Separation of CsCl and SrCl2 from a ternary CsCl-SrCl2-LiCl via a zone refining process for waste salt minimization of pyroprocessing

NASA Astrophysics Data System (ADS)

Shim, Moonsoo; Choi, Ho Gil; Yi, Kyung Woo; Hwang, Il Soon; Lee, Jong Hyeon

2016-11-01

The purification of LiCl salt mixture has traditionally been carried out by a melt crystallization process. To improve the throughput of zone refining, three heaters were installed in the zone refiner. The zone refining method was used to grow pure LiCl salt ingots from LiCl-CsCl-SrCl2 salt mixture. The main investigated parameters were the heater speed and the number of passes. A change in the LiCl crystal grain size was observed according to the horizontal direction. From each zone refined salt ingot, samples were collected horizontally. To analyze the concentrations of Sr and Cs, an inductively coupled plasma optical emission spectrometer and inductively coupled plasma mass spectrometer were used, respectively. The experimental results show that Sr and Cs concentrations at the initial region of the ingot were low and reached their peak at the final freezing region of the salt ingot. Concentration results of zone refined salt were compared with theoretical results yielded by the proposed model to validate its predictions. The keff of Sr and Cs were 0.13 and 0.11, respectively. The decontamination factors of Sr and Cs were 450 and 1650, respectively.

75 FR 8461 - Airworthiness Directives; Bombardier, Inc. Model CL-600-1A11 (CL-600), CL-600-2A12 (CL-601), and...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-02-25

... Model CL-600-1A11 AFM (Winglets). These two TRs are approved by TCCA, and should be replaced in AD 2009... the Canadair Challenger Model CL-600-1A11 AFM (Winglets). We agreed and proposed to revise Table 2 of...) 600-1/17 August 16, 2006.. Canadair Challenger Model CL-600-1A11 AFM (Winglets). (iii) 601/14 August...

Simple preparations of Pd6Cl12, Pt6Cl12, and Qn[Pt2Cl8+n], n=1, 2 (Q=TBA+, PPN+) and structural characterization of [TBA][Pt2Cl9] and [PPN]2[Pt2Cl10].C7H8.

PubMed

Dell'Amico, Daniela Belli; Calderazzo, Fausto; Marchetti, Fabio; Ramello, Stefano; Samaritani, Simona

2008-02-04

The hexanuclear Pd6Cl12, i.e., the crystal phase classified as beta-PdCl2, was obtained by reacting [TBA]2[Pd2Cl6] with AlCl3 (or FeCl3) in CH2Cl2. The action of AlCl3 on PtCl42-, followed by digestion of the resulting solid in 1,2-C2H4Cl2 (DCE), CHCl3, or benzene, produced Pt6Cl12.DCE, Pt6Cl12.CHCl3, or Pt6Cl12.C6H6, respectively. Treating [TBA]2[PtCl6] with a slight excess of AlCl3 afforded [TBA][Pt2Cl9], whose anion was established crystallographically to be constituted by two "PtCl6" octahedra sharing a face. Dehydration of H2PtCl6.nH2O with SOCl2 gave an amorphous compound closely analyzing as PtCl4, reactive with [Q]Cl in SOCl2 to yield [Q][Pt2Cl9] or [Q]2[Pt2Cl10], depending on the [Q]Cl/Pt molar ratio (Q=TBA+, PPN+). A single-crystal X-ray diffraction study has shown [PPN]2[Pt2Cl10].C7H8 to contain dinuclear anions formed by two edge-sharing PtCl6 octahedra.

State-specific enhancement of Cl+ and Cl- desorption for SiCl4 adsorbed on a Si(100) surface following Cl 2 p and Si 2 p core-level excitations.

PubMed

Chen, J M; Lu, K T

2001-04-02

State-specific desorption for SiCl4 adsorbed on a Si(100) surface at approximately 90 K with variable coverage following the Cl 2p and Si 2p core-level excitations has been investigated using synchrotron radiation. The Cl+ yields show a significant enhancement following the Cl 2p-->8a*1 excitation. The Cl- yields are notably enhanced at the 8a*1 resonance at both Cl 2p and Si 2p edges. The enhancement of the Cl- yield occurs through the formation of highly excited states of the adsorbed molecules. These results provide some new dissociation processes from adsorbates on surfaces via core-level excitation.

Heterogeneous Reaction of ClONO2(g) + NaCl(s) to Cl2(g) + NaNO3(s)

NASA Technical Reports Server (NTRS)

Timonen, Raimo S.; Chu, Liang T.; Leu, Ming-Taun; Keyser, Leon F.

1994-01-01

The heterogeneous reaction of ClON02 + NaCl yields Cl2 + NaNO3 (eq 1) was investigated over a temperature range 220-300 K in a flow-tube reactor interfaced with a differentially pumped quadrupole mass spectrometer. Partial pressures of ClON02 in the range 10(exp -8) - 10(exp -5) Torr were used. Granule sizes and surface roughness of the NaCl substrates were determined by using a scanning electron microscope, and in separate experiments, surface areas of the substrates were measured by using BET analysis of gas-adsorption isotherms. For dry NaCl substrates, both the decay rates of ClON02 and the growth rates Of C12 were used to obtain reaction probabilities, gamma(sub l) = (4.6 +/- 3.0) x 10(exp -3) at 296 K and (6.7 +/- 3.2) x 10(exp -1) at 225 K, after considering the internal surface area, The error bars represent 1 standard deviation. The Cl2 yield based on the ClONO2 reacted was measured to be 1.0 +/- 0.2. In order to mimic the conditions encountered in the lower stratosphere, the effect of water vapor pressures between 5 x 10(exp -5) and 3 x 10(exp -4) Torr on reaction 1 was also studied. With added H20, reaction probabilities, gamma = (4.1 +/- 2.1) x 10(exp -3) at 296 K and (4.7 +/- 2.9) x 10(exp -3) at 225 K, were obtained. A trace of HOCl, the reaction product from the ClON02 + H20 yield HOCl + HN03 reaction, was observed in addition to the C12 product from reaction 1. The implications of this result for the enhancement of hydrogen chloride in the stratosphere after the El Chichon volcanic eruption and for the marine troposphere are discussed.

Isotopic ratios of 36Cl/Cl in Japanese surface soil

NASA Astrophysics Data System (ADS)

Seki, R.; Matsuhiro, T.; Nagashima, Y.; Takahashi, T.; Sasa, K.; Sueki, K.; Tosaki, Y.; Bessho, K.; Matsumura, H.; Miura, T.

2007-06-01

We have measured the 36Cl/Cl ratio of uncultivated surface soil samples collected from 11 areas distributed throughout Japan to determine the undisturbed value of the ratio. The ratio was found to be on the order of 10-13 except for the Tokai-mura area, where four research reactors, two commercial nuclear power plants and a nuclear fuel reprocessing plant have been operated. The observed ratio in the Tokai-mura area was higher than 10-12. Notably, soil samples collected from a site of commercial BWR nuclear power plants in Fukushima prefecture showed no significant increase in 36Cl/Cl ratio. The 36Cl/Cl ratio depth profiles of soil samples collected at both of Makabe-town and Tokai-mura were also measured. Since Makabe-town is located about 50 km apart from Tokai-mura, we do not expect it to be affected by the nuclear facilities. No large variations were observed in the Makabe depth profile; the measured ratios ranged from ∼3 to ∼5 × 10-13. The result obtained for Tokai-mura is significantly different in that from the surface to about 80 cm depth, the measured ratios, ∼10-12, are much higher than any at Makabe. At depth below 80 cm, the Tokai-mura ratios are lower and become indistinguishable from those at Makabe. The 36Cl/Cl ratio in unaffected areas of Japan is estimated to be 3-4 × 10-13.

Electrical conductivity of low-temperature NaCl-KCl-ZrCl4 melts

NASA Astrophysics Data System (ADS)

Salyulev, A. B.; Khokhlov, V. A.; Red'kin, A. A.

2014-08-01

The dependences of the electrical conductivity of NaCl-KCl-ZrCl4 molten mixtures with a molar ratio NaCl : KCl = 8 : 29 on the temperature (temperature range of 300-540°C) and the ZrCl4 concentration (54.3-75.2 mol %) have been measured for the first time using unique cells.

121Sb and 35Cl NQR in RCN · SbCl5 Complexes

NASA Astrophysics Data System (ADS)

Semin, G. K.; Kuznetsov, S. I.; Raevsky, A. M.; Bryukhova, E. V.

1994-05-01

35Cl and 121Sb NQR spectra of RCN · SbCl5 complexes with R = Et, n-Pr, i-Pr, n-Bu, n-C5H11 , Cl(CH2)2, C6H4CH2, Ph, Cl, Me, CCl3 were measured and /or refined at 77 K. Redistribution of the "transferred charge" in the SbCl5 fragment of the complexes under study was investigated. The existence of a specific region of dispersion of the electron-nuclear motions (DENM) in RCN · SbCl5 complexes was established.

Kinetic and thermochemical studies of the ClO + ClO + M ↔ Cl2O2 + M reaction

NASA Astrophysics Data System (ADS)

Ferracci, V.; Rowley, D. M.

2009-12-01

Chlorine monoxide (ClO) radicals play a crucial role in polar ozone destruction events and the ClO dimer cycle has been identified as one of the most effective ozone-depleting catalytic cycles operating in the polar winter. A recent paper by von Hobe et al.1 highlighted significant inconsistencies between laboratory results, theoretical calculations and field observations concerning the ClO dimer ozone destruction cycle. This work has investigated the temperature dependence of the equilibrium constant of one of the key reactions in this cycle, ClO + ClO + M ↔ Cl2O2 + M (1, -1), by means of laser flash photolysis coupled with time-resolved UV absorption spectroscopy. ClO radicals were generated via laser flash photolysis of Cl2/Cl2O mixtures in synthetic air. The concentration of radicals was monitored via UV absorption spectroscopy: the use of a Charge Coupled Device (CCD) detector allowed time resolution over a broad range of wavelengths. The equilibrium constant Keq was determined as the ratio of the rate constants of the forward and reverse reaction (1, -1) over the T range 256 - 312 K. Second Law and Third Law analytical methods were employed to determine the standard enthalpy and entropy changes of reaction 1, ΔrH° and ΔrS°, from the measured equilibrium constants. The values obtained from the Second Law analysis (ΔrH° = - 80.8 ± 2.2 kJ mol-1; ΔrS° = - 168.4 ± 7.9 J K-1 mol-1) are in good agreement with previous work 2 but greater in magnitude than current NASA recommendations 3. It was also found that, under typical laboratory conditions employed in this work, [ClO] decay exhibits pure second order kinetics at T ≤ 250 K. A higher rate constant for the ClO recombination reaction (1) was also observed in this work (compared to the NASA evaluation 3), implying a higher Keq and a different partitioning between ClO and Cl2O2, shifting towards the dimer. 1. M. Von Hobe, R. J. Salawitch, T. Canty, H. Keller-Rudek, G. K. Moortgat, J.-U. Grooss, R. M�

Ab initio chemical kinetic study on Cl + ClO and related reverse processes.

PubMed

Xu, Z F; Lin, M C

2010-11-04

The reaction of ClO with Cl and its related reverse processes have been studied theoretically by ab initio quantum chemical and statistical mechanical calculations. The geometric parameters of the reactants, products, and transition states are optimized by both UMPW1PW91 and unrestricted coupled-cluster single and double excitation (UCCSD) methods with the 6-311+G(3df) basis set. The potential energy surface has been further refined (with triple excitations, T) at the UCCSD(T)/6-311+G(3df) level of theory. The results show that Cl(2) and O ((3)P) can be produced by chlorine atom abstraction via a tight transition state, while ClOCl ((1)A(1)) and ClClO ((1)A') can be formed by barrierless association processes with exothermicities of 31.8 and 16.0 kcal/mol, respectively. In principle the O ((1)D) atom can be generated with a large endothermicity of 56.9 kcal/mol; on the other hand, its barrierless reaction with Cl(2) can readily form ClClO ((1)A'), which fragments rapidly to give ClO + Cl. The rate constants of both forward and reverse processes have been predicted at 150-2000 K by the microcanonical variational transition state theory (VTST)/Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The predicted rate constants are in good agreement with available experimental data within reported errors.

Measurements of the liquidus surface and solidus transitions of the NaCl-UCl3 and NaCl-UCl3-CeCl3 phase diagrams

NASA Astrophysics Data System (ADS)

Sooby, E. S.; Nelson, A. T.; White, J. T.; McIntyre, P. M.

2015-11-01

NaCl-UCl3-PuCl3 is proposed as the fuel salt for a number of molten salt reactor concepts. No experimental data exists for the ternary system, and limited data is available for the binary compositions of this salt system. Differential scanning calorimetry is used in this study to examine the liquidus surface and solidus transition of a surrogate fuel-salt (NaCl-UCl3-CeCl3) and to reinvestigate the NaCl-UCl3 eutectic phase diagram. The results of this study show good agreement with previously reported data for the pure salt compounds used (NaCl, UCl3, and CeCl3) as well as for the eutectic points for the NaCl-UCl3 and NaCl-CeCl3 binary systems. The NaCl-UCl3 liquidus surface produced in this study predicts a 30-40 °C increase on the NaCl-rich side of the binary phase diagram. The increase in liquidus temperature could prove significant to molten salt reactor modeling.

Oxalyl chloride, ClC(O)C(O)Cl: UV/vis spectrum and Cl atom photolysis quantum yields at 193, 248, and 351 nm

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

Ghosh, Buddhadeb; Papanastasiou, Dimitrios K.; Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado 80309

2012-10-28

Oxalyl chloride, (ClCO){sub 2}, has been used as a Cl atom photolytic precursor in numerous laboratory kinetic and photochemical studies. In this study, the UV/vis absorption spectrum of (ClCO){sub 2} and the Cl atom quantum yields in its photolysis at 193, 248, and 351 nm are reported. The UV/vis spectrum was measured between 200 and 450 nm at 296 K using diode array spectroscopy in conjunction with an absolute cross section obtained at 213.9 nm. Our results are in agreement with the spectrum reported by Baklanov and Krasnoperov [J. Phys. Chem. A 105, 97-103 (2001)], which was obtained at 11more » discrete wavelengths between 193.3 and 390 nm. Cl atom quantum yields, {Phi}({lambda}), were measured using pulsed laser photolysis coupled with time resolved atomic resonance fluorescence detection of Cl. The UV photolysis of (ClCO){sub 2} has been shown in previous studies to occur via an impulsive three-body dissociation mechanism, (COCl){sub 2}+ hv{yields} ClCO*+ Cl + CO (2), where the excited ClCO radical, ClCO*, either dissociates or stabilizes ClCO*{yields} Cl + CO (3a), {yields} ClCO (3b). ClCO is thermally unstable at the temperatures (253-298 K) and total pressures (13-128 Torr) used in our experiments ClCO + M {yields} Cl + CO + M (4) leading to the formation of a secondary Cl atom that was resolvable in the Cl atom temporal profiles obtained in the 248 and 351 nm photolysis of (ClCO){sub 2}. {Phi}(193 nm) was found to be 2.07 {+-} 0.37 independent of bath gas pressure (25.8-105.7 Torr, N{sub 2}), i.e., the branching ratio for channel 2a or the direct formation of 2Cl + 2CO in the photolysis of (ClCO){sub 2} is >0.95. At 248 nm, the branching ratio for channel 2a was determined to be 0.79 {+-} 0.15, while the total Cl atom yield, i.e., following the completion of reaction (4), was found to be 1.98 {+-} 0.26 independent of bath gas pressure (15-70 Torr, N{sub 2}). {Phi}(351 nm) was found to be pressure dependent between 7.8 and 122.4 Torr (He, N{sub 2}). The

Oxalyl chloride, ClC(O)C(O)Cl: UV/vis spectrum and Cl atom photolysis quantum yields at 193, 248, and 351 nm.

PubMed

Ghosh, Buddhadeb; Papanastasiou, Dimitrios K; Burkholder, James B

2012-10-28

Oxalyl chloride, (ClCO)(2), has been used as a Cl atom photolytic precursor in numerous laboratory kinetic and photochemical studies. In this study, the UV/vis absorption spectrum of (ClCO)(2) and the Cl atom quantum yields in its photolysis at 193, 248, and 351 nm are reported. The UV∕vis spectrum was measured between 200 and 450 nm at 296 K using diode array spectroscopy in conjunction with an absolute cross section obtained at 213.9 nm. Our results are in agreement with the spectrum reported by Baklanov and Krasnoperov [J. Phys. Chem. A 105, 97-103 (2001)], which was obtained at 11 discrete wavelengths between 193.3 and 390 nm. Cl atom quantum yields, Φ(λ), were measured using pulsed laser photolysis coupled with time resolved atomic resonance fluorescence detection of Cl. The UV photolysis of (ClCO)(2) has been shown in previous studies to occur via an impulsive three-body dissociation mechanism, (COCl)(2) + hv → ClCO* + Cl + CO (2), where the excited ClCO radical, ClCO*, either dissociates or stabilizes ClCO* → Cl + CO (3a), → ClCO (3b). ClCO is thermally unstable at the temperatures (253-298 K) and total pressures (13-128 Torr) used in our experiments ClCO + M → Cl + CO + M (4) leading to the formation of a secondary Cl atom that was resolvable in the Cl atom temporal profiles obtained in the 248 and 351 nm photolysis of (ClCO)(2). Φ(193 nm) was found to be 2.07 ± 0.37 independent of bath gas pressure (25.8-105.7 Torr, N(2)), i.e., the branching ratio for channel 2a or the direct formation of 2Cl + 2CO in the photolysis of (ClCO)(2) is >0.95. At 248 nm, the branching ratio for channel 2a was determined to be 0.79 ± 0.15, while the total Cl atom yield, i.e., following the completion of reaction (4), was found to be 1.98 ± 0.26 independent of bath gas pressure (15-70 Torr, N(2)). Φ(351 nm) was found to be pressure dependent between 7.8 and 122.4 Torr (He, N(2)). The low-pressure limit of the total Cl atom quantum yield, Φ(0)(351 nm), was 2

Methadone but not morphine inhibits lubiprostone-stimulated Cl- currents in T84 intestinal cells and recombinant human ClC-2, but not CFTR Cl- currents.

PubMed

Cuppoletti, John; Chakrabarti, Jayati; Tewari, Kirti; Malinowska, Danuta H

2013-05-01

In clinical trials, methadone, but not morphine, appeared to prevent beneficial effects of lubiprostone, a ClC-2 Cl(-) channel activator, on opioid-induced constipation. Effects of methadone and morphine on lubiprostone-stimulated Cl(-) currents were measured by short circuit current (Isc) across T84 cells. Whole cell patch clamp of human ClC-2 (hClC-2) stably expressed in HEK293 cells and in a high expression cell line (HEK293EBNA) as well as human CFTR (hCFTR) stably expressed in HEK293 cells was used to study methadone and morphine effects on recombinant hClC-2 and hCFTR Cl(-) currents. Methadone but not morphine inhibited lubiprostone-stimulated Isc in T84 cells with half-maximal inhibition at 100 nM. Naloxone did not affect lubiprostone stimulation or methadone inhibition of Isc. Lubiprostone-stimulated Cl(-) currents in hClC-2/HEK293 cells, but not forskolin/IBMX-stimulated Cl(-) currents in hCFTR/HEK293 cells, were inhibited by methadone, but not morphine. HEK293EBNA cells expressing hClC-2 showed time-dependent, voltage-activated, CdCl2-inhibited Cl(-) currents in the absence (control) and the presence of lubiprostone. Methadone, but not morphine, inhibited control and lubiprostone-stimulated hClC-2 Cl(-) currents with half-maximal inhibition at 100 and 200-230 nM, respectively. Forskolin/IBMX-stimulated hClC-2 Cl(-) currents were also inhibited by methadone. Myristoylated protein kinase inhibitor (a specific PKA inhibitor) inhibited forskolin/IBMX- but not lubiprostone-stimulated hClC-2 Cl(-) currents. Methadone caused greater inhibition of lubiprostone-stimulated currents added before patching (66.1 %) compared with after patching (28.7 %). Methadone caused inhibition of lubiprostone-stimulated Cl(-) currents in T84 cells and control; lubiprostone- and forskolin/IBMX-stimulated recombinant hClC-2 Cl(-) currents may be the basis for reduced efficacy of lubiprostone in methadone-treated patients.

ZnCl 2- and NH 4Cl-hydroponics gel electrolytes for zinc-carbon batteries

NASA Astrophysics Data System (ADS)

Khalid, N. H.; Ismail, Y. M. Baba; Mohamad, A. A.

Absorbency testing is used to determine the percentage of ZnCl 2 or NH 4Cl solution absorbed by a hydroponics gel (HPG). It is found that the absorbency of ZnCl 2 or NH 4Cl solution decreases with increasing solution concentration. The conductivity of ZnCl 2- and NH 4Cl-HPG electrolytes is dependent on the solution concentration. A mixture of salt solution with HPG yields excellent gel polymer electrolytes with conductivities of 0.026 and 0.104 S cm -1 at 3 M ZnCl 2 and 7 M NH 4Cl, respectively. These gel electrolytes are then used to produce zinc-carbon cells. The fabricated cells give capacities of 8.8 and 10.0 mAh, have an internal resistance of 25.4 and 19.8 Ω, a maximum power density of 12.7 and 12.2 mW cm -2, and a short-circuit current density of 29.1 and 33.9 mA cm -2 for ZnCl 2- and NH 4Cl-HPG electrolytes, respectively.

The distribution of meteoric 36Cl/Cl in the United States: A comparison of models

USGS Publications Warehouse

Moysey, S.; Davis, S.N.; Zreda, M.; Cecil, L.D.

2003-01-01

The natural distribution of 36Cl/Cl in groundwater across the continental United States has recently been reported by Davis et al. (2003). In this paper, the large-scale processes and atmospheric sources of 36Cl and chloride responsible for controlling the observed 36Cl/Cl distribution are discussed. The dominant process that affects 36Cl/Cl in meteoric groundwater at the continental scale is the fallout of stable chloride from the atmosphere, which is mainly derived from oceanic sources. Atmospheric circulation transports marine chloride to the continental interior, where distance from the coast, topography, and wind patterns define the chloride distribution. The only major deviation from this pattern is observed in northern Utah and southern Idaho where it is inferred that a continental source of chloride exists in the Bonneville Salt Flats, Utah. In contrast to previous studies, the atmospheric flux of 36Cl to the land surface was found to be approximately constant over the United States, without a strong correlation between local 36Cl fallout and annual precipitation. However, the correlation between these variables was significantly improved (R 2=0.15 to R 2=0.55) when data from the southeastern USA, which presumably have lower than average atmospheric 36Cl concentrations, were excluded. The total mean flux of 36Cl over the continental United States and total global mean flux of 36Cl are calculated to be 30.5??7.0 and 19.6??4.5 atoms m-2 s-1, respectively. The 36Cl/Cl distribution calculated by Bentley et al. (1996) underestimates the magnitude and variability observed for the measured 36Cl/Cl distribution across the continental United States. The model proposed by Hainsworth (1994) provides the best overall fit to the observed 36Cl/Cl distribution in this study. A process-oriented model by Phillips (2000) generally overestimates 36Cl/Cl in most parts of the country and has several significant local departures from the empirical data.

XAFS Study of Molten ZrCl4 in LiCl-KCl Eutectic

NASA Astrophysics Data System (ADS)

Okamoto, Yoshihiro; Motohashi, Haruhiko

2002-05-01

The local structure of motlen ZrCl4 in LiCl-KCl eutectic was investigated by using an X-ray absorption fine structure (XAFS) of the Zr K-absorption edge. The nearest Zr4+-Cl- distance and coordination number from the curve fitting analysis were (2.51±0.02) Å and 5.9±0.6, respectively. These suggest that a 6-fold coordination (ZrCl6)2- is predominant in the molten mixture.

Ab initio studies of ClOx reactions. VII. Isomers of Cl2O3 and their roles in the ClO+OClO reaction

NASA Astrophysics Data System (ADS)

Zhu, R. S.; Lin, M. C.

2003-05-01

The mechanism for the reaction ClO+OClO has been investigated by ab initio molecular orbital and transition state theory calculations. Nine stable isomers of Cl2O3 (including optical isomers) are located at the B3LYP/6-311+G(3df ) level. The transition states between pairs of isomers are explored and the stability of the isomers and their dissociation mechanisms are discussed. The relative stability predicted by the modified Gaussian-2 (G2M) method at the G2M//B3LYP/6-311+G(3df ) level is ClOCl(O)O>ClOOOCl(C2)>ClOOOCl(Cs)>ClClO3(C3v)>cyc-ClOOCl(O)>ClOOClO. The formation of ClOCl(O)O is dominant at low temperatures, taking place barrierlessly with the second and third order rate constant, k1∞=3.0×10-10 cm3molecule-1 s-1 and k10=1.1×10-17 T-5.5 exp(-398/T) cm6 molecule-2 s-1 in the temperature range of 200-400 K for N2 as the third-body. Over 500 K, formation of ClOO+ClO becomes dominant and ClOCl+1O2 is also competitive. Their overall rate constants can be given by kClOO=1.0×10-22 T2.8 exp(-78/T) and kClOCl=9.6×10-22 T2.4 exp(-1670/T)cm3 molecule-1 s-1, respectively, in the temperature range of 500-2500 K.

Selective synthesis of cis- and trans-[(NHC(Me))2PtCl2] and [NHC(Me)Pt(cod)Cl][NHC(Me)PtCl3] using NHC(Me)SiCl4.

PubMed

Lewis-Alleyne, Lesley C; Bassil, Bassem S; Böttcher, Tobias; Röschenthaler, Gerd-Volker

2014-11-14

NHC(Me)SiCl4 (NHC(Me) = 1,3-dimethylimidazolidin-2-ylidene) was used to synthesise novel NHC(Me)-Pt(ii) complexes. An atypical trans-cis isomerisation process was also achieved for [(NHC(Me))2PtCl2], while the synthesis of the unique double-complex salt [(NHC(Me))Pt(cod)Cl] [(NHC(Me))PtCl3] (cod = 1,5-cyclooctadiene) revealed the first-ever N-heterocyclic carbene analogue of the Cossa's salt anion.

Different blocking effects of HgCl2 and NaCl on aquaporins of pepper plants.

PubMed

Martínez-Ballesta, M Carmen; Diaz, Rafael; Martínez, Vicente; Carvajal, Micaela

2003-12-01

In this study we have compared the short-term effects of both NaCl and HgCl2 on aquaporins of Capsicum annuum L. plants, in order to determine whether or not they are similar. Stomatal conductance, turgor, root hydraulic conductance and water status were measured after 0.5, 2, 4 and 6 h of NaCl (60 mmol/L) or HgCl2 (50 micromol/L) treatment. When 60 mmol/L NaCl was added to the nutrient solution, a large decrease in stomatal conductance was observed after 2 h. However, when HgCl2 (50 micromol/L) was added, the decrease occurred after 4 h. The number of open stomata closed was always lower in plants treated with HgCl2 than in plants treated with NaCl. The water content of the Hg(2+)-treated plants was decreased, compared with controls and NaCl-treated. The root hydraulic conductance decreased after HgCl2 and NaCl treatment plants. Turgor of leaf epidermal cells was greatly reduced in plants treated with HgCl2, but remained constant in the NaCl treatment, compared with control plants. The fact that the stomatal conductance was reduced more rapidly after NaCl addition, followed by the stomatal closure, and that both water content and turgor did not differ from the control suggests that in NaCl-treated plants there must be a signal moving from root to shoot. Therefore, the control of plant homeostasis through a combined regulation of root and stomatal exchanges may be dependent on aquaporin regulation.

Separate Cl^- Conductances Activated by cAMP and Ca2+ in Cl^--Secreting Epithelial Cells

NASA Astrophysics Data System (ADS)

Cliff, William H.; Frizzell, Raymond A.

1990-07-01

We studied the cAMP- and Ca2+-activated secretory Cl^- conductances in the Cl^--secreting colonic epithelial cell line T84 using the whole-cell patch-clamp technique. Cl^- and K^+ currents were measured under voltage clamp. Forskolin or cAMP increased Cl^- current 2-15 times with no change in K^+ current. The current-voltage relation for cAMP-activated Cl^- current was linear from -100 to +100 mV and showed no time-dependent changes in current during voltage pulses. Ca2+ ionophores or increased pipette Ca2+ increased both Cl^- and K^+ currents 2-30 times. The Ca2+-activated Cl^- current was outwardly rectified, activated during depolarizing voltage pulses, and inactivated during hyperpolarizing voltage pulses. Addition of ionophore after forskolin further increased Cl^- conductance 1.5-5 times, and the current took on the time-dependent characteristics of that stimulated by Ca2+. Thus, cAMP and Ca2+ activate Cl^- conductances with different properties, implying that these second messengers activate different Cl^- channels or that they induce different conductive and kinetic states in the same Cl^- channel.

The Electrochemical Co-reduction of Mg-Al-Y Alloys in the LiCl-NaCl-MgCl2-AlF3-YCl3 Melts

NASA Astrophysics Data System (ADS)

Li, Mei; Liu, Yaochen; Han, Wei; Wang, Shanshan; Zhang, Milin; Yan, Yongde; Shi, Weiqun

2015-04-01

The electrochemical formation of Mg-Al-Y alloys was studied in the LiCl-NaCl-MgCl2 melts by the addition of AlF3 and YCl3 on a molybdenum electrode at 973 K (700 °C). In order to reduce the volatilization of salt solvent in the electrolysis process, the volatile loss of LiCl-NaCl-MgCl2 and LiCl-KCl-MgCl2 melts was first measured in the temperature range from 873 K to 1023 K (600 °C to 750 °C). Then, the electrochemical behaviors of Mg(II), Al(III), Y(III) ions and alloy formation processes were investigated by cyclic voltammetry, chronopotentiometry, and open circuit chronopotentiometry. The cyclic voltammograms indicate that the under-potential deposition of magnesium and yttrium on pre-deposited Al leads to formation of Mg-Al and Al-Y intermetallic compounds. The Mg-Al-Y alloys were prepared by galvanostatic electrolysis in the LiCl-NaCl-MgCl2-AlF3-YCl3 melts and characterized by X-ray diffraction and scanning electron microscopy with energy dispersive spectrometry. Composition of the alloys was analyzed by inductively coupled plasma-atomic emission spectrometer, and current efficiency was also determined by the alloy composition.

Viscosity of NaCl and other solutions up to 350{sup 0}C and 50 MPa pressures

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

Phillips, S.L.; Ozbek, H.; Igbene, A.

1980-11-01

Experimental values for the viscosity of sodium chloride solutions are critically reviewed for application to geothermal energy. Data published recently by Kestin, Los, Pepinov, and Semenyuk as well as earlier data are included. A theoretically based equation for calculating relative viscosity was developed, and used to generate tables of smoothed values over the ranges 20{sup 0}C to 350{sup 0}C, 0 to 5 m and pressures up to 50 MPa. The equation reproduces selected data to an average of better than 2 percent over the entire range of temperatures and pressures. Selected tables of data are included for KCl up tomore » 150{sup 0}C, CaCl{sub 2} solutions up to 100{sup 0}C, and for mixtures of NaCl with KCl and CaCl{sub 2}. Recommendations are given for additional data needs.« less

Improved method for efficient imaging of intracellular Cl(-) with Cl-Sensor using conventional fluorescence setup.

PubMed

Friedel, Perrine; Bregestovski, Piotr; Medina, Igor

2013-01-01

Chloride (Cl(-)) homeostasis is known to be fundamental for central nervous system functioning. Alterations in intracellular Cl(-) concentration ([Cl(-)]i) and changes in the efficacy of Cl(-) extrusion are involved in numerous neurological disorders. Therefore, there is a strong need for studies of the dynamics of [Cl(-)]i in different cell types under physiological conditions and during pathology. Several previous works reported having successfully achieved recording of [Cl(-)]i using genetically encoded Cl-Sensor that is composed of the cyan fluorescent protein (CFP) and Cl(-)-sensitive mutant of the yellow fluorescent protein (YFPCl). However, all reported works were performed using specially designed setups with ultra-sensitive CCD cameras. Our multiple attempts to monitor Cl(-)-dependent fluorescence of Cl-Sensor using conventional epifluorescence microscopes did not yield successful results. In the present work, we have analysed the reason of our failures and found that they were caused by a strong inactivation of the YFPCl component of Cl-Sensor during excitation of the CFP with 430 nm light. Based on the obtained results, we reduced 20-fold the intensity of the 430 nm excitation and modified the recording protocol that allows now stable long-lasting ratiometric measurements of Cl-Sensor fluorescence in different cell types including cultured hippocampal neurons and their tiny dendrites and spines. Simultaneous imaging and patch clamp recording revealed that in mature neurons, the novel protocol allows detection of as little as 2 mM changes of [Cl(-)]i from the resting level of 5-10 mM. We demonstrate also a usefulness of the developed [Cl(-)]i measurement procedure for large scale screening of the activity of exogenously expressed potassium-chloride co-transporter KCC2, a major neuronal Cl(-) extruder that is implicated in numerous neurological disorders and is a target for novel therapeutical treatments.

A thermochemical explanation for the stability of NaCl3 and NaCl7

NASA Astrophysics Data System (ADS)

Fernandes de Farias, Robson

2017-03-01

Thermodynamically stable cubic and orthorhombic NaCl3 as well as NaCl7 have been synthesized (Zhang et al., 2013). In the present work, a thermochemical explanation for the stability of such unusual sodium chlorides is provided, based on lattice energy values. Using the Glasser-Jenkins generalized equation (Glasser and Jenkins, 2000) lattice energies (kJ mol-1) of -162.5, -168.9 and -113.1 are calculated for Pm3n NaCl3, Pnma NaCl3 and NaCl7, respectively. It is postulated that any NaxCly compound could be synthesized, if the ionic character of the Nasbnd Cl bond in the prepared compound remains around 80%, and the sodium charge below unit.

Influence of pH and ionic strength (NaCl/Na2SO4) on the reaction HO Cl/ClO- + NO2-

NASA Astrophysics Data System (ADS)

Marcellos da Rosa, M.; Zetzsch, C.

2003-04-01

Equilibria such as HOCl + NO_2^- leftrightarrow ClNO_2 + OH^- and ClNO_2 + H_2O leftrightarrow NO_3^- + 2H^+ + Cl^- play an important role in halogen activation in the troposphere. We studied the oxidation of NO_2^- by HOCl/ClO^- in aqueous phase by stopped-flow measurements at different ionic strengths (bidestilled water, 0.1M NaCl, 1.0M NaCl and 1.0M Na_2SO^4) at various pH values (4.0, 5.5, 6.2 and 10.0) at 293K. The experiments were performed using a SX.18MV Applied Photophysics spectrophotometer, observing the exponential decay of HOCl/ClO^- at λ = 290nm between 10ms and 100s. HOCl (pK_a= 7.50) was obtained by bubbling N_2 with 1% Cl_2 through bidestilled water. The pH of the aqueous solutions of HOCl was determined by a pH meter (CG820, Schott) with a glass electrode N6180 (calibrated with standard buffer solutions at pH = 3.0, 4.0, 7.0 and 10.0), and the pH values were adjusted by dropwise addition of HClO_4 or NaOH. The concentrations of HOCl (ɛHOCl (230nm) = 100M-1cm-1) ([HOCl] = 1.3mM - 10mM) and ClO- (ɛClO- (292nm) = 350 M-1cm-1) ([ClO^-] = 1.3mM - 5mM) were determined by UV spectrometry (Kontron UVIKON 860) at a resolution of 2 nm in 1 cm cells at various pH values. The concentration range of NO_2^- was between 5mM and 50mM. The following second-order rate constant kII were obtained at 293K at various pH values (in units of M-1s-1) in H_2O: pH 4.0, (5.6±0.3)\\cdot 10^3; pH 5.5, (5.0±0.4)\\cdot 10^3; pH 10.0, 3.9±0.4; in 0.1M NaCl: pH 5.5, (4.3±0.4)\\cdot 10^3; pH 10.0, 2.6±0.4; in 1.0M NaCl: pH 5.5, (4.0±0.3); pH 10.0, 0.7±0.2 and in 1.0M Na_2SO_4: pH 5.5, (3.0±0.3)\\cdot 10^3; pH 10.0, 1.9±0.4. There is a strong effect of the pH on the reaction HOCl/ClO^- + NO_2^-, as reflected in the ratio kII_a(pH 5.5, HOCl)/kII_b(pH 10.0, ClO^-): in H_2O (kII_a ˜ 1200 \\cdot kII_b), in 0.1M NaCl (kII_a ˜ 1900 \\cdot kII_b), in 1.0M NaCl (kII_a ˜ 5700 \\cdot kII_b) and in 1.0 M Na_2SO_4 (kII_a ˜ 1500 \\cdot kII_b). A mechanism for the oxidation of NO

Spectroelectrochemistry of EuCl 3 in Four Molten Salt Eutectics; 3 LiCl−NaCl, 3 LiCl−2 KCl, LiCl−RbCl, and 3 LiCl−2 CsCl; at 873 K

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

Schroll, Cynthia A.; Chatterjee, Sayandev; Levitskaia, Tatiana

Key electrochemical properties affecting pyroprocessing of nuclear fuel were examined in four eutectic melts using using Eu3+/2+ as a representative probe. We report the electrochemical and spectroelectrochemical behavior of EuCl3 in four molten salt eutectics (3 LiCl – NaCl, 3 LiCl – 2 KCl, LiCl – RbCl and 3 LiCl – 2 CsCl) at 873 K. Cyclic voltammetry was used to determine the redox potential for Eu3+/2+ and the applied potentials for spectroelectrochemistry. Single step chronoabsorptometry and thin-layer spectroelectrochemistry were used to obtain the number of electrons transferred, redox potentials and diffusion coefficients for Eu3+ in each eutectic melt. Themore » redox potentials determined by thin-layer spectroelectrochemistry were extremely close to those obtained using cyclic voltammetry. The redox potential for Eu3+/2+ was most positive in the 3 LiCl - NaCl melt, showed a negative shift in the 3 LiCl - 2 KCl melt, and was the most negative in the LiCl - RbCl and 3 LiCl - 2 CsCl eutectics. The diffusion coefficient for Eu3+ followed this same trend; it was the largest in the 3 LiCl - NaCl melt and the smallest in the LiCl - RbCl and 3 LiCl - 2 CsCl melts. The basic one-electron reversible electron transfer for Eu3+/2+ was not changed by melt composition.« less

Electrical conductivity of KAlCl4-ZrCl4 molten mixtures

NASA Astrophysics Data System (ADS)

Salyulev, A. B.; Khokhlov, V. A.; Moskalenko, N. I.

2017-02-01

The electrical conductivity of commercially challenging KAlCl4-ZrCl4 molten mixtures has been studied as a function of temperature (in the range from 345°C to 500°C) and the ZrCl4 concentration (0‒32.5mol %) using cells of a unique design. It is found to vary in the range from 0.41 to 0.80 S cm-1, increasing with temperature or when the mole concentration of zirconium tetrachloride in molten mixtures decreases.

Na/beta-alumina/NaAlCl4, Cl2/C circulating cell

NASA Technical Reports Server (NTRS)

Cherng, Jing-Yih; Bennion, Douglas N.

1987-01-01

A study was made of a high specific energy battery based on a sodium negative electrode and a chlorine positive electrode with molten AlCl3-NaCl electrolyte and a solid beta alumina separator. The basic performance of a Na beta-alumina NaAlCl4, Cl2/C circulating cell at 200 C was demonstrated. This cell can be started at 150 C. The use of melting sodium chloroaluminate electrolyte overcomes some of the material problems associated with the high working temperatures of present molten salt systems, such as Na/S and LiAl/FeS, and retains the advantages of high energy density and relatively efficient electrode processes. Preliminary investigations were conducted on a sodium-chlorine static cell, material compability, electrode design, wetting, and theoretical calculations to assure a better chance of success before assembling a Na/Cl2 circulating cell. Mathematical models provide a theoretical explanation for the performance of the NaCl2 battery. The results of mathematical models match the experimental results very well. According to the result of the mathematical modeling, an output at 180 mA/sq cm and 3.2 V can be obtained with optimized cell design.

Effect of EtOH/MgCl(2) molar ratios on the catalytic properties of MgCl(2)-SiO(2)/TiCl(4) Ziegler-Natta catalyst for ethylene polymerization.

PubMed

Patthamasang, Supanan; Jongsomjit, Bunjerd; Praserthdam, Piyasan

2011-09-29

MgCl(2)-SiO(2)/TiCl(4) Ziegler-Natta catalysts for ethylene polymerization were prepared by impregnation of MgCl(2) on SiO(2) in heptane and further treatment with TiCl(4). MgCl(2)·nEtOH adduct solutions were prepared with various EtOH/MgCl(2) molar ratios for preparation of the MgCl(2)-supported and MgCl(2)-SiO(2)-supported catalysts in order to investigate the effect on polymerization performance of both catalyst systems. The catalytic activities for ethylene polymerization decreased markedly with increased molar ratios of [EtOH]/[MgCl(2)] for the MgCl(2)-supported catalysts, while for the bi-supported catalysts, the activities only decreased slightly. The MgCl(2)-SiO(2)-supported catalyst had relatively constant activity, independent of the [EtOH]/[MgCl(2)] ratio. The lower [EtOH]/[MgCl(2)] in MgCl(2)-supported catalyst exhibited better catalytic activity. However, for the MgCl(2)-SiO(2)-supported catalyst, MgCl(2) can agglomerate on the SiO(2) surface at low [EtOH]/[MgCl(2)] thus not being not suitable for TiCl(4) loading. It was found that the optimized [EtOH]/[MgCl(2)] value for preparation of bi-supported catalysts having high activity and good spherical morphology with little agglomerated MgCl(2) was 7. Morphological studies indicated that MgCl(2)-SiO(2)-supported catalysts have good morphology with spherical shapes that retain the morphology of SiO(2). The BET measurement revealed that pore size is the key parameter dictating polymerization activity. The TGA profiles of the bi-supported catalyst also confirmed that it was more stable than the mono-supported catalyst, especially in the ethanol removal region.

"JCE" Classroom Activity Connections: NaCl or CaCl[subscript 2], Smart Polymer Gel Tells More

ERIC Educational Resources Information Center

Chen, Yueh-Huey; Lin, Jia-Ying; Wang, Yu-Chen; Yaung, Jing-Fun

2010-01-01

This classroom activity connection demonstrates the differences between the effects of NaCl (a salt of monovalent metal ions) and CaCl[subscript 2] (a salt of polyvalent metal ions) on swollen superabsorbent polymer gels. Being ionic compounds, NaCl and CaCl[subscript 2] both collapse the swollen polymer gels. The gel contracted by NaCl reswells…

The Cathodic Behavior of Ti(III) Ion in a NaCl-2CsCl Melt

NASA Astrophysics Data System (ADS)

Song, Yang; Jiao, Shuqiang; Hu, Liwen; Guo, Zhancheng

2016-02-01

The cathodic behavior of Ti(III) ions in a NaCl-2CsCl melt was investigated by cyclic voltammetry, chronopotentiometry, and square wave voltammetry with a tungsten electrode being the working electrode at different temperatures. The results show that the cathodic behavior of Ti(III) ion consists of two irreversible steps: Ti3+ + e = Ti2+ and Ti2+ + 2 e = Ti. The diffusion coefficient for the Ti(III) ion in the NaCl-2CsCl eutectic is 1.26 × 10-5 cm2 s-1 at 873 K (600 °C), increases to be 5.57 × 10-5 cm2 s-1 at 948K (675°C), and further rises to 10.8 × 10-5 cm2 s-1 at 1023 (750 °C). Moreover, galvanostatic electrolysis performed on a titanium electrode further presents the feasibility of electrodepositing metallic titanium in the molten NaCl-2CsCl-TiCl3 system.

ClO radical yields in the reaction of O(1D) with Cl2, HCl, chloromethanes, and chlorofluoromethanes.

PubMed

Feierabend, Karl J; Papanastasiou, Dimitrios K; Burkholder, James B

2010-11-18

Absolute ClO radical product yields in the gas-phase reactions of O((1)D) with Cl(2), HCl, CCl(4), CHCl(3), CH(2)Cl(2), CH(3)Cl, CFCl(3), CF(2)Cl(2), CF(3)Cl, CHFCl(2), and CHF(2)Cl are reported. Product yields were measured using pulsed-laser photolysis of O(3) to produce O((1)D) in the presence of excess reactant combined with dual wavelength differential cavity ring-down spectroscopic detection of the ClO radical. ClO radical absorption cross sections for the A(2)Π(v = 10) ← X(2)Π(v = 0) transition band head near 280 nm were determined between 200 and 296 K as part of this work. The ClO product yields obtained at room temperature were Cl(2) (0.77 ± 0.10), HCl (0.20 ± 0.04), CCl(4) (0.79 ± 0.04), CHCl(3) (0.77 ± 0.04), CH(2)Cl(2) (0.73 ± 0.04), CH(3)Cl (0.46 ± 0.06), CFCl(3) (0.79 ± 0.04), CF(2)Cl(2) (0.76 ± 0.06), CF(3)Cl (0.82 ± 0.06), CHFCl(2) (0.73 ± 0.05), and CHF(2)Cl (0.56 ± 0.03), where the quoted error limits are 2σ of the measurement precision. ClO product yields in the O((1)D) + Cl(2) and CFCl(3) reactions were found to be independent of temperature between 200 and 296 K, within the precision of the measurements. The absolute ClO yields obtained in this study are compared with previously reported values determined using relative and indirect methods.

Lifetimes and Oscillator Strengths for Ultraviolet Transitions in P II, Cl II and Cl III

NASA Technical Reports Server (NTRS)

Cheng, S.; Federman, S. R.; Schectman, R. M.; Brown, M.; Irving, R. E.; Fritts, M. C.; Gibson, N. D.

2006-01-01

Oscillator strengths for transitions in P II, Cl II and Cl III are derived from lifetimes and branching factions measured with beam-foil techniques. The focus is on the multiplets with a prominent interstellar line at 1153 A in P II which is seen in spectra of hot stars, and the lines at 1071 A in Cl II and 1011 A in Cl III whose lines are seen in spectra of diffuse interstellar clouds and the Io torus acquired with the Far Ultraviolet Spectroscopic Explorer. These data represent the first complete set of experimental f-values for the lines in the multiplets. Our results for P II (lambda)1153 agree well with Curtis semi-empirical predictions, as well as the large scale computations by Hibbert and by Tayal. The data for Cl II (lambda)1071 also agree very well with the most recent theoretical effort and with Morton s newest recommendations. For Cl III, however, our f-values are significantly larger than those given by Morton; instead, they are more consistent with recent large-scale theoretical calculations. Extensive tests provide confirmation that LS coupling rules apply to the transitions for the multiplets in Cl II and Cl III.

Thermodynamic description of Tc(iv) solubility and hydrolysis in dilute to concentrated NaCl, MgCl2 and CaCl2 solutions.

PubMed

Yalçıntaş, Ezgi; Gaona, Xavier; Altmaier, Marcus; Dardenne, Kathy; Polly, Robert; Geckeis, Horst

2016-06-07

We present the first systematic investigation of Tc(iv) solubility, hydrolysis and speciation in dilute to concentrated NaCl, MgCl2 and CaCl2 systems, and comprehensive thermodynamic and activity models for the system Tc(4+)-H(+)-Na(+)-Mg(2+)-Ca(2+)-OH(-)-Cl(-)-H2O using both SIT and Pitzer approaches. The results are advancing the fundamental scientific understanding of Tc(iv) solution chemistry and are highly relevant in the applied context of nuclear waste disposal. The solubility of Tc(iv) was investigated in carbonate-free NaCl-NaOH (0.1-5.0 M), MgCl2 (0.25-4.5 M) and CaCl2 (0.25-4.5 M) solutions within 2 ≤ pHm≤ 14.5. Undersaturation solubility experiments were performed under an Ar atmosphere at T = 22 ± 2 °C. Strongly reducing conditions (pe + pHm≤ 2) were imposed with Na2S2O4, SnCl2 and Fe powder to stabilize technetium in the +IV redox state. The predominance of Tc(iv) in the aqueous phase was confirmed by solvent extraction and XANES/EXAFS spectroscopy. Solid phase characterization was accomplished after attaining thermodynamic equilibrium using XRD, SEM-EDS, XANES/EXAFS, TG-DTA and quantitative chemical analysis, and indicated that TcO2·0.6H2O(s) exerts solubility-control in all evaluated systems. The definition of the polyatomic Tc3O5(2+) species instead of TcO(2+) is favoured under acidic conditions, consistently with slope analysis (mTcvs. pHm) of the solubility data gained in this work and spectroscopic evidence previously reported in the literature. The additional formation of Tc(iv)-OH/O-Cl aqueous species in concentrated chloride media ([Cl(-)] = 9 M) and pHm≤ 4 is suggested by solubility and EXAFS data. The pH-independent behaviour of the solubility observed under weakly acidic to weakly alkaline pHm conditions can be explained with the equilibrium reaction TcO2·0.6H2O(s) + 0.4H2O(l) ⇔ TcO(OH)2(aq). Solubility data determined in dilute NaCl systems with pHm≥ 11 follow a well-defined slope of +1, consistent with the predominance of

Production of Cl2O2 from the self-reaction of the ClO radical

NASA Technical Reports Server (NTRS)

Molina, L. T.; Molina, M. J.

1987-01-01

The species Cl2O2 has been generated in a gaseous flow system at 220-240 K by reacting Cl atoms with one of three different ClO precursors: O3, Cl2O, or OClO. The infrared spectra of the reactive mixture indicate that at least two different dimers are produced: a predominant form with bands centered at 1225 and 1057/cm attributed to ClOOCl, and a second form with a band at 650/cm attributed to ClOClO. The UV spectrum of the predominant form shows a maximum absorption cross section of about 6.5 x 10 to the -18th sq cm/molecule around 270 nm, with a wing extending beyond 300 nm. The implications of these results for the chemistry of the stratosphere are discussed.

Separation of CsCl from a Ternary CsCl-LiCl-KCl Salt via a Melt Crystallization Technique for Pyroprocessing Waste Minimization

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

Ammon Williams; Supathorn Phongikaroon; Michael Simpson

A parametric study has been conducted to identify the effects of several parameters on the separation of CsCl from molten LiCl-KCl salt via a melt crystallization process. A reverse vertical Bridgman technique was used to grow the salt crystals. The investigated parameters were: (1) the advancement rate, (2) the crucible lid configuration, (3) the amount of salt mixture, (4) the initial composition of CsCl, and (5) the temperature difference between the high and low furnace zones. From each grown crystal, samples were taken axially and analyzed using inductively coupled plasma mass spectrometry (ICP-MS). Results show that CsCl concentrations at themore » top of the crystals were low and increased to a maximum at the bottom of the salt. Salt (LiCl-KCl) recycle percentages for the experiments ranged from 50% to 75% and the CsCl composition in the waste salt was low. To increase the recycle percentage and the concentration of CsCl in the waste form, the possibility of using multiple crystallization stages was explored to further optimize the process. Results show that multiple crystallization stages are practical and the optimal experimental conditions should be operated at 5.0 mm/hr rate with a lid configuration and temperature difference of 200 °C for a total of five crystallization stages. Under these conditions, up to 88% of the salt can be recycled.« less

UV absorption spectrum of the ClO dimer (Cl2O2) between 200 and 420 nm.

PubMed

Papanastasiou, Dimitrios K; Papadimitriou, Vassileios C; Fahey, David W; Burkholder, James B

2009-12-10

The UV photolysis of Cl(2)O(2) (dichlorine peroxide) is a key step in the catalytic destruction of polar stratospheric ozone. In this study, the gas-phase UV absorption spectrum of Cl(2)O(2) was measured using diode array spectroscopy and absolute cross sections, sigma, are reported for the wavelength range 200-420 nm. Pulsed laser photolysis of Cl(2)O at 248 nm or Cl(2)/Cl(2)O mixtures at 351 nm at low temperature (200-228 K) and high pressure (approximately 700 Torr, He) was used to produce ClO radicals and subsequently Cl(2)O(2) via the termolecular ClO self-reaction. The Cl(2)O(2) spectrum was obtained from spectra recorded following the completion of the gas-phase ClO radical chemistry. The spectral analysis used observed isosbestic points at 271, 312.9, and 408.5 nm combined with reaction stoichiometry and chlorine mass balance to determine the Cl(2)O(2) spectrum. The Cl(2)O(2) UV absorption spectrum peaks at 244.5 nm with a cross section of 7.6(-0.5)(+0.8) x 10(-18) cm(2) molecule(-1) where the quoted error limits are 2sigma and include estimated systematic errors. The Cl(2)O(2) absorption cross sections obtained for wavelengths in the range 300-420 nm are in good agreement with the Cl(2)O(2) spectrum reported previously by Burkholder et al. (J. Phys. Chem. A 1990, 94, 687) and significantly higher than the values reported by Pope et al. (J. Phys. Chem. A 2007, 111, 4322). A possible explanation for the discrepancy in the Cl(2)O(2) cross section values with the Pope et al. study is discussed. Representative, atmospheric photolysis rate coefficients are calculated and a range of uncertainty estimated based on the determination of sigma(Cl(2)O(2))(lambda) in this work. Although improvements in our fundamental understanding of the photochemistry of Cl(2)O(2) are still desired, this work indicates that major revisions in current atmospheric chemical mechanisms are not required to simulate observed polar ozone depletion.

UV Absorption Spectrum of the ClO Dimer (Cl2O2) between 200 and 420 nm

NASA Astrophysics Data System (ADS)

Papanastasiou, Dimitrios K.; Papadimitriou, Vassileios C.; Fahey, David W.; Burkholder, James B.

2009-11-01

The UV photolysis of Cl2O2 (dichlorine peroxide) is a key step in the catalytic destruction of polar stratospheric ozone. In this study, the gas-phase UV absorption spectrum of Cl2O2 was measured using diode array spectroscopy and absolute cross sections, σ, are reported for the wavelength range 200-420 nm. Pulsed laser photolysis of Cl2O at 248 nm or Cl2/Cl2O mixtures at 351 nm at low temperature (200-228 K) and high pressure (˜700 Torr, He) was used to produce ClO radicals and subsequently Cl2O2 via the termolecular ClO self-reaction. The Cl2O2 spectrum was obtained from spectra recorded following the completion of the gas-phase ClO radical chemistry. The spectral analysis used observed isosbestic points at 271, 312.9, and 408.5 nm combined with reaction stoichiometry and chlorine mass balance to determine the Cl2O2 spectrum. The Cl2O2 UV absorption spectrum peaks at 244.5 nm with a cross section of 7.6-0.5+0.8 × 10-18 cm2 molecule-1 where the quoted error limits are 2σ and include estimated systematic errors. The Cl2O2 absorption cross sections obtained for wavelengths in the range 300-420 nm are in good agreement with the Cl2O2 spectrum reported previously by Burkholder et al. (J. Phys. Chem. A 1990, 94, 687) and significantly higher than the values reported by Pope et al. (J. Phys. Chem. A 2007, 111, 4322). A possible explanation for the discrepancy in the Cl2O2 cross section values with the Pope et al. study is discussed. Representative, atmospheric photolysis rate coefficients are calculated and a range of uncertainty estimated based on the determination of σCl2O2(λ) in this work. Although improvements in our fundamental understanding of the photochemistry of Cl2O2 are still desired, this work indicates that major revisions in current atmospheric chemical mechanisms are not required to simulate observed polar ozone depletion.

Chloride Channelopathies of ClC-2

PubMed Central

Bi, Miao Miao; Hong, Sen; Zhou, Hong Yan; Wang, Hong Wei; Wang, Li Na; Zheng, Ya Juan

2014-01-01

Chloride channels (ClCs) have gained worldwide interest because of their molecular diversity, widespread distribution in mammalian tissues and organs, and their link to various human diseases. Nine different ClCs have been molecularly identified and functionally characterized in mammals. ClC-2 is one of nine mammalian members of the ClC family. It possesses unique biophysical characteristics, pharmacological properties, and molecular features that distinguish it from other ClC family members. ClC-2 has wide organ/tissue distribution and is ubiquitously expressed. Published studies consistently point to a high degree of conservation of ClC-2 function and regulation across various species from nematodes to humans over vast evolutionary time spans. ClC-2 has been intensively and extensively studied over the past two decades, leading to the accumulation of a plethora of information to advance our understanding of its pathophysiological functions; however, many controversies still exist. It is necessary to analyze the research findings, and integrate different views to have a better understanding of ClC-2. This review focuses on ClC-2 only, providing an analytical overview of the available literature. Nearly every aspect of ClC-2 is discussed in the review: molecular features, biophysical characteristics, pharmacological properties, cellular function, regulation of expression and function, and channelopathies. PMID:24378849

Direct formation of (CH sub 3 ) sub 2 HSiCl from silicon and CH sub 3 Cl

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

Magrini, K.A.; Falconer, J.L.; Koel, B.E.

1989-07-13

A Cu-catalyzed reaction procedure was found for the selective formation of dimethylchlorosilane ((CH{sub 3}){sub 2}HSiCl) from the direct reaction of CH{sub 3}Cl with solid Si. The new procedure is a two-step process. A Cu/Si sample is prepared by evaporating Cu onto clean polycrystalline Si under ultrahigh vacuum, and the Cu/Si surface is first activated by exposure to 10% HSiCl{sub 3}/CH{sub 3}Cl at 598 K. After the HSiCl{sub 3}CH{sub 3}Cl mixture is evacuated from the reactor, the activated Cu/Si surface is reacted in fresh CH{sub 3}Cl. For low surface concentrations of Cu, the partially hydrogenated silane, (CH{sub 3}){sub 2}HSiCl, is selectivelymore » produced. Trichlorosilane was also found to activate polycrystalline Si (in the absence of Cu) for production of highly chlorinated methylchlorosilanes at a much higher rate than on the Cu/Si surface but with poor selectively to (CH{sub 3}){sub 2}HSiCl. All reactions are carried out at atmospheric pressure in a reactor that is attached to an ultrahigh-vacuum chamber. This allows surface analysis of Auger electron spectroscopy, which detected SiCl{sub x} on reacted surfaces. These SiCl{sub x} sites, which appear necessary for methylchlorosilane formation, are apparently formed during activation by HSiCl{sub 3}.« less

Electrodeposition of Al-Ta alloys in NaCl-KCl-AlCl3 molten salt containing TaCl5

NASA Astrophysics Data System (ADS)

Sato, Kazuki; Matsushima, Hisayoshi; Ueda, Mikito

2016-12-01

To form Al-Ta alloys for high temperature oxidation resistance components, molten salt electrolysis was carried out in an AlCl3-NaCl-KCl melt containing TaCl5 at 423 K. The voltammogram showed two cathodic waves at 0.45 V and 0.7 V vs. Al/Al(III), which may correspond to reduction from Ta(V) to Ta(III) and from Ta(III) to tantalum metal, respectively. Electrodeposits of Al and Ta were obtained in the range from -0.05 to 0.3 V and the highest concentration of Ta in the electrodeposit was 72 at% at 0.3 V. With increasing Ta content in the alloy, the morphology of the electrodeposits became powdery and the particle size smaller.

Rechargeable Al/Cl2 battery with molten AlCl4/-/ electrolyte.

NASA Technical Reports Server (NTRS)

Holleck, G. L.; Giner, J.; Burrows, B.

1972-01-01

A molten salt system based on Al- and Cl2 carbon electrodes, with an AlCl3 alkali chloride eutectic as electrolyte, offers promise as a rechargeable, high energy density battery which can operate at a relatively low temperature. Electrode kinetic studies showed that the electrode reactions at the Al anode were rapid and that the observed passivation phenomena were due to the formation at the electrode surface of a solid salt layer resulting from concentration changes on anodic or cathodic current flow. It was established that carbon electrodes were intrinsically active for chlorine reduction in AlCl3-alkali chloride melts. By means of a rotating vitreous carbon disk electrode, the kinetic parameters were determined.

Electrochemical Formation of Mg-Li-Sm Alloys by Codeposition from LiCl-KCl-MgCl2-SmCl3 Molten Salts

NASA Astrophysics Data System (ADS)

Han, Wei; Wang, Fengli; Tian, Yang; Zhang, Milin; Yan, Yongde

2011-12-01

In this article, the electrochemical method of preparing Mg-Li-Sm alloys by codeposition in LiCl-KCl-MgCl2-SmCl3 melts was investigated. Transient electrochemical techniques, such as cyclic voltammetry, chronopotentiometry, and chronoamperometry were used to explore the electrochemical formation of Mg-Li-Sm alloys. Chronopotentiograms demonstrated that the codepositon of Mg, Li, and Sm occurred when current densities were more negative than -0.31 A cm-2. Chronoamperograms indicated that the onset potential for the codeposition of Mg, Li, and Sm was -2.40 V, and the codeposition of Mg, Li, and Sm was formed when the applied potentials were more negative than -2.40 V. The different phases of Mg-Li-Sm alloys were prepared by galvanostatic electrolysis and characterized by X-ray diffraction (XRD), optical microscope (OM), and scanning electron microscopy (SEM). An inductively coupled plasma (ICP) analysis showed that the lithium and samarium contents in Mg-Li-Sm alloys could be controlled by the concentrations of MgCl2 and SmCl3. The results demonstrated that Sm could refine the grains dramatically. When the Sm content was 0.8 wt pct, the grain size was the finest.

The Role of MgCl 2 as a Lewis Base in ROMgCl-MgCl 2 Electrolytes for Magnesium-Ion Batteries

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

Pan, Baofei; Huang, Jinhua; He, Meinan

2016-02-04

A series of strong Lewis acid-free alkoxide/siloxide-based Mg electrolytes were deliberately developed with remarkable oxidative stability up to 3.5 V (vs. Mg/Mg2+). Despite the perception of ROMgCl (R=alkyl, silyl) as a strong base, ROMgCl acts like Lewis acid, whereas the role of MgCl2 in was unambiguously demonstrated as a Lewis base through the identification of the key intermediate using single crystal X-ray crystallography. This Lewis-acid-free strategy should provide a prototype system for further investigation of Mg-ion batteries.

Structural morphology of cotunnite, PbCl 2, laurionite, Pb(OH)Cl, and SbSI

NASA Astrophysics Data System (ADS)

Woensdregt, C. F.; Hartman, P.

1988-03-01

The structural morphology of compounds having the PbCl 2 and the closely related SbSI structures has been determined. Based upon the nine-coordination of the Pb atoms the F forms of the PbCl 2 structure are {110}, {020}, {120}, {011}, {200}, {111} , {201}, {121} and {211}. These forms are arranged in an order of increasing attachment energies, that were calculated using a broken bond model. In the SbSI structure type the Sb atom has a seven-coordination with the consequence that {020} becomes a different surface structure and that {120} is an S face. The theoretical habit of PbCl 2 and Pb(OH)Cl is short prismatic, elongated along the c axis, with {011} as terminal form. The appearance of {211} as main form on PbCl 2 when growth takes place from pure aqueous solution is ascribed to the preferential adsorption of OH - ions on that face. The predominance of {020} and {121} on PbCl 2 from solutions containing HCl is explained by adsorption of H 3O + on these faces. The theoretical habit of the SbSI structure type is slender prismatic {110} with {011} as terminal form.

Research and progress on ClC-2

PubMed Central

Wang, Hongwei; Xu, Minghui; Kong, Qingjie; Sun, Peng; Yan, Fengyun; Tian, Wenying; Wang, Xin

2017-01-01

Chloride channel 2 (ClC-2) is one of the nine mammalian members of the ClC family. The present review discusses the molecular properties of ClC-2, including CLCN2, ClC-2 promoter and the structural properties of ClC-2 protein; physiological properties; functional properties, including the regulation of cell volume. The effects of ClC-2 on the digestive, respiratory, circulatory, nervous and optical systems are also discussed, in addition to the mechanisms involved in the regulation of ClC-2. The review then discusses the diseases associated with ClC-2, including degeneration of the retina, Sjögren's syndrome, age-related cataracts, degeneration of the testes, azoospermia, lung cancer, constipation, repair of impaired intestinal mucosa barrier, leukemia, cystic fibrosis, leukoencephalopathy, epilepsy and diabetes mellitus. It was concluded that future investigations of ClC-2 are likely to be focused on developing specific drugs, activators and inhibitors regulating the expression of ClC-2 to treat diseases associated with ClC-2. The determination of CLCN2 is required to prevent and treat several diseases associated with ClC-2. PMID:28534947

Association and Dissociation of Grignard Reagents RMgCl and Their Turbo Variant RMgCl⋅LiCl.

PubMed

Schnegelsberg, Christoph; Bachmann, Sebastian; Kolter, Marlene; Auth, Thomas; John, Michael; Stalke, Dietmar; Koszinowski, Konrad

2016-06-01

Grignard reagents RMgCl and their so-called turbo variant, the highly reactive RMgCl⋅LiCl, are of exceptional synthetic utility. Nevertheless, it is still not fully understood which species these compounds form in solution and, in particular, in which way LiCl exerts its reactivity-enhancing effect. A combination of electrospray-ionization mass spectrometry, electrical conductivity measurements, NMR spectroscopy (including diffusion-ordered spectroscopy), and quantum chemical calculations is used to analyze solutions of RMgCl (R=Me, Et, Bu, Hex, Oct, Dec, iPr, tBu, Ph) in tetrahydrofuran and other ethereal solvents in the absence and presence of stoichiometric amounts of LiCl. In tetrahydrofuran, RMgCl forms mononuclear species, which are converted into trinuclear anions as a result of the concentration increase experienced during the electrospray process. These trinuclear anions are theoretically predicted to adopt open cubic geometries, which remarkably resemble structural motifs previously found in the solid state. The molecular constituents of RMgCl and RMgCl⋅LiCl are interrelated via Schlenk equilibria and fast intermolecular exchange processes. A small portion of the Grignard reagent also forms anionic ate complexes in solution. The abundance of these more electron-rich and hence supposedly more nucleophilic ate complexes strongly increases upon the addition of LiCl, thus rationalizing its beneficial effect on the reactivity of Grignard reagents. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Temperature-dependent formation of NaCl dihydrate in levitated NaCl and sea salt aerosol particles.

PubMed

Peckhaus, Andreas; Kiselev, Alexei; Wagner, Robert; Duft, Denis; Leisner, Thomas

2016-12-28

Recent laboratory studies indicate that the hydrated form of crystalline NaCl is potentially important for atmospheric processes involving depositional ice nucleation on NaCl dihydrate particles under cirrus cloud conditions. However, recent experimental studies reported a strong discrepancy between the temperature intervals where the efflorescence of NaCl dihydrate has been observed. Here we report the measurements of the volume specific nucleation rate of crystalline NaCl in the aqueous solution droplets of pure NaCl suspended in an electrodynamic balance at constant temperature and humidity in the range from 250 K to 241 K. Based on these measurements, we derive the interfacial energy of crystalline NaCl dihydrate in a supersaturated NaCl solution and determined its temperature dependence. Taking into account both temperature and concentration dependence of nucleation rate coefficients, we explain the difference in the observed fractions of NaCl dihydrate reported in the previous studies. Applying the heterogeneous classical nucleation theory model, we have been able to reproduce the 5 K shift of the NaCl dihydrate efflorescence curve observed for the sea salt aerosol particles, assuming the presence of super-micron solid inclusions (hypothetically gypsum or hemihydrate of CaSO 4 ). These results support the notion that the phase transitions in microscopic droplets of supersaturated solution should be interpreted by accounting for the stochastic nature of homogeneous and heterogeneous nucleation and cannot be understood on the ground of bulk phase diagrams alone.

Temperature-dependent formation of NaCl dihydrate in levitated NaCl and sea salt aerosol particles

NASA Astrophysics Data System (ADS)

Peckhaus, Andreas; Kiselev, Alexei; Wagner, Robert; Duft, Denis; Leisner, Thomas

2016-12-01

Recent laboratory studies indicate that the hydrated form of crystalline NaCl is potentially important for atmospheric processes involving depositional ice nucleation on NaCl dihydrate particles under cirrus cloud conditions. However, recent experimental studies reported a strong discrepancy between the temperature intervals where the efflorescence of NaCl dihydrate has been observed. Here we report the measurements of the volume specific nucleation rate of crystalline NaCl in the aqueous solution droplets of pure NaCl suspended in an electrodynamic balance at constant temperature and humidity in the range from 250 K to 241 K. Based on these measurements, we derive the interfacial energy of crystalline NaCl dihydrate in a supersaturated NaCl solution and determined its temperature dependence. Taking into account both temperature and concentration dependence of nucleation rate coefficients, we explain the difference in the observed fractions of NaCl dihydrate reported in the previous studies. Applying the heterogeneous classical nucleation theory model, we have been able to reproduce the 5 K shift of the NaCl dihydrate efflorescence curve observed for the sea salt aerosol particles, assuming the presence of super-micron solid inclusions (hypothetically gypsum or hemihydrate of CaSO4). These results support the notion that the phase transitions in microscopic droplets of supersaturated solution should be interpreted by accounting for the stochastic nature of homogeneous and heterogeneous nucleation and cannot be understood on the ground of bulk phase diagrams alone.

Dissociative recombination of HCl+, H2Cl+, DCl+, and D2Cl+ in a flowing afterglow

NASA Astrophysics Data System (ADS)

Wiens, Justin P.; Miller, Thomas M.; Shuman, Nicholas S.; Viggiano, Albert A.

2016-12-01

Dissociative recombination of electrons with HCl+, H2Cl+, DCl+, and D2Cl+ has been measured under thermal conditions at 300, 400, and 500 K using a flowing afterglow-Langmuir probe apparatus. Measurements for HCl+ and DCl+ employed the variable electron and neutral density attachment mass spectrometry (VENDAMS) method, while those for H2Cl+ and D2Cl+ employed both VENDAMS and the more traditional technique of monitoring electron density as a function of reaction time. At 300 K, HCl+ and H2Cl+ recombine with kDR = 7.7±2.14.5 × 10-8 cm3 s-1 and 2.6 ± 0.8 × 10-7 cm3 s-1, respectively, whereas D2Cl+ is roughly half as fast as H2Cl+ with kDR = 1.1 ± 0.3 × 10-7 cm3 s-1 (2 σ confidence intervals). DCl+ recombines with a rate coefficient below the approximate detection limit of the method (≲5 × 10-8 cm3 s-1) at all temperatures. Relatively slow dissociative recombination rates have been speculated to be responsible for the large HCl+ and H2Cl+ abundances in interstellar clouds compared to current astrochemical models, but our results imply that the discrepancy must originate elsewhere.

Temperature invariance of NaCl solubility in water: inferences from salt-water cluster behavior of NaCl, KCl, and NH4Cl.

PubMed

Bharmoria, Pankaj; Gupta, Hariom; Mohandas, V P; Ghosh, Pushpito K; Kumar, Arvind

2012-09-27

The growth and stability of salt-water clusters have been experimentally studied in aqueous solutions of NaCl, KCl, and NH(4)Cl from dilute to near-saturation conditions employing dynamic light scattering and zeta potential measurements. In order to examine cluster stability, the changes in the cluster sizes were monitored as a function of temperature. Compared to the other cases, the average size of NaCl-water clusters remained almost constant over the studied temperature range of 20-70 °C. Information obtained from the temperature-dependent solution compressibility (determined from speed of sound and density measurements), multinuclear NMR ((1)H, (17)O, (35)Cl NMR), and FTIR were utilized to explain the cluster behavior. Comparison of NMR chemical shifts of saturated salt solutions with solid-state NMR data of pure salts, and evaluation of spectral modifications in the OH stretch region of saturated salt solutions as compared to that of pure water, provided important clues on ion pair-water interactions and water structure in the clusters. The high stability and temperature independence of the cluster sizes in aqueous NaCl shed light on the temperature invariance of its solubility.

Bumetanide increases Cl--dependent short-circuit current in late distal colon: Evidence for the presence of active electrogenic Cl- absorption.

PubMed

Tang, Lieqi; Fang, Xiefan; Winesett, Steven P; Cheng, Catherine Y; Binder, Henry J; Rivkees, Scott A; Cheng, Sam X

2017-01-01

Mammalian colonic epithelia consist of cells that are capable of both absorbing and secreting Cl-. The present studies employing Ussing chamber technique identified two opposing short-circuit current (Isc) responses to basolateral bumetanide in rat distal colon. Apart from the transepithelial Cl--secretory Isc in early distal colon that was inhibited by bumetanide, bumetanide also stimulated Isc in late distal colon that had not previously been identified. Since bumetanide inhibits basolateral Na+-K+-2Cl- cotransporter (NKCC) in crypt cells and basolateral K+-Cl- cotransporter (KCC) in surface epithelium, we proposed this stimulatory Isc could represent a KCC-mediated Cl- absorptive current. In support of this hypothesis, ion substitution experiments established Cl- dependency of this absorptive Isc and transport inhibitor studies demonstrated the involvement of an apical Cl- conductance. Current distribution and RNA sequencing analyses revealed that this Cl- absorptive Isc is closely associated with epithelial Na+ channel (ENaC) but is not dependent on ENaC activity. Thus, inhibition of ENaC by 10 μM amiloride or benzamil neither altered the direction nor its activity. Physiological studies suggested that this Cl- absorptive Isc senses dietary Cl- content; thus when dietary Cl- was low, Cl- absorptive Isc was up-regulated. In contrast, when dietary Cl- was increased, Cl- absorptive Isc was down-regulated. We conclude that an active Cl- extrusion mechanism exists in ENaC-expressing late distal colon and likely operates in parallel with ENaC to facilitate NaCl absorption.

Revisiting the SOLVE ClOOCl and ClO measurements in consideration of the Pope et al., 2007 results.

NASA Astrophysics Data System (ADS)

Stimpfle, R. M.; Wilmouth, D. M.; Anderson, J. G.

2008-12-01

The interpretation of the SOLVE measurements of ClOOCl and ClO has recently acquired renewed interest with the publication of new ClOOCl cross section measurements (Pope et al, 2007) that are significantly smaller than expected. The SOLVE analysis showed agreement with J values based upon the JPL 2002 or Burkholder 1990 cross sections, dependent upon various values for the rate constant for dimer production. J values based upon Pope are currently not in agreement with the SOLVE observations and/or their analysis. As various hypotheses emerge to possibly rationalize the Pope results, it is worthwhile to consider two critical constraints that the SOLVE halogen data place on any newly considered Clx photochemistry. The first constraint is the lack of a detectable Cl atom signal in the observed background signal at the temperature used for thermal dissociation of ClOOCl. The second constraint is the observed SZA dependence of the partitioning of ClO and ClOOCl. Here we present evidence of the Cl atom constraint.

Kinetics and Thermochemistry of ClCO Formation from the Cl + CO Association Reaction

NASA Technical Reports Server (NTRS)

Nicovich, J. M.; Kreutter, K. D.; Wine, P. H.

1997-01-01

Laser flash photolysis of Cl2/CO/M mixtures (M = N2, CO, Ar, CO2) has been employed in conjunction with Cl((sup 2)P(sub J)) detection by time-resolved resonance fluorescence spectroscopy to investigate equilibration kinetics in the reactions Cl((sup 2)P(sub J)) + CO ClCO as a function of temperature (185-260 K) and pressure (14-200 Torr). The association and dissociation reactions are found to be in the low-pressure limit over the range of experimental conditions investigated. In N2 and/or CO buffer gases, the temperature dependences of the ClCO formation and dissociation reaction rate constants are described by the Arrhenius expressions k(sub 1) = (1.05 +/- 0.36) x 10(exp -34) exp[(810 +/- 70)/T] cm(exp 6)/molecules(exp 2).s and k(sub -1) = (4.1 +/- 3.1) x 10(exp -10) exp[(-2960 +/- 60)/T]cu cm/(molecule.s) (errors are 2 sigma). Second- and third-law analyses of the temperature dependence of the equilbrium constant (k/k-1) lead to the following thermodynamic parameters for the association reaction: Delta-H(sub 298) = -7.7 +/- 0.6 kcal/mol, Delta-H(sub 0) = -6.9 +/- 0.7 kcal/mol, Delta-S(sub 298) = -23.8 +/- 2.0 cal/mole.K, Delta-H(sub f,298)(ClCO) = 5.2 +/- 0.6 kcal/mol (errors are 2 sigma). The results repported in this study significantly reduce the uncertainties in all reported kinetic and thermodynamic parameters.

Characterization of the human pH- and PKA-activated ClC-2G(2 alpha) Cl- channel.

PubMed

Sherry, A M; Stroffekova, K; Knapp, L M; Kupert, E Y; Cuppoletti, J; Malinowska, D H

1997-08-01

A ClC-2G(2 alpha) Cl- channel was identified to be present in human lung and stomach, and a partial cDNA for this Cl- channel was cloned from a human fetal lung library. A full-length expressible human ClC-2G(2 alpha) cDNA was constructed by ligation of mutagenized expressible rabbit ClC-2G(2 alpha) cDNA with the human lung ClC-2G(2 alpha) cDNA, expressed in oocytes, and characterized at the single-channel level. Adenosine 3',5'-cyclic monophosphate-dependent protein kinase (PKA) treatment increased the probability of opening of the channel (Po). After PKA activation, the channel exhibited a linear (r = 0.99) current-voltage curve with a slope conductance of 22.1 +/- 0.8 pS in symmetric 800 mM tetraethylammonium chloride (TEACl; pH 7.4). Under fivefold gradient conditions of TEACl, a reversal potential of +21.5 +/- 2.8 mV was measured demonstrating anion-to-cation discrimination. As previously demonstrated for the rabbit ClC-2G(2 alpha) Cl- channel, the human analog, hClC-2G(2 alpha), was active at pH 7.4 as well as when the pH of the extracellular face of the channel (trans side of the bilayer; pHtrans) was asymmetrically reduced to pH 3.0. The extent of PKA activation was dependent on pHtrans. With PKA treatment, Po increased fourfold with a pHtrans of 7.4 and eightfold with a pHtrans of 3.0. Effects of sequential PKA addition followed by pHtrans reduction on the same channel suggested that the PKA- and pH-dependent increases in channel Po were separable and cumulative. Northern analysis showed ClC-2G(2 alpha) mRNA to be present in human adult and fetal lung and adult stomach, and quantitative reverse transcriptase-polymerase chain reaction showed this channel to be present in the adult human lung and stomach at about one-half the level found in fetal lung. The findings of the present study suggest that the ClC-2G(2 alpha) Cl- channel may play an important role in Cl- transport in the fetal and adult human lung.

Phenolic Compounds and Expression of 4CL Genes in Silver Birch Clones and Pt4CL1a Lines

PubMed Central

Sutela, Suvi; Hahl, Terhi; Tiimonen, Heidi; Aronen, Tuija; Ylioja, Tiina; Laakso, Tapio; Saranpää, Pekka; Chiang, Vincent; Julkunen-Tiitto, Riitta; Häggman, Hely

2014-01-01

A small multigene family encodes 4-coumarate:CoA ligases (4CLs) catalyzing the CoA ligation of hydroxycinnamic acids, a branch point step directing metabolites to a flavonoid or monolignol pathway. In the present study, we examined the effect of antisense Populus tremuloides 4CL (Pt4CL1) to the lignin and soluble phenolic compound composition of silver birch (Betula pendula) Pt4CL1a lines in comparison with non-transgenic silver birch clones. The endogenous expression of silver birch 4CL genes was recorded in the stems and leaves and also in leaves that were mechanically injured. In one of the transgenic Pt4CL1a lines, the ratio of syringyl (S) and guaiacyl (G) lignin units was increased. Moreover, the transcript levels of putative silver birch 4CL gene (Bp4CL1) were reduced and contents of cinnamic acid derivatives altered. In the other two Pt4CL1a lines changes were detected in the level of individual phenolic compounds. However, considerable variation was found in the transcript levels of silver birch 4CLs as well as in the concentration of phenolic compounds among the transgenic lines and non-transgenic clones. Wounding induced the expression of Bp4CL1 and Bp4CL2 in leaves in all clones and transgenic lines, whereas the transcript levels of Bp4CL3 and Bp4CL4 remained unchanged. Moreover, minor changes were detected in the concentrations of phenolic compounds caused by wounding. As an overall trend the wounding decreased the flavonoid content in silver birches and increased the content of soluble condensed tannins. The results indicate that by reducing the Bp4CL1 transcript levels lignin composition could be modified. However, the alterations found among the Pt4CL1a lines and the non-transgenic clones were within the natural variation of silver birches, as shown in the present study by the clonal differences in the transcripts levels of 4CL genes, soluble phenolic compounds and condensed tannins. PMID:25502441

Quantum scattering studies of spin-orbit effects in the Cl({sup 2}P) + HCl {yields} ClH + Cl({sup 2}P) reaction

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

Schatz, G.C.; McCabe, P.; Connor, J.N.L.

1998-07-01

The authors present quantum scattering calculations for the Cl + HCl {yields} ClH + Cl reaction in which they include the three electronic states that correlate asymptotically to the ground state of Cl({sup 2}P) + HCl(X{sup 1}{Sigma}{sup +}). The potential surfaces and couplings are taken from the recent work of C.S. Maierle, G.C. Schatz, M.S. Gordon, P. McCabe and J.N.L. Connor, J. Chem. Soc. Farad. Trans. (1997). They are based on extensive ab initio calculations for geometries in the vicinity of the lowest energy saddle point, and on an electrostatic expansion (plus empirical dispersion and repulsion) for long range geometriesmore » including the van der Waals wells. Spin-orbit coupling has been included using a spin-orbit coupling parameter {lambda} that is assumed to be independent of nuclear geometry, and Coriolis interactions are incorporated accurately. The scattering calculations use a hyperspherical coordinate coupled channel method in full dimensionality. AJ-shifting approximation is employed to convert cumulative reaction probabilities for total angular momentum quantum number J = 1/2 into state selected and thermal rate coefficients. Two issues have been studied: (a) the influence of the magnitude of {lambda} on the fine-structure resolved cumulative probabilities and rate coefficients (the authors consider {lambda}`s that vary from 0 to {+-}100% of the true Cl value), and (b) the transition state resonance spectrum, and its variation with {lambda} and with other parameters in the calculations. Cl + HCl is a simple hydrogen transfer reaction which serves as a canonical model both for heavy-light-heavy atom reactions, and for the reactions of halogen atoms with closed shell molecules.« less

Interaction of different poisons with MgCl2/TiCl4 based Ziegler-Natta catalysts

NASA Astrophysics Data System (ADS)

Bahri-Laleh, Naeimeh

2016-08-01

Adsorption of different poison molecules on activated MgCl2 is investigated within DFT using a cluster model of the MgCl2 surface with (MgCl2)16 formula containing four 4-coordinated and eight 5-coordinated Mg atoms as (110) and (104) surfaces, respectively. Studied poison molecules are chosen as possible impurities in hydrocarbon solvents and monomer feeds and contain water, hydrogensulfide, carbondioxide, molecular oxygen and methanol. First, adsorption of 1-4 molecules of different poisons to the (104) and (110) lateral cuts of MgCl2, as well as their adsorption on [MgCl2]/TiCl2Et active center and AlEt3 cocatalyst is considered. Results reveal that poisons strongly stabilize both crystal surfaces, mostly Ti active center relative to the unpoisoned solid. Second, energy barrier (ETS) for ethylene insertion in the presence of different poisons located on the first and second Mg atom relative to the active Ti is calculated. While poison molecule located on the second Mg does not change ETS, coordination of it into the first Mg atom increases ETS by 0.9-1.2 kcal mol-1. In the last part of this manuscript, the stereoselective behavior of active Ti species, with and without poison molecules and external electron donor, is fully explored.

Biodegradation of the nitramine explosive CL-20.

PubMed

Trott, Sandra; Nishino, Shirley F; Hawari, Jalal; Spain, Jim C

2003-03-01

The cyclic nitramine explosive CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) was examined in soil microcosms to determine whether it is biodegradable. CL-20 was incubated with a variety of soils. The explosive disappeared in all microcosms except the controls in which microbial activity had been inhibited. CL-20 was degraded most rapidly in garden soil. After 2 days of incubation, about 80% of the initial CL-20 had disappeared. A CL-20-degrading bacterial strain, Agrobacterium sp. strain JS71, was isolated from enrichment cultures containing garden soil as an inoculum, succinate as a carbon source, and CL-20 as a nitrogen source. Growth experiments revealed that strain JS71 used 3 mol of nitrogen per mol of CL-20.

Biodegradation of the Nitramine Explosive CL-20

PubMed Central

Trott, Sandra; Nishino, Shirley F.; Hawari, Jalal; Spain, Jim C.

2003-01-01

The cyclic nitramine explosive CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) was examined in soil microcosms to determine whether it is biodegradable. CL-20 was incubated with a variety of soils. The explosive disappeared in all microcosms except the controls in which microbial activity had been inhibited. CL-20 was degraded most rapidly in garden soil. After 2 days of incubation, about 80% of the initial CL-20 had disappeared. A CL-20-degrading bacterial strain, Agrobacterium sp. strain JS71, was isolated from enrichment cultures containing garden soil as an inoculum, succinate as a carbon source, and CL-20 as a nitrogen source. Growth experiments revealed that strain JS71 used 3 mol of nitrogen per mol of CL-20. PMID:12620886

7 CFR 761.210 - CL funds.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 7 Agriculture 7 2011-01-01 2011-01-01 false CL funds. 761.210 Section 761.210 Agriculture... SPECIAL PROGRAMS GENERAL PROGRAM ADMINISTRATION Allocation of Farm Loan Programs Funds to State Offices § 761.210 CL funds. (a) The following applicants and conservation projects will receive priority for CL...

Progress and developments in the turbo Grignard reagent i-PrMgCl·LiCl: a ten-year journey.

PubMed

Bao, Robert Li-Yuan; Zhao, Rong; Shi, Lei

2015-04-25

Over the past decade, the effectiveness of i-PrMgCl·LiCl has been constantly highlighted by a number of research groups. Its enhanced nucleophilicity brings prosperity to highly functionalized Grignard reagents, other useful bimetallic (alkali-metal) agents and nucleophilic alkylation products under mild reaction conditions. In this feature article, a comprehensive, systematical and in-depth overview of i-PrMgCl·LiCl is provided in a multidisciplinary idea. It involves the structural and kinetic perspectives of i-PrMgCl·LiCl as well as its unique reactivity and selectivity, with knowledge of the former helping to rationalize trends of the later.

Two-center three-electron bonding in ClNH 3 revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH 3 → ClNH 2 + H reaction

DOE PAGES

Moradi, Christopher P.; Xie, Changjian; Kaufmann, Matin; ...

2016-04-22

Pyrolytic dissociation of Cl 2 is employed to dope helium droplets with single Cl atoms. Sequential addition of NH 3 to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH 3 → ClNH 2 + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C 3v symmetric top. Frequency shifts from NH 3 and dipole moment measurements are consistent with a ClNH 3 complex containing a relatively strong two-center three-electron (2c–3e) bond. The nature of the 2c–3e bonding in ClNH 3more » is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. As a result, computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence in experimental spectra of two other complexes, NH 3Cl and Cl–HNH 2, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH 3 → HCl + NH 2.« less

An enzyme-linked immunosorbent assay (ELISA) for quantification of human collectin 11 (CL-11, CL-K1)

PubMed Central

Selman, L.; Henriksen, M.L.; Brandt, J.; Palarasah, Y.; Waters, A.; Beales, P.L.; Holmskov, U.; Jørgensen, T.J.D.; Nielsen, C.; Skjodt, K.; Hansen, S.

2012-01-01

Collectin 11 (CL-11), also referred to as collectin kidney 1 (CL-K1), is a pattern recognition molecule that belongs to the collectin group of proteins involved in innate immunity. It interacts with glycoconjugates on pathogen surfaces and has been found in complex with mannose-binding lectin-associated serine protease 1 (MASP-1) and/or MASP-3 in circulation. Mutation in the CL-11 gene was recently associated with the developmental syndrome 3MC. In the present study, we established and thoroughly validated a sandwich enzyme-linked immunosorbent assay (ELISA) based on two different monoclonal antibodies. The assay is highly sensitive, specific and shows excellent quantitative characteristics such as reproducibility, dilution linearity and recovery (97.7–104%). The working range is 0.15–34 ng/ml. The CL-11 concentration in two CL-11-deficient individuals affected by the 3MC syndrome was determined to be below 2.1 ng/ml. We measured the mean serum CL-11 concentration to 284 ng/ml in 100 Danish blood donors, with a 95% confidence interval of 269–299 ng/ml. There was no significant difference in the CL-11 concentration measured in matched serum and plasma samples. Storage of samples and repeated freezing and thawing to a certain extent did not influence the ELISA. This ELISA offers a convenient and reliable method for studying CL-11 levels in relation to a variety of human diseases and syndromes. PMID:22301270

γ spectroscopy of states in Cl 32 relevant for the S 31 ( p , γ ) Cl 32 reaction rate

DOE PAGES

Afanasieva, L.; Blackmon, J. C.; Deibel, C. M.; ...

2017-09-01

Background: The 31S(p,gamma) 32Cl reaction becomes important for sulfur production in novae if the P-31(p, alpha)Si-28 reaction rate is somewhat greater than currently accepted. The rate of the S-31(p,gamma) Cl-32 reaction is uncertain, primarily due to the properties of resonances at E-c.m. = 156 and 549 keV. Purpose: We precisely determined the excitation energies of states in Cl-32 through high-resolution. spectroscopy including the two states most important for the S-31(p,gamma) Cl-32 reaction at nova temperatures. Method: Excited states in Cl-32 were populated using the B-10(Mg-24, 2n) Cl-32 reaction with a Mg-24 beam from the ATLAS facility at Argonne National Laboratory.more » The reaction channel of interest was selected using recoils in the Fragment Mass Analyzer, and we determined precise level energies by detecting. rays with Gammasphere. Results: We also observed. rays from the decay of six excited states in Cl-32. The excitation energies for two unbound levels at E-x = 1738.1 (6) keV and 2130.5 (10) keV were determined and found to be in agreement with a previous high-precision measurement of the S-32(He-3, t) Cl-32 reaction [1]. Conclusions: An updated 31S(p,gamma) Cl-32 reaction rate is presented. With the excitation energies of important levels firmly established, the dominant uncertainty in the reaction rate at nova temperatures is due to the strength of the resonance corresponding to the 2131-keV state in Cl-32.« less

75 FR 12152 - Airworthiness Directives; Bombardier, Inc. Model CL-600-2B19 (Regional Jet Series 100 & 440), CL...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-03-15

... DEPARTMENT OF TRANSPORTATION Federal Aviation Administration 14 CFR Part 39 [Docket No. FAA-2010.... Model CL-600-2B19 (Regional Jet Series 100 & 440), CL-600-2C10 (Regional Jet Series 700, 701 & 702), CL-600-2D15 (Regional Jet Series 705), and CL-600-2D24 (Regional Jet Series 900) Airplanes AGENCY...

Light and variable 37Cl/35Cl ratios in rocks from Gale Crater, Mars: Possible signature of perchlorate

NASA Astrophysics Data System (ADS)

Farley, K. A.; Martin, P.; Archer, P. D.; Atreya, S. K.; Conrad, P. G.; Eigenbrode, J. L.; Fairén, A. G.; Franz, H. B.; Freissinet, C.; Glavin, D. P.; Mahaffy, P. R.; Malespin, C.; Ming, D. W.; Navarro-Gonzalez, R.; Sutter, B.

2016-03-01

Cl isotope ratios measured on HCl thermally evolved from as-yet-unknown phases in sedimentary rocks and sand in Gale Crater provide unexpected insights to the Martian surficial Cl cycle. The seven samples yield δ37Cl values ranging from - 1 ± 25 ‰ to - 51 ± 5 ‰. Five analyses from two samples of the Sheepbed mudstone (Yellowknife Bay study area) are analytically indistinguishable with a mean δ37Cl of - 11 ± 7 ‰ (1 σ). In contrast, four mudstones/sandstones from the Kimberley and Pahrump study areas also yielded indistinguishable ratios, but with a mean δ37Cl of - 43 ± 6 ‰. The Rocknest sand deposit gave a highly uncertain δ37Cl value of - 7 ± 44 ‰. These light and highly variable δ37Cl values are unique among known solar system materials. Two endmember models are offered to account for these observations, and in both, perchlorate, with its extreme ability to fractionate Cl isotopes, is critical. In the first model, SAM is detecting HCl from an oxychlorine compound (e.g., perchlorate) produced from volcanic gas emissions by atmospheric chemical reactions. Similar reactions in Earth's atmosphere may be responsible for the isotopically lightest known Cl outside of this study, in perchlorate from the Atacama Desert. Some of the Gale Crater δ37Cl values are more negative than those in Atacama perchlorate, but because reaction mechanisms and associated fractionation factors are unknown, it is impossible to assess whether this difference is prohibitive. If the negative δ37Cl signal is produced in this fashion, the isotopic variability among samples could arise either from variations in the relative size of the reactant chloride and product perchlorate reservoirs, or from variations in the fraction of perchlorate reduced back to chloride after deposition. Such reduction strongly enriches 37Cl in the residual perchlorate. Perchlorate reduction alone offers an alternative endmember model that can explain the observed data if SAM measured HCl derived

Effect of the ZrCl4 concentration in the (NaCl-KCl)eqiv-UO2Cl2-ZrCl4 melt and the electrolysis current density on the quantitative composition of UO2-ZrO2 cathode deposits. Calculation and experiment

NASA Astrophysics Data System (ADS)

Krotov, V. E.; Filatov, E. C.

2014-08-01

A method is proposed for calculating the ZrO2 content in the (NaCl-KCl)eqiv-UO2Cl2-ZrCl4 melt. Based on the known composition of a UO2-ZrO2 cathode deposit, the content is calculated at current densities of 0.08-0.63 A/cm2 and ZrCl4 concentrations of 0-12.3 wt %. The calculated and experimental ZrO2 contents in UO2-ZrO2 cathode deposits are in qualitative and adequate quantitative agreement.

Understanding the kinetics of the ClO dimer cycle

NASA Astrophysics Data System (ADS)

von Hobe, M.; Salawitch, R. J.; Canty, T.; Keller-Rudek, H.; Moortgat, G. K.; Grooß, J.-U.; Müller, R.; Stroh, F.

2006-08-01

Among the major factors controlling ozone loss in the polar winter is the kinetics of the ClO dimer catalytic cycle. The most important issues are the thermal equilibrium between ClO and Cl2O2, the rate of Cl2O2 formation, and the Cl2O2 photolysis rate. All these issues have been addressed in a large number of laboratory, field and theoretical studies, but large discrepancies between individual results exist and a self-consistent set of parameters compatible with field observations of ClO and Cl2O2 has not been identified. Here, we use thermodynamic calculations and unimolecular rate theory to constrain the ClO/Cl2O2 equilibrium constant and the rate constants for Cl2O2 formation and dissociation. This information is used together with available atmospheric data to examine Cl2O2 photolysis rates based on different Cl2O2 absorption cross sections. Good overall consistency is achieved using a ClO/Cl2O2 equilibrium constant recently suggested by Plenge et al. (2005), the Cl2O2 recombination rate constant reported by Nickolaisen et al. (1994) and Cl2O2 photolysis rates based on averaged absorption cross sections that are roughly intermediate between the JPL 2002 assessment and a laboratory study by Burkholder et al. (1990).

The structure of PbCl2 on the {100} surface of NaCl and its consequences for crystal growth

NASA Astrophysics Data System (ADS)

Townsend, Eleanor R.; Brugman, Sander J. T.; Blijlevens, Melian A. R.; Smets, Mireille M. H.; de Poel, Wester; van Enckevort, Willem J. P.; Meijer, Jan A. M.; Vlieg, Elias

2018-04-01

The role that additives play in the growth of sodium chloride is a topic which has been widely researched but not always fully understood at an atomic level. Lead chloride (PbCl2) is one such additive which has been reported to have growth inhibition effects on NaCl {100} and {111}; however, no definitive evidence has been reported which details the mechanism of this interaction. In this investigation, we used the technique of surface x-ray diffraction to determine the interaction between PbCl2 and NaCl {100} and the structure at the surface. We find that Pb2+ replaces a surface Na+ ion, while a Cl- ion is located on top of the Pb2+. This leads to a charge mismatch in the bulk crystal, which, as energetically unfavourable, leads to a growth blocking effect. While this is a similar mechanism as in the anticaking agent ferrocyanide, the effect of PbCl2 is much weaker, most likely due to the fact that the Pb2+ ion can more easily desorb. Moreover, PbCl2 has an even stronger effect on NaCl {111}.

Ab initio quantum mechanical calculation of the reaction probability for the Cl-+PH2Cl→ClPH2+Cl- reaction

NASA Astrophysics Data System (ADS)

Farahani, Pooria; Lundberg, Marcus; Karlsson, Hans O.

2013-11-01

The SN2 substitution reactions at phosphorus play a key role in organic and biological processes. Quantum molecular dynamics simulations have been performed to study the prototype reaction Cl-+PH2Cl→ClPH2+Cl-, using one and two-dimensional models. A potential energy surface, showing an energy well for a transition complex, was generated using ab initio electronic structure calculations. The one-dimensional model is essentially reflection free, whereas the more realistic two-dimensional model displays involved resonance structures in the reaction probability. The reaction rate is almost two orders of magnitude smaller for the two-dimensional compared to the one-dimensional model. Energetic errors in the potential energy surface is estimated to affect the rate by only a factor of two. This shows that for these types of reactions it is more important to increase the dimensionality of the modeling than to increase the accuracy of the electronic structure calculation.

Water activities of NaClO4, Ca(ClO4)2, and Mg(ClO4)2 brines from experimental heat capacities: Water activity >0.6 below 200 K

NASA Astrophysics Data System (ADS)

Toner, J. D.; Catling, D. C.

2016-05-01

Perchlorate salts found on Mars are extremely hygroscopic and form low eutectic temperature aqueous solutions, which could allow liquid water to exist on Mars despite cold and dry conditions. The formation, dynamics, and potential habitability of perchlorate salt solutions can be broadly understood in terms of water activity. Water activity controls condensation and evaporation of water vapor in brines, deliquescence and efflorescence of crystalline salts, and ice formation during freezing. Furthermore, water activity is a basic parameter defining the habitability of aqueous solutions. Despite the importance of water activity, its value in perchlorate solutions has only been measured at 298.15 K and at the freezing point of water. To address this lack of data, we have determined water activities in NaClO4, Ca(ClO4)2, and Mg(ClO4)2 solutions using experimental heat capacities measured by Differential Scanning Calorimetry. Our results include concentrations up to near-saturation and temperatures ranging from 298.15 to 178 K. We find that water activities in NaClO4 solutions increase with decreasing temperature, by as much as 0.25 aw from 298.15 to 178 K. Consequently, aw reaches ∼0.6-0.7 even for concentrations up to 15 molal NaClO4 below 200 K. In contrast, water activities in Ca(ClO4)2 and Mg(ClO4)2 solutions generally decrease with decreasing temperature. The temperature dependence of water activity indicates that low-temperature NaClO4 solutions will evaporate and deliquesce at higher relative humidity, crystallize ice at higher temperature, and potentially be more habitable for life (at least in terms of water activity) compared to solutions at 298.15 K. The opposite effects occur in Ca(ClO4)2 and Mg(ClO4)2 solutions.

Analytical investigation of AlCl[3]/SO[2]Cl[2] catholyte materials for secondary fuze reserve batteries.

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

Butler, Paul Charles; Rodriguez, Mark Andrew; Segall, Judith M.

2004-05-01

Exploration of the fundamental chemical behavior of the AlCl{sub 3}/SO{sub 2}Cl{sub 2} catholyte system for the ARDEC Self-Destruct Fuze Reserve Battery Project under accelerated aging conditions was completed using a variety of analytical tools. Four different molecular species were identified in this solution, three of which are major. The relative concentrations of the molecular species formed were found to depend on aging time, initial concentrations, and storage temperature, with each variable affecting the kinetics and thermodynamics of this complex reaction system. We also evaluated the effect of water on the system, and determined that it does not play a rolemore » in dictating the observed molecular species present in solution. The first Al-containing species formed was identified as the dimer [Al({mu}-Cl)Cl{sub 2}]{sub 2}, and was found to be in equilibrium with the monomer, AlCl{sub 3}. The second species formed in the reaction scheme was identified by single crystal X-ray diffraction studies as [Cl{sub 2}Al({mu}-O{sub 2}SCl)]{sub 2} (I), a scrambled AlCl{sub 3}{center_dot}SO{sub 2} adduct. The SO{sub 2}(g) present, as well as CL{sub 2}(g), was formed through decomposition of SO{sub 2}CL{sub 2}. The SO{sub 2}(g) generated was readily consumed by AlCl{sub 3} to form the adduct 1 which was experimentally verified when 1 was also isolated from the reaction of SO{sub 2}(g) and AlCl {sub 3}. The third species found was tentatively identified as a compound having the general formula {l_brace}[Al(O)Cl{sub 2}][OSCl{sub 2}]{r_brace}{sub n}. This was based on {sup 27}Al NMR data that revealed a species with tetrahedrally coordinated Al metal centers with increased oxygen coordination and the fact that the precipitate, or gel, that forms over time was shown by Raman spectroscopic studies to possess a component that is consistent with SOCl{sub 2}. The precursor to the precipitate should have similar constituents, thus the assignment of {l_brace}[Al(O)Cl{sub 2

Single-Crystal Growth of Cl-Doped n-Type SnS Using SnCl2 Self-Flux.

PubMed

Iguchi, Yuki; Inoue, Kazutoshi; Sugiyama, Taiki; Yanagi, Hiroshi

2018-06-05

SnS is a promising photovoltaic semiconductor owing to its suitable band gap energy and high optical absorption coefficient for highly efficient thin film solar cells. The most significant carnage is demonstration of n-type SnS. In this study, Cl-doped n-type single crystals were grown using SnCl 2 self-flux method. The obtained crystal was lamellar, with length and width of a few millimeters and thickness ranging between 28 and 39 μm. X-ray diffraction measurements revealed the single crystals had an orthorhombic unit cell. Since the ionic radii of S 2- and Cl - are similar, Cl doping did not result in substantial change in lattice parameter. All the elements were homogeneously distributed on a cleaved surface; the Sn/(S + Cl) ratio was 1.00. The crystal was an n-type degenerate semiconductor with a carrier concentration of ∼3 × 10 17 cm -3 . Hall mobility at 300 K was 252 cm 2 V -1 s -1 and reached 363 cm 2 V -1 s -1 at 142 K.

XAFS Study on Chlorination of Y2O3 in LiCl-KCl-ZrCl4 Melt

NASA Astrophysics Data System (ADS)

Okamoto, Yoshihiro; Yaita, Tsuyoshi; Shiwaku, Hideaki; Suzuki, Shinichi

2008-11-01

The chlorination reaction of Y2O3 with ZrCl4 in LiCl-KCl eutectic melt was investigated by X-ray absorption fine structure (XAFS) technique. The chlorination reaction was observed between 773 K and 823 K as the 1st peak shift of the Fourier transform magnitude function |FT(k3χ(k))|. The peak corresponding to the nearest Y3+-Cl- correlation was observed in the XAFS analysis at 823 K as the result of the chlorination. It was confirmed that the mixture melts after the reaction is almost equivalent to a molten 5% YCl3-(LiCl-KCl eutectic) mixture.

Electron ionization of SiCl4

NASA Astrophysics Data System (ADS)

King, Simon J.; Price, Stephen D.

2011-02-01

Relative partial ionization cross sections (PICS) for the formation of fragment ions following electron ionization of SiCl4, in the electron energy range 30-200 eV, have been determined using time-of-flight mass spectrometry coupled with an ion coincidence technique. By this method, the contributions to the yield of each fragment ion from dissociative single, double, and triple ionization, are distinguished. These yields are quantified in the form of relative precursor-specific PICS, which are reported here for the first time for SiCl4. For the formation of singly charged ionic fragments, the low-energy maxima appearing in the PICS curves are due to contributions from single ionization involving predominantly indirect ionization processes, while contributions to the yields of these ions at higher electron energies are often dominated by dissociative double ionization. Our data, in the reduced form of relative PICS, are shown to be in good agreement with a previous determination of the PICS of SiCl4. Only for the formation of doubly charged fragment ions are the current relative PICS values lower than those measured in a previous study, although both datasets agree within combined error limits. The relative PICS data presented here include the first quantitative measurements of the formation of Cl2+ fragment ions and of the formation of ion pairs via dissociative double ionization. The peaks appearing in the 2D ion coincidence data are analyzed to provide further information concerning the mechanism and energetics of the charge-separating dissociations of SiCl42+. The lowest energy dicationic precursor state, leading to SiCl3+ + Cl+ formation, lies 27.4 ± 0.3 eV above the ground state of SiCl4 and is in close agreement with a calculated value of the adiabatic double ionization energy (27.3 eV).

Electron ionization of SiCl4.

PubMed

King, Simon J; Price, Stephen D

2011-02-21

Relative partial ionization cross sections (PICS) for the formation of fragment ions following electron ionization of SiCl(4), in the electron energy range 30-200 eV, have been determined using time-of-flight mass spectrometry coupled with an ion coincidence technique. By this method, the contributions to the yield of each fragment ion from dissociative single, double, and triple ionization, are distinguished. These yields are quantified in the form of relative precursor-specific PICS, which are reported here for the first time for SiCl(4). For the formation of singly charged ionic fragments, the low-energy maxima appearing in the PICS curves are due to contributions from single ionization involving predominantly indirect ionization processes, while contributions to the yields of these ions at higher electron energies are often dominated by dissociative double ionization. Our data, in the reduced form of relative PICS, are shown to be in good agreement with a previous determination of the PICS of SiCl(4). Only for the formation of doubly charged fragment ions are the current relative PICS values lower than those measured in a previous study, although both datasets agree within combined error limits. The relative PICS data presented here include the first quantitative measurements of the formation of Cl(2) (+) fragment ions and of the formation of ion pairs via dissociative double ionization. The peaks appearing in the 2D ion coincidence data are analyzed to provide further information concerning the mechanism and energetics of the charge-separating dissociations of SiCl(4) (2+). The lowest energy dicationic precursor state, leading to SiCl(3) (+) + Cl(+) formation, lies 27.4 ± 0.3 eV above the ground state of SiCl(4) and is in close agreement with a calculated value of the adiabatic double ionization energy (27.3 eV).

Cross sections for elastic scattering of electrons by CF3Cl, CF2Cl2, and CFCl3

NASA Astrophysics Data System (ADS)

Hoshino, M.; Horie, M.; Kato, H.; Blanco, F.; García, G.; Limão-Vieira, P.; Sullivan, J. P.; Brunger, M. J.; Tanaka, H.

2013-06-01

Differential, integral, and momentum transfer cross sections have been determined for the elastic scattering of electrons from the molecules CF3Cl, CF2Cl2, and CFCl3.With the help of a crossed electron beam-molecular beam apparatus using the relative flow technique, the ratios of the elastic differential cross sections (DCSs) of CF3Cl, CF2Cl2, and CFCl3 to those of He were measured in the energy region from 1.5 to 100 eV and at scattering angles in the range 15° to 130°. From those ratios, the absolute DCSs were determined by utilizing the known DCS of He. For CF3Cl and CF2Cl2, at the common energies of measurement, we find generally good agreement with the results from the independent experiments of Mann and Linder [J. Phys. B 25, 1621 (1992), 10.1088/0953-4075/25/7/030; Mann and Linder J. Phys. B 25, 1633 (1992), 10.1088/0953-4075/25/7/031]. In addition, as a result of progressively substituting a Cl-atom, undulations in the angular distributions have been found to vary in a largely systematic manner in going from CF4 to CF3Cl to CF2Cl2 to CFCl3 and to CCl4. These observed features suggest that the elastic scattering process is, in an independently additive manner, dominated by the atomic-Cl atoms of the molecules. The present independent atom method calculation typically supports the experimental evidence, within the screened additivity rule formulation, for each species and for energies greater than about 10-20 eV. Integral elastic and momentum transfer cross sections were also derived from the measured DCSs, and are compared to the other available theoretical and experimental results. The elastic integral cross sections are also evaluated as a part of their contribution to the total cross section.

Electrical Conductivity of Molten DyCl3-NaCl and DyCl3-KCl Systems: An Approach to Structural Interpretations of Rare Earth Chloride Melts

NASA Astrophysics Data System (ADS)

Iwadate, Yasuhiko; Ohkubo, Takahiro

2017-11-01

Electrical conductivities (κs) of molten DyCl3-NaCl and DyCl3-KCl systems were estimated by measuring the impedances of each mixture melt at any temperature and/or frequency. The molar volumes (Vms) were measured by dilatometry and represented as a polynomial empirical equation of temperature and composition. Due to both the properties, the molar conductivities (Λms) were calculated and their temperature and/or composition dependences were discussed from the standpoint of structural features as well. The κs increased curvilinearly with increasing temperature across the whole composition ranges. This trend was also applied to the Λms which was fitted by an Arrhenius-type equation. The relationship of Λms with melt composition was studied and the Λms were found to decrease with increasing composition of DyCl3. These findings were interpreted based on the results of structural science so far reported, and finally, the relationship between Λms and the structures of pure rare earth chloride melts was discussed.

Understanding the kinetics of the ClO dimer cycle

NASA Astrophysics Data System (ADS)

von Hobe, M.; Salawitch, R. J.; Canty, T.; Keller-Rudek, H.; Moortgat, G. K.; Grooß, J.-U.; Müller, R.; Stroh, F.

2007-06-01

Among the major factors controlling ozone loss in the polar vortices in winter/spring is the kinetics of the ClO dimer catalytic cycle. Here, we propose a strategy to test and improve our understanding of these kinetics by comparing and combining information on the thermal equilibrium between ClO and Cl2O2, the rate of Cl2O2 formation, and the Cl2O2 photolysis rate from laboratory experiments, theoretical studies and field observations. Concordant with a number of earlier studies, we find considerable inconsistencies of some recent laboratory results with rate theory calculations and stratospheric observations of ClO and Cl2O2. The set of parameters for which we find the best overall consistency - namely the ClO/Cl2O2 equilibrium constant suggested by Plenge et al. (2005), the Cl2O2 recombination rate constant reported by Nickolaisen et al. (1994) and Cl2O2 photolysis rates based on absorption cross sections in the range between the JPL 2006 assessment and the laboratory study by Burkholder et al. (1990) - is not congruent with the latest recommendations given by the JPL and IUPAC panels and does not represent the laboratory studies currently regarded as the most reliable experimental values. We show that the incorporation of new Pope et al. (2007) Cl2O2 absorption cross sections into several models, combined with best estimates for other key parameters (based on either JPL and IUPAC evaluations or on our study), results in severe model underestimates of observed ClO and observed ozone loss rates. This finding suggests either the existence of an unknown process that drives the partitioning of ClO and Cl2O2, or else some unidentified problem with either the laboratory study or numerous measurements of atmospheric ClO. Our mechanistic understanding of the ClO/Cl2O2 system is grossly lacking, with severe implications for our ability to simulate both present and future polar ozone depletion.

NHC→SiCl4 : an ambivalent carbene-transfer reagent.

PubMed

Böttcher, Tobias; Steinhauer, Simon; Lewis-Alleyne, Lesley C; Neumann, Beate; Stammler, Hans-Georg; Bassil, Bassem S; Röschenthaler, Gerd-Volker; Hoge, Berthold

2015-01-07

The addition of BCl3 to the carbene-transfer reagent NHC→SiCl4 (NHC=1,3-dimethylimidazolidin-2-ylidene) gave the tetra- and pentacoordinate trichlorosilicon(IV) cations [(NHC)SiCl3 ](+) and [(NHC)2 SiCl3 ](+) with tetrachloroborate as counterion. This is in contrast to previous reactions, in which NHC→SiCl4 served as a transfer reagent for the NHC ligand. The addition of BF3 ⋅OEt2 , on the other hand, gave NHC→BF3 as the product of NHC transfer. In addition, the highly Lewis acidic bis(pentafluoroethyl)silane (C2 F5 )2 SiCl2 was treated with NHC→SiCl4 . In acetonitrile, the cationic silicon(IV) complexes [(NHC)SiCl3 ](+) and [(NHC)2 SiCl3 ](+) were detected with [(C2 F5 )SiCl3 ](-) as counterion. A similar result was already reported for the reaction of NHC→SiCl4 with (C2 F5 )2 SiH2 , which gave [(NHC)2 SiCl2 H][(C2 F5 )SiCl3 ]. If the reaction medium was changed to dichloromethane, the products of carbene transfer, NHC→Si(C2 F5 )2 Cl2 and NHC→Si(C2 F5 )2 ClH, respectively, were obtained instead. The formation of the latter species is a result of chloride/hydride metathesis. These compounds may serve as valuable precursors for electron-poor silylenes. Furthermore, the reactivity of NHC→SiCl4 towards phosphines is discussed. The carbene complex NHC→PCl3 shows similar reactivity to NHC→SiCl4 , and may even serve as a carbene-transfer reagent as well. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two-center three-electron bonding in ClNH{sub 3} revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH{sub 3} → ClNH{sub 2} + H reaction

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

Moradi, Christopher P.; Douberly, Gary E., E-mail: douberly@uga.edu; Xie, Changjian

2016-04-28

Pyrolytic dissociation of Cl{sub 2} is employed to dope helium droplets with single Cl atoms. Sequential addition of NH{sub 3} to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH{sub 3} → ClNH{sub 2} + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C{sub 3v} symmetric top. Frequency shifts from NH{sub 3} and dipole moment measurements are consistent with a ClNH{sub 3} complex containing a relatively strong two-center three-electron (2c–3e) bond. The nature of the 2c–3e bonding in ClNH{sub 3}more » is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. Computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence in experimental spectra of two other complexes, NH{sub 3}Cl and Cl–HNH{sub 2}, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH{sub 3} → HCl + NH{sub 2}.« less

The stability of Cl-CO3-scapolite relative to plagioclase + CaCO3 + CaSO4 in the presence of NaCl brines as a function of P-T-XNaCl

NASA Astrophysics Data System (ADS)

Harlov, D. E.; Budzyn, B.

2008-12-01

Cl-CO3-scapolite [(Na,Ca)4[Al3 (Al,Si) 3 Si3 O24](Cl, CO3 , SO4 )] occurs as a common partial to total alteration of plagioclase in deep-crustal xenoliths, skarns, marbles, gabbros, metabasites, calc-silicate gneisses, as well as in quartzofeldspathic granulite-facies rocks in general (Moecher and Essene, 1990, J Petrol 31, 997). Alteration of plagioclase to Cl-CO3-scapolite is presumed due to metasomatism by CO2-NaCl-H2O fluids (Satish-Kumar and Santosh, 1998, Geol Mag 135, 27). Previous experimental work on CO3-scapolite has focused on reversing the equilibrium 3 CaAl2 Si2 O8 + CaCO3 = Ca4 Al6 Si6 O24 CO3 in either pure CO2 (Goldschmidt and Newton, 1977, Am Mineral 62, 1063) or in CO2-H2O (Huckenholz and Seiberl, 1989 Abs IGC 28, 2.79). These experiments have determined that the anorthite- calcite-scapolite equilibrium is nearly pressure-invariant in P-T space (200 to 1500 MPa) occurring at approximately 790 to 820 °C (Huckenholz and Seiberl, 1989). In this study, a series of experiments, involving the equilibrium 3 Plagioclase(An60) + 0.5 CaCO3 + 0.5 CaSO4 = [(Na,Ca)4[Al3 (Al,Si)3 Si3 O24](Cl, CO3, SO4 )] plus an NaCl brine (10/90, 20/80, 30/70, and 50/50 molar NaCl/H2O) have been done at 500, 1000, and 1500 MPa and 600 to 900 °C. Natural plagioclase and scapolite, along with synthetic calcite and anhydrite, were lightly ground together in equi-molar amounts in ethanol. The mineral mix (10 mg) + NaCl brine (5 mg), or pure H2O (1.5 mg), were loaded into 3 mm diameter/1.3 mm long Pt capsules which were arc-welded shut, folded, and placed horizontally in a CaF2 setup (with graphite oven), such that the thermocouple tip touched the Pt capsule, or placed in a hydrothermal autoclave (600 and 700 °C; 500 MPa) with an internal thermocouple. A series of duplicate experiments for the same mineral mix, at the same P-T conditions, were done utilizing pure H2O as the flux. The H2O-only experiments duplicated the P-T reversals of Huckenholz and Seiberl (1989). In contrast

A micro-CL system and its applications

NASA Astrophysics Data System (ADS)

Wei, Zenghui; Yuan, Lulu; Liu, Baodong; Wei, Cunfeng; Sun, Cuili; Yin, Pengfei; Wei, Long

2017-11-01

The computed laminography (CL) method is preferable to computed tomography for the non-destructive testing of plate-like objects. A micro-CL system is developed for three-dimensional imaging of plate-like objects. The details of the micro-CL system are described, including the system architecture, scanning modes, and reconstruction algorithm. The experiment results of plate-like fossils, insulated gate bipolar translator module, ball grid array packaging, and printed circuit board are also presented to demonstrate micro-CL's ability for 3D imaging of flat specimens and universal applicability in various fields.

A micro-CL system and its applications.

PubMed

Wei, Zenghui; Yuan, Lulu; Liu, Baodong; Wei, Cunfeng; Sun, Cuili; Yin, Pengfei; Wei, Long

2017-11-01

The computed laminography (CL) method is preferable to computed tomography for the non-destructive testing of plate-like objects. A micro-CL system is developed for three-dimensional imaging of plate-like objects. The details of the micro-CL system are described, including the system architecture, scanning modes, and reconstruction algorithm. The experiment results of plate-like fossils, insulated gate bipolar translator module, ball grid array packaging, and printed circuit board are also presented to demonstrate micro-CL's ability for 3D imaging of flat specimens and universal applicability in various fields.

Characterization of glial cell K-Cl cotransport.

PubMed

Gagnon, Kenneth B E; Adragna, Norma C; Fyffe, Robert E W; Lauf, Peter K

2007-01-01

The molecular mechanism of K-Cl cotransport (KCC) consists of at least 4 isoforms, KCC 1, 2, 3, and 4 which, in multiple combinations, exist in most cells, including erythrocytes and neuronal cells. We utilized reverse-transcriptase-polymerase chain reaction (RT-PCR) and ion flux studies to characterize KCC activity in an immortalized in vitro cell model for fibrous astrocytes, the rat C6 glioblastoma cell. Isoform-specific sets of oligonucleotide primers were synthesized for NKCC1, KCC1, KCC2, KCC3, KCC4, and also for NKCC1 and actin. K-Cl cotransport activity was determined by measuring either the furosemide-sensitive, or the Cl(-)-dependent bumetanide-insensitive Rb(+) (a K(+) congener) influx in the presence of the Na/K pump inhibitor ouabain. Rb(+) influx was measured at a fixed external Cl concentrations, [Cl(-)](e), as a function of varying external Rb concentrations, [Rb(+)](e), and at a fixed [Rb(+)](e) as a function of varying [Cl(-)](e), and with equimolar Cl replacement by anions of the chaotropic series. RT-PCR of C6 glioblastoma (C6) cells identified mRNA for three KCC isoforms (1, 3, and 4). NKCC1 mRNA was also detected. The apparent K(m) for KCC-mediated Rb(+) influx was 15 mM [Rb(+)](e), and V(max) 12.5 nmol Rb(+) * mg protein(-1) * minute(-1). The calculated apparent K(m) for external Cl(-) was 13 mM and V(max) 14.4 nmol Rb(+) * mg protein(-1) * minute(-1). The anion selectivity sequence of the furosemide-sensitive Rb(+) influx was Cl(-)>Br-=NO(3)(-)>I(-)=SCN(-)>Sfm(-) (sulfamate). Established activators of K-Cl cotransport, hyposmotic shock and N-ethylmaleimide (NEM) pretreatment, stimulated furosemide-sensitive Rb(+) influx. A ñ50% NEM-induced loss of intracellular K(+) was prevented by furosemide. We have identified by RT-PCR the presence of three distinct KCC isoforms (1, 3, and 4) in rat C6 glioblastoma cells, and functionally characterized the anion selectivity and kinetics of their collective sodium-independent cation-chloride cotransport

Molecular dynamics simulations of Si etching in Cl- and Br-based plasmas: Cl{sup +} and Br{sup +} ion incidence in the presence of Cl and Br neutrals

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

Nakazaki, Nobuya, E-mail: nakazaki.nobuya.58x@st.kyoto-u.ac.jp; Takao, Yoshinori; Eriguchi, Koji

Classical molecular dynamics (MD) simulations have been performed for Cl{sup +} and Br{sup +} ions incident on Si(100) surfaces with Cl and Br neutrals, respectively, to gain a better understanding of the ion-enhanced surface reaction kinetics during Si etching in Cl- and Br-based plasmas. The ions were incident normally on surfaces with translational energies in the range E{sub i} = 20–500 eV, and low-energy neutrals of E{sub n} = 0.01 eV were also incident normally thereon with the neutral-to-ion flux ratio in the range Γ{sub n}{sup 0}/Γ{sub i}{sup 0} = 0–100, where an improved Stillinger--Weber potential form was employed for the interatomic potential concerned. The etch yieldsmore » and thresholds presently simulated were in agreement with the experimental results previously reported for Si etching in Cl{sub 2} and Br{sub 2} plasmas as well as in Cl{sup +}, Cl{sub 2}{sup +}, and Br{sup +} beams, and the product stoichiometry simulated was consistent with that observed during Ar{sup +} beam incidence on Si in Cl{sub 2}. Moreover, the surface coverage of halogen atoms, halogenated layer thickness, surface stoichiometry, and depth profile of surface products simulated for Γ{sub n}{sup 0}/Γ{sub i}{sup 0} = 100 were in excellent agreement with the observations depending on E{sub i} reported for Si etching in Cl{sub 2} plasmas. The MD also indicated that the yield, coverage, and surface layer thickness are smaller in Si/Br than in Si/Cl system, while the percentage of higher halogenated species in product and surface stoichiometries is larger in Si/Br. The MD further indicated that in both systems, the translational energy distributions of products and halogen adsorbates desorbed from surfaces are approximated by two Maxwellians of temperature T{sub 1} ≈ 2500 K and T{sub 2} ≈ 7000–40 000 K. These energy distributions are discussed in terms of the desorption or evaporation from hot spots formed through chemically enhanced

Biodegradation of the High Explosive Hexanitrohexaazaiso-wurtzitane (CL-20)

PubMed Central

Karakaya, Pelin; Christodoulatos, Christos; Koutsospyros, Agamemnon; Balas, Wendy; Nicolich, Steve; Sidhoum, Mohammed

2009-01-01

The aerobic biodegradability of the high explosive CL-20 by activated sludge and the white rot fungus Phanerochaete chrysosporium has been investigated. Although activated sludge is not effective in degrading CL-20 directly, it can mineralize the alkaline hydrolysis products. Phanerochaete chrysosporium degrades CL-20 in the presence of supplementary carbon and nitrogen sources. Biodegradation studies were conducted using various nutrient media under diverse conditions. Variables included the CL-20 concentration; levels of carbon (as glycerol) and ammonium sulfate and yeast extract as sources of nitrogen. Cultures that received CL-20 at the time of inoculation transformed CL-20 completely under all nutrient conditions studied. When CL-20 was added to pre-grown cultures, degradation was limited. The extent of mineralization was monitored by the 14CO2 time evolution; up to 51% mineralization was achieved when the fungus was incubated with [14C]-CL-20. The kinetics of CL-20 biodegradation by Phanerochaete chrysosporium follows the logistic kinetic growth model. PMID:19440524

Biodegradation of the high explosive hexanitrohexaazaiso-wurtzitane (CL-20).

PubMed

Karakaya, Pelin; Christodoulatos, Christos; Koutsospyros, Agamemnon; Balas, Wendy; Nicolich, Steve; Sidhoum, Mohammed

2009-04-01

The aerobic biodegradability of the high explosive CL-20 by activated sludge and the white rot fungus Phanerochaete chrysosporium has been investigated. Although activated sludge is not effective in degrading CL-20 directly, it can mineralize the alkaline hydrolysis products. Phanerochaete chrysosporium degrades CL-20 in the presence of supplementary carbon and nitrogen sources. Biodegradation studies were conducted using various nutrient media under diverse conditions. Variables included the CL-20 concentration; levels of carbon (as glycerol) and ammonium sulfate and yeast extract as sources of nitrogen. Cultures that received CL-20 at the time of inoculation transformed CL-20 completely under all nutrient conditions studied. When CL-20 was added to pre-grown cultures, degradation was limited. The extent of mineralization was monitored by the (14)CO(2) time evolution; up to 51% mineralization was achieved when the fungus was incubated with [(14)C]-CL-20. The kinetics of CL-20 biodegradation by Phanerochaete chrysosporium follows the logistic kinetic growth model.

High-level ab initio calculations on HGeCl and the equilibrium geometry of the A1A'' state derived from Franck-Condon analysis of the single-vibronic-level emission spectra of HGeCl and DGeCl.

PubMed

Mok, Daniel K W; Chau, Foo-Tim; Lee, Edmond P F; Dyke, John M

2010-02-01

CCSD(T) and/or CASSCF/MRCI calculations have been carried out on the X(1)A' and A(1)A'' states of HGeCl. The fully relativistic effective core potential, ECP10MDF, and associated standard valence basis sets of up to the aug-cc-pV5Z quality were employed for Ge. Contributions from core correlation and extrapolation to the complete basis set limit were included in determining the computed equilibrium geometrical parameters and relative electronic energy of these two states of HGeCl. Based on the currently, most systematic CCSD(T) calculations performed in this study, the best theoretical geometrical parameters of the X(1)A' state are r(e)(HGe) = 1.580 +/- 0.001 A, theta(e) = 93.88 +/- 0.01 degrees and r(e)(GeCl) = 2.170 +/- 0.001 A. In addition, Franck-Condon factors including allowance for anharmonicity and Duschinsky rotation between these two states of HGeCl and DGeCl were calculated employing CCSD(T) and CASSCF/MRCI potential energy functions, and were used to simulate A(1)A'' --> X(1)A' SVL emission spectra of HGeCl and DGeCl. The iterative Franck-Condon analysis (IFCA) procedure was carried out to determine the equilibrium geometrical parameters of the A(1)A'' state of HGeCl by matching the simulated, and available experimental SVL emission spectra of HGeCl and DGeCl of Tackett et al., J Chem Phys 2006, 124, 124320, using the available, estimated experimental equilibrium (r(e)(z)) structure for the X(1)A' state, while varying the equilibrium geometrical parameters of the A(1)A'' state systematically. Employing the derived IFCA geometry of r(e)(HGe) = 1.590 A, r(e)(GeCl) = 2.155 A and theta(e)(HGeCl) = 112.7 degrees for the A(1)A'' state of HGeCl in the spectral simulation, the simulated absorption and SVL emission spectra of HGeCl and DGeCl agree very well with the available experimental LIF and SVL emission spectra, respectively. Copyright 2009 Wiley Periodicals, Inc.

3. LOS ANGELES RIVER AND FIGUEROA STREET VIADUCTS ACROSS LOS ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

3. LOS ANGELES RIVER AND FIGUEROA STREET VIADUCTS ACROSS LOS ANGELES RIVER. LOOKING 18° N. - Arroyo Seco Parkway, Figueroa Street Viaduct, Spanning Los Angeles River, Los Angeles, Los Angeles County, CA

Preparation and Characterization of Nano-CL-20 Explosive

NASA Astrophysics Data System (ADS)

Bayat, Yadollah; Zeynali, Vida

2011-10-01

Nano-CL-20 was prepared via precipitative crystallization by spraying a solution of CL-20 in a solvent (ethyl acetate) into a nonsolvent (isooctane). Scanning electron microscopy (SEM) and X-ray powder diffraction (XRD) were used to characterize the appearance and the size of the particles. The results revealed that nano-CL-20 particles have the shape of spheres or ellipsoids with an average size of 95 nm. Due to their small diameter and high surface energy, the particles tended to agglomerate. Impact sensitivity of nanosize CL-20 was decreased in comparison to micrometer-size CL-20.

Evaluation of the OpenCL AES Kernel using the Intel FPGA SDK for OpenCL

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

Jin, Zheming; Yoshii, Kazutomo; Finkel, Hal

The OpenCL standard is an open programming model for accelerating algorithms on heterogeneous computing system. OpenCL extends the C-based programming language for developing portable codes on different platforms such as CPU, Graphics processing units (GPUs), Digital Signal Processors (DSPs) and Field Programmable Gate Arrays (FPGAs). The Intel FPGA SDK for OpenCL is a suite of tools that allows developers to abstract away the complex FPGA-based development flow for a high-level software development flow. Users can focus on the design of hardware-accelerated kernel functions in OpenCL and then direct the tools to generate the low-level FPGA implementations. The approach makes themore » FPGA-based development more accessible to software users as the needs for hybrid computing using CPUs and FPGAs are increasing. It can also significantly reduce the hardware development time as users can evaluate different ideas with high-level language without deep FPGA domain knowledge. In this report, we evaluate the performance of the kernel using the Intel FPGA SDK for OpenCL and Nallatech 385A FPGA board. Compared to the M506 module, the board provides more hardware resources for a larger design exploration space. The kernel performance is measured with the compute kernel throughput, an upper bound to the FPGA throughput. The report presents the experimental results in details. The Appendix lists the kernel source code.« less

Accurate ab Initio Quartic Force Fields, Vibrational Frequencies, and Heats of Formation for FCN, FNC, ClCN, and ClNC

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Martin, Jan M. L.; Dateo, Christopher E.; Taylor, Peter R.

1995-01-01

The XCN and XNC (X = F, Cl) isomers have been investigated using the CCSD(T) method in conjunction with correlation consistent basis sets. Equilibrium geometries, harmonic frequencies, anharmonic constants, fundamental frequencies, and heats of formation have been evaluated. Agreement with experiment for the fundamental frequencies is very good, even for nu(sub 2), for CICN, which is subject to a strong Fermi resonance with 2nu(sub 3). It is also shown that a second-order perturbation theory approach to solving the nuclear Schroedinger equation gives results in excellent agreement with essentially exact variational calculations. This is true even for nu(sub 2) of ClCN, provided that near-singular terms are eliminated from the perturbation theory formulas and the appropriate Fermi interaction energy matrix is then diagonalized. A band at 615/cm, tentatively assigned as the Cl-N stretch in ClNC in matrix isolation experiments, is shown not to be due to ClNC. Accurate atomization energies are determined and are used to evaluate accurate heats of formation (3.1 +/- 1.5, 33.2 +/- 1.5, 72.6 +/- 1.5, and 75.9 +/- 1.5 kcal/mol for FCN, ClCN, FNC, and ClNC, respectively). It is expected that the theoretical heats of formation for FCN, FNC, and ClNC are the most accurate available.

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

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

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

Millimeter-wave spectroscopy of the SiCl+ ion

NASA Astrophysics Data System (ADS)

Takeda, Kazuki; Masuda, Satoshi; Harada, Kensuke; Tanaka, Keiichi

2016-05-01

The millimeter-wave spectrum of the SiCl+ ion in the ground and first excited vibrational states was observed for the two isotopic (35Cl and 37Cl) species. The ion was generated in a free-space absorption cell by a hollow cathode discharge of SiCl4 diluted with He and discriminated from neutral species by the magnetic field effect on the absorption lines. The observed millimeter-wave spectrum was combined with a previously reported diode laser spectrum in an analysis to determine mass-independent Dunham coefficients as well as the mass scaling parameters. The equilibrium bond length of SiCl+ determined is re = 1.943 978(2) Å.

An infrared band system of the ZrCl molecule

NASA Astrophysics Data System (ADS)

Phillips, J. G.; Davis, S. P.; Galehouse, D. C.

1980-07-01

A series of infrared bands in the 0.97-1.15 micron region which is attributed to ZrCl is analyzed in light of the possibility that the bands may be observable in stellar spectra. Spectra of ZrO and ZrCl were produced by microwave discharge through a mixture of He, O and ZrCl4 and observed by Fourier transform spectrometer, resulting in the observation of 10 bands of the ZrCl system. Rotational quantum number assignments to the lines of the P and R branches observed are obtained and used to derive effective rotational constants for each substate, as well as zero-rotation origins of each subband. Shifts in wave numbers of rotational lines of the isotopes (Zr-92)(Cl-35)(Zr-94)(Cl-35) and (Zr-90)(Cl-37) relative to the more abundant (Zr-90)(Cl-35) are also observed. The observed molecular constants are shown to be in good agreement with those calculated in previous theoretical estimates.

Deposition, Accumulation, and Alteration of Cl(-), NO3(-), ClO4(-) and ClO3(-) Salts in a Hyper-Arid Polar Environment: Mass Balance and Isotopic Constraints

NASA Technical Reports Server (NTRS)

Jackson, Andrew; Davila, Alfonso F.; Boehlke, J. K.; Sturchio, Neil C.; Sevanthi, Ritesh; Estrada, Nubia; Brundrette, Megan; Lacell, Denis; McKay, Christopher P.; Poghosyan, Armen;

Deposition, accumulation, and alteration of Cl-, NO3-, ClO4- and ClO3- salts in a hyper-arid polar environment: Mass balance and isotopic constraints

NASA Astrophysics Data System (ADS)

Jackson, Andrew; Davila, Alfonso F.; Böhlke, John Karl; Sturchio, Neil C.; Sevanthi, Ritesh; Estrada, Nubia; Brundrett, Maeghan; Lacelle, Denis; McKay, Christopher P.; Poghosyan, Armen; Pollard, Wayne; Zacny, Kris

2016-06-01

The salt fraction in permafrost soils/sediments of the McMurdo Dry Valleys (MDV) of Antarctica can be used as a proxy for cold desert geochemical processes and paleoclimate reconstruction. Previous analyses of the salt fraction in MDV permafrost soils have largely been conducted in coastal regions where permafrost soils are variably affected by aqueous processes and mixed inputs from marine and stratospheric sources. We expand upon this work by evaluating permafrost soil/sediments in University Valley, located in the ultraxerous zone where both liquid water transport and marine influences are minimal. We determined the abundances of Cl-, NO3-, ClO4- and ClO3- in dry and ice-cemented soil/sediments, snow and glacier ice, and also characterized Cl- and NO3- isotopically. The data are not consistent with salt deposition in a sublimation till, nor with nuclear weapon testing fall-out, and instead point to a dominantly stratospheric source and to varying degrees of post depositional transformation depending on the substrate, from minimal alteration in bare soils to significant alteration (photodegradation and/or volatilization) in snow and glacier ice. Ionic abundances in the dry permafrost layer indicate limited vertical transport under the current climate conditions, likely due to percolation of snowmelt. Subtle changes in ClO4-/NO3- ratios and NO3- isotopic composition with depth and location may reflect both transport related fractionation and depositional history. Low molar ratios of ClO3-/ClO4- in surface soils compared to deposition and other arid systems suggest significant post depositional loss of ClO3-, possibly due to reduction by iron minerals, which may have important implications for oxy-chlorine species on Mars. Salt accumulation varies with distance along the valley and apparent accumulation times based on multiple methods range from ∼10 to 30 kyr near the glacier to 70-200 kyr near the valley mouth. The relatively young age of the salts and

Secretory NaCl and volume flow in renal tubules.

PubMed

Beyenbach, K W

1986-05-01

This review attempts to give a retrospective survey of the available evidence concerning the secretion of NaCl and fluid in renal tubules of the vertebrate kidney. In the absence of glomerular filtration, epithelial secretory mechanisms, which to this date have not been elucidated, are responsible for the renal excretion of NaCl and water in aglomerular fish. However, proximal tubules isolated from glomerular fish kidneys of the flounder, killifish, and the shark also have the capacity to secrete NaCl and fluid. In shark proximal tubules, fluid secretion appears to be driven via secondary active transport of Cl. In another marine vertebrate, the sea snake, secretion of Na (presumably NaCl) and fluid is observed in freshwater-adapted and water-loaded animals. Proximal tubules of mammals can be made to secrete NaCl in vitro together with secretion of aryl acids. An epithelial cell line derived from dog kidney exhibits secondary active secretion of Cl when stimulated with catecholamines. Tubular secretion of NaCl and fluid may serve a variety of renal functions, all of which are considered here. The occurrence of NaCl and fluid secretion in glomerular proximal tubules of teleosts, elasmobranchs, and reptiles and in mammalian renal tissue cultures suggests that the genetic potential for NaCl secretion is present in every vertebrate kidney.

Studies on the thermal behavior of CS:LiTFSI:[Amim] Cl polymer electrolytes exerted by different [Amim] Cl content

NASA Astrophysics Data System (ADS)

Ramesh, S.; Shanti, R.; Morris, Ezra

2012-01-01

The principle motivation of this research work is to develop environmental-friendly polymer electrolytes utilizing corn starch (CS), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 1-allyl-3-methylimidazolium chloride ([Amim] Cl) by solution casting technique. The highest ionic conductivity value was achieved for the composition CS:LiTFSI:[Amim] Cl (14 wt. %:6 wt. %:80 wt. %) which exhibits the ionic conductivity value of 5.68 × 10 -2 S cm -1 at 40 °C with the activation energy of 4.86 kJ mol -1. This sample possess high concentration of amorphous phase coupled with greater presence of conducting cations (lithium, Li + and imidazolium, [Amim] +) as depicted by the dielectric loss tangent plot. The conductivity-temperature plots were found to obey Arrhenius rule in which the conductivity mechanism is thermally assisted. The melting temperature of polymer electrolyte decreases with increase in [Amim] Cl content. This is attributed to the good miscibility of [Amim] Cl in CS:LiTFSI matrix inducing structural disorderliness. Reference to the TGA results it is found that the addition of [Amim] Cl diminishes the heat-resistivity whereas enhancement in the thermal stability occurred at the initial addition and declines with further doping of [Amim] Cl.

Vertically resolved measurements of nighttime radical reservoirs in Los Angeles and their contribution to the urban radical budget.

PubMed

Young, Cora J; Washenfelder, Rebecca A; Roberts, James M; Mielke, Levi H; Osthoff, Hans D; Tsai, Catalina; Pikelnaya, Olga; Stutz, Jochen; Veres, Patrick R; Cochran, Anthony K; VandenBoer, Trevor C; Flynn, James; Grossberg, Nicole; Haman, Christine L; Lefer, Barry; Stark, Harald; Graus, Martin; de Gouw, Joost; Gilman, Jessica B; Kuster, William C; Brown, Steven S

2012-10-16

Photolabile nighttime radical reservoirs, such as nitrous acid (HONO) and nitryl chloride (ClNO(2)), contribute to the oxidizing potential of the atmosphere, particularly in early morning. We present the first vertically resolved measurements of ClNO(2), together with vertically resolved measurements of HONO. These measurements were acquired during the California Nexus (CalNex) campaign in the Los Angeles basin in spring 2010. Average profiles of ClNO(2) exhibited no significant dependence on height within the boundary layer and residual layer, although individual vertical profiles did show variability. By contrast, nitrous acid was strongly enhanced near the ground surface with much smaller concentrations aloft. These observations are consistent with a ClNO(2) source from aerosol uptake of N(2)O(5) throughout the boundary layer and a HONO source from dry deposition of NO(2) to the ground surface and subsequent chemical conversion. At ground level, daytime radical formation calculated from nighttime-accumulated HONO and ClNO(2) was approximately equal. Incorporating the different vertical distributions by integrating through the boundary and residual layers demonstrated that nighttime-accumulated ClNO(2) produced nine times as many radicals as nighttime-accumulated HONO. A comprehensive radical budget at ground level demonstrated that nighttime radical reservoirs accounted for 8% of total radicals formed and that they were the dominant radical source between sunrise and 09:00 Pacific daylight time (PDT). These data show that vertical gradients of radical precursors should be taken into account in radical budgets, particularly with respect to HONO.

(CH3)3SiCl/SiCl4 azeotrope grows superhydrophobic nanofilaments.

PubMed

Gao, Lichao; McCarthy, Thomas J

2008-01-15

We describe the vapor-phase reaction (at room temperature and 40-45% relative humidity) of silicon wafers with the azeotropic mixture of trimethylchlorosilane and tetrachlorosilane. Water contact angle analysis indicates that surfaces become nearly perfectly hydrophobic (thetaA/thetaR > or =176 degrees/> or =176 degrees) after 2 min of reaction. SEM analysis at various reaction times shows the growth of nanofilaments with diameters of approximately 30 nm. X-ray photoelectron spectroscopy of oxidized titanium surfaces that were exposed to the azeotrope vapor indicates that the product is derived from a approximately 10:1 ratio of SiCl4 and (CH3)3SiCl. A mechanism for filament growth is proposed.

Regulation of Cl(-) secretion by AMPK in vivo.

PubMed

Kongsuphol, Patthara; Hieke, Bernhard; Ousingsawat, Jiraporn; Almaca, Joana; Viollet, Benoit; Schreiber, Rainer; Kunzelmann, Karl

2009-03-01

Previous in vitro studies suggested that Cl(-) currents produced by the cystic fibrosis transmembrane conductance regulator (CFTR; ABCC7) are inhibited by the alpha1 isoform of the adenosine monophosphate (AMP)-stimulated kinase (AMPK). AMPK is a serine/threonine kinase that is activated during metabolic stress. It has been proposed as a potential mediator for transport-metabolism coupling in epithelial tissues. All previous studies have been performed in vitro and thus little is known about the regulation of Cl(-) secretion by AMPK in vivo. Using AMPKalpha1(-/-) mice and wild-type littermates, we demonstrate that phenformin, an activator of AMPK, strongly inhibits cAMP-activated Cl(-) secretion in mouse airways and colon, when examined in ex vivo in Ussing chamber recordings. However, phenformin was equally effective in AMPKalpha1(-/-) and wild-type animals, suggesting additional AMPK-independent action of phenformin. Phenformin inhibited CFTR Cl(-) conductance in basolaterally permeabilized colonic epithelium from AMPKalpha1(+/+) but not AMPKalpha1(-/-) mice. The inhibitor of AMPK compound C enhanced CFTR-mediated Cl(-) secretion in epithelial tissues of AMPKalpha1(-/-) mice, but not in wild-type littermates. There was no effect on Ca(2+)-mediated Cl(-) secretion, activated by adenosine triphosphate or carbachol. Moreover CFTR-dependent Cl(-) secretion was enhanced in the colon of AMPKalpha1(-/-) mice, as indicated in Ussing chamber ex vivo and rectal PD measurements in vivo. Taken together, these data suggest that epithelial Cl(-) secretion mediated by CFTR is controlled by AMPK in vivo.

ROSAT PSPC Observations of CL0016+16

NASA Technical Reports Server (NTRS)

Hughes, John P. (Principal Investigator)

1996-01-01

Several ROSAT observations concerning with complex spatial structures in Sunyaev-Zel'dovich decrement clusters Abell 665 and CL0016+16, discovery of Be/X-ray stars in two supernova remnants in the Small Magellanic Cloud, a new transient pulsar in the Small Magellanic Cloud with an unusual x-ray spectrum, a new x-ray-discovered cluster of galaxies associated with CL0016+16, and the distance to CL0016+16 vs. the Hubble constant, are presented.

Preparation and spectroscopic characterization of two HoCl 3-galactitol complexes and one ErCl 3-galactitol complex

NASA Astrophysics Data System (ADS)

Hua, Xiaohui; Pan, Qinghua; Yu, Lei; Xue, Junhui; Yang, Limin; Xu, Yizhuang; Zhao, Guozhong; Li, Weihong; Wang, Zheming; Wu, Jinguang; Liu, Kexin; Chen, Jia'er

2011-07-01

The interactions between metal ions and hydroxyl groups of carbohydrates are important for their possible biological activities. Here two HoCl 3-galactitol complexes ([Ho(galac)(H 2O) 3)]Cl 3·0.5galac) (HoG(I)) and ([Ho 2(galac)(H 2O) 12)]Cl 6·2H 2O) (HoG(II))) and one ErCl 3-galactitol complex ([Er(galac)(H 2O) 3)]Cl 3·0.5galac)(ErG)) were prepared and characterized. The possible structures of HoG(I) and ErG were deduced from FTIR, elemental analysis, ESI-MS, FIR, THz and TGA results. It is suggested that Ho 3+ or Er 3+ is 9-coordinated with six hydroxyl groups from two galactitol molecules and three water molecules, and another galactitol molecule is hydrogen-bonded in HoG(I) and ErG and the ratio of metal to ligand is 1:1.5. The structure of HoG(II) was determined by FTIR and X-ray diffraction analyses. The results demonstrate that lanthanide ions with galactitol may form two compounds in a system and different topological structures can be obtained.

Characterization of CuCl quantum dots grown in NaCl single crystals via optical measurements, X-ray diffraction, and transmission electron microscopy

NASA Astrophysics Data System (ADS)

Miyajima, Kensuke; Akatsu, Tatsuro; Itoh, Ken

2018-05-01

We evaluated the crystal size, shape, and alignment of the lattice planes of CuCl quantum dots (QDs) embedded in NaCl single crystals by optical measurements, X-ray diffraction (XRD) patterns, and transmission electron microscopy (TEM). We obtained, for the first time, an XRD pattern and TEM images for CuCl QDs in NaCl crystals. The XRD pattern showed that the lattice planes of the CuCl QDs were parallel to those of the NaCl crystals. In addition, the size of the QDs was estimated from the diffraction width. It was apparent from the TEM images that almost all CuCl QDs were polygonal, although some cubic QDs were present. The mean size and size distribution of the QDs were also obtained. The dot size obtained from optical measurements, XRD, and TEM image were almost consistent. Our new findings can help to reveal the growth mechanism of semiconductor QDs embedded in a crystallite matrix. In addition, this work will play an important role in progressing the study of optical phenomena originating from assembled semiconductor QDs.

Superconductivity could occur Na-supersaturated NaCl

NASA Astrophysics Data System (ADS)

Hanaki, Koji

1997-04-01

A flow-into electron and a flow-out hole mean flow-into of two unit electric c harges. Even if an exciton consisting of an electron and a hole is a neutral q uasi-particle, overlapping of excitons, namely, the bose condensation changes into a superconductor where half the electric current is due to holes moving t oward the reverse direction. The Meisner effect of the bose condensation comes from the precession of the each exciton under the magnetic field^1. Moreo ver, the present mechanism is supported with that superconducting material alw ays has two kinds of carriers. The superconductivity of NaCl comes from the ab ove-mentioned theory. Free stable holes at first and then electrons are produc ed in NaCl when considerable number of Cl^- lattice vacancies are brought in NaCl mainly because some electrons in the Cl-3p filled band fall into the v acancies. The coexistence of two kinds of stable carriers does not always mean the presence of excitons like VO with electrons not paired and localized in e ach V atom though. While, the absorption spectrum of the NaCl has already conf irmed the presence of excitons; the strength of the spectrum seems to indicate the formation of the bose condensation. Thus we could expect a new supercondu ctor. 1) Hanaki B.Am.P.Soc.,40-1(1995)568

77 FR 56525 - Special Conditions: Bombardier, Model CL-600-2B16 Airplane (CL-601-3A, CL-601-3R, and CL-604...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-09-13

... and CL- 604. This airplane, as modified by Atlantic Aero, Inc., will have a novel or unusual design... airworthiness regulations do not contain adequate or appropriate safety standards for this design feature. These... documents or comments received may be read at http://www.regulations.gov/ at any time. Follow the online...

High Pressure Strength Study on NaCl

NASA Astrophysics Data System (ADS)

Mi, Z.; Shieh, S. R.; High Pressure Mineral Physics Group

2010-12-01

Yield strength is regarded as one important property related to rheological characteristics of minerals in the Earth’s interior. The strength study of NaCl, a popular pressure medium in static high pressure experiments, has been carried out under non-hydrostatic conditions in a diamond anvil cell up to 43 GPa at room temperature using radial energy dispersive X-ray diffraction technique. Phase transformation from B1 (rock salt structure) to B2 (CsCl structure) starts at 29.4 GPa, and is complete at 32.1 GPa. Bulk modulus obtained by third order Birch-Manurgham equation of state is 25.5 GPa with pressure derivative 4.6 for B1 phase, and 30.78 GPa with pressure derivative 4.32 GPa for B2 phase, which are in a good agreement with previous studies. The differential stress of NaCl B1 phase shows very gentle increase with pressure, which indicates that NaCl is a very good pressure-transmitting medium at pressure below 30 GPa. However, the differential stress increases more abruptly for B2 phase and this may imply that NaCl can no longer be regarded as a “soft” pressure medium at very high pressures. For B1 phase, (111) is the strongest plane and (200) is the weakest plane, while (200) becomes the strongest plane in B2 phase. Pure NaCl is weaker than mixture MgO and NaCl, which indicates that soft material become stronger when mixed with hard material. The yield strength of B2 obtained through energy dispersive X-ray diffraction technique increase linearly, while the value derived by pressure gradient method shows jagged trend.

Water Quality Assessment of the Los Angeles River Watershed, California, USA in Wet and Dry Weather Periods

NASA Astrophysics Data System (ADS)

Rezaie Boroon, M. H.; Von L Coo, C.

2015-12-01

The purpose of this study is to identify sources of potential pollutants and characterize urban water quality along the Los Angeles River from its head to the mouth during dry and wet weather periods. Los Angeles (LA) River flows through heavily populated urbanized area in the Los Angeles downtown. The LA River is an effluent-dominated water body during the dry season. The three waste water treatment plants (WWTP) including the Tillman, Burbank, and Glendale discharge the majority of the volume flowing in the LA River during the dry and wet period. The concentration values (ppm) for anions in the dry season ranging 5.5-16,027 (Cl), 0-1.0 (F), 0-21(NO3), 0-1.6 (PO4), and 13.3-2,312 (SO4); whereas the values (ppm) for anions in the wet season ranging 3.4-5,860 (Cl), 0-0.66 (F), 0-17 (NO3), 0-0.67 (PO4), 7.9- 745 (SO4). Dry season concentrations values for trace metals were obtained with values (ppb) ranging 0.9-10 (Ni), 0.8-62 (Zn), 1-4 (As), 0-1 (Pb) and 0-3 (Se). As for wet season trace metals (ppb) ranging 0.001-0.008 (Ni), 0.000001-0.038 (Zn), 0.0016-0.016 (As), 0.00099-0.0058 (Pb), 0.000001-0.0093 (Se). Higher concentrations values during the dry period in the LA River watershed may be attributed to the three WWTPs discharge (75% of the volume of water flowing in the LA River). In water-limited areas such as the Los Angeles basin, urban runoff is a water resource that could enhance restricted water supplies and to enhance localized renewable groundwater resources, thus an assessment of this precious water resource is important for local city and regulatory organizations. In water-limited areas such as the LA basin, urban runoff is a water resource that could enhance restricted water supplies and groundwater resources, thus an assessment of this precious water resource is important for local regulatory organizations.

Identification of the pH sensor and activation by chemical modification of the ClC-2G Cl- channel.

PubMed

Stroffekova, K; Kupert, E Y; Malinowska, D H; Cuppoletti, J

1998-10-01

Rabbit and human ClC-2G Cl- channels are voltage sensitive and activated by protein kinase A and low extracellular pH. The objective of the present study was to investigate the mechanism involved in acid activation of the ClC-2G Cl- channel and to determine which amino acid residues play a role in this acid activation. Channel open probability (Po) at +/-80 mV holding potentials increased fourfold in a concentration-dependent manner with extracellular H+ concentration (that is, extracellular pH, pHtrans), with an apparent acidic dissociation constant of pH 4.95 +/- 0.27. 1-Ethyl-3(3-dimethylaminopropyl)carbodiimide-catalyzed amidation of the channel with glycine methyl ester increased Po threefold at pHtrans 7.4, at which the channel normally exhibits low Po. With extracellular pH reduction (protonation) or amidation, increased Po was due to a significant increase in open time constants and a significant decrease in closed time constants of the channel gating, and this effect was insensitive to applied voltage. With the use of site-directed mutagenesis, the extracellular region EELE (amino acids 416-419) was identified as the pH sensor and amino acid Glu-419 was found to play the key or predominant role in activation of the ClC-2G Cl- channel by extracellular acid.

Cell degradation of a Na–NiCl 2 (ZEBRA) battery

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

Li, Guosheng; Lu, Xiaochuan; Kim, Jin Y.

2013-09-23

In this work, the parameters influencing the degradation of a Na-NiCl 2 (ZEBRA) battery were investigated. Planar Na-NiCl 2 cells using β”-alumina solid electrolyte (BASE) were tested with different C-rates, Ni/NaCl ratios, and capacity windows, in order to identify the key parameters for the degradation of Na-NiCl 2 battery. The morphology of NaCl and Ni particles were extensively investigated after 60 cycles under various test conditions using a scanning electron microscope. A strong correlation between the particle size (NaCl and Ni) and battery degradation was observed in this work. Even though the growth of both Ni and NaCl can influencemore » the cell degradation, our results indicate that the growth of NaCl is a dominant factor in cell degradation. The use of excess Ni seems to play a role in tolerating the negative effects of particle growth on degradation since the available active surface area of Ni particles can be still sufficient even after particle growth. For NaCl, a large cycling window was the most significant factor, of which effects were amplified with decrease in Ni/NaCl ratio.« less

Al/Cl2 molten salt battery

NASA Technical Reports Server (NTRS)

Giner, J.

1972-01-01

Molten salt battery has been developed with theoretical energy density of 5.2 j/kg (650 W-h/lb). Battery, which operates at 150 C, can be used in primary mode or as rechargeable battery. Battery has aluminum anode and chlorine cathode. Electrolyte is mixture of AlCl3, NaCl, and some alkali metal halide such as KCl.

Kinetin Reversal of NaCl Effects

PubMed Central

Katz, Adriana; Dehan, Klara; Itai, Chanan

1978-01-01

Leaf discs of Nicotiana rustica L. were floated on NaCl in the presence of kinetin or abscisic acid. On the 5th day 14CO2 fixation, [3H]leucine incorporation, stomatal conductance, and chlorophyll content were determined. Kinetin either partially or completely reversed the inhibitory effects of NaCl while ABA had no effect. PMID:16660618

Interplay between structure and transport properties of molten salt mixtures of ZnCl2-NaCl-KCl: A molecular dynamics study.

PubMed

Manga, Venkateswara Rao; Swinteck, Nichlas; Bringuier, Stefan; Lucas, Pierre; Deymier, Pierre; Muralidharan, Krishna

2016-03-07

Molten mixtures of network-forming covalently bonded ZnCl2 and network-modifying ionically bonded NaCl and KCl salts are investigated as high-temperature heat transfer fluids for concentrating solar power plants. Specifically, using molecular dynamics simulations, the interplay between the extent of the network structure, composition, and the transport properties (viscosity, thermal conductivity, and diffusion) of ZnCl2-NaCl-KCl molten salts is characterized. The Stokes-Einstein/Eyring relationship is found to break down in these network-forming liquids at high concentrations of ZnCl2 (>63 mol. %), while the Eyring relationship is seen with increasing KCl concentration. Further, the network modification due to the addition of K ions leads to formation of non-bridging terminal Cl ions, which in turn lead to a positive temperature dependence of thermal conductivity in these melts. This new understanding of transport in these ternary liquids enables the identification of appropriate concentrations of the network formers and network modifiers to design heat transfer fluids with desired transport properties for concentrating solar power plants.

Kinetics and Thermochemistry of the Cl((sup 2)P(sub J)) + C2Cl4 Association Reaction

NASA Technical Reports Server (NTRS)

Nicovich, J. M.; Wang, S.; Mckee, M. L.; Wine, P. H.

1997-01-01

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the Cl(sup 2)P(sub j) + C2Cl4 association reaction as a function of temperature (231-390 K) and pressure (3-700 Torr) in nitrogen buffer gas. The reaction is found to be in the falloff regime between third and second order over the range of conditions investigated, although the second-order limit is approached at the highest pressures and lowest temperatures. At temperatures below 300 K, the association reaction is found to be irreversible on the experimental time scale of approximately 20 m-s. The kinetic data at T is less than 300 K have been employed to obtain falloff parameters in a convenient format for atmospheric modeling. At temperatures above 330 K, reversible addition is observed, thus allowing equilibrium constants for C2Cl5 formation and dissociation to be determined. Second- and third-law analyses of the equilibrium data lead to the following thermochemical parameters for the association reaction: Delta-H(298) = -18.1 +/- 1.3 kcal/mol, Delta-H(0) = -17.6 +/- 1.3 kcal/mol, and Delta-S(298) = -27.7 +/- 3.0 cal/mol.K. In conjunction with the well-known heats of formation of Cl((sup 2)P(sub j)) and C2Cl4 the above Delta-H values lead to the following heats of formation for C2Cl5, at 298 and 0 K: Delta-H(f,298) = 8.0 +/- 1.3 kcal/mol and Delta-H(f,0) = 8.1 +/- 1.5 kcal/mol. The kinetic and thermochemical parameters reported above are compared with other reported values, and the significance of reported association rate coefficients for understanding tropospheric chlorine chemistry is discussed.

Effects of NaCl and CaCl2 on Water Transport across Root Cells of Maize (Zea mays L.) Seedlings 1

PubMed Central

Azaizeh, Hassan; Gunse, Benito; Steudle, Ernst

1992-01-01

The effect of salinity and calcium levels on water flows and on hydraulic parameters of individual cortical cells of excised roots of young maize (Zea mays L. cv Halamish) plants have been measured using the cell pressure probe. Maize seedlings were grown in one-third strength Hoagland solution modified by additions of NaCl and/or extra calcium so that the seedlings received one of four treatments: control; +100 millimolar NaCl; +10 millimolar CaCl2; +100 millimolar NaCl + 10 millimolar CaCl2. From the hydrostatic and osmotic relaxations of turgor, the hydraulic conductivity (Lp) and the reflection coefficient (σs) of cortical cells of different root layers were determined. Mean Lp values in the different layers (first to third, fourth to sixth, seventh to ninth) of the four different treatments ranged from 11.8 to 14.5 (Control), 2.5 to 3.8 (+NaCl), 6.9 to 8.7 (+CaCl2), and 6.6 to 7.2 · 10−7 meter per second per megapascal (+NaCl + CaCl2). These results indicate that salinization of the growth media at regular calcium levels (0.5 millimolar) decreased Lp significantly (three to six times). The addition of extra calcium (10 millimolar) to the salinized media produced compensating effects. Mean cell σs values of NaCl ranged from 1.08 to 1.16, 1.15 to 1.22, 0.94 to 1.00, and 1.32 to 1.46 in different root cell layers of the four different treatments, respectively. Some of these σs values were probably overestimated due to an underestimation of the elastic modulus of cells, σs values of close to unity were in line with the fact that root cell membranes were practically not permeable to NaCl. However, the root cylinder exhibited some permeability to NaCl as was demonstrated by the root pressure probe measurements that resulted in σsr of less than unity. Compared with the controls, salinity and calcium increased the root cell diameter. Salinized seedlings grown at regular calcium levels resulted in shorter cell length compared with control (by a factor of 2

Natural variability in Drosophila larval and pupal NaCl tolerance.

PubMed

Riedl, Craig A L; Oster, Sara; Busto, Macarena; Mackay, Trudy F C; Sokolowski, Marla B

2016-05-01

The regulation of NaCl is essential for the maintenance of cellular tonicity and functionality, and excessive salt exposure has many adverse effects. The fruit fly, Drosophila melanogaster, is a good osmoregulator and some strains can survive on media with very low or high NaCl content. Previous analyses of mutant alleles have implicated various stress signaling cascades in NaCl sensitivity or tolerance; however, the genes influencing natural variability of NaCl tolerance remain for the most part unknown. Here, we use two approaches to investigate natural variation in D. melanogaster NaCl tolerance. We describe four D. melanogaster lines that were selected for different degrees of NaCl tolerance, and present data on their survival, development, and pupation position when raised on varying NaCl concentrations. After finding evidence for natural variation in salt tolerance, we present the results of Quantitative Trait Loci (QTL) mapping of natural variation in larval and pupal NaCl tolerance, and identify different genomic regions associated with NaCl tolerance during larval and pupal development. Copyright © 2016 Elsevier Ltd. All rights reserved.

Measurement and Modeling of Setschenow Constants for Selected Hydrophilic Compounds in NaCl and CaCl2 Simulated Carbon Storage Brines.

PubMed

Burant, Aniela; Lowry, Gregory V; Karamalidis, Athanasios K

2017-06-20

Carbon capture, utilization, and storage (CCUS), a climate change mitigation strategy, along with unconventional oil and gas extraction, generates enormous volumes of produced water containing high salt concentrations and a litany of organic compounds. Understanding the aqueous solubility of organic compounds related to these operations is important for water treatment and reuse alternatives, as well as risk assessment purposes. The well-established Setschenow equation can be used to determine the effect of salts on aqueous solubility. However, there is a lack of reported Setschenow constants, especially for polar organic compounds. In this study, the Setschenow constants for selected hydrophilic organic compounds were experimentally determined, and linear free energy models for predicting the Setschenow constant of organic chemicals in concentrated brines were developed. Solid phase microextraction was employed to measure the salting-out behavior of six selected hydrophilic compounds up to 5 M NaCl and 2 M CaCl 2 and in Na-Ca-Cl brines. All compounds, which include phenol, p-cresol, hydroquinone, pyrrole, hexanoic acid, and 9-hydroxyfluorene, exhibited log-linear behavior up to these concentrations, meaning Setschenow constants previously measured at low salt concentrations can be extrapolated up to high salt concentrations for hydrophilic compounds. Setschenow constants measured in NaCl and CaCl 2 brines are additive for the compounds measured here; meaning Setschenow constants measured in single salt solutions can be used in multiple salt solutions. The hydrophilic compounds in this study were selected to elucidate differences in salting-out behavior based on their chemical structure. Using data from this study, as well as literature data, linear free energy relationships (LFERs) for prediction of NaCl, CaCl 2 , LiCl, and NaBr Setschenow constants were developed and validated. Two LFERs were improved. One LFER uses the Abraham solvation parameters, which include

A model analysis of halogen kinetics: the ClOOCl catalytic cycle revisited

NASA Astrophysics Data System (ADS)

Canty, T. P.; Salawitch, R. J.; Wilmouth, D. M.

2016-12-01

We revisit prior analyses of simultaneous in situ observations of [ClO] and [ClOOCl] obtained in the Arctic polar vortex to evaluate recommended updates that govern the kinetics of the ClOOCl catalytic cycle. Available laboratory measurements of the ClOOCl absorption cross sections, the ClO+ClO reaction rate constant, and the ClO/ClOOCl equilibrium constant are considered, along with compendium evaluations of these kinetic parameters. We show that the latest recommendations for the kinetics that govern the partitioning of ClO and ClOOCl put forth by the JPL panel in Spring 2016 (JPL 15-10) are in good agreement with atmospheric observations of [ClO] and [ClOOCl]. Hence, we suggest that studies of polar ozone loss adopt these most recent recommendations. The latest JPL recommendation for the equilibrium constant suggests that ClOOCl is less stable than previously assumed, resulting in a shift in the termination temperature of polar ozone loss due to the ClOOCl catalytic cycle. Remaining uncertainties in our knowledge of the kinetics that govern the partitioning of ClO and ClOOCl within the activated vortex, and hence the efficiency of O3 loss by the ClO+ClO cycle, will be best addressed by future laboratory determinations of the absolute cross section of ClOOCl as well as measurements designed to reduce the uncertainty in the rate constant of the ClO+ClO reaction at cold temperatures characteristic of the polar, lower stratosphere.

20 Years of ClO Measurements in the Antarctic Lower Stratosphere

NASA Technical Reports Server (NTRS)

Nedoluha, Gerald E.; Connor, Brian J.; Mooney, Thomas; Barrett, James W.; Parrish, Alan; Gomez, R. Michael; Boyd, Ian; Allen, Douglas R.; Kotkamp, Michael; Kremser, Stefanie;

Ion Binding Energies Determining Functional Transport of ClC Proteins

NASA Astrophysics Data System (ADS)

Yu, Tao; Guo, Xu; Zou, Xian-Wu; Sang, Jian-Ping

2014-06-01

The ClC-type proteins, a large family of chloride transport proteins ubiquitously expressed in biological organisms, have been extensively studied for decades. Biological function of ClC proteins can be reflected by analyzing the binding situation of Cl- ions. We investigate ion binding properties of ClC-ec1 protein with the atomic molecular dynamics simulation approach. The calculated electrostatic binding energy results indicate that Cl- at the central binding site Scen has more binding stability than the internal binding site Sint. Quantitative comparison between the latest experimental heat release data isothermal titration calorimetry (ITC) and our calculated results demonstrates that chloride ions prefer to bind at Scen than Sint in the wild-type ClC-ec1 structure and prefer to bind at Sext and Scen than Sint in mutant E148A/E148Q structures. Even though the chloride ions make less contribution to heat release when binding to Sint and are relatively unstable in the Cl- pathway, they are still part contributors for the Cl- functional transport. This work provides a guide rule to estimate the importance of Cl- at the binding sites and how chloride ions have influences on the function of ClC proteins.

Electrochemical measurements of diffusion coefficients and activity coefficients for MnCl2 in molten eutectic LiCl-KCl

NASA Astrophysics Data System (ADS)

Horvath, D.; Rappleye, D.; Bagri, P.; Simpson, M. F.

2017-09-01

An electrochemical study of manganese chloride in molten salt mixtures of eutectic LiCl-KCl was carried out using a variety of electrochemical methods in a high temperature cell including cyclic voltammetry (CV), chronopotentiometry (CP), chronoamperometry (CA), and open circuit potentiometry. Single step reduction from Mn2+ to Mn(0) was observed on both W and Mo working electrodes. Using a combination of these methods, measurements were made of activity coefficient and diffusion coefficient for MnCl2 in LiCl-KCl as a function of concentration (3.54 × 10-4 to 3.60 × 10-3 mol fraction of MnCl2) at 773K. From OCP measurements, values for activity coefficient varied from 0.014 to 0.0071. Diffusion coefficients varied with concentration and differed based on measurement method (CV, CA, or CP). Based on cyclic Mn(II) ranged from 1.1 to 2.8 × 10-5 cm2/s depending on concentration.

Comparison of the catalytic activity for the Suzuki-Miyaura reaction of (η(5)-Cp)Pd(IPr)Cl with (η(3)-cinnamyl)Pd(IPr)(Cl) and (η(3)-1-t-Bu-indenyl)Pd(IPr)(Cl).

PubMed

Melvin, Patrick R; Hazari, Nilay; Lant, Hannah M C; Peczak, Ian L; Shah, Hemali P

2015-01-01

Complexes of the type (η(3)-allyl)Pd(L)(Cl) and (η(3)-indenyl)Pd(L)(Cl) are highly active precatalysts for the Suzuki-Miyaura reaction. Even though allyl and indenyl ligands are similar to cyclopentadienyl (Cp) ligands, there have been no detailed comparative studies exploring the activity of precatalysts of the type (η(5)-Cp)Pd(L)(Cl) for Suzuki-Miyaura reactions. Here, we compare the catalytic activity of (η(5)-Cp)Pd(IPr)(Cl) (IPr = 1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene, Cp) with two commercially available catalysts (η(3)-cinnamyl)Pd(IPr)(Cl) (Cin) and (η(3)-1-t-Bu-indenyl)Pd(IPr)(Cl) ( (tBu) Ind). We show that Cp gives slightly better catalytic activity than Cin, but significantly inferior activity than (tBu) Ind. This order of activity is rationalized by comparing the rates at which the precatalysts are activated to the monoligated Pd(0) active species along with the tendency of the starting precatalysts to comproportionate with monoligated Pd(0) to form inactive Pd(I) dimers. As part of this work the Cp supported Pd(I) dimer (μ-Cp)(μ-Cl)Pd2(IPr)2 (Cp (Dim) ) was synthesized and crystallographically characterized. It does not readily disproportionate to form monoligated Pd(0) and consequently Cp (Dim) is a poor catalyst for the Suzuki-Miyaura reaction.

Comparison of the catalytic activity for the Suzuki–Miyaura reaction of (η5-Cp)Pd(IPr)Cl with (η3-cinnamyl)Pd(IPr)(Cl) and (η3-1-t-Bu-indenyl)Pd(IPr)(Cl)

PubMed Central

Melvin, Patrick R; Lant, Hannah M C; Peczak, Ian L; Shah, Hemali P

2015-01-01

Summary Complexes of the type (η3-allyl)Pd(L)(Cl) and (η3-indenyl)Pd(L)(Cl) are highly active precatalysts for the Suzuki–Miyaura reaction. Even though allyl and indenyl ligands are similar to cyclopentadienyl (Cp) ligands, there have been no detailed comparative studies exploring the activity of precatalysts of the type (η5-Cp)Pd(L)(Cl) for Suzuki–Miyaura reactions. Here, we compare the catalytic activity of (η5-Cp)Pd(IPr)(Cl) (IPr = 1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene, Cp) with two commercially available catalysts (η3-cinnamyl)Pd(IPr)(Cl) (Cin) and (η3-1-t-Bu-indenyl)Pd(IPr)(Cl) (tBu Ind). We show that Cp gives slightly better catalytic activity than Cin, but significantly inferior activity than tBu Ind. This order of activity is rationalized by comparing the rates at which the precatalysts are activated to the monoligated Pd(0) active species along with the tendency of the starting precatalysts to comproportionate with monoligated Pd(0) to form inactive Pd(I) dimers. As part of this work the Cp supported Pd(I) dimer (μ-Cp)(μ-Cl)Pd2(IPr)2 (Cp Dim) was synthesized and crystallographically characterized. It does not readily disproportionate to form monoligated Pd(0) and consequently Cp Dim is a poor catalyst for the Suzuki–Miyaura reaction. PMID:26732227

Molecular identification of Leishmania spp. isolates causes cutaneous leishmaniasis (CL) in Sanliurfa Province, Turkey, where CL is highly endemic.

PubMed

Gurses, Gulcan; Ozaslan, Mehmet; Zeyrek, Fadile Yıldız; Kılıç, Ibrahim H; Doni, Nebiye Yentür; Karagöz, I Didem; Uluca, Nermin

2018-05-01

Cutaneous leishmaniasis (CL) is an important public health problem in Turkey. CL has been most frequently seen in Sanliurfa. There is an expectation of increase in the population of leishmaniasis cases with the influence of Syrian refugees arriving in Turkey. In this study we aimed to diagnosis of CL and identifying of parasite from Leishmania isolates by using ITS 1 PCR RFLP. Samples were collected from 135 CL patients in Sanliurfa. After the specimens were inoculated in medium NNN, the ones which were cultures positive were cultivated in RPMI 1640 followed by PCR-RFLP. Genomic DNA was extracted phenol-chloroform procedure. Samples were examined by using ITS 1 PCR followed by RFLP analysis. Our results indicated that two species, L. tropica (132 samples) and L. major (3 samples), are responsible for cutaneous leishmaniasis in Sanlıurfa. Our study is the first scientific study in which it is reported molecular analyses of cutaneous leishmaniasis cases caused by L. major in Sanliurfa in Southestern Anatolia Region. Because CL cases caused by L.major are detected in our study, it is considered that genotyping is important for diagnosis of Leishmania and following change of epidemiology.

Ultraviolet spectrum and chemical reactivity of the ClO dimer

NASA Technical Reports Server (NTRS)

Demore, W. B.; Tschuikow-Roux, E.

1990-01-01

The ClO dimer was prepared by photolysis (wavelength greater than 300 nm) of Cl2/Cl2O or Cl2/O3 mixtures or by photolysis of Cl2O alone. Temperatures were in the range 195-217 K, and experiments were carried out both in the gas phase and in the cryogenic solvents CF4, CO2, and N2O. Dimer cross sections in the range 190-400 nm are reported both in the gas phase and in the solvents. Results indicate that ClOOCl is the only dimer structure formed as a stable product. Upper limits of 1 x 10 to the -19th and 1 x 10 to the -20th cu cm/s are placed on the reactions of ClOOCl with O3 and with itself, respectively.

Temperature dependence of fluorescence for EuCl3 in LiCl-KCl eutectic melt.

PubMed

Im, Hee-Jung; Kim, Tack-Jin; Song, Kyuseok

2010-08-15

The fluorescence of EuCl(3) in LiCl-KCl eutectic melt according to temperature changes was investigated, and the spontaneous partial reduction of Eu(3+) to Eu(2+) at high temperature was confirmed by the fluorescence results. The fluorescence decreases when the temperature increases, and this was examined in detail. The studies of fluorescence provided information regarding the chemical and physical behavior of europium ions in the molten salt according to the temperature changes. It is applicable for monitoring species and concentrations and estimating the approximate chemical structure of the ions in molten salts. Copyright 2010 Elsevier B.V. All rights reserved.

Fourier transform microwave spectroscopy of the SiCl+ ion

NASA Astrophysics Data System (ADS)

Tanaka, Keiichi; Harada, Kensuke; Cabezas, Carlos; Endo, Yasuki

2018-03-01

Fourier transform microwave spectra for the J = 1 ← 0 and 2 ← 1 rotational transitions of the SiCl+ ion were observed for two isotopologues (35 Cl and 37 Cl) in the ground and the first excited vibrational states of the ground 1Σ+ electronic state. Thanks to the high resolution of the FTMW spectrometer, hyperfine structures due to the quadrupole moment of the chlorine nucleus and the nuclear spin-rotation interaction were fully resolved. The observed FTMW spectra were combined with previously reported MMW and diode laser spectra in an analysis to determine the mass-independent Dunham coefficients Uk,l as well as a mass scaling parameter Δ01Cl = - 0.856 (30) . The equilibrium bond length of SiCl+ determined is re = 1.9439729 (10) Å and the nuclear quadrupole coupling constant of Si35 Cl+ is eQqe = - 11.8788 (23) MHz.

Solubility relations in the ternary system NaCl-CsCl-H2O at 1 atm. 1. Solubilities of halite from 20 to 100 °C

USGS Publications Warehouse

Chou, I.-Ming; Lee, R.D.

1983-01-01

Solubilities of halite in the ternary system NaCl-CsCl-H2O have been determined by the visual polythermal method at 1 atm from 20 to 100??C along five constant CsCl/(CsCl + H2O) weight ratio lines. These five constant weight ratios are 0.1, 0.2, 0.3, 0.4, and 0.5. The maximum uncertainties in these measurements are ??0.02 wt % NaCl and ??0.15??C. The data along each constant CsCl/(CsCl + H2O) weight ratio line were regressed to a smooth curve. The maximum deviation of the measured solubilities from the smooth curves is 0.06 wt % NaCl. Isothermal solubilities of halite were calculated from smoothed curves at 25, 50, and 75??C.

Electron scattering in graphene with adsorbed NaCl nanoparticles

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

Drabińska, Aneta, E-mail: Aneta.Drabinska@fuw.edu.pl; Kaźmierczak, Piotr; Bożek, Rafał

2015-01-07

In this work, the results of contactless magnetoconductance and Raman spectroscopy measurements performed for a graphene sample after its immersion in NaCl solution were presented. The properties of the immersed sample were compared with those of a non-immersed reference sample. Atomic force microscopy and electron spin resonance experiments confirmed the deposition of NaCl nanoparticles on the graphene surface. A weak localization signal observed using contactless magnetoconductance showed the reduction of the coherence length after NaCl treatment of graphene. Temperature dependence of the coherence length indicated a change from ballistic to diffusive regime in electron transport after NaCl treatment. The mainmore » inelastic scattering process was of the electron-electron type but the major reason for the reduction of the coherence length at low temperatures was additional, temperature independent, inelastic scattering. We associate it with spin flip scattering, caused by NaCl nanoparticles present on the graphene surface. Raman spectroscopy showed an increase in the D and D′ bands intensities for graphene after its immersion in NaCl solution. An analysis of the D, D′, and G bands intensities proved that this additional scattering is related to the decoration of vacancies and grain boundaries with NaCl nanoparticles, as well as generation of new on-site defects as a result of the decoration of the graphene surface with NaCl nanoparticles. The observed energy shifts of 2D and G bands indicated that NaCl deposition on the graphene surface did not change carrier concentration, but reduced compressive biaxial strain in the graphene layer.« less

Gene expression profiles in the bovine corpus luteum (CL) during the estrous cycle and pregnancy: Possible roles of chemokines in regulating CL function during pregnancy

PubMed Central

SAKUMOTO, Ryosuke; HAYASHI, Ken-Go; HOSOE, Misa; IGA, Kosuke; KIZAKI, Keiichiro; OKUDA, Kiyoshi

2014-01-01

To determine functional differences between the corpus luteum (CL) of the estrous cycle and pregnancy in cows, gene expression profiles were compared using a 15 K bovine oligo DNA microarray. In the pregnant CL at days 20–25, 40–45 and 150–160, the expressions of 138, 265 and 455 genes differed by a factor of > 2-fold (P < 0.05) from their expressions in the cyclic CL (days 10–12 of the estrous cycle). Messenger RNA expressions of chemokines (eotaxin, lymphotactin and ENA-78) and their receptors (CCR3, XCR1 and CXCR2) were validated by quantitative real-time PCR. Transcripts of eotaxin were more abundant in the CL at days 40–45 and 150–160 of pregnancy than in the cyclic CL (P < 0.01). In contrast, the mRNA expressions of lymphotactin, ENA-78 and XCR1 were lower in the CL of pregnancy (P < 0.05). Messenger RNAs of CCR3 and CXCR2 were similarly detected both in the cyclic and pregnant CL. Tissue protein levels of eotaxin were significantly higher in the CL at days 150–160 of pregnancy than in the CL at other stages, whereas the lymphotactin protein levels in the CL at days 20–25 of pregnancy were lower (P < 0.05). Immunohistochemical staining showed that CCR3 was expressed in the luteal cells and that XCR1 was expressed in both the luteal cells and endothelial cells. Collectively, the different gene expression profiles may contribute to functional differences between the cyclic and pregnant CL, and chemokines including eotaxin and lymphotactin may regulate CL function during pregnancy in cows. PMID:25382605

Ab initio characterization of ClOOH - Implications for atmospheric chemistry

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Rendell, Alistair P.

1993-01-01

The equilibrium structure, dipole moment, harmonic vibrational frequencies, and infrared intensities of ClOOH are determined using the CCSD(T) (singles and doubles coupled-cluster theory plus a perturbational estimate of the effects of connected triple excitations) electronic structure method in conjunction with a TZ2P (triple xi plus double polarization) basis set. The heat of formation of CIOOH is determined (using two different isodesmic reactions) to be +1.5 +/- 1 kcal/mol at 0 K or +0.2 +/- 1 kcal/mol at 298.15 K. Using the computed heat of formation, we examined the stability of ClOOH with respect to the ClO + OH, ClOO + H, and HOO + Cl dissociation limits. Since ClOOH is found to be quite stable, it is argued that the chemistry of ClOOH should be included in any accurate modeling of the stratosphere.

High-Order Ca(II)-Chloro Complexes in Mixed CaCl2-LiCl Aqueous Solution: Insights from Density Functional Theory and Molecular Dynamics Simulations.

PubMed

Wang, Yu-Lin; Wang, Ying; Yi, Hai-Bo

2016-07-21

In this study, the structural characteristics of high-coordinated Ca-Cl complexes present in mixed CaCl2-LiCl aqueous solution were investigated using density functional theory (DFT) and molecular dynamics (MD) simulations. The DFT results show that [CaClx](2-x) (x = 4-6) clusters are quite unstable in the gas phase, but these clusters become metastable when hydration is considered. The MD simulations show that high-coordinated Ca-chloro complexes are possible transient species that exist for up to nanoseconds in concentrated (11.10 mol·kg(-1)) Cl(-) solution at 273 and 298 K. As the temperature increases to 423 K, these high-coordinated structures tend to disassociate and convert into smaller clusters and single free ions. The presence of high-order Ca-Cl species in concentrated LiCl solution can be attributed to their enhanced hydration shell and the inadequate hydration of ions. The probability of the [CaClx](2-x)aq (x = 4-6) species being present in concentrated LiCl solution decreases greatly with increasing temperature, which also indicates that the formation of the high-coordinated Ca-Cl structure is related to its hydration characteristics.

Stable isotope analyses of oxygen (18O:17O:16O) and chlorine (37Cl:35Cl) in perchlorate: reference materials, calibrations, methods, and interferences

USGS Publications Warehouse

Böhlke, John Karl; Mroczkowski, Stanley J.; Sturchio, Neil C.; Heraty, Linnea J.; Richman, Kent W.; Sullivan, Donald B.; Griffith, Kris N.; Gu, Baohua; Hatzinger, Paul B.

2017-01-01

RationalePerchlorate (ClO4−) is a common trace constituent of water, soils, and plants; it has both natural and synthetic sources and is subject to biodegradation. The stable isotope ratios of Cl and O provide three independent quantities for ClO4− source attribution and natural attenuation studies: δ37Cl, δ18O, and δ17O (or Δ17O or 17Δ) values. Documented reference materials, calibration schemes, methods, and interferences will improve the reliability of such studies.MethodsThree large batches of KClO4 with contrasting isotopic compositions were synthesized and analyzed against VSMOW-SLAP, atmospheric O2, and international nitrate and chloride reference materials. Three analytical methods were tested for O isotopes: conversion of ClO4− to CO for continuous-flow IRMS (CO-CFIRMS), decomposition to O2 for dual-inlet IRMS (O2-DIIRMS), and decomposition to O2 with molecular-sieve trap (O2-DIIRMS+T). For Cl isotopes, KCl produced by thermal decomposition of KClO4 was reprecipitated as AgCl and converted into CH3Cl for DIIRMS.ResultsKClO4 isotopic reference materials (USGS37, USGS38, USGS39) represent a wide range of Cl and O isotopic compositions, including non-mass-dependent O isotopic variation. Isotopic fractionation and exchange can affect O isotope analyses of ClO4− depending on the decomposition method. Routine analyses can be adjusted for such effects by normalization, using reference materials prepared and analyzed as samples. Analytical errors caused by SO42−, NO3−, ReO42−, and C-bearing contaminants include isotope mixing and fractionation effects on CO and O2, plus direct interference from CO2 in the mass spectrometer. The results highlight the importance of effective purification of ClO4− from environmental samples.ConclusionsKClO4 reference materials are available for testing methods and calibrating isotopic data for ClO4− and other substances with widely varying Cl or O isotopic compositions. Current ClO4−extraction, purification

Diphosphine- and CO-Induced Fragmentation of Chloride-bridged Dinuclear Complex and Cp*Ir(mu-Cl)(3)Re(CO)(3) and Attempted Synthesis of Cp*Ir(mu-Cl)(3)Mn(CO)(3): Spectroscopic Data and X-ray Diffraction Structures of the Pentamethylcyclopentadienyl Compounds [Cp*IrCl{(Z)-Ph2PCH = CHPPh2}][Cl]center dot 2CHCl(3) and Cp*Ir(CO)Cl-2

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

Hammons, Casey; Wang, Xiaoping; Nesterov, Vladimir

2010-01-01

The confacial bioctahedral compound Cp*Ir(mu-Cl)(3)Re(CO)(3) (1) undergoes rapid fragmentation in the presence of the unsaturated diphosphine ligand (Z)-Ph2PCH = CHPPh2 to give the mononuclear compounds [Cp*IrCl {(Z)-Ph2PCH = CHPPh2}][Cl] (2) and fac-ClRe(CO)(3)[(Z)-Ph2PCH = CHPPh2] (3). 2 has been characterized by H-1 and P-31 NMR spectroscopy and X-ray diffraction analysis. 2 center dot 2CHCl(3) crystallizes in the monoclinic space group C2/c, a = 35.023 (8) angstrom, b = 10.189 (2) angstrom, c = 24.003 (6) angstrom, b = 103.340 (3), V = 8,335 (3) angstrom 3, Z = 8, and d(calc) = 1.647 Mg/m(3); R = 0.0383, R-w = 0.1135 formore » 8,178 reflections with I> 2 sigma(I). The Ir(III) center in 2 exhibits a six-coordinate geometry and displays a chelating diphosphine group. Compound 1 reacts with added CO with fragmentation to yield the known compounds Cp*Ir(CO)Cl-2 (4) and ClRe(CO)(5) (5) in near quantitative yield by IR spectroscopy. Using the protocol established by our groups for the synthesis of 1, we have explored the reaction of [Cp*IrCl2](2) with ClMn(CO)(5) as a potential route to Cp*Ir(mu-Cl)(3)Mn(CO)(3); unfortunately, 4 was the only product isolated from this reaction. The solid-state structure of 4 was determined by X-ray diffraction analysis. 4 crystallizes in the triclinic space group P-1, a = 7.4059 (4) angstrom, b = 7.8940 (4) angstrom, c = 11.8488 (7) angstrom, alpha = 80.020 (1), beta = 79.758 (1), gamma = 68.631 (1), V = 630.34 (6) angstrom(3), Z = 2, and d(calc) = 2.246 Mg/m(3); R = 0.0126, R-w = 0.0329 for 2,754 reflections with I> 2 sigma(I). The expected three-legged piano-stool geometry in 4 has been crystallographically confirmed.« less

First-Principles Study of Chemical Mixtures of CaCl2 and MgCl2 Hydrates for Optimized Seasonal Heat Storage

PubMed Central

2017-01-01

Chloride-based salt hydrates form a promising class of thermochemical materials (TCMs), having high storage capacity and fast kinetics. In the charging cycles of these hydrates however hydrolysis might appear along with dehydration. The HCl produced during the hydrolysis degrades and corrodes the storage system. Our GGA-DFT results show that the enthalpy charge during proton formation (an important step in hydrolysis) is much higher for CaCl2·2H2O (33.75 kcal/mol) than for MgCl2·2H2O (19.55 kcal/mol). This is a strong indicator that hydrolysis can be minimized by appropriate chemical mixing of CaCl2 and Mg Cl2 hydrates, which is also confirmed by recent experimental studies. GGA-DFT calculations were performed to obtain and analyze the optimized structures, charge distributions, bonding indicators and harmonic frequencies of various chemical mixtures hydrates and compared them to their elementary salts hydrates. We have further assessed the equilibrium products concentration of dehydration/hydrolysis of the chemical mixtures under a wide range of operating conditions. We observed that chemical mixing leads to an increase of the onset hydrolysis temperature with a maximum value of 79 K, thus increasing the resistance against hydrolysis with respect to the elementary salt hydrates. We also found that the chemical mixing of CaCl2 and MgCl2 hydrates widens the operating dehydration temperature range by a maximum value of 182 K (CaMg2Cl6·2H2O) and lowers the binding enthalpy with respect to the physical mixture by ≈65 kcal/mol for TCM based heat storage systems. PMID:28983386

NaCl intake and preference threshold of spontaneously hypertensive rats.

PubMed

Fregly, M J

1975-09-01

Both male and female spontaneously hypertensive (SH) rats have an appetite for NaCl solution. The appetite is present when a choice is offered between distilled water and either isotonic or hypertonic (0.25 M) NaCl solution to drink. Total fluid intake (water plus NaCl solution) was greater for SH rats than for controls while food intakes (g/100 g body wt/day) of SH rats were not different from controls. Mean body weight of SH rats was always less than that of controls. The appetite for NaCl solution was accompanied by a significant reduction in preference (detection) threshold. SH rats could detect the difference between distilled water and NaCl solution when the concentration of the latter was 12 mEq/liter compared to a control threshold of 30 mEq/liter. The NaCl appetite and reduced NaCl preference threshold induced by spontaneous hypertension is in marked contrast to the NaCl aversion induced by other types of experimentally induced hypertension in rats. The mechanism or mechanisms responsible for these differences remain for further study.

Vertical profiles of ClNO2 measured in Utah: dry deposition of N2O5 as a source of ClNO2

NASA Astrophysics Data System (ADS)

McLaren, Robert; Roberts, James M.; Kercher, James P.; Thornton, Joel A.; Brown, Steven S.; Edwards, Peter M.; Young, Cora Y.; Dube, William P.; Washenfelder, Rebecca A.; Williams, Eric J.; Holloway, John S.; Bates, Timothy S.; Quinn, Patricia K.

2013-04-01

Several recent observations of nitryl chloride (ClNO2) have suggested that this compound can accumulate to significant levels (several ppb) in the nocturnal boundary layer at night. Its photolytic loss the next day can be a significant source of chlorine atom radicals. The source of ClNO2 is known to be the heterogeneous reaction of N2O5 with aerosol chloride, not just confined to coastal regions but also observed thousands of kilometers inland in urban areas. During the Uintah Basin Winter Ozone Study (2012), we made measurements of ClNO2 by CIMS on a tower in a remote region of Utah where intensive natural gas extraction operations via hydraulic fracturing were occurring. Levels of ClNO2 were surprisingly high at night (up to 2 ppb) even though coastal aerosols were not present. Soils in the region were alkaline with high chloride content. To address the potential of N2O5 dry deposition as a source of ClNO2, we measured vertical profiles of ClNO2 from 1 to 12 m agl with a movable inlet. We observed negative gradients of ClNO2 and positive gradients of N2O5, which suggest that dry deposition of N2O5 and reaction with soil chloride as a source of ClNO2.

Chlorination of UO 2, PuO 2 and rare earth oxides using ZrCl 4 in LiCl-KCl eutectic melt

NASA Astrophysics Data System (ADS)

Sakamura, Yoshiharu; Inoue, Tadashi; Iwai, Takashi; Moriyama, Hirotake

2005-04-01

A new chlorination method using ZrCl 4 in a molten salt bath has been investigated for the pyrometallurgical reprocessing of nuclear fuels. ZrCl 4 has a high reactivity with oxygen but is not corrosive to refractory metals such as steel. Rare earth oxides (La 2O 3, CeO 2, Nd 2O 3 and Y 2O 3) and actinide oxides (UO 2 and PuO 2) were allowed to react with ZrCl 4 in a LiCl-KCl eutectic salt at 773 K to give a metal chloride solution and a precipitate of ZrO 2. An addition of zirconium metal as a reductant was effective in chlorinating the dioxides. When the oxides were in powder form, the reaction was observed to progress rapidly. Cyclic voltammetry provided a convenient way of establishing when the reaction was completed. It was demonstrated that the ZrCl 4 chlorination method, free from corrosive gas, was very simple and useful.

Re-evaluation of colorimetric Cl- data from natural waters with DOC

USGS Publications Warehouse

Norton, S.A.; Handlet, M.J.; Kahl, J.S.; Peters, N.E.

1996-01-01

Colorimetric Cl- data from natural solutions that contain dissolved organic carbon (DOC) may be biased high. We evaluated aquatic Cl- concentrations in ecosystem compartments at the Bear Brook Watershed, Maine, and from lakes in Maine, using ion chromatography and colorimetry. DOC imparts a positive interference on colorimetric Cl- results proportional to DOC concentrations at approximately 0.8 ??eq Cl-/L per mg DOC/L. The interference is not a function of Cl- concentration. The resulting bias in concentrations of Cl- may be 50% or more of typical environmental values for Cl- in areas remote from atmospheric deposition of marine aerosols. Such biased data in the literature appear to have led to spurious conclusions about recycling of Cl- by forests, the usefulness of Cl- as a conservative tracer in watershed studies, and calculations of elemental budgets, ion balance, charge density of DOC, and dry deposition factors.

Improved process for generating ClF/sub 3/ from ClF and F/sub 2/

DOEpatents

Reiner, R.H.; Pashley, J.H.; Barber, E.J.

The invention is an improvement in the process for producing gaseous ClF/sub 3/ by reacting ClF and F/sub 2/ at elevated temperature. The improved process comprises conducting the reaction in the presence of NiF/sub 2/, which preferably is in the form of particles or in the form of a film or layer on a particulate substrate. The nickel fluoride acts as a reaction catalyst, significantly increasing the reaction rate and thus permitting valuable reductions in process temperature, pressure, and/or reactor volume.

Electron-impact ionization of silicon tetrachloride (SiCl4).

PubMed

Basner, R; Gutkin, M; Mahoney, J; Tarnovsky, V; Deutsch, H; Becker, K

2005-08-01

We measured absolute partial cross sections for the formation of various singly charged and doubly charged positive ions produced by electron impact on silicon tetrachloride (SiCl4) using two different experimental techniques, a time-of-flight mass spectrometer (TOF-MS) and a fast-neutral-beam apparatus. The energy range covered was from the threshold to 900 eV in the TOF-MS and to 200 eV in the fast-neutral-beam apparatus. The results obtained by the two different experimental techniques were found to agree very well (better than their combined margins of error). The SiCl3(+) fragment ion has the largest partial ionization cross section with a maximum value of slightly above 6x10(-20) m2 at about 100 eV. The cross sections for the formation of SiCl4(+), SiCl+, and Cl+ have maximum values around 4x10(-20) m2. Some of the cross-section curves exhibit an unusual energy dependence with a pronounced low-energy maximum at an energy around 30 eV followed by a broad second maximum at around 100 eV. This is similar to what has been observed by us earlier for another Cl-containing molecule, TiCl4 [R. Basner, M. Schmidt, V. Tamovsky, H. Deutsch, and K. Becker, Thin Solid Films 374 291 (2000)]. The maximum cross-section values for the formation of the doubly charged ions, with the exception of SiCl3(++), are 0.05x10(-20) m2 or less. The experimentally determined total single ionization cross section of SiCl4 is compared with the results of semiempirical calculations.

Application of Liquid Paraffin in Castable CL-20-Based PBX

NASA Astrophysics Data System (ADS)

Zhang, Pu; Guo, Xue-Yong; Zhang, Jing-Yuan; Jiao, Qing-Jie

2014-10-01

Hydroxy-terminated polybutadiene (HTPB)/CL-20 castable explosives plasticized with liquid paraffin were processed successfully by a cast-curing method. The compatibility of liquid paraffin with CL-20, influence of liquid paraffin on CL-20 phase transition, and viscosity of the cast mixture were tested and analyzed. The thermal decomposition characteristics, thermal stability, mechanical sensitivity, and velocity of detonation (VOD) of the HTPB/CL-20 plastic-bonded explosives (PBXs) were also measured. The experimental results showed that liquid paraffin was well compatible with CL-20, and it did not have a distinct effect on the ɛ- to γ-phase transition of CL-20. In addition, the casting mixture was free-flowing with sufficiently low viscosity. When the content of CL-20 is 90% by weight, the measured VOD reached 8,775 m/s (density of 1.78 g/cm3), and the PBXs exhibited moderate mechanical sensitivity and good thermal stability.

Spectroscopic study of the charge-transfer complexes TiCl4/styrene and TiCl4/polystyrene

NASA Astrophysics Data System (ADS)

Gonçalves, Norberto S.; Noda, Lúcia. K.

2017-10-01

In this work, solutions of TiCl4/styrene and TiCl4/polystyrene charge-transfer complexes in CHCl3 or CDCl3 were investigated by UV-vis, resonance Raman and 1H NMR spectroscopies in order to study their molecular and electronic structures. Both show a yellow colour due to absorption in the 400 nm region, related to a charge-transfer transition. In Raman spectra, as the excitation approaches the resonance region, the primary enhancement of aromatic ring modes was mainly observed, rather than intensification of the vinylic double-bond stretch. Under the experimental conditions it was observed that formation of polystyrene takes place, as showed by 1H NMR spectra, and the most significant interaction occurs at the aromatic ring, as supported by the results from interaction of TiCl4 with polystyrene, as indicated by the charge-transfer band and resonant intensification of the aromatic ring modes.

Physiology and pathophysiology of ClC-K/barttin channels.

PubMed

Fahlke, Christoph; Fischer, Martin

2010-01-01

ClC-K channels form a subgroup of anion channels within the ClC family of anion transport proteins. They are expressed predominantly in the kidney and in the inner ear, and are necessary for NaCl resorption in the loop of Henle and for K+ secretion by the stria vascularis. Subcellular distribution as well as the function of these channels are tightly regulated by an accessory subunit, barttin. Barttin improves the stability of ClC-K channel protein, stimulates the exit from the endoplasmic reticulum and insertion into the plasma membrane and changes its function by modifying voltage-dependent gating processes. The importance of ClC-K/barttin channels is highlighted by several genetic diseases. Dysfunctions of ClC-K channels result in Bartter syndrome, an inherited human condition characterized by impaired urinary concentration. Mutations in the gene encoding barttin, BSND, affect the urinary concentration as well as the sensory function of the inner ear. Surprisingly, there is one BSND mutation that causes deafness without affecting renal function, indicating that kidney function tolerates a reduction of anion channel activity that is not sufficient to support normal signal transduction in inner hair cells. This review summarizes recent work on molecular mechanisms, physiology, and pathophysiology of ClC-K/barttin channels.

Ion-binding properties of the ClC chloride selectivity filter

PubMed Central

Lobet, Séverine; Dutzler, Raimund

2006-01-01

The ClC channels are members of a large protein family of chloride (Cl−) channels and secondary active Cl− transporters. Despite their diverse functions, the transmembrane architecture within the family is conserved. Here we present a crystallographic study on the ion-binding properties of the ClC selectivity filter in the close homolog from Escherichia coli (EcClC). The ClC selectivity filter contains three ion-binding sites that bridge the extra- and intracellular solutions. The sites bind Cl− ions with mM affinity. Despite their close proximity within the filter, the three sites can be occupied simultaneously. The ion-binding properties are found conserved from the bacterial transporter EcClC to the human Cl− channel ClC-1, suggesting a close functional link between ion permeation in the channels and active transport in the transporters. In resemblance to K+ channels, ions permeate the ClC channel in a single file, with mutual repulsion between the ions fostering rapid conduction. PMID:16341087

PbCl2-tuned inorganic cubic CsPbBr3(Cl) perovskite solar cells with enhanced electron lifetime, diffusion length and photovoltaic performance

NASA Astrophysics Data System (ADS)

Li, Bo; Zhang, Yanan; Zhang, Luyuan; Yin, Longwei

2017-08-01

Inorganic CsPbBr3 perovskite is arousing great interest following after organic-inorganic hybrid halide perovskites, and is found as a good candidate for photovoltaic devices for its prominent photoelectric property and stability. Herein, we for the first time report on PbCl2-tuned inorganic Cl-doped CsPbBr3(Cl) perovskite solar cells with adjustable crystal structure and Cl doping for enhanced carrier lifetime, extraction rate and photovoltaic performance. The effect of PbCl2 on the morphologies, structures, optical, and photovoltaic performance of CsPbBr3 perovskite solar cells is investigated systemically. Compared with orthorhombic CsPbBr3, cubic CsPbBr3 demonstrates a significant improvement for electron lifetime (from 6.7 ns to 12.3 ns) and diffusion length (from 69 nm to 197 nm), as well as the enhanced electron extraction rate from CsPbBr3 to TiO2. More importantly, Cl doping benefits the further enhancement of carrier lifetime (14.3 ns) and diffusion length (208 nm). The Cl doped cubic CsPbBr3(Cl) perovskite solar cell exhibits a Jsc of 8.47 mA cm-2 and a PCE of 6.21%, superior to that of pure orthorhombic CsPbBr3 (6.22 mA cm-2 and 3.78%). The improvement of photovoltaic performance can be attributed to enhanced carrier lifetime, diffusion length and extraction rates, as well as suppressed nonradiative recombination.

The Crystal Structure of Ba 17Sm 10Cl 64

NASA Astrophysics Data System (ADS)

Liu, Guo; Eick, Harry A.

1999-08-01

The structure of Ba17Sm10Cl64, prepared by solvolytic extraction of a program-cooled 1:1 BaCl2:SmCl3 molar mixture sealed in a quartz tube and heated to 750°C, was determined from single-crystal X-ray diffraction data. The compound exhibits cubic symmetry, space group Pa3 (No. 205) with a=21.366(2) Å and Z=4. Refinement effected with I>2σ(I) yielded R1= 0.0926 and wR2=0.216. One Ba atom is 12-coordinated by Cl atoms in a distorted icosahedral arrangement; the three other Ba atoms are 10-coordinated in a distorted bicapped cubic arrangement. There are two Sm atom sites. The coordination around one Sm atom is best described as square antiprismatic, but one Sm-Cl distance is too long for effective bonding. The other Sm atom site, occupied statistically by {1}/{3}Ba and {2}/{3}Sm atoms, is 9-coordinated by Cl atoms in a monocapped square antiprismatic arrangement. The two types of Sm sites combine to form an M6Cl37 cuboctahedral cluster of the composition BaSm5Cl37. It is shown that the cβ phase identified previously in the Yb-F and related fluoride systems is probably isostructural with Ba17Sm10Cl64.

Characterization and identification of Na-Cl sources in ground water

USGS Publications Warehouse

Panno, S.V.; Hackley, Keith C.; Hwang, H.-H.; Greenberg, S.E.; Krapac, I.G.; Landsberger, S.; O'Kelly, D. J.

2006-01-01

Elevated concentrations of sodium (Na+) and chloride (Cl -) in surface and ground water are common in the United States and other countries, and can serve as indicators of, or may constitute, a water quality problem. We have characterized the most prevalent natural and anthropogenic sources of Na+ and Cl- in ground water, primarily in Illinois, and explored techniques that could be used to identify their source. We considered seven potential sources that included agricultural chemicals, septic effluent, animal waste, municipal landfill leachate, sea water, basin brines, and road deicers. The halides Cl-, bromide (Br-), and iodide (I-) were useful indicators of the sources of Na+-Cl- contamination. Iodide enrichment (relative to Cl-) was greatest in precipitation, followed by uncontaminated soil water and ground water, and landfill leachate. The mass ratios of the halides among themselves, with total nitrogen (N), and with Na+ provided diagnostic methods for graphically distinguishing among sources of Na+ and Cl- in contaminated water. Cl/Br ratios relative to Cl- revealed a clear, although overlapping, separation of sample groups. Samples of landfill leachate and ground water known to be contaminated by leachate were enriched in I- and Br-; this provided an excellent fingerprint for identifying leachate contamination. In addition, total N, when plotted against Cl/Br ratios, successfully separated water contaminated by road salt from water contaminated by other sources. Copyright ?? 2005 National Ground Water Association.

Stable Cl isotope composition of the Changjiang River water

NASA Astrophysics Data System (ADS)

Lang, Y.; Liu, C. Q.; LI, S. L.; Aravena, R.; Ding, H.; WANG, B.; Benjamin, C.

2017-12-01

To understand chemical wreathing, nutrient cycling, and the impact of human activities on eco-environments of the Changjiang River (Yangtze River) Basin, we carried out a geochemical study on water chemistry and multiple isotopes (C, N, S, Sr…...) of Changjiang River water in the summer season. Some of the research results about the water chemistry, boron isotope geochemistry and suspended matter have been published (Chetelat et al., 2008; Li et al., 2010). Ten samples were selected for the measurement of δ37Cl values, among which 7 samples were collected from main stream and 3 samples from tributaries. The range of δ37Cl values varies between 0.02‰ and 0.33‰ in the main stream and between 0.16‰ and 0.71‰ in the tributary waters. The δ37Cl values in general are negatively correlated with Cl- concentrations for both main stream and tributary waters. δ37Cl value of Wujiang, which is one of the large tributaries in the upper reach of Changjiang and dominated by carbonate rocks in lithology of the watershed, has the maximum value but minimum value of Cl- concentration in this study. The lowest δ37Cl value was measured for the water collected from the estuary of Changjiang River. The variation of δ37Cl values in the waters would be attributed to mixing of different sources of chlorine, which most likely include rain water, ground water, seawater, and pollutants. Systematic characterization of different Cl sources in terms of their chlorine isotope composition is imperative for better understanding of sources and processes of chlorine cycling. Acknowledgements: This work was financially supported by NSFC through project 41073099. (Omit references)

37Cl/35Cl isotope ratio analysis in perchlorate by ion chromatography/multi collector -ICPMS: Analytical performance and implication for biodegradation studies.

PubMed

Zakon, Yevgeni; Ronen, Zeev; Halicz, Ludwik; Gelman, Faina

2017-10-01

In the present study we propose a new analytical method for 37 Cl/ 35 Cl analysis in perchlorate by Ion Chromatography(IC) coupled to Multicollector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS). The accuracy of the analytical method was validated by analysis of international perchlorate standard materials USGS-37 and USGS -38; analytical precision better than ±0.4‰ was achieved. 37 Cl/ 35 Cl isotope ratio analysis in perchlorate during laboratory biodegradation experiment with microbial cultures enriched from the contaminated soil in Israel resulted in isotope enrichment factor ε 37 Cl = -13.3 ± 1‰, which falls in the range reported previously for perchlorate biodegradation by pure microbial cultures. The proposed analytical method may significantly simplify the procedure for isotope analysis of perchlorate which is currently applied in environmental studies. Copyright © 2017. Published by Elsevier Ltd.

20 years of ClO measurements in the Antarctic lower stratosphere

NASA Astrophysics Data System (ADS)

Nedoluha, Gerald E.; Connor, Brian J.; Mooney, Thomas; Barrett, James W.; Parrish, Alan; Gomez, R. Michael; Boyd, Ian; Allen, Douglas R.; Kotkamp, Michael; Kremser, Stefanie; Deshler, Terry; Newman, Paul; Santee, Michelle L.

2016-08-01

We present 20 years (1996-2015) of austral springtime measurements of chlorine monoxide (ClO) over Antarctica from the Chlorine Oxide Experiment (ChlOE1) ground-based millimeter wave spectrometer at Scott Base, Antarctica, as well 12 years (2004-2015) of ClO measurements from the Aura Microwave Limb Sounder (MLS). From August onwards we observe a strong increase in lower stratospheric ClO, with a peak column amount usually occurring in early September. From mid-September onwards we observe a strong decrease in ClO. In order to study interannual differences, we focus on a 3-week period from 28 August to 17 September for each year and compare the average column ClO anomalies. These column ClO anomalies are shown to be highly correlated with the average ozone mass deficit for September and October of each year. We also show that anomalies in column ClO are strongly anti-correlated with 30 hPa temperature anomalies, both on a daily and an interannual timescale. Making use of this anti-correlation we calculate the linear dependence of the interannual variations in column ClO on interannual variations in temperature. By making use of this relationship, we can better estimate the underlying trend in the total chlorine (Cly = HCl + ClONO2 + HOCl + 2 × Cl2 + 2 × Cl2O2 + ClO + Cl). The resultant trends in Cly, which determine the long-term trend in ClO, are estimated to be -0.5 ± 0.2, -1.4 ± 0.9, and -0.6 ± 0.4 % year-1, for zonal MLS, Scott Base MLS (both 2004-2015), and ChlOE (1996-2015) respectively. These trends are within 1σ of trends in stratospheric Cly previously found at other latitudes. The decrease in ClO is consistent with the trend expected from regulations enacted under the Montreal Protocol.

A Convenient, TiCl4/SnCl4-Mediated Synthesis of N-Phenyl or N-Aryl Benzamidines and N-Phenylpicolinamidines

PubMed Central

Patil, Umesh D.; Mahulikar, Pramod P.

2012-01-01

A new, TiCl4-or SnCl4-mediated, solvent-free method was developed for the synthesis of N-Aryl benzamidines and N-phenylpicolinamidines, in moderate-to-good yield, using suitable amines and nitriles as starting materials. PMID:24052858

Electrochemical characterisation of CaCl2 deficient LiCl-KCl-CaCl2 eutectic melt and electro-deoxidation of solid UO2

NASA Astrophysics Data System (ADS)

Sri Maha Vishnu, D.; Sanil, N.; Mohandas, K. S.; Nagarajan, K.

2016-03-01

The CaCl2 deficient ternary eutectic melt LiCl-KCl-CaCl2 (50.5: 44.2: 5.3 mol %) was electrochemically characterised by cyclic voltammetry and polarization techniques in the context of its probable use as the electrolyte in the electrochemical reduction of solid UO2 to uranium metal. Tungsten (cathodic polarization) and graphite (anodic polarization) working electrodes were used in these studies carried out in the temperature range 623 K-923 K. The cathodic limit of the melt was observed to be set by the deposition of Ca2+ ions followed by Li+ ions on the tungsten electrode and the anodic limit by oxidation of chloride ions on the graphite electrode (chlorine evolution). The difference between the onset potential of deposition of Ca2+ and Li+ was found to be 0.241 V at a scan rate of 20 mV/s at 623 K and the difference decreased with increase in temperature and vanished at 923 K. Polarization measurements with stainless steel (SS) cathode and graphite anode at 673 K showed the possibility of low-energy reactions occurring on the UO2 electrode in the melt. UO2 pellets were cathodically polarized at 3.9 V for 25 h to test the feasibility of electro-reduction to uranium in the melt. The surface of the pellets was found reduced to U metal.

Chemical Analysis through CL-Detection Assisted by Periodate Oxidation

PubMed Central

Evmiridis, Nicholaos P.; Vlessidis, Athanasios G.; Thanasoulias, Nicholas C.

2007-01-01

The progress of the research work of the author and his colleagues on the field of CL-emission generated by pyrogallol oxidation and further application for the direct determination of periodate and indirect or direct determination of other compounds through flow-injection manifold/CL-detection set up is described. The instrumentation used for these studies was a simple flow-injection manifold that provides good reproducibility, coupled to a red sensitive photomultiplier that gives sensitive CL-detection. In addition, recent reports on studies and analytical methods based on CL-emission generated by periodate oxidation by other authors are included. PMID:17611611

A laboratory study of the UV Absorption Spectrum of the ClO Dimer (Cl2O2) and the Implications for Polar Stratospheric Ozone Depletion

NASA Astrophysics Data System (ADS)

Papanastasiou, D. K.; Papadimitriou, V. C.; Fahey, D. W.; Burkholder, J. B.

2009-12-01

Chlorine containing species play an important role in catalytic ozone depleting cycles in the Antarctic and Arctic stratosphere. The ClO dimer (Cl2O2) catalytic ozone destruction cycle accounts for the majority of the observed polar ozone loss. A key step in this catalytic cycle is the UV photolysis of Cl2O2. The determination of the Cl2O2 UV absorption spectrum has been the subject of several studies since the late 1980’s. Recently, Pope et al. (J. Phys. Chem. A, 111, 4322, 2007) reported significantly lower absorption cross sections for Cl2O2 for the atmospherically relevant wavelength region, >300 nm, than currently recommended for use in atmospheric models. If correct, the Pope et al. results would alter our understanding of the chemistry of polar ozone depletion significantly. In this study, the UV absorption spectrum and absolute cross sections of gas-phase Cl2O2 are reported for the wavelength range 200 - 420 nm at ~200 K. Sequential pulsed laser photolysis of various precursors were used to produce the ClO radical and Cl2O2 via the subsequent ClO + ClO + M reaction under static conditions. UV absorption spectra of the reaction mixture were measured using a diode array spectrometer after completion of the gas-phase radical chemistry. The spectral analysis utilized the observed isosbestic points, reaction stoichiometry, and chlorine mass balance to determine the UV spectrum and absolute cross section of Cl2O2. A complementary experimental technique similar to that used by Pope et al. was also used in this study. We obtained consistent Cl2O2 UV absorption spectra using the two different techniques. The Cl2O2 absorption cross sections for wavelengths in the 300 - 420 nm range were found to be in very good agreement with the values reported previously by Burkholder et al. (J. Phys. Chem. A, 94, 687, 1990) and significantly greater than the Pope et al. values in this atmospherically important wavelength region. A possible explanation for the disagreement with

Spray-dried chitosan/acid/NaCl microparticles enhance saltiness perception.

PubMed

Yi, Cheng; Tsai, Min-Lang; Liu, Tristan

2017-09-15

The composition, physicochemical properties and salinity of spray-dried chitosan/acid/NaCl microparticles were tested to ensure a low-sodium and high-salinity salty agent. The spray-dried chitosan/acid/NaCl microparticles were hollow and had a favourable hygroscopicity, and increased NaCl content and decreased organic acid content. Their size of the microparticles was 15.4-32.0μm and increased with NaCl concentration. The microparticles of acetic and lactic acid groups had a NaCl crystal size of 1-2 and 1-4μm, respectively. The NaCl crystals of acetic, lactic and citric acid group microparticles were distributed on the microparticle matrices, mostly on the microparticle surface and mainly on the inner walls of the microparticles walls, respectively. The acetic and lactic acid group microparticles were relatively smaller than general salt, with NaCl crystals distributed on the particle surfaces. Consequently, they were perceived as saltier than general salt and could potentially be regarded as a low-sodium salt for surface-salted foods. Copyright © 2017 Elsevier Ltd. All rights reserved.

Rate constants for reactions of ClO/x/ of atmospheric interest

NASA Technical Reports Server (NTRS)

Watson, R. T.

1977-01-01

Chemical kinetics measurements on 82 gas phase reactions of chlorine containing species are reviewed. Recommended rate constants are given. The principal species of interest are Cl, Cl2, ClO, Cl2O, ClOO, OClO, CINO, HCl and halo derivatives of methane and ethane. Absorption spectra are given for 21 species. In addition the chemical kinetics methods used to obtain these data are discussed with regard to their applicability and reliability.

Four new chalcohalides, NaBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Br and CsBa{sub 2}SnS{sub 4}Cl: Syntheses, crystal structures and optical properties

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

Li, Chao; Feng, Kai; Tu, Heng

Four new chalcohalides, namely NaBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Br, and CsBa{sub 2}SnS{sub 4}Cl, have been synthesized by the conventional high temperature solid-state reactions. They crystallize in three different space groups: space group I4/mcm for NaBa{sub 2}SnS{sub 4}Cl and KBa{sub 2}SnS{sub 4}Cl, Pnma for KBa{sub 2}SnS{sub 4}Br, and P2{sub 1}/c for CsBa{sub 2}SnS{sub 4}Cl. In all four compounds, the X{sup −} halide anions are only connected to six alkali metal or Ba cations, and the Sn atoms are only tetrahedrally enjoined to four S atoms. However, the M–X–Ba pseudo layers and the SnS{sub 4} tetrahedra are arrangedmore » in different ways in the three structural types, which demonstrates the interesting effect of ionic radii on the crystal structures. UV–vis–NIR spectroscopy measurements indicate that NaBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Br, and CsBa{sub 2}SnS{sub 4}Cl have band gaps of 2.28, 2.30, 1.95, and 2.06 eV, respectively. - Graphical abstract: A new series of chalcohalides, NaBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Br and CsBa{sub 2}SnS{sub 4}Cl have been obtained. They present three different space groups: NaBa{sub 2}SnS{sub 4}Cl and KBa{sub 2}SnS{sub 4}Cl in space group I4/mcm, KBa{sub 2}SnS{sub 4}Br in Pnma and CsBa{sub 2}SnS{sub 4}Cl in space group P2{sub 1}/c. UV–vis–NIR spectroscopy measurements indicate that NaBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Br and CsBa{sub 2}SnS{sub 4}Cl have band gaps of 2.28, 2.30 1.95, and 2.06 eV, respectively. - Highlights: • Four new chalcohalides, NaBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Br and CsBa{sub 2}SnS{sub 4}Cl were obtained. • They adopt three different structures owing to different ionic radii and elemental electronegativity. • NaBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Br and CsBa{sub 2}SnS{sub 4}Cl have

Experimental and theoretical determination of the dipole-quadrupole and dipole-octopole polarizabilities of the group IV tetrachlorides TiCl4, ZrCl4, and HfCl4

NASA Astrophysics Data System (ADS)

Hohm, Uwe; Maroulis, G.

2006-03-01

The dipole-quadrupole and dipole-octopole polarizabilities A and E of TiCl4, ZrCl4, and HfCl4 have been determined from collision-induced light-scattering experiments. Our respective experimental results for ∣A ∣ are (165±10), (110±30), and (140±20) e2a03Eh-1, whereas ∣E∣ is determined to be (675±125), (750±200), and (670±400) e2a04Eh-1. Theory predicts values convincingly close to experiment, as A =(181.4±9.1), (167.6±8.4), and (139.8±7.0) e2a03Eh-1, and E =(-671±67), (-688±69), and (-574±57) e2a04Eh-1. In addition our quantum chemical ab initio calculations give reliable values for the dipole polarizability α, as well as for the octopole and hexadecapole moments Ω and Φ for all three substances.

Double Knockout of the Na+-Driven Cl-/HCO3- Exchanger and Na+/Cl- Cotransporter Induces Hypokalemia and Volume Depletion.

PubMed

Sinning, Anne; Radionov, Nikita; Trepiccione, Francesco; López-Cayuqueo, Karen I; Jayat, Maximilien; Baron, Stéphanie; Cornière, Nicolas; Alexander, R Todd; Hadchouel, Juliette; Eladari, Dominique; Hübner, Christian A; Chambrey, Régine

2017-01-01

We recently described a novel thiazide-sensitive electroneutral NaCl transport mechanism resulting from the parallel operation of the Cl - /HCO 3 - exchanger pendrin and the Na + -driven Cl - /2HCO 3 - exchanger (NDCBE) in β-intercalated cells of the collecting duct. Although a role for pendrin in maintaining Na + balance, intravascular volume, and BP is well supported, there is no in vivo evidence for the role of NDCBE in maintaining Na + balance. Here, we show that deletion of NDCBE in mice caused only subtle perturbations of Na + homeostasis and provide evidence that the Na + /Cl - cotransporter (NCC) compensated for the inactivation of NDCBE. To unmask the role of NDCBE, we generated Ndcbe/Ncc double-knockout (dKO) mice. On a normal salt diet, dKO and single-knockout mice exhibited similar activation of the renin-angiotensin-aldosterone system, whereas only dKO mice displayed a lower blood K + concentration. Furthermore, dKO mice displayed upregulation of the epithelial sodium channel (ENaC) and the Ca 2+ -activated K + channel BKCa. During NaCl depletion, only dKO mice developed marked intravascular volume contraction, despite dramatically increased renin activity. Notably, the increase in aldosterone levels expected on NaCl depletion was attenuated in dKO mice, and single-knockout and dKO mice had similar blood K + concentrations under this condition. In conclusion, NDCBE is necessary for maintaining sodium balance and intravascular volume during salt depletion or NCC inactivation in mice. Furthermore, NDCBE has an important role in the prevention of hypokalemia. Because NCC and NDCBE are both thiazide targets, the combined inhibition of NCC and the NDCBE/pendrin system may explain thiazide-induced hypokalemia in some patients. Copyright © 2016 by the American Society of Nephrology.

Cl sup minus -HCO sub 3 sup minus exchange is present with Na sup + -K sup + -Cl sup minus cotransport in rabbit parotid acinar basolateral membranes

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

Turner, R.J.; George, J.N.

1988-03-01

The presence of a sodium-independent electroneutral Cl{sup {minus}}-anion exchanger in a basolateral membrane vesicle preparation from the rabbit parotid is demonstrated. This exchanger is shared by HCO{sub 3}{sup {minus}}, NO{sub 3}{sup {minus}}, Br{sup {minus}}, F{sup {minus}}, and formate, but not by thiocyanate, acetate, methylsulfate, gluconate, or hydroxyl ions. In order of relative potency, the exchanger is inhibited by SITS {ge} phloretin > furosemide > bumetanide {ge} phlorizin. A Na{sup +}-K{sup +}-dependent component of chloride flux, presumably due to the Na{sup +}-K{sup +}-Cl{sup {minus}} cotransporter already characterized in this preparation, was also observed. {sup 36}Cl uptake into vesicles loaded with KClmore » exhibited an overshoot of intravesicular ({sup 36}Cl) due to {sup 36}Cl-Cl exchange. However, when vesicles were loaded with both KCl and NaCl the height of the overshoot was considerably decreased indicating a Na{sup +}-K{sup +}-dependent dissipation of the intravesicular to extravesicular chloride gradient. This experiment provides strong evidence that the Na{sup +}-K{sup +}Cl{sup {minus}} cotransporter and the Cl{sup {minus}} HCO{sub 3}{sup {minus}} exchange are present in the same membrane vesicles. These results indicate that Cl{sup {minus}}-HCO{sub 3}{sup {minus}} exchange is present in the basolateral membrane of parotid acinar cells and thus that this transporter may play a significant role in salivary secretion.« less

Molecular salt effects in the gas phase: tuning the kinetic basicity of [HCCLiCl]⁻ and [HCCMgCl₂]⁻ by LiCl and MgCl₂.

PubMed

Khairallah, George N; da Silva, Gabriel; O'Hair, Richard A J

2014-10-06

A combination of gas-phase ion-molecule reaction experiments and theoretical kinetic modeling is used to examine how a salt can influence the kinetic basicity of organometallates reacting with water. [HC≡CLiCl](-) reacts with water more rapidly than [HC≡CMgCl2](-), consistent with the higher reactivity of organolithium versus organomagnesium reagents. Addition of LiCl to [HC≡CLiCl](-) or [HC≡CMgCl2](-) enhances their reactivity towards water by a factor of about 2, while addition of MgCl2 to [HC≡CMgCl2](-) enhances its reactivity by a factor of about 4. Ab initio calculations coupled with master equation/RRKM theory kinetic modeling show that these reactions proceed via a mechanism involving formation of a water adduct followed by rearrangement, proton transfer, and acetylene elimination as either discrete or concerted steps. Both the energy and entropy requirements for these elementary steps need to be considered in order to explain the observed kinetics. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Noradrenaline induces CX3CL1 production and release by neurons.

PubMed

Madrigal, José L M; Caso, Javier R; García-Bueno, Borja; Gutiérrez, Irene L; Leza, Juan C

2017-03-01

CX3CL1 is a chemokine for which neurons constitute its primary source within the brain. Besides acting as a chemokine, CX3CL1 regulates multiple processes and is known to inhibit microglial activation. Because of this, CX3CL1 is considered as a messenger used by neurons to communicate with microglia. Similarly, the neurotransmitter noradrenaline reduces microglial activation and production of neurotoxic agents. Based on this, the regulation of neuronal CX3CXL1 by noradrenaline was analyzed. In primary cortical neurons, noradrenaline induced the accumulation of CX3CL1 protein and mRNA. Noradrenaline also increased CX3CL1 in its soluble form despite the inhibition of the activity and synthesis of ADAM10 and ADAM17, the main proteases known to cleave CX3CL1 from the neuronal membrane. Noradrenaline-treated neurons displayed a higher degree of dendritic arborization and a characteristic accumulation of CX3CL1 in the dendritic bifurcation zones. The soluble CX3CL1 produced by neurons after noradrenaline treatment, reduced the accumulation of nitrites in microglia. These findings indicate that NA anti-inflammatory actions are mediated by neuronal CX3CL1. In addition, CX3CL1 seems to be involved in the development of neuronal processes stimulated by noradrenaline. Copyright © 2016 Elsevier Ltd. All rights reserved.

Vertical profiles of ClNO2 at a remote terrestrial site: evidence of N2O5 dry deposition as a source of ClNO2?

NASA Astrophysics Data System (ADS)

McLaren, R.; Roberts, J. M.; Kercher, J. P.; Thornton, J. A.; Brown, S. S.; Edwards, P. M.; Young, C. J.; Dube, W. P.; Washenfelder, R. A.; Williams, E. J.; Holloway, J. S.; Bates, T. S.; Quinn, P.

2012-12-01

Recent observations of nitryl chloride (ClNO2) have suggested that this compound can accumulate to significant levels (several ppb) in the nocturnal boundary layer at night. Its photolytic loss the next day can be a significant source of chlorine atom radicals. The source of ClNO2 is largely thought to be the heterogeneous reaction of N2O5 with aerosol chloride, not just confined to coastal regions but also observed thousands of kilometers inland in urban areas. During the Uintah Basin Winter Ozone Study, we made measurements of ClNO2 by CIMS on a tower in a remote region of Utah. Levels of ClNO2 were surprisingly high at night (up to 2 ppb) even though sea salt aerosols were not present. Soils in the region were alkaline with high chloride content. To address the potential of N2O5 dry deposition as a source of ClNO2, we measured vertical profiles of ClNO2 from 1 to 12 m agl with a movable inlet. We observed negative gradients of ClNO2 and positive gradients of nitrate (a surrogate for N2O5), which suggests that dry deposition of N2O5 and reaction with Cl- in soils is a source of ClNO2 in this region.

F-Cl-OH partitioning between biotite and apatite

NASA Astrophysics Data System (ADS)

Zhu, Chen; Sverjensky, Dimitri A.

1992-09-01

An assessment of F-C1-OH partitioning between natural apatite and biotite in a variety of rocks was used to evaluate reciprocal (Mg, Fe 2+, Al VI) (F, Cl, OH) mixing properties for biotite according to the reciprocal salt solution model of WOOD and NICHOLLS (1978). Ideal mixing of F-C1-OH and Fe-Mg-Al VI in the hydroxyl and octahedral sites is assumed for biotites with dilute Cl concentrations. The reciprocal interaction parameters, in terms of Gibbs free energies, for the reactions KMg3[ AlSi3O10]( OH) 2 + KFe3[ AlSi3O10]( F) 2 = KMg3[ AlSi3O10]( F) 2 + KFe3[ AlSi3O10]( OH) 2 Phl Fann Fphl Ann and KMg3[ AlSi3O10]( Cl) 2 + KFe3[ AlSi3O10]( OH) 2 = KMg3[ AlSi3O10]( OH) 2 + KFe3[ AlSi3O10] ( Cl) 2 Clphl Ann Phl Clann are about -10 kcal/mol and -4.5 kcal/mol, respectively. These mixing properties are consistent with standard state thermodynamic properties for F and Cl endmember phases from ZHU and SVERJENSKY (1991). The approach of studying F-C1-OH partitioning between biotite and apatite permits distinguishing the reciprocal effects from the effects of temperature, pressure, and fluid composition. The resultant mixing properties are consistent with observations both in hydrothermal experiments and in natural mineral assemblages. The mixing properties presented in this study enable us now to predict F and Cl concentrations of hydrothermal fluids from the measured F and Cl concentrations in biotite with variable Fe-Mg-Al VI proportions. A case study of the Santa Rita porphyry copper deposits, New Mexico, shows that hydrothermal fluids responsible for the phyllic alteration had a salinity about 3 molal Cl -, in agreement with fluid inclusion studies. Our internally consistent standard thermodynamic properties and solid solution models also lead to recalibration of the apatite-biotite geothermometer. The revised geothermometer predicts temperatures that agree with those estimated from other independent geothermometers. The large reciprocal effects in biotite also point

Hyperfine-resolved transition frequency list of fundamental vibration bands of H35Cl and H37Cl

NASA Astrophysics Data System (ADS)

Iwakuni, Kana; Sera, Hideyuki; Abe, Masashi; Sasada, Hiroyuki

2014-12-01

Sub-Doppler resolution spectroscopy of the fundamental vibration bands of H35Cl and H37Cl has been carried out from 87.1 to 89.9 THz. We have determined the absolute transition frequencies of the hyperfine-resolved R(0) to R(4) transitions with a typical uncertainty of 10 kHz. We have also yielded six molecular constants for each isotopomer in the vibrational excited state, which reproduce the determined frequencies with a standard deviation of about 10 kHz.

Identification of the fatty acid activation site on human ClC-2.

PubMed

Cuppoletti, John; Tewari, Kirti P; Chakrabarti, Jayati; Malinowska, Danuta H

2017-06-01

Fatty acids (including lubiprostone and cobiprostone) are human ClC-2 (hClC-2) Cl - channel activators. Molecular and cellular mechanisms underlying this activation were examined. Role of a four-amino acid PKA activation site, RGET 691 , of hClC-2 was investigated using wild-type (WT) and mutant (AGET, RGEA, and AGAA) hClC-2 expressed in 293EBNA cells as well as involvement of PKA, intracellular cAMP concentration ([cAMP] i ), EP 2 , or EP 4 receptor agonist activity. All fatty acids [lubiprostone, cobiprostone, eicosatetraynoic acid (ETYA), oleic acid, and elaidic acid] caused significant rightward shifts in concentration-dependent Cl - current activation (increasing EC 50 s) with mutant compared with WT hClC-2 channels, without changing time and voltage dependence, current-voltage rectification, or methadone inhibition of the channel. As with lubiprostone, cobiprostone activation of hClC-2 occurred with PKA inhibitor (myristoylated protein kinase inhibitor) present or when using double PKA activation site (RRAA 655 /RGEA 691 ) mutant. Cobiprostone did not activate human CFTR. Fatty acids did not increase [cAMP] i in hClC-2/293EBNA or T84 cells. Using T84 CFTR knockdown cells, cobiprostone increased hClC-2 Cl - currents without increasing [cAMP] i, while PGE 2 and forskolin-IBMX increased both. Fatty acids were not agonists of EP 2 or EP 4 receptors. L-161,982, a supposed EP 4 -selective inhibitor, had no effect on lubiprostone-activated hClC-2 Cl - currents but significantly decreased T84 cell barrier function measured by transepithelial resistance and fluorescent dextran transepithelial movement. The present findings show that RGET 691 of hClC-2 (possible binding site) plays an important functional role in fatty acid activation of hClC-2. PKA, [cAMP] i , and EP 2 or EP 4 receptors are not involved. These studies provide the molecular basis for fatty acid regulation of hClC-2. Copyright © 2017 the American Physiological Society.

NaCl responsive taste cells in the mouse fungiform taste buds.

PubMed

Yoshida, R; Horio, N; Murata, Y; Yasumatsu, K; Shigemura, N; Ninomiya, Y

2009-03-17

Previous studies have demonstrated that rodents' chorda tympani (CT) nerve fibers responding to NaCl can be classified according to their sensitivities to the epithelial sodium channel (ENaC) blocker amiloride into two groups: amiloride-sensitive (AS) and -insensitive (AI). The AS fibers were shown to respond specifically to NaCl, whereas AI fibers broadly respond to various electrolytes, including NaCl. These data suggest that salt taste transduction in taste cells may be composed of at least two different systems; AS and AI ones. To further address this issue, we investigated the responses to NaCl, KCl and HCl and the amiloride sensitivity of mouse fungiform papilla taste bud cells which are innervated by the CT nerve. Comparable with the CT data, the results indicated that 56 NaCl-responsive cells tested were classified into two groups; 25 cells ( approximately 44%) narrowly responded to NaCl and their NaCl response were inhibited by amiloride (AS cells), whereas the remaining 31 cells ( approximately 56%) responded not only to NaCl, but to KCl and/or HCl and showed no amiloride inhibition of NaCl responses (AI cells). Amiloride applied to the basolateral side of taste cells had no effect on NaCl responses in the AS and AI cells. Single cell reverse transcription-polymerase chain reaction (RT-PCR) experiments indicated that ENaC subunit mRNA was expressed in a subset of AS cells. These findings suggest that the mouse fungiform taste bud is composed of AS and AI cells that can transmit taste information differently to their corresponding types of CT fibers, and apical ENaCs may be involved in the NaCl responses of AS cells.

Correction to: Molecular identification of Leishmania spp. isolates causes cutaneous leishmaniasis (CL) in Sanliurfa Province, Turkey, where CL is highly endemic.

PubMed

Gurses, Gulcan; Ozaslan, Mehmet; Yıldız Zeyrek, Fadile; Kılıç, Ibrahim H; Yentür Doni, Nebiye; Karagoz, I Didem; Uluca, Nermin

2018-05-01

In published article (Molecular Identification of Leishmania spp. Isolates Causes Cutaneous Leishmaniasis (CL) in Sanliurfa Province, Turkey, Where CL is Highly Endemic) Table 1 titled "The pH values of yogurts collected from villages in Turkey" doesn't belong to this article.

Delta 37Cl and Characterisation of Petroleum-gas Reservoirs

NASA Astrophysics Data System (ADS)

Woulé Ebongué, V.; Jendrzejewski, N.; Walgenwitz, F.; Pineau, F.; Javoy, M.

2003-04-01

The geochemical characterisation of formation waters from oil/gas fields is used to detect fluid-flow barriers in reservoirs and to reconstruct the system dynamic. During the progression of the reservoir filling, the aquifer waters are pushed by hydrocarbons toward the reservoir bottom and their compositions evolve due to several parameters such as water-rock interactions, mixing with oil-associated waters, physical processes etc. The chemical and isotopic evolution of these waters is recorded in irreducible waters that have been progressively "fossilised" in the oil/gas column. Residual salts precipitated from these waters were recovered. Chloride being the most important dissolved anion in these waters and not involved in diagenetic reactions, its investigation should give insights into the different transport or mixing processes taking place in the sedimentary basin and point out to the formation waters origins. The first aim of our study was to test the Cl-RSA technique (Chlorine Residual Salts Analysis) based on the well-established Sr-RSA technique. The main studied area is a turbiditic sandstone reservoir located in the Lower Congo basin in Angola. Present-day aquifer waters, irreducible waters from sandstone and shale layers as well as drilling mud and salt dome samples were analysed. Formation waters (aquifer and irreducible trapped in shale) show an overall increase of chlorinity with depth. Their δ37Cl values range from -1.11 ppm to +2.30 ppm ± 0.05 ppm/ SMOC. Most Cl-RSA data as well as the δ37Cl obtained on a set of water samples (from different aquifers in the same area) are lower than -0.13 ppm with lower δ37Cl values at shallower depths. In a δ37Cl versus chlorinity diagram, they are distributed along a large range of chlorinity: 21 to 139 g/l, in two distinct groups. (1) Irreducible waters from one of the wells display a positive correlation between chlorinity and the δ37Cl values. (2) In contrary, the majority of δ37Cl measured on aquifers

Salt exclusion and mycorrhizal symbiosis increase tolerance to NaCl and CaCl2 salinity in ‘Siam Queen’ basil

USDA-ARS?s Scientific Manuscript database

A study was conducted to evaluate the effects of salinity on growth and nutrient uptake in basil (Ocimum basilicum L.). Plants were fertilized with a complete nutrient solution and exposed to no, low, or moderate levels of salinity from NaCl or CaCl2. Plants in the control and moderate salinity tre...

Franck-Condon Simulations including Anharmonicity of the Ã(1)A''-X̃(1)A' Absorption and Single Vibronic Level Emission Spectra of HSiCl and DSiCl.

PubMed

Mok, Daniel W K; Lee, Edmond P F; Chau, Foo-Tim; Dyke, John M

2009-03-10

RCCSD(T) and/or CASSCF/MRCI calculations have been carried out on the X̃(1)A' and Ã(1)A'' states of HSiCl employing basis sets of up to the aug-cc-pV5Z quality. Contributions from core correlation and extrapolation to the complete basis set limit were included in determining the computed equilibrium geometrical parameters and relative electronic energy of these two states of HSiCl. Franck-Condon factors which include allowance for anharmonicity and Duschinsky rotation between these two states of HSiCl and DSiCl were calculated employing RCCSD(T) and CASSCF/MRCI potential energy functions, and were used to simulate the Ã(1)A'' ← X̃(1)A' absorption and Ã(1)A'' → X̃(1)A' single vibronic level (SVL) emission spectra of HSiCl and DSiCl. Simulated absorption and experimental LIF spectra, and simulated and observed Ã(1)A''(0,0,0) → X̃(1)A' SVL emission spectra, of HSiCl and DSiCl are in very good agreement. However, agreement between simulated and observed Ã(1)A''(0,1,0) → X̃(1)A' and Ã(1)A''(0,2,1) → X̃(1)A' SVL emission spectra of DSiCl is not as good. Preliminary calculations on low-lying excited states of HSiCl suggest that vibronic interaction between low-lying vibrational levels of the Ã(1)A'' state and highly excited vibrational levels of the ã(3)A'' is possible. Such vibronic interaction may change the character of the low-lying vibrational levels of the Ã(1)A'' state, which would lead to perturbation in the SVL emission spectra from these vibrational levels.

Cloning, functional expression, and characterization of a PKA-activated gastric Cl- channel.

PubMed

Malinowska, D H; Kupert, E Y; Bahinski, A; Sherry, A M; Cuppoletti, J

1995-01-01

cDNA encoding a Cl- channel was isolated from a rabbit gastric library, sequenced, and expressed in Xenopus oocytes. The predicted protein (898 amino acids, relative molecular mass 98,433 Da) was overall 93% similar to the rat brain ClC-2 Cl- channel. However, a 151-amino acid stretch toward the COOH-terminus was 74% similar to ClC-2 with six amino acids deleted. Two new potential protein kinase A (PKA) phosphorylation sites (also protein kinase C phosphorylation sites) were introduced. cRNA-injected Xenopus oocytes expressed a Cl- channel that was active at pHtrans 3 and had a linear current-voltage (I-V) curve and a slope conductance of 29 +/- 1 pS at 800 mM CsCl. A fivefold Cl- gradient caused a rightward shift in the I-V curve with a reversal potential of +30 +/- 3 mV, indicating anion selectivity. The selectivity was I- > Cl- > NO3-. The native and recombinant Cl- channel were both activated in vitro by PKA catalytic subunit and ATP. The electrophysiological and regulatory properties of the cloned and the native channel were similar. The cloned protein may be the Cl- channel involved in gastric HCl secretion.

Structure and properties of Mn4Cl9: an antiferromagnetic binary hyperhalogen.

PubMed

Li, Yawei; Zhang, Shunhong; Wang, Qian; Jena, Puru

2013-02-07

Calculations based on density functional theory show that the structure of Mn(4)Cl(9) anion is that of a Mn atom at the core surrounded by three MnCl(3) moieties. Since Mn is predominantly divalent and MnCl(3) is known to be a superhalogen with a vertical detachment energy (VDE) of 5.27 eV, Mn(4)Cl(9) can be viewed as a hyperhalogen with the formula unit Mn(MnCl(3))(3). Indeed, the calculated VDE of Mn(4)Cl(9) anion, namely 6.76 eV, is larger than that of MnCl(3) anion. More importantly, unlike previously discovered hyperhalogens, Mn(4)Cl(9) is the first such hyperhalogen species composed of only two constituent atoms. We further show that Mn(4)Cl(9) can be used as a ligand to design molecules with even higher VDEs. For example, Li[Mn(MnCl(3))(3)](2) anion has a VDE of 7.26 eV. These negatively charged clusters are antiferromagnetic with most of the magnetic moments localized at the Mn sites. Our studies show new pathways for creating binary hyperhalogens.

Structure and properties of Mn4Cl9: An antiferromagnetic binary hyperhalogen

NASA Astrophysics Data System (ADS)

Li, Yawei; Zhang, Shunhong; Wang, Qian; Jena, Puru

2013-02-01

Calculations based on density functional theory show that the structure of Mn4Cl9 anion is that of a Mn atom at the core surrounded by three MnCl3 moieties. Since Mn is predominantly divalent and MnCl3 is known to be a superhalogen with a vertical detachment energy (VDE) of 5.27 eV, Mn4Cl9 can be viewed as a hyperhalogen with the formula unit Mn(MnCl3)3. Indeed, the calculated VDE of Mn4Cl9 anion, namely 6.76 eV, is larger than that of MnCl3 anion. More importantly, unlike previously discovered hyperhalogens, Mn4Cl9 is the first such hyperhalogen species composed of only two constituent atoms. We further show that Mn4Cl9 can be used as a ligand to design molecules with even higher VDEs. For example, Li[Mn(MnCl3)3]2 anion has a VDE of 7.26 eV. These negatively charged clusters are antiferromagnetic with most of the magnetic moments localized at the Mn sites. Our studies show new pathways for creating binary hyperhalogens.

Formation of AlCl by radiative association

NASA Astrophysics Data System (ADS)

Andreazza, C. M.; de Almeida, A. A.; Vichietti, R. M.

2018-06-01

The rate coefficient for the formation of aluminium monochloride, AlCl, from the radiative association of aluminium and chlorine atoms is estimated as a function of temperature. The coupling of the Al and Cl atoms through the A1Π molecular electronic state, which undergoes radiative transition to the X1Σ+ ground state, is the most efficient transition to form AlCl. The rate constant was found to vary with temperature according to the expressions k(T) = 1.22 × 10-16(T/300)0.40exp (-748/T) cm3 s-1 for temperatures between 300 and 1000 K, and k(T) = 2.20 × 10-16(T/300)0.175exp (-1067/T) cm3 s-1 for temperatures between 1000 and 14 000 K.

Cl(-) concentration dependence of photovoltage generation by halorhodopsin from Halobacterium salinarum.

PubMed Central

Muneyuki, Eiro; Shibazaki, Chie; Wada, Yoichiro; Yakushizin, Manabu; Ohtani, Hiroyuki

2002-01-01

The photovoltage generation by halorhodopsin from Halobacterium salinarum (shR) was examined by adsorbing shR-containing membranes onto a thin polymer film. The photovoltage consisted of two major components: one with a sub-millisecond range time constant and the other with a millisecond range time constant with different amplitudes, as previously reported. These components exhibited different Cl(-) concentration dependencies (0.1-9 M). We found that the time constant for the fast component was relatively independent of the Cl(-) concentration, whereas the time constant for the slow component increased sigmoidally at higher Cl(-) concentrations. The fast and the slow processes were attributed to charge (Cl(-)) movements within the protein and related to Cl(-) ejection, respectively. The laser photolysis studies of shR-membrane suspensions revealed that they corresponded to the formation and the decay of the N intermediate. The photovoltage amplitude of the slow component exhibited a distorted bell-shaped Cl(-) concentration dependence, and the Cl(-) concentration dependence of its time constant suggested a weak and highly cooperative Cl(-)-binding site(s) on the cytoplasmic side (apparent K(D) of approximately 5 M and Hill coefficient > or =5). The Cl(-) concentration dependence of the photovoltage amplitude and the time constant for the slow process suggested a competition between spontaneous relaxation and ion translocation. The time constant for the relaxation was estimated to be >100 ms. PMID:12324398

Diversity of phytoplankton in some domestic wastewater-fed urban fish pond ecosystems of the Chota Nagpur Plateau in Bankura, India

NASA Astrophysics Data System (ADS)

Das, Debjyoti; Pathak, Arabinda; Pal, Sudin

2018-06-01

The present limnological investigation is conducted to study the relationship between phytoplankton abundance and five important physicochemical factors in urban wastewater-fed seven fish ponds of Chota Nagpur Plateau area. A total number of 43 phytoplankton taxa representing four classes, namely Cyanophyceae (7), Chlorophyceae (29), Bacillariophyceae (5) and Euglenophyceae (2), are thriving in these ponds which may suggest that different nutrient-rich wastewater supports the diversity and abundance of the phytoplankton. Different values of diversity indices, results of post hoc analysis and rarefaction curve are depicted spatial variations of phytoplankton abundance and physicochemical factors. From the Principal Component Analysis, out of 43 phytoplankton species, 23 important species are extracted. The canonical correspondence analysis presents that most of the phytoplankton species densities are associated with higher values of the physicochemical variables in these ponds. Correspondingly, in the present study, Algal Genus Pollution Index (AGPI) is employed to study the water quality of seven sites. From the AGPI score, it is revealed that Site 4 has probable high organic pollution and Site 2 and Site 3 have moderate organic pollution. Therefore, long-term intensive studies and proper management are necessary to protect these ponds toward eutrophication and degradation, because these ponds not only act as a safeguard of livelihoods but also contribute significantly at local level food and water security and economic prosperity.

The Salty Scrambled Egg: Detection of NaCl Toward CRL 2688

NASA Astrophysics Data System (ADS)

Highberger, J. L.; Thomson, K. J.; Young, P. A.; Arnett, D.; Ziurys, L. M.

2003-08-01

NaCl has been detected toward the circumstellar envelope of the post-AGB star CRL 2688 using the IRAM 30 m telescope, the first time this molecule has been identified in a source other than IRC +10216. The J=7-->6, 11-->10, 12-->11, and 18-->17 transitions of NaCl at 1, 2, and 3 mm have been observed, as well as the J=8-->7 line of the 37Cl isotopomer. The J=12-->11 line was also measured at the ARO 12 m telescope. An unsuccessful search was additionally conducted for AlCl toward CRL 2688, although in the process new transitions of NaCN were observed. Both NaCl and NaCN were found to be present in the AGB remnant wind, as suggested by their U-shaped line profiles, indicative of emission arising from an optically thin, extended shell-like source of radius ~10"-12". These data contrast with past results in IRC +10216, where the distribution of both molecules is confined to within a few arcseconds of the star. A high degree of excitation is required for the transitions observed for NaCl and NaCN; therefore, these two species likely arise in the region where the high-velocity outflow has collided with the remnant wind. Here the effects of shocks and clumping due to Rayleigh-Taylor instabilities have raised the densities and temperatures significantly. The shell source is thus likely to be clumpy and irregular. The chemistry producing the sodium compounds is consequently more complex than simple LTE formation. Abundances of NaCl and NaCN, relative to H2, are f~1.6×10-10 and ~5.2×10-9, respectively, while the upper limit to AlCl is f<2×10-9. These values differ substantially from those in IRC +10216, where AlCl has an abundance near 10-7. The NaCl observations additionally indicate a chlorine isotope ratio of 35Cl/37Cl=2.1+/-0.8 in CRL 2688, suggestive of s-process enhancement of chlorine 37.

Characterization of TlBrxCl1-x Crystals for Radiation Detectors

NASA Astrophysics Data System (ADS)

Onodera, Toshiyuki; Hitomi, Keitaro; Onodera, Chikara; Shoji, Tadayoshi; Mochizuki, Katsumi

2012-08-01

Thallium bromide chloride TlBrxCl1-x crystals have been evaluated as a material used for fabrication of room temperature radiation detectors. In this study, TlBrxCl1-x crystals with various chlorine (Cl) concentrations were grown by the travelling molten zone method and the detectors were fabricated from the crystals. The optical properties of the crystals were evaluated by measuring the transmittances. The charge transport properties were characterized by the Hecht analysis. The band gap energy of the crystals proportionally increased with Cl concentration. Mobility-lifetime products (μτ) of the crystals decreased with increasing Cl concentration.

Circumstellar chlorine chemistry and a search for AlCl

NASA Astrophysics Data System (ADS)

Clegg, R. E. S.; Wootten, H. A.

1980-09-01

The J = 7-6 transition of AlCl has been sought in carbon-rich circumstellar shells, Orion A, and Sgr B-2. The upper limit for IRC + 10216 is 20 times less than the predicted value for fully associated AlCl. It is suggested that either the initial density in the circumstellar gas flow (not greater than 10 to the 10th per cu cm) or the gaseous Al and Cl are depleted by grains in this object.

High energy KrCl electric discharge laser

DOEpatents

Sze, Robert C.; Scott, Peter B.

1981-01-01

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

High energy KrCl electric discharge laser

DOEpatents

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

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

The Gaussian CL s method for searches of new physics

DOE PAGES

Qian, X.; Tan, A.; Ling, J. J.; ...

2016-04-23

Here we describe a method based on the CL s approach to present results in searches of new physics, under the condition that the relevant parameter space is continuous. Our method relies on a class of test statistics developed for non-nested hypotheses testing problems, denoted by ΔT, which has a Gaussian approximation to its parent distribution when the sample size is large. This leads to a simple procedure of forming exclusion sets for the parameters of interest, which we call the Gaussian CL s method. Our work provides a self-contained mathematical proof for the Gaussian CL s method, that explicitlymore » outlines the required conditions. These conditions are milder than that required by the Wilks' theorem to set confidence intervals (CIs). We illustrate the Gaussian CL s method in an example of searching for a sterile neutrino, where the CL s approach was rarely used before. We also compare data analysis results produced by the Gaussian CL s method and various CI methods to showcase their differences.« less

Probing the conformation of a conserved glutamic acid within the Cl- pathway of a CLC H+/Cl- exchanger.

PubMed

Vien, Malvin; Basilio, Daniel; Leisle, Lilia; Accardi, Alessio

2017-04-03

The CLC proteins form a broad family of anion-selective transport proteins that includes both channels and exchangers. Despite extensive structural, functional, and computational studies, the transport mechanism of the CLC exchangers remains poorly understood. Several transport models have been proposed but have failed to capture all the key features of these transporters. Multiple CLC crystal structures have suggested that a conserved glutamic acid, Glu ex , can adopt three conformations and that the interconversion of its side chain between these states underlies H + /Cl - exchange. One of these states, in which Glu ex occupies the central binding site (S cen ) while Cl - ions fill the internal and external sites (S int and S ext ), has only been observed in one homologue, the eukaryotic cmCLC. The existence of such a state in other CLCs has not been demonstrated. In this study, we find that during transport, the prototypical prokaryotic CLC exchanger, CLC-ec1, adopts a conformation with functional characteristics that match those predicted for a cmCLC-like state, with Glu ex trapped in S cen between two Cl - ions. Transport by CLC-ec1 is reduced when [Cl - ] is symmetrically increased on both sides of the membrane and mutations that disrupt the hydrogen bonds stabilizing Glu ex in S cen destabilize this trapped state. Furthermore, inhibition of transport by high [Cl - ] is abolished in the E148A mutant, in which the Glu ex side chain is removed. Collectively, our results suggest that, during the CLC transport cycle, Glu ex can occupy S cen as well as the S ext position in which it has been captured crystallographically and that hydrogen bonds with the side chains of residues that coordinate ion binding to S cen play a role in determining the equilibrium between these two conformations. © 2017 Vien et al.

Validation of UARS Microwave Limb Sounder ClO Measurements

NASA Technical Reports Server (NTRS)

Waters, J. W.; Read, W. G.; Froidevaux, L.; Lungu, T. A.; Perun, V. S.; Stachnik, R. A.; Jarnot, R. F.; Cofield, R. E.; Fishbein, E. F.; Flower, D. A.;

LASER RADIATION CHARACTERISTICS (BRIEF COMMUNICATIONS): Conversion of KrCl and XeCl laser radiation to the visible spectral range by stimulated Raman scattering in lead vapor

NASA Astrophysics Data System (ADS)

Evtushenko, Gennadii S.; Mel'chenko, S. V.; Panchenko, Aleksei N.; Tarasenko, Viktor F.

1990-04-01

Conversion of KrCl and XeCl laser radiation by stimulated Raman scattering was achieved in lead vapor. The KrCl laser radiation was converted into three lines in the visible region at λ = 406, 590, and 723 nm by transitions from both the ground and first excited levels of the lead atom. The conversion efficiency of XeCl laser radiation of low spatial coherence was found to be limited by the activation of a competing nonlinear process.

Los Alamos Science Facilities

Science.gov Websites

Los Alamos National Laboratory Search Site submit About Mission Business Newsroom Publications Los Innovation in New Mexico Los Alamos Collaboration for Explosives Detection (LACED) SensorNexus Exascale Computing Project (ECP) User Facilities Center for Integrated Nanotechnologies (CINT) Los Alamos Neutron

Living in Los Alamos

Science.gov Websites

Los Alamos National Laboratory Search Site submit About Mission Business Newsroom Publications Los Innovation in New Mexico Los Alamos Collaboration for Explosives Detection (LACED) SensorNexus Exascale Computing Project (ECP) User Facilities Center for Integrated Nanotechnologies (CINT) Los Alamos Neutron

Unificando los criterios de sepsis neonatal tardía: propuesta de un algoritmo de vigilancia diagnóstica

PubMed Central

Zea-Vera, Alonso; Turin, Christie G.; Ochoa, Theresa J.

2015-01-01

Las infecciones constituyen una de las principales causas de muerte en el periodo neonatal. El diagnóstico de sepsis neonatal representa un gran desafío ya que los recién nacidos presentan signos clínicos muy inespecíficos y los exámenes auxiliares tienen una baja sensibilidad. Con el objetivo de mejorar el diagnóstico correcto de esta patología proponemos un algoritmo de vigilancia diagnóstica para sepsis neonatal tardía en el Perú y países de la región. El algoritmo permite clasificar a los episodios como sepsis confirmada, probable o posible, y sobretodo busca identificar aquellos episodios que no corresponden a sepsis, evitando calificar otras patologías como “sepsis”. Un mejor diagnóstico permitiría tener tasas más reales de sepsis neonatal, mejorar el uso de antibióticos y evitar sus efectos negativos en el recién nacido, así como una visión más exacta de su impacto en la salud pública. PMID:25123879

Anion exchange pathways for Cl sup minus transport in rabbit renal microvillus membranes

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

Karniski, L.P.; Aronson, P.S.

1987-09-01

The authors evaluated the mechanisms of chloride transport in microvillus membrane vesicles isolated from the rabbit renal cortex. The presence of Cl-formate exchange was confirmed. Outward gradients of oxaloacetate, HCO{sub 3}, acetate, lactate, succinate, sulfate, and p-aminohippurate (PAH) stimulated the rate of Cl uptake minimally or not at all. However, an outward gradient of oxalate stimulated Cl uptake by 70%, and an outward Cl gradient induced uphill oxalate uptake, indicting Cl-oxalate exchange. Moreover, an outward formate gradient induced uphill oxalate uptake, indicating formate-oxalate exchange. Studies of inhibitor and substrate specificity indicated the probably operation of at least two separate anionmore » exchangers in mediating Cl transport. The Cl-formate exchanger accepted Cl and formate as substrates, had little or no affinity for oxalate, was sensitive to inhibition by furosemide, and was less sensitive to inhibition by 4,4{prime}-diisothiocyanostilbene-2,2{prime}-disulfonic acid (DIDS). The Cl (formate)-oxalate exchanger also accepted Cl and formate as substrates but had high affinity for oxalate, was highly sensitive to inhibition by DIDS, and was less sensitive to inhibition by furosemide. The Cl-formate exchanger was electroneutral, whereas the Cl (formate)-oxalate exchanger was electrogenic. They conclude that at least separate anion exchangers mediating Cl transport are present on the luminal membrane of the rabbit proximal tubule cell. These exchangers may play important roles in mediating transtubular Cl and oxalate transport in this nephron segment.« less

Characterization of NaCl tolerance in Desulfovibrio vulgaris Hildenborough through experimental evolution

PubMed Central

Zhou, Aifen; Baidoo, Edward; He, Zhili; Mukhopadhyay, Aindrila; Baumohl, Jason K; Benke, Peter; Joachimiak, Marcin P; Xie, Ming; Song, Rong; Arkin, Adam P; Hazen, Terry C; Keasling, Jay D; Wall, Judy D; Stahl, David A; Zhou, Jizhong

2013-01-01

Desulfovibrio vulgaris Hildenborough strains with significantly increased tolerance to NaCl were obtained via experimental evolution. A NaCl-evolved strain, ES9-11, isolated from a population cultured for 1200 generations in medium amended with 100 mM NaCl, showed better tolerance to NaCl than a control strain, EC3-10, cultured for 1200 generations in parallel but without NaCl amendment in medium. To understand the NaCl adaptation mechanism in ES9-11, we analyzed the transcriptional, metabolite and phospholipid fatty acid (PLFA) profiles of strain ES9-11 with 0, 100- or 250 mM-added NaCl in medium compared with the ancestral strain and EC3-10 as controls. In all the culture conditions, increased expressions of genes involved in amino-acid synthesis and transport, energy production, cation efflux and decreased expression of flagellar assembly genes were detected in ES9-11. Consistently, increased abundances of organic solutes and decreased cell motility were observed in ES9-11. Glutamate appears to be the most important osmoprotectant in D. vulgaris under NaCl stress, whereas, other organic solutes such as glutamine, glycine and glycine betaine might contribute to NaCl tolerance under low NaCl concentration only. Unsaturation indices of PLFA significantly increased in ES9-11. Branched unsaturated PLFAs i17:1 ω9c, a17:1 ω9c and branched saturated i15:0 might have important roles in maintaining proper membrane fluidity under NaCl stress. Taken together, these data suggest that the accumulation of osmolytes, increased membrane fluidity, decreased cell motility and possibly an increased exclusion of Na+ contribute to increased NaCl tolerance in NaCl-evolved D. vulgaris. PMID:23575373

23Na and 35/37Cl as NMR probes of growth and shape of sodium taurodeoxycholate micellar aggregates in the presence of NaCl.

PubMed

Asaro, Fioretta; Feruglio, Luigi; Galantini, Luciano; Nardelli, Alessia

2013-02-15

The growth of the aggregates of the dihydroxylated bile salt sodium taurodeoxycholate (NaTDC) upon NaCl addition and the involvement of the counterion were investigated by NMR spectroscopy of monoatomic ionic species. (23)Na T(1) values from 0.015, 0.100, and 0.200 mol kg(-1) NaTDC solutions in D(2)O, at variable NaCl content, proved to be sensitive to the transition from primary to secondary aggregates, which occurs in the former sample, and to intermicellar interaction. Some (79)Br NMR measurements were performed on a 0.100 mol kg(-1) NaTDC sample added by NaBr in place of NaCl for comparison purposes. The (23)Na, (35)Cl, and (37)Cl double quantum filtered (DQF) patterns, from the 0.100 mol kg(-1) NaTDC sample, and (23)Na ones also from the 0.200 mol kg(-1) NaTDC one, in the presence of 0.750 mol kg(-1) NaCl, are a clear manifestation of motional anisotropy. Moreover, the DQF spectra of (23)Na and (37)Cl, which possess close quadrupole moments, display a striking similarity. The DQF lineshapes were simulated exploiting the Scilab environment to obtain an estimate of the residual quadrupole splitting magnitude. These results support the description of NaTDC micelles as cylindrical aggregates, strongly interacting at high ionic strengths, and capable of association with added electrolytes. Copyright © 2012 Elsevier Inc. All rights reserved.

An EPR investigation of the dynamic Jahn-Teller effect in SrCl2:y(2 plus) and SrCl2:Sc(2 plus)

NASA Technical Reports Server (NTRS)

Herrington, J. R.; Estle, T. L.; Boatner, L. A.

1972-01-01

EPR spectra have been observed for SrCl2:Y(2+) and SrCl2:Sc(2+) at liquid helium temperatures. At 1.2 K the spectra were dominated by anisotropic hyperfine patterns whose lineshapes and angular dependences were explained using second order solutions of the effective Hamiltonian for an isolated 2Eg state split by large random internal strains. Pronounced asymmetries in some of the strin produced lineshapes for Srcl2:Sc(2+) are shown to result from second order terms in the solution of the effective Hamiltonian. Coexisting with the anisotropic hyperfine patterns are weak nearly isotropic hyperfine patterns with typical lineshapes. Variations in the apparent intensity of lines in these weak hyperfine patterns as functions of the applied magnetic field direction and temperature imply that these lines result from averaging by vibronic relaxation of a portion of the anisotropic pattern. The effective Hamiltonian parameters for SrCl2:La(2+), SrCl2:y(2+), and SrCl2:SC(2+) are analyzed in terms of crystal field theory modified to include a dynamic Jahn-Teller effect.

Thermochemistry and Kinetics of the Cl+O2 Association Reaction

NASA Technical Reports Server (NTRS)

Nicovich, J. M.; Kreutter, K. D.; Shackelford, C. J.; Wine, P. H.

1997-01-01

Laser flash photolysis of Cl2/O2 mixtures has been employed in conjunction with Cl((sup 2)P(sub 3/2)) detection by time-resolved fluorescence spectroscopy to investigate equilibration kinetics for the reactions Cl + O2 + O is in equilibrium with ClOO + O2 at temperatures of 181-200 K and O2 pressures of 15-40 Torr. The third-order rate coefficient for the association reaction at 186.5 +/- 5.5 K is (8.9 +/- 2.9) x 10(exp -33) cm(exp 6) molecule(exp -2) s(exp -1) and the equilibrium constant (K(p)) at 185.4 K is 18.9 atm(exp -1) (factor of 1.7 uncertainty). A third law analysis of our data leads to a value for the Cl-OO bond dissociation energy of 4.76 +/- 0.49 kcal mol(exp -1).

Hg0 and HgCl2 Reference Gas Standards: ?NIST Traceability ...

EPA Pesticide Factsheets

EPA and NIST have collaborated to establish the necessary procedures for establishing the required NIST traceability of commercially-provided Hg0 and HgCl2 reference generators. This presentation will discuss the approach of a joint EPA/NIST study to accurately quantify the true concentrations of Hg0 and HgCl2 reference gases produced from high quality, NIST-traceable, commercial Hg0 and HgCl2 generators. This presentation will also discuss the availability of HCl and Hg0 compressed reference gas standards as a result of EPA's recently approved Alternative Methods 114 and 118. Gaseous elemental mercury (Hg0) and oxidized mercury (HgCl2) reference standards are integral to the use of mercury continuous emissions monitoring systems (Hg CEMS) for regulatory compliance emissions monitoring. However, a quantitative disparity of approximately 7-10% has been observed between commercial Hg0 and HgCl2 reference gases which currently limits the use of (HgCl2) reference gas standards. Resolving this disparity would enable the expanded use of (HgCl2) reference gas standards for regulatory compliance purposes.

Electrodeposited Cu2O doped with Cl: Electrical and optical properties

NASA Astrophysics Data System (ADS)

Pelegrini, S.; Tumelero, M. A.; Brandt, I. S.; Della Pace, R. D.; Faccio, R.; Pasa, A. A.

2018-04-01

For understanding the electrical and optical properties of electrodeposited Cl-doped Cu2O thin films, we have studied layers with increasing thickness and Cl concentrations of 0.8 and 1.2 at. %. The deposits were characterized by measuring the charge transport, the optical reflectance, and the photoluminescence. No significant decrease of electrical resistivity was observed in doped samples compared to undoped ones. A decrease of about five orders of magnitude was measured and ascribed to the presence of pinholes, as confirmed by scanning electron microscopy analyses. From optical measurements, we concluded that the Cl atoms are incorporated into substitutional sites of Cu2O lattices in agreement with photoluminescence results showing a strong reduction in the peak intensity of VO+2 defects in comparison to undoped layers. Computational calculation using density functional theory has pointed out high formation energy for single Cl related defects, but low formation energy for Cl-defect complexes, such as ClO + VCu, that strongly compensate the carriers generated by the Cl doping.

Urea inhibits NaK2Cl cotransport in human erythrocytes.

PubMed Central

Lim, J; Gasson, C; Kaji, D M

1995-01-01

We examined the effect of urea on NaK2Cl cotransport in human erythrocytes. In erythrocytes from nine normal subjects, the addition of 45 mM urea, a concentration commonly encountered in uremic subjects, inhibited NaK2Cl cotransport by 33 +/- 7%. Urea inhibited NaK2Cl cotransport reversibly, and in a concentration-dependent fashion with half-maximal inhibition at 63 +/- 10 mM. Acute cell shrinkage increased, and acute cell swelling decreased NaK2Cl cotransport in human erythrocytes. Okadaic acid (OA), a specific inhibitor of protein phosphatase 1 and 2A, increased NaK2Cl cotransport by nearly 80%, suggesting an important role for these phosphatases in the regulation of NaK2Cl cotransport. Urea inhibited bumetanide-sensitive K influx even when protein phosphatases were inhibited with OA, suggesting that urea acted by inhibiting a kinase. In cells subjected to shrinking and OA pretreatment, maneuvers expected to increase the net phosphorylation, urea inhibited cotransport only minimally, suggesting that urea acted by causing a net dephosphorylation of the cotransport protein, or some key regulatory protein. The finding that concentrations of urea found in uremic subjects inhibited NaK2Cl cotransport, a widespread transport pathway with important physiological functions, suggests that urea is not only a marker for accumulation of other uremic toxins, but may be a significant uremic toxin itself. PMID:7593597

Interaction of chromatin with NaCl and MgCl2. Solubility and binding studies, transition to and characterization of the higher-order structure.

PubMed

Ausio, J; Borochov, N; Seger, D; Eisenberg, H

1984-08-15

Chicken erythrocyte chromatin containing histones H1 and H5 was carefully separated into a number of well-characterized fractions. A distinction could be made between chromatin insoluble in NaCl above about 80 mM, and chromatin soluble at all NaCl concentrations. Both chromatin forms were indistinguishable electrophoretically and both underwent the transition from the low salt "10 nm" coil to the "30 nm" higher-order structure solenoid by either raising the MgCl2 concentration to about 0.3 mM or the NaCl concentration to about 75 mM. The transitions were examined in detail by elastic light-scattering procedures. It could be shown that the 10 nm form is a flexible coil. For the 30 nm solenoid, the assumption of a rigid cylindrical structure was in good agreement with 5.7 nucleosomes per helical turn. However, disagreement of calculated frictional parameters with values derived from quasielastic light-scattering and sedimentation introduced the possibility that the higher-order structure, under these conditions, is more extended, flexible, or perhaps a mixture of structures. Values for density and refractive index increments of chromatin are also given. To understand the interaction of chromatin with NaCl and with MgCl2, a number of experiments were undertaken to study solubility, precipitation, conformational transitions and binding of ions over a wide range of experimental conditions, including chromatin concentration.

Determination of product branching ratio of the ClO self-reaction at 298 K

NASA Astrophysics Data System (ADS)

Horowitz, A.; Bauer, D.; Crowley, J. N.; Moortgat, G. K.

1993-07-01

The Cl2-sensitized continuous photolysis of O3 mixtures in O2 was investigated at 298 K using time resolved single wavelength and diode array spectroscopy to monitor the decay of O3 and the formation of OClO. Φ-O3 was found to be 4.1±0.4. This value, combined with the determination of the initial rates of OClO formation, allowed the evaluation of the following branching ratios into the three bimolecular disproportionation channels of ClO reactions; k3a/k3 = 0.40 ± 0.08, k3b/k3 = 0.42 ± 0.08 and k3c/k3 = 0.18 ± 0.02 where ClO + ClO → Cl2 + O2 (3a), ClO + ClO → Cl + Cl + O2 (3b) and ClO + ClO → Cl + OClO (3c).

Rotational spectrum of CH3CN⋯ClF and evidence for the +I effect of a CH3 group on the ‘chlorine’ bond N⋯ClF

NASA Astrophysics Data System (ADS)

Page, M. D.; Waclawik, E. R.; Holloway, J. H.; Legon, A. C.

1999-10-01

The ground-state rotational spectra of the isotopomers CH 3C 14N⋯ 35ClF, CH 3C 14N⋯ 37ClF, CD 3C 14N⋯ 35ClF and CH 3C 15N⋯ 35ClF of a symmetric-rotor complex formed by methyl cyanide and chlorine monofluoride have been observed and analysed to give the spectroscopic constants B0, DJ, DJK, χaa( 14N), χaa(Cl) and Mbb. Interpretations of these quantities on the basis of simple models enabled the geometry and strength of binding of the complex to be determined. It is found that the atoms C-CN⋯ClF lie on the C 3 axis of this complex of C 3v symmetry and that the distance r(N⋯Cl)=2.561(2) Å. The quadratic force constants associated with the intermolecular stretching mode and with the bending motion of the CH 3CN subunit pivoted at its mass centre were determined from the centrifugal distortion constants DJ and 2 DJ+ DJK. Their values were k σ=13.9(3) N m -1 and k α=3.0(1)×10 -20 J rad -2, respectively. A comparison of r(N⋯Cl) values and of k σ values establishes that the +I effect of the CH 3 group when it replaces H in HCN leads to a similar shortening of r(N⋯Cl) and to a similar increase in k σ in the two series RCN⋯ClF and RCN⋯HCl (R=H or CH 3).

Sesión clínica de los NIH de tumores del estroma gastrointestinal (TEGI) infantiles y de tipo natural | Center for Cancer Research

Cancer.gov

Fecha de la sesión: Del 20 al 22 de junio de 2018 Esta solicitud es el primero de un proceso de varios pasos para considerar su participación en nuestra próxima sesión clínica de TEGI infantiles y de tipo natural. Por favor, lea las tres páginas y responda completamente todas las preguntas:

Luminescence upconversion under hydrostatic pressure in the 3d-metal systems Ti2+:NaCl and Ni2+:CsCdCl3

NASA Astrophysics Data System (ADS)

Wenger, Oliver S.; Salley, G. Mackay; Valiente, Rafael; Güdel, Hans U.

2002-06-01

We present a study of upconversion materials and processes under external hydrostatic pressure. The near-infrared to visible photon upconversion properties of Ti2+-doped NaCl and Ni2+-doped CsCdCl3 at 15 K are studied as a function of external hydrostatic pressure. It is found that in Ti2+:NaCl pressure can be used to switch on an efficient upconversion mechanism, which is inactive at ambient pressure, leading to an order-of-magnitude enhancement of the overall upconversion efficiency of this material. For Ni2+:CsCdCl3 it is demonstrated that upconversion luminescence excitation spectroscopy can be used to study the pressure dependence of excited state absorption transitions. The results demonstrate the ability to tune upconversion properties by altering the local crystal field of active ions, in addition to probing the pressure dependence of excited state absorption transitions via upconversion spectroscopy.

Targeting multiple heterogeneous hardware platforms with OpenCL

NASA Astrophysics Data System (ADS)

Fox, Paul A.; Kozacik, Stephen T.; Humphrey, John R.; Paolini, Aaron; Kuller, Aryeh; Kelmelis, Eric J.

2014-06-01

The OpenCL API allows for the abstract expression of parallel, heterogeneous computing, but hardware implementations have substantial implementation differences. The abstractions provided by the OpenCL API are often insufficiently high-level to conceal differences in hardware architecture. Additionally, implementations often do not take advantage of potential performance gains from certain features due to hardware limitations and other factors. These factors make it challenging to produce code that is portable in practice, resulting in much OpenCL code being duplicated for each hardware platform being targeted. This duplication of effort offsets the principal advantage of OpenCL: portability. The use of certain coding practices can mitigate this problem, allowing a common code base to be adapted to perform well across a wide range of hardware platforms. To this end, we explore some general practices for producing performant code that are effective across platforms. Additionally, we explore some ways of modularizing code to enable optional optimizations that take advantage of hardware-specific characteristics. The minimum requirement for portability implies avoiding the use of OpenCL features that are optional, not widely implemented, poorly implemented, or missing in major implementations. Exposing multiple levels of parallelism allows hardware to take advantage of the types of parallelism it supports, from the task level down to explicit vector operations. Static optimizations and branch elimination in device code help the platform compiler to effectively optimize programs. Modularization of some code is important to allow operations to be chosen for performance on target hardware. Optional subroutines exploiting explicit memory locality allow for different memory hierarchies to be exploited for maximum performance. The C preprocessor and JIT compilation using the OpenCL runtime can be used to enable some of these techniques, as well as to factor in hardware

Effect of the SiCl4 Flow Rate on SiBN Deposition Kinetics in SiCl4-BCl3-NH3-H2-Ar Environment

PubMed Central

Li, Jianping; Qin, Hailong; Liu, Yongsheng; Ye, Fang; Li, Zan; Cheng, Laifei; Zhang, Litong

2017-01-01

To improve the thermal and mechanical stability of SiCf/SiC or C/SiC composites with SiBN interphase, SiBN coating was deposited by low pressure chemical vapor deposition (LPCVD) using SiCl4-BCl3-NH3-H2-Ar gas system. The effect of the SiCl4 flow rate on deposition kinetics was investigated. Results show that deposition rate increases at first and then decreases with the increase of the SiCl4 flow rate. The surface of the coating is a uniform cauliflower-like structure at the SiCl4 flow rate of 10 mL/min and 20 mL/min. The surface is covered with small spherical particles when the flow rate is 30 mL/min. The coatings deposited at various SiCl4 flow rates are all X-ray amorphous and contain Si, B, N, and O elements. The main bonding states are B-N, Si-N, and N-O. B element and B-N bonding decrease with the increase of SiCl4 flow rate, while Si element and Si-N bonding increase. The main deposition mechanism refers to two parallel reactions of BCl3+NH3 and SiCl4+NH3. The deposition process is mainly controlled by the reaction of BCl3+NH3. PMID:28772986

The aluminum electrode in AlCl3-alkali-halide melts.

NASA Technical Reports Server (NTRS)

Holleck, G. L.; Giner, J.

1972-01-01

Passivation phenomena have been observed upon cathodic and anodic polarization of the Al electrode in AlCl3-KCl-NaCl melts between 100 and 160 C. They are caused by formation of a solid salt layer at the electrode surface resulting from concentration changes upon current flow. The anodic limiting currents increased with temperature and with decreasing AlCl3 content of the melt. Current voltage curves obtained on a rotating aluminum disk showed a linear relationship between the anodic limiting current and omega to the minus 1/2 power. Upon cathodic polarization, dendrite formation occurs at the Al electrode. The activation overvoltage in AlCl3-KCl-NaCl was determined by galvanostatic current step methods. An apparent exchange current density of 270 mA/sq cm at 130 C and a double layer capacity of 40 plus or minus 10 microfarad/sq cm were measured.

Biotic and abiotic degradation of CL-20 and RDX in soils.

PubMed

Crocker, Fiona H; Thompson, Karen T; Szecsody, James E; Fredrickson, Herbert L

2005-01-01

The caged cyclic nitramine 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) is a new explosive that has the potential to replace existing military explosives, but little is known about its environmental toxicity, transport, and fate. We quantified and compared the aerobic environmental fate of CL-20 to the widely used cyclic nitramine explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in surface and subsurface soil microcosms. Soil-free controls and biologically attenuated soil controls were used to separate abiotic processes from biologically mediated processes. Both abiotic and biological processes significantly degraded CL-20 in all soils examined. Apparent abiotic, first-order degradation rates (k) for CL-20 were not significantly different between soil-free controls (0.018 < k < 0.030 d(-1)) and biologically attenuated soil controls (0.003 < k < 0.277 d(-1)). The addition of glucose to biologically active soil microcosms significantly increased CL-20 degradation rates (0.068 < k < 1.22 d(-1)). Extents of mineralization of (14)C-CL-20 to (14)CO(2) in biologically active soil microcosms were 41.1 to 55.7%, indicating that the CL-20 cage was broken, since all carbons are part of the heterocyclic cage. Under aerobic conditions, abiotic degradation rates of RDX were generally slower (0 < k < 0.032 d(-1)) than abiotic CL-20 degradation rates. In biologically active soil microcosms amended with glucose aerobic RDX degradation rates varied between 0.010 and 0.474 d(-1). Biodegradation was a key factor in determining the environmental fate of RDX, while a combination of biotic and abiotic processes was important with CL-20. Our data suggest that CL-20 should be less recalcitrant than RDX in aerobic soils.

Virtual screening of cocrystal formers for CL-20

NASA Astrophysics Data System (ADS)

Zhou, Jun-Hong; Chen, Min-Bo; Chen, Wei-Ming; Shi, Liang-Wei; Zhang, Chao-Yang; Li, Hong-Zhen

2014-08-01

According to the structure characteristics of 2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (CL-20) and the kinetic mechanism of the cocrystal formation, the method of virtual screening CL-20 cocrystal formers by the criterion of the strongest intermolecular site pairing energy (ISPE) was proposed. In this method the strongest ISPE was thought to determine the first step of the cocrystal formation. The prediction results for four sets of common drug molecule cocrystals by this method were compared with those by the total ISPE method from the reference (Musumeci et al., 2011), and the experimental results. This method was then applied to virtually screen the CL-20 cocrystal formers, and the prediction results were compared with the experimental results.

Efficient 'Foton' electric-discharge KrCl laser

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

Panchenko, Aleksei N; Tarasenko, Viktor F

The design of the 'Foton' electric-discharge laser, optimised for operation on the basis of KrCl* molecules, and its energy parameters were investigated. At {lambda} = 222 nm the radiation energy was up to 250 mJ per pulse. The specific output radiation energy was 2.5 J litre{sup -1} and the laser efficiency was in excess of 0.8%. The possibility of further improvement of the characteristics of electric-discharge KrCl lasers are discussed. (lasers)

Electrochemical Codeposition of Al-Li-Mg Alloys at Solid Aluminum Electrode from LiCl-KCl-MgCl2 Molten Salt System

NASA Astrophysics Data System (ADS)

Ye, Ke; Zhang, Mi Lin; Chen, Ye; Han, Wei; de Yan, Yong; Cao, Peng

2010-06-01

The electrochemical codeposition of Mg and Li at an aluminium electrode in LiCl-KCl (50:50 wt pct) melts containing different concentrations of MgCl2 at 893 K (620 °C) to form Al-Li-Mg alloys was investigated. Cyclic voltammograms showed that the potential of Li metal deposition at an Al electrode, before the addition of MgCl2, is more positive than that of Li metal deposition at an Mo electrode, which indicated the formation of an Al-Li alloy. The underpotential deposition of magnesium at an aluminium electrode leads to the formation of Al-Mg alloys, and the succeeding underpotential deposition of lithium on predeposited Al-Mg alloys leads to the formation of Al-Li-Mg alloys. Chronopotentiometric measurements indicated that the codeposition of Mg and Li occurs at current densities lower than -0.668 A cm-2 in LiCl-KCl-MgCl2 (8 wt pct) melts at an aluminium electrode. The chronoamperometric studies indicated that the onset potential for the codeposition of Mg and Li is -2.000 V, and the codeposition of Mg and Li at an aluminium electrode is formed into Al-Li-Mg alloys when the applied potentials are more negative than -2.000 V. X-ray diffraction and inductively coupled plasma analysis indicated that Al-Li-Mg alloys with different lithium and magnesium contents were prepared via potentiostatic and galvanostatic electrolysis. The microstructure of typical dual phases of the Al-Li-Mg alloy was characterized by an optical microscope and by scanning electron microscopy. The analysis of energy dispersive spectrometry showed that the elements of Al and Mg distribute homogeneously in the Al-Li-Mg alloy. The lithium and magnesium contents of Al-Li-Mg alloys can be controlled by MgCl2 concentrations and by electrolytic parameters.

Inelastic neutron scattering investigation of low temperature phase transition in Rb2ZnCl4 and K2ZnCl4

NASA Astrophysics Data System (ADS)

Quilichini, M.; Dvořák, V.; Boutrouille, P.

1991-09-01

Inelastic scattering of neutrons has revealed soft optic modes at the T point frac{1}{2}({b}^*+{c}^*) of the Brillouin zone both in Rb2ZnCl4 and K2ZnCl4 which are responsible for the phase transition from the ferroelectric to the lowest temperature phase of these materials. Moreover, in K2ZnCl4 near the T point a minimum on the soft optic branch in the direction (μ{b}^*+frac{1}{2}{c}^*) has been found which confirms the existence of a new incommensurate phase recently discovered by Gesi. The origin of this incommensurate phase is discussed from a phenomenological point of view and formulae for elastic constants are derived describing their behaviour near transition into incommensurate phase. Des mesures de diffusion inélastique des neutrons ont mis en évidence l'existence d'un mode optique mou au point T(frac{1}{2}({b}^*+{c}^*)) de la zone de Brillouin responsable de la transition de la phase ferroélectrique vers la phase basse température dans les deux composés Rb2ZnCl4 and K2ZnCl4. Pour K2ZnCl4 on montre que la branche optique molle présente un minimum au voisinage de T dans la direction (μ{b}^*+frac{1}{2}{c}^*), ce qui confirme l'existence de la nouvelle phase incommensurable récemment trouvée par Gesi. L'origine de cette phase est discutée sur la base d'un modèle phénoménologique dont on dérive aussi les formules des constantes élastiques et leur comportement au voisinage de la transition vers la phase incommensurable.

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br

NASA Technical Reports Server (NTRS)

Hsu, K.-J.; Demore, W. B.

1994-01-01

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2) and (for CH2Cl2) HFC-161 (CH3CH2F). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.

Cosmogenic Cl-36 production rates in meteorites and the lunar surface

NASA Technical Reports Server (NTRS)

Nishiizumi, K.; Arnold, J. R.; Kubik, P. W.; Elmore, D.; Reedy, R. C.

1989-01-01

Activity vs. depth profiles of cosmic ray produced Cl-36 were measured in metal from two cores each in the St. Severin and Jilin chondrites and in lunar core 15008. Production of Cl-36 in these samples range from high-energy reactions with Fe and Ni to low-energy reactions with Ca and K and possibly neutron-capture reactions with Cl-36. The cross sections used in the Reedy-Arnold model for neutron-induced reactions were adjusted to get production rates that fit the measured Cl-36 activities in St. Severin metal and in the lunar soil of core 15008. The Cl-36 in metal from St. Severin has a fairly flat activity-vs-depth profile, unlike most other cosmogenic nuclides in bulk samples from St. Severin, which increase in concentration with depth. In metal from Jilin, a decrease in Cl-36 was observed near its center. The length of Jilin's most recent cosmic-ray exposure was approximately 0.5 My. Lunar core 15008 has an excess in Cl-36 of about 4 dpm/kg near its surface that was produced by solar-proton-induced reactions. The calculated production rates are consistent with these measured trends in 15008.

Effect of NaCl treatments on glucosinolate metabolism in broccoli sprouts*

PubMed Central

Guo, Rong-fang; Yuan, Gao-feng; Wang, Qiao-mei

2013-01-01

To understand the regulation mechanism of NaCl on glucosinolate metabolism in broccoli sprouts, the germination rate, fresh weight, contents of glucosinolates and sulforaphane, as well as myrosinase activity of broccoli sprouts germinated under 0, 20, 40, 60, 80, and 100 mmol/L of NaCl were investigated in our experiment. The results showed that glucoerucin, glucobrassicin, and 4-hydroxy glucobrassicin in 7-d-old broccoli sprouts were significantly enhanced and the activity of myrosinase was inhibited by 100 mmol/L of NaCl. However, the total glucosinolate content in 7-d-old broccoli sprouts was markedly decreased although the fresh weight was significantly increased after treatment with NaCl at relatively low concentrations (20, 40, and 60 mmol/L). NaCl treatment at the concentration of 60 mmol/L for 5 d maintained higher biomass and comparatively higher content of glucosinolates in sprouts of broccoli with decreased myrosinase activity. A relatively high level of NaCl treatment (100 mmol/L) significantly increased the content of sulforaphane in 7-d-old broccoli sprouts compared with the control. These results indicate that broccoli sprouts grown under a suitable concentration of NaCl could be desirable for human nutrition. PMID:23365011

Swan: A tool for porting CUDA programs to OpenCL

NASA Astrophysics Data System (ADS)

Harvey, M. J.; De Fabritiis, G.

2011-04-01

The use of modern, high-performance graphical processing units (GPUs) for acceleration of scientific computation has been widely reported. The majority of this work has used the CUDA programming model supported exclusively by GPUs manufactured by NVIDIA. An industry standardisation effort has recently produced the OpenCL specification for GPU programming. This offers the benefits of hardware-independence and reduced dependence on proprietary tool-chains. Here we describe a source-to-source translation tool, "Swan" for facilitating the conversion of an existing CUDA code to use the OpenCL model, as a means to aid programmers experienced with CUDA in evaluating OpenCL and alternative hardware. While the performance of equivalent OpenCL and CUDA code on fixed hardware should be comparable, we find that a real-world CUDA application ported to OpenCL exhibits an overall 50% increase in runtime, a reduction in performance attributable to the immaturity of contemporary compilers. The ported application is shown to have platform independence, running on both NVIDIA and AMD GPUs without modification. We conclude that OpenCL is a viable platform for developing portable GPU applications but that the more mature CUDA tools continue to provide best performance. Program summaryProgram title: Swan Catalogue identifier: AEIH_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEIH_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GNU Public License version 2 No. of lines in distributed program, including test data, etc.: 17 736 No. of bytes in distributed program, including test data, etc.: 131 177 Distribution format: tar.gz Programming language: C Computer: PC Operating system: Linux RAM: 256 Mbytes Classification: 6.5 External routines: NVIDIA CUDA, OpenCL Nature of problem: Graphical Processing Units (GPUs) from NVIDIA are preferentially programed with the proprietary CUDA programming toolkit. An

The sources and evolution of mineralising fluids in iron oxide-copper-gold systems, Norrbotten, Sweden: Constraints from Br/Cl ratios and stable Cl isotopes of fluid inclusion leachates

NASA Astrophysics Data System (ADS)

Gleeson, S. A.; Smith, M. P.

2009-10-01

We have analysed the halogen concentrations and chlorine stable isotope composition of fluid inclusion leachates from three spatially associated Fe-oxide ± Cu ± Au mineralising systems in Norrbotten, Sweden. Fluid inclusions in late-stage veins in Fe-oxide-apatite deposits contain saline brines and have a wide range of Br/Cl molar ratios, from 0.2 to 1.1 × 10 -3 and δ 37Cl values from -3.1‰ to -1.0‰. Leachates from saline fluid inclusions from the Greenstone and Porphyry hosted Cu-Au prospects have Br/Cl ratios that range from 0.2 to 0.5 × 10 -3 and δ 37Cl values from -5.6‰ to -1.3‰. Finally, the Cu-Au deposits hosted by the Nautanen Deformation Zone (NDZ) have Br/Cl molar ratios from 0.4 to 1.1 × 10 -3 and δ 37Cl values that range from -2.4‰ to +0.5‰, although the bulk of the data fall within 0‰ ± 0.5‰. The Br/Cl ratios of leachates are consistent with the derivation of salinity from magmatic sources or from the dissolution of halite. Most of the isotopic data from the Fe-oxide-apatite and Greenstone deposits are consistent with a mantle derived source of the chlorine, with the exception of the four samples with the most negative values. The origin of the low δ 37Cl values in these samples is unknown but we suggest that there may have been some modification of the Cl-isotope signature due to fractionation between the mineralising fluids and Cl-rich silicate assemblages found in the alteration haloes around the deposits. If such a process has occurred then a modified crustal source of the chlorine for all the samples cannot be ruled out although the amount of fractionation necessary to generate the low δ 37Cl values would be significantly larger. The source of Cl in the NDZ deposits has a crustal signature, which suggests the Cl in this system may be derived from (meta-) evaporites or from input from crustal melts such as granitic pegmatites of the Lina Suite.

Pressure induced structural phase transition from NaCl-type (B1) to CsCl-type (B2) structure in sodium chloride

NASA Astrophysics Data System (ADS)

Jain, Aayushi; Dixit, R. C.

2018-05-01

Pressure induced structural phase transition of NaCl-type (B1) to CsCl-type (B2) structure in Sodium Chloride NaCl are presented. An effective interionic interaction potential (EIOP) with long range Coulomb, van der Waals (vdW) interaction and the short-range repulsive interaction upto second-neighbor ions within the Hafemeister and Flygare approach with modified ionic charge is reported here. The reckon value of the phase transition pressure (Pt) and the magnitude of the discontinuity in volume at the transition pressure are compatible as compared with reported data. The variations of elastic constants and their combinations with pressure follow ordered behavior. The present approach has also succeeded in predicting the Born and relative stability criteria.

A Novel Mechanism of pH Buffering in C. elegans Glia: Bicarbonate Transport via the Voltage-Gated ClC Cl- Channel CLH-1.

PubMed

Grant, Jeff; Matthewman, Cristina; Bianchi, Laura

2015-12-16

An important function of glia is the maintenance of the ionic composition and pH of the synaptic microenvironment. In terms of pH regulation, HCO3 (-) buffering has been shown to be important in both glia and neurons. Here, we used in vivo fluorescent pH imaging and RNA sequencing of the amphid sheath glia of Caenorhabditis elegans to reveal a novel mechanism of cellular HCO3 (-) uptake. While the classical mechanism of HCO3 (-) uptake involves Na(+)/HCO3 (-) cotransporters, here we demonstrate that the C. elegans ClC Cl(-) channel CLH-1 is highly permeable to HCO3 (-) and mediates HCO3 (-) uptake into amphid sheath glia. CLH-1 has homology and electrophysiological properties similar to the mammalian ClC-2 Cl(-) channel. Our data suggest that, in addition to maintaining synaptic Cl(-) concentration, these channels may also be involved in maintenance of synaptic pH via HCO3 (-) flux. These findings provide an exciting new facet of study regarding how pH is regulated in the brain. Maintenance of pH is essential for the physiological function of the nervous system. HCO3 (-) is crucial for pH regulation and is transported into the cell via ion transporters, including ion channels, the molecular identity of which remains unclear. In this manuscript, we describe our discovery that the C. elegans amphid sheath glia regulate intracellular pH via HCO3 (-) flux through the voltage-gated ClC channel CLH-1. This represents a novel function for ClC channels, which has implications for their possible role in mammalian glial pH regulation. This discovery may also provide a novel therapeutic target for pathologic conditions, such as ischemic stroke where acidosis leads to widespread death of glia and subsequently neurons. Copyright © 2015 the authors 0270-6474/15/3516377-21$15.00/0.

Analysis of CL-20 in environmental matrices: water and soil.

PubMed

Larson, Steven L; Felt, Deborah R; Davis, Jeffrey L; Escalon, Lynn

2002-04-01

Analytical techniques for the detection of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo(5.5.0.05,9.03,11)dodecane (CL-20) in water and soil are developed by adapting methods traditionally used for the analysis of nitroaromatics. CL-20 (a new explosives compound) is thermally labile, exhibits high polarity, and has low solubility in water. These constraints make the use of specialized sample handling, preparation, extraction, and analysis necessary. The ability to determine the concentrations of this new explosive compound in environmental matrices is helpful in understanding the environmental fate and effects of CL-20; understanding the physical, chemical, and biological fate of CL-20; and can be used in developing remediation technologies and determining their efficiency. The toxicity and mobility of new explosives in soil and groundwater are also of interest, and analytical techniques for quantitating CL-20 and its degradation products in soil and natural waters make these investigations possible.

Physical and Chemical Microstructural Damage in Pressed CL-20 explosives

NASA Astrophysics Data System (ADS)

Demol, Gauthier; Sandusky, Harold W.

1999-06-01

Based upon its molecular composition, its structure, and its heat of formation, it was expected that CL-20 (hexanitrohexaazaisowurtzitane) would be more energetic and more sensitive than RDX and HMX. Reports of batch-to-batch variations in the sensitivity of neat CL-20 have led to its sensitivity being ranked in the range between the sensitivity of RDX and that of PETN. The ultimate utility of CL-20 as an ingredient in explosive and propellant formulations will depend upon the ability to understand the factors that are responsible for this batch-to-batch variability, and to control the sensitivity in formulations within acceptable limits. This work is a characterization of CL-20 at various stages in its life cycle. The evolution of damage from the initial neat crystals of CL-20 to the ready-to-use pressed pellets will be described. This characterization includes physical documentation using light microscopy and Scanning Electron Microscopy. Spatially resolved chemical analysis is also performed using Fourier-Transform Infrared Spectroscopy.

SO2 absorption in EmimCl-TEG deep eutectic solvents.

PubMed

Yang, Dezhong; Zhang, Shaoze; Jiang, De-En; Dai, Sheng

2018-06-06

Deep eutectic solvents (DESs) based on 1-ethyl-3-methylimidazolium chloride (EmimCl) and triethylene glycol (TEG) with different molar ratios (from 6 : 1 to 1 : 1) were prepared. FTIR and theoretical calculation indicated that the C2-H on the imidazolium ring form hydrogen bonds with the hydroxyl group rather than the ether O atom of the TEG. The EmimCl-TEG DESs can efficiently capture SO2; in particular, EmimCl-TEG (6 : 1) can capture 0.54 g SO2 per gram of solvent at 0.10 atm and 20 °C, the highest absorption amount for DESs under the same conditions. Theoretical calculation showed that the high SO2 absorption capacity was mainly due to the strong charge-transfer interaction between SO2 and the anion Cl-. Moreover, SO2 desorption in the DESs can be controlled by tuning the interaction between EmimCl and TEG, and the DESs can be cycled many times.

Atmospheric chemistry of the reaction ClO + O2 reversible reaction ClO (center dot) O2: Where it stands, what needs to be done, and why?

NASA Technical Reports Server (NTRS)

Prasad, Sheo S.; Lee, Timothy J.

1994-01-01

Possible existence and chemistry of ClO (center dot) O2 was originally proposed to explain the Norrish-Neville effect that O2 suppresses chlorine photosensitized loss of ozone. It was also thought that ClO (center dot) O2 might have some atmospheric chemistry significance. Recently, doubts have been cast on this proposal, because certain laboratory data seem to imply that the equilibrium constant of the title reaction is so small that ClO (center dot) O2 may be too unstable to matter. However, those data create only a superficial illusion to that effect, because on a closer analysis they do not disprove a moderately stable and chemically significant ClO (center dot) O2. Furthermore, our state-of-the-science accurate computational chemistry calculations also suggest that ClO (center dot) O2 may be a weakly bound ClOOO radical with a reactive (2)A ground electronic state. There is therefore a need to design and perform definitive experimental tests of the existence and chemistry of the ClO (center dot) O2 species, which we discuss and which have the potential to mediate the chlorine-catalyzed stratospheric ozone depletion.

ClC Channels and Transporters: Structure, Physiological Functions, and Implications in Human Chloride Channelopathies

PubMed Central

Poroca, Diogo R.; Pelis, Ryan M.; Chappe, Valérie M.

2017-01-01

The discovery of ClC proteins at the beginning of the 1990s was important for the development of the Cl- transport research field. ClCs form a large family of proteins that mediate voltage-dependent transport of Cl- ions across cell membranes. They are expressed in both plasma and intracellular membranes of cells from almost all living organisms. ClC proteins form transmembrane dimers, in which each monomer displays independent ion conductance. Eukaryotic members also possess a large cytoplasmic domain containing two CBS domains, which are involved in transport modulation. ClC proteins function as either Cl- channels or Cl-/H+ exchangers, although all ClC proteins share the same basic architecture. ClC channels have two gating mechanisms: a relatively well-studied fast gating mechanism, and a slow gating mechanism, which is poorly defined. ClCs are involved in a wide range of physiological processes, including regulation of resting membrane potential in skeletal muscle, facilitation of transepithelial Cl- reabsorption in kidneys, and control of pH and Cl- concentration in intracellular compartments through coupled Cl-/H+ exchange mechanisms. Several inherited diseases result from C1C gene mutations, including myotonia congenita, Bartter’s syndrome (types 3 and 4), Dent’s disease, osteopetrosis, retinal degeneration, and lysosomal storage diseases. This review summarizes general features, known or suspected, of ClC structure, gating and physiological functions. We also discuss biophysical properties of mammalian ClCs that are directly involved in the pathophysiology of several human inherited disorders, or that induce interesting phenotypes in animal models. PMID:28386229

Density-based parallel skin lesion border detection with webCL

PubMed Central

2015-01-01

Background Dermoscopy is a highly effective and noninvasive imaging technique used in diagnosis of melanoma and other pigmented skin lesions. Many aspects of the lesion under consideration are defined in relation to the lesion border. This makes border detection one of the most important steps in dermoscopic image analysis. In current practice, dermatologists often delineate borders through a hand drawn representation based upon visual inspection. Due to the subjective nature of this technique, intra- and inter-observer variations are common. Because of this, the automated assessment of lesion borders in dermoscopic images has become an important area of study. Methods Fast density based skin lesion border detection method has been implemented in parallel with a new parallel technology called WebCL. WebCL utilizes client side computing capabilities to use available hardware resources such as multi cores and GPUs. Developed WebCL-parallel density based skin lesion border detection method runs efficiently from internet browsers. Results Previous research indicates that one of the highest accuracy rates can be achieved using density based clustering techniques for skin lesion border detection. While these algorithms do have unfavorable time complexities, this effect could be mitigated when implemented in parallel. In this study, density based clustering technique for skin lesion border detection is parallelized and redesigned to run very efficiently on the heterogeneous platforms (e.g. tablets, SmartPhones, multi-core CPUs, GPUs, and fully-integrated Accelerated Processing Units) by transforming the technique into a series of independent concurrent operations. Heterogeneous computing is adopted to support accessibility, portability and multi-device use in the clinical settings. For this, we used WebCL, an emerging technology that enables a HTML5 Web browser to execute code in parallel for heterogeneous platforms. We depicted WebCL and our parallel algorithm design. In

Density-based parallel skin lesion border detection with webCL.

PubMed

Lemon, James; Kockara, Sinan; Halic, Tansel; Mete, Mutlu

2015-01-01

Dermoscopy is a highly effective and noninvasive imaging technique used in diagnosis of melanoma and other pigmented skin lesions. Many aspects of the lesion under consideration are defined in relation to the lesion border. This makes border detection one of the most important steps in dermoscopic image analysis. In current practice, dermatologists often delineate borders through a hand drawn representation based upon visual inspection. Due to the subjective nature of this technique, intra- and inter-observer variations are common. Because of this, the automated assessment of lesion borders in dermoscopic images has become an important area of study. Fast density based skin lesion border detection method has been implemented in parallel with a new parallel technology called WebCL. WebCL utilizes client side computing capabilities to use available hardware resources such as multi cores and GPUs. Developed WebCL-parallel density based skin lesion border detection method runs efficiently from internet browsers. Previous research indicates that one of the highest accuracy rates can be achieved using density based clustering techniques for skin lesion border detection. While these algorithms do have unfavorable time complexities, this effect could be mitigated when implemented in parallel. In this study, density based clustering technique for skin lesion border detection is parallelized and redesigned to run very efficiently on the heterogeneous platforms (e.g. tablets, SmartPhones, multi-core CPUs, GPUs, and fully-integrated Accelerated Processing Units) by transforming the technique into a series of independent concurrent operations. Heterogeneous computing is adopted to support accessibility, portability and multi-device use in the clinical settings. For this, we used WebCL, an emerging technology that enables a HTML5 Web browser to execute code in parallel for heterogeneous platforms. We depicted WebCL and our parallel algorithm design. In addition, we tested

Platelet-derived growth factor regulates K-Cl cotransport in vascular smooth muscle cells.

PubMed

Zhang, Jing; Lauf, Peter K; Adragna, Norma C

2003-03-01

Platelet-derived growth factor (PDGF), a potent serum mitogen for vascular smooth muscle cells (VSMCs), plays an important role in membrane transport regulation and in atherosclerosis. K-Cl cotransport (K-Cl COT/KCC), the coupled-movement of K and Cl, is involved in ion homeostasis. VSMCs possess K-Cl COT activity and the KCC1 and KCC3 isoforms. Here, we report on the effect of PDGF on K-Cl COT activity and mRNA expression in primary cultures of rat VSMCs. K-Cl COT was determined as the Cl-dependent Rb influx and mRNA expression by semiquantitative RT-PCR. Twenty four-hour serum deprivation inhibited basal K-Cl COT activity. Addition of PDGF increased total protein content and K-Cl COT activity in a time-dependent manner. PDGF activated K-Cl COT in a dose-dependent manner, both acutely (10 min) and chronically (12 h). AG-1296, a selective inhibitor of the PDGF receptor tyrosine kinase, abolished these effects. Actinomycin D and cycloheximide had no effect on the acute PDGF activation of K-Cl COT, suggesting posttranslational regulation by the drug. Furthermore, PDGF increased KCC1 and decreased KCC3 mRNA expression in a time-dependent manner. These results indicate that chronic activation of K-Cl COT activity by PDGF may involve regulation of the two KCC mRNA isoforms, with KCC1 playing a dominant role in the mechanism of PDGF-mediated activation.

New {sup 34}Cl proton-threshold states and the thermonuclear {sup 33}S(p,{gamma}){sup 34}Cl rate in ONe novae

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

Parikh, A.; Faestermann, T.; Kruecken, R.

2009-07-15

Analysis of presolar grains in primitive meteorites has shown isotopic ratios largely characteristic of the conditions thought to prevail in various astrophysical environments. A possible indicator for a grain of ONe nova origin is a large {sup 33}S abundance: nucleosynthesis calculations predict as much as 150 times the solar abundance of {sup 33}S in the ejecta of nova explosions on massive ONe white dwarfs. This overproduction factor may, however, vary by factors of at least 0.01-3 because of uncertainties of several orders of magnitude in the {sup 33}S(p,{gamma}){sup 34}Cl reaction rate at nova peak temperatures (T{sub peak}{approx}0.1-0.4 GK). These uncertaintiesmore » arise due to the lack of nuclear physics information for states within {approx}600 keV of the {sup 33}S+p threshold in {sup 34}Cl (S{sub p}({sup 34}Cl) = 5143 keV). To better constrain this rate we have measured, for the first time, the {sup 34}S({sup 3}He,t){sup 34}Cl reaction over the region E{sub x}({sup 34}Cl) = 4.9-6 MeV. We confirm previous states and find 15 new states in this energy region. New {sup 33}S(p,{gamma}){sup 34}Cl resonances at E{sub R}=281(2), 301(2), and 342(2) keV may dominate this rate at relevant nova temperatures. Our results could affect predictions of sulphur isotopic ratios in nova ejecta (e.g., {sup 32}S/{sup 33}S) that may be used as diagnostic tools for the nova paternity of grains.« less

Chloride (Cl-) ion-mediated shape control of palladium nanoparticles

NASA Astrophysics Data System (ADS)

Nalajala, Naresh; Chakraborty, Arup; Bera, Bapi; Neergat, Manoj

2016-02-01

The shape control of Pd nanoparticles is investigated using chloride (Cl-) ions as capping agents in an aqueous medium in the temperature range of 60-100 °C. With weakly adsorbing and strongly etching Cl- ions, oxygen plays a crucial role in shape control. The experimental factors considered are the concentration of the capping agents, reaction time and reaction atmosphere. Thus, Pd nanoparticles of various shapes with high selectivity can be synthesized. Moreover, the removal of Cl- ions from the nanoparticle surface is easier than that of Br- ions (moderately adsorbing and etching) and I- ions (strongly adsorbing and weakly etching). The cleaned Cl- ion-mediated shape-controlled Pd nanoparticles are electrochemically characterized and the order of the half-wave potential of the oxygen reduction reaction in oxygen-saturated 0.1 M HClO4 solution is of the same order as that observed with single-crystal Pd surfaces.

Comparison of Cl2 and HCl Adsorption on Si(100)-(2x1)

DTIC Science & Technology

1992-06-01

amount of SiCl4 at ~ 500K. For HC1, the only observed etching product is SiCl2. 3 1. Introduction It is important to understand the basic chemistry of...as SiCl2 (a), SiCl3 (a) or SiCl4 (a), are not observed following either C12 or HCl adsorption at 100K. These chlorides should exhibit an asymmetric

Crystal structures of Ca(ClO4)2·4H2O and Ca(ClO4)2·6H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The title compounds, calcium perchlorate tetra­hydrate and calcium perchlorate hexa­hydrate, were crystallized at low temperatures according to the solid–liquid phase diagram. The structure of the tetra­hydrate consists of one Ca2+ cation eightfold coordinated in a square-anti­prismatic fashion by four water mol­ecules and four O atoms of four perchlorate tetra­hedra, forming chains parallel to [01-1] by sharing corners of the ClO4 tetra­hedra. The structure of the hexa­hydrate contains two different Ca2+ cations, each coordinated by six water mol­ecules and two O atoms of two perchlorate tetra­hedra, forming [Ca(H2O)6(ClO4)]2 dimers by sharing two ClO4 tetra­hedra. The dimers are arranged in sheets parallel (001) and alternate with layers of non-coordinating ClO4 tetra­hedra. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ClO4 tetra­hedra and water mol­ecules as acceptor groups lead to the formation of a three-dimensional network in the two structures. Ca(ClO4)2·6H2O was refined as a two-component inversion twin, with an approximate twin component ratio of 1:1 in each of the two structures. PMID:25552974

Electronic spectrum of non-tetrahedral acceptors in CdTe:Cl and CdTe:Bi,Cl single crystals

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

Krivobok, V. S., E-mail: krivobok@lebedev.ru; Moscow Institute of Physics and Technology; Nikolaev, S. N.

2016-02-07

The electronic spectra of complex acceptors in compensated CdTe:Cl, CdTe:Ag,Cl, and CdTe:Bi,Cl single crystals are studied using low-temperature photoluminescence (PL) measurements under both nonresonant and resonant excitation of distant donor–acceptor pairs (DAP). The wavelength modulation of the excitation source combined with the analysis of the differential PL signal is used to enhance narrow spectral features obscured because of inhomogeneous line broadening and/or excitation transfer for selectively excited DAPs. For the well-known tetrahedral (T{sub D}) Ag{sub Cd} acceptor, the energies of four excited states are measured, and the values obtained are shown to be in perfect agreement with the previous data.more » Moreover, splitting between the 2P{sub 3/2} (Γ{sub 8}) and 2S{sub 3/2} (Γ{sub 8}) states is clearly observed for Ag{sub Cd} centers located at a short distance (5–7 nm) from a hydrogen-like donor (Cl{sub Te}). This splitting results from the reduction of the T{sub D} symmetry taking place when the acceptor is a member of a donor–acceptor pair. For the Cl-related complex acceptor with an activation energy of ∼121 meV (A-center), the energies of eight excited states are measured. It is shown that this defect produces low-symmetry central-cell correction responsible for the strong splitting of S-like T{sub D} shells. The energy spectrum of the Bi-related shallow acceptor with an activation energy of ∼36 meV is measured as well. The spectrum obtained differs drastically from the hydrogen-like set of levels, which indicates the existence of repulsive low-symmetry perturbation of the hydrogen-like Coulomb potential. It is also shown that the spectra of selectively excited PL recorded for a macroscopic ensemble of distant donor–acceptor pairs allow one to detect the low symmetry of acceptors of a given type caused by their complex nature or by the Jahn–Teller distortion. This method does not require any additional (external) field

Effect of NaCl concentration on productivity and mineral composition of Salicornia europaea as a potential crop for utilization NaCl in LSS

NASA Astrophysics Data System (ADS)

Ushakova, S. A.; Kovaleva, N. P.; Gribovskaya, I. V.; Dolgushev, V. A.; Tikhomirova, N. A.

The accumulation of solid and liquid wastes in manmade ecosystems presents a problem that has not been efficiently solved yet. Urine, containing NaCl, are part of these products. This is an obstacle to the creation of biological systems with a largely closed material cycling, because the amount of solid and liquid wastes in them must be reduced to a minimum. A possible solution to the problem is to select plant species capable of utilizing sufficiently high concentrations of NaCl, edible for humans, and featuring high productivity. Until recently, the life support systems have included the higher plants that were either sensitive to salinization (wheat, many of the legumes, carrot, potato, maize) or relatively salt-resistant (barley, sugar beet, spinach). Salicomia europaea, whose above-ground part is fully edible for humans, is one of the most promising candidates to be included in life support systems. It is reported in the literature that this plant is capable of accumulating up to 50% NaCl (dry basis). Besides, excessive accumulation of sodium ions should bring forth a decrease in the uptake of potassium ions and other biogenic elements. The aim of this work is to study the feasibility of using S. europaea plants in growth chambers to involve NaCl into material cycling. Plants were grown in vegetation chambers at the irradiance of 100 or 150 W/m 2 PAR (photosynthetically active radiation) and the air temperature 24 °C, by two methods. The first method was to grow the plants on substrate - peat. The peat was supplemented with either 3% NaCl (Variant 1) or 6% NaCl (Variant 2) of the oven-dry mass of the peat. The second method was to grow the plants in water culture, using the solution with a full complement of nutrients, which contained 0.0005% of NaCl, 1% or 2%. The study showed that the addition of NaCl to the substrate or to the solution resulted in the formation of more succulent plants, which considerably increased their biomass. The amount of NaCl uptake

Electronic effects on the catalytic disproportionation of formic acid to methanol by [Cp*Ir(III)(R-bpy)Cl]Cl complexes.

PubMed

Sasayama, A F; Moore, C E; Kubiak, C P

2016-02-14

A series of [Cp*Ir(III)(R-bpy)Cl]Cl (R-bpy = 4,4'-di-R-2,2'-bipyridine; R = CF3, H, Me, tBu, OMe) complexes was prepared and studied for catalytic formic acid disproportionation. The relationship between the electron donating strength of the bipyridine substituents and methanol production of the corresponding complexes was analyzed; the unsubstituted (R = H) complex was the most selective for methanol formation.

High-resolution Measurement of Contact Ion-pair Structures in Aqueous RbCl Solutions from the Simultaneous Corefinement of their Rb and Cl K-edge XAFS and XRD Spectra

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

Pham, Van-Thai; Fulton, John L.

2016-06-21

In concentrated solutions of aqueous RbCl, all of the Rb+ and Cl- ions exist as contact ion pairs. This full structural assessment is derived from the refinement of three independent experimental measurements: the Rb and Cl K-edge x-ray absorption fine structure (XAFS) and the x-ray diffraction spectra (XRD). This simultaneous refinement of the XAFS and XRD data provides high accuracy since each method probes the structure of different local regions about the ions with high sensitivity. At high RbCl concentration (6 m (mol/kg )) the solution is dominated by Rb+ - Cl- contact ion pairs yielding an average of 1.5more » pairs at an Rb-Cl distance of 3.24 Å. Upon formation of these ion pairs, approximately 1.1 waters molecules are displaced from the Rb+ and 1.4 water molecules from Cl-. The hydration shells about both the cation and anion are also determined. These results greatly improve the understanding of monovalent ions and provide a basis for testing the Rb+-Cl- interaction potentials used in molecular dynamics (MD) simulation. This research was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.« less

Decomposition of the polycyclic nitramine explosive, CL-20, by Fe(0).

PubMed

Balakrishnan, Vimal K; Monteil-Rivera, Fanny; Halasz, Annamaria; Corbeanu, Aurelian; Hawari, Jalal

2004-12-15

CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane), C6H6N12O12, is an emerging energetic chemical that may replace RDX, but its degradation pathways are not well-known. In the present study, zerovalent iron was used to degrade CL-20 with the aim of determining its products and degradation pathways. In the absence of O2, CL-20 underwent a rapid decomposition with the concurrent formation of nitrite to ultimately produce nitrous oxide, ammonium, formate, glyoxal, and glycolate. LC/MS (ES-) showed the presence of several key products carrying important information on the initial reactions involved in the degradation of CL-20. For instance, a doubly denitrated intermediate of CL-20 was detected together with the mono- and dinitroso derivatives of the energetic chemical. Two other intermediates with [M-H]- at 392 and 376 Da, matching empirical formulas of C6H7N11O10 and C6H7N11O9, respectively, were detected. Using 15N-labeled CL-20, the two intermediates were tentatively identified as the denitrohydrogenated products of CL-20 and its mononitroso derivative, respectively. The present experimental findings suggest that CL-20 degraded via at least two initial routes: one involving denitration and the second involving sequential reduction of the N-NO2 to the corresponding nitroso (N-NO) derivatives prior to denitration and ring cleavage.

Solubility of NaCl in aqueous electrolyte solutions from 10 to 100°C

USGS Publications Warehouse

Clynne, M.A.; Potter, R.W.; Haas, J.L.

1981-01-01

The solubilities of NaCl in aqueous KCl, MgCl2, CaCl2, and mixed CaCl2-KCl solutions have been determined from 10 to 100??C. The data were fit to an equation, and the equation was used to calculate values of the change in solubility of NaCl, ???[NaCl]/???T. These values are required for calculations of the rate of migration of fluids in a thermal gradient in rock salt. The data obtained here indicate that the values of ???[NaCl]/???T are 36-73% greater for solutions containing divalent ions than for the NaCl-H2O system.

An Efficient, Solvent-Free Process for Synthesizing Anhydrous MgCl 2

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

Motkuri, Radha K.; Vemuri, Venkata Rama S.; Barpaga, Dushyant

A new efficient and solvent-free method for the synthesis of anhydrous MgCl2 from its hexahydrate is proposed. Fluidized dehydration of MgCl 2·6H 2O feedstock at 200 °C in a porous bed reactor yields MgCl2·nH2O (0 < n < 1), which has a similar diffraction pattern as activated MgCl2. The MgCl 2·nH 2O is then ammoniated directly using liquefied NH 3 in the absence of solvent to form MgCl 2·6NH 3. Calcination of the hexammoniate complex at 300 °C then yields anhydrous MgCl 2. Both dehydration and deammoniation were thoroughly studied using in situ as well as ex situ characterization techniques.more » Specifically, a detailed understanding of the dehydration process was monitored by in situ PXRD and in situ FTIR techniques where formation of salt with nH 2O (n = 4, 2, 1, <1) was characterized. Given the reduction in thermal energy required to produce dehydrated feedstock with this method compared with current strategies, significant cost benefits are expected. Overall, the combined effect of activation, macroporosity, and coordinated water depletion allows the formation of hexammoniate without using solvent, thus minimizing waste formation.« less

Effect of AgCl NPs: Physical, thermal, absorption and luminescence properties

NASA Astrophysics Data System (ADS)

Nurhafizah, H.; Rohani, M. S.

2017-06-01

Silver nanoparticles (AgCl NPs) are embedded in Er3+/Nd3+ co-doped lithium niobate tellurite glasses of the form (68-x)TeO2-15Li2CO3-15Nb2O5-1Er2O3-1Nd2O3-(x)AgCl with x = 1,2 and 3 mol% via conventional melt-quenching technique. The physical properties such as density, ionic packing density, refractive index and electronic polarizability are computed utilizing the usual method. The existence of AgCl NPs with an average size of 3.7 nm is confirmed using TEM analysis. Moreover, the thermal stability and Hruby criterion of the glass decreases as the AgCl NPs content increases. The direct optical band gap are found decrease as the AgCl NPs content increase, but both indirect optical band gap and Urbach energy are found increases as AgCl NPs content increases. The luminescence spectra shows two strong emission which is the purple emission at 436 nm and red emission at 724 nm which also been observed has strong quenching due to the AgCl NPs, Er3+/Nd3+ dopant and modifier, lithium niobate which possessed magnetic penetration. These glass compositions may be potential for various applications such as solid state devices including laser.

Optically stimulated luminescence in doped NaCl

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

Gaikwad, S. U., E-mail: gaikwadsonali09@yahoo.com; Patil, R. R.; Kulkarni, M. S.

NaCl:Ca,Cu,P NaCl:Mg,Cu,P OSL phosphors are synthesized. Intense OSL is observed in these samples which is 14 times more than Al{sub 2}O{sub 3}:C. Same samples coated with PVA (poly vinyl actetae) polymer also show similar OSL properties and these coated samples are found to be less susceptible to the moisture due to protected layer of hydrophobic polymer. These coated samples may be useful as OSL dosimetersdue to high sensitivity and less or no susceptibility to moisture.

Virus purification by CsCl density gradient using general centrifugation.

PubMed

Nasukawa, Tadahiro; Uchiyama, Jumpei; Taharaguchi, Satoshi; Ota, Sumire; Ujihara, Takako; Matsuzaki, Shigenobu; Murakami, Hironobu; Mizukami, Keijirou; Sakaguchi, Masahiro

2017-11-01

Virus purification by cesium chloride (CsCl) density gradient, which generally requires an expensive ultracentrifuge, is an essential technique in virology. Here, we optimized virus purification by CsCl density gradient using general centrifugation (40,000 × g, 2 h, 4 °C), which showed almost the same purification ability as conventional CsCl density gradient ultracentrifugation (100,000 × g, 1 h, 4 °C) using phages S13' and φEF24C. Moreover, adenovirus strain JM1/1 was also successfully purified by this method. We suggest that general centrifugation can become a less costly alternative to ultracentrifugation for virus purification by CsCl densiy gradient and will thus encourage research in virology.

A high-throughput method to measure NaCl and acid taste thresholds in mice.

PubMed

Ishiwatari, Yutaka; Bachmanov, Alexander A

2009-05-01

To develop a technique suitable for measuring NaCl taste thresholds in genetic studies, we conducted a series of experiments with outbred CD-1 mice using conditioned taste aversion (CTA) and two-bottle preference tests. In Experiment 1, we compared conditioning procedures involving either oral self-administration of LiCl or pairing NaCl intake with LiCl injections and found that thresholds were the lowest after LiCl self-administration. In Experiment 2, we compared different procedures (30-min and 48-h tests) for testing conditioned mice and found that the 48-h test is more sensitive. In Experiment 3, we examined the effects of varying strength of conditioned (NaCl or LiCl taste intensity) and unconditioned (LiCl toxicity) stimuli and concluded that 75-150 mM LiCl or its mixtures with NaCl are the optimal stimuli for conditioning by oral self-administration. In Experiment 4, we examined whether this technique is applicable for measuring taste thresholds for other taste stimuli. Results of these experiments show that conditioning by oral self-administration of LiCl solutions or its mixtures with other taste stimuli followed by 48-h two-bottle tests of concentration series of a conditioned stimulus is an efficient and sensitive method to measure taste thresholds. Thresholds measured with this technique were 2 mM for NaCl and 1 mM for citric acid. This approach is suitable for simultaneous testing of large numbers of animals, which is required for genetic studies. These data demonstrate that mice, like several other species, generalize CTA from LiCl to NaCl, suggesting that they perceive taste of NaCl and LiCl as qualitatively similar, and they also can generalize CTA of a binary mixture of taste stimuli to mixture components.

Ftmw Observation and Analysis of the {p}-H_2-{AgCl} and {o}-H_2-{AgCl} Complex

NASA Astrophysics Data System (ADS)

Grubbs, G. S.; Obenchain, D. A.; Pickett, H. M.; Novick, S. E.

2013-06-01

The rotational spectrum of p-H_2-{AgCl} and o-H_2-{AgCl} has been measured for the first time using a Balle-Flygare type Fourier transform microwave (FTMW) spectrometer. {(B+C)}/{2}'s, nuclear quadrupole coupling constants, and centrifugal distortion constants have been determined for multiple isotopologues of both species while spin-spin coupling constants have also been determined for at least one isotopologue of the o-H_2 species. Substantial changes in the eQq value from the monomer occur at the Cl nucleus upon complexation with the H_2 and will be discussed. Experimental r_0's for the H_2 C.O.M. distance to Ag and Ag distance to Cl are 1.809(2)Å and 2.2656(2)Å , respectively, for the p-H_2 species and will be compared to theory. Quantum chemical calculations were performed with an APFD density functional and MP2 with an aug-cc-pVQZ basis set for the hydrogen and chlorine with the effective core potential ECP28MDF_AVQZ for the Ag and will be presented. K. D. Hensel, C. Styger, W. Jäger, A. J. Merer, and M. C. L. Gerry, J. Chem. Phys., 99(1993) 3320. A. Austin, G. A. Petersson, M. J. Frisch, F. J. Dobek, G. Scalmani, and K. J. Throsselll. Chem. Theor. Comp., 8(2012) 4989. D. Figgen, G. Rauhut, M. Dolg, and H. Stoll. Chem. Phys., 311(2005) 227. K. A. Peterson and C. Puzzarini. Theor. Chem. Acc., 114(2005) 283.

A tale of two CLCs: biophysical insights toward understanding ClC-5 and ClC-7 function in endosomes and lysosomes

PubMed Central

Zifarelli, Giovanni

2015-01-01

Abstract The CLC protein family comprises both Cl− channels and H+-coupled anion transporters. The understanding of the critical role of CLC proteins in a number of physiological functions has greatly contributed to a revision of the classical paradigm that attributed to Cl− ions only a marginal role in human physiology. The endosomal ClC-5 and the lysosomal ClC-7 are the best characterized human CLC transporters. Their dysfunction causes Dent’s disease and osteopetrosis, respectively. It had been originally proposed that they would provide a Cl− shunt conductance allowing efficient acidification of intracellular compartments. However, this model seems to conflict with the transport properties of these proteins and with recent physiological evidence. Currently, there is no consensus on their specific physiological role. CLC proteins present also a number of peculiar biophysical properties, such as the dimeric architecture, the co-existence of intrinsically different thermodynamic modes of transport based on similar structural principles, and the gating mechanism recently emerging for the transporters, just to name a few. This review focuses on the biophysical properties and physiological roles of ClC-5 and ClC-7. PMID:26036722

Los Angeles Beach Harbors, Los Angeles County, California.

DTIC Science & Technology

1974-10-01

predicted at this time. The presently proposed project is not dependent upon nor contributory to further navigation development in the V" Los Angeles...as Long Beach and Compton. The Los Angeles Harbor probably exhibited similar intensities ranging from VII to IX depending on the soil conditions...the harbor. The water quality in these aquifers is dependent upon the rates of recharge and extraction (natural and otherwise). The Dominguez Gap

Dynamic [Cl-]i measurement with chloride sensing quantum dots nanosensor in epithelial cells

NASA Astrophysics Data System (ADS)

Wang, Yuchi; Mao, Hua; Wong, Lid B.

2010-02-01

We have synthesized a chloride sensing quantum dots (QD) nanosensor, Cl-QD, for the dynamic measurements of chloride ion concentration in the millimolar range, a sensitivity that is applicable to most physiological intracellular chloride ion concentration ([Cl-]i) measurements in epithelial cells. The Cl-QD is synthesized by conjugating an anion receptor, 1-(2-mercapto-ethyl)-3-phenyl-thiourea (MEPTU) to a water soluble CdSe/ZnS QD at an emission wavelength of 620 nm. Upon binding of chloride ions to the Cl-QD, a photo-induced electron transfer mechanism caused the fluorescence of the QD to quench. This resulted in an inversely proportional relationship between the chloride ion concentration and the fluorescence intensity of the Cl-QD. We have utilized this Cl-QD to measure [Cl-]i in T84 and CF-PAC cultured cells, with either the C1C-2 or CFTR chloride channels being manipulated by pharmacological chloride channel activators and inhibitors. Activations of C1C-2 and CFTR chloride channels in T84 by the respective lubiprostone and genistein caused predictive increases in the fluorescence of the Cl-QD, i.e., a decrease of [Cl-]i. Conversely, glibenclamide, a chloride channel inhibitor, applied to the CF-PAC cells caused a predictable decrease in the fluorescence of Cl-QD due to the increase of [Cl-]i. These are the first data in using QD-based chloride ion sensors for dynamic measurements of intracellular chloride ion concentrations in epithelial cells.

Aniline chlorination by in situ formed Ag-Cl complexes under simulated solar light irradiation.

PubMed

Hu, Xuefeng; Wang, Xiaowen; Dong, Liuliu; Chang, Fei; Luo, Yongming

2015-01-01

Ag speciation in a chloride medium was dependent upon the Cl/Ag ratio after releasing into surface water. In this study, the photoreaction of in situ formed Ag-Cl species and their effects on aniline photochlorination were systematically investigated. Our results suggested that formation of chloroaniline was strongly relevant to the Cl/Ag ratio and could be interpreted using the thermodynamically expected speciation of Ag in the presence of Cl-. AgCl was the main species responsible for the photochlorination of aniline. Both photoinduced hole and •OH drove the oxidation of Cl- to radical •Cl, which promoted the chlorination of aniline. Ag0 formation was observed from the surface plasmon resonance absorption during AgCl photoreaction. This study revealed that Ag+ released into Cl--containing water may result in the formation of chlorinated intermediates of organic compounds under solar light irradiation.

Preparation of Ferrotitanium Alloys by Electrolysis-Assisted Calciothermic Reduction of Ilmenite in Equimolar CaCl2-NaCl Electrolyte: Effect of Calcium Oxide

NASA Astrophysics Data System (ADS)

Zhou, Zhongren; Zhang, Yingjie; Hua, Yixin; Xu, Cunying; Dong, Peng; Zhang, Qibo; Wang, Ding

2018-04-01

The effect of CaO content on the preparation of ferrotitanium alloys from ilmenite with the method of the electrolysis-assisted calciothermic reduction has been investigated by use of ilmenite powders as raw materials that positions them next to the cathodic molybdenum plate, equimolar CaCl2-NaCl molten salt with 2-7 mol.% CaO as electrolyte and graphite as anode at 700°C with cell voltage of 2.8 V under argon atmosphere. It is demonstrated that increasing the reactant CaO content is beneficial to the calciothermic reduction of ilmenite and the intermediate CaTiO3. Experimental results also show that after 14 h of calciothermic reduction process, the products are ferrotitanium alloys and the specific energy consumption is only about 10.21 kWh kg-1 when adding 5 mol.% CaO into equimolar CaCl2-NaCl molten salt and approximately 14.40 kWh kg-1 when CaO content is increased to 7 mol.%.

Zinc phthalocyanine nanowires based flexible sensor for room temperature Cl2 detection

NASA Astrophysics Data System (ADS)

Devi, Pooja; Saini, Rajan; Singh, Rajinder; Mahajan, A.; Bedi, R. K.; Aswal, D. K.; Debnath, A. K.

2018-04-01

We have fabricated highly sensitive and Cl2 selective flexible sensor by depositing solution processed zinc phthalocyanine nanowires onto the flexible PET substrate and studied its Cl2 sensing characteristics in Cl2 concentration range 5-1500 ppb. The flexible sensor has a minimum detection limit as low as 5 ppb of Cl2 and response as high as 550% within 10 seconds. Interestingly, the sensor exhibited enhanced and faster response kinetics under bending conditions. The gas sensing mechanism of sensor has been discussed on the basis of XPS and Raman spectroscopic studies which revealed that zinc ions were the preferred sites for Cl2 interactions.

Halides Held by Bifurcated Chalcogen-Hydrogen Bonds. Effect of μ(S,N-H)Cl Contacts on Dimerization of Cl(carbene)PdII Species.

PubMed

Mikherdov, Alexander S; Novikov, Alexander S; Kinzhalov, Mikhail A; Boyarskiy, Vadim P; Starova, Galina L; Ivanov, Alexander Yu; Kukushkin, Vadim Yu

2018-03-19

The reaction of cis-[PdCl 2 (CNCy) 2 ] (1) with thiazol-2-amines (2-10) leads to the C,N-chelated diaminocarbene-like complexes [PdCl{ C(N(H)4,5-R 2 -thiazol-2-yl)NHCy}(CNCy)] (11-14; 82-91%) in the case of 4,5-R 2 -thiazol-2-amines (R, R = H, H (2), Me, Me (3), -(CH 2 ) 4 - (4)) and benzothiazol-2-amine (5) or gives the diaminocarbene species cis-[PdCl 2 {C(N(H)Cy)N(H)4-R-thiazol-2-yl}(CNCy)] (15-19; 73-93%) for the reaction with 4-aryl-substituted thiazol-2-amines (R = Ph (6), 4-MeC 6 H 4 (7), 4-FC 6 H 4 (8), 4-ClC 6 H 4 (9), 3,4-F 2 C 6 H 3 (10)). Inspection of the single-crystal X-ray diffraction data for 15-17 and 19 suggests that the structures of all these species exhibit previously unrecognized bifurcated chalcogen-hydrogen bonding μ (S,N-H) Cl and also Pd II ···Pd II metallophilic interactions. These noncovalent interactions collectively connect two symmetrically located molecules of 15-17 and 19, resulting in their solid-state dimerization. The existence of the μ (S,N-H) Cl system and its strength (6-9 kcal/mol) were additionally verified/estimated by a Hirshfeld surface analysis and DFT calculations combined with a topological analysis of the electron density distribution within the formalism of Bader's theory (AIM method) and NBO analysis. The observed noncovalent interactions are jointly responsible for the dimerization of 15-19 not only in the solid phase but also in CHCl 3 solutions, as predicted theoretically by DFT calculations and confirmed experimentally by FTIR, HRESI-MS, 1 H NMR, and diffusion coefficient NMR measurements. Available CCDC data were processed under the new moiety angle, and the observed μ (S,E-H) Cl systems were classified accordingly to E (E = N, O, C) type atoms.

Improved line parameters for the Chi 2Pi-Chi 2Pi (1-0) bands of (35)ClO and (37)ClO

NASA Technical Reports Server (NTRS)

Goldman, Aaron; Gillis, James R.; Rinsland, Curtis P.; Burkholder, James B.

1994-01-01

Improved line parameters at 296 K for the Chi 2Pi-Chi 2Pi (1-0) bands of (35)ClO and (37)ClO have been calculated with J up to 43.5. The integrated intensity for the 2048 lines in the main and satellite bands has been normalized to 9.68-sq cm/atm at 296K.

Dynamical spin structure factors of α-RuCl3

NASA Astrophysics Data System (ADS)

Suzuki, Takafumi; Suga, Sei-ichiro

2018-03-01

Honeycomb-lattice magnet α-RuCl3 is considered to be a potential candidate of realizing Kitaev spin liquid, although this material undergoes a phase transition to the zigzag magnetically ordered state at T N ∼ 7 K. Quite recently, inelastic neutron-scattering experiments using single crystal α-RuCl3 have unveiled characteristic dynamical properties. We calculate dynamical spin structure factors of three ab-initio models for α-RuCl3 with an exact numerical diagonalization method. We also calculate temperature dependences of the specific heat by employing thermal pure quantum states. We compare our numerical results with the experiments and discuss characteristics obtained by using three ab-initio models.

Multisite Ion Model in Concentrated Solutions of Divalent Cations (MgCl2 and CaCl2): Osmotic Pressure Calculations

PubMed Central

2015-01-01

Accurate force field parameters for ions are essential for meaningful simulation studies of proteins and nucleic acids. Currently accepted models of ions, especially for divalent ions, do not necessarily reproduce the right physiological behavior of Ca2+ and Mg2+ ions. Saxena and Sept (J. Chem. Theor. Comput.2013, 9, 3538–3542) described a model, called the multisite-ion model, where instead of treating the ions as an isolated sphere, the charge was split into multiple sites with partial charge. This model provided accurate inner shell coordination of the ion with biomolecules and predicted better free energies for proteins and nucleic acids. Here, we expand and refine the multisite model to describe the behavior of divalent ions in concentrated MgCl2 and CaCl2 electrolyte solutions, eliminating the unusual ion–ion pairing and clustering of ions which occurred in the original model. We calibrate and improve the parameters of the multisite model by matching the osmotic pressure of concentrated solutions of MgCl2 to the experimental values and then use these parameters to test the behavior of CaCl2 solutions. We find that the concentrated solutions of both divalent ions exhibit the experimentally observed behavior with correct osmotic pressure, the presence of solvent separated ion pairs instead of direct ion pairs, and no aggregation of ions. The improved multisite model for (Mg2+ and Ca2+) can be used in classical simulations of biomolecules at physiologically relevant salt concentrations. PMID:25482831

Physiological responses to salt stress of salt-adapted and directly salt (NaCl and NaCl+Na2SO4 mixture)-stressed cyanobacterium Anabaena fertilissima.

PubMed

Swapnil, Prashant; Rai, Ashwani K

2018-05-01

Soil salinity in nature is generally mixed type; however, most of the studies on salt toxicity are performed with NaCl and little is known about sulfur type of salinity (Na 2 SO 4 ). Present study discerns the physiologic mechanisms responsible for salt tolerance in salt-adapted Anabaena fertilissima, and responses of directly stressed parent cells to NaCl and NaCl+Na 2 SO 4 mixture. NaCl at 500 mM was lethal to the cyanobacterium, whereas salt-adapted cells grew luxuriantly. Salinity impaired gross photosynthesis, electron transport activities, and respiration in parent cells, but not in the salt-adapted cells, except a marginal increase in PSI activity. Despite higher Na + concentration in the salt mixture, equimolar NaCl appeared more inhibitive to growth. Sucrose and trehalose content and antioxidant activities were maximal in 250 mM NaCl-treated cells, followed by salt mixture and was almost identical in salt-adapted (exposed to 500 mm NaCl) and control cells, except a marginal increase in ascorbate peroxidase activity and an additional fourth superoxide dismutase isoform. Catalase isoform of 63 kDa was induced only in salt-stressed cells. Salinity increased the uptake of intracellular Na + and Ca 2+ and leakage of K + in parent cells, while cation level in salt-adapted cells was comparable to control. Though there was differential increase in intracellular Ca 2+ under different salt treatments, ratio of Ca 2+ /Na + remained the same. It is inferred that stepwise increment in the salt concentration enabled the cyanobacterium to undergo priming effect and acquire robust and efficient defense system involving the least energy.

Thermodynamic Modeling of Poorly Complexing Metals in Concentrated Electrolyte Solutions: An X-Ray Absorption and UV-Vis Spectroscopic Study of Ni(II) in the NiCl2-MgCl2-H2O System

PubMed Central

Zhang, Ning; Brugger, Joël; Etschmann, Barbara; Ngothai, Yung; Zeng, Dewen

2015-01-01

Knowledge of the structure and speciation of aqueous Ni(II)-chloride complexes is important for understanding Ni behavior in hydrometallurgical extraction. The effect of concentration on the first-shell structure of Ni(II) in aqueous NiCl2 and NiCl2-MgCl2 solutions was investigated by Ni K edge X-ray absorption (XAS) and UV-Vis spectroscopy at ambient conditions. Both techniques show that no large structural change (e.g., transition from octahedral to tetrahedral-like configuration) occurs. Both methods confirm that the Ni(II) aqua ion (with six coordinated water molecules at R Ni-O = 2.07(2) Å) is the dominant species over the whole NiCl2 concentration range. However, XANES, EXAFS and UV-Vis data show subtle changes at high salinity (> 2 mol∙kg-1 NiCl2), which are consistent with the formation of small amounts of the NiCl+ complex (up to 0.44(23) Cl at a Ni-Cl distance of 2.35(2) Å in 5.05 mol∙kg-1 NiCl2) in the pure NiCl2 solutions. At high Cl:Ni ratio in the NiCl2-MgCl2-H2O solutions, small amounts of [NiCl2]0 are also present. We developed a speciation-based mixed-solvent electrolyte (MSE) model to describe activity-composition relationships in NiCl2-MgCl2-H2O solutions, and at the same time predict Ni(II) speciation that is consistent with our XAS and UV-Vis data and with existing literature data up to the solubility limit, resolving a long-standing uncertainty about the role of chloride complexing in this system. PMID:25885410

A study of 36Cl production in the early Solar System

NASA Astrophysics Data System (ADS)

Bowers, Matthew R.

Short-lived radionuclides (SLRs) with lifetimes tau < 100 Ma are known to have been extant when the Solar System formed 4.568 billion years ago from meteoritic studies of their decay products. Identifying the origins of SLRs can provide insight into the origins and timescales of our Solar System and the processes that shaped it. There are two proposed production scenarios for the origins of SLRs with tau < 5 Ma. Freshly synthesized material could be incorporated in the Solar System by a nearby stellar source (e.g., supernova, AGB star, Wolf-Rayet star), or SLRs could have also been produced by the bombardment of gas and dust by solar energetic particles (SEP) emitted by our young Sun. The origin of extinct 36Cl (t1/2 = 0.301 Ma) in the early Solar System is thought to have been produced by local particle irradiation. However the models that attempt to recreate the production of 36Cl in the early Solar System lack experimental data for the nuclear reactions considered. The first measurement of the 33S(alpha,p) 36Cl reaction, an important reaction in the production of 36Cl , was performed. The cross section measurement was performed by bombarding a target and collecting the recoiled 36Cl atoms produced in the reaction, chemically processing the samples, and measuring the 36Cl/Cl concentration of the samples with accelerator mass spectrometry (AMS). The cross section was measured at six energies that ranged from 0.70 up to 2.42 MeV/A, within the SEP energy spectrum. The experimental results were found to be systematically higher than the predicted cross sections. However, the deviations lead to < 7 % increase in total production of 36Cl under the x-wind model. From the experimental measurement and a study of the other reactions' contributions to 36Cl production, 36Cl could have been produced close to the protoSun by reactions on Ca targets using the x-wind model, or in a late-stage irradiation event on a volatile-rich reservoir by 3He and alpha reactions on S targets.

Registration of 'Thunder CL' Wheat

USDA-ARS?s Scientific Manuscript database

'Thunder CL' (Reg. No. CV- , PI XXXXXX) hard white winter wheat (Triticum aestivum L.) was developed by the Colorado Agricultural Experiment Station and released in August 2008 through a marketing agreement with the Colorado Wheat Research Foundation. In addition to researchers at Colorado State Uni...

AMS Measurement of 36Cl with a Q3D Magnetic Spectrometer at CIAE

NASA Astrophysics Data System (ADS)

Li, Chaoli; He, Ming; Zhang, Wei; Wu, Shaoyong; Li, Zhenyu; He, Xianwen; Liu, Jiancheng; Dong, Kejun; Jiang, Shan

2012-06-01

The ratio of 36Cl/Cl can determine the exposure age of surface rocks and monitor the secular equilibrium of 36Cl of sedimentary and igneous rock in groundwater. Due to the uncertainty effects of different chemical separation processes for removing 36S, there is a high degree of uncertainty in 36Cl accelerator mass spectrometry (AMS) measurements if the ratio of 36Cl/Cl is lower than 10-14. A 36Cl AMS higher sensitivity measurement has been set up by using a ΔE-Q3D method at the China Institute of Atomic Energy (CIAE). The performances of ΔE-Q3D method for 36Cl-AMS measurement had been systemically studied. The experimental results show that the ΔE-Q3D method has a higher isobar suppression factor. Taking advantage of direct removing 36S, the sample preparation can be simplified and the uncertainty effects of different chemical separation processes can be reduced in 36Cl AMS measurements.

Investigation of the hydrogenation of SiCl4

NASA Technical Reports Server (NTRS)

Mui, J. Y. P.; Seyferth, D.

1981-01-01

A laboratory scale pressure reactor was constructed to study the 3 SiCl + 2H2 + Si yields 4 SiHCl3 reaction at pressures up to 500 psig. Reaction kinetic measurements were carried out as a function of reactor pressure, reaction temperature and H2/SiCl4 feed ratio. Based on the reaction kinetic data, the hydroclorination of SiCl4 and m.g. silicon metal is found to be an efficient process to produce SiHCl3 in good conversions and in high yields. Copper is an effective catalyst. Results of the corrosion study show that conventional nickel chromium alloys are suitable material of construction for the hydrochlorination reactor. The hydrochlorination reaction is relatively insensitive to external process parameters such as silicon particle size distribution and the impurities in the m.g. silicon metal.

Tratamiento Quirúrgico de los Meningiomas del Foramen Óptico, Técnicay Resultados de una Serie de 18 Pacientes

PubMed Central

Goldschmidt, Ezequiel; Ajler, Pablo; Campero, Álvaro; Landriel, Federico; Sposito, Maximiliano; Carrizo, Antonio

2014-01-01

Introducción: los meningiomas del foramen óptico producen un rápido deterioro de la función visual aún cuando su tamaño es pequeño, por eso su diagnóstico y manejo difiere del resto de los meningiomas clinoideos. El propósito de este estudio es presentar la técnica y los resultados de nuestro manejo quirúrgico de meningiomas foraminales (MF). Pacientes y Métodos: se llevó a cabo una revisión de las historias clínicas de 47 pacientes con meningiomas primarios intraorbitarios. Se realizaron 52 cirugías en los pacientes con MF. Se empleó una craneotomía fronto-orbitaria, seguida de una descompresión extradural del canal óptico, resección del componente intraorbitario y exploración intradural del nervio óptico. Resultados: de los 12 pacientes con MF que presentaban la visión conservada, la agudeza visual fue preservada en 7 casos, mejoró en 2, y empeoró en 3. En 18 pacientes, el principal síntoma fue exoftalmos y en 35 pacientes ceguera unilateral. Ocurrieron 6 recurrencias, 2 a 10 años después de la resección quirúrgica. Cinco de ellos fueron reoperados. Se indicó radioterapia después de la recurrencia en 3 pacientes. Conclusión: el manejo de los MF continúa siendo controvertido y frecuentemente se propone un tratamiento conservador. Basados en nuestros hallazgos de frecuente extensión intracraneal, proponemos realizar una resección total o subtotal del tumor, preservando el nervio óptico en pacientes con visión prequirúrgica conservada. PMID:25165616

Photodissociation of the CH3Cl/+/ and N2O/+/ cations.

NASA Technical Reports Server (NTRS)

Dunbar, R. C.

1971-01-01

Use of the ion cyclotron resonance (icr) technique to observe the photodissociation of the cations CH3Cl(+) and N2O(+) in the gas phase. Ions were trapped in the icr cell for periods of the order of seconds, which permitted the photodissociation process to be observed with wavelength-selected light. A cyclotron resonance ejection technique was employed to show that CH3Cl(+) ions were being dissociated rather than the CH3ClH(+) ions which were also present. The photodissociation cross section for N2O(+) was found to be without strong wavelength dependence between 4000 and 6500 A. The cross section for CH3Cl(+) showed a large peak at 3150 A. Possible assignments of this peak are considered, and it is suggested that a photodissociation occurs through an ion excitation involving a change in occupation of the bonding or antibonding orbitals of the C-Cl bond.

Lithium fluxes indicate presence of Na-Cl cotransport (NCC) in human lens epithelial cells.

PubMed

Lauf, Peter K; Chimote, Ameet A; Adragna, Norma C

2008-01-01

During regulatory volume decrease (RVD) of human lens epithelial cells (hLECs) by clotrimazole (CTZ)-sensitive K fluxes, Na-K-2Cl cotransport (NKCC) remains active and K-Cl cotransport (KCC) inactive. To determine whether such an abnormal behavior was caused by RVD-induced cell shrinkage, NKCC was measured in the presence of either CTZ or in high K media to prevent RVD. NKCC transports RbCl + NaCl, and LiCl + KCl; thus ouabain-insensitive, bumetanide-sensitive (BS) or Cl-dependent (ClD) Rb and Li fluxes were determined in hyposmotic high NaCl media with CTZ, or in high KCl media alone, or with sulfamate (Sf) or nitrate as Cl replacement at varying Rb, Li or Cl mol fractions (MF). Unexpectedly, NKCC was inhibited by 80% with CTZ (IC(50) = 31 microM). In isosmotic (300 mOsM) K, Li influx was approximately 1/3 of Rb influx in Na, 50% lower in Sf, and bumetanide-insensitive (BI). In hypotonic (200 mOsM) K, only the ClD but not BS Li fluxes were detected. At Li MFs from 0.1-1, Li fluxes fitted a bell-shaped curve maxing at approximately 0.6 Li MF, with the BS fluxes equaling approximately 1/4 of the ClD-Li influx. The difference, i.e. the BI/ClD Li influx, saturated with increasing Li and Cl MFs, with K(ms) for Li of 11 with, and 7 mM without K, and of approximately 46 mM for Cl. Inhibition of this K-independent Li influx by thiazides was weak whilst furosemide (<100 microM) was ineffective. Reverse transcription polymerase chain reaction and Western blots verified presence of both NKCC1 and Na-Cl cotransport (NCC). In conclusion, in hyposmotic high K media, which prevents CTZ-sensitive K flux-mediated RVD in hLECs, NKCC1, though molecularly expressed, was functionally silent. However, a K-independent and moderately thiazide-sensitive ClD-Li flux, i.e. LiCC, likely occurring through NCC was detected operationally and molecularly. (c) 2008 S. Karger AG, Basel.

Syntheses, Spectroscopic Data, and X-ray Diffraction Structures of the Heterometallic RuRe Face-shared Bioctahedral (eta(6)-cymene)Ru(mu-Cl)(3)Re(CO)(3) and MnRu2 Edge-shared Trioctahedral [fac-ClRu(CO)(3)](2)(mu-Cl)(4)Mn(H2O)(2) Complexes

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

Wang, Xiaoping; Hunt, Sean W; Richmond, Michael G.

2009-01-01

Thermolysis of the diruthenium compound [(eta(6)-cymene)RuCl2](2) (1) with ClRe(CO)(5) (2) leads to the formation of the new confacial bioctahedral compound (eta(6)-cymene) Ru(mu-Cl)(3)Re(CO)(3) (3) in good yields; the same product has also been isolated when a mixture of 1 and 2 is irradiated with near UV-vis light for an extended period of time. Heating 1 and ClMn(CO)(5) (4) does not furnish the corresponding manganese analogue of 3 but rather the trioctahedral halide-bridged product [fac-ClRu(CO)(3)](2)(mu-Cl)(4)Mn(H2O)(2) (5). 3 and 5 have been fully characterized in solution and their molecular structures established by X-ray crystallography.

The distribution of meteoric Cl-36 in precipitation across Europe in spring 2007

NASA Astrophysics Data System (ADS)

Johnston, Vanessa E.; McDermott, Frank

2008-10-01

The cosmogenic isotope 36Cl is a valuable tool for understanding many Earth system processes, but an improved knowledge of its spatial distribution at the Earth's surface is critical for several applications. Meteoric 36Cl fallout reflects complex interactions between atmospheric production, transport, and deposition processes, and predictive models require experimental validation. This study investigates, for the first time in a systematic way, the spatial distribution of meteoric 36Cl on a continental scale within the European landmass using precipitation samples collected during spring 2007. 36Cl/Cl ratios increase with distance inland and the new data exhibit a strong exponential relationship with δ18O values of precipitation ( RS = - 0.75), yielding a useful predictive framework for future studies. Precipitation events in central European regions are characterised by high 36Cl/Cl ratios, with a maximum measured in Lyon, France of 746 (± 134) × 10 - 15 . The new data confirm models for the dependence of 36Cl fallout on latitude, with the highest mean springtime fallout (53.6 atoms m - 2 s - 1 ) occurring in the 40-50°N latitudinal band, with sharp decreases in fallout in high latitude regions and more gradual decreases towards the lower latitudes. The 36Cl bomb pulse, introduced by thermonuclear weapon testing, predominantly in the 1950's, has persisted in the environment for c. 50 years, but the new data indicate that 36Cl fallout has now essentially returned to natural, pre-bomb values.

BowMapCL: Burrows-Wheeler Mapping on Multiple Heterogeneous Accelerators.

PubMed

Nogueira, David; Tomas, Pedro; Roma, Nuno

2016-01-01

The computational demand of exact-search procedures has pressed the exploitation of parallel processing accelerators to reduce the execution time of many applications. However, this often imposes strict restrictions in terms of the problem size and implementation efforts, mainly due to their possibly distinct architectures. To circumvent this limitation, a new exact-search alignment tool (BowMapCL) based on the Burrows-Wheeler Transform and FM-Index is presented. Contrasting to other alternatives, BowMapCL is based on a unified implementation using OpenCL, allowing the exploitation of multiple and possibly different devices (e.g., NVIDIA, AMD/ATI, and Intel GPUs/APUs). Furthermore, to efficiently exploit such heterogeneous architectures, BowMapCL incorporates several techniques to promote its performance and scalability, including multiple buffering, work-queue task-distribution, and dynamic load-balancing, together with index partitioning, bit-encoding, and sampling. When compared with state-of-the-art tools, the attained results showed that BowMapCL (using a single GPU) is 2 × to 7.5 × faster than mainstream multi-threaded CPU BWT-based aligners, like Bowtie, BWA, and SOAP2; and up to 4 × faster than the best performing state-of-the-art GPU implementations (namely, SOAP3 and HPG-BWT). When multiple and completely distinct devices are considered, BowMapCL efficiently scales the offered throughput, ensuring a convenient load-balance of the involved processing in the several distinct devices.

OpenCL Implementation of NeuroIsing

NASA Astrophysics Data System (ADS)

Zapart, C. A.

Recent advances in graphics card hardware combined with anintroduction of the OpenCL standard promise to accelerate numerical simulations across diverse scientific disciplines. One such field benefiting from new hardware/software paradigms is econophysics. The paper describes an OpenCL implementation of a selected econophysics model: NeuroIsing, which has been designed to execute in parallel on a vendor-independent graphics card. Originally introduced in the paper [C.~A.~Zapart, ``Econophysics in Financial Time Series Prediction'', PhD thesis, Graduate University for Advanced Studies, Japan (2009)], at first it was implemented on a CELL processor running inside a SONY PS3 games console. The NeuroIsing framework can be applied to predicting and trading foreign exchange as well as stock market index futures.

Heterogeneous compute in computer vision: OpenCL in OpenCV

NASA Astrophysics Data System (ADS)

Gasparakis, Harris

2014-02-01

We explore the relevance of Heterogeneous System Architecture (HSA) in Computer Vision, both as a long term vision, and as a near term emerging reality via the recently ratified OpenCL 2.0 Khronos standard. After a brief review of OpenCL 1.2 and 2.0, including HSA features such as Shared Virtual Memory (SVM) and platform atomics, we identify what genres of Computer Vision workloads stand to benefit by leveraging those features, and we suggest a new mental framework that replaces GPU compute with hybrid HSA APU compute. As a case in point, we discuss, in some detail, popular object recognition algorithms (part-based models), emphasizing the interplay and concurrent collaboration between the GPU and CPU. We conclude by describing how OpenCL has been incorporated in OpenCV, a popular open source computer vision library, emphasizing recent work on the Transparent API, to appear in OpenCV 3.0, which unifies the native CPU and OpenCL execution paths under a single API, allowing the same code to execute either on CPU or on a OpenCL enabled device, without even recompiling.

As-synthesis of nanostructure AgCl/Ag/MCM-41 composite

NASA Astrophysics Data System (ADS)

Sohrabnezhad, Sh.; Pourahmad, A.

2012-02-01

In this work, we present the simple synthetic route for silver chloride/silver nanoparticles (AgCl/Ag-NPs) using as-synthesis method. The structure, composition and optical properties of such material were investigated by transmission electron microscopy (TEM), UV-visible diffuse reflectance spectroscopy (UV-vis DRS), X-ray diffraction (XRD) and FTIR. Powder X-ray diffraction showed that when AgNO 3 content is below 0.1 wt.% in synthetic gel, the guest AgCl/Ag-NPs is formed on the silica channel wall, and lower exists in the crystalline state. When AgNO 3 content exceeds this value, AgCl/Ag nanoparticles can be observed in high crystalline state. The absorption at 327 nm ascribed to the characteristic absorption of the AgCl semiconductor. Ag nanoparticles have been shown to exist in the nanocomposite at 375 nm. When AgNO 3 content is above 0.1 wt.% in synthetic gel, spectra exhibited stronger absorption at 450-700 nm that was attributed to the surface plasmonic resonance of silver nanoparticles. The obtained AgCl/Ag/MCM-41 sample exhibit enhanced photocatalytic activity for the degradation of methylene blue under visible-light irradiation.

Role of endolymphatic anion transport in forskolin-induced Cl- activity increase of scala media.

PubMed

Kitano, I; Mori, N; Matsunaga, T

1995-03-01

To determine the role of anion transport in the forskolin-induced Cl- increase of scala media (SM), effects of forskolin on the EP (endocochlear potential) and Cl- activity (ACl) in SM were examined with double-barrelled Cl(-)-selective microelectrodes. The experiments were carried out on guinea pig cochleae, using a few anion transport inhibitors: IAA-94 for a Cl- channel blocker, bumetanide (BU) for an Na+/K+/2Cl- cotransport blocker, and SITS and DIDS for Cl-/HCO3- exchange blockers. The application of forskolin (200 microM) into scala vestibuli (SV) caused a 20 mEq increase of endolymphatic ACl and a 15 mV elevation of EP, and IAA-94 with forskolin completely abolished these responses. Although each application of BU, SITS or DIDS did not completely suppress EP elevation, the concurrent application of these inhibitors completely suppressed EP with endolymphatic ACl increase. The results indicate the involvement of Cl- channels, Na+/K+/2Cl- cotransport and Cl-/HCO3- exchange in forskolin-induced increase of ACl and EP. The role of adenylate cyclase activation and Cl- transport in endolymph homeostasis was discussed.

Inductively coupled Cl2/Ar plasma: Experimental investigation and modeling

NASA Astrophysics Data System (ADS)

Efremov, A. M.; Kim, Dong-Pyo; Kim, Chang-Il

2003-07-01

Electrophysical and kinetic characteristics of Cl2/Ar plasma were investigated to understand the influence of the addition of Ar on the volume densities and fluxes of active particles, both neutral and charged. Our analysis combined both experimental methods and plasma modeling. It was found that addition of Ar to Cl2 leads to deformation of the electron energy distribution function and an increase of the electron mean energy due to the ``transparency'' effect. Direct electron impact dissociation of Cl2 molecules represents the main source of chlorine atoms in the plasma volume. The contributions of stepwise dissociation and ionization involving Ar metastable atoms were found to be negligible. Addition of Ar to Cl2 causes the decrease of both electron and ion densities due to a decrease in the total ionization rate and the acceleration of heterogeneous decay of charged particles.

Mercuric chloride (HgCl2)

Integrated Risk Information System (IRIS)

Mercuric chloride ( HgCl2 ) ; CASRN 7487 - 94 - 7 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 Nonc

New molten salt systems for high temperature molten salt batteries: Ternary and quaternary molten salt systems based on LiF-LiCl, LiF-LiBr, and LiCl-LiBr

NASA Astrophysics Data System (ADS)

Fujiwara, Syozo; Inaba, Minoru; Tasaka, Akimasa

Using a new simulative technique developed by us, we systematically investigated new ternary or quaternary molten salt systems, which are based on LiF-LiCl, LiF-LiBr, and LiCl-LiBr binary systems, for use as electrolytes in thermal batteries, and evaluated their ionic conductivities and melting points experimentally. It was confirmed experimentally that LiF-LiBr-KF (melting point: 425 °C, ionic conductivity at 500 °C: 2.52 S cm -1), LiCl-LiBr-KF (405 °C, 2.56 S cm -1), LiCl-LiBr-NaF-KF (425 °C, 3.11 S cm -1), LiCl-LiBr-NaCl-KCl (420 °C, 2.73 S cm -1), and LiCl-LiBr-NaBr-KBr (420 °C, 2.76 S cm -1) meet our targets for both melting point (350-430 °C) and ionic conductivity (2.0 S cm -1 and higher at 500 °C). A single cell using the newly developed LiCl-LiBr-NaCl-KCl molten salt as an electrolyte was prepared, and the DC-IR of the cell decreased by 20% than that of a single cell using the conventional LiCl-KCl molten salt. It was therefore concluded that the use of new quaternary molten salt systems can improve the discharge rate-capability in practical battery applications because of their high ionic conductivities.

Ion Association in AlCl3 Aqueous Solutions from Constrained First-Principles Molecular Dynamics

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

Cauet, Emilie L.; Bogatko, Stuart A.; Bylaska, Eric J.

2012-10-15

Ab initio molecular dynamics was used to investigate the ion pairing behavior between Cl- and the Al3+ ion in an aqueous AlCl3 solution containing 63 water molecules. A series of constrained simulations was carried out at 300 K for up to 16 ps each, by fixing the inter-nuclear separation (rAl-Cl) between the Al3+ ion and one of the Cl- ions. The calculated potential of mean force of the Al3+-Cl- ion pair shows a pronounced minimum at rAl-Cl = 2.3 Å corresponding to a contact ion pair (CIP). Two local minima assigned to solvent separated ion pairs (SSIP) are identified atmore » rAl-Cl= 4.4 and 6.0 Å. The positions of the free energy minima coincide with the hydration shell intervals of the Al3+ cation suggesting that the Cl- ion is inclined to reside in regions of low concentration of waters, i.e. between the 1st and 2nd shells of Al3+ and between the 2nd shell and bulk. A detailed analysis of solvent structure around the Al3+ and Cl- ions as a function of rAl-Cl is presented. The results are compared to structure data from X-ray measurements and unconstrained AIMD simulations of single ions Al3+ and Cl- and AlCl3 solutions. The dipole moment of the water molecules inside the 1st and 2nd hydration shells of Al3+ and in the bulk region and those of the Clion were calculated as a function of rAl-Cl. Major changes in the electronic structure of the system result from the removal of Cl- from the 1st hydration shell of the Al3+ cation. Finally, two unconstrained AIMD simulations of aqueous AlCl3 solutions corresponding to CIP and SSIP configurations were performed (17 ps, 300 K). Only minor structural changes are observed in these systems, confirming their stability.« less

Los Angeles-Long Beach Harbor Areas Regional Cultural History, Los Angeles County, California,

DTIC Science & Technology

1978-04-01

which they named islands, such as Mormon Island. The Los ’ Bahia de los Fumos’ on Angeles River, when discovered by the account of the many smokes...value because of its Fermin Francisco de Lasuen, "padre historically valuable fittings of museum quality. presidente" of the Franciscan missions. This...BUREAU OF STANDARDS-1963-k -4 L L LOS ANOELES BEC ABOR AREAS REIONAL GULTAL ISonY 2 Los Angels County, California AD-A144 450 "I~~~ -1lroe its ’ c*1 rpi

Proteome Analyses of Staphylococcus aureus Biofilm at Elevated Levels of NaCl

PubMed Central

Islam, Nazrul; Ross, Julia M; Marten, Mark R

2016-01-01

Our studies demonstrate that sodium chloride (NaCl) induces changes in biofilm, mediated by increased production of polysaccharides intercellular adhesion (PIA). We identified 12 proteins that showed higher abundance in increased level of NaCl. This includes one important protein (IsaA) known to be associated with biofilm stability. In addition, we also found higher abundance of a cold shock protein, CspA, at higher NaCl. We have also identified several other proteins that are differentially expressed to the elevated levels of NaCl and mapped them in the regulatory pathways of PIA. The majority of proteins are involved with various aspects bacterial metabolic function. Our results demonstrated that NaCl influences gene regulatory networks controlling exopolysaccharide expression. PMID:26973848

Evidence for Live Cl-36 in Ca-Al-rich Inclusions from the Ningqiang Carbonaceous Chondrite

NASA Technical Reports Server (NTRS)

Lin, Y.; Guan, Y.; Leshin, L. A.; Ouyang, Z.; Wang, D.

2004-01-01

The short-lived radionuclide Cl-36 decays to either Ar-36 (98.1%, beta(sup -)) or S-36 (1.9%, epsilon and beta(sup +)), with a half life of 3.01 x 10(exp 5) yr. Both the nucleosynthetic and spallation models suggest high initial Cl-36/Cl-35 ratios ((Cl-36/Cl-35)o up to approximately 10(exp -4)) in the early solar system. Previous observed excess Ar-36 in Efremovka matrix has been interpreted to represent a much lower (Cl-36/Cl-35)o ratio of approximately 1 x 10(exp -6). From the observed S-36 excesses in sodalite in calcium aluminum-rich inclusions (CAIs), we report in this study the first direct evidence of the presence of Cl-36 in primitive meteorites. The inferred (Cl-36/Cl-35)o ratios range from approximately 5 x 10(exp -6) to approximately 1 x 10(exp -5).

Theoretical analysis of the formation driving force and decreased sensitivity for CL-20 cocrystals

NASA Astrophysics Data System (ADS)

Zhou, Jun-Hong; Shi, Liang-Wei; Zhang, Chao-Yang; Li, Hong-Zhen; Chen, Min-Bo; Chen, Wei-Ming

2016-07-01

Methods that analyze the driving force in the formation of the new energetic cocrystal are proposed in this paper. Various intermolecular interactions in the 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo [5.5.0.05,9.03,11]dodecane (CL-20) cocrystals are compared with those in pure CL-20 and coformer crystals by atom in molecule (AIM) and Hirshfeld surface methods under the supramolecular cluster model. The driving force in the formation of the CL-20 cocrystals is analyzed. The main driving force in the formation of the cocrystal CL-20/HMX comes from the O···H interactions, that in the formation of the cocrystal CL-20/TNT from the O···H and C···O interactions, and that in the formation of the cocrystal CL-20/BTF from the N···H and N···O interactions. Other interactions in the CL-20 cocrystals only contribute to their stabilization. At the same time, the reasons for the decreased impact sensitivity of the CL-20 cocrystals are also analyzed. They are the strengthening of the intermolecular interactions, the reducing of the free space, and the changing of the surrounding of CL-20 molecule in the CL-20 cocrystals in comparison with those in the pure CL-20 crystal.

Cosmogenic 36Cl in karst waters: Quantifying contributions from atmospheric and bedrock sources

NASA Astrophysics Data System (ADS)

Johnston, V. E.; McDermott, F.

2009-12-01

Improved reconstructions of cosmogenic isotope production through time are crucial to understand past solar variability. As a preliminary step to derive atmospheric 36Cl/Cl solar proxy time-series from speleothems, we quantify 36Cl sources in cave dripwaters. Atmospheric 36Cl fallout rates are a potential proxy for solar output; however extraneous 36Cl derived from in-situ production in cave host-rocks could complicate the solar signal. Results from numerical modeling and preliminary geochemical data presented here show that the atmospheric 36Cl source dominates in many, but not all cave dripwaters. At favorable low elevation, mid-latitude sites, 36Cl based speleothem solar irradiance reconstructions could extend back to 500 ka, with a possible centennial scale temporal resolution. This would represent a marginal improvement in resolution compared with existing polar ice core records, with the added advantages of a wider geographic range, independent U-series constrained chronology, and the potential for contemporaneous climate signals within the same speleothem material.

Direct observation of ClO from chlorine nitrate photolysis. [as mechanism of polar ozone depletion

NASA Technical Reports Server (NTRS)

Minton, Timothy K.; Nelson, Christine M.; Moore, Teresa A.; Okumura, Mitchio

1992-01-01

Chlorine nitrate photolysis has been investigated with the use of a molecular beam technique. Excitation at both 248 and 193 nanometers led to photodissociation by two pathways, ClONO2 yields ClO + NO2 and ClONO2 yields Cl + NO3, with comparable yields. This experiment provides a direct measurement of the ClO product channel and consequently raises the possibility of an analogous channel in ClO dimer photolysis. Photodissociation of the ClO dimer is a critical step in the catalytic cycle that is presumed to dominate polar stratospheric ozone destruction. A substantial yield of ClO would reduce the efficiency of this cycle.

76 FR 66620 - Airworthiness Directives; Bombardier, Inc. Model CL-215-1A10, CL-215-6B11 (CL-215T Variant), and...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-10-27

... effective date of this AD: Perform an in situ eddy current inspection for cracks on the forward lug of the...-6B11 (CL-415 Variant) airplanes). Thereafter, repeat the in situ eddy current inspection at intervals not to exceed 165 land landings. (2) If no crack is found: Repeat the in situ eddy current inspection...

Dynamics of the reactions of O(1D) with HCl, DCl, and Cl2

NASA Astrophysics Data System (ADS)

Matsumi, Yutaka; Tonokura, Kenichi; Kawasaki, Masahiro; Tsuji, Kazuhide; Obi, Kinichi

1993-05-01

The reactions O(1D)+HCl→OH+Cl (1a) and OCl+H (1b), O(1D)+DCl→OD+Cl (2a) and OCl+D (2b), and O(1D)+Cl2→OCl+Cl (3) are studied at an average collision energy of 7.6, 7.7, and 8.8 kcal/mol for (1), (2), and (3), respectively. H, D, and Cl atoms are detected by the resonance-enhanced multiphoton ionization technique. The average kinetic energies released to the products are estimated from Doppler profile measurements of the product atoms. The relative yields [OCl+H]/[OH+Cl] and [OCl+D]/[OD+Cl] are directly measured, and a strong isotope effect (H/D) on the relative yields is found. The fine-structure branding ratios [Cl(2P1/2]/[Cl(2P3/2)] of the reaction products are also measured. The results suggest that nonadiabatic couplings take place at the exit channels of the reactions (1a) and (2a), while the reaction (3) is totally adiabatic.

On the Ground Electronic States of TiF and TiCl

NASA Astrophysics Data System (ADS)

Boldyrev, Alexander I.; Simons, Jack

1998-04-01

The low-lying electronic states of TiF and TiCl have been studied using high levelab initiotechniques. Both are found to have two low-lying excited electronic states,4Σ-(0.080 eV (TiF) and 0.236 eV (TiCl)) and2Δ (0.266 eV (TiF) and 0.348 eV (TiCl)), and4Φ ground states at the highest CCSD(T)/6-311++G(2d,2f) level of theory. Our theoretical predictions of4Φ ground electronic states for TiF and TiCl support recent experimental findings by Ram and Bernath, and our calculated bond lengths and vibrational frequencies are in reasonable agreement with their experimental data.

Vacuum ultraviolet photoabsorption spectroscopy of CH2Cl2 and CD2Cl2 in the energy region 50,000-95,000 cm-1

NASA Astrophysics Data System (ADS)

Mandal, Anuvab; Singh, Param Jeet; Shastri, Aparna; Jagatap, B. N.

2014-12-01

A consolidated study of the VUV absorption spectra of CH2Cl2 and CD2Cl2 in the 50,000-95,000 cm-1 region using synchrotron radiation is presented. Rydberg series and vibronic analysis are carried out and supported by quantum chemical calculations. The broad absorption band of CH2Cl2 in the region 50,000-60,000 cm-1 is attributed to the valence states 11B2, 11B1 and 11A1. Most of the bands in the 60,000-95,000 cm-1 region are fitted to Rydberg series of ns, np and nd type converging to the first four ionization potentials 11.320, 11.357, 12.152 and 12.271 eV of CH2Cl2 arising from excitation of an electron from one of the four outermost Cl non-bonding orbitals (2b1, 3b2, 1a2 and 4a1). Vertical excited states of CH2Cl2 calculated using TDDFT are correlated with experimentally observed electronic states based on the symmetries of the initial and final MOs involved in a transition. A few Rydberg transitions viz. 2b1→5s, 4p, 5p, 6p; 3b2→4p, 5p; 1a2→4p are accompanied by vibronic features. Observed vibronic bands are assigned mainly to the CCl symmetric stretch (ν3‧) mode with smaller contributions from the CH symmetric stretch (ν1‧), CH2 bend (ν2‧) and CH2 wag (ν8‧) modes. Assignments are corroborated by comparison with the VUV absorption spectrum of the deuterated isotopologue CD2Cl2, reported here for the first time. The high underlying intensities seen in several sub-regions are explained by valence or valence-Rydberg mixed type transitions predicted with high oscillator strengths by the TDDFT calculations.

Uptake of hexanitrohexaazaisowurtzitane (CL-20) by the earthworm Eisenia fetida through dermal contact.

PubMed

Gong, Ping; Escalon, B Lynn; Hayes, Charolett A; Perkins, Edward J

2008-02-01

The explosive compound hexanitrohexaazaisowurtzitane (CL-20) has been shown to cause both lethal and sublethal (reproductive and neurotoxic) effects in exposed oligochaetes. However, whether worms take up CL-20 and how much CL-20 enters worm bodies leading to toxicity (e.g., lethality) remain to be determined. In the present study, we used high performance liquid chromatography (HPLC) and radiolabeled tracer methods to investigate the CL-20 uptake in the whole worm body after contact exposures. Worms (Eisenia fetida) were exposed to filter paper spiked with non-radioactive or [U-(14)C]-labeled CL-20 for 1-3 d. The radiolabeled tracer method allowed us to detect the parent compound and transformation products in worms exposed to as low as 0.04 microg CL-20 cm(-2) of filter paper. The HPLC method without radiolabeled tracer was far less sensitive with a detection limit of 2.17 microg CL-20 cm(-2). Using the radiolabeled tracer, we were able to demonstrate that the worm body concentration linearly correlated to the filter paper concentration < or =0.34 microg cm(-2) (r=0.94) if no breakdown products are assumed. At higher concentrations, the body concentration increased slowly and saturated at around 11 microg g(-1) dry mass resulting in an estimated lethal critical body burden of 10-15 microg CL-20 g(-1) dry mass. These findings demonstrate that CL-20 or potential transformation products are taken into the earthworm body through dermal contact. This information should prove valuable in assessing the bioaccumulation potential and ecological risks of CL-20.

Water-Soluble Epitaxial NaCl Thin Film for Fabrication of Flexible Devices.

PubMed

Lee, Dong Kyu; Kim, Sungjoo; Oh, Sein; Choi, Jae-Young; Lee, Jong-Lam; Yu, Hak Ki

2017-08-18

We studied growth mechanisms of water-soluble NaCl thin films on single crystal substrates. Epitaxial growth of NaCl(100) on Si(100) and domain-matched growth of NaCl(111) on c-sapphire were obtained at thicknesses below 100 nm even at room temperature from low lattice mismatches in both cases. NaCl thin film, which demonstrates high solubility selectivity for water, was successfully applied as a water-soluble sacrificial layer for fabrication of several functional materials, such as WO 3 nano-helix and Sn doped In 2 O 3 nano-branches.

Fractalkine (CX3CL1), a new factor protecting β-cells against TNFα.

PubMed

Rutti, Sabine; Arous, Caroline; Schvartz, Domitille; Timper, Katharina; Sanchez, Jean-Charles; Dermitzakis, Emmanouil; Donath, Marc Y; Halban, Philippe A; Bouzakri, Karim

2014-10-01

We have previously shown the existence of a muscle-pancreas intercommunication axis in which CX3CL1 (fractalkine), a CX3C chemokine produced by skeletal muscle cells, could be implicated. It has recently been shown that the fractalkine system modulates murine β-cell function. However, the impact of CX3CL1 on human islet cells especially regarding a protective role against cytokine-induced apoptosis remains to be investigated. Gene expression was determined using RNA sequencing in human islets, sorted β- and non-β-cells. Glucose-stimulated insulin secretion (GSIS) and glucagon secretion from human islets was measured following 24 h exposure to 1-50 ng/ml CX3CL1. GSIS and specific protein phosphorylation were measured in rat sorted β-cells exposed to CX3CL1 for 48 h alone or in the presence of TNFα (20 ng/ml). Rat and human β-cell apoptosis (TUNEL) and rat β-cell proliferation (BrdU incorporation) were assessed after 24 h treatment with increasing concentrations of CX3CL1. Both CX3CL1 and its receptor CX3CR1 are expressed in human islets. However, CX3CL1 is more expressed in non-β-cells than in β-cells while its receptor is more expressed in β-cells. CX3CL1 decreased human (but not rat) β-cell apoptosis. CX3CL1 inhibited human islet glucagon secretion stimulated by low glucose but did not impact human islet and rat sorted β-cell GSIS. However, CX3CL1 completely prevented the adverse effect of TNFα on GSIS and on molecular mechanisms involved in insulin granule trafficking by restoring the phosphorylation (Akt, AS160, paxillin) and expression (IRS2, ICAM-1, Sorcin, PCSK1) of key proteins involved in these processes. We demonstrate for the first time that human islets express and secrete CX3CL1 and CX3CL1 impacts them by decreasing glucagon secretion without affecting insulin secretion. Moreover, CX3CL1 decreases basal apoptosis of human β-cells. We further demonstrate that CX3CL1 protects β-cells from the adverse effects of TNFα on their function

Regulation of K-Cl cotransport: from function to genes.

PubMed

Adragna, N C; Di Fulvio, M; Lauf, P K

2004-10-01

This review intends to summarize the vast literature on K-Cl cotransport (COT) regulation from a functional and genetic viewpoint. Special attention has been given to the signaling pathways involved in the transporter's regulation found in several tissues and cell types, and more specifically, in vascular smooth muscle cells (VSMCs). The number of publications on K-Cl COT has been steadily increasing since its discovery at the beginning of the 1980s, with red blood cells (RBCs) from different species (human, sheep, dog, rabbit, guinea pig, turkey, duck, frog, rat, mouse, fish, and lamprey) being the most studied model. Other tissues/cell types under study are brain, kidney, epithelia, muscle/smooth muscle, tumor cells, heart, liver, insect cells, endothelial cells, bone, platelets, thymocytes and Leishmania donovani. One of the salient properties of K-Cl-COT is its activation by cell swelling and its participation in the recovery of cell volume, a process known as regulatory volume decrease (RVD). Activation by thiol modification with N-ethylmaleimide (NEM) has spawned investigations on the redox dependence of K-Cl COT, and is used as a positive control for the operation of the system in many tissues and cells. The most accepted model of K-Cl COT regulation proposes protein kinases and phosphatases linked in a chain of phosphorylation/dephosphorylation events. More recent studies include regulatory pathways involving the phosphatidyl inositol/protein kinase C (PKC)-mediated pathway for regulation by lithium (Li) in low-K sheep red blood cells (LK SRBCs), and the nitric oxide (NO)/cGMP/protein kinase G (PKG) pathway as well as the platelet-derived growth factor (PDGF)-mediated mechanism in VSMCs. Studies on VSM transfected cells containing the PKG catalytic domain demonstrated the participation of this enzyme in K-Cl COT regulation. Commonly used vasodilators activate K-Cl COT in a dose-dependent manner through the NO/cGMP/PKG pathway. Interaction between the

Nanoscale structural and electronic characterization of α-RuCl3 layered compound

NASA Astrophysics Data System (ADS)

Ziatdinov, Maxim; Maksov, Artem; Banerjee, Arnab; Zhou, Wu; Berlijn, Tom; Yan, Jiaqiang; Nagler, Stephen; Mandrus, David; Baddorf, Arthur; Kalinin, Sergei

The exceptional interplay of spin-orbit effects, Coulomb interaction, and electron-lattice coupling is expected to produce an elaborate phase space of α-RuCl3 layered compound, which to date remains largely unexplored. Here we employ a combination of scanning transmission electron microscopy (STEM) and scanning tunneling microscopy (STM) for detailed evaluation of the system's microscopic structural and electronic orders with a sub-nanometer precision. The STM and STEM measurements are further supported by neutron scattering, X-Ray diffraction, density functional theory (DFT), and multivariate statistical analysis. Our results show a trigonal distortion of Cl octahedral ligand cage along the C3 symmetry axes in each RuCl3 layer. The lattice distortion is limited mainly to the Cl subsystem leaving the Ru honeycomb lattice nearly intact. The STM topographic and spectroscopic characterization reveals an intra unit cell electronic symmetry breaking in a spin-orbit coupled Mott insulating phase on the Cl-terminated surface of α-RuCl3. The associated long-range charge order (CO) pattern is linked to a surface component of Cl cage distortion. We finally discuss a fine structure of CO and its potential relation to variations of average unit cell geometries found in multivariate analysis of STEM data. The research was sponsored by the U.S. Department of Energy.

Cl-rich hydrous mafic mineral assemblages in the Highiș massif, Apuseni Mountains, Romania

NASA Astrophysics Data System (ADS)

Bonin, Bernard; Tatu, Mihai

2016-08-01

The Guadalupian (Mid-Permian) Highiș massif (Apuseni Mountains, Romania) displays a bimodal igneous suite of mafic (gabbro, diorite) and A-type felsic (alkali feldspar granite, albite granite, and hybrid granodiorite) rocks. Amphibole is widespread throughout the suite, and yields markedly high chlorine contents. Three groups are identified: Cl-rich potassic hastingsite (2.60-3.40 wt% Cl) within A-type felsic rocks and diorite, mildly Cl-rich pargasite to hornblende (0.80-1.90 wt% Cl) within gabbro, and low F-Cl hornblende within gabbro and hybrid granodiorite. Coexisting biotite is either Cl-rich within diorite, or F-Cl-poor to F-rich within A-type felsic rocks. Chlorine and fluorine are distributed in both mafic phases, according to the F-Fe and Cl-Mg avoidance rules. The low-Ti contents suggest subsolidus compositions. Cl-rich amphibole within diorite and A-type felsic rocks yields a restricted temperature range - from 575 °C down to 400 °C, whereas mildly Cl-rich amphibole within gabbro displays the highest range - from 675 to 360 °C. Temperatures recorded by Cl-rich biotite within diorite range from 590 to 410 °C. Biotite within A-type felsic rocks yields higher temperatures than amphibole: the highest values- from 640 to 540 °C - are recorded in low-F-Cl varieties, whereas the lowest values- from 535 to 500 °C - are displayed by F-rich varieties. All data point to halogen-rich hydrothermal fluids at upper greenschist facies conditions percolating through fractures and shear zones and pervasively permeating the whole Highiș massif, with F precipitating as interstitial fluorite and Cl incorporating into amphibole, during one, or possibly several, hydrothermal episodes that would have occurred during a ~ 150 My-long period of time extending from the Guadalupian (Mid-Permian) to the Albian (Mid-Cretaceous).

Interaction of antitumor drug Sn(CH 3) 2Cl 2 with DNA and RNA

NASA Astrophysics Data System (ADS)

Nafisi, Shohreh; Sobhanmanesh, Amir; Esm-Hosseini, Majid; Alimoghaddam, Kamran; Tajmir-Riahi, Heidar Ali

2005-08-01

Sn(CH3)2Cl2 exerts its antitumor activity in a specific way. Unlike anticancer cis-Pt(NH3)2Cl2 drug which binds strongly to the nitrogen atoms of DNA bases, Sn(CH3)2Cl2 shows no major affinity towards base binding. Thus, the mechanism of action by which tinorganometallic compounds exert antitumor activity would be different from that of the cisplatin drug. The aim of this study was to examine the binding of Sn(CH3)2Cl2 with calf thymus DNA and yeast RNA in aqueous solutions at pH 7.1-6.6 with constant concentrations of DNA and RNA and various molar ratios of Sn(CH3)2Cl2/DNA (phosphate) and Sn(CH3)2Cl2/RNA of 1/40, 1/20, 1/10, 1/5. Fourier transform infrared (FTIR) and UV-visible difference spectroscopic methods were used to determine the Sn(CH3)2Cl2 binding mode, binding constant, sequence selectivity and structural variations of Sn(CH3)2Cl2/DNA and Sn(CH3)2Cl2/RNA complexes in aqueous solution. Sn(CH3)2Cl2 hydrolyzes in water to give Sn(CH3)2(OH)2 and [Sn(CH3)2(OH)(H2O)n]+ species. Spectroscopic evidence showed that interaction occurred mainly through (CH3)2Sn(IV) hydroxide and polynucleotide backbone phosphate group with overall binding constant of K(Sn(CH3)2Cl2-DNA)=1.47×105 M-1 and K(Sn(CH3)2Cl2-RNA)=7.33×105 M-1. Sn(CH3)2Cl2 induced no biopolymer conformational changes with DNA remaining in the B-family structure and RNA in A-conformation upon drug complexation.

CH3Cl, CH2Cl2, CHCl3, and CCl4: Infrared spectra, radiative efficiencies, and global warming potentials

NASA Astrophysics Data System (ADS)

Wallington, Timothy J.; Pivesso, Bruno Pasquini; Lira, Alane Moura; Anderson, James E.; Nielsen, Claus Jørgen; Andersen, Niels Højmark; Hodnebrog, Øivind

2016-05-01

Infrared spectra for the title compounds were measured experimentally in 700 Torr of air at 295 K and systematically modeled in B3LYP, M06-2X and MP2 calculations employing various basis sets. Calibrated infrared spectra over the wavenumber range 600-3500 cm-1 are reported and combined with literature data to provide spectra for use in experimental studies and radiative transfer calculations. Integrated absorption cross sections are (units of cm-1 molecule-1): CH3Cl, 660-780 cm-1, (3.89±0.19)×10-18; CH2Cl2, 650-800 cm-1, (2.16±0.11)×10-17; CHCl3, 720-810 cm-1, (4.08±0.20)×10-17; and CCl4, 730-825 cm-1, (6.30±0.31)×10-17. CH3Cl, CH2Cl2, CHCl3, and CCl4 have radiative efficiencies of 0.004, 0.028, 0.070, and 0.174 W m-2 ppb-1 and global warming potentials (100 year horizon) of 5, 8, 15, and 1775, respectively. Quantum chemistry calculations generally predict larger band intensities than the experimental values. The best agreement with experiments is obtained in MP2(Full) calculations employing basis sets of at least triple-zeta quality augmented by diffuse functions. The B3LYP functional is found ill-suited for calculating vibrational frequencies and infrared intensities of halocarbons.

Characterisation of a PdCl 2/SnCl 2 electroless plating catalyst system adsorbed on barium titanate-based electroactive ceramics

NASA Astrophysics Data System (ADS)

Meenan, B. J.; Brown, N. M. D.; Wilson, J. W.

1994-03-01

A PdCl 2/SnCl 2 metallisation catalyst system, of the type used to activate non-conducting surfaces for electroless metal deposition, has been characterised by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The substrate is a barium titanate (BaTiO 3)-based electroactive ceramic of the type used in the fabrication of multilayer ceramic capacitors (MLCC). The treatment of the substrate surface with the PdCl 2/SnCl 2 "sensitiser" solution leads to the adsorption of catalytically inactive compounds of palladium and tin. Subsequent treatment of this surface with an "accelerator" solution removes excess oxides, hydroxides and salts of tin thereby leaving the active catalyst species, Pd xSn y, on the surface. Such sites, on exposure to the appropriete electroless plating bath, are then responsible for the metal deposition. In this study, the chemical state and relative quantities of the various surface species present after each of the processing stages have been determined by XPS. The surface roughness of the substrate results in less of the tin compounds present thereon being removed on washing the catalysed surface in the accelerator solution than normally reported for such systems, thereby affecting the measured Pd: Sn ratio. SEM studies show that the accelerator solution treatment generates crystalline areas, which may be a result of coagulation of the Pd xSn y particles present, in the otherwise amorphous catalyst coating.

Heterogeneous reactions of HNO3(g) + NaCl(s) yields HCl(g) + NaNO3(s) and N2O5(g) + NaCl(s) yields ClNO2(g) + NaNO3(s)

NASA Technical Reports Server (NTRS)

Leu, Ming-Taun; Timonen, Raimo S.; Keyser, Leon F.; Yung, Yuk L.

1995-01-01

The heterogeneous reactions of HNO3(g) + NaCl(s) yields HCl(g) + NaNO3(s) (eq 1) and N2O5(g) + NaCl(s) yields ClNO2(g) + NaNO3(S) (eq 2) were investigated over the temperature range 223-296 K in a flow-tube reactor coupled to a quadrupole mass spectrometer. Either a chemical ionization mass spectrometer (CIMS) or an electron-impact ionization mass spectrometer (EIMS) was used to provide suitable detection sensitivity and selectivity. In order to mimic atmospheric conditions, partial pressures of HNO3 and N2O5 in the range 6 x 10(exp -8) - 2 x 10(exp -6) Torr were used. Granule sizes and surface roughness of the solid NaCl substrates were determined by using a scanning electron microscope. For dry NaCl substrates, decay rates of HNO3 were used to obtain gamma(1) = 0.013 +/- 0.004 (1sigma) at 296 K and > 0.008 at 223 K, respectively. The error quoted is the statistical error. After all corrections were made, the overall error, including systematic error, was estimated to be about a factor of 2. HCl was found to be the sole gas-phase product of reaction 1. The mechanism changed from heterogeneous reaction to predominantly physical adsorption when the reactor was cooled from 296 to 223 K. For reaction 2 using dry salts, gamma(2) was found to be less than 1.0 x 10(exp -4) at both 223 and 296 K. The gas-phase reaction product was identified as ClNO2 in previous studies using an infrared spectrometer. An enhancement in reaction probability was observed if water was not completely removed from salt surfaces, probably due to the reaction of N2O5(g) + H2O(s) yields 2HNO3(g). Our results are compared with previous literature values obtained using different experimental techniques and conditions. The implications of the present results for the enhancement of the hydrogen chloride column density in the lower stratosphere after the El Chichon volcanic eruption and for the chemistry of HCl and HNO3 in the marine troposphere are discussed.

Experimental studies of Cl-atom reactions at high temperatures: Cl + H{sub 2} {yields} HCl + H from 291 to 1283 K

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

Adusei, G.Y.; Fontijn, A.

1994-12-31

A method is presented for producing Cl atoms for kinetic experiments above 750 K. Combined with a low temperature Cl-atom production technique, rate coefficients for the title reaction have been obtained over a wide temperature range. The Cl atoms were generated by flash photolysis of CCl{sub 4} for the low-temperature measurements and by pulsed laser photolysis of NaCl for the high-temperature measurements. The relative Cl-atom concentrations were monitored by time-resolved resonance fluorescence. The data are well fitted by the expression k{sub 1}(291--1,283 K) = 4.4 {times} 10{sup {minus}11} exp({minus}2568 K/T) cm{sup 3}/molecule, with 2{sigma} precision limits of {+-} 9 {+-}16more » %, depending on temperature, and corresponding 2{sigma} accuracy limits of about {+-} 26 %. There is good agreement between the rate coefficients measured here and those from previous low-temperature studies, leading to the recommendation k{sub 1}(200--1,283 K) = 2.3 {times} 10{sup {minus}16} (T/K){sup 1.63} exp({minus}1592 K/T) cm{sup 3}/molecule s, with a suggested 2{sigma} accuracy limit of {+-}28% for the combined data. A transition state theory calculation base don a semiempirical London-Eyring-Polanyi-Sato (LEPS) potential energy surface gives excellent agreement with the combined experimental results. Extension of their previous recommendation for the reverse reaction to lower temperatures leads to k{sub 2}(200--1,200 K) = 6.6 {times} 10{sup {minus}16} (T/K){sup 1.44} exp({minus}1241 K/T) cm{sup 3}/molecule s, with 2{sigma} accuracy limits within {+-}25 %. There is excellent agreement between the present data and the predicted expression from that reaction and equilibrium data.« less

NaCl and water responses across the frog tongue epithelium in vitro.

PubMed

Soeda, H; Sakudo, F

1990-01-01

Isolated dorsal epithelium of the frog tongue elicited transepithelial NaCl and water responses across the tissue when NaCl was added to or removed from the adapting Ringer solution in the mucosal surface, respectively. The NaCl response which was a negative polarization in the mucosa with respect to the serosa was associated with a decrease in resistance across the tissue, whereas the water response which was a positive polarization was associated with an increase in the resistance. The decrease and increase in the tissue resistance remained unchanged by various polarizations of the transepithelial potential difference across the tissue. Characteristics of the NaCl and water responses were similar in many respects to those in the taste cells and nerves of frogs. Thus the NaCl and water responses may relate to taste reception.

The influence of ocean halogen and sulfur emissions in the air quality of a coastal megacity: The case of Los Angeles.

PubMed

Muñiz-Unamunzaga, Maria; Borge, Rafael; Sarwar, Golam; Gantt, Brett; de la Paz, David; Cuevas, Carlos A; Saiz-Lopez, Alfonso

2018-01-01

The oceans are the main source of natural halogen and sulfur compounds, which have a significant influence on the oxidizing capacity of the marine atmosphere; however, their impact on the air quality of coastal cities is currently unknown. We explore the effect of marine halogens (Cl, Br and I) and dimethyl sulfide (DMS) on the air quality of a large coastal city through a set of high-resolution (4-km) air quality simulations for the urban area of Los Angeles, US, using the Community Multiscale Air Quality (CMAQ model). The results indicate that marine halogen emissions decrease ozone and nitrogen dioxide levels up to 5ppbv and 2.5ppbv, respectively, in the city of Los Angeles. Previous studies suggested that the inclusion of chlorine in air quality models leads to the generation of ozone in urban areas through photolysis of nitryl chloride (ClNO 2 ). However, we find that when considering the chemistry of Cl, Br and I together the net effect is a reduction of surface ozone concentrations. Furthermore, combined ocean emissions of halogens and DMS cause substantial changes in the levels of key urban atmospheric oxidants such as OH, HO 2 and NO 3 , and in the composition and mass of fine particles. Although the levels of ozone, NO 3 and HO x are reduced, we find a 10% increase in secondary organic aerosol (SOA) mean concentration, attributed to the increase in aerosol acidity and sulfate aerosol formation when combining DMS and bromine. Therefore, this new pathway for enhanced SOA formation may potentially help with current model under predictions of urban SOA. Although further observations and research are needed to establish these preliminary conclusions, this first city-scale investigation suggests that the inclusion of oceanic halogens and DMS in air quality models may improve regional air quality predictions over coastal cities around the world. Copyright © 2017 Elsevier B.V. All rights reserved.

Sorption and oxic degradation of the explosive CL-20 during transport in subsurface sediments.

PubMed

Szecsody, J E; Girvin, D C; Devary, B J; Campbell, J A

2004-08-01

The abiotic sorption and oxic degradation processes that control the fate of the explosive CL-20, Hexanitrohexaazaisowurtzitane, in the subsurface environment were investigated to determine the potential for vadose and groundwater contamination. Sorption of aqueous CL-20 is relatively small (K(d) = 0.02-3.83 cm3 g(-1) for 7 sediments and 12 minerals), which results in only slight retardation relative to water movement. Thus, CL-20 could move quickly through unsaturated and saturated sediments of comparable composition to groundwater, similar to the subsurface behavior of RDX. CL-20 sorption was mainly to mineral surfaces of the sediments, and the resulting isotherm was nonlinear. CL-20 abiotically degrades in oxic environments at slow rates (i.e., 10s to 100s of hours) with a wide variety of minerals, but at fast rates (i.e., minutes) in the presence of 2:1 phyllosilicate clays (hectorite, montmorillonite, nontronite), micas (biotite, illite), and specific oxides (MnO2 and the ferrous-ferric iron oxide magnetite). High concentrations of surface ferrous iron in a dithionite reduced sediment degraded CL-20 the fastest (half-life < 0.05 h), but 2:1 clays containing no structural or adsorbed ferrous iron (hectorite) could also quickly degrade CL-20 (half-life < 0.2 h). CL-20 degradation rates were slower in natural sediments (half-life 3-800 h) compared to minerals. Sediments with slow degradation rates and small sorption would exhibit the highest potential for deep subsurface migration. Products of CL-20 oxic degradation included three high molecular weight compounds and anions (nitrite and formate). The 2-3.5 moles of nitrite produced suggest CL-20 nitro-groups are degraded, and the amount of formate produced (0.2-1.2 moles) suggests the CL-20 cage structure is broken in some sediments. Identification of further degradation products and CL-20 mineralization rates is needed to fully assess the impact of these CL-20 transformation rates on the risk of CL-20 (and

Physical and chemical microstructural damage in pressed CL-20 explosives

NASA Astrophysics Data System (ADS)

Demol, Gauthier; Sandusky, Harold W.

2000-04-01

The ultimate utility of CL-20 as an ingredient in explosive and propellant formulations will depend upon the ability to understand the factors that are responsible for batch-to-batch variability with respect to sensitivity, and also to control the sensitivity in formulations within acceptable limits. We used light microscopy of cold-mounted, polished samples to characterize CL-20 at various stages in its life cycle. The evolution of damage from the initial neat crystals of CL-20 to the ready-to-use pressed pellets shows that processing seriously damages the crystals. These crystals are very brittle, and several explanations are proposed.

Experimental studies on cycling stable characteristics of inorganic phase change material CaCl2·6H2O-MgCl2·6H2O modified with SrCl2·6H2O and CMC

NASA Astrophysics Data System (ADS)

He, Meizhi; Yang, Luwei; Zhang, Zhentao

2018-01-01

By means of mass ratio method, binary eutectic hydrated salts inorganic phase change thermal energy storage system CaCl2·6H2O-20wt% MgCl2·6H2O was prepared, and through adding nucleating agent 1wt% SrCl2·6H2O and thickening agent 0.5wt% carboxy methyl cellulose (CMC), inoganic phase change material (PCM) modified was obtained. With recording cooling-melting curves simultaneously, this PCM was frozen and melted for 100 cycles under programmable temperature control. After per 10 cycles, the PCM was charaterized by differential scanning calorimeter (DSC), X-ray diffraction (XRD) and density meter, then analysing variation characteristics of phase change temperature, supercooling degree, superheat degree, latent heat, crystal structure and density with the increase of cycle index. The results showed that the average values of average phase change temperature for cooling and heating process were 25.70°C and 27.39°C respectively with small changes. The average values of average supercooling and superheat degree were 0.59°C and 0.49°C respectively, and the maximum value was 1.10°C. The average value and standard deviation of latent heat of fusion were 120.62 J/g and 1.90 J/g respectively. Non-molten white solid sediments resulted from phase separation were tachyhydrite (CaMg2Cl6·12H2O), which was characterized by XRD. Measuring density of the PCM after per 10 cycles, and the results suggested that the total mass of tachyhydrite was limited. In summary, such modified inoganic PCM CaCl2·6H2O-20wt% MgCl2·6H2O-1wt% SrCl2·6H2O-0.5wt% CMC could stay excellent circulation stability within 100 cycles, and providing reference value in practical use.

On the Ground Electronic States of TiF and TiCl

PubMed

Boldyrev; Simons

1998-04-01

The low-lying electronic states of TiF and TiCl have been studied using high level ab initio techniques. Both are found to have two low-lying excited electronic states, 4Sigma- (0.080 eV (TiF) and 0.236 eV (TiCl)) and 2Delta (0.266 eV (TiF) and 0.348 eV (TiCl)), and 4Phi ground states at the highest CCSD(T)/6-311++G(2d,2f) level of theory. Our theoretical predictions of 4Phi ground electronic states for TiF and TiCl support recent experimental findings by Ram and Bernath, and our calculated bond lengths and vibrational frequencies are in reasonable agreement with their experimental data. Copyright 1998 Academic Press.

Static and Dynamic Compaction of CL-20 Powders

NASA Astrophysics Data System (ADS)

Cooper, Marcia; Brundage, Aaron; Dudley, Evan

2009-06-01

Hexanitrohexaazaisowurtzitane (CL-20) powders were compacted under quasi-static and dynamic loading conditions. A uniaxial compression apparatus quasi-statically compressed the powders to 90% theoretical maximum density with applied stresses up to 0.5 GPa. Dynamic compaction measurements using low-density pressings (62-70% theoretical maximum density) were obtained in a single-stage gas gun at impact velocities between 0.17-0.70 km/s. Experiments were conducted in a reverse ballistic arrangement in which the CL-20 ladened projectile impacted a target consisting of an aluminized window. VISAR-measured particle velocities at the explosive-window interface determined the shock Hugoniot states for pressures up to 0.9 GPa. The powder compaction behavior is found to be stiffer under dynamic loading than under quasi-static loading. Additional gas gun tests were conducted in which the low-density CL-20 pressings were confined within a target cup by the aluminized window. This arrangement enabled temporal measurement of the transmitted wave profiles in which elastic wave precursors were observed.

Easy methods to study the smart energetic TNT/CL-20 co-crystal.

PubMed

Li, Huarong; Shu, Yuanjie; Gao, Shijie; Chen, Ling; Ma, Qing; Ju, Xuehai

2013-11-01

2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) is a high-energy nitramine explosive with high mechanical sensitivity. 2,4,6-trinitrotoluene (TNT) is insensitive but by no means a high performance explosive. To reveal the significant importance and smart-material functionality of the energetic-energetic co-crystals, the stability, mechanical and explosive properties TNT/CL-20 co-crystal, TNT crystal and CL-20 crystal were studied. Non-hydrogen bonded non-covalent interactions govern the structures of energetic-energetic co-crystals. However, it is very difficult to accurately calculate the non-covalent intermolecular interaction energies. In this paper, the local conformation and the intricate non-covalent interactions were effectively mapped and analyzed from the electron density (ρ) and its derivatives. The results show that the two components TNT and CL-20 are connected mainly by nitro-aromatic interactions, and nitro-nitro interactions. The steric interactions in TNT/CL-20 could not be confronted with the attractive interactions. Moreover, the scatter graph of TNT crystal reveals the reason why TNT is brittle. The detailed electrostatic potential analysis predicted that the detonation velocities (D) and impact sensitivity for the compounds both increase in the sequence of CL-20 > TNT/CL-20 co-crystal > TNT. Additionally, TNT/CL-20 co-crystal has better malleability than its pure components. This demonstrates the capacity and the feasibility of realizing explosive smart materials by co-crystallization, even if strong hydrogen bonding schemes are generally lacking in energetic materials.

Infrared absorption of 1-chloro-2-methyl-2-propyl [⋅C(CH3)2CH2Cl] and 2-chloro-2-methylpropyl [⋅CH2C(CH3)2Cl] radicals produced in the addition reactions of Cl with isobutene (i-C4H8) in solid para-hydrogen.

PubMed

Chou, Ching-Yin; Lee, Yuan-Pern

2016-10-07

The addition reactions of chlorine atom with isobutene (i-C 4 H 8 ) in solid para-hydrogen (p-H 2 ) were investigated with infrared (IR) absorption spectra. When a p-H 2 matrix containing Cl 2 and isobutene was irradiated with ultraviolet light at 365 nm, intense lines in a set at 534.5, 1001.0, 1212.9, 1366.0, 2961.6, and 2934.7 cm -1 , and several weaker others due to the 1-chloro-2-methyl-2-propyl radical, ⋅ C(CH 3 ) 2 CH 2 Cl, and those in a second set including intense ones at 642.7, 799.2, 1098.2, 1371.8, and 3027.3 cm -1 due to the 2-chloro-2-methylpropyl radical, ⋅ CH 2 C(CH 3 ) 2 Cl, appeared; the ratio of ⋅ C(CH 3 ) 2 CH 2 Cl to ⋅ CH 2 C(CH 3 ) 2 Cl was approximately (3 ± 1):1. The observed wavenumbers and relative intensities agree with the vibrational wavenumbers and IR intensities predicted with the B3PW91/aug-cc-pVTZ method. That the Cl atom adds to both carbons of the C=C bond of isobutene with the terminal site slightly favored is consistent with the energies of products predicted theoretically, but is in contrast to the reaction of Cl + propene in solid p-H 2 in which the addition of Cl to mainly the central C atom was previously reported. The role of the p-H 2 matrix in affecting the reaction paths is discussed. Absorption lines of the complex i-C 4 H 8 ⋅Cl 2 and the dichloro-product anti-1,2-dichloro-2-methylpropane, a-CH 2 ClCCl(CH 3 ) 2 , are also characterized.

Regulation of Cl^- Channels in Normal and Cystic Fibrosis Airway Epithelial Cells by Extracellular ATP

NASA Astrophysics Data System (ADS)

Stutts, M. J.; Chinet, T. C.; Mason, S. J.; Fullton, J. M.; Clarke, L. L.; Boucher, R. C.

1992-03-01

The rate of Cl^- secretion by human airway epithelium is determined, in part, by apical cell membrane Cl^- conductance. In cystic fibrosis airway epithelia, defective regulation of Cl^- conductance decreases the capability to secrete Cl^-. Here we report that extracytosolic ATP in the luminal bath of cultured human airway epithelia increased transepithelial Cl^- secretion and apical membrane Cl^- permeability. Single-channel studies in excised membrane patches revealed that ATP increased the open probability of outward rectifying Cl^- channels. The latter effect occurs through a receptor mechanism that requires no identified soluble second messengers and is insensitive to probes of G protein function. These results demonstrate a mode of regulation of anion channels by binding ATP at the extracellular surface. Regulation of Cl^- conductance by external ATP is preserved in cystic fibrosis airway epithelia.

Integrando la historia clínica ambiental en el consejo prenatal y cuidado de 2 casos de gastrosquisis

PubMed Central

García, J.A. Ortega; Martín, M.; Lamas, A. Brea; De Paco-Matallana, C.; Jiménez, J.I. Ruiz; Soldin, O.P.

2017-01-01

Introducción La gastroquisis es una malformación de etiología desconocida en la que se han implicado factores de riesgo (FR) genéticos y medioambientales. El objetivo de este trabajo es desarrollar la historia clínica medioambiental pediátrica (HCMAP) de la gastroquisis en 2 pacientes. Pacientes y métodos Revisión bibliográfica en Pubmed y en el Developmental and Reproductive Toxicology Database. Búsqueda selectiva de sustancias con capacidad teratogénica en el Hazardous Substances Data Bank. Palabras clave utilizadas fueron: «gastroschisis» y «gastroschisis and risk factor». Resultados En ambos casos están presentes los siguientes FR descritos en la literatura: corta cohabitación, embarazos no planificados de madres relativamente jóvenes, cambio de pareja reciente, ingesta de alcohol, déficits nutricionales importantes, tabaquismo activo/pasivo. Un caso estuvo expuesto a cocaína, humo de cannabis y se realizó una ortopantografía durante el embarazo. Conclusiones 1) Es necesario obtener la HCMAP en todo paciente con gastroquisis; 2) una cuidadosa HCMAP requiere una adecuada revisión de los FR relacionados e instrucción básica para caracterizar y cuantificar las exposiciones medioambientales, y 3) siguiendo estos pasos, complementaremos nuestras labores asistenciales y preventivas. PMID:20122885

Calculated rate constants for the reaction ClO + O yields Cl + O2 between 220 and 1000 deg K. [molecular trajectories and stratospheric ozone

NASA Technical Reports Server (NTRS)

Jaffee, R. L.

1978-01-01

Classical trajectory calculations are presented for the reaction ClO + O yields Cl + O2, a reaction which is an important step in the chlorine-catalyzed destruction of ozone which is thought to occur in the 220 and 1000 K. The calculated rate constant is 4.36 x 10 to the minus 11th power exp (-191/T)cu cm molecule (-1)s(-1) and its value at 300 K is 2.3 plus or minus 10 to the 11th power cu cm molecule (-1)s(-1), about a factor of 2 lower than recent experimental data. The empirical potential energy surface used in the calculations was constructed to fit experimental data for ClO, O2 and ClOO molecules. Other important features of this potential surface, such as the barrier to reaction, were varied systematically and calculations were performed for a range of conditions to determine the best theoretical rate constants. Results demonstrate the utility of classical trajectory methods for determining activation energies and other kinetic data for important atmospheric reactions.

Energetics of acclimation to NaCl by submerged, anoxic rice seedlings

PubMed Central

Kurniasih, Budiastuti; Greenway, Hank; Colmer, Timothy David

2017-01-01

Background and aims Our aim was to elucidate how plant tissues under a severe energy crisis cope with imposition of high NaCl, which greatly increases ion fluxes and hence energy demands. The energy requirements for ion regulation during combined salinity and anoxia were assessed to gain insights into ion transport processes in the anoxia-tolerant coleoptile of rice. Methods We studied the combined effects of anoxia plus 50 or 100 mm NaCl on tissue ions and growth of submerged rice (Oryza sativa) seedlings. Excised coleoptiles allowed measurements in aerated or anoxic conditions of ion net fluxes and O2 consumption or ethanol formation and by inference energy production. Key Results Over 80 h of anoxia, coleoptiles of submerged intact seedlings grew at 100 mm NaCl, but excised coleoptiles, with 50 mm exogenous glucose, survived only at 50 mm NaCl, possibly due to lower energy production with glucose than for intact coleoptiles with sucrose as substrate. Rates of net uptake of Na+ and Cl− by coleoptiles in anoxia were about half those in aerated solution. Ethanol formation in anoxia and O2 uptake in aerobic solution were each increased by 13–15 % at 50 mm NaCl, i.e. ATP formation was stimulated. For acclimation to 50 mm NaCl, the anoxic tissues used only 25 % of the energy that was expended by aerobic tissues. Following return of coleoptiles to aerated non-saline solution, rates of net K+ uptake recovered to those in continuously aerated solution, demonstrating there was little injury during anoxia with 50 mm NaCl. Conclusion Rice seedlings survive anoxia, without the coleoptile incurring significant injury, even with the additional energy demands imposed by NaCl (100 mm when intact, 50 mm when excised). Energy savings were achieved in saline anoxia by less coleoptile growth, reduced ion fluxes as compared to aerobic coleoptiles and apparent energy-economic ion transport systems. PMID:27694332

Intermolecular C-H···O, Cl···Cl and π-π interactions in the 2-dichloromethyl derivative of vitamin K3.

PubMed

Soave, Raffaella; Colombo, Pietro

2013-12-15

The title 1,4-naphthoquinone, 2-dichloromethyl-3-methyl-1,4-dihydronaphthalene-1,4-dione, C12H8Cl2O2, is a chlorinated derivative of vitamin K3, which is a synthetic compound also known as menadione. Molecules of (I) are planar and lie on a crystallographic mirror plane (Z' = 0.5) in the space group Pnma. They are connected to each other by C-H···O hydrogen bonds, forming two-dimensional layers parallel to the ac plane. In addition, Cl···Cl and π-π interactions link adjacent molecules in different layers, thus forming zigzag ribbons along the b axis, such that a three-dimensional architecture is generated.

Canadair CL-227 Remotely Piloted Vehicle

NASA Astrophysics Data System (ADS)

Clark, Andrew S.

1983-08-01

The Canadair CL-227 is a rotary winged Remotely Piloted Vehicle (RPV) intended initially as the air-vehicle for a medium range battlefield surveillance and target acquisition system. The concept on which this vehicle is based brings together in-house expertise as a designer and manufacturer of surveillance drones (AN-USD-50l -MIDGE-) with experience in rigid rotor technology from the CL-84 tilt wing VTOL program. The vehicle is essentially modular in design with a power module containing the engine, fuel and related systems, a rotor module containing the two counter-rotating rotors and control actuators, and a control module containing the autopilot, data link and sensor system. The vehicle is a true RPV (as opposed to a drone) as it is flown in real time by an operator on the ground and requires relatively little skill to pilot.

[Pd(μ-Cl)Cl(IPr*)]2: a highly hindered pre-catalyst for the synthesis of tetra-ortho-substituted biaryls via Grignard reagent cross-coupling.

PubMed

Lesieur, Mathieu; Slawin, Alexandra M Z; Cazin, Catherine S J

2014-08-14

The new well-defined catalyst [Pd(μ-Cl)Cl(IPr*)]2 enables the efficient Grignard reagent cross-coupling for the synthesis of tetra-ortho-substituted biaryls. The high reactivity of the complex is associated with the important bulkiness of the IPr* ligand. The dimer represents the most efficient catalyst reported to date for this challenging transformation.

Textural improvement of salt-reduced Alaska pollack (Theragra chalcogramma) roe product by CaCl2.

PubMed

Chen, Chaoping; Okazaki, Emiko; Osako, Kazufumi

2016-12-15

Salt-reduced Alaska pollack roe benefits public health by decreasing NaCl intake; however, it has a poor texture with low breaking strength. This study addresses the feasibility of NaCl reduction in salted roe products, with focusing on the improvement of breaking strength using CaCl2. Salted roe products were prepared by immersing Alaska pollack roe in either NaCl solutions (3.5, 7.0, 15.0, 20.0, and 25.0%) or 7.0% NaCl solutions with added CaCl2 (0.0, 0.5, 1.0, 2.0, and 3.0%). Breaking strength, moisture and salt contents, eggshell protein composition of the salted roe products, as well as total endogenous transglutaminase (TGase) activity in various NaCl and CaCl2 concentrations were analyzed. CaCl2 addition enhanced eggshell protein crosslinking and breaking strength of the salt-reduced roe products. An acyl transfer reaction catalyzed by calcium-dependent TGase may be responsible for the eggshell protein crosslinking and improved texture. Thus, we successfully developed a salt-reduced Alaska roe product using CaCl2. Copyright © 2016 Elsevier Ltd. All rights reserved.

Dechlorination Mechanism of CuCl Residue from Zinc Hydrometallurgy by Microwave Roasting

NASA Astrophysics Data System (ADS)

Lu, Shuaidan; Ju, Shaohua; Peng, Jinhui; Zhu, Xiaoping; Srinivasakannan, C.; Zhang, Libo; Tu, Ganfeng

2015-04-01

Removal of chlorine (Cl) from the CuCl residue in the process of zinc hydrometallurgy is of great importance to improve the process economics. The current processing methods result in generation of large quantities of polluted discharge necessitating waste treatment systems. The present work attempts to de-chlorinate the CuCl residue through thermal treatment with application of microwave, towards which the effect of the major experimental factors such as roasting temperature, heating duration and particle size of samples on the process has been investigated. And the changes of Gibbs free energy (ΔG) of the dechlorination reactions are calculated which show that: 1) CuCl can react with H2O and air to produce CuO and HCl(g); 2) CuCl can be oxidized by air into CuO and Cl2 would be released. The tail gas chromatography, XRD and SEM-EDS analysis results of samples before and after microwave roasting verified the thermodynamics study results. Thus, the process of dechlorination by microwave roasting technology is feasible, and the tail gas can be mainly HCl(g) and air which can be absorbed with water and produce hydrochloride easily.

Synthesis of palm-based polyurethane-LiClO{sub 4} via prepolymerization

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

Sien, Jason Wong Chee; School of Biosciences, Taylor’s University, Subang Jaya; Badri, Khairiah Haji

2015-09-25

Palm-based polyurethane (pPU) with varying lithium salt (LiClO{sub 4}) content was synthesized. Higher loading percentage of LiClO{sub 4} in the pPU led to the inhibition of prepolymerization process from taking place. Hydrogen bonded C=O was detected in the FTIR spectrum indicating the hydrogen bonding between the urethane bonds. Ordered complexed C=O was observed in the FTIR spectrum confirming the complex formation between urethane bond and Li{sup +} ion. DSC thermogram showed the increase in the LiClO{sub 4} content could increase the glass transition temperature. SEM micrographs exhibited that more bubbles were formed when the LiClO{sub 4} increased from 10 tomore » 30wt% indicating the reaction between free isocyanate groups with moisture presence in the salt due to the hygroscopic properties of LiClO{sub 4}.« less

Dental and Cranial Pathologies in Mice Lacking the Cl−/H+-Exchanger ClC-7

PubMed Central

WEN, Xin; LACRUZ, Rodrigo S.; PAINE, Michael L.

2015-01-01

ClC-7 is a 2Cl−/1H+-exchanger expressed at late endosomes and lysosomes, as well as the ruffled border of osteoclasts. ClC-7 deficiencies in mice and humans lead to impaired osteoclast function and therefore osteopetrosis. Failure of tooth eruption is also apparent in ClC-7 mutant animals, and this has been attributed to the osteoclast dysfunction and the subsequent defect in alveolar bone resorptive activity surrounding tooth roots. Ameloblasts also express ClC-7, and this study aims to determine the significance of ClC-7 in enamel formation by examining the dentitions of ClC-7 mutant mice. Micro-CT analysis revealed that the molar teeth of 3-week old ClC-7 mutant mice had no roots, and the incisors were smaller than their age-matched controls. Despite these notable developmental differences, the enamel and dentin densities of the mutant mice were comparable to those of the wild type littermates. Scanning electron microscopy (SEM) showed normal enamel crystallite and prismatic organization in the ClC-7 mutant mice, although the enamel was thinner (hypoplastic) than in controls. These results suggested that ClC-7 was not critical to enamel and dentin formation, and the observed tooth defects may be related more to a resulting alveolar bone phenotype. Micro-CT analysis also revealed abnormal features in the calvarial bones of the mutant mice. The cranial sutures in ClC-7 mutant mice remained open compared to the closed sutures seen in the control mice at 3 weeks. These data demonstrate that ClC-7 deficiency impacts the development of the dentition and calvaria, but does not significantly disrupt amelogenesis. PMID:25663454

Activation of intestinal Cl- secretion by lubiprostone requires the cystic fibrosis transmembrane conductance regulator.

PubMed

Bijvelds, Marcel J C; Bot, Alice G M; Escher, Johanna C; De Jonge, Hugo R

2009-09-01

Lubiprostone alleviates constipation by stimulating intestinal fluid secretion, purportedly through activation of ClC-2-type Cl(-) channels. Intestinal obstruction is also a recurrent cause of distress in cystic fibrosis (CF) patients, caused by loss of CF transmembrane conductance regulator (CFTR) Cl(-) channel activity. Because ClC-2 recruitment might be beneficial to CF patients, we investigated lubiprostone's mode of action. Cl(-) transport was measured in an Ussing chamber, in 3 model systems: (1) T84 colonocytes, (2) intestinal epithelium of wild-type and CF mice, and (3) intestinal epithelium of CF patients and controls. In T84 monolayers, lubiprostone induced a robust secretory response. Selective permeabilization of the basolateral plasma membrane revealed that lubiprostone activated an apical Cl(-) conductance. The lubiprostone response was attenuated by H89, an inhibitor of the cAMP-dependent protein kinase, and lubiprostone precluded responsiveness to the cAMP agonist forskolin. CFTR blockage by CFTRinh172, but not ClC-2 blockage by CdCl(2), inhibited the lubiprostone response. Lubiprostone induced a CdCl(2)-insensitive secretory response in mouse intestine, but failed to induce intestinal Cl(-) secretion in Cftr-null mice. Correspondingly, lubiprostone induced a secretory response in human intestinal epithelium, but not in tissue of CF patients. The EP(4)-type prostanoid receptor antagonist L-161,982 blocked the lubiprostone response in all 3 models studied. In T84 cells, lubiprostone induced a rise in cAMP levels that was sensitive to EP(4)-receptor blockage. Lubiprostone enhances intestinal Cl(-) and fluid secretion via prostanoid receptor signaling, triggering activation of CFTR. Therefore, it is of limited use for treatment of CF-related intestinal disease.

Extracellular determinants of anion discrimination of the Cl-/H+ antiporter protein CLC-5.

PubMed

De Stefano, Silvia; Pusch, Michael; Zifarelli, Giovanni

2011-12-23

Mammalian CLC proteins comprise both Cl- channels and Cl-/H+ antiporters that carry out fundamental physiological tasks by transporting Cl- across plasma membrane and intracellular compartments. The NO3- over Cl- preference of a plant CLC transporter has been pinpointed to a conserved serine residue located at Scen and it is generally assumed that the other two binding sites of CLCs, Sext and Sin, do not substantially contribute to anion selectivity. Here we show for the Cl-/H+ antiporter CLC-5 that the conserved and extracellularly exposed Lys210 residue is critical to determine the anion specificity for transport activity. In particular, mutations that neutralize or invert the charge at this position reverse the NO3- over Cl- preference of WT CLC-5 at a concentration of 100 mm, but do not modify the coupling stoichiometry with H+. The importance of the electrical charge is shown by chemical modification of K210C with positively charged cysteine-reactive compounds that reintroduce the WT preference for Cl-. At saturating extracellular anion concentrations, neutralization of Lys210 is of little impact on the anion preference, suggesting an important role of Lys210 on the association rate of extracellular anions to Sext.

NaCl-triggered self-assembly of hydrophilic poloxamine block copolymers.

PubMed

Bahadur, Anita; Cabana-Montenegro, Sonia; Aswal, Vinod Kumar; Lage, Emilio V; Sandez-Macho, Isabel; Concheiro, Angel; Alvarez-Lorenzo, Carmen; Bahadur, Pratap

2015-10-15

Tetronic 1307 (T1307) is a hydrophilic poloxamine (HLB>24) with a high molecular mass owing to its long PEO and PPO blocks. In spite of good biocompatibility, its use as a component of drug delivery systems is limited by its high critical micelle concentration (CMC) and temperature (CMT). The aim of this work was to elucidate whether the addition of NaCl or the combination of salts and temperature may bring T1307 micellization and gelling features into more practically useful values. Increasing NaCl concentration in the 0.154 M (isotonic) to 2M (hypertonic) range made the copolymer more hydrophobic and more prone to self-assemble into unimodal micelles, as observed by means of π-A isotherms, (1)H NMR, dynamic light scattering (DLS), small-angle neutron scattering (SANS), and pyrene fluorescence. The decrease in CMC and CMT observed for T1307 in 0.5 M NaCl medium (tolerable hypertonic solution), compared to water, notably favored the solubility of hydrophobic drugs such as curcumin and quercetin. Moreover, phase diagram, intrinsic viscosity and sol-to-gel transition were markedly affected by NaCl concentration. Overall, the strong dependence of T1307 self-assembly features on NaCl opens interesting possibilities for tuning the performance of T1307 as a component of nanocarriers and in situ gelling systems. Copyright © 2015 Elsevier B.V. All rights reserved.

High-pressure X-ray diffraction, Raman, and computational studies of MgCl2 up to 1 Mbar: Extensive pressure stability of the β-MgCl2 layered structure.

PubMed

Stavrou, Elissaios; Yao, Yansun; Zaug, Joseph M; Bastea, Sorin; Kalkan, Bora; Konôpková, Zuzana; Kunz, Martin

2016-08-12

Magnesium chloride (MgCl2) with the rhombohedral layered CdCl2-type structure (α-MgCl2) has been studied experimentally using synchrotron angle-dispersive powder x-ray diffraction and Raman spectroscopy using a diamond-anvil cell up to 100 GPa at room temperature and theoretically using first-principles density functional calculations. The results reveal a pressure-induced second-order structural phase transition to a hexagonal layered CdI2-type structure (β-MgCl2) at 0.7 GPa: the stacking sequence of the Cl anions are altered resulting in a reduction of the c-axis length. Theoretical calculations confirm this phase transition sequence and the calculated transition pressure is in excellent agreement with the experiment. Lattice dynamics calculations also reproduce the experimental Raman spectra measured for the ambient and high-pressure phase. According to our experimental results MgCl2 remains in a 2D layered phase up to 100 GPa and further, the 6-fold coordination of Mg cations is retained. Theoretical calculations of relative enthalpy suggest that this extensive pressure stability is due to a low enthalpy of the layered structure ruling out kinetic barrier effects. This observation is unusual, as it contradicts with the general structural behavior of highly compressed AB2 compounds.

High-pressure X-ray diffraction, Raman, and computational studies of MgCl 2 up to 1 Mbar: Extensive pressure stability of the β-MgCl 2 layered structure

DOE PAGES

Stavrou, Elissaios; Yao, Yansun; Zaug, Joseph M.; ...

2016-08-12

We studied magnesium chloride (MgCl 2) with the rhombohedral layered CdCl 2-type structure (α-MgCl 2), experimentally, using synchrotron angle-dispersive powder x-ray diffraction and Raman spectroscopy using a diamond-anvil cell up to 100 GPa at room temperature and theoretically using first-principles density functional calculations. Our results reveal a pressure-induced second-order structural phase transition to a hexagonal layered CdI 2-type structure (β-MgCl 2) at 0.7 GPa: the stacking sequence of the Cl anions are altered resulting in a reduction of the c-axis length. Theoretical calculations confirm this phase transition sequence and the calculated transition pressure is in excellent agreement with the experiment.more » Lattice dynamics calculations also reproduce the experimental Raman spectra measured for the ambient and high-pressure phase. According to our experimental results MgCl 2 remains in a 2D layered phase up to 100 GPa and further, the 6-fold coordination of Mg cations is retained. Theoretical calculations of relative enthalpy suggest that this extensive pressure stability is due to a low enthalpy of the layered structure ruling out kinetic barrier effects. Our observation is unusual, as it contradicts with the general structural behavior of highly compressed AB 2 compounds.« less

Bonding in d9 complexes derived from EPR: Application to CuCl2-4, CuBr2-4, and CdCl2:Cu2+

NASA Astrophysics Data System (ADS)

Aramburu, J. A.; Moreno, M.

1985-12-01

In this work are reported the theoretical expressions for the [g], hyperfine, and superhyperfine (shf) tensors of a d9 square-planar complex within a molecular orbital (MO) scheme. These expressions include contributions arising from crystal field and charge transfer excitations calculated up to third and second order perturbations, respectively. This makes the present framework more general than those previously used. Through those expressions we have derived from the experimental EPR and optical data the MO coefficients corresponding to the valence b1g(x2-y2), b2g(xy), and eg(xz,yz) levels and also the core polarization contribution K to the hyperfine tensor for the systems CuCl2-4, CuBr2-4, and CdCl2:Cu2+. The 3d charge obtained for CuCl2-4 is equal to 0.61, 0.83, and 0.85 for the antibonding 3b1g, 2b2g, and 2eg levels, respectively. These figures are much closer to the Xα results by Bencini and Gatteschi [J. Am. Chem. Soc. 105, 5535 (1983)] than to those by Desjardins et al. [J. Am. Chem. Soc. 105, 4590 (1983)]. The σ and π covalency for CuBr2-4 are both higher than for CuCl2-4 in accord to the lower electronegativity for bromine. However, only for the antibonding 3b1g level of CuBr2-4 have we obtained an electronic charge lying mainly on ligands. The covalency of CdCl2:Cu2+ is smaller than that found for CuCl2-4, a fact associated to a higher metal-ligand distance for the former. Evidence of this statement are also given from the analysis of crystal-field spectra and isotropic shf constant. The values of K derived for CuCl2-4 (128.1×10-4 cm-1), CuBr2-4 (103.6×10-4 cm-1), and CdCl2:Cu2+ (123.9×10-4 cm-1) point out the dependence of K on the equatorial covalency but also on the existence of axial ligands. The [g] tensor of CuBr2-4 is dominated by the charge transfer contribution while the crystal field one is negative. Finally an analysis of the importance of each one of the involved contributions to the spin-Hamiltonian parameters is reported for the

Aqueous solubility and alkaline hydrolysis of the novel high explosive hexanitrohexaazaisowurtzitane (CL-20).

PubMed

Karakaya, Pelin; Sidhoum, Mohammed; Christodoulatos, Christos; Nicolich, Steve; Balas, Wendy

2005-04-11

The recently developed polycyclic nitramine CL-20 is considered as a possible replacement for the monocyclic nitramines RDX and HMX. The present study reports aqueous solubility data for CL-20, as well as the kinetic parameters for its alkaline hydrolysis with sodium hydroxide below and above its solubility limits. Aqueous solubility of CL-20 was measured in the temperature range of 4-69 degrees C and the data were fitted to a generalized solubility model. Alkaline hydrolysis experiments were conducted at 15, 20, 30 and 40 degrees C, with hydroxide concentrations ranging from 0.25 to 300 mM. Like RDX and HMX, alkaline hydrolysis of CL-20 follows second-order kinetics. CL-20 alkaline hydrolysis was found to proceed at a significantly faster rate than RDX. The temperature dependency of the second-order rate constants was evaluated using the Arrhenius model. The activation energy for CL-20 was found to be within close range of the activation energies reported for RDX and HMX.

Dynamics of water in LiCl and CaCl 2 aqueous solutions confined in silica matrices: A backscattering neutron spectroscopy study

NASA Astrophysics Data System (ADS)

Mamontov, E.; Cole, D. R.; Dai, S.; Pawel, M. D.; Liang, C. D.; Jenkins, T.; Gasparovic, G.; Kintzel, E.

2008-09-01

Backscattering neutron spectroscopy was used to probe the dynamics of water molecules in LiCl and CaCl 2 aqueous solutions confined in 2.7, 1.9, and 1.4 nm diameter pores of various silica matrices. The pore size of 2.7 nm was found to be sufficiently large for the confined liquids to exhibit characteristic traits of bulk behavior, such as a freezing-melting transition and a phase separation. On the other hand, none of the fluids in the 1.4 nm pores exhibited a clear freezing-melting transition; instead, their dynamics at low temperatures gradually became too slow for the nanosecond resolution of the experiment. The greatest suppression of water mobility was observed in the CaCl 2 solutions, which suggests that cation charge and perhaps the cation hydration environment have a profound influence on the dynamics of the water molecules. Quasielastic neutron scattering measurements of pure H 2O and 1 m LiCl-H 2O solution confined in 1.9 nm pores revealed a dynamic transition in both liquids at practically the same temperature of 225-226 K, even though the dynamics of the solution at room temperature appeared to slow down by more than an order of magnitude compared to the pure water. The observation of the dynamic transition in the solution suggests that this transition may be a universal feature of water governed by processes acting on the local scale, such as a change in the hydrogen bonding.

AgCl precipitates in isolated cuticular membranes reduce rates of cuticular transpiration.

PubMed

Schreiber, Lukas; Elshatshat, Salem; Koch, Kerstin; Lin, Jinxing; Santrucek, Jiri

2006-01-01

Counter diffusion of chloride, applied as NaCl at the inner side of isolated cuticles, and silver, applied as AgNO(3) at the outer side, lead to the formation of insoluble AgCl precipitates in isolated cuticles. AgCl precipitates could be visualized by light and scanning electron microscopy. The presence of AgCl precipitates in isolated cuticles was verified by energy dispersive X-ray analysis. It is argued that insoluble AgCl precipitates formed in polar pores of cuticles and as a consequence, cuticular transpiration of 13 out of 15 investigated species was significantly reduced up to three-fold. Water as a small and uncharged but polar molecule penetrates cuticles via two parallel paths: a lipophilic path, formed by lipophilic cutin and wax domains, and a aqueous pathe, formed by polar pores. Thus, permeances P (m s(-1)) of water, which is composed of the two quantities P (Lipid) and P (Pore), decreased, since water transport across polar pores was affected by AgCl precipitates. Cuticles with initially high rates of cuticular transpiration were generally more sensitive towards AgCl precipitates compared to cuticles with initially low rates of transpiration. Results presented here, significantly improves the current model of the structure of the cuticular transpiration barrier, since the pronounced heterogeneity of the cuticular transport barrier, composed of lipophilic as well as polar paths of diffusion, has to be taken into account in future.

Nitrogen doped microporous carbon by ZnCl2 activation of protein

NASA Astrophysics Data System (ADS)

Wilson, Praveen; Vijayan, Sujith; Prabhakaran, K.

2017-09-01

ZnCl2 activation of protein containing biomass has been studied for the preparation of N-doped activated carbon (NDC) using powdered dry fish as a source of protein. Nearly 52% increase in the yield of NDC is observed by activation with ZnCl2 due to an increase in the thermal stability of Zn2+-fish protein complex compared to the protein alone. The NDCs obtained are characterized by XRD, IR, XPS, Raman spectroscopy, SEM, TEM, elemental analysis and N2 adsorption-desorption studies. The activation at 550 °C produces NDC with the highest surface area and total pore volume of 1001 m2 g-1 and 0.719 cm3 g-1, respectively, at a ZnCl2 to fish powder weight ratio of 3. A maximum micropore volume of 0.273 cm3 g-1 is obtained at a ZnCl2 to fish powder weight ratio of 1:1. The N-content (12.4-5.2 wt%) decreases with an increase in activation temperature and ZnCl2 to fish powder weight ratio. The NDC obtained by activation at 550 °C at a ZnCl2 to fish powder weight ratio of 1:1 shows the maximum CO2 adsorption capacity of 2.4 and 3.73 mmol g-1 at 25 and 0 °C, respectively, at 1 atmosphere. The CO2 adsorption on the NDC shows excellent cyclic stability and high selectivity over nitrogen gas.

Preparation of Ferrotitanium from Ilmenite by Electrolysis-Assisted Calciothermic Reduction in CaCl2-NaCl Molten Salt

NASA Astrophysics Data System (ADS)

Zhou, Zhongren; Hua, Yixin; Xu, Cunying; Li, Jian; Li, Yan; Gong, Kai; Ru, Juanjian; Xiong, Li

2016-02-01

Electrolysis-assisted calciothermic reduction method is proposed and successfully used to prepare ferrotitanium alloy from ilmenite by using equal-molar CaCl2-NaCl molten salt as electrolyte, molybdenum rod as cathode, and graphite as anode at 973 K with cell voltages of 3.2-4.4 V under inert atmosphere. Thermodynamics analysis of the process is presented, and the products obtained are examined with x-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy. It is demonstrated that the calciothermic reduction of ilmenite is a stepwise process since intermediate CaTiO3 is observed in the products partially reduced. In the calciothermic reduction process, the reduction of FeTiO3 first gives rise to the formation of Fe and CaTiO3, which as intermediates will further react with calcium metal to form ferrotitanium alloys. This is in good agreement with the prediction of thermodynamics. Experimental results also show that increasing cell voltage can accelerate the formation of calcium metal through electrolysis of CaO and CaCl2 and, hence, promote the calciothermic reduction of ilmenite. As the electrolytic zone and reduction zone are combined in the same bath, the theoretical energy requirement for the production of FeTi in the calciothermic process is lower than that in the aluminothermic process.

Crystallization of D-mannitol in binary mixtures with NaCl: phase diagram and polymorphism.

PubMed

Telang, Chitra; Suryanarayanan, Raj; Yu, Lian

2003-12-01

To study the crystallization, polymorphism, and phase behavior of D-mannitol in binary mixtures with NaCl to better understand their interactions in frozen aqueous solutions. Differential scanning calorimetry, hot-stage microscopy, Raman microscopy, and variable-temperature X-ray diffractometry were used to characterize D-mannitol-NaCl mixtures. NaCl and D-mannitol exhibited significant melt miscibility (up to 7.5% w/w or 0.20 mole fraction of NaCl) and a eutectic phase diagram (eutectic composition 7.5% w/w NaCl; eutectic temperature 150 degrees C for the alpha and beta polymorphs of D-mannitol and 139 degrees C for the delta). The presence of NaCl did not prevent mannitol from crystallizing but, depending on sample size, affected the polymorph crystallized: below 10 mg, delta was obtained; above 100 mg, alpha was obtained. Pure mannitol crystallized under the same conditions first as the delta polymorph and then as the a polymorph, with the latter nucleating on the former. KCl showed similar eutectic points and melt miscibility with D-mannitol as NaCl. LiCl yielded lower eutectic melting points, inhibited the crystallization of D-mannitol during cooling, and enabled the observation of its glass transition. Despite their structural dissimilarity, significant melt miscibility exists between D-mannitol and NaCl. Their phase diagram has been determined and features polymorph-dependent eutectic points. NaCl influences the polymorphic behavior of mannitol, and the effect is linked to the crystallization of mannitol in two polymorphic stages.

Science and Innovation at Los Alamos

Science.gov Websites

Los Alamos National Laboratory Search Site submit About Mission Business Newsroom Publications Los Innovation in New Mexico Los Alamos Collaboration for Explosives Detection (LACED) SensorNexus Exascale Computing Project (ECP) User Facilities Center for Integrated Nanotechnologies (CINT) Los Alamos Neutron

Laser generation of XeCl exciplex molecules in a longitudinal repetitively pulsed discharge in a Xe - CsCl mixture

NASA Astrophysics Data System (ADS)

Boichenko, A. M.; Klenovskii, M. S.

2015-12-01

By using the previously developed kinetic model, we have carried out simulations to study the possibility of laser generation of XeCl exciplex molecules in the working medium based on a mixture of Xe with CsCl vapours, excited by a longitudinal repetitively pulsed discharge. The formation mechanism of exciplex molecules in this mixture is fundamentally different from the formation mechanisms in the traditional mixtures of exciplex lasers. The conditions that make the laser generation possible are discussed. For these conditions, with allowance for available specific experimental conditions of the repetitively pulsed discharge excitation, we have obtained the calculated dependences of the power and efficiency of generation on the reflectivity of mirrors in a laser cavity.

Sorption and stability of the polycyclic nitramine explosive CL-20 in soil.

PubMed

Balakrishnan, Vimal K; Monteil-Rivera, Fanny; Gautier, Mathieu A; Hawari, Jalal

2004-01-01

The polycyclic nitramine CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) is being considered for use as a munition, but its environmental fate and impact are unknown. The present study consisted of two main elements. First, sorption-desorption data were measured with soils and minerals to evaluate the respective contributions of organic matter and minerals to CL-20 immobilization. Second, since CL-20 hydrolyzes at a pH of >7, the effect of sorption on CL-20 degradation was examined in alkaline soils. Sorption-desorption isotherms measured using five slightly acidic soils (5.1 < pH < 6.9) containing various amounts of total organic carbon (TOC) revealed a nonlinear sorption that increased with TOC [K(d) (0.33% TOC) = 2.4 L kg(-1); K(d) (20% TOC) = 311 L kg(-1)]. Sorption to minerals (Fe(2)O(3), silica, kaolinite, montmorillonite, illite) was very low (0 < K(d) < 0.6 L kg(-1)), suggesting that mineral phases do not contribute significantly to CL-20 sorption. Degradation of CL-20 in sterile soils having different pH values increased as follows: sandy agricultural topsoil from Varennes, QC, Canada (VT) (pH = 5.6; K(d) = 15 L kg(-1); 8% loss) < clay soil from St. Sulpice, QC, Canada (CSS) (pH = 8.1; K(d) = 1 L kg(-1); 82% loss) < sandy soil provided by Agriculture Canada (SAC) (pH = 8.1, K(d) = approximately 0 L kg(-1); 100% loss). The faster degradation in SAC soil compared with CSS soil was attributed to the absence of sorption in the former. In summary, CL-20 is highly immobilized by soils rich in organic matter. Although sorption retards abiotic degradation, CL-20 still decomposes in soils where pH is >7.5, suggesting that it will not persist in even slightly alkaline soils.

Temperature dependence of thermal pressure for NaCl

NASA Astrophysics Data System (ADS)

Singh, Chandra K.; Pande, Brijesh K.; Pandey, Anjani K.

2018-05-01

Engineering applications of the materials can be explored upto the desired limit of accuracy with the better knowledge of its mechanical and thermal properties such as ductility, brittleness and Thermal Pressure. For the resistance to fracture (K) and plastic deformation (G) the ratio K/G is treated as an indication of ductile or brittle character of solids. In the present work we have tested the condition of ductility and brittleness with the calculated values of K/G for the NaCl. It is concluded that the nature of NaCl can be predicted upto high temperature simply with the knowledge of its elastic stiffness constant only. Thermoelastic properties of materials at high temperature is directly related to thermal pressure and volume expansion of the materials. An expression for the temperature dependence of thermal pressure is formulated using basic thermodynamic identities. It is observed that thermal pressure ΔPth calculated for NaCl by using Kushwah formulation is in good agreement with the experimental values also the thermal pressure increases with the increase in temperature.

A Sensor Based on LiCl/NaA Zeolite Composites for Effective Humidity Sensing.

PubMed

Zhang, Ying; Xiang, Hongyu; Sun, Liang; Xie, Qiuhong; Liu, Man; Chen, Yu; Ruan, Shengping

2018-03-01

LiCl/NaA zeolite composites were successfully prepared by doping 1 wt%, 2 wt%, 5 wt%, and 8 wt% of LiCl into NaA zeolite. The humidity sensing properties of LiCl/NaA composites were investigated among 11% 95% relative humidity (RH). The LiCl/NaA composites exhibited better humidity sensing properties than pure NaA zeolite. The sensor made by 2 wt% Li-doped NaA zeolite possesses the best linearly in the whole RH. These results demonstrate that the LiCl/NaA composites have the potential application in humidity sensing.

The study for the incipient solvation process of NaCl in water: the observation of the NaCl-(H2O)n (n = 1, 2, and 3) complexes using Fourier-transform microwave spectroscopy.

PubMed

Mizoguchi, Asao; Ohshima, Yasuhiro; Endo, Yasuki

2011-08-14

Pure rotational spectra of the sodium chloride-water complexes, NaCl-(H(2)O)(n) (n = 1, 2, and 3), in the vibronic ground state have been observed by a Fourier- transform microwave spectrometer coupled with a laser ablation source. The (37)Cl-isotopic species and a few deuterated species have also been observed. From the analyses of the spectra, the rotational constants, the centrifugal distortion constants, and the nuclear quadrupole coupling constants of the Na and Cl nuclei were determined precisely for all the species. The molecular structures of NaCl-(H(2)O)(n) were determined using the rotational constants and the molecular symmetry. The charge distributions around Na and Cl nuclei in NaCl are dramatically changed by the complex formation with H(2)O. Prominent dependences of the bond lengths r(Na-Cl) on the number of H(2)O were also observed. By a comparison with results of theoretical studies, it is shown that the structure of NaCl-(H(2)O)(3) is approaching to that of the contact ion-pair, which is considered to be an intermediate species in the incipient solvation process.

Los cambios en la velocidad de rotación terrestre y los fenómenos geomagnéticos

NASA Astrophysics Data System (ADS)

Gianibelli, J. C.

Uno de los aspectos importantes relativos a la geodinámica del interior terrestre es la correlación entre los eventos de cambio en la velocidad de rotación terrestre y los determinados en los elementos del campo geomagnético por ejemplo, la Declinación Magnética, o los coeficientes de los modelos matemáticos de representación global de dicho campo. En este trabajo se presentan los resultados de las características espectrales de los cambios observados en la longitud del día (ldd), y su relación con la estructura espectral de las coeficientes de los modelos matemáticos de campo denominados Campo Internacional Geomagnético de Referencia (CIGR). El intervalo estudiado comprende los últimos 100 años. Los resultados muestran una correlación en las bandas de 60 y 30 años, con posibles períodos mucho mayores que no son posibles determinar a partir de los modelos de CIRG. Se efectúa una simulación a partir de los resultados obtenidos por la aplicación del método de máxima entropía con longitudes del filtro predictor de error comprendida entre el 10% y el 95% de la longitud de la serie analizada. Se observan procesos sicrónicos y asincrónicos que, en muy largos intervalos de tiempos, podrían suponerse como caóticos.

Dielectric evidence for possible type-II multiferroicity in α-RuCl3

NASA Astrophysics Data System (ADS)

Zheng, JiaCheng; Cui, Yi; Li, TianRun; Ran, KeJing; Wen, JinSheng; Yu, WeiQiang

2018-05-01

$\\alpha$-RuCl$_3$ is a Mott insulator with a honeycomb lattice with strong spin-orbit coupling. We report dielectric measurements on $\\alpha$-RuCl$_3$ single crystals under field. At zero field, the dielectric constant, $\\epsilon$, drops rapidly when cooled through the magnetic transition temperature T$_N$. With increasing field, the onset of the drop in $\\epsilon$ tracks the T$_N$. Such behavior is absent with field above a critical value H$_c$ ~ 7.5 T, indicating the onset of a quantum phase transition. Our data suggest that the dielectric constant can be used as a probe of magnetic ordering in $\\alpha$-RuCl$_3$, and $\\alpha$-RuCl$_3$ is a possible type-II multiferroics.

Highly Productive Application Development with ViennaCL for Accelerators

NASA Astrophysics Data System (ADS)

Rupp, K.; Weinbub, J.; Rudolf, F.

2012-12-01

The use of graphics processing units (GPUs) for the acceleration of general purpose computations has become very attractive over the last years, and accelerators based on many integrated CPU cores are about to hit the market. However, there are discussions about the benefit of GPU computing when comparing the reduction of execution times with the increased development effort [1]. To counter these concerns, our open-source linear algebra library ViennaCL [2,3] uses modern programming techniques such as generic programming in order to provide a convenient access layer for accelerator and GPU computing. Other GPU-accelerated libraries are primarily tuned for performance, but less tailored to productivity and portability: MAGMA [4] provides dense linear algebra operations via a LAPACK-comparable interface, but no dedicated matrix and vector types. Cusp [5] is closest in functionality to ViennaCL for sparse matrices, but is based on CUDA and thus restricted to devices from NVIDIA. However, no convenience layer for dense linear algebra is provided with Cusp. ViennaCL is written in C++ and uses OpenCL to access the resources of accelerators, GPUs and multi-core CPUs in a unified way. On the one hand, the library provides iterative solvers from the family of Krylov methods, including various preconditioners, for the solution of linear systems typically obtained from the discretization of partial differential equations. On the other hand, dense linear algebra operations are supported, including algorithms such as QR factorization and singular value decomposition. The user application interface of ViennaCL is compatible to uBLAS [6], which is part of the peer-reviewed Boost C++ libraries [7]. This allows to port existing applications based on uBLAS with a minimum of effort to ViennaCL. Conversely, the interface compatibility allows to use the iterative solvers from ViennaCL with uBLAS types directly, thus enabling code reuse beyond CPU-GPU boundaries. Out-of-the-box support

Aluminium(III) amidinates formed from reactions of `AlCl' with lithium amidinates.

PubMed

Mayo, Dennis H; Peng, Yang; Zavalij, Peter; Bowen, Kit H; Eichhorn, Bryan W

2013-10-01

The disproportionation of AlCl(THF)n (THF is tetrahydrofuran) in the presence of lithium amidinate species gives aluminium(III) amidinate complexes with partial or full chloride substitution. Three aluminium amidinate complexes formed during the reaction between aluminium monochloride and lithium amidinates are presented. The homoleptic complex tris(N,N'-diisopropylbenzimidamido)aluminium(III), [Al(C13H19N2)3] or Al{PhC[N(i-Pr)]2}3, (I), crystallizes from the same solution as the heteroleptic complex chloridobis(N,N'-diisopropylbenzimidamido)aluminium(III), [Al(C13H19N2)2Cl] or Al{PhC[N(i-Pr)]2}2Cl, (II). Both have two crystallographically independent molecules per asymmetric unit (Z' = 2) and (I) shows disorder in four of its N(i-Pr) groups. Changing the ligand substituent to the bulkier cyclohexyl allows the isolation of the partial THF solvate chloridobis(N,N'-dicyclohexylbenzimidamido)aluminium(III) tetrahydrofuran 0.675-solvate, [Al(C19H27N2)2Cl]·0.675C4H8O or Al[PhC(NCy)2]2Cl·0.675THF, (III). Despite having a twofold rotation axis running through its Al and Cl atoms, (III) has a similar molecular structure to that of (II).

Immobilization of Alkali Metal Fluorides via Recrystallization in a Cationic Lamellar Material, [Th(MoO4)(H2O)4Cl]Cl·H2O.

PubMed

Lin, Jian; Bao, Hongliang; Qie, Meiying; Silver, Mark A; Yue, Zenghui; Li, Xiaoyun; Zhu, Lin; Wang, Xiaomei; Zhang, Linjuan; Wang, Jian-Qiang

2018-06-05

Searching for cationic extended materials with a capacity for anion exchange resulted in a unique thorium molybdate chloride (TMC) with the formula of [Th(MoO 4 )(H 2 O) 4 Cl]Cl·H 2 O. The structure of TMC is composed of zigzagging cationic layers [Th(MoO 4 )(H 2 O) 4 Cl] + with Cl - as interlamellar charge-balancing anions. Instead of performing ion exchange, alkali thorium fluorides were formed after soaking TMC in AF (A = Na, K, and Cs) solutions. The mechanism of AF immobilization is elucidated by the combination of SEM-EDS, PXRD, FTIR, and EXAFS spectroscopy. It was observed that four water molecules coordinating with the Th 4+ center in TMC are vulnerable to competition with F - , due to the formation of more favorable Th-F bonds compared to Th-OH 2 . This leads to a single crystal-to-polycrystalline transformation via a pathway of recrystallization to form alkali thorium fluorides.

80 A/cm2 electron beams from metal targets irradiated by KrCl and XeCl excimer lasers

NASA Astrophysics Data System (ADS)

Beloglazov, A.; Martino, M.; Nassisi, V.

1996-05-01

Due to the growing demand for high-current and long-duration electron-beam devices, laser electron sources were investigated in our laboratory. Experiments on electron-beam generation and propagation from aluminium and copper targets illuminated by XeCl (308 nm) and KrCl (222 nm) excimer lasers, were carried out under plasma ignition due to laser irradiation. This plasma supplied a spontaneous accelerating electric field of about 370 kV/m without an external accelerating voltage. By applying the modified one-dimensional Poisson equation, we computed the expected current and we also estimated the plasma concentration during the accelerating process. At 40 kV of accelerating voltage, an output current pulse of about 80 A/cm2 was detected from an Al target irradiated by the shorter wavelength laser.

Charging Properties of Cassiterite (alpha-SnO2) Surfaces in NaCl and RbCl Ionic Media.

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

Rosenqvist, Jorgen K; Machesky, Michael L.; Vlcek, Lukas

2009-01-01

The acid-base properties of cassiterite ({alpha}-SnO{sub 2}) surfaces at 10-50 C were studied using potentiometric titrations of powder suspensions in aqueous NaCl and RbCl media. The proton sorption isotherms exhibited common intersection points in the pH range of 4.0-4.5 under all conditions, and the magnitude of charging was similar but not identical in NaCl and RbCl. The hydrogen bonding configuration at the oxide-water interface, obtained from classical molecular dynamics (MD) simulations, was analyzed in detail, and the results were explicitly incorporated in calculations of protonation constants for the reactive surface sites using the revised MUSIC model. The calculations indicated thatmore » the terminal SnOH{sub 2} group is more acidic than the bridging Sn{sub 2}OH group, with protonation constants (log K{sub H}) of 3.60 and 5.13 at 25 C, respectively. This is contrary to the situation on the isostructural {alpha}-TiO{sub 2} (rutile), apparently because of the difference in electronegativity between Ti and Sn. MD simulations and speciation calculations indicated considerable differences in the speciation of Na{sup +} and Rb{sup +}, despite the similarities in overall charging. Adsorbed sodium ions are almost exclusively found in bidentate surface complexes, whereas adsorbed rubidium ions form comparable numbers of bidentate and tetradentate complexes. Also, the distribution of adsorbed Na{sup +} between the different complexes shows a considerable dependence on the surface charge density (pH), whereas the distribution of adsorbed Rb{sup +} is almost independent of pH. A surface complexation model (SCM) capable of accurately describing both the measured surface charge and the MD-predicted speciation of adsorbed Na{sup +}/Rb{sup +} was formulated. According to the SCM, the deprotonated terminal group (SnOH{sup -0.40}) and the protonated bridging group (Sn{sub 2}OH{sup +0.36}) dominate the surface speciation over the entire pH range of this study (2

Charging Properties of Cassiterite (alpha-SnO2) surfaces in NaCl and RbCl Ionic Media.

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

Rosenqvist, Jorgen K; Machesky, Michael L.; Vlcek, Lukas

2009-01-01

The acid-base properties of cassiterite (alpha-SnO2) surfaces at 10-50 degrees C were studied using potentiometric titrations of powder suspensions in aqueous NaCl and RbCl media. The proton sorption isotherms exhibited common intersection points in the pH range of 4.0-4.5 under all conditions, and the magnitude of charging was similar but not identical in NaCl and RbCl. The hydrogen bonding configuration at the oxide-water interface, obtained from classical molecular dynamics (MD) simulations, was analyzed in detail, and the results were explicitly incorporated in calculations of protonation constants for the reactive surface sites using the revised MUSIC model. The calculations indicated thatmore » the terminal SnOH2 group is more acidic than the bridging Sn2OH group, with protonation constants (log KH) of 3.60 and 5.13 at 25 degrees C, respectively. This is contrary to the situation on the isostructural alpha-TiO2 (rutile), apparently because of the difference in electronegativity between Ti and Sn. MD simulations and speciation calculations indicated considerable differences in the speciation of Na+ and Rb+, despite the similarities in overall charging. Adsorbed sodium ions are almost exclusively found in bidentate surface complexes, whereas adsorbed rubidium ions form comparable numbers of bidentate and tetradentate complexes. Also, the distribution of adsorbed Na+ between the different complexes shows a considerable dependence on the surface charge density (pH), whereas the distribution of adsorbed Rb+ is almost independent of pH. A surface complexation model (SCM) capable of accurately describing both the measured surface charge and the MD-predicted speciation of adsorbed Na+/Rb+ was formulated. According to the SCM, the deprotonated terminal group (SnOH(-0.40)) and the protonated bridging group (Sn2OH+0.36) dominate the surface speciation over the entire pH range of this study (2.7-10). The complexation of medium cations increases significantly with

First-principles study of roles of Cu and Cl in polycrystalline CdTe

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

Yang, Ji -Hui; Yin, Wan -Jian; Park, Ji -Sang

2016-01-25

In this study, Cu and Cl treatments are important processes to achieve high efficiency polycrystalline cadmium telluride (CdTe) solar cells, thus it will be beneficial to understand the roles they play in both bulk CdTe and CdTe grain boundaries (GBs). Using first-principles calculations, we systematically study Cu and Cl-related defects in bulk CdTe. We find that Cl has only a limited effect on improving p-type doping and too much Cl can induce deep traps in bulk CdTe, whereas Cu can enhance ptype doping of bulk CdTe. In the presence of GBs, we find that, in general, Cl and Cu willmore » prefer to stay at GBs, especially for those with Te-Te wrong bonds, in agreement with experimental observations.« less

First-principles study of roles of Cu and Cl in polycrystalline CdTe

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

Yang, Ji-Hui; Park, Ji-Sang; Metzger, Wyatt

2016-01-28

Cu and Cl treatments are important processes to achieve high efficiency polycrystalline cadmium telluride (CdTe) solar cells, thus it will be beneficial to understand the roles they play in both bulk CdTe and CdTe grain boundaries (GBs). Using first-principles calculations, we systematically study Cu and Cl-related defects in bulk CdTe. We find that Cl has only a limited effect on improving p-type doping and too much Cl can induce deep traps in bulk CdTe, whereas Cu can enhance p-type doping of bulk CdTe. In the presence of GBs, we find that, in general, Cl and Cu will prefer to staymore » at GBs, especially for those with Te-Te wrong bonds, in agreement with experimental observations.« less

Hole doping and structural transformation in CsTl1-xHgxCl3.

PubMed

Retuerto, Maria; Yin, Zhiping; Emge, Thomas J; Stephens, Peter W; Li, Man-Rong; Sarkar, Tapati; Croft, Mark C; Ignatov, Alexander; Yuan, Z; Zhang, S J; Jin, Changqing; Paria Sena, Robert; Hadermann, Joke; Kotliar, Gabriel; Greenblatt, Martha

2015-02-02

CsTlCl(3) and CsTlF(3) perovskites have been theoretically predicted to be superconductors when properly hole-doped. Both compounds have been previously prepared as pure compounds: CsTlCl(3) in a tetragonal (I4/m) and a cubic (Fm3̅m) perovskite polymorph and CsTlF(3) as a cubic perovskite (Fm3̅m). In this work, substitution of Tl in CsTlCl(3) with Hg is reported, in an attempt to hole-dope the system and induce superconductivity. The whole series CsTl(1-x)HgxCl(3) (x = 0.0, 0.1, 0.2, 0.4, 0.6, and 0.8) was prepared. CsTl(0.9)Hg(0.1)Cl(3) is tetragonal as the more stable phase of CsTlCl(3). However, CsTl(0.8)Hg(0.2)Cl(3) is already cubic with the space group Fm3̅m and with two different positions for Tl(+) and Tl(3+). For x = 0.4 and 0.5, solid solutions could not be formed. For x ≥ 0.6, the samples are primitive cubic perovskites with one crystallographic position for Tl(+), Tl(3+), and Hg(2+). All of the samples formed are insulating, and there is no signature of superconductivity. X-ray absorption spectroscopy indicates that all of the samples have a mixed-valence state of Tl(+) and Tl(3+). Raman spectroscopy shows the presence of the active Tl-Cl-Tl stretching mode over the whole series and the intensity of the Tl-Cl-Hg mode increases with increasing Hg content. First-principle calculations confirmed that the phases are insulators in their ground state and that Hg is not a good dopant in the search for superconductivity in this system.

N-ethylmaleimide activates a Cl(-)-independent component of K(+) flux in mouse erythrocytes.

PubMed

Shmukler, Boris E; Hsu, Ann; Alves, Jessica; Trudel, Marie; Rust, Marco B; Hubner, Christian A; Rivera, Alicia; Alper, Seth L

2013-06-01

The K-Cl cotransporters (KCCs) of mouse erythrocytes exhibit higher basal activity than those of human erythrocytes, but are similarly activated by cell swelling, by hypertonic urea, and by staurosporine. However, the dramatic stimulation of human erythroid KCCs by N-ethylmaleimide (NEM) is obscured in mouse erythrocytes by a prominent NEM-stimulated K(+) efflux that lacks Cl(-)-dependence. The NEM-sensitivity of Cl(-)-independent K(+) efflux of mouse erythrocytes is lower than that of KCC. The genetically engineered absence of the K-Cl cotransporters KCC3 and KCC1 from mouse erythrocytes does not modify Cl(-)-independent K(+) efflux. Mouse erythrocytes genetically devoid of the Gardos channel KCNN4 show increased NEM-sensitivity of both Cl(-)-independent K(+) efflux and K-Cl cotransport. The increased NEM-sensitivity and stimulation magnitude of Cl(-)-independent K(+) efflux in mouse erythrocytes expressing transgenic hypersickling human hemoglobin SAD (HbSAD) are independent of the presence of KCC3 and KCC1, but absence of KCNN4 reduces the stimulatory effect of HbSAD. NEM-stimulated Cl(-)-independent K(+) efflux of mouse red cells is insensitive to ouabain and bumetanide, but partially inhibited by chloroquine, barium, and amiloride. The NEM-stimulated activity is modestly reduced at pH6.0 but not significantly altered at pH8.0, and is abolished at 0°C. Although the molecular identity of this little-studied K(+) efflux pathway of mouse erythrocytes remains unknown, its potential role in the pathophysiology of sickle red cell dehydration will be important for the extrapolation of studies in mouse models of sickle cell disease to our understanding of humans with sickle cell anemia. Copyright © 2013 Elsevier Inc. All rights reserved.

Signal transduction mechanisms of K+-Cl- cotransport regulation and relationship to disease.

PubMed

Adragna, N C; Ferrell, C M; Zhang, J; Di Fulvio, M; Temprana, C F; Sharma, A; Fyffe, R E W; Cool, D R; Lauf, P K

2006-01-01

The K+-Cl- cotransport (COT) regulatory pathways recently uncovered in our laboratory and their implication in disease state are reviewed. Three mechanisms of K+-Cl- COT regulation can be identified in vascular cells: (1) the Li+-sensitive pathway, (2) the platelet-derived growth factor (PDGF)-sensitive pathway and (3) the nitric oxide (NO)-dependent pathway. Ion fluxes, Western blotting, semi-quantitative RT-PCR, immunofluorescence and confocal microscopy were used. Li+, used in the treatment of manic depression, stimulates volume-sensitive K+-Cl- COT of low K+ sheep red blood cells at cellular concentrations <1 mM and inhibits at >3 mM, causes cell swelling, and appears to regulate K+-Cl- COT through a protein kinase C-dependent pathway. PDGF, a potent serum mitogen for vascular smooth muscle cells (VSMCs), regulates membrane transport and is involved in atherosclerosis. PDGF stimulates VSM K+-Cl- COT in a time- and concentration-dependent manner, both acutely and chronically, through the PDGF receptor. The acute effect occurs at the post-translational level whereas the chronic effect may involve regulation through gene expression. Regulation by PDGF involves the signalling molecules phosphoinositides 3-kinase and protein phosphatase-1. Finally, the NO/cGMP/protein kinase G pathway, involved in vasodilation and hence cardiovascular disease, regulates K+-Cl- COT in VSMCs at the mRNA expression and transport levels. A complex and diverse array of mechanisms and effectors regulate K+-Cl- COT and thus cell volume homeostasis, setting the stage for abnormalities at the genetic and/or regulatory level thus effecting or being affected by various pathological conditions.

Stockpile Stewardship: Los Alamos

ScienceCinema

McMillan, Charlie; Morgan, Nathanial; Goorley, Tom; Merrill, Frank; Funk, Dave; Korzekwa, Deniece; Laintz, Ken

2018-01-16

"Heritage of Science" is a short video that highlights the Stockpile Stewardship program at Los Alamos National Laboratory. Stockpile Stewardship was conceived in the early 1990s as a national science-based program that could assure the safety, security, and effectiveness of the U.S. nuclear deterrent without the need for full-scale underground nuclear testing. This video was produced by Los Alamos National Laboratory for screening at the Lab's Bradbury Science Museum in Los Alamos, NM and is narrated by science correspondent Miles O'Brien.

Long Life Na/NiCl2 Cells

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar V. (Inventor); Surampudi, Subbarao (Inventor); Halpert, Gerald (Inventor)

1996-01-01

The premature capacity failure of Na/NiCl2 secondary cells due to agglomeration of nickel particles on the surface of the NiCl2 cathode is prevented by addition of a minor amount such as 10 percent by weight of a transition metal such as Co, Fe or Mn to the cathode. The chlorides of the transition metals have lower potentials than nickel chloride and chlorinate during charge. A uniform dispersion of the transition metals in the cathodes prevents agglomeration of nickel, maintains morphology of the electrode, maintains the electrochemical area of the electrode and thus maintains capacity of the electrode. The additives do not effect sintering. The addition of sulfur to the liquid catholyte is expected to further reduce agglomeration of nickel in the cathode.

Crystal structure, vibrational spectra, optical and DFT studies of bis (3-azaniumylpropyl) azanium pentachloroantimonate (III) chloride monohydrate (C6H20N3)SbCl5·Cl·H2O.

PubMed

Ahmed, Houssem Eddine; Kamoun, Slaheddine

2017-09-05

The crystal structure of (C 6 H 20 N 3 )SbCl 5 ·Cl·H 2 O is built up of [NH 3 (CH 2 ) 3 NH 2 (CH 2 ) 3 NH 3 ] 3+ cations, [SbCl 5 ] 2- anions, free Cl - anions and neutral water molecules connected together by NH⋯Cl, NH⋯O and OH⋯Cl hydrogen bonds. The optical band gap determined by diffuse reflection spectroscopy (DRS) is 3.78eV for a direct allowed transition. Optimized molecular geometry, atomic Mulliken charges, harmonic vibrational frequencies, HOMO-LUMO and related molecular properties of the (C 6 H 20 N 3 )SbCl 5 ·Cl·H 2 O compound were calculated by Density functional theory (DFT) using B3LYP method with GenECP sets. The calculated structural parameters (bond lengths and angles) are in good agreement with the experimental XRD data. The vibrational unscaled wavenumbers were calculated and scaled by a proper scaling factor of 0.984. Acceptable consistency was observed between calculated and experimental results. The assignments of wavenumbers were made on the basis of potential energy distribution (PED) using Vibrational Energy Distribution Analysis (VEDA) software. The HOMO-LUMO study was extended to calculate various molecular parameters like ionization potential, electron affinity, global hardness, electro-chemical potential, electronegativity and global electrophilicity of the given molecule. Copyright © 2017 Elsevier B.V. All rights reserved.

Crystal structure, vibrational spectra, optical and DFT studies of bis (3-azaniumylpropyl) azanium pentachloroantimonate (III) chloride monohydrate (C6H20N3)SbCl5·Cl·H2O

NASA Astrophysics Data System (ADS)

Ahmed, Houssem Eddine; Kamoun, Slaheddine

2017-09-01

The crystal structure of (C6H20N3)SbCl5·Cl·H2O is built up of [NH3(CH2)3NH2(CH2)3NH3]3 + cations, [SbCl5]2 - anions, free Cl- anions and neutral water molecules connected together by Nsbnd H ⋯ Cl, Nsbnd H ⋯ O and Osbnd H ⋯ Cl hydrogen bonds. The optical band gap determined by diffuse reflection spectroscopy (DRS) is 3.78 eV for a direct allowed transition. Optimized molecular geometry, atomic Mulliken charges, harmonic vibrational frequencies, HOMO-LUMO and related molecular properties of the (C6H20N3)SbCl5·Cl·H2O compound were calculated by Density functional theory (DFT) using B3LYP method with GenECP sets. The calculated structural parameters (bond lengths and angles) are in good agreement with the experimental XRD data. The vibrational unscaled wavenumbers were calculated and scaled by a proper scaling factor of 0.984. Acceptable consistency was observed between calculated and experimental results. The assignments of wavenumbers were made on the basis of potential energy distribution (PED) using Vibrational Energy Distribution Analysis (VEDA) software. The HOMO-LUMO study was extended to calculate various molecular parameters like ionization potential, electron affinity, global hardness, electro-chemical potential, electronegativity and global electrophilicity of the given molecule.

The ground state of metallic nano-structures in heavily irradiated NaCl-KBF4

NASA Astrophysics Data System (ADS)

Cherkasov, F. G.; L'Vov, S. G.; Tikhonov, D. A.; den Hartog, H. W.; Vainshtein, D. I.

ESR, NMR and static magnetic susceptibility measurements of heavily irradiated NaCl-K and NaCl-KBF4 are reported. Up to 10% of the NaCl-molecules are transformed into metallic Na nanoparticles and Cl-2 precipitates. In addition, there are paramagnetic F- and F-aggregates, which are coupled by exchange interactions to the conduction electrons in the nanoparticles. Above 160 K the NMR and ESR signals of NaCl-K and NaCl-KBF4 show Pauli paramagnetism and the properties of the Na nanoparticles are similar to bulk sodium. A single ESR line is observed revealing exchange interaction between conduction electrons in the nano-particles and F-aggregates. The observed decrease of the ESR susceptibility with decreasing temperature is due to a metal-insulator transition. The conduction electrons are localized below 40 K and the above mentioned F-aggregate centers contribute significantly to the overall ESR signal. For NaCl-KBF4 we observed that with decreasing temperature the ESR line shifts towards lower fields due to antiferromagnetic ordering and internal magnetic fields.

Atomic-scale imaging of the dissolution of NaCl islands by water at low temperature

NASA Astrophysics Data System (ADS)

Peng, Jinbo; Guo, Jing; Ma, Runze; Meng, Xiangzhi; Jiang, Ying

2017-03-01

The dissolution of sodium chloride (NaCl) in water is a frequently encountered process in our daily lives. While the NaCl dissolution process in liquid water has been extensively studied, whether and how the dissolution occurs below the freezing point is still not clear. Using a low-temperature scanning tunneling microscope (STM), here we were able to directly visualize the dissolution of Au-supported NaCl (0 0 1) bilayer islands by water at atomic level. We found that the single water molecule on the STM tip can assist the extraction of single Na+ from the NaCl surface even at 5 K, while leaving the Cl- intact. When covered with a full water monolayer, the NaCl islands started to dissolve from the step edges and also showed evidence of dissolution inside the terraces as the temperature was raised up to 145 K. At 155 K, the water molecules completely desorbed from the surface, which was accompanied with the decomposition and restructuring of the bilayer NaCl islands. Those results suggest that the dissolution of NaCl may occur well below the freezing point at the ice/NaCl interfaces and is mainly driven by the interaction between the water molecules and the Na+, which is in clear contrast with the NaCl dissolution in liquid water.

Aspects of Salt Tolerance in a NaCl-Selected Stable Cell Line of Citrus sinensis.

PubMed

Ben-Hayyim, G; Kochba, J

1983-07-01

A NaCl-tolerant cell line which was selected from ovular callus of ;Shamouti' orange (Citrus sinensis L. Osbeck) proved to be a true cell line variant. This conclusion is based on the following observations. (a) Cells which have been removed from the selection pressure for at least four passages retain the same NaCl tolerance as do cells which are kept constantly on 0.2 molar NaCl. (b) Na(+) and Cl(-) uptake are considerably lower in salt-tolerant cells (R-10) than in salt-sensitive cells (L-5) at a given external NaCl concentration. (c) Growth of salt-tolerant cells is markedly suppressed upon replacement of NaCl by KCl, whereas the growth of salt-sensitive cells is only slightly affected. Accumulation of K(+) and Cl(-) accompanies the inhibition of growth. Experiments carried out with sodium and potassium sulfate suggest that the toxic effect is due to the accumulated Cl(-). (d) Removal of Ca(2+) from the growth medium severely inhibits the growth of salt-tolerant cells in the presence of NaCl, while it has a minor effect on growth of salt-sensitive cells in the presence of NaCl. (e) Electron micrographs show that the salt-tolerant cells have very big vacuoles when exposed to salt, while the size of the vacuoles of the salt-sensitive cells does not change.

Low-energy electron stimulated desorption of neutrals from multilayers of SiCl4 on Si(111).

PubMed

Lane, Christopher D; Orlando, Thomas M

2006-04-28

The interaction of low-energy electrons with multilayers of SiCl(4) adsorbed on Si(111) leads to production and desorption of Cl((2)P(32)), Cl((2)P(12)), Si, and SiCl. Resonant structure in the yield versus incident electron energy (E(i)) between 6 and 12 eV was seen in all neutral channels and assigned to dissociative electron attachment (DEA), unimolecular decay of excited products produced via autodetachment and direct dissociation. These processes yield Cl((2)P(32)) and Cl((2)P(12)) with nonthermal kinetic energies of 425 and 608 meV, respectively. The Cl((2)P(12)) is produced solely at the vacuum surface interface, whereas the formation of Cl((2)P(32)) likely involves subsurface dissociation, off-normal trajectories, and collisions with neighbors. Structure in the Cl((2)P(32)) yield near 14 and 25 eV can originate from excitation of electrons in the 2e, 7t(2) and 6t(2), 6a(1) levels, respectively. Although the 14 eV feature was not present in the Cl((2)P(12)) yield, the broad 25 eV feature, which involves complex Auger filling of holes in the 6t(2) and 6a(1) levels of SiCl(4), is observed. Direct ionization, exciton decay, and DEA from secondary electron scattering all occur at E(i)>14 eV. Si and SiCl were detected via nonresonant ionization of SiCl(x) precursors that are produced via the same states and mechanisms that yield Cl. The Si retains the kinetic energy profile of the desorbed precursors.

NO2/NO partitioning as a test of stratospheric ClO concentrations over Antarctica

NASA Technical Reports Server (NTRS)

Webster, Christopher R.

1987-01-01

Physical conditions in the 10-20 km region of the Antarctic stratosphere make the (NO2)/(NO) ratio particularly sensitive to high chlorine levels in the form of ClO. According to simple known photochemical relationships between NO2, NO, ClO, and O3, high ClO levels of 1 ppbv over Antarctica must be accompanied by large values of the (NO2)/(NO) ratio. At high ClO abundances, the (NO2)/(NO) ratio is approximately proportional to the ClO concentration. It is proposed that in-situ measurements of the (NO2)/(NO) ratio could be used to test the high chlorine hypothesis.

New Mexico: Los Alamos

Atmospheric Science Data Center

2014-05-15

article title:  Los Alamos, New Mexico     View Larger JPEG image ... kb) Multi-angle views of the Fire in Los Alamos, New Mexico, May 9, 2000. These true-color images covering north-central New Mexico ...

Experimental Study of Codeposition Electrochemistry Using Mixtures of ScCl 3 and YCl 3 in LiCl-KCl Eutectic Salt at 500°C

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

Shaltry, Michael R.; Yoo, Tae-Sic; Fredrickson, Guy L.

2017-09-12

Cyclic voltammetry and chronopotentiometry tests were applied to molten LiCl-KCl eutectic at 500 °C including amounts of ScCl 3 and YCl 3. The purpose of the testing was to observe the effect of applied electrical current on the codeposition of scandium and yttrium, which were chosen as surrogate elements for uranium and plutonium, respectively. Features of the work were to vary the concentration of ScCl 3 (at relatively low concentrations) as well as varying the applied current, all with a fixed concentration of YCl 3. Results of the experiments could provide insight of uranium electrorefining and may provide evidence, whichmore » suggests the electrorefiner could be operated at lower UCl 3 concentration whereby codeposition (U and Pu) could be more effectively controlled.« less

Origin of halides (Cl- and Br-) and of their stable isotopes (d37Cl and d81Br) at the Tournemire URL (France) - Experimental and numerical approach

NASA Astrophysics Data System (ADS)

Bachir-Bey, Nassim; Matray, Jean-Michel

2014-05-01

This work is part of research conducted by the Institute of Radiological and Nuclear Safety (IRSN) on the geological disposal of High-Level and Intermediate-Level Long-Lived (HL-ILLL) radioactive waste in deep clayrocks. In France, the choice of the potential host rock for the geological storage is focused on the Callovian-Oxfordian (COx) of Meuse/Haute-Marne from its low permeability, capacity for self- sealing, high sorption and ability to radionuclide (RN) transport by diffusion. IRSN, which plays an expert role for ASN has its own underground research laboratory in a clayrock which has strong analogies to the COx. This is the Toarcian/Domerian clayrock located at Tournemire in southern Aveyron in France. The purpose of this study was to assess the transfer of RN in the Tournemire clayrock through the study of halides contents and of their stable isotopes (Cl-, Br-, Cl-/Br-, d37Cl, d81Br). The approach used was multiple and consisted for halides to: 1) Assess their stock in different fractions of the rock by applying several techniques including i) alkaline fusion for their total stock, ii) leaching to access their stock in porewater and to mineral phases sensitive to dissolution iii) cubic diffusion for their stock in porewater, 2) Get their diffusive transport parameters of a selection of samples from the upper Toarcian by cubic diffusion experiments modelled using the Hytec transport code developed by Mines ParisTech and 3) Model their transport after palaeohydrogeological known changes of the Tournemire massif. The experimental approach, conducted at the LAME lab, did not lead to an operational protocol for the alkaline fusion due to an incomplete rock dissolution. Leaching was used to characterize the concentrations of halides in the fractions of pore water and of minerals sensitive to dissolution. The results show levels of halides much higher than those of pore water with very low Cl/Br ratios likely resulting from the dissolution of mineral species. The

Crystal structure and explosive performance of a new CL-20/caprolactam cocrystal

NASA Astrophysics Data System (ADS)

Guo, Changyan; Zhang, Haobin; Wang, Xiaochuan; Xu, Jinjiang; Liu, Yu; Liu, Xiaofeng; Huang, Hui; Sun, Jie

2013-09-01

Co-crystallization is an effective way to improve performance of the high explosive 2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (CL-20). A new CL-20/caprolactam (CPL) cocrystal has been prepared by a rapid solvent evaporation method, and the crystal structure investigations show that the cocrystal is formed by strong intermolecular hydrogen bond interaction. The cocrystal can only be prepared with low moisture content of the air, because water in the air has a profound effect on the cocrystal formation, and it can lead to crystal form conversion of CL-20, but not the formation of cocrystal. The CL20/CPL explosive possess very low sensitivity, and may be used as additive in explosives formulation to desensitize other high explosives.

Neutralization of Hydroxide Ion in Melt-Grown NaCl Crystals

NASA Technical Reports Server (NTRS)

Otterson, Dumas A.

1961-01-01

Many recent studies of solid-state phenomena, particularly in the area of crystal imperfections, have involved the use of melt-grown NaCl single crystals. Quite often trace impurities in these materials have had a prominent effect on these phenomena. Trace amounts of hydroxide ion have been found in melt-grown NaCl crystals. This paper describes a nondestructive method of neutralizing the hydroxide ion in such crystals. Crystals of similar hydroxide content are maintained at an elevated temperature below the melting point of NaCl in a flowing atmosphere containing. dry hydrogen chloride. Heat treatment is continued until an analysis of the test specimens shows no excess hydroxide ion. A colorimetric method previously described4 is used for this analysis.

Quantum Dynamics Study of the Potential Energy Minima Effect on Energy Efficiency for the F- + CH3Cl → FCH3 + Cl- Reaction.

PubMed

Li, Yida; Wang, Yuping; Wang, Dunyou

2017-04-13

The Polanyi rules on the energy efficiency on reactivity are summarized solely from the locations of barriers on the potential energy surfaces. Here, our quantum dynamics study for the F - + CH 3 Cl → FCH 3 + Cl - reaction shows that the two potential energy minima in the entrance channel on the potential energy surface play an essential role in energy efficiency on reactivity. The reactivity of this reaction is dominated by the low collision energies where two distinctive reaction mechanisms involve the two minima in the entrance channel. Overall, the Cl-CH 3 stretching motion and C-H 3 umbrella motion both are more efficient than the translational motion in promoting this reaction. Although this reaction has a negative energy barrier, our study shows that it is the minima in the entrance channel, together with the energy barrier relative to these minima, that determine the energy efficacy on reactivity.

Molecular and electronic structure of thin films of protoporphyrin(IX)Fe(III)Cl

NASA Astrophysics Data System (ADS)

Snyder, Shelly R.; White, Henry S.

1991-11-01

Electrochemical, scanning tunneling microscopy (STM), and tunneling spectroscopy studies of the molecular and electronic properties of thin films of protoporphyrin(IX)Fe(III)Cl (abbreviated as PP(IX)Fe(III)Cl) on highly oriented pyrolytic graphite (HOPG) electrodes are reported. PP(IX)Fe(III)Cl films are prepared by two different methods: (1) adsorption, yielding an electrochemically-active film, and (2) irreversible electrooxidative polymerization, yielding an electrochemically-inactive film. STM images, in conjunction with electro-chemical results, indicate that adsorption of PP(IX)Fe(III)Cl from aqueous solutions onto freshly cleaved HOPG results in a film comprised of molecular aggregates. In contrast, films prepared by irreversible electrooxidative polymerization of PP(IX)Fe(III)Cl have a denser, highly structured morphology, including what appear to be small pinholes (approx. 50A diameter) in an otherwise continuous film.

Analysis of GaN Damage Induced by Cl2/SiCl4/Ar Plasma

NASA Astrophysics Data System (ADS)

Minami, Masaki; Tomiya, Shigetaka; Ishikawa, Kenji; Matsumoto, Ryosuke; Chen, Shang; Fukasawa, Masanaga; Uesawa, Fumikatsu; Sekine, Makoto; Hori, Masaru; Tatsumi, Tetsuya

2011-08-01

GaN-based optical devices are fabricated using a GaN/InGaN/GaN sandwiched structure. The effect of radicals, ions, and UV light on the GaN optical properties during Cl2/SiCl4/Ar plasma etching was evaluated using photoluminescence (PL) analysis. The samples were exposed to plasma (radicals, ions, and UV light) using an inductively coupled plasma (ICP) etching system and a plasma ion beam apparatus that can separate the effects of UV and ions both with and without covering the SiO2 window on the surface. Etching damage in an InGaN single quantum well (SQW) was formed by exposing the sample to plasma. The damage, which decreases PL emission intensity, was generated not only by ion beam irradiation but also by UV light irradiation. PL intensity decreased when the thickness of the upper GaN layer was etched to less than 60 nm. In addition, simultaneous irradiation of UV light and ions slightly increased the degree of damage. There seems to be a synergistic effect between the UV light and the ions. For high-quality GaN-based optoelectronics and power devices, UV light must be controlled during etching processes in addition to the etching profile, selectivity, and ion bombardment damage.

The initial stages of NaCl dissolution: Ion or ion pair solvation?

NASA Astrophysics Data System (ADS)

Klimes, Jiri; Michaelides, Angelos

2009-03-01

The interaction of water with rock salt (NaCl) is important in a wide variety of natural processes and human activities. A lot is known about NaCl dissolution at the macroscopic level but we do not yet have a detailed atomic scale picture of how salt crystals dissolve. Here we report an extensive series of density functional theory, forcefield and molecular dynamics studies of water clusters at flat and defective NaCl surfaces and NaCl clusters. The focus is on answering seemingly elementary questions such as how many water molecules are needed before it becomes favorable to extract an ion or a pair of ions from the crystal or the cluster. It turns out, however, that the answers to these questions are not so straightforward: below a certain number of water molecules (˜ 12) solvation of individual ions is less costly and above this number solvation of ion pairs is favored. These results reveal a hitherto unknown complexity in the NaCl dissolution process born out of a subtle interplay between water-water and water-ion interactions.

Identification and utilization of cleistogamy gene cl7(t) in rice (Oryza sativa L.).

PubMed

Ni, Da-Hu; Li, Juan; Duan, Yong-Bo; Yang, Ya-Chun; Wei, Peng-Cheng; Xu, Rong-Fang; Li, Chun-Rong; Liang, Dan-Dan; Li, Hao; Song, Feng-Shun; Ni, Jin-Long; Li, Li; Yang, Jian-Bo

2014-05-01

Gene transformation is an important method for improvement of plants into elite varieties. However, the possibility of gene flow between genetically modified (GM) crops and similar species is a serious public issue that may potentially endanger ecological stability. Cleistogamy is expected to be an ideal genetic tool for preventing transgene propagation from GM crops. A rice mutant, cl7(t), was created by ethyl methanesulfonate mutagenesis. The mutant exhibited cleistogamy, and had closed spikelets, reduced plant height, and altered morphology of the leaves, panicle, and seeds. Anatomical investigations revealed that the cl7(t) mutant contained more vascular bundles and thicker stems than the wild type, which increased the mechanical strength of its internodes, and anti-lodging ability. Further studies demonstrated that the force required to open the lemma and palea was higher in the cl7(t) mutant, and there was weak swelling ability in the lodicules, which leads to cleistogamy. Allelic analyses and complementation tests indicated that cl7(t) was a novel allele of dep2, a mutant that was previously reported to have similar panicle morphology. Sequence analysis showed that cl7(t) had a single nucleotide substitution (C to A) in the third exon that leads to a Ser substitution with a stop codon, giving a truncated DEP2 protein. Quantitative RT-PCR and in situ hybridization tests demonstrated that there was lower CL7(t) expression level in the spikelets and weaker CL7(t) signals in the lodicules of the cl7(t) mutant compared with wild type, which implies that CL7(t) might participate in the development of lodicules. To improve the agronomic traits of cl7(t) to fit the needs of field production, the cl7(t) mutant was crossed with an intermediate-type rice variety named Guanghui102, which bears some important agronomic traits, including increased grain numbers and high rate of seed setting. Through multi-generational pedigree selection, cleistogamy lines with improved

Chlorination Revisited: Does Cl- Serve as a Catalyst in the Chlorination of Phenols?

PubMed

Lau, Stephanie S; Abraham, Sonali M; Roberts, A Lynn

2016-12-20

The aqueous chlorination of (chloro)phenols is one of the best-studied reactions in the environmental literature. Previous researchers have attributed these reactions to two chlorine species: HOCl (at circum-neutral and high pH) and H 2 OCl + (at low pH). In this study, we seek to examine the roles that two largely overlooked chlorine species, Cl 2 and Cl 2 O, may play in the chlorination of (chloro)phenols. Solution pH, chloride concentration, and chlorine dose were systematically varied in order to assess the importance of different chlorine species as chlorinating agents. Our findings indicate that chlorination rates at pH < 6 increase substantially when chloride is present, attributed to the formation of Cl 2 . At pH 6.0 and a chlorine dose representative of drinking water treatment, Cl 2 O is predicted to have at best a minor impact on chlorination reactions, whereas Cl 2 may contribute more than 80% to the overall chlorination rate depending on the (chloro)phenol identity and chloride concentration. While it is not possible to preclude H 2 OCl + as a chlorinating agent, we were able to model our low-pH data by considering Cl 2 only. Even traces of chloride can generate sufficient Cl 2 to influence chlorination kinetics, highlighting the role of chloride as a catalyst in chlorination reactions.

Effect of pH on Cl sup minus transport in TAL of Henle's loop

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

Kondo, Yoshiaki; Yoshitomi, Koji; Imai, Masashi

1987-12-01

To further characterize the mechanism of Cl{sup {minus}} transport across the hamster thin ascending limb (TAL) of Henle's loop, the authors examined effects of pH on Cl{sup {minus}} permeability as determined by either the choline chloride diffusion voltage or the lumen-to-bath {sup 36}Cl flux in the isolated segments perfused in vitro. When pH of the bathing fluid or the perfusate was reduced from 7.4 to 5.8, the Cl{sup {minus}}-Na{sup +} permeability ratio was reduced from 2.77 {plus minus} 0.21 to 0.48 {plus minus} 0.02 or from 2.55 {plus minus} 0.15 to 0.81 {plus minus} 0.11, respectively. At 37{degree}C, when themore » pH of the bathing fluid was reduced from 7.4 to 6.2, the lumen-to-bath flux coefficient for {sup 36}Cl was reduced from 84.8 {plus minus} 7.5 to 20.4 {plus minus} 3.2, whereas the value for {sup 22}Na was unchanged. From the pH titration curves for P{sub Cl}/P{sub Na}, pK{sub a} values for proton binding were 6.31 and 5.78, and Hill's coefficients were 2.1 and 2.3 on the basolateral side and on the luminal side, respectively. Intracellular acidification with o-nitrophenylacetate also decreased the Cl{sup {minus}} permeability. They conclude that (1) Cl{sup {minus}} transport across the TAL is mediated by a process that is sensitive to ambient pH, (2) the basolateral side is more sensitive to pH, (3) the proton binding exhibits positive cooperativity in the modulation of Cl{sup {minus}} transport, and (4) intracellular pH might also modulate Cl{sup {minus}} transport.« less

Phase relations in the system NaCl-KCl-H2O II: Differential thermal analysis of the halite liquidus in the NaCl-H2O binary above 450°c

USGS Publications Warehouse

Gunter, W.D.; Chou, I.-Ming; Girsperger, Sven

1983-01-01

The solubility of halite can be expressed as a function of the mole-fractional-based activity of NaCl in the liquid phase (L) in temperature (T, °K) and pressure (P, bars) In  Our liquidus data (based on 10 compositions) above 500 bars for these brines were combined with this equation to generate activity coefficients of NaCl which were fit within their experimental uncertainties to the following one parameter Margules equation In . Concentrated solutions of NaCl show negative deviations from ideality which rapidly increase in magnitude with decreasing XNaCl.

Fractionation of Cl/Br during fluid phase separation in magmatic-hydrothermal fluids

NASA Astrophysics Data System (ADS)

Seo, Jung Hun; Zajacz, Zoltán

2016-06-01

Brine and vapor inclusions were synthesized to study Cl/Br fractionation during magmatic-hydrothermal fluid phase separation at 900 °C and pressures of 90, 120, and 150 MPa in Li/Na/K halide salt-H2O systems. Laser ablation ICP-MS microanalysis of high-density brine inclusions show an elevated Cl/Br ratio compared to the coexisting low-density vapor inclusions. The degree of Cl/Br fractionation between vapor and brine is significantly dependent on the identity of the alkali metal in the system: stronger vapor partitioning of Br occurs in the Li halide-H2O system compared to the systems of K and Na halide-H2O. The effect of the identity of alkali-metals in the system is stronger compared to the effect of vapor-brine density contrast. We infer that competition between alkali-halide and alkali-OH complexes in high-temperature fluids might cause the Cl/Br fractionation, consistent with the observed molar imbalances of alkali metals compared to halides in the analyzed brine inclusions. Our experiments show that the identity of alkali metals controls the degrees of Cl/Br fractionation between the separating aqueous fluid phases at 900 °C, and suggest that a significant variability in the Cl/Br ratios of magmatic fluids can arise in Li-rich systems.

Isolation and Characterization of a High Affinity Peptide Inhibitor of ClC-2 Chloride Channels*

PubMed Central

Thompson, Christopher H.; Olivetti, Pedro R.; Fuller, Matthew D.; Freeman, Cody S.; McMaster, Denis; French, Robert J.; Pohl, Jan; Kubanek, Julia; McCarty, Nael A.

2009-01-01

The ClC protein family includes voltage-gated chloride channels and chloride/proton exchangers. In eukaryotes, ClC proteins regulate membrane potential of excitable cells, contribute to epithelial transport, and aid in lysosomal acidification. Although structure/function studies of ClC proteins have been aided greatly by the available crystal structures of a bacterial ClC chloride/proton exchanger, the availability of useful pharmacological tools, such as peptide toxin inhibitors, has lagged far behind that of their cation channel counterparts. Here we report the isolation, from Leiurus quinquestriatus hebraeus venom, of a peptide toxin inhibitor of the ClC-2 chloride channel. This toxin, GaTx2, inhibits ClC-2 channels with a voltage-dependent apparent KD of ∼20 pm, making it the highest affinity inhibitor of any chloride channel. GaTx2 slows ClC-2 activation by increasing the latency to first opening by nearly 8-fold but is unable to inhibit open channels, suggesting that this toxin inhibits channel activation gating. Finally, GaTx2 specifically inhibits ClC-2 channels, showing no inhibitory effect on a battery of other major classes of chloride channels and voltage-gated potassium channels. GaTx2 is the first peptide toxin inhibitor of any ClC protein. The high affinity and specificity displayed by this toxin will make it a very powerful pharmacological tool to probe ClC-2 structure/function. PMID:19574231

Volumetric, rheological, and optical properties of hydroxylamine hydrochloride aqueous solutions containing NaCl, KCl, and NH4Cl at 30°C

NASA Astrophysics Data System (ADS)

Deosarkar, S. D.; Puyad, A. L.; Shaikh, U. B.; Solanke, S. S.

2014-04-01

Densities, viscosities, and refractive indices of aqueous solutions of hydroxylamine hydrochloride containing 0.05, 0.10, and 0.15 mol/dm3 NaCl, KCl, and NH4Cl were measured at different concentrations of hydroxylamine hydrochloride at 30°C. Viscosity coefficients A and B representing ion-ion and ion-solvent interactions were determined from Jones-Dole equation. Experimental properties and viscosity coefficients have been interpreted in terms of ion-ion and ion-solvent interactions. Ion-solvent interactions were found to be dominating over the ion-ion interactions in studied systems.

Age related decreases in neural sensitivity to NaCl in SHR-SP.

PubMed

Osada, Kazumi; Komai, Michio; Bryant, Bruce P; Suzuki, Hitoshi; Tsunoda, Kenji; Furukawa, Yuji

2003-03-01

To determine whether neurophysiological taste responses of young and old rats are different, recordings were made from the whole chorda tympani nerve which innervates taste buds on the anterior tongue. SHR-SP (Stroke-Prone Spontaneously Hypertensive Rats) in two age groups were studied. Chemical stimuli included single concentrations of 250 mM NH(4)Cl, 100 mM NaCl, 100 mM KCl, 500 mM sucrose, 20 mM quinine-hydrochloride, 10 mM HCl, 10 mM monosodium glutamate (MSG), 10 mM L- glutamic acid (L-Glu) and an NaCl concentration series. The magnitude of the neural response (response ratio) was calculated by dividing the amplitude of the integrated response by the amplitude of the spontaneous activity that preceded it. Substantial neural responses to all chemicals were obtained at both ages. The responses to KCl, sucrose, quinine-hydrochloride, HCl, monosodium glutamate (MSG) and glutamic acid (Glu) did not change with age, but the response to NaCl did decrease significantly. The profile of the response/concentration function for NaCl differed with age. In particular, the responses to solutions more concentrated than 100 mM NaCl were significantly weaker in aged than in young SHR-SPs. We also observed that recovery from amiloride treatment on the tongue of SHR-SPs was faster in aged rats than in young ones, suggesting that there is some functional difference in the sodium-specific channels on the taste cell. These results suggest that aged SHR-SP may be less able than young SHR-SPs to discriminate among higher concentrations of NaCl solutions.

Ab initio and RRKM study of the reaction of ClO with HOCO radicals.

PubMed

Yu, Hua-Gen; Francisco, Joseph S

2009-11-19

The reaction pathways for the ClO + HOCO reaction have been explored using the coupled-cluster method to locate and optimize the critical points on the ground-state potential-energy surface. Results show that the ClO + HOCO reaction can produce Cl + HOC(O)O, HOCl + CO(2), HCl + CO(3), and HClO + CO(2) via an addition or a direct hydrogen abstraction reaction mechanism. The reaction kinetics has been studied using the variational RRKM theory. It is found that the ClO + HOCO reaction is fast and has a negative temperature dependence at low temperatures. At room temperature, the thermal rate coefficient is obtained as 4.26 x 10(-12) cm(3) molecules(-1) s(-1) with product branching fractions of Cl (0.518), HOCl (0.469), HCl (0.01), and HClO (0.003) at zero pressure. The Cl + HOC(O)O products are major, compared to the HOCl + CO(2) products, because of the loose transition state along the dissociation pathway to eliminate Cl. In addition, the RRKM/master equation simulations indicate that the stabilization of the HOC(O)OCl intermediates is noticeable at moderate pressures as its thermal rate constants reach about 6.0 x 10(-13) cm(3) molecules(-1) s(-1). In contrast, the other product branching ratios for the ClO + HOCO reaction are weakly dependent on pressure.

Accurate Wavelength Measurement of High-Energy Gamma Rays from the 35Cl(n,{gamma}) Reactions

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

Belgya, T.; Molnar, G.L.; Mutti, P.

2005-05-24

The energies of eight gamma rays in the 36Cl level scheme have been measured with high precision using the 35Cl(n,{gamma}) reaction and the GAMS4 spectrometer. From these energies, a skeleton decay scheme for 36Cl was constructed, and the binding energy of 36Cl was determined to higher precision than previously. It is shown that using this new information, binding energy determination from Ge detector experiments for other nuclei can also be made with higher precision than now available. The measurement of additional weaker 36Cl gamma rays is continuing.

Amiloride-Sensitive and Amiloride-Insensitive Responses to NaCl + Acid Mixtures in Hamster Chorda Tympani Nerve

PubMed Central

Hettinger, Thomas P.; Savoy, Lawrence D.; Frank, Marion E.

2012-01-01

Component signaling in taste mixtures containing both beneficial and dangerous chemicals depends on peripheral processing. Unidirectional mixture suppression of chorda tympani (CT) nerve responses to sucrose by quinine and acid is documented for golden hamsters (Mesocricetus auratus). To investigate mixtures of NaCl and acids, we recorded multifiber responses to 50 mM NaCl, 1 and 3 mM citric acid and acetic acid, 250 μM citric acid, 20 mM acetic acid, and all binary combinations of each acid with NaCl (with and without 30 μM amiloride added). By blocking epithelial Na+ channels, amiloride treatment separated amiloride-sensitive NaCl-specific responses from amiloride-insensitive electrolyte-generalist responses, which encompass all of the CT response to the acids as well as responses to NaCl. Like CT sucrose responses, the amiloride-sensitive NaCl responses were suppressed by as much as 50% by citric acid (P = 0.001). The amiloride-insensitive electrolyte-generalist responses to NaCl + acid mixtures approximated the sum of NaCl and acid component responses. Thus, although NaCl-specific responses to NaCl were weakened in NaCl–acid mixtures, electrolyte-generalist responses to acid and NaCl, which tastes KCl-like, were transmitted undiminished in intensity to the central nervous system. The 2 distinct CT pathways are consistent with known rodent behavioral discriminations. PMID:22451526

Experimental Determination of Lead Interactions with Citrate and EDTA in NaCl and MgCl2 Solutions to High Ionic Strength and Its Applications.

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

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

For this study, the interactions of lead with citrate and ethylenediaminetetraacetate (EDTA) are investigated based on solubility measurements as a function of ionic strength at room temperature (22.5 ± 0.5°C) in NaCl and M gCl 2 solutions. The formation constants (log β 1 0 ) for Pb[C 3H 5O(COO) 3]– (abbreviated as PbCitrate –) and Pb[(CH 2COO) 2N(CH2) 2N(CH 2COO) 2)] 2– (abbreviated as PbEDTA 2–) Pb 2+ + [C 3H 5O(COO) 3] 3– = Pb[C 3H 5O(COO) 3] – (1) Pb 2+ + (CH 2COO) 2N(CH 2) 2N(CH 2COO) 2) 4- = Pb[(CH 2COO) 2N(CH 2) 2N(CH 2COO) 2)]more » 2– (2) are evaluated as 7.28 ± 0.18 (2σ) and 20.00 ± 0.20 (2σ), respectively, with a set of Pitzer parameters describing the specific interactions in NaCl and M gCl 2 media. Based on these parameters, the interactions of lead with citrate and EDTA in various low temperature environments can be accurately modelled.« less

Comprension de los conceptos de los enlaces ionico y covalente en estudiantes universitarios del primer curso de quimica general

NASA Astrophysics Data System (ADS)

Ballesteros Benavides, Maria Elvira

Para este trabajo utilizamos el estudio de casos cualitativo que se llevo a cabo en una universidad privada de Puerto Rico. Empleamos como unidad de analisis el concepto de enlace quimico, ionico y covalente. Los participantes fueron los estudiantes de la seccion nocturna del curso de Quimica General I. La investigacion se desarrollo por medio de dos entrevistas de persona a persona, observaciones de las expresiones no verbales y la hoja de identificacion de conceptos. Para la triangulacion tomamos en consideracion las preconcepciones erroneas, las concepciones alternativas y el mapa de conceptos de cada participante. Preparamos un mapa de conceptos para el enlace quimico validado por un comite de expertos. Tambien, elaboramos los mapas de conceptos de los participantes que sirvieron para varios propositos: conocer la estructura conceptual, expresar los logros, hacer comparaciones e identificar la presencia de concepciones alternativas. Entre los hallazgos encontramos que todos los participantes poseen conocimiento previo de los enlaces quimicos ionico y covalente y dentro de ese conocimiento existen preconcepciones erroneas mas numerosas para el enlace ionico. Al principio del semestre el 50% de los participantes demostraron tener "carencia fuerte de conceptos" tanto para el enlace ionico como para el covalente. Al finalizar el semestre encontramos en el 40% de los participantes concepciones alternativas tanto para el enlace ionico como para el covalente y el 90% no lograron distinguir un enlace del otro. Nuestras conclusiones fueron que los participantes sin distincion del aprovechamiento academico demostraron tener la tendencia de "carencia fuerte de conceptos" tanto para el enlace ionico como para el covalente, presentaron dificultad al integrar los conceptos de los enlaces quimicos ionico y covalente que se pusieron de manifiesto al dar los ejemplos. Las preconcepciones erroneas contribuyen en el desarrollo de las concepciones alternativas. Ademas, los