Sample records for a2 a3 a4

  1. Synthesis, luminescence, and energy-transfer properties of β-Na2Ca4(PO4)2(SiO4):A (A = Eu(2+), Dy(3+), Ce(3+)/Tb(3+)) phosphors.

    PubMed

    Li, Kai; Shang, Mengmeng; Geng, Dongling; Lian, Hongzhou; Zhang, Yang; Fan, Jian; Lin, Jun

    2014-07-07

    A series of β-Na2Ca4(PO4)2(SiO4) (β-NCPS):A (A = Eu(2+), Dy(3+), Ce(3+)/Tb(3+)) phosphors were prepared via a high-temperature solid-state reaction route. The X-ray diffraction, Fourier transform infrared, photoluminescence (PL), cathodoluminescence (CL) properties, fluorescent lifetimes, and absolute quantum yield were exploited to characterize the samples. Under UV radiation, the β-NCPS:Eu(2+) phosphors present bright green emissions, and the β-NCPS:Ce(3+) phosphors show strong blue emissions, which are attributed to their 4f(6)5d(1) → 4f(7) and 5d-4f allowed transitions, respectively. The β-NCPS:Ce(3+), Tb(3+) phosphors display intense tunable color from blue to green and high absolute quantum yields (81% for β-NCPS:0.12Ce(3+) and 83% for β-NCPS:0.12Ce(3+), 0.08Tb(3+)) when excited at 365 nm. Simultaneously, the energy transfer from Ce(3+) to Tb(3+) ions is deduced from the spectral overlap between Ce(3+) emission and Tb(3+) excitation spectra and demonstrated by the change of emission spectra and decay lifetimes. Moreover, the energy-transfer mechanism from Ce(3+) to Tb(3+) ions is confirmed to be exchange interaction according to the discussion of expression from Dexter and Reisfeld. Under a low-voltage electron-beam excitation, the β-NCPS:A (A = Eu(2+), Dy(3+), Ce(3+)/Tb(3+)) phosphors exhibit their characteristic emissions, and the emission profiles of β-NCPS:Ce(3+),Tb(3+) phosphors are obviously different from those of the PL spectra; this difference might be ascribed to their different luminescence mechanisms. These results in PL and CL properties suggest that β-NCPS:A (A = Eu(2+), Dy(3+), Ce(3+)/Tb(3+)) phosphors are potential candidates for solid-state lighting and field-emission displays.

  2. 3-(Fur-2-yl)-10-(2-phenylethyl)-[1,2,4]triazino[4,3-a]benzimidazol-4(10H)-one, a novel adenosine receptor antagonist with A(2A)-mediated neuroprotective effects.

    PubMed

    Scatena, Alessia; Fornai, Francesco; Trincavelli, Maria Letizia; Taliani, Sabrina; Daniele, Simona; Pugliesi, Isabella; Cosconati, Sandro; Martini, Claudia; Da Settimo, Federico

    2011-09-21

    In this study, compound FTBI (3-(2-furyl)-10-(2-phenylethyl)[1,2,4]triazino[4,3-a]benzimidazol-4(10H)-one) was selected from a small library of triazinobenzimidazole derivatives as a potent A(2A) adenosine receptor (AR) antagonist and tested for its neuroprotective effects against two different kinds of dopaminergic neurotoxins, 1-methyl-4-phenylpyridinium (MPP+) and methamphetamine (METH), in rat PC12 and in human neuroblastoma SH-SY5Y cell lines. FTBI, in a concentration range corresponding to its affinity for A(2A) AR subtype, significantly increased the number of viable PC12 cells after their exposure to METH and, to a similar extent, to MPP+, as demonstrated in both trypan blue exclusion assay and in cytological staining. These neuroprotective effects were also observed with a classical A(2A) AR antagonist, ZM241385, and appeared to be completely counteracted by the AR agonist, NECA, supporting A(2A) ARs are directly involved in FTBI-mediated effects. Similarly, in human SH-SY5Y cells, FTBI was able to prevent cell toxicity induced by MPP+ and METH, showing that this A(2A) AR antagonist has a neuroprotective effect independently by the specific cell model. Altogether these results demonstrate that the A(2A) AR blockade mediates cell protection against neurotoxicity induced by dopaminergic neurotoxins in dopamine containing cells, supporting the potential use of A(2A) AR antagonists in dopaminergic degenerative diseases including Parkinson's disease.

  3. 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.

  4. 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.

  5. Luminescence and energy transfer properties of Ca2Ba3(PO4)3Cl and Ca2Ba3(PO4)3Cl:A (A = Eu2+/Ce3+/Dy3+/Tb3+) under UV and low-voltage electron beam excitation.

    PubMed

    Shang, Mengmeng; Geng, Dongling; Yang, Dongmei; Kang, Xiaojiao; Zhang, Yang; Lin, Jun

    2013-03-18

    Pure Ca2Ba3(PO4)3Cl and rare earth ion (Eu(2+)/Ce(3+)/Dy(3+)/Tb(3+)) doped Ca2Ba3(PO4)3Cl phosphors with the apatite structure have been prepared via a Pechini-type sol-gel process. X-ray diffraction (XRD) and structure refinement, photoluminescence (PL) spectra, cathodoluminescence (CL) spectra, absolute quantum yield, as well as lifetimes were utilized to characterize samples. Under UV light excitation, the undoped Ca2Ba3(PO4)3Cl sample shows broad band photoluminescence centered near 480 nm after being reduced due to the defect structure. Eu(2+) and Ce(3+) ion doped Ca2Ba3(PO4)3Cl samples also show broad 5d → 4f transitions with cyan and blue colors and higher quantum yields (72% for Ca2Ba3(PO4)3Cl:0.04Eu(2+); 67% for Ca2Ba3(PO4)3Cl:0.016Ce(3+)). For Dy(3+) and Tb(3+) doped Ca2Ba3(PO4)3Cl samples, they give strong line emissions coming from 4f → 4f transitions. Moreover, the Ce(3+) ion can transfer its energy to the Tb(3+) ion in the Ca2Ba3(PO4)3Cl host, and the energy transfer mechanism has been demonstrated to be a resonant type, via a dipole-quadrupole interaction. However, under the low voltage electron beam excitation, Tb(3+) ion doped Ca2Ba3(PO4)3Cl samples present different luminescence properties compared with their PL spectra, which is ascribed to the different excitation mechanism. On the basis of the good PL and CL properties of the Ca2Ba3(PO4)3Cl:A (A = Ce(3+)/Eu(2+)/Tb(3+)/Dy(3+)), Ca2Ba3(PO4)3Cl might be promising for application in solid state lighting and field-emission displays.

  6. Effect of the cation size on the framework structures of magnesium tungstate, A4Mg(WO4)3 (A = Na, K), R2Mg2(WO4)3 (R = Rb, Cs).

    PubMed

    Han, Shujuan; Wang, Ying; Jing, Qun; Wu, Hongping; Pan, Shilie; Yang, Zhihua

    2015-03-28

    A series of alkali metal magnesium tungstates, A4Mg(WO4)3 (A = Na, K), R2Mg2(WO4)3 (R = Rb, Cs), were synthesized from a high temperature solution, and their structures were determined by single-crystal X-ray diffraction. Interestingly, Na4Mg(WO4)3 crystallizes in the monoclinic space group C2/c, while K4Mg(WO4)3 having an identical stoichiometry with Na4Mg(WO4)3, exhibits a different framework structure belonging to triclinic symmetry with the space group P1[combining macron]. Isostructural Rb2Mg2(WO4)3 and Cs2Mg2(WO4)3 crystallize in the space group P213 of cubic symmetry and reveal a three dimensional framework composed of isolated WO4 tetrahedra, MgO6 octahedra and RO12 (R = Rb, Cs) polyhedra. The effect of the alkali metal cation size on the framework structures of magnesium tungstate has been discussed in detail. In addition, the infrared spectra, as well as the UV-Vis-NIR diffuse reflectance spectroscopy data, are reported. The first-principles theoretical studies are also carried out to aid the understanding of electronic structures and linear optical properties.

  7. Synthesis of 2,3-trans-3,4-cis- and 2,3-trans-3,4-trans-2,3,4-triphenyltetrahydrofurans.

    PubMed

    Munshi, K L; Dikshit, D K; Kapil, R S; Anand, N

    1974-04-01

    The synthesis of 2,3-trans-3,4-cis- and 2,3-trans-3,4-trans-2,3,4-triphenyltetrahydrofurans was undertaken because these compounds incorportae the essential structural features of certain 2,3-diphenyl-benzofurans and 1,2,3-triphenylalkanones reported earlier to have marked antifertility activity. The synthesis of the 2 tetrahydrofurans was achieved by the cyclization of corresponding 2,3,4-triphenylbutane-1,4-diols upon heating with dimethyl sulfoxide (DMSO). The butane 1,4-diols were in turn prepared either by direct litium aluminum hydride (LAH) reduction of methyl 3-benzoyl-2,3-diphenylpropionates or by conversion of these propionates to delta-3,4-butryrolactones followed by LAH reduction. The propionates were prepared from the Fiedel-Crafts reaction of 2,3-diphenylsuccinic anhydride with benzene. Tetrahydrofurans were tested for their antiimplantation activity in rats. 2,3-trans-3,4-cis-2,4-diphenyl-3-p -(beta-pyrrolidinoethoxy) phenyltetrahydrofuran oxalate was found to inhibit implantation completely at 50 mg/kg, but was inefective at a lower dose.

  8. A novel open-framework with non-crossing channels in the uranyl vanadates A(UO 2) 4(VO 4) 3 ( A=Li, Na)

    NASA Astrophysics Data System (ADS)

    Obbade, S.; Dion, C.; Rivenet, M.; Saadi, M.; Abraham, F.

    2004-06-01

    A new sodium uranyl vanadate Na(UO 2) 4(VO 4) 3 has been synthesized by solid-state reaction and its structure determined from single-crystal X-ray diffraction data. It crystallizes in the tetragonal symmetry with space group I4 1/ amd and following cell parameters: a=7.2267(4) Å and c=34.079(4) Å, V=1779.8(2) Å 3, Z=4 with ρmes=5.36(3) g/cm 3 and ρcal=5.40(2) g/cm 3. A full-matrix least-squares refinement on the basis of F2 yielded R1=0.028 and w R2=0.056 for 52 parameters with 474 independent reflections with I⩾2 σ( I) collected on a BRUKER AXS diffractometer with Mo Kα radiation and a CCD detector. The crystal structure is characterized by ∞2[(UO 2) 2(VO 4)] sheets parallel to (001) formed by corner-shared UO 6 distorted octahedra and V(2)O 4 tetrahedra, connected by V(1)O 4 tetrahedra to ∞1[UO 5] 4- chains of edge-shared UO 7 pentagonal bipyramids alternately parallel to the a- and b-axis. The resulting three-dimensional framework creates mono-dimensional channels running down the a- and b-axis formed by face-shared oxygen octahedra half occupied by Na. The powder of Li analog compound Li(UO 2) 4(VO 4) 3 has been synthesized by solid-state reaction. The two compounds exhibit high mobility of the alkaline ions within the two-dimensional network of non-intersecting channels.

  9. 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

  10. Novel 1H-1,2,3-, 2H-1,2,3-, 1H-1,2,4- and 4H-1,2,4-triazole derivatives: a patent review (2008 - 2011).

    PubMed

    Ferreira, Vitor F; da Rocha, David R; da Silva, Fernando C; Ferreira, Patrícia G; Boechat, Núbia A; Magalhães, Jorge L

    2013-03-01

    The triazoles represent a class of five-membered heterocyclic compounds of great importance for the preparation of new drugs with diverse biological activities because they may present several structural variations with the same numbers of carbon and nitrogen atoms. Due to the success of various triazoles that entered the pharmaceutical market and are still being used in medicines, many companies and research groups have shown interest in developing new methods of synthesis and biological evaluation of potential uses for these compounds. In this review, the authors explored aspects of patents for the 1H-1,2,3-, 2H-1,2,3-, 1H-1,2,4- and 4H-1,2,4-triazole families, including prototypes being considered in clinical studies between 2008 and 2011. The triazoles have been studied for over a century as an important class of heterocyclic compounds and still attract considerable attention due to their broad range of biological activities. More recently, there has been considerable interest in the development of novel triazoles with anti-inflammatory, antiplatelet, antimicrobial, antimycobacterial, antitumoral and antiviral properties and activity against several neglected diseases. This review emphasizes recent perspective and advances in the therapeutically active 1H-1,2,3-, 2H-1,2,3-, 1H-1,2,4- and 4H-1,2,4-triazole derivative patents between 2008 and 2011, covering the development of new chemical entities and new pharmaceuticals. Many studies have focused on these compounds as target structures and evaluated them in several biological targets. The preparation of 1H-1,2,3-, 2H-1,2,3-, 1H-1,2,4- and 4H-1,2,4-triazole derivatives brings to light several issues. There is a need to find new, more efficient preparations for these triazoles that take into consideration current issues in green chemistry, energy saving and sustainability. New diseases are discovered and new viruses and bacteria continue to challenge mankind, so it is imperative to find new prototypes for these

  11. Synthesis and biological activity of pyrazolo[3,4-d]thiazolo[3,2-a]pyrimidin-4-one derivatives: in silico approach.

    PubMed

    Khobragade, Chandrahas N; Bodade, Ragini G; Dawane, Bhaskar S; Konda, Shankaraiah G; Khandare, Namdev T

    2010-10-01

    Xanthine oxidase (XO) is responsible for the pathological condition called gout. Inhibition of XO activity by various pyrazolo[3,4-d]thiazolo[3,2-a]pyrimidine-4-one derivatives was assessed and compared with the standard inhibitor allopurinol. Out of 10 synthesized compounds, two compounds, viz. 3-amino-6-(2-hydroxyphenyl)-1H-pyrazolo[3,4-d]thiazolo[3,2-a]pyrimidin-4-one (3b) and 3-amino-6-(4-chloro-2-hydroxy-5-methylphenyl)-1H-pyrazolo[3,4-d]thiazolo[3,2-a]pyrimidin-4-one (3g) were found to have promising XO inhibitory activity of the same order as allopurinol. Both compounds and allopurinol inhibited competitively with comparable Ki (3b: 3.56 microg, 3g: 2.337 microg, allopurinol: 1.816 microg) and IC(50) (3b: 4.228 microg, 3g: 3.1 microg, allopurinol: 2.9 microg) values. The enzyme-ligand interaction was studied by molecular docking using Autodock in BioMed Cache V. 6.1 software. The results revealed a significant dock score for 3b (-84.976 kcal/mol) and 3g (-90.921 kcal/mol) compared with allopurinol (-55.01 kcal/mol). The physiochemical properties and toxicity of the compounds were determined in silico using online computational tools. Overall, in vitro and in silico study revealed 3-amino-6-(4-chloro-2-hydroxy-5-methylphenyl)-1H-pyrazolo[3,4-d]thiazolo[3,2-a]pyrimidin-4-one (3g) as a potential lead compound for the design and development of XO inhibitors.

  12. Synthesis, structure and NMR characterization of a new monomeric aluminophosphate [ dl-Co(en) 3] 2[Al(HPO 4) 2(H 1.5PO 4) 2(H 2PO 4) 2](H 3PO 4) 4 containing four different types of monophosphates

    NASA Astrophysics Data System (ADS)

    Chen, Peng; Li, Jiyang; Xu, Jun; Duan, Fangzheng; Deng, Feng; Xu, Ruren

    2009-03-01

    A new zero-dimensional (0D) aluminophosphate monomer [ dl-Co(en) 3] 2[Al(HPO 4) 2(H 1.5PO 4) 2(H 2PO 4) 2](H 3PO 4) 4 (designated AlPO-CJ38) with Al/P ratio of 1/6 has been solvothermally prepared by using racemic cobalt complex dl-Co(en) 3Cl 3 as the template. The Al atom is octahedrally linked to six P atoms via bridging oxygen atoms, forming a unique [Al(HPO 4) 2(H 1.5PO 4) 2(H 2PO 4) 2] 6- monomer. Notably, there exists intramolecular symmetrical O⋯H⋯O bonds, which results in pseudo-4-rings stabilized by the strong H-bonding interactions. The structure is also featured by the existence of four different types of monophosphates that have been confirmed by 31P NMR and 1H NMR spectra. The crystal data are as follows: AlPO-CJ38, [ dl-Co(en) 3] 2[Al(HPO 4) 2(H 1.5PO 4) 2(H 2PO 4) 2](H 3PO 4) 4, M = 1476.33, monoclinic, C2/ c (No. 15), a = 36.028(7) Å, b = 8.9877(18) Å, c = 16.006(3) Å, β = 100.68(3)°, U = 5093.2(18) Å 3,Z = 4, R1 = 0.0509 ( I > 2 σ( I)) and wR2 = 0.1074 (all data). CCDC number 689491.

  13. Formation of a 1,4-diamino-2,3-disila-1,3-butadiene derivative.

    PubMed

    Mondal, Kartik Chandra; Roesky, Herbert W; Dittrich, Birger; Holzmann, Nicole; Hermann, Markus; Frenking, Gernot; Meents, Alke

    2013-10-30

    A 1,4-diamino-2,3-disila-1,3-butadiene derivative of composition (Me2-cAAC)2(Si2Cl2) (Me2-cAAC = :C(CMe2)2(CH2)N-2,6-iPr2C6H3) was synthesized by reduction of the Me2-cAAC:SiCl4 adduct with KC8. This compound is stable at 0 °C for 3 months in an inert atmosphere. Theoretical studies reveal that the silicon atoms exhibit pyramidal coordination, where the Cl-Si-Si-Cl dihedral angle is twisted by 43.3° (calcd 45.9°). The two silicon-carbon bonds are intermediates between single and double Si-C bonds due to twisting of the C-Si-Si-C dihedral angle (163.6°).

  14. Thermally stable compositions including 2,4,8,10-tetranitro-5H-pyrido[3',2':4,5][1,2,3]triazolo[1,2-a]benzotriazo- l-6-ium, inner salt

    DOEpatents

    Hiskey, Michael A.; Huynh, My Hang

    2010-01-26

    An explosive formulation including 2,4,8,10-tetranitro-5H-pyrido[3',2':4,5][1,2,3]triazolo[1,2-a]benzotriazo- l-6-ium, inner salt and a high temperature binder is disclosed together with a process of preparing 2,4,8,10-tetranitro-5H-pyrido[3',2':4,5][1,2,3]triazolo[1,2-a]benzotriazo- l-6-ium, inner salt.

  15. Hexafluoroisopropyl alcohol mediated synthesis of 2,3-dihydro-4H-pyrido[1,2-a]pyrimidin-4-ones.

    PubMed

    Alam, Mohammad A; Alsharif, Zakeyah; Alkhattabi, Hessa; Jones, Derika; Delancey, Evan; Gottsponer, Adam; Yang, Tianhong

    2016-11-02

    An efficient synthesis of novel 2,3-dihydro-4H-pyrido[1,2-a]pyrimidin-4-ones has been reported. Inexpensive and readily available substrates, environmentally benign reaction condition, and product formation up to quantitative yield are the key features of this methodology. Products are formed by the aza-Michael addition followed by intramolecular acyl substitution in a domino process. The polar nature and strong hydrogen bond donor capability of 1,1,1,3,3,3-hexafluoropropan-2-ol is pivotal in this cascade protocol.

  16. Hexafluoroisopropyl alcohol mediated synthesis of 2,3-dihydro-4H-pyrido[1,2-a]pyrimidin-4-ones

    PubMed Central

    Alam, Mohammad A.; Alsharif, Zakeyah; Alkhattabi, Hessa; Jones, Derika; Delancey, Evan; Gottsponer, Adam; Yang, Tianhong

    2016-01-01

    An efficient synthesis of novel 2,3-dihydro-4H-pyrido[1,2-a]pyrimidin-4-ones has been reported. Inexpensive and readily available substrates, environmentally benign reaction condition, and product formation up to quantitative yield are the key features of this methodology. Products are formed by the aza-Michael addition followed by intramolecular acyl substitution in a domino process. The polar nature and strong hydrogen bond donor capability of 1,1,1,3,3,3-hexafluoropropan-2-ol is pivotal in this cascade protocol. PMID:27805054

  17. A facile iodine(III)-mediated synthesis of 3-(3-aryl-1-phenyl-1H-pyrazol-4-yl)-[1,2,4]triazolo[4,3-a]pyridines via oxidation of 2-((3-aryl-1-phenyl-1H-pyrazol-4-yl)methylene)-1-(pyridin-2-yl)hydrazines and their antimicrobial evaluations

    PubMed Central

    2011-01-01

    Background Fused heterocyclic 1,2,4-triazoles have acquired much importance because of their interesting biological properties. Although a number of methods have been reported in the literature which includes oxidation with phosphorus oxychloride, lead tetraacetate, bromine, etc., hypervalent iodine reagents have emerged as reagents of choice for various synthetically useful transformations due to their low toxicity, ready availability and ease of handling. Results A series of new 3-(3-aryl-1-phenyl-1H-pyrazol-4-yl)-[1,2,4]triazolo[4,3-a]pyridines 4 has been conveniently synthesized by oxidative cyclization of 2-(3-aryl-1-phenyl-1H-pyrazol-4-yl)methylene)-1-(pyridin-2-yl)hydrazines 3 promoted with iodobenzene diacetate under mild conditions (up to 90% isolated yields). All the new compounds were tested in vitro for their antimicrobial activity. Conclusions Iodine(III)-mediated oxidative approach has offered an easy access to new 3-(3-aryl-1-phenyl-1H-pyrazol-4-yl)-[1,2,4]triazolo[4,3-a]pyridines 4. The antibacterial and antifungal activities of newly synthesized compounds have proved them potent antimicrobial agents. PMID:22373059

  18. (2R)-4-Oxo-4[3-(Trifluoromethyl)-5,6-diihydro:1,2,4}triazolo[4,3-a}pyrazin-7(8H)-y1]-1-(2,4,5-trifluorophenyl)butan-2-amine: A Potent, Orally Active Dipeptidyl Peptidase IV Inhibitor for the Treatment of Type 2 Diabetes

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

    Kim, D.; Wang, L.; Beconi, M.

    2010-11-10

    A novel series of {beta}-amino amides incorporating fused heterocycles, i.e., triazolopiperazines, were synthesized and evaluated as inhibitors of dipeptidyl peptidase IV (DPP-IV) for the treatment of type 2 diabetes. (2R)-4-Oxo-4-[3-(trifluoromethyl)-5,6-dihydro[1,2,4]triazolo[4,3-a]pyrazin-7(8H)-yl]-1-(2,4,5-trifluorophenyl)butan-2-amine (1) is a potent, orally active DPP-IV inhibitor (IC{sub 50} = 18 nM) with excellent selectivity over other proline-selective peptidases, oral bioavailability in preclinical species, and in vivo efficacy in animal models. MK-0431, the phosphate salt of compound 1, was selected for development as a potential new treatment for type 2 diabetes.

  19. Cs 2 Hg 3 S 4 : A Low-Dimensional Direct Bandgap Semiconductor

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

    Islam, Saiful M.; Vanishri, S.; Li, Hao

    2015-01-13

    Cs2Hg3S4 was synthesized by slowly cooling a melted stoichiometric mixture of Hg and Cs2S4. Cs2Hg3S4 crystallizes in the Ibam spacegroup with a = 6.278(1) angstrom, b = 11.601(2) angstrom, and c = 14.431(3)angstrom; d(calc) = 6.29 g/cm(3). Its crystal structure consists of straight chains of [Hg3S4](n)(2n-) that engage in side-by-side weak bonding interactions forming layers and are charge balanced by Cs+ cations. The thermal stability of this compound was investigated with differential thermal analysis and temperature dependent in situ synchrotron powder diffraction. The thermal expansion coefficients of the a, b, and c axes were assessed at 1.56 x 10(-5), 2.79more » x10(-5), and 3.04 x 10(-5) K-1, respectively. Large single-crystals up to similar to 5 cm in length and similar to 1 cm in diameter were grown using a vertical Bridgman method. Electrical conductivity and photoconductivity measurements on naturally cleaved crystals of Cs2Hg3S4 gave resistivity rho of >= 10(8) Omega.cm and carrier mobility-lifetime (mu tau) products of 4.2 x 10(-4) and 5.82 x 10(-5) cm(2) V-1 for electrons and holes, respectively. Cs2Hg3S4 is a semiconductor with a bandgap E-g similar to 2.8 eV and exhibits photoluminescence (PL) at low temperature. Electronic band structure calculations within the density functional theory (DFT) framework employing the nonlocal hybrid functional within Heyd-Scuseria-Ernzerhof (HSE) formalism indicate a direct bandgap of 2.81 eV at Gamma. The theoretical calculations show that the conduction band minimum has a highly dispersive and relatively isotropic mercury-based s-orbital-like character while the valence band maximum features a much less dispersive and more anisotropic sulfur orbital-based band.« less

  20. Cytotoxicity of chloroacetanilide herbicide alachlor in HepG2 cells independent of CYP3A4 and CYP3A7.

    PubMed

    Miranda, Sonia R; Meyer, Sharon A

    2007-05-01

    Alachlor is cytotoxic to human hepatoblastoma HepG2s, a cell line that expresses constitutive CYP3A7 and dexamethasone (DEX)-inducible CYP3A4 and CYP3A7. CYP3A4 catalyzes alachlor N-dealkylation to 2-chloro-N-(2,6-diethylphenyl)acetamide (CDEPA), precursor of 2,6-diethylbenzoquinoneimine, putative reactive metabolite for rat nasal carcinogenicity. We hypothesized that HepG2 alachlor cytotoxicity would be mediated by CYP3A4/7 and increased with DEX. Here, we report time-dependent alachlor cytotoxicity (EC(50) approximately 500 microM and 264+/-17 microM at 6 and 24h, respectively) as assessed by lactate dehydrogenase leakage. DEX pretreatment (25 microM, 48 h) significantly increased CYP3A7-catalyzed luciferin 6' benzylether O-debenzylation, but had no effect on alachlor toxicity. Further, CYP3A4/7 inhibitor triacetyloleandomycin did not prevent, but rather potentiated, alachlor cytotoxicity. In agreement, CDEPA was less toxic than parent alachlor. HepG2 CYP3A4 activity was unaffected by 48 h DEX pretreatment; therefore, studies were done in DPX-2 cells, a HepG2 derivative engineered to overexpress pregnane-X receptor (PXR) that exhibits rifampicin (RIF)-inducible endogenous CYP3A4. Alachlor cytotoxicity in DPX-2 cells occurred over a concentration range equivalent to that in HepG2. CYP3A4 activity of DPX-2 cells treated with RIF (10 microM, 48 h) was twice that of untreated cells, but RIF did not increase alachlor toxicity. These results demonstrate that neither CYP3A4 nor CYP3A7 initiate a pathway leading to a toxic alachlor metabolite.

  1. Vibrational spectroscopic (FT-IR, FT-Raman) and quantum mechanical study of 4-(2-chlorophenyl)-2-ethyl-9-methyl-6H-thieno[3,2-f] [1,2,4]triazolo[4,3-a][1,4] diazepine

    NASA Astrophysics Data System (ADS)

    Kuruvilla, Tintu K.; Prasana, Johanan Christian; Muthu, S.; George, Jacob

    2018-04-01

    The spectroscopic properties of 4-(2-chlorophenyl)-2-ethyl-9-methyl-6H-thieno [3,2-f] [1,2,4] triazolo [4,3-a] [1,4] diazepine were investigated in the present study using FT-IR and FT-Raman techniques. The results obtained were compared with quantum mechanical methods, as it serves as an important tool in interpreting and predicting vibrational spectra. The optimized molecular geometry, the vibrational wavenumbers, the infrared intensities and Raman scattering were calculated using density functional theory B3LYP method with 6-311++g (d,p) basis set. All the experimental results were in line with the theoretical data. The molecular electrostatic potential (MEP) and HOMO LUMO energies of the title compound were accounted. The results indicated that the title compound has a lower softness value (0.27) and high electrophilicity index (4.98) hence describing its biological activity. Further, natural bond orbital was also analyzed as part of the work. Fukui functions were calculated in order to explain the chemical selectivity or the reactivity site in 4-(2-chlorophenyl)-2-ethyl-9-methyl-6H-thieno [3,2-f] [1,2,4] triazolo [4,3-a] [1,4] diazepine. The thermodynamic properties of the title compound were closely examined at different temperatures. It revealed the correlations between heat capacity (C), entropy (S) and enthalpy changes (H) with temperatures. The paper further explains that the title compound can act as good antidepressant through molecular docking studies.

  2. CYP3A4 and CYP3A5 genotyping by Pyrosequencing

    PubMed Central

    Garsa, Adam A; McLeod, Howard L; Marsh, Sharon

    2005-01-01

    Background Human cytochrome P450 3A enzymes, particularly CYP3A4 and CYP3A5, play an important role in drug metabolism. CYP3A expression exhibits substantial interindividual variation, much of which may result from genetic variation. This study describes Pyrosequencing assays for key SNPs in CYP3A4 (CYP3A4*1B, CYP3A4*2, and CYP3A4*3) and CYP3A5 (CYP3A5*3C and CYP3A5*6). Methods Genotyping of 95 healthy European and 95 healthy African volunteers was performed using Pyrosequencing. Linkage disequilibrium, haplotype inference, Hardy-Weinberg equilibrium, and tag SNPs were also determined for these samples. Results CYP3A4*1B allele frequencies were 4% in Europeans and 82% in Africans. The CYP3A4*2 allele was found in neither population sample. CYP3A4*3 had an allele frequency of 2% in Europeans and 0% in Africans. The frequency of CYP3A5*3C was 94% in Europeans and 12% in Africans. No CYP3A5*6 variants were found in the European samples, but this allele had a frequency of 16% in the African samples. Allele frequencies and haplotypes show interethnic variation, highlighting the need to analyze clinically relevant SNPs and haplotypes in a variety of ethnic groups. Conclusion Pyrosequencing is a versatile technique that could improve the efficiency of SNP analysis for pharmacogenomic research with the ultimate goal of pre-screening patients for individual therapy selection. PMID:15882469

  3. Crystal structure of (2R*,3aR*)-2-phenyl-sulfonyl-2,3,3a,4,5,6-hexa-hydro-pyrrolo-[1,2-b]isoxazole.

    PubMed

    Hernández, Yaiza; Marcos, Isidro; Garrido, Narciso M; Sanz, Francisca; Diez, David

    2017-01-01

    The title compound, C 12 H 15 NO 3 S, was prepared by 1,3-dipolar cyclo-addition of 3,4-di-hydro-2 H -pyrrole 1-oxide and phenyl vinyl sulfone. In the mol-ecule, both fused five-membered rings display a twisted conformation. In the crystal, C-H⋯O hydrogen bonds link neighbouring mol-ecules, forming chains running parallel to the b axis.

  4. A series of substituted (2E)-3-(2-fluoro-4-phenoxyphenyl)-1-phenylprop-2-en-1-ones.

    PubMed

    Chopra, Deepak; Mohan, T P; Vishalakshi, B; Row, T N Guru

    2007-12-01

    In the molecular structures of a series of substituted chalcones, namely (2E)-3-(2-fluoro-4-phenoxyphenyl)-1-phenylprop-2-en-1-one, C21H15FO2, (I), (2E)-3-(2-fluoro-4-phenoxyphenyl)-1-(4-fluorophenyl)prop-2-en-1-one, C21H14F2O2, (II), (2E)-1-(4-chlorophenyl)-3-(2-fluoro-4-phenoxyphenyl)prop-2-en-1-one, C21H14ClFO2, (III), (2E)-3-(2-fluoro-4-phenoxyphenyl)-1-(4-methylphenyl)prop-2-en-1-one, C22H17FO2, (IV), and (2E)-3-(2-fluoro-4-phenoxyphenyl)-1-(4-methoxyphenyl)prop-2-en-1-one, C22H17FO3, (V), the configuration of the keto group with respect to the olefinic double bond is s-cis. The molecules pack utilizing weak C-H...O and C-H...pi intermolecular contacts. Identical packing motifs involving C-H...O interactions, forming both chains and dimers, along with C-H...pi dimers and pi-pi aromatic interactions are observed in the fluoro, chloro and methyl derivatives.

  5. Photoluminescence analysis of Ce3+:Zn2SiO4 & Li++ Ce3+:Zn2SiO4: phosphors by a sol-gel method

    NASA Astrophysics Data System (ADS)

    Babu, B. Chandra; Vandana, C. Sai; Guravamma, J.; Rudramadevi, B. Hemalatha; Buddhudu, S.

    2015-06-01

    Here, we report on the development and photoluminescence analysis of Zn2SiO4, Ce3+:Zn2SiO4 & Li+ + Ce3+: Zn2SiO4 novel powder phosphors prepared by a sol-gel technique. The total amount of Ce3+ ions was kept constant in this experiment at 0.05 mol% total doping. The excitation and emission spectra of undoped (Zn2SiO4) and Ce3+ doped Zn2SiO4 and 0.05 mol% Li+ co-doped samples have been investigated. Cerium doped Zn2SiO4 powder phosphors had broad blue emission corresponding to the 2D3/22FJ transition at 443nm. Stable green-yellow-red emission has been observed from Zn2SiO4 host matrix and also we have been observed the enhanced luminescence of Li+ co-doped Zn2SiO4:Ce3+. Excitation and emission spectra of these blue luminescent phosphors have been analyzed in evaluating their potential as luminescent screen coating phosphors.

  6. A synthesis of 4-hydroxy-2-trans-nonenal and 4-(3H) 4-hydroxy-2-trans-nonenal.

    PubMed

    Chandra, A; Srivastava, S K

    1997-07-01

    4-Hydroxy-2-trans-nonenal, the most abundant and toxic unsaturated aldehyde generated during membrane lipid peroxidation, was synthesized starting from fumaraldehyde dimethyl acetal. In the first step of the synthesis, the fumaraldehyde dimethyl acetal was partially hydrolyzed using amberlyst catalyst to obtain the monoacetal. The 4-hydroxy-2-trans-nonenal was synthesized by the Grignard reaction of the fumaraldehyde monoacetal with 1-bromopentane. 4-Hydroxy-2-trans-nonenal, obtained as its dimethylacetal, was oxidized to its corresponding 4-keto derivative using pyridinium chlorochromate buffered with sodium acetate as the oxidizing agent. 4-(3H) 4-Hydroxy-2-trans-nonenal was obtained in one step by the sodium borotriteride reduction of the 4-keto derivative.

  7. 3-nitro-1,2,4-triazol-5-one: A less sensitive explosive

    DOEpatents

    Lee, Kien-Yin; Coburn, M.D.

    1987-01-30

    A less sensitive explosive, 3-nitro-1,2,4-triazol-5-one. The compound 3-nitro--1,2,4-triazol-5-one (NTO) has a crystal density of 1.93 g/cm/sup 3/ and calculated detonation velocity and pressure equivalent to those of RDX. It can be prepared in high yield from inexpensive starting materials in a safe synthesis. Results from initial small-scale sensitivity tests indicate that NTO is less sensitive than RDX and HMX in all respects. A 4.13 cm diameter, unconfined plate-dent test at 92% of crystal density gave the detonation pressure predicted for NTO by the BKW calculation. 3 tabs.

  8. 3-nitro-1,2,4-triazol-5-one, a less sensitive explosive

    DOEpatents

    Lee, Kien-Yin; Coburn, Michael D.

    1988-01-01

    A less sensitive explosive, 3-nitro-1,2,4-triazol-5-one. The compound 3-nitro-1,2,4-triazol-5-one (NTO) has a crystal density of 1.93 g/cm.sup.3 and calculated detonation velocity and pressure equivalent to those of RDX. It can be prepared in high yield from inexpensive starting materials in a safe synthesis. Results from initial small-scale sensitivity tests indicate that NTO is less sensitive than RDX and HMX in all respects. A 4.13 cm diameter, unconfined plate-dent test at 92% of crystal density gave the detonation pressure predicted for NTO by the BKW calculation.

  9. Color-tunable and white luminescence properties via energy transfer in single-phase KNaCa2(PO4)2:A (A = Ce3+, Eu2+, Tb3+, Mn2+, Sm3+) phosphors.

    PubMed

    Geng, Dongling; Shang, Mengmeng; Zhang, Yang; Lian, Hongzhou; Lin, Jun

    2013-12-02

    A series of single-phase phosphors based on KNaCa2(PO4)2 (KNCP):A (A = Ce(3+), Eu(2+), Tb(3+), Mn(2+), Sm(3+)) have been prepared via the Pechini-type sol-gel method. Photoluminescence (PL) and cathodoluminescence (CL) properties of Ce(3+)-, Eu(2+)-, Tb(3+)-, Mn(2+)-, and Sm(3+)-activated KNCP phosphors were investigated. For the A singly doped KNCP samples, they exhibit the characteristic emissions of the A activator. Na(+) ions exhibit the best charge compensation result among Li(+), Na(+), and K(+) ions for Ce(3+)-, Tb(3+)-, and Sm(3+)-doped KNCP samples. The energy transfers from Ce(3+) to Tb(3+) and Mn(2+) ions as well as Eu(2+) to Tb(3+) and Mn(2+) have been validated. The emission colors of KNCP:Ce(3+)/Eu(2+), Tb(3+)/Mn(2+), Na(+) samples can be adjusted by energy transfer process and changing the Tb(3+)/Mn(2+) concentration. More importantly, white light emission in KNCP:Eu(2+), Mn(2+) system has been obtained. The KNCP:Tb(3+), Na(+) sample shows tunable luminescence from blue to cyan and then to green with the change of Tb(3+) concentration due to the cross-relaxation from (5)D3 to (5)D4. A white emission can also be realized in the single-phase KNCP host by reasonably adjusting the doping concentrations of Tb(3+) and Sm(3+) (reddish-orange emission) under low-voltage electron beam excitation. Additionally, the temperature-dependent PL properties of as-prepared phosphors reveal that the KNCP host has good thermal stability. Therefore, the KNCP:A (A = Ce(3+), Eu(2+), Tb(3+), Mn(2+), Sm(3+)) phosphors could be regarded as good candidates for UV W-LEDs and FEDs.

  10. Refined Synthesis of 2,3,4,5-Tetrahydro-1,3,3-trimethyldipyrrin, a Deceptively Simple Precursor to Hydroporphyrins

    PubMed Central

    Ptaszek, Marcin; Bhaumik, Jayeeta; Kim, Han-Je; Taniguchi, Masahiko; Lindsey, Jonathan S.

    2008-01-01

    2,3,4,5-Tetrahydro-1,3,3-trimethyldipyrrin (1) is a crucial building block in the rational synthesis of chlorins and oxochlorins. The prior 5-step synthesis of 1 from pyrrole-2-carboxaldehyde (2) employed relatively simple and well-known reactions yet suffered from several drawbacks, including limited scale (≥ 0.5 g of 1 per run). A streamlined preparation of 1 has been developed that entails four steps: (i) nitro-aldol condensation of 2 and nitromethane under neat conditions to give 2-(2-nitrovinyl)pyrrole (3), (ii) reduction of 3 with NaBH4 to give 2-(2-nitroethyl)pyrrole (4), (iii) Michael addition of 4 with mesityl oxide under neat conditions or at high concentration to give γ-nitrohexanonepyrrole 5, and (iv) reductive cyclization of 5 with zinc/ammonium formate to give 1. Several multistep transformations have been established, including the direct conversion of 2 → 1. The advantages of the new procedures include (1) fewer steps, (2) avoidance of several problematic reagents, (3) diminished consumption of solvents and reagents, (4) lessened reliance on chromatography, and (5) scalability. The new procedures facilitate the preparation of 1 at the multigram scale. PMID:19132135

  11. (3,3-Difluoro-pyrrolidin-1-yl)-[(2S,4S)-(4-(4-pyrimidin-2-yl-piperazin-1-yl)-pyrrolidin-2-yl]-methanone: A potent, selective, orally active dipeptidyl peptidase IV inhibitor

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

    Ammirati, Mark J.; Andrews, Kim M.; Boyer, David D.

    2010-10-01

    A series of 4-substituted proline amides was synthesized and evaluated as inhibitors of dipeptidyl pepdidase IV for the treatment of type 2 diabetes. (3,3-Difluoro-pyrrolidin-1-yl)-[(2S,4S)-(4-(4-pyrimidin-2-yl-piperazin-1-yl)-pyrrolidin-2-yl]-methanone (5) emerged as a potent (IC{sub 50} = 13 nM) and selective compound, with high oral bioavailability in preclinical species and low plasma protein binding. Compound 5, PF-00734200, was selected for development as a potential new treatment for type 2 diabetes.

  12. 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.

  13. A novel synthesis of octahydropyrido[3,2-c]carbazole framework of aspidospermidine alkaloids and a combined computational, FT-IR, NMR, NBO, NLO, FMO, MEP study of the cis-4a-Ethyl-1-(2hydroxyethyl)-2,3,4,4a,5,6,7,11c-octahydro-1H-pyrido[3,2-c]carbazole

    NASA Astrophysics Data System (ADS)

    Uludağ, Nesimi; Serdaroğlu, Goncagul; Yinanc, Abdullah

    2018-06-01

    In this study, we performed a novel synthesis of the octahydropyrido[3,2-c]carbazole derivative 6 from 1 in five steps with a 34% overall yield. We also developed a unique compound 2 by a cyclization reaction from the cyanoethylation of compound 1, which is an intermediate step in the synthesis of Aspidospermidine. The parent compound of Aspidospermidine alkaloids, comprise a large family of diverse structures. As a result, we obtained octahydropyrido[3,2-c]carbazole (6)and the proposed method may be applicable to other alkaloids. All quantum chemical calculations of the cis-4a-Ethyl-1-(2-hydroxyethyl)-2,3,4,4a,5,6,7,11c-octahydro-1H-pyrido[3,2-c]carbazole have been performed with the DFT/B3LYP and HF methods by using the Gaussian 09W software package. The most stable conformer obtained from the Potential Energy Surface (PES) scan analysis at the B3LYP/6-31G** level of theory in the gas phase was used as the starting structure of the title compound to further computational analysis. The Natural Bond Orbital (NBO) and NLO analyses were performed to evaluate the intra-molecular interactions contributing to the molecular stability and to predict the optical properties of the title compound, respectively. Gauge-Independent Atomic Orbital (GIAO) approach was used to determine the 1H and 1C NMR chemical shifts of the title compound by subtracting the shielding constants of TMS at both methods. The calculated vibrational frequencies of the title compound were assigned by using the VEDA program and were scaled down by using the scaling factor 0.9668 for B3LYP/6-311++G(d, p) and 0.9050 for HF/6-311++G(d, p) to improve the calculated vibrational frequencies. The FMO (frontier molecular orbital) analysis was evaluated to predict the chemical and physical properties of the title compound and the HOMO, LUMO, and MEP diagrams were visualized by GaussView 4.1 program to present the reactive site of the title compound.

  14. Metabolism of the insecticidally active GABA sub A receptor antagonist 4-sec-(3,4- sup 3 H sub 2 )butyl-1-(4-cyanophenyl)-2,6,7-trioxabicyclo(2. 2. 2)octane

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

    Deng, Yanli; Palmer, C.J.; Toia, R.F.

    1990-03-01

    4-sec-(3,4-{sup 3}H{sub 2})Butyl-1-(4-cyanophenyl)-2,6,7-trioxabicyclo(2.2.2)octane (referred to as ({sup 3}H)COB) was examined as an example of a new class of insecticidally active compounds that block the {gamma}-aminobutyric acid gated chloride channel. Metabolites were identified by thin-layer cochromatography with standards from synthesis and by consideration of their hydrolytic and oxidative degradation products formed in situ on two-dimensional silica gel chromatoplates. Metabolism of ({sup 3}H)COB by mouse liver and housefly abdomen microsomes is dependent on fortification with NADPH. The O-methylene and sec-butyl sites are sensitive to oxidation. Each carbon of the sec-butyl group is individually functionalized with strong preference for the methylene site inmore » the mouse but not the housefly microsomal system. O-Methylene hydroxylation initiates spontaneous cage opening to form an aldehyde that undergoes metabolic reduction, ultimately yielding the same cyanobenzoate ester of 2,2-bis-(hydroxymethyl)-3-methylpentan-1-ol formed by direct hydrolysis. Houseflies injected with ({sup 3}H)COB form many if not all of the same metabolites, with major products being the aforementioned cyanobenzoate, the orthoester oxidized at the sec-butyl methylene site, and polar conjugates.« less

  15. A Reappraisal of the 4/3/2 Activity

    ERIC Educational Resources Information Center

    Boers, Frank

    2014-01-01

    In the 4/3/2 activity learners deliver the same talk three times under increasing time pressure. The activity is intended first and foremost to foster fluency, but accuracy and complexity have also been said to benefit from this activity. The present study investigates whether immediate repetition of monologues under increasing time pressure…

  16. Fourier Transform Emission Spectroscopy of the [7.3] 2Δ- a2Φ and [9.4] 2Φ- a2Φ Systems of ZrCl

    NASA Astrophysics Data System (ADS)

    Ram, R. S.; Bernath, P. F.

    1999-08-01

    The emission spectrum of ZrCl has been observed in the 1800-12 000 cm-1 region using a Fourier transform spectrometer. The molecules were excited in a microwave discharge of a mixture of helium and a trace of ZrCl4 vapor. In addition to the C4Δ-X4Φ transition reported previously, numerous new bands observed in the near infrared have been classified into two electronic transitions, [7.3]2Δ-a2Φ and [9.4]2Φ-a2Φ. Five new bands observed in the 6700-7400 cm-1 region have been assigned as 2Δ3/2-2Φ5/2 and 2Δ5/2-2Φ7/2 subbands of a new electronic transition, [7.3]2Δ-a2Φ. The two subbands of the [9.4]2Φ-a2Φ transition were previously observed by G. Phillips, S. P. Davis, and D. C. Galehouse [Astrophys. J. Suppl. 43, 417-434 (1980)], who tentatively labeled them as 2Π1/2-2Π1/2 and 2Π3/2-2Π3/2 subbands. A number of new bands involving higher vibrational levels have been identified for these two subbands. A rotational analysis of a number of bands of both transitions has been obtained and spectroscopic constants have been determined. Global perturbations have been observed in both spin components of the a2Φ state. The assignment of the observed electronic states has been discussed in light of recent theoretical calculations.

  17. 2,3-Dihydro-2,5-dihydroxy-4H-benzopyran-4-one: a nonphysiological substrate for fungal melanin biosynthetic enzymes.

    PubMed

    Thompson, J E; Basarab, G S; Pierce, J; Hodge, C N; Jordan, D B

    1998-02-01

    We have synthesized an alternate substrate for trihydroxynaphthalene reductase (3HNR) and scytalone dehydratase (SD), two enzymes in the fungal melanin biosynthetic pathway. The oxidation of 2,3-dihydro-2,5-dihydroxy-4H-benzopyran-4-one (DDBO) to 4,5-dihydroxy-2H-benzopyran-2-one (DBO) with concomitant reduction of NADP+ is catalyzed by 3HNR. DDBO is dehydrated by SD to 5-hydroxy-4H-1-benzopyran-4-one (HBO). These reactions can be monitored using continuous spectrophotometric assays. DDBO race-mizes rapidly, so chiral synthesis to mimic the natural substrate is not required. DDBO, DBO, and HBO are stable in aerated aqueous solution, in contrast to the rapidly autooxidizing trihydroxynaphthalene, a physiological substrate for 3HNR and product of SD. Unlike the natural substrates, DDBO, DBO, and HBO do not change protonation state between pH's 4 and 9. Oxidation of DDBO is effectively irreversible at pH 7, as DBO deprotonates with a pKa of 2.5. At pH 7.0 and 25 degrees C, the kcat for 3HNR catalyzed DDBO oxidation is 14 s-1 and the K(m) is 5 microM; the kcat for SD catalyzed DDBO dehydration is 400 s-1 and the K(m) is 15 microM. Based on these kinetic constants, DDBO is a better substrate than the natural substrate scytalone for both 3HNR and SD at neutral pH. An explanation for the preference of DDBO over scytalone in the oxidation and dehydration reactions is offered.

  18. 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

  19. 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.

  20. Enterovirus inhibitory activity of C-8-tert-butyl substituted 4-aryl-6,7,8,9-tetrahydrobenzo[4,5]thieno[3,2-e][1,2,4]triazolo[4,3-a]pyrimidin-5(4H)-ones.

    PubMed

    Kumar Biswas, Bishyajit; Malpani, Yashwardhan R; Ha, Neul; Kwon, Do-Hyun; Soo Shin, Jin; Kim, Hae-Soo; Kim, Chonsaeng; Bong Han, Soo; Lee, Chong-Kyo; Jung, Young-Sik

    2017-08-01

    Members of a series of 4-aryl-6,7,8,9-tetrahydrobenzo[4,5]thieno[3,2-e][1,2,4]triazolo[4,3-a]pyrimidin-5(4H)-ones (1, Fig. 2) were prepared and tested against representative enteroviruses including Human Coxsackievirus B1 (Cox B1), Human Coxsackievirus B3 (Cox B3), human Poliovirus 3 (PV3), human Rhinovirus 14 (HRV14), human Rhinovirus 21 (HRV 21) and human Rhinovirus 71 (HRV 71). The C-8-tert-butyl group on the tetrahydrobenzene ring in these substances was found to be crucial for their enterovirus activity. One member of this group, 1e, showed single digit micromolar activities (1.6-8.85μM) against a spectrum of viruses screened, and the highest selectivity index (SI) values for Cox B1 (>11.2), for Cox B3 (>11.5), and for PV3 (>51.2), respectively. In contrast, 1p, was the most active analog against the selected HRVs (1.8-2.6μM), and showed the highest selectivity indices among the group of compounds tested. The SI values for 1p were 11.5 for HRV14, 8.4 for HRV21, and 12.1 for HRV71, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Gold-catalyzed sequential annulations towards 3,4-fused bi/tri-cyclic furans involving a [3+2+2]-cycloaddition.

    PubMed

    Liu, Suna; Yang, Pu; Peng, Shiyong; Zhu, Chenghao; Cao, Shengyu; Li, Jian; Sun, Jiangtao

    2017-01-17

    A gold-catalyzed sequential annulation reaction to prepare 3,4-fused bicyclic furan compounds has been realized by employing 2-(1-alkynyl)-2-alken-1-ones and 1,3,5-triazines as the starting materials under mild reaction conditions. This protocol features multiple bond formation in a single operation with the incorporation of two nitrogen and two carbon atoms into the final products. A mechanistic investigation reveals that the sequential annulations involved an unprecedented stepwise [3+2+2]-cycloaddition.

  2. A Palladium-Catalyzed Method for the Synthesis of 2-(α-Styryl)-2,3-dihydroquinazolin-4-ones and 3-(α-Styryl)-3,4-dihydro-1,2,4-benzothiadiazine-1,1-dioxide: Access to 2-(α-Styryl)quinazolin-4(3H)-ones and 3-(α-Styryl)-1,2,4-benzothiadiazine-1,1-dioxides.

    PubMed

    Kundu, Priyanka; Mondal, Amrita; Chowdhury, Chinmay

    2016-08-05

    An efficient synthesis of 2-(α-styryl)-2,3-dihydroquinazolin-4-ones and 3-(α-styryl)-3,4-dihydro-1,2,4-benzothiadiazine-1,1-dioxides has been achieved in 39-94% yield through palladium-catalyzed cyclocondensation of aryl/vinyl iodides with allenamides 13-15 and 22, respectively. Base treatment of the N-tosylated products provides an easy access to 2-(α-styryl)quinazolin-4(3H)-ones and 3-(α-styryl)-1,2,4-benzothiadiazine-1,1-dioxides, hitherto unknown heterocycles. The method has been tested with phenyl substituted allenamides, applied for bis-heteroannulation, and used in the preparation of analogues of the natural product Luotonin F.

  3. Luminescence Properties of Ca19Ce(PO4)14:A (A = Eu3+/Tb3+/Mn2+) Phosphors with Abundant Colors: Abnormal Coexistence of Ce4+/3+-Eu3+ and Energy Transfer of Ce3+ → Tb3+/Mn2+ and Tb3+-Mn2.

    PubMed

    Shang, Mengmeng; Liang, Sisi; Lian, Hongzhou; Lin, Jun

    2017-06-05

    A series of Eu 3+ /Tb 3+ /Mn 2+ -ion-doped Ca 19 Ce(PO 4 ) 14 (CCPO) phosphors have been prepared via the conventional high-temperature solid-state reaction process. Under UV radiation, the CCPO host presents a broad blue emission band from Ce 3+ ions, which are generated during the preparation process because of the formation of deficiency. The Eu 3+ -doped CCPO phosphors can exhibit magenta to red-orange emission as a result of the abnormal coexistence of Ce 3+ /Ce 4+ /Eu 3+ and the metal-metal charge-transfer (MMCT) effect between Ce 3+ and Eu 3+ . When Tb 3+ /Mn 2+ are doped into the hosts, the samples excited with 300 nm UV light present multicolor emissions due to energy transfer (ET) from the host (Ce 3+ ) to the activators with increasing activator concentrations. The emitting colors of CCPO:Tb 3+ phosphors can be tuned from blue to green, and the CCPO:Mn 2+ phosphors can emit red light. The ET mechanism from the host (Ce 3+ ) to Tb 3+ /Mn 2+ is demonstrated to be a dipole-quadrapole interaction for Ce 3+ → Tb 3+ and an exchange interaction for Ce 3+ → Mn 2+ in CCPO:Tb 3+ /Mn 2+ . Abundant emission colors containing white emission were obtained in the Tb 3+ - and Mn 2+ -codoped CCPO phosphors through control of the levels of doped Tb 3+ and Mn 2+ ions. The white-emitted CCPO:Tb 3+ /Mn 2+ phosphor exhibited excellent thermal stability. The photoluminescence properties have shown that these materials might have potential for UV-pumped white-light-emitting diodes.

  4. 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

  5. Toxicity and tissue distribution of 2,2',4,4'- and 3,3',4, 4'-tetrachlorobiphenyls in houseflies.

    PubMed

    Saghir, S A; Hansen, L G

    1999-02-01

    Insects selectively retain different polychlorinated biphenyls (PCBs) which are then contributed to the food chain. To quantitate specific differences, adult female houseflies (Musca domestica L.) were topically dosed with 0.5 microgram of two structurally distinct PCB congeners (14C-2,2',4,4'-tetraCB or 14C-3,3',4,4'-tetraCB). Total radioactivity in the acetone rinse of intact flies, several tissues, and excrement was determined at 11 time points over a 48-h period. Ninety-seven percent of the applied 2,2',4,4'-tetraCB disappeared from the surface following an initial rapid absorption of 79% within 3 h. The absorbed 2,2',4,4'-tetraCB was immediately found within the thoracic cuticle, then spreading laterally to the abdominal cuticle and head, through the wax layers, or penetrating to the alimentary canal and ovaries. Penetration of 3,3',4, 4'-tetraCB was markedly slower; even though 87% of the applied dose was absorbed within 48 h, only 19% of the dose penetrated into the fly body within the first 3 h. This PCB very slowly distributed into the tissues. Toxicities of the sublethal doses were determined by monitoring changes in activity of houseflies following dosing with 0. 5 microg of radioactive PCBs. Flies treated with 2,2',5-triCB and 3, 3',4,4'-tetraCB remained very active, whereas 2,2',4, 4'-tetraCB-treated flies were less active, consistent with the previously reported toxicity of this congener. Copyright 1999 Academic Press.

  6. Boric acid increases the expression levels of human anion exchanger genes SLC4A2 and SLC4A3.

    PubMed

    Akbas, F; Aydin, Z

    2012-04-03

    Boron is an important micronutrient in plants and animals. The role of boron in living systems includes coordinated regulation of gene expression, growth and proliferation of higher plants and animals. There are several well-defined genes associated with boron transportation and tolerance in plants and these genes show close homology with human anion exchanger genes. Mutation of these genes also characterizes some genetic disorders. We investigated the toxic effects of boric acid on HEK293 cells and mRNA expression of anion exchanger (SLC4A1, SLC4A2 and SLC4A3) genes. Cytotoxicity of boric acid at different concentrations was tested by using the methylthiazolyldiphenyl-tetrazolium bromide assay. Gene expression profiles were examined using quantitative real-time PCR. In the HEK293 cells, the nontoxic upper concentration of boric acid was 250 μM; more than 500 μM caused cytotoxicity. The 250 μM boric acid concentration increased gene expression level of SLC4A2 up to 8.6-fold and SLC4A3 up to 2.6-fold, after 36-h incubation. There was no significant effect of boric acid on SLC4A1 mRNA expression levels.

  7. 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)24H2O. 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).

  8. 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.

  9. 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.

  10. 47 CFR 80.1093 - Ship radio equipment-Sea areas A1, A2, A3, and A4.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 47 Telecommunication 5 2014-10-01 2014-10-01 false Ship radio equipment-Sea areas A1, A2, A3, and A4. 80.1093 Section 80.1093 Telecommunication FEDERAL COMMUNICATIONS COMMISSION (CONTINUED) SAFETY AND SPECIAL RADIO SERVICES STATIONS IN THE MARITIME SERVICES Global Maritime Distress and Safety...

  11. 47 CFR 80.1093 - Ship radio equipment-Sea areas A1, A2, A3, and A4.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 47 Telecommunication 5 2011-10-01 2011-10-01 false Ship radio equipment-Sea areas A1, A2, A3, and A4. 80.1093 Section 80.1093 Telecommunication FEDERAL COMMUNICATIONS COMMISSION (CONTINUED) SAFETY AND SPECIAL RADIO SERVICES STATIONS IN THE MARITIME SERVICES Global Maritime Distress and Safety...

  12. 47 CFR 80.1093 - Ship radio equipment-Sea areas A1, A2, A3, and A4.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 47 Telecommunication 5 2012-10-01 2012-10-01 false Ship radio equipment-Sea areas A1, A2, A3, and A4. 80.1093 Section 80.1093 Telecommunication FEDERAL COMMUNICATIONS COMMISSION (CONTINUED) SAFETY AND SPECIAL RADIO SERVICES STATIONS IN THE MARITIME SERVICES Global Maritime Distress and Safety...

  13. 47 CFR 80.1093 - Ship radio equipment-Sea areas A1, A2, A3, and A4.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 47 Telecommunication 5 2013-10-01 2013-10-01 false Ship radio equipment-Sea areas A1, A2, A3, and A4. 80.1093 Section 80.1093 Telecommunication FEDERAL COMMUNICATIONS COMMISSION (CONTINUED) SAFETY AND SPECIAL RADIO SERVICES STATIONS IN THE MARITIME SERVICES Global Maritime Distress and Safety...

  14. Production of 2,3-butanediol by a low-acid producing Klebsiella oxytoca NBRF4.

    PubMed

    Han, Sung-Hyuk; Lee, Jung-Eun; Park, Kyungmoon; Park, Yong-Cheol

    2013-01-25

    2,3-Butanediol (2,3-BDO) is a value-added chemical with great potential for the industrial production of synthetic rubber, plastic and solvent. For microbial production of 2,3-BDO, in this study, Klebsiella oxytoca NBRF4 was constructed by chemical mutation and screening against NaBr, NaBrO(3) and fluoroacetate. Among metabolic enzymes involved in the production of lactate, acetate and 2,3-BDO, K. oxytoca NBRF4 possessed 1.2 times lower specific activities of lactate dehydrogenase and phosphotransacetylase, and 22% higher specific acetoin reductase activity than the K. oxytoca ATCC43863 control strain. A series of batch fermentations in a defined medium and application of a statistical tool of response surface method led to the determination of optimal culture conditions: 10% dissolved oxygen level, pH 4.3 and 38°C. The actual results of batch fermentation at the optimal conditions using 44 g/L glucose were coincident with the predetermined values: 14.4 g/L 2,3-BDO concentration, 0.32 g/g yield. To increase 2,3-BDO titer, fed-batch fermentation of K. oxytoca NBRF4 was performed by an intermittent feeding of 800 g/L glucose to control its concentration around 5-20 g/L in the culture broth. Finally, 34.2g/L 2,3-BDO concentration and 0.35 g/g yield were obtained without organic acid production in 70 hours of the fed-batch culture, which were 2.4 and 1.2 times higher than those of the batch fermentation using 44 g/L glucose. Copyright © 2012 Elsevier B.V. All rights reserved.

  15. Bobjonesite, V4+ O (SO4) (H2O 3, a new mineral species from Temple Mountain, Emery County, Utah, U.S.A

    USGS Publications Warehouse

    Schindler, M.; Hawthorne, F.C.; Huminicki, D.M.C.; Haynes, P.; Grice, Joel D.; Evans, H.T.

    2003-01-01

    Bobjonesite, V4+ O (SO4) (H2O 3, is a new mineral species from Temple Mountain, Emery County, Utah, U.S.A. It occurs as blue-green crusts and efflorescences in fractures in a fossil (Triassic) tree: individual crystals are ??1 mm and are intimately intergrown. Bobjonesite hydrates very easily, and is unstable in all but the driest atmosphere. Its structure was determined on a crystal of bobjonesite: however, the physical properties, optical properties and X-ray powder-diffraction pattern were recorded on the synthetic equivalent, and an electron-microprobe analysis was not possible. Bobjonesite has a pale blue streak, a vitreous luster and no observable fluorescence under ultraviolet light. It has no cleavage or parting. The Mohs hardness is ???1, and the calculated density is 2.28 g/cm3. Bobjonesite is biaxial positive, with ?? 1.555(2 , ?? 1.561(1), ?? 1.574(2), 2V(obs.) = 72(1)??, 2V(calc.) = 69??; it is non-pleochroic, X = b, Y ??? 19?? (in ?? obtuse). Bobjonesite is monoclinic, space group P21/n, cell dimensions from single-crystal data: a 7.3940(5), b 7.4111(3), c 12.0597(9) A??, ?? 106.55(1)??, V 633.5(1) A??3, Z=4. The strongest seven lines in the X-ray powder-diffraction pattern [d in A??(I)(hkl)] are as follows: 5.795(100)(002), 3.498(90)(112), 3.881(48)(1??03), 5.408(37) (101), 4.571(20)(012), 6.962(11 (1??01) and 6.254(11)(011). The chemical formula was derived from crystal-structure analysis; the end-member formula is V O (SO4) (H2O)3. The crystal structure of bobjonesite was refined to an R index of 3.6% for 1105 observed (Fo> 5??F) reflections measured with an automated four-circle X-ray diffractometer using MoK?? X-radiation. There is one V site occupied by V4+ and surrounded by three O atoms and three (H2O) groups in an octahedral arrangement, with one short vanadyl bond (1.577 A??), four similar equatorial bonds (<2.022 A??), and one longer V-O bond (2.278 A??) trans to the vanadyl bond. The structure consists of isolated [V4+2 O2 (H2O)6 (SO4)2

  16. Growth and characterization of a Li2Mg2(MoO4)3 scintillating bolometer

    NASA Astrophysics Data System (ADS)

    Danevich, F. A.; Degoda, V. Ya.; Dulger, L. L.; Dumoulin, L.; Giuliani, A.; de Marcillac, P.; Marnieros, S.; Nones, C.; Novati, V.; Olivieri, E.; Pavlyuk, A. A.; Poda, D. V.; Trifonov, V. A.; Yushina, I. V.; Zolotarova, A. S.

    2018-05-01

    Lithium magnesium molybdate (Li2Mg2(MoO4)3) crystals were grown by the low-thermal-gradient Czochralski method. Luminescence properties of the material (emission spectra, thermally stimulated luminescence, dependence of intensity on temperature, phosphorescence) have been studied under X-ray excitation in the temperature interval from 8 to 400 K, while at the same being operated as a scintillating bolometer at 20 mK for the first time. We demonstrated that Li2Mg2(MoO4)3 crystals are a potentially promising detector material to search for neutrinoless double beta decay of 100Mo.

  17. 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

  18. A Case of 3,4-Dimethoxyamphetamine (3,4-DMA) and 3,4-Methylenedioxymethamphetamine (MDMA) Toxicity with Possible Metabolic Interaction.

    PubMed

    Darracq, Michael A; Thornton, Stephen L; Minns, Alicia B; Gerona, Roy R

    2016-01-01

    We present a case of "ecstasy" ingestion revealing 3,4-methylenedioxymethamphetamine (MDMA) and 3,4-dimethoxyamphetamine (3,4-DMA) and absence of cytochrome P450 (CYP)-2D6 MDMA metabolites. A 19-year-old presented following a seizure. Initial vital signs were normal. Laboratories were normal with the exception of sodium 127 mEq/L and urine drugs of abuse screen positive for amphetamines. Twelve hours later, serum sodium was 114 mEq/L and a second seizure occurred. After receiving hypertonic saline (3%), the patient had improvement in mental status and admitted to taking "ecstasy" at a rave prior to her initial presentation. Liquid chromatography-time-of-flight mass spectrometry (LC-TOF/MS) of serum and urine revealed MDMA, 3,4-DMA, and the CYP-2B6 MDMA metabolites 3,4-methylendioxyamphetamine (MDA) and 4-hydroxy-3-methoxyamphetamine (HMA). The CYP2D6 metabolites of MDMA, 3,4-dihydromethamphetamine (HHMA) and 4-hydroxy-3-methoxymethamphetamine (HMMA), were detected at very low levels. This case highlights the polypharmacy which may exist among users of psychoactive illicit substances and demonstrates that concurrent use of MDMA and 3,4-DMA may predispose patients to severe toxicity. Toxicologists and other healthcare providers should be aware of this potential toxicity.

  19. A promising tritium breeding material: Nanostructured 2Li2TiO3-Li4SiO4 biphasic ceramic pebbles

    NASA Astrophysics Data System (ADS)

    Dang, Chen; Yang, Mao; Gong, Yichao; Feng, Lan; Wang, Hailiang; Shi, Yanli; Shi, Qiwu; Qi, Jianqi; Lu, Tiecheng

    2018-03-01

    As an advanced tritium breeder material for the fusion reactor blanket of the International Thermonuclear Experimental Reactor (ITER), Li2TiO3-Li4SiO4 biphasic ceramic has attracted widely attention due to its merits. In this paper, the uniform precursor powders were prepared by hydrothermal method, and nanostructured 2Li2TiO3-Li4SiO4 biphasic ceramic pebbles were fabricated by an indirect wet method at the first time. In addition, the composition dependence (x/y) of their microstructure characteristics and mechanical properties were investigated. The results indicated that the crush load of biphasic ceramic pebbles was better than that of single phase ceramic pebbles under identical conditions. The 2Li2TiO3-Li4SiO4 ceramic pebbles have good morphology, small grain size (90 nm), satisfactory crush load (37.8 N) and relative density (81.8 %T.D.), which could be a promising breeding material in the future fusion reactor.

  20. Stereoselective synthesis of ( E)-4-(imidazo[1,2- a]pyrid-2-yl)-3-(4-methylphenylsulfonyl)but-3-en-2-one. X-ray crystal structure and conformational analysis

    NASA Astrophysics Data System (ADS)

    Roche, D.; Force, L.; Carpy, A.; Gardette, D.; Madesclaire, M.

    1998-06-01

    The title compound, gem-ketovinylsulfone 3, was obtained stereoselectively (de > 98%) by the action of the α-anion from p-tolylsulfonylacetone 1 on imidazol[1,2- a]pyridine-2-carbaldehyde 2 in chelation-controlled conditions in the presence of a Lewis acid (ZnCl 2). The X-ray crystal structure of 3 [C 18H 16N 2O 3S: Mt = 340.4, orthorhombic, Pbca, a = 12.208(3) Å, b = 18.848(4) Å, c = 14.566(11) Å, V = 3.351(3) Å3, Z = 8, Dcalc = 1.349 g cm -3, λ( CuKα) = 1.54178 Å, μ = 1.83 mm -1, F(000) = 1424, T = 293 K, R = 0.061 for 2.046 observed reflections] was determined, and confirmed the ( E) configuration. Despite the conjugate position of the vinyl double bond, quasi-coplanar with the imidazopyridine heterocycle, there is no evidence of p-electron delocalization. The crystal cohesion is ensured by a dense network of van der Waals contacts. The conformational analysis of the ( E) and ( Z) stereoisomers was performed by molecular dynamics simulation, and showed the ( E) isomer to be 9.1 kJ mol -1 more stable than the ( Z) isomer.

  1. A mass spectrometric study of gaseous H4PO+3 and H2PO-3 ions

    NASA Astrophysics Data System (ADS)

    de Petris, Giulia; Occhiucci, Giorgio; Pepi, Federico

    1994-09-01

    H4PO+3 ions have been generated in a mass spectrometer by proton-transfer to H3PO3 from different Brønsted acids. The proton affinity of H3PO3 has been estimated by bracketing and kinetic methods to be 198.6 ± 2 kcal mol-1. Gaseous H4PO+3 ions have been structurally assessed by metastable ion kinetic energy (MIKE) and collisionally induced dissociation (CID) mass spectrometry leading to the detection of a single isomeric species. The chemistry of H2PO-3 is characterized by facile addition-elimination reactions leading to formation of polyanions. Species containing up to six P atoms have been detected.

  2. Thermodynamics of triple helix formation: spectrophotometric studies on the d(A)10.2d(T)10 and d(C+3T4C+3).d(G3A4G3).d(C3T4C3) triple helices.

    PubMed Central

    Pilch, D S; Brousseau, R; Shafer, R H

    1990-01-01

    We have stabilized the d(A)10.2d(T)10 and d(C+LT4C+3).d(G3A4G3).d(C3T4C3) triple helices with either NaCl or MgCl2 at pH 5.5. UV mixing curves demonstrate a 1:2 stoichiometry of purine to pyrimidine strands under the appropriate conditions of pH and ionic strength. Circular dichroic titrations suggest a possible sequence-independent spectral signature for triplex formation. Thermal denaturation profiles indicate the initial loss of the third strand followed by dissociation of the underlying duplex with increasing temperature. Depending on the base sequence and ionic conditions, the binding affinity of the third strand for the duplex at 25 degrees C is two to five orders of magnitude lower than that of the two strands forming the duplex. Thermodynamic parameters for triplex formation were determined for both sequences in the presence of 50 mM MgCl2 and/or 2.0 M NaCl. Hoogsteen base pairs are 0.22-0.64 kcal/mole less stable than Watson-Crick base pairs, depending on ionic conditions and base composition. C+.G and T.A Hoogsteen base pairs appear to have similar stability in the presence of Mg2+ ions at low pH. PMID:2216768

  3. THE STRUCTURE, MAGNETISM AND CONDUCTIVITY OF Li3V2(PO4)3: A THEORETICAL AND EXPERIMENTAL STUDY

    NASA Astrophysics Data System (ADS)

    Lin, Zhi-Ping; Zhao, Yu-Jun; Zhao, Yan-Ming

    2013-10-01

    In this paper, we present a combination of first-principles and experimental investigations on the structural, magnetic and electronic properties of monoclinic Li3V2(PO4)3. The change of dielectric constant indicates that the structural phase transition appear around the temperature 120°C. The first-principles calculation and magnetic measurement display that Li3V2(PO4)3 is a compound with weak ferromagnetism, with Curie constant of C = 0.004 and Curie temperature of 140 K. The experimental and theoretical results demonstrated that the Li3V2(PO4)3 is a typical semiconductor.

  4. Synthesis and characterization of a new and electronically unusual uranium metallacyclocumulene, (C 5Me 5) 2U(η 4-1,2,3,4-PhC 4Ph)

    DOE PAGES

    Pagano, Justin K.; Erickson, Karla A.; Scott, Brian L.; ...

    2016-10-22

    A new uranium metallacyclocumulene, (C 5Me 5) 2U(η 4-1,2,3,4-PhC 4Ph), was synthesized by both reaction of (C 5Me 5) 2UCl 2 with 1,4-diphenylbutadiyne in the presence of KC 8 and by ligand exchange between (C 5Me 5) 2U(η 2-Me 3SiC 2SiMe 3) and 1,4-diphenylbutadiyne. Lastly, full characterization of (C 5Me 5) 2U(η 4-1,2,3,4-PhC 4Ph) is reported, including the solid-state structure. (C 5Me 5) 2U(η 4-1,2,3,4-PhC 4Ph) displays an unusually detailed UV–visible spectrum, which is rare for uranium(IV) metallocene complexes.

  5. Synthesis and characterization of a new and electronically unusual uranium metallacyclocumulene, (C 5Me 5) 2U(η 4-1,2,3,4-PhC 4Ph)

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

    Pagano, Justin K.; Erickson, Karla A.; Scott, Brian L.

    A new uranium metallacyclocumulene, (C 5Me 5) 2U(η 4-1,2,3,4-PhC 4Ph), was synthesized by both reaction of (C 5Me 5) 2UCl 2 with 1,4-diphenylbutadiyne in the presence of KC 8 and by ligand exchange between (C 5Me 5) 2U(η 2-Me 3SiC 2SiMe 3) and 1,4-diphenylbutadiyne. Lastly, full characterization of (C 5Me 5) 2U(η 4-1,2,3,4-PhC 4Ph) is reported, including the solid-state structure. (C 5Me 5) 2U(η 4-1,2,3,4-PhC 4Ph) displays an unusually detailed UV–visible spectrum, which is rare for uranium(IV) metallocene complexes.

  6. CH(X2∏, a4∑-) ... OH2 and CH2(X˜3B1, ã1A1) ... OH2 interactions. A first principles investigation

    NASA Astrophysics Data System (ADS)

    Tzeli, Demeter; Mavridis, Aristides

    We have investigated the interaction of the methylidene, CH(X2∏, a4∑-) and methylene, CH2(X˜3B1, ã1A1) with H2O, employing the (P)MPn (n = 2, 4) techniques in conjunction with the sequence of correlation consistent basis sets aug-cc-pVxZ, x = 2, 3, and 4. For the CH ... OH2 system, we have located four minima (m) and three transition states (ts) and for the CH2 ... OH2, five minima and four transition states. All our results have been corrected for zero-point energy (ZPE) and basis set superposition errors (BSSE), while for the most important m_ structures, we report complete basis set (CBS) interaction limits. We also report fully optimized geometries, harmonic frequencies, dipole moments, Mulliken charges, and potential energy curves. The highest CH(X2∏) ... OH2 (m1_2∏) and CH2(ã1A1) ... OH2 (m1_1A1) interactions are the result of electron transfer from the oxygen atom to the empty pπ orbitals of CH(X2∏) and CH2(ã1A1), respectively (ylide-like structures). At the (P)MP4/AQZ//MP2/ATZ level, including ZPE, BSSE, and CBS extrapolation, we obtain ΔE0(BSSE)+CBS = -9.36 kcal/mol at rC ... O = 1.752 Å, and -9.73 kcal/mol at rC ... O = 1.741 Å for the m1_2∏ and m1_1A1, respectively.

  7. 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

  8. Novel reassortant clade 2.3.4.4 avian influenza A (H5N8) virus in a grey heron in South Korea in 2017.

    PubMed

    Woo, Chanjin; Kwon, Jung-Hoon; Lee, Dong-Hun; Kim, Youngsik; Lee, Kwanghee; Jo, Seong-Deok; Son, Ki Dong; Oem, Jae-Ku; Wang, Seung-Jun; Kim, Yongkwan; Shin, Jeonghwa; Song, Chang-Seon; Jheong, Weonhwa; Jeong, Jipseol

    2017-12-01

    We report the identification of a novel reassortant clade 2.3.4.4 H5N8 virus from a dead grey heron in Korea in 2017. Outbreaks of clade 2.3.4.4 H5 HPAIVs have been reported worldwide, and they have evolved into multiple genotypes among wild birds. Phylogenetic analysis indicated that this virus likely originated from Qinghai Lake and Western Siberia and further evolved through reassortment with Eurasian LPAI during the 2016 fall migration of wild birds. Enhanced surveillance and comparative genetic analysis will help to monitor the further evolution and dissemination of clade 2.3.4.4 HPAIVs.

  9. Synthesis, crystal structure and spectroscopy properties of Na 3AZr(PO 4) 3 ( A=Mg, Ni) and Li 2.6Na 0.4NiZr(PO 4) 3 phosphates

    NASA Astrophysics Data System (ADS)

    Chakir, M.; El Jazouli, A.; de Waal, D.

    2006-06-01

    Na 3AZr(PO 4) 3 ( A=Mg, Ni) phosphates were prepared at 750 °C by coprecipitation route. Their crystal structures have been refined at room temperature from X-ray powder diffraction data using Rietveld method. Li 2.6Na 0.4NiZr(PO 4) 3 was synthesized through ion exchange from the sodium analog. These materials belong to the Nasicon-type structure. Raman spectra of Na 3AZr(PO 4) 3 ( A=Mg, Ni) phosphates present broad peaks in favor of the statistical distribution in the sites around PO 4 tetrahedra. Diffuse reflectance spectra indicate the presence of octahedrally coordinated Ni 2+ ions.

  10. Synthesis and antitumor screening of new 1,7-diphenyl-3-(1,3-disubstituted-1H-pyrazole-4-carbonyl)-[1,2,4]triazolo[4,3-a]pyrimidin-5(1H)-ones.

    PubMed

    Shawali, Ahmad S; Sherif, Sherif M; Darwish, Manal A A; El-merzabani, Mahmoud M

    2010-01-01

    A new series of 3-(1,3-disubstituted-1H-pyrazole-4-carbonyl)-1,7-diphenyl-[1,2,4]triazolo[4,3-a]pyrimidin-5(1H)-ones 4 was prepared by reaction of the enaminone 2 with hydrazonoyl halides 3. The preliminary screening for antitumor activity of the synthesized compounds was carried out against Ehrlich Ascites Carcinoma tumor cells. The results revealed that the studied compounds 4 have low or no antitumor activity towards EAC tumor cells.

  11. Ca3La2(BO3)4 crystal: a new candidate host material for the ytterbium ion

    NASA Astrophysics Data System (ADS)

    Wang, Yeqing; You, Zhenyu; Zhu, Zhaojie; Xu, Jinlong; Li, Jianfu; Wang, Yan; Wang, Hongyan; Tu, Chaoyang

    2013-10-01

    A disordered laser crystal Yb3+-doped Ca3La2(BO3)4 crystal was grown by the Czochralski technique. The characterized room temperature polarized spectra, re-absorption possibility and laser performance showed that this crystal should be a promising gain material, not only suitable for diode pumping, but also a good candidate for the generation of tunable and short pulse lasers. End pumped by a diode laser at 976 nm in plano-concave and plano-plano cavity, a 3.65 W output power with a slope efficiency of 65% was achieved by using a c-cut Yb3+:Ca3La2(BO3)4 crystal. The output laser wavelength shifted from 1042 to 1062 nm.

  12. 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.

  13. Ti 3CrCu 4: A possible 2-D ferromagnetic spin fluctuating system

    DOE PAGES

    Dhar, S. K.; Provino, A.; Manfrinetti, P.; ...

    2016-03-09

    Ti 3CrCu 4 is a new ternary compound which crystallizes in the tetragonal Ti 3Pd 5 structure type. The Cr atoms form square nets in the a-b plane (a = 3.124 Å) which are separated by an unusually large distance c = 11.228 Å along the tetragonal axis, thus forming a -2-D Cr-sublattice. The paramagnetic susceptibility is characterized by a low effective moment, μ eff = 1.1 μ B, a low paramagnetic Curie temperature θ P (below 7 K) and a temperature independent χ0 = 6.7 x 10 –4 emu/mol. The magnetization at 1.8 K increases rapidly with field nearlymore » saturating to 0.2 μ B/f.u. The zero field heat capacity C/T shows an upturn below 7 K (~190 mJ/mol K 2 at ~0.1K) which is suppressed in applied magnetic fields and interpreted as suggesting the presence of spin fluctuations. The resistivity at low temperatures shows non-Fermi liquid behavior. Overall, the experimental data thus reveal an unusual magnetic state in Ti 3CrCu 4, which likely has its origin in the layered nature of the Cr sub-lattice and ferromagnetic spin fluctuations. Here, density functional theoretical calculations reveal a sharp Cr density of states peak just above the Fermi level, indicating the propensity of Ti 3CrCu 4 to become magnetic.« less

  14. Phosphoinnelite, Ba4Na3Ti3Si4O14(PO4,SO4)2(O,F)3, a new mineral species from peralkaline pegmatite of the Kovdor pluton, Kola Peninsula

    NASA Astrophysics Data System (ADS)

    Pekov, I. V.; Chukanov, N. V.; Kulikova, I. M.; Belakovsky, D. I.

    2007-12-01

    Phosphoinnelite, an analogue of innelite with P > S, has been found in a peralkaline pegmatite vein crosscutting calcite carbonatite at the phlogopite deposit, Kovdor pluton, Kola Peninsula. Cancrinite (partly replaced with thomsonite-Ca), orthoclase, aegirine-augite, pectolite, magnesioarfvedsonite, golyshevite, and fluorapatite are associated minerals. Phosphoinnelite occurs as lath-shaped crystals up to 0.2 × 1 × 6 mm in size, which are combined typically in bunch-, sheaf-, and rosettelike segregations. The color is yellow-brown, with vitreous luster on crystal faces and greasy luster on broken surfaces. The mineral is transparent. The streak is pale yellowish. Phosphoinnelite is brittle, with perfect cleavage parallel to the {010} and good cleavage parallel to the {100}; the fracture is stepped. The Mohs hardness is 4.5 to 5. Density is 3.82 g/cm3 (meas.) and 3.92 g/cm3 (calc.). Phosphoinnelite is biaxial (+), α = 1.730, β = 1.745, and γ = 1.764, 2V (meas.) is close to 90°. Optical orientation is Z^c ˜ 5°. Chemical composition determined by electron microprobe is as follows (wt %): 6.06 Na2O, 0.04 K2O, 0.15 CaO, 0.99 SrO, 41.60 BaO, 0.64 MgO, 1.07 MnO, 1.55 Fe2O3, 0.27 Al2O3, 17.83 SiO2, 16.88 TiO2, 0.74 Nb2O5, 5.93 P2O5, 5.29 SO3, 0.14 F, -O=F2 = -0.06, total is 99.12. The empirical formula calculated on the basis of (Si,Al)4O14 is (Ba3.59Sr0.13K0.01)Σ3.73(Na2.59Mg0.21Ca0.04)Σ3.04(Ti2.80Fe{0.26/3+}Nb0.07)Σ3.13[(Si3.93Al0.07)Σ4O14(P1.11S0.87)Σ1.98O7.96](O2.975F0.10)Σ3.075. The simplified formula is Ba4Na3Ti3Si4O14(PO4,SO4)2(O,F)3. The mineral is triclinic, space group P overline 1 or P1. The unit cell dimensions are a = 5.38, b = 7.10, c = 14.76 Å; α = 99.00°, β = 94.94°, γ = 90.14°; and V = 555 Å3, Z = 1. The strongest lines of the X-ray powder pattern [ d, Å in ( I)( hkl)] are: 14.5(100)(001), 3.455(40)(103), 3.382(35)(0overline 2 2), 2.921(35)(005), 2.810(40)(1overline 1 4), 2.683(90)(200, overline 2 01), 2.133(80)(overline 2 overline

  15. 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

  16. A Co3O4-CDots-C3N4 three component electrocatalyst design concept for efficient and tunable CO2 reduction to syngas.

    PubMed

    Guo, Sijie; Zhao, Siqi; Wu, Xiuqin; Li, Hao; Zhou, Yunjie; Zhu, Cheng; Yang, Nianjun; Jiang, Xin; Gao, Jin; Bai, Liang; Liu, Yang; Lifshitz, Yeshayahu; Lee, Shuit-Tong; Kang, Zhenhui

    2017-11-28

    Syngas, a CO and H 2 mixture mostly generated from non-renewable fossil fuels, is an essential feedstock for production of liquid fuels. Electrochemical reduction of CO 2 and H + /H 2 O is an alternative renewable route to produce syngas. Here we introduce the concept of coupling a hydrogen evolution reaction (HER) catalyst with a CDots/C 3 N 4 composite (a CO 2 reduction catalyst) to achieve a cheap, stable, selective and efficient route for tunable syngas production. Co 3 O 4 , MoS 2 , Au and Pt serve as the HER component. The Co 3 O 4 -CDots-C 3 N 4 electrocatalyst is found to be the most efficient among the combinations studied. The H 2 /CO ratio of the produced syngas is tunable from 0.07:1 to 4:1 by controlling the potential. This catalyst is highly stable for syngas generation (over 100 h) with no other products besides CO and H 2 . Insight into the mechanisms balancing between CO 2 reduction and H 2 evolution when applying the HER-CDots-C 3 N 4 catalyst concept is provided.

  17. Cyclic guanidines: synthesis and antiplatelet activity of 4,6,7,8-tetrahydro-1H-imidazo[1,2-a]pyrazolo[3,4-d]pyrimidin-7-ones and 1,4,6,7,8,9-hexahydropyrazolo [3',4':4,5]pyrimido[2,1-c] [1,2,4]triazin-7-ones.

    PubMed

    Ferroni, R; Simoni, D; Orlandini, P; Bardi, A; Franze, G P; Guarneri, M

    1990-12-01

    A series of 4,6,7,8-tetrahydro-1H-imidazo[1,2-a]pyrazolo [3,4-d]pyrimidin-7-ones (1b-n) and 1,4,6,7,8,9-hexahydropyrazolo [3',4':4,5]pyrimido [2,1-c][1,2,4]triazin-7-ones (2a-d) has been synthesized. In view of their potential anti-aggregating activity the compounds were tested in vitro for inhibitory activity towards ADP- and collagen-induced aggregation of human platelets. Among the compounds studied, 8-benzyl-1-(2,5-dichlorophenyl)-4,6,7,8-tetrahydro-1H-imidazo [1,2-a]pyrazolo[3,4-d]pyrimidin-7-one (1n) exhibited the most favorable activity. The 2,5-dichlorophenyl side chain is an important lipophilic and/or steric pharmacophore.

  18. 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

  19. Gas-phase acidities of cysteine-polyalanine peptides I: A(3,4)CSH and HSCA(3,4).

    PubMed

    Ren, Jianhua; Tan, John P; Harper, Robert T

    2009-10-15

    The gas-phase acidities of four cysteine-polyalanine peptides, A(3,4)CSH and HSCA(3,4), were determined using the extended Cooks kinetic method with full entropy analysis. A triple-quadrupole mass spectrometer with an electrospray interface was employed for the experimental study. The ion activation was achieved via collision-induced dissociation (CID) experiments. The deprotonation enthalpies (Delta(acid)H) of the peptides were determined to be 332.2 +/- 2.0 kcal/mol (A(3)CSH), 325.9 +/- 2.0 kcal/mol (A(4)CSH), 319.3 +/- 3.0 kcal/mol (HSCA(3)), and 319.2 +/- 4.0 kcal/mol (HSCA(4)). The deprotonation entropies (Delta(acid)S) of the peptides were estimated based on the entropy term (Delta(DeltaS)) and the deprotonation entropies of the reference acids. By using the deprotonation enthalpies and entropies, the gas-phase acidities (Delta(acid)G) of the peptides were derived: 325.0 +/- 2.0 kcal/mol (A(3)CSH), 320.2 +/- 2.0 kcal/mol (A(4)CSH), 316.3 +/- 3.0 kcal/mol (HSCA(3)), and 315.4 +/- 4.0 kcal/mol (HSCA(4)). Conformations and energetic information of the peptides were calculated through simulated annealing (Tripos), geometry optimization (AM1), and single-point energy calculations (B3LYP/6-31+G(d)), respectively. The calculated theoretical deprotonation enthalpies (Delta(acid)H) of 334.2 kcal/mol (A(3)CSH), 327.7 kcal/mol (A(4)CSH), 320.6 kcal/mol (HSCA(3)), and 318.6 kcal/mol (HSCA(4)) are in good agreement with the experimentally determined values. Both the experimental and computational studies suggest that the two N-terminal cysteine peptides, HSCA(3,4), are significantly more acidic than the corresponding C-terminal ones, A(3,4)CSH. The high acidities of the former are likely due to the helical conformational effects for which the thiolate anion may be strongly stabilized by the interaction with the helix macrodipole.

  20. 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.

  1. Pharmacogenetics in American Indian populations: analysis of CYP2D6, CYP3A4, CYP3A5, and CYP2C9 in the Confederated Salish and Kootenai Tribes.

    PubMed

    Fohner, Alison; Muzquiz, LeeAnna I; Austin, Melissa A; Gaedigk, Andrea; Gordon, Adam; Thornton, Timothy; Rieder, Mark J; Pershouse, Mark A; Putnam, Elizabeth A; Howlett, Kevin; Beatty, Patrick; Thummel, Kenneth E; Woodahl, Erica L

    2013-08-01

    Cytochrome P450 enzymes play a dominant role in drug elimination and variation in these genes is a major source of interindividual differences in drug response. Little is known, however, about pharmacogenetic variation in American Indian and Alaska Native (AI/AN) populations. We have developed a partnership with the Confederated Salish and Kootenai Tribes (CSKT) in northwestern Montana to address this knowledge gap. We resequenced CYP2D6 in 187 CSKT individuals and CYP3A4, CYP3A5, and CYP2C9 in 94 CSKT individuals. We identified 67 variants in CYP2D6, 15 in CYP3A4, 10 in CYP3A5, and 41 in CYP2C9. The most common CYP2D6 alleles were CYP2D6*4 and *41 (20.86 and 11.23%, respectively). CYP2D6*3, *5, *6, *9, *10, *17, *28, *33, *35, *49, *1xN, *2xN, and *4xN frequencies were less than 2%. CYP3A5*3, CYP3A4*1G, and *1B were detected with frequencies of 92.47, 26.81, and 2.20%, respectively. Allelic variation in CYP2C9 was low: CYP2C9*2 (5.17%) and *3 (2.69%). In general, allele frequencies in CYP2D6, CYP2C9, and CYP3A5 were similar to those observed in European Americans. There was, however, a marked divergence in CYP3A4 for the CYP3A4*1G allele. We also observed low levels of linkage between CYP3A4*1G and CYP3A5*1 in the CSKT. The combination of nonfunctional CYP3A5*3 and putative reduced function CYP3A4*1G alleles may predict diminished clearance of CYP3A substrates. These results highlight the importance of carrying out pharmacogenomic research in AI/AN populations and show that extrapolation from other populations is not appropriate. This information could help optimize drug therapy for the CSKT population.

  2. Pharmacogenetics in American Indian Populations: Analysis of CYP2D6, CYP3A4, CYP3A5, and CYP2C9 in the Confederated Salish and Kootenai Tribes

    PubMed Central

    Fohner, Alison; Muzquiz, LeeAnna I.; Austin, Melissa A.; Gaedigk, Andrea; Gordon, Adam; Thornton, Timothy; Rieder, Mark J.; Pershouse, Mark A.; Putnam, Elizabeth A.; Howlett, Kevin; Beatty, Patrick; Thummel, Kenneth E.; Woodahl, Erica L.

    2014-01-01

    Objectives Cytochrome P450 enzymes play a dominant role in drug elimination and variation in these genes is a major source of interindividual differences in drug response. Little is known, however, about pharmacogenetic variation in American Indian and Alaska Native (AI/AN) populations. We have developed a partnership with the Confederated Salish and Kootenai Tribes (CSKT) in northwestern Montana to address this knowledge gap. Methods We resequenced CYP2D6 in 187 CSKT subjects and CYP3A4, CYP3A5, and CYP2C9 in 94 CSKT subjects. Results We identified 67 variants in CYP2D6, 15 in CYP3A4, 10 in CYP3A5, and 41 in CYP2C9. The most common CYP2D6 alleles were CYP2D6*4 and *41 (20.86 and 11.23%, respectively). CYP2D6*3, *5, *6, *9, *10, *17, *28, *33, *35, *49, *1xN, *2xN, and *4xN frequencies were less than 2%. CYP3A5*3, CYP3A4*1G, and *1B were detected with frequencies of 92.47, 26.81, and 2.20%, respectively. Allelic variation in CYP2C9 was low: CYP2C9*2 (5.17%) and *3 (2.69%). In general, allele frequencies in CYP2D6, CYP2C9 and CYP3A5 were similar to those observed in European Americans. There was, however, a marked divergence in CYP3A4 for the CYP3A4*1G allele. We also observed low levels of linkage between CYP3A4*1G and CYP3A5*1 in the CSKT. The combination of nonfunctional CYP3A5*3 and putative reduced function CYP3A4*1G alleles may predict diminished clearance of CYP3A substrates. Conclusions These results highlight the importance of conducting pharmacogenomic research in AI/AN populations and demonstrate that extrapolation from other populations is not appropriate. This information could help to optimize drug therapy for the CSKT population. PMID:23778323

  3. Synthesis of a novel 'smart' bifunctional chelating agent 1-(2-[beta,D-galactopyranosyloxy]ethyl)-7-(1-carboxy-3-[4-aminophenyl]propyl)-4,10-bis(carboxymethyl)-1,4,7,10-tetraazacyclododecane (Gal-PA-DO3A-NH2) and its Gd(III) complex.

    PubMed

    Wardle, Nick J; Herlihy, Amy H; So, Po-Wah; Bell, Jimmy D; Bligh, S W Annie

    2007-07-15

    A new synthetic pathway to 1-(2-[beta,D-galactopyranosyloxy]ethyl)-7-(1-carboxy-3-[4-aminophenyl]propyl)-4,10-bis(carboxymethyl)-1,4,7,10-tetraazacyclododecane (Gal-PA-DO3A-NH2) and 1-(2-[beta,D-galactopyranosyloxy]ethyl)-4,7,10-tris(carboxymethyl)-1, 4,7,10-tetraazacyclododecane (Gal-DO3A) chelating agents was developed involving full hydroxyl- and carboxyl-group protection in precursors to product. Two sequences of cyclen-N-functionalisation were subsequently investigated, one successfully, towards synthesis of the novel 'smart' bifunctional Gal-PA-DO3A-NH2 chelate. The longitudinal proton relaxivities of the neutral [Gd-(Gal-PA-DO3A-NH2)] and [Gd-(Gal-DO3A)] complexes were increased by 28% and 37% in the presence of beta-galactosidase, respectively.

  4. Crystal structure and absolute configuration of (3aS,4S,5R,7aR)-2,2,7-trimethyl-3a,4,5,7a-tetra-hydro-1,3-benzodioxole-4,5-diol.

    PubMed

    Macías, Mario A; Suescun, Leopoldo; Pandolfi, Enrique; Schapiro, Valeria; Tibhe, Gaurao D; Mombrú, Álvaro W

    2015-09-01

    The absolute configuration of the title compound, C10H16O4, determined as 3aS,4S,5R,7aR on the basis of the synthetic pathway, was confirmed by X-ray diffraction. The mol-ecule contains a five- and a six-membered ring that adopt twisted and envelope conformations, respectively. The dihedral angle between the mean planes of the rings is 76.80 (11)° as a result of their cis-fusion. In the crystal, mol-ecules are linked by two pairs of O-H⋯O hydrogen bonds, forming chains along [010]. These chains are further connected by weaker C-H⋯O inter-actions along [100], creating (001) sheets that inter-act only by weak van der Waals forces.

  5. N(4)-[B-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan)methyl]-2'-deoxycytidine as a potential boron delivery agent with respect to glioblastoma.

    PubMed

    Uram, Łukasz; Nizioł, Joanna; Maj, Piotr; Sobich, Justyna; Rode, Wojciech; Ruman, Tomasz

    2017-11-01

    Glioblastoma multiforme (GBM) is a central nervous system tumor of grade IV, according to the WHO classification, extremely resistant to all currently used forms of therapy, including resection, radiotherapy, chemotherapy or combined therapy. Therefore, more effective treatment strategies of this tumor are needed, with boron neutron capture therapy (BNCT) being a potential solution, provided a proper cancer cells-targeted 10B delivery agent is found. In search of such an agent, toxicity and capacity to target DNA of a boronated derivative of 2'-deoxycytidine, N(4)-[B-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan)methyl]-2'-deoxycytidine (1), was tested against human tumor vs. normal cells. The present in vitro results revealed 1 to show low toxicity for human U-118 MG glioma cells (in the mM range) and even by 3-4 - fold lower against normal human fibroblasts. In accord, induction of apoptosis dependent on caspase-3 and caspase-7 was detected at high (>20mM) concentration of 1. Although demonstrated to be susceptible to phosphorylation by human deoxycytidine kinase and to undergo incorporation in cellular DNA, the boron analogue did not disturb cell proliferation when applied at non-toxic concentrations and showed low toxicity to a model metazoan organism, Caenorhabditis elegans. Thus, N(4)-[B-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan)methyl]-2'-deoxycytidine appears a promising candidate for a 10B delivery agent to be used in BNCT, with C. elegans indicated as a good model for in vivo studies. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  6. QSAR studies in substituted 1,2,3,4,6,7,12,12a-octa-hydropyrazino[2',1':6,1]pyrido[3,4-b]indoles--a potent class of neuroleptics.

    PubMed

    Saxena, Anil K; Ram, Siya; Saxena, Mridula; Singh, Nidhi; Prathipati, Philip; Jain, Padam C; Singh, H K; Anand, Nitya

    2003-05-01

    A series of nineteen substituted 1,2,3,4,6,7,12,12a-octahydropyrazino[2',1':6,1]pyrido[3, 4-b]indoles analogues of neuroleptic drug, Centbutindole have been studied using quantitative structure-activity relationship analysis. The derived models display good fits to the experimental data (r>or=0.75) having good predictive power (r(cv)>or=0.688). The best model describes a high correlation between predicted and experimental activity data (r=0.967). Statistical analysis of the equation populations indicates that hydrophobicity (as measured by pi(R), logP(o/w) and SlogP_VSA8), dipole y and structural parameters in terms of indicator variable, (In(1)) and globularity are important variables in describing the variation in the neuroleptic activity in the series.

  7. Pharmacokinetics of S-3-(4-acetylamino-phenoxy)-2-hydroxy-2-methyl-N-(4-nitro-3-trifluoromethyl-phenyl)-propionamide in rats, a non-steroidal selective androgen receptor modulator

    PubMed Central

    KEARBEY, J. D.; WU, D.; GAO, W.; MILLER, D. D.; DALTON, J. T.

    2007-01-01

    1. S-3-(4-acetylamino-phenoxy)-2-hydroxy-2-methyl-N-(4-nitro-3-trifluoromethyl-phenyl)-propionamide (also known as S-4) is a non-steroidal selective androgen receptor modulator demonstrating tissue-selective androgenic and anabolic effects. The purpose of the present study was to examine the systemic pharmacokinetics, elimination and oral bioavailability of S-4 in rats. 2. Thirty-five male Sprague–Dawley rats weighing approximately 250 g were randomly assigned to one of seven treatment groups. Intravenous doses of 0.5, 1, 10, and 30 mg kg−1 were given via a jugular catheter. Oral doses of 1, 10 and 30 mg kg−1 were administered via gavage. Plasma concentrations were determined using a validated high-performance liquid chromatography or by a high-performance liquid chromatography/mass spectrometry method. 3. Clearances ranged between 1.0 and 2.1 ml min−1 kg−1 and varied with dose. The volume of distribution was approximately 0.448 l kg−1 in all treatment groups. Oral bioavailability was also dose dependent, with the lower doses showing complete oral bioavailability. The half-life of S-4 over the dose range tested was between 2.6 and 5.3 h. 4. It was demonstrated that S-4 is rapidly absorbed, slowly cleared, and has a moderate volume of distribution in rats. The pharmacokinetics and oral bioavailability of S-4 indicate that it is an excellent candidate for clinical development. PMID:15204699

  8. A new organic superconductor, beta-(BDA-TTP)2GaCl4 [BDA-TTP = 2,5-(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene].

    PubMed

    Yamada, Jun-ichi; Toita, Takashi; Akutsu, Hiroki; Nakatsuji, Shin'ichi; Nishikawa, Hiroyuki; Ikemoto, Isao; Kikuchi, Koichi; Choi, Eun S; Graf, David; Brooks, James S

    2003-09-07

    The preparation, crystal structure and physical properties of beta-(BDA-TTP)2GaCl4 has been investigated; the salt exhibits superconductivity at 3.1 K (onset) under a hydrostatic pressure of 7.6 kbar.

  9. SSR126768A (4-chloro-3-[(3R)-(+)-5-chloro-1-(2,4-dimethoxybenzyl)-3-methyl-2-oxo-2,3-dihydro-1H-indol-3-yl]-N-ethyl-N-(3-pyridylmethyl)-benzamide, hydrochloride): a new selective and orally active oxytocin receptor antagonist for the prevention of preterm labor.

    PubMed

    Serradeil-Le Gal, Claudine; Valette, Gérard; Foulon, Loïc; Germain, Guy; Advenier, Charles; Naline, Emmanuel; Bardou, Marc; Martinolle, Jean-Pierre; Pouzet, Brigitte; Raufaste, Danielle; Garcia, Corinne; Double-Cazanave, Eléonore; Pauly, Maxime; Pascal, Marc; Barbier, Alain; Scatton, Bernard; Maffrand, Jean-Pierre; Le Fur, Gérard

    2004-04-01

    4-chloro-3-[(3R)-(+)-5-chloro-1-(2,4-dimethoxybenzyl)-3-methyl-2-oxo-2,3-dihydro-1H-indol-3-yl]-N-ethyl-N-(3-pyridylmethyl)benzamide, hydrochloride (SSR126768A), a new potent and selective, orally active oxytocin (OT) receptor antagonist was characterized in several biochemical and pharmacological models. In binding studies, SSR126768A showed nanomolar affinity for rat and human recombinant and native OT receptors (K(i) = 0.44 nM) and exhibited much lower affinity for V(1a), V(1b), and V(2) receptors. In addition, it did not interact with a large number of other receptors, enzymes, and ion channels (1 microM). In autoradiographic experiments performed on at-term human pregnant uterus sections, SSR126768A dose dependently displaced [I(125)]d(CH(2))(5)[Tyr(Me)(2), Thr(4), Orn(8) (125)I-Tyr-NH(2)(9)]VT in situ labeling to OT receptors highly expressed in these tissues. In functional studies, SSR126768A behaved as a full antagonist and potently antagonized OT-induced intracellular Ca(2+) increase (K(i) = 0.50 nM) and prostaglandin release (K(i) = 0.45 nM) in human uterine smooth muscle cells. In rat isolated myometrium, OT-induced uterine contractions were competitively antagonized by SSR126768A (pA(2) = 8.47). Similarly, in human pregnant myometrial strips, SSR126768A inhibited the contractile uterine response to OT. In conscious telemetrated rats, oral administration of SSR126768A (1-10 mg/kg) produced a competitive inhibition of the dose response to OT on uterine contractions up to 24 h at 3 mg/kg p.o.; no tachyphylaxis was observed after 4-day repeated treatment. Finally, SSR126768A (30 mg/kg p.o.) significantly delayed parturition in pregnant rats in labor similar to ritodrine (10 mg/kg p.o.). Thus, SSR126768A is a potent, highly selective, orally active OT receptor antagonist with a long duration of action. This molecule could find therapeutic application as a tocolytic agent for acute and chronic oral management of preterm labor.

  10. The system K2Mg2(SO4)3 (langbeinite)-K2Ca2(SO4)3 (calcium-langbeinite)

    USGS Publications Warehouse

    Morey, G.W.; Rowe, J.J.; Fournier, R.O.

    1964-01-01

    The join between the compositions K2Mg2(SO4)3 and K2Ca2(SO4)3 was studied by means of high-temperature equilibrium quenching techniques and by means of a heating stage mounted on an X-ray diffractometer. Complete solid solution exists in the system, but at 25??C members of the solid solution series are isometric only in the composition range 0-73??5 wt. per cent K2Ca2(SO4)3. At compositions richer in K2Ca2(SO4)3 than 73??5 wt. per cent, members of the series are optically biaxial. At higher temperatures members of the solid solution series are isometric at successively more calcium-rich compositions and pure K2Ca2(SO4)3 is isometric above about 200 ?? 2??C. The system is not binary, as mixtures richer in K2Ca2(SO4)3 than 42 wt. per cent decompose with the formation of liquid and CaSO4. ?? 1964.

  11. Discovery of 1-((2R,4aR,6R,7R,7aR)-2-Isopropoxy-2-oxidodihydro-4H,6H-spiro[furo[3,2-d][1,3,2]dioxaphosphinine-7,2'-oxetan]-6-yl)pyrimidine-2,4(1H,3H)-dione (JNJ-54257099), a 3'-5'-Cyclic Phosphate Ester Prodrug of 2'-Deoxy-2'-Spirooxetane Uridine Triphosphate Useful for HCV Inhibition.

    PubMed

    Jonckers, Tim H M; Tahri, Abdellah; Vijgen, Leen; Berke, Jan Martin; Lachau-Durand, Sophie; Stoops, Bart; Snoeys, Jan; Leclercq, Laurent; Tambuyzer, Lotke; Lin, Tse-I; Simmen, Kenny; Raboisson, Pierre

    2016-06-23

    JNJ-54257099 (9) is a novel cyclic phosphate ester derivative that belongs to the class of 2'-deoxy-2'-spirooxetane uridine nucleotide prodrugs which are known as inhibitors of the HCV NS5B RNA-dependent RNA polymerase (RdRp). In the Huh-7 HCV genotype (GT) 1b replicon-containing cell line 9 is devoid of any anti-HCV activity, an observation attributable to inefficient prodrug metabolism which was found to be CYP3A4-dependent. In contrast, in vitro incubation of 9 in primary human hepatocytes as well as pharmacokinetic evaluation thereof in different preclinical species reveals the formation of substantial levels of 2'-deoxy-2'-spirooxetane uridine triphosphate (8), a potent inhibitor of the HCV NS5B polymerase. Overall, it was found that 9 displays a superior profile compared to its phosphoramidate prodrug analogues (e.g., 4) described previously. Of particular interest is the in vivo dose dependent reduction of HCV RNA observed in HCV infected (GT1a and GT3a) human hepatocyte chimeric mice after 7 days of oral administration of 9.

  12. A novel synthesis of acyclonucleosides via allylation of 3-[1-(phenylhydrazono)-L-threo-2,3,4-trihydroxybut-1-yl]quinoxalin-2(1H)one.

    PubMed

    Hamid, Hamida Mohamed Abdel

    2003-10-31

    The allylation of 3-[1-(phenylhydrazono)-L-threo-2,3,4-trihydroxybut-1-yl]quinoxalin-2(1H)one (1) gave, in addition to the anticipated 1-N-allyl derivative (2), a dehydrative cyclized product, 1-N-allyl-3-[5-(hydroxymethyl)-1-phenylpyrazol-3-yl]quinoxalin-2-one (4) and its isomeric O-allyl derivative 3. The O-allyl group in 3 underwent acetolysis under acetylation conditions, in addition to the acetylation of the hydroxyl group, to afford 2-acetoxy-3-[5-(acetoxymethyl)-1-phenylpyrazol-3-yl]quinoxaline (8) instead of the O-acetyl derivative of 3. Allylation of the tri-O-acetyl derivative of 1 caused the elimination of a molecule of acetic acid in addition to N-allylation to give 1-N-allyl-3-[3,4-di-O-acetyl-2-deoxy-1-(phenylhydrazono)but-2-en-1-yl]quinoxalin-2-one (11). Hydroxylation of the allyl group gave a glycerol-1-yl acyclonucleoside which can be alternatively obtained by a displacement reaction of the tosyloxy group in 2,3-O-isopropylidene-1-O-(p-tolylsulfonyl)glycerol (14), followed by deisopropylidenation. 1-N-(2,3-Dibromopropyl)-3-[5-(hydroxymethyl)-1-(4-bromophenyl)pyrazol-3-yl]quinoxalin-2-one (15) underwent azidolysis to give a 2,3-diazido derivative. The assigned structures were based on spectral analysis. The activity of compounds 2, 4, 6, and 15 against hepatitis B virus was studied.

  13. One-pot Sequential Reactions Featuring a Copper-catalyzed Amination Leading to Pyrido[2',1':2,3]imidazo[4,5-c]quinolines and Dihydropyrido[2',1':2,3]imidazo[4,5-c]quinolines.

    PubMed

    Fan, Xue-Sen; Zhang, Ju; Li, Bin; Zhang, Xin-Ying

    2015-06-01

    Tetracyclic skeletons combining an imidazo[1,2-a]pyridine moiety with a quinoline framework such as pyrido[2',1':2,3]imidazo[4,5-b]quinoline are stimulating increasing interests since they are close isosteres of a series of powerful antiproliferative compounds. In this paper, we report a novel methodology for the synthesis of pyrido[2',1':2,3]imidazo[4,5-c]quinolines through one-pot sequential reactions of commercially available or readily obtainable 2-aminopyridines, 2-bromophenacyl bromides, aqueous ammonia, and aldehydes. Moreover, dihydropyrido[2',1':2,3]imidazo[4,5-c]quinolines could also be obtained in a similar manner by using various ketones as the substrates in place of aldehydes. Notably, the whole procedure combines condensation/amination/cyclization reactions in one pot to give complex compounds in a simple and practical manner. Compared with literature methods, the synthetic strategy reported herein has the advantages of readily available starting materials, structural diversity of products, good functional group tolerance, and obviation of step-by-step operations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Structural and Computational Studies of Cp(CO)2(PCy3)MoFBF3, a Complex with a Bound BF4- Ligand

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

    Cheng, Tan-Yun; Szalda, David J.; Franz, James A.

    2010-02-15

    Hydride transfer from Cp(CO)2(PCy3)MoH to Ph3C+BF4 gives Cp(CO)2(PCy3)MoFBF3, and the crystal structure of this complex was determined. In the weakly bound FBF3 ligand, the B-F(bridging) bond length is 1.475(8) Å, which is 0.15 Å longer than the average length of the three B-F(terminal) bonds. The PCy3 and FBF3 ligands are cis to each other in the four-legged piano stool structure. Electronic structure (DFT) calculations predict the trans isomer of Cp(CO)2(PCy3)MoFBF3 to be 9.5 kcal/mol (in ΔGog,298)) less stable than the cis isomer that was crystallographically characterized. Hydride transfer from Cp(CO)2(PCy3)MoH to Ph3C+BAr'4 [Ar' = 3,5-bis(trifluoromethyl)phenyl] in CH2Cl2 solvent produces [Cp(CO)2(PCy3)Mo(ClCH2Cl)]+[BAr'4]more » , in which CH2Cl2 is coordinated to the metal. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

  15. [4,4‧-bi(1,3,2-dioxathiolane)] 2,2‧-dioxide: A novel cathode additive for high-voltage performance in lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Lee, Sang Hyun; Yoon, Sukeun; Hwang, Eui-Hyung; Kwon, Young-Gil; Lee, Young-Gi; Cho, Kuk Young

    2018-02-01

    High-voltage operation of lithium-ion batteries (LIBs) is a facile approach to obtaining high specific energy density, especially for LiNi0·5Mn0·3Co0·2O2 (NMC532) cathodes currently used in mid- and large-sized energy storage devices. However, high-voltage charging (>4.3 V) is accompanied by a rapid capacity fade over long cycles due to severe continuous electrolyte decomposition and instability at the cathode surface. In this study, the sulfite-based compound, [4,4‧-bi(1,3,2-dioxathiolane)] 2,2‧-dioxide (BDTD) is introduced as a novel electrolyte additive to enhance electrochemical performances of alumina-coated NMC532 cathodes cycled in the voltage range of 3.0-4.6 V. X-ray photoelectron spectroscopy (XPS) and AC impedance of cells reveal that BDTD preferentially oxidizes prior to the electrolyte solvents and forms stable film layers on to the cathode surface, preventing increased impedance caused by repeated electrolyte solvent decomposition in high-voltage operation. The cycling performance of the Li/NMC532 half-cell using an electrolyte of 1.0 M LiPF6 in ethylene carbonate/ethyl methyl carbonate (3/7, in volume) can be improved by adding a small amount of BDTD into the electrolyte. BDTD enables the usage of sulfite-type additives for cathodes in high-voltage operation.

  16. Natural product-based 6-hydroxy-2 3 4 6-tetrahydropyrrolo[1 2-a]pyrimidinium Scaffold as a new antifungal template

    USDA-ARS?s Scientific Manuscript database

    Synthetic analogues of the marine-derived class of natural products phloeodictines have been prepared and exhibited potent in vitro fungicidal activities against a broad array of fungal pathogens including drug-resistant strains. The 6-hydroxy-2,3,4,6-tetrahydropyrrolo[1,2-a] pyrimidinium structura...

  17. Reoccurrence of avian influenza A(H5N2) virus clade 2.3.4.4 in wild birds, Alaska, USA, 2016

    USDA-ARS?s Scientific Manuscript database

    We report reoccurrence of highly pathogenic avian influenza A(H5N2) virus clade 2.3.4.4 in a wild mallard in Alaska, USA, in August 2016. Identification of this virus in a migratory species confirms low-frequency persistence in North America and the potential for re-dissemination of the virus during...

  18. Novel routes to 1,2,3,4-tetrahydropyrrolo[1,2-a]pyrazines and 5,6,9,10,11,11a-hexahydro-8H-pyrido[1,2-a]pyrrolo[2,1-c]pyrazines.

    PubMed

    Katritzky, Alan R; Jain, Ritu; Xu, Yong-Jiang; Steel, Peter J

    2002-11-15

    Condensation reactions of benzotriazole and 2-(pyrrol-1-yl)-1-ethylamine (1) with formaldehyde and glutaric dialdehyde, respectively, afforded intermediates 2 and 6. Subsequent nucleophilic substitutions of the benzotriazole group in 2 and 6 with Grignard reagents, sodium cyanide, and sodium borohydride gave 1,2,3,4-tetrahydropyrrolo[1,2-a]pyrazines 3a-e, 4, 5 and 5,6,9,10,11,11a-hexahydro-8H-pyrido[1,2-a]pyrrolo[2,1-c]pyrazines 7a-c, 8, 9, respectively, in good yields.

  19. A one-dimensional nickel(II) coordination polymer containing 2,6-dipicolinate and dipyrido[3,2-a:2',3'-c]phenazine.

    PubMed

    Ma, Yi; Zhang, Li-Tian; Wang, Xiao-Fang; He, Yong-Ke; Han, Zheng-Bo

    2007-12-01

    A new coordination polymer, catena-poly[[(dipyrido[3,2-a:2',3'-c]phenazine-kappa(2)N,N')nickel(II)]-mu-2,6-dipicolinato-kappa(4)O(2),N,O(6):O(2')], [Ni(C7H3NO4)(C18H10N4)]n, exhibits a one-dimensional structure in which 2,6-dipicolinate acts as a bridging ligand interconnecting adjacent nickel(II) centers to form a chain structure. The asymmetric unit contains one Ni(II) center, one dipyrido[3,2-a:2',3'-c]phenazine ligand and one 2,6-dipicolinate ligand. Each Ni(II) center is six-coordinated and surrounded by three N atoms and three O atoms from one dipyrido[3,2-a:2',3'-c]phenazine ligand and two different 2,6-dipicolinate ligands, leading to a distorted octahedral geometry. Adjacent chains are linked by pi-pi stacking interactions and weak interactions to form a three-dimensional supramolecular network.

  20. Magnetic domain interactions of Fe3O4 nanoparticles embedded in a SiO2 matrix.

    PubMed

    Fuentes-García, J A; Diaz-Cano, A I; Guillen-Cervantes, A; Santoyo-Salazar, J

    2018-03-23

    Currently, superparamagnetic functionalized systems of magnetite (Fe 3 O 4 ) nanoparticles (NPs) are promising options for applications in hyperthermia therapy, drug delivery and diagnosis. Fe 3 O 4 NPs below 20 nm have stable single domains (SSD), which can be oriented by magnetic field application. Dispersion of Fe 3 O 4 NPs in silicon dioxide (SiO 2 ) matrix allows local SSD response with uniaxial anisotropy and orientation to easy axis, 90° <001> or 180° <111>. A successful, easy methodology to produce Fe 3 O 4 NPs (6-17 nm) has been used with the Stöber modification. NPs were embedded in amorphous and biocompatible SiO 2 matrix by mechanical stirring in citrate and tetraethyl orthosilicate (TEOS). Fe 3 O 4 NPs dispersion was sampled in the range of 2-12 h to observe the SiO 2 matrix formation as time function. TEM characterization identified optimal conditions at 4 h stirring for separation of SSD Fe 3 O 4 in SiO 2 matrix. Low magnetization (M s ) of 0.001 emu and a coercivity (H c ) of 24.75 Oe indicate that the embedded SSD Fe 3 O 4 in amorphous SiO 2 reduces the M s by a diamagnetic barrier. Magnetic force microscopy (MFM) showed SSD Fe 3 O 4 of 1.2 nm on average embedded in SiO 2 matrix with uniaxial anisotropy response according to Fe 3+ and Fe 2+ electron spin coupling and rotation by intrinsic Neél contribution.

  1. Reoccurrence of Avian Influenza A(H5N2) Virus Clade 2.3.4.4 in Wild Birds, Alaska, USA, 2016.

    PubMed

    Lee, Dong-Hun; Torchetti, Mia K; Killian, Mary Lea; DeLiberto, Thomas J; Swayne, David E

    2017-02-01

    We report reoccurrence of highly pathogenic avian influenza A(H5N2) virus clade 2.3.4.4 in a wild mallard in Alaska, USA, in August 2016. Identification of this virus in a migratory species confirms low-frequency persistence in North America and the potential for re-dissemination of the virus during the 2016 fall migration.

  2. Human reductive halothane metabolism in vitro is catalyzed by cytochrome P450 2A6 and 3A4.

    PubMed

    Spracklin, D K; Thummel, K E; Kharasch, E D

    1996-09-01

    The anesthetic halothane undergoes extensive oxidative and reductive biotransformation, resulting in metabolites that cause hepatotoxicity. Halothane is reduced anaerobically by cytochrome P450 (P450) to the volatile metabolites 2-chloro-1,1-difluoroethene (CDE) and 2-chloro-1,1,1-trifluoroethane (CTE). The purpose of this investigation was to identify the human P450 isoform(s) responsible for reductive halothane metabolism. CDE and CTE formation from halothane metabolism by human liver microsomes was determined by GC/MS analysis. Halothane metabolism to CDE and CTE under reductive conditions was completely inhibited by carbon monoxide, which implicates exclusively P450 in this reaction. Eadie-Hofstee plots of both CDE and CTE formation were nonlinear, suggesting multiple P450 isoform involvement. Microsomal CDE and CTE formation were each inhibited 40-50% by P450 2A6-selective inhibitors (coumarin and 8-methoxypsoralen) and 55-60% by P450 3A4-selective inhibitors (ketoconazole and troleandomycin). P450 1A-, 2B6-, 2C9/10-, and 2D6-selective inhibitors (7,8-benzoflavone, furafylline, orphenadrine, sulfaphenazole, and quinidine) had no significant effect on reductive halothane metabolism. Measurement of product formation catalyzed by a panel of cDNA-expressed P450 isoforms revealed that maximal rates of CDE formation occurred with P450 2A6, followed by P450 3A4. P450 3A4 was the most effective catalyst of CTE formation. Among a panel of 11 different human livers, there were significant linear correlations between the rate of CDE formation and both 2A6 activity (r = 0.64, p < 0.04) and 3A4 activity (r = 0.64, p < 0.03). Similarly, there were significant linear correlations between CTE formation and both 2A6 activity (r = 0.55, p < 0.08) and 3A4 activity (r = 0.77, p < 0.005). The P450 2E1 inhibitors 4-methylpyrazole and diethyldithiocarbamate inhibited CDE and CTE formation by 20-45% and 40-50%, respectively; however, cDNA-expressed P450 2E1 did not catalyze

  3. (CH3 NH3 )2 PdCl4 : A Compound with Two-Dimensional Organic-Inorganic Layered Perovskite Structure.

    PubMed

    Huang, Tang Jiao; Thiang, Zhang Xian; Yin, Xuesong; Tang, Chunhua; Qi, Guojun; Gong, Hao

    2016-02-01

    The synthesis of previously unknown perovskite (CH 3 NH 3 ) 2 PdCl 4 is reported. Despite using an organic cation with the smallest possible alkyl group, a 2D organic-inorganic layered Pd-based perovskites was still formed. This demonstrates that Pd-based 2D perovskites can be obtained even if the size of the organic cation is below the size limit predicted by the Goldschmidt tolerance-factor formula. The (CH 3 NH 3 ) 2 PdCl 4 phase has a bulk resistivity of 1.4 Ω cm, a direct optical gap of 2.22 eV, and an absorption coefficient on the order of 10 4  cm -1 . XRD measurements suggest that the compound is moderately stable in air, an important advantage over several existing organic-inorganic perovskites that are prone to phase degradation problems when exposed to the atmosphere. Given the recent interest in organic-inorganic perovskites, the synthesis of this new Pd-based organic-inorganic perovskite may be helpful in the preparation and understanding of other organic-inorganic perovskites. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. 3.0 V High Energy Density Symmetric Sodium-Ion Battery: Na4V2(PO4)3∥Na3V2(PO4)3.

    PubMed

    Yao, Xuhui; Zhu, Zixuan; Li, Qi; Wang, Xuanpeng; Xu, Xiaoming; Meng, Jiashen; Ren, Wenhao; Zhang, Xinhe; Huang, Yunhui; Mai, Liqiang

    2018-03-28

    Symmetric sodium-ion batteries (SIBs) are considered as promising candidates for large-scale energy storage owing to the simplified manufacture and wide abundance of sodium resources. However, most symmetric SIBs suffer from suppressed energy density. Here, a superior congeneric Na 4 V 2 (PO 4 ) 3 anode is synthesized via electrochemical preintercalation, and a high energy density symmetric SIB (Na 3 V 2 (PO 4 ) 3 as a cathode and Na 4 V 2 (PO 4 ) 3 as an anode) based on the deepened redox couple of V 4+ /V 2+ is built for the first time. When measured in half cell, both electrodes show stabilized electrochemical performance (over 3000 cycles). The symmetric SIBs exhibit an output voltage of 3.0 V and a cell-level energy density of 138 W h kg -1 . Furthermore, the sodium storage mechanism under the expanded measurement range of 0.01-3.9 V is disclosed through an in situ X-ray diffraction technique.

  5. Cation Dependence of the Dimerization Enthalpy for A2 [tetracyanoethylene]2 (A=NMe4 , Mepy, NEt4 ) Possessing a Long, Multicenter Bond.

    PubMed

    Graham, Adora G; Fedin, Matvey V; Miller, Joel S

    2017-09-12

    [TCNE] .- (TCNE=tetracyanoethylene) has been isolated as D 2h π-[TCNE] 2 2- possessing a long, 2.9 Å multicenter 2-electron-4-center (2e - /4c) C-C bond, and as C 2 π-[TCNE] 2 2- possessing a longer, 3.04 Å multicenter 2e - /6c (4 C+2 N atoms) bond. Temperature-dependent UV/Vis spectroscopic measurements in 2-methyltetrahydrofuran (MeTHF) has led to the determination of the dimerization, 2[TCNE] .- ⇌π-[TCNE] 2 2- , equilibrium constants, K eq (T), [[TCNE] 2 2- ]/[[TCNE] .- ] 2 , enthalpy, ΔH, and entropy, ΔS, of dimerization for [Mepy] 2 [TCNE] 2 (Mepy=N-methylpyridinium, H 3 CNC 5 H 5 + ) possessing D 2h π-[TCNE] 2 2- and [NMe 4 ] 2 [TCNE] 2 possessing C 2 π-[TCNE] 2 2- conformations in the solid state; however, both form D 2h π-[TCNE] 2 2- in MeTHF solution. Based on ΔH=-3.6±0.1 kcal mol -1 (-15.2 kJ mol -1 ), and ΔS=-11±1 eu (-47 J mol -1  K -1 ) and ΔH=-2.4±0.2 kcal mol -1 (-10.2 kJ mol -1 ), and ΔS=-8±1 eu (-32 J mol -1  K -1 ) in MeTHF for [NMe 4 ] 2 [TCNE] 2 and [Mepy] 2 [TCNE] 2 , respectively, the calculated K eq (298 K) are 1.6 and 1.3 m -1 , respectively. The observed K eq (145 K) are 3 and 2 orders of magnitude greater for [NMe 4 ] 2 [TCNE] 2 and [Mepy] 2 [TCNE] 2 , respectively. The K eq (130 K) is 4470, 257, ≈0.8, and ≪0.1 m -1 for [NMe 4 ] 2 [TCNE] 2 , [Mepy] 2 [TCNE] 2 , [NEt 4 ] 2 [TCNE] 2 , and [N(nBu) 4 ] 2 [TCNE] 2 , respectively, decreasing with increasing cation size. At standard conditions and below ambient temperature the equilibrium favors the dimer for the NMe 4 + and Mepy + cations. From the decreasing enthalpy, NMe 4 + >Mepy + , along with the decrease in dimer formation K eq (T) as NMe 4 + >Mepy + >NEt 4 + >N(nBu) 4 + , the dimer bond energy decreases with increasing cation size in MeTHF. This is attributed to a decrease in the [A] + ⋅⋅⋅[TCNE] - attractive interactions with increasing cation size. Solid state UV/Vis spectroscopic determinations of [NMe 4 ] 2

  6. Methanol Synthesis from CO2 Hydrogenation over a Pd4/In2O3 Model Catalyst: A Combined DFT and Kinetic Study

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

    Ye, Jingyun; Liu, Changjun; Mei, Donghai

    2014-08-01

    Methanol synthesis from CO2 hydrogenation on Pd4/In2O3 has been investigated using density functional theory (DFT) and microkinetic modeling. In this study, three possible routes in the reaction network of CO2 + H2 → CH3OH + H2O have been examined. Our DFT results show that the HCOO route competes with the RWGS route whereas a high activation barrier kinetically blocks the HCOOH route. DFT results also suggest that H2COO* + H* ↔ H2CO* +OH* and cis-COOH* + H* ↔CO* + H2O* are the rate limiting steps in the HCOO route and the RWGS route, respectively. Microkinetic modeling results demonstrate that themore » HCOO route is the dominant reaction route for methanol synthesis from CO2 hydrogenation. We found that the activation of H adatom on the small Pd cluster and the presence of H2O on the In2O3 substrate play important roles in promoting the methanol synthesis. The hydroxyl adsorbed at the interface of Pd4/In2O3 induces the transformation of the supported Pd4 cluster from a butterfly structure into a tetrahedron structure. This important structure change not only indicates the dynamical nature of the supported nanoparticle catalyst structure during the reaction but also shifts the final hydrogenation step from H2COH to CH3O.« less

  7. A fast synthesis of Li 3V 2(PO 4) 3 crystals via glass-ceramic processing and their battery performance

    NASA Astrophysics Data System (ADS)

    Nagamine, Kenta; Honma, Tsuyoshi; Komatsu, Takayuki

    A synthesis of Li 3V 2(PO 4) 3 being a potential cathode material for lithium ion batteries was attempted via a glass-ceramic processing. A glass with the composition of 37.5Li 2O-25V 2O 5-37.5P 2O 5 (mol%) was prepared by a melt-quenching method and precursor glass powders were crystallized with/without 10 wt% glucose in N 2 or 7%H 2/Ar atmosphere. It was found that heat treatments with glucose at 700 °C in 7%H 2/Ar can produce well-crystallized Li 3V 2(PO 4) 3 in the short time of 30 min. The battery performance measurements revealed that the precursor glass shows the discharge capacity of 14 mAh g -1 at the rate of 1 μA cm -2 and the glass-ceramics with Li 3V 2(PO 4) 3 prepared with glucose at 700 °C in 7%H 2/Ar show the capacities of 117-126 mAh g -1 (∼96% of the theoretical capacity) which are independent of heat treatment time. The present study proposes that the glass-ceramic processing is a fast synthesizing route for Li 3V 2(PO 4) 3 crystals.

  8. PHF13 is a molecular reader and transcriptional co-regulator of H3K4me2/3

    PubMed Central

    Chung, Ho-Ryun; Xu, Chao; Fuchs, Alisa; Mund, Andreas; Lange, Martin; Staege, Hannah; Schubert, Tobias; Bian, Chuanbing; Dunkel, Ilona; Eberharter, Anton; Regnard, Catherine; Klinker, Henrike; Meierhofer, David; Cozzuto, Luca; Winterpacht, Andreas; Di Croce, Luciano; Min, Jinrong; Will, Hans; Kinkley, Sarah

    2016-01-01

    PHF13 is a chromatin affiliated protein with a functional role in differentiation, cell division, DNA damage response and higher chromatin order. To gain insight into PHF13's ability to modulate these processes, we elucidate the mechanisms targeting PHF13 to chromatin, its genome wide localization and its molecular chromatin context. Size exclusion chromatography, mass spectrometry, X-ray crystallography and ChIP sequencing demonstrate that PHF13 binds chromatin in a multivalent fashion via direct interactions with H3K4me2/3 and DNA, and indirectly via interactions with PRC2 and RNA PolII. Furthermore, PHF13 depletion disrupted the interactions between PRC2, RNA PolII S5P, H3K4me3 and H3K27me3 and resulted in the up and down regulation of genes functionally enriched in transcriptional regulation, DNA binding, cell cycle, differentiation and chromatin organization. Together our findings argue that PHF13 is an H3K4me2/3 molecular reader and transcriptional co-regulator, affording it the ability to impact different chromatin processes. DOI: http://dx.doi.org/10.7554/eLife.10607.001 PMID:27223324

  9. Nature of phase transitions in ammonium oxofluorovanadates, a vibrational spectroscopy study of (NH4)3VO2F4 and (NH4)3VOF5.

    PubMed

    Gerasimova, Yu V; Oreshonkov, A S; Laptash, N M; Vtyurin, A N; Krylov, A S; Shestakov, N P; Ershov, A A; Kocharova, A G

    2017-04-05

    Two ammonium oxofluorovanadates, (NH 4 ) 3 VO 2 F 4 and (NH 4 ) 3 VOF 5 , have been investigated by temperature-dependent infrared and Raman spectroscopy methods to determine the nature of phase transitions (PT) in these compounds. Dynamics of quasioctahedral groups was simulated within the framework of semi-empirical approach, which justified the cis-conformation of VO 2 F 4 3- (C 2v ) and the C 4v geometry of VOF 5 3- . The observed infrared and Raman spectra of both compounds at room temperature (RT) revealed the presence at least of two crystallographically independent octahedral groups. The first order PT at elevated temperatures is connected with a complete dynamic disordering of these groups with only single octahedral state. At lower temperatures, the octahedra are ordered and several octahedral states appear. This PT is the most pronounced in the case of (NH 4 ) 3 VOF 5 , when at least seven independent VOF 5 3- octahedra are present in the structure below 50K, in accordance with the Raman spectra. Ammonium groups do not take part in PTs at higher and room temperatures but their reorientational motion freezes at lower temperatures. Copyright © 2017. Published by Elsevier B.V.

  10. X-Ray study of hetero ring flexibility in norbornane, norbornene-fused 1,3-oxazin-2-thiones Structure of 5,8-methano- r-4-phenyl-c-4a, c-5,6,7, c-8, c- 8a-hexahydro-4H- 1 ,3-benzoxazin-2 (3H)-thione

    NASA Astrophysics Data System (ADS)

    Kálmán, A.; Argay, Gy.; Stájer, G.; Bernáth, G.

    1991-08-01

    The structure of S,8-methano- r-4-phenyl c4a, c5,6,7 c8 c8ahexahydro4 H 1,3 -benzoxazin- 2 (3 H)-thione (C 15H 17N0S, M r=259.37) has been established by X-ray crystallography from diffractometer data: it crystallizes in the monoclinic space group P2 1/n with a=6.150(2) Å, b=9.655(1) Å, c=22.093(4) Å,β=96.75(2)† V=1302.7(8) Å 3,4,D c=1.32gcm -3and p( Cu K) =20.4cm -. The structure has been solved by direct methods, refined to R=0.050 for 2193 observed reflections. The X-ray analysis substantiated the structure: the NMR spectra in- dicated that the 4-phenyl group assumes an exo-equatorial position. The puckering parameters of D. Cremer, J.A. Pople, J. Am. Chem. Soc., 97 (1975), 1354 (ref.1), of the distorted hetero ring (a transitional form between E 4-envelope, ( 5S 4-screw-boat) show that, depending on the positions of the hetero atoms, both the norbornane, norbornene skeletons markedly alter the characteristic transitional ( 5E/ 5H 6) shape of the 1,3-oxazine ring observed in other saturated, partly saturated l,3-benzoxazin-2-ones, analogous thiones.

  11. 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.

  12. A novel (S)-(+)-decursin derivative, (S)-(+)-3-(3,4-dihydroxy-phenyl)-acrylic acid 2,2-dimethyl-8-oxo-3,4-dihydro-2H,8H-pyrano[3,2-g]chromen-3-yl-ester, inhibits ovalbumin-induced lung inflammation in a mouse model of asthma.

    PubMed

    Yang, Eun Ju; Song, Gyu-Yong; Lee, Ji-Sook; Yun, Chi-Young; Kim, In Sik

    2009-03-01

    (S)-(+)-Decursin is a coumarin compound present in herbal extracts that has various biological activities. (S)-(+)-Decursin attenuates pathophysiologic progression in cancer, bacterial infection and neuropathy. Asthma is an inflammatory disease associated with increased infiltration of leukocytes, especially eosinophils, and secretion of mucus into the airways. Although (S)-(+)-decursin, as well as (S)-(+)-decursin analogues, have various pharmacological properties, the effect of these compounds on asthma is not known. In the present study, we synthesized (S)-(+)-3-(3,4-dihydroxy-phenyl)-acrylic acid 2,2-dimethyl-8-oxo-3,4-dihydro-2H,8H-pyrano[3,2-g]chromen-3-yl-ester (compound 6, C6) from (S)-(+)-decursin and examined if C6 had any inhibitory effects on lung inflammation in a mouse model of ovalbumin-induced asthma. C6 significantly inhibited the leukocytosis (p < 0.01) and eosinophilia (p < 0.05) in bronchoalveolar lavage (BAL) fluid. Examination of lung tissues stained with hematoxylin and eosin and periodic acid Schiff reagents showed that C6 suppressed the increased infiltration of inflammatory cells and elevated mucus hypersecretion. Protein levels of interleukin (IL)-5 (p < 0.05) and eotaxin (p < 0.01) were significantly reduced in BAL fluid by C6. C6 also significantly reduced total and ovalbumin-specific immunoglobulin E (IgE) levels in BAL fluid (p < 0.01) as well as that in serum (p < 0.05). C6 may have pharmacological effects for asthma and may be a potent therapeutic agent for the treatment of allergic airway diseases.

  13. Thermal analysis of a diffusion bonded Er3+,Yb3+:glass/Co2+: MgAl2O4 microchip lasers

    NASA Astrophysics Data System (ADS)

    Belghachem, Nabil; Mlynczak, Jaroslaw; Kopczynski, krzysztof; Mierczyk, Zygmunt; Gawron, Michal

    2016-10-01

    The analysis of thermal effects in a diffusion bonded Er3+,Yb3+:glass/Co2+:MgAl2O4 microchip laser is presented. The analysis is performed for both wavelengths at 940 nm and at 975 nm as well as for two different sides of pumping, glass side and saturable absorber side. The heat sink effect of Co2+:MgAl2O4, as well as the impact of the thermal expansion and induced stress on the diffusion bonding are emphasised. The best configurations for reducing the temperature peaks, the Von Mises stresses on the diffusion bonding, and the thermal lensing are determined.

  14. A short and facile synthesis of 2-(1Z)-(3-hydroxy-3,7-dimethylocta-1,6-dienyl)-1,4-benzenediol and 1-(3'-methoxypropanoyl)-2,4,5-trimethoxybenzene isolated from Cordia alliodora.

    PubMed

    Kaur, Sukhbir; Singh, Vasundhara; Kumar, Gulshan; Kad, G L; Singh, Jasvinder

    2010-03-01

    A novel synthesis of 2-(1Z)-(3-hydroxy-3,7-dimethylocta-1,6-dienyl)-1,4-benzenediol and 1-(3'-methoxypropanoyl)-2,4,5-trimethoxybenzene has been carried out by making use of an easily available starting material, acceleration by MW irradiation and the use of water as a green solvent in the key steps.

  15. Catalytic Silylation of N 2 and Synthesis of NH 3 and N 2H 4 by Net Hydrogen Atom Transfer Reactions Using a Chromium P 4 Macrocycle

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

    Kendall, Alexander J.; Johnson, Samantha I.; Bullock, R. Morris

    We report the first discrete molecular Cr-based catalysts for the reduction of N2. This study is focused on the reactivity of the Cr-N2 complex, trans-[Cr(N2)2(PPh4NBn4)] P4Cr(N2)2, bearing a 16-membered tetraphosphine macrocycle. The architecture of the [16]-PPh4NBn4 ligand is critical to preserve the structural integrity of the catalyst. P4Cr(N2)2 was found to mediate the reduction of N2 by three complementary reaction pathways: (1) Cr-catalyzed reduction of N2 to N(SiMe3)3 by Na and Me3SiCl affording up to 34 equiv N(SiMe3)3; (2) stoichiometric reduction of N2 by protons and electrons. For example, the reaction of cobaltocene (CoCp2) and collidinium triflate (ColH[OTf]) at roommore » temperature to afforded 1.9 equiv of NH3, or at -78 °C to afforded a mixture of NH3 and N2H4; (3) the first example of NH3 formation from the reaction of a terminally bound N2 ligand with a traditional H atom source, TEMPOH, (2,2,6,6-tetramethylpiperidine-1-ol). We found that trans-[Cr(15N2)2(PPh4NBn4)] reacts with excess TEMPOH to afford a 1.4 equiv of 15NH3.« less

  16. 3-(3-Hydroxy-4-methoxyphenyl)-4-(3,4,5-trimethoxyphenyl)-1,2,5-selenadiazole (G-1103), a novel combretastatin A-4 analog, induces G2/M arrest and apoptosis by disrupting tubulin polymerization in human cervical HeLa cells and fibrosarcoma HT-1080 cells.

    PubMed

    Zuo, Daiying; Guo, Dandan; Jiang, Xuewei; Guan, Qi; Qi, Huan; Xu, Jingwen; Li, Zengqiang; Yang, Fushan; Zhang, Weige; Wu, Yingliang

    2015-02-05

    Microtubule is a popular target for anticancer drugs. In this study, we describe the effect 3-(3-hydroxy-4-methoxyphenyl)-4-(3,4,5-trimethoxyphenyl)-1,2,5-selenadiazole (G-1103), a newly synthesized analog of combretastatin A-4 (CA-4), showing a strong time- and dose-dependent anti-proliferative effect on human cervical cancer HeLa cells and human fibrosarcoma HT-1080 cells. We demonstrated that the growth inhibitory effects of G-1103 in HeLa and HT-1080 cells were associated with microtubule depolymerization and proved that G-1103 acted as microtubule destabilizing agent. Furthermore, cell cycle analysis revealed that G-1103 treatment resulted in cell cycle arrest at the G2/M phase in a time-dependent manner with subsequent apoptosis induction. Western blot analysis revealed that down-regulation of cdc25c and up-regulation of cyclin B1 was related with G2/M arrest in HeLa and HT-1080 cells treatment with G-1103. In addition, G-1103 induced HeLa cell apoptosis by up-regulating cleaved caspase-3, Fas, cleaved caspase-8 expression, which indicated that G-1103 induced HeLa cell apoptosis was mainly associated with death receptor pathway. However, G-1103 induced HT-1080 cell apoptosis by up-regulating cleaved caspase-3, Fas, cleaved caspase-8, Bax and cleaved caspase-9 expression and down-regulating anti-apoptotic protein Bcl-2 expression, which indicated that G-1103 induced HT-1080 cell apoptosis was associated with both mitochondrial and death receptor pathway. Taken together, all the data demonstrated that G-1103 exhibited its antitumor activity through disrupting the microtubule assembly, causing cell cycle arrest and consequently inducing apoptosis in HeLa and HT-1080 cells. Therefore, the novel compound G-1103 is a promising microtubule inhibitor that has great potentials for therapeutic treatment of various malignancies. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  17. Neutron scattering studies of K3H(SO4)2 and K3D(SO4)2: the particle-in-a-box model for the quantum phase transition.

    PubMed

    Fillaux, François; Cousson, Alain

    2012-08-21

    In the crystal of K(3)H(SO(4))(2) or K(3)D(SO(4))(2), dimers SO(4)···H···SO(4) or SO(4)···D···SO(4) are linked by strong centrosymmetric hydrogen or deuterium bonds whose O···O length is ≈2.50 Å. We address two open questions. (i) Are H or D sites split or not? (ii) Is there any structural counterpart to the phase transition observed for K(3)D(SO(4))(2) at T(c) ≈ 85.5 K, which does not exist for K(3)H(SO(4))(2)? Neutron diffraction by single-crystals at cryogenic or room temperature reveals no structural transition and no resolvable splitting of H or D sites. However, the width of the probability densities suggest unresolved splitting of the wavefunctions suggesting rigid entities H(L1/2)-H(R1/2) or D(L1/2)-D(R1/2) whose separation lengths are l(H) ≈ 0.16 Å or l(D) ≈ 0.25 Å. The vibrational eigenstates for the center of mass of H(L1/2)-H(R1/2) revealed by inelastic neutron scattering are amenable to a square-well and we suppose the same potential holds for D(L1/2)-D(R1/2). In order to explain dielectric and calorimetric measurements of mixed crystals K(3)D((1-ρ))H(ρ)(SO(4))(2) (0 ≤ ρ ≤ 1), we replace the classical notion of order-disorder by the quantum notion of discernible (e.g., D(L1/2)-D(R1/2)) or indiscernible (e.g., H(L1/2)-H(R1/2)) components depending on the separation length of the split wavefunction. The discernible-indiscernible isostructural transition at finite temperatures is induced by a thermal pure quantum state or at 0 K by ρ.

  18. Hematite (α-Fe2O3) - A potential Ce4+ carrier in red mud.

    PubMed

    Bolanz, Ralph M; Kiefer, Stefan; Göttlicher, Jörg; Steininger, Ralph

    2018-05-01

    Cerium is the most abundant rare earth element (REE) within the waste product of alumina production (red mud), but its speciation in this complex material is still barely understood. Previous studies showed evidence for a correlation between Ce and the main constituent of red mud, iron oxides, which led us to investigate the most abundant iron oxide in red mud, hematite, as possible carrier phase for Ce. Synthetic hematite can incorporate up to 1.70±0.01wt% Ce, which leads to a systematical increase of all unit cell parameters. Investigations by extended X-ray absorption fine structure spectroscopy suggest an incorporation of Ce 4+ O 6 into the hematite structure by a novel atomic arrangement, fundamentally different from the close-range order around Fe 3+ in hematite. Samples of red mud were taken in Lauta (Saxony), Germany and analyzed by powder X-ray diffraction, inductively coupled plasma mass and optical emission spectrometry, electron microprobe analysis and X-ray absorption near-edge structure spectroscopy. Red mud samples consist of hematite (Fe 2 O 3 ) (34-58wt%), sodalite (Na 8 Al 6 Si 6 O 24 Cl 2 ) (4-30wt%), gibbsite (Al(OH) 3 ) (0-25wt%), goethite (FeOOH) (10-23wt%), böhmite (AlOOH) (0-11wt%), rutile (TiO 2 ) (4-8wt%), cancrinite (Na 6 Ca 2 Al 6 Si 6 O 24 (CO 3 ) 2 ) (0-5wt%), nordstrandite (Al(OH) 3 ) (0-5wt%) and quartz (SiO 2 ) (0-4wt%). While the main elemental composition is Fe>Al>Na>Ti>Ca (Si not included), the average concentration of REE is 1109±6mg/kg with an average Ce concentration of 464±3mg/kg. The main carrier of Ce was located in the Fe-rich fine-grained fraction of red mud (0.10wt% Ce 2 O 3 ), while other potential Ce carriers like monazite, lead oxides, secondary Ce-minerals and particles of potentially anthropogenic origin are of subordinated relevance. Cerium in red mud occurs predominantly as Ce 4+ , which further excludes Ce 3+ minerals as relevant sources. Copyright © 2017. Published by Elsevier B.V.

  19. A Case Report of a Patient Carrying CYP2C9*3/4 Genotype with Extremely Low Warfarin Dose Requirement

    PubMed Central

    Lee, Soo-Youn; Nam, Myung-Hyun; Kim, June Soo

    2007-01-01

    We report a case of intolerance to warfarin dosing due to impaired drug metabolism in a patient with CYP2C9*3/*4. A 73-yr-old woman with atrial fibrilation was taking warfarin. She attained a high prothrombin time international normalized ratio (INR) at the standard doses during the induction of anticoagulation and extremely low dose of warfarin (6.5 mg/week) was finally chosen to reach the target INR. Genotyping for CYP2C9 revealed that this patient had a genotype CYP2C9*3/*4. This is the first Korean compound heterozygote for CYP2C9*3 and *4. This case suggests the clinical usefulness of pharmacogenetic testing for individualized dosage adjustments of warfarin. PMID:17596671

  20. A case report of a patient carrying CYP2C9*3/4 genotype with extremely low warfarin dose requirement.

    PubMed

    Lee, Soo Youn; Nam, Myung Hyun; Kim, June Soo; Kim, Jong Won

    2007-06-01

    We report a case of intolerance to warfarin dosing due to impaired drug metabolism in a patient with CYP2C9*3/*4. A 73-yr-old woman with atrial fibrilation was taking warfarin. She attained a high prothrombin time international normalized ratio (INR) at the standard doses during the induction of anticoagulation and extremely low dose of warfarin (6.5 mg/week) was finally chosen to reach the target INR. Genotyping for CYP2C9 revealed that this patient had a genotype CYP2C9*3/*4. This is the first Korean compound heterozygote for CYP2C9*3 and *4. This case suggests the clinical usefulness of pharmacogenetic testing for individualized dosage adjustments of warfarin.

  1. Growth of In/sub 2/S/sub 3/ and CdIn/sub 2/S/sub 4/ single crystals from a solution in a melt

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

    Buzhor, V.P.; Lyalikova, R. Yu.; Radautsan, S.I.

    1986-08-01

    The authors studied the reaction of In/sub 2/S/sub 3/ and CdIn/sub 2/S/sub 4/ with melts based on cadmium chloride. As the initial materials, they used polycrystalline In/sub 2/S/sub 3/ and CdIn/sub 2/S/sub 4/, cadmium chloride, and cadmium sulfide. The studies were carried out by the method of thermal analysis in sealed quartz ampules on an MOM derivatotograph. The solubility curve of In/sub 2/S/sub 3/ in a cadmium chloride melt is given. Nucleation occurs both within the liquid pahse and on the walls of the reaction container. At cooling rates of 4-5 K/h, with a charge of 100 g in amore » reaction container of diameter 20 mm the authors obtained In/sub 2/S/sub 3/ and CdIn/sub 2/S/sub 4/ crystals measuring 10-12 mm in size.« less

  2. High transport and excellent optical property of a two-dimensional single-layered hybrid perovskite (C4H9NH3)2PbBr4: a theoretical study.

    PubMed

    Lei, Jun-Hui; Zhao, Yu-Qing; Tang, Qiong; Lin, Jian-Guo; Cai, Meng-Qiu

    2018-05-16

    Organic-inorganic hybrid perovskites are developed to pursue high charge carrier mobility and light absorption coefficient. In this study, we present a detailed comparative research of the atomic and electronic structures of single-layered perovskites (C4H9NH3)2PbBr4 with two-dimensional/three-dimensional (2D/3D) spatial arrangement to predict the in plane charge carrier mobility along with the charge effective mass, elastic constant, and deformation potential. The calculated results reveal that the intrinsic in plane carrier mobilities of 2D single-layered hybrid perovskite (C4H9NH3)2PbBr4 along the 100 and 010 directions are superior to those of the 3D structure. Furthermore, the optical properties are calculated from the electronic structure; it is found that the light absorption spectrum of 2D single-layered perovskite (C4H9NH3)2PbBr4 with a high absorption coefficient is wider than that of the 3D phase. We speculate that the superior mobility and wider absorption spectrum of the 2D mono-layered perovskite are due to high charge density and ferroelectricity originating from structure distortion upon 3D-to-2D structure transformation. These results indicate that the 2D single-layered hybrid perovskite (C4H9NH3)2PbBr4 is a potential candidate for application in the optoelectronic and photovoltaic fields.

  3. Total synthesis of 4-acetyl-1,3-dihydroimidazo[4,5-c]pyridin-2-one, a new microbial metabolite from a Streptomyces species.

    PubMed

    Bender, Tobias; von Zezschwitz, Paultheo

    2009-07-01

    The structure of a new secondary metabolite from Streptomyces sp. was determined as 4-acetyl-1,3-dihydroimidazo[4,5-c]pyridin-2-one by synthesis of the natural product itself and of the regioisomeric 7-acetylimidazo[4,5-b]pyridine derivative. The former compound was prepared, in 28% overall yield, in a sequence of nitration, reduction, condensation, and Stille reaction of 4-aminopyridine, while the regioisomer was obtained in 5% overall yield by amination, nitration, reduction, condensation, and oxidation of 4-ethylpyridine.

  4. [(CH3)3NCH2CH2NH3]SnI4: a layered perovskite with quaternary/primary ammonium dications and short interlayer iodine-iodine contacts.

    PubMed

    Xu, Zhengtao; Mitzi, David B; Medeiros, David R

    2003-03-10

    The organic-inorganic hybrid [(CH(3))(3)NCH(2)CH(2)NH(3)]SnI(4) presents a layered perovskite structure, templated by an organic dication containing both a primary and a quaternary ammonium group. Due to the high charge density and small size of the organic cation, the separation of the perovskite layers is small and short iodine-iodine contacts of 4.19 A are formed between the layers. Optical thin-film measurements on this compound indicate a significant red shift of the exciton peak (630 nm) associated with the band gap, as compared with other SnI(4)(2)(-)-based layered perovskite structures.

  5. Synthesis and crystal structures of nitratocobaltates Na2[Co(NO3)4], K2[Co(NO3)4], and Ag[Co(NO3)3] and potassium nitratonickelate K2[Ni(NO3)4

    NASA Astrophysics Data System (ADS)

    Morozov, I. V.; Fedorova, A. A.; Albov, D. V.; Kuznetsova, N. R.; Romanov, I. A.; Rybakov, V. B.; Troyanov, S. I.

    2008-03-01

    The cobalt(II) and nickel(II) nitrate complexes with an island structure (Na2[Co(NO3)4] ( I) and K2[Co(NO3)4] ( II)] and a chain structure [Ag[Co(NO3)3] ( III) and K2[Ni(NO3)4] ( IV)] are synthesized and investigated using X-ray diffraction. In the anionic complex [Co(NO3)4]2- of the crystal structure of compound I, the Co coordination polyhedron is a twisted tetragonal prism formed by the O atoms of four asymmetric bidentate nitrate groups. In the anion [Co(NO3)4]2- of the crystal structure of compound II, one of the four NO3 groups is monodentate and the other NO3 groups are bidentate (the coordination number of the cobalt atom is equal to seven, and the cobalt coordination polyhedron is a monocapped trigonal prism). The crystal structures of compounds III and IV contain infinite chains of the compositions [Co(NO3)2(NO3)2/2]- and [Ni(NO3)3(NO3)2/2]2-, respectively. In the crystal structure of compound III, seven oxygen atoms of one monodentate and three bidentate nitrate groups form a dodecahedron with an unoccupied vertex of the A type around the Co atom. In the crystal structure of compound IV, the octahedral polyhedron of the Ni atom is formed by five nitrate groups, one of which is terminal bidentate. The data on the structure of Co(II) coordination polyhedra in the known nitratocobaltates are generalized.

  6. Reactions at the Metal Vertex of a Monometal Metallocarborane Cluster. The Chemistry of (closo-3,3-(PPh3)2-3-(HSO4)-3,1,2-RhC2B9H11) and (closo-3-(PPh3)-3,3-(NO3)-3,1,2RhC2B9H11).

    DTIC Science & Technology

    1982-03-09

    4) produced by dissociation of PPh 3 from (2) or through an ionic species such as [closo-3,3- (PPh 3)2 -3,1,2-RhC 289 H ] [HSO4 (4a). Secondly, the...acetylene molecule and subsequent insertion into a metal-carbon bond has been observed in the linear oligomerization of acetylere catalyzed by [Ni(CO...monoxide were obtained from Liquid Carbonic and used without further treatment. Phenylacetylene (Aldrich) was distilled under vacuum before use and n

  7. Catalytic Properties of Botulinum Neurotoxins Subtypes A3 and A4

    PubMed Central

    Henkel, James S.; Jacobson, Mark; Tepp, William; Pier, Christina; Johnson, Eric A.; Barbieri, Joseph T.

    2009-01-01

    Botulinum toxins (BoNT) are zinc proteases (serotypes A-G) which cause flaccid paralysis through the cleavage of SNARE proteins within motor neurons. BoNT/A was originally organized into two subtypes: BoNT/A1 and BoNT/A2, which are ~ 95 % homologous and possess similar catalytic activities. Subsequently, two additional subtypes were identified; BoNT/A3 (Loch Maree), and BoNT/A4 (657Ba), which have 81 and 88% homology with BoNT/A1, respectively. Alignment studies predicted that BoNT/A3 and BoNT/A4 were sufficiently different to BoNT/A1 to affect SNAP25 binding and cleavage. Recombinant Light Chain (LC) of BoNT/A3 (LC/A3) and BoNT/A4 (LC/A4) were subjected to biochemical analysis. LC/A3 cleaved SNAP25 at 50% the rate of LC/A1, but cleaved SNAPtide® at a faster rate than LC/A1, while LC/A4 cleaved SNAP25 and SNAPtide® at slower rates than LC/A1. LC/A3 and LC/A4 had similar Kms for SNAP25 relative to LC/A1, while the kcat for LC/A4 was 10- fold slower than LC/A1, suggesting a defect in substrate cleavage. Neither LC/A3 nor LC/A4 possessed autocatalytic activity, a property of LC/A1 and LC/A2. Thus, the four subtypes of BoNT/A bind SNAP25 with similar affinity but have different catalytic capacities for SNAP25 cleavage, SNAPtide® cleavage, and autocatalysis. The catalytic properties identified among the subtypes of LC/A may influence strategies for the development of small molecule- or peptide- inhibitors as therapies against botulism. PMID:19256469

  8. Effect of (R)-2-(2-aminothiazol-4-yl)-4'-{2-[(2-hydroxy-2-phenylethyl)amino]ethyl} acetanilide (YM178), a novel selective beta3-adrenoceptor agonist, on bladder function.

    PubMed

    Takasu, Toshiyuki; Ukai, Masashi; Sato, Shuichi; Matsui, Tetsuo; Nagase, Itsuro; Maruyama, Tatsuya; Sasamata, Masao; Miyata, Keiji; Uchida, Hisashi; Yamaguchi, Osamu

    2007-05-01

    We evaluated the pharmacological characteristics of (R)-2-(2-aminothiazol-4-yl)-4'-{2-[(2-hydroxy-2-phenylethyl)amino]-ethyl} acetanilide (YM178). YM178 increased cyclic AMP accumulation in Chinese hamster ovary (CHO) cells expressing human beta3-adrenoceptor (AR). The half-maximal effective concentration (EC50) value was 22.4 nM. EC50 values of YM178 for human beta1- and beta2-ARs were 10,000 nM or more, respectively. The ratio of intrinsic activities of YM178 versus maximal response induced by isoproterenol (nonselective beta-AR agonist) was 0.8 for human beta3-ARs, 0.1 for human beta1-ARs, and 0.1 for human beta2-ARs. The relaxant effects of YM178 were evaluated in rats and humans bladder strips precontracted with carbachol (CCh) and compared with those of isoproterenol and 4-[3-[(1,1-dimethylethyl)amino]-2-hydroxypropoxy]-1,3-dihydro-2H-benzimidazol-2-one hydrochloride (CGP-12177A) (beta3-AR agonist). EC50 values of YM178 and isoproterenol in rat bladder strips precontracted with 10(-6) M CCh were 5.1 and 1.4 microM, respectively, whereas those in human bladder strips precontracted with 10(-7) M CCh were 0.78 and 0.28 microM, respectively. In in vivo study, YM178 at a dose of 3 mg/kg i.v. decreased the frequency of rhythmic bladder contraction induced by intravesical filling with saline without suppressing its amplitude in anesthetized rats. These findings suggest the suitability of YM178 as a therapeutic drug for the treatment of symptoms of overactive bladder such as urinary frequency, urgency, and urge incontinence.

  9. A vibrational spectroscopic study of the phosphate mineral vantasselite Al4(PO4)3(OH)3·9H2O

    NASA Astrophysics Data System (ADS)

    Frost, Ray L.; Scholz, Ricardo; Belotti, Fernanda Maria; López, Andrés; Theiss, Frederick L.

    2015-08-01

    We have studied the phosphate mineral vantasselite Al4(PO4)3(OH)3·9H2O using a combination of SEM with EDX and Raman and infrared spectroscopy. Qualitative chemical analysis shows Al, Fe and P. Raman bands at 1013 and 1027 cm-1 are assigned to the PO43- ν1 symmetric stretching mode. The observation of two bands suggests the non-equivalence of the phosphate units in the vantasselite structure. Raman bands at 1051, 1076 and 1090 cm-1 are attributed to the PO43- ν3 antisymmetric stretching vibration. A comparison is made with the spectroscopy of wardite. Strong infrared bands at 1044, 1078, 1092, 1112, 1133, 1180 and 1210 cm-1 are attributed to the PO43- ν3 antisymmetric stretching mode. Some of these bands may be due to δAl2OH deformation modes. Vibrational spectroscopy offers a mechanism for the study of the molecular structure of vantasselite.

  10. Synthesis, structure, biochemical, and docking studies of a new dinitrosyl iron complex [Fe2(μ-SC4H3SCH2)2(NO)4

    NASA Astrophysics Data System (ADS)

    Davidovich, P. B.; Fischer, A. I.; Korchagin, D. V.; Panchuk, V. V.; Shchukarev, A. V.; Garabadzhiu, A. V.; Belyaev, A. N.

    2015-07-01

    A new dinitrosyl iron complex of binuclear structure [Fe2(μ-S-2-methylthiophene)2(NO)4] was first synthesized and structurally characterized by XRD and theoretical methods. Using caspase-3 as an example it was shown that [Fe2(μ-S-2-methylthiophene)2(NO)4] and its analog [Fe2(μ-S-2-methylfurane)2(NO)4] can inhibit the action of active site cysteine proteins; the difference in inhibitory activity was explained by molecular docking studies. Biochemical and in silico studies give grounds that the biological activity of dinitrosyl iron complexes is a μ-SR bridging ligand structure function. Thus the rational design strategy of [Fe2(μ-SR)2(NO)4] complexes can be applied to make NO prodrugs with high affinity to therapeutically significant targets involved in cancer and inflammation.

  11. Catalytic Silylation of N2 and Synthesis of NH3 and N2H4 by Net Hydrogen Atom Transfer Reactions Using a Chromium P4 Macrocycle.

    PubMed

    Kendall, Alexander J; Johnson, Samantha I; Bullock, R Morris; Mock, Michael T

    2018-02-21

    We report the first discrete molecular Cr-based catalysts for the reduction of N 2 . This study is focused on the reactivity of the Cr-N 2 complex, trans-[Cr(N 2 ) 2 (P Ph 4 N Bn 4 )] (P 4 Cr(N 2 ) 2 ), bearing a 16-membered tetraphosphine macrocycle. The architecture of the [16]-P Ph 4 N Bn 4 ligand is critical to preserve the structural integrity of the catalyst. P 4 Cr(N 2 ) 2 was found to mediate the reduction of N 2 at room temperature and 1 atm pressure by three complementary reaction pathways: (1) Cr-catalyzed reduction of N 2 to N(SiMe 3 ) 3 by Na and Me 3 SiCl, affording up to 34 equiv N(SiMe 3 ) 3 ; (2) stoichiometric reduction of N 2 by protons and electrons (for example, the reaction of cobaltocene and collidinium triflate at room temperature afforded 1.9 equiv of NH 3 , or at -78 °C afforded a mixture of NH 3 and N 2 H 4 ); and (3) the first example of NH 3 formation from the reaction of a terminally bound N 2 ligand with a traditional H atom source, TEMPOH (2,2,6,6-tetramethylpiperidine-1-ol). We found that trans-[Cr( 15 N 2 ) 2 (P Ph 4 N Bn 4 )] reacts with excess TEMPOH to afford 1.4 equiv of 15 NH 3 . Isotopic labeling studies using TEMPOD afforded ND 3 as the product of N 2 reduction, confirming that the H atoms are provided by TEMPOH.

  12. Metabolism and disposition of a novel antineoplastic JS-38 (Benzamide, N-[4-(2,4-dimethoxyphenyl)-4,5-dihydro-5-oxo-1,2-dithiolo[4,3-b]pyrrol-6-yl]-3,5-bis (trifluoromethyl)-(9Cl)) in rats.

    PubMed

    Zhang, Hong; Liu, Quanhai; Fan, Tingting; Fang, Yu; Li, Ying; Wang, Guoping

    2012-03-01

    The metabolism and catabolism of a novel antineoplastic (ID code JS-38),Benzamide, N-[4-(2,4-dimethoxyphenyl)-4,5-dihydro-5-oxo-1,2-dithiolo[4,3-b]pyrrol-6-yl]-3,5-bis (trifluoromethyl)-(9Cl), were investigated in Wistar rats (3 female, 3 male). LC/UV, LC/MS, LC/MS/MS, NMR and acid hydrolysis methods showed that the metabolic process of JS-38 consists of a series of acetylation and glucoronation that form a metabolic product with a unique pharmacologic property of accelerating bone-marrow cell formation, and also showed a novel metabolic pathway of being acetylated and glucuronated in series.

  13. Luminescent properties of SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} and its luminescence improvement by incorporating A{sup +} (A=Li, Na, and K)

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

    Li, Panlai, E-mail: li_panlai@126.com; Wang, Zhijun, E-mail: wangzj1998@126.com; Yang, Zhiping

    2014-12-15

    A novel green phosphor SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} is synthesized by a high temperature solid-state method, and its luminescent property is investigated. X-ray diffraction patterns of SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} indicate a similarity crystalline phase to SrZn{sub 2}(PO{sub 4}){sub 2}. SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} shows green emission under 369 nm excitation, and the prominent luminescence in green (544 nm) due to {sup 5}D{sub 4}–{sup 7}F{sub 5} transition of Tb{sup 3+}. For the 544 nm emission, excitation spectrum has several excitation band from 200 nm to 400 nm. Emission intensity of SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} is influencedmore » by Tb{sup 3+} concentration, and concentration quenching effect of Tb{sup 3+} in SrZn{sub 2}(PO{sub 4}){sub 2} is also observed. With incorporating A{sup +} (A=Li, Na, and K) as compensator charge, the emission intensity of SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} can be obviously enhanced. CIE color coordinates of SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} locate in the green region. The results indicate this phosphor may be a potential application in white LEDs. - Graphical abstract: SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} can produce green emission under near-UV excitation, and its luminescent properties can be improved by incorporating A{sup +} (A=Li, Na, and K). - Highlights: • SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} can produce green emission under near-UV excitation. • Concentration quenching effect of Tb{sup 3+} in SrZn{sub 2}(PO{sub 4}){sub 2} is observed. • Emission intensities of SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} are enhanced by codoped A{sup +} (A=Li, Na, K)« less

  14. Two actinide-organic frameworks constructed by a tripodal flexible ligand: Occurrence of infinite {(UO2)O2(OH)3}4n and hexanuclear {Th6O4(OH)4} motifs

    NASA Astrophysics Data System (ADS)

    Liang, Lingling; Zhang, Ronglan; Zhao, Jianshe; Liu, Chiyang; Weng, Ng Seik

    2016-11-01

    Two new actinide metal-organic frameworks were constructed by using a tripodal flexible ligand tris (2-carboxyethyl) isocyanurate (H3tci) under hydrothermal condition. The combination of H3tci and uranyl nitrate hexahydrate in aqueous solution leads to the isolation of [(UO2)2(H2O)4]0.5(tci)2(UO2)4(OH)4·18H2O (1), which contains two distinct UO22+ coordination environments. Four uranyl cations, linked through μ3-OH respectively, result in the edge-sharing ribbons. Then, the layer structure is constructed by U-O clusters linked through other eight-coordinated uranyl unions, giving rise to a porous structure in the space. Topological analysis reveals that complex 1 belongs to a (4, 8)-connected net with a schläfli symbol of (34.26.3)2(34.46.56.68.73.8). Th3(tci)2O2(OH)2(H2O)3·12H2O (2) generated by the reaction of H3tci and thorium nitrate tetrahydrate, possesses nine-fold coodinated Th(IV) centers with a monocapped square antiprismatic geometry. The hexamers "Th6O4(OH)4" motifs are connected together by the carboxylate groups, showing a three-dimensional structures. Complex 2 takes on an 8-connected architecture and the point symbol is (424.64).

  15. New silicate-germanate Cs2Pb2[(Si0.6Ge0.4)2O7] from the series A2Pb2[B2O7], A = K, Cs, B = Si, Ge with the umbrella-like [PbO3]4- group

    NASA Astrophysics Data System (ADS)

    Belokoneva, Elena L.; Morozov, Ivan A.; Volkov, Anatoly S.; Dimitrova, Olga V.; Stefanovich, Sergey Yu.

    2018-04-01

    New silicate-germanate Cs2Pb2[(Si0.6Ge0.4)2O7] was synthesized in multi-components hydrothermal solution with 20 w.% concentration of Cs2CO3 mineralizer, pH = 10. Novel mixed compound belongs to the structure type A2Pb2[B2O7] previously indicated for powders with A = K, B=Si or Ge. Singe crystal structure determination of Cs2Pb2[(Si0.6Ge0.4)2O7] revealed the need for the correction of the space group of the earlier suggested structural model from P-3 to P-3m1, as well as for the splitting of the Pb-atom position. Umbrella-like groups [PbO3]4- are located between [(Si,Ge)O4]4- tetrahedra in mica-like honeycomb layers and play the role of tetrahedra with the Pb-lone-pair as the forth apex. Crystal chemical comparison revealed similarities and differences with the classical structure type of α-celsian Ba[Al2Si2O8] with the tetrahedral double layer. Recently investigated nonlinear optical acentric borates Pb2(BO3)(NO3) and Pb2(BO3)Cl are both related to this structural type, possessing umbrella-like groups [PbO3]4- and honeycomb layers [Pb2(BO3)]+ with the BO3-triangles on the tetrahedral positions.

  16. 3,4,5,6-Tetrafluorophenylnitren-2-yl: a ground-state quartet triradical.

    PubMed

    Grote, Dirk; Finke, Christopher; Kossmann, Simone; Neese, Frank; Sander, Wolfram

    2010-04-19

    The photochemistry of 2-iodo-3,4,5,6-tetrafluorophenyl azide (7 d) has been investigated in argon and neon matrices at 4 K, and the products characterized by IR and EPR spectroscopy. The primary photochemical step is loss of a nitrogen molecule and formation of phenyl nitrene 1 d. Further irradiation with UV or visible light results in mixtures of 1 d with azirine 5 d', ketenimine 6 d', nitreno radical 2 d, and azirinyl radical 9. The relative amounts of these products strongly depend on the matrix and on the irradiation conditions. Nitreno radical 2 d with a quartet ground state was characterized by EPR spectroscopy. Electronic structure calculations in combination with the experimental results allow for a detailed understanding of the properties of this unusual new type of organic high-spin molecules. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. 2-Amino-1,3,4-thiadiazole as a potential scaffold for promising antimicrobial agents.

    PubMed

    Serban, Georgeta; Stanasel, Oana; Serban, Eugenia; Bota, Sanda

    2018-01-01

    Pathogenic microorganisms are causative agents for different types of serious and even lethal infectious diseases. Despite advancements in medication, bacterial and fungal infections continue to be a growing problem in health care. As more and more bacteria become resistant to antibiotics used in therapy and an increasing number of invasive fungal species become resistant to current antifungal medications, there is considerable interest in the development of new compounds with antimicrobial activity. The compounds containing a heterocyclic ring play an important role among organic compounds with biological activity used as drugs in human and veterinary medicine or as insecticides and pesticides in agriculture. Thiadiazoles belong to the classes of nitrogen-sulfur heterocycles with extensive application as structural units of biologically active molecules and as useful intermediates in medicinal chemistry. The potency of the thiadiazole nucleus is demonstrated by the drugs currently used. 1,3,4-Thiadiazoles and some of their derivatives are extensively studied because of their broad spectrum of pharmacological activities. The aim of this review was to highlight the main antimicrobial properties exhibited by derivatives possessing 2-amino-1,3,4-thiadiazole moiety. Many of the reported 2-amino-1,3,4-thiadiazole derivatives can be considered as lead compounds for drug synthesis, and several of them have demonstrated higher antimicrobial activity in comparison to standard drugs. Furthermore, taking into account the reactivity of the amine group in the derivatization process, 2-amino-1,3,4-thiadiazole moiety may be a good scaffold for future pharmacologically active 1,3,4-thiadiazole derivatives.

  18. Spinel, YbFe2O4, and Yb2Fe3O7 types of structure for compounds in the In2O3 and Sc2O3-A2O3-BO systems (A: Fe, Ga, or Al; B: Mg, Mn, Fe, Ni, Cu, or Zn) at temperatures over 1000C

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

    Kimizuka, N.; Mohri, T.

    In the Sc2O3-Ga2O3-CuO, Sc2O3-Ga2O3-ZnO, and Sc2O3-Al2O3-CuO systems, ScGaCuO4, ScGaZnO4, and ScAlCuO4 with the YbFe2O4-type structure and Sc2Ga2CuO7 with the Yb2Fe3O7-type structure were obtained. In the In2O3-A2O3-BO systems (A: Fe, Ga, or Al; B: Mg, Mn, Fe, Ni, or Zn), InGaFeO4, InGaNiO4, and InFeT MgO4 with the spinel structure, InGaZnO4, InGaMgO4, and InAl-CuO4 with the YbFe2O4-type structure, and In2Ga2MnO7 and In2Ga2ZnO7 with the Yb2Fe3O7-type structure were obtained. InGaMnO4 and InFe2O4 had both the YbFe2O4-type and spinel-type structures. The revised classification for the crystal structures of AB2O4 compounds is presented, based upon the coordination numbers of constituent A and B cations. 5more » references, 2 tables.« less

  19. A polymorphic form of 4,4-dimethyl-8-methylene-3-azabicyclo[3.3.1]non-2-en-2-yl 3-indolyl ketone, an indole alkaloid extracted from Aristotelia chilensis (maqui).

    PubMed

    Paz, Cristian; Becerra, José; Silva, Mario; Freire, Eleonora; Baggio, Ricardo

    2013-12-15

    The title compound [systematic name: (4,4-dimethyl-8-methylene-3-azabicyclo[3.3.1]non-2-en-2-yl)(1H-indol-3-yl)methanone], C20H22N2O, (II), was obtained from mother liquors extracted from Aristotelia chilensis (commonly known as maqui), a native Chilean tree. The compound is a polymorphic form of that obtained from the same source and reported by Watson, Nagl, Silva, Cespedes & Jakupovic [Acta Cryst. (1989), C45, 1322-1324], (Ia). The molecule consists of an indolyl ketone fragment and a nested three-ring system, with both groups linked by a C-C bridge. Comparison of both forms shows that they do not differ in their gross features but in the relative orientation of the two ring systems, due to different rotations around the bridge, as measured by the O=C-C=N torsion angle [130.0 (7)° in (Ia) and 161.6 (2)° in (II)]. The resulting slight conformational differences are reflected in a number of intramolecular contacts being observed in (II) but not in (Ia). Regarding intermolecular interactions, both forms share a similar N-H···O synthon but with differing hydrogen-bonding strength, leading in both cases to C(6) catemers with different chain motifs. There are marked differences between the two forms regarding colour and the (de)localization of a double bond, which allows speculation about the possible existence of different variants of this type of molecule.

  20. A PXR reporter gene assay in a stable cell culture system: CYP3A4 and CYP2B6 induction by pesticides.

    PubMed

    Lemaire, Géraldine; de Sousa, Georges; Rahmani, Roger

    2004-12-15

    A stable hepatoma cell line expressing the human pregnane X receptor (hPXR) and the cytochrome P4503A4 (CYP3A4) distal and proximal promoters plus the luciferase reporter gene was developed to assess the ability of several xenobiotic agents to induce CYP3A4 and CYP2B6. After selection for neomycin resistance, one clone, displaying high luciferase activity in response to rifampicin (RIF), was isolated and the stable expression of hPXR was confirmed by reverse transcription polymerase chain reaction (RT-PCR). Dose-response curves were generated by treating these cells with increasing concentrations of RIF, phenobarbital (PB), clotrimazole (CLOT) or 5beta-pregnane-3,20-dione (5beta-PREGN). The effective concentrations for half maximal response (EC50) were determined for each of these compounds. RIF was the most effective compound, with maximal luciferase activity induced at 10 microM. The agonist activities of PXR-specific inducers measured using our stable model were consistent with those measured in transient transfectants. The abilities of organochlorine (OC), organophosphate (OP) and pyrethroid pesticides (PY) to activate hPXR were also assessed and found to be consistent with the abilities of these compounds to induce CYP3A4 and CYP2B6 in primary culture of human hepatocytes. These results suggest that CYP3A4 and CYP2B6 regulation through PXR activation by persistent pesticides may have an impact on the metabolism of xenobiotic agents and endogenous steroid hormones. Our model provides a useful tool for studying hPXR activation and for identifying agents capable of inducing CYP3A4 and CYP2B6.

  1. Syntheses, structures and luminescence for zinc coordination polymers based on a multifunctional 4‧-(3-carboxyphenyl)- 3,2‧:6‧,3″-terpyridine ligand

    NASA Astrophysics Data System (ADS)

    Cheng, Yue; Yang, Meng-Lin; Hu, Huai-Ming; Xu, Bing; Wang, Xiaofang; Xue, Ganglin

    2016-07-01

    Six new coordination polymers, [ZnLCl]n(1), [ZnL2]n·2nH2O (2), [Zn2L(o-bdc)(OH)]n·0.5nH2O (3), [Zn2L(m-bdc)(OH)]n·nH2O (4), [Zn2L2(p-bdc) (H2O)2]n·nH2O (5), [Zn2L(1,2,4-btc)(H2O)]n(6), (HL=4‧-(3-carboxyphenyl)- 3,2‧:6‧,3″-terpyridine, H2(o-bdc)= benzene-1,2-dicarboxylic acid, H2(m-bdc)= benzene-1,3-dicarboxylic acid, H2(p-bdc)= benzene-1,4-dicarboxylic acid, H3(1,2,4-btc)= benzene-1,2,4-tricarboxylic acid) have been synthesized under the hydrothermal conditions. Compound 1 displays a 3-connected 2D network structure with point symbol of {82.10}. Compound 2 exhibits 1D infinite loop chain structure. Compound 3 possesses a (3,8)-connected 3D framework composed of tetranuclear units with point symbol of {43}2{46.618.84}. Compound 4 features a typical 2D hcb network based on tetranuclear zinc(II) units with point symbol of {44.62}. Compound 5 presents a classical two-fold penetration sql network with point symbol of {63}. Compound 6 can be seen as a (3,3,6)-connected 3D net with point symbol of {42.64.89}{42.6}{63}. The thermal stability and luminescent properties of compounds 1-6 in the solid state are discussed in detail.

  2. Nomenclature updates resulting from the evolution of avian influenza A(H5) virus clades 2.1.3.2a, 2.2.1, and 2.3.4 during 2013-2014.

    PubMed

    Smith, Gavin J D; Donis, Ruben O

    2015-09-01

    The A/goose/Guangdong/1/96-like hemagglutinin (HA) genes of highly pathogenic avian influenza (HPAI) A(H5) viruses have continued to rapidly evolve since the most recent update to the H5 clade nomenclature by the WHO/OIE/FAO H5N1 Evolution Working Group. New clades diverging beyond established boundaries need to be identified and designated accordingly. Hemagglutinin sequences deposited in publicly accessible databases up to December 31, 2014, were analyzed by phylogenetic and average pairwise distance methods to identify new clades that merit nomenclature changes. Three new clade designations were recommended based on division of clade 2·1·3·2a (Indonesia), 2·2·1 (Egypt), and 2·3·4 (widespread detection in Asia, Europe, and North America) that includes newly emergent HPAI virus subtypes H5N2, H5N3, H5N5, H5N6, and H5N8. Continued global surveillance for HPAI A(H5) viruses in all host species and timely reporting of sequence data will be critical to quickly identify new clades and assess their potential impact on human and animal health. © 2015 The Authors. Influenza and Other Respiratory Viruses Published by John Wiley & Sons Ltd.

  3. Supercritical water oxidation of 2-, 3- and 4-nitroaniline: A study on nitrogen transformation mechanism.

    PubMed

    Yang, Bowen; Cheng, Zhiwen; Fan, Maohong; Jia, Jinping; Yuan, Tao; Shen, Zhemin

    2018-08-01

    Supercritical water oxidation (SCWO) of 2-, 3- and 4-nitroaniline (NA) was investigated under residence time of 1-6 min, pressure of 18-26 MPa, temperature of 350-500 °C, with initial concentration of 1 mM and 300% excess oxygen. Among these operating conditions, temperature and residence time played a more significant role in decomposing TOC and TN than pressure. Moreover, the products of N-containing species were mainly N 2 , ammonia and nitrate. When temperature, pressure and retention time enhanced, the yields of NO 3 - and org-N were reduced, the amount of N 2 was increasing, the proportion of NH 4 + , however, presented a general trend from rise to decline in general. The experiment of aniline/nitrobenzene indicated that TN removal behavior between amino and nitro groups would prefer to happen in the molecule rather than between the molecules, therefore, the smaller interval between the amino and nitro group was the more easily to interreact. This might explain the reason why TN removal efficiency was in an order that 2-NA > 3-NA > 4-NA. The NH 4 + /NO 3 - experiment result demonstrated that ammonia and nitrate did convert into N 2 during SCWO, however, the formation of N 2 was little without auxiliary fuel. Density functional theory (DFT) method was used to calculate the molecular structures of 2-, 3- and 4-NA to further explore reaction mechanism, which verified that amino group was more easily to be attacked than nitro group. Based on these results, the conceivable reaction pathways of 2-, 3- and 4-NA were proposed, which contained three parts, namely denitrification, ring-open and mineralization. Copyright © 2018. Published by Elsevier Ltd.

  4. Polymorphism in Bi2(SO4)3

    NASA Astrophysics Data System (ADS)

    Subban, Chinmayee V.; Rousse, Gwenaëlle; Courty, Matthieu; Barboux, Philippe; Tarascon, Jean-Marie

    2014-12-01

    A new polymorph of Bi2(SO4)3 was prepared by reaction of LiBiO2 with H2SO4 and its crystal structure was solved from X-ray powder diffraction. This new polymorph crystallizes in C2/c space group with lattice parameters a = 17.3383(3) Å, b = 6.77803(12) Å, c = 8.30978(13) Å, β = 101.4300(12)°. Bi2(SO4)3 presents a layered structure made of SO4 sulfate groups and signs of stereochemically active Bi3+ lone pairs. The new Bi2(SO4)3 absorbs water to form Bi2(H2O)2(SO4)2(OH)2 through an intermediate Bi2O(OH)2SO4 phase, and the transition is reversible when heated under vacuum.

  5. 3 D Co3 (PO4 )2 -Reduced Graphene Oxide Flowers for Photocatalytic Water Splitting: A Type II Staggered Heterojunction System.

    PubMed

    Samal, Alaka; Swain, Smrutirekha; Satpati, Biswarup; Das, Dipti Prakasini; Mishra, Barada Kanta

    2016-11-23

    The design, synthesis, and photoelectrochemical characterization of Co 3 (PO 4 ) 2 , a hydrogen evolving catalyst modified with reduced graphene oxide (RGO), is reported. The 3 D flowerlike Co 3 (PO 4 ) 2 heterojunction system, consisting of 3 D flowerlike Co 3 (PO 4 ) 2 and RGO sheets, was synthesized by a one-pot in situ photoassisted method under visible-light irradiation, which was achieved without the addition of surfactant or a structure-directing reagent. For the first time, Co 3 (PO 4 ) 2 is demonstrated to act as a hydrogen evolving catalyst rather than being used as an oxygen evolving photoanode. In particular, 3 D flowerlike Co 3 (PO 4 ) 2 anchored to RGO nanosheets is shown to possess dramatically improved photocatalytic activity. This enhanced photoactivity is mainly due to the staggered type II heterojunction system, in which photoinduced electrons from 3 D flowerlike Co 3 (PO 4 ) 2 transfer to the RGO sheets and result in decreased charge recombination, as evidenced by photoluminescence spectroscopy. The band gap of Co 3 (PO 4 ) 2 was calculated to be 2.35 eV by the Kubelka-Munk method. Again, the Co 3 (PO 4 ) 2 semiconductor displays n-type behavior, as observed from Mott-Schottky measurements. These RGO-Co 3 (PO 4 ) 2 conjugates are active in the visible range of solar light for water splitting and textile dye degradation, and can be used towards the development of greener and cheaper photocatalysts by exploiting solar light. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. 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.

  7. Human SLC4A11 Is a Novel NH3/H+ Co-transporter*

    PubMed Central

    Zhang, Wenlin; Ogando, Diego G.; Bonanno, Joseph A.; Obukhov, Alexander G.

    2015-01-01

    SLC4A11 has been proposed to be an electrogenic membrane transporter, permeable to Na+, H+ (OH−), bicarbonate, borate, and NH4+. Recent studies indicate, however, that neither bicarbonate or borate is a substrate. Here, we examined potential NH4+, Na+, and H+ contributions to electrogenic ion transport through SLC4A11 stably expressed in Na+/H+ exchanger-deficient PS120 fibroblasts. Inward currents observed during exposure to NH4Cl were determined by the [NH3]o, not [NH4+]o, and current amplitudes varied with the [H+] gradient. These currents were relatively unaffected by removal of Na+, K+, or Cl− from the bath but could be reduced by inclusion of NH4Cl in the pipette solution. Bath pH changes alone did not generate significant currents through SLC4A11, except immediately following exposure to NH4Cl. Reversal potential shifts in response to changing [NH3]o and pHo suggested an NH3/H+-coupled transport mode for SLC4A11. Proton flux through SLC4A11 in the absence of ammonia was relatively small, suggesting that ammonia transport is of more physiological relevance. Methylammonia produced currents similar to NH3 but with reduced amplitude. Estimated stoichiometry of SLC4A11 transport was 1:2 (NH3/H+). NH3-dependent currents were insensitive to 10 μm ethyl-isopropyl amiloride or 100 μm 4,4′- diisothiocyanatostilbene-2,2′-disulfonic acid. We propose that SLC4A11 is an NH3/2H+ co-transporter exhibiting unique characteristics. PMID:26018076

  8. A Layered Solution Crystal Growth Technique and the Crystal Structure of (C 6H 5C 2H 4NH 3) 2PbCl 4

    NASA Astrophysics Data System (ADS)

    Mitzi, D. B.

    1999-07-01

    Single crystals of the organic-inorganic perovskite (C6H5C2H4NH3)2PbCl4 have been grown at room temperature using a layered solution approach. The bottom solution layer, contained within a long straight tube, consists of PbCl2 dissolved in concentrated aqueous HCl. A less dense layer of methanol is carefully placed on top of the HCl/PbCl2 solution using a syringe. Finally, a stoichiometric quantity of C6H5C2H4NH2 (relative to the PbCl2) is added to the top of the column. As the layers slowly diffuse together, well-formed crystals of (C6H5C2H4NH3)2PbCl4 appear near the interface between the HCl/PbCl2 and C6H5C2H4NH2 solutions. The thick, plate-like crystals are well suited for X-ray crystallography studies. Room temperature intensity data were refined using a triclinic (Poverline1) cell (a=11.1463(3) Å, b=11.2181(3) Å, c=17.6966(5) Å, α= 99.173(1)°, β=104.634(1)°, γ=89.999(1)°, V=2111.8(1) Å3, Z=4, Rf/Rw=0.031/0.044). The organic-inorganic layered perovskite structure features well-ordered sheets of corner-sharing distorted PbCl6 octahedra separated by bilayers of phenethylammonium cations. Tilting and rotation of the PbCl6 octahedra within the perovskite sheets, coupled with organic cation ordering, leads to the unusual in-sheet 2ap×2ap superstructure, where ap is the lattice constant for the ideal cubic perovskite.

  9. Effect of CYP3A4 genetic polymorphisms on the genotoxicity of 4,4'-methylene-bis(2-chloroaniline)-exposed workers.

    PubMed

    Wang, Chung-Ching; Chen, Wei-Liang; Hsiung, Chia-Ni; Chiang, Sheng-Ta; Wang, Ying-Chuan; Loh, Ching-Hui; Lin, I-Shen; Chen, Hong-I; Liou, Saou-Hsing

    2017-01-01

    We investigated the relationship between 4,4'-methylene-bis(2-chloroaniline) (MBOCA) exposure and micronucleus (MN) frequency, and how this association was affected by genetic polymorphism of the cytochrome P450 enzyme (CYP3A4). We divided the study population into an exposed group (n=44 with total urine MBOCA ≥20 μg/g creatinine) and a control group (n=47 with total urine MBOCA <20 μg/g creatinine). Lymphocyte MN frequency (MNF) and micronucleated cell (MNC) frequency were measured by the cytokinesis-block MN assay method. MNF reported as the number of micronuclei in binucleated cells per 1000 cells, and MNC reported as the number of binucleated cells with the presence of MN per 1000 cells. CYP3A4 alleles were measured by PCR-based restriction fragment length polymorphism (PCR-RFLP). The mean MNF (6.11 vs 4.46 MN/1000 cells, p<0.001) and MNC (5.75 vs 4.15 MN/1000 cells, p<0.001) in the exposed workers was significantly higher than that in the controls. The CYP3A4 polymorphism A/A+A/G influenced the difference in the mean MNF (5.97 vs 4.38 MN/1000 cells, p<0.001) and MNC (5.60 vs 4.15 MN/1000 cells, p<0.001) between the MBOCA-exposed and control groups. After adjusting risk factors, the MNF level in the MBOCA-exposed workers was 0.520 MN cells/1000 cells (p<0.001) higher than the control group among the CYP3A4 A/A+A/G genotype. Similarly, the MNC level in the MBOCA-exposed workers was 0.593 MN/1000 cells (p<0.001) higher than the control group among the CYP3A4 A/A+A/G genotype. However, the difference in adjusted MNF and MNC between the exposed and control groups was not significant for the CYP3A4 polymorphism with the G/G genotype. We recommend that lymphocytes MNF and MNC are good indicators to evaluate MBOCA genotoxicity. Individuals with the CYP3A4 polymorphism A/A and A/G genotypes appear to be more susceptible to MBOCA genotoxicity. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a

  10. 2,4,5-TMBA, a natural inhibitor of cyclooxygenase-2, suppresses adipogenesis and promotes lipolysis in 3T3-L1 adipocytes.

    PubMed

    Wu, Man-Ru; Hou, Ming-Hon; Lin, Ya-Lin; Kuo, Chia-Feng

    2012-07-25

    Obesity is a global health problem. Because of the high costs and side effects of obesity-treatment drugs, the potential of natural products as alternatives for treating obesity is under exploration. 2,4,5-Trimethoxybenzaldehyde (2,4,5-TMBA) present in plant roots, seeds, and leaves was reported to be a significant inhibitor of cyclooxygenase-2 (COX-2) activity at the concentration of 100 μg/mL. Because COX-2 is associated with differentiation of preadipocytes, the murine 3T3-L1 cells were cultured with 100 μg/mL of 2,4,5-TMBA during differentiation and after the cells were fully differentiated to study the effect of 2,4,5-TMBA on adipogenesis and lipolysis. Oil Red O staining and triglyceride assay revealed that 2,4,5-TMBA inhibited the formation of lipid droplets during differentiation; moreover, 2,4,5-TMBA down-regulated the protein levels of adipogenic signaling molecules and transcription factors MAP kinase kinase (MEK), extracellular signal-regulated kinase (ERK), CCAAT/enhancer binding protein (C/EBP)α, β, and δ, peroxisome proliferator-activated receptor (PPAR)γ, adipocyte determination and differentiation-dependent factor 1 (ADD1), and the rate-limiting enzyme for lipid synthesis acetyl-CoA carboxylase (ACC). In fully differentiated adipocytes, treatment with 2,4,5-TMBA for 72 h significantly decreased lipid accumulation by increasing the hydrolysis of triglyceride through suppression of perilipin A (lipid droplet coating protein) and up-regulation of hormone-sensitive lipase (HSL). The results of this in vitro study will pioneer future in vivo studies on antiobesity effects of 2,4,5-TMBA and selective COX-2 inhibitors.

  11. 40 CFR 721.5279 - 2,7-Naphthalenedisulfonic acid, 4-amino-3-[[42-amino-4-[(3-butoxy-2-hydroxypropyl)amino]phebyl...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... reporting. (1) The chemical substance identified as 2,7-naphthalenedisulfonic acid, 4-amino-3-[[42-amino-4... 40 Protection of Environment 31 2011-07-01 2011-07-01 false 2,7-Naphthalenedisulfonic acid, 4-amino-3-[[4â²2-amino-4-[(3-butoxy-2-hydroxypropyl)amino]phebyl]azo]-3,3â²-dimethyl[1,1â²-biphenyl]-4-yl...

  12. 40 CFR 721.5279 - 2,7-Naphthalenedisulfonic acid, 4-amino-3-[[42-amino-4-[(3-butoxy-2-hydroxypropyl)amino]phebyl...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... reporting. (1) The chemical substance identified as 2,7-naphthalenedisulfonic acid, 4-amino-3-[[42-amino-4... 40 Protection of Environment 30 2010-07-01 2010-07-01 false 2,7-Naphthalenedisulfonic acid, 4-amino-3-[[4â²2-amino-4-[(3-butoxy-2-hydroxypropyl)amino]phebyl]azo]-3,3â²-dimethyl[1,1â²-biphenyl]-4-yl...

  13. Effects of CYP1A2 on disposition of 2,3,7, 8-tetrachlorodibenzo-p-dioxin, 2,3,4,7,8-pentachlorodibenzofuran, and 2,2',4,4',5,5'-hexachlorobiphenyl in CYP1A2 knockout and parental (C57BL/6N and 129/Sv) strains of mice.

    PubMed

    Diliberto, J J; Burgin, D E; Birnbaum, L S

    1999-08-15

    TCDD is the prototype and most potent member of the highly lipophilic polyhalogenated aromatic hydrocarbons (PHAHs), which are persistent and ubiquitous environmental contaminants. In both acute and subchronic animal studies, there is a specific accumulation of TCDD in liver greater than in adipose tissue. The inducible hepatic binding protein responsible for this hepatic sequestration of TCDD and its congeners has been shown by our laboratory to be CYP1A2 (J. J. Diliberto, D. Burgin, and L. S. Birnbaum, 1997, Biochem. Biophys. Res. Commun. 236, 431-433). The present study was conducted using knockout (KO) mice lacking expression of CYP1A2 (CYP1A2-/-) in order to investigate the role of CYP1A2 gene on the disposition of TCDD, 4-PeCDF (a dioxin-like PHAH), and PCB 153 (a nondioxin-like PCB) in KO (CYP1A2-/-) mice and age-matched parental mice strains (C57BL/6N: CYP1A2+/+, Ah(b/b) and 129/Sv: CYP1A2+/+, Ah(d/d)). Mice were dosed (25 microgram [(3)H]TCDD/kg, 300 microgram [(14)C]4-PeCDF/kg, or 35.8 mg [(14)C]PCB 153/kg bw in a corn oil vehicle) orally and terminated after 4 days. Residues of administered compounds in collected tissues and daily excreta were quantitated using (3)H or (14)C activity. Results demonstrated differential effects in disposition for the various treatments within the three genetically different groups of mice. In KO mice, TCDD, 4-PeCDF, and PCB 153 had very little hepatic localization of chemical, and the major depot was adipose tissue. In contrast, parental strains demonstrated hepatic sequestration of TCDD and 4-PeCDF, whereas disposition of PCB 153 in parental strains was similar to that in KO mice. Another difference between KO mice and parental strains was the enhanced urinary excretion of 4-PeCDF. This study demonstrates the importance of CYP1A2 in pharmacokinetic behavior and mechanistic issues for TCDD and related compounds. Copyright 1999 Academic Press.

  14. Synthesis and Pharmacological Characterization of C4-(Thiotriazolyl)-substituted-2-aminobicyclo[3.1.0]hexane-2,6-dicarboxylates. Identification of (1R,2S,4R,5R,6R)-2-Amino-4-(1H-1,2,4-triazol-3-ylsulfanyl)bicyclo[3.1.0]hexane-2,6-dicarboxylic Acid (LY2812223), a Highly Potent, Functionally Selective mGlu2 Receptor Agonist.

    PubMed

    Monn, James A; Prieto, Lourdes; Taboada, Lorena; Hao, Junliang; Reinhard, Matthew R; Henry, Steven S; Beadle, Christopher D; Walton, Lesley; Man, Teresa; Rudyk, Helene; Clark, Barry; Tupper, David; Baker, S Richard; Lamas, Carlos; Montero, Carlos; Marcos, Alicia; Blanco, Jaime; Bures, Mark; Clawson, David K; Atwell, Shane; Lu, Frances; Wang, Jing; Russell, Marijane; Heinz, Beverly A; Wang, Xushan; Carter, Joan H; Getman, Brian G; Catlow, John T; Swanson, Steven; Johnson, Bryan G; Shaw, David B; McKinzie, David L

    2015-09-24

    Identification of orthosteric mGlu(2/3) receptor agonists capable of discriminating between individual mGlu2 and mGlu3 subtypes has been highly challenging owing to the glutamate-site sequence homology between these proteins. Herein we detail the preparation and characterization of a series of molecules related to (1S,2S,5R,6S)-2-aminobicyclo[3.1.0]hexane-2,6-dicarboxylate 1 (LY354740) bearing C4-thiotriazole substituents. On the basis of second messenger responses in cells expressing other recombinant human mGlu2/3 subtypes, a number of high potency and efficacy mGlu2 receptor agonists exhibiting low potency mGlu3 partial agonist/antagonist activity were identified. From this, (1R,2S,4R,5R,6R)-2-amino-4-(1H-1,2,4-triazol-3-ylsulfanyl)bicyclo[3.1.0]hexane-2,6-dicarboxylic acid 14a (LY2812223) was further characterized. Cocrystallization of 14a with the amino terminal domains of hmGlu2 and hmGlu3 combined with site-directed mutation studies has clarified the underlying molecular basis of this unique pharmacology. Evaluation of 14a in a rat model responsive to mGlu2 receptor activation coupled with a measure of central drug disposition provides evidence that this molecule engages and activates central mGlu2 receptors in vivo.

  15. Synthesis of 2,3-dihydronaphtho[2,3-d][1,3]thiazole-4,9-diones and 2,3-dihydroanthra[2,3-d][1,3]thiazole-4,11-diones and novel ring contraction and fusion reaction of 3H-spiro[1,3-thiazole-2,1'-cyclohexanes] into 2,3,4,5-tetrahydro-1H-carbazole-6,11-diones

    PubMed Central

    Konstantinova, Lidia S; Lysov, Kirill A; Souvorova, Ljudmila I

    2013-01-01

    Summary Treatment of N-substituted 2-(methylamino)naphthoquinones 3 and -anthracene-1,4-diones 4 with S2Cl2 and DABCO in chlorobenzene gave the corresponding 2,3-dihydronaphtho[2,3-d][1,3]thiazole-4,9-diones 1 and 2,3-dihydroanthra[2,3-d][1,3]thiazole-4,11-diones 2 by triethylamine addition, in high to moderate yields. The DABCO replacement for N-ethyldiisopropylamine in the reaction of anthracene-1,4-diones 4 led unexpectedly to the corresponding 2-thioxo-2,3-dihydroanthra[2,3-d][1,3]thiazole-4,11-diones 10. The reaction of 3H-spiro[1,3-thiazole-2,1'-cyclohexanes] 1d, 2d with Et3N in chlorobenzene under reflux yielded 2,3,4,5-tetrahydro-1H-carbazole-6,11-diones 15, 16, i.e., ring contraction and fusion products. A plausible mechanism was proposed for the formation of the products. PMID:23616798

  16. Human Liver Cytochrome P450 3A4 Ubiquitination

    PubMed Central

    Wang, YongQiang; Kim, Sung-Mi; Trnka, Michael J.; Liu, Yi; Burlingame, A. L.; Correia, Maria Almira

    2015-01-01

    CYP3A4 is an abundant and catalytically dominant human liver endoplasmic reticulum-anchored cytochrome P450 enzyme engaged in the biotransformation of endo- and xenobiotics, including >50% of clinically relevant drugs. Alterations of CYP3A4 protein turnover can influence clinically relevant drug metabolism and bioavailability and drug-drug interactions. This CYP3A4 turnover involves endoplasmic reticulum-associated degradation via the ubiquitin (Ub)-dependent 26 S proteasomal system that relies on two highly complementary E2 Ub-conjugating-E3 Ub-ligase (UBC7-gp78 and UbcH5a-C terminus of Hsc70-interacting protein (CHIP)-Hsc70-Hsp40) complexes, as well as protein kinases (PK) A and C. We have documented that CYP3A4 Ser/Thr phosphorylation (Ser(P)/Thr(P)) by PKA and/or PKC accelerates/enhances its Lys ubiquitination by either of these E2-E3 systems. Intriguingly, CYP3A4 Ser(P)/Thr(P) and ubiquitinated Lys residues reside within the cytosol-accessible surface loop and/or conformationally assembled acidic Asp/Glu clusters, leading us to propose that such post-translational Ser/Thr protein phosphorylation primes CYP3A4 for ubiquitination. Herein, this possibility was examined through various complementary approaches, including site-directed mutagenesis, chemical cross-linking, peptide mapping, and LC-MS/MS analyses. Our findings reveal that such CYP3A4 Asp/Glu/Ser(P)/Thr(P) surface clusters are indeed important for its intermolecular electrostatic interactions with each of these E2-E3 subcomponents. By imparting additional negative charge to these Asp/Glu clusters, such Ser/Thr phosphorylation would generate P450 phosphodegrons for molecular recognition by the E2-E3 complexes, thereby controlling the timing of CYP3A4 ubiquitination and endoplasmic reticulum-associated degradation. Although the importance of phosphodegrons in the CHIP targeting of its substrates is known, to our knowledge this is the first example of phosphodegron involvement in gp78-substrate

  17. Identification of 4-(3-Pyridyl)-4-oxobutyl-2'-deoxycytidine Adducts Formed in the Reaction of DNA with 4-(Acetoxymethylnitrosamino)-1-(3-pyridyl)-1-butanone: A Chemically Activated Form of Tobacco-Specific Carcinogens.

    PubMed

    Michel, Anna K; Zarth, Adam T; Upadhyaya, Pramod; Hecht, Stephen S

    2017-03-31

    Metabolic activation of the carcinogenic tobacco-specific nitrosamines 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK, 1 ) and N '-nitrosonornicotine (NNN, 2 ) results in the formation of 4-(3-pyridyl)-4-oxobutyl (POB)-DNA adducts, several of which have been previously identified both in vitro and in tissues of laboratory animals treated with NNK or NNN. However, 2'-deoxycytidine adducts formed in this process have been incompletely examined in previous studies. Therefore, in this study we prepared characterized standards for the identification of previously unknown 2'-deoxycytidine and 2'-deoxyuridine adducts that could be produced in these reactions. The formation of these products in reactions of 4-(acetoxymethylnitrosamino)-1-(3-pyridyl)-1-butanone (NNKOAc, 3 ), a model 4-(3-pyridyl)-4-oxobutylating agent, with DNA was investigated. The major 2'-deoxycytidine adduct, identified as its stable cytosine analogue O 2 -[4-(3-pyridyl)-4-oxobut-1-yl]-cytosine ( 12 ), was O 2 -[4-(3-pyridyl)-4-oxobut-1-yl]-2'-deoxycytidine ( 13 ), whereas lesser amounts of 3-[4-(3-pyridyl)-4-oxobut-1-yl]-2'-deoxycytidine ( 14 ) and N 4 -[4-(3-pyridyl)-4-oxobut-1-yl]-2'-deoxycytidine ( 15 ) were also observed. The potential conversion of relatively unstable 2'-deoxycytidine adducts to stable 2'-deoxyuridine adducts by treatment of the adducted DNA with bisulfite was also investigated, but the harsh conditions associated with this approach prevented quantitation. The results of this study provide new validated standards for the study of 4-(3-pyridyl)-4-oxobutylation of DNA, a critical reaction in the carcinogenesis by 1 and 2 , and demonstrate the presence of previously unidentified 2'-deoxycytidine adducts in this DNA.

  18. 1-[3-(4-Butylpiperidin-1-yl)propyl]-1,2,3,4-tetrahydroquinolin-2-one (77-LH-28-1) as a Model for the Rational Design of a Novel Class of Brain Penetrant Ligands with High Affinity and Selectivity for Dopamine D4 Receptor.

    PubMed

    Del Bello, Fabio; Bonifazi, Alessandro; Giorgioni, Gianfabio; Cifani, Carlo; Micioni Di Bonaventura, Maria Vittoria; Petrelli, Riccardo; Piergentili, Alessandro; Fontana, Stefano; Mammoli, Valerio; Yano, Hideaki; Matucci, Rosanna; Vistoli, Giulio; Quaglia, Wilma

    2018-04-26

    In the present article, the M 1 mAChR bitopic agonist 1-[3-(4-butylpiperidin-1-yl)propyl]-1,2,3,4-tetrahydroquinolin-2-one (77-LH-28-1, 1) has been demonstrated to show unexpected D 4 R selectivity over D 2 R and D 3 R and to behave as a D 4 R antagonist. To better understand the structural features required for the selective interaction with the D 4 R and to obtain compounds unable to activate mAChRs, the aliphatic butyl chain and the piperidine nucleus of 1 were modified, affording compounds 2-14. The 4-benzylpiperidine 9 and the 4-phenylpiperazine 12 showed high D 4 R affinity and selectivity not only over the other D 2 -like subtypes, but also over M 1 -M 5 mAChRs. Derivative 12 was also highly selective over some selected off-targets. This compound showed biased behavior, potently and partially activating G i protein and inhibiting β-arrestin2 recruitment in functional studies. Pharmacokinetic studies demonstrated that it was characterized by a relevant brain penetration. Therefore, 12 might be a useful tool to better clarify the role played by D 4 R in disorders in which this subtype is involved.

  19. meso-4,4′-Dimeth­oxy-2,2′-{[(3aR,7aS)-2,3,3a,4,5,6,7,7a-octa­hydro-1H-benz­imidazole-1,3-di­yl]bis­(methyl­ene)}diphenol

    PubMed Central

    Rivera, Augusto; Quiroga, Diego; Ríos-Motta, Jaime; Kučeraková, Monika; Dušek, Michal

    2013-01-01

    The title compound, C23H30N2O4, a di-Mannich base derived from 4-meth­oxy­phenol and cis-1,2-di­amine­cyclo­hexane, has a perhydro­benzimidazolidine nucleus, in which the cyclo­hexane ring adopts a chair conformation and the heterocyclic ring has a half-chair conformation with a C—N—C—C torsion angles of −48.14 (15) and −14.57 (16)°. The mean plane of the heterocycle makes dihedral angles of 86.29 (6) and 78.92 (6)° with the pendant benzene rings. The mol­ecular structure of the title compound shows the presence of two inter­actions between the N atoms of the imidazolidine ring and the hydroxyl groups through intra­molecular O—H⋯N hydrogen bonds with graph-set motif S(6). The unobserved lone pairs of the N atoms are presumed to be disposed in a syn conformation, being only the second example of an exception to the typical ‘rabbit-ears’ effect in 1,2-di­amines. PMID:24046631

  20. Crystal Structures and Phase Relationships of 2 Polymorphs of 1,4-Diazabicyclo[3.2.2]nonane-4-Carboxylic Acid 4-Bromophenyl Ester Fumarate, A Selective α-7 Nicotinic Receptor Partial Agonist.

    PubMed

    Robert, Benoît; Perrin, Marc-Antoine; Barrio, Maria; Tamarit, Josep-Lluis; Coquerel, Gérard; Ceolin, René; Rietveld, Ivo B

    2016-01-01

    Two polymorphs of the 1:1 fumarate salt of 1,4-diazabicyclo[3.2.2]nonane-4-carboxylic acid 4-bromophenyl ester, developed for the treatment of cognitive symptoms of schizophrenia and Alzheimer disease, have been characterized. The 2 crystal structures have been solved, and their phase relationships have been established. The space group of form I is P2₁/c with a unit-cell volume of 1811.6 (5) Å(3) with Z = 4. The crystals of form I were 2-component nonmerohedral twins. The space group of form II is P2₁/n with a unit-cell volume of 1818.6 (3) Å(3) with Z = 4. Relative stabilities have been inferred from experimental and topological P-T diagrams exhibiting an overall enantiotropic relationship between forms I and II although the solid-solid transition has never been observed. The slope of the I-II equilibrium in the P-T diagram is negative, form II is the stable phase below the solid-solid transition temperature of 371 K, and form I exhibits a stable melting equilibrium. The I-II transition temperature has been obtained from the intersection of the sublimation curves of the 2 solid forms. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  1. A review on g-C3N4 for photocatalytic water splitting and CO2 reduction

    NASA Astrophysics Data System (ADS)

    Ye, Sheng; Wang, Rong; Wu, Ming-Zai; Yuan, Yu-Peng

    2015-12-01

    Solar fuel generation through water splitting and CO2 photoreduction is an ideal route to provide the renewable energy sources and mitigate global warming. The main challenge in photocatalysis is finding a low-cost photocatalyst that can work efficiently to split water into hydrogen and reduce CO2 to hydrocarbon fuels. Metal-free g-C3N4 photocatalyst shows great potentials for solar fuel production. In this mini review, we summarize the most current advances on novel design idea and new synthesis strategy for g-C3N4 preparation, insightful ideas on extending optical absorption of pristine g-C3N4, overall water splitting and CO2 photoreduction over g-C3N4 based systems. The research challenges and perspectives on g-C3N4 based photocatalysts were also suggested.

  2. A study of Pd/SO4/ZrO2/Al2O3 catalysts in n-hexane isomerization

    NASA Astrophysics Data System (ADS)

    Dzhikiya, O. V.; Smolikov, M. D.; Kazantsev, K. V.; Yablokova, S. S.; Kireeva, T. V.; Paukshtis, E. A.; Gulyaeva, T. I.; Belyi, A. S.

    2017-08-01

    The effect of palladium concentration in a range from 0.02 to 1.6 wt.% on characteristics of n-hexane isomerization was studied. The (O2-Hchem) titration and O2 chemisorption study revealed that palladium in Pd/SO4/ZrO2/Al2O3 systems adsorbs hydrogen in a ratio H/Pds = 1.13-1.65 at./at. Investigation of the charge state of the metal by IR spectroscopy of adsorbed CO showed the presence of both the metallic (Pd0) and charged palladium species. Pd/SO4/ZrO2/Al2O3 catalysts with charged palladium atoms exhibit high activity and selectivity in n-hexane isomerization.

  3. Cd4As2Br3

    PubMed Central

    Kars, Mohammed; Roisnel, Thierry; Dorcet, Vincent; Rebbah, Allaoua; Otero-Diáz, L. Carlos

    2014-01-01

    Single crystals of Cd4As2Br3 (tetra­cadmium biarsenide tri­bromide) were grown by a chemical transport reaction. The structure is isotypic with the members of the cadmium and mercury pnictidohalides family with general formula M 4 A 2 X 3 (M = Cd, Hg; A = P, As, Sb; X = Cl, Br, I) and contains two independent As atoms on special positions with site symmetry -3 and two independent Cd atoms, of which one is on a special position with site symmetry -3. The Cd4As2Br3 structure consists of AsCd4 tetra­hedra sharing vertices with isolated As2Cd6 octa­hedra that contain As–As dumbbells in the centre of the octahedron. The Br atoms are located in the voids of this three-dimensional arrangement and bridge the different polyhedra through Cd⋯Br contacts. PMID:24764933

  4. A Boy with an LCR3/4-Flanked 10q22.3q23.2 Microdeletion and Uncommon Phenotypic Features

    PubMed Central

    Petrova, E.; Neuner, C.; Haaf, T.; Schmid, M.; Wirbelauer, J.; Jurkutat, A.; Wermke, K.; Nanda, I.; Kunstmann, E.

    2014-01-01

    The recurrent 10q22.3q23.2 deletion with breakpoints within low copy repeats 3 and 4 is a rare genomic disorder, reported in only 13 patients to date. The phenotype is rather uncharacteristic, which makes a clinical diagnosis difficult. A phenotypic feature described in almost all patients is a delay in speech development, albeit systematic studies are still pending. In this study, we report on a boy with an LCR3/4-flanked 10q22.3q23.2 deletion exhibiting an age-appropriate language development evaluated by a standardized test at an age of 2 years and 3 months. The boy was born with a cleft palate – a feature not present in any of the patients described before. Previously reported cases are reviewed, and the role of the BMPR1A gene is discussed. The phenotype of patients with an LCR3/4-flanked 10q22.3q23.2 deletion can be rather variable, so counseling the families regarding the prognosis of an affected child should be done with caution. Long-term studies of affected children are needed to delineate the natural history of this rare disorder. PMID:24550761

  5. Incommensurate structure of a lillianite-type samarium chromium sulfide Sm{sub 2/3}Cr{sub 2}S{sub 4}

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

    Lafond, A.; Cario, L.; Meerschaut, A.

    1996-12-01

    The structure of Sm{sub 2/3}Cr{sub 2}S{sub 4} has been solved from single-crystal X-ray diffraction data. This compound presents a 3 X a superstructure along a and an incommensurate superstructure along b close to 3 x b. The basic structure is described in the space group Pmnb with a = 3.5030(3) {Angstrom}, b = 10.9199(8) {Angstrom}, c = 12.7987(8) {Angstrom}, Z = 4, R = 0.046 for 916 observed reflections. The modulated structure refinement, taking into account the two superstructures, was carried out in a (3 + 2)D superspace group and leads to R = 0.063 for 1706 reflections. This structuremore » consists of staggered double columns of [CrS{sub 6}] octahedra connected by samarium atoms in a trigonal prismatic bicapped environment. This structure is reminiscent of that found in the lillianite mineral family. The statistical occupancy of samarium atoms (1/3), in agreement with the charge equilibrium (Sm{sup 3+}, Cr{sup 3+}, S{sup 2-}), is related to the superstructure.« less

  6. Isolation and characterization of mimosine, 3, 4 DHP and 2, 3 DHP degrading bacteria from a commercial rumen inoculum.

    PubMed

    Derakhshani, Hooman; Corley, Sean W; Al Jassim, Rafat

    2016-05-01

    The presence of the toxic amino acid mimosine in Leucaena leucocephala restricts its use as a protein source for ruminants. Rumen bacteria degrade mimosine to 3,4- and 2,3-dihydroxypyridine (DHP), which remain toxic. Synergistes jonesii is believed to be the main bacterium responsible for degradation of these toxic compounds but other bacteria may also be involved. In this study, a commercial inoculum provided by the Queensland's Department of Agriculture, Fisheries, and Forestry was screened for isolation and characterization of mimosine, 3,4- and 2,3-DHP degrading bacterial strains. A new medium for screening of 2,3-DHP degrading bacteria was developed. Molecular and biochemical approaches used in this study revealed four bacterial isolates - Streptococcus lutetiensis, Clostridium butyricum, Lactobacillus vitulinus, and Butyrivibrio fibrisolvens - to be able to completely degrade mimosine within 7 days of incubation. It was also observed that C. butyricum and L. vitulinus were able to partially degrade 2,3-DHP within 12 days of incubation, while S. lutetiensis, was able to fully degrade both 3,4 and 2,3 DHP. Collectively, we concluded that S. jonesii is not the sole bacterium responsible for detoxification of Leucaena. Comprehensive screening of rumen fluid of cattle grazing on Leucaena pastures is needed to identify additional mimosine-detoxifying bacteria and contribute to development of more effective inoculums to be used by farmers against Leucaena toxicity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Structure, thermal, and impedance study of a new organic-inorganic hybrid [(CH2)7(NH3)2]CoCl4

    NASA Astrophysics Data System (ADS)

    Mostafa, M. F.; El-khiyami, Sh. S.; Alal, S. K.

    2018-07-01

    [(CH2)7(NH3)2]CoCl4 crystallizes in the triclinic system, space group P-1 with two molecules per asymmetric unit cell (Z = 2). The unit cell dimensions are a = 7.3107 (2) Å, b = 10.1841 (3) Å, c = 11.2690 (4) Å, α = 66.81 (2), β = 78.85 (12), and γ = 87.66 (2). The unit cell volume and the calculated density are 756.11 (4) Å3 and 1.463 Mg m-3, respectively. The structure of the hybrid is characterized by alternating layers of inorganic [CoCl4]2- anion and heptane diammonium cation. The organic hydrocarbon layers are packed in a stacked herring-bone manner with hydrogen bonds to the halide ions. The lattice potential energy Upot and the cation molecular volume V+ are 1856.2 kJ/mol and 0.37 nm3, respectively. DSC showed a compound (broad) peak at T1 = 331 K, T2 = 328 K with total entropy ΔS = 36.2 J/K. mol, and a λ-like endothermic peak at T3 = 296 K (ΔS = 24.9 J/K. mol). Dielectric properties are investigated at different temperatures and frequencies [260 K < T < 360 K and 0.06 kHz < f < 60 kHz, respectively]. Super-linear power law is observed for the AC conductivity, which is analyzed based on the jump relaxation model.

  8. Photoluminescence analysis of Ce{sup 3+}:Zn{sub 2}SiO{sub 4} & Li{sup +}+ Ce{sup 3+}:Zn{sub 2}SiO{sub 4}: phosphors by a sol-gel method

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

    Babu, B. Chandra, E-mail: chandrababuphd@gmail.com; Vandana, C. Sai; Guravamma, J.

    2015-06-24

    Here, we report on the development and photoluminescence analysis of Zn{sub 2}SiO{sub 4}, Ce{sup 3+}:Zn{sub 2}SiO{sub 4} & Li{sup +} + Ce{sup 3+}: Zn{sub 2}SiO{sub 4} novel powder phosphors prepared by a sol-gel technique. The total amount of Ce{sup 3+} ions was kept constant in this experiment at 0.05 mol% total doping. The excitation and emission spectra of undoped (Zn{sub 2}SiO{sub 4}) and Ce{sup 3+} doped Zn{sub 2}SiO{sub 4} and 0.05 mol% Li{sup +} co-doped samples have been investigated. Cerium doped Zn{sub 2}SiO{sub 4} powder phosphors had broad blue emission corresponding to the 2D{sub 3/2}→2F{sub J} transition at 443nm. Stable green-yellow-red emissionmore » has been observed from Zn{sub 2}SiO{sub 4} host matrix and also we have been observed the enhanced luminescence of Li{sup +} co-doped Zn{sub 2}SiO{sub 4}:Ce{sup 3+}. Excitation and emission spectra of these blue luminescent phosphors have been analyzed in evaluating their potential as luminescent screen coating phosphors.« less

  9. Synthesis, crystal structure determination and antiproliferative activity of novel 2-amino-4-aryl-4,10-dihydro[1,3,5]triazino[1,2- a]benzimidazoles

    NASA Astrophysics Data System (ADS)

    Hranjec, Marijana; Pavlović, Gordana; Karminski-Zamola, Grace

    2012-01-01

    This manuscript describes the synthesis of novel 2-amino-4-aryl-4,10-dihydro-[1,3,5]triazino[1,2- a]benzimidazoles as hydrochloride salts 4a-n and 5b which were prepared in the reaction of cyclocondensation between 2-guanidinobenzimidazole and versatile heteroaromatic aldehydes. Structures of all prepared compounds have been studied by using 1H and 13C NMR, IR and UV/Vis spectroscopy. The crystal and molecular structure of 4f was determined by X-ray diffraction on single crystals. The molecule of 2-amino-4-(4'-methylphenyl)-4,10-dihydro[1,3,5]triazino[1,2- a]benzimidazole hydrochloride 4f (C 16H 16N 5+·Cl -) exists in the solid state in one of the possible tautomeric forms, being protonated at the one of the nitrogen atoms of the 1,4-dihydrotriazine ring. The molecule is highly delocalized within the 4,10-dihydro[1,3,5]triazino[1,2- a]benzimidazole moiety with the highest deviation from the plane for the methine carbon atom and the protonated nitrogen atom of the 1,4-dihydrotriazine ring. The cations are joined via N-H⋯N hydrogen bonds into R22(8) centrosymmetric dimers. Cation dimers are further connected with Cl - ions via N-H⋯Cl and C-H⋯Cl hydrogen bonds into 2D chains spreading along the b axis. The obtained single-crystal X-ray structure determination unequivocally confirms tautomeric form of the compound present in the solid-state and can represent tantative pattern for other prepared compounds. All prepared compounds were tested on their antiproliferative activity in vitro on several human cancer cell lines. Compound 4m was the most active one (IC 50 ≈ 20 μM), while compounds 4d, 4f, 4k, 4l4m showed moderate, but non-selective, antiproliferative activity with IC 50 25-60 μM.

  10. CYP2C8 but not CYP3A4 is important in the pharmacokinetics of montelukast

    PubMed Central

    Karonen, Tiina; Neuvonen, Pertti J; Backman, Janne T

    2012-01-01

    AIM According to product information, montelukast is extensively metabolized by CYP3A4 and CYP2C9. However, CYP2C8 was also recently found to be involved. Our aim was to study the effects of selective CYP2C8 and CYP3A4 inhibitors on the pharmacokinetics of montelukast. METHODS In a randomized crossover study, 11 healthy subjects ingested gemfibrozil 600 mg, itraconazole 100 mg (first dose 200 mg) or both, or placebo twice daily for 5 days, and on day 3, 10 mg montelukast. Plasma concentrations of montelukast, gemfibrozil, itraconazole and their metabolites were measured up to 72 h. RESULTS The CYP2C8 inhibitor gemfibrozil increased the AUC(0,∞) of montelukast 4.3-fold and its t1/2 2.1-fold (P < 0.001). Gemfibrozil impaired the formation of the montelukast primary metabolite M6, reduced the AUC and Cmax of the secondary (major) metabolite M4 by more than 90% (P < 0.05) and increased those of M5a and M5b (P < 0.05). The CYP3A4 inhibitor itraconazole had no significant effect on the pharmacokinetic variables of montelukast or its M6 and M4 metabolites, but markedly reduced the AUC and Cmax of M5a and M5b (P < 0.05). The effects of the gemfibrozil-itraconazole combination on the pharmacokinetics of montelukast did not differ from those of gemfibrozil alone. CONCLUSIONS CYP2C8 is the dominant enzyme in the biotransformation of montelukast in humans, accounting for about 80% of its metabolism. CYP3A4 only mediates the formation of the minor metabolite M5a/b, and is not important in the elimination of montelukast. Montelukast may serve as a safe and useful CYP2C8 probe drug. PMID:21838784

  11. A top-down method to fabricate SrAl2O4:Eu2+,Dy3+ nanosheets from commercial blocky phosphors

    NASA Astrophysics Data System (ADS)

    Zhang, Haoran; Xue, Zhiping; Lei, Bingfu; Dong, Hanwu; Zhang, Haiming; Deng, Suqing; Zheng, Mingtao; Liu, Yingliang; Xiao, Yong

    2014-09-01

    By using commercial SrAl2O4:Eu2+,Dy3+ phosphor as raw material, we have developed a novel and simple top-down method to fabricate SrAl2O4:Eu2+,Dy3+ nanosheets that are useful for potential practical applications, especially as fluorescent labels for biomolecules and mechano-optical nano-devices. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX) results demonstrate that the treated samples are still pure-phase of SrAl2O4:Eu2+,Dy3+. The field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) results indicate that the treated SrAl2O4:Eu2+,Dy3+ phosphors are built up by nanosheets bundles. Excitation and emission spectra, afterglow emission spectra and decay curves are used to analyze the luminescence properties of SrAl2O4:Eu2+,Dy3+ nanosheets, and the results show that, compared with commercial samples, the treated samples show similar spectra characteristic including the spectra shapes and the band position. Furthermore, the fluorescence and afterglow intensity of SrAl2O4:Eu2+,Dy3+ nanosheets can be tuned linearly by changing the circumstance temperatures, which further indicates its potential applications in fiber-optical thermometer materials.

  12. 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

  13. Structural and computational characterization of 4‧,4‧,6‧,6‧-tetrachloro-3-(2-methoxyethyl)-3H,4H-spiro-1,3,2-benzoxaza phosphinine-2,2‧- [1,3,5,2,4,6] triazatriphosphinine

    NASA Astrophysics Data System (ADS)

    Işıklan, Muhammet; Yıldırım, Erdem Kamil; Atiş, Murat; Sonkaya, Ömer; Çoşut, Bünyemin

    2016-08-01

    In this study a new monospirocyclic phosphazene derivative, 4‧,4‧,6‧,6‧-tetrachloro-3-(2-methoxyethyl)-3H,4H-spiro [1,3,2-benzoxazaphosphinine-2,2‧- [1,3,5,2,4,6] triazatriphosphinine] (SP1) was synthesized from the reaction of hexachlorocyclotriphosphazene (N3P3Cl6) with N/O donor-type, 2-{[(2-Metoxyethyl) amino]methyl}phenol. The structural investigations of the compound were verified by elemental analyses, MS, FTIR, 1H, 13C, 31P NMR spectroscopy and the single crystal X-ray diffraction analysis. The structural and spectroscopic data of the molecule in the ground state were calculated by using density functional method (DFT) using 6-311++G (d, p) basis set. The complete assignments of all vibrational modes were performed on the basis of the total energy distributions (TED). Isotropic chemical shifts (31P, 1H and 13C NMR) were calculated using the gauge-invariant atomic orbital (GIAO) method. Theoretical calculations of bond parameters, harmonic vibration frequencies and nuclear magnetic resonance are in good agreement with experimental results. The electrophilic and nucleophilic attack centers in SP1 were predicted with the local softness values (sk+, and sk-) of individual atoms and it is confirmed that P atoms of the PCl2 groups are nucleophilic attack centers.

  14. 29 CFR 4.154 - Employees covered by sections 2(a)(3) and (4).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 4.154 Labor Office of the Secretary of Labor LABOR STANDARDS FOR FEDERAL SERVICE CONTRACTS Application of the McNamara-O'Hara Service Contract Act Employees Covered by the Act § 4.154 Employees covered... contract subject to section 2(a) of the Act. ...

  15. Synthesis, structure characterization and biological studies on a new aromatic hydrazone, 5-(2-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)hydrazono)-2,2-dimethyl-1,3-dioxane-4,6-dione, and its transition metal complexes

    NASA Astrophysics Data System (ADS)

    Kumar, Shubha S.; Biju, S.; Sadasivan, V.

    2018-03-01

    A new aromatic hydrazone 5-(2-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)hydrazono)-2,2-dimethyl-1,3-dioxane-4,6-dione has been synthesized by Japp-Klingemann reaction from diazotized 4-aminoantipyrine and Meldrum's acid. A few 3d-metal ion complexes of this hydrazone were synthesized. The compound and its complexes were characterized by UV-Visible, 1H NMR, ESR, Mass spectral, molar conductance and magnetic susceptibility measurements. The compound was found to exist in hydrazone form in solid state and solution from SXRD and 1H NMR study. The influence of pH on the molecule was studied and found that it shows azo/enol-hydrazone tautomerism in solution. This molecule act as a univalent tridentate ligand and the complexes were assigned to have a 1:2 stoichiometry (M:L). The antioxidant properties of the compounds were explored by DPPH assay and found that the ligand possesses better free radical scavenging effect than the complexes. Antimicrobial activities of these compounds were investigated and were found to be active.

  16. Highly pathogenic avian influenza H5N1 clade 2.3.2.1 and clade 2.3.4 viruses do not induce a clade-specific phenotype in mallard ducks

    PubMed Central

    Crumpton, Jeri Carol; Rubrum, Adam; Phommachanh, Phouvong; Douangngeun, Bounlom; Peiris, Malik; Guan, Yi; Webster, Robert; Webby, Richard

    2017-01-01

    Among the diverse clades of highly pathogenic avian influenza (HPAI) H5N1 viruses of the goose/Guangdong lineage, only a few have been able to spread across continents: clade 2.2 viruses spread from China to Europe and into Africa in 2005–2006, clade 2.3.2.1 viruses spread from China to Eastern Europe in 2009–2010 and clade 2.3.4.4 viruses of the H5Nx subtype spread from China to Europe and North America in 2014/2015. While the poultry trade and wild-bird migration have been implicated in the spread of HPAI H5N1 viruses, it has been proposed that robust virus-shedding by wild ducks in the absence of overt clinical signs may have contributed to the wider dissemination of the clade 2.2, 2.3.2.1 and 2.3.4.4 viruses. Here we determined the phenotype of two divergent viruses from clade 2.3.2.1, a clade that spread widely, and two divergent viruses from clade 2.3.4, a clade that was constrained to Southeast Asia, in young (ducklings) and adult (juvenile) mallard ducks. We found that the virus-shedding magnitude and duration, transmission pattern and pathogenicity of the viruses in young and adult mallard ducks were largely independent of the virus clade. A clade-specific pattern could only be detected in terms of cumulative virus shedding, which was higher with clade 2.3.2.1 than with clade 2.3.4 viruses in juvenile mallards, but not in ducklings. The ability of clade 2.3.2.1c A/common buzzard/Bulgaria/38 WB/2010-like viruses to spread cross-continentally may, therefore, have been strain-specific or independent of phenotype in wild ducks. PMID:28631606

  17. 2,3-Diphosphoglycerate is a nonselective inhibitor of inositol 1,4,5-trisphosphate action and metabolism.

    PubMed

    Guillemette, G; Favreau, I; Lamontagne, S; Boulay, G

    1990-04-25

    Inositol 1,4,5-trisphosphate (InsP3) is an important second messenger generated from the hydrolysis of phosphatidylinositol 4,5-bisphosphate by phospholipase C in response to Ca2(+)-mobilizing stimuli. InsP3 interacts with specific intracellular receptors and triggers the release of sequestered Ca2+ from an intracellular store. We have looked at the influence of 2,3-diphosphoglycerate on the action and metabolism of InsP3 in the bovine adrenal cortex. 2,3-Diphosphoglycerate blocked InsP3 binding to adrenal cortex microsomes with a half-maximal efficiency of 0.5 mM. Scatchard analyses revealed that 2,3-diphosphoglycerate did not change the maximal capacity of the microsomes, but decreased their binding affinity for InsP3. The Ca2(+)-releasing activity of InsP3 on the same microsomal preparation was monitored with the fluorescent indicator, Fura-2. 2,3-Diphosphoglycerate blocked this activity with a half-maximal efficiency of 2 mM. The effect of 2,3-diphosphoglycerate could be overcome by supramaximal doses of InsP3, indicating a competitive inhibitory effect. The activity of InsP3 phosphatase from bovine adrenal cortex microsomes was also studied. 2,3-Diphosphoglycerate inhibited the activity of the phosphatase with a half-maximal efficiency of 0.3 mM. Lineweaver-Burke plots revealed that this effect was competitive. Finally, 2,3-diphosphoglycerate was also able to inhibit the activity of a partially purified preparation of InsP3 kinase from bovine adrenal cortex cytosol. The half-maximal dose was around 10 mM and the Lineweaver-Burke plot showed that the inhibition was competitive. These results show that 2,3-diphosphoglycerate can be considered as a structural analog of InsP3. Its inhibitory effects, however, are not selective enough to use it as an InsP3 protective agent in Ca2(+)-mobilization studies.

  18. Cluster transformation of [Cu33-H)(μ3-BH4)((PPh2)2NH)3](BF4) to [Cu33-H)(μ2,μ1-S2CH)((PPh2)2NH)3](BF4) via reaction with CS2. X-ray structural characterisation and reactivity of cationic clusters explored by multistage mass spectrometry and computational studies.

    PubMed

    Ma, Howard Z; Li, Jiaye; Canty, Allan J; O'Hair, Richard A J

    2017-11-07

    The copper nanocluster [Cu 33 -H)(μ 3 -BH 4 )L Ph 3 ](BF 4 ), 1a·BF4 (L Ph = (PPh 2 ) 2 NH = dppa), can potentially react with substrates at either the coordinated hydride or borohydride sites. Reaction of 1a·BF4 with CS 2 has given rise to [Cu 33 -H)(μ 2 ,μ 1 -S 2 CH)L Ph 3 ](BF 4 ), (2a·BF4), which was structurally characterised using electrospray ionisation (ESI) with high-resolution mass spectrometry (HRMS), X-ray crystallography, NMR, IR and UV-Vis spectroscopy. The copper(i) atoms adopt a planar trinuclear Cu 3 geometry coordinated on the bottom face by a μ 3 -hydride, on the top face by a μ 2 ,μ 1 -dithioformate and surrounded by three bridging L Ph ligands. Reaction of 1a·BF4 with elemental sulfur gives the known cluster [Cu 4 (L Ph -H + 2S) 3 ](BF 4 ), (3·BF4), which was structurally characterised via X-ray crystallography. ESI-MS of 2a·BF4 produces [Cu 3 (H)(S 2 CH)L Ph 3 ] + and its gas-phase ion chemistry was examined under multistage mass spectrometry conditions using collision-induced dissociation (CID). The primary product, [Cu 3 (H)(S 2 CH)L Ph 2 ] + , formed via ligand loss, undergoes further fragmentation via loss of thioformaldehyde to give [Cu 3 (S)L Ph 2 ] + . DFT calculations exploring rearrangement and fragmentation of the model system [Cu 3 (H)(S 2 CH)L Me 2 ] + (L Me = (PMe 2 ) 2 NH = dmpa) provide a feasible mechanism. Thus, coupling of the coordinated hydride with the dithioformate ligands gives [Cu 3 (S 2 CH 2 )L Me 2 ] + , which then undergoes CH 2 S extrusion via C-S bond cleavage to give [Cu 3 (S)L Me 2 ] + .

  19. Ca4As3a new binary calcium arsenide

    PubMed Central

    Hoffmann, Andrea V.; Hlukhyy, Viktor; Fässler, Thomas F.

    2015-01-01

    The crystal structure of the binary compound tetra­calcium triarsenide, Ca4As3, was investigated by single-crystal X-ray diffraction. Ca4As3 crystallizes in the Ba4P3 structure type and is thus a homologue of isotypic Sr4As3. The unit cell contains 32 Ca2+ cations, 16 As3− isolated anions and four centrosymmetric [As2]4– dumbbells. The As atoms in each of the dumbbells are connected by a single bond, thus this calcium arsenide is a Zintl phase. PMID:26870427

  20. Synthesis, stereochemical, structural, and biological studies of a series of N‧-(2r,4c-diaryl-3-azabicyclo[3.3.1]nonan-9-ylidene)pyrazine-2-carbohydrazides

    NASA Astrophysics Data System (ADS)

    Mangalam, M.; Sebastian Antony Selvan, C.; Sankar, C.

    2017-02-01

    A new series of N‧-(2r,4c-diaryl-3-azabicyclo[3.3.1]nonan-9-ylidene)pyrazine-2-carbohydrazides (8-14) were synthesized by the corresponding 2r,4c-diaryl-3-azabicyclo[3.3.1]nonan-9-ones (1-7) reaction with pyrazine-2-carbohydrazide. The stereochemistry of the newly synthesized compounds were unambiguously assigned using FT-IR, 1H, 13C, and 2D (COSY, HSQC, HMBC, ROESY) nuclear magnetic resonance (NMR) spectral data. The chemical shifts suggest that all these compounds adopt twin-chair conformation with equatorial orientation of aryl substitutions in solution. Hydrazones were screened for their in vitro antitubercular activity against Mycobacterium tuberculosis H37Rv and antibacterial activity against a set of pathogenic bacteria. Most of the halogenated compounds showed promising antitubercular and antibacterial activities.

  1. Treatment for GaSb surfaces using a sulphur blended (NH4)2S/(NH4)2SO4 solution

    NASA Astrophysics Data System (ADS)

    Murape, D. M.; Eassa, N.; Neethling, J. H.; Betz, R.; Coetsee, E.; Swart, H. C.; Botha, J. R.; Venter, A.

    2012-07-01

    A sulphur based chemical, [(NH4)2S/(NH4)2SO4] to which S has been added, not previously reported for the treatment of (1 0 0) n-GaSb surfaces, is introduced and benchmarked against the commonly used passivants Na2S·9H2O and (NH4)2S. The surfaces of the treated material were studied by scanning electron microscopy (SEM), Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). It has been found that the native oxides present on the GaSb surface are more effectively removed when treated with ([(NH4)2S/(NH4)2SO4] + S) than with (NH4)2S or Na2S·9H2O, as evidenced by the ratio of the O506 eV to Sb457 eV AES peaks. XPS results reveal that Sb2S3/Sb2S5 "replaces" Sb2O3/Sb2O5, suggesting that sulphur atoms substitute oxygen atoms in Sb2O3/Sb2O5 to form Sbsbnd S. It seems sulphurization only partially removes Ga2O3. Treatment with ([(NH4)2S/(NH4)2SO4] + S) also results in a noteworthy improvement in the current-voltage (I-V) characteristics of Au/n-GaSb Schottky contacts compared to those fabricated on as-received material.

  2. 40 CFR 721.9730 - 1,3,5-Triazin-2-amine, 4-di-meth-yl-a-mino-6-substituted-.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false 1,3,5-Triazin-2-amine, 4-di-meth-yl-a... New Uses for Specific Chemical Substances § 721.9730 1,3,5-Triazin-2-amine, 4-di-meth-yl-a-mino-6... substances generically identified as 1,3,5-triazin-2-amine, 4-di-meth-yl-a-mino-6-substituted- (PMN Nos. P-92...

  3. 40 CFR 721.9730 - 1,3,5-Triazin-2-amine, 4-di-meth-yl-a-mino-6-substituted-.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false 1,3,5-Triazin-2-amine, 4-di-meth-yl-a... New Uses for Specific Chemical Substances § 721.9730 1,3,5-Triazin-2-amine, 4-di-meth-yl-a-mino-6... substances generically identified as 1,3,5-triazin-2-amine, 4-di-meth-yl-a-mino-6-substituted- (PMN Nos. P-92...

  4. 40 CFR 721.9730 - 1,3,5-Triazin-2-amine, 4-di-meth-yl-a-mino-6-substituted-.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false 1,3,5-Triazin-2-amine, 4-di-meth-yl-a... New Uses for Specific Chemical Substances § 721.9730 1,3,5-Triazin-2-amine, 4-di-meth-yl-a-mino-6... substances generically identified as 1,3,5-triazin-2-amine, 4-di-meth-yl-a-mino-6-substituted- (PMN Nos. P-92...

  5. 40 CFR 721.9730 - 1,3,5-Triazin-2-amine, 4-di-meth-yl-a-mino-6-substituted-.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false 1,3,5-Triazin-2-amine, 4-di-meth-yl-a... New Uses for Specific Chemical Substances § 721.9730 1,3,5-Triazin-2-amine, 4-di-meth-yl-a-mino-6... substances generically identified as 1,3,5-triazin-2-amine, 4-di-meth-yl-a-mino-6-substituted- (PMN Nos. P-92...

  6. A 0.4-2.3 GHz broadband power amplifier extended continuous class-F design technology

    NASA Astrophysics Data System (ADS)

    Chen, Peng; He, Songbai

    2015-08-01

    A 0.4-2.3 GHz broadband power amplifier (PA) extended continuous class-F design technology is proposed in this paper. Traditional continuous class-F PA performs in high-efficiency only in one octave bandwidth. With the increasing development of wireless communication, the PA is in demand to cover the mainstream communication standards' working frequencies from 0.4 GHz to 2.2 GHz. In order to achieve this objective, the bandwidths of class-F and continuous class-F PA are analysed and discussed by Fourier series. Also, two criteria, which could reduce the continuous class-F PA's implementation complexity, are presented and explained to investigate the overlapping area of the transistor's current and voltage waveforms. The proposed PA design technology is based on the continuous class-F design method and divides the bandwidth into two parts: the first part covers the bandwidth from 1.3 GHz to 2.3 GHz, where the impedances are designed by the continuous class-F method; the other part covers the bandwidth from 0.4 GHz to 1.3 GHz, where the impedance to guarantee PA to be in high-efficiency over this bandwidth is selected and controlled. The improved particle swarm optimisation is employed for realising the multi-impedances of output and input network. A PA based on a commercial 10 W GaN high electron mobility transistor is designed and fabricated to verify the proposed design method. The simulation and measurement results show that the proposed PA could deliver 40-76% power added efficiency and more than 11 dB power gain with more than 40 dBm output power over the bandwidth from 0.4-2.3 GHz.

  7. Endosulfan induces CYP2B6 and CYP3A4 by activating the pregnane X receptor

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

    Casabar, Richard C.T.; Das, Parikshit C.; DeKrey, Gregory K.

    Endosulfan is an organochlorine pesticide commonly used in agriculture. Endosulfan has affects on vertebrate xenobiotic metabolism pathways that may be mediated, in part, by its ability to activate the pregnane X receptor (PXR) and/or the constitutive androstane receptor (CAR) which can elevate expression of cytochrome P450 (CYP) enzymes. This study examined the dose-dependency and receptor specificity of CYP induction in vitro and in vivo. The HepG2 cell line was transiently transfected with CYP2B6- and CYP3A4-luciferase promoter reporter plasmids along with human PXR (hPXR) or hCAR expression vectors. In the presence of hPXR, endosulfan-alpha exposure caused significant induction of CYP2B6 (16-fold)more » and CYP3A4 (11-fold) promoter activities over control at 10 {mu}M. The metabolite endosulfan sulfate also induced CYP2B6 (12-fold) and CYP3A4 (6-fold) promoter activities over control at 10 {mu}M. In the presence of hCAR-3, endosulfan-alpha induced CYP2B6 (2-fold) promoter activity at 10 {mu}M, but not at lower concentrations. These data indicate that endosulfan-alpha significantly activates hPXR strongly and hCAR weakly. Using western blot analysis of human hepatocytes, the lowest concentrations at which CYP2B6 and CYP3A4 protein levels were found to be significantly elevated by endosulfan-alpha were 1.0 {mu}M and 10 {mu}M, respectively. In mPXR-null/hPXR-transgenic mice, endosulfan-alpha exposure (2.5 mg/kg/day) caused a significant reduction of tribromoethanol-induced sleep times by approximately 50%, whereas no significant change in sleep times was observed in PXR-null mice. These data support the role of endosulfan-alpha as a strong activator of PXR and inducer of CYP2B6 and CYP3A4, which may impact metabolism of CYP2B6 or CYP3A4 substrates.« less

  8. Endosulfan induces CYP2B6 and CYP3A4 by activating the pregnane X receptor.

    PubMed

    Casabar, Richard C T; Das, Parikshit C; Dekrey, Gregory K; Gardiner, Catherine S; Cao, Yan; Rose, Randy L; Wallace, Andrew D

    2010-06-15

    Endosulfan is an organochlorine pesticide commonly used in agriculture. Endosulfan has affects on vertebrate xenobiotic metabolism pathways that may be mediated, in part, by its ability to activate the pregnane X receptor (PXR) and/or the constitutive androstane receptor (CAR) which can elevate expression of cytochrome P450 (CYP) enzymes. This study examined the dose-dependency and receptor specificity of CYP induction in vitro and in vivo. The HepG2 cell line was transiently transfected with CYP2B6- and CYP3A4-luciferase promoter reporter plasmids along with human PXR (hPXR) or hCAR expression vectors. In the presence of hPXR, endosulfan-alpha exposure caused significant induction of CYP2B6 (16-fold) and CYP3A4 (11-fold) promoter activities over control at 10 microM. The metabolite endosulfan sulfate also induced CYP2B6 (12-fold) and CYP3A4 (6-fold) promoter activities over control at 10 microM. In the presence of hCAR-3, endosulfan-alpha induced CYP2B6 (2-fold) promoter activity at 10 microM, but not at lower concentrations. These data indicate that endosulfan-alpha significantly activates hPXR strongly and hCAR weakly. Using western blot analysis of human hepatocytes, the lowest concentrations at which CYP2B6 and CYP3A4 protein levels were found to be significantly elevated by endosulfan-alpha were 1.0 microM and 10 microM, respectively. In mPXR-null/hPXR-transgenic mice, endosulfan-alpha exposure (2.5mg/kg/day) caused a significant reduction of tribromoethanol-induced sleep times by approximately 50%, whereas no significant change in sleep times was observed in PXR-null mice. These data support the role of endosulfan-alpha as a strong activator of PXR and inducer of CYP2B6 and CYP3A4, which may impact metabolism of CYP2B6 or CYP3A4 substrates. Copyright 2010 Elsevier Inc. All rights reserved.

  9. A highly predictive A 4 flavor 3-3-1 model with radiative inverse seesaw mechanism

    NASA Astrophysics Data System (ADS)

    Cárcamo Hernández, A. E.; Long, H. N.

    2018-04-01

    We build a highly predictive 3-3-1 model, where the field content is extended by including several SU(3) L scalar singlets and six right handed Majorana neutrinos. In our model the {SU}{(3)}C× {SU}{(3)}L× U{(1)}X gauge symmetry is supplemented by the {A}4× {Z}4× {Z}6× {Z}16× {Z}16{\\prime } discrete group, which allows to get a very good description of the low energy fermion flavor data. In the model under consideration, the {A}4× {Z}4× {Z}6× {Z}16× {Z}16{\\prime } discrete group is broken at very high energy scale down to the preserved Z 2 discrete symmetry, thus generating the observed pattern of SM fermion masses and mixing angles and allowing the implementation of the loop level inverse seesaw mechanism for the generation of the light active neutrino masses, respectively. The obtained values for the physical observables in the quark sector agree with the experimental data, whereas those ones for the lepton sector also do, only for the case of inverted neutrino mass spectrum. The normal neutrino mass hierarchy scenario of the model is ruled out by the neutrino oscillation experimental data. We find an effective Majorana neutrino mass parameter of neutrinoless double beta decay of m ee = 46.9 meV, a leptonic Dirac CP violating phase of -81.37° and a Jarlskog invariant of about 10-2 for the inverted neutrino mass hierarchy. The preserved Z 2 symmetry allows for a stable scalar dark matter candidate.

  10. CYP3A4-dependent cellular response does not relate to CYP3A4-catalysed metabolites of C-1748 and C-1305 acridine antitumor agents in HepG2 cells.

    PubMed

    Augustin, Ewa; Niemira, Magdalena; Hołownia, Adam; Mazerska, Zofia

    2014-11-01

    High CYP3A4 expression sensitizes tumor cells to certain antitumor agents while for others it can lower their therapeutic efficacy. We have elucidated the influence of CYP3A4 overexpression on the cellular response induced by antitumor acridine derivatives, C-1305 and C-1748, in two hepatocellular carcinoma (HepG2) cell lines, Hep3A4 stably transfected with CYP3A4 isoenzyme, and HepC34 expressing empty vector. The compounds were selected considering their different chemical structures and different metabolic pathways seen earlier in human and rat liver microsomes C-1748 was transformed to several metabolites at a higher rate in Hep3A4 than in HepC34 cells. In contrast, C-1305 metabolism in Hep3A4 cells was unchanged compared to HepC34 cells, with each cell line producing a single metabolite of comparable concentration. C-1748 resulted in a progressive appearance of sub-G1 population to its high level in both cell lines. In turn, the sub-G1 fraction was dominated in CYP3A4-overexpressing cells following C-1305 exposure. Both compounds induced necrosis and to a lesser extent apoptosis, which were more pronounced in Hep3A4 than in wild-type cells. In conclusion, CYP3A4-overexpressing cells produce higher levels of C-1748 metabolites, but they do not affect the cellular responses to the drug. Conversely, cellular response was modulated following C-1305 treatment in CYP3A4-overexpressing cells, although metabolism of this drug was unaltered. © 2014 International Federation for Cell Biology.

  11. Synthesis and Biological Evaluation of Some [1,2,4]Triazolo[4,3-a]quinoxaline Derivatives as Novel Anticonvulsant Agents

    PubMed Central

    Ghiaty, Adel; El-Morsy, Ahmed; El-Gamal, Kamal

    2013-01-01

    2-([1,2,4]Triazolo[4,3-a]quinoxalin-4-ylthio)acetic acid hydrazide (10) was used as a precursor for the syntheses of novel quinoxaline derivatives with potential anticonvulsant properties. The newly synthesized compounds have been characterized by IR, 1H NMR, and mass spectral data followed by elemental analysis. The anticonvulsant evaluation was carried out for eleven of the synthesized compounds using metrazol induced convulsions model and phenobarbitone sodium as a standard. Among this set of tested compounds, two of them (14, and 15b) showed the best anticonvulsant activities. PMID:24198971

  12. 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

  13. Reassortant clade 2.3.4.4 of highly pathogenic avian influenza A (H5N6) virus, Taiwan, 2017

    USDA-ARS?s Scientific Manuscript database

    A highly pathogenic avian influenza A(H5N6) virus of clade 2.3.4.4 was detected in a domestic duck found dead in Taiwan during February 2017. The endemic situation and continued evolution of various reassortant highly pathogenic avian influenza viruses in Taiwan warrant concern about further reassor...

  14. Ligand design, synthesis and biological anti-HCV evaluations for genotypes 1b and 4a of certain 4-(3- & 4-[3-(3,5-dibromo-4-hydroxyphenyl)-propylamino]phenyl) butyric acids and 3-(3,5-dibromo-4-hydroxyphenyl)-propylamino-acetamidobenzoic acid esters.

    PubMed

    Ismail, Mohamed Abdel Hamid; Abouzid, Khaled A M; Mohamed, Nasser Saad; Dokla, Eman Mahmoud Elawady

    2013-12-01

    4-(4-[N-1-carboxy-3-(3,5-dibromo-4-hydroxyphenyl)-3-oxo-propylamino]phenyl)-4-oxo-butyric acid (V), 4-(3- & 4-[N-1-carboxy-3-(3,5-dibromo-4-hydroxyphenyl)-3-oxo-propylaminophenyl]-2-aryl-4-oxo-butyric acids (Xa-e) and 4-(2-alkyl-2-[N-3-(3,5-dibromo-4-hydroxyphenyl)-1-carboxy-3-oxo-propylamino]acetamido) benzoate esters (XVa-e) were designed, synthesized and biologically evaluated as anti-HCV for genotypes 1b and 4a. The design was based on their docking scores with HCV NS3/4A protease-binding site of the genotype 1b (1W3C), which is conserved in the genotype 4a structure. The docking scores predicted that most of these molecules have higher affinity to the HCV NS3/4A enzyme more than Indoline lead. These compounds were synthesized and evaluated for their cytopathic inhibitory activity against RAW HCV cell cultures of genotype 4a and also examined against Huh 5-2 HCV cell culture of genotype 1b, utilizing Luciferase and MTS assays. Compounds Xa and Xb have 95 and 80% of the activity of Ribavirin against genotype 4a and compounds XVa, XVb and XVd exerted high percentage inhibitory activity against genotype 1b equal 87.7, 84.3 and 82.8%, respectively, with low EC50 doses.

  15. 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.

  16. 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.

  17. Synthesis of 2',4-dihydroxy-3-methoxychalcone and 2',4',4-trihydroxy-3-methoxychalcone as a candidate anticancer against cervical (WiDr), colon (HeLa), and breast (T47d) cancer cell lines in vitro

    NASA Astrophysics Data System (ADS)

    Matsjeh, Sabirin; Swasono, Respati Tri; Anwar, Chairil; Solikhah, Eti Nurwening; Lestari, Endang

    2017-03-01

    The compound 2',4-dihydroxy-3-methoxychalcone and 2',4',4-trihydroxy-3-methoxychalcone have been synthesized through Claisen-Schmidt reaction from 2-hydroxyacetophenone and 2,4-dihydroxyacetophenone with 4-hydroxy-3-methoxy benzaldehida (vanillin) in aqueous KOH 40% and KSF montmorillonite as catalyst in methanol. All these products were characterized by FT-IR, TLC Scanner, GC-MS, MS-Direct, and 1H-NMR and 13C-NMR spectrometer. Both of these compounds were tested citotoxycity activity as an anticancer against cervical, colon, and breast cancer cells (Hela, WiDr, and T47D cell lines) using MTT assay in vitro. Dose series given test solution concentration on Hela, WiDr, and T47D cells started from 6,25; 25; 50 and 100 µg/mL with incubation treatment for 24 hours. The result of study showed that the 2',4-dihydroxy-3-methoxychalcone as bright yellow crystal with the melting point of 114-115 °C and the yield of 13.77% and the 2',4',4-trihydroxy-3-methoxychalcone as bright yellow crystals with the melting point of 195-197 °C and the yield of 6%. Other 2',4-dihydroxy-3-methoxychalcone and 2',4',4-trihydroxy-3-methoxychalcone also exhibited cytotoxic activity against the cancer cell lines, with the 2',4',4-trihydroxy-3-methoxychalcone showed greater activities than the 2',4-dihydroxy-3-methoxychalcone in WiDr cell lines. The 2',4-dihydroxy-3-methoxychalcone and 2',4',4-trihydroxy-3-methoxychalcone exhibited strong anticancer activities with IC50 value below 20 µg/mL. The activity of 2',4',4-trihydroxy-3-methoxychalcone showed the most active against Hela and WiDr cell lines with IC50 value 8.53 and 2.66 µg/mL respectively, than T47D cell lines with IC50 value 24.61 µg/mL. The test results cytotoxic of 2',4-dihydroxy-3-methoxychalcone showed the most active against Hela and WiDr cell lines with IC50 value 12.80, 19.57 µg/mL than T47D cell lines with IC50 value of 20.73 µg/mL. IC50 value indicated that 2',4-dihydroxy-3-methoxychalcone and 2',4',4-trihydroxy-3

  18. A Hierarchical Z-Scheme α-Fe2 O3 /g-C3 N4 Hybrid for Enhanced Photocatalytic CO2 Reduction.

    PubMed

    Jiang, Zhifeng; Wan, Weiming; Li, Huaming; Yuan, Shouqi; Zhao, Huijun; Wong, Po Keung

    2018-03-01

    The challenge in the artificial photosynthesis of fossil resources from CO 2 by utilizing solar energy is to achieve stable photocatalysts with effective CO 2 adsorption capacity and high charge-separation efficiency. A hierarchical direct Z-scheme system consisting of urchin-like hematite and carbon nitride provides an enhanced photocatalytic activity of reduction of CO 2 to CO, yielding a CO evolution rate of 27.2 µmol g -1 h -1 without cocatalyst and sacrifice reagent, which is >2.2 times higher than that produced by g-C 3 N 4 alone (10.3 µmol g -1 h -1 ). The enhanced photocatalytic activity of the Z-scheme hybrid material can be ascribed to its unique characteristics to accelerate the reduction process, including: (i) 3D hierarchical structure of urchin-like hematite and preferable basic sites which promotes the CO 2 adsorption, and (ii) the unique Z-scheme feature efficiently promotes the separation of the electron-hole pairs and enhances the reducibility of electrons in the conduction band of the g-C 3 N 4 . The origin of such an obvious advantage of the hierarchical Z-scheme is not only explained based on the experimental data but also investigated by modeling CO 2 adsorption and CO adsorption on the three different atomic-scale surfaces via density functional theory calculation. The study creates new opportunities for hierarchical hematite and other metal-oxide-based Z-scheme system for solar fuel generation. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. The effect of calcination temperature on the performance of Co3O4-Bi2O3 as a heterogeneous catalyst of peroxymonosulfate

    NASA Astrophysics Data System (ADS)

    Zhang, Guangshan; Hu, Limin; Wang, Peng; Yuan, Yixing

    2017-11-01

    In this work, a time-saving microwave-assisted method for synthesis of Co3O4-Bi2O3 was reported. The synthesized Co3O4-Bi2O3 samples were characterized with different techniques to probe their crystalline structures and morphologies. The catalytic performances of synthesized Co3O4-Bi2O3 as peroxymonosulfate activator were evaluated by the degradation of bisphenol A. The effect of calcination temperature on Co3O4-Bi2O3 products was explored and the result showed that the sample calcined at 400 °C possessing superior catalytic activity.

  20. The high-resolution structure of the Centaurus A nucleus at 2.3 and 8.4 GHz

    NASA Technical Reports Server (NTRS)

    Meier, David L.; Preston, Robert A.; Morabito, David D.; Skjerve, Lyle; Slade, Martin A.; Wehrle, Ann E.; Niell, Arthur E.; Jauncey, David L.; Batchelor, Robert; Tzioumis, Anastasios K.

    1989-01-01

    VLBI observations of the nucleus of Centaurus A have been made at two frequencies with an array of five Australian radio telescopes as part of the Southern Hemisphere VLBI Experiment. Observations were made at 2.3 GHz with all five antennas, while only two were employed at 8.4 GHz. At 2.3 GHz seven tracks in the (u,v) plane with coverage of 6-8 hr each were obtained, yielding significant information on the structure of the nuclear jet. At 8.4 GHz a compact unresolved core was detected as well. It is found that the source consists of the compact self-absorbed core, a jet containing a set of three knots extending from 100 to 160 mas from the core, and a very long, narrow component elongated along the same position angle as the knots. The allowable range for the position angle of the jet is 51 + or - 3 deg, in agreement with that of the radio and X-ray structure on arcsecond and arcminute scales. The jet has brightened at 2.3 GHz by about 4 Jy, a factor of nearly 3, since the early 1970s, 1.8 Jy of which has occurred in the last 2 yr with no discernable changes in structure.

  1. Emergence of novel clade 2.3.4 influenza A (H5N1) virus subgroups in Yunnan Province, China.

    PubMed

    Hu, Tingsong; Song, Jianling; Zhang, Wendong; Zhao, Huanyun; Duan, Bofang; Liu, Qingliang; Zeng, Wei; Qiu, Wei; Chen, Gang; Zhang, Yingguo; Fan, Quanshui; Zhang, Fuqiang

    2015-07-01

    From December 2013 to March 2014, a major wave of highly pathogenic avian influenza outbreak occurred in poultry in Yunnan Province, China. We isolated and characterized eight highly pathogenic avian influenza A (H5N1) viruses from poultry. Full genome influenza sequences and analyses have been performed. Sequence analyses revealed that they belonged to clade 2.3.4 but did not fit within the three defined subclades. The isolated viruses were provisional subclade 2.3.4.4e. The provisional subclade 2.3.4.4e viruses with six internal genes from avian influenza A (H5N2) viruses in 2013 were the novel reassortant influenza A (H5N1) viruses which were associated with the outbreak of H5N1 occurred in egg chicken farms in Yunnan Province. The HA genes were similar to subtype H5 viruses isolated from January to March of 2014 in Asia including H5N6 and H5N8. The NA genes were most closely related to A/chicken/Vietnam/NCVD-KA423/2013 (H5N1) from the subclade 2.3.2. The HI assay demonstrated a lack of antigenic relatedness between clades 2.3.4.4e and 2.3.4.1 (RE-5 vaccine strain) or 2.3.2.2 (RE-6 vaccine strain). Copyright © 2015 Elsevier B.V. All rights reserved.

  2. 10 CFR 960.3-2-2-4 - The environmental assessment.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ...; and an assessment of the regional and local impacts of locating a repository at the site. The draft... 10 Energy 4 2012-01-01 2012-01-01 false The environmental assessment. 960.3-2-2-4 Section 960.3-2... FOR A NUCLEAR WASTE REPOSITORY Implementation Guidelines § 960.3-2-2-4 The environmental assessment...

  3. 10 CFR 960.3-2-2-4 - The environmental assessment.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ...; and an assessment of the regional and local impacts of locating a repository at the site. The draft... 10 Energy 4 2014-01-01 2014-01-01 false The environmental assessment. 960.3-2-2-4 Section 960.3-2... FOR A NUCLEAR WASTE REPOSITORY Implementation Guidelines § 960.3-2-2-4 The environmental assessment...

  4. 10 CFR 960.3-2-2-4 - The environmental assessment.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ...; and an assessment of the regional and local impacts of locating a repository at the site. The draft... 10 Energy 4 2013-01-01 2013-01-01 false The environmental assessment. 960.3-2-2-4 Section 960.3-2... FOR A NUCLEAR WASTE REPOSITORY Implementation Guidelines § 960.3-2-2-4 The environmental assessment...

  5. Reassortant Clade 2.3.4.4 of Highly Pathogenic Avian Influenza A(H5N6) Virus, Taiwan, 2017.

    PubMed

    Chen, Li-Hsuan; Lee, Dong-Hun; Liu, Yu-Pin; Li, Wan-Chen; Swayne, David E; Chang, Jen-Chieh; Chen, Yen-Ping; Lee, Fan; Tu, Wen-Jane; Lin, Yu-Ju

    2018-06-01

    A highly pathogenic avian influenza A(H5N6) virus of clade 2.3.4.4 was detected in a domestic duck found dead in Taiwan during February 2017. The endemic situation and continued evolution of various reassortant highly pathogenic avian influenza viruses in Taiwan warrant concern about further reassortment and a fifth wave of intercontinental spread.

  6. Tuning of magnetic frustration in S = 1 / 2 Kagomé lattices {[Cu3(CO3)2(bpe)3](CLO4)2}n and {[Cu3(CO3)2(bpy)3](CLO4)2}n through rigid and flexible ligands

    NASA Astrophysics Data System (ADS)

    Ajeesh, M. O.; Yogi, A.; Padmanabhan, M.; Nath, R.

    2015-04-01

    Single crystalline and polycrystalline samples of S = 1 / 2 Kagomé lattices { [Cu3(CO3)2(bpe)3 ](CLO4)2 } n and { [Cu3(CO3)2(bpy)3 ](CLO4)2 } n, respectively were synthesized. Their structural and magnetic properties were characterized by means of x-ray diffraction and magnetization measurements. Both compounds crystalize in a hexagonal structure (space group P-6) consisting of CuO4 Kagomé layers in the ab-plane but linked along c direction through either rigid bpy or flexible bpe ligands to form 3D frame works. Magnetic measurements reveal that both the compounds undergo ferromagnetic ordering (TC) at low temperatures and the TC and the extent of frustration could be tuned by changing the nature of the pillar ligands. {[Cu3(CO3)2(bpe)3](CLO4)2}n which is made up of flexible bpe ligands has a TC of 5.7 K and a Curie-Weiss temperature (θCW) of -39.7 K giving rise to a frustration parameter of |θCW | /TC ≃ 6.96. But the replacement of bpe by a more rigid and electronically delocalized bpy ligand leads to an enhanced TC ≃ 9.3 K and a reduced frustration parameter of |θCW | /TC ≃ 3.54.

  7. Anticonvulsant activity of a mGlu(4alpha) receptor selective agonist, (1S,3R,4S)-1-aminocyclopentane-1,2,4-tricarboxylic acid.

    PubMed

    Chapman, A G; Talebi, A; Yip, P K; Meldrum, B S

    2001-07-20

    The metabotropic Group III agonist, (1S,3R,4S)-1-aminocyclopentane-1,2,4-tricarboxylic acid (ACPT-1), selective for the mGlu(4alpha) receptor, suppresses sound-induced seizures in DBA/2 mice following its intracerebroventricular (i.c.v.) administration (ED(50) 5.6 [2.9-10.7], nmol i.c.v., 15 min, clonic phase) and in genetically epilepsy-prone (GEP) rats following focal administration into the inferior colliculus (ED(50) 0.08 [0.01-0.50], nmol, 60 min, clonic phase). ACPT-1 also protects against clonic seizures induced in DBA/2 mice by the Group I agonist, (RS)-3,5-dihydroxyphenylglycine (3,5-DHPG) (ED(50) 0.60 [0.29-1.2], nmol i.c.v.) and by the Group III antagonist, (RS)-alpha-methylserine-O-phosphate (MSOP) (ED(50) 49.3 [37.9-64.1], nmol i.c.v.). Another Group III agonist, (RS)-4-phosphonophenyl-glycine (PPG), preferentially activating the mGlu(8) receptor, previously shown to protect against sound-induced seizures in DBA/2 mice and GEP rats, also protects against seizures induced in DBA/2 by 3,5-DHPG (ED(50) 3.7 [2.4-5.7], nmol i.c.v.) and by the Group III antagonist, MSOP (ED(50) 40.2 [21.0-77.0], nmol i.c.v.). At very high doses (500 nmol i.c.v. and above), Group III antagonists have pro-convulsant and convulsant activity. The anticonvulsant protection against sound-induced seizures in DBA/2 mice provided by a fully protective dose (20 nmol, i.c.v.) of the mGlu(4) receptor agonist ACPT-1, is partially reversed by the co-administration of the Group III antagonists, MSOP, (RS)-alpha-methyl-4-phosphonophenylglycine (MPPG) or (S)-2-amino-2-methyl-4-phosphonobutanoic acid (MAP4), in the 20-50 nmol dose range. At doses of 50-200 nmol, MPPG and MAP4 cause further reversal of the ACPT-1 anticonvulsant protection, while the MSOP effect on ACPT-1 protection is abolished at higher doses. In contrast, the anticonvulsant protection against sound-induced seizures in DBA/2 mice provided by a fully protective dose (20 nmol, i.c.v.) of the mGlu(8) receptor agonist PPG, is not

  8. Characterization of a Highly Enriched Microbial Consortium Reductively Dechlorinating 2,3-Dichlorophenol and 2,4,6-Trichlorophenol and the Corresponding cprA Genes from River Sediment.

    PubMed

    El-Sayed, Wael S

    2016-08-26

    Anaerobic reductive dechlorination of 2,3-dichlorophenol (2,3DCP) and 2,4,6-trichlorophenol (2,4,6TCP) was investigated in microcosms from River Nile sediment. A stable sediment-free anaerobic microbial consortium reductively dechlorinating 2,3DCP and 2,4,6TCP was established. Defined sediment-free cultures showing stable dechlorination were restricted to ortho chlorine when enriched with hydrogen as the electron donor, acetate as the carbon source, and either 2,3-DCP or 2,4,6-TCP as electron acceptors. When acetate, formate, or pyruvate were used as electron donors, dechlorination activity was lost. Only lactate can replace dihydrogen as an electron donor. However, the dechlorination potential was decreased after successive transfers. To reveal chlororespiring species, the microbial community structure of chlorophenol-reductive dechlorinating enrichment cultures was analyzed by PCR-denaturing gradient gel electrophoresis (DGGE) of 16S rRNA gene fragments. Eight dominant bacteria were detected in the dechlorinating microcosms including members of the genera Citrobacter, Geobacter, Pseudomonas, Desulfitobacterium, Desulfovibrio and Clostridium. Highly enriched dechlorinating cultures were dominated by four bacterial species belonging to the genera Pseudomonas, Desulfitobacterium, and Clostridium. Desulfitobacterium represented the major fraction in DGGE profiles indicating its importance in dechlorination activity, which was further confirmed by its absence resulting in complete loss of dechlorination. Reductive dechlorination was confirmed by the stoichiometric dechlorination of 2,3DCP and 2,4,6TCP to metabolites with less chloride groups and by the detection of chlorophenol RD cprA gene fragments in dechlorinating cultures. PCR amplified cprA gene fragments were cloned and sequenced and found to cluster with the cprA/pceA type genes of Dehalobacter restrictus.

  9. Synthesis and structural study on (1E,2E,1'E,2'E)-3,3'-bis[(4-bromophenyl)-3,3'-(4-methy-1,2-phenylene diimine)] acetaldehyde dioxime: A combined experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Topal, T.; Kart, H. H.; Tunay Taşlı, P.; Karapınar, E.

    2015-06-01

    Tetradentate (1E,2E,1'E,2'E)-3,3'-bis[(4-bromophenyl)-3,3'-(4-methy-1,2-phenylene diimine)] acetaldehyde dioxime which possess N4 donor sets derived from the condensation of isonitroso- p-bromoacetophenone and 3,4-diaminotoluene are synthesized and characterized. The characterization of tetradentate Schiff base ligand has been deduced from LC-MS, FTIR, 13C and 1H NMR spectra and elemental analysis. Furthermore, the molecular geometry, infrared and NMR spectra of the title molecule in the ground state have been calculated by using the quantum chemical computational methods such as density functional theory (DFT) and ab initio Hartree-Fock (HF) methods with the 6-31G(d) and 6-311G(d) basis sets. The computed bond lengths and bond angles by using the both methods show the good agreement with each other. Moreover, the vibrational frequencies have been calculated and the scaled values have been compared with the experimental FTIR spectroscopic data. Assignments of the vibrational modes are made on the basis of potential energy distribution (PED) calculated from by using VEDA program. The correlations between the observed and calculated frequencies are in good agreement with each other as well as the correlation of the NMR data.

  10. Processes of Molecular Relaxation in Binary Crystalline Systems KNO3-KClO4, KNO3-KNO2, and K2CO3-K2SO4

    NASA Astrophysics Data System (ADS)

    Aliev, A. R.; Akhmedov, I. R.; Kakagasanov, M. G.; Aliev, Z. A.; Gafurov, M. M.; Rabadanov, K. Sh.; Amirov, A. M.

    2018-03-01

    The processes of molecular relaxation in binary crystalline systems KNO3-KClO4, KNO3-KNO2, and K2CO3-K2SO4 are studied via differential thermal analysis and Raman spectroscopy. It is found that the relaxation time of the vibrations ν1( A) of anions NO- 3 and CO2- 3 in systems KNO3-KClO4, KNO3-KNO2, and K2CO3-K2SO4 is less than that in KNO3 and K2CO3, respectively. It is shown that the increased rate of relaxation is explained by an additional relaxation mechanism presented in the system. This mechanism is associated with the excitation of vibrations of anions ClO- 4, NO- 2, and SO2- 4 and the lattice phonons that emerge. It is found that this relaxation mechanism requires correspondence of the frequency difference of these vibrations to the region of sufficiently high density of states of the phonon spectrum.

  11. Metabolism of 1,2,3,4-, 1,2,3,5-, and 1,2,4,5-tetrachlorobenzene in the squirrel monkey

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

    Schwartz, H.; Chu, I.; Villeneuve, D.C.

    1987-01-01

    The metabolism of three tetrachlorobenzene isomers (TeCB) was investigated in the squirrel monkey. The animals were administered orally 6 single doses of /sup 14/C-labeled 1,2,3,4-, 1,2,4,5-, or 1,2,3,5-tetrachlorobenzene over a 3-wk period at levels ranging from 50 to 100 mg/kg body weight (b.w) and kept in individual metabolism cages to collect urine and feces for radioassay. Approximately 38% (1,2,3,4-TeCB), 36% (1,2,3,5-TeCB), and 18% (1,2,4,5-TeCB) of the doses were excreted respectively in the feces 48 h post administration. In monkeys dosed with 1,2,3,4-TeCB, unchanged compound accounted for 50% of the fecal radioactivity. Unchanged compound accounted for more than 50% of themore » fecal radioactivity found in the monkeys dosed with 1,2,3,5-TeCB. The fecal metabolites were identified in both groups. No metabolites were detected in the feces of monkeys dosed with 1,2,4,5-TeCB. While the fecal route represented the major route of excretion for 1,2,3,4-TeCB, the other two isomers were eliminated exclusively in the feces. The above data in the squirrel monkey are different from those obtained with the rat and the rabbit, and demonstrate the different metabolic pathways for the isomers.« less

  12. Structure determination of two structural analogs, named 3-[1-(2-fluoro-4-biphenyl)ethyl]-6-(4-fluorophenyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (C23H16F2N4S) and 3-[1-(2-fluoro-4-biphenyl)ethyl]-6-(4-chlorophenyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (C23H16ClFN4S) by synchrotron X-ray powder diffraction

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

    Gündoğdu, Gülsüm; Aytaç, Sevim Peri; Müller, Melanie

    Two novel compounds, 3-[1-(2-fluoro-4-biphenyl)ethyl]-6-(4-fluorophenyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (C 23H 16F 2N 4S) (1) and 3-[1-(2-fluoro-4-biphenyl)ethyl]-6-(4-chlorophenyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (C 23H 16ClFN 4S) (2), have been designed and synthesized as cytotoxic agents. The compounds were characterized by infrared, proton nuclear magnetic resonance, mass spectral data, elemental analysis and X-ray powder diffraction. The present study comprises spectral data and crystal structures of these novel compounds determined from synchrotron X-ray powder diffraction data. The structure solutions were obtained by simulated annealing. The final structures were achieved by Rietveld refinement using soft restraints for all bond lengths, bond angles, and planar groups. Both compounds crystallize in space groupmore » $$P\\bar 1$$,Z= 2, with the unit-cell parametersa= 6.37433(9),b= 11.3641(2),c= 14.09115(19) Å,α= 80.1740(8)°,β= 85.1164(8)°,γ= 80.9831(10)°,V= 991.55(3) Å 3of compound (1) anda= 6.53736(6),b= 11.55725(15),c= 14.01373(13) Å,α= 80.3323(7)°,β= 84.8939(6)°,γ= 79.3954(8)°,V= 1024.08(2) Å 3of compound (2). Structural analyses reveal that the title compounds are isostructural.« less

  13. Trans-tail regulation of MLL4-catalyzed H3K4 methylation by H4R3 symmetric dimethylation is mediated by a tandem PHD of MLL4

    PubMed Central

    Dhar, Shilpa S.; Lee, Sung-Hun; Kan, Pu-Yeh; Voigt, Philipp; Ma, Li; Shi, Xiaobing; Reinberg, Danny; Lee, Min Gyu

    2012-01-01

    Mixed-lineage leukemia 4 (MLL4; also called MLL2 and ALR) enzymatically generates trimethylated histone H3 Lys 4 (H3K4me3), a hallmark of gene activation. However, how MLL4-deposited H3K4me3 interplays with other histone marks in epigenetic processes remains largely unknown. Here, we show that MLL4 plays an essential role in differentiating NT2/D1 stem cells by activating differentiation-specific genes. A tandem plant homeodomain (PHD4–6) of MLL4 recognizes unmethylated or asymmetrically dimethylated histone H4 Arg 3 (H4R3me0 or H4R3me2a) and is required for MLL4's nucleosomal methyltransferase activity and MLL4-mediated differentiation. Kabuki syndrome mutations in PHD4–6 reduce PHD4–6's binding ability and MLL4's catalytic activity. PHD4–6's binding strength is inhibited by H4R3 symmetric dimethylation (H4R3me2s), a gene-repressive mark. The protein arginine methyltransferase 7 (PRMT7), but not PRMT5, represses MLL4 target genes by up-regulating H4R3me2s levels and antagonizes MLL4-mediated differentiation. Consistently, PRMT7 knockdown increases MLL4-catalyzed H3K4me3 levels. During differentiation, decreased H4R3me2s levels are associated with increased H3K4me3 levels at a cohort of genes, including many HOXA and HOXB genes. These findings indicate that the trans-tail inhibition of MLL4-generated H3K4me3 by PRMT7-regulated H4R3me2s may result from H4R3me2s's interference with PHD4–6's binding activity and is a novel epigenetic mechanism that underlies opposing effects of MLL4 and PRMT7 on cellular differentiation. PMID:23249737

  14. Trans-tail regulation of MLL4-catalyzed H3K4 methylation by H4R3 symmetric dimethylation is mediated by a tandem PHD of MLL4.

    PubMed

    Dhar, Shilpa S; Lee, Sung-Hun; Kan, Pu-Yeh; Voigt, Philipp; Ma, Li; Shi, Xiaobing; Reinberg, Danny; Lee, Min Gyu

    2012-12-15

    Mixed-lineage leukemia 4 (MLL4; also called MLL2 and ALR) enzymatically generates trimethylated histone H3 Lys 4 (H3K4me3), a hallmark of gene activation. However, how MLL4-deposited H3K4me3 interplays with other histone marks in epigenetic processes remains largely unknown. Here, we show that MLL4 plays an essential role in differentiating NT2/D1 stem cells by activating differentiation-specific genes. A tandem plant homeodomain (PHD(4-6)) of MLL4 recognizes unmethylated or asymmetrically dimethylated histone H4 Arg 3 (H4R3me0 or H4R3me2a) and is required for MLL4's nucleosomal methyltransferase activity and MLL4-mediated differentiation. Kabuki syndrome mutations in PHD(4-6) reduce PHD(4-6)'s binding ability and MLL4's catalytic activity. PHD(4-6)'s binding strength is inhibited by H4R3 symmetric dimethylation (H4R3me2s), a gene-repressive mark. The protein arginine methyltransferase 7 (PRMT7), but not PRMT5, represses MLL4 target genes by up-regulating H4R3me2s levels and antagonizes MLL4-mediated differentiation. Consistently, PRMT7 knockdown increases MLL4-catalyzed H3K4me3 levels. During differentiation, decreased H4R3me2s levels are associated with increased H3K4me3 levels at a cohort of genes, including many HOXA and HOXB genes. These findings indicate that the trans-tail inhibition of MLL4-generated H3K4me3 by PRMT7-regulated H4R3me2s may result from H4R3me2s's interference with PHD(4-6)'s binding activity and is a novel epigenetic mechanism that underlies opposing effects of MLL4 and PRMT7 on cellular differentiation.

  15. A study of Na(x)Pt3O4 as an O2 electrode bifunctional electrocatalyst

    NASA Technical Reports Server (NTRS)

    Fielder, William L.; Singer, Joseph

    1991-01-01

    The present study suggests that polytetrafluoroethylene (PTFE) bonded Na(X)Pt3O4 gas porous diffusion electrodes may be a viable candidate for bifunctional O2 reduction and evolution activity. The electrodes exhibited Tafel slopes of about 0.06 V/decade for both O2 reduction an evolution. For O2 reduction, the 0.06 slope doubled to 0.12 V/decade at larger current densities. Preliminary stability testing at 24 C suggest that the Na(x)Pt3O4 electrodes were relatively stable at reducing and oxidizing potentials typically encountered at the O2 electrodes in a regenerative fuel cell.

  16. Hypovalency--a kinetic-energy density description of a 4c-2e bond.

    PubMed

    Jacobsen, Heiko

    2009-06-07

    A bond descriptor based on the kinetic energy density, the localized-orbital locator (LOL), is used to characterize the nature of the chemical bond in electron deficient multi-center bonds. The boranes B(2)H(6), B(4)H(4), B(4)H(10), [B(6)H(6)](2-), and [B(6)H(7)](-) serve as prototypical examples of hypovalent 3c-2e and 4c-2e bonding. The kinetic energy density is derived from a set of Kohn-Sham orbitals obtained from pure density functional calculations (PBE/TZVP), and the topology of LOL is analyzed in terms of (3,-3) attractors (Gamma). The B-B-B and B-H-B 3c-2e, and the B-B-H-B 4c-2e bonding situations are defined by their own characteristic LOL profiles. The presence of one attractor in relation to the three or four atoms that are engaged in electron deficient bonding provides sufficient indication of the type of 3c-2e or 4c-2e bond present. For the 4c-2e bond in [B(6)H(7)](-) the LOL analysis is compared to results from an experimental QTAIM study.

  17. Reassortment of influenza A viruses in wild birds in Alaska before H5 Clade 2.3.4.4 Outbreaks

    USGS Publications Warehouse

    Hill, Nichola J.; Hussein, Islam T. M.; Davis, Kimberly R.; Ma, Eric J.; Spivey, Timothy; Ramey, Andy M.; Puryear, Wendy Blay; Das, Suman R.; Halpin, Rebecca A.; Lin, Xudong; Federova, Nadia B.; Suarez, David L.; Boyce, Walter M.; Runstadler, Jonathan A.

    2017-01-01

    Sampling of mallards in Alaska during September 2014–April 2015 identified low pathogenic avian influenza A virus (subtypes H5N2 and H1N1) that shared ancestry with highly pathogenic reassortant H5N2 and H5N1 viruses. Molecular dating indicated reassortment soon after interhemispheric movement of H5N8 clade 2.3.4.4, suggesting genetic exchange in Alaska or surrounds before outbreaks.

  18. The bovine TRPV3 as a pathway for the uptake of Na+, Ca2+, and NH4+

    PubMed Central

    Liebe, Franziska; Liebe, Hendrik

    2018-01-01

    Absorption of ammonia from the gastrointestinal tract results in problems that range from hepatic encephalopathy in humans to poor nitrogen efficiency of cattle with consequences for the global climate. Previous studies on epithelia and cells from the native ruminal epithelium suggest functional involvement of the bovine homologue of TRPV3 (bTRPV3) in ruminal NH4+ transport. Since the conductance of TRP channels to NH4+ has never been studied, bTRPV3 was overexpressed in HEK-293 cells and investigated using the patch-clamp technique and intracellular calcium imaging. Control cells contained the empty construct. Divalent cations blocked the conductance for monovalent cations in both cell types, with effects higher in cells expressing bTRPV3. In bTRPV3 cells, but not in controls, menthol, thymol, carvacrol, or 2-APB stimulated whole cell currents mediated by Na+, Cs+, NH4+, and K+, with a rise in intracellular Ca2+ observed in response to menthol. While only 25% of control patches showed single-channel events (with a conductance of 40.8 ± 11.9 pS for NH4+ and 25.0 ± 5.8 pS for Na+), 90% of bTRPV3 patches showed much larger conductances of 127.8 ± 4.2 pS for Na+, 240.1 ± 3.6 pS for NH4+, 34.0 ± 1.7 pS for Ca2+, and ~ 36 pS for NMDG+. Open probability, but not conductance, rose with time after patch excision. In conjunction with previous research, we suggest that bTRPV3 channels may play a role in the transport of Na+, K+, Ca2+ and NH4+ across the rumen with possible repercussions for understanding the function of TRPV3 in other epithelia. PMID:29494673

  19. The bovine TRPV3 as a pathway for the uptake of Na+, Ca2+, and NH4.

    PubMed

    Schrapers, Katharina T; Sponder, Gerhard; Liebe, Franziska; Liebe, Hendrik; Stumpff, Friederike

    2018-01-01

    Absorption of ammonia from the gastrointestinal tract results in problems that range from hepatic encephalopathy in humans to poor nitrogen efficiency of cattle with consequences for the global climate. Previous studies on epithelia and cells from the native ruminal epithelium suggest functional involvement of the bovine homologue of TRPV3 (bTRPV3) in ruminal NH4+ transport. Since the conductance of TRP channels to NH4+ has never been studied, bTRPV3 was overexpressed in HEK-293 cells and investigated using the patch-clamp technique and intracellular calcium imaging. Control cells contained the empty construct. Divalent cations blocked the conductance for monovalent cations in both cell types, with effects higher in cells expressing bTRPV3. In bTRPV3 cells, but not in controls, menthol, thymol, carvacrol, or 2-APB stimulated whole cell currents mediated by Na+, Cs+, NH4+, and K+, with a rise in intracellular Ca2+ observed in response to menthol. While only 25% of control patches showed single-channel events (with a conductance of 40.8 ± 11.9 pS for NH4+ and 25.0 ± 5.8 pS for Na+), 90% of bTRPV3 patches showed much larger conductances of 127.8 ± 4.2 pS for Na+, 240.1 ± 3.6 pS for NH4+, 34.0 ± 1.7 pS for Ca2+, and ~ 36 pS for NMDG+. Open probability, but not conductance, rose with time after patch excision. In conjunction with previous research, we suggest that bTRPV3 channels may play a role in the transport of Na+, K+, Ca2+ and NH4+ across the rumen with possible repercussions for understanding the function of TRPV3 in other epithelia.

  20. Pioglitazone, an in vitro inhibitor of CYP2C8 and CYP3A4, does not increase the plasma concentrations of the CYP2C8 and CYP3A4 substrate repaglinide.

    PubMed

    Kajosaari, Lauri I; Jaakkola, Tiina; Neuvonen, Pertti J; Backman, Janne T

    2006-03-01

    Pioglitazone, a thiazolidinedione antidiabetic, inhibits cytochrome P450 (CYP) 2C8 and CYP3A4 enzymes in vitro. Repaglinide, a meglitinide analogue antidiabetic, is metabolised by CYP2C8 and CYP3A4. In patients with type 2 diabetes, the pioglitazone-repaglinide combination has acted synergistically on glycaemic parameters. Our aim was to determine whether pioglitazone increases the plasma concentrations of repaglinide. In a randomized, 2-phase cross-over study, 12 healthy volunteers received 30 mg pioglitazone or placebo once daily for 5 days. On day 5, they ingested a single 0.25 mg dose of repaglinide 1 h after the last pretreatment dose. Plasma repaglinide and pioglitazone, and blood glucose concentrations were measured for 12 h. During the pioglitazone phase, the mean peak plasma repaglinide concentration (C(max)) and the total area under the concentration-time curve [AUC(0-infinity)] of repaglinide were 100% (range 53-157%, P=0.99) and 90% (range 63-120%, P=0.22), respectively, of those during the placebo phase. Also the half-life of repaglinide was unaffected, but the median peak time of repaglinide was shortened from 40 min to 20 min by pioglitazone (P=0.014). The short-term pioglitazone administration did not modify the blood glucose-lowering effect of a single dose of repaglinide. Pioglitazone does not increase the plasma concentrations of repaglinide, indicating that the inhibitory effect of pioglitazone on CYP2C8 and CYP3A4 is very weak in vivo, probably due to its extensive plasma protein binding. The synergistic effect of repaglinide and pioglitazone on the glycaemic parameters, seen in patients with type 2 diabetes during their long-term use, is unlikely to be caused by inhibition of repaglinide metabolism by pioglitazone.

  1. Rational synthesis of high nuclearity Mo/Fe/S clusters: the reductive coupling approach in the convenient synthesis of (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et, (n)Pr, (n)Bu] and the new [(Cl(4)-cat)(2)Mo(2)Fe(2)S(3)O(PEt(3))(3)Cl]-1/2(Fe(PEt(3))(2)(MeCN)(4)) and (Cl(4)-cat)(2)Mo(2)Fe(3)S(5)(PEt(3))(5) clusters.

    PubMed

    Han, J; Koutmos, M; Ahmad, S A; Coucouvanis, D

    2001-11-05

    A general method for the synthesis of high nuclearity Mo/Fe/S clusters is presented and involves the reductive coupling of the (Et(4)N)(2)[(Cl(4)-cat)MoOFeS(2)Cl(2)] (I) and (Et(4)N)(2)[Fe(2)S(2)Cl(4)] (II) clusters. The reaction of I and II with Fe(PR(3))(2)Cl(2) or sodium salts of noncoordinating anions such as NaPF(6) or NaBPh(4) in the presence of PR(3) (R = Et, (n)Pr, or (n)Bu) affords (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et (IIIa), (n)Pr (IIIb), (n)Bu (IIIc)], Fe(6)S(6)(PEt(3))(4)Cl(2) (IV) and (PF(6))[Fe(6)S(8)(P(n)Pr(3))(6)] (V) as byproducts. The isolation of (Et(4)N)[Fe(PEt(3))Cl(3)] (VI), NaCl, and SPEt(3) supports a reductive coupling mechanism. Cluster IV and V also have been synthesized by the reductive self-coupling of compound II. The reductive coupling reaction between I and II by PEt(3) and NaPF(6) in a 1:1 ratio produces the (Et(4)N)(2)[(Cl(4)-cat)Mo(L)Fe(3)S(4)Cl(3)] clusters [L = MeCN (VIIa), THF (VIIb)]. The hitherto unknown [(Cl(4)-cat)(2)Mo(2)Fe(2)S(3)O(PEt(3))(3)Cl](+) cluster (VIII) has been isolated as the 2:1 salt of the (Fe(PEt(3))(2)(MeCN)(4))(2+) cation after the reductive self-coupling reaction of I in the presence of Fe(PEt(3))(2)Cl(2). Cluster VIII crystallizes in the monoclinic space group P2(1)/c with a = 11.098(3) A, b = 22.827(6) A, c = 25.855(6) A, beta = 91.680(4) degrees, and Z = 4. The formal oxidation states of metal atoms in VIII have been assigned as Mo(III), Mo(IV), Fe(II), and Fe(III) on the basis of zero-field Mössbauer spectra. The Fe(PEt(3))(2)(MeCN)(4) cation of VIII is also synthesized independently, isolated as the BPh(4)(-) salt (IX), and has been structurally characterized. The reductive coupling of compound I also affords in low yield the new (Cl(4)-cat)(2)Mo(2)Fe(3)S(5)(PEt(3))(5) cluster (X) as a byproduct. Cluster X crystallizes in the monoclinic space group P2(1)/n with a = 14.811(3) A, b = 22.188(4) A, c = 21.864(4) A, beta = 100.124(3) degrees, and Z = 4 and the structure shows very short Mo

  2. 2-(1,3-Dithiolan-2-ylidene)-5-(1,3-dithian-2-ylidene)-1,3,4,6- tetrathiapentalene(DHDA-TTP), a hybrid of BDH-TTP and BDA-TTP, and its metallic cation-radical salts.

    PubMed

    Yamada, Jun-ichi; Watanabe, Maki; Toita, Takashi; Akutsu, Hiroki; Nakatsuji, Shin'ichi; Nishikawa, Hiroyuki; Ikemoto, Isao; Kikuchi, Koichi

    2002-05-21

    The synthesis and electrochemical properties of the DHDA-TTP donor, a hybrid of 2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene (BDH-TTP) and 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP), has been investigated, and its ability to form metallic cation-radical salts is elucidated.

  3. Effect of dinucleoside pyrophosphates on the oligomerization of activated mononucleotides on Na(+)-montmorillonite: reaction of 5'-phosphoro-4-(dimethylamino)pyridinium [4-(CH3)2NpypA] with A5'ppA

    NASA Technical Reports Server (NTRS)

    Prabahar, K. J.; Ferris, J. P.

    1997-01-01

    The oligomerization of adenosine 5'-phosphoro-4-(dimethylamino)pyridinium (4-(CH3)2-NpypA) and diadenosine 5',5'-pyrophosphate (A5'ppA) (9:1) on Na(+)-montmorillonite was studied. The oligomers were isolated and analyzed by selective enzymatic hydrolyses and the oligomeric composition and the percent of 3',5'-phosphodiester linkages present in each fraction was determined. The longest oligomers formed (11-mers) are slightly shorter than those produced in the absence of A5'ppA (12-mers). Smaller amounts of A5'ppA are incorporated into the oligomers than in the ImpA/A5'ppA reaction. The regioselectivity of 3',5'-phosphodiester bond formation is comparable to that of the oligomerization of 4-(CH3)2NpypA alone. An explanation of these data is proposed and the possible effect of dinucleoside pyrophosphate on prebiotic RNA formation is discussed.

  4. A discrete water hexamer with a new planar tetrameric water moiety trapped in the crystal host of [Ag(azelate)(4,4‧-bipyridine)]·(H2O)3

    NASA Astrophysics Data System (ADS)

    Luo, Geng-Geng; Wu, Dong-Liang; Liu, Li; Xia, Jiu-Xu; Li, Dong-Xu; Dai, Jing-Cao; Xiao, Zi-Jing

    2011-11-01

    The ultrasonic reaction of Ag 2O, bipy and H 2aze gave rise to a novel Ag(I) mixed-ligand coordination polymer, namely [Ag(aze)(bipy)]·(H 2O) 3 ( 1) (bipy = 4,4'-bipyridine, H 2aze = azelaic acid). In 1, Ag(I) ions are linked by bipy and aze ligands to form a single two-dimensional (2D) undulated net with a (6,3) topology, incorporating Ag 6(bipy) 4(aze) 2 windows of 22.58 × 11.06 Å based on Ag⋯Ag distances. A pair of identical 2D single nets are interconnected via π⋯π stacking and unsupported Ag⋯Ag interactions to generate a 2D double-layered net. A discrete water hexamer composed of a new planar tetrameric water ring and two pendent water molecules is perpendicularly located in each hydrophilic cavity of the 2D bilayer and acts as a 'glue' to assemble adjacent 2D double-layered nets into a three-dimensional (3D) structure.

  5. 40 CFR 721.9730 - 1,3,5-Triazin-2-amine, 4-di-meth-yl-a-mino-6-substituted-.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false 1,3,5-Triazin-2-amine, 4-di-meth-yl-a... New Uses for Specific Chemical Substances § 721.9730 1,3,5-Triazin-2-amine, 4-di-meth-yl-a-mino-6...-2-amine, 4-di-meth-yl-a-mino-6-substituted- (PMN Nos. P-92-343 and P-92-344) are subject to...

  6. Is inositol (1,3,4,5)-tetrakisphosphate a new second messenger

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

    Hansen, C.A.; Williamson, J.R.

    1986-05-01

    Hormone-stimulated hydrolysis of inositol (Ins) lipids results in the rapid formation of Ins(1,4,5)P/sub 3/, the second messenger for intracellular Ca/sup 2 +/ mobilization. Recently, a more polar inositol phosphate, Ins(1,3,4,5)P/sub 4/ as well as its probable hydrolysis product Ins(1,3,4)P/sub 3/ have been reported to accumulate in carbachol-stimulated brain slices. Vasopressin addition to hepatocytes prelabeled with (/sup 3/H)-Ins also showed a rapid increase of Ins(1,3,4,5)P/sub 4/, which was similar to that of Ins(1,4,5)P/sub 3/, while the accumulation of Ins(1,3,4)P/sub 3/ was slower. In order to examine whether Ins(1,3,4,5)P/sub 4/ has any functional effects on Ca/sup 2 +/ homeostasis, it was synthesizedmore » enzymatically from (/sup 3/H)-Ins(1,4,5)P/sub 3/ using a partially purified phosphoinositol kinase activity from rat brain cortex. (/sup 3/H)-labeled inositol phosphates were separated by anion exchange chromatography and analyzed by HPLC using ammonium formate/phosphoric acid gradient elution. Preliminary experiments indicate that Ins(1,3,4,5)P/sub 4/ up to 10 ..mu..M does not release Ca/sup 2 +/ from vesicular pools in saponin-permeabilized hepatocytes. It has a slight inhibitory effect on Ins(1,4,5)P/sub 3/-induced Ca/sup 2 +/ release. The effect of Ins(1,3,4,5)P/sub 4/ on plasma membrane Ca/sup 2 +/ fluxes are presently being investigated.« less

  7. Degradation of herbicide 2,4-dichlorophenoxybutanoic acid in the photolysis of [FeOH]2+ and [Fe(Ox)3]3- complexes: A mechanistic study.

    PubMed

    Pozdnyakov, Ivan; Sherin, Peter; Grivin, Vjacheslav; Plyusnin, Victor

    2016-03-01

    In the present work the Fe(III)-assisted photodegradation of the herbicide 2,4-dichlorophenoxybutanoic acid (2,4-DB) has been studied by means of stationary (308 nm) and laser flash (355 nm) photolysis. The initial quantum yield of 2,4-DB photodegradation in [FeOH](2+) and [Fe(Ox)3](3-) systems was evaluated to be 0.11 and 0.17 upon 308 nm exposure, respectively. The prolonged photolysis of [FeOH](2+) and [Fe(Ox)3](3-) systems results in the complete degradation of 2,4-DB with almost complete mineralization of herbicide and its aromatic products in the case of [FeOH](2+) photolysis and the accumulation of some persistent aromatic products in the case of [Fe(Ox)3](3-) photolysis. For both systems the main primary products of 2,4-DB photolysis determined by liquid chromatography - mass spectrometry are products of the hydroxylation, the substitution of chlorine atom to OH group, the loss of aliphatic tail and the opening of benzene ring. The obtained results indicate ROS species (mainly OH radical) to be responsible for the herbicide photodegradation. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Update on N2O4 Molecular Sieving with 3A Material at NASA/KSC

    NASA Technical Reports Server (NTRS)

    Davis, Chuck; Dorn, Claudia

    2000-01-01

    During its operational life, the Shuttle Program has experienced numerous failures in the Nitrogen Tetroxide (N2O4) portion of Reaction Control System (RCS), many of which were attributed to iron-nitrate contamination. Since the mid-1980's, N2O4 has been processed through a molecular sieve at the N2O4 manufacturer's facility which results in an iron content typically less than 0.5 parts-per-million-by-weight (ppmw). In February 1995, a Tiger Team was formed to attempt to resolve the iron nitrate problem. Eighteen specific actions were recommended as possibly reducing system failures. Those recommended actions include additional N2O4 molecular sieving at the Shuttle launch site. Testing at NASA White Sands Test Facility (WSTF) determined an alternative molecular sieve material could also reduce the water-equivalent content (free water and HNO3) and thereby further reduce the natural production of iron nitrate in N2O4 while stored in iron-alloy storage tanks. Since April '96, NASA Kennedy Space Center (KSC) has been processing N2O4 through the alternative molecular sieve material prior to delivery to Shuttle launch pad N2O4 storage tanks. A new, much larger capacity molecular sieve unit has also been used. This paper will evaluate the effectiveness of N2O4 molecular sieving on a large-scale basis and attempt to determine if the resultant lower-iron and lower-water content N2O4 maintains this new purity level in pad storage tanks and shuttle flight systems.

  9. A 2,4-dichlorophenoxyacetic acid analog screened using a maize coleoptile system potentially inhibits indole-3-acetic acid influx in Arabidopsis thaliana

    PubMed Central

    Suzuki, Hiromi; Matano, Naoyuki; Nishimura, Takeshi; Koshiba, Tomokazu

    2014-01-01

    Studies using inhibitors of indole-3-acetic acid (IAA) transport, not only for efflux but influx carriers, provide many aspects of auxin physiology in plants. 1-Naphtoxyacetic acid (1-NOA), an analog of the synthetic auxin 1-N-naphtalene acetic acid (NAA), inhibits the IAA influx carrier AUX1. However, 1-NOA also shows auxin activity because of its structural similarity to NAA. In this study, we have identified another candidate inhibitor of the IAA influx carrier. The compound, “7-B3; ethyl 2-[(2-chloro-4-nitrophenyl)thio]acetate,” is a 2,4-dichlorophenoxyacetic acid (2,4-D) analog. At high concentrations (> 300 µM), 7-B3 slightly reduced IAA transport and tropic curvature of maize coleoptiles, whereas lower concentrations had almost no effect. We have analyzed the effects of 7-B3 on Arabidopsis thaliana seedlings. 7-B3 rescued the 2,4-D-inhibited root elongation, but not the NAA-inhibited root elongation. The effect of 7-B3 was weaker than that of 1-NOA. Both 1-NOA and 7-B3 inhibited DR5::GUS expression induced by IAA and 2,4-D, but not that induced by NAA. At high concentrations, 1-NOA exhibited auxin activity, but 7-B3 did not. Furthermore, 7-B3 inhibited apical hook formation in etiolated seedlings more effectively than 1-NOA did. These results indicate that 7-B3 is a potential inhibitor of IAA influx that has almost no effect on IAA efflux or auxin signaling. PMID:24800738

  10. A Resumable Fluorescent Probe BHN-Fe3O4@SiO2 Hybrid Nanostructure for Fe3+ and its Application in Bioimaging

    NASA Astrophysics Data System (ADS)

    Zhou, Xi; Wang, Yujiao; Peng, Qi; Liu, Weisheng

    2017-12-01

    A multifunctional fluorescent probe BHN-Fe3O4@SiO2 nanostructure for Fe3+ was designed and developed. It has a good selective response to Fe3+ with fluorescence quenching and can be recycled using an external magnetic field. With adding EDTA (2.5 × 10-5 M) to the consequent product Fe3+-BHN-Fe3O4@SiO2, Fe3+ can be removed from the complex, and its fluorescence probing ability recovers, which means that this constituted on-off type fluorescence probe could be reversed and reused. At the same time, the probe has been successfully applied for quantitatively detecting Fe3+ in a linear mode with a low limit of detection 1.25 × 10-8 M. Furthermore, the BHN-Fe3O4@SiO2 nanostructure probe is successfully used to detect Fe3+ in living HeLa cells, which shows its great potential in bioimaging detection.

  11. A theoretical study on 3-(4-methoxyphenyl)-1-(pyridin-2-Yl) prop-2-en-1-one

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

    Öner, Nazmiye, E-mail: fizikcinaz@gmail.com; Tamer, Ömer, E-mail: omertamer@sakarya.edu.tr; Avci, Davut, E-mail: davcir@sakarya.edu.tr

    This study reports the geometric parameters, vibration frequencies, {sup 13}C and {sup 1}H NMR chemical shifts of 3-(4-Methoxyphenyl)-1-(pyridin-2-yl) prop-2-en-1-one (MPP) molecule calculated by B3LYP level of density functional theory (DFT) with 6-311++G(d,p) basis set. {sup 13}C and {sup 1}H NMR chemical shifts were calculated within GIAO approach which is one of the most common approaches. Additionally, 3D molecular surfaces such as molecular electrostatic potential (MEP) and electrostatic potential (ESP), were simulated by the same level. As a result, obtained theoretical results were found to be consistent with experimental ones. All of calculations were carried out Gaussian 09 package program.

  12. 3' Phosphatase activity toward phosphatidylinositol 3,4-bisphosphate [PI(3,4)P2] by voltage-sensing phosphatase (VSP).

    PubMed

    Kurokawa, Tatsuki; Takasuga, Shunsuke; Sakata, Souhei; Yamaguchi, Shinji; Horie, Shigeo; Homma, Koichi J; Sasaki, Takehiko; Okamura, Yasushi

    2012-06-19

    Voltage-sensing phosphatases (VSPs) consist of a voltage-sensor domain and a cytoplasmic region with remarkable sequence similarity to phosphatase and tensin homolog deleted on chromosome 10 (PTEN), a tumor suppressor phosphatase. VSPs dephosphorylate the 5' position of the inositol ring of both phosphatidylinositol 3,4,5-trisphosphate [PI(3,4,5)P(3)] and phosphatidylinositol 4,5-bisphosphate [PI(4,5)P(2)] upon voltage depolarization. However, it is unclear whether VSPs also have 3' phosphatase activity. To gain insights into this question, we performed in vitro assays of phosphatase activities of Ciona intestinalis VSP (Ci-VSP) and transmembrane phosphatase with tensin homology (TPTE) and PTEN homologous inositol lipid phosphatase (TPIP; one human ortholog of VSP) with radiolabeled PI(3,4,5)P(3). TLC assay showed that the 3' phosphate of PI(3,4,5)P(3) was not dephosphorylated, whereas that of phosphatidylinositol 3,4-bisphosphate [PI(3,4)P(2)] was removed by VSPs. Monitoring of PI(3,4)P(2) levels with the pleckstrin homology (PH) domain from tandem PH domain-containing protein (TAPP1) fused with GFP (PH(TAPP1)-GFP) by confocal microscopy in amphibian oocytes showed an increase of fluorescence intensity during depolarization to 0 mV, consistent with 5' phosphatase activity of VSP toward PI(3,4,5)P(3). However, depolarization to 60 mV showed a transient increase of GFP fluorescence followed by a decrease, indicating that, after PI(3,4,5)P(3) is dephosphorylated at the 5' position, PI(3,4)P(2) is then dephosphorylated at the 3' position. These results suggest that substrate specificity of the VSP changes with membrane potential.

  13. Molecular modeling of cytochrome P450 3A4

    NASA Astrophysics Data System (ADS)

    Szklarz, Grazyna D.; Halpert, James R.

    1997-05-01

    The three-dimensional structure of human cytochrome P450 3A4 was modeled based on crystallographic coordinates of four bacterial P450s: P450 BM-3, P450cam, P450terp, and P450eryF. The P450 3A4 sequence was aligned to those of the known proteins using a structure-based alignment of P450 BM-3, P450cam, P450terp, and P450eryF. The coordinates of the model were then calculated using a consensus strategy, and the final structure was optimized in the presence of water. The P450 3A4 model resembles P450 BM-3 the most, but the B' helix is similar to that of P450eryF, which leads to an enlarged active site when compared with P450 BM-3, P450cam, and P450terp. The 3A4 residues equivalent to known substrate contact residues of the bacterial proteins and key residues of rat P450 2B1 are located in the active site or the substrate access channel. Docking of progesterone into the P450 3A4 model demonstrated that the substrate bound in a 6β-orientation can interact with a number of active site residues, such as 114, 119, 301, 304, 305, 309, 370, 373, and 479, through hydrophobic interactions. The active site of the enzyme can also accommodate erythromycin, which, in addition to the residues listed for progesterone, also contacts residues 101, 104, 105, 214, 215, 217, 218, 374, and 478. The majority of 3A4 residues which interact with progesterone and/or erythromycin possess their equivalents in key residues of P450 2B enzymes, except for residues 297, 480 and 482, which do not contact either substrate in P450 3A4. The results from docking of progesterone and erythromycin into the enzyme model make it possible to pinpoint residues which may be important for 3A4 function and to target them for site-directed mutagenesis.

  14. 2,4,5-trihydroxy-3-methylacetophenone: A cellulosic chromophore as a case study of aromaticity

    Treesearch

    Nele Sophie Zwirchmayr; Thomas Elder; Markus Bacher; Andreas Hofinger-Horvath; Paul Kosma; Thomas Rosenau

    2017-01-01

    The title compound (2,4,5-trihydroxy-3-methylacetophenone, 1) was isolated as chromophore from aged cellulosic pulps. The peculiar feature of the compound is its weak aromatic system that can be converted into nonaromatic (quinoid or cyclic aliphatic) tautomers, depending on the conditions and reaction partners. In alkaline media, the participation of quinoid canonic...

  15. Novel mutations of CYP3A4 in Chinese.

    PubMed

    Hsieh, K P; Lin, Y Y; Cheng, C L; Lai, M L; Lin, M S; Siest, J P; Huang, J D

    2001-03-01

    Human cytochrome P450 3A4 is a major P450 enzyme in the liver and gastrointestinal tract. It plays important roles in the metabolism of a wide variety of drugs, some endogenous steroids, and harmful environmental contaminants. CYP3A4 exhibits a remarkable interindividual activity variation as high as 20-fold. To investigate whether the interindividual variation in CYP3A4 levels can be partly explained by genetic polymorphism, we analyzed DNA samples from 102 Chinese subjects by polymerase chain reaction (PCR)-single-strand conformation polymorphism analysis for novel point mutation in the CYP3A4 coding sequence and promoter region. Using PCR and directed sequencing method to establish the complete intron sequence of CYP3A4 from leukocytes, the complete genomic sequence from exon 1 through 13 of CYP3A4 was determined and published in the GenBank database (accession no. AF209389). CYP3A4-specific primers were designed accordingly. After PCR-single-strand conformation polymorphism and restriction fragment length polymorphism screening, we found three novel mutations; two are point mutations and one is insertion. The first variant allele (CYP3A4*4), an Ile118Val change, was found in 3 of 102 Chinese subjects. The next allele (CYP3A4*5), which causes a Pro218Arg amino acid change, was found in 2 of 102 subjects. We found an insertion in A(17776), designated as CYP3A4*6, which causes frame shift and an early stop codon in exon 9, in one heterozygous subject. We also investigated the CYP3A4 activity in these mutant subjects by measuring the morning spot urinary 6beta-hydroxycortisol to free cortisol ratio with the enzyme-linked immunosorbent assay method. When compared with healthy Chinese population data, the 6beta-hydroxycortisol to free cortisol ratio data suggested that these alleles (CYP3A4*4, CYP3A4*5, and CYP3A4*6) may decrease the CYP3A4 activity. Incidences of these mutations in Chinese subjects are rare. The prevalence of these point mutations in other ethnic

  16. Comprehensive physicochemical studies of a new hybrid material: 2-Amino-4-methyl-3-nitropyridinium hydrogen oxalate

    NASA Astrophysics Data System (ADS)

    Bryndal, I.; Kucharska, E.; Wandas, M.; Lorenc, J.; Hermanowicz, K.; Mączka, M.; Lis, T.; Marchewka, M.; Hanuza, J.

    2014-01-01

    A new organic-organic salt, 2-amino-4-methyl-3-nitropyridinium hydrogen oxalate (AMNPO), and its deuterium analogue have been synthesized and characterized by means of FT-IR, FT-Raman, DSC and single crystal X-ray studies. The DSC measurements and temperature dependence of the IR and Raman spectra in the range 4-295 K show that it undergoes a reversible phase transition at ∼240 K. At room temperature it crystallizes in noncentrosymmetric space group P21. The unit-cell is built of the 2-amino-4-methyl-3-nitropyridinium cations and oxalate monoanions which are connected via the Nsbnd H⋯O and Osbnd H⋯O hydrogen bonds. The geometrical and hydrogen bond parameters are similar for non-deuterated (at 120 and 293 K) and deuterated compounds (at 90 K). The phase transition is probably a consequence of order-disorder transition inside of hydrogen network. The 6-311G(2d,2p) basis set with B3LYP functional have been used to discuss the structure and vibrational spectra of the studied compound.

  17. Synthesis and pharmacological profile of a new selective G protein-coupled receptor 119 agonist; 6-((2-fluoro-3-(1-(3-isopropyl-1,2,4-oxadiazol-5-yl)piperidin-4-yl)propyl)amino)-2,3-dihydro-1H-inden-1-one.

    PubMed

    Sakairi, Masao; Kogami, Masakazu; Torii, Masafumi; Makino, Mitsuhiro; Kataoka, Daisuke; Okamoto, Ryuji; Miyazawa, Toshiyuki; Inoue, Megumi; Takahashi, Naoki; Harada, Satoko; Watanabe, Nobuhide

    2012-01-01

    6-((2-Fluoro-3-(1-(3-isopropyl-1,2,4-oxadiazol-5-yl)piperidin-4-yl)propyl)amino)-2,3-dihydro-1H-inden-1-one is a potent drug-like G protein-coupled receptor 119 (GPR119) agonist. It is hoped that this compound would be instrumental in probing the pharmacological potential of GPR119 agonists.

  18. Synthesis of Benzo[a]carbazoles and an Indolo[2,3-a]carbazole from 3-Aryltetramic Acids.

    PubMed

    Truax, Nathanyal J; Banales Mejia, Fernando; Kwansare, Deborah O; Lafferty, Megan M; Kean, Maeve H; Pelkey, Erin T

    2016-08-05

    A simple and flexible approach to 3-pyrrolin-2-one fused carbazoles is disclosed. The key step involves the BF3-mediated electrophilic substitution of indoles with N-alkyl-substituted 3-aryltetramic acids, which provides access to indole-substituted 3-pyrrolin-2-ones. Scholl-type oxidative cyclizations of these materials led to the formation of the corresponding 3-pyrrolin-2-one-fused benzo[a]carbazoles and indolo[2,3-a]carbazoles. This work represents the first synthesis of the benzo[a]pyrrolo[3,4-c]carbazol-3(8H)-one ring system, while the indolo[2,3-a]pyrrolo[3,4-c]carbazol-5-one ring system is found in a number of biologically active compounds including the protein kinase C (PKC) inhibitor, staurosporine.

  19. Facile synthesis of Fe3O4/g-C3N4/HKUST-1 composites as a novel biosensor platform for ochratoxin A.

    PubMed

    Hu, Shuisheng; Ouyang, Wenjun; Guo, Longhua; Lin, Zhenyu; Jiang, Xiaohua; Qiu, Bin; Chen, Guonan

    2017-06-15

    A fluorescent biosensor for ochratoxin A was fabricated on the basis of a new nanocomposite (Fe 3 O 4 /g-C 3 N 4 /HKUST-1 composites). Fe 3 O 4 /g-C 3 N 4 /HKUST-1 was synthesized in this work for the first time, which combined HKUST-1 with g-C 3 N 4 to improve its chemical stability. Fe 3 O 4 /g-C 3 N 4 /HKUST-1 composites have strong adsorption capacity for dye-labeled aptamer and are able to completely quench the fluorescence of the dye through the photoinduced electron transfer (PET) mechanism. In the presence of ochratoxin A (OTA), it can bind with the aptamer with high affinity, causing the releasing of the dye-labeled aptamer from the Fe 3 O 4 /g-C 3 N 4 /HKUST-1 and therefore results in the recovery of fluorescence. The fluorescence intensity of the biosensor has a linear relationship with the OTA concentration in the range of 5.0-160.0ng/mL. The LOD of sensor is 2.57ng/mL (S/N=3). This fluorescence sensor based on the Fe 3 O 4 /g-C 3 N 4 /HKUST-1 composites has been applied to detect OTA in corn with satisfying results. Copyright © 2016. Published by Elsevier B.V.

  20. Batagayite, CaZn2(Zn,Cu)6(PO4)4(PO3OH)3·12H2O, a new phosphate mineral from Këster tin deposit (Yakutia, Russia): occurrence and crystal structure

    NASA Astrophysics Data System (ADS)

    Yakovenchuk, Victor N.; Pakhomovsky, Yakov A.; Konopleva, Nataliya G.; Panikorovskii, Taras L.; Bazai, Ayya; Mikhailova, Julia A.; Bocharov, Vladimir N.; Ivanyuk, Gregory Yu.; Krivovichev, Sergey V.

    2017-12-01

    Batagayite, CaZn2(Zn,Cu)6(PO4)4(PO3OH)3·12H2O, is a new secondary phosphate mineral from the Këster deposit, Arga-Ynnykh-Khai massif, NE Yakutia, Russia. It is monoclinic, P21, a = 8.4264(4), b = 12.8309(6), c = 14.6928(9) Å, β = 98.514(6)o, V = 1571.05(15) Å3 and Z = 2 (from single-crystal X-ray diffraction data). Batagayite crystals are blades up to 2 mm long, flattened on {001} and elongated on [100]; blades often grow in radial aggregates. Associated minerals are arsenolite, native copper, epifanovite, fluorapatite, libethenite, Na-analogue of batagayite, pseudomalachite, quartz, sampleite, tobermorite, and Mg-analogue of hopeite. The streak is white and the luster is vitreous. The mineral is brittle and has a perfect cleavage on {001}, no parting was observed. The Mohs hardness is 3. Density, determined by the float-sink method in Clerici solution, is 2.90(3) g/cm3, and the calculated density is 3.02 g/cm3 (using the empirical formula and single-crystal unit-cell parameters). Batagayite is biaxial, optically negative, α = 1.566 ± 0.002, β = 1.572 ± 0.002, γ = 1.573 ± 0.002 at 589 nm. 2V meas. = 40(5)°, 2V calc = 44.3°. Optical orientation: Z is perpendicular to (001), further details unclear. No dispersion or pleochroism were observed. The mean chemical composition determined by electron microprobe is: Na2O 0.31, MgO 1.39, Al2O3 0.55, SiO2 0.48, P2O5 34.37, K2O 0.17, CaO 2.76, MnO 1.03, CuO 5.80, ZnO 35.62, CdO 0.24 wt%. The H2O content estimated from the crystal-structure refinement is 16.83 wt%, giving a total of 99.55 wt%. The empirical formula calculated on the basis of P + Si = 7 is (Zn6.22Cu1.04Ca0.70Mg0.49Mn0.21Al0.15Na0.14K0.05Cd0.03)Σ9.03(P6.89Si0.11)Σ7.00O24.91(OH)3.09·12.10H2O. The mineral easily dissolves in 10% room-temperature HCl. The eight diagnostic lines in the X-ray powder-diffraction pattern are (I-d[Å]-hkl): 100-14.59-001, 25-6.34-012, 11-6.02-111, 37-4.864-003, 13-4.766-112, 20-3.102-1 \\overline {2} \\overline {4} , 11-2.678-2

  1. Perrierite-(La), (La,Ce,Ca)4(Fe2+,Mn)(Ti,Fe3+,Al)4(Si2O7)2O8, a new mineral species from the Eifel volcanic district, Germany

    NASA Astrophysics Data System (ADS)

    Chukanov, N. V.; Blass, G.; Pekov, I. V.; Belakovskiy, D. I.; Van, K. V.; Rastsvetaeva, R. K.; Aksenov, S. M.

    2012-12-01

    Non-metamict perrierite-(La) discovered in the Dellen pumice quarry, near Mendig, in the Eifel volcanic district, Rheinland-Pfalz, Germany has been approved as a new mineral species (IMA no. 2010-089). The mineral was found in the late assemblage of sanidine, phlogopite, pyrophanite, zirconolite, members of the jacobsite-magnetite series, fluorcalciopyrochlore, and zircon. Perrierite-(La) occurs as isolated prismatic crystals up to 0.5 × 1 mm in size within cavities in sanidinite. The new mineral is black with brown streak; it is brittle, with the Mohs hardness of 6 and distinct cleavage parallel to (001). The calculated density is 4.791 g/cm3. The IR spectrum does not contain absorption bands that correspond to H2O and OH groups. Perrierite-(La) is biaxial (-), α = 1.94(1), β = 2.020(15), γ = 2.040(15), 2 V meas = 50(10)°, 2 V calc = 51°. The chemical composition (electron microprobe, average of seven point analyses, the Fe2+/Fe3+ ratio determined from the X-ray structural data, wt %) is as follows: 3.26 CaO, 22.92 La2O3, 19.64 Ce2O3, 0.83 Pr2O2, 2.09 Nd2O3, 0.25 MgO, 2.25 MnO, 3.16 FeO, 5.28 Fe2O3, 2.59 Al2O3, 16.13 TiO2, 0.75 Nb2O5, and 20.06 SiO2, total is 99.21. The empirical formula is (La1.70Ce1.45Nd0.15Pr0.06Ca0.70)Σ4.06(Fe{0.53/2+}Mn0.38Mg0.08)Σ0.99(Ti2.44Fe{0.80/3+}Al0.62Nb0.07)Σ3.93Si4.04O22. The simplified formula is (La,Ce,Ca)4(Fe2+,Mn)(Ti,Fe3+,Al)4(Si2O7)2O8. The crystal structure was determined by a single crystal. Perrierite-(La) is monoclinic, space group P21/ a, and the unit-cell dimensions are as follows: a =13.668(1), b = 5.6601(6), c = 11.743(1) Å, β = 113.64(1)°; V = 832.2(2) Å3, Z = 2. The strong reflections in the X-ray powder diffraction pattern are [ d, Å ( I, %) ( hkl)]: 5.19 (40) (110), 3.53 (40) (overline 3 11), 2.96 (100) (overline 3 13, 311), 2.80 (50) (020), 2.14 (50) (overline 4 22, overline 3 15, 313), 1.947 (50) (024, 223), 1.657 (40) (overline 4 07, overline 4 33, 331). The holotype specimen of perrierite-(La) is

  2. Reintroduction of highly pathogenic avian influenza A/H5N8 virus of clade 2.3.4.4. in Russia.

    PubMed

    Marchenko, Vasiliy Y; Susloparov, Ivan M; Komissarov, Andrey B; Fadeev, Artem; Goncharova, Nataliya I; Shipovalov, Andrey V; Svyatchenko, Svetlana V; Durymanov, Alexander G; Ilyicheva, Tatyana N; Salchak, Lyudmila K; Svintitskaya, Elena P; Mikheev, Valeriy N; Ryzhikov, Alexander B

    2017-05-01

    In the spring of 2016, a loss of wild birds was observed during the monitoring of avian influenza virus activity in the Republic of Tyva. That outbreak was caused by influenza H5N8 virus of clade 2.3.4.4. In the fall, viruses of H5N8 clade 2.3.4.4 were propagated in European countries. This paper presents some results of analysis of the virus strains isolated during the spring and fall seasons in 2016 in the Russian Federation. The investigated strains were highly pathogenic for mice, and some of their antigenic and genetic features differed from those of an H5N8 strain that circulated in 2014 in Russia.

  3. 21 CFR 73.3122 - 4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false 4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one. 73.3122 Section 73.3122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical...

  4. 21 CFR 73.3122 - 4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 false 4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one. 73.3122 Section 73.3122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical...

  5. 21 CFR 73.3122 - 4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false 4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one. 73.3122 Section 73.3122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical...

  6. 21 CFR 73.3122 - 4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false 4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one. 73.3122 Section 73.3122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical...

  7. 21 CFR 73.3122 - 4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false 4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one. 73.3122 Section 73.3122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical...

  8. Crystal structure of (NH4)2[Fe(II) 5(HPO3)6], a new open-framework phosphite.

    PubMed

    Berrocal, Teresa; Mesa, Jose Luis; Larrea, Edurne; Arrieta, Juan Manuel

    2014-11-01

    Di-ammonium hexa-phosphito-penta-ferrate(II), (NH4)2[Fe5(HPO3)6], was synthesized under mild hydro-thermal conditions and autogeneous pressure, yielding twinned crystals. The crystal structure exhibits an [Fe(II) 5(HPO3)6](2-) open framework with NH4 (+) groups as counter-cations. The anionic skeleton is based on (001) sheets of [FeO6] octa-hedra (one with point-group symmetry 3.. and one with .2.) linked along [001] through [HPO3](2-) oxoanions. Each sheet is constructed from 12-membered rings of edge-sharing [FeO6] octa-hedra, giving rise to channels with a radius of ca 3.1 Å in which the disordered NH4 (+) cations are located. The IR spectrum shows vibrational bands typical for phosphite and ammonium groups.

  9. A (S)-(+)-decursin derivative, (S)-(+)-3-(3,4-dihydroxy-phenyl)-acrylic acid 2,2-dimethyl-8-oxo-3,4-dihydro-2H,8H-pyrano[3,2-g]-chromen-3-yl-ester, attenuates the development of atopic dermatitis-like lesions in NC/Nga mice.

    PubMed

    Kim, In Sik; Kim, Dong-Hee; Yun, Chi-Young; Lee, Ji-Sook

    2013-03-01

    (S)-(+)-decursin is a biological coumarin compound isolated from Angelica gigas Nakai. (S)-(+)-decursin and its analogue have a variety of pharmacological activities. In the present study, the anti-inflammatory effect of a (S)-(+)-decursin derivative, (S)-(+)-3-(3,4-dihydroxy-phenyl)-acrylic acid 2,2-dimethyl-8-oxo-3,4-dihydro-2H,8H-pyrano [3,2-g]-chromen-3-yl-ester (Compound 6, C6), on in vitro and in vivo atopic dermatitis was investigated. C6 suppressed the secretion of IL-6, IL-8, and monocyte chemotactic protein-1 increase by the house dust mite extract in the eosinophilic leukemia cell line and THP-1 cells. C6 inhibited the production of TARC, IL-6, and IL-8 increase by IFN-γ and TNF-α in the human keratinocyte cell line. In the in vivo experiment, NC/Nga mice were sensitized to 2,4-dinitrochlorobenzene, and then C6 or dexamethasone (Dex) were orally and dorsally administered for three weeks. C6 treatment reduced the skin severity score compared with that of the control group. C6 inhibited the thickening of the epidermis and inflammatory cell infiltration into the dermis by evaluating the histological examination. The serum immunoglobulin E (IgE) level decreased in the C6-treated group compared with that of the control group. The inhibitory effect of C6 on IgE concentration was similar to that of Dex. The levels of IL-4, IL-5, IL-13, and eotaxin increased after treatment with concanavalin A in mouse splenocytes. The cytokine levels of the C6-treated group were lower than those of the control group. Taken together, C6 may attenuate atopic dermatitis-like lesions through its anti-inflammatory effect, such as inhibition of IgE and inflammatory cytokines, and it may be valuable as a therapeutic drug for the treatment of atopic dermatitis.

  10. Surface treatment to form a dispersed Y2O3 layer on Zircaloy-4 tubes

    NASA Astrophysics Data System (ADS)

    Jung, Yang-Il; Kim, Hyun-Gil; Guim, Hwan-Uk; Lim, Yoon-Soo; Park, Jung-Hwan; Park, Dong-Jun; Yang, Jae-Ho

    2018-01-01

    Zircaloy-4 is a traditional zirconium-based alloy developed for application in nuclear fuel cladding tubes. The surfaces of Zircaloy-4 tubes were treated using a laser beam to increase their mechanical strength. Laser beam scanning of a tube coated with yttrium oxide (Y2O3) resulted in the formation of a dispersed oxide layer in the tube's surface region. Y2O3 particles penetrated the Zircaloy-4 during the laser treatment and were distributed uniformly in the surface region. The thickness of the dispersed oxide layer varied from 50 to 140 μm depending on the laser beam trajectory. The laser treatment also modified the texture of the tube. The preferred basal orientation along the normal to the tube surface disappeared, and a random structure appeared after laser processing. The most obvious result was an increase in the mechanical strength. The tensile strength of Zircaloy-4 increased by 10-20% with the formation of the dispersed oxide layer. The compressive yield stress also increased, by more than 15%. Brittle fracture was observed in the surface-treated samples during tensile and compressive deformation at room temperature; however, the fracture behavior was changed in ductile at elevated temperatures.

  11. Tm:GdVO4 microchip laser Q-switched by a Sb2Te3 topological insulator

    NASA Astrophysics Data System (ADS)

    Loiko, Pavel; Bogusławski, Jakub; Serres, Josep Maria; Kifle, Esrom; Kowalczyk, Maciej; Mateos, Xavier; Sotor, Jarosław; Zybała, Rafał; Mars, Krzysztof; Mikuła, Andrzej; Aguiló, Magdalena; Díaz, Francesc; Griebner, Uwe; Petrov, Valentin

    2018-02-01

    We report on the first application of a topological insulator based on antimony telluride (Sb2Te3) as a saturable absorber (SA) in a bulk microchip laser. The transmission-type SA consisted of a thin film of Sb2Te3 (thickness: 3 nm) deposited on a glass substrate by pulsed magnetron sputtering. The saturable absorption of the Sb2Te3 film was confirmed for ns-long pulses. The microchip laser was based on a Tm:GdVO4 crystal diode-pumped at 802 nm. In the continuous-wave regime, this laser generated 3.54 W at 1905-1921 nm with a slope efficiency η of 37%. The Q-switched laser generated a maximum average output power of 0.70 W at 1913 nm. The pulse energy and duration were 3.5 μJ and 223 ns, respectively, at a repetition rate of 200 kHz. The Sb2Te3 SAs are promising for passively Q-switched waveguide lasers at 2 μm.

  12. Method for preparation of 7-hydroxy-1,2,3,4-tetrahydroquinoline from 1,2,3,4-tetrahydroquinoline

    DOEpatents

    Field, G.; Hammond, P.R.

    1994-02-01

    Methods for the efficient preparation of 7-hydroxy-1,2,3,4-tetrahydroquinoline include a first method in which the acylation of m-aminophenol obtains a lactam which is reduced to give the desired quinoline and a second method in which tetrahydroquinoline is nitrated and hydrogenated and then hydrolyzed to obtain the desire quinoline. 7-hydroxy-1,2,3,4-tetrahydroquinoline is used in the efficient synthesis of four lasing dyes of the rhodamine class.

  13. Method for preparation of 7-hydroxy-1,2,3,4-tetrahydroquinoline from 1,2,3,4-tetrahydroquinoline

    DOEpatents

    Field, George; Hammond, Peter R.

    1994-01-01

    Methods for the efficient preparation of 7-hydroxy-1,2,3,4-tetrahydroquinoline include a first method in which the acylation of m-aminophenol obtains a lactam which is reduced to give the desired quinoline and a second method in which tetrahydroquinoline is nitrated and hydrogenated and then hydrolyzed to obtain the desire quinoline. 7-hydroxy-1,2,3,4-tetrahydroquinoline is used in the efficient synthesis of four lasing dyes of the rhodamine class.

  14. 40 CFR 721.9662 - Thieno[3,4-b]-1,4-dioxin, 2,3-dihydro- (9CI).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Thieno[3,4-b]-1,4-dioxin, 2,3-dihydro... Specific Chemical Substances § 721.9662 Thieno[3,4-b]-1,4-dioxin, 2,3-dihydro- (9CI). (a) Chemical...-b]-1,4-dioxin, 2,3-dihydro- (9CI) (PMN P-95-1825; CAS No. 126213-50-1) is subject to reporting under...

  15. 2,3,4,6-Tetrachlorophenol

    Integrated Risk Information System (IRIS)

    2,3,4,6 - Tetrachlorophenol ; CASRN 58 - 90 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncar

  16. Modulation of human cytochrome P450 3A4 (CYP3A4) and P-glycoprotein (P-gp) in Caco-2 cell monolayers by selected commercial-source milk thistle and goldenseal products.

    PubMed

    Budzinski, Jason W; Trudeau, Vance L; Drouin, Cathy E; Panahi, Mitra; Arnason, J Thor; Foster, Brian C

    2007-09-01

    In this study, we used an in vitro Caco-2 cell monolayer model to evaluate aqueous extracts of commercial-source goldenseal (Hydrastis canadensis) and milk thistle (Silybum marianum) capsule formulations, their marker phytochemicals (berberine and silibinin, respectively), as well as dillapiol, vinblastine, and the HIV protease inhibitor saquinavir for their ability to modulate CYP3A4 and ABCB1 expression after short-term exposure (48 h). Both upregulation and downregulation of CYP3A4 expression was observed with extracts of varying concentrations of the two natural health products (NHPs). CYP3A4 was highly responsive in our system, showing a strong dose-dependent modulation by the CYP3A4 inhibitor dillapiol (upregulation) and the milk thistle flavonolignan silibinin (downregulation). ABCB1 was largely unresponsive in this cellular model and appears to be of little value as a biomarker under our experimental conditions. Therefore, the modulation of CYP3A4 gene expression can serve as an important marker for the in vitro assessment of NHP-drug interactions.

  17. Densities and apparent molar volumes of atmospherically important electrolyte solutions. 2. The systems H(+)-HSO4(-)-SO4(2-)-H2O from 0 to 3 mol kg(-1) as a function of temperature and H(+)-NH4(+)-HSO4(-)-SO4)2-)-H2O from 0 to 6 mol kg(-1) at 25 °C using a Pitzer ion interaction model, and NH4HSO4-H2O and (NH4)3H(SO4)2-H2O over the entire concentration range.

    PubMed

    Clegg, S L; Wexler, A S

    2011-04-21

    A Pitzer ion interaction model has been applied to the systems H(2)SO(4)-H(2)O (0-3 mol kg(-1), 0-55 °C) and H(2)SO(4)-(NH(4))(2)SO(4)-H(2)O (0-6 mol kg(-1), 25 °C) for the calculation of apparent molar volume and density. The dissociation reaction HSO(4)(-)((aq)) ↔ H(+)((aq)) + SO(4)(2-)((aq)) is treated explicitly. Apparent molar volumes of the SO(4)(2-) ion at infinite dilution were obtained from part 1 of this work, (1) and the value for the bisulfate ion was determined in this study from 0 to 55 °C. In dilute solutions of both systems, the change in the degree of dissociation of the HSO(4)(-) ion with concentration results in much larger variations of the apparent molar volumes of the solutes than for conventional strong (fully dissociated) electrolytes. Densities and apparent molar volumes are tabulated. Apparent molar volumes calculated using the model are combined with other data for the solutes NH(4)HSO(4) and (NH(4))(3)H(SO(4))(2) at 25 °C to obtain apparent molar volumes and densities over the entire concentration range (including solutions supersaturated with respect to the salts).

  18. Synthesis of carbon-11 labeled 1-(3,4-dimethoxybenzyl)-2,2-dimethyl-1,2,3,4-tetrahydroisoquinolinium derivatives as new potential PET SKCa channel imaging agents.

    PubMed

    Gao, Mingzhang; Wang, Min; Zheng, Qi-Huang

    2008-02-01

    Small conductance Ca2+-activated K+ (SKCa) channels play an important role in many functions such as neuronal communication and behavioral plasticity, secretion, and cell proliferation. SKCa channel modulation is associated with various brain, heart, and cancer diseases. N-methyl-laudanosine and its structurally related derivatives, substituted 1-(3,4-dimethoxybenzyl)-2,2-dimethyl-1,2,3,4-tetrahydroisoquinoliniums, are reversible and selective SKCa channel blockers. Carbon-11 labeled N-methyl-laudanosine and its tetrahydroisoquinolinium derivatives may serve as new probes for positron emission tomography (PET) to image SKCa channels in the brain, heart, and cancer. The key intermediates, substituted isoquinolines (3a-c), were synthesized using a modification of the Pomeranz-Fritsch procedure. The precursors, substituted 1-(3,4-dimethoxybenzyl)-2-methyl-1,2,3,4-tetrahydroisoquinolines (8a-c), and their corresponding reference standards, substituted 1-(3,4-dimethoxybenzyl)-2,2-dimethyl-1,2,3,4-tetrahydroisoquinoliniums (9a-c), were synthesized from compounds 3a-c with 3,4-dimethoxybenzyl chloride (2) in multiple steps with moderate to excellent chemical yields. The precursor 6,7-dimethoxy-1-(3,4-dimethoxybenzyl)-2-methyl-1,2,3,4-tetrahydroisoquinoline (10) was commercially available, and the methylation of compound 10 with methyl iodide provided N-methyl-laudanosine (11). The target quaternary ammonium tracers, carbon-11 labeled 1-(3,4-dimethoxybenzyl)-2,2-dimethyl-1,2,3,4-tetrahydroisoquinoliniums ([11C]9a-c and [11C]11), were prepared by N-[11C]methylation of the tertiary amine precursors (8a-c and 10) with [11C]methyl triflate and isolated by a simplified solid-phase extraction (SPE) purification using a SiO2 or cation-exchange CM Sep-Pak cartridge in 40-65% radiochemical yields.

  19. A pilot study of pNGVL4a-CRT/E7(detox) for the treatment of patients with HPV16+ cervical intraepithelial neoplasia 2/3 (CIN2/3).

    PubMed

    Alvarez, Ronald D; Huh, Warner K; Bae, Sejong; Lamb, Lawrence S; Conner, Michael G; Boyer, Jean; Wang, Chenguang; Hung, Chien-Fu; Sauter, Elizabeth; Paradis, Mihaela; Adams, Emily A; Hester, Shirley; Jackson, Bradford E; Wu, T C; Trimble, Cornelia L

    2016-02-01

    The purpose of this study was to evaluate the safety, efficacy, and immunogenicity of a plasmid vaccine, pNGVL4a-CRT-E7(detox), administered either intradermally, intramuscularly, or directly into the cervical lesion, in patients with HPV16-associated CIN2/3. Eligible patients with HPV16(+) CIN2/3 were enrolled in treatment cohorts evaluating pNGVL4a-CRT-E7(detox), administered by either particle-mediated epidermal delivery (PMED), intramuscular injection (IM), or cervical intralesional injection, at study weeks 0, 4, and 8. Patients were monitored for local injection site and systemic toxicity. A standard therapeutic resection was performed at week 15. The primary endpoints were safety and tolerability. Secondary endpoints included histologic regression and change in cervical HPV viral load. Exploratory endpoints included immune responses in the blood and in the target tissue. Thirty-two patients with HPV16(+) CIN2/3 were enrolled onto the treatment phase of the study, and were vaccinated. Twenty-two of 32 patients (69%) experienced vaccine-specific related adverse events. The most frequent vaccine-related events were constitutional and local injection site in nature, and were grade 1 or less in severity. Histologic regression to CIN 1 or less occurred in 8 of 27 (30%) patients who received all vaccinations and underwent LEEP. In subject-matched comparisons, intraepithelial CD8+ T cell infiltrates increased after vaccination in subjects in the intralesional administration cohort. pNGVL4a-CRT-E7(detox) was well-tolerated, elicited the most robust immune response when administered intralesionally, and demonstrated preliminary evidence of potential clinical efficacy. Copyright © 2015 Elsevier Inc. All rights reserved.

  20. A Pilot Study of pNGVL4a-CRT/E7(detox) for the Treatment of Patients with HPV16+ Cervical Intraepithelial Neoplasia 2/3 (CIN2/3)

    PubMed Central

    Alvarez, Ronald D.; Huh, Warner K.; Bae, Sejong; Lamb, Lawrence S.; Conner, Michael G.; Boyer, Jean; Wang, Chenguang; Hung, Chien-Fu; Sauter, Elizabeth; Paradis, Mihaela; Adams, Emily A.; Hester, Shirley; Jackson, Bradford E.; Wu, T.C.; Trimble, Cornelia

    2015-01-01

    Objective The purpose of this study was to evaluate the safety, efficacy, and immunogenicity of a plasmid vaccine, pNGVL4a-CRT-E7(detox), administered either intradermally, intramuscularly, or directly into the cervical lesion, in patients with HPV16-associated CIN2/3. Methods Eligible patients with HPV16+ CIN2/3 were enrolled in treatment cohorts evaluating pNGVL4a-CRT-E7(detox), administered by either particle-mediated epidermal delivery (PMED), intramuscular injection (IM), or cervical intralesional injection, at study weeks 0, 4, and 8. Patients were monitored for local injection site and systemic toxicity. A standard therapeutic resection was performed at week 15. The primary endpoints were safety and tolerability. Secondary endpoints included histologic regression and change in cervical HPV viral load. Exploratory endpoints included immune responses in the blood and in the target tissue. Results Thirty-two patients with HPV16+ CIN2/3 were enrolled onto the treatment phase of the study, and were vaccinated. Twenty-two of 32 patients (69%) experienced vaccine-specific related adverse events. The most frequent vaccine-related events were constitutional and local injection site in nature, and were grade 1 or less in severity. Histologic regression to CIN 1 or less occurred in 8 of 27 (30%) patients who received all vaccinations and underwent LEEP. In subject-matched comparisons, intraepithelial CD8+ T cell infiltrates increased after vaccination in subjects in the intralesional administration cohort. Conclusion pNGVL4a-CRT-E7(detox) was well-tolerated, elicited the most robust immune response when administered intralesionally, and demonstrated preliminary evidence of potential clinical efficacy. PMID:26616223

  1. A 3D chiral metal-organic framework based on left-handed helices containing 3-amino-1 H-1,2,4-triazole ligand

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

    Liu, Bing, E-mail: bliu_1203@163.com; Yang, Tian-Yi; Feng, Hui-Jun

    2015-10-15

    A chiral metal-organic framework, [Cu(atr)(OH)]·0.5H{sub 2}O·0.5en (1) (Hatr=3-amino-1 H-1,2,4-triazole, en=ethylenediamine), was constructed via diffusion reaction of the achiral Hatr ligand and CuSO{sub 4} as starting materials. Compound 1 crystallizes in the chiral space group P3{sub 2}21 and features a porous metal-organic framework with 44.1% solvent-accessible volume fabricated by left-handed helices with a pitch height of l{sub p}=10.442 Å. Six helices gather around in a cycle forming a large honeycomb channel with a 6.58 Å inner diameter. Cu(II) center and atr{sup ‒} ligand regarded as 3-connected nodes, compound 1 can be simplified to a 3-c uninodal (4.12{sup 2}) (qtz-h) topological network.more » A gradual decreasing in the magnetic moment depending on temperature decreasing indicates an antiferromagnetic interaction in 1. The powder XRD confirms the bulk sample is a single crystal pure phase, and the thermogravimetric analysis shows the thermal stability of 1 is up to ca. 240 °C. - Highlights: • The present 3D chiral MOF is built from achiral Hatr ligand. • Six left-handed helices gather into a honeycomb channel in chiral sp P3{sub 2}21. • Compound 1 shows a 3-c uninodal (4.12{sup 2}) or qtz-h topological network. • Compound 1 indicates an antiferromagnetic interaction.« less

  2. Chemical and Electrochemical Asymmetric Dihydroxylation of Olefins in I(2)-K(2)CO(3)-K(2)OsO(2)(OH)(4) and I(2)-K(3)PO(4)/K(2)HPO(4)-K(2)OsO(2)(OH)(4) Systems with Sharpless' Ligand.

    PubMed

    Torii, Sigeru; Liu, Ping; Bhuvaneswari, Narayanaswamy; Amatore, Christian; Jutand, Anny

    1996-05-03

    Iodine-assisted chemical and electrochemical asymmetric dihydroxylation of various olefins in I(2)-K(2)CO(3)-K(2)OsO(2)(OH)(4) and I(2)-K(3)PO(4)/K(2)HPO(4)-K(2)OsO(2)(OH)(4) systems with Sharpless' ligand provided the optically active glycols in excellent isolated yields and high enantiomeric excesses. Iodine (I(2)) was used stoichiometrically for the chemical dihydroxylation, and good results were obtained with nonconjugated olefins in contrast to the case of potassium ferricyanide as a co-oxidant. The potentiality of I(2) as a co-oxidant under stoichiometric conditions has been proven to be effective as an oxidizing mediator in electrolysis systems. Iodine-assisted asymmetric electro-dihydroxylation of olefins in either a t-BuOH/H(2)O(1/1)-K(2)CO(3)/(DHQD)(2)PHAL-(Pt) or t-BuOH/H(2)O(1/1)-K(3)PO(4)/K(2)HPO(4)/(DHQD)(2)PHAL-(Pt) system in the presence of potassium osmate in an undivided cell was investigated in detail. Irrespective of the substitution pattern, all the olefins afforded the diols in high yields and excellent enantiomeric excesses. A plausible mechanism is discussed on the basis of cyclic voltammograms as well as experimental observations.

  3. Highly selective SiO2 etching over Si3N4 using a cyclic process with BCl3 and fluorocarbon gas chemistries

    NASA Astrophysics Data System (ADS)

    Matsui, Miyako; Kuwahara, Kenichi

    2018-06-01

    A cyclic process for highly selective SiO2 etching with atomic-scale precision over Si3N4 was developed by using BCl3 and fluorocarbon gas chemistries. This process consists of two alternately performed steps: a deposition step using BCl3 mixed-gas plasma and an etching step using CF4/Ar mixed-gas plasma. The mechanism of the cyclic process was investigated by analyzing the surface chemistry at each step. BCl x layers formed on both SiO2 and Si3N4 surfaces in the deposition step. Early in the etching step, the deposited BCl x layers reacted with CF x radicals by forming CCl x and BF x . Then, fluorocarbon films were deposited on both surfaces in the etching step. We found that the BCl x layers formed in the deposition step enhanced the formation of the fluorocarbon films in the CF4 plasma etching step. In addition, because F radicals that radiated from the CF4 plasma reacted with B atoms while passing through the BCl x layers, the BCl x layers protected the Si3N4 surface from F-radical etching. The deposited layers, which contained the BCl x , CCl x , and CF x components, became thinner on SiO2 than on Si3N4, which promoted the ion-assisted etching of SiO2. This is because the BCl x component had a high reactivity with SiO2, and the CF x component was consumed by the etching reaction with SiO2.

  4. Polar materials with isolated V 4+ S = 1/2 Triangles: NaSr 2V 3O 3(Ge 4O 13)Cl and KSr 2V 3O 3(Ge 4O 13)Cl

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

    Sanjeewa, Liurukara D.; McGuire, Michael A.; McMillen, Colin D.

    Here, crystals of ASr 2V 3O 3(Ge 4O 13)Cl, A = Na, K, were synthesized from high-temperature hydrothermal brines, and their structure and magnetic properties were investigated. These materials present a unique combination of a salt inclusion lattice, a polar crystal structure, and isolated V 4+ ( S = 1/2) trimer magnetic clusters. The structures consist of a trimeric V 3O 13 unit based on V 4+ ( S = 1/2), having rigorous 3-fold symmetry with a short V–V separation of 3.325(3) Å. The trinuclear V 4+ units are formed by three edge shared VO 6 octahedra sharing a centralmore » μ3-oxygen atom, which also imparts a polar sense on the structure. The V 3O 13 units are isolated from one another by tetranuclear Ge 4O 13 units, which are similarly arranged in a polar fashion, providing a unique opportunity to study the magnetic behavior of this triangular d 1 system as a discrete unit. Magnetization measurements indicate spin-1/2 per V atom at high temperature, and spin-1/2 per V 3 trimer at low temperature, where two V moments in each triangle are antiferromagnetically aligned and the third remains paramagnetic. The crossover between these two behaviors occurs between 20 and 100 K and is well-described by a model incorporating strong antiferromagnetic intra-trimer interactions and weak but nonzero inter-trimer interactions. More broadly, the study highlights the ability to obtain new materials with interesting structure–property relationships via chemistry involving unconventional solvents and reaction conditions.« less

  5. Polar materials with isolated V 4+ S = 1/2 Triangles: NaSr 2V 3O 3(Ge 4O 13)Cl and KSr 2V 3O 3(Ge 4O 13)Cl

    DOE PAGES

    Sanjeewa, Liurukara D.; McGuire, Michael A.; McMillen, Colin D.; ...

    2017-01-03

    Here, crystals of ASr 2V 3O 3(Ge 4O 13)Cl, A = Na, K, were synthesized from high-temperature hydrothermal brines, and their structure and magnetic properties were investigated. These materials present a unique combination of a salt inclusion lattice, a polar crystal structure, and isolated V 4+ ( S = 1/2) trimer magnetic clusters. The structures consist of a trimeric V 3O 13 unit based on V 4+ ( S = 1/2), having rigorous 3-fold symmetry with a short V–V separation of 3.325(3) Å. The trinuclear V 4+ units are formed by three edge shared VO 6 octahedra sharing a centralmore » μ3-oxygen atom, which also imparts a polar sense on the structure. The V 3O 13 units are isolated from one another by tetranuclear Ge 4O 13 units, which are similarly arranged in a polar fashion, providing a unique opportunity to study the magnetic behavior of this triangular d 1 system as a discrete unit. Magnetization measurements indicate spin-1/2 per V atom at high temperature, and spin-1/2 per V 3 trimer at low temperature, where two V moments in each triangle are antiferromagnetically aligned and the third remains paramagnetic. The crossover between these two behaviors occurs between 20 and 100 K and is well-described by a model incorporating strong antiferromagnetic intra-trimer interactions and weak but nonzero inter-trimer interactions. More broadly, the study highlights the ability to obtain new materials with interesting structure–property relationships via chemistry involving unconventional solvents and reaction conditions.« less

  6. Stereostructure of a norbornane diexo-condensed 1,3-oxazine[2,3-a]isoindolone An X-ray study

    NASA Astrophysics Data System (ADS)

    Argay, Gy.; Kálmán, A.; Stájer, G.; Bernáth, G.

    1994-12-01

    The structure of 3,6-methano-12b-p-tolyl-2a,3,4,5,6,6a,7,12b-octahydro-2H-3,1-benzoxazino[2,3-a]isoindol-8-one (C23H23NO2, Mr = 345.42), prepared from 2-p-toluoylbenzoic acid and diexo-3-hydroxymethylbicyclo[2.2.1]heptyl-2-amine, has been established by X-ray crystallography from diffractometer data: it crystallizes in the triclinic space group Poverline1 with a = 8.186(2) Å, b = 8.683(2) Å, c = 13.324(5) Å, α = 83.46(4)°, β = 75.48(6)°, γ = 77.60(4)°, V = 893.6(4) Å3, Z = 2, Dc = 1.284 g cm-3 and μ(Cu Kα) = 0.641 mm-1. The structure was solved by direct methods and refined to R = 0.061 for 3685 observed reflections. The molecule exhibits diexo-annelation between the 1,3-oxazine ring and the norbornane moiety. The p-tolyl group and norbonane annelation hydrogens are trans and the 1,3-oxazine ring is fused to an almost planar γ-lactam ring. Consequently, the six-membered hetero ring assumes an irregular conformation among the canonical forms 1S6, 1T3 and B3,6.

  7. Propellant Containing 3, 6bis(1h-1,2,3,4-Tetrazol-5-Ylamino)-1,2,4,5- Tetrazine Or Salt Thereof

    DOEpatents

    Hiskey, Michael A.; Chavez, David E.; Naud, Darren

    2003-12-02

    The compound 3,6-bis(1H-1,2,3,4-tetrazol-5-ylamino)-1,2,4,5-tetrazine and its salts are provided together with a propellant composition including an oxidizer, a binder and 3,6-bis(1H-1,2,3,4-tetrazol-5-ylamino)-1,2,4,5-tetrazine or its salts.

  8. Comprehensive physicochemical studies of a new hybrid material: 2-amino-4-methyl-3-nitropyridinium hydrogen oxalate.

    PubMed

    Bryndal, I; Kucharska, E; Wandas, M; Lorenc, J; Hermanowicz, K; Mączka, M; Lis, T; Marchewka, M; Hanuza, J

    2014-01-03

    A new organic-organic salt, 2-amino-4-methyl-3-nitropyridinium hydrogen oxalate (AMNPO), and its deuterium analogue have been synthesized and characterized by means of FT-IR, FT-Raman, DSC and single crystal X-ray studies. The DSC measurements and temperature dependence of the IR and Raman spectra in the range 4-295 K show that it undergoes a reversible phase transition at ~240 K. At room temperature it crystallizes in noncentrosymmetric space group P21. The unit-cell is built of the 2-amino-4-methyl-3-nitropyridinium cations and oxalate monoanions which are connected via the N-H···O and O-H···O hydrogen bonds. The geometrical and hydrogen bond parameters are similar for non-deuterated (at 120 and 293 K) and deuterated compounds (at 90K). The phase transition is probably a consequence of order-disorder transition inside of hydrogen network. The 6-311G(2d,2p) basis set with B3LYP functional have been used to discuss the structure and vibrational spectra of the studied compound. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. Discovery of sodium R-(+)-4-{2-[5-(2-fluoro-3-methoxyphenyl)-3-(2-fluoro-6-[trifluoromethyl]benzyl)-4-methyl-2,6-dioxo-3,6-dihydro-2H-pyrimidin-1-yl]-1-phenylethylamino}butyrate (elagolix), a potent and orally available nonpeptide antagonist of the human gonadotropin-releasing hormone receptor.

    PubMed

    Chen, Chen; Wu, Dongpei; Guo, Zhiqiang; Xie, Qiu; Reinhart, Greg J; Madan, Ajay; Wen, Jenny; Chen, Takung; Huang, Charles Q; Chen, Mi; Chen, Yongsheng; Tucci, Fabio C; Rowbottom, Martin; Pontillo, Joseph; Zhu, Yun-Fei; Wade, Warren; Saunders, John; Bozigian, Haig; Struthers, R Scott

    2008-12-11

    The discovery of novel uracil phenylethylamines bearing a butyric acid as potent human gonadotropin-releasing hormone receptor (hGnRH-R) antagonists is described. A major focus of this optimization was to improve the CYP3A4 inhibition liability of these uracils while maintaining their GnRH-R potency. R-4-{2-[5-(2-fluoro-3-methoxyphenyl)-3-(2-fluoro-6-[trifluoromethyl]benzyl)-4-methyl-2,6-dioxo-3,6-dihydro-2H-pyrimidin-1-yl]-1-phenylethylamino}butyric acid sodium salt, 10b (elagolix), was identified as a potent and selective hGnRH-R antagonist. Oral administration of 10b suppressed luteinizing hormone in castrated macaques. These efforts led to the identification of 10b as a clinical compound for the treatment of endometriosis.

  10. A novel COL4A3 mutation causes autosomal-recessive Alport syndrome in a large Turkish family.

    PubMed

    Uzak, Asli Subasioglu; Tokgoz, Bulent; Dundar, Munis; Tekin, Mustafa

    2013-03-01

    Alport syndrome (AS) is a genetically heterogeneous disorder that is characterized by hematuria, progressive renal failure typically resulting in end-stage renal disease, sensorineural hearing loss, and variable ocular abnormalities. Only 15% of cases with AS are autosomal recessive and are caused by mutations in the COL4A3 or COL4A4 genes, encoding type IV collagen. Clinical data in a large consanguineous family with four affected members were reviewed, and genomic DNA was extracted. For mapping, 15 microsatellite markers flanking COL4A3, COL4A4, and COL4A5 in 16 family members were typed. For mutation screening, all coding exons of COL4A3 were polymerase chain reaction- amplified and Sanger-sequenced from genomic DNA. The disease locus was mapped to chromosome 2q36.3, where COL4A3 and COL4A4 reside. Sanger sequencing revealed a novel mis-sense mutation (c.2T>C; p.M1T) in exon 1 of COL4A3. The identified nucleotide change was not found in 100 healthy ethnicity-matched controls via Sanger sequencing. We present a large consanguineous Turkish family with AS that was found to have a COL4A3 mutation as the cause of the disease. Although the relationship between the various genotypes and phenotypes in AS has not been fully elucidated, detailed clinical and molecular analyses are helpful for providing data to be used in genetic counseling. It is important to identify new mutations to clarify their clinical importance, to assess the prognosis of the disease, and to avoid renal biopsy for final diagnosis.

  11. 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].

  12. Decomposition of L a2 -xS rxCu O4 into several L a2O3 phases at elevated temperatures in ultrahigh vacuum inside a transmission electron microscope

    NASA Astrophysics Data System (ADS)

    Jeong, Jong Seok; Wu, Wangzhou; Topsakal, Mehmet; Yu, Guichuan; Sasagawa, Takao; Greven, Martin; Mkhoyan, K. Andre

    2018-05-01

    We report the decomposition of L a2 -xS rxCu O4 into L a2O3 and Cu nanoparticles in ultrahigh vacuum, observed by in situ heating experiments in a transmission electron microscope. The analysis of electron diffraction data reveals that the phase decomposition process starts at about 150 °C and is considerably expedited in the temperature range of 350 °C-450 °C. Two major resultant solid phases are identified as metallic Cu and L a2O3 by electron diffraction, simulation, and electron energy-loss spectroscopy (EELS) analyses. With the aid of calculations, L a2O3 phases are further identified to be derivatives of a fluorite structure—fluorite, pyrochlore, and (distorted) bixbyite—characterized by different oxygen-vacancy order. Additionally, the bulk plasmon energy and the fine structures of the O K and La M4 ,5 EELS edges are reported for these structures, along with simulated O K x-ray absorption near-edge structure. The resultant Cu nanoparticles and L a2O3 phases remain unchanged after cooling to room temperature.

  13. CYP1A2 and NAT2 phenotyping and 3-aminobiphenyl and 4-aminobiphenyl hemoglobin adduct levels in smokers and non-smokers

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

    Sarkar, Mohamadi; Department of Pharmaceutics, Virginia Commonwealth University, Richmond, VA 23298; Stabbert, Regina

    Some aromatic amines are considered to be putative bladder carcinogens. Hemoglobin (Hb) adducts of 3-aminobiphenyl (3-ABP) and 4-aminobiphenyl (4-ABP) have been used as biomarkers of exposure to aromatic amines from cigarette smoke. One of the goals of this study was to determine intra- and inter-individual variability in 3-ABP and 4-ABP Hb adducts and to explore the predictability of ABP Hb adduct levels based on caffeine phenotyping. The study was conducted in adult smokers (S, n = 65) and non-smokers (NS, n 65). The subjects were phenotyped for CYP1A2 and NAT2 using urinary caffeine metabolites. Blood samples were collected twice withinmore » 6 weeks and adducts measured by GC/MS. The levels of 4-ABP Hb adducts were significantly (p < 0.0001) greater in S (34.5 {+-} 21.06 pg/g Hb) compared to NS (6.3 {+-} 3.02 pg/g Hb). The levels of 3-ABP Hb adducts were below the limit of quantification (BLOQ) in most (82%) of the NS and about 10-fold lower in S (3.6 {+-} 3.29 pg/g Hb) compared to 4-ABP Hb adducts. No differences were observed in the adduct levels between weeks 1 and 6 in the smokers, suggesting that a single sample would be adequate to monitor cigarette smoke exposure. The regression model developed with CYP1A2, NAT2 phenotype and number of cigarettes smoked (NCIG) accounted for 47% of the variability in 3-ABP adducts, whereas 32% variability in 4-ABP adducts was accounted by CYP1A2 and NCIG. The ratio of 4-ABP Hb adducts in adult S:NS was {approx} 5:1, whereas 3-ABP Hb adducts levels were BLOQ in some S, exhibited large interindividual variability ({approx} 91% compared to 57% for 4-ABP Hb) and poor dose response relationship. Therefore, 4-ABP Hb adduct levels may be a more useful biomarker of aminobiphenyl exposure from cigarette smoke.« less

  14. Synthesis and antibacterial activities of new 1 beta-methylcarbapenems having a 1,3-diazabicyclo[3.3.0]octan-2,4-dione moiety.

    PubMed

    Nam, K H; Oh, C H; Ham, Y W; Lee, K S; Cho, J H

    1997-08-01

    The synthesis of a new series of 1 beta-methylcarbapenems having a 1,3-diazabicyclo[3.3.0]octane-2,4-dione moiety is described. Their in vitro antibacterial activities against both Gram-positive and Gram-negative bateria are determined and the effect of substituent on the bicyclic ring as well as stereoisomerism was investigated.

  15. Raman spectroscopic study of the mineral qingheiite Na2(Mn2+,Mg,Fe2+)2(Al,Fe3+)(PO4)3, a pegmatite phosphate mineral from Santa Ana pegmatite, Argentina.

    PubMed

    Frost, Ray L; Xi, Yunfei; Scholz, Ricardo; López, Andrés; Moreira, Caio; de Lena, Jorge Carvalho

    2013-10-01

    The pegmatite mineral qingheiite Na2(Mn(2+),Mg,Fe(2+))2(Al,Fe(3+))(PO4)3 has been studied by a combination of SEM and EMP, Raman and infrared spectroscopy. The studied sample was collected from the Santa Ana pegmatite, Argentina. The mineral occurs as a primary mineral in lithium bearing pegmatite, in association with beausite and lithiophilite. The Raman spectrum is characterized by a very sharp intense Raman band at 980 cm(-1) assigned to the PO4(3-) symmetric stretching mode. Multiple Raman bands are observed in the PO4(3-) antisymmetric stretching region, providing evidence for the existence of more than one phosphate unit in the structure of qingheiite and evidence for the reduction in symmetry of the phosphate units. This concept is affirmed by the number of bands in the ν4 and ν2 bending regions. No intensity was observed in the OH stretching region in the Raman spectrum but significant intensity is found in the infrared spectrum. Infrared bands are observed at 2917, 3195, 3414 and 3498 cm(-1) are assigned to water stretching vibrations. It is suggested that some water is coordinating the metal cations in the structure of qingheiite. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. Immunocytochemical localization of metabotropic (mGluR2/3 and mGluR4a) and ionotropic (GluR2/3) glutamate receptors in adrenal medullary ganglion cells.

    PubMed

    Sarría, R; Díez, J; Losada, J; Doñate-Oliver, F; Kuhn, R; Grandes, P

    2006-02-01

    The localization of metabotropic glutamate receptors of groups II (mGluR2/3) and III (mGluR4a) and the subunits 2 and 3 of alfa-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid (AMPA) ionotropic glutamate receptors (GluR2/3) was investigated with immunocytochemical methods in the rat adrenal gland. MGluR2/3, mGluR4a and GluR2/3 immunoreactivities were observed in large-sized, centrally located type I adrenal medullary ganglion neurons. Furthermore, the small-sized type II adrenal ganglion neurons identified by their immunoreactivity to brain nitric oxide synthase (bNOS), also expressed mGluR2/3, mGluR4a and GluR2/3. These cells were disposed in the peripheral portion of the adrenal medulla. None of the type I neurons were positively labeled for bNOS. These morphological observations suggest that activation of glutamate receptors in ganglion neurons may be instrumental in the control of adrenal endocrine systems as well as blood regulation.

  17. Synthesis of fused 1,2,4-dithiazines and 1,2,3,5-trithiazepines.

    PubMed

    Koyioni, Maria; Manoli, Maria; Koutentis, Panayiotis A

    2014-10-17

    Reacting (Z)-N-(4-chloro-5H-1,2,3-dithiazol-5-ylidene)-1H-pyrazol-5-amines 5 with Et2NH and then with concd H2SO4 gives 5H-pyrazolo[3,4-e][1,2,4]dithiazine-3-carbonitriles 7 in good yields (74-85%) and 6H-pyrazolo[3,4-f][1,2,3,5]trithiazepine-4-carbonitriles 9 as minor products (0-6%). Furthermore, the 1,3-dimethylpyrazole analogue 5a was transformed into the dithiazine 7a in two discrete steps, allowing the isolation of a disulfide intermediate (Z)-2-[(diethylamino)disulfan-yl]-2-[(1H-pyrazol-5-yl)imino]acetonitrile (8a). The one-pot, two-step reaction also worked with electron-rich hydroxy- and methoxy-substituted anilines. Thermolysis of the pyrazolo[3,4-e][1,2,4]dithiazines 7 gave the ring-contracted 1H-pyrazolo[3,4-d]thiazole-5-carbonitriles 6 (94-100%). With active sulfur, 1,3-dimethyl-5H-pyrazolo[3,4-e][1,2,4]dithiazine-3-carbonitrile (7a) gave 1,3-dimethyl-6H-pyrazolo[3,4-f][1,2,3,5]trithiazepine-4-carbonitrile (9a), but on prolonged reaction times, it gave 5,7-dimethyl-5H-[1,2,3]dithiazolo[4,5-b]pyrazolo[3,4-e][1,4]thiazine (13). Finally, in the absence of acid, heating a solution of (Z)-2-[(diethylamino)disulfanyl]-2-[(1,3-dimethyl-1H-pyrazol-5-yl)imino]acetonitrile (8a) gave 4,6,10,12-tetramethyl-6H-pyrazolo[3,4-f]pyrazolo[3',4':4,5]pyrimido[6,1-d][1,2,3,5]trithiazepine-8,12b(10H)-dicarbonitrile (19) (67%).

  18. Ultrasound-assisted synthesis of novel 4-(2-phenyl-1,2,3-triazol-4-yl)-3,4-dihydropyrimidin-(1H)-(thio)ones catalyzed by Sm(ClO(4))(3).

    PubMed

    Liu, Chen-Jiang; Wang, Ji-De

    2010-03-24

    An efficient synthesis of novel 4-(2-phenyl-1,2,3-triazol-4-yl)-3,4-dihydro-pyrimidin-2(1H)-(thio)ones from 1,3-dicarbonyl compounds, 2-phenyl-1,2,3-triazole-4-carbaldehyde and urea or thiourea under ultrasound irradiation and using samarium perchlorate as catalyst is described. Compared with conventional methods, the main advantages of the present methodology are milder conditions, shorter reaction times and higher yields.

  19. Kampelite, Ba3Mg1.5Sc4(PO4)6(OH)3·4H2O, a new very complex Ba-Sc phosphate mineral from the Kovdor phoscorite-carbonatite complex (Kola Peninsula, Russia)

    NASA Astrophysics Data System (ADS)

    Yakovenchuk, Victor N.; Ivanyuk, Gregory Yu.; Pakhomovsky, Yakov A.; Panikorovskii, Taras L.; Britvin, Sergei N.; Krivovichev, Sergey V.; Shilovskikh, Vladimir V.; Bocharov, Vladimir N.

    2018-02-01

    Kampelite, Ba3Mg1.5Sc4(PO4)6(OH)3·4H2O, is a new Ba-Sc phosphate from the Kovdor phoscorite-carbonatite complex (Kola Peninsula, Russia). It is orthorhombic, Pnma, a = 11.256(1), b = 8.512(1), c = 27.707(4) Å, V = 2654.6(3) Å3 and Z = 4 (from powder diffraction data) or a = 11.2261(9), b = 8.5039(6), c = 27.699(2) Å, V = 2644.3(3) Å3 (from single-crystal diffraction data). The mineral was found in a void within the calcite-magnetite phoscorite (enriched in hydroxylapatite and Sc-rich baddeleyite) inside the axial zone of the Kovdor phoscorite-carbonatite pipe. Kampelite forms radiated aggregates (up to 1.5 mm in diameter) of platy crystals grown on the surfaces of crystals of quintinite-2 H in close association with pyrite, bobierrite and quintinite-3 R. Kampelite is colourless, with a pearly lustre and a white streak. The cleavage is perfect on {001}, the fracture is smooth. Mohs hardness is about 1. In transmitted light, the mineral is colourless without pleochroism or dispersion. Kampelite is biaxial + (pseudouniaxial), α ≈ β = 1.607(2), γ = 1.612(2) (589 nm), and 2 V calc = 0°. The calculated and measured densities are 3.28 and 3.07(3) g·cm-3, respectively. The mean chemical composition determined by electron microprobe is: MgO 4.79, Al2O3 0.45, P2O5 31.66, K2O 0.34, Sc2O3 16.17, Mn2O3 1.62, Fe2O3 1.38, SrO 3.44, and BaO 29.81 wt%. The H2O content estimated from the crystal-structure refinement is 7.12 wt%, giving a total of 96.51 wt%. The empirical formula calculated on the basis of P = 6 apfu (atoms per formula unit) is (Ba2.62Sr0.45K0.10Ca0.06)Σ3.23Mg1.60Mn0.28(Sc3.15Fe3+ 0.23Al0.12)Σ3.50(PO4)6(OH)2.61·4.01H2O. The simplified formula is Ba3Mg1.5Sc4(PO4)6(OH)3·4H2O. The mineral easily dissolves in 10% cold HCl. The strongest X-ray powder-diffraction lines [listed as d in Å ( I) ( hkl)] are as follows: 15.80(100)(001), 13.86(45)(002), 3.184(18)(223), 3.129(19)(026), 2.756(16)(402), 2.688(24)(10 10). The crystal structure of kampelite was

  20. Design and synthesis of highly potent benzodiazepine gamma-secretase inhibitors: preparation of (2S,3R)-3-(3,4-difluorophenyl)-2-(4-fluorophenyl)-4- hydroxy-N-((3S)-1-methyl-2-oxo-5- phenyl-2,3-dihydro-1H-benzo[e][1,4]-diazepin-3-yl)butyramide by use of an asymmetric Ireland-Claisen rearrangement.

    PubMed

    Churcher, Ian; Williams, Susie; Kerrad, Sonia; Harrison, Timothy; Castro, José L; Shearman, Mark S; Lewis, Huw D; Clarke, Earl E; Wrigley, Jonathan D J; Beher, Dirk; Tang, Yui S; Liu, Wensheng

    2003-06-05

    Novel benzodiazepine-containing gamma-secretase inhibitors for potential use in Alzheimer's disease have been designed that incorporate a substituted hydrocinnamide C-3 side chain. A syn combination of alpha-alkyl or aryl and beta-hydroxy or hydroxymethyl substituents was shown to give highly potent compounds. In particular, (2S,3R)-3-(3,4-difluorophenyl)-2-(4-fluorophenyl)-4-hydroxy-N-((3S)-2-oxo-5-phenyl-2,3-dihydro-1H-benzo[e][1,4]diazepin-3-yl)butyramide (34) demonstrated excellent in vitro potency (IC(50) = 0.06 nM). 34 could also be selectively methylated to give [(3)H]-28, which is of use in radioligand binding assays.

  1. On local structural changes in lizardite-1 T: {Si4+/Al3+}, {Si4+/Fe3+}, [Mg2+/Al3+], [Mg2+/Fe3+] substitutions

    NASA Astrophysics Data System (ADS)

    Scholtzová, Eva; Smrčok, Ľubomír

    2005-09-01

    Geometrical changes induced by cation substitutions {Si4+/Al3+}[Mg2+/Al3+], {2Si4+/2Al3+} [2Mg2+/2Al3+], {Si4+/Fe3+} [Mg2+/Al3+] or [Mg2+/Fe3+], where {} and [] indicate tetrahedral and octahedral sheet in lizardite 1 T, are studied by ab-initio quantum chemistry calculations. The majority of the models are based on the chemical compositions reported for various lizardite polytypes with the amount of Al in the tetrahedral sheets reported to vary from 3.5% to 8% in the 1 T and 2 H 1, up to 30% in the 2 H 2 polytype. Si4+ by Fe3+ substitution in the tetrahedral sheet with an Al3+ (Fe3+) in the role of a charge compensating cation in the octahedral sheet is also examined. The cation substitutions result in the geometrical changes in the tetrahedral sheets, while the octahedral sheets remain almost untouched. Substituted tetrahedra are tilted and their basal oxygens pushed down from the plane of basal oxygens. Ditrigonal deformation of tetrahedral sheets depends on the substituting cation and the degree of substitution.

  2. Synthesis of 7-azabicyclo[2.2.1]heptane and 2-oxa-4-azabicyclo[3.3.1]non-3-ene derivatives by base-promoted heterocyclization of alkyl N-(cis(trans)-3,trans(cis)-4-dibromocyclohex-1-yl)carbamates and N-(cis(trans)-3,trans(cis)-4-dibromocyclohex-1-yl)-2,2,2-trifluoroacetamides.

    PubMed

    Gómez-Sanchez, Elena; Soriano, Elena; Marco-Contelles, José

    2007-11-09

    We have studied the base-promoted heterocyclization of alkyl N-(cis(trans)-3,trans(cis)-4-dibromocyclohex-1-yl)carbamates and N-(cis(trans)-3,trans(cis)-4-dibromocyclohex-1-yl)-2,2,2-trifluoroacetamides, investigating the effect of the nitrogen protecting group and the relative configuration of the leaving group at C3 and C4 on the outcome of this reaction. We have observed that the sodium hydride-promoted heterocyclization of alkyl N-(cis-3,trans-4-dibromocyclohex-1-yl)carbamates (10, 12, 14, 16, 18) is a convenient method for the synthesis of 7-azabicyclo[2.2.1]heptane derivatives. For instance, the reaction of tert-butyl N-(cis-3,trans-4-dibromocyclohex-1-yl)carbamate (10) with sodium hydride in DMF at room temperature provides 2-bromo-7-[(tert-butoxy)carbonyl]-7-azabicyclo[2.2.1]heptane (2) (52% yield), whose t-BuOK-promoted hydrogen bromide elimination affords 7-[(tert-butoxy)carbonyl]-7-azabicyclo[2.2.1]hept-2-ene (31) in 78% yield, an intermediate in the total synthesis of epibatidine (1). However, the NaH/DMF-mediated heterocyclization of alkyl N-(trans-3,cis-4-dibromocyclohex-1-yl)carbamates (11, 13) is a more structure dependent reaction, where the nucleophilic attack of the oxygen atom of the protecting group controls the outcome of the reaction, giving rise to benzooxazolone and 2-oxa-4-azabicyclo[3.3.1]non-3-ene derivatives, respectively, from low to moderate yields, in complex reaction mixtures. Conversely, the NaH/DMF heterocyclizations of N-(cis-3,trans-4-dibromocyclohex-1-yl)-2,2,2-trifluoroacetamide (40) or N-(trans-3,cis-4-dibromocyclohex-1-yl)-2,2,2-trifluoroacetamide (42) are very clean reactions giving 7-azabicyclo[2.2.1]heptane or 2-oxa-4-azabicyclo[3.3.1]non-3-ene derivatives, respectively, in good yields. Finally, a mechanistic investigation, based on DFT calculations, has been carried out to rationalize the formation of the different adducts.

  3. 10 CFR 960.4-2-3 - Rock characteristics.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 4 2013-01-01 2013-01-01 false Rock characteristics. 960.4-2-3 Section 960.4-2-3 Energy... REPOSITORY Postclosure Guidelines § 960.4-2-3 Rock characteristics. (a) Qualifying condition. The present and expected characteristics of the host rock and surrounding units shall be capable of accommodating the...

  4. Intramolecular inverse-electron-demand Diels-Alder reactions of imidazoles with 1,2,4-triazines: a new route to 1,2,3,4-tetrahydro-1,5-naphthyridines and related heterocycles.

    PubMed

    Lahue, Brian R; Lo, Sie-Mun; Wan, Zhao-Kui; Woo, Grace H C; Snyder, John K

    2004-10-15

    The intramolecular inverse-electron-demand Diels-Alder reaction between imidazoles and 1,2,4-triazines linked by a trimethylene tether from the imidazole N1 position to the triazine C3 proceed in excellent yields to produce 1,2,3,4-tetrahydro-1,5-naphthyridines. The reaction proceeds by a cycloaddition with subsequent loss of nitrogen, followed by a presumed stepwise loss of a nitrile. The analogous intramolecular cycloadditions employing a tetramethylene tether also proceeded to give 2,3,4,5-tetrahydro-1H-pyrido[3,2-b]azepines in acceptable yields. The reaction to produce the tetrahydro-1,5-naphthyridines can also be promoted with microwave irradiation.

  5. Effects of environment of the activated nonradiative decay of the /sup 3/A/sub 2/ state of Rh/sub 2/(TMB)/sub 4//sup 2 +/

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

    Milder, S.J.

    1985-10-09

    The effect of environment on the temperature dependence of the nonradiative decay of the /sup 3/A/sup 2/ state of Rh/sub 2/(TMB)/sub 4//sup 2 +/ (TMB = 2,5-dimethyl-2,5-diisocyanohexane) is studied. The temperature dependence of the observed nonradiative decay rate can be approximately fit to an Arrhenius-like expression: k/sub obsd/ = k/sub 0/ + Ae/sup -E/sub a//RT/. Arrhenius parameters are obtained in seven different environments, with the activation energies varying from 1970 to 3420 cm/sup -1/. A plot of 1n A vs. E/sub a/, known as a Barclay-Butler plot, is linear, with slope = 3.3 x 10/sup -3/ cm and y interceptmore » = 20.0. The linear Barclay-Butler plot suggests that the activated decay from the /sup 3/A/sub 2/ state of Rh/sub 2/(TMB)/sub 4//sup 2 +/ has the same mechanism, regardless of environment. Single-crystal, dilute-plastic, and dilute-crystal environments have been tested. 13 references, 4 figures.« less

  6. Structure elucidation of 3-[1-(6-methoxy-2-naphtyl)ethyl]-6-(2,4-dichlorophenyl)-7H-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazine, C 23H 18Cl 2N 4OS from synchrotron X-ray powder diffraction

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

    Gündoğdu, Gülsüm; Aytaç, Sevim Peri; Müller, Melanie

    The 3-[1-(6-methoxy-2-naphtyl)ethyl]-6-(2,4-dichlorophenyl)-7H-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazine, C 23H 18Cl 2N 4OS compound was synthesized, as a member of the family of novel potential anticancer agents. The structure of the title compound was characterized by IR, 1H-NMR, mass spectroscopy, and elemental analysis, previously. In this study, the crystal structure of this compound has been determined from synchrotron X-ray powder diffraction data. The crystal structure was solved by simulated annealing and the final structure was achieved by Rietveld refinement method using soft restrains on all interatomic bond lengths and angles. This compound crystallizes in space groupP21,Z= 2, with the unit-cell parametersa= 15.55645(11) Å,b= 8.61693(6) Å,c= 8.56702(6)more » Å,β= 104.3270(4)°, andV= 1112.68(1) Å 3. In the crystal structure, strong C-H∙∙∙πand weak intermolecular hydrogen-bonding interactions link the molecules into a three-dimensional network. The molecules are in a head-to-head arrangement in the unit cell.« less

  7. Pharmacology of 1-(3,4-dichlorobenzyl)-3,4,5,6-tetrahydro-2(1H)-pyrimidone, a novel antidepressant compound with antianxiety activity.

    PubMed

    Ellis, K O; Wessels, F L; Burns, R H; Pong, S F

    1980-10-01

    1-(3,4-dichlorobenzyl)-3,4,5,6-tetrahydro-2(1H)-pyrimidone (I) was evaluated in selected pharmacological tests, and its activity was compared to that of some clinically useful psychotropic drugs. Based on the results, it is evident that I has a unique profile of antidepressant and antianxiety activities that are evident in the same dose range. The mechanism of its antidepressant activity is proposed to be similar to the tricyclic antidepressants, that is, inhibition of norepinephrine uptake. Neither I nor the tricyclic antidepressants possess monoamine oxidase-inhibiting activity. However, unlike the tricyclic antidepressants, I is devoid of any significant anticholinergic activity and presumably is free of anticholinergic side effects.

  8. Association between cytochrome CYP17A1, CYP3A4, and CYP3A43 polymorphisms and prostate cancer risk and aggressiveness in a Korean study population

    PubMed Central

    Han, Jun Hyun; Lee, Yong Seong; Kim, Hae Jong; Lee, Shin Young; Myung, Soon Chul

    2015-01-01

    In this study, we evaluated genetic variants of the androgen metabolism genes CYP17A1, CYP3A4, and CYP3A43 to determine whether they play a role in the development of prostate cancer (PCa) in Korean men. The study population included 240 pathologically diagnosed cases of PCa and 223 age-matched controls. Among the 789 single-nucleotide polymorphism (SNP) database variants detected, 129 were reported in two Asian groups (Han Chinese and Japanese) in the HapMap database. Only 21 polymorphisms of CYP17A1, CYP3A4, and CYP3A43 were selected based on linkage disequilibrium in Asians (r2 = 1), locations (SNPs in exons were preferred), and amino acid changes and were assessed. In addition, we performed haplotype analysis for the 21 SNPs in CYP17A1, CYP3A4, and CYP3A43 genes. To determine the association between genotype and haplotype distributions of patients and controls, logistic analyses were carried out, controlling for age. Twelve sequence variants and five major haplotypes were identified in CYP17A1. Five sequence variants and two major haplotypes were identified in CYP3A4. Four sequence variants and four major haplotypes were observed in CYP3A43. CYP17A1 haplotype-2 (Ht-2) (odds ratio [OR], 1.51; 95% confidence interval [CI], 1.04–2.18) was associated with PCa susceptibility. CYP3A4 Ht-2 (OR: 1.87; 95% CI: 1.02–3.43) was associated with PCa metastatic potential according to tumor stage. rs17115149 (OR: 1.96; 95% CI: 1.04–3.68) and CYP17A1 Ht-4 (OR: 2.01; 95% CI: 1.07–4.11) showed a significant association with histologic aggressiveness according to Gleason score. Genetic variants of CYP17A1 and CYP3A4 may play a role in the development of PCa in Korean men. PMID:25337833

  9. Association between cytochrome CYP17A1, CYP3A4, and CYP3A43 polymorphisms and prostate cancer risk and aggressiveness in a Korean study population.

    PubMed

    Han, Jun Hyun; Lee, Yong Seong; Kim, Hae Jong; Lee, Shin Young; Myung, Soon Chul

    2015-01-01

    In this study, we evaluated genetic variants of the androgen metabolism genes CYP17A1, CYP3A4, and CYP3A43 to determine whether they play a role in the development of prostate cancer (PCa) in Korean men. The study population included 240 pathologically diagnosed cases of PCa and 223 age-matched controls. Among the 789 single-nucleotide polymorphism (SNP) database variants detected, 129 were reported in two Asian groups (Han Chinese and Japanese) in the HapMap database. Only 21 polymorphisms of CYP17A1, CYP3A4, and CYP3A43 were selected based on linkage disequilibrium in Asians (r2 = 1), locations (SNPs in exons were preferred), and amino acid changes and were assessed. In addition, we performed haplotype analysis for the 21 SNPs in CYP17A1, CYP3A4, and CYP3A43 genes. To determine the association between genotype and haplotype distributions of patients and controls, logistic analyses were carried out, controlling for age. Twelve sequence variants and five major haplotypes were identified in CYP17A1. Five sequence variants and two major haplotypes were identified in CYP3A4. Four sequence variants and four major haplotypes were observed in CYP3A43. CYP17A1 haplotype-2 (Ht-2) (odds ratio [OR], 1.51; 95% confidence interval [CI], 1.04-2.18) was associated with PCa susceptibility. CYP3A4 Ht-2 (OR: 1.87; 95% CI: 1.02-3.43) was associated with PCa metastatic potential according to tumor stage. rs17115149 (OR: 1.96; 95% CI: 1.04-3.68) and CYP17A1 Ht-4 (OR: 2.01; 95% CI: 1.07-4.11) showed a significant association with histologic aggressiveness according to Gleason score. Genetic variants of CYP17A1 and CYP3A4 may play a role in the development of PCa in Korean men.

  10. 2-Propyl-4H-thia­zolo[3,2-a][1,3,5]triazine-4-thione

    PubMed Central

    Yunus, Uzma; Tahir, Muhammad Kalim; Bhatti, Moazzam Hussain; Wong, Wai-Yeung

    2008-01-01

    In the title compound, C8H9N3S2, the n-propyl chain is disordered over two orientations (site-occupancy ratio = 0.522:0.478) and is roughly perpendicular to the fused thia­zolotriazine system. The angle between the fused ring and the propyl chain is 83.6 (1)° [ 82.2 (1)° for the disordered chain]. The structure is stabilized by C—H⋯N hydrogen bonds. PMID:21202112

  11. Enhanced visible light photocatalytic water reduction from a g-C 3N 4/SrTa 2O 6 heterojunction

    DOE PAGES

    Adhikari, Shiba P.; Hood, Zachary D.; Wang, Hui; ...

    2017-06-02

    In this paper, a new g-C 3N 4/SrTa 2O 6 heterojunction photocatalyst was designed and prepared by chimie douce (soft chemistry) method where carbon nitride (g-C 3N 4) was deposited over the metastable perovskite phase of SrTa 2O 6. The morphological study of the heterojunction using SEM and STEM revealed that g-C 3N 4 nanofibers are dispersed uniformly on the surface of SrTa 2O 6 plates leading to the intimate contact between them. The heterojunction could achieve a high and stable visible light photocatalytic H 2 generation of 137 mmol/h/mole of g-C 3N 4, which is much larger than themore » amount of hydrogen generated by one mole of pristine g-C 3N 4. Finally, a plausible mechanism for the observed enhanced photocatalytic activity for the heterojunction is proposed on the basis of effective charge separation of photogenerated electron-hole pairs, supported by band position calculations and photo-physical properties of g-C 3N 4 and SrTa 2O 6.« less

  12. Enhanced visible light photocatalytic water reduction from a g-C 3N 4/SrTa 2O 6 heterojunction

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

    Adhikari, Shiba P.; Hood, Zachary D.; Wang, Hui

    In this paper, a new g-C 3N 4/SrTa 2O 6 heterojunction photocatalyst was designed and prepared by chimie douce (soft chemistry) method where carbon nitride (g-C 3N 4) was deposited over the metastable perovskite phase of SrTa 2O 6. The morphological study of the heterojunction using SEM and STEM revealed that g-C 3N 4 nanofibers are dispersed uniformly on the surface of SrTa 2O 6 plates leading to the intimate contact between them. The heterojunction could achieve a high and stable visible light photocatalytic H 2 generation of 137 mmol/h/mole of g-C 3N 4, which is much larger than themore » amount of hydrogen generated by one mole of pristine g-C 3N 4. Finally, a plausible mechanism for the observed enhanced photocatalytic activity for the heterojunction is proposed on the basis of effective charge separation of photogenerated electron-hole pairs, supported by band position calculations and photo-physical properties of g-C 3N 4 and SrTa 2O 6.« less

  13. 3′ Phosphatase activity toward phosphatidylinositol 3,4-bisphosphate [PI(3,4)P2] by voltage-sensing phosphatase (VSP)

    PubMed Central

    Kurokawa, Tatsuki; Takasuga, Shunsuke; Sakata, Souhei; Yamaguchi, Shinji; Horie, Shigeo; Homma, Koichi J.; Sasaki, Takehiko; Okamura, Yasushi

    2012-01-01

    Voltage-sensing phosphatases (VSPs) consist of a voltage-sensor domain and a cytoplasmic region with remarkable sequence similarity to phosphatase and tensin homolog deleted on chromosome 10 (PTEN), a tumor suppressor phosphatase. VSPs dephosphorylate the 5′ position of the inositol ring of both phosphatidylinositol 3,4,5-trisphosphate [PI(3,4,5)P3] and phosphatidylinositol 4,5-bisphosphate [PI(4,5)P2] upon voltage depolarization. However, it is unclear whether VSPs also have 3′ phosphatase activity. To gain insights into this question, we performed in vitro assays of phosphatase activities of Ciona intestinalis VSP (Ci-VSP) and transmembrane phosphatase with tensin homology (TPTE) and PTEN homologous inositol lipid phosphatase (TPIP; one human ortholog of VSP) with radiolabeled PI(3,4,5)P3. TLC assay showed that the 3′ phosphate of PI(3,4,5)P3 was not dephosphorylated, whereas that of phosphatidylinositol 3,4-bisphosphate [PI(3,4)P2] was removed by VSPs. Monitoring of PI(3,4)P2 levels with the pleckstrin homology (PH) domain from tandem PH domain-containing protein (TAPP1) fused with GFP (PHTAPP1-GFP) by confocal microscopy in amphibian oocytes showed an increase of fluorescence intensity during depolarization to 0 mV, consistent with 5′ phosphatase activity of VSP toward PI(3,4,5)P3. However, depolarization to 60 mV showed a transient increase of GFP fluorescence followed by a decrease, indicating that, after PI(3,4,5)P3 is dephosphorylated at the 5′ position, PI(3,4)P2 is then dephosphorylated at the 3′ position. These results suggest that substrate specificity of the VSP changes with membrane potential. PMID:22645351

  14. Muscarinic subtypes profile modulation within a series of new antagonists, bridged bicyclic derivatives of 2,2-diphenyl-[1,3]-dioxolan-4-ylmethyl-dimethylamine.

    PubMed

    Piergentili, Alessandro; Gentili, Francesco; Ghelfi, Francesca; Marucci, Gabriella; Pigini, Maria; Quaglia, Wilma; Giannella, Mario

    2003-09-01

    A set of new muscarinic antagonists, bridged bicyclic derivatives of 2,2-diphenyl-[1,3]-dioxolan-4-ylmethyl-dimethylamine (1), was synthesized and tested to evaluate their affinity and selectivity for M(1), M(2), M(3) and M(4) receptor subtypes. The conformational constraint of 1 in a bicyclic structure, and the variation in distance and stereochemistry of the active functions allowed us to modulate the selectivity of interaction with the M(1)-M(3) receptor subtypes. The most interesting compound was (cis,trans)-2-(2,2-diphenylethyl)-5-methyl-tetrahydro-[1,3]dioxolo[4,5-c]pyrrole oxalate (6), which is equipotent with Pirenzepine on rabbit vas deferens (M(1)-putative) but shows a better selectivity profile.

  15. Two actinide-organic frameworks constructed by a tripodal flexible ligand: Occurrence of infinite ((UO{sub 2})O{sub 2}(OH){sub 3}){sub 4n} and hexanuclear (Th{sub 6}O{sub 4}(OH){sub 4}) motifs

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

    Liang, Lingling; Zhang, Ronglan; Zhao, Jianshe, E-mail: jszhao@nwu.edu.cn

    Two new actinide metal-organic frameworks were constructed by using a tripodal flexible ligand tris (2-carboxyethyl) isocyanurate (H{sub 3}tci) under hydrothermal condition. The combination of H{sub 3}tci and uranyl nitrate hexahydrate in aqueous solution leads to the isolation of [(UO{sub 2}){sub 2}(H{sub 2}O){sub 4}]{sub 0.5}(tci){sub 2}(UO{sub 2}){sub 4}(OH){sub 4}·18H{sub 2}O (1), which contains two distinct UO{sub 2}{sup 2+} coordination environments. Four uranyl cations, linked through μ{sub 3}-OH respectively, result in the edge-sharing ribbons. Then, the layer structure is constructed by U-O clusters linked through other eight-coordinated uranyl unions, giving rise to a porous structure in the space. Topological analysis reveals thatmore » complex 1 belongs to a (4, 8)-connected net with a schläfli symbol of (3{sup 4.}2{sup 6.}3){sub 2}(3{sup 4.}4{sup 6.}5{sup 6.}6{sup 8.}7{sup 3.}8). Th{sub 3}(tci){sub 2}O{sub 2}(OH){sub 2}(H{sub 2}O){sub 3}·12H{sub 2}O (2) generated by the reaction of H{sub 3}tci and thorium nitrate tetrahydrate, possesses nine-fold coodinated Th(IV) centers with a monocapped square antiprismatic geometry. The hexamers “Th{sub 6}O{sub 4}(OH){sub 4}” motifs are connected together by the carboxylate groups, showing a three-dimensional structures. Complex 2 takes on an 8-connected architecture and the point symbol is (4{sup 24.}6{sup 4}). - Graphical abstract: Two new 3D actinide metal-organic frameworks were constructed by using a tripodal flexible ligand tris (2-carboxyethyl) isocyanurate (H3tci) and their topological structures were displayed. The infinite ((UO{sub 2})O{sub 2}(OH){sub 3}){sub 4n} and hexanuclear (Th{sub 6}O{sub 4}(OH){sub 4}) motifs were found in the title actinides networks.« less

  16. 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

  17. Ni(ClO4)(2)-catalysed regio- and diastereoselective [3+2] cycloaddition of indoles and aryl oxiranyl-dicarboxylates/diketones: a facile access to furo[3,4-b]indoles.

    PubMed

    Zhang, Jieming; Chen, Zuliang; Wu, Hai-Hong; Zhang, Junliang

    2012-02-07

    Ni(ClO(4))(2)·6H(2)O-catalysed regioselective and diastereoselective [3+2]-annulations of aryl oxiranyl-dicarboxylates and indoles via selective C-C bond cleavage of oxirane were revealed. The cycloadditions proceed smoothly with high regio- and diastereoselectivity under mild conditions leading to 1H-furo[3,4-b]indoles in good to excellent yields. This journal is © The Royal Society of Chemistry 2012

  18. A WISE Measurement of the 2:4 mum Galaxy Luminosity Function and its Implications for the Extragalactic Background Light at 3:4 mum

    NASA Astrophysics Data System (ADS)

    Lake, Sean Earl

    2017-05-01

    The measurement of the the Extragalactic Background Light (EBL) has seen some controversy in recent works, with direct and indirect measures conflicting. Specifi- cally, upper limits based on analyzing the plausible opacity obscuring TeV spectra of blazars suggests that the density of radiation with wavelengths near 3.4 mum is onethirdtoonehalfasintenseasdirectmeasuresofthesame(forexample: Aharonian et al., 2006; Levenson et al., 2007; Matsumoto et al., 2005). The dominant contributor of the EBL at 3.4mum is expected to be ordinary starlight from relatively local, z < 1, galaxies, so an estimate of the amount of light emitted by galaxies based on the galaxy Luminosity Function (LF) should provide a useful lower limit to the EBL. While analyses of this sort have been done by others (Dominguez et al., 2011; Helgason et al., 2012), the full sky coverage of the AllWISE database has made it possible for us to improve the measurement of both the LF at 2.4 mum and the EBL using the large public spectroscopic redshift surveys. In order to do so, we had to develop a mathematical model for the measurement of a generalization of the LF, which is the density of galaxies per unit comoving volume per unit luminosity, to the Spectro-Luminosity Functional (SLF), which replaces the density per unit single luminosity, dL, with the density per luminosi- ii ties at all frequencies, DL nu. Our best combined analysis of the data yields present day Shechter Function LF parameters of: L⋆ = 6.4+/-[0.1 stat, 0.3sys]x1010 L2.4mum [solar mass](M⋆ = -21.67+/-[0.02 stat, 0.05sys] AB mag), φ⋆ = 5.8+/-[0.3stat, 0.3sys]x10 -3 Mpc-3, and alpha = -1.050 +/- [0.004stat, 0.03sys]; this implies a present day density of galaxies of 0.08 Mpc-3 brighter that 106 L2.4mum [solar mass] (10-3 Mpc-3 brighter than L⋆) and a luminosity density equivalent to 3.8 x 108 L2.4mum [solar mass] Mpc-3. The net EBL at 3.4mum that our synthesis model produces from galaxies closer than z = 5 is Inu = 9.0 +/- 0.5 k

  19. Fe4Nb2O9 : A magnetoelectric antiferromagnet

    NASA Astrophysics Data System (ADS)

    Maignan, Antoine; Martin, Christine

    2018-04-01

    The structural, magnetic, and electrical properties of a Fe4Nb2O9 polycrystalline sample have been characterized. It is found that this compound crystallizes in the P 3 ¯c 1 space group of the α -A l2O3 structure and is thus isostructural to Co4Nb2O9 and Mn4Nb2O9 , two linear magnetoelectric oxides. But in marked contrast, its ɛ'(T ) curve reveals two broad transitions at TN 1≅90 K and TN 2≅77 K , the former corresponding to the antiferromagnetic ordering temperature. Below TN 1, the M(H ) magnetization curves reveal the existence of spin flop at about 6 T. In this temperature region, a H-induced electric polarization for μ0H >6 T is evidenced by both sets of Ip(T) H and P (H) T curves. All these results point towards Fe4Nb2O9 being a magnetoelectric member of the A4B2O9 family (A =Mn , Fe, Co and B =Nb , Ta).

  20. Influences of neodymium doping on magnetic and electrochemical properties of Li3V2(PO4)3/C synthesized via a sol-gel method

    NASA Astrophysics Data System (ADS)

    Liu, Liying; Qiu, Yongbin; Mai, Yongzhi; Wu, Qibai; Zhang, Haiyan

    2015-11-01

    A series of neodymium doped Li3V2-xNdx(PO4)3/C cathode materials have been successfully synthesized by a citric acid assisted sol-gel method. Nd doped samples (x ≤ 0.10) have well developed monoclinic structure of Li3V2(PO4)3 with enlarged unit cell volume. All samples present typical characteristics of paramagnetism in 4 < T ≤ 300 K, but the magnetic susceptibilities of Nd doped samples increase with Nd content (except for x = 0.15). Nd doped composites show better electrochemical property than that of the undoped one. Among them, the Li3V1.95Nd0.05(PO4)3/C displays the highest capacity and best cycle stability. The Li3V1.95Nd0.05(PO4)3/C presents the first discharge capacity of 129.2 mAh g-1 at 1 C rate in the voltage range of 3.0-4.3 V, 21.7% higher than that of Li3V2(PO4)3/C. And no capacity loss occurs after 100 cycles. The high structural stability, low charge-transfer resistance and rapid Li+ diffusion due to the presence of Nd3+ are mainly responsible for the superior electrochemical performance of Nd doped Li3V2(PO4)3/C cathode materials.

  1. Synthetic and Spectroscopic Studies on N-(i,j-Disubstituted Phenyl)-4- Substituted Benzenesulphonamides, 4-X'C6H4SO2NH(i,j-X2C6H3), where X' = H, CH3, C2H5, F, Cl or Br; i, j = 2, 3; 2, 4; 2, 5; 2, 6 or 3, 4; and X = CH3 or Cl

    NASA Astrophysics Data System (ADS)

    Shetty, Mahesha; Gowda, B. Thimme

    2005-02-01

    Fifty four N-(i,j-disubstituted phenyl)-4-substituted benzenesulphonamides of the general formula 4-X'C6H4SO2NH(i,j-X2C6H3), where X' = H, CH3, C2H5, F, Cl or Br; i,j = 2,3; 2,4; 2,5; 2,6 or 3, 4; and X = CH3 or Cl, are prepared and characterized and their infrared, 1H and 13C NMR spectra in solution are studied. The N-H stretching vibrations νN-H absorb in the range 3305 - 3205 cm-1, while the asymmetric and symmetric SO2 vibrations vary in the ranges 1377 - 1307 cm-1 and 1184 - 1128 cm-1, respectively. The N-(i,j-disubstituted phenyl)-4-substituted benzenesulphonamides show C-S, S-N and C-N stretching vibrations in the ranges 844 - 800 cm-1, 945 - 891 cm-1 and 1309 - 1170 cm-1, respectively. The compounds do not exhibit particular trends in the variation of these frequencies on substitution either at ortho or meta positions with either a methyl group or Cl. The observed 1H and 13C chemical shifts of 2.jpg" /> are assigned to protons and carbon atoms of the two benzene rings. Incremental shifts of the ring protons and carbon atoms due to -SO2NH(i,j-X2C6H3) groups in C6H5SO2NH(i,j-X2C6H3) and 4-X'C6H4SO2NH- groups in 4-X'C6H4SO2NH(C6H*) are computed and employed to calculate the chemical shifts of the ring protons and carbon atoms in the substituted compounds 4-X'C6H4SO2NH(i,j-X2C6H3). The different methods of calculation lead to almost the same values in most cases and agree well with the observed chemical shifts, indicating the validity of the principle of additivity of the substituent effects with chemical shifts in these compounds.

  2. Pb4(BO3)2(SO4) and Pb2[(BO2)(OH)](SO4): New lead(II) borate-sulfate mixed-anion compounds with two types of 3D network structures

    NASA Astrophysics Data System (ADS)

    Ruan, Ting-Ting; Wang, Wen-Wen; Hu, Chun-Li; Xu, Xiang; Mao, Jiang-Gao

    2018-04-01

    Two new lead(II) borate-sulfate mixed-anion compounds, namely, Pb4(BO3)2(SO4) and Pb2[(BO2)(OH)](SO4), have been prepared by using high-temperature melt method or hydrothermal reaction. These compounds exhibit two different types of 3D structures composed of the same anionic units of BO3 triangles and SO4 tetrahedra which are interconnected by lead(II) cations. In Pb4(BO3)2(SO4), the lead(II) ions are bridged by borate anions into 3D [Pb4(BO3)2]2+ architectures with 1D tunnels of 8-member rings along the a-axis, which are filled by the sulfate anions. In Pb2[(BO2)(OH)](SO4), the lead(II) ions are interconnected by borate and sulfate anions into 2D Pb-B-O and Pb-S-O layers parallel to the ab plane, respectively, and these layers are further condensed into the 3D lead(II) borate-sulfate framework. TGA and DSC studies indicate that Pb4(BO3)2(SO4) is congruently melting with a melting point of 689 °C whereas Pb2[(BO2)(OH)](SO4) decomposes at approximately 335 °C. UV/Vis/NIR optical diffuse reflectance spectrum measurements reveal the optical band gaps of 4.03 and 4.08 eV for Pb4(BO3)2(SO4) and Pb2[(BO2)(OH)](SO4), respectively. Furthermore, the electronic structures of Pb4(BO3)2(SO4) have also been calculated.

  3. Sulfate-doped Fe3O4/Al2O3 nanoparticles as a novel adsorbent for fluoride removal from drinking water.

    PubMed

    Chai, Liyuan; Wang, Yunyan; Zhao, Na; Yang, Weichun; You, Xiangyu

    2013-08-01

    A novel adsorbent of sulfate-doped Fe3O4/Al2O3 nanoparticles with magnetic separability was developed for fluoride removal from drinking water. The nanosized adsorbent was characterized and its performance in fluoride removal was evaluated. Kinetic data reveal that the fluoride adsorption was rapid in the beginning followed by a slower adsorption process, nearly 90% adsorption can be achieved within 20 min and only 10-15% additional removal occurred in the following 8 h. The fluoride adsorption isotherm was well described by Elovich model. The calculated adsorption capacity of this nanoadsorbent for fluoride by two-site Langmuir model was 70.4 mg/g at pH 7.0. Moreover, this nanoadsorbent performed well over a considerable wide pH range of 4-10, and the fluoride removal efficiencies reached up to 90% and 70% throughout the pH range of 4-10 with initial fluoride concentrations of 10 mg/L and 50 mg/L, respectively. The observed sulfate-fluoride displacement and decreased sulfur content on the adsorbent surface reveal that anion exchange process was an important mechanism for fluoride adsorption by the sulfate-doped Fe3O4/Al2O3 nanoparticles. Moreover, a shift of the pH of zero point charge (pHPZC) of the nanoparticles and surface analysis based on X-ray photoelectron spectroscopy (XPS) suggest the formation of inner-sphere fluoride complex at the aluminum center as another adsorption mechanism. With the exception of PO4(3-), other co-existing anions (NO3(-), Cl(-) and SO4(2-)) did not evidently inhibit fluoride removal by the nanoparticles. Findings of this study demonstrate the potential utility of the nanoparticles as an effective adsorbent for fluoride removal from drinking water. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. Molecular Relaxation in LiNO3-LiClO4 and Li2CO3-Li2SO4 Solid Binary Systems

    NASA Astrophysics Data System (ADS)

    Aliev, A. R.; Akhmedov, I. R.; Kakagasanov, M. G.; Aliev, Z. A.; Gafurov, M. M.; Amirov, A. M.

    2018-06-01

    The paper presents spectroscopic combinational scattering investigations of the molecular relaxation in LiNO3-LiClO4 and Li2CO3-Li2SO4 solid binary systems. It is found that the relaxation time for ν1(A) vibrations of NO3 - anion in LiNO3-LiClO4 system is lower than in LiNO3 crystal. And the relaxation time for ν1(A) vibrations of CO3 2- anion in Li2CO3-Li2SO4 system is lower than in Li2CO3 crystal. The increase in the relaxation time is explained by the additional relaxation mechanism of the excited mode of nitrate and carbon ions which is observed in these systems. This mechanism is linked to the vibrations of other anions (ClO4 - or SO4 2-) and a nucleation of the lattice phonon. Experiments show that the additional relaxation mechanism occurs due to the vibration difference which corresponds to the area of rather a high density of states of the phonon spectrum.

  5. A complex study of 5-amino-3-methyl-4-[2-(5-amino-1,3,4-oxadiazolo)]-isoxazole monohydrate: A new low-molecular-weight immune response modifier

    NASA Astrophysics Data System (ADS)

    Ryng, Stanisław; Zimecki, Michał; Jezierska-Mazzarello, Aneta; Panek, Jarosław J.; Mączyński, Marcin; Głowiak, Tadeusz; Sawka-Dobrowolska, Wanda; Koll, Aleksander

    2011-07-01

    A new potential lead structure with immunological activity, 5-amino-3-methyl-4-[2-(5-amino-1,3,4-oxadiazolo)]-isoxazole monohydrate, was synthesized. A detailed description of synthesis is presented together with X-ray structural analysis. In vitro assays showed that the compound had a potent immunosuppressive activity. Next, Density Functional Theory (DFT) was employed to shed a light on molecular properties of the investigated isoxazole derivative. The molecular modeling part included geometric as well as electronic structure descriptions: (i) the conformational analysis was performed to localize the most appropriate conformation; (ii) the coordination energy and Basis Set Superposition Error (BSSE) were estimated for the complex of the isoxazole derivative interacting with water molecule; (iii) the potential energy distribution was used to assign molecular vibrations, and NBO population analysis served to describe the electronic structure; (iv) the electrostatic potential map was generated to provide the graphical presentation of regions exposed for intermolecular interactions. The contacts between the water molecule and the nitrogen atom of the isoxazole ring edge were present in the solid phase. On the other hand, the theoretical DFT prediction was that the oxygen atom of the edge should form a more stable complex with the water molecule.

  6. Phthalocyanine-Conjugated Upconversion NaYF4 :Yb3+ /Er3+ @SiO2 Nanospheres for NIR-Triggered Photodynamic Therapy in a Tumor Mouse Model.

    PubMed

    Kostiv, Uliana; Patsula, Vitalii; Noculak, Agnieszka; Podhorodecki, Artur; Větvička, David; Poučková, Pavla; Sedláková, Zdenka; Horák, Daniel

    2017-12-19

    Photodynamic therapy (PDT) has garnered immense attention as a minimally invasive clinical treatment modality for malignant cancers. However, its low penetration depth and photodamage of living tissues by UV and visible light, which activate a photosensitizer, limit the application of PDT. In this study, monodisperse NaYF 4 :Yb 3+ /Er 3+ nanospheres 20 nm in diameter, that serve as near-infrared (NIR)-to-visible light converters and activators of a photosensitizer, were synthesized by high-temperature co-precipitation of lanthanide chlorides in a high-boiling organic solvent (octadec-1-ene). The nanoparticles were coated with a thin shell (≈3 nm) of homogenous silica via the hydrolysis and condensation of tetramethyl orthosilicate. The NaYF 4 :Yb 3+ /Er 3+ @SiO 2 particles were further functionalized by methacrylate-terminated groups via 3-(trimethoxysilyl)propyl methacrylate. To introduce a large number of reactive amino groups on the particle surface, methacrylate-terminated NaYF 4 :Yb 3+ /Er 3+ @SiO 2 nanospheres were modified with a branched polyethyleneimine (PEI) via Michael addition. Aluminum carboxyphthalocyanine (Al Pc-COOH) was then conjugated to NaYF 4 :Yb 3+ /Er 3+ @SiO 2 -PEI nanospheres via carbodiimide chemistry. The resulting NaYF 4 :Yb 3+ /Er 3+ @SiO 2 -PEI-Pc particles were finally modified with succinimidyl ester of poly(ethylene glycol) (PEG) in order to alleviate their future uptake by the reticuloendothelial system. Upon 980 nm irradiation, the intensive red emission of NaYF 4 :Yb 3+ /Er 3+ @SiO 2 -PEI-Pc-PEG nanoparticles completely vanished, indicating efficient energy transfer from the nanoparticles to Al Pc-COOH, which generates singlet oxygen ( 1 O 2 ). Last but not least, NaYF 4 :Yb 3+ /Er 3+ @SiO 2 -PEI-Pc-PEG nanospheres were intratumorally administered into mammary carcinoma MDA-MB-231 growing subcutaneously in athymic nude mice. Extensive necrosis developed at the tumor site of all mice 24-48 h after irradiation by laser at

  7. Photolabeling a Nicotinic Acetylcholine Receptor (nAChR) with an (α4)32)2 nAChR-Selective Positive Allosteric Modulator

    PubMed Central

    Deba, Farah; Wang, Ze-Jun; Cohen, Jonathan B.

    2016-01-01

    Positive allosteric modulators (PAMs) of nicotinic acetylcholine (ACh) receptors (nAChRs) have potential clinical applications in the treatment of nicotine dependence and many neuropsychiatric conditions associated with decreased brain cholinergic activity, and 3-(2-chlorophenyl)-5-(5-methyl-1-(piperidin-4-yl)-1H-pyrrazol-4-yl)isoxazole (CMPI) has been identified as a PAM selective for neuronal nAChRs containing the α4 subunit. In this report, we compare CMPI interactions with low-sensitivity (α4)32)2 and high-sensitivity (α4)22)3 nAChRs, and with muscle-type nAChRs. In addition, we use the intrinsic reactivity of [3H]CMPI upon photolysis at 312 nm to identify its binding sites in Torpedo nAChRs. Recording from Xenopus oocytes, we found that CMPI potentiated maximally the responses of (α4)32)2 nAChR to 10 μM ACh (EC10) by 400% and with an EC50 of ∼1 µM. CMPI produced a left shift of the ACh concentration-response curve without altering ACh efficacy. In contrast, CMPI inhibited (∼35% at 10 µM) ACh responses of (α4)22)3 nAChRs and fully inhibited human muscle and Torpedo nAChRs with IC50 values of ∼0.5 µM. Upon irradiation at 312 nm, [3H]CMPI photoincorporated into each Torpedo [(α1)2β1γδ] nAChR subunit. Sequencing of peptide fragments isolated from [3H]CMPI-photolabeled nAChR subunits established photolabeling of amino acids contributing to the ACh binding sites (αTyr190, αTyr198, γTrp55, γTyr111, γTyr117, δTrp57) that was fully inhibitable by agonist and lower-efficiency, state-dependent [3H]CMPI photolabeling within the ion channel. Our results establish that CMPI is a potent potentiator of nAChRs containing an α44 subunit interface, and that its intrinsic photoreactivy makes it of potential use to identify its binding sites in the (α4)32)2 nAChR. PMID:26976945

  8. Genetic Predictors of Interindividual Variability in Hepatic CYP3A4 ExpressionS⃞

    PubMed Central

    Lamba, Vishal; Panetta, John C.; Strom, Stephen

    2010-01-01

    Variability in hepatic CYP3A4 cannot be explained by common CYP3A4 coding variants. We previously identified polymorphisms in pregnane X receptor (PXR) and ATP-binding cassette subfamily B member 1 (ABCB1) associated with CYP3A4 mRNA levels in small cohorts of human livers. However, the relative contributions of these genetic variations or of polymorphisms in other CYP3A4 regulators to variable CYP3A4 expression were not known. We phenotyped livers from white donors (n = 128) by quantitative real-time polymerase chain reaction for expression of CYP3A4, CYP3A5, and CYP3A7 and nine transcriptional regulators, coactivators, and corepressors. We resequenced hepatic nuclear factor-3-β (HNF3β, FoxA2), HNF4α, HNF3γ (FoxA3), nuclear receptor corepressor 2 (NCoR2), and regions of the CYP3A4 promoter and genotyped informative single-nucleotide polymorphisms in PXR and ABCB1 in the same livers. CYP3A4 mRNA was positively correlated with PXR and FoxA2 and negatively correlated with NCoR2 mRNA. A common silent polymorphism and a polymorphic trinucleotide (CCT) repeat in FoxA2 were associated with CYP3A4 expression. The transcriptional activity of the FoxA2 polymorphic CCT repeat alleles (wild-type, n = 14 and variant, n = 13, 15, and 19) when assayed by luciferase reporter transactivation assays was greatest for the wild-type repeat, with deviations from this number having decreased transcriptional activity. This corresponded with higher expression of FoxA2 mRNA and its targets PXR and CYP3A4 in human livers with (CCT) n = 14 genotypes. Multiple linear regression analysis was used to quantify the contributions of selected genetic polymorphisms to variable CYP3A4 expression. This approach identified sex and polymorphisms in FoxA2, HNF4α, FoxA3, PXR, ABCB1, and the CYP3A4 promoter that together explained as much as 24.6% of the variation in hepatic CYP3A4 expression. PMID:19934400

  9. Thermo and mechanoluminescence of Dy3+ activated K2Mg2(SO4)3 phosphor

    NASA Astrophysics Data System (ADS)

    Panigrahi, A. K.; Dhoble, S. J.; Kher, R. S.; Moharil, S. V.

    2003-08-01

    A solid state diffusion method for the preparation of (K2 : Dy)Mg2(SO4)3 and (K2 : Dy,P)Mg2(SO4)3 phosphors is reported. Thermoluminescence (TL) and mechanoluminescence (ML) characteristics are studied. TL, shown by the (K2 : Dy,P)Mg2(SO4)3 phosphor is 60% as intense as the conventional CaSO4 : Dy phosphor used in the TLD of ionization radiation. It has a linear TL dose response and a negligible fading. These properties of (K2 : Dy,P)Mg2(SO4)3 should be suitable in dosimetry of ionization radiation using TL technique. ML of (K2 : Dy)Mg2(SO4)3 shows one peak which has been observed in ML intensity versus time curve. The ML peak shows the recombination of electrons with free radicals (anion radicals produced by γ-irradiation) released from traps during the mechanical pressure applied on the Dy activated K2Mg2(SO4)3 phosphor. This ML mechanism is proposed for γ-irradiated sulfate based phosphors. It has been found that the total light output, i.e. ML intensity, increases with concentration of dopant, strain rate and irradiation dose of the phosphor. Mechanoluminescence and ML emission spectra of (K2 : Dy)Mg2(SO4)3 were recorded for better understanding of the ML process. The TL and ML measurements have also been performed to elucidate the mechanism of ML. Some correlation between ML and TL has also been found.

  10. 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...

  11. Synthesis and photoluminescence properties of a cyan-emitting phosphor Ca3(PO4)2:Eu2+ for white light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Zhou, Wenli; Han, Jin; Zhang, Xuejie; Qiu, Zhongxian; Xie, Qingji; Liang, Hongbin; Lian, Shixun; Wang, Jing

    2015-01-01

    In this paper, a cyan-emitting phosphor Ca3(PO4)2:Eu2+ (TCP:Eu2+) was synthesized and evaluated as a candidate for white light emitting diodes (WLEDs). This phosphor shows strong and broad absorption in 250-450 nm region, but the emission spectrum is prominent at around 480 nm. The emission intensity of the TCP:Eu2+ was found to be 60% and 82% of that of the commercial BaMgAl10O17:Eu2+ (BAM) under excitation at 340 nm and 370 nm, respectively. Upon excitation at 370 nm, the absolute internal and external quantum efficiencies of the Ca3(PO4)2:1.5%Eu2+ are 60% and 42%, respectively. Moreover, a white LED lamp was fabricated by coating TCP:Eu2+ with a blue-emitting BAM and a red-emitting CaAlSiN3:Eu2+ on a near-ultraviolet (375 nm) LED chip, driven by a 350 mA forward bias current, and it produces an intense white light with a color rendering index of 75.

  12. Preventing structural degradation from Na3V2(PO4)3 to V2(PO4)3: F-doped Na3V2(PO4)3/C cathode composite with stable lifetime for sodium ion batteries

    NASA Astrophysics Data System (ADS)

    Chen, Yanjun; Xu, Youlong; Sun, Xiaofei; Zhang, Baofeng; He, Shengnan; Li, Long; Wang, Chao

    2018-02-01

    A prospective NASICON-type F-doped Na3V2(PO4)2.93F0.07/C (F-0.07-NVP/C) composite is synthesized by a solid-state reaction method. F-doping can restrain the structural degradation from Na3V2(PO4)3 to V2(PO4)3 and enhance the structural stability. Meanwhile, it can decrease the particle size to diminish the pathway of Na+ diffusion, which can increase ionic conductivity efficiently. The kinetic behavior is significantly improved and it is beneficial to reinforcing the electrochemical performance of F-doping composites. Compared with Undoped-NVP/C sample, F-0.07-NVP/C composite delivers a 113 mAh g-1 discharge capacity at 10 mA g-1, which is very close to the theoretical capacity (117 mAh g-1). As for cycle performance, a reversible capacity of 97.8 mAh g-1 can be obtained and it retains 86% capacity after 1000 cycles at 200 mA g-1. F-0.07-NVP/C composite presents the highest DNa+ (2.62 × 10-15 cm2s-1), two orders of magnitude higher than the undoped sample (4.8 × 10-17 cm2s-1). This outstanding electrochemical performance is ascribed to the synergetic effect from improved kinetic behavior and enhanced structural stability due to F-doping. Hence, the F-doped composite would be a promising cathode material in SIB for energy storage and conversion.

  13. A library synthesis of 4-hydroxy-3-methyl-6-phenylbenzofuran-2-carboxylic acid ethyl ester derivatives as anti-tumor agents.

    PubMed

    Hayakawa, Ichiro; Shioya, Rieko; Agatsuma, Toshinori; Furukawa, Hidehiko; Naruto, Shunji; Sugano, Yuichi

    2004-09-06

    As a result of a hit-to-lead program using a technique of solution-phase parallel synthesis, a highly potent (2,4-dimethoxyphenyl)-[6-(3-fluorophenyl)-4-hydroxy-3-methylbenzofuran-2-yl]methanone (15b) was synthesized as an optimized derivative of 4-hydroxy-3-methyl-6-phenylbenzofuran-2-carboxylic acid ethyl ester (1), which was discovered as a screening hit from small-molecule libraries and exhibited selective cytotoxicity against a tumorigenic cell line.

  14. A comparative study on vibrational, conformational and electronic structure of 2-chloro-4-methyl-3-nitropyridine and 2-chloro-6-methylpyridine

    NASA Astrophysics Data System (ADS)

    Arjunan, V.; Saravanan, I.; Marchewka, Mariusz K.; Mohan, S.

    Experimental FTIR and FT-Raman spectroscopic analysis of 2-chloro-4-methyl-3-nitropyridine (2C4M3NP) and 2-chloro-6-methylpyridine (2C6MP) have been performed. A detailed quantum chemical calculations have been carried out using B3LYP and B3PW91 methods with 6-311++G** and cc-pVTZ basis sets. Conformation analysis was carried for 2C4M3NP and 2C6MP. The temperature dependence of thermodynamic properties has been analysed. The atomic charges, electronic exchange interaction and charge delocalisation of the molecule have been performed by natural bond orbital (NBO) analysis. Molecular electrostatic surface potential (MESP), total electron density distribution and frontier molecular orbitals (FMOs) are constructed at B3LYP/6-311++G** level to understand the electronic properties. The charge density distribution and site of chemical reactivity of the molecules have been obtained by mapping electron density isosurface with electrostatic potential surfaces (ESP). The electronic properties, HOMO and LUMO energies were measured by time-dependent TD-DFT approach.

  15. Heteromorphic NiCo2S4/Ni3S2/Ni Foam as a Self-Standing Electrode for Hydrogen Evolution Reaction in Alkaline Solution.

    PubMed

    Liu, Hui; Ma, Xiao; Rao, Yuan; Liu, Yang; Liu, Jialiang; Wang, Luyang; Wu, Mingbo

    2018-04-04

    Considerable works have been devoted on developing high-efficiency nonplatinum electrocatalysts for hydrogen evolution reaction (HER). Herein, 3D heteromorphic NiCo 2 S 4 /Ni 3 S 2 nanosheets network has been constructed on Ni foam (denoted as NiCo 2 S 4 /Ni 3 S 2 /NF) serving as a self-standing electrocatalyst through directly thermal sulfurization of a single-source NiCo-layered double hydroxide precursor. The resultant NiCo 2 S 4 /Ni 3 S 2 /NF electrode exhibits outstanding electrocatalytic HER performance with an extremely low onset overpotential of 15 mV and long-term durability in alkaline solution. Such enhanced HER performance can be credited to (1) the massive exposed active sites provided by mixed transition metal chalcogenides (NiCo 2 S 4 and Ni 3 S 2 ), (2) the strong interfacial interaction at NiCo 2 S 4 /Ni 3 S 2 heterojunction interfaces with the strengthened H binding, and (3) the porous highly conductive Ni foam substrate with accelerated electron transfer. This work opens up a new direction to fabricate effective and non-noble-metal electrodes for water splitting and hydrogen generation.

  16. Synthesis, crystal structure, and ionic conductivity of a new layered metal phosphate, Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3}

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

    Kim, Sung-Chul; Kwak, Hyun-Jung; Yoo, Chung-Yul

    2016-11-15

    A new layered metal phosphate, Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3}, was synthesized in the form of either a single-crystal or polycrystalline powder using the molten hydroxide flux method or a solid-state reaction, respectively. Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3} crystallizes to the P2{sub 1}/n (Z=4) monoclinic space group with lattice parameters a≈4.95 Å, b≈22.06 Å, c≈8.63 Å, and β≈91.5°. The structure is composed of stacked [LiSrAl(PO{sub 4}){sub 2}] layers alternating regularly with [LiSrPO{sub 4}] layers. In the [LiSrAl(PO{sub 4}){sub 2}] sublattice, the AlO{sub 6} octahedra and PO{sub 4} tetrahedra are tilted cooperatively to form an anionic, corrugated, two-dimensional [Al(PO{sub 4}){sub 2}]{supmore » 3−} framework that can be regarded as a “distorted-glaserite” structure. The [LiSrPO{sub 4}] sublattice is that of a layered block containing a six-membered ring formed from alternating linkages of LiO{sub 4} and PO{sub 4} tetrahedra. The six-membered rings show a boat-type arrangement with the up(U) or down(D) pointing sequence, UUDUUD. The interspace between the two sublattices generates a two-dimensional pathway for Li{sup +} ion conduction. The impedance measurement indicated that Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3} had a moderate ion conductivity (σ≈1.30×10{sup −4} S cm{sup −1} at 667 K), with an activation energy E{sub a}≈1.02 eV. - Graphical abstract: Polyhedral view of Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3}. Li{sup +} ions are represented by green spheres, Sr atoms by white spheres, AlO{sub 6} groups by octahedra, and PO{sub 4} groups by tetrahedra. - Highlights: • New compound Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3} is reported. • The crystal structure is investigated by single-crystal XRD analysis. • The structure is formed by the alternate stacking of two different sublattices. • Correlation between the crystal structure and ionic conductivity is discussed.« less

  17. Vibronic Structure of the tilde{X} ^2A_2' State of NO_3

    NASA Astrophysics Data System (ADS)

    Fukushima, Masaru

    2015-06-01

    We have measured dispersed fluorescence ( DF ) spectra from the single vibronic levels ( SVL's ) of the tilde{B} ^2E' state of jet cooled 14NO_3 and 15NO_3, and found a new vibronic band around the ν_1 fundamental This new band has two characteristics; (1) inverse isotope shift, and (2) unexpectedly strong intensity, i.e. comparable with that of the ν_1 fundamental. We concluded on the basis of the isotope effect that the terminated ( lower ) vibrational level of the new vibronic band should have vibrationally a_1' symmetry, and assigned to the third over-tone of the ν_4 asymmetric (e') mode, 3 ν_4 (a_1'). We also assigned a weaker band at about 160 cm-1 above the new band to one terminated to 3 ν_4 (a_2'). The 3 ν_4 (a_1') and (a_2') levels are ones with l = ±3. Hirota proposed new vibronic coupling mechanism which suggests that degenerate vibrational modes can induce electronic orbital angular momentum ( L ) even in non-degenerate electronic states. %It is thus thought the surprisingly wide splitting of 3 ν_4, a_1' and a_2', is resulted from vibronic coupling, and the explanation we proposed is as follows. We interpret this as a sort of break-down of the Born-Oppenheimer approximation, and think that ± l induces ∓barΛ, where barΛ expresses the pseudo-L; for the present system, one of the components of the third over-tone level, | Λ = 0; v_4 = 3, l = +3 rangle, can have contributions of | barΛ = -1; v_4 = 3, l = +2 rangle and | -2; 3, +1 rangle. Under this interpretation, it is expected that there is sixth-order vibronic coupling, (q_+^3Q_-^3 + q_-^3Q_+^3), between | 0; 3, +3 rangle and | 0; 3, -3 rangle. The sixth-order coupling is weaker than the Renner-Teller term ( the fourth-order term, (q_+^2Q_-^2 + q_-^2Q_+^2) ), but stronger than the eighth-order term, (q_+^4Q_-^4 + q_-^4Q_+^4). It is well known in linear molecules that the former shows huge separation, comparable with vibrational frequency, among the vibronic levels of Π electronic states

  18. TiO{sub 2} nanobelts with a uniform coating of g-C{sub 3}N{sub 4} as a highly effective heterostructure for enhanced photocatalytic activities

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

    Zhong, Xing; Jin, Meimei; Dong, Huaqing

    2014-12-15

    A novel g-C{sub 3}N{sub 4}/TiO{sub 2} nanobelt (NB) heterostructure was successfully designed and prepared. The as-prepared g-C{sub 3}N{sub 4}/TiO{sub 2} NB heterostructure exhibited high photocatalytic activity not only in the photodegradation of Rhodamine B (RhB) but also in photocatalytic H{sub 2} production. The g-C{sub 3}N{sub 4}/TiO{sub 2} NB heterostructure with a mass ratio of 1:1 demonstrated the best performance in the photodegradation of RhB, whereas a mass ratio of 3:1 demonstrated the highest H{sub 2} production rate of 46.6 μmol h{sup −1} in photocatalytic H{sub 2} production. We conclude that the synergistic effect between g-C{sub 3}N{sub 4} and TiO{sub 2}more » NBs promotes the photogenerated carrier separation in space. This valuable insight into the rational architectural design of nanostructure-based photocatalysts is expected to shed light on other photocatalytic reaction systems in the future. - Graphical abstract: A novel strategy to fabricate the g-C{sub 3}N{sub 4}/TiO{sub 2} nanobelt (NB) heterostructures was reported. The g-C{sub 3}N{sub 4}/TiO{sub 2} NB heterostructures exhibited highly effective photocatalytic activities for photodegradation of Rhodamine B and H{sub 2} production. - Highlights: • A novel strategy to fabricate the g-C{sub 3}N{sub 4}/TiO{sub 2} NB heterostructures was reported. • The heterostructure exhibited high catalytic activity in photodegradation of RhB. • The heterostructure showed good H{sub 2} productivity in photocatalytic water splitting. • The synergistic effect between g-C{sub 3}N{sub 4} and TiO{sub 2} NBs are important. • This study shows that the heterostructure can be an effective photocatalyst.« less

  19. EPR Spectroscopy of Radical Ions of a 2,3-Diamino-1,4-naphthoquinone Derivative.

    PubMed

    Tarábek, Ján; Wen, Jin; Dron, Paul I; Pospíšil, Lubomír; Michl, Josef

    2018-05-18

    We report the electron paramagnetic resonance spectra of the radical cation and radical anion of 1,2,2,3-tetramethyl-2,3-dihydro-1 H-naphtho[2,3- d]imidazole-4,9-dione (1) and its doubly 13 C labeled analogue 2, of interest for singlet fission. The hyperfine coupling constants are in excellent agreement with density functional theory calculations and establish the structures beyond doubt. Unlike the radical cation 1 •+ , the radical anion 1 •- and its parent 1 have pyramidalized nitrogen atoms and inequivalent methyl groups 15 and 16, in agreement with the calculations. The distinction is particularly clear with the labeled analogue 2 •- .

  20. Effective identification of (NH4)2CO3 and NH4HCO3 concentrations in NaHCO3 regeneration process from desulfurized waste.

    PubMed

    Govindan, Muthuraman; Karunakaran, Kannan; Nallasamy, Palanisami; Moon, Il Shik

    2015-01-01

    This work describes the quantitative analysis of (NH4)2CO3 and NH4HCO3 using a simple solution phase titration method. Back titration results at various (NH4)2CO3-NH4HCO3 ratios demonstrated that 6:4 ratio caused a 3% error in their differentiation, but very high errors were found at other ratios. A similar trend was observed for the double indicator method, especially when strong acid HCl was used as a titrant, where still less errors (2.5%) at a middle ratio of (NH4)2CO3-NH4HCO3 was found. Remaining ratios with low (NH4)2CO3 (2:8, 4:6) show high +ve error (found concentration is less) and high (NH4)2CO3 (7:3, 8:2, and 9:1) show high -ve error (found concentration is higher) and vice versa for NH4HCO3. In replacement titration using Na2SO4, at both higher end ratios of (NH4)2CO3-NH4HCO3 (2:8 and 9:1), both -ve and +ve errors were minimized to 75% by partial equilibrium arrest between (NH4)2CO3 and NH2COONH4, instead of more than 100% observed in back titration and only double indicator methods. In the presence of (NH4)2SO4 both -ve and +ve error% are completely reduced to 3±1 at ratios 2:8, 4:6, and 6:4 of (NH4)2CO3-NH4HCO3, which demonstrates that the equilibrium transformation between NH2COONH4 and (NH4)2CO3 is completely controlled. The titration conducted at lower temperature (5 °C) in the presence of (NH4)2SO4 at higher ratios of (NH4)2CO3-NH4HCO3 (7:3, 8:2,and 9:1) shows complete minimization of both -ve and +ve errors to 2±1%, which explains the complete arresting of equilibrium transformation. Finally, the developed method shows 2±1% error in differentiation of CO3(2-) and HCO3(-) in the regeneration process of NaHCO3 from crude desulfurized sample. The developed method is more promising to differentiate CO3(2-) and HCO3(-) in industrial applications. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. The interdomain interface in bifunctional enzyme protein 3/4A (NS3/4A) regulates protease and helicase activities.

    PubMed

    Aydin, Cihan; Mukherjee, Sourav; Hanson, Alicia M; Frick, David N; Schiffer, Celia A

    2013-12-01

    Hepatitis C (HCV) protein 3/4A (NS3/4A) is a bifunctional enzyme comprising two separate domains with protease and helicase activities, which are essential for viral propagation. Both domains are stable and have enzymatic activity separately, and the relevance and implications of having protease and helicase together as a single protein remains to be explored. Altered in vitro activities of isolated domains compared with the full-length NS3/4A protein suggest the existence of interdomain communication. The molecular mechanism and extent of this communication was investigated by probing the domain-domain interface observed in HCV NS3/4A crystal structures. We found in molecular dynamics simulations that the two domains of NS3/4A are dynamically coupled through the interface. Interestingly, mutations designed to disrupt this interface did not hinder the catalytic activities of either domain. In contrast, substrate cleavage and DNA unwinding by these mutants were mostly enhanced compared with the wild-type protein. Disrupting the interface did not significantly alter RNA unwinding activity; however, the full-length protein was more efficient in RNA unwinding than the isolated protease domain, suggesting a more direct role in RNA processing independent of the interface. Our findings suggest that HCV NS3/4A adopts an "extended" catalytically active conformation, and interface formation acts as a switch to regulate activity. We propose a unifying model connecting HCV NS3/4A conformational states and protease and helicase function, where interface formation and the dynamic interplay between the two enzymatic domains of HCV NS3/4A potentially modulate the protease and helicase activities in vivo. © 2013 The Protein Society.

  2. Multiplex pyrosequencing method to determine CYP2C9*3, VKORC1*2, and CYP4F2*3 polymorphisms simultaneously: its application to a Korean population and comparisons with other ethnic groups.

    PubMed

    Kim, Kyoung-Ah; Song, Wan-Geun; Lee, Hae-Mi; Joo, Hyun-Jin; Park, Ji-Young

    2014-11-01

    Warfarin is an anticoagulant that is difficult to administer because of the wide variation in dose requirements to achieve a therapeutic effect. CYP2C9, VKROC1, and CYP4F2 play important roles in warfarin metabolism, and their genetic polymorphisms are related to the variability in dose determination. In this study we describe a new multiplex pyrosequencing method to identify CYP2C9*3 (rs1057910), VKORC1*2 (rs9923231), and CYP4F2*3 (rs2108661) simultaneously. A multiplex pyrosequencing method to simultaneously detect CYP2C9*3, VKORC1*2, and CYP4F2*3 alleles was designed. We assessed the allele frequencies of the polymorphisms in 250 Korean subjects using the multiplex pyrosequencing method. The results showed 100 % concordance between single and multiplex pyrosequencing methods, and the polymorphisms identified by pyrosequencing were also validated with the direct sequencing method. The allele frequencies of these polymorphisms in this population were as follows: 0.040 for CYP2C9*3, 0.918 for VKORC1*2, and 0.416 for CYP4F2*3. Although the allele frequencies of the CYP2C9*3 and VKROC1*2 were comparable to those in Japanese and Chinese populations, their frequencies in this Korean population differed from those in other ethnic groups; the CYP4F2*3 frequency was the highest among other ethnic populations including Chinese and Japanese populations. The pyrosequencing methods developed were rapid and reliable for detecting CYP2C9*3, VKORC1*2, and CYP4F2*3. Large ethnic differences in the frequency of these genetic polymorphisms were noted among ethnic groups. CYP4F2*3 exhibited its highest allele frequency among other ethnic populations compared to that in a Korean population.

  3. Crystal structure and absolute configuration of (3aR,3aR,7aS,7′aS)-2,2,2′,2′-tetra­methyl-3a,6,7,7a,3a,6′,7′,7′a-octa­hydro-4,4′-bi[1,3-benzodioxol­yl], obtained from a Pd-catalyzed homocoupling reaction

    PubMed Central

    Macías, Mario A.; Pandolfi, Enrique; Schapiro, Valeria; Silveira, Gustavo P.; Vilela, Guilherme D.; Suescun, Leopoldo

    2017-01-01

    The absolute configuration, i.e. (3aR,3aR,7aS,7′aS), of the title compound, C18H26O4, synthesized via a palladium-catalyzed homocoupling reaction, was determined on the basis of the synthetic pathway and was confirmed by X-ray diffraction. The homocoupled mol­ecule is formed by two chemically identical moieties built up from two five- and six-membered fused rings. The supra­molecular assembly is controlled mainly by C—H⋯O inter­actions that lead to the formation of hydrogen-bonded chains of mol­ecules along the [001] direction, while weak dipolar inter­actions and van der Waals forces hold the chains together in the crystal structure. PMID:28083142

  4. Neutron diffraction studies of the Na-ion battery electrode materials NaCoCr{sub 2}(PO{sub 4}){sub 3}, NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3}

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

    Yahia, H. Ben; Essehli, R., E-mail: ressehli@qf.org.qa; Avdeev, M.

    The new compounds NaCoCr{sub 2}(PO{sub 4}){sub 3}, NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3} were synthesized by sol-gel method and their crystal structures were determined by using neutron powder diffraction data. These compounds were characterized by galvanometric cycling and cyclic voltammetry. NaCoCr{sub 2}(PO{sub 4}){sub 3}, NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3} crystallize with a stuffed α-CrPO{sub 4}-type structure. The structure consists of a 3D-framework made of octahedra and tetrahedra that are sharing corners and/or edges generating channels along [100] and [010], in which the sodium atoms are located. Of significance, in the structuresmore » of NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3} a statistical disorder Ni{sup 2+}/Cr{sup 3+} was observed on both the 8g and 4a atomic positions, whereas in NaCoCr{sub 2}(PO{sub 4}){sub 3} the statistical disorder Co{sup 2+}/Cr{sup 3+} was only observed on the 8g atomic position. When tested as negative electrode materials, NaCoCr{sub 2}(PO{sub 4}){sub 3}, NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3} delivered specific capacities of 352, 385, and 368 mA h g{sup −1}, respectively, which attests to the electrochemical activity of sodium in these compounds. - Highlights: • NaCoCr{sub 2}(PO{sub 4}){sub 3}, NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3} were synthesized by sol-gel method. • The crystal structures were determined by using neutron powder diffraction data. • The three compounds crystallize with a stuffed α-CrPO{sub 4}-type structure. • The three compounds were tested as anodes in sodium-ion batteries. • Relatively high specific capacities were obtained for these compounds.« less

  5. Constituents of Indonesian medicinal plant Averrhoa bilimbi and their cytochrome P450 3A4 and 2D6 inhibitory activities.

    PubMed

    Auw, Lidyawati; Subehan; Sukrasno; Kadota, Shigetoshi; Tezuka, Yasuhiro

    2015-01-01

    As constituents of Averrhoa bilimbi leaves we identified three new compounds (1-3) together with 12 known ones (4-15); their inhibitory activities on cytochrome P450 3A4 (CYP3A4) and 2D6 (CYP2D6) were examined. Among the isolated compounds, the mixture of 1 and 2, and compounds 4 and 9 showed strong inhibition on CYP3A4, but mild or no inhibition on CYP2D6. These compounds revealed the characteristics of 1) time- and concentration-dependent inhibition, 2) requirement of NADPH for the inhibition, 3) no protection by nucleophiles, and 4) suppression of the inhibition by competitive inhibitor. Thus, they are suggested to be mechanism-based inactivators of CYP3A4 and CYP2D6. The kinetic parameters for the inactivation (k(inact) and K(I)) were 0.19 min(-1) and 36.7 μM for the mixture of 1 and 2, 0.126 min(-1) and 10.5 μM for 4, and 0.29 min(-1) and 23.4 μM for 9.

  6. Synthesis and structure of spiro[2-(2-methylphenyl)-4H-1,3-benzoxazine-4,2′-adamantane

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

    Osyanin, V. A., E-mail: orgchem@samgtu.ru; Ivleva, E. A.; Rybakov, V. B.

    2015-01-15

    Synthesis and an X-ray diffraction study of spiro[2-(2-methylphenyl)-4H-1,3-benzoxazine-4,2′-adamantane] C{sub 24}H{sub 25}NO are performed: monoclinic crystal system, space group P2{sub 1}/c, a = 13.9424(3) Å, b = 7.56554(17) Å, c = 17.0155(3) Å, β = 99.6457(18)°, Z = 4, V = 1769.45(6) Å{sup 3}. ρ{sub calcd} = 1.244 g/cm{sup 3}, R = 0.0339 [T = 100(2) K]. The oxazine ring of the molecule adopts the boat conformation. The bond lengths and angles are standard for this class of compounds.

  7. Zincoberaunite, ZnFe3+ 5(PO4)4(OH)5ṡ6H2O, a new mineral from the Hagendorf South pegmatite, Germany

    NASA Astrophysics Data System (ADS)

    Chukanov, Nikita V.; Pekov, Igor V.; Grey, Ian E.; Price, Jason R.; Britvin, Sergey N.; Krzhizhanovskaya, Maria G.; Kampf, Anthony R.; Dünkel, Bernhard; Keck, Erich; Belakovskiy, Dmitry I.; MacRae, Colin M.

    2017-06-01

    The new mineral zincoberaunite, ideally ZnFe3+ 5(PO4)4(OH)5·6H2O, the Zn analogue of beraunite, is found in the Hagendorf South granitic pegmatite, Hagendorf, Bavaria, Germany, in two associations: (1) with potassium feldspar, quartz, jungite, phosphophyllite and mitridatite (the holotype) and (2) with flurlite, plimerite, Zn-bearing beraunite, schoonerite, parascholzite/scholzite, robertsite and altered phosphophyllite (the cotype). Zincoberaunite occurs as radial or randomly oriented aggregates of flexible fibers up to 1.5 mm long and up to 3 μm thick. D calc is 2.92 g/cm3 for the holotype and 2.94 g/cm3 for the cotype. Zincoberaunite is optically biaxial (-), α = 1.745(5), β = 1.760(5), γ = 1.770(5), 2 V meas = 80(5)°. Chemical composition of the holotype (electron probe microanalyser; H2O by gas chromatography of ignition products) is: MgO 0.28 wt%, CaO 0.47 wt%, ZnO 7.36 wt%, Al2O3 0.88 wt%, Fe2O3 42.42 wt%, P2O5 31.63 wt%, H2O 16.2 wt%, total 101.1 wt%. The empirical formula calculated on the basis of 27 oxygen atoms per formula unit is (Zn0.83Ca0.08Mg0.06)∑0.97(Fe3+ 4.88Al0.16)∑5.04(PO4)4.09(OH)4.78 · 5.86H2O. Zincoberaunite is monoclinic, space group C2 /c; refined unit cell parameters (for the holotype at room temperature and the cotype at 100 K, respectively) are: a 20.837(2) and 20.836(4), b 5.1624(4) and 5.148(1), c 19.250(1) and 19.228(4) Å, β 93.252(5) and 93.21(3)°, V 2067.3(3) and 2059.2(7) Å3, Z = 4. The crystal structure of the holotype specimen has been refined by the Rietveld method ( R p = 0.30 %; R B = 0.18 %) whereas the structure of the cotype has been solved from the single crystal data and refined to R 1 = 0.056 based on 1900 unique reflections with I > 2σ( I). The strongest reflections of the powder X-ray diffraction pattern of the holotype specimen [( d, Å) ( I, %) ( hkl)] are: 10.37 (100) (200), 9.58 (32) (002), 7.24 (26) (20-2), 4.817 (22) (111), 4.409 (13) (112), 3.483 (14) (11-4, 600), 3.431 (14) (404), 3.194 (15

  8. Tungsten phosphanylarylthiolato complexes [W{PhP(2-SC6H4)2-kappa3S,S',P} 2] and [W{P(2-SC6H4)3-kappa4S,S',S",P}2]: synthesis, structures and redox chemistry.

    PubMed

    Hildebrand, Alexandra; Lönnecke, Peter; Silaghi-Dumitrescu, Luminita; Hey-Hawkins, Evamarie

    2008-09-14

    PhP(2-SHC6H4)2 (PS2H2) reacts with WCl6 with reduction of tungsten to give the air-sensitive tungsten(IV) complex [W{PhP(2-SC6H4)2-kappa(3)S,S',P}2] (1). 1 is oxidised in air to [WO{PhPO(2-SC6H4)2-kappa(3)S,S',O}{PhP(2-SC6H4)2-kappa(3)S,S',P}] (2). The attempted synthesis of 2 by reaction of 1 with iodosobenzene as oxidising agent was unsuccessful. [W{P(2-SC6H4)3-kappa(4)S,S',S",P}2] (3) was formed in the reaction of P(2-SHC6H4)3 (PS3H3) with WCl6. The W(VI) complex 3 contains two PS3(3-) ligands, each coordinated in a tetradentate fashion resulting in a tungsten coordination number of eight. The reaction of 3 with AgBF4 yields the dinuclear tungsten complex [W2{P(2-SC6H4)3-kappa(4)S,S',S",P}3]BF4 (4). Complexes 1-4 were characterised by spectral methods and X-ray structure determination.

  9. Detailed investigation of Na2.24FePO4CO3 as a cathode material for Na-ion batteries

    PubMed Central

    Huang, Weifeng; Zhou, Jing; Li, Biao; Ma, Jin; Tao, Shi; Xia, Dingguo; Chu, Wangsheng; Wu, Ziyu

    2014-01-01

    Na-ion batteries are gaining an increased recognition as the next generation low cost energy storage devices. Here, we present a characterization of Na3FePO4CO3 nanoplates as a novel cathode material for sodium ion batteries. First-principles calculations reveal that there are two paths for Na ion migration along b and c axis. In-situ and ex-situ Fe K-edge X-ray absorption near edge structure (XANES) point out that in Na3FePO4CO3 both Fe2+/Fe3+ and Fe3+/Fe4+ redox couples are electrochemically active, suggesting also the existence of a two-electron intercalation reaction. Ex-situ X-ray powder diffraction data demonstrates that the crystalline structure of Na3FePO4CO3 remains stable during the charging/discharging process within the range 2.0–4.55 V. PMID:24595232

  10. 47 CFR 80.1093 - Ship radio equipment-Sea areas A1, A2, A3, and A4.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 47 Telecommunication 5 2010-10-01 2010-10-01 false Ship radio equipment-Sea areas A1, A2, A3, and... AND SPECIAL RADIO SERVICES STATIONS IN THE MARITIME SERVICES Global Maritime Distress and Safety System (GMDSS) Equipment Requirements for Ship Stations § 80.1093 Ship radio equipment—Sea areas A1, A2...

  11. Discovery of (+)-N-(3-aminopropyl)-N-[1-(5-benzyl-3-methyl-4-oxo-[1,2]thiazolo[5,4-d]pyrimidin-6-yl)-2-methylpropyl]-4-methylbenzamide (AZD4877), a kinesin spindle protein inhibitor and potential anticancer agent.

    PubMed

    Theoclitou, Maria-Elena; Aquila, Brian; Block, Michael H; Brassil, Patrick J; Castriotta, Lillian; Code, Erin; Collins, Michael P; Davies, Audrey M; Deegan, Tracy; Ezhuthachan, Jayachandran; Filla, Sandra; Freed, Ellen; Hu, Haiqing; Huszar, Dennis; Jayaraman, Muthusamy; Lawson, Deborah; Lewis, Paula M; Nadella, Murali V P; Oza, Vibha; Padmanilayam, Maniyan; Pontz, Timothy; Ronco, Lucienne; Russell, Daniel; Whitston, David; Zheng, Xiaolan

    2011-10-13

    Structure-activity relationship analysis identified (+)-N-(3-aminopropyl)-N-[1-(5-benzyl-3-methyl-4-oxo-[1,2]thiazolo[5,4-d]pyrimidin-6-yl)-2-methylpropyl]-4-methylbenzamide (AZD4877), from a series of novel kinesin spindle protein (KSP) inhibitors, as exhibiting both excellent biochemical potency and pharmaceutical properties suitable for clinical development. The selected compound arrested cells in mitosis leading to the formation of the monopolar spindle phenotype characteristic of KSP inhibition and induction of cellular death. A favorable pharmacokinetic profile and notable in vivo efficacy supported the selection of this compound as a clinical candidate for the treatment of cancer.

  12. Molecular and electronic structure of Re 2Br 4(PMe 3) 4

    DOE PAGES

    Johnstone, Erik V.; Poineau, Frederic; Todorova, Tanya K.; ...

    2016-07-07

    The dinuclear rhenium(II) complex Re 2Br 4(PMe 3) 4 was prepared from the reduction of [Re 2Br 8] 2– with ( n-Bu 4N)BH 4 in the presence of PMe 3 in propanol. The complex was characterized by single-crystal X-ray diffraction (SCXRD) and UV–visible spectroscopy. It crystallizes in the monoclinic C2/c space group and is isostructural with its molybdenum and technetium analogues. The Re–Re distance (2.2521(3) Å) is slightly longer than the one in Re 2Cl 4(PMe 3) 4 (2.247(1) Å). The molecular and electronic structure of Re 2X 4(PMe 3) 4 (X = Cl, Br) were studied by multiconfigurational quantummore » chemical methods. The computed ground-state geometry is in excellent agreement with the experimental structure determined by SCXRD. The calculated total bond order (2.75) is consistent with the presence of an electron-rich triple bond and is similar to the one found for Re 2Cl 4(PMe 3) 4. The electronic absorption spectrum of Re 2Br 4(PMe 3) 4 was recorded in benzene and shows a series of low-intensity bands in the range 10 000–26 000 cm –1. The absorption bands were assigned based on calculations of the excitation energies with the multireference wave functions followed by second-order perturbation theory using the CASSCF/CASPT2 method. As a result, calculations predict that the lowest energy band corresponds to the δ* → σ* transition, while the next higher energy bands were attributed to the δ* → π*, δ → σ*, and δ → π* transitions.« less

  13. Pregnane X receptor-dependent induction of the CYP3A4 gene by o,p'-1,1,1,-trichloro-2,2-bis (p-chlorophenyl)ethane.

    PubMed

    Medina-Díaz, Irma M; Arteaga-Illán, Georgina; de León, Mario Bermudez; Cisneros, Bulmaro; Sierra-Santoyo, Adolfo; Vega, Libia; Gonzalez, Frank J; Elizondo, Guillermo

    2007-01-01

    CYP3A4, the predominant cytochrome P450 (P450) expressed in human liver and intestine, contributes to the metabolism of approximately half the drugs in clinical use today. CYP3A4 catalyzes the 6beta-hydroxylation of a number of steroid hormones and is involved in the bioactivation of environmental procarcinogens. The expression of CYP3A4 is affected by several stimuli, including environmental factors such as insecticides and pesticides. The o,p'-1,1,1,-trichloro-2,2-bis (p-chlorophenyl)ethane (DDT) isomer of DDT comprises approximately 20% of technical grade DDT, which is an organochloride pesticide. We have recently shown that o,p'-DDT exposure increases CYP3A4 mRNA levels in HepG2 cells. To determine the mechanism by which o,p'-DDT induces CYP3A4 expression, transactivation and electrophoretic mobility shift assays were carried out, revealing that o,p'-DDT activates the CYP3A4 gene promoter through the pregnane X receptor (PXR). CYP3A4 gene promoter activation resulted in both an increase in CYP3A4 mRNA levels and an increase in the total CYP3A4 activity in HepG2 cells. We also observed induction of CYP3A4 and mouse Cyp3a11 mRNA in the intestine of CYP3A4-transgenic mice after exposure to 1 mg/kg o,p'-DDT. At higher doses, a decrease of CYP3A4 inducibility was observed together with an increase in levels of interleukin 6 mRNA, a proinflammatory cytokine that strongly represses CYP3A4 transcription. The present study indicates that regulation of other genes under PXR control may be altered by o,p'-DDT exposure.

  14. Development of a new fluorescent probe: 1,3,5,7-tetramethyl-8-(4'-aminophenyl)-4,4-difluoro-4-bora-3a,4a-diaza- s-indacence for the determination of trace nitrite

    NASA Astrophysics Data System (ADS)

    Li, Mengling; Wang, Hong; Zhang, Xian; Zhang, Hua-shan

    2004-03-01

    A new fluorescent probe, 1,3,5,7-tetramethyl-8-(4'-aminophenyl)-4,4-difluoro-4-bora-3a,4a-diaza- s-indacence (TMABODIPY) has been developed for the determination of trace nitrite in terms of the reaction of nitrite with TMABODIPY first in acidic solution and then in alkaline solution to form diazotate, a stable and highly fluorescent reagent. The method offered the advantage of specificity, sensitivity and simplicity. The linear calibration range for nitrite was 8-300 nmol l -1 s with a 3 σ detection limit of 0.65 nmol l -1. The proposed method has been applied to monitor the trace nitrite in drinking water and vegetable without extraction.

  15. p38 MAP kinase inhibitors. Part 3: SAR on 3,4-dihydropyrimido[4,5-d]pyrimidin-2-ones and 3,4-dihydropyrido[4,3-d]pyrimidin-2-ones.

    PubMed

    Natarajan, Swaminathan R; Wisnoski, David D; Thompson, James E; O'Neill, Edward A; O'Keefe, Stephen J

    2006-08-15

    p38 inhibitors based on 3,4-dihydropyrimido[4,5-d]pyrimidin-2-one and 3,4-dihydropyrido[4,3-d]pyrimidin-2-one platforms were synthesized and preliminary SAR explored. Among the pyrimido-pyrimidones the emergence of two sub-types of analogs-C7-amino-pyrimidines such as 24 and C7-amino-piperidines such as 42-characterized with good p38 inhibition and better off-target profiles in terms of ion channel activities was significant. Representative compound 54 in the pyrido-pyrimidone class was found to be equipotent with corresponding analog in the quinazolinone series.

  16. SPR and electrochemical analyses of interactions between CYP3A4 or 3A5 and cytochrome b5

    NASA Astrophysics Data System (ADS)

    Gnedenko, O. V.; Yablokov, E. O.; Usanov, S. A.; Mukha, D. V.; Sergeev, G. V.; Bulko, T. V.; Kuzikov, A. V.; Moskaleva, N. E.; Shumyantseva, V. V.; Ivanov, A. S.; Archakov, A. I.

    2014-02-01

    The combination of SPR biosensor with electrochemical analysis was used for the study of protein-protein interaction between cytochromes CYP3A4 or 3А5 and cytochromes b5: the microsomal, mitochondrial forms of this protein, and 2 ≪chimeric≫ proteins. Kinetic constants of CYP3A4 and CYP3А5 complex formation with cytochromes b5 were determined by the SPR biosensor. Essential distinction between CYP3A4 and CYP3A5 was observed upon their interactions with mitochondrial cytochrome b5. The electrochemical analysis of CYP3A4, CYP3A5, and cytochromes b5 immobilized on screen printed graphite electrodes modified with membranous matrix revealed that these proteins have very close reduction potentials -0.435 to -0.350 V (vs. Ag/AgCl).

  17. Unusual ion UO(4)(-) formed upon collision induced dissociation of [UO(2)(NO(3))(3)](-), [UO(2)(ClO(4))(3)](-), [UO(2)(CH(3)COO)(3)](-) ions.

    PubMed

    Sokalska, Marzena; Prussakowska, Małgorzata; Hoffmann, Marcin; Gierczyk, Błazej; Frański, Rafał

    2010-10-01

    The following ions [UO(2)(NO(3))(3)](-), [UO(2)(ClO(4))(3)](-), [UO(2)(CH(3)COO)(3)](-) were generated from respective salts (UO(2)(NO(3))(2), UO(2)(ClO(4))(3), UO(2)(CH(3)COO)(2)) by laser desorption/ionization (LDI). Collision induced dissociation of the ions has led, among others, to the formation of UO(4)(-) ion (m/z 302). The undertaken quantum mechanical calculations showed this ion is most likely to possess square planar geometry as suggested by MP2 results or strongly deformed geometry in between tetrahedral and square planar as indicated by DFT results. Interestingly, geometrical parameters and analysis of electron density suggest it is an U(VI) compound, in which oxygen atoms bear unpaired electron and negative charge. Copyright © 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

  18. A new synthetic approach to functionalize pyrimido[4,5-b]quinoline-2,4(1H,3H)-diones via a three-component one-pot reaction.

    PubMed

    Aknin, Karen; Desbène-Finck, Stéphanie; Helissey, Philippe; Giorgi-Renault, Sylviane

    2010-02-01

    Functionalized pyrimido[4,5-b]quinoline-2,4 (1H,3H)-diones were synthesized by a three-component one-pot reaction involving barbituric acid, aldehydes, and anilines. The use of commercially available anilines allowed the facile syntheses of pyrimido[4,5-b]quinolinediones substituted in all the positions on the benzene ring with electron donor or electron withdrawing groups. This straightforward method circumvents the preparation of unstable substituted 2-aminobenzaldehydes that limits the scope of previously described syntheses. Furthermore, access to the 5-substituted derivatives is now also possible starting from aliphatic or aromatic aldehydes. Our strategy and methodology offer significant and practical improvements over other methodologies.

  19. Identification of epoxybergamottin as a CYP3A4 inhibitor in grapefruit peel.

    PubMed

    Wangensteen, H; Molden, E; Christensen, H; Malterud, K E

    2003-02-01

    The oral availability of many drugs metabolised by the enzyme cytochrome P(450) 3A4 (CYP3A4) is increased if co-administered with grapefruit juice. Extracts from grapefruit peel have also demonstrated inhibitory activity and, during commercial manufacturing of grapefruit juice, inhibitory components might be squeezed into the juice from the peel. Thus, the aim of this in vitro study was to identify CYP3A4 inhibitors in grapefruit peel. Grapefruit peel was extracted with diethyl ether, and the extract was further fractionated by normal-phase chromatography. Fractions demonstrating significant CYP3A4 inhibitory activity, as measured by the relative reduction in N-demethylation of diltiazem in transfected human liver epithelial cells, were subsequently separated by preparative thin-layer chromatography. Constituents of the fractions and isolated compounds were identified by nuclear magnetic resonance spectroscopy. Analysis of diltiazem and N-demethyl-diltiazem was performed using high-performance liquid chromatography. Of the identified components in grapefruit peel, only epoxybergamottin demonstrated a concentration-dependent inhibition of the CYP3A4-mediated N-demethylation of diltiazem. The IC(50) value was calculated to be 4.2+/-1.1 micro M. Coumarins without the furan ring and flavonoids isolated from grapefruit peel did not interfere with the metabolism of diltiazem. The results indicated the presence of other CYP3A4 inhibitors in grapefruit peel, but these agents were lost during the purification process excluding their identification. The furanocoumarin epoxybergamottin, present in grapefruit peel, is an inhibitor of CYP3A4. In commercial manufacturing of grapefruit juice, epoxybergamottin is possibly distributed into the juice. During manufacturing, however, epoxybergamottin may be hydrolysed to 6',7'-dihydroxybergamottin, which has been suggested as an important CYP3A4 inhibitor in grapefruit juice.

  20. 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.

  1. CCl 4 chemistry on the reduced selvedge of a α-Fe 2O 3(0 0 0 1) surface: a scanning tunneling microscopy study

    NASA Astrophysics Data System (ADS)

    Rim, Kwang Taeg; Fitts, Jeffrey P.; Müller, Thomas; Adib, Kaveh; Camillone, Nicholas; Osgood, Richard M.; Joyce, S. A.; Flynn, George W.

    2003-09-01

    Scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) were used to study the degradation of CCl 4 on the reduced selvedge of a natural single crystal α-Fe 2O 3(0 0 0 1) surface in ultrahigh vacuum. Before exposure to CCl 4, STM images indicate that approximately 85% of the reduced surface exhibits a Fe 3O 4(1 1 1) 2 × 2 termination, while the remaining 15% is terminated by 1 × 1 and superstructure phases. Images obtained after room temperature dosing with CCl 4 and subsequent flashing to 600 K reveal that chlorine atoms are adsorbed only on surface regions with the Fe 3O 4(1 1 1) 2 × 2 termination, not on 1 × 1 and superstructure regions. Chlorine atoms from dissociative adsorption of CCl 4 are observed to occupy two distinct positions located atop lattice protrusions and in threefold oxygen vacancy sites. However, in companion chemical labeling experiments, chlorine atoms provided by room temperature, dissociative Cl 2 adsorption on this surface are found to occupy sites atop lattice protrusions exclusively. The clear dissimilarity in STM feature shape and brightness at the two distinct chlorine adsorption sites arising from CCl 4 dissociation as well as the results of the Cl 2 chemical labeling experiments are best explained via reactions on a Fe 3O 4(1 1 1) 2 × 2 selvedge terminated by a 1/4 monolayer of tetrahedrally coordinated iron atoms. On this surface, adsorption atop an iron atom occurs for both the CCl 4 and Cl 2 dissociative reactions. A second adsorption site, assigned as binding to second layer iron atoms left exposed following surface oxygen atom abstraction resulting in the formation of phosgene (COCl 2), only appears in the case of reaction with CCl 4. The reaction mechanism and active site requirements for CCl 4 degradation on iron oxide surfaces are discussed in light of this evidence and in the context of our previously reported results from Auger electron spectroscopy (AES), LEED, temperature-programmed desorption

  2. Degradation of 4-chloro-3-nitrophenol via a novel intermediate, 4-chlororesorcinol by Pseudomonas sp. JHN

    PubMed Central

    Arora, Pankaj Kumar; Srivastava, Alok; Singh, Vijay Pal

    2014-01-01

    A 4-chloro-3-nitrophenol (4C3NP)-mineralizing bacterium, Pseudomonas sp. JHN was isolated from a waste water sample collected from a chemically-contaminated area, India by an enrichment method. Pseudomonas sp. JHN utilized 4C3NP as a sole carbon and energy source and degraded it with the release of stoichiometric amounts of chloride and nitrite ions. Gas chromatography and gas chromatography-mass spectrometry detected 4-chlororesorcinol as a major metabolite of the 4C3NP degradation pathway. Inhibition studies using 2,2′-dipyridyl showed that 4-chlororesorcinol is a terminal aromatic compound in the degradation pathway of 4C3NP. The activity for 4C3NP-monooxygenase was detected in the crude extracts of the 4C3NP-induced JHN cells that confirmed the formation of 4-chlororesorcinol from 4C3NP. The capillary assay showed that Pseudomonas sp. JHN exhibited chemotaxis toward 4C3NP. The bioremediation capability of Pseudomonas sp. JHN was monitored to carry out the microcosm experiments using sterile and non-sterile soils spiked with 4C3NP. Strain JHN degraded 4C3NP in sterile and non-sterile soil with same degradation rates. This is the first report of (i) bacterial degradation and bioremediation of 4C3NP, (ii) formation of 4-chlororesorcinol in the degradation pathway of 4C3NP, (iii) bacterial chemotaxis toward 4C3NP. PMID:24667329

  3. Synthesis and anti-HIV activity of novel 3-substituted phenyl-6,7-dimethoxy-3a,4-dihydro-3H-indeno[1,2-c]isoxazole analogues.

    PubMed

    Ali, Mohamed A; Ismail, Rusli; Choon, Tan S; Yoon, Yeong K; Wei, Ang C; Pandian, Suresh; Samy, Jeyabalan G; De Clercq, Eric; Pannecouque, Christophe

    2011-01-01

    A series of novel 3-(substituted phenyl)-6,7-dimethoxy-3a,4-dihydro-3H-indeno[1,2-c]isoxazole analogues were synthesized by the reaction of 5,6-dimethoxy-2-[(E)-1-phenylmethylidene]-1-indanone with hydroxylamine hydrochloride. The title compounds were tested for their in vitro anti-HIV activity. Among the compounds, (4g) showed a promising anti-HIV activity in the in vitro testing against IIIB and ROD strains. The IC50 of both IIIB and ROD were found to be 9.05 microM and > 125 microM, respectively.

  4. Synthesis, Characterization and Cytotoxicity of Novel Multifunctional Fe3O4@SiO2@GdVO4:Dy3+ Core-Shell Nanocomposite as a Drug Carrier

    PubMed Central

    Li, Bo; Fan, Huitao; Zhao, Qiang; Wang, Congcong

    2016-01-01

    In this study, multifunctional Fe3O4@SiO2@GdVO4:Dy3+ nanocomposites were successfully synthesized via a two-step method. Their structure, luminescence and magnetic properties were characterized by X-ray diffraction (XRD), scanning electronic microscope (SEM), transmission electron microscopy (TEM), photoluminescence (PL) spectra and vibrating sample magnetometer (VSM). The results indicated that the as-prepared multifunctional composites displayed a well-defined core-shell structure. The composites show spherical morphology with a size distribution of around 360 nm. Additionally, the composites exhibit high saturation magnetization (20.40 emu/g) and excellent luminescence properties. The inner Fe3O4 cores and the outer GdVO4:Dy3+ layers endow the composites with good responsive magnetic properties and strong fluorescent properties, which endow the nanoparticles with great potential applications in drug delivery, magnetic resonance imaging, and marking and separating of cells in vitro. PMID:28773275

  5. Tunable-color luminescence via energy transfer in NaCa13/18Mg5/18PO4:A (A = Eu2+/Tb3+/Mn2+, Dy3+) phosphors for solid state lighting.

    PubMed

    Li, Kai; Fan, Jian; Mi, Xiaoyun; Zhang, Yang; Lian, Hongzhou; Shang, Mengmeng; Lin, Jun

    2014-11-17

    A series of NaCa13/18Mg5/18PO4(NCMPO):A (A = Eu(2+)/Tb(3+)/Mn(2+), Dy(3+)) phosphors have been prepared by the high-temperature solid-state reaction method. The X-ray diffraction (XRD) and Rietveld refinement, X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), cathodoluminescence (CL), decay lifetimes, and PL quantum yields (QYs) were utilized to characterize the phosphors. The pure crystalline phase of as-prepared samples has been demonstrated via XRD measurement and Rietveld refinements. XPS reveals that the Eu(2+)/Tb(3+)/Mn(2+) can be efficiently doped into the crystal lattice. NCMPO:Eu(2+)/Tb(3+)/Mn(2+) phosphors can be effectively excited under UV radiation, which show tunable color from purple-blue to red including white emission based on energy transfer from Eu(2+) to Tb(3+)/Mn(2+) ions. Under low-voltage electron beam bombardment, the NCMPO:A (A = Eu(2+)/Tb(3+)/Mn(2+), Dy(3+)) display their, respectively, characteristic emissions with different colors, and the CL spectrum of NCMPO:0.04Tb(3+) has the comparable intensity to the ZnO:Zn commercial product. In addition, the calculated CIE coordinate of NCMPO:0.04Tb(3+) (0.252, 0.432) is more saturated than it (0.195, 0.417). These results reveal that NCMPO:A (A = Eu(2+)/Tb(3+)/Mn(2+), Dy(3+)) may be potential candidate phosphors for WLEDs and FEDs.

  6. Identification of high-risk Listeria monocytogenes serotypes in lineage I (serotype 1/2a, 1/2c, 3a and 3c) using multiplex PCR

    USDA-ARS?s Scientific Manuscript database

    Aims: Using molecular subtyping techniques, Listeria monocytogenes is divided into three major phylogenetic lineages, and a multiplex PCR method can differentiate five L. monocytogenes subgroups: 1/2a-3a, 1/2c-3c, 1/2b-3b-7, 4b-4d-4e, and 4a-4c. In the current study, we conducted genome comparison...

  7. Rational construction of a 3D hierarchical NiCo2O4/PANI/MF composite foam as a high-performance electrode for asymmetric supercapacitors.

    PubMed

    Cui, Fen; Huang, Yunpeng; Xu, Le; Zhao, Yan; Lian, Jiabiao; Bao, Jian; Li, Huaming

    2018-04-19

    A 3D hierarchical NiCo2O4/PANI/MF composite foam with a macroporous 3D skeleton, a conductive PANI coating and highly electrochemically active NiCo2O4 nanosheets is synthesized as a lightweight and low-cost electrode material. Due to the collaborative contribution of all the components, the prepared composite foam exhibits excellent capacitive performances when incorporated into an asymmetric supercapacitor.

  8. Investigations on the synthesis and pharmacological properties of 4-alkoxy-2-[2-hydroxy-3-(4-aryl-1-piperazinyl)propyl]-6-methyl-1H-pyrrolo[3,4-c]pyridine-1,3(2H)-diones.

    PubMed

    Sladowska, Helena; Filipek, Barbara; Szkatuła, Dominika; Sabiniarz, Aleksandra; Kardasz, Małgorzata; Potoczek, Joanna; Sieklucka-Dziuba, Maria; Rajtar, Grazyna; Kleinrok, Zdzisław; Lis, Tadeusz

    2002-11-01

    Synthesis of 2-[2-hydroxy-3-(4-aryl-1-piperazinyl)propyl] derivatives of 4-alkoxy-6-methyl-1H-pyrrolo[3,4-c]pyridine-1,3(2H)-diones (8-12) is described. The chlorides used in the above synthesis can exist in two isomeric forms: chain (18-20) and cyclic (19a, 20a). The compounds 8-12 exhibited potent analgesic activity which was superior than that of acetylsalicylic acid in two different tests. Most of the investigated imides suppressed significantly spontaneous locomotor activity in mice.

  9. Design, synthesis, radiolabeling and in vivo evaluation of carbon-11 labeled N-[2-[4-(3-cyanopyridin-2-yl)piperazin-1-yl]ethyl]-3-methoxybenzamide, a potential Positron Emission Tomography tracer for the dopamine D4 receptors

    PubMed Central

    Lacivita, Enza; De Giorgio, Paola; Lee, Irene T.; Rodeheaver, Sean I.; Weiss, Bryan A.; Fracasso, Claudia; Caccia, Silvio; Berardi, Francesco; Perrone, Roberto; Zhang, Ming-Rong; Maeda, Jun; Higuchi, Makoto; Suhara, Tetsuya; Schetz, John A.; Leopoldo, Marcello

    2010-01-01

    Here we describe the design, synthesis, physicochemical, and pharmacological evaluation of D4 dopamine receptor ligands related to N-[2-[4-(4-chlorophenyl)piperazin-1-yl]ethyl]-3-methoxybenzamide (2). Structural features were incorporated to increase affinity for the target receptor, to improve selectivity over D2 and sigma1 receptors, to enable labeling with carbon-11 or fluorine-18, and to adjust lipophilicity within the range considered optimal for brain penetration and low nonspecific binding. Compounds 7 and 13 showed the overall best characteristics: nanomolar affinity for the D4 receptor, > 100-fold selectivity over D2 and D3 dopamine receptor 5-HT1A, 5-HT2A and 5-HT2C serotonin receptors and sigma1 receptors, and logP = 2.37–2.55. Following intraperitoneal administration, both compounds rapidly entered the central nervous system. The methoxy of N-[2-[4-(3-cyanopyridin-2-yl)piperazin-1-yl]ethyl]-3-methoxybenzamide (7) was radiolabelled with carbon-11 and subjected to PET analysis in non-human primate. [11C]7 time-dependently accumulated to saturation in the posterior eye in the region of the retina, a tissue containing a high density of D4 receptors. PMID:20873719

  10. Characterization of a chemical artifact in the liquid chromatographic determination of 3-butyn-2-one using the 2,4-dinitrophenylhydrazine method.

    PubMed

    Vogel, M; Pötter, W; Karst, U

    2000-07-21

    This study reports the identification of a chemical artifact occurring in the liquid chromatographic analysis of 3-butyn-2-one by means of the 2,4-dinitrophenylhydrazine (DNPH) method. Besides the expected derivatization reaction to the corresponding butynone DNPhydrazone, a rearrangement was observed, thus leading to the formation of 3-methyl-1-(2',4'-dinitrophenyl)pyrazol (DNPP). Although the rearrangement product and the hydrazone can easily be separated by means of liquid chromatography, problems arise from coelution of the pyrazol with the formaldehyde DNPhydrazone. Identification of the artifact by means of UV-Vis spectroscopy using dual wavelength or diode array detection is discussed.

  11. 2-chloroethanol formation as evidence for a 2-chloroethyl alkylating intermediate during chemical degradation of 1-(2-chloroethyl)-3-cyclohexyl-1-nitrosourea and 1-(2-chloroethyl)-3-(trans-4-methylcyclohexyl)-1-nitrosourea.

    PubMed

    Reed, D J; May, H E; Boose, R B; Gregory, K M; Beilstein, M A

    1975-03-01

    Chemical degradation of 1-(2-chloroethyl)-3-cyclohexyl-1-nitrosourea or 1-(2-chloroethyl)-3-(trans-4-methylcyclohexyl)-1-nitrosourea in buffer under physiological conditions resulted in the formation of a significant quantity of 2-chlorethanol (18 to 25% of the initial nitrosourea concentration). Other degradation products observed included acetaldehyde (5 to 10%), vinyl chloride (1 to 2%), ethylene (1 to 2%), and cyclohexylamine (32%), but not 1,3-dicyclohexylurea. The 2-chlorethyl moiety of 1-(2-chloroethyl)-3-cyclohexyl-1-nitrosourea was trapped with halide ions, CI-, BR-, and I-, to form the corresponding dihaloethanes which were identified by gas chromatography-mass spectrometry techniques. High-pressure liquid chromatographic procedures were developed for the separation and quantiation of the nitrosoureas and many of their degradation products. It is postulated that a new mode of 1(2-chloreoethyl)-3-cyclohexyl-1-nitrosourea and 1-(2-chloroethyl)-3-(trans-4-methylcyclohexyl)-1-nitrosourea degradation can occur that is not the loss of the chloro group as chloride ion, but the loss of the N-3 hydrogen as a proton. Then the corresponding isocyanate and 2-chloroethyidiazene hydroxide are formed, with the latter intermidiate becoming an alkylating species, possibly in part as a 2-chloroethyl carbonium ion.

  12. NIR emitting K2SrCl4:Eu2+, Nd3+ phosphor as a spectral converter for CIGS solar cell

    NASA Astrophysics Data System (ADS)

    Tawalare, P. K.; Bhatkar, V. B.; Omanwar, S. K.; Moharil, S. V.

    2018-05-01

    Intense near-infrared emitting phosphor K2SrCl4:Eu2+,Nd3+ with various concentrations of Nd3+ were synthesized. These are characterized with X-ray diffraction, reflectance, photoluminescence emission and photoluminescence excitation spectroscopy, PL lifetime measurements. The emission can be excited by a broad band in near ultra violet region as a consequence of Eu2+→Nd3+ energy transfer. The efficiency of Eu2+→Nd3+ energy transfer is as high as 95%. Fluorescence decay curves for Eu2+ doped samples are almost exponential and described by τ = 500 ns. Eu2+ lifetimes are shortened after Nd3+ doping. Near infrared Emission intensity is limited by Nd3+→Nd3+ energy transfer and the consequent concentration quenching. Nd3+ emission matches well with the spectral response of CIGS and CIS solar cells. Absorption of near ultra violet radiations followed by conversion to near infrared indicates the potential application in solar photovoltaics.

  13. Nedd4 is a Specific E3 Ubiquitin Ligase for the NMDA Receptor Subunit GluN2D

    PubMed Central

    Gautam, Vivek; Trinidad, Jonathan C.; Rimerman, Ronald A.; Costa, Blaise M.; Burlingame, Alma L.; Monaghan, Daniel T.

    2013-01-01

    NMDA receptors are a family of glutamate-gated ion channels that regulate various CNS functions such as synaptic plasticity and learning. However hypo-or hyper-activation of NMDA receptors is critically involved in many neurological and psychiatric conditions such as pain, stroke, epilepsy, neurodegeneration, schizophrenia, and depression. Thus, it is important to identify mechanisms (such as by targeted ubiquitination) that regulate the levels of individual subtypes of NMDA receptors. In this study, we used a series of tagged, carboxy terminal constructs of GluN2D to identify associating proteins from rat brain. Of seven different GluN2D C-terminal fragments used as bait, only the construct containing amino acids 983-1097 associated with an E3 ligase, Nedd4. A direct interaction between GluN2D and Nedd4 was confirmed both in vivo and in vitro. This association is mediated by an interaction between GluN2D's C-terminal PPXY motif and the 2nd and 3rd WW domains of Nedd4. Of the four GluN2 subunits, Nedd4 directly interacted with GluN2D and also weakly with GluN2A. Nedd4 coexpression with GluN2D enhances GluN2D ubiquitination and reduces GluN1/GluN2D NMDA receptor responses. These results identify Nedd4 as a novel binding partner for GluN2D and suggest a mechanism for the regulation of NMDA receptors that contains GluN2D subunit through ubiquitination-dependent downregulation. PMID:23639431

  14. Novel Tandem Biotransformation Process for the Biosynthesis of a Novel Compound, 4-(2,3,5,6-Tetramethylpyrazine-1)-4′-Demethylepipodophyllotoxin▿

    PubMed Central

    Tang, Ya-Jie; Zhao, Wei; Li, Hong-Mei

    2011-01-01

    According to the structure of podophyllotoxin and its structure-function relationship, a novel tandem biotransformation process was developed for the directional modification of the podophyllotoxin structure to directionally synthesize a novel compound, 4-(2,3,5,6-tetramethylpyrazine-1)-4′-demethylepipodophyllotoxin (4-TMP-DMEP). In this novel tandem biotransformation process, the starting substrate of podophyllotoxin was biotransformed into 4′-demethylepipodophyllotoxin (product 1) with the demethylation of the methoxyl group at the 4′ position by Gibberella fujikuroi SH-f13, which was screened out from Shennongjia prime forest humus soil (Hubei, China). 4′-Demethylepipodophyllotoxin (product 1) was then biotransformed into 4′-demethylpodophyllotoxone (product 2) with the oxidation of the hydroxyl group at the 4 position by Alternaria alternata S-f6, which was screened out from the gathered Dysosma versipellis plants in the Wuhan Botanical Garden, Chinese Academy of Sciences. Finally, 4′-demethylpodophyllotoxone (product 2) and ligustrazine were linked with a transamination reaction to synthesize the target product 4-TMP-DMEP (product 3) by Alternaria alternata S-f6. Compared with podophyllotoxin (i.e., a 50% effective concentration [EC50] of 529 μM), the EC50 of 4-TMP-DMEP against the tumor cell line BGC-823 (i.e., 0.11 μM) was significantly reduced by 5,199 times. Simultaneously, the EC50 of 4-TMP-DMEP against the normal human proximal tubular epithelial cell line HK-2 (i.e., 0.40 μM) was 66 times higher than that of podophyllotoxin (i.e., 0.006 μM). Furthermore, compared with podophyllotoxin (i.e., log P = 0.34), the water solubility of 4-TMP-DMEP (i.e., log P = 0.66) was significantly enhanced by 94%. For the first time, the novel compound 4-TMP-DMEP with superior antitumor activity was directionally synthesized from podophyllotoxin by the novel tandem biotransformation process developed in this work. PMID:21398491

  15. Rate coefficients for the reactions of C2(a(3)Pi(u)) and C2(X(1)Sigma(g)(+)) with various hydrocarbons (CH4, C2H2, C2H4, C2H6, and C3H8): a gas-phase experimental study over the temperature range 24-300 K.

    PubMed

    Páramo, Alejandra; Canosa, André; Le Picard, Sébastien D; Sims, Ian R

    2008-10-02

    The kinetics of reactions of C2(a(3)Pi(u)) and C2(X(1)Sigma(g)(+)) with various hydrocarbons (CH4, C2H2, C2H4, C2H6, and C3H8) have been studied in a uniform supersonic flow expansion over the temperature range 24-300 K. Rate coefficients have been obtained by using the pulsed laser photolysis-laser induced fluorescence technique, where both radicals were produced at the same time but detected separately. The reactivity of the triplet state was found to be significantly lower than that of the singlet ground state for all reactants over the whole temperature range of the study. Whereas C2(X(1)Sigma(g)(+)) reacts with a rate coefficient close to the gas kinetic limit with all hydrocarbons studied apart from CH4, C2(a(3)Pi(u)) appears to be more sensitive to the molecular and electronic structure of the reactant partners. The latter reacts at least one order of magnitude faster with unsaturated hydrocarbons than with alkanes, and the rate coefficients increase very significantly with the size of the alkane. Results are briefly discussed in terms of their potential astrophysical impact.

  16. Binding of [3H]MSX-2 (3-(3-hydroxypropyl)-7-methyl-8-(m-methoxystyryl)-1-propargylxanthine) to rat striatal membranes--a new, selective antagonist radioligand for A(2A) adenosine receptors.

    PubMed

    Müller, C E; Maurinsh, J; Sauer, R

    2000-01-01

    The present study describes the preparation and binding properties of a new, potent, and selective A(2A) adenosine receptor (AR) antagonist radioligand, [3H]3-(3-hydroxypropyl)-7-methyl-8-(m-methoxystyryl)-1-propargy lxanth ine ([3H]MSX-2). [3H]MSX-2 binding to rat striatal membranes was saturable and reversible. Saturation experiments showed that [3H]MSX-2 labeled a single class of binding sites with high affinity (K(d)=8.0 nM) and limited capacity (B(max)=1.16 fmol.mg(-1) of protein). The presence of 100 microM GTP, or 10 mM magnesium chloride, respectively, had no effect on [3H]MSX-2 binding. AR agonists competed with the binding of 1 nM [3H]MSX-2 with the following order of potency: 5'-N-ethylcarboxamidoadenosine (NECA)>2-[4-(carboxyethyl)phenylethylamino]-5'-N-ethylcarboxami doaden osine (CGS-21680)>2-chloroadenosine (2-CADO)>N(6)-cyclopentyladenosine (CPA). AR antagonists showed the following order of potency: 8-(m-bromostyryl)-3, 7-dimethyl-1-propargylxanthine (BS-DMPX)>1, 3-dipropyl-8-cyclopentylxanthine (DPCPX)>(R)-5, 6-dimethyl-7-(1-phenylethyl)-2-(4-pyridyl)-7H-pyrrolo[2, 3-d]pyrimidine-4-amine (SH-128)>3,7-dimethyl-1-propargylxanthine (DMPX)>caffeine. The K(i) values for antagonists were in accordance with data from binding studies with the agonist radioligand [3H]CGS21680, while agonist affinities were 3-7-fold lower. [3H]MSX-2 is a highly selective A(2A) AR antagonist radioligand exhibiting a selectivity of at least two orders of magnitude versus all other AR subtypes. The new radioligand shows high specific radioactivity (85 Ci/mmol, 3150 GBq/mmol) and acceptable nonspecific binding at rat striatal membranes of 20-30%, at 1 nM.

  17. [Effects of acute exposure to high altitude on hepatic function and CYP1A2 and CYP3A4 activities in rats].

    PubMed

    Li, Wenbin; Jia, Zhengping; Xie, Hua; Zhang, Juanhong; Wang, Yanling; Hao, Ying; Wang, Rong

    2014-07-01

    To investigate the changes in hepatic functions and activities of CYP1A2 and CYP3A4 in rats after acute exposure to high altitude. Twelve healthy male Wistar rats were randomly divided into control group and exposure group for acute exposure to normal and high altitude (4010 m) environment. Blood samples were collected from the vena orbitalis posterior for detection of the hepatic function. Hepatic pathologies of the rats were examined microscopically with HE staining. Liver microsomes were extracted by differential centrifugation to assess the activities of CYP1A2 and 3A4 using P450-GloTM kit. In rats with acute exposure to high altitude, AST, ALT, and ALP all increased significantly by 48.50%, 47.90%, and 103.02%, respectively, and TP decreased significantly by 17.80% as compared with those in rats maintained in normal altitude environment (P<0.05). Pathological examination of the liver revealed edema of the central vein of the liver and hepatocyte karyopyknosis in rats after acute exposure to high altitude, which also resulted in significantly lowered activities of CYP1A2 and 3A4 in the liver (by 96.56% and 43.53%, respectively). Acute exposure to high altitude can cause obvious liver injuries and lowered activities of CYP1A2 and 3A4 in rats to severely affect drug metabolism in the liver and result in increased concentration, prolonged half-life and reduced clearance of drugs.

  18. Identification and SAR of novel diaminopyrimidines. Part 1: The discovery of RO-4, a dual P2X(3)/P2X(2/3) antagonist for the treatment of pain.

    PubMed

    Carter, David S; Alam, Muzaffar; Cai, Haiying; Dillon, Michael P; Ford, Anthony P D W; Gever, Joel R; Jahangir, Alam; Lin, Clara; Moore, Amy G; Wagner, Paul J; Zhai, Yansheng

    2009-03-15

    P2X purinoceptors are ligand-gated ion channels whose endogenous ligand is ATP. Both the P2X(3) and P2X(2/3) receptor subtypes have been shown to play an important role in the regulation of sensory function and dual P2X(3)/P2X(2/3) antagonists offer significant potential for the treatment of pain. A high-throughput screen of the Roche compound collection resulted in the identification of a novel series of diaminopyrimidines; subsequent optimization resulted in the discovery of RO-4, a potent, selective and drug-like dual P2X(3)/P2X(2/3) antagonist.

  19. In vivo effects of goldenseal, kava kava, black cohosh, and valerian on human cytochrome P450 1A2, 2D6, 2E1, and 3A4 phenotypes

    PubMed Central

    Gardner, Stephanie F.; Hubbard, Martha A.; Williams, D. Keith; Gentry, W. Brooks; Khan, Ikhlas A.; Shah., Amit

    2007-01-01

    Objectives Phytochemical-mediated modulation of cytochrome P-450 activity may underlie many herb-drug interactions. Single time-point, phenotypic metabolic ratios were used to determine whether long-term supplementation of goldenseal (Hydrastis canadensis), black cohosh (Cimicifuga racemosa), kava kava (Piper methysticum), or valerian (Valeriana officinalis) extracts affected CYP1A2, CYP2D6, CYP2E1, or CYP3A4/5 activity. Methods Twelve healthy volunteers (6 females) were randomly assigned to receive goldenseal, black cohosh, kava kava, or valerian for 28 days. For each subject, a 30-day washout period was interposed between each supplementation phase. Probe drug cocktails of midazolam and caffeine, followed 24 hours later by chlorzoxazone and debrisoquine were administered before (baseline) and at the end of supplementation. Pre- and post-supplementation phenotypic trait measurements were determined for CYP3A4/5, CYP1A2, CYP2E1, and CYP2D6 using 1-hydroxymidazolam/midazolam serum ratios (1-hour sample), paraxanthine/caffeine serum ratios (6-hour sample), 6-hydroxychlorzoxazone/chlorzoxazone serum ratios (2-hour sample), and debrisoquine urinary recovery ratios (8-hour collection), respectively. The content of purported “active” phytochemicals was determined for each supplement. Results Comparisons of pre- and post-supplementation phenotypic ratio means revealed significant inhibition (~40%) of CYP2D6 (difference = −0.228; 95% CI = −0.268 to −0.188) and CYP3A4/5 (difference = −1.501; 95% CI = −1.840 to −1.163) activity for goldenseal. Kava produced significant reductions (~40%) in CYP2E1 only (difference = −0.192; 95% CI = −0.325 to −0.060). Black cohosh also exhibited statistically significant inhibition of CYP2D6 (difference = −0.046; 95% CI = −0.085 to −0.007), but the magnitude of the effect (~7%) did not appear clinically relevant. No significant changes in phenotypic ratios were observed for valerian. Conclusions Botanical

  20. GW627368X ((N-{2-[4-(4,9-diethoxy-1-oxo-1,3-dihydro-2H-benzo[f]isoindol-2-yl)phenyl]acetyl} benzene sulphonamide): a novel, potent and selective prostanoid EP4 receptor antagonist

    PubMed Central

    Wilson, Richard J; Giblin, Gerard M P; Roomans, Susan; Rhodes, Sharron A; Cartwright, Kerri-Ann; Shield, Vanessa J; Brown, Jason; Wise, Alan; Chowdhury, Jannatara; Pritchard, Sara; Coote, Jim; Noel, Lloyd S; Kenakin, Terry; Burns-Kurtis, Cynthia L; Morrison, Valerie; Gray, David W; Giles, Heather

    2006-01-01

    N-{2-[4-(4,9-diethoxy-1-oxo-1,3-dihydro-2H-benzo[f]isoindol-2-yl)phenyl]acetyl}benzene sulphonamide (GW627368X) is a novel, potent and selective competitive antagonist of prostanoid EP4 receptors with additional human TP receptor affinity. At recombinant human prostanoid EP4 receptors expressed in HEK293 cells, GW627368X produced parallel rightward shifts of PGE2 concentration–effect (E/[A]) curves resulting in an affinity (pKb) estimate of 7.9±0.4 and a Schild slpoe not significantly different from unity. The affinity was independent of the agonist used. In rings of phenylephrine precontracted piglet saphenous vein, GW627368X (30–300 nM) produced parallel rightward displacement of PGE2 E/[A] curves (pKb=9.2±0.2; slope=1). GW627368X appears to bind to human prostanoid TP receptors but not the TP receptors of other species. In human washed platelets, GW627368X (10 μM) produced 100% inhibition of U-46619 (EC100)-induced aggregation (approximate pA2 ∼7.0). However, in rings of rabbit and piglet saphenous vein and of guinea-pig aorta GW627368X (10 μM) did not displace U-46619 E/[A] curves indicating an affinity of <5.0 for rabbit and guinea-pig prostanoid TP receptors. In functional assays GW627368X is devoid of both agonism and antagonist affinity for prostanoid CRTH2, EP2, EP3, IP and FP receptors. At prostanoid EP1 receptors, GW627368X was an antagonist with a pA2 of 6.0, and at prostanoid IP receptors the compound increased the maximum effect of iloprost by 55%. At rabbit prostanoid EP2 receptors the pA2 of GW627368X was <5.0. In competition radioligand bioassays, GW627368X had affinity for human prostanoid EP4 and TP receptors (pKi=7.0±0.2 (n=10) and 6.8 (n=2), respectively). Affinity for all other human prostanoid receptors was <5.3. GW627368X will be a valuable tool to explore the role of the prostanoid EP4 receptor in many physiological and pathological settings. PMID:16604093

  1. SCP4 Promotes Gluconeogenesis Through FoxO1/3a Dephosphorylation.

    PubMed

    Cao, Jin; Yu, Yi; Zhang, Zhengmao; Chen, Xi; Hu, Zhaoyong; Tong, Qiang; Chang, Jiang; Feng, Xin-Hua; Lin, Xia

    2018-01-01

    FoxO1 and FoxO3a (collectively FoxO1/3a) proteins regulate a wide array of cellular processes, including hepatic gluconeogenesis. Phosphorylation of FoxO1/3a is a key event that determines its subcellular location and transcriptional activity. During glucose synthesis, the activity of FoxO1/3a is negatively regulated by Akt-mediated phosphorylation, which leads to the cytoplasmic retention of FoxO1/3a. However, the nuclear phosphatase that directly regulates FoxO1/3a remains to be identified. In this study, we discovered a nuclear phosphatase, SCP4/CTDSPL2 (SCP4), that dephosphorylated FoxO1/3a and promoted FoxO1/3a transcription activity. We found that SCP4 enhanced the transcription of FoxO1/3a target genes encoding PEPCK1 and G6PC, key enzymes in hepatic gluconeogenesis. Ectopic expression of SCP4 increased, while knockdown of SCP4 inhibited, glucose production. Moreover, we demonstrated that gene ablation of SCP4 led to hypoglycemia in neonatal mice. Consistent with the positive role of SCP4 in gluconeogenesis, expression of SCP4 was regulated under pathophysiological conditions. SCP4 expression was induced by glucose deprivation in vitro and in vivo and was elevated in obese mice caused by genetic (A vy ) and dietary (high-fat) changes. Thus, our findings provided experimental evidence that SCP4 regulates hepatic gluconeogenesis and could serve as a potential target for the prevention and treatment of diet-induced glucose intolerance and type 2 diabetes. © 2017 by the American Diabetes Association.

  2. Preparation of 1,1'-dinitro-3,3'-azo-1,2,4-triazole. [1,1'-dinitro-3,3'-azo-1,2,4-triazole

    DOEpatents

    Lee, K.Y.

    1985-03-05

    A new high density composition of matter, 1,1'-dinitro-3,3'-azo-1,2,4-triazole, has been synthesized using inexpensive, commonly available compounds. This compound has been found to be an explosive, and its use as a propellant is anticipated. 1 fig., 1 tab.

  3. TiO2-based (Fe3O4, SiO2, reduced graphene oxide) magnetically recoverable photocatalysts for imazalil degradation in a synthetic wastewater.

    PubMed

    Santiago, Dunia E; Pastrana-Martínez, Luisa M; Pulido-Melián, Elisenda; Araña, Javier; Faria, Joaquim L; Silva, Adrián M T; González-Díaz, Óscar; Doña-Rodríguez, José M

    2018-03-02

    Magnetite (Fe 3 O 4 ), a core-shell material (SiO 2 @Fe 3 O 4 ), and reduced graphene oxide-Fe 3 O 4 (referred as rGO-MN) were used as supports of a specific highly active TiO 2 photocatalyst. Thermal treatments at 200 or 450 °C, different atmospheres (air or N 2 ), and TiO 2 :support weight ratios (1.0, 1.5, or 2.0) were investigated. X-ray diffractograms revealed that magnetite is not oxidized to hematite when the core-shell SiO 2 @Fe 3 O 4 material-or a N 2 atmosphere (instead of air) in the thermal treatment-was employed to prepare the TiO 2 -based catalysts (the magnetic properties being preserved). The materials treated with N 2 were first tested for degradation of imazalil (a well-known fungicide) in deionized water. The best compromise between the photocatalytic activity, magnetic separation, and Fe leached (1.61 mg L -1 , i.e., below the threshold for water reuse in irrigation) was found for the magnetic catalyst prepared with SiO 2 @Fe 3 O 4 , an intermediate TiO 2 :support ratio (1.5), and treated at 200 °C under N 2 atmosphere (i.e., SiO 2 @Fe 3 O 4 -EST-1.5-200-N 2 ). This material was then tested for the treatment of imazalil in a synthetic wastewater, SW (with a chemical composition simulating an effluent resulting from fruit postharvest activity). This SW has a pH of 4.2 and the experiments were carried out at this natural pH 0 and at neutral conditions (keeping pH at 7 along the reaction). The magnetic catalyst was more active than bare TiO 2 for the treatment of imazalil in SW at natural pH. Since Fe leaching was observed (3.53 mg L -1 ), added H 2 O 2 enhanced both imazalil degradation and mineralization. Conveniently, these catalysts can be readily recovered by using a conventional magnetic field, as demonstrated over three consecutive recycling runs. Graphical abstract % Imazalil conversion using different magnetic catalysts and comparison with bare TiO 2 .

  4. Superior performance asymmetric supercapacitors based on a directly grown commercial mass 3D Co3O4@Ni(OH)2 core-shell electrode.

    PubMed

    Tang, Chun-hua; Yin, Xuesong; Gong, Hao

    2013-11-13

    Pseudocapacitors based on fast surface Faradaic reactions can achieve high energy densities together with high power densities. Usually, researchers develop a thin layer of active materials to increase the energy density by enhancing the surface area; meanwhile, this sacrifices the mass loading. In this work, we developed a novel 3D core-shell Co3O4@Ni(OH)2 electrode that can provide high energy density with very high mass loading. Core-shell porous nanowires (Co3O4@Ni(OH)2) were directly grown on a Ni current collector as an integrated electrode/collector for the supercapacitor anode. This Co3O4@Ni(OH)2 core-shell nanoarchitectured electrode exhibits an ultrahigh areal capacitance of 15.83 F cm(-2). The asymmetric supercapacitor prototypes, assembled using Co3O4@Ni(OH)2 as the anode, reduced graphene oxide (RGO) or active carbon (AC) as the cathode, and 6 M aqueous KOH as the electrolyte, exhibit very high energy densities falling into the energy-density range of Li-ion batteries. Because of the large mass loading and high energy density, the prototypes can drive a minifan or light a bulb even though the size is very small. These results indicate that our asymmetric supercapacitors have outstanding potential in commercial applications. Systematic study and scientific understanding were carried out.

  5. Preparation, Spectroscopic Characterization, and Frontier MO Study of the Heteronuclear Luminescent [Pt(2)Au(2)(dmb)(2)(PPh(3))(4)](PF(6))(2) Cluster (dmb = 1,8-Diisocyano-p-menthane). A Cluster with a Formal Au(0)-Au(0) Bond Encapsulated inside a "Pt(2)(dmb)(2)(2+) " Fragment.

    PubMed

    Zhang, Tianle; Drouin, Marc; Harvey, Pierre D.

    1999-11-01

    The title compound is prepared from the direct reaction of Pt(2)(dba)(3) (dba = dibenzylideneacetone) and [Au(PPh(3))(2)](PF(6)) in the presence of 1,8-diisocyano-p-methane (dmb), with Pt(2)(dmb)(2)Cl(2), [Pt(4)(dmb)(4)(PPh(3))(2)](PF(6))(2), and (PPh(3))AuCl being formed as parallel products. X-ray crystallography reveals the presence of a quasi-linear PPh(3)Au-AuPPh(3) fragment encapsulated inside a "Pt(2)(dmb)(2)(2+)" ring which is axially coordinated with two PPh(3) ligands. The d(AuAu) is 2.5977(6) Å and is indicative of a strong Au-Au single bond. The IR nu(CN) data reveal that the Pt oxidation state is I, which places the Au oxidation state at 0. The PtAu distances are 2.8422(5) and 2.8082(5) Å. The Raman-active nu(Au(2)), nu(PtAu) (b(2g) + a(g)), nu(PtP), nu(AuP), and nu(PtC) are found at 121.2, approximately 100, 85.5, 162.1, 183.1, and 457.2, and 440.9 cm(-)(1), respectively. The PtAu (0.67 mdyn Å(-)(1)) and Au(2) (1.21 mdyn Å(-)(1)) force constants (F) confirm the presence of medium PtAu and strong Au(2) bonding interactions. The absorption spectra are characterized by strong bands at lambda(max) (epsilon, M(-1) cm(-1)) at 316 (32 300), 366 (37 800), and 418 nm (21 500) and lower intensity features at 516 (2860) and 655 nm (834). The cluster is luminescent at low temperatures (solid and frozen glasses), and in the solid state at room temperature, and exhibits an emission band at approximately 875 nm, and an emission lifetime, tau(e), of 4.4 +/- 0.4 ns (solvent = butyronitrile, T = 77 K).

  6. Dual-Color Fluorescence Imaging to Monitor CYP3A4 and CYP3A7 Expression in Human Hepatic Carcinoma HepG2 and HepaRG Cells

    PubMed Central

    Kubiura, Musashi; Hayashi, Ayaka; Ohbayashi, Tetsuya; Kazuki, Yasuhiro; Chesné, Christophe; Oshimura, Mitsuo; Tada, Masako

    2014-01-01

    Human adult hepatocytes expressing CYP3A4, a major cytochrome P450 enzyme, are required for cell-based assays to evaluate the potential risk of drug-drug interactions caused by transcriptional induction of P450 enzymes in early-phase drug discovery and development. However, CYP3A7 is preferentially expressed in premature hepatoblasts and major hepatic carcinoma cell lines. The human hepatocellular carcinoma cell line HepaRG possesses a high self-renewal capacity and can differentiate into hepatic cells similar to human adult hepatocytes in vitro. Transgenic HepaRG cells, in which the expression of fluorescent reporters is regulated by 35 kb regulatory elements of CYP3A4, have a distinct advantage over human hepatocytes isolated by collagenase perfusion, which are unstable in culture. Thus, we created transgenic HepaRG and HepG2 cells by replacing the protein-coding regions of human CYP3A4 and CYP3A7 with enhanced green fluorescent protein (EGFP) and DsRed reporters, respectively, in a bacterial artificial chromosome vector that included whole regulatory elements. The intensity of DsRed fluorescence was initially high during the proliferation of transgenic HepaRG cells. However, most EGFP-positive cells were derived from those in which DsRed fluorescence was extinguished. Comparative analyses in these transgenic clones showed that changes in the total fluorescence intensity of EGFP reflected fold changes in the mRNA level of endogenous CYP3A4. Moreover, CYP3A4 induction was monitored by the increase in EGFP fluorescence. Thus, this assay provides a real-time evaluation system for quality assurance of hepatic differentiation into CYP3A4-expressing cells, unfavourable CYP3A4 induction, and fluorescence-activated cell sorting-mediated enrichment of CYP3A4-expressing hepatocytes based on the total fluorescence intensities of fluorescent reporters, without the need for many time-consuming steps. PMID:25101946

  7. Dual-color fluorescence imaging to monitor CYP3A4 and CYP3A7 expression in human hepatic carcinoma HepG2 and HepaRG cells.

    PubMed

    Tsuji, Saori; Kawamura, Fumihiko; Kubiura, Musashi; Hayashi, Ayaka; Ohbayashi, Tetsuya; Kazuki, Yasuhiro; Chesné, Christophe; Oshimura, Mitsuo; Tada, Masako

    2014-01-01

    Human adult hepatocytes expressing CYP3A4, a major cytochrome P450 enzyme, are required for cell-based assays to evaluate the potential risk of drug-drug interactions caused by transcriptional induction of P450 enzymes in early-phase drug discovery and development. However, CYP3A7 is preferentially expressed in premature hepatoblasts and major hepatic carcinoma cell lines. The human hepatocellular carcinoma cell line HepaRG possesses a high self-renewal capacity and can differentiate into hepatic cells similar to human adult hepatocytes in vitro. Transgenic HepaRG cells, in which the expression of fluorescent reporters is regulated by 35 kb regulatory elements of CYP3A4, have a distinct advantage over human hepatocytes isolated by collagenase perfusion, which are unstable in culture. Thus, we created transgenic HepaRG and HepG2 cells by replacing the protein-coding regions of human CYP3A4 and CYP3A7 with enhanced green fluorescent protein (EGFP) and DsRed reporters, respectively, in a bacterial artificial chromosome vector that included whole regulatory elements. The intensity of DsRed fluorescence was initially high during the proliferation of transgenic HepaRG cells. However, most EGFP-positive cells were derived from those in which DsRed fluorescence was extinguished. Comparative analyses in these transgenic clones showed that changes in the total fluorescence intensity of EGFP reflected fold changes in the mRNA level of endogenous CYP3A4. Moreover, CYP3A4 induction was monitored by the increase in EGFP fluorescence. Thus, this assay provides a real-time evaluation system for quality assurance of hepatic differentiation into CYP3A4-expressing cells, unfavourable CYP3A4 induction, and fluorescence-activated cell sorting-mediated enrichment of CYP3A4-expressing hepatocytes based on the total fluorescence intensities of fluorescent reporters, without the need for many time-consuming steps.

  8. High efficiency Cu2ZnSn(S,Se)4 solar cells by applying a double In2S3/CdS emitter.

    PubMed

    Kim, Jeehwan; Hiroi, Homare; Todorov, Teodor K; Gunawan, Oki; Kuwahara, Masaru; Gokmen, Tayfun; Nair, Dhruv; Hopstaken, Marinus; Shin, Byungha; Lee, Yun Seog; Wang, Wei; Sugimoto, Hiroki; Mitzi, David B

    2014-11-26

    High-efficiency Cu2ZnSn(S,Se)4 solar cells are reported by applying In2S3/CdS double emitters. This new structure offers a high doping concentration within the Cu2ZnSn(S,Se)4 solar cells, resulting in a substantial enhancement in open-circuit voltage. The 12.4% device is obtained with a record open-circuit voltage deficit of 593 mV. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. A novel 5HT3 antagonist 4i (N-(3-chloro-2-methylphenyl)quinoxalin-2-carboxamide) prevents diabetes-induced depressive phenotypes in mice: Modulation of serotonergic system.

    PubMed

    Gupta, Deepali; Thangaraj, Devadoss; Radhakrishnan, Mahesh

    2016-01-15

    Despite the presence of a multitudinous pharmacotherapy, diabetes-induced depressive disorder remains undertreated. Evidence suggests that brain serotonergic deficits are associated with depressive-like behavior in diabetes and that 5HT3 receptor (5HT3R) antagonists have serotonergic facilitatory effects. This study examined the effects of a novel 5HT3R antagonist, 4i (N-(3-chloro-2-methylphenyl)quinoxalin-2-carboxamide), in diabetes-induced depressive phenotypes. Experimentally, (1) to evaluate the effects of 4i, mice with 8-weeks of diabetes (induced by streptozotocin, 200mg/kg, i.p.) were treated with vehicle, 4i (0.5 and 1mg/kg/day, i.p.), fluoxetine (10mg/kg/day, i.p.) for 4-weeks and subjected to neurobehavioral assays, followed by biochemical estimation of serotonin levels in midbrain, prefrontal-cortex and cerebellum. (2) To evaluate the role of 5HT3R in the postulated effect of 4i, diabetic mice were given 4i (1mg/kg/day, i.p.) after 1h of 1-(m-chlorophenyl)-biguanide (mCPBG, a 5HT3R agonist, 10mg/kg/day, i.p.) treatment and subjected to the same protocol. The results showed that diabetic mice exhibited a significant behavioral deficit, including depression-like behavior in forced swim test, anxiety-like in open field test and sociability deficits in social interaction test, along with a significant decrease in serotonin level in these brain regions. 4i (1mg/kg), similar to fluoxetine, prevented these behavioral abnormalities and normalized brain serotonin levels. 4i (0.5mg/kg) ameliorated only diabetes-induced depressive-like behavior and serotonin deficits, but not anxiety-like effects. mCPBG blunted 4i-mediated behavioral response and increase in brain serotonin levels. Altogether, this study suggests that 4i prevents diabetes-induced depressive phenotypes in mice, which may involve antagonism of 5HT3Rs and increase in serotonin levels in discrete brain regions. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. The Unique α4(+)/(−)α4 Agonist Binding Site in (α4)32)2 Subtype Nicotinic Acetylcholine Receptors Permits Differential Agonist Desensitization Pharmacology versus the (α4)22)3 Subtype

    PubMed Central

    Eaton, J. Brek; Lucero, Linda M.; Stratton, Harrison; Chang, Yongchang; Cooper, John F.; Lindstrom, Jon M.; Lukas, Ronald J.

    2014-01-01

    Selected nicotinic agonists were used to activate and desensitize high-sensitivity (HS) (α4)22)3) or low-sensitivity (LS) (α4)32)2) isoforms of human α4β2-nicotinic acetylcholine receptors (nAChRs). Function was assessed using 86Rb+ efflux in a stably transfected SH-EP1-hα4β2 human epithelial cell line, and two-electrode voltage-clamp electrophysiology in Xenopus laevis oocytes expressing concatenated pentameric HS or LS α4β2-nAChR constructs (HSP and LSP). Unlike previously studied agonists, desensitization by the highly selective agonists A-85380 [3-(2(S)-azetidinylmethoxy)pyridine] and sazetidine-A (Saz-A) preferentially reduced α4β2-nAChR HS-phase versus LS-phase responses. The concatenated-nAChR experiments confirmed that approximately 20% of LS-isoform acetylcholine-induced function occurs in an HS-like phase, which is abolished by Saz-A preincubation. Six mutant LSPs were generated, each targeting a conserved agonist binding residue within the LS-isoform-only α4(+)/(−)α4 interface agonist binding site. Every mutation reduced the percentage of LS-phase function, demonstrating that this site underpins LS-phase function. Oocyte-surface expression of the HSP and each of the LSP constructs was statistically indistinguishable, as measured using β2-subunit–specific [125I]mAb295 labeling. However, maximum function is approximately five times greater on a “per-receptor” basis for unmodified LSP versus HSP α4β2-nAChRs. Thus, recruitment of the α4(+)/(−)α4 site at higher agonist concentrations appears to augment otherwise-similar function mediated by the pair of α4(+)/(−)β2 sites shared by both isoforms. These studies elucidate the receptor-level differences underlying the differential pharmacology of the two α4β2-nAChR isoforms, and demonstrate that HS versus LS α4β2-nAChR activity can be selectively manipulated using pharmacological approaches. Since α4β2 nAChRs are the predominant neuronal subtype, these discoveries likely

  11. A new mineral species ferricoronadite, Pb[Mn6 4+(Fe3+, Mn3+)2]O16: mineralogical characterization, crystal chemistry and physical properties

    NASA Astrophysics Data System (ADS)

    Chukanov, Nikita V.; Aksenov, Sergey M.; Jančev, Simeon; Pekov, Igor V.; Göttlicher, Jörg; Polekhovsky, Yury S.; Rusakov, Vyacheslav S.; Nelyubina, Yuliya V.; Van, Konstantin V.

    2016-07-01

    A new mineral ferricoronadite with the simplified formula Pb(Mn6 4+Fe2 3+)O16 was discovered in the orogenetic zone related to the "Mixed Series" metamorphic complex near the Nežilovo village, Pelagonian massif, Republic of Macedonia. Associated minerals are franklinite, gahnite, hetaerolite, roméite, almeidaite, Mn-analogue of plumboferrite, zincohögbomite analogue with Fe3+ > Al, zincochromite, Zn-bearing talc, Zn-bearing muscovite, baryte, quartz and zircon. Ferricoronadite is a late hydrothermal mineral forming veinlets up to 8 mm thick in granular aggregate predominantly composed by zinc-dominant spinels. The new mineral is opaque, black, with brownish black streak. The luster is strong submetallic to metallic. The micro-indentation hardness is 819 kg/mm2. Distinct cleavage is observed on (100). Ferricoronadite is brittle, with uneven fracture. The density calculated from the empirical formula is 5.538 g/cm3. In reflected light, ferricoronadite is light gray. The reflectance values [ R max/ R min, % ( λ, nm)] are: 28.7/27.8 (470), 27.6/26.6 (546), 27.2/26.1 (589), 26.5/25.5 (650). The IR spectrum shows the absence of H2O and OH groups. According to the Mössbauer spectrum, all iron is trivalent. The Mn K-edge XANES spectroscopy shows that Mn is predominantly tetravalent, with subordinate Mn3+. The chemical composition is (wt%; electron microprobe, Mn apportioned between MnO2 and Mn2O3 based on the charge-balance requirement): BaO 5.16, PbO 24.50, ZnO 0.33, Al2O3 0.50, Mn2O3 9.90, Fe2O3 11.45, TiO2 4.19, MnO2 44.81, total 100.84. The empirical formula based on 8 cations Mn + Fe + Ti + Al + Zn pfu is Pb1.03Ba0.32(Mn 4.85 4+ Fe 1.35 3+ Mn 1.18 3+ Ti0.49Al0.09Zn0.04)Σ8.00O16. The crystal structure was determined using single-crystal X-ray diffraction data. The new mineral is tetragonal, space group I4/ m, a = 9.9043(7), c = 2.8986(9) Å, V = 284.34(9) Å3, Z = 1. In ferricoronadite, double chains of edge-sharing (Mn, Fe, Ti)-centered octahedra are connected

  12. Mutation analysis of COL4A3 and COL4A4 genes in a Chinese autosomal-dominant Alport syndrome family.

    PubMed

    Guo, Liwei; Li, Duan; Dong, Shuangshuang; Wan, Donghao; Yang, Baosheng; Huang, Yanmei

    2017-06-01

    Autosomal dominant Alport syndrome (ADAS) accounts for 5% of all cases of Alport syndrome (AS), a primary basement membrane disorder arising from mutations in genes encoding the type IV collagen protein family.Mutations in COL4A3 and COL4A4 genes were reported to be associated with ADAS. In this study, clinical data in a large consanguineous family with seven affected members were reviewed, and genomic DNA was extracted. For mutation screening, all exons of COL4A3 and COL4A4 genes were polymerase chain reaction-amplified and direct sequenced from genomic DNA, and the mutations were analyzed by comparing with members in this family, 100 ethnicitymatched controls and the sequence of COL4A3 and COL4A4 genes from GenBank. A novel mutation determining a nucleotide change was found, i.e. c.4195 A>T (p.Met1399Leu) at 44th exon of COL4A4 gene, and this mutation showed heterozygous in all patients of this family. Also a novel intron mutation (c.4127+11 C>T) was observed at COL4A4 gene. Thus the novel missense mutation c.4195 A>T (p.Met1399Leu) and the intron mutation (c.4127+11 C>T) at COL4A4 gene might be responsible for ADAS of this family. Our results broadened the spectrum of mutations in COL4A4 and had important implications in the diagnosis, prognosis, and genetic counselling of ADAS.

  13. Three-Dimensional LiMnPO4·Li3V2(PO4)3/C Nanocomposite as a Bicontinuous Cathode for High-Rate and Long-Life Lithium-Ion Batteries.

    PubMed

    Luo, Yanzhu; Xu, Xu; Zhang, Yuxiang; Pi, Yuqiang; Yan, Mengyu; Wei, Qiulong; Tian, Xiaocong; Mai, Liqiang

    2015-08-12

    Olivine-type LiMnPO4 has been extensively studied as a high-energy density cathode material for lithium-ion batteries. To improve both the ionic and electronic conductivities of LiMnPO4, a series of carbon-decorated LiMnPO4·Li3V2(PO4)3 nanocomposites are synthesized by a facile sol-gel method combined with the conventional solid-state method. The optimized composite presents a three-dimensional hierarchical structure with active nanoparticles well-embedded in a conductive carbon matrix. The combination of the nanoscale carbon coating and the microscale carbon network could provide a more active site for electrochemical reaction, as well as a highly conductive network for both electron and lithium-ion transportation. When cycled at 20 C, an initial specific capacity of 103 mA h g(-1) can be obtained and the capacity retention reaches 68% after 3000 cycles, corresponding to a capacity fading of 0.013% per cycle. The stable capacity and excellent rate capability make this carbon-decorated LiMnPO4·Li3V2(PO4)3 nanocomposite a promising cathode for lithium-ion batteries.

  14. Non-aqueous synthesis of water-dispersible Fe3O4-Ca3(PO4)2 core-shell nanoparticles

    NASA Astrophysics Data System (ADS)

    Liu, HongLing; Wu, JunHua; Min, Ji Hyun; Hou, Peng; Song, Ah-Young; Kim, Young Keun

    2011-02-01

    The Fe3O4-Ca3(PO4)2 core-shell nanoparticles were prepared by one-pot non-aqueous nanoemulsion with the assistance of a biocompatible triblock copolymer, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEO-PPO-PEO), integrating the magnetic properties of Fe3O4 and the bioactive functions of Ca3(PO4)2 into single entities. The Fe3O4 nanoparticles were pre-formed first by thermal reduction of Fe(acac)3 and then the Ca3(PO4)2 layer was coated by simultaneous deposition of Ca2 + and PO43 - . The characterization shows that the combination of the two materials into a core-shell nanostructure retains the magnetic properties and the Ca3(PO4)2 shell forms an hcp phase (a = 7.490 Å, c = 9.534 Å) on the Fe3O4 surface. The magnetic hysteresis curves of the nanoparticles were further elucidated by the Langevin equation, giving an estimation of the effective magnetic dimension of the nanoparticles and reflecting the enhanced susceptibility response as a result of the surface covering. Fourier transform infrared (FTIR) analysis provides the characteristic vibrations of Ca3(PO4)2 and the presence of the polymer surfactant on the nanoparticle surface. Moreover, the nanoparticles could be directly transferred to water and the aqueous dispersion-collection process of the nanoparticles was demonstrated for application readiness of such core-shell nanostructures in an aqueous medium. Thus, the construction of Fe3O4 and Ca3(PO4)2 in the core-shell nanostructure has conspicuously led to enhanced performance and multi-functionalities, offering various possible applications of the nanoparticles.

  15. Method of refining 2,2-isopropylidenebis-3,5- dibromophenylene-4-oxydiethanol

    NASA Technical Reports Server (NTRS)

    Kobayashi, T.; Nawata, K.; Hiratsuka, K.

    1982-01-01

    A method of refining 2,2-isopropylidenebis-3,5-dibromophenylene-4-oxydiethanol is described which is characterized by recrystallization of 2,2-isopropylidenebis-3,5-dibromophenylene-4-oxydiethanol using one or more aromatic hydrocarbons such as benzene, xylene, toluene, ethylbenzene or pseudocumene.

  16. Analysis of 3',5'-dichloro-2,3,4-trihydroxy-2-methylbutylanilide (DTMBA) as a new potential biomarker of exposure to vinclozolin in urine.

    PubMed

    Cruz-Hurtado, Marycarmen; López-González, Ma de Lourdes; Escobar-Wilches, Derly Constanza; Sierra-Santoyo, Adolfo

    2018-05-01

    Vinclozolin (V) is a fungicide with anti-androgenic properties whose metabolism is not fully understood, and data on urinary elimination of either V or its metabolites are limited. Therefore the kinetics of urinary elimination of V and its metabolites, after an oral dose in adult male rats were investigated. A single oral dose of V (100 mg/kg) suspended in corn oil was administered to male adult Wistar rats, and urine was collected at different times after dosing. V and its metabolites were extracted from urine, then enzymatically hydrolyzed using β-glucuronidase/sulfatase of H. pomatia, and analyzed by HPLC/DAD. Urinary pharmacokinetic parameters were calculated using the analyte concentrations adjusted by creatinine levels. V and its metabolites 3',5'-dichloro-2,3,4-trihydroxy-2-methylbutylanilide (DTMBA, formerly denoted as M5), 2-[[(3,5-dichlorophenyl)-carbamoyl]oxy]-2-methyl-3-butenoic acid (M1), 3,5-dichloroaniline (M3), and 3',5'-dichloro-2-hydroxy-2-methylbut-3-enanilide (M2) were efficiently detected. The mean urine concentrations of V and M1 metabolite were fitted to a two-compartmental model for pharmacokinetic analysis. DTMBA approximately represented 88% of the total excreted metabolites, it was easily detected up to 168 h after dosing and its half-lives were 21.5 and 74.1 h, respectively. M1 was the second most abundant metabolite and was detected up to 144 h after being void. V and M3 were detected before 48 h, and M2 exhibited the lowest levels during the first 8 h after dosing. DTMBA, the most abundant V metabolite is quickly eliminated by urine, it is chemically stable, specific and could represent a useful alternative to be used as a biomarker of exposure to V. Copyright © 2018 Elsevier Inc. All rights reserved.

  17. Synthesis and properties of 2-(4-substituted)butyl derivatives of some 2,3-dihydro-1,3-dioxo-1H-pyrrolo[3,4-c]pyridines.

    PubMed

    Sladowska, H; Szkatuła, D; Filipek, B; Maciag, D; Sapa, J; Zygmunt, M

    2001-02-01

    The synthesis of 2-(4-substituted)butyl derivatives of 4-alkoxy-2,3-dihydro-6-methyl-1,3-dioxo-1H-pyrrolo[3,4-c]pyridine (10-15) and the results of preliminary pharmacological screening are described in this paper. All the compounds tested showed a strong analgesic action, suppressed spontaneous locomotor activity and prolonged barbiturate sleep. Except 10, all significantly decreased systolic and diastolic blood pressure.

  18. Synthesis and anticancer evaluation of 1,3,4-oxadiazoles, 1,3,4-thiadiazoles, 1,2,4-triazoles and Mannich bases.

    PubMed

    Megally Abdo, Nadia Youssef; Kamel, Mona Monir

    2015-01-01

    A series of 5-(pyridin-4-yl)-N-substituted-1,3,4-oxadiazol-2-amines (3a-d), 5-(pyridin-4-yl)-N-substituted-1,3,4-thiadiazol-2-amines (4a-d) and 5-(pyridin-4-yl)-4-substituted-1,2,4-triazole-3-thiones (5a-d) were obtained by the cyclization of hydrazinecarbothioamide derivatives 2a-d derived from isonicotinic acid hydrazide. Aminoalkylation of compounds 5a-d with formaldehyde and various secondary amines furnished the Mannich bases 6a-p. The structures of the newly synthesized compounds were confirmed on the basis of their spectral data and elemental analyses. All the compounds were screened for their in vitro anticancer activity against six human cancer cell lines and normal fibroblast cells. Sixteen of the tested compounds exhibited significant cytotoxicity against most cell lines. Among these derivatives, the Mannich bases 6j, 6m and 6p were found to exhibit the most potent activity. The Mannich base 6m showed more potent cytotoxic activity against gastric cancer NUGC (IC50=0.021 µM) than the standard CHS 828 (IC50=0.025 µM). Normal fibroblast cells WI38 were affected to a much lesser extent (IC50>10 µM).

  19. DNA Polymerases η and ζ Combine to Bypass O(2)-[4-(3-Pyridyl)-4-oxobutyl]thymine, a DNA Adduct Formed from Tobacco Carcinogens.

    PubMed

    Gowda, A S Prakasha; Spratt, Thomas E

    2016-03-21

    4-(Methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) and N'-nitrosonornicotine (NNN) are important human carcinogens in tobacco products. They are metabolized to produce a variety 4-(3-pyridyl)-4-oxobutyl (POB) DNA adducts including O(2)-[4-(3-pyridyl)-4-oxobut-1-yl]thymidine (O(2)-POB-dT), the most abundant POB adduct in NNK- and NNN-treated rodents. To evaluate the mutagenic properties of O(2)-POB-dT, we measured the rate of insertion of dNTPs opposite and extension past O(2)-POB-dT and O(2)-Me-dT by purified human DNA polymerases η, κ, ι, and yeast polymerase ζ in vitro. Under conditions of polymerase in excess, polymerase η was most effective at the insertion of dNTPs opposite O(2)-alkyl-dTs. The time courses were biphasic suggesting the formation of inactive DNA-polymerase complexes. The kpol parameter was reduced approximately 100-fold in the presence of the adduct for pol η, κ, and ι. Pol η was the most reactive polymerase for the adducts due to a higher burst amplitude. For all three polymerases, the nucleotide preference was dATP > dTTP ≫ dGTP and dCTP. Yeast pol ζ was most effective in bypassing the adducts; the kcat/Km values were reduced only 3-fold in the presence of the adducts. The identity of the nucleotide opposite the O(2)-alkyl-dT did not significantly affect the ability of pol ζ to bypass the adducts. The data support a model in which pol η inserts ATP or dTTP opposite O(2)-POB-dT, and then, pol ζ extends past the adduct.

  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. K(2)MM'(3)Se(6) (M = Cu, Ag; M' = Ga, In), A new series of metal chalcogenides with chain-sublayer-chain slabs: (infinity)(1)[M'Se(4)]-(infinity)(2)[(MSe(4))(M'Se(4))]-(infinity)(1)[M'Se(4)].

    PubMed

    Ma, Hong-Wei; Guo, Guo-Cong; Wang, Ming-Sheng; Zhou, Guo-Wei; Lin, Shan-Hou; Dong, Zhen-Chao; Huang, Jin-Shun

    2003-02-24

    A new series of novel isostructural metal chalcogenides, K(2)CuIn(3)Se(6) (1), K(2)CuGa(3)Se(6) (2), and K(2)AgIn(3)Se(6) (3), were obtained by a reactive flux technique and structurally characterized. Compounds 1, 2, and 3 crystallize in the space group C2/c of the monoclinic system with eight formula units in a cell: a = 11.445(2) A, b = 11.495(2) A, c = 21.263(4) A, beta = 97.68(3) degrees, V = 2772(1) A(3), R1/wR2 = 0.0676/0.1652 for 1; a = 11.031(2) A, b = 11.050(4) A, c = 20.808(7) A, beta = 97.71(2) degrees, V = 2513(1) A(3), R1/wR2 = 0.0301/0.0511 for 2; and a = 11.633(1) A, b = 11.587(1) A, c = 21.355(1) A, beta = 98.010(8) degrees, V = 2850.4(4) A(3), R1/wR2 = 0.0471/0.0732 for 3. These isostructural compounds are characterized by a chain-sublayer-chain slab structure. The sublayer, composed of alternative corner-sharing mixed-metal tetrahedra, is sandwiched by parallel corner-sharing tetrahedral chains. Optical absorption spectra of compounds 1, 2, and 3 reveal the presence of a sharp optical gap of 1.68, 1.72, and 1.64 eV, respectively, suggesting that these materials are semiconductors and suitable for efficient absorption of solar radiation in solar cell applications. IR spectra show no obvious absorption in the range 800-4000 cm(-)(1).

  2. 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

  3. (2E)-3-(6-methoxynaphthalen-2-yl)-1-(pyridin-3-yl)prop-2-en-1-one and its cyclocondensation product with guanidine, (4RS)-2-amino-4-(6-methoxynaphthalen-2-yl)-6-(pyridin-3-yl)-3,4-dihydropyrimidine monohydrate: two types of hydrogen-bonded sheet.

    PubMed

    Nayak, Prakash S; Narayana, Badiadka; Yathirajan, Hemmige S; Hosten, Eric C; Betz, Richard; Glidewell, Christopher

    2014-11-01

    The structures of a chalcone and of its cyclocondensation product with guanidine are reported. In (2E)-3-(6-methoxynaphthalen-2-yl)-1-(pyridin-3-yl)prop-2-en-1-one, C19H15NO2, (I), the planes of the pyridine and naphthalene units make dihedral angles with that of the central spacer unit of 23.61 (13) and 23.57 (15)°, respectively, and a dihedral angle of 47.24 (9)° with each other. The molecules of (I) are linked into sheets by a combination of C-H···O and C-H···π(arene) hydrogen bonds. In the cyclocondensation product (4RS)-2-amino-4-(6-methoxynaphthalen-2-yl)-6-(pyridin-3-yl)-3,4-dihydropyrimidine monohydrate, C20H18N4O·H2O, (II), the dihydropyrimidine ring adopts a conformation best described as a shallow boat. The molecular components are linked by two N-H···O hydrogen bonds, two O-H···N hydrogen bonds and one N-H···N hydrogen bond to form complex sheets, with the methoxynaphthalene interdigitated between inversion-related pairs of sheets.

  4. Surface chemistry reactions of alpha-terpineol [(R)-2-(4-methyl-3-cyclohexenyl)isopropanol] with ozone and air on a glass and a vinyl tile.

    PubMed

    Ham, J E; Wells, J R

    2008-10-01

    The surface-phase reaction products of alpha-terpineol [(R)-2-(4-methyl-3-cyclohexenyl)isopropanol] with ozone (O(3)), air or nitrogen (N(2)) on both a glass and vinyl flooring tile were investigated using the recently published FLEC Automation and Control System (FACS). The FACS was used to deliver O(3) (100 ppb), air or N(2) to the surface at a specified flow rate (300 ml/min) and relative humidity (50%) after application of a 1.6%alpha-terpineol solution in methanol. Oxidation products were detected using the derivatization agents: O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine and N,O-bis(trimethysilyl)trifluoroacetamide. The positively identified reaction products were glyoxal, methylglyoxal and 4-oxopentanal. The proposed oxidation products based on previously published VOC/O(3) reaction mechanisms were: 4-methylcyclohex-3-en-1-one, 6-hydroxyhept-en-2-one, 3-(1-hydroxy-1-methylethyl)-6-methylcyclohex-2-en-1-one) and one surface-enhanced reaction product: 5-(1-hydroxy-1-methylethyl)-2-methylcyclohex-2-en-1-one. Though similar products were observed in gas-phase alpha-terpineol/O(3) reactions, the ratio of the reaction products were different suggesting stabilization of larger molecular weight species by the surface. Emission profiles of these oxidation products over 72 h are also reported. Volatile organic compounds (VOCs) can interact with indoor initiators [such as hydroxyl radicals (OH*), ozone and nitrate radicals (NO(3)*)] to form a number of oxygenated by-products in the gas-phase. However, when VOCs are applied to or are present on the surface, heterogeneous chemistry with indoor initiators can also occur. The surface can influence the reaction mechanism to produce new surface reaction products. The work, described here, shows the interaction of alpha-terpineol (major component of pine oil) with ozone and air on both glass and vinyl flooring. These results demonstrated emissions of oxygenated organic compounds as a result of reaction and that further

  5. Metabolism of endosulfan-alpha by human liver microsomes and its utility as a simultaneous in vitro probe for CYP2B6 and CYP3A4.

    PubMed

    Casabar, Richard C T; Wallace, Andrew D; Hodgson, Ernest; Rose, Randy L

    2006-10-01

    Endosulfan-alpha is metabolized to a single metabolite, endosulfan sulfate, in pooled human liver microsomes (Km = 9.8 microM, Vmax = 178.5 pmol/mg/min). With the use of recombinant cytochrome P450 (P450) isoforms, we identified CYP2B6 (Km = 16.2 microM, Vmax = 11.4 nmol/nmol P450/min) and CYP3A4 (Km = 14.4 microM, Vmax = 1.3 nmol/nmol P450/min) as the primary enzymes catalyzing the metabolism of endosulfan-alpha, although CYP2B6 had an 8-fold higher intrinsic clearance rate (CL(int) = 0.70 microl/min/pmol P450) than CYP3A4 (CL(int) = 0.09 microl/min/pmol P450). Using 16 individual human liver microsomes (HLMs), a strong correlation was observed with endosulfan sulfate formation and S-mephenytoin N-demethylase activity of CYP2B6 (r(2) = 0.79), whereas a moderate correlation with testosterone 6 beta-hydroxylase activity of CYP3A4 (r(2) = 0.54) was observed. Ticlopidine (5 microM), a potent CYP2B6 inhibitor, and ketoconazole (10 microM), a selective CYP3A4 inhibitor, together inhibited approximately 90% of endosulfan-alpha metabolism in HLMs. Using six HLM samples, the percentage total normalized rate (% TNR) was calculated to estimate the contribution of each P450 in the total metabolism of endosulfan-alpha. In five of the six HLMs used, the percentage inhibition with ticlopidine and ketoconazole in the same incubation correlated with the combined % TNRs for CYP2B6 and CYP3A4. This study shows that endosulfan-alpha is metabolized by HLMs to a single metabolite, endosulfan sulfate, and that it has potential use, in combination with inhibitors, as an in vitro probe for CYP2B6 and 3A4 catalytic activities.

  6. Synthesis, crystal growth, single crystal X-ray analysis and vibrational spectral studies of (2E)-3-(2-chloro-4-fluorophenyl)-1-(3,4-dimethoxyphenyl)prop-2-en-1-one: A combined DFT study

    NASA Astrophysics Data System (ADS)

    Chidan Kumar, C. S.; Balachandran, V.; Fun, Hoong-Kun; Chandraju, Siddegowda; Quah, Ching Kheng

    2015-11-01

    A new chalcone derivative, (2E)-3-(2-chloro-4-fluorophenyl)-1-(3,4-dimethoxyphenyl)prop-2-en-1-one (a) was synthesized and single crystals were grown by slow evaporation technique. The FT-Raman and FT-IR spectra of the sample were recorded in the region 3500-100 cm-1 and 4000-400 cm-1 respectively. The spectra were interpreted with the aid of normal coordinate analysis, following structure optimizations and force field calculations based on B3LYP/6-31G (d) level of theory. Normal coordinate calculations were performed using the DFT force field corrected by a recommended set of scaling factors yielding fairly good agreement between the observed and calculated wavenumbers. The total electron density and molecular electrostatic potential surfaces of the molecule were constructed using B3LYP/6-31G (d) method to display electrostatic potential (electron + nuclei) distribution, molecular shape, size, and dipole moments of the molecule. HOMO and LUMO energies were also calculated. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Global and local reactivity descriptors and dipole moment (μ), static polarizability (α), first order hyperpolarizability (β) and optical gap (ΔE) were also calculated to study the NLO property of our title compound.

  7. 7-tert-Butyl-6-(4-chloro-phenyl)-2-thioxo-2,3-dihydro-1H-pyrido[2,3-d]pyrimidin-4-one, a classic polymodal inhibitor of transient receptor potential vanilloid type 1 with a reduced liability for hyperthermia, is analgesic and ameliorates visceral hypersensitivity.

    PubMed

    Nash, Mark S; McIntyre, Peter; Groarke, Alex; Lilley, Elliot; Culshaw, Andrew; Hallett, Allan; Panesar, Moh; Fox, Alyson; Bevan, Stuart

    2012-08-01

    The therapeutic potential of transient receptor potential vanilloid type 1 (TRPV1) antagonists for chronic pain has been recognized for more than a decade. However, preclinical and clinical data revealed that acute pharmacological blockade of TRPV1 perturbs thermoregulation, resulting in hyperthermia, which is a major hurdle for the clinical development of these drugs. Here, we describe the properties of 7-tert-butyl-6-(4-chloro-phenyl)-2-thioxo-2,3-dihydro-1H-pyrido[2,3-d]pyrimidin-4-one (BCTP), a TRPV1 antagonist with excellent analgesic properties that does not induce significant hyperthermia in rodents at doses providing maximal analgesia. BCTP is a classic polymodal inhibitor of TRPV1, blocking activation of the human channel by capsaicin and low pH with IC(50) values of 65.4 and 26.4 nM, respectively. Similar activity was observed with rat TRPV1, and the inhibition by BCTP was competitive and reversible. BCTP also blocked heat-induced activation of TRPV1. In rats, the inhibition of capsaicin-induced mechanical hyperalgesia was observed with a D(50) value of 2 mg/kg p.o. BCTP also reversed visceral hypersensitivity and somatic inflammatory pain, and using a model of neuropathic pain in TRPV1 null mice we confirmed that its analgesic properties were solely through the inhibition of TRPV1. We were surprised to find that BCTP administered orally induced only a maximal 0.6°C increase in core body temperature at the highest tested doses (30 and 100 mg/kg), contrasting markedly with N-[4-({6-[4-(trifluoromethyl)phenyl]pyrimidin-4-yl}oxy)-1,3-benzothiazol-2-yl]acetamide (AMG517), a clinically tested TRPV1 antagonist, which induced marked hyperthermia (>1°C) at doses eliciting submaximal reversal of capsaicin-induced hyperalgesia. The combined data indicate that TRPV1 antagonists with a classic polymodal inhibition profile can be identified where the analgesic action is separated from the effects on body temperature.

  8. 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)44H2O (H2DSPTP=4'-(2,4-disulfophenyl)-3,2':6'3"-terpyridine, 1 and 2), {[Ni(DSPTP)(H2O)43H2O}n (3), {[Cu(HDSPTP)2(H2O)3]·8H2O}n (4), {[Cu(HDSPTP)2(H2O)3]·6H2O}n (5), {[Cu(DSPTP)(H2O)2]·H2O}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

  9. Supramolecular features of 2-(chlorophenyl)-3-[(chlorobenzylidene)-amino]-2,3-dihydroquinazolin-4(1H)-ones: A combined experimental and computational study

    NASA Astrophysics Data System (ADS)

    Mandal, Arkalekha; Patel, Bhisma K.

    2018-03-01

    The molecular structures of two isomeric 2-(chlorophenyl)-3-[(chlorobenzylidene)-amino] substituted 2,3-dihydroquinazolin-4(1H)-ones have been determined via single crystal XRD. Both isomers contain chloro substitutions on each of the phenyl rings and as a result a broad spectrum of halogen mediated weak interactions are viable in their crystal structures. The crystal packing of these compounds is stabilized by strong N-H⋯O hydrogen bond and various weak, non-classical hydrogen bonds acting synergistically. Both the molecules contain a chiral center and the weak interactions observed in them are either chiral self-discriminatory or chiral self-recognizing in nature. The weak interactions and spectral features of the compounds have been studied through experimental as well as computational methods including DFT, MEP, NBO and Hiresfeld surface analyses. In addition, the effect of different weak interactions to dictate either chiral self-recognition or self-discrimination in crystal packing has been elucidated.

  10. 3D-QSAR modeling and molecular docking studies on a series of 2,5 disubstituted 1,3,4-oxadiazoles

    NASA Astrophysics Data System (ADS)

    Ghaleb, Adib; Aouidate, Adnane; Ghamali, Mounir; Sbai, Abdelouahid; Bouachrine, Mohammed; Lakhlifi, Tahar

    2017-10-01

    3D-QSAR (comparative molecular field analysis (CoMFA)) and comparative molecular similarity indices analysis (CoMSIA) were performed on novel 2,5 disubstituted 1,3,4-oxadiazoles analogues as anti-fungal agents. The CoMFA and CoMSIA models using 13 compounds in the training set gives Q2 values of 0.52 and 0.51 respectively, while R2 values of 0.92. The adapted alignment method with the suitable parameters resulted in reliable models. The contour maps produced by the CoMFA and CoMSIA models were employed to determine a three-dimensional quantitative structure-activity relationship. Based on this study a set of new molecules with high predicted activities were designed. Surflex-docking confirmed the stability of predicted molecules in the receptor.

  11. 40 CFR 721.10078 - Butanamide, 2-[(2-methoxy-4-nitrophenyl)azo]-N-(2-methoxyphenyl)-3-oxo-, 4-[(17-substituted-3,6,9...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...-nitrophenyl)azo]-N-(2-methoxyphenyl)-3-oxo-, 4-[(17-substituted-3,6,9,12,15-pentaazaheptadec-1-yl)substituted...-nitrophenyl)azo]-N-(2-methoxyphenyl)-3-oxo-, 4-[(17-substituted-3,6,9,12,15-pentaazaheptadec-1-yl)substituted...]-N-(2-methoxyphenyl)-3-oxo-, 4-[(17-substituted-3,6,9,12,15-pentaazaheptadec-1-yl)substituted]phenyl...

  12. 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

  13. Decaaquabis(μ3-4-hydroxypyridine-2,6-dicarboxylato)bis(4-hydroxypyridine-2,6-dicarboxylato)tetramanganese(II) 3.34-hydrate: a new three-dimensional open metal-organic framework based on a tetranuclear Mn(II) complex of chelidamic acid and undecameric stitching water clusters.

    PubMed

    Mirzaei, M; Lippolis, V; Eshtiagh-Hosseini, H; Mahjoobizadeh, M

    2012-01-01

    4-Hydroxypyridine-2,6-dicarboxylic acid (chelidamic acid, cdaH(3)) reacts with MnCl(22H(2)O in the presence of 2-amino-4-methylpyrimidine in water to afford the tetranuclear title complex, [Mn(4)(C(8)H(3)NO(5))(4)(H(2)O)(10)]·3.34H(2)O, built through carboxylate bridging. The tetranuclear complex sits on a centre of inversion at (½, ½, ½). In the crystal, discrete undecameric (H(2)O)(10.34) water clusters (involving both coordinated and uncoordinated water molecules, with one site of an uncoordinated water molecule not fully occupied) assemble these tetranuclear Mn(II) complex units via an intricate array of hydrogen bonding into an overall three-dimensional network. The degree of structuring of the (H(2)O)(10.34) supramolecular association of water molecules observed in the present compound, imposed by its environment and vice versa, will be discussed in comparison to that observed for the (H(2)O)(14) supramolecular clusters in the case of the dinuclear complex [Mn(2)(cdaH)(2)(H(2)O)(4)]·4H(2)O [Ghosh et al. (2005). Inorg. Chem. 44, 3856-3862]. © 2012 International Union of Crystallography

  14. Tailored Engineering of an Unusual (C4 H9 NH3 )2 (CH3 NH3 )2 Pb3 Br10 Two-Dimensional Multilayered Perovskite Ferroelectric for a High-Performance Photodetector.

    PubMed

    Li, Lina; Sun, Zhihua; Wang, Peng; Hu, Weida; Wang, Sasa; Ji, Chengmin; Hong, Maochun; Luo, Junhua

    2017-09-25

    Two-dimensional (2D) layered hybrid perovskites have shown great potential in optoelectronics, owing to their unique physical attributes. However, 2D hybrid perovskite ferroelectrics remain rare. The first hybrid ferroelectric with unusual 2D multilayered perovskite framework, (C 4 H 9 NH 3 ) 2 (CH 3 NH 3 ) 2 Pb 3 Br 10 (1), has been constructed by tailored alloying of the mixed organic cations into 3D prototype of CH 3 NH 3 PbBr 3 . Ferroelectricity is created through molecular reorientation and synergic ordering of organic moieties, which are unprecedented for the known 2D multilayered hybrid perovskites. Single-crystal photodetectors of 1 exhibit fascinating performances, including extremely low dark currents (ca. 10 -12  A), large on/off current ratios (ca. 2.5×10 3 ), and very fast response rate (ca. 150 μs). These merits are superior to integrated detectors of other 2D perovskites, and compete with the most active CH 3 NH 3 PbI 3 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Spin-canting magnetization in an unusual Co4 cluster-based layer compound from a 2,3-dihydroxyquinoxaline ligand.

    PubMed

    Yang, Chen-I; Chuang, Po-Hsiang; Lee, Gene-Hsiang; Peng, Shie-Ming; Lu, Kuang-Lieh

    2012-01-16

    The self-assembly of Co(O(2)CPh)(2) with a 2,3-dihydroxyquinoxaline (H(2)dhq) linker has revealed a new two-dimensional cluster-based compound, [Co(4)(OMe)(2)(O(2)CPh)(2)(dhq)(2)(MeOH)(2)](n), which shows spin-canted magnetization and a definite magnetic hysteresis loop.

  16. 40 CFR 721.1637 - 1,2-Propanediol, 3-(2-propenyloxy)-, bis(4-methylbenzene sulfonate); 2-propanol, 1-[2-[[(4...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false 1,2-Propanediol, 3-(2-propenyloxy)-, bis(4-methylbenzene sulfonate); 2-propanol, 1-[2-[[(4-methylphenyl)sulfonyl] oxy]ethoxy]-3-(2...)-, bis(4-methylbenzene sulfonate); 2-propanol, 1-[2-[[(4-methylphenyl)sulfonyl] oxy]ethoxy]-3-(2...

  17. 40 CFR 721.1637 - 1,2-Propanediol, 3-(2-propenyloxy)-, bis(4-methylbenzene sulfonate); 2-propanol, 1-[2-[[(4...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false 1,2-Propanediol, 3-(2-propenyloxy)-, bis(4-methylbenzene sulfonate); 2-propanol, 1-[2-[[(4-methylphenyl)sulfonyl] oxy]ethoxy]-3-(2...)-, bis(4-methylbenzene sulfonate); 2-propanol, 1-[2-[[(4-methylphenyl)sulfonyl] oxy]ethoxy]-3-(2...

  18. Discovery of selective ATP-competitive eIF4A3 inhibitors.

    PubMed

    Ito, Masahiro; Iwatani, Misa; Kamada, Yusuke; Sogabe, Satoshi; Nakao, Shoichi; Tanaka, Toshio; Kawamoto, Tomohiro; Aparicio, Samuel; Nakanishi, Atsushi; Imaeda, Yasuhiro

    2017-04-01

    Eukaryotic initiation factor 4A3 (eIF4A3), an ATP-dependent RNA helicase, is a core component of exon junction complex (EJC). EJC has a variety of roles in RNA metabolism such as translation, surveillance, and localization of spliced RNA. It is worthwhile to identify selective eIF4A3 inhibitors with a view to investigating the functions of eIF4A3 and EJC further to clarify the roles of the ATPase and helicase activities in cells. Our chemical optimization of hit compound 2 culminated in the discovery of ATP-competitive eIF4A3 inhibitor 18 with submicromolar ATPase inhibitory activity and excellent selectivity over other helicases. Hence, compound 18 could be a valuable chemical probe to elucidate the detailed functions of eIF4A3 and EJC. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. 2,3-trans-3,4-trans-3,4-Dihydroxy-L-proline: An amino acid in toxic peptides of Amanita virosa mushrooms

    PubMed Central

    Buku, A.; Faulstich, H.; Wieland, T.; Dabrowski, J.

    1980-01-01

    Among the four possible stereoisomers of 3,4-dihydroxy-L-proline,2,3-trans-3,4-trans-3,4-dihydroxy-L-proline (IV) had not been found in nature previously. It has now been detected as a component of virotoxins, toxic peptides of Amanita virosa mushrooms. Because periodate failed to effect an oxidative glycol splitting reaction, the two hydroxyl groups in positions 3 and 4 were expected to be in a trans configuration. Furthermore, the formation of a 4-lactone on treatment with acids pointed to the carboxyl group and the hydroxyl group at position 4 being in a cis configuration. These results are in agreement with structure IV only. Final proof for structure IV was given by NMR spectroscopy and direct comparison with the 2,3-cis-3,4-trans-3,4-dihydroxy-L-proline isomer. PMID:16592813

  20. A 2,4-dichlorophenoxyacetic acid induced fatality.

    PubMed

    Jorens, P G; Heytens, L; De Paep, R J; Bossaert, L; Selala, M I; Schepens, P J

    1995-03-01

    This paper reports on a fatal intoxication by oral ingestion of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). At admission, the victim was unconscious. His condition deteroriated rapidly with blood loss from his mouth and nose. Since the cause of this condition was not known, gastroscopy was performed and haemorrhagic mucosa was observed in the mouth, oesophagus and stomach. Gastric contents (removed by lavage), urine and blood were submitted for toxicological analysis. Unfortunately, within 3 h of admission (about 5 h following ingestion of the toxin) profound cardiogenic shock developed and the patient died. The identity of the toxic xenobiotic was revealed by gas chromatography-mass spectrometry. Analytical quantification of the herbicide was performed by acid extraction prior to gas chromatographic examination using electron capture detection. His blood level of 2,4-D was 192 mg l-1.

  1. A[Bi(3)Ti(4)O(13)] and A[Bi(3)PbTi(5)O(16)] (A = K, Cs): New n = 4 and n = 5 Members of the Layered Perovskite Series, A[A'(n)()(-)(1)B(n)()O(3)(n)()(+1)], and Their Hydrates.

    PubMed

    Gopalakrishnan, J.; Sivakumar, T.; Thangadurai, V.; Subbanna, G. N.

    1999-06-14

    We describe the synthesis and structural characterization of new layered bismuth titanates, A[Bi(3)Ti(4)O(13)] and A[Bi(3)PbTi(5)O(16)] for A = K, Cs, corresponding to n = 4 and 5 members of the Dion-Jacobson series of layered perovskites of the general formula, A[A'(n)()(-)(1)B(n)()O(3)(n)()(+1)]. These materials have been prepared by solid state reaction of the constituents containing excess alkali, which is required to suppress the formation of competitive Aurivillius phases. Unlike the isostructural niobates and niobium titanates of the same series, the new phases reported here are spontaneously hydrated-a feature which could make them potentially useful as photocatalysts for water splitting reaction. On hydration of the potassium compounds, the c axis expands by ca. 2 Å and loses its doubling [for example, the tetragonal lattice parameters of K[Bi(3)Ti(4)O(13)] and its dihydrate are respectively a = 3.900(1) Å, c = 37.57(2) Å; a = 3.885(1) Å, c = 20.82(4) Å]; surprisingly, the cesium analogues do not show a similar change on hydration.

  2. 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.

  3. 3D-QSAR studies on 1,2,4-triazolyl 5-azaspiro [2.4]-heptanes as D3R antagonists

    NASA Astrophysics Data System (ADS)

    Zhang, Xin; Zhang, Hui

    2018-07-01

    Dopamine D3 receptor has become an attractive target in the treatment of abused drugs. 3D-QSAR studies were performed on a novel series of D3 receptor antagonists, 1,2,4-triazolyl 5-azaspiro [2.4]-heptanes, using CoMFA and CoMSIA methods. Two predictive 3D-QSAR models have been generated for the modified design of D3R antagonists. Based on the steric, electrostatic, hydrophobic and hydrogen-bond acceptor information of contour maps, key structural factors affecting the bioactivity were explored. This work gives helpful suggestions on the design of novel D3R antagonists with increased activities.

  4. An Inducible Cytochrome P450 3A4-Dependent Vitamin D Catabolic Pathway

    PubMed Central

    Wang, Zhican; Lin, Yvonne S.; Zheng, Xi Emily; Senn, Tauri; Hashizume, Takanori; Scian, Michele; Dickmann, Leslie J.; Nelson, Sidney D.; Baillie, Thomas A.; Hebert, Mary F.; Blough, David; Davis, Connie L.

    2012-01-01

    Vitamin D3 is critical for the regulation of calcium and phosphate homeostasis. In some individuals, mineral homeostasis can be disrupted by long-term therapy with certain antiepileptic drugs and the antimicrobial agent rifampin, resulting in drug-induced osteomalacia, which is attributed to vitamin D deficiency. We now report a novel CYP3A4-dependent pathway, the 4-hydroxylation of 25-hydroxyvitamin D3 (25OHD3), the induction of which may contribute to drug-induced vitamin D deficiency. The metabolism of 25OHD3 was fully characterized in vitro. CYP3A4 was the predominant source of 25OHD3 hydroxylation by human liver microsomes, with the formation of 4β,25-dihydroxyvitamin D3 [4β,25(OH)2D3] dominating (Vmax/Km = 0.85 ml · min−1 · nmol enzyme−1). 4β,25(OH)2D3 was found in human plasma at concentrations comparable to that of 1α,25-dihydroxyvitamin D3, and its formation rate in a panel of human liver microsomes was strongly correlated with CYP3A4 content and midazolam hydroxylation activity. Formation of 4β,25(OH)2D3 in primary human hepatocytes was induced by rifampin and inhibited by CYP3A4-specific inhibitors. Short-term treatment of healthy volunteers (n = 6) with rifampin selectively induced CYP3A4-dependent 4β,25(OH)2D3, but not CYP24A1-dependent 24R,25-dihydroxyvitamin D3 formation, and altered systemic mineral homeostasis. Our results suggest that CYP3A4-dependent 25OHD3 metabolism may play an important role in the regulation of vitamin D3 in vivo and in the etiology of drug-induced osteomalacia. PMID:22205755

  5. A Discovery-Learning 2,4-Dinitrophenylhydrazone Experiment

    ERIC Educational Resources Information Center

    Vittimberga, Bruno M.; Ruekberg, Ben

    2006-01-01

    Selections of liquid aldehydes and ketones are proposed for students to determine what property is the best predictor of the color (yellow to red) of their 2,4-dinitrophenylhydrazone derivative. Students may use a computer (spreadsheet or word processor) to analyze results. (Contains 1 table and 3 notes.)

  6. MF498 [N-{[4-(5,9-Diethoxy-6-oxo-6,8-dihydro-7H-pyrrolo[3,4-g]quinolin-7-yl)-3-methylbenzyl]sulfonyl}-2-(2-methoxyphenyl)acetamide], a selective E prostanoid receptor 4 antagonist, relieves joint inflammation and pain in rodent models of rheumatoid and osteoarthritis.

    PubMed

    Clark, Patsy; Rowland, Steven E; Denis, Danielle; Mathieu, Marie-Claude; Stocco, Rino; Poirier, Hugo; Burch, Jason; Han, Yongxin; Audoly, Laurent; Therien, Alex G; Xu, Daigen

    2008-05-01

    Previous evidence has implicated E prostanoid receptor 4 (EP4) in mechanical hyperalgesia induced by subplantar inflammation. However, its role in chronic arthritis remains to be further defined because previous attempts have generated two conflicting lines of evidence, with one showing a marked reduction of arthritis induced by a collagen antibody in mice lacking EP4, but not EP1-EP3, and the other showing no impact of EP4 antagonism on arthritis induced by collagen. Here, we assessed the effect of a novel and selective EP4 antagonist MF498 [N-{[4-(5,9-diethoxy-6-oxo-6,8-dihydro-7H-pyrrolo[3,4-g]quinolin-7-yl)-3-methylbenzyl]sulfonyl}-2-(2-methoxyphenyl)acetamide] on inflammation in adjuvant-induced arthritis (AIA), a rat model for rheumatoid arthritis (RA), and joint pain in a guinea pig model of iodoacetate-induced osteoarthritis (OA). In the AIA model, MF498, but not the antagonist for EP1, MF266-1 [1-(5-{3-[2-(benzyloxy)-5-chlorophenyl]-2-thienyl}pyridin-3-yl)-2,2,2-trifluoroethane-1,1-diol] or EP3 MF266-3 [(2E)-N-[(5-bromo-2-methoxyphenyl)sulfonyl]-3-[5-chloro-2-(2-naphthylmethyl)phenyl]acrylamide], inhibited inflammation, with a similar efficacy as a selective cyclooxygenase 2 (COX-2) inhibitor MF-tricyclic. In addition, MF498 was as effective as an nonsteroidal anti-inflammatory drug, diclofenac, or a selective microsomal prostaglandin E synthase-1 inhibitor, MF63 [2-(6-chloro-1H-phenanthro[9,10-d]imidazol-2-yl)isophthalonitrile], in relieving OA-like pain in guinea pigs. When tested in rat models of gastrointestinal toxicity, the EP4 antagonist was well tolerated, causing no mucosal leakage or erosions. Lastly, we evaluated the renal effect of MF498 in a furosemide-induced diuresis model and demonstrated that the compound displayed a similar renal effect as MF-tricyclic [3-(3,4-difluorophenyl)-4-(4-(methylsulfonyl)phenyl)-2-(5H)-furanone], reducing furosemide-induced natriuresis by approximately 50%. These results not only suggest that EP4 is the major EP

  7. A luminescent zinc(ii) coordination polymer with unusual (3,4,4)-coordinated self-catenated 3D network for selective detection of nitroaromatics and ferric and chromate ions: a versatile luminescent sensor.

    PubMed

    Zhang, Ya-Qian; Blatov, Vladislav A; Zheng, Tian-Rui; Yang, Chang-Hao; Qian, Lin-Lu; Li, Ke; Li, Bao-Long; Wu, Bing

    2018-05-01

    A zinc(ii) coordination polymer {[Zn3(mtrb)3(btc)23H2O}n (1) was synthesized and characterized (mtrb = 1,3-bis(1,2,4-triazole-4-ylmethyl)benzene, btc = 1,3,5-benzenetricarboxylate). The polymer 1 shows an unusual (3,4,4)-coordinated self-catenated 3D network with the point symbol of {63}2{62·82·102}{64·82}2. The polymer 1 is the first luminescent sensor for the detection of 2-amino-4-nitrophenol (ANP). The polymer 1 is also a good luminescence sensor for detection of TNP, 2,4-DNP, 4-NP, ANP and 2-NP in MeOH, particularly for TNP. The order of detection efficiency is TNP > 2,4-DNP > 4-NP > ANP > 2-NP. The polymer 1 also exhibits high sensitivity and selectivity as a luminescence sensor for the detection of Fe3+, Cr2O72- and CrO42- in aqueous solution. Our experiments showed that the presence of interfering ions had no significant effect on the sensing of Fe3+, Cr2O72- or CrO42- ions. The detection limits for TNP, ANP, Fe3+, Cr2O72- and CrO42- are 0.22 μM, 4.12 μM, 1.78 μM, 2.83 μM, and 4.52 μM, respectively. The luminescence sensor is stable and can be recycled for detection at least five times. The possible quenching mechanisms are discussed. The polymer 1 is also an effective photocatalyst for degradation of methylene blue (MB) under visible or UV light irradiation.

  8. 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.

  9. Crystal structure of 3-[(4-benzyl-piperazin-1-yl)meth-yl]-5-(thio-phen-2-yl)-2,3-di-hydro-1,3,4-oxa-diazole-2-thione.

    PubMed

    Al-Omary, Fatmah A M; El-Emam, Ali A; Ghabbour, Hazem A; Chidan Kumar, C S; Quah, Ching Kheng; Fun, Hoong-Kun

    2015-03-01

    The title 1,3,4-oxa-diazole-2-thione derivative, C18H20N4OS2, crystallized with two independent mol-ecules (A and B) in the asymmetric unit. The 2-thienyl rings in both mol-ecules are rotationally disordered over two orientations by approximately 180° about the single C-C bond that connects it to the oxa-diazole thione ring; the ratios of site occupancies for the major and minor components were fixed in the structure refinement at 0.8:0.2 and 0.9:0.1 in mol-ecules A and B, respectively. The 1,3,4-oxa-diazole-2-thione ring forms dihedral angles of 7.71 (16), 10.0 (11) and 77.50 (12)° (mol-ecule A), and 6.5 (3), 6.0 (9) and 55.30 (12)° (mol-ecule B) with the major and minor parts of the disordered thio-phene ring and the mean plane of the adjacent piperazine ring, respectively, resulting in approximately V-shaped conformations for the mol-ecules. The piperazine ring in both mol-ecules adopts a chair conformation. The terminal benzene ring is inclined towards the mean plane of the piperazine ring with N-C-C-C torsion angles of -58.2 (3) and -66.2 (3)° in mol-ecules A and B, respectively. In the crystal, no inter-molecular hydrogen bonds are observed. The crystal packing features short S⋯S contacts [3.4792 (9) Å] and π-π inter-actions [3.661 (3), 3.664 (11) and 3.5727 (10) Å], producing a three-dimensional network.

  10. Solid state coordination chemistry: structural consequences of variations in tether length in the oxovanadium-copper-bisterpy-[O3P(CH2)nPO3]4- system, n= 1-6 (bisterpy = 2,2':4',4'':2'',2'''-quarterpyridyl-6',6''-di-2-pyridine).

    PubMed

    Ouellette, Wayne; Koo, Bon-Kweon; Burkholder, Eric; Golub, Vladimir; O'Connor, C J; Zubieta, Jon

    2004-05-21

    Hydrothermal reactions of Na3VO4, an appropriate Cu(II) source, bisterpy and an organodiphosphonate, H2O3P(CH2)nPO3H2 (n = 1-6) yielded a family of materials of the type [Cu2(bisterpy)]4+/VxOy(n-)/[O3P(CH2)nPO3]4-. This family of bimetallic oxides is characterized by an unusual structural diversity. The oxides [[Cu2(bisterpy)]V2O4[O3PCH2PO3H]2] (1), [[Cu2(bisterpy)(H2O)]VO2[O3P(CH2)3PO3][HO3P(CH2)3PO3H2

  11. In-Situ and Real-time Monitoring of Mechanochemical Preparation of Li2 Mg(NH2 BH3 )4 and Na2 Mg(NH2 BH3 )4 and Their Thermal Dehydrogenation.

    PubMed

    Biliškov, Nikola; Borgschulte, Andreas; Užarević, Krunoslav; Halasz, Ivan; Lukin, Stipe; Milošević, Sanja; Milanović, Igor; Novaković, Jasmina Grbović

    2017-11-16

    For the first time, in situ monitoring of uninterrupted mechanochemical synthesis of two bimetallic amidoboranes, M 2 Mg(NH 2 BH 3 ) 4 (M=Li, Na), by means of Raman spectroscopy, has been applied. This approach allowed real-time observation of key intermediate phases, and a straightforward follow-up of the reaction course. Detailed analysis of time-dependent spectra revealed a two-step mechanism through MNH 2 BH 3 ⋅NH 3 BH 3 adducts as key intermediate phases which further reacted with MgH 2 , giving M 2 Mg(NH 2 BH 3 ) 4 as final products. The intermediates partially take a competitive pathway toward the oligomeric M(BH 3 NH 2 BH 2 NH 2 BH 3 ) phases. The crystal structure of the novel bimetallic amidoborane Li 2 Mg(NH 2 BH 3 ) 4 was solved from high-resolution powder diffraction data and showed an analogous metal coordination to Na 2 Mg(NH 2 BH 3 ) 4 , but a significantly different crystal packing. Li 2 Mg(NH 2 BH 3 ) 4 thermally dehydrogenates releasing highly pure H 2 in the amount of 7 wt.%, and at a lower temperature then its sodium analogue, making it significantly more viable for practical applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. PTEN Regulates PI(3,4)P2 Signaling Downstream of Class I PI3K.

    PubMed

    Malek, Mouhannad; Kielkowska, Anna; Chessa, Tamara; Anderson, Karen E; Barneda, David; Pir, Pınar; Nakanishi, Hiroki; Eguchi, Satoshi; Koizumi, Atsushi; Sasaki, Junko; Juvin, Véronique; Kiselev, Vladimir Y; Niewczas, Izabella; Gray, Alexander; Valayer, Alexandre; Spensberger, Dominik; Imbert, Marine; Felisbino, Sergio; Habuchi, Tomonori; Beinke, Soren; Cosulich, Sabina; Le Novère, Nicolas; Sasaki, Takehiko; Clark, Jonathan; Hawkins, Phillip T; Stephens, Len R

    2017-11-02

    The PI3K signaling pathway regulates cell growth and movement and is heavily mutated in cancer. Class I PI3Ks synthesize the lipid messenger PI(3,4,5)P 3 . PI(3,4,5)P 3 can be dephosphorylated by 3- or 5-phosphatases, the latter producing PI(3,4)P 2 . The PTEN tumor suppressor is thought to function primarily as a PI(3,4,5)P 3 3-phosphatase, limiting activation of this pathway. Here we show that PTEN also functions as a PI(3,4)P 2 3-phosphatase, both in vitro and in vivo. PTEN is a major PI(3,4)P 2 phosphatase in Mcf10a cytosol, and loss of PTEN and INPP4B, a known PI(3,4)P 2 4-phosphatase, leads to synergistic accumulation of PI(3,4)P 2 , which correlated with increased invadopodia in epidermal growth factor (EGF)-stimulated cells. PTEN deletion increased PI(3,4)P 2 levels in a mouse model of prostate cancer, and it inversely correlated with PI(3,4)P 2 levels across several EGF-stimulated prostate and breast cancer lines. These results point to a role for PI(3,4)P 2 in the phenotype caused by loss-of-function mutations or deletions in PTEN. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

  13. In vivo effects of goldenseal, kava kava, black cohosh, and valerian on human cytochrome P450 1A2, 2D6, 2E1, and 3A4/5 phenotypes.

    PubMed

    Gurley, Bill J; Gardner, Stephanie F; Hubbard, Martha A; Williams, D Keith; Gentry, W Brooks; Khan, Ikhlas A; Shah, Amit

    2005-05-01

    Phytochemical-mediated modulation of cytochrome P450 (CYP) activity may underlie many herb-drug interactions. Single-time point phenotypic metabolic ratios were used to determine whether long-term supplementation of goldenseal ( Hydrastis canadensis ), black cohosh ( Cimicifuga racemosa ), kava kava ( Piper methysticum ), or valerian ( Valeriana officinalis ) extracts affected CYP1A2, CYP2D6, CYP2E1, or CYP3A4/5 activity. Twelve healthy volunteers (6 women) were randomly assigned to receive goldenseal, black cohosh, kava kava, or valerian for 28 days. For each subject, a 30-day washout period was interposed between each supplementation phase. Probe drug cocktails of midazolam and caffeine, followed 24 hours later by chlorzoxazone and debrisoquin (INN, debrisoquine), were administered before (baseline) and at the end of supplementation. Presupplementation and postsupplementation phenotypic trait measurements were determined for CYP3A4/5, CYP1A2, CYP2E1, and CYP2D6 by use of 1-hydroxymidazolam/midazolam serum ratios (1-hour sample), paraxanthine/caffeine serum ratios (6-hour sample), 6-hydroxychlorzoxazone/chlorzoxazone serum ratios (2-hour sample), and debrisoquin urinary recovery ratios (8-hour collection), respectively. The content of purported "active" phytochemicals was determined for each supplement. Comparisons of presupplementation and postsupplementation phenotypic ratio means revealed significant inhibition (approximately 40%) of CYP2D6 (difference, -0.228; 95% confidence interval [CI], -0.268 to -0.188) and CYP3A4/5 (difference, -1.501; 95% CI, -1.840 to -1.163) activity for goldenseal. Kava produced significant reductions (approximately 40%) in CYP2E1 only (difference, -0.192; 95% CI, -0.325 to -0.060). Black cohosh also exhibited statistically significant inhibition of CYP2D6 (difference, -0.046; 95% CI, -0.085 to -0.007), but the magnitude of the effect (approximately 7%) did not appear to be clinically relevant. No significant changes in phenotypic

  14. Crystal structure of 3-{[4-(2-meth-oxy-phen-yl)piperazin-1-yl]meth-yl}-5-(thio-phen-2-yl)-1,3,4-oxa-diazole-2(3H)-thione.

    PubMed

    Al-Alshaikh, Monirah A; Abuelizz, Hatem A; El-Emam, Ali A; Abdelbaky, Mohammed S M; Garcia-Granda, Santiago

    2016-02-01

    The title compound, C18H20N4O2S2, is a new 1,3,4-oxa-diazole and a key pharmacophore of several biologically active agents. It is composed of a meth-yl(thio-phen-2-yl)-1,3,4-oxa-diazole-2(3H)-thione moiety linked to a 2-meth-oxy-phenyl unit via a piperazine ring that has a chair conformation. The thio-phene ring mean plane lies almost in the plane of the oxa-diazole ring, with a dihedral angle of 4.35 (9)°. The 2-meth-oxy-phenyl ring is almost normal to the oxa-diazole ring, with a dihedral angle of 84.17 (10)°. In the crystal, mol-ecules are linked by weak C-H⋯S hydrogen bonds and C-H⋯π inter-actions, forming layers parallel to the bc plane. The layers are linked via weak C-H⋯O hydrogen bonds and slipped parallel π-π inter-actions [inter-centroid distance = 3.6729 (10) Å], forming a three-dimensional structure. The thio-phene ring has an approximate 180° rotational disorder about the bridging C-C bond.

  15. Fabrication, patterning and luminescence properties of X 2-Y 2SiO 5:A (A=Eu 3+, Tb 3+, Ce 3+) phosphor films via sol-gel soft lithography

    NASA Astrophysics Data System (ADS)

    Han, X. M.; Lin, J.; Fu, J.; Xing, R. B.; Yu, M.; Zhou, Y. H.; Pang, M. L.

    2004-04-01

    X 2-Y 2SiO 5:A (A=Eu 3+, Tb 3+, Ce 3+) phosphor films and their patterning were fabricated by a sol-gel process combined with a soft lithography. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy (AFM), scanning electron microscopy (SEM) optical microscopy and photoluminescence (PL) were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 900 °C with X 1-Y 2SiO 5, which transformed completely to X 2-Y 2SiO 5 at 1250 °C. Patterned thin films with different band widths (5 μm spaced by 5 μm and 16 μm spaced by 24 μm) were obtained by a soft lithography technique (micromoulding in capillaries, MIMIC). The SEM and AFM study revealed that the nonpatterned phosphor films were uniform and crack free, and the films mainly consisted of closely packed grains with an average size of 350 nm. The doped rare earth ions (A) showed their characteristic emissions in X 2-Y 2SiO 5 phosphor films, i.e., 5D 0- 7F J ( J=0,1,2,3,4) for Eu 3+, 5D 3, 4- 7F J ( J=6,5,4,3) for Tb 3+ and 5d ( 2D)-4f ( 2F 2/5, 2/7) for Ce 3+, respectively. The optimum doping concentrations for Eu 3+, Tb 3+ were determined to be 13 and 8 mol% of Y 3+ in X 2-Y 2SiO 5 films, respectively.

  16. Synthesis,and structural characterization of [(CH3(C5H4N))Ga(SCH2(CO)O)]-[(4-MepyH)]+, a novel Ga(III) five coordinate complex.

    NASA Technical Reports Server (NTRS)

    Banger, Kulbinder K.; Duraj, Stan A.; Fanwic, Phillp E.; Hepp, Aloysius F.; Martuch, Robert A.

    2003-01-01

    The synthesis and structural characterization of a novel ionic Ga(III) five coordinate complex [{CH3(C5H4N)}Ga(SCH2(CO)O)2]-[(4-MepyH)]+, (4-Mepy = CH3(C5H5N)) from the reaction between Ga2Cl4 with sodium mercapto-acetic acid in 4-methylpyridine is described. Under basic reaction conditions the mercapto ligand is found to behave as a 2e- bidentate ligand. Single crystal X-ray diffraction studies show the complex to have a distorted square pyramidal geometry with the [(-SCH2(CO)CO-)] ligands in a trans conformation. The compound crystallizes in the P2(sub 1)/c (No. 14) space group with a = 7.7413(6) A, b = 16.744(2) A, c = 14.459(2) A, V = 1987.1(6) A(sup 3), R(F) = 0.032 and R(sub w) = 0.038.

  17. A kinetic study on the catalysis of KCl, K2SO4, and K2CO3 during oxy-biomass combustion.

    PubMed

    Deng, Shuanghui; Wang, Xuebin; Zhang, Jiaye; Liu, Zihan; Mikulčić, Hrvoje; Vujanović, Milan; Tan, Houzhang; Duić, Neven

    2018-07-15

    Biomass combustion under the oxy-fuel conditions (Oxy-biomass combustion) is one of the approaches achieving negative CO 2 emissions. KCl, K 2 CO 3 and K 2 SO 4 , as the major potassium species in biomass ash, can catalytically affect biomass combustion. In this paper, the catalysis of the representative potassium salts on oxy-biomass combustion was studied using a thermogravimetric analyzer (TGA). Effects of potassium salt types (KCl, K 2 CO 3 and K 2 SO 4 ), loading concentrations (0, 1, 3, 5, 8 wt%), replacing N 2 by CO 2 , and O 2 concentrations (5, 20, 30 vol%) on the catalysis degree were discussed. The comparison between TG-DTG curves of biomass combustion before and after water washing in both the 20%O 2 /80%N 2 and 20%O 2 /80%CO 2 atmospheres indicates that the water-soluble minerals in biomass play a role in promoting the devolatilization and accelerating the char-oxidation; and the replacement of N 2 by CO 2 inhibits the devolatilization and char-oxidation processes during oxy-biomass combustion. In the devolatilization stage, the catalysis degree of potassium monotonously increases with the increase of potassium salt loaded concentration. The catalysis degree order of the studied potassium salts is K 2 CO 3  > KCl > K 2 SO 4 . In the char-oxidation stage, with the increase of loading concentration the three kinds of potassium salts present inconsistent change tendencies of the catalysis degree. In the studied loading concentrations from 0 to 8 wt%, there is an optimal loading concentration for KCl and K 2 CO 3 , at 3 and 5 wt%, respectively; while for K 2 SO 4 , the catalysis degree on char-oxidation monotonically increases with the loading potassium concentration. For most studied conditions, regardless of the potassium salt types or the loading concentrations or the combustion stages, the catalysis degree in the O 2 /CO 2 atmosphere is stronger than that in the O 2 /N 2 atmosphere. The catalysis degree is also affected by the O 2

  18. A single phase, red emissive Mg2SiO4:Sm3+ nanophosphor prepared via rapid propellant combustion route

    NASA Astrophysics Data System (ADS)

    Naik, Ramachandra; Prashantha, S. C.; Nagabhushana, H.; Sharma, S. C.; Nagaswarupa, H. P.; Anantharaju, K. S.; Nagabhushana, B. M.; Premkumar, H. B.; Girish, K. M.

    2015-04-01

    Mg2SiO4:Sm3+ (1-11 mol%) nanoparticles were prepared by a rapid low temperature solution combustion route. The powder X-ray diffraction (PXRD) patterns exhibit orthorhombic structure with α-phase. The average crystallite size estimated using Scherer's method, W-H plot and strain-size plots were found to be in the range 25-50 nm and the same was confirmed by Transmission Electron Microscopy (TEM). Scanning electron microscopy (SEM) pictures show porous structure and crystallites were agglomerated. The effect of Sm3+ cations on luminescence of Mg2SiO4 was well studied. Interestingly the samples could be effectively excited with 315 nm and emitted light in the red region, which was suitable for the demands of high efficiency WLEDs. The emission spectra consists of four main peaks which can be assigned to the intra 4-f orbital transitions of Sm3+ ions 4G5/2 → 6H5/2 (576 nm), 4G5/2 → 6H7/2 (611 nm), 4G5/2 → 6H9/2 (656 nm) and 4G5/2 → 6H11/2 (713 nm). The optimal luminescence intensity was obtained for 5 mol% Sm3+ ions. The CIE (Commission International de I'Eclairage) chromaticity co-ordinates were calculated from emission spectra, the values (0.588, 0.386) were close to the NTSC (National Television Standard Committee) standard value of red emission. Coordinated color temperature (CCT) was found to be 1756 K. Therefore optimized Mg2SiO4:Sm3+ (5 mol%) phosphor was quite useful for solid state lighting.

  19. Highly visible-light-responsive Cu2O/rGO decorated with Fe3O4@SiO2 nanoparticles as a magnetically recyclable photocatalyst

    NASA Astrophysics Data System (ADS)

    Liu, Shou-Heng; Lu, Jun-Sheng; Yang, Sheng-Wei

    2018-07-01

    The rhombic dodecahedral cuprous oxide-reduced graphene oxide/core–shell Fe3O4@SiO2 composites (denoted as rCu2O-rGO/Fe3O4@SiO2) are successfully synthesized facilely via a wet-chemical route. The resulting rCu2O-rGO/Fe3O4@SiO2 combines the unique structure of Cu2O, electronic characteristics of reduced graphene oxide (rGO) and magnetic property of Fe3O4@SiO2 to be an effective and recoverable photocatalyst for the degradation of methyl orange (MO). The obtained results show that rCu2O-rGO/Fe3O4@SiO2 is capable of completely degrading MO in the presence of a very low catalyst concentration (0.125 g l‑1) within a short time (60 min) under visible light compared to the reported catalysts. The observations may be due to the distinctive interfacial structures of rhombic dodecahedral Cu2O nanoparticles connected to rGO sheets that can enhance the separation of photogenerated electron–hole pairs, stabilize the Cu2O and increase MO adsorption, as evidenced by a variety of spectroscopic analyses (transmission electron microscopy, x-ray photoelectron spectroscopy and photoluminescence). More importantly, these efficient photocatalysts can easily be recovered under a magnetic field and remain highly photoactive towards the degradation of MO after cyclic tests, and may be promising photocatalysts for practical applications in the solar-energy purification of wastewater.

  20. Highly visible-light-responsive Cu2O/rGO decorated with Fe3O4@SiO2 nanoparticles as a magnetically recyclable photocatalyst.

    PubMed

    Liu, Shou-Heng; Lu, Jun-Sheng; Yang, Sheng-Wei

    2018-07-27

    The rhombic dodecahedral cuprous oxide-reduced graphene oxide/core-shell Fe 3 O 4 @SiO 2 composites (denoted as rCu 2 O-rGO/Fe 3 O 4 @SiO 2 ) are successfully synthesized facilely via a wet-chemical route. The resulting rCu 2 O-rGO/Fe 3 O 4 @SiO 2 combines the unique structure of Cu 2 O, electronic characteristics of reduced graphene oxide (rGO) and magnetic property of Fe 3 O 4 @SiO 2 to be an effective and recoverable photocatalyst for the degradation of methyl orange (MO). The obtained results show that rCu 2 O-rGO/Fe 3 O 4 @SiO 2 is capable of completely degrading MO in the presence of a very low catalyst concentration (0.125 g l -1 ) within a short time (60 min) under visible light compared to the reported catalysts. The observations may be due to the distinctive interfacial structures of rhombic dodecahedral Cu 2 O nanoparticles connected to rGO sheets that can enhance the separation of photogenerated electron-hole pairs, stabilize the Cu 2 O and increase MO adsorption, as evidenced by a variety of spectroscopic analyses (transmission electron microscopy, x-ray photoelectron spectroscopy and photoluminescence). More importantly, these efficient photocatalysts can easily be recovered under a magnetic field and remain highly photoactive towards the degradation of MO after cyclic tests, and may be promising photocatalysts for practical applications in the solar-energy purification of wastewater.

  1. Cytochrome P450 2D6 and 3A4 enzyme inhibition by amine stimulants in dietary supplements.

    PubMed

    Liu, Yitong; Santillo, Michael F

    2016-01-01

    A number of dietary supplements used for weight loss and athletic performance enhancement have been recently shown to contain a variety of stimulants, for which there is a lack of pharmacological and toxicological information. One concern for these emerging compounds is their potential to inhibit metabolic enzymes in the liver such as cytochromes P450 (CYP), which can lead to unexpected interactions among dietary supplements, drugs, and other xenobiotics. In this study, inhibition of human recombinant CYP2D6 and CYP3A4 by 27 amine stimulants associated with dietary supplements and their analogs was evaluated by luminescence assays. The strongest CYP2D6 inhibitors were coclaurine (IC50  = 0.14 ± 0.01 μM) and N-benzylphenethylamine (IC50  = 0.7 ± 0.2 μM), followed by several other relatively strong inhibitors (IC50 , 2-12 μM) including β-methylphenethylamine, N,β-dimethylphenethylamine (phenpromethamine), 1,3-dimethylamylamine (DMAA), N,α-diethylphenethylamine, higenamine (norcoclaurine) and N,N-diethylphenethylamine. Only nine compounds inhibited CYP3A4 by 20-55% at 100 μM. Results of this study illustrate that several amine stimulants associated with dietary supplements inhibit CYP2D6 and CYP3A4 in vitro, and these compounds may participate in adverse drug-dietary supplement interactions in vivo. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

  2. Profound Interfacial Effects in CoFe2O4/Fe3O4 and Fe3O4/CoFe2O4 Core/Shell Nanoparticles

    NASA Astrophysics Data System (ADS)

    Polishchuk, Dmytro; Nedelko, Natalia; Solopan, Sergii; Ślawska-Waniewska, Anna; Zamorskyi, Vladyslav; Tovstolytkin, Alexandr; Belous, Anatolii

    2018-03-01

    Two sets of core/shell magnetic nanoparticles, CoFe2O4/Fe3O4 and Fe3O4/CoFe2O4, with a fixed diameter of the core ( 4.1 and 6.3 nm for the former and latter sets, respectively) and thickness of shells up to 2.5 nm were synthesized from metal chlorides in a diethylene glycol solution. The nanoparticles were characterized by X-ray diffraction, transmission electron microscopy, and magnetic measurements. The analysis of the results of magnetic measurements shows that coating of magnetic nanoparticles with the shells results in two simultaneous effects: first, it modifies the parameters of the core-shell interface, and second, it makes the particles acquire combined features of the core and the shell. The first effect becomes especially prominent when the parameters of core and shell strongly differ from each other. The results obtained are useful for optimizing and tailoring the parameters of core/shell spinel ferrite magnetic nanoparticles for their use in various technological and biomedical applications.

  3. Selective hydrodesulfurization of 4,6-dimethyldibenzothiophene in the dominant presence of naphthalene over hybrid CoMo/A{sub 2}O{sub 3} and Ru/Al{sub 2}Al{sub 2}O{sub 3} catalyst

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

    Isoda, T.; Nagao, S.; Ma, X.

    1995-12-31

    Hydrodesulfurization of 4,6-dimethyldibenzothiophene (4,6-DMDBT) in decane containing significant amount of naphthalene was examined over a hybrid of CoMo/Al{sub 2}O{sub 3} and Ru/Al{sub 2}O{sub 3} to design the selective hydrogenation and successive desulfurization of 4,6-DMDBT in aromatic moiety, and its activity was compared to those of CoMo/Al{sub 2}O{sub 3}, NiMo/Al{sub 2}O{sub 3} and Ru/Al{sub 2}O{sub 3} in their single use. HDS activity of 4,6-DMDBT over NiMo/Al{sub 2}O{sub 3} was inferior to CoMo/Al{sub 2}O{sub 3}, although that of highest hydrogenation activity for naphthalene. The hybrid showed the highest activity for HDS of 4,6-DMDBT among these catalysts without excess hydrogenation of nahthalene.

  4. From {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}]{sup 6-} to {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} infinite chains in A{sub 6}U{sub 2}Mo{sub 4}O{sub 21} (A=Na, K, Rb, Cs) compounds: Synthesis and crystal structure of Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})

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

    Yagoubi, S.; Groupe de Radiochimie, Institut de Physique Nucleaire d'Orsay, Universite Paris-Sud XI, 91406 Orsay Cedex; Obbade, S., E-mail: said.obbade@phelma.grenoble-inp.f

    2011-05-15

    A new caesium uranyl molybdate belonging to the M{sub 6}U{sub 2}Mo{sub 4}O{sub 21} family has been synthesized by solid-state reaction and its structure determined from single-crystal X-ray diffraction data. Contrary to the other alkali uranyl molybdates of this family (A=Na, K, Rb) where molybdenum atoms adopt only tetrahedral coordination and which can be formulated A{sub 6}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}], the caesium compound Cs{sub 6}U{sub 2}Mo{sub 4}O{sub 21} should be written Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] with molybdenum atoms in tetrahedral and square pyramidal environments. Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] crystallizes in the triclinic symmetry withmore » space group P1-bar and a=10.4275(14) A, b=15.075(2) A, c=17.806(2) A, {alpha}=70.72(1){sup o}, {beta}=80.38(1){sup o} and {gamma}=86.39(1){sup o}, V=2604.7(6) A{sup 3}, Z=4, {rho}{sub mes}=5.02(2) g/cm{sup 3} and {rho}{sub cal}=5.08(3) g/cm{sup 3}. A full-matrix least-squares refinement on the basis of F{sup 2} yielded R{sub 1}=0.0464 and wR{sub 2}=0.0950 for 596 parameters with 6964 independent reflections with I{>=}2{sigma}(I) collected on a BRUKER AXS diffractometer with Mo(K{alpha}) radiation and a CCD detector. The crystal structure of Cs compound is characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} parallels chains built from U{sub 2}O{sub 13} dimeric units, MoO{sub 4} tetrahedra and MoO{sub 5} square pyramids, whereas, Na, K and Rb compounds are characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}]{sup 6-} parallel chains formulated simply of U{sub 2}O{sub 13} units and MoO{sub 4} tetrahedra. Infrared spectroscopy measurements using powdered samples synthesized by solid-state reaction, confirm the structural results. The thermal stability and the electrical conductivity are also studied. The four compounds decompose at low temperature (between 540 and 610

  5. Solvent- and DNA-Controlled Phototriggered Linkage Isomerization in a Ruthenium Sulfoxide Complex Incorporating Dipyrido[3,2-a:2',3'-c]phenazine (dppz).

    PubMed

    Phapale, Daulat; Ghosh, Rajib; Das, Dipanwita

    2017-06-05

    A new tris-heteroleptic complex [Ru(bpy)(dppz)(OSO)](ClO 4 ), [1](ClO 4 ) (bpy = 2,2'-bipyridine, dppz = dipyrido[3,2-a:2',3'-c]phenazine and OSO = 2-methylsulfinylbenzoate), was synthesized and characterized to control the photochromic Ru-S → Ru-O linkage isomerization. Details isomerization kinetics studied by UV-visible absorption spectroscopy and cyclic voltammetry revealed that efficient photochromic S → O isomerization and thermal O → S reversal take place in solvents like propylene carbonate (PC), methanol, and dichloromethane. Strikingly, photoisomerization of [1](ClO 4 ) is arrested in water although is active in the analogous compound [Ru(bpy) 2 (OSO)](ClO 4 ). Effective excited state deactivation through dark 3 MLCT state involving dppz ligand of [1](ClO 4 ) switches off photochromism in aqueous medium. Interestingly, the photochromism is activated in aqueous solution in the presence of DNA which shields the dppz localized dark state through intercalation. Ultrafast transient absorption spectroscopic measurement sheds light on the differential behavior of photochromism in aqueous and nonaqueous solvents.

  6. Expression of A-type K channel alpha subunits Kv 4.2 and Kv 4.3 in rat spinal lamina II excitatory interneurons and colocalization with pain-modulating molecules.

    PubMed

    Huang, Hsin-Yi; Cheng, Jen-Kun; Shih, Yang-Hsin; Chen, Pei-Hsuan; Wang, Chin-Lin; Tsaur, Meei-Ling

    2005-09-01

    Voltage-gated K(+) channel alpha subunits Kv 4.2 and Kv 4.3 are the major contributors of somatodendritic A-type K(+) currents in many CNS neurons. A recent hypothesis suggests that Kv 4 subunits may be involved in pain modulation in dorsal horn neurons. However, whether Kv 4 subunits are expressed in dorsal horn neurons remains unknown. Using immunohistochemistry, we found that Kv 4.2 and Kv 4.3 immunoreactivity was concentrated in the superficial dorsal horn, mainly in lamina II. Both Kv 4.2 and Kv 4.3 appeared on many rostrocaudally orientated dendrites, whereas Kv 4.3 could be also detected from certain neuronal somata. Kv 4.3(+) neurons were a subset of excitatory inerneurons with calretinin(+)/calbindin(-)/PKCgamma(-) markers, and a fraction of them expressed micro-opioid receptors. Kv 4.3(+) neurons also expressed ERK 2 and mGluR 5, which are molecules related to the induction of central sensitization, a mechanism mediating nociceptive plasticity. Together with the expression of Kv 4.3 in VR 1(+) DRG neurons, our data suggest that Kv C4 subunits could be involved in pain modulation.

  7. 15 CFR 4a.3 - Classification levels.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 15 Commerce and Foreign Trade 1 2013-01-01 2013-01-01 false Classification levels. 4a.3 Section 4a.3 Commerce and Foreign Trade Office of the Secretary of Commerce CLASSIFICATION, DECLASSIFICATION... E.O. 12958. The levels established by E.O. 12958 (Top Secret, Secret, and Confidential) are the only...

  8. 15 CFR 4a.3 - Classification levels.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 15 Commerce and Foreign Trade 1 2014-01-01 2014-01-01 false Classification levels. 4a.3 Section 4a.3 Commerce and Foreign Trade Office of the Secretary of Commerce CLASSIFICATION, DECLASSIFICATION... E.O. 12958. The levels established by E.O. 12958 (Top Secret, Secret, and Confidential) are the only...

  9. 15 CFR 4a.3 - Classification levels.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 15 Commerce and Foreign Trade 1 2011-01-01 2011-01-01 false Classification levels. 4a.3 Section 4a.3 Commerce and Foreign Trade Office of the Secretary of Commerce CLASSIFICATION, DECLASSIFICATION... E.O. 12958. The levels established by E.O. 12958 (Top Secret, Secret, and Confidential) are the only...

  10. 15 CFR 4a.3 - Classification levels.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 15 Commerce and Foreign Trade 1 2012-01-01 2012-01-01 false Classification levels. 4a.3 Section 4a.3 Commerce and Foreign Trade Office of the Secretary of Commerce CLASSIFICATION, DECLASSIFICATION... E.O. 12958. The levels established by E.O. 12958 (Top Secret, Secret, and Confidential) are the only...

  11. 15 CFR 4a.3 - Classification levels.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 15 Commerce and Foreign Trade 1 2010-01-01 2010-01-01 false Classification levels. 4a.3 Section 4a.3 Commerce and Foreign Trade Office of the Secretary of Commerce CLASSIFICATION, DECLASSIFICATION... E.O. 12958. The levels established by E.O. 12958 (Top Secret, Secret, and Confidential) are the only...

  12. Peptide selectivity between the PDZ domains of human pregnancy-related serine proteases (HtrA1, HtrA2, HtrA3, and HtrA4) can be reshaped by different halogen probes.

    PubMed

    Sun, Mei-Ling; Sun, Li-Mei; Wang, Yong-Qing

    2018-06-01

    The human HtrA family of serine proteases (HtrA1, HtrA2, HtrA3, and HtrA4) are the key enzymes associated with pregnancy and closely related to the development and progression of many pathological events. Previously, it was found that halogen substitution at the indole moiety of peptide Trp-1 residue can form a geometrically satisfactory halogen bond with the Drosophila discs large, zona occludens-1 (PDZ) domain of HtrA proteases. Here, we attempt to systematically investigate the effect of substitution with 4 halogen types and 2 indole positions on the binding affinity and specificity of peptide ligands to the 4 HtrA PDZ domains. The complex structures, interaction energies, halogen-bonding strength, and binding affinity of domain-peptide systems were modeled, analyzed, and measured via computational modeling and fluorescence-based assay. It is revealed that there is a compromise between the local rearrangement of halogen bond involving different halogen atoms and the global optimization of domain-peptide interaction; the substitution position is fundamentally important for peptide-binding affinity, while the halogen type can effectively shift peptide selectivity between the 4 domains. The HtrA1-PDZ and HtrA4-PDZ as well as HtrA2-PDZ and HtrA3-PDZ respond similarly to different halogen substitutions of peptide; -Br substitution at R2-position and -I substitution at R4-position are most effective in improving peptide selectivity for HtrA1-PDZ/HtrA4-PDZ and HtrA2-PDZ/HtrA3-PDZ, respectively; -F substitution would not address substantial effect on peptide selectivity for all the 4 domains. Consequently, the binding affinities of a native peptide ligand DSRIWWV -COOH as well as its 4 R2-halogenated counterparts were determined as 1.9, 1.4, 0.5, 0.27, and 0.92 μM, which are basically consistent with computational analysis. This study would help to rationally design selective peptide inhibitors of HtrA family members by using different halogen substitutions. Copyright

  13. E3024, 3-but-2-ynyl-5-methyl-2-piperazin-1-yl-3,5-dihydro-4H-imidazo[4,5-d]pyridazin-4-one tosylate, is a novel, selective and competitive dipeptidyl peptidase-IV inhibitor.

    PubMed

    Yasuda, Nobuyuki; Nagakura, Tadashi; Inoue, Takashi; Yamazaki, Kazuto; Katsutani, Naruo; Takenaka, Osamu; Clark, Richard; Matsuura, Fumiyoshi; Emori, Eita; Yoshikawa, Seiji; Kira, Kazunobu; Ikuta, Hironori; Okada, Toshimi; Saeki, Takao; Asano, Osamu; Tanaka, Isao

    2006-10-24

    Dipeptidyl peptidase IV (DPP-IV) inhibitors are expected to become a useful new class of anti-diabetic agent. The aim of the present study is to characterize the in vitro and in vivo profile of E3024, 3-but-2-ynyl-5-methyl-2-piperazin-1-yl-3,5-dihydro-4H-imidazo[4,5-d]pyridazin-4-one tosylate, which is a novel imidazopyridazinone-derived DPP-IV inhibitor. E3024 inhibited recombinant human and mouse DPP-IV with IC50 values of approximately 100 nM. E3024 inhibited DPP-IV in human, mouse, rat and canine plasma with IC50 values of 140 to 400 nM. In contrast, E3024 did not inhibit DPP-8 or DPP-9 activity. Kinetic analysis indicated that E3024 is a competitive DPP-IV inhibitor. In Zucker fa/fa rats, E3024 (1 mg/kg) reduced glucose excursion after glucose load, with increases in plasma insulin and active glucagon-like peptide-1 levels. In fasted rats, this compound did not cause hypoglycemia. In a rat 4-week toxicological study, no notable changes were found at doses up to 750 mg/kg. The present preclinical studies indicate that E3024 is a novel selective DPP-IV inhibitor with anti-diabetic effects and a good safety profile.

  14. A highly efficient g-C3N4/SiO2 heterojunction: the role of SiO2 in the enhancement of visible light photocatalytic activity.

    PubMed

    Hao, Qiang; Niu, Xiuxiu; Nie, Changshun; Hao, Simeng; Zou, Wei; Ge, Jiangman; Chen, Daimei; Yao, Wenqing

    2016-11-23

    SiO 2 , an insulator, hardly has any photocatalytic acitivity due to its intrinsic property, and it is generally used as a hard template to increase the surface area of catalysts. However, in this work, we found that the surface state of the insulator SiO 2 can promote the migration of photogenerated charge carriers, leading to the enhancement of the photooxidation ability of graphitic carbon nitride (g-C 3 N 4 ). A one-pot calcination method was employed to prepare g-C 3 N 4 /SiO 2 composites using melamine and SiO 2 as precursors. The composites present considerably high photocatalytic degradation activities for 2,4-dichlorophenol (2,4-DCP) and rhodamine B (RhB) under visible light (λ > 420 nm) irradiation, which are about 1.53 and 4.18 times as high as those of bulk g-C 3 N 4 , respectively. The enhancement of the photocatalytic activity is due to the fact that the introduction of the insulator SiO 2 in g-C 3 N 4 /SiO 2 composites can greatly improve the specific surface area of the composites; more importantly, the impurity energy level of SiO 2 can help accelerate the separation and transfer of electron-hole pairs of g-C 3 N 4 . Electron paramagnetic resonance (EPR) spectroscopy and trapping experiments with different radical scavengers show that the main active species of g-C 3 N 4 are superoxide radicals, while holes also play a role in photodegradation. For g-C 3 N 4 /SiO 2 -5, besides superoxide radicals and holes, the effect of hydroxyl radicals was greatly improved. Finally, a possible mechanism for the photogenerated charge carrier migration of the g-C 3 N 4 /SiO 2 photocatalyst was proposed.

  15. Use of vibrational spectroscopy to study 4-benzyl-3-(thiophen-2-yl)-4,5-dihydro-1H-1,2,4-triazole-5-thione: A combined theoretical and experimental approach

    NASA Astrophysics Data System (ADS)

    Sert, Yusuf; El-Emam, Ali A.; Al-Abdullah, Ebtehal S.; Al-Tamimi, Abdul-Malek S.; Çırak, Çağrı; Ucun, Fatih

    In this study, the experimental and theoretical vibrational frequencies of a newly synthesized potential anti-inflammatory agent namely, 4-benzyl-3-(thiophen-2-yl)-4,5-dihydro-1H-1,2,4-triazole-5-thione have been investigated. The experimental FT-IR (4000-400 cm-1) and Laser-Raman spectra (4000-100 cm-1) of the molecule in solid phase have been recorded. The theoretical vibrational frequencies and the optimized geometric parameters (bond lengths, bond angles and dihedral angles) have been calculated using density functional theory methods (DFT/B3LYP: Becke, 3-parameter, Lee-Yang-Parr and DFT/M06-2X: the highly parameterized, empirical exchange correlation function) with 6-311++G(d,p) basis set by Gaussian 09W software, for the first time. The assignments of the vibrational frequencies have been done by potential energy distribution (PED) analysis using VEDA 4 software program. The theoretical optimized geometric parameters and vibrational frequencies have been found to be in good agreement with the corresponding experimental data and results in the literature. In addition, the highest occupied molecular orbital (HOMO) energy, the lowest unoccupied molecular orbital (LUMO) energy and the other related molecular energy values of the compound have been investigated using the same theoretical calculations.

  16. N-Substituted cis-4a-(3-Hydroxyphenyl)-8a-methyloctahydroisoquinolines Are Opioid Receptor Pure Antagonists

    PubMed Central

    Carroll, F. Ivy; Chaudhari, Sachin; Thomas, James B.; Mascarella, S. Wayne; Gigstad, Kenneth M.; Deschamps, Jeffrey; Navarro, Hernán A.

    2008-01-01

    N-Substituted cis-4a-(3-hydroxyphenyl)-8a-methyloctahydroisoquinolines (6a–g) were designed and synthesized as conformationally constrained analogues of the trans-3,4-dimethyl-4-(3-hydroxyphenyl)piperidine (4) class of opioid receptor pure antagonists. The methyloctahydroisoquinolines 6a–g can exist in conformations where the 3-hydroxyphenyl substituent is either axial or equatorial similar to the (3-hydroxyphenyl)piperidines 4. The 3-hydroxyphenyl equatorial conformation is responsible for the antagonist activity observed in the (3-hydroxyphenyl)piperidine antagonists. Single crystal X-ray analysis of 6a shows that the 3-hydroxyphenyl equatorial conformation is favored in the solid state. Molecular modeling studies also suggest that the equatorial conformation has the lower potential energy relative to the axial conformation. Evaluation of compounds 6a–g in the [35S]GTP-γ-S in vitro functional assay showed that they were opioid receptor pure antagonists. N-[4a-(3-Hydroxyphenyl)-8a-methyl-2-(3-phenylpropyl)octahydroisoquinoline-6-yl]-3-(piperidin-1-yl)propionamide (6d) with a Ke of 0.27 nM at the κ opioid receptor with 154- and 46-fold selectively relative to the μ and δ receptors, respectively, possessed the best combination of κ potency and selectivity. PMID:16366600

  17. CXCL12/CXCR4 pathway is activated by oncogenic JAK2 in a PI3K-dependent manner

    PubMed Central

    Abdelouahab, Hadjer; Zhang, Yanyan; Wittner, Monika; Oishi, Shinya; Fujii, Nobutaka; Besancenot, Rodolphe; Plo, Isabelle; Ribrag, Vincent; Solary, Eric; Vainchenker, William; Barosi, Giovanni; Louache, Fawzia

    2017-01-01

    JAK2 activation is the driver mechanism in BCR-ABL-negative myeloproliferative neoplasms (MPN). These diseases are characterized by an abnormal retention of hematopoietic stem cells within the bone marrow microenvironment and their increased trafficking to extramedullary sites. The CXCL12/CXCR4 axis plays a central role in hematopoietic stem cell/ progenitor trafficking and retention in hematopoietic sites. The present study explores the crosstalk between JAK2 and CXCL12/CXCR4 signaling pathways in MPN. We show that JAK2, activated by either MPL-W515L expression or cytokine stimulation, cooperates with CXCL12/CXCR4 signaling to increase the chemotactic response of human cell lines and primary CD34+ cells through an increased phosphatidylinositol-3-kinase (PI3K) signaling. Accordingly, primary myelofibrosis (MF) patient cells demonstrate an increased CXCL12-induced chemotaxis when compared to controls. JAK2 inhibition by knock down or chemical inhibitors decreases this effect in MPL-W515L expressing cell lines and reduces the CXCL12/CXCR4 signaling in some patient primary cells. Taken together, these data indicate that CXCL12/CXCR4 pathway is overactivated in MF patients by oncogenic JAK2 that maintains high PI3K signaling over the threshold required for CXCR4 activation. These results suggest that inhibition of this crosstalk may contribute to the therapeutic effects of JAK2 inhibitors. PMID:28903325

  18. Metabolism of Endosulfan-Alpha by Human Liver Microsomes and its Utility as a Simultaneous In Vitro Probe for CYP2B6 and CYP3A4

    DTIC Science & Technology

    2006-03-30

    METABOLISM OF ENDOSULFAN-ALPHA BY HUMAN LIVER MICROSOMES AND ITS UTILITY AS A SIMULTANEOUS IN VITRO PROBE FOR CYP2B6 AND CYP3A4 Richard C.T. Casabar...MICROSOMES AND ITS UTILITY AS A SIMULTANEOUS IN VITRO PROBE FOR CYP2B6 AND CYP3A4 Corresponding Author: Randy L. Rose Department of Environmental and Molecular...ALPHA BY HUMAN LIVER MICROSOMES AND ITS UTILITY AS A SIMULTANEOUS IN VITRO PROBE FOR CYP2B6 AND CYP3A4 . 6. AUTHOR(S) CAPT CASABAR RICHARD C 7

  19. Association between H3K4 methylation and cancer prognosis: A meta-analysis.

    PubMed

    Li, Simin; Shen, Luyan; Chen, Ke-Neng

    2018-05-08

    Histone H3 lysine 4 methylation (H3K4 methylation), including mono-methylation (H3K4me1), di-methylation (H3K4me2), or tri-methylation (H3K4me3), is one of the epigenetic modifications to histone proteins, which are related to the transcriptional activation of genes. H3K4 methylation has both tumor inhibiting and promoting effects, and the prognostic value of H3K4 methylation in cancer remains controversial. Therefore, we performed a systematic review and meta-analysis to examine the association between H3K4 methylation and cancer prognosis. A comprehensive search of PubMed, Web of Science, ScienceDirect, Embase, and Ovid databases was conducted to identify studies investigating the association between H3K4 methylation and prognosis of patients with malignant tumors. The data and characteristics of each study were extracted, and the hazard ratio (HR) at a 95% confidence interval (CI) was calculated to estimate the effect. A total of 1474 patients in 10 studies were enrolled in this meta-analysis. The pooled HR of 1.52 (95% CI 1.02-2.26) indicated that patients with a lower level of H3K4me2 expression were expected to have shorter overall survival, while the pooled HR of 0.45 (95% CI 0.27-0.74) indicated that patients with a lower level of H3K4me3 expression were expected to have longer overall survival. This meta-analysis indicates that increased H3K4me3 expression and decreased H3K4me2 expression might be predictive factors of poor prognosis in cancer. Further large cohort studies are needed to confirm these findings. © 2018 The Authors. Thoracic Cancer published by China Lung Oncology Group and John Wiley & Sons Australia, Ltd.

  20. Virtual screening, SAR, and discovery of 5-(indole-3-yl)-2-[(2-nitrophenyl)amino] [1,3,4]-oxadiazole as a novel Bcl-2 inhibitor.

    PubMed

    Ziedan, Noha I; Hamdy, Rania; Cavaliere, Alessandra; Kourti, Malamati; Prencipe, Filippo; Brancale, Andrea; Jones, Arwyn T; Westwell, Andrew D

    2017-07-01

    A new series of oxadiazoles were designed to act as inhibitors of the anti-apoptotic Bcl-2 protein. Virtual screening led to the discovery of new hits that interact with Bcl-2 at the BH3 binding pocket. Further study of the structure-activity relationship of the most active compound of the first series, compound 1, led to the discovery of a novel oxadiazole analogue, compound 16j, that was a more potent small-molecule inhibitor of Bcl-2. 16j had good in vitro inhibitory activity with submicromolar IC 50 values in a metastatic human breast cancer cell line (MDA-MB-231) and a human cervical cancer cell line (HeLa). The antitumour effect of 16j is concomitant with its ability to bind to Bcl-2 protein as shown by an enzyme-linked immunosorbent assay (IC 50  = 4.27 μm). Compound 16j has a great potential to develop into highly active anticancer agent. © 2017 John Wiley & Sons A/S.

  1. Improved water resistance of SrAl2O4: Eu2+, Dy3+ phosphor directly achieved in a water-containing medium

    NASA Astrophysics Data System (ADS)

    Qi, Tonggang; Xia, Haofu; Zhang, Zhanhui; Kong, Shijin; Peng, Weikang; Zhao, Qi; Huang, Zhiliang

    2017-03-01

    In this paper, a heterogeneous precipitation method utilizing urea hydrolysis was adopted to coat a SiO2 layer on the surface of SrAl2O4:Eu2+, Dy3+ long persistence phosphors. To avoid phosphor hydrolysis in a water-containing coating medium, the hydrolysis and polymerization reactions of tetraethyl orthosilicate (TEOS) were concerned and carried out. The crystal phases, surface morphologies, hydrolysis stability and water resistance on afterglow properties of coated phosphors were investigated. Scanning electron microscopy, energy dispersive spectrum analysis, transmission electron microscope and Fourier transform infrared spectrum results confirmed that a continuous, uniform and compact SiO2 coating layer was successfully obtained on the phosphors surface. A theoretical coating amount of 5% or higher was found to be good for hydrolysis stability. Photoluminescence results revealed the coated phosphors showed much better water resistance on afterglow properties than the uncoated phosphor. We also discussed and proposed the hydrolysis restriction mechanism of SrAl2O4:Eu2+, Dy3+ in the water-containing coating medium.

  2. INDUCTION AND POST-TRANSCRIPTIONAL SUPPRESSION OF HEPATIC CYTOCHROME P450 1A1 BY 3,3',4,4'-TETRACHLOROBIPHENYL. (R827102)

    EPA Science Inventory

    2>Abstract2>

    3,3',4,4'-Tetrachlorobiphenyl (TCB) can induce and inhibit cytochrome P450 1A1 (CYP1A1) in vertebrates. TCB may also suppress CYP1A1 protein levels, but the mechanism is unknown. This study examined transcriptional and translational aspects of hepatic ...

  3. Solvothermal synthesis and structural characterization of a three-dimensional metal organic polymer [NaZn(1,2,4-BTC)] (1,2,4-BTC=1,2,4-benzenetricarboxylate)

    NASA Astrophysics Data System (ADS)

    Wang, Lei; Shi, Zhan; Li, Guanghua; Fan, Yong; Fu, Wensheng; Feng, Shouhua

    2004-01-01

    A new three-dimensional metal-organic polymer, [NaZn(1,2,4-BTC)] (where 1,2,4-BTC=1,2,4-benzenetricarboxylate), has been prepared under solvothermal conditions and characterized by single crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P2 1/ c, with cell parameters: a=9.7706(4) Å, b=12.3549(5) Å, c=6.8897(3) Å, β=91.640(2)°, V=831.35(6) Å 3 and Z=4. In the three-dimensional structure of the compound, each Zn atom is five-coordinated in distorted trigonal bipyramidal geometry, while the sixfold coordination of Na corresponds to a slightly distorted triangular prism. The organic ligand, 1,2,4-BTC, shows a novel and unprecedented coordination mode: 11 bonds to 10 metals with each carboxylate function exhibiting different linkages. It remains stable when desolvated and when heated up to 410 °C.

  4. Effects of the potential antidepressant OPC-14523 [1-[3-[4-(3-chlorophenyl)-1-piperazinyl]propyl]-5-methoxy-3,4-dihydro-2-quinolinone monomethanesulfonate] a combined sigma and 5-HT1A ligand: modulation of neuronal activity in the dorsal raphe nucleus.

    PubMed

    Bermack, Jordanna E; Haddjeri, Nasser; Debonnel, Guy

    2004-08-01

    OPC-14523 (OPC; [1-[3-[4-(3-chlorophenyl)-1-piperazinyl]propyl]-5-methoxy-3,4-dihydro-2-quinolinone monomethanesulfonate)] is a novel compound with high affinity for sigma and 5-HT(1A) receptors as well as for the 5-HT transporter. OPC has previously been shown to produce antidepressant-like effects in animal models of depression. This project set out to determine the effect of OPC on serotonergic neurotransmission and to shed light on its mechanism(s) of action. In an electrophysiological model of in vivo extracellular recordings in anesthetized rats, a 2-day treatment (1 mg/kg/day) with OPC induced a significant increase in dorsal raphe nucleus (DRN) putative 5-HT neurons' firing activity. This increase was blocked by the coadministration of NE-100 [N,N-dipropyl-2-(4-methoxy-3-(2-phenylethoxy)phenyl)-thylamine], a selective sigma(1) antagonist (10 mg/kg/day). Furthermore, after 2-day treatments with OPC, the 5-HT(1A) autoreceptor response was altered, as demonstrated by the dramatically reduced response to an increase of endogenous 5-HT induced by the acute administration of paroxetine (500 microg/kg, i.v.). However, the 5-HT(1A) agonist 8-hydroxy-2-(di-n-propylamino)tetralin (8-OH-DPAT) (4 microg/kg, i.v.) maintained its ability to decrease 5-HT firing activity, an effect that was reversible by the subsequent administration of the 5-HT(1A) antagonist WAY 100635 [N-[2-(4-[2-methoxyphenyl]-1-piperazinyl)ethyl]-N-2-pyridinylcyclohexanecarboxamide] (100 microg/kg, i.v.). As 8-OH-DPAT has been shown to act preferentially through postsynaptic 5-HT(1A) receptors, our data suggests that this effect of OPC is mediated primarily by the 5-HT(1A) autoreceptor. The decreased response of the 5-HT(1A) autoreceptor to paroxetine was not blocked by the coadministration of NE-100 indicating that sigma(1) receptors are not involved in this effect. Thus, both sigma and 5-HT(1A) receptors play a role in the "antidepressant-like" effects produced by OPC, which is in keeping with

  5. Spectroscopic studies and structure of 3-methoxy-2 -[(2,4,4,6,6-pentachloro-1,3,5,2{lambda}{sup 5},4{lambda}{sup 5},6{lambda}{sup 5}-triazatriphosphin-2-yl)oxy] benzaldehyde

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

    Oezay, H.; Yildiz, M., E-mail: myildiz@comu.edu.tr; Uenver, H.

    2013-01-15

    The compound called 3-methoxy-2- [(2,4,4,6,6-pentachloro-1,3,5,2{lambda}{sup 5},4{lambda}{sup 5},6{lambda}{sup 5}-triazatriphosphin-2-yl)oxy] benzaldehyde has been synthesized from the reaction of 2-hydroxy-3-methoxybenzaldehyde with hexachlorocyclotriphosphazene. It has been characterized by elemental analysis, MS, IR, {sup 1}H NMR, {sup 13}C NMR, {sup 31}P NMR and UV-visible spectroscopic techniques. The structure of the title compound has been determind by X-ray analysis. Crystals are orthorhombic, space group P2{sub 1}2{sub 1}2{sub 1}, Z = 4, a = 7.705(1), b = 12.624(1), c = 17.825(2) A, R{sub 1} = 0.0390 and wR{sub 2} = 0.1074 [I > 2{sigma}(I)], respectively.

  6. The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO2(N3)2, MO2(N3)22 CH3CN, (bipy)MO2(N3)2, and [MO2(N3)4](2-) (M=Mo, W).

    PubMed

    Haiges, Ralf; Skotnitzki, Juri; Fang, Zongtang; Dixon, David A; Christe, Karl O

    2015-08-10

    Molybdenum(VI) and tungsten(VI) dioxodiazide, MO2(N3)2 (M=Mo, W), were prepared through fluoride-azide exchange reactions between MO2F2 and Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride-azide exchange resulted in the isolation of the adducts MO2(N3)22 CH3CN. The subsequent reaction of MO2(N3)2 with 2,2'-bipyridine (bipy) gave the bipyridine adducts (bipy)MO2(N3)2. The hydrolysis of (bipy)MoO2(N3)2 resulted in the formation and isolation of [(bipy)MoO2N3]2O. The tetraazido anions [MO2(N3)4](2-) were obtained by the reaction of MO2(N3)2 with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO2(N3)2, (bipy)WO2(N3)2, [PPh4]2[MoO2(N3)4], [PPh4]2[WO2(N3)4], and [(bipy)MoO2N3]2O by their X-ray crystal structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. The Cytoprotective Effects of E-α-(4-Methoxyphenyl)-2’,3,4,4'-Tetramethoxychalcone (E-α-p-OMe-C6H4-TMC)—A Novel and Non-Cytotoxic HO-1 Inducer

    PubMed Central

    Kaufmann, Kai B.; Al-Rifai, Nafisah; Ulbrich, Felix; Schallner, Nils; Rücker, Hannelore; Enzinger, Monika; Petkes, Hermina; Pitzl, Sebastian

    2015-01-01

    Cell protection against different noxious stimuli like oxidative stress or chemical toxins plays a central role in the treatment of many diseases. The inducible heme oxygenase isoform, heme oxygenase-1 (HO-1), is known to protect cells against a variety of harmful conditions including apoptosis. Because a number of medium strong electrophiles from a series of α-X-substituted 2’,3,4,4’-tetramethoxychalcones (α-X-TMCs, X = H, F, Cl, Br, I, CN, Me, p-NO2-C6H4, Ph, p-OMe-C6H4, NO2, CF3, COOEt, COOH) had proven to activate Nrf2 resulting in HO-1 induction and inhibit NF-κB downstream target genes, their protective effect against staurosporine induced apoptosis and reactive oxygen species (ROS) production was investigated. RAW264.7 macrophages treated with 19 different chalcones (15 α-X-TMCs, chalcone, 2’-hydroxychalcone, calythropsin and 2’-hydroxy-3,4,4’-trimethoxychalcone) prior to staurosporine treatment were analyzed for apoptosis and ROS production, as well as HO-1 protein expression and enzyme activity. Additionally, Nrf2 and NF-κB activity was assessed. We found that amongst all tested chalcones only E-α-(4-methoxyphenyl)-2’,3,4,4'-tetramethoxychalcone (E-α-p-OMe-C6H4-TMC) demonstrated a distinct, statistically significant antiapoptotic effect in a dose dependent manner, showing no toxic effects, while its double bond isomer Z-α-p-OMe-C6H4-TMC displayed no significant activity. Also, E-α-p-OMe-C6H4-TMC induced HO-1 protein expression and increased HO-1 activity, whilst inhibition of HO-1 by SnPP-IX abolished its antiapoptotic effect. The only weakly electrophilic chalcone E-α-p-OMe-C6H4-TMC reduced the staurosporine triggered formation of ROS, while inducing the translocation of Nrf2 into the nucleus. Furthermore, staurosporine induced NF-κB activity was attenuated following E-α-p-OMe-C6H4-TMC treatment. Overall, E-α-p-OMe-C6H4-TMC demonstrated its effective cytoprotective potential via a non-toxic induction of HO-1 in RAW264

  8. 8-Methly-4-(3-diethylaminopropylamino) pyrimido [4',5';4,5] thieno (2,3-b) quinoline (MDPTQ), a quinoline derivate that causes ROS-mediated apoptosis in leukemia cell lines

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

    Shenoy, Sudheer; Vasania, Viraf S.; Gopal, M.

    2007-07-01

    The present study reports the biological activity of 8-methly-4-(3-diethylamino-propylamino) pyrimido [4';5';4,5] thieno (2,3-b) quinoline (MDPTQ), a quinoline derivative structurally related to ellipticine and suggests a possible mechanism through which the compound induces apoptosis in carcinoma cell lines. Out of the 8 cell lines used in the study as representatives of different types of cancer, MDPTQ was found to be effective only against leukemia cell lines (HL-60 and K-562) whereas it had no effect on normal human bone marrow cells (BMC) which were used as controls. Fall mitochondrial membrane potential and increased reactive oxygen species (ROS) were mainly responsible for inducingmore » apoptosis in the two cell lines. Cell death was demonstrated by increase in caspase 3 activity as well as phosphatidyl serine exposure. Pre-incubation with N-acetylcysteine (NAC) reduced the increased ROS and caspase 3 activity as well as phosphatidyl serine exposure. MDPTQ also caused cell cycle arrest in these cell lines. The above study for the first time reports the mode of action of a quinoline derivative, which could be a possible future candidate for leukemia therapy. However, there are lot of questions that need to be answered in terms of signalling pathways and its effects on animal models.« less

  9. Photo-reorganization of 3-alkoxy-6-chloro-2-(benzo[b]thiophen-2-yl)-4H-chromen-4-ones: a green and convenient synthesis of angular pentacyclics.

    PubMed

    Dalal, Aarti; Khanna, Radhika; Kumar, Parvin; Kamboj, Ramesh C

    2017-05-17

    Photo-reorganization of 3-alkoxy-6-chloro-2-(benzo[b]thiophen-2-yl)-4H-chromen-4-ones in methanol with Pyrex filtered UV-light from a medium pressure 125 W Hg-vapor lamp led to the formation of angular pentacyclic compounds (dihydro and aromatic products) along with some rearranged chromenones where the product(s) distribution depended upon the structure of 3-alkoxy groups (methoxy, ethoxy, allyloxy and benzyloxy). The phenyl moiety in the 3-benzyloxy group had a profound effect on the dihydro product(s) formation as the latter was in high yield when the alkoxy group was benzyloxy followed by allyloxy, ethoxy and methoxy groups. The present photochemical study represents a general method for the synthesis of some angular pentacyclic - benzothiophene fused xanthenone derivatives in a single step without using any specific and toxic reagent. The structures of the new organic scaffolds obtained were established by their spectral data (UV, IR and NMR).

  10. Experimental FT-IR, Laser-Raman and DFT spectroscopic analysis of a potential chemotherapeutic agent 6-(2-methylpropyl)-4-oxo-2-sulfanylidene-1,2,3,4-tetrahydropyrimidine-5-carbonitrile.

    PubMed

    Sert, Yusuf; Al-Turkistani, Abdulghafoor A; Al-Deeb, Omar A; El-Emam, Ali A; Ucun, Fatih; Çırak, Çağrı

    2014-01-01

    In this study, the experimental and theoretical vibrational frequencies of a newly synthesized potential chemotherapeutic agent namely, 6-(2-methylpropyl)-4-oxo-2-sulfanylidene-1,2,3,4-tetrahydropyrimidine-5-carbonitrile have been investigated. The experimental FT-IR (4000-400 cm(-1)) and Laser-Raman spectra (4000-100 cm(-1)) of the molecule in solid phase have been recorded. The theoretical vibrational frequencies and optimized geometric parameters (bond lengths and bond angles) have been calculated by using density functional theory (DFT/B3LYP: Becke, 3-parameter, Lee-Yang-Parr) and M06-2X (the highly parametrized, empirical exchange correlation function) quantum chemical methods with 6-311++G(d,p) basis set by Gaussian 09 W software, for the first time. The assignments of the vibrational frequencies have been done by potential energy distribution (PED) analysis by using VEDA 4 software. The theoretical optimized geometric parameters and vibrational frequencies have been found to be in good agreement with the corresponding experimental data, and with the results in the literature. In addition, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energies and the other related molecular energy values have been calculated and depicted. Copyright © 2013 Elsevier B.V. All rights reserved.

  11. Electrochemical treatment of 2, 4-dichlorophenol using a nanostructured 3D-porous Ti/Sb-SnO2-Gr anode: Reaction kinetics, mechanism, and continuous operation.

    PubMed

    Asim, Sumreen; Zhu, Yunqing; Batool, Aisha; Hailili, Reshalaiti; Luo, Jianmin; Wang, Yuanhao; Wang, Chuanyi

    2017-10-01

    2, 4-dichlorophenol (2, 4-DCP) is considered to be a highly toxic, mutagenic, and possibly carcinogenic pollutant. This study is focused on the electrochemical oxidation of 2, 4-DCP on nanostructured 3D-porous Ti/Sb-SnO 2 -Gr anodes, with the aim of presenting a comprehensive elucidation of mineralization process through the investigation of influential kinetics, the reactivity of hydroxyl radical's and analysis of intermediates. High efficiency was achieved at pH of 3 using Na 2 SO 4 electrolytes at a current density of 30 mA cm -2 . Under the optimized conditions, a maximum removal of 2, 4-DCP of up to 99.9% was reached, whereas a TOC removal of 81% was recorded with the lowest EC TOC (0.49 kW h g -1 ) within 40 min of electrolysis. To explore the stability of the 3D-Ti/Sb-SnO 2 -Gr electrodes, a continuous electrochemical operation was established, and the consistent mineralization results indicated the effectiveness of the 3D-Ti/Sb-SnO 2 -Gr system concerning its durability and practical utilization. EPR studies demonstrated the abundant generation of OH radicals on 3D-Ti/Sb-SnO 2 -Gr, resulting in fast recalcitrant pollutant incineration. From dechlorination and the reactivity of the OH radicals, several intermediates including six cyclic byproducts and three aliphatic carboxylic acids were detected, and two possible degradation pathways were proposed that justify the complete mineralization of 2, 4-DCP. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Electron excitation cross sections for the 2s(2)2p(3)4S(O) -- 2s(2)2p(3)2D(O) (forbidden) and 4S(O) -- 2s2p(4) 4P (resonance) transitions in O II

    NASA Technical Reports Server (NTRS)

    Zuo, M.; Smith, Steven J.; Chutjian, A.; Williams, I. D.; Tayal, S. S.; Mclaughlin, Brendan M.

    1995-01-01

    Experimental and theoretical excitation cross sections are reported for the first forbidden transition 4S(O) -- 2S(2)2p(3) 2D(O) (lambda-lambda 3726, 3729) and the first allowed (resonance) transition 4S(O) -- 2s2p(4) 4P(lambda-833) in O II. Use is made of electron energy loss and merged-beams methods. The electron energy range covered is 3.33 (threshold) to 15 eV for the S -- D transition, and 14.9 (threshold) to 40 eV for the S -- P transition. Care was taken to assess and minimize the metastable fraction of the O II beam. An electron mirror was designed and tested to reflect inelastically backscattered electrons into the forward direction to account for the full range of polar scattering angles. Comparisons are made between present experiments and 11-state R-matrix calculations. Calculations are also presented for the 4S(O) -- 2s(2)2p(3)2P(O) (lambda-2470) transition.

  13. 4-Sulphobenzoate 3,4-dioxygenase. Purification and properties of a desulphonative two-component enzyme system from Comamonas testosteroni T-2.

    PubMed Central

    Locher, H H; Leisinger, T; Cook, A M

    1991-01-01

    Cell-free extracts of Comamonas testosteroni T-2 grown in toluene-p-sulphonate/salts medium catalyse the conversion of p-sulphobenzoate (PSB) into protocatechuate and sulphite by an NADH-requiring and Fe2(+)-activated dioxygenase. Anion-exchange chromatography of extracts yielded red (A) and yellow (B) protein fractions, both of which were necessary for dioxygenative activity. Further purification of each fraction by hydrophobic interaction chromatography and gel filtration led to two homogeneous protein components (A and B), which together converted 1 mol each of PSB, O2 and NADH into 1 mol each of protocatechuate, sulphite and, presumably, NAD+. The system was named 4-sulphobenzoate 3,4-dioxygenase (PSB dioxygenase system). Monomeric component B (Mr 36,000) was determined to be a reductase that contained 1 mol of FMN and about 2 mol each of iron and inorganic sulphur per mol. This component transferred electrons from NADH to the oxygenase component (A) or to, e.g., cytochrome c. Homodimeric component A (subunit Mr 50,000) of the PSB dioxygenase system contained one [2Fe-2S] centre per subunit and its u.v.-visible-absorption spectrum corresponded to a Rieske-type iron-sulphur centre. The requirement for activation by iron was interpreted as partial loss of mononuclear iron during purification of component A. Component A could be reduced by dithionite or by NADH plus catalytic amounts of component B. The PSB dioxygenase system displayed a narrow substrate range: none of 18 sulphonated or non-sulphonated analogues of PSB showed significant substrate-dependent O2 uptake. The physical properties of the PSB dioxygenase system resemble those of other bacterial multi-component dioxygenase, especially phthalate dioxygenase. However, it differs from most characterized systems in its overall reaction; the product is a vicinal diphenol, and not a dihydrodiol. Images Fig. 3. PMID:2012609

  14. The molecular architecture of QdtA, a sugar 3,4-ketoisomerase from Thermoanaerobacterium thermosaccharolyticum.

    PubMed

    Thoden, James B; Holden, Hazel M

    2014-06-01

    Unusual di- and trideoxysugars are often found on the O-antigens of Gram-negative bacteria, on the S-layers of Gram-positive bacteria, and on various natural products. One such sugar is 3-acetamido-3,6-dideoxy-D-glucose. A key step in its biosynthesis, catalyzed by a 3,4-ketoisomerase, is the conversion of thymidine diphosphate (dTDP)-4-keto-6-deoxyglucose to dTDP-3-keto-6-deoxyglucose. Here we report an X-ray analysis of a 3,4-ketoisomerase from Thermoanaerobacterium thermosaccharolyticum. For this investigation, the wild-type enzyme, referred to as QdtA, was crystallized in the presence of dTDP and its structure solved to 2.0-Å resolution. The dimeric enzyme adopts a three-dimensional architecture that is characteristic for proteins belonging to the cupin superfamily. In order to trap the dTDP-4-keto-6-deoxyglucose substrate into the active site, a mutant protein, H51N, was subsequently constructed, and the structure of this protein in complex with the dTDP-sugar ligand was solved to 1.9-Å resolution. Taken together, the structures suggest that His 51 serves as a catalytic base, that Tyr 37 likely functions as a catalytic acid, and that His 53 provides a proton shuttle between the C-3' hydroxyl and the C-4' keto group of the hexose. This study reports the first three-dimensional structure of a 3,4-ketoisomerase in complex with its dTDP-sugar substrate and thus sheds new molecular insight into this fascinating class of enzymes. © 2014 The Protein Society.

  15. A new donors' CYP3A5 and recipients' CYP3A4 cluster predicting tacrolimus disposition, and new-onset hypertension in Chinese liver transplant patients.

    PubMed

    Liu, Yuan; Zhang, Tao; Zhang, Xiaoqing; Ye, Ling; Gu, Haitao; Zhong, Lin; Sun, Hongcheng; Song, Chenlong; Peng, Zhihai; Fan, Junwei

    2017-09-19

    The purpose of the current study was to investigate individualized therapy of tacrolimus (Tac), as well as complications after liver transplantation (LT) with the known genetic determinants and clinical factors. In this retrospective study, two cohorts (n=170) from the China Liver Transplant Registry (CLTR) database from July 2007 to March 2015 were included. Both donors' CYP3A5 *3 and recipients' CYP3A4 *1G had a correlation with Tac pharmacokinetics at four weeks (all P <0.05), except recipients' CYP3A4 *1G nearly had an association at week 2 ( P =0.055). The model of donors' CYP3A5 *3, recipients' CYP3A4*1G , and total bilirubin (TBL), for the prediction of Tac disposition, was better than donors' CYP3A5 *3 only at week 1, 2, and 3 ( P =0.010, P =0.007, and P =0.010, respectively), but not apparent at week 4 ( P =0.297). Besides, when the P value was greater than or equal to 0.6685 after considering the false-positive rate R=10%, the patients were considered to have a faster metabolism, according to the mentioned model. Interestingly, we found that if more than or equal to two alleles A were present in the combination of donors' CYP3A5 *3 and recipients' CYP3A4 *1G genotype, there was a lower Tac C/D ration at week 1, 2, and 3 ( P <0.001, P =0.001, and P <0.001), except at week 4 ( P =0.082), and the probability of new-onset hypertension was lesser ( P <0.001). These data provided a potential basis for a comprehensive approach to predicting the Tac dose requirement in individual patients and provided a strategy for the effective prevention, early diagnosis of new-onset hypertension in Chinese LT recipients.

  16. NH3 molecule adsorption on spinel-type ZnFe2O4 surface: A DFT and experimental comparison study

    NASA Astrophysics Data System (ADS)

    Zou, Cong-yang; Ji, Wenchao; Shen, Zhemin; Tang, Qingli; Fan, Maohong

    2018-06-01

    Ammonia (NH3) is a caustic environment pollutant which contributes to haze formation and water pollution. Zinc ferrite (ZnFe2O4) exhibits good catalytic activity in NH3 removal. The density functional theory (DFT) was applied to explore the interaction mechanism of NH3 molecule adsorption on spinel-type ZnFe2O4 (1 1 0) surface with GGA-PW91 method in atomic and electronic level. The results indicated that NH3 molecule preferred to adsorb on surface Zn atom with the formation of H3Nsbnd Zn coordinate bond over ZnFe2O4 (1 1 0) surface. The H3Nsbnd Zn state was exothermic process with adsorption energy of -203.125 kJ/mol. About 0.157e were transferred from NH3 molecule to the surface which resulted in strong interaction. Higher activation degree occurred in H3Nsbnd Zn configuration with two Nsbnd H bonds elongated and NH3 structure became more flat on the surface. The PDOS change of NH3 molecule was consistent with the result of adsorption energy. It was concluded that s orbital of NH3 (N) and s, p orbitals of Zn atom overlapped at -0.619 Ha. The p orbital of NH3 (N) has interaction with d orbital of Zn atom suggesting the hybridization between them. Based on NH3 removal experimental and XPS spectra results, NH3sbnd ZnFe2O4 interaction was mainly depended on the coordination between Zn atom and NH3 molecule. The DFT calculations have deepened our understanding on NH3sbnd ZnFe2O4 interaction system.

  17. Synthesis and antitumoral activity of novel 3-(2-substituted-1,3,4-oxadiazol-5-yl) and 3-(5-substituted-1,2,4-triazol-3-yl) beta-carboline derivatives.

    PubMed

    Formagio, Anelise S Nazari; Tonin, Lilian T Düsman; Foglio, Mary Ann; Madjarof, Christiana; de Carvalho, João Ernesto; da Costa, Willian Ferreira; Cardoso, Flávia P; Sarragiotto, Maria Helena

    2008-11-15

    Several novel 1-substituted-phenyl beta-carbolines bearing the 2-substituted-1,3,4-oxadiazol-5-yl and 5-substituted-1,2,4-triazol-3-yl groups at C-3 were synthesized and evaluated for their in vitro anticancer activity. The assay results pointed thirteen compounds with growth inhibition effect (GI(50)<100 microM) for all eight different types of human cancer cell lines tested. The beta-carbolines 7a and 7h, bearing the 3-(2-metylthio-1,3,4-oxadiazol-5-yl) group, displayed high selectivity and potent anticancer activity against ovarian cell line with GI(50) values lying in the nanomolar concentration range (GI(50)=10 nM for both compounds). The 1-(N,N-dimethylaminophenyl)-3-(5-thioxo-1,2,4-triazol-3-yl) beta-carboline (8g) was the most active compound, showing particular effectiveness on lung (GI(50)=0.06 microM), ovarian and renal cell lines. The potent anticancer activity presented for synthesized compounds 7a, 7h, and 8g, together with their easiness of synthesis, makes these compounds promising anticancer agents.

  18. A Low Temperature Infrared Study Of Deuterated NH4VO3

    NASA Astrophysics Data System (ADS)

    de Waal, D.; Heyns, A. M.

    1989-12-01

    The existence of (NH4)2V6016 as an intermediate in the thermal decomposition of NH4V03 to V205 has been confirmed by vibrational spectroscopy, resulting in the following reaction in an open systeml: NH4VO3 1 bar, air, 50-200°C/(1) (NH4)2v6o16 1 bar, air, ca.360°C/(2) V205 The kinetics of reaction (1) was studied by means of Raman spectroscopy, and structural information on NH4V03 and (N114)V60 16 was required to obtain an accurate description of the reaction mechanism2. Information on the site symmetry of an ammonium ion and hydrogen bonding in a crystal can be obtained by considering the infrared spectra of isotopically dilute NH3D+ ions in the lattice at liquid nitrogen temperatures3, especially as the position of hydrogen atoms in (NHO2V6016 could not be determined by X-ray methods.

  19. Membrane Order Is a Key Regulator of Divalent Cation-Induced Clustering of PI(3,5)P2 and PI(4,5)P2.

    PubMed

    Sarmento, Maria J; Coutinho, Ana; Fedorov, Aleksander; Prieto, Manuel; Fernandes, Fábio

    2017-10-31

    Although the evidence for the presence of functionally important nanosized phosphorylated phosphoinositide (PIP)-rich domains within cellular membranes has accumulated, very limited information is available regarding the structural determinants for compartmentalization of these phospholipids. Here, we used a combination of fluorescence spectroscopy and microscopy techniques to characterize differences in divalent cation-induced clustering of PI(4,5)P 2 and PI(3,5)P 2 . Through these methodologies we were able to detect differences in divalent cation-induced clustering efficiency and cluster size. Ca 2+ -induced PI(4,5)P 2 clusters are shown to be significantly larger than the ones observed for PI(3,5)P 2 . Clustering of PI(4,5)P 2 is also detected at physiological concentrations of Mg 2+ , suggesting that in cellular membranes, these molecules are constitutively driven to clustering by the high intracellular concentration of divalent cations. Importantly, it is shown that lipid membrane order is a key factor in the regulation of clustering for both PIP isoforms, with a major impact on cluster sizes. Clustered PI(4,5)P 2 and PI(3,5)P 2 are observed to present considerably higher affinity for more ordered lipid phases than the monomeric species or than PI(4)P, possibly reflecting a more general tendency of clustered lipids for insertion into ordered domains. These results support a model for the description of the lateral organization of PIPs in cellular membranes, where both divalent cation interaction and membrane order are key modulators defining the lateral organization of these lipids.

  20. A toxological study of 3,6-BIS(3,5-Dimethyl-1-1-Pyrazolyl)1,2-Dihydro-1,2,4,5-Tetrazine

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

    London, J.E.

    1993-03-01

    The acute oral LD{sub 30/50} values for 3,6-BIS(3,5-Dimethyl-1-Pyrazolyl)-1,2-Dihydro-1,2,4,5-Tetrazine BIS(DMP)DHT are greater than 5g/kg. According to classical guidelines, the material would be considered only slightly toxic or practically nontoxic in both rats and mice. The sensitization study in the guinea pig did not show BIS(DMP)SHT to have potential sensitizing effects. Skin application studies on the rabbit demonstrated the material was cutaneously nonirritating. This material was also nonirritating in the rabbit eye application studies.

  1. A toxological study of 3,6-BIS(3,5-Dimethyl-1-1-Pyrazolyl)1,2-Dihydro-1,2,4,5-Tetrazine

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

    London, J.E.

    1993-03-01

    The acute oral LD[sub 30/50] values for 3,6-BIS(3,5-Dimethyl-1-Pyrazolyl)-1,2-Dihydro-1,2,4,5-Tetrazine BIS(DMP)DHT are greater than 5g/kg. According to classical guidelines, the material would be considered only slightly toxic or practically nontoxic in both rats and mice. The sensitization study in the guinea pig did not show BIS(DMP)SHT to have potential sensitizing effects. Skin application studies on the rabbit demonstrated the material was cutaneously nonirritating. This material was also nonirritating in the rabbit eye application studies.

  2. Highly enantioselective reduction of 4-(trimethylsilyl)-3-butyn-2-one to enantiopure (R)-4-(trimethylsilyl)-3-butyn-2-ol using a novel strain Acetobacter sp. CCTCC M209061.

    PubMed

    Xiao, Zi-Jun; Zong, Min-Hua; Lou, Wen-Yong

    2009-12-01

    The biocatalytic reduction of 4-(trimethylsilyl)-3-butyn-2-one to enantiopure (R)-4-(trimethylsilyl)-3-butyn-2-ol was successfully conducted with high enantioselectivity using immobilized whole cells of a novel strain Acetobacter sp. CCTCC M209061, newly isolated from kefir. Compared with other microorganisms that were investigated, Acetobacter sp. CCTCC M209061 was shown to be more effective for the bioreduction reaction, and afforded much higher yield and product enantiomeric excess (e.e.). The optimal buffer pH, co-substrate concentration, reaction temperature, substrate concentration and shaking rate were 5.0, 130.6 mM, 30 degrees C, 6.0 mM and 180 r/min, respectively. Under the optimized conditions, the maximum yield and the product e.e. were 71% and >99%, respectively, which are much higher than those reported previously. Additionally, the established biocatalytic system proved to be efficient for the bioreduction of acetyltrimethylsilane to (R)-1-trimethylsilylethanol with excellent yield and product e.e. The immobilized cells manifested a good operational stability under the above reaction conditions since they retained 70% of their catalytic activity after ten cycles of use.

  3. Kapundaite, (Na,Ca)[subscript 2]Fe[subscript 4][superscript 3+](PO[subscript 4])[subscript 4](OH)[subscript 3]·5H[subscript 2]O, a new phosphate species from Toms quarry, South Australia: Description and structural relationship to mélonjosephite

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

    Mills, Stuart J.; Birch, William D.; Kampf, Anthony R.

    2010-06-22

    Kapundaite, ideally (Na,Ca){sub 2}Fe{sub 4}{sup 3+}(PO{sub 4}){sub 4}(OH){sub 3}{center_dot}5H{sub 2}O, is a new mineral (IMA2009-047) from Toms phosphate quarry, Kapunda, South Australia, Australia. The new mineral occurs as cavernous aggregates of fibers up to several centimeters across, associated with leucophosphite, natrodufrenite, and meurigite-Na crystals and amorphous brown, black, and/or greenish coatings. Individual kapundaite crystals are very thin flattened fibers up to a few millimeters in length, but typically no more than a few micrometers in thickness. The main form observed is {l_brace}100{r_brace}; other forms in the [010] zone are present, but cannot be measured. Crystals of kapundaite are pale tomore » golden yellow, transparent to translucent, have a yellow streak and silky luster, and are non-fluorescent. Mohs hardness is estimated to be about 3; no twinning or cleavage was observed. Kapundaite is biaxial (+), with indices of refraction = 1.717(3), {beta} = 1.737(3), and {gamma} = 1.790(3). 2V could not be measured; 2V{sub calc} is 64.7{sup o}. The optical orientation is Z = b, Y {approx} c with weak pleochroism: X = nearly colorless, Y = light brown, Z = pale brown; absorption: Y > Z > X. No dispersion was observed. The empirical chemical formula (mean of seven electron microprobe analyses) calculated on the basis of 24 O is (Ca{sub 1.13}Na{sub 0.95}){sub {Sigma}2.08}(Fe{sub 3.83}{sup 3+}Mn{sub 0.03}Al{sub 0.02}Mg{sub 0.01}){sub {Sigma}3.89}P{sub 3.92}O{sub 16}(OH){sub 3}{center_dot}5H{sub 2.11}O. Kapundaite is triclinic, space group P{sub {bar 1}}, a = 6.317(5), b = 7.698(6), c = 9.768(7) {angstrom}, {alpha} = 105.53(1){sup o}, {beta} = 99.24(2){sup o}, {gamma} = 90.09(2){sup o}, V = 451.2(6) {angstrom}{sup 3}, and Z = 1. The five strongest lines in the powder X-ray diffraction pattern are [d{sub obs} in {angstrom} (I) (hkl)]: 9.338 (100) (001), 2.753 (64) (2{sub {bar 1}}1), 5.173 (52) (011), 2.417 (48) ({sub {ovr 21}}3, 202, 0{sub {bar 1}}4

  4. Ferromagnetism in a hexagonal PrRh3 with 4f2 configuration

    NASA Astrophysics Data System (ADS)

    Park, G. B.; Yamane, Y.; Onimaru, T.; Umeo, K.; Takabatake, T.

    2018-05-01

    Electrical resistivity ρ , magnetization M and specific heat C are reported for polycrystalline samples of the hexagonal system PrRh3. The magnetic susceptibility M/B obeys the Curie-Weiss law with the effective magnetic moment μeff = 3.88 μB/Pr and the paramagnetic Curie temperature θp = +2.9 K, which indicates ferro-type magnetic interaction between the trivalent Pr ions. A cusp in C(T) at 3.0 K coincides with a bend in ρ (T). Applying magnetic fields, the peak broadens and shifts to higher temperatures. The field dependence indicates a ferro-type magnetic order. The magnetic entropy Sm is (1/3)Rln2 at TC = 3.0 K, suggesting that part of the Pr ions take part in the magnetic order. A broad tail of the magnetic specific heat Cm observed above TC may result from short-range correlations and/or fluctuations of the active magnetic dipole and quadrupoles in the ground state doublet.

  5. A facile and regioselective synthesis of 1,4-disubstituted 1,2,3-triazoles using click chemistry

    EPA Science Inventory

    The reaction of α-tosyloxy ketones, sodium azide and terminal alkynes in presence of copper(I) in aqueous polyethylene glycol afforded regioselectively 1,4-disubstituted 1,2,3-triazoles in good yield at ambient temperature. The one-pot exclusive formation of 1,4-disubstituted 1,2...

  6. Insights into the photocatalytic mechanism of mediator-free direct Z-scheme g-C3N4/Bi2MoO6(010) and g-C3N4/Bi2WO6(010) heterostructures: A hybrid density functional theory study

    NASA Astrophysics Data System (ADS)

    Opoku, Francis; Govender, Krishna Kuben; Sittert, Cornelia Gertina Catharina Elizabeth van; Govender, Penny Poomani

    2018-01-01

    Graphite-like carbon nitride (g-C3N4)-based heterostructures have received much attention due to their prominent photocatalytic activity. The g-C3N4/Bi2WO6 and g-C3N4/Bi2MoO6 heterostructures, which follow a typical hetero-junction charge transfer mechanisms show a weak potential for hydrogen evolution and reactive radical generation under visible light irradiation. A mediator-free Z-scheme g-C3N4/Bi2MoO6(010) and g-C3N4/Bi2WO6(010) heterostructures photocatalyst are designed for the first time using first-principles studies. Moreover, theoretical understanding of the underlying mechanism, the effects of interfacial composition and the role the interface play in the overall photoactivity is still unexplained. The calculated band gap of the heterostructures is reduced compared to the bulk Bi2WO6 and Bi2MoO6. In this study, we systematically calculated energy band structure, optical properties and charge transfer of the g-C3N4/Bi2MoO6(010) and g-C3N4/Bi2WO6(010) heterostructures using the hybrid density functional theory approach. The results show that the charge transfer at the interface of the heterostructures induces a built-in potential, which benefits the separation of photogenerated charge carriers. The g-C3N4/Bi2MoO6(010) heterostructure with more negative adhesion energy (-1.10 eVA-2) is predicted to have a better adsorptive ability and can form more easily compared to the g-C3N4/Bi2WO6(010) interface (-1.16 eVA-2). Therefore, our results show that the g-C3N4 interaction with Bi2MoO6 is stronger than Bi2WO6, which is also verified by the smaller vertical separation (3.25 Å) between Bi2MoO6 and g-C3N4 compared to the g-C3N4/Bi2WO6(010) interface (3.36 Å). The optical absorption verifies that these proposed Z-scheme heterostructures are excellent visible light harvesting semiconductor photocatalyst materials. This enhancement is ascribed to the role of g-C3N4 monolayer as an electron acceptor and the direct Z-scheme charge carrier transfer at the interface of

  7. Inhibition of the human liver microsomal and human cytochrome P450 1A2 and 3A4 metabolism of estradiol by deployment-related and other chemicals.

    PubMed

    Usmani, Khawja A; Cho, Taehyeon M; Rose, Randy L; Hodgson, Ernest

    2006-09-01

    Cytochromes P450 (P450s) are major catalysts in the metabolism of xenobiotics and endogenous substrates such as estradiol (E2). It has previously been shown that E2 is predominantly metabolized in humans by CYP1A2 and CYP3A4 with 2-hydroxyestradiol (2-OHE2) the major metabolite. This study examines effects of deployment-related and other chemicals on E2 metabolism by human liver microsomes (HLM) and individual P450 isoforms. Kinetic studies using HLM, CYP3A4, and CYP1A2 showed similar affinities (Km) for E2 with respect to 2-OHE2 production. Vmax and CLint values for HLM are 0.32 nmol/min/mg protein and 7.5 microl/min/mg protein; those for CYP3A4 are 6.9 nmol/min/nmol P450 and 291 microl/min/nmol P450; and those for CYP1A2 are 17.4 nmol/min/nmol P450 and 633 microl/min/nmol P450. Phenotyped HLM use showed that individuals with high levels of CYP1A2 and CYP3A4 have the greatest potential to metabolize E2. Preincubation of HLM with a variety of chemicals, including those used in military deployments, resulted in varying levels of inhibition of E2 metabolism. The greatest inhibition was observed with organophosphorus compounds, including chlorpyrifos and fonofos, with up to 80% inhibition for 2-OHE2 production. Carbaryl, a carbamate pesticide, and naphthalene, a jet fuel component, inhibited ca. 40% of E2 metabolism. Preincubation of CYP1A2 with chlorpyrifos, fonofos, carbaryl, or naphthalene resulted in 96, 59, 84, and 87% inhibition of E2 metabolism, respectively. Preincubation of CYP3A4 with chlorpyrifos, fonofos, deltamethrin, or permethrin resulted in 94, 87, 58, and 37% inhibition of E2 metabolism. Chlorpyrifos inhibition of E2 metabolism is shown to be irreversible.

  8. 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.

  9. High resolution FTIR spectroscopic study of the ν4 band of CH 3CHF 2 enclosed in a flow of cold N 2 gas

    NASA Astrophysics Data System (ADS)

    Appadoo, Dominique R. T.; Robertson, Evan G.; McNaughton, Don

    2003-01-01

    An enclosive flow cooling (EFC) cell has been constructed, and coupled to a Brüker IFS 120HR high resolution Fourier transform spectrometer to record rotationally cold absorption spectra of gases of atmospheric interest at high spectral resolution. The new system has been characterized using N 2O, revealing that rotational temperatures as cold as 110 K are readily attainable using liquid nitrogen as a cryogen. Infrared spectra of the ν4 band of 1,1-difluoroethane (R152a), CH 3CHF 2, cooled in the EFC cell have been measured at a resolution of 0.0019 cm-1. Eight hundred and twenty rovibrational transitions of the weak ν4 band with 2⩽ J'⩽46 and Kc'⩽16 were assigned and fitted to Watson's A-reduced Hamiltonian. The ν4 CH 3 symmetric deformation ( a/c-type) was found to be coupled to the ν13 asymmetric deformation ( b-type) via an a-axis Coriolis interaction. In the ensuing analysis, values of spectroscopic constants were obtained for both the ν4 and dark ν13 states. Supporting ab initio calculations up to the MP2/TZV+(3 df,3 p) level are presented.

  10. CYP3A4 Mediates Oxidative Metabolism of the Synthetic Cannabinoid AKB-48.

    PubMed

    Holm, Niels Bjerre; Nielsen, Line Marie; Linnet, Kristian

    2015-09-01

    Synthetic cannabinoid designer drugs have emerged as drugs of abuse during the last decade, and acute intoxication cases are documented in the scientific literature. Synthetic cannabinoids are extensively metabolized, but our knowledge of the involved enzymes is limited. Here, we investigated the metabolism of N-(1-adamantyl)-1-pentyl-1H-indazole-3-carboxamide (AKB-48), a compound identified in herbal blends from 2012 and onwards. We screened for metabolite formation using a panel of nine recombinant cytochrome P450 (CYP) enzymes (CYP1A2, 2B6, 2C8, 2C9, 2C18, 2C19, 2D6, 2E1, and 3A4) and compared the formed metabolites to human liver microsomal (HLM) incubations with specific inhibitors against CYP2D6, 2C19, and 3A4, respectively. The data reported here demonstrate CYP3A4 to be the major CYP enzyme responsible for the oxidative metabolism of AKB-48, preferentially performing the oxidation on the adamantyl moiety. Genetic polymorphisms are likely not important with regard to toxicity given the major involvement of CYP3A4. Adverse drug-drug interactions (DDIs) could potentially occur in cases with co-intake of strong CYP3A4 inhibitors, e.g., HIV antivirals and azole antifungal agents.

  11. The mGlu(2/3) agonist 2R,4R-4-aminopyrrolidine-2,4-dicarboxylate, is anti- and proconvulsant in DBA/2 mice.

    PubMed

    Moldrich, R X; Talebi, A; Beart, P M; Chapman, A G; Meldrum, B S

    2001-02-16

    The anticonvulsant activity of the selective group II metabotropic glutamate receptor (mGlu) agonist 2R,4R-4-aminopyrrolidine-2,4-dicarboxylate (2R,4R-APDC) has been evaluated in chemoconvulsant and sound-induced models of epileptic seizures in DBA/2 mice. 2R,4R-APDC (> or =10 nmol, intracerebroventricularly (i.c.v.), -15 min) transiently reduced sound-induced seizure activity including clonic seizures to 40% of vehicle at 20 nmol (i.c.v.) and 30% of vehicle at 100 mg/kg (intraperitoneally (i.p.), -15 min). 2R,4R-APDC inhibited clonic seizures induced by the group III mGlu antagonist (R,S)-alpha-methylserine-O-phosphate (2.5 micromol, i.c.v.) when co-injected at 20-40 nmol and inhibited limbic seizure activity induced by the mGlu(1/5) agonist (R,S)-3,5-dihydroxyphenylglycine (1.5 micromol, i.c.v.) when co-injected at 10-40 nmol. A reversal of the anticonvulsant activity of 2R,4R-APDC was observed at (>20 nmol) in each of the chemoconvulsant and sound-induced models of epileptic seizures. 2R,4R-APDC (0.1-1 micromol, i.c.v.) induced stimulus-independent, rapid and dose-dependent clonic seizures. Selective mGlu(2/3) agonists represent a novel class of potential anti-epileptic drugs, however due to the proconvulsant activity observed here, 2R,4R-APDC is obviously limited in this regard.

  12. Dietary Omega-3 Fatty Acids Prevented Adipocyte Hypertrophy by Downregulating DGAT-2 and FABP-4 in a Sex-Dependent Fashion.

    PubMed

    Balogun, Kayode A; Cheema, Sukhinder K

    2016-01-01

    Obesity is characterized by an increase in fat mass primarily as a result of adipocyte hypertrophy. Diets enriched in omega (n)-3 polyunsaturated fatty acids (PUFA) are suggested to reduce obesity, however, the mechanisms are not well understood. We investigated the effect of n-3 PUFA on adipocyte hypertrophy and the key genes involved in adipocyte hypertrophy. Female C57BL/6 mice were fed semi-purified diets (20 % w/w fat) containing high n-3 PUFA before mating, during pregnancy, and until weaning. Male and female offspring were continued on high n-3 PUFA (10 % w/w), medium n-3 PUFA (4 % w/w), or low n-3 PUFA (2 % w/w) diet for 16 weeks postweaning. Adipocyte area was quantified using microscopy, and gonadal mRNA expression of acyl CoA:diacylglycerol acyltransferase-2 (DGAT-2), fatty acid binding protein-4 (FABP-4) and leptin were measured. The high n-3 PUFA group showed higher levels of total n-3 PUFA in gonadal TAG compared to the medium and low n-3 PUFA groups (P < 0.001). The high n-3 PUFA male group had a lower adipocyte area compared to the medium and low n-3 PUFA group (P < 0.001); however, no difference was observed in females. The high n-3 PUFA male group showed lower mRNA expression of FABP-4, DGAT-2 and leptin compared to the low n-3 PUFA group, with no difference in females. Plasma lipid levels were lower in the high n-3 PUFA group compared to the other groups. Our findings show for the first time that n-3 PUFA prevents adipocyte hypertrophy by downregulating FABP-4, DGAT-2 and leptin; the effects are however sex-specific.

  13. Synthesis, molecular modeling, and opioid receptor affinity of 9, 10-diazatricyclo[4.2.1.1(2,5)]decanes and 2,7-diazatricyclo[4.4.0. 0(3,8)]decanes structurally related to 3,8-diazabicyclo[3.2. 1]octanes.

    PubMed

    Vianello, P; Albinati, A; Pinna, G A; Lavecchia, A; Marinelli, L; Borea, P A; Gessi, S; Fadda, P; Tronci, S; Cignarella, G

    2000-06-01

    Various lines of evidence, including molecular modeling studies, imply that the endoethylenic bridge of 3,8-diazabicyclo[3.2. 1]octanes (DBO, 1) plays an essential role in modulating affinity toward mu opioid receptors. This hypothesis, together with the remarkable analgesic properties observed for N(3) propionyl, N(8) arylpropenyl derivatives (2) and of the reverted isomers (3), has prompted us to insert an additional endoethylenic bridge on the piperazine moiety in order to identify derivatives with increased potency toward this receptor class. In the present report, we describe the synthesis of the novel compounds 9,10-diazatricyclo[4.2. 1.1(2,5)]decane (4) and 2,7-diazatricyclo[4.4.0.0(3,8)]decane (5), as well as the representative derivatives functionalized at the two nitrogen atoms by propionyl and arylpropenyl groups (6a-e, 7a-d). Opioid receptor binding assays revealed that, among the compounds tested, the N-propionyl-N-cinnamyl derivatives 6a and 7a exhibited the highest mu-receptor affinity, and remarkably, compound 7a displayed in vivo (mice) an analgesic potency 6-fold that of morphine.

  14. Determination of Diacetyl in Beer by a Precolumn Derivatization-HPLC-UV Method Using 4-(2,3-Dimethyl-6-quinoxalinyl)-1,2-benzenediamine as a Derivatizing Reagent.

    PubMed

    Wang, Ji-Yu; Wang, Xin-Jie; Hui, Xian; Hua, Shui-Hong; Li, Heng; Gao, Wen-Yun

    2017-03-29

    Diacetyl is an important flavoring compound in many foods, especially in beer. In the present study, we developed and validated a new precolumn derivatization HPLC-UV method for the determination of diacetyl using 4-(2,3-dimethyl-6-quinoxalinyl)-1,2-benzenediamine as a novel derivatizing reagent. After derivatization with the reagent at a pH value 4.0 at ambient temperature for 10 min, diacetyl was analyzed on an ODS column and detected at 254 nm. The results show that the correlation coefficient of the method is 0.9991 in the range of 0.10 to 100.0 μM diacetyl, and the limit of detection is 0.02 μM. The method was further evaluated in the analysis of beer samples with the recoveries ranging from 94.4 to 102.6% and RSDs from 1.36 to 3.33%. The concentrations of diacetyl in 8 beer samples were determined in the range of 0.19 to 0.42 μM. The method established in this study may be well suitable for the determination of diacetyl in beer.

  15. Calcination Method Synthesis of SnO2/g-C3N4 Composites for a High-Performance Ethanol Gas Sensing Application

    PubMed Central

    Cao, Jianliang; Qin, Cong; Wang, Yan; Zhang, Bo; Gong, Yuxiao; Zhang, Huoli; Sun, Guang; Bala, Hari; Zhang, Zhanying

    2017-01-01

    The SnO2/g-C3N4 composites were synthesized via a facile calcination method by using SnCl4·5H2O and urea as the precursor. The structure and morphology of the as-synthesized composites were characterized by the techniques of X-ray diffraction (XRD), the field-emission scanning electron microscopy and transmission electron microscopy (SEM and TEM), energy dispersive spectrometry (EDS), thermal gravity and differential thermal analysis (TG-DTA), and N2-sorption. The analysis results indicated that the as-synthesized samples possess the two dimensional structure. Additionally, the SnO2 nanoparticles were highly dispersed on the surface of the g-C3N4nanosheets. The gas-sensing performance of the as-synthesized composites for different gases was tested. Moreover, the composite with 7 wt % g-C3N4 content (SnO2/g-C3N4-7) SnO2/g-C3N4-7 exhibits an admirable gas-sensing property to ethanol, which possesses a higher response and better selectivity than that of the pure SnO2-based sensor. The high surface area of the SnO2/g-C3N4 composite and the good electronic characteristics of the two dimensional graphitic carbon nitride are in favor of the elevated gas-sensing property. PMID:28468245

  16. Simultaneous quantification of T4, T3, rT3, 3,5-T2 and 3,3'-T2 in larval zebrafish (Danio rerio) as a model to study exposure to polychlorinated biphenyls.

    PubMed

    Chen, Xiaopeng; Walter, Kyla M; Miller, Galen W; Lein, Pamela J; Puschner, Birgit

    2018-06-01

    Environmental toxicants that interfere with thyroid hormone (TH) signaling can impact growth and development in animals and humans. Zebrafish represent a model to study chemically induced TH disruption, prompting the need for sensitive detection of THs. Simultaneous quantification of 3,3',5-triiodo-l-thyronine (T3), thyroxine (T4), 3,3',5'-triiodo-l-thyronine (rT3), 3,5-diiodo-l-thyronine (3,5-T2) and 3,3'-diiodo-l-thyronine (3,3'-T2) in zebrafish larvae was achieved by ultra-performance liquid chromatography-tandem mass spectrometry in positive ion mode. Solid-phase extraction with SampliQ cartridges and derivatization with 3 m hydrochloric acid in n-butanol reduced matrix effects. Derivatized compounds were separated on an Acquity UPLC BEH C 18 column with mobile phases consisting of 0.1% acetic acid in deionized water and 0.1% acetic acid in methanol. The limits of detection ranged from 0.5 to 0.6 pg injected on column. The method was validated by evaluating recovery (77.1-117.2%), accuracy (87.3-123.9%) and precision (0.5-12.4%) using diluted homogenized zebrafish embryos spiked with all target compounds. This method was then applied to zebrafish larvae collected after 114 h of exposure to polychlorinated biphenyls (PCBs), including PCB 28, PCB 66 and PCB 95, or the technical mixture Aroclor 1254. Exposure to PCB 28 and PCB 95 increased the T4:T3 ratio and decreased the T3:rT3 ratio, demonstrating that this method can effectively detect PCB-induced alterations in THs. Copyright © 2018 John Wiley & Sons, Ltd.

  17. Use of vibrational spectroscopy to study 4-benzyl-3-(thiophen-2-yl)-4,5-dihydro-1H-1,2,4-triazole-5-thione: A combined theoretical and experimental approach.

    PubMed

    Sert, Yusuf; El-Emam, Ali A; Al-Abdullah, Ebtehal S; Al-Tamimi, Abdul-Malek S; Cırak, Cağrı; Ucun, Fatih

    2014-05-21

    In this study, the experimental and theoretical vibrational frequencies of a newly synthesized potential anti-inflammatory agent namely, 4-benzyl-3-(thiophen-2-yl)-4,5-dihydro-1H-1,2,4-triazole-5-thione have been investigated. The experimental FT-IR (4000-400cm(-1)) and Laser-Raman spectra (4000-100cm(-1)) of the molecule in solid phase have been recorded. The theoretical vibrational frequencies and the optimized geometric parameters (bond lengths, bond angles and dihedral angles) have been calculated using density functional theory methods (DFT/B3LYP: Becke, 3-parameter, Lee-Yang-Parr and DFT/M06-2X: the highly parameterized, empirical exchange correlation function) with 6-311++G(d,p) basis set by Gaussian 09W software, for the first time. The assignments of the vibrational frequencies have been done by potential energy distribution (PED) analysis using VEDA 4 software program. The theoretical optimized geometric parameters and vibrational frequencies have been found to be in good agreement with the corresponding experimental data and results in the literature. In addition, the highest occupied molecular orbital (HOMO) energy, the lowest unoccupied molecular orbital (LUMO) energy and the other related molecular energy values of the compound have been investigated using the same theoretical calculations. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Transition metal complexes of 2-amino-3,5-dihalopyridines: Syntheses, structures and magnetic properties of (3,5-diCAPH)2CuX4 and (3,5-diBAPH)2CuX4.

    PubMed

    Tremelling, Grant W; Foxman, Bruce M; Landee, Christopher P; Turnbull, Mark M; Willett, Roger D

    2009-12-21

    A family of bis(2-amino-3,5-dihalopyridinium)tetrahalocuprate(II) compounds has been synthesized, including (3,5-diCAPH)2CuCl4 (1), (3,5-diCAPH)2CuBr4 (2), (3,5-diBAPH)2CuCl4 (3), and (3,5-diBAPH)2CuBr4 (4) [3,5-diCAPH = 2-amino-3,5-dichloropyridinium; 3,5-diBAPH = 2-amino-3,5-dibromopyridinium]. These complexes have been analyzed through single crystal X-ray diffraction and temperature dependent magnetic susceptibility. Compound 1 crystallizes in the P-1 space group and the tetrachlorocuprate ion is best described as possessing a distorted square planar geometry. Compounds 2-4 are structurally similar and crystallized in the P2(1)/n, P2(1)/c, and P2(1)/n space groups respectively. The tetrahalocuprate ions are best described as distorted tetrahedra. All four compounds show antiferromagnetic interactions and were fit to the uniform chain Heisenberg model with resulting 2J/kB values of -11.71(2) K, -2.21(1) K, -12.43 (2) K, and -1.36(1) K, respectively. The exchange values correlate well with the two-halide exchange pathway parameters. The unusual observation that the chloride complexes show stronger magnetic exchange than the bromide complexes provides strong support that the exchange can be strongly dependent upon the Cu-X...X angles and Cu-X...X-Cu torsion angles.

  19. Energies and spin states of FeS(0/-), FeS2(0/-), Fe2S2(0/-), Fe3S4(0/-), and Fe4S4(0/-) clusters.

    PubMed

    Li, Yan-Ni; Wang, Shengguang; Wang, Tao; Gao, Rui; Geng, Chun-Yu; Li, Yong-Wang; Wang, Jianguo; Jiao, Haijun

    2013-04-15

    The structures and energies of the electronic ground states of the FeS(0/-), FeS2(0/-), Fe2S2(0/-), Fe3S4(0/-), and Fe4S4(0/-) neutral and anionic clusters have been computed systematically with nine computational methods in combination with seven basis sets. The computed adiabatic electronic affinities (AEA) have been compared with available experimental data. Most reasonable agreements between theory and experiment have been found for both hybrid B3LYP and B3PW91 functionals in conjugation with 6-311+G* and QZVP basis sets. Detailed comparisons between the available experimental and computed AEA data at the B3LYP/6-311+G* level identified the electronic ground state of (5)Δ for FeS, (4)Δ for FeS(-), (5)B2 for FeS2, (6)A1 for FeS2(-), (1)A1 for Fe2S2, (8)A' for Fe2S2(-), (5)A'' for Fe3S4, (6)A'' for Fe3S4(-), (1)A1 for Fe4S4, and (1)A2 for Fe4S4(-). In addition, Fe2S2, Fe3S4, Fe3S4(-), Fe4S4, and Fe4S4(-) are antiferromagnetic at the B3LYP/6-311+G* level. The magnetic properties are discussed on the basis of natural bond orbital analysis. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Molecular modeling studies of 4,5-dihydro-1H-pyrazolo[4,3-h] quinazoline derivatives as potent CDK2/Cyclin a inhibitors using 3D-QSAR and docking.

    PubMed

    Ai, Yong; Wang, Shao-Teng; Sun, Ping-Hua; Song, Fa-Jun

    2010-09-28

    CDK2/cyclin A has appeared as an attractive drug targets over the years with diverse therapeutic potentials. A computational strategy based on comparative molecular fields analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) followed by molecular docking studies were performed on a series of 4,5-dihydro-1H-pyrazolo[4,3-h]quinazoline derivatives as potent CDK2/cyclin A inhibitors. The CoMFA and CoMSIA models, using 38 molecules in the training set, gave r(2) (cv) values of 0.747 and 0.518 and r(2) values of 0.970 and 0.934, respectively. 3D contour maps generated by the CoMFA and CoMSIA models were used to identify the key structural requirements responsible for the biological activity. Molecular docking was applied to explore the binding mode between the ligands and the receptor. The information obtained from molecular modeling studies may be helpful to design novel inhibitors of CDK2/cyclin A with desired activity.

  1. Molecular Modeling Studies of 4,5-Dihydro-1H-pyrazolo[4,3-h] quinazoline Derivatives as Potent CDK2/Cyclin A Inhibitors Using 3D-QSAR and Docking

    PubMed Central

    Ai, Yong; Wang, Shao-Teng; Sun, Ping-Hua; Song, Fa-Jun

    2010-01-01

    CDK2/cyclin A has appeared as an attractive drug targets over the years with diverse therapeutic potentials. A computational strategy based on comparative molecular fields analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) followed by molecular docking studies were performed on a series of 4,5-dihydro-1H-pyrazolo[4,3-h]quinazoline derivatives as potent CDK2/cyclin A inhibitors. The CoMFA and CoMSIA models, using 38 molecules in the training set, gave r2cv values of 0.747 and 0.518 and r2 values of 0.970 and 0.934, respectively. 3D contour maps generated by the CoMFA and CoMSIA models were used to identify the key structural requirements responsible for the biological activity. Molecular docking was applied to explore the binding mode between the ligands and the receptor. The information obtained from molecular modeling studies may be helpful to design novel inhibitors of CDK2/cyclin A with desired activity. PMID:21152296

  2. Poly[4,4'-(propane-1,3-diyl)dipyridinium bis{tetraaquabis(μ2-5-carboxybenzene-1,2,4-tricarboxylato)bis[μ2-1,3-bis(4-pyridyl)propane]dicobalt(II)} pentahydrate].

    PubMed

    Atria, Ana María; Corsini, Gino; Garland, Maria Teresa; Baggio, Ricardo

    2011-11-01

    The title polymeric compound, {(C(13)H(16)N(2))[Co(C(10)H(3)O(8))(C(13)H(14)N(2))(H(2)O)(2)](2)·5H(2)O}(n), is an ionic structure comprising an anionic two-dimensional mesh characterized by a {[Co(Hbtc)(bpp)(H(2)O)(2)](-)}(2) motif [Hbtc is 5-carboxybenzene-1,2,4-tricarboxylate and bpp is 1,3-bis(4-pyridyl)propane], with interspersed 4,4'-(propane-1,3-diyl)dipyridinium cations, denoted (H(2)bpp)(2+), and water molecules providing the charge balance and structure stabilization. The reticular mesh consists of two independent types of [Co(H(2)O)(2)](2+) cationic nodes (lying on inversion centres), interconnected in the [101] direction by two independent sets of neutral bridging bpp ligands, both types of ligands being split by non-equivalent twofold axes. One set is formed by genuinely symmetric moieties, while those in the second set are only symmetric by disorder in the central propane bridge. These chains contain only one type of Co(II) centre and one type of bpp ligand; the metal cations therein are laterally bridged by Hbtc anions, thus forming transverse chains of alternating types of Co(II) cations. The elemental motif of the resulting grid is a highly distorted parallelogram, with metal-metal distances of 13.5242 (14) Å in the bpp direction and 9.105 (2) Å in the Hbtc direction, and a large internal angle of 138.42 (18)°. These two-dimensional structures have a profusion of hydrogen-bonding interactions with each other, either directly (with the aqua molecules as donors and the Hbtc anions as acceptors) or mediated by the unbound (H(2)bpp)(2+) cations and water molecules of hydration. These interactions generate a very complex hydrogen-bonding scheme involving all of the available N-H and O-H groups and which links these two-dimensional grids into a three-dimensional network.

  3. Time-dependent inhibition (TDI) of CYP3A4 and CYP2C9 by noscapine potentially explains clinical noscapine-warfarin interaction.

    PubMed

    Fang, Zhong-Ze; Zhang, Yan-Yan; Ge, Guang-Bo; Huo, Hong; Liang, Si-Cheng; Yang, Ling

    2010-02-01

    To investigate the inhibition potential and kinetic information of noscapine to seven CYP isoforms and extrapolate in vivo noscapine-warfarin interaction magnitude from in vitro data. The activities of seven CYP isoforms (CYP3A4, CYP1A2, CYP2A6, CYP2E1, CYP2D6, CYP2C9, CYP2C8) in human liver microsomes were investigated following co- or preincubation with noscapine. A two-step incubation method was used to examine in vitro time-dependent inhibition (TDI) of noscapine. Reversible and TDI prediction equations were employed to extrapolate in vivo noscapine-warfarin interaction magnitude from in vitro data. Among seven CYP isoforms tested, the activities of CYP3A4 and CYP2C9 were strongly inhibited with an IC(50) of 10.8 +/- 2.5 microm and 13.3 +/- 1.2 microm. Kinetic analysis showed that inhibition of CYP2C9 by noscapine was best fit to a noncompetitive type with K(i) value of 8.8 microm, while inhibition of CYP3A4 by noscapine was best fit to a competitive manner with K(i) value of 5.2 microm. Noscapine also exhibited TDI to CYP3A4 and CYP2C9. The inactivation parameters (K(I) and k(inact)) were calculated to be 9.3 microm and 0.06 min(-1) for CYP3A4 and 8.9 microm and 0.014 min(-1) for CYP2C9, respectively. The AUC of (S)-warfarin and (R)-warfarin was predicted to increase 1.5% and 1.1% using C(max) or 0.5% and 0.4% using unbound C(max) with reversible inhibition prediction equation, while the AUC of (S)-warfarin and (R)-warfarin was estimated to increase by 110.9% and 48.9% using C(max) or 41.8% and 32.7% using unbound C(max) with TDI prediction equation. TDI of CYP3A4 and CYP2C9 by noscapine potentially explains clinical noscapine-warfarin interaction.

  4. A brominated flame retardant, 2,2',4,4',5-pentabromodiphenyl ether: uptake, retention, and induction of neurobehavioral alterations in mice during a critical phase of neonatal brain development.

    PubMed

    Eriksson, P; Viberg, H; Jakobsson, E; Orn, U; Fredriksson, A

    2002-05-01

    Polybrominated diphenyl ethers (PBDEs) are used in large quantities as flame retardant additives. In a recent study, we have seen that neonatal exposure to some brominated flame retardants can cause permanent aberrations in spontaneous motor behavior that seem to worsen with age. In view of an increasing amount of PBDEs in mother's milk and in the environment, the present study was undertaken to investigate whether there is a critical and limited phase, during neonatal life, for induction of persistent neurotoxic effects of 2,2',4,4',5-pentaBDE (PBDE 99). Neonatal NMRI male mice were exposed on day 3, 10, or 19 to 8 mg 2,2',4,4',5-pentaBDE/kg body weight. Uptake and retention of 2,2',4,4',5-penta[(14)C]BDE were studied in the mouse brain after exposure to 1.5 M becquerel (Bq) 2,2',4,4',5-penta[(14)C]BDE /kg body weight (bw) on postnatal day 3, 10, or 19. Spontaneous motor behavior was observed in 4-month-old mice. Mice exposed to 2,2',4,4',5-pentaBDE on day 3 or 10 showed significantly impaired spontaneous motor behavior, whereas no effect was seen in mice exposed on day 19. Neonatal mice exposed to 2,2',4,4',5-penta[(14)C]BDE 99 on postnatal day 3, 10, or 19 were sacrificed 24 h or 7 days posttreatment. The amount of radioactivity, given as per mille ( per thousand) of total amount administered, was between 3.7 and 5.1 per thousand in the three different age categories at 24 h after administration. Seven days after the administration, 2,2',4,4',5-penta[(14)C]BDE or its metabolites could still be detected in the brain. The amount of radioactivity in the brain was not higher in mice exposed on day 3 or 10 when compared to exposure on day 19. Thus, the behavioral disturbances observed in adult mice following neonatal exposure to 2,2',4,4',5-pentaBDE are induced during a defined critical period of neonatal brain development.

  5. Synthesis, characterization and crystal structure of (2RS,4R)-2-(2-hydroxy-3-methoxyphenyl)thiazolidine-4-carboxylic acid

    NASA Astrophysics Data System (ADS)

    Muche, Simon; Müller, Matthias; Hołyńska, Małgorzata

    2018-03-01

    The condensation reaction of ortho-vanillin and L-cysteine leads to formation of a racemic mixture of (2RS,4R)-2-(2-hydroxy-3-methoxyphenyl)thiazolidine-4-carboxylic acid and not, as reported in the available literature, to a Schiff base. The racemic mixture was fully characterized by 1D and 2D NMR techniques, ESI-MS and X-ray diffraction. Addition of ZnCl2 led to formation of crystals in form of colorless needles, suitable for X-ray diffraction studies. The measured crystals were identified as the diastereomer (2R,4R)-2-(2-hydroxy-3-methoxyphenyl)thiazolidine-4-carboxylic acid 1. The bulk material is racemic. Thiazolidine exists as zwitterion in solid state, as indicated by the crystal structure.

  6. New metal oxides of the family Am[( TO) q]: ALiMn 3O 4 and ALiZn 3O 4 ( A = K, Rb)

    NASA Astrophysics Data System (ADS)

    Hoppe, R.; Seipp, E.; Baier, R.

    1988-01-01

    The new compounds KLiMn 3O 4 ( I), RbLiMn 3O 4 ( II), KLiZn 3O 4 ( III) and RbLiZn 3O 4 ( IV) have been prepared by solid state reaction of A2O ( A = K, Rb), Li 2O, and MO ( M = Mn, Zn). The isomorphous compounds are tetragonal, space group {I4}/{m}, Z = 2 , with lattice constants a = 838.32(4) pm, c = 341.88(3) pm for I; a = 840.66(8) pm, c = 344.85(4) pm for II; a = 819.27(9) pm, c = 334.20(7) pm for III,a = 823.62(9) pm, c = 339.73(7) pm for IV, as determined from Guinier X-ray powder patterns. The orange-colored manganates and colorless zincates are sensitive to moisture. The crystal structures of II and III have been determined by single-crystal X-ray techniques and refined to R = 0.09 ( II) and R = 0.06 ( III). The structure is built up from chains of face-shared cubes, 1∞[A O{8}/{2}] (A = K, Rb) , running parallel to the c axis. These are connected by Li + and M2+ ( M = Mn, Zn), statistically distributed on tetrahedral positions between the chains.

  7. Genome-wide Analysis of the H3K4 Histone Demethylase RBP2 Reveals a Transcriptional Program Controlling Differentiation

    PubMed Central

    Lopez-Bigas, Nuria; Kisiel, Tomasz A.; DeWaal, Dannielle C.; Holmes, Katie B.; Volkert, Tom L.; Gupta, Sumeet; Love, Jennifer; Murray, Heather L.; Young, Richard A.; Benevolenskaya, Elizaveta V.

    2010-01-01

    SUMMARY Retinoblastoma protein (pRB) mediates cell-cycle withdrawal and differentiation by interacting with a variety of proteins. RB-Binding Protein 2 (RBP2) has been shown to be a key effector. We sought to determine transcriptional regulation by RBP2 genome-wide by using location analysis and gene expression profiling experiments. We describe that RBP2 shows high correlation with the presence of H3K4me3 and its target genes are separated into two functionally distinct classes: differentiation-independent and differentiation-dependent genes. The former class is enriched by genes that encode mitochondrial proteins, while the latter is represented by cell-cycle genes. We demonstrate the role of RBP2 in mitochondrial biogenesis, which involves regulation of H3K4me3-modified nucleosomes. Analysis of expression changes upon RBP2 depletion depicted genes with a signature of differentiation control, analogous to the changes seen upon reintroduction of pRB. We conclude that, during differentiation, RBP2 exerts inhibitory effects on multiple genes through direct interaction with their promoters. PMID:18722178

  8. Key functions analysis of a novel nonlinear optical D-π-A bridge type (2E)-3-(4-Methylphenyl)-1-(3-nitrophenyl) prop-2-en-1-one chalcone: An experimental and theoretical approach

    NASA Astrophysics Data System (ADS)

    Patil, Parutagouda Shankaragouda; Shkir, Mohd; Maidur, Shivaraj R.; AlFaify, S.; Arora, M.; Rao, S. Venugopal; Abbas, Haider; Ganesh, V.

    2017-10-01

    In the current work a new third-order nonlinear optical organic single crystal of (2E)-3-(4-Methylphenyl)-1-(3-nitrophenyl) prop-2-en-1-one (ML3NC) has been grown with well-defined morphology using the slow evaporation solution growth technique. X-ray diffraction technique was used to confirm the crystal system. The presence of functional groups in the molecular structure was identified by robust FT-IR and FT-Raman spectra by experimental and theoretical analysis. The ultraviolet-visible-near infrared and photoluminescence studies shows that the grown crystals possess excellent transparency window and green emission band (∼560 nm) confirms their use in green OLEDs. The third-order nonlinear and optical limiting studies have been performed using femtosecond (fs) Z-scan technique. The third-order nonlinear optical susceptibility (χ(3)), second-order hyperpolarizability (γ), nonlinear refractive index (n2) and limiting threshold values are found to be 4.03 × 10-12 esu, 14.2 × 10-32 esu, -4.33 × 10-14 cm2/W and 2.41 mJ/cm2, respectively. Furthermore, the quantum chemical studies were carried out to achieve the ground state molecular geometry and correlate with experimental results. The experimental value of absorption wavelength (λabs = 328 nm) is found to be in excellent accord with the theoretical value (λabs = 328 nm) at TD-DFT/B3LYP/6-31G* level of theory. To understand the static and dynamic NLO behavior, the polarizability (α) and second hyperpolarizability (γ) values were determined using TD-HF method. The computed second hyperpolarizability γ(-3ω; ω,ω,ω) at 800 nm wavelength was found to be 0.499 × 10-32 esu which is in good agreement with experimental value at the same wavelength. These results confirms the applied nature of title molecule in optoelectronic and nonlinear optical devices.

  9. In vitro and in vivo evaluation of N-{2-[4-(3-Cyanopyridin-2-yl)piperazin-1-yl]ethyl}-3-[(11) C]methoxybenz-amide, a positron emission tomography (PET) radioligand for dopamine D4 receptors, in rodents.

    PubMed

    Leopoldo, Marcello; Selivanova, Svetlana V; Müller, Adrienne; Lacivita, Enza; Schetz, John A; Ametamey, Simon M

    2014-09-01

    The D4 dopamine receptor belongs to the D2 -like family of dopamine receptors, and its exact regional distribution in the central nervous system is still a matter of considerable debate. The availability of a selective radioligand for the D4 receptor with suitable properties for positron emission tomography (PET) would help resolve issues of D4 receptor localization in the brain, and the presumed diurnal change of expressed protein in the eye and pineal gland. We report here on in vitro and in vivo characteristics of the high-affinity D4 receptor-selective ligand N-{2-[4-(3-cyanopyridin-2-yl)piperazin-1-yl]ethyl}-3-[(11) C]methoxybenzamide ([(11) C]2) in rat. The results provide new insights on the in vitro properties that a brain PET dopamine D4 radioligand should possess in order to have improved in vivo utility in rodents. Copyright © 2014 Verlag Helvetica Chimica Acta AG, Zürich.

  10. A reduced graphene oxide/Co 3O 4 composite for supercapacitor electrode

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

    Xiang, Chengcheng; Li, Ming; Zhi, Mingjia

    2013-03-01

    20 nm sized Co 3O 4 nanoparticles are in-situ grown on the chemically reduced graphene oxide (rGO) sheets to form a rGO-Co 3O 4 composite during hydrothermal processing. The rGO-Co 3O 4 composite is employed as the pseudocapacitor electrode in the 2 M KOH aqueous electrolyte solution. The rGOCo 3O 4 composite electrode exhibits a specific capacitance of 472 F/g at a scan rate of 2 mV/s in a two-electrode cell. 82.6% of capacitance is retained when the scan rate increases to 100 mV/s. The rGOCo 3O 4 composite electrode shows high rate capability and excellent long-term stability. It alsomore » exhibits high energy density at relatively high power density. The energy density reaches 39.0 Wh/kg at a power density of 8.3 kW/kg. The super performance of the composite electrode is attributed to the synergistic effects of small size and good redox activity of the Co 3O 4 particles combined with high electronic conductivity of the rGO sheets.« less

  11. The structures of 1,4-diaryl-5-trifluoromethyl-1H-1,2,3-triazoles related to J147, a drug for treating Alzheimer's disease.

    PubMed

    Farrán, M Ángeles; Bonet, M Ángels; Claramunt, Rosa M; Torralba, M Carmen; Alkorta, Ibon; Elguero, José

    2018-04-01

    J147 [N-(2,4-dimethylphenyl)-2,2,2-trifluoro-N'-(3-methoxybenzylidene)acetohydrazide] has recently been reported as a promising new drug for the treatment of Alzheimer's disease. The X-ray structures of seven new 1,4-diaryl-5-trifluoromethyl-1H-1,2,3-triazoles, namely 1-(3,4-dimethylphenyl)-4-phenyl-5-trifluoromethyl-1H-1,2,3-triazole (C 17 H 14 F 3 N 3 , 1), 1-(3,4-dimethylphenyl)-4-(3-methoxyphenyl)-5-trifluoromethyl-1H-1,2,3-triazole (C 18 H 16 F 3 N 3 O, 2), 1-(3,4-dimethylphenyl)-4-(4-methoxyphenyl)-5-trifluoromethyl-1H-1,2,3-triazole (C 18 H 16 F 3 N 3 O, 3), 1-(2,4-dimethylphenyl)-4-(4-methoxyphenyl)-5-trifluoromethyl-1H-1,2,3-triazole (C 18 H 16 F 3 N 3 O, 4), 1-[2,4-bis(trifluoromethyl)phenyl]-4-(3-methoxyphenyl)-5-trifluoromethyl-1H-1,2,3-triazole (C 18 H 10 F 9 N 3 O, 5), 1-(3,4-dimethoxyphenyl)-4-(3,4-dimethoxyphenyl)-5-trifluoromethyl-1H-1,2,3-triazole (C 19 H 18 F 3 N 3 O 4 , 6) and 3-[4-(3,4-dimethoxyphenyl)-5-(trifluoromethyl)-1H-1,2,3-triazol-1-yl]phenol (C 17 H 14 F 3 N 3 O 3 , 7), have been determined and compared to that of J147. B3LYP/6-311++G(d,p) calculations have been performed to determine the potential surface and molecular electrostatic potential (MEP) of J147, and to examine the correlation between hydrazone J147 and the 1,2,3-triazoles, both bearing a CF 3 substituent. Using MEPs, it was found that the minimum-energy conformation of 4, which is nearly identical to its X-ray structure, is closely related to one of the J147 seven minima.

  12. Concept for polychromatic laser guide stars: one-photon excitation of the 4P3/2 level of a sodium atom.

    PubMed

    Pique, Jean-Paul; Moldovan, Ioana Cristina; Fesquet, Vincent

    2006-11-01

    One challenge for polychromatic laser guide stars is to create a sufficiently intense source in the UV. The flux required for the measurement of differential tip-tilt is the main issue that we address. We describe a model that has been validated using on-sky data. We present a method that excites the 4P3/2 sodium level using a one-photon excitation at 330 nm. It is more efficient than the two-photon excitation previously suggested since its power slope flux is 3 x 10(4) photons/s/m2/W instead of 1.3 x 10(3) photons/s/m2/W. This method is very promising both in terms of flux and system simplicity.

  13. Characterization and Thermal Decomposition of Nanometer 2,2', 4,4', 6,6'-Hexanitro-Stilbene and 1,3,5-Triamino-2,4,6-Trinitrobenzene Fabricated by a Mechanical Milling Method

    NASA Astrophysics Data System (ADS)

    Song, Xiaolan; Wang, Yi; Zhao, Shanshan; An, Chongwei; Wang, Jingyu; Zhang, Jinglin

    2018-04-01

    Nanometer 2,2', 4,4', 6,6'-hexanitro-stilbene (HNS) and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) were fabricated on a high-energy ball mill. The particle sizes of nano-HNS and nano-TATB were 98.4 and 57.8 nm, respectively. An SEM analysis was employed to image the micron morphology of nano-explosives. The particle size distribution was calculated by measuring the size of 300 particles in SEM images. XRD, IR, and XPS analyses were used to confirm whether the crystal phase, molecule structure, and surface elements were changed by the milling process. Thermal decomposition of nano-HNS and nano-TATB was investigated by differential scanning calorimetry (DSC) and thermal-infrared spectrometry online (DSC-IR) analyses. Using DSC traces collected from different heating rates, the kinetic and thermodynamic parameters of thermolysis of raw and nano-explosives were calculated (activation energy (EK), pre-exponential factor (lnAK), rate constant (k), activation heat (ΔH≠), activation free energy (ΔG≠), activation entropy (ΔS≠), critical temperature of thermal explosion (Tb), and critical heating rate of thermal explosion (dT/dt)Tb). The results indicated that nano-explosives were of different kinetic and thermodynamic properties from starting explosives. In addition, the gas products for thermal decomposition of nano-HNS and nano-TATB were detected. Although HNS and TATB are both nitro explosives, the decomposition products of the two were different. A mechanism to explain the difference is proposed.

  14. A facile growth process of CeO2-Co3O4 composite nanotubes and its catalytic stability for CO oxidation

    NASA Astrophysics Data System (ADS)

    Oh, Hyerim; Kim, Il Hee; Lee, Nam-Suk; Dok Kim, Young; Kim, Myung Hwa

    2017-08-01

    Hybrid cerium dioxide (CeO2)-cobalt oxide (Co3O4) composite nanotubes were successfully prepared by a combination of electrospinning and thermal annealing using CeO2 and Co3O4 precursors for the first time. Electrospun CeO2-Co3O4 composite nanotubes represent relatively porous surface texture with small dimensions between 80 and 150 nm in the outer diameter. The microscopic investigations indicate that the nanoparticle like crystalline structures of CeO2 and Co3O4 are homogenously distributed and continuously connected to form the shape of nanotube in the length of a few micrometers during thermal annealing. It is expected that the different evaporation behaviors of solvents and matrix polymer between the core and the shell in as-spun nanofibers in the course of thermal annealing could be reasonably responsible for the formation of well-defined CeO2/Co3O4 hybrid nanotubes. Additionally, the general catalytic activities of electrospun CeO2/Co3O4 hybrid nanotubes toward the oxidation of carbon monoxide (CO) were carefully examined by a continuous flow system, resulting in favorable catalytic activity as well as catalytic stability for CO oxidation between 150 °C and 200 °C without the deactivation of the catalyst with time stems from accumulation of reaction intermediates such as carbonate species.

  15. ELECTRONIC STRUCTURE AND LINEAR OPTICAL PROPERTIES OF MIXED ALKALI-METAL BOROPHOSPHATES (LiK2BP2O8, Li3K2BP4O14): A FIRST-PRINCIPLES STUDY

    NASA Astrophysics Data System (ADS)

    Zhang, Bei; Jing, Qun; Yang, Zhihua; Wang, Ying; Su, Xin; Pan, Shilie; Zhang, Jun

    2013-07-01

    LiK2BP2O8 and Li3K2BP4O14 are synthesized by high-temperature solution method with the same elements, while contain different fundamental building units. Li3K2BP4O14 is a novel P-O-P linking structure which gives a rare example of violation of Pauling's fourth rule. The electronic structures of LiK2BP2O8 and Li3K2BP4O14 are investigated by density functional calculations. Direct gaps of 5.038 eV (LiK2BP2O8) and 5.487 eV (Li3K2BP4O14) are obtained. By analyzing the density of states (DOS) of LiK2BP2O8 and Li3K2BP4O14, the P-O-P linking in fundamental building units of Li3K2BP4O14 crystal is proved theoretically. Based on the electronic properties, the linear optical information is captured.

  16. Design of a highly sensitive ethanol sensor using a nano-coaxial p-Co3O4/n-TiO2 heterojunction synthesized at low temperature.

    PubMed

    Liang, Y Q; Cui, Z D; Zhu, S L; Li, Z Y; Yang, X J; Chen, Y J; Ma, J M

    2013-11-21

    In this paper, we describe the design, fabrication and gas-sensing tests of nano-coaxial p-Co3O4/n-TiO2 heterojunction. Specifically, uniform TiO2 nanotubular arrays have been assembled by anodization and used as templates for generation of the Co3O4 one-dimensional nanorods. The structure morphology and composition of as-prepared products have been characterized by SEM, XRD, TEM, and XPS. A possible growth mechanism governing the formation of such nano-coaxial heterojunctions is proposed. The TiO2 nanotube sensor shows a normal n-type response to reducing ethanol gas, whereas TiO2-Co3O4 exhibits p-type response with excellent sensing performances. This conversion of sensing behavior can be explained by the formation of p-n heterojunction structures. A possible sensing mechanism is also illustrated, which can provide theoretical guidance for the further development of advanced gas-sensitive materials with p-n heterojunction.

  17. Experimental and computational approaches of a novel methyl (2E)-2-{[N-(2-formylphenyl)(4-methylbenzene)sulfonamido]methyl}-3-(4-chlorophenyl)prop-2-enoate: A potential antimicrobial agent and an inhibition of penicillin-binding protein

    NASA Astrophysics Data System (ADS)

    Murugavel, S.; Vetri velan, V.; Kannan, Damodharan; Bakthadoss, Manickam

    2016-07-01

    The title compound methyl(2E)-2-{[N-(2-formylphenyl) (4-methylbenzene)sulfonamido]methyl}-3-(4-chlorophenyl) prop-2-enoate (MFMSC) has been synthesized and single crystals were grown by slow evaporation solution growth technique at room temperature. Structural and vibrational spectroscopic studies were carried out by using single crystal X-ray diffraction, FT-IR and NMR spectral analysis together with DFT method using GAUSSIAN'03 software. The detailed interpretation of the vibrational spectra has been carried out by VEDA program. NBO analysis, Mulliken charge analysis, HOMO-LUMO, MEP, Global chemical reactivity descriptors and thermodynamic properties have been analyzed. The hyperpolarisability calculation reveals the present material has a reasonably good propensity for nonlinear optical activity. The obtained antimicrobial activity results indicate that the compound shows good to moderate activity against all tested bacterial and fungal pathogens. A computational study was also carried out to predict the drug-likeness and ADMET properties of the title compound. Due to the different potential biological activity of the title compound, molecular docking study is also reported and the compound might exhibit inhibitory activity against penicillin-binding protein PBP-2X.

  18. Monothiol Glutaredoxins Can Bind Linear [Fe3S4]+ and [Fe4S4]2+ Clusters in Addition to [Fe2S2]2+ Clusters: Spectroscopic Characterization and Functional Implications

    PubMed Central

    Zhang, Bo; Bandyopadhyay, Sibali; Shakamuri, Priyanka; Naik, Sunil G.; Huynh, Boi Hanh; Couturier, Jérémy; Rouhier, Nicolas; Johnson, Michael K.

    2013-01-01

    Saccharomyces cerevisiae mitochondrial glutaredoxin 5 (Grx5) is the archetypical member of a ubiquitous class of monothiol glutaredoxins with a strictly conserved CGFS active-site sequence that has been shown to function in biological [Fe2S2]2+ cluster trafficking. In this work, we show that recombinant S. cerevisiae Grx5 purified aerobically after prolonged exposure of the cell-free extract to air or after anaerobic reconstitution in the presence of glutathione, predominantly contains a linear [Fe3S4]+ cluster. The excited state electronic properties and ground state electronic and vibrational properties of the linear [Fe3S4]+ cluster have been characterized using UV-visible absorption/CD/MCD, EPR, Mössbauer and resonance Raman spectroscopies. The results reveal a rhombic S = 5/2 linear [Fe3S4]+ cluster with properties similar to those reported for synthetic linear [Fe3S4]+ clusters and the linear [Fe3S4]+ clusters in purple aconitase. Moreover, the results indicate that the Fe-S cluster content previously reported for many monothiol Grxs has been misinterpreted exclusively in terms of [Fe2S2]2+ clusters, rather than linear [Fe3S4]+ clusters or mixtures of linear [Fe3S4]+ and [Fe2S2]2+ clusters. In the absence of GSH, anaerobic reconstitution of Grx5 yields a dimeric form containing one [Fe4S4]2+ cluster that competent for in vitro activation of apo-aconitase, via intact cluster transfer. The ligation of the linear [Fe3S4]+ and [Fe4S4]2+ clusters in Grx5 has been assessed by spectroscopic, mutational and analytical studies. Potential roles for monothiol Grx5 in scavenging and recycling linear [Fe3S4]+ clusters released during protein unfolding under oxidative stress conditions and in maturation of [Fe4S4]2+ cluster-containing proteins are discussed in light of these results. PMID:24032439

  19. Toxicological evaluation of two novel bitter modifying flavour compounds: 3-(1-((3,5-dimethylisoxazol-4-yl)methyl)-1H-pyrazol-4-yl)-1-(3-hydroxybenzyl)imidazolidine-2,4-dione and 3-(1-((3,5-dimethylisoxazol-4-yl)methyl)-1H-pyrazol-4-yl)-1-(3-hydroxybenzyl)-5,5-dimethylimidazolidine-2,4-dione.

    PubMed

    Karanewsky, Donald S; Arthur, Amy J; Liu, Hanghui; Chi, Bert; Ida, Lily; Markison, Stacy

    2016-01-01

    A toxicological evaluation of two novel bitter modifying flavour compounds, 3-(1-((3,5-dimethylisoxazol-4-yl)methyl)-1 H -pyrazol-4-yl)-1-(3-hydroxybenzyl)imidazolidine-2,4-dione (S6821, CAS 1119831-25-2) and 3-(1-((3,5-dimethylisoxazol-4-yl)methyl)-1 H -pyrazol-4-yl)-1-(3-hydroxybenzyl)-5,5-dimethylimidazolidine-2,4-dione (S7958, CAS 1217341-48-4), were completed for the purpose of assessing their safety for use in food and beverage applications. S6821 undergoes oxidative metabolism in vitro , and in rat pharmacokinetic studies both S6821 and S7958 are rapidly converted to the corresponding O-sulfate and O-glucuronide conjugates. S6821 was not found to be mutagenic or clastogenic in vitro , and did not induce micronuclei in bone marrow polychromatic erythrocytes in vivo . S7958, a close structural analog of S6821, was also found to be non-mutagenic in vitro . In short term and subchronic oral toxicity studies in rats, the no-observed-adverse-effect-level (NOAEL) for both S7958 and S6821 was 100 mg/kg bw/day (highest dose tested) when administered as a food ad-mix for either 28 or 90 consecutive days, respectively. Furthermore, S6821 demonstrated a lack of maternal toxicity, as well as adverse effects on fetal morphology at the highest dose tested, providing a NOAEL of 1000 mg/kg bw/day for both maternal toxicity and embryo/fetal development when administered orally during gestation to pregnant rats.

  20. 1-(substituted benzyl)-3,4,5,6-tetrahydro-2(1H)-pyrimidones: a series with stimulant and depressant activities.

    PubMed

    Ellis, K O; Schwan, T J; Wessels, F L; Miles, N J

    1980-10-01

    A series of 1-(substituted benzyl)-3,4,5,6-tetrahydro-2(1H)-pyrimidones was synthesized primarily by catalytic hydrogenation of the corresponding 1-(substituted benzyl)-2(1H)-pyrimidone. The pharmacological evaluation of these compounds in mice revealed a unique profile that included evidence of CNS stimulation and depression within the series and in the same compounds. Some members of this series induced signs of only CNS stimulation, some compounds caused signs of only CNS depression and skeletal muscle relaxation, and some caused signs of both stimulation and depression in the same animal. This apparent dual activity was assessed further in mice with antidepressant tests based on tetrabenazine antagonism and with antianxiety/anticonvulsant tests on the antagonism of a number of convulsants. The 4-chloro-, 4-fluoro-, 4-bromo-, and 3,4-dichlorobenzyl compounds exhibited antidepressant and antianxiety activities in the same dose range. Among these four compounds, the 3,4-dichlorobenzyl compound possessed the lowest antitetrabenazine (17 mg/kg po) and antipentylenetetrazol (23 mg/kg po) ED50 values. The 4-fluoro compound antagonized tetrabenazine-, pentylenetetrazol-, and isoniazid-induced tonic convulsions in the same dose range (congruent to 50 mg/kg po).