Pentanuclear heterometallic {Mn(III)(2)Ln(3)} (Ln = Gd, Dy, Tb, Ho) assemblies in an open-book type structural topology: appearance of slow relaxation of magnetization in the Dy(III) and Ho(III) analogues.

PubMed

Bag, Prasenjit; Chakraborty, Amit; Rogez, Guillaume; Chandrasekhar, Vadapalli

2014-07-07

The reaction of Ln(III) nitrate and Mn(ClO4)2·6H2O salts in the presence of a multidentate sterically unencumbered ligand, (E)-2,2'-(2-hydroxy-3-((2-hydroxyphenylimino)methyl)-5-methylbenzylazanediyl)diethanol (LH4) leads to the isolation of four isostructural pentanuclear hetereometallic complexes [Mn(III)2Gd3(LH)4(NO3)(HOCH3)]ClO4·NO3 (1), [Mn(III)2Dy3(LH)4(NO3)(HOCH3)]ClO4·NO3 (2), [Mn(III)2Tb3(LH)4(NO3)(HOCH3)]ClO4·NO3 (3), and [Mn(III)2Ho3(LH)4(NO3)(HOCH3)]ClO4·NO3 (4) with an open-book type structural topology. 1-4 are dicationic and crystallize in the achiral space group, P21/n. A total of four triply deprotonated ligands, [LH](3-), are involved in holding the pentameric metal framework, {Mn(III)2Ln3}. In these complexes both the lanthanide and the manganese(III) ions are doubly bridged, involving phenolate or ethoxide oxygen atoms. The magnetochemical analysis reveals the presence of global antiferromagnetic interactions among the spin centers at low temperatures in all the four compounds. AC susceptibility measurements show the presence of temperature dependent out-of-phase ac signal for compounds 2 and 4 indicating an SMM behavior.

Atacama perchlorate as an agricultural contaminant in groundwater: Isotopic and chronologic evidence from Long Island, New York

USGS Publications Warehouse

Böhlke, J.K.; Hatzinger, P.B.; Sturchio, N.C.; Gu, B.; Abbene, I.; Mroczkowski, S.J.

2009-01-01

Perchlorate (ClO4-) is a common groundwater constituent with both synthetic and natural sources. A potentially important source of ClO4- is past agricultural application of ClO4--bearing natural NO3- fertilizer imported from the Atacama Desert, Chile, but evidence for this hasbeenlargely circumstantial. Here we report ClO4- stable isotope data (??37Cl, ??18O, and ??17O), along with other supporting chemical and isotopic environmental tracer data, to document groundwater ClO4- contamination sources and history in parts of Long Island, New York. Sampled groundwaters were oxic and ClO4- apparently was not affected by biodegradation within the aquifers. Synthetic ClO4- was indicated by the isotopic method in groundwater near a fireworks disposal site at a former missile base. Atacama ClO4- was indicated in agricultural and urbanizing areas in groundwaters with apparent ages >20 years. In an agricultural area, ClO4- concentrations and ClO4-/NO3- ratios increased withgroundwaterage, possiblybecauseof decreasing application rates of Atacama NO3- fertilizers and/or decreasing ClO4- concentrations in Atacama NO 3- fertilizers in recent years. Because ClO 4-/NO3- ratios of Atacama NO 3- fertilizers imported in the past (???2 ?? 10-3 mol mol-1) were much higher than the ClO 4-/NO3- ratio of recommended drinking-water limits (7 ?? 10-5 mol mol-1 in New York), ClO4- could exceed drinkingwater limits even where NO3- does not, and where Atacama NO3- was only a minor source of N. Groundwater ClO4- with distinctive isotopic composition was a sensitive indicator of past Atacama NO3- fertilizer use on Long Island and may be common in other areas that received NO3- fertilizers from the late 19th century through the 20th century. ?? 2009 American Chemical Society.

Electrochemical performance of LiNi0.4Co0.2Mn0.4O2 prepared by different molten salt flux: LiNO3-LiCl and LiNO3-KNO3

NASA Astrophysics Data System (ADS)

Satyanarayana, M.; James, Joseph; U. V., Varadaraju

2017-10-01

LiNi0.4Co0.2Mn0.4O2 material synthesized at different temperatures by using LiNO3-LiCl and LiNO3-KNO3 molten salt as a reaction medium. The phase purity of the samples obtained by powder X-ray diffraction measurement which suggests layered α-NaFeO2 type is obtained at 800-900 °C using LiNO3-LiCl flux and at 750-850 °C using LiNO3-KNO3 flux. The surface morphology change with flux media at different temperature are obtained by scanning electron microscopy analysis. The galvanostatic cycling results show that the high stable reversible discharge capacity of 155 (±3) mAh g-1 obtained for treated compound at 900 °C for 1 h (using LiNO3-LiCl) with coloumbic efficiency of 99%. The reversible discharge capacity of 140 and 130 (±3) mAh g-1 obtained for treated compound at 750 and 850 °C, respectively (using LiNO3-KNO3).

Fluorescence Quenching of Humic Acid by Coated Metallic Silver Particles.

PubMed

Zhu, Guocheng; Yin, Jun

2017-07-01

Natural organic matter is an important component of the aquatic environments, which has attracted wide attention to its influence of interaction with other pollutants. The present work aimed to investigate its fluorescence quenching (FQ) by coated metallic silver particles (AgNPs). In this work, using fluorescence spectroscopy in conjunction with UV-Vis spectroscopy and dynamic light scattering, the effect of coated AgNPs on fluorescence quenching intensity (FQI) of humic acid (HA) was assessed. In addition, the influence of electrolytes (NaCl, NaNO 3 and CaNO 3 ) in the FQI was observed. Results showed that with AgNPs dosage increased (>1.17X10 -3  mM), fluorescence quantum yield of HA gradually decreased, which implies that the FQ occurred. Furher observation showed that the FQ process followed both first-order and second-order Stern-Volmer functions. The FQ process was affected by the electrolytes: NaCl had an effect on reduction of FQI, possibly resulting from dissolution of AgNPs; Both of NaNO 3 and Ca(NO 3 ) 2 had an effect on the FQ of HA but Ca(NO 3 ) 2 presented greater degree. As a result, the FQ degree of HA by alone electrolyte was listed in descent order as Ca(NO 3 ) 2  > NaNO 3  > NaCl, which also implies the subsequent experimental results, indicating the FQ degree of HA by mutual electrolytes as Ca(NO 3 ) 2  + NaNO 3  > Ca(NO 3 ) 2  + NaCl > NaNO 3  + NaCl.

Synergistic effect among Cl2, SO2 and NO2 in their heterogeneous reactions on gamma-alumina

NASA Astrophysics Data System (ADS)

Huang, Zhenling; Zhang, Zhaohui; Kong, Weiheng; Feng, Shuo; Qiu, Ye; Tang, Siqun; Xia, Chuanqin; Ma, Lingling; Luo, Min; Xu, Diandou

2017-10-01

Severe haze in China has been a global concern in recent years. Most studies about the mechanism of haze formation mare only focused on the heterogeneous reactions of SO2 and NO2 on mineral aerosols. However, little is known about the role of molecular chlorine (Cl2) in those reactions. Here, we investigated the heterogeneous uptake of Cl2, SO2 and NO2 on γ-Al2O3 particles under different conditions using a quartz-based flow reactor. We found that the existence of γ-Al2O3 seed aerosols significantly promotes the formation of secondary chloride, sulfate and nitrate aerosols, and Cl2, NO2 and SO2 have synergistic effects when they react on γ-Al2O3 surface under humid condition. The results also shows that Cl2 can promote the formation of secondary sulfate and nitrate aerosols on γ-Al2O3 surface. Moreover, Cl2 is much easier to react with the surface of γ-Al2O3 and form secondary Cl- aerosol when comparing with NO2 and SO2, suggesting that Cl2 is of great importance in atmospheric chemistry, it has the potential to alter the surface properties (e.g., chemical composition and fraction) of mineral aerosol, enhance the production of secondary inorganic aerosols in the troposphere, and thus cause adverse effects on the climate and human health.

Anti-MRSA-acting carbamidocyclophanes H-L from the Vietnamese cyanobacterium Nostoc sp. CAVN2.

PubMed

Preisitsch, Michael; Harmrolfs, Kirsten; Pham, Hang T L; Heiden, Stefan E; Füssel, Anna; Wiesner, Christoph; Pretsch, Alexander; Swiatecka-Hagenbruch, Monika; Niedermeyer, Timo H J; Müller, Rolf; Mundt, Sabine

2015-09-01

Correction to: The Journal of Antibiotics (2015) 68, 165–177; doi:10.1038/ja.2014.118, published online 3 September 2014. The authors noted errors upon publication of this article in the ‘Results and Discussion’ section. The molecular formulas presented for compounds 1–5 in the "Isolation procedure and structure elucidation" section are incorrect. These formulas should read as follows: 1. C37H57NO7 2. C37H56ClNO7 3. C38H56Cl2N2O8 4. C37H55Cl2NO7 5. C37H54Cl3NO7

Chromium(IV)–Peroxo Complex Formation and Its Nitric Oxide Dioxygenase Reactivity

PubMed Central

Yokoyama, Atsutoshi; Han, Jung Eun; Cho, Jaeheung; Kubo, Minoru; Ogura, Takashi; Siegler, Maxime A.; Karlin, Kenneth D.; Nam, Wonwoo

2012-01-01

The O2 and NO reactivity of a Cr(II) complex bearing a 12-membered tetraazamacrocyclic TMC ligand, [CrII(12-TMC)(Cl)]+ (1), and the NO reactivity of its peroxo derivative, [CrIV(12-TMC)(O2)(Cl)]+ (2), are described. By contrast to the previously reported Cr(III)-superoxo complex, [CrIII(14-TMC)(O2)(Cl)]+, a Cr(IV)-peroxo complex (2) is formed in the reaction of 1 and O2. Full spectroscopic and X-ray analysis reveals that 2 possesses a side-on η2-peroxo ligation. A quantitative reaction of 2 with NO affords a reduction in Cr oxidation state and production of a Cr(III)-nitrato complex, [CrIII(12-TMC)(NO3)(Cl)]+ (3). The latter is suggested to form via a Cr(III)-peroxynitrite intermediate. A Cr(II)-nitrosyl complex, [CrII(12-TMC)(NO)(Cl)]+ (4), derived from 1 andNO could also be synthesized; however, it does not react with O2. PMID:22950528

ATMOS/ATLAS-3 Measurements of Stratospheric Chlorine and Reactive Nitrogen Partitioning Inside and Outside the November 1994 Antarctic Vortex

NASA Technical Reports Server (NTRS)

Rinsland, C. P.; Gunson, M. R.; Salawitch, R. J.; Michelsen, H. A.; Zander, R.; Newchurch, M. J.; Abbas, M. M.; Abrams, M. C.; Manney, G. L.; Chang, A. Y.;

Nqrs Data for C3H2Cl10N2PSb[C3HCl4N2P·Cl6HSb](Subst. No. 0601)

NASA Astrophysics Data System (ADS)

Chihara, H.; Nakamura, N.

This document is part of Subvolume A `Substances Containing Ag … C10H15' of Volume 48 `Nuclear Quadrupole Resonance Spectroscopy Data' of Landolt-Börnstein - Group III `Condensed Matter'. It contains an extract of Section `3.2 Data tables' of the Chapter `3 Nuclear quadrupole resonance data' providing the NQRS data for C3H2Cl10N2PSb [C3HCl4N2P·Cl6HSb] (Subst. No. 0601)

Thermal emission spectroscopy of the middle atmosphere

NASA Technical Reports Server (NTRS)

Kunde, V. G.; Brasunas, J. C.; Conrath, B. J.; Herman, J. R.; Maguire, W. C.; Massie, S. T.; Abbas, Mian M.

1990-01-01

The general objective of this research is to obtain, via remote sensing, simultaneous measurements of the vertical distributions of stratospheric temperature, ozone, and trace constituents that participate in the catalytic destruction of ozone (NO(sub y): NO, NO2, NO3, HNO3, ClONO2, N2O5, HNO4; Cl(sub x): HOCl), and the source gases for the catalytic cycles (H2O, CH4, N2O, CF2Cl2, CFCl3, CCl4, CH3Cl, CHF2Cl, etc.). Data are collected during a complete diurnal cycle in order to test our present understanding of ozone chemistry and its associate catalytic cycles. The instrumentation employed is an emission-mode, balloon-borne, liquid-nitrogen-cooled Michelson interferometer-spectrometer (SIRIS), covering the mid-infrared range with a spectral resolution of 0.020 cm(exp -1). Cryogenic cooling combined with the use of extrinsic silicon photoconductor detectors allows the detection of weak emission features of stratospheric gaseous species. Vertical distributions of these species are inferred from scans of the thermal emission of the limb in a sequence of elevation angles. The fourth SIRIS balloon flight was carried out from Palestine, Texas on September 15-16, 1986 with 9 hours of nighttime data (40 km). High quality data with spectral resolution 0.022 cm(exp -1), were obtained for numerous limb sequences. Fifteen stratospheric species have been identified to date from this flight: five species from the NO(sub y) family (HNO3, NO2, NO, ClONO2, N2O5), plus CO2, O3, H2O, N2O, CH4, CCl3F, CCl2F2, CHF2Cl, CF4, and CCl4. The nighttime values of N2O5, ClONO2, and total odd nitrogen have been measured for the first time, and compared to model results. Analysis of the diurnal variation of N2O5 within the 1984 and 1986 data sets, and of the 1984 ClONO2 measurements, were presented in the literature. The demonstrated ability of SIRIS to measure all the major NO(sub y) species, and therefore to determine the partitioning of the nitrogen family over a continuous diurnal cycle, is a powerful tool in the verification and improvement of photochemical modeling.

Thermodynamic modeling of Cl(-), NO3(-) and SO4(2-) removal by an anion exchange resin and comparison with Dubinin-Astakhov isotherms.

PubMed

Dron, Julien; Dodi, Alain

2011-03-15

The removal of chloride, nitrate, and sulfate ions from wastewaters by a macroporous ion-exchange resin is studied through the experimental results obtained for six ion exchange systems, OH(-)/Cl(-), OH(-)/NO3(-), OH(-)/SO4(2-), and HCO3(-)/Cl(-), Cl(-)/NO3(-), Cl(-)/SO4(2-). The results are described through thermodynamic modeling, considering either an ideal or a nonideal behavior of the ionic species in the liquid and solid phases. The nonidealities are determined by the Davies equation and Wilson equations in the liquid and solid phases, respectively. The results show that the resin has a strong affinity for all the target ions, and the order of affinity obtained is OH(-) < HCO3(-) < Cl(-) < NO3(-) < SO4(2-). The calculation of the changes in standard Gibbs free energies (ΔG(0)) shows that even though HCO3(-) has a lower affinity to the resin, it may affect the removal of Cl(-), and in the same way that Cl(-) may affect the removal of NO3(-) and SO4(2-). The application of nonidealities in the thermodynamic model leads to an improved fit of the model to the experimental data with average relative deviations below 1.5% except for the OH(-)/SO4(2-) system. On the other hand, considering ideal or nonideal behaviors has no significant impact on the determination of the selectivity coefficients. The thermodynamic modeling is also compared with the Dubinin-Astakhov adsorption isotherms obtained for the same ion exchange systems. Surprisingly, the latter performs significantly better than the ideal thermodynamic model and nearly as well as the nonideal thermodynamic model.

The Kinetic Nonequilibrium Processes in the Internal Flow and in the Plume of Subsonic and Supersonic Aircrafts

NASA Technical Reports Server (NTRS)

Starik, Alexander M.

1997-01-01

(1) Our results show that under combustion of thermal destruction products of n-C8H18, and other hydrocarbon fuels with air at the equivalent ratio -0.5 and less the chemical equilibrium is not realized at the exit plane of combustion chamber and in the gas turbine and nozzle for most of small components such as NO2, NO3, HNO, HNO2, HNO3, N(x)H(y), HO2, OH. The chemical equilibrium is not realized in the internal flow of ramjet hydrogen combustion engine too. So at the nozzle exit plane both of gas-turbine hydrocarbon combustion engine and of ramjet hydrogen combustion engine the relatively large values of concentration of such small components as NO3, HNO2, N2O, HNO3, HNO, NH, N2H, HO2, H2O2 may be realized. The exact definition of these component concentration as well as concentration of NO(x), OH, SO2, O, H, H2, H2O at the nozzle exit plane is very important for plume chemistry. (2) The results which were obtained for subsonic and hypersonic aircrafts indicate on the considerable change of the composition of the gas mixture along the plume. This change can be caused not only by the mixture of combustion products with the atmosphere air but by proceeding of whole complex of nonequilibrium photochemical reactions. The photodissociation processes begin to influence on the formation of the free atoms and radicals at flight altitude H greater than or equal to 18 km. Neglect of these processes can result in essential (up to 10(exp 4) times) mistakes of values gamma(sub OH), gamma(sub O), gamma(sub H), gamma(sub HSO3) and some products of CFC's disintegration. It was found that penetration of Cl-containing species from the atmosphere into the exhaust flow and its interaction with nitrogen oxides leads to essential increasing of the concentration of Cl, Cl2, ClO2, ClNO3, CH3Cl and sometimes HCl and the decreasing of ClO concentration by comparison with background values. The results of our analysis show that the plume aircraft with both hydrocarbon and hydrogen combustion engine may be source of various pollutant components such as HNO, HNO4,ClO2, CH3NO2, CH3NO3, CH2O, Cl, H2O2, but not only NO, NO2, HNO2, HNO3, N2O5, SO2, SO3, H2SO4 as it was supposed before.

Spectroscopic and computational studies of ionic clusters as models of solvation and atmospheric reactions

NASA Astrophysics Data System (ADS)

Kuwata, Keith T.

Ionic clusters are useful as model systems for the study of fundamental processes in solution and in the atmosphere. Their structure and reactivity can be studied in detail using vibrational predissociation spectroscopy, in conjunction with high level ab initio calculations. This thesis presents the applications of infrared spectroscopy and computation to a variety of gas-phase cluster systems. A crucial component of the process of stratospheric ozone depletion is the action of polar stratospheric clouds (PSCs) to convert the reservoir species HCl and chlorine nitrate (ClONO2) to photochemically labile compounds. Quantum chemistry was used to explore one possible mechanism by which this activation is effected: Cl- + ClONO2 /to Cl2 + NO3- eqno(1)Correlated ab initio calculations predicted that the direct reaction of chloride ion with ClONO2 is facile, which was confirmed in an experimental kinetics study. In the reaction a weakly bound intermediate Cl2-NO3- is formed, with ~70% of the charge localized on the nitrate moiety. This enables the Cl2-NO3- cluster to be well solvated even in bulk solution, allowing (1) to be facile on PSCs. Quantum chemistry was also applied to the hydration of nitrosonium ion (NO+), an important process in the ionosphere. The calculations, in conjunction with an infrared spectroscopy experiment, revealed the structure of the gas-phase clusters NO+(H2O)n. The large degree of covalent interaction between NO+ and the lone pairs of the H2O ligands is contrasted with the weak electrostatic bonding between iodide ion and H2O. Finally, the competition between ion solvation and solvent self-association is explored for the gas-phase clusters Cl/-(H2O)n and Cl-(NH3)n. For the case of water, vibrational predissociation spectroscopy reveals less hydrogen bonding among H2O ligands than predicted by ab initio calculations. Nevertheless, for n /ge 5, cluster structure is dominated by water-water interactions, with Cl- only partially solvated by the water cluster. Preliminary infrared spectra and computations on Cl- (NH3)n indicate that NH3 preferentially binds to Cl- ion instead of forming inter-solvent networks.

75 FR 28471 - Airworthiness Directives; Bombardier, Inc. Model CL-600-1A11 (CL-600), CL-600-2A12 (CL-601), and...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-05-21

... the No. 3 hydraulic system can result in an uncommanded NLG retraction. * * * * * We are issuing this... pressure, in the No. 3 hydraulic system can result in an uncommanded NLG retraction. Although there have... retraction. Although there have been no such cases reported on the Challenger models covered by this...

Genotoxicity of two heavy metal compounds: lead nitrate and cobalt chloride in Polychaete Perinereis cultrifera.

PubMed

Singh, Nisha; Bhagat, Jacky; Ingole, Baban S

2017-07-01

The present study explores the in vivo and in vitro genotoxic effects of lead nitrate, [Pb(NO 3 ) 2 ] a recognized environmental pollutant and cobalt chloride (CoCl 2 ), an emerging environmental pollutant in polychaete Perinereis cultrifera using comet assay. Despite widespread occurrence and extensive industrial applications, no previous published reports on genotoxicity of these compounds are available in polychaete as detected by comet assay. Polychaetes were exposed in vivo to Pb(NO 3 ) 2 (0, 100, 500, and 1000 μg/l) and CoCl 2 (0, 100, 300, and 500 μg/l) for 5 days. At 100 μg/l Pb(NO 3 ) 2 concentration, tail DNA (TDNA) values in coelomocytes were increase by 1.16, 1.43, and 1.55-fold after day 1, day 3, and day 5, whereas, OTM showed 1.12, 2.33, and 2.10-fold increase in in vivo. Pb(NO 3 ) 2 showed a concentration and time-dependent genotoxicity whereas CoCl 2 showed a concentration-dependent genotoxicity in in vivo. A concentration-dependent increase in DNA damage was observed in in vitro studies for Pb(NO 3 ) 2 and CoCl 2 . DNA damage at 500 μg/L showed almost threefold increase in TDNA and approximately fourfold increase in OTM as compared to control in in vitro. Our studies suggest that Pb(NO 3 ) 2 and CoCl 2 have potential to cause genotoxic damage, with Pb(NO 3 ) 2 being more genotoxic in polychaete and should be used more carefully in industrial and other activities. Graphical abstract.

Nocturnal chlorine radical reservoir species at noon during CalNex-LA 2010

NASA Astrophysics Data System (ADS)

Mielke, L. H.; Griffith, S. M.; Hansen, R. F.; Dusanter, S.; Stevens, P. S.; Flynn, J. H.; Grossberg, N.; Lefer, B. L.; Veres, P. R.; Roberts, J. M.; Gilman, J. B.; Kuster, W. C.; Young, C. J.; Washenfelder, R. A.; Cochran, A. K.; Osthoff, H. D.

2011-12-01

While the role of the hydroxyl radical (OH) in the oxidation of volatile organic compounds (VOCs) is relatively well understood and recognized, less attention has been paid to Cl as an oxidant even though Cl is more reactive towards VOCs than OH. In the troposphere, mixing ratios of chlorine atoms are quite low (103 - 105 atoms cm-3), making them difficult to quantify directly in the atmosphere. The presence of chlorine atoms has been inferred only indirectly using hydrocarbon ratios, but this approach works well only in very remote environments. In polluted coastal urban areas such as Los Angeles, modeling studies have indicated that Cl radical initiated chemistry can have a significant impact on ozone formation. Here, chlorine atoms are produced by reaction of OH with hydrochloric acid and by photolysis of photolabile chlorine containing species, such as the nocturnally formed nitryl chloride (ClNO2) and molecular chlorine (Cl2). In this presentation, measurements of ClNO2 and Cl2 mixing ratios using chemical ionization mass spectrometry (CIMS) at the Calnex-LA campaign ground site between May 15, and June 15, 2010 are presented with a focus on their daytime abundances and photolysis to produce Cl atoms. Photolysis of ClNO2 in the morning (7 am to 10 am) produced Cl atoms at a median rate of 6.1×105 atoms cm-3 s-1. Daytime ClNO2 was observed with a median mixing ratio of 14 parts-per-trillion by volume (pptv). Assuming a steady state between ClNO2 photolysis and its formation via the reaction of Cl atom with NO2, we calculate a median Cl atom concentration of up to 1×105 atoms cm-3, approximately 3% of that of OH, which was quantified by laser induced fluorescence. Implications of Cl on the oxidation of VOCs in the Los Angeles area will be discussed. For example, methane is oxidized by Cl at a relative rate of up to half that of OH under the conditions outlined above.

[Effect of simulated inorganic anion leaching solution of electroplating sludge on the bioactivity of Acidithiobacillus ferrooxidans].

PubMed

Chen, Yan; Huang, Fang; Xie, Xin-Yuan

2014-04-01

An Acidithiobacillus ferrooxidans strain WZ-1 (GenBank sequence number: JQ968461) was used as the research object. The effects of Cl-, NO3-, F- and 4 kinds of simulated inorganic anions leaching solutions of electroplating sludge on the bioactivity of Fe2+ oxidation and apparent respiratory rate of WZ-1 were investigated. The results showed that Cl-, NO3(-)- didn't have any influence on the bioactivity of WZ-1 at concentrations of 5.0 g x L(-1), 1.0 g x L(-1), respectively. WZ-1 showed tolerance to high levels of Cl- and NO3- (about 10.0 g x L(-1), 5.0 g x L(-1), respectively), but it had lower tolerance to F- (25 mg x L(-1)). Different kinds of simulated inorganic anions leaching solutions of electroplating sludge had significant differences in terms of their effects on bioactivity of WZ-1 with a sequence of Cl-/NO3(-)/F(-) > or = NO3(-)/F(-) > Cl-/F(-) > Cl(-)/NO3(-).

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.

Atacama perchlorate as an agricultural contaminant in groundwater: Isotopic and chronologic evidence from Long Island, New York

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

Bohlke, J. K.; Hatzinger, Paul B.; Sturchio, N. C.

2009-01-01

Perchlorate (ClO{sub 4}{sup -}) is a common groundwater constituent with both synthetic and natural sources. A potentially important source of ClO{sub 4}{sup -} is past agricultural application of ClO{sub 4}{sup -}-bearing natural NO{sub 3}{sup -} fertilizer imported from the Atacama Desert, Chile, but evidence for this has been largely circumstantial. Here we report ClO{sub 4}{sup -} stable isotope data ({delta}{sup 37}Cl, {delta}{sup 18}O, and {Delta}{sup 17}O), along with other supporting chemical and isotopic environmental tracer data, to document groundwater ClO{sub 4}{sup -} contamination sources and history in parts of Long Island, New York. Sampled groundwaters were oxic and ClO{sub 4}{supmore » -} apparently was not affected by biodegradation within the aquifers. Synthetic ClO{sub 4}{sup -} was indicated by the isotopic method in groundwater near a fireworks disposal site at a former missile base. Atacama ClO{sub 4}{sup -} was indicated in agricultural and urbanizing areas in groundwaters with apparent ages >20 years. In an agricultural area, ClO{sub 4}{sup -} concentrations and ClO{sub 4}{sup -}/NO{sub 3}{sup -} ratios increased with groundwater age, possibly because of decreasing application rates of Atacama NO{sub 3}{sup -} fertilizers and/or decreasing ClO{sub 4}{sup -} concentrations in Atacama NO{sub 3}{sup -} fertilizers in recent years. Because ClO{sub 4}{sup -}/NO{sub 3}{sup -} ratios of Atacama NO{sub 3}{sup -} fertilizers imported in the past (2 x 10{sup -3} mol mol{sup -1}) were much higher than the ClO{sub 4}{sup -}/NO{sub 3}{sup -} ratio of recommended drinking-water limits (7 x 10{sup -5} mol mol{sup -1} in New York), ClO{sub 4}{sup -} could exceed drinking-water limits even where NO{sub 3}{sup -} does not, and where Atacama NO{sub 3}{sup -} was only a minor source of N. Groundwater ClO{sub 4}{sup -} with distinctive isotopic composition was a sensitive indicator of past Atacama NO{sub 3}{sup -} fertilizer use on Long Island and may be common in other areas that received NO{sub 3}{sup -} fertilizers from the late 19th century through the 20th century.« less

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

P3N-PIPO, a Frameshift Product from the P3 Gene, Pleiotropically Determines the Virulence of Clover Yellow Vein Virus in both Resistant and Susceptible Peas

PubMed Central

Suzuki, Haruka; Miyashita, Yuri; Choi, Sun Hee; Hisa, Yusuke; Rihei, Shunsuke; Shimada, Ryoko; Jeon, Eun Jin; Abe, Junya; Uyeda, Ichiro

2016-01-01

ABSTRACT Peas carrying the cyv1 recessive resistance gene are resistant to clover yellow vein virus (ClYVV) isolates No.30 (Cl-No.30) and 90-1 (Cl-90-1) but can be infected by a derivative of Cl-90-1 (Cl-90-1 Br2). The main determinant for the breaking of cyv1 resistance by Cl-90-1 Br2 is P3N-PIPO produced from the P3 gene via transcriptional slippage, and the higher level of P3N-PIPO produced by Cl-90-1 Br2 than by Cl-No.30 contributes to the breaking of resistance. Here we show that P3N-PIPO is also a major virulence determinant in susceptible peas that possess another resistance gene, Cyn1, which does not inhibit systemic infection with ClYVV but causes hypersensitive reaction-like lethal systemic cell death. We previously assumed that the susceptible pea cultivar PI 226564 has a weak allele of Cyn1. Cl-No.30 did not induce cell death, but Cl-90-1 Br2 killed the plants. Our results suggest that P3N-PIPO is recognized by Cyn1 and induces cell death. Unexpectedly, heterologously strongly expressed P3N-PIPO of Cl-No.30 appears to be recognized by Cyn1 in PI 226564. The level of P3N-PIPO accumulation from the P3 gene of Cl-No.30 was significantly lower than that of Cl-90-1 Br2 in a Nicotiana benthamiana transient assay. Therefore, Cyn1-mediated cell death also appears to be determined by the level of P3N-PIPO. The more efficiently a ClYVV isolate broke cyv1 resistance, the more it induced cell death systemically (resulting in a loss of the environment for virus accumulation) in susceptible peas carrying Cyn1, suggesting that antagonistic pleiotropy of P3N-PIPO controls the resistance breaking of ClYVV. IMPORTANCE Control of plant viral disease has relied on the use of resistant cultivars; however, emerging mutant viruses have broken many types of resistance. Recently, we revealed that Cl-90-1 Br2 breaks the recessive resistance conferred by cyv1, mainly by accumulating a higher level of P3N-PIPO than that of the nonbreaking isolate Cl-No.30. Here we show that a susceptible pea line recognized the increased amount of P3N-PIPO produced by Cl-90-1 Br2 and activated the salicylic acid-mediated defense pathway, inducing lethal systemic cell death. We found a gradation of virulence among ClYVV isolates in a cyv1-carrying pea line and two susceptible pea lines. This study suggests a trade-off between breaking of recessive resistance (cyv1) and host viability; the latter is presumably regulated by the dominant Cyn1 gene, which may impose evolutionary constraints upon P3N-PIPO for overcoming resistance. We propose a working model of the host strategy to sustain the durability of resistance and control fast-evolving viruses. PMID:27279605

Hydrogen/Chlorine exchange reactions of gaseous carbanions.

PubMed

Chen, Hao; Cooks, R Graham; Meurer, Eduardo C; Eberlin, Marcos N

2005-12-01

Gas-phase reactions of three typical carbanions CH(2)NO(2)(-), CH(2)CN(-), and CH(2)S(O)CH(3)(-) with the chloromethanes CH(2)Cl(2), CHCl(3), and CCl(4), examined by tandem mass spectrometry, show a novel hydrogen/chlorine exchange reaction. For example, reaction between the nitromethyl anion CH(2)NO(2)(-) and carbon tetrachloride CCl(4) forms the ion CHClNO(2)(-). The suggested reaction mechanism involves nucleophilic attack by CH(2)NO(2)(-) at the chlorine of CCl(4) followed by proton transfer within the resulting complex [CH(2)ClNO(2) + CCl(3)(-)] to form CHClNO(2)(-) and CHCl(3). Two other carbanions CH(2)CN(-) and CH(2)S(O)CH(3)(-) also undergo the novel hydrogen/chlorine exchange reactions with CCl(4) but to a much smaller extent, their higher nucleophilicities favoring competitive nucleophilic attack reactions. Proton abstraction is the exclusive pathway in the reactions of these carbanions with CHCl(3). While CH(2)CN(-) and CH(2)S(O)CH(3)(-) promote mainly proton abstraction and nucleophilic displacement in reactions with CH(2)Cl(2), CH(2)NO(2)(-) does not react.

2016 winter campaigns on ClNO2 and N2O5 at a mountain top and a semi-rural site in southern China: overview and initial results

NASA Astrophysics Data System (ADS)

Wang, T.; Wang, W.; Yun, H.; Tham, Y. J.; Xia, M.; Yu, C.; Wang, Z.; Zhang, N.; Cui, L.; Poon, S.; Lee, S.; Ou, Y.; Yue, D.; Zhai, Y.

2017-12-01

In the past decade, heterogeneous uptake of dinitrogen pentoxide (N2O5) on aerosol and subsequent production of nitryl chloride (ClNO2) have been found to impact the oxidative capacity, NOx fate, and the formation of aerosol nitrate and photochemical ozone. However, the detailed processes and effects are not completely understand for diverse environments of the globe. Our previous measurements at a mountain top (957 m a.s.l) in Hong Kong in winter 2013 revealed elevated concentrations of N2O5 (up to 7.7 ppb) and ClNO2 (up to 4.7 ppb) and that the polluted air masses originated from inland urban areas of the Pearl River delta (PRD). To understand the detailed uptake processes, an intensive measurement campaign was conducted at the same site (Tai Mo Shan, TMS) during October-December 2016 and at a semi-rural site (Heshan) in the center of the PRD in January 2017. Key parameters related to N2O5 and ClNO2 processes, including aerosol ionic composition, aerosol number and size, volatile organic compounds as well as ozone, NOx and NOy, were measured during the two campaigns. Elevated (up to 3.4 ppb) ClNO2 concentrations were observed at the mountain site on many nights a few hours after sunset, and extremely high levels of ClNO2 (up to 8.3 ppb) were measured in the inland site during a heavy pollution event. The meteorological conditions and variations of ClNO2 will be examined with concurrently measured parameters to elucidate factors determining N2O5 uptake and ClNO2 production. The 2016 results at TMS will be compared with those from 2013.

Kinetic studies of the reaction of the SO radical with NO2 and ClO from 210 to 363 K

NASA Technical Reports Server (NTRS)

Brunning, J.; Stief, L. J.

1986-01-01

The rates of the reactions of the SO radical with NO2 and ClO (significant in the upper atmosphere of earth and Venus) were determined in a discharge flow system near 1 torr pressure with detection of radical and molecular species using collision-free sampling mass spectrometry. The rate constants were obtained from the decay of SO radicals in the presence of an excess of NO2 and ClO. The NO2 reaction was examined between 210 and 363 K and found to be temperature invariant: SO + NO2 yields SO2 + NO; k1 = (1.37 + or - 0.10) x 10 to the -11th cu cm/s. In addition, the ClO reaction was observed to be independent of temperature between 248 and 363 K: SO + ClO yields SO2 + Cl; k2 = (3.22 + or - 0.48) x 10 to the -11th cu cm/s. A comparison was made with previous investigations of these reactions at room temperature and with other radical-radical reactions involving SO or ClO.

Rigid 2D networks of copper(II) complexes containing diallylbis(pyridin-3-yl)silane: Insight into anion and media effects on catechol oxidation catalysis

NASA Astrophysics Data System (ADS)

Ryu, Minjoo; Lee, Young-A.; Jung, Ok-Sang

2018-01-01

The self-assembly of CuX2 (X- = Cl-, Br-, NO3-, ClO4-, and BF4-) with a new diallylbis(pyridin-3-yl)silane ligand (L) gives rise to the similar 2D coordination networks with composition of Cu(II) and L of 1: 2 irrespective of anions and solvents. The 2D networks of [CuCl2L2]·2H2O, [CuBr2L2]·2H2O, and [Cu(H2O)2L2]·(NO3)2 are packed in a staggered mode while the similar networks of [Cu(BF4)2L2] and [Cu(ClO4)2L2] are arrayed in a eclipsed fashion. These crystals of all 2D networks have been employed as catalysts for 3,5-di-tert-butylcatechol (3,5-DBCat) oxidation, showing the catalytic effects in the order of [CuCl2L2]·2H2O > [CuBr2L2]·2H2O > [Cu(H2O)2L2]·(NO3)2 > [Cu(ClO4)2L2] > [Cu(BF4)2L2] in chloroform and exhibiting the catalytic effects of only [Cu(H2O)2L2]·(NO3)2 in acetone. Thus, the catalytic effect on catechol oxidation is strongly dependent on anions and media.

Pressure-Dependent Yields and Product Branching Ratios in the Broadband Photolysis of Chlorine Nitrate

NASA Technical Reports Server (NTRS)

Nickolaisen, Scott L.; Sander, Stanley P.; Friedl, Randall R.

1996-01-01

The photolysis of chlorine nitrate was studied using broadband flash photolysis coupled with long-path ultraviolet-visible absorption spectroscopy. Branching ratios for the Cl + NO3 and ClO + NO2 product channels were determined from time-dependent measurements of ClO and NO3 concentrations. Yields of the ClO and NO3 products displayed a dependence on the bath gas density and the spectral distribution of the photolysis pulse. Product yields decreased with increasing bath gas density regardless of the spectral distribution of the photolysis pulse; however, the decrease in product yield was much more pronounced when photolysis was limited to longer wavelengths. For photolysis in a quartz cell (lambda > 200 nm) the yield decreased by a factor of 2 over the pressure 10-100 Torr. In a Pyrex cell (lambda > 300 nm), the yield decreased by a factor of 50 over the same pressure range. When photolysis was limited to lambda > 350 nm, the yield decreased by a factor of 250. Branching ratios for the photolysis channels [ClONO2 + h.nu yields ClO + NO2 (1a) and ClONO2 + h.nu yields Cl + NO3 (lb)] were determined from the relative ClO and NO3 product yields at various pressures. Although the absolute product yield displayed a pressure dependence, the branching between the two channels was independent of pressure. The relative branching ratios (assuming negligible contributions from other channels) are 0.61 +/- 0.20 for channel 1a and 0.39 +/- 0.20 for channel lb for photolysis with lambda > 200 nm and 0.44 +/- 0.08 for channel 1a and 0.56 +/- 0.08 for channel 1b for photolysis with lambda > 300 nm. The implications of these results for the chemistry of the lower stratosphere are discussed.

Global patterns and environmental controls of perchlorate and nitrate co-occurrence in arid and semi-arid environments

NASA Astrophysics Data System (ADS)

Jackson, W. Andrew; Böhlke, J. K.; Andraski, Brian J.; Fahlquist, Lynne; Bexfield, Laura; Eckardt, Frank D.; Gates, John B.; Davila, Alfonso F.; McKay, Christopher P.; Rao, Balaji; Sevanthi, Ritesh; Rajagopalan, Srinath; Estrada, Nubia; Sturchio, Neil; Hatzinger, Paul B.; Anderson, Todd A.; Orris, Greta; Betancourt, Julio; Stonestrom, David; Latorre, Claudio; Li, Yanhe; Harvey, Gregory J.

2015-09-01

Natural perchlorate (ClO4-) is of increasing interest due to its wide-spread occurrence on Earth and Mars, yet little information exists on the relative abundance of ClO4- compared to other major anions, its stability, or long-term variations in production that may impact the observed distributions. Our objectives were to evaluate the occurrence and fate of ClO4- in groundwater and soils/caliche in arid and semi-arid environments (southwestern United States, southern Africa, United Arab Emirates, China, Antarctica, and Chile) and the relationship of ClO4- to the more well-studied atmospherically deposited anions NO3- and Cl- as a means to understand the prevalent processes that affect the accumulation of these species over various time scales. ClO4- is globally distributed in soil and groundwater in arid and semi-arid regions on Earth at concentrations ranging from 10-1 to 106 μg/kg. Generally, the ClO4- concentration in these regions increases with aridity index, but also depends on the duration of arid conditions. In many arid and semi-arid areas, NO3- and ClO4- co-occur at molar ratios (NO3-/ClO4-) that vary between ∼104 and 105. We hypothesize that atmospheric deposition ratios are largely preserved in hyper-arid areas that support little or no biological activity (e.g. plants or bacteria), but can be altered in areas with more active biological processes including N2 fixation, N mineralization, nitrification, denitrification, and microbial ClO4- reduction, as indicated in part by NO3- isotope data. In contrast, much larger ranges of Cl-/ClO4- and Cl-/NO3- ratios indicate Cl- varies independently from both ClO4- and NO3-. The general lack of correlation between Cl- and ClO4- or NO3- implies that Cl- is not a good indicator of co-deposition and should be used with care when interpreting oxyanion cycling in arid systems. The Atacama Desert appears to be unique compared to all other terrestrial locations having a NO3-/ClO4- molar ratio ∼103. The relative enrichment in ClO4- compared to Cl- or NO3- and unique isotopic composition of Atacama ClO4- may reflect either additional in-situ production mechanism(s) or higher relative atmospheric production rates in that specific region or in the geological past. Elevated concentrations of ClO4- reported on the surface of Mars, and its enrichment with respect to Cl- and NO3-, could reveal important clues regarding the climatic, hydrologic, and potentially biologic evolution of that planet. Given the highly conserved ratio of NO3-/ClO4- in non-biologically active areas on Earth, it may be possible to use alterations of this ratio as a biomarker on Mars and for interpreting major anion cycles and processes on both Mars and Earth, particularly with respect to the less-conserved NO3- pool terrestrially.

Distorted tetrahedral nickel-nitrosyl complexes: spectroscopic characterization and electronic structure.

PubMed

Soma, Shoko; Van Stappen, Casey; Kiss, Mercedesz; Szilagyi, Robert K; Lehnert, Nicolai; Fujisawa, Kiyoshi

2016-09-01

The linear nickel-nitrosyl complex [Ni(NO)(L3)] supported by a highly hindered tridentate nitrogen-based ligand, hydrotris(3-tertiary butyl-5-isopropyl-1-pyrazolyl)borate (denoted as L3), was prepared by the reaction of the potassium salt of the ligand with the nickel-nitrosyl precursor [Ni(NO)(Br)(PPh 3 ) 2 ]. The obtained nitrosyl complexes as well as the corresponding chlorido complexes [Ni(NO)(Cl)(PPh 3 ) 2 ] and [Ni(Cl)(L3)] were characterized by X-ray crystallography and different spectroscopic methods including IR/far-IR, UV-Vis, NMR, and multi-edge X-ray absorption spectroscopy at the Ni K-, Ni L-, Cl K-, and P K-edges. For comparative electronic structure analysis we also performed DFT calculations to further elucidate the electronic structure of [Ni(NO)(L3)]. These results provide the nickel oxidation state and the character of the Ni-NO bond. The complex [Ni(NO)(L3)] is best described as [Ni (II) (NO (-) )(L3)], and the spectroscopic results indicate that the phosphane complexes have a similar [Ni (II) (NO (-) )(X)(PPh 3 ) 2 ] ground state.

Quantitative and Qualitative Involvement of P3N-PIPO in Overcoming Recessive Resistance against Clover Yellow Vein Virus in Pea Carrying the cyv1 Gene

PubMed Central

Choi, Sun Hee; Hagiwara-Komoda, Yuka; Atsumi, Go; Shimada, Ryoko; Hisa, Yusuke; Naito, Satoshi

2013-01-01

In pea carrying cyv1, a recessive gene for resistance to Clover yellow vein virus (ClYVV), ClYVV isolate Cl-no30 was restricted to the initially infected cells, whereas isolate 90-1 Br2 overcame this resistance. We mapped the region responsible for breaking of cyv1-mediated resistance by examining infection of cyv1 pea with chimeric viruses constructed from parts of Cl-no30 and 90-1 Br2. The breaking of resistance was attributed to the P3 cistron, which is known to produce two proteins: P3, from the main open reading frame (ORF), and P3N-PIPO, which has the N-terminal part of P3 fused to amino acids encoded by a small open reading frame (ORF) called PIPO in the +2 reading frame. We introduced point mutations that were synonymous with respect to the P3 protein but nonsynonymous with respect to the P3N-PIPO protein, and vice versa, into the chimeric viruses. Infection of plants with these mutant viruses revealed that both P3 and P3N-PIPO were involved in overcoming cyv1-mediated resistance. Moreover, P3N-PIPO quantitatively affected the virulence of Cl-no30 in cyv1 pea. Additional expression in trans of the P3N-PIPO derived from Cl-no30, using White clover mosaic virus as a vector, enabled Cl-no30 to move to systemic leaves in cyv1 pea. Susceptible pea plants infected with chimeric ClYVV possessing the P3 cistron of 90-1 Br2, and which were therefore virulent toward cyv1 pea, accumulated more P3N-PIPO than did those infected with Cl-no30, suggesting that the higher level of P3N-PIPO in infected cells contributed to the breaking of resistance by 90-1 Br2. This is the first report showing that P3N-PIPO is a virulence determinant in plants resistant to a potyvirus. PMID:23616656

P3N-PIPO, a Frameshift Product from the P3 Gene, Pleiotropically Determines the Virulence of Clover Yellow Vein Virus in both Resistant and Susceptible Peas.

PubMed

Atsumi, Go; Suzuki, Haruka; Miyashita, Yuri; Choi, Sun Hee; Hisa, Yusuke; Rihei, Shunsuke; Shimada, Ryoko; Jeon, Eun Jin; Abe, Junya; Nakahara, Kenji S; Uyeda, Ichiro

2016-08-15

Peas carrying the cyv1 recessive resistance gene are resistant to clover yellow vein virus (ClYVV) isolates No.30 (Cl-No.30) and 90-1 (Cl-90-1) but can be infected by a derivative of Cl-90-1 (Cl-90-1 Br2). The main determinant for the breaking of cyv1 resistance by Cl-90-1 Br2 is P3N-PIPO produced from the P3 gene via transcriptional slippage, and the higher level of P3N-PIPO produced by Cl-90-1 Br2 than by Cl-No.30 contributes to the breaking of resistance. Here we show that P3N-PIPO is also a major virulence determinant in susceptible peas that possess another resistance gene, Cyn1, which does not inhibit systemic infection with ClYVV but causes hypersensitive reaction-like lethal systemic cell death. We previously assumed that the susceptible pea cultivar PI 226564 has a weak allele of Cyn1 Cl-No.30 did not induce cell death, but Cl-90-1 Br2 killed the plants. Our results suggest that P3N-PIPO is recognized by Cyn1 and induces cell death. Unexpectedly, heterologously strongly expressed P3N-PIPO of Cl-No.30 appears to be recognized by Cyn1 in PI 226564. The level of P3N-PIPO accumulation from the P3 gene of Cl-No.30 was significantly lower than that of Cl-90-1 Br2 in a Nicotiana benthamiana transient assay. Therefore, Cyn1-mediated cell death also appears to be determined by the level of P3N-PIPO. The more efficiently a ClYVV isolate broke cyv1 resistance, the more it induced cell death systemically (resulting in a loss of the environment for virus accumulation) in susceptible peas carrying Cyn1, suggesting that antagonistic pleiotropy of P3N-PIPO controls the resistance breaking of ClYVV. Control of plant viral disease has relied on the use of resistant cultivars; however, emerging mutant viruses have broken many types of resistance. Recently, we revealed that Cl-90-1 Br2 breaks the recessive resistance conferred by cyv1, mainly by accumulating a higher level of P3N-PIPO than that of the nonbreaking isolate Cl-No.30. Here we show that a susceptible pea line recognized the increased amount of P3N-PIPO produced by Cl-90-1 Br2 and activated the salicylic acid-mediated defense pathway, inducing lethal systemic cell death. We found a gradation of virulence among ClYVV isolates in a cyv1-carrying pea line and two susceptible pea lines. This study suggests a trade-off between breaking of recessive resistance (cyv1) and host viability; the latter is presumably regulated by the dominant Cyn1 gene, which may impose evolutionary constraints upon P3N-PIPO for overcoming resistance. We propose a working model of the host strategy to sustain the durability of resistance and control fast-evolving viruses. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

The role of counter ions in nano-hematite synthesis: Implications for surface area and selenium adsorption capacity.

PubMed

Lounsbury, Amanda W; Yamani, Jamila S; Johnston, Chad P; Larese-Casanova, Philip; Zimmerman, Julie B

2016-06-05

Nano metal oxides are of interest for aqueous selenium (Se) remediation, and as such, nano-hematite (nα-Fe2O3) was examined for use as a Se adsorbent. The effect of surface area on adsorption was also studied. nα-Fe2O3 particles were synthesized from Fe(NO3)3 and FeCl3 via forced hydrolysis. The resulting particles have similar sizes, morphologies, aggregate size, pore size, and PZC. The nα-Fe2O3 from FeCl3 (nα-Fe2O3-C) differs from the nα-Fe2O3 from Fe(NO3)3 (nα-Fe2O3-N) with a ∼25±2m(2)/g greater surface area. Selenite Se(IV) adsorption capacity on nα-Fe2O3 has a qmax ∼17mg/g for the freeze-dried and re-suspended nα-Fe2O3. The Δqmax for nα-Fe2O3 from Fe(NO3)3 and FeCl3 that remained in suspension was 4.6mg/g. For selenate Se(VI), the freeze-dried and re-suspended particles realize a Δqmax= 1.5mg/g for nα-Fe2O3 from Fe(NO3)3 and FeCl3. The nα-Fe2O3 from Fe(NO3)3 and FeCl3 that remained in suspension demonstrated Se(VI) Δqmax=5.4mg/g. In situ ATR-FTIR isotherm measurements completed for Se(VI) at a pH 6 suggest that Se(VI) forms primarily outer-sphere complexes with nα-Fe2O3 synthesized from both salts. Copyright © 2016 Elsevier B.V. All rights reserved.

Lasagna-type arrays with halide-nitromethane cluster filling. The first recognition of the Hal(-)···HCH2NO2 (Hal = Cl, Br, I) hydrogen bonding.

PubMed

Gushchin, Pavel V; Kuznetsov, Maxim L; Wang, Qian; Karasik, Andrey A; Haukka, Matti; Starova, Galina L; Kukushkin, Vadim Yu

2012-06-21

The previously predicted ability of the methyl group of nitromethane to form hydrogen bonding with halides is now confirmed experimentally based on X-ray data of novel nitromethane solvates followed by theoretical ab initio calculations at the MP2 level of theory. The cationic (1,3,5-triazapentadiene)Pt(II) complexes [Pt{HN=C(NC(5)H(10))N(Ph)C(NH(2))=NPh}(2)](Cl)(2), [1](Hal)(2) (Hal = Cl, Br, I), and [Pt{HN=C(NC(4)H(8)O)N(Ph)C(NH(2))=NPh}(2)](Cl)(2), [2](Cl)(2), were crystallized from MeNO(2)-containing systems providing nitromethane solvates studied by X-ray diffraction. In the crystal structure of [1][(Hal)(2)(MeNO(2))(2)] (Hal = Cl, Br, I) and [2][(Cl)(2)(MeNO(2))(2)], the solvated MeNO(2) molecules occupy vacant spaces between lasagna-type layers and connect to the Hal(-) ion through a weak hydrogen bridge via the H atom of the methyl thus forming, by means of the Hal(-)···HCH(2)NO(2) contact, the halide-nitromethane cluster "filling". The quantum-chemical calculations demonstrated that the short distance between the Hal(-) anion and the hydrogen atom of nitromethane in clusters [1][(Hal)(2)(MeNO(2))(2)] and [2][(Cl)(2)(MeNO(2))(2)] is not just a consequence of the packing effect but a result of the moderately strong hydrogen bonding.

Tripodal polyphosphine ligands as inductors of chelate ring-opening processes in mononuclear palladium(II) and platinum(II) compounds. The X-ray crystal structure of two derivatives containing dangling phosphorus.

PubMed

Fernández-Anca, Damián; García-Seijo, M Inés; García-Fernández, M Esther

2010-03-07

The reaction of NP(3) (tris[2-(diphenylphosphino)ethyl]amine and PP(3) (tris[2-(diphenylphosphino)ethyl]phosphine) with the five-coordinate complexes [PdCl(NP(3))]Cl (1) and [MX(PP(3))]X [M = Pd: X = Cl(2), Br(3), I(4); M = Pt: X = Cl(5), Br(6), I(7)], respectively, followed by (31)P{(1)H}NMR when X = Cl, led to the formation of unprecedented four-coordinate halides in a 1 : 2 metal to ligand ratio, [M(AP(3))(2)]X(2) [A = N, M = Pd: X = Cl(8); A = P, M = Pd: X = Cl(9), Br(10), I(11); A = P, M = Pt: X = Cl(12), Br(13), I (14)], containing reactive dangling phosphorus. Given the non characterised precursors [M(ONO(2))(PP(3))](NO(3))], the interaction between the heteronuclear species [MAg(NO(3))(3)(PP(3))] [M = Pd(15), Pt(16)] and PP(3) was explored. It was found that the addition of 1 equivalent of phosphine afforded [MAg(NO(3))(PP(3))(2)](NO(3))(2) [M = Pd(15*), Pt(16*)] containing Ag(I) bound to two dangling phosphorus while the reaction with 2 equivalents led to the complexes [M(PP(3))(2)](NO(3))(2) [M = Pd (17), Pt (18)] in coexistence with [Ag(2)(mu-PP(3))(2)](NO(3))(2). The fate of Ag(I) on the reaction of the mixed metal compounds with excess PP(3) consisted of preventing dissociation, observed in solution for halides, and acting as an assistant for crystallization. Colourless single crystals of 18 and 10, studied by X-ray diffraction, were afforded by reaction of 16 with 4 equivalents of PP(3) and from solutions of 10 in chloroform coexisting with red crystals of 3, respectively. The structures revealed the presence of dications [M(PP(3))(2)](2+) that show two five-membered chelate rings to M(II) in a square-planar arrangement and four uncoordinated phosphine arms with the counter anions being symmetrically placed at 4.431 (Br(-)) and 13.823 (NO(3)(-)) A from M(II) above and below its coordination, MP(4), plane. Complexes 9 and 12 were shown to undergo an interesting reactivity in solution versus group 11 monocations. The reactions consisted of conversions of the two five-membered chelate rings to M into three (structure I) or two (structure II) fused five-membered chelate rings, formation of species where Pt(II) retained its square-planar environment with the two dangling phosphine arms of each PP(3) bound to Cu(I) or Ag(I) (structure III) and complexes bearing distorted square-planar (P(2)MCl(2)) and presumably tetrahedral (AuP(4)+ P(2)AuCl(2)) arrangements (structure IV). The processes with Ag(I) salts also gave mixtures of I+III (chloride and nitrate) or II+III (nitrate).

A series of transition metal-organic frameworks based on a bipyridinium carboxylate ligand: Syntheses, structures and photoluminescent properties

NASA Astrophysics Data System (ADS)

Pei, Ru-Bo; Cao, Ming-Yang; Li, Lin-Ke; Dong, Xi-Yan; Zang, Shuang-Quan

2017-09-01

Based on a bipyridinium carboxylate ligand 1-(3,5-dicarboxy)-benzyl-1,2-di(pyridine-4-yl)ethylene chloride (H2L+Cl-), eight transition metal coordination polymers, namely, {[Zn(L)Cl]ṡ4H2O}n (1), {[Zn(L)H2O]ṡNO3ṡ2H2O}n (2), {[Zn(L) (H2O)]ṡ(NO3)0.5ṡ(Cl)0.5ṡ2H2O}n (3), {[Cd(L)(H2O)(NO3)]ṡ2H2O}n (4), {[Cd1.5(L) (Cl)2]ṡ2H2O}n (5), {[Cu(L)(H2O)]ṡNO3ṡH2O}n (6), {[Cu(HL)2(H2O)2]·Cl2·6H2O}n (7) and {[Ni(L)(H2O)Cl]ṡ4H2O}n (8) have been synthesized and characterized by single-crystal X-ray diffraction analyses. Complexes 1 and 8 display 2D wave-like layer structures with a 3-connected 63 topology. Complexes 2 and 6 demonstrate 3D 2-fold interpenetrating frameworks with uninodal, 3-connected (10,3)-d utp-topology. Another pair of 3D 2-fold interpenetrating frameworks 3 and 4 possess 3-connected, uninodal 103ThSi2 (ths)-topology. Complex 5 shows a 2D layer structure based on the extending of trinuclear Cd(II) subunits. Complex 7 presents 1D double-chain structure, in which the central Cu(II) ions are connected by the partially deprotonated ligand HL. Additionally, powder X-ray diffractions (PXRD) and thermogravimetric analyses of complexes 1-8, as well as the solid-state luminescent properties of d10 metal complexes 1-4 at room temperature have also been discussed.

Brines formed by multi-salt deliquescence

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

Carroll, S; Rard, J; Alai, M

2005-11-04

The FY05 Waste Package Environment testing program at Lawrence Livermore National Laboratory focused on determining the temperature, relative humidity, and solution compositions of brines formed due to the deliquescence of NaCl-KNO{sub 3}-NaNO{sub 3} and NaCl-KNO{sub 3}-NaNO{sub 3}-Ca(NO{sub 3}){sub 2} salt mixtures. Understanding the physical and chemical behavior of these brines is important because they define conditions under which brines may react with waste canister surfaces. Boiling point experiments show that NaCl-KNO{sub 3}-NaNO{sub 3} and NaCl-KNO{sub 3}-NaNO{sub 3}-Ca(NO{sub 3}){sub 2} salt mixtures form brines that transform to hydrous melts that do not truly 'dry out' until temperatures exceed 300 and 400more » C, respectively. Thus a conducting solution is present for these salt assemblages over the thermal history of the repository. The corresponding brines form at lower relative humidity at higher temperatures. The NaCl-KNO{sub 3}-NaNO{sub 3} salt mixture has a mutual deliquescence relative humidity (MDRH) of 25.9% at 120 C and 10.8% at 180 C. Similarly, the KNO{sub 3}-NaNO{sub 3} salt mixture has MDRH of 26.4% at 120 C and 20.0% at 150 C. The KNO{sub 3}-NaNO{sub 3} salt mixture salts also absorb some water (but do not appear to deliquesce) at 180 C and thus may also contribute to the transfer of electrons at interface between dust and the waste package surface. There is no experimental evidence to suggest that these brines will degas and form less deliquescent salt assemblages. Ammonium present in atmospheric and tunnel dust (as the chloride, nitrate, or sulfate) will readily decompose in the initial heating phase of the repository, and will affect subsequent behavior of the remaining salt mixture only through the removal of a stoichiometric equivalent of one or more anions. Although K-Na-NO{sub 3}-Cl brines form at high temperature and low relative humidity, these brines are dominated by nitrate, which is known to inhibit corrosion at lower temperature. Nitrate to chloride ratios of the NaCl-KNO{sub 3}-NaNO{sub 3} salt mixture are about NO{sub 3}:Cl = 19:1. The role of nitrate on corrosion at higher temperatures is addressed in a companion report (Dixit et al., 2005).« less

75 FR 8559 - 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

... the No. 3 hydraulic system can result in an uncommanded NLG retraction. The proposed AD would require... can result in an uncommanded NLG retraction. Although there have been no such cases reported on the... hydraulic system can result in an uncommanded NLG retraction. ``Although there have been no such cases...

THE INTERSECTION OF STABLE AND NON-EQUILIBRIUM TETRAHEDRA IN A MUTUAL 7- COMPONENT SYSTEM OF Li, Na, Rb, T1/Br, C1, NO$sub 3$, SO$sub 4$ (in Russian)

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

Dombrovskaya, N.S.; Khakhlova, N.V.; Alekseeva, E.A.

1961-04-21

The most stable configuration of the mixture of the 16 salts formed from Li, Na, Rb, Tl/Br, Cl, NO/sub 3/, and S0/sub 4/ con ture which however interact, resulting in a stable mixture. On the basis of exchange reactions the following equation has been derived: LiBr + NaNO/sub 3/ + RbCl + 1/2Tl/sub 2/SO/sub 4/ = 1/ 2LiSO/sub 4/ + NaCl + RbNO/sub 3/ + TlBr. In addition, several binary complexes are also formed, such as Li/sub 2/SO/sub 4/ - Rb/sub 2/SO/sub 4/, 4Li/sub 2/SO/ sub 4/ - RbSO /sub 4/, RbCl - 2Li/sub 2/SO/sub 4/ and possible others. Inmore » view of the great interest, the intersection of stable and non-equilibrium tetrahedra consisting of components of both, was experimentally studied by thermai analysis. On the basis of cooling curves the following deflection points have been observed: 453 deg C, precipitation of the first Li/sub 2/SO/sub 4/ crystals; 409 deg , coprecipitation of Li/sub 2/SO/sub 4/ and NaCl; 391 deg , coprecipitation of Li/sub 2/SO/sub 4/, NaCl snd TlBr; and finally at 107 deg , formation of the quaternary eutectic with the previously mentioned salts + RbNO/sub 3/. The microstructures of the stable and non-equilibrium phases are quite similar. (TTT)« less

Dietary Nitrate Fails to Improve 1 and 4 km Cycling Performance in Highly Trained Cyclists.

PubMed

McQuillan, Joseph A; Dulson, Deborah K; Laursen, Paul B; Kilding, Andrew E

2017-06-01

We aimed to compare the effects of two different dosing durations of dietary nitrate (NO 3 - ) supplementation on 1 and 4 km cycling time-trial performance in highly trained cyclists. In a double-blind crossover-design, nine highly trained cyclists ingested 140ml of NO 3 - -rich beetroot juice containing ~8.0mmol [NO 3 - ], or placebo, for seven days. Participants completed a range of laboratory-based trials to quantify physiological and perceptual responses and cycling performance: time-trials on day 3 and 6 (4km) and on day 4 and 7 (1km) of the supplementation period. Relative to placebo, effects following 3- and 4-days of NO 3 - supplementation were unclear for 4 (-0.8; 95% CL, ± 2.8%, p = .54) and likely harmful for 1km (-1.9; ± 2.5% CL, p = .17) time-trial mean power. Effects following 6- and 7-days of NO 3 - supplementation resulted in unclear effects for 4 (0.1; ± 2.2% CL, p = .93) and 1km (-0.9; ± 2.6%CL, p = .51) time-trial mean power. Relative to placebo, effects for 40, 50, and 60% peak power output were unclear for economy at days 3 and 6 of NO 3 - supplementation (p > .05). Dietary NO 3 - supplementation appears to be detrimental to 1km time-trial performance in highly trained cyclists after 4-days. While, extending NO 3 - dosing to ≥ 6-days reduced the magnitude of harm in both distances, overall performance in short duration cycling time-trials did not improve relative to placebo.

Heterogeneous kinetics of N2O5 reactive uptake and chlorine activation in authentic biomass burning aerosol

NASA Astrophysics Data System (ADS)

Sullivan, R. C.; Jahl, L.; Goldberger, L.; Ahern, A.; Thornton, J. A.

2017-12-01

Nitryl chloride (ClNO2) is a nighttime reservoir of NOx that is formed from the uptake of dinitrogen pentoxide (N2O5) into particles containing chloride. The formation of ClNO2 from heterogeneous reactions of N2O5(g) with authentic biomass burning aerosol has not previously been studied. We observed the rapid production of N2O5 and then ClNO2 during dark chemical transformations of biomass burning aerosol produced from a variety of fuels using both a smog chamber and an aerosol flow tube reactor. Iodide adduct chemical ionization mass spectrometry was used to measure gas phase ClNO2 and N2O5, and acetate chemical ionization mass spectrometry to measure gaseous HCl and other compounds, while a soot particle aerosol mass spectrometer measured changes in aerosol composition as chloride was displaced by nitrate. Upon the addition of ozone to the biomass burning smoke, N2O5 was always rapidly formed and ClNO2 was subsequently detected in the gas phase. During experiments at high relative humidity, we observed decreases in particulate chloride and increases in particulate nitrate which we believe are due to acid displacement of HCl(g) by HNO3 since no additional ClNO2 was produced in the gas phase. The reactive uptake probability of N2O5 on authentic biomass burning aerosol and the yield of ClNO2 were determined for the first time using chamber and flow tube experiments on smoke from biomass fuels including sawgrass, giant cutgrass, palmetto leaves, and ponderosa pine. These experiments confirm the formation of N2O5 and ClNO2 in biomass burning emissions and suggest that biomass burning is a likely source of continental ClNO2 and HCl.

Enhancement of nitrate uptake and growth of barley seedlings by calcium under saline conditions

NASA Technical Reports Server (NTRS)

Ward, M. R.; Aslam, M.; Huffaker, R. C.

1986-01-01

The effect of Ca2+ on NO3- assimilation in young barley (Hordeum vulgare L. var CM 72) seedlings in the presence and absence of NaCl was studied. Calcium increased the activity of the NO3- transporter under saline conditions, but had little effect under nonsaline conditions. Calcium decreased the induction period for the NO3- transporter under both saline and nonsaline conditions but had little effect on its apparent Km for NO3- both in the presence and absence of NaCl. The enhancement of NO3- transport by Ca2+ under saline conditions was dependent on the presence of Ca2+ in the uptake solution along with the salt, since Ca2+ had no effect when supplied before or after salinity stress. Although Mn2+ and Mg2+ enhanced NO3- uptake under saline conditions, neither was as effective as Ca2+. In longer studies, increasing the Ca2+ concentration in saline nutrient solutions resulted in increases in NO3- assimilation and seedling growth.

Chloryl nitrate - A novel product of the OClO + NO3 + M recombination

NASA Technical Reports Server (NTRS)

Friedl, Randall R.; Sander, Stanley P.; Yung, Yuk L.

1992-01-01

The products of the reaction of OClO with NO3 were investigated between 220 and 298 K using a flow reactor and infrared, visible, and ultraviolet analysis. At temperatures below 250 K new infrared and ultraviolet absorption features were observed and assigned to the novel compound chloryl nitrate (O2ClONO2). Additionally, ClO and NO2 were observed as reaction products, indicating the existence of a second reaction channel. O2ClONO2 formation predominates at temperatures below 230 K. The reaction rate constant at 220 K is estimated to be on the order of 10 exp -14 cu cm/molecule s in 1-5 Torr of helium. These observations suggest that O2ClONO2 may exist in the terrestrial stratosphere.

The Nitrate/Perchlorate Ratio on Mars As an Indicator for Habitability

NASA Astrophysics Data System (ADS)

Stern, J. C.; Sutter, B.; McKay, C. P.; Navarro-Gonzalez, R.; Freissinet, C.; Conrad, P. G.; Mahaffy, P. R.; Archer, P. D., Jr.; Ming, D. W.; Martín-Torres, J.; Zorzano, M. P.

2014-12-01

Discovery of indigenous martian nitrogen in Mars surface materials has important implications for habitability and the potential development of a nitrogen cycle at some point in martian history. The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) Curiosity Rover detected evolved nitric oxide (NO) gas during pyrolysis of scooped aeolian sediments and drilled mudstone acquired in Gale Crater. The detection of NO suggests an indigenous source of fixed nitrogen, and may indicate a mineralogical sink for atmospheric N2 in the form of nitrate. The ratio of nitrate to oxychlorine species (e.g. perchlorate) may provide insight into the extent of development of a nitrogen cycle on Mars. Nitrate and perchlorate on Earth are geochemically related in arid environments such as the Atacama Desert and the Dry Valleys of Antarctica due to their similar mobilities and deposition mechanisms [1,2]. Here, low NO3-/ClO4- molar ratios (~1000) dominate, in comparison to other places on Earth, where the main nitrate source is biological fixation of N2 to NO3-, and there is no corresponding biological source of perchlorate, resulting in much higher NO3-/ClO4- molar ratios (~10,000). The NO3-/ClO4- molar ratio is estimated to be ~ 0.05 on Mars based on SAM measurements at Gale Crater [3]. The possibility exists that perchlorate brines could leach and increase nitrate concentrations at depth, increasing the martian NO3-/ClO4- ratio in the subsurface. However, it is unknown whether terrestrial NO3-/ClO4- molar ratios could be achieved by this mechanism. Nevertheless, the low NO3-/ClO4- the ratio detected by SAM suggests that N fixation to nitrate on Mars, whether biologically mediated or abiotic, was extremely limited compared to the potentially ongoing abiotic formation and deposition of oxychlorine species on the martian surface. [1] Kounaves, S.P. et al. "Discovery of natural perchlorate in the Antarctic dry valleys and its global implications." ES&T44, no. 7 (2010): 2360-2364. [2] Lybrand, R.A., et al. "The geochemical associations of nitrate and naturally formed perchlorate in the Mojave Desert, California, USA." GCA104 (2013): 136-147. [3] Ming, D. W. et al. "Volatile and organic compositions of sedimentary rocks in Yellowknife Bay, Gale crater, Mars." Science 343, no. 6169 (2014): 1245267.

Comparison of ultraviolet absorbance and NO-chemiluminescence for ozone measurement in wildfire plumes at the Mount Bachelor Observatory

NASA Astrophysics Data System (ADS)

Gao, Honglian; Jaffe, Daniel A.

2017-10-01

The goal of this paper is to evaluate the accuracy of the commonly used ozone (O3) instrument (the ultraviolet (UV) photometer) against a Federal Reference Method (Nitric Oxide -chemiluminescence) for ozone measurement in wildfire smoke plumes. We carried out simultaneous ozone measurement with two UV O3 photometers and one nitric oxide-chemiluminescence (NO-CL) ozone detectors during wildfire season (Aug. 1-Sept. 30) in 2015 at the Mount Bachelor Observatory (MBO, 2763 m above mean sea level, Oregon, USA). The UV O3 shows good agreement and excellent correlation to NO-CL O3, with linear regression slopes close to unity and R2 of 0.92 for 1-h average data and R2 of 0.93 for O3 daily maximum 8-h average (MDA8). During this two-month period we identified 35 wildfire events. Ozone enhancements in those wildfire plumes measured by NO-CL O3 and UV O3 monitors also show good agreement and excellent linear correlation, with a slope and R2 of 1.03 and 0.86 for O3 enhancements (ΔO3) and 1.00 and 0.98 for carbon monoxide (CO)-normalized ozone enhancement ratios (ΔO3/ΔCO), respectively. Overall, the UV O3 was found to have a positive bias of 4.7 ± 2.8 ppbv compared to the NO-CL O3. The O3 bias between NO-CL O3 and UV O3 is independent of wildfire plume tracers such as CO, particulate matter (PM1), aerosol scattering, and ultrafine particles. The results demonstrate that the UV O3 absorbance method is reliable, even in highly concentrated wildfire plumes.

New half sandwich-type Ru(II) coordination compounds characterized by the fac-Ru(dmso-S)3 fragment: influence of the face-capping group on the chemical behavior and in vitro anticancer activity.

PubMed

Bratsos, Ioannis; Simonin, Camilla; Zangrando, Ennio; Gianferrara, Teresa; Bergamo, Alberta; Alessio, Enzo

2011-10-07

The Ru(II) complex fac-[RuCl(dmso-S)(3)(dmso-O)(2)][PF(6)] (P2) was found to be an excellent precursor for the facile preparation in high yield of half sandwich-type compounds of the general formula fac-[RuCl(dmso-S)(3)(N)(2)][PF(6)] (e.g. (N)(2) = 1,2-diaminoethane (en, 4), trans-1,2-diaminocyclohexane (dach, 5), or 2 NH(3) (6)). Neutral half sandwich-type compounds of the general formula fac-[RuCl(dmso-S)(3)(N-O)] where N-O is an anionic chelating ligand (e.g. N-O = picolinate (pic, 7)) are best prepared from the universal Ru(II)-dmso precursor cis-[RuCl(2)(dmso)(4)] (P1). These complexes, that were fully characterized in solution and in the solid state, are structurally similar to the anticancer organometallic compounds [Ru(η(6)-arene)(chel)Cl][PF(6)](n) but, in place of a face-capping arene, have the fac-Ru(dmso-S)(3) fragment. In contrast to what observed for the corresponding arene compounds, that rapidly hydrolyze the Cl ligand upon dissolution in water, compounds 4-6 are very stable and inert in aqueous solution. Probably their inertness is the reason why they showed no significant cytotoxicity against the MDA-MB-231 cancer cell line.

Ion chemistry and source identification of coarse and fine aerosols in an urban area of eastern central India

NASA Astrophysics Data System (ADS)

Verma, Santosh K.; Deb, Manas K.; Suzuki, Yukio; Tsai, Ying I.

2010-01-01

This work focuses on size segregated atmospheric aerosol mass concentrations and water soluble inorganic components in Chhattisgarh, the eastern central India. Investigation on the monitoring of ambient air levels of atmospheric particulates were done around a large source of primary anthropogenic particulate emissions: the industrial area and coal based power plants. Chemical characterization was carried out for aerosol samples collected in urban area, Raipur, (21°14'N, 81°38'E) of Chhattisgarh region over a period of one year, using cascade impactor. Annual mean of mass concentration for coarse (PM 2.5-10) and fine (PM 2.5) aerosols were monitored to be 238.1 ± 89.9 and 167.0 ± 75.3 µg m - 3 respectively This work deals with the seasonal variation and meteorological influences of inorganic components of the aerosols viz. NO 3-, Cl - and SO 42-, Mg 2+, Na +, K +, Ca 2+ and NH 4+. The annual mean concentration of the inorganic components were monitored to be 3.8 ± 2.5, 8.9 ± 2.7, 10.2 ± 1.5, 2.6 ± 0.6, 8.7 ± 7.2, 4.6 ± 1.8, 16.4 ± 6.9 and 0.4 ± 0.5 µg m - 3 respectively in coarse particles and 8.2 ± 7.1, 6.8 ± 3.6, 46.5 ± 32.8, 1.7 ± 0.6, 7.4 ± 3.6, 5.9 ± 3.4, 10.2 ± 2.9, and 8.8 ± 7.7 µg m - 3 respectively in fine particles, for the above ions. The average distribution of nitrate and sulphate in PM 2.5-10 were found to be 1.6 and 4.2% and in PM 2.5 were 4.9 and 27.9% respectively indicating the dominance of sulphate in both PM 2.5-10 and PM 2.5 particles. Here, industrial emission plays important role for contribution of PM 2.5 particle loading in the atmosphere. The cation-anion rational analysis indicated that the PM 2.5-10 particles were mostly neutralized and PM 2.5 particle were acidic. The major ions were mainly in the form of NaCl > CaSO 4 > K 2SO 4 > MgSO 4 > KCl > NH 4Cl > Ca(NO 3) 2 > KNO 3 > MgCl 2 > Mg(NO 3) 2 > NH 4NO 3 > (NH 4) 2SO 4 in coarse aerosol particles and (NH 4) 2SO 4 > K 2SO 4 > CaSO 4 > NaCl > NH 4NO 3 > CaCl 2 > KNO 3 > MgCl 2 > Ca(NO 3) 2 > KCl > NH 4Cl in fine particles.

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.

Removal of NO from flue gas by aqueous chlorine-dioxide scrubbing solution in a lab-scale bubbling reactor.

PubMed

Deshwal, Bal Raj; Jin, Dong Seop; Lee, Si Hyun; Moon, Seung Hyun; Jung, Jong Hyeon; Lee, Hyung Keun

2008-02-11

The present study attempts to clean up nitric oxide from the simulated flue gas using aqueous chlorine-dioxide solution in the bubbling reactor. Chlorine-dioxide is generated by chloride-chlorate process. Experiments are carried out to examine the effect of various operating variables like input NO concentration, presence of SO(2), pH of the solution and NaCl feeding rate on the NO(x) removal efficiency at 45 degrees C. Complete oxidation of nitric oxide into nitrogen dioxide occurred on passing sufficient ClO(2) gas into the scrubbing solution. NO is finally converted into nitrate and ClO(2) is reduced into chloride ions. A plausible reaction mechanism concerning NO(x) removal by ClO(2) is suggested. DeNO(x) efficiency increased slightly with the increasing input NO concentration. The presence of SO(2) improved the NO(2) absorption but pH of solution showed marginal effect on NO(2) absorption. NO(x) removal mechanism changed when medium of solution changed from acidic to alkaline. A constant NO(x) removal efficiency of about 60% has been achieved in the wide pH range of 3-11 under optimized conditions.

Fast heterogeneous N2O5 uptake and ClNO2 production in power plant and industrial plumes observed in the nocturnal residual layer over the North China Plain

NASA Astrophysics Data System (ADS)

Wang, Zhe; Wang, Weihao; Tham, Yee Jun; Li, Qinyi; Wang, Hao; Wen, Liang; Wang, Xinfeng; Wang, Tao

2017-10-01

Dinitrogen pentoxide (N2O5) and nitryl chloride (ClNO2) are key species in nocturnal tropospheric chemistry and have significant effects on particulate nitrate formation and the following day's photochemistry through chlorine radical production and NOx recycling upon photolysis of ClNO2. To better understand the roles of N2O5 and ClNO2 in the high-aerosol-loading environment of northern China, an intensive field study was carried out at a high-altitude site (Mt. Tai, 1465 m a.s.l.) in the North China Plain (NCP) during the summer of 2014. Elevated ClNO2 plumes were frequently observed in the nocturnal residual layer with a maximum mixing ratio of 2.1 ppbv (1 min), whilst N2O5 was typically present at very low levels (< 30 pptv), indicating fast heterogeneous N2O5 hydrolysis. Combined analyses of chemical characteristics and backward trajectories indicated that the ClNO2-laden air was caused by the transport of NOx-rich plumes from the coal-fired industry and power plants in the NCP. The heterogeneous N2O5 uptake coefficient (γ) and ClNO2 yield (ϕ) were estimated from steady-state analysis and observed growth rate of ClNO2. The derived γ and ϕ exhibited high variability, with means of 0.061 ± 0.025 and 0.28 ± 0.24, respectively. These values are higher than those derived from previous laboratory and field studies in other regions and cannot be well characterized by model parameterizations. Fast heterogeneous N2O5 reactions dominated the nocturnal NOx loss in the residual layer over this region and contributed to substantial nitrate formation of up to 17 µg m-3. The estimated nocturnal nitrate formation rates ranged from 0.2 to 4.8 µg m-3 h-1 in various plumes, with a mean of 2.2 ± 1.4 µg m-3 h-1. The results demonstrate the significance of heterogeneous N2O5 reactivity and chlorine activation in the NCP, and their unique and universal roles in fine aerosol formation and NOx transformation, and thus their potential impacts on regional haze pollution in northern China.

Purification and some properties of rose (Fructus cynosbati) hips invertase.

PubMed

Sacan, Ozlem; Yanardag, Refiye

2012-04-01

Invertase was purified from rose (Fructus cynosbati) hips by ammonium sulfate fractionation and hydroxyapatite column chromatography. The enzyme was obtained with a yield of 4.25% and about 10.48-fold purification and had a specific activity of 8.59 U/mg protein. The molecular mass of invertase was estimated to be 66.51 kDa by PAGE and 34 kDa by SDS-PAGE, indicating that the native enzyme was a homodimer. The enzyme was a glycoprotein and contained 5.86% carbohydrate. The K(m) for sucrose was 14.55 mM and the optimum pH and temperature of the enzyme were 4.5 and 40 degrees C, respectively. Sucrose was the most preferred substrate of the enzyme. The enzyme also hydrolyzed D(+) raffinose, D(+) trehalose and inulin (activity 39.88, 8.12 and 4.94%, respectively of that of sucrose), while D(+) lactose, cellobiose and D(+) maltose showed no effect on the enzyme. The substrate specificity was consistent with that for a beta-fructofuranoside, which is the most popular type in the higher plants. The enzyme was completely inhibited by HgCl2, MnCl2, MnSO4, FeCl3, Pb(NO3)2, ammonium heptamolybdate, iodoacetamide and pyridoxine hydrochloride. It was also inhibited by Ba(NO3)2 (86.32%), NH4Cl (84.91%), MgCl2 (74.45%), urea (71.63%), I2 (69.64%), LiCl (64.99%), BaCl2 (50.30%), Mg(NO3)2 (49.90%), CrCl3 (31.90%) and CuSO4 (21.45%) and but was activated by Tris (73.99%) and methionine (12.47%).

Specific ion-protein interactions dictate solubility behavior of a monoclonal antibody at low salt concentrations.

PubMed

Zhang, Le; Zhang, Jifeng

2012-09-04

The perturbation of salt ions on the solubility of a monoclonal antibody was systematically studied at various pHs in Na(2)SO(4), NaNO(3), NaCl, NaF, MgSO(4), Mg(NO(3))(2) and MgCl(2) solutions below 350 mM. At pH 7.1, close to the pI, all of the salts increased the solubility of the antibody, following the order of SO(4)(2-) > NO(3)(-) > Cl(-) > F(-) for anions and Mg(2+) > Na(+) for cations. At pH 5.3 where the antibody had a net positive charge, the anions initially followed the order of SO(4)(2-) > NO(3)(-) > Cl(-) > F(-) for effectiveness in reducing the solubility and then switched to increasing the solubility retaining the same order. Furthermore, the antibody was more soluble in the Mg(2+) salt solutions than in the corresponding Na(+) salt solutions with the same anion. At pH 9.0 where the antibody had a net negative charge, an initial decrease in the protein solubility was observed in the solutions of the Mg(2+) salts and NaF, but not in the rest of the Na(+) salt solutions. Then, the solubility of the antibody was increased by the anions in the order of SO(4)(2-) > NO(3)(-) > Cl(-) > F(-). The above complex behavior is explained based on the ability of both cation and anion from a salt to modulate protein-protein interactions through their specific binding to the protein surface.

Unusual ion UO(4)(-) formed upon collision induced dissociation of [UO(2)(NO(3))(3)](-), [UO(2)(ClO(4))(3)](-), [UO(2)(CH(3)COO)(3)](-) ions.

PubMed

Sokalska, Marzena; Prussakowska, Małgorzata; Hoffmann, Marcin; Gierczyk, Błazej; Frański, Rafał

2010-10-01

The following ions [UO(2)(NO(3))(3)](-), [UO(2)(ClO(4))(3)](-), [UO(2)(CH(3)COO)(3)](-) were generated from respective salts (UO(2)(NO(3))(2), UO(2)(ClO(4))(3), UO(2)(CH(3)COO)(2)) by laser desorption/ionization (LDI). Collision induced dissociation of the ions has led, among others, to the formation of UO(4)(-) ion (m/z 302). The undertaken quantum mechanical calculations showed this ion is most likely to possess square planar geometry as suggested by MP2 results or strongly deformed geometry in between tetrahedral and square planar as indicated by DFT results. Interestingly, geometrical parameters and analysis of electron density suggest it is an U(VI) compound, in which oxygen atoms bear unpaired electron and negative charge. Copyright © 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

Global patterns and environmental controls of perchlorate and nitrate co-occurrence in arid and semi-arid environments

USGS Publications Warehouse

Jackson, W Andrew; Böhlke, John Karl; Andraski, Brian J.; Fahlquist, Lynne S.; Bexfield, Laura M.; Eckardt, Frank D.; Gates, John B.; Davila, Alfonso F.; McKay, Christopher P.; Rao, Balaji; Sevanthi, Ritesh; Rajagopalan, Srinath; Estrada, Nubia; Sturchio, Neil C.; Hatzinger, Paul B.; Anderson, Todd A.; Orris, Greta J.; Betancourt, Julio L.; Stonestrom, David A.; Latorre, Claudio; Li, Yanhe; Harvey, Gregory J.

2015-01-01

Natural perchlorate (ClO4−) is of increasing interest due to its wide-spread occurrence on Earth and Mars, yet little information exists on the relative abundance of ClO4− compared to other major anions, its stability, or long-term variations in production that may impact the observed distributions. Our objectives were to evaluate the occurrence and fate of ClO4− in groundwater and soils/caliche in arid and semi-arid environments (southwestern United States, southern Africa, United Arab Emirates, China, Antarctica, and Chile) and the relationship of ClO4− to the more well-studied atmospherically deposited anions NO3−and Cl− as a means to understand the prevalent processes that affect the accumulation of these species over various time scales. ClO4− is globally distributed in soil and groundwater in arid and semi-arid regions on Earth at concentrations ranging from 10−1to 106 μg/kg. Generally, the ClO4− concentration in these regions increases with aridity index, but also depends on the duration of arid conditions. In many arid and semi-arid areas, NO3− and ClO4− co-occur at molar ratios (NO3−/ClO4−) that vary between ∼104and 105. We hypothesize that atmospheric deposition ratios are largely preserved in hyper-arid areas that support little or no biological activity (e.g. plants or bacteria), but can be altered in areas with more active biological processes including N2 fixation, N mineralization, nitrification, denitrification, and microbial ClO4− reduction, as indicated in part by NO3− isotope data. In contrast, much larger ranges of Cl−/ClO4− and Cl−/NO3−ratios indicate Cl− varies independently from both ClO4− and NO3−. The general lack of correlation between Cl− and ClO4− or NO3− implies that Cl− is not a good indicator of co-deposition and should be used with care when interpreting oxyanion cycling in arid systems. The Atacama Desert appears to be unique compared to all other terrestrial locations having a NO3−/ClO4− molar ratio ∼103. The relative enrichment in ClO4−compared to Cl− or NO3− and unique isotopic composition of Atacama ClO4− may reflect either additional in-situ production mechanism(s) or higher relative atmospheric production rates in that specific region or in the geological past. Elevated concentrations of ClO4− reported on the surface of Mars, and its enrichment with respect to Cl− and NO3−, could reveal important clues regarding the climatic, hydrologic, and potentially biologic evolution of that planet. Given the highly conserved ratio of NO3−/ClO4− in non-biologically active areas on Earth, it may be possible to use alterations of this ratio as a biomarker on Mars and for interpreting major anion cycles and processes on both Mars and Earth, particularly with respect to the less-conserved NO3− pool terrestrially.

Ionic composition of TSP and PM 2.5 during dust storms and air pollution episodes at Xi'an, China

NASA Astrophysics Data System (ADS)

Shen, Zhenxing; Cao, Junji; Arimoto, Richard; Han, Zhiwei; Zhang, Renjian; Han, Yuemei; Liu, Suixin; Okuda, Tomoaki; Nakao, Shunsuke; Tanaka, Shigeru

TSP and PM 2.5 samples were collected at Xi'an, China during dust storms (DSs) and several types of pollution events, including haze, biomass burning, and firework displays. Aerosol mass concentrations were up to 2 times higher during the particulate matter (PM) events than on normal days (NDs), and all types of PM led to decreased visibility. Water-soluble ions (Na +, NH 4+, K +, Mg 2+, Ca 2+, F -, Cl -, NO 3-, and SO 42-). were major aerosol components during the pollution episodes, but their concentrations were lower during DSs. NH 4+, K +, F -, Cl -, NO 3-, and SO 42- were more abundant in PM 2.5 than TSP but the opposite was true for Mg 2+ and Ca 2+. PM collected on hazy days was enriched with secondary species (NH 4+, NO 3-, and SO 42) while PM from straw combustion showed high K + and Cl -. Firework displays caused increases in K + and also enrichments of NO 3- relative to SO 42-. During DSs, the concentrations of secondary aerosol components were low, but Ca 2+ was abundant. Ion balance calculations indicate that PM from haze and straw combustion was acidic while the DSs samples were alkaline and the fireworks' PM was close to neutral. Ion ratios (SO 42-/K +, NO 3-/SO 42-, and Cl -/K +) proved effective as indicators for different pollution episodes.

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.

Characteristics of injury and recovery of net NO3- transport of barley seedlings from treatments of NaCl

NASA Technical Reports Server (NTRS)

Klobus, G.; Ward, M. R.; Huffaker, R. C.

1988-01-01

The nature of the injury and recovery of nitrate uptake (net uptake) from NaCl stress in young barley (Hordeum vulgare L, var CM 72) seedlings was investigated. Nitrate uptake was inhibited rapidly by NaCl, within 1 minute after exposure to 200 millimolar NaCl. The duration of exposure to saline conditions determined the time of recovery of NO3- uptake from NaCl stress. Recovery was dependent on the presence of NO3- and was inhibited by cycloheximide, 6-methylpurine, and cerulenin, respective inhibitors of protein, RNA, and sterol/fatty acid synthesis. These inhibitors also prevented the induction of the NO3- uptake system in uninduced seedlings. Uninduced seedlings exhibited endogenous NO3- transport activity that appeared to be constitutive. This constitutive activity was also inhibited by NaCl. Recovery of constitutive NO3- uptake did not require the presence of NO3-.

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.

Stable Isotope Analysis of Chlorate

NASA Astrophysics Data System (ADS)

Brundrett, M.; Jackson, W. A.; Sturchio, N. C.; Bohlke, J. K.; Hatzinger, P.

2016-12-01

Studies have confirmed the presence of chlorate (ClO3-) throughout terrestrial and extraterrestrial systems generally in excess of perchlorate (ClO4-) [1, 2]. ClO3- occurrence, production, and post depositional transformation has significant implications to our understanding of atmospheric Cl cycling and potential biogeochemical reactions on Earth and Mars. The isotopic composition of oxyanions can be used to evaluate their production mechanisms and post-depositional alteration [3, 4]. However, no information is available on the natural isotopic composition of ClO3-. The objective of this study was to develop a method to measure the stable isotope composition (δ18O, δ17O and δ37Cl) of ClO3- and to determine the isotopic composition of ClO3- in natural desert salt accumulations that have been studied previously for NO3- and ClO4- isotopic composition. The process of ClO3- purification and analysis of δ18O, δ 17O and δ37Cl is problematic but has recently been resolved by adapting previously published methods for ClO4-. Competitive anions (e.g. NO3-, Cl-, ClO4-, and SO4-2) are removed through a series of processes including biological reduction, solid phase extraction, and anion or cation exchange. Initial results for control samples treated with the above method have a maximum variation of ± 2 ‰. These methods are being applied to representative samples to determine if various sources of natural and synthetic ClO3- have distinctive isotopic compositions, as reported previously for ClO4- [3, 4]. Establishing the range of isotopic composition of natural ClO3- also could provide information about atmospheric ClO3- production mechanisms and post-depositional processing, with implications for the atmospheric chemistry of oxychlorine compounds and the global biogeochemical cycling of Cl. [1] Jackson et al. (2015) EPSL 430, 470-476. [2] Rao et al. (2010) ES&T 44, 8429-8434. [3] Jackson et al. (2010) ES&T 44, 4869-4876. [4] Bao and Gu (2004) ES&T 38, 5073-5077.

Inorganic chemistry: Direct syntheses from pure liquid SO3 and from trivalent and pentavalent nitrogen derivatives

NASA Technical Reports Server (NTRS)

Vandorpe, B.; Heubel, J.

1977-01-01

From pure liquid SO3 direct synthesis reactions were carried out with N2O5, NO2Cl, NOCl which yielded N2O54SO3, 3SO3, 2SO3-NO2Cl2SO3-NOCl2SO3 and NOCl2SO3, the latter being obtained for the first time in the pure state. In all cases the crystallized product was obtained by separating the constituents of the mixture and then going through a single viscous liquid phase.

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.

Effects of electron acceptors on soluble reactive phosphorus in the overlying water during algal decomposition.

PubMed

Wang, Jinzhi; Jiang, Xia; Zheng, Binghui; Niu, Yuan; Wang, Kun; Wang, Wenwen; Kardol, Paul

2015-12-01

Endogenous phosphorus (P) release from sediments is an important factor to cause eutrophication and, hence, algal bloom in lakes in China. Algal decomposition depletes dissolved oxygen (DO) and causes anaerobic conditions and therefore increases P release from sediments. As sediment P release is dependent on the iron (Fe) cycle, electron acceptors (e.g., NO3 (-), SO4 (2-), and Mn(4+)) can be utilized to suppress the reduction of Fe(3+) under anaerobic conditions and, as such, have the potential to impair the release of sediment P. Here, we used a laboratory experiment to test the effects of FeCl3, MnO2, and KNO3 on soluble reactive phosphorus (SRP) concentration and related chemical variables in the overlying water column during algal decomposition at different algal densities. Results showed that algal decomposition significantly depleted DO and thereby increased sediment Fe-bound P release. Compared with the control, addition of FeCl3 significantly decreased water SRP concentration through inhibiting sediment P release. Compared with FeCl3, addition of MnO2 has less potential to suppress sediment P release during algal decomposition. Algal decomposition has the potential for NO3 (-) removal from aquatic ecosystem through denitrification and by that alleviates the suppressing role of NO3 (-) on sediment P release. Our results indicated that FeCl3 and MnO2 could be efficient in reducing sediment P release during algal decomposition, with the strongest effect found for FeCl3; large amounts of NO3 (-) were removed from the aquatic ecosystem through denitrification during algal decomposition. Moreover, the amounts of NO3 (-) removal increased with increasing algal density.

An intercomparison of airborne nitrogen dioxide instruments

NASA Technical Reports Server (NTRS)

Gregory, G. L.; Hoell, J. M., Jr.; Carroll, M. A.; Ridley, B. A.; Davis, D. D.; Bradshaw, J.; Rodgers, M. O.; Sandholm, S. T.; Schiff, H. I.; Torres, A. L.

1990-01-01

Results on NO2 instruments are reported from the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 (CITE 2) program in summer 1986. The instruments tested were (1) a two-photon LIF system using a laser for NO2-NO photolysis, (2) a chemiluminescence (CL) detector using FeSO4 for NO2-NO conversion, (3) a CL detector using an arc lamp for NO2-NO photolysis, and (4) a tunable-laser-diode multipath-absorption system. The procedures for the CITE 2 ground-based and flight tests are described in detail, and the results are presented in extensive graphs. Instrument (2) was eliminated because the FeSO4 converted atmospheric PAN to NO, resulting in spuriously high NO2 values. The remaining instruments gave readings in 30-40-percent agreement at NO2 mixing ratios of 100-200 parts per trillion by volume (pptv). At ratios below 50 pptv, the correlation among the measurements was very poor, with a tendency for system (4) to give higher values than (1) or (3).

Reactive Nitrogen Multiphase Chemistry and Chlorine Activation on Authentic Biomass Burning Aerosol

NASA Astrophysics Data System (ADS)

Goldberger, Lexie

Biomass burning is both a major source of particulate matter and reactive nitrogen oxide radicals, yet the rate and products of the multiphase chemistry between the two has not been well studied. Nitryl chloride (ClNO2), formed by the multiphase reaction of dinitrogen pentoxide (N2O 5) on chloride-containing particles, is known to occur in polluted marine environments where it contributes significantly to the oxidant budget. Since the observation of ClNO2 levels in a moderately polluted region far from the coast, there has been motivation to determine the source of particulate chloride, postulated as the limiting ingredient to ClNO2 formation. Using a smog chamber reactor at Carnegie Mellon University coupled to a biomass combustion chamber with controlled particle and gas injection, we simulated the nocturnal evolution of N2O5 in biomass burning plumes mixed with ozone. A range of authentic fuel types, including saw grass, cut grass, and white European birch were burned in the combustion chamber and a portion of the smoke plume was then mixed into the 12 m3 chamber, where it was exposed to 70-150 ppb of ozone and relative humidity ranging from 0-60% in the dark. Gaseous N 2O5, nitric acid (HNO3), ClNO 2, Cl2, and HCl were monitored using a high resolution time of flight iodide adduct chemical ionization mass spectrometer, and particle size distributions and composition were monitored continuously with an SMPS and a Soot-Particle Aerosol Mass Spectrometer among other instruments. With chemical mechanism modeling I attempt to abstract N2O 5 uptake coefficients as well as molar yields of ClNO2 and report correlated changes in Cl2 and HCl. I analyze dependences on combustion fuel type. These results suggest a potentially important impact of chlorine atom initiated oxidation in biomass burning plumes. The uptake of N2O5 and yields of ClNO2, Cl2, and HCl determined from this study will allow for more robust parameterizations of these compounds in atmospheric models.

Crystal structures of three 3-chloro-3-methyl-2,6-di­aryl­piperidin-4-ones

PubMed Central

Arulraj, R.; Sivakumar, S.; Kaur, Manpreet; Jasinski, Jerry P.

2017-01-01

The syntheses and crystal structure of 3-chloro-3-methyl-r-2,c-6-di­phenyl­piperidin-4-one, C18H18ClNO, (I), 3-chloro-3-methyl-r-2,c-6-di-p-tolyl­piperidin-4-one, C20H22ClNO, (II), and 3-chloro-3-methyl-r-2,c-6-bis­(4-chloro­phen­yl)piperidin-4-one, C18H16Cl3NO, (III), are described. In each structure, the piperidine ring adopts a chair conformation and dihedral angles between the mean planes of the phenyl rings are 58.4 (2), 73.5 (5) and 78.6 (2)° in (I), (II) and (III), respectively. In the crystals, mol­ecules are linked into C(6) chains by weak N—H⋯O hydrogen bonds and C—H⋯π inter­actions are also observed. PMID:28217321

UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation.

PubMed

Hull, Emily A; West, Aaron C; Pestovsky, Oleg; Kristian, Kathleen E; Ellern, Arkady; Dunne, James F; Carraher, Jack M; Bakac, Andreja; Windus, Theresa L

2015-02-28

Transition metal complexes (NH3)5CoX(2+) (X = CH3, Cl) and L(H2O)MX(2+), where M = Rh or Co, X = CH3, NO, or Cl, and L is a macrocyclic N4 ligand are examined by both experiment and computation to better understand their electronic spectra and associated photochemistry. Specifically, irradiation into weak visible bands of nitrosyl and alkyl complexes (NH3)5CoCH3(2+) and L(H2O)M(III)X(2+) (X = CH3 or NO) leads to photohomolysis that generates the divalent metal complex and ˙CH3 or ˙NO, respectively. On the other hand, when X = halide or NO2, visible light photolysis leads to dissociation of X(-) and/or cis/trans isomerization. Computations show that visible bands for alkyl and nitrosyl complexes involve transitions from M-X bonding orbitals and/or metal d orbitals to M-X antibonding orbitals. In contrast, complexes with X = Cl or NO2 exhibit only d-d bands in the visible, so that homolytic cleavage of the M-X bond requires UV photolysis. UV-Vis spectra are not significantly dependent on the structure of the equatorial ligands, as shown by similar spectral features for (NH3)5CoCH3(2+) and L(1)(H2O)CoCH3(2+).

UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation

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

Hull, Emily A.; West, Aaron C.; Pestovsky, Oleg

2015-01-22

In this paper, transition metal complexes (NH 3) 5CoX2 + (X = CH 3, Cl) and L(H 2O)MX 2+, where M = Rh or Co, X = CH 3, NO, or Cl, and L is a macrocyclic N 4 ligand are examined by both experiment and computation to better understand their electronic spectra and associated photochemistry. Specifically, irradiation into weak visible bands of nitrosyl and alkyl complexes (NH 3) 5CoCH 3 2+ and L(H 2O)M IIIX 2+ (X = CH 3 or NO) leads to photohomolysis that generates the divalent metal complex and ˙CH3 or ˙NO, respectively. On the othermore » hand, when X = halide or NO 2, visible light photolysis leads to dissociation of X – and/or cis/trans isomerization. Computations show that visible bands for alkyl and nitrosyl complexes involve transitions from M–X bonding orbitals and/or metal d orbitals to M–X antibonding orbitals. In contrast, complexes with X = Cl or NO 2 exhibit only d–d bands in the visible, so that homolytic cleavage of the M–X bond requires UV photolysis. UV-Vis spectra are not significantly dependent on the structure of the equatorial ligands, as shown by similar spectral features for (NH 3) 5CoCH 3 2+ and L 1(H 2O)CoCH 3 2+.« less

The ion chemistry, seasonal cycle, and sources of PM 2.5 and TSP aerosol in Shanghai

NASA Astrophysics Data System (ADS)

Wang, Ying; Zhuang, Guoshun; Zhang, Xingying; Huang, Kan; Xu, Chang; Tang, Aohan; Chen, Jianmin; An, Zhisheng

Daily total suspended particulate (TSP), particle size smaller than 100 μm and particle size smaller than 2.5 μm (PM 2.5) aerosol samples were collected at two sites in Shanghai in four seasons from September 2003 to January 2005. Concentrations of the water-soluble ions (SO 42-, NO 3-, Cl -, F -, PO 43-, HCOO -, CH 3COO -, NO 2-, MSA, C 2O 42-, NH 4+, Ca 2+, Na +, K +, Mg 2+) were measured for a total of 202 samples. Daily TSP and PM 2.5 mass concentrations ranged from 66.1 to 666.8 μg m -3 and 17.8 to 217.9 μg m -3, with annual average concentrations of 230.5 and 94.6 μg m -3, respectively. The sum of ions contributed an average of 26% and 32% of TSP and PM 2.5 mass concentrations, respectively. In PM 2.5, the concentration of the major ions followed the order of SO 42->NO 3->NH 4+>Cl ->Ca 2+>K +, while in TSP was SO 42->NO 3->Cl ->Ca 2+>NH 4+>Na +. These major ions were mainly in the form of (NH 4) 2SO 4, Ca(NO 3) 2, CaCl 2, and CaSO 4 in aerosol particles. The aerosol was slightly acidic in the fine particle size range, and alkaline in the coarse mode. Seasonal variation of ion concentrations was significant, with the highest concentrations observed in winter and spring and the lowest in summer and autumn. Three types of air masses, i.e. marine, mixing, and continental, were frequently observed, and their distribution in four seasons might result in the clear seasonal variation. It is Shanghai that has the highest NO 3-/SO 42- value among all of those cities in China, indicating that as the biggest city in China the mobile source of the air pollution becomes more and more predominant. However, stationary emissions were still the dominant source in Shanghai indicated by the NO 3-/SO 42- ratio of lower than 1. The formation of NO 3- was largely from the gas-phase photochemical reaction in the cold season, and from the heterogeneous reaction in the warm season, while the formation of SO 42- might be from the heterogeneous reaction in the entire year round. NH 4+, K +, Cl -, NO 3-, and SO 42- were mainly influenced by the anthropogenic emissions in land, meanwhile Cl - and SO 42- might be partly influenced by the sea. Na +, Mg 2+, and Ca 2+ were derived from both inland crustal and marine sources. Chloride depletion was found especially in summer. The air pollution in Shanghai has proved to be under the influence of both the local emissions and the long-range transport from outside areas.

Atmospheric chemistry of C 2F 5CHO: reaction with Cl atoms and OH radicals, IR spectrum of C 2F 5C(O)O 2NO 2

NASA Astrophysics Data System (ADS)

Sulbaek Andersen, M. P.; Hurley, M. D.; Wallington, T. J.; Ball, J. C.; Martin, J. W.; Ellis, D. A.; Mabury, S. A.; Nielsen, O. J.

2003-09-01

Smog chamber/FTIR techniques were used to measure k(Cl + C 2F 5CHO)=(1.96 ± 0.28) × 10 -12 and k(OH + C 2F 5CHO)=(5.26 ± 0.80) × 10 -13 cm 3 molecule -1 s -1 in 700 Torr of N 2 or air at 296 ± 2 K. The Cl initiated oxidation of C 2F 5CHO in the presence of NO in air diluent gave COF 2, CF 3ONO 2, and C 2F 5C(O)O 2NO 2 in molar yields of 180 ± 19%, 6.1 ± 0.6%, and 1.0 ± 0.3%, respectively. The IR spectrum for C 2F 5C(O)O 2NO 2 is reported. Results are discussed with respect to the potential for the atmospheric degradation of fluorinated aldehydes, C nF 2 n+1 CHO, to contribute to the observed environmental burden of fluorinated carboxylic acids, C nF 2 n+1 C(O)OH.

New treatment method for boron in aqueous solutions using Mg-Al layered double hydroxide: Kinetics and equilibrium studies.

PubMed

Kameda, Tomohito; Oba, Jumpei; Yoshioka, Toshiaki

2015-08-15

Mg-Al layered double hydroxides (LDHs) intercalated with NO3(-) (NO3 · Mg - Al LDHs) and with Cl(-) (Cl · Mg - Al LDHs) were found to take up boron from aqueous solutions. Boron was removed by anion exchange of B(OH)4(-) in solution with NO3(-) and Cl(-) intercalated in the interlayer of the LDH. Using three times the stoichiometric quantity of NO3 · Mg-Al LDH, the residual concentration of B decreased from 100 to 1.9 mg L(-1) in 120 min. Using five times the stoichiometric quantity of Cl · Mg - Al LDH, the residual concentration of B decreased from 100 to 5.6 mg L(-1) in 120 min. It must be emphasized that, in both cases, the residual concentration of B was less than the effluent standards in Japan (10 mg L(-1)). The rate-determining step of B removal by the NO3 · Mg - Al and Cl · Mg - Al LDHs was found to be chemical adsorption involving anion exchange of B(OH)4(-) with intercalated NO3(-) and Cl(-). The removal of B was well described by a pseudo second-order kinetic equation. The adsorption of B by NO3 · Mg - Al LDH and Cl · Mg - Al LDH followed a Langmuir-type adsorption. The values of the maximum adsorption and the equilibrium adsorption constant were 3.6 mmol g(-1) and 1.7, respectively, for NO3 · Mg - Al LDH, and 3.8 mmol g(-1) and 0.7, respectively, for Cl · Mg-Al LDH. The B(OH)4(-) in B(OH)4 · Mg - Al LDH produced by removal of B was found to undergo anion exchange with NO3(-) and Cl(-) in solution. The NO3 · Mg - Al and Cl · Mg - Al LDHs obtained after this regeneration treatment were able to remove B from aqueous solutions, indicating the possibility of recycling NO3 · Mg - Al and Cl · Mg - Al LDHs for B removal. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis, properties, and reactivity of a series of non-heme {FeNO}(7/8) complexes: implications for Fe-nitroxyl coordination.

PubMed

Sanders, Brian C; Patra, Ashis K; Harrop, Todd C

2013-01-01

The biochemical properties of nitroxyl (HNO/NO(-)) are distinct from nitric oxide (NO). Metal centers, particularly Fe, appear as suitable sites of HNO activity, both for generation and targeting. Furthermore, reduced Fe-NO(-)/Fe-HNO or {FeNO}(8) (Enemark-Feltham notation) species offer unique bonding profiles that are of fundamental importance. Given the unique chemical properties of {FeNO}(8) systems, we describe herein the synthesis and properties of {FeNO}(7) and {FeNO}(8) non-heme complexes containing pyrrole donors that display heme-like properties, namely [Fe(LN(4)(R))(NO)] (R = C(6)H(4) or Ph for 3; and R = 4,5-Cl(2)C(6)H(2) or PhCl for 4) and K[Fe(LN(4)(R))(NO)] (R = Ph for 5; R = PhCl for 6). X-ray crystallography establishes that the Fe-N-O angle is ~155° for 3, which is atypical for low-spin square-pyramidal {FeNO}(7) species. Both 3 and 4 display ν(NO) at ~1700 cm(-1) in the IR and reversible diffusion-controlled cyclic voltammograms (CVs) (E(1/2)=~-1.20 V vs. Fc/Fc(+) (ferrocene/ferrocenium redox couple) in MeCN) suggesting that the {FeNO}(8) compounds 5 and 6 are stable on the CV timescale. Reduction of 3 and 4 with stoichiometric KC(8) provided the {FeNO}(8) compounds 5 and 6 in near quantitative yield, which were characterized by the shift in ν(NO) to 1667 and ~1580 cm(-1), respectively. While the ν(NO) for 6 is consistent with FeNO reduction, the ν(NO) for 5 appears more indicative of ligand-based reduction. Additionally, 5 and 6 engage in HNO-like chemistry in their reactions with ferric porphyrins [Fe(III)(TPP)X] (TPP = tetraphenylporphyrin; X = Cl(-), OTf(-) (trifluoromethanesulfonate anion or CF(3)SO(3)(-))) to form [Fe(TPP)NO] in stoichiometric yield via reductive nitrosylation. Copyright © 2012 Elsevier Inc. All rights reserved.

Atmospheric chemistry of CF3CF═CH2 and (Z)-CF3CF═CHF: Cl and NO3 rate coefficients, Cl reaction product yields, and thermochemical calculations.

PubMed

Papadimitriou, Vassileios C; Lazarou, Yannis G; Talukdar, Ranajit K; Burkholder, James B

2011-01-20

Rate coefficients, k, for the gas-phase reactions of Cl atoms and NO(3) radicals with 2,3,3,3-tetrafluoropropene, CF(3)CF═CH(2) (HFO-1234yf), and 1,2,3,3,3-pentafluoropropene, (Z)-CF(3)CF═CHF (HFO-1225ye), are reported. Cl-atom rate coefficients were measured in the fall-off region as a function of temperature (220-380 K) and pressure (50-630 Torr; N(2), O(2), and synthetic air) using a relative rate method. The measured rate coefficients are well represented by the fall-off parameters k(0)(T) = 6.5 × 10(-28) (T/300)(-6.9) cm(6) molecule(-2) s(-1) and k(∞)(T) = 7.7 × 10(-11) (T/300)(-0.65) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and k(0)(T) = 3 × 10(-27) (T/300)(-6.5) cm(6) molecule(-2) s(-1) and k(∞)(T) = 4.15 × 10(-11) (T/300)(-0.5) cm(3) molecule(-1) s(-1) for (Z)-CF(3)C═CHF with F(c) = 0.6. Reaction product yields were measured in the presence of O(2) to be (98 ± 7)% for CF(3)C(O)F and (61 ± 4)% for HC(O)Cl in the CF(3)CF═CH(2) reaction and (108 ± 8)% for CF(3)C(O)F and (112 ± 8)% for HC(O)F in the (Z)-CF(3)CF═CHF reaction, where the quoted uncertainties are 2σ (95% confidence level) and include estimated systematic errors. NO(3) reaction rate coefficients were determined using absolute and relative rate methods. Absolute measurements yielded upper limits for both reactions between 233 and 353 K, while the relative rate measurements yielded k(3)(295 K) = (2.6 ± 0.25) × 10(-17) cm(3) molecule(-1) s(-1) and k(4)(295 K) = (4.2 ± 0.5) × 10(-18) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF, respectively. The Cl-atom reaction with CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF leads to decreases in their atmospheric lifetimes and global warming potentials and formation of a chlorine-containing product, HC(O)Cl, for CF(3)CF═CH(2). The NO(3) reaction has been shown to have a negligible impact on the atmospheric lifetimes of CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF. The energetics for the reaction of Cl, NO(3), and OH with CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF in the presence of O(2) were investigated using density functional theory (DFT).

Insertion-release of guest species and ionic conduction in polyoxometalate solids with a layer-like Anderson structure

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

Naruke, Haruo, E-mail: hnaruke@res.titech.ac.j; Kajitani, Naoyuki; Konya, Takayuki

The precipitation of Na{sup +} and K{sup +} mixed salts of Anderson type [SbW{sub 6}O{sub 24}]{sup 7-} by addition of excess of NaNO{sub 3} and NaCl yielded polycrystalline powders of Na{sub 2.5}K{sub 5.3}[SbW{sub 6}O{sub 24}](NO{sub 3}){sub 0.8}.12H{sub 2}O (1) and Na{sub 2}K{sub 5.35}[SbW{sub 6}O{sub 24}]Cl{sub 0.35}.12H{sub 2}O (2), respectively. The two compounds are isomorphous and exhibit a layer-like Anderson (LLA) type structure, which consists of [SbW{sub 6}O{sub 24}]{sup 7-}-containing layers and interstitial Na{sup +}, K{sup +}, NO{sub 3}{sup -} or Cl{sup -}, and water O atoms. Recrystallization of 1 and 2 from hot water yielded Na{sub 2}K{sub 5.4}[SbW{sub 6}O{sub 24}](NO{submore » 3}){sub 0.4}.12H{sub 2}O (1-recry) and Na{sub 2}K{sub 5.25}[SbW{sub 6}O{sub 24}]Cl{sub 0.25}.12H{sub 2}O (2-recry) as a result of partial release of NO{sub 3}{sup -} and Cl{sup -} (and Na{sup +} and K{sup +} for charge compensation). Dehydration of 1 and 2 at 400 and 500 {sup o}C (1-dehyd400 and 2-dehyd500) caused a shrinkage of lattice, but their the LLA structures retained. Simulation of X-ray diffraction (XRD) patterns for the dehydrated forms allowed to presume that the each [SbW{sub 6}O{sub 24}]{sup 7-} anion had been 30{sup o}-rotated within its molecular plane in order to avoid intermolecular repulsion. A compressed powder of 1-dehyd400 exhibited fast alkaline-ion conduction with a bulk conductivity of 1.2x10{sup -2} {Omega}{sup -1} cm{sup -1} at 400 {sup o}C. The hosting of a sufficient amount of NO{sub 3}{sup -} together with Na{sup +} for charge compensation into the lattice is crucial for high conduction. -- Graphical abstract: Two compounds Na{sub 2.5}K{sub 5.3}[SbW{sub 6}O{sub 24}](NO{sub 3}){sub 0.8}.12H{sub 2}O (1) and Na{sub 2}K{sub 5.35}[SbW{sub 6}O{sub 24}]Cl{sub 0.35}.12H{sub 2}O (2) possessing a layer-like Anderson (LLA) structure exhibited pseudo intercalation-deintercalation behavior. The dehydrated form of 1 is a high alkaline cation conductor with a conductivity of 1.2x10{sup -2} {Omega}{sup -1} cm{sup -1} at 400 {sup o}C. Display Omitted Research highlights: {yields} Layer-like Anderson-type POM solid accommodates and releases NO{sub 3}{sup -} and Cl{sup -}. {yields} The POM exhibits reversible dehydration by heat treatment. {yields} The dehydration involves rotation of POM molecule retaining layer structure. {yields} The dehydrated POM shows good Na{sup +} and K{sup +} conduction.« less

Substitution and Redox Chemistry of [Bu(4)N](2)[Ta(6)Cl(12)(OSO(2)CF(3))(6)].

PubMed

Prokopuk, Nicholas; Kennedy, Vance O.; Stern, Charlotte L.; Shriver, Duward F.

1998-09-21

Two sequential electrochemical reductions occur for the cluster anion [Ta(6)Cl(12)(OSO(2)CF(3))(6)](2)(-) at 0.89 and 0.29 V vs Ag/AgCl, with the generation [Ta(6)Cl(12)(OSO(2)CF(3))(6)](3)(-) and [Ta(6)Cl(12)(OSO(2)CF(3))(6)](4)(-). Chemical reduction of [Ta(6)Cl(12)(OSO(2)CF(3))(6)](2)(-) by ferrocene produces [Ta(6)Cl(12)(OSO(2)CF(3))(6)](3)(-) with the concomitant shift of the nu(SO(2)) stretch from 1002 to 1018 cm(-)(1). Reaction of [Bu(4)N](2)[Ta(6)Cl(12)(OSO(2)CF(3))(6)] (1) with [Bu(4)N]X (X = Cl, Br, I, NCS) occurs by reduction and substitution, yielding [Bu(4)N](3)[Ta(6)Cl(12)X(6)], where the clusters with X = Br, I, and NCS are new. Spectroscopic (IR and UV-vis) evidence indicates that the reduced cluster core {Ta(6)Cl(12)}(2+) is produced in reaction mixtures of 1 with the halide and pseudohalide ions. Concomitant substitution of the triflate ligands of 1 by X(-) occurs and the rates for the overall reduction and substitution increase in the order X(-) = Cl(-) < Br(-) < NCS(-) < I(-) < CN(-). Reduction of 1 with ferrocene followed by addition of [Bu(4)N]O(2)CCH(3) produces the new cluster [Ta(6)Cl(12)(O(2)CCH(3))(6)](3)(-) isolated as the tetrabutylammonium salt. Cyclic voltammetry and UV-vis spectroscopy on the new clusters [Bu(4)N](3)[Ta(6)Cl(12)X(6)] (X = Br, I, NCS, and O(2)CCH(3)) are reported. Crystal data for [Bu(4)N](3)[Ta(6)Cl(12)(NCS)(6)].CH(2)Cl(2): monoclinic, space group, P2(1)/c (No. 14); a = 25.855(6) Å, b = 21.843(6) Å, c = 16.423(3) Å; beta = 100.03(2) degrees; V = 9133(3) Å(3); Z = 4.

Chemistry of [Et4N][MoIV(SPh)(PPh3)(mnt)2] as an analogue of dissimilatory nitrate reductase with its inactivation on substitution of thiolate by chloride.

PubMed

Majumdar, Amit; Pal, Kuntal; Sarkar, Sabyasachi

2006-04-05

Structural-functional analogue of the reduced site of dissimilatory nitrate reductase is synthesized as [Et4N][MoIV(SPh)(PPh3)(mnt)2].CH2Cl2 (1). PPh3 in 1 is readily dissociated in solution to generate the active site of the reduced site of dissimilatory nitrate reductase. This readily reacts with nitrate. The nitrate reducing system is characterized by substrate saturation kinetics. Oxotransfer to and from substrate has been coupled to produce a catalytic system, NO3- + PPh3 --> NO2- + OPPh3, where NO3- is the substrate for dissimilatory nitrate reductase. The corresponding chloro complex, [Et4N][MoIV(Cl)(PPh3)(mnt)2].CH2Cl2 (2), responds to similar PPh3 dissociation but is unable to react with nitrate, showing the indispensable role of thiolate coordination for such oxotransfer reaction. This investigation provides the initial demonstration of the ligand specificity in a model system similar to single point mutation involving site directed mutagenesis in this class of molybdoenzymes.

Lanthanide contraction effect on crystal structures of lanthanide coordination polymers with cyclohexanocucurbit[6]uril ligand

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

Zheng, Li-Mei; Liu, Jing-Xin, E-mail: jxliu411@ahut.edu.cn

A series of compounds based on the macrocyclic ligand cyclohexanocucurbit[6]uril (Cy6Q[6]) with formulas (Ln(H{sub 2}O){sub 6}Cy6Q[6])·2(CdCl{sub 4})·H{sub 3}O·xH{sub 2}O [isomorphous with Ln=La (1), Ce (2), Pr (3) and Nd (4), x=11 (1), 11 (2), 10 (3) and 11 (4)], (Sm(H{sub 2}O){sub 5}Cy6Q[6])·2(CdCl{sub 4})·H{sub 3}O·10H{sub 2}O (5) and (Ln(H{sub 2}O){sub 5}(NO{sub 3})@Cy6Q[6])·2(CdCl{sub 4})·2H{sub 3}O·xH{sub 2}O [isomorphous with Ln=Gd (6), Tb (7) and Dy (8), x=8 (6), 6 (7) and 6 (8)], have been successfully synthesized by the self-assembly of Cy6Q[6] with the corresponding lanthanide nitrate under hydrochloric acid aqueous solution in the presence of CdCl{sub 2}. Single-crystal X-ray diffraction analyses revealedmore » that compounds 1–8 all crystallize in monoclinic space group P2{sub 1}/c, and display 1D coordination polymer structures. The lanthanide contraction effect on the structures of 1–8 has also been investigated and discussed in detail. In contrast, the reaction of Cy6Q[6] with the Ho(NO){sub 3}, Tm(NO){sub 3}, Yb(NO){sub 3} under the same conditions resulted in the compounds 9–11 with formulas Cy6Q[6]·2(CdCl{sub 4})·2H{sub 3}O·xH{sub 2}O [isomorphous with x=10 (9), 10 (10), and 9 (11)], in which no lanthanide cations are observed. The structural difference of these compounds indicates that the Cy6Q[6] may be used in the separation of lanthanide cations. - Graphical abstract: The reaction of cyclohexanocucurbit[6]uril with lanthanide ions (La{sup 3+}, Ce{sup 3+}, Pr{sup 3+}, Nd{sup 3+}, Sm{sup 3+}, Gd{sup 3+}, Tb{sup 3+}, Dy{sup 3+}, Ho{sup 3+}, Tm{sup 3+} and Yb{sup 3+}) under hydrochloric acid in the presence of CdCl{sub 2} resulted in eleven compounds, which demonstrate interesting lanthanide contraction effect and provide a means of separating lanthanide ions. - Highlights: • Eleven compounds of the Ln{sup 3+} with the Cy6Q[6] were synthesized and described. • Compounds 1-8 demonstrate interesting lanthanide contraction effect. • In solid-state structures of compounds 9-11, no lanthanide ions were observed. • This study provides a means of separating lanthanides cations.« less

Atmospheric chemistry of n-butanol: kinetics, mechanisms, and products of Cl atom and OH radical initiated oxidation in the presence and absence of NO(x).

PubMed

Hurley, M D; Wallington, T J; Laursen, L; Javadi, M S; Nielsen, O J; Yamanaka, T; Kawasaki, M

2009-06-25

Smog chamber/FTIR techniques were used to determine rate constants of k(Cl+n-butanol) = (2.21 +/- 0.38) x 10(-10) and k(OH+n-butanol) = (8.86 +/- 0.85) x 10(-12) cm(3) molecule(-1) s(-1) in 700 Torr of N(2)/O(2) diluent at 296 +/- 2K. The sole primary product identified from the Cl atom initiated oxidation of n-butanol in the absence of NO was butyraldehyde (38 +/- 2%, molar yield). The primary products of the Cl atom initiated oxidation of n-butanol in the presence of NO were (molar yield) butyraldehyde (38 +/- 2%), propionaldehyde (23 +/- 3%), acetaldehyde (12 +/- 4%), and formaldehyde (33 +/- 3%). The substantially lower yields of propionaldehyde, acetaldehyde, and formaldehyde as primary products in experiments conducted in the absence of NO suggests that chemical activation is important in the atmospheric chemistry of CH(3)CH(2)CH(O)CH(2)OH and CH(3)CH(O)CH(2)CH(2)OH alkoxy radicals. The primary products of the OH radical initiated oxidation of n-butanol in the presence of NO were (molar yields) butyraldehyde (44 +/- 4%), propionaldehyde (19 +/- 2%), and acetaldehyde (12 +/- 3%). In all cases, the product yields were independent of oxygen concentration over the partial pressure range of 10-600 Torr. The yields of propionaldehyde, acetaldehyde, and formaldehyde quoted above were not corrected for secondary formation via oxidation of higher aldehydes and should be treated as upper limits. The reactions of Cl atoms and OH radicals with n-butanol proceed 38 +/- 2 and 44 +/- 4%, respectively, via attack on the alpha-position to give an alpha-hydroxy alkyl radical which reacts with O(2) to give butyraldehyde. The results are discussed with respect to the atmospheric chemistry of n-butanol.

Effect of nitric oxide on photochemical ozone formation in mixtures of air with molecular chlorine and with trichlorofluoromethane

NASA Technical Reports Server (NTRS)

Bittker, D. A.; Wong, E. L.

1978-01-01

Ozone formation in a reaction chamber at room temperature and atmospheric pressure were studied for the photolysis of mixtures of NO with either Cl2 or CFCl3 in air. Both Cl2 + NO and CFCl3 + NO in air strongly inhibited O3 formation during the entire 3 to 4 hour reaction. A chemical mechanism that explains the results was presented. An important part of this mechanism was the formation and destruction of chlorine nitrate. Computations were performed with this same mechanism for CFCl3-NO-air mixtures at stratospheric temperatures, pressures, and concentrations. Results showed large reductions in steady-state O3 concentrations in these mixtures as compared with pure air.

Spermicidal activity of some halides.

PubMed

Narayan, J P; Singh, J N

1979-01-01

Though most of the metallic ions are spermicidal in action, the present investigation emphasises the spermicidal activity of anions. Among the inorganic compounds screened at 4 concentrations (0.01%, 0.1%, 1% and 5%) halides are mainly spermicidal, except NaCl, KCl & CsCl which are spermiostatic; sulphates and nitrates are mainly spermiostatic except ZnSO4 at 1% concentration and above; CuSO4, Al2 (SO4)3, Uo2(NO3)2.6H2O and AgNO3 at 5% concentration where they become spermicidal.

C(3i)-symmetric octanuclear cadmium cages: double-anion-templated synthesis, formation mechanism, and properties.

PubMed

Sun, Jie; Sun, Di; Yuan, Shuai; Tian, Dongxu; Zhang, Liangliang; Wang, Xingpo; Sun, Daofeng

2012-12-14

A series of C(3i)-symmetric bicapped trigonal antiprismatic Cd(8) cages [2X@Cd(8)L(6)(H(2)O)(6)]⋅n Y⋅solvents (X = Cl(-), Y = NO(3)(-), n = 2: MOCC-4; X = Br(-), Y = NO(3)(-), n = 2: MOCC-5; X = NO(3)(-), Y = NO(3)(-), n = 2: MOCC-6; X = NO(3)(-), Y = BF(4)(-), n = 2: MOCC-7; X = NO(3)(-), Y = ClO(4)(-), n = 2: MOCC-8; X = CO(3)(2-), n = 0: MOCC-9), doubly anion templated by different anions, were solvothermally synthesized by means of a flexible ligand. Interestingly, the CO(3)(2-) template for MOCC-9 was generated in situ by two-step decomposition of DMF solvent. For other MOCCs, spherical or trigonal monovalent anions could also play the role of template in their formation. The template abilities of these anions in the formation of the cages were experimentally studied and are discussed for the first time. Anion exchange of MOCC-8 was carried out and showed anion-size selectivity. All of the cage-like compounds emit strong luminescence at room temperature. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In Situ Detection of OH, HO2, ClO, BrO, NO2, ClONO2, BrONO2, ClOOCl, H2O, and O3 from the ER2

NASA Technical Reports Server (NTRS)

Anderson, James G.

2001-01-01

We review here the scientific progress that has emerged during the period January 1, 1998 through March 31, 2001. Results from the Sage III Ozone Loss and Validation Experiment (SOLVE) and Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission, and continuing work on prior missions, taken in order, including radical control of ozone on the northern hemisphere stratosphere, evolution of NO2 over the arctic winter and its effects on reactive chlorine, and the first measurements of ClOOCl in the stratosphere.

Chlorine as a primary radical: evaluation of methods to understand its role in initiation of oxidative cycles

NASA Astrophysics Data System (ADS)

Young, C. J.; Washenfelder, R. A.; Edwards, P. M.; Parrish, D. D.; Gilman, J. B.; Kuster, W. C.; Mielke, L. H.; Osthoff, H. D.; Tsai, C.; Pikelnaya, O.; Stutz, J.; Veres, P. R.; Roberts, J. M.; Griffith, S.; Dusanter, S.; Stevens, P. S.; Flynn, J.; Grossberg, N.; Lefer, B.; Holloway, J. S.; Peischl, J.; Ryerson, T. B.; Atlas, E. L.; Blake, D. R.; Brown, S. S.

2014-04-01

The role of chlorine atoms (Cl) in atmospheric oxidation has been traditionally thought to be limited to the marine boundary layer, where they are produced through heterogeneous reactions involving sea salt. However, recent observation of photolytic Cl precursors (ClNO2 and Cl2) formed from anthropogenic pollution has expanded the potential importance of Cl to include coastal and continental urban areas. Measurements of ClNO2 in Los Angeles during CalNex (California Nexus - Research at the Nexus of Air Quality and Climate Change) showed it to be an important primary (first generation) radical source. Evolution of ratios of volatile organic compounds (VOCs) has been proposed as a method to quantify Cl oxidation, but we find no evidence from this approach for a significant role of Cl oxidation in Los Angeles. We use a box model with the Master Chemical Mechanism (MCM v3.2) chemistry scheme, constrained by observations in Los Angeles, to examine the Cl sensitivity of commonly used VOC ratios as a function of NOx and secondary radical production. Model results indicate VOC tracer ratios could not detect the influence of Cl unless the ratio of [OH] to [Cl] was less than 200 for at least a day. However, the model results also show that secondary (second generation) OH production resulting from Cl oxidation of VOCs is strongly influenced by NOx, and that this effect obscures the importance of Cl as a primary oxidant. Calculated concentrations of Cl showed a maximum in mid-morning due to a photolytic source from ClNO2 and loss primarily to reactions with VOCs. The [OH] to [Cl] ratio was below 200 for approximately 3 h in the morning, but Cl oxidation was not evident from the measured ratios of VOCs. Instead, model simulations show that secondary OH production causes VOC ratio evolution to follow that expected for OH oxidation, despite the significant input of primary Cl from ClNO2 photolysis in the morning. Even though OH is by far the dominant oxidant in Los Angeles, Cl atoms do play an important role in photochemistry there, constituting 9% of the primary radical source. Furthermore, Cl-VOC reactivity differs from that of OH, being more than an order of magnitude larger and dominated by VOCs, such as alkanes, that are less reactive toward OH. Primary Cl is also slightly more effective as a radical source than primary OH due to its greater propensity to initiate radical propagation chains via VOC reactions relative to chain termination via reaction with nitrogen oxides.

Modification of elastic stable intramedullary nailing with a 3rd nail in a femoral spiral fracture model - results of biomechanical testing and a prospective clinical study.

PubMed

Kaiser, Martin M; Stratmann, Christine; Zachert, Gregor; Schulze-Hessing, Maaike; Gros, Nina; Eggert, Rebecca; Rapp, Marion

2014-01-08

Elastic stable intramedullary nailing (ESIN) is the standard treatment for displaced diaphyseal femoral fractures in children. However, high complication rates (10-50%) are reported in complex fractures. This biomechanical study compares the stiffness with a 3rd nail implanted to that in the classical 2C-shaped configuration and presents the application into clinical practice. For each of the 3 configurations of ESIN-osteosynthesis with titanium nails eight composite femoral grafts (Sawbones®) with an identical spiral fracture were used: 2C configuration (2C-shaped nails, 2 × 3.5 mm), 3CM configuration (3rd nail from medial) and 3CL configuration (3rd nail from lateral). Each group underwent biomechanical testing in 4-point bending, internal/external rotation and axial compression. 2C and 3CM configurations showed no significant differences in this spiroid type fracture model. 3CL had a significantly higher stiffness during anterior-posterior bending, internal rotation and 9° compression than 2C, and was stiffer in the lateral-medial direction than 3CM. The 3CL was less stable during p-a bending and external rotation than both the others. As biomechanical testing showed a higher stability for the 3CL configuration in two (a-p corresponding to recurvation and 9° compression to shortening) of three directions associated with the most important clinical problems, we added a 3rd nail in ESIN-osteosynthesis for femoral fractures. 11 boys and 6 girls (2.5-15 years) were treated with modified ESIN of whom 12 were '3CL'; due to the individual character of the fractures 4 patients were treated with '3CM' (third nail from medial) and as an exception 1 adolescent with 4 nails and one boy with plate osteosynthesis. No additional stabilizations or re-operations were necessary. All patients achieved full points in the Harris-Score at follow-up; no limb length discrepancy occurred. The 3CL configuration provided a significantly higher stiffness than 2C and 3CM configurations in this biomechanical model. These results were successfully transmitted into clinical practice. All children, treated by 3CL or 3CM according to the individual character of each fracture, needed no additional stabilization and had no Re-Do operations. As a consequence, at our hospital all children with femoral diaphyseal fractures with open physis are treated with this modified ESIN-technique.

21 CFR 184.1193 - Calcium chloride.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Calcium chloride. 184.1193 Section 184.1193 Food... Specific Substances Affirmed as GRAS § 184.1193 Calcium chloride. (a) Calcium chloride (CaCl2·2H2O, CAS Reg. No. 10035-04-8) or anhydrous calcium chloride (CaCl2, CAS Reg. No. 10043-52-4) may be commercially...

21 CFR 184.1193 - Calcium chloride.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Calcium chloride. 184.1193 Section 184.1193 Food... Specific Substances Affirmed as GRAS § 184.1193 Calcium chloride. (a) Calcium chloride (CaCl2·2H2O, CAS Reg. No. 10035-04-8) or anhydrous calcium chloride (CaCl2, CAS Reg. No. 10043-52-4) may be commercially...

21 CFR 184.1193 - Calcium chloride.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Calcium chloride. 184.1193 Section 184.1193 Food... GRAS § 184.1193 Calcium chloride. (a) Calcium chloride (CaCl2·2H2O, CAS Reg. No. 10035-04-8) or anhydrous calcium chloride (CaCl2, CAS Reg. No. 10043-52-4) may be commercially obtained as a byproduct in...

Glucose-6-phosphate dehydrogenase plays a pivotal role in nitric oxide-involved defense against oxidative stress under salt stress in red kidney bean roots.

PubMed

Liu, Yinggao; Wu, Ruru; Wan, Qi; Xie, Gengqiang; Bi, Yurong

2007-03-01

The pivotal role of glucose-6-phosphate dehydrogenase (G-6-PDH)-mediated nitric oxide (NO) production in the tolerance to oxidative stress induced by 100 mM NaCl in red kidney bean (Phaseolus vulgaris) roots was investigated. The results show that the G-6-PDH activity was enhanced rapidly in the presence of NaCl and reached a maximum at 100 mM. Western blot analysis indicated that the increase of G-6-PDH activity in the red kidney bean roots under 100 mM NaCl was mainly due to the increased content of the G-6-PDH protein. NO production and nitrate reductase (NR) activity were also induced by 100 mM NaCl. The NO production was reduced by NaN(3) (an NR inhibitor), but not affected by N(omega)-nitro-L-arginine (L-NNA) (an NOS inhibitor). Application of 2.5 mM Na(3)PO(4), an inhibitor of G-6-PDH, blocked the increase of G-6-PDH and NR activity, as well as NO production in red kidney bean roots under 100 mM NaCl. The activities of antioxidant enzymes in red kidney bean roots increased in the presence of 100 mM NaCl or sodium nitroprusside (SNP), an NO donor. The increased activities of all antioxidant enzymes tested at 100 mM NaCl were completely inhibited by 2.5 mM Na(3)PO(4). Based on these results, we conclude that G-6-PDH plays a pivotal role in NR-dependent NO production, and in establishing tolerance of red kidney bean roots to salt stress.

Electrochemical Grafting of Graphene Nano Platelets with Aryl Diazonium Salts.

PubMed

Qiu, Zhipeng; Yu, Jun; Yan, Peng; Wang, Zhijie; Wan, Qijin; Yang, Nianjun

2016-10-26

To vary interfacial properties, electrochemical grafting of graphene nano platelets (GNP) with 3,5-dichlorophenyl diazonium tetrafluoroborate (aryl-Cl) and 4-nitrobenzene diazonium tetrafluoroborate (aryl-NO 2 ) was realized in a potentiodynamic mode. The covalently bonded aryl layers on GNP were characterized using atomic force microscopy and X-ray photoelectron spectroscopy. Electrochemical conversion of aryl-NO 2 into aryl-NH 2 was conducted. The voltammetric and impedance behavior of negatively and positively charged redox probes (Fe(CN) 6 3-/4- and Ru(NH 3 ) 6 2+/3+ ) on three kinds of aryl layers grafted on GNP reveal that their interfacial properties are determined by the charge states of redox probes and reactive terminal groups (-Cl, -NO 2 , -NH 2 ) in aryl layers. On aryl-Cl and aryl-NH 2 garted GNP, selective and sensitive monitoring of positively charged lead ions as well as negatively charged nitrite and sulfite ions was achieved, respectively. Such a grafting procedure is thus a perfect way to design and control interfacial properties of graphene.

High-Temperature Reactions of Metal Triangles: The Influence of Counterion, Ligand, and Metal on the Structure Observed

NASA Astrophysics Data System (ADS)

Coxall, Robert A.; Parkin, Andrew; Parsons, Simon; Smith, Andrew A.; Timco, Grigore A.; Winpenny, Richard E. P.

2001-07-01

A series of oxo-centered metal carboxylate triangles have been heated to 200-400°C under a stream of N2. The products of this treatment depend on the metal, carboxylate, and counterion present. Heating [Cr3O(O2CC6H4Cl)6(H2O)3][NO3]to 200°C gives a compound that crystallizes as [Cr(OH)(O2CC6H4Cl)2]8 [Cr3O(O2CC6H4Cl)6]2[O2CC6H4Cl], indicating incomplete dehydration of [Cr3O(O2CC6H4Cl)6(H2O)3][NO3] at this temperature. For [Cr3O(O2CCMe3)6][O2CCMe3] heating to 400°C gives a new salt containing the hexanuclear cages [Cr6O2(OH)2(O2CCMe3)11] [Cr6O4(O2CCMe3)11]. For [Mn3O(O2CPh)6(NC5H5)2(H2O)] a reduction of the metal occurs and a polymeric complex [Mn4(O2CPh)8(EtOH)6]n can be crystallized from EtOH.

Ion Pair Formation between Tertiary Aliphatic Amines and Perchlorate in the Biphasic Water/Dichloromethane System.

PubMed

Badocco, Denis; Di Marco, Valerio; Venzo, Alfonso; Frasconi, Marco; Frezzato, Diego; Pastore, Paolo

2017-10-12

The ability of aliphatic amines (AAs), namely, tripropylamine (TPrA), trisobutylamine (TisoBuA), and tributylamine (TBuA), to form ion pairs with perchlorate anion (ClO 4 - ) in biphasic aqueous/dichloromethane (CH 2 Cl 2 ) mixtures containing ClO 4 - 0.1 M has been demonstrated by GC with flame ionization (FID) and mass detectors (MS) and by NMR measurements. The extraction efficiency of the AAs to the organic phase was modeled by equations that were used to fit the experimental GC data, allowing us to determine values for K P (partition constant of the free AA), K IP (formation constant of the ion pair), and K P IP (partition constant of the ion pair) for TPrA, TisoBuA, and TBuA at 25 °C. Ion pairs were shown to form in CH 2 Cl 2 also when ClO 4 - is replaced by other inorganic anions, like NO 3 - , ClO 3 - , Cl - , H 2 PO 4 - , and IO 3 - . No ion pairs formed when CH 2 Cl 2 was replaced by n-hexane, suggesting that aliphatic amine ion pairs can form in polar organic solvents but not in nonpolar ones.

Contribution Of Spray Irrigation Of Wastewater To Groundwater Contamination In The Karst Of Southeastern Minnesota, USA

NASA Astrophysics Data System (ADS)

Mooers, H. D.; Alexander, E. C., Jr.

1994-01-01

A vegetable- and meat-canning facility located in the karst of southeastern Minnesota disposes ≈2.85×105 m3 yr-1 of wastewater by spray irrigation of an 83.7-ha field located atop the local groundwater divide. Cannery effluent contains high levels of chloride and nitrogen (organic and ammonia), in excess of 7000 mg/l and 400 mg/l, respectively. Nitrate-nitrogen concentrations are generally < 5 mg/l. Agricultural, domestic, and municipal sources of chloride and nitrate are common in the region, and water supplies frequently exceed the drinking-water limit for nitrate-nitrogen of 10 mg/l. Fifty-two area wells and thirteen surface-water locations were sampled and analyzed for five ionic species, including: chloride (Cl), nitrate-nitrogen (NO3-N), sulfate (SO4), nitrite-nitrogen (NO2-N), and phosphate (PO4). Two distinct chloride plumes flowing outward from the groundwater divide were identified, and 65% of the wells sampled had nitrate-nitrogen concentrations in excess of 10 mg/l. The data were divided into two groups: one group of samples from wells located near the canning facility and another group from outside that area. A correlation coefficient of R2= 0.004 for Cl vs. NO3-N in the vicinity of the irrigation fields indicates essentially no relationship between the source of Cl and NO3. In areas of agricultural and domestic activities located away from the cannery, an R2 of 0.54 suggests that Cl and NO3 have common sources in these areas.

Exhaustive Conversion of Inorganic Nitrogen to Nitrogen Gas Based on a Photoelectro-Chlorine Cycle Reaction and a Highly Selective Nitrogen Gas Generation Cathode.

PubMed

Zhang, Yan; Li, Jinhua; Bai, Jing; Shen, Zhaoxi; Li, Linsen; Xia, Ligang; Chen, Shuai; Zhou, Baoxue

2018-02-06

A novel method for the exhaustive conversion of inorganic nitrogen to nitrogen gas is proposed in this paper. The key properties of the system design included an exhaustive photoelectrochemical cycle reaction in the presence of Cl - , in which Cl· generated from oxidation of Cl - by photoholes selectively converted NH 4 + to nitrogen gas and some NO 3 - or NO 2 - . The NO 3 - or NO 2 - was finally reduced to nitrogen gas on a highly selective Pd-Cu-modified Ni foam (Pd-Cu/NF) cathode to achieve exhaustive conversion of inorganic nitrogen to nitrogen gas. The results indicated total nitrogen removal efficiencies of 30 mg L -1 inorganic nitrogen (NO 3 - , NH 4 + , NO 3 - /NH 4 + = 1:1 and NO 2 - /NO 3 - /NH 4 + = 1:1:1) in 90 min were 98.2%, 97.4%, 93.1%, and 98.4%, respectively, and the remaining nitrogen was completely removed by prolonging the reaction time. The rapid reduction of nitrate was ascribed to the capacitor characteristics of Pd-Cu/NF that promoted nitrate adsorption in the presence of an electric double layer, eliminating repulsion between the cathode and the anion. Nitrate was effectively removed with a rate constant of 0.050 min -1 , which was 33 times larger than that of Pt cathode. This system shows great potential for inorganic nitrogen treatment due to the high rate, low cost, and clean energy source.

Stable isotopic composition of perchlorate and nitrate accumulated in plants: Hydroponic experiments and field data.

PubMed

Estrada, Nubia Luz; Böhlke, J K; Sturchio, Neil C; Gu, Baohua; Harvey, Greg; Burkey, Kent O; Grantz, David A; McGrath, Margaret T; Anderson, Todd A; Rao, Balaji; Sevanthi, Ritesh; Hatzinger, Paul B; Jackson, W Andrew

2017-10-01

Natural perchlorate (ClO 4 - ) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ 37 Cl, δ 18 O, and Δ 17 O), indicating that ClO 4 - may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO 4 - , but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO 4 - in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO 4 - was transported from solutions into plants similarly to NO 3 - but preferentially to Cl - (4-fold). The ClO 4 - isotopic compositions of initial ClO 4 - reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO 4 - uptake or accumulation. The ClO 4 - isotopic composition of field-grown snap beans was also consistent with that of ClO 4 - in varying proportions from irrigation water and precipitation. NO 3 - uptake had little or no effect on NO 3 - isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε ( 15 N/ 18 O) ratio of 1.05 was observed between NO 3 - in hydroponic solutions and leaf extracts, consistent with partial NO 3 - reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO 4 - in commercial produce, as illustrated by spinach, for which the ClO 4 - isotopic composition was similar to that of indigenous natural ClO 4 - . Our results indicate that some types of plants can accumulate and (presumably) release ClO 4 - to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO 4 - and NO 3 - in plants may be useful for determining sources of fertilizers and sources of ClO 4 - in their growth environments and consequently in food supplies. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis and structures of six closely related N-[3-(2-chlorobenzoyl)-5-ethylthiophen-2-yl]arylamides, together with an isolated reaction intermediate: order versus disorder, molecular conformations and hydrogen bonding in zero, one and two dimensions.

PubMed

Sagar, Belakavadi K; Yathirajan, Hemmige S; Rathore, Ravindranath S; Glidewell, Christopher

2018-02-01

Six closely related N-[3-(2-chlorobenzoyl)-5-ethylthiophen-2-yl]arylamides have been synthesized and structurally characterized, together with a representative reaction intermediate. In each of N-[3-(2-chlorobenzoyl)-5-ethylthiophen-2-yl]benzamide, C 20 H 16 ClNO 2 S, (I), N-[3-(2-chlorobenzoyl)-5-ethylthiophen-2-yl]-4-phenylbenzamide, C 26 H 20 ClNO 2 S, (II), and 2-bromo-N-[3-(2-chlorobenzoyl)-5-ethylthiophen-2-yl]benzamide, C 20 H 15 BrClNO 2 S, (III), the molecules are disordered over two sets of atomic sites, with occupancies of 0.894 (8) and 0.106 (8) in (I), 0.832 (5) and 0.168 (5) in (II), and 0.7006 (12) and 0.2994 (12) in (III). In each of N-[3-(2-chlorobenzoyl)-5-ethylthiophen-2-yl]-2-iodobenzamide, C 20 H 15 ClINO 2 S, (IV), and N-[3-(2-chlorobenzoyl)-5-ethylthiophen-2-yl]-2-methoxybenzamide, C 21 H 18 ClNO 3 S, (V), the molecules are fully ordered, but in N-[3-(2-chlorobenzoyl)-5-ethylthiophen-2-yl]-2,6-difluorobenzamide, C 20 H 14 ClF 2 NO 2 S, (VI), which crystallizes with Z' = 2 in the space group C2/c, one of the two independent molecules is fully ordered, while the other is disordered over two sets of atomic sites having occupancies of 0.916 (3) and 0.084 (3). All of the molecules in compounds (I)-(VI) exhibit an intramolecular N-H...O hydrogen bond. The molecules of (I) and (VI) are linked by C-H...O hydrogen bonds to form finite zero-dimensional dimers, which are cyclic in (I) and acyclic in (VI), those of (III) are linked by C-H...π(arene) hydrogen bonds to form simple chains, and those of (IV) and (V) are linked into different types of chains of rings, built in each case from a combination of C-H...O and C-H...π(arene) hydrogen bonds. Two C-H...O hydrogen bonds link the molecules of (II) into sheets containing three types of ring. In benzotriazol-1-yl 3,4-dimethoxybenzoate, C 15 H 13 N 3 O 4 , (VII), the benzoate component is planar and makes a dihedral angle of 84.51 (6)° with the benzotriazole unit. Comparisons are made with related compounds.

Examining the impact of nitryl chloride chemistry on summertime air quality

NASA Astrophysics Data System (ADS)

Sarwar, G.; Simon, H. A.; Bhave, P.; Hutzell, W. T.

2011-12-01

Results of recent field campaigns suggest that heterogeneous reactions can form nitryl chloride (ClNO2) at night. ClNO2 photodissociates into nitrogen dioxide and chlorine radicals during the day. Subsequent photolysis of nitrogen dioxide and reactions of chlorine radicals with volatile organic compounds increase ozone production. Thus, the presence of ClNO2 in the atmosphere can enhance ozone. In this study, the impact of the heterogeneous production of ClNO2 on summertime air quality in the United States is examined by using the Community Multiscale Air Quality (CMAQ) model. Laboratory chamber experimental studies have parameterized the yield of ClNO2 and the heterogeneous uptake of dinitrogen pentoxide on aerosols. We implement these parameterizations into the CMAQ model. In addition to the typical emissions, the model also includes emissions of sea-salt, anthropogenic particulate chloride, anthropogenic hydrochloric acid and molecular chlorine from the National Emissions Inventory. Model simulations are conducted without and with the heterogeneous ClNO2 formation reaction for September 1-10, 2006. The results of the study suggest that the heterogeneous reaction produces ClNO2 in many coastal areas as well as inland locations in the United States. The ClNO2 increase in coastal areas is caused by chloride emissions from sea-salt and in inland-areas by chloride emissions from fire and anthropogenic sources. Predicted ClNO2 levels reach nighttime peaks of up to 4.0 ppb in the Los Angeles area and up to 1.2 ppb near Houston, similar to the measured values reported in the literature. The ClNO2 chemistry decreases nitric acid as well as particulate nitrate by a large margin; consequently it changes composition of NOz. It increases hourly and daily maximum 8-hr ozone by up to 9 ppbv and 6 ppbv, respectively. It increases aerosol sulfate while decreasing aerosol nitrate and ammonium. The accompanying presentation identifies predicted spatial patterns of ClNO2 concentrations across the United States and describes the detailed impact of the ClNO2 chemistry on ozone, nitric acid, sulfate, particulate nitrate, ammonium, and particulate chloride. To evaluate the impact of the ClNO2 chemistry on an ozone control strategy, two additional model simulations were conducted with reduced NOx emissions. Relative response factors were determined without and with the ClNO2 chemistry; the accompanying presentation discusses the impact on ozone control strategy.

Kinetics of the Reactions of F((sup 2)P) and Cl((sup 2)P) with HNO3

NASA Technical Reports Server (NTRS)

Wine, P. H.; Wells, J. R.; Nicovich, J. M.

1997-01-01

The kinetics of the reactions of HNO3 with fluorine (k(sub 1)) and Chlorine (k(sub 2)) atoms have been studied by using a time-resolved long-path laser absorption technique to monitor the appearance of product NO3 radicals following 351-nm pulsed laser photolysis of X2/HNO3/He mixtures (X = F,Cl). Absolute rate coefficients for the F((sup 2)P) + HNO reaction have been determined over the temperature range 260-373 K. Between 260 and 320 K, the data are adequately represented by the Arrhenius expression k(sub 1)(T) = (6.0 +/- 2.6) x 10(exp -12) exp[(40 +/- 120)/T]cu cm/(molecule.s). Between 335 and 373 K, the rate coefficient is found to be (2.0 +/- 0.3) x 10(exp -11)cu cm/(molecule.s) independent of temperature. The observed temperature dependence suggests that reaction proceeds via competing direct abstraction and complex pathways. No NO3 production was observed in the experiments with X equals Cl, thus establishing that k(sub 2)(298 K) is less than 2 x 10(exp -16) cu cm/(molecule.s). The Cl((sup 2)P) + HNO reaction was also investigated by using a pulsed laser photolysis-resonance fluorescence technique to monitor the decay of Cl((sup 2)P). Upper limit values for k(sub 2) obtained from these experiments, in units of 10(exp -16)cu cm/(molecule.s), are 13 at 298 K and 10 at 400 K.

Stable isotopic composition of perchlorate and nitrate accumulated in plants: Hydroponic experiments and field data

USGS Publications Warehouse

Estrada, Nubia Luz; Böhlke, John Karl; Sturchio, Neil C.; Gu, Baohua; Harvey, Greg; Burkey, Kent O.; Grantz, David A.; McGrath, Margaret T.; Anderson, Todd A.; Rao, Balaji; Sevanthi, Ritesh; Hatzinger, Paul B.; Jackson, W. Andrew

2017-01-01

Natural perchlorate (ClO4−) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ37Cl, δ18O, and Δ17O), indicating that ClO4− may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO4−, but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO4− in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO4− was transported from solutions into plants similarly to NO3− but preferentially to Cl− (4-fold). The ClO4− isotopic compositions of initial ClO4− reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO4− uptake or accumulation. The ClO4− isotopic composition of field-grown snap beans was also consistent with that of ClO4− in varying proportions from irrigation water and precipitation. NO3− uptake had little or no effect on NO3− isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε (15N/18O) ratio of 1.05 was observed between NO3− in hydroponic solutions and leaf extracts, consistent with partial NO3− reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO4− in commercial produce, as illustrated by spinach, for which the ClO4− isotopic composition was similar to that of indigenous natural ClO4−. Our results indicate that some types of plants can accumulate and (presumably) release ClO4− to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO4−and NO3− in plants may be useful for determining sources of fertilizers and sources of ClO4− in their growth environments and consequently in food supplies.

Modeling the impact of chlorine emissions from coal combustion and prescribed waste incineration on tropospheric ozone formation in China

NASA Astrophysics Data System (ADS)

Liu, Yiming; Fan, Qi; Chen, Xiaoyang; Zhao, Jun; Ling, Zhenhao; Hong, Yingying; Li, Weibiao; Chen, Xunlai; Wang, Mingjie; Wei, Xiaolin

2018-02-01

Chlorine radicals can enhance atmospheric oxidation, which potentially increases tropospheric ozone concentration. However, few studies have been done to quantify the impact of chlorine emissions on ozone formation in China due to the lack of a chlorine emission inventory used in air quality models with sufficient resolution. In this study, the Anthropogenic Chlorine Emissions Inventory for China (ACEIC) was developed for the first time, including emissions of hydrogen chloride (HCl) and molecular chlorine (Cl2) from coal combustion and prescribed waste incineration (waste incineration plant). The HCl and Cl2 emissions from coal combustion in China in 2012 were estimated to be 232.9 and 9.4 Gg, respectively, while HCl emission from prescribed waste incineration was estimated to be 2.9 Gg. Spatially the highest emissions of HCl and Cl2 were found in the North China Plain, the Yangtze River Delta, and the Sichuan Basin. Air quality model simulations with the Community Multiscale Air Quality (CMAQ) modeling system were performed for November 2011, and the modeling results derived with and without chlorine emissions were compared. The magnitude of the simulated HCl, Cl2 and ClNO2 agreed reasonably with the observation when anthropogenic chlorine emissions were included in the model. The inclusion of the ACEIC increased the concentration of fine particulate Cl-, leading to enhanced heterogeneous reactions between Cl- and N2O5, which resulted in the higher production of ClNO2. Photolysis of ClNO2 and Cl2 in the morning and the reaction of HCl with OH in the afternoon produced chlorine radicals which accelerated tropospheric oxidation. When anthropogenic chlorine emissions were included in the model, the monthly mean concentrations of fine particulate Cl-, daily maximum 1 h ClNO2, and Cl radicals were estimated to increase by up to about 2.0 µg m-3, 773 pptv, and 1.5 × 103 molecule cm-3 in China, respectively. Meanwhile, the monthly mean daily maximum 8 h O3 concentration was found to increase by up to 2.0 ppbv (4.1 %), while the monthly mean NOx concentration decreased by up to 0.5 ppbv (6.1 %). The anthropogenic chlorine emissions potentially increased the 1 h O3 concentration by up to 7.7 ppbv in China. This study highlights the need for the inclusion of anthropogenic chlorine emission in air quality modeling and demonstrated its importance in tropospheric ozone formation.

Synthesis and oxidation of CpIrIII compounds: functionalization of a Cp methyl group.

PubMed

Park-Gehrke, Lisa S; Freudenthal, John; Kaminsky, Werner; Dipasquale, Antonio G; Mayer, James M

2009-03-21

[CpIrCl(2)](2) () and new CpIr(III)(L-L)X complexes (L-L = N-O or C-N chelating ligands; X = Cl, I, Me) have been prepared and their reactivity with two-electron chemical oxidants explored. Reaction of with PhI(OAc)(2) in wet solvents yields a new chloro-bridged dimer in which each of the Cp ligands has been singly acetoxylated to form [Cp(OAc)Ir(III)Cl(2)](2) () (Cp(OAc) = eta(5)-C(5)Me(4)CH(2)OAc). Complex and related carboxy- and alkoxy-functionalized Cp(OR) complexes can also be prepared from plus (PhIO)(n) and ROH. [Cp(OAc)Ir(III)Cl(2)](2) () and the methoxy analogue [Cp(OMe)Ir(III)Cl(2)](2) () have been structurally characterized. Treatment of [CpIrCl(2)](2) () with 2-phenylpyridine yields CpIr(III)(ppy)Cl () (ppy = cyclometallated 2-phenylpyridyl) which is readily converted to its iodide and methyl analogues CpIr(III)(ppy)I and CpIr(III)(ppy)Me (). CpIr(III) complexes were also prepared with N-O chelating ligands derived from anthranilic acid (2-aminobenzoic acid) and alpha-aminoisobutyric acid (H(2)NCMe(2)COOH), ligands chosen to be relatively oxidation resistant. These complexes and were reacted with potential two-electron oxidants including PhI(OAc)(2), hexachlorocyclohexadienone (C(6)Cl(6)O), N-fluoro-2,4,6-trimethylpyridinium (Me(3)pyF(+)), [Me(3)O]BF(4) and MeOTf (OTf = triflate, CF(3)SO(3)). Iridium(V) complexes were not observed or implicated in these reactions, despite the similarity of the potential products to known CpIr(V) species. The carbon electrophiles [Me(3)O]BF(4) and MeOTf appear to react preferentially at the N-O ligands, to give methyl esters in some cases. Overall, the results indicate that Cp is not inert under oxidizing conditions and is therefore not a good supporting ligand for oxidizing organometallic complexes.

Combined impacts of nitrous acid and nitryl chloride on lower-tropospheric ozone: new module development in WRF-Chem and application to China

NASA Astrophysics Data System (ADS)

Zhang, Li; Li, Qinyi; Wang, Tao; Ahmadov, Ravan; Zhang, Qiang; Li, Meng; Lv, Mengyao

2017-08-01

Nitrous acid (HONO) and nitryl chloride (ClNO2) - through their photolysis - can have profound effects on the nitrogen cycle and oxidation capacity of the lower troposphere. Previous numerical studies have separately considered and investigated the sources/processes of these compounds and their roles in the fate of reactive nitrogen and the production of ozone (O3), but their combined impact on the chemistry of the lower part of the troposphere has not been addressed yet. In this study, we updated the WRF-Chem model with the currently known sources and chemistry of HONO and chlorine in a new chemical mechanism (CBMZ_ReNOM), and applied it to a study of the combined effects of HONO and ClNO2 on summertime O3 in the boundary layer over China. We simulated the spatial distributions of HONO, ClNO2, and related compounds at the surface and within the lower troposphere. The results showed that the modeled HONO levels reached up to 800-1800 ppt at the surface (0-30 m) over the North China Plain (NCP), the Yangtze River Delta (YRD), and the Pearl River Delta (PRD) regions and that HONO was concentrated within a 0-200 m layer. In comparison, the simulated surface ClNO2 mixing ratio was around 800-1500 ppt over the NCP, YRD, and central China regions and was predominantly present in a 0-600 m layer. HONO enhanced daytime ROx (OH + HO2 + RO2) and O3 at the surface (0-30 m) by 2.8-4.6 ppt (28-37 %) and 2.9-6.2 ppb (6-13 %), respectively, over the three most developed regions, whereas ClNO2 increased surface O3 in the NCP and YRD regions by 2.4-3.3 ppb (or 5-6 %) and it also had a significant impact (3-6 %) on above-surface O3 within 200-500 m. The combined effects increased surface O3 by 11.5, 13.5, and 13.3 % in the NCP, YRD, and PRD regions, respectively. Over the boundary layer (0-1000 m), the HONO and ClNO2 enhanced O3 by up to 5.1 and 3.2 %, respectively, and their combined effect increased O3 by 7.1-8.9 % in the three regions. The new module noticeably improved O3 predictions at ˜ 900 monitoring stations throughout China by reducing the mean bias from -4.3 to 0.1 ppb. Our study suggests the importance of considering these reactive nitrogen species simultaneously into chemical transport models to better simulate the formation of summertime O3 in polluted regions.

NQRS Data for C7H8Cl3Osb (Subst. No. 1005)

NASA Astrophysics Data System (ADS)

Chihara, H.; Nakamura, N.

This document is part of Subvolume A `Substances Containing Ag … C10H15' of Volume 48 `Nuclear Quadrupole Resonance Spectroscopy Data' of Landolt-Börnstein - Group III `Condensed Matter'. It contains an extract of Section `3.2 Data tables' of the Chapter `3 Nuclear quadrupole resonance data' providing the NQRS data for C7H8Cl3OSb (Subst. No. 1005)

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

Massa, Christopher B.; Scott, Pamela; Abramova, Elena

Acute Cl{sub 2} exposure following industrial accidents or military/terrorist activity causes pulmonary injury and severe acute respiratory distress. Prior studies suggest that antioxidant depletion is important in producing dysfunction, however a pathophysiologic mechanism has not been elucidated. We propose that acute Cl{sub 2} inhalation leads to oxidative modification of lung lining fluid, producing surfactant inactivation, inflammation and mechanical respiratory dysfunction at the organ level. C57BL/6J mice underwent whole-body exposure to an effective 60 ppm-hour Cl{sub 2} dose, and were euthanized 3, 24 and 48 h later. Whereas pulmonary architecture and endothelial barrier function were preserved, transient neutrophilia, peaking at 24more » h, was noted. Increased expression of ARG1, CCL2, RETLNA, IL-1b, and PTGS2 genes was observed in bronchoalveolar lavage (BAL) cells with peak change in all genes at 24 h. Cl{sub 2} exposure had no effect on NOS2 mRNA or iNOS protein expression, nor on BAL NO{sub 3}{sup −} or NO{sub 2}{sup −}. Expression of the alternative macrophage activation markers, Relm-α and mannose receptor was increased in alveolar macrophages and pulmonary epithelium. Capillary surfactometry demonstrated impaired surfactant function, and altered BAL phospholipid and surfactant protein content following exposure. Organ level respiratory function was assessed by forced oscillation technique at 5 end expiratory pressures. Cl{sub 2} exposure had no significant effect on either airway or tissue resistance. Pulmonary elastance was elevated with time following exposure and demonstrated PEEP refractory derecruitment at 48 h, despite waning inflammation. These data support a role for surfactant inactivation as a physiologic mechanism underlying respiratory dysfunction following Cl{sub 2} inhalation. - Highlights: • Effect of 60 ppm*hr Cl{sub 2} gas on lung inflammation and mechanical function examined. • Pulmonary inflammation is transient and minor. • Alterations in surfactant homeostasis and pulmonary mechanics are noted. • No increase in the caliber of larger airways was suggested. • Small airways stability appears impaired based on PEEP response of mechanics.« less

Surface tensions of inorganic multicomponent aqueous electrolyte solutions and melts.

PubMed

Dutcher, Cari S; Wexler, Anthony S; Clegg, Simon L

2010-11-25

A semiempirical model is presented that predicts surface tensions (σ) of aqueous electrolyte solutions and their mixtures, for concentrations ranging from infinitely dilute solution to molten salt. The model requires, at most, only two temperature-dependent terms to represent surface tensions of either pure aqueous solutions, or aqueous or molten mixtures, over the entire composition range. A relationship was found for the coefficients of the equation σ = c(1) + c(2)T (where T (K) is temperature) for molten salts in terms of ion valency and radius, melting temperature, and salt molar volume. Hypothetical liquid surface tensions can thus be estimated for electrolytes for which there are no data, or which do not exist in molten form. Surface tensions of molten (single) salts, when extrapolated to normal temperatures, were found to be consistent with data for aqueous solutions. This allowed surface tensions of very concentrated, supersaturated, aqueous solutions to be estimated. The model has been applied to the following single electrolytes over the entire concentration range, using data for aqueous solutions over the temperature range 233-523 K, and extrapolated surface tensions of molten salts and pure liquid electrolytes: HCl, HNO(3), H(2)SO(4), NaCl, NaNO(3), Na(2)SO(4), NaHSO(4), Na(2)CO(3), NaHCO(3), NaOH, NH(4)Cl, NH(4)NO(3), (NH(4))(2)SO(4), NH(4)HCO(3), NH(4)OH, KCl, KNO(3), K(2)SO(4), K(2)CO(3), KHCO(3), KOH, CaCl(2), Ca(NO(3))(2), MgCl(2), Mg(NO(3))(2), and MgSO(4). The average absolute percentage error between calculated and experimental surface tensions is 0.80% (for 2389 data points). The model extrapolates smoothly to temperatures as low as 150 K. Also, the model successfully predicts surface tensions of ternary aqueous mixtures; the effect of salt-salt interactions in these calculations was explored.

Heterogeneous reaction kinetics and mechanism of the nitration of aerosolized protein by O3 and NO2

NASA Astrophysics Data System (ADS)

Shiraiwa, Manabu; Sosedova, Yulia; Rouvière, Aurélie; Ammann, Markus; Pöschl, Ulrich

2010-05-01

The effects of air pollution on allergic diseases are not yet well-understood. Proteins contained in biogenic aerosol particles (pollen, spores, bacteria, etc.), which accounts for up to 5% of urban air particulate matter, are efficiently nitrated in polluted environments before inhalation and deposition in the human respiratory tract [1], which is likely to trigger immune reactions for allergies. Proteins undergo a nitration reaction that leads to the formation of 3-nitrotyrosine residues. The kinetics and reaction mechanism of protein nitration are still largely unknown. The kinetics of nitration of protein particles by O3 and NO2 was measured using the short-lived radioactive tracer 13N. The routine for the online production of 13N-labeled nitrogen dioxide and the main experimental setup were reported previously [2]. Bovine serum albumin (BSA) was used as a model protein compound. Deliquesced NaCl particles were also used as a reference. Particles generated by an ultrasonic nebulizer were mixed with O3 (0 - 150 ppb) and NO2 (5 - 100 ppb) in a flow tube reactor under humid conditions (30 - 75 % RH), which lead to gel-like swelling of the protein [3, 4]. The reaction time was varied in the range of 4 -10 min by changing the position of the inlet of the reactor. The surface concentration of particles was monitored by a scanning mobility particle sizer (SMPS). After passing through the flow tube reactor, the gas and aerosol flow entered a narrow parallel-plate diffusion denuder coated to selectively absorb gas phase NO2, followed by a particle filter collecting the particles. The γ detectors were attached to each denuders and the filter to count the amount of gamma quanta, which are emitted in the decay of 13N. From the count-rate, the concentration of the corresponding species was derived, which was used for the calculation of uptake coefficients of NO2 (γNO2). In absence of O3 in the flow tube reactor, NO2 uptake by both BSA and deliquesced NaCl were below the detection limit (γNO2 < ~10-6). The γNO2 by BSA is of the order of 10-5, strongly depending on gas phase ozone concentration, which indicates that O3 plays an important role in NO2 uptake. The γNO2 by deliquesced NaCl is one order of magnitude smaller, which is likely to be attributed to the formation of gas phase NO3 and N2O5, as neither O3 nor NO2 is expected to rapidly react with deliquesced NaCl. This amount of uptake is considered to be maximum contribution of gas phase NO3 radicals and N2O5 to uptake of 13N-labeled species by protein particles. The possible mechanisms of high NO2 uptake by protein particles are: 1) surface reaction between adsorbed O3 and NO2 forming NO3 radicals on the surface which react with protein [5], 2) O3 first reacts with protein forming intermediates, followed by reaction with NO2. Further experiments and modelling are under way. REFERENCES [1] Franze et al., Environ. Sci. Tech., 39, 1673 (2005). [2] Sosedova et al., J. Phys. Chem A., 113, 10979 (2009). [3] Mikhailov et al., Atmos. Chem. Phys., 4, 323 (2004). [4] Mikhailov et al., Atmos. Chem. Phys., 9, 9491 (2009). [5] Shiraiwa et al., Atmos. Chem. Phys., 9, 9571 (2009)

Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ2-dmpe).

PubMed

Holmes, Aaron S; Patrick, Brian O; Levesque, Taleah M; Legzdins, Peter

2017-09-18

Reaction of Cp*Mo(NO)Cl 2 with 1 equiv of 1,2-bis(dimethylphosphino)ethane (dmpe) in THF at ambient temperature forms [Cp*Mo(NO)(Cl)(κ 2 -dmpe)]Cl (1), which is isolable as an analytically pure yellow powder in 65% yield. Further addition of 2 equiv of Cp 2 Co to 1 in CH 2 Cl 2 affords dark red Cp*Mo(NO)(κ 2 -dmpe) (2), which was isolated in 36% yield by recrystallization from Et 2 O at -30 °C. Reaction of a benzene solution of 2 with an equimolar amount of elemental sulfur results in the immediate production of dark blue (μ-S)[Cp*Mo(NO)(κ 1 -dmpeS)] 2 (3), which is a rare example of a bimetallic transition-metal complex bridged by only a single sulfur atom and involving Mo═S═Mo bonding. In contrast, reaction of 2 with an excess of sulfur in benzene results in the formation of Cp*Mo(NO)(η 2 -S 2 )(κ 1 -dmpeS) (4). Complex 4 can also be formed by the addition of elemental sulfur to 3, thereby indicating that 3 is a precursor to 4. Cp*Mo(NO)(κ 2 -dmpe) (2) also undergoes interesting transformations when treated with organic bromides. For instance, reaction of 2 with 5 equiv benzyl bromide in THF produces the bimetallic complex (μ-dmpe)[Cp*Mo(NO)Br 2 ] 2 (5) and bibenzyl after 4 d at 70 °C probably via radical intermediates. In contrast to its reaction with benzyl bromide, complex 2 forms [Mo(NO)Br 2 (κ 2 -dmpe)] 2 (6), olefin, alkane, and Cp*H when treated with 5 equiv of 1-bromopropane or 1-bromooctane in THF at 70 °C for 72 h. Interestingly, complex 2 does not display any reactivity with bromobenzene or 1-bromoadamantane even after being heated for several days at 70 °C. All new complexes were characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them were established by single-crystal X-ray crystallographic analyses.

DETANO and nitrated lipids increase chloride secretion across lung airway cells.

PubMed

Chen, Lan; Bosworth, Charles A; Pico, Tristant; Collawn, James F; Varga, Karoly; Gao, Zhiqian; Clancy, John Paul; Fortenberry, James A; Lancaster, Jack R; Matalon, Sadis

2008-08-01

We investigated the cellular mechanisms by which nitric oxide (NO) increases chloride (Cl-) secretion across lung epithelial cells in vitro and in vivo. Addition of (Z)-1-[2-(2-aminoethyl)-N-(2-ammonioethyl) amino] diazen-1-ium-1, 2-diolate (DETANONOate [DETANO];1-1,000 microM) into apical compartments of Ussing chambers containing Calu-3 cells increased short-circuit currents (I(sc)) from 5.2 +/- 0.8 to 15.0 +/- 2.1 microA/cm(2) (X +/- 1 SE; n = 7; P < 0.001). NO generated from two nitrated lipids (nitrolinoleic and nitrooleic acids; 1-10 microM) also increased I(sc) by about 100%. Similar effects were noted across basolaterally, but not apically, permeabilized Calu-3 cells. None of these NO donors increased I(sc) in Calu-3 cells pretreated with 10 microM 1H-[1,2,4]oxadiazolo[4,3-a]quinoxalin-1-one (an inhibitor of soluble guanylyl cyclase). Scavenging of NO either prevented or reversed the increase of I(sc). These data indicate that NO stimulation of soluble guanylyl cyclase was sufficient and necessary for the increase of I(sc) via stimulation of the apical cystic fibrosis transmembrane regulator (CFTR). Both Calu-3 and alveolar type II (ATII) cells contained CFTR, as demonstrated by in vitro phosphorylation of immunoprecipitated CFTR by protein kinase (PK) A. PKGII (but not PKGI) phosphorylated CFTR immuniprecipitated from Calu-3 cells. Corresponding values in ATII cells were below the threshold of detection. Furthermore, DETANO, 8-Br-cGMP, or 8-(4-chlorophenylthio)-cGMP (up to 2 mM each) did not increase Cl- secretion across amiloride-treated ATII cells in vitro. Measurements of nasal potential differences in anesthetized mice showed that perfusion of the nares with DETANO activated glybenclamide-sensitive Cl- secretion. These findings suggest that small concentrations of NO donors may prove beneficial in stimulating Cl- secretion across airway cells without promoting alveolar edema.

Quantitative analysis of ions in spring water in three different areas of Hyogo Prefecture in Japan by far ultraviolet spectroscopy.

PubMed

Mitsuoka, Motoki; Shinzawa, Hideyuki; Morisawa, Yusuke; Kariyama, Naomi; Higashi, Noboru; Tsuboi, Motohiro; Ozaki, Yukihiro

2011-01-01

Far-ultraviolet (FUV) spectra in the 190-300 nm region were measured for spring water in Awaji-Akashi area, Tamba area and Rokko-Arima area in Hyogo Prefecture, Japan, these areas have quite different geology features. The spectra of the spring water in the Awaji-Akashi area can be divided into two groups: the spring water samples containing large amounts of NO(3)(-) and/or Cl(-), and those containing only small amounts of NO(3)(-) and Cl(-). The former shows a saturated band below 190 nm due to NO(3)(-) and/or Cl(-). These two types of spectra correspond to different lithological areas: sedimentary lithology near the sea shore containing many ions in the seawater and gravitic lithology far from the sea side, in the Awaji-Akashi area. The spring water from the Tamba area, which is far from the sea, contains relatively small amounts of NO(3)(-) and Cl(-); it does not yield a strong band in the region observed. The FUV spectra of three of four kinds of spring water samples in the Arima Hotspring show characteristic spectral patterns. They are quite different from the spectra of the spring water samples of the Rokko area. Calibration models were developed for NO(3)(-), Cl(-), SO(4)(2-), Na(+), and Mg(2+) in the nine kinds of spring water collected in the Awaji-Akashi area, Tamba, and Rokko-Arima area by using univariate analysis of the first derivative spectra and the actual values obtained by ion chromatography. NO(3)(-) yields the best results: correlation coefficient of 0.999 and standard deviation of 0.09 ppm with the wavelength of 212 nm. Cl(-) also gives good results: correlation coefficient of 0.993 and standard deviation of 0.5 ppm with the wavelength of 192 nm.

Matrix isolation infrared spectra of hydrogen halide and halogen complexes with nitrosyl halides

NASA Technical Reports Server (NTRS)

Allamandola, Louis J.; Lucas, Donald; Pimentel, George C.

1982-01-01

Matrix isolation infrared spectra of nitrosyl halide (XNO) complexes with HX and X2 (X = Cl, Br) are presented. The relative frequency shifts of the HX mode are modest (ClNO H-Cl, delta-nu/nu = -0.045; BrNO H-Br, delta-nu/nu = -0.026), indicating weak hydrogen bonds 1-3 kcal/mol. These shifts are accompanied by significant shifts to higher frequencies in the XN-O stretching mode (CIN-O HCl, delta-nu/nu = +0.016; BrN-O HBr, delta-nu/nu = +0.011). Similar shifts were observed for the XN-O X2 complexes (ClN-O Cl2, delta-nu/nu = +0.009; BrN-O-Br2, delta-nu/nu = +0.013). In all four complexes, the X-NO stretching mode relative shift is opposite in sign and about 1.6 times that of the NO stretching mode. These four complexes are considered to be similar in structure and charge distribution. The XN-O frequency shift suggests that complex formation is accompanied by charge withdrawal from the NO bond ranging from about .04 to .07 electron charges. The HX and X2 molecules act as electron acceptors, drawing electrons out of the antibonding orbital of NO and strengthening the XN-O bond. The implications of the pattern of vibrational shifts concerning the structure of the complexes are discussed.

Electronic Absorption and MCD Spectra for Pd(AuPPh(3))(8)(2+), Pt(AuPPh(3))(8)(2+), and Related Platinum-Centered Gold Cluster Complexes.

PubMed

Adrowski, Michael J.; Mason, W. Roy

1997-03-26

Electronic absorption and 7.0 T magnetic circular dichroism (MCD) spectra in the UV-vis region, 1.6 to approximately 4.0 &mgr;m(-)(1) (1 &mgr;m(-)(1) = 10(4) cm(-)(1)) are reported for [Pd(AuPPh(3))(8)](NO(3))(2) and [Pt(AuPPh(3))(8)](NO(3))(2) in acetonitrile solutions at room temperature. The MCD spectra are better resolved than the absorption spectra and consist of both A and B terms. The spectra are interpreted in terms of D(4)(d)() skeletal geometry and MO's that are approximated by 5s and 6s orbitals for Pd and Pt/Au atoms, respectively. The lowest energy excited configurations and states are attributed to intraframework (IF) Au(8)(2+) transitions. Evidence is also presented for Pt 5d --> Au 6s transitions in the MCD spectra for Pt(AuPPh(3))(8)(2+). Acetonitrile solution absorption and MCD spectra for the related Pt-centered cluster complexes [Pt(CO)(AuPPh(3))(8)](NO(3))(2), [Pt(AuP(p-tolyl)(3))(8)](NO(3))(2), [Pt(CuCl)(AuPPh(3))(8)](NO(3))(2), [Pt(AgNO(3))(AuPPh(3))(8)](NO(3))(2), [Pt(Hg)(2)(AuPPh(3))(8)](NO(3))(2), [Pt(HgCl)(2)(AuPPh(3))(8)](BF(4))(2), and [Pt(HgNO(3))(2)(AuPPh(3))(8)](BF(4))(2) are also reported and interpreted within the context of the model developed for the M(AuPPh(3))(8)(2+) complexes.

Observations of nitryl chloride and modeling its source and effect on ozone in the planetary boundary layer of southern China

NASA Astrophysics Data System (ADS)

Wang, Tao; Tham, Yee Jun; Xue, Likun; Li, Qinyi; Zha, Qiaozhi; Wang, Zhe; Poon, Steven C. N.; Dubé, William P.; Blake, Donald R.; Louie, Peter K. K.; Luk, Connie W. Y.; Tsui, Wilson; Brown, Steven S.

2016-03-01

Nitryl chloride (ClNO2) plays potentially important roles in atmospheric chemistry, but its abundance and effect are not fully understood due to the small number of ambient observations of ClNO2 to date. In late autumn 2013, ClNO2 was measured with a chemical ionization mass spectrometer (CIMS) at a mountain top (957 m above sea level) in Hong Kong. During 12 nights with continuous CIMS data, elevated mixing ratios of ClNO2 (>400 parts per trillion by volume) or its precursor N2O5 (>1000 pptv) were observed on six nights, with the highest ever reported ClNO2 (4.7 ppbv, 1 min average) and N2O5 (7.7 ppbv, 1 min average) in one case. Backward particle dispersion calculations driven by winds simulated with a mesoscale meteorological model show that the ClNO2/N2O5-laden air at the high-elevation site was due to transport of urban/industrial pollution north of the site. The highest ClNO2/N2O5 case was observed in a later period of the night and was characterized with extensively processed air and with the presence of nonoceanic chloride. A chemical box model with detailed chlorine chemistry was used to assess the possible impact of the ClNO2 in the well-processed regional plume on next day ozone, as the air mass continued to downwind locations. The results show that the ClNO2 could enhance ozone by 5-16% at the ozone peak or 11-41% daytime ozone production in the following day. This study highlights varying importance of the ClNO2 chemistry in polluted environments and the need to consider this process in photochemical models for prediction of ground-level ozone and haze.

Ultrasound promoted synthesis of 2-imidazolines in water: a greener approach toward monoamine oxidase inhibitors.

PubMed

Sant' Anna, Gabriela da S; Machado, Pablo; Sauzem, Patricia D; Rosa, Fernanda A; Rubin, Maribel A; Ferreira, Juliano; Bonacorso, Helio G; Zanatta, Nilo; Martins, Marcos A P

2009-01-15

A series of sixteen 2-substituted-2-imidazolines (where the substituent R=Ph, Me-4-Ph; MeO-4-Ph; (MeO)(2)-3,4-Ph; (MeO)(3)-3,4,5-Ph; Ph-4-O-C(O)-Ph; Cl-4-Ph; Cl-2-Ph; Cl(2)-2,4-Ph; NO(2)-4-Ph; NO(2)-3-Ph; Naphth-2-yl; Fur-2-yl; Benzofur-2-yl; Pyridin-2-yl; Quinolin-2-yl) has been synthesized from the reaction of the substituted-aldehydes and ethylenediamine by ultrasound irradiation with NBS in an aqueous medium in high yields (80-99%). The 2-imidazoline ability to inhibit the activity of the A and B isoforms of monoamine oxidase (MAO) was investigated and some of them showed potent and selective MAO inhibitory activity especially for the MAO-B isoform and could become promising candidates for future development.

Heteropentanuclear Oxalato-Bridged nd–4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity

PubMed Central

Kuhn, Paul-Steffen; Cremer, Laura; Gavriluta, Anatolie; Jovanović, Katarina K; Filipović, Lana; Hummer, Alfred A; Büchel, Gabriel E; Dojčinović, Biljana P; Meier, Samuel M; Rompel, Annette; Radulović, Siniša; Tommasino, Jean Bernard; Luneau, Dominique; Arion, Vladimir B

2015-01-01

A series of heteropentanuclear oxalate-bridged Ru(NO)-Ln (4d–4f) metal complexes of the general formula (nBu4N)5[Ln{RuCl3(μ-ox)(NO)}4], where Ln=Y (2), Gd (3), Tb (4), Dy (5) and ox=oxalate anion, were obtained by treatment of (nBu4N)2[RuCl3(ox)(NO)] (1) with the respective lanthanide salt in 4:1 molar ratio. The compounds were characterized by elemental analysis, IR spectroscopy, electrospray ionization (ESI) mass spectrometry, while 1, 2, and 5 were in addition analyzed by X-ray crystallography, 1 by Ru K-edge XAS and 1 and 2 by 13C NMR spectroscopy. X-ray diffraction showed that in 2 and 5 four complex anions [RuCl3(ox)(NO)]2− are coordinated to YIII and DyIII, respectively, with formation of [Ln{RuCl3(μ-ox)(NO)}4]5− (Ln=Y, Dy). While YIII is eight-coordinate in 2, DyIII is nine-coordinate in 5, with an additional coordination of an EtOH molecule. The negative charge is counterbalanced by five nBu4N+ ions present in the crystal structure. The stability of complexes 2 and 5 in aqueous medium was monitored by UV/Vis spectroscopy. The antiproliferative activity of ruthenium-lanthanide complexes 2–5 were assayed in two human cancer cell lines (HeLa and A549) and in a noncancerous cell line (MRC-5) and compared with those obtained for the previously reported Os(NO)-Ln (5d–4f) analogues (nBu4N)5[Ln{OsCl3(ox)(NO)}4] (Ln=Y (6), Gd (7), Tb (8), Dy (9)). Complexes 2–5 were found to be slightly more active than 1 in inhibiting the proliferation of HeLa and A549 cells, and significantly more cytotoxic than 5d–4f metal complexes 6–9 in terms of IC50 values. The highest antiproliferative activity with IC50 values of 20.0 and 22.4 μM was found for 4 in HeLa and A549 cell lines, respectively. These cytotoxicity results are in accord with the presented ICP-MS data, indicating five- to eightfold greater accumulation of ruthenium versus osmium in human A549 cancer cells. PMID:26260662

Refractivity of Molten Nitrates and Chlorides: Binary Mixtures Containing Cesium Ions

NASA Astrophysics Data System (ADS)

Uchiyama, Yohji; Karawacki, Ernest

1981-05-01

By using an interferometric technique, the refractive index of some molten salt mixtures containing Cs+ ions was measured with high accuracy: (Li-Cs)NO3, (Na-Cs)NO3, (Ag-Cs)NO3, (Li-Cs)Cl, and also pure RbCl. The isotherms of molar refractivity show a small negative deviation from additivity in the (Li-Cs)NO3 and (Li-Cs)Cl systems and a positive deviation in the (Ag-Cs)NO3 mixture. A tentative attempt was made to relate the excess molar refractivities with the absorption bands of the ions.

DNA as a Target for Anticancer Phen-Imidazole Pd(II) Complexes.

PubMed

Heydari, Maryam; Moghadam, Mahboube Eslami; Tarlani, AliAkbar; Farhangian, Hossein

2017-05-01

Imidazole ring is a known structure in many natural or synthetic drug molecules and its metal complexes can interact with DNA and do the cleavage. Hence, to study the influence of the structure and size of the ligand on biological behavior of metal complexes, two water-soluble Pd(II) complexes of phen and FIP ligands (where phen is 1,10-phenanthroline and FIP is 2-(Furan-2-yl)-1H-Imidazo[4,5-f][1, 10]phenanthroline) with the formula of [Pd(phen)(FIP)](NO 3 ) 2 and [Pd(FIP) 2 ]Cl 2 , that were activated against chronic myelogenous leukemia cell line, K562, were selected. Also, the interaction of these anticancer Pd(II) complexes with highly polymerized calf thymus DNA was extensively studied by means of electronic absorption, fluorescence, and circular dichroism in Tris-buffer. The results showed that the binding was positive cooperation and [Pd(phen)(FIP)](NO 3 ) 2 (K f  = 127 M -1 G = 1.2) exhibited higher binding constant and number of binding sites than [Pd(FIP) 2 ]Cl 2 (K f  = 13 M -1 G = 1.03) upon binding to DNA. The fluorescence data indicates that quenching effect for [Pd(phen)(FIP)](NO 3 ) 2 (K SV  = 58 mM -1 ) was higher than [Pd(FIP) 2 ]Cl 2 (K SV  = 12 mM -1 ). Also, [Pd(FIP) 2 ]Cl 2 interacts with ethidium bromide-DNA, as non-competitive inhibition, and can bind to DNA via groove binding and [Pd(phen)(FIP)](NO 3 ) 2 can intercalate in DNA. These results were confirmed by circular dichroism spectra. Docking data revealed that longer complexes have higher interaction energy and bind to DNA via groove binding. Graphical Abstract Two anticancer Pd(II) complexes of imidazole derivative have been synthesized and interacted with calf thymus DNA. Modes of binding have been studied by electronic absorption, fluorescence, and CD measurements. [Pd(FIP) 2 ]Cl 2 can bind to DNA via groove binding while intercalation mode of binding is observed for [Pd(phen)(FIP)](NO 3 ) 2 .

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.

Production of N2O5 and ClNO2 through Nocturnal Processing of Biomass-Burning Aerosol.

PubMed

Ahern, Adam T; Goldberger, Lexie; Jahl, Lydia; Thornton, Joel; Sullivan, Ryan C

2018-01-16

Biomass burning is a source of both particulate chloride and nitrogen oxides, two important precursors for the formation of nitryl chloride (ClNO 2 ), a source of atmospheric oxidants that is poorly prescribed in atmospheric models. We investigated the ability of biomass burning to produce N 2 O 5 (g) and ClNO 2 (g) through nocturnal chemistry using authentic biomass-burning emissions in a smog chamber. There was a positive relationship between the amount of ClNO 2 formed and the total amount of particulate chloride emitted and with the chloride fraction of nonrefractory particle mass. In every fuel tested, dinitrogen pentoxide (N 2 O 5 ) formed quickly, following the addition of ozone to the smoke aerosol, and ClNO 2 (g) production promptly followed. At atmospherically relevant relative humidities, the particulate chloride in the biomass-burning aerosol was rapidly but incompletely displaced, likely by the nitric acid produced largely by the heterogeneous uptake of N 2 O 5 (g). Despite this chloride acid displacement, the biomass-burning aerosol still converted on the order of 10% of reacted N 2 O 5 (g) into ClNO 2 (g). These experiments directly confirm that biomass burning is a potentially significant source of atmospheric N 2 O 5 and ClNO 2 to the atmosphere.

ABA, GA(3), and nitrate may control seed germination of Crithmum maritimum (Apiaceae) under saline conditions.

PubMed

Atia, Abdallah; Debez, Ahmed; Barhoumi, Zouhaier; Smaoui, Abderrazak; Abdelly, Chedly

2009-08-01

Impaired germination is common among halophyte seeds exposed to salt stress, partly resulting from the salt-induced reduction of the growth regulator contents in seeds. Thus, the understanding of hormonal regulation during the germination process is a main key: (i) to overcome the mechanisms by which NaCl-salinity inhibit germination; and (ii) to improve the germination of these species when challenged with NaCl. In the present investigation, the effects of ABA, GA(3), NO(-)(3), and NH(+)(4) on the germination of the oilseed halophyte Crithmum maritimum (Apiaceae) were assessed under NaCl-salinity (up to 200 mM NaCl). Seeds were collected from Tabarka rocky coasts (N-W of Tunisia). The exogenous application of GA(3), nitrate (either as NaNO(3) or KNO(3)), and NH(4)Cl enhanced germination under NaCl salinity. The beneficial impact of KNO(3) on germination upon seed exposure to NaCl salinity was rather due to NO(-)(3) than to K(+), since KCl failed to significantly stimulate germination. Under optimal conditions for germination (0 mM NaCl), ABA inhibited germination over time in a dose dependent manner, but KNO(3) completely restored the germination parameters. Under NaCl salinity, the application of fluridone (FLU) an inhibitor of ABA biosynthesis, stimulated substantially seed germination. Taken together, our results point out that NO(-)(3) and GA(3) mitigate the NaCl-induced reduction of seed germination, and that NO(-)(3) counteracts the inhibitory effect of ABA on germination of C. maritimum.

17 CFR 151.3 - Spot months for Referenced Contracts.

Code of Federal Regulations, 2014 CFR

2014-04-01

... Referenced Futures Contract for the ICE Futures U.S. Sugar No. 11 (SB) Referenced Contract; (3) At the close... delivery period in the underlying Core Referenced Futures Contract for the ICE Futures U.S. Sugar No. 16... Exchange Light Sweet Crude Oil (CL) contract; (2) New York Mercantile Exchange New York Harbor No. 2...

17 CFR 151.3 - Spot months for Referenced Contracts.

Code of Federal Regulations, 2013 CFR

2013-04-01

... Contract for the ICE Futures U.S. Sugar No. 11 (SB) Referenced Contract; (3) At the close of business on... in the underlying Core Referenced Futures Contract for the ICE Futures U.S. Sugar No. 16 (SF... Exchange Light Sweet Crude Oil (CL) contract; (2) New York Mercantile Exchange New York Harbor No. 2...

17 CFR 151.3 - Spot months for Referenced Contracts.

Code of Federal Regulations, 2012 CFR

2012-04-01

... Contract for the ICE Futures U.S. Sugar No. 11 (SB) Referenced Contract; (3) At the close of business on... in the underlying Core Referenced Futures Contract for the ICE Futures U.S. Sugar No. 16 (SF... Exchange Light Sweet Crude Oil (CL) contract; (2) New York Mercantile Exchange New York Harbor No. 2...

Reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl2(κ3N4,N8,N11(1-carboxypropyl)cyclam)]Cl·H2O.

PubMed

Doro, Fabio G; Pepe, Iuri M; Galembeck, Sergio E; Carlos, Rose M; da Rocha, Zenis N; Bertotti, Mauro; Tfouni, Elia

2011-06-28

Chemical reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam, fac-[Ru(NO)Cl(2)(κ(3)N(4),N(8),N(11)(1-carboxypropyl)cyclam)]Cl·H(2)O ((1-carboxypropyl)cyclam = 3-(1,4,8,11-tetraazacyclotetradecan-1-yl)propionic acid)), (I) are described. Chloride ligands do not undergo aquation reactions (at 25 °C, pH 3). The rate of nitric oxide (NO) dissociation (k(obs-NO)) upon reduction of I is 2.8 s(-1) at 25 ± 1 °C (in 0.5 mol L(-1) HCl), which is close to the highest value found for related complexes. The uncoordinated carboxyl of I has a pK(a) of ∼3.3, which is close to that of the carboxyl of the non coordinated (1-carboxypropyl)cyclam (pK(a) = 3.4). Two additional pK(a) values were found for I at ∼8.0 and ∼11.5. Upon electrochemical reduction or under irradiation with light (λ(irr) = 350 or 520 nm; pH 7.4), I releases NO in aqueous solution. The cyclam ring N bound to the carboxypropyl group is not coordinated, resulting in a fac configuration that affects the properties and chemical reactivities of I, especially as NO donor, compared with analogous trans complexes. Among the computational models tested, the B3LYP/ECP28MDF, cc-pVDZ resulted in smaller errors for the geometry of I. The computational data helped clarify the experimental acid-base equilibria and indicated the most favourable site for the second deprotonation, which follows that of the carboxyl group. Furthermore, it showed that by changing the pH it is possible to modulate the electron density of I with deprotonation. The calculated NO bond length and the Ru/NO charge ratio indicated that the predominant canonical structure is [Ru(III)NO], but the Ru-NO bond angles and bond index (b.i.) values were less clear; the angles suggested that [Ru(II)NO(+)] could contribute to the electronic structure of I and b.i. values indicated a contribution from [Ru(IV)NO(-)]. Considering that some experimental data are consistent with a [Ru(II)NO(+)] description, while others are in agreement with [Ru(III)NO], the best description for I would be a linear combination of the three canonical forms, with a higher weight for [Ru(II)NO(+)] and [Ru(III)NO]. This journal is © The Royal Society of Chemistry 2011

Mechanism of single metal exchange in the reactions of [M4(SPh)10]2- (M = Zn or Fe) with CoX2 (X = Cl or NO3) or FeCl2.

PubMed

Autissier, Valerie; Henderson, Richard A

2008-07-21

The kinetics of the reactions between [Zn4(SPh)10](2-) and an excess of MX2 (M = Co, X = NO3 or Cl; M = Fe, X = Cl), in which a Zn(II) is replaced by M(II), have been studied in MeCN at 25.0 degrees C. (1)H NMR spectroscopy shows that the ultimate product of the reactions is an equilibrium mixture of clusters of composition [Zn(n)M(4-n)(SPh)10](2-), and this is reflected in the multiphasic absorbance-time curves observed over protracted times (several minutes) using stopped-flow spectrophotometry to study the reactions. The kinetics of only the first phase have been determined, corresponding to the equilibrium formation of [Zn3M(SPh)10](2-). The effects of varying the concentrations of cluster, MX2, and ZnCl2 on the kinetics have been investigated. The rate law is consistent with the equilibrium nature of the metal exchange process and indicates a mechanism for the formation of [Zn3M(SPh)10](2-) involving two coupled equilibria. In the initial step binding of MX2 to a bridging thiolate in [Zn4(SPh)10](2-) results in breaking of a Zn-bridging thiolate bond. In the second step replacement of the cluster Zn involves transfer of the bridging thiolates from the Zn to M, with breaking of a Zn-bridged thiolate bond being rate-limiting. The kinetics for the reaction of ZnCl2 with [Zn3M(SPh)10](2-) (M = Fe or Co)} depends on the identity of M. This behavior indicates attack of ZnCl2 at a M-mu-SPh-Zn bridged thiolate. Similar studies on the analogous reactions between [Fe4(SPh)10](2-) and an excess of CoX2 (X = NO3 or Cl) in MeCN exhibit simpler kinetics but these are also consistent with the same mechanism.

116 kDa glycoprotein isolated from Ulmus davidiana Nakai (UDN) inhibits glucose/glucose oxidase (G/GO)-induced apoptosis in BNL CL.2 cells.

PubMed

Ko, Jeong-Hyeon; Lee, Sei-Jung; Lim, Kye-Taek

2005-09-14

Ulmus davidiana Nakai (UDN) has been used in folk medicine for its anti-inflammatory activity. In the present study, we investigated the antiapoptotic effect of UDN glycoprotein in glucose/glucose oxidase (G/GO)-induced BNL CL.2 cells. To evaluate the antiapoptotic effect of UDN glycoprotein, experiments were carried out using Western blot analysis for nuclear factor-kappa B (NF-kappaB), caspase-3, and poly(ADP-ribose) polymerase (PARP). We also examined nitric oxide (NO) production and nuclear staining. When BNL CL.2 cells were treated with G/GO (50 mU/ml), viability of the cells was 54.1%. However, the number of living cells after the addition of UDN glycoprotein in the presence of G/GO increased. UDN glycoprotein protected from cell damage caused by G/GO. Interestingly, UDN glycoprotein decreased NF-kappaB activation and stimulated NO production in G/GO-induced BNL CL.2 cells. In apoptotic parameters, UDN glycoprotein inhibited activations of caspase-3 and PARP cleavage in G/GO-induced BNL CL.2 cells. The results of nuclear staining indicated that UDN glycoprotein (50 microg/ml) has a protective ability from apoptotic cell death caused G/GO (50 mU/ml). In conclusion, UDN glycoprotein has a protective effect on apoptosis induced by G/GO through the inhibition of NF-kappaB, caspase-3, and PARP activity, and the stimulation of NO production in BNL CL.2 cells.

Effects of inorganic electrolyte anions on enrichment of Cu(II) ions with aminated Fe3O4/graphene oxide: Cu(II) speciation prediction and surface charge measurement.

PubMed

Hu, Xin-jiang; Liu, Yun-guo; Zeng, Guang-ming; Wang, Hui; You, Shao-hong; Hu, Xi; Tan, Xiao-fei; Chen, An-wei; Guo, Fang-ying

2015-05-01

The present work evaluated the effects of six inorganic electrolyte anions on Cu(II) removal using aminated Fe3O4/graphene oxide (AMGO) in single- and multi-ion systems. A 2(6-2) fractional factorial design (FFD) was employed for assessing the effects of multiple anions on the adsorption process. The results indicated that the Cu(II) adsorption was strongly dependent on pH and could be significantly affected by inorganic electrolyte anions due to the changes in Cu(II) speciation and surface charge of AMGO. In the single-ion systems, the presence of monovalent anions (Cl(-), ClO4(-), and NO3(-)) slightly increased the Cu(II) adsorption onto AMGO at low pH, while the Cu(II) adsorption was largely enhanced by the presence of SO4(2-), CO3(2-), and HPO4(2-). Based on the estimates of major effects and interactions from FFD, the factorial effects of the six selected species on Cu(II) adsorption in multi-ion system were in the following sequence: HPO4(2-)>CO3(2-)>Cl(-)>SO4(2-)>NO3(-)=ClO4(-), and the combined factors of AD (Cl(-)×SO4(2-)) and EF (Cl(-)×SO4(2-)) had significant effects on Cu(II) removal. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effects of aqueous chlorine dioxide treatment on nutritional components and shelf-life of mulberry fruit (Morus alba L.).

PubMed

Chen, Zhao; Zhu, Chuanhe; Han, Ziqiang

2011-06-01

Effects of aqueous chlorine dioxide (ClO(2)) treatment on nutritional components and shelf-life of mulberry fruit (Morus alba L.) were investigated. Mulberry fruit were immersed into 20, 60, and 80 mg/l ClO(2) solutions for 5, 10, and 15 min, respectively. Mulberries were then rinsed with potable tap water for 1 min and stored at -1°C for 14 d. ClO(2) treatment was effective in retention of flavonoid, ascorbic acid, reducing sugar, and titratable acid. ClO(2) concentration and treatment time were significant factors affecting ClO(2) treatment. The shelf-life of the samples treated by 60 mg/l ClO(2) for 15 min was extended to 14 d compared to 8 d for the control. No ClO(2), ClO(2)(-), or ClO(3)(-) residues were detected in samples treated by 60 mg/l ClO(2) for 15 min. These results indicated that ClO(2) treatment was a promising approach to preserve mulberry fruit with no significant risks of chemical residues. Copyright © 2011 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Crystal structures of five (2-chloro­quinolin-3-yl)methyl ethers: supra­molecular assembly in one and two dimensions mediated by hydrogen bonding and π–π stacking

PubMed Central

Sowmya, Haliwana B. V.; Suresha Kumara, Tholappanavara H.; Gopalpur, Nagendrappa; Jasinski, Jerry P.; Millikan, Sean P.; Yathirajan, Hemmige S.; Glidewell, Christopher

2015-01-01

In the mol­ecules of the title compounds, methyl 5-bromo-2-[(2-chloro­quinolin-3-yl)meth­oxy]benzoate, C18H13BrClNO3, (I), methyl 5-bromo-2-[(2-chloro-6-methyl­quinolin-3-yl)meth­oxy]benzoate, C19H15BrClNO3, (II), methyl 2-[(2-chloro-6-methyl­quinolin-3-yl)meth­oxy]benzoate, C19H16ClNO3, (III), which crystallizes with Z′ = 4 in space group P212121, and 2-chloro-3-[(naphthalen-1-yl­oxy)meth­yl]quinoline, C20H14ClNO, (IV), the non-H atoms are nearly coplanar, but in {5-[(2-chloro­quinolin-3-yl)meth­oxy]-4-(hy­droxy­meth­yl)-6-methyl­pyridin-3-yl}methanol, C18H17ClN2O3, (V), the planes of the quinoline unit and of the unfused pyridine ring are almost parallel, although not coplanar. The mol­ecules of (I) are linked by two independent π–π stacking inter­actions to form chains, but there are no hydrogen bonds present in the structure. In (II), the mol­ecules are weakly linked into chains by a single type of π–π stacking inter­action. In (III), three of the four independent mol­ecules are linked by π–π stacking inter­actions but the other mol­ecule does not participate in such inter­actions. Weak C—H⋯O hydrogen bonds link the mol­ecules into three types of chains, two of which contain just one type of independent mol­ecule while the third type of chain contains two types of mol­ecule. The mol­ecules of (IV) are linked into chains by a C—H⋯π(arene) hydrogen bond, but π–π stacking inter­actions are absent. In (V), there is an intra­molecular O—H⋯O hydrogen bond, and mol­ecules are linked into sheets by a combination of O—H⋯N hydrogen bonds and π–π stacking inter­actions. PMID:26090133

Rhodiola sachalinesis induces the expression of inducible nitric oxide synthase gene by murine fetal hepatocytes (BNL CL.2).

PubMed

Pae, H O; Seo, W G; Oh, G S; Kim, N Y; Kim, Y M; Kwon, T O; Shin, M K; Chai, K Y; Chung, H T

2001-02-01

We have examined the effect of the aqueous extract of Rhodiola sachalinensis root (RSE), a traditional herbal medicine, on nitric oxide (NO) synthesis in murine fetal hepatocytes (BNL CL.2) by measuring the stable end-product nitrite and the mRNA of inducible NO synthase (iNOS). Interferon-gamma (IFN-gamma) by itself failed to induce NO synthesis in BNL CL.2 cells. RSE also did not elicit NO synthesis at concentrations up to 1,000 microg/ml, but dose- and time-dependently induced NO synthesis in the presence of IFN-gamma in BNL CL.2 cells. Whereas RSE or IFN-gamma failed to induce detectable levels of iNOS mRNA, a combination of RSE and IFN-gamma markedly induced iNOS mRNA in BNL CL.2 cells. Thus, we found that RSE triggered IFN-gamma-primed BNL CL.2 cells to synthesize NO by inducing iNOS gene expression. The capability of RSE to induce NO synthesis might be related to the therapeutic efficacy of RSE on the liver diseases.

Seasonal variations in the major chemical species of snow at the South East Dome in Greenland

NASA Astrophysics Data System (ADS)

Oyabu, Ikumi; Matoba, Sumito; Yamasaki, Tetsuhide; Kadota, Moe; Iizuka, Yoshinori

2016-03-01

We analyze snow-pit samples collected in May 2015 at the South East Dome (SE Dome) on the Greenland ice sheet. The analysis includes high-resolution records of δD and δ18O, as well as the major ions, CH3SO3-, Cl-, NO3-, SO42-, Na+, NH4+, K+, Ma2+, and Ca2+. We find that the 3.55-m snow pit recorded temperature and aerosol proxies back to summer or autumn of 2014. This indicates a higher accumulation rate than those at other major drilling sites in Greenland. Due to this high accumulation rate, ion concentrations except Na+ are lower than those typical of the central Greenland ice sheet. Concerning seasonal variability, the Na+, Cl-, Ca2+, Mg2+, and NO3- vary similarly to other sites in Greenland, with the Na+ and Cl- peaking in winter to early spring, Ca2+ peaking in spring, Mg2+ peaking in winter to spring, and NO3- towards a peak in summer while showing smaller peaks in winter to spring. The NH4+ increased in spring, and SO42- increased in autumn to winter at SE Dome. On the other hand, the seasonal trend in the Cl-/Na+ ratio differs from those in the inland region. As we did not fully recover one seasonal cycle, some seasonal peaks may have been missed.

Silver accumulation in Pseudomonas stutzeri AG259.

PubMed

Gadd, G M; Laurence, O S; Briscoe, P A; Trevors, J T

1989-01-01

Silver toxicity to Pseudomonas stutzeri AG259 was strongly dependent on the NaCl concentration in the medium, which reduced the availability of Ag+ by precipitation as AgCl. Accumulation of Ag by growing cultures was low being less than or equal to 7.5 nmol (mg dry mass)-1 over all treatments examined. The presence of NaCl in the growth medium did not markedly affect the amounts of Ag accumulated by the cells but influenced toxicity as manifest by a lag period which was greatest at low NaCl concentrations (less than or equal to 0.1% mass/vol.). In NaCl-free medium, P. stutzeri did not grow in the presence of 0.5 mM AgNO3 in contrast to Ag-free controls. The majority of Ag accumulation by resting cells of P. stutzeri occurred within 1 min of incubation and there was little difference in uptake capacities between cells previously grown in the absence or presence of AgNO3. Lowest amounts of Ag uptake by resting cells occurred when suspended in 1 mM Mes pH 6.5, containing 1% (mass/vol.) NaCl. Prior exposure of P. stutzeri to Cu(NO3)2 resulted in a marked reduction in Ag uptake when suspended in 1 mM Mes pH 6.5, containing 0.5 mM AgNO3.

Mercury(II) complexes of unsymmetric phosphorus ylides: Synthesis, spectroscopic and antibacterial activity studies

NASA Astrophysics Data System (ADS)

Sabounchei, Seyyed Javad; Panahimehr, Mohammad; Hosseinzadeh, Marjan; Karamian, Roya; Asadbegy, Mostafa; Masumi, Azadeh

2014-03-01

The reaction of Ph2PCH2PPh2 (dppm) with 2-bromo-3-nitroacetophenone and 2,2‧,4‧-trichloroacetophenone in chloroform produce the new phosphonium salts [Ph2PCH2PPh2CH2C(O)C6H4NO2]Br (1) and [Ph2PCH2PPh2CH2C(O)C6H3Cl2]Cl (2). Further, by reaction of the monophosphonium salts of dppm with the strong base triethylaminethe corresponding bidentate phosphorus ylides, Ph2PCH2PPh2C(H)C(O)C6H4NO2 (3) and Ph2PCH2PPh2C(H)C(O)C6H3Cl2 (4) were obtained. The reaction of these ligands with mercury(II) halides in dry methanol led to the formation of the mononuclear complexes {HgX2[(Ph2PCH2PPh2C(H)C(O)C6H4NO2)]} [X = Cl (5), Br (6), I (7)] and {HgX2[(Ph2PCH2PPh2C(H)C(O)C6H3Cl2)]} [X = Cl (8), Br (9), I (10)]. Characterization of the obtained compounds was performed by elemental analysis, IR, 1H, 31P and 13C NMR. The structure of compound 1 being unequivocally determined by single crystal X-ray diffraction techniques. The mass spectrum of compound 6 (as an instance) also demonstrates the synthesize of these compounds. In all complexes the title ylides are coordinated through the ylidic carbon and the phosphine atom. These compounds form five membered ring under complexation. The antibacterial effects of DMSO solutions of the ligands and their metal complexes were evaluated by the disc diffusion method against six Gram positive and negative bacteria. All compounds represent antibacterial activity against these bacteria with high levels of inhibitory potency exhibited against the Gram positive species.

Interferon-gamma alone triggers the production of nitric oxide from serum-starved BNL CL.2, murine embryonic liver cells.

PubMed

Pae, H O; Yoo, J C; Choi, B M; Paik, S G; Kim, Y H; Jin, H S; Chung, H T

1999-01-01

A previous study has demonstrated that both interferon-gamma (IFN-gamma) and lipopolysaccharide (LPS) were needed to induce the production of nitric oxide (NO) in BNL CL.2 cells, murine embryonic liver cells. We here demonstrate that when BNL CL.2 cells were cultured with serum-free medium, they were induced to produce NO by the stimulation of IFN-gamma alone. BNL CL.2 cells were cultured with serum-free or serum-containing medium for 1-3 days and then stimulated to synthesize NO by IFN-gamma. Surprisingly, only serum-starved cells showed significant amount of nitrite accumulation and iNOS protein expression in response to IFN-gamma in dose- and time-dependent manners, but serum-supplied cells did not. When the cells were stimulated with IFN-gamma, tumor necrosis factor-alpha (TNF-alpha), or LPS in combinations, only the combination of IFN-gamma and LPS produced more NO than that produced by IFN-gamma alone. The production of NO by the cells stimulated with IFN-gamma or IFN-gamma plus LPS was blocked by the addition of N(G)-monomethyl-L-arginine (N(G)MMA), a NO synthesis inhibitor. To address the intracellular signal pathway responsible for the production of NO by the cells stimulated with IFN-gamma aloneor IFN-gamma plus LPS, we examined the effects of several protein kinase inhibitors on the production of NO from the cells. The production of NO was significantly inhibited by protein tyrosine kinase (PTK) inhibitors, genistein and herbimycin A, but not by protein kinase A or C inhibitors. These results suggest that the deprivation of serum from BNL CL.2 cell culture medium might prime the cells to induce NO synthesis when the cells are triggered by IFN-gamma and the involvement of PTK signal transduction pathway in the expression of inducible NO synthase gene in murine hepatoma cells.

Effects of lead mineralogy on soil washing enhanced by ferric salts as extracting and oxidizing agents.

PubMed

Yoo, Jong-Chan; Park, Sang-Min; Yoon, Geun-Seok; Tsang, Daniel C W; Baek, Kitae

2017-10-01

In this study, we evaluated the feasibility of using ferric salts including FeCl 3 and Fe(NO 3 ) 3 as extracting and oxidizing agents for a soil washing process to remediate Pb-contaminated soils. We treated various Pb minerals including PbO, PbCO 3 , Pb 3 (CO 3 ) 2 (OH) 2 , PbSO 4 , PbS, and Pb 5 (PO 4 ) 3 (OH) using ferric salts, and compared our results with those obtained using common washing agents of HCl, HNO 3 , disodium-ethylenediaminetetra-acetic acid (Na 2 -EDTA), and citric acid. The use of 50 mM Fe(NO 3 ) 3 extracted significantly more Pb (above 96% extraction) from Pb minerals except PbSO 4 (below 55% extraction) compared to the other washing agents. In contrast, washing processes using FeCl 3 and HCl were not effective for extraction from Pb minerals because of PbCl 2 precipitation. Yet, the newly formed PbCl 2 could be dissolved by subsequent wash with distilled water under acidic conditions. When applying our washing method to remediate field-contaminated soil from a shooting range that had high concentrations of Pb 3 (CO 3 ) 2 (OH) 2 and PbCO 3 , we extracted more Pb (approximately 99% extraction) from the soil using 100 mM Fe(NO 3 ) 3 than other washing agents at the same process conditions. Our results show that ferric salts can be alternative washing agents for Pb-contaminated soils in view of their extracting and oxidizing abilities. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sea salt aerosols as a reactive surface for inorganic and organic acidic gases in the arctic troposphere

NASA Astrophysics Data System (ADS)

Chi, J. W.; Li, W. J.; Zhang, D. Z.; Zhang, J. C.; Lin, Y. T.; Shen, X. J.; Sun, J. Y.; Chen, J. M.; Zhang, X. Y.; Zhang, Y. M.; Wang, W. X.

2015-06-01

Sea salt aerosols (SSA) are dominant particles in the arctic atmosphere and determine the polar radiative balance. SSA react with acidic pollutants that lead to changes of physical and chemical properties of their surface, which in turn alter their hygroscopic and optical properties. Transmission electron microscopy with energy-dispersive X-ray spectrometry was used to analyze morphology, composition, size, and mixing state of individual SSA at Ny-Ålesund, Svalbard in summertime. Individual fresh SSA contained cubic NaCl coated by certain amounts of MgCl2 and CaSO4. Individual partially aged SSA contained irregular NaCl coated by a mixture of NaNO3, Na2SO4, Mg(NO3)2, and MgSO4. The comparison suggests the hydrophilic MgCl2 coating in fresh SSA likely intrigued the heterogeneous reactions at the beginning of SSA and acidic gases. Individual fully aged SSA normally had Na2SO4 cores and an amorphous coating of NaNO3. Elemental mappings of individual SSA particles revealed that as the particles ageing Cl gradually decreased but the C, N, O, and S content increased. 12C14N- mapping from nanoscale secondary ion mass spectrometry indicates that organic matter increased in the aged SSA compared with the fresh SSA. 12C14N- line scans further show that organic matter was mainly concentrated on the aged SSA surface. These new findings indicate that this mixture of organic matter and NaNO3 on particle surfaces determines their hygroscopic and optical properties. These abundant SSA, whose reactive surfaces absorb inorganic and organic acidic gases in the arctic troposphere, need to be incorporated into atmospheric chemical models.

Sea salt aerosols as a reactive surface for inorganic and organic acidic gases in the Arctic troposphere

NASA Astrophysics Data System (ADS)

Chi, J. W.; Li, W. J.; Zhang, D. Z.; Zhang, J. C.; Lin, Y. T.; Shen, X. J.; Sun, J. Y.; Chen, J. M.; Zhang, X. Y.; Zhang, Y. M.; Wang, W. X.

2015-10-01

Sea salt aerosols (SSA) are dominant particles in the Arctic atmosphere and determine the polar radiative balance. SSA react with acidic pollutants that lead to changes in physical and chemical properties of their surface, which in turn alter their hygroscopic and optical properties. Transmission electron microscopy with energy-dispersive X-ray spectrometry was used to analyze morphology, composition, size, and mixing state of individual SSA at Ny-Ålesund, Svalbard, in summertime. Individual fresh SSA contained cubic NaCl coated by certain amounts of MgCl2 and CaSO4. Individual partially aged SSA contained irregular NaCl coated by a mixture of NaNO3, Na2SO4, Mg(NO3)2, and MgSO4. The comparison suggests the hydrophilic MgCl2 coating in fresh SSA likely intrigued the heterogeneous reactions at the beginning of SSA and acidic gases. Individual fully aged SSA normally had Na2SO4 cores and an amorphous coating of NaNO3. Elemental mappings of individual SSA particles revealed that as the particles ageing Cl gradually decreased, the C, N, O, and S content increased. 12C- mapping from nanoscale secondary ion mass spectrometry indicates that organic matter increased in the aged SSA compared with the fresh SSA. 12C- line scan further shows that organic matter was mainly concentrated on the aged SSA surface. These new findings indicate that this mixture of organic matter and NaNO3 on particle surfaces likely determines their hygroscopic and optical properties. These abundant SSA as reactive surfaces adsorbing inorganic and organic acidic gases can shorten acidic gas lifetime and influence the possible gaseous reactions in the Arctic atmosphere, which need to be incorporated into atmospheric chemical models in the Arctic troposphere.

Sea salt aerosols as a reactive surface for inorganic and organic acidic gases in the arctic troposphere

NASA Astrophysics Data System (ADS)

Li, W.

2016-12-01

Sea salt aerosols (SSA) are dominant particles in the arctic atmosphere and determine the polar radiative balance. SSA react with acidic pollutants that lead to changes of physical and chemical properties of their surface, which in turn alter their hygroscopic and optical properties. Transmission electron microscopy with energy-dispersive X-ray spectrometry was used to analyze morphology, composition, size, and mixing state of individual SSA at Ny-Ålesund, Svalbard in summertime. Individual fresh SSA contained cubic NaCl coated by certain amounts of MgCl2 and CaSO4. Individual partially aged SSA contained irregular NaCl coated by a mixture of NaNO3, Na2SO4, Mg(NO3)2, and MgSO4. The comparison suggests the hydrophilic MgCl2 coating in fresh SSA likely intrigued the heterogeneous reactions at the beginning of SSA and acidic gases. Individual fully aged SSA normally had Na2SO4 cores and an amorphous coating of NaNO3. Elemental mappings of individual SSA particles revealed that as the particles ageing Cl gradually decreased but the C, N, O, and S content increased. 12C- mapping from nanoscale secondary ion mass spectrometry indicates that organic matter increased in the aged SSA compared with the fresh SSA. 12C- line scan further shows that organic matter was mainly concentrated on the aged SSA surface. These new findings indicate that this mixture of organic matter and NaNO3 on particle surfaces likely determines their hygroscopic and optical properties. These abundant SSA as reactive surfaces absorbing inorganic and organic acidic gases can shorten acidic gas lifetime and influence the possible gaseous reactions in the arctic atmosphere, which need to be incorporated into atmospheric chemical models in the arctic troposphere.

Impacts of inorganic anions and natural organic matter on thermally activated persulfate oxidation of BTEX in water.

PubMed

Ma, Jie; Yang, Yongqi; Jiang, Xianchenghao; Xie, Zhuoting; Li, Xiaoxuan; Chen, Changzhao; Chen, Hongkun

2018-01-01

The present study investigated the impacts of water matrix constituents (CO 3 2- , HCO 3 - , Cl - , Br - , PO 4 3- , HPO 4 2- , H 2 PO 4 - , NO 3 - , SO 4 2- and natural organic matters (NOM) on the oxidation of a mixture of benzene, toluene, ethylbenzene, and xylenes (BTEX) by thermally activated persulfate (PS). In the absence of matrix constituents, the BTEX oxidation rates decreased in the following order: xylenes > toluene ≈ ethylbenzene > benzene. HCO 3 - /CO 3 2- and NOM inhibited the BTEX oxidation and the inhibiting effects became more pronounced as the HCO 3 - /CO 3 2- /NOM concentration increased. SO 4 2- , NO 3 - , PO 4 3- and H 2 PO 4 - did not affect the BTEX oxidation while HPO 4 2- slightly inhibited the reaction. The impacts of Cl - and Br - were complex. Cl - inhibited the benzene oxidation while 100 mM and 500 mM of Cl - promoted the oxidation of m-xylene and p-xylene. Br - completely suppressed the benzene oxidation while 500 mM of Br - strongly promoted the oxidation of xylenes. Detailed explanations on the influence of each matrix constituent were discussed. In addition, various halogenated degradation byproducts were detected in the treatments containing Cl - and Br - . Overall, this study indicates that some matrix constituents such as NOM, HCO 3 - , CO 3 2- , H 2 PO 4 - , Cl - and Br - may reduce the BTEX removal efficiency of sulfate radical-based advanced oxidation process (SR-AOP) and the presence of Cl - and Br - may even lead to the formation of toxic halogenated byproducts. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of Sodium Sulfate, Ammonium Chloride, Ammonium Nitrate, and Salt Mixtures on Aqueous Phase Partitioning of Organic Compounds.

PubMed

Wang, Chen; Lei, Ying Duan; Wania, Frank

2016-12-06

Dissolved inorganic salts influence the partitioning of organic compounds into the aqueous phase. This influence is especially significant in atmospheric aerosol, which usually contains large amounts of ions, including sodium, ammonium, chloride, sulfate, and nitrate. However, empirical data on this salt effect are very sparse. Here, the partitioning of numerous organic compounds into solutions of Na 2 SO 4 , NH 4 Cl, and NH 4 NO 3 was measured and compared with existing data for NaCl and (NH 4 ) 2 SO 4 . Salt mixtures were also tested to establish whether the salt effect is additive. In general, the salt effect showed a decreasing trend of Na 2 SO 4 > (NH) 2 SO 4 > NaCl > NH 4 Cl > NH 4 NO 3 for the studied organic compounds, implying the following relative strength of the salt effect of individual anions: SO 4 2- > Cl - > NO 3 - and of cations: Na + > NH 4 + . The salt effect of different salts is moderately correlated. Predictive models for the salt effect were developed based on the experimental data. The experimental data indicate that the salt effect of mixtures may not be entirely additive. However, the deviation from additivity, if it exists, is small. Data of very high quality are required to establish whether the effect of constituent ions or salts is additive or not.

Nitryl chloride as a 'new' radical source and its role in production of ozone in polluted troposphere: an overview of the results from four field campaigns in China

NASA Astrophysics Data System (ADS)

Wang, Tao; Tham, Yee Jun; Xue, Likun; Wang, Zhe; Wang, Xinfeng; Wang, Weihao; Wang, Hao; Yun, Hui; Lu, Keding; Shao, Min; Louie, Peter K. K.; Blake, Donald R.; Brown, Steven S.; Zhang, Yuanhang

2016-04-01

Nitryl chloride (ClNO2) - a trace gas produced from heterogeneous reactions of dinitrogen pentoxide (N2O5) on aerosols containing chorine - can significantly affect radical budget and concentrations of ozone and other secondary pollutants. However, the abundance, formation kinetics, and impact of ClNO2are not fully understood under different environmental conditions. This presentation gives an overview of recent field campaigns of ClNO2 and related chemical constituents in China, including one at a mountain top (957 m a.s.l) in Hong Kong of South China in winter 2013 and three in North China (urban Ji'nan, semi-rural Wangdu, and Mt Tai (1534 m a.s.l)) in summer 2014. ClNO2 and N2O5 were measured with a chemical ionization mass spectrometry (CIMS) system with iodide as the primary ions. Ambient concentrations of several hundreds ppts and up to 4.7 ppbv of ClNO2were observed in these locations, suggesting existence of elevated ClNO2 in both coastal and inland atmospheres of China. Measurements in North China exhibited generally low concentrations of N2O5, indicative of its fast uptake of on aerosols under aerosol and humid conditions. Indications of anthropogenic sources of chloride were observed at all these sites. The impact of photolysis of ClNO2 on radical budget and ozone enhancement was assessed with a MCM model which was updated with detailed chlorine chemistry and constrained by measurement data for the southern and a northern site. The results show that the ClNO2 could increase ozone production by 2-16% in the following day. Overall, our study re-affirms the need to include ClNO2 related reactions in photochemical models for prediction of ground-level ozone in polluted environments.

76 FR 41653 - Airworthiness Directives; Bombardier, Inc. Model CL-600-2A12 (CL-601) and CL-600-2B16 (CL-601-3A...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-07-15

... AD docket shortly after receipt. List of Subjects in 14 CFR Part 39 Air transportation, Aircraft... DEPARTMENT OF TRANSPORTATION Federal Aviation Administration 14 CFR Part 39 [Docket No. FAA-2010... Transportation (DOT). ACTION: Final rule. SUMMARY: We are adopting a new airworthiness directive (AD) for the...

Isotopic composition and origin of indigenous natural perchlorate and co-occurring nitrate in the southwestern United States

USGS Publications Warehouse

Jackson, W. Andrew; Böhlke, John Karl; Gu, Baohua; Hatzinger, Paul B.; Sturchio, Neil C.

2010-01-01

Perchlorate (ClO4−) has been detected widely in groundwater and soils of the southwestern United States. Much of this ClO4− appears to be natural, and it may have accumulated largely through wet and dry atmospheric deposition. This study evaluates the isotopic composition of natural ClO4− indigenous to the southwestern U.S. Stable isotope ratios were measured in ClO4− (δ18O, Δ17O, δ37Cl) and associated NO3− (δ18O, Δ17O, δ15N) in groundwater from the southern High Plains (SHP) of Texas and New Mexico and the Middle Rio Grande Basin (MRGB) in New Mexico, from unsaturated subsoil in the SHP, and from NO3−-rich surface caliche deposits near Death Valley, California. The data indicate natural ClO4− in the southwestern U.S. has a wide range of isotopic compositions that are distinct from those reported previously for natural ClO4− from the Atacama Desert of Chile as well as all known synthetic ClO4−. ClO4− in Death Valley caliche has a range of high Δ17O values (+8.6 to +18.4 ‰), overlapping and extending the Atacama range, indicating at least partial atmospheric formation via reaction with ozone (O3). However, the Death Valley δ37Cl values (−3.1 to −0.8 ‰) and δ18O values (+2.9 to +26.1‰) are higher than those of Atacama ClO4−. In contrast, ClO4− from western Texas and New Mexico has much lower Δ17O (+0.3 to +1.3‰), with relatively high δ37Cl (+3.4 to +5.1 ‰) and δ18O (+0.5 to +4.8 ‰), indicating either that this material was not primarily generated with O3 as a reactant or that the ClO4− was affected by postdepositional O isotope exchange. High Δ17O values in ClO4− (Atacama and Death Valley) are associated with high Δ17O values in NO3−, indicating that both compounds preserve characteristics of O3-related atmospheric production in hyper-arid settings, whereas both compounds have low Δ17O values in less arid settings. Although Δ17O variations in terrestrial NO3− can be attributed to mixing of atmospheric (high Δ17O) and biogenic (low Δ17O) NO3−, variations in Δ17O of terrestrial ClO4− are not readily explained in the same way. This study provides important new constraints for identifying natural sources of ClO4− in different environments by multicomponent isotopic characteristics, while presenting the possibilities of divergent ClO4− formation mechanisms and(or) ClO4− isotopic exchange in biologically active environments.

Application of a Re-Pd bimetallic catalyst for treatment of perchlorate in waste ion-exchange regenerant brine.

PubMed

Liu, Jinyong; Choe, Jong Kwon; Sasnow, Zachary; Werth, Charles J; Strathmann, Timothy J

2013-01-01

Concentrated sodium chloride (NaCl) brines are often used to regenerate ion-exchange (IX) resins applied to treat drinking water sources contaminated with perchlorate (ClO(4)(-)), generating large volumes of contaminated waste brine. Chemical and biological processes for ClO(4)(-) reduction are often inhibited severely by high salt levels, making it difficult to recycle waste brines. Recent work demonstrated that novel rhenium-palladium bimetallic catalysts on activated carbon support (Re-Pd/C) can efficiently reduce ClO(4)(-) to chloride (Cl(-)) under acidic conditions, and here the applicability of the process for treating waste IX brines was examined. Experiments conducted in synthetic NaCl-only brine (6-12 wt%) showed higher Re-Pd/C catalyst activity than in comparable freshwater solutions, but the rate constant for ClO(4)(-) reduction measured in a real IX waste brine was found to be 65 times lower than in the synthetic NaCl brine. Through a series of experiments, co-contamination of the IX waste brine by excess NO(3)(-) (which the catalyst reduces principally to NH(4)(+)) was found to be the primary cause for deactivation of the Re-Pd/C catalyst, most likely by altering the immobilized Re component. Pre-treatment of NO(3)(-) using a different bimetallic catalyst (In-Pd/Al(2)O(3)) improved selectivity for N(2) over NH(4)(+) and enabled facile ClO(4)(-) reduction by the Re-Pd/C catalyst. Thus, sequential catalytic treatment may be a promising strategy for enabling reuse of waste IX brine containing NO(3)(-) and ClO(4)(-). Copyright © 2012 Elsevier Ltd. All rights reserved.

Differential role of ethylene and hydrogen peroxide in dark-induced stomatal closure.

PubMed

Kar, R K; Parvin, N; Laha, D

2013-12-15

Regulation of stomatal aperture is crucial in terrestrial plants for controlling water loss and gaseous exchange with environment. While much is known of signaling for stomatal opening induced by blue light and the role of hormones, little is known about the regulation of stomatal closing in darkness. The present study was aimed to verify their role in stomatal regulation in darkness. Epidermal peelings from the leaves of Commelina benghalensis were incubated in a defined medium in darkness for 1 h followed by a 1 h incubation in different test solutions [H2O2, propyl gallate, ethrel (ethylene), AgNO3, sodium orthovanadate, tetraethyl ammonium chloride, CaCl2, LaCl3, separately and in combination] before stomatal apertures were measured under the microscope. In the dark stomata remained closed under treatments with ethylene and propyl gallate but opened widely in the presence of H2O2 and AgNO3. The opening effect was largely unaffected by supplementing the treatment with Na-vanadate (PM H+ ATPase inhibitor) and tetraethyl ammonium chloride (K(+)-channel inhibitor) except that opening was significantly inhibited by the latter in presence of H2O2. On the other hand, H2O2 could not override the closing effect of ethylene at any concentrations while a marginal opening of stomata was found when Ag NO3 treatment was given together with propyl gallate. CaCl2 treatment opened stomata in the darkness while LaCl3 maintained stomata closed. A combination of LaCl3 and propyl gallate strongly promoted stomatal opening. A probable action of ethylene in closing stomata of Commelina benghalensis in dark has been proposed.

Preparation and Single-Crystal X-Ray Structures of Four Related Mixed-Ligand 4-Methylpyridine Indium Halide Complexes

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Clark, Eric B.; Schupp, John D.; Williams, Jennifer N.; Duraj, Stan A.; Fanwick, Philip E.

2013-01-01

We describe the structures of four related indium complexes obtained during synthesis of solid-state materials precursors. Indium adducts of halides and 4-methylpyridine, InX3(pic)3 (X = Cl, Br; pic = 4-methylpyridine) consist of octahedral molecules with meridional (mer) geometry. Crystals of mer-InCl3(pic)3 (1) are triclinic, space group P1(bar) (No. 2), with a = 9.3240(3), b = 13.9580(6), c = 16.7268 (7) A, alpha = 84.323(2), beta = 80.938(2), gamma = 78.274(3)Z = 4, R = 0.035 for 8820 unique reflections. Crystals of mer-InBr3(pic)3 (2) are monoclinic, space group P21/n (No. 14), with a = 15.010(2), b = 19.938(2), c = 16.593(3), beta = 116.44(1)Z = 8, R = 0.053 for 4174 unique reflections. The synthesis and structures of related compounds with phenylsulfide (chloride) (3) and a dimeric complex with bridging hydroxide (bromide) (4) coordination is also described. Crystals of trans-In(SC6H5)Cl2(pic)3 (3) are monoclinic, space group P21/n (No. 14), with a = 9.5265(2), b = 17.8729(6), c = 13.8296(4), beta = 99.7640(15)Z = 4, R = 0.048 for 5511 unique reflections. Crystals of [In(mu-OH)Br2(pic)22 (4) are tetragonal, space group = I41cd (No. 110) with a = 19.8560(4), b = 19.8560(4), c = 25.9528(6), Z = 8, R = 0.039 for 5982 unique reflections.

Investigation of Heterogeneous N2O5 Uptake and ClNO2 Yield at a Rural and a Mountain-top Site in Northern China

NASA Astrophysics Data System (ADS)

Wang, Z.; Tham, Y. J.; Wang, W.; LI, Q.; Yun, H.; Wang, X.; Xue, L.; Wang, T.

2017-12-01

Dinitrogen pentoxide (N2O5) is a reactive intermediate in the atmospheric oxidation of nitrogen oxides (NOx), and its heterogeneous reaction plays key roles in the chemical transformation and removal of NOx, as well as the production of nitrate and nitryl chloride (ClNO2) that affects the radical budget and photochemical ozone formation. Ambient measurements at a rural site and a mountain top site in northern China in the summer of 2014 revealed significant ClNO2 mixing ratios (up to 2.1 ppbv) produced by fast heterogeneous N2O5 uptake on atmospheric aerosols. Frequently intercepted ClNO2-laden plumes at the mountain site indicate significant ClNO2 production occurred in the nocturnal residual layer, and could help explain the sustained ClNO2 peaks after sunrise observed in the ground site in the region. The meteorological and chemical analysis suggested that elevated ClNO2 plumes were mostly associated with nocturnal buoyant emission from point combustion sources, such as power and industry plants. The uptake coefficients (γ) of N2O5 and yields (ϕ) of ClNO2 were then derived for different plumes observed at the ground and mountain sites, and the factors affecting the variability of γ and ϕ under different conditions were also investigated. The uptake coefficients and yields obtained in this study in northern China will be compared with other observations in the world, and also compared to the existing parameterizations based on aerosol compositions. The contribution of fast N2O5 heterogeneous reaction to the nocturnal NOx processing and nitrate aerosol formation will be further examined, to better understand the impacts of heterogeneous reactive nitrogen chemistry on air quality in northern China.

Synthesis, characterisation and antibacterial activity of [(p-cym)RuX(L)](+/2+) (X = Cl, H2O; L = bpmo, bpms) complexes.

PubMed

Tripathy, Suman Kumar; Taviti, Ashoka Chary; Dehury, Niranjan; Sahoo, Anupam; Pal, Satyanaryan; Beuria, Tushar Kant; Patra, Srikanta

2015-03-21

Mononuclear half-sandwiched complexes [(p-cym)RuCl(bpmo)](ClO4) {[1](ClO4)} and [(p-cym)RuCl(bpms)](PF6) {[2](PF6)} have been prepared by reacting heteroscorpionate ligands bpmo = 2-methoxyphenyl-bis(3,5-dimethylpyrazol-1-yl)methane and bpms = 2-methylthiophenyl-bis(3,5-dimethylpyrazol-1-yl)methane, respectively, with a dimeric precursor complex [(p-cym)RuCl(μ-Cl)]2 (p-cym = 1-isopropyl-4-methylbenzene) in methanol. The corresponding aqua derivatives [(p-cym)Ru(H2O)(bpmo)](ClO4)2 {[3](ClO4)2} and [(p-cym)Ru(H2O)(bpms)](PF6)2 {[4](PF6)2} are obtained from {[1](ClO4)} and {[2](PF6)}, respectively, via Cl(-)/H2O exchange process in the presence of appropriate equivalents of AgClO4/AgNO3 + KPF6 in a methanol-water mixture. The molecular structures of the complexes {[1]Cl, [3](ClO4)2 and [4](PF6)(NO3)} are authenticated by their single crystal X-ray structures. The complexes show the expected piano-stool geometry with p-cym in the η(6) binding mode. The aqua complexes [3](ClO4)2 and [4](PF6)2 show significantly good antibacterial activity towards E. coli (gram negative) and B. subtilis (gram positive) strains, while chloro derivatives ({[1](ClO4)} and {[2](PF6)} are found to be virtually inactive. The order of antibacterial activity of the complexes according to their MIC values is [1](ClO4) (both 1000 μg mL(-1)) < [2](PF6) (580 μg mL(-1) and 750 μg mL(-1)) < [3](ClO4)2 (both 100 μg mL(-1)) < [4](PF6)2 (30 μg mL(-1) and 60 μg mL(-1)) for E. coli and B. subtilis strains, respectively. Further, the aqua complexes [3](ClO4)2 and [4](PF6)2 show clear zones of inhibition against kanamycin, ampicillin and chloramphenicol resistant E. coli strains. The detailed mechanistic aspects of the aforesaid active aqua complexes [3](ClO4)2 and [4](PF6)2 have been explored, and it reveals that both the complexes inhibit the number of nucleoids per cell in vivo and bind to DNA in vitro. The results indeed demonstrate that both [3](ClO4)2 and [4](PF6)2 facilitate the inhibition of bacterial growth by binding to DNA.

Using corona discharge-ion mobility spectrometry for detection of 2,4,6-Trichloroanisole.

PubMed

Lichvanová, Zuzana; Ilbeigi, Vahideh; Sabo, Martin; Tabrizchi, Mahmoud; Matejčík, Stefan

2014-09-01

In this work possible application of the corona discharge-ion mobility spectrometer (CD-IMS) for detection of 2,4,6-Trichloroanisole (TCA) has been investigated. We applied CD-IMS interfaced with orthogonal acceleration time of flight mass spectrometer (CD-IMS-oaTOF) to study the ion processes within the CD-IMS technique. The CD-IMS instrument was operated in two modes, (i) standard and (ii) reverse flow modes resulting in different chemical ionisation schemes by NO3(-)(HNO3)n (n=0,1,2) and O2(-)(H2O)n (n=0,1,2), respectively. The O2(-)(H2O)n ionisation was associated with formation of Cl(-) and (TCA-CH3)(-) ions from TCA. The NO3(-)(HNO3)n ionisation, resulted in formation of NO3(-)(HNO3)(TCA-Cl) adduct ions. Limit of detection (LOD) for TCA was determined in gas (100 ppb) and solid phases (150 ng). Copyright © 2014 Elsevier B.V. All rights reserved.

Trapping Experiments on a Trichlorosilanide Anion: a Key Intermediate of Halogenosilane Chemistry.

PubMed

Teichmann, Julian; Bursch, Markus; Köstler, Benedikt; Bolte, Michael; Lerner, Hans-Wolfram; Grimme, Stefan; Wagner, Matthias

2017-08-07

Treatment of Si 2 Cl 6 with [Et 4 N][BCl 4 ] in CH 2 Cl 2 furnished the known products of a chloride-induced disproportionation reaction of the disilane, such as SiCl 4 , [Si(SiCl 3 ) 3 ] - , and [Si 6 Cl 12 ·2Cl] 2- . No Si-B-bonded products were detectable. In contrast, the addition of Si 2 Cl 6 to [Et 4 N][BI 3 Cl] afforded the Si-B adduct [Et 4 N][I 3 SiBI 3 ]. Thus, a quantitative Cl/I exchange at the silicon atom accompanies the trihalogenosilanide formation. [Et 4 N][I 3 SiBI 3 ] was also accessible from a mixture of Si 2 I 6 , [Et 4 N]I, and BI 3 . According to X-ray crystallography, the anion [I 3 SiBI 3 ] - adopts a staggered conformation with an Si-B bond length of 1.977(6) Å. Quantum-chemical calculations revealed a polar covalent Si-B bond with significant contributions from intramolecular I···I dispersion interactions.

Heteropentanuclear Oxalato-Bridged nd-4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity.

PubMed

Kuhn, Paul-Steffen; Cremer, Laura; Gavriluta, Anatolie; Jovanović, Katarina K; Filipović, Lana; Hummer, Alfred A; Büchel, Gabriel E; Dojčinović, Biljana P; Meier, Samuel M; Rompel, Annette; Radulović, Siniša; Tommasino, Jean Bernard; Luneau, Dominique; Arion, Vladimir B

2015-09-21

A series of heteropentanuclear oxalate-bridged Ru(NO)-Ln (4d-4f) metal complexes of the general formula (nBu4N)5[Ln{RuCl3(μ-ox)(NO)}4], where Ln=Y (2), Gd (3), Tb (4), Dy (5) and ox=oxalate anion, were obtained by treatment of (nBu4N)2[RuCl3(ox)(NO)] (1) with the respective lanthanide salt in 4:1 molar ratio. The compounds were characterized by elemental analysis, IR spectroscopy, electrospray ionization (ESI) mass spectrometry, while 1, 2, and 5 were in addition analyzed by X-ray crystallography, 1 by Ru K-edge XAS and 1 and 2 by (13)C NMR spectroscopy. X-ray diffraction showed that in 2 and 5 four complex anions [RuCl3(ox)(NO)](2-) are coordinated to Y(III) and Dy(III), respectively, with formation of [Ln{RuCl3(μ-ox)(NO)}4](5-) (Ln=Y, Dy). While Y(III) is eight-coordinate in 2, Dy(III) is nine-coordinate in 5, with an additional coordination of an EtOH molecule. The negative charge is counterbalanced by five nBu4N(+) ions present in the crystal structure. The stability of complexes 2 and 5 in aqueous medium was monitored by UV/Vis spectroscopy. The antiproliferative activity of ruthenium-lanthanide complexes 2-5 were assayed in two human cancer cell lines (HeLa and A549) and in a noncancerous cell line (MRC-5) and compared with those obtained for the previously reported Os(NO)-Ln (5d-4f) analogues (nBu4N)5[Ln{OsCl3(ox)(NO)}4] (Ln=Y (6), Gd (7), Tb (8), Dy (9)). Complexes 2-5 were found to be slightly more active than 1 in inhibiting the proliferation of HeLa and A549 cells, and significantly more cytotoxic than 5d-4f metal complexes 6-9 in terms of IC50 values. The highest antiproliferative activity with IC50 values of 20.0 and 22.4 μM was found for 4 in HeLa and A549 cell lines, respectively. These cytotoxicity results are in accord with the presented ICP-MS data, indicating five- to eightfold greater accumulation of ruthenium versus osmium in human A549 cancer cells. © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Depressor action and vasorelaxation of methylene chloride fraction extracted from Rubus coreanum.

PubMed

Yu, Byung-Sik; Choi, Mee-Sung; Lim, Dong-Yoon

2014-01-01

The present study was designed to examine whether methylene chloride (CH2Cl2) fraction extracted from Rubus coreanum affects the contractility of the isolated thoracic aortic strips and blood pressure of normotensive rats. One of the common carotid arteries or of the femoral arteries was catheterized with a polyethylene tubing. The tubing was connected to a pressure transducer, and pulse of the mean arterial blood pressure was recorded on a biological polygraph continuously. The CH2Cl2 fraction (range, 200 to 800 μg/mL) significantly depressed both phenylephrine (PE, 10 μM)- and high K(+) (56 mM)-induced contractile responses of the isolated thoracic aortic strips in a concentration-dependent fashion. In the simultaneous presence of N(ω)-nitro-L-arginine methyl ester hydrochloride (L-NAME) (an inhibitor of nitric oxide [NO] synthase, 300 μM) and the CH2Cl2 fraction (400 μg/mL), both PE- and high K(+)-induced contractile responses were recovered to the significant level of the corresponding control response in comparison with inhibition of CH2Cl2 fraction treatment alone. Moreover, in the simultaneous presence of the CH2Cl2 fraction after pretreatment with 0.4% CHAPS (3-[(3-cholamidopropyl) dimethylammonio]-1-propane sulfonate), both PE- and high K(+)-induced contractile responses were recovered to the significant level of the corresponding control response compared to the inhibitory response of CH2Cl2 fraction treatment alone. Also, in anesthetized rats, the CH2Cl2 fraction (range, 0.3 to 3.0 mg/kg) injected into a femoral vein dose-dependently produced depressor responses. This hypotensive action of the CH2Cl2 fraction was greatly inhibited after treatment with phentolamine (1 mg/kg), chlorisondamine (1 mg/kg), L-NAME (3 mg/kg/30 min), or sodium nitroprusside (30 μg/kg/30 min). Intravenous infusion of the CH2Cl2 fraction (range, 1.0 to 10.0 mg/kg/30 min) markedly inhibited norepinephrine-induced pressor responses. Taken together, these results demonstrate that the CH2Cl2 fraction causes vascular relaxation in the isolated rat thoracic aortic strips as well as hypotensive action in anesthetized rats. These vasorelaxation and hypotension of the CH2Cl2 fraction seem to be mediated at least by the increased NO production through the activation of NO synthase of the vascular endothelium and the inhibitory adrenergic modulation.

Interactions of aerosols (ammonium sulfate, ammonium nitrate and ammonium chloride) and of gases (HCl, HNO 3) with fogwater

NASA Astrophysics Data System (ADS)

Ruprecht, Heidi; Sigg, Laura

The concentrations of aerosols (NH 4NO 3, (NH 4) 2SO 4 and NH 4Cl) and of gases (HCl (g), HNO 3(g), NH 3(g) were determined by denuder methods under different conditions (in the absence of fog, before, during and after fog events). At this site situated in an urban region, high concentrations of the gaseous strong acids HCl (g) and HNO 3(g) are observed. NH 4Cl and NH 4NO 3 aerosols represent a major fraction of the Cl - and NO 3- aerosols (<2.4 μm)collected by denuders. During a fog event, very high concentrations of SO 42- were found in small aerosols, which are attributed to the aqueous phase oxidation of SO 2 under the influence of high pH due to the presence of NH 3. Differences in SO 42- concentrations measured in aerosols (<2.4 μm) and in fog droplets were probably due to mass-transport limitations of the SO 2 oxidation. Ammonium sulfate aerosols represent in some cases a significant fraction of the total S present (SO 2(g) + SO 42-. Soluble aerosols and gases contribute to the composition of fogwater and are released again after fog dissipation.

Ionizing radiation potentiates the induction of nitric oxide synthase by interferon-gamma (Ifn-gamma) or Ifn-gamma and lipopolysaccharide in bnl cl.2 murine embryonic liver cells: role of hydrogen peroxide.

PubMed

Yoo, J C; Pae, H O; Choi, B M; Kim, W I; Kim, J D; Kim, Y M; Chung, H T

2000-02-01

The effects of ionizing irradiation on the nitric oxide (NO) production in murine embryonic liver cell line, BNL CL.2 cells, were investigated. Various doses (5-40 Gy) of radiation made BNL CL.2 cells responsive to interferon-gamma alone for the production of NO in a dose-dependent manner. Small amounts of lipopolysaccharide (LPS) or tumor necrosis factor-alpha (TNF-alpha) synergized with IFN-gamma in the production of NO from irradiated BNL CL.2 cells, even though LPS or TNF-alpha alone did not induce NO production from the same cells. Immunoblots showed parallel induction of inducible nitric oxide synthase (iNOS). NO production in irradiated BNL CL.2 cells by IFN-gamma or IFN-gamma plus LPS was decreased by the addition of catalase, suggesting that H(2)O(2) produced by ionizing irradiation primed the cells to trigger NO production in response to IFN-gamma or IFN-gamma plus LPS. Furthermore, the treatment of nongamma-irradiated BNL CL.2 cells with H(2)O(2) made the cells responsive to IFN-gamma or IFN-gamma plus LPS for the production of NO. This study shows that ionizing irradiation has the ability to induce iNOS gene expression in responsive to IFN-gamma via the formation of H(2)O(2) in BNL CL.2 murine embryonic liver cells.

Balloon-Borne Measurements of CLO, NO and O3 in a Volcanic Cloud: An Analysis of Heterogeneous Chemistry between 20 and 30 KM

NASA Technical Reports Server (NTRS)

Dessler, A. E.; Stimpfle, R. M.; Daube, B. C.; Salawitch, R. J.; Weinstock, E. M.; Judah, D. M.; Burley, J. D.; Munger, J. W.; Wofsy, S. C.; Anderson, J. G.;

Impact of four training conditions on physician use of a web-based clinical decision support system.

PubMed

Kealey, Edith; Leckman-Westin, Emily; Finnerty, Molly T

2013-09-01

Training has been identified as an important barrier to implementation of clinical decision support systems (CDSSs), but little is known about the effectiveness of different training approaches. Using an observational retrospective cohort design, we examined the impact of four training conditions on physician use of a CDSS: (1) computer lab training with individualized follow-up (CL-FU) (n=40), (2) computer lab training without follow-up (CL) (n=177), (3) lecture demonstration (LD) (n=16), or (4) no training (NT) (n=134). Odds ratios of any use and ongoing use under training conditions were compared to no training over a 2-year follow-up period. CL-FU was associated with the highest percent of active users and odds for any use (90.0%, odds ratio (OR)=10.2, 95% confidence interval (CI): 3.2-32.9) and ongoing use (60.0%, OR=6.1 95% CI: 2.6-13.7), followed by CL (any use=81.4%, OR=5.3, CI: 2.9-9.6; ongoing use=28.8%, OR=1.7, 95% CI: 1.0-3.0). LD was not superior to no training (any use=47%, ongoing use=22.4%). Training format may have differential effects on initial and long-term follow-up of CDSSs use by physicians. Copyright © 2013 Elsevier B.V. All rights reserved.

Influence of the current density on the electrochemical treatment of concentrated 1-butyl-3-methylimidazolium chloride solutions on diamond electrodes.

PubMed

Marcionilio, Suzana M L de Oliveira; Alves, Gisele M; E Silva, Rachel B Góes; Marques, Pablo J Lima; Maia, Poliana D; Neto, Brenno A D; Linares, José J

2016-10-01

This paper focuses on the influence of the current density treatment of a concentrated 1-butyl-3-methylimidazolium chloride (BMImCl) solution on an electrochemical reactor with a boron-doped diamond (BDD) anode. The decrease in the total organic carbon (TOC) and the BMImCl concentration demonstrate the capability of BDD in oxidizing ionic liquids (ILs) and further mineralizing (to CO2 and NO3 (-)) more rapidly at higher current densities in spite of the reduced current efficiency of the process. Moreover, the presence of Cl(-) led to the formation of oxychlorinated anions (mostly ClO3 (-) and ClO4 (-)) and, in combination with the ammonia generated in the cathode from the nitrate reduction, chloramines, more intensely at higher current density. Finally, the analysis of the intermediates formed revealed no apparent influence of the current density on the BMImCl degradation mechanism. The current density presents therefore a complex influence on the IL treatment process that is discussed throughout this paper.

Ab initio molecular dynamics study on the initial chemical events in nitramines: thermal decomposition of CL-20.

PubMed

Isayev, Olexandr; Gorb, Leonid; Qasim, Mo; Leszczynski, Jerzy

2008-09-04

CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane or HNIW) is a high-energy nitramine explosive. To improve atomistic understanding of the thermal decomposition of CL-20 gas and solid phases, we performed a series of ab initio molecular dynamics simulations. We found that during unimolecular decomposition, unlike other nitramines (e.g., RDX, HMX), CL-20 has only one distinct initial reaction channelhomolysis of the N-NO2 bond. We did not observe any HONO elimination reaction during unimolecular decomposition, whereas the ring-breaking reaction was followed by NO 2 fission. Therefore, in spite of limited sampling, that provides a mostly qualitative picture, we proposed here a scheme of unimolecular decomposition of CL-20. The averaged product population over all trajectories was estimated at four HCN, two to four NO2, two to four NO, one CO, and one OH molecule per one CL-20 molecule. Our simulations provide a detailed description of the chemical processes in the initial stages of thermal decomposition of condensed CL-20, allowing elucidation of key features of such processes as composition of primary reaction products, reaction timing, and Arrhenius behavior of the system. The primary reactions leading to NO2, NO, N 2O, and N2 occur at very early stages. We also estimated potential activation barriers for the formation of NO2, which essentially determines overall decomposition kinetics and effective rate constants for NO2 and N2. The calculated solid-phase decomposition pathways correlate with available condensed-phase experimental data.

Chemodenitrification in the cryoecosystem of Lake Vida, Victoria Valley, Antarctica.

PubMed

Ostrom, N E; Gandhi, H; Trubl, G; Murray, A E

2016-11-01

Lake Vida, in the Victoria Valley of East Antarctica, is frozen, yet harbors liquid brine (~20% salt, >6 times seawater) intercalated in the ice below 16 m. The brine has been isolated from the surface for several thousand years. The brine conditions (permanently dark, -13.4 °C, lack of O 2 , and pH of 6.2) and geochemistry are highly unusual. For example, nitrous oxide (N 2 O) is present at a concentration among the highest reported for an aquatic environment. Only a minor 17 O anomaly was observed in N 2 O, indicating that this gas was predominantly formed in the lake. In contrast, the 17 O anomaly in nitrate (NO3-) in Lake Vida brine indicates that approximately half or more of the NO3- present is derived from atmospheric deposition. Lake Vida brine was incubated in the presence of 15 N-enriched substrates for 40 days. We did not detect microbial nitrification, dissimilatory reduction of NO3- to ammonium (NH4+), anaerobic ammonium oxidation, or denitrification of N 2 O under the conditions tested. In the presence of 15 N-enriched nitrite (NO2-), both N 2 and N 2 O exhibited substantial 15 N enrichments; however, isotopic enrichment declined with time, which is unexpected. Additions of 15 N-NO2- alone and in the presence of HgCl 2 and ZnCl 2 to aged brine at -13 °C resulted in linear increases in the δ 15 N of N 2 O with time. As HgCl 2 and ZnCl 2 are effective biocides, we interpret N 2 O production in the aged brine to be the result of chemodenitrification. With this understanding, we interpret our results from the field incubations as the result of chemodenitrification stimulated by the addition of 15 N-enriched NO2- and ZnCl 2 and determined rates of N 2 O and N 2 production of 4.11-41.18 and 0.55-1.75 nmol L -1  day -1 , respectively. If these rates are representative of natural production, the current concentration of N 2 O in Lake Vida could have been reached between 6 and 465 years. Thus, chemodenitrification alone is sufficient to explain the high levels of N 2 O present in Lake Vida. © 2016 John Wiley & Sons Ltd.

Toxicity and uptake of cyclic nitramine explosives in ryegrass Lolium perenne.

PubMed

Rocheleau, Sylvie; Lachance, Bernard; Kuperman, Roman G; Hawari, Jalal; Thiboutot, Sonia; Ampleman, Guy; Sunahara, Geoffrey I

2008-11-01

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) are cyclic nitramines used as explosives. Their ecotoxicities have been characterized incompletely and little is known about their accumulation potential in soil organisms. We assessed the toxicity and uptake of these explosives in perennial ryegrass Lolium perenne L. exposed in a Sassafras sandy loam (SSL) or in a sandy soil (DRDC, CL-20 only) containing contrasting clay contents (11% and 0.3%, respectively). A 21-d exposure to RDX, HMX or CL-20 in either soil had no adverse effects on ryegrass growth. RDX and HMX were translocated to ryegrass shoots, with bioconcentration factors (BCF) of up to 15 and 11, respectively. In contrast, CL-20 was taken up by the roots (BCF up to 19) with no translocation to the shoots. These studies showed that RDX, HMX, and CL-20 can accumulate in plants and may potentially pose a risk of biomagnification across the food chain.

Atmospheric dry deposition in the vicinity of the Salton Sea, California - I: Air pollution and deposition in a desert environment

USGS Publications Warehouse

Alonso, R.; Bytnerowicz, A.; Boarman, W.I.

2005-01-01

Air pollutant concentrations and atmospheric dry deposition were monitored seasonally at the Salton Sea, southern California. Measurements of ozone (O 3), nitric acid vapor (HNO3), ammonia (NH3), nitric oxide (NO), nitrogen dioxide (NO2) and sulfur dioxide (SO 2) were performed using passive samplers. Deposition rates of NO 3-, NH4+, Cl-, SO 42-, Na+, K+ and Ca2+ to creosote bush branches and nylon filters as surrogate surfaces were determined for one-week long exposure periods. Maximum O3 values were recorded in spring with 24-h average values of 108.8 ??g m-3. Concentrations of NO and NO2 were low and within ranges of the non-urban areas in California (0.4-5.6 and 3.3-16.2 ??g m-3 ranges, respectively). Concentrations of HNO3 (2.0-6.7 ??g m-3) and NH 3 (6.4-15.7 ??g m-3) were elevated and above the levels typical for remote locations in California. Deposition rates of Cl-, SO42-, Na+, K+ and Ca2+ were related to the influence of sea spray or to suspended soil particles, and no strong enrichments caused by ions originated by human activities were detected. Dry deposition rates of NO3- and NH4+ were similar to values registered in areas where symptoms of nitrogen saturation and changes in species composition have been described. Deposition of nitrogenous compounds might be contributing to eutrophication processes at the Salton Sea. ?? 2005 Elsevier Ltd. All rights reserved.

Synthesis and Characterization of Atomically Precise Copper Nanoclusters

NASA Astrophysics Data System (ADS)

Nguyen, Thuy-Ai Dang

The reactivity of MCl3(eta1-TEMPO) (M = Fe, Al; TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) with a variety of lignin models, including 3,4-dimethoxybenzyl alcohol, 1-phenyl-2-phenoxyethanol and 1,2-diphenyl-2-methoxyethanol is investigated. FeCl3(TEMPO) is effective in cleanly converting these substrates to the corresponding aldehyde or ketone. AlCl3(eta1-TEMPO) is also able to oxidize these substrates, however in a few instances the products of over-oxidation are also observed. In contrast, 2-phenoxyethanol is not oxidized by MCl 3(eta1-TEMPO); instead it likely coordinates to the metal center, forming a 2-phenoxyethoxide complex. Oxidation of activated alkanes by MCl3(eta1-TEMPO) suggests that the reactions proceed via an initial 1-electron concerted proton-electron transfer (CPET) event. Finally, reaction of TEMPO with FeBr3 in Et 2O results in oxidation of the solvent. The copper hydride clusters [Cu14H12(phen) 6(PPh3)4][X]2 (X = Cl, OTf) are obtained in good yields by reaction of [(Ph3P)CuH]6 with 1,10-phenanthroline, in the presence of a halide or pseudohalide source. [Cu14H 12(phen)6(PPh3)4][Cl]2 reacts with CO2 in CH2Cl2, in the presence of excess Ph3P, to form the formate complex, [(Ph3P)2Cu(kappa 2-O2CH)], along with [(phen)(Ph3P)CuCl]. [Cu25H22(PPh3)12]Cl and [Cu 18H17(PPh3)10]Cl, are isolated from the reaction of Cu(OAc) and CuCl with Ph2SiH2, in the presence of PPh3. [Cu25H22(PPh3) 12]Cl formally features partial Cu(0) character. Subsequent reaction with Ph2phen resulted in the isolation of [Cu29Cl 4H22(Ph2phen)12]Cl (Ph2phen = 4,7-diphenyl-1,10-phenanthroline), in good yields. A time-resolved kinetic evaluation of the formation of [Cu29Cl4H22(Ph 2phen)12]Cl reveals that the mechanism of cluster growth is initiated by rapid ligand exchange, followed by slower extrusion of CuCl monomer, transport, and subsequent capture by intact clusters. Two Cu26 nanoclusters, tentatively formulated as [Cu 26H17(PPh3)9(OAc)3] and [Cu26H22(PPh3)10(OAc)2], are isolated from the reaction of Cu(OAc) with Ph2SiH2, in the presence of PPh3. As formulated, [Cu26H 17(PPh3)9(OAc)3] features a magic number N* = 6, which is unprecedented for a copper nanocluster. XANES supports an assignment of more Cu(0) character than [Cu25H 22(PPh3)12]Cl (N* = 2) for this complex. A critical reevaluation of the synthesis and characterization of Cu 8(MPP)4 is reported. This product was reportedly formed by reaction of Cu(NO3)2 with 2-mercapto-5-n-propylpyrimidine (HMPP) and NaBH4, in ethanol, in the presence of [N(C8H 17)4][Br]. However, upon reevaluation, no experimental evidence to support the existence of Cu8(MPP)4 was found. Instead, the material isolated from this reaction is a complex mixture containing [N(C8H17)4]+, Br -, NO3-, 2-mercapto-5-n-propyl-1,6-dihydropyrimidine (H2MPP*), along with the Cu(I) coordination polymer, [Cu(MPP)]n. H2MPP* and [Cu(MPP)]n, as well as the related Cu(I) coordination complexes, [Cu(HMPP*)]n and [Cu2(MPP*)]n are independently synthesized to support these conclusions.

Physico-chemical measurements of CL-20 for environmental applications. Comparison with RDX and HMX.

PubMed

Monteil-Rivera, Fanny; Paquet, Louise; Deschamps, Stéphane; Balakrishnan, Vimal K; Beaulieu, Chantale; Hawari, Jalal

2004-01-30

CL-20 is a polycyclic energetic nitramine, which may soon replace the monocyclic nitramines RDX and HMX, because of its superior explosive performance. Therefore, to predict its environmental fate, analytical and physico-chemical data must be made available. An HPLC technique was thus developed to measure CL-20 in soil samples based on the US Environmental Protection Agency method 8330. We found that the soil water content and aging (21 days) had no effect on the recoveries (>92%) of CL-20, provided that the extracts were kept acidic (pH 3). The aqueous solubility of CL-20 was poor (3.6 mg l(-1) at 25 degrees C) and increased with temperature to reach 18.5 mg l(-1) at 60 degrees C. The octanol-water partition coefficient of CL-20 (log KOW = 1.92) was higher than that of RDX (log KOW = 0.90) and HMX (log KOW = 0.16), indicating its higher affinity to organic matter. Finally, CL-20 was found to decompose in non-acidified water upon contact with glass containers to give NO2- (2 equiv.), N2O (2 equiv.), and HCOO- (2 equiv.). The experimental findings suggest that CL-20 should be less persistent in the environment than RDX and HMX.

Perchlorate in pleistocene and holocene groundwater in North-Central New Mexico

USGS Publications Warehouse

Plummer, Niel; Böhlke, J.K.; Doughten, M.W.

2006-01-01

Groundwater from remote parts of the Middle Rio Grande Basin in north-central New Mexico has perchlorate (ClO4-) concentrations of 0.12-1.8 ??g/L Because the water samples are mostly preanthropogenic in age (0-28 000 years) and there are no industrial sources in the study area, a natural source of the ClO4- is likely. Most of the samples have Br-, Cl-, and SO42- concentrations that are similar to those of modern bulk atmospheric deposition with evapotranspiration (ET) factors of about 7-40. Most of the ET values for Pleistocene recharge were nearly twice that for Holocene recharge. The NO3-/Cl- and ClO4-/Cl- ratios are more variable than those of Br -/Cl- or SO42-/Cl-. Samples thought to have recharged under the most arid conditions in the Holocene have relatively high NO3-/Cl- ratios and low ??15N values (+1 per mil (???)) similar to those of modern bulk atmospheric N deposition. The ??18O values of the NO 3- (-4 to 0 ???) indicate that atmospheric N0 3- was not transmitted directly to the groundwater but may have been cycled in the soils before infiltrating. Samples with nearly atmospheric NO3-/Cl- ratios have relatively high ClO4- concentrations (1.0-1.8 ??g/L) with a nearly constant ClO4-/Cl- mole ratio of (1.4 ?? 0.1) ?? 10-4, which would be consistent with an average ClO 4- concentration of 0.093 ?? 0.005 ??g/L in bulk atmospheric deposition during the late Holocene in north-central NM. Samples thought to have recharged underwetter conditions have higher ??15N values (+3 to +8 ???), lower N03-/Cl- ratios, and lower ClO4-/Cl- ratios than the ones most likely to preserve an atmospheric signal. Processes in the soils that may have depleted atmospherically derived NO3- also may have depleted ClO4- to varying degrees prior to recharge. If these interpretations are correct, then ClO4- concentrations of atmospheric origin as high as 4 ??g/L are possible in preanthropogenic groundwater in parts of the Southwest where ET approaches a factor of 40. Higher ClO4- concentrations in uncontaminated groundwater could occur in recharge beneath arid areas where ET is greater than 40, where long-term accumulations of atmospheric salts are leached suddenly from dry soils, or where other (nonatmospheric) natural sources of ClO/4- exist.

Effects of Sodium Chloride, Potassium Chloride and Calcium Chloride on the Formation of α-Dicarbonyl Compounds, Furfurals and Development of Browning in Cookies during Baking.

PubMed

Kocadağlı, Tolgahan; Gökmen, Vural

2016-10-02

Effect of NaCl, KCl, CaCl2, NaHCO3, and NH4HCO3 on the formation of glucosone, 1-deoxyglucosone, 3-deoxyglucosone, glyoxal, methylglyoxal, diacetyl, 5-hydroxymethyl-2-furfural, 2-furfural and browning were investigated in cookies. Presence of 1.5% NaCl, 1% KCl, and 1% CaCl2 on flour basis had no effect on α-dicarbonyl compounds, except 1-deoxyglucosone increased in the presence of KCl and CaCl2. The increase in 5-hydroxymethyl-2-furfural formation in the presence of NaCl, KCl, and CaCl2 did not relate to 3-deoxyglucosone formation and pH changes. NaCl, KCl, and CaCl2 increased browning in cookies. Model reaction systems indicated that NaCl, KCl, and CaCl2 enhance browning by increasing furfurals in caramelization. NaCl, KCl, and CaCl2 decreased browning intensity in heated glucose-glycine system. Usage of CaCl2 in cookies may considerably increase furfurals but not α-dicarbonyl compounds. Sodium reduction can be obtained by replacement with potassium without sacrificing the desired consequences of caramelization in sugar rich bakeries.

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

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

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

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

The variation of characteristics and formation mechanisms of aerosols in dust, haze, and clear days in Beijing

NASA Astrophysics Data System (ADS)

Wang, Ying; Zhuang, Guoshun; Sun, Yele; An, Zhisheng

A 4-year campaign from 2001 to 2004 monitoring PM 2.5 and TSP in the spring season in urban Beijing, China was performed to study the variation of characteristics and the different formation mechanisms of aerosols in dust, haze, and clear days. A total of 315 aerosol samples were collected and used in this study. The aerosols were more basic in dust days and more acidic in haze days. The ions presented in the order of SO42->Ca 2+≫ NO3->Cl -> NH4+>Na + in dust days, and of SO42-> NO3-> NH4+≫Cl ->Ca 2+>K + in haze days. Ions has been classified into three groups, "Na +, Mg 2+, Ca 2+", "K +, SO42-, Cl -", and " NO3-, NH4+", representing crust, pollution-crust, and pollution species, respectively. Crust and pollution ions were the main ion fractions in dust and haze days, respectively. The variation of Ca 2+/Al showed that the increase of dust in dust and haze days was from soil and construction, respectively. "CaCO 3, CaSO 4, and (NH 4) 2SO 4" and "(NH 4) 2SO 4, NH 4NO 3, and Ca(NO 3) 2" were the major species in dust and haze days, respectively. The formation of CaSO 4 on airborne soil particles and the formation of (NH 4) 2SO 4 and NH 4NO 3 were the predominant pathways of sulfate and nitrate formations in dust and haze days, respectively. Sulfate might be mainly formed through heterogeneous reactions in the aqueous surface layer on the pre-existing particles, while nitrate mainly through homogeneous gas-phase reactions in the spring season in Beijing. The formation of sulfate and nitrate was accelerated in dust and haze days.

The toxicity of different lead salts to Enchytraeus crypticus in relation to bioavailability in soil.

PubMed

Zhang, Lulu; Van Gestel, Cornelis A M

2017-08-01

The present study aimed to assess the bioavailability and toxicity of lead nitrate and lead chloride to Enchytraeus crypticus in a natural standard soil. Worms were exposed to Pb-spiked soil for 21 d, and survival and reproduction were related to total, 0.01 M CaCl 2 -extractable, and porewater Pb concentrations in the soil and internal concentrations in the surviving animals. The Pb availability for Pb(NO 3 ) 2 and PbCl 2 was similar, as confirmed by Langmuir and Freundlich isotherms. The Pb concentrations in surviving worms increased with increasing Pb concentrations in the soil and did not differ for the 2 Pb salts. Lead was toxic to E. crypticus at median lethal concentrations (LC50s) of 543 and 779 mg Pb/kg dry soil and median effect concentrations (EC50s) of 189 and 134 mg Pb/kg dry soil, for Pb(NO 3 ) 2 and PbCl 2 , respectively. Mortality of E. crypticus was related to internal Pb concentrations in the worms rather than to total or available Pb concentrations in the soil, whereas reproduction toxicity was better explained from Pb concentrations in 0.01 M CaCl 2 extracts or porewater of the test soil than from total Pb concentrations in the soil or Pb concentrations in the worms. Overall, the bioavailability and toxicity of Pb(NO 3 ) 2 and PbCl 2 to E. crypticus in LUFA 2.2 soil did not differ. Environ Toxicol Chem 2017;36:2083-2091. © 2017 SETAC. © 2017 SETAC.

Effect of the electronegativity on the electrosorption selectivity of anions during capacitive deionization.

PubMed

Sun, Zhumei; Chai, Liyuan; Liu, Mingshi; Shu, Yude; Li, Qingzhu; Wang, Yunyan; Qiu, Dingfan

2018-03-01

The effect of electronegativity on the electrosorption selectivity of anions during capacitive deionization was investigated via a combination of experimental and theoretical studies. A model was developed based on chemical thermodynamics and the classic Stern's model to reveal the role of the anode potential and to describe electrosorption selectivity behavior during capacitive deionization. The effects of the anode potential on the adsorption of Cl - and ReO 4 - were studied and the obtained data were used to validate the model. Using the validated model, the effects of the anode potential and electronegativity of various anions, including Cl - , ReO 4 - , SO 4 2- and NO 3 - were assessed. The experimental results for the electrosorption of Cl - and ReO 4 - corresponded well with the developed model. The electrosorption capacity demonstrates a logarithmic relationship with the anode potential. The model showed that the electronegativity significantly affects the selectivity. In a mixed Cl - , ReO 4 - , SO 4 2- and NO 3 - solution, ReO 4 - was preferentially adsorbed over the other three anions, and the following selectivity was exhibited: ReO 4 -  > NO 3 -  > Cl -  > SO 4 2- . The results showed that the effect of flow rates on the electrosorption selectivity can be considered negligible when the flow rates are higher than 112 mL min -1 . The anions selectivity can be further enhanced by increasing the anode potential, and electrosorption selectivity is no appreciable decline after 6 experiments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Highly selective transformation of ammonia nitrogen to N2 based on a novel solar-driven photoelectrocatalytic-chlorine radical reactions system.

PubMed

Ji, Youzhi; Bai, Jing; Li, Jinhua; Luo, Tao; Qiao, Li; Zeng, Qingyi; Zhou, Baoxue

2017-11-15

A highly selective method for transforming ammonia nitrogen to N 2 was proposed, based on a novel solar-driven photoelectrocatalytic-chlorine radical reactions (PEC-chlorine) system. The PEC-chlorine system was facilitated by a visible light response WO 3 nanoplate array (NPA) electrode in an ammonia solution containing chloride ions (Cl - ). Under illumination, photoholes from WO 3 promote the oxidation of Cl - to chlorine radical (Cl). This radical can selectively transform ammonia nitrogen to N 2 (79.9%) and NO 3 - (19.2%), similar to the breakpoint chlorination reaction. The ammonia nitrogen removal efficiency increased from 10.6% (PEC without Cl - ) to 99.9% with the PEC-chlorine system within 90 min operation, which can be attributed to the cyclic reactions between Cl - /Cl and the reaction intermediates (NH 2 , NHCl, etc.) that expand the degradation reactions from the surface of the electrodes to the whole solution system. Moreover, Cl is the main radical species contributing to the transformation of ammonia nitrogen to N 2 , which is confirmed by the tBuOH capture experiment. Compared to conventional breakpoint chlorination, the PEC-chlorine system is a more economical and efficient means for ammonia nitrogen degradation because of the fast removal rate, no additional chlorine cost, and its use of clean energy (since it is solar-driven). Copyright © 2017 Elsevier Ltd. All rights reserved.

Study the chemical composition and biological outcomes resulting from the interaction of the hormone adrenaline with heavy elements: Infrared, Raman, electronic, 1H NMR, XRD and SEM studies

NASA Astrophysics Data System (ADS)

Ibrahim, Omar B.; Mohamed, Mahmoud A.; Refat, Moamen S.

2014-01-01

Heavy metal adrenaline complexes formed from the reaction of adrenaline with Al3+, Zn2+, Sn2+, Sb3+, Pb2+and Bi3+ ions in methanolic solvent at 60 °C. The final reaction products have been isolated and characterization using elemental analyses (% of carbon, hydrogen and nitrogen), conductivity measurements, mid infrared, Raman laser, UV-Vis, 1H NMR spectra, X-ray powder diffraction, scanning electron microscopy and energy-dispersive X-ray spectroscopy (EDX). Upon the spectroscopic, conductivity and elemental analyses, the stoichiometric reactions indicated that the data obtained refer to 1:2 (M:L) for Zn2+, Sn2+, Pb2+and Bi3+ complexes [Zn(Adr)2(Cl)2], [Sn(Adr)2]Cl2, [Pb(Adr)2](NO3)2 and [Bi(Adr)2(Cl)2]Cl, while the molar ratio 1:3 (M:L) for Al3+ and Sb3+ with formulas [Al(Adr)3](NO3)3 and [Sb(Adr)3]Cl3. The infrared and Raman laser spectra interpreted the mode of interactions which associated through the two phenolic groups of catechol moiety. The adrenaline chelates have been screened for their in vitro antibacterial activity against four bacteria, Gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) and two strains of fungus (Aspergillus flavus and Candida albicans). The metal chelates were shown to possess more antibacterial and antifungal activities than the free adrenaline chelate.

Observed and model-calculated NO2/NO ratios in tropospheric air sampled during the NASA GTE/CITE-2 field study

NASA Technical Reports Server (NTRS)

Chameides, W. L.; Davis, D. D.; Bradshaw, J.; Sandholm, S.; Rodgers, M.; Baum, B.; Ridley, B.; Gregory, G.; Torres, A.; Condon, E.

1990-01-01

Airborne measurements of NO2/NO ratios in the free troposphere, obtained using two-photon LIF (TP-LIF) and chemiluminescence (CL) detectors during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 (CITE 2) program in summer 1986, are analyzed and compared with the predictions of a photochemical model. The derivation of the model is outlined, with an emphasis on the role of peroxy radicals in the fast photochemical cycling of NO and NO2 and the production of O3; the CITE 2 instruments and flight protocols are described; and the results are presented in extensive tables and graphs and discussed in detail. It was found that on three CITE 2 flights the CL data were systematically greater than the TP-LIF data; when these data were removed, the averaged values of the two instruments agreed to within 1 percent. The NO2/NO ratios predicted by the model are shown to be consistent with the measurements, although usually 20-25 percent lower.

A kinetic study of the interaction between atomic oxygen and aerosols

NASA Technical Reports Server (NTRS)

Akers, F. I.; Wightman, J. P.

1976-01-01

This study was concerned with the effects of NH4Cl and (NH4)2SO4 aerosols on the kinetics of disappearance of atomic oxygen. Atomic oxygen was generated by a 2.45-GHz microwave discharge and the kinetics of disappearance measured in a fast flow system using NO2 titration. Values of the recombination coefficient for heterogeneous wall recombination were determined for clean, H2SO4-coated, and (NH4)2SO4-coated Pyrex to be 0.000050, 0.000020, and 0.000019, respectively. A rapid exothermic chemical reaction was found to occur between atomic oxygen and an NH4Cl wall coating; the products were NH3, NO, H2O, and HCl. The NH4Cl aerosol was generated by gas phase reaction of NH3 with HCl. The aerosol particles were approximately spherical and nearly monodisperse with a mean diameter of 1.6 plus or minus 0.2 micron. The rate constant for the disappearance of atomic oxygen in the presence of NH4Cl aerosol was measured. No significant decrease was observed in the rate of disappearance of atomic oxygen in the presence of an (NH4)2SO4 aerosol at a concentration of 285 mg per cu m.

[Water-soluble anions of atmosphere on Tianwan nuclear power station].

PubMed

Zhao, Heng-Qiang; He, Ying; Zheng, Xiao-Ling; Chen, Fa-Rong; Pang, Shi-Ping; Wang, Cai-Xia; Wang, Xiao-Ru

2010-11-01

Three major water-soluble anions (Cl-, SO4(2-) and NO3-) in the atmosphere of the Tianwan nuclear power station in Lianyungang were determined by ion chromatography from June 2005 to May 2006. The results showed that the annual average concentration of Cl-, SO4(2-) and NO3- in the atmosphere of Tianwan nuclear power station was (33.12 +/- 53.63) microg x m(-3), (53.34 +/- 30.34) microg x m(-3) and (8.34 +/- 4.47) microg x m(-3), respectively. The concentrations of the three water-soluble anions showed evident trend of seasonal variation. The concentrations of Cl-, SO4(2-) reached the highest level in summer and the lowest level in winter, while the concentration of NO3- in autumn and winter was higher than those in summer and spring. Meteorological parameters such as wind direction, wind speed, temperature and relative humidity were studied and showed definite influence to the anions concentration of the atmosphere. This is the first simultaneous monitoring of corrosive anions in the atmosphere of Chinese coastal nuclear power plant, and it will provide basis for the prevention of marine atmospheric corrosion, which will ensure the safely operating of our nuclear power industry.

Factors controlling nitrate fluxes in groundwater in agricultural areas

USGS Publications Warehouse

Liao, Lixia; Green, Christopher T.; Bekins, Barbara A.; Böhlke, J.K.

2012-01-01

The impact of agricultural chemicals on groundwater quality depends on the interactions of biogeochemical and hydrologic factors. To identify key processes affecting distribution of agricultural nitrate in groundwater, a parsimonious transport model was applied at 14 sites across the U.S. Simulated vertical profiles of NO3-, N2 from denitrification, O2, Cl-, and environmental tracers of groundwater age were matched to observations by adjusting the parameters for recharge rate, unsaturated zone travel time, fractions of N and Cl- inputs leached to groundwater, O2 reduction rate, O2 threshold for denitrification, and denitrification rate. Model results revealed important interactions among biogeochemical and physical factors. Chloride fluxes decreased between the land surface and water table possibly because of Cl- exports in harvested crops (averaging 22% of land-surface Cl- inputs). Modeled zero-order rates of O2 reduction and denitrification were correlated. Denitrification rates at depth commonly exceeded overlying O2 reduction rates, likely because shallow geologic sources of reactive electron donors had been depleted. Projections indicated continued downward migration of NO3- fronts at sites with denitrification rates -1 yr-1. The steady state depth of NO3- depended to a similar degree on application rate, leaching fraction, recharge, and NO3- and O2 reaction rates. Steady state total mass in each aquifer depended primarily on the N application rate. In addition to managing application rates at land surface, efficient water use may reduce the depth and mass of N in groundwater because lower recharge was associated with lower N fraction leached. Management actions to reduce N leaching could be targeted over aquifers with high-recharge and low-denitrification rates.

Predictors of Sick Sinus Syndrome in Patients after Successful Radiofrequency Catheter Ablation of Atrial Flutter

PubMed Central

Song, Changho; Jin, Moo-Nyun; Lee, Jung-Hee; Kim, In-Soo; Uhm, Jae-Sun; Pak, Hui-Nam; Lee, Moon-Hyoung

2015-01-01

Purpose The identification of sick sinus syndrome (SSS) in patients with atrial flutter (AFL) is difficult before the termination of AFL. This study investigated the patient characteristics used in predicting a high risk of SSS after AFL ablation. Materials and Methods Out of 339 consecutive patients who had undergone radiofrequency ablation for AFL from 1991 to 2012, 27 (8%) had SSS (SSS group). We compared the clinical characteristics of patients with and without SSS (n=312, no-SSS group). Results The SSS group was more likely to have a lower body mass index (SSS: 22.5±3.2; no-SSS: 24.0±3.0 kg/m2; p=0.02), a history of atrial septal defects (ASD; SSS: 19%; no-SSS: 6%; p=0.01), a history of coronary artery bypass graft surgery (CABG; SSS: 11%; no-SSS: 2%; p=0.002), and a longer flutter cycle length (CL; SSS: 262.3±39.2; no-SSS: 243.0±40; p=0.02) than the no-SSS group. In multivariate analysis, a history of ASD [odds ratio (OR) 3.7, 95% confidence interval (CI) 1.2-11.4, p=0.02] and CABG (7.1, 95% CI 1.5-32.8, p=0.01) as well as longer flutter CL (1.1, 95% CI 1.0-1.2, p=0.04) were independent risk factors for SSS. Conclusion A history of ASD and CABG as well as longer flutter CL increased the risk of SSS after AFL ablation. While half of the patients with SSS after AFL ablation experienced transient SSS, heart failure was associated with irreversible SSS. PMID:25510744

Syntheses and structures of [UO2( L)5](ClO4)2 and [U( L')4(H2O)4](ClO4)4 ( L is dimethylformamide, L' is N,N-dimethylcarbamide)

NASA Astrophysics Data System (ADS)

Serezhkin, V. N.; Vologzhanina, A. V.; Pushkin, D. V.; Astashkina, D. A.; Savchenkov, A. V.; Serezhkina, L. B.

2017-09-01

The reaction of aqueous solutions of uranyl perchlorate with selected organic amides was studied in the dark and under the sunlight. The complexes [UVIO2(C3H7NO)5](ClO4)2 ( I) and [UIV(C3H8N2O)4(H2O)4](ClO4)4 ( II), where C3H7NO is N,N-dimethylformamide ( Dmfa) and C3H8N2O is N,N-dimethylcarbamide ( a-Dmur), were studied by X-ray diffraction. Complex II and the complex UIV( s-Dmur)4(H2O)4(ClO4)4 ( III), where s-Dmur is N,N'-dimethylcarbamide, were studied by IR spectroscopy. Crystals I and II are composed of mononuclear [UO2( Dmfa)5]2+ and [U( Dmur)4(H2O)4]4+ groups as uranium-containing structural units belonging to the crystal-chemical groups AM 7 1 ( A = UVI, M 1 = O2- and Dmfa) and AM 8 1 ( A = UIV, M 1 = Dmur and H2O) of uranium complexes, respectively. The mononuclear uranium- containing complexes in the crystals of U(IV) and U(VI) perchlorates were found to obey the 14 neighbors rule.

Glyoxal and Methylglyoxal Setschenow Salting Constants in Sulfate, Nitrate, and Chloride Solutions: Measurements and Gibbs Energies.

PubMed

Waxman, Eleanor M; Elm, Jonas; Kurtén, Theo; Mikkelsen, Kurt V; Ziemann, Paul J; Volkamer, Rainer

2015-10-06

Knowledge about Setschenow salting constants, KS, the exponential dependence of Henry's Law coefficients on salt concentration, is of particular importance to predict secondary organic aerosol (SOA) formation from soluble species in atmospheric waters with high salt concentrations, such as aerosols. We have measured KS of glyoxal and methylglyoxal for the atmospherically relevant salts (NH4)2SO4, NH4NO3, NaNO3, and NaCl and find that glyoxal consistently "salts-in" (KS of -0.16, -0.06, -0.065, -0.1 molality(-1), respectively) while methylglyoxal "salts-out" (KS of +0.16, +0.075, +0.02, +0.06 molality(-1)). We show that KS values for different salts are additive and present an equation for use in atmospheric models. Additionally, we have performed a series of quantum chemical calculations to determine the interactions between glyoxal/methylglyoxal monohydrate with Cl(-), NO3(-), SO4(2-), Na(+), and NH4(+) and find Gibbs free energies of water displacement of -10.9, -22.0, -22.9, 2.09, and 1.2 kJ/mol for glyoxal monohydrate and -3.1, -10.3, -7.91, 6.11, and 1.6 kJ/mol for methylglyoxal monohydrate with uncertainties of 8 kJ/mol. The quantum chemical calculations support that SO4(2-), NO3(-), and Cl(-) modify partitioning, while cations do not. Other factors such as ion charge or partitioning volume effects likely need to be considered to fully explain salting effects.

Matrix influences on the determination of common ions by using ion chromatography part 1--determination of inorganic anions.

PubMed

Michalski, Rajmund; Lyko, Aleksandra; Kurzyca, Iwona

2012-07-01

Ion chromatography is the most popular instrumental analytical method used for the determination of anions and cations in water and wastewater. Isocratic ion chromatography with suppressed conductivity detection is frequently used in laboratories carrying out routine analyses of inorganic anions. The paper presents the results of the research into the influence of selected inorganic anions dominant in environmental samples (Cl(-), NO(3)(-), SO(4)(2-)) on the possibility of simultaneous determination of F(-), Cl(-), NO(2)(-), NO(3)(-), PO(4)(3-) and SO(4)(2-) with the application of this most popular ion chromatography type in standard separation conditions. Four Dionex and four Metrohm anion-exchange columns were tested in standard separation conditions recommended by their manufacturers with both standard solutions and environmental samples with complex matrix.

Evolution of aerosol chemistry in Xi'an, inland China, during the dust storm period of 2013 - Part 1: Sources, chemical forms and formation mechanisms of nitrate and sulfate

NASA Astrophysics Data System (ADS)

Wang, G. H.; Cheng, C. L.; Huang, Y.; Tao, J.; Ren, Y. Q.; Wu, F.; Meng, J. J.; Li, J. J.; Cheng, Y. T.; Cao, J. J.; Liu, S. X.; Zhang, T.; Zhang, R.; Chen, Y. B.

2014-11-01

A total suspended particulate (TSP) sample was collected hourly in Xi'an, an inland megacity of China near the Loess Plateau, during a dust storm event of 2013 (9 March 18:00-12 March 10:00 LT), along with a size-resolved aerosol sampling and an online measurement of PM2.5. The TSP and size-resolved samples were determined for elemental carbon (EC), organic carbon (OC), water-soluble organic carbon (WSOC) and nitrogen (WSON), inorganic ions and elements to investigate chemistry evolution of dust particles. Hourly concentrations of Cl-, NO3-, SO42-, Na+ and Ca2+ in the TSP samples reached up to 34, 12, 180, 72 and 28 μg m-3, respectively, when dust peak arrived over Xi'an. Chemical compositions of the TSP samples showed that during the whole observation period NH4+ and NO3- were linearly correlated with each other (r2=0.76) with a molar ratio of 1 : 1, while SO42- and Cl- were well correlated with Na+, Ca2+, Mg2+ and K+ (r2 > 0.85). Size distributions of NH4+ and NO3- presented a same pattern, which dominated in the coarse mode (> 2.1 μm) during the event and predominated in the fine mode (< 2.1 μm) during the non-event. SO42- and Cl- also dominated in the coarse mode during the event hours, but both exhibited two equivalent peaks in both the fine and the coarse modes during the non-event, due to the fine-mode accumulations of secondarily produced SO42- and biomass-burning-emitted Cl- and the coarse-mode enrichments of urban soil-derived SO42- and Cl-. Linear fit regression analysis further indicated that SO42- and Cl- in the dust samples possibly exist as Na2SO4, CaSO4 and NaCl, which directly originated from Gobi desert surface soil, while NH4+ and NO3- in the dust samples exist as NH4NO3. We propose a mechanism to explain these observations in which aqueous phase of dust particle surface is formed via uptake of water vapor by hygroscopic salts such as Na2SO4 and NaCl, followed by heterogeneous formation of nitrate on the liquid phase and subsequent absorption of ammonia. Our data indicate that 54 ± 20% and 60 ± 23% of NH4+ and NO3- during the dust period were secondarily produced via this pathway, with the remaining derived from the Gobi desert and Loess Plateau, while SO42- in the event almost entirely originated from the desert regions. Such cases are different from those in the East Asian continental outflow region, where during Asia dust storm events SO42- is secondarily produced and concentrates in sub-micrometer particles as (NH4)2SO4 and/or NH4HSO4. To the best of our knowledge, the current work for the first time revealed an infant state of the East Asian dust ageing process in the regions near the source, which is helpful for researchers to understand the panorama of East Asian dust ageing process from the desert area to the downwind region.

Nitrite ion mitigates the formation of N-nitrosodimethylamine (NDMA) during chloramination of ranitidine.

PubMed

Seid, Mingizem Gashaw; Cho, Kangwoo; Lee, Changha; Park, Hyun-Mee; Hong, Seok Won

2018-08-15

Ranitidine (RNT) has been an important tertiary amine precursor of N-nitrosodimethylamine (NDMA) in chlorine-based water treatment, due to reaction with monochloramine (NH 2 Cl) with exceptionally high molar yields up to 90%. This study examined the effects of nitrite ions (NO 2 - ) on the kinetics of NDMA formation during the chloramination of RNT under variable concentrations of dissolved oxygen (DO, 0.7-7.5mg/L), RNT (5-30μM), NH 2 Cl (5-20mM), NO 2 - or NO 3 - (0-2mM) and pH (5.6-8.6). In the absence of the NO 2 - , the ultimate molar yield of NDMA after 6h of reaction was primarily influenced by [DO] and pH, while marginally affected by initial [RNT] and [NH 2 Cl]. A kinetic model, prepared in accordance with the reaction sequence of NDMA formation, suggested that the rate determining step was accelerated with increasing [NH 2 Cl] 0 , [DO], and pH. A Kinetic study together with ultra-performance liquid chromatography-quadrupole-time of flight mass spectrometer (UPLC-Q-TOF MS) and gas chromatography (GC)/TOF MS analyses in parallel demonstrated that the nitrite ion inhibited the nucleophilic substitution of the terminal amine on NH 2 Cl, and reduced the pseudo-steady state concentration of N-peroxyl radicals, significantly decreasing the ultimate yields of NDMA. Copyright © 2018 Elsevier B.V. All rights reserved.

Nitrate retention in riparian ground water at natural and elevated nitrate levels in North Central Minnesota

USGS Publications Warehouse

Duff, J.H.; Jackman, A.P.; Triska, F.J.; Sheibley, R.W.; Avanzino, R.J.

2007-01-01

The relationship between local ground water flows and NO3- transport to the channel was examined in three well transects from a natural, wooded riparian zone adjacent to the Shingobee River, MN. The hillslope ground water originated as recharge from intermittently grazed pasture up slope of the site. In the hillslope transect perpendicular to the stream, ground water NO3- concentrations decreased from ???3 mg N L-1 beneath the ridge (80 m from the channel) to 0.01 to 1.0 mg N L-1 at wells 1 to 3 m from the channel. The Cl- concentrations and NO3/Cl ratios decreased toward the channel indicating NO3- dilution and biotic retention. In the bankside well transect parallel to the stream, two distinct ground water environments were observed: an alluvial environment upstream of a relict beaver dam influenced by stream water and a hillslope environment downstream of the relict beaver dam. Nitrate was elevated to levels representative of agricultural runoff in a third well transect looted ???5 m from the stream to assess the effectiveness of the riparian zone as a NO3- sink. Subsurface NO3- injections revealed transport of up to 15 mg N L-1 was nearly conservative in the alluvial riparian environment. Addition of glucose stimulated dissolved oxygen uptake and promoted NO3- retention under both background and elevated NO 3- levels in summer and winter. Disappearance of added NO3- was followed by transient NO2- formation and, in the presence of C2H2, by N2O formation, demonstrating potential denitrification. Under current land use, most NO3- associated with local ground water is biotically retained or diluted before reaching the channel. However, elevating NO 3- levels through agricultural cultivation would likely result in increased NO3- transport to the channel. ?? ASA, CSSA, SSSA.

Chemotaxis-mediated biodegradation of cyclic nitramine explosives RDX, HMX, and CL-20 by Clostridium sp. EDB2.

PubMed

Bhushan, Bharat; Halasz, Annamaria; Thiboutot, Sonia; Ampleman, Guy; Hawari, Jalal

2004-04-09

Cyclic nitramine explosives, RDX, HMX, and CL-20 are hydrophobic pollutants with very little aqueous solubility. In sediment and soil environments, they are often attached to solid surfaces and/or trapped in pores and distribute heterogeneously in aqueous environments. For efficient bioremediation of these explosives, the microorganism(s) must access them by chemotaxis ability. In the present study, we isolated an obligate anaerobic bacterium Clostridium sp. strain EDB2 from a marine sediment. Strain EDB2, motile with numerous peritrichous flagella, demonstrated chemotactic response towards RDX, HMX, CL-20, and NO(2)(-). The three explosives were biotransformed by strain EDB2 via N-denitration with concomitant release of NO(2)(-). Biotransformation rates of RDX, HMX, and CL-20 by the resting cells of strain EDB2 were 1.8+/-0.2, 1.1+/-0.1, and 2.6+/-0.2nmol h(-1)mgwet biomass(-1) (mean+/-SD; n=3), respectively. We found that commonly seen RDX metabolites such as TNX, methylenedinitramine, and 4-nitro-2,4-diazabutanal neither produced NO(2)(-) during reaction with strain EDB2 nor they elicited chemotaxis response in strain EDB2. The above data suggested that NO(2)(-) released from explosives during their biotransformation might have elicited chemotaxis response in the bacterium. Biodegradation and chemotactic ability of strain EDB2 renders it useful in accelerating the bioremediation of explosives under in situ conditions.

Ecohydrological factors affecting nitrate concentrations in a phreatic desert aquifer in northwestern China

USGS Publications Warehouse

Gates, J.B.; Böhlke, J.K.; Edmunds, W.M.

2008-01-01

Aerobic conditions in desert aquifers commonly allow high nitrate (NO 3-) concentrations in recharge to persist for long periods of time, an important consideration for N-cycling and water quality. In this study, stable isotopes of NO3- (??15N NO3 and ??18ONO3) were used to trace NO3- cycling processes which affect concentrations in groundwater and unsaturated zone moisture in the arid Badain Jaran Oesert in northwestern China. Most groundwater NO3- appears to be depleted relative to Cl- in rainfall concentrated by evapotranspiration, indicating net N losses. Unsaturated zone NO 3- is generally higher than groundwater NO 3- in terms of both concentration (up to 15 476 ??M, corresponding to 3.6 mg NO3--N per kg sediment) and ratios with Cl-. Isotopic data indicate that the NO3- derives primarily from nitrification, with a minor direct contribution of atmospheric NO3- inferred for some samples, particularly in the unsaturated zone. Localized denitrification in the saturated zone is suggested by isotopic and geochemical indicators in some areas. Anthropogenic inputs appear to be minimal, and variability is attributed to environmental factors. In comparison to other arid regions, the sparseness of vegetation in the study area appears to play an important role in moderating unsaturated zone NO3- accumulation by allowing solute flushing and deterring extensive N2 fixation. ?? 2008 American Chemical Society.

Temperature dependence of the NO3 absorption spectrum

NASA Technical Reports Server (NTRS)

Sander, Stanley P.

1986-01-01

The absorption spectrum of the gas-phase NO3 radical has been studied between 220 and 700 nm by using both flash photolysis and discharge flow reactors for the production of NO3. In the flash photolysis method, cross sections at the peak of the (0,0) band at 661.9 nm were measured relative to the cross section of ClONO2 at several different wavelengths. From the best current measurements of the ClONO2 spectrum, the NO3 cross section at 661.9 nm was determined to be (2.28 + or 0.34) x 10 to the -17th sq cm/molecule at 298 K. Measurements at 230 K indicated that the cross section increases by a factor of 1.18 at the peak of the (0,0) band. The discharge flow method was used both to obtain absolute cross sections at 661.9 nm and to obtain relative absorption spectra between 300 and 700 nm at 298 and 230 K. A value of (1.83 + or - 0.27) x 10 to the -17th sq cm/molecule was obtained for sigma NO3 at 661.9 nm at 298 K. Upper limits to the NO3 cross sections were also measured between 220 and 260 nm with the discharge flow method.

Predictors of sick sinus syndrome in patients after successful radiofrequency catheter ablation of atrial flutter.

PubMed

Song, Changho; Jin, Moo-Nyun; Lee, Jung-Hee; Kim, In-Soo; Uhm, Jae-Sun; Pak, Hui-Nam; Lee, Moon-Hyoung; Joung, Boyoung

2015-01-01

The identification of sick sinus syndrome (SSS) in patients with atrial flutter (AFL) is difficult before the termination of AFL. This study investigated the patient characteristics used in predicting a high risk of SSS after AFL ablation. Out of 339 consecutive patients who had undergone radiofrequency ablation for AFL from 1991 to 2012, 27 (8%) had SSS (SSS group). We compared the clinical characteristics of patients with and without SSS (n=312, no-SSS group). The SSS group was more likely to have a lower body mass index (SSS: 22.5±3.2; no-SSS: 24.0±3.0 kg/m²; p=0.02), a history of atrial septal defects (ASD; SSS: 19%; no-SSS: 6%; p=0.01), a history of coronary artery bypass graft surgery (CABG; SSS: 11%; no-SSS: 2%; p=0.002), and a longer flutter cycle length (CL; SSS: 262.3±39.2; no-SSS: 243.0±40; p=0.02) than the no-SSS group. In multivariate analysis, a history of ASD [odds ratio (OR) 3.7, 95% confidence interval (CI) 1.2-11.4, p=0.02] and CABG (7.1, 95% CI 1.5-32.8, p=0.01) as well as longer flutter CL (1.1, 95% CI 1.0-1.2, p=0.04) were independent risk factors for SSS. A history of ASD and CABG as well as longer flutter CL increased the risk of SSS after AFL ablation. While half of the patients with SSS after AFL ablation experienced transient SSS, heart failure was associated with irreversible SSS.

Evaluating evidence for Cl sources and oxidation chemistry in a coastal, urban environment

NASA Astrophysics Data System (ADS)

Young, C. J.; Washenfelder, R. A.; Edwards, P. M.; Parrish, D. D.; Gilman, J. B.; Kuster, W. C.; Mielke, L. H.; Osthoff, H. D.; Tsai, C.; Pikelnaya, O.; Stutz, J.; Veres, P. R.; Roberts, J. M.; Griffith, S.; Dusanter, S.; Stevens, P. S.; Flynn, J.; Grossberg, N.; Lefer, B.; Holloway, J. S.; Peischl, J.; Ryerson, T. B.; Atlas, E. L.; Blake, D. R.; Brown, S. S.

2013-05-01

The role of chlorine atoms (Cl) in atmospheric oxidation was traditionally thought to be limited to the marine boundary layer, where they are produced through heterogeneous reactions involving sea salt. However, recent observation of photolytic Cl precursors (ClNO2 and Cl2) formed from anthropogenic pollution has expanded the potential importance of Cl to include coastal and continental urban areas. Measurements of ClNO2 in Los Angeles during CalNex showed it to be an important primary (first generation) radical source. Ratios of volatile organic compounds (VOCs) have been proposed as a sensitive method to quantify Cl oxidation, but have shown little evidence for a significant role of Cl outside of the Arctic. We used a box model with the Master Chemical Mechanism (MCM v3.2) chemistry scheme, constrained by observations in Los Angeles, to examine the Cl-sensitivity of the most commonly used VOC ratios (i-butane, n-butane, and propane) as a function of NOx and secondary radical production. Model results indicated these and faster reacting VOC tracer ratios could not detect the influence of Cl unless the sustained ratio of OH to Cl was below 200. However, the model results also show that secondary (second generation) OH production resulting from Cl oxidation of VOCs is strongly influenced by NOx, and that this effect can obscure the importance of Cl as a primary oxidant. Calculated concentrations of Cl showed a maximum in mid-morning due to a photolytic source from ClNO2 and loss primarily to reactions with VOCs. The OH to Cl ratio was below 200 for approximately three hours in the morning, but Cl oxidation was not evident from the measured ratios of VOCs. Instead, model simulations show that secondary OH production causes VOC ratios to follow the values expected for OH oxidation despite the significant input of primary Cl from ClNO2 photolysis in the morning. Despite the prevalence of secondary OH as an oxidant in Los Angeles, Cl may play an important role in tropospheric chemistry. The reactivity of Cl in Los Angeles during CalNex was more than an order of magnitude larger than that of OH. In addition, because of its reactivity toward different classes of VOCs and its greater propensity to participate in chain propagation rather than sink reactions, Cl atoms have a different impact on regional atmospheric oxidation than do OH radicals.

The effect of NO-donors on chloride efflux, intracellular Ca(2+) concentration and mRNA expression of CFTR and ENaC in cystic fibrosis airway epithelial cells.

PubMed

Oliynyk, Igor; Hussain, Rashida; Amin, Ahmad; Johannesson, Marie; Roomans, Godfried M

2013-06-01

Since previous studies showed that the endogenous bronchodilator, S-nitrosglutathione (GSNO), caused a marked increase in CFTR-mediated chloride (Cl(-)) efflux and improved the trafficking of CFTR to the plasma membrane, and that also the nitric oxide (NO)-donor GEA3162 had a similar, but smaller, effect on Cl(-) efflux, it was investigated whether the NO-donor properties of GSNO were relevant for its effect on Cl(-) efflux from airway epithelial cells. Hence, the effect of a number of other NO-donors, sodium nitroprusside (SNP), S-nitroso-N-acetyl-DL-penicillamine (SNAP), diethylenetriamine/nitric oxide adduct (DETA-NO), and diethylenetriamine/nitric oxide adduct (DEA-NONOate) on Cl(-) efflux from CFBE (∆F508/∆F508-CFTR) airway epithelial cells was tested. Cl(-) efflux was determined using the fluorescent N-(ethoxycarbonylmethyl)-6-methoxyquinoliniu bromide (MQAE)-technique. Possible changes in the intracellular Ca(2+) concentration were tested by the fluorescent fluo-4 method in a confocal microscope system. Like previously with GSNO, after 4 h incubation with the NO-donor, an increased Cl(-) efflux was found (in the order SNAP>DETA-NO>SNP). The effect of DEA-NONOate on Cl(-) efflux was not significant, and the compound may have (unspecific) deleterious effects on the cells. Again, as with GSNO, after a short (5 min) incubation, SNP had no significant effect on Cl(-) efflux. None of the NO-donors that had a significant effect on Cl(-) efflux caused significant changes in the intracellular Ca(2+) concentration. After 4 h preincubation, SNP caused a significant increase in the mRNA expression of CFTR. SNAP and DEA-NONOate decreased the mRNA expression of all ENaC subunits significantly. DETA-NO caused a significant decrease only in α-ENaC expression. After a short preincubation, none of the NO-donors had a significant effect, neither on the expression of CFTR, nor on that of the ENaC subunits in the presence and absence of L-cysteine. It can be concluded that the effect of GSNO on Cl(-) efflux is, at least in part, due to its properties as an NO-donor, and the effect is likely to be mediated by CFTR, not by Ca(2+)-activated Cl(-) channels. Copyright © 2013. Published by Elsevier Inc.

A newly synthesized thiazole derivative as a fluoride ion chemosensor: naked-eye, spectroscopic, electrochemical and NMR studies.

PubMed

Sarıgüney, Ahmet Burak; Saf, Ahmet Özgür; Coşkun, Ahmet

2014-07-15

2,3-Indoledione 3-thiosemicarbazone (TSCI) and a novel compound 3-(2-(4-(4-phenoxyphenyl)thiazol-2-yl)hydrazono)indolin-2-one (FTHI) were synthesized with high yield and characterized by spectroscopic techniques. The complexation behaviors of TSCI and FTHI for various anionic species (F(-), Cl(-), Br(-), I(-), NO2(-), NO3(-), BzO(-), HSO4(-), ClO4(-)) in CH3CN were investigated and compared by UV-vis spectroscopy, cyclic voltammetry and (1)H NMR titration techniques. FTHI showed high degree of selectivity for fluoride over other anions. This selectivity could be easily observed by the naked eye, indicating that FTHI is potential colorimetric sensor for fluoride anion. Copyright © 2014 Elsevier B.V. All rights reserved.

Studies on the movements of ionic selectivity, compatible solutes, and intracellular ions caused in the leaves of spinach (Spinacia oleracea L.) plants cultured in a nutrient solution with seawater.

PubMed

Sun, Jin; Jia, Yongxia; Guo, Shirong; Chen, Lifang

2010-01-01

Analyses of ionic selectivity, compatible solutes, and intracellular ions in the leaves of spinach (Spinacia oleracea L.) plants cultured in the Hoagland's nutrient solution with or.without seawater (40%) were carried out using two cultivars--the Helan No.3 (seawater tolerant) and the Yuanye (seawater sensitive). When both cultivars were subjected to seawater stress, the leaves of the Helan No. 3 spinach preferred potassium (K+), calcium (Ca2+), magnesium (Mg2+), and sulfate (SO4(2-)) over sodium (Na+) and chlorine (Cl-) to keep high ratios of K/Na, Mg/Na, Ca/Na, and SO4(2-)/Cl- compared with the Yanye spinach. Moreover, those of the Helan No. 3 spinach under the seawater stress showed high efficiency of accumulation of compatible solutes (sugars and proline), low degradation of proteins, and suppression of free amino acids. However, the activities of plasma membrane H+ -ATPase and tonoplast H+ -ATPase in the leaves of spinach with the stress were enhanced. Taken together, the Helan No. 3 spinach under the seawater stress seems to acquire a high tolerance to the seawater salinity by inducing a high ion uptake, low concentration of Na+ and Cl-, efficient accumulation of compatible solutes, low decomposition of proteins, and suppression of free amino acids in the leaves.

Myeloperoxidase-oxidized high density lipoprotein impairs atherosclerotic plaque stability by inhibiting smooth muscle cell migration.

PubMed

Zhou, Boda; Zu, Lingyun; Chen, Yong; Zheng, Xilong; Wang, Yuhui; Pan, Bing; Dong, Min; Zhou, Enchen; Zhao, Mingming; Zhang, Youyi; Zheng, Lemin; Gao, Wei

2017-01-10

High density lipoprotein (HDL) has been proved to be a protective factor for coronary heart disease. Notably, HDL in atherosclerotic plaques can be nitrated (NO 2 -oxHDL) and chlorinated (Cl-oxHDL) by myeloperoxidase (MPO), likely compromising its cardiovascular protective effects. Here we determined the effects of NO 2 -oxHDL and Cl-oxHDL on SMC migration using wound healing and transwell assays, proliferation using MTT and BrdU assays, and apoptosis using Annexin-V assay in vitro, as well as on atherosclerotic plaque stability in vivo using a coratid artery collar implantation mice model. Our results showed that native HDL promoted SMC proliferation and migration, whereas NO 2 -oxHDL and Cl-oxHDL inhibited SMC migration and reduced capacity of stimulating SMC proliferation as well as migration, respectively. OxHDL had no significant influence on SMC apoptosis. In addition, we found that ERK1/2-phosphorylation was significantly lower when SMCs were incubated with NO 2 -oxHDL and Cl-oxHDL. Furthermore, transwell experiments showed that differences between native HDL, NO 2 -oxHDL and Cl-oxHDL was abolished after PD98059 (MAPK kinase inhibitor) treatment. In aortic SMCs from scavenger receptor BI (SR-BI) deficient mice, differences between migration of native HDL, NO 2 -oxHDL and Cl-oxHDL treated SMCs vanished, indicating SR-BI's possible role in HDL-associated SMC migration. Importantly, NO 2 -oxHDL and Cl-oxHDL induced neointima formation and reduced SMC positive staining cells in atherosclerotic plaque, resulting in elevated vulnerable index of atherosclerotic plaque. These findings implicate MPO-catalyzed oxidization of HDL may contribute to atherosclerotic plaque instability by inhibiting SMC proliferation and migration through MAPK-ERK pathway which was dependent on SR-BI.

Ethyl 2-(4-chloro-2-oxo-2,3-dihydro-1,3-benzothia­zol-3-yl)acetate

PubMed Central

Shen, Wen-Tong; Yao, Cheng

2009-01-01

In the mol­ecule of the title compound, C11H10ClNO3S, the benzene and thia­zole rings are oriented at a dihedral angle of 1.25 (3)°. Intra­molecular C—H⋯O and C—H⋯Cl inter­actions result in the formation of two five-membered rings which both adopt envelope conformations. PMID:21582452

Effects of Simulated Nitrogen Deposition on Soil Net Nitrogen Mineralization in the Meadow Steppe of Inner Mongolia, China

PubMed Central

Liu, Xing-ren; Ren, Jian-qiang; Li, Sheng-gong; Zhang, Qing-wen

2015-01-01

Effects of simulated nitrogen (N) deposition on soil net nitrogen mineralization (NNM) were examined in situ during two growing seasons, using the resin-core technique in the semiarid meadow steppe in Inner Mongolia, China. The aim of this study is to clarify the effect of N levels (0, 10, and 20 kg N ha−1yr−1) and forms (NH4 + and NO3 -) on soil mineral N and NNM. Our results showed that N levels had no significant differences on soil mineral N and NNM. In the first year, three N treatments ((NH4)2SO4, NH4Cl and KNO3) increased soil NH4 + concentrations but had no significant effects on soil NO3 - concentrations. In the second year, (NH4)2SO4 treatment increased soil NO3 - concentrations, NH4Cl and KNO3 treatments decreased them. Three N treatments significantly decreased soil NH4 + concentrations in the later stages of the second year. As for the soil NNM, three N treatments had no significant effects on the rates of soil NNM (R m) and net nitrification (R n) in the first year, but significantly decreased them in the second year. The contribution of N addition to Rm was higher from (NH4)2SO4 than from NH4Cl and KNO3. However, Soil R m was mainly affected by soil water content (SWC), accumulated temperature (Ta), and soil total N (TN). These results suggest that the short-term atmospheric N deposition may inhibit soil NNM in the meadow steppe of Inner Mongolia. PMID:26218275

Mono- and binuclear molybdenum and tungsten complexes containing asymmetric bridging ligands: Effects of ligand conjugation and conformation on metal-metal interactions

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

Das, A.; Jeffery, J.C.; Maher, J.P.

The authors have prepared the new monodentate ligands 4-(4-methoxyphenyl)pyridine, 1-(4-pyridyl)-2-(4-methoxyphenyl)ethene, 1-(4-pyridyl)-2-(3-methoxyphenyl)ethene, and 1-(3-pyridyl)-2-(4-methoxyphenyl)ethene (L[sup 5]-L[sup 8]); demethylation of the methoxy group in each case afforded the new bridging bidentate ligands HL[sup 1]-HL[sup 4], which contain one pyridyl and one phenolate donor. Attachment of a MoL*(NO)Cl [L* = hydrotris(3,5-dimethylpyrazolyl)borate] moiety to the pyridyl groups of L[sup 5]-L[sup 8] gave the 17-electron complexes [Mo(NO)L*ClL[prime

Understanding the insight into the mechanisms and dynamics of the Cl-initiated oxidation of (CH3)3CC(O)X and the subsequent reactions in the presence of NO and O2 (X = F, Cl, and Br).

PubMed

Bai, Feng-Yang; Lv, Shuang; Ma, Yuan; Liu, Chun-Yu; He, Chun-Fang; Pan, Xiu-Mei

2017-03-01

In this work, the density functional and high-level ab initio theories are adopted to investigate the mechanisms and kinetics of reaction of (CH 3 ) 3 CC(O)X (X = F, Cl, and Br) with atomic chlorine. Rate coefficients for the reactions of chlorine atom with (CH 3 ) 3 CC(O)F (k 1 ), (CH 3 ) 3 CC(O)Cl (k 2 ), and (CH 3 ) 3 CC(O)Br (k 3 ) are calculated using canonical variational transition state theory coupled with small curvature tunneling method over a wide range of temperatures from 250 to 1000 K. The dynamic calculations are performed by the variational transition state theory with the interpolated single-point energies method at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-311++G(d,p) level of theory. Computed rate constant is in good line with the available experimental value. The rate constants for the title reactions are in this order: k 1

High-performance polymeric photovoltaic cells with a gold chloride-treated polyacrylonitrile hole extraction interlayer

NASA Astrophysics Data System (ADS)

Jeong, Ji-Ho; Noh, Yong-Jin; Kim, Seok-Soon; Kwon, Sung-Nam; Na, Seok-In

2018-03-01

We introduce a high efficiency polymeric photovoltaic cell (PPV) to be obtained by polyacrylonitrile (PAN) hole extraction layer (HEL) modification with gold chloride (AuCl3). The role of PAN HELs with AuCl3 and their effects on solar cell performances were studied with ultraviolet photoemission spectroscopy, atomic force microscopy, internal resistances in PPVs, and current-voltage power curves. The resultant PPVs with AuCl3-treated PAN HELs showed improved cell efficiency compared to PSCs with no interlayer and PAN without AuCl3. Furthermore, with AuCl3-treated PAN, we finally achieved a high efficiency of 6.91%, and a desirable PPV-stability in poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b‧]dithiophe-ne-2,6-diyl][3-fluoro-2-[(2-thylhexyl)carbonyl]-thieno[3,4-b]thiophenediyl

Electrochemical characterization of cerium-based conversion coatings on aluminum alloy 7075-T6

NASA Astrophysics Data System (ADS)

Joshi, Simon

This research used electrochemical techniques to characterize the deposition and corrosion protection behavior of cerium-based conversion coatings on Al 7075-T6. Alkaline activation decreased native oxide impedance (5.9 kO-cm2) by ˜25% promoting deposition of 250--500 nm coatings. Activation in NaOH solutions deposited coatings with large cracks and craters, whereas Na2CO3 activation resulted in uniform coatings, i.e., fewer cracks and almost no craters. Uniformly deposited coatings exhibited better cathodic inhibition and higher impedance (˜200 kO-cm 2) than on NaOH activated substrates (˜100 kO-cm 2). Subsurface crevices, caused by Cl- and H 2O2 in the deposition solution, were found under large cracks and craters. Thus, Na2CO3 activation produced fewer subsurface crevices. To reduce subsurface crevice formation, Ce(NO3) 3 and CeCl3 were used in different ratios. Coatings made using 100% Ce(NO3)3 solutions were ˜60 nm thick without subsurface crevices, but the coatings offered little corrosion protection. Despite formation of subsurface crevices, Cl- was necessary as impedance increased linearly with Cl- concentration in the deposition solution. To characterize the different non-uniform features of the coatings, microelectrochemical testing was performed and it showed three distinct regions: active, intermediate, and passive. Humidity experiments were performed to understand the effect of moisture during salt spray testing and showed an increase in coating impedance by making the exposed substrate oxide more passive. However, this passive oxide could not provide corrosion resistance in a chloride environment. Dissolution studies showed that cerium migration was only possible at pH ≤2. Overall, deposition of uniform 250--500 nm thick outings was essential to make it an effective barrier to Cl - attach and prevent subsurface crevices on Al 7075-T6.

Detection of orbicularis oris muscle defects in first degree relatives of cleft lip children using ultrasound.

PubMed

Mittal, M; Maheshwari, N; Ahlawat, K; Sharma, V; Sultan, A; Chopra, R

2012-01-01

The severity of cleft lip (CL) varies considerably from complete bilateral CL and palate at one end of the spectrum to a minimal CL at the other. In some cases of microform clefting, there may be no visible manifestation of the defect on the lip surface (i.e., the defect is occult) and no residual functional deficit. This study used high resolution ultrasonography to detect subclinical anomalies of orbicularis oris muscle (OOM) in first degree relatives of CL +- cleft palate children and compared it with controls. Thirty relatives of 25 children with non-syndromic CL or CL+ CP were identified for the study. Thirty subjects having negative family history of CL/P in three generations and absence of any minimal cleft features were taken as controls. Ultrasound scans of OOM of all the controls and relatives were taken. Statistical analysis was performed using standard χ2 tests with Yates correction. Defects were seen in 13.3% of relatives and no defects were seen in controls, this was not statistically significant. The data support the hypothesis that subclinical CL cases with subepithelial OOM defects do exist and Orbicularis oris discontinuities represent the mildest form of CL.

Highly active, low-valence molybdenum- and tungsten-amide catalysts for bifunctional imine-hydrogenation reactions.

PubMed

Chakraborty, Subrata; Blacque, Olivier; Fox, Thomas; Berke, Heinz

2014-01-01

The reactions of [M(NO)(CO)4(ClAlCl3)] (M=Mo, W) with (iPr2PCH2CH2)2NH, (PN(H)P) at 90 °C afforded [M(NO)(CO)(PN(H)P)Cl] complexes (M=Mo, 1a; W, 1b). The treatment of compound 1a with KOtBu as a base at room temperature yielded the alkoxide complex [Mo(NO)(CO)(PN(H)P)(OtBu)] (2a). In contrast, with the amide base Na[N(SiMe3 )2 ], the PN(H) P ligand moieties in compounds 1a and 1b could be deprotonated at room temperature, thereby inducing dehydrochlorination into amido complexes [M(NO)(CO)(PNP)] (M=Mo, 3a; W, 3b; PNP=(iPr2PCH2CH2)2N)). Compounds 3a and 3b have pseudo-trigonal-bipyramidal geometries, in which the amido nitrogen atom is in the equatorial plane. At room temperature, compounds 3a and 3b were capable of adding dihydrogen, with heterolytic splitting, thereby forming pairs of isomeric amine-hydride complexes [Mo(NO)(CO)H(PN(H)P)] (4a(cis) and 4a(trans)) and [W(NO)(CO)H(PN(H)P)] (4b(cis) and 4b(trans); cis and trans correspond to the position of the H and NO groups). H2 approaches the Mo/W=N bond in compounds 3a,b from either the CO-ligand side or from the NO-ligand side. Compounds 4a(cis) and 4a(trans) were only found to be stable under a H2 atmosphere and could not be isolated. At 140 °C and 60 bar H2 , compounds 3a and 3b catalyzed the hydrogenation of imines, thereby showing maximum turnover frequencies (TOFs) of 2912 and 1120 h(-1), respectively, for the hydrogenation of N-(4-methoxybenzylidene)aniline. A Hammett plot for various para-substituted imines revealed linear correlations with a negative slope of -3.69 for para substitution on the benzylidene side and a positive slope of 0.68 for para substitution on the aniline side. Kinetics analysis revealed the initial rate of the hydrogenation reactions to be first order in c(cat.) and zeroth order in c(imine). Deuterium kinetic isotope effect (DKIE) experiments furnished a low kH /kD value (1.28), which supported a Noyori-type metal-ligand bifunctional mechanism with H2 addition as the rate-limiting step. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Local environment around gold (III) in aqueous chloride solutions: An EXAFS spectroscopy study

NASA Astrophysics Data System (ADS)

Farges, Franã§Ois; Sharps, Julia A.; Brown, Gordon E., Jr.

1993-03-01

The local environment around Au (III) in aqueous solutions containing 1 M NaCl was determined as a function of pH and Au concentration using X-ray absorption spectroscopy (XAS) at ambient temperature and pressure. The solution Au concentrations studied were 10 - to 10 -3 M and the pH ranged between 2 and 9.2. No significant changes of Au speciation were detected with increasing Au concentration; however, major speciation changes were caused by variations in pH. At pH = 2, Au is coordinated by four Cl atoms ( mean d [AuCl] = 2.28 -2.29 ± 0.01 Å), whereas at pH 7.5 and 9.2, Au is coordinated by three Cl and one O (or OH) and by two Cl and two O (or OH), respectively ( mean d[AuCl] = 2.28 ± 0.02 Å; mean d[AuO or AuOH] = 1.97 ± 0.02 Å), indicating replacement of Cl by O (or OH) with increasing pH. In all solutions studied, the number of first-neighbors around Au(III) is close to four. XANES analysis suggests the presence of a square-planar geometry for AuX 4 ( X = Cl, O) at all pH values studied. These results are in excellent agreement with those from our previous Raman, resonance Raman, and UV/visible spectroscopy study of gold(III)-chloride solutions (PECK et al., 1991), which found that AuCl 4-, AuCl 3(OH) -, and AuCl 2(OH) 2- are the majority species in the pH ranges 2-6, 6-8.5, and 8.5-11, respectively. We did not find evidence for Au(I)Cl 2- or Au(I)Cl(OH) - complexes in our pH 7.5 and 9.2 solutions, as was recently suggested by PAN and WOOD (1991) for acidic gold chloride solutions at temperatures > 100°C, although we can't rule these complexes out as minority species (<10% of the total Au in solution). Our EXAFS results also provide the first direct evidence for Cl second neighbors around AuCl 4- complexes in the most acidic solutions studied ( pH = 2 and 4.5). These second-neighbor Cl atoms were also detected at low Au concentrations (10 -3 M) and are similar in number and arrangement to those observed in crystalline KAuCL 4·2H 2O (two Cl at a mean d[Au-Cl(2)] = 4.42 ± 0.03 Å). No evidence was found for second-neighbor Au atoms, which indicates little or no Au polymers or colloidal particles in any of the solutions studied. Our EXAFS results are in broad agreement with earlier predictions of Au speciation based on a variety of chemical measurements. Moreover, they directly confirm that mixed chloro-hydroxo Au (III) complexes are more stable than predicted on the basis of thermodynamically estimated stability constants.

Stability of numerous novel potassium chlorides at high pressure

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

Zhang, Weiwei; Oganov, Artem R.; Lobanov, Sergey S.

K-Cl is a simple system displaying all four main types of bonding, as it contains (i) metallic potassium, (ii) elemental chlorine made of covalently bonded Cl 2 molecules held together by van der Waals forces, and (iii) an archetypal ionic compound KCl. The charge balance rule, assigning classical charges of “+1” to K and “–1” to Cl, predicts that no compounds other than KCl are possible. However, our quantum-mechanical variable-composition evolutionary simulations predict an extremely complex phase diagram, with new thermodynamically stable compounds K 3Cl, K 2Cl, K 3Cl 2, K 4Cl 3, K 5Cl 4, K 3Cl 5, KClmore » 3 and KCl 7. Of particular interest are 2D-metallic homologs K n+1Cl n, the presence of positively charged Cl atoms in KCl 7, and the predicted stability of KCl 3 already at nearly ambient pressures at zero Kelvin. We have synthesized cubic Pm3¯n -KCl 3 at 40–70 GPa and trigonal P3¯cl -KCl 3 at 20–40 GPa in a laser-heated diamond anvil cell (DAC) at temperature exceeding 2000 K from KCl and Cl 2. These phases were identified using in situ synchrotron X-ray diffraction and Raman spectroscopy. Lastly, upon unloading to 10 GPa, P3¯cl -KCl 3 transforms to a yet unknown structure before final decomposition to KCl and Cl 2 at near-ambient conditions.« less

Stability of numerous novel potassium chlorides at high pressure

DOE PAGES

Zhang, Weiwei; Oganov, Artem R.; Lobanov, Sergey S.; ...

2016-05-23

K-Cl is a simple system displaying all four main types of bonding, as it contains (i) metallic potassium, (ii) elemental chlorine made of covalently bonded Cl 2 molecules held together by van der Waals forces, and (iii) an archetypal ionic compound KCl. The charge balance rule, assigning classical charges of “+1” to K and “–1” to Cl, predicts that no compounds other than KCl are possible. However, our quantum-mechanical variable-composition evolutionary simulations predict an extremely complex phase diagram, with new thermodynamically stable compounds K 3Cl, K 2Cl, K 3Cl 2, K 4Cl 3, K 5Cl 4, K 3Cl 5, KClmore » 3 and KCl 7. Of particular interest are 2D-metallic homologs K n+1Cl n, the presence of positively charged Cl atoms in KCl 7, and the predicted stability of KCl 3 already at nearly ambient pressures at zero Kelvin. We have synthesized cubic Pm3¯n -KCl 3 at 40–70 GPa and trigonal P3¯cl -KCl 3 at 20–40 GPa in a laser-heated diamond anvil cell (DAC) at temperature exceeding 2000 K from KCl and Cl 2. These phases were identified using in situ synchrotron X-ray diffraction and Raman spectroscopy. Lastly, upon unloading to 10 GPa, P3¯cl -KCl 3 transforms to a yet unknown structure before final decomposition to KCl and Cl 2 at near-ambient conditions.« less

Crystallographic investigations of select cathinones: emerging illicit street drugs known as `bath salts'.

PubMed

Wood, Matthew R; Lalancette, Roger A; Bernal, Ivan

2015-01-01

The name `bath salts', for an emerging class of synthetic cathinones, is derived from an attempt to evade prosecution and law enforcement. These are truly illicit drugs that have psychoactive CNS (central nervous system) stimulant effects and they have seen a rise in abuse as recreational drugs in the last few years since first having been seen in Japan in 2006. The ease of synthesis and modification of specific functional groups of the parent cathinone make these drugs particularly difficult to regulate. MDPV (3,4-methylenedioxypyrovalerone) is commonly encountered as its hydrochloride salt (C16H21NO3·HCl), in either the hydrated or the anhydrous forms. This `bath salt' has various names in the US, e.g. `Super Coke', `Cloud Nine', and `Ivory Wave', to name just a few. We report here the structures of two forms of the HCl salt, one as a mixed bromide/chloride salt, C16H22NO3(+)·0.343Br(-)·0.657Cl(-) [systematic name: 1-(benzo[d][1,3]dioxol-5-yl)-2-(pyrrolidin-1-ium-1-yl)pentan-1-one bromide/chloride (0.343/0.657)], and the other with the H7O3(+) cation, as well as the HCl counter-ion [systematic name: hydroxonium 1-(benzo[d][1,3]dioxol-5-yl)-2-(pyrrolidin-1-ium-1-yl)pentan-1-one dichloride, H7O3(+)·C16H22NO3(+)·2Cl(-)]. This is one of a very few structures (11 to be exact) in which we have a new example of a precisely determined hydroxonium cation. During the course of researching the clandestine manufacture of MDPV, we were surprised by the fact that a common precursor of this illicit stimulant is known to be the fragrant species piperonal, which is present in the fragrances of orchids, most particularly in the case of the vanilla orchid. We found that MDPV can be made by a Grignard reaction of this heliotropin. This may also explain the unexpected appearance of the bromide counter-ion in some of the salts we encountered (C16H21NO3·HBr), one of which is presented here [systematic name: 1-(benzo[d][1,3]dioxol-5-yl)-2-(pyrrolidin-1-ium-1-yl)pentan-1-one bromide, C16H22NO3(+)·Br(-)]. Complexation of MDPV with a forensic crystallizing reagent, HAuCl4, yields the tetrachloridoaurate salt of this drug, (C16H22NO3)[AuCl4]. The heavy-metal complexing agent HAuCl4 has been used for over a century to identify common quarternary nitrogen-containing drugs via microscopic identification. Another street drug, called ethylone (3,4-methylenedioxyethylcathinone), is regularly sold and abused as its hydrochloride salt (C12H15NO3·HCl), and its structure is herein described (systematic name: N-{1-[(benzo[d][1,3]dioxol-5-yl)carbonyl]ethyl}ethanaminium chloride, C12H16NO3(+)·Cl(-)). Marketed and sold as a `bath salt', `plant feeder', or `cleaning product', this drug is nothing more than a slight chemical modification of the banned drug methylone (3,4-methylenedioxymethcathinone). As with previously popular synthetic cathinones, the abuse of ethylone has seen a recent increase due to regulatory efforts on previous generations of cathinones that are now banned.

Resveratrol increases nitric oxide production in the rat thick ascending limb via Ca2+/calmodulin.

PubMed

Gonzalez-Vicente, Agustin; Cabral, Pablo D; Garvin, Jeffrey L

2014-01-01

The thick ascending limb of the loop of Henle reabsorbs 30% of the NaCl filtered through the glomerulus. Nitric oxide (NO) produced by NO synthase 3 (NOS3) inhibits NaCl absorption by this segment. Resveratrol, a polyphenol, has beneficial cardiovascular and renal effects, many of which are mediated by NO. Resveratrol increases intracellular Ca2+ (Cai) and AMP kinase (AMPK) and NAD-dependent deacetylase sirtuin1 (SIRT1) activities, all of which could activate NO production. We hypothesized that resveratrol stimulates NO production by thick ascending limbs via a Ca2+/calmodulin-dependent mechanism. To test this, the effect of resveratrol on NO bioavailability was measured in thick ascending limb suspensions. Cai was measured in single perfused thick ascending limbs. SIRT1 activity and expression were measured in thick ascending limb lysates. Resveratrol (100 µM) increased NO bioavailability in thick ascending limb suspensions by 1.3±0.2 AFU/mg/min (p<0.03). The NOS inhibitor L-NAME blunted resveratrol-stimulated NO bioavailability by 96±11% (p<0.03). The superoxide scavenger tempol had no effect. Resveratrol elevated Cai from 48±7 to 135±24 nM (p<0.01) in single tubules. In Ca2+-free media, the resveratrol-induced increase in NO was blunted by 60±20% (p<0.05) and the rise in Cai reduced by 80%. Calmodulin inhibition prevented the resveratrol-induced increase in NO (p<0.002). AMPK inhibition had no effect. Resveratrol did not increase SIRT1 activity. We conclude that resveratrol increases NO production in thick ascending limbs via a Ca2+/calmodulin dependent mechanism, and SIRT1 and AMPK do not participate. Resveratrol-stimulated NO production in thick ascending limbs may account for part of its beneficial effects.

Fractionation of Saprolegnia diclina (Oomycetes) satelite DNAs by AgNO3/Cs2SO4 density gradient centrifugation.

PubMed

Neish, G A; Green, B R

1977-12-14

Saprolegnia diclina DNA has been fractionated using preparative AgNO3/Cs2SO4 and CsCl density gradients. In addition to the previously identified major satellite DNA, there are two minor DNA components banding at 1.682 and 1.701 g - cm(-3) in CsCl. Purified major satellite DNA bands at 1.707 g - cm(-3) giving a base composition of 48% G + C in good agreement with 47% G + C calculated from its Tm value. The nuclear DNA base composition is 58% G + C by both methods. The base composition of the major satellite DNA suggests that it may represent ribosomal DNA cistrons.

1,3-Bis(chloro-meth-yl)-2-methyl-5-nitro-benzene.

PubMed

Shao, Chang-Lun; Li, Chunyuan; Liu, Zhen; Wei, Mei-Yan; Wang, Chang-Yun

2008-03-20

The title compound, C(9)H(9)Cl(2)NO(2), is a natural product isolated from the endophytic fungus No. B77 of the mangrove tree from the South China Sea coast. In the crystal structure, the mol-ecules lie on twofold axes and form offset stacks through face-to-face π-π inter-actions. Adjacent mol-ecules in each stack are related by a centre of inversion and have an inter-planar separation of 3.53 (1) Å, with a centroid-centroid distance of 3.76 (1) Å. Between stacks, there are C-H⋯O inter-actions to the nitro groups and Cl⋯Cl contacts of 3.462 (1) Å.

Effect of ammonium sulfate, ammonium chloride and root-zone acidity on inorganic ion content of tobacco

NASA Technical Reports Server (NTRS)

Vessey, J. K.; Raper, C. D. Jr; Henry, L. T.; Raper CD, J. r. (Principal Investigator)

1990-01-01

Tobacco plants (Nicotiana tabacum L. cv NC82) were supplied with (NH4)2SO4 or NH4Cl at root-zone pH of 6.0 and 4.5 in hydroponic culture for 28 days. Dry matter accumulation, total N and C content, and leaf area and number were not affected by the NH4+ source or root-zone pH. Plants supplied with NH4Cl accumulated up to 1.2 mM Cl g DW-1, but accumulated 37% less inorganic H2PO4- and 47% less SO4(2-) than plants supplied with (NH4)2SO4. The large Cl- accumulation resulted in NH4Cl- supplied plants having a 31% higher inorganic anion (NO3-, H2, PO4-, SO4(2-), and Cl-) charge. This higher inorganic anion charge in the NH4Cl-supplied plants was balanced by a similar increase in K+ charge. Plants supplied with NH4Cl accumulated greater concentrations of Cl- in leaves (up to 5.1% of DW) than plants supplied with (NH4)2SO4 (less than -% DW). Despite the high Cl- concentration of leaves in NH4Cl supplied plants, these plants showed no symptoms of Cl- toxicity. This demonstrates that toxicity symptoms are not due solely to an interaction between high Cl- concentration in tissue and NH4+ nutrition. The increase in root-zone acidity to pH 4.5 from 6.0 did not induce toxicity symptoms.

Properties of the anion-binding site of pharaonis Halorhodopsin studied by ultrafast pump-probe spectroscopy and low-temperature FTIR spectroscopy.

PubMed

Nakashima, Keisuke; Nakamura, Takumi; Takeuchi, Satoshi; Shibata, Mikihiro; Demura, Makoto; Tahara, Tahei; Kandori, Hideki

2009-06-18

Halorhodopsin (HR) is a light-driven chloride pump. Cl(-) is bound in the Schiff base region of the retinal chromophore, and unidirectional Cl(-) transport is probably enforced by the specific hydrogen-bonding interaction with the protonated Schiff base and internal water molecules. It is known that HR from Natronobacterium pharaonis (pHR) also pumps NO(3)(-) with similar efficiency, suggesting that NO(3)(-) binds to the Cl(-)-binding site. In the present study, we investigated the properties of the anion-binding site by means of ultrafast pump-probe spectroscopy and low-temperature FTIR spectroscopy. The obtained data were surprisingly similar between pHR-NO(3)(-) and pHR-Cl(-), even though the shapes and sizes of the two anions are quite different. Femtosecond pump-probe spectroscopy showed very similar excited-state dynamics between pHR-NO(3)(-) and pHR-Cl(-). Low-temperature FTIR spectroscopy of unlabeled and [zeta-(15)N]Lys-labeled pHR revealed almost identical hydrogen-bonding strengths of the protonated retinal Schiff base between pHR-NO(3)(-) and pHR-Cl(-), which is similarly strengthened after retinal isomerization. There were spectral variations for water stretching vibrations between pHR-NO(3)(-) and pHR-Cl(-), suggesting that the water molecules hydrate each anion. Nevertheless, the overall spectral features were similar for the two species. These observations strongly suggest that the anion-binding site has a flexible structure and that the interaction between retinal and the anions is weak, despite the presence of an electrostatic interaction. Such a flexible hydrogen-bonding network in the Schiff base region in HR appears to be in remarkable contrast to that in light-driven proton-pumping proteins.

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.

Radical pathway in catecholase activity with zinc-based model complexes of compartmental ligands.

PubMed

Guha, Averi; Chattopadhyay, Tanmay; Paul, Nanda Dulal; Mukherjee, Madhuparna; Goswami, Somen; Mondal, Tapan Kumar; Zangrando, Ennio; Das, Debasis

2012-08-20

Four dinuclear and three mononuclear Zn(II) complexes of phenol-based compartmental ligands (HL(1)-HL(7)) have been synthesized with the aim to investigate the viability of a radical pathway in catecholase activity. The complexes have been characterized by routine physicochemical studies as well as X-ray single-crystal structure analysis: [Zn(2)(H(2)L(1))(OH)(H(2)O)(NO(3))](NO(3))(3) (1), [Zn(2)L(2)Cl(3)] (2), [Zn(2)L(3)Cl(3)] (3), [Zn(2)(L(4))(2)(CH(3)COO)(2)] (4), [Zn(HL(5))Cl(2)] (5), [Zn(HL(6))Cl(2)] (6), and [Zn(HL(7))Cl(2)] (7) [L(1)-L(3) and L(5)-L(7) = 2,6-bis(R-iminomethyl)-4-methylphenolato, where R= N-ethylpiperazine for L(1), R = 2-(N-ethyl)pyridine for L(2), R = N-ethylpyrrolidine for L(3), R = N-methylbenzene for L(5), R = 2-(N-methyl)thiophene for L(6), R = 2-(N-ethyl)thiophene for L(7), and L(4) = 2-formyl-4-methyl-6-N-methylbenzene-iminomethyl-phenolato]. Catecholase-like activity of the complexes has been investigated in methanol medium by UV-vis spectrophotometric study using 3,5-di-tert-butylcatechol as model substrate. All complexes are highly active in catalyzing the aerobic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butylbenzoquinone (3,5-DTBQ). Conversion of 3,5-DTBC to 3,5-DTBQ catalyzed by mononuclear complexes (5-7) is observed to proceed via formation of two enzyme-substrate adducts, ES1 and ES2, detected spectroscopically, a finding reported for the first time in any Zn(II) complex catalyzed oxidation of catechol. On the other hand, no such enzyme-substrate adduct has been identified, and 3,5-DTBC to 3,5-DTBQ conversion is observed to be catalyzed by the dinuclear complexes (1-4) very smoothly. EPR experiment suggests generation of radicals in the presence of 3,5-DTBC, and that finding has been strengthened by cyclic voltammetric study. Thus, it may be proposed that the radical pathway is probably responsible for conversion of 3,5-DTBC to 3,5-DTBQ promoted by complexes of redox-innocent Zn(II) ion. The ligand-centered radical generation has further been verified by density functional theory calculation.

Chlorine gas exposure disrupts nitric oxide homeostasis in the pulmonary vasculature

PubMed Central

Honavar, Jaideep; Bradley, Eddie; Bradley, Kelley; Oh, Joo Yeun; Vallejo, Matthew O.; Kelley, Eric E.; Cantu-Medellin, Nadiezhda; Doran, Stephen; Dell’italia, Louis J.; Matalon, Sadis; Patel, Rakesh P.

2014-01-01

Exposure to chlorine (Cl2) gas during industrial accidents or chemical warfare leads to significant airway and distal lung epithelial injury that continues post exposure. While lung epithelial injury is prevalent, relatively little is known about whether Cl2 gas also promotes injury to the pulmonary vasculature. To determine this, rats were subjected to a sub-lethal Cl2 gas exposure (400ppm, 30min) and then brought back to room air. Pulmonary arteries (PA) were isolated from rats at various times post-exposure and contractile (phenylephrine) and nitric oxide (NO)-dependent vasodilation (acetylcholine and mahmanonoate) responses measured ex-vivo. PA contractility did not change, however significant inhibition of NO-dependent vasodilation was observed that was maximal at 24–48 hours post exposure. Superoxide dismutase restored NO-dependent vasodilation suggesting a role for increased superoxide formation. This was supported by ~2-fold increase in superoxide formation (measured using 2-hydroethidine oxidation to 2-OH-E+) from PA isolated from Cl2 exposed rats. We next measured PA pressures in anesthetized rats. Surprisingly, PA pressures were significantly (~4mmHg) lower in rats that had been exposed to Cl2 gas 24 hours earlier suggesting that deficit in NO-signaling observed in isolated PA experiments did not manifest as increased PA pressures in vivo. Administration of the iNOS selective inhibitor 1400W, restored PA pressures to normal in Cl2 exposed, but not control rats suggesting that any deficit in NO-signaling due to increased superoxide formation in the PA, is offset by increased NO-formation from iNOS. These data indicate that disruption of endogenous NO-signaling mechanisms that maintain PA tone is an important aspect of post-Cl2 gas exposure toxicity. PMID:24769334

Using vadose zone data and spatial statistics to assess the impact of cultivated land and dairy waste lagoons on groundwater contamination

NASA Astrophysics Data System (ADS)

Baram, S.; Ronen, Z.; Kurtzman, D.; Peeters, A.; Dahan, O.

2013-12-01

Land cultivation and dairy waste lagoons are considered to be nonpoint and point sources of groundwater contamination by chloride (Cl-) and nitrate (NO3-). The objective of this work is to introduce a methodology to assess the past and future impacts of such agricultural activities on regional groundwater quality. The method is based on mass balances and on spatial statistical analysis of Cl- and NO3-concentration distributions in the saturated and unsaturated zones. The method enables quantitative analysis of the relation between the locations of pollution point sources and the spatial variability in Cl- and NO3- concentrations in groundwater. The method was applied to the Beer-Tuvia region, Israel, where intensive dairy farming along with land cultivation has been practiced for over 50 years above the local phreatic aquifer. Mass balance calculations accounted for the various groundwater recharge and abstraction sources and sinks in the entire region. The mass balances showed that leachates from lagoons and the cultivated land have contributed 6.0 and 89.4 % of the total mass of Cl- added to the aquifer and 12.6 and 77.4 % of the total mass of NO3-. The chemical composition of the aquifer and vadose zone water suggested that irrigated agricultural activity in the region is the main contributor of Cl- and NO3- to the groundwater. A low spatial correlation between the Cl- and NO3- concentrations in the groundwater and the on-land location of the dairy farms strengthened this assumption, despite the dairy waste lagoon being a point source for groundwater contamination by Cl- and NO3-. Results demonstrate that analyzing vadose zone and groundwater data by spatial statistical analysis methods can significantly contribute to the understanding of the relations between groundwater contaminating sources, and to assessing appropriate remediation steps.

Development of a chlorine chemistry module for the Master Chemical Mechanism

NASA Astrophysics Data System (ADS)

Xue, L. K.; Saunders, S. M.; Wang, T.; Gao, R.; Wang, X. F.; Zhang, Q. Z.; Wang, W. X.

2015-06-01

The chlorine atom (Cl·) has a high potential to perturb atmospheric photochemistry by oxidizing volatile organic compounds (VOCs), but the exact role it plays in the polluted troposphere remains unclear. The Master Chemical Mechanism (MCM) is a near explicit mechanism that has been widely applied in the atmospheric chemistry research. While it addresses comprehensively the chemistry initiated by the OH, O3 and NO3 radicals, its representation of the Cl· chemistry is incomplete as it only considers the reactions for alkanes. In this paper, we develop a more comprehensive Cl· chemistry module that can be directly incorporated within the MCM framework. A suite of 199 chemical reactions describes the Cl·-initiated degradation of alkenes, aromatics, aldehydes, ketones, alcohols, and some organic acids and nitrates, along with the inorganic chemistry involving Cl· and its precursors. To demonstrate the potential influence of the new chemistry module, it was incorporated into a MCM box model to evaluate the impacts of nitryl chloride (ClNO2), a product of nocturnal halogen activation by nitrogen oxides (NOx), on the following-day's atmospheric photochemistry. With constraints of recent observations collected at a coastal site in Hong Kong, southern China, the modeling analyses suggest that the Cl· produced from ClNO2 photolysis may substantially enhance the atmospheric oxidative capacity, VOC oxidation, and O3 formation, particularly in the early morning period. The results demonstrate the critical need for photochemical models to include more fully chlorine chemistry in order to better understand the atmospheric photochemistry in polluted environments subject to intense emissions of NOx, VOCs and chlorine-containing constituents.

Development of a chlorine chemistry module for the Master Chemical Mechanism

NASA Astrophysics Data System (ADS)

Xue, L. K.; Saunders, S. M.; Wang, T.; Gao, R.; Wang, X. F.; Zhang, Q. Z.; Wang, W. X.

2015-10-01

The chlorine atom (Cl·) has a high potential to perturb atmospheric photochemistry by oxidizing volatile organic compounds (VOCs), but the exact role it plays in the polluted troposphere remains unclear. The Master Chemical Mechanism (MCM) is a near-explicit mechanism that has been widely applied in the atmospheric chemistry research. While it addresses comprehensively the chemistry initiated by the OH, O3 and NO3 radicals, its representation of the Cl· chemistry is incomplete as it only considers the reactions for alkanes. In this paper, we develop a more comprehensive Cl· chemistry module that can be directly incorporated within the MCM framework. A suite of 205 chemical reactions describes the Cl·-initiated degradation of alkenes, aromatics, alkynes, aldehydes, ketones, alcohols, and some organic acids and nitrates, along with the inorganic chemistry involving Cl· and its precursors. To demonstrate the potential influence of the new chemistry module, it was incorporated into a MCM box model to evaluate the impacts of nitryl chloride (ClNO2), a product of nocturnal halogen activation by nitrogen oxides (NOX), on the following day's atmospheric photochemistry. With constraints of recent observations collected at a coastal site in Hong Kong, southern China, the modeling analyses suggest that the Cl· produced from ClNO2 photolysis may substantially enhance the atmospheric oxidative capacity, VOC oxidation and O3 formation, particularly in the early morning period. The results demonstrate the critical need for photochemical models to include more detailed chlorine chemistry in order to better understand the atmospheric photochemistry in polluted environments subject to intense emissions of NOX, VOCs and chlorine-containing constituents.

Copper(I), silver(I) and gold(I) halide complexes with the dithioformamidinium dihalides

NASA Astrophysics Data System (ADS)

Peyronel, Giorgio; Malavasi, Wanda; Pignedoli, Anna

Some copper(I), silver(I) and gold(I) halide complexes with the dithioformamidinium dihalides (Tu 2X 2) were prepared and studied by infrared spectroscopy and conductometry: 3CuX.2Tu 2X 2(XCl,I), CuBr.Tu 2Br 2, 4CuBr.3.5Tu 2Br 2.MeOH, 2CuBr.Tu 2Br 2.0.66EtOH, 3CuI.2Tu 2I 2, 2AgCl.2.5Tu 2Cl 2, 3AgCl.2Tu 2Cl 2.0.5EtOH, 3AgCl.Tu 2Cl 2, 2AgBr.2Tu 2Br 2.0.5Tu 2(NO 3) 2.H 2O, AgBr.Tu 2Br 2, 4AgBr.Tu 2Br 2, 4AgI.0.5Tu 2I 2.EtOH, AuCl.1.5Tu 2Cl 2, 4AuCl.3.5Tu 2Cl 2.2DMF, AuBr.4Tu 2Br 2, AuBr.2Tu 2Br 2.1.5DMF, AuI.5Tu 2I 2, AuI.Tu 2I 2. A decrease of the ν(NH), δ(NH 2) and ν(CN 2) frequencies and an increase of the ν(CS) frequencies indicate an N-coordination of the dithioformamidinium cation to the metal ions; ν(MN) and ν(MX) frequencies are tentatively assigned in the far-infrared spectra.

Atmospheric oxidation of selected chlorinated alkenes by O3, OH, NO3 and Cl

NASA Astrophysics Data System (ADS)

Zhang, Qun; Chen, Yi; Tong, Shengrui; Ge, Maofa; Shenolikar, Justin; Johnson, Matthew S.; Wang, Yifeng; Tsona, Narcisse T.; Mellouki, Abdelwahid; Du, Lin

2017-12-01

An experimental study on the 3-chloro-2-methyl-1-propene (CMP), 2,3-dichloropropene (DCP) and 3,4-dichlorobutene (DCB) reactions with atmospheric oxidants at (298 ± 1) K and atmospheric pressure is reported. Rate constants for the gas phase reactions of the three chlorinated alkenes with O3, OH and NO3 radicals and Cl atom were determined in a 100 L Teflon reactor by gas chromatography with flame ionization detector (GC-FID). The obtained rate constants are (3.03 ± 0.15) × 10-18, (3.83 ± 1.30) × 10-11, (1.99 ± 0.19) × 10-14, and (2.40 ± 0.41) × 10-10 cm3 molecule-1 s-1 for CMP reactions with O3, OH, NO3, and Cl, respectively, (4.62 ± 1.41) × 10-20, (1.37 ± 1.02) × 10-11, (1.45 ± 0.15) × 10-15 and (1.30 ± 0.99) × 10-11 cm3 molecule-1 s-1 for DCP reactions and (2.09 ± 0.24) × 10-19, (1.45 ± 0.59) × 10-11, (3.00 ± 0.82) × 10-16 and (1.91 ± 0.19) × 10-10 cm3 molecule-1 s-1 for DCB reactions. The CMP reaction products were detected and possible reaction mechanisms of their formation were proposed. Chloroacetone was found to be the major product in all four oxidation reactions. The loss process of CMP in the atmosphere is mostly controlled by its reaction with the OH radical during daytime and with NO3 during nighttime, with lifetimes of 3.6 h and 27.9 h respectively. Atmospheric implications of both these reactions and their potential products are discussed.

The inorganic speciation of tin(II) in aqueous solution

NASA Astrophysics Data System (ADS)

Cigala, Rosalia Maria; Crea, Francesco; De Stefano, Concetta; Lando, Gabriele; Milea, Demetrio; Sammartano, Silvio

2012-06-01

This paper reports new voltammetric measurements on the interactions between tin(II) and the most important natural inorganic ligands, OH-, Cl-, F-, CO32-, SO42- and PO43-. For a better understanding of tin(II) speciation, an analysis is also given of prior data on the same systems from the literature. The formation constants were determined at t = 25 °C in different ionic media and at different ionic strengths, specifically the following: Sn(OH)q (0.1 ⩽ I/mol L-1 ⩽ 1.0 in NaNO3), SnClr and Sn(OH)Cl (0.1 ⩽ I/mol L-1 ⩽ 2.3 in Na(NO3, Cl)), Sn(SO4)r (0.1 ⩽ I/mol L-1 ⩽ 1.6 in Na(NO3, SO4)), SnHqCO3 and SnHqPO4 (0.15 ⩽ I/mol L-1 ⩽ 1.0 in NaNO3), where the subscripts r and q represent the stoichiometric coefficients. Concerning the SnFr species, reliable literature values were considered (0.15 ⩽ I/mol L-1 ⩽ 1.0 in NaClO4). Fifteen voltammetric measurements were performed in synthetic seawater; the total seawater binding ability was evaluated by a model in which synthetic seawater is expressed as a single salt, BA. The formation of species between tin(II) and the anion of the marine salt (A) was also proposed, and the corresponding stability constants at different salinities (5 ⩽ S ⩽ 50) were reported. In addition, studies on the solubility of Sn(OH)2(s) were carried out using voltammetry and light scattering measurements. The "extra-stability" of the mixed species with respect to the parent species was evaluated, in particular for Sn(OH)Cl and the corresponding species involving the anion of the marine salt (A). The dependence of the formation constants on ionic strength was analysed using extended Debye-Hückel and Specific ion Interaction Theory (SIT) type equations. Tin(II) speciation was also evaluated in different natural fluid conditions, where, in all cases, carbonate complexation was predominant, hampering the formation of hydrolytic species throughout the investigated pH range. Moreover, some formation enthalpy changes were calculated for the Sn(OH)+, Sn(OH)2(aq), Sn(OH)2(s), Sn(OH)3-, Sn(OH)22+, Sn(OH)42+, Sn(OH)Cl, SnCl+, SnCl2 and SnCl3- species on the basis of the available literature stability constant values at different temperatures and using the empirical relationships reported in the literature. The ΔH values at t = 25 °C were positive in all cases except for the Sn(OH)2(s) and Sn(OH)3- species, indicating an increase in the stability constant values with increasing temperature. This work represents an advance in the knowledge, understanding and modelling of the inorganic speciation of tin(II) in natural fluids, particularly for solutions containing chloride, fluoride, sulphate, carbonate and phosphate anions.

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

Kim, S.; Sorescu, D.C.; Yates, J., Jr.

The effect of triethylenediamine (TEDA) (also named 1,4-diazabicyclo [2.2.2]octane, DABCO) on the adsorption of ClCN on a y-Al2O3 absorbent has been investigated. Both Fourier transform infrared (FTIR) and theoretical studies indicate that no direct interaction between amine groups of TEDA and ClCN molecules takes place. Instead, we found that TEDA competes with ClCN for active surface sites on y-Al2O3. In addition, the adsorption behavior of cyanogen chloride (ClCN) on a clean y-Al2O3 surface has been studied. The sequence of the thermally activated processes of diffusion, adsorption, desorption, and decomposition of ClCN molecules on the clean y-Al2O3 surface following icelike ClCNmore » layer formation at lower temperature was observed. One of the decomposition products, Al-NCO, was assigned by using an Al-18OH labeled surface for reaction with ClCN. In addition, Al-CN and Al2-OCN species were also detected upon ClCN decomposition. Good correlation of the calculated vibrational frequencies for the adsorbed species with experimental data is found.« less

High-Altitude Aircraft and Balloon-Borne Observations of OH, HO2, ClO, BrO, NO2, ClONO2, ClOOCl, H2O, and O3 in Earth's Stratosphere

NASA Technical Reports Server (NTRS)

Anderson, James G.

1999-01-01

Using observations from balloon-borne instruments and aircraft-borne instruments the investigation arrived at the following developments.: (1) Determination of the dominant catalytic cycles that destroy ozone in the lower stratosphere; (2) The partial derivatives of the rate limiting steps are observables in the lower stratosphere; (3) Recognition that the "Low NOx" condition is the regime that holds the greatest potential for misjudgement of Ozone loss rates; (4) Mapping of the Bromine radical contribution to the ozone destruction rate in the lower stratosphere; (5) Observation of OH, HO2 and ClO in the plume of the Concorde SST in the stratosphere; (6) Determination of the diurnal behavior of OH in the lower stratosphere; (7) Observed OH and H02 in the Troposphere and the interrelationship between Ozone and OH, HO2, CO and NO; (8) Analysis of the Catalytic Production of Ozone and Reactions that Couple OH and H02 in the Troposphere; (9) The continuing development of the understanding of the Tropopause temperatures, water vapor mixing ratios, and vertical advection and the mixing in of mid-latitude air; (10) Performed Multiple Tracer Analyses as a diagnostic of water vapor intrusion into the "Middle World" (i.e., the lowermost stratsophere); (11) Flight testing of a new instrument for the In Situ detection of ClON02 from the ER-2; (12) Laser induced fluorescence detection of NO2. There is included an in depth discussion of each of these developments and observations.

Stability of numerous novel potassium chlorides at high pressure

NASA Astrophysics Data System (ADS)

Zhang, Weiwei; Oganov, Artem R.; Zhu, Qiang; Lobanov, Sergey S.; Stavrou, Elissaios; Goncharov, Alexander F.

2016-05-01

K-Cl is a simple system displaying all four main types of bonding, as it contains (i) metallic potassium, (ii) elemental chlorine made of covalently bonded Cl2 molecules held together by van der Waals forces, and (iii) an archetypal ionic compound KCl. The charge balance rule, assigning classical charges of “+1” to K and “-1” to Cl, predicts that no compounds other than KCl are possible. However, our quantum-mechanical variable-composition evolutionary simulations predict an extremely complex phase diagram, with new thermodynamically stable compounds K3Cl, K2Cl, K3Cl2, K4Cl3, K5Cl4, K3Cl5, KCl3 and KCl7. Of particular interest are 2D-metallic homologs Kn+1Cln, the presence of positively charged Cl atoms in KCl7, and the predicted stability of KCl3 already at nearly ambient pressures at zero Kelvin. We have synthesized cubic -KCl3 at 40-70 GPa and trigonal -KCl3 at 20-40 GPa in a laser-heated diamond anvil cell (DAC) at temperature exceeding 2000 K from KCl and Cl2. These phases were identified using in situ synchrotron X-ray diffraction and Raman spectroscopy. Upon unloading to 10 GPa, -KCl3 transforms to a yet unknown structure before final decomposition to KCl and Cl2 at near-ambient conditions.

Effects of metal salt catalysts on yeast cell growth in ethanol conversion

Treesearch

Chung-Yun Hse; Yin Lin

2009-01-01

The effects of the addition of metal salts and metal salt-catalyzed hydrolyzates on yeast cell growth in ethanol fermentation were investigated. Four yeast strains (Saccharomyces cerevisiae WT1, Saccharomyces cerevisiae MT81, Candida sp. 1779, and Klumaromyces fragilis), four metal salts (CuCl2, FeCl3, AgNO3, and I2), two metal salt-catalyzed hydrolyzates (...

New RuII pincer complexes: synthesis, characterization and biological evaluation for photodynamic therapy.

PubMed

Tabrizi, Leila; Chiniforoshan, Hossein

2016-11-15

Three new ruthenium(ii) complexes of NCN pincer and phenylcyanamide derivative ligands of the formula [Ru(L)(Ph 2 phen)(3,5-(NO 2 ) 2 pcyd)], 1, [Ru(L)(Me 2 phen)(3,5-(NO 2 ) 2 pcyd)], 2, and [Ru(L)(Cl 2 phen)(3,5-(NO 2 ) 2 pcyd)], 3 (HL: 5-methoxy-1,3-bis(1-methyl-1H-benzo[d]imidazol-2-yl)benzene, 3,5-(NO 2 ) 2 pcyd: 3,5-(NO 2 ) 2 pcyd, Ph 2 phen: 4,7-diphenyl-1,10-phenanthroline, Me 2 phen: 4,7-dimethyl-1,10-phenanthroline, Cl 2 phen: 4,7-dichloro-1,10-phenanthroline) have been synthesized and studied as potential photosensitizers (PSs) in photodynamic therapy (PDT). The complexes exhibited promising 1 O 2 production quantum yields comparable with PSs available on the market. The DNA-binding interactions of the complexes with calf thymus DNA have been studied by absorption, emission, and viscosity measurements. All complexes cleave SC-DNA efficiently on photoactivation at 350 nm with the formation of singlet oxygen ( 1 O 2 ) and hydroxyl radicals (˙OH) in type-II and photoredox pathways. Complexes 1-3 showed very good uptake in cervical cancer cells (HeLa). The compounds studied were found to exhibit low toxicity against HeLa cells (IC 50 > 300 μM) and, remarkably, on non-cancerous MRC-5 cells (IC 50 > 100 μM) in the dark. However, 1 showed very promising behavior with an increment of about 90 times, in its cytotoxicity upon light illumination at 420 nm in addition to very good human plasma stability.

Reconfigurable Flight Control System for a STOL (Short Take-Off and Landing) Aircraft Using Quantitative Feedback Theory.

DTIC Science & Technology

1984-12-01

XD2, XD3, XD4, XD5, XD6, XD7, XDS, 7M1, MA, MH, M0,MU, MDl,MD2, MD3, MD4, M5, MOS, MD7, MDS REAL CNB, CYB, CL, L, N DIMENSION AMAT(4,4), BMAT (4,S...NO, MU, ND1, MD2, ND3, MD4,ND5, MD6, ND7, NO REAL CNB, CYB, CL, L, N DIMENSION AMAT(4,4), BMAT (4,S)V DIMENSION DIRMAT(5, 5) ,DIRBMAT(5, SJ CHARACTER*3...INPUT MATRIX 8 C BMAT (l,1) - XO1 BMAT (1,2) - X02 BMAT (1,3) = XD3 BMAT (1,4) -XO4 SMAT(1,5) -XD5 BMAT (1,&) - XDG BMQT(1,7) = XD7 EMAT(I,8) - XDB BMAT (,1

Analysis of the structure and the FT-IR and Raman spectra of 2-(4-nitrophenyl)-4H-3,1-benzoxazin-4-one. Comparisons with the chlorinated and methylated derivatives

NASA Astrophysics Data System (ADS)

Castillo, María V.; Rudyk, Roxana A.; Davies, Lilian; Brandán, Silvia Antonia

2017-07-01

In this work, the structural, topological and vibrational properties of the monomer and three dimers of the 2-(4-nitrophenyl)-4H-3,1-benzoxazin-4-one (NPB) derivative were studied combining the experimental FTIR and FT-Raman spectra in the solid phase with DFT calculations. Here, Natural Bond Orbital (NBO), Atoms in Molecules (AIM) and HOMO and LUMO calculations were performed by using the hybrid B3LYP/6-31G*and B3LYP/6-311++G** methods in order to compute those properties and to predict their reactivities. The comparisons with the properties reported for the chlorinated (Cl-PB) and methylated (CH3-PB) derivatives at the same levels of theory can be clearly justified by the activating (CH3) and deactivating (NO2 and Cl) characteristics of the different groups linked to oxaxin rings. The NBO and AIM studies evidence the following stability orders: Cl-PB > NO2-PB > CH3-PB in very good concordance with the f(νC23-X26) force constants values. The frontier orbitals analyses reveal that the Cl-PB and NO2-PB derivatives have good stabilities and high chemical hardness while CH3-PB has a higher chemical reactivity. On the other hand, the complete vibrational assignments for monomer and dimers species of NPB were presented. The presence of the IR bands at 1574 and 1037 cm-1 and, of the Raman bands at 1571 and 1038 cm-1 support clearly the presence of the different dimeric species proposed for NPB.

D-region ion-neutral coupled chemistry (Sodankylä Ion Chemistry, SIC) within the Whole Atmosphere Community Climate Model (WACCM 4) - WACCM-SIC and WACCM-rSIC

NASA Astrophysics Data System (ADS)

Kovács, Tamás; Plane, John M. C.; Feng, Wuhu; Nagy, Tibor; Chipperfield, Martyn P.; Verronen, Pekka T.; Andersson, Monika E.; Newnham, David A.; Clilverd, Mark A.; Marsh, Daniel R.

2016-09-01

This study presents a new ion-neutral chemical model coupled into the Whole Atmosphere Community Climate Model (WACCM). The ionospheric D-region (altitudes ˜ 50-90 km) chemistry is based on the Sodankylä Ion Chemistry (SIC) model, a one-dimensional model containing 307 ion-neutral and ion recombination, 16 photodissociation and 7 photoionization reactions of neutral species, positive and negative ions, and electrons. The SIC mechanism was reduced using the simulation error minimization connectivity method (SEM-CM) to produce a reaction scheme of 181 ion-molecule reactions of 181 ion-molecule reactions of 27 positive and 18 negative ions. This scheme describes the concentration profiles at altitudes between 20 km and 120 km of a set of major neutral species (HNO3, O3, H2O2, NO, NO2, HO2, OH, N2O5) and ions (O2+, O4+, NO+, NO+(H2O), O2+(H2O), H+(H2O), H+(H2O)2, H+(H2O)3, H+(H2O)4, O3-, NO2-, O-, O2, OH-, O2-(H2O), O2-(H2O)2, O4-, CO3-, CO3-(H2O), CO4-, HCO3-, NO2-, NO3-, NO3-(H2O), NO3-(H2O)2, NO3-(HNO3), NO3-(HNO3)2, Cl-, ClO-), which agree with the full SIC mechanism within a 5 % tolerance. Four 3-D model simulations were then performed, using the impact of the January 2005 solar proton event (SPE) on D-region HOx and NOx chemistry as a test case of four different model versions: the standard WACCM (no negative ions and a very limited set of positive ions); WACCM-SIC (standard WACCM with the full SIC chemistry of positive and negative ions); WACCM-D (standard WACCM with a heuristic reduction of the SIC chemistry, recently used to examine HNO3 formation following an SPE); and WACCM-rSIC (standard WACCM with a reduction of SIC chemistry using the SEM-CM method). The standard WACCM misses the HNO3 enhancement during the SPE, while the full and reduced model versions predict significant NOx, HOx and HNO3 enhancements in the mesosphere during solar proton events. The SEM-CM reduction also identifies the important ion-molecule reactions that affect the partitioning of odd nitrogen (NOx), odd hydrogen (HOx) and O3 in the stratosphere and mesosphere.

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride

PubMed Central

Raff, Jonathan D.; Njegic, Bosiljka; Chang, Wayne L.; Gordon, Mark S.; Dabdub, Donald; Gerber, R. Benny; Finlayson-Pitts, Barbara J.

2009-01-01

Gaseous HCl generated from a variety of sources is ubiquitous in both outdoor and indoor air. Oxides of nitrogen (NOy) are also globally distributed, because NO formed in combustion processes is oxidized to NO2, HNO3, N2O5 and a variety of other nitrogen oxides during transport. Deposition of HCl and NOy onto surfaces is commonly regarded as providing permanent removal mechanisms. However, we show here a new surface-mediated coupling of nitrogen oxide and halogen activation cycles in which uptake of gaseous NO2 or N2O5 on solid substrates generates adsorbed intermediates that react with HCl to generate gaseous nitrosyl chloride (ClNO) and nitryl chloride (ClNO2), respectively. These are potentially harmful gases that photolyze to form highly reactive chlorine atoms. The reactions are shown both experimentally and theoretically to be enhanced by water, a surprising result given the availability of competing hydrolysis reaction pathways. Airshed modeling incorporating HCl generated from sea salt shows that in coastal urban regions, this heterogeneous chemistry increases surface-level ozone, a criteria air pollutant, greenhouse gas and source of atmospheric oxidants. In addition, it may contribute to recently measured high levels of ClNO2 in the polluted coastal marine boundary layer. This work also suggests the potential for chlorine atom chemistry to occur indoors where significant concentrations of oxides of nitrogen and HCl coexist. PMID:19620710

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

Using Rising Limb Analysis to Estimate Uptake of Reactive Solutes in Advective and Transient Storage Sub-compartments of Stream Ecosystems

NASA Astrophysics Data System (ADS)

Thomas, S. A.; Valett, H.; Webster, J. R.; Mulholland, P. J.; Dahm, C. N.

2001-12-01

Identifying the locations and controls governing solute uptake is a recent area of focus in studies of stream biogeochemistry. We introduce a technique, rising limb analysis (RLA), to estimate areal nitrate uptake in the advective and transient storage (TS) zones of streams. RLA is an inverse approach that combines nutrient spiraling and transient storage modeling to calculate total uptake of reactive solutes and the fraction of uptake occurring within the advective sub-compartment of streams. The contribution of the transient storage zones to solute loss is determined by difference. Twelve-hour coinjections of conservative (Cl-) and reactive (15NO3) tracers were conducted seasonally in several headwater streams among which AS/A ranged from 0.01 - 2.0. TS characteristics were determined using an advection-dispersion model modified to include hydrologic exchange with a transient storage compartment. Whole-system uptake was determined by fitting the longitudinal pattern of NO3 to first-order, exponential decay model. Uptake in the advective sub-compartment was determined by collecting a temporal sequence of samples from a single location beginning with the arrival of the solute front and concluding with the onset of plateau conditions (i.e. the rising limb). Across the rising limb, 15NO3:Cl was regressed against the percentage of water that had resided in the transient storage zone (calculated from the TS modeling). The y-intercept thus provides an estimate of the plateau 15NO3:Cl ratio in the absence of NO3 uptake within the transient storage zone. Algebraic expressions were used to calculate the percentage of NO3 uptake occurring in the advective and transient storage sub-compartments. Application of RLA successfully estimated uptake coefficients for NO3 in the subsurface when the physical dimensions of that habitat were substantial (AS/A > 0.2) and when plateau conditions at the sampling location consisted of waters in which at least 25% had resided in the transient storage zone. In those cases, the TS zone accounted for 8 - 47 % of overall NO3 uptake and uptake rates within the subsurface ranged from 0.7 - 14.3 mg N m-2 d-1.

Stabilization of molten salt materials using metal chlorides for solar thermal storage.

PubMed

Dunlop, T O; Jarvis, D J; Voice, W E; Sullivan, J H

2018-05-29

The effect of a variety of metal-chlorides additions on the melting behavior and thermal stability of commercially available salts was investigated. Ternary salts comprised of KNO 3, NaNO 2, and NaNO 3 were produced with additions of a variety of chlorides (KCl, LiCl, CaCl 2 , ZnCl 2 , NaCl and MgCl 2 ). Thermogravimetric analysis and weight loss experiments showed that the quaternary salt containing a 5 wt% addition of LiCl and KCl led to an increase in short term thermal stability compared to the ternary control salts. These additions allowed the salts to remain stable up to a temperature of 630 °C. Long term weight loss experiments showed an upper stability increase of 50 °C. A 5 wt% LiCl addition resulted in a weight loss of only 25% after 30 hours in comparison to a 61% loss for control ternary salts. Calorimetry showed that LiCl additions allow partial melting at 80 °C, in comparison to the 142 °C of ternary salts. This drop in melting point, combined with increased stability, provided a molten working range increase of almost 100 °C in total, in comparison to the control ternary salts. XRD analysis showed the oxidation effect of decomposing salts and the additional phase created with LiCl additions to allow melting point changes to occur.

Observations of Dinitrogen Pentoxide and Nitryl Chloride at two inland sites in North China: Abundances, Origins, and Impact on Photochemistry

NASA Astrophysics Data System (ADS)

LI, Q.; Xue, L.; Tham, Y. J.; Wang, W.; Yun, H.; Wang, T.; Wang, Z.; Wang, X.; Zhang, L.; Yao, L.; Wen, L.; Lu, K.; Zhang, Y.; Wang, W.

2015-12-01

Dinitrogen pentoxide (N2O5) and nitryl chloride (ClNO2) are key players in the nocturnal tropospheric chemistry, and also have potential to perturb the next-day's photochemistry. We here present the first ambient measurements of N2O5 and ClNO2 in inland regions of northern China, which is suffering from severe photochemical smog and haze pollution. A chemical ionization mass spectrometer (CIMS) was deployed at a semi-rural site in Wangdu, Hebei and on the top of Mt Tai, Shandong (1500 m a.s.l.) during the summer of 2014. At Wangdu, significant levels of ClNO2 were observed persistently throughout the campaign, with the maximum concentration of up to 2.1 ppbv (1-min data). N2O5 were generally in small concentrations but on few occasions reached up to hundreds of pptv. Clear variation of ClNO2 and N2O5 from night to night suggests the variability of N2O5 heterogeneous reactivity under different conditions over the region. On the mountain-top, elevated ClNO2-laden plumes were frequently observed around mid-night with a 1-min maximum of 2.1 ppbv, whilst N2O5 was always in very low levels indicating a fast N2O5 hydrolysis. The elevated ClNO2 levels at both locations were significantly influenced by the high NOx-saturated urban plumes and non-oceanic sources of chloride like biomass burning and coal-fired power plants in the region. MCM (Master Chemical Mechanism) modeling analyses indicate the significance of ClNO2 photolysis to the daytime radical and ozone production. Our study implies that the N2O5 reactivity and chlorine activation are significant in North China, and should be also important in other non-marine regions of China where NOx and particle chloride are in great abundances.

Crystal structure, quantum mechanical investigation, IR and NMR spectroscopy of two new organic salts: (C8H12NO)·[NO3] (I) and (C8H14N4)·[ClO4]2 (II)

NASA Astrophysics Data System (ADS)

Bayar, I.; Khedhiri, L.; Soudani, S.; Lefebvre, F.; Pereira da Silva, P. S.; Ben Nasr, C.

2018-06-01

Two new organic-inorganic hybrid materials, 4-methoxybenzylammonium nitrate, (C8H12NO)·[NO3] (I), and 2-(1-piperazinyl)pyrimidinium bis(perchlorate), (C8H14N4)·[ClO4]2(II), have been synthesized by an acid/base reaction at room temperature, their structures were determined by single crystal X-ray diffraction. Compound (I) crystallizes in the orthorhombic system and Pnma space group with a = 15.7908 (7), b = 6.8032 (3), c = 8.7091 (4) Å, V = 935.60 (7) Å3 with Z = 4. Full-matrix least-squares refinement converged at R = 0.038 and wR(F2) = 0.115. Compound (II) belongs to the monoclinic system, space group P21/c with the following parameters: a = 10.798(2), b = 7.330(1), c = 21.186(2) Å, β = 120.641 (4)°, V = 1442.7 (3) Å3and Z = 4. The structure was refined to R = 0.044, wR(F2) = 0.132. In the structures of (I) and (II), the anionic and cationic entities are interconnected by hydrogen bonding contacts forming three-dimensional networks. Intermolecular interactions were investigated by Hirshfeld surfaces and the contacts of the four different chloride atoms in (II) were compared. The Molecular Electrostatic Potential (MEP) maps and the HOMO and LUMO energy gaps of both compounds were computed. The vibrational absorption bands were identified by infrared spectroscopy. These compounds were also investigated by solid-state 13C, 35Cl and 15N NMR spectroscopy. DFT calculations allowed the attribution of the IR and NMR bands.

Water Evaporation from Acoustically Levitated Aqueous Solution Droplets.

PubMed

Combe, Nicole A; Donaldson, D James

2017-09-28

We present a systematic study of the effect of solutes on the evaporation rate of acoustically levitated aqueous solution droplets by suspending individual droplets in a zero-relative humidity environment and measuring their size as a function of time. The ratios of the early time evaporation rates of six simple salts (NaCl, NaBr, NaNO 3 , KCl, MgCl 2 , CaCl 2 ) and malonic acid to that of water are in excellent agreement with predictions made by modifying the Maxwell equation to include the time-dependent water activity of the evaporating aqueous salt solution droplets. However, the early time evaporation rates of three ammonium salt solutions (NH 4 Cl, NH 4 NO 3 , (NH 4 ) 2 SO 4 ) are not significantly different from the evaporation rate of pure water. This finding is in accord with a previous report that ammonium sulfate does not depress the evaporation rate of its solutions, despite reducing its water vapor pressure, perhaps due to specific surface effects. At longer evaporation times, as the droplets approach crystallization, all but one (MgCl 2 ) of the solution evaporation rates are well described by the modified Maxwell equation.

Carbon Monoxide-releasing Molecule-3 (CORM-3; Ru(CO)3Cl(Glycinate)) as a Tool to Study the Concerted Effects of Carbon Monoxide and Nitric Oxide on Bacterial Flavohemoglobin Hmp

PubMed Central

Tinajero-Trejo, Mariana; Denby, Katie J.; Sedelnikova, Svetlana E.; Hassoubah, Shahira A.; Mann, Brian E.; Poole, Robert K.

2014-01-01

CO and NO are small toxic gaseous molecules that play pivotal roles in biology as gasotransmitters. During bacterial infection, NO, produced by the host via the inducible NO synthase, exerts critical antibacterial effects while CO, generated by heme oxygenases, enhances phagocytosis of macrophages. In Escherichia coli, other bacteria and fungi, the flavohemoglobin Hmp is the most important detoxification mechanism converting NO and O2 to the ion nitrate (NO3−). The protoheme of Hmp binds not only O2 and NO, but also CO so that this ligand is expected to be an inhibitor of NO detoxification in vivo and in vitro. CORM-3 (Ru(CO)3Cl(glycinate)) is a metal carbonyl compound extensively used and recently shown to have potent antibacterial properties. In this study, attenuation of the NO resistance of E. coli by CORM-3 is demonstrated in vivo. However, polarographic measurements showed that CO gas, but not CORM-3, produced inhibition of the NO detoxification activity of Hmp in vitro. Nevertheless, CO release from CORM-3 in the presence of soluble cellular compounds is demonstrated by formation of carboxy-Hmp. We show that the inability of CORM-3 to inhibit the activity of purified Hmp is due to slow release of CO in protein solutions alone i.e. when sodium dithionite, widely used in previous studies of CO release from CORM-3, is excluded. Finally, we measure intracellular CO released from CORM-3 by following the formation of carboxy-Hmp in respiring cells. CORM-3 is a tool to explore the concerted effects of CO and NO in vivo. PMID:25193663

Synthesis and structural features of U VI and V IV chelate complexes with (hhmmbH)Cl·H 2O [hhmmb = {3-hydroxyl-5-(hydroxymethyl)-2-methylpyridine-4-yl-methylene}benzohydrazide], a new Schiff base ligand derived from vitamin B6

NASA Astrophysics Data System (ADS)

Back, Davi Fernando; Ballin, Marco Aurélio; de Oliveira, Gelson Manzoni

2009-10-01

The Schiff base ligand {3-hydroxyl-5-(hydroxymethyl)-2-methylpyridine-4-yl-methylene}benzohydrazide hydrochloride monohydrated {(hhmmbH)Cl·H 2O} ( 1) was prepared by reaction of pyridoxine hydrochloride with benzoic acid hydrazide. The reaction of 1 with [VO(acac) 2] and triethylamine yields the neutral vanadium IV complex [VO 2(hhmmb)]·Py ( 2), with a distorted quadratic pyramidal configuration. The Schiff base 1 reacts also with UO 2(NO 3) 2·6H 2O and triethylamine under deprotonation giving the uranium VI cationic complexes [UO 2(hhmmb)(H 2O)Cl] + ( 3) and [UO 2(hhmmb)(CH 3OH)Cl] + ( 4), both showing the classical pentagonal bipyrimidal geometry of UO22+ complexes. The structural features of all compounds are discussed.

Cd(II) and Zn(II) complexes of two new hexadentate Schiff base ligands derived from different aldehydes and ethanol amine; X-ray crystal structure, IR and NMR spectroscopy studies

NASA Astrophysics Data System (ADS)

Golbedaghi, Reza; Rezaeivala, Majid; Albeheshti, Leila

2014-11-01

Four new [Cd(H2L1)(NO3)]ClO4 (1), [Zn(H2L1)](ClO4)2 (2), [Cd(H2L2)(NO3)]ClO4 (3), and [Zn(H2L2)](ClO4)2 (4), complexes were prepared by the reaction of two new Schiff base ligands and Cd(II) and Zn(II) metal ions in equimolar ratios. The ligands H2L1 and H2L2 were synthesized by reaction of 2-[2-(2-formyl phenoxy)ethoxy]benzaldehyde and/or 2-[2-(3-formyl phenoxy)propoxy]benzaldehyde and ethanol amine and characterized by IR, 1H and 13C NMR spectroscopy. All complexes were characterized by IR, 1H and 13C NMR, COSY, and elemental analysis. Also, the complex 1 was characterized by X-ray in addition to the above methods. The X-ray crystal structure of compound 1 showed that all nitrogen and oxygen atoms of ligand (N2O4) and a molecule of nitrate with two donor oxygen atom have been coordinated to the metal ion and the Cd(II) ion is in an eight-coordinate environment that is best described as a distorted dodecahedron geometry.

Tibial coverage, meniscus position, size and damage in knees discordant for joint space narrowing – data from the Osteoarthritis Initiative

PubMed Central

Bloecker, K.; Guermazi, A.; Wirth, W.; Benichou, O.; Kwoh, C.K.; Hunter, D.J.; Englund, M.; Resch, H.; Eckstein, F.

2013-01-01

SUMMARY Introduction Meniscal extrusion is thought to be associated with less meniscus coverage of the tibial surface, but the association of radiographic disease stage with quantitative measures of tibial plateau coverage is unknown. We therefore compared quantitative and semi-quantitative measures of meniscus position and morphology in individuals with bilateral painful knees discordant on medial joint space narrowing (mJSN). Methods A sample of 60 participants from the first half (2,678 cases) of the Osteoarthritis Initiative cohort fulfilled the inclusion criteria: bilateral frequent pain, Osteoarthritis Research Society International (OARSI) mJSN grades 1–3 in one, no-JSN in the contra-lateral (CL), and no lateral JSN in either knee (43 unilateral mJSN1; 17 mJSN2/3; 22 men, 38 women, body mass index (BMI) 31.3 ± 3.9 kg/m2). Segmentation and three-dimensional quantitative analysis of the tibial plateau and meniscus, and semi-quantitative evaluation of meniscus damage (magnetic resonance imaging (MRI) osteoarthritis knee score – MOAKS) was performed using coronal 3T MR images (MPR DESSwe and intermediate-weighted turbo spin echo (IW-TSE) images). CL knees were compared using paired t-tests (between-knee, within-person design). Results Medial tibial plateau coverage was 36 ± 9% in mJSN1 vs 45 ± 8% in CL no-JSN knees, and was 31 ± 9% in mJSN2/3 vs 46 ± 6% in no-JSN knees (both P < 0.001). mJSN knees showed greater meniscus extrusion and damage (MOAKS), but no significant difference in meniscus volume. No significant differences in lateral tibial coverage, lateral meniscus morphology or position were observed. Conclusions Knees with medial JSN showed substantially less medial tibial plateau coverage by the meniscus. We suggest that the less meniscal coverage, i.e., less mechanical protection may be a reason for greater rates of cartilage loss observed in JSN knees. PMID:23220556

Ligand assisted carbon dioxide activation and hydrogenation using molybdenum and tungsten amides.

PubMed

Chakraborty, Subrata; Blacque, Olivier; Berke, Heinz

2015-04-14

The hepta-coordinated isomeric M(NO)Cl3(PN(H)P) complexes {M = Mo, ; W, , PN(H)P = (iPr2PCH2CH2)2NH, (HN atom of PN(H)P syn and anti to the NO ligand)} and the paramagnetic species M(NO)Cl2(PN(H)P) (M = Mo, ; W, ) could be prepared via a new synthetic pathway. The pseudo trigonal bipyramidal amides M(NO)(CO)(PNP) {M = Mo, ; W, ; [PNP](-) = [(iPr2PCH2CH2)2N](-)} were reacted with CO2 at room temperature with CO2 approaching the M[double bond, length as m-dash]N double bond in the equatorial (CO,NO,N) plane trans to the NO ligand and forming the pseudo-octahedral cyclic carbamates M(NO)(CO)(PNP)(OCO) (M = Mo, ; W = ). DFT calculations revealed that the approach to form the isomer is kinetically determined. The amine hydrides M(NO)H(CO)(PN(H)P) {M = Mo, ; W, }, obtained by H2 addition to , insert CO2 (2 bar) at room temperature into the M-H bond generating isomeric mixtures of the η(1)-formato complexes M(NO)(CO)(PN(H)P)(η(1)-OCHO), (M = Mo, ; M = W, ). Closing the stoichiometric cycles for sodium formate formation the isomeric mixtures were reacted with 1 equiv. of Na[N(SiMe3)2] regenerating . Attempts to turn the stoichiometric formate production into catalytic CO2 hydrogenation using in the presence of various types of sterically congested bases furnished yields of formate salts of up to 4%.

Computational study on night-time reaction of 1, 1-Dichlorodimethylether (DCDME) CH3OCHCl2 with NO3 radical and the fortuity of alkoxy radical CH3OC(Orad)Cl2

NASA Astrophysics Data System (ADS)

Gour, Nand Kishor; Begum, Saheen Shehnaz; Deka, Ramesh Chandra

2018-06-01

Degradation of 1,1-Dichlorodimethylether by NO3 radical in the troposphere has been modelled theoretically by employing Gaussian09 suite at BHandHLYP/6-311++G(d,p) level. Energies of all optimized electronic structures have been further refined at CCSD(T) method along with the same basis set to characterize stationary points on the potential energy surface including transition states. The rate constants of the titled reaction are obtained over the temperature range 200-450 K. Results show that H-abstraction is highly favourable for sbnd CHCl2 group of CH3OCHCl2. The atmospheric lifetime and global warming potential of the titled molecule have been reported. The thermal decomposition of CH3OC(Orad)Cl2 has also been explored.

Magnetic Ordering of Antiferromagnetic Trimer System 2b·3CuCl2·2H2O

NASA Astrophysics Data System (ADS)

Sanda, M.; Kubo, K.; Asano, T.; Morodomi, H.; Inagaki, Y.; Kawae, T.; Wang, J.; Matsuo, A.; Kindo, K.; Sato, T. J.

2012-12-01

In this paper, we present the magnetic properties of 2b·3CuCl2·2H2O (b = betaine, C5H11NO2). 2b·3CuCl2·2H2O is the first model substance for a two-dimensional S = 1/2 orthogonal antiferromagnetic trimer system. We have performed magnetic susceptibility, magnetization curve, and specific heat under extreme conditions: low temperatures and high magnetic fields in this system. The experimental results indicate that this substance is a magnetically S = 1/2 antiferromagnetic trimer system. The magnetization also shows one-third of the saturation value (MS ~ 3.2μB/f.u.) between 5 and 14T The specific heat in a zero field shows a sharp peak at 1.38K corresponding to a long-range magnetic ordering, TN. As the magnetic field increases, the TN shifts remarkably to a lower temperature and is suppressed. Above 5T, the specific heat has no anomaly down to 150mK In the plateau region with an energy gap, the magnetic ordering seems to be disappeared.

Lower stratosphere measurements of variation with latitude of CF2Cl2, CFCl3, CCl4, and N2O profiles in the northern hemisphere

NASA Technical Reports Server (NTRS)

Vedder, J. F.; Tyson, B. J.; Brewer, R. B.; Inn, E. C. Y.; Boitnott, C. A.

1978-01-01

Measurements were made from a U-2 aircraft of profiles of CF2Cl2, CFCl3, CCl4 and N2O in the lower stratosphere in a meridional survey at a longitude of 159 deg W during the period October 1 to November 14, 1976. The latitude distributions obtained show a marked decrease in mixing ratio with increasing latitude from about 7 deg N in the Intertropical Convergence Zone to about 79 deg N. The results suggest the importance of meridional transport and mixing in the stratosphere in accounting, at least in part, for the observed profile variation with latitude. The contaminants C2F4Cl2, C2F3Cl3, CHCCl3 and SF6 were also detected but their mixing ratios were small and no accurate standards were prepared for them.

Nitrogen Species in the Post-Pinatubo Stratosphere: Model Analysis Utilizing UARS Measurements

NASA Technical Reports Server (NTRS)

Danilin, M. Y.; Rodriquez, J. M.; Hu, W.; Ko, M. K. W.; Weisenstein, D. K.; Mergenthaler, J. L.; Russell, J. M., III; Koike, M.; Yue, G. K.

1998-01-01

We present an analysis of the impact of heterogeneous chemistry on the partitioning of nitrogen species measured by the Upper Atmosphere Research Satellite (UARS) instruments. The UARS measurements utilized include: N2O, HNO3 and ClONO2 (Cryogen Limb Array Etalon Spectrometer (CLAES), version 7), temperature, methane, ozone, H2O, HCl, NO and NO2 (HALogen Occultation Experiment (HALOE), version 18). The analysis is carried out for the data from January 1992 to September 1994 in the 100-1 mbar (approx.17-47 km) altitude range and over 10 degree latitude bins from 70degS to 70degN. Temporal-spatial evolution of aerosol surface area density (SAD) is adopted according to the Stratospheric Aerosol and Gas Experiment (SAGE) 11 data. A diurnal steady-state photochemical box model, constrained by the temperature, ozone, H2O, CH4, aerosol SAD and columns of O2 and O3 above the point of interest, has been used as the main tool to analyze these data. Total inorganic nitrogen (NO(y)) is obtained by three different methods: (1) as a sum of the UARS measured NO, NO2, HNO3, and ClONO2; (2) from the N2O-NO(y) correlation, and (3) from the CH4-NO(y) correlation. To validate our current understanding of stratospheric heterogeneous chemistry for post-Pinatubo conditions, the model-calculated NO(x)/NO(y) ratios and the NO, NO2, and HNO3 profiles are compared to the UARS-derived data. In general, the UARS-constrained box model captures the main features of nitrogen species partitioning in the post-Pinatubo years. However, the model underestimates the NO2 content, particularly, in the 30-7 mbar (approx. 23-32 km) range. Comparisons of the calculated temporal behavior of the partial columns of NO2 and HNO3 and ground based measurements at 45degS and 45degN are also presented. Our analysis indicates that ground-based and HALOE v. 18 measurements of the NO2 vertical columns are consistent within the range of their uncertainties and are systematically higher (up to 50%) than the model results at mid-latitudes in both hemispheres. Reasonable agreement is obtained for HNO3 columns at 45degS suggesting some problems with nitrogen species partitioning in the model. Outstanding uncertainties are discussed.

AN EXPERIMENTAL STUDY ON ARTIFICIAL CONDENSATION NUCLEI,

DTIC Science & Technology

NH4Cl, CaCl2, P205, NH4NO3, (NH4)2SO4, etc.) and suspensoids such as camphor , silicon minerals, kaolin, lamp black, and calcium lime (CaO). The...findings reveal that the above mentioned soluble nuclei and camphor powder are active artificial hygroscopic condensation nuclei and that lamp black

Air quality status during Diwali festival of India: a case study.

PubMed

Rao, Padma S; Gajghate, D G; Gavane, A G; Suryawanshi, P; Chauhan, C; Mishra, S; Gupta, N; Rao, C V C; Wate, S R

2012-08-01

The PM(2.5) and PM(10) samples were collected during Diwali celebration from study area and characterized for ionic concentration of four anions (NO(3) (-), NO(2) (-), Cl(-), SO(4) (2-)) and five cations (K(+), Mg(2+), NH(4) (+), Ca(2+), Na(+)). The results showed that the ionic concentrations were three times compared to those on pre and post Diwali days. Predominant ions for PM(2.5) were K(+) 33.7 μg/m(3), Mg(+) 31.6 μg/m(3), SO(4) (2-) 22.1 μg/m(3), NH(4) (+) 17.5 μg/m(3) and NO(3) (-) 18 μg/m(3) and for PM(10) the ionic concentrations were Mg(+) 29.6 μg/m(3), K(+) 26 μg/m(3), SO(4) (2-) 19.9 μg/m(3), NH(4) (+) 16.8 μg/m(3) and NO(3) (-) 16 μg/m(3). While concentration of SO(2) and NO(2) were 17.23, 70.33 μg/m(3) respectively.

An Electronic Tongue Designed to Detect Ammonium Nitrate in Aqueous Solutions

PubMed Central

Campos, Inmaculada; Pascual, Lluis; Soto, Juan; Gil-Sánchez, Luis; Martínez-Máñez, Ramón

2013-01-01

An electronic tongue has been developed to monitor the presence of ammonium nitrate in water. It is based on pulse voltammetry and consists of an array of eight working electrodes (Au; Pt; Rh; Ir; Cu; Co; Ag and Ni) encapsulated in a stainless steel cylinder. In a first step the electrochemical response of the different electrodes was studied in the presence of ammonium nitrate in water in order to further design the wave form used in the voltammetric tongue. The response of the electronic tongue was then tested in the presence of a set of 15 common inorganic salts; i.e.; NH4NO3; MgSO4; NH4Cl; NaCl; Na2CO3; (NH4)2SO4; MgCl2; Na3PO4; K2SO4; K2CO3; CaCl2; NaH2PO4; KCl; NaNO3; K2HPO4. A PCA plot showed a fairly good discrimination between ammonium nitrate and the remaining salts studied. In addition Fuzzy Art map analyses determined that the best classification was obtained using the Pt; Co; Cu and Ni electrodes. Moreover; PLS regression allowed the creation of a model to correlate the voltammetric response of the electrodes with concentrations of ammonium nitrate in the presence of potential interferents such as ammonium chloride and sodium nitrate. PMID:24145916

Interactions in L-phenylalanine/L-leucine/L-glutamic Acid/L-proline + 2 M aqueous NaCl/2 M NaNO3 systems at different temperatures

NASA Astrophysics Data System (ADS)

Riyazuddeen, Imran Khan; Afrin, Sadaf

2012-12-01

Density (ρ) and speed of sound ( u) in 2 M aqueous NaCl and 2 M NaNO3 solutions of amino acids: L-phenylalanine, L-leucine, L-glutamic acid, and L-proline have been measured for several molal concentrations of amino acids at different temperatures. The ρ and u data have been used to calculate the values of isothermal compressibility and internal pressure at different temperatures. The trends of variations of κ T and P i with an increase in molal concentration of amino acid and temperature have been discussed in terms of solute-solvent and solute-solute interactions in the systems.

Structural variety in copper(II) complexes of 3-formylchromone: Synthesis, spectral, thermal, molecular modeling and biological studies

NASA Astrophysics Data System (ADS)

Shebl, Magdy; Adly, Omima M. I.; Taha, A.; Elabd, N. N.

2017-11-01

The compound in the title (L) was synthesized and reacted with Cu(II) metal ion with different anions (OAc-, NO3-, SO42-, ClO4-, Cl- and Br-) in absence and presence of auxiliary ligands (L‧); N,O-donor; or N,N-donor; to form binary and ternary Cu(II)-chelates. The metal complexes were fully characterized by analytical and spectral techniques in addition to thermal, conductivity and magnetic susceptibility measurements. The obtained results showed that the ligand behaves as a neutral bidentate, forming chelates with molar ratios: 1:1, 1:2 and 1:3; M:L for binary and 1:2:1 and 1:1:1; M:L:L‧ for ternary complexes, which can be formulated as: [LmCuXn(H2O)y]·zH2O, m = 1 or 2, n = 0, 1 or 2, X = OAc-, SO42-, Cl- or Br-, y = 0 or 2, z = 0 or 0.5; [LmCu(H2O)n]X2·zMeOH, m = 2 or 3, n = 0 or 2, X = ClO4- or NO3-, z = 0 or 1 and [Lm L'Cu(H2O)n](NO3)x·yS, m = 1 or 2, n = 0 or 2, X = 1 or 2, y = 0.5 or 4, S = H2O or MeOH. The ESR spin Hamiltonian parameters of some complexes were calculated. Kinetic parameters (Ea, A, ΔH, ΔS and ΔG) of the thermal decomposition stages have been evaluated using Coats-Redfern equations. The structural parameters of the ligand and its metal complexes have been calculated and correlated with the experimental data. The metal complexes exhibited octahedral and square planar geometrical arrangements according to the nature of the anion. The ligand and its metal complexes showed antibacterial activity towards Gram-positive bacteria, Gram-negative bacteria, yeast and fungus.

Chelation, spectroscopic characterization, biological activity and crystal structure of 2,3-butanedione isonicotinylhydrazone: Determination of Zr4+ after flotation separation

NASA Astrophysics Data System (ADS)

Al-Fulaij, O. A.; Jeragh, B.; El-Sayed, A. E. M.; El-Defrawy, M. M.; El-Asmy, A. A.

2015-02-01

New metal complexes of Co(II), Ni(II) Cu(II), Zn(II), Cd(II), Pd(II) and Hg(II) with 2,3-butanedione isonicotinylhydrazone [BINH] have been prepared and investigated. Single crystal for BINH is grown and solved as orthorhombic with P 21 21 2 space group. The formula of the ligand was assigned based on the elemental analysis, mass spectra and conductivity measurements. The complexes assigned the formulae [M(BINH-H)Cl]ṡnH2O (Mdbnd Co(II), Ni(II), Cu(II), Zn(II); n = 0 or 1); [Hg(BINH-H)(H2O)2Cl]; [Cd(BINH)Cl2]ṡ2H2O and [Pd(BINH)Cl2]ṡH2O. All complexes are nonelectrolytes. BINH acts as a tridentate ligand in [M(BINH-H)Cl]ṡnH2O and [Hg(BINH-H)(H2O)2Cl] coordinating through Cdbnd Oketonic, Csbnd Oamedic and Cdbnd Nhy and as a neutral bidentate through Cdbnd Oketonic and Cdbnd Nhy in [Cd(BINH)Cl2]ṡ2H2O and [Pd(BINH)Cl2]ṡH2O; the pyridine nitrogen has no rule in coordination. The data are supported by NMR (1H and 13C) spectra. The magnetic moments and electronic spectra provide a tetrahedral structure for the Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes; square-planar for the Pd(II) complex and octahedral for the Hg(II) complex. The TGA of the complexes depicted the outer and inner water molecules as well as the final residue. The cobalt and cadmium complexes ended with the metal while the Cu(II), Zn(II) and Pd(II) complexes ended with complex species. [Hg(BINH-H)(H2O)2Cl] has no residue. The ligand is inactive against all tested organisms except for Bacillus thuringiensis. The Hg(II) complex is found more active than the other complexes. The flotation technique is found applicable for the separation of micro amount (10 ppm) of Zr4+ using 10 ppm of BINH and 1 × 10-5 mol L-1 of oleic acid at pH 6 with efficiency of 98% with no interferences.

Seasonal variations and size distributions of water-soluble ions of atmospheric particulate matter at Shigatse, Tibetan Plateau.

PubMed

Yang, Yongjie; Zhou, Rui; Yan, Yan; Yu, Yue; Liu, Junqing; Di, Yi'an; Du, Zhenyu; Wu, Dan

2016-02-01

Size-segregated atmospheric particulate matter (PM) samples were collected from July 2012 to September 2013 at Shigatse, high-altitude (3836 m above sea level) site on the south Tibetan Plateau (TP); objectives were to determine the characteristics and size distribution of water-soluble ions (WSIs). Eight major WSIs (Na(+), K(+), Mg(2+), Ca(2+), NH4(+), Cl(-), SO4(2-), and NO3(-)) were detected by ion chromatography. The total concentrations of WSIs were 6370 ± 1916 ng m(-3) in dry season (October - December, January - April), and 5261 ± 769 ng/m(3) during wet phase (May - September). The contribution of K(+) (130 ng m(-3)), Cl(-) (2035 ng m(-3)), SO4(2-) (1176 ng m(-3)), and NO3(-) (706 ng m(-3))(-)were significantly enhanced in dry season, and that of Na(+) (455 ng m(-3)), Mg(2+)(65.4 ng m(-3)), Ca(2+)(1034 ng m(-3)), and NH4(+) (1948 ng m(-3)) were significantly enhanced during wet phase. Mg(2+) and Ca(2+) were concentrated in the coarse mode, and the other ions concentrated in fine mode and coarse mode during two seasons. The correlation coefficients between K(+) and NH4(+), Cl(-), SO4(2-) and NO3(-) were 0.58 (P < 0.01), 0.40 (P < 0.05), 0.82 (P < 0.01) and 0.69 (P < 0.01), indicating their dominant contribution from biomass burning in dry season. The significant correlation between NH4(+) and HCO3(-) which were calculated by ion balance (r = 0.89, P < 0.01), suggesting the source from nitrogen fertilizers during wet phase. Copyright © 2015 Elsevier Ltd. All rights reserved.

Ba{sub 3}GeS{sub 5} and Ba{sub 3}InS{sub 4}Cl: Interesting size effects originated from the tetrahedral anions

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

Pan, Ming-Yan; Xia, Sheng-Qing, E-mail: shqxia@sdu.edu.cn; Liu, Xiao-Cun

2014-11-15

Two new barium chalcogenides, Ba{sub 3}GeS{sub 5} and Ba{sub 3}InS{sub 4}Cl, were synthesized by using high temperature solid-state reactions and their structures were determined by single-crystal X-ray diffraction technique. Despite the similar chemical formula, the structures of Ba{sub 3}GeS{sub 5} and Ba{sub 3}InS{sub 4}Cl are subtly different due to the size effects originated from the tetrahedral anions. Ba{sub 3}GeS{sub 5} crystallizes in the orthorhombic space group Pnma (no. 62) with cell parameters of a=12.0528(9) Å, b=9.5497(7) Å and c=8.5979(6) Å, while Ba{sub 3}InS{sub 4}Cl adopts a different tetragonal system (space group: I4/mcm, no. 140, a=b=8.3613(6) Å, c=14.3806(18) Å). The measuredmore » optical band gap of Ba{sub 3}GeS{sub 5} is 3.0 eV, a little smaller than the value of 3.42 eV in Ba{sub 3}InS{sub 4}Cl. Theoretical calculations by Wien2k are provided as well in order to better understand these results. - Graphical abstract: The polyhedral structure view for Ba{sub 3}GeS{sub 5} and Ba{sub 3}InS{sub 4}Cl in which Ba, S and Cl atoms are plotted in purple, red and green spheres. - Highlights: • Two new barium chalcogenides, Ba{sub 3}GeS{sub 5} and Ba{sub 3}InS{sub 4}Cl, were synthesized from the BaCl{sub 2}-flux reactions. • Their crystal structures feature discrete [MS{sub 4}] tetrahedra which embody interesting size effects. • Both compounds exhibit a band gap around 3.0 eV. • They are thermally stable up to 1073 K.« less

Three different product types from reactions of lithiated cyclic aminals with trivalent organometal chlorides.

PubMed

Hellmann, Benjamin J; Kamps, Ina; Mix, Andreas; Neumann, Beate; Stammler, Hans-Georg; Mitzel, Norbert W

2010-09-21

The reaction of 2-lithio-1,3,5-trimethyl-1,3,5-triazacyclohexane with YCp(2)Cl leads to the formation of a donor-functionalised mono-anionic amide ligand, 1,3,5-trimethyl-2-(methylamidomethyl)-1,3,5-triazacyclohexane, bonded to the YCp(2) unit. The reaction involves a cleavage of the 1,3,5-triazacyclohexane ring and such a cleavage is also observed in the analogous reaction with (Me(3)C)(2)GaCl, where a MeN[double bond, length as m-dash]CH(-) fragment is formed. No such cleavage occurs in the reaction of the related dilithiated bicyclic bis(3-methyl-1,3-diazacyclohex-1-yl)methane with YCpCl(2).3thf, which affords a mixed lithium-yttrium organyl.

Centrifugal and Numerical Modeling of Buried Structures. Volume 2. Dynamic Soil-Structure Interaction.

DTIC Science & Technology

1987-07-14

RD-RISE 368 CENTRIFUGAL AND NUMERICAL MODELING OF BURIED STRUCTURES 1/3 VOLUME 2 DYNAMIC..(U) COLORADO UNIV AT BOULDER DEPT OF CIVIL ENVIRONMENTAL...20332-6448 ELEMENT NO NO. NO ACCESSION NO 61102F 2302 Cl 11 TITLE (Include Security Classification) (U) Centrifugal and Numerical Modeling of Buried ...were buried in a dry sand and tested in the centrifuge to simulate the effects of gravity-induced overburden stresses which played a major role in

Particulate matter characteristics during agricultural waste burning in Taichung City, Taiwan.

PubMed

Cheng, Man-Ting; Horng, Chuen-Liang; Su, Yi-Ru; Lin, Li-Kai; Lin, Yu-Chi; Chou, Charles C-K

2009-06-15

Agricultural waste burning is performed after harvest periods in June and November in Taiwan. Typically, farmers use open burning to dispose of excess rice straw. PM(2.5) and PM(2.5-10) measurements were conducted at National Chung Hsing University in Taichung City using a dichotomous sampler. The sampling times were during straw burning periods after rice harvest during 2002-2005. Ionic species including SO(4)(2-), NO(3)(-), NH(4)(+), K(+), Ca(2+), Cl(-) and Na(+) and carbonaceous species (EC and OC) in PM(2.5) and PM(2.5-10) were analyzed. The results showed that the average PM(2.5) and PM(2.5-10) concentrations were 123.6 and 31.5 microg m(-3) during agricultural waste burning periods and 32.6 and 21.4 microg m(-3) during non-waste burning periods, respectively. The fine aerosol ionic species including Cl(-), K(+) and NO(3)(-) increased 11.0, 6.7 and 5.5 times during agricultural burning periods compared with periods when agricultural waste burning is not performed. K(+) was found mainly in the fine mode during agricultural burning. High nitrogen oxidation ratio was found during agricultural waste burning periods which might be caused by the conversion of Nitrogen dioxide (NO(2)) to NO(3)(-). It is concluded that agricultural waste burning with low dispersion often causes high PM(2.5) and gases pollutant events.

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 relatively low and homogeneous anion concentrations in the ice-cemented sediments point to either a mechanism of recent salt removal, or to relatively modern permafrost soils (<1 million years). Together, our results show that near surface salts in University Valley serve as an end-member of stratospheric sources not subject to biological processes or extensive remobilization.

Indoor/outdoor of PM10 relationships and its water-soluble ions composition in selected primary schools in Malaysia

NASA Astrophysics Data System (ADS)

Mohamad, Noorlin; Latif, Mohd Talib

2013-11-01

Measurements of PM10 and water-soluble ions were carried out on indoor and outdoor PM10 (particles > 10 μm in aerodynamic diameter) aerosols sampled at selected primary schools of Kuala Lumpur (S1) and Putrajaya (S2), respectively. Samples were collected using a low volume sampler on Teflon filters. The water-soluble ions chloride (Cl-), nitrate (NO3-), sulfate (SO42-), calcium (Ca2+), magnesium (Mg2+), sodium (Na+), potassium (K+) and ammonium (NH4+) was analyzed using ion chromatography. The results showed that the indoor PM10 mass concentrations in S1 and S2 were 96.6 and 69.5 μg/m3, while the outdoor PM10 mass concentrations were 80.1 and 85.2 μg/m3, respectively. This indicated that NO3- were the most dominant ions, followed by SO42-, Ca2+, K+ and Na+, while Cl-, Mg2+ and Na+ were present at low concentrations. Pearson's correlation test applied to all the data showed high correlation between SO42- and NO3-, indicating a common anthropogenic origin. In addition, the correlations between Na+ and Ca2+ indicated crustal origins that significantly contributed to human exposure.

Hydrogeochemical investigation of groundwater in shallow coastal aquifer of Khulna District, Bangladesh

NASA Astrophysics Data System (ADS)

Islam, S. M. Didar-Ul; Bhuiyan, Mohammad Amir Hossain; Rume, Tanjena; Azam, Gausul

2017-12-01

Groundwater acts as a lifeline in the coastal regions to meet out the domestic, drinking, irrigational and industrial needs. To investigate the hydrogeochemical characteristics of groundwater and its suitability, twenty samples were collected from the shallow tubewells of study area having screen depth 21-54 m. The water quality assessment has been carried out by evaluating the physicochemical parameters such as temperature, pH, EC, TDS and major ions i.e., Na+, K+, Ca2+, Mg2+, Cl-, SO4 2-, NO3 -, HCO3 -. Results found that, the water is slightly alkaline and brackish in nature. The trends of cations and anions are Na+ > Ca2+ > Mg2+ > K+ and Cl- > HCO3 - > SO4 2- > NO3 -, respectively and Na-Cl-HCO3 is the dominant groundwater type. The analyzed samples were also characterized with different indices, diagram and permissible limit i.e., electric conductivity (EC), total dissolved solids (TDS), chloride content (Cl), soluble sodium percentage (SSP), sodium adsorption ratio (SAR), residual sodium carbonate (RSC), magnesium adsorption ratio (MAR), Kelley's ratio (KR), Wilcox diagram and USSL diagram, and results showed that groundwater are not suitable for drinking and irrigational use. The factors responsible for the geochemical characterization were also attempted by using standard plot and it was found that mixing of seawater with entrapped water plays a significant role in the study area.

Syntheses, crystal structures and supramolecular topologies of copper(II)-main group metal complexes derived from N,N‧-o-phenylenebis(3-ethoxysalicylaldimine)

NASA Astrophysics Data System (ADS)

Mondal, Suraj; Hazra, Susanta; Sarkar, Sohini; Sasmal, Sujit; Mohanta, Sasankasekhar

2011-10-01

The work in the present investigation reports the syntheses, crystal structures and supramolecular topologies of 11 copper(II)-main group metal ion complexes [Cu IILNa I(NO 3)(H 2O)]·2CH 3CN ( 1), [Cu IILNa I(N 3)(CH 3OH)]·CH 3OH ( 2), [Cu IILNa I(ClO 4)(CH 3CN)]·0.5CH 3CN ( 3), [Cu IILNa I(BF 4)(CH 3OH)]·H 2O ( 4), [{Cu IILNa I(H 2O)} 2(Cu IIL)](BPh 4) 2 ( 5), [Cu IILK I(ClO 4)(CH 3COCH 3)] ( 6), [Cu IILCa II(ClO 4) 2(H 2O)] ( 7), [{Cu IILCa II(NO 3)(μ-NO 3)(H 2O)}(Cu IIL)]·H 2O·CH 3COCH 3 ( 8), [(Cu IIL) 2Ba II(NO 3) 2]·CH 3OH ( 9), [Cu IILPb II(NO 3) 2]·CH 3OH ( 10) and [Cu IILBi III(NO 3) 3]·CH 3COCH 3 ( 11), where H 2L = N, N'- o-phenylenebis(3-ethoxysalicylaldimine). Among these, eight ( 1-4, 6, 7, 10 and 11) are dinuclear compounds, one ( 9) is trinuclear double-decker sandwich compound, one ( 8) is a [2 × 1 + 1 × 1] trimetallic cocrystal of a dinuclear and a mononuclear units and the remaining ( 5) is a [2 × 2 + 1 × 1] pentametallic cocrystal of two dinuclear and one mononuclear units. All the 11 compounds 1-11 contain one or more deprotonated ligand, L 2-, the salen type N 2O 2 compartment of each of which is occupied by a Cu II ion to result in the formation of a [Cu IIL] moiety. On the other hand, the larger and open O(phenoxo) 2O(ethoxy) 2 compartment of the ligand in one or more [Cu IIL] moieties interact (s) with the metal ions Na I ( 1-5)/K I ( 6)/Ca II ( 7 and 8)/Ba II ( 9)/Pb II ( 10)/Bi III ( 11) to produce the title compounds. It has been observed that the neighbouring di/trinuclear units in 1/ 3/ 4/ 6/ 9/ 10/ 11 are self-assembled to one-/two-dimensional topologies as a result of one or more C sbnd H⋯O/O sbnd H⋯O hydrogen bonding interaction (s). Following self-assemblies are observed: one-dimensional in 4, one-dimensional helical in 1, one-dimensional double-chain (ladder) in 3, 6 and 10, two-dimensional in 9 and 11.

Metal phosphide catalysts and methods for making the same and uses thereof

DOEpatents

Habas, Susan Ellen; Wang, Jun; Ruddy, Daniel A.; Baddour, Frederick Raymond Gabriel; Schaidle, Joshua

2017-05-02

The present disclosure relates to a method that includes heating a mixture that includes a metal phenylphosphine-containing precursor that includes at least one of Mo(PPh.sub.3).sub.2(CO).sub.4, Pd(PPh.sub.3).sub.4, Ru(PPh.sub.3).sub.3Cl.sub.2, Ru(PPh.sub.3).sub.2(CO).sub.2Cl.sub.2, Co(PPh.sub.3)(CO).sub.2(NO), and/or Rh(PPh.sub.3).sub.2(CO)Cl, a surfactant, and a solvent. The heating is to a target temperature to form a heated mixture containing a metal phosphide nanoparticle that includes at least one of MoP, Ru.sub.2P, Co.sub.2P, Rh.sub.2P, and/or Pd.sub.3P, and the metal phosphide nanoparticle is not hollow.

Hydro-chemical Survey and Quantifying Spatial Variations of Groundwater Quality in Dwarka, Sub-city of Delhi, India

NASA Astrophysics Data System (ADS)

Rawat, Kishan Singh; Tripathi, Vinod Kumar

2015-06-01

Hydrological and geological aspect of the region play vital role for water resources utilization and development. Protection and management of groundwater resources are possible with the study of spatio-temporal water quality parameters. The study was undertaken to assess the deterioration in groundwater quality, through systematic sampling during post monsoon seasons of the year 2008 by collecting water samples from thirty bore wells located in Dwarka, sub-city of Delhi, India. The average concentrations of groundwater quality parameters namely Calcium (Ca2+), Magnesium (Mg2+), Nitrate (NO3 -), Chloride (Cl-), sulphate (SO4 2-), total hardness (TH), total dissolved solids (TDS), and electrical conductivity were 300, 178, 26.5, 301, 103, 483, 1042 mg/l and 1909 μS/cm respectively. Estimated physico-chemical parameters revealed that 7 % of the groundwater samples shown nitrate concentrations higher than safe limit prescribed by World Health Organization (WHO). Groundwater quality the in study region was poor due to come out result that NO3 - concentration exceeding the threshold value of 50 mg/l, and main cause is disposal of sewage and animal wastes to Najafgarh drain. Dominant cations are Mg2+, Ca2+ and anions are SO4 2- and Cl-. The abundance of the major ions in groundwater is in the order: Ca2+ > Mg2+ and Cl- > SO4 2- > NO3. TH have strong correlation with Ca2+ (r = 0.81), Mg2+ (r = 0.82), Cl- (r = 0.86) but poor correlation with TDS (r = 0.52). Knowledge of correlation values between water quality parameters is helpful to take decision of appropriate management strategy for controlling groundwater pollution.

Effects of the Mount Pinatubo eruption on the radiative and chemical processes in the troposphere and stratosphere

NASA Technical Reports Server (NTRS)

Kinnison, Douglas E.; Grant, Keith E.; Connell, Peter S.; Wuebbles, Donald J.

1994-01-01

The Lawrence Livermore National Laboratory two-dimensional zonally-averaged chemical-radiative-transport model of the global atmosphere was used to study the effects of the 15 June 1991 eruption of the Mt. Pinatubo volcano on stratospheric processes. SAGE 2 time-dependent aerosol surface area density and optical extinction data were used as input into the model. By 22 December 1991, a maximum equatorial change of -1.8 percent in column ozone was derived from heterogeneous chemical processes that convert NO(x) into HNO3 on sulfuric acid aerosols. Radiative feedbacks from increased aerosol optical thickness independently changes column ozone by approximately -3.5 percent for the same period. This occurs from increasing the net heating of the lower stratosphere, which indirectly increases chemical reaction rates via their temperature dependence and from changes in actinic fluxes, which directly modify photodissociation rates. Including both heterogeneous and radiative effects changes column ozone by -5.5 percent. The model-derived change overestimates the decrease in column ozone relative to the TOMS instrument on the Nimbus 7 satellite. Maximum local ozone decreases of 12 percent were derived in the equatorial region, at 25 km. Model-derived column NO2 peaked (-14 percent) at 30 deg S in October 1991. The timing of the NO2 peak is consistent with observation, but the model underestimates the magnitude of the decrease. Local concentrations of NO(x) (NO + NO2), ClO(x) (Cl + ClO), and HO(x) (OH + HO2), in the lower stratosphere between 30 deg S and 30 deg N, were calculated to have changed by -40 percent, +100 to +160 percent, and +120 to +140 percent respectively.

Refractory concretes

DOEpatents

Holcombe, Jr., Cressie E.

1979-01-01

Novel concrete compositions comprise particles of aggregate material embedded in a cement matrix, said cement matrix produced by contacting an oxide selected from the group of Y.sub.2 O.sub.3, La.sub.2 O.sub.3, Nd.sub.2 O.sub.3, Sm.sub.2 O.sub.3, Eu.sub.2 O.sub.3 and Gd.sub.2 O.sub.3 with an aqueous solution of a salt selected from the group of NH.sub.4 NO.sub.3, NH.sub.4 Cl, YCl.sub.3 and Mg(NO.sub.3).sub.2 to form a fluid mixture; and allowing the fluid mixture to harden.

Measurements of NO and total reactive odd-nitrogen, NOy, in the Antarctic stratosphere

NASA Technical Reports Server (NTRS)

Fahey, D. W.; Murphy, D. M.; Eubank, C. S.; Ferry, G. V.; Chan, K. Roland; Ko, Malcolm K. W.

1988-01-01

Measurements of NO and total reactive N, NOy, were made as part of the Airborne Antarctic Ozone Experiment conducted in Punta Arenas, Chile during Aug. and Sept. 1987. The total reactive N reservoir includes the species NO, NO2, NO3, N2 O5, HNO3, and ClONO2. The instrument was located on board the NASA ER2 aircraft which conducted 12 flights over the Antarctic continent reaching altitudes of 18 km at 72 deg S latitude. The NOy technique utilized the conversion of component NOy species to NO on a gold catalyst and the subsequent detection of NO by the chemiluminescence reaction of NO with ozone. Since the inlet sample line is heated and the catalyst operates at 300 C, NOy incorporated in aerosols evaporates and is converted to NO. NO was measured on two separate flights by removing the catalyst from the sample inlet line.

Resveratrol Increases Nitric Oxide Production in the Rat Thick Ascending Limb via Ca2+/Calmodulin

PubMed Central

Gonzalez-Vicente, Agustin; Cabral, Pablo D.; Garvin, Jeffrey L.

2014-01-01

The thick ascending limb of the loop of Henle reabsorbs 30% of the NaCl filtered through the glomerulus. Nitric oxide (NO) produced by NO synthase 3 (NOS3) inhibits NaCl absorption by this segment. Resveratrol, a polyphenol, has beneficial cardiovascular and renal effects, many of which are mediated by NO. Resveratrol increases intracellular Ca2+ (Cai) and AMP kinase (AMPK) and NAD-dependent deacetylase sirtuin1 (SIRT1) activities, all of which could activate NO production. We hypothesized that resveratrol stimulates NO production by thick ascending limbs via a Ca2+/calmodulin-dependent mechanism. To test this, the effect of resveratrol on NO bioavailability was measured in thick ascending limb suspensions. Cai was measured in single perfused thick ascending limbs. SIRT1 activity and expression were measured in thick ascending limb lysates. Resveratrol (100 µM) increased NO bioavailability in thick ascending limb suspensions by 1.3±0.2 AFU/mg/min (p<0.03). The NOS inhibitor L-NAME blunted resveratrol-stimulated NO bioavailability by 96±11% (p<0.03). The superoxide scavenger tempol had no effect. Resveratrol elevated Cai from 48±7 to 135±24 nM (p<0.01) in single tubules. In Ca2+-free media, the resveratrol-induced increase in NO was blunted by 60±20% (p<0.05) and the rise in Cai reduced by 80%. Calmodulin inhibition prevented the resveratrol-induced increase in NO (p<0.002). AMPK inhibition had no effect. Resveratrol did not increase SIRT1 activity. We conclude that resveratrol increases NO production in thick ascending limbs via a Ca2+/calmodulin dependent mechanism, and SIRT1 and AMPK do not participate. Resveratrol-stimulated NO production in thick ascending limbs may account for part of its beneficial effects. PMID:25314136

Selective Solid-liquid Extraction and Liquid-liquid Extraction of Lithium Chloride using Strapped Calix[4]pyrroles

DOE PAGES

He, Qing; Williams, Neil J.; Oh, Ju; ...

2018-05-25

LiCl is a classic "hard" ion salt that is present in lithium-rich brines and a key component in end-of-life materials (i.e., used lithium-ion batteries). Its isolation and purification from like salts is a recognized challenge with potential strategic and economic implications. Here in this paper, we describe two ditopic calix[4]pyrrole-based ion pair receptors (2 and 3), that are capable of selectively capturing LiCl. Under solid-liquid extraction conditions, using 2 as the extractant, LiCl could be separated from a NaCl-KCl salt mixture containing as little as 1% LiCl with ~100% selectivity, while receptor 3 achieved similar separations when the LiCl levelmore » was as low as 200 ppm. Under liquid-liquid extraction conditions using nitrobenzene as the non-aqueous phase, the extraction preference displayed by 2 is KCl > NaCl > LiCl. Lastly, in contrast, 3 exhibits high selectivity towards LiCl over NaCl and KCl, with no appreciable extraction being observed for the latter two salts.« less

Selective Solid-liquid Extraction and Liquid-liquid Extraction of Lithium Chloride using Strapped Calix[4]pyrroles

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

He, Qing; Williams, Neil J.; Oh, Ju

LiCl is a classic "hard" ion salt that is present in lithium-rich brines and a key component in end-of-life materials (i.e., used lithium-ion batteries). Its isolation and purification from like salts is a recognized challenge with potential strategic and economic implications. Here in this paper, we describe two ditopic calix[4]pyrrole-based ion pair receptors (2 and 3), that are capable of selectively capturing LiCl. Under solid-liquid extraction conditions, using 2 as the extractant, LiCl could be separated from a NaCl-KCl salt mixture containing as little as 1% LiCl with ~100% selectivity, while receptor 3 achieved similar separations when the LiCl levelmore » was as low as 200 ppm. Under liquid-liquid extraction conditions using nitrobenzene as the non-aqueous phase, the extraction preference displayed by 2 is KCl > NaCl > LiCl. Lastly, in contrast, 3 exhibits high selectivity towards LiCl over NaCl and KCl, with no appreciable extraction being observed for the latter two salts.« less

Evaluation of refractive correction for standard automated perimetry in eyes wearing multifocal contact lenses

PubMed Central

Hirasawa, Kazunori; Ito, Hikaru; Ohori, Yukari; Takano, Yui; Shoji, Nobuyuki

2017-01-01

AIM To evaluate the refractive correction for standard automated perimetry (SAP) in eyes with refractive multifocal contact lenses (CL) in healthy young participants. METHODS Twenty-nine eyes of 29 participants were included. Accommodation was paralyzed in all participants with 1% cyclopentolate hydrochloride. SAP was performed using the Humphrey SITA-standard 24-2 and 10-2 protocol under three refractive conditions: monofocal CL corrected for near distance (baseline); multifocal CL corrected for distance (mCL-D); and mCL-D corrected for near vision using a spectacle lens (mCL-N). Primary outcome measures were the foveal threshold, mean deviation (MD), and pattern standard deviation (PSD). RESULTS The foveal threshold of mCL-N with both the 24-2 and 10-2 protocols significantly decreased by 2.2-2.5 dB (P<0.001), while that of mCL-D with the 24-2 protocol significantly decreased by 1.5 dB (P=0.0427), as compared with that of baseline. Although there was no significant difference between the MD of baseline and mCL-D with the 24-2 and 10-2 protocols, the MD of mCL-N was significantly decreased by 1.0-1.3 dB (P<0.001) as compared with that of both baseline and mCL-D, with both 24-2 and 10-2 protocols. There was no significant difference in the PSD among the three refractive conditions with both the 24-2 and 10-2 protocols. CONCLUSION Despite the induced mydriasis and the optical design of the multifocal lens used in this study, our results indicated that, when the dome-shaped visual field test is performed with eyes with large pupils and wearing refractive multifocal CLs, distance correction without additional near correction is to be recommended. PMID:29062776

Evaluation of refractive correction for standard automated perimetry in eyes wearing multifocal contact lenses.

PubMed

Hirasawa, Kazunori; Ito, Hikaru; Ohori, Yukari; Takano, Yui; Shoji, Nobuyuki

2017-01-01

To evaluate the refractive correction for standard automated perimetry (SAP) in eyes with refractive multifocal contact lenses (CL) in healthy young participants. Twenty-nine eyes of 29 participants were included. Accommodation was paralyzed in all participants with 1% cyclopentolate hydrochloride. SAP was performed using the Humphrey SITA-standard 24-2 and 10-2 protocol under three refractive conditions: monofocal CL corrected for near distance (baseline); multifocal CL corrected for distance (mCL-D); and mCL-D corrected for near vision using a spectacle lens (mCL-N). Primary outcome measures were the foveal threshold, mean deviation (MD), and pattern standard deviation (PSD). The foveal threshold of mCL-N with both the 24-2 and 10-2 protocols significantly decreased by 2.2-2.5 dB ( P <0.001), while that of mCL-D with the 24-2 protocol significantly decreased by 1.5 dB ( P =0.0427), as compared with that of baseline. Although there was no significant difference between the MD of baseline and mCL-D with the 24-2 and 10-2 protocols, the MD of mCL-N was significantly decreased by 1.0-1.3 dB ( P <0.001) as compared with that of both baseline and mCL-D, with both 24-2 and 10-2 protocols. There was no significant difference in the PSD among the three refractive conditions with both the 24-2 and 10-2 protocols. Despite the induced mydriasis and the optical design of the multifocal lens used in this study, our results indicated that, when the dome-shaped visual field test is performed with eyes with large pupils and wearing refractive multifocal CLs, distance correction without additional near correction is to be recommended.

Cationic and Neutral Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) Complexes of Molybdenum and Tungsten: Lewis-Acid-Induced Intramolecular C-H Activation.

PubMed

Handford, Rex C; Wakeham, Russell J; Patrick, Brian O; Legzdins, Peter

2017-03-20

Treatment of CH 2 Cl 2 solutions of Cp*M(NO)Cl 2 (Cp* = η 5 -C 5 (CH 3 ) 5 ; M = Mo, W) first with 2 equiv of AgSbF 6 in the presence of PhCN and then with 1 equiv of Ph 2 PCH 2 CH 2 PPh 2 affords the yellow-orange salts [Cp*M(NO)(PhCN)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 )](SbF 6 ) 2 in good yields (M = Mo, W). Reduction of [Cp*M(NO)(PhCN)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 )](SbF 6 ) 2 with 2 equiv of Cp 2 Co in C 6 H 6 at 80 °C produces the corresponding 18e neutral compounds, Cp*M(NO)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) which have been isolated as analytically pure orange-red solids. The addition of 1 equiv of the Lewis acid, Sc(OTf) 3 , to solutions of Cp*M(NO)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) at room temperature results in the immediate formation of thermally stable Cp*M(NO→Sc(OTf) 3 )(H)(κ 3 -(C 6 H 4 )PhPCH 2 CH 2 PPh 2 ) complexes in which one of the phenyl substituents of the Ph 2 PCH 2 CH 2 PPh 2 ligands has undergone intramolecular orthometalation. In a similar manner, addition of BF 3 produces the analogous Cp*M(NO→BF 3 )(H)(κ 3 -(C 6 H 4 )PhPCH 2 CH 2 PPh 2 ) complexes. In contrast, B(C 6 F 5 ) 3 forms the 1:1 Lewis acid-base adducts, Cp*M(NO→B(C 6 F 5 ) 3 )(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) in CH 2 Cl 2 at room temperature. Upon warming to 80 °C, Cp*Mo(NO→B(C 6 F 5 ) 3 )(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) converts cleanly to the orthometalated product Cp*Mo(NO→B(C 6 F 5 ) 3 )(H)(κ 3 -(C 6 H 4 )PhPCH 2 CH 2 PPh 2 ), but Cp*W(NO→B(C 6 F 5 ) 3 )(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) generates a mixture of products whose identities remain to be ascertained. Attempts to extend this chemistry to include related Ph 2 PCH 2 PPh 2 compounds have had only limited success. All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.

FIGAERO ToF CIMS measurements of chlorine photochemical activation by nitryl chloride chemistry at a semi-rural site in Beijing

NASA Astrophysics Data System (ADS)

Le Breton, Michael; Hallquist, Åsa M.; Kant Pathak, Ravi; Simpson, David; Wang, Yujue; Zheng, Jing; Yang, Yudong; Shang, Dongjie; Wang, Haichao; Lu, Keding; Guo, Song; Hu, Min; Hallquist, Mattias

2017-04-01

Severe pollution events across China pose a major threat to air quality and climate through the direct emission of pollutants, but also via the production of photochemically induced secondary pollutants. Nitryl chloride (ClNO2), produced from heterogeneous reactions of dinitrogen pentoxide (N2O5) and aerosols containing chloride, is photolysed rapidly in sunlight and activates chlorine. Subsequent daytime oxidation via the chlorine atom can proceed orders of magnitude faster than that of the hydroxyl radical and therefore significantly perturb radical budgets and concentrations of ozone and secondary pollutants. Knowledge of the formation pathways, abundance and fate of these secondary pollutants, which can depend on ClNO2 abundance, is not fully understood but is necessary to support abatement strategies which will efficiently account for both primary and secondary pollutants. A Time of Flight Chemical Ionisation Mass Spectrometer (ToF CIMS) utilising the Filter Inlet for Gases and AEROsols (FIGAERO) was deployed in Changping, Beijing, during June and July, 2016 as part of an intercollaborative project to assess the photochemical smog in China. Concentrations of ClNO2 regularly exceeded 500 ppt throughout the campaign and reached a maximum concentration of 2.8 ppb, whereas relatively low N2O5 concentrations were observed, indicating a rapid heterogeneous production of ClNO2. Correlation of particulate chloride and carbon monoxide during the campaign suggests an anthropogenic chlorine source, also supported by high daytime Cl2 concentrations. Observations of ClNO2 desorptions using the FIGAERO suggest a possible unaccounted particulate reservoir of active chlorine in highly polluted regions. The persistence of ClNO2 several hours passed sunrise significantly increases the atomic chlorine production rate throughout the day further perturbing standard daytime oxidation processes. Simultaneous ToF CIMS measurements of Cl2, ClNO2, HCl, HOCl, OClO and ClONO2 were implemented into steady state calculations using the Master Chemical Mechanism (MCM) to assess how the daytime activation of chlorine competes with OH as a dominant oxidant in this heavily polluted region. The reactions of atomic chlorine with VOCs are traced and assessed via the gas and particle phase measurements of chlorinated VOCs and supporting Proton Transfer Reaction Mass Spectrometer (PTR MS) VOC measurements. This provides the first high frequency measurements of unique tracers for chlorine atom chemistry, several of which are represented in the MCM, in both the gas and particle phase and enable the detailed assessment of their diurnal variation and importance for photochemical smog formation.

Ab initio study of the chlorine nitrate protonation reaction - Implications for loss of ClONO2 in the stratosphere

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Rice, Julia E.

1993-01-01

Ab initio quantum mechanical methods, including coupled-cluster theory, are used to determine the equilibrium geometries, dipole moments, and harmonic vibrational frequencies of ClONO2, NO2(+), and four isomers of protonated ClONO2. It was found that, for the equilibrium structures and harmonic frequencies of ClONO2, HOCl, and NO2(+), the highest-level theoretical predictions are consistent with the available experimental information concerning the reactions of ClONO2 and HOCl with HCl on the surface of polar stratospheric clouds (PSCs). The study supports a recent hypothesis that the reaction of ClONO2 on the surface of PSCs is proton catalyzed, although the mechanism is different.

The consequences of global biomass burning

NASA Technical Reports Server (NTRS)

Levine, Joel S.

1991-01-01

Global biomass burning encompasses forest burning for land clearing, the annual burning of grasslands, the annual burning of agricultural stubble and waste after harvests, and the burning of wood as fuel. These activities generate CO2, CH4 and other hydrocarbons, CO, H2, NO, NH3, and CH3Cl; of these, CO, CH4 and the hydrocarbons, and NO, are involved in the photochemical production of tropospheric O3, while NO is transformed to NO2 and then to nitric acid, which falls as acid rain. Biomass burning is also a major source of atmospheric particulates and aerosols which affect the transmission of incoming solar radiation and outgoing IR radiation through the atmosphere, with significant climatic effects.

Groundwater quality from a part of Prakasam District, Andhra Pradesh, India

NASA Astrophysics Data System (ADS)

Subba Rao, N.

2018-03-01

Quality of groundwater is assessed from a part of Prakasam district, Andhra Pradesh, India. Groundwater samples collected from thirty locations from the study area were analysed for pH, electrical conductivity (EC), total dissolved solids (TDS), calcium (Ca2+), magnesium (Mg2+), sodium (Na+), potassium (K+), bicarbonate ( {HCO}3^{ - } ), chloride (Cl-), sulphate ( {SO}4^{2 - } ), nitrate ( {NO}3^{ - } ) and fluoride (F-). The results of the chemical analysis indicate that the groundwater is alkaline in nature and are mainly characterized by Na+- {HCO}3^{ - } and Na+-Cl- facies. Groundwater chemistry reflects the dominance of rock weathering and is subsequently modified by human activities, which are supported by genetic geochemical evolution and hydrogeochemical relations. Further, the chemical parameters (pH, TDS, Ca2+, Mg2+, Na+, {HCO}3^{ - } , Cl-, {SO}4^{2 - } , {NO}3^{ - } and F-) were compared with the drinking water quality standards. The sodium adsorption ratio, percent sodium, permeability index, residual sodium carbonate, magnesium ratio and Kelly's ratio were computed and USSL, Wilcox and Doneen's diagrams were also used for evaluation of groundwater quality for irrigation. For industrial purpose, the pH, TDS, {HCO}3^{ - } , Cl- and {SO}4^{2 - } were used to assess the impact of incrustation and corrosion activities on metal surfaces. As a whole, it is observed that the groundwater quality is not suitable for drinking, irrigation and industrial purposes due to one or more chemical parameters exceeding their standard limits. Therefore, groundwater management measures were suggested to improve the water quality.

A redox-based mechanism for induction of interleukin-1 production by nitric oxide in a human colonic epithelial cell line (HT29-Cl.16E).

PubMed Central

Vallette, G; Jarry, A; Branka, J E; Laboisse, C L

1996-01-01

We evaluated the effects of two NO donors, sodium nitroprusside (SNP) and 3-morpholino-sydnonimine (SIN-1), characterized by alternative redox states, i.e. nitrosonium ion (NO+) and nitric oxide (NO.) respectively, on intracellular interleukin-1 (IL-1) production, by a human colonic epithelial cell line (HT29-Cl.16E). SNP was able to induce intracellular IL-1 alpha production up to 10 h incubation, in a dose-dependent manner. Several experiments provide evidence that the NO+ redox form, and not the free radical NO., is implicated in the IL-1 alpha production: (i) SIN-1, devoid of any NO+ character, led to a very weak IL-1 production as compared with SNP; (ii) the reductive action of a thiol such as cysteine on NO+ led to a dose-dependent increase in NO, concentration, measured as NO2-/NO3- accumulation, and to large decrease in IL-1 production. Dibutyryl cGMP had no effect on IL-1 production, this finding supporting the concept that a cGMP-independent pathway is involved in the intracellular signalling of NO+. Together these results point out that NO, depending on its redox form, is able to modulate IL-1 production in cultured colonic epithelial cells. PMID:8546706

A redox-based mechanism for induction of interleukin-1 production by nitric oxide in a human colonic epithelial cell line (HT29-Cl.16E).

PubMed

Vallette, G; Jarry, A; Branka, J E; Laboisse, C L

1996-01-01

We evaluated the effects of two NO donors, sodium nitroprusside (SNP) and 3-morpholino-sydnonimine (SIN-1), characterized by alternative redox states, i.e. nitrosonium ion (NO+) and nitric oxide (NO.) respectively, on intracellular interleukin-1 (IL-1) production, by a human colonic epithelial cell line (HT29-Cl.16E). SNP was able to induce intracellular IL-1 alpha production up to 10 h incubation, in a dose-dependent manner. Several experiments provide evidence that the NO+ redox form, and not the free radical NO., is implicated in the IL-1 alpha production: (i) SIN-1, devoid of any NO+ character, led to a very weak IL-1 production as compared with SNP; (ii) the reductive action of a thiol such as cysteine on NO+ led to a dose-dependent increase in NO, concentration, measured as NO2-/NO3- accumulation, and to large decrease in IL-1 production. Dibutyryl cGMP had no effect on IL-1 production, this finding supporting the concept that a cGMP-independent pathway is involved in the intracellular signalling of NO+. Together these results point out that NO, depending on its redox form, is able to modulate IL-1 production in cultured colonic epithelial cells.

Reactivity of 2-ethyl-1-hexanol in the atmosphere.

PubMed

Gallego-Iniesta García, María Paz; Moreno Sanroma, Alberto; Martín Porrero, María Pilar; Tapia Valle, Araceli; Cabañas Galán, Beatriz; Salgado Muñoz, María Sagrario

2010-04-07

Rate coefficients at room temperature for the reaction of 2-ethyl-1-hexanol with OH and NO(3) radicals and with Cl atoms have been determined in a 150 L PTFE chamber using GC-FID/SPME and FTIR as detection systems. The rate coefficients k (in units of cm(3) molecule(-1) s(-1)) obtained were: (1.13 +/- 0.31) 10(-11) for the OH reaction, (2.93 +/- 0.92) 10(-15) for the NO(3) reaction and (1.88 +/- 0.25) 10(-10) for the Cl reaction. Despite the high concentrations of 2-ethyl-1-hexanol, especially in indoor air, this is the first kinetic study carried out to date for these reactions. The results are consistent with the expected reactivity given the chemical structure of 2-ethyl-1-hexanol. Calculated atmospheric lifetimes reveal that the dominant loss process for 2-ethyl-1-hexanol is clearly the daytime reaction with the hydroxyl radical.

CHAiOS: Chemistry of Halogens at the Isles of Shoals

NASA Astrophysics Data System (ADS)

Keene, W. C.; Stutz, J.; Pszenny, A. A.; Russell, L.; von Glasow, R.; Sive, B.; Varner, R.

2005-12-01

During summer 2004, a comprehensive suite of reactive trace gases (including halogen radicals and precursors, O3, reactive N, soluble acids, NH3, HCHO, SO2, hydrocarbons, and halocarbons), the chemical and physical characteristics of size-resolved aerosols, actinic flux, and related physical conditions was measured at Appledore Island, ME as part of the International Consortium for Atmospheric Research on Transport and Transformations (ICARTT). Acid displacement of sea-salt Cl- primarily by HNO3 sustained high HCl mixing ratios (often >2000 pptv or >5 * 1010 cm-3) during daytime. HCl + OH produced 105 to 106 Cl atoms cm-3 sec-1. Cl* (including HOCl and Cl2) typically ranged from <20 (<5 * 108 cm-3) to about 100 pptv (3 * 109 cm-3). Depending on its assumed composition, Cl* photolysis yielded an additional source for Cl ranging from <104 to 107 atoms cm-3 sec-1. Maximum steady-state Cl concentrations during daytime (104 to 106 atoms cm-3) indicated significant contributions to oxidizing capacity. IO, OIO, and I2 were quantified simultaneously by long-path and MAX DOAS. IO ranged from <1.8 to 7 pptv, was detected only during daytime at wind speeds >2 m sec-1, and was uncorrelated with tidal height. For the first time, OIO was detected during daytime indicating that photolysis was an unimportant sink. The presence of OIO at high NOx implies unknown chemical pathways. Calculations with the 1-D photochemical model MISTRA predict longer lifetimes for OIO relative to IO, consistent with observations. I chemistry influenced ozone significantly by direct reaction (e.g., I + O3 → IO + O2) and by changing OH/HO2 and NO/NO2 ratios. Aerosols in all size fractions were highly enriched in I relative to sea salt (factors of 102 to 105) indicating active multiphase transformations. Numerous aerosol growth events were detected some of which were associated with elevated IO and OIO. However, the lack of consistent correlation with iodine species suggests that I chemistry may not be the dominant nucleation pathway in polluted coastal New England air. Br radical chemistry was relatively unimportant.

ClC-3 deficiency protects preadipocytes against apoptosis induced by palmitate in vitro and in type 2 diabetes mice.

PubMed

Huang, Yun-Ying; Huang, Xiong-Qin; Zhao, Li-Yan; Sun, Fang-Yun; Chen, Wen-Liang; Du, Jie-Yi; Yuan, Feng; Li, Jie; Huang, Xue-Lian; Liu, Jie; Lv, Xiao-Fei; Guan, Yong-Yuan; Chen, Jian-Wen; Wang, Guan-Lei

2014-11-01

Palmitate, a common saturated free fatty acid (FFA), has been demonstrated to induce preadipocyte apoptosis in the absence of adipogenic stimuli, suggesting that preadipocytes may be prone to apoptosis under adipogenic insufficient conditions, like type 2 diabetes mellitus (T2DM). ClC-3, encoding Cl(-) channel or Cl(-)/H(+) antiporter, is critical for cell fate choices of proliferation versus apoptosis under diseased conditions. However, it is unknown whether ClC-3 is related with preadipocyte apoptosis induced by palmitate or T2DM. Palmitate, but not oleate, induced apoptosis and increase in ClC-3 protein expression and endoplasmic reticulum (ER) stress in 3T3-L1 preadipocyte. ClC-3 specific siRNA attenuated palmitate-induced apoptosis and increased protein levels of Grp78, ATF4, CHOP and phosphorylation of JNK1/2, whereas had no effects on increased phospho-PERK and phospho-eIF2α protein expression. Moreover, the enhanced apoptosis was shown in preadipocytes from high-sucrose/fat, low-dose STZ induced T2DM mouse model with hyperglycemia, hyperlipidemia (elevated serum TG and FFA levels) and insulin resistance. ClC-3 knockout significantly attenuated preadipocyte apoptosis and the above metabolic disorders in T2DM mice. These data demonstrated that ClC-3 deficiency prevent preadipocytes against palmitate-induced apoptosis via suppressing ER stress, and also suggested that ClC-3 may play a role in regulating cellular apoptosis and disorders of glucose and lipid metabolism during T2DM.

Chloride fluxes in crab muscle fibres

PubMed Central

Richards, C. D.

1969-01-01

1. Isotopic techniques were used to study the efflux of Cl- from single cannulated muscle fibres of the crab Maia squinado. 2. The efflux of 36Cl- was found to be exponential with steady rate constants ranging from 0·01 to 0·07 min-1. The steady efflux was ca. 1000-2000 pM cm-2 sec-1. The efflux was slightly depressed by K+-free saline and was unaffected by 40 mM-K+ saline and NO3- saline. The influx and efflux of Cl- were presumed independent. 3. The membrane conductance calculated from 36Cl- flux data was consistent with that determined by the method of electrotonic spread for other marine crustacean muscle fibres. Cl- accounted for most of the membrane conductance. PMID:5770889

Binding of (/sup 3/H)Forskolin to rat brain membranes

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

Seamon, K.B.; Vaillancourt, R.; Edwards, M.

1984-08-01

(12-/sup 3/H)Forskolin (27 Ci/mmol) has been used to study binding sites in rat brain tissue by using both centrifugation and filtration assays. The binding isotherm measured in the presence of 5 mM MgCl/sub 2/ by using the centrifugation assay is described best by a two-site model: K/sub d1/ = 15 nM, B/sub max/sub 1// (maximal binding) = 270 fmol/mg of protein; K/sub d2/ = 1.1 ..mu..M; B/sub max/sub 2// = 4.2 pmol/mg of protein. Only the high-affinity binding sites are detected when the binding is determined by using a filtration assay; K/sub d/ = 26 nM, B/sub max/ = 400more » fmol/mg of protein. Analogs of forskolin that do not activate adenylate cyclase (EC 4.6.1.1) do not compete effectively for (/sup 3/H)forskolin binding sites. Analogs of forskolin that are less potent than forskolin in activating adenylate cyclase are also less potent in competing for forskolin binding sites. The presence of 5 mM MgCl/sub 2/ or MnCl/sub 2/ was found to enhance binding. In the presence of 1 mM EDTA the amount of high-affinity binding is reduced to 110 fmol/mg of protein with no change in K/sub d/. There is no effect of CaCl/sub 2/ (20 mM) or NaCl (100 mM) on the binding. No high-affinity binding can be detected in membranes from ram sperm, which contains an adenylate cyclase that is not activated by forskolin. It is proposed that the high-affinity binding sites for forskolin are associated with the activated complex of catalytic subunit and stimulatory guanine nucleotide binding protein. 23 references, 5 figures, 2 tables.« less

Phosphine and diphosphine complexes of silicon(IV) halides.

PubMed

Levason, William; Pugh, David; Reid, Gillian

2013-05-06

The reaction of SiX4 (X = Cl or Br) with PMe3 in anhydrous CH2Cl2 forms trans-[SiX4(PMe3)2], while the diphosphines, Me2P(CH2)2PMe2, Et2P(CH2)2PEt2, and o-C6H4(PMe2)2 form cis-[SiX4(diphosphine)], all containing six-coordinate silicon centers. With Me2PCH2PMe2 the product was trans-[SiCl4(κ(1)-Me2PCH2PMe2)2]. The complexes have been characterized by X-ray crystallography, microanalysis, IR, and multinuclear ((1)H, (13)C{(1)H}, and (31)P{(1)H}) NMR spectroscopies. The complexes are stable solids and not significantly dissociated in nondonor solvents, although they are very moisture and oxygen sensitive. This stability conflicts with the predictions of recent density functional theory (DFT) calculations (Wilson et al. Inorg. Chem. 2012, 51, 7657-7668) which suggested six-coordinate silicon phosphines would be unstable, and also contrasts with the failure to isolate complexes with SiF4 (George et al. Dalton Trans. 2011, 40, 1584-1593). No reaction occurred between phosphines and SiI4, or with SiX4 and arsine ligands including AsMe3 and o-C6H4(AsMe2)2. Attempts to make five-coordinate [SiX4(PR3)] using the sterically bulky phosphines, P(t)Bu3, P(i)Pr3, or PCy3 failed, with no apparent reaction occurring, consistent with predictions (Wilson et al. Inorg. Chem. 2012, 51, 7657-7668) that such compounds would be very endothermic, while the large cone angles of the phosphines presumably preclude formation of six-coordination at the small silicon center. The reaction of Si2Cl6 with PMe3 or the diphosphines in CH2Cl2 results in instant disproportionation to the SiCl4 adducts and polychlorosilanes, but from hexane solution very unstable white [Si2Cl6(PMe3)2] and [Si2Cl6(diphosphine)] (diphosphine = Me2P(CH2)2PMe2 or o-C6H4(PMe2)2) precipitate. The reactions of SiHCl3 with PMe3 and Me2P(CH2)2PMe2 also produce the SiCl4 adducts, but using Et2P(CH2)2PEt2, colorless [SiHCl3{Et2P(CH2)2PEt2}] was isolated, which was characterized by an X-ray structure which showed a pseudo-octahedral complex with the Si-H trans to P. Attempts to reduce the silicon(IV) phosphine complexes to silicon(II) were unsuccessful, contrasting with the isolation of stable N-heterocyclic carbene adducts of Si(II).

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.

Regulation of net bicarbonate transport in rabbit cortical collecting tubule by peritubular pH, carbon dioxide tension, and bicarbonate concentration.

PubMed Central

Breyer, M D; Kokko, J P; Jacobson, H R

1986-01-01

The effects of changes in peritubular pH, carbon dioxide tension (PCO2), and HCO3- concentration on net HCO3- transport was examined in in vitro perfused cortical collecting tubules (CCTs) from unpretreated New Zealand white rabbits. Lowering peritubular HCO3- concentration and pH by reciprocal replacement of HCO3- with Cl-, significantly stimulated net HCO3- absorption. Lowering peritubular HCO3- concentration and pH, by substitution of HCO3- with gluconate, while keeping Cl- concentration constant, also stimulated net HCO3- absorption. Raising peritubular HCO3- concentration and pH, by reciprocal replacement of Cl- with HCO3-, inhibited net HCO3- absorption (or stimulated net HCO3- secretion). When the tubule was cooled, raising peritubular HCO3- concentration had no effect on net HCO3- transport, suggesting these results are not due to the passive flux of HCO3- down its concentration gradient. The effect of changes in ambient PCO2 on net HCO3- transport were also studied. Increasing the ambient PCO2 from 40 mmHg to either 80 or 120 mmHg, allowing pH to fall, had no effect on net HCO3- transport. Similarly, lowering ambient PCO2 to 14 mmHg had no effect on net HCO3- transport. Simultaneously increasing peritubular HCO3- concentration and PCO2, without accompanying changes in peritubular pH, i.e., isohydric changes, stimulated net HCO3- secretion to the same degree as nonisohydric increases in peritubular HCO3- concentration. Likewise, isohydric lowering of peritubular HCO3- concentration and PCO2 stimulated net HCO3- absorption. We conclude that: acute changes in peritubular HCO3- concentration regulate acidification in the CCT and these effects are mediated by a transcellular process; acute changes in ambient PCO2 within the physiologic range have no effect on HCO3- transport in the in vitro perfused CCT; and acute in vitro regulation of CCT acidification is independent of peritubular pH. PMID:3084564

Balloon profiles of stratospheric NO2 and HNO3 for testing the heterogeneous hydrolysis of N2O5 on sulfate aerosols

NASA Technical Reports Server (NTRS)

Webster, C. R.; May, R. D.; Allen, M.; Jaegle, L.; Mccormick, M. P.

1994-01-01

Simultaneous in situ measurements of stratospheric NO2, HNO3, HCl, and CH4 from 34 to 24 km were made in August 1992 from Palestine, Texas, using the Balloon-borne Laser In-Situ Sensor (BLISS) tunable diode laser spectrometer. Although the measurements of NO2, HNO3, and NO2/HNO3 agree well with gas-phase model calculations near 34 km where Stratospheric Aerosol and Gas Experiment (SAGE) 2 data show little sulfate aerosol, this is not true at the lower altitudes where SAGE 2 shows high aerosol loadings. At 24 km the BLISS NO2 and HNO3 measurements are 70% lower and 50% higher, respectively, than the gas phase model predictions, with a measured NO2/HNO3 ratio 5 times smaller. When the heterogeneous hydrolysis of N2O5 and ClONO2 on sulfate aerosol of surface area densities matching the SAGE 2 measurements is added to the model, good agreement with the BLISS measurements is found over the whole altitude range.

Survival and reproduction of enchytraeid worms, Oligochaeta, in different soil types amended with energetic cyclic nitramines.

PubMed

Dodard, Sabine G; Sunahara, Geoffrey I; Kuperman, Roman G; Sarrazin, Manon; Gong, Ping; Ampleman, Guy; Thiboutot, Sonia; Hawari, Jalal

2005-10-01

Hexanitrohexaazaisowurtzitane (CL-20), a new polycyclic polynitramine, has the same functional nitramine groups (N-NO2) as the widely used energetic chemicals hexahydro-1,3,5-trinitro-1,3,5-triazacyclohexane (royal demolition explosive [RDX]) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (high-melting explosive [HMX]). Potential impacts of CL-20 as an emerging contaminant must be assessed before its use. The effects of CL-20, RDX, or HMX on adult survival and juvenile production by potworms Enchytraeus albidus and Enchytraeus crypticus were studied in three soil types, including Sassafras sandy loam (1.2% organic matter [OM], 11% clay, pH 5.5), an agricultural soil (42% OM, 1% clay, pH 8.2), and a composite agricultural-forest soil (23% OM, 2% clay, pH 7.9) by using ISO method 16387 (International Standard Organization, Geneva, Switzerland). Results showed that CL-20 was toxic to E. crypticus with median lethal concentration values for adult survival ranging from 0.1 to 0.7 mg/kg dry mass (DM) when using the three tested soils. In addition, CL-20 adversely affected juvenile production by both species in all soils tested, with median effective concentration (EC50) values ranging from 0.08 to 0.62 mg/kg DM. Enchytraeus crypticus and E. albidus were similarly sensitive to CL-20 exposure in the composite agricultural-forest soil, which supported reproduction by both species and enabled comparisons. Correlation analysis showed weak or no relationship overall among the soil properties and reproduction toxicity endpoints. Neither RDX nor HMX affected (p > 0.05) adult survival of either species below 658 and 918 mg/kg DM, respectively, indicating that CL-20 is more toxic to enchytraeids than RDX or HMX. Examination of data shows that CL-20 should be considered as a potential reproductive toxicant to soil invertebrates, and that safeguards should be considered to minimize the potential for release of CL-20 into the environment.

Exploring the Reactivity Trends in the E2 and SN2 Reactions of X(-) + CH3CH2Cl (X = F, Cl, Br, HO, HS, HSe, NH2 PH2, AsH2, CH3, SiH3, and GeH3).

PubMed

Wu, Xiao-Peng; Sun, Xiao-Ming; Wei, Xi-Guang; Ren, Yi; Wong, Ning-Bew; Li, Wai-Kee

2009-06-09

The reactivity order of 12 anions toward ethyl chloride has been investigated by using the G2(+) method, and the competitive E2 and SN2 reactions are discussed and compared. The reactions studied are X(-) + CH3CH2Cl → HX + CH2═CH2 + Cl(-) and X(-) + CH3CH2Cl → CH3CH2X + Cl(-), with X = F, Cl, Br, HO, HS, HSe, NH2 PH2, AsH2, CH3, SiH3, and GeH3. Our results indicate that there is no general and straightforward relationship between the overall barriers and the proton affinity (PA) of X(-); instead, discernible linear correlations only exist for the X's within the same group of the periodic table. Similar correlations are also found with the electronegativity of central atoms in X, deformation energy of the E2 transition state (TS), and the overall enthalpy of reaction. It is revealed that the electronegativity will significantly affect the barrier height, and a more electronegative X will stabilize the E2 and SN2 transition states. Multiple linear regression analysis shows that there is a reasonable linear correlation between E2 (or SN2) overall barriers and the linear combination of PA of X(-) and electronegativity of the central atom.

Biotic and abiotic processes controlling water chemistry during snowmelt at rabbit ears pass, Rocky Mountains, Colorado, U.S.A.

USGS Publications Warehouse

Peters, N.E.; Leavesley, G.H.

1995-01-01

The chemical composition of snowmelt, groundwater, and streamwater was monitored during the spring of 1991 and 1992 in a 200-ha subalpine catchment on the western flank of the Rocky Mountains near Steamboat Springs, Colorado. Most of the snowmelt occurred during a one-month period annually that began in mid-May 1991 and mid-April 1992. The average water quality characteristics of individual sampling sites (meltwater, streamwater, and groundwater) were similar in 1991 and 1992. The major ions in meltwater were differentially eluted from the snowpack, and meltwater was dominated by Ca2+, SO4/2-, and NO3/-. Groundwater and streamwater were dominated by weathering products, including Ca2+, HCO3/- (measured as alkalinity), and SiO2, and their concentrations decreased as snowmelt progressed. One well had extremely high NO3/- concentrations, which were balanced by Ca2+ concentrations. For this well, hydrogen ion was hypothesized to be generated from nitrification in overlying soils, and subsequently exchanged with other cations, particularly Ca2+. Solute concentrations in streamwater also decreased as snowmelt progressed. Variations in groundwater levels and solute concentrations indicate thai most of the meltwater traveled through the surficial materials. A mass balance for 1992 indicated that the watershed retained H+, NH4/+, NO3/-, SO4/2- and Cl- and was the primary source of base cations and other weathering products. Proportionally more SO4/2- was deposited with the unusually high summer rainfall in 1992 compared to that released from snowmelt, whereas NO3/- was higher in snowmelt and Cl- was the same. The sum of snowmelt and rainfall could account for greater than 90% of the H+ and NH4/+ retained by the watershed and greater than 50% of the NO3/-.The chemical composition of snowmelt, groundwater, and streamwater was monitored during the spring of 1991 and 1992 in a 200-ha subalpine catchment on the western flank of the Rocky Mountains near Steamboat Springs, Colorado. The major ions in meltwater were differentially eluted from the snowpack, and meltwater was dominated by Ca2+, SO42-, and NO3-. Groundwater and streamwater were dominated by weathering products and their concentrations decreased as snowmelt progressed. Solute concentrations in streamwater also decreased as snowmelt progressed. A mass balance for 1992 showed that the watershed retained H+, NH4+, NO3-, SO42- and Cl- and was the primary source of base cations and other weathering products.

Microbiological, physicochemical, and heavy metals assessment of groundwater quality in the Triffa plain (eastern Morocco)

NASA Astrophysics Data System (ADS)

Yahya, Hameed Saleh Ali; Jilali, Abdelhakim; Mostareh, Mohammed Mohammed Mohammed; Chafik, Zouheir; Chafi, Abdelhafid

2017-12-01

The focus of this study is the physicochemical and bacteriological characteristics of groundwater in the Triffa plain, Morocco. In total, 34 groundwater samples were analyzed for major elements (Tp, pH, EC, K+, Na+, Ca2+, Mg2+, Cl-, SO4 2-, NO3 -, NO2 -, NH4 +, H2PO4 -, CO3, and HCO3 -) and trace metal (Al, Cd, Cu, Fe, and Zn) content. The results show that the pH values range between 6.7 and 8.9, electrical conductivity ranges between 740 and 7340 µS/cm, and nitrate content ranges between 1.7 and 212 mg/l. Hydrochemical facies represented using a Piper diagram indicate an Na-K-Cl type water. All the trace metal concentrations are within the admissible standard range except for Cd. The bacteriological analysis showed that the majority of groundwater samples are contaminated. Generally, the content of total coliforms, fecal coliforms, and fecal streptococci ranged from 0 to 140, 0 to 125, and 0 to 108 CFU/100 ml, respectively. The samples are grouped according to three factors. Factor 1 shows strong positive loadings of EC, Mg, Cl, Na and K with 51.91% of total variance (TV); factor 2 shows strong negative loadings of NO3, SO4 and Ca with 17.98% of TV; and factor 3 shows strong negative loading of HCO3 with 15.56 of TV. We conclude that the quality of this groundwater is suitable for irrigation and domestic use (cleaning house, ect).

Impact of supersonic and subsonic aircraft on ozone: Including heterogeneous chemical reaction mechanisms

NASA Technical Reports Server (NTRS)

Kinnison, Douglas E.; Wuebbles, Donald J.

1994-01-01

Preliminary calculations suggest that heterogeneous reactions are important in calculating the impact on ozone from emissions of trace gases from aircraft fleets. In this study, three heterogeneous chemical processes that occur on background sulfuric acid aerosols are included and their effects on O3, NO(x), Cl(x), HCl, N2O5, ClONO2 are calculated.

Ion chromatography for determination of nitrite and nitrate in seawater using monolithic ODS columns.

PubMed

Ito, Kazuaki; Takayama, Yohichi; Makabe, Nobuyuki; Mitsui, Ryo; Hirokawa, Takeshi

2005-08-12

A fast and highly sensitive ion chromatographic method using monolithic ODS columns was developed for the determination of nitrite (NO2-) and nitrate (NO3-) in seawater. Two monolithic ODS columns (50 mm x 4.6 mm i.d. + 100 mm x 4.6 mm i.d.) connected in series were coated and equilibrated with 5 mM cetyltrimethylammonium chloride (CTAC) aqueous solution. The column efficiency with 0.5 M NaCl as the mobile phase did not decrease in spite of the increase in flow rate of the mobile phase. Thus, good chromatograms were obtained within 3 minutes for NO2- and NO3 in artificial seawater without interferences by coexisting ions. The detection limit (S/N = 3) with UV detection at 225 nm was 0.8 and 1.6 microg/L for NO2- and NO3-, respectively. The characteristics of the monolithic CTA(+)-coated ODS columns were discussed. The present method was successfully applied to the fast and sensitive determination of NO2- and NO3- in real seawater samples.

The indoor-outdoor characteristics of water-soluble ion in PM2.5 in Tianjin wintertime.

PubMed

Wang, Baoqing; Niu, Honghong; Liu, Bowei; Hu, Xinxin; Ren, Zihui

2018-05-15

The indoor and outdoor PM 2.5 mass concentration, water-soluble ion by filter sampler was analyzed on December 3-21, 2015 during wintertime in Tianjin, China. The results indicate that high humidity conditions result in the accumulation of atmospheric pollutants and reduce atmosphere visibility. The I/O ratio for PM 2.5 concentration in dormitory and lab are less than 1 in haze days. Indoor PM 2.5 concentration increases rapidly with outdoor PM 2.5 concentration increasing in haze days. The filtration factors of the dormitory and lab indicate nearly half of the outdoor PM 2.5 enters indoor environment. The human activities in dormitory could cause more the formation of PM 2.5 than those in lab. The concentration of SO 4 2- is the highest ion in water-soluble ion for outdoor PM 2.5 . The SO 4 2- , NO 3 - , NH 4 + , and Cl - are generated mainly by outdoor sources; however, the Na + , Ca 2+ , and Mg 2+ are generated mainly by indoor sources. The NH 4 NO 3 , (NH 4 ) 2 SO 4 , and NH 4 Cl accounts for 20.2~41.8%, 32.0~51.4%, and 6.4~10.6% of the total water-soluble ion in different indoor-outdoor environment. The total secondary aerosols including NH 4 NO 3 , (NH 4 ) 2 SO 4 , and NH 4 Cl in PM 2.5 are 28.3, 42.1, 28.2, 31.0, and 33.9% in outdoor environment for haze days, outdoor environment for non-haze days, dormitory for haze days, dormitory for non-haze days, and lab for haze days, respectively.

Effect of temperature on chlorine dioxide inactivation of Escherichia coli O157:H7, Salmonella typhimurium, and Listeria monocytogenes on spinach, tomatoes, stainless steel, and glass surfaces.

PubMed

Park, Sang-Hyun; Kang, Dong-Hyun

2018-06-20

The objective of this study was to evaluate how treatment temperature influences the solubility of ClO 2 gas and the antimicrobial effect of ClO 2 gas against Escherichia coli O157:H7, Salmonella Typhimurium, and Listeria monocytogenes on produce and food contact surfaces. Produce and food contact surfaces inoculated with a combined culture cocktail of three strains each of the three foodborne pathogens were processed in a treatment chamber with 20 ppmv ClO 2 gas at 15 or 25 °C under the same conditions of absolute humidity (11.2-12.3 g/m 3 ) for up to 30 min. As treatment time increased, ClO 2 gas treatment at 15 °C caused significantly more (p < 0.05) inactivation of the three pathogens than treatment at 25 °C. ClO 2 gas treatment at 25 °C for 30 min resulted in 1.15 to 1.54, 1.53 to 1.88, and 1.00 to 1.78 log reductions of the three pathogens on spinach leaves, tomatoes, and stainless steel No.4, respectively. ClO 2 gas treatment at 15 °C for 30 min caused 2.53 to 2.88, 2.82 to 3.23, and 2.37 to 3.03 log reductions of the three pathogens on spinach leaves, tomatoes, and stainless steel No.4, respectively. Treatment with ClO 2 gas at 25 °C for 20 min resulted in 1.88 to 2.31 log reductions of the three pathogens on glass while >5.91 to 6.82 log reductions of these pathogens occurred after 20 min when treated at 15 °C. Residual ClO 2 levels after gas treatment at 15 °C were significantly (p < 0.05) higher than those at 25 °C. The results of this study can help the food processing industry establish optimum ClO 2 gas treatment conditions for maximizing the antimicrobial efficacy of ClO 2 gas. Published by Elsevier B.V.

MILSCAP: Military Standard Contract Administration Procedures. Change 1

DTIC Science & Technology

1994-06-15

AD-A284 618 DEFENSE LOGISTICS AGENCY 0DoD4000.25-5-K HEADQUARTERSDO40.25- CAMERON STATION ALEXANDRIA, VIRGINIA 22304-6100 DLMSO CHANGE NO. 1 15 Jun...effective upon receipt. II. Incorporated in change 1 are AMCL 1 , recent changes to the Transportation Priority Codes (appendix A29), updates to...A52- 1 xvii to xix xvii to xix Cl-i to C1-3 Cl-i to Cl-3 1 -7 to 1 -10 1 -7 to 1 -10 C19- 1 and C19-2 C19- 1 and C19-2 5-3 and 5-4 5-3 and 5-4 C24- 1 to C24-3

A thermodynamic study of electroneutral K-Cl cotransport in pH- and volume-clamped low K sheep erythrocytes with normal and low internal magnesium.

PubMed

Lauf, P K; Adragna, N C

1996-10-01

Swelling-induced human erythrocyte K-Cl cotransport is membrane potential independent and capable of uphill transport. However, a complete thermodynamic analysis of basal and stimulated K-Cl cotransport, at constant cell volume, is missing. This study was performed in low K sheep red blood cells before and after reducing cellular free Mg into the nanomolar range with the divalent cation ionophore A23187 and a chelator, an intervention known to stimulate K-Cl cotransport. The anion exchange inhibitor 4,4'diisothiocyanato-2,2'disulfonic stilbene was used to clamp intracellular pH and Cl or NO3 concentrations. Cell volume was maintained constant as external and internal pH differed by more than two units. K-Cl cotransport was calculated from the K effluxes and Rb (as K congener) influxes measured in Cl and NO3, at constant internal K and external anions, and variable concentrations of extracellular Rb and internal anions, respectively. The external Rb concentration at which net K-Cl cotransport is zero was defined as flux reversal point which changed with internal pH and hence Cl. Plots of the ratio of external Rb concentrations corresponding to the flux reversal points and the internal K concentration versus the ratio of the internal and external Cl concentrations (i.e., the Donnan ratio of the transported ions) yielded slopes near unity for both control and low internal Mg cells. Thus, basal as well as low internal Mg-stimulated net K-Cl cotransport depends on the electrochemical potential gradient of KCl.

A thermodynamic study of electroneutral K-Cl cotransport in pH- and volume-clamped low K sheep erythrocytes with normal and low internal magnesium

PubMed Central

1996-01-01

Swelling-induced human erythrocyte K-Cl cotransport is membrane potential independent and capable of uphill transport. However, a complete thermodynamic analysis of basal and stimulated K-Cl cotransport, at constant cell volume, is missing. This study was performed in low K sheep red blood cells before and after reducing cellular free Mg into the nanomolar range with the divalent cation ionophore A23187 and a chelator, an intervention known to stimulate K- Cl cotransport. The anion exchange inhibitor 4,4'diisothiocyanato- 2,2'disulfonic stilbene was used to clamp intracellular pH and Cl or NO3 concentrations. Cell volume was maintained constant as external and internal pH differed by more than two units. K-Cl cotransport was calculated from the K effluxes and Rb (as K congener) influxes measured in Cl and NO3, at constant internal K and external anions, and variable concentrations of extracellular Rb and internal anions, respectively. The external Rb concentration at which net K-Cl cotransport is zero was defined as flux reversal point which changed with internal pH and hence Cl. Plots of the ratio of external Rb concentrations corresponding to the flux reversal points and the internal K concentration versus the ratio of the internal and external Cl concentrations (i.e., the Donnan ratio of the transported ions) yielded slopes near unity for both control and low internal Mg cells. Thus, basal as well as low internal Mg-stimulated net K-Cl cotransport depends on the electrochemical potential gradient of KCl. PMID:8894982

Comparisons of MN2S2vs. bipyridine as redox-active ligands to manganese and rhenium in (L-L)M'(CO)3Cl complexes.

PubMed

Lunsford, Allen M; Goldstein, Kristina F; Cohan, Matthew A; Denny, Jason A; Bhuvanesh, Nattamai; Ding, Shengda; Hall, Michael B; Darensbourg, Marcetta Y

2017-04-19

The bipyridine ligand is renowned as a photo- and redox-active ligand in catalysis; the latter has been particularly explored in the complex Re(bipy)(CO) 3 Cl for CO 2 reduction. We ask whether a bidentate, redox-active MN 2 S 2 metallodithiolate ligand in heterobimetallic complexes of Mn and Re might similarly serve as a receptor and conduit of electrons. In order to assess the electrochemical features of such designed bimetallics, a series of complexes featuring redox active MN 2 S 2 metallodithiolates, with M = Ni 2+ , {Fe(NO)} 2+ , and {Co(NO)} 2+ , bound to M'(CO) 3 X, where M' = Mn and Re, were synthesized and characterized using IR and EPR spectroscopies, X-ray diffraction, cyclic voltammetry, and density functional theory (DFT) computations. Butterfly type structures resulted from binding of the convergent lone pairs of the cis-sulfur atoms to the M'(CO) 3 X unit. Bond distances and angles are similar across the M' metal series regardless of the ligand attached. Electrochemical characterizations of [MN 2 S 2 ·Re(CO) 3 Cl] showed the redox potential of the Re is significantly altered by the identity of the metal in the N 2 S 2 pocket. DFT calculations proved useful to identify the roles played by the MN 2 S 2 ligands, upon reduction of the bimetallics, in altering the lability of the Re-Cl bond and the ensuing effect on the reduction of Re I to Re 0 .

The chemistry of the severe acidic precipitation in Shanghai, China

NASA Astrophysics Data System (ADS)

Huang, Kan; Zhuang, Guoshun; Xu, Chang; Wang, Ying; Tang, Aohan

2008-07-01

Seventy-six rain samples from forty-seven rain events and TSP aerosol samples throughout the entire year of 2005 were collected in Shanghai, China. The annual mean pH in rain was 4.49 with the lowest pH of 2.95, and the frequency of acid rain was 71% in 2005. The acidity of rain increased more than 15 times in the past 8 years compared to 1997. The volume-weighted mean ionic concentrations of the acidic ions, SO 42- and NO 3- in rainwater were 199.59 and 49.80 μeq/L with maximum of 832.67 and 236.59 μeq/L, respectively. The concentration of SO 42- was higher than the most polluted cities abroad, indicating Shanghai has been a severe polluted city over the world. The high coal/fuel consumption from urbanization and the rapid increase of vehicles resulted in the high emission of SO 2 and NO x, the precursor of the high concentration of acidic ions, SO 42- and NO 3-, which were the main reason of the severe acid rain in Shanghai. The major ions showed clear temporal variations with higher concentrations of SO 42-, NO 3-, NH 4+, and Ca 2+ in spring/winter, of Na +, Cl -, K +, and Mg 2+ in autumn, and the lowest of all the ions in summer. SO 42- and NO 3- were mainly in the form of CaSO 4 and Ca(NO 3) 2, which showed the dominant neutralization effect of Ca 2+ over NH 4+. Source identification indicated that SO 42-, NO 3-, NH 4+ and most Ca 2+ derived from anthropogenic sources, K +, Mg 2+ and partial Ca 2+ originated from mineral, and almost all the Cl - and Na + from the sea. The chemistry of precipitation in Shanghai was under the influence of local pollution sources and the long- and moderate-range transport through back trajectory analysis.

Calcium ascorbate as a potential partial substitute for NaCl in dry fermented sausages: effect on colour, texture and hygienic quality at different concentrations.

PubMed

Gimeno, O; Astiasarán, I; Bello, J

2001-01-01

A control product (2.6% NaCl) and different treatments with reduced levels of salt (1, 2.3% NaCl; 2, 2.0% NaCl; 3, 1.7% NaCl; 4, 1.4% NaCl) and increased amounts of calcium ascorbate with an equivalent ionic strength to that of the control were assayed. The percentages of reduction of sodium content in relation to the control were 15, 24, 37 and 45% and the supply of calcium was 26, 33, 42 and 50% of the Recommended Dietary Allowance (RDAs established by NRC, US) for treatments 1, 2, 3 and 4, respectively. Partial substitution of NaCl by calcium ascorbate caused higher acidification related with the higher lactic acid bacteria development and probably with the presence of calcium. The instrumental measurement of colour gave rise to some significant differences especially with the highest amount of calcium ascorbate (treatment 4), giving rise to significant higher a* and b* values and lower L* values in relation to the control. Treatments 2, 3 and 4 lead to products with lower hardness and gumminess values than the control. No problems related to the hygienic quality were observed.

Four transition metal complexes with a semicarbazone ligand bearing pyrazine unit

NASA Astrophysics Data System (ADS)

Chen, Hong; Ma, Xiu-qin; Lv, Yan-yun; Jia, Lei; Xu, Jun; Wang, Yuan; Ge, Zhi-jun

2016-04-01

Four new complexes based on L (where L = 3-ethyl-2-acetylpyrazine semicarbazone), namely [CoL2]Cl2·0.5H2O (1), [CoL2](NO3)2 (2), [CdL(H2O)2(NO3)](NO3)·H2O (3) and [CuL(CH3OH)Cl2]·[CuLCl2] (4) have been synthesized and characterized by X-ray diffraction analyses. The results show that the semicarbazone acts as a tridentate neutral ligand in all complexes. Each of complex 1 and 2 reveals a distorted octahedral geometry around the metal ion provided by two units of the ligand, while the ratio of the ligand and metal is 1:1 in complexes 3 and 4. The effect of complexes 1-4 on cell proliferation, apoptosis of human pancreatic cancer (Patu8988), human gastric cancer (SGC7901) and human hepatic cancer (SMMC7721) cell lines have been detected by MTT assay, Annexin V/PI double staining flow cytometry and TUNEL assay. The results show that complexes 1-4 can inhibit cell proliferation of Patu8988, SGC7901 and SMMC7721 cells, significantly higher than the effect of the ligand. However, the complex 4 reveals higher apoptosis rate, and displays up-regulated expression level of caspase 3, detected by western blotting, which also indicates the complex 4 can induce caspase-dependent cell apoptosis in SMMC7721.

Measurements of ClONO2 by Improved Limb Atmospheric Spectrometer (ILAS) in the high latitude stratosphere

NASA Astrophysics Data System (ADS)

Nakajima, H.; Irie, H.; Sugita, T.; Yokota, T.; Sasano, Y.

2003-12-01

Improved Limb Atmospheric Spectrometer (ILAS) was a solar-occultation sensor onboard the ADEOS satellite. ILAS measured vertical profiles of O3, HNO3, NO2, N2O, CH4, H2O, and aerosol extinction coefficients at high latitude stratosphere from November 1996 to June 1997 [JGR, ILAS Special Section, Vol. 107, No. D24, 2002]. The latest retrieval algorithm of ILAS (Version 6.0) enabled us to retrieve vertical profiles of ClONO2 and N2O5 with typical vertical resolution of 1.6-2.0 km in addition to these species. The advantage of ILAS ClONO2 measurements is that it continuously measured this gas species at high latitude stratosphere with high vertical resolution. ILAS ClONO2 profiles were compared with correlative balloon-borne measurements by MIPAS-B2 [Fischer and Oelhaf, 1996], FIRS-2 [Johnson et al., 1995], and MkIV [Toon, 1991]. In all comparisons, it was found that ILAS ClONO2 values were systematically lower by around 30% between 15 and 32 km altitudes. Also, the precision and accuracy of ILAS ClONO2 for altitude of 15-35 km were estimated to be around 20-40% and 30%, respectively. The Arctic winter/spring in 1996/1997 was characterized its relatively low temperature and its long lasting polar vortex. Many PSC activities were observed by ILAS in January-March 1997 [Hayashida et al., 2000]. ILAS succeeded to measure vertical profiles of ClONO2 for whole period of this Arctic winter/spring. After the PSC activity in February, enhancement of ClONO2 reaching 1.5 ppbv at around 20 km was observed for the data inside the polar vortex in March. In April 1997, enhanced ClONO2 amount decreased towards 1.0 ppbv at more than 10 days prior to the polar vortex breakup. This suggest the change of partitioning of chlorine species from ClONO2 into HCl at this period. Initial measurements of ClONO2 resumed by ILAS-II onboard the ADEOS-II satellite from April 2003 will also be presented at the meeting.

The effect of anions on bound acetylcholine in frog sartorius muscle.

PubMed Central

Ceccarelli, B; Molenaar, P C; Oen, B S; Polak, R L; Torri-Tarelli, F; van Kempen, G T

1989-01-01

1. Frog sartorius muscles were treated with an irreversible cholinesterase inhibitor and then incubated in isotonic potassium propionate solution (isotonic KPr). Total and bound, presumably vesicular, acetylcholine (ACh) in the tissue and ACh in the medium were assayed by mass fragmentography, miniature end-plate potentials (MEPPs) were recorded and the end-plates were investigated by electron microscopy. 2. Incubation in isotonic KPr for 30 min stimulated ACh release and concomitantly decreased total and bound ACh. Nerve stimulation for 30 min by trains of impulses (0.1 s trains of 100 Hz, 1 train s-1) in normal-potassium propionate-containing solution had the same effects. 3. When the tissue was incubated in normal-K+ Ringer solution for 3 h, following chemical or electric stimulation, bound ACh recovered to about 75% of the initial value, provided that Cl- ions were present in the medium. In the presence of propionate instead of Cl- ions almost no recovery of bound ACh took place. There was also recovery of bound ACh in the presence of either NO3- or gluconate ions. In NO3- it was the same as in Cl-, but in gluconate it was less than found in Cl- -containing medium. 4. Recovery of total ACh, in contrast to bound ACh, took place even in the presence of propionate ions, showing that extracellular Cl- is not required for the synthesis of ACh. 5. In terminals recovered in normal Ringer solution, many synaptic vesicles were found, but terminals 'recovered' in propionate solution were depleted of vesicles. 6. From these and other results it is concluded that the recycling of synaptic vesicles normally requires the presence of extracellular chloride. Images Fig. 1 Fig. 2 PMID:2789283

Kinetic response study in chemiresistive gas sensor based on carbon nanotube surface functionalized with substituted phthalocyanines

NASA Astrophysics Data System (ADS)

Sharma, Anshul Kumar; Kumar, Pankaj; Saini, Rajan; Bedi, R. K.; Mahajan, Aman

2016-05-01

A kind of hybrid material is prepared by functionalizing multi-wall carbon nanotubes (MWCNTs-COOH) with substituted copper phthalocyanine and the formation of CuPcOC8/MWCNTs-COOH hybrid is confirmed by scanning electron microscopy and transmission electron microscopy. The results indicated that on the surface of nanotubes substituted CuPcOC8 derivatives has been successfully anchored through π-π stacking interaction. The gas sensing application of the fabricated hybrid material is tested upon exposure to different hazardous species, specifically NO2, NO, Cl2 and NH3 at operating temperature of 150˚C. It has been demonstrated that for Cl2 minimum detection limit of CuPcOC8/MWCNTs-COOH hybrid is 100 ppb. The response of hybrid sensor is found to be increased with increase in the concentration of Cl2.

Kinetic response study in chemiresistive gas sensor based on carbon nanotube surface functionalized with substituted phthalocyanines

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

Sharma, Anshul Kumar; Saini, Rajan; Bedi, R. K.

2016-05-06

A kind of hybrid material is prepared by functionalizing multi-wall carbon nanotubes (MWCNTs-COOH) with substituted copper phthalocyanine and the formation of CuPcOC{sub 8}/MWCNTs-COOH hybrid is confirmed by scanning electron microscopy and transmission electron microscopy. The results indicated that on the surface of nanotubes substituted CuPcOC{sub 8} derivatives has been successfully anchored through π-π stacking interaction. The gas sensing application of the fabricated hybrid material is tested upon exposure to different hazardous species, specifically NO{sub 2}, NO, Cl{sub 2} and NH{sub 3} at operating temperature of 150°C. It has been demonstrated that for Cl{sub 2} minimum detection limit of CuPcOC{sub 8}/MWCNTs-COOHmore » hybrid is 100 ppb. The response of hybrid sensor is found to be increased with increase in the concentration of Cl{sub 2}.« less

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.

Atlas of absorption lines from 0 to 17 900 cm(-1)

NASA Technical Reports Server (NTRS)

Park, J. H.; Rothman, L. S.; Rinsland, C. P.; Smith, M. A. H.; Richardson, D. J.; Larsen, J. C.

1981-01-01

Plots of absorption line strength versus line position for wavenumbers from 0 to 17,900 cm(-1) are shown for 20 atmospheric gases (H2O, CO2, O3, N2O, CO, CH4, O2, NO, SO2, NO2, NH3, HNO3, OH, HF, HCl, HBr, HI, ClO, OCS, H2CO). Also shown are similar plots of lower-state energy values for adsorption lines for the strongly adsorbing atmospheric gases (H2O, CO2, O3, and CH4) for wavenumbers from 0 to 5000 cm(-1).

Polymethylated [Fe(η6-arene)2]2+ dications: methyl-group rearrangements and application of the EINS mechanism.

PubMed

Štíbr, Bohumil; Bakardjiev, Mario; Hájková, Zuzana; Holub, Josef; Padělková, Zdenka; Růžička, Aleš; Kennedy, John D

2011-06-14

Reactions between the methylated arenes ArMe(n) [where ArMe(n) = C(6)Me(n)H((6-n)), and n = 1-6] and FeCl(2) in heptane at 90 °C in the presence of anhydrous AlCl(3) give, for the arenes with n = 1-5, extensive isomerisations and disproportionations involving the methyl groups on the arene rings, and the formation of mixtures of [Fe(ArMe(n))(2)](2+) dications that defy separation into pure species. GC-MS studies of AlCl(3)/mesitylene and AlCl(3)/durene reactions in the absence of FeCl(2) (90 °C, 2 h) allow quantitative assessments of the rearrangements, and the EINS mechanism (electrophile-induced nucleophilic substitution) is applied to rationalise the phenomena. By contrast, ArMe(n) / FeCl(2) /AlCl(3) reactions in heptane for 24-36 h at room-temperature proceed with no rearrangements, allowing the synthesis of the complete series of pure [Fe(ArMen)](2+) cations in yields of 48-71%. The pure compounds are characterised by (1)H NMR spectroscopy and electrospray-ionization mass-spectrometry (ESI-MS), and the structures of [Fe(m-xylene)(2)][PF(6)](2) and [Fe(durene)(2)][PF(6)](2) are established by single-crystal X-ray diffraction analyses.

PDGF activates K-Cl cotransport through phosphoinositide 3-kinase and protein phosphatase-1 in primary cultures of vascular smooth muscle cells.

PubMed

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

2005-07-15

K-Cl cotransport (K-Cl COT, KCC) is an electroneutrally coupled movement of K and Cl present in most cells. In this work, we studied the pathways of regulation of K-Cl COT by platelet-derived growth factor (PDGF) in primary cultures of vascular smooth muscle cells (VSMCs). Wortmannin and LY 294002 blocked the PDGF-induced K-Cl COT activation, indicating that the phosphoinositide 3-kinase (PI 3-K) pathway is involved. However, PD 98059 had no effect on K-Cl COT activation by PDGF, suggesting that the mitogen-activated protein kinase pathway is not involved under the experimental conditions tested. Involvement of phosphatases was also examined. Sodium orthovanadate, cyclosporin A and okadaic acid had no effect on PDGF-stimulated K-Cl COT. Calyculin A blocked the PDGF-stimulated K-Cl COT by 60%, suggesting that protein phosphatase-1 (PP-1) is a mediator in the PDGF signaling pathway/s. In conclusion, our results indicate that the PDGF-mediated pathways of K-Cl COT regulation involve the signaling molecules PI 3-K and PP-1.

Heme oxygenase-1 induction improves ischemic renal failure: role of nitric oxide and peroxynitrite.

PubMed

Salom, Miguel G; Cerón, Susana Nieto; Rodriguez, Francisca; Lopez, Bernardo; Hernández, Isabel; Martínez, José Gil; Losa, Adoración Martínez; Fenoy, Francisco J

2007-12-01

The present study evaluated the effects of heme oxygenase-1 (HO-1) induction on the changes in renal outer medullary nitric oxide (NO) and peroxynitrite levels during 45-min renal ischemia and 30-min reperfusion in anesthetized rats. Glomerular filtration rate (GFR), outer medullary blood flow (OMBF), HO and nitric oxide synthase (NOS) isoform expression, and renal low-molecular-weight thiols (-SH) were also determined. During ischemia significant increases in NO levels and peroxynitrite signal were observed (from 832.1 +/- 129.3 to 2,928.6 +/- 502.0 nM and from 3.8 +/- 0.7 to 9.0 +/- 1.6 nA before and during ischemia, respectively) that dropped to preischemic levels during reperfusion. OMBF and -SH significantly decreased after 30 min of reperfusion. Twenty-four hours later, an acute renal failure was observed (GFR 923.0 +/- 66.0 and 253.6 +/- 55.3 microl.min(-1).g kidney wt(-1) in sham-operated and ischemic kidneys, respectively; P < 0.05). The induction of HO-1 (CoCl(2) 60 mg/kg sc, 24 h before ischemia) decreased basal NO concentration (99.7 +/- 41.0 nM), although endothelial and neuronal NOS expression were slightly increased. CoCl(2) administration also blunted the ischemic increase in NO and peroxynitrite (maximum values of 1,315.6 +/- 445.6 nM and 6.3 +/- 0.5 nA, respectively; P < 0.05), preserving postischemic OMBF and GFR (686.4 +/- 45.2 microl.min(-1).g kidney wt(-1)). These beneficial effects of CoCl(2) on ischemic acute renal failure seem to be due to HO-1 induction, because they were abolished by stannous mesoporphyrin, a HO inhibitor. In conclusion, HO-1 induction has a protective effect on ischemic renal failure that seems to be partially mediated by decreasing the excessive production of NO with the subsequent reduction in peroxynitrite formation observed during ischemia.

Nitrate pollution and surface water chemistry in Shimabara, Nagasaki Prefecture, Japan

NASA Astrophysics Data System (ADS)

Nakagawa, K.; Amano, H.

2017-12-01

Shimabara city has been experiencing serious nitrate pollution in groundwater. To evaluate nitrate pollution and water chemistry in surface water, water samples were collected at 42 sampling points in 15 rivers in Shimabara including a part of Unzen city from January to February 2017. Firstly, spatial distribution of water chemistry was assessed by describing stiff and piper-trilinear diagrams using major ions concentrations. Most of the samples showed Ca-HCO3 or Ca-(NO3+SO4) water types. It corresponds to groundwater chemistry. Some samples were classified into characteristic water types such as Na-Cl, (Na+K)-HCO3, and Ca-Cl. These results indicate sea water mixing and anthropogenic pollution. At the upstream of Nishi-river, although water chemistry showed Ca-HCO3, ions concentrations were higher than that of the other rivers. It indicates that this site was affected by the peripheral anthropogenic activities. Secondly, nitrate-pollution assessment was performed by using NO3-, NO2-, coprostanol (5β(H)-Cholestan-3β-ol), and cholestanol (5α(H)-Cholestan-3β-ol). NO2-N was detected at the 2 sampling points and exceeded drinking standard 0.9 mg L-1 for bottle-fed infants (WHO, 2011). NO3-N + NO2-N concentrations exceeded Japanese drinking standard 10 mg L-1 at 18 sampling points. The highest concentration was 27.5 mg L-1. Higher NO3-N levels were observed in the rivers in the northern parts of the study area. Coprostanol has been used as a fecal contamination indicator, since it can be found in only feces of higher animals. Coprostanol concentrations at 8 sampling points exceeded 700 ng L-1 (Australian drinking water standard). Coprostanol has a potential to distinguish the nitrate pollution sources between chemical fertilizer or livestock wastes, since water samples with similar NO3-N + NO2-N concentration showed distinct coprostanol concentration. The sterols ratio (5β/ (5β+5α)) exceeded 0.5 at 18 sampling points. This reveals that fecal pollution has occurred.

Molecular beam studies of stratospheric photochemistry

NASA Astrophysics Data System (ADS)

Moore, Teresa Anne

1998-12-01

Photochemistry of chlorine oxide containing species plays a major role in stratospheric ozone depletion. This thesis discusses two photodissociation studies of the key molecules ClONO2 and ClOOCl which were previously thought to only produce Cl-atom (ozone depleting) products at wavelengths relevant to the stratosphere. The development of a molecular beam source of ClOOCl and the photodissociation dynamics of the model system Cl2O are also discussed. In the first chapter, the photochemistry of ClONO2 is examined at 308 nm using the technique of photofragment translational spectroscopy. Two primary decomposition pathways, leading to Cl + NO3 and ClO + NO2, were observed, with a lower limit of 0.33 for the relative yield of ClO. The angular distributions for both channels were anisotropic, indicating that the dissociation occurs within a rotational period. Chapter two revisits the photodissociation dynamics of Cl2O at 248 and 308 nm, on which we had previously reported preliminary findings. At 248 nm, three distinct dissociation pathways leading to Cl + ClO products were resolved. At 308 nm, the angular distribution was slightly more isotropic that previously reported, leaving open the possibility that Cl2O excited at 308 nm lives longer than a rotational period. Chapter three describes the development and optimization of a molecular beam source of ClOOCl. We utilized pulsed laser photolysis of ClA2O to generate ClO radicals, and cooled the cell to promote three body recombination to form ClOOCl. The principal components in the beam were Cl2, Cl2O, and ClOOCl. In the fourth chapter, the photodissociation dynamics of ClOOCl are investigated at 248 and 308 nm. We observed multiple dissociation pathways which produced ClO + ClO and 2Cl + O2 products. The relative Cl:ClO product yields are 1.0:0.13 and 1.0:0.20 for ClOOCl photolysis at 248 and 308 nm, respectively. The upper limit for the relative yield of the ClO + ClO channel was 0.19 at 248 nm and 0.31 at 308 nm. These results substantially confirm the current assumption but decrease somewhat the efficiency of the ClOOCl ozone-depleting catalytic cycle. At 248 nm, ClOOCl photolysis exhibited novel dissociation dynamics which appeared to depend on the symmetry of the excited state.

Origin of the Okrouhlá Radouň episyenite-hosted uranium deposit, Bohemian Massif, Czech Republic: fluid inclusion and stable isotope constraints

NASA Astrophysics Data System (ADS)

Dolníček, Zdeněk; René, Miloš; Hermannová, Sylvie; Prochaska, Walter

2014-04-01

The Okrouhlá Radouň shear zone hosted uranium deposit is developed along the contact of Variscan granites and high-grade metasedimentary rocks of the Moldanubian Zone of the Bohemian Massif. The pre-ore pervasive alteration of wall rocks is characterized by chloritization of mafic minerals, followed by albitization of feldspars and dissolution of quartz giving rise to episyenites. The subsequent fluid circulation led to precipitation of disseminated uraninite and coffinite, and later on, post-ore quartz and carbonate mineralization containing base metal sulfides. The fluid inclusion and stable isotope data suggest low homogenization temperatures (˜50-140 °C during pre-ore albitization and post-ore carbonatization, up to 230 °C during pre-ore chloritization), variable fluid salinities (0-25 wt.% NaCl eq.), low fluid δ18O values (-10 to +2 ‰ V-SMOW), low fluid δ13C values (-9 to -15 ‰ V-PDB), and highly variable ionic composition of the aqueous fluids (especially Na/Ca, Br/Cl, I/Cl, SO4/Cl, NO3/Cl ratios). The available data suggest participation of three fluid endmembers of primarily surficial origin during alteration and mineralization at the deposit: (1) local meteoric water, (2) Na-Ca-Cl basinal brines or shield brines, (3) SO4-NO3-Cl-(H)CO3 playa-like fluids. Pre-ore albitization was caused by circulation of alkaline, oxidized, and Na-rich playa fluids, whereas basinal/shield brines and meteoric water were more important during the post-ore stage of alteration.

The mechanism of potentiation of the glutamate-induced neurotoxicity by serum albumin. A possible role of nitric oxide.

PubMed

Sorokina, E G; Reutov, V P; Pinelis, V G; Vinskaya, N P; Vergun, O V; Khodorov, B I

2000-01-01

Potentiation of the delayed (Glu)-induced neurotoxicity by serum albumin (SA) was studied in experiments with cultured cerebellar granule cells. The delayed neuronal death (DND) was evaluated by counting neurons containing or excluding Trypan Blue 4 h after treatment with Glu. Cytoplasmic Ca2+ ([Ca2+]i) was measured in individual Fura-2-loaded neurons. It was shown that a 15-min application of bovine SA (4 mg/ml) together with Glu (100 microM, 10 microM glycine, Mg2+-free solution) enhanced DND in the culture 1.7 times (43.1+/-3.1%) with respect to the effect induced by Glu alone (24.6+/-0.6%). The bovine SA application did not change the dynamics of [Ca2+]i response during a short-term (1 min) and long-term (15 min) Glu-treatment. DND was prevented by simultaneous application of Glu and inhibitor of NO-synthase N omega-nitro-L-arginine methyl ester (L-NAME), 100 microM) (10.8+/-1.0%) as well as by the application of Glu with SA and L-NAME (9.8+/-1.2%). In order to evaluate the role of nitric oxide (NO) in the SA effect, the cells were incubated for 15 min with the NO-donors sodium nitroprusside (SNP, 10 and 100 microM) and sodium nitrite (NaNO2, 10 and 100 microM) together with SA and in its absence. SA also greatly enhanced the DND induced by SNP and NaNO2. Thus, the DND after simultaneous treatment with SA and SNP was 16.3+/-2.5% (10 microM) or 29.6+/-2.1% (100 microM), and 9.6+/-0.8% (10 microM) and 19.7+/-2.1% after treatment with SNP alone. Exposure to SA together with NaNO2 led to the DND increase up to 26.5+/-1.9% (10 microM) and 37.7+/-3.5% (100 microM) in comparison with 7.4+/-2.0% (10 microM) and 18.9+/-0.8% (100 microM) in experiments with NaNO2 alone. Taking into account the ability of NO and NO2 to oxidize unsaturated fatty acids and the ability of SA to bind them after their hydrolytic removal, we suggested that the SA-induced potentiation of Glu neurotoxicity resulted from exacerbation of the toxic effects of NO and other trace radicals on the neuronal membranes. This hypothesis was supported by the finding that SA also enhanced the neurotoxicity of the lipid prooxidant FeCl2. The simultaneous 15-min application of FeCl2 (10 microM) and SA caused a 51.5+/-4.0% increase in DND, which exceeded 2.4 times the effect produced by FeCl2 alone (21.3+/-2.3%).

Aggregation kinetics of microplastics in aquatic environment: Complex roles of electrolytes, pH, and natural organic matter.

PubMed

Li, Shuocong; Liu, Hong; Gao, Rui; Abdurahman, Abliz; Dai, Juan; Zeng, Feng

2018-06-01

Microplastics are an emerging contaminants of concern in aquatic environments. The aggregation behaviors of microplastics governing their fate and ecological risks in aquatic environments is in need of evaluation. In this study, the aggregation behavior of polystyrene microspheres (micro-PS) in aquatic environments was systematically investigated over a range of monovalent and divalent electrolytes with and without natural organic matter (i.e., Suwannee River humic acid (HA)), at pH 6.0, respectively. The zeta potentials and hydrodynamic diameters of micro-PS were measured and the subsequent aggregation kinetics and attachment efficiencies (α) were calculated. The aggregation kinetics of micro-PS exhibited reaction- and diffusion-limited regimes in the presence of monovalent or divalent electrolytes with distinct critical coagulation concentration (CCC) values, followed the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The CCC values of micro-PS were14.9, 13.7, 14.8, 2.95 and 3.20 mM for NaCl, NaNO 3 , KNO 3 , CaCl 2 and BaCl 2 , respectively. As expected, divalent electrolytes (i.e., CaCl 2 and BaCl 2 ) had stronger influence on the aggregation behaviors of micro-PS as compared to monovalent electrolytes (i.e., NaCl, NaNO 3 and KNO 3 ). HA enhanced micro-PS stability and shifted the CCC values to higher electrolyte concentrations for all types of electrolytes. The CCC values of micro-PS were lower than reported carbonaceous nanoparticles CCC values. The CCC[Ca 2+ ]/CCC [Na + ] ratios in the absence and presence of HA at pH 6.0 were proportional to Z -2.34 and Z -2.30 , respectively. These ratios were in accordance with the theoretical Schulze-Hardy rule, which considers that the CCC is proportional to z -6 -z -2 . These results indicate that the stability of micro-PS in the natural aquatic environment and the possibility of significant aqueous transport of micro-PS. Copyright © 2018 Elsevier Ltd. All rights reserved.

Adenosine, lidocaine and Mg2+ (ALM) fluid therapy attenuates systemic inflammation, platelet dysfunction and coagulopathy after non-compressible truncal hemorrhage.

PubMed

Letson, Hayley; Dobson, Geoffrey

2017-01-01

Systemic inflammation and coagulopathy are major drivers of injury progression following hemorrhagic trauma. Our aim was to examine the effect of small-volume 3% NaCl adenosine, lidocaine and Mg2+ (ALM) bolus and 0.9% NaCl/ALM 'drip' on inflammation and coagulation in a rat model of hemorrhagic shock. Sprague-Dawley rats (429±4 g) were randomly assigned to: 1) shams, 2) no-treatment, 3) saline-controls, 4) ALM-therapy, and 5) Hextend®. Hemorrhage was induced in anesthetized-ventilated animals by liver resection (60% left lateral lobe and 50% medial lobe). After 15 min, a bolus of 3% NaCl ± ALM (0.7 ml/kg) was administered intravenously (Phase 1) followed 60 min later by 4 hour infusion of 0.9% NaCl ± ALM (0.5 ml/kg/hour) with 1-hour monitoring (Phase 2). Plasma cytokines were measured on Magpix® and coagulation using Stago/Rotational Thromboelastometry. After Phase 1, saline-controls, no-treatment and Hextend® groups showed significant falls in white and red cells, hemoglobin and hematocrit (up to 30%), whereas ALM animals had similar values to shams (9-15% losses). After Phase 2, these deficits in non-ALM groups were accompanied by profound systemic inflammation. In contrast, after Phase 1 ALM-treated animals had undetectable plasma levels of IL-1α and IL-1β, and IL-2, IL-6 and TNF-α were below baseline, and after Phase 2 they were less or similar to shams. Non-ALM groups (except shams) also lost their ability to aggregate platelets, had lower plasma fibrinogen levels, and were hypocoagulable. ALM-treated animals had 50-fold higher ADP-induced platelet aggregation, and 9.3-times higher collagen-induced aggregation compared to saline-controls, and had little or no coagulopathy with significantly higher fibrinogen shifting towards baseline. Hextend® had poor outcomes. Small-volume ALM bolus/drip mounted a frontline defense against non-compressible traumatic hemorrhage by defending immune cell numbers, suppressing systemic inflammation, improving platelet aggregation and correcting coagulopathy. Saline-controls were equivalent to no-treatment. Possible mechanisms of ALM's immune-bolstering effect are discussed.

Sequential Sedimentation-Biofiltration System for the purification of a small urban river (the Sokolowka, Lodz) supplied by stormwater.

PubMed

Szklarek, S; Wagner, I; Jurczak, T; Zalewski, M

2018-01-01

The study analyses the efficiency of a Sequentional Sedimentation-Biofiltration System (SSBS) built on the Sokolowka river in Lodz (Poland). It was constructed to purify a small urban river whose hydrological regime is dominated by stormwater and meltwater. The SSBS was constructed on a limited area as multi-zone constructed wetlands. The SSBS consists of three zones: sedimentation zone with structures added to improve sedimentation, a geochemical barrier made of limestone deposit and biofiltration zone. The purification processes of total suspended solids (TSS), total phosphorus (TP), total nitrogen (TP) and other nutrients: phosphates (PO 4 3- ), ammonium (NH 4 + ) and nitrates (NO 3 - ) of the SSBS were analyzed. Chloride (Cl - ) reduction was investigated. Monitoring conducted in the first two hydrological years after construction indicated that the SSBS removed 61.4% of TSS, 37.3% of TP, 30.4% of PO 4 3- , 46.1% of TN, 2.8% of NH4+, 44.8% of NO 3 - and 64.0% of Cl - . The sedimentation zone played a key role in removing TSS and nutrients. The geochemical barrier and biofiltration zone each significantly improved overall efficiency by 4-10% for TSS, PO 4 3- , TN, NO 3 - and Cl - . Although the system reduced the concentration of chloride, further studies are needed to determine the circulation of Cl - in constructed wetlands (CWs), and to assess its impact on purification processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chloride and bicarbonate transport in rat resistance arteries.

PubMed Central

Aalkjaer, C; Hughes, A

1991-01-01

1. The role of chloride and bicarbonate in the control of intracellular pH (pHi) was assessed in segments of rat mesenteric resistance arteries (internal diameter about 200 microns) by measurements of chloride efflux with 36Cl-, of pHi with the pH-sensitive dye 2',7'-bis-(2-carboxyethyl)-5 (and-6)-carboxyfluorescein (BCECF) and of membrane potential with intracellular electrodes. 2. The main questions addressed were whether the previously demonstrated sodium-coupled uptake of bicarbonate in these arteries was also coupled to chloride efflux, and whether sodium-independent Cl(-)-HCO3- exchange was present and played a role in regulation of pHi. 3. The 36Cl- efflux was unaffected by acidification induced by an NH4Cl pre-pulse in the presence as well as in the absence of bicarbonate. This was also true in sodium-free media and in vessels depolarized by high potassium. 4. The membrane potential was unaffected by the acidification associated with wash-out of NH4Cl, and the net acid extrusion during recovery of pHi from the acidification was not affected significantly by depolarization. 5. In the absence of bicarbonate, omission of extracellular chloride caused no change in pHi, but reduced 36Cl- efflux. By contrast, in the presence of bicarbonate, omission of chloride caused an increase in pHi but no change in 36Cl- efflux. Furthermore, the anion transport inhibitor 4,4'-diisothiocyanatostilbene-2,2'-disulphonic acid (DIDS) inhibited the increase in pHi seen in the presence of bicarbonate and reduced the 36Cl- efflux in the presence of bicarbonate. 6. The presence of bicarbonate had no significant effect on the rate of recovery of pHi or the rate of increase of intracellular acid equivalents after an NH4Cl induced alkalinization; also the buffering power was not significantly different in the absence and presence of bicarbonate. Moreover these parameters were not significantly affected by DIDS, although DIDS as previously demonstrated reduced the rate of recovery of pHi from acidification. 7. The membrane potential was not significantly affected by the alkalinization associated with addition of NH4Cl and the rate of recovery of pHi from the alkalinization was not affected by depolarization. 8. The effects of NH4Cl and PCO2 on 36Cl- efflux were complex and could not easily be explained by the changes in pHi.(ABSTRACT TRUNCATED AT 400 WORDS) PMID:2061847

Preparation and characterization of silk fibroin as a biomaterial with potential for drug delivery

PubMed Central

2012-01-01

Background Degummed silk fibroin from Bombyx mori (silkworm) has potential carrier capabilities for drug delivery in humans; however, the processing methods have yet to be comparatively analyzed to determine the differential effects on the silk protein properties, including crystalline structure and activity. Methods In this study, we treated degummed silk with four kinds of calcium-alcohol solutions, and performed secondary structure measurements and enzyme activity test to distinguish the differences between the regenerated fibroins and degummed silk fibroin. Results Gel electrophoresis analysis revealed that Ca(NO3)2-methanol, Ca(NO3)2-ethanol, or CaCl2-methanol treatments produced more lower molecular weights of silk fibroin than CaCl2-ethanol. X-ray diffraction and Fourier-transform infrared spectroscopy showed that CaCl2-ethanol produced a crystalline structure with more silk I (α-form, type II β-turn), while the other treatments produced more silk II (β-form, anti-parallel β-pleated sheet). Solid-State 13C cross polarization and magic angle spinning-nuclear magnetic resonance measurements suggested that regenerated fibroins from CaCl2-ethanol were nearly identical to degummed silk fibroin, while the other treatments produced fibroins with significantly different chemical shifts. Finally, enzyme activity test indicated that silk fibroins from CaCl2-ethanol had higher activity when linked to a known chemotherapeutic drug, L-asparaginase, than the fibroins from other treatments. Conclusions Collectively, these results suggest that the CaCl2-ethanol processing method produces silk fibroin with biomaterial properties that are appropriate for drug delivery. PMID:22676291

[Relations between location of elements in periodic table and affinity for the kidneys (author's transl)].

PubMed

Ando, A; Hisada, K; Ando, I

1977-10-01

The distribution of many inorganic compounds in rats was investigated in order to evaluate kidney affinity of inorganic compounds. In these experiments, 30%, 10-20% and 4-10% of administered dose was localized in the kidneys in 203Hg-acetate and 203 Bi-acetate, in H198AuCl4, 103PdCl2, 201TlCl, 210Pd(NO3)2 and H2(127M)TeO3, and in Na2(51)CrO4, 54MnCl2, (114m)InCl3 and 7BeCl2, respectively. Some bipositive ions and anions was hardly taken up into the kidneys. And in many hard acids according to classification of Lewis acids, the uptake rate into the kidneys was usually small. On the other hand, Hg, Au and Bi, which have strong binding power to the protein, showed high uptake rate in the kidneys. As Hg++, Au+ and Bi+++ was soft acids according to classification of Lewis acids, it was thought that these elements would bind strongly to soft base (RSH, RS-) present in the kidney.

Slow relaxation in a one-dimensional rational assembly of antiferromagnetically coupled [Mn4] single-molecule magnets.

PubMed

Lecren, Lollita; Roubeau, Olivier; Coulon, Claude; Li, Yang-Guang; Le Goff, Xavier F; Wernsdorfer, Wolfgang; Miyasaka, Hitoshi; Clérac, Rodolphe

2005-12-14

Four discrete Mn(III)/Mn(II) tetranuclear complexes with a double-cuboidal core, [Mn(4)(hmp)(6)(CH(3)CN)(2)(H(2)O)(4)](ClO(4))(4).2CH(3)CN (1), [Mn(4)(hmp)(6)(H(2)O)(4)](ClO(4))(4).2H(2)O (2), [Mn(4)(hmp)(6)(H(2)O)(2)(NO(3))(2)](ClO(4))(2).4H(2)O (3), and [Mn(4)(hmp)(6)(Hhmp)(2)](ClO(4))(4).2CH(3)CN (4), were synthesized by reaction of Hhmp (2-hydroxymethylpyridine) with Mn(ClO(4))(2).6H(2)O in the presence of tetraethylammonium hydroxide and subsequent addition of NaNO(3) (3) or an excess of Hhmp (4). Direct current (dc) magnetic measurements show that both Mn(2+)-Mn(3+) and Mn(3+)-Mn(3+) magnetic interactions are ferromagnetic in 1-3 leading to an S(T) = 9 ground state for the Mn(4) unit. Furthermore, these complexes are single-molecule magnets (SMMs) clearly showing both thermally activated and ground-state tunneling regimes. Slight changes in the [Mn(4)] core geometry result in an S(T) = 1 ground state in 4. A one-dimensional assembly of [Mn(4)] units, catena-{[Mn(4)(hmp)(6)(N(3))(2)](ClO(4))(2)} (5), was obtained in the same synthetic conditions with the subsequent addition of NaN(3). Double chairlike N(3)(-) bridges connect identical [Mn(4)] units into a chain arrangement. This material behaves as an Ising assembly of S(T) = 9 tetramers weakly antiferromagnetically coupled. Slow relaxation of the magnetization is observed at low temperature for the first time in an antiferromagnetic chain, following an activated behavior with Delta(tau)/k(B) = 47 K and tau(0) = 7 x 10(-)(11) s. The observation of this original thermally activated relaxation process is induced by finite-size effects and in particular by the noncompensation of spins in segments of odd-number units. Generalizing the known theories on the dynamic properties of polydisperse finite segments of antiferromagnetically coupled Ising spins, the theoretical expressions of the characteristic energy gaps Delta(xi) and Delta(tau) were estimated and successfully compared to the experimental values.

Nitrogen Species in the Post-Pinatubo Stratosphere: Model Analysis Utilizing UARS Measurements. Appendix F

NASA Technical Reports Server (NTRS)

Danilin, Michael Y.; Rodriguez, Jose M.; Hu, Wenjie; Ko, Malcolm K. W.; Weisenstein, Debra K.; Kumer, John B.; Mergenthaler, John L.; Russell, James M., III; Koike, Makoto; Yue, Glenn K.

1999-01-01

We present an analysis of the impact of heterogeneous chemistry on the partitioning of nitrogen species measured by the Upper Atmosphere Research Satellite (UARS) instruments. The UARS measurements utilized include N2O, HNO3, and ClONO2 from the cryogenic limb array etalon spectrometer (CLAES), version 7 (v.7), and temperature, methane, ozone, H2O, HCl, NO and NO2 from the halogen occultation experiment (HALOE), version 18. The analysis is carried out for the UARS data obtained between January 1992 and September 1994 in the 100- to 1-mbar (approx. 17-47 km) altitude range and over 10 deg latitude bins from 70 deg S to 70 deg N. The spatiotemporal evolution of aerosol surface area density (SAD) is adopted from analysis of the Stratospheric Aerosol and Gas Experiment (SAGE) II data. A diurnal steady state photochemical box model, constrained by the temperature, ozone, H2O, CH4, aerosol SAD, and columns of O2 and O3 above the point of interest, has been used as the main tool to analyze these data. Total inorganic nitrogen (NOY) is obtained by three different methods: (1) as a sum of the UARS-measured NO, NO2, HNO3, and ClONO2; (2) from the N2O-NOY correlation; and (3) from the CH4-NOY correlation. To validate our current understanding of stratospheric heterogeneous chemistry for post-Pinatubo conditions, the model-calculated monthly averaged NO(x)/NO(y) ratios and the NO, NO2, and HNO3 profiles are compared with the UARS-derived data. In general, the UARS-constrained box model captures the main features of nitrogen species partitioning in the post-Pinatubo years, such as recovery of NO(x) after the eruption, their seasonal variability and vertical profiles. However, the model underestimates the NO2 content, particularly in the 30- to 7-mbar (approx. 23-32 km) range. Comparisons of the calculated temporal behavior of the partial columns of NO2 and HNO3 and ground-based measurements at 45 deg S and 45 deg N are also presented. Our analysis indicates that ground-based and HALOE v.18 measurements of the NO2 vertical columns are consistent within the range of their uncertainties and are systematically higher (up to 50%) than the model results at midlatitudes in both hemispheres. Reasonable agreement is obtained for HNO3 columns at 45 deg S, suggesting some problems with nitrogen species partitioning in the model. Outstanding uncertainties are discussed.

Tropospheric photooxidation of CF3CH2CHO and CF3(CH2)2CHO initiated by Cl atoms and OH radicals

NASA Astrophysics Data System (ADS)

Antiñolo, M.; Jiménez, E.; Notario, A.; Martínez, E.; Albaladejo, J.

2010-02-01

The absolute rate coefficients for the tropospheric reactions of chlorine (Cl) atoms and hydroxyl (OH) radicals with CF3CH2CHO and CF3(CH2)2CHO were measured as a function of temperature (263-371 K) and pressure (50-215 Torr of He) by pulsed UV laser photolysis techniques. Vacuum UV resonance fluorescence was employed to detect and monitor the time evolution of Cl atoms. Laser induced fluorescence was used in this work for the detection of OH radicals as a function of reaction time. No pressure dependence of the bimolecular rate coefficients, kCl and kOH, was found at all temperatures. At room temperature kCl and kOH were (in 10-11 cm3 molecule-1 s-1): kCl(CF3CH2CHO) = (1.55±0.53); kCl(CF3(CH2)2CHO) = (3.39±1.38); kCl(CF3CH2CHO) = (0.259±0.050); kCl(CF3(CH2)2CHO) = (1.28±0.24). A slightly positive temperature dependence of kCl was observed for CF3CH2CHO and CF3(CH2)2CHO, and kOH(CF3CH2CHO). In contrast, kOH(CF3(CH2)2CHO) did not exhibit a temperature dependence over the range investigated. Arrhenius expressions for these reactions were: kCl(CF3CH2CHO) = (4.4±1.0)×10-11 exp{-(316±68)/T} cm3 molecule-1 s-1 kCl(CF3(CH2)2CHO) = (2.9±0.7)×10-10 exp{-(625±80)/T} cm3 molecule-1 s-1 kOH(CF3CH2CHO) = (7.8±2.2)×10-12 exp{-(314±90)/T} cm3 molecule-1 s-1 The atmospheric impact of the homogeneous removal by OH radicals and Cl atoms of these fluorinated aldehydes is discussed in terms of the global atmospheric lifetimes, taking into account different degradation pathways. The calculated lifetimes show that atmospheric oxidation of CF3(CH2)x CHO are globally dominated by OH radicals, however reactions initiated by Cl atoms can act as a source of free radicals at dawn in the troposphere.

Theoretical Design on a Series of Novel Bicyclic and Cage Nitramines as High Energy Density Compounds.

PubMed

Pan, Yong; Zhu, Weihua

2017-11-30

We designed four bicyclic nitramines and three cage nitramines by incorporating -N(NO 2 )-CH 2 -N(NO 2 )-, -N(NO 2 )-, and -O- linkages based on the HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane) framework. Then, their electronic structure, heats of formation, energetic properties, strain energy, thermal stability, and impact sensitivity were systematically studied using density functional theory (DFT). Compared to the parent compound HMX, all the title compounds have much higher density, better detonation properties, and better oxygen balance. Among them, four compounds have extraordinary high detonation properties (D > 9.70 km/s and P > 44.30 GPa). Moreover, most of the title compounds exhibit better thermal stability and lower impact sensitivity than CL-20 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) or HNHAA (hexanitrohexaazaadamantane). Thus, all of the seven new nitramine compounds are promising candidates for high energy density compounds. In particular, five compounds exhibit a best combination of better oxygen balance, good thermal stability, excellent detonation properties superior to or comparable to CL-20 or HNHAA, and lower impact sensitivity than CL-20 or HNHAA. The results indicate that our unusual design strategy that constructing bicyclic or cage nitramines based on the HMX framework by incorporating the intramolecular linkages is very useful for developing novel energetic compounds with excellent detonation performance and low sensitivity.

Syntheses of amide based anion receptors and investigation of their associations with anions and their molecular structures using proton NMR titration and DFT methods

NASA Astrophysics Data System (ADS)

Navakhun, Korakot; Sawangsri, Ranu; Ruangpornvisuti, Vithaya

2014-03-01

The synthesized disubstituted isophthalamide and pyridine-2,6dicarboxamide derivatives of nine compounds were prepared. Their association constants with tetrabutylammonium fluoride (TBA·F), tetrabutylammonium chloride (TBA·Cl), tetrabutylammonium bromide (TBA·Br), tetrabutylammonium dihydrogenphosphate (TBA·H2PO4), tetrabutylammonium hydrogensulphate (TBA·HSO4) and tetrabutylammonium nitrate (TBA·NO3) were obtained by 1H NMR titration technique. The optimized structures of compounds 1-9 and their association with F-, Cl-, Br-, HPO4-, HSO4- and NO3- were obtained using the B3LYP/6-31+G(d) method. The most favorable complex of compound 3 with Br- was found. The high association constants of complexes 1-6 with F- are expected. Associations of all receptors with anions are exothermic and spontaneous reactions. Thermodynamic properties of all associations obtained using B3LYP/6-31+G(d) method are reported.

Vinclozolin: 3-(3,5-di-chloro-phen-yl)-5-ethenyl-5-methyl-1,3-oxazolidine-2,4-dione.

PubMed

Cho, Seonghwa; Kim, Jineun; Lee, Sangjin; Kim, Tae Ho

2014-07-01

In the title compound, C12H9Cl2NO3, which is the fungicide vinclozolin, the dihedral angle between the oxazolidine ring mean plane [r.m.s. deviation = 0.029 Å] and the benzene ring is 77.55 (8)°. In the crystal, mol-ecules are linked via C-H⋯O hydrogen bonds, forming chains along [010]. The chains are linked by short Cl⋯Cl contacts [3.4439 (3) and 3.5798 (3) Å], resulting in a three-dimensional architecture.

Isomorphous rare-earth bis[bis(2,6-diisopropylphenyl)phosphate] complexes and their self-assembly into two-dimensional frameworks by intramolecular hydrogen bonds.

PubMed

Minyaev, Mikhail E; Nifant'ev, Ilya E; Tavtorkin, Alexander N; Korchagina, Sof'ya A; Zeynalova, Shadana Sh; Ananyev, Ivan V; Churakov, Andrei V

2017-10-01

The crystal structures of rare-earth diaryl- or dialkylphosphate derivatives are poorly explored. Crystals of bis[bis(2,6-diisopropylphenyl)phosphato-κO]chloridotetrakis(methanol-κO)neodymium methanol disolvate, [Nd(C 24 H 34 O 4 P)Cl(CH 4 O) 4 ]·2CH 3 OH, (1), and of the lutetium, [Lu(C 24 H 34 O 4 P)Cl(CH 4 O) 4 ]·2CH 3 OH, (2), and yttrium, [Y(C 24 H 34 O 4 P)Cl(CH 4 O) 4 ]·2CH 3 OH, (3), analogues have been obtained by reactions between lithium bis(2,6-diisopropylphenyl)phosphate and LnCl 3 (H 2 O) 6 (in a 2:1 ratio) in methanol. Compounds (1)-(3) crystallize in the C2/c space group. Their crystal structures are isomorphous. The molecule possesses C 2 symmetry with a twofold crystallographic axis passing through the Ln and Cl atoms. The bis(2,6-diisopropylphenyl)phosphate ligands all display a κ 1 O-monodentate coordination mode. The coordination polyhedron for the metal atom [coordination number (CN) = 7] is a distorted pentagonal bipyramid. Each [Ln{O 2 P(O-2,6- i Pr 2 C 6 H 3 ) 2 } 2 Cl(CH 3 OH) 4 ] molecular unit exhibits two intramolecular O-H...O hydrogen bonds, forming six-membered rings, and two intramolecular O-H...Cl interactions, forming four-membered rings. Intermolecular O-H...O hydrogen bonds connect each unit via four noncoordinating methanol molecules with four other units, forming a two-dimensional hydrogen-bond network. Crystals of bis[bis(2,6-diisopropylphenyl)phosphato-κO]tetrakis(methanol-κO)(nitrato-κ 2 O,O')neodymium methanol disolvate, [Nd(C 24 H 34 O 4 P)(NO 3 )(CH 4 O) 4 ]·2CH 3 OH, (4), have been obtained in an analogous manner from NdCl 3 (H 2 O) 6 . Compound (4) also crystalizes in the C2/c space group. Its crystal structure is similar to those of (1)-(3). The κ 2 O,O'-bidentate nitrate anion is disordered over a twofold axis, being located nearly on it. Half of the molecule is crystallographically unique (CN Nd = 8). Unlike (1)-(3), complex (4) exhibits disorder of all three methanol molecules, one isopropyl group of the phosphate ligand and the NO 3 - ligand. The structure of (4) displays intra- and intermolecular O-H...O hydrogen bonds similar to those in (1)-(3). Compounds (1)-(4) represent the first reported mononuclear bis[bis(diaryl/dialkyl)phosphate] rare-earth complexes.

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.

Molecular Dynamics Simulations of the Interfacial Region between Boehmite and Gibbsite Basal Surfaces and High Ionic Strength Aqueous Solutions

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

Shen, Zhizhang; Ilton, Eugene S.; Prange, Micah P.

Classical molecular dynamics (MD) simulations were used to study the interactions of up to 2 M NaCl and NaNO3 aqueous solutions with the presumed inert boehmite (010) and gibbsite (001) surfaces. The force field parameters used in these simulations were validated against density functional theory calculations of Na+ and Cl- hydrated complexes adsorbed at the boehmite (010) surface. In all the classical MD simulations and regardless of the ionic strength or the nature of the anion, Na+ ions were found to preferably form inner-sphere complexes over outer-sphere complexes at the aluminum (oxy)hydroxide surfaces, adsorbing closer to the surface than bothmore » water molecules and anions. In contrast, Cl- ions were distributed almost equally between inner- and outer-sphere positions. The resulting asymmetry in adsorption strengths offers molecular-scale evidence for the observed isoelectric point (IEP) shift to higher pH at high ionic strength for aluminum (oxy)hydroxides. As such, the MD simulations also provided clear evidence against the assumption that the basal surfaces of boehmite and gibbsite are inert to background electrolytes. Finally, the MD simulations indicated that, although the adsorption behavior of Na+ in NaNO3 and NaCl solutions was similar, the different affinities of NO3- and Cl- for the aluminum (oxy)hydroxide surfaces might have macroscopic consequences, such as difference in the sensitivity of the IEP to the electrolyte concentration.« less

Basolateral membrane chloride permeability of A6 cells: implication in cell volume regulation.

PubMed

Brochiero, E; Banderali, U; Lindenthal, S; Raschi, C; Ehrenfeld, J

1995-11-01

The permeability to Cl- of the basolateral membrane (blm) was investigated in renal (A6) epithelial cells, assessing their role in transepithelial ion transport under steady-state conditions (isoosmotic) and following a hypoosmotic shock (i.e. in a regulatory volume decrease, RVD). Three different complementary studies were made by measuring: (1) the Cl- transport rates (delta F/Fo s-1 (x10(-3))), where F is the fluorescence of N-(6-methoxyquinoyl) acetoethyl ester, MQAE, and Fo the maximal fluorescence (x10(-3)) of both membranes by following the intracellular Cl- activities (ai Cl-, measured with MQAE) after extracellular Cl- substitution (2) the blm 86Rb and 36Cl uptakes and (3) the cellular potential and Cl- current using the whole-cell patch-clamp technique to differentiate between the different Cl- transport mechanisms. The permeability of the blm to Cl- was found to be much greater than that of the apical membranes under resting conditions: aiCl- changes were 5.3 +/- 0.7 mM and 25.5 +/- 1.05 mM (n = 79) when Cl- was substituted by NO3(-) in the media bathing apical and basolateral membranes. The Cl- transport rate of the blm was blocked by bumetanide (100 microM) and 5-nitro-2-(3-phenylpropylamino)benzoic acid (NPPB, 50 microM) but not by N-phenylanthranilic acid (DPC, 100 microM). 86Rb and 36Cl uptake experiments confirmed the presence of a bumetanide- and a NPPB-sensitive Cl- pathway, the latter being approximately three times more important than the former (Na/K/2Cl cotransporter). Appli-cation of a hypoosmotic medium to the serosal side of the cell increased delta F/Fo s-1 (x10(-3)) after extracellular Cl- substitution (1.03 +/- 0.10 and 2.45 +/- 0.17 arbitrary fluorescent units s-1 for isoosmotic and hypoosmotic conditions respectively, n = 11); this delta F/Fo s-1 (x10(-3)) increase was totally blocked by serosal NPPB application; on the other hand, cotransporter activity was decreased by the hypoosmotic shock. Cellular Ca2+ depletion had no effect on delta F/Fo s-1 (x10(-3)) under isoosmotic conditions, but blocked the delta F/Fo s-1 (x10(-3)) increase induced by a hypoosmotic stress. Under isotonic conditions the measured cellular potential at rest was -37.2 +/- 4.0 mV but reached a maximal and transient depolarization of -25.1 +/- 3.7 mV (n = 9) under hypoosmotic conditions. The cellular current at a patch-clamping cellular potential of -85 mV (close to the Nernst equilibrium potential for K+) was blocked by NPPB and transiently increased by hypoosmotic shock (≈50% maximum increase). This study demonstrates that the major component of Cl- transport through the blm of the A6 monolayer is a conductive pathway (NPPB-sensitive Cl- channels) and not a Na/K/2Cl cotransporter. These channels could play a role in transepithelial Cl- absorption and cell volume regulation. The increase in the blm Cl- conductance, inducing a depolarization of these membranes, is proposed as one of the early events responsible for the stimulation of the 86Rb efflux involved in cell volume regulation.

Molecular and electronic structures of mononuclear iron complexes using strongly electron-donating ligands and their oxidized forms.

PubMed

Strautmann, Julia B H; George, Serena DeBeer; Bothe, Eberhard; Bill, Eckhard; Weyhermüller, Thomas; Stammler, Anja; Bögge, Hartmut; Glaser, Thorsten

2008-08-04

The ligand L (2-) (H 2L = N, N'-dimethyl- N, N'-bis(3,5-di- t-butyl-2-hydroxybenzyl)-1,2-diaminoethane) has been employed for the synthesis of two mononuclear Fe (III) complexes, namely, [LFe(eta (2)-NO 3)] and [LFeCl]. L (2-) is comprised of four strongly electron-donating groups (two tert-amines and two phenolates) that increase the electron density at the coordinated ferric ions. This property should facilitate oxidation of the complexes, that is, stabilization of the oxidized species. The molecular structures in the solid state have been established by X-ray diffraction studies. [LFeCl] is five-coordinate in a square-pyramidal coordination environment with the ligand adopting a trans-conformation, while [LFe(eta (2)-NO 3)] is six-coordinate in a distorted octahedral environment with the ligand in a beta-cis conformation. The electronic structures have been studied using magnetization, EPR, Mossbauer (with and without applied field), UV-vis-NIR, and X-ray absorption spectroscopies, which demonstrate highly anisotropic covalency from the strong sigma- and pi-donating phenolates. This analysis is supported by DFT calculations on [LFeCl]. The variations of the well-understood spectroscopic data in the solid state to the spectroscopic data in solution have been used to obtain insight in the molecular structure of the two complexes in solution. While the molecular structures of the solid states are retained in solutions of nonpolar aprotic solvents, there is, however, one common molecular structure in all protic polar solvents. The analysis of the LMCT transitions and the rhombicity E/ D clearly establish that both compounds exhibit a beta-cis conformation in these protic polar solvents. These two open coordination sites, cis to each other, allow access for two potential ligands in close proximity. Electrochemical analysis establishes two reversible oxidation waves for [LFeCl] at +0.55 V and +0.93 V vs Fc (+)/Fc and one reversible oxidation wave at +0.59 V with an irreversible oxidation at +1.07 V vs Fc (+)/Fc for [LFe(eta (2)-NO 3)]. The one- and the two-electron oxidations of [LFeCl] by chronoamperometry have been followed spectroscopically. The increase of a strong band centered at 420 nm indicates the formulation of [LFeCl] (+) as a Fe (III) monophenoxyl radical complex and of [LFeCl] (2+) as a Fe (III) bisphenoxyl radical complex. These studies imply that the ligand L (2-) is capable of providing a flexible coordination geometry with two binding sites for substrates and the allocation of two oxidation equivalents on the ligand.

Zirconium tetrachloride revisited

DOE PAGES

Borjas Nevarez, Rosendo; Balasekaran, Samundeeswari Mariappan; Kim, Eunja; ...

2018-02-19

We present that zirconium tetrachloride, ZrCl 4, is a strategic material with wide-ranging applications. Until now, only one crystallographic study on ZrCl 4has been reported [Krebs (1970).Z. Anorg. Allg. Chem.378, 263–272] and that was more than 40 years ago. The compound used for the previous determination was prepared from ZrO 2 and Cl 2–CCl 4, and single-crystal X-ray diffraction (SCXRD) studies on ZrCl 4 obtained from Zr metal have not yet been reported. In this context, we prepared ZrCl 4 from the reaction of Zr metal and Cl 2 gas in a sealed tube and investigated its structure at 100,more » 150, 200, 250, and 300 K. At 300 K, the SCXRD analysis indicates that ZrCl 4 crystallizes in the orthorhombic space group Pca2 1 [a= 6.262 (9),b= 7.402 (11),c= 12.039 (17) Å, andV= 558.0 (14) Å 3] and consists of infinite zigzag chains of edge-sharing ZrCl 6 octahedra. This chain motif is similar to that observed previously in ZrCl 4, but the structural parameters and space group differ. Finally, in the temperature range 100–300 K, no phase transformation was identified, while elongation of intra-chain Zr...Zr [3.950 (1) Å at 100 K and 3.968 (5) Å at 300 K] and inter-chain Cl...Cl [3.630 (3) Å at 100 K and 3.687 (9) Å at 300 K] distances occurred.« less

An infrared study of the nitro—nitrito linkage isomerization in solid nitro- and nitritopentamminecobalt(III) chloride

NASA Astrophysics Data System (ADS)

Heyns, A. M.; de Waal, D.

1989-01-01

The photochemical isomerization reaction of [Co(NH 3) 5NO 2]Cl 2 to [Co(NH 3) 5ONO]Cl 2 has been studied in the solid state by means of i.r. spectroscopy. The reaction is first order with k = 2.53±0.05 × 10 -4s -1 and is much faster ( t1/2=49min) than the well-known spontaneous nitrito → nitro isomerization ( t1/2 = 6 days). The i.r. bands of both the NH 3 and ONO - -groups in the range 4000-50 cm -1 indicate minor differences between the structures of freshly and photochemically prepared [Co(NH 3) 5ONO]Cl 2. The far i.r. spectra indicate the disorder existing in the intermediate products during the isomerization processes.

Separation of rare earths from transition metals by liquid-liquid extraction from a molten salt hydrate to an ionic liquid phase.

PubMed

Rout, Alok; Binnemans, Koen

2014-02-28

The solvent extraction of trivalent rare-earth ions and their separation from divalent transition metal ions using molten salt hydrates as the feed phase and an undiluted fluorine-free ionic liquid as the extracting phase were investigated in detail. The extractant was tricaprylmethylammonium nitrate, [A336][NO3], and the hydrated melt was calcium nitrate tetrahydrate, Ca(NO3)2·4H2O. The extraction behavior of rare-earth ions was studied for solutions of individual elements, as well as for mixtures of rare earths in the hydrated melt. The influence of different extraction parameters was investigated: the initial metal loading in the feed phase, percentage of water in the feed solution, equilibration time, and the type of hydrated melt. The extraction of rare earths from Ca(NO3)2·4H2O was compared with extraction from CaCl2·4H2O by [A336][Cl] (Aliquat 336). The nitrate system was found to be the better one. The extraction and separation of rare earths from the transition metals nickel, cobalt and zinc were also investigated. Remarkably high separation factors of rare-earth ions over transition metal ions were observed for extraction from Ca(NO3)2·4H2O by the [A336][NO3] extracting phase. Furthermore, rare-earth ions could be separated efficiently from transition metal ions, even in melts with very high concentrations of transition metal ions. Rare-earth oxides could be directly dissolved in the Ca(NO3)2·4H2O phase in the presence of small amounts of Al(NO3)3·9H2O or concentrated nitric acid. The efficiency of extraction after dissolving the rare-earth oxides in the hydrated nitrate melt was identical to extraction from solutions with rare-earth nitrates dissolved in the molten phase. The stripping of the rare-earth ions from the loaded ionic liquid phase and the reuse of the recycled ionic liquid were also investigated in detail.

Probing cosmic anisotropy with gravitational waves as standard sirens

NASA Astrophysics Data System (ADS)

Cai, Rong-Gen; Liu, Tong-Bo; Liu, Xue-Wen; Wang, Shao-Jiang; Yang, Tao

2018-05-01

The gravitational wave (GW) as a standard siren directly determines the luminosity distance from the gravitational waveform without reference to the specific cosmological model, of which the redshift can be obtained separately by means of the electromagnetic counterpart like GW events from binary neutron stars and massive black hole binaries (MBHBs). To see to what extent the standard siren can reproduce the presumed dipole anisotropy written in the simulated data of standard siren events from typical configurations of GW detectors, we find that (1) for the Laser Interferometer Space Antenna with different MBHB models during five-year observations, the cosmic isotropy can be ruled out at 3 σ confidence level (C.L.) and the dipole direction can be constrained roughly around 20% at 2 σ C.L., as long as the dipole amplitude is larger than 0.04, 0.06 and 0.03 for MBHB models Q3d, pop III and Q3nod with increasing constraining ability, respectively; (2) for the Einstein telescope with no less than 200 standard siren events, the cosmic isotropy can be ruled out at 3 σ C.L. if the dipole amplitude is larger than 0.06, and the dipole direction can be constrained within 20% at 3 σ C.L. if the dipole amplitude is near 0.1; (3) for the Deci-Hertz Interferometer Gravitational wave Observatory with no less than 100 standard siren events, the cosmic isotropy can be ruled out at 3 σ C.L. for dipole amplitude larger than 0.03, and the dipole direction can even be constrained within 10% at 3 σ C.L. if the dipole amplitude is larger than 0.07. Our work manifests the promising perspective of the constraint ability on the cosmic anisotropy from the standard siren approach.

Simulated nitrogen deposition reduces CH4 uptake and increases N2O emission from a subtropical plantation forest soil in southern China.

PubMed

Wang, Yongsheng; Cheng, Shulan; Fang, Huajun; Yu, Guirui; Xu, Minjie; Dang, Xusheng; Li, Linsen; Wang, Lei

2014-01-01

To date, few studies are conducted to quantify the effects of reduced ammonium (NH4+) and oxidized nitrate (NO3-) on soil CH4 uptake and N2O emission in the subtropical forests. In this study, NH4Cl and NaNO3 fertilizers were applied at three rates: 0, 40 and 120 kg N ha(-1) yr(-1). Soil CH4 and N2O fluxes were determined twice a week using the static chamber technique and gas chromatography. Soil temperature and moisture were simultaneously measured. Soil dissolved N concentration in 0-20 cm depth was measured weekly to examine the regulation to soil CH4 and N2O fluxes. Our results showed that one year of N addition did not affect soil temperature, soil moisture, soil total dissolved N (TDN) and NH4+-N concentrations, but high levels of applied NH4Cl and NaNO3 fertilizers significantly increased soil NO3(-)-N concentration by 124% and 157%, respectively. Nitrogen addition tended to inhibit soil CH4 uptake, but significantly promoted soil N2O emission by 403% to 762%. Furthermore, NH4+-N fertilizer application had a stronger inhibition to soil CH4 uptake and a stronger promotion to soil N2O emission than NO3(-)-N application. Also, both soil CH4 and N2O fluxes were driven by soil temperature and moisture, but soil inorganic N availability was a key integrator of soil CH4 uptake and N2O emission. These results suggest that the subtropical plantation soil sensitively responses to atmospheric N deposition, and inorganic N rather than organic N is the regulator to soil CH4 uptake and N2O emission.

Study on lithium/air secondary batteries-Stability of NASICON-type lithium ion conducting glass-ceramics with water

NASA Astrophysics Data System (ADS)

Hasegawa, Satoshi; Imanishi, Nobuyuki; Zhang, Tao; Xie, Jian; Hirano, Atsushi; Takeda, Yasuo; Yamamoto, Osamu

The water stability of the fast lithium ion conducting glass-ceramic electrolyte, Li 1+ x+ yAl xTi 2- xSi yP 3- yO 12 (LATP), has been examined in distilled water, and aqueous solutions of LiNO 3, LiCl, LiOH, and HCl. This glass-ceramics are stable in aqueous LiNO 3 and aqueous LiCl, and unstable in aqueous 0.1 M HCl and 1 M LiOH. In distilled water, the electrical conductivity slightly increases as a function of immersion time in water. The Li-Al/Li 3- xPO 4- yN y/LATP/aqueous 1 M LiCl/Pt cell, where lithium phosphors oxynitrides Li 3- xPO 4- yN y (LiPON) are used to protect the direct reaction of Li and LATP, shows a stable open circuit voltage (OCV) of 3.64 V at 25 °C, and no cell resistance change for 1 week. Lithium phosphors oxynitride is effectively used as a protective layer to suppress the reaction between the LATP and Li metal. The water-stable Li/LiPON/LATP system can be used in Li/air secondary batteries with the air electrode containing water.

A displaced and low-frequency vibration of phosphorescent state of trans-[Rh(ethylenediamine)2Cl2]PF6 in a range of 5-497 K

NASA Astrophysics Data System (ADS)

Islam, Ashraful; Ikeda, Noriaki; Nozaki, Koichi; Ohno, Takeshi

1998-09-01

The lowest 3(dπ-dσ*) excited states of both cis- and trans-isomers of [Rh(en)2Cl2]X (en=ethylenediamine; X=PF6-, NO3-) and the deuteriated crystal of trans-[Rh(en-d4)2Cl2]PF6 have been investigated in the solid state and in a wide temperature range of 5-497 K by means of emission spectra, lifetime and quantum yield measurements. Emission spectral simulation of trans-[Rh(en)2Cl2]PF6 shows that the emission from the lowest 3(dπ-dσ*) excited state exhibits a progression of a low-frequency metal-chloride stretching vibration (250 cm-1) with a large Huang-Rhys factor (S) of 21 and a progression of a high-frequency N-H stretching vibration (3000 cm-1). The increasing full-width at half maximum (2200 cm-1→4400 cm-1) with increasing temperature (77 K→468 K) is ascribed to hot bands from the excited levels of low-frequency vibration. The luminescence quantum yields of the crystal samples are determined to 0.0008 at 298 K and 0.003 at 80 K for trans-[Rh(en)2Cl2]PF6 and 0.18 at 298 K and 0.40 at 80 K for trans-[Rh(en-d4)2Cl2]PF6. From a combination of lifetime and emission quantum yield measurements, values for kr and knr have been obtained. The observed temperature dependence of nonradiative decay rates of trans-[Rh(en-d4)2Cl2]PF6 in a low-temperature region (<300 K) is possible to reconstitute by using the emission spectral fitting parameters and assuming nuclear tunneling mechanism. The temperature effect and deuteriation effect on the nonradiative rate definitively establishes that the dominant "accepting" modes in the nonradiative transition are a highly displaced (S=21) vibrational mode of low-frequency Cl-Rh-Cl stretching and a weakly displaced (S=0.1) vibrational mode of high-frequency N-D stretching. The nonradiative transition in a high-temperature region occurs via barrier passing along a displaced coordinate of Cl-Rh-Cl vibration with a pre-exponential factor of 1011s-1 and is relatively insensitive to the high-frequency vibrational mode. The crystal of cis-[Rh(en)2Cl2]NO3 shows a red shift of the emission peak energy and an increase in the full-width at half maximum with increasing temperature. The results of temperature-dependent decay and spectra of emission can be interpreted in terms of two 3(dπ-dσ*) emitting states model.

Perchlorate Destruction and Potable Water Production Using Membrane Biofilm Reduction and Membrane Filtration

DTIC Science & Technology

2013-09-01

fraction of SRB could be active in O2 respiration, fermentation of organics, and even NO3- respiration. Therefore, the metabolic diversity of SRB...the case with PRB, which are able to reduce NO3- and ClO4-. To evaluate the model, we simulated effluent H2, UAP, and BAP concentrations, along with...effluent_experiment 56 Figure 36. Model- simulated concentrations of H2, UAP, and BAP in the effluent. Figure 37. Model- simulated

Vibrational spectra of carboxylato complexes—III. Trinuclear 'basic' acetates and formates of chromium(III), iron(III) and other transition metals

NASA Astrophysics Data System (ADS)

Johnson, M. K.; Powell, D. B.; Cannon, R. D.

The i.r. and Raman spectra of a series of complexes [M III3O(OOCR) 6L 3]X· xH 2O (M = Cr, Fe, Mn, Ru, Rh; L = H 2O, pyridine, γ-picoline; X = Cl, Br, I, NO 3, ClO 3, ClO 4, BF 4) have been analysed in detail. The vibrational modes of the central M 3O and the three surrounding MO 4 units, are identified. The metal—nitrogen stretching vibrations and the MOH 2 modes are assigned. The 'basic' chromium(III) formate is shown to be [Cr 3O(OOCH) 6(OH 2) 2(OOCH)] xH 2O, containing monodentate, inner-sphere coordinated formate ion. The use of the symmetric and asymmetric OCO stretching frequencies in characterizing bridging carboxylate ions is discussed.

Understanding in-situ ozone production in the summertime through radical observations and modelling studies during the Clean air for London project

NASA Astrophysics Data System (ADS)

Whalley, Lisa; Stone, Daniel; Sharp, Thomas; Garraway, Shani; Bannan, Thomas; Percival, Carl; Hopkins, James; Holmes, Rachel; Hamilton, Jacqui; Lee, James; Laufs, Sebastian; Kleffmann, Jörg; Heard, Dwayne

2014-05-01

With greater than 50 % of the global population residing in urban conurbations, poor urban air quality has a demonstrable effect on human health. OH and HO2 radicals, (collectively termed HOx) together with RO2 radicals, mediate virtually all of the oxidative chemistry in the atmosphere, being responsible for the transformation of primary emissions into secondary pollutants such as NO2, O3 and particulates. Here we present measurements of OH, HO2, partially speciated RO2 (distinguishing smaller alkane related RO2 from larger alkane/alkene/aromatic related RO2), ClNO2 and OH reactivity measurements taken during the ClearfLo campaign in central London in the summer of 2012. Comparison with calculations from a detailed box model utilising the Master Chemical Mechanism v3.2 tested our ability to reproduce radical levels, and enabled detailed radical budgets to be determined, highlighting for example the important role of the photolysis of nitrous acid (HONO) and carbonyl species as radical sources. Speciation of RO2 enabled the break-down of ozone production from different classes of VOCs to be calculated directly and compared with model calculations. Summertime observations of radicals have helped to identify that increases in photolytic sources of radicals on warm, sunny days can significantly increase local ozone concentrations leading to exceedances of EU air quality recommendations of 60 ppbV. The photolytic breakdown of ClNO2 to Cl atoms can more than double radical concentrations in the early morning; although the integrated increase in radical concentrations over a 24 hr period in model runs when ClNO2 photolysis is included is more modest. On average we calculate just under a 1 ppb increase in ozone due to the presence of ClNO2 in London air. OH reactivity was found to be greatest during morning and evening rush hours. Good agreement between the modelled OH reactivity and observations could be achieved when reactivity associated with model generated photo-oxidation products was considered in addition to the measured primary OH reactants. Carbonyl species such as formaldehyde, acetaldehyde and acetone have been identified as the VOC class dominating organic OH reactivity. As such, together with the direct radical source contribution by photolysis, these species dominate local ozone production in London. Modelling studies comparing the observed carbonyl concentrations with model predictions suggest that over 50% of the total concentration may be directly emitted and, hence, London's in-situ chemistry may be considered to contribute significantly to the ozone levels observed.

Efficiency of N use by wheat as a function of influx and efflux of NO sub 3

NASA Technical Reports Server (NTRS)

Huffaker, R. C.; Aslam, M.; Ward, M. R.

1989-01-01

Since N assimilation is one of the most costly functions of a plant, its efflux before assimilation results in a serious energy cost and loss in efficiency which could decrease yields. Efficient crop production is critical to the Controlled Ecological Life-Support System (CELSS). The objective is to determine the extent of efflux of the N species NO3(-), NH4(+), NO2(-), and urea after uptake, and possible means of regulation. It was found that NO3(-) efflux became serious as its substrate level increased. Efflux/Influx (E/I) of 3NO3(-) was greater in darkness (35 pct) than in light (14 pct) and the ratio greatly increased with increased substrate NO3(-), (up to 45 pct at 10 mM). It seems advantageous to use the lowest possible nutrient concentration of NO3(-). The feasibility of using ClO3(-) as a trapping agent (competitive inhibitor of NO3(-) uptake) for effluxed NO3(-) was assessed and its toxicity determined.

Preparation, structure and microbial evaluation of metal complexes of the second generation quinolone antibacterial drug lomefloxacin

NASA Astrophysics Data System (ADS)

Sadeek, Sadeek A.; El-Shwiniy, Walaa H.

2010-09-01

Lomefloxacinate of Y(III), Zr(IV) and U(VI) were isolated as solids with the general formula; [Y(LFX) 2Cl 2]Cl·12H 2O, [ZrO(LFX) 2Cl]Cl·15H 2O and [UO 2(LFX) 3](NO 3) 2·4H 2O. The new synthesized complexes were characterized with physicochemical and diverse spectroscopic techniques (IR, UV-Vis. and 1H NMR spectroscopies) as well as thermal analyses. In these complexes lomefloxacin act as bidentate ligand bound to the metal ions through the pyridone oxygen and one carboxylate oxygen. The kinetic parameters of thermogravimetric (TGA) and its differential (DTG), such as entropy of activation, activation energy, enthalpy of activation and Gibbs free energy evaluated by using Coats- Redfern and Horowitz- Metzger equations for free lomefloxacin and three complexes were carried out. The bond stretching force constant and length of the U dbnd O bond for the [UO 2(LFX) 3](NO 3) 2·4H 2O complex were calculated. The antimicrobial activity of lomefloxacin and its metal complexes was tested against different bacterial species, such as Staphylococcus aureus ( S. aureus), Escherichia coli ( E. coli) and Pseudomonas aeruginosa ( P. aeruginosa) as Gram-positive and Gram-negative bacterial species and also against two species of antifungal, penicillium ( P. rotatum) and trichoderma ( T. sp.). The three complexes are of a good action against three bacterial species but the Y(III) complex exhibit excellent activity against Pseudomonas aeruginosa ( P. aeruginosa), when compared to the free lomefloxacin.

Cadmium poisoning of oxygen reduction on platinum electrode in potassium hydroxide

NASA Technical Reports Server (NTRS)

Miller, R. O.

1972-01-01

Experiment with a rotating disk and ring apparatus showed no poisoning by cadmium in 8.5 M KOH, alone or with Cl(-) or CO3(=). Poisoning does not occur either in 0.1 M KOH supernatant at CdO, but a partially reversible poisoning results from .0001 M CdCl2 and traces of fatty acid are present. Evidence indicates that the catastrophic poisoning affects the four-electron O2 reduction more than it does the one-electron H3O(+) discharge.

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

Inorganic N and P dynamics of Antarctic glacial meltwater streams as controlled by hyporheic exchange and benthic autotrophic communities

USGS Publications Warehouse

McKnight, Diane M.; Runkel, R.L.; Tate, C.M.; Duff, J.H.; Moorhead, D.L.

2004-01-01

The McMurdo Dry Valleys of South Victoria Land, Antarctica, contain numerous glacial meltwater streams that drain into lakes on the valley floors. Many of the streams have abundant perennial mats of filamentous cyanobacteria. The algal mats grow during streamflow in the austral summer and are in a dormant freeze-dried state during the rest of the year. NO3 and soluble reactive P (SRP) concentrations were lower in streams with abundant algal mats than in streams with sparse algal mats. NO3 and SRP concentrations were higher in the hyporheic zone of a stream with abundant algal mats than in the stream itself. An experimental injection of LiCl, NaNO3, and K3PO4 was conducted in Green Creek, which has abundant algal mats. Substantial hyporheic exchange occurred. The NO3 and PO4 concentrations at 50 m below the injection were 55 ??M and 18 ??M, respectively, during the experiment. NO3 and PO4 concentrations were below the detection limit of 1 to 2 ??M at a site 497 m below the injection during the Cl tracer arrival, indicating a high capacity for nutrient uptake by algal communities. NO2 and NH4 were present at sites 226 and 327 m below the injection, indicating that, in addition to denitrification and algal uptake, dissimilatory NO3 reduction to NO2 and NH4 may be a NO3 sink during transport. Transport modelling with nutrient uptake represented as a 1st-order process yielded reach-scale parameters of 4.3 ?? 10-5 to 3.9 ?? 10-4/s and 1.4 ?? 10-4 to 3.8 ?? 10 -4/s for uptake of NO3 and PO4, respectively. The best match with the observed data was a model in which PO4 uptake occurred only in the main channel and NO3 uptake occurred in the main channel and in the hyporheic zone. Hyporheic NO3 uptake was 7 to 16% of the total uptake for the different stream reaches. These results demonstrate that nutrient flux to the lakes is controlled by hyporheic exchange and nutrient uptake by algal mats in dry valley streams. Streams without algal mats contribute more nutrients to the lakes than streams with algal mats.

Ammonia Vapor-Assisted Synthesis of Cu(OH)2 and CuO Nanostructures: Anionic (Cl-, NO3 -, SO4 2-) Influence on the Product Morphology

NASA Astrophysics Data System (ADS)

Mansournia, Mohammadreza; Arbabi, Akram

2017-01-01

Shape control of inorganic nanostructures generally requires using surfactants or ligands to passivate certain crystallographic planes. This paper describes a novel additive-free synthesis of cupric oxide nanostructures with different morphologies from the aqueous solutions of copper(II) with Cl-, NO3 -, and SO4 2- as counter ions. Through a one-step approach, CuO nanoleaves, nanoparticles and flower-like microspheres were directly synthesized at 80°C upon exposure to ammonia vapor using a cupric solution as a single precursor. Furthermore, during a two-step process, Cu(OH)2 nanofibers and nanorods were prepared under an ammonia atmosphere, then converted to CuO nanostructures with morphology preservation by heat treatment in air. The as-prepared Cu(OH)2 and CuO nanostructures are characterized using x-ray diffraction, scanning electron microscopy and Fourier transformation infrared spectroscopy techniques.

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.

Modeling Heterogeneous CINO2 Formation, Chloride Availability, and Chlorine Cycling in Southeast Texas

EPA Science Inventory

Nitryl chloride (ClNO₂) mixing ratios above 1 ppbv have been measured off the coast of Southeast Texas. ClNO₂ formation, the result of heterogeneous N₂0₅ uptake on chloride-containing aerosols, has a significant impact on oxidant form...

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.

Headspace Analysis of Ammonium Nitrate

DTIC Science & Technology

2017-01-25

to an Agilent 7890 gas chromatograph (GC) (Agilent Technologies, Santa Clara, CA). Methane CI was used to optimize instrument parameters, which...order of 0.1 mTorr, as were CF2Cl2, CF3Cl, methane , and isobutane. Figure 2. Analyte sorbent tube mounted and interfaced with a modified GC...observed at no more than 22% abundance of m/z 17. When larger gases such as methane were mixed in significant proportion with 500 ppm carbon

Method of synthesis of anhydrous thorium(IV) complexes

DOEpatents

Kiplinger, Jaqueline L; Cantat, Thibault

2013-04-30

Method of producing anhydrous thorium(IV) tetrahalide complexes, utilizing Th(NO.sub.3).sub.4(H.sub.2O).sub.x, where x is at least 4, as a reagent; method of producing thorium-containing complexes utilizing ThCl.sub.4(DME).sub.2 as a precursor; method of producing purified ThCl.sub.4(ligand).sub.x compounds, where x is from 2 to 9; and novel compounds having the structures: ##STR00001##

Crystal structures of bis-[(9S,13S,14S)-3-meth-oxy-17-methyl-morphinanium] tetra-chlorido-cobaltate and tetra-chlorido-cuprate.

PubMed

Gauchat, Eric; Nazarenko, Alexander Y

2017-01-01

(9 S ,13 S ,14 S )-3-Meth-oxy-17-methyl-morphinan (dextromethorphan) forms two isostructural salts with ( a ) tetra-chlorido-cobaltate, namely bis-[(9 S ,13 S ,14 S )-3-meth-oxy-17-methyl-morphinanium] tetra-chlorido-cobaltate, (C 18 H 26 NO) 2 [CoCl 4 ], and ( b ) tetra-chlorido-cuprate, namely bis-[(9 S ,13 S ,14 S )-3-meth-oxy-17-methyl-morphinanium] tetra-chlorido-cuprate, (C 18 H 26 NO) 2 [CuCl 4 ]. The distorted tetra-hedral anions are located on twofold rotational axes. The dextromethorphan cation can be described as being composed of two ring systems, a tetra-hydro-naphthalene system A + B and a deca-hydro-isoquinolinium subunit C + D , that are nearly perpendicular to one another: the angle between mean planes of the A + B and C + D moieties is 78.8 (1)° for ( a ) and 79.0 (1)° for ( b ). Two symmetry-related cations of protonated dextromethorphan are connected to the tetra-chlorido-cobaltate (or tetra-chlorido-cuprate) anions via strong N-H⋯Cl hydrogen bonds, forming neutral ion associates. These associates are packed in the (001) plane with no strong attractive bonding between them. Both compounds are attractive crystalline forms for unambiguous identification of the dextromethorphan and, presumably, of its optical isomer, levomethorphan.

Efficiency of N use by wheat as a function of influx and efflux of NO3

NASA Technical Reports Server (NTRS)

Huffaker, R. C.; Aslam, M.; Ward, M. R.

1990-01-01

Since N assimilation is one of the most costly functions of a plant, its efflux before assimilation results in a serious energy cost and loss in efficiency which could decrease yields. Efficient crop production is critical to the Closed Ecology Life Support System (CELSS). The objective is to determine the extent of efflux of the N species NO3(-), NH4(+), NO2(-), and urea after uptake, and possible means of regulation. Researchers found that NO3 efflux became serious as its substrate level increased. Efflux/Influx (E/I) of NO3(-) was greater in darkness (35 percent) than in light (14 percent), and the ratio greatly increased with substrate NO3 (-), (up to 45 percent at 10 mM). It seems advantageous to use the lowest possible nutrient concentration of NO3(-). The feasibility of using ClO3(-) was assessed and its toxicity determined.

1-(3,3-Dichloro-all-yloxy)-2-nitro-benzene.

PubMed

Ren, Dong-Mei; Wang, Yong-Yi

2012-04-01

In the title compound, C(9)H(7)Cl(2)NO(3), the dihedral angle between the benzene ring and the plane of the nitro group is 50.2 (1)°, and that between the benzene ring and the best plane through the dichloro-allyl fragment is 40.1 (1)°.

Hydrogeochemical analysis and evaluation of surface water quality of Pratapgarh district, Uttar Pradesh, India

NASA Astrophysics Data System (ADS)

Tiwari, Ashwani Kumar; Singh, Abhay Kumar; Singh, Amit Kumar; Singh, M. P.

2017-07-01

The hydrogeochemical study of surface water in Pratapgarh district has been carried out to assess the major ion chemistry and water quality for drinking and domestic purposes. For this purpose, twenty-five surface water samples were collected from river, ponds and canals and analysed for pH, electrical conductivity, total dissolved solids (TDS), turbidity, hardness, major cations (Ca2+, Mg2+, Na+ and K+), major anions (HCO3 -, F-, Cl-, NO3 -, SO4 2-) and dissolved silica concentration. The analytical results show mildly acidic to alkaline nature of surface water resources of Pratapgarh district. HCO3 - and Cl- are the dominant anions, while cation chemistry is dominated by Na+ and Ca2+. The statistical analysis and data plotted on the Piper diagram reveals that the surface water chemistry is mainly controlled by rock weathering with secondary contributions from agriculture and anthropogenic sources. Ca2+-Mg2+-HCO3 -, Ca2+-Mg2+-Cl- and Na+-HCO3 --Cl- are the dominant hydrogeochemical facies in the surface water of the area. For quality assessment, values of analysed parameters were compared with Indian and WHO water quality standards, which shows that the concentrations of TDS, F-, NO3 -, Na+, Mg2+ and total hardness are exceeding the desirable limits in some water samples. Water Quality Index (WQI) is one of the most effective tools to communicate information on the quality of any water body. The computed WQI values of Pratapgarh district surface water range from 28 to 198 with an average value of 82, and more than half of the study area is under excellent to good category.

5-Chloro-2-nitro-phenol.

PubMed

Ren, Dong-Mei

2012-05-01

The asymmetric unit of the title compound, C(6)H(4)ClNO(3), contains two independent mol-ecules in which the dihedral angles between the benzene ring and the nitro groups are 2.5 (1) and 8.5 (1)°. Intra-molecular O-H⋯O hydrogen bonds involving the hy-droxy and nitro substituents result in the formation of S(6) six-membered rings. In the crystal, O-H⋯O, O-H⋯Cl and C-H⋯O hydrogen bonds together with Cl⋯O contacts [3.238 (3) and 3.207 (3) Å] generate a three-dimensional network.

The area postrema does not modulate the long-term salt sensitivity of arterial pressure.

PubMed

Collister, J P; Osborn, J W

1998-10-01

The hindbrain circumventricular organ, the area postrema (AP), receives multiple signals linked to body fluid homeostasis. In addition to baroreceptor input, AP cells contain receptors for ANG II, vasopressin, and atrial natriuretic peptide. Hence, it has been proposed that the AP is critical in long-term adjustments in sympathetic outflow in response to changes in dietary NaCl. The present study was designed to test the hypothesis that long-term control of arterial pressure over a range of dietary NaCl requires an intact AP. Male Sprague-Dawley rats were randomly selected for lesion of the AP (APx) or sham lesion. Three months later, rats were instrumented with radiotelemetry transmitters for continuous monitoring of mean arterial pressure (MAP) and heart rate and were placed in individual metabolic cages. Rats were given 1 wk postoperative recovery. The dietary salt protocol consisted of a 7-day period of 1.0% NaCl (control), 14 days of 4.0% NaCl (high), 7 days of 1.0% NaCl, and finally 14 days of 0.1% NaCl (low). The results are reported as the average arterial pressure observed on the last day of the given dietary salt period: APx (n = 7) 114 +/- 2 (1.0%), 110 +/- 3 (4.0%), 110 +/- 3 (1.0%), and 114 +/- 4 (0.1%) mmHg; sham (n = 6) 115 +/- 2 (1.0%), 114 +/- 3 (4.0%), 111 +/- 3 (1. 0%), and 113 +/- 2 (0.1%) mmHg. Neither group of rats demonstrated significant changes in MAP throughout the entire dietary salt protocol. Furthermore, no significant differences in MAP were detected between groups throughout the protocol. All lesions were histologically verified. These results suggest that the area postrema plays no role in long-term control of arterial pressure during chronic changes in dietary salt.

Facile synthesis and characterization of silver nanoparticle/bis(o-phenolpropyl)silicone composites using a gold catalyst.

PubMed

Roh, Sung-Hee; Cheong, Hyeonsook; Kim, Do-Heyoung; Woo, Hee-Gweon; Lee, Byeong-Gweon; Yang, Kap-Seung; Kim, Bo-Hye; Sohn, Honglae

2013-01-01

The generation of silver nanoparticle/bis(o-phenolpropyl)silicone composites have been facilitated by the addition of sodium tetrachloroaurate or gold(Ill) chloride (< 1 wt% of NaAuCl4 or AuCl3) to the reaction of silver nitrate (AgNO3) with bis(o-phenolpropyl)silicone [BPPS, (o-phenolpropyl)2(SiMe2O)n, n = 2,3,8,236]. TEM and FE-SEM data showed that the silver nanoparticles having the size of < 20 nm are well dispersed throughout the BPPS silicone matrix in the composites. XRD patterns are consistent with those for polycrystalline silver. The size of silver nanoparticles augmented with increasing the relative molar concentration of AgNO3 added with respect to BPPS. The addition of gold complexes (1-3 wt%) did not affect the size distribution of silver nanoparticles appreciably. In the absence of BPPS, the macroscopic precipitation of silver by agglomeration, indicating that BPPS is necessary to stabilize the silver nanoparticles surrounded by coordination.

Identification of inadequate maternal progesterone concentrations in nulliparous dairy heifers and treatment with human chorionic gonadotrophin.

PubMed

King, S G; Dobson, H; Royal, M D; Christley, R M; Murray, R D; Routly, J E; Smith, R F; Mann, G E

2013-11-09

Plasma progesterone concentrations were estimated for 381 nulliparous dairy heifers from eight farms on days 4-6 after insemination. Heifers were synchronised using two treatments of prostaglandin F2α (PGF2α) 11 days apart. Alternate heifers were treated with 1500 IU human chorionic gonadotrophin (hCG) at the time of sampling, and the pregnancy status assessed ~35 days after insemination. Heifers with no corpus luteum (CL; n-30) at the second PGF2α had lower progesterone concentrations (P<0.001) and pregnancy rates (PR; P=0.001) compared with heifers with CL (n=351, defined as cyclic). The risk of no CL increased in heifers <15 months of age (OR=7.5, P<0.001) and with body condition score <2.5 (OR=4.5, P=0.001). Those with no CL were removed from further analysis. The 20 per cent cyclic control heifers with progesterone concentrations ≤2 ng/ml on days 4-6 had lower PRs compared with those with higher concentrations (42 per cent vs 64 per cent, OR=0.3, P=0.01). There was no overall effect of hCG on PR compared with controls (51 per cent vs 60 per cent, P=0.10). However, heifers with high progesterone on days 4-6 (>2 ng/ml) had a lower PR after treatment (51 per cent vs 64 per cent, OR=0.6, P=0.02). Heifers inseminated with sexed (n=18) compared with conventional (n=333) semen had a decreased PR (33 per cent vs 57 per cent, OR=0.2, P=0.01). This study demonstrates that higher plasma progesterone concentrations as early as days 4-6 after insemination have a positive effect on first insemination PR, but there was no beneficial effect of hCG treatment on these days in dairy heifers.

The synthesis of PNP-supported low-spin nitro manganese(I) carbonyl complexes

DOE PAGES

Tondreau, Aaron M.; Boncella, James M.

2016-09-01

In this study, the coordination chemistry of Mn(CO) 5Br was investigated with a series of PNP-pincer ligands. The ligands iPrPONOP ( iPrPONOP = 2,6-bis(diisopropylphosphinito)pyridine) and iPrPN HP ( iPrPN HP = HN{CH 2CH 2(PiPr 2)} 2) gave the desired organometallic manganese complexes ( iPrPONOP)Mn(CO) 2Br and ( iPrPN HP)Mn(CO) 2Br, respectively, upon chelation to Mn(CO) 5Br. The reactivity of iPrPNNNP ( iPrPNNNP = N,N'-bis(diisopropylphosphino)-2,6-diaminopyridine) with Mn(CO) 5Br yielded a pair of products, [( iPrPNNNP)Mn(CO) 3][Br] and ( iPrPNNNCO)Mn(CO) 3. The formation of the asymmetric chelate arises from a formal loss of iPr 2PBr and C–N bond formation from a carbonylmore » ligand and NH, yielding a Mn(I) amide core. The nitration reactions of ( iPrPONOP)Mn(CO) 2Br and ( iPrPN HP)Mn(CO) 2Br were carried out using silver nitrite, yielding the nitro compounds ( iPrPONOP)Mn(CO) 2(NO 2) and ( iPrPN HP)Mn(CO) 2(NO 2), respectively. The analogous iron complex ( iPrPONOP)Fe(CO)Cl 2 was nitrated under the same conditions to yield the salt pair [( iPrPONOP)Fe(CO) 2][FeCl 3NO]. This reactivity underlines the difference between iso-valent iron and manganese centers. The manganese complexes ( iPrPONOP)Mn(CO) 2(NO 2) and ( iPrPN HP)Mn(CO) 2(NO 2) were ineffective as oxygen atom transfer reagents for a variety of substrates.« less

The effect of dietary sodium on right ventricular failure-induced ascites, gain and fat deposition in meat-type chickens.

PubMed Central

Julian, R J; Caston, L J; Leeson, S

1992-01-01

Experiments were carried out using various levels of sodium (Na+) from NaCl or NaHCO3 to determine: 1) the level of Na+ required to induce ascites alone or in combination with cold temperature and 2) the effect of Na+ on weight gain and fat deposition in broiler chickens. In experiment 1, there were no cases of ascites using levels of Na+, from NaCl at 0.14% to 0.44% in the feed from day 3 or using added Na+, from NaCl at 0.0% to 0.12% in the water from day 3 with a level of 0.14% in the feed. There was no significant difference in 21 or 42 day body weight, feed conversion, or right ventricle:total ventricle (RV:TV) ratio between treatment groups. Day 3 to 4 body weight gains were significantly increased in all treatment groups with added Na+ (p less than 0.01). In experiment 2, with levels of added Na+, from NaCl, at 0.0% to 0.12% in the water with a level of 0.20% in the feed there were two cases of ascites, one at day 7 and one at day 40 at the 0.12% level. There were no significant differences in body weight at days 21 or 42 or in the RV:TV ratios between groups. Feed conversions were improved (p less than 0.01) with the lowest and highest levels of Na+ and a significant increase in day 3 to 4 body weight gain, with increasing Na+ in all treatment groups, was observed.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:1423057

A pragmatic approach to study the groundwater quality suitability for domestic and agricultural usage, Saq aquifer, northwest of Saudi Arabia.

PubMed

Nazzal, Yousef; Ahmed, Izrar; Al-Arifi, Nassir S N; Ghrefat, Habes; Zaidi, Faisal K; El-Waheidi, Mahmud M; Batayneh, Awni; Zumlot, Taisser

2014-08-01

The present study deals with detailed hydrochemical assessment of groundwater within the Saq aquifer. The Saq aquifer which extends through the NW part of Saudi Arabia is one of the major sources of groundwater supply. Groundwater samples were collected from about 295 groundwater wells and analyzed for various physico-chemical parameters such as electrical conductivity (EC), pH, temperature, total dissolved solids (TDS), Na(+), K(+), Ca(2+), Mg(2+), CO3 (-), HCO3 (-), Cl(-), SO4 (2-), and NO3 (-). Groundwater in the area is slightly alkaline and hard in nature. Electrical conductivity (EC) varies between 284 and 9,902 μS/cm with an average value of 1,599.4 μS/cm. The groundwater is highly mineralized with approximately 30 % of the samples having major ion concentrations above the WHO permissible limits. The NO3 (-) concentration varies between 0.4 and 318.2 mg/l. The depth distribution of NO3 (-) concentration shows higher concentration at shallow depths with a gradual decrease at deeper depths. As far as drinking water quality criteria are concerned, study shows that about 33 % of samples are unfit for use. A detailed assessment of groundwater quality in relation to agriculture use reveals that 21 % samples are unsuitable for irrigation. Using Piper's classification, groundwater was classified into five different groups. Majority of the samples show Mix-Cl-SO4- and Na-Cl-types water. The abundances of Ca(2+) and Mg(2+) over alkalis infer mixed type of groundwater facies and reverse exchange reactions. The groundwater has acquired unique chemical characteristics through prolonged rock-water interactions, percolation of irrigation return water, and reactions at vadose zone.

Tropospheric photooxidation of CF3CH2CHO and CF3(CH2)2CHO initiated by Cl atoms and OH radicals

NASA Astrophysics Data System (ADS)

Antiñolo, M.; Jiménez, E.; Notario, A.; Martínez, E.; Albaladejo, J.

2009-11-01

The absolute rate coefficients for the tropospheric reactions of chlorine (Cl) atoms and hydroxyl (OH) radicals with CF3CH2CHO and CF3(CH2)2CHO were measured as a function of temperature (263-371 K) and pressure (50-215 Torr of He) by pulsed UV laser photolysis techniques. Vacuum UV resonance fluorescence was employed to detect and monitor the time evolution of Cl atoms. Laser induced fluorescence was used in this work as a detection of OH radicals as a function of reaction time. No pressure dependence of the bimolecular rate coefficients, kCl and kOH, was found at all temperatures. At room temperature kCl and kOH were (in 10-11 cm3 molecule-1 s-1): kCl(CF3CH2CHO) = (1.55±0.53); kCl(CF3(CH2)2CHO) = (3.39±1.38); kOH(CF3CH2CHO) = (0.259±0.050); kOH(CF3(CH2)2CHO) = (1.28±0.24). A slightly negative temperature dependence of kCl was observed for CF3CH2CHO and CF3(CH2)2CHO, and kOH(CF3CH2CHO). In contrast, kOH(CF3(CH2)2CHO) did not exhibit a temperature dependence in the studied ranged. Arrhenius expressions for these reactions were: kCl(CF3CH2CHO) =(4.4±1.0) × 10-11 exp{-(316±68)/T} cm3 molecule-1 s-1, kCl(CF3(CH2)2CHO) = (2.9±0.7) × 10-10 exp{-625±80)/T} cm3 molecule-1 s-1, kOH(CF3CH2CHO) = (7.8±2.2) × 10-12 exp{-(314±90)/T} cm3 molecule-1 s-1. The atmospheric impact of the homogeneous removal by OH radicals and Cl atoms of these fluorinated aldehydes is discussed in terms of the global atmospheric lifetimes, taking into account different degradation pathways. The calculated lifetimes show that atmospheric oxidation of CF3(CH2)xCHO are globally dominated by OH radicals, however reactions initiated by Cl atoms can act as a source of free radicals at dawn in the troposphere.

[Analysis of different endodontic sealers and strategies of root canal irrigation on the bond strength of fiber posts].

PubMed

Zhu, Shujin; Liu, Cuiling; Zheng, Zheng; Yang, Liyuan; Gao, Xu

2015-06-01

To evaluate the influence of eugenol-containing and resin-containing endodontic sealers on the bond strength of fiber posts using different strategies of root canal irrigation. Forty-eight mandibular premolars were endodontically treated. The specimens were randomly assigned into two groups according to different endodontic sealers. Group A used Endofil (eugenol-containing endodontic sealer), and group B used AH-plus (resin-containing endodontic sealer). After post space preparation, each group was randomly assigned into three subgroups according to the strategies of root canal irrigation (eight premolars in each subgroup). Group Al and B1: 0.9%NaCl irrigation; Group A2 and B2: 17% ethylene diamine tetraacetic acid (EDTA)+5.25%NaClO+0.9%NaCl irrigation; Group A3 and B3: ultrasonic agitation associated with 1 7%EDTA+5.25%NaClO+0.9%NaCl. One week after the cementation of fiber posts using RelyX™ Unicem, a push-out test was performed to measure the bond strength of the posts. The microstructure of the root canal surface was examined under scanning electron microscope (SEM). The bond strengths of the six groups were as follows: Al (7.96±2.23) MPa, A2 (9.95±2.89) MPa, A3 (18.88±3.69) MPa, B1 (11.41±3.71) MPa, B2 (14.00±4.04) MPa, and B3 (19.14±3.27) MPa. Statistical analysis revealed a significant interaction between the different endodontic sealers and the strategies of root canal irrigation (P<0.05). Lower bond strength was found in group Al but not in group BI (P<0.05), and the same result was revealed when comparing group A2 and B2. No significant difference was observed between group A3 and B3 (P>0.05). SEM showed that the root canal in group A3 and B3 achieved the cleanest surface with nearly all dentine tubules opened. The eugenol-containing endodontic sealer can impair the bond strength of fiber posts compared with the resin-containing sealer when the root canal is irrigated by 0.9% NaCl or 17%EDTA+5.25%NaClO+0.9%NaC. No difference was observed between the two sealers when using 17%EDTA+5.25% NaCIO+0.9%NaCl combined with ultrasonic irrigation.

Excited electronic state decomposition mechanisms and dynamics of nitramine energetic materials and model systems

NASA Astrophysics Data System (ADS)

Greenfield, Margo

Energetic materials play an important role in aeronautics, the weapon industry, and the propellant industry due to their broad applications as explosives and fuels. RDX (1,3,5-trinitrohexahydro-s-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), and CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) are compounds which contain high energy density. Although RDX and HMX have been studied extensively over the past several decades a complete understanding of their decomposition mechanisms and dynamics is unknown. Time of flight mass spectroscopy (TOFMS) UV photodissociation (ns) experiments of gas phase RDX, HMX, and CL-20 generate the NO molecule as the initial decomposition product. Four different vibronic transitions of the initial decomposition product, the NO molecule, are observed: A2Sigma(upsilon'=0)←X 2pi(upsilon"=0,1,2,3). Simulations of the rovibronic intensities for the A←X transitions demonstrate that NO dissociated from RDX, HMX, and CL-20 is rotationally cold (˜20 K) and vibrationally hot (˜1800 K). Conversely, experiments on the five model systems (nitromethane, dimethylnitramine (DMNA), nitropyrrolidine, nitropiperidine and dinitropiperazine) produce rotationally hot and vibrationally cold spectra. Laser induced fluorescence (LIF) experiments are performed to rule out the possible decomposition product OH, generated along with NO, perhaps from the suggested HONO elimination mechanism. The OH radical is not observed in the fluorescence experiments, indicating the HONO decomposition intermediate is not an important pathway for the excited electronic state decomposition of cyclic nitramines. The NO molecule is also employed to measure the dynamics of the excited state decomposition. A 226 nm, 180 fs light pulse is utilized to photodissociate the gas phase systems. Stable ion states of DMNA and nitropyrrolidine are observed while the energetic materials and remaining model systems present the NO molecule as the only observed product. Pump-probe transients of the resonant A←X (0-0) transition of the NO molecule show a constant signal indicating these materials decompose faster than the time duration of the 226 nm laser light. Calculational results together with the experimental results indicate the energetic materials decompose through an internal conversion to very highly excited (˜5 eV of vibrational energy) vibrational states of their ground electronic state, while the model systems follow an excited electronic state decomposition pathway.

Characterization of major pollution events (dust, haze, and two festival events) at Agra, India.

PubMed

Pachauri, Tripti; Singla, Vyoma; Satsangi, Aparna; Lakhani, Anita; Kumari, K Maharaj

2013-08-01

Total suspended particulate (TSP) samples were collected during dust, haze, and two festival events (Holi and Diwali) from February 2009 to June 2010. Pollutant gases (NO2, SO2, and O3) along with the meteorological parameters were also measured during the four pollution events at Agra. The concentration of pollutant gases decreases during dust events (DEs), but the levels of the gases increase during other pollution events indicating the impact of anthropogenic emissions. The mass concentrations were about two times higher during pollution events than normal days (NDs). High TSP concentrations during Holi and Diwali events may be attributed to anthropogenic activities while increased combustion sources in addition to stagnant meteorological conditions contributed to high TSP mass during haze events. On the other hand, long-range transport of atmospheric particles plays a major role during DEs. In the dust samples, Ca(2+), Cl(-), NO3 (-), and SO4 (2-) were the most abundant ions and Ca(2+) alone accounted for 22 % of the total ionic mass, while during haze event, the concentrations of secondary aerosols species, viz., NO3 (-), SO4 (2-), and NH4 (+), were 3.6, 3.3, and 5.1 times higher than the normal days. During Diwali, SO4 (2-) concentration (17.8 μg m(-3)) was highest followed by NO3 (-), K(+), and Cl(-) while the Holi samples were strongly enriched with Cl(-) and K(+) which together made up 32.7 % of the total water-soluble ions. The ion balances indicate that the haze samples were acidic. On the other hand, Holi, Diwali, and DE samples were enriched with cations. The carbonaceous aerosol shows strong variation with the highest concentration during Holi followed by haze, Diwali, DEs, and NDs. However, the secondary organic carbon concentration follows the order haze > DEs > Diwali > Holi > NDs. The scanning electron microscope/EDX results indicate that KCl and carbon-rich particles were more dominant during Holi and haze events while DE samples were enriched with particles of crustal origin.

Nitric oxide modulates cadmium influx during cadmium-induced programmed cell death in tobacco BY-2 cells.

PubMed

Ma, Wenwen; Xu, Wenzhong; Xu, Hua; Chen, Yanshan; He, Zhenyan; Ma, Mi

2010-07-01

Nitric oxide (NO) is a bioactive gas and functions as a signaling molecule in plants exposed to diverse biotic and abiotic stresses including cadmium (Cd(2+)). Cd(2+) is a non-essential and toxic heavy metal, which has been reported to induce programmed cell death (PCD) in plants. Here, we investigated the role of NO in Cd(2+)-induced PCD in tobacco BY-2 cells (Nicotiana tabacum L. cv. Bright Yellow 2). In this work, BY-2 cells exposed to 150 microM CdCl(2) underwent PCD with TUNEL-positive nuclei, significant chromatin condensation and the increasing expression of a PCD-related gene Hsr203J. Accompanied with the occurring of PCD, the production of NO increased significantly. The supplement of NO by sodium nitroprusside (SNP) had accelerated the PCD, whereas the NO synthase inhibitor Nomega-nitro-L-arginine methyl ester hydrochloride (L-NAME) and NO-specific scavenger 2-(4-carboxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (cPTIO) alleviated this toxicity. To investigate the mechanism by which NO exerted its function, Cd(2+) concentration was measured subsequently. SNP led more Cd(2+) content than Cd(2+) treatment alone. By contrast, the prevention of NO by L-NAME decreased Cd(2+) accumulation. Using the scanning ion-selective electrode technique, we analyzed the pattern and rate of Cd(2+) fluxes. This analysis revealed the promotion of Cd(2+) influxes into cells by application of SNP, while L-NAME and cPTIO reduced the rate of Cd(2+) uptake or even resulted in net Cd(2+) efflux. Based on these founding, we concluded that NO played a positive role in CdCl(2)-induced PCD by modulating Cd(2+) uptake and thus promoting Cd(2+) accumulation in BY-2 cells.

Ion-enhanced chemical etching of ZrO2 in a chlorine discharge

NASA Astrophysics Data System (ADS)

Sha, Lin; Cho, Byeong-Ok; Chang, Jane P.

2002-09-01

Chlorine plasma is found to chemically etch ZrO2 thin films in an electron cyclotron resonance reactor, and the etch rate scaled linearly with the square root of ion energy at high ion energies with a threshold energy between 12-20 eV. The etching rate decreased monotonically with increasing chamber pressures, which corresponds to reduced electron temperatures. Optical emission spectroscopy and quadrupole mass spectrometry were used to identify the reaction etching products. No Zr, O, or ZrCl were detected as etching products, but highly chlorinated zirconium compounds (ZrCl2, ZrCl3, and ZrCl4) and ClO were found to be the dominant etching products. ZrCl3 was the dominant etching products at low ion energies, while ZrCl4 became dominant at higher ion energies. This is consistent with greater momentum transfer and enhanced surface chlorination, as determined by x-ray photoelectron spectroscopy, at increased ion energies. Several ion-enhanced chemical reactions are proposed to contribute to the ZrO2 etching. copyright 2002 American Vacuum Society.

Geochemical signatures of groundwater in the coastal aquifers of Thiruvallur district, south India

NASA Astrophysics Data System (ADS)

Senthilkumar, S.; Balasubramanian, N.; Gowtham, B.; Lawrence, J. F.

2017-03-01

An attempt has been made to identify the chemical processes that control the hydrochemistry of groundwater in the coastal aquifers of Thiruvallur coastal village of Thiruvallur district, Tamil Nadu, south India. The parameters such as pH, EC, TDS and major ion concentrations of Na, K, Ca, Mg, Cl, HCO3, SO4 and NO3 of the groundwater were analyzed. Abundances of these ions are in the following order Na > Ca > Mg > K and HCO3 > Cl > SO4 > NO3. The dominant water types are in the order of NaCl> mixed CaMgCl > CaHCO3 > CaNaHCO3. Water types (mixed CaHCO3, mixed CaMgCl and NaCl) suggest that the mixing of high salinity water caused from surface contamination sources such as irrigation return flow, domestic wastewater and septic tank effluents with existing water followed by ion exchange reaction processes, silicate weathering and evaporation are responsible for the groundwater chemistry of the study area. The above statement is further supported by Gibbs plot where most of the samples fall within the evaporation zone.

Nonenzymatic and enzymatic hydrolysis of alkyl halides: A theoretical study of the SN2 reactions of acetate and hydroxide ions with alkyl chlorides

PubMed Central

Maulitz, Andreas H.; Lightstone, Felice C.; Zheng, Ya-Jun; Bruice, Thomas C.

1997-01-01

The SN2 displacements of chloride ion from CH3Cl, C2H5Cl, and C2H4Cl2 by acetate and hydroxide ions have been investigated, using ab initio molecular orbital theory at the HF/6–31+G(d), MP2/6–31+G(d), and MP4/6–31+G(d) levels of theory. The central barriers (calculated from the initial ion–molecule complex) of the reactions, the differences of the overall reaction energies, and the geometries of the transition states are compared. Essential stereochemical changes before and after the displacement reactions are described for selected cases. The gas phase reactions of hydroxide with CH3Cl, C2H5Cl, and C2H4Cl2 have no overall barrier, but there is a small overall barrier for the reactions of acetate with CH3Cl, C2H5Cl, and C2H4Cl2. A self-consistent reaction field solvation model was used to examine the SN2 reactions between methyl chloride and hydroxide ion and between 1,2-dichloroethane and acetate in solution. As expected, the reactions in polar solvent have a large barrier. However, the transition state structures determined by ab initio calculations change only slightly in the presence of a highly polar solvent as compared with the gas phase. We also calibrated the PM3 method for future study of an enzymatic SN2 displacement of halogen. PMID:9192609

21 CFR 184.1845 - Stannous chloride (anhydrous and dihydrated).

Code of Federal Regulations, 2010 CFR

2010-04-01

.... Anhydrous stannous chloride (SnCl2, CAS Reg. No. 7772-99-8) is the chloride salt of metallic tin. It is prepared by reacting molten tin with either chlorine or gaseous tin tetrachloride. Dihydrated stannous chloride (SnCl2·2H2O, CAS Reg. No. 10025-0969-091) is the chloride salt of metallic tin that contains two...

21 CFR 184.1845 - Stannous chloride (anhydrous and dihydrated).

Code of Federal Regulations, 2013 CFR

2013-04-01

.... Anhydrous stannous chloride (SnCl2, CAS Reg. No. 7772-99-8) is the chloride salt of metallic tin. It is prepared by reacting molten tin with either chlorine or gaseous tin tetrachloride. Dihydrated stannous chloride (SnCl2·2H2O, CAS Reg. No. 10025-69-1) is the chloride salt of metallic tin that contains two...

21 CFR 184.1845 - Stannous chloride (anhydrous and dihydrated).

Code of Federal Regulations, 2011 CFR

2011-04-01

.... Anhydrous stannous chloride (SnCl2, CAS Reg. No. 7772-99-8) is the chloride salt of metallic tin. It is prepared by reacting molten tin with either chlorine or gaseous tin tetrachloride. Dihydrated stannous chloride (SnCl2·2H2O, CAS Reg. No. 10025-0969-091) is the chloride salt of metallic tin that contains two...

21 CFR 184.1845 - Stannous chloride (anhydrous and dihydrated).

Code of Federal Regulations, 2012 CFR

2012-04-01

.... Anhydrous stannous chloride (SnCl2, CAS Reg. No. 7772-99-8) is the chloride salt of metallic tin. It is prepared by reacting molten tin with either chlorine or gaseous tin tetrachloride. Dihydrated stannous chloride (SnCl2·2H2O, CAS Reg. No. 10025-69-1) is the chloride salt of metallic tin that contains two...

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...

Dietary linoleate preserves cardiolipin and attenuates mitochondrial dysfunction in the failing rat heart

PubMed Central

Mulligan, Christopher M.; Sparagna, Genevieve C.; Le, Catherine H.; De Mooy, Anthony B.; Routh, Melissa A.; Holmes, Michael G.; Hickson-Bick, Diane L.; Zarini, Simona; Murphy, Robert C.; Xu, Fred Y.; Hatch, Grant M.; McCune, Sylvia A.; Moore, Russell L.; Chicco, Adam J.

2012-01-01

Aims Cardiolipin (CL) is a tetra-acyl phospholipid that provides structural and functional support to several proteins in the inner mitochondrial membrane. The majority of CL in the healthy mammalian heart contains four linoleic acid acyl chains (L4CL). A selective loss of L4CL is associated with mitochondrial dysfunction and heart failure in humans and animal models. We examined whether supplementing the diet with linoleic acid would preserve cardiac L4CL and attenuate mitochondrial dysfunction and contractile failure in rats with hypertensive heart failure. Methods and results Male spontaneously hypertensive heart failure rats (21 months of age) were administered diets supplemented with high-linoleate safflower oil (HLSO) or lard (10% w/w; 28% kilocalorie fat) or without supplemental fat (control) for 4 weeks. HLSO preserved L4CL and total CL to 90% of non-failing levels (vs. 61–75% in control and lard groups), and attenuated 17–22% decreases in state 3 mitochondrial respiration observed in the control and lard groups (P < 0.05). Left ventricular fractional shortening was significantly higher in HLSO vs. control (33 ± 2 vs. 29 ± 2%, P < 0.05), while plasma insulin levels were lower (5.4 ± 1.1 vs. 9.1 ± 2.3 ng/mL; P < 0.05), with no significant effect of lard supplementation. HLSO also increased serum concentrations of several eicosanoid species compared with control and lard diets, but had no effect on plasma glucose or blood pressure. Conclusion Moderate consumption of HLSO preserves CL and mitochondrial function in the failing heart and may be a useful adjuvant therapy for this condition. PMID:22411972

Chemical synthesis of hexagonal indium nitride nanocrystallines at low temperature

NASA Astrophysics Data System (ADS)

Wang, Liangbiao; Shen, Qianli; Zhao, Dejian; Lu, Juanjuan; Liu, Weiqiao; Zhang, Junhao; Bao, Keyan; Zhou, Quanfa

2017-08-01

In this study, hexagonal indium nitride nanocystallines with high crystallinity have been prepared by the reaction of InCl3·4H2O, sulfur and NaNH2 in an autoclave at 160 °C. The crystal structures and morphologies of the obtained InN sample are characterized by X-ray diffraction and scanning electron microscope. As InCl3·4H2O is substituted by In(NO3)3·4.5H2O, InN nanocrystallines could also be obtained by using the similar method. The photoluminescence spectrum shows that the InN emits a broad peak positioned at 2.3 eV.

Biochemical basis of improvement of defense in tomato plant against Fusarium wilt by CaCl2.

PubMed

Chakraborty, Nilanjan; Chandra, Swarnendu; Acharya, Krishnendu

2017-07-01

The objective of this study was to investigate the effectiveness of calcium chloride (CaCl 2 ), as potential elicitor, on tomato plants against Fusarium oxysporum f. sp. lycopersici . Foliar application of CaCl 2 showed significant reduction of wilt incidence after challenge inoculation. Increased production of defense and antioxidant enzymes was observed in elicitor treated sets over control. Simultaneously, altered amount of phenolic acids were analyzed spectrophotometrically and by using high performance liquid chromatography. Significant induction of defense-related genes expressions was measured by semi-quantitative RT-PCR. Greater lignifications by microscopic analysis were also recorded in elicitor treated plants. Simultaneously, generation of nitric oxide (NO) in elicitor treated plants was confirmed by spectrophotometrically and microscopically by using membrane permeable fluorescent dye. Furthermore, plants treated with potential NO donor and NO modulators showed significant alteration of all those aforesaid defense molecules. Transcript analysis of nitrate reductase and calmodulin gene showed positive correlation with elicitor treatment. Furthermore, CaCl 2 treatment showed greater seedling vigor index, mean trichome density etc. The result suggests that CaCl 2 have tremendous potential to elicit defense responses as well as plant growth in co-relation with NO, which ultimately leads to resistance against the wilt pathogen.

Biochar produced from oak sawdust by Lanthanum (La)-involved pyrolysis for adsorption of ammonium (NH4(+)), nitrate (NO3(-)), and phosphate (PO4(3-)).

PubMed

Wang, Zhanghong; Guo, Haiyan; Shen, Fei; Yang, Gang; Zhang, Yanzong; Zeng, Yongmei; Wang, Lilin; Xiao, Hong; Deng, Shihuai

2015-01-01

A series of biochars were prepared by pyrolyzing oak sawdust with/without LaCl3 involvement at temperature of 300-600 °C, and approximate and ultimate analyses were carried out to check their basic characteristics. Meanwhile, the releases of readily soluble NH4(+), NO3(-) and PO4(3-) from biochars and the adsorption of NH4(+), NO3(-) and PO4(3-) by biochars were investigated. Results indicated that the involvement of LaCl3 in pyrolysis could advance the temperature of maximum mass loss by 10 °C compared with oak sawdust (CK), and potentially promoted biochar yield. Overall, the releases of readily soluble NH4(+), NO3(-) and PO4(3-) from biochars were negatively related to pyrolysis temperature, and the releases were greatly weakened by La-biochars. Additionally, the adsorption to NH4(+) can be promoted by the biochars produced at low temperature. On the contrary, the NO3(-) adsorption can be improved by increasing pyrolysis temperature. The highest PO4(3-) adsorption was achieved by the biochars produced at 500 °C. According to the results of adsorption isotherms, the maximum adsorption capacity of NH4(+), NO3(-) and PO4(3-) can be significantly promoted by 1.9, 11.2, and 4.5 folds using La-biochars. Based on the observations of FT-IR, SEM-EDS, and surface functional groups, the improvement of NH4(+) adsorption was potentially associated with the existing acidic function groups (phenolic-OH and carboxyl C=O). The increased basic functional groups on La-biochars were beneficial to improve NO3(-) and PO4(3-) adsorption. Besides, PO4(3-) adsorption was also potentially related to the formed La2O3. Copyright © 2014 Elsevier Ltd. All rights reserved.

Screening and characterization of bacteria that can utilize ammonium and nitrate ions simultaneously under controlled cultural conditions.

PubMed

Zhou, Qi; Takenaka, Shinji; Murakami, Shuichiro; Seesuriyachan, Phisit; Kuntiya, Ampin; Aoki, Kenji

2007-02-01

Eighteen bacterial stock cultures were examined for their ability to utilize NH(4)(+) and NO(3)(-) simultaneously in a medium containing NH(4)NO(3) with shaking using a test tube capped with a cotton stopper. Pseudomonas aeruginosa NBRC 12689 utilized 1 mg/ml of NH(4)NO(3) most rapidly of the cultures tested. The bacterium could completely utilize 5 mg/ml of NH(4)NO(3) within 3 d, 6 mg/ml of NH(4)Cl within 3 d, and 20 mg/ml of NaNO(3) within 2 d under optimum conditions. The addition of Fe(2+) to the NH(4)NO(3) medium markedly promoted the utilization of the two ions. When the Pseudomonas strain utilized 5 mg/ml of NH(4)NO(3) completely, the total nitrogen in the culture including its cells decreased to 41% of that of the NH(4)NO(3) originally provided. GC-MS analysis showed that the removed nitrogen was probably denitrified. When the bacterium was incubated in the NH(4)NO(3) medium with shaking in a vial sealed with a rubber stopper, N(2) accumulated, but not N(2)O at the final phase of cultivation. On the other hand, both N(2) and N(2)O were detected in the NaNO(3) medium. We concluded that the bacterium removed NH(4)(+) from NH(4)NO(3) as a nitrogen source for its cell components, together with the denitrification of NO(3)(-) under controlled shaking conditions. In addition, NH(4)(+) promoted the cell growth of the bacterium and denitrification to N(2), preventing the accumulation of N(2)O.

Production of an extracellular thermohalophilic lipase from a moderately halophilic bacterium, Salinivibrio sp. strain SA-2.

PubMed

Amoozegar, Mohammad Ali; Salehghamari, Ensieh; Khajeh, Khosro; Kabiri, Mahbube; Naddaf, Saied

2008-06-01

Fifty strains of moderately halophilic bacteria were isolated from various salty environments in Iran. A strain designated as SA-2 was shown to be the best producer of extracellular lipase and was selected for further studies. Biochemical and physiological characterization along with 16S rDNA sequence analysis placed SA-2 in the genus Salinivibrio. The optimum salt, pH, temperature and aeration for enzyme production were 0.1 M KCl, pH 8, 35 degrees C and 150 rpm, respectively. The enzyme production was synchronized bacterial growth and reached a maximum level during the early-stationary phase in the basal medium containing 1 M NaCl. Triacylglycerols enhanced lipase production, while carbohydrates had inhibitory effects on it. The maximum lipase activity was obtained at pH 7.5, 50 degrees C and CaCl(2) concentration of 0.01 M. The enzyme was stable at pH range of 7.5-8 and retained 90% of its activity at 80 degrees C for 30 min. Different concentrations of NaNO(3), Na(2)SO(4), KCl and NaCl had no affect on lipase stability for 3 h. These results suggest that the lipase secreted by Salinivibrio sp. strain SA-2 is industrially important from the perspective of its tolerance to a broad temperature range, its moderate thermoactivity and its high tolerance to a wide range of salt concentrations (0-3 M NaCl).

[Size distributions and source apportionment of soluble ions in aerosol in Nanjing].

PubMed

Xue, Guo-Qiang; Zhu, Bin; Wang, Hong-Lei

2014-05-01

To explore the seasonal variation and source apportionment of soluble ions in PM10, PM2.1 and PM1.1, the aerosol mass. concentration and soluble ion concentration were investigated during a one-year observation in the urban-district and north suburb. As the results showed, (1)The concentrations of PM10, PM2.1, PM1.1 were in the order of winter > spring > autumn > summer. In spring, summer and autumn, the concentrations of PM10, PM2.1, PM1.1 in the north suburb were higher than in the urban, while the situation, was opposite in winter. (2) SO(2-)(4), NO(-)(3), Ca2+, NH(+)(4), Cl-, K+, Na+, F-, NO;, Mg2+ were measured, and their total concentration in PM10 was 46 microg.m -3 in urban sites and 39.6 microg m in north suburbs. Mass fraction percentage o f water soluble ion in PM2.1-10, PM1 1-2.1, PM1.1 in the urban district increased from 20.4% to 49.5% and 56% , and the value in the north suburb increased from 18.3% to 37. 9% and 42.5%. (3) Major ions, SO(2-)(4), NO(-)(3) , NH(+)(4) , second components and Ca2+ , had significant seasonal variation. In the urban district, the highest concentrations were observed in winter, and the lowest in summer, while in the. north suburb, the highest concentrations were observed in spring, and the lowest in summer. The seasonal changing climate in Nanjing and different anthropogenic influences with land surface in urban-suburb may be the major factors for the ions' seasonal variation. (4) NH(+)(4) , SO(2-)(4) , NO(-)(3) came from secondary chemical reactions of NH3, SO2, NO,, and these precursors mostly came from automobile exhaust in Summer while equally came from automobile exhaust and fossil fuel in winter. Cl- came from biomass burning in Winter . while transported from sea salt with Na+ in Summer. Ca2+ and Mg2+ came from ground dust and construction dust. K+, F- , NO(-)(2) may come from biomass burning and industrial emissions.

Abiotic stress and phytohormones affect enzymic activity of 1-O-(indole-3-acetyl)-β-d-glucose: myo-inositol indoleacetyl transferase from rice (Oryza sativa).

PubMed

Ciarkowska, Anna; Ostrowski, Maciej; Jakubowska, Anna

2016-10-20

Indole-3-acetic acid (IAA) conjugation is a part of mechanism regulating free auxin concentration. 1-O-(indole-3-acetyl)-β-d-glucose: myo-inositol indoleacetyl transferase (IAInos synthase) is an enzyme involved in IAA-ester conjugates biosynthesis. Biotic and abiotic stress conditions can modulate auxin conjugates formation in plants. In this study, we investigated effect of plant hormones (IAA, ABA, SA and 2,4-D) and abiotic stress (drought and salt stress: 150mM NaCl and 300mM NaCl) on expression level and catalytic activity of rice IAInos synthase. Enzymic activity assay indicated that all tested phytohormones affected activity of IAInos synthase, but only ABA had inhibiting effect, while IAA, SA and 2,4-D activated the enzyme. Drought and salt stress induced with lower NaCl concentration resulted in decreased activity of IAInos synthase, but 300mM NaCl had no effect on the enzyme. Despite observed differences in enzymic activities, no changes of expression level, tested by semiquantitative RT-PCR and Western blot, were detected. Based on our results it has been supposed that plant hormones and stress conditions affect IAInos synthase activity on posttranslational level. Copyright © 2016 Elsevier GmbH. All rights reserved.

Enhanced adsorption of chromium onto activated carbon by microwave-assisted H(3)PO(4) mixed with Fe/Al/Mn activation.

PubMed

Sun, Yuanyuan; Yue, Qinyan; Mao, Yanpeng; Gao, Baoyu; Gao, Yuan; Huang, Lihui

2014-01-30

FeCl3, AlCl3 and MnCl2 were used as the assisted activation agent in activated carbon preparation by H3PO4 activation using microwave heating method. The physico-chemical properties of activated carbons were investigated by scanning electron microscope (SEM), N2 adsorption/desorption, Boehm's titration, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). To investigate the adsorption performances of chromium onto these newly developed activated carbons, a batch of experiments were performed under different adsorption conditions: solution pH, initial Cr(VI) ion concentration, contact time and co-existing ions. The results suggested that carbon with MnCl2 as assisted activation agent displayed the highest BET surface area (1332m(2)/g) and the highest pore volume (1.060cm(3)/g). FeCl3, AlCl3 and MnCl2 had successfully improved Cr(VI) adsorption and activated carbon with FeCl3 as assisted activation agent exhibited the best uptake capacity. To study the transformation of Cr(VI) in adsorption process, total chromium in the aqueous solution was also recorded. The ratio of the amount of Cr(VI) to Cr(III) on each adsorbent was explained by XPS analysis results. Both the co-existing salts (Na2SO4 and NaNO3) demonstrated promoted effects on Cr(VI) removal by four carbons. The pseudo-second-order model and Freundlich equation displayed a good correlation with adsorption data. Copyright © 2013 Elsevier B.V. All rights reserved.

Ageing of a phosphate ceramic used to immobilize chloride contaminated actinide waste

NASA Astrophysics Data System (ADS)

Metcalfe, B. L.; Donald, I. W.; Fong, S. K.; Gerrard, L. A.; Strachan, D. M.; Scheele, R. D.

2009-03-01

A process for the immobilization of intermediate level waste containing a significant quantity of chloride using Ca3(PO4)2 as the host material has been developed. Waste ions are incorporated into two phosphate-based phases, chlorapatite [Ca5(PO4)3Cl] and spodiosite [Ca2(PO4)Cl]. Non-active trials performed using Sm as the actinide surrogate demonstrated the durability of these phases in aqueous solution. Trials of the process, in which actinide-doped materials were used, were performed at PNNL which confirmed the wasteform resistant to aqueous leaching. Initial leach trials conducted on 239Pu/241Am loaded ceramic at 313 K/28 days gave normalized mass losses of 1.2 × 10-5 g m-2 and 2.7 × 10-3 g m-2 for Pu and Cl, respectively. In order to assess the response of the phases to radiation-induced damage, accelerated ageing trials were performed on samples in which the 239Pu was replaced with 238Pu. No changes to the crystalline structure of the waste were detected in the XRD spectra after the samples had experienced an α radiation fluence of 4 × 1018 g-1. Leach trials showed that there was an increase in the P and Ca release rates but no change in the Pu release rate.

The effect of ionic environment and mercury(II) binding on the alternative structures of DNA. An infrared spectroscopic study

NASA Astrophysics Data System (ADS)

Keller, P. B.; Hartman, K. A.

Infrared spectroscopy was used to measure the effects of NaCl, NaNO 3 and HgCl 2 on the structure and structural transitions of DNA in hydrated films. The following conclusions are supported by the data. (1) The transition from the B- to the A-structural form in films of salt-free, calf-thymus DNA occurs between 86 and 75% r.h. Previous failures to obtain this transition in salt-free films and the finding that ca 4% (w/w) NaCl is needed to observe the B to A transition in films of DNA appear to be anomalies produced by the very slow kinetics for this transition. (2) The addition of NaCl to DNA increases the quantity of water absorbed at a given r.h. value and shifts the B to A transition to lower r.h. values. (3) Highly hydrated DNA (100% r.h.) with or without added NaCl exists in the B-helical structure for all samples examined. (4) DNA films containing one NaNO 3 per 6.7 nucleotide residues remained in the B-helical form to very low values of hydration. (5) The interaction of HgCl 2 with DNA to form the type I complex prevents the transition of DNA from the B- to the A-helical form but a conformational variation within the B family of structures was observed to occur between 94 and 75% r.h. (6) The primary sites of binding of Hg 2+ in the type-1 complex with the DNA are the AT base pairs. Hg 2+ binds to the N3 atom of thymine. Binding of Hg 2+ to AT pairs perturbs the CG pairs but has only a minor effect on the sugar—phosphate conformation.

Effect of 5% Chlorine Dioxide Irrigant on Micro Push Out Bond Strength of Resin Sealer to Radicular Dentin: An In Vitro Study

PubMed Central

Devarasanahalli, Swapna V; Aswathanarayana, Ranjini M; Rashmi, K; Gowda, Yashwanth; Nadig, Roopa R

2017-01-01

Introduction Chlorine dioxide (ClO2) has been recently investigated as a possible root canal irrigant due to its broad spectrum of antimicrobial action, tissue dissolution and smear layer removal properties. Literature is scarce on the effect of chlorine dioxide irrigation on the resin sealer dentin bond strength. Aim To compare 5% chlorine dioxide (ClO2) with or without Ethylene Diamine Tetra Acetic acid (EDTA) with 3% Sodium hypochlorite (NaOCl) and EDTA combination as endodontic irrigants on the adhesion of AH Plus sealer to radicular dentin using micro- Push out Bond Strength (µPBS) test. Materials and Methods Forty freshly extracted central incisors were decoronated and randomly divided into four groups based on the different irrigation regimes followed during irrigation: Group I - 3% NaOCl + 17% EDTA, Group II - 5% ClO2 + 17% EDTA, Group III - 5% ClO2 and Group IV – Saline, and canal enlarged till Protaper F3. All the samples were obturated with F3 gutta-percha cones using AH Plus sealer and sectioned perpendicular to long axis to obtain 1mm thick slices from the middle and coronal portions for µPBS measurement in universal testing machine followed by assessment of failure pattern under stereomicroscope. Data was analysed using One-way analysis of variance (ANOVA), Bonferroni and t-test. Results Bond strength values were in the following order: Group I>Group II>Group III>Group IV, with no statistically significant difference amongst experimental groups on intergroup comparison, except with saline. The µPBS values were more in coronal third than middle third in all specimens, with no statistical significant difference. Mode of failure showed mixed patterns in all experimental groups except saline. Conclusion In the present study, the bond strength values of ClO2 were comparable with conventional NaOCl and EDTA combination and hence, ClO2 can be considered as an effective alternative endodontic irrigant. PMID:28658907

Ferric Sulfate and Proline Enhance Heavy-Metal Tolerance of Halophilic/Halotolerant Soil Microorganisms and Their Bioremediation Potential for Spilled-Oil Under Multiple Stresses

PubMed Central

Al-Mailem, Dina M.; Eliyas, Mohamed; Radwan, Samir S.

2018-01-01

The aim of this study was to explore the heavy-metal resistance and hydrocarbonoclastic potential of microorganisms in a hypersaline soil. For this, hydrocarbonoclastic microorganisms were counted on a mineral medium with oil vapor as a sole carbon source in the presence of increasing concentrations of ZnSO4, HgCl2, CdSO4, PbNO3, CuSO4, and Na2HAsO4. The colony-forming units counted decreased in number from about 150 g-1 on the heavy-metal-free medium to zero units on media with 40–100 mg l-1 of HgCl2, CdSO4, PbNO3, or Na2HAsO4. On media with CuSO4 or ZnSO4 on the other hand, numbers increased first reaching maxima on media with 50 mg l-1 CuSO4 and 90 mg l-1 ZnSO4. Higher concentrations reduced the numbers, which however, still remained considerable. Pure microbial isolates in cultures tolerated 200–1600 mg l-1 of HgCl2, CdSO4, PbNO3, CuSO4, and Na2HAsO4 in the absence of crude oil. In the presence of oil vapor, the isolates tolerated much lower concentrations of the heavy metals, only 10–80 mg l-1. The addition of 10 Fe2(SO4)3 and 200 mg l-1 proline (by up to two- to threefold) enhanced the tolerance of several isolates to heavy metals, and consequently their potential for oil biodegradation in their presence. The results are useful in designing bioremediation technologies for oil spilled in hypersaline areas. PMID:29563904

Impact of environmental conditions on aggregation kinetics of hematite and goethite nanoparticles

NASA Astrophysics Data System (ADS)

Xu, Chen-yang; Deng, Kai-ying; Li, Jiu-yu; Xu, Ren-kou

2015-10-01

Hematite and goethite nanoparticles were used as model minerals to investigate their aggregation kinetics under soil environmental conditions in the present study. The hydrodynamic diameters of hematite and goethite nanoparticles were 34.4 and 66.3 nm, respectively. The positive surface charges and zeta potential values for goethite were higher than for hematite. The effective diameter for goethite was much larger than for hematite due to anisotropic sticking of needle-shaped goethite during aggregation. Moreover, the critical coagulation concentration (CCC) values of nanoparticles in solutions of NaNO3, NaCl, NaF, and Na2SO4 were 79.2, 75.0, 7.8, and 0.5 mM for hematite and they were 54.7, 62.6, 5.5, and 0.2 mM for goethite, respectively. The disparity of anions in inducing hematite or goethite aggregation lay in the differences in interfacial interactions. NO3 - and Cl- could decrease the zeta potential and enhance aggregation mainly through increasing ionic strength and compressing electric double layers of hematite and goethite nanoparticles. F- and SO4 2- highly destabilized the suspensions of nanoparticles mainly through specific adsorption and then neutralizing the positive surface charges of nanoparticles. Specific adsorption of cations could increase positive surface charges and stabilize hematite and goethite nanoparticles. The Hamaker constants of hematite and goethite nanoparticles were calculated to be 2.87 × 10-20 and 2.29 × 10-20 J-1, respectively. The predicted CCC values based on DLVO theory were consistent well with the experimentally determined CCC values in NaNO3, NaCl, NaF, and Na2SO4 systems, which demonstrated that DLVO theory could successfully predict the aggregation kinetics even when specific adsorption of ions occurred.

Assessment of roadside surface water quality of Savar, Dhaka, Bangladesh using GIS and multivariate statistical techniques

NASA Astrophysics Data System (ADS)

Ahmed, Fahad; Fakhruddin, A. N. M.; Imam, MD. Toufick; Khan, Nasima; Abdullah, Abu Tareq Mohammad; Khan, Tanzir Ahmed; Rahman, Md. Mahfuzur; Uddin, Mohammad Nashir

2017-11-01

In this study, multivariate statistical techniques in collaboration with GIS are used to assess the roadside surface water quality of Savar region. Nineteen water samples were collected in dry season and 15 water quality parameters including TSS, TDS, pH, DO, BOD, Cl-, F-, NO3 2-, NO2 -, SO4 2-, Ca, Mg, K, Zn and Pb were measured. The univariate overview of water quality parameters are TSS 25.154 ± 8.674 mg/l, TDS 840.400 ± 311.081 mg/l, pH 7.574 ± 0.256 pH unit, DO 4.544 ± 0.933 mg/l, BOD 0.758 ± 0.179 mg/l, Cl- 51.494 ± 28.095 mg/l, F- 0.771 ± 0.153 mg/l, NO3 2- 2.211 ± 0.878 mg/l, NO2 - 4.692 ± 5.971 mg/l, SO4 2- 69.545 ± 53.873 mg/l, Ca 48.458 ± 22.690 mg/l, Mg 19.676 ± 7.361 mg/l, K 12.874 ± 11.382 mg/l, Zn 0.027 ± 0.029 mg/l, Pb 0.096 ± 0.154 mg/l. The water quality data were subjected to R-mode PCA which resulted in five major components. PC1 explains 28% of total variance and indicates the roadside and brick field dust settle down (TDS, TSS) in the nearby water body. PC2 explains 22.123% of total variance and indicates the agricultural influence (K, Ca, and NO2 -). PC3 describes the contribution of nonpoint pollution from agricultural and soil erosion processes (SO4 2-, Cl-, and K). PC4 depicts heavy positively loaded by vehicle emission and diffusion from battery stores (Zn, Pb). PC5 depicts strong positive loading of BOD and strong negative loading of pH. Cluster analysis represents three major clusters for both water parameters and sampling sites. The site based on cluster showed similar grouping pattern of R-mode factor score map. The present work reveals a new scope to monitor the roadside water quality for future research in Bangladesh.

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

Comparison of Sodium Chloride Tablets-Induced, Sodium Chloride Solution-Induced, and Glycerol-Induced Hyperhydration on Fluid Balance Responses in Healthy Men.

PubMed

Savoie, Félix A; Asselin, Audrey; Goulet, Eric D B

2016-10-01

Savoie, FA, Asselin, A, and Goulet, EDB. Comparison of sodium chloride tablets-induced, sodium chloride solution-induced, and glycerol-induced hyperhydration on fluid balance responses in healthy men. J Strength Cond Res 30(10): 2880-2891, 2016-Sodium chloride solution-induced hyperhydration (NaCl-SolIH) is a powerful strategy to increase body water before exercise. However, NaCl-SolIH is associated with an unpleasant salty taste, potentially dissuading some athletes from using it and coaches from recommending it. Therefore, we evaluated the hyperhydrating potential of sodium chloride tablets-induced hyperhydration (NaCl-TabIH), which bypasses the palatability issue of NaCl-SolIH without sacrificing sodium chloride content, and compared it to NaCl-SolIH and glycerol-induced hyperhydration (GIH). Sixteen healthy males (age: 21 ± 2 years; fat-free mass (FFM): 65 ± 6 kg) underwent three, 3-hour long passive hyperhydration protocols during which they drank, over the first 60 minutes, 30-ml·kg FFM of an artificially sweetened solution. During NaCl-TabIH, participants swallowed 7.5, 1 g each, sodium chloride tablets with every liter of solution. During NaCl-SolIH, an equal quantity of sodium chloride tablets was dissolved in each liter of solution. With GIH, the glycerol concentration was 46.7 g·L. Urine production, fluid retention, hemoglobin, hematocrit, plasma volume, and perceptual variables were monitored throughout the trials. Total fluid intake was 1948 ± 182 ml. After 3 hour, there were no significant differences among treatments for hemoglobin, hematocrit, and plasma volume changes. Fluid retention was significantly greater with NaCl-SolIH (1150 ± 287 ml) than NaCl-TabIH (905 ± 340 ml) or GIH (800 ± 211 ml), with no difference between NaCl-TabIH and GIH. No differences were found among treatments for perceptual variables. NaCl-TabIH and GIH are equally effective, but inferior than NaCl-SolIH. NaCl-TabIH represents an alternative to hyperhydration induced with glycerol, which is prohibited by the World Anti-Doping Agency.

Computational studies of atmospherically-relevant chemical reactions in water clusters and on liquid water and ice surfaces.

PubMed

Gerber, R Benny; Varner, Mychel E; Hammerich, Audrey D; Riikonen, Sampsa; Murdachaew, Garold; Shemesh, Dorit; Finlayson-Pitts, Barbara J

2015-02-17

CONSPECTUS: Reactions on water and ice surfaces and in other aqueous media are ubiquitous in the atmosphere, but the microscopic mechanisms of most of these processes are as yet unknown. This Account examines recent progress in atomistic simulations of such reactions and the insights provided into mechanisms and interpretation of experiments. Illustrative examples are discussed. The main computational approaches employed are classical trajectory simulations using interaction potentials derived from quantum chemical methods. This comprises both ab initio molecular dynamics (AIMD) and semiempirical molecular dynamics (SEMD), the latter referring to semiempirical quantum chemical methods. Presented examples are as follows: (i) Reaction of the (NO(+))(NO3(-)) ion pair with a water cluster to produce the atmospherically important HONO and HNO3. The simulations show that a cluster with four water molecules describes the reaction. This provides a hydrogen-bonding network supporting the transition state. The reaction is triggered by thermal structural fluctuations, and ultrafast changes in atomic partial charges play a key role. This is an example where a reaction in a small cluster can provide a model for a corresponding bulk process. The results support the proposed mechanism for production of HONO by hydrolysis of NO2 (N2O4). (ii) The reactions of gaseous HCl with N2O4 and N2O5 on liquid water surfaces. Ionization of HCl at the water/air interface is followed by nucleophilic attack of Cl(-) on N2O4 or N2O5. Both reactions proceed by an SN2 mechanism. The products are ClNO and ClNO2, precursors of atmospheric atomic chlorine. Because this mechanism cannot result from a cluster too small for HCl ionization, an extended water film model was simulated. The results explain ClNO formation experiments. Predicted ClNO2 formation is less efficient. (iii) Ionization of acids at ice surfaces. No ionization is found on ideal crystalline surfaces, but the process is efficient on isolated defects where it involves formation of H3O(+)-acid anion contact ion pairs. This behavior is found in simulations of a model of the ice quasi-liquid layer corresponding to large defect concentrations in crystalline ice. The results are in accord with experiments. (iv) Ionization of acids on wet quartz. A monolayer of water on hydroxylated silica is ordered even at room temperature, but the surface lattice constant differs significantly from that of crystalline ice. The ionization processes of HCl and H2SO4 are of high yield and occur in a few picoseconds. The results are in accord with experimental spectroscopy. (v) Photochemical reactions on water and ice. These simulations require excited state quantum chemical methods. The electronic absorption spectrum of methyl hydroperoxide adsorbed on a large ice cluster is strongly blue-shifted relative to the isolated molecule. The measured and calculated adsorption band low-frequency tails are in agreement. A simple model of photodynamics assumes prompt electronic relaxation of the excited peroxide due to the ice surface. SEMD simulations support this, with the important finding that the photochemistry takes place mainly on the ground state. In conclusion, dynamics simulations using quantum chemical potentials are a useful tool in atmospheric chemistry of water media, capable of comparison with experiment.

Effect of sulphur deprivation on osmotic potential components and nitrogen metabolism in oilseed rape leaves: identification of a new early indicator.

PubMed

Sorin, Elise; Etienne, Philippe; Maillard, Anne; Zamarreño, Angel-Mari; Garcia-Mina, José-Maria; Arkoun, Mustapha; Jamois, Frank; Cruz, Florence; Yvin, Jean-Claude; Ourry, Alain

2015-10-01

Identification of early sulphur (S) deficiency indicators is important for species such as Brassica napus, an S-demanding crop in which yield and the nutritional quality of seeds are negatively affected by S deficiency. Because S is mostly stored as SO4 (2-) in leaf cell vacuoles and can be mobilized during S deficiency, this study investigated the impact of S deprivation on leaf osmotic potential in order to identify compensation processes. Plants were exposed for 28 days to S or to chlorine deprivation in order to differentiate osmotic and metabolic responses. While chlorine deprivation had no significant effects on growth, osmotic potential and nitrogen metabolism, Brassica napus revealed two response periods to S deprivation. The first one occurred during the first 13 days during which plant growth was maintained as a result of vacuolar SO4 (2-) mobilization. In the meantime, leaf osmotic potential of S-deprived plants remained similar to control plants despite a reduction in the SO4 (2-) osmotic contribution, which was fully compensated by an increase in NO3 (-), PO4 (3-) and Cl(-) accumulation. The second response occurred after 13 days of S deprivation with a significant reduction in growth, leaf osmotic potential, NO3 (-) uptake and NO3 (-) reductase activity, whereas amino acids and NO3 (-) were accumulated. This kinetic analysis of S deprivation suggested that a ([Cl(-)]+[NO3 (-)]+[PO4 (3-)]):[SO4 (2-)] ratio could provide a relevant indicator of S deficiency, modified nearly as early as the over-expression of genes encoding SO4 (2-) tonoplastic or plasmalemmal transporters, with the added advantage that it can be easily quantified under field conditions. © The Author 2015. Published by Oxford University Press on behalf of the Society for Experimental Biology. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Three oxime ether derivatives: Synthesis, crystallographic study, electronic structure and molecular electrostatic potential calculation

NASA Astrophysics Data System (ADS)

Dey, Tanusri; Praveena, Koduru Sri Shanthi; Pal, Sarbani; Mukherjee, Alok Kumar

2017-06-01

Three oxime ether derivatives, (E)-3-methoxy-4-(prop-2-ynyloxy)-benzaldehyde-O-prop-2-ynyl-oxime (C14H13NO3) (2), benzophenone-O-prop-2-ynyl-oxime (C16H13NO) (3) and (E)-2-chloro-6-methylquinoline-3-carbaldehyde-O-prop-2-ynyl-oxime (C14H11ClN2O) (4), have been synthesized and their crystal structures have been determined. The DFT optimized molecular geometries in 2-4 agree closely with those obtained from the crystallographic study. An interplay of intermolecular Csbnd H⋯O, Csbnd H⋯N, Csbnd H⋯Cl and Csbnd H···π(arene) hydrogen bonds and π···π interactions assembles molecules into a 2D columnar architecture in 2, a 1D molecular ribbon in 3 and a 3D framework in 4. Hirshfeld surface analysis showed that the structures of 2 and 3 are mainly characterized by H⋯H, H⋯C and H⋯O contacts but some contribution of H⋯N and H⋯Cl contacts is also observed in 4. Hydrogen-bond based interactions in 2-4 have been complemented by calculating molecular electrostatic potential (MEP) surfaces. The electronic structures of molecules reveal that the estimated band gap in 3, in which both aldehyde hydrogen atoms of formaldehyde-O-prop-2-ynyl-oxime (1) have been substituted by two benzene rings, is higher than that of 2 and 4 with only one aldehyde hydrogen atom replaced.

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.

Chemical characterisation of meltwater draining from Gangotri Glacier, Garhwal Himalaya, India

NASA Astrophysics Data System (ADS)

Singh, Virendra Bahadur; Ramanathan, Al; Pottakkal, Jose George; Sharma, Parmanand; Linda, Anurag; Azam, Mohd Farooq; Chatterjee, C.

2012-06-01

A detailed analytical study of major cations (Ca2 + , Mg2 + , Na + , K + ) and anions (SO4^{2-}, HCO3-, Cl - , NO3-) of meltwater draining from Gangotri Glacier was carried out to understand major ion chemistry and to get an insight into geochemical weathering processes controlling hydrochemistry of the glacier. In the meltwater, the abundance order of cations and anions varied as follows: Ca2 + > Mg2 + > K + > Na + and SO4^{2-} > HCO3- > Cl - > NO3-, respectively. Calcium and magnesium are dominant cations while sulphate and bicarbonate are dominant anions. Weathering of rocks is the dominant mechanism controlling the hydrochemistry of drainage basin. The relative high contribution of (Ca+Mg) to the total cations (TZ + ), high (Ca+Mg)/(Na+K) ratio (2.63) and low (Na+K)/TZ + ratio (0.29) indicate the dominance of carbonate weathering as a major source for dissolved ions in the glacier meltwater. Sulphide oxidation and carbonation are the main proton supplying geochemical reactions controlling the rock weathering in the study area. Statistical analysis was done to identify various factors controlling the dissolved ionic strength of Gangotri Glacier meltwater.

N leaching to groundwater from dairy production involving grazing over the winter on a clay-loam soil.

PubMed

Necpalova, M; Fenton, O; Casey, I; Humphreys, J

2012-08-15

This study investigated concentrations of various N species in shallow groundwater (<2.2m below ground level) and N losses from dairy production involving grazing over the winter period on a clay loam soil with a high natural attenuation capacity in southern Ireland (52°51'N, 08°21'W) over a 2-year period. A dense network of shallow groundwater piezometers was installed to determine groundwater flow direction and N spatial and temporal variation. Estimated vertical travel times through the unsaturated zone (<0.5 yr, time lag) allowed the correlation of management with groundwater N within a short space of time. There was a two way interaction of the system and sampling date (P<0.05) on concentrations of DON, oxidised N and NO(3)(-)-N. In contrast, concentrations of NH(4)(+)-N and NO(2)(-)-N were unaffected by the dairy system. Grazing over the winter had no effect on N losses to groundwater. Mean concentrations of DON, NH(4)(+)-N, NO(2)(-)-N and NO(3)(-)-N were 2.16, 0.35, 0.01 and 0.37 mg L(-1) respectively. Soil attenuation processes such as denitrification and DNRA resulted in increased NH(4)(+)-N levels. For this reason, DON and NH(4)(+)-N represented the highest proportion of N losses from the site. Some of the spatial and temporal variation of N concentrations was explained by correlations with selected chemical and hydro-topographical parameters (NO(3)(-)-N/Cl(-) ratio, distance of the sampling point from the closest receptor, watertable depth, depth of sampling piezometer, DOC concentration). A high explanatory power of NO(3)(-)-N/Cl(-) ratio and the distance of the sampling point from the closest receptor indicated the influence of point sources and groundwater-surface water interactions. Copyright © 2012 Elsevier B.V. All rights reserved.

Mechanism of anion permeation through the muscle fibre membrane of an elasmobranch fish, Taeniura lymma.

PubMed

Hagiwara, S; Takahashi, K

1974-04-01

1. Properties of anion permeation through the membrane of skeletal muscle fibres of the stingray, Taeniura lymma, were studied with intracellular recording and polarization techniques.2. The Cl conductance of the resting membrane in the normal stingray saline at pH 7.7 is 8-10 times greater than the K conductance.3. The Cl conductance decreases with decreasing external pH, with an apparent pK of 5.3, whereas the K conductance is independent of pH between 4 and 9.4. The Q(10) of the Cl conductance is about 2.0, compared with a value of 1.2-1.4 for the K conductance.5. The Cl conductance is proportional to the external Cl concentration when observed after the fibre is equilibrated in the test solution.6. The permeability sequence obtained by potential measurement is SCN > NO(3) > Cl = Br > I > ClO(3) and the permeability ratio is independent of the mole fraction of anions.7. The conductance sequence determined by total replacement of the external Cl with other anion species differs from the permeability sequence and the conductance observed for partial replacement deviates significantly from that expected from the independence principle.8. Possible mechanisms of anion permeation are discussed.

Mechanism of anion permeation through the muscle fibre membrane of an elasmobranch fish, Taeniura lymma

PubMed Central

Hagiwara, Susumu; Takahashi, Kunitaro

1974-01-01

1. Properties of anion permeation through the membrane of skeletal muscle fibres of the stingray, Taeniura lymma, were studied with intracellular recording and polarization techniques. 2. The Cl conductance of the resting membrane in the normal stingray saline at pH 7·7 is 8-10 times greater than the K conductance. 3. The Cl conductance decreases with decreasing external pH, with an apparent pK of 5·3, whereas the K conductance is independent of pH between 4 and 9. 4. The Q10 of the Cl conductance is about 2·0, compared with a value of 1·2-1·4 for the K conductance. 5. The Cl conductance is proportional to the external Cl concentration when observed after the fibre is equilibrated in the test solution. 6. The permeability sequence obtained by potential measurement is SCN > NO3 > Cl = Br > I > ClO3 and the permeability ratio is independent of the mole fraction of anions. 7. The conductance sequence determined by total replacement of the external Cl with other anion species differs from the permeability sequence and the conductance observed for partial replacement deviates significantly from that expected from the independence principle. 8. Possible mechanisms of anion permeation are discussed. PMID:4838800

Structure, phase transitions, and isotope effects in [(CH3)4N]2PuCl6

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

Wilson, Richard E.

2015-11-02

The single crystal X-ray diffraction structure of [(CH3)4N]2PuCl6 is presented for the first time, resolving long standing confusion and speculation regarding the structure of this compound in the literature. A temperature dependent study of this compound shows that the structure of [(CH3)4N]2PuCl6 undergoes no fewer than two phase transitions between 100 and 360 K. The phase of [(CH3)4N]2PuCl6 at room temperature is Fd-3c a = 26.012(3) Å. At 360 K, the structure is in space group Fm-3m with a = 13.088(1) Å. The plutonium octahedra and tetramethylammonium cations undergo a rotative displacement and the degree of rotation varies with temperature,more » giving rise to the phase transition from Fm-3m to Fd-3c as the crystal is cooled. Synthesis and structural studies of the deuterated salt [(CD3)4N]2PuCl6 suggest that there is an isotopic effect associated with this phase transition as revealed by a changing transition temperature in the deuterated versus protonated compound indicating that the donor-acceptor interactions between the tetramethylammonium cations and the hexachloroplutonate anions are driving the phase transformation.« less

Remote sensing of the troposphere by infrared emission spectroscopy

NASA Technical Reports Server (NTRS)

Beer, Reinhard; Glavich, Thomas A.

1989-01-01

This paper describes the concept of a cryogenic IR imaging Fourier transform spectrometer, called the Tropospheric Emission Spectrometer (TES), designed for observations of the troposphere and lower stratosphere from a near-earth orbit, using natural thermal emission and reflected sunlight. The principal molecular species to be measured by TES are O3, CO, CO2, N2O, H2O, H2O2, NO, NO2, HNO3, NH3, CH4, C2H6, C2H2, SO2, COS, CFCl3, and CF2Cl2. The TES is scheduled for a launch on the second polar platform of the Earth Observing System in 1998.

Reactions of salts of hexakis(pyridine N-oxide)M(II) complexes (M = Co, Ni, Zn) and alkali halides used in infrared spectroscopy

NASA Astrophysics Data System (ADS)

Padmos, J.; van Veen, A.

A number of salts of hexakis(pyridine N-oxide)zinc(II) complexes decompose in alkali halide pellets. Initially ion exchange occurs, often followed by the formation of Zn(pyno) 3X 2 (pyno = pyridine N-oxide; X = Br, Cl). The analogous cobalt and nickel compounds are nearly always stable. A mull between alkali halide plates gives greater amounts of the same product Washing this product with toluene gives Zn(pyno) 2X 2. Examples of i.r. and far i.r. spectra are given. Energetical and structural effects are discussed. Far i.r. spectra of M(pyno) 3X 2(M = Co, Zn) confirm the structure [M(pyno) 6][MX 4] for these compounds. New compounds are [Zn(pyno) 2(NO 3) 2], [Zn(pyno- d5) 2[NO 3) 2], [Zn(pyno- d5) 6](NO 3) 2 and [Zn(pyno) 6]I 2.

NMR studies on Na+ transport in Synechococcus PCC 6311

NASA Technical Reports Server (NTRS)

Nitschmann, W. H.; Packer, L.

1992-01-01

The freshwater cyanobacterium Synechococcus PCC 6311 is able to adapt to grow after sudden exposure to salt (NaCl) stress. We have investigated the mechanism of Na+ transport in these cells during adaptation to high salinity. Na+ influx under dark aerobic conditions occurred independently of delta pH or delta psi across the cytoplasmic membrane, ATPase activity, and respiratory electron transport. These findings are consistent with the existence of Na+/monovalent anion cotransport or simultaneous Na+/H+ +anion/OH- exchange. Na+ influx was dependent on Cl-, Br-, NO3-, or NO2-. No Na+ uptake occurred after addition of NaI, NaHCO3, or Na2SO4. Na+ extrusion was absolutely dependent on delta pH and on an ATPase activity and/or on respiratory electron transport. This indicates that Na+ extrusion via Na+/H+ exchange is driven by primary H+ pumps in the cytoplasmic membrane. Cells grown for 4 days in 0.5 m NaCl medium, "salt-grown cells," differ from control cells by a lower maximum velocity of Na+ influx and by lower steady-state ratios of [Na+]in/[Na+]out. These results indicate that cells grown in high-salt medium increase their capacity to extrude Na+. During salt adaptation Na+ extrusion driven by respiratory electron transport increased from about 15 to 50%.

Aerosol composition, chemistry, and source characterization during the 2008 VOCALS Experiment

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

Lee, Y.; Springston, S.; Jayne, J.

2010-03-15

Chemical composition of fine aerosol particles over the northern Chilean coastal waters was determined onboard the U.S. DOE G-1 aircraft during the VOCALS (VAMOS Ocean-Cloud-Atmosphere-Land Study) field campaign between October 16 and November 15, 2008. SO42-, NO3-, NH4+, and total organics (Org) were determined using an Aerodyne Aerosol Mass Spectrometer, and SO42-, NO3-, NH4+, Na+, Cl-, CH3SO3-, Mg2+, Ca2+, and K+ were determined using a particle-into-liquid sampler-ion chromatography technique. The results show the marine boundary layer (MBL) aerosol mass was dominated by non- sea-salt SO42- followed by Na+, Cl-, Org, NO3-, and NH4+, in decreasing importance; CH3SO3-, Ca2+, and K+more » rarely exceeded their respective limits of detection. The SO42- aerosols were strongly acidic as the equivalent NH4+ to SO42- ratio was only {approx}0.25 on average. NaCl particles, presumably of sea-salt origin, showed chloride deficits but retained Cl- typically more than half the equivalency of Na+, and are externally mixed with the acidic sulfate aerosols. Nitrate was observed only on sea-salt particles, consistent with adsorption of HNO3 on sea-salt aerosols, responsible for the Cl- deficit. Dust particles appeared to play a minor role, judging from the small volume differences between that derived from the observed mass concentrations and that calculated based on particle size distributions. Because SO42- concentrations were substantial ({approx}0.5 - {approx}3 {micro}g/m3) with a strong gradient (highest near the shore), and the ocean-emitted dimethylsulfide and its unique oxidation product, CH3SO3-, were very low (i.e., {le} 40 parts per trillion and <0.05 {micro}g/m3, respectively), the observed SO42- aerosols are believed to be primarily of terrestrial origin. Back trajectory calculations indicate sulfur emissions from smelters and power plants along coastal regions of Peru and Chile are the main sources of these SO4- aerosols. However, compared to observations, model calculations appeared to underestimate sulfate concentrations based on an existing emission inventory. The agreement between observations and model predictions of CO as well as total sulfur is reexamined in this work with a new emission inventory made available recently.« less

Name that compound: The numbers game for CFCs, HFCs, HCFCs, and Halons

DOE Data Explorer

Blasing, T. J.; Jones, Sonja

2012-02-01

Chlorofluorocarbons (CFCs) contain Carbon and some combination of Fluorine and Chlorine atoms. Hydrofluorocarbons (HFCs) contain Hydrogen, Fluorine, and Carbon (no chlorine). Hydrochlorofluorocarbons (HCFCs) contain Hydrogen, Chlorine, Fluorine, and Carbon atoms. Hydrobromofluorocarbons (HBFCs) contain Hydrogen, Bromine, Fluorine, and Carbon atoms. Perfluorocarbons contain Fluorine, Carbon, and Bromine atoms, and some contain Chlorine and/or Hydrogen atoms. These compounds are often designated by a combination of letters and numbers (e.g., CFC-11, HCFC-142b). In the latter example, the lower-case b refers to an isomer, which has no relationship to the chemical formula (C2H3F2Cl), but designates a particular structural arrangement of the atoms included. For example, HCFC-142b identifies the isomer in which all three hydrogen atoms are attached to the same carbon atom, and the structural formula is written as CH3CF2Cl. By contrast, HCFC-142 (without the b) refers to an arrangement in which one carbon atom is attached to two hydrogen atoms and one chlorine atom, while the other carbon atom is attached to the third hydrogen atom and two fluorine atoms. Hence, it has a different structural formula (CH2ClCHF2).

75 FR 47249 - Airworthiness Directives; Bombardier, Inc. Model CL-600-2B19 (Regional Jet Series 100 & 440...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-05

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

Ozone Production and Loss Rate Measurements in the Middle Stratosphere

NASA Technical Reports Server (NTRS)

Jucks, Kenneth W.; Johnson, David G.; Chance, K. V.; Traub, Wesley A.; Salawitch, R. J.; Stachnik, R. A.

1996-01-01

The first simultaneous measurements of HO(x), NO(x), and Cl(x) radicals in the middle stratosphere show that NO(x) catalytic cycles dominate loss of ozone (O3) for altitudes between 24 and 38 km; Cl(x) catalytic cycles are measured to be less effective than previously expected; and there is no 'ozone deficit' in the photochemically dominated altitude range from 31 and 38 km, contrary to some previous theoretical studies.

Reactive Nitrogen in Asian Continental Outflow over the Western Pacific: Results from the NASA Transport and Chemical Evolution over the Pacific (TRACE-P)Airborne Mission

NASA Technical Reports Server (NTRS)

Talbot, R.; Dibb, J.; Scheuer, E.; Seid, G.; Russo, R.; Sandholm, S.; Tan, D.; Blake, D.; Blake, N.; Singh, H.

2003-01-01

We present here results for reactive nitrogen species measured aboard the NASA DC-8 aircraft during the Transport and Chemical Evolution over the Pacific TRACE-P) mission. The large-scale distributions total reactive nitrogen (NO(sub y,sum) = NO + NO2 + HNO3 + PAN + C(sub 1)-C(sub 5) alkyl nitrates) and O3 and CO were better defined in the boundary layer with significant degradation of the relationships as altitude increased. Typically, NO(sub y,sum) was enhanced over background levels of approx.260 pptv by 20-to-30-fold. The ratio C2H2/CO had values of 1-4 at altitudes up to 10 km and as far eastward as 150degE, implying significant vertical mixing of air parcels followed by rapid advection across the Pacific. Analysis air parcels originating from five principal Asian source regions showed that HNO3 and PAN dominated NO(sub y,sum). Correlations of NO(sub y,sum) with C2Cl4 (urban tracer) were not well defined in any of the source regions, and they were only slightly better with CH3Cl (biomass tracer). Air parcels over the western Pacific contained a complex mixture of emission sources that are not easily resolvable as shown by analysis of the Shanghai mega-city plume. It contained an intricate mixture of pollution emissions and exhibited the highest mixing ratios of NO(sub y,sum) species observed during TRACE-P. Comparison of tropospheric chemistry between the earlier PEM-West B mission and the recent TRACE-P data showed that in the boundary layer significant increases in the mixing ratios of NO(sub y,sum)species have occurred, but the middle and upper troposphere seems to have been affected minimally by increasing emissions on the Asian continent over the last 7 years.

(Tetramethylthiophene)ruthenium in dichloride dimer: A versatile synthetic intermediate in thiophene coordination chemistry

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

Lockemeyer, J.R.; Rauchfuss, T.B.; Wilson, S.R.

1989-11-22

The thermal reaction of ((cymene)RuCl{sub 2}){sub 2} and tetramethylthiophene (TMT) gives ((TMT)RuCl{sub 2}){sub 2} (1). Treatment of 1 with silver salts in the presence of various ligands gives salts of ((TMT)RuL{sub 3}){sup 2+} where L{sub 3} = (H{sub 2}O){sub 3}, (CH{sub 3}CN){sub 3}, and TMT. A crystallographic study demonstrated that ((TMT){sub 2}Ru)(BF{sub 4}){sub 2} {times} 2CH{sub 3}NO{sub 2} adopts a sandwich structure with sulfur atoms sited cis on the pseudooctahedron. Cyclic voltammetry studies show that ((TMT){sub 2}Ru){sup 2+} undergoes 2 reversible one-electron reductions. Solutions of 1 and phosphine and amine donors react to give well-behaved monometallic derivatives of the typemore » (TMT)RuCl{sub 2}L where L is PR{sub 3} and NH{sub 2}C{sub 6}H{sub 4}Me. For bulky L = PPh{sub 3} and P(C{sub 6}H{sub 4}Me){sub 3}, variable-temperature NMR studies demonstrate hindered rotation about the Ru-P and Ru{hor ellipsis} TMT axes. Treatment of 1 with (Me{sub 3}Si){sub 2}S gives the cluster ((TMT)RuCl){sub 3}S{sup +} whose PF{sub 6}{sup {minus}} salt was examined by X-ray crystallography. The cluster is comprised of 3 conjoined pseudooctahedral Ru centers bridged by 1 {mu}{sub 3}-S and 3 {mu}-Cl atoms.« less

Sodium hypochlorite oxidation of petroleum aliphatic contaminants in calcareous soils.

PubMed

Picard, François; Chaouki, Jamal

2016-02-01

This research project investigated the sodium hypochlorite (NaClO) oxidation of aliphatic petroleum contaminants (C10-C50) in a calcareous soil (average 5473 ppm C10-C50, 15 wt% Ca), which had been excavated from a contaminated industrial site. The decontamination objective was to lower the C10-C50 concentration to 700 ppm. CO2 acidity was used in the project to boost the NaClO oxidation yield and seems to have played a role in desorbing the natural organic matter. The experimental conditions were a 2- to 16-h reaction time, at room temperature, with a 1 to 12.5 wt% NaClO oxidative solution and a fixed 2:1 solution-to-soil ratio. With a 3 wt% NaClO solution and with a CO2 overhead, the NaClO dosage requirement was maintained below 60 g NaClO/g of oxidized C10-C50 over the entire decontamination range. The strong chlorine smell remaining after the reaction was completed suggests that part of the NaClO requirement can be recycled. Except traces of chloroform, there were no regulation-listed organochloride contaminants detected on either the treated soil samples or leachates and the total count of chlorinated compounds in treated soil samples was below the detection limit of 250 mg/kg. The NaClO oxidation mechanism on aliphatic substrates might be triggered by transition metals, such as manganese, but no attempt has been made to investigate the oxidation mechanism. Further investigations would include a constant-fed NaClO system and other techniques to lower the required NaClO dosage. Copyright © 2015 Elsevier Ltd. All rights reserved.

Acetate-Bridged Platinum(III) Complexes Derived from Cisplatin

PubMed Central

Wilson, Justin J.

2012-01-01

Oxidation of the acetate-bridged half-lantern platinum(II) complex, cis-[PtII(NH3)2(µ-OAc)2PtII(NH3)2](NO3)2, [1](NO3)2, with iodobenzene dichloride or bromine generates the halide-capped platinum(III) species, cis-[XPtIII(NH3)2(µ-OAc)2PtIII(NH3)2X](NO3)2, where X is Cl in [2](NO3)2, or Br in [3](NO3)2, respectively. These three complexes, characterized structurally by X-ray crystallography, feature short (≈ 2.6 Å) Pt–Pt separations, consistent with formation of a formal metal-metal bond upon oxidation. Elongated axial Pt–X distances occur, reflecting the strong trans influence of the metal-metal bond. The three structures are compared to those of other known dinuclear platinum complexes. A combination of 1H, 13C, 14N, and 195Pt NMR spectroscopy was used to characterize [1]2+–[3]2+ in solution. All resonances shift downfield upon oxidation of [1]2+ to [2]2+ and [3]2+. For the platinum(III) complexes, the 14N and 195Pt resonances exhibit decreased linewidths by comparison to those of [1]2+. Density functional theory (DFT) calculations suggest that the decrease in 14N linewidth arises from a diminished electric field gradient (EFG) at the 14N nuclei in the higher valent compounds. The oxidation of [1](NO3)2 with the alternative oxidizing agent, bis(trifluoroacetoxy) iodobenzene, affords the novel tetranuclear complex, cis-[(O2CCF3)PtIII(NH3)2(µ-OAc)2PtIII(NH3)(µ-NH2)]2(NO3)4, [4](NO3)4, also characterized structurally by X-ray crystallography. In solution, this complex exists as a mixture of species, the identities of which are proposed. PMID:22946515

Comparative studies of mononuclear Ni(II) and UO2(II) complexes having bifunctional coordinated groups: Synthesis, thermal analysis, X-ray diffraction, surface morphology studies and biological evaluation

NASA Astrophysics Data System (ADS)

Fahem, Abeer A.

2012-03-01

Two Schiff base ligands derived from condensation of phthalaldehyde and o-phenylenediamine in 1:2 (L1) and 2:1 (L2) having bifunctional coordinated groups (NH2 and CHO groups, respectively) and their metal complexes with Ni(II) and UO2(II) have been synthesized and characterized by elemental analysis, molar conductance, magnetic susceptibilities and spectral data (IR, 1H NMR, mass and solid reflectance) as well as thermal, XRPD and SEM analysis. The formula [Ni(L1)Cl2]·2.5H2O, [UO2(L1)(NO3)2]·2H2O, [Ni(L2)Cl2]·1.5H2O and [UO2(L2)(NO3)2] have been suggested for the complexes. The vibrational spectral data show that the ligands behave as neutral ligands and coordinated to the metal ions in a tetradentate manner. The Ni(II) complexes are six coordinate with octahedral geometry and the ligand field parameters: Dq, B, β and LFSE were calculated while, UO2(II) complexes are eight coordinate with dodecahedral geometry and the force constant, FUsbnd O and bond length, RUsbnd O were calculated. The thermal decomposition of complexes ended with metal chloride/nitrate as a final product and the highest thermal stability is displayed by [UO2(L2)(NO3)2] complex. The X-ray powder diffraction data revealed the formation of nano sized crystalline complexes. The SEM analysis provides the morphology of the synthesized compounds and SEM image of [UO2(L2)(NO3)2] complex exhibits nano rod structure. The growth-inhibiting potential of the ligands and their complexes has been assessed against a variety of bacterial and fungal strains.

Study on the decomposition of trace benzene over V2O5-WO3 ...

EPA Pesticide Factsheets

Commercial and laboratory-prepared V2O5–WO3/TiO2-based catalysts with different compositions were tested for catalytic decomposition of chlorobenzene （ClBz） in simulated flue gas. Resonance enhanced multiphoton ionization-time of flight mass spectrometry (REMPI-TOFMS) was employed to measure real-time, trace concentrations of ClBz contained in the flue gas before and after the catalyst. The effects of various parameters, including vanadium content of the catalyst, the catalyst support, as well as the reaction temperature on decomposition of ClBz were investigated. The results showed that the ClBz decomposition efficiency was significantly enhanced when nano-TiO2 instead of conventional TiO2 was used as the catalyst support. No promotion effects were found in the ClBz decomposition process when the catalysts were wet-impregnated with CuO and CeO2. Tests with different concentrations (1,000, 500, and 100 ppb) of ClBz showed that ClBz-decomposition efficiency decreased with increasing concentration, unless active sites were plentiful. A comparison between ClBz and benzene decomposition on the V2O5–WO3/TiO2-based catalyst and the relative kinetics analysis showed that two different active sites were likely involved in the decomposition mechanism and the V=O and V-O-Ti groups may only work for the degradation of the phenyl group and the benzene ring rather than the C-Cl bond. V2O5-WO3/TiO2 based catalysts, that have been used for destruction of a wide variet

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.

Exposure of cultured human proximal tubular cells to cadmium, mercury, zinc and bismuth: toxicity and metallothionein induction.

PubMed

Rodilla, V; Miles, A T; Jenner, W; Hawksworth, G M

1998-08-14

The kidney, in particular the proximal convoluted tubule, is a major target site for the toxic effects of various metals. However, little is known about the early effects of these metals after acute exposure in man. In the present study we have evaluated the toxicity of several inorganic metal compounds (CdCl2, HgCl2, ZnCl2, and Bi(NO3)3) and the induction of metallothionein by these compounds in cultured human proximal tubular (HPT) cells for up to 4 days. The results showed that bismuth was not toxic even at the highest dose (100 microM) used, while zinc, cadmium and mercury exhibited varying degrees of toxicity, zinc being the least toxic and mercury the most potent. A significant degree of interindividual variation between the different isolates used in these experiments was also observed. All metals used in the present study induced MT, as revealed by immunocytochemistry. All metals showed maximal induction between 1 and 3 days after treatment. Although a certain amount of constitutive MT was present in the cultures, the intensity of the staining varied with time in culture and between the different isolates studied. No correlation could be made between the intensity of the staining in control cultures (indicating total amount of constitutive MT) and the susceptibility of a given isolate to metal toxicity. Furthermore, no correlation could be made between metal-induced MT and the susceptibility of a given isolate to that particular metal.

Tropical land-cover change alters biogeochemical inputs to ecosystems in a Mexican montane landscape.

PubMed

Ponette-González, A G; Weathers, K C; Curran, L M

2010-10-01

In tropical regions, the effects of land-cover change on nutrient and pollutant inputs to ecosystems remain poorly documented and may be pronounced, especially in montane areas exposed to elevated atmospheric deposition. We examined atmospheric deposition and canopy interactions of sulfate-sulfur (SO4(2-)-S), chloride (Cl-), and nitrate-nitrogen (NO(3-)-N) in three extensive tropical montane land-cover types: clearings, forest, and coffee agroforest. Bulk and fog deposition to clearings was measured as well as throughfall (water that falls through plant canopies) ion fluxes in seven forest and five coffee sites. Sampling was conducted from 2005 to 2008 across two regions in the Sierra Madre Oriental, Veracruz, Mexico. Annual throughfall fluxes to forest and coffee sites ranged over 6-27 kg SO4(2-)-S/ha, 12-69 kg Cl-/ha, and 2-6 kg NO(3-)-N/ha. Sulfate-S in forest and coffee throughfall was higher or similar to bulk S deposition measured in clearings. Throughfall Cl- inputs, however, were consistently higher than Cl- amounts deposited to cleared areas, with net Cl- fluxes enhanced in evergreen coffee relative to semi-deciduous forest plots. Compared to bulk nitrate-N deposition, forest and coffee canopies retained 1-4 kg NO(3-)-N/ha annually, reducing NO(3-)-N inputs to soils. Overall, throughfall fluxes were similar to values reported for Neotropical sites influenced by anthropogenic emissions, while bulk S and N deposition were nine- and eightfold greater, respectively, than background wet deposition rates for remote tropical areas. Our results demonstrate that land-cover type significantly alters the magnitude and spatial distribution of atmospheric inputs to tropical ecosystems, primarily through canopy-induced changes in fog and dry deposition. However, we found that land cover interacts with topography and climate in significant ways to produce spatially heterogeneous patterns of anion fluxes, and that these factors can converge to create deposition hotspots. For land managers, this finding suggests that there is potential to identify species and ecosystems at risk of excess and increasing deposition in montane watersheds undergoing rapid transformation. Our data further indicate that montane ecosystems are vulnerable to air pollution impacts in this and similar tropical regions downwind of urban, industrial, and agricultural emission sources.

Plasticity of Cl-Te-Cl Fragments. Synthesis, Single-Crystal X-ray, and NBO Study of (1-Thia-2-tellura-1-phenyl-4-chloro)cyclopentane 2,2,2-Trichloride.

PubMed

Sundberg, Markku R.; Laitalainen, Tarja; Bergman, Jan; Uggla, Rolf; Matikainen, Jorma; Kaltia, Seppo

1998-06-01

Tellurium tetrachloride and allylphenyl sulfide react to form (1-thia-2-tellura-1-phenyl-4-chloro)cyclopentane 2,2,2-trichloride. The crystal and molecular structure were determined by single-crystal X-ray techniques. The crystals belong to the monoclinic system, space group P2(1)/c (No. 14) with a = 6.020(3) Å, b = 11.46(1) Å, c = 20.156(2) Å, beta = 97.53(2) degrees, V = 1379(1) Å(3), and Z = 4. The structure was refined to the final R value of 0.036. The coordination around Te(IV) is distorted psi octahedral with three Cl atoms in the equatorial positions. The axial Te(1)-C(1) bond opposite to the lone pair of electrons at the Te(IV) atom completes the coordination polyhedron. The intramolecular Te-S distance is 2.903(3) Å. Symmetric and asymmetric deformation modes were established to describe the plasticity of the Cl-Te-Cl fragments extracted from the Cambridge Structural Database. The hypervalency of Te(IV) manifests itself as plasticity in the equatorial plane of the coordination sphere. The NBO calculations show that all of the equatorial Te-Cl bonds are highly polarized and the electrons reside mainly on the Cl atoms.

A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

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

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO 2 2+, UO 2Cl +, and UO 2Cl 2°. UO 2Cl 3 - is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species showmore » fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO 2Cl 4 2- and UO 2Cl 5 3- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T >150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO 2Cl 2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO 2 2+ + Cl - = UO 2Cl + are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO 2 2+ + 2Cl - = UO 2Cl 2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.« less

A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

DOE PAGES

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.; ...

2017-10-24

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO 2 2+, UO 2Cl +, and UO 2Cl 2°. UO 2Cl 3 - is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species showmore » fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO 2Cl 4 2- and UO 2Cl 5 3- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T >150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO 2Cl 2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO 2 2+ + Cl - = UO 2Cl + are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO 2 2+ + 2Cl - = UO 2Cl 2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.« less

The promotion effect of coexisting hygroscopic composition on the reaction between oxalic acid and calcite during humidifying process

NASA Astrophysics Data System (ADS)

Ma, Q.; He, H.

2012-12-01

Internally mixed oxalic acid with mineral dust has been frequently detected in field measurements (Sullivan and Prather, 2007; Wang et al., 2012; Yang et al., 2009). Meanwhile, Furukawa and Takahashi (Furukawa and Takahashi, 2011) found that most of the oxalic acid in mineral mixture is present as metal oxalate complexes in the aerosols, however, the formation mechanism of these complexes is not well known. It was reported that cloud process of H2C2O4/CaCO3 mixture could lead to the formation of calcium oxalate (Gierlus et al., 2012). Recently, we used Raman spectroscopy to investigate the hygroscopic behavior of H2C2O4/CaCO3 mixture below saturation condition as well as the effect of coexisting hygroscopic compositions, e.g. Ca(NO3)2, NaCl, NH4NO3, and (NH4)2SO4. It was found that there was no interaction between H2C2O4 and calcite without third component during humidifying process under ambient condition. In contrast, the presence of coexisting Ca(NO)3, NaCl, or NH4NO3 could promote the reaction between H2C2O4 and calcite by providing an aqueous circumstance after deliquescence, resulting in the formation of calcium oxalate hydrates. Moreover, substitution of strong acid (HNO3) by medium acid (H2C2O4) occurred when water vapor was absorbed in Ca(NO3)2/H2C2O4 mixture (Ma and He, 2012). As for (NH4)2SO4, there existed a competition effect between (NH4)2SO4 and H2C2O4 for the reaction with CaCO3. CaCO3 was preferentially reacted with (NH4)2SO4 to form gypsum in the solution, while the residual NH4+ and C2O42- ions were bonded to (NH4)2C2O4 after efflorescence. These results implies a potential formation pathway of metal oxalate complexes in the atmosphere and also suggests that synergistic effect between different constituents in humidifying process of mixed particles should be considered in future hygroscopic behavior studies.

Chemical Characteristics of Continental Outflow Over the Tropical South Atlantic Ocean from Brazil and Africa

NASA Technical Reports Server (NTRS)

Talbot, R. W.; Bradshaw, J. D.; Sandholm, S. T.; Smyth, S.; Blake, D. R.; Blake, N. R.; Sachse, G. W.; Collins, J. E.; Heikes, B. G.; Anderson, B. E.;

Synthesis, anion exchange, and delamination of Co-Al layered double hydroxide: assembly of the exfoliated nanosheet/polyanion composite films and magneto-optical studies.

PubMed

Liu, Zhaoping; Ma, Renzhi; Osada, Minoru; Iyi, Nobuo; Ebina, Yasuo; Takada, Kazunori; Sasaki, Takayoshi

2006-04-12

This paper describes a systematic study on the synthesis, anion exchange, and delamination of Co-Al layered double hydroxide (LDH), with the aim of achieving fabrication and clarifying the properties of LDH nanosheet/polyanion composite films. Co-Al-CO3 LDH hexagonal platelets of 4 mum in lateral size were synthesized by the urea method under optimized reaction conditions. The as-prepared CO3(2-)-LDH was converted to Cl- -LDH by treating with a NaCl-HCl mixed solution, retaining its high crystallinity and hexagonal platelike morphology. LDHs intercalated with a variety of anions (such as NO3-, ClO4-, acetate, lactate, dodecyl sulfate, and oleate) were further prepared from Cl- -LDH via an anion-exchange process employing corresponding salts. Exchanged products in various anion forms were found to show different delamination behaviors in formamide. Among them, best results were observed for NO3- -LDH in terms of the exfoliating degree and the quality of the exfoliated nanosheets. The delamination gave a pink transparent suspension containing well-defined nanosheets with lateral sizes of up to 2 microm. The resulting nanosheets were assembled layer-by-layer with an anionic polymer, poly(sodium styrene 4-sulfonate) (PSS), onto quartz glass substrates to produce composite films. Magnetic circular dichroism (MCD) measurements revealed that the assembled multilayer films exhibited an interesting magneto-optical response.

Optical band gaps of organic semiconductor materials

NASA Astrophysics Data System (ADS)

Costa, José C. S.; Taveira, Ricardo J. S.; Lima, Carlos F. R. A. C.; Mendes, Adélio; Santos, Luís M. N. B. F.

2016-08-01

UV-Vis can be used as an easy and forthright technique to accurately estimate the band gap energy of organic π-conjugated materials, widely used as thin films/composites in organic and hybrid electronic devices such as OLEDs, OPVs and OFETs. The electronic and optical properties, including HOMO-LUMO energy gaps of π-conjugated systems were evaluated by UV-Vis spectroscopy in CHCl3 solution for a large number of relevant π-conjugated systems: tris-8-hydroxyquinolinatos (Alq3, Gaq3, Inq3, Al(qNO2)3, Al(qCl)3, Al(qBr)3, In(qNO2)3, In(qCl)3 and In(qBr)3); triphenylamine derivatives (DDP, p-TTP, TPB, TPD, TDAB, m-MTDAB, NPB, α-NPD); oligoacenes (naphthalene, anthracene, tetracene and rubrene); oligothiophenes (α-2T, β-2T, α-3T, β-3T, α-4T and α-5T). Additionally, some electronic properties were also explored by quantum chemical calculations. The experimental UV-Vis data are in accordance with the DFT predictions and indicate that the band gap energies of the OSCs dissolved in CHCl3 solution are consistent with the values presented for thin films.

[Effects of Ca2+ on nitric oxide-induced adventitious rooting in cucumber under drought stress].

PubMed

Li, Chun Lan; Niu, Li Juan; Hu, Lin Li; Liao, Wei Biao; Chen, Yue

2017-11-01

Cucumber (Cucumis sativus L. 'Xinchun 4') was used to explore the relationship between nitric oxide (NO) and calcium (Ca 2+ ) during adventitious rooting under drought stress. Rooting parameters, endogenous Ca 2+ fluorescent intensity and the antioxidant enzymes activity (SOD, CAT and APX) in cucumber explants under drought stress were investigated. The results showed that treatment with 200 μmol·L -1 CaCl 2 and 0.05% PEG significantly improved the number and length of adventitious root in cucumber explants under drought stress, while the application of Ca 2+ chelating agent (EGTA) and channel inhibitor (BAPTA/AM) significantly decreased NO-induced number and length of adventitious root under drought stress. Under drought stress, the fluorescence intensity of Ca 2+ in hypocotyls treated with NO and CaCl 2 was improved, however, the Ca 2+ fluorescence intensity in the hypocotyls treated with NO scavenger (cPTIO) was significantly lower than that in the hypocotyls treated with NO. Under drought stress, the activities of antioxidant enzymes in the cucumber explants were significantly promoted by the treatments with NO and CaCl 2 , however, Ca 2+ chelating agent and channel inhibitor significantly decreased the activity of antioxidant enzymes induced by NO. In conclusion, Ca 2+ might be involved in the process of NO-adjusted antioxidant enzymes activity during adventitious rooting under drought stress, which alleviated the negative effects of drought on the adventitious rooting and promoted the formation of adventitious roots.

Nitrogen Species in the Post-Pinatubo Stratosphere: Model Analysis Utilizing UARS Measurements

NASA Technical Reports Server (NTRS)

Danilin, Michael Y.; Rodriguez, Jose M.; Hu, Wen-Jie; Ko, Malcolm K. W.; Weisenstein, Debra K.; Kumer, John B.; Mergenthaler, John L.; Russel, James M., III; Koike, Makoto; Yue, Glenn K.

1999-01-01

We present an analysis of the impact of heterogeneous chemistry on the partitioning of nitrogen species measured by the Upper Atmosphere Research Satellite (UARS) instruments. The UARS measurements utilized include N2O, HNO3, and ClONO2 from the cryogenic limb array etalon spectrometer (CLAES), version 7 (v.7), and temperature, methane, ozone, H2O, HCl, NO and NO2 from the halogen occultation experiment (HALOE), version 18. The analysis is carried out for the UARS data obtained between January 1992 and September 1994 in the 100-to 1-mbar (approx. 17-47 km) altitude range and over 10 degrees latitude bins from 70 S to 70 N. The spatiotemporal evolution of aerosol surface area density (SAD) is adopted from analysis of the Stratospheric Aerosol and Gas Experiment (SAGE) II data. A diurnal steady state photochemical box model, constrained by the temperature, ozone, H2O, CH4, aerosol SAD, and columns of O2 and O3 above the point of interest, has been used as the main tool to analyze these data. Total inorganic nitrogen (NOy) is obtained by three different methods: (1) as a sum of the UARS-measured NO, NO2, HNO3, and ClONO2; (2) from the N2O-NOy correlation, and (3) from the CH4-NOy correlation. To validate our current understanding of stratospheric heterogeneous chemistry for post-Pinatubo conditions, the model-calculated monthly averaged NOx/NOy ratios and the NO, NO2, and HNO3 profiles are compared with the UARS-derived data. In general, the UARS-constrained box model captures the main features of nitrogen species partitioning in the post-Pinatubo years, such as recovery of NOx after the eruption, their seasonal variability and vertical profiles. However, the model underestimates the NO2 content, particularly in the 30- to 7-mbar (approx.23-32 km) range. Comparisons of the calculated temporal behavior of the partial columns of NO2 and HNO3 and ground-based measurements at 45 S and 45 N are also presented. Our analysis indicates that ground-based and HALOE v.18 measurements of the NO2 vertical columns are consistent within the range of their uncertainties and are systematically higher (up to 50%) than the model results at midlatitudes in both hemispheres. Reasonable agreement is obtained for HNO3 columns at 45 S, suggesting some problems with nitrogen species partitioning in the model. Outstanding uncertainties are discussed.

Development of Specialized Equipment to Measure Piezoelectric Coefficients of Polymer Piezoelectric Materials,

DTIC Science & Technology

1980-02-22

definition g.l = (Voc/t)(F/wt) = field/stress 2. C =KT K 1E w/t (parallel plate capacitdnce formula) ’. VL = Voc Cx’/CL for CL > Cx 4.v g/wF Kt Eoewlt...V = (g3 1 /w)F 2. V L =(Cg/c,.v oc 3. V =(Cg/CL)(g31/w)F 4. Vstd = "d3 3"/C std F 5. V L/ Vst d = (C /C ) (g ’)(C /"d " )Sg L 31 std 33 01. 6. R (in...34 and the second T " e’hicial Note No. 1 - Theory of the use of Channel Products (’DT (X() d., meteor to measure d31 direct.]y on Piezoelect.rlc Ceramic

Weak hydrogen bonding and fluorous interactions in the chloride and bromide salts of 4-[(2,2,3,3-tetrafluoropropoxy)methyl]pyridinium.

PubMed

Lu, Norman; Wei, Rong Jyun; Lin, Kwan Yu; Alagesan, Mani; Wen, Yuh Sheng; Liu, Ling Kang

2017-04-01

Neutralization of 4-[(2,2,3,3-tetrafluoropropoxy)methyl]pyridine with hydrohalo acids HX (X = Cl and Br) yielded the pyridinium salts 4-[(2,2,3,3-tetrafluoropropoxy)methyl]pyridinium chloride, C 9 H 10 F 4 NO + ·Cl - , (1), and 4-[(2,2,3,3-tetrafluoropropoxy)methyl]pyridinium bromide, C 9 H 10 F 4 NO + ·Br - , (2), both carrying a fluorous side chain at the para position of the pyridinium ring. Single-crystal X-ray diffraction techniques revealed that (1) and (2) are isomorphous. The halide anions accept four hydrogen bonds from N-H, ortho-C-H and CF 2 -H groups. Two cations and two anions form a centrosymmetric dimeric building block, utilizing complimentary N-H...X...H-Csp 3 connections. These dimers are further crosslinked, utilizing another complimentary Csp 2 -H...X...H-Csp 2 connection. The pyridinium rings are π-stacked, forming columns running parallel to the a axis that make angles of ca 44-45° with the normal to the pyridinium plane. There are also supramolecular C-H...F-C interactions, namely bifurcated C-H...F and bifurcated C-F...H interactions; additionally, one type II C-F...F-C halogen bond has been observed.

Contact Lens-Induced Discomfort and Inflammatory Mediator Changes in Tears.

PubMed

Masoudi, Simin; Zhao, Zhenjun; Stapleton, Fiona; Willcox, Mark

2017-01-01

Studies indicate that contact lens (CL) discontinuation mostly occurs because of dryness and discomfort symptoms. This study aimed to investigate relationships between changes in the concentration of tear inflammatory mediators with subjective comfort ratings with CL wear and no contact lens wear between morning and evening. Forty-five subjects collected tears twice daily in the morning and in the evening with or without lenses. Comfort was rated subjectively on a scale from 1 to 100 (where 100 was extremely comfortable) just before each tear collection. Tear samples were assayed for complement components (C3 and C3a), leukotriene B4 (LTB4), secretory phospholipase A2 (sPLA2), secretory immunoglobulin A (sIgA), and bradykinin using commercially available immuno-based assay kits. Comfort ratings showed a statistically significant decline from morning to evening both with CL (89.0±10.1 AM vs. 76.7±15.2 PM; P<0.001) and without CL (89.1±10.2 AM vs. 84.2±12.6 PM; P<0.005) wear. The decline was steeper with lens wear (P<0.001). Bradykinin and sPLA2 levels did not change between morning and evening or with CL wear (P>0.05). Leukotriene B4 levels were slightly higher in CL (CL 43.4±12.6 pg/ml vs. No CL 39.4±13.4 pg/mL; P=0.034), whereas the concentration of LTB4, C3, C3a, and sIgA dropped by the end of the day in the presence or absence of lens wear (P<0.001). For most mediators, tear levels were not correlated with comfort ratings in any of the conditions. Leukotriene B4 had a higher concentration in the evening, and when measured as a ratio to sIgA, there was a trend for increased concentration of this mediator during CL wear. Although specific mediators showed changes from morning to evening with and without lens wear, most of these were not correlated with subjective comfort ratings in lens wear. The only mediator that showed an increase in concentration during the day and during lens wear was LTB4, and further studies on this mediator are warranted.

Aluminum exposure for one hour decreases vascular reactivity in conductance and resistance arteries in rats

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

Schmidt, Patrícia Medeiros; Escobar, Alyne Goulart

Aims: Aluminum (Al) is an important environmental contaminant; however, there are not enough evidences of Al-induced cardiovascular dysfunction. We investigated the effects of acute exposure to aluminum chloride (AlCl{sub 3}) on blood pressure, vascular reactivity and oxidative stress. Methods and results: Male Wistar rats were divided into two groups: Untreated: vehicle (ultrapure water, ip) and AlCl{sub 3}: single dose of AlCl{sub 3} (100 mg/kg,ip). Concentration-response curves to phenylephrine in the absence and presence of endothelium, the nitric oxide synthase inhibitor L-NAME, the potassium channel blocker tetraethylammonium, and the NADPH oxidase inhibitor apocynin were performed in segments from aortic and mesentericmore » resistance arteries. NO released was assessed in aorta and reactive oxygen species (ROS), malondialdehyde, non-protein thiol levels, antioxidant capacity and enzymatic antioxidant activities were investigated in plasma, aorta and/or mesenteric arteries. After one hour of AlCl{sub 3} exposure serum Al levels attained 147.7 ± 25.0 μg/L. Al treatment: 1) did not affect blood pressure, heart rate and vasodilator responses induced by acetylcholine or sodium nitroprusside; 2) decreased phenylephrine-induced vasoconstrictor responses; 3) increased endothelial modulation of contractile responses, NO release and vascular ROS production from NADPH oxidase; 4) increased plasmatic, aortic and mesenteric malondialdehyde and ROS production, and 5) decreased antioxidant capacity and affected the antioxidant biomarkers non-protein thiol levels, glutathione peroxidase, glutathione-S-transferase, superoxide dismutase and catalase enzymatic activities. Conclusion: AlCl{sub 3}-acute exposure reduces vascular reactivity. This effect is associated with increased NO production, probably acting on K{sup +} channels, which seems to occur as a compensatory mechanism against Al-induced oxidative stress. Our results suggest that Al exerts toxic effects to the vascular system. - Highlights: • One hour of aluminum exposure decreases vascular reactivity. • Vascular imbalance after aluminum exposure is related to increased oxidative stress. • Enhanced NO release is the first step against the effects of Al at vascular system.« less

Reactions of a Chromium(III)-Superoxo Complex and Nitric Oxide That Lead to the Formation of Chromium(IV)-Oxo and Chromium(III)-Nitrito Complexes

PubMed Central

Yokoyama, Atsutoshi; Cho, Kyung-Bin

2013-01-01

The reaction of an end-on Cr(III)-superoxo complex bearing a 14-membered tetraazamacrocyclic TMC ligand, [CrIII(14-TMC)(O2)(Cl)]+, with nitric oxide (NO) resulted in the generation of a stable Cr(IV)-oxo species, [CrIV(14-TMC)(O)(Cl)]+, via the formation of a Cr(III)-peroxynitrite intermediate and homolytic O-O bond cleavage of the peroxynitrite ligand. Evidence for the latter comes from EPR spectroscopy, computational chemistry, and the observation of phenol nitration chemistry. The Cr(IV)-oxo complex does not react with nitrogen dioxide (NO2), but reacts with NO to afford a Cr(III)-nitrito complex, [CrIII(14-TMC)(NO2)(Cl)]+. The Cr(IV)-oxo and Cr(III)-nitrito complexes were also characterized spectroscopically and/or structurally. PMID:24066924

Investigation of efflorescence of inorganic aerosols using fluorescence spectroscopy.

PubMed

Choi, Man Yee; Chan, Chak K

2005-02-17

The phase transition is one of the most fundamental phenomena affecting the physical and chemical properties of atmospheric aerosols. Efflorescence, in particular, is not well understood, partly because the molecular interactions between the solute and water molecules of saturated or supersaturated solution droplets have not been well characterized. Recently, we developed a technique that combines the use of an electrodynamic balance and a fluorescence dye, 8-hydroxyl-1,3,6-pyrenetrisulfonate (pyranine), to study the distributions of solvated and free water in aqueous droplets (Choi, M. Y.; Chan, C. K.; Zhang, Y. H. J. Phys. Chem. A 2004, 108, 1133). We found that the equality of the amounts of solvated and free water is a necessary but not sufficient condition for efflorescence. For efflorescing compounds such as Na2SO4, (NH4)2SO4, and a mixture of NaCl and Na2SO4, the amount of free water decreases, while that of solvated water is roughly constant in bulk measurements and decreases less dramatically than that of free water in single-particle measurements as the relative humidity (RH) decreases. Efflorescence of the supersaturated droplets of these solutions occurs when the amounts of free and solvated water are equal, which is consistent with our previous observation for NaCl. For nonefflorescing compounds in single-particle levitation experiments such as MgSO4 and Mg(NO3)2, the amounts of free and solvated water are equal at a water-to-solute molar ratio of about 6, at which spectral changes due to the formation of contact ion pairs between magnesium and the anions occur as shown by Raman spectroscopy. Fluorescence imaging shows that the droplets of diluted Mg(NO3)2 (at 80% RH) and MgSO4 are homogeneous but those of NaCl, Na2SO4, (NH4)2SO4, and supersaturated Mg(NO3)2 (at 10% RH) are heterogeneous in terms of the solvated-to-free water distribution. The solvated-to-free water ratios in NaCl, Na2SO4, and (NH4)2SO4 droplets are higher in the outer regions by about half a radius deep than at the center of the droplets.

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.

Azobenzene Pd(II) complexes with N^N- and N^O-type ligands

NASA Astrophysics Data System (ADS)

Nikolaeva, M. V.; Puzyk, An. M.; Puzyk, M. V.

2017-05-01

Methods of synthesis of cyclometalated azobenzene palladium(II) complexes of [Pd(N^N)Azb]ClO4 and [Pd(N^O)Azb]ClO4 types (where Azb- is the deprotonated form of azobenzene; N^N is 2NH3, ethylenediamine, or 2,2'-bipyridine; and (N^O)- is the deprotonated form of amino acid (glycine, α-alanine, β-alanine, tyrosine, or tryptophan)) are developed. The electronic absorption and the electrochemical properties of these complexes are studied.

Regulation of intracellular pH in the rabbit cortical collecting tubule.

PubMed Central

Weiner, I D; Hamm, L L

1990-01-01

The cortical collecting tubule (CCT) is an important nephron segment for Na+, K+, water and acid-base transport. Differential loading characteristics of the pH sensitive dye 2',7'-bis-(2-carboxyethyl)-5(and-6)carboxyfluorescein (BCECF) and basolateral Cl- removal were used to identify and study intracellular pH (pHi) regulation in each of three cell types involved in this transport. Both principal cells and beta-intercalated cells were found to have a basolateral Na+/H+ exchanger based on the Na+ and amiloride sensitivity of pHi recovery from acid loads. Intercalated cells demonstrated abrupt pHi changes with basolateral Cl- removal. alpha-intercalated cells alkalinized; beta-intercalated cells acidified. In the beta-intercalated cells, luminal Cl- removal blocked changes in pHi in response to changes in luminal HCO3- or peritubular Cl-, providing direct evidence for a luminal Cl-/HCO3- exchanger. In principal cells, brief removal of either peritubular or luminal Cl- resulted in no change in pHi; however, return of peritubular Cl- after prolonged removal resulted in a rapid fall in pHi consistent with a basolateral Cl-/HCO3- exchanger, which may be relatively inactive under baseline conditions. Therefore, Cl-/HCO3- exchange is present in all three cell types but varies in location and activity. PMID:2153152

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

USGS Publications Warehouse

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

2016-01-01

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 relatively low and homogeneous anion concentrations in the ice-cemented sediments point to either a mechanism of recent salt removal, or to relatively modern permafrost soils (<1 million years). Together, our results show that near surface salts in University Valley serve as an end-member of stratospheric sources not subject to biological processes or extensive remobilization.

Case studies on the chemical composition of fogwater: The influence of local gaseous emissions

NASA Astrophysics Data System (ADS)

Johnson, C. Annette; Sigg, Laura; Zobrist, Jürg

In order to study the mechanisms governing the composition of fogwater, sequential samples were taken during two fog events over several hours and analyzed chemically. In addition, preliminary measurements of gases (HCl, HNO 3, NH 3) and aerosols (H 2SO 4, NH 4NO 3, NH 4Cl and ammonium sulfates) were made. The uptake of gaseous HCl in the fog droplets was a major source of acidity: in extreme cases pH values of 2.08 and 1.94 and Cl - concentrations up to 10 -2 M were observed. HCl originated from a local source, most probably a refuse incinerator from which plumes of the stack gas reached the sampling site. The NH +4, NO -3 and SO -24 concentrations (in the range of 0.1-2 mrnol l-1) were regulated by the inputs of aerosols and the liquid water content of the fog. The contribution of dissolved S(IV) (0.06-0.27 mmol l-1) to the total aqueous sulfur varied with time, according to the pH-dependent solubility of SO 2 and to oxidation reactions.

Luminal flow regulates NO and O2− along the nephron

PubMed Central

Cabral, Pablo D.

2011-01-01

Urinary flow is not constant but in fact highly variable, altering the mechanical forces (shear stress, stretch, and pressure) exerted on the epithelial cells of the nephron as well as solute delivery. Nitric oxide (NO) and superoxide (O2−) play important roles in various processes within the kidney. Reductions in NO and increases in O2− lead to abnormal NaCl and water absorption and hypertension. In the last few years, luminal flow has been shown to be a regulator of NO and O2− production along the nephron. Increases in luminal flow enhance fluid, Na, and bicarbonate transport in the proximal tubule. However, we know of no reports directly addressing flow regulation of NO and O2− in this segment. In the thick ascending limb, flow-stimulated NO and O2− formation has been extensively studied. Luminal flow stimulates NO production by nitric oxide synthase type 3 and its translocation to the apical membrane in medullary thick ascending limbs. These effects are mediated by flow-induced shear stress. In contrast, flow-induced stretch and NaCl delivery stimulate O2− production by NADPH oxidase in this segment. The interaction between flow-induced NO and O2− is complex and involves more than one simply scavenging the other. Flow-induced NO prevents flow from increasing O2− production via cGMP-dependent protein kinase in thick ascending limbs. In macula densa cells, shear stress increases NO production and this requires that the primary cilia be intact. The role of luminal flow in NO and O2− production in the distal tubule is not known. In cultured inner medullary collecting duct cells, shear stress enhances nitrite accumulation, a measure of NO production. Although much progress has been made on this subject in the last few years, there are still many unanswered questions. PMID:21345976

Estimates of water and solute release from a coal waste rock dump in the Elk Valley, British Columbia, Canada.

PubMed

Villeneuve, S A; Barbour, S L; Hendry, M J; Carey, S K

2017-12-01

Long term (1999 to 2014) flow and water quality data from a rock drain located at the base of a coal waste rock dump constructed in the Elk Valley, British Columbia was used to characterize the release of three solutes (NO 3 - , Cl - and SO 4 2- ) from the dump and obtain whole dump estimates of net percolation (NP). The concentrations of dump derived solutes in the rock drain water were diluted by snowmelt waters from the adjacent natural watershed during the spring freshet and reached a maximum concentration during the winter baseflow period. Historical peak baseflow concentrations of conservative ions (NO 3 - and Cl - ) increased until 2006/07 after which they decreased. This decrease was attributed to completion of the flushing of the first pore volume of water stored within the dump. The baseflow SO 4 2- concentrations increased proportionally with NO 3 - and Cl - to 2007, but then continued to slowly increase as NO 3 - and Cl - concentrations decreased. This was attributed to ongoing production of SO 4 2- due to oxidation of sulfide minerals within the dump. Based on partitioning of the annual volume of water discharged from the rock drain to waste rock effluent (NP) and water entering the rock drain laterally from the natural watershed, the mean NP values were estimated to be 446±50mm/a (area normalized net percolation/year) for the dump and 172±71mm/a for the natural watershed. The difference was attributed to greater rates of recharge in the dump from summer precipitation compared to the natural watershed where rainfall interception and enhanced evapotranspiration will increase water losses. These estimates included water moving through subsurface pathways. However, given the limitations in quantifying these flows the estimated NP rates for both the natural watershed and the waste rock dump are considered to be low, and could be much higher (e.g. ~450mm/a and ~800mm/a). Copyright © 2017 Elsevier B.V. All rights reserved.

New layered double hydroxides by prepared by the intercalation of gibbsite

NASA Astrophysics Data System (ADS)

Rees, Jennifer R.; Burden, Chloe S.; Fogg, Andrew M.

2015-04-01

New layered double hydroxides (LDHs) with the composition [MAl4(OH)12]Cl2·1.5H2O (M=Co, Ni) have been prepared by reacting gibbsite, γ-Al(OH)3, with the appropriate chloride salt in a synthesis in which the water of crystallization is the only solvent present and fully characterized. These LDHs have been shown to undergo facile anion exchange reactions with both organic and inorganic anions at room temperature making them comparable to other LDHs in this respect. Reactions under the same conditions with CuCl2·2H2O and ZnCl2 failed to form the desired LDHs but those with nitrate salts did lead to the formation of the previously reported [MAl4(OH)12](NO3)2·1.5H2O (M=Co, Ni) compounds.

Acid-base responses to feeding and intestinal Cl- uptake in freshwater- and seawater-acclimated killifish, Fundulus heteroclitus, an agastric euryhaline teleost.

PubMed

Wood, Chris M; Bucking, Carol; Grosell, Martin

2010-08-01

Marine teleosts generally secrete basic equivalents (HCO(3)(-)) and take up Na(+) and Cl(-) in the intestine so as to promote absorption of H(2)O. However, neither the integration of these functions with feeding nor the potential role of the gut in ionoregulation and acid-base balance in freshwater have been well studied. The euryhaline killifish (Fundulus heteroclitus) is unusual in lacking both an acid-secreting stomach and a mechanism for Cl(-) uptake at the gills in freshwater. Responses to a satiation meal were evaluated in both freshwater- and seawater-acclimated killifish. In intact animals, there was no change in acid or base flux to the external water after the meal, in accord with the absence of any post-prandial alkaline tide in the blood. Indeed, freshwater animals exhibited a post-prandial metabolic acidosis ('acidic tide'), whereas seawater animals showed no change in blood acid-base status. In vitro gut sac experiments revealed a substantially higher rate of Cl(-) absorption by the intestine in freshwater killifish, which was greatest at 1-3 h after feeding. The Cl(-) concentration of the absorbate was higher in preparations from freshwater animals than from seawater killifish and increased with fasting. Surprisingly, net basic equivalent secretion rates were also much higher in preparations from freshwater animals, in accord with the 'acidic tide'; in seawater preparations, they were lowest after feeding and increased with fasting. Bafilomycin (1 micromol l(-1)) promoted an 80% increase in net base secretion rates, as well as in Cl(-) and fluid absorption, at 1-3 h post-feeding in seawater preparations only, explaining the difference between freshwater and seawater fish. Preparations from seawater animals at 1-3 h post-feeding also acidified the mucosal saline, and this effect was associated with a marked rise in P(CO(2)), which was attenuated by bafilomycin. Measurements of chyme pH from intact animals confirmed that intestinal fluid (chyme) pH and basic equivalent concentration were lowest after feeding in seawater killifish, whereas P(CO(2)) was greatly elevated (80-95 Torr) in chyme from both seawater and freshwater animals but declined to lower levels (13 Torr) after 1-2 weeks fasting. There were no differences in pH, P(CO(2)) or the concentrations of basic equivalents in intestinal fluid from seawater versus freshwater animals at 12-24 h or 1-2 weeks post-feeding. The results are interpreted in terms of the absence of gastric HCl secretion, the limitations of the gills for acid-base balance and Cl(-) transport, and therefore the need for intestinal Cl(-) uptake in freshwater killifish, and the potential for O(2) release from the mucosal blood flow by the high P(CO(2)) in the intestinal fluids. At least in seawater killifish, H(+)-ATPase running in parallel to HCO(3)(-):Cl(-) exchange in the apical membranes of teleost enterocytes might reduce net base secretion and explain the high P(CO(2)) in the chyme after feeding.

Cationic aza-macrocyclic complexes of germanium(II) and silicon(IV).

PubMed

Everett, Matthew; Jolleys, Andrew; Levason, William; Light, Mark E; Pugh, David; Reid, Gillian

2015-12-28

[GeCl2(dioxane)] reacts with the neutral aza-macrocyclic ligands L, L = Me3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane), Me4cyclen (1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane) or Me4cyclam (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and two mol. equiv. of Me3SiO3SCF3 in thf solution to yield the unusual and hydrolytically very sensitive [Ge(L)][O3SCF3]2 as white solids in moderate yield. Using shorter reaction times [Ge(Me3tacn)]Cl2 and [Ge(Me3tacn)]Cl[O3SCF3] were also isolated; the preparation of [Ge(Me4cyclen)][GeCl3]2 is also described. The structures of the Me3tacn complexes show κ(3)-coordination of the macrocycle, with the anions interacting only weakly to produce very distorted five- or six-coordination at germanium. In contrast, the structure of [Ge(Me4cyclen)][O3SCF3]2 shows no anion interactions, and a distorted square planar geometry at germanium from coordination to the tetra-aza macrocycle. Crystal structures of the Si(iv) complexes, [SiCl3(Me3tacn)]Y (Y = O3SCF3, BAr(F); [B{3,5-(CF3)2C6H3}4]) and [SiHCl2(Me3tacn)][BAr(F)], obtained from reaction of SiCl4 or SiHCl3 with Me3tacn, followed by addition of either Me3SiO3SCF3 or Na[BAr(F)], contain distorted octahedral cations, with facialκ(3)-coordinated Me3tacn. The open-chain triamine, Me2NCH2CH2N(Me)CH2CH2NMe2 (pmdta), forms [SiCl3(pmdta)][BAr(F)] and [SiBr3(pmdta)][BAr(F)] under similar conditions, containing mer-octahedral cations.

Balloon profiles of stratospheric NO[sub 2] and HNO[sub 3] for testing the heterogeneous hydrolysis of N[sub 2]O[sub 5] on sulfate aerosols

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

Webster, C.R.; May, R.D.; Allen, M.

1994-01-01

Simultaneous in situ measurements of stratospheric NO[sub 2], HNO[sub 3], HCl, and CH[sub 4] from 34 to 24 km were made in August 1992 from Palestine, Texas, using the Balloon-borne Laser In-Situ Sensor (BLISS) tunable diode laser spectrometer. Although the measurements of NO[sub 2], HNO[sub 3], and NO[sub 2]/HNO[sub 3] agree well with gas-phase model calculations near 34 km where SAGE II data show little sulfate aerosol, this is not true at the lower altitudes where SAGE II shows high aerosol loadings. At 24 km the BLISS NO[sub 2] and HNO[sub 3] measurements are 70% lower, and 50% higher, respectively,more » than the gas phase model predictions, with a measured NO[sub 2]/HNO[sub 3] ratio 5 times smaller. When the heterogeneous hydrolysis of N[sub 2]O[sub 5] and ClONO[sub 2] on sulfate aerosol of surface area densities matching the SAGE II measurements is added to the model, good agreement with the BLISS measurements is found over the whole altitude range. 24 refs., 4 figs., 1 tab.« less

Ion composition of coarse and fine particles in Iasi, north-eastern Romania: Implications for aerosols chemistry in the area

NASA Astrophysics Data System (ADS)

Arsene, Cecilia; Olariu, Romeo Iulian; Zarmpas, Pavlos; Kanakidou, Maria; Mihalopoulos, Nikolaos

2011-02-01

Atmospheric loadings of the aerosols coarse (particles of AED > 1.5 μm) and fine fractions (particles of AED < 1.5 μm) were determined in Iasi, north-eastern Romania from January 2007 to March 2008. Concentrations of water soluble ions (SO 42-, NO 3-, Cl -, C 2O 42-, NH 4+, K +, Na +, Ca 2+ and Mg 2+) were measured using ion chromatography (IC). In the coarse particles, calcium and carbonate are the main ionic constituents (˜65%), whereas in the fine particles SO 42-, NO 3-, Cl - and NH 4+ are the most abundant. Temperature and relative humidity (RH) associated with increased concentrations of specific ions might be the main factors controlling the aerosol chemistry at the investigated site. From August 2007 to March 2008 high RH (as high as 80% for about 82% of the investigated period) was prevailing in Iasi and the collected particles were expected to have deliquesced and form an internal mixture. We found that in fine particles ammonium nitrate (NH 4NO 3) is important especially under conditions of NH 4+/SO 42- ratio higher than 1.5 and high RH (RH above deliquescence of NH 4Cl, NH 4NO 3 and (NH 4) 2SO 4). At the investigated site large ammonium artifacts may occur due to inter-particle interaction especially under favorable meteorological conditions. A methodology for estimating the artifact free ambient ammonium concentration is proposed for filter pack sampling data of deliquesced particles. Nitrate and sulfate ions in coarse particles are probably formed via reactions of nitric and sulfuric acid with calcium carbonate and sodium chloride which during specific seasons are abundant at the investigated site. In the fine mode sulfate concentration maximized during summer (due to enhanced photochemistry) and winter (due to high concentration of SO 2 emitted from coal burning). Natural contributions, dust or sea-salt related, prevail mainly in the coarse particles. From May 2007 to August 2007, when air masses originated mainly from Black Sea, in the coarse particles an nss-Cl/Na ratio of 1.11 was measured. Elevated levels of chloride in fine particles have been attributed to waste burning in the proximity of the investigated site or to NaCl salt widely spread on roads during winter. Considering the importance of atmospheric aerosols, this study may constitute a reference point for Eastern Europe.

IGF-1 and insulin exert opposite actions on ClC-K2 activity in the cortical collecting ducts.

PubMed

Zaika, Oleg; Mamenko, Mykola; Boukelmoune, Nabila; Pochynyuk, Oleh

2015-01-01

Despite similar stimulatory actions on the epithelial sodium channel (ENaC)-mediated sodium reabsorption in the distal tubule, insulin promotes kaliuresis, whereas insulin-like growth factor-1 (IGF-1) causes a reduction in urinary potassium levels. The factors contributing to this phenomenon remain elusive. Electrogenic distal nephron ENaC-mediated Na(+) transport establishes driving force for Cl(-) reabsorption and K(+) secretion. Using patch-clamp electrophysiology, we document that a Cl(-) channel is highly abundant on the basolateral plasma membrane of intercalated cells in freshly isolated mouse cortical collecting duct (CCD) cells. The channel has characteristics attributable to the ClC-K2: slow gating kinetics, conductance ∼10 pS, voltage independence, Cl(-)>NO3 (-) anion selectivity, and inhibition/activation by low/high pH, respectively. IGF-1 (100 and 500 nM) acutely stimulates ClC-K2 activity in a reversible manner. Inhibition of PI3-kinase (PI3-K) with LY294002 (20 μM) abrogates activation of ClC-K2 by IGF-1. Interestingly, insulin (100 nM) reversibly decreases ClC-K2 activity in CCD cells. This inhibitory action is independent of PI3-K and is mediated by stimulation of a mitogen-activated protein kinase-dependent cascade. We propose that IGF-1, by stimulating ClC-K2 channels, promotes net Na(+) and Cl(-) reabsorption, thus reducing driving force for potassium secretion by the CCD. In contrast, inhibition of ClC-K2 by insulin favors coupling of Na(+) reabsorption with K(+) secretion at the apical membrane contributing to kaliuresis. Copyright © 2015 the American Physiological Society.

Groundwater chemistry and occurrence of arsenic in the Meghna floodplain aquifer, southeastern Bangladesh

USGS Publications Warehouse

Zahid, A.; Hassan, M.Q.; Balke, K.-D.; Flegr, M.; Clark, D.W.

2008-01-01

Dissolved major ions and important heavy metals including total arsenic and iron were measured in groundwater from shallow (25-33 m) and deep (191-318 m) tube-wells in southeastern Bangladesh. These analyses are intended to help describe geochemical processes active in the aquifers and the source and release mechanism of arsenic in sediments for the Meghna Floodplain aquifer. The elevated Cl- and higher proportions of Na+ relative to Ca2+, Mg2+, and K+ in groundwater suggest the influence by a source of Na+ and Cl-. Use of chemical fertilizers may cause higher concentrations of NH 4+ and PO 43- in shallow well samples. In general, most ions are positively correlated with Cl-, with Na+ showing an especially strong correlation with Cl-, indicating that these ions are derived from the same source of saline waters. The relationship between Cl-/HCO 3- ratios and Cl- also shows mixing of fresh groundwater and seawater. Concentrations of dissolved HCO 3- reflect the degree of water-rock interaction in groundwater systems and integrated microbial degradation of organic matter. Mn and Fe-oxyhydroxides are prominent in the clayey subsurface sediment and well known to be strong adsorbents of heavy metals including arsenic. All five shallow well samples had high arsenic concentration that exceeded WHO recommended limit for drinking water. Very low concentrations of SO 42- and NO 3- and high concentrations of dissolved Fe and PO 43- and NH 4+ ions support the reducing condition of subsurface aquifer. Arsenic concentrations demonstrate negative co-relation with the concentrations of SO 42- and NO 3- but correlate weakly with Mo, Fe concentrations and positively with those of P, PO 43- and NH 4+ ions. ?? 2007 Springer-Verlag.

Growth/no growth boundary of Clostridium perfringens from spores in cooked meat: A logistic analysis.

PubMed

Huang, Lihan; Li, Changcheng; Hwang, Cheng-An

2018-02-02

Clostridium perfringens is a major foodborne health hazard that can cause acute gastroenteritis in consumers, and is often associated with cooked meat and poultry products. Improper cooling after cooking may allow this pathogen to grow in a product, producing an enterotoxin that causes food poisoning. This study was conducted to evaluate the effect of common ingredients, including sodium tripolyphosphate (STPP), sodium lactate (NaL), and sodium chloride (NaCl), on the germination and outgrowth of C. perfringens spores in meat products. The growth/no growth test was conducted in Shahidi Ferguson Perfringens agar mixed with STPP (0-2500ppm), NaL (0-4%), and NaCl (0-4%) in microplates. Turbidity measurements at 600nm were compared before and after anaerobic incubation at 46°C to evaluate growth and no growth conditions. The dichotomous responses were analyzed by logistic regression to develop a model for estimating the growth probability of C. perfringens. The probability model was used to define the threshold of growth (probability >0.1 or 0.2) of C. perfringens and validated using inoculated ground beef under optimum temperature. Inoculated ground beef was mixed with different combinations of STPP, NaL, and NaCl to observe growth or no growth of C. perfringens, and the probability was calculated from the formulation. If the threshold of growth was set to 0.2, the accuracy of the growth and no growth predictions was 95.7%, with 4.3% over-prediction of growth events (fail-safe). The results from this study suggested that proper combinations of STPP, NaL, and NaCl could be used to control the growth of C. perfringens in cooked beef under the optimum temperature. The results may also suggest that proper combinations of STPP, NaL, and NaCl in cooked meat and poultry products could be used to prevent the growth of C. perfringens during cooling. Published by Elsevier B.V.

Efficacy of chlorine dioxide on Escherichia coli inactivation during pilot-scale fresh-cut lettuce processing.

PubMed

Banach, J L; van Overbeek, L S; Nierop Groot, M N; van der Zouwen, P S; van der Fels-Klerx, H J

2018-03-23

Controlling water quality is critical in preventing cross-contamination during fresh produce washing. Process wash water (PWW) quality can be controlled by implementing chemical disinfection strategies. The aim of this study was to evaluate the pilot-scale efficacy of chlorine dioxide (ClO 2 ) during processing on the reduction of Escherichia coli in the PWW and on processed fresh-cut 'Lollo Rossa' lettuce. The objective was to have a residual target concentration of either 5 or 3 mg/L ClO 2 in the washing tank (3.5 m 3 ) before and during 800 kg of lettuce processing (90 min). After 90 min., a nonpathogenic, non-Extended Spectrum Beta-Lactamase (ESBL) E. coli inoculum from an overnight culture broth (37 °C) was added to the tank resulting in an approximate final level of 10 6  CFU/mL. PWW and lettuce samples for microbiological and chemical analyses were taken before and after the input and supply halted. ClO 2 concentrations quickly decreased after ClO 2 input halted, yet a residual concentration of ≥2.5 mg/L and ≥2.1 mg/L ClO 2 , respectively for 5 and 3 mg/L pilots, was present 12 min after the supply halted. No detectable levels of E. coli (limit of detection 5 log) were determined in the water within 1 min after E. coli was added to the ClO 2 containing wash water. Results demonstrated that ClO 2 use at the semi-commercial pilot scale was able to reduce the E. coli peak contamination in the PWW. After storage (5 days, 4 °C), background microbial communities (i.e., fluorescent Pseudomonads and total heterotrophic bacteria) grew out on lettuce. Overall, ClO 2 decreased the potential for cross-contamination between batches compared to when no sanitizer was used. Chlorate levels of the lettuce sampled before entering the wash water ranged from 7.3-11.6 μg/kg. The chlorate levels of the lettuce sampled after being washed in the ClO 2 containing wash water, as well as after rinsing and centrifugation, ranged from 22.8-60.4 μg/kg; chlorite levels ranged from 1.3-1.6 mg/kg, while perchlorate levels were below the limit of quantification (LOQ, <5 ng/g). In this study, we report the semi-commercial pilot-scale evaluation of ClO 2 , for its ability to maintain the PWW quality and to prevent cross-contamination in the washing tank during fresh-cut lettuce processing. Furthermore, we provide quantitative values of ClO 2 disinfection by-products chlorate and chlorite as well as of perchlorate from PWW and/or lettuce samples. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

Prevention and treatment of Nitrite toxicity in juvenile steelhead trout (Salmo gairdneri)

USGS Publications Warehouse

Wedemeyer, Gary A.; Yasutake, W.T.

1978-01-01

The efficacy of mineral salts, pH, and tetramethylthianine (methylene blue) treatment in reducing the acute toxicity of nitrite to fingerling steelhead trout (Salmo gairdneri) was determined using a static bioassay system at 10 °C. The acute toxicity (96-h LC50) was reduced by a factor of about 24 for 5-g steelhead and 13 for 10-g fish when the total water hardness was increased from 25 to 300 mg/L (as CaCO3). NaCl or CaCl2 additions (0–200 mg/L) reduced toxicity by a factor of up to 3 for NaCl and 50 for CaCl2. Increasing the pH from 6.0 to 8.0 decreased toxicity by a factor of about 8 for the smaller and 3 for the larger fish. Methylene blue at 0.1 or 1.0 mg/L was effective in decreasing acute toxicity. For alleviating methemoglobinemia, removing the fish to freshwater for 48 h was about as effective as 1.0 mg/L methylene blue. Chronic exposure in soft water to 0.03 mg/L NO2-N for 6 mo caused no significant growth reduction, gill histological changes, hematological dyscrasias, or impaired ability of the smolts to adapt to 30‰ seawater and grow for an additional 2 mo. Key words: nitrite, toxicity, fish, methylene blue, pH, salts, acute toxicity, chronic toxicity

Genotoxicity testing of two lead-compounds in somatic cells of Drosophila melanogaster.

PubMed

Carmona, Erico R; Creus, Amadeu; Marcos, Ricard

2011-09-18

The in vivo genotoxic activity of two inorganic lead compounds was studied in Drosophila melanogaster by measurement of two different genetic endpoints. We used the wing-spot test and the comet assay. The comet assay was conducted with larval haemocytes. The results from the wing-spot test showed that neither lead chloride, PbCl(2), nor lead nitrate, Pb(NO(3))(2), were able to induce significant increases in the frequency of mutant spots. In addition, the combined treatments with gamma-radiation and PbCl(2) or Pb(NO(3))(2) did not show significant variations in the frequency of the three categories of mutant spots recorded, compared with the frequency induced by gamma-radiation alone. This seems to indicate that the lead compounds tested do not interact with the repair of the genetic damage induced by ionizing radiation. When the lead compounds were evaluated in the in vivo comet assay with haemocytes, Pb(NO(3))(2) was effective in inducing significant increases of DNA damage with a direct dose-response pattern. These results confirm the usefulness of the comet assay with haemocytes as an in vivo model and support the assumption that there is a genotoxic risk associated with lead exposure. Copyright © 2011 Elsevier B.V. All rights reserved.

A kinetics investigation of several reactions involving chlorine containing compounds

NASA Technical Reports Server (NTRS)

Davis, D. D.

1978-01-01

The technique of flash photolysis-resonance fluorescence was utilized to study nine reactions of stratospheric importance. The tropospheric degradation reactions of seven halogenated hydrocarbons were studied to assess their possible influx into the stratosphere. There are reactions of either Cl, OH, or O(3P) species with hydrogenated species, O3 or chlorinated compounds. Apart from the kinetic measurements, the quantum yield for the production of O(1D) from O3 in the crucial wavelength region of 293 to 316.5 nm was studied by utilizing a narrow wavelength laser as the photolysis source. The product formation was monitored by measuring the fluorescence of NO2 formed through O(1D) reaction with N2O followed by NO reaction with O3 to give NO2.

Effects of added CeCl3 on resistance of fifth-instar larvae of silkworm to Bombyx mori nucleopolyhedrovirus infection.

PubMed

Li, Bing; Xie, Yi; Cheng, Zhe; Cheng, Jie; Hu, Rengping; Cui, Yaling; Gong, Xiaolan; Shen, Weide; Hong, Fashui

2012-06-01

One of the most important agents causing lethal disease in the silkworm is the Bombyx mori nucleopolyhedrovirus (BmNPV), while low-dose rare earths are demonstrated to increase immune capacity in animals. However, very little is known about the effects of added CeCl(3) on decreasing BmNPV infection of silkworm. The present study investigated the effects of added CeCl(3) to an artificial diet on resistance of fifth-instar larvae of silkworm to BmNPV infection. Our findings indicated that added CeCl(3) significantly decreased inhibition of growth and mortality of fifth-instar larvae caused by BmNPV infection. Furthermore, the added CeCl(3) obviously decreased lipid peroxidation level and accumulation of reactive oxygen species such as O(2)(-), H(2)O(2), (·)OH, and NO and increased activities of the antioxidant enzymes including superoxide dismutase, catalase, ascorbate peroxidase, glutathione peroxidase, ascorbate, and glutathione contents in the BmNPV-infected fifth-instar larvae. In addition, the added CeCl(3) could significantly promote acetylcholine esterase activity and attenuate the activity of inducible nitric oxide synthase in the BmNPV-infected fifth-instar larvae. These findings suggested that added CeCl(3) may relieve oxidative damage and neurotoxicity of silkworm caused by BmNPV infection via increasing antioxidant capacity and acetylcholine esterase activity.

XM746 Practice Fuze.

DTIC Science & Technology

1980-07-01

34 t"Codes LIST OF ILLUSTRATIONS Figure No. Title Page 1 ARRADCOM XM747 ( M739 ) Practice Fuze 2 2A Cover, Spotting Charge 4 2B Cup, Spotting Charge 5 3...Plastic Practice Fuze XM746 Preliminary Design 6 4 Modified PDM739 Fuze 7 5 XM746 All Plastic Fuze 9 6 ARRADCOM XK747 ( M739 ) Practice Fuze 11 7...Assembly 18 11 Smoke Exit Relationship 19 12A XM747 MBA TiCl4 Configuration 23 12B Fuze M739 MOD F 24 13 TiCl4 Assembly 25 14 BKNO3 Assembly 26 15

NO, hydrogen sulfide does not come first during tomato response to high salinity.

PubMed

da-Silva, Cristiane J; Mollica, Débora C F; Vicente, Mateus H; Peres, Lázaro E P; Modolo, Luzia V

2018-06-01

High salinity greatly impacts agriculture, particularly in tomato (Solanum lycopersicum), a crop that is a model to study this abiotic stress. This work investigated whether hydrogen sulfide (H 2 S) acts upstream or downstream of nitric oxide (NO) in the signaling cascade during tomato response to salt stress. An NO-donor incremented H 2 S levels by 12-18.9% while an H 2 S-donor yielded 10% more NO in roots. The NO accumulated in roots one-hour after NaCl treatment while H 2 S accumulation started two-hour later. The NO stimulated H 2 S accumulation in roots/leaves, but not the opposite (i.e H 2 S was unable to stimulate NO accumulation) two-hour post NaCl treatment. Also, NO accumulation was accompanied by an increment of transcript levels of genes that encode for H 2 S-synthesizing enzymes. Our results indicate that H 2 S acts downstream of NO in the mitigation of oxidative stress, which helps tomato plants to tolerate high salinity. Copyright © 2017 Elsevier Inc. All rights reserved.

Determination of NH(3) gas by combination of nanosized LaCoO(3) converter with chemiluminescence detector.

PubMed

Shi, Jinjun; Yan, Ruoxue; Zhu, Yongfa; Zhang, Xinrong

2003-10-17

Combination of a novel NH(3) converter based on nanosized materials with chemiluminescence (CL) detector for the determination of NH(3) gas was demonstrated in this paper. NH(3) gas is oxidized on different nanosized catalysts to produce NO(x), which can react with luminol to generate CL emission. Eight nanosized materials were investigated as catalyst, and CL was detected from seven of them. The nanosized LaCoO(3) was chosen as the catalyst for preparing the converter because of its higher activity than others. Under the optimized conditions, the linear range of CL intensity versus concentration of NH(3) gas is 0.04-10 ppm (r=0.9951, n=14) with the detection limit of 0.014 ppm. The method offers advantages of long lifetime of the converter, fast response and high selectivity to NH(3). There was no response while the foreign substances, such as hydrogen, oxygen, nitrogen, formaldehyde, acetone and gasoline passing through the CL detection system, and the interference of CCl(4), ethanol, ethylene and toluene was insignificant.

Citric acid production using immobilized conidia of Aspergillus niger TMB 2022

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

Tsay, S.S.; To, K.Y.

1987-02-20

Conidia of Aspergillus niger TMB 2022 were immobilized in calcium alginate for the production of citric acid. A 1-ml condidia suspension containing ca. 2.32 x 10/sup 8/ conidia were entrapped into sodium alginate solution in order to prepare 3% Ca-alginate (w/v) gel bead. Immobilized conidia were inoculated into productive medium containing 14% sucrose, 0.25% (NH/sub 4/)/sub 2/CO/sub 3/, 0.25% KH/sub 2/PO/sub 4/, and 0.025% MgSO/sub 4/.7H/sub 2/O with addition of 0.06 mg/l CuSO/sub 4/.5H/sub 2/O, 0.25 mg/l ZnCl/sub 2/, 1.3 mg/l FeCl/sub 3/.6H/sub 2/O, pH 3.8, and incubated at 35 degrees C for 13 days by surface culture to producemore » 61.53 g/l anhydrous citric acid. Under the same conditions with a batchwise culture, it was found that immobilized conidia could maintain a longer period for citric acid production (31 days): over 70 g/l anhydrous citric acid from runs No. 2-4, with the maximum yield for anhydrous citric acid reaching 77.02 g/l for run No. 2. In contrast, free conidia maintained a shorter acid-producing phase, circa 17 days; the maximum yield for anhydrous citric acid was 71.07 g/l for run No. 2 but dropped quickly as the run number increased. 14 references.« less

Ultrasonically-enhanced preparation, characterization of CaFe-layered double hydroxides with various interlayer halide, azide and oxo anions (CO32-, NO3-, ClO4-).

PubMed

Szabados, Márton; Varga, Gábor; Kónya, Zoltán; Kukovecz, Ákos; Carlson, Stefan; Sipos, Pál; Pálinkó, István

2018-01-01

An ultrasonically-enhanced mechanochemical method was developed to synthesize CaFe-layered double hydroxides (LDHs) with various interlayer anions (CO 3 2- , NO 3 - , ClO 4 - , N 3 - , F - , Cl - , Br - and I - ). The duration of pre-milling and ultrasonic irradiation and the variation of synthesis temperature in the wet chemical step were investigated to obtain the optimal parameters of preparation. The main method to characterize the products was X-ray diffractometry, but infrared and synchrotron-based X-ray absorption spectroscopies as well as thermogravimetric measurements were also used to learn about fine structural details. The synthesis method afforded successful intercalation of the anions, among others the azide anion, a rarely used counter ion providing a system, which enables safe handling the otherwise highly reactive anion. The X-ray absorption spectroscopic measurements revealed that the quality of the interlayered anions could modulate the spatial arrangement of the calcium ions around the iron(III) ions, but only in the second coordination sphere. Copyright © 2017 Elsevier B.V. All rights reserved.

The effect of pH on the toxicity of zinc oxide nanoparticles to Folsomia candida in amended field soil.

PubMed

Waalewijn-Kool, Pauline L; Ortiz, Maria Diez; Lofts, Stephen; van Gestel, Cornelis A M

2013-10-01

The effect of soil pH on the toxicity of 30 nm ZnO to Folsomia candida was assessed in Dorset field soils with pHCaCl2 adjusted to 4.31, 5.71, and 6.39. To unravel the contribution of particle size and dissolved Zn, 200 nm ZnO and ZnCl2 were tested. Zinc sorption increased with increasing pH, and Freundlich kf values ranged from 98.9 (L/kg)(1/n) to 333 (L/kg)(1/n) for 30 nm ZnO and from 64.3 (L/kg)(1/n) to 187 (L/kg)(1/n) for ZnCl2. No effect of particle size was found on sorption, and little difference was found in toxicity between 30 nm and 200 nm ZnO. The effect on reproduction decreased with increasing pH for all Zn forms, with 28-d median effective concentrations (EC50s) of 553 mg Zn/kg, 1481 mg Zn/kg, and 3233 mg Zn/kg for 30 nm ZnO and 331 mg Zn/kg, 732 mg Zn/kg, and 1174 mg Zn/kg for ZnCl2 at pH 4.31, 5.71, and 6.39, respectively. The EC50s based on porewater Zn concentrations increased with increasing pH for 30 nm ZnO from 4.77 mg Zn/L to 18.5 mg Zn/L, while for ZnCl2 no consistent pH-related trend in EC50s was found (21.0-63.3 mg Zn/L). Porewater calcium levels were 10 times higher in ZnCl2 -spiked soils than in ZnO-spiked soils. The authors' results suggest that the decreased toxicity of ZnCl2 compared with 30 nm ZnO based on porewater concentrations was because of a protective effect of calcium and not a particle effect. © 2013 SETAC.

The Perceptual Characteristics of Sodium Chloride to Sodium-Depleted Rats

PubMed Central

2017-01-01

Three experiments assessed potential changes in the rat’s perception of sodium chloride (NaCl) during a state of sodium appetite. In Experiment 1, sodium-sufficient rats licking a range of NaCl concentrations (0.028–0.89M) in 15s trials showed an inverted U-shaped concentration response function peaking at 0.281M. Depleted rats (furosemide) showed an identical function, merely elevated, suggesting altered qualitative or hedonic perception but no change in perceived intensity. In Experiment 2, sodium-depleted rats were tested with NaCl, sodium gluconate, and potassium chloride (KCl; 0.028–0.89M) similar to Experiment 1. KCl was licked at the same rate as water except for a slight elevation at 0.158; sodium gluconate and NaCl were treated similarly, but rats showed more licking for hypertonic sodium gluconate than hypertonic NaCl. Sodium-depleted rats were also tested with NaCl mixed in amiloride (10–300 μM). Amiloride reduced licking but did not alter the shape of the concentration–response function. Collectively, these results suggest that transduction of sodium by epithelial sodium channels (which are blocked by amiloride and are more dominant in sodium gluconate than NaCl transduction) is crucial for the perception of sodium during physiological sodium depletion. In Experiment 3, sodium-deplete rats were tested with NaCl as in Experiment 1 but after taste aversion conditioning to 0.3M NaCl or sucrose. Rats conditioned to avoid NaCl but not sucrose failed to express a sodium appetite, strongly suggesting that NaCl does not undergo a change in taste quality during sodium appetite—rats show no confusion between sucrose and NaCl in this paradigm. PMID:27660150

The Perceptual Characteristics of Sodium Chloride to Sodium-Depleted Rats.

PubMed

St John, Steven J

2017-02-01

Three experiments assessed potential changes in the rat's perception of sodium chloride (NaCl) during a state of sodium appetite. In Experiment 1, sodium-sufficient rats licking a range of NaCl concentrations (0.028-0.89M) in 15s trials showed an inverted U-shaped concentration response function peaking at 0.281M. Depleted rats (furosemide) showed an identical function, merely elevated, suggesting altered qualitative or hedonic perception but no change in perceived intensity. In Experiment 2, sodium-depleted rats were tested with NaCl, sodium gluconate, and potassium chloride (KCl; 0.028-0.89M) similar to Experiment 1. KCl was licked at the same rate as water except for a slight elevation at 0.158; sodium gluconate and NaCl were treated similarly, but rats showed more licking for hypertonic sodium gluconate than hypertonic NaCl. Sodium-depleted rats were also tested with NaCl mixed in amiloride (10-300 μM). Amiloride reduced licking but did not alter the shape of the concentration-response function. Collectively, these results suggest that transduction of sodium by epithelial sodium channels (which are blocked by amiloride and are more dominant in sodium gluconate than NaCl transduction) is crucial for the perception of sodium during physiological sodium depletion. In Experiment 3, sodium-deplete rats were tested with NaCl as in Experiment 1 but after taste aversion conditioning to 0.3M NaCl or sucrose. Rats conditioned to avoid NaCl but not sucrose failed to express a sodium appetite, strongly suggesting that NaCl does not undergo a change in taste quality during sodium appetite-rats show no confusion between sucrose and NaCl in this paradigm. Published by Oxford University Press on behalf of US Government 2016.

Kinetic modeling and energy efficiency of UV/H₂O₂ treatment of iodinated trihalomethanes.

PubMed

Xiao, Yongjun; Zhang, Lifeng; Yue, Junqi; Webster, Richard D; Lim, Teik-Thye

2015-05-15

Photodegradation of I-THMs including CHCl2I and CHI3 by the UV/H2O2 system was investigated in this study. CHCl2I and CHI3 react rapidly with hydroxyl radical (OH) produced by the UV/H2O2 system, with second-order rate constants of 8.0 × 10(9) and 8.9 × 10(9) M(-1) s(-1), respectively. A fraction of CHCl2I could be completely mineralized within 15 min and the remaining fraction was mainly converted to formic acid (HCO2H). Cl(-) and I(-) were identified as the predominant end-products. No ClO3(-) was observed during the photodegradation process, while IO3(-) was detected but at less than 2% of the total liberated iodine species at the end of the reaction. The effects of pH, H2O2 dose, and matrix species such as humic acid (HA), HCO3(-), SO4(2-), Cl(-), NO3(-) on the photodegradation kinetics were evaluated. The steady-state kinetic model has been proven to successfully predict the destruction of CHCl2I and CHI3 by UV/H2O2 in different water matrices. On this basis, the kinetic model combined with electrical energy per order (EE/O) concept was applied to evaluate the efficiency of the photodegradation process and to optimize the H2O2 dose for different scenarios. The optimal H2O2 doses in deionized (DI) water, model natural water, and surface water are estimated at 5, 12, and 16 mg L(-1), respectively, which correspond to the lowest total energy consumption (EE/Ototal) of 0.2, 0.31, and 0.45 kWhm(-3)order(-1). Copyright © 2015 Elsevier Ltd. All rights reserved.

[Effect of calcium and magnesium ions on the interaction of corticosterone with the cytosol receptor(s) in the rat brain].

PubMed

Ueda, M

1981-01-01

The effects of calcium and magnesium ions on the corticosterone binding to rat brain cytosol receptor protein(s) were investigated. The increasing amounts of CaCl2 or MgCl2 up to 5.0 mM were added, the specific [3H] corticosterone binding increased 1.3-fold and 1.5 respectively. The addition of MnCl2 and KCl did not affect this binding. The binding of corticosterone with rat brain cytosol receptor(s) were decreased by increasing amounts of EDTA and complete inhibition was observed at concentration equal to and greater than 2.5 mM. Inhibition of this binding by EDTA was less than by EGTA. Either theophylline or dibutyryl cyclic AMP had no effect on this binding.

Facile synthesis of hierarchical porous γ-Al2O3 hollow microspheres for water treatment.

PubMed

Li, Mingyang; Si, Zhichun; Wu, Xiaodong; Weng, Duan; Kang, Feiyu

2014-03-01

Hierarchical porous γ-Al2O3 hollow microspheres were synthesized by a modified spray drying method. Ageing the precipitated precursor and spray-drying assisted by NH4Cl salts are considered as two key steps for the synthesis of γ-Al2O3 hollow microspheres. The mechanism of the formation of hierarchical porous γ-Al2O3 hollow microsphere was proposed involving phase transformation from aluminum hydroxide to laminar boehmite during ageing and a following self-assembling process with NH4Cl as the template during spray drying. The meso-/macro-pores in γ-Al2O3 mainly arise from the stacking of the laminar boehmites which are obtained by ageing the precipitated precursors at 90°C. NH4Cl, which was the byproduct from the reaction between AlCl3·6H2O and NH3·H2O, was demonstrated to be an excellent template to act as the core and the barrier for separation of laminar boehmites. No extra NH4Cl was added. The as-synthesized hierarchical porous γ-Al2O3 hollow microsphere presented remarkably higher adsorption capacity, which is thirty times higher adsorption rate for Congo Red than the solid microsphere containing only small mesopores. Copyright © 2013 Elsevier Inc. All rights reserved.

Assessing the impact of dairy waste lagoons on groundwater quality using a spatial analysis of vadose zone and groundwater information in a coastal phreatic aquifer.

PubMed

Baram, S; Kurtzman, D; Ronen, Z; Peeters, A; Dahan, O

2014-01-01

Dairy waste lagoons are considered to be point sources of groundwater contamination by chloride (Cl(-)), different nitrogen-species and pathogens/microorganisms. The objective of this work is to introduce a methodology to assess the past and future impacts of such lagoons on regional groundwater quality. The method is based on a spatial statistical analysis of Cl(-) and total nitrogen (TN) concentration distributions in the saturated and the vadose (unsaturated) zones. The method provides quantitative data on the relation between the locations of dairy lagoons and the spatial variability in Cl(-) and TN concentrations in groundwater. The method was applied to the Beer-Tuvia region, Israel, where intensive dairy farming has been practiced for over 50 years above the local phreatic aquifer. Mass balance calculations accounted for the various groundwater recharge and abstraction sources and sinks in the entire region. The mass balances showed that despite the small surface area covered by the dairy lagoons in this region (0.8%), leachates from lagoons have contributed 6.0% and 12.6% of the total mass of Cl(-) and TN (mainly as NO3(-)-N) added to the aquifer. The chemical composition of the aquifer and vadose zone water suggested that irrigated agricultural activity in the region is the main contributor of Cl(-) and TN to the groundwater. A low spatial correlation between the Cl(-) and NO3(-)-N concentrations in the groundwater and the on-land location of the dairy farms strengthened this assumption, despite the dairy waste lagoon being a point source for groundwater contamination by Cl(-) and NO3(-)-N. Mass balance calculations, for the vadose zone of the entire region, indicated that drying of the lagoons would decrease the regional groundwater salinization process (11% of the total Cl(-) load is stored under lagoons). A more considerable reduction in the groundwater contamination by NO3(-)-N is expected (25% of the NO3(-)-N load is stored under lagoons). Results demonstrate that analyzing vadose zone and groundwater data by spatial statistical analysis methods can significantly contribute to the understanding of the relations between groundwater contaminating sources, and to assessing appropriate remediation steps. Copyright © 2013 Elsevier Ltd. All rights reserved.

Two Voriconazole salts: Syntheses, crystal structures, solubility and bioactivities

NASA Astrophysics Data System (ADS)

Tang, Gui-Mei; Wang, Yong-Tao

2018-01-01

Two Voriconazole salts, namely, (H2FZ)2+·2(Cl-) (1) and (HFZ)+·NO3- (2) (FZ = (2R,3S)-2-(2,4-difluorophenyl)-3-(5-fluoro-4-pyrimidiny)-1-(1H-1,2,4-triazol-1-yl)-2-butanol) have been obtained through the reaction of Voriconazole, hydrochloric acid and nitrate acid, respectively. They were structurally characterized by FT-IR, elemental analyses (EA), single crystal X-ray diffraction, and thermogravimetric analysis (TGA). A variety of hydrogen bonds (Osbnd H⋯N, Nsbnd H⋯Cl/O, Csbnd H⋯N/OF/Cl) were observed in the compounds 1 and 2, through which a 3D supramolecular architecture is generated. Both two salts 1 and 2 show the promising bioactivities against Aspergillus species (Aspergillus niger, Aspergillus terreus, Aspergillus fumigatus and Aspergillus flavus) and Candida ones (Candida albicans, Candida krusei, Candida glabrata and Cryptococcus neoformans), which is obviously more excellent than that of FZ. Additionally, the solubility of two salts is considerably higher than that of the drug Voriconazole.

Chemical characteristics of size-resolved atmospheric aerosols in Iasi, north-eastern Romania: nitrogen-containing inorganic compounds control aerosol chemistry in the area

NASA Astrophysics Data System (ADS)

Giorgiana Galon-Negru, Alina; Iulian Olariu, Romeo; Arsene, Cecilia

2018-04-01

This study assesses the effects of particle size and season on the content of the major inorganic and organic aerosol ionic components in the Iasi urban area, north-eastern Romania. Continuous measurements were carried out over 2016 using a cascade Dekati low-pressure impactor (DLPI) performing aerosol size classification in 13 specific fractions over the 0.0276-9.94 µm size range. Fine-particulate Cl-, NO3-, NH4+, and K+ exhibited clear minima during the warm season and clear maxima over the cold season, mainly due to trends in emission sources, changes in the mixing layer depth and specific meteorological conditions. Fine-particulate SO42- did not show much variation with respect to seasons. Particulate NH4+ and NO3- ions were identified as critical parameters controlling aerosol chemistry in the area, and their measured concentrations in fine-mode (PM2.5) aerosols were found to be in reasonable good agreement with modelled values for winter but not for summer. The likely reason is that NH4NO3 aerosols are lost due to volatility over the warm season. We found that NH4+ in PM2.5 is primarily associated with SO42- and NO3- but not with Cl-. Actually, indirect ISORROPIA-II estimations showed that the atmosphere in the Iasi area might be ammonia rich during both the cold and warm seasons, enabling enough NH3 to be present to neutralize H2SO4, HNO3, and HCl acidic components and to generate fine-particulate ammonium salts, in the form of (NH4)2SO4, NH4NO3, and NH4Cl. ISORROPIA-II runs allowed us to estimate that over the warm season ˜ 35 % of the total analysed samples had very strongly acidic pH (0-3), a fraction that rose to ˜ 43 % over the cold season. Moreover, while in the cold season the acidity is mainly accounted for by inorganic acids, in the warm ones there is an important contribution by other compounds, possibly organic. Indeed, changes in aerosol acidity would most likely impact the gas-particle partitioning of semi-volatile organic acids. Overall, we estimate that within the aerosol mass concentration the ionic mass brings a contribution as high as 40.6 %, with the rest still being unaccounted for.

Ruthenium-Nitrosyl Complexes with Glycine, l-Alanine, l-Valine, l-Proline, d-Proline, l-Serine, l-Threonine, and l-Tyrosine: Synthesis, X-ray Diffraction Structures, Spectroscopic and Electrochemical Properties, and Antiproliferative Activity

PubMed Central

2014-01-01

The reactions of [Ru(NO)Cl5]2– with glycine (Gly), l-alanine (l-Ala), l-valine (l-Val), l-proline (l-Pro), d-proline (d-Pro), l-serine (l-Ser), l-threonine (l-Thr), and l-tyrosine (l-Tyr) in n-butanol or n-propanol afforded eight new complexes (1–8) of the general formula [RuCl3(AA–H)(NO)]−, where AA = Gly, l-Ala, l-Val, l-Pro, d-Pro, l-Ser, l-Thr, and l-Tyr, respectively. The compounds were characterized by elemental analysis, electrospray ionization mass spectrometry (ESI-MS), 1H NMR, UV–visible and ATR IR spectroscopy, cyclic voltammetry, and X-ray crystallography. X-ray crystallography studies have revealed that in all cases the same isomer type (from three theoretically possible) was isolated, namely mer(Cl),trans(NO,O)-[RuCl3(AA–H)(NO)], as was also recently reported for osmium analogues with Gly, l-Pro, and d-Pro (see Z. Anorg. Allg. Chem.2013, 639, 1590–1597). Compounds 1, 4, 5, and 8 were investigated by ESI-MS with regard to their stability in aqueous solution and reactivity toward sodium ascorbate. In addition, cell culture experiments in three human cancer cell lines, namely, A549 (nonsmall cell lung carcinoma), CH1 (ovarian carcinoma), and SW480 (colon carcinoma), were performed, and the results are discussed in conjunction with the lipophilicity of compounds. PMID:24555845

Synthesis of Mg-Fe-Cl hydrotalcite-like nanoplatelets as an oral phosphate binder: evaluations of phosphorus intercalation activity and cellular cytotoxicity

NASA Astrophysics Data System (ADS)

Lung, Yung-Feng; Sun, Ying-Sui; Lin, Chun-Kai; Uan, Jun-Yen; Huang, Her-Hsiung

2016-09-01

The patients with end-stage of renal disease (ESRD) need to take oral phosphate binder. Traditional phosphate binders may leave the disadvantage of aluminum intoxication or cardiac calcification. Herein, Mg-Fe-Cl hydrotalcite-like nanoplatelet (HTln) is for the first time characterized as potential oral phosphate binder, with respect to its phosphorus uptake capacity in cow milk and cellular cytotoxicity. A novel method was developed for synthesizing the Mg-Fe-Cl HTln powder in different Mg2+: Fe3+ ratios where the optimization was 2.8:1. Addition of 0.5 g Mg-Fe-Cl HTln in cow milk could reduce its phosphorus content by 40% in 30 min and by 65% in 90 min. In low pH environment, the Mg-Fe-Cl HTln could exhibit relatively high performance for uptaking phosphorus. During a 90 min reaction of the HTln in milk, no phosphorus restoration occurred. In-vitro cytotoxicity assay of Mg-Fe-Cl HTln revealed no potential cellular cytotoxicity. The cells that were cultured in the HTln extract-containing media were even more viable than cells that were cultured in extract-free media (blank control). The Mg-Fe-Cl HTln extract led to hundred ppm of Mg ion and some ppm of Fe ion in the media, should be a positive effect on the good cell viability.

INORGANIC PM2.5 AT A U.S. AGRICULTURAL SITE

EPA Science Inventory

In this study, we present approximately two years (January 1999–December 2000) of atmospheric NH₃, NH₄⁺, HCl, Cl^-, HNO₃, NO₃^-, SO₂, and SO₄⁼ concentrations measured by t...

Temporal variations of groundwater quality in the Western Jianghan Plain, China.

PubMed

Niu, Beibei; Wang, Huanhuan; Loáiciga, Hugo A; Hong, Song; Shao, Wei

2017-02-01

The Western Jianghan Plain (WJHP) lies in the middle reaches of the Yangtze River. It has been impacted by anthropogenic activities during the past decades. The long-term variations of the WJHP's regional aquifer's hydrochemistry and groundwater quality have not been previously assessed. Sixteen physiochemical parameters at 29 monitoring wells within the Western Jianghan Plain were monitored during 1992-2010 and analyzed with multiple approaches. The confined groundwater is predominantly of the HCO 3 -Ca-Mg type with Cl - , SO 4 2- , NH 4 -N, and NO 3 -N showing remarkable spatial variations. Correlation analysis was used to identify the origins and contamination sources of groundwater. The seasonal Mann-Kendall test revealed that pH, NO 3 -N, and Cl - concentrations at 27, 26 and 15 wells, respectively, exhibited significant increasing trends during 1992-2010. The increase of pH may be attributed to CO 2 degassing caused by extensive groundwater extraction. Regional average NO 3 -N concentrations of groundwater increased coincidently with the increased use of fertilizer, which suggests that nitrate pollution is caused by agricultural activities. Abnormally high values of Cl - and SO 4 2- at some wells were induced by industrial chemicals. In addition, the similarity of the temporal variations of the regional average of pH, NH 4 -N, and NO 3 -N concentrations in groundwater with those in the Yangtze River at the outlet of the Three Gorges Reservoir (TGR) suggests that the variations of these parameters in the WJHP is partly due to water storage by the TGR. This study presents an analysis of temporal variations of groundwater quality in the WJHP that reveals a relation between the creation of the TGR and downstream groundwater quality. This paper's findings provide clues for measures that could be taken to protect the groundwater quality of the WJHP's aquifer. Copyright © 2016. Published by Elsevier B.V.

Impact of leather industries on fluoride dynamics in groundwater around a tannery cluster in South India.

PubMed

Sajil Kumar, P J

2013-03-01

The aim of this study was to investigate the controls of leather industries on fluoride contamination in and around a tannery cluster in Vaniyambadi. Hydrochemical analysis, mineral saturation indices and statistical methods were used to evaluate the intervening factors that controls the contamination processes. Fluoride in groundwater is exceeded the WHO guideline value (1.5 mg/L), in 62 % of the samples, mostly with Na-HCO3 and Na-Cl type of water. Results of the principal component analysis grouped Na, F, HCO3 and NO3 under component 1. This result was in agreement with the cross plot indicating high positive correlation between F and Na (r (2)  = 0.87), HCO3 (r (2)  = 0.84) and NO3 (r (2)  = 0.55). Fluorite (CaF2) and Halite (NaCl) was undersaturated, while calcite (CaCO3) was oversaturated for all the samples. This suggest more dissolution of F-rich minerals under the active supports of Na. Bivariate plots of Na versus Cl and Na + K versus HCO3 showed a combined origin of Na from tannery effluent as well as silicate weathering. Two major clusters, based on the Na, HCO3 and F concentration showed that groundwater is affected by tanneries and silicate weathering. Fluoride concentration in 38 % of samples (n = 5) have significantly affected by the high Na concentration from tanneries.

Using Kalman Filter Chemical Data Assimilation to Study Ozone Catalytic Loss Cycles in January 1992

NASA Technical Reports Server (NTRS)

Lary, David J.

2002-01-01

This paper presents for the first time a global study of the ozone catalytic destruction cycles operating in the stratosphere using a stratospheric analyses for January 1992. The chemical analyses were produced using a Kalman filter data assimilation system. Because a major component of the variability of trace gases is due to the atmospheric motions the analyses have been cast in a flow-tracking coordinate system that moves with the large scale flow pattern. Particular attention is paid to the kinetic aspects of these cycles such as the rate limiting step and chain length. Although it is an important kinetic parameter, the chain length of the various cycles is seldom considered when the various catalytic cycles are discussed. This survey highlights that in the low stratosphere the cycles involving HO2 and halogens (notably bromine) are particularly important. In approximate order of effectiveness the most important ozone loss cycles in the polar lower stratosphere are the BrO/ClO, HO2/BrO, and OH/HO2 cycles. The ClO/ClO cycle clearly delineates the regions of chlorine activation. The chain length of the HO2/ClO, OH/HO2, Br/BrO, and ClO/NO2, clearly delineate the vortex edge region. The chain length of the BrO/NO2 and Cl/NO2 cycles highlight the regions of chemical processing outside the vortex where streamers of chemically processed air are stripped-off and transported away from the vortex. This is also true in the very low stratosphere for the Cl/ClO and BrO/ClO cycles.

Geochemical evolution of groundwater in the Western Delta region of River Godavari, Andhra Pradesh, India

NASA Astrophysics Data System (ADS)

Nageswara Rao, P. V.; Appa Rao, S.; Subba Rao, N.

2017-05-01

The present study on geochemical evolution of groundwater is taken up to assess the controlling processes of water chemistry in the Western Delta region of the River Godavari (Andhra Pradesh), which is one of the major rice-producing centers in India. The study region is underlain by coarse sand with black clay (buried channels), black silty clay of recent origin (floodplain) and gray/white fine sand of modern beach sediment of marine source (coastal zone), including brown silty clay with fine sand (paleo-beach ridges). Groundwater is mostly brackish and very hard. It is characterized by Na+ > Mg2+ > Ca2+:HCO3 - > Cl- > SO4 2- > NO3 -, Na+ > Mg2+ > Ca2+:Cl- > HCO3 - > SO4 2-, and Mg2+ > Na+ > Ca2+ > or < K+:HCO3 - > Cl- > or > SO4 2- facies. The ionic relations (Ca2+ + Mg2+:HCO3 -, Ca2+ + Mg2+:SO4 2- + HCO3 -, Na+ + K+:TC, Na+ + K+:Cl- + SO4 2-, HCO3 -:TC, HCO3 -:Ca2+ + Mg2+, Na+:Cl- and Na+:Ca2+) indicate that the rock weathering, mineral dissolution, evaporation and ion exchange are the processes to control the aquifer chemistry. Anthropogenic and marine sources are also the supplementary factors for brackish water quality. These observations are further supported by Gibbs mechanisms that control the water chemistry. Thus, the study suggests that the initial quality of groundwater of geogenic origin has been subsequently modified by the influences of anthropogenic and marine sources.

Spatiotemporal evaluation of the groundwater quality in Gharbiya Governorate, Egypt.

PubMed

Masoud, Alaa A; El Bouraie, Mohamed M; El-Nashar, Wafaa; Mashaly, Hamdy

2017-03-01

Groundwater quality indicators were monitored over 6 years (2007-2012) from 55 drinking water supply wells in Gharbiya Governorate (Egypt). The prime objective was to characterize, for the first time, the governorate-wide significant and sustained trends in the concentrations of the groundwater pollutants. Quality indicators included turbidity, pH, total dissolved solid (TDS), electric conductivity (EC), Cl - , SO 4 2- , Na + , total alkalinity, hardness (total, Mg, and Ca), Fe 2+ , Mn 2+ , Cu 2+ , Zn 2+ , F - , NH 4 + , NO 2 - , NO 3 - , PO 4 3- , dissolved oxygen (DO), and SiO 2 contents. Detection and estimation of trends and magnitude were carried out applying the non-parametric Mann-Kendall and Thiel-Sen trend statistical tests, respectively. Factor analysis was applied to identify significant sources of quality variation and their loads. Violation of groundwater quality standards clarified emergence of Mn 2+ (46%), Fe 2+ (35%), and NH 4 + (33%). Out of the 55 wells, notable upward trends (deterioration) were significant (>95% level) for TDS (89%), NO 3 - (85), PO 4 3- (75%), NH 4 + (65%), total alkalinity (62%), Fe 2+ (58%), NO 2 - (47%), Mg hardness (36%), turbidity (25%), and Mn 2+ (24%). Ranges of attenuation rates (mg/l/year) varied for TDS (24.3, -0.7), Mg hardness (3.8, -0.85), total alkalinity (1.4, -1.2), NO 3 - (0.52, -0.066), PO 4 3- (0.069, -0.064), NH 4 + (0.038, -0.019), Mn 2+ (0.015, -0.044), Fe 2+ (0.006, -0.014), and NO 2 - (0.006, -0.00003). Highest rates marked Tanta (total alkalinity and Fe 2+ ), Al-Mehala Al-Kubra (TDS, Mg hardness, and NO 3 - ), Kafr Al-Zayat (NH 4 + ), Zifta (Mn 2+ ), Bassyun (NO 2 - ), and Qutur (PO 4 3- ). Precision of the trend estimate varied in goodness of fit, for TDS (86%), Mg hardness (76%), total alkalinity (73%), PO 4 3- (67.4%), NH 4 + (66.8%), Mn 2+ (55%), and Fe 2+ (49.6%), arranged in decreasing order. Two main varimax-rotated factors counted for more than 55% of the quality variance and, in particular, significant loads of salinity (TDS, EC, Cl - , Na + , and SO 4 2- ), followed by the alkalinity, hardness, redox potentials (Mn 2+ and Fe 2+ ), and NH 4 + , in decreasing order were identified. The spatial-temporal variation in pollutants originated from organic matter degradation, either naturally from the aquifer peaty sediments or anthropogenic due to improper well head protection in the urban centers or from the agricultural drains in low relief areas. Considering the latest contents of indicators and their rate of increase, the time that the permissible limits would be reached can be accurately estimated and alleviative actions could be effectively set.

Ligand Noninnocence in Iron Corroles: Insights from Optical and X-ray Absorption Spectroscopies and Electrochemical Redox Potentials

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

Ganguly, Sumit; Giles, Logan J.; Thomas, Kolle E.

Two new series of iron meso-tris(para-X-phenyl)corrole (TpXPC) complexes, Fe[TpXPC]Ph and Fe[TpXPC]Tol, in which X=CF 3, H, Me, and OMe, and Tol=p-methylphenyl (p-tolyl), have been synthesized, allowing a multitechnique electronic–structural comparison with the corresponding FeCl, FeNO, and Fe 2(μ-O) TpXPC derivatives. Optical spectroscopy revealed that the Soret maxima of the FePh and FeTol series are insensitive to the phenyl para substituent, consistent with the presumed innocence of the corrole ligand in these compounds. Accordingly, we may be increasingly confident in the ability of the substituent effect criterion to serve as a probe of corrole noninnocence. Furthermore, four complexes—Fe[TPC]Cl, Fe[TPC](NO), {Fe[TPC]} 2O,more » and Fe[TPC]Ph—were selected for a detailed XANES investigation of the question of ligand noninnocence. The intensity-weighted average energy (IWAE) positions were found to exhibit rather modest variations (0.8 eV over the series of corroles). The integrated Fe-K pre-edge intensities, on the other hand, vary considerably, with a 2.5 fold increase for Fe[TPC]Ph relative to Fe[TPC]Cl and Fe[TPC](NO). Given the approximately C 4v local symmetry of the Fe in all the complexes, the large increase in intensity for Fe[TPC]Ph may be attributed to a higher number of 3d holes, consistent with an expected Fe IV-like description, in contrast to Fe[TPC]Cl and Fe[TPC](NO), in which the Fe is thought to be Fe III-like. In conclusion, these results afford strong validation of XANES as a probe of ligand noninnocence in metallocorroles. Electrochemical redox potentials, on the other hand, were found not to afford a simple probe of ligand noninnocence in Fe corroles.« less

Ligand Noninnocence in Iron Corroles: Insights from Optical and X-ray Absorption Spectroscopies and Electrochemical Redox Potentials

DOE PAGES

Ganguly, Sumit; Giles, Logan J.; Thomas, Kolle E.; ...

2017-10-06

Two new series of iron meso-tris(para-X-phenyl)corrole (TpXPC) complexes, Fe[TpXPC]Ph and Fe[TpXPC]Tol, in which X=CF 3, H, Me, and OMe, and Tol=p-methylphenyl (p-tolyl), have been synthesized, allowing a multitechnique electronic–structural comparison with the corresponding FeCl, FeNO, and Fe 2(μ-O) TpXPC derivatives. Optical spectroscopy revealed that the Soret maxima of the FePh and FeTol series are insensitive to the phenyl para substituent, consistent with the presumed innocence of the corrole ligand in these compounds. Accordingly, we may be increasingly confident in the ability of the substituent effect criterion to serve as a probe of corrole noninnocence. Furthermore, four complexes—Fe[TPC]Cl, Fe[TPC](NO), {Fe[TPC]} 2O,more » and Fe[TPC]Ph—were selected for a detailed XANES investigation of the question of ligand noninnocence. The intensity-weighted average energy (IWAE) positions were found to exhibit rather modest variations (0.8 eV over the series of corroles). The integrated Fe-K pre-edge intensities, on the other hand, vary considerably, with a 2.5 fold increase for Fe[TPC]Ph relative to Fe[TPC]Cl and Fe[TPC](NO). Given the approximately C 4v local symmetry of the Fe in all the complexes, the large increase in intensity for Fe[TPC]Ph may be attributed to a higher number of 3d holes, consistent with an expected Fe IV-like description, in contrast to Fe[TPC]Cl and Fe[TPC](NO), in which the Fe is thought to be Fe III-like. In conclusion, these results afford strong validation of XANES as a probe of ligand noninnocence in metallocorroles. Electrochemical redox potentials, on the other hand, were found not to afford a simple probe of ligand noninnocence in Fe corroles.« less

Lubiprostone Activates CFTR, but not ClC-2, via the Prostaglandin Receptor (EP4)

PubMed Central

Norimatsu, Yohei; Moran, Aurelia R.; MacDonald, Kelvin D.

2012-01-01

The goal of this study was to determine the mechanism of lubiprostone activation of epithelial chloride transport. Lubiprostone is a bicyclic fatty acid approved for the treatment of constipation [1]. There is uncertainty, however, as to how lubiprostone increases epithelial chloride transport. Direct stimulation of ClC-2 and CFTR chloride channels as well as stimulation of these channels via the EP4 receptor has been described [2; 3; 4; 5]. To better define this mechanism, two-electrode voltage clamp was used to assay Xenopus oocytes expressing ClC-2, with or without co-expression of the EP4 receptor or β adrenergic receptor (βAR), for changes in conductance elicited by lubiprostone. Oocytes co-expressing CFTR and either βAR or the EP4 receptor were also studied. In oocytes co-expressing ClC-2 and βAR conductance was stimulated by hyperpolarization and acidic pH (pH=6), but there was no response to the β adrenergic agonist, isoproterenol. Oocytes expressing ClC-2 only or co-expressing ClC-2 and EP4 did not respond to the presence of 0.1, 1, or 10 µM lubiprostone in the superperfusate. Oocytes co-expressing CFTR and βAR did not respond to hyperpolarization, acidic pH, or 1µM lubiprostone. However, conductance was elevated by isoproterenol and inhibited by CFTRinh172. Co-expression of CFTR and EP4 resulted in lubiprostone-stimulated conductance, which was also sensitive to CFTRinh172. The EC50 for lubiprostone mediated CFTR activation was ~ 10 nM. These results demonstrate no direct action of lubiprostone on either ClC-2 or CFTR channels expressed in oocytes. However, the results confirm that CFTR can be activated by lubiprostone via the EP4 receptor in oocytes. PMID:22960173

Interaction between dietary content of protein and sodium chloride on milk urea concentration, urinary urea excretion, renal recycling of urea, and urea transfer to the gastrointestinal tract in dairy cows.

PubMed

Spek, J W; Bannink, A; Gort, G; Hendriks, W H; Dijkstra, J

2013-09-01

Dietary protein and salt affect the concentration of milk urea nitrogen (MUN; mg of N/dL) and the relationship between MUN and excretion of urea nitrogen in urine (UUN; g of N/d) of dairy cattle. The aim of the present study was to examine the effects of dietary protein and sodium chloride (NaCl) intake separately, and their interaction, on MUN and UUN, on the relationship between UUN and MUN, on renal recycling of urea, and on urea transfer to the gastrointestinal tract. Twelve second-parity cows (body weight of 645±37 kg, 146±29 d in milk, and a milk production of 34.0±3.28 kg/d), of which 8 were previously fitted with a rumen cannula, were fitted with catheters in the urine bladder and jugular vein. The experiment had a split-plot arrangement with dietary crude protein (CP) content as the main plot factor [116 and 154 g of CP/kg of dry matter (DM)] and dietary NaCl content as the subplot factor (3.1 and 13.5 g of Na/kg of DM). Cows were fed at 95% of the average ad libitum feed intake of cows receiving the low protein diets. Average MUN and UUN were, respectively, 3.90 mg of N/dL and 45 g of N/d higher for the high protein diets compared with the low protein diets. Compared with the low NaCl diets, MUN was, on average, 1.74 mg of N/dL lower for the high NaCl diets, whereas UUN was unaffected. We found no interaction between dietary content of protein and NaCl on performance characteristics or on MUN, UUN, urine production, and renal clearance characteristics. The creatinine clearance rate was not affected by dietary content of protein and NaCl. Urea transfer to the gastrointestinal tract, expressed as a fraction of plasma urea entry rate, was negatively related to dietary protein, whereas it was not affected by dietary NaCl content. We found no interaction between dietary protein and NaCl content on plasma urea entry rate and gastrointestinal urea entry rate or their ratio. The relationship between MUN and UUN was significantly affected by the class variable dietary NaCl content: UUN=-17.7±7.24 + 10.09±1.016 × MUN + 2.26±0.729 × MUN (for high NaCl); R(2)=0.85. Removal of the MUN × NaCl interaction term lowered the coefficient of determination from 0.85 to 0.77. In conclusion, dietary protein content is positively related to MUN and UUN, whereas dietary NaCl content is negatively correlated to MUN but NaCl content is not related to UUN. We found no interaction between dietary protein and NaCl content on performance, MUN, UUN, or renal urea recycling, nor on plasma urea entry rate and urea transfer to the gastrointestinal tract. For a proper interpretation of the relationship between MUN and UUN, the effect of dietary NaCl should be taken into account, but we found no evidence that the effect of dietary NaCl on MUN is dependent on dietary protein content. Copyright © 2013 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Evaluation of Copper and Hydrogen Peroxide Treatments on the Biology, Biomechanics, and Cytotoxicity of Decellularized Dermal Allografts.

PubMed

Leow-Dyke, Sophie F; Rooney, Paul; Kearney, John N

2016-03-01

Decellularized tissue allografts are paving the way as an alternative to cellular tissue transplantation. Effective sterilization or decontamination of tissue allografts is paramount for the safety of the allograft; however, some of the current sterilization procedures have a detrimental effect on the tissue scaffold. The bactericidal and virucidal activity of copper (II) ions and hydrogen peroxide (H2O2) have been widely reported, however, their effect on the biology, biochemistry, and biocompatibility of decellularized tissue have yet to be elucidated. In this study, decellularized human dermis (dCELL human dermis) was treated with copper (II) chloride (CuCl2) and H2O2; both singly and in combination, and parameters, including concentration, pH, and synergy between CuCl2 and H2O2, were evaluated to identify conditions where any detrimental effects on the tissue scaffold were observed. Skin from 13 human donors was retrieved with appropriate consent and processed into dCELL human dermis. The dCELL human dermis was then treated for 3 h with 0.1 mg/L-1 g/L (w/v) CuCl2 and 0.01-7.5% (v/v) H2O2 and combinations of both of these in the same concentration range. dCELL human dermis treated with solutions of 0.1 mg/L-1 g/L CuCl2 or 0.01-7.5% H2O2 caused no detrimental effects on gross histology, collagen denaturation, collagen orientation, and biomechanical properties of the tissue or cytotoxicity. The highest combined concentration of CuCl2 and H2O2 demonstrated an increase in ultimate tensile strength, loss of collagen type IV immunostaining at the dermal-epidermal junction, and in vitro cytotoxicity. Combinations within the range of up to 10 mg/L CuCl2 with up to 0.5% H2O2 had no effect. The data identify the concentrations of CuCl2 and H2O2 solutions that have no effect on the biological, biomechanical, and biochemical properties of dCELL human dermis, while retaining biocompatibility. These treatments may be suitable for use as sterilization/decontamination agents on human decellularized tissues.

Dissolution of uranophane: An AFM, XPS, SEM and ICP study

NASA Astrophysics Data System (ADS)

Schindler, Michael; Freund, Michael; Hawthorne, Frank C.; Burns, Peter C.; Maurice, Patricia A.

2009-05-01

Dissolution experiments on single crystals of uranophane and uranophane-β, Ca(H 2O) 5[(UO 2)(SiO 3(OH)] 2, from the Shinkolobwe mine of the Democratic Republic of Congo, were done in an aqueous HCl solution of pH 3.5 for 3 h, in HCl solutions of pH 2 for 5, 10 and 30 min, and in Pb 2+-, Ba-, Sr-, Ca- and Mg-HCl solutions of pH 2 for 30 min. The basal surfaces of the treated uranophane crystals were examined using atomic-force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Solutions after dissolution experiments on single crystals and synthetic powders were analysed with inductively coupled plasma-optical emission spectroscopy (ICP-OES) and mass spectroscopy (ICP-MS). The morphology of the observed etch pits (measured by AFM) were compared to the morphology, predicted on the basis of the bond-valence deficiency of polyhedron chains along the edges of the basal surface. Etch pits form in HCl solutions of pH 2. Their decrease in depth with the duration of the dissolution experiment is explained with the stepwave dissolution model, which describes the lowering of the surrounding area of an etch pit with continuous waves of steps emanated from the etch pit into the rest of the crystal surface. Hillocks form in an HCl solution of pH 3.5, and the chemical composition of the surface (as indicated by XPS) shows that these hillocks are the result of the precipitation of a uranyl-hydroxy-hydrate phase. Well-orientated hillocks form on the surface of uranophane in a SrCl 2-HCl solution of pH 2. They are part of an aged silica coating of composition Si 2O 2(OH) 4(H 2O) n. An amorphous layer forms on the surface of uranophane in a MgCl 2-HCl solution of pH 2, which has a composition and structure similar to silicic acid. Small crystallites of uranyl-hydroxy-hydrate phases form on the surface of uranophane after treatment in Pb(NO 3) 2-HCl and BaCl 2-HCl solutions of pH 2. Dissolution experiments on synthetic uranophane powders show that in the early stage of the experiments, the dissolution rate of uranophane increase in the sequence Pb(NO 3) 2-HCl < BaCl 2-HCl < CaCl 2-HCl < HCl < SrCl 2-HCl < MgCl 2-HCl, indicating that the dissolution of uranophane is more enhanced in solutions containing divalent cations of small ionic radii and high Lewis acidity (Mg, MgCl +).

Evolution of chemically processed air parcels in the lower stratosphere

NASA Technical Reports Server (NTRS)

Stolarski, Richard S.; Douglass, Anne R.; Schoeberl, Mark R.

1994-01-01

Aircraft, ground-based, and satellite measurements indicate large concentrations of ClO in the lower stratosphere in and near the polar vortex. The amount of local ozone depletion caused by these large ClO concentrations will depend on the relative rates of ozone loss and ClO recovery. ClO recovery occurs when NO(x), from HNO3 photolysis, reacts with ClO to form ClONO2. We show that air parcels with large amounts of ClO will experience a subsequent ozone depletion that depends on the solar zenith angle. When the solar zenith angle is large in the middle of winter, the recovery of the ClO concentration in the parcel is slow relative to ozone depletion. In the spring, when the solar zenith angle is smaller, the ClO recovery is much faster. After ClO recovery, the chlorine chemistry has not returned to normal. The ClO has been converted to ClONO2. ClO production from further encounters with PSCs will be limited by the heterogeneous reaction of ClONO2 with water. Large ozone depletions, of the type seen in the Antarctic, occur only if there is significant irreversible denitrification in the air parcel.

From a Dy(III) single molecule magnet (SMM) to a ferromagnetic [Mn(II)Dy(III)Mn(II)] trinuclear complex.

PubMed

Bhunia, Asamanjoy; Gamer, Michael T; Ungur, Liviu; Chibotaru, Liviu F; Powell, Annie K; Lan, Yanhua; Roesky, Peter W; Menges, Fabian; Riehn, Christoph; Niedner-Schatteburg, Gereon

2012-09-17

The Schiff base compound 2,2'-{[(2-aminoethyl)imino]bis[2,1-ethanediyl-nitriloethylidyne]}bis-2-hydroxy-benzoic acid (H(4)L) as a proligand was prepared in situ. This proligand has three potential coordination pockets which make it possible to accommodate from one to three metal ions allowing for the possible formation of mono-, di-, and trinuclear complexes. Reaction of in situ prepared H(4)L with Dy(NO(3))(3)·5H(2)O resulted in the formation of a mononuclear complex [Dy(H(3)L)(2)](NO(3))·(EtOH)·8(H(2)O) (1), which shows SMM behavior. In contrast, reaction of in situ prepared H(4)L with Mn(ClO(4))(2)·6H(2)O and Dy(NO(3))(3)·5H(2)O in the presence of a base resulted in a trinuclear mixed 3d-4f complex (NHEt(3))(2)[Dy{Mn(L)}(2)](ClO(4))·2(H(2)O) (2). At low temperatures, compound 2 is a weak ferromagnet. Thus, the SMM behavior of compound 1 can be switched off by incorporating two Mn(II) ions in close proximity either side of the Dy(III). This quenching behavior is ascribed to the presence of the weak ferromagnetic interactions between the Mn(II) and Dy(III) ions, which at T > 2 K act as a fluctuating field causing the reversal of magnetization on the dysprosium ion. Mass spectrometric ion signals related to compounds 1 and 2 were both detected in positive and negative ion modes via electrospray ionization mass spectrometry. Hydrogen/deuterium exchange (HDX) reactions with ND(3) were performed in a FT-ICR Penning-trap mass spectrometer.

Stratospheric ozone depletion

PubMed Central

Rowland, F. Sherwood

2006-01-01

Solar ultraviolet radiation creates an ozone layer in the atmosphere which in turn completely absorbs the most energetic fraction of this radiation. This process both warms the air, creating the stratosphere between 15 and 50 km altitude, and protects the biological activities at the Earth's surface from this damaging radiation. In the last half-century, the chemical mechanisms operating within the ozone layer have been shown to include very efficient catalytic chain reactions involving the chemical species HO, HO2, NO, NO2, Cl and ClO. The NOX and ClOX chains involve the emission at Earth's surface of stable molecules in very low concentration (N2O, CCl2F2, CCl3F, etc.) which wander in the atmosphere for as long as a century before absorbing ultraviolet radiation and decomposing to create NO and Cl in the middle of the stratospheric ozone layer. The growing emissions of synthetic chlorofluorocarbon molecules cause a significant diminution in the ozone content of the stratosphere, with the result that more solar ultraviolet-B radiation (290–320 nm wavelength) reaches the surface. This ozone loss occurs in the temperate zone latitudes in all seasons, and especially drastically since the early 1980s in the south polar springtime—the ‘Antarctic ozone hole’. The chemical reactions causing this ozone depletion are primarily based on atomic Cl and ClO, the product of its reaction with ozone. The further manufacture of chlorofluorocarbons has been banned by the 1992 revisions of the 1987 Montreal Protocol of the United Nations. Atmospheric measurements have confirmed that the Protocol has been very successful in reducing further emissions of these molecules. Recovery of the stratosphere to the ozone conditions of the 1950s will occur slowly over the rest of the twenty-first century because of the long lifetime of the precursor molecules. PMID:16627294

Speciation and Elemental Mapping of Metal Containing Aerosols

NASA Astrophysics Data System (ADS)

Fraund, M. W.; Moffet, R.; Harder, T.; Williams, G.; Chen-Wiegart, Y. C. K.; Laskin, A.; Gilles, M. K.; Schoonen, M. A.; Thieme, J.

2017-12-01

Transition metals play a key roles in biogeochemical processes and health effects of aerosols. The Submicron Resolution X-ray (SRX) beamline at the second National Synchrotron Light Source (NSLS-II) can be used to obtain spatially resolved elemental composition using X-ray fluorescence (XRF) as well as element specific molecular information through X-ray absorption near edge structure (XANES) spectroscopy. Here, XANES spectroscopy was used to identify the oxidation state of iron-rich particles collected from the Cape Hedo Observatory on the island of Okinawa, Japan which is subject to aerosols from both biogenic (Gobi desert) and anthropogenic sources (e.g. Beijing and Shanghai). This data was compared with standards to help classify the minerology and source of these aerosol particles with regards to their potential solubility and bioavailability. In another application of the XRF/XANES measurements from NSLS-II, Pb rich particles from Mexico City were probed for distribution and speciation of Pb. Prior study has indicated that elevated concentrations of Pb occur in an industrialized section of northern Mexico City. It has been established that Pb and Zn are internally mixed in atmospheric aerosol and that Zn primarily exists as ZnCl2 and Zn(NO3)2. Based on these observations, it is hypothesized that Pb also exists as PbCl2 and Pb(NO3)­2. In this study it is shown that X-ray absorption near edge structure (XANES) spectroscopy at the Pb L-edge supports Pb being present as PbCl2 and Pb(NO3)2. Submicron resolution X-ray fluorescence mapping is also used to provide complimentary information on the collocation of other high-Z elements.

MICRURGICAL STUDIES IN CELL PHYSIOLOGY

PubMed Central

Chambers, Robert; Reznikoff, Paul

1926-01-01

By means of micro-dissection and injection Amœba proteus was treated with the chlorides of Na, K, Ca, and Mg alone, in combination, and with variations of pH. I. The Plasmalemma. 1. NaCl weakens and disrupts the surface membrane of the ameba. Tearing the membrane accelerates the disruption which spreads rapidly from the site of the tear. KCl has no disruptive effect on the membrane but renders it adhesive. 2. MgCl2 and CaCl2 have no appreciable effect on the integrity of the surface membrane of the ameba when applied on the outside. No spread of disruption occurs when the membrane is torn in these salts. When these salts are introduced into the ameba they render the pellicle of the involved region rigid. II. The Internal Protoplasm. 3. Injected water either diffuses through the protoplasm or becomes localized in a hyaline blister. Large amounts when rapidly injected produce a "rushing effect". 4. HCl at pH 1.8 solidifies the internal protoplasm and at pH 2.2 causes solidification only after several successive injections. The effect of the subsequent injections may be due to the neutralization of the cell-buffers by the first injection. 5. NaCl and KCl increase the fluidity of the internal protoplasm and induce quiescence. 6. CaCl2 and MgCl2 to a lesser extent solidify the internal protoplasm. With CaCl2 the solidification tends to be localized. With MgCl2 it tends to spread. The injection of CaCl2 accelerates movement in the regions not solidified whereas the injection of MgCl2 induces quiescence. III. Pinching-Off Reaction. 7. A hyaline blister produced by the injection of water may be pinched off. The pinched-off blister is a liquid sphere surrounded by a pellicle. 8. Pinching off always takes place with injections of HCl when the injected region is solidified. 9. The injection of CaCl2 usually results in the pinching off of the portion solidified. The rate of pinching off varies with the concentration of the salt. The injection of MgCl2 does not cause pinching off. IV. Reparability of Torn Surfaces. 10. The repair of a torn surface takes place readily in distilled water. In the different salt solutions, reparability varies specifically with each salt, with the concentration of the salt, and with the extent of the tear. In NaCl and in KCl repair occurs less readily than in water. In MgCl2 repair takes place with great difficulty. In CaCl2 a proper estimate of the process of repair is complicated by the pinching-off phenomenon. However, CaCl2 is the only salt found to increase the mobility of the plasmalemma, and this presumably enhances its reparability. 11. The repair of the surface is probably a function of the internal protoplasm and depends upon an interaction of the protoplasm with the surrounding medium. V. Permeability. 12. NaCl and KCl readily penetrate the ameba from the exterior. CaCl2 and MgCl2 do not. 13. All four salts when injected into an ameba readily diffuse through the internal protoplasm. In the case of CaCl2 the diffusion may be arrested by the pinching-off process. VI. Toxicity. 14. NaCl and KCl are more toxic to the exterior of the cell than to the interior, and the reverse is true for CaCl2 and MgCl2. 15. The relative non-toxicity of injected NaCl to the interior of the ameba is not necessarily due to its diffusion outward from the cell. 16. HCl is much more toxic to the exterior of a cell than to the interior; at pH 5.5 it is toxic to the surface whereas at pH 2.5 it is not toxic to the interior. NaOH to pH 9.8 is not toxic either to the surface or to the interior. VII. Antagonism. 17. The toxic effects of NaCl and of KCl on the exterior of the cell can be antagonized by CaCl2 and this antagonism occurs at the surface. Although the lethal effect of NaCl is thus antagonized, NaCl still penetrates but at a slower rate than if the ameba were immersed in a solution of this salt alone. 18. NaCl and HCl are mutually antagonistic in the interior of the ameba. No antagonism between the salts and HCl was found on the exterior of the ameba. No antagonism between the salts and NaOH was found on the interior or exterior of the ameba. 19. The pinching-off phenomenon can be antagonized by NaCl or by KCl, and the rate of the retardation of the pinching-off process varies with the concentration of the antagonizing salt. 20. The prevention of repair of a torn membrane by toxic solutions of NaCl or KCl can be antagonized by CaCl2. These experiments show directly the marked difference between the interior and the exterior of the cell in their behavior toward the chlorides of Na, K, Ca, and Mg. PMID:19872206

Study of the surface-enhanced Raman spectroscopy of residual impurities in hydroxylamine-reduced silver colloid and the effects of anions on the colloid activity.

PubMed

Dong, Xiao; Gu, Huaimin; Liu, Fangfang

2012-03-01

The paper investigated the residual ions in hydroxylamine-reduced silver colloid (HRSC) and the relationship between the condition of HRSC and the enhanced mechanisms of this colloid. We also detected the SERS of MB and studied the effects of anions on the Raman signal. In the case of HRSC, the bands of residual ions diminish while the bands of Ag-anions increase gradually with increasing the concentrations of Cl(-) and NO(3)(-). It means the affinity of residual ions on the silver surface is weaker than that of Cl(-) and NO(3)(-) and the residual ions are replaced gradually by the added Cl(-) or NO(3)(-). The Raman signal of residual ions can be detected by treatment with anions that do not bind strongly to the silver surface, such as SO(4)(2-). The most intense band of Ag-anions bonds can be also observed when adding weakly binding anions to the colloid. However, the anions which make up the Ag-anions bonds are residual Cl(-) and the effect of weakly binding anions is only to aggregate the silver particles. Residual Cl(-) can be replaced by I(-) which has the highest affinity. From the detection of methylene blue (MB), the effects of anions on the enhancement of Raman signal are discussed in detail, and these findings could make the conditions suitable for detecting analytes in high efficiency. This study will have a profound implication to SERS users about their interpretation of SERS spectra when obtaining these anomalous bands. Copyright © 2011 Elsevier B.V. All rights reserved.

Na(+) regulation by combined nitrogen in Azolla pinnata-Anabaena azollae symbiotic association during salt toxicity.

PubMed

Singh, Satya S; Singh, Santosh K; Mishra, Arun K

2008-01-01

To study the regulation of Na(+) ion by combined-N sources in Azolla pinnata-Anabaena azollae, Na(+) influx, intracellular Na(+) and Na(+) efflux were investigated in the presence of different N-sources (N(2), NH(4)(+), NO(3)(-) and urea) and various NaCl concentrations. Sodium influx by Azolla pinnata fronds was minimum in the presence of NO(3)(-). Almost identical levels of intracellular sodium, although less than N(2) and NH(4)(+) incubated fronds were observed in the presence of NO(3)(-) and urea. Efflux of sodium was minimum in urea and NO(3)(-) grown fronds. A low residual sodium was observed in the fronds incubated in NO(3)(-) and urea supplemented media. Results suggest that nitrate and urea curtailed the entry of sodium, reduced salt toxicity maximally by maintaining the minimum level of sodium and also conserved energy due to slow influx and efflux of Na(+) within the fronds during salt shock and the process of adaptation.