; Lakshminarayana, G.; Kostka, P.

    2018-03-01

    In this work, glasses in the MeO-PbCl2-TeO2 (MeO = Bi2O3, MoO3, Sb2O3, WO3, ZnO) system, which show a great potential for optoelectronic applications, were used to evaluate their resistance under high energy ionizing radiations. The basic shielding quantities for determining the penetration of radiation in glass, such as mass attenuation coefficient (μ/ρ), half value layer (HVL), mean free path (MFP) and exposure buildup factor (EBF) values were investigated within the energy range 0.015 MeV ‒ 15 MeV using XCOM program and variation of shielding parameters were compared with different glass systems and ordinary concrete. From the derived results, it was determined that MeO-PbCl2-TeO2 (MeO = Bi2O3, MoO3, Sb2O3, WO3, ZnO) glasses show great potentiality to be used under high energy radiations. Among the studied glass compositions, Bi2O3 and WO3 containing glasses were found to possess superior gamma-ray shielding effectiveness.

  16. Effects of nano-YAG (Y 3Al 5O 12) crystallization on the structure and photoluminescence properties of Nd 3+-doped K 2O-SiO 2-Y 2O 3-Al 2O 3 glasses

    NASA Astrophysics Data System (ADS)

    Tarafder, Anal; Molla, Atiar Rahaman; Karmakar, Basudeb

    2010-10-01

    Nd 3+-doped precursor glass in the K 2O-SiO 2-Y 2O 3-Al 2O 3 (KSYA) system was prepared by the melt-quench technique. The transparent Y 3Al 5O 12 (YAG) glass-ceramics were derived from this glass by a controlled crystallization process at 750 °C for 5-100 h. The formation of YAG crystal phase, size and morphology with progress of heat-treatment was examined by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and Fourier transformed infrared reflectance spectroscopy (FT-IRRS). The crystallite sizes obtained from XRD are found to increase with heat-treatment time and vary in the range 25-40 nm. The measured photoluminescence spectra have exhibited emission transitions of 4F 3/2 → 4I J ( J = 9/2, 11/2 and 13/2) from Nd 3+ ions upon excitation at 829 nm. It is observed that the photoluminescence intensity and excited state lifetime of Nd 3+ ions decrease with increase in heat-treatment time. The present study indicates that the incorporation of Nd 3+ ions into YAG crystal lattice enhance the fluorescence performance of the glass-ceramic nanocomposites.

  17. Reduction Mechanisms of Cu2+-Doped Na2O-Al2O3-SiO2 Glasses during Heating in H2 Gas.

    PubMed

    Nogami, Masayuki; Quang, Vu Xuan; Ohki, Shinobu; Deguchi, Kenzo; Shimizu, Tadashi

    2018-01-25

    Controlling valence state of metal ions that are doped in materials has been widely applied for turning optical properties. Even though hydrogen has been proven effective to reduce metal ions because of its strong reducing capability, few comprehensive studies focus on practical applications because of the low diffusion rate of hydrogen in solids and the limited reaction near sample surfaces. Here, we investigated the reactions of hydrogen with Cu 2+ -doped Na 2 O-Al 2 O 3 -SiO 2 glass and found that a completely different reduction from results reported so far occurs, which is dominated by the Al/Na concentration ratio. For Al/Na < 1, Cu 2+ ions were reduced via hydrogen to metallic Cu, distributing in glass body. For Al/Na > 1, on the other hand, the reduction of Cu 2+ ions occurred simultaneously with the formation of OH bonds, whereas the reduced Cu metal moved outward and formed a metallic film on glass surface. The NMR and Fourier transform infrared results indicated that the Cu 2+ ions were surrounded by Al 3+ ions that formed AlO 4 , distorted AlO 4 , and AlO 5 units. The diffused H 2 gas reacted with the Al-O - ···Cu + units, forming Al-OH and metallic Cu, the latter of which moved freely toward glass surface and in return enhanced H 2 diffusion.

  18. Nqrs Data for C26H38N2O3 (Subst. No. 1607)

    NASA Astrophysics Data System (ADS)

    Chihara, H.; Nakamura, N.

    This document is part of Subvolume B 'Substances Containing C10H16 … Zn' of Volume 48 'Nuclear Quadrupole Resonance Spectroscopy Data' of Landolt-Börnstein - Group III 'Condensed Matter'. It contains an extract of Section '3.2 Data tables' of the Chapter '3 Nuclear quadrupole resonance data' providing the NQRS data for C26H38N2O3 (Subst. No. 1607)

  19. Hygroscopic La[B{sub 5}O{sub 8}(OH)]NO{sub 32H{sub 2}O: Insight into the evolution of borate fundamental building blocks

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

    Zhao, Biao-Chun, E-mail: zhaobiaochun@sohu.com; Sun, Wei, E-mail: 421221789@qq.com; Ren, Wei-Jian, E-mail: 935428502@qq.com

    2013-10-15

    Borates have exceptionally diverse fundamental building blocks (FBBs), but factors controlling the formation of borate FBBs are poorly understood. The title compound La[B{sub 5}O{sub 8}(OH)]NO{sub 32H{sub 2}O crystallizes in the space group P2{sub 1}/n with a=6.5396(12) Å, b=15.550(3) Å, c=10.6719(19) Å, β=90.44(1)° and Z=4 at 173(2) K. Its structure has been refined from single-crystal X-ray diffraction data to R{sub 1}=0.049 (for 2465) and wR{sub 2}=0.173 (for 2459 I>2σ(I)). This structure analysis and first-principles calculations show that the change of the FBB from 3Δ2□ in the title compound to 2Δ3□ in La[B{sub 5}O{sub 8}(OH)(H{sub 2}O)]NO{sub 32H{sub 2}O is accompanied by amore » rotation of the NO{sub 3} group. FTIR, Rietveld and thermal analysis results show that the hygroscopic title compound is partially changed to La[B{sub 5}O{sub 8}(OH)(H{sub 2}O)]NO{sub 32H{sub 2}O, with the conversion of [BO{sub 3}] to [BO{sub 3}(H{sub 2}O)] by water absorption. - Graphical abstract: The change of fundamental building blocks from La[B{sub 5}O{sub 8}(OH)]NO{sub 32H{sub 2}O to La[B{sub 5}O{sub 8}(OH)(H{sub 2}O)]NO{sub 32H{sub 2}O is accompanied by a rotation of the NO{sub 3} group . Display Omitted - Highlights: • Synthesis of a new hydrous lanthanum polyborate nitrate. • Single-crystal XRD structure with the 3Δ2⎕ FBB and an oriented NO{sub 3} group. • DFT calculations locate the H positions in three lanthanide polyborate nitrates. • Rietveld, FTIR and DFT results show hygroscopicity changes the FBBs.« less

  20. Theoretical insight into OH- and Cl-initiated oxidation of CF3OCH(CF3)2 and CF3OCF2CF2H & fate of CF3OC(X•)(CF3)2 and CF3OCF2CF2X• radicals (X=O, O2)

    PubMed Central

    Bai, Feng-Yang; Ma, Yuan; Lv, Shuang; Pan, Xiu-Mei; Jia, Xiu-Juan

    2017-01-01

    In this study, the mechanistic and kinetic analysis for reactions of CF3OCH(CF3)2 and CF3OCF2CF2H with OH radicals and Cl atoms have been performed at the CCSD(T)//B3LYP/6-311++G(d,p) level. Kinetic isotope effects for reactions CF3OCH(CF3)2/CF3OCD(CF3)2 and CF3OCF2CF2H/CF3OCF2CF2D with OH and Cl were estimated so as to provide the theoretical estimation for future laboratory investigation. All rate constants, computed by canonical variational transition state theory (CVT) with the small-curvature tunneling correction (SCT), are in reasonable agreement with the limited experimental data. Standard enthalpies of formation for the species were also calculated. Atmospheric lifetime and global warming potentials (GWPs) of the reaction species were estimated, the large lifetimes and GWPs show that the environmental impact of them cannot be ignored. The organic nitrates can be produced by the further oxidation of CF3OC(•)(CF3)2 and CF3OCF2CF2• in the presence of O2 and NO. The subsequent decomposition pathways of CF3OC(O•)(CF3)2 and CF3OCF2CF2O• radicals were studied in detail. The derived Arrhenius expressions for the rate coefficients over 230–350 K are: k T(1) = 5.00 × 10−24T3.57 exp(−849.73/T), k T(2) = 1.79 × 10−24T4.84 exp(−4262.65/T), kT(3) = 1.94 × 10−24 T4.18 exp(−884.26/T), and k T(4) = 9.44 × 10−28T5.25 exp(−913.45/T) cm3 molecule−1 s−1. PMID:28067283

  1. Theoretical insight into OH- and Cl-initiated oxidation of CF3OCH(CF3)2 and CF3OCF2CF2H & fate of CF3OC(X•)(CF3)2 and CF3OCF2CF2X• radicals (X=O, O2)

    NASA Astrophysics Data System (ADS)

    Bai, Feng-Yang; Ma, Yuan; Lv, Shuang; Pan, Xiu-Mei; Jia, Xiu-Juan

    2017-01-01

    In this study, the mechanistic and kinetic analysis for reactions of CF3OCH(CF3)2 and CF3OCF2CF2H with OH radicals and Cl atoms have been performed at the CCSD(T)//B3LYP/6-311++G(d,p) level. Kinetic isotope effects for reactions CF3OCH(CF3)2/CF3OCD(CF3)2 and CF3OCF2CF2H/CF3OCF2CF2D with OH and Cl were estimated so as to provide the theoretical estimation for future laboratory investigation. All rate constants, computed by canonical variational transition state theory (CVT) with the small-curvature tunneling correction (SCT), are in reasonable agreement with the limited experimental data. Standard enthalpies of formation for the species were also calculated. Atmospheric lifetime and global warming potentials (GWPs) of the reaction species were estimated, the large lifetimes and GWPs show that the environmental impact of them cannot be ignored. The organic nitrates can be produced by the further oxidation of CF3OC(•)(CF3)2 and CF3OCF2CF2• in the presence of O2 and NO. The subsequent decomposition pathways of CF3OC(O•)(CF3)2 and CF3OCF2CF2O• radicals were studied in detail. The derived Arrhenius expressions for the rate coefficients over 230-350 K are: k T(1) = 5.00 × 10-24T3.57 exp(-849.73/T), k T(2) = 1.79 × 10-24T4.84 exp(-4262.65/T), kT(3) = 1.94 × 10-24 T4.18 exp(-884.26/T), and k T(4) = 9.44 × 10-28T5.25 exp(-913.45/T) cm3 molecule-1 s-1.

  2. An H2A Histone Isotype, H2ac, Associates with Telomere and Maintains Telomere Integrity

    PubMed Central

    Tzeng, Tsai-Yu; Lin, I-Hsuan; Hsu, Ming-Ta

    2016-01-01

    Telomeres are capped at the ends of eukaryotic chromosomes and are composed of TTAGGG repeats bound to the shelterin complex. Here we report that a replication-dependent histone H2A isotype, H2ac, was associated with telomeres in human cells and co-immunoprecipitates with telomere repeat factor 2 (TRF2) and protection of telomeres protein 1 (POT1), whereas other histone H2A isotypes and mutations of H2ac did not bind to telomeres or these two proteins. The amino terminal basic domain of TRF2 was necessary for the association with H2ac and for the recruitment of H2ac to telomeres. Depletion of H2ac led to loss of telomeric repeat sequences, the appearance of dysfunctional telomeres, and chromosomal instability, including chromosomal breaks and anaphase bridges, as well as accumulation of telomere-associated DNA damage factors in H2ac depleted cells. Additionally, knockdown of H2ac elicits an ATM-dependent DNA damage response at telomeres and depletion of XPF protects telomeres against H2ac-deficiency-induced G-strand overhangs loss and DNA damage response, and prevents chromosomal instability. These findings suggest that the H2A isotype, H2ac, plays an essential role in maintaining telomere functional integrity. PMID:27228173

  3. (1→3)-β-d-Glucan oligosaccharides monomers purification and its H2O2 induction effect study.

    PubMed

    Fu, Yunbin; Wang, Mengyu; Wang, Wenxia; Tuo, Yaqin; Guo, Zhimou; Du, Yuguang; Yin, Heng

    2015-11-01

    In order to produce highly purified (1→3)-β-d-glucan oligosaccharides ((1→3)-β-d-GOS) monomers, a hydrophilic interaction liquid chromatography (HILIC) system with X-Amide stationary phase was performed. Nine (1→3)-β-d-GOS monomers with degree of polymerization (DP) from 2 to 10 were successfully separated. Matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS) demonstrated that these monomers were with high purity. Furthermore, a hydrogen peroxide (H2O2) online detection method was established to monitor H2O2 releases in tobacco cells. This is the first report on nine consecutive (1→3)-β-d-GOS monomers purification and its effect upon H2O2-releasing in plants. It was found that (1→3)-β-d-GOS monomers with higher DP induced stronger defense responses in plants, which will pave the way for elucidating the relationship between (1→3)-β-d-GOS and biological activities. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. The TAED/H2O2/NaHCO3 system as an approach to low-temperature and near-neutral pH bleaching of cotton.

    PubMed

    Long, Xiaoxia; Xu, Changhai; Du, Jinmei; Fu, Shaohai

    2013-06-05

    A low-temperature and near-neutral pH bleaching system was conceived for cotton by incorporating TAED, H2O2 and NaHCO3. The TAED/H2O2/NaHCO3 system was investigated and optimized for bleaching of cotton using a central composite design (CCD) combined with response surface methodology (RSM). CCD experimental data were fitted to create a response surface quadratic model (RSQM) describing the degree of whiteness of bleached cotton fabric. Analysis of variance for the RSQM revealed that temperature was the most significant variable, followed by [TAED] and time, while [NaHCO3] was insignificant. An effective system was conducted by adding 5.75 g L(-1) TAED together with H2O2 and NaHCO3 at a molar ratio of 1:2.4:2.8 and applied to bleaching of cotton at 70 °C for 40 min. Compared to a commercial bleaching method, the TAED/H2O2/NaHCO3 system provided cotton with comparable degree of whiteness, slightly inferior water absorbency and acceptable dyeability, but had competitive advantage in protecting cotton from severe chemical damage in bleaching. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. 14-3-3ζ turns TGF-β’s function from tumor suppressor to metastasis promoter in breast cancer by contextual changes of Smad partners from p53 to Gli2

    PubMed Central

    Xu, Jia; Acharya, Sunil; Sahin, Ozgur; Zhang, Qingling; Saito, Yohei; Yao, Jun; Wang, Hai; Li, Ping; Zhang, Lin; Lowery, Frank J; Kuo, Wen-Ling; Xiao, Yi; Ensor, Joe; Sahin, Aysegul A; Zhang, Xiang H.-F.; Hung, Mien-Chie; Zhang, Jitao David; Yu, Dihua

    2015-01-01

    Summary Transforming growth factor-β (TGF-β) functions as a tumor suppressor in pre-malignant cells but as a metastasis promoter in cancer cells. The dichotomous functions of TGF-β are proposed to be dictated by different partners of its downstream effectors Smads. However, the mechanism for the contextual changes of Smad partners remained undefined. Here, we demonstrate that 14-3-3ζ destabilizes p53, a Smad partner in pre-malignant mammary epithelial cells, by downregulating 14-3-3σ, thus turning off TGF-β’s tumor suppression function. Conversely, 14-3-3ζ stabilizes Gli2 in breast cancer cells, and Gli2 partners with Smads to activate PTHrP and promote TGF-β-induced bone metastasis. The 14-3-3ζ-driven contextual changes of Smad partners from p53 to Gli2 may serve as biomarkers and therapeutic targets of TGF-β-mediated cancer progression. PMID:25670079

  6. Visible spectrum photofragmentation of O{sub 3}{sup −}(H{sub 2}O){sub n}, n ≤ 16

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

    Lehman, Julia H.; Lineberger, W. Carl, E-mail: wcl@jila.colorado.edu

    2014-10-21

    Photofragmentation of ozonide solvated in water clusters, O{sub 3}{sup −}(H{sub 2}O){sub n}, n ≤ 16, has been studied as a function of photon energy as well as the degree of solvation. Using mass selection, the effect of the presence of the solvent molecule on the O{sub 3}{sup −} photodissociation process is assessed one solvent molecule at a time. The O{sub 3}{sup −} acts as a visible light chromophore within the water cluster, namely the O{sub 3}{sup −}(H{sub 2}O) total photodissociation cross-section exhibits generally the same photon energy dependence as isolated O{sub 3}{sup −} throughout the visible wavelength range studied (430–620more » nm). With the addition of a single solvent molecule, new photodissociation pathways are opened, including the production of recombined O{sub 3}{sup −}. As the degree of solvation of the parent anion increases, recombination to O{sub 3}{sup −}-based products accounts for close to 40% of photoproducts by n = 16. The remainder of the photoproducts exist as O{sup −}-based; no O{sub 2}{sup −}-based products are observed. Upper bounds on the O{sub 3}{sup −} solvation energy (530 meV) and the O{sup −}-OO bond dissociation energy in the cluster (1.06 eV) are derived.« less

  7. A novel highly efficient adsorbent {[Co4(L)23-OH)2(H2O)3(4,4‧-bipy)2]·(H2O)2}n: Synthesis, crystal structure, magnetic and arsenic (V) absorption capacity

    NASA Astrophysics Data System (ADS)

    Zhang, Chong; Xiao, Yu; Qin, Yan; Sun, Quanchun; Zhang, Shuhua

    2018-05-01

    A novel highly efficient adsorbent-microporous tetranuclear Co(II)-based polymer, {[Co4(L)23-OH)2(H2O)3(4,4‧-bipy)2]·(H2O)2}n (1, H3L = 4-(N,N‧-bis(4-carboxybenzyl)amino) benzenesulfonic acid, 4,4‧-bipy = 4,4‧-bipyridine), was hydrothermally synthesized. The complex 1 is a metal-organic framework (MOF) material which was characterized by single-crystal X-ray diffraction, BET and platon software. Co-MOF (complex 1) reveals excellent adsorption property. The capacity of Co-MOF to remove arsenic As(V) from sodium arsenate aqueous solutions was investigated (The form of As(V) is AsO43-). The experimental results showed that Co-MOF had a higher stable and relatively high As(V) removal rate (> 98%) at pH 4-10. The adsorption kinetics followed a pseudo-second-order kinetic model, and the adsorption isotherm followed the Langmuir equation. Co-MOF exhibits a very high adsorption capacity of As(V) in aqueous solution (Qmax of 96.08 mg/g). Finally, the optimal adsorption conditions for the model were obtained through a Box-Behnken response surface experiment which was designed with adsorption time, dose, temperature and rotational speed of the shaker as the influencing factors to determine two-factor interaction effects. Co-MOF was further characterized using FTIR, PXRD, X-ray photoelectron spectroscopy before and after adsorption As (V). The magnetism of Co-MOF was also discussed.

  8. On the Formation of the C2H6O Isomers Ethanol (C2H5OH) and Dimethyl Ether (CH3OCH3) in Star-forming Regions

    NASA Astrophysics Data System (ADS)

    Bergantini, Alexandre; Maksyutenko, Pavlo; Kaiser, Ralf I.

    2017-06-01

    The structural isomers ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3) were detected in several low-, intermediate-, and high-mass star-forming regions, including Sgr B2, Orion, and W33A, with the relative abundance ratios of ethanol/dimethyl ether varying from about 0.03 to 3.4. Until now, no experimental data regarding the formation mechanisms and branching ratios of these two species in laboratory simulation experiments could be provided. Here, we exploit tunable photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS) to detect and analyze the production of complex organic molecules (COMs) resulting from the exposure of water/methane (H2O/CH4) ices to energetic electrons. The main goal is to understand the formation mechanisms in star-forming regions of two C2H6O isomers: ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3). The results show that the experimental branching ratios favor the synthesis of ethanol versus dimethyl ether (31 ± 11:1). This finding diverges from the abundances observed toward most star-forming regions, suggesting that production routes on interstellar grains to form dimethyl ether might be missing; alternatively, ethanol can be overproduced in the present simulation experiments, such as via radical-radical recombination pathways involving ethyl and hydroxyl radicals. Finally, the PI-ReTOF-MS data suggest the formation of methylacetylene (C3H4), ketene (CH2CO), propene (C3H6), vinyl alcohol (CH2CHOH), acetaldehyde (CH3CHO), and methyl hydroperoxide (CH3OOH), in addition to ethane (C2H6), methanol (CH3OH), and CO2 detected from infrared spectroscopy. The yield of all the confirmed species is also determined.

  9. Synthesis and X-ray crystal structure of (OsO(3)F(2))(2)2XeOF(4) and the Raman spectra of (OsO(3)F(2))(infinity), (OsO(3)F(2))(2), and (OsO(3)F(2))(2)2XeOF(4).

    PubMed

    Hughes, Michael J; Mercier, Hélène P A; Schrobilgen, Gary J

    2009-05-18

    The adduct, (OsO(3)F(2))(2)2XeOF(4), was synthesized by dissolution of the infinite chain polymer, (OsO(3)F(2))(infinity), in XeOF(4) solvent at room temperature followed by removal of excess XeOF(4) under dynamic vacuum at 0 degrees C. Continued pumping at 0 degrees C resulted in removal of associated XeOF(4), yielding (OsO(3)F(2))(2), a new low-temperature phase of OsO(3)F(2). Upon standing at 25 degrees C for 1(1)/(2) h, (OsO(3)F(2))(2) underwent a phase transition to the known monoclinic phase, (OsO(3)F(2))(infinity). The title compounds, (OsO(3)F(2))(infinity), (OsO(3)F(2))(2), and (OsO(3)F(2))(2)2XeOF(4) have been characterized by low-temperature (-150 degrees C) Raman spectroscopy. Crystallization of (OsO(3)F(2))(2)2XeOF(4) from XeOF(4) solution at 0 degrees C yielded crystals suitable for X-ray structure determination. The structural unit contains the (OsO(3)F(2))(2) dimer in which the OsO(3)F(3) units are joined by two Os---F---Os bridges having fluorine bridge atoms that are equidistant from the osmium centers (2.117(5) and 2.107(4) A). The dimer coordinates to two XeOF(4) molecules through Os-F...Xe bridges in which the Xe...F distances (2.757(5) A) are significantly less than the sum of the Xe and F van der Waals radii (3.63 A). The (OsO(3)F(2))(2) dimer has C(i) symmetry in which each pseudo-octahedral OsO(3)F(3) unit has a facial arrangement of oxygen ligands with XeOF(4) molecules that are only slightly distorted from their gas-phase C(4v) symmetry. Quantum-chemical calculations using SVWN and B3LYP methods were employed to calculate the gas-phase geometries, natural bond orbital analyses, and vibrational frequencies of (OsO(3)F(2))(2), (OsO(3)F(2))(2)2XeOF(4), XeOF(4), OsO(2)F(4), and (mu-FOsO(3)F(2))(2)OsO(3)F(-) to aid in the assignment of the experimental vibrational frequencies of (OsO(3)F(2))(2), (OsO(3)F(2))(2)2XeOF(4), and (OsO(3)F(2))(infinity). The vibrational modes of the low-temperature polymeric phase, (OsO(3)F(2))(infinity), have been

  10. Photocrystallographic structure determination of a new geometric isomer of [Ru(NH3)4(H2O)(eta1-OSO)][MeC6H4SO3]2.

    PubMed

    Bowes, Katharine F; Cole, Jacqueline M; Husheer, Shamus L G; Raithby, Paul R; Savarese, Teresa L; Sparkes, Hazel A; Teat, Simon J; Warren, John E

    2006-06-21

    The structure of a new metastable geometric isomer of [Ru(NH3)4(H2O)(SO2)][MeC6H4SO3]2 in which the SO2 group is coordinated through a single oxygen in an eta1-OSO bonding mode has been determined at 13 K; the new isomer was obtained as a 36% component of the structure within a single crystal upon irradiation using a tungsten lamp.

  11. Morphological control of La0.7Sr0.3Co0.2Fe0.8O3-δ and La0.7Sr0.3MnO3-δ catalytic membrane using PEG-H2O additive

    NASA Astrophysics Data System (ADS)

    Iqbal, R. M.; Nurherdiana, S. D.; Hartanto, D.; Othman, M. H. D.; Fansuri, H.

    2018-04-01

    Methane is the primary combustible component in non condensable part of natural gas. It is a promising source for syngas (CO and H2) production by partial oxidation method. The conversion of methane to syngas by partial oxidation method needs a controlled amount of oxygen. Membrane which has asymmetric structure and selectively permeates oxygen can be used to supply just enough oxygen to the reaction. One pathway to the fabricate asymmetric membrane is phase inversion method with an addition of PEG to increase pore size. La0.7Sr0.3Co0.2Fe0.8O3-δ (LSCF 7328) and Laa0.7Sr0.3MnO3-δ (LSM 73) powder were synthesized by solid-state method and they were characterized by XRD. The green membrane was prepared by phase inversion method. A dope solution was made by mixing LSCF 7328 or LSM 73 powder with PEG and stirred them in NMP for 24 h. PESf was then added into the dope solution and the stirring was continued to another 24 h. The resulted dope solution was degassed by immersing the solution inside and conical flask in an ultrasonic bath to remove air bubbles. The degassed mixture was then casted by spreading it on a glass surface (with a thickness of 2 mm) followed by immersion in a water bath for 24 h to coagulate the degassed mixture. Membrane morphology was characterized by Scanning Electron Microscopy (SEM) while the decomposition temperature of the polymer binder was analyzed by Thermogravimetric Analyzer (TGA). The XRD results show that phase of LSCF 7328 and LSM 73 are similar to LaCoO3 and LaMnO3, respectively. It indicated that the perovskite synthesis was successful. SEM micrograph of membrane cross sections show that the green membrane have finger like pores and a dense layer. Pores also appear on top and bottom surface of the membrane. Based on TGA results, the highest weight lost of green membrane at 550-600°C which represents the decomposition of PESf binder.

  12. Cooperativity effect involving drug-DNA/RNA intermolecular interaction: A B3LYP-D3 and MP2 theoretical investigation on ketoprofen⋯cytosine⋯H2O system.

    PubMed

    Zhen, Jun-Ping; Wei, Xiao-Chun; Shi, Wen-Jing; Huang, Zhu-Yuan; Jin, Bo; Zhou, Yu-Kun

    2017-11-14

    In order to examine the origin of the drug action and design new DNA/RNA-targeted drugs, the cooperativity effect involving drug-DNA/RNA intermolecular interaction in ketoprofen⋯cytosine⋯H 2 O ternary system were investigated by the B3LYP, B3LYP-D3, and MP2 methods with the 6-311++G(2d,p) basis set. The thermodynamic cooperativity was also evaluated at 310.15 K. The N-H⋯O, O-H⋯O, O-H⋯N, C-H⋯N, and C-H⋯O H bonds coexist in ternary complexes. The intermolecular interactions obtained by B3LYP-D3 are close to those calculated by MP2. The steric effects and van der Waals interactions have little influence on the cooperativity effects. The anti-cooperativity effect in ket⋯cyt⋯H 2 O is far more notable than the cooperativity effect, and the stability of the cyclic structure with anti-cooperativity effect is higher than that of the linear structure with cooperativity effect, as is confirmed by the AIM (atoms in molecules) and RDG (reduced density gradient) analysis. Thus, it can be inferred that, in the presence of H 2 O, the anti-cooperativity effect plays a dominant role in the drug-DNA/RNA interaction, and the nature of the hydration in the binding of drugs to DNA/RNA bases is the H-bonding anti-cooperativity effect. Furthermore, the drug always links simultaneously with DNA/RNA base and H 2 O, and only in this way can the biological activity of drugs play a role. In most cases, the enthalpy change is the major factor driving the cooperativity, as is different from most of biomacromolecule complexes.

  13. Large Conformational Changes of Insertion 3 in Human Glycyl-tRNA Synthetase (hGlyRS) during Catalysis

    DOE PAGES

    Deng, Xiangyu; Qin, Xiangjing; Chen, Lei; ...

    2016-01-21

    Glycyl-tRNA synthetase (GlyRS) is the enzyme that covalently links glycine to cognate tRNA for translation. It is of great interest because of its nonconserved quaternary structures, unique species-specific aminoacylation properties, and noncanonical functions in neurological diseases, but none of these is fully understood. We report two crystal structures of human GlyRS variants, in the free form and in complex with tRNA Gly respectively, and reveal new aspects of the glycylation mechanism. We discover that insertion 3 differs considerably in conformation in catalysis and that it acts like a "switch" and fully opens to allow tRNA to bind in a cross-subunitmore » fashion. The flexibility of the protein is supported by molecular dynamics simulation, as well as enzymatic activity assays. The biophysical and biochemical studies suggest that human GlyRS may utilize its flexibility for both the traditional function (regulate tRNA binding) and alternative functions (roles in diseases).« less

  14. Thermodynamic data of lawsonite and zoisite in the system CaO-Al2O3-SiO2-H2O based on experimental phase equilibria and calorimetric work

    NASA Astrophysics Data System (ADS)

    Grevel, Klaus-Dieter; Schoenitz, Mirko; Skrok, Volker; Navrotsky, Alexandra; Schreyer, Werner

    2001-08-01

    The enthalpy of drop-solution in molten 2PbO.B2O3 of synthetic and natural lawsonite, CaAl2(Si2O7)(OH)2.H2O, was measured by high-temperature oxide melt calorimetry. The enthalpy of formation determined for the synthetic material is ΔfHOxides=-168.7+/-3.4 kJ mol-1, or ΔfH0298=-4,872.5+/-4.0 kJ mol-1. These values are in reasonable agreement with previously published data, although previous calorimetric work yielded slightly more exothermic data and optimisation methods resulted in slightly less exothermic values. The equilibrium conditions for the dehydration of lawsonite to zoisite, kyanite and quartz/coesite at pressures and temperatures up to 5 GPa and 850 °C were determined by piston cylinder experiments. These results, other recent phase equilibrium data, and new calorimetric and thermophysical data for lawsonite and zoisite, Ca2Al3(SiO4)(Si2O7)O(OH), were used to constrain a mathematical programming analysis of the thermodynamic data for these two minerals in the chemical system CaO-Al2O3-SiO2-H2O (CASH). The following data for lawsonite and zoisite were obtained: ΔfH0298 (lawsonite)=-4,865.68 kJ mol-1 , S0298 (lawsonite)=229.27 J K-1 mol-1 , ΔfH0298 (zoisite)=-6,888.99 kJ mol-1 , S0298 (zoisite)=297.71 J K-1 mol-1 . Additionally, a recalculation of the bulk modulus of lawsonite yielded K=120.7 GPa, which is in good agreement with recent experimental work.

  15. Physical chemistry of the H2SO4/HNO3/H2O system - Implications for polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Molina, M. J.; Zhang, R.; Wooldridge, P. J.; Mcmahon, J. R.; Kim, J. E.; Chang, H. Y.; Beyer, K. D.

    1993-01-01

    Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO3 hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H2SO4/H2O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO3 vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO3 and H2O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H2SO4 solutions and on solid H2SO4 hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.

  16. Association rate constants for reactions between resonance-stabilized radicals: C 3H 3 + C 3H 3, C 3H 3 + C 3H 5, and C 3H 5 + C 3H 5

    DOE PAGES

    Georgievskii, Yuri; Miller, James A.; Klippenstein, Stephen J.

    2007-05-18

    Reactions between resonance-stabilized radicals play an important role in combustion chemistry. The theoretical prediction of rate coefficients and product distributions for such reactions is complicated by the fact that the initial complex-formation steps and some dissociation steps are barrierless. In this work, direct variable reaction coordinate transition state theory (VRC-TST) is used to predict accurately the association rate constants for the self and cross reactions of propargyl and allyl radicals. For each reaction, a set of multifaceted dividing surfaces is used to account for the multiple possible addition channels. Because of their resonant nature the geometric relaxation of the radicalsmore » is important. Here, the effect of this relaxation is explicitly calculated with the UB3LYP/cc-pvdz method for each mutual orientation encountered in the configurational integrals over the transition state dividing surfaces. The final energies are obtained from CASPT2/cc-pvdz calculations with all π-orbitals in the active space. Evaluations along the minimum energy path suggest that basis set corrections are negligible. The VRC-TST approach was also used to calculate the association rate constant and the corresponding number of states for the C 6H 5 + H → C 6H 6 exit channel of the C 3H 3 + C 3H 3 reaction, which is also barrierless. For this reaction, the interaction energies were evaluated with the CASPT2(2e,2o)/cc-pvdz method and a 1-D correction is included on the basis of CAS+1+2+QC/aug-cc-pvtz calculations for the CH 3 + H reference system. For the C 3H 3 + C 3H 3 reaction, the VRC-TST results for the energy and angular momentum resolved numbers of states in the entrance channels and in the C 6H 5 + H exit channel are incorporated in a master equation simulation to determine the temperature and pressure dependence of the phenomenological rate coefficients. The rate constants for the C 3H 3 + C 3H 3 and C 3H 5 + C 3H 5 self-reactions compare favorably

  17. Comparison of photo-Fenton, O3/H2O2/UV and photocatalytic processes for the treatment of gray water.

    PubMed

    Hassanshahi, Nahid; Karimi-Jashni, Ayoub

    2018-06-21

    This research was carried out to compare and optimize the gray water treatment performance by the photo-Fenton, photocatalysis and ozone/H 2 O 2 /UV processes. Experimental design and optimization were carried out using Central Composite Design of Response Surface Methodology. The results of experiments showed that the most effective and influencing factors in photo-Fenton process were H 2 O 2 /Fe 2+ ratio, in ozone/H 2 O 2 /UV experiment were O 3 concentration, H 2 O 2 concentration, reaction time and pH and in photocatalytic process were TiO 2 concentration, pH and reaction time. The highest COD removal in photo-Fenton, ozone/H 2 O 2 /UV and photocatalytic process were 90%, 92% and 55%, respectively. The results were analyzed by design expert software and for all three processes second-order models were proposed to simulate the COD removal efficiency. In conclusion the ozone/H 2 O 2 /UV process is recommended for the treatment of gray water, since it was able to remove both COD and turbidity by 92% and 93%, respectively. Copyright © 2018 Elsevier Inc. All rights reserved.

  18. Removal of arsenic from water by Friedel's salt (FS: 3CaO·Al2O3·CaCl2·10H2O).

    PubMed

    Zhang, Danni; Jia, Yongfeng; Ma, Jiayu; Li, Zhibao

    2011-11-15

    Low levels of arsenic can be effectively removed from water by adsorption onto various materials and searching for low-cost, high-efficiency new adsorbents has been a hot topic in recent years. In the present study, the performance of Friedel's salt (FS: 3CaO·Al(2)O(3)·CaCl(2)·10H(2)O), a layered double hydroxide (LDHs), as an adsorbent for arsenic removal from aqueous solution was investigated. Friedel's salt was synthesized at lower temperature (50°C) compared to traditional autoclave methods by reaction of calcium chloride with sodium aluminate. Kinetic study revealed that adsorption of arsenate by Friedel's salt was fast in the first 12h and equilibrium was achieved within 48 h. The adsorption kinetics are well described by second-order Lageren equation. The adsorption capacity of the synthesized sorbent for arsenate at pH 4 and 7 calculated from Langmuir adsorption isotherms was 11.85 and 7.80 mg/g, respectively. Phosphate and silicate markedly decreased the removal of arsenate, especially at higher pH, but sulfate was found to suppress arsenate adsorption at lower pH and the adverse effect was disappeared at pH ≥ 6. Common metal cations (Ca(2+), Mg(2+)) enhanced arsenate adsorption. The results suggest that Friedel's salt is a potential cost-effective adsorbent for arsenate removal in water treatment. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. Direct Dynamics Simulation of the Thermal 3CH2 + 3O2 Reaction. Rate Constant and Product Branching Ratios.

    PubMed

    Lakshmanan, Sandhiya; Pratihar, Subha; Machado, Francisco B C; Hase, William L

    2018-05-31

    The reaction of 3 CH 2 with 3 O 2 is of fundamental importance in combustion, and the reaction is complex as a result of multiple extremely exothermic product channels. In the present study, direct dynamics simulations were performed to study the reaction on both the singlet and triplet potential energy surfaces (PESs). The simulations were performed at the UM06/6-311++G(d,p) level of theory. Trajectories were calculated at a temperature of 300 K, and all reactive trajectories proceeded through the carbonyl oxide Criegee intermediate, CH 2 OO, on both the singlet and triplet PESs. The triplet surface leads to only one product channel, H 2 CO + O( 3 P), while the singlet surface leads to eight product channels with their relative importance as CO + H 2 O > CO + OH + HH 2 CO + O( 1 D) > HCO + OH ∼ CO 2 + H 2 ∼ CO + H 2 + O( 1 D) > CO 2 + H + H > HCO + O( 1 D) + H. The reaction on the singlet PES is barrierless, consistent with experiment, and the total rate constant on the singlet surface is (0.93 ± 0.22) × 10 -12 cm 3 molecule -1 s -1 in comparison to the recommended experimental rate constant of 3.3 × 10 -12 cm 3 molecule -1 s -1 . The simulation product yields for the singlet PES are compared with experiment, and the most significant differences are for H, CO 2 , and H 2 O. The reaction on the triplet surface is also barrierless, inconsistent with experiment. A discussion is given of the need for future calculations to address (1) the barrier on the triplet PES for 3 CH 2 + 3 O 23 CH 2 OO, (2) the temperature dependence of the 3 CH 2 + 3 O 2 reaction rate constant and product branching ratios, and (3) the possible non-RRKM dynamics of the 1 CH 2 OO Criegee intermediate.

  20. Ab Initio Chemical Kinetics for the CH3 + O((3)P) Reaction and Related Isomerization-Decomposition of CH3O and CH2OH Radicals.

    PubMed

    Xu, Z F; Raghunath, P; Lin, M C

    2015-07-16

    The kinetics and mechanism of the CH3 + O reaction and related isomerization-decomposition of CH3O and CH2OH radicals have been studied by ab initio molecular orbital theory based on the CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVTZ, CCSD/aug-cc-pVDZ, and G2M//B3LYP/6-311+G(3df,2p) levels of theory. The predicted potential energy surface of the CH3 + O reaction shows that the CHO + H2 products can be directly generated from CH3O by the TS3 → LM1 → TS7 → LM2 → TS4 path, in which both LM1 and LM2 are very loose and TS7 is roaming-like. The result for the CH2O + H reaction shows that there are three low-energy barrier processes including CH2O + H → CHO + H2 via H-abstraction and CH2O + H → CH2OH and CH2O + H → CH3O by addition reactions. The predicted enthalpies of formation of the CH2OH and CH3O radicals at 0 K are in good agreement with available experimental data. Furthermore, the rate constants for the forward and some key reverse reactions have been predicted at 200-3000 K under various pressures. Based on the new reaction pathway for CH3 + O, the rate constants for the CH2O + H and CHO + H2 reactions were predicted with the microcanonical variational transition-state/Rice-Ramsperger-Kassel-Marcus (VTST/RRKM) theory. The predicted total and individual product branching ratios (i.e., CO versus CH2O) are in good agreement with experimental data. The rate constant for the hydrogen abstraction reaction of CH2O + H has been calculated by the canonical variational transition-state theory with quantum tunneling and small-curvature corrections to be k(CH2O + H → CHO + H2) = 2.28 × 10(-19) T(2.65) exp(-766.5/T) cm(3) molecule(-1) s(-1) for the 200-3000 K temperature range. The rate constants for the addition giving CH3O and CH2OH and the decomposition of the two radicals have been calculated by the microcanonical RRKM theory with the time-dependent master equation solution of the multiple quantum well system in the 200-3000 K temperature range at 1 Torr to

  1. Sonochemical synthesis of highly luminescent Ln 2O 3:Eu 3+ (Y, La, Gd) nanocrystals

    DOE PAGES

    Alammar, Tarek; Cybinska, Joanna; Campbell, Paul S.; ...

    2015-05-12

    In this study, sonication of Ln(CH 3COO) 3·H 2O, Eu(CH 3COO) 3·H 2O and NaOH dissolved in the ionic liquid-butyl-3-methylimidazolium bis(trifluoromethane)sulfonylamide lead to Ln(OH) 3:Eu (Ln: Gd, La, Y) nanoparticles. Subsequent calcination at 800 °C for 3 h allowed to obtain Ln 2O 3:Eu nanopowders. Gd 2O 3 and Y 2O 3 were obtained in the C-type lanthanide sequioxide structure, whereas La 2O 3 crystallized in the A-type. Structure, morphology, and luminescent properties of the nano-oxides were investigated by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), dispersive X-ray (EDX), and photoluminescence (PL). SEM studies revealed that the synthesized Gdmore » 2O 3:Eu, La 2O 3:Eu, and Y 2O 3:Eu formed nano-spindle, -sheets, and -rods in shape, respectively. The nanoscale materials show very efficient red emission due to the intraconfigurational f–f transitions of Eu 3+. The quantum yields for Ln 2O 3:Eu (5%) were determined to be 4.2% for Ln=Gd, 13.8% for Ln=Y and 5.2% for Ln=La. The asymmetric ratio I 02/I 01 of Eu 3+ varies from 5.3 for Gd 2O 3, to 5.6 for Y 2O 3 to 6.5 for La 2O 3, which increased the color chromaticity.« less

  2. ON THE REACTION OF COMPONENETS IN MeNO$sub 3$-UO$sub 2$(NO$sub 3$)$sub 2$- H$sub 2$O TYPE SYSTEMS (in Russian)

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

    Yakimov, M.A.; Nosova, N.F.; Degtyarev, A.Ya.

    1963-01-01

    Solubility in ternary systems TlNO/sub 3/--UO/sub 2/(NO/sub 3/)/sub 2/-- H/sub 2/ O and CsNO/sub 3/--UO/sub 2/(NO/sub 3/)/sub 2/--H/sub 2/O at 0 to 25 c- C was studi ed by the isothermal method. The first system did not form solid phase compounds; the second system formed two compounds Cs/sub 2/UO/ sub 2/(NO/sub 3/)/sub 4/ and CsUO/sub 2/(NO/sub 3/)/sub 3/ at 25 c- and of water vapor pressure over the systems at 25 c- showed that water activity in the ternary systems at certain concentrations does not exceed the water activity in binary uranyl nitratewater system (at identical uranyl nitrate concentrations) confirmingmore » the observed complex formation in the solution. The mechanism of complex formation was analyzed and expanded for alkali metal - metal salt-complexing agent water systems. (R.V.J.)« less

  3. Sonocatalytic activity of a heterostructured β-Bi2O3/Bi2O2CO3 nanoplate in degradation of bisphenol A.

    PubMed

    Lee, Gooyong; Ibrahim, Shaliza; Kittappa, Shanmuga; Park, Heekyung; Park, Chang Min

    2018-06-01

    Novel heterostructured β-Bi 2 O 3 /Bi 2 O 2 CO 3 nanoplates (hBN) were synthesized to observe the sonocatalytic degradation of bisphenol A (BPA) (widely used as a model pollutant) under ultrasonic (US) irradiation. Prior to obtaining the hBN, the Bi 2 O 2 CO 3 micropowder precursor was prepared under hydrothermal conditions and then converted to hBN by increasing the calcination temperature to 300 °C. The synthesized hBN samples were characterized by field emission scanning electron microscope with energy dispersive X-ray analysis (FESEM/EDX), transmission electron microscopy (TEM), X-ray diffraction (XRD), ultraviolet-visible spectrophotometer diffuse reflection spectroscopy (UV-vis DRS), and X-ray photoelectron spectroscopy (XPS). The hBN/US system exhibited greater sonocatalytic activity for the degradation of BPA than the US treatment with the single element bismuth oxide, β-Bi 2 O 3 prepared by annealing the Bi 2 O 2 CO 3 precursor at 400 °C for 1 h. The US frequency and US power intensity in the hBN/US system were the key operating parameters, which were responsible for the complete degradation of BPA during 6 h of reactions. The degradation efficiency of BPA under the US irradiation was positively correlated with the dose of hBN. Our findings indicate that heterostructured hBN can be used as an efficient sonocatalyst for the catalytic degradation of BPA in water and wastewater treatment. Copyright © 2018 Elsevier B.V. All rights reserved.

  4. Effect of pH on particles size and gas sensing properties of In2O3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Anand, Kanica; Thangaraj, Rengasamy; Singh, Ravi Chand

    2016-05-01

    In this work, indium oxide (In2O3) nanoparticles have been synthesized by co-precipitation method and the effect of pH on the structural and sensor response values of In2O3 nanoparticles has been reported. X-ray diffraction pattern (XRD) revealed the formation of cubic phase In2O3 nanoparticles. FESEM results indicate the formation of nearly spherical shape In2O3 nanoparticles. The band gap energy value changed with change in pH value and found to have highest value at pH 9. Indium oxide nanoparticles thus prepared were deposited as thick films on alumina substrates to act as gas sensors and their sensing response to ethanol vapors and LPG at 50 ppm was investigated at different operating temperatures. It has been observed that all sensors exhibited optimum response at 300°C towards ethanol and at 400°C towards LPG. In2O3 nanoparticles prepared at pH 9, being smallest in size as compared to other, exhibit highest sensor response (SR).

  5. Morphology-controlled synthesis of α-Fe 2O 3 nanostructures with magnetic property and excellent electrocatalytic activity for H 2O 2

    NASA Astrophysics Data System (ADS)

    Li, Xiyan; Lei, Yongqian; Li, Xiaona; Song, Shuyan; Wang, Cheng; Zhang, Hongjie

    2011-12-01

    α-Fe 2O 3 nanocrystals (NCs) with different morphologies are successfully synthesized via a facile template-free hydrothermal route. By simply changing the volume ratio of ethanol to water, we obtained three different α-Fe 2O 3 nanostructures of rhombohedra, truncated rhombohedra and hexagonal sheet. The morphologies and structures of the as-obtained products have been confirmed by varieties of characterizations such as X-ray diffraction (XRD), X-ray photoelectron spectrometry (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The influences of the experimental conditions, such as the amount of NaOH and reaction temperature on the morphologies of the as-prepared α-Fe 2O 3 NCs, have been well investigated. Additionally, magnetic investigations show that the as-obtained α-Fe 2O 3 nanostructures show structure-dependent magnetic properties. Furthermore, the electrochemical experiments indicate that the as-prepared α-Fe 2O 3 hexagonal sheets exhibit strong electrocatalytic reduction activity for H 2O 2.

  6. Melatonin partially protects 661W cells from H2O2-induced death by inhibiting Fas/FasL-caspase-3.

    PubMed

    Sánchez-Bretaño, Aída; Baba, Kenkichi; Janjua, Uzair; Piano, Ilaria; Gargini, Claudia; Tosini, Gianluca

    2017-01-01

    Previous studies have shown that melatonin (MEL) signaling is involved in the modulation of photoreceptor viability during aging. Recent work by our laboratory suggested that MEL may protect cones by modulating the Fas/FasL-caspase-3 pathway. In this study, we first investigated the presence of MEL receptors (MT 1 and MT 2 ) in 661W cells, then whether MEL can prevent H 2 O 2 -induced cell death, and last, through which pathway MEL confers protection. The mRNA and proteins of the MEL receptors were detected with quantitative PCR (q-PCR) and immunocytochemistry, respectively. To test the protective effect of MEL, 661W cells were treated with H 2 O 2 for 2 h in the presence or absence of MEL, a MEL agonist, and an antagonist. To study the pathways involved in H 2 O 2 -mediated cell death, a Fas/FasL antagonist was used before the exposure to H 2 O 2 . Finally, Fas/FasL and caspase-3 mRNA was analyzed with q-PCR and immunocytochemistry in cells treated with H 2 O 2 and/or MEL. Cell viability was analyzed by using Trypan Blue. Both MEL receptors (MT 1 and MT 2 ) were detected at the mRNA and protein levels in 661W cells. MEL partially prevented H 2 O 2 -mediated cell death (20-25%). This effect was replicated with IIK7 (a melatonin receptor agonist) when used at a concentration of 1 µM. Preincubation with luzindole (a melatonin receptor antagonist) blocked MEL protection. Kp7-6, an antagonist of Fas/FasL, blocked cell death caused by H 2 O 2 similarly to what was observed for MEL. Fas, FasL, and caspase-3 expression was increased in cells treated with H 2 O 2 , and this effect was prevented by MEL. Finally, MEL treatment partially prevented the activation of caspase-3 caused by H 2 O 2 . The results demonstrate that MEL receptors are present and functional in 661W cells. MEL can prevent photoreceptor cell death induced by H 2 O 2 via the inhibition of the proapoptotic pathway Fas/FasL-caspase-3.

  7. Using a modified Marcus model to analyze the Brønsted correlation of gas-phase reactions of the deprotonation of para-substituted toluenes by CH2Cl-, H(O)C-, CH3O-, H(F)N-, NH2C≡C-, and CH3C≡C- anions

    NASA Astrophysics Data System (ADS)

    Romanskii, I. A.

    2017-10-01

    Ab initio calculations of the energy parameters for a series of gas-phase reactions of the deprotonation of para-substituted toluenes (OH, CH3, H, Cl, NC, CN, and NO2 substituents) by CH2Cl-, H(O)C-, CH3O-, H(F)N-, NH2C≡C-, and CH3C≡C- anions (the conjugated acids are chloromethane (CH3Cl), formaldehyde (H2CO), methanol (CH3OH), fluoroamine (NH2F), aminoacetylene (NH2C≡CH), and methylacetylene (CH3C≡CH), respectively) is performed using a technique of intramolecular reorganization proposed earlier. The equilibrium ( E a eq) and nonequilibrium ( E a neq ) contributions to energy of activation E a are found for distance Q(C…B) = 3.0 Å (where C and B are the central atoms of the acid and base). At this value of Q, the tunneling mechanism of proton transfer predominates. The results from calculations, together with similar data obtained earlier for reactions of the deprotonation of toluenes by CH2CN- anions, are considered from the viewpoint of the harmonic Marcus model. It is found that in the graph Δ E 0 - E a neq (where Δ E 0 is the internal energy of the reaction (for a collision complex)), the points for five reaction series with C-bases fall on the same quadratic (within the -11 to 12 kcal/mol range of Δ E 0) curve; the second curve, which includes points for the series with N- and O-bases (OCH3 - and H(F)N-) is shifted below the first curve by 1.5 kcal/mol. For most reaction series (except the one with the strongest bases, CH2Cl- and H(O)C-), the curvature and slope of graph Δ E 0 - E a neq are in agreement with the theory. The correlations of energies E a neq , E a eq, E a, and Δ E 0 with the energy of reaction Δ E 00 are satisfactorily described by quadratic equations as well. Differences between the structures of bases are reflected most by energy E a eq and the height of the proton tunneling barrier in the activated complex (AC) E b. For the series of reactions of toluene with a set of bases, graphs Δ E 00 - E a eq and Δ E 0 - E b show

  8. Application of Mixed H2/H Infinity Optimization

    DTIC Science & Technology

    1991-11-01

    Standard Form .................. . 29 4.4 a-Plot of the Open Loop System .. ......... .. 31 4.5 o-Plot of the H2 & H. Optimal Td ........... . 32 4.6 o...o.34 4.9 o-Plot of Mixed SolutiCo,,, Te.. .......... 35 4.10 a-Plot of H. Central Solution Td ........ 36 4.11 a-Plot of the Mixed Controllers...norm = 3.7) .. .. ......... 41 4.18 a3-Plot of Ted (V-norm 2.8) .......... o.42 v 4.19 a-Plot of Td (ac-norm = 2.5) . . . . . .. 0 42 4.20 a-Plot

  9. Influence of pH and europium concentration on the luminescent and morphological properties of Y2O3 powders

    NASA Astrophysics Data System (ADS)

    Esquivel-Castro, Tzipatly; Carrillo-Romo, Felipe de J.; Oliva-Uc, Jorge; García-Murillo, Antonieta; Hirata-Flores, Gustavo A.; Cayetano-Castro, Nicolás; De la Rosa, Elder; Morales-Ramírez, Angel de J.

    2015-10-01

    This work reports on the synthesis and characterization of Y2O3:Eu3+ powders obtained by the hydrothermal method. We studied the influence of different pH values (7-12) and Eu3+ concentrations (2.5-25 mol%) on the structural, morphological and luminescent characteristics of Y2O3:Eu3+ powders. The hydrothermal synthesis was performed at 200 °C for 12 h by employing Y2O3, HNO3, H2O and Eu (NO3)3 as precursors, in order to obtain two sets of samples. The first set of powders was obtained with different pH values and named Eu5PHx (x = 7, 8, 9, 10, 11, and 12), and the second set was obtained by using a constant pH = 7 with different Eu concentrations, named EuxPH7 (x = 2.5, 5, 8, 15, 20 and 25). The XRD spectra showed that the Y2O3:Eu3+ powders exhibited a cubic phase, regardless of the pH values and Eu3+ concentrations. The SEM observations indicated that pH influenced the morphology and size of phosphors; for instance, for pH = 7, hexagonal microplatelets were obtained, and microrods at pH values from 8 to 12. Doping Y2O3 with various Eu3+ concentrations (in mol%) also produced changes in morphology, in these cases, hexagonal microplatelets were obtained in the range of 2.5-5 mol%, and non uniform plates were observed at higher doping concentrations ranging from 8 to 25 mol%. According to our results, the microplatelets synthesized with a pH of 7 and an 8 mol% Eu3+ concentration presented the highest luminescence under excitation at 254 nm. All of these results indicate that our phosphors could be useful for applications of controlled drug delivery, photocatalysis and biolabeling.

  10. Scalable cross-point resistive switching memory and mechanism through an understanding of H2O2/glucose sensing using an IrOx/Al2O3/W structure.

    PubMed

    Chakrabarti, Somsubhra; Maikap, Siddheswar; Samanta, Subhranu; Jana, Surajit; Roy, Anisha; Qiu, Jian-Tai

    2017-10-04

    The resistive switching characteristics of a scalable IrO x /Al 2 O 3 /W cross-point structure and its mechanism for pH/H 2 O 2 sensing along with glucose detection have been investigated for the first time. Porous IrO x and Ir 3+ /Ir 4+ oxidation states are observed via high-resolution transmission electron microscope, field-emission scanning electron spectroscopy, and X-ray photo-electron spectroscopy. The 20 nm-thick IrO x devices in sidewall contact show consecutive long dc cycles at a low current compliance (CC) of 10 μA, multi-level operation with CC varying from 10 μA to 100 μA, and long program/erase endurance of >10 9 cycles with 100 ns pulse width. IrO x with a thickness of 2 nm in the IrO x /Al 2 O 3 /SiO 2 /p-Si structure has shown super-Nernstian pH sensitivity of 115 mV per pH, and detection of H 2 O 2 over the range of 1-100 nM is also achieved owing to the porous and reduction-oxidation (redox) characteristics of the IrO x membrane, whereas a pure Al 2 O 3 /SiO 2 membrane does not show H 2 O 2 sensing. A simulation based on Schottky, hopping, and Fowler-Nordheim tunneling conduction, and a redox reaction, is proposed. The experimental I-V curve matches very well with simulation. The resistive switching mechanism is owing to O 2- ion migration, and the redox reaction of Ir 3+ /Ir 4+ at the IrO x /Al 2 O 3 interface through H 2 O 2 sensing as well as Schottky barrier height modulation is responsible. Glucose at a low concentration of 10 pM is detected using a completely new process in the IrO x /Al 2 O 3 /W cross-point structure. Therefore, this cross-point memory shows a method for low cost, scalable, memory with low current, multi-level operation, which will be useful for future highly dense three-dimensional (3D) memory and as a bio-sensor for the future diagnosis of human diseases.

  11. pH sensing via bicarbonate-regulated “soluble” adenylyl cyclase (sAC)

    PubMed Central

    Rahman, Nawreen; Buck, Jochen; Levin, Lonny R.

    2013-01-01

    Soluble adenylyl cyclase (sAC) is a source of the second messenger cyclic adenosine 3′, 5′ monophosphate (cAMP). sAC is directly regulated by bicarbonate (HCO−3) ions. In living cells, HCO−3 ions are in nearly instantaneous equilibrium with carbon dioxide (CO2) and pH due to the ubiquitous presence of carbonic anhydrases. Numerous biological processes are regulated by CO2, HCO−3, and/or pH, and in a number of these, sAC has been shown to function as a physiological CO2/HCO3/pH sensor. In this review, we detail the known pH sensing functions of sAC, and we discuss two highly-studied, pH-dependent pathways in which sAC might play a role. PMID:24324443

  12. Magnetic properties of TM3[Cr(CN)6]2.n H2O

    NASA Astrophysics Data System (ADS)

    Zentková, M.; Mihalik, M.; Ková, J.; Zentko, A.; Mitróová, Z.; Lukáová, M.; Kaveanský, V.; Kiss, L. F.

    2006-01-01

    Magnetization measurements performed on Prussian blue analogs TM2+3[CrIII(CN)6]2.n H2O (TM = Cr, Mn, Fe, Co, Ni, Cu) confirmed the dual character of the exchange interaction (antiferromagnetic AFM and ferromagnetic FM) in this system. AFM interaction dominates for the Cr2+ sample and with rising atomic number Z the FM interaction becomes more important reaching pure FM character for the Cu2+ sample.

  13. Removing polysaccharides-and saccharides-related coloring impurities in alkyl polyglycosides by bleaching with the H2O2/TAED/NaHCO3 system.

    PubMed

    Yanmei, Liu; Jinliang, Tao; Jiao, Sun; Wenyi, Chen

    2014-11-04

    The effect of H2O2/TAED/NaHCO3 system, namely NaHCO3 as alkaline agent with the (tetra acetyl ethylene diamine (TAED)) TAED-activated peroxide system, bleaching of alkyl polyglycosides solution was studied by spectrophotometry. The results showed that the optimal bleaching conditions about H2O2/TAED/NaHCO3 system bleaching of alkyl polyglycosides solution were as follows: molar ratio of TAED to H2O2 was 0.06, addition of H2O2 was 8.6%, addition of NaHCO3 was 3.2%, bleaching temperature of 50-65 °C, addition of MgO was 0.13%, and bleaching time was 8h. If too much amount of NaHCO3 was added to the system and maintained alkaline pH, the bleaching effect would be greatly reduced. Fixing molar ratio of TAED to H2O2 and increasing the amount of H2O2 were beneficial to improve the whiteness of alkyl polyglycosides, but adding too much amount of H2O2 would reduce the transparency. In the TAED-activated peroxide system, NaHCO3 as alkaline agent and buffer agent, could overcome the disadvantage of producing black precipitates when NaOH as alkaline agent. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Organic Contaminant Abatement in Reclaimed Water by UV/H2O2 and a Combined Process Consisting of O3/H2O2 Followed by UV/H2O2: Prediction of Abatement Efficiency, Energy Consumption, and Byproduct Formation.

    PubMed

    Lee, Yunho; Gerrity, Daniel; Lee, Minju; Gamage, Sujanie; Pisarenko, Aleksey; Trenholm, Rebecca A; Canonica, Silvio; Snyder, Shane A; von Gunten, Urs

    2016-04-05

    UV/H2O2 processes can be applied to improve the quality of effluents from municipal wastewater treatment plants by attenuating trace organic contaminants (micropollutants). This study presents a kinetic model based on UV photolysis parameters, including UV absorption rate and quantum yield, and hydroxyl radical (·OH) oxidation parameters, including second-order rate constants for ·OH reactions and steady-state ·OH concentrations, that can be used to predict micropollutant abatement in wastewater. The UV/H2O2 kinetic model successfully predicted the abatement efficiencies of 16 target micropollutants in bench-scale UV and UV/H2O2 experiments in 10 secondary wastewater effluents. The model was then used to calculate the electric energies required to achieve specific levels of micropollutant abatement in several advanced wastewater treatment scenarios using various combinations of ozone, UV, and H2O2. UV/H2O2 is more energy-intensive than ozonation for abatement of most micropollutants. Nevertheless, UV/H2O2 is not limited by the formation of N-nitrosodimethylamine (NDMA) and bromate whereas ozonation may produce significant concentrations of these oxidation byproducts, as observed in some of the tested wastewater effluents. The combined process of O3/H2O2 followed by UV/H2O2, which may be warranted in some potable reuse applications, can achieve superior micropollutant abatement with reduced energy consumption compared to UV/H2O2 and reduced oxidation byproduct formation (i.e., NDMA and/or bromate) compared to conventional ozonation.

  15. [(H2O)(terpy)Mn(μ-O)2Mn(terpy)(OH2)](NO3)3 (terpy = 2,2′:6,2″-terpyridine) and its relevance to the oxygen-evolving complex of photosystem II examined through pH dependent cyclic voltametry

    PubMed Central

    Cady, Clyde W.; Shinopoulos, Katherine E.; Crabtree, Robert H.; Brudvig, Gary W.

    2010-01-01

    Photosynthetic water oxidation occurs naturally at a tetranuclear manganese center in the photosystem II protein complex. Synthetically mimicking this tetramanganese center, known as the oxygen-evolving complex (OEC), has been an ongoing challenge of bioinorganic chemistry. Most past efforts have centered on water-oxidation catalysis using chemical oxidants. However, solar energy applications have drawn attention to electrochemical methods. In this paper, we examine the electrochemical behavior of the biomimetic water-oxidation catalyst [(H2O)(terpy)Mn(μ-O)2Mn(terpy)(H2O)](NO3)3 [terpy = 2,2′:6′,2″-terpyridine] (1) in water under a variety of pH and buffered conditions and in the presence of acetate that binds to 1 in place of one of the terminal water ligands. These experiments will show that 1 not only exhibits proton-coupled electron-transfer reactivity analogous to the OEC, but also may be capable of electrochemical oxidation of water to oxygen. PMID:20372724

  16. Construction of New Coordination Polymers from 4'-(2,4-disulfophenyl)- 3,2':6'3"-terpyridine: Polymorphism, pH-dependent syntheses, structures, and properties

    NASA Astrophysics Data System (ADS)

    Zhang, Li; Li, Chao-Jie; He, Jia-En; Chen, Yin-Yu; Zheng, Sheng-Run; Fan, Jun; Zhang, Wei-Guang

    2016-01-01

    Nine new coordination compounds, namely, [Co(HDSPTP)2(H2O)4]·4H2O (H2DSPTP=4'-(2,4-disulfophenyl)-3,2':6'3"-terpyridine, 1 and 2), {[Ni(DSPTP)(H2O)4]·3H2O}n (3), {[Cu(HDSPTP)2(H2O)3]·8H2O}n (4), {[Cu(HDSPTP)2(H2O)3]·6H2O}n (5), {[Cu(DSPTP)(H2O)2H2O}n (6), {[Zn(DSPTP)(H2O)22H2O}n (7), {[Cd(DSPTP)(H2O)22H2O}n (8), and [Ag2(DSPTP)(H2O)]n (9), were constructed based on a new ligand containing both terpyridyl and sulfo groups. The reactions of H2DSPTP with Co(NO3)2.6H2O resulted in two mononuclear complexes (compounds 1 and 2). They are polymorphisms that display different hydrogen bonding networks. They are selectively synthesized by altering the added alkalis. The reaction of H2DSPTP with Ni(NO3)2·6H2O resulted in a 1D "S-shaped" coordination chain (compound 3). The reactions of Cu(II) with H2DSPTP at different pH value resulted in the following three compounds: two kinds of 1D chains obtained at pH 3.0 and 4.0 for compounds 4 and 5, respectively, and a 3D framework based on binuclear ring units with 4-connected sra topology (Compound 6). The reactions of H2DSPTP with ds-block ions resulted in the following three compounds: a Zn(II) (compound 7) and a Cd(II) (compound 8) 3D frameworks with structures similar to that in compound 6, and a 3D framework based on tetranuclear Ag(I) SBUs with binodal (4,8)-connected flu type 3D framework topology. The structural diversity is mainly attributed to the rich coordination modes (from monodentate to μ7-mode) and conformations (cis-cis and cis-trans) of HDSPTP-/DSPTP2- ligands and the metal center and can be controllable synthesized by altering the alkalis, and pH value. Thermal stability of all compounds was performed, and the thermal behaviors of compounds 6 and 8 were further explored by PXRD. Compound 6 exhibits low thermal stability and undergo a crystalline-crystalline-amorphous phase transition as temperature increases from 25 °C to 200 °C, and show amorphous-crystalline phase transition when rehydrated

  17. Effect of deuteration on hydrogen bonding: A comparative concentration dependent Raman and DFT study of pyridine in CH3OH and CD3OD and pyrimidine in H2O and D2O

    NASA Astrophysics Data System (ADS)

    Singh, Anurag; Gangopadhyay, Debraj; Popp, Jürgen; Singh, Ranjan K.

    2012-12-01

    The relative effect of hydrogen bonding of pyrimidine (Pyr) in H2O/D2O and pyridine (Py) in CH3OH/CD3OD has been analyzed using Raman Difference Spectroscopic (RDS) technique and DFT calculations. This study is focused on analyzing the concentration dependent variation of linewidth, peak position and intensity of ring breathing mode of Py and Pyr. The ring breathing mode of Pyr in H2O and D2O has three components; due to free Pyr, lighter complexes of mPyr + nH2O/D2O and heavier complexes of mPyr + nH2O/D2O. The pyridine molecules, however, show only two components in CH3OH and CD3OD. Of these two components, one corresponds to free Py and the other inhomogeneously broadened profile corresponds to all mPy + nCH3OH/CD3OD complexes. The variation of peak position and linewidth establishes the role of dipole moment of complexes and the diffusion in the mixture. In case of CD3OD solution splitting was observed in ˜1030 cm-1 band of Py, where an additional band at ˜1034 cm-1 appears at x(Py) ⩽ 0.4. However, this band remains single at all concentrations in case of CH3OH solvent.

  18. Three-dimensional hierarchical NiCo2O4 nanowire@Ni3S2 nanosheet core/shell arrays for flexible asymmetric supercapacitors

    NASA Astrophysics Data System (ADS)

    Liu, Bo; Kong, Dezhi; Huang, Zhi Xiang; Mo, Runwei; Wang, Ye; Han, Zhaojun; Cheng, Chuanwei; Yang, Hui Ying

    2016-05-01

    Three-dimensional (3D) hierarchical NiCo2O4@Ni3S2 core/shell arrays on Ni foam were synthesized by a facile, stepwise synthesis approach. The 3D heterogeneous NiCo2O4 nanostructure forms an interconnected web-like scaffold and serves as the core for the Ni3S2 shell. The as-prepared NiCo2O4@Ni3S2 nanowire array (NWA) electrodes exhibited excellent electrochemical performance, such as high specific areal capacitance and excellent cycling stability. The specific areal capacitance of 3.0 F cm-2 at a current density of 5 mA cm-2 is among the highest values and the only 6.7% capacitance decay after 10 000 cycles demonstrates the excellent cycling stability. A flexible asymmetric supercapacitor (ASC) was fabricated with activated carbon (AC) as the anode and the obtained NiCo2O4@Ni3S2 NWAs as the cathode. The ASC device exhibited a high energy density of 1.89 mW h cm-3 at 5.81 W cm-3 and a high power density of 56.33 W cm-3 at 0.94 mW h cm-3. As a result, the hybrid nanoarchitecture opens a new way to design high performance electrodes for electrochemical energy storage applications.Three-dimensional (3D) hierarchical NiCo2O4@Ni3S2 core/shell arrays on Ni foam were synthesized by a facile, stepwise synthesis approach. The 3D heterogeneous NiCo2O4 nanostructure forms an interconnected web-like scaffold and serves as the core for the Ni3S2 shell. The as-prepared NiCo2O4@Ni3S2 nanowire array (NWA) electrodes exhibited excellent electrochemical performance, such as high specific areal capacitance and excellent cycling stability. The specific areal capacitance of 3.0 F cm-2 at a current density of 5 mA cm-2 is among the highest values and the only 6.7% capacitance decay after 10 000 cycles demonstrates the excellent cycling stability. A flexible asymmetric supercapacitor (ASC) was fabricated with activated carbon (AC) as the anode and the obtained NiCo2O4@Ni3S2 NWAs as the cathode. The ASC device exhibited a high energy density of 1.89 mW h cm-3 at 5.81 W cm-3 and a high power

  19. Ab initio Quantum Chemical Studies of Reactions in Astrophysical Ices. Reactions Involving CH3OH, CO2, CO, HNCO in H2CO/NH3/H2O Ices

    NASA Technical Reports Server (NTRS)

    Woon, David E.

    2006-01-01

    While reactions between closed shell molecules generally involve prohibitive barriers in the gas phase, prior experimental and theoretical studies have demonstrated that some of these reactions are significantly enhanced when confined within an icy grain mantle and can occur efficiently at temperatures below 100 K with no additional energy processing. The archetypal case is the reaction of formaldehyde (H2CO) and ammonia (NH3) to yield hydroxymethylamine (NH2CH2OH). In the present work we have characterized reactions involving methanol (CH3OH), carbon dioxide (CO2), carbon monoxide (CO), and isocyanic acid (HNCO) in search of other favorable cases. Most of the emphasis is on CH3OH, which was investigated in the two-body reaction with one H2CO and the three-body reaction with two H2CO molecules. The addition of a second H2CO to the product of the reaction between CH3OH and H2CO was also considered as an alternative route to longer polyoxymethylene polymers of the -CH2O- form. The reaction between HNCO and NH3 was studied to determine if it can compete against the barrierless charge transfer process that yields OCN(-) and NH4(+). Finally, the H2CO + NH3 reaction was revisited with additional benchmark calculations that confirm that little or no barrier is present when it occurs in ice.

  20. U 3Si 2 behavior in H 2O environments: Part II, pressurized water with controlled redox chemistry

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

    Nelson, Andrew Thomas; Migdisov, Artaches; Wood, Elizabeth Sooby

    Recent interest in U 3Si 2 as an advanced light water reactor fuel has driven assessment of numerous properties, but characterization of its response to H 2O environments is sparse in available literature. The behavior of U 3Si 2 in H 2O containing atmospheres is investigated and presented in a two-part series of articles. This work examines the behavior of U 3Si 2 following exposure to pressurized H 2O at temperatures from 300 to 350 °C. Testing was performed using two autoclave configurations and multiple redox conditions. Use of solid state buffers to attain a controlled water chemistry is alsomore » presented as a means to test actinide-bearing systems. Buffers were used to vary the hydrogen concentration between 1 and 30 parts per million H 2. Testing included UN, U 3Si 5, and UO 2. Both UN and U 3Si 5 were found to rapidly pulverize in less than 5 h at 300 °C. Uranium dioxide was included as a control for the autoclave system, and was found to be minimally impacted by exposure to pressurized water at the conditions tested for extended time periods. Testing of U 3Si 2 at 300 °C found reasonable stability through 30 days in 1–5 ppm H 2. However, pulverization was observed following 35 days. The redox condition of testing strongly affected pulverization. Characterization of the resulting microstructures suggests that the mechanism responsible for pulverization under more strongly reducing conditions differs from that previously identified. Hydride formation is hypothesized to drive this transition. In conclusion, testing performed at 350 °C resulted in rapid pulverization of U 3Si 2 in under 50 h.« less

  1. U 3Si 2 behavior in H 2O environments: Part II, pressurized water with controlled redox chemistry

    DOE PAGES

    Nelson, Andrew Thomas; Migdisov, Artaches; Wood, Elizabeth Sooby; ...

    2017-12-16

    Recent interest in U 3Si 2 as an advanced light water reactor fuel has driven assessment of numerous properties, but characterization of its response to H 2O environments is sparse in available literature. The behavior of U 3Si 2 in H 2O containing atmospheres is investigated and presented in a two-part series of articles. This work examines the behavior of U 3Si 2 following exposure to pressurized H 2O at temperatures from 300 to 350 °C. Testing was performed using two autoclave configurations and multiple redox conditions. Use of solid state buffers to attain a controlled water chemistry is alsomore » presented as a means to test actinide-bearing systems. Buffers were used to vary the hydrogen concentration between 1 and 30 parts per million H 2. Testing included UN, U 3Si 5, and UO 2. Both UN and U 3Si 5 were found to rapidly pulverize in less than 5 h at 300 °C. Uranium dioxide was included as a control for the autoclave system, and was found to be minimally impacted by exposure to pressurized water at the conditions tested for extended time periods. Testing of U 3Si 2 at 300 °C found reasonable stability through 30 days in 1–5 ppm H 2. However, pulverization was observed following 35 days. The redox condition of testing strongly affected pulverization. Characterization of the resulting microstructures suggests that the mechanism responsible for pulverization under more strongly reducing conditions differs from that previously identified. Hydride formation is hypothesized to drive this transition. In conclusion, testing performed at 350 °C resulted in rapid pulverization of U 3Si 2 in under 50 h.« less

  2. U3Si2 behavior in H2O environments: Part II, pressurized water with controlled redox chemistry

    NASA Astrophysics Data System (ADS)

    Nelson, A. T.; Migdisov, A.; Wood, E. Sooby; Grote, C. J.

    2018-03-01

    Recent interest in U3Si2 as an advanced light water reactor fuel has driven assessment of numerous properties, but characterization of its response to H2O environments is sparse in available literature. The behavior of U3Si2 in H2O containing atmospheres is investigated and presented in a two-part series of articles. This work examines the behavior of U3Si2 following exposure to pressurized H2O at temperatures from 300 to 350 °C. Testing was performed using two autoclave configurations and multiple redox conditions. Use of solid state buffers to attain a controlled water chemistry is also presented as a means to test actinide-bearing systems. Buffers were used to vary the hydrogen concentration between 1 and 30 parts per million H2. Testing included UN, U3Si5, and UO2. Both UN and U3Si5 were found to rapidly pulverize in less than 50 h at 300 °C. Uranium dioxide was included as a control for the autoclave system, and was found to be minimally impacted by exposure to pressurized water at the conditions tested for extended time periods. Testing of U3Si2 at 300 °C found reasonable stability through 30 days in 1-5 ppm H2. However, pulverization was observed following 35 days. The redox condition of testing strongly affected pulverization. Characterization of the resulting microstructures suggests that the mechanism responsible for pulverization under more strongly reducing conditions differs from that previously identified. Hydride formation is hypothesized to drive this transition. Testing performed at 350 °C resulted in rapid pulverization of U3Si2 in under 50 h.

  3. Electrical properties of AC{sub 3}B{sub 4}O{sub 12}-type perovskite ceramics with different cation vacancies

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

    Li, Guizhong; Chen, Zhi; Sun, Xiaojun

    2015-05-15

    Highlights: • AC{sub 3}B{sub 4}O{sub 12} perovskite with different concentration cation vacancies were prepared. • Cell parameter decreases with the increase of concentration of cation vacancies. • PTCO and CTO remain high dielectric permittivity but depress loss greatly. • Dielectric loss associates with cation vacancies and motion of oxygen vacancies. - Abstract: AC{sub 3}B{sub 4}O{sub 12}-type perovskite CaCu{sub 3}Ti{sub 4}O{sub 12} (CCTO), □{sub 0.34}Pr{sub 0.67}Cu{sub 3}Ti{sub 4}O{sub 12} (PCTO), □{sub 1}Cu{sub 3}Ta{sub 2}Ti{sub 2}O{sub 12} (CTTO), □{sub 2}Cu{sub 2}Ta{sub 4}O{sub 12} (CTO) ceramics with different concentration cation vacancies were prepared through traditional solid state reaction method. X-ray diffraction analysis indicatedmore » that CCTO and PCTO are perovskite cubic with space group Im-3 (no. 204) while CTTO and CTO are Pm-3 (no. 200). Cell parameter of the samples dramatically increases with the increase of cation vacancies. Dielectric permittivity of them maintains very high value of ∼10{sup 4} from room temperature to 550 K but the dielectric loss is depressed with the increase of cation vacancies in the same space group. The dielectric properties and conductivity behavior were described by the Debye relaxation and the universal dielectric response, respectively. The effect mechanism of cation vacancy and crystal structure on carrier transposition were discussed.« less

  4. The 2:1 salt-type adduct formed between 6-amino-3-methyl-5-nitrosopyrimidine-2,4(1H,3H)-dione and piperidine: sheets containing 20 independent hydrogen bonds.

    PubMed

    Orozco, Fabián; Insuasty, Braulio; Cobo, Justo; Glidewell, Christopher

    2009-05-01

    The title compound, piperidinium 6-amino-3-methyl-5-nitroso-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-ide 6-amino-3-methyl-5-nitrosopyrimidine-2,4(1H,3H)-dione, C(5)H(12)N(+).C(5)H(5)N(4)O(3)(-).C(5)H(6)N(4)O(3), (I), crystallizes with Z' = 2 in the space group P1. There is an intramolecular N-H...O hydrogen bond in each pyrimidine unit and within the selected asymmetric unit the six independent components are linked by 11 hydrogen bonds, seven of the N-H...O type and four of the N-H...N type. These six-component aggregates are linked into sheets by five further hydrogen bonds, three of the N-H...O type and one each of the N-H...N and C-H...O types.

  5. Preparation of 7-hydroxy-2-oxoindolin-3-ylacetic acid and its [13C2], [5-n-3H], and [5-n-3H]-7-O-glucosyl analogues for use in the study of indol-3-ylacetic acid catabolism

    NASA Technical Reports Server (NTRS)

    Lewer, P.; Bandurski, R. S. (Principal Investigator)

    1987-01-01

    An improved synthesis of 7-hydroxy-2-oxoindolin-3-ylacetic acid via the base-induced condensation reaction between oxalate esters and 7-benzyloxyindolin-2-one is described. 7-Benzyloxyindolin-2-one was prepared in four steps and 50% overall yield from 3-hydroxy-2-nitrotoluene. The yield of the title compound from 7-benzyloxyindolin-2-one was 56%. This route was used to prepare 7-hydroxy-2-oxoindolin-3-yl[13C2]acetic acid in 30% yield from [13C2]oxalic acid dihydrate. The method could not be extended to the preparation of the corresponding [14C2]-compound. However, an enzyme preparation from Zea mays roots catalysed the conversion of carrier-free [5-n-3H]indol-3-ylacetic acid with a specific activity of 16.7 Ci mmol-1 to a mixture of 7-hydroxy-2-oxo[5-n-3H]indolin-3-ylacetic acid and its [5-n-3H]-7-O-glucoside in ca. 3 and 40% radiochemical yield respectively. The glucoside was converted into the 7-hydroxy compound in 80% yield by means of beta-glucosidase.

  6. Low Temperature Synthesized H2Ti3O7 Nanotubes with a High CO2 Adsorption Property by Amine Modification.

    PubMed

    Ota, Misaki; Hirota, Yuichiro; Uchida, Yoshiaki; Sakamoto, Yasuhiro; Nishiyama, Norikazu

    2018-06-12

    Carbon dioxide (CO 2 ) capture and storage (CCS) technologies have been attracting attention in terms of tackling with global warming. To date, various CO 2 capture technologies including solvents, membranes, cryogenics, and solid adsorbents have been proposed. Currently, a liquid adsorption method for CO 2 using amine solution (monoethanolamine) has been practically used. However, this liquid phase CO 2 adsorption process requires heat regeneration, and it can cause many problems such as corrosion of equipment and degradation of the solution. Meanwhile, solid adsorption methods using porous materials are more advantageous over the liquid method at these points. In this context, we here evaluated if hydrogen titanate (H 2 Ti 3 O 7 ) nanotubes and the surface modification effectively capture CO 2 . For this aim, we first developed a facile synthesis method of H 2 Ti 3 O 7 nanotubes different from any conventional methods. Briefly, they were converted from the precursors-amorphous TiO 2 nanoparticles at room temperature (25 °C). We then determined the outer and the inner diameters of the H 2 Ti 3 O 7 nanotubes as 3.0 and 0.7 nm, respectively. It revealed that both values were much smaller than the reported ones; thus the specific surface area showed the highest value (735 m 2 /g). Next, the outer surface of H 2 Ti 3 O 7 nanotubes was modified using ethylenediamine to examine if CO 2 adsorption capacity increases. The ethylendiamine-modified H 2 Ti 3 O 7 nanotubes showed a higher CO 2 adsorption capacity (50 cm 3 /g at 0 °C, 100 kPa). We finally concluded that the higher CO 2 adsorption capacity could be explained, not only by the high specific surface area of the nanotubes but also by tripartite hydrogen bonding interactions among amines, CO 2 , and OH groups on the surface of H 2 Ti 3 O 7 .

  7. Structure of H2Ti3O7 and its evolution during sodium insertion as anode for Na ion batteries.

    PubMed

    Eguía-Barrio, Aitor; Castillo-Martínez, Elizabeth; Zarrabeitia, Maider; Muñoz-Márquez, Miguel A; Casas-Cabanas, Montse; Rojo, Teófilo

    2015-03-14

    H2Ti3O7 was prepared as a single phase material by ionic exchange from Na2Ti3O7. The complete ionic exchange was confirmed by (1)H and (23)Na solid state Nuclear Magnetic Resonance (NMR). The atomic positions of H2Ti3O7 were obtained from the Rietveld refinement of powder X-ray diffraction (PXRD) and neutron diffraction experimental data, the latter collected at two different wavelengths to precisely determine the hydrogen atomic positions in the structure. All H(+) cations are hydrogen bonded to two adjacent [Ti3O7](2-) layers leading to the gliding of the layers and lattice centring with respect to the parent Na2Ti3O7. In contrast with a previous report where protons were located in two different positions of H2Ti3O7, 3 types of proton positions were found. Two of the three types of proton are bonded to the only oxygen linked to a single titanium atom forming an H-O-H angle close to that of the water molecule. H2Ti3O7 is able to electrochemically insert Na(+). The electrochemical insertion of sodium into H2Ti3O7 starts with a solid solution regime of the C-centred phase. Then, between 0.6 and 1.2 inserted Na(+) the reaction proceeds through a two phase reaction and a plateau at 1.3 V vs. Na(+)/Na is observed in the voltage-composition curve. The second phase resembles the primitive Na2Ti3O7 cell as detected by in situ PXRD. Upon oxidation, from 0.9 to 2.2 V, the PXRD pattern remains mostly unchanged probably due to H(+) removal instead of Na(+), with the capacity quickly fading upon cycling. Conditioning H2Ti3O7 for two cycles at 0.9-2.2 V before cycling in the 0.05-1.6 V range yields similar specific capacity and better retention than the original Na2Ti3O7 in the same voltage range.

  8. DFT studies of elemental mercury oxidation mechanism by gaseous advanced oxidation method: Co-interaction with H2O2 on Fe3O4 (111) surface

    NASA Astrophysics Data System (ADS)

    Zhou, Changsong; Song, Zijian; Zhang, Zhiyue; Yang, Hongmin; Wang, Ben; Yu, Jie; Sun, Lushi

    2017-12-01

    Density functional theory calculations have been carried out for H2O2 and Hg0 co-interaction on Fe3O4 (111) surface. On the Fetet1-terminated Fe3O4 (111) surface, the most favored configurations are H2O2 decomposition and produce two OH groups, which have strong interaction with Hg atom to form an OHsbnd Hgsbnd OH intermediate. The adsorbed OHsbnd Hgsbnd OH is stable and hardly detaches from the catalyst surface due to the highly endothermic process. A large amount of electron transfer has been found from Hg to the produced OH groups and has little irreversible effect on the Fe3O4 (111) surface. On the Feoct2-terminated Fe3O4 (111) surface, the Feoct2 site is more active than Fetet1 site. H2O2 decomposition and Hg0 oxidation processes are more likely to occur due to that the Feoct2 site both contains Fe2+ and Fe3+ cations. The calculations reveal that Hg0 oxidation by the OH radical produced from H2O2 is energetically favored. Additionally, Hg0 and H2O2 co-interaction mechanism on the Fe3O4 (111) interface has been investigated on the basis of partial local density of state calculation.

  9. Promotion effect of H2 on ethanol oxidation and NOx reduction with ethanol over Ag/Al2O3 catalyst.

    PubMed

    Yu, Yunbo; Li, Yi; Zhang, Xiuli; Deng, Hua; He, Hong; Li, Yuyang

    2015-01-06

    The catalytic partial oxidation of ethanol and selective catalytic reduction of NOx with ethanol (ethanol-SCR) over Ag/Al2O3 were studied using synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS). The intermediates were identified by PIMS and their photoionization efficiency (PIE) spectra. The results indicate that H2 promotes the partial oxidation of ethanol to acetaldehyde over Ag/Al2O3, while the simultaneously occurring processes of dehydration and dehydrogenation were inhibited. H2 addition favors the formation of ammonia during ethanol-SCR over Ag/Al2O3, the occurrence of which creates an effective pathway for NOx reduction by direct reaction with NH3. Simultaneously, the enhancement of the formation of ammonia benefits its reaction with surface enolic species, resulting in producing -NCO species again, leading to enhancement of ethanol-SCR over Ag/Al2O3 by H2. Using VUV-PIMS, the reactive vinyloxy radical was observed in the gas phase during the NOx reduction by ethanol for the first time, particularly in the presence of H2. Identification of such a reaction occurring in the gas phase may be crucial for understanding the reaction pathway of HC-SCR over Ag/Al2O3.

  10. Ethylene induces combinatorial effects of histone H3 acetylation in gene expression in Arabidopsis.

    PubMed

    Wang, Likai; Zhang, Fan; Rode, Siddharth; Chin, Kevin K; Ko, Eun Esther; Kim, Jonghwan; Iyer, Vishwanath R; Qiao, Hong

    2017-07-17

    Histone acetylation and deacetylation are essential for gene regulation and have been implicated in the regulation of plant hormone responses. Many studies have indicated the role of histone acetylation in ethylene signaling; however, few studies have investigated how ethylene signaling regulates the genomic landscape of chromatin states. Recently, we found that ethylene can specifically elevate histone H3K14 acetylation and the non-canonical histone H3K23 acetylation in etiolated seedlings and the gene activation is positively associated with the elevation of H3K14Ac and H3K23Ac in response to ethylene. To assess the role of H3K9, H3K14, and H3K23 histone modifications in the ethylene response, we examined how ethylene regulates histone acetylation and the transcriptome at global level and in ethylene regulated genes both in wild type (Col-0) and ein2-5 seedlings. Our results revealed that H3K9Ac, H3K14Ac, and H3K23Ac are preferentially enriched around the transcription start sites and are positively correlated with gene expression levels in Col-0 and ein2-5 seedlings both with and without ethylene treatment. In the absence of ethylene, no combinatorial effect of H3K9Ac, H3K14Ac, and H3K23Ac on gene expression was detected. In the presence of ethylene, however, combined enrichment of the three histone acetylation marks was associated with high gene expression levels, and this ethylene-induced change was EIN2 dependent. In addition, we found that ethylene-regulated genes are expressed at medium or high levels, and a group of ethylene regulated genes are marked by either one of H3K9Ac, H3K14Ac or H3K23Ac. In this group of genes, the levels of H3K9Ac were altered by ethylene, but in the absence of ethylene the levels of H3K9Ac and peak breadths are distinguished in up- and down- regulated genes. In the presence of ethylene, the changes in the peak breadths and levels of H3K14Ac and H3K23Ac are required for the alteration of gene expressions. Our study reveals that

  11. Vaporization of SiO2 and MgSiO3

    NASA Astrophysics Data System (ADS)

    Stixrude, L. P.; Xiao, B.

    2016-12-01

    Vaporization of SiO2 and MgSiO3B Xiaoa and L Stixrude*a, a Department of Earth Sciences, University College London, WC1E 6BT London, UK *presenting author, email: l.stixrude@ucl.ac.uk Vaporization is an important process in Earth's earliest evolution during which giant impacts are thought to have produced a transient silicate atmosphere. As experimental data are very limited, little is known of the near-critical vaporization of Earth's major oxide components: MgO and SiO2. We have performed novel ab initio molecular dynamics simulations of vapor-liquid coexistence in the SiO2 and MgSiO3 systems. The simulations, based on density functional theory using the VASP code, begin with a suitably prepared liquid slab embedded in a vacuum. During the dynamical trajectory in the canonical ensemble, we see spontaneous vaporization, leading eventually to a steady-state chemical equilibrium between the two coexisting phases. We locate the liquid-vapor critical point at 6600 K and 0.40 g/cm3 for MgSiO3 and 5300 K and 0.43 g/cm3 for SiO2. By carefully examining the trajectories, we determine the composition and speciation of the vapor. For MgSiO3, We find that the vapor is significantly richer in Mg, O, and atomic (non-molecular) species than extrapolation of low-temperature experimental data has suggested. These results will have important implications for our understanding of the initial chemistry of the Earth and Moon and the initial thermal state of Earth.

  12. Phase change of hydromagnesite, Mg5(CO3)4(OH)2 4H2O by thermal decomposition

    NASA Astrophysics Data System (ADS)

    Yamamoto, G. I.; Kyono, A.; Tamura, T.

    2017-12-01

    In recent years, the global warming is the most important environment problem, and thus attempts of CO2 geological storage have been made to remove carbon dioxide from the atmosphere all over the world (XUE and Nakao 2008). Regarding mineral CO2 sequestration, CO2 is chemically stored in solid carbonates by carbonation of minerals. Magnesium and calcium carbonates have long been known as a good CO2 storage. Hydrous magnesium carbonates can be, however, considered as much better candidates for CO2 storage because they precipitate easily from aqueous solutions. The typical hydrous magnesium carbonates are nesquehonite, MgCO3 3H2O and hydromagnesite, Mg5(CO3)4(OH)2 4H2O. Concerning their thermal properties, the former has been studied in detail, whereas, the latter is not enough. In this study, we performed in-site high-temperature X-ray diffraction (XRD) and thermogravimetric and differential thermal (TG-DTA) analyses to reveal the phase change of hydromagnesite at high temperature. The high-temperature XRD and TG-DTA were measured up to 320 oC and 550 oC, respectively. The results of in-site high-temperature XRD showed that, no significant change was observed up to 170 oC. With increasing temperature, the intensities of started to decrease at 200 oC, and all peaks disappeared at 290 oC. Above the temperature of the decomposition a few peaks corresponding to periclase appeared. The results of TG-DTA clearly showed that there were two weight loss steps in the temperature range of 200 to 340 oC and 340 to 500 oC, which correspond to the dehydration and decarbonation of hydromagnesite, respectively. These weight losses were accompanied by the endothermic maxima in the DTA. The dihydroxylation of hydromagnesite is spread over the two steps. Therefore, hydromagnesite decomposes into periclase, carbon dioxide, and water without passing through magnesite around 300 oC as following reaction: Mg5(CO3)4(OH)2 4H2O → 5MgO + 4CO2 + 5H2O.

  13. Photolysis of H2O-H2O2 Mixtures: The Destruction of H2O2

    NASA Technical Reports Server (NTRS)

    Loeffler, M. J.; Fama, M.; Baragiola, R. A.; Carlson, R. W.

    2013-01-01

    We present laboratory results on the loss of H2O2 in solid H2O + H2O2 mixtures at temperatures between 21 and 145 K initiated by UV photolysis (193 nm). Using infrared spectroscopy and microbalance gravimetry, we measured the decrease of the 3.5 micrometer infrared absorption band during UV irradiation and obtained a photodestruction cross section that varies with temperature, being lowest at 70 K. We use our results, along with our previously measured H2O2 production rates via ionizing radiation and ion energy fluxes from the spacecraft to compare H2O2 creation and destruction at icy satellites by ions from their planetary magnetosphere and from solar UV photons. We conclude that, in many cases, H2O2 is not observed on icy satellite surfaces because the H2O2 photodestruction rate is much higher than the production rate via energetic particles, effectively keeping the H2O2 infrared signature at or below the noise level.

  14. Magnetic Ordering of Antiferromagnetic Trimer System 23CuCl2·2H2O

    NASA Astrophysics Data System (ADS)

    Sanda, M.; Kubo, K.; Asano, T.; Morodomi, H.; Inagaki, Y.; Kawae, T.; Wang, J.; Matsuo, A.; Kindo, K.; Sato, T. J.

    2012-12-01

    In this paper, we present the magnetic properties of 23CuCl2·2H2O (b = betaine, C5H11NO2). 23CuCl2·2H2O is the first model substance for a two-dimensional S = 1/2 orthogonal antiferromagnetic trimer system. We have performed magnetic susceptibility, magnetization curve, and specific heat under extreme conditions: low temperatures and high magnetic fields in this system. The experimental results indicate that this substance is a magnetically S = 1/2 antiferromagnetic trimer system. The magnetization also shows one-third of the saturation value (MS ~ 3.2μB/f.u.) between 5 and 14T The specific heat in a zero field shows a sharp peak at 1.38K corresponding to a long-range magnetic ordering, TN. As the magnetic field increases, the TN shifts remarkably to a lower temperature and is suppressed. Above 5T, the specific heat has no anomaly down to 150mK In the plateau region with an energy gap, the magnetic ordering seems to be disappeared.

  15. Syntheses and structural characterization of vanado-tellurites and vanadyl-selenites: SrVTeO{sub 5}(OH), Cd{sub 2}V{sub 2}Te{sub 2}O{sub 11}, Ca{sub 3}VSe{sub 4}O{sub 13}·H{sub 2}O and Ba{sub 2}VSe{sub 3}O{sub 10}

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

    Konatham, Satish; Vidyasagar, Kanamaluru, E-mail: kvsagar@iitm.ac.in

    Four new quaternary vanado-tellurites and vanadyl-selenites, namely, SrVTeO{sub 5}(OH)(1), Cd{sub 2}V{sub 2}Te{sub 2}O{sub 11}(2), Ca{sub 3}VSe{sub 4}O{sub 13}·H{sub 2}O(3) and Ba{sub 2}VSe{sub 3}O{sub 10}(4) have been synthesized and structurally characterized by single crystal X-ray diffraction. The oxidation state of vanadium is +5 in tellurites 1 and 2 and +4 in selenites 3 and 4. The structures of SrVTeO{sub 5}(OH)(1) and Cd{sub 2}V{sub 2}Te{sub 2}O{sub 11}(2) compounds consist of (VTeO{sub 5}(OH)){sup 2-} and (V{sub 2}Te{sub 2}O{sub 11}){sup 4-}anionic chains respectively, which are built from tetrahedral VO{sub 4} and disphenoidal TeO{sub 4} moieties. Similarly the structures of Ca{sub 3}VSe{sub 4}O{sub 13}·H{sub 2}O(3)more » and Ba{sub 2}VSe{sub 3}O{sub 10}(4) respectively contain (VSe{sub 2}O{sub 7}){sup 2-} and (VSe{sub 3}O{sub 10}){sup 4-} anionic chains, which are made up of octahedral VO{sub 6} and pyramidal SeO{sub 3} units. Compounds 1 and 3 have been characterized by thermogravimetric and infrared spectroscopic methods. Compounds 1 and 2 are wide band gap semiconductors. - Graphical abstract: Ca{sub 3}VSe{sub 4}O{sub 13}·H{sub 2}O and Ba{sub 2}VSe{sub 3}O{sub 10} compounds contain (VSe{sub 2}O{sub 7}){sup 2-} and (VSe{sub 3}O{sub 10}){sup 4-} chains. - Highlights: • Four new vanado-tellurites and vanadyl-selenites are synthesized. • Their structural features are different. • The vanado-tellurites are wide band gap semiconductors.« less

  16. Temperature compensation effects of TiO2 on Ca[(Li1/3Nb2/3)0.8Sn0.2]O3-δ microwave dielectric ceramic

    NASA Astrophysics Data System (ADS)

    Hu, Mingzhe; Wei, Huanghe; Xiao, Lihua; Zhang, Kesheng; Hao, Yongde

    2017-10-01

    The crystal structure and dielectric properties of TiO2-modified Ca[(Li1/3Nb2/3)0.8Sn0.2]O3-δ microwave ceramics are investigated in the present paper. The crystal structure is probed by XRD patterns and their Rietveld refinement, results show that a single perovskite phase is formed in TiO2-modified Ca[(Li1/3Nb2/3)0.8Sn0.2]O3-δ ceramics with the crystal structure belonging to the orthorhombic Pbnm 62 space group. Raman spectra results indicate that the B-site order-disorder structure transition is a key point to the dielectric loss of TiO2-modified Ca[(Li1/3Nb2/3)0.8Sn0.2]O3-δ ceramics at microwave frequencies. After properly modified by TiO2, the large negative temperature coefficient of Ca[(Li1/3Nb2/3)0.8Sn0.2]O3-δ ceramic can be compensated and the optimal microwave dielectric properties can reach 𝜀r = 25.66, Qf = 18,894 GHz and TCF = -6.3 ppm/∘C when sintered at 1170∘C for 2.5 h, which manifests itself for potential use in microwave dielectric devices for modern wireless communication.

  17. 5-AIQ inhibits H2O2-induced apoptosis through reactive oxygen species scavenging and Akt/GSK-3β signaling pathway in H9c2 cardiomyocytes.

    PubMed

    Park, Eun-Seok; Kang, Jun Chul; Kang, Do-Hyun; Jang, Yong Chang; Yi, Kyu Yang; Chung, Hun-Jong; Park, Jong Seok; Kim, Bokyung; Feng, Zhong-Ping; Shin, Hwa-Sup

    2013-04-01

    Poly(adenosine 5'-diphosphate ribose) polymerase (PARP) is a nuclear enzyme activated by DNA strand breaks and plays an important role in the tissue injury associated with ischemia and reperfusion. The aim of the present study was to investigate the protective effect of 5-aminoisoquinolinone (5-AIQ), a PARP inhibitor, against oxidative stress-induced apoptosis in H9c2 cardiomyocytes. 5-AIQ pretreatment significantly protected against H2O2-induced cell death, as determined by the XTT assay, cell counting, terminal deoxynucleotidyl transferase-mediated dUTP nick end labeling assay, and Western blot analysis of apoptosis-related proteins such as caspase-3, Bax, and Bcl-2. Upregulation of antioxidant enzymes such as manganese superoxide dismutase and catalase accompanied the protective effect of 5-AIQ on H2O2-induced cell death. Our data also showed that 5-AIQ pretreatment protected H9c2 cells from H2O2-induced apoptosis by triggering activation of Akt and glycogen synthase kinase-3β (GSK-3β), and that the protective effect of 5-AIQ was diminished by the PI3K inhibitor LY294002 at a concentration that effectively abolished 5-AIQ-induced Akt and GSK-3β activation. In addition, inhibiting the Akt/GSK-3β pathway by LY294002 significantly attenuated the 5-AIQ-mediated decrease in cleaved caspase-3 and Bax activation and H9c2 cell apoptosis induction. Taken together, these results demonstrate that 5-AIQ prevents H2O2-induced apoptosis in H9c2 cells by reducing intracellular reactive oxygen species production, regulating apoptosis-related proteins, and activating the Akt/GSK-3β pathway. Copyright © 2013 Elsevier Inc. All rights reserved.

  18. Applications of molybdenum-95 NMR spectroscopy. 7. Studies of metal-metal bonded systems including aqueous molybdenum(IV) and molybdenum(V). Crystal and molecular structure of Na/sub 2/(Mo/sub 3/O/sub 4/((O/sub 2/CCH/sub 2/)/sub 2/NCH/sub 3/)/sub 3/). 7H/sub 2/O

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

    Ghellar, S.F.; Hambley, T.W.; Brownlee, R.T.

    1983-03-23

    Solution /sup 95/Mo NMR studies are reported on spin-coupled polynuclear systems of Mo(V), Mo(IV), and Mo(II). Resonances occur at low fields compared to mononuclear species. The chemical shifts of the Mo(IV)-aquo ion in 4 M p-toluenesulfonic and methanesulfonic acid media and those of the Mo(IV) complexes containing oxalate, EDTA, and methyliminodiacetate ligands (whose solid-state structures are based on the (Mo/sub 3/O/sub 4/)/sup 4 +/ cluster) fall in the narrow range of 172 ppm spanning 990-1162 ppm. As the known chemical shift scale for the /sup 95/Mo nucleus covers 7000 ppm, this observation indicates that the /sup 95/Mo nucleus is inmore » a similar chemical environment in each of the species examined and, taken with published evidence, confirms formulation of the Mo(IV)-aquo ion as (Mo/sub 3/O/sub 4/(H/sub 2/O)/sub 9/)/sup 4 +/. Two resonances are detected in the above range for Mo(IV)/sub aq/ in 4 M hydrochloric acid and for ((Mo/sub 3/O/sub 4/)/sub 2/(PDTA)/sub 3/)/sup 4 -/. Additional resonances appear at 539-608 ppm in the methanesulfonic acid, hydrochloric acid, and EDTA systems when stored in air. These are assigned to (Mo/sup v//sub 2/O/sub 4/)/sup 2 +/-based species by comparison with the observed resonances of the Mo(V)-aquo ion, (Mo/sup v//sub 2/O/sub 4/(H/sub 2/O)/sub 6/)/sup 2 +/, in the relevant acid media and with (Mo/sup v//sub 2/O/sub 4/(EDTA))/sup 2 -/ in H/sub 2/O. The (Mo/sup v//sub 2/O/sub 4/(PDTA))/sup 2 -/ anion exhibits two resonances associated with inequivalent molybdenum sites. Resonances for (Mo/sup II//sub 2/(O/sub 2/CR)/sub 4/) (R = CF/sub 3/, n-Pr), which contain formal quadruple bonds, have been observed for the first time and are the most deshielded /sup 95/Mo NMR signals detected to date. The methyliminodiacetate complex, Na/sub 2/(Mo/sub 3/O/sub 4/((O/sub 2/CCH/sub 2/)/sub 2/NCH/sub 3/)/sub 3/).7H/sub 2/O, was isolated. Its crystal structure contains a discrete trinuclear (Mo/sup IV//sub 3/O/sub 4/((O/sub 2/CCH/sub 2

  19. Surface-enhanced Raman spectrum of Gly-Gly adsorbed on the silver colloidal surface

    NASA Astrophysics Data System (ADS)

    Xiaojuan, Yuan; Huaimin, Gu; Jiwei, Wu

    2010-08-01

    Raman and SERS spectra of homodipeptide Gly-Gly and Gly were recorded and compared in this paper, and band assignment for the functional groups contained in these molecules was analyzed in detail. Time-dependent and pH-dependent SERS spectra of Gly-Gly molecule adsorbed on nano-colloidal silver surface were also studied. The time-dependent SERS spectra of Gly-Gly are characterized by the increase in intensity of bands primarily representing the vibrational signatures emanating from the amino and amide moiety of Gly-Gly molecule. It is found that the adsorption style of Gly-Gly on the silver colloid changes as time goes on; at 5 min after adding the sample to the silver colloid, Gly-Gly adsorbs on silver surface firstly through the carboxylate, amino and amide groups, and then the carboxylate group is far away from the silver surface at 10 min to 3 days. The SERS variation of Gly-Gly with the change of pH suggests that the adsorption style is pH-dependent, the different adsorption behavior of the Gly-Gly occurs on silver surface at different pH values.

  20. New Insight into SO2 Poisoning and Regeneration of CeO2-WO3/TiO2 and V2O5-WO3/TiO2 Catalysts for Low-Temperature NH3-SCR.

    PubMed

    Xu, Liwen; Wang, Chizhong; Chang, Huazhen; Wu, Qingru; Zhang, Tao; Li, Junhua

    2018-06-19

    In this study, the poisoning effects of SO 2 on the V 2 O 5 -WO 3 /TiO 2 (1%VWTi) and CeO 2 -WO 3 /TiO 2 (5%CeWTi) selective catalytic reduction (SCR) catalysts were investigated in the presence of steam, and also the regeneration of deactivated catalysts was studied. After pretreating the catalysts in a flow of NH 3 + SO 2 + H 2 O + O 2 at 200 °C for 24 h, it was observed that the low-temperature SCR (LT-SCR) activity decreased significantly over the 1%VWTi and 5%CeWTi catalysts. For 1%VWTi, NH 4 HSO 4 (ABS) was the main product detected after the poisoning process. Both of NH 4 HSO 4 and cerium sulfate species were formed on the poisoned 5%CeWTi catalyst, indicating that SO 2 reacted with Ce 3+ /Ce 4+ , even in the presence of high concentration of NH 3 . The decrease of BET specific surface area, NO x adsorption capacity, the ratio of chemisorbed oxygen, and reducibility were responsible for the irreversible deactivation of the poisoned 5%CeWTi catalyst. Meanwhile, the LT-SCR activity could be recovered over the poisoned 1%VWTi after regeneration at 400 °C, but not for the 5%CeWTi catalyst. For industrial application, it is suggested that the regeneration process can be utilized for 1%VWTi catalysts after a period of time after NH 4 HSO 4 accumulated on the catalysts.

  1. Comparison of the potential for developmental toxicity of prenatal exposure to two dietary chromium supplements, chromium picolinate and [Cr3O(O2CCH2CH3)(6(H2O)3]+, in mice.

    PubMed

    Bailey, M M; Sturdivant, J; Jernigan, P L; Townsend, M B; Bushman, J; Ankareddi, I; Rasco, J F; Hood, R D; Vincent, J B

    2008-02-01

    Chromium(III) is generally thought to be an essential trace element that allows for proper glucose metabolism. However, chromium(III) picolinate, Cr(pic)3, a popular dietary supplement form of chromium, has been shown to be capable of generating hydroxyl radicals and oxidative DNA damage in rats. The cation [Cr3O(O2CCH2CH3)(6(H2O)3]+, Cr3, has been studied as an alternative supplemental source of chromium. It has been shown to increase insulin sensitivity and lower glycated hemoglobin levels in rats, making it attractive as a potential therapeutic treatment for gestational diabetes. To date, no studies have been published regarding the safety of Cr3 supplementation to a developing fetus. From gestation days (GD) 6-17, mated CD-1 female mice were fed diets delivering either 25 mg Cr/kg/day as Cr(pic)(3), 3.3 or 26 mg Cr/kg/day as Cr3, or the diet only to determine if Cr3 could cause developmental toxicity. Dams were sacrificed on GD 17, and their litters were examined for adverse effects. No signs of maternal toxicity were observed. No decrease in fetal weight or significantly increased incidence of skeletal defects was observed in the Cr3 or Cr(pic)3 exposed fetuses compared to the controls. Maternal exposure to either Cr(pic)3 or Cr3 at the dosages employed did not appear to cause deleterious effects to the developing offspring in mice. (c) 2007 Wiley-Liss, Inc.

  2. Spectroscopic properties of Er(3+)/Yb(3+) co-doped Bi(2)O(3)-B(2)O(3)-GeO(2) glasses.

    PubMed

    Zhang, Xudong; Xu, Tiefeng; Nie, Qiuhua; Dai, Shixun; Shen, Xiang; Zhang, Xianghua

    2007-05-01

    Er(3+)/Yb(3+) co-doped 60Bi(2)O(3)-(40 - x)B(2)O(3)-xGeO(2) (BBG; x=0, 5, 10, 15 mol%) glasses that are suitable for fiber lasers, amplifiers have been fabricated and characterized. The absorption spectra, emission spectra, and lifetime of the (4)I(13/2) level and quantum efficiency of Er(3+):(4)I(13/2) --> (4)I(15/2) transition were measured and calculated. With the substitution of GeO(2) for B(2)O(3), both Delta lambda(eff) and sigma(e) decrease from 75 to 71 nm and 9.88 to 8.12 x 10(-21) cm(2), respectively. The measured lifetime of the (4)I(13/2) level and quantum efficiency of Er(3+):(4)I(13/2) --> (4)I(15/2) transition increase from 1.18 to 1.5 ms and 36.2% to 43.2%, respectively. The emission spectra of Er(3+):(4)I(13/2) --> (4)I(15/2) transition was also analyzed using a peak-fit routine, and an equivalent four-level system was proposed to estimate the stark splitting for the (4)I(15/2) and (4)I(13/2) levels of Er(3+) in the BBG glasses. The results indicate that the (4)I(13/2) --> (4)I(15/2) emission of Er(3+) can be exhibit a considerable broadening due to a significant enhance the peak A, and D emission.

  3. EPR study of gamma irradiated N-methyl taurine (C3H9NO3S) and sodium hydrogen sulphate monohydrate (NaHSO3·H2O) single crystals.

    PubMed

    Yıldırım, Ilkay; Karabulut, Bünyamin

    2011-03-01

    EPR study of gamma irradiated C(3)H(9)NO(3)S and NaHSO(3).H(2)O single crystals have been carried out at room temperature. There is one site for the radicals in C(3)H(9)NO(3)S and two magnetically distinct sites for the radicals in NaHSO(3). The observed lines in the EPR spectra have been attributed to the species of SO(3)(-) and RH radicals for N-methyl taurine, and to the SO(3)(-) and OH radicals for sodium hydrogen sulfate monohydrate single crystals. The principal values of the g for SO(3)(-), the hyperfine values of RH and OH proton splitting have been calculated and discussed. Copyright © 2010 Elsevier B.V. All rights reserved.

  4. Remarkably high apparent quantum yield of the overall photocatalytic H2O splitting achieved by utilizing Zn ion added Ga2O3 prepared using dilute CaCl2 solution.

    PubMed

    Sakata, Yoshihisa; Hayashi, Takuya; Yasunaga, Ryō; Yanaga, Nobuyuki; Imamura, Hayao

    2015-08-21

    Remarkably high photocatalytic activity for the overall H2O splitting, where the activity was 32 mmol h(-1) for H2 production and 16 mmol h(-1) for O2 production under irradiation from a 450 W high-pressure Hg lamp and the apparent quantum yield (AQY) was 71% under irradiation at 254 nm, was achieved by utilizing a Rh(0.5)Cr(1.5)O3(Rh; 0.5 wt%)/Zn(3 mol%)-Ga2O3 photocatalyst when Ga2O3 was prepared using dilute CaCl2 aqueous solution having a concentration of 0.001 mol l(-1).

  5. Zn0-CNTs-Fe3O4 catalytic in situ generation of H2O2 for heterogeneous Fenton degradation of 4-chlorophenol.

    PubMed

    Yang, Zhao; Gong, Xiao-Bo; Peng, Lin; Yang, Dan; Liu, Yong

    2018-06-04

    A novel Zn 0 -CNTs-Fe 3 O 4 composite was synthesized by the chemical co-precipitation combined with high sintering process at nitrogen atmosphere. The as-prepared composite was characterized by SEM, EDS, XRD, XPS, VSM and N 2 adsorption/desorption experiments. A novel heterogeneous Fenton-like system, composed of Zn 0 -CNTs-Fe 3 O 4 composite and dissolved oxygen (O 2 ) in solution, which can in situ generate H 2 O 2 and OH, was used for the degradation of 4-chlorophenol (4-CP). The influences of various operational parameters, including the initial pH, dosage of Zn 0 -CNTs-Fe 3 O 4 and initial concentration of 4-CP on the removal of 4-CP were investigated. The removal efficiencies of 4-CP and total organic carbon (TOC) were 99% and 57%, respectively, at the initial pH of 1.5, Zn 0 -CNTs-Fe 3 O 4 dosage of 2 g/L, 4-CP initial concentration of 50 mg/L and oxygen flow rate of 400 mL/min. Based on the results of the radical scavenger effect study, the hydroxyl radical was considered as the main reactive oxidants in Zn 0 -CNTs-Fe 3 O 4 /O 2 system and a possible degradation pathway of 4-CP was proposed. Copyright © 2018. Published by Elsevier Ltd.

  6. Growth Oscillatory Zoning in Erythrite, Ideally Co3(AsO4)2·8H2O: Structural Variations in Vivianite-Group Minerals

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

    Antao, Sytle M.; Dhaliwal, Inayat

    The crystal structure of an oscillatory zoned erythrite sample from Aghbar mine, Bou Azzer, Morocco, was refined using synchrotron high-resolution powder X-ray diffraction (HRPXRD) data, Rietveld refinement, space group C2/m, and Z = 2. The crystal contains two sets of oscillatory zones that appear to have developed during epitaxial growth. The unit-cell parameters obtained are a = 10.24799(3) Å, b = 13.42490(7) Å, c = 4.755885(8) Å, β = 105.1116(3)°, and V = 631.680(4) Å3. The empirical formula for erythrite, obtained with electron-probe micro-analysis (EPMA), is [Co2.78Zn0.11Ni0.07Fe0.04]Σ3.00(AsO4)2·8H2O. Erythrite belongs to the vivianite-type structure that contains M1O2(H2O)4 octahedra and M22O6(H2O)4 octahedralmore » dimers that are linked by TO4 (T5+ = As or P) tetrahedra to form complex layers parallel to the (010) plane. These layers are connected by hydrogen bonds. The average [6] = 2.122(1) Å and average [6] = 2.088(1) Å. With space group C2/m, there are two solid solutions: M3(AsO4)2·8H2O and M3(PO4)2·8H2O where M2+ = Mg, Fe, Co, Ni, or Zn. In these As- and P-series, using data from this study and from the literature, we find that their structural parameters evolve linearly with V and in a nearly parallel manner despite of the large difference in size between P5+ (0.170 Å) and As5+ (0.355 Å) cations. Average [4], [6], and [6] distances increase linearly with V. The average distance is affected by M atoms, whereas the average distance is unaffected because it contains shorter and stronger P–O bonds. Although As- and P-series occur naturally, there is no structural reason why similar V-series vivianite-group minerals do not occur naturally or cannot be synthesized.« less

  7. Air Plasma-Sprayed La2Zr2O7-SrZrO3 Composite Thermal Barrier Coating Subjected to CaO-MgO-Al2O3-SiO2 (CMAS)

    NASA Astrophysics Data System (ADS)

    Cai, Lili; Ma, Wen; Ma, Bole; Guo, Feng; Chen, Weidong; Dong, Hongying; Shuang, Yingchai

    2017-08-01

    La2Zr2O7-SrZrO3 composite thermal barrier coatings (TBCs) were prepared by air plasma spray (APS). The La2Zr2O7-SrZrO3 composite TBCs covered with calcium-magnesium-aluminum-silicate (CMAS) powder, as well as the powder mixture of CMAS and spray-dried La2Zr2O7-SrZrO3 composite powder, were heat-treated at 1250 °C in air for 1, 4, 8, and 12 h. The phase constituents and microstructures of the reaction products were characterized by x-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy. Experimental results showed that the La2Zr2O7-SrZrO3 composite TBCs had higher CMAS resistance than 8YSZ coating. A dense new layer developed between CMAS and La2Zr2O7-SrZrO3 composite TBCs during interaction, and this new layer consisted mostly of apatite (Ca2La8(SiO4)6O2) and c-ZrO2. The newly developed layer effectively protected the La2Zr2O7-SrZrO3 composite TBCs from further CMAS attack.

  8. Nqrs Data for C26H34N2O3V (Subst. No. 1601)

    NASA Astrophysics Data System (ADS)

    Chihara, H.; Nakamura, N.

    This document is part of Subvolume B 'Substances Containing C10H16 … Zn' of Volume 48 'Nuclear Quadrupole Resonance Spectroscopy Data' of Landolt-Börnstein - Group III 'Condensed Matter'. It contains an extract of Section '3.2 Data tables' of the Chapter '3 Nuclear quadrupole resonance data' providing the NQRS data for C26H34N2O3V (Subst. No. 1601)

  9. 1-(2-Hy-droxy-eth-yl)-3-[(2-hy-droxy-eth-yl)amino]-4-(1H-indol-3-yl)-1H-pyrrole-2,5-dione.

    PubMed

    Xie, Zhi-Xiong; Zhao, Sheng-Yin

    2011-04-01

    There are four molecules in the asymmetric unit of the title compound, C(16)H(17)N(3)O(4), in which the dihedral angles between the indole ring system and maleimide ring are 4.5 (3), 8.3 (3), 8.4 (2) and 10.4 (2)°. In the crystal, mol-ecules are linked by numerous N-H⋯O and O-H⋯O hydrogen bonds, generating a three-dimensional network.

  10. Spin-forbidden and spin-allowed cyclopropenone (c-H{sub 2}C{sub 3}O) formation in interstellar medium

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

    Ahmadvand, Seyedsaeid; Zaari, Ryan R.; Varganov, Sergey A., E-mail: svarganov@unr.edu

    2014-11-10

    Three proposed mechanisms of cyclopropenone (c-H{sub 2}C{sub 3}O) formation from neutral species are studied using high-level electronic structure methods in combination with nonadiabatic transition state and collision theories to deduce the likelihood of each reaction mechanism under interstellar conditions. The spin-forbidden reaction involving the singlet electronic state of cyclopenylidene (c-C{sub 3}H{sub 2}) and the triplet state of atomic oxygen is studied using nonadiabatic transition state theory to predict the rate constant for c-H{sub 2}C{sub 3}O formation. The spin-allowed reactions of c-C{sub 3}H{sub 2} with molecular oxygen and acetylene with carbon monoxide were also investigated. The reaction involving the ground electronicmore » states of acetylene and carbon monoxide has a very large reaction barrier and is unlikely to contribute to c-H{sub 2}C{sub 3}O formation in interstellar medium. The spin-forbidden reaction of c-C{sub 3}H{sub 2} with atomic oxygen, despite the high probability of nonadiabatic transition between the triplet and singlet states, was found to have a very small rate constant due to the presence of a small (3.8 kcal mol{sup –1}) reaction barrier. In contrast, the spin-allowed reaction between c-C{sub 3}H{sub 2} and molecular oxygen is found to be barrierless, and therefore can be an important path to the formation of c-H{sub 2}C{sub 3}O molecule in interstellar environment.« less

  11. Hydrothermal synthesis of Y{sub 2}O{sub 3} coated Y{sub 2}O{sub 3}:Eu{sup 3+} nanotubes for enhanced photoluminescence properties

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

    Gao, Linhui, E-mail: gaolhui@zstu.edu.cn; Wang, Guangfa; Zhu, Hongliang

    Highlights: • Eu{sup 3+} doped Y{sub 2}O{sub 3} nanotubes. • Hydrothermal synthesis of Y{sub 2}O{sub 3} coated Y{sub 2}O{sub 3}:Eu{sup 3+} nanostructures assissted with a further heat treatment. • Tunable coating ratios of Y{sub 2}O{sub 3} coated Y{sub 2}O{sub 3}:Eu{sup 3+} nanophosphor. • Enhanced photoluminescence intensity of Y{sub 2}O{sub 3}:Eu{sup 3+} more than 60% by Y{sub 2}O{sub 3} surface coating. - Abstract: Novel Y{sub 2}O{sub 3} coated Y{sub 2}O{sub 3}:Eu{sup 3+} nanotubes with different coating ratios were synthesized successfully by a facile two-step process, including hydrothermal synthesis of Y(OH){sub 3} coated Y(OH){sub 3}:Eu{sup 3+} as precursors and then calcination ofmore » them at 1000 °C for 2 h. X-ray diffraction patterns and field emission scanning electron microscope images indicated these Y{sub 2}O{sub 3} coated Y{sub 2}O{sub 3}:Eu{sup 3+} phosphors possess tubular nanostructures. The photoluminescence properties of Y{sub 2}O{sub 3} coated Y{sub 2}O{sub 3}:Eu{sup 3+} were systematically investigated by photoluminescence spectra, and photoluminescence enhancement was observed after proper coating. In other words, the coating ratio played a crucial role in photoluminescence efficiency. When it was 1/9, the photoluminescence intensity of {sup 5}D{sub 0} → {sup 7}F{sub 2} emission (about 613 nm) was 60% higher than that of Y{sub 2}O{sub 3}: Eu{sup 3+} phosphors under 255 nm excitation. Therefore, surface coating may be an alternative route for enhanced photoluminescence properties of the Y{sub 2}O{sub 3}:Eu{sup 3+} red-emitting phosphor.« less

  12. Bulk Crystallization in a SiO2/Al2O3/Y2O3/AlF3/B2O3/Na2O Glass: Fivefold Pseudo Symmetry due to Monoclinic Growth in a Glassy Matrix Containing Growth Barriers

    PubMed Central

    Wisniewski, Wolfgang; Seyring, Martin; Patzig, Christian; Höche, Thomas; Keshavarzi, Ashkan; Rüssel, Christian

    2016-01-01

    A glass with the mol% composition 17 Y2O3·33 Al2O3·40 SiO2·2 AlF3·3 Na22 CeF3·3 B2O3 is heat treated at 1000 °C for 6–24 h. This results in the surface nucleation and growth of YAG. Nucleation and growth of star-shaped alumina and later of monoclinic β-Y2Si2O7 and orthorhombic δ-Y2Si2O7 are additionally observed in the bulk. Phase identification and localization are performed by electron backscatter diffraction (EBSD) as well as TEM analysis. The monoclinic β-Y2Si2O7 observed in the bulk occurs in the form of large, crystal agglomerates which range from 50 to 120 μm in size. The individual crystals are aligned along the c-axis which is the fastest growing axis. Ten probability maxima are observed in the pole-figures illustrating the rotation of orientations around the c-axes indicating a fivefold symmetry. This symmetry is caused by multiple twinning which results in a high probability of specific orientation relationships with rotation angles of ~36°, ~108° (also referred to as the pentagon angle) and ~144° around the c-axis. All these rotation angles are close to the multiples of 36° which are required for an ideal fivefold symmetry. This is the first report of a fivefold symmetry triggered by the presence of barriers hindering crystal growth. PMID:26813152

  13. Air-surface exchange of H2O, CO2, and O3 at a tallgrass prairie in relation to remotely sensed vegetation indices

    NASA Technical Reports Server (NTRS)

    Gao, W.; Wesely, M. L.; Cook, D. R.; Hart, R. L.

    1992-01-01

    Parameters derived from eddy correlation measurements of the air-surface exchange rates of H2O, CO2, and O3 over a tallgrass prairie are examined in terms of their relationships with spectral reflectance data remotely sensed from aircraft and satellites during the four 1987 intensive field campaigns of the First ISLSCP Field Experiment (FIFE). The surface conductances were strongly modulated by photosynthetically active radiation received at the surface when the grass was green and well watered; mesophyll resistances were large for CO2 but negligible for H2O and O3.

  14. A fruitful demonstration in sensors based on upconversion luminescence of Yb3+/Er3+codoped Sb2O3-WO3-Li2O (SWL) glass-ceramic

    NASA Astrophysics Data System (ADS)

    Prasad Sukul, Prasenjit; Kumar, Kaushal

    2016-07-01

    In this article, erbium and ytterbium doped lithium tungsten antimonate (Yb3+/Er3+:Sb2O3-WO3-Li2O) glass-ceramics (GC) is synthesized and its novel applications in temperature sensing and detection of latent fingerprints is studied. It is also estimated that this material could be useful as a solar cell concentrator. The upconversion emission studies on Yb3+/Er3+:SWL glass-ceramics have shown intense green emission at 525 nm (2H11/2 → 4I15/2) & 545 nm (4s3/2 → 4I15/2). The variation of UC intensities with external temperature have shown a well-fashioned pattern, which suggests that the 2H11/2 and 4S3/2 levels of Er3+ ion are thermally coupled and can act as a temperature sensor in the 300-500 K temperature range. Dry powder of Yb3+/Er3+:SWL glass-ceramic is used to develop latent fingerprint with high contrast in green color on glass slide.

  15. Studies of dispersion energy in hydrogen-bonded systems. H2O-HOH, H2O-HF, H3N-HF, HF-HF

    NASA Astrophysics Data System (ADS)

    Szcześniak, M. M.; Scheiner, Steve

    1984-02-01

    Dispersion energy is calculated in the systems H2O-HOH, H2O-HF, H3N-HF, and HF-HF as a function of the intermolecular separation using a variety of methods. M≂ller-Plesset perturbation theory to second and third orders is applied in conjunction with polarized basis sets of 6-311G** type and with an extended basis set including a second set of polarization functions (DZ+2P). These results are compared to a multipole expansion of the dispersion energy, based on the Unsöld approximation, carried out to the inverse tenth power of the intermolecular distance. Pairwise evaluation is also carried out using both atom-atom and bond-bond formulations. The MP3/6-311G** results are in generally excellent accord with the leading R-6 term of the multipole expansion. This expansion, if carried out to the R-10 term, reproduces extremely well previously reported dispersion energies calculated via variation-perturbation theory. Little damping of the expansion is required for intermolecular distances equal to or greater than the equilibrium separation. Although the asymptotic behavior of the MP2 dispersion energy is somewhat different than that of the other methods, augmentation of the basis set by a second diffuse set of d functions leads to quite good agreement in the vicinity of the minima. Both the atom-atom and bond-bond parametrization schemes are in good qualitative agreement with the other methods tested. All approaches produce similar dependence of the dispersion energy upon the angular orientation between the two molecules involved in the H bond.

  16. 3-Amino-1,2,4-triazolium ion in [24(3at)]Cl and [24(3at)]2SnCl6·H2O. Comparative X-ray, vibrational and theoretical studies

    NASA Astrophysics Data System (ADS)

    Daszkiewicz, Marek; Marchewka, Mariusz K.

    2012-09-01

    Crystal structures of 3-amino-1,2,4-triazolium chloride and bis(3-amino-1,2,4-triazolium) hexachloridostannate monohydrate were determined by means of X-ray single crystal diffraction. The route of protonation of organic molecule and tautomer equilibrium constants for the cationic forms were calculated using B3LYP/6-31G* method. The most stable protonated species is 2,4-H2-3-amino-1,2,4-triazolium ion, 24(3at)+. Very good agreement between theoretical and experimental frequencies was achieved due to very weak interactions existing in studied compounds. Significantly weaker intermolecular interactions are found in [24(3at)]2SnCl6·H2O than in [24(3at)]Cl. The differences in strength of interactions are manifested in red and blue shifts for stretching and bending motions, respectively. PED calculations show that for 24(3at)+ ion the stretching type of motion of two Nringsbnd H bonds is independent, whereas bending is coupled.

  17. High pressure structure studies of 6H-SrIrO3 and the octahedral tilting in 3C-SrIrO3 towards a post-perovskite

    NASA Astrophysics Data System (ADS)

    Kronbo, Camilla H.; Nielsen, Morten B.; Kevy, Simone M.; Parisiades, Paraskevas; Bremholm, Martin

    2016-06-01

    The high pressure behaviors of the two perovskite structures (hexagonal 6H-SrIrO3 and orthorhombic 3C-SrIrO3) have been studied in diamond anvil cells to 43 and 60 GPa, respectively, using synchrotron powder X-ray diffraction. 6H-SrIrO3 was first synthesized at ambient pressure and subsequently transformed into 3C-SrIrO3 in a large volume press at 8.8 GPa and 1000 °C. Both polymorphs were found to retain the initial symmetry up to the highest pressures measured, but in the case of 6H-SrIrO3, two anomalies were identified: a change in the axial compressibilities at 24 GPa and a change in both the axial and volume compressibilities at 32 GPa. Fitting a 3rd order Birch-Murnaghan equation of state to the obtained P-V data yielded bulk moduli of K0=151.5(12) GPa (fitted range 0H-SrIrO3 and K0=187.1(9) GPa for 3C-SrIrO3. Analysis of the structural parameters for 6H-SrIrO3 aided by F-f plots suggests the anomalies are caused by changes in the compression mechanism. Comparison of the two polymorphs reveals that 6H-SrIrO3 becomes less compressible than 3C-SrIrO3 above 32 GPa as a result of the mechanistic change, and a crossing of their P-V curves is avoided. For 3C-SrIrO3, analysis of the octahedral tilt angles shows that these increase monotonically from the ambient value of 7.23(6) to 23.0(2)° at 60 GPa suggesting that a transition to a post-perovskite is approached.

  18. Bulk Kosterlitz-Thouless Type Molecular Superconductor β″-(BEDT-TTF)2[(H2O)(NH4)2Cr(C2O4)3]·18-crown-6.

    PubMed

    Martin, Lee; Lopez, Jordan R; Akutsu, Hiroki; Nakazawa, Yasuhiro; Imajo, Shusaku

    2017-11-20

    A new molecular superconductor, β″-(BEDT-TTF) 2 [(H 2 O)(NH 4 ) 2 Cr(C 2 O 4 ) 3 ]·18-crown-6, has been synthesized from the organic donor molecule BEDT-TTF with the anion Cr(C 2 O 4 ) 3 3- . The crystal structure consists of conducting organic layers of BEDT-TTF molecules which adopt the β″ packing motif (layer A), layers of NH 4 + and Λ-Cr(C 2 O 4 ) 3 3- (layer B), layers of (H 2 O)(NH 4 )18-crown-6 (layer C), and layers of NH 4 + and Δ-Cr(C 2 O 4 ) 3 3- (layer D) which produce a superstructure with a repeating pattern of ABCDABCDA. As a result of this packing arrangement, this is the 2D superconductor with the widest gap between conducting layers where only a single donor packing motif is present (β″). Superconducting critical temperatures at ambient pressure observed by electrical transport and magnetic measurements are 4.0-4.9 and 2.5 K, respectively. The strong 2D nature of this system, the broad transition to T zero at 1.8K, and the transition of α of V ∝ I α from 1 to 3 on I-V curves strongly suggest that the superconducting transition is very close to a Kosterlitz-Thouless transition. The magnetic field dependence of the superconducting critical temperature parallel to the conducting plane gives an upper critical field μ 0 H c2∥ > 8 T, which is over the calculated Pauli-Clogston limit for this material.

  19. Violet-green excitation for NIR luminescence of Yb3+ ions in Bi2O3-B2O3-SiO2-Ga2O3 glasses.

    PubMed

    Li, Weiwei; Cheng, Jimeng; Zhao, Guoying; Chen, Wei; Hu, Lili; Guzik, Malgorzata; Boulon, Georges

    2014-04-21

    60Bi(2)O(3)-20B(2)O(3)-10SiO(2)-10Ga(2)O(3) glasses doped with 1-9 mol% Yb(2)O(3) were prepared and investigated mainly on their violet-green excitation for the typical NIR emission of Yb(3+), generally excited in the NIR. Two violet excitation bands at 365 nm and 405 nm are related to Yb(2+) and Bi(3+). 465 nm excitation band and 480 nm absorption band in the blue-green are assigned to Bi(0) metal nanoparticles/grains. Yb-content-dependence of the excitation and absorption means that Bi(0) is the reduced product of Bi(3+), but greatly competed by the redox reaction of Yb(2+) ↔ Yb(3+). It is proved that the violet-green excitations result in the NIR emission of Yb(3+). On the energy transfer, the virtual level of Yb(3+)-Yb(3+) as well as Bi(0) dimers probably plays an important role. An effective and controllable way is suggested to achieve nano-optical applications by Bi(0) metal nanoparticles/grains and Yb(3+).

  20. 5-AIQ inhibits H{sub 2}O{sub 2}-induced apoptosis through reactive oxygen species scavenging and Akt/GSK-3β signaling pathway in H9c2 cardiomyocytes

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

    Park, Eun-Seok; Kang, Jun Chul; Kang, Do-Hyun

    2013-04-01

    Poly(adenosine 5′-diphosphate ribose) polymerase (PARP) is a nuclear enzyme activated by DNA strand breaks and plays an important role in the tissue injury associated with ischemia and reperfusion. The aim of the present study was to investigate the protective effect of 5-aminoisoquinolinone (5-AIQ), a PARP inhibitor, against oxidative stress-induced apoptosis in H9c2 cardiomyocytes. 5-AIQ pretreatment significantly protected against H{sub 2}O{sub 2}-induced cell death, as determined by the XTT assay, cell counting, terminal deoxynucleotidyl transferase-mediated dUTP nick end labeling assay, and Western blot analysis of apoptosis-related proteins such as caspase-3, Bax, and Bcl-2. Upregulation of antioxidant enzymes such as manganese superoxidemore » dismutase and catalase accompanied the protective effect of 5-AIQ on H{sub 2}O{sub 2}-induced cell death. Our data also showed that 5-AIQ pretreatment protected H9c2 cells from H{sub 2}O{sub 2}-induced apoptosis by triggering activation of Akt and glycogen synthase kinase-3β (GSK-3β), and that the protective effect of 5-AIQ was diminished by the PI3K inhibitor LY294002 at a concentration that effectively abolished 5-AIQ-induced Akt and GSK-3β activation. In addition, inhibiting the Akt/GSK-3β pathway by LY294002 significantly attenuated the 5-AIQ-mediated decrease in cleaved caspase-3 and Bax activation and H9c2 cell apoptosis induction. Taken together, these results demonstrate that 5-AIQ prevents H{sub 2}O{sub 2}-induced apoptosis in H9c2 cells by reducing intracellular reactive oxygen species production, regulating apoptosis-related proteins, and activating the Akt/GSK-3β pathway. - Highlights: ► 5-AIQ, a PARP inhibitor, decreased H{sub 2}O{sub 2}-induced H9c2 cell death and apoptosis. ► 5-AIQ upregulated antioxidant Mn-SOD and catalase, while decreasing ROS production. ► 5-AIQ decreased H{sub 2}O{sub 2}-induced increase in cleaved caspase-3 and Bax and decrease in Bcl2. ► 5-AIQ activated Akt and

  1. Cr6+-containing phases in the system CaO-Al2O3-CrO42--H2O at 23 °C

    NASA Astrophysics Data System (ADS)

    Pöllmann, Herbert; Auer, Stephan

    2012-01-01

    Synthesis and investigation of lamellar calcium aluminium hydroxy salts was performed to study the incorporation of chromate ions in the interlayer of lamellar calcium aluminium hydroxy salts. Different AFm-phases (calcium aluminate hydrate with alumina, ferric oxide, mono-anion phase) containing chromate were synthesized. These AFm-phases belong to the group of layered double hydroxides (LDHs). 3CaO·Al2O3·CaCrO4·nH2O and C3A·1/2Ca(OH)2·1/2CaCrO4·12H2O were obtained as pure phases and their different distinct interlayer water contents and properties determined. Solid solution of chromate-containing phases and tetracalcium-aluminate-hydrate (TCAH) were studied. The uptake of chromate into TCAH from solutions was proven. Chromate contents in solution decrease to <0.2 mg/l.

  2. Rotational Spectroscopy of the NH3-H2 Molecular Complex

    NASA Astrophysics Data System (ADS)

    Surin, L. A.; Tarabukin, I. V.; Schlemmer, S.; Breier, A. A.; Giesen, T. F.; McCarthy, M. C.; van der Avoird, A.

    2017-03-01

    We report the first high resolution spectroscopic study of the NH3-H2 van der Waals molecular complex. Three different experimental techniques, a molecular beam Fourier transform microwave spectrometer, a millimeter-wave intracavity jet OROTRON spectrometer, and a submillimeter-wave jet spectrometer with multipass cell, were used to detect pure rotational transitions of NH3-H2 in the wide frequency range from 39 to 230 GHz. Two nuclear spin species, (o)-NH3-(o)-H2 and (p)-NH3-(o)-H2, have been assigned as carriers of the observed lines on the basis of accompanying rovibrational calculations performed using the ab initio intermolecular potential energy surface (PES) of Maret et al. The experimental spectra were compared with the theoretical bound state results, thus providing a critical test of the quality of the NH3-H2 PES, which is a key issue for reliable computations of the collisional excitation and de-excitation of ammonia in the dense interstellar medium.

  3. The interstellar chemistry of C3H and C3H2 isomers

    PubMed Central

    Loison, Jean-Christophe; Agúndez, Marcelino; Wakelam, Valentine; Roueff, Evelyne; Gratier, Pierre; Marcelino, Núria; Nuñez Reyes, Dianailys; Cernicharo, José; Gerin, Maryvonne

    2017-01-01

    We report the detection of linear and cyclic isomers of C3H and C3H2 towards various starless cores and review the corresponding chemical pathways involving neutral (C3Hx with x=1,2) and ionic (C3Hx+ with x = 1,2,3) isomers. We highlight the role of the branching ratio of electronic Dissociative Recombination (DR) reactions of C3H2+ and C3H3+ isomers showing that the statistical treatment of the relaxation of C3H* and C3H2* produced in these DR reactions may explain the relative c,l-C3H and c,l-C3H2 abundances. We have also introduced in the model the third isomer of C3H2 (HCCCH). The observed cyclic-to-linear C3H2 ratio vary from 110 ± 30 for molecular clouds with a total density around 1×104 molecules.cm-3 to 30 ± 10 for molecular clouds with a total density around 4×105 molecules.cm-3, a trend well reproduced with our updated model. The higher ratio for low molecular cloud densities is mainly determined by the importance of the H + l-C3H2H + c-C3H2 and H + t-C3H2H + c-C3H2 isomerization reactions. PMID:29142332

  4. The interstellar chemistry of C3H and C3H2 isomers

    NASA Astrophysics Data System (ADS)

    Loison, Jean-Christophe; Agúndez, Marcelino; Wakelam, Valentine; Roueff, Evelyne; Gratier, Pierre; Marcelino, Núria; Reyes, Dianailys Nuñez; Cernicharo, José; Gerin, Maryvonne

    2017-10-01

    We report the detection of linear and cyclic isomers of C3H and C3H2 towards various starless cores and review the corresponding chemical pathways involving neutral (C3Hx with x = 1,2) and ionic (C3Hx+ with x = 1,2,3) isomers. We highlight the role of the branching ratio of electronic dissociative recombination (DR) reactions of C3H2+ and C3H3+ isomers, showing that the statistical treatment of the relaxation of C3H* and C3H2* produced in these DR reactions may explain the relative c,l-C3H and c,l-C3H2 abundances. We have also introduced in the model the third isomer of C3H2 (HCCCH). The observed cyclic-to-linear C3H2 ratio varies from 110 ± 30 for molecular clouds with a total density of about 1 × 104 molecules cm-3 to 30 ± 10 for molecular clouds with a total density of about 4 × 105 molecules cm-3, a trend well reproduced with our updated model. The higher ratio for molecular clouds with low densities is determined mainly by the importance of the H + l-C3H2H + c-C3H2 and H + t-C3H2H + c-C3H2 isomerization reactions.

  5. Method for determination of .sup.18 O/.sup.16 O and .sup.2 H/.sup.1 H ratios and .sup.3 H (tritium) concentrations of xylem waters and subsurface waters using time series sampling

    DOEpatents

    Smith, Brian; Menchaca, Leticia

    1999-01-01

    A method for determination of .sup.18 O/.sup.16 O and .sup.2 H/.sup.1 H ratios and .sup.3 H concentrations of xylem and subsurface waters using time series sampling, insulating sampling chambers, and combined .sup.18 O/.sup.16 O, .sup.2 H/.sup.1 H and .sup.3 H concentration data on transpired water. The method involves collecting water samples transpired from living plants and correcting the measured isotopic compositions of oxygen (.sup.18 O/.sup.16 O) and hydrogen (.sup.2 H/.sup.1 H and/or .sup.3 H concentrations) to account for evaporative isotopic fractionation in the leafy material of the plant.

  6. Fabrication and assembly of two-dimensional TiO2/WO3·H2O heterostructures with type II band alignment for enhanced photocatalytic performance

    NASA Astrophysics Data System (ADS)

    Xu, Tao; Wang, Yun; Zhou, Xiaofang; Zheng, Xiaoli; Xu, Qun; Chen, Zhimin; Ren, Yumei; Yan, Bo

    2017-05-01

    The recombination of photo-induced charges is one of the main issues to limit the large-scale applications in photocatalysis and photoelectrocatalysis. To improve the charge separation, we fabricate a novel type II 2D ultrathin TiO2/WO3·H2O heterostructures with the assistance of supercritical CO2 (SC CO2) in this work. The as-fabricated heterostructures possess high photocatalytic activity for the degradation of methyl orange(MO) and high photocurrent response under simulated solar light (AM 1.5). For the TiO2/WO3·H2O heterostructures, the MO solution could be degraded by 95.5% in 150 min, and the photocurrent density reaches to 6.5 μA cm-2, exhibiting a significant enhancement compared with pure TiO2 and WO3·H2O nanosheets.

  7. Monodisperse Fe3O4 and γ-Fe2O3 magnetic mesoporous microspheres as anode materials for lithium-ion batteries.

    PubMed

    Xu, Jing-San; Zhu, Ying-Jie

    2012-09-26

    Monodisperse Fe(3)O(4) and γ-Fe(2)O(3) magnetic mesoporous microspheres are prepared via a surfactant-free solvothermal combined with precursor thermal transformation method. The as-prepared Fe(3)O(4) and γ-Fe(2)O(3) magnetic mesoporous microspheres have a relatively high specific surface area of 122.3 and 138.6 m(2)/g, respectively. The Fe(3)O(4) and γ-Fe(2)O(3) magnetic mesoporous microspheres are explored as the anode materials for lithium-ion batteries, and they have a high initial discharge capacity of 1307 and 1453 mA h/g, respectively, and a good reversible performance (450 mA h/g for Fe(3)O(4) and 697 mA h/g for γ-Fe(2)O(3) after 110 cycles) at the current density of 0.2C.

  8. Crystal structure of bis-(μ-3-nitro-benzoato)-κ3O,O':O3O:O,O'-bis-[bis-(3-cyano-pyridine-κN1)(3-nitro-benzoato-κ2O,O')cadmium].

    PubMed

    Hökelek, Tuncer; Akduran, Nurcan; Özen, Azer; Uğurlu, Güventürk; Necefoğlu, Hacali

    2017-03-01

    The asymmetric unit of the title compound, [Cd 2 (C 7 H 4 NO 4 ) 4 (C 6 H 4 N 2 ) 4 ], contains one Cd II atom, two 3-nitro-benzoate (NB) anions and two 3-cyano-pyridine (CPy) ligands. The two CPy ligands act as monodentate N(pyridine)-bonding ligands, while the two NB anions act as bidentate ligands through the carboxyl-ate O atoms. The centrosymmetric dinuclear complex is generated by application of inversion symmetry, whereby the Cd II atoms are bridged by the carboxyl-ate O atoms of two symmetry-related NB anions, thus completing the distorted N 2 O 5 penta-gonal-bipyramidal coordination sphere of each Cd II atom. The benzene and pyridine rings are oriented at dihedral angles of 10.02 (7) and 5.76 (9)°, respectively. In the crystal, C-H⋯N hydrogen bonds link the mol-ecules, enclosing R 2 2 (26) ring motifs, in which they are further linked via C-H⋯O hydrogen bonds, resulting in a three-dimensional network. In addition, π-π stacking inter-actions between parallel benzene rings and between parallel pyridine rings of adjacent mol-ecules [shortest centroid-to-centroid distances = 3.885 (1) and 3.712 (1) Å, respectively], as well as a weak C-H⋯π inter-action, may further stabilize the crystal structure.

  9. Topologically identical, but geometrically isomeric layers in hydrous α-, β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O and anhydrous Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})

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

    Yu, Na; Klepov, Vladislav V.; Villa, Eric M.

    2014-07-01

    The hydrothermal reaction of uranyl nitrate with rubidium nitrate and arsenic (III) oxide results in the formation of polymorphic α- and β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O (α-, β-RbUAs) and the anhydrous phase Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] (RbUAs). These phases were structurally, chemically and spectroscopically characterized. The structures of all three compounds are based upon topologically identical, but geometrically isomeric layers. The layers are linked with each other by means of the Rb cations and hydrogen bonding. Dehydration experiments demonstrate that water deintercalation from hydrous α- and β-RbUAs yields anhydrous RbUAs via topotactic reactions. - Graphical abstract: Three differentmore » layer geometries observed in the structures of Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] and α- and β- Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O. Two different coordination environments of uranium polyhedra (types I and II) are shown schematically on the top of the figure. - Highlights: • Three new uranyl arsenates were synthesized from the hydrothermal reactions. • The phases consist of the topologically identical but geometrically different layers. • Topotactic transitions were observed in the processes of mono-hyrates dehydration.« less

  10. Enrichment of Sc2O3 and TiO2 from bauxite ore residues.

    PubMed

    Deng, Bona; Li, Guanghui; Luo, Jun; Ye, Qing; Liu, Mingxia; Peng, Zhiwei; Jiang, Tao

    2017-06-05

    As a major byproduct generated in the alumina industry, bauxite ore residue is an important reserve of scandium and titanium. In this study, the feasibility and mechanism of enriching Sc 2 O 3 and TiO 2 from a non-magnetic material, which was obtained from carbothermal reductive roasting and magnetic separation of bauxite ore residue, were investigated based on a two-step (acidic and alkali) leaching process. It was revealed that approximately 78% SiO 2 and 30-40% of CaO, FeO and Al 2 O 3 were removed from a non-magnetic material with 0.0134wt.% Sc 2 O 3 and 7.64wt.% TiO 2 by phosphoric acidic leaching, while about 95% Al 2 O 3 and P 2 O 5 were further leached by subsequent sodium hydroxide leaching of the upper-stream leach residue. A Sc 2 O 3 -, TiO 2 - rich material containing 0.044wt.% Sc 2 O 3 and 25.5wt.% TiO 2 was obtained, the recovery and the enrichment factor of Sc 2 O 3 and TiO 2 were about 85% and 5, respectively. The enrichment of Sc 2 O 3 was attributed to higher pH (>3.3) of phosphoric acid solution than its dissolution pH 0 , and the enrichment of TiO 2 was mainly associated with the insoluble perovskite (CaTiO 3 ) in the acidic solution at ambient temperature. As Sc 2 O 3 and TiO 2 cannot be dissolved in the alkali solution, they were further enriched in the leach residue. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Metal-organic framework: Structure and magnetic properties of [Cu3(BTC)2 (L)x·(CuO)y]n (L=H2O, DMF)

    NASA Astrophysics Data System (ADS)

    da Silva, Gilvaldo G.; Machado, F. L. A.; Junior, S. Alves; Padrón-Hernández, E.

    2017-09-01

    The compounds [Cu3(BTC)2(L)x·(CuO)y], with BTC (benzene 1,3,5-tricarboxylate) and L (H2O or DMF) were prepared using electrochemical synthesis. Structural and morphologic characterizations were performed by X-ray diffraction and scanning electronic microscopy. The [Cu3(BTC)2 (L)x·(CuO)y] contain dimeric [Cu2(O2CR)]4 units with three possible spin configurations arising from Cu(II) 3d9 states and Cu-Cu δ bond. We observed an unusual very strong antiferromagnetic coupling in temperatures ranging from 100 K to 350 K for [Cu3(BTC)2.(H2O)3. (CuO)y]n. The inverse susceptibility versus temperature shows a linearity from 20 K up to 65 K fitting the Curie-Weiss law, for L = DMF. The CW X-band electron paramagnetic resonance spectroscopy (EPR) was important to explore the coordination state for DMF in the network. It was observed that DMF is located in an equatorial geometry of the coordination network experimenting interactions from the nitrogen and copper ions.

  12. Structure and properties of hopeites (Mg xZn 1- x) 3(PO 4) 2 · 4H 2O

    NASA Astrophysics Data System (ADS)

    Haussühl, S.; Middendorf, B.; Dörffel, M.

    1991-07-01

    Mg-hopeites (Mg xZn 1- x) 3(PO 4) 2 · 4H 2O were prepared by crystallization from hot aqueous solutions (70°C). The structure of (Mg 0.206Zn 0.794) 3(PO 4) 2 · 4H 2O has been determined from 1612 unique reflections (MoKα, R = 0.033): Pnma, a1 = 10.594(2), a2 = 18.333(2), a3 = 5.029(2)Å, Z = 4, Dcalc = 2.943g cm -3. The structure resembles that of pure hopeite. However, the magnesium atoms occupy only the sixcoordinated site. The thermal behavior of hopeites is strongly influenced by the substitution of Zn by Mg. The dehydration range is shifted to higher temperatures with increasing Mg content. A strongly anisotropic thermal expansion was measured by X-ray diffraction in a temperature range of -40° to 50°C. Experiments to substitute Zn by Ca, Sr, and Ba in the hopeite failed. A hitherto unknown monoclinic phase with the composition BaZn 2(PO 4) 2 · H 2O and a1 = 4.707(2), a2 = 7.840(2), a3 = 8.061(3)Å, and α 2 = 88.99(4)° was found.

  13. Reactions of fac-[Re(CO)3(H2O)3]+ with nucleoside diphosphates and thiamine diphosphate in aqueous solution investigated by multinuclear NMR spectroscopy.

    PubMed

    Adams, Kristie M; Marzilli, Patricia A; Marzilli, Luigi G

    2007-10-29

    Products formed between monoester diphosphates (MDPs) and fac-[Re(CO)3(H2O)3]OTf at pH 3.6 were examined. Such adducts of the fac-[Re(CO)3]+ moiety have an uncommon combination of properties for an "inert" metal center in that sharp NMR signals can be observed, yet the products are equilibrating at rates allowing NMR EXSY cross-peaks to be observed. Thiamine diphosphate (TDP) and uridine 5'-diphosphate (5'-UDP) form 1:1 bidentate {Palpha,Pbeta} chelates, in which the MDP binds Re(I) via Palpha and Pbeta phosphate groups. Asymmetric centers are created at Re(I) (RRe/SRe) and Palpha (Delta/Lambda), leading to four diastereomers. The two mirror pairs of diastereomers (RReDelta/SReLambda) and (RReLambda/SReDelta) for TDP (no ribose) and for all four diastereomers (RReDelta, RReLambda, SReDelta, SReLambda) for 5'-UDP (asymmetric ribose) gave two and four sets of NMR signals for the bound MDP, respectively. 31Palpha-31Palpha EXSY cross-peaks indicate that the fac-[Re(CO)3(H2O)({Palpha,Pbeta}MDP)]- isomers interchange slowly on the NMR time scale, with an average k approximately equal to 0.8 s(-1) at 32 degrees C; the EXSY cross-peaks could arise from chirality changes at only Re(I) or at only Palpha. Guanosine 5'-diphosphate (5'-GDP), with a ribose moiety and a Re(I)-binding base, formed both possible diastereomers (RRe and SRe) of the fac-[Re(CO)3(H2O)({N7,Pbeta}GDP)]- macrochelate, with one slightly more abundant diastereomer suggested to be RRe by Mn2+ ion 1H NMR signal line-broadening combined with distances from molecular models. Interchange of the diastereomers requires that the coordination site of either N7 or Pbeta move to the H2O site. 31Palpha-31Palpha EXSY cross-peaks indicate a k approximately equal to 0.5 s(-1) at 32 degrees C for RRe-to-SRe interchange. The similarity of the rate constants for interchange of fac-[Re(CO)3(H2O)({Palpha,Pbeta}MDP)]- and fac-[Re(CO)3(H2O)({N7,Pbeta}GDP)]- adducts suggest strongly that interchange of Pbeta and H2O coordination

  14. Heterogeneous kinetics of H2O, HNO3 and HCl on HNO3 hydrates (α-NAT, β-NAT, NAD) in the range 175-200 K

    NASA Astrophysics Data System (ADS)

    Iannarelli, Riccardo; Rossi, Michel J.

    2016-09-01

    Experiments on the title compounds have been performed using a multidiagnostic stirred-flow reactor (SFR) in which the gas phase as well as the condensed phase has been simultaneously investigated under stratospheric temperatures in the range 175-200 K. Wall interactions of the title compounds have been taken into account using Langmuir adsorption isotherms in order to close the mass balance between deposited and desorbed (recovered) compounds. Thin solid films at 1 µm typical thickness have been used as a proxy for atmospheric ice particles and have been deposited on a Si window of the cryostat, with the optical element being the only cold point in the deposition chamber. Fourier transform infrared (FTIR) absorption spectroscopy in transmission as well as partial and total pressure measurement using residual gas mass spectrometry (MS) and sensitive pressure gauges have been employed in order to monitor growth and evaporation processes as a function of temperature using both pulsed and continuous gas admission and monitoring under SFR conditions. Thin solid H2O ice films were used as the starting point throughout, with the initial spontaneous formation of α-NAT (nitric acid trihydrate) followed by the gradual transformation of α- to β-NAT at T > 185 K. Nitric acid dihydrate (NAD) was spontaneously formed at somewhat larger partial pressures of HNO3 deposited on pure H2O ice. In contrast to published reports, the formation of α-NAT proceeded without prior formation of an amorphous HNO3 / H2O layer and always resulted in β-NAT. For α- and β-NAT, the temperature-dependent accommodation coefficient α(H2O) and α(HNO3), the evaporation flux Jev(H2O) and Jev(HNO3) and the resulting saturation vapor pressure Peq(H2O) and Peq(HNO3) were measured and compared to binary phase diagrams of HNO3 / H2O in order to afford a thermochemical check of the kinetic parameters. The resulting kinetic and thermodynamic parameters of activation energies for evaporation (Eev) and

  15. DFT studies on H 2O adsorption and its effect on CO oxidation over spinel Co 3O 4 (110) surface

    NASA Astrophysics Data System (ADS)

    Xu, Xiang Lan; Li, Jun Qian

    2011-12-01

    Adsorption of H2O and its effect on CO oxidation over spinel Co3O4 (110) surface were studied by density functional theory calculations. H2O is adsorbed favorably at the octahedral cobalt (Cooct) site through O atom on the surface. Hydrogen bonding interaction between 1s orbitals of H atoms in H2O and the 2p orbitals of surface active oxygen sites plays a key role for H2O adsorption. The inhibition effect of H2O adsorption on the CO oxidation over the surfaces is attributed to the competition between H2O and CO molecules for the surface twofold coordinated oxygen site.

  16. Presynaptic Dopamine D2 Receptors Modulate [3H]GABA Release at StriatoPallidal Terminals via Activation of PLC → IP3 → Calcineurin and Inhibition of AC → cAMP → PKA Signaling Cascades.

    PubMed

    Jijón-Lorenzo, Rafael; Caballero-Florán, Isaac Hiram; Recillas-Morales, Sergio; Cortés, Hernán; Avalos-Fuentes, José Arturo; Paz-Bermúdez, Francisco Javier; Erlij, David; Florán, Benjamín

    2018-02-21

    Striatal dopamine D2 receptors activate the PLC → IP3 → Calcineurin-signaling pathway to modulate the neural excitability of En+ Medium-sized Spiny GABAergic neurons (MSN) through the regulation of L-type Ca 2+ channels. Presynaptic dopaminergic D2 receptors modulate GABA release at striatopallidal terminals through L-type Ca 2+ channels as well, but their signaling pathway is still undetermined. Since D2 receptors are Gi/o-coupled and negatively modulate adenylyl cyclase (AC), we investigated whether presynaptic D2 receptors modulate GABA release through the same signaling cascade that controls excitability in the striatum or by the inhibition of AC and decreased PKA activity. Activation of D2 receptors stimulated formation of [ 3 H]IP 1 and decreased Forskolin-stimulated [ 3 H]cAMP accumulation in synaptosomes from rat Globus Pallidus. D2 receptor activation with Quinpirole in the presence of L 745,870 decreased, in a dose-dependent manner, K + -induced [ 3 H]GABA release in pallidal slices. The effect was prevented by the pharmacological blockade of Gi/o βγ subunit effects with Gallein, PLC with U 73122, IP3 receptor activation with 4-APB, Calcineurin with FK506. In addition, when release was stimulated with Forskolin to activate AC, D2 receptors also decreased K + -induced [ 3 H]GABA release, an effect occluded with the effect of the blockade of PKA with H89 or stimulation of release with the cAMP analog 8-Br-cAMP. These data indicate that D2 receptors modulate [ 3 H]GABA release at striatopallidal terminals by activating the PLC → IP3 → Calcineurin-signaling cascade, the same one that modulates excitability in soma. Additionally, D2 receptors inhibit release when AC is active. Both mechanisms appear to converge to regulate the activity of presynaptic L-type Ca 2+ channels. Copyright © 2018 IBRO. Published by Elsevier Ltd. All rights reserved.

  17. Highly efficient visible-light driven photocatalytic hydrogen production from a novel Z-scheme Er3+:YAlO3/Ta2O5-V5+||Fe3+-TiO2/Au coated composite

    NASA Astrophysics Data System (ADS)

    Wang, Guowei; Ma, Xue; Wei, Shengnan; Li, Siyi; Qiao, Jing; Wang, Jun; Song, Youtao

    2018-01-01

    In this work, the preparation of a novel Z-scheme photocatalyst, Er3+:YAlO3/Ta2O5-V5+||Fe3+-TiO2/Au coated composite, for visible-light photocatalytic hydrogen production is reported for the first time. In this photocatalyst, Au nanoparticles as conduction band co-catalyst provide more active sites to enrich electrons. Ta2O5-V5+||Fe3+-TiO2 as composite redox cycle system thoroughly separates the photo-generated electrons and holes. In addition, Er3+:YAlO3 as up-conversion luminescence agent (from visible-light to ultraviolet-light) provides enough ultraviolet-light for satisfying the energy demand of wide band-gap semiconductors (TiO2 and Ta2O5). The photocatalytic hydrogen production can be achieved from methanol as sacrificial agent (electron donor) under visible-light irradiation. The main influence factors such as initial solution pH and molar ratio of TiO2 and Ta2O5 on visible-light photocatalytic hydrogen production activity of Er3+:YAlO3/Ta2O5-V5+||Fe3+-TiO2/Au coated composite are discussed in detail. The results show that the Er3+:YAlO3/Ta2O5-V5+||Fe3+-TiO2/Au coated composite with 1.0:0.5 M ratio of TiO2 and Ta2O5 in methanol aqueous solution at pH = 6.50 displays the highest photocatalytic hydrogen production activity. Furthermore, a high level of photocatalytic activity can be still maintained within three cycles under the same conditions. It implies that the prepared Z-scheme Er3+:YAlO3/Ta2O5-V5+||Fe3+-TiO2/Au coated composite may be a promising photocatalyst utilizing solar energy for hydrogen production.

  18. OPTICAL AND SPECTROSCOPIC STUDIES OF Fe2O3-Bi2O3-B2O3:V2O5 GLASSES

    NASA Astrophysics Data System (ADS)

    Sanjay; Kishore, N.; Agarwal, A.; Dahiya, S.; Pal, Inder; Kumar, Navin

    2013-11-01

    The glasses of compositions xFe2O3ṡ (40 - x)Bi2O3ṡ60B2O32V2O5 have been prepared by the standard melt-quenching technique. Amorphous nature of these samples is ascertained by XRD patterns. The presence of BO3 and BO4 units is identified by IR spectra of glass samples. The absorption edge (λcut-off) shifts toward longer wavelengths with an increase in Fe2O3 content in the glass matrix. The values of optical band gap energy for indirect allowed and forbidden transitions have been determined and it is found to decrease with increase in transition metal ions. The Urbach's energy is used to characterize the degree of disorder in amorphous solids.

  19. Cis-regulatory underpinnings of human GLI3 expression in embryonic craniofacial structures and internal organs.

    PubMed

    Abbasi, Amir A; Minhas, Rashid; Schmidt, Ansgar; Koch, Sabine; Grzeschik, Karl-Heinz

    2013-10-01

    The zinc finger transcription factor Gli3 is an important mediator of Sonic hedgehog (Shh) signaling. During early embryonic development Gli3 participates in patterning and growth of the central nervous system, face, skeleton, limb, tooth and gut. Precise regulation of the temporal and spatial expression of Gli3 is crucial for the proper specification of these structures in mammals and other vertebrates. Previously we reported a set of human intronic cis-regulators controlling almost the entire known repertoire of endogenous Gli3 expression in mouse neural tube and limbs. However, the genetic underpinning of GLI3 expression in other embryonic domains such as craniofacial structures and internal organs remain elusive. Here we demonstrate in a transgenic mice assay the potential of a subset of human/fish conserved non-coding sequences (CNEs) residing within GLI3 intronic intervals to induce reporter gene expression at known regions of endogenous Gli3 transcription in embryonic domains other than central nervous system (CNS) and limbs. Highly specific reporter expression was observed in craniofacial structures, eye, gut, and genitourinary system. Moreover, the comparison of expression patterns directed by these intronic cis-acting regulatory elements in mouse and zebrafish embryos suggests that in accordance with sequence conservation, the target site specificity of a subset of these elements remains preserved among these two lineages. Taken together with our recent investigations, it is proposed here that during vertebrate evolution the Gli3 expression control acquired multiple, independently acting, intronic enhancers for spatiotemporal patterning of CNS, limbs, craniofacial structures and internal organs. © 2013 The Authors Development, Growth & Differentiation © 2013 Japanese Society of Developmental Biologists.

  20. Msx genes are important apoptosis effectors downstream of the Shh/Gli3 pathway in the limb.

    PubMed

    Lallemand, Yvan; Bensoussan, Vardina; Cloment, Cécile Saint; Robert, Benoît

    2009-07-15

    In tetrapods, the anteroposterior (AP) patterning of the limb is under the control of the antagonistic activities of the secreted factor Sonic hedgehog (Shh) and Gli3R, the truncated repressor form of the transcription factor Gli3. In this report, we show that Msx1 and Msx2 are targets and downstream effectors of Gli3R. Consequently, in Shh null mutants, Msx genes are overexpressed and, furthermore, partially responsible for the limb phenotype. This is exemplified by the fact that reducing Msx activity in Shh mutants partially restores a normal limb development. Finally, we show that the main action of the Msx genes, in both normal and Shh(-/-) limb development, is to control cell death in the mesenchyme. We propose that, in the limb, Msx genes act downstream of the Shh/Gli3 pathway by transducing BMP signaling and that, in the absence of Shh signaling, their deregulation contributes to the extensive apoptosis that impairs limb development.

  1. Isotope analysis of diamond-surface passivation effect of high-temperature H{sub 2}O-grown atomic layer deposition-Al{sub 2}O{sub 3} films

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

    Hiraiwa, Atsushi, E-mail: hiraiwa@aoni.waseda.jp, E-mail: qs4a-hriw@asahi-net.or.jp; Saito, Tatsuya; Matsumura, Daisuke

    2015-06-07

    The Al{sub 2}O{sub 3} film formed using an atomic layer deposition (ALD) method with trimethylaluminum as Al precursor and H{sub 2}O as oxidant at a high temperature (450 °C) effectively passivates the p-type surface conduction (SC) layer specific to a hydrogen-terminated diamond surface, leading to a successful operation of diamond SC field-effect transistors at 400 °C. In order to investigate this excellent passivation effect, we carried out an isotope analysis using D{sub 2}O instead of H{sub 2}O in the ALD and found that the Al{sub 2}O{sub 3} film formed at a conventional temperature (100 °C) incorporates 50 times more CH{sub 3} groups thanmore » the high-temperature film. This CH{sub 3} is supposed to dissociate from the film when heated afterwards at a higher temperature (550 °C) and causes peeling patterns on the H-terminated surface. The high-temperature film is free from this problem and has the largest mass density and dielectric constant among those investigated in this study. The isotope analysis also unveiled a relatively active H-exchange reaction between the diamond H-termination and H{sub 2}O oxidant during the high-temperature ALD, the SC still being kept intact. This dynamic and yet steady H termination is realized by the suppressed oxidation due to the endothermic reaction with H{sub 2}O. Additionally, we not only observed the kinetic isotope effect in the form of reduced growth rate of D{sub 2}O-oxidant ALD but found that the mass density and dielectric constant of D{sub 2}O-grown Al{sub 2}O{sub 3} films are smaller than those of H{sub 2}O-grown films. This is a new type of isotope effect, which is not caused by the presence of isotopes in the films unlike the traditional isotope effects that originate from the presence of isotopes itself. Hence, the high-temperature ALD is very effective in forming Al{sub 2}O{sub 3} films as a passivation and/or gate-insulation layer of high-temperature-operation diamond SC devices, and the

  2. One-dimensional Cu(II) coordination polymers containing C2h-symmetric 1,1':4',1''-terphenyl-3,3'-dicarboxylate linkers.

    PubMed

    Kim, Hyun Chul; Gu, Ja Min; Huh, Seong; Yo, Chul Hyun; Kim, Youngmee

    2015-10-01

    Two new one-dimensional Cu(II) coordination polymers (CPs) containing the C2h-symmetric terphenyl-based dicarboxylate linker 1,1':4',1''-terphenyl-3,3'-dicarboxylate (3,3'-TPDC), namely catena-poly[[bis(dimethylamine-κN)copper(II)]-μ-1,1':4',1''-terphenyl-3,3'-dicarboxylato-κ(4)O,O':O'':O'''] monohydrate], {[Cu(C20H12O4)(C2H7N)2H2O}n, (I), and catena-poly[[aquabis(dimethylamine-κN)copper(II)]-μ-1,1':4',1''-terphenyl-3,3'-dicarboxylato-κ(2)O(3):O(3')] monohydrate], {[Cu(C20H12O4)(C2H7N)2(H2O)]·H2O}n, (II), were both obtained from two different methods of preparation: one reaction was performed in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) as a potential pillar ligand and the other was carried out in the absence of the DABCO pillar. Both reactions afforded crystals of different colours, i.e. violet plates for (I) and blue needles for (II), both of which were analysed by X-ray crystallography. The 3,3'-TPDC bridging ligands coordinate the Cu(II) ions in asymmetric chelating modes in (I) and in monodenate binding modes in (II), forming one-dimensional chains in each case. Both coordination polymers contain two coordinated dimethylamine ligands in mutually trans positions, and there is an additional aqua ligand in (II). The solvent water molecules are involved in hydrogen bonds between the one-dimensional coordination polymer chains, forming a two-dimensional network in (I) and a three-dimensional network in (II).

  3. pH-Dependence of Binding Constants and Desorption Rates of Phosphonate- and Hydroxamate-Anchored [Ru(bpy)3]2+ on TiO2 and WO3.

    PubMed

    Esarey, Samuel L; Bartlett, Bart M

    2018-04-17

    The binding constants and rate constants for desorption of the modified molecular dye [Ru(bpy) 3 ] 2+ anchored by either phosphonate or hydroxamate on the bipyridine ligand to anatase TiO 2 and WO 3 have been measured. In aqueous media at pH 1-10, repulsive electrostatic interactions between the negatively charged anchor and the negatively charged surface govern phosphonate desorption under neutral and basic conditions for TiO 2 anatase due to the high acidity of phosphonic acid (p K a,4 = 5.1). In contrast, the lower acidity of hydroxamate (p K a,1 = 6.5, p K a,2 = 9.1) leads to little change in adsorption/desorption properties as a function of pH from 1 to 7. The binding constant for hydroxamate is 10 3 in water, independent of pH in this range. These results are true for WO 3 as well, but are not reported at pH > 4 due to its Arrhenius acidity. Kinetics for desorption as a function of pH are reported, with a proposed mechanism for phosphonate desorption at high pH being the electrostatic repulsion of negative charges between the surface and the anionic anchor. Further, the hydroxamic acid anchor itself is likely the site of quasi-reversible redox activity in [Ru(bpy) 2 (2,2'-bpy-4,4'-(C(O)N(OH)) 2 )] 2+ , which does not lead to any measurable deterioration of the complex within 2 h of dark cyclic voltammogram scans in aqueous media. These results posit phosphonate as the preferred anchoring group under acidic conditions and hydroxamate for neutral/basic conditions.

  4. Evolution of resistive switching mechanism through H2O2 sensing by using TaOx-based material in W/Al2O3/TaOx/TiN structure

    NASA Astrophysics Data System (ADS)

    Chakrabarti, Somsubhra; Panja, Rajeswar; Roy, Sourav; Roy, Anisha; Samanta, Subhranu; Dutta, Mrinmoy; Ginnaram, Sreekanth; Maikap, Siddheswar; Cheng, Hsin-Ming; Tsai, Ling-Na; Chang, Ya-Ling; Mahapatra, Rajat; Jana, Debanjan; Qiu, Jian-Tai; Yang, Jer-Ren

    2018-03-01

    Understanding of resistive switching mechanism through H2O2 sensing and improvement of switching characteristics by using TaOx-based material in W/Al2O3/TaOx/TiN structure have been reported for the first time. Existence of amorphous Al2O3/TaOx layer in the RRAM devices has been confirmed by transmission electron microscopy. By analyzing the oxidation states of Ta2+/Ta5+ for TaOx switching material and W0/W6+ for WOx layer at the W/TaOx interface through X-ray photoelectron spectroscopy and H2O2 sensing, the reduction-oxidation mechanism under Set/Reset occurs only in the TaOx layer for the W/Al2O3/TaOx/TiN structures. This leads to higher Schottky barrier height at the W/Al2O3 interface (0.54 eV vs. 0.46 eV), higher resistance ratio, and long program/erase endurance of >108 cycles with 100 ns pulse width at a low operation current of 30 μA. Stable retention of more than 104 s at 85 °C is also obtained. Using conduction mechanism and reduction-oxidation reaction, current-voltage characteristic has been simulated. Both TaOx and WOx membranes have high pH sensitivity values of 47.65 mV/pH and 49.25 mV/pH, respectively. Those membranes can also sense H2O2 with a low concentration of 1 nM in an electrolyte-insulator-semiconductor structure because of catalytic activity, while the Al2O3 membrane does not show sensing. The TaOx material in W/Al2O3/TaOx/TiN structure does not show only a path towards high dense, small size memory application with understanding of switching mechanism but also can be used for H2O2 sensors.

  5. Measurements of CH4, N2O, CO, H2O and O3 in the middle atmosphere by the ATMOS experiment on Spacelab 3

    NASA Technical Reports Server (NTRS)

    Gunson, M. R.; Farmer, C. B.; Norton, R. H.; Zander, R.; Rinsland, C. P.; Shaw, J. H.; Gao, Bo-Cai

    1989-01-01

    The volume mixing ratios of five minor gases (CH4, N2O, CO, H2O, and O3) were retrieved through the middle atmosphere from the analysis of 0.01/cm resolution infrared solar occultation spectra recorded near 28 N and 48 S latitudes with the ATMOS (Atmospheric Trace Molecule Spectroscopy) instrument, flown on board Spacelab 3. The results, which constitute the first simultaneous observations of continuous profiles through the middle atmosphere for these gases, are in general agreement with reported measurements from ground, balloon and satellite-based instruments for the same seasons. In detail, the vertical profiles of these gases show the effects of the upper and middle atmospheric transport patterns dominant during the season of these observations. The profiles inferred at different longitudes around 28 N suggest a near-uniform zonal distribution of these gases. Although based on fewer observations, the sunrise occultation measurements point to a larger variability in the vertical distribution of these gases at 48 S.

  6. CO2-assisted fabrication of novel heterostructures of h-MoO3/1T-MoS2 for enhanced photoelectrocatalytic performance

    NASA Astrophysics Data System (ADS)

    Zhu, Chuanhui; Xu, Qun; Liu, Wei; Ren, Yumei

    2017-12-01

    Combining the peculiar properties of different ingredients in one ultimate material is an efficient route to achieve the desired functional materials. Compared to 2H-MoS2, 1T-MoS2 nanosheets display the perfect performance of hydrogen evolution reaction (HER) because of the excellent electronic conductivity. However, how to further realize HER in the visual and near-infrared (NIR) region is a great challenge. Herein, we develop an efficient method to locally pattern h-MoO3 on the ultrathin metallic 1T-MoS2 nanosheets and obtain the novel heterostructures of h-MoO3/1T-MoS2. The enhanced photoelectrochemical performance of the as-prepared heterostructures has been demonstrated. Our study indicates it is originated from the synergistic effect between h-MoO3 and 1T-MoS2, i.e., the strong optical absorption of h-MoO3 in the visible and NIR region, the excellent electronic conductivity of 1T-MoS2 and as well as the efficient separation of the photo-induced carriers from the heterostructures.

  7. Characterization of Gly-D-Phe, Gly-L-Leu, and D-Phe as affinity ligands to thermolysin.

    PubMed

    Yasukawa, Kiyoshi; Kusano, Masayuki; Nakamura, Koji; Inouye, Kuniyo

    2006-04-01

    In this study, glycyl-D-phenylalanine (Gly-D-Phe), glycyl-L-leucine (Gly-L-Leu), and D-phenylalanine (D-Phe) were characterized for their abilities as affinity ligands to thermolysin. Each of the ligands was immobilized to the resin. The optimum pH for adsorption of thermolysin is 5.0-6.0 for each of the ligands. By the affinity column chromatography in which 2mg thermolysin was applied onto 4 ml volume of the resins at pH 5.5, the adsorption ratios based on casein hydrolysis activity were 100% for each of the ligands. However, the adsorption ratios of the resins containing Gly-L-Leu and D-Phe, unlike that of Gly-D-Phe, were progressively decreased with increasing the amounts of thermolysin applied to the column. Measurement of adsorption isotherms showed that the association constant to thermolysin at pH 5.5 of the resins containing Gly-D-Phe was (3.3+/-0.8)x10(5)M(-1), while those of Gly-L-Leu and D-Phe were approximately ten times less. This result is coincident with the observations of performances in affinity column chromatography. On the other hand, maximum thermolysin binding capacities were almost the same among the resins examined. These results indicate that Gly-D-Phe is more suitable than Gly-L-Leu and D-Phe as an affinity ligand for purification of thermolysin.

  8. Microscopic adaptation of BaHfO3 and Y2O3 artificial pinning centers for strong and isotropic pinning landscape in YBa2Cu3O7-x thin films

    NASA Astrophysics Data System (ADS)

    Gautam, Bibek; Sebastian, Mary Ann; Chen, Shihong; Haugan, Timothy; Zhang, Wenrui; Huang, Jijie; Wang, Haiyan; Wu, Judy Z.

    2018-07-01

    A study of 3 vol% Y2O3 + 2-6 vol% BaHfO3 double-doped YBa2Cu3O7-x (BHO DD) epitaxial thin films was carried out to explore the morphology adaption of c-axis aligned one-dimensional BHO artificial pinning centers (1D APCs) to secondary Y2O3 nanoparticles (3D APCs). BHO 1D APCs have been predicted to have the least rigidity in an elastic strain energy model in APC/YBa2Cu3O7-x nanocomposite films. Consequently, they could be best ‘tuned’ away from the c-axis alignment by local strains generated by the Y2O3 3D APCs. This provides an opportunity to generate mixed-morphology APCs, especially at high BHO concentrations. Motivated by this, we have carried out a systematic study of the transport critical current density J c(H, T, θ) on the BHO DD samples in magnetic fields (H) up to 90 kOe at different H orientations from H//c-axis (θ = 0), to θ = 45°, and to H//ab-plane (θ = 90°). Enhanced pinning at all three orientations was observed as illustrated in the comparable low alpha (α) values in the range of 0.13-0.25 at 65 K, which is consistent with the mixed 1D (in c-axis) + 2D (in ab-plane) + 3D APCs observed in transmission electron microscopy (TEM). Upon increasing BHO concentration from 2 to 4 vol%, a monotonic increase of the accommodation field H* at θ = 0°, 45° and 90° was observed, indicative of the APC concentration increase of the mixed morphologies. At 6 vol% BHO, the H* continues the increase to 85 kOe at H//c-axis (θ = 0), and >90 kOe H//ab-plane (θ = 90°), while it decreases from 80 to 85 kOe at 2-4 vol% to 60 kOe at 6 vol% at θ = 45°, which is consistent with the TEM observation of the connection of 3D APCs, appeared at lower BHO concentration into 2D ones in ab-plane at the higher BHO concentrations. These results shed light on the quantitative adaptation of APCs of mixed morphologies with increasing BHO doping in the BHO DD thin films and are important for controlling the APC pinning landscape towards minimal angular dependence.

  9. A Sequential Method to Prepare Polymorphs and Solvatomorphs of [Fe(1,3-bpp)2 ](ClO4 )2 ⋅nH2 O (n=0, 1, 2) with Varying Spin-Crossover Behaviour.

    PubMed

    Bartual-Murgui, Carlos; Codina, Carlota; Roubeau, Olivier; Aromí, Guillem

    2016-08-26

    Two polymorphs of the spin crossover (SCO) compound [Fe(1,3-bpp)2 ](ClO4 )2 (1 and 2; 1,3-bpp=2-(pyrazol-1-yl)-6-(pyrazol-3-yl)pyridine) were prepared using a novel, stepwise procedure. Crystals of 1 deposit from dry solvents, while 2 is obtained from a solid-state procedure, by sequentially removing lattice H2 O molecules from the solvatomorph [Fe(1,3-bpp)2 ](ClO4 )22H2 O (22H2 O), using single-crystal-to-single-crystal (SCSC) transformations. Hydrate 22H2 O is obtained through the same reaction as 1, now with 2.5 % of water added. Compounds 2 and 22H2 O are unstable in the atmosphere and absorb or lose one equivalent of water, respectively, to both yield the stable solvatomorph [Fe(1,3-bpp)2 ](ClO4 )2H2 O (2H2 O), also following SCSC processes. The four derivatives have been characterised by single-crystal X-ray diffraction (SCXRD). Furthermore, the homogeneity of the various compounds as well as their SCSC interconversions have been confirmed by powder X-ray diffraction (PXRD). Polymorphs 1 and 2 exhibit abrupt SCO behaviour near room temperature with T1/2↑ =279/316 K and T1/2↓ =276/314 K (near 40 K of shift) and different cooperativity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Development of Al2O3 fiber-reinforced Al2O3-based ceramics.

    PubMed

    Tanimoto, Yasuhiro; Nemoto, Kimiya

    2004-09-01

    The purpose of this study was to use a tape casting technique to develop an Al2O3 fiber-reinforced Al2O3-based ceramic material (Al2O3-fiber/Al2O3 composite) into a new type of dental ceramic. The Al2O3-based ceramic used a matrix consisting of 60 wt% Al2O3 powder and 40 wt% SiO2-B2O3 powder. The prepreg sheets of Al2O3-fiber/Al2O3 composite (in which uniaxially aligned Al2O3 fibers were infiltrated with the Al2O3-based matrix) were fabricated continuously using tape casting technique with a doctor blade system. Multilayer preforms of Al2O3-fiber/Al2O3 composite sheets were then sintered at a maximum temperature of 1000 degrees C under an atmospheric pressure in a furnace. The results showed that the shrinkage and bending properties of Al2O3-fiber/Al2O3 composite exceeded those of unreinforced Al2O3--hence demonstrating the positive effects of fiber reinforcement. In conclusion, the tape casting technique has been utilized to successfully develop a new type of dental ceramic material.

  11. Design of plasmonic Ag-TiO2/H3PW12O40 composite film with enhanced sunlight photocatalytic activity towards o-chlorophenol degradation.

    PubMed

    Lu, Nan; Wang, Yaqi; Ning, Shiqi; Zhao, Wenjing; Qian, Min; Ma, Ying; Wang, Jia; Fan, Lingyun; Guan, Jiunian; Yuan, Xing

    2017-12-11

    A series of plasmonic Ag-TiO 2 /H 3 PW 12 O 40 composite films were fabricated and immobilized by validated preparation technique. The chemical composition and phase, optical, SPR effect and pore-structure properties together with the morphology of as-prepared composite film are well-characterized. The multi-synergies of as-prepared composite films were gained by combined action of electron-capture action via H 3 PW 12 O 40 , visible-response induced by Ag, and Schottky-junction formed between TiO 2 -Ag. Under simulated sunlight, the maximal K app of o-chlorophenol (o-CP) reached 0.0075 min -1 which was 3.95-fold larger than that of TiO 2 film, while it was restrained obviously under acid condition. In the photocatalytic degradation process, ·OH and ·O 2 - attacked preferentially ortho and para position of o-CP molecule, and accordingly the specific degradation pathways were speculated. The novel composite film exhibited an excellent applicability due to self-regeneration of H 3 PW 12 O 40 , well-protection of metal Ag° and favorable immobilization.

  12. Rb3In(H2O)Si5O13: a novel indium silicate with a CdSO4-topological-type structure.

    PubMed

    Hung, Ling-I; Wang, Sue-Lein; Chen, Chia-Yi; Chang, Bor-Chen; Lii, Kwang-Hwa

    2005-05-02

    A novel indium silicate, Rb3In(H2O)Si5O13, has been synthesized using a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction. The structure consists of five-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to four adjacent five-membered rings to form a 3D silicate framework that belongs to the CdSO4 topological type. The InO6 octahedron shares five of its corners with five different SiO4 tetrahedra to form a 3D frame-work that delimits two types of channels to accommodate the rubidium cations. The sixth corner of InO6 is coordinated H2O. The structure is related to that of the titanium silicate ETS-10, and these are the only two metal silicates that have the CdSO4-topological-type structure. In addition, the crystal of Rb3In(H2O)Si5O13 shows an intense second harmonic generation signal. Crystal data: H2Rb3InSi5O14, monoclinic, space group Cc (No. 9), a = 9.0697(5) A, b = 11.5456(6) A, c = 13.9266(8) A, beta = 102.300(1) degrees, V = 1424.8(1) A3, and Z = 4.

  13. One-dimensional ferromagnetic array compound [Co3(SBA)2(OH)2(H2O)2]n, (SBA = 4-sulfobenzoate)

    NASA Astrophysics Data System (ADS)

    Honda, Zentaro; Nomoto, Naoyuki; Fujihara, Takashi; Hagiwara, Masayuki; Kida, Takanori; Sawada, Yuya; Fukuda, Takeshi; Kamata, Norihiko

    2018-06-01

    We report on the syntheses, crystal structure, and magnetic properties of the transition metal coordination polymer [Co3(SBA)2(OH)2(H2O)2]n, (SBA = 4-sulfobenzoate) in which CoO6 octahedra are linked through their edges, forming one-dimensional (1D) Co(II) arrays running along the crystal a-axis. These arrays are further perpendicularly bridged by SBA ligand to construct a three-dimensional framework. Its magnetic properties have been investigated, and ferromagnetic interactions within the arrays have been found. From heat capacity measurements, we have found that this compound exhibits a three-dimensional ferromagnetic phase transition at TC = 1.54 K, and the specific heat just above TC shows a Schottky anomaly which originates from an energy gap caused by uniaxial magnetic anisotropy. These results suggest that [Co3(SBA)2(OH)2(H2O)2]n consists of weakly coupled 1D ferromagnetic Ising arrays.

  14. Assembly of flexible CoMoO4@NiMoO4·xH2O and Fe2O3 electrodes for solid-state asymmetric supercapacitors

    PubMed Central

    Wang, Jing; Zhang, Leipeng; Liu, Xusong; Zhang, Xiang; Tian, Yanlong; Liu, Xiaoxu; Zhao, Jiupeng; Li, Yao

    2017-01-01

    In this work, CoMoO4@NiMoO4·xH2O core-shell heterostructure electrode is directly grown on carbon fabric (CF) via a feasible hydrothermal procedure with CoMoO4 nanowires (NWs) as the core and NiMoO4 nanosheets (NSs) as the shell. This core-shell heterostructure could provide fast ion and electron transfer, a large number of active sites, and good strain accommodation. As a result, the CoMoO4@NiMoO4·xH2O electrode yields high-capacitance performance with a high specific capacitance of 1582 F g−1, good cycling stability with the capacitance retention of 97.1% after 3000 cycles and good rate capability. The electrode also shows excellent mechanical flexibility. Also, a flexible Fe2O3 nanorods/CF electrode with enhanced electrochemical performance was prepared. A solid-state asymmetric supercapacitor device is successfully fabricated by using flexible CoMoO4@NiMoO4·xH2O as the positive electrode and Fe2O3 as the negative electrode. The asymmetric supercapacitor with a maximum voltage of 1.6 V demonstrates high specific energy (41.8 Wh kg−1 at 700 W kg−1), high power density (12000 W kg−1 at 26.7 Wh kg−1), and excellent cycle ability with the capacitance retention of 89.3% after 5000 cycles (at the current density of 3A g−1). PMID:28106170

  15. Spectroscopic Properties of B2O3-PbO-Nd2O3 Glasses

    NASA Astrophysics Data System (ADS)

    Simon, V.; Ardelean, I.; Milea, I.; Peteanu, M.; Simon, S.

    Samples belonging to xNd2O3(100-x) [2B2O3·PbO] glass system, with 0≤ x≤ 40 mol%, are investigated by IR and UV-VIS spectroscopies in order to obtain evidence for the influence of Nd2O3 on the local order from 2B2O3·PbO glass matrix. Besides the IR absorption bands characteristic to lead and boron arrangements, typical absorption lines of Nd3+ ions around 4000 cm-1 and 6000 cm-1 are recorded. The 6000 cm-1 band appears only for the samples with x≥25 mol% Nd2O3. The split of some UV-VIS absorption bands arising from transitions of neodymium ions in doublet lines as well as the shift of the absorption bands as the Nd2O3 content increases denote the influence of the lead-borate matrix on the radiative transitions of the lanthanide ion.

  16. GLI1 inhibitor GANT61 exhibits antitumor efficacy in T-cell lymphoma cells through down-regulation of p-STAT3 and SOCS3

    PubMed Central

    Geng, Lingyun; Lu, Kang; Li, Peipei; Li, Xinyu; Zhou, Xiangxiang; Li, Ying; Wang, Xin

    2017-01-01

    T-cell lymphomas are lymphoid malignancies with aggressive clinical course and poor prognosis. Increasing evidences suggest that deregulation of signal transducer and activator of transcription-3 (STAT3) and suppressor of cytokine signaling 3 (SOCS3) is associated with the pathogenesis of T-cell lymphomas. The hedgehog (Hh)/glioma-associated oncogene-1 (GLI1) pathway, aberrantly activated in a number of tumors, has also been extensively studied. We found that protein expressions of GL11, p-STAT3, STAT3, and SOCS3 were up-regulated in T-cell lymphoma tissues and cell lines. Moreover, the protein expressions of p-STAT3 and SOCS3 were positively correlated with GLI1 in T-cell lymphomas. GLI1 inhibitor GANT61 and lentivirus-mediated siGLI1 exhibited inhibitory effects in the three T-cell lines (Jurkat, Karpass299 and Myla3676 cells). The protein expressions of p-STAT3 and SOCS3 were decreased accompanied with the inhibition of GLI1. These findings indicated that GANT61 is a promising agent against T-cell lymphoma and the antitumor activity might be partly mediated by down-regulating p-STAT3 and SOCS3. PMID:27275540

  17. Hydrothermal synthesis of nanostructured Y2O3 and (Y0.75Gd0.25)2O3 based phosphors

    NASA Astrophysics Data System (ADS)

    Mančić, Lidija; Lojpur, Vesna; Marinković, Bojan A.; Dramićanin, Miroslav D.; Milošević, Olivera

    2013-08-01

    Examples of (Y2O3-Gd2O3):Eu3+ and Y2O3:(Yb3+/Er3+) rare earth oxide-based phosphors are presented to highlight the controlled synthesis of 1D and 2D nanostructures through simple hydrothermal method. Conversion of the starting nitrates mixture into carbonate hydrate phase is performed with the help of ammonium hydrogen carbonate solution during hydrothermal treatment at 200 °C/3 h. Morphological architectures of rare earth oxides obtained after subsequent powders thermal treatment at 600 and 1100 °C for 3 and 12 h and their correlation with the optical characteristics are discussed based on X-ray powder diffractometry, field emission scanning electron microscopy, infrared spectroscopy and photoluminescence measurements. Strong red and green emission followed by the superior decay times are attributed to the high powders purity and homogeneous dopants distribution over the host lattice matrix.

  18. H2O Paradox and its Implications on H2O in Moon

    NASA Astrophysics Data System (ADS)

    Zhang, Youxue

    2017-04-01

    The concentration of H2O in the mantle of a planetary body plays a significant role in the viscosity and partial melting and hence the convection and evolution of the planetary body. Even though the composition of the primitive terrestrial mantle (PTM) is thought to be well known [1-2], the concentration of H2O in PTM remains paradoxial because different methods of estimation give different results [3]: Using H2O/Ce ratio in MORB and OIB and Ce concentration in PTM, the H2O concentration in PTM would be (300÷×1.5) ppm; using mass balance by adding surface water to the mantle [3-4], H2O concentration in PTM would be (900÷×1.3) ppm [2-3]. The inconsistency based on these two seemingly reliable methods is referred to as the H2O paradox [3]. For Moon, H2O contents in the primitive lunar mantle (PLM) estimated from H2O in plagioclase in lunar anorthosite and that from H2O/Ce ratio in melt inclusions are roughly consistent at ˜110 ppm [5-6] even though there is still debate about the volatile depletion trend [7]. One possible solution to the H2O paradox in PTM is to assume that early Earth experienced whole mantle degassing, which lowered the H2O/Ce ratio in the whole mantle but without depleting Ce in the mantle. The second possible solution is that some deep Earth reservoirs with high H2O/Ce ratios have not been sampled by MORB and OIB. Candidates include the transition zone [8] and the D" layer. The third possible solution is that ocean water only partially originated from mantle degassing, but partially from extraterrestrial sources such as comets [9-10]. At present, there is not enough information to determine which scenario is the answer to the H2O paradox. On the other hand, each scenario would have its own implications to H2O in PLM. If the first scenario applies to Moon, because degassed H2O or H2 would have escaped from the lunar surface, the very early lunar mantle could have much higher H2O [11] than that obtained using the H2O/Ce ratio method. The

  19. Polymorph (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}RE{sub 3}F{sub 10}·xH{sub 2}O (RE = Ho-Lu, Y) and REF{sub 3} nanocrystals: Hydrothermal synthesis, characterization and luminescence

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

    Jia, Li-Ping; Zhang, Qiang; Yan, Bing, E-mail: byan@tongji.edu.cn

    Graphical abstract: A hydrothermal system is developed to prepare one new polymorph of (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}RE{sub 3}F{sub 10}·xH{sub 2}O and known rare earth fluorides involving REF{sub 3} nanocrystals under mild condition. Highlights: ► A new polymorph of (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}RE{sub 3}F{sub 10}·xH{sub 2}O has been synthesized. ► The RE{sup 3+} radius decides the shape evolution and phase control for REF{sub 3} NCs. ► The RE{sup 3+} radius has influence on the microstructure and morphology of REF{sub 3} NCs. -- Abstract: In this paper, a solvents-thermal system is developed to prepare one new polymorph of (C{sub 2}N{submore » 2}H{sub 10}){sub 0.5}Ho{sub 3}F{sub 10}·xH{sub 2}O and rare earth fluorides REF{sub 3} nanocrystals under mild condition. It is found that the ionic radius of RE{sup 3+} is the key factor responsible for the shape evolution and phase control for rare earth fluorides nanocrystals at selected temperatures, which has an influence on the microstructure and morphology of the products to some extent. With the increase of the atomic number, the shape of fluoride changes from hexagonal REF{sub 3} phase (RE = La, Sm) to orthorhombic REF{sub 3} phase (RE = Eu-Dy), and finally to diamond structure (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}Ho{sub 3}F{sub 10}·xH{sub 2}O (RE = Ho, Er, Tm, Yb, Lu, Y). In addition, the characteristic energy level transition {sup 5}D{sub 0}–{sup 7}F{sub 1} of Eu{sup 3+} splits into 585 and 591 nm emission peaks, and the dominant peak is the orange emission at 591 nm.« less

  20. Investigation of collision-induced dissociation products and structures of gas-phase [ M·GlyGlyHis-H]+ ( M = Fe, Ni, Cu, and Zn) complexes.

    PubMed

    Gannamani, Bharathi; Shin, Joong-Won

    2017-02-01

    Collision-induced dissociation is carried out for electrosprayed [Fe·GlyGlyHis-H] + , [Ni·GlyGlyHis-H] + , [Cu·GlyGlyHis-H] + , and [Zn·GlyGlyHis-H] + complexes. [Fe·GlyGlyHis-H] + , [Ni·GlyGlyHis-H] + , and [Zn·GlyGlyHis-H] + yield metal-bound peptide sequence ions and dehydrated ions as primary products, whereas [Cu·GlyGlyHis-H] + generates a more extensive series of metal-bound sequence ions and a product arising from the unusual loss of a formaldehyde moiety; dehydration is significantly suppressed for this complex. Density functional theory calculations show that the copper ion-deprotonated peptide binding energy is substantially higher than those in other complexes, suggesting that there is a correlation between ion-ligand binding energy and their fragmentation behavior.

  1. A global view of the extratropical tropopause transition layer from Atmospheric Chemistry Experiment Fourier Transform Spectrometer O3, H2O, and CO

    NASA Astrophysics Data System (ADS)

    Hegglin, M. I.; Boone, C. D.; Manney, G. L.; Walker, K. A.

    2009-04-01

    The global behavior of the extratropical tropopause transition layer (ExTL) is investigated using O3, H2O, and CO measurements from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) on Canada's SCISAT-1 satellite obtained between February 2004 and May 2007. The ExTL depth is derived using H2O-O3 and CO-O3 correlations. The ExTL top derived from H2O-O3 shows an increase from roughly 1-1.5 km above the thermal tropopause in the subtropics to 3-4 km (2.5-3.5 km) in the north (south) polar region, implying somewhat weaker troposphere-stratosphere-transport in the Southern Hemisphere. The ExTL bottom extends ˜1 km below the thermal tropopause, indicating a persistent stratospheric influence on the troposphere at all latitudes. The ExTL top derived from the CO-O3 correlation is lower, at 2 km or ˜345 K (1.5 km or ˜335 K) in the Northern (Southern) Hemisphere. Its annual mean coincides with the relative temperature maximum just above the thermal tropopause. The vertical CO gradient maximizes at the thermal tropopause, indicating a local minimum in mixing within the tropopause region. The seasonal changes in and the scales of the vertical H2O gradients show a similar pattern as the static stability structure of the tropopause inversion layer (TIL), which provides observational support for the hypothesis that H2O plays a radiative role in forcing and maintaining the structure of the TIL.

  2. 3,4-Dimethyl-1-phenyl­pyrano[2,3-c]pyrazol-6(1H)-one

    PubMed Central

    Ahmad, Neman; Tahir, M. Nawaz; Khan, Misbahul Ain; Ather, Abdul Qayyum; Khan, Muhammad Naeem

    2011-01-01

    In the title compound, C14H12N2O2, the dihedral angle between the phenyl ring and the 3,4-dimethyl­pyrano[2,3-c]pyrazol-6(1H)-one system is 7.28 (6)°. An intra­molecular C—H⋯O inter­action generates an S(6) ring. In the crystal, the mol­ecules are linked by C—H⋯O hydrogen bonds, forming C(8) chains. C–H⋯π and π–π inter­actions [centroid–centroid separation = 3.6374 (12) Å] further consolidate the packing. PMID:21754037

  3. Surfactant-assisted hydrothermal crystallization of nanostructured lithium metasilicate (Li{sub 2}SiO{sub 3}) hollow spheres: II-Textural analysis and CO{sub 2}-H{sub 2}O sorption evaluation

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

    Ortiz-Landeros, Jose; Gomez-Yanez, Carlos; Pfeiffer, Heriberto, E-mail: pfeiffer@iim.unam.mx

    In a previous work, the synthesis and structural-microstructural characterization of different nanocrystalline lithium metasilicate (Li{sub 2}SiO{sub 3}) samples were performed. Then, in this work, initially, a textural analysis was performed over the same samples. Li{sub 2}SiO{sub 3} samples prepared with a non-ionic surfactant (TRITON X-114) presented the best textural properties. Therefore, this sample was selected to evaluate its water vapor (H{sub 2}O) and carbon dioxide (CO{sub 2}) sorption properties. Sorption experiments were performed at low temperatures (30-80 deg. C) in presence of water vapor using N{sub 2} or CO{sub 2} as carrier gases. Results clearly evidenced that CO{sub 2} sorptionmore » on these materials is highly improved by H{sub 2}O vapor, and of course, textural properties enhanced the H{sub 2}O-CO{sub 2} sorption efficiency, in comparison with the solid-state reference sample. - Graphical abstract: Li{sub 2}SiO{sub 3} varied significantly its capacity of CO{sub 2} absorption as a function of the microstructural properties and by the water presence. Highlights: > We studied the CO{sub 2} absorption on different Li{sub 2}SiO{sub 3} samples in presence of H{sub 2}O vapor. > It was proved that CO{sub 2} absorption on Li{sub 2}SiO{sub 3} is controlled by different factors. > Li{sub 2}SiO{sub 3} with a porous microstructure produces a higher CO{sub 2} absorption. > H{sub 2}O vapor favors the CO{sub 2} absorption on Li{sub 2}SiO{sub 3} due to a surface hydroxylation.« less

  4. 3D hierarchical porous cobalt monoxide nanoplates with a book-like structure derived from Co(CO3)0.5(OH)·0.11H2O: two-steps oriented attachment and high-performance asymmetric supercapacitors

    NASA Astrophysics Data System (ADS)

    Xiao, Yuanhua; Zhao, Xiaobing; Jin, Qingxian; Su, Dangcheng; Wang, Xuezhao; Wu, Shide; Zhou, Liming; Fang, Shaoming

    2017-10-01

    3D Hierarchical porous cobalt monoxide (CoO) nanoplates with a book-like structure derive from Co(CO3)0.5(OH)·0.11H2O by a two-steps oriented attachment mechanism in the solvothermal process. Firstly, nanoplates are formed by oriented attachment of nanorods. Secondly, new nanoplates could be generated on the old nanoplates by a sloped oriented attachment of nanorods with the based nanoplates shape into a 3D hierarchical book-like structure. The CoO nanoplates show superior specific capacitance about 1221.7 F g-1 at 1 A g-1 to most of the Co-based supercapacitor materials up to date. An asymmetric supercapacitor (ASC) based on positive electrode CoO and negative electrode active carbon (AC) exhibits an excellent energy density of 50.1 Wh kg-1 at a power density of 589 W kg-1 and gets a satisfactory cycling stability (86.3% of its initial capacitance retention at 10 A g-1 over 10 000 cycles).

  5. Stratospheric H2O and HNO3 profiles derived from solar occultation measurements

    NASA Technical Reports Server (NTRS)

    Fischer, H.; Fergg, F.; Rabus, D.; Burkert, P.

    1985-01-01

    Compact two-channel radiometers for solar occultation experiments have been constructed in order to measure stratospheric trace gases. The instruments can be used as filter- or correlation-type radiometers, depending on the trace gas under investigation. Within the LIMS correlative measurement program, balloon flights were performed with a payload of up to four of these two-channel radiometers. From the filter-type measurements, profiles of the trace gases H2O and HNO3 are inferred for the height region between the tropopause and the balloon float level. The data evaluation also includes a comprehensive analysis of the error sources and their effect on the accuracy of the trace gas profiles. The derived H2O and HNO3 profiles are assessed against the observations of other authors and are discussed in the light of the trace gas distributions calcualted from photochemical models.

  6. Photomagnetic switching of heterometallic complexes [M(dmf)4(H2O)3(mu-CN)Fe(CN)5].H2O (M=Nd, La, Gd, Y) analyzed by single-crystal X-ray diffraction and ab initio theory.

    PubMed

    Svendsen, Helle; Overgaard, Jacob; Chevallier, Marie A; Collet, Eric; Chen, Yu-Sheng; Jensen, Frank; Iversen, Bo B

    2010-06-25

    Single-crystal X-ray diffraction measurements have been carried out on [Nd(dmf)(4)(H(2)O)(3)(mu-CN)Fe(CN)(5)].H(2)O (1; dmf=dimethylformamide), [Nd(dmf)(4)(H(2)O)(3)(mu-CN)Co(CN)(5)].H(2)O (2), [La(dmf)(4)(H(2)O)(3)(mu-CN)Fe(CN)(5)].H(2)O (3), [Gd(dmf)(4)(H(2)O)(3)(mu-CN)Fe(CN)(5)].H(2)O (4), and [Y(dmf)(4)(H(2)O)(3)(mu-CN)Fe(CN)(5)].H(2)O (5), at 15(2) K with and without UV illumination of the crystals. Significant changes in unit-cell parameters were observed for all the iron-containing complexes, whereas 2 showed no response to UV illumination. Photoexcited crystal structures have been determined for 1, 3, and 4 based on refinements of two-conformer models, and excited-state occupancies of 78.6(1), 84(6), and 86.6(7)% were reached, respectively. Significant bond-length changes were observed for the Fe-ligand bonds (up to 0.19 A), the cyano bonds (up to 0.09 A), and the lanthanide-ligand bonds (up to 0.10 A). Ab initio theoretical calculations were carried out for the experimental ground-state geometry of 1 to understand the electronic structure changes upon UV illumination. The calculations suggest that UV illumination gives a charge transfer from the cyano groups on the iron atom to the lanthanide ion moiety, {Nd(dmf)(4)(H(2)O)(3)}, with a distance of approximately 6 A from the iron atom. The charge transfer is accompanied by a reorganization of the spin state on the {Fe(CN)(6)} complex, and a change in geometry that produces a metastable charge-transfer state with an increased number of unpaired electrons, thus accounting for the observed photomagnetic effect.

  7. A new series of mixed oxalates MM'(C 2O 4) 3(H 2O) 3· nH 2O (M = Cd, Hg, Pb; M' = Zr, Hf) based on eight-fold coordinated metals: Synthesis, crystal structure from single-crystal and powder diffraction data and thermal behaviour

    NASA Astrophysics Data System (ADS)

    Gavilan, Elisabeth; Audebrand, Nathalie; Jeanneau, Erwann

    2007-11-01

    A new series of mixed oxalates MM'(C 2O 4) 3(H 2O) 3· nH 2O (M = Cd, Hg, Pb; M' = Zr, Hf) has been prepared. The crystal structures have been solved from single-crystal and powder diffraction data. The isotypical compounds crystallise with space group P2 1/ c (No. 14). The structures consist of honeycomb layers formed by eight-fold coordinated metals, in a distorted square-based antiprismatic conformation, connected together via oxalates which act as bidentate ligands and also as monodentate in a less-common μ3-bridging mode. Sheets are built from two shifted honeycomb layers and linked to each other through a hydrogen network. The resulting frameworks of the series display a compact two-dimensional arrangement of polyhedra MO 8 and M'O 8. Weakly-bonded water molecules are located between and within the sheets. Comparisons with the 3D open-framework structures of related metal oxalates are made. The dehydration processes occur in three or four steps. The final products are MO, M'O 2 and PbZrO 3 resulting from the sublimation of PbO in air. The size of PbZrO 3 crystallites, which are on average isotropic, has been evaluated to be 1055 Å from line-broadening analysis.

  8. NH4+-NH3 removal from simulated wastewater using UV-TiO2 photocatalysis: effect of co-pollutants and pH.

    PubMed

    Vohra, M S; Selimuzzaman, S M; Al-Suwaiyan, M S

    2010-05-01

    The main objective of the present study was to investigate the efficiency of titanium dioxide (TiO2) assisted photocatalytic degradation (PCD) process for the removal of ammonium-ammonia (NH4(+)-NH3) from the aqueous phase and in the presence of co-pollutants thiosulfate (S2O3(2-)) and p-cresol (C6H4CH3OH) under varying mixed conditions. For the NH4(+)-NH3 only PCD experiments, results showed higher NH4 -NH3 removal at pH 12 compared to pH 7 and 10. For the binary NH4(+)-NH3/S2O3(2-) studies the respective results indicated a significant lowering in NH4(+)-NH3 PCD in the presence of S2O32- at pH 7/12 whereas at pH 10 a marked increase in NH4(+)-NH3 removal transpired. A similar trend was noted for the p-cresol/NH4(+)-NH3 binary system. Comparing findings from the binary (NH4(+)-NH3/S2O3(2-) and p-cresol/NH4(+)-NH3) and tertiary (NH4(+)-NH3/S2O3(2-)/p-cresol) systems, at pH 10, showed fastest NH4(+)-NH3 removal transpiring for the tertiary system as compared to the binary systems, whereas both the binary systems indicated comparable NH4(+)-NH3 removal trends. The respective details have been discussed.

  9. The effect of Fe2O3 crystal phases on CO2 hydrogenation

    PubMed Central

    Wang, Tianqi; Chen, Hongxian; Yang, Xiazhen; Jin, Yangfu

    2017-01-01

    The effect of Fe2O3 crystal phases on their performance in CO2 hydrogenation was studied. α-Fe2O3 crystal was prepared by precipitation method from Fe(NO3)3·9H2O and (NH4)2CO3, and γ-Fe2O3 was prepared by grinding Fe(NO3)3·9H2O and L(+)-Tartaric acid in agate mortar completely. The crystal phases of Fe2O3 influence the distribution of promoter Zn, K and Cu on catalysts. The dispersity of K on γ-Fe2O3 surface is higher than α-Fe2O3. On the contrary, Cu and Zn are more dispersive on α-Fe2O3 surface than γ-Fe2O3. The catalyst in γ-Fe2O3 phase is easily reduced relative to the catalyst in α-Fe2O3 phase. The former presents higher CO2 conversion and C2+ hydrocarbon selectivity than the latter in CO2 hydrogenation. PMID:28806421

  10. The effect of Fe2O3 crystal phases on CO2 hydrogenation.

    PubMed

    Ning, Wensheng; Wang, Tianqi; Chen, Hongxian; Yang, Xiazhen; Jin, Yangfu

    2017-01-01

    The effect of Fe2O3 crystal phases on their performance in CO2 hydrogenation was studied. α-Fe2O3 crystal was prepared by precipitation method from Fe(NO3)3·9H2O and (NH4)2CO3, and γ-Fe2O3 was prepared by grinding Fe(NO3)3·9H2O and L(+)-Tartaric acid in agate mortar completely. The crystal phases of Fe2O3 influence the distribution of promoter Zn, K and Cu on catalysts. The dispersity of K on γ-Fe2O3 surface is higher than α-Fe2O3. On the contrary, Cu and Zn are more dispersive on α-Fe2O3 surface than γ-Fe2O3. The catalyst in γ-Fe2O3 phase is easily reduced relative to the catalyst in α-Fe2O3 phase. The former presents higher CO2 conversion and C2+ hydrocarbon selectivity than the latter in CO2 hydrogenation.

  11. Epitaxial growth of SrTiO3/YBa2Cu3O7 - x heterostructures by plasma-enhanced metalorganic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Liang, S.; Chern, C. S.; Shi, Z. Q.; Lu, P.; Safari, A.; Lu, Y.; Kear, B. H.; Hou, S. Y.

    1994-06-01

    We report heteroepitaxial growth of SrTiO3 on YBa2Cu3O7-x/LaAlO3 substrates by plasma-enhanced metalorganic chemical vapor deposition. X-ray diffraction results indicated that SrTiO3 films were epitaxially grown on a (001) YBa2Cu3O7-x surface with [100] orientation perpendicular to the surface. The film composition, with Sr/Ti molar ratio in the range of 0.9 to 1.1, was determined by Rutherford backscattering spectrometry and energy dispersive spectroscopy. The thickness of the SrTiO3 films is 0.1-0.2 μm. The epitaxial growth was further evidenced by high-resolution transmission electron microscopy and selected area diffraction. Atomically abrupt SrTiO3/YBa2Cu3O7-x interface and epitaxial growth with [100]SrTiO3∥[001]YBa2Cu3O7-x were observed in this study. The superconducting transition temperature of the bottom YBa2Cu3O7-x layer, as measured by ac susceptometer, did not significantly degrade after the growth of overlayer SrTiO3. The capacitance-voltage measurements showed that the dielectric constant of the SrTiO3 films was as high as 315 at a signal frequency of 100 KHz. The leakage current density through the SrTiO3 films is about 1×10-6 A/cm2 at 2-V operation. Data analysis on the current-voltage characteristic indicated that the conduction process is related to bulk-limited Poole-Frenkel emission.

  12. Cr[(H3N-(CH2)2-PO3)(Cl)(H2O)]: X-ray single-crystal structure and magnetism of a polar organic-inorganic hybrid chromium(II) organophosphonate.

    PubMed

    Bauer, Elvira M; Bellitto, Carlo; Colapietro, Marcello; Portalone, Gustavo; Righini, Guido

    2003-10-06

    Cr[(H(3)N-(CH(2))(2)-PO(3))(Cl)(H(2)O)], a rare example of a polar organic-inorganic hybrid material containing Cr(2+), was prepared from CrCl(2), 2-aminoethylphosphonic acid, and urea in water and isolated as light-blue crystals. It crystallizes in the noncentrosymmetric monoclinic space group P2(1), with a = 5.249(1) A, b = 14.133(3) A, c = 5.275(1) A, and beta = 105.55(2) degrees. The inorganic layer of the hybrid network is formed by Cr(II) five-coordinated by three oxygen atoms from the phosphonates and one from the water molecule in a square pyramidal unit, whose apical position is occupied by the Cl(-) ion. Hydrogen bonds are established between the coordinating water molecule and the oxygen atoms of adjacent phosphonate ligands. The inorganic network is interspersed by ethylammonium groups, and the terminal ammonium moiety is linked to the apical Cl(-) ions through hydrogen bonds. Electrostatic interactions as well as hydrogen bonds and the coordinated chlorine atoms ensure the cohesion of the 3D structure. The lattice is polar (lack of inversion center), and this fact determines the magnetic behavior of the compound at low temperatures. The magnetic susceptibility data in the temperature range from 300 to 50 K show Curie-Weiss behavior, with C = 2.716 cm(3) K mol(-1) and the Weiss constant theta = -2.2 K. The corresponding effective magnetic moment of 4.7 mu(B) compares well with the expected value for Cr(2+) in d(4) high-spin configuration. A slight decrease of the chiT product versus T observed at temperatures below 50 K indicates nearest-neighbor antiferromagnetic exchange interactions. On cooling below T = 6 K, the magnetic susceptibility increases sharply up to a maximum at ca. 5 K and then decreases again. Below T = 6 K, hysteresis loops taken at different temperatures show that Cr[(H(3)N-(CH(2))(2)-PO(3))(Cl)(H(2)O)] behaves as a weak ferromagnet with the critical temperature T(N) at 5.5 K. The spin canting is responsible of the long-range magnetic

  13. Electron Scattering and Doping Mechanisms in Solid-Phase-Crystallized In2O3:H Prepared by Atomic Layer Deposition.

    PubMed

    Macco, Bart; Knoops, Harm C M; Kessels, Wilhelmus M M

    2015-08-05

    Hydrogen-doped indium oxide (In2O3:H) has recently emerged as an enabling transparent conductive oxide for solar cells, in particular for silicon heterojunction solar cells because its high electron mobility (>100 cm(2)/(V s)) allows for a simultaneously high electrical conductivity and optical transparency. Here, we report on high-quality In2O3:H prepared by a low-temperature atomic layer deposition (ALD) process and present insights into the doping mechanism and the electron scattering processes that limit the carrier mobility in such films. The process consists of ALD of amorphous In2O3:H at 100 °C and subsequent solid-phase crystallization at 150-200 °C to obtain large-grained polycrystalline In2O3:H films. The changes in optoelectronic properties upon crystallization have been monitored both electrically by Hall measurements and optically by analysis of the Drude response. After crystallization, an excellent carrier mobility of 128 ± 4 cm(2)/(V s) can be obtained at a carrier density of 1.8 × 10(20) cm(-3), irrespective of the annealing temperature. Temperature-dependent Hall measurements have revealed that electron scattering is dominated by unavoidable phonon and ionized impurity scattering from singly charged H-donors. Extrinsic defect scattering related to material quality such as grain boundary and neutral impurity scattering was found to be negligible in crystallized films indicating that the carrier mobility is maximized. Furthermore, by comparison of the absolute H-concentration and the carrier density in crystallized films, it is deduced that <4% of the incorporated H is an active dopant in crystallized films. Therefore, it can be concluded that inactive H atoms do not (significantly) contribute to defect scattering, which potentially explains why In2O3:H films are capable of achieving a much higher carrier mobility than conventional In2O3:Sn (ITO).

  14. Energy transfer mechanism of Sm3+/Eu3+ co-doped 2CaO-B2O3-P2O5 phosphors

    NASA Astrophysics Data System (ADS)

    Prasad, V. Reddy; Damodaraiah, S.; Ratnakaram, Y. C.

    2018-04-01

    Sm3+/Eu3+ co-doped calcium borophosphate phosphors were synthesized by solid state reaction method. 2CaO-B2O3-P2O5: Sm3+/Eu3+ co-doped phosphors were characterized by XRD, SEM, 31P solid state NMR, excitation, photoluminescence (PL) and decay profiles.. XRD profiles showed that the prepared phosphors exhibit a hexagonal phase in crystal structure and SEM results showed that the particles are more irregular morphologies. From 31P NMR spectra of Sm3+/Eu3+ co-doped 2CaO-B2O3-P2O5 phosphors, the chemical shifts located in the positive frequency region indicating the presence of mono-phosphate complexes Q0-(PO43 - ) . Photoluminescence spectra of Sm3+/Eu3+ co-doped 2CaO-B2O3-P2O5 phosphors show enhancement in emission intensity of Eu3+ ion due to co-doping with Sm3+ ions through energy transfer process. The energy level mechanism between Sm3+ and Eu3+ ions has been clearly explained. The energy transfer process has also been evidenced by lifetime decay profiles. These results suggest that the prepared phosphors are potential red luminescent optical materials.

  15. Electrical and magnetic properties of 0-3 Ba(Fe1/2Nb1/2)O3/PVDF composites

    NASA Astrophysics Data System (ADS)

    Ranjan, Hars; Mahto, Uttam K.; Chandra, K. P.; Kulkarni, A. R.; Prasad, A.; Prasad, K.

    Lead-free Ba(Fe1/2Nb1/2)O3/PVDF 0-3 composites were fabricated using melt-mixing technique. X-ray diffraction, scanning electron microscopy, dielectric, impedance, ac conductivity, magnetic force microscopy (MFM) and vibrating sample magnetometer studies were undertaken to characterize the samples. Average crystallite size of the Ba(Fe1/2Nb1/2)O3 powder, estimated using Williamson-Hall approach, was found to be ˜42nm. The filler particles of ˜0.5-1μm were found to disperse in the polymer matrix of all the composites. Filler concentration-dependent values of real and imaginary parts of complex permittivity showed increasing trend and were seen to follow Bruggeman and Furukawa equations. The data for ac conductivity exhibited negative temperature coefficient of resistance character of the test materials and were found to obey Jonscher’s power law. The correlated barrier hopping model was found to explain satisfactorily the mechanism of charge transport occurring in the system. MFM confirmed the presence of magnetic phases in the composites. Typical magnetization versus applied field curves indicated the possibility of magnetoelectric coupling in the system. Hence, the present composites have shown themselves as potential multi-functional candidate materials for use in high density data storage applications.

  16. Removal of petroleum hydrocarbons from contaminated groundwater by the combined technique of adsorption onto perlite followed by the O3/H2O2 process.

    PubMed

    Moussavi, Gholamreza; Bagheri, Amir

    2012-09-01

    Groundwater contaminated with petroleum hydrocarbons was treated using a combined system of adsorption onto powdered expanded perlite (PEP) followed by the O3/H2O2 process. The pretreatment investigations indicated a high capacity for PEP to remove petroleum hydrocarbons from the contaminated water. An experimental total petroleum hydrocarbon (TPH) adsorption capacity of 275 mg/g PEP was obtained at the natural pH of water. The experimental data fit best with the Freundlich isotherm model and pseudo-second-order adsorption model. The second phase of the experiment evaluated the performance of the O3/H2O2 process in the removal of residual TPH from pretreated water and compared the results with that of raw water. The O3/H202 process attained a maximum TPH removal rate for the pretreated water after 70 min, when 93% of the residual TPH in the effluent of the adsorption system was removed. Overall, the combination of adsorption onto PEP for 100 min and the subsequent treatment with the O3/H2O2 process for 70min eliminated over 99% of the TPH of highly petroleum-contaminated groundwater, with initial values of 162 mg/L. Therefore, we can conclude that the developed treatment system is an appropriate method of remediation for petroleum-contaminated waters.

  17. H2O2 rejuvenation-mediated synthesis of stable mixed-morphology Ag3PO4 photocatalysts.

    PubMed

    Agbe, Henry; Raza, Nadeem; Dodoo-Arhin, David; Chauhan, Aditya; Kumar, Ramachandran Vasant

    2018-04-01

    Ag 3 PO 4 photocatalyst has attracted interest of the scientific community in recent times due to its reported high efficiency for water oxidation and dye degradation. However, Ag 3 PO 4 photo-corrodes if electron accepter such as AgNO 3 is not used as scavenger. Synthesis of efficient Ag 3 PO 4 followed by a simple protocol for regeneration of the photocatalyst is therefore a prerequisite for practical application. Herein, we present a facile method for the synthesis of a highly efficient Ag 3 PO 4 , whose photocatalytic efficiency was demonstrated using 3 different organic dyes: Methylene Blue (MB), Methyl orange (MO) and Rhodamine B (RhB) organic dyes for degradation tests. Approximately, 19 % of Ag 3 PO 4 is converted to Ag 0 after 4.30 hours of continuous UV-Vis irradiation in presence of MB organic dye. We have shown that the Ag/Ag 3 PO 4 composite can be rejuvenated by a simple chemical oxidation step after several cycles of photocatalysis tests. At an optimal pH of 6.5, a mixture of cubic, rhombic dodecahedron, nanosphere and nanocrystals morphologies of the photocatalyst was formed. H 2 O 2 served as the chemical oxidant to re-insert the surface metallic Ag into the Ag 3 PO 4 photocatalyst but also as the agent that can control morphology of the regenerated as-prepared photocatalyst without the need for any other morphology controlling Agent (MCA). Surprisingly, the as- regenerated Ag 3 PO 4 was found to have higher photocatalytic reactivity than the freshly made material and superior at least 17 times in comparison with the conventional Degussa TiO 2 , and some of TiO 2 composites tested in this work.

  18. Stratospheric O3, H2O, and HDO distributions from balloon-based far-infrared observations

    NASA Technical Reports Server (NTRS)

    Abbas, M. M.; Guo, J.; Carli, B.; Mencaraglia, F.; Bonetti, A.

    1987-01-01

    Limb thermal emission spectra of the earth's stratosphere in the FIR obtained as part of the Balloon Intercomparison Campaign (BIC), have been analyzed for retrieval of trace constituent distributions. The observations analyzed here were made with a balloon-borne high-resolution Michelson interferometer operating in the 20-100/cm region, with an unapodized spectral resolution of 0.0033/cm. In this paper the vertical profiles of O3, H2O, and HDO retrieved from the observed spectra are presented and compared with the results from other BIC experiments. The retrieved profiles are found to be in good agreement with other measurements. The measurement of the HDO profile provides information about the sources of stratospheric water vapor. The variation of the D/H ratio of water vapor is derived from an analysis of HDO and H2O lines observed in the FIR spectra and is compared with the available measurements in the literature.

  19. The effect of sulfate on aluminum concentrations in natural waters: some stability relations in the system Al2O3-SO3-H2O at 298 K

    USGS Publications Warehouse

    Nordstrom, D. Kirk

    1982-01-01

    While gibbsite and kaolinite solubilities usually regulate aluminum concentrations in natural waters, the presence of sulfate can dramatically alter these solubilities under acidic conditions, where other, less soluble minerals can control the aqueous geochemistry of aluminum. The likely candidates include alunogen, Al2(SO4)3 ?? 17H2O, alunite, KAl3(SO4)2(OH)6, jurbanite, Al(SO4)(OH) ?? 5H2O, and basaluminite, Al4(SO4)(OH)10 ?? 5H2O. An examination of literature values shows that the log Ksp = -85.4 for alunite and log Ksp = -117.7 for basaluminite. In this report the log Ksp = -7.0 is estimated for alunogen and log Ksp = -17.8 is estimated for jurbanite. The solubility and stability relations among these four minerals and gibbsite are plotted as a function of pH and sulfate activity at 298 K. Alunogen is stable only at pH values too low for any natural waters (<0) and probably only forms as efflorescences from capillary films. Jurbanite is stable from pH < 0 up to the range of 3-5 depending on sulfate activity. Alunite is stable at higher pH values than jurbanite, up to 4-7 depending on sulfate activity. Above these pH limits gibbsite is the most stable phase. Basaluminite, although kinetically favored to precipitate, is metastable for all values of pH and sulfate activity. These equilibrium calculations predict that both sulfate and aluminum can be immobilized in acid waters by the precipitation of aluminum hydroxysulfate minerals. Considerable evidence supports the conclusion that the formation of insoluble aluminum hydroxy-sulfate minerals may be the cause of sulfate retention in soils and sediments, as suggested by Adams and Rawajfih (1977), instead of adsorption. ?? 1982.

  20. Endohedral complexes of fullerene-like silica molecules with H2O, CH4, and CH3NH2 molecules

    NASA Astrophysics Data System (ADS)

    Filonenko, O. V.; Lobanov, V. V.

    2013-07-01

    The possibility of formation of (SiO2)60@H2O, (SiO2)60@CH4, and (SiO2)60@CH3NH2 endohedral complexes was studied by the density functional (DFT) method (B3LYP exchange correlation functional, 6-31G** basis). The penetration of these molecules into the cavity of fullerene-like silica molecules is hindered by high activation barriers, which ensures the stability of the complexes formed during the synthesis of these molecules.

  1. Identification and Characterization of the Spodoptera Su(var) 3-9 Histone H3K9 trimethyltransferase and Its Effect in AcMNPV Infection

    PubMed Central

    Li, Binbin; Li, Sisi; Yin, Juan; Zhong, Jiang

    2013-01-01

    Histone H3-lysine9 (H3K9) trimethyltransferase gene Su(var) 3-9 was cloned and identified in three Spodoptera insects, Spodoptera frugiperda ( S . frugiperda ), S . exigua and S . litura . Sequence analysis showed that Spodoptera Su(var) 3-9 is highly conserved evolutionarily. Su(var) 3-9 protein was found to be localized in the nucleus in Sf9 cells, and interact with histone H3, and the heterochromatin protein 1a (HP1a) and HP1b. A dose-dependent enzymatic activity was found at both 27 °C and 37 °C in vitro, with higher activity at 27 °C. Addition of specific inhibitor chaetocin resulted in decreased histone methylation level and host chromatin relaxation. In contrast, overexpression of Su(var) 3-9 caused increased histone methylation level and cellular genome compaction. In AcMNV-infected Sf9 cells, the transcription of Su(var) 3-9 increased at late time of infection, although the mRNA levels of most cellular genes decreased. Pre-treatment of Sf9 cells with chaetocin speeded up viral DNA replication, and increased the transcription level of a variety of virus genes, whereas in Sf9 cells pre-transformed with Su(var) 3-9 expression vector, viral DNA replication slow down slightly. These findings suggest that Su(var) 3-9 might participate in the viral genes expression an genome replication repression during AcMNPV infection. It provided a new insight for the understanding virus–host interaction mechanism. PMID:23894480

  2. Improved Tribological Performance of Amorphous Carbon (a-C) Coating by ZrO2 Nanoparticles

    PubMed Central

    Tang, Jinzhu; Ding, Qi; Zhang, Songwei; Wu, Guizhi; Hu, Litian

    2016-01-01

    Nanomaterials, such as Graphene, h-BN nanoparticles and MoS2 nanotubes, have shown their ability in improving the tribological performance of amorphous carbon (a-C) coatings. In the current study, the effectiveness of ZrO2 nanoparticles (ZrO2-NPs) in lubricating the self-mated nonhydrogenated a-C contacts was investigated in boundary lubrication regime. The results showed that 13% less friction and 50% less wear compared to the base oil were achieved by employing ZrO2-NPs in the base oil in self-mated a-C contacts. Via analyzing the ZrO2-NPs and the worn a-C surface after tests, it was found that the improved lubrication by ZrO2-NPs was based on “polishing effects”, which is a new phenomenon observed between a-C and nanoparticles. Under the “polishing effect”, micro-plateaus with extremely smooth surface and uniform height were produced on the analyzed a-C surface. The resulting topography of the a-C coating is suitable for ZrO2-NPs to act as nano-bearings between rubbing surfaces. Especially, the ZrO2-NPs exhibited excellent mechanical and chemical stability, even under the severe service condition, suggesting that the combination of nonhydrogenated a-C coating with ZrO2-NPs is an effective, long lasting and environment-friendly lubrication solution. PMID:28773916

  3. Ni doped Fe3O4 magnetic nanoparticles.

    PubMed

    Larumbe, S; Gómez-Polo, C; Pérez-Landazábal, J I; García-Prieto, A; Alonso, J; Fdez-Gubieda, M L; Cordero, D; Gómez, J

    2012-03-01

    In this work, the effect of nickel doping on the structural and magnetic properties of Fe3O4 nanoparticles is analysed. Ni(x)Fe(3-x)O4 nanoparticles (x = 0, 0.04, 0.06 and 0.11) were obtained by chemical co-precipitation method, starting from a mixture of FeCl2 x 4H2O and Ni(AcO)2 x 4H2O salts. The analysis of the structure and composition of the synthesized nanoparticles confirms their nanometer size (main sizes around 10 nm) and the inclusion of the Ni atoms in the characteristic spinel structure of the magnetite Fe3O4 phase. In order to characterize in detail the structure of the samples, X-ray absorption (XANES) measurements were performed on the Ni and Fe K-edges. The results indicate the oxidation of the Ni atoms to the 2+ state and the location of the Ni2+ cations in the Fe2+ octahedral sites. With respect to the magnetic properties, the samples display the characteristic superparamagnetic behaviour, with anhysteretic magnetic response at room temperature. The estimated magnetic moment confirms the partial substitution of the Fe2+ cations by Ni2+ atoms in the octahedral sites of the spinel structure.

  4. Crystal structure, vibrational spectra, optical and DFT studies of bis (3-azaniumylpropyl) azanium pentachloroantimonate (III) chloride monohydrate (C6H20N3)SbCl5·Cl·H2O

    NASA Astrophysics Data System (ADS)

    Ahmed, Houssem Eddine; Kamoun, Slaheddine

    2017-09-01

    The crystal structure of (C6H20N3)SbCl5·Cl·H2O is built up of [NH3(CH2)3NH2(CH2)3NH3]3 + cations, [SbCl5]2 - anions, free Cl- anions and neutral water molecules connected together by Nsbnd H ⋯ Cl, Nsbnd HO and Osbnd H ⋯ Cl hydrogen bonds. The optical band gap determined by diffuse reflection spectroscopy (DRS) is 3.78 eV for a direct allowed transition. Optimized molecular geometry, atomic Mulliken charges, harmonic vibrational frequencies, HOMO-LUMO and related molecular properties of the (C6H20N3)SbCl5·Cl·H2O compound were calculated by Density functional theory (DFT) using B3LYP method with GenECP sets. The calculated structural parameters (bond lengths and angles) are in good agreement with the experimental XRD data. The vibrational unscaled wavenumbers were calculated and scaled by a proper scaling factor of 0.984. Acceptable consistency was observed between calculated and experimental results. The assignments of wavenumbers were made on the basis of potential energy distribution (PED) using Vibrational Energy Distribution Analysis (VEDA) software. The HOMO-LUMO study was extended to calculate various molecular parameters like ionization potential, electron affinity, global hardness, electro-chemical potential, electronegativity and global electrophilicity of the given molecule.

  5. Middendorfite, K3Na2Mn5Si12(O,OH)36 · 2H2O, a new mineral species from the Khibiny pluton, Kola Peninsula

    NASA Astrophysics Data System (ADS)

    Pekov, I. V.; Chukanov, N. V.; Dubinchuk, V. T.; Zadov, A. E.

    2007-12-01

    Middendorfite, a new mineral species, has been found in a hydrothermal assemblage in Hilairite hyperperalkaline pegmatite at the Kirovsky Mine, Mount Kukisvumchorr apatite deposit, Khibiny alkaline pluton, Kola Peninsula, Russia. Microcline, sodalite, cancrisilite, aegirine, calcite, natrolite, fluorite, narsarsukite, labuntsovite-Mn, mangan-neptunite, and donnayite are associated minerals. Middendorfite occurs as rhombshaped lamellar and tabular crystals up to 0.1 × 0.2 × 0.4 mm in size, which are combined in worm-and fanlike segregations up to 1 mm in size. The color is dark to bright orange, with a yellowish streak and vitreous luster. The mineral is transparent. The cleavage (001) is perfect, micalike; the fracture is scaly; flakes are flexible but not elastic. The Mohs hardness is 3 to 3.5. Density is 2.60 g/cm3 (meas.) and 2.65 g/cm3 (calc.). Middendorfite is biaxial (-), α = 1.534, β = 1.562, and γ = 1.563; 2 V (meas.) = 10°. The mineral is pleochroic strongly from yellowish to colorless on X through brown on Y and to deep brown on Z. Optical orientation: X = c. The chemical composition (electron microprobe, H2O determined with Penfield method) is as follows (wt %): 4.55 Na2O, 10.16 K2O, 0.11 CaO, 0.18 MgO, 24.88 MnO, 0.68 FeO, 0.15 ZnO, 0.20 Al2O3, 50.87 SiO2, 0.17 TiO2, 0.23 F, 7.73 H2O; -O=F2-0.10, total is 99.81. The empirical formula calculated on the basis of (Si,Al)12(O,OH,F)36 is K3.04(Na2.07Ca0.03)Σ2.10(Mn4.95Fe0.13Mg0.06Ti0.03Zn0.03)Σ5.20(Si11.94Al0.06)Σ12O27.57(OH)8.26F0.17 · 1.92H2O. The simplified formula is K3Na2Mn5Si12(O,OH)36 · 2H2O. Middenforite is monoclinic, space group: P21/ m or P21. The unit cell dimensions are a = 12.55, b = 5.721, c = 26.86 Å; β = 114.04°, V = 1761 Å3, Z = 2. The strongest lines in the X-ray powder pattern [ d, Å, ( I)( hkl)] are: 12.28(100)(002), 4.31(81)(11overline 4 ), 3.555(62)(301, 212), 3.063(52)(008, 31overline 6 ), 2.840(90)(312, 021, 30overline 9 ), 2.634(88)(21overline 9 , 1.0.overline 1 0

  6. Carbonato-bridged Ni(II)2Ln(III)2 (Ln(III) = Gd(III), Tb(III), Dy(III)) complexes generated by atmospheric CO2 fixation and their single-molecule-magnet behavior: [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH or H2O)Ln(III)(NO3)}2]·solvent [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato].

    PubMed

    Sakamoto, Soichiro; Fujinami, Takeshi; Nishi, Koshiro; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Re, Nazzareno

    2013-06-17

    Atmospheric CO2 fixation of [Ni(II)(3-MeOsaltn)(H2O)22.5H2O [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato], Ln(III)(NO3)3·6H2O, and triethylamine occurred in methanol/acetone, giving a first series of carbonato-bridged Ni(II)2Ln(III)2 complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH)Ln(III)(NO3)}2] (1Gd, 1Tb, and 1Dy). When the reaction was carried out in acetonitrile/water, it gave a second series of complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(H2O)Ln(III)(NO3)}22CH3CN·2H2O (2Gd, 2Tb, and 2Dy). For both series, each Ni(II)2Ln(III)2 structure can be described as two di-μ-phenoxo-bridged Ni(II)Ln(III) binuclear units bridged by two carbonato CO3(2-) units to form a carbonato-bridged (μ4-CO3)2{Ni(II)2Ln(III)2} structure. The high-spin Ni(II) ion has octahedral coordination geometry, and the Ln(III) ion is coordinated by O9 donor atoms from Ni(II)(3-MeOsaltn), bidentate NO3(-), and one and two oxygen atoms of two CO3(2-) ions. The NO3(-) ion for the first series roughly lie on Ln-O(methoxy) bonds and are tilted toward the outside, while for the second series, the two oxygen atoms roughly lie on one of the Ln-O(phenoxy) bonds due to the intramolecular hydrogen bond. The temperature-dependent magnetic susceptibilities indicated a ferromagnetic interaction between the Ni(II) and Ln(III) ions (Ln(III) = Gd(III), Tb(III), Dy(III)) for all of the complexes, with a distinctly different magnetic behavior between the two series in the lowest-temperature region due to the Ln(III)-Ln(III) magnetic interaction and/or different magnetic anisotropies of the Tb(III) or Dy(III) ion. Alternating-current susceptibility measurements under the 0 and 1000 Oe direct-current (dc) bias fields showed no magnetic relaxation for the Ni(II)2Gd(III)2 complexes but exhibited an out-of-phase signal for Ni(II)2Tb(III)2 and Ni(II)2Dy(III)2, indicative of slow relaxation of magnetization. The energy barriers, Δ/kB, for the spin flipping were estimated from the Arrhenius

  7. Synthesis of 4-substituted pyrido[2,3-d]pyrimidin-4(1H)-one as analgesic and anti-inflammatory agents.

    PubMed

    El-Gazzar, Abdel-Rahman B A; Hafez, Hend N

    2009-07-01

    4-Substituted-pyrido[2,3-d]pyrimidin-4(1H)-ones 4a-c were synthesized by oxidation of 4-substituted-dihydropyrido[2,3-d]pyrimidin-4(1H)-ones 3a-c which were in turn prepared from arylidenemalononitriles 1a-c and 6-aminothiouracil 2. The reactivity of compounds 4a-c towards some reagents such as formamide, carbon disulfide, urea, thiourea, formic and acetic acids were studied. All the synthesized compounds were characterized by spectroscopic means and elemental analysis. Compound 4c exhibited 64% and 72% analgesic activity. Also, compound 4b showed 50% and 65% anti-inflammatory activity. Interestingly these compounds showed one-third of ulcer index of the reference aspirin and diclofenac.

  8. Magneto-optical properties of α-Fe2O3@ZnO nanocomposites prepared by the high energy ball-milling technique

    NASA Astrophysics Data System (ADS)

    Chaudhury, Chandana Roy; Roychowdhury, Anirban; Das, Anusree; Das, Dipankar

    2016-05-01

    Magnetic-fluorescent nanocomposites (NCs) with 10 wt% of α-Fe2O3 in ZnO have been prepared by the high energy ball-milling. The crystallite sizes of α-Fe2O3 and ZnO in the NCs are found to vary from 65 nm to 20 nm and 47 nm to 15 nm respectively as milling time is increased from 2 to 30 h. XRD analysis confirms presence of α-Fe2O3 and ZnO in pure form in all the NCs. UV-vis study of the NCs shows a continuous blue-shift of the absorption peak and a steady increase of band gap of ZnO with increasing milling duration that are assigned to decreasing particle size of ZnO in the NCs. Photoluminescence (PL) spectra of the NCs reveal three weak emission bands in the visible region at 421, 445 and 485 nm along with the strong near band edge emission at 391 nm. These weak emission bands are attributed to different defect - related energy levels e.g. Zn-vacancy, Zn interstitial and oxygen vacancy. Dc and ac magnetization measurements show presence of weakly interacting superparamagnetic (SPM) α-Fe2O3 particles in the NCs. 57Fe-Mössbauer study confirms presence of SPM hematite in the sample milled for 30 h. Positron annihilation lifetime measurements indicate presence of cation vacancies in ZnO nanostructures confirming results of PL studies.

  9. Catalytic activity of CuOn-La2O3/gamma-Al2O3 for microwave assisted ClO2 catalytic oxidation of phenol wastewater.

    PubMed

    Bi, Xiaoyi; Wang, Peng; Jiang, Hong

    2008-06-15

    In order to develop a catalyst with high activity and stability for microwave assisted ClO2 catalytic oxidation, we prepared CuOn-La2O3/gamma-Al2O3 by impregnation-deposition method, and determined its properties using BET, XRF, XPS and chemical analysis techniques. The test results show that, better thermal ability of gamma-Al2O3 and high loading of Cu in the catalyst can be achieved by adding La2O3. The microwave assisted ClO2 catalytic oxidation process with CuOn-La2O3/gamma-Al2O3 used as catalyst was also investigated, and the results show that the catalyst has an excellent catalytic activity in treating synthetic wastewater containing 100 mg/L phenol, and 91.66% of phenol and 50.35% of total organic carbon (TOC) can be removed under the optimum process conditions. Compared with no catalyst process, CuOn-La2O3/gamma-Al2O3 can effectively degrade contaminants in short reaction time and with low oxidant dosage, extensive pH range. The comparison of phenol removal efficiency in the different process indicates that microwave irradiation and catalyst work together to oxidize phenol effectively. It can therefore be concluded from results and discussion that CuOn-La2O3/gamma-Al2O3 is a suitable catalyst in microwave assisted ClO2 catalytic oxidation process.

  10. Tinnunculite, C5H4N4O3 · 2H2O: Occurrences on the Kola Peninsula and Redefinition and Validation as a Mineral Species

    NASA Astrophysics Data System (ADS)

    Pekov, I. V.; Chukanov, N. V.; Yapaskurt, V. O.; Belakovskiy, D. I.; Lykova, I. S.; Zubkova, N. V.; Shcherbakova, E. P.; Britvin, S. N.; Chervonnyi, A. D.

    2017-12-01

    Based on a study of samples found in the Khibiny (Mt. Rasvumchorr: the holotype) and Lovozero (Mts Alluaiv and Vavnbed) alkaline complexes on the Kola Peninsula, Russia, tinnunculite was approved by the IMA Commission on New Minerals, Nomenclature, and Classification as a valid mineral species (IMA no. 2015-02la) and, taking into account a revisory examination of the original material from burnt dumps of coal mines in the southern Urals, it was redefined as crystalline uric acid dihydrate (UAD), C5H4N4O3 · 2H2O. Tinnunculite is poultry manure mineralized in biogeochemical systems, which could be defined as "guano microdeposits." The mineral occurs as prismatic or tabular crystals up to 0.01 × 0.1 × 0.2 mm in size and clusters of them, as well as crystalline or microglobular crusts. Tinnunculite is transparent or translucent, colorless, white, yellowish, reddish or pale lilac. Crystals show vitreous luster. The mineral is soft and brittle, with a distinct (010) cleavage. D calc = 1.68 g/cm3 (holotype). Tinnunculite is optically biaxial (-), α = 1.503(3), β = 1.712(3), γ = 1.74(1), 2 V obs = 40(10)°. The IR spectrum is given. The chemical composition of the holotype sample (electron microprobe data, content of H is calculated by UAD stoichiometry) is as follows, wt %: 37.5 O, 28.4 C, 27.0 N, 3.8 Hcalc, total 96.7. The empirical formula calculated on the basis of (C + N+ O) = 14 apfu is: C4.99H8N4.07O4.94. Tinnunculite is monoclinic, space group (by analogy with synthetic UAD) P21/ c. The unit cell parameters of the holotype sample (single crystal XRD data) are a = 7.37(4), b = 6.326(16), c = 17.59(4) Å, β = 90(1)°, V = 820(5) Å3, Z = 4. The strongest reflections in the XRD pattern ( d, Å- I[ hkl]) are 8.82-84[002], 5.97-15[011], 5.63-24[102̅, 102], 4.22-22[112], 3.24-27[114̅,114], 3.18-100[210], 3.12-44[211̅, 211], 2.576-14[024].

  11. Simultaneous purifying of Hg0, SO2, and NOx from flue gas by Fe3+/H2O2: the performance and purifying mechanism.

    PubMed

    Xing, Yi; Li, Liuliu; Lu, Pei; Cui, Jiansheng; Li, Qianli; Yan, Bojun; Jiang, Bo; Wang, Mengsi

    2018-03-01

    Hg 0 , SO 2 , and NOx result in heavily global environmental pollution and serious health hazards. Up to now, how to efficiently remove mercury with SO 2 and NOx from flue gas is still a tough task. In this study, series of high oxidizing Fenton systems were employed to purify the pollutants. The experimental results showed that Fe 3+ /H 2 O 2 was more suitable to purify Hg 0 than Fe 2+ /H 2 O 2 and Cu 2+ /H 2 O 2. The optimal condition includes Fe 3+ concentration of 0.008 mol/L, Hg 0 inlet concentration of 40 μg/m 3 , solution temperature of 50 °C, pH of 3, H 2 O 2 concentration of 0.7 mol/L, and O 2 percentage of 6%. When SO 2 and NOx were taken into account under the optimal condition, Hg 0 removal efficiency could be enhanced to 91.11% while the removal efficiency of both NOx and SO 2 was slightly declined, which was consistent to the analysis of purifying mechanism. The removal efficiency of Hg 0 was stimulated by accelerating the conversion of Fe 2+ to Fe 3+ , which resulted from the existence of SO 2 and NOx. The results of this study suggested that simultaneously purifying Hg 0 , SO 2 , and NOx from flue gas is feasible.

  12. Atmospheric Chemistry of (CF3)2CHOCH3, (CF3)2CHOCHO, and CF3C(O)OCH3.

    PubMed

    Østerstrøm, Freja From; Wallington, Timothy J; Sulbaek Andersen, Mads P; Nielsen, Ole John

    2015-10-22

    Smog chambers with in situ FTIR detection were used to measure rate coefficients in 700 Torr of air and 296 ± 2 K of: k(Cl+(CF3)2CHOCH3) = (5.41 ± 1.63) × 10(-12), k(Cl+(CF3)2CHOCHO) = (9.44 ± 1.81) × 10(-15), k(Cl+CF3C(O)OCH3) = (6.28 ± 0.98) × 10(-14), k(OH+(CF3)2CHOCH3) = (1.86 ± 0.41) × 10(-13), and k(OH+(CF3)2CHOCHO) = (2.08 ± 0.63) × 10(-14) cm(3) molecule(-1) s(-1). The Cl atom initiated oxidation of (CF3)2CHOCH3 gives (CF3)2CHOCHO in a yield indistinguishable from 100%. The OH radical initiated oxidation of (CF3)2CHOCH3 gives the following products (molar yields): (CF3)2CHOCHO (76 ± 8)%, CF3C(O)OCH3 (16 ± 2)%, CF3C(O)CF3 (4 ± 1)%, and C(O)F2 (45 ± 5)%. The primary oxidation product (CF3)2CHOCHO reacts with Cl atoms to give secondary products (molar yields): CF3C(O)CF3 (67 ± 7)%, CF3C(O)OCHO (28 ± 3)%, and C(O)F2 (118 ± 12)%. CF3C(O)OCH3 reacts with Cl atoms to give: CF3C(O)OCHO (80 ± 8)% and C(O)F2 (6 ± 1)%. Atmospheric lifetimes of (CF3)2CHOCH3, (CF3)2CHOCHO, and CF3C(O)OCH3 were estimated to be 62 days, 1.5 years, and 220 days, respectively. The 100-year global warming potentials (GWPs) for (CF3)2CHOCH3, (CF3)2CHOCHO, and CF3C(O)OCH3 are estimated to be 6, 121, and 46, respectively. A comprehensive description of the atmospheric fate of (CF3)2CHOCH3 is presented.

  13. [Preparation and photoluminescence study of Er3+ : Y2O3 transparent ceramics].

    PubMed

    Luo, Jun-ming; Li, Yong-xiu; Deng, Li-ping

    2008-10-01

    Y2O3 acted as the matrix material, which was doped with different concentrations of Er3+, Er3+ : Y2O3 nanocrystalline powder was prepared by co-precipitation method, and Er3+ : Y2O3 transparent ceramics was fabricated by vacuum sintering at 1700 degrees C, 1 x 10(-3) Pa for 8 h. By using the X-ray diffraction (D/MAX-RB), transmission electron microscopy(Philips EM420), automatic logging spectrophotometer(DMR-22), fluorescence analyzer (F-4500) and 980 nm diode laser, the structural, morphological and luminescence properties of the sample were investigated. The results show that Er3+ dissolved completely in the Y2O3 cubic phase, the precursor was amorphous, weak diffraction peaks appeared after calcination at 400 degrees C, and if calcined at 700 degrees C, the precursor turned to pure cubic phase. With increasing the calcining temperature, the diffraction peaks became sharp quickly, and when the calcining temperature reached 1100 degrees C, the diffraction peaks became very sharp, indicating that the grains were very large. The particles of Er+ : Y2O3 is homogeneous and nearly spherical, the average diameter of the particles is in the range of 40-60 nm after being calcined at 1000 degrees C for 2 h. The relative density of Er3+ : Y2O3 transparent ceramics is 99.8%, the transmittance of the Er2+ : Y2O3 transparent ceramics is markedly lower than the single crystal at the short wavelength, but the transmittance is improved noticeably with increasing the wavelength, and the transmittance exceeds 60% at the wavelength of 1200 nm. Excited under the 980 nm diode laser, there are two main up-conversion emission bands, green emission centers at 562 nm and red emission centers at 660 nm, which correspond to (4)S(3/2) / (2)H(11/2) - (4)I(15/2) and (4)F(9/2) - (4)I(15/2) radiative transitions respectively. By changing the doping concentrations of Er3+, the color of up-conversion luminescence can be tuned from green to red gradually. The luminescence intensity is not reinforce

  14. Size-driven magnetic transitions in La1/3Ca2/3MnO3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Markovich, V.; Fita, I.; Wisniewski, A.; Mogilyansky, D.; Puzniak, R.; Titelman, L.; Gorodetsky, G.

    2010-09-01

    Magnetic properties of electron-doped La1/3Ca2/3MnO3 manganite nanoparticles with average particle size ranging from 12 to 42 nm, prepared by the glycine-nitrate method, have been investigated in temperature range 5-300 K and in magnetic fields up to 90 kOe. Reduction in the particle size suppresses antiferromagnetism and decreases the Néel temperature. In contrast to bulk crystals, the charge ordering does not occur in all studied nanoparticles, while a weak ferromagnetism appears above 200 K. Low temperature magnetic hysteresis loops indicate upon exchange bias effect displayed by horizontal and vertical shifts in field cooled processes. The spontaneous and remanent magnetization at low temperature shows a relatively complex variation with particle size. The size-induced structural/magnetic disorder drives the La1/3Ca2/3MnO3 nanoparticles to a pronounced glassy behavior for the smallest 12 nm particles, as evidenced by large difference between zero field cooled and field cooled magnetization, frequency dependent ac-susceptibility, as well as characteristic slowing down in the spin dynamics. Time evolution of magnetization recorded in magnetic fields after field cooling to low temperatures exhibits pronounced relaxation and a very noisy behavior that may be caused by formation of some collective states. Magnetic properties of the nanoparticle samples are compared with those of La0.2Ca0.8MnO3 nanoparticles. These results shed some light on the coupling between charges and spin degrees of freedom in antiferromagnetic manganite nanoparticles.

  15. Theoretical study on the spectroscopic properties of CO3(*-).nH2O clusters: extrapolation to bulk.

    PubMed

    Pathak, Arup K; Mukherjee, Tulsi; Maity, Dilip K

    2008-10-24

    Vertical detachment energies (VDE) and UV/Vis absorption spectra of hydrated carbonate radical anion clusters, CO(3)(*-).nH(2)O (n=1-8), are determined by means of ab initio electronic structure theory. The VDE values of the hydrated clusters are calculated with second-order Moller-Plesset perturbation (MP2) and coupled cluster theory using the 6-311++G(d,p) set of basis functions. The bulk VDE value of an aqueous carbonate radical anion solution is predicted to be 10.6 eV from the calculated weighted average VDE values of the CO(3)(*-).nH(2)O clusters. UV/Vis absorption spectra of the hydrated clusters are calculated by means of time-dependent density functional theory using the Becke three-parameter nonlocal exchange and the Lee-Yang-Parr nonlocal correlation functional (B3LYP). The simulated UV/Vis spectrum of the CO(3)(*-).8H(2)O cluster is in excellent agreement with the reported experimental spectrum for CO(3)(*-) (aq), obtained based on pulse radiolysis experiments.

  16. A new set of K3Fe3(PO4)4·yH2O (0 ≤ y ≤ 1) layered phases obtained by topotactic reactions

    NASA Astrophysics Data System (ADS)

    Trad, Khiem; Wattiaux, Alain; Ben Amara, Mongi; Delmas, Claude; Carlier, Dany

    2018-06-01

    K3Fe3(PO4)4·H2O powder was synthesized by Na+/K+ exchange reaction from Na3Fe3(PO4)4 in aqueous medium. The replacement of the sodium cations by the potassium larger ones and water molecules causes a structural distortion leading to P2/n monoclinic K3Fe3(PO4)4·H2O. This new layered phase was characterized by XRD, Mössbauer spectroscopy and magnetic measurements. The study of its thermal stability reveals that other new layered K3Fe3(PO4)4·yH2O with (0 ≤ y ≤ 1) phases can be stabilized up to 600 °C and finally at higher temperature a new K3Fe3(PO4)4 polymorph with a different structural type is irreversibility formed.

  17. Histone deacetylase and Cullin3-REN(KCTD11) ubiquitin ligase interplay regulates Hedgehog signalling through Gli acetylation.

    PubMed

    Canettieri, Gianluca; Di Marcotullio, Lucia; Greco, Azzura; Coni, Sonia; Antonucci, Laura; Infante, Paola; Pietrosanti, Laura; De Smaele, Enrico; Ferretti, Elisabetta; Miele, Evelina; Pelloni, Marianna; De Simone, Giuseppina; Pedone, Emilia Maria; Gallinari, Paola; Giorgi, Alessandra; Steinkühler, Christian; Vitagliano, Luigi; Pedone, Carlo; Schinin, M Eugenià; Screpanti, Isabella; Gulino, Alberto

    2010-02-01

    Hedgehog signalling is crucial for development and is deregulated in several tumours, including medulloblastoma. Regulation of the transcriptional activity of Gli (glioma-associated oncogene) proteins, effectors of the Hedgehog pathway, is poorly understood. We show here that Gli1 and Gli2 are acetylated proteins and that their HDAC-mediated deacetylation promotes transcriptional activation and sustains a positive autoregulatory loop through Hedgehog-induced upregulation of HDAC1. This mechanism is turned off by HDAC1 degradation through an E3 ubiquitin ligase complex formed by Cullin3 and REN, a Gli antagonist lost in human medulloblastoma. Whereas high HDAC1 and low REN expression in neural progenitors and medulloblastomas correlates with active Hedgehog signalling, loss of HDAC activity suppresses Hedgehog-dependent growth of neural progenitors and tumour cells. Consistent with this, abrogation of Gli1 acetylation enhances cellular proliferation and transformation. These data identify an integrated HDAC- and ubiquitin-mediated circuitry, where acetylation of Gli proteins functions as an unexpected key transcriptional checkpoint of Hedgehog signalling.

  18. First quadruple-glycine bridging mono-lanthanide-substituted borotungstate hybrids.

    PubMed

    Liu, Jiancai; Yu, Jing; Han, Qing; Wen, Yue; Chen, Lijuan; Zhao, Junwei

    2016-10-18

    A class of novel organic-inorganic hybrid lanthanide (Ln)-substituted Keggin-type borotungstates K 4 Na 4 H 4 [Ln 2 (gly) 4 (α-BW 11 O 39 ) 2 ]·23H 2 O [Ln = Ce 3+ (1), Pr 3+ (2), Nd 3+ (3), Sm 3+ (4), Eu 3+ (5), Tm 3+ (6); gly = glycine] have been synthesized from the reaction of K 8 [BW 11 O 39 H]·13H 2 O, NaAc·6H 2 O and Ln(NO 3 ) 3 ·6H 2 O by employing gly ligands as structure-stabilizing agents in the conventional aqueous solution system and structurally characterized by elemental analyses, IR spectroscopy, thermogravimetric (TG) analyses, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The common prominent structural feature of isomorphic 1-6 is that all of them consist of two mono-Ln-substituted Keggin [Ln(α-BW 11 O 39 )] 6- fragments linked by four gly ligands, furnishing an intriguing dimeric assembly of the quadruple-gly-connective mono-Ln-substituted borotungstate, in which each carboxylic oxygen atom from gly ligands is bound to Ln 3+ cations in the μ 2 -O or μ 3 -O mode. To the best of our knowledge, 1-6 represent the first examples of inorganic-organic hybrid Ln-substituted borotungstates functionalized by quadruple amino acid bridges. The solid-state photoluminescence properties of 3-5 have been determined at ambient temperature and the photoluminescence emission spectra exhibit the characteristic emission bands derived from Ln 3+ centers. The thermostability of 1-6 has been studied and the thermal decomposition procedure of 3 has been comprehensively investigated with the assistance of variable-temperature PXRD patterns and variable-temperature IR spectra. Furthermore, magnetic susceptibility measurements of 1, 2 and 4 have been conducted.

  19. Effect of pH value on structural and photoluminescence properties of Tb3+ -doped Lu2O3 nanopowders synthesized by sol-gel route

    NASA Astrophysics Data System (ADS)

    Mendoud, A.; Guerbous, L.; Boukerika, A.; Boudine, B.; Benrekaa, N.

    2018-01-01

    Tb3+-doped Lu2O3 nanophosphors were prepared via simple sol-gel method, at different pH value of solution (2, 5, 8 and 11), using diethanolamine (DEA) as polymerization agent. The nanopowder samples were characterized by X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, room temperature steady and time resolved photoluminescence spectroscopy. The structural analysis reveals that all samples mainely crystallized in the cubic bixbyite structure with Ia3 space group. Also, it was found that the pH value of solution strongly influences the crystallite size, the vibrational frequency modes and the surface morphology of Lu2O3:Tb3+ nanocrystals. All samples show blue-greenish emissions, corresponding to 5D4 → 7FJ (J = 3, 4, 5 and 6) intraconfigurationnelles transitions. The intense green emission peak situated at 542 nm is assigned to 5D4 → 7F5 transition. The 4f8 → 4f75d1 spin-allowed and forbidden transitions, the charge transfer band (CTB) O2- → Tb3+ and the host absorption bands were observed and their dependence on pH value is discussed.

  20. Effect of surface moisture on dielectric behavior of ultrafine BaTiO3 particulates.

    NASA Technical Reports Server (NTRS)

    Mountvala, A. J.

    1971-01-01

    The effects of adsorbed H2O on the dielectric properties of ultrafine BaTiO3 particulates of varying particle size and environmental history were determined. The dielectric behavior depends strongly on surface hydration. No particle size dependence of dielectric constant was found for dehydroxylated surfaces in ultrafine particulate (unsintered) BaTiO3 materials. For equivalent particle sizes, the ac conductivity is sensitive to surface morphology. Reactions with H2O vapor appear to account for the variations in dielectric properties. Surface dehydration was effectively accomplished by washing as-received powders in isopropanol.