Characterization of solvated electrons in hydrogen cyanide clusters: (HCN)n- (n=3, 4)

Science.gov (United States)

Wu, Di; Li, Ying; Li, Zhuo; Chen, Wei; Li, Zhi-Ru; Sun, Chia-Chung

2006-02-01

Theoretical studies of the solvated electrons (HCN)n- (n =3, 4) reveal a variety of electron trapping possibilities in the (HCN)n (n =3, 4) clusters. Two isomers for (HCN)3- and four isomers for (HCN)4- are obtained at the MP2/aug -cc-pVDZ+dBF (diffusive bond functions) level of theory. In view of vertical electron detachment energies (VDEs) at the CCSD(T) level, the excess electron always "prefers" locating in the center of the system, i.e., the isomer with higher coordination number shows larger VDE value. However, the most stable isomers of the solvated electron state (HCN)3- and (HCN)4- are found to be the linear C∞ν and D∞h structures, respectively, but not the fullyl symmetric structures which have the largest VDE values.

High-mobility germanium p-MOSFETs by using HCl and (NH4)2S surface passivation

International Nuclear Information System (INIS)

Xue Bai-Qing; Wang Sheng-Kai; Han Le; Chang Hu-Dong; Sun Bing; Zhao Wei; Liu Hong-Gang

2013-01-01

To achieve a high-quality high-κ/Ge interfaces for high hole mobility Ge p-MOSFET applications, a simple chemical cleaning and surface passivation scheme is introduced, and Ge p-MOSFETs with effective channel hole mobility up to 665 cm 2 /V·s are demonstrated on a Ge (111) substrate. Moreover, a physical model is proposed to explain the dipole layer formation at the metal—oxide—semiconductor (MOS) interface by analyzing the electrical characteristics of HCl- and (NH 4 ) 2 S-passivated samples. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

Adsorption behavior of Co anchored on graphene sheets toward NO, SO2, NH3, CO and HCN molecules

International Nuclear Information System (INIS)

Tang, Yanan; Chen, Weiguang; Li, Chenggang; Pan, Lijun; Dai, Xianqi; Ma, Dongwei

2015-01-01

Graphical abstract: - Highlights: • In contrast to the pristine graphene, a vacancy defect in graphene strongly stabilizes the Co atom. • The positively charged of Co atom on graphene can regulate the stability of gas molecules. • Different gas molecules can modulate the electronic structure of Co–graphene systems. • The adsorbed NO on Co–graphene can effectively regulate the magnetic properties of systems. - Abstract: Based on the first-principles of density-functional theory (DFT), the effects of gas adsorption on the change in geometric stability, electronic structure and magnetic properties of graphene with anchored Co (Co–graphene) systems were investigated. A single Co adatom interacts much weaker with pristine graphene (Co/pri–graphene) than with the graphene containing a single vacancy (Co/SV–graphene). The Co dopant provides more electrons to the dangling bonds of carbon atom at defective site and exhibits more positive charges, which makes Co/SV–graphene less prone to be adsorbed by gas molecules in comparison to Co/pri–graphene. It is found that the electronic structure and magnetic properties of Co–graphene systems can be modulated by adsorbing gas molecules. Except the NH 3 molecule, the adsorbed NO, SO 2 , CO or HCN as electron acceptors on the Co/pri–graphene can exhibit semiconducting properties. Among the gas molecules, the strong adsorption of NO molecule can effectively regulate the magnetic properties of Co–graphene systems. Moreover, the stable configuration of Co/SV–graphene is more likely to be the gas sensor for detecting NO and SO 2 . The results validate that the reactivity of atomic-scale catalyst is supported on graphene sheets, which is expected to be potentially efficient in the gas sensors and electronic device

An Ab Initio MP2 Study of HCN-HX Hydrogen Bonded Complexes

Directory of Open Access Journals (Sweden)

Araújo Regiane C.M.U.

1998-01-01

Full Text Available An ab initio MP2/6-311++G** study has been performed to obtain geometries, binding energies and vibrational properties of HCN-HX H-bonded complexes with X = F, Cl, NC, CN and CCH. These MP2/6-311++G** results have revealed that: (i the calculated H-bond lengths are in very good agreement with the experimental ones; (ii the H-bond strength is associated with the intermolecular charge transfer and follows the order: HCN-HNC ~ HCN-HF > HCN-HCl ~ HCN-HCN > HCN-HCCH; (iii BSSE correction introduces an average reduction of 2.4 kJ/mol on the MP2/6-311++G** binding energies, i.e. 11% of the uncorrected binding energy; (iv the calculated zero-point energies reduce the stability of these complexes and show a good agreement with the available experimental values; (v the H-X stretching frequency is shifted downward upon H-bond formation. This displacement is associated with the H-bond length; (vi The more pronounced effect on the infrared intensities occurs with the H-X stretching intensity. It is much enhanced after complexation due to the charge-flux term; (vii the calculated intermolecular stretching frequencies are in very good agreement with the experimental ones; and, finally, (viii the results obtained for the HCN-HX complexes follow the same profile as those found for the acetylene-HX series but, in the latter case, the effects on the properties of the free molecules due to complexation are less pronounced than those in HCN-HX.

Development and Evaluation of a Hyperbaric Toxic Gas Monitor (SubTox) for Disabled Submarines

Science.gov (United States)

2013-08-01

air near the CO2 scrubbers was sampled, the common amine/ ammonia smell was present. And while no NH3 sensor was installed in the SubTox, no monitored...under pressure, the eight gases — ammonia , carbon monoxide, chlorine, hydrogen chloride, hydrogen cyanide, hydrogen sulfide, nitrogen dioxide, and...gases for which SEALs have been defined: ammonia (NH3), carbon monoxide (CO), chlorine (Cl2), hydrogen chloride (HCl), hydrogen cyanide (HCN

Ion exchange in HCl, NH2OH x HCl and N2H4 x 2HCl solutions

International Nuclear Information System (INIS)

Tohyama, Itiro; Otozai, Kiyoteru

1977-01-01

Distribution coefficients for 73 elements have been determined by the batch method in HCl, hydroxylamine and hydrazine solutions using strongly acidic and strongly basic exchanger resins. In general, a similar behaviour was observed. In some cases, however, the kind of onium ion was of considerable influence. Hydroxylamine and hydrazine solutions are useful as a substitute for HCl in many separations, as they are easily handled and can rapidly be decomposed by nitric acid. (orig./RB) [de

Experimental conditions affecting the kinetics of aqueous HCN polymerization as revealed by UV-vis spectroscopy.

Science.gov (United States)

Marín-Yaseli, Margarita R; Moreno, Miguel; de la Fuente, José L; Briones, Carlos; Ruiz-Bermejo, Marta

2018-02-15

HCN polymerization is one of the most important and fascinating reactions in prebiotic chemistry, and interest in HCN polymers in the field of materials science is growing. However, little is known about the kinetics of the HCN polymerization process. In the present study, a first approach to the kinetics of two sets of aqueous HCN polymerizations, from NH 4 CN and NaCN, at middle temperatures between 4 and 38°C, has been carried out. For each series, the presence of air and salts in the reaction medium has been systematically explored. A previous kinetic analysis was conducted during the conversion of the insoluble black HCN polymers obtained as gel fractions in these precipitation polymerizations for a reaction of one month, where a limit conversion was achieved at the highest polymerization temperature. The kinetic description of the gravimetric data for this complex system shows a clear change in the linear dependence with the polymerization temperature for the reaction from NH 4 CN, besides a relevant catalytic effect of ammonium, in comparison with those data obtained from the NaCN series. These results also demonstrated the notable influence of air, oxygen, and the saline medium in HCN polymer formation. Similar conclusions were reached when the sol fractions were monitored by UV-vis spectroscopy, and a Hill type correlation was used to describe the polymerization profiles obtained. This technique was chosen because it provides an easy, prompt and fast method to follow the evolution of the liquid or continuous phase of the process under study. Copyright © 2017 Elsevier B.V. All rights reserved.

Adsorption behavior of Co anchored on graphene sheets toward NO, SO{sub 2}, NH{sub 3}, CO and HCN molecules

Energy Technology Data Exchange (ETDEWEB)

Tang, Yanan, E-mail: yntang2010@hotmail.com [College of Physics and Electronic Engineering, Zhengzhou Normal University, Zhengzhou, Henan 450044 (China); Quantum Materials Research Center, Zhengzhou Normal University, Henan 450044 (China); Chen, Weiguang; Li, Chenggang; Pan, Lijun [College of Physics and Electronic Engineering, Zhengzhou Normal University, Zhengzhou, Henan 450044 (China); Quantum Materials Research Center, Zhengzhou Normal University, Henan 450044 (China); Dai, Xianqi, E-mail: xqdai@henannu.edu.cn [College of Physics and Electronic Engineering, Zhengzhou Normal University, Zhengzhou, Henan 450044 (China); Quantum Materials Research Center, Zhengzhou Normal University, Henan 450044 (China); Ma, Dongwei [College of Physics and Electrical Engineering, Anyang Normal University, Anyang, Henan 455000 (China)

2015-07-01

Graphical abstract: - Highlights: • In contrast to the pristine graphene, a vacancy defect in graphene strongly stabilizes the Co atom. • The positively charged of Co atom on graphene can regulate the stability of gas molecules. • Different gas molecules can modulate the electronic structure of Co–graphene systems. • The adsorbed NO on Co–graphene can effectively regulate the magnetic properties of systems. - Abstract: Based on the first-principles of density-functional theory (DFT), the effects of gas adsorption on the change in geometric stability, electronic structure and magnetic properties of graphene with anchored Co (Co–graphene) systems were investigated. A single Co adatom interacts much weaker with pristine graphene (Co/pri–graphene) than with the graphene containing a single vacancy (Co/SV–graphene). The Co dopant provides more electrons to the dangling bonds of carbon atom at defective site and exhibits more positive charges, which makes Co/SV–graphene less prone to be adsorbed by gas molecules in comparison to Co/pri–graphene. It is found that the electronic structure and magnetic properties of Co–graphene systems can be modulated by adsorbing gas molecules. Except the NH{sub 3} molecule, the adsorbed NO, SO{sub 2}, CO or HCN as electron acceptors on the Co/pri–graphene can exhibit semiconducting properties. Among the gas molecules, the strong adsorption of NO molecule can effectively regulate the magnetic properties of Co–graphene systems. Moreover, the stable configuration of Co/SV–graphene is more likely to be the gas sensor for detecting NO and SO{sub 2}. The results validate that the reactivity of atomic-scale catalyst is supported on graphene sheets, which is expected to be potentially efficient in the gas sensors and electronic device.

Reduction of nitrogen compounds in oceanic basement and its implications for HCN formation and abiotic organic synthesis.

Science.gov (United States)

Holm, Nils G; Neubeck, Anna

2009-10-22

Hydrogen cyanide is an excellent organic reagent and is central to most of the reaction pathways leading to abiotic formation of simple organic compounds containing nitrogen, such as amino acids, purines and pyrimidines. Reduced carbon and nitrogen precursor compounds for the synthesis of HCN may be formed under off-axis hydrothermal conditions in oceanic lithosphere in the presence of native Fe and Ni and are adsorbed on authigenic layer silicates and zeolites. The native metals as well as the molecular hydrogen reducing CO2 to CO/CH4 and NO3-/NO2- to NH3/NH4+ are a result of serpentinization of mafic rocks. Oceanic plates are conveyor belts of reduced carbon and nitrogen compounds from the off-axis hydrothermal environments to the subduction zones, where compaction, dehydration, desiccation and diagenetic reactions affect the organic precursors. CO/CH4 and NH3/NH4+ in fluids distilled out of layer silicates and zeolites in the subducting plate at an early stage of subduction will react upon heating and form HCN, which is then available for further organic reactions to, for instance, carbohydrates, nucleosides or even nucleotides, under alkaline conditions in hydrated mantle rocks of the overriding plate. Convergent margins in the initial phase of subduction must, therefore, be considered the most potent sites for prebiotic reactions on Earth. This means that origin of life processes are, perhaps, only possible on planets where some kind of plate tectonics occur.

Reduction of nitrogen compounds in oceanic basement and its implications for HCN formation and abiotic organic synthesis

Directory of Open Access Journals (Sweden)

Neubeck Anna

2009-10-01

Full Text Available Abstract Hydrogen cyanide is an excellent organic reagent and is central to most of the reaction pathways leading to abiotic formation of simple organic compounds containing nitrogen, such as amino acids, purines and pyrimidines. Reduced carbon and nitrogen precursor compounds for the synthesis of HCN may be formed under off-axis hydrothermal conditions in oceanic lithosphere in the presence of native Fe and Ni and are adsorbed on authigenic layer silicates and zeolites. The native metals as well as the molecular hydrogen reducing CO2 to CO/CH4 and NO3-/NO2- to NH3/NH4+ are a result of serpentinization of mafic rocks. Oceanic plates are conveyor belts of reduced carbon and nitrogen compounds from the off-axis hydrothermal environments to the subduction zones, where compaction, dehydration, desiccation and diagenetic reactions affect the organic precursors. CO/CH4 and NH3/NH4+ in fluids distilled out of layer silicates and zeolites in the subducting plate at an early stage of subduction will react upon heating and form HCN, which is then available for further organic reactions to, for instance, carbohydrates, nucleosides or even nucleotides, under alkaline conditions in hydrated mantle rocks of the overriding plate. Convergent margins in the initial phase of subduction must, therefore, be considered the most potent sites for prebiotic reactions on Earth. This means that origin of life processes are, perhaps, only possible on planets where some kind of plate tectonics occur.

Qualification of a Multi-Channel Infrared Laser Absorption Spectrometer for Monitoring CO, HCl, HCN, HF, and CO2 Aboard Manned Spacecraft

Science.gov (United States)

Briggs, Ryan M.; Frez, Clifford; Forouhar, Siamak; May, Randy D.; Meyer, Marit E.; Kulis, Michael J.; Berger, Gordon M.

2015-01-01

Monitoring of specific combustion products can provide early-warning detection of accidental fires aboard manned spacecraft and also identify the source and severity of combustion events. Furthermore, quantitative in situ measurements are important for gauging levels of exposure to hazardous gases, particularly on long-duration missions where analysis of returned samples becomes impractical. Absorption spectroscopy using tunable laser sources in the 2 to 5 micrometer wavelength range enables accurate, unambiguous detection of CO, HCl, HCN, HF, and CO2, which are produced in varying amounts through the heating of electrical components and packaging materials commonly used aboard spacecraft. Here, we report on calibration and testing of a five-channel laser absorption spectrometer designed to accurately monitor ambient gas-phase concentrations of these five compounds, with low-level detection limits based on the Spacecraft Maximum Allowable Concentrations. The instrument employs a two-pass absorption cell with a total optical pathlength of 50 cm and a dedicated infrared semiconductor laser source for each target gas. We present results from testing the five-channel sensor in the presence of trace concentrations of the target compounds that were introduced using both gas sources and oxidative pyrolysis (non-flaming combustion) of solid material mixtures.

In situ measurements of HCN and CH3CN over the Pacific Ocean: Sources, sinks, and budgets

Science.gov (United States)

Singh, H. B.; Salas, L.; Herlth, D.; Kolyer, R.; Czech, E.; Viezee, W.; Li, Q.; Jacob, D. J.; Blake, D.; Sachse, G.; Harward, C. N.; Fuelberg, H.; Kiley, C. M.; Zhao, Y.; Kondo, Y.

2003-10-01

We report the first in situ measurements of hydrogen cyanide (HCN) and methyl cyanide (CH3CN, acetonitrile) from the Pacific troposphere (0-12 km) obtained during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) airborne mission (February-April 2001). Mean HCN and CH3CN mixing ratios of 243 ± 118 (median 218) ppt and 149 ± 56 (median 138) ppt, respectively, were measured. These in situ observations correspond to a mean tropospheric HCN column of 4.2 × 1015 molecules cm-2 and a CH3CN column of 2.5 × 1015 molecules cm-2. This is in good agreement with the 0-12 km HCN column of 4.4 (±0.6) × 1015 molecules cm-2 derived from infrared solar spectroscopic observations over Japan. Mixing ratios of HCN and CH3CN were greatly enhanced in pollution outflow from Asia and were well correlated with each other as well as with known tracers of biomass combustion (e.g., CH3Cl, CO). Volumetric enhancement (or emission) ratios (ERs) relative to CO in free tropospheric plumes, likely originating from fires, were 0.34% for HCN and 0.17% for CH3CN. ERs with respect to CH3Cl and CO in selected biomass burning (BB) plumes in the free troposphere and in boundary layer pollution episodes are used to estimate a global BB source of 0.8 ± 0.4 Tg (N) yr-1 for HCN and 0.4 ± 0.1 Tg (N) yr-1 for CH3CN. In comparison, emissions from industry and fossil fuel combustion are quite small (atmospheric residence time of 5.0 months for HCN and 6.6 months for CH3CN is calculated. A global budget analysis shows that the sources and sinks of HCN and CH3CN are roughly in balance but large uncertainties remain in part due to a lack of observational data from the atmosphere and the oceans. Pathways leading to the oceanic (and soil) degradation of these cyanides are poorly known but are expected to be biological in nature.

Effects of humidity on the quantitative determination of HCl, NOx, H2S, and NH3 using a three-stage filter pack with ion chromatography analysis

International Nuclear Information System (INIS)

Borek, T.T.; Wu, C.F.

1993-01-01

Low-level transuranic (TRU) waste to be stored underground at the Waste Isolation Pilot Plant (WIPP) has the potential to generate low levels of reactive gases such as HCl, NO x H 2 S, and NH 3 through radiological, biological, and chemical (corrosion) processes. Because of the low levels of gas expected to be produced (< 1 ppM), a method was developed which includes the simultaneous sampling of gases using chemically treated filter papers and analysis of the extracted ions by ion chromatography. To determine the effects of humidification on the collection and determination of reactive gases, a humidification system was added to the trace gas generator system to produce a relative humidity approximately equal to that in the Humid Test Bin. This humidification system consisted of gas washing bottles filled with saturated brine (NaCl) that has been shown to produce a relative humidity of approximately 75% in the temperature range of 68 degree F to 86 degree

Mechanism of NH{sub 3} desorption during the reaction of H{sub 2} with nitrogen containing carbonaceous materials

Energy Technology Data Exchange (ETDEWEB)

Juan F. Espinal; Thanh N. Truong; Fanor Mondragon [University of Antioquia, Medellin (Colombia). Institute of Chemistry

2005-07-01

The continued increase in demand for natural gas has stimulated the interest in coal conversion to methane as synthetic natural gas by hydropyrolysis of coal (pyrolysis in a H{sub 2} atmosphere). Because the produced raw gas contains considerable amounts of gaseous N-containing products that have to be removed before delivering to final users, the information on distribution of coal-N is important for designing purification processes. It has been reported in the literature that NH{sub 3} is the main nitrogen containing gas that is released during the hydropyrolysis process. Other gases such as HCN and N{sub 2} are also released but in a much smaller amount. To the best of our knowledge, the mechanism for NH{sub 3} desorption during hydrogen reaction with carbonaceous materials has not been studied. We carried out a molecular modeling study using Density Functional Theory in order to get an insight of the mechanism and thermodynamics for NH{sub 3} evolution using pyridinic nitrogen as a model of N-containing carbonaceous material. We propose a mechanism that involves consecutive hydrogenation steps that lead to C-N bond breakage and NH{sub 3} desorption to the gas phase. It was found that the first hydrogenation reaction is highly exothermic. However, further hydrogenations are endothermic. Several pathways for NH{sub 3} evolution were proposed and most of them show high exothermicity. 17 refs., 2 figs.

Entrained bed gasification of coal: prediction of contaminant levels using thermodynamic calculations

Energy Technology Data Exchange (ETDEWEB)

Furimsky, E.; Zheng, L.; Boudreau, F.; Kovacik, G. (CANMET, Ottawa, ON (Canada). Energy Research Labs.)

1993-10-01

The F.A.C.T. method was used for predicting the emissions of S-, Cl-, N-, Pb- and As-containing contaminants from entrained bed gasification of one bituminous coal and one subbituminous coal. When the effect of mineral matter was included, the emissions of H[sub 2]S, CS[sub 2], COS, HCl and HCN decreased substantially whereas the amount of predicted NH[sub 3] remained unaffected. The decrease was offset by increased formation of metal sulphides, chlorides and cyanides. Relatively large amounts of Na, K, Mg, Ca, Pb and As in the gas were predicted by the method. The chlorides of these metals are also rather volatile. The presence of steam increased the amount of H[sub 2]S and HCl and decreased the amount of HCN in the products. 8 refs., 5 figs., 5 tabs.

ALMA HCN AND HCO{sup +} J  = 3 − 2 OBSERVATIONS OF OPTICAL SEYFERT AND LUMINOUS INFRARED GALAXIES: CONFIRMATION OF ELEVATED HCN-TO-HCO{sup +} FLUX RATIOS IN AGNS

Energy Technology Data Exchange (ETDEWEB)

Imanishi, Masatoshi; Nakanishi, Kouichiro [National Astronomical Observatory of Japan, National Institutes of Natural Sciences (NINS), 2-21-1 Osawa, Mitaka, Tokyo 181-8588 (Japan); Izumi, Takuma, E-mail: masa.imanishi@nao.ac.jp [Institute of Astronomy, School of Science, The University of Tokyo, 2-21-1 Osawa, Mitaka, Tokyo 181-0015 (Japan)

2016-12-01

We present the results of our ALMA observations of three active galactic nucleus (AGN)-dominated nuclei in optical Seyfert 1 galaxies (NGC 7469, I Zw 1, and IC 4329 A) and eleven luminous infrared galaxies (LIRGs) with various levels of infrared estimated energetic contributions by AGNs at the HCN and HCO{sup +} J  = 3 − 2 emission lines. The HCN and HCO{sup +} J  = 3 − 2 emission lines are clearly detected at the main nuclei of all sources, except for IC 4329 A. The vibrationally excited ( v {sub 2} = 1f) HCN J  = 3 − 2 and HCO{sup +} J  = 3 − 2 emission lines are simultaneously covered, and HCN v {sub 2} = 1f J  = 3 − 2 emission line signatures are seen in the main nuclei of two LIRGs, IRAS 12112+0305 and IRAS 22491–1808, neither of which shows clear buried AGN signatures in the infrared. If the vibrational excitation is dominated by infrared radiative pumping, through the absorption of infrared 14 μ m photons, primarily originating from AGN-heated hot dust emission, then these two LIRGs may contain infrared-elusive, but (sub)millimeter-detectable, extremely deeply buried AGNs. These vibrationally excited emission lines are not detected in the three AGN-dominated optical Seyfert 1 nuclei. However, the observed HCN v {sub 2} = 1f to v  = 0 flux ratios in these optical Seyferts are still consistent with the intrinsic flux ratios in LIRGs with detectable HCN v {sub 2} = 1f emission lines. The observed HCN-to-HCO{sup +} J  = 3 − 2 flux ratios tend to be higher in galactic nuclei with luminous AGN signatures compared with starburst-dominated regions, as previously seen at J  = 1 − 0 and J  = 4 − 3.

Preparation and characterization of a layered perovskite-type organic-inorganic hybrid compound (C8NH6-CH2CH2NH3)2CuCl4

International Nuclear Information System (INIS)

Zheng Yingying; Wu Gang; Deng Meng; Chen Hongzheng; Wang Mang; Tang, B.-Z.

2006-01-01

The organic-inorganic hybrid compound (C 8 NH 6 -CH 2 CH 2 NH 3 ) 2 CuCl 4 (AEI-CuCl 4 ) was synthesized from ethanol solution containing copper chloride and 3-2-(aminoethyl) indole hydrochloride (AEI-HCl). High order diffraction peaks corresponding to (0 0 l; l = 2, 4, 6, ...) observed in the X-ray diffraction profile of AEI-CuCl 4 indicated the formation of hybrid crystal with layered perovskite structure. The organic-inorganic hybrid crystal thin film can be easily prepared by spin-coating method from the ethanol solution of the AEI-CuCl 4 perovskite and it showed characteristic absorptions of CuCl-based layered perovskite centered at 288 and 388 nm, as well as the photoluminescence peak at around 420 nm. The unaided-eye-detectable blue fluorescence emission comes from the cooperation of AEI-HCl and AEI-CuCl 4 perovskite, in which protonized aminoethyl indole dominates the shape of the spectrum and the enhancement of emission intensity is due to the formation of the perovskite structure. The thermal analysis presented that the AEI-CuCl 4 perovskite started to melt at 182 deg. C, together with the beginning of the decomposition of the hybrids. Compared with the organic-inorganic perovskite hybrids reported previously, the AEI-CuCl 4 perovskite shows a novel stepwise decomposition behavior

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

Science.gov (United States)

Mitzi, D. B.

1999-07-01

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

Detection of the HC3NH+ and HCNH+ ions in the L1544 pre-stellar core

Science.gov (United States)

Quénard, D.; Vastel, C.; Ceccarelli, C.; Hily-Blant, P.; Lefloch, B.; Bachiller, R.

2017-09-01

The L1544 pre-stellar core was observed as part of the ASAI (Astrochemical Surveys At IRAM) Large Program. We report the first detection in a pre-stellar core of the HCNH+ and HC3NH+ ions. The high spectral resolution of the observations allows us to resolve the hyperfine structure of HCNH+. Local thermodynamic equilibrium (LTE) analysis leads to derive a column density equal to (2.0 ± 0.2) × 1013 cm-2 for HCNH+ and (1.5 ± 0.5) × 1011 cm-2 for HC3NH+. We also present non-LTE analysis of five transitions of HC3N, three transitions of H13CN and one transition of HN13C, all of them linked to the chemistry of HCNH+ and HC3NH+. We computed for HC3N, HCN and HNC a column density of (2.0 ± 0.4) × 1013 cm-2, (3.6 ± 0.9) × 1014 cm-2 and (3.0 ± 1.0) × 1014 cm-2, respectively. We used the gas-grain chemical code nautilus to predict the abundances of all these species across the pre-stellar core. Comparison of the observations with the model predictions suggests that the emission from HCNH+ and HC3NH+ originates in the external layer where non-thermal desorption of other species was previously observed. The observed abundance of both ionic species ([HCNH+] ≃ 3 × 10-10 and [HC3NH+] ≃ [1.5 - 3.0] × 10-12, with respect to H2) cannot be reproduced at the same time by the chemical modelling within the error bars of the observations only. We discuss the possible reasons for the discrepancy and suggest that the current chemical models are not fully accurate or complete. However, the modelled abundances are within a factor of 3, consistent with the observations, considering a late stage of the evolution of the pre-stellar core, compatible with previous observations.

Densities and apparent molar volumes of atmospherically important electrolyte solutions. 1. The solutes H2SO4, HNO3, HCl, Na2SO4, NaNO3, NaCl, (NH4)2SO4, NH4NO3, and NH4Cl from 0 to 50 °C, including extrapolations to very low temperature and to the pure liquid state, and NaHSO4, NaOH, and NH3 at 25 °C.

Science.gov (United States)

Clegg, S L; Wexler, A S

2011-04-21

Calculations of the size and density of atmospheric aerosols are complicated by the fact that they can exist at concentrations highly supersaturated with respect to dissolved salts and supercooled with respect to ice. Densities and apparent molar volumes of solutes in aqueous solutions containing the solutes H(2)SO(4), HNO(3), HCl, Na(2)SO(4), NaNO(3), NaCl, (NH(4))(2)SO(4), NH(4)NO(3), and NH(4)Cl have been critically evaluated and represented using fitted equations from 0 to 50 °C or greater and from infinite dilution to concentrations saturated or supersaturated with respect to the dissolved salts. Using extrapolated densities of high-temperature solutions and melts, the relationship between density and concentration is extended to the hypothetical pure liquid solutes. Above a given reference concentration of a few mol kg(-1), it is observed that density increases almost linearly with decreasing temperature, and comparisons with available data below 0 °C suggest that the fitted equations for density can be extrapolated to very low temperatures. As concentration is decreased below the reference concentration, the variation of density with temperature tends to that of water (which decreases as temperature is reduced below 3.98 °C). In this region below the reference concentration, and below 0 °C, densities are calculated using extrapolated apparent molar volumes which are constrained to agree at the reference concentrations with an equation for the directly fitted density. Calculated volume properties agree well with available data at low temperatures, for both concentrated and dilute solutions. Comparisons are made with literature data for temperatures of maximum density. Apparent molar volumes at infinite dilution are consistent, on a single ion basis, to better than ±0.1 cm(3) mol(-1) from 0 to 50 °C. Volume properties of aqueous NaHSO(4), NaOH, and NH(3) have also been evaluated, at 25 °C only. In part 2 of this work (ref 1 ) an ion interaction (Pitzer

Detection of interstellar vibrationally excited HCN

International Nuclear Information System (INIS)

Ziurys, L.M.; Turner, B.E.

1986-01-01

Vibrationally excited HCN has been observed for the first time in the interstellar medium. The J = 3-2 rotational transitions of the l-doubled (0,1/sup 1d/,1c, 0) bending mode of HCN have been detected toward Orion-KL and IRC +10216. In Orion, the overall column density in the (0,1,0) mode, which exclusively samples the ''hot core,'' is 1.7-10 16 cm -2 and can be understood in terms of the ''doughnut'' model for Orion. The ground-state HCN column density implied by the excited-state observations is 2.3 x 10 18 cm -2 in the hot core, at least one order of magnitude greater than the column densities derived for HCN in its spike and plateau/doughnut components. Radiative excitation by 14 μm flux from IRc2 accounts for the (0,1,0) population provided the hot core is approx.6-7 x 10 16 cm distant from IRc2, in agreement with the ''cavity'' model for KL. Toward IRC +10216 we have detected J = 3-2 transitions of both (0,1/sup 1c/,/sup 1d/,0) and (0,2 0 ,0) excited states. The spectral profiles have been modeled to yield abundances and excitation conditions throughout the expanding envelope

Gabapentin Modulates HCN4 Channel Voltage-Dependence

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Han-Shen Tae

2017-08-01

Full Text Available Gabapentin (GBP is widely used to treat epilepsy and neuropathic pain. There is evidence that GBP can act on hyperpolarization-activated cation (HCN channel-mediated Ih in brain slice experiments. However, evidence showing that GBP directly modulates HCN channels is lacking. The effect of GBP was tested using two-electrode voltage clamp recordings from human HCN1, HCN2, and HCN4 channels expressed in Xenopus oocytes. Whole-cell recordings were also made from mouse spinal cord slices targeting either parvalbumin positive (PV+ or calretinin positive (CR+ inhibitory neurons. The effect of GBP on Ih was measured in each inhibitory neuron population. HCN4 expression was assessed in the spinal cord using immunohistochemistry. When applied to HCN4 channels, GBP (100 μM caused a hyperpolarizing shift in the voltage of half activation (V1/2 thereby reducing the currents. Gabapentin had no impact on the V1/2 of HCN1 or HCN2 channels. There was a robust increase in the time to half activation for HCN4 channels with only a small increase noted for HCN1 channels. Gabapentin also caused a hyperpolarizing shift in the V1/2 of Ih measured from HCN4-expressing PV+ inhibitory neurons in the spinal dorsal horn. Gabapentin had minimal effect on Ih recorded from CR+ neurons. Consistent with this, immunohistochemical analysis revealed that the majority of CR+ inhibitory neurons do not express somatic HCN4 channels. In conclusion, GBP reduces HCN4 channel-mediated currents through a hyperpolarized shift in the V1/2. The HCN channel subtype selectivity of GBP provides a unique tool for investigating HCN4 channel function in the central nervous system. The HCN4 channel is a candidate molecular target for the acute analgesic and anticonvulsant actions of GBP.

Interaction of N-hydroxyurea with strong proton donors: HCl and HF

International Nuclear Information System (INIS)

Sałdyka, Magdalena

2014-01-01

Highlights: • 1:1 and 1:2 N-hydroxyurea complexes with HCl and HF are trapped in argon matrices. • The complexes are stabilized by strong X–H⋯O bond. • Hydrogen bonds in the cyclic 1:2 complexes show strong cooperativity. • The C=O group is the strongest proton acceptor centre in the N-hydroxyurea molecule. - Abstract: An infrared spectroscopic and MP2/6-311++G(2d,2p) study of strong hydrogen bonded complexes of N-hydroxyurea (NH 2 CONHOH) with hydrogen halides (HCl and HF) trapped in solid argon matrices is reported. 1:1 and 1:2 complexes between N-hydroxyurea and hydrogen chloride, hydrogen fluoride have been identified in the NH 2 CONHOH/HCl/Ar, NH 2 CONHOH/HF/Ar matrices, respectively; their structures were determined by comparison of the spectra with the results of calculations. In the 1:1 complexes, identified for both hydrogen halide molecules, the cyclic structure stabilized by the X–H⋯O and N–H⋯X bonds is present; for the NH 2 CONHOH⋯HF system another isomeric 1:1 complex is also observed. Two 1:2 complexes were identified for the N-hydroxyurea–hydrogen chloride system characterised by the Cl–H⋯O and N–H⋯Cl bonds. The results of the study evidence that N-hydroxyurea is an oxygen base in the gas-phase with the carbonyl group as the strongest proton acceptor centre in the molecule

Interaction of N-hydroxyurea with strong proton donors: HCl and HF

Energy Technology Data Exchange (ETDEWEB)

Sałdyka, Magdalena, E-mail: magdalena.saldyka@chem.uni.wroc.pl

2014-11-24

Highlights: • 1:1 and 1:2 N-hydroxyurea complexes with HCl and HF are trapped in argon matrices. • The complexes are stabilized by strong X–H⋯O bond. • Hydrogen bonds in the cyclic 1:2 complexes show strong cooperativity. • The C=O group is the strongest proton acceptor centre in the N-hydroxyurea molecule. - Abstract: An infrared spectroscopic and MP2/6-311++G(2d,2p) study of strong hydrogen bonded complexes of N-hydroxyurea (NH{sub 2}CONHOH) with hydrogen halides (HCl and HF) trapped in solid argon matrices is reported. 1:1 and 1:2 complexes between N-hydroxyurea and hydrogen chloride, hydrogen fluoride have been identified in the NH{sub 2}CONHOH/HCl/Ar, NH{sub 2}CONHOH/HF/Ar matrices, respectively; their structures were determined by comparison of the spectra with the results of calculations. In the 1:1 complexes, identified for both hydrogen halide molecules, the cyclic structure stabilized by the X–H⋯O and N–H⋯X bonds is present; for the NH{sub 2}CONHOH⋯HF system another isomeric 1:1 complex is also observed. Two 1:2 complexes were identified for the N-hydroxyurea–hydrogen chloride system characterised by the Cl–H⋯O and N–H⋯Cl bonds. The results of the study evidence that N-hydroxyurea is an oxygen base in the gas-phase with the carbonyl group as the strongest proton acceptor centre in the molecule.

Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 perovskites for solar cell applications.

Science.gov (United States)

Umari, Paolo; Mosconi, Edoardo; De Angelis, Filippo

2014-03-26

Hybrid AMX3 perovskites (A = Cs, CH3NH3; M = Sn, Pb; X = halide) have revolutionized the scenario of emerging photovoltaic technologies, with very recent results demonstrating 15% efficient solar cells. The CH3NH3PbI3/MAPb(I(1-x)Cl(x))3 perovskites have dominated the field, while the similar CH3NH3SnI3 has not been exploited for photovoltaic applications. Replacement of Pb by Sn would facilitate the large uptake of perovskite-based photovoltaics. Despite the extremely fast progress, the materials electronic properties which are key to the photovoltaic performance are relatively little understood. Density Functional Theory electronic structure methods have so far delivered an unbalanced description of Pb- and Sn-based perovskites. Here we develop an effective GW method incorporating spin-orbit coupling which allows us to accurately model the electronic, optical and transport properties of CH3NH3SnI3 and CH3NH3PbI3, opening the way to new materials design. The different CH3NH3SnI3 and CH3NH3PbI3 electronic properties are discussed in light of their exploitation for solar cells, and found to be dominantly due to relativistic effects. These effects stabilize the CH3NH3PbI3 material towards oxidation, by inducing a deeper valence band edge. Relativistic effects, however, also increase the material band-gap compared to CH3NH3SnI3, due to the valence band energy downshift (~0.7 eV) being only partly compensated by the conduction band downshift (~0.2 eV).

Abundances and implications of volatile-bearing species from evolved gas analysis of the Rocknest aeolian deposit, Gale Crater, Mars

Science.gov (United States)

Archer, Paul Douglas; Franz, Heather B.; Sutter, Brad; Arevalo, Ricardo D.; Coll, Patrice; Eigenbrode, Jennifer L.; Glavin, Daniel P.; Jones, John J.; Leshin, Laurie A.; Mahaffy, Paul R.; McAdam, Amy C.; McKay, Christopher P.; Ming, Douglas W.; Morris, Richard V.; Navarro-González, Rafael; Niles, Paul B.; Pavlov, Alex; Squyres, Steven W.; Stern, Jennifer C.; Steele, Andrew; Wray, James J.

2014-01-01

The Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) rover Curiosity detected evolved gases during thermal analysis of soil samples from the Rocknest aeolian deposit in Gale Crater. Major species detected (in order of decreasing molar abundance) were H2O, SO2, CO2, and O2, all at the µmol level, with HCl, H2S, NH3, NO, and HCN present at the tens to hundreds of nmol level. We compute weight % numbers for the major gases evolved by assuming a likely source and calculate abundances between 0.5 and 3 wt.%. The evolution of these gases implies the presence of both oxidized (perchlorates) and reduced (sulfides or H-bearing) species as well as minerals formed under alkaline (carbonates) and possibly acidic (sulfates) conditions. Possible source phases in the Rocknest material are hydrated amorphous material, minor clay minerals, and hydrated perchlorate salts (all potential H2O sources), carbonates (CO2), perchlorates (O2 and HCl), and potential N-bearing materials (e.g., Martian nitrates, terrestrial or Martian nitrogenated organics, ammonium salts) that evolve NH3, NO, and/or HCN. We conclude that Rocknest materials are a physical mixture in chemical disequilibrium, consistent with aeolian mixing, and that although weathering is not extensive, it may be ongoing even under current Martian surface conditions.

Ultrasonic irradiation-promoted one-pot synthesis of CH3NH3PbBr3 quantum dots without using flammable CH3NH2 precursor

Science.gov (United States)

Jiang, Han; Wang, Chunlei; Lv, Changgui; Xu, Shuhong; Zhu, Li; Zhang, Ruohu; Cui, Yiping

2017-02-01

At present, the CH3NH3PbBr3 quantum dots (QDs) reported in the literature usually contain two synthesis steps: the initial preparation of CH3NH3Br via the reaction of flammable CH3NH2 and HBr, together with the subsequent formation of CH3NH3PbBr3 QDs. To avoid the use of dangerous CH3NH2, this work develops a novel one-pot method for synthesizing CH3NH3PbBr3 QDs using safe and commercially available reactants (CH3NH3Cl, KBr and PbCl2). It is found that ultrasonic treatment plays a key role during the synthesis of CH3NH3PbBr3 QDs. Without ultrasonic irradiation, it is not possible to synthesize CH3NH3PbBr3 QDs under heating or vigorous stirring. Aliquots of samples taken at different ultrasonic irradiation time intervals show a time-dependent redshift in the emission wavelength. This suggests the formation of CH3NH3PbCl3 QDs first, followed by the formation of CH3NH3PbBr3 QDs through ultrasonically promoted halide exchange. Moreover, mixed CH3NH3PbCl x Br3-x QDs with a tunable emission wavelength can also be prepared through this one-pot method by controlling the ultrasonic irradiation time. In comparison to the previous two-step method, the current one-pot method is simpler, less time-consuming and does not use flammable CH3NH2. The as-prepared CH3NH3PbBr3 QDs show a comparable photoluminescence (PL) quantum yield (QY) to that of the literature. What is more, the ultrasonic time-controlled emission wavelength of CH3NH3PbCl x Br3-x QDs also provides an alternative way of tuning QD emission to the traditional way of controlling the halide ratios.

Flavonoid Regulation of HCN2 Channels*

Science.gov (United States)

Carlson, Anne E.; Rosenbaum, Joel C.; Brelidze, Tinatin I.; Klevit, Rachel E.; Zagotta, William N.

2013-01-01

The hyperpolarization-activated cyclic nucleotide-modulated (HCN) channels are pacemaker channels whose currents contribute to rhythmic activity in the heart and brain. HCN channels open in response to hyperpolarizing voltages, and the binding of cAMP to their cyclic nucleotide-binding domain (CNBD) facilitates channel opening. Here, we report that, like cAMP, the flavonoid fisetin potentiates HCN2 channel gating. Fisetin sped HCN2 activation and shifted the conductance-voltage relationship to more depolarizing potentials with a half-maximal effective concentration (EC50) of 1.8 μm. When applied together, fisetin and cAMP regulated HCN2 gating in a nonadditive fashion. Fisetin did not potentiate HCN2 channels lacking their CNBD, and two independent fluorescence-based binding assays reported that fisetin bound to the purified CNBD. These data suggest that the CNBD mediates the fisetin potentiation of HCN2 channels. Moreover, binding assays suggest that fisetin and cAMP partially compete for binding to the CNBD. NMR experiments demonstrated that fisetin binds within the cAMP-binding pocket, interacting with some of the same residues as cAMP. Together, these data indicate that fisetin is a partial agonist for HCN2 channels. PMID:24085296

A new NH 3 orbital of the NH 3/Ni(110) surface observed by metastable quenching spectroscopy

Science.gov (United States)

Lee, Lihwa; Arias, Jose; Hanrahan, Ciaran; Martin, Richard M.; Metiu, Horia

1986-01-01

By using metastable quenching spectroscopy we have found a new NH 3 filled orbital (in the language of one electron theory) for NH 3/Ni(110), located at the Fermi level of the surface. The orbital is not observed when NH 3 is adsorbed on Ni(110), but it is detected for NH 3 adsorbed on polycrystalline Al.

NH3 and NH4+ permeability in aquaporin-expressing Xenopus oocytes

DEFF Research Database (Denmark)

Holm, Lars M.; Jahn, Thomas Paul; Møller, Anders Laurell Blom

2005-01-01

We have shown recently, in a yeast expression system, that some aquaporins are permeable to ammonia. In the present study, we expressed the mammalian aquaporins AQP8, AQQP9, AQP3, AQP1 and a plant aquaporin TIP2;1 in Xenopus oocytes to study the transport of ammonia (NH3) and ammonium (NH4+) under...... inwards currents carried by NH4+. This conductivity increased as a sigmoid function of external [NH3]: for AQP8 at a bath pH (pH(e)) of 6.5, the conductance was abolished, at pH(e) 7.4 it was half maximal and at pH(e) 7.8 it saturated. NY4+ influx was associated with oocyte swelling. In comparison, native...... oocytes as well as AQP1 and tip2;1-expressing oocytes showed small currents that were associated with small and even negative volume changes. We conclude that AQP8, AQP9, AQP3, and TIP2;1, apart from being water channels, also support significant fluxes of NH3. These aquaporins could support NH4...

Crystal structure of [UO2(NH35]NO3·NH3

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Patrick Woidy

2016-12-01

Full Text Available Pentaammine dioxide uranium(V nitrate ammonia (1/1, [UO2(NH35]NO3·NH3, was obtained in the form of yellow crystals from the reaction of caesium uranyl nitrate, Cs[UO2(NO33], and uranium tetrafluoride, UF4, in dry liquid ammonia. The [UO2]+ cation is coordinated by five ammine ligands. The resulting [UO2(NH35] coordination polyhedron is best described as a pentagonal bipyramid with the O atoms forming the apices. In the crystal, numerous N—H...N and N—H...O hydrogen bonds are present between the cation, anion and solvent molecules, leading to a three-dimensional network.

Different transport behaviors of NH4 (+) and NH3 in transmembrane cyclic peptide nanotubes.

Science.gov (United States)

Zhang, Mingming; Fan, Jianfen; Xu, Jian; Weng, Peipei; Lin, Huifang

2016-10-01

Two water-filled transmembrane cyclic peptide nanotubes (CPNTs) of 8×cyclo-(WL)n=4,5/POPE were chosen to investigate the dependences of the transport properties of the positive NH4 (+) and neutral NH3 on the channel radius. Molecular dynamic simulations revealed that molecular charge, size, ability to form H-bonds and channel radius all significantly influence the behaviors of NH4 (+) and NH3 in a CPNT. Higher electrostatic interactions, more H-bonds, and water-bridges were found in the NH4 (+) system, resulting in NH4 (+) meeting higher energy barriers, while NH3 can enter, exit and permeate the channels effortlessly. This work sheds a first light on the differences between the mechanisms of NH4 (+) and NH3 moving in a CPNT at an atomic level. Graphical Abstract Snapshot of the simulation system of NH4 (+)_octa-CPNT with an NH4 (+) initially positioned at one mouth of the tube, PMF profiles for single NH4 (+) ion and NH3 molecule moving through water-filled transmembrane CPNTs of 8×cyclo-(WL)n=4,5/POPE and sketch graphs of the possible H-bond forms of NH3 and NH4 (+) with the neighboring water.

Depletion of the heaviest stable N isotope is associated with NH4+/NH3 toxicity in NH4+-fed plants.

Science.gov (United States)

Ariz, Idoia; Cruz, Cristina; Moran, Jose F; González-Moro, María B; García-Olaverri, Carmen; González-Murua, Carmen; Martins-Loução, Maria A; Aparicio-Tejo, Pedro M

2011-05-16

In plants, nitrate (NO3-) nutrition gives rise to a natural N isotopic signature (δ15N), which correlates with the δ15N of the N source. However, little is known about the relationship between the δ15N of the N source and the 14N/15N fractionation in plants under ammonium (NH4+) nutrition. When NH4+ is the major N source, the two forms, NH4+ and NH3, are present in the nutrient solution. There is a 1.025 thermodynamic isotope effect between NH3 (g) and NH4+ (aq) which drives to a different δ15N. Nine plant species with different NH4+-sensitivities were cultured hydroponically with NO3- or NH4+ as the sole N sources, and plant growth and δ15N were determined. Short-term NH4+/NH3 uptake experiments at pH 6.0 and 9.0 (which favours NH3 form) were carried out in order to support and substantiate our hypothesis. N source fractionation throughout the whole plant was interpreted on the basis of the relative transport of NH4+ and NH3. Several NO3--fed plants were consistently enriched in 15N, whereas plants under NH4+ nutrition were depleted of 15N. It was shown that more sensitive plants to NH4+ toxicity were the most depleted in 15N. In parallel, N-deficient pea and spinach plants fed with 15NH4+ showed an increased level of NH3 uptake at alkaline pH that was related to the 15N depletion of the plant. Tolerant to NH4+ pea plants or sensitive spinach plants showed similar trend on 15N depletion while slight differences in the time kinetics were observed during the initial stages. The use of RbNO3 as control discarded that the differences observed arise from pH detrimental effects. This article proposes that the negative values of δ15N in NH4+-fed plants are originated from NH3 uptake by plants. Moreover, this depletion of the heavier N isotope is proportional to the NH4+/NH3 toxicity in plants species. Therefore, we hypothesise that the low affinity transport system for NH4+ may have two components: one that transports N in the molecular form and is associated with

Depletion of the heaviest stable N isotope is associated with NH4+/NH3 toxicity in NH4+-fed plants

Science.gov (United States)

2011-01-01

Background In plants, nitrate (NO3-) nutrition gives rise to a natural N isotopic signature (δ15N), which correlates with the δ15N of the N source. However, little is known about the relationship between the δ15N of the N source and the 14N/15N fractionation in plants under ammonium (NH4+) nutrition. When NH4+ is the major N source, the two forms, NH4+ and NH3, are present in the nutrient solution. There is a 1.025 thermodynamic isotope effect between NH3 (g) and NH4+ (aq) which drives to a different δ15N. Nine plant species with different NH4+-sensitivities were cultured hydroponically with NO3- or NH4+ as the sole N sources, and plant growth and δ15N were determined. Short-term NH4+/NH3 uptake experiments at pH 6.0 and 9.0 (which favours NH3 form) were carried out in order to support and substantiate our hypothesis. N source fractionation throughout the whole plant was interpreted on the basis of the relative transport of NH4+ and NH3. Results Several NO3--fed plants were consistently enriched in 15N, whereas plants under NH4+ nutrition were depleted of 15N. It was shown that more sensitive plants to NH4+ toxicity were the most depleted in 15N. In parallel, N-deficient pea and spinach plants fed with 15NH4+ showed an increased level of NH3 uptake at alkaline pH that was related to the 15N depletion of the plant. Tolerant to NH4+ pea plants or sensitive spinach plants showed similar trend on 15N depletion while slight differences in the time kinetics were observed during the initial stages. The use of RbNO3 as control discarded that the differences observed arise from pH detrimental effects. Conclusions This article proposes that the negative values of δ15N in NH4+-fed plants are originated from NH3 uptake by plants. Moreover, this depletion of the heavier N isotope is proportional to the NH4+/NH3 toxicity in plants species. Therefore, we hypothesise that the low affinity transport system for NH4+ may have two components: one that transports N in the

Interaction of N-hydroxyurea with strong proton donors: HCl and HF

Science.gov (United States)

Sałdyka, Magdalena

2014-11-01

An infrared spectroscopic and MP2/6-311++G(2d,2p) study of strong hydrogen bonded complexes of N-hydroxyurea (NH2CONHOH) with hydrogen halides (HCl and HF) trapped in solid argon matrices is reported. 1:1 and 1:2 complexes between N-hydroxyurea and hydrogen chloride, hydrogen fluoride have been identified in the NH2CONHOH/HCl/Ar, NH2CONHOH/HF/Ar matrices, respectively; their structures were determined by comparison of the spectra with the results of calculations. In the 1:1 complexes, identified for both hydrogen halide molecules, the cyclic structure stabilized by the X-H⋯O and N-H⋯X bonds is present; for the NH2CONHOH⋯HF system another isomeric 1:1 complex is also observed. Two 1:2 complexes were identified for the N-hydroxyurea-hydrogen chloride system characterised by the Cl-H⋯O and N-H⋯Cl bonds. The results of the study evidence that N-hydroxyurea is an oxygen base in the gas-phase with the carbonyl group as the strongest proton acceptor centre in the molecule.

Depletion of the heaviest stable N isotope is associated with NH4+/NH3 toxicity in NH4+-fed plants

Directory of Open Access Journals (Sweden)

Martins-Loução Maria A

2011-05-01

Full Text Available Abstract Background In plants, nitrate (NO3- nutrition gives rise to a natural N isotopic signature (δ15N, which correlates with the δ15N of the N source. However, little is known about the relationship between the δ15N of the N source and the 14N/15N fractionation in plants under ammonium (NH4+ nutrition. When NH4+ is the major N source, the two forms, NH4+ and NH3, are present in the nutrient solution. There is a 1.025 thermodynamic isotope effect between NH3 (g and NH4+ (aq which drives to a different δ15N. Nine plant species with different NH4+-sensitivities were cultured hydroponically with NO3- or NH4+ as the sole N sources, and plant growth and δ15N were determined. Short-term NH4+/NH3 uptake experiments at pH 6.0 and 9.0 (which favours NH3 form were carried out in order to support and substantiate our hypothesis. N source fractionation throughout the whole plant was interpreted on the basis of the relative transport of NH4+ and NH3. Results Several NO3--fed plants were consistently enriched in 15N, whereas plants under NH4+ nutrition were depleted of 15N. It was shown that more sensitive plants to NH4+ toxicity were the most depleted in 15N. In parallel, N-deficient pea and spinach plants fed with 15NH4+ showed an increased level of NH3 uptake at alkaline pH that was related to the 15N depletion of the plant. Tolerant to NH4+ pea plants or sensitive spinach plants showed similar trend on 15N depletion while slight differences in the time kinetics were observed during the initial stages. The use of RbNO3 as control discarded that the differences observed arise from pH detrimental effects. Conclusions This article proposes that the negative values of δ15N in NH4+-fed plants are originated from NH3 uptake by plants. Moreover, this depletion of the heavier N isotope is proportional to the NH4+/NH3 toxicity in plants species. Therefore, we hypothesise that the low affinity transport system for NH4+ may have two components: one that

WARM HCN IN THE PLANET FORMATION ZONE OF GV TAU N

Energy Technology Data Exchange (ETDEWEB)

Fuente, Asuncion [Observatorio Astronomico Nacional (OAN,IGN), Apdo 112, E-28803 Alcala de Henares (Spain); Cernicharo, Jose; Agundez, Marcelino, E-mail: a.fuente@oan.es [Centro de Astrobiologia (CSIC/INTA), Laboratory of Molecular Astrophysics, Ctra. Ajalvir km. 4, E-28850 Torrejon de Ardoz (Spain)

2012-07-20

The Plateau de Bure Interferometer has been used to map the continuum emission at 3.4 mm and 1.1 mm together with the J = 1{yields}0 and J = 3{yields}2 lines of HCN and HCO{sup +} toward the binary star GV Tau. The 3.4 mm observations did not resolve the binary components, and the HCN J = 1{yields}0 and HCO{sup +} J 1{yields}0 line emissions trace the circumbinary disk and the flattened envelope. However, the 1.1 mm observations resolved the individual disks of GV Tau N and GV Tau S and allowed us to study their chemistry. We detected the HCN 3{yields}2 line only toward the individual disk of GV Tau N, and the emission of the HCO{sup +} 3{yields}2 line toward GV Tau S. Simple calculations indicate that the 3{yields}2 line of HCN is formed in the inner R < 12 AU of the disk around GV Tau N where the HCN/HCO{sup +} abundance ratio is >300. On the contrary, this ratio is <1.6 in the disk around GV Tau S. The high HCN abundance measured in GV Tau N is well explained by photochemical processes in the warm (>400 K) and dense (n > 10{sup 7} cm{sup -3}) disk surface.

CO and HCN observations of carbon stars

NARCIS (Netherlands)

Baas, F; deJong, T; Loup, C

We present CO and HCN observations of carbon stars. They consist of partly new detections in the (CO)-C-12 J = (1-0), (2-1) and HCN(1-0) lines obtained with the SEST and the IRAM telescope, and of (CO)-C-12 and (CO)-C-13 J = (1-0), (2-1) and (3-2) observations with IRAM and the JCMT of some of the

Dysfunctional HCN ion channels in neurological diseases

Directory of Open Access Journals (Sweden)

Jacopo C. DiFrancesco

2015-03-01

Full Text Available Hyperpolarization-activated cyclic nucleotide-gated (HCN channels are expressed as four different isoforms (HCN1-4 in the heart and in the central and peripheral nervous systems. HCN channels are activated by membrane hyperpolarization at voltages close to resting membrane potentials and carry the hyperpolarization-activated current, dubbed If (funny current in heart and Ih in neurons. HCN channels contribute in several ways to neuronal activity and are responsible for many important cellular functions, including cellular excitability, generation and modulation of rhythmic activity, dendritic integration, transmission of synaptic potentials and plasticity phenomena. Because of their role, defective HCN channels are natural candidates in the search for potential causes of neurological disorders in humans. Several data, including growing evidence that some forms of epilepsy are associated with HCN mutations, support the notion of an involvement of dysfunctional HCN channels in different experimental models of the disease. Additionally, some anti-epileptic drugs are known to modify the activity of the Ih current. HCN channels are widely expressed in the peripheral nervous system and recent evidence has highlighted the importance of the HCN2 isoform in the transmission of pain. HCN channels are also present in the midbrain system, where they finely regulate the activity of dopaminergic neurons, and a potential role of these channels in the pathogenesis of Parkinson’s disease has recently emerged. The function of HCN channels is regulated by specific accessory proteins, which control the correct expression and modulation of the neuronal Ih current. Alteration of these proteins can severely interfere with the physiological channel function, potentially predisposing to pathological conditions. In this review we address the present knowledge of the association between HCN dysfunctions and neurological diseases, including clinical, genetic and

ALMA DETECTION OF THE VIBRATIONALLY EXCITED HCN J = 4-3 EMISSION LINE IN THE AGN-HOSTING LUMINOUS INFRARED GALAXY IRAS 20551–4250

Energy Technology Data Exchange (ETDEWEB)

Imanishi, Masatoshi [Subaru Telescope, 650 North A' ohoku Place, Hilo, Hawaii, 96720 (United States); Nakanishi, Kouichiro, E-mail: masa.imanishi@nao.ac.jp [Joint ALMA Observatory, Alonso de Córdova 3107, Vitacura 763-0355, Santiago de Chile (Chile)

2013-10-01

We present results from our ALMA Cycle 0 observations, at the frequencies around the HCN, HCO{sup +}, and HNC J = 4-3 transition lines, of the luminous infrared galaxy IRAS 20551–4250 at z = 0.043, which is known to host an energetically important obscured active galactic nucleus (AGN). In addition to the targeted HCN, HCO{sup +}, and HNC J = 4-3 emission lines, two additional strong emission lines are seen, which we attribute to H{sub 2}S and CH{sub 3}CN(+CCH). The HCN-to-HCO{sup +} J = 4-3 flux ratio (∼0.7) is higher than in the other starburst-dominated galaxy (∼0.2) observed in our ALMA Cycle 0 program. We tentatively (∼5σ) detected the vibrationally excited (v {sub 2} = 1) HCN J = 4-3 (l = 1f) emission line, which is important for testing an infrared radiative pumping scenario for HCN. This is the second detection of this molecular transition in external galaxies. The most likely reason for this detection is not only the high flux of this emission line, but also the small molecular line widths observed in this galaxy, suggesting that vibrational excitation of HCN may be relatively common in AGN-hosting galaxies.

Performance evaluation of poly-urethane foam packed-bed chemical scrubber for the oxidative absorption of NH3 and H2S gases.

Science.gov (United States)

Nisola, Grace M; Valdehuesa, Kris Niño G; Anonas, Alex V; Ramos, Kristine Rose M; Lee, Won-Keun; Chung, Wook-Jin

2018-01-02

The feasibility of open-pore polyurethane (PU) foam as packing material for wet chemical scrubber was tested for NH 3 and H 2 S removals. The foam is inexpensive, light-weight, highly porous (low pressure drop) and provides large surface area per unit volume, which are desirable properties for enhanced gas/liquid mass transfer. Conventional HCl/HOCl (for NH 3 ) and NaOH/NaOCl (for H 2 S) scrubbing solutions were used to absorb and oxidize the gases. Assessment of the wet chemical scrubbers reveals that pH and ORP levels are important to maintain the gas removal efficiencies >95%. A higher re-circulation rate of scrubbing solutions also proved to enhance the performance of the NH 3 and H 2 S columns. Accumulation of salts was confirmed by the gradual increase in total dissolved solids and conductivity values of scrubbing solutions. The critical elimination capacities at >95% gas removals were found to be 5.24 g NH 3 -N/m 3 -h and 17.2 g H 2 S-S/m 3 -h at an empty bed gas residence time of 23.6 s. Negligible pressure drops (scrubbers for NH 3 and H 2 S removals from high-volume dilute emissions.

MEG3, HCN3 and linc01105 influence the proliferation and apoptosis of neuroblastoma cells via the HIF-1α and p53 pathways.

Science.gov (United States)

Tang, Weitao; Dong, Kuiran; Li, Kai; Dong, Rui; Zheng, Shan

2016-11-08

The purpose of this study was to investigate the differential expression and functional roles of long non-coding RNAs (lncRNAs) in neuroblastoma tissue. LncRNA microarrays were used to identify differentially expressed lncRNAs between tumor and para-tumor tissues. In total, in tumor tissues, 3,098 and 1,704 lncRNAs were upregulated and downregulated, respectively. HCN3 and linc01105 exhibited the higher expression (P INSS) stage were -0.48, -0.58 and -0.55, respectively. In conclusion, we have identified lncRNAs that are differentially expressed in neuroblastoma tissues. The lncRNAs HCN3, linc01105, and MEG3 may be important in biological behaviors of neuroblastoma through mechanisms involving p53 pathway members such as HIF-1α, Noxa, and Bid. The expressions of MEG3, HCN3 and linc01105 are all negatively correlated with the INSS stage.

Low Temperature Growth of In2O3and InN Nanocrystals on Si(111 via Chemical Vapour Deposition Based on the Sublimation of NH4Cl in In

Directory of Open Access Journals (Sweden)

Tsokkou Demetra

2009-01-01

Full Text Available Abstract Indium oxide (In2O3 nanocrystals (NCs have been obtained via atmospheric pressure, chemical vapour deposition (APCVD on Si(111 via the direct oxidation of In with Ar:10% O2at 1000 °C but also at temperatures as low as 500 °C by the sublimation of ammonium chloride (NH4Cl which is incorporated into the In under a gas flow of nitrogen (N2. Similarly InN NCs have also been obtained using sublimation of NH4Cl in a gas flow of NH3. During oxidation of In under a flow of O2the transfer of In into the gas stream is inhibited by the formation of In2O3around the In powder which breaks up only at high temperatures, i.e.T > 900 °C, thereby releasing In into the gas stream which can then react with O2leading to a high yield formation of isolated 500 nm In2O3octahedrons but also chains of these nanostructures. No such NCs were obtained by direct oxidation forT G < 900 °C. The incorporation of NH4Cl in the In leads to the sublimation of NH4Cl into NH3and HCl at around 338 °C which in turn produces an efficient dispersion and transfer of the whole In into the gas stream of N2where it reacts with HCl forming primarily InCl. The latter adsorbs onto the Si(111 where it reacts with H2O and O2leading to the formation of In2O3nanopyramids on Si(111. The rest of the InCl is carried downstream, where it solidifies at lower temperatures, and rapidly breaks down into metallic In upon exposure to H2O in the air. Upon carrying out the reaction of In with NH4Cl at 600 °C under NH3as opposed to N2, we obtain InN nanoparticles on Si(111 with an average diameter of 300 nm.

Radiation chemical behavior of Rh(III) in HClO4 and HNO3

International Nuclear Information System (INIS)

Vladimirova, M.V.; Khalkina, E.V.

1995-01-01

The radiation chemical behavior of Rh is very interesting since Rh accumulates in irradiated U but has not been reported in the literature. Scattered data do exist for the radiation chemical behavior of Rh(III) in weakly acidic and alkaline solutions. Pulsed radiolysis was used to investigate the formation of unstable oxidation states of Rh during reduction and oxidation of Rh(III) in neutral solutions. The rate constant of the reaction Rh(III) + e aq - was found to be 6·10 10 liter/mole·sec. The radiation chemical behavior of Rh(III) toward γ-radiolysis in neutral, weakly acidic (up to 0.1 N), and alkaline solutions was examined. In neutral solutions of [Rh(NH 3 ) 5 Cl]Cl 2 and RhCl 3 , metallic Rh is formed. The degree of reduction is ∼ 1%. In neutral and weakly acidic solutions of Rh(NO 3 ) 3 , Rh 2 O 3 ·xH 2 O is formed. Irradiation of Rh(ClO 4 ) 3 solutions produces no reduction. The radiation chemical behavior of Rh(III) in HClO 4 and HNO 3 solutions at concentrations > 1 M is studied in the present work

Aquaporin 4 as a NH3 Channel

DEFF Research Database (Denmark)

Assentoft, Mette; Kaptan, Shreyas; Schneider, Hans-Peter

2016-01-01

-brain-interface, participate in the exchange of ammonia, which is required to sustain the glutamate-glutamine cycle. Here we observe that AQP4-expressing Xenopus oocytes display a reflection coefficient NH4Cl at pH 8.0, at which pH an increased amount of the ammonia occurs in the form of NH3 Taken together with an NH4......Cl-mediated intracellular alkalization (or lesser acidification) of AQP4-expressing oocytes, these data suggest that NH3 is able to permeate the pore of AQP4. Exposure to NH4Cl increased the membrane currents to a similar extent in uninjected oocytes and in oocytes expressing AQP4, indicating...... that the ionic NH4 (+) did not permeate AQP4. Molecular dynamics simulations revealed partial pore permeation events of NH3 but not of NH4 (+) and a reduced energy barrier for NH3 permeation through AQP4 compared with that of a cholesterol-containing lipid bilayer, suggesting AQP4 as a favored transmembrane...

Biomolecules from HCN

Science.gov (United States)

Ferris, J. P.; Wos, J. D.; Ryan, T. J.; Lobo, A. P.; Donner, D. B.

1974-01-01

It has been suggested by Sanchez et al. (1967) that HCN might have been one of the more important precursors of biological molecules on the primitive earth. Studies were conducted to determine the mechanisms involved in HCN oligomerizations in dilute aqueous solutions and to identify the compounds which are produced in these oligomerization mixtures. Indirect evidence for the formation of cyanate was obtained along with direct evidence for the formation of citrulline, aspartic acid, and orotic acid.

Real-time observation of formation and relaxation dynamics of NH4 in (CH3OH)m(NH3)n clusters.

Science.gov (United States)

Yamada, Yuji; Nishino, Yoko; Fujihara, Akimasa; Ishikawa, Haruki; Fuke, Kiyokazu

2009-03-26

The formation and relaxation dynamics of NH4(CH3OH)m(NH3)n clusters produced by photolysis of ammonia-methanol mixed clusters has been observed by a time-resolved pump-probe method with femtosecond pulse lasers. From the detailed analysis of the time evolutions of the protonated cluster ions, NH4(+)(CH3OH)m(NH3)n, the kinetic model has been constructed, which consists of sequential three-step reaction: ultrafast hydrogen-atom transfer producing the radical pair (NH4-NH2)*, the relaxation process of radical-pair clusters, and dissociation of the solvated NH4 clusters. The initial hydrogen transfer hardly occurs between ammonia and methanol, implying the unfavorable formation of radical pair, (CH3OH2-NH2)*. The remarkable dependence of the time constants in each step on the number and composition of solvents has been explained by the following factors: hydrogen delocalization within the clusters, the internal conversion of the excited-state radical pair, and the stabilization of NH4 by solvation. The dependence of the time profiles on the probe wavelength is attributed to the different ionization efficiency of the NH4(CH3OH)m(NH3)n clusters.

NMR Spectroscopic Characterization of Methylcobalt(III) Compounds with Classical Ligands. Crystal Structures of [Co(NH(3))(5)(CH(3))]S(2)O(6), trans-[Co(en)(2)(NH(3))(CH(3))]S(2)O(6) (en = 1,2-Ethanediamine), and [Co(NH(3))(6)]-mer,trans-[Co(NO(2))(3)(NH(

DEFF Research Database (Denmark)

Kofod, Pauli; Harris, Pernille; Larsen, Sine

1997-01-01

magnetic resonance spectroscopy and by absorption spectroscopy. Single-crystal X-ray structure determinations at 122.0(5) K were performed on [Co(NH(3))(5)(CH(3))]S(2)O(6) (1), trans-[Co(en)(2)(NH(3))(CH(3))]S(2)O(6) (2), and [Co(NH(3))(6)]-mer,trans-[Co(NO(2))(3)(NH(3))(2)(CH(3))](2)-trans-[Co(NO(2...

A liquid-based eutectic system: LiBH4·NH 3-nNH3BH3 with high dehydrogenation capacity at moderate temperature

KAUST Repository

Tan, Yingbin; Guo, Yanhui; Li, Shaofeng; Sun, Weiwei; Zhu, Yihan; Li, Qi; Yu, Xuebin

2011-01-01

A novel eutectic hydrogen storage system, LiBH4·NH 3-nNH3BH3, which exists in a liquid state at room temperature, was synthesized through a simple mixing of LiBH 4·NH3 and NH3BH3 (AB). In the temperature range of 90-110 °C, the eutectic system

Photostriction of CH3NH3PbBr3 Perovskite Crystals

KAUST Repository

Wei, Tzu-Chiao

2017-07-17

Organic-inorganic hybrid perovskite materials exhibit a variety of physical properties. Pronounced coupling between phonon, organic cations, and the inorganic framework suggest that these materials exhibit strong light-matter interactions. The photoinduced strain of CH3 NH3 PbBr3 is investigated using high-resolution and contactless in situ Raman spectroscopy. Under illumination, the material exhibits large blue shifts in its Raman spectra that indicate significant structural deformations (i.e., photostriction). From these shifts, the photostrictive coefficient of CH3 NH3 PbBr3 is calculated as 2.08 × 10-8 m2 W-1 at room temperature under visible light illumination. The significant photostriction of CH3 NH3 PbBr3 is attributed to a combination of the photovoltaic effect and translational symmetry loss of the molecular configuration via strong translation-rotation coupling. Unlike CH3 NH3 PbI3 , it is noted that the photostriction of CH3 NH3 PbBr3 is extremely stable, demonstrating no signs of optical decay for at least 30 d. These results suggest the potential of CH3 NH3 PbBr3 for applications in next-generation optical micro-electromechanical devices.

CN and HCN in the infrared spectrum of IRC + 10216

Science.gov (United States)

Wiedemann, G. R.; Deming, D.; Jennings, D. E.; Hinkle, Kenneth H.; Keady, John J.

1991-01-01

The abundance of HCN in the inner circumstellar shell of IRC + 10216 has been remeasured using the 12-micron nu2 band. The 12-micron lines are less saturated than HCN 3-micron lines previously detected in the spectrum of IRC + 10216. The observed 12-micron HCN line is formed in the circumstellar shell from about 4 to 12 R sub * in accord with a photospheric origin for HCN. The derived HCN abundance in the 4 to 12 R sub* region is 4 x 10 exp-5 and the column density is 7 x 10 exp 18/sq cm. The 5-micron CN vibration-rotation fundamental band was detected for the first time in an astronomical source. Using four CN lines, the CN column density was determined to be 2.6 x 10 exp 15/sq cm and the rotational temperature to be 8 +/-2 K. The peal radial abundance is 1 x 10 exp -5. The values for the temperature and abundance are in good agreement with microwave results and with the formation of CN from the photolysis of HCN.

Investigation on thermal evaporated CH3NH3PbI3 thin films

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Youzhen Li

2015-09-01

Full Text Available CH3NH3I, PbI2 and CH3NH3PbI3 films were fabricated by evaporation and characterized with X-ray Photoelectron Spectroscopy (XPS and X-ray diffraction (XRD. The XPS results indicate that the PbI2 and CH3NH3PbI3 films are more uniform and stable than the CH3NH3I film. The atomic ratio of the CH3NH3I, PbI2 and CH3NH3PbI3 films are C:N:I=1.00:1.01:0.70, Pb:I= 1.00:1.91 and C: N: Pb: I = 1.29:1.07:1.00:2.94, respectively. The atomic ratio of CH3NH3PbI3 is very close to that of the ideal perovskite. Small angle x-ray diffraction results demonstrate that the as evaporated CH3NH3PbI3 film is crystalline. The valence band maximum (VBM and work function (WF of the CH3NH3PbI3 film are about 0.85eV and 4.86eV, respectively.

Glycine formation in CO2:CH4:NH3 ices induced by 0-70 eV electrons

Science.gov (United States)

Esmaili, Sasan; Bass, Andrew D.; Cloutier, Pierre; Sanche, Léon; Huels, Michael A.

2018-04-01

Glycine (Gly), the simplest amino-acid building-block of proteins, has been identified on icy dust grains in the interstellar medium, icy comets, and ice covered meteorites. These astrophysical ices contain simple molecules (e.g., CO2, H2O, CH4, HCN, and NH3) and are exposed to complex radiation fields, e.g., UV, γ, or X-rays, stellar/solar wind particles, or cosmic rays. While much current effort is focused on understanding the radiochemistry induced in these ices by high energy radiation, the effects of the abundant secondary low energy electrons (LEEs) it produces have been mostly assumed rather than studied. Here we present the results for the exposure of multilayer CO2:CH4:NH3 ice mixtures to 0-70 eV electrons under simulated astrophysical conditions. Mass selected temperature programmed desorption (TPD) of our electron irradiated films reveals multiple products, most notably intact glycine, which is supported by control measurements of both irradiated or un-irradiated binary mixture films, and un-irradiated CO2:CH4:NH3 ices spiked with Gly. The threshold of Gly formation by LEEs is near 9 eV, while the TPD analysis of Gly film growth allows us to determine the "quantum" yield for 70 eV electrons to be about 0.004 Gly per incident electron. Our results show that simple amino acids can be formed directly from simple molecular ingredients, none of which possess preformed C—C or C—N bonds, by the copious secondary LEEs that are generated by ionizing radiation in astrophysical ices.

Biopesticide activity of sugarcane associated rhizobacteria: Ochrobactrum intermedium strain NH-5 and Stenotrophomonas maltophilia strain NH-300 against red rot under field conditions

Directory of Open Access Journals (Sweden)

Muhammad Nadeem HASSAN

2014-09-01

Full Text Available Colletotrichum falcatum is the major fungal pathogen causing sugarcane red rot. Four antagonistic bacterial strains exhibiting biocontrol activity against this pathogen in greenhouse conditions were characterized for production of different antifungal metabolites and biocontrol determinants to elucidate the mechanism of action involved in their antagonistic activity. The strains were also evaluated under field conditions to assess their biocontrol potential. All the strains produced hydrogen cyanide (HCN, and volatile and diffusible antibiotics. In addition, the Ochrobactrum intermedium strain NH-5 produced siderophores and the broad spectrum antibiotic 2, 4-diacetylphloroglucinol (2,4-DAPG; Pseudomonas sp. NH-203 produced siderophores, and Pseudomonas sp. NH-276 produced protease. Two strains, Ochrobactrum intermedium NH-5 and Stenotrophomonas maltophilia NH-300, exhibited good biocontrol activity, suppressing red rot by 44–52% on two sugarcane varieties, SPF-234 and Co-1148, in field experiments. The strains gave consistent results in three consecutive years and showed potential to be used as biopesticides.

Kinetics of the CH3 + HCl/DCl → CH4/CH3D + Cl and CD3 + HCl/DCl → CD3H/CD4 + Cl reactions: An experimental H atom tunneling investigation

International Nuclear Information System (INIS)

Eskola, Arkke J.; Seetula, Jorma A.; Timonen, Raimo S.

2006-01-01

The kinetics of the radical reactions of CH 3 with HCl or DCl and CD 3 with HCl or DCl have been investigated in a temperature controlled tubular reactor coupled to a photoionization mass spectrometer. The CH 3 (or CD 3 ) radical, R, was produced homogeneously in the reactor by a pulsed 193 nm exciplex laser photolysis of CH 3 COCH 3 (or CD 3 COCD 3 ). The decay of CH 3 /CD 3 was monitored as a function of HCl/DCl concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature, typically from 188 to 500 K. The rate constants of the CH 3 and CD 3 reactions with HCl had strong non-Arrhenius behavior at low temperatures. The rate constants were fitted to a modified Arrhenius expression k = QA exp (-E a /RT) (error limits stated are 1σ + Students t values, units in cm 3 molecule -1 s -1 ): k(CH 3 + HCl) = [1.004 + 85.64 exp (-0.02438 x T/K)] x (3.3 ± 1.3) x 10 -13 exp [-(4.8 ± 0.6) kJ mol -1 /RT] and k(CD 3 + HCl) = [1.002 + 73.31 exp (-0.02505 x T/K)] x (2.7 ± 1.2) x 10 -13 exp [-(3.5 ± 0.5) kJ mol -1 /RT]. The radical reactions with DCl were studied separately over a wide ranges of temperatures and in these temperature ranges the rate constants determined were fitted to a conventional Arrhenius expression k = A exp (-E a /RT) (error limits stated are 1σ + Students t values, units in cm 3 molecule -1 s -1 ): k(CH 3 + DCl) = (2.4 ± 1.6) x 10 -13 exp [-(7.8 ± 1.4) kJ mol -1 /RT] and k(CD 3 + DCl) = (1.2 ± 0.4) x 10 -13 exp [-(5.2 ± 0.2) kJ mol -1 /RT] cm 3 molecule -1 s -1 . Curvature in the Arrhenius plots of the H-atom abstraction reactions at low temperatures was analyzed by considering H-atom tunneling through the reaction barrier and primary kinetic isotope effect. Contribution of tunneling in it was concluded to be negligible. In addition, secondary isotope effect was measured

A liquid-based eutectic system: LiBH4·NH 3-nNH3BH3 with high dehydrogenation capacity at moderate temperature

KAUST Repository

Tan, Yingbin

2011-01-01

A novel eutectic hydrogen storage system, LiBH4·NH 3-nNH3BH3, which exists in a liquid state at room temperature, was synthesized through a simple mixing of LiBH 4·NH3 and NH3BH3 (AB). In the temperature range of 90-110 °C, the eutectic system showed significantly improved dehydrogenation properties compared to the neat AB and LiBH 4·NH3 alone. For example, in the case of the LiBH4·NH3/AB with a mole ratio of 1:3, over 8 wt.% hydrogen could be released at 90 °C within 4 h, while only 5 wt.% hydrogen released from the neat AB at the same conditions. Through a series of experiments it has been demonstrated that the hydrogen release of the new system is resulted from an interaction of AB and the NH3 group in the LiBH4·NH3, in which LiBH4 works as a carrier of ammonia and plays a crucial role in promoting the interaction between the NH3 group and AB. The enhanced dehydrogenation of LiBH 4·NH3/AB may result from the polar liquid state reaction environments and the initially promoted formation of the diammoniate of diborane, which will facilitate the B-H⋯H-N interaction between LiBH4·NH3 and AB. Kinetics analysis revealed that the rate-controlling steps of the dehydrogenation process are three-dimensional diffusion of hydrogen at temperatures ranging from 90 to 110 °C. This journal is © The Royal Society of Chemistry.

Low Temperature Catalyst for NH3 Removal

Science.gov (United States)

Monje, Oscar; Melendez, Orlando

2013-01-01

Air revitalization technologies maintain a safe atmosphere inside spacecraft by the removal of C02, ammonia (NH3), and trace contaminants. NH3 onboard the International Space Station (ISS) is produced by crew metabolism, payloads, or during an accidental release of thermal control refrigerant. Currently, the ISS relies on removing NH3 via humidity condensate and the crew wears hooded respirators during emergencies. A different approach to cabin NH3 removal is to use selective catalytic oxidation (SCO), which builds on thermal catalytic oxidation concepts that could be incorporated into the existing TCCS process equipment architecture on ISS. A low temperature platinum-based catalyst (LTP-Catalyst) developed at KSC was used for converting NH3 to H20 and N2 gas by SCO. The challenge of implementing SCO is to reduce formation of undesirable byproducts like NOx (N20 and NO). Gas mixture analysis was conducted using FTIR spectrometry in the Regenerable VOC Control System (RVCS) Testbed. The RVCS was modified by adding a 66 L semi-sealed chamber, and a custom NH3 generator. The effect of temperature on NH3 removal using the LTP-Catalyst was examined. A suitable temperature was found where NH3 removal did not produce toxic NO, (NO, N02) and N20 formation was reduced.

Thin-Film Transformation of NH4 PbI3 to CH3 NH3 PbI3 Perovskite: A Methylamine-Induced Conversion-Healing Process.

Science.gov (United States)

Zong, Yingxia; Zhou, Yuanyuan; Ju, Minggang; Garces, Hector F; Krause, Amanda R; Ji, Fuxiang; Cui, Guanglei; Zeng, Xiao Cheng; Padture, Nitin P; Pang, Shuping

2016-11-14

Methylamine-induced thin-film transformation at room-temperature is discovered, where a porous, rough, polycrystalline NH 4 PbI 3 non-perovskite thin film converts stepwise into a dense, ultrasmooth, textured CH 3 NH 3 PbI 3 perovskite thin film. Owing to the beneficial phase/structural development of the thin film, its photovoltaic properties undergo dramatic enhancement during this NH 4 PbI 3 -to-CH 3 NH 3 PbI 3 transformation process. The chemical origins of this transformation are studied at various length scales. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

WARM HCN IN THE PLANET FORMATION ZONE OF GV TAU N

International Nuclear Information System (INIS)

Fuente, Asunción; Cernicharo, José; Agúndez, Marcelino

2012-01-01

The Plateau de Bure Interferometer has been used to map the continuum emission at 3.4 mm and 1.1 mm together with the J = 1→0 and J = 3→2 lines of HCN and HCO + toward the binary star GV Tau. The 3.4 mm observations did not resolve the binary components, and the HCN J = 1→0 and HCO + J 1→0 line emissions trace the circumbinary disk and the flattened envelope. However, the 1.1 mm observations resolved the individual disks of GV Tau N and GV Tau S and allowed us to study their chemistry. We detected the HCN 3→2 line only toward the individual disk of GV Tau N, and the emission of the HCO + 3→2 line toward GV Tau S. Simple calculations indicate that the 3→2 line of HCN is formed in the inner R + abundance ratio is >300. On the contrary, this ratio is 400 K) and dense (n > 10 7 cm –3 ) disk surface.

Role of NH3 and NH4+ transporters in renal acid-base transport.

Science.gov (United States)

Weiner, I David; Verlander, Jill W

2011-01-01

Renal ammonia excretion is the predominant component of renal net acid excretion. The majority of ammonia excretion is produced in the kidney and then undergoes regulated transport in a number of renal epithelial segments. Recent findings have substantially altered our understanding of renal ammonia transport. In particular, the classic model of passive, diffusive NH3 movement coupled with NH4+ "trapping" is being replaced by a model in which specific proteins mediate regulated transport of NH3 and NH4+ across plasma membranes. In the proximal tubule, the apical Na+/H+ exchanger, NHE-3, is a major mechanism of preferential NH4+ secretion. In the thick ascending limb of Henle's loop, the apical Na+-K+-2Cl- cotransporter, NKCC2, is a major contributor to ammonia reabsorption and the basolateral Na+/H+ exchanger, NHE-4, appears to be important for basolateral NH4+ exit. The collecting duct is a major site for renal ammonia secretion, involving parallel H+ secretion and NH3 secretion. The Rhesus glycoproteins, Rh B Glycoprotein (Rhbg) and Rh C Glycoprotein (Rhcg), are recently recognized ammonia transporters in the distal tubule and collecting duct. Rhcg is present in both the apical and basolateral plasma membrane, is expressed in parallel with renal ammonia excretion, and mediates a critical role in renal ammonia excretion and collecting duct ammonia transport. Rhbg is expressed specifically in the basolateral plasma membrane, and its role in renal acid-base homeostasis is controversial. In the inner medullary collecting duct (IMCD), basolateral Na+-K+-ATPase enables active basolateral NH4+ uptake. In addition to these proteins, several other proteins also contribute to renal NH3/NH4+ transport. The role and mechanisms of these proteins are discussed in depth in this review.

Broadening of spectral lines of CO2, N2O , H2CO, HCN, and H2S by pressure of gases dominant in planetary atmospheres (H2, He and CO2)

Science.gov (United States)

Samuels, Shanelle; Gordon, Iouli; Tan, Yan

2018-01-01

HITRAN1,2 is a compilation of spectroscopic parameters that a variety of computer codes use to predict and simulate the transmission and emission of light in planetary atmospheres. The goal of this project is to add to the potential of the HITRAN database towards the exploration of the planetary atmospheres by including parameters describing broadening of spectral lines by H2, CO2, and He. These spectroscopic data are very important for the study of the hydrogen and helium-rich atmospheres of gas giants as well as rocky planets with volcanic activities, including Venus and Mars, since their atmospheres are dominated by CO2. First step in this direction was accomplished by Wilzewski et al.3 where this was done for SO2, NH3, HF, HCl, OCS and C2H2. The molecules investigated in this work were CO2, N2O, H2CO, HCN and H2S. Line-broadening coefficients, line shifts and temperature-dependence exponents for transitions of these molecules perturbed by H2, CO2 and He have been assembled from available peer-reviewed experimental and theoretical sources. The data was evaluated and the database was populated with these data and their extrapolations/interpolations using semi-empirical models that were developed to this end.Acknowledgements: Financial support from NASA PDART grant NNX16AG51G and the Smithsonian Astrophysical Observatory Latino Initiative Program from the Latino Initiatives Pool, administered by the Smithsonian Latino Center is gratefully acknowledged.References: 1. HITRAN online http://hitran.org/2. Gordon, I.E., Rothman, L.S., Hill, C., Kochanov, R.V., Tan, Y., et al., 2017. The HITRAN2016 Molecular Spectroscopic Database. J. Quant. Spectrosc. Radiat. Transf. doi:10.1016/j.jqsrt.2017.06.0383. Wilzewski, J.S., Gordon, I.E., Kochanov, R. V., Hill, C., Rothman, L.S., 2016. H2, He, and CO2 line-broadening coefficients, pressure shifts and temperature-dependence exponents for the HITRAN database. Part 1: SO2, NH3, HF, HCl, OCS and C2H2. J. Quant. Spectrosc. Radiat

Generation of nanopores during desorption of NH3 from Mg(NH3)6Cl2

DEFF Research Database (Denmark)

Hummelshøj, Jens Strabo; Sørensen, Rasmus Zink; Kostova, M.Y.

2006-01-01

It is shown that nanopores are formed during desorption of NH3 from Mg(NH3)6Cl2, which has been proposed as a hydrogen storage material. The system of nanopores facilitates the transport of desorbed ammonia away from the interior of large volumes of compacted storage material. DFT calculations sh...

Communication: Equivalence between symmetric and antisymmetric stretching modes of NH3 in promoting H + NH3 → H2 + NH2 reaction

Science.gov (United States)

Song, Hongwei; Yang, Minghui; Guo, Hua

2016-10-01

Vibrational excitations of reactants sometimes promote reactions more effectively than the same amount of translational energy. Such mode specificity provides insights into the transition-state modulation of reactivity and might be used to control chemical reactions. We report here a state-of-the-art full-dimensional quantum dynamical study of the hydrogen abstraction reaction H + NH3 → H2 + NH2 on an accurate ab initio based global potential energy surface. This reaction serves as an ideal candidate to study the relative efficacies of symmetric and degenerate antisymmetric stretching modes. Strong mode specificity, particularly for the NH3 stretching modes, is demonstrated. It is further shown that nearly identical efficacies of the symmetric and antisymmetric stretching modes of NH3 in promoting the reaction can be understood in terms of local-mode stretching vibrations of the reactant molecule.

The extraction of uranyl nitrate and chloride in octaethyltetraamidopyrophosphate (OETAPP)-HCl, HNO3 systems

International Nuclear Information System (INIS)

Jankowska, M.; Kulawik, J.; Mikulski, J.

1975-01-01

The extraction of uranium was studied in the system of 0.1 M OETAPP in CHCl 3 /HCl or HNO 3 . The distribution coefficients of HCl and HNO 3 were calculated as a function of OETAPP concentration. The amount of OETAPP in the aqueous phase containing HCl and HNO 3 was found from the measurements of surface tension of this phase. The distribution of HCl or HNO 3 between the organic and aqueous phases was studied as a function of the concentration of the acid used in the aqueous phase. The solvation energy of the extracted complexes was calculated from the measured potential differences. Cohesion and adhesion energies of the studied systems are also given. (author)

Formation of simple nitrogen hydrides NH and NH2 at cryogenic temperatures through N + NH3→ NH + NH2 reaction: dark cloud chemistry of nitrogen.

Science.gov (United States)

Nourry, Sendres; Krim, Lahouari

2016-07-21

Although NH3 molecules interacting with ground state nitrogen atoms N((4)S) seem not to be a very reactive system without providing additional energy to initiate the chemical process, we show through this study that, in the solid phase, at very low temperature, NH3 + N((4)S) reaction leads to the formation of the amidogen radical NH2. Such a dissociation reaction previously thought to occur exclusively through UV photon or energetic particle irradiation is in this work readily occurring just by stimulating the mobility of N((4)S)-atoms in the 3-10 K temperature range in the solid sample. The N((4)S)-N((4)S) recombination may be the source of metastable molecular nitrogen N2(A), a reactive species which might trigger the NH3 dissociation or react with ground state nitrogen atoms N((4)S) to form excited nitrogen atoms N((4)P/(2)D) through energy transfer processes. Based on our obtained results, it is possible to propose reaction pathways to explain the NH2 radical formation which is the first step in the activation of stable species such as NH3, a chemical induction process that, in addition to playing an important role in the origin of molecular complexity in interstellar space, is known to require external energy supplies to occur in the gas phase.

Rapid ammonia gas transport accounts for futile transmembrane cycling under NH3/NH4+ toxicity in plant roots.

Science.gov (United States)

Coskun, Devrim; Britto, Dev T; Li, Mingyuan; Becker, Alexander; Kronzucker, Herbert J

2013-12-01

Futile transmembrane NH3/NH4(+) cycling in plant root cells, characterized by extremely rapid fluxes and high efflux to influx ratios, has been successfully linked to NH3/NH4(+) toxicity. Surprisingly, the fundamental question of which species of the conjugate pair (NH3 or NH4(+)) participates in such fluxes is unresolved. Using flux analyses with the short-lived radioisotope (13)N and electrophysiological, respiratory, and histochemical measurements, we show that futile cycling in roots of barley (Hordeum vulgare) seedlings is predominately of the gaseous NH3 species, rather than the NH4(+) ion. Influx of (13)NH3/(13)NH4(+), which exceeded 200 µmol g(-1) h(-1), was not commensurate with membrane depolarization or increases in root respiration, suggesting electroneutral NH3 transport. Influx followed Michaelis-Menten kinetics for NH3 (but not NH4(+)), as a function of external concentration (Km = 152 µm, Vmax = 205 µmol g(-1) h(-1)). Efflux of (13)NH3/(13)NH4(+) responded with a nearly identical Km. Pharmacological characterization of influx and efflux suggests mediation by aquaporins. Our study fundamentally revises the futile-cycling model by demonstrating that NH3 is the major permeating species across both plasmalemma and tonoplast of root cells under toxicity conditions.

Health Code Number (HCN) Development Procedure

Energy Technology Data Exchange (ETDEWEB)

Petrocchi, Rocky; Craig, Douglas K.; Bond, Jayne-Anne; Trott, Donna M.; Yu, Xiao-Ying

2013-09-01

This report provides the detailed description of health code numbers (HCNs) and the procedure of how each HCN is assigned. It contains many guidelines and rationales of HCNs. HCNs are used in the chemical mixture methodology (CMM), a method recommended by the department of energy (DOE) for assessing health effects as a result of exposures to airborne aerosols in an emergency. The procedure is a useful tool for proficient HCN code developers. Intense training and quality assurance with qualified HCN developers are required before an individual comprehends the procedure to develop HCNs for DOE.

Determination of Pu Oxidation states in the HCl Media Using with UV-Visible Absorption Spectroscopic Techniques

International Nuclear Information System (INIS)

Lee, Myung Ho; Suh, Mu Yeol; Park, Kyoung Kyun; Park, Yeong Jae; Kim, Won Ho

2006-01-01

The spectroscopic characteristics of Pu (III, IV, V, VI) in the HCl media were investigated by measuring Pu oxidation states using a UV-Vis-NIR spectrophotometer (400-1200 nm) after adjusting Pu oxidation states with oxidation/reduction reagents. Pu in stock solution was reduced to Pu(III) with NH 2 OH · HCl, and oxidized to Pu(IV) and Pu(VI) with NaNO 2 and HCIO 4 , respectively. Also, Pu(V) was adjusted in the Pu(VI) solution with NH 2 OH · HCl. The major absorption peaks of Pu (IV) and Pu(III) were measured in the 470 nm and 600 nm, respectively. The major absorption peaks of Pu (VI) and Pu(V) were measured in the 830 nm and 1135 nm, respectively. There was not found to be significant changes of UV-V is absorption spectra for Pu(III), Pu(IV) and Pu(VI) with aging time, except that an unstable Pu(V) immediately reduced to Pu(III).

The HNC/HCN ratio in star-forming regions

International Nuclear Information System (INIS)

Graninger, Dawn M.; Öberg, Karin I.; Herbst, Eric; Vasyunin, Anton I.

2014-01-01

HNC and HCN, typically used as dense gas tracers in molecular clouds, are a pair of isomers that have great potential as a temperature probe because of temperature dependent, isomer-specific formation and destruction pathways. Previous observations of the HNC/HCN abundance ratio show that the ratio decreases with increasing temperature, something that standard astrochemical models cannot reproduce. We have undertaken a detailed parameter study on which environmental characteristics and chemical reactions affect the HNC/HCN ratio and can thus contribute to the observed dependence. Using existing gas and gas-grain models updated with new reactions and reaction barriers, we find that in static models the H + HNC gas-phase reaction regulates the HNC/HCN ratio under all conditions, except for very early times. We quantitatively constrain the combinations of H abundance and H + HNC reaction barrier that can explain the observed HNC/HCN temperature dependence and discuss the implications in light of new quantum chemical calculations. In warm-up models, gas-grain chemistry contributes significantly to the predicted HNC/HCN ratio and understanding the dynamics of star formation is therefore key to model the HNC/HCN system.

The Photodissociation of HCN and HNC: Effects on the HNC/HCN Abundance Ratio in the Interstellar Medium

Energy Technology Data Exchange (ETDEWEB)

Aguado, Alfredo [Departamento de Química Física Aplicada (UAM), Unidad Asociada a IFF-CSIC, Facultad de Ciencias Módulo 14, Universidad Autónoma de Madrid, E-28049, Madrid (Spain); Roncero, Octavio; Zanchet, Alexandre [Instituto de Física Fundamental (IFF-CSIC), C.S.I.C., Serrano 123, E-28006 Madrid (Spain); Agúndez, Marcelino; Cernicharo, José, E-mail: octavio.roncero@csic.es [Instituto de Ciencia de Materiales de Madrid, CSIC, C/ Sor Juana Inés de la Cruz 3, Cantoblanco E-28049 (Spain)

2017-03-20

The impact of the photodissociation of HCN and HNC isomers is analyzed in different astrophysical environments. For this purpose, the individual photodissociation cross sections of HCN and HNC isomers have been calculated in the 7–13.6 eV photon energy range for a temperature of 10 K. These calculations are based on the ab initio calculation of three-dimensional adiabatic potential energy surfaces of the 21 lower electronic states. The cross sections are then obtained using a quantum wave packet calculation of the rotational transitions needed to simulate a rotational temperature of 10 K. The cross section calculated for HCN shows significant differences with respect to the experimental one, and this is attributed to the need to consider non-adiabatic transitions. Ratios between the photodissociation rates of HCN and HNC under different ultraviolet radiation fields have been computed by renormalizing the rates to the experimental value. It is found that HNC is photodissociated faster than HCN by a factor of 2.2 for the local interstellar radiation field and 9.2 for the solar radiation field, at 1 au. We conclude that to properly describe the HNC/HCN abundance ratio in astronomical environments illuminated by an intense ultraviolet radiation field, it is necessary to use different photodissociation rates for each of the two isomers, which are obtained by integrating the product of the photodissociation cross sections and ultraviolet radiation field over the relevant wavelength range.

Effect of CH3COOH on Hydrometallurgical Purification of Metallurgical-Grade Silicon Using HCl-HF Leaching

Science.gov (United States)

Tian, Chunjin; Lu, Haifei; Wei, Kuixian; Ma, Wenhui; Xie, Keqiang; Wu, Jijun; Lei, Yun; Yang, Bin; Morita, Kazuki

2018-04-01

The present study investigated the effects of adding CH3COOH to HCl and HF used to purify metallurgical-grade Si (MG-Si). After 6 h of leaching MG-Si with an acid mixture consisting of 4 mol L-1 HCl, 3 mol L-1 HF, and 3 mol L-1 CH3COOH at 348 K, the total impurity removal efficiency was 88.5%, exceeding the 81.5% removal efficiency obtained without addition of CH3COOH. The microstructural evolution of Si after etching with the two lixiviants indicated better dissolution of metal impurities in MG-Si when using the HCl-HF-CH3COOH mixture. Furthermore, the leaching kinetics of Fe using the HCl-HF and HCl-HF-CH3COOH mixtures were observed to depend on the interfacial chemical reactions.

Photostriction of CH3NH3PbBr3 Perovskite Crystals

KAUST Repository

Wei, Tzu-Chiao; Wang, Hsin-Ping; Li, Ting-You; Lin, Chun-Ho; Hsieh, Ying-Hui; Chu, Ying-Hao; He, Jr-Hau

2017-01-01

.e., photostriction). From these shifts, the photostrictive coefficient of CH3 NH3 PbBr3 is calculated as 2.08 × 10-8 m2 W-1 at room temperature under visible light illumination. The significant photostriction of CH3 NH3 PbBr3 is attributed to a combination

Key intermediates in nitrogen transformation during microwave pyrolysis of sewage sludge: a protein model compound study.

Science.gov (United States)

Zhang, Jun; Tian, Yu; Cui, Yanni; Zuo, Wei; Tan, Tao

2013-03-01

The nitrogen transformations with attention to NH3 and HCN were investigated at temperatures of 300-800°C during microwave pyrolysis of a protein model compound. The evolution of nitrogenated compounds in the char, tar and gas products were conducted. The amine-N, heterocyclic-N and nitrile-N compounds were identified as three important intermediates during the pyrolysis. NH3 and HCN were formed with comparable activation energies competed to consume the same reactive substances at temperatures of 300-800°C. The deamination and dehydrogenation of amine-N compounds from protein cracking contributed to the formation of NH3 (about 8.9% of Soy-N) and HCN (6.6%) from 300 to 500°C. The cracking of nitrile-N and heterocyclic-N compounds from the dehydrogenation and polymerization of amine-N generated HCN (13.4%) and NH3 (31.3%) between 500 and 800°C. It might be able to reduce the HCN and NH3 emissions through controlling the intermediates production at temperatures of 500-800°C. Copyright © 2013 Elsevier Ltd. All rights reserved.

ALMA OBSERVATIONS OF HCN AND ITS ISOTOPOLOGUES ON TITAN

Energy Technology Data Exchange (ETDEWEB)

Molter, Edward M.; Nixon, C. A.; Cordiner, M. A.; Charnley, S. B.; Lindberg, J. E. [NASA Goddard Space Flight Center, 8800 Greenbelt Road, Greenbelt, MD 20771 (United States); Serigano, J. [Department of Earth and Planetary Sciences, Johns Hopkins University, Baltimore, MD 21218 (United States); Irwin, P. G. J. [Atmospheric, Oceanic, and Planetary Physics, Clarendon Laboratory, University of Oxford, Parks Road, Oxford, OX1 3PU (United Kingdom); Teanby, N. A., E-mail: edward.m.molter@nasa.gov [School of Earth Sciences, University of Bristol, Wills Memorial Building, Queens Road, Bristol, BS8 1RJ (United Kingdom)

2016-08-01

We present sub-millimeter spectra of HCN isotopologues on Titan, derived from publicly available ALMA flux calibration observations of Titan taken in early 2014. We report the detection of a new HCN isotopologue on Titan, H{sup 13}C{sup 15}N, and confirm an earlier report of detection of DCN. We model high signal-to-noise observations of HCN, H{sup 13}CN, HC{sup 15}N, DCN, and H{sup 13}C{sup 15}N to derive abundances and infer the following isotopic ratios: {sup 12}C/{sup 13}C = 89.8 ± 2.8, {sup 14}N/{sup 15}N = 72.3 ± 2.2, D/H = (2.5 ± 0.2) × 10{sup −4}, and HCN/H{sup 13}C{sup 15}N = 5800 ± 270 (1 σ errors). The carbon and nitrogen ratios are consistent with and improve on the precision of previous results, confirming a factor of ∼2.3 elevation in {sup 14}N/{sup 15}N in HCN compared to N{sub 2} and a lack of fractionation in {sup 12}C/{sup 13}C from the protosolar value. This is the first published measurement of D/H in a nitrile species on Titan, and we find evidence for a factor of ∼2 deuterium enrichment in hydrogen cyanide compared to methane. The isotopic ratios we derive may be used as constraints for future models to better understand the fractionation processes occurring in Titan’s atmosphere.

Photoelectric characteristics of CH3NH3PbI3/p-Si heterojunction

Science.gov (United States)

Yamei, Wu; Ruixia, Yang; Hanmin, Tian; Shuai, Chen

2016-05-01

Organic-inorganic hybrid perovskite CH3NH3PbI3 film is prepared on p-type silicon substrate using the one-step solution method to form a CH3NH3PbI3/p-Si heterojunction. The film morphology and structure are characterized by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The photoelectric properties of the CH3NH3PbI3/p-Si heterojunction are studied by testing the current-voltage (I-V) with and without illumination and capacitance-voltage (C-V) characteristics. It turns out from the I-V curve without illumination that the CH3NH3PbI3/p-Si heterojunction has a rectifier feature with the rectification ratio over 70 at the bias of ±5 V. Also, there appears a photoelectric conversion phenomenon on this heterojunction with a short circuit current (Isc) of 0.16 μA and an open circuit voltage (Voc) of about 10 mV The high frequency C-V characteristic of the Ag/CH3NH3PbI3/p-Si heterojunction turns out to be similar to that of the metal-insulator-semiconductor (MIS) structure, and a parallel translation of the C-V curve along the forward voltage axis is found. This parallel translation means the existence of defects at the CH3NH3PbI3/p-Si interface and positive fixed charges in the CH3NH3PbI3 layer. The defects at the interface of the CH3NH3PbI3/p-Si heterojunction result in the dramatic decline of the Voc. Besides, the C-V test of CH3NH3PbI3 film shows a non-linear dielectric property and the dielectric value is about 4.64 as calculated. Project supported by the Hebei Province Natural Science Foundation of China (No. F2014202184) and the Tianjin Natural Science Foundation of China (No. 15JCZDJC37800).

Ab initio study of low-energy electrons interacting with HCN molecules

International Nuclear Information System (INIS)

Jain, A.; Norcross, D.W.

1984-01-01

Our earlier study of low-energy electron scattering with HCN molecules is further improved by treating exchange exactly (in a separable exchange approximation 2 ) in Σ, π and Δ symmetries: the 3.8 eV π resonance is shifted towards lower energy (2.56 eV, the experimental position is around 2.26 eV 3 ), while in Σ and the Δ symmetries the difference is within 15%. We also study possible negative ion states of HCN by calculating potential energy curves with respect to C-H and C-N stretches. For example, there is evidence of an avoiding crossing between a 1Σ + and a 2Σ + state (C-H stretch) of HCN -

NH4+-NH3 removal from simulated wastewater using UV-TiO2 photocatalysis: effect of co-pollutants and pH.

Science.gov (United States)

Vohra, M S; Selimuzzaman, S M; Al-Suwaiyan, M S

2010-05-01

The main objective of the present study was to investigate the efficiency of titanium dioxide (TiO2) assisted photocatalytic degradation (PCD) process for the removal of ammonium-ammonia (NH4(+)-NH3) from the aqueous phase and in the presence of co-pollutants thiosulfate (S2O3(2-)) and p-cresol (C6H4CH3OH) under varying mixed conditions. For the NH4(+)-NH3 only PCD experiments, results showed higher NH4 -NH3 removal at pH 12 compared to pH 7 and 10. For the binary NH4(+)-NH3/S2O3(2-) studies the respective results indicated a significant lowering in NH4(+)-NH3 PCD in the presence of S2O32- at pH 7/12 whereas at pH 10 a marked increase in NH4(+)-NH3 removal transpired. A similar trend was noted for the p-cresol/NH4(+)-NH3 binary system. Comparing findings from the binary (NH4(+)-NH3/S2O3(2-) and p-cresol/NH4(+)-NH3) and tertiary (NH4(+)-NH3/S2O3(2-)/p-cresol) systems, at pH 10, showed fastest NH4(+)-NH3 removal transpiring for the tertiary system as compared to the binary systems, whereas both the binary systems indicated comparable NH4(+)-NH3 removal trends. The respective details have been discussed.

Noise-induced plasticity of KCNQ2/3 and HCN channels underlies vulnerability and resilience to tinnitus

Science.gov (United States)

Li, Shuang; Kalappa, Bopanna I; Tzounopoulos, Thanos

2015-01-01

Vulnerability to noise-induced tinnitus is associated with increased spontaneous firing rate in dorsal cochlear nucleus principal neurons, fusiform cells. This hyperactivity is caused, at least in part, by decreased Kv7.2/3 (KCNQ2/3) potassium currents. However, the biophysical mechanisms underlying resilience to tinnitus, which is observed in noise-exposed mice that do not develop tinnitus (non-tinnitus mice), remain unknown. Our results show that noise exposure induces, on average, a reduction in KCNQ2/3 channel activity in fusiform cells in noise-exposed mice by 4 days after exposure. Tinnitus is developed in mice that do not compensate for this reduction within the next 3 days. Resilience to tinnitus is developed in mice that show a re-emergence of KCNQ2/3 channel activity and a reduction in HCN channel activity. Our results highlight KCNQ2/3 and HCN channels as potential targets for designing novel therapeutics that may promote resilience to tinnitus. DOI: http://dx.doi.org/10.7554/eLife.07242.001 PMID:26312501

HCN Channels Modulators: The Need for Selectivity

Science.gov (United States)

Romanelli, Maria Novella; Sartiani, Laura; Masi, Alessio; Mannaioni, Guido; Manetti, Dina; Mugelli, Alessandro; Cerbai, Elisabetta

2016-01-01

Hyperpolarization-activated, cyclic nucleotide-gated (HCN) channels, the molecular correlate of the hyperpolarization-activated current (If/Ih), are membrane proteins which play an important role in several physiological processes and various pathological conditions. In the Sino Atrial Node (SAN) HCN4 is the target of ivabradine, a bradycardic agent that is, at the moment, the only drug which specifically blocks If. Nevertheless, several other pharmacological agents have been shown to modulate HCN channels, a property that may contribute to their therapeutic activity and/or to their side effects. HCN channels are considered potential targets for developing drugs to treat several important pathologies, but a major issue in this field is the discovery of isoform-selective compounds, owing to the wide distribution of these proteins into the central and peripheral nervous systems, heart and other peripheral tissues. This survey is focused on the compounds that have been shown, or have been designed, to interact with HCN channels and on their binding sites, with the aim to summarize current knowledge and possibly to unveil useful information to design new potent and selective modulators. PMID:26975509

The excitation of HCN and HCO{sup +} in the galactic center circumnuclear disk

Energy Technology Data Exchange (ETDEWEB)

Mills, E. A. C. [National Radio Astronomy Observatory, P.O. Box O 1009, Lopezville Drive, Socorro, NM 87801 (United States); Güsten, R.; Requena-Torres, M. A. [Max Planck Institut für Radioastronomie, Auf Dem Huegel 69, D-53121 Bonn (Germany); Morris, M. R., E-mail: millsb@astro.ucla.edu [Department of Physics and Astronomy, University of California, Physics and Astronomy Building, 430 Portola Plaza, Box 951547 Los Angeles, CA 90095-1547 (United States)

2013-12-10

We present new observations of HCN and HCO{sup +} in the circumnuclear disk (CND) of the Galaxy, which we obtained with the Atacama Pathfinder Experiment telescope. We mapped emission in rotational lines of HCN J = 3-2, 4-3, and 8-7, as well as of HCO{sup +} J = 3-2, 4-3, and 9-8. We also present spectra of H{sup 13}CN J = 3-2 and 4-3 as well as H{sup 13}CO{sup +} J = 3-2 and 4-3 toward four positions in the CND. Using the intensities of all of these lines, we present an excitation analysis for each molecule using the non-LTE radiative transfer code RADEX. The HCN line intensities toward the northern emission peak of the CND yield log densities (cm{sup –3}) of 5.6{sub −0.6}{sup +0.6}, consistent with those measured with HCO{sup +} as well as with densities recently reported for this region from an excitation analysis of highly excited lines of CO. These densities are too low for the gas to be tidally stable. The HCN line intensities toward the CND's southern emission peak yield log densities of 6.5{sub −0.7}{sup +0.5}, higher than densities determined for this part of the CND with CO (although the densities measured with HCO{sup +}, log [n] = 5.6{sub −0.2}{sup +0.2}, are more consistent with the CO-derived densities). We investigate whether the higher densities we infer from HCN are affected by midinfrared radiative excitation of this molecule through its 14 μm rovibrational transitions. We find that radiative excitation is important for at least one clump in the CND, where we additionally detect the J = 4-3, v {sub 2} = 1 vibrationally excited transition of HCN, which is excited by dust temperatures of ≳125-150 K. If this hot dust is present elsewhere in the CND, it could lower our inferred densities, potentially bringing the HCN-derived densities for the southern part of the CND into agreement with those measured using HCO{sup +} and CO. Additional sensitive, high-resolution submillimeter observations, as well as midinfrared observations, would be

Sick sinus syndrome in HCN1-deficient mice.

Science.gov (United States)

Fenske, Stefanie; Krause, Stefanie C; Hassan, Sami I H; Becirovic, Elvir; Auer, Franziska; Bernard, Rebekka; Kupatt, Christian; Lange, Philipp; Ziegler, Tilman; Wotjak, Carsten T; Zhang, Henggui; Hammelmann, Verena; Paparizos, Christos; Biel, Martin; Wahl-Schott, Christian A

2013-12-17

Sinus node dysfunction (SND) is a major clinically relevant disease that is associated with sudden cardiac death and requires surgical implantation of electric pacemaker devices. Frequently, SND occurs in heart failure and hypertension, conditions that lead to electric instability of the heart. Although the pathologies of acquired SND have been studied extensively, little is known about the molecular and cellular mechanisms that cause congenital SND. Here, we show that the HCN1 protein is highly expressed in the sinoatrial node and is colocalized with HCN4, the main sinoatrial pacemaker channel isoform. To characterize the cardiac phenotype of HCN1-deficient mice, a detailed functional characterization of pacemaker mechanisms in single isolated sinoatrial node cells, explanted beating sinoatrial node preparation, telemetric in vivo electrocardiography, echocardiography, and in vivo electrophysiology was performed. On the basis of these experiments we demonstrate that mice lacking the pacemaker channel HCN1 display congenital SND characterized by bradycardia, sinus dysrhythmia, prolonged sinoatrial node recovery time, increased sinoatrial conduction time, and recurrent sinus pauses. As a consequence of SND, HCN1-deficient mice display a severely reduced cardiac output. We propose that HCN1 stabilizes the leading pacemaker region within the sinoatrial node and hence is crucial for stable heart rate and regular beat-to-beat variation. Furthermore, we suggest that HCN1-deficient mice may be a valuable genetic disease model for human SND.

Probing highly obscured, self-absorbed galaxy nuclei with vibrationally excited HCN

Science.gov (United States)

Aalto, S.; Martín, S.; Costagliola, F.; González-Alfonso, E.; Muller, S.; Sakamoto, K.; Fuller, G. A.; García-Burillo, S.; van der Werf, P.; Neri, R.; Spaans, M.; Combes, F.; Viti, S.; Mühle, S.; Armus, L.; Evans, A.; Sturm, E.; Cernicharo, J.; Henkel, C.; Greve, T. R.

2015-12-01

We present high resolution (0.̋4) IRAM PdBI and ALMA mm and submm observations of the (ultra) luminous infrared galaxies ((U)LIRGs) IRAS 17208-0014, Arp220, IC 860 and Zw049.057 that reveal intense line emission from vibrationally excited (ν2 = 1) J = 3-2 and 4-3 HCN. The emission is emerging from buried, compact (r 5 × 1013 L⊙ kpc-2. These nuclei are likely powered by accreting supermassive black holes (SMBHs) and/or hot (>200 K) extreme starbursts. Vibrational, ν2 = 1, lines of HCN are excited by intense 14 μm mid-infrared emission and are excellent probes of the dynamics, masses, and physical conditions of (U)LIRG nuclei when H2 column densities exceed 1024 cm-2. It is clear that these lines open up a new interesting avenue to gain access to the most obscured AGNs and starbursts. Vibrationally excited HCN acts as a proxy for the absorbed mid-infrared emission from the embedded nuclei, which allows for reconstruction of the intrinsic, hotter dust SED. In contrast, we show strong evidence that the ground vibrational state (ν = 0), J = 3-2and 4-3 rotational lines of HCN and HCO+ fail to probe the highly enshrouded, compact nuclear regions owing to strong self- and continuum absorption. The HCN and HCO+ line profiles are double-peaked because of the absorption and show evidence of non-circular motions - possibly in the form of in- or outflows. Detections of vibrationally excited HCN in external galaxies are so far limited to ULIRGs and early-type spiral LIRGs, and we discuss possible causes for this. We tentatively suggest that the peak of vibrationally excited HCN emission is connected to a rapid stage of nuclear growth, before the phase of strong feedback. Based on observations carried out with the IRAM Plateau de Bure and ALMA Interferometers. IRAM is supported by INSU/CNRS (France), MPG (Germany), and IGN (Spain). ALMA is a partnership of ESO (representing its member states), NSF (USA), and NINS (Japan), together with NRC (Canada) and NSC and ASIAA

The Impact of HCl Precleaning and Sulfur Passivation on the Al2O3/Ge Interface in Ge Metal-Oxide-Semiconductor Capacitors

International Nuclear Information System (INIS)

Xue Bai-Qing; Chang Hu-Dong; Sun Bing; Wang Sheng-Kai; Liu Hong-Gang

2012-01-01

Surface treatment for Ge substrates using hydrogen chlorine cleaning and chemical passivation are investigated on AuTi/Al 2 O 3 /Ge metal-oxide-semiconductor capacitors. After hydrogen chlorine cleaning, a smooth Ge surface almost free from native oxide is demonstrated by atomic force microscopy and x-ray photoelectron spectroscopy observations. Passivation using a hydrogen chlorine solution is found to form a chlorine-terminated surface, while aqueous ammonium sulfide pretreatment results in a surface terminated by Ge-S bonding. Compared with chlorine-passivated samples, the sulfur-passivated ones show less frequency dispersion and better thermal stability based on capacitance-voltage characterizations. The samples with HCl pre-cleaning and (NH 4 ) 2 S passivation show less frequency dispersion than the HF pre-cleaning and (NH 4 ) 2 S passivated ones. The surface treatment process using hydrogen chlorine cleaning followed by aqueous ammonium sulfide passivation demonstrates a promising way to improve gate dielectric/Ge interface quality. (condensed matter: structure, mechanical and thermal properties)

A comparative study of nitrogen conversion during pyrolysis of coconut fiber, its corresponding biochar and their blends with lignite.

Science.gov (United States)

Liu, Zhengang; Balasubramanian, Rajasekhar

2014-01-01

In the present study, the conversion of fuel-N to HCN and NH3 was investigated during rapid pyrolysis of raw biomass (coconut fiber), its corresponding biochar and their blends with lignite within a temperature range of 600-900°C. The results showed that the raw biomass and the biochar showed totally different nitrogen partitioning between NH3 and HCN. HCN was the dominant nitrogen pollutant from pyrolysis of raw biomass, while for the biochar pyrolysis the yield of NH3 was slightly higher than that of HCN. Synergistic interactions occurred within both raw biomass/lignite and biochar/lignite blends, especially for the biochar/lignite blend, and resulted in reduced yields of HCN and NH3, decreased the total nitrogen percentage retained in the char and promoted harmless N2 formation. These findings suggest that biochar/lignite co-firing for energy production may have the enhanced benefit of reduced emissions of nitrogen pollutants than raw biomass/lignite. Copyright © 2013 Elsevier Ltd. All rights reserved.

The Puzzle of HCN in Comets: Is it both a Product and a Primary Species?

Science.gov (United States)

Mumma, Michael J.; Bonev, Boncho P.; Charnley, Steven B.; Cordiner, Martin A.; DiSanti, Michael A.; Gibb, Erika L.; Magee-Sauer, Karen; Paganini, Lucas; Villanueva, Geronimo L.

2014-11-01

Hydrogen cyanide has long been regarded as a primary volatile in comets, stemming from its presence in dense molecular cloud cores and its supposed storage in the cometary nucleus. Here, we examine the observational evidence for and against that hypothesis, and argue that HCN may also result from near-nucleus chemical reactions in the coma. The distinction (product vs. primary species) is important for multiple reasons: 1. HCN is often used as a proxy for water when the dominant species (H2O) is not available for simultaneous measurement, as at radio wavelengths. 2. HCN is one of the few volatile carriers of nitrogen accessible to remote sensing. If HCN is mainly a product species, its precursor becomes the more important metric for compiling a taxonomic classification based on nitrogen chemistry. 3. The stereoisomer HNC is now confirmed as a product species. Could reaction of a primary precursor (X-CN) with a hydrocarbon co-produce both HNC and HCN? 4. The production rate for CN greatly exceeds that of HCN in some comets, demonstrating the presence of another (more important) precursor of CN. Several puzzling lines of evidence raise issues about the origin of HCN: a. The production rates of HCN measured through rotational (radio) and vibrational (infrared) spectroscopy agree in some comets - in others the infrared rate exceeds the radio rate substantially. b. With its strong dipole moment and H-bonding character, HCN should be linked more strongly in the nuclear ice to other molecules with similar properties (H2O, CH3OH), but instead its spatial release in some comets seems strongly coupled to volatiles that lack a dipole moment and thus do not form H-bonds (methane, ethane). c. The nucleus-centered rotational temperatures measured for H2O and other species (C2H6, CH3OH) usually agree within error, but those for HCN are often slightly smaller. d. In comet ISON, ALMA maps of HCN and the dust continuum show a slight displacement 80 km) in the centroids. We will

Long-lasting spatial learning and memory impairments caused by chronic cerebral hypoperfusion associate with a dynamic change of HCN1/HCN2 expression in hippocampal CA1 region.

Science.gov (United States)

Luo, Pan; Lu, Yun; Li, Changjun; Zhou, Mei; Chen, Cheng; Lu, Qing; Xu, Xulin; He, Zhi; Guo, Lianjun

2015-09-01

Chronic cerebral hypoperfusion (CCH) causes learning and memory impairments and increases the risk of Alzheimer disease (AD) and vascular dementia (VD) through several biologically plausible pathways, yet the mechanisms underlying the disease process remained unclear particularly in a temporal manner. We performed permanent bilateral occlusion of the common carotid arteries (two-vessel occlusion, 2VO) to induce CCH. To determine whether hyperpolarization-activated cyclic nucleotide-gated (HCN) channels are altered at different stages of cognitive impairment caused by CCH, adult male SD rats were randomly distributed into sham-operated 4, 8 and 12weeks group, 2VO 4, 8 and 12weeks group. Learning and memory performance were evaluated with Morris water maze (MWM) and long-term potentiation (LTP) was used to address the underlying synaptic mechanisms. Expression of NeuN, HCN1 and HCN2 in hippocampal CA1, DG and CA3 areas was quantified by immunohistochemistry and western blotting. Our data showed that CCH induced a remarkable spatial learning and memory deficits in rats of 2VO 4, 8, and 12weeks group although neuronal loss only occurred after 4weeks of 2VO surgery in CA1. In addition, a significant reduction of HCN1 surface expression in CA1 was observed in the group that suffered 4weeks ischemia but neither 8 nor 12weeks. However, HCN2 surface expression in CA1 increased throughout the ischemia time-scales (4, 8 and 12w). Our findings indicate spatial learning and memory deficits in the CCH model are associated with disturbed HCN1 and HCN2 surface expression in hippocampal CA1. The altered patterns of both HCN1 and HCN2 surface expression may be implicated in the early stage (4w) of spatial learning and memory impairments; and the stable and long-lasting impairments of spatial learning and memory may partially attribute to the up-regulated HCN2 surface expression. Copyright © 2015 Elsevier Inc. All rights reserved.

Nitrogen conversion during rapid pyrolysis of coal and petroleum coke in a high-frequency furnace

International Nuclear Information System (INIS)

Yuan, Shuai; Zhou, Zhi-jie; Li, Jun; Wang, Fu-chen

2012-01-01

Highlights: ► Use a high-frequency furnace to study N-conversion during rapid pyrolysis of coal. ► Scarcely reported N-conversion during rapid pyrolysis of petroleum coke was studied. ► Both of NH 3 and HCN can be formed directly from coal during rapid pyrolysis. ► NH 3 –N yields are higher than HCN–N yields in most conditions. ► NH 3 –N yields of petroleum coke increase with temperature and no HCN detected. -- Abstract: Rapid pyrolysis of three typical Chinese coals, lignite from Inner Mongolia, bituminous from Shenfu coalfield, and anthracite from Guizhou, as well as a petroleum coke were carried out in a drop-style high-frequency furnace. The reactor was induction coil heated and had a very small high-temperature zone, which could restrain secondary conversions of nitrogen products. The effects of temperature and coal rank on conversions of fuel-N to primary nitrogen products (char-N, HCN–N, NH 3 –N and (tar + N 2 )–N) have been investigated. The results showed that, the increasing temperature reduced the yields of char-N and promoted the conversion of fuel-N to N 2 . Char-N yields increased, while volatile-N yields decreased as the coal rank increased. In most of the conditions, NH 3 –N yields were higher than HCN–N yields during rapid pyrolysis of coal. In the case of petroleum coke, NH 3 –N yields increased gradually with the increasing temperature, but no HCN was detected. We argue that NH 3 –N can be formed directly through the primary pyrolysis without secondary reactions. Although volatile-N yields of lignite were higher than those of bituminous, yields of (HCN + NH 3 )–N in volatile-N of lignite were lower than those of bituminous. While the (HCN + NH 3 )–N yields of anthracite were the lowest of the three coals. Both of the (HCN + NH 3 )–N yields and (HCN + NH 3 )–N proportions in volatile-N of petroleum coke were lower than the three coals.

Imaging a multidimensional multichannel potential energy surface: Photodetachment of H(-)(NH3) and NH4 (.).

Science.gov (United States)

Hu, Qichi; Song, Hongwei; Johnson, Christopher J; Li, Jun; Guo, Hua; Continetti, Robert E

2016-06-28

Probes of the Born-Oppenheimer potential energy surfaces governing polyatomic molecules often rely on spectroscopy for the bound regions or collision experiments in the continuum. A combined spectroscopic and half-collision approach to image nuclear dynamics in a multidimensional and multichannel system is reported here. The Rydberg radical NH4 and the double Rydberg anion NH4 (-) represent a polyatomic system for benchmarking electronic structure and nine-dimensional quantum dynamics calculations. Photodetachment of the H(-)(NH3) ion-dipole complex and the NH4 (-) DRA probes different regions on the neutral NH4 PES. Photoelectron energy and angular distributions at photon energies of 1.17, 1.60, and 2.33 eV compare well with quantum dynamics. Photoelectron-photofragment coincidence experiments indicate dissociation of the nascent NH4 Rydberg radical occurs to H + NH3 with a peak kinetic energy of 0.13 eV, showing the ground state of NH4 to be unstable, decaying by tunneling-induced dissociation on a time scale beyond the present scope of multidimensional quantum dynamics.

Comparative genomic and physiological analysis of nutrient response to NH4+, NH4+:NO3- and NO3- in barley seedlings.

Science.gov (United States)

Lopes, Marta S; Araus, José L

2008-09-01

Long-term differences in photosynthesis, respiration and growth of plants receiving distinct nitrogen (N) sources imply that N metabolism generates signals that regulate metabolism and development. The molecular basis of these signals remains unclear. Here we studied the gene expression profiles of barley (Hordeum vulgare L. cv. Graphic) seedlings fertilized either with ammonium (NH4+), with ammonium and nitrate (NH4+:NO3-), or with nitrate (NO3-) only. Our transcriptome analysis after 48 h of growth in these N sources showed major changes in the expression of genes involved in N metabolism (nitrate reductase), signalling (protein kinases and protein phosphatases), photosynthesis (chlorophyll a/b-binding protein and a PsbQ domain), where increases in NO3- as compared with NH4+ were observed. Moreover, NH4+ assimilation induced genes participating in C and sugars metabolism (phosphoglycerate kinase, glucosyltranferase and galactokinase), respiration (cytochrome c oxidase), protein fate (heat shock proteins) and development (MTN3-like protein). These changes in gene expression could well explain the long-term growth depression observed in NH4+ plants. Even if a few genes participating in protein fate (proteases) and development (OsNAC5) were upregulated in NH4+ as compared with NH4+:NO3-, the general pattern of expression was quite similar between these two N sources. Taken together, these results indicated that other downstream mechanisms should be involved in the synergetic long-term response of NH4+:NO3-.

Simple Organics and Biomonomers Identified in HCN Polymers: An Overview

Directory of Open Access Journals (Sweden)

Susana Osuna-Esteban

2013-07-01

Full Text Available Hydrogen cyanide (HCN is a ubiquitous molecule in the Universe. It is a compound that is easily produced in significant yields in prebiotic simulation experiments using a reducing atmosphere. HCN can spontaneously polymerise under a wide set of experimental conditions. It has even been proposed that HCN polymers could be present in objects such as asteroids, moons, planets and, in particular, comets. Moreover, it has been suggested that these polymers could play an important role in the origin of life. In this review, the simple organics and biomonomers that have been detected in HCN polymers, the analytical techniques and procedures that have been used to detect and characterise these molecules and an exhaustive classification of the experimental/environmental conditions that favour the formation of HCN polymers are summarised. Nucleobases, amino acids, carboxylic acids, cofactor derivatives and other compounds have been identified in HCN polymers. The great molecular diversity found in HCN polymers encourages their placement at the central core of a plausible protobiological system.

Rate-based modelling of combined SO2 removal and NH3 recycling integrated with an aqueous NH3-based CO2 capture process

International Nuclear Information System (INIS)

Li, Kangkang; Yu, Hai; Qi, Guojie; Feron, Paul; Tade, Moses; Yu, Jingwen; Wang, Shujuan

2015-01-01

Highlights: • A rigorous, rate-based model for an NH 3 –CO 2 –SO 2 –H 2 O system was developed. • Model predictions are in good agreement with pilot plant results. • >99.9% of SO 2 was captured and >99.9% of slipped ammonia was reused. • The process is highly adaptable to the variations of SO 2 /NH 3 level, temperatures. - Abstract: To reduce the costs of controlling emissions from coal-fired power stations, we propose an advanced and effective process of combined SO 2 removal and NH 3 recycling, which can be integrated with the aqueous NH 3 -based CO 2 capture process to simultaneously achieve SO 2 and CO 2 removal, NH 3 recycling and flue gas cooling in one process. A rigorous, rate-based model for an NH 3 –CO 2 –SO 2 –H 2 O system was developed and used to simulate the proposed process. The model was thermodynamically and kinetically validated by experimental results from the open literature and pilot-plant trials, respectively. Under typical flue gas conditions, the proposed process has SO 2 removal and NH 3 reuse efficiencies of >99.9%. The process is strongly adaptable to different scenarios such as high SO 2 levels in flue gas, high NH 3 levels from the CO 2 absorber and high flue gas temperatures, and has a low energy requirement. Because the process simplifies flue gas desulphurisation and resolves the problems of NH 3 loss and SO 2 removal, it could significantly reduce the cost of CO 2 and SO 2 capture by aqueous NH 3

HCN Channels—Modulators of Cardiac and Neuronal Excitability

Directory of Open Access Journals (Sweden)

Stefan Herrmann

2015-01-01

Full Text Available Hyperpolarization-activated cyclic nucleotide-gated (HCN channels comprise a family of cation channels activated by hyperpolarized membrane potentials and stimulated by intracellular cyclic nucleotides. The four members of this family, HCN1–4, show distinct biophysical properties which are most evident in the kinetics of activation and deactivation, the sensitivity towards cyclic nucleotides and the modulation by tyrosine phosphorylation. The four isoforms are differentially expressed in various excitable tissues. This review will mainly focus on recent insights into the functional role of the channels apart from their classic role as pacemakers. The importance of HCN channels in the cardiac ventricle and ventricular hypertrophy will be discussed. In addition, their functional significance in the peripheral nervous system and nociception will be examined. The data, which are mainly derived from studies using transgenic mice, suggest that HCN channels contribute significantly to cellular excitability in these tissues. Remarkably, the impact of the channels is clearly more pronounced in pathophysiological states including ventricular hypertrophy as well as neural inflammation and neuropathy suggesting that HCN channels may constitute promising drug targets in the treatment of these conditions. This perspective as well as the current therapeutic use of HCN blockers will also be addressed.

Synthesis, Resistivity, and Thermal Properties of the Cubic Perovskite NH 2CH=NH 2SnI 3and Related Systems

Science.gov (United States)

Mitzi, D. B.; Liang, K.

1997-12-01

Combining concentrated hydriodic acid solutions of tin(II) iodide and formamidine acetate in an inert atmosphere results in the precipitation of a new conducting organic-inorganic compound, NH 2CH=NH 2SnI 3, which at room temperature adopts a cubic perovskite structure. The lattice constant for NH 2CH=NH 2SnI 3is found to be a=6.316(1) Å, which is approximately 1.2% larger than that for the isostructural compound CH 3NH 3SnI 3. The electrical resistivity of a pressed pellet of the new compound exhibits semimetallic temperature dependence from 10 to 300 K, with evidence of a structural transition at approximately 75 K. NH 2CH=NH 2SnI 3begins to slowly decompose in an inert atmosphere at temperatures as low as 200°C, with bulk decomposition/melting occurring above 300°C. The properties of the formamidinium-based perovskite are compared with those of the related cubic (at room temperature) perovskite CH 3NH 3SnI 3and the mixed-cation system (CH 3NH 3) 1- x(NH 2CH=NH 2) xSnI 3.

Rapid Ammonia Gas Transport Accounts for Futile Transmembrane Cycling under NH3/NH4+ Toxicity in Plant Roots1[C][W

Science.gov (United States)

Coskun, Devrim; Britto, Dev T.; Li, Mingyuan; Becker, Alexander; Kronzucker, Herbert J.

2013-01-01

Futile transmembrane NH3/NH4+ cycling in plant root cells, characterized by extremely rapid fluxes and high efflux to influx ratios, has been successfully linked to NH3/NH4+ toxicity. Surprisingly, the fundamental question of which species of the conjugate pair (NH3 or NH4+) participates in such fluxes is unresolved. Using flux analyses with the short-lived radioisotope 13N and electrophysiological, respiratory, and histochemical measurements, we show that futile cycling in roots of barley (Hordeum vulgare) seedlings is predominately of the gaseous NH3 species, rather than the NH4+ ion. Influx of 13NH3/13NH4+, which exceeded 200 µmol g–1 h–1, was not commensurate with membrane depolarization or increases in root respiration, suggesting electroneutral NH3 transport. Influx followed Michaelis-Menten kinetics for NH3 (but not NH4+), as a function of external concentration (Km = 152 µm, Vmax = 205 µmol g–1 h–1). Efflux of 13NH3/13NH4+ responded with a nearly identical Km. Pharmacological characterization of influx and efflux suggests mediation by aquaporins. Our study fundamentally revises the futile-cycling model by demonstrating that NH3 is the major permeating species across both plasmalemma and tonoplast of root cells under toxicity conditions. PMID:24134887

HCN Polymers: Toward Structure Comprehension Using High Resolution Mass Spectrometry

Science.gov (United States)

Bonnet, Jean-Yves; Thissen, Roland; Frisari, Ma; Vuitton, Veronique; Quirico, Eric; Le Roy, Léna; Fray, Nicolas; Cottin, Hervé; Horst, Sarah; Yelle, Roger

A lot of solar system materials, including cometary ices and Titan aerosols, contain dark matter that can be interpreted as complex nitrogen bearing organic matter [1]. In laboratory experi-ments, HCN polymers are thus analogs of great interest. In fact they may be present in Titan atmosphere and in comet nuclei and then reprocessed as a CN distributed source [2], when ices began to sublimate and ejects from the nucleus organic matter grains [3]. The presence of HCN polymers is suggested because HCN molecule has been directly observed in 1P/Halley comet [4] and others. HCN polymers are also of prebiotic interest [5] as it can form amino acid under hydrolysis conditions. Even if they have been studied during the last decades, their chemical composition and structure are still poorly understood, and a great analytical effort has to be continued. In this way we present a high resolution mass spectrometry (HRMS) and a high resolution tandem mass spectrometry (MS/HRMS) analysis of HCN polymers. It was shown [6] that this is a suitable technique to elucidate composition and structure of the soluble part of tholins analogs of Titan's atmosphere aerosols. HCN polymers have never been studied by HRMS, thus we used a LTQ-Orbitrap XL high resolution mass spectrometer to analyse the HCN polymers. These are produced at LISA by direct polymerisation of pure liquid HCN, catalyzed by ammonia. HCN polymers have been completely dissolved in methanol and then injected in the mass spectrometer by ElectroSpray Ionization (ESI). This atmospheric pressure ionization process produces protonated or deprotonated ions, but it does not fragment molecules. Thus HRMS, allows a direct access to the stoechiometry of all the ionizable molecules present in the samples. Fragmentation analyses (MS/MS) of selected ions have also been performed. Thess analysis provide information about the different chemical fonctionnalities present in HCN poly-mers and also about their structure. Thus we are able to

Structural determinants of NH3 and NH4+ transport by mouse Rhbg, a renal Rh glycoprotein.

Science.gov (United States)

Abdulnour-Nakhoul, Solange; Le, Trang; Rabon, Edd; Hamm, L Lee; Nakhoul, Nazih L

2016-12-01

Renal Rhbg is localized to the basolateral membrane of intercalated cells and is involved in NH 3 /NH 4 + transport. The structure of Rhbg is not yet resolved; however, a high-resolution crystal structure of AmtB, a bacterial homolog of Rh, has been determined. We aligned the sequence of Rhbg to that of AmtB and identified important sites of Rhbg that may affect transport. Our analysis positioned three conserved amino acids, histidine 183 (H183), histidine 342 (H342), and tryptophan 230 (W230), within the hydrophobic pore where they presumably serve to control NH 3 transport. A fourth residue, phenylalanine 128 (F128) was positioned at the upper vestibule, presumably contributing to recruitment of NH 4 + We generated three mutations each of H183, H342, W230, and F128 and expressed them in frog oocytes. Immunolabeling showed that W230 and F128 mutants were localized to the cell membrane, whereas H183 and H342 staining was diffuse and mostly intracellular. To determine function, we compared measurements of NH 3 /NH 4 + and methyl amine (MA)/methyl ammonium (MA + )-induced currents, intracellular pH, and surface pH (pHs) among oocytes expressing the mutants, Rhbg, or injected with H 2 O. In H183 and W230 mutants, NH 4 + -induced current and intracellular acidification were inhibited compared with that of Rhbg, and MA-induced intracellular alkalinization was completely absent. Expression of H183A or W230A mutants inhibited NH 3 /NH 4 + - and MA/MA + -induced decrease in pHs to the level observed in H 2 O-injected oocytes. Mutations of F128 did not significantly affect transport of NH 3 or NH 4 + These data demonstrated that mutating H183 or W230 caused loss of function but not F128. H183 and H342 may affect membrane expression of the transporter.

Kinetics of the CH{sub 3} + HCl/DCl {sup {yields}} CH{sub 4}/CH{sub 3}D + Cl and CD{sub 3} + HCl/DCl {sup {yields}} CD{sub 3}H/CD{sub 4} + Cl reactions: An experimental H atom tunneling investigation

Energy Technology Data Exchange (ETDEWEB)

Eskola, Arkke J. [Laboratory of Physical Chemistry, P.O. Box 55 (A.I. Virtasen aukio 1), FIN-00014, University of Helsinki, Helsinki (Finland); Seetula, Jorma A. [Laboratory of Physical Chemistry, P.O. Box 55 (A.I. Virtasen aukio 1), FIN-00014, University of Helsinki, Helsinki (Finland)], E-mail: seetula@csc.fi; Timonen, Raimo S. [Laboratory of Physical Chemistry, P.O. Box 55 (A.I. Virtasen aukio 1), FIN-00014, University of Helsinki, Helsinki (Finland)

2006-12-11

The kinetics of the radical reactions of CH{sub 3} with HCl or DCl and CD{sub 3} with HCl or DCl have been investigated in a temperature controlled tubular reactor coupled to a photoionization mass spectrometer. The CH{sub 3} (or CD{sub 3}) radical, R, was produced homogeneously in the reactor by a pulsed 193 nm exciplex laser photolysis of CH{sub 3}COCH{sub 3} (or CD{sub 3}COCD{sub 3}). The decay of CH{sub 3}/CD{sub 3} was monitored as a function of HCl/DCl concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature, typically from 188 to 500 K. The rate constants of the CH{sub 3} and CD{sub 3} reactions with HCl had strong non-Arrhenius behavior at low temperatures. The rate constants were fitted to a modified Arrhenius expression k = QA exp (-E {sub a}/RT) (error limits stated are 1{sigma} + Students t values, units in cm{sup 3} molecule{sup -1} s{sup -1}): k(CH{sub 3} + HCl) = [1.004 + 85.64 exp (-0.02438 x T/K)] x (3.3 {+-} 1.3) x 10{sup -13} exp [-(4.8 {+-} 0.6) kJ mol{sup -1}/RT] and k(CD{sub 3} + HCl) = [1.002 + 73.31 exp (-0.02505 x T/K)] x (2.7 {+-} 1.2) x 10{sup -13} exp [-(3.5 {+-} 0.5) kJ mol{sup -1}/RT]. The radical reactions with DCl were studied separately over a wide ranges of temperatures and in these temperature ranges the rate constants determined were fitted to a conventional Arrhenius expression k = A exp (-E {sub a}/RT) (error limits stated are 1{sigma} + Students t values, units in cm{sup 3} molecule{sup -1} s{sup -1}): k(CH{sub 3} + DCl) = (2.4 {+-} 1.6) x 10{sup -13} exp [-(7.8 {+-} 1.4) kJ mol{sup -1}/RT] and k(CD{sub 3} + DCl) = (1.2 {+-} 0.4) x 10{sup -13} exp [-(5.2 {+-} 0.2) kJ mol{sup -1}/RT] cm{sup 3} molecule{sup -1} s{sup -1}. Curvature in the Arrhenius plots of the H-atom abstraction reactions at low temperatures was analyzed by considering H-atom tunneling through the reaction barrier and primary kinetic isotope effect. Contribution of tunneling in it was concluded to be

CH3NH3Pb1-xMgxI3 perovskites as environmentally friendly photovoltaic materials

Science.gov (United States)

Zhang, Y. D.; Feng, J.

2018-01-01

In an effort to reduce the toxicity of Pb in perovskite solar cells, the band structures, electron and hole effective masses, and electronic and optical properties of the novel perovskites CH3NH3Pb1-xMgxI3 were predicted using density functional theory with the scalar relativistic generalized gradient approximation. The calculation results indicated that the introduction of the Mg component caused the band gaps of the CH3NH3Pb1-xMgxI3 compounds to exceed that of CH3NH3PbI3. The calculated absorption coefficients of the CH3NH3PbI3 and CH3NH3Pb1-xMgxI3 perovskites revealed that substituting 12.5 mol % of the Pb in CH3NH3PbI3 with Mg had little effect on the absorption ability. Surprisingly, it was also found that CH3NH3Pb0.75Mg0.25I3 retained up to 83% of the absorption performance relative to CH3NH3PbI3. This indicates that the amount of toxic Pb used in perovskite solar cells could be reduced by a quarter while retaining over 80% of the light-absorbing ability. In general, these novel CH3NH3Pb1-xMgxI3 (x ≤ 0.25) perovskites represent promising candidates for environmentally friendly light-harvesting materials for use in solar cells.

Optical monitoring of CH3NH3PbI3 thin films upon atmospheric exposure

International Nuclear Information System (INIS)

Ghimire, Kiran; Zhao, Dewei; Cimaroli, Alex; Ke, Weijun; Yan, Yanfa; Podraza, Nikolas J

2016-01-01

CH 3 NH 3 PbI 3 perovskite films of interest for photovoltaic (PV) devices have been prepared by (i) vapor deposition and (ii) solution processing. Complex dielectric function ( ε   =   ε 1   +  i ε 2 ) spectra and structural parameters of the films have been extracted using near infrared to ultraviolet spectroscopic ellipsometry. In situ real time spectroscopic ellipsometry (RTSE) over a 48 h period has been performed on vapor deposited CH 3 NH 3 PbI 3 after the deposition in normal atmospheric laboratory ambient conditions. Analysis of RTSE data for vapor deposited CH 3 NH 3 PbI 3 film prepared under un-optimized conditions identifies phase segregated PbI 2 and CH 3 NH 3 I at the substrate/film interface and unreacted PbI 2 and CH 3 NH 3 I on the film surface. This analysis also provides the time dependence of the effective thicknesses of perovskite film, unreacted components, and phase segregated layers to track CH 3 NH 3 PbI 3 decomposition. (paper)

Photovoltaic properties of Cu-doped CH3NH3PbI3 with perovskite structure

Science.gov (United States)

Shirahata, Yasuhiro; Oku, Takeo

2017-01-01

Photovoltaic properties of copper (Cu)-doped perovskite (CH3NH3PbCuxI3+x) photovoltaic devices with different Cu content were investigated. The CH3NH3PbCuxI3+x films were polycrystalline with a tetragonal system, and their lattice constants and crystallite size varied with Cu doping. Compared to conversion efficiencies of non-doped CH3NH3PbI3 photovoltaic device, those of CH3NH3PbCuxI3+x photovoltaic devises increased. The improvement of photovoltaic properties was attributed to partial substitution of Cu at the Pb sites.

Sugar-to-base correlation in nucleic acids with a 5D APSY-HCNCH or two 3D APSY-HCN experiments

Energy Technology Data Exchange (ETDEWEB)

Kraehenbuehl, Barbara; Hofmann, Daniela; Maris, Christophe; Wider, Gerhard, E-mail: gsw@mol.biol.ethz.ch [Institute of Molecular Biology and Biophysics (Switzerland)

2012-02-15

A five-dimensional (5D) APSY (automated projection spectroscopy) HCNCH experiment is presented, which allows unambiguous correlation of sugar to base nuclei in nucleic acids. The pulse sequence uses multiple quantum (MQ) evolution which enables long constant-time evolution periods in all dimensions, an improvement that can also benefit non-APSY applications. Applied with an RNA with 23 nucleotides the 5D APSY-HCNCH experiment produced a complete and highly precise 5D chemical shift list within 1.5 h. Alternatively, and for molecules where the out-and-stay 5D experiment sensitivity is not sufficient, a set of out-and-back 3D APSY-HCN experiments is proposed: an intra-base (3D APSY-b-HCN) experiment in an MQ or in a TROSY version, and an MQ sugar-to-base (3D APSY-s-HCN) experiment. The two 3D peak lists require subsequent matching via the N1/9 chemical shift values to one 5D peak list. Optimization of the 3D APSY experiments for maximal precision in the N1/9 dimension allowed matching of all {sup 15}N chemical shift values contained in both 3D peak lists. The precise 5D chemical shift correlation lists resulting from the 5D experiment or a pair of 3D experiments also provide a valuable basis for subsequent connection to chemical shifts derived with other experiments.

Sugar-to-base correlation in nucleic acids with a 5D APSY-HCNCH or two 3D APSY-HCN experiments

International Nuclear Information System (INIS)

Krähenbühl, Barbara; Hofmann, Daniela; Maris, Christophe; Wider, Gerhard

2012-01-01

A five-dimensional (5D) APSY (automated projection spectroscopy) HCNCH experiment is presented, which allows unambiguous correlation of sugar to base nuclei in nucleic acids. The pulse sequence uses multiple quantum (MQ) evolution which enables long constant-time evolution periods in all dimensions, an improvement that can also benefit non-APSY applications. Applied with an RNA with 23 nucleotides the 5D APSY-HCNCH experiment produced a complete and highly precise 5D chemical shift list within 1.5 h. Alternatively, and for molecules where the out-and-stay 5D experiment sensitivity is not sufficient, a set of out-and-back 3D APSY-HCN experiments is proposed: an intra-base (3D APSY-b-HCN) experiment in an MQ or in a TROSY version, and an MQ sugar-to-base (3D APSY-s-HCN) experiment. The two 3D peak lists require subsequent matching via the N1/9 chemical shift values to one 5D peak list. Optimization of the 3D APSY experiments for maximal precision in the N1/9 dimension allowed matching of all 15 N chemical shift values contained in both 3D peak lists. The precise 5D chemical shift correlation lists resulting from the 5D experiment or a pair of 3D experiments also provide a valuable basis for subsequent connection to chemical shifts derived with other experiments.

On the growth of CH3NH3PbI3-xClx single crystal and characterization

Science.gov (United States)

Su, J.; Wang, W. F.; Lei, Y.; Zhang, L.; Xu, L. H.; Wang, D.; Lu, D.; Bai, Y.

2018-05-01

In this paper, CH3NH3PbI3-xClx crystal was grown by solution cooling method with CH3NH3I and PbCl2 as raw materials. Lead compounds and CH3NH3PbI3-xClx crystal with size about 6 mm × 4 mm × 2 mm were obtained. The chemical reactions with different CH3NH3I/PbCl2 ratios were analyzed. XPS shows the content of chlorine in CH3NH3PbI3-xClx is about 0.91%. PXRD, FT-IR, Raman and absorbance spectra were used to study the structure and optical properties of CH3NH3PbI3-xClx by comparing with CH3NH3PbI3 crystal. The CH3NH3PbI3-xClx crystal grown is of tetragonal structure with the lattice constants a = b = 8.8165 Å, c = 12.7920 Å and the bandgap value of 1.57 eV.

[UO2(NH3)5]Br2·NH3: synthesis, crystal structure, and speciation in liquid ammonia solution by first-principles molecular dynamics simulations.

Science.gov (United States)

Woidy, Patrick; Bühl, Michael; Kraus, Florian

2015-04-28

Pentaammine dioxido uranium(VI) dibromide ammonia (1/1), [UO2(NH3)5]Br2·NH3, was synthesized in the form of yellow crystals by the reaction of uranyl bromide, UO2Br2, with dry liquid ammonia. The compound crystallizes orthorhombic in space group Cmcm and is isotypic to [UO2(NH3)5]Cl2·NH3 with a = 13.2499(2), b = 10.5536(1), c = 8.9126(1) Å, V = 1246.29(3) Å(3) and Z = 4 at 123 K. The UO2(2+) cation is coordinated by five ammine ligands and the coordination polyhedron can be best described as pentagonal bipyramid. Car-Parrinello molecular dynamics simulations are reported for [UO2(NH3)5](2+) in the gas phase and in liquid NH3 solution (using the BLYP density functional). According to free-energy simulations, solvation by ammonia has only a small effect on the uranyl-NH3 bond strength.

Ammonothermal synthesis of alkali-alkaline earth metal and alkali-rare earth metal carbodiimides. K{sub 5-x}M{sub x}(CN{sub 2}){sub 2+x}(HCN{sub 2}){sub 1-x} (M = Sr, Eu) and Na{sub 4.32}Sr{sub 0.68}(CN{sub 2}){sub 2.68}(HCN{sub 2}){sub 0.32}

Energy Technology Data Exchange (ETDEWEB)

Mallmann, Mathias; Haeusler, Jonas; Cordes, Niklas; Schnick, Wolfgang [Department of Chemistry, University of Munich (LMU) (Germany)

2017-12-13

Alkali-alkaline earth metal and alkali-rare earth metal carbodiimides, namely K{sub 5-x}M{sub x}(CN{sub 2}){sub 2+x}(HCN{sub 2}){sub 1-x} (x = 0 - 1) (M = Sr, Eu) and Na{sub 4.32}Sr{sub 0.68}(CN{sub 2}){sub 2.68}(HCN{sub 2}){sub 0.32}, were synthesized under ammonothermal conditions in high-pressure autoclaves. The structures of the three compounds can be derived from homeotypic K{sub 5}H(CN{sub 2}){sub 3} and Na{sub 5}H(CN{sub 2}){sub 3} by partial substitution of K{sup +} or Na{sup +}by Sr{sup 2+} or Eu{sup 2+}. The reactions were carried out in two step syntheses (T{sub 1} = 673 K, T{sub 2} = 823 K) starting from sodium or potassium azide, dicyandiamide and strontium or Eu(NH{sub 2}){sub 2}, respectively. The crystal structures were solved and refined from single-crystal X-ray diffraction data [K{sub 4.16}Sr{sub 0.84}(CN{sub 2}){sub 2.84}(HCN{sub 2}){sub 0.16}: space group Im3m (no. 229), a = 7.8304(5) Aa, Z = 2, R{sub 1} = 0.024, wR{sub 2} = 0.052; K{sub 4.40}Eu{sub 0.60}(CN{sub 2}){sub 2.60}(HCN{sub 2}){sub 0.40}: space group Im anti 3m (no. 229), a = 7.8502(6) Aa, Z = 2, R{sub 1} = 0.022, wR{sub 2} = 0.049]. In contrast to the potassium carbodiimides, the sodium-strontium carbodiimide was only synthesized as microcrystalline powder. The crystal structure was determined by powder X-ray diffraction and refined by the Rietveld method [Na{sub 4.32}Sr{sub 0.68}(CN{sub 2}){sub 2.68}(HCN{sub 2}){sub 0.32}: space group Im3m (no. 229), a = 7.2412(1) Aa, Z = 2, R{sub wp} = 0.050]. The presence of hydrogencyanamide units ([HNCN]{sup -}) next to carbodiimide units ([CN{sub 2}]{sup 2-}) in all compounds was confirmed by FT-IR spectroscopy. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

CH3NH3PbI3 based solar cell: Modified by antisolvent treatment

Science.gov (United States)

Nandi, Pronoy; Giri, Chandan; Bansode, Umesh; Topwal, D.

2017-05-01

Solar cells based on new class of organic inorganic hybrid perovskite CH3NH3PbI3 were prepared by Ethyl acetate (EA); antisolvent treatment for the first time. This treatment results in new morphology for CH3NH3PbI3 thin film. FESEM image shows microrod type structures of CH3NH3PbI3 after EA antisolvent treatment. Energy band diagram was constructed using photoluminescence and photoemission studies. A better power conversion efficiency was achieved in EA treated film compare to without EA treated film.

HCN Production via Impact Ejecta Reentry During the Late Heavy Bombardment

Science.gov (United States)

Parkos, Devon; Pikus, Aaron; Alexeenko, Alina; Melosh, H. Jay

2018-04-01

Major impact events have shaped the Earth as we know it. The Late Heavy Bombardment is of particular interest because it immediately precedes the first evidence of life. The reentry of impact ejecta creates numerous chemical by-products, including biotic precursors such as HCN. This work examines the production of HCN during the Late Heavy Bombardment in more detail. We stochastically simulate the range of impacts on the early Earth and use models developed from existing studies to predict the corresponding ejecta properties. Using multiphase flow methods and finite-rate equilibrium chemistry, we then find the HCN production due to the resulting atmospheric heating. We use Direct Simulation Monte Carlo to develop a correction factor to account for increased yields due to thermochemical nonequilibrium. We then model 1-D atmospheric turbulent diffusion to find the time accurate transport of HCN to lower altitudes and ultimately surface water. Existing works estimate the necessary HCN molarity threshold to promote polymerization that is 0.01 M. For a mixing depth of 100 m, we find that the Late Heavy Bombardment will produce at least one impact event above this threshold with probability 24.1% for an oxidized atmosphere and 56.3% for a partially reduced atmosphere. For a mixing depth of 10 m, the probability is 79.5% for an oxidized atmosphere and 96.9% for a partially reduced atmosphere. Therefore, Late Heavy Bombardment impact ejecta is likely an HCN source sufficient for polymerization in shallow bodies of water, particularly if the atmosphere were in a partially reduced state.

Response of Si- and Al-doped graphenes toward HCN: A computational study

International Nuclear Information System (INIS)

Rastegar, Somayeh F.; Peyghan, Ali Ahmadi; Hadipour, Nasser L.

2013-01-01

Highlights: ► Sensitivity of Si- and Al-doped graphene (SiG and AlG) toward HCN is investigated. ► The electronic properties of AlG are significantly changed in the presence of HCN. ► It is established that AlG can be a good sensor for HCN molecule. - Abstract: Sensitivity of Si- and Al-doped graphenes (SiG and AlG) toward toxic HCN has been investigated using density functional theory (DFT) in terms of energetic, geometric and electronic properties. Optimized configurations corresponding to physisorption and, subsequently, chemisorption of HCN on each surface have been identified. It is found that HCN molecule can be adsorbed on impurity atoms with adsorption energies about −27.20 and −38.75 kcal/mol on the SiG and the AlG, respectively. By comparing to HCN adsorption on SiG, it can be inferred that molecular HCN adsorbed on AlG can induce significant change in AlG conductivity. On the basis of calculated changes in the HOMO/LUMO energy gap it is found that electronic properties of AlG are sensitive toward adsorption of HCN and the reverse is correct for SiG, suggesting that the AlG may be a promising sensor for HCN.

Preparation of silver chloride nanoparticles by a mechanical treatment of the system NH4Cl−AgNO3−NH4NO3

Directory of Open Access Journals (Sweden)

Farit Urakaev

2014-08-01

Full Text Available Silver chloride nanoparticles dispersed within ammonium nitrate matrix have been prepared though displacement mechanochemical reaction NH4Cl + AgNO3 + z NH4NO3 = (z+1 NH4 NO3 + AgCl at various z coefficients z1 = 7.22 and z2 = 3.64. The intermediate compound of NH4Ag(NO32 were recorded after mechanochemical processing of studied system. By using simultaneous TG and DSC measurements possibilities to prepare silver chloride in its free form have been discussed by using thermal treatment.

CH3NH3Pb1−xMgxI3 perovskites as environmentally friendly photovoltaic materials

Directory of Open Access Journals (Sweden)

Y. D. Zhang

2018-01-01

Full Text Available In an effort to reduce the toxicity of Pb in perovskite solar cells, the band structures, electron and hole effective masses, and electronic and optical properties of the novel perovskites CH3NH3Pb1−xMgxI3 were predicted using density functional theory with the scalar relativistic generalized gradient approximation. The calculation results indicated that the introduction of the Mg component caused the band gaps of the CH3NH3Pb1−xMgxI3 compounds to exceed that of CH3NH3PbI3. The calculated absorption coefficients of the CH3NH3PbI3 and CH3NH3Pb1−xMgxI3 perovskites revealed that substituting 12.5 mol % of the Pb in CH3NH3PbI3 with Mg had little effect on the absorption ability. Surprisingly, it was also found that CH3NH3Pb0.75Mg0.25I3 retained up to 83% of the absorption performance relative to CH3NH3PbI3. This indicates that the amount of toxic Pb used in perovskite solar cells could be reduced by a quarter while retaining over 80% of the light-absorbing ability. In general, these novel CH3NH3Pb1−xMgxI3 (x ≤ 0.25 perovskites represent promising candidates for environmentally friendly light-harvesting materials for use in solar cells.

Parallel Changes in Intracellular Water Volume and pH Induced by NH3/NH4+ Exposure in Single Neuroblastoma Cells

Directory of Open Access Journals (Sweden)

Víctor M. Blanco

2013-12-01

Full Text Available Background: Increased blood levels of ammonia (NH3 and ammonium (NH4+, i.e. hyperammonemia, leads to cellular brain edema in humans with acute liver failure. The pathophysiology of this edema is poorly understood. This is partly due to incomplete understanding of the osmotic effects of the pair NH3/NH4+ at the cellular and molecular levels. Cell exposure to solutions containing NH3/NH4+ elicits changes in intracellular pH (pHi, which can in turn affect cell water volume (CWV by activating transport mechanisms that produce net gain or loss of solutes and water. The occurrence of CWV changes caused by NH3/NH4+ has long been suspected, but the mechanisms, magnitude and kinetics of these changes remain unknown. Methods: Using fluorescence imaging microscopy we measured, in real time, parallel changes in pHi and CWV caused by brief exposure to NH3/NH4+ of single cells (N1E-115 neuroblastoma or NG-108 neuroblastoma X glioma loaded with the fluorescent indicator BCECF. Changes in CWV were measured by exciting BCECF at its intracellular isosbestic wavelength (∼438 nm, and pHi was measured ratiometrically. Results: Brief exposure to isosmotic solutions (i.e. having the same osmolality as that of control solutions containing NH4Cl (0.5- 30 mM resulted in a rapid, dose-dependent swelling, followed by isosmotic regulatory volume decrease (iRVD. NH4Cl solutions in which either extracellular [NH3] or [NH4+] was kept constant while the other was changed by varying the pH of the solution, demonstrated that [NH3]o rather than [NH4+]o is the main determinant of the NH4Cl-induced swelling. The iRVD response was sensitive to the anion channel blocker NPPB, and partly dependent on external Ca2+. Upon removal of NH4Cl, cells shrank and displayed isosmotic regulatory volume increase (iRVI. Regulatory volume responses could not be activated by comparable CWV changes produced by anisosmotic solutions, suggesting that membrane stretch or contraction by themselves are

ORIGINS OF SCATTER IN THE RELATIONSHIP BETWEEN HCN 1-0 AND DENSE GAS MASS IN THE GALACTIC CENTER

Energy Technology Data Exchange (ETDEWEB)

Mills, Elisabeth A. C. [San Jose State University, 1 Washington Square, San Jose, CA 95192 (United States); Battersby, Cara, E-mail: elisabeth.mills@sjsu.edu [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States)

2017-01-20

We investigate the correlation of HCN 1-0 with gas mass in the central 300 pc of the Galaxy. We find that on the ∼10 pc size scale of individual cloud cores, HCN 1-0 is well correlated with dense gas mass when plotted as a log–log relationship. There is ∼0.75 dex of scatter in this relationship from clouds like Sgr B2, which has an integrated HCN 1-0 intensity of a cloud less than half its mass, and others that have HCN 1-0 enhanced by a factor of 2–3 relative to clouds of comparable mass. We identify the two primary sources of scatter to be self-absorption and variations in HCN abundance. We also find that the extended HCN 1-0 emission is more intense per unit mass than in individual cloud cores. In fact the majority (80%) of HCN 1-0 emission comes from extended gas with column densities below 7 × 10{sup 22} cm{sup −2}, accounting for 68% of the total mass. We find variations in the brightness of HCN 1-0 would only yield a ∼10% error in the dense gas mass inferred from this line in the Galactic center. However, the observed order of magnitude HCN abundance variations, and the systematic nature of these variations, warn of potential biases in the use of HCN as dense gas mass tracer in more extreme environments such as an active galactic nucleus and shock-dominated regions. We also investigate other 3 mm tracers, finding that HNCO is better correlated with mass than HCN, and might be a better tracer of cloud mass in this environment.

INHIBITION OF CORROSION OF ZINC IN (HNO3 + HCl) ACID ...

African Journals Online (AJOL)

2015-05-01

May 1, 2015 ... corrosion inhibitor for zinc in phosphoric acid. Vashi et al.[8-9] studied the corrosion inhibition of zinc in (HNO3 + H2SO4) and (HNO3 + H3PO4) binary acid mixture by aniline. In the present work, the role of aniline as inhibitor for corrosion of zinc in (HNO3 + HCl) binary acid mixture has been reported. 2.

Development of a high power HCN waveguide laser for plasma diagnostic

International Nuclear Information System (INIS)

Deng Zhongchao; Zhou Yan; Tang Yiwu; Yi Jiang; Gao Bingyi; Tian Chongli

2007-06-01

Both design and development of a high power cw HCN waveguide laser is described for multichannel FIR laser interferometer on the HL-2A divertor tokamak. The geometry parameters of stracture of the HCN laser are calculated according to scaling laws for cw 337 μm HCN waveguide laser offered by P. Belland et al. The designed value of output power of the laser that is more than 400 mW with discharge length of 5.6 m and 6.3 cm inner diameter of tube have been chosen in case of external loss of the cavity of 2%. At the same time, in order to get a laser system of stable output both of configuration and operating condition is discussed. In developed laser a hot LaB 6 cathode is employed to en- sure a stable discharge, the cavity mirrors are spaced using four invar rod of φ25 mm in diameter and an structure of adjusting machine for axially movable flat mirror in cavity has been also designed, and that it can be taken down many times without badly destroying alignment of the cavity etc.. A suit of pipes sys- tem of cw HCN laser is schemed out so that some experiments of operating parameter optimization can be done. The results of primary test of operating waveguide HCN laser are briefly showed. (authors)

The energy level alignment at the CH_3NH_3PbI_3/pentacene interface

International Nuclear Information System (INIS)

Ji, Gengwu; Zhao, Bin; Song, Fei; Zheng, Guanhaojie; Zhang, Xiaonan; Shen, Kongchao; Yang, Yingguo; Chen, Shi; Gao, Xingyu

2017-01-01

Highlights: • The Energy Level Alignment at the CH_3NH_3PbI_3/Pentacene Interface was resolved experimentally. • The downward band bending and the dipole found at the pentacene side would favorably drive holes away from the interface into pentacene. • A ∼0.7 eV offset between pentacene HOMO and CH_3NH_3PbI_3 VBM would be in favor of hole transfer whereas a ∼1.35 eV offset between pentacene LUMO and CH_3NH_3PbI_3 CBM should efficiently block the unwanted electron transfer from perovskite to pentacene. • Pentacene could be a viable hole transfer material candidate on perovskite to be explored in perovskite devices. - Abstract: Pentacene thin film on CH_3NH_3PbI_3 was studied by in-situ X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy to determine their interfacial energy level alignment. A 0.2 eV downward band bending together with a 0.1 eV interfacial dipole was found at the pentacene side, whereas there was no band bending found at the CH_3NH_3PbI_3 side. The offset between CH_3NH_3PbI_3 Valance Band Maximum (VBM) and pentacene Highest Occupied Molecular Orbital (HOMO) and that between CH_3NH_3PbI_3 Conduction Band Minimum (CBM) and pentacene Lowest Unoccupied Molecular Orbital (LUMO) was determined to be 0.7 and 1.35 eV, respectively. The band alignment at this interface is favor of efficient hole transfer, which suggests pentacene as a viable HTL candidate to be explored in perovskite solar cells.

Refinement of crystal structures of CaHCl, SrHCl, BaHCl, BaHBr, and BaHI

International Nuclear Information System (INIS)

Beck, H.P.; Limmer, A.

1983-01-01

The structures of CaHCl, SrHCl, BaHBr, BaHCl, and BaHI have been refined using single crystal data. The comparison of the parameters with the corresponding data of isotypic fluorohalide compounds gives a valuable insight into the bonding interactions in this structure type. (author)

Refinement of crystal structures of CaHCl, SrHCl, BaHCl, BaHBr, and BaHI

Energy Technology Data Exchange (ETDEWEB)

Beck, H.P.; Limmer, A. (Erlangen-Nuernberg Univ., Erlangen (Germany, F.R.). Inst. fuer Anorganische Chemie)

1983-07-01

The structures of CaHCl, SrHCl, BaHBr, BaHCl, and BaHI have been refined using single crystal data. The comparison of the parameters with the corresponding data of isotypic fluorohalide compounds gives a valuable insight into the bonding interactions in this structure type.

Herschel/HIFI deepens the circumstellar NH3 enigma

NARCIS (Netherlands)

Menten, K. M.; Wyrowski, F.; Alcolea, J.; De Beck, E.; Decin, L.; Marston, A. P.; Bujarrabal, V.; Cernicharo, J.; Dominik, C.; Justtanont, K.; de Koter, A.; Melnick, G.; Neufeld, D. A.; Olofsson, H.; Planesas, P.; Schmidt, M.; Schoier, F. L.; Szczerba, R.; Teyssier, D.; Waters, L. B. F. M.; Edwards, K.; Olberg, M.; Phillips, T. G.; Morris, P.; Salez, M.; Caux, E.

2010-01-01

Context. Circumstellar envelopes (CSEs) of a variety of evolved stars have been found to contain ammonia (NH3) in amounts that exceed predictions from conventional chemical models by many orders of magnitude. Aims. The observations reported here were performed in order to better constrain the NH3

Contribution of presynaptic HCN channels to excitatory inputs of spinal substantia gelatinosa neurons.

Science.gov (United States)

Peng, S-C; Wu, J; Zhang, D-Y; Jiang, C-Y; Xie, C-N; Liu, T

2017-09-01

Hyperpolarization-activated cyclic nucleotide-gated (HCN) channels are pathological pain-associated voltage-gated ion channels. They are widely expressed in central nervous system including spinal lamina II (also named the substantia gelatinosa, SG). Here, we examined the distribution of HCN channels in glutamatergic synaptic terminals as well as their role in the modulation of synaptic transmission in SG neurons from SD rats and glutamic acid decarboxylase-67 (GAD67)-GFP mice. We found that the expression of the HCN channel isoforms was varied in SG. The HCN4 isoform showed the highest level of co-localization with VGLUT2 (23±3%). In 53% (n=21/40 neurons) of the SG neurons examined in SD rats, application of HCN channel blocker, ZD7288 (10μM), decreased the frequency of spontaneous (s) and miniature (m) excitatory postsynaptic currents (EPSCs) by 37±4% and 33±4%, respectively. Consistently, forskolin (FSK) (an activator of adenylate cyclase) significantly increased the frequency of mEPSCs by 225±34%, which could be partially inhibited by ZD7288. Interestingly, the effects of ZD7288 and FSK on sEPSC frequency were replicated in non-GFP-expressing neurons, but not in GFP-expressing GABAergic SG neurons, in GAD67-GFP transgenic C57/BL6 mice. In summary, our results represent a previously unknown cellular mechanism by which presynaptic HCN channels, especially HCN4, regulate the glutamate release from presynaptic terminals that target excitatory, but not inhibitory SG interneurons. Copyright © 2017 IBRO. Published by Elsevier Ltd. All rights reserved.

De novo mutations in HCN1 cause early infantile epileptic encephalopathy

DEFF Research Database (Denmark)

Nava, Caroline; Dalle, Carine; Rastetter, Agnès

2014-01-01

Hyperpolarization-activated, cyclic nucleotide-gated (HCN) channels contribute to cationic Ih current in neurons and regulate the excitability of neuronal networks. Studies in rat models have shown that the Hcn1 gene has a key role in epilepsy, but clinical evidence implicating HCN1 mutations in ...

De novo mutations in HCN1 cause early infantile epileptic encephalopathy.

Science.gov (United States)

Nava, Caroline; Dalle, Carine; Rastetter, Agnès; Striano, Pasquale; de Kovel, Carolien G F; Nabbout, Rima; Cancès, Claude; Ville, Dorothée; Brilstra, Eva H; Gobbi, Giuseppe; Raffo, Emmanuel; Bouteiller, Delphine; Marie, Yannick; Trouillard, Oriane; Robbiano, Angela; Keren, Boris; Agher, Dahbia; Roze, Emmanuel; Lesage, Suzanne; Nicolas, Aude; Brice, Alexis; Baulac, Michel; Vogt, Cornelia; El Hajj, Nady; Schneider, Eberhard; Suls, Arvid; Weckhuysen, Sarah; Gormley, Padhraig; Lehesjoki, Anna-Elina; De Jonghe, Peter; Helbig, Ingo; Baulac, Stéphanie; Zara, Federico; Koeleman, Bobby P C; Haaf, Thomas; LeGuern, Eric; Depienne, Christel

2014-06-01

Hyperpolarization-activated, cyclic nucleotide-gated (HCN) channels contribute to cationic Ih current in neurons and regulate the excitability of neuronal networks. Studies in rat models have shown that the Hcn1 gene has a key role in epilepsy, but clinical evidence implicating HCN1 mutations in human epilepsy is lacking. We carried out exome sequencing for parent-offspring trios with fever-sensitive, intractable epileptic encephalopathy, leading to the discovery of two de novo missense HCN1 mutations. Screening of follow-up cohorts comprising 157 cases in total identified 4 additional amino acid substitutions. Patch-clamp recordings of Ih currents in cells expressing wild-type or mutant human HCN1 channels showed that the mutations had striking but divergent effects on homomeric channels. Individuals with mutations had clinical features resembling those of Dravet syndrome with progression toward atypical absences, intellectual disability and autistic traits. These findings provide clear evidence that de novo HCN1 point mutations cause a recognizable early-onset epileptic encephalopathy in humans.

Genetic variation in Hyperpolarization-activated cyclic nucleotide-gated (HCN channels and its relationship with neuroticism, cognition and risk of depression

Directory of Open Access Journals (Sweden)

Andrew Mark Mcintosh

2012-07-01

Full Text Available Hyperpolarization-activated cyclic nucleotide-gated (HCN channels are encoded by four genes (HCN1-4 and, through activation by cyclic AMP (cAMP, represent a point of convergence for several psychosis risk genes. On the basis of positive preliminary data, we sought to test whether genetic variation in HCN1-4 conferred risk of depression or cognitive impairment in the Generation Scotland: Scottish Family Health Study. HCN1, HCN2, HCN3 and HCN4 were genotyped for 43 haplotype-tagging SNPs and tested for association with DSM-IV depression, neuroticism and a battery of cognitive tests assessing cognitive ability, memory, verbal fluency and psychomotor performance. No association was found between any HCN channel gene SNP and risk of depression, neuroticism or on any cognitive measure. The current study does not support a genetic role for HCN channels in conferring risk of depression or cognitive impairment in human subjects within the Scottish population.

Small functional If current in sinoatrial pacemaker cells of the brown trout (Salmo trutta fario) heart despite strong expression of HCN channel transcripts.

Science.gov (United States)

Hassinen, Minna; Haverinen, Jaakko; Vornanen, Matti

2017-12-01

Funny current ( I f ), formed by hyperpolarization-activated cyclic nucleotide-gated channels (HCN channels), is supposed to be crucial for the membrane clock regulating the cardiac pacemaker mechanism. We examined the presence and activity of HCN channels in the brown trout ( Salmo trutta fario ) sinoatrial (SA) pacemaker cells and their putative role in heart rate ( f H ) regulation. Six HCN transcripts (HCN1, HCN2a, HCN2ba, HCN2bb, HCN3, and HCN4) were expressed in the brown trout heart. The total HCN transcript abundance was 4.0 and 4.9 times higher in SA pacemaker tissue than in atrium and ventricle, respectively. In the SA pacemaker, HCN3 and HCN4 were the main isoforms representing 35.8 ± 2.7 and 25.0 ± 1.5%, respectively, of the total HCN transcripts. Only a small I f with a mean current density of -1.2 ± 0.37 pA/pF at -140 mV was found in 4 pacemaker cells out of 16 spontaneously beating cells examined, despite the optimization of recording conditions for I f activity. I f was not found in any of the 24 atrial myocytes and 21 ventricular myocytes examined. HCN4 coexpressed with the MinK-related peptide 1 (MiRP1) β-subunit in CHO cells generated large I f currents. In contrast, HCN3 (+MiRP1) failed to produce I f in the same expression system. Cs + (2 mM), which blocked 84 ± 12% of the native I f , reversibly reduced f H 19.2 ± 3.6% of the excised multicellular pacemaker tissue from 53 ± 5 to 44 ± 5 beats/min ( P brown trout heart is largely independent on I f . Copyright © 2017 the American Physiological Society.

Mesoscopic CH 3 NH 3 PbI 3 /TiO 2 Heterojunction Solar Cells

KAUST Repository

Etgar, Lioz

2012-10-24

We report for the first time on a hole conductor-free mesoscopic methylammonium lead iodide (CH 3NH 3PbI 3) perovskite/TiO 2 heterojunction solar cell, produced by deposition of perovskite nanoparticles from a solution of CH 3NH 3I and PbI 2 in γ-butyrolactone on a 400 nm thick film of TiO 2 (anatase) nanosheets exposing (001) facets. A gold film was evaporated on top of the CH 3NH 3PbI 3 as a back contact. Importantly, the CH 3NH 3PbI 3 nanoparticles assume here simultaneously the roles of both light harvester and hole conductor, rendering superfluous the use of an additional hole transporting material. The simple mesoscopic CH 3NH 3PbI 3/TiO 2 heterojunction solar cell shows impressive photovoltaic performance, with short-circuit photocurrent J sc= 16.1 mA/cm 2, open-circuit photovoltage V oc = 0.631 V, and a fill factor FF = 0.57, corresponding to a light to electric power conversion efficiency (PCE) of 5.5% under standard AM 1.5 solar light of 1000 W/m 2 intensity. At a lower light intensity of 100W/m 2, a PCE of 7.3% was measured. The advent of such simple solution-processed mesoscopic heterojunction solar cells paves the way to realize low-cost, high-efficiency solar cells. © 2012 American Chemical Society.

Degradation mechanism of CH3NH3PbI3 perovskite materials upon exposure to humid air

International Nuclear Information System (INIS)

Shirayama, Masaki; Kato, Masato; Fujiseki, Takemasa; Hara, Shota; Kadowaki, Hideyuki; Murata, Daisuke; Fujiwara, Hiroyuki; Miyadera, Tetsuhiko; Sugita, Takeshi; Chikamatsu, Masayuki

2016-01-01

Low stability of organic-inorganic perovskite (CH 3 NH 3 PbI 3 ) solar cells in humid air environments is a serious drawback which could limit practical application of this material severely. In this study, from real-time spectroscopic ellipsometry characterization, the degradation mechanism of ultra-smooth CH 3 NH 3 PbI 3 layers prepared by a laser evaporation technique is studied. We present evidence that the CH 3 NH 3 PbI 3 degradation in humid air proceeds by two competing reactions of (i) the PbI 2 formation by the desorption of CH 3 NH 3 I species and (ii) the generation of a CH 3 NH 3 PbI 3 hydrate phase by H 2 O incorporation. In particular, rapid phase change occurs in the near-surface region and the CH 3 NH 3 PbI 3 layer thickness reduces rapidly in the initial 1 h air exposure even at a low relative humidity of 40%. After the prolonged air exposure, the CH 3 NH 3 PbI 3 layer is converted completely to hexagonal platelet PbI 2 /hydrate crystals that have a distinct atomic-scale multilayer structure with a period of 0.65 ± 0.05 nm. We find that conventional x-ray diffraction and optical characterization in the visible region, used commonly in earlier works, are quite insensitive to the surface phase change. Based on results obtained in this work, we discuss the degradation mechanism of CH 3 NH 3 PbI 3 in humid air.

A Reduced Reaction Scheme for Volatile Nitrogen Conversion in Coal Combustion

DEFF Research Database (Denmark)

Pedersen, Lars Saaby; Glarborg, Peter; Dam-Johansen, Kim

1998-01-01

In pulverised coal flames, the most important volatile nitrogen component forming NOx is HCN. To be able to model the nitrogen chemistry in coal flames it is necessary to have an adequate model for HCN oxidation. The present work was concerned with developing a model for HCN/NH3/NO conversion based...... that the CO/H-2 chemistry was described adequately, the reduced HCN/NH3/NO model compared very well with the detailed model over a wide range of stoichiometries. Decoupling of the HCN chemistry from the CO/H-2 chemistry resulted in over-prediction of the HCN oxidation rate under fuel rich conditions, but had...... negligible effect on the CO/H-2 chemistry. Comparison with simplified HCN models from the literature revealed significant differences, indicating that these models should be used cautiously in modelling volatile nitrogen conversion....

Probing interfacial electronic properties of graphene/CH3NH3PbI3 heterojunctions: A theoretical study

Science.gov (United States)

Hu, Jisong; Ji, Gepeng; Ma, Xinguo; He, Hua; Huang, Chuyun

2018-05-01

Interfacial interactions and electronic properties of graphene/CH3NH3PbI3 heterojunctions were investigated by first-principles calculations incorporating semiempirical dispersion-correction scheme to describe van der Waals interactions. Two lattice match configurations between graphene and CH3NH3PbI3(0 0 1) slab were constructed in parallel contact and both of them were verified to form remarkable van der Waals heterojunctions with similar work functions. Our calculated energy band structures show that the Dirac-cone of graphene and the direct band gap of CH3NH3PbI3 are still preserved in the heterojunctions, thus graphene can be a promising candidate either as a capping or supporting layer for encapsulating CH3NH3PbI3 layer. It is identified that the Schottky barrier of graphene/CH3NH3PbI3 heterojunctions can be controlled by the interlayer distance and affected by the stacking pattern of graphene and CH3NH3PbI3. The 3D charge density differences present the build-in internal electric field from graphene to CH3NH3PbI3 after interface equilibrium and thus, a low n-type Schottky barrier is needed for high efficient charge transferring in the interface. The possible mechanism of the band edge modulations in the heterojunctions and corresponding photoinduced charge transfer processes are also described.

NH{sub 4}-doped anodic WO{sub 3} prepared through anodization and subsequent NH{sub 4}OH treatment for water splitting

Energy Technology Data Exchange (ETDEWEB)

Choi, Yong-Wook; Kim, Sunkyu; Seong, Mijeong; Yoo, Hyeonseok; Choi, Jinsub, E-mail: jinsub@inha.ac.kr

2015-01-01

Highlights: • NN{sub 4}-doped WO{sub 3} was successfully fabricated by a wet-based method using ammonium hydroxide (NH{sub 4}OH). • (NH{sub 4}){sub 10}W{sub 12}O{sub 41} phase was formed during the NH{sub 4}OH treatment. • Over-doped NH{sub 4} in WO{sub 3} led to reduced photo-electrochemical performance for OER. • The optimized surface was achieved by thermal treatment of anodic WO{sub 3} with 2 g of NH{sub 4}OH solution. - Abstract: Tungsten trioxide (WO{sub 3}) prepared by anodization of a W foil was doped with NH{sub 4} through NH{sub 4}OH treatment at 450 °C. Since aqueous NH{sub 4}OH was used during doping instead of NH{sub 3} gas, the treatment step does not require complicated annealing facilities. Moreover, the state of doped N is a form of NH{sub 3}-W instead of W{sub 2}N, which lowers the bandgap but increases photocorrosion. We found that incorporation of NH{sub 4} into WO{sub 3} leads to reduction of the bandgap from 2.9 eV to 2.2 eV, regardless of the amount of NH{sub 4}OH treatment, lowering the onset potential and increasing the current density at fixed potential for oxygen evolution reaction under illumination. Scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy were employed to investigate the surface morphologies, crystallinities of tungsten oxides and existence of NH{sub 4} doping, respectively. The bandgap energy was determined by UV–Vis spectroscopy to measure the transmittance and refraction. The water splitting performance of each sample was measured by electrochemical linear sweep voltammetry in a 3-electrode configuration under illumination.

Novel insights into the distribution of cardiac HCN channels: an expression study in the mouse heart.

Science.gov (United States)

Herrmann, Stefan; Layh, Beate; Ludwig, Andreas

2011-12-01

HCN pacemaker channels (I(f) channels) are believed to contribute to important functions in the heart; thus these channels became an attractive target for generating transgenic mouse mutants to elucidate their role in physiological and pathophysiological cardiac conditions. A full understanding of cardiac I(f) and the interpretation of studies using HCN mouse mutants require detailed information about the expression profile of the individual HCN subunits. Here we investigate the cardiac expression pattern of the HCN isoforms at the mRNA as well as at the protein level. The specificity of antibodies used was strictly confirmed by the use of HCN1, HCN2 and HCN4 knockout animals. We find a low, but highly differential HCN expression profile outside the cardiac conduction pathway including left and right atria and ventricles. Additionally HCN distribution was investigated in tissue slices of the sinoatrial node, the atrioventricular node, the bundle of His and the bundle branches. The conduction system was marked by acetylcholine esterase staining. HCN4 was confirmed as the predominant isoform of the primary pacemaker followed by a distinct expression of HCN1. In contrast HCN2 shows only a confined expression to individual pacemaker cells. Immunolabeling of the AV-node reveals also a pronounced specificity for HCN1 and HCN4. Compared to the SN and AVN we found a low but selective expression of HCN4 as the only isoform in the atrioventricular bundle. However in the bundle branches HCN1, HCN4 and also HCN2 show a prominent and selective expression pattern. Our results display a characteristic distribution of individual HCN isoforms in several cardiac compartments and reveal that beside HCN4, HCN1 represents the isoform which is selectively expressed in most parts of the conduction system suggesting a substantial contribution of HCN1 to pacemaking. 2011 Elsevier Ltd. All rights reserved.

Mixed adenine/guanine quartets with three trans-a2 Pt(II) (a=NH(3) or MeNH(2)) cross-links: linkage and rotational isomerism, base pairing, and loss of NH(3).

Science.gov (United States)

Albertí, Francisca M; Rodríguez-Santiago, Luis; Sodupe, Mariona; Mirats, Andrea; Kaitsiotou, Helena; Sanz Miguel, Pablo J; Lippert, Bernhard

2014-03-17

Of the numerous ways in which two adenine and two guanines (N9 positions blocked in each) can be cross-linked by three linear metal moieties such as trans-a2 Pt(II) (with a=NH3 or MeNH2 ) to produce open metalated purine quartets with exclusive metal coordination through N1 and N7 sites, one linkage isomer was studied in detail. The isomer trans,trans,trans-[{Pt(NH3 )2 (N7-9-EtA-N1)2 }{Pt(MeNH2 )2 (N7-9-MeGH)}2 ][(ClO4 )6 ]⋅3H2 O (1) (with 9-EtA=9-ethyladenine and 9-MeGH=9-methylguanine) was crystallized from water and found to adopt a flat Z-shape in the solid state as far as the trinuclear cation is concerned. In the presence of excess 9-MeGH, a meander-like construct, trans,trans,trans-[{Pt(NH3 )2 (N7-9-EtA-N1)2 }{Pt(MeNH2 )2 (N7-9-MeGH)2 }][(ClO4 )6 ]⋅[(9-MeGH)2 ]⋅7 H2 O (2) is formed, in which the two extra 9-MeGH nucleobases are hydrogen bonded to the two terminal platinated guanine ligands of 1. Compound 1, and likewise the analogous complex 1 a (with NH3 ligands only), undergo loss of an ammonia ligand and formation of NH4 (+) when dissolved in [D6 ]DMSO. From the analogy between the behavior of 1 and 1 a it is concluded that a NH3 ligand from the central Pt atom is lost. Addition of 1-methylcytosine (1-MeC) to such a DMSO solution reveals coordination of 1-MeC to the central Pt. In an analogous manner, 9-MeGH can coordinate to the central Pt in [D6 ]DMSO. It is proposed that the proton responsible for formation of NH4 (+) is from one of the exocyclic amino groups of the two adenine bases, and furthermore, that this process is accompanied by a conformational change of the cation from Z-form to U-form. DFT calculations confirm the proposed mechanism and shed light on possible pathways of this process. Calculations show that rotational isomerism is not kinetically hindered and that it would preferably occur previous to the displacement of NH3 by DMSO. This displacement is the most energetically costly step, but it is compensated by the proton

Effects of atmospheric ammonia (NH3) on terrestrial vegetation: a review

International Nuclear Information System (INIS)

Krupa, S.V.

2003-01-01

A review of atmospheric ammonia (NH 3 ) and ammonium (NH 4 + ) deposition and their effects on plants. - At the global scale, among all N (nitrogen) species in the atmosphere and their deposition on to terrestrial vegetation and other receptors, NH 3 (ammonia) is considered to be the foremost. The major sources for atmospheric NH 3 are agricultural activities and animal feedlot operations, followed by biomass burning (including forest fires) and to a lesser extent fossil fuel combustion. Close to its sources, acute exposures to NH 3 can result in visible foliar injury on vegetation. NH 3 is deposited rapidly within the first 4-5 km from its source. However, NH 3 is also converted in the atmosphere to fine particle NH 4 + (ammonium) aerosols that are a regional scale problem. Much of our current knowledge of the effects of NH 3 on higher plants is predominantly derived from studies conducted in Europe. Adverse effects on vegetation occur when the rate of foliar uptake of NH 3 is greater than the rate and capacity for in vivo detoxification by the plants. Most to least sensitive plant species to NH 3 are native vegetation > forests > agricultural crops. There are also a number of studies on N deposition and lichens, mosses and green algae. Direct cause and effect relationships in most of those cases (exceptions being those locations very close to point sources) are confounded by other environmental factors, particularly changes in the ambient SO 2 (sulfur dioxide) concentrations. In addition to direct foliar injury, adverse effects of NH 3 on higher plants include alterations in: growth and productivity, tissue content of nutrients and toxic elements, drought and frost tolerance, responses to insect pests and disease causing microorganisms (pathogens), development of beneficial root symbiotic or mycorrhizal associations and inter species competition or biodiversity. In all these cases, the joint effects of NH 3 with other air pollutants such as all-pervasive O 3 or

Impact of Contaminants Present in Coal-Biomass Derived Synthesis Gas on Water-gas Shift and Fischer-Tropsch Synthesis Catalysts

Energy Technology Data Exchange (ETDEWEB)

Alptekin, Gokhan [TDA Research, Inc., Wheat Ridge, CO (United States)

2013-02-15

Co-gasification of biomass and coal in large-scale, Integrated Gasification Combined Cycle (IGCC) plants increases the efficiency and reduces the environmental impact of making synthesis gas ("syngas") that can be used in Coal-Biomass-to-Liquids (CBTL) processes for producing transportation fuels. However, the water-gas shift (WGS) and Fischer-Tropsch synthesis (FTS) catalysts used in these processes may be poisoned by multiple contaminants found in coal-biomass derived syngas; sulfur species, trace toxic metals, halides, nitrogen species, the vapors of alkali metals and their salts (e.g., KCl and NaCl), ammonia, and phosphorous. Thus, it is essential to develop a fundamental understanding of poisoning/inhibition mechanisms before investing in the development of any costly mitigation technologies. We therefore investigated the impact of potential contaminants (H₂S, NH₃, HCN, AsH₃, PH₃, HCl, NaCl, KCl, AS₃, NH₄NO₃, NH₄OH, KNO₃, HBr, HF, and HNO₃) on the performance and lifetime of commercially available and generic (prepared in-house) WGS and FT catalysts.

ALMA INVESTIGATION OF VIBRATIONALLY EXCITED HCN/HCO{sup +}/HNC EMISSION LINES IN THE AGN-HOSTING ULTRALUMINOUS INFRARED GALAXY IRAS 20551−4250

Energy Technology Data Exchange (ETDEWEB)

Imanishi, Masatoshi [Subaru Telescope, 650 North A’ohoku Place, Hilo, HI 96720 (United States); Nakanishi, Kouichiro [National Astronomical Observatory of Japan, 2-21-1 Osawa, Mitaka, Tokyo 181-8588 (Japan); Izumi, Takuma, E-mail: masa.imanishi@nao.ac.jp [Institute of Astronomy, School of Science, The University of Tokyo, 2-21-1 Osawa, Mitaka, Tokyo 181-0015 (Japan)

2016-07-01

We present the results of ALMA Cycle 2 observations of the ultraluminous infrared galaxy IRAS 20551−4250 at HCN/HCO{sup +}/HNC J = 3–2 lines at both vibrational ground ( v = 0) and vibrationally excited ( v {sub 2} = 1) levels. This galaxy contains a luminous buried active galactic nucleus (AGN), in addition to starburst activity, and our ALMA Cycle 0 data revealed a tentatively detected vibrationally excited HCN v {sub 2} = 1f J = 4–3 emission line. In our ALMA Cycle 2 data, the HCN/HCO{sup +}/HNC J = 3–2 emission lines at v = 0 are clearly detected. The HCN and HNC v {sub 2} = 1f J = 3–2 emission lines are also detected, but the HCO{sup +} v {sub 2} = 1f J = 3–2 emission line is not. Given the high energy level of v {sub 2} = 1 and the resulting difficulty of collisional excitation, we compared these results with those of the calculation of infrared radiative pumping, using the available infrared 5–35 μ m spectrum. We found that all of the observational results were reproduced if the HCN abundance was significantly higher than that of HCO{sup +} and HNC. The flux ratio and excitation temperature between v {sub 2} = 1f and v = 0, after correction for possible line opacity, suggests that infrared radiative pumping affects rotational ( J -level) excitation at v = 0 at least for HCN and HNC. The HCN-to-HCO{sup +} v = 0 flux ratio is higher than those of starburst-dominated regions, and will increase even more when the derived high HCN opacity is corrected. The enhanced HCN-to-HCO{sup +} flux ratio in this AGN-hosting galaxy can be explained by the high HCN-to-HCO{sup +} abundance ratio and sufficient HCN excitation at up to J = 4, rather than the significantly higher efficiency of infrared radiative pumping for HCN than HCO{sup +}.

Fabrication of CH3NH3PbI3/PVP Composite Fibers via Electrospinning and Deposition

Science.gov (United States)

Chao, Li-Min; Tai, Ting-Yu; Chen, Yueh-Ying; Lin, Pei-Ying; Fu, Yaw-Shyan

2015-01-01

In our study, one-dimensional PbI2/polyvinylpyrrolidone (PVP) composition fibers have been prepared by using PbI2 and PVP as precursors dissolved in N,N-dimethylformamide via a electrospinning process. Dipping the fibers into CH3NH3I solution changed its color, indicating the formation of CH3NH3PbI3, to obtain CH3NH3PbI3/PVP composite fibers. The structure, morphology and composition of the all as-prepared fibers were characterized by using X-ray diffraction and scanning electron microscopy. PMID:28793517

Fabrication of CH3NH3PbI3/PVP Composite Fibers via Electrospinning and Deposition

Directory of Open Access Journals (Sweden)

Li-Min Chao

2015-08-01

Full Text Available In our study, one-dimensional PbI2/polyvinylpyrrolidone (PVP composition fibers have been prepared by using PbI2 and PVP as precursors dissolved in N,N-dimethylformamide via a electrospinning process. Dipping the fibers into CH3NH3I solution changed its color, indicating the formation of CH3NH3PbI3, to obtain CH3NH3PbI3/PVP composite fibers. The structure, morphology and composition of the all as-prepared fibers were characterized by using X-ray diffraction and scanning electron microscopy.

Effects of atmospheric ammonia (NH3) on terrestrial vegetation: a review.

Science.gov (United States)

Krupa, S V

2003-01-01

At the global scale, among all N (nitrogen) species in the atmosphere and their deposition on to terrestrial vegetation and other receptors, NH3 (ammonia) is considered to be the foremost. The major sources for atmospheric NH3 are agricultural activities and animal feedlot operations, followed by biomass burning (including forest fires) and to a lesser extent fossil fuel combustion. Close to its sources, acute exposures to NH3 can result in visible foliar injury on vegetation. NH3 is deposited rapidly within the first 4-5 km from its source. However, NH3 is also converted in the atmosphere to fine particle NH4+ (ammonium) aerosols that are a regional scale problem. Much of our current knowledge of the effects of NH3 on higher plants is predominantly derived from studies conducted in Europe. Adverse effects on vegetation occur when the rate of foliar uptake of NH3 is greater than the rate and capacity for in vivo detoxification by the plants. Most to least sensitive plant species to NH3 are native vegetation > forests > agricultural crops. There are also a number of studies on N deposition and lichens, mosses and green algae. Direct cause and effect relationships in most of those cases (exceptions being those locations very close to point sources) are confounded by other environmental factors, particularly changes in the ambient SO2 (sulfur dioxide) concentrations. In addition to direct foliar injury, adverse effects of NH3 on higher plants include alterations in: growth and productivity, tissue content of nutrients and toxic elements, drought and frost tolerance, responses to insect pests and disease causing microorganisms (pathogens), development of beneficial root symbiotic or mycorrhizal associations and inter species competition or biodiversity. In all these cases, the joint effects of NH3 with other air pollutants such as all-pervasive O3 or increasing CO2 concentrations are poorly understood. While NH3 uptake in higher plants occurs through the shoots, NH4

Inferior Olive HCN1 Channels Coordinate Synaptic Integration and Complex Spike Timing

Directory of Open Access Journals (Sweden)

Derek L.F. Garden

2018-02-01

Full Text Available Cerebellar climbing-fiber-mediated complex spikes originate from neurons in the inferior olive (IO, are critical for motor coordination, and are central to theories of cerebellar learning. Hyperpolarization-activated cyclic-nucleotide-gated (HCN channels expressed by IO neurons have been considered as pacemaker currents important for oscillatory and resonant dynamics. Here, we demonstrate that in vitro, network actions of HCN1 channels enable bidirectional glutamatergic synaptic responses, while local actions of HCN1 channels determine the timing and waveform of synaptically driven action potentials. These roles are distinct from, and may complement, proposed pacemaker functions of HCN channels. We find that in behaving animals HCN1 channels reduce variability in the timing of cerebellar complex spikes, which serve as a readout of IO spiking. Our results suggest that spatially distributed actions of HCN1 channels enable the IO to implement network-wide rules for synaptic integration that modulate the timing of cerebellar climbing fiber signals.

13N-NH3 PET in the diagnosis of astrocytomas: preliminary result

International Nuclear Information System (INIS)

Zhang Xiangsong; He Zuoxiang; Tang Anwu

2004-01-01

Objective: To evaluate the feasibility of diagnosing the astrocytoma with 13N-NH3 PET imaging. Methods 13N-NH3 and 18F-fluorodeoxyglucose (FDG) PET imaging were performed in seven cases of astrocytomas including 3 anteoperative astrocytomas, 2 recurrent astrocytomas, 2 brain injury or necrosis after the operation and radiotherapy. The radioactivity ratios of the tumor and normal white matter (T/WM) were calculated. Results: The tumor lesions in 3 anteoperative astrocytomas and 2 recurrent astrocytomas all uptake 13N-NH3. The average T/WM on 13N-NH3 images was 1.82±0.21, and T/WM on 13N-NH3 and 18F-FDG images were 1.98 and 0.97 for one case with grade 1 astrocytoma. 13N-NH3 and 18F-FDG PET imaging both showed decreased uptake in 2 brain injury or necrosis after the operation and radiotherapy of astrocytomas. Conclusions: 13N-NH3 was uptaken in astrocytomas. 13N-NH3 can be useful in the diagnosis of astrocytoma, and potentially improve diagnostic accuracy of astrocytoma, especially in low-grade astrocytoma. (authors)

13N-NH3 PET in the diagnosis of astrocytomas: preliminary result

International Nuclear Information System (INIS)

Zhang Xiangsong; He Zuoxiang; Tang Anwu

2004-01-01

Objective: To evaluate the feasibility of diagnosing the astrocytoma with 13N-NH3 PET imaging. Methods: 13N-NH3 and 18F-fluorodeoxyglucose (FDG) PET imaging were performed in seven cases of astrocytomas including 3 anteoperative astrocytomas, 2 recurrent astrocytomas, 2 brain injury or necrosis after the operation and radiotherapy. The radioactivity ratios of the tumor and normal white matter (T/WM) were calculated. Results: The tumor lesions in 3 anteoperative astrocytomas and 2 recurrent astrocytomas all uptake 13N-NH3 .The average T/WM on 13N-NH3 images was 1.82±0.21, and T/WM on 13N-NH3 and 18F-FDG images were 1.98 and 0.97 for one case with grade 1 astrocytoma. 13N-NH3 and 18F-FDG PET imaging both showed decreased uptake in 2 brain injury or necrosis after the operation and radiotherapy of astrocytomas. Conclusions: 13N-NH3 was uptaken in astrocytomas. 13N-NH3 can be useful in the diagnosis of astrocytoma, and potentially improve diagnostic accuracy of astrocytoma, especially in low-grade astrocytoma. (authors)

HCN channels are not required for mechanotransduction in sensory hair cells of the mouse inner ear.

Directory of Open Access Journals (Sweden)

Geoffrey C Horwitz

Full Text Available The molecular composition of the hair cell transduction channel has not been identified. Here we explore the novel hypothesis that hair cell transduction channels include HCN subunits. The HCN family of ion channels includes four members, HCN1-4. They were originally identified as the molecular correlates of the hyperpolarization-activated, cyclic nucleotide gated ion channels that carry currents known as If, IQ or Ih. However, based on recent evidence it has been suggested that HCN subunits may also be components of the elusive hair cell transduction channel. To investigate this hypothesis we examined expression of mRNA that encodes HCN1-4 in sensory epithelia of the mouse inner ear, immunolocalization of HCN subunits 1, 2 and 4, uptake of the transduction channel permeable dye, FM1-43 and electrophysiological measurement of mechanotransduction current. Dye uptake and transduction current were assayed in cochlear and vestibular hair cells of wildtype mice exposed to HCN channel blockers or a dominant-negative form of HCN2 that contained a pore mutation and in mutant mice that lacked HCN1, HCN2 or both. We found robust expression of HCNs 1, 2 and 4 but little evidence that localized HCN subunits in hair bundles, the site of mechanotransduction. Although high concentrations of the HCN antagonist, ZD7288, blocked 50-70% of the transduction current, we found no reduction of transduction current in either cochlear or vestibular hair cells of HCN1- or HCN2- deficient mice relative to wild-type mice. Furthermore, mice that lacked both HCN1 and HCN2 also had normal transduction currents. Lastly, we found that mice exposed to the dominant-negative mutant form of HCN2 had normal transduction currents as well. Taken together, the evidence suggests that HCN subunits are not required for mechanotransduction in hair cells of the mouse inner ear.

Process-based modelling of NH3 exchange with grazed grasslands

Science.gov (United States)

Móring, Andrea; Vieno, Massimo; Doherty, Ruth M.; Milford, Celia; Nemitz, Eiko; Twigg, Marsailidh M.; Horváth, László; Sutton, Mark A.

2017-09-01

In this study the GAG model, a process-based ammonia (NH3) emission model for urine patches, was extended and applied for the field scale. The new model (GAG_field) was tested over two modelling periods, for which micrometeorological NH3 flux data were available. Acknowledging uncertainties in the measurements, the model was able to simulate the main features of the observed fluxes. The temporal evolution of the simulated NH3 exchange flux was found to be dominated by NH3 emission from the urine patches, offset by simultaneous NH3 deposition to areas of the field not affected by urine. The simulations show how NH3 fluxes over a grazed field in a given day can be affected by urine patches deposited several days earlier, linked to the interaction of volatilization processes with soil pH dynamics. Sensitivity analysis showed that GAG_field was more sensitive to soil buffering capacity (β), field capacity (θfc) and permanent wilting point (θpwp) than the patch-scale model. The reason for these different sensitivities is dual. Firstly, the difference originates from the different scales. Secondly, the difference can be explained by the different initial soil pH and physical properties, which determine the maximum volume of urine that can be stored in the NH3 source layer. It was found that in the case of urine patches with a higher initial soil pH and higher initial soil water content, the sensitivity of NH3 exchange to β was stronger. Also, in the case of a higher initial soil water content, NH3 exchange was more sensitive to the changes in θfc and θpwp. The sensitivity analysis showed that the nitrogen content of urine (cN) is associated with high uncertainty in the simulated fluxes. However, model experiments based on cN values randomized from an estimated statistical distribution indicated that this uncertainty is considerably smaller in practice. Finally, GAG_field was tested with a constant soil pH of 7.5. The variation of NH3 fluxes simulated in this way

Molecular beam epitaxy of GaN(0001) utilizing NH3 and/or NH+x ions: Growth kinetics and defect structure

International Nuclear Information System (INIS)

Lee, N.; Powell, R.C.; Kim, Y.; Greene, J.E.

1995-01-01

Gas-source molecular beam epitaxy (GS-MBE), utilizing Ga and NH 3 , and reactive-ion MBE (RIMBE), incorporating both thermal NH 3 and low-energy NH + x ions, were used to grow single crystal GaN(0001) layers on Al 2 O 3 (0001) at temperatures T s between 700 and 850 degree C with deposition rates of 0.2--0.5 μm h -1 . The RIMBE experiments were carried out with incident NH + x /Ga flux ratios J NH + x /J Ga =1.9--3.2 and NH + x acceleration energies E NH + x =45--90 eV. Plan-view and cross-sectional transmission electron microscopy analyses showed that the primary defects in the GS-MBE films were threading dislocations having either pure edge or mixed edge/screw characteristics with Burgers vectors bar b=1/3 left-angle 2 bar 1 bar 10 right-angle, basal-plane stacking faults with displacement vectors bar R=1/6 left-angle 02 bar 23 right-angle, and prismatic stacking faults with bar R=1/2 left-angle bar 1101 right-angle. In the case of RIMBE films, no stacking faults or residual ion-induced defects were observed with E NH + x =45 eV and T s ≥800 degree C. However, increasing E NH + x to ≥60 eV at T s =800 degree C gave rise to the formation of residual ion-induced point-defect clusters observable by transmission electron microscopy (TEM). Increasing T s to 850 degree C with E NH + x ≥60 eV resulted in the ion-induced defects aggregating to form interstitial basal and prismatic dislocation loops, whose number densities depended upon the ion flux, with Burgers vectors 1/2 left-angle 0001 right-angle and 1/3 left-angle 2 bar 1 bar 10 right-angle, respectively. (Abstract Truncated)

Atmospheric NH3 as plant nutrient: A case study with Brassica oleracea

International Nuclear Information System (INIS)

Castro, Ana; Stulen, Ineke; De Kok, Luit J.

2008-01-01

Nutrient-sufficient and nitrate- or sulfate-deprived plants of Brassica oleracea L. were exposed to 4 μl l -1 NH 3 (2.8 mg m -3 ), and effects on biomass production and allocation, N-compounds and root morphology investigated. Nitrate-deprived plants were able to transfer to atmospheric NH 3 as nitrogen source, but biomass allocation in favor of the root was not changed by exposure to NH 3 . NH 3 reduced the difference in total root length between nitrate-sufficient and nitrate-deprived plants, and increased the specific root length in the latter. The internal N status, therefore, might be involved in controlling root length in B. oleracea. Root surface area, volume and diameter were unaffected by both nitrate deprivation and NH 3 exposure. In sulfate-deprived plants an inhibitory effect of NH 3 on root morphological parameters was observed. These plants, therefore, might be more susceptible to atmospheric NH 3 than nitrate-deprived plants. The relevance of the present data under field conditions is discussed. - Atmospheric NH 3 can serve as sole N source for Brassica oleracea, but does not change root biomass allocation in nitrate-deprived plants

Adsorption of HCN molecules on Ni, Pd and Pt-doped (7, 0) boron nitride nanotube: a DFT study

Science.gov (United States)

Habibi-Yangjeh, Aziz; Basharnavaz, Hadi

2018-05-01

We studied affinity of pure and Ni, Pd and Pt-doped (7, 0) boron nitride nanotubes (BNNTs) to toxic HCN molecules using density functional theory calculations. The results indicated that the pure (7, 0) BNNTs can weakly adsorb HCN molecules with adsorption energy of -0.2474 eV. Upon adsorption of HCN molecules on this nanotube, the band gap energy was decreased from 3.320 to 2.960 eV. The more negative adsorption energy between these transition metal-doped (7, 0) BNNTs and HCN molecules indicated that doping of (7, 0) BNNTs with Ni, Pd and Pt elements can significantly improve the affinity of BNNTs toward this gas. Additionally, it was found that the interaction energy between HCN molecules and Pt-doped BNNTs is more negative than those of the Ni and Pd-doped BNNTs. These observations suggested that the Pt-doped (7, 0) BNNTs are strongly sensitive to HCN molecules and therefore it may be used in gas sensor devices for detecting this toxic gas.

HCN(1-0) enhancement in the bar of NGC 2903

Science.gov (United States)

Leon, S.; Jeyakumar, S.; Pérez-Ramírez, D.; Verdes-Montenegro, L.; Lee, S. W.; Ocaña Flaquer, B.

2008-12-01

We have mapped the HCN(1-0) emission from two spiral galaxies, NGC 2903 and NGC 3504 to study the gas properties in the bars. The HCN(1-0) emission is detected in the center and along the bar of NGC 2903. The line ratio HCN(1-0)/ 12CO(1-0) ranges from 0.07 to 0.12 with the lowest value in the center. The enhancement of HCN(1-0) emission along the bar indicates a higher fraction of dense molecular gas in the bar than at the center. The mass of dense molecular gas in the center (2.2 × 107 M⊙) is about 6 times lower than that in the bar (1.2 × 108 M⊙). The total star formation rate (SFR) is estimated to be 1.4 M⊙ yr-1, where the SFR at the center is 1.9 times higher than that in the bar. The time scale of consumption of the dense molecular gas in the center is about ~ 3 × 107 yr which is much shorter than that in the bar of about 2 to 10 × 108 yr. The dynamical time scale of inflow of the gas from the bar to the center is shorter than the consumption time scale in the bar, which suggests that the star formation (SF) activity at the center is not deprived of fuel. In the bar, the fraction of dense molecular gas mass relative to the total molecular gas mass is twice as high along the leading edge than along the central axis of the bar. The HCN(1-0) emission has a large velocity dispersion in the bar, which can be attributed partially to the streaming motions indicative of shocks along the bar. In NGC 3504, the HCN(1-0) emission is detected only at the center. The fraction of dense molecular gas mass in the center is about 15%. Comparison of the SFR with the predictions from numerical simulations suggest that NGC 2903 harbors a young type B bar with a strong inflow of gas toward the center whereas NGC 3504 has an older bar and has already passed the phase of inflow of gas toward the center.

Rate Coefficients for Reactions of Ethynyl Radical (C2H) With HCN and CH3CN: Implications for the Formation of Comples Nitriles on Titan

Science.gov (United States)

Hoobler, Ray J.; Leone, Stephen R.

1997-01-01

Rate coefficients for the reactions of C2H + HCN yields products and C2H + CH3CN yields products have been measured over the temperature range 262-360 K. These experiments represent an ongoing effort to accurately measure reaction rate coefficients of the ethynyl radical, C2H, relevant to planetary atmospheres such as those of Jupiter and Saturn and its satellite Titan. Laser photolysis of C2H2 is used to produce C2H, and transient infrared laser absorption is employed to measure the decay of C2H to obtain the subsequent reaction rates in a transverse flow cell. Rate constants for the reaction C2H + HCN yields products are found to increase significantly with increasing temperature and are measured to be (3.9-6.2) x 10(exp 13) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 297-360 K. The rate constants for the reaction C2H + CH3CN yields products are also found to increase substantially with increasing temperature and are measured to be (1.0-2.1) x 10(exp -12) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 262-360 K. For the reaction C2H + HCN yields products, ab initio calculations of transition state structures are used to infer that the major products form via an addition/elimination pathway. The measured rate constants for the reaction of C2H + HCN yields products are significantly smaller than values currently employed in photochemical models of Titan, which will affect the HC3N distribution.

SPATIALLY RESOLVED HCN ABSORPTION FEATURES IN THE CIRCUMNUCLEAR REGION OF NGC 1052

Energy Technology Data Exchange (ETDEWEB)

Sawada-Satoh, Satoko [Mizusawa VLBI Observatory, National Astronomical Observatory of Japan, 2-12 Hoshigaoka-cho, Mizusawa-ku, Oshu, Iwate 023-0861 (Japan); Roh, Duk-Gyoo; Oh, Se-Jin; Lee, Sang-Sung; Byun, Do-Young; Yeom, Jae-Hwan; Jung, Dong-Kyu; Kim, Hyo-Ryoung; Hwang, Ju-Yeon [Korea Astronomy and Space Science Institute, 776 Daedeok-daero, Yuseong, Daejeon 34055 (Korea, Republic of); Kameno, Seiji, E-mail: satoko.ss@nao.ac.jp, E-mail: sss@mx.ibaraki.ac.jp [Joint ALMA Observatory, Alonso de Cordova 3107 Vitacura, Santiago 763 0355 (Chile)

2016-10-10

We present the first VLBI detection of HCN molecular absorption in the nearby active galactic nucleus NGC 1052. Utilizing the 1 mas resolution achieved by the Korean VLBI Network, we have spatially resolved the HCN absorption against a double-sided nuclear jet structure. Two velocity features of HCN absorption are detected significantly at the radial velocity of 1656 and 1719 km s{sup −1}, redshifted by 149 and 212 km s{sup −1} with respect to the systemic velocity of the galaxy. The column density of the HCN molecule is estimated to be 10{sup 15}–10{sup 16} cm{sup −2}, assuming an excitation temperature of 100–230 K. The absorption features show high optical depth localized on the receding jet side, where the free–free absorption occurred due to the circumnuclear torus. The size of the foreground absorbing molecular gas is estimated to be on approximately one-parsec scales, which agrees well with the approximate size of the circumnuclear torus. HCN absorbing gas is likely to be several clumps smaller than 0.1 pc inside the circumnuclear torus. The redshifted velocities of the HCN absorption features imply that HCN absorbing gas traces ongoing infall motion inside the circumnuclear torus onto the central engine.

The importance of fuel properties in the formation of nitrogen oxides and in combustion

International Nuclear Information System (INIS)

Huotari, J.; Aho, M.; Haemaelaeinen, J.; Huotari, J.; Saastamoinen, J.; Rantanen, J.

1995-01-01

The goal of this work is to find new information about the effects of pressure, temperature and fuel properties (Fuel-O/Fuel-N) on the formation of nitrogen oxides through the most important intermediates (NH 3 and HCN). In addition, a single particle model for the simultaneous pyrolysis and char combustion will be improved to be used for calculating combustion under pressure. Experimental work is done with an electrically heated pressurized entrained flow reactor (PEFR) which is equipped with modern analytics (as FT-IR for the analysis of N 2 O, NO and NO 2 and FT-IR pyrometry for the measurement of particle temperatures). The experimental work is carried out in several stages: (a) Study of the formation of HCN and NH 3 during pressurized pyrolysis (b) Oxidation of HCN and NH 3 to nitrogen oxides in pressurized combustion (c) Reduction of NO by NH 3 under pressure (thermax denox) Task a is performed with fuels of various O/N ratio. Task b is performed with pure HCN and NH 3 and with more complicated gas mixtures including HCN and NH 3 . A large part of these results are utilized in kinetic modelling in Aabo Akademi University, Finland in project LIEKKI 2-201. Two kinds of modelling work is performed in VTT in this project (a) Simultaneous modelling of the composition of solid and gaseous phases in the pyrolysis and combustion of a small fuel particle (multiphase modelling) (b) Modelling of pyrolysis and combustion of a single fuel particle under pressurized conditions (single particle modelling). The results can be used in planning of pressurized combustors and in minimizing the emissions of nitrogen oxides. (author)

Shape-Evolution Control of hybrid perovskite CH3NH3PbI3 crystals via solvothermal synthesis

Science.gov (United States)

Zhang, Baohua; Guo, Fuqiang; Yang, Lianhong; Jia, Xiuling; Liu, Bin; Xie, Zili; Chen, Dunjun; Lu, Hai; Zhang, Rong; Zheng, Youdou

2017-02-01

We systematically synthesized CH3NH3PbI3 crystals using solvothermal process, and the reaction conditions such as concentration of the precursor, temperature, time, and lead source have been comprehensively investigated to obtain shape-controlled CH3NH3PbI3 crystals. The results showed that the CH3NH3PbI3 crystals exhibit tetragonal phase and the crystals change from nanoparticles to hopper-faced cuboids. Photoluminescence spectra of the crystals obtained with different lead sources show a blue shift due to the presence of defects in the crystals, and the peak intensity is very sensitive to the lead sources. Moreover, impurities (undesirable byproducts and excess components like HI or CH3NH2) presented during crystal growth can result in hopper growth.

HCl Flow-Induced Phase Change of α-, β-, and ε-Ga2O3 Films Grown by MOCVD

KAUST Repository

Sun, Haiding

2018-03-06

Precise control of the heteroepitaxy on a low-cost foreign substrate is often the key to drive the success of fabricating semiconductor devices in scale when a large low-cost native substrate is not available. Here, we successfully synthesized three different phases of Ga2O3 (α, β, and ε) films on c-plane sapphire by only tuning the flow rate of HCl along with other precursors in an MOCVD reactor. A 3-fold increase in the growth rate of pure β-Ga2O3 was achieved by introducing only 5 sccm of HCl flow. With continuously increased HCl flow, a mixture of β- and ε-Ga2O3 was observed, until the Ga2O3 film transformed completely to a pure ε-Ga2O3 with a smooth surface and the highest growth rate (∼1 μm/h) at a flow rate of 30 sccm. At 60 sccm, we found that the film tended to have a mixture of α- and ε-Ga2O3 with a dominant α-Ga2O3, while the growth rate dropped significantly (∼0.4 μm/h). The film became rough as a result of the mixture phases since the growth rate of ε-Ga2O3 is much higher than that of α-Ga2O3. In this HCl-enhanced MOCVD mode, the Cl impurity concentration was almost identical among the investigated samples. On the basis of our density functional theory calculation, we found that the relative energy between β-, ε-, and α-Ga2O3 became smaller, thus inducing the phase change by increasing the HCl flow in the reactor. Thus, it is plausible that the HCl acted as a catalyst during the phase transformation process. Furthermore, we revealed the microstructure and the epitaxial relationship between Ga2O3 with different phases and the c-plane sapphire substrates. Our HCl-enhanced MOCVD approach paves the way to achieving highly controllable heteroepitaxy of Ga2O3 films with different phases for device applications.

Transparent CH{sub 3}NH{sub 3}SnCl{sub 3}/Al-ZnO p-n heterojunction diode

Energy Technology Data Exchange (ETDEWEB)

Kumar, Sunil, E-mail: skbgudha@gmail.com; Ansari, Mohd Zubair; Khare, Neeraj [Department of Physics, Indian Institute of Technology, Hauz Khas, New Delhi, Delhi-110016 (India)

2016-05-23

A p-type Organic inorganic tin chloride (CH{sub 3}NH{sub 3}SnCl{sub 3}) perovskite thin film has been synthesized by solution method. An n-type 1% Al doped ZnO (AZO) film has been deposited on FTO substrate by ultrasonic assisted chemical vapor deposition technique. A transparent CH{sub 3}NH{sub 3}SnCl{sub 3}/AZO p-n heterojunction diode has been fabricated by spin coating technique. CH{sub 3}NH{sub 3}SnCl{sub 3}/AZO p-n heterojunction shows 75% transparency in the visible region. I-V characteristic of CH{sub 3}NH{sub 3}SnCl{sub 3}/AZO p-n heterojunction shows rectifying behavior of the diode. The diode parameters calculated as ideality factor η=2.754 and barrier height Φ= 0.76 eV. The result demonstrates the potentiality of CH{sub 3}NH{sub 3}SnCl{sub 3}/AZO p-n heterojunction for transparent electronics.

Urban NH3 levels and sources in six major Spanish cities.

Science.gov (United States)

Reche, Cristina; Viana, Mar; Karanasiou, Angeliki; Cusack, Michael; Alastuey, Andrés; Artiñano, Begoña; Revuelta, M Aranzazu; López-Mahía, Purificación; Blanco-Heras, Gustavo; Rodríguez, Sergio; Sánchez de la Campa, Ana M; Fernández-Camacho, Rocío; González-Castanedo, Yolanda; Mantilla, Enrique; Tang, Y Sim; Querol, Xavier

2015-01-01

A detailed spatial and temporal assessment of urban NH3 levels and potential emission sources was made with passive samplers in six major Spanish cities (Barcelona, Madrid, A Coruña, Huelva, Santa Cruz de Tenerife and Valencia). Measurements were conducted during two different periods (winter-autumn and spring-summer) in each city. Barcelona showed the clearest spatial pattern, with the highest concentrations in the old city centre, an area characterised by a high population density and a dense urban architecture. The variability in NH3 concentrations did not follow a common seasonal pattern across the different cities. The relationship of urban NH3 with SO2 and NOX allowed concluding on the causes responsible for the variations in NH3 levels between measurement periods observed in Barcelona, Huelva and Madrid. However, the factors governing the variations in A Coruña, Valencia and Santa Cruz de Tenerife are still not fully understood. This study identified a broad variability in NH3 concentrations at the city-scale, and it confirms that NH3 sources in Spanish urban environments are vehicular traffic, biological sources (e.g. garbage containers), wastewater treatment plants, solid waste treatment plants and industry. The importance of NH3 monitoring in urban environments relies on its role as a precursor of secondary inorganic species and therefore PMX. Further research should be addressed in order to establish criteria to develop and implement mitigation strategies for cities, and to include urban NH3 sources in the emission inventories. Copyright © 2014 Elsevier Ltd. All rights reserved.

[Ag(NH3)2]Ag(OsO3N)2: a new nitridoosmate(VIII)

International Nuclear Information System (INIS)

Wickleder, M.S.; Pley, Martin

2004-01-01

Dark brown single crystals of [Ag(NH 3 ) 2 ]Ag(OsO 3 N) 2 were obtained from the reaction of Ag 2 CO 3 , OsO 4 , and NH 3 in aqueous solution. The crystal structure was solved in the monoclinic space group C2/m, with the following unit-cell dimensions: a=1962.5(3), b=633.1(1), c=812.6(1) pm, β=96.71(1) deg. The final reliability factor was R=0.0256 for 1034 reflections with I>2σ(I). Linear [Ag(NH 3 ) 2 ] + ions are present oriented perpendicular to the [010] direction, leading to short Ag + -Ag + distances of 316 pm. A second type of Ag + ions in the crystal structure present coordination number '6+1' and are surrounded by oxygen and nitrogen atoms of the nitridoosmate groups. Within the first of the two crystallographically distinguishable anions one can clearly differentiate between oxygen and nitrogen atoms while the second one exhibits a N/O disorder over two positions. The infrared spectrum of [Ag(NH 3 ) 2 ]Ag(OsO 3 N) 2 shows the typical absorptions which can be attributed to the complex anions and the NH 3 ligands

Crystal Structure Formation of CH3NH3PbI3-xClx Perovskite

Directory of Open Access Journals (Sweden)

Shiqiang Luo

2016-02-01

Full Text Available Inorganic-organic hydride perovskites bring the hope for fabricating low-cost and large-scale solar cells. At the beginning of the research, two open questions were raised: the hysteresis effect and the role of chloride. The presence of chloride significantly improves the crystallization and charge transfer property of the perovskite. However, though the long held debate over of the existence of chloride in the perovskite seems to have now come to a conclusion, no prior work has been carried out focusing on the role of chloride on the electronic performance and the crystallization of the perovskite. Furthermore, current reports on the crystal structure of the perovskite are rather confusing. This article analyzes the role of chloride in CH3NH3PbI3-xClx on the crystal orientation and provides a new explanation about the (110-oriented growth of CH3NH3PbI3 and CH3NH3PbI3-xClx.

THE KINETICS OF NH(4)+ AND NO3(-) UPTAKE BY DOUGLAS-FIR FROM SINGLE N-SOLUTIONS AND FROM SOLUTIONS CONTAINING BOTH NH(4)+ AND NO3(-)

NARCIS (Netherlands)

KAMMINGAVANWIJK, C; PRINS, HBA

The kinetics of NH4+ and NO3- uptake in young Douglas fir trees (Pseudotsuga menziesii [Mirb.] Franco) were studied in solutions, containing either one or both N species. Using solutions containing a single N species, the V(max) of NH4+ uptake was higher than that of NO3- uptake. The K(m) of NH4+

[Seasonal variation patterns of NH4(+) -N/NO3(-) -N ratio and delta 15 NH4(+) value in rainwater in Yangtze River Delta].

Science.gov (United States)

Xie, Ying-Xin; Zhang, Shu-Li; Zhao, Xu; Xiong, Zheng-Qin; Xing, Guang-Xi

2008-09-01

By using a customized manual rainwater sampler made of polyvinyl chloride plastic, the molar ratio of NH4(+) -N/NO3(-) -N and the natural 15N abundance of NH4(+) (delta 15 NH4(+) in rainwater was monitored all year round from June 2003 to July 2005 at three observation sites (Changshu, Nanjing, and Hangzhou) in the Yangtze River Delta. The results indicated that at the three sites, the NH4(+) -N/NO3(-) -N ratio and the delta 15 NH4(+) value in rainwater had the similar seasonal variation trend, being more obvious in Changshu (rural monitoring type) site than in Nanjing (urban monitoring type) and Hangzhou (urban-rural monitoring type) sites. The NH4(+) -N/NO3(-) -N ratio peaked from early June to early August, declined gradually afterwards, and reached the bottom in winter; while the delta 15 NH4(+) value was negative from late June to mid-August, turned positive from late August to mid or late November, became negative again when winter dominated from December to March, but turned positive again in next May and negative again in next July. These seasonal variation patterns of NH4(+) -N/NO3(-) -N ratio and delta 15 NH4(+) value were found in relation to the application of chemical nitrogen fertilizers during different crop growth periods, and also, the alternation of seasons and the NH3 volatilization from other NH3 emission sources (including excrements of human and animals, nitrogen- polluted water bodies, and organic nitrogen sources, etc.), which could be taken as an indicator of defining the sources and form composition of NH4(+) in atmospheric wet deposition and the intensity of various terrestrial NH3 emission sources.

Infrared spectra of the ammonium ion in ammonium metavanadate NH 4VO 3

Science.gov (United States)

de Waal, D.; Heyns, A. M.; Range, K.-J.; Eglmeier, C.

The ND stretching modes of isotopically dilute NH 3D + ions in NH 4VO 3 are in agreement with the predicted splitting into C s, C s and C1(2) components under C s site symmetry for the NH +4 ion. The three bands observed represent the three NH bonding distances in the crystal, and the position, shape and low temperature behaviour of each band confirms the existence of two types of hydrogen bonding in NH 4VO 3. The low temperature infrared modes of NH +4 and ND +4 in NH 4VO 3 and ND 4VO 3, respectively, can be assigned under space group Pbcm. Temperature dependence of these modes also reflects the presence of both normal and bifurcated hydrogen bonds in NH 4VO 3.

Thermodynamic modeling of NH_3-CO_2-SO_2-K_2SO_4-H_2O system for combined CO_2 and SO_2 capture using aqueous NH_3

International Nuclear Information System (INIS)

Qi, Guojie; Wang, Shujuan

2017-01-01

Highlights: • A new application of aqueous NH_3 based combined CO_2 and SO_2 process was proposed. • A thermodynamic model simulated the heat of absorption and the K_2SO_4 precipitation. • The CO_2 content can be regenerated in a stripper with lower heat of desorption. • The SO_2 content can be removed by K_2SO_4 precipitation from the lean NH_3 solvent. - Abstract: A new application of aqueous NH_3 based post-combustion CO_2 and SO_2 combined capture process was proposed to simultaneously capture CO_2 and SO_2, and remove sulfite by solid (K_2SO_4) precipitation method. The thermodynamic model of the NH_3-CO_2-SO_2-K_2SO_4-H_2O system for the combined CO_2 and SO_2 capture process was developed and validated in this work to analyze the heat of CO_2 and SO_2 absorption in the NH_3-CO_2-SO_2-H_2O system, and the K_2SO_4 precipitation characteristics in the NH_3-CO_2-SO_2-K_2SO_4-H_2O system. The average heat of CO_2 absorption in the NH_3-CO_2-H_2O system at 40 °C is around −73 kJ/mol CO_2 in 2.5 wt% NH_3 with CO_2 loading between 0.2 and 0.5 C/N. The average heat of SO_2 absorption in the NH_3-SO_2-H_2O system at 40 °C is around −120 kJ/mol SO_2 in 2.5 wt% NH_3 with SO_2 loading between 0 and 0.5 S/N. The average heat of CO_2 absorption in the NH_3-CO_2-SO_2-H_2O system at 40 °C is 77, 68, and 58 kJ/mol CO_2 in 2.5 wt% NH_3 with CO_2 loading between 0.2 and 0.5 C/N, when SO_2 loading is 0, 0.1, 0.2 S/N, respectively. The solubility of K_2SO_4 increases with temperature, CO_2 and SO_2 loadings, but decreases with NH_3 concentration in the CO_2 and SO_2 loaded aqueous NH_3. The thermodynamic evaluation indicates that the combined CO_2 and SO_2 capture process could employ the typical absorption/regeneration process to simultaneously capture CO_2 and SO_2 in an absorber, thermally desorb CO_2 in a stripper, and feasibly remove sulfite (oxidized to sulfate) content by precipitating K_2SO_4 from the lean NH_3 solvent after the lean/rich heat exchanger.

Charge carrier localised in zero-dimensional (CH3NH3)3Bi2I9 clusters.

Science.gov (United States)

Ni, Chengsheng; Hedley, Gordon; Payne, Julia; Svrcek, Vladimir; McDonald, Calum; Jagadamma, Lethy Krishnan; Edwards, Paul; Martin, Robert; Jain, Gunisha; Carolan, Darragh; Mariotti, Davide; Maguire, Paul; Samuel, Ifor; Irvine, John

2017-08-01

A metal-organic hybrid perovskite (CH 3 NH 3 PbI 3 ) with three-dimensional framework of metal-halide octahedra has been reported as a low-cost, solution-processable absorber for a thin-film solar cell with a power-conversion efficiency over 20%. Low-dimensional layered perovskites with metal halide slabs separated by the insulating organic layers are reported to show higher stability, but the efficiencies of the solar cells are limited by the confinement of excitons. In order to explore the confinement and transport of excitons in zero-dimensional metal-organic hybrid materials, a highly orientated film of (CH 3 NH 3 ) 3 Bi 2 I 9 with nanometre-sized core clusters of Bi 2 I 9 3- surrounded by insulating CH 3 NH 3 + was prepared via solution processing. The (CH 3 NH 3 ) 3 Bi 2 I 9 film shows highly anisotropic photoluminescence emission and excitation due to the large proportion of localised excitons coupled with delocalised excitons from intercluster energy transfer. The abrupt increase in photoluminescence quantum yield at excitation energy above twice band gap could indicate a quantum cutting due to the low dimensionality.Understanding the confinement and transport of excitons in low dimensional systems will aid the development of next generation photovoltaics. Via photophysical studies Ni et al. observe 'quantum cutting' in 0D metal-organic hybrid materials based on methylammonium bismuth halide (CH 3 NH 3 )3Bi 2 I 9 .

Photodissociation of HCN and HNC isomers in the 7-10 eV energy range

Energy Technology Data Exchange (ETDEWEB)

Chenel, Aurelie; Roncero, Octavio, E-mail: octavio.roncero@csic.es [Instituto de Física Fundamental (IFF-CSIC), C.S.I.C., Serrano 123, 28006 Madrid (Spain); Aguado, Alfredo [Departamento de Química Física Aplicada (UAM), Unidad Asociada a IFF-CSIC, Facultad de Ciencias Módulo 14, Universidad Autónoma de Madrid, 28049 Madrid (Spain); Agúndez, Marcelino; Cernicharo, José [Instituto de Ciencia de Materiales de Madrid, CSIC, C/ Sor Juana Inés de la Cruz 3, 28049 Cantoblanco (Spain)

2016-04-14

The ultraviolet photoabsorption spectra of the HCN and HNC isomers have been simulated in the 7-10 eV photon energy range. For this purpose, the three-dimensional adiabatic potential energy surfaces of the 7 lowest electronic states, and the corresponding transition dipole moments, have been calculated, at multireference configuration interaction level. The spectra are calculated with a quantum wave packet method on these adiabatic potential energy surfaces. The spectra for the 3 lower excited states, the dissociative electronic states, correspond essentially to predissociation peaks, most of them through tunneling on the same adiabatic state. The 3 higher electronic states are bound, hereafter electronic bound states, and their spectra consist of delta lines, in the adiabatic approximation. The radiative lifetime towards the ground electronic states of these bound states has been calculated, being longer than 10 ns in all cases, much longer that the characteristic predissociation lifetimes. The spectra of HCN is compared with the available experimental and previous theoretical simulations, while in the case of HNC there are no previous studies to our knowledge. The spectrum for HNC is considerably more intense than that of HCN in the 7-10 eV photon energy range, which points to a higher photodissociation rate for HNC, compared to HCN, in astrophysical environments illuminated by ultraviolet radiation.

Towards validation of ammonia (NH3) measurements from the IASI satellite

Science.gov (United States)

Van Damme, M.; Clarisse, L.; Dammers, E.; Liu, X.; Nowak, J. B.; Clerbaux, C.; Flechard, C. R.; Galy-Lacaux, C.; Xu, W.; Neuman, J. A.; Tang, Y. S.; Sutton, M. A.; Erisman, J. W.; Coheur, P. F.

2015-03-01

Limited availability of ammonia (NH3) observations is currently a barrier for effective monitoring of the nitrogen cycle. It prevents a full understanding of the atmospheric processes in which this trace gas is involved and therefore impedes determining its related budgets. Since the end of 2007, the Infrared Atmospheric Sounding Interferometer (IASI) satellite has been observing NH3 from space at a high spatio-temporal resolution. This valuable data set, already used by models, still needs validation. We present here a first attempt to validate IASI-NH3 measurements using existing independent ground-based and airborne data sets. The yearly distributions reveal similar patterns between ground-based and space-borne observations and highlight the scarcity of local NH3 measurements as well as their spatial heterogeneity and lack of representativity. By comparison with monthly resolved data sets in Europe, China and Africa, we show that IASI-NH3 observations are in fair agreement, but they are characterized by a smaller variation in concentrations. The use of hourly and airborne data sets to compare with IASI individual observations allows investigations of the impact of averaging as well as the representativity of independent observations for the satellite footprint. The importance of considering the latter and the added value of densely located airborne measurements at various altitudes to validate IASI-NH3 columns are discussed. Perspectives and guidelines for future validation work on NH3 satellite observations are presented.

THE NITROGEN ISOTOPIC COMPOSITION OF METEORITIC HCN

Energy Technology Data Exchange (ETDEWEB)

Pizzarello, Sandra, E-mail: pizzar@asu.edu [Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ 85018-1604 (United States)

2014-12-01

HCN is ubiquitous in extraterrestrial environments and is central to current theories on the origin of early solar system organic compounds such as amino acids. These compounds, observed in carbonaceous meteorites, were likely important in the origin and/or evolution of early life. As part of our attempts to understand the origin(s) of meteoritic CN{sup –}, we have analyzed the {sup 15}N/{sup 14}N isotopic composition of HCN gas released from water extracts of the Murchison meteorite and found its value to be near those of the terrestrial atmosphere. The findings, when evaluated viz-a-viz molecular abundances and isotopic data of meteoritic organic compounds, suggest that HCN formation could have occurred during the protracted water alteration processes known to have affected the mineralogy of many asteroidal bodies during their solar residence. This was an active synthetic stage, which likely involved simple gasses, organic molecules, their presolar precursors, as well as mineral catalysts and would have lead to the formation of molecules of differing isotopic composition, including some with solar values.

EXTENDED HCN AND HCO{sup +} EMISSION IN THE STARBURST GALAXY M82

Energy Technology Data Exchange (ETDEWEB)

Salas, P.; Galaz, G. [Instituto de Astrofísica, Facultad de Física, Pontificia Universidad Católica de Chile, Av. Vicua Mackenna 4860, 782-0436 Macul, Santiago (Chile); Salter, D.; Herrera-Camus, R.; Bolatto, A. D. [Department of Astronomy and Laboratory for Millimeter-Wave Astronomy, University of Maryland, College Park, MD 20742 (United States); Kepley, A. [National Radio Astronomy Observatory, 520 Edgemont Road, Charlottesville, VA 22903-2475 (United States)

2014-12-20

We mapped 3 mm continuum and line emission from the starburst galaxy M82 using the Combined Array for Research in Millimeter-wave Astronomy. We targeted the HCN, HCO{sup +}, HNC, CS, and HC{sub 3}N lines, but here we focus on the HCN and HCO{sup +} emission. The map covers a field of 1.'2 with an ≈5'' resolution. The HCN and HCO{sup +} observations are short spacings corrected. The molecular gas in M82 had been previously found to be distributed in a molecular disk, coincident with the central starburst, and a galactic scale outflow which originates in the central starburst. With the new short spacings-corrected maps we derive some of the properties of the dense molecular gas in the base of the outflow. From the HCN and HCO{sup +} J = (1-0) line emission, and under the assumptions of the gas being optically thin and in local thermodynamic equilibrium, we place lower limits on the amount of dense molecular gas in the base of the outflow. The lower limits are 7 × 10{sup 6} M {sub ☉} and 21 × 10{sup 6} M {sub ☉}, or ≳ 2% of the total molecular mass in the outflow. The kinematics and spatial distribution of the dense gas outside the central starburst suggests that it is being expelled through chimneys. Assuming a constant outflow velocity, the derived outflow rate of dense molecular gas is ≥0.3 M {sub ☉} yr{sup –1}, which would lower the starburst lifetime by ≥5%. The energy required to expel this mass of dense gas is (1-10) × 10{sup 52} erg.

A Low Temperature Infrared Study Of Deuterated NH4VO3

Science.gov (United States)

de Waal, D.; Heyns, A. M.

1989-12-01

The existence of (NH4)2V6016 as an intermediate in the thermal decomposition of NH4V03 to V205 has been confirmed by vibrational spectroscopy, resulting in the following reaction in an open systeml: NH4VO3 1 bar, air, 50-200°C/(1) (NH4)2v6o16 1 bar, air, ca.360°C/(2) V205 The kinetics of reaction (1) was studied by means of Raman spectroscopy, and structural information on NH4V03 and (N114)V60 16 was required to obtain an accurate description of the reaction mechanism2. Information on the site symmetry of an ammonium ion and hydrogen bonding in a crystal can be obtained by considering the infrared spectra of isotopically dilute NH3D+ ions in the lattice at liquid nitrogen temperatures3, especially as the position of hydrogen atoms in (NHO2V6016 could not be determined by X-ray methods.

Rotational excitation of HCN by para- and ortho-H{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Vera, Mario Hernández, E-mail: marhvera@gmail.com [LOMC - UMR 6294, CNRS-Université du Havre, 25 rue Philippe Lebon, BP 1123, 76 063 Le Havre cedex (France); InSTEC, Quinta de Los Molinos, Plaza, La Habana 10600 (Cuba); Kalugina, Yulia [LOMC - UMR 6294, CNRS-Université du Havre, 25 rue Philippe Lebon, BP 1123, 76 063 Le Havre cedex (France); Tomsk State University, 36 Lenin av., Tomsk 634050 (Russian Federation); Denis-Alpizar, Otoniel [Université de Bordeaux, ISM, CNRS UMR 5255, 33405 Talence Cedex (France); Departamento de Física, Universidad de Matanzas, Matanzas 40100 (Cuba); Stoecklin, Thierry [Université de Bordeaux, ISM, CNRS UMR 5255, 33405 Talence Cedex (France); Lique, François, E-mail: francois.lique@univ-lehavre.fr [LOMC - UMR 6294, CNRS-Université du Havre, 25 rue Philippe Lebon, BP 1123, 76 063 Le Havre cedex (France)

2014-06-14

Rotational excitation of the hydrogen cyanide (HCN) molecule by collisions with para-H{sub 2}( j = 0, 2) and ortho-H{sub 2}( j = 1) is investigated at low temperatures using a quantum time independent approach. Both molecules are treated as rigid rotors. The scattering calculations are based on a highly correlated ab initio 4-dimensional (4D) potential energy surface recently published. Rotationally inelastic cross sections among the 13 first rotational levels of HCN were obtained using a pure quantum close coupling approach for total energies up to 1200 cm{sup −1}. The corresponding thermal rate coefficients were computed for temperatures ranging from 5 to 100 K. The HCN rate coefficients are strongly dependent on the rotational level of the H{sub 2} molecule. In particular, the rate coefficients for collisions with para-H{sub 2}( j = 0) are significantly lower than those for collisions with ortho-H{sub 2}( j = 1) and para-H{sub 2}( j = 2). Propensity rules in favor of even Δj transitions were found for HCN in collisions with para-H{sub 2}( j = 0) whereas propensity rules in favor of odd Δj transitions were found for HCN in collisions with H{sub 2}( j ⩾ 1). The new rate coefficients were compared with previously published HCN-para-H{sub 2}( j = 0) rate coefficients. Significant differences were found due the inclusion of the H{sub 2} rotational structure in the scattering calculations. These new rate coefficients will be crucial to improve the estimation of the HCN abundance in the interstellar medium.

Effects of atmospheric ammonia (NH{sub 3}) on terrestrial vegetation: a review

Energy Technology Data Exchange (ETDEWEB)

Krupa, S.V

2003-07-01

A review of atmospheric ammonia (NH{sub 3}) and ammonium (NH{sub 4}{sup +}) deposition and their effects on plants. - At the global scale, among all N (nitrogen) species in the atmosphere and their deposition on to terrestrial vegetation and other receptors, NH{sub 3} (ammonia) is considered to be the foremost. The major sources for atmospheric NH{sub 3} are agricultural activities and animal feedlot operations, followed by biomass burning (including forest fires) and to a lesser extent fossil fuel combustion. Close to its sources, acute exposures to NH{sub 3} can result in visible foliar injury on vegetation. NH{sub 3} is deposited rapidly within the first 4-5 km from its source. However, NH{sub 3} is also converted in the atmosphere to fine particle NH{sub 4}{sup +} (ammonium) aerosols that are a regional scale problem. Much of our current knowledge of the effects of NH{sub 3} on higher plants is predominantly derived from studies conducted in Europe. Adverse effects on vegetation occur when the rate of foliar uptake of NH{sub 3} is greater than the rate and capacity for in vivo detoxification by the plants. Most to least sensitive plant species to NH{sub 3} are native vegetation > forests > agricultural crops. There are also a number of studies on N deposition and lichens, mosses and green algae. Direct cause and effect relationships in most of those cases (exceptions being those locations very close to point sources) are confounded by other environmental factors, particularly changes in the ambient SO{sub 2} (sulfur dioxide) concentrations. In addition to direct foliar injury, adverse effects of NH{sub 3} on higher plants include alterations in: growth and productivity, tissue content of nutrients and toxic elements, drought and frost tolerance, responses to insect pests and disease causing microorganisms (pathogens), development of beneficial root symbiotic or mycorrhizal associations and inter species competition or biodiversity. In all these cases, the joint

Moessbauer study of 57Fe isolated in NH3 and NH3/Xe matrices

International Nuclear Information System (INIS)

Saitovitch, E.M.B.; Litterst, F.J.; Micklitz, H.

1981-01-01

Moessbauer studies on 57 Fe isolated in solid ammonia and ammonia/xenon mixtures were perfomed at 4.2 K and 77 K. They show clearly that atomic iron reacts only with one ammonia molecule forming FeNH 3 which is stable in an ammonia matrix up to 77 K. In addition a compound is formed which is attributed to an iron (II) hexammine. (Author) [pt

General working principles of CH3NH3PbX3 perovskite solar cells.

Science.gov (United States)

Gonzalez-Pedro, Victoria; Juarez-Perez, Emilio J; Arsyad, Waode-Sukmawati; Barea, Eva M; Fabregat-Santiago, Francisco; Mora-Sero, Ivan; Bisquert, Juan

2014-02-12

Organometal halide perovskite-based solar cells have recently realized large conversion efficiency over 15% showing great promise for a new large scale cost-competitive photovoltaic technology. Using impedance spectroscopy measurements we are able to separate the physical parameters of carrier transport and recombination in working devices of the two principal morphologies and compositions of perovskite solar cells, viz. compact thin films of CH3NH3PbI(3-x)Clx and CH3NH3PbI3 infiltrated on nanostructured TiO2. The results show nearly identical spectral characteristics indicating a unique photovoltaic operating mechanism that provides long diffusion lengths (1 μm). Carrier conductivity in both devices is closely matched, so that the most significant differences in performance are attributed to recombination rates. These results highlight the central role of the CH3NH3PbX3 semiconductor absorber in carrier collection and provide a new tool for improved optimization of perovskite solar cells. We report for the first time a measurement of the diffusion length in a nanostructured perovskite solar cell.

First principles study of NH3 molecular adsorption on LiH (100) surfaces

International Nuclear Information System (INIS)

Lu Xiaoxia; Chen Yuhong; Dong Xiao

2012-01-01

The adsorption of NH 3 on LiH (100) crystal surfaces was studied by first principles method. The preferred adsorption sites, adsorption energy, dissociation energy and electronic structure of the LiH (100)/NH 3 systems were calculated separately. It is found that chemical adsorption happened mainly when NH 3 molecules are on the LiH (100) crystal surfaces. When NH 3 is adsorbed on the Li top site, NH 2 is formed on the LiH (100) crystal surfaces after loss of H atom, the calculated adsorption energy, 0.511 eV, belongs to strong chemical adsorption, then the interaction is strongest. The interaction between NH 2 and the neighboring Li, H are ionic. The covalent bonds are formed between N and H atoms in NH 2 . One H 2 molecule is formed by another H atom in NH 3 and H atom from LiH (100) crystal sur- faces. The covalent bonds are formed between H and H atoms in H 2 . (authors)

Evolution of Chemical Composition, Morphology, and Photovoltaic Efficiency of CH 3 NH 3 PbI 3 Perovskite under Ambient Conditions

KAUST Repository

Huang, Weixin; Manser, Joseph S.; Kamat, Prashant V.; Ptasinska, Sylwia

2016-01-01

© 2015 American Chemical Society. The surface composition and morphology of CH3NH3PbI3 perovskite films stored for several days under ambient conditions were investigated by X-ray photoelectron spectroscopy, scanning electron microscopy, and X-ray diffraction techniques. Chemical analysis revealed the loss of CH3NH3 + and I- species from CH3NH3PbI3 and its subsequent decomposition into lead carbonate, lead hydroxide, and lead oxide. After long-term storage under ambient conditions, morphological analysis revealed the transformation of randomly distributed defects and cracks, initially present in the densely packed crystalline structure, into relatively small grains. In contrast to PbI2 powder, CH3NH3PbI3 exhibited a different degradation trend under ambient conditions. Therefore, we propose a plausible CH3NH3PbI3 decomposition pathway that explains the changes in the chemical composition of CH3NH3PbI3 under ambient conditions. In addition, films stored under such conditions were incorporated into photovoltaic cells, and their performances were examined. The chemical changes in the decomposed films were found to cause a significant decrease in the photovoltaic efficiency of CH3NH3PbI3.

Evolution of Chemical Composition, Morphology, and Photovoltaic Efficiency of CH 3 NH 3 PbI 3 Perovskite under Ambient Conditions

KAUST Repository

Huang, Weixin

2016-01-12

© 2015 American Chemical Society. The surface composition and morphology of CH3NH3PbI3 perovskite films stored for several days under ambient conditions were investigated by X-ray photoelectron spectroscopy, scanning electron microscopy, and X-ray diffraction techniques. Chemical analysis revealed the loss of CH3NH3 + and I- species from CH3NH3PbI3 and its subsequent decomposition into lead carbonate, lead hydroxide, and lead oxide. After long-term storage under ambient conditions, morphological analysis revealed the transformation of randomly distributed defects and cracks, initially present in the densely packed crystalline structure, into relatively small grains. In contrast to PbI2 powder, CH3NH3PbI3 exhibited a different degradation trend under ambient conditions. Therefore, we propose a plausible CH3NH3PbI3 decomposition pathway that explains the changes in the chemical composition of CH3NH3PbI3 under ambient conditions. In addition, films stored under such conditions were incorporated into photovoltaic cells, and their performances were examined. The chemical changes in the decomposed films were found to cause a significant decrease in the photovoltaic efficiency of CH3NH3PbI3.

Vibrational relaxation of matrix-isolated CH3F and HCl

International Nuclear Information System (INIS)

Young, L.

1981-08-01

Kinetic and spectroscopic studies have been performed on CH 3 F and HCl as a function of host matrix and temperature. Temporally and spectrally resolved infrared fluorescence was used to monitor the populations of both the initially excited state and the lower lying levels which participate in the relaxation process. For CH 3 F, relaxation from any of the levels near 3.5 μ, i.e. the CH stretching fundamentals or bend overtones, occurs via rapid ( 3 with subsequent relaxation of the ν 3 (CF stretch) manifold. Lifetimes of 2ν 3 and ν 3 were determined through overtone, ΔV = 2, and fundamental fluorescence. These lifetimes show a dramatic dependence on host lattice, an increase of two orders of magnitude in going from Xe and Ar matrices. Lifetimes depend only weakly on temperature. The relaxation of 2ν 3 and ν 3 is consistent with a model in which production of a highly rotationally excited guest via collisions with the repulsive wall of the host is the rate limiting step. For HCl, lifetimes of v = 1,2,3 have been determined. In all hosts, the relaxation is non-radiative. For a given vibrational state, v, the relaxation rate increases in the series k(Ar) < k(Kr) < k(Xe). The dependence of the relaxation rate; on v is superlinear in all matrices, the deviation from linearity increasng in the order Ar < Kr < Xe. The relaxation rates become more strongly temperature dependent with increasing vibrational excitation. The results are consistent with a mechanism in which complex formation introduces the anisotropy necessary to induce a near resonant V → R transition in the rate limiting step

Increase in Ice Nucleation Efficiency of Feldspars, Kaolinite and Mica in Dilute NH3 and NH4+-containing Solutions

Science.gov (United States)

Kumar, A.; Marcolli, C.; Luo, B.; Krieger, U. K.; Peter, T.

2017-12-01

Semivolatile species present in the atmosphere are prone to adhere to mineral dust particle surfaces during long range transport, and could potentially change the particle surface properties and its ice nucleation (IN) efficiency. Immersion freezing experiments were performed with microcline (K-feldspar), known to be highly IN active, suspended in aqueous solutions of ammonia, (NH4)2SO4, NH4HSO4, NH4NO3, NH4Cl, Na2SO4, H2SO4, K2SO4 and KCl to investigate the effect of solutes on the IN efficiency. Freezing of emulsified droplets investigated with a differential scanning calorimeter (DSC) showed that the heterogeneous ice nucleation temperatures deviate from the water activity-based IN theory, describing heterogeneous ice nucleation temperatures as a function of solution water activity by a constant offset with respect to the ice melting point curve (Zobrist et al. 2008). IN temperatures enhanced up to 4.5 K were observed for very dilute NH3 and NH4+-containing solutions while a decrease was observed as the concentration was further increased. For all solutes with cations other than NH4+, the IN efficiency decreased. An increase of the IN efficiency in very dilute NH3 and NH4+-containing solutions followed by a decrease with increasing concentration was also observed for sanidine (K-feldspar) and andesine (Na/Ca-feldspar). This is an important indication towards specific chemical interactions between solutes and the feldspar surface which is not captured by the water activity-based IN theory. A similar trend is present but less pronounced in case of kaolinite and mica, while quartz is barely affected. We hypothesize that the hydrogen bonding of NH3 molecules with surface -OH groups could be the reason for the enhanced freezing temperatures in dilute ammonia and ammonium containing solutions as they could form an ice-like overlayer providing hydrogen bonding groups for ice to nucleate on top of it. This implies to possibilities of enhanced IN efficiency, especially

HCN Producing Bacteria Enable Sensing Of Non-Bioavailable Hg Species by the Whole Cell Biosensor

Science.gov (United States)

Horvat, M.; Rijavec, T.; Koron, N.; Lapanje, A.

2015-12-01

Bacteria play an important role in Hg transformation reactions. The production of cyanide (HCN) and other secondary metabolites seems to be key elements involved in these transformations. Current hypotheses link the role of HCN production to growth inhibition of nonHCN producing competitor organisms (role of an antimicrobial agent). Our past investigations showed that HCN production did not correlate with antimicrobial activity and since pK value of HCN is very high (pK = 9,21), it can be expected that most of the produced HCN is removed from the microenvironment. This way, the expected inhibitory concentrations can hardly be reached. Accordingly, we proposed a new concept, where the ability of complexation of transient metals by HCN served as a regulation process for the accessibility of micro-elements. In our study, we focused on the presence of HCN producing bacteria and carried it out in the Hg contaminated environment connected to the Idrija Mercury Mine, Slovenia. We characterised the isolates according to the presence of Hg resistance (HgR), level of HCN production and genetic similarities. In laboratory setups, using our merR whole cell based biosensor, we determined the transformation of low bioavailable Hg0 and HgS forms into bioavailable Hg by these HCN producing bacteria. We observed that HgR strains producing HCN had the highest impact on increased Hg bioavailability. In the proposed ecological strategy HgR HCN producing bacteria increase their competitive edge over non-HgR competitors through the increase of Hg toxicity. Due to their activity, Hg is made available to other organisms as well and thus enters into the ecosystem. Finally, using some of the characteristics of bacteria (e.g. Hg resistance genetic elements), we developed a fully automated sensing approach, combining biosensorics and mechatronics, to measure the bioavailability of Hg in situ.

Adsorption Mechanisms of NH3 on Chlorinated Si(100)-2 x 1 Surface

International Nuclear Information System (INIS)

Lee, Hee Soon; Choi, Cheol Ho

2012-01-01

The potential energy surfaces of ammonia molecule adsorptions on the symmetrically chlorinated Si(100)- 2 x 1 surface were explored with SIMOMM:MP2/6-31G(d). It was found that the initial nucleophilic attack by ammonia nitrogen to the surface Si forms a S N 2 type transition state, which eventually leads to an HCl molecular desorption. The second ammonia molecule adsorption requires much less reaction barrier, which can be rationalized by the surface cooperative effect. In general, it was shown that the surface Si-Cl bonds can be easily subjected to the substitution reactions by ammonia molecules yielding symmetric surface Si-NH 2 bonds, which can be a good initial template for subsequent surface chemical modifications. The ammonia adsorptions are in general more facile than the corresponding water adsorption, since ammonia is better nucleophile

The energy level alignment at the CH{sub 3}NH{sub 3}PbI{sub 3}/pentacene interface

Energy Technology Data Exchange (ETDEWEB)

Ji, Gengwu [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204 (China); University of Chinese Academy of Science, Beijing 100049 (China); Zhao, Bin; Song, Fei [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204 (China); Zheng, Guanhaojie; Zhang, Xiaonan [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204 (China); University of Chinese Academy of Science, Beijing 100049 (China); Shen, Kongchao [Department of Physics, Zhejiang University, Hangzhou 310027 (China); Yang, Yingguo [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204 (China); Chen, Shi, E-mail: ChenShi@ntu.edu.sg [Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371 (Singapore); Gao, Xingyu, E-mail: gaoxingyu@sinap.ac.cn [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204 (China)

2017-01-30

Highlights: • The Energy Level Alignment at the CH{sub 3}NH{sub 3}PbI{sub 3}/Pentacene Interface was resolved experimentally. • The downward band bending and the dipole found at the pentacene side would favorably drive holes away from the interface into pentacene. • A ∼0.7 eV offset between pentacene HOMO and CH{sub 3}NH{sub 3}PbI{sub 3} VBM would be in favor of hole transfer whereas a ∼1.35 eV offset between pentacene LUMO and CH{sub 3}NH{sub 3}PbI{sub 3} CBM should efficiently block the unwanted electron transfer from perovskite to pentacene. • Pentacene could be a viable hole transfer material candidate on perovskite to be explored in perovskite devices. - Abstract: Pentacene thin film on CH{sub 3}NH{sub 3}PbI{sub 3} was studied by in-situ X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy to determine their interfacial energy level alignment. A 0.2 eV downward band bending together with a 0.1 eV interfacial dipole was found at the pentacene side, whereas there was no band bending found at the CH{sub 3}NH{sub 3}PbI{sub 3} side. The offset between CH{sub 3}NH{sub 3}PbI{sub 3} Valance Band Maximum (VBM) and pentacene Highest Occupied Molecular Orbital (HOMO) and that between CH{sub 3}NH{sub 3}PbI{sub 3} Conduction Band Minimum (CBM) and pentacene Lowest Unoccupied Molecular Orbital (LUMO) was determined to be 0.7 and 1.35 eV, respectively. The band alignment at this interface is favor of efficient hole transfer, which suggests pentacene as a viable HTL candidate to be explored in perovskite solar cells.

Study of the structural phase transitions of (CH 3NH 3) 3Sb 2Cl 9 (MACA) and (CH 3NH 3) 3Bi 2Cl 9 (MACB) by infrared spectroscopy

Science.gov (United States)

Bator, G.; Jakubas, R.; Malarski, Z.

1991-06-01

Infrared spectra of polycrystalline (CH 3NH 3) 3Sb 2Cl 9 and (CH 3NH 3) 3Bi 2Cl 9 have been studied in the temperature range 90-300 K. A systematic temperature dependence study of the internal modes has been carried out. We discuss the effects of the dynamic state of methylammonium (MA) cations on their vibrational spectra. The results show that the dynamics of MA cations in both compounds is similar in higher (about 300 K) and lower temperature (in the vicinity of 100 K) regions. Substantial differences are revealed in the intermediate temperature interval. The results are in good agreement with earlier dielectric, calorimetric and 1H NMR studies.

Targeted deletion of Kcne2 impairs HCN channel function in mouse thalamocortical circuits.

Directory of Open Access Journals (Sweden)

Shui-Wang Ying

Full Text Available Hyperpolarization-activated, cyclic nucleotide-gated (HCN channels generate the pacemaking current, I(h, which regulates neuronal excitability, burst firing activity, rhythmogenesis, and synaptic integration. The physiological consequence of HCN activation depends on regulation of channel gating by endogenous modulators and stabilization of the channel complex formed by principal and ancillary subunits. KCNE2 is a voltage-gated potassium channel ancillary subunit that also regulates heterologously expressed HCN channels; whether KCNE2 regulates neuronal HCN channel function is unknown.We investigated the effects of Kcne2 gene deletion on I(h properties and excitability in ventrobasal (VB and cortical layer 6 pyramidal neurons using brain slices prepared from Kcne2(+/+ and Kcne2(-/- mice. Kcne2 deletion shifted the voltage-dependence of I(h activation to more hyperpolarized potentials, slowed gating kinetics, and decreased I(h density. Kcne2 deletion was associated with a reduction in whole-brain expression of both HCN1 and HCN2 (but not HCN4, although co-immunoprecipitation from whole-brain lysates failed to detect interaction of KCNE2 with HCN1 or 2. Kcne2 deletion also increased input resistance and temporal summation of subthreshold voltage responses; this increased intrinsic excitability enhanced burst firing in response to 4-aminopyridine. Burst duration increased in corticothalamic, but not thalamocortical, neurons, suggesting enhanced cortical excitatory input to the thalamus; such augmented excitability did not result from changes in glutamate release machinery since miniature EPSC frequency was unaltered in Kcne2(-/- neurons.Loss of KCNE2 leads to downregulation of HCN channel function associated with increased excitability in neurons in the cortico-thalamo-cortical loop. Such findings further our understanding of the normal physiology of brain circuitry critically involved in cognition and have implications for our understanding of

Vapor-phase etching of InP using anhydrous HCl and PH/sub 3/ gas

International Nuclear Information System (INIS)

Pak, K.; Koide, Y.; Imai, K.; Yoshida, A.; Nakamura, T.; Yasuda, Y.; Nishinaga, T.

1986-01-01

In situ etching of the substrate surface for vapor-phase epitaxy is a useful technique for obtaining a smooth and damage-free surface prior to the growth. Previous work showed that the incorporation of in situ etching of InP substrate with anhydrous HCl gas resulted in a significant improvement in the surface morphologies for MOVPE-grown InGaAs/InP and InP epitaxial layers. However, the experiment on the HCl etching of the InP substrate for a wide temperature range has not been performed as yet. In this note, the authors describe the effect of the substrate temperature on the etching morphology of InP substrate by using the anhydrous HCl and PH/sub 3/ gases. In the experiment, they used a standard MOVPE horizontal system. A quartz reactor tube in a 60 mm ID, 60 cm long, was employed

NO3-/NH4+ proportions affect cadmium bioaccumulation and tolerance of tomato.

Science.gov (United States)

Nogueirol, Roberta Corrêa; Monteiro, Francisco Antonio; de Souza Junior, João Cardoso; Azevedo, Ricardo Antunes

2018-05-01

With the growth of the world population, cadmium (Cd) concentration in the environment has increased considerably as a result of human activities such as foundry, battery disposal, mining, application of fertilizers containing toxic elements as impurities, and disposal of metal-containing waste. Higher plants uptake N as ammonium (NH 4 + ), nitrate (NO 3 - ), and many other water-soluble compounds such as urea and amino acids, and nourishing plants with N, providing part of it as NH 4 + , is an interesting alternative to the supply of this nutrient in the exclusive form of NO 3 - under Cd toxicity. The objective was to evaluate the influence of NO 3 - /NH 4 + proportions on the development and tolerance of tomato plants grown under the presence of Cd in the culture medium. The experiment was conducted in a completely randomized block design in a 3 × 3 factorial arrangement consisting of three Cd rates (0, 50, and 100 μmol L -1 ) and three NO 3 - /NH 4 + proportions (100/0, 70/30, and 50/50) in the nutrient solution. To this end, we quantified the responses of the antioxidant enzymatic system and productive and functional changes in Solanum lycopersicum var. esculentum (Calabash Rouge). Shoot biomass production decreased with the maximum Cd rate (100 μmol L -1 ) tested in the growth medium, whereas the NO 3 - /NH 4 + proportions and other Cd rates did not significantly influence this variable. The lowest SPAD values were observed at the 100/0 NO 3 - /NH 4 + proportion and in plants exposed to Cd. The largest accumulation of the metal occurred in the shoots at the NO 3 - /NH 4 + proportion of 70/30 and at 100 μmol L -1 Cd and in the roots at 100/0 NO 3 - /NH 4 + and with 50 and 100 μmol L -1 Cd. The concentration and accumulation of NO 3 - were highest at the NO 3 - /NH 4 + proportion of 100/0 in the shoots and at 50/50 NO 3 - /NH 4 + in the roots, whereas for NH 4 + , values were higher as the proportion of N supplied in the form of NH 4 + was

Rotational spectrum of the NH3–He van der Waals complex

Directory of Open Access Journals (Sweden)

Surin L.

2017-01-01

Full Text Available The interaction between ammonia and helium has attracted considerable interest over many years, partly because of the observation of interstellar ammonia. The rate coefficients of NH3–He scattering are an important ingredient for numerical modeling of astrochemical environments. Another, though quite different application in which the NH3–He interaction can play an important role is the doping of helium clusters with NH3 molecules to perform high-resolution spectroscopy. Such experiments are directed on the detection of non-classical response of molecular rotation in helium clusters addressing fundamental questions related to the microscopic nature of superfluidity. High-resolution spectroscopy on the NH3–He complex is an important tool for increasing our understanding of intermolecular forces between NH3 and He.

HCl Flow-Induced Phase Change of α-, β-, and ε-Ga2O3 Films Grown by MOCVD

KAUST Repository

Sun, Haiding; Li, Kuang-Hui; Castanedo, C. G. Torres; Okur, Serdal; Tompa, Gary S.; Salagaj, Tom; Lopatin, Sergei; Genovese, Alessandro; Li, Xiaohang

2018-01-01

inducing the phase change by increasing the HCl flow in the reactor. Thus, it is plausible that the HCl acted as a catalyst during the phase transformation process. Furthermore, we revealed the microstructure and the epitaxial relationship between Ga2O3

Hypoosmotic cell swelling as a novel mechanism for modulation of cloned HCN2 channels

DEFF Research Database (Denmark)

Calloe, Kirstine; Elmedyb, Pernille; Olesen, Søren-Peter

2005-01-01

This work demonstrates cell swelling as a new regulatory mechanism for the cloned hyperpolarization-activated, cyclic nucleotide-gated channel 2 (HCN2). HCN2 channels were coexpressed with aquaporin1 in Xenopus laevis oocytes and currents were monitored using a two-electrode voltage-clamp. HCN2...... channels were activated by hyperpolarization to -100 mV and the currents were measured before and during hypoosmotic cell swelling. Cell swelling increased HCN2 currents by 30% without changing the kinetics of the currents. Injection of 50 nl intracellular solution resulted in a current increase of 20......%, indicating that an increase in cell volume also under isoosmotic conditions may lead to activation of HCN2. In the absence of aquaporin1 only negligible changes in oocyte cell volume occur during exposure to hypoosmotic media and no significant change in HCN2 channel activity was observed during perfusion...

Observation of lower defect density in CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} solar cells by admittance spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Jiang, Minlin; Lan, Fei; Tao, Quan; Li, Guangyong, E-mail: gaod@pitt.edu, E-mail: gul6@pitt.edu [Department of Electrical and Computer Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15260 (United States); Zhao, Bingxin [Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15260 (United States); Key Laboratory of Advanced Functional Materials, College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124 (China); Wu, Jiamin; Gao, Di, E-mail: gaod@pitt.edu, E-mail: gul6@pitt.edu [Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15260 (United States)

2016-06-13

The introduction of Cl into CH{sub 3}NH{sub 3}PbI{sub 3} precursors is reported to enhance the performance of CH{sub 3}NH{sub 3}PbI{sub 3} solar cell, which is attributed to the significantly increased diffusion lengths of carriers in CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} solar cell. It has been assumed but never experimentally approved that the defect density in CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} solar cell should be reduced according to the higher carrier lifetime observed from photoluminescence (PL) measurement. We have fabricated CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} solar cell by adding a small amount of Cl source into CH{sub 3}NH{sub 3}PbI{sub 3} precursor. The performance of CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} solar cell is significantly improved from 15.39% to 18.60%. Results from scanning electron microscopy and X-ray diffraction indicate that the morphologies and crystal structures of CH{sub 3}NH{sub 3}PbI{sub 3} and CH{sub 3}NH{sub 3}Pb(I,Cl){sub 3} thin films remain unchanged. Open circuit voltage decay and admittance spectroscopy characterization jointly approve that Cl plays an extremely important role in suppressing the formation of defects in perovskite solar cells.

Wet Mechanochemical Processing of Celestine using (NH42CO3

Directory of Open Access Journals (Sweden)

Deniz Bingöl

2017-06-01

Full Text Available In this study, traditional (univariate method of processing to the wet mechanochemical treatment were applied to obtain both SrCO3 and (NH42SO4 from celestite (SrSO4-(NH42CO3-H2O mixtures in a planetary ball mill. X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and chemical analysis were used to analyze products formed during wet milling. A hydrometallurgical process was carried out to examine milling time, ball to grinding material mass ratio, (NH42CO3 to SrSO4 mole ratio and rotational speed of the mill in a planetary mill. Under optimum conditions, a conversion approaching 100% of SrCO3 was obtained.

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

Science.gov (United States)

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

1997-09-24

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

Chemical equilibrium in the GaP-HCl and InP-HCl systems

International Nuclear Information System (INIS)

Goliusov, V.A.; Voronin, V.A.; Chuchmarev, S.K.

1983-01-01

Chemical equilibrium in the GaP-HCl and InP-HCl systems is investigated experimentally, polynomial dependence of the total pressure on temperature (800-1100 K) and hydrochloric aci concntration under the experimental conditions is obtained. The technique for equilibrium calculation in hydrogencontaining chemical systems based on the tensimetric investigation results is suggested. The equilibrium gas phase composition in the GaP(InP)-HCl systems and self consistent, within the framework of the designed equilibrium model thermodynamic characteristics are determined. The effectiveness of gas-phase indium- and gallium phosphides precipitation in the GaP(InP)-HCl systems is calculated

A search for the millimetre lines of HCN in Comets Wilson 1987 VII and Machholz 1988 XV

Science.gov (United States)

Crouvisier, J.; Despois, D.; Bockelee-Morvan, D.; Gerard, E.; Paubert, G.; Johansson, L. E. B.; Ekelund, L.; Winnberg, A.; Ge, W.; Irvine, W. M.; Kinzel, W. M.; Schloerb, F. P.

1990-08-01

The J(1-0) lines of HCN at 89 GHz were searched for in Comet Wilson 1987 VII, with the FCRAO, the SEST and the IRAM radio telescopes between February and June 1987. There was no firm detection, but significant upper limits were obtained, which put severe constraints on the HCN production rate in that comet. A direct comparison with the observations of P/Halley suggests that the HCN abundance relative to water might be smaller in Comet Wilson by at least a factor of two. The J(1-0) and J(3-2) lines of HCN at 89 and 266 GHz were searched for in Comet Machholz 1988 XV when it was close to perihelion at 0.17 AU from the sun. There was no detection. At that moment, the comet was probably no longer active.

Pressure induced polymorphism in ammonium azide (NH{sub 4}N{sub 3})

Energy Technology Data Exchange (ETDEWEB)

Medvedev, S.A., E-mail: s.medvedev@mpic.de [Max-Planck-Institute for Chemistry, Postfach 3060, D-55020 Mainz (Germany); Institute fuer Anorganische und Analytische Chemie, Johannes Gutenberg-Universitaet, D-55099 Mainz (Germany); Eremets, M.I. [Max-Planck-Institute for Chemistry, Postfach 3060, D-55020 Mainz (Germany); Evers, J.; Klapoetke, T.M. [Energetic Materials Research, Ludwig-Maximilian University Munich (LMU), Butenandtstrasse 5-13(D), D-81377 Munich (Germany); Palasyuk, T. [Max-Planck-Institute for Chemistry, Postfach 3060, D-55020 Mainz (Germany); Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Trojan, I.A. [Max-Planck-Institute for Chemistry, Postfach 3060, D-55020 Mainz (Germany)

2011-07-28

Graphical abstract: Polymorph phase transition is observed in NH{sub 4}N{sub 3} at {approx}3 GPa by pressure dependent Raman studies. The strength of hydrogen bond appears to be modified at the phase transition as illustrated by dependence of N-H stretching frequency on pressure shown on figure. Highlights: {yields} Ammonium azide (NH{sub 4}N{sub 3}) studied at high pressures by Raman spectroscopy. {yields} Phase transition is observed at pressure {approx}3 GPa. {yields} Strength of hydrogen bond appears to be modified at the phase transition. {yields} NH{sub 4}N{sub 3} remain in molecular form up to pressures above 50 GPa. - Abstract: Pressure-dependent Raman spectroscopy studies reveal polymorph phase transition in simple molecular ionic crystal NH{sub 4}N{sub 3} at pressure {approx}3 GPa unobserved by recent abinitio evolutionary structure searches. Hydrogen bonding is spectroscopically evident in both low- and high-pressure phases. The strength of hydrogen bond appears to be modified at the phase transition: in the low-pressure phase NH{sub 4}N{sub 3} behaves as system with very strong hydrogen bonding whereas changes of spectra with pressure in the high-pressure phase are indicative of weak or medium-strength hydrogen bonds. The high pressure phase is most likely thermodynamically stable at least up to pressure {approx}55 GPa contradicting the abinitio studies predicting transformation of NH{sub 4}N{sub 3} to nonmolecular hydronitrogen solid at 36 GPa.

Imaging a multidimensional multichannel potential energy surface: Photodetachment of H{sup −}(NH{sub 3}) and NH{sub 4}{sup −}

Energy Technology Data Exchange (ETDEWEB)

Hu, Qichi; Johnson, Christopher J.; Continetti, Robert E., E-mail: hguo@umn.edu, E-mail: rcontinetti@ucsd.edu [Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, California 92093-0340 (United States); Song, Hongwei; Guo, Hua, E-mail: hguo@umn.edu, E-mail: rcontinetti@ucsd.edu [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States); Li, Jun [School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China)

2016-06-28

Probes of the Born-Oppenheimer potential energy surfaces governing polyatomic molecules often rely on spectroscopy for the bound regions or collision experiments in the continuum. A combined spectroscopic and half-collision approach to image nuclear dynamics in a multidimensional and multichannel system is reported here. The Rydberg radical NH{sub 4} and the double Rydberg anion NH{sub 4}{sup −} represent a polyatomic system for benchmarking electronic structure and nine-dimensional quantum dynamics calculations. Photodetachment of the H{sup −}(NH{sub 3}) ion-dipole complex and the NH{sub 4}{sup −} DRA probes different regions on the neutral NH{sub 4} PES. Photoelectron energy and angular distributions at photon energies of 1.17, 1.60, and 2.33 eV compare well with quantum dynamics. Photoelectron-photofragment coincidence experiments indicate dissociation of the nascent NH{sub 4} Rydberg radical occurs to H + NH{sub 3} with a peak kinetic energy of 0.13 eV, showing the ground state of NH{sub 4} to be unstable, decaying by tunneling-induced dissociation on a time scale beyond the present scope of multidimensional quantum dynamics.

Optical constants of CH3NH3PbBr3 perovskite thin films measured by spectroscopic ellipsometry

KAUST Repository

Alias, Mohd Sharizal

2016-07-14

The lack of optical constants information for hybrid perovskite of CH3NH3PbBr3 in thin films form can delay the progress of efficient LED or laser demonstration. Here, we report on the optical constants (complex refractive index and dielectric function) of CH3NH3PbBr3 perovskite thin films using spectroscopic ellipsometry. Due to the existence of voids, the refractive index of the thin films is around 8% less than the single crystals counterpart. The energy bandgap is around 2.309 eV as obtained from photoluminescence and spectrophotometry spectra, and calculated from the SE analysis. The precise measurement of optical constants will be useful in designing optical devices using CH3NH3PbBr3 thin films.

Characterization of a right atrial subsidiary pacemaker and acceleration of the pacing rate by HCN over-expression.

Science.gov (United States)

Morris, Gwilym M; D'Souza, Alicia; Dobrzynski, Halina; Lei, Ming; Choudhury, Moinuddin; Billeter, Rudi; Kryukova, Yelena; Robinson, Richard B; Kingston, Paul A; Boyett, Mark R

2013-10-01

Although the right atrium (RA contains subsidiary atrial pacemaker (SAP) tissue that can take over from the sinoatrial node (SAN) in sick sinus syndrome (SSS), SAP tissue is bradycardic. Little is known about SAP tissue and one aim of the study was to characterize ion channel expression to obtain insight into SAP pacemaker mechanisms. A second aim was to determine whether HCN over-expression (a 'biopacemaker'-like strategy) can accelerate the pacemaker rate producing a pacemaker that is similar in nature to the SAN. SAP tissue was isolated from the rat and the leading pacemaker site was characterized. Cell size at the leading pacemaker site in the SAP was smaller than in the RA and comparable to that in the SAN. mRNA levels showed the SAP to be similar to, but distinct from, the SAN. For example, in the SAN and SAP, expression of Tbx3 and HCN1 was higher and Nav1.5 and Cx43 lower than in the RA. Organ-cultured SAP tissue beat spontaneously, but at a slower rate than the SAN. Adenovirus-mediated gene transfer of HCN2 and the chimeric protein HCN212 significantly increased the pacemaker rate of the SAP close to that of the native SAN, but HCN4 was ineffective. SAP tissue near the inferior vena cava is bradycardic, but shares characteristics with the SAN. Pacing can be accelerated by the over-expression of HCN2 or HCN212. This provides proof of concept for the use of SAP tissue as a substrate for biopacemaking in the treatment of SSS.

A Simplified Model for Volatile-N Oxidation

DEFF Research Database (Denmark)

Hansen, Stine; Glarborg, Peter

2010-01-01

In solid fuel flames, NO is largely formed from the oxidation of volatile nitrogen compounds such as HCN and NH3. To be able to model the nitrogen chemistry in these flames, it is necessary to have an adequate model for volatile-N oxidation. Simple global models for oxidation of HCN and NH3 from...... the literature should be used cautiously, since their predictive capabilities are limited, particularly under reducing conditions. Models for HCN/NH3/NO conversion based on the systematic reduction of a detailed chemical kinetic model offer high accuracy but rely on input estimates of combustion intermediates...... for the sub-bituminous and bituminous coals, especially at lower temperatures. The semiempirical correlations for estimating radical concentrations may also be useful in combination with models for other trace species, such as sulfur oxides, organic species, etc....

Inhibition of Corrosion of Zinc in (HNO 3 + HCl) acid mixture by ...

African Journals Online (AJOL)

Corrosion of Zinc metal in (HNO3 + HCl) binary acid mixture and inhibition efficiency of aniline has been studied by weight loss method and polarization technique. Corrosion rate increases with the concentration of acid mixture and the temperature. Inhibition efficiency (I.E.) of aniline increases with the concentration of ...

Degradation mechanism of CH{sub 3}NH{sub 3}PbI{sub 3} perovskite materials upon exposure to humid air

Energy Technology Data Exchange (ETDEWEB)

Shirayama, Masaki; Kato, Masato; Fujiseki, Takemasa; Hara, Shota; Kadowaki, Hideyuki; Murata, Daisuke; Fujiwara, Hiroyuki, E-mail: fujiwara@gifu-u.ac.jp [Department of Electrical, Electronic and Computer Engineering, Gifu University, 1-1 Yanagido, Gifu 501-1193 (Japan); Miyadera, Tetsuhiko; Sugita, Takeshi; Chikamatsu, Masayuki [Research Center for Photovoltaics, National Institute of Advanced Industrial Science and Technology (AIST), Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8568 (Japan)

2016-03-21

Low stability of organic-inorganic perovskite (CH{sub 3}NH{sub 3}PbI{sub 3}) solar cells in humid air environments is a serious drawback which could limit practical application of this material severely. In this study, from real-time spectroscopic ellipsometry characterization, the degradation mechanism of ultra-smooth CH{sub 3}NH{sub 3}PbI{sub 3} layers prepared by a laser evaporation technique is studied. We present evidence that the CH{sub 3}NH{sub 3}PbI{sub 3} degradation in humid air proceeds by two competing reactions of (i) the PbI{sub 2} formation by the desorption of CH{sub 3}NH{sub 3}I species and (ii) the generation of a CH{sub 3}NH{sub 3}PbI{sub 3} hydrate phase by H{sub 2}O incorporation. In particular, rapid phase change occurs in the near-surface region and the CH{sub 3}NH{sub 3}PbI{sub 3} layer thickness reduces rapidly in the initial 1 h air exposure even at a low relative humidity of 40%. After the prolonged air exposure, the CH{sub 3}NH{sub 3}PbI{sub 3} layer is converted completely to hexagonal platelet PbI{sub 2}/hydrate crystals that have a distinct atomic-scale multilayer structure with a period of 0.65 ± 0.05 nm. We find that conventional x-ray diffraction and optical characterization in the visible region, used commonly in earlier works, are quite insensitive to the surface phase change. Based on results obtained in this work, we discuss the degradation mechanism of CH{sub 3}NH{sub 3}PbI{sub 3} in humid air.

LPG and NH3 sensing characteristics of DC electrochemically deposited Co3O4 films

Science.gov (United States)

Shelke, P. N.; Khollam, Y. B.; Gunjal, S. D.; Koinkar, P. M.; Jadkar, S. R.; Mohite, K. C.

2015-03-01

Present communication reports the LPG and NH3 sensing properties of Co3O4 films prepared on throughly cleaned stainless steel (SS) and copper (CU) substrates by using DC electrochemical deposition method followed by air annealing at 350°C/2 h. The resultant films are characterized by using X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy (SEM). The LPG and NH3 gas sensing properties of these films are measured at room temperature (RT) by using static gas sensing system at different concentrations of test gas ranging from 25 ppm to 350 ppm. The XRD and Raman spectroscopy studies clearly indicated the formation of pure cubic spinel Co3O4 in all films. The LPG and NH3 gas sensing properties of films showed (i) the increase in sensitivity factor (S.F.) with gas concentrations and (ii) more sensibility to LPG as compared to NH3 gas. In case of NH3 gas (conc. 150 ppm) and LPG gas (conc. 60 ppm) sensing, the maximum S.F. = 270 and 258 are found for the films deposited on CU substrates, respectively. For all films, the response time (3-5 min.) is found to be much higher than the recovery time (30-50 sec). For all films, the response and recovery time are found to be higher for LPG as compared to NH3 gas. Further, repeatability-reproducibility in gas sensing properties is clearly noted by analysis of data for number of cycles recorded for all films from different set of depositions.

Synthesis, characterization, and application of Zn(NH 3)(CO3) for selective adsorptive separation of CO2

Science.gov (United States)

Khazeni, Naasser

This study explores the potential of Zn(NH3)(CO3) for selective CO2 separation. It develops a novel, highly controllable, single-pot synthesis approach based on urea hydrolysis and solvothermal aging to increase the feasibility of synthesizing Zn(NH3)(CO3), determines the structure of Zn(NH3)(CO3) in detail through single crystal X-ray diffraction and powder X-ray diffraction analyses, and performs adsorption analyses for the compound using CO2, N 2, H2, O2, and CH4 as adsorptives. Through adsorptive characterization, a systematic adsorbent selection screening is performed to assess the potential application of Zn(NH3)(CO 3) for adsorptive separation of CO2 from an upstream gas mixture of power generation, hydrogen production, and natural gas industries. Structural analysis shows Zn(NH3)(CO3) to have an inorganic helical framework that consists of a small helix of (ZnOCO) 2 and a large helix of (ZnOCO)4 with two ammines (NH 3) pendant from every other zinc. In terms of adsorption capacity and CO2 selectivity, Zn(NH3)(CO3) adsorbed 0.550 mmole/g CO2 at 293 K and 4500 mmHg, but only 0.047 mmole/g N 2, 0.084 mmole/g H2, 0.207 mmole/g 02, and 0.060 mmole/g CH4 at the same temperature and pressure. This behavior demonstrates considerable equilibrium selectivities - 36, 31, 63, and 11 - for separating CO2 from CH4, CO2 from H 2, CO2 from N2, and CO2 from 02, respectively. During adsorption, the pendant ammines act as the gates of check-valves: applied pressure opens the gates for adsorption; and during desorption, the gates are closed, trapping the adsorbates, until a reduction of pressure to near-atmospheric levels. Therefore, Zn(NH3)(CO3) exhibits low-pressure H3 or H4 hysteresis, indicating that the Zn(NH3)(CO3) framework can achieve gas storage at near-atmospheric pressures. Additionally, the compound proves structurally stable, with an adsorption decrease of 0.8% after 20 adsorption/desorption cycles - a factor that, considered with the other characteristics of Zn(NH

Detection of HCN and C2H2 in ISO Spectra of Oxygen-Rich AGB Stars

Science.gov (United States)

Carbon, Duane F.; Chiar, Jean; Goorvitch, David; Kwak, Dochan (Technical Monitor)

2002-01-01

Cool oxygen-rich AGB stars were not expected to have organic molecules like HCN in either their photospheres or circumstellar envelopes (CSEs). The discovery of HCN and CS microwave emission from the shallowest CSE layers of these stars was a considerable surprise and much theoretical effort has been expended in explaining the presence of such organics. To further explore this problem, we have undertaken a systematic search of oxygen-rich AGB stellar spectra in the Infrared Space Observatory (ISO) data archive. Our purposes are to find evidence regarding critical molecular species that could be of value in choosing among the proposed theoretical models, to locate spectral features which might give clues to conditions deeper in the CSEs, and to lay the groundwork for future SIRTF (Space Infrared Telescope Facility) and SOFIA (Stratospheric Observatory for Infrared Astronomy) observations. Using carefully reduced observations, we have detected weak absorption features arising from HCN and possibly C2H2 in a small number of oxygen-rich AGB stars. The most compelling case is NML Cyg which shows both HCN (14 microns) and CO2 (15 microns). VY CMa, a similar star, shows evidence for HCN, but not CO2. Two S-type stars show evidence for the C-H bending transitions: W Aql at 14 microns (HCN) and both W Aql and S Cas at 13.7 microns (C2H2). Both W Aql and S Cas as well as S Lyr, a SC-type star, show 3 micron absorption which may arise from the C-H stretch of HCN and C2H2. In the case of NML Cyg, we show that the HCN and CO2 spectral features are formed in the CSE at temperatures well above those of the outermost CSE layers and derive approximate column densities. In the case of the S-stars, we discuss the evidence for the organic features and their photospheric origin.

Photovoltaic performance and the energy landscape of CH3NH3PbI3.

Science.gov (United States)

Zhou, Yecheng; Huang, Fuzhi; Cheng, Yi-Bing; Gray-Weale, Angus

2015-09-21

Photovoltaic cells with absorbing layers of certain perovskites have power conversion efficiencies up to 20%. Among these materials, CH3NH3PbI3 is widely used. Here we use density-functional theory to calculate the energies and rotational energy barriers of a methylammonium ion in the α or β phase of CH3NH3PbI3 with differently oriented neighbouring methylammonium ions. Our results suggest the methylammonium ions in CH3NH3PbI3 prefer to rotate collectively, and to be parallel to their neighbours. Changes in polarization on rotation of methylammonium ions are two to three times larger than those on relaxation of the lead ion from the centre of its coordination shell. The preferences for parallel configuration and concerted rotation, with the polarisation changes, are consistent with ferroelectricity in the material, and indicate that this polarisation is governed by methylammonium orientational correlations. We show that the field due to this polarisation is strong enough to screen the field hindering charge transport, and find this screening field in agreement with experiment. We examine two possible mechanisms for the effect of methylammonium ion rotation on photovoltaic performance. One is that rearrangement of methylammoniums promotes the creation and transport of charge carriers. Some effective masses change greatly, but changes in band structure with methylammonium rotation are not large enough to explain current-voltage hysteresis behaviour. The second possible mechanism is that polarization screens the hindering electric field, which arises from charge accumulation in the transport layers. Polarization changes on methylammonium rotation favour this second mechanism, suggesting that collective reorientation of methylammonium ions in the bulk crystal are in significant part responsible for the hysteresis and power conversion characteristics of CH3NH3PbI3 photovoltaic cells.

Reaction kinetics of nitrous acid with acetohydroxamic acid in HClO4 and HNO3 medium

International Nuclear Information System (INIS)

Zheng Weifang; Yan Taihong; Bian Xiaoyan; Zhang Yu

2007-01-01

The presence of nitrous acid in feed solution of PUREX process is unavoidable. Owing to its effect on the valence of plutonium and other nuclides, nitrous acid should be scavenged. The kinetics of reaction of AHA with nitrous acid was studied in HClO 4 and HNO 3 medium. The reaction rate equation in HClO 4 and HNO 3 medium is obtained as. --dc(HNO 2 )/dr= k·c(HNO 2 ) 1 ·c(AHA) 0.75 ·c(HClO 4 ) 0.5 and --dc(HNO 2 )/dt=k·c(HNO 2 ) 1 ·c(AHA) 0.25 .· c(HNO 3 ) 1 , respectively. In HClO 4 medium, the reaction rate constant (k) is found to be (2.37±0.21) L 1.25 /(mol 1.25 ·s) at θ=5 degree C, I=0.5 mol/kg. Reaction rate constant is increased slightly with the increased ion strength in the range of 0.5-2.0 mol/kg. In HNO 3 medium, the reaction rate constant (k) is found to be (0.482±0.048) L 1.25 /(mol 1.25 ·s) at θ=10 degree C and I= 0.5 mol/kg. Reaction rate constant is also increased slightly with the increased ion strength in the range of 0.5-3.0 mol/kg. The effect of temperature to the reaction rate is also studied. The results show that with the increase of temperature, the reaction rate increases quickly. And the activation energy is found to be 99.0 kJ/mol and 46.9 kJ/mol respectively in HNO 3 . (authors)

The electronic and optical properties of CH3NH3MoI3 perovskite

Science.gov (United States)

Kansara, Shivam; Sonvane, Yogesh; Gupta, Sanjeev K.

2018-05-01

In this work, a first-principles theoretical study of hybrid perovskite CH3NH3MoI3 is performed using PBE exchange-correlation approximations in density functional theory. The results of electronic band structure are 0.90 eV (M-point: Direct) and 0.60 eV (R-X point: Indirect), respectively. We have also calculated the dielectric properties such as real, imaginary, extension coefficient (K) and reflectivity (R) properties of hybrid perovskite CH3NH3MoI3. The low-bandgap molecules are used to absorb near-IR range and typically having a bandgap smaller than 1.6 eV. This is particularly attractive in organic photovoltaics (OPV), photodetectors (PDs), and ambipolar field-effect transistors (FETs).

Irradiated NH3 and ND3 - two new target materials for polarized targets

International Nuclear Information System (INIS)

Meyer, W.

1982-11-01

A study of dynamic nuclear polarization (DNP) in NH 3 and ND 3 was made at the Bonn 2.5 GeV electron synchrotron. The paramagnetic radicals in the polycristalline ammonia beads were created by irradiation in the high intensity 20 MeV electron beam (> 10 14 electrons/sec) of the injection linac. During irradiation the ammonia beads, produced by dropping into liquid nitrogen, were cooled in liquid argon at approx.= 90 K. DNP measurements were performed at 1 K, 0.5 K and 0.2 K in a 2.5 T magnetic field. Samples of NH 3 , prepared in this way, yielded a maximum proton polarization of 66% at a temperature of 0.5 K with a short polarization build-up time of 9 minutes. ND 3 could be polarized at a temperature of 0.2 K up to 31%. The radiation resistance of the polarization of NH 3 is better than that of butanol. (orig.)

Formation of nitrogen compounds from nitrogen-containing rings during oxidative regeneration of spent hydroprocessing catalysts

Energy Technology Data Exchange (ETDEWEB)

Furimsky, E.; Nielsen, M.; Jurasek, P. [CANMET, Ottawa, ON (Canada). Energy Research Laboratories

1995-05-01

Commercial CoMo and NiMo catalysts in an oxidic and sulfided form and a {gamma}-alumina were deposited with pyrrole, pyridine, and quinoline. The deposited catalysts and two spent hydroprocessing catalysts were pyrolyzed and oxidized under conditions typical of regeneration of hydroprocessing catalysts. The formation of NH{sub 3} and HCN, as well as selected cases of N{sub 2}O and NO, was monitored during the experiments. NH{sub 3} and HCN were formed during pyrolysis of pyrrole-deposited catalysts whereas only NH{sub 3} was formed during that of pyridine-and quinoline-deposited catalysts. For all deposited catalysts, both NH{sub 3} and HCN were formed during temperature programmed oxidation in 2% O{sub 2}. For spent catalysts, a small amount of N{sub 2}O was formed in 2 and 4% O{sub 2}. For pyrrole-deposited catalysts, large yields of N{sub 2}O were formed in 4% O{sub 2}. Under the same conditions, N{sub 2}O yields for pyridine- and quinoline-deposited catalysts were very small. 13 refs., 12 figs., 6 tabs.

Order-disorder phase transition in the peroxidovanadium complex NH4[VO(O2)2(NH3)].

Science.gov (United States)

Schwendt, Peter; Gyepes, Róbert; Chrappová, Jana; Němec, Ivan; Vaněk, Přemysl

2018-07-05

Complex NH 4 [VO(O 2 ) 2 (NH 3 )] (1) undergoes an order-disorder phase transition at T c ~258K. This transition is accompanied by change in the space group of the orthorhombic lattice and also by significant structural rearrangements of the constituent molecules, which are pertinent mostly to their NH 4 + ions and their ammonia ligands. The low-temperature solid state IR and Raman spectra of 1 were corroborated by solid-state computations that employed Gaussian functions as the basis set. Results of these computations yielded excellent agreement with experimental data. On the curves of temperature dependence of vibrational modes, the phase transition is expressed by an abrupt change of the slope above T c . Copyright © 2018 Elsevier B.V. All rights reserved.

Rietveld refinement of the crystal structure of perovskite solar cells using CH3NH3PbI3 and other compounds

Science.gov (United States)

Ando, Yuji; Ohishi, Yuya; Suzuki, Kohei; Suzuki, Atsushi; Oku, Takeo

2018-01-01

The crystal structures of perovskite thin films including CH3NH3PbI3, CH3NH3Pb1-xSbxI3, and CH3NH3PbI3-yCly in the solar cell configuration were studied by using Rietveld refinement. For the CH3NH3PbI3 and CH3NH3Pb1-xSbxI3 samples, satisfactory agreement with the measured profiles was obtained with a weighted profile R-factor (Rwp) of as low as 3%. It was shown that the site occupancy of methylammonium (MA) was decreased in the antimonized cell due to the compensation effect of an increased positive charge brought about by replacing Pb2+ with Sb3+. Photovoltaic measurements showed that the power conversion efficiency was enhanced by adding a small amount of Sb to the CH3NH3PbI3 cell, but it was monotonically decreased as the mole fraction of Sb exceeded 0.03. This variation of the conversion efficiency was considered as a result of suppressed crystallization of PbI2 and carrier recombination via MA vacancies in the antimonized cells. In the case of CH3NH3PbI2.88Cl0.12 sample, the agreement with the measured profile with an Rwp of as high as 7% suggested the co-existence of cubic and tetragonal phases in the chlorinated cell.

THE HCN/HNC ABUNDANCE RATIO TOWARD DIFFERENT EVOLUTIONARY PHASES OF MASSIVE STAR FORMATION

Energy Technology Data Exchange (ETDEWEB)

Jin, Mihwa; Lee, Jeong-Eun [School of Space Research, Kyung Hee University, Yongin-Si, Gyeonggi-Do 446-701 (Korea, Republic of); Kim, Kee-Tae, E-mail: mihwajin.sf@gmail.com, E-mail: jeongeun.lee@khu.ac.kr, E-mail: ktkim@kasi.re.kr [Korea Astronomy and Space Science Institute, 776 Daedeokdae-ro, Yuseong-gu, Daejeon 305-348 (Korea, Republic of)

2015-07-20

Using the H{sup 13}CN and HN{sup 13}C J = 1–0 line observations, the abundance ratio of HCN/HNC has been estimated for different evolutionary stages of massive star formation: infrared dark clouds (IRDCs), high-mass protostellar objects (HMPOs), and ultracompact H ii regions (UCH iis). IRDCs were divided into “quiescent IRDC cores (qIRDCc)” and “active IRDC cores (aIRDCc),” depending on star formation activity. The HCN/HNC ratio is known to be higher at active and high temperature regions related to ongoing star formation, compared to cold and quiescent regions. Our observations toward 8 qIRDCc, 16 aIRDCc, 23 HMPOs, and 31 UCH iis show consistent results; the ratio is 0.97 (±0.10), 2.65 (±0.88), 4.17 (±1.03), and 8.96 (±3.32) in these respective evolutionary stages, increasing from qIRDCc to UCH iis. The change of the HCN/HNC abundance ratio, therefore, seems directly associated with the evolutionary stages of star formation, which have different temperatures. One suggested explanation for this trend is the conversion of HNC to HCN, which occurs effectively at higher temperatures. To test the explanation, we performed a simple chemical model calculation. In order to fit the observed results, the energy barrier of the conversion must be much lower than the value provided by theoretical calculations.

Photochemistry of methane and the formation of hydrocyanic acid (HCN) in the earth's early atmosphere

Science.gov (United States)

Zahnle, K. J.

1986-01-01

A one-dimensional photochemical model is used to analyze the photochemistries of CH4 and HCN in the primitive terrestrial atmosphere. CH4, N2, and HCN photolysis are examined. The background atmosphere and boundary conditions applied in the analysis are described. The formation of HCN as a by-product of N2 and CH4 photolysis is investigated; the effects of photodissociation and rainfall on HCN is discussed. The low and high CH4 mixing ratios and radical densities are studied.

Study of various NH4+/NO3- mixtures for enhancing growth of potatoes

Science.gov (United States)

Cao, W.; Tibbitts, T. W.

1993-01-01

Two experiments were conducted to determine the effects of various NH4(+)-N/NO3(-)-N percentages on growth and mineral concentrations in potato (Solanum tuberosum L.) plants using a non-recirculating nutrient film system in a controlled environment. The first experiment included six NH4(+)-N/NO3(-)-N percentages at 0/100, 20/80, 40/60, 60/40, 80/20, and 100/0 with the same total N concentration of 4 mM. The second experiment included six NH4(+)-N/NO3(-)-N percentages at 0/100, 4/96, 8/92, 12/88, 16/84, and 20/80 again with the same total N of 4 mM. In each experiment, plants were harvested 35 days after transplanting when tubers had been initiated and started to enlarge. Dry weights of shoots, tubers, and whole plant at the harvest were increased significantly with all mixed nitrogen treatments as compared with single NH4+ or NO3- form. The enhanced growth with mixed nitrogen was greatest at 8% to 20% NH4(+)-N. Also, the concentrations and accumulation of total N in the shoots and roots were greater with mixed nitrogen than with separate NH4+ or NO3- nutrition. With NH4+ present in the solutions, the concentrations of P and Cl in the shoots were increased compared to NO3- alone, whereas the tissue concentrations of Ca and Mg were decreased. It was concluded that nitrogen fertilization provided with combined NH4+ and NO3- forms, even at small proportions of NH4+, can enhance nitrogen uptake and productivity in potato plants.

New CO and HCN sources associated with IRAS carbon stars

Science.gov (United States)

NGUYEN-Q-RIEU; Epchtein, N.; TRUONG-BACH; Cohen, M.

1987-01-01

Emission of CO and HCN was detected in 22 out of a sample of 53 IRAS sources classified as unidentified carbon-rich objects. The sample was selected according to the presence of the silicon carbide feature as revealed by low-resolution spectra. The molecular line widths indicate that the CO and HCN emission arises from the circumstellar envelopes of very highly evolved stars undergoing mass loss. The visible stars tend to be deficient in CO as compared with unidentified sources. Most the detected CO and HCN IRAS stars are distinct and thick-shelled objects, but their infrared and CO luminosities are similar to those of IRC + 102156 AFGL and IRC-CO evolved stars. The 12 micron flux seems to be a good indicator of the distance, hence a guide for molecular searches.

Searching for Faint Traces of CO(2-1) and HCN(4-3) Gas In Debris Disks

Science.gov (United States)

Stafford Lambros, Zachary; Hughes, A. Meredith

2018-01-01

The surprising presence of molecular gas in the debris disks around main sequence stars provides an opportunity to study the dissipation of primordial gas and, potentially, the composition of gas in other solar systems. Molecular gas is not expected to survive beyond the pre-main sequence phase, and it is not yet clear whether the gas is a remnant of the primordial protoplanetary material or whether the gas, like the dust, is second-generation material produced by collisional or photodesorption from planetesimals, exocomets, or the icy mantles of dust grains. Here we present two related efforts to characterize the prevalence and properties of gas in debris disks. First, we place the lowest limits to date on the CO emission from an M star debris disk, using 0.3" resolution observations of CO(2-1) emission from the AU Mic system with the Atacama Large Millimeter/submillimeter Array (ALMA). We place a 3-sigma upper limit on the integrated flux of 0.39 Jy km/s, corresponding to a maximum CO mass of 5e10-6 (Earth Masses) if the gas is in LTE. We also present the results of an ALMA search for HCN(4-3) emission from the prototypical gas-rich debris disk around 49 Ceti at a spatial resolution of 0.3". Despite hosting one of the brightest CO-rich debris disks yet discovered, our observations of 49 Ceti also yield a low upper limit of 0.057 Jy km/s in the HCN line, leaving CO as the only molecule clearly detected in emission from a debris disk. We employ several methods of detecting faint line emission from debris disks, including a model based on Keplerian kinematics as well as a spectral shifting method previously used to detect faint CO emission from the Fomalhaut debris disk, and compare our results.

NH3 Abatement in Fluidized Bed Co-Gasification of RDF and Coal

Science.gov (United States)

Gulyurtlu, I.; Pinto, Filomena; Dias, Mário; Lopes, Helena; André, Rui Neto; Cabrita, I.

Gasification of wastes may come out as an alternative technology to produce a gas with many potential applications, from direct burning in a boiler or motor to the production of synthetic chemicals and hydrogen. High tar production and high operational costs are preventing gasification wider dissemination. Besides these problems, the presence of NH3 in the syngas may have a negative impact as it can be converted into nitrogen oxides if the gas is further burnt. To reduce NH3 formation it is required a full understanding of how operational parameters contribute to the formation/reduction of this pollutant. A full studyon the effect of fuel composition, temperature and equivalence ratio on the formation of NH3 is given. Experimental results are compared to theoretical ones obtained with FactSage software. It is also analyzed the effect of feedstock mineral matterin NH3 release during gasification. Toaccomplish a significant decrease in the release of NH3, different catalysts and sorbents were tested with the aim of achieving high energy conversions and low environmental impact.

Molecular modelling of the decomposition of NH{sub 3} over CoO(100)

Energy Technology Data Exchange (ETDEWEB)

Shojaee, Kambiz; Haynes, Brian S.; Montoya, Alejandro, E-mail: alejandro.montoya@sydney.edu.au

2015-04-15

Spin-polarised density functional theory using the PBE + U approach are used to determine reaction pathways of successive NH{sub 3} dehydrogenation on the CoO(100) surface. NH{sub 3} dehydrogenation promotes noticeable displacements of the surface CoO sites, in particular due to the binding of NH{sub 2} and H species. Surface lattice O has low activity towards dehydrogenation, reflected in energy barriers that are in the range of 292 kJ mol{sup −1} to 328 kJ mol{sup −1}. There is a preference of surface NH{sub 3} dehydrogenation to N{sub 2} rather than towards NO, due to a high-energy penalty of surface O vacancy formation. The presence of CoO in cobalt oxide catalysts not only may decline the ammonia conversion but also alter the selectivity towards N{sub 2} rather than NO. - Highlights: • Minimum reactions pathways of ammonia decomposition were studied using density functional theory. • The bonding characteristics of NH{sub x} and H on the CoO(100) surface were analysed using Layer-projected density of states. • Dehydrogenations of NH{sub 3}, NH{sub 2} and NH are highly activated. • The presence of strongly bound lattice oxygen favours the ammonia decomposition towards N{sub 2}.

A new ppb-gas analyzer by means of GC-ion mobility spectrometry (GC-IMS)

International Nuclear Information System (INIS)

Leonhardt, J.W.

2003-01-01

IMS-detectors are using beta-sources like tritium or nickel-63. This detection principle uses fast ion-molecular reactions between air cluster ions, produced by beta ionization and the analyte. The system works at normal pressure, the very high sensitivity and selectivity is used widely in industry, research, medicine and environmental control. In the last few years especially, small tritium sources were reduced to a level of some 50 MBq, which is 20 times less than the exemption levels for these sources. One of the handicaps of that technology is the problem of cross sensitivities. To overcome these problems a special GC-column of 1 m length has been included into the gas inlet and mixtures of compounds get separated by their retention times before entering the drift sensor. By means of that method a new analytical quality of IMS is arrived. The application of these analytical devices got a spin off in the last year. The main applications being discussed are as follows: (1) anti terror systems in buildings and facilities, (2) working place monitoring in chemical industry, (3) microelectronics: HF, HCl, Cl 2 , NMP, NH 3 , NO 2 , SO 2 , (4) environment: NH 3 , HCN, HCl, CH 2 O, organic compounds, SO 2 , NO 2 , (5) gas and petrol: gas-carottage, H 2 S, mercaptans, (6) household, furniture: solvents, clue, organic vapour from furniture, and (7) health care: diagnostics of various diseases. (author)

Synthesis of 15N-enriched urea (CO(15NH22 from 15NH3, CO, and S in a discontinuous process

Directory of Open Access Journals (Sweden)

C. R. Sant Ana Filho

2012-12-01

Full Text Available CO(15NH22 enriched with the stable isotope 15N was synthesized based on a reaction involving CO, 15NH3, and S in the presence of CH3OH. The method differs from the industrial method; a stainless steel reactor internally lined with polytetrafluoroethylene (PTFE was used in a discontinuous process under low pressure and temperature. The yield of the synthesis was evaluated as a function of the parameters: the amount of reagents, reaction time, addition of H2S, liquid solution and reaction temperature. The results showed that under optimum conditions (1.36, 4.01, and 4.48 g of 15NH3, CO, and S, respectively, 40 ml CH3OH, 40 mg H2S, 100 ºC and 120 min of reaction 1.82 g (yield 76.5% of the compound was obtained per batch. The synthesized CO(15NH22 contained 46.2% N, 0.55% biuret, melting point of 132.55 ºC and did not exhibit isotopic fractionation. The production cost of CO(15NH22 with 90.0 at. % 15N was US$ 238.60 per gram.

Effects of CsBr addition on the performance of CH3NH3PbI3-xClx-based solar cells

Science.gov (United States)

Ueoka, Naoki; Oku, Takeo; Ohishi, Yuya; Tanaka, Hiroki; Suzuki, Atsushi; Sakamoto, Hiroki; Yamada, Masahiro; Minami, Satoshi; Tsukada, Shinichiro

2018-01-01

Perovskite-type photovoltaic devices were prepared by a spin-coating method using a precursor solution of CH3NH3I and lead(II) chloride in N,N-dimethylformamide. Effects of cesium bromide (CsBr) addition on the photovoltaic properties and microstructures of the perovskite phase were investigated. The fill factor was increased by adding the CsBr to the CH3NH3PbI3-xClx precursor solution, which resulted in increase of the conversion efficiency. The crystallinity of the CH3NH3PbI3-xClx perovskite phase was also improved by adding the CsBr to the H3NH3PbI3-xClx precursor solution.

Syngas to Synfuels Process Development Unit Final Scientific/Technical Report

Energy Technology Data Exchange (ETDEWEB)

Brown, Robert C. [Iowa State Univ., Ames, IA (United States)

2012-03-30

The process described is for the gasification of 20 kg/h of biomass (switchgrass) to produce a syngas suitable for upgrading to Fischer-Tropsch (FT) liquid fuels (gas, diesel, waxes, etc.). The gas stream generated from gasification is primarily composed of carbon monoxide (CO), hydrogen (H₂), carbon dioxide (CO₂), steam (H₂O), and methane (CH₄), but also includes tars, particulate matter, ammonia (NH₃), hydrogen cyanide (HCN), hydrogen chloride (HCl), hydrogen sulfide ( H₂S), carbonyl sulfide (COS), etc. as contaminants. The gas stream passes through an array of cleaning devices to remove the contaminants to levels suitable for FT synthesis of fuels/chemicals. These devices consist primarily of an oil scrubber (to remove tars and remaining particulates), sulfur scrubber (to remove sulfur compounds), and a wet scrubber (to remove NH₃, HCl and remaining water soluble contaminants). The ammonia and oil scrubbers are absorption columns with a combination of random and structured packing materials, using water and oil as the adsorption liquids respectively. The ammonia scrubber performed very well, while operating the oil scrubber proved to be more difficult due to the nature of tar compounds. The sulfur scrubber is a packed bed absorption device with solid extrudates of adsorbent material, primarily composed of ZnO and CuO. It performed well, but over a limited amount of time due to fouling created by excess tar/particulate matter and oil aerosols. Overall gas contaminants were reduced to below 1 ppm NH₃, and less than 1 ppm collective sulfur compounds.

Enhanced photovoltaic performance of CH3NH3PbBrXI3-X-based perovskite solar cells via anti-solvent extraction

Science.gov (United States)

Jiang, Zhaoyi; Zhang, Weijia; Lu, Chaoqun; Ma, Denghao; Liu, Haixu; Yu, Wei; Zhang, Yu; Ma, Qiang; Zhang, Yulong

2018-06-01

In this paper, the two-step sequential deposition method was used to prepare the CH3NH3PbBrXI3-X films by introducing CH3NH3Br in the precursors. The surface morphology of the PbI2 films was controlled by anti-solvent extraction (ASE) to improve the microstructure and photo-physical properties of the perovskite films. It was noteworthy that, compared to the compact PbI2 films, the porous PbI2 films facilitated the growth of crystals and bromine incorporation in films, and the prepared perovskite films exhibited enlarged grain size, increased light absorption, enhanced Br incorporation and prolonged carrier lifetime, which resulted in excellent photo-electrical properties of the CH3NH3PbBrXI3-X films. With porous PbI2 templates, the inverted planar perovskite solar cells based on films with appropriate Br incorporation (CH3NH3Br/CH3NH3I mole ratio = 3/7) showed a photovoltaic conversion efficiency (PCE) of 14.9%, and the stability of the devices in air was elevated. Consequently, the high-quality CH3NH3PbBrXI3-X films can be obtained with porous PbI2 templates for improving the performance of the perovskite solar cells.

Sequence of phase transitions in (NH4)3SiF7.

Science.gov (United States)

Mel'nikova, S V; Molokeev, M S; Laptash, N M; Pogoreltsev, E I; Misyul, S V; Flerov, I N

2017-02-21

Single crystals of silicon double salt (NH 4 ) 3 SiF 7 = (NH 4 ) 2 SiF 6 ·NH 4 F = (NH 4 ) 3 [SiF 6 ]F were grown and studied by the methods of polarization optics, X-ray diffraction and calorimetry. A sequence of symmetry transformations with the temperature change was established: P4/mbm (Z = 2) (G 1 ) ↔ Pbam (Z = 4) (G 2 ) ↔ P2 1 /c (Z = 4) (G 3 ) ↔ P1[combining macron] (Z = 4) (G 4 ) ↔ P2 1 /c (Z = 8) (G 5 ). Crystal structures of different phases were determined. The experimental data were also interpreted by a group-theoretical analysis of the complete condensate of order parameters taking into account critical and noncritical atomic displacements. Strengthening of the N-HF hydrogen bonds can be a driving force of the observed phase transitions.

A 1D coordination polymer of UF{sub 5} with HCN as a ligand

Energy Technology Data Exchange (ETDEWEB)

Scheibe, Benjamin; Rudel, Stefan S.; Buchner, Magnus R.; Kraus, Florian [Fachbereich Chemie, Philipps-Universitaet Marburg (Germany); Karttunen, Antti J. [Department of Chemistry, Aalto University (Finland)

2017-01-05

β-Uranium(V) fluoride was reacted with liquid anhydrous hydrogen cyanide to obtain a 1D coordination polymer with the composition {sup 1}{sub ∞}[UF{sub 5}(HCN){sub 2}], {sup 1}{sub ∞}[UF{sub 4/1}F{sub 2/2}-(HCN){sub 2/1}], revealed by single-crystal X-ray structure determination. The reaction system was furthermore studied by means of vibrational and NMR spectroscopy, as well as by quantum chemical calculations. The compound presents the first described polymeric HCN Lewis adduct and the first HCN adduct of a uranium fluoride. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Synthesis and structural characterization of two cobalt phosphites: 1-D (H3NC6H4NH3)Co(HPO3)2 and 2-D (NH4)2Co2(HPo3)3

International Nuclear Information System (INIS)

Cheng, C.-C.; Chang, W.-K.; Chiang, R.-K.; Wang, S.-L.

2010-01-01

Two new cobalt phosphites, (H 3 NC 6 H 4 NH 3 )Co(HPO 3 ) 2 (1) and (NH 4 ) 2 Co 2 (HPO 3 ) 3 (2), have been synthesized and characterized by single-crystal X-ray diffraction. All the cobalt atoms of 1 are in tetrahedral CoO 4 coordination. The structure of 1 comprises twisted square chains of four-rings, which contain alternating vertex-shared CoO 4 tetrahedra and HPO 3 groups. These chains are interlinked with trans-1,4-diaminocyclohexane cations by hydrogen bonds. The 2-D structure of 2 comprises anionic complex sheets with ammonium cations present between them. An anionic complex sheet contains three-deck phosphite units, which are interconnected by Co 2 O 9 to form complex layers. Magnetic susceptibility measurements of 1 and 2 showed that they have a weak antiferromagnetic interaction. - Graphical abstract: The 2-D structure of (NH 4 ) 2 Co 2 (HPO 3 ) 3 comprises anionic complex sheets with ammonium cations present between them. An anionic complex sheet contains three-deck phosphite units, which are interconnected by dimmeric Co 2 O 9 to form complex layers.

Lamellar γ-AlOOH architectures: Synthesis and application for the removal of HCN

International Nuclear Information System (INIS)

Hou Hongwei; Zhu You; Tang Gangling; Hu Qingyuan

2012-01-01

Using hexadecyl trimethyl ammonium bromide (CTAB) as a structure-directing agent and precipitator, the complete synthesis of lamellar γ-AlOOH architectures was successfully accomplished via a hydrothermal route. Different product structures were obtained by varying the molar ratio of aluminum nitrate and CTAB. Several techniques, including X-ray powder diffraction, Fourier transform infrared spectroscopy, field-emission scanning electron microscopy, transmission electron microscopy, and differential scanning calorimetry thermal analysis, were used to characterize the products. The effects of CTAB concentration, reaction temperature and time, and the molar ratio of Al 3+ /CTAB on the product morphologies were investigated. The nitrogen adsorption and desorption measurements indicated that the γ-AlOOH architectures possess a Brunauer–Emmett–Teller surface area of approximately 75.02 m 2 /g. It was also demonstrated that 10 mg γ-AlOOH architectures can remove 45.3% of the HCN (1.68 μg/mL) from model wastewater. When 0.03 mg/cig γ-AlOOH architectures were combined with cigarette paper, 8.12% of the present HCN was adsorbed. These results indicate that lamellar γ-AlOOH architectures may be a potential adsorbent for removing HCN from highly toxic pollutant solutions and harmful cigarette smoke. Highlights: ► Hexadecyl trimethyl ammonium bromide (CTAB) was used as a structure-directing agent and precipitator. ► Hydrothermal treatment enables growth of lamellar γ-AlOOH architectures. ► Lamellar γ-AlOOH architectures were demonstrated to exhibit high BET surface area and excellent adsorptive capacity. ► HCN in contaminated water and cigarette smoke can be effectively removed by the prepared lamellar γ-AlOOH superstructures.

The international research progress of Ammonia(NH3) emissions and emissions reduction technology in farmland ecosystem

Science.gov (United States)

Yang, W. Z.; Jiao, Y.

2017-03-01

NH3 is the important factor leading to the grey haze, and one of the main causes of environmental problems of serious ecological imbalance, such as acid rain and air quality deterioration. The fertilizer excessive application of the current farmland results NH3 emissions intensity greatly. In order to clear the farmland NH3 emissions research status and achievements, the literature of farmland NH3 emission related were retrievaled by the SCI journals and Chinese science citation database. Some factors of NH3 emission were analyzed such as soil factors, climate factors and farmland management measures. The research progress was inductived on farmland NH3 emission reduction technology. The results will help to clarify farmland NH3 emissions research progress. The theoretical guidance was provided on the future of farmland NH3 emissions research.

Field-effect transistors with high mobility and small hysteresis of transfer characteristics based on CH3NH3PbBr3 films

Science.gov (United States)

Aleshin, A. N.; Shcherbakov, I. P.; Trapeznikova, I. N.; Petrov, V. N.

2017-12-01

Field-effect transistor (FET) structures based on soluble organometallic perovskites, CH3NH3PbBr3, were obtained and their electrical properties were studied. FETs made of CH3NH3PbBr3 films possess current- voltage characteristics (IVs) typical for ambipolar FETs with saturation regime. The transfer characteristics of FETs based on CH3NH3PbBr3 have an insignificant hysteresis and slightly depend on voltage at the source-drain. Mobilities of charge carriers (holes) calculated from IVs of FETs based on CH3NH3PbBr3 at 300 K in saturation and weak field regimes were 5 and 2 cm2/V s, respectively, whereas electron mobility is 3 cm2/V s, which exceeds the mobility value 1 cm2/V s obtained earlier for FETs based on CH3NH3PbI3.

Electron transport in NH3/NO2 sensed buckled antimonene

Science.gov (United States)

Srivastava, Anurag; Khan, Md. Shahzad; Ahuja, Rajeev

2018-04-01

The structural and electronic properties of buckled antimonene have been analysed using density functional theory based ab-initio approach. Geometrical parameters in terms of bond length and bond angle are found close to the single ruffle mono-layer of rhombohedral antimony. Inter-frontier orbital analyses suggest localization of lone pair electrons at each atomic centre. Phonon dispersion along with high symmetry point of Brillouin zone does not signify any soft mode. With an electronic band gap of 1.8eV, the quasi-2D nano-surface has been further explored for NH3/NO2 molecules sensing and qualities of interaction between NH3/NO2 gas and antimonene scrutinized in terms of electronic charges transfer. A current-voltage characteristic has also been analysed, using Non Equilibrium Green's function (NEGF), for antimonene, in presence of incoming NH3/NO2 molecules.

MARVEL analysis of the measured high-resolution spectra of 14NH3

International Nuclear Information System (INIS)

Al Derzi, Afaf R.; Furtenbacher, Tibor; Tennyson, Jonathan; Yurchenko, Sergei N.; Császár, Attila G.

2015-01-01

Accurate, experimental rotational–vibrational energy levels and line positions, with associated labels and uncertainties, are reported for the ground electronic state of the symmetric-top 14 NH 3 molecule. All levels and lines are based on critically reviewed and validated high-resolution experimental spectra taken from 56 literature sources. The transition data are in the 0.7–17 000 cm −1 region, with a large gap between 7000 and 15 000 cm −1 . The MARVEL (Measured Active Rotational–Vibrational Energy Levels) algorithm is used to determine the energy levels. Out of the 29 450 measured transitions 10 041 and 18 947 belong to ortho- and para- 14 NH 3 , respectively. A careful analysis of the related experimental spectroscopic network (SN) allows 28 530 of the measured transitions to be validated, 18 178 of these are unique, while 462 transitions belong to floating components. Despite the large number of spectroscopic measurements published over the last 80 years, the transitions determine only 30 vibrational band origins of 14 NH 3 , 8 for ortho- and 22 for para- 14 NH 3 . The highest J value, where J stands for the rotational quantum number, for which an energy level is validated is 31. The number of experimental-quality ortho- and para- 14 NH 3 rovibrational energy levels is 1724 and 3237, respectively. The MARVEL energy levels are checked against ones in the BYTe first-principles database, determined previously. The lists of validated lines and levels for 14 NH 3 are deposited in the Supporting Information to this paper. Combination of the MARVEL energy levels with first-principles absorption intensities yields a huge number of experimental-quality rovibrational lines, which should prove to be useful for the understanding of future complex high-resolution spectroscopy on 14 NH 3 ; these lines are also deposited in the Supporting Information to this paper

MARVEL analysis of the measured high-resolution spectra of 14NH3

Science.gov (United States)

Al Derzi, Afaf R.; Furtenbacher, Tibor; Tennyson, Jonathan; Yurchenko, Sergei N.; Császár, Attila G.

2015-08-01

Accurate, experimental rotational-vibrational energy levels and line positions, with associated labels and uncertainties, are reported for the ground electronic state of the symmetric-top 14NH3 molecule. All levels and lines are based on critically reviewed and validated high-resolution experimental spectra taken from 56 literature sources. The transition data are in the 0.7-17 000 cm-1 region, with a large gap between 7000 and 15 000 cm-1. The MARVEL (Measured Active Rotational-Vibrational Energy Levels) algorithm is used to determine the energy levels. Out of the 29 450 measured transitions 10 041 and 18 947 belong to ortho- and para-14NH3, respectively. A careful analysis of the related experimental spectroscopic network (SN) allows 28 530 of the measured transitions to be validated, 18 178 of these are unique, while 462 transitions belong to floating components. Despite the large number of spectroscopic measurements published over the last 80 years, the transitions determine only 30 vibrational band origins of 14NH3, 8 for ortho- and 22 for para-14NH3. The highest J value, where J stands for the rotational quantum number, for which an energy level is validated is 31. The number of experimental-quality ortho- and para-14NH3 rovibrational energy levels is 1724 and 3237, respectively. The MARVEL energy levels are checked against ones in the BYTe first-principles database, determined previously. The lists of validated lines and levels for 14NH3 are deposited in the Supporting Information to this paper. Combination of the MARVEL energy levels with first-principles absorption intensities yields a huge number of experimental-quality rovibrational lines, which should prove to be useful for the understanding of future complex high-resolution spectroscopy on 14NH3; these lines are also deposited in the Supporting Information to this paper.

Tunable far infrared laser spectroscopy of van der Waals bonds: Ar-NH3

International Nuclear Information System (INIS)

Gwo, Dz-Hung; California Univ., Berkeley, CA

1989-11-01

Hyperfine resolved vibration-rotation-tunneling spectra of Ar--NH 3 and (NH 3 ) 2 , generated in a planar supersonic jet, have been measured with the Berkeley tunable far infrared laser spectrometer. Among the seven rotationally assigned bands, one band belongs to Ar--NH 3 , and the other six belong to (NH 3 ) 2 . To facilitate the intermolecular vibrational assignment for Ar--NH 3 , a dynamics study aided by a permutation-inversion group theoretical treatment is performed on the rovibrational levels. The rovibrational quantum number correlation between the free internal rotor limit and the semi-rigid limit is established to provide a basic physical picture of the evolution of intermolecular vibrational component states. An anomalous vibronically allowed unique Q branch vibrational band structure is predicted to exist for a near prolate binary complex containing an inverting subunit. According to the model developed in this work, the observed band of Ar--NH 3 centered at 26.470633(17) cm -1 can correlate only to either the fundamental dimeric stretching band for the A 2 states with the NH 3 inversional quantum number v i = 1, or the K a = 0 left-arrow 0 subband of the lowest internal-rotation-inversion difference band. Although the estimated nuclear quadrupole coupling constant favors a tentative assignment in terms of the first possibility, a definitive assignment will require far infrared data and a dynamical model incorporating a potential surface

Crystallographic Investigations into Properties of Acentric Hybrid Perovskite Single Crystals NH(CH3)3SnX3(X = Cl, Br)

KAUST Repository

Dang, Yangyang

2016-10-11

The hybrid perovskites with special optoelectronic properties have attracted more attention to the scientific and industrial applications. However, because of the toxicity and instability of lead complexes, there is interest in finding a nontoxic substitute for the lead in the halides perovskites and solving the ambiguous crystal structures and phase transition of NH(CH3)3SnX3 (X = Cl, Br). Here, we report the bulk crystal growths and different crystal morphologies of orthorhombic hybrid perovskites NH(CH3)3SnX3 (X = Cl, Br) in an ambient atmosphere by bottom-seeded solution growth (BSSG) method. More importantly, detailed structural determination and refinements, phase transition, band gap, band structure calculations, nonlinear optical (NLO) properties, XPS, thermal properties, and stability of NH(CH3)3SnX3 (X = Cl, Br) single crystals are demonstrated. NH(CH3)3SnCl3 single crystal undergoes reversible structural transformation from orthorhombic space group Cmc21 (no. 36) to monoclinic space group Cc (no. 9) and NH(CH3)3SnBr3 belongs to the orthorhombic space group Pna21 (no. 33) by DSC, single-crystal X-ray diffraction and temperature-dependent SHG measurements, which clarify the former results. These results should pave the way for further studies of these materials in optoelectronics.

Experimental study of rapid brown coal pyrolysis at high temperature

Energy Technology Data Exchange (ETDEWEB)

Qian, Lin; Sun, Shaozeng; Meng, Shun; Meng, Xianyu; Guo, Yangzhou [Harbin Institute of Technology, Harbin (China). Combustion Engineering Research Inst.

2013-07-01

Rapid coal pyrolysis is a very important step in the early stage of combustion. Rapid pyrolysis experiments of a brown coal at high temperature have been studied on a laminar drop tube furnace. The volatile mass release measured in this study is high for low rank coal. The activation energy and pre-exponential factor of pyrolysis are 19901.22 kJ/mol and 102.71, respectively. The nitrogen distribution between volatile and char is 0.54. With the increase of temperature, the yields of NH{sub 3} decreases, while those of HCN increases, leading the value of HCN/NH{sub 3} to become larger. At high temperature, the main nitrogen- containing species of pyrolysis in volatile is HCN.

Theoretical study on the gas adsorption capacity and selectivity of CPM-200-In/Mg and CPM-200-In/Mg-X (-X = -NH2, -OH, -N, -F).

Science.gov (United States)

Liu, Xiao-le; Chen, Guang-Hui; Wang, Xiu-Jun; Li, Peng; Song, Yi-Bing; Li, Rui-Yan

2017-11-15

The adsorption capacities of a heterometallic metal-organic framework (CPM-200-In/Mg) to VOCs (HCHO, C 2 H 4 , CH 4 , C 2 H 2 , C 3 H 8 , C 2 H 6 , C 2 H 3 Cl, C 2 H 2 Cl 2 , CH 2 Cl 2 and CHCl 3 ) and some inorganic gas molecules (HCN, SO 2 , NO, CO 2 , CO, H 2 S and NH 3 ), as well as its selectivity in ternary mixture systems of natural gas and post-combustion flue gas are theoretically explored at the grand canonical Monte Carlo (GCMC) and density functional theory (DFT) levels. It is shown that CPM-200-In/Mg is suitable for the adsorption of VOCs, particularly for HCHO (up to 0.39 g g -1 at 298 K and 1 bar), and the adsorption capacities of some inorganic gas molecules such as SO 2 , H 2 S and CO 2 match well with the sequence of their polarizability (SO 2 > H 2 S > CO 2 ). The large adsorption capacities of HCN and HCHO in the framework result from the strong interaction between adsorbates and metal centers, based on analyzing the radial distribution functions (RDF). Comparing C 2 H 4 and CH 4 molecules interacting with CPM-200-In/Mg by VDW interaction, we speculate that the high adsorption capacities of their chlorine derivatives in the framework could be due to the existence of halogen bonding or strong electrostatic and VDW interactions. It is found that the basic groups, including -NH 2 , -N and -OH, can effectively improve both the adsorption capacities and selectivity of CPM-200-In/Mg for harmful gases. Note that the adsorption capacity of CPM-200-In/Mg-NH 2 (site 2) (245 cm 3 g -1 ) for CO 2 exceeded that of MOF-74-Mg (228 cm 3 g -1 ) at 273 K and 1 bar and that for HCHO can reach 0.41 g g -1 , which is almost twice that of 438-MOF and nearly 45 times of that in active carbon. Moreover, for natural gas mixtures, the decarburization and desulfurization abilities of CPM-200-In/Mg-NH 2 (site 2) have exceeded those of the MOF-74 series, while for post-combustion flue gas mixtures, the desulfurization ability of CPM-200-In/Mg-NH 2 (site 2) is still

An N-Terminal ER Export Signal Facilitates the Plasma Membrane Targeting of HCN1 Channels in Photoreceptors.

Science.gov (United States)

Pan, Yuan; Laird, Joseph G; Yamaguchi, David M; Baker, Sheila A

2015-06-01

Hyperpolarization-activated cyclic nucleotide-gated 1 (HCN1) channels are widely expressed in the retina. In photoreceptors, the hyperpolarization-activated current (Ih) carried by HCN1 is important for shaping the light response. It has been shown in multiple systems that trafficking HCN1 channels to specific compartments is key to their function. The localization of HCN1 in photoreceptors is concentrated in the plasma membrane of the inner segment (IS). The mechanisms controlling this localization are not understood. We previously identified a di-arginine endoplasmic reticulum (ER) retention motif that negatively regulates the surface targeting of HCN1. In this study, we sought to identify a forward trafficking signal that could counter the function of the ER retention signal. We studied trafficking of HCN1 and several mutants by imaging their subcellular localization in transgenic X. laevis photoreceptors. Velocity sedimentation was used to assay the assembly state of HCN1 channels. We found the HCN1 N-terminus can redirect a membrane reporter from outer segments (OS) to the plasma membrane of the IS. The sequence necessary for this behavior was mapped to a 20 amino acid region containing a leucine-based ER export motif. The ER export signal is necessary for forward trafficking but not channel oligomerization. Moreover, this ER export signal alone counteracted the di-arginine ER retention signal. We identified an ER export signal in HCN1 that functions with the ER retention signal to maintain equilibrium of HCN1 between the endomembrane system and the plasma membrane.

Study of NH3 Line Intensities in the THz and Far-IR Region

Science.gov (United States)

Yu, Shanshan

Ammonia (NH3) exists in the interstellar medium, late-type stars and giant planets of our solar system. Its temperature and abundance profiles in these environments, which are derived with its line parameters as fixed input , are commonly used to provide constraints on retrieving minor species. Therefore NH3 line parameters are essential for interpreting astrophysical and planetary spectra from Herschel, SOFIA, ALMA and JWST. However, our work under a predecessor grant with the APRA program revealed significant deficiencies in NH3 intensities in the terahertz and FIR region, including some weak Delta(K)=3 forbidden transitions predicted to be 100 times stronger. The Delta(K)=3 transitions are the ones connecting levels with different K values and therefore the only way other than collisions and l-doubled states to excite NH3 to K>0 levels. Their intensities have to be corrected to explain the observed high K excitation, such as the detection of NH3 (J,K) = (1,1), (2,2)&(14,14) and (18,18) transitions toward the galactic center star forming region Sgr B2, and to provide insights into the radiative- transfer vs. collision excitation mechanics of interstellar NH3. This proposal will remedy the serious deficiencies in the current databases involving NH3 line parameters in the terahertz and FIR region. We will target transitions with intensities greater than 10^{-23} cm-1/ (molecule/cm2) at 296 K, which will be among new astrophysical detections made by SOFIA, ALMA and JWST, and are 1000 times weaker than the strongest ground state transitions. We will retrieve new positions and intensities from existing laboratory spectra, use them to evaluate the current databases and ab initio calculations, and repair the line positions and intensities by replacing poorly calculated values with our new measurements. The proposed research will result in (1) a validated linelist containing the positions, intensities and lower state energies for the very important Delta(K)=3 NH3 FIR

Thermal properties and phase transition in the fluoride, (NH4)3SnF7

International Nuclear Information System (INIS)

Kartashev, A.V.; Gorev, M.V.; Bogdanov, E.V.; Flerov, I.N.; Laptash, N.M.

2016-01-01

Calorimetric, dilatometric and differential thermal analysis studies were performed on (NH 4 ) 3 SnF 7 for a wide range of temperatures and pressures. Large entropy (δS 0 =22 J/mol K) and elastic deformation (δ(ΔV/V) 0 =0.89%) jumps have proven that the Pa-3↔Pm-3m phase transition is a strong first order structural transformation. A total entropy change of ΔS 0 =32.5 J/mol K is characteristic for the order–disorder phase transition, and is equal to the sum of entropy changes in the related material, (NH 4 ) 3 TiF 7 , undergoing transformation between the two cubic phases through the intermediate phases. Hydrostatic pressure decreases the stability of the high temperature Pm-3m phase in (NH 4 ) 3 SnF 7 , contrary to (NH 4 ) 3 TiF 7 , characterised by a negative baric coefficient. The effect of experimental conditions on the chemical stability of (NH 4 ) 3 SnF 7 was observed. - Graphical abstract: Strong first order structural transformation Pa-3↔Pm-3m in (NH 4 ) 3 SnF 7 is associated with very large total entropy change of ΔS 0 =32.5 J/mol K characteristic for the ordering processes and equal to the sum of entropy changes in the related (NH 4 ) 3 TiF 7 undergoing transformation between the same two cubic phases through the intermediate phases. - Highlights: • (NH 4 ) 3 SnF 7 undergoes strong first order Pa-3↔Pm-3m phase transition. • Anomalous behaviour of ΔC p and ΔV/V exists far below phase transition temperature. • Structural distortions are accompanied by huge total entropy change ΔS≈Rln50. • High pressure strongly increases the stability of Pa-3 phase in (NH 4 ) 3 SnF 7 . • Entropy of the Pa-3↔Pm-3m phase transition does not depend on pressure.

The phytotoxic effects of present NH3 immissions

International Nuclear Information System (INIS)

Adaros, G.; Daemmgen, U.

1994-01-01

The phytotoxic effects of NH 3 have been known since the end of the previous century. The significance of ammonia as harmful substance or stressor even in ambient concentrations has been only realized and investigated during the last decades. This volume is aimed at accounting the effects produced by ambient doses of NH 3 . The entities relevant for the description of potential dose response relationships are discussed. The major source of potential dose response relationships are discussed. The major source of atmospheric pollution of ammonia and ammonium is intensive agriculture, in particular intensive cattle production. However, sources and transmission processes are not dealt with in this paper. Potential pathways of ammonia into the plants and the respective reaction mechanisms are discussed in detail. (orig./MG) [de

UV photoprocessing of NH3 ice: photon-induced desorption mechanisms

Science.gov (United States)

Martín-Doménech, R.; Cruz-Díaz, G. A.; Muñoz Caro, G. M.

2018-01-01

Ice mantles detected on the surface of dust grains towards the coldest regions of the interstellar medium can be photoprocessed by the secondary ultraviolet (UV) field present in dense cloud interiors. In this work, we present UV-irradiation experiments under astrophysically relevant conditions of pure NH3 ice samples in an ultra-high vacuum chamber where solid samples were deposited on to a substrate at 8 K. The ice analogues were subsequently photoprocessed with a microwave-discharged hydrogen-flow lamp. The induced radiation and photochemistry led to the production of H2, N2 and N2H4. In addition, photodesorption to the gas phase of the original ice component, NH3, and two of the three detected photoproducts, H2 and N2, was observed thanks to a quadrupole mass spectrometer (QMS). Calibration of the QMS allowed quantification of the photodesorption yields, leading to Ypd (NH3) = 2.1^{+2.1}_{-1.0} × 10-3 molecules/{incident photon}, which remained constant during the whole experiments, while photodesorption of H2 and N2 increased with fluence, pointing towards an indirect photodesorption mechanism involving energy transfer for these species. Photodesorption yield of N2 molecules after a fluence equivalent to that experienced by ice mantles in space was similar to that of the NH3 molecules (Ypd (N2) = 1.7^{+1.7}_{-0.9} × 10-3 molecules/{incident photon}).

An evaluation of IASI-NH3 with ground-based Fourier transform infrared spectroscopy measurements

Directory of Open Access Journals (Sweden)

E. Dammers

2016-08-01

Full Text Available Global distributions of atmospheric ammonia (NH3 measured with satellite instruments such as the Infrared Atmospheric Sounding Interferometer (IASI contain valuable information on NH3 concentrations and variability in regions not yet covered by ground-based instruments. Due to their large spatial coverage and (bi-daily overpasses, the satellite observations have the potential to increase our knowledge of the distribution of NH3 emissions and associated seasonal cycles. However the observations remain poorly validated, with only a handful of available studies often using only surface measurements without any vertical information. In this study, we present the first validation of the IASI-NH3 product using ground-based Fourier transform infrared spectroscopy (FTIR observations. Using a recently developed consistent retrieval strategy, NH3 concentration profiles have been retrieved using observations from nine Network for the Detection of Atmospheric Composition Change (NDACC stations around the world between 2008 and 2015. We demonstrate the importance of strict spatio-temporal collocation criteria for the comparison. Large differences in the regression results are observed for changing intervals of spatial criteria, mostly due to terrain characteristics and the short lifetime of NH3 in the atmosphere. The seasonal variations of both datasets are consistent for most sites. Correlations are found to be high at sites in areas with considerable NH3 levels, whereas correlations are lower at sites with low atmospheric NH3 levels close to the detection limit of the IASI instrument. A combination of the observations from all sites (Nobs = 547 give a mean relative difference of −32.4 ± (56.3 %, a correlation r of 0.8 with a slope of 0.73. These results give an improved estimate of the IASI-NH3 product performance compared to the previous upper-bound estimates (−50 to +100 %.

Nitrogen metabolism, acid-base regulation, and molecular responses to ammonia and acid infusions in the spiny dogfish shark (Squalus acanthias).

Science.gov (United States)

Nawata, C Michele; Walsh, Patrick J; Wood, Chris M

2015-07-01

Although they are ureotelic, marine elasmobranchs express Rh glycoproteins, putative ammonia channels. To address questions raised by a recent study on high environmental ammonia (HEA) exposure, dogfish were intravascularly infused for 24 h at 3 ml kg(-1) h(-1) with isosmotic NaCl (500 mmol l(-1), control), NH4HCO3 (500 mmol l(-1)), NH4Cl (500 mmol l(-1)), or HCl (as 125 mmol l(-1) HCl + 375 mmol l(-1) NaCl). While NaCl had no effect on arterial acid-base status, NH4HCO3 caused mild alkalosis, NH4Cl caused strong acidosis, and HCl caused lesser acidosis, all predominantly metabolic in nature. Total plasma ammonia (T(Amm)) and excretion rates of ammonia (J(Amm)) and urea-N (J(Urea-N)) were unaffected by NaCl or HCl. However, despite equal loading rates, plasma T(Amm) increased to a greater extent with NH4Cl, while J(Amm) increased to a greater extent with NH4HCO3 due to much greater increases in blood-to-water PNH3 gradients. As with HEA, both treatments caused large (90%) elevations of J(Urea-N), indicating that urea-N synthesis by the ornithine-urea cycle (OUC) is driven primarily by ammonia rather than HCO3(-). Branchial mRNA expressions of Rhbg and Rhp2 were unaffected by NH4HCO3 or NH4Cl, but v-type H(+)-ATPase was down-regulated by both treatments, and Rhbg and Na(+)/H(+) exchanger NHE2 were up-regulated by HCl. In the kidney, Rhbg was unresponsive to all treatments, but Rhp2 was up-regulated by HCl, and the urea transporter UT was up-regulated by HCl and NH4Cl. These responses are discussed in the context of current ideas about branchial, renal, and OUC function in this nitrogen-limited predator.

Effects of two litter amendments on air NH3 levels in broiler closed-houses

Science.gov (United States)

Atapattu, N. S. B. M; Lakmal, L. G. E.; Perera, P. W. A.

2017-01-01

Objective High NH3 emissions from poultry houses are reported to have negative impacts on health, welfare and safety of birds and humans, and on the environment. Objective of the present study was to determine the effects of two litter amendments on the NH3 levels in broiler closed houses under hot-humid conditions. Methods Giving a completely randomize design, nine closed houses, each housed 32,500 birds on paddy husk litter, were randomly allocated into two treatment (Mizuho; a bacterial culture mix and Rydall OE; an enzymatic biocatalyst) and control groups. NH3 levels were determined thrice a day (0600, 1200, and 1800 h), at three heights from the litter surface (30, 90, and 150 cm), at 20 predetermined locations of a house, from day 1 to 41. Results Rydall significantly reduced the NH3 level compared to control and Mizuho. NH3 levels at 30 cm were significantly higher than that of 90 and 150 cm. The NH3 levels at 30 cm height were higher than 25 ppm level from day 9, 11, and 13 in Mizuho, control, and Rydall groups, respectively to day 41. NH3 levels at 150 cm height were higher than maximum threshold limit of 50 ppm for human exposure from day 12, 14, and 15 in Mizuho, control, and Rydall groups, respectively to day 33. Being significantly different among each other, the NH3 level was highest and lowest at 0600 and 1800 h. Litter amendments had no significant effects on growth performance. Rydall significantly increased the litter N content on day 24. Conclusion It was concluded that the NH3 levels of closed house broiler production facilities under tropical condition are so high that both birds and workers are exposed to above recommended levels during many days of the growing period. Compared to microbial culture, the enzymatic biocatalyst was found to be more effective in reducing NH3 level. PMID:28423888

Lead-free Perovskite Materials (NH4 )3 Sb2 Ix Br9-x.

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Zuo, Chuantian; Ding, Liming

2017-06-01

A family of perovskite light absorbers (NH 4 ) 3 Sb 2 I x Br 9-x (0≤x≤9) was prepared. These materials show good solubility in ethanol, a low-cost, hypotoxic, and environmentally friendly solvent. The light absorption of (NH 4 ) 3 Sb 2 I x Br 9-x films can be tuned by adjusting I and Br content. The absorption onset for (NH 4 ) 3 Sb 2 I x Br 9-x films changes from 558 nm to 453 nm as x changes from 9 to 0. (NH 4 ) 3 Sb 2 I 9 single crystals were prepared, exhibiting a hole mobility of 4.8 cm 2  V -1  s -1 and an electron mobility of 12.3 cm 2  V -1  s -1 . (NH 4 ) 3 Sb 2 I 9 solar cells gave an open-circuit voltage of 1.03 V and a power conversion efficiency of 0.51 %. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Distribution and function of HCN channels in the apical dendritic tuft of neocortical pyramidal neurons.

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Harnett, Mark T; Magee, Jeffrey C; Williams, Stephen R

2015-01-21

The apical tuft is the most remote area of the dendritic tree of neocortical pyramidal neurons. Despite its distal location, the apical dendritic tuft of layer 5 pyramidal neurons receives substantial excitatory synaptic drive and actively processes corticocortical input during behavior. The properties of the voltage-activated ion channels that regulate synaptic integration in tuft dendrites have, however, not been thoroughly investigated. Here, we use electrophysiological and optical approaches to examine the subcellular distribution and function of hyperpolarization-activated cyclic nucleotide-gated nonselective cation (HCN) channels in rat layer 5B pyramidal neurons. Outside-out patch recordings demonstrated that the amplitude and properties of ensemble HCN channel activity were uniform in patches excised from distal apical dendritic trunk and tuft sites. Simultaneous apical dendritic tuft and trunk whole-cell current-clamp recordings revealed that the pharmacological blockade of HCN channels decreased voltage compartmentalization and enhanced the generation and spread of apical dendritic tuft and trunk regenerative activity. Furthermore, multisite two-photon glutamate uncaging demonstrated that HCN channels control the amplitude and duration of synaptically evoked regenerative activity in the distal apical dendritic tuft. In contrast, at proximal apical dendritic trunk and somatic recording sites, the blockade of HCN channels decreased excitability. Dynamic-clamp experiments revealed that these compartment-specific actions of HCN channels were heavily influenced by the local and distributed impact of the high density of HCN channels in the distal apical dendritic arbor. The properties and subcellular distribution pattern of HCN channels are therefore tuned to regulate the interaction between integration compartments in layer 5B pyramidal neurons. Copyright © 2015 the authors 0270-6474/15/351024-14$15.00/0.

Surface study of platinum decorated graphene towards adsorption of NH_3 and CH_4

International Nuclear Information System (INIS)

Rad, Ali Shokuhi; Pazoki, Hossein; Mohseni, Soheil; Zareyee, Daryoush; Peyravi, Majid

2016-01-01

To distinguish the potential of graphene sensors, there is a need to recognize the interaction between graphene sheet and adsorbing molecules. We used density functional theory (DFT) calculations to study the properties of pristine as well as Pt-decorated graphene sheet upon adsorption of NH_3 and CH_4 on its surface to exploit its potential to be as gas sensors for them. We found much higher adsorption, higher charge transfer, lower intermolecular distance, and higher orbital hybridizing upon adsorption of NH_3 and CH_4 gas molecules on Pt-decorated graphene compared to pristine graphene. Also our calculations reveal that the adsorption energies on Pt-decorated graphene sheet are in order of NH_3 >CH_4 which could be corresponded to the order of their sensitivity on this modified surface. We used orbital analysis including density of states as well as frontier molecular orbital study for all analyte-surface systems to more understanding the kind of interaction (physisorption or chemisorption). Consequently, the Pt-decorated graphene can transform the existence of NH_3 and CH_4 molecules into electrical signal and it may be potentially used as an ideal sensor for detection of NH_3 and CH_4 in ambient situation. - Highlights: • Pt-decorated graphene was investigated as an adsorbent for NH_3 and CH_4. • Much higher adsorption of NH_3 and CH_4 on Pt-decorated graphene than pristine graphene. • Higher adsorption of NH_3 compared to CH_4 on Pt-decorated graphene. • Pt influences the electronic structure of graphene.

X-ray and NQR studies of bromoindate(III) complexes. [C2H5NH3]4InBr7, [C(NH2)3]3InBr6, and [H3NCH2C(CH3)2CH2NH3]InBr5

International Nuclear Information System (INIS)

Iwakiri, Takeharu; Ishihara, Hideta; Terao, Hiromitsu; Lork, Enno; Gesing, Thorsten M.

2017-01-01

The crystal structures of [C 2 H 5 NH 3 ] 4 InBr 7 (1), [C(NH 2 ) 3 ] 3 InBr 6 (2), and [H 3 NCH 2 C(CH 3 ) 2 CH 2 NH 3 ]InBr 5 (3) were determined at 100(2) K: monoclinic, P2 1 /n, a=1061.94(3), b=1186.40(4), c=2007.88(7) pm, β= 104.575(1) , Z=4 for 1; monoclinic, C2/c, a=3128.81(12), b=878.42(3), c=2816.50(10) pm, β=92.1320(10) , Z=16 for 2; orthorhombic, P2 1 2 1 2 1 , a=1250.33(5), b=1391.46(6), c=2503.22(9) pm, Z=4 for 3. The structure of 1 contains an isolated octahedral [InBr 6 ] 3- ion and a Br - ion. The structure of 2 contains three different isolated octahedral [InBr 6 ] 3- ions. The structure of 3 has a corner-shared double-octahedral [In 2 Br 11 ] 5- ion and an isolated tetrahedral [InBr 4 ] - ion. The 81 Br nuclear quadrupole resonance (NQR) lines of the terminal Br atoms of the compounds are widely spread in frequency, and some of them show unusual positive temperature dependence. These observations manifest the N-H..Br-In hydrogen bond networks developed between the cations and anions to stabilize the crystal structures. The 81 Br NQR and differential thermal analysis (DTA) measurements have revealed the occurrence of unique phase transitions in 1 and 3. When the bond angles were estimated from the electric field gradient (EFG) directions calculated by the molecular orbital (MO) methods, accurate values were obtained for [InBr 6 ] 3- of 1 and for [In 2 Br 11 ] 5- and [InBr 4 ] - of 3, except for several exceptions in those for the latter two ions. On the other hand, the calculations of 81 Br NQR frequencies have produced up to 1.4 times higher values than the observed ones.

Rotational Spectroscopy of the NH{sub 3}–H{sub 2} Molecular Complex

Energy Technology Data Exchange (ETDEWEB)

Surin, L. A.; Schlemmer, S. [I. Physikalisches Institut, University of Cologne, Zülpicher Str. 77, D-50937 Cologne (Germany); Tarabukin, I. V. [Institute of Spectroscopy of Russian Academy of Sciences, Fizicheskaya Str. 5, 108840 Troitsk, Moscow, Russia (Russian Federation); Breier, A. A.; Giesen, T. F. [Institute of Physics, University of Kassel, Heinrich-Plett-Str. 40, D-34132 Kassel (Germany); McCarthy, M. C. [Harvard-Smithsonian Center for Astrophysics, Cambridge, MA 02138 (United States); Avoird, A. van der, E-mail: surin@ph1.uni-koeln.de, E-mail: A.vanderAvoird@theochem.ru.nl [Theoretical Chemistry, Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen (Netherlands)

2017-03-20

We report the first high resolution spectroscopic study of the NH{sub 3}–H{sub 2} van der Waals molecular complex. Three different experimental techniques, a molecular beam Fourier transform microwave spectrometer, a millimeter-wave intracavity jet OROTRON spectrometer, and a submillimeter-wave jet spectrometer with multipass cell, were used to detect pure rotational transitions of NH{sub 3}–H{sub 2} in the wide frequency range from 39 to 230 GHz. Two nuclear spin species, ( o )-NH{sub 3}–( o )-H{sub 2} and ( p )-NH{sub 3}–( o )-H{sub 2}, have been assigned as carriers of the observed lines on the basis of accompanying rovibrational calculations performed using the ab initio intermolecular potential energy surface (PES) of Maret et al. The experimental spectra were compared with the theoretical bound state results, thus providing a critical test of the quality of the NH{sub 3}–H{sub 2} PES, which is a key issue for reliable computations of the collisional excitation and de-excitation of ammonia in the dense interstellar medium.

Selective Catalytic Reduction of NO with NH3 Over V-MCM-41 Catalyst.

Science.gov (United States)

Kwon, Woo Hyun; Park, Sung Hoon; Kim, Ji Man; Park, Su Bin; Jung, Sang-Chul; Kim, Sang Chai; Jeon, Jong-Ki; Park, Young-Kwon

2016-02-01

V-MCM-41, a mesoporous catalyst doped with V2O5, was applied for the first time to the removal of atmospheric NO. The quantity of V2O5 added was 10 wt% and 30 wt%. The characteristics of the synthesized catalysts were examined using XRD, N2 soprtion, and NH3-TPD. With increasing quantity of V2O5 added, specific surface area decreased and pore size increased. When the quantity of V2O5 was 10 wt%, the MCM-41 structure was retained, whereas considerable collapse of mesoporous structure was observed when 30 wt% V2O5 was added. The examination of acid characteristics using NH3-TPD showed that 30 wt% V-MCM-41 had the higher NH3 adsorption ability, implying that it would exhibit high activity for NH3 SCR reaction. In the NO removal experiments, 30 wt% V-MCM-41 showed much higher NO removal efficiency than 10 wt% V-MCM-41, which was attributed to its high NH3 adsorption ability.

CH3NH3PbI3 grain growth and interfacial properties in meso-structured perovskite solar cells fabricated by two-step deposition

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Yao, Zhibo; Wang, Wenli; Shen, Heping; Zhang, Ye; Luo, Qiang; Yin, Xuewen; Dai, Xuezeng; Li, Jianbao; Lin, Hong

2017-12-01

Although the two-step deposition (TSD) method is widely adopted for the high performance perovskite solar cells (PSCs), the CH3NH3PbI3 perovskite crystal growth mechanism during the TSD process and the photo-generated charge recombination dynamics in the mesoporous-TiO2 (mp-TiO2)/CH3NH3PbI3/hole transporting material (HTM) system remains unexploited. Herein, we modified the concentration of PbI2 (C(PbI2)) solution to control the perovskite crystal properties, and observed an abnormal CH3NH3PbI3 grain growth phenomenon atop mesoporous TiO2 film. To illustrate this abnormal grain growth mechanism, we propose that a grain ripening process is taking place during the transformation from PbI2 to CH3NH3PbI3, and discuss the PbI2 nuclei morphology, perovskite grain growing stage, as well as Pb:I atomic ratio difference among CH3NH3PbI3 grains with different morphology. These C(PbI2)-dependent perovskite morphologies resulted in varied charge carrier transfer properties throughout the mp-TiO2/CH3NH3PbI3/HTM hybrid, as illustrated by photoluminescence measurement. Furthermore, the effect of CH3NH3PbI3 morphology on light absorption and interfacial properties is investigated and correlated with the photovoltaic performance of PSCs.

Chromatographic methods for the simultaneous determination of binary mixture of Saxagliptin HCl and Metformin HCl

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Hanan A. Merey

2017-12-01

Full Text Available Two chromatographic methods were suggested for the simultaneous determination of a binary mixture containing Saxagliptin HCl (SAG and Metformin HCl (MET. First method was RP-HPLC method. Chromatographic separation was done on Kinetex™ column–C18 (4.6 × 150 mm, 2.6 µm using mobile phase consisted of acetonitrile:phosphate buffer pH = 4.5 ± 0.1 adjusted with orthophosphoric acid (13:87, v/v. Isocratic elution at a flow rate 1.5 mL/min and UV detection at 220.0 nm was performed. Second method was spectro-densitometric method. Chromatographic separation was done on precoated silica gel aluminium plates 60 F254 as a stationary phase and developing system consisting of chloroform:methanol:formic acid (80:20:0.3, by volume. The density of the separated bands was measured by UV detector at 210.0 nm. The proposed methods were validated as per the ICH guidelines parameters like Linearity, precision, accuracy, selectivity, limit of detection and limit of quantitation. Statistical comparison was done between the obtained results and those obtained by the reported methods, showing no significant difference with respect to accuracy and precision. Keywords: Saxagliptin HCl, Metformin HCl, RP-HPLC, TLC

Dissociation of NH3 and NH2D by high power CO2 laser radiation

International Nuclear Information System (INIS)

Jacobs, R.R.

1976-08-01

Multiquantum dissociation of polyatomics using intense CO 2 lasers resulting in isotopic enrichment has been demonstrated for several molecules. In this presentation, the possibility of selective dissociation of NH 3 and NH 2 D by high power laser radiation at 10 μm will be considered. Relevant work performed at the Lawrence Livermore Laboratory and elsewhere will be summarized. In this review, attention will be given to four distinct mechanisms that can play varying degrees of importance in such investigations. Discussion will deal with the usefulness of two-resonant-frequency molecular excitation, the role of buffer gases, and the need to monitor the yields into the ground and excited electronic states of the dissociated fragments

Interfacial electronic structures revealed at the rubrene/CH3NH3PbI3 interface.

Science.gov (United States)

Ji, Gengwu; Zheng, Guanhaojie; Zhao, Bin; Song, Fei; Zhang, Xiaonan; Shen, Kongchao; Yang, Yingguo; Xiong, Yimin; Gao, Xingyu; Cao, Liang; Qi, Dong-Chen

2017-03-01

The electronic structures of rubrene films deposited on CH 3 NH 3 PbI 3 perovskite have been investigated using in situ ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). It was found that rubrene molecules interacted weakly with the perovskite substrate. Due to charge redistribution at their interface, a downward 'band bending'-like energy shift of ∼0.3 eV and an upward band bending of ∼0.1 eV were identified at the upper rubrene side and the CH 3 NH 3 PbI 3 substrate side, respectively. After the energy level alignment was established at the rubrene/CH 3 NH 3 PbI 3 interface, its highest occupied molecular orbital (HOMO)-valence band maximum (VBM) offset was found to be as low as ∼0.1 eV favoring the hole extraction with its lowest unoccupied molecular orbital (LUMO)-conduction band minimum (CBM) offset as large as ∼1.4 eV effectively blocking the undesired electron transfer from perovskite to rubrene. As a demonstration, simple inverted planar solar cell devices incorporating rubrene and rubrene/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole transport layers (HTLs) were fabricated in this work and yielded a champion power conversion efficiency of 8.76% and 13.52%, respectively. Thus, the present work suggests that a rubrene thin film could serve as a promising hole transport layer for efficient perovskite-based solar cells.

Interfacial Charge-Carrier Trapping in CH3NH3PbI3-Based Heterolayered Structures Revealed by Time-Resolved Photoluminescence Spectroscopy.

Science.gov (United States)

Yamada, Yasuhiro; Yamada, Takumi; Shimazaki, Ai; Wakamiya, Atsushi; Kanemitsu, Yoshihiko

2016-06-02

The fast-decaying component of photoluminescence (PL) under very weak pulse photoexcitation is dominated by the rapid relaxation of the photoexcited carriers into a small number of carrier-trapping defect states. Here, we report the subnanosecond decay of the PL under excitation weaker than 1 nJ/cm(2) both in CH3NH3PbI3-based heterostructures and bare thin films. The trap-site density at the interface was evaluated on the basis of the fluence-dependent PL decay profiles. It was found that high-density defects determining the PL decay dynamics are formed near the interface between CH3NH3PbI3 and the hole-transporting Spiro-OMeTAD but not at the CH3NH3PbI3/TiO2 interface and the interior regions of CH3NH3PbI3 films. This finding can aid the fabrication of high-quality heterointerfaces, which are required improving the photoconversion efficiency of perovskite-based solar cells.

Unconventional hydrogen bonding to organic ions in the gas phase: Stepwise association of hydrogen cyanide with the pyridine and pyrimidine radical cations and protonated pyridine

Energy Technology Data Exchange (ETDEWEB)

Hamid, Ahmed M.; El-Shall, M. Samy, E-mail: mselshal@vcu.edu [Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284 (United States); Hilal, Rifaat; Elroby, Shaaban; Aziz, Saadullah G. [Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 21589 (Saudi Arabia)

2014-08-07

Equilibrium thermochemical measurements using the ion mobility drift cell technique have been utilized to investigate the binding energies and entropy changes for the stepwise association of HCN molecules with the pyridine and pyrimidine radical cations forming the C{sub 5}H{sub 5}N{sup +·}(HCN){sub n} and C{sub 4}H{sub 4}N{sub 2}{sup +·}(HCN){sub n} clusters, respectively, with n = 1–4. For comparison, the binding of 1–4 HCN molecules to the protonated pyridine C{sub 5}H{sub 5}NH{sup +}(HCN){sub n} has also been investigated. The binding energies of HCN to the pyridine and pyrimidine radical cations are nearly equal (11.4 and 12.0 kcal/mol, respectively) but weaker than the HCN binding to the protonated pyridine (14.0 kcal/mol). The pyridine and pyrimidine radical cations form unconventional carbon-based ionic hydrogen bonds with HCN (CH{sup δ+}⋯NCH). Protonated pyridine forms a stronger ionic hydrogen bond with HCN (NH{sup +}⋯NCH) which can be extended to a linear chain with the clustering of additional HCN molecules (NH{sup +}⋯NCH··NCH⋯NCH) leading to a rapid decrease in the bond strength as the length of the chain increases. The lowest energy structures of the pyridine and pyrimidine radical cation clusters containing 3-4 HCN molecules show a strong tendency for the internal solvation of the radical cation by the HCN molecules where bifurcated structures involving multiple hydrogen bonding sites with the ring hydrogen atoms are formed. The unconventional H-bonds (CH{sup δ+}⋯NCH) formed between the pyridine or the pyrimidine radical cations and HCN molecules (11–12 kcal/mol) are stronger than the similar (CH{sup δ+}⋯NCH) bonds formed between the benzene radical cation and HCN molecules (9 kcal/mol) indicating that the CH{sup δ+} centers in the pyridine and pyrimidine radical cations have more effective charges than in the benzene radical cation.

Reduction of RuVI≡N to RuIII-NH3 by Cysteine in Aqueous Solution.

Science.gov (United States)

Wang, Qian; Man, Wai-Lun; Lam, William W Y; Yiu, Shek-Man; Tse, Man-Kit; Lau, Tai-Chu

2018-05-21

The reduction of metal nitride to ammonia is a key step in biological and chemical nitrogen fixation. We report herein the facile reduction of a ruthenium(VI) nitrido complex [(L)Ru VI (N)(OH 2 )] + (1, L = N, N'-bis(salicylidene)- o-cyclohexyldiamine dianion) to [(L)Ru III (NH 3 )(OH 2 )] + by l-cysteine (Cys), an ubiquitous biological reductant, in aqueous solution. At pH 1.0-5.3, the reaction has the following stoichiometry: [(L)Ru VI (N)(OH 2 )] + + 3HSCH 2 CH(NH 3 )CO 2 → [(L)Ru III (NH 3 )(OH 2 )] + + 1.5(SCH 2 CH(NH 3 )CO 2 ) 2 . Kinetic studies show that at pH 1 the reaction consists of two phases, while at pH 5 there are three distinct phases. For all phases the rate law is rate = k 2 [1][Cys]. Studies on the effects of acidity indicate that both HSCH 2 CH(NH 3 + )CO 2 - and - SCH 2 CH(NH 3 + )CO 2 - are kinetically active species. At pH 1, the reaction is proposed to go through [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a), [(L)Ru III (NH 2 SCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (3), and [(L)Ru IV (NH 2 )(OH 2 )] + (4) intermediates. On the other hand, at pH around 5, the proposed intermediates are [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 )(OH 2 )] + (2b) and [(L)Ru IV (NH 2 )(OH 2 )] + (4). The intermediate ruthenium(IV) sulfilamido species, [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a) and the final ruthenium(III) ammine species, [(L)Ru III (NH 3 )(MeOH)] + (5) (where H 2 O was replaced by MeOH) have been isolated and characterized by various spectroscopic methods.

Improvement of photovoltaic performance of the inverted planar perovskite solar cells by using CH3NH3PbI3-xBrx films with solvent annealing

Science.gov (United States)

Wang, Shan; Zhang, Weijia; Ma, Denghao; Jiang, Zhaoyi; Fan, Zhiqiang; Ma, Qiang; Xi, Yilian

2018-01-01

In this paper, the CH3NH3PbI3-xBrx films with various Br-doping contents were successfully prepared by solution processed deposition and followed by annealing process. This method simultaneously modified the morphology and composition of the CH3NH3PbI3 film. The effects of annealing treatment of CH3NH3PbI3-xBrx films under N2 and DMSO conditions on the microstructure of films and photoelectric properties of the solar cells were systematically investigated. The relationship of the component ratio of RBr/I= CH3NH3PbI3-xBrx/CH3NH3PbI3 in the resulting perovskite versus CH3NH3Br concentration also was explored. The results revealed that the CH3NH3PbI3-xBrx films annealed under DMSO exhibited increased grain sizes, enhanced crystallinity, enlarged bandgap and reduced defect density compared with that of the N2 annealing. It also was found that the RBr/I linearly increased in the resulting perovskite with the increased of CH3NH3Br concentration in the methylammonium halide mixture solutions. Furthermore, the photovoltaic performances of devices fabricated using DMSO precursor solvent were worse than that of DMF under N2 annealing atmosphere. When CH3NH3Br concentration was 7.5 mg ml-1, the planar perovskite solar cell based on CH3NH3PbI3-xBrx annealed under DMSO showed the best efficiency of 13.7%.

Room temperature three-photon pumped CH3NH3PbBr3 perovskite microlasers

Science.gov (United States)

Gao, Yisheng; Wang, Shuai; Huang, Can; Yi, Ningbo; Wang, Kaiyang; Xiao, Shumin; Song, Qinghai

2017-03-01

Hybrid lead halide perovskites have made great strides in next-generation light-harvesting and light emitting devices. Recently, they have also shown great potentials in nonlinear optical materials. Two-photon absorption and two-photon light emission have been thoroughly studied in past two years. However, the three-photon processes are rarely explored, especially for the laser emissions. Here we synthesized high quality CH3NH3PbBr3 perovskite microstructures with solution processed precipitation method and studied their optical properties. When the microstructures are pumped with intense 1240 nm lasers, we have observed clear optical limit effect and the band-to-band photoluminescence at 540 nm. By increasing the pumping density, whispering-gallery-mode based microlasers have been achieved from CH3NH3PbBr3 perovskite microplate and microrod for the first time. This work demonstrates the potentials of hybrid lead halide perovskites in nonlinear photonic devices.

Release of nitrogen precursors from coal and biomass residues in a bubbling fluidized bed

Energy Technology Data Exchange (ETDEWEB)

P. Abelha; I. Gulyurtlu; I. Cabrita [Instituto Nacional de Engenharia, Lisbon (Portugal)

2008-01-15

This work was undertaken with the aim of quantifying the relative amounts of NH{sub 3} and HCN released from different residues during their devolatilization under fluidized bed conditions. The results were compared with data collected for bituminous coals of different origin. The relation between amounts of HCN and NH{sub 3} released and the levels of NOX and N{sub 2}O formed during cocombustion was also addressed. The partitioning of nitrogen between volatiles and char was also quantified. The pyrolysis studies were undertaken in a small fluidized bed reactor of 80 mm of ID and 500 mm high using an inert atmosphere (N{sub 2}). The HCN and NH{sub 3} were quantified by bubbling the pyrolysis gases in absorbing solutions which were subsequently analyzed with selective electrodes. The combustion studies were carried out on a pilot installation. The fluidized bed combustor is square in cross section with each side being 300 mm long. There is secondary air supply to the freeboard at different heights to deal with high volatile fuels as almost all waste materials are. The temperatures in the bed and in the freeboard and that of the flue gases leaving the reactor were continuously monitored. The results obtained suggest that, while coal releases nitrogen mostly as HCN, residues like RDF and sewage sludge give out fuel-N in greater quantities as NH{sub 3}. Residues at fluidized bed combustion (FBC) temperatures release more than 80% of the fuel-N with the volatiles. The NH{sub 3} evolved during pyrolysis acted as a reducing agent on NOX emissions. The presence of calcium significantly reduces the emission of N{sub 2}O probably by interfering with HCN chemistry. With high amounts of residues in the fuel mixture, the relative importance of char on the nitrogen chemistry substantially decreases. By using cocombustion, it is possible to reduce fuel-N conversion to NOX and N{sub 2}O, by tuning the amounts of coal and residue in the mixture. 29 refs., 18 figs., 3 tabs.

Effects of alkali and alkaline earth metals on nitrogen release during temperature programmed pyrolysis of coal

Energy Technology Data Exchange (ETDEWEB)

Ohtsuka, Y.; Wu, Z.; Furimsky, E. [Tohoku University, Sendai (Japan). Inst. for Chemical Reaction Science

1997-11-01

The paper reports that the formation of HCN, NH{sub 3} and N{sub 2} during fixed-bed pyrolysis at 10 K min{sup -1} has been studied using coal samples after partial demineralization followed by addition of metal hydroxides from aqueous systems. Without additives, NH{sub 3} is the predominant product at {le} 700{degree}C, showing the two peaks in the formation rate profile, whereas N{sub 2} is the only product at {ge} 800{degree}C. The presence of NaOH, KOH and Ca(OH){sub 2} promotes considerable NH{sub 3} formation between 450 and 600{degree}C, but in contrast suppresses HCN formation in this region. The Ca shows the largest effect on both the promotion and suppression. It is likely that the NH{sub 3} increased by Ca addition arises partly from HCN, but mainly from secondary reactions of tar-N. These hydroxides affect N{sub 2} formation in quite different manners: the Na decreases the rate between 700 and 950{degree}C, and the K changes it less significantly than the Na, but the Ca remarkably increases the rate in a low temperature region of 550-700{degree}C. These different features are discussed in terms of solid-phase reactions of alkali metal carbonates with char-N and secondary decomposition reactions of tar-N on CaO particles. As a result, total conversion of coal-N to HCN, NH{sub 3} and N{sub 2} up to 1000{degree}C increases in the sequence of Na {lt} none {lt} K {lt} Ca. 40 refs., 10 figs., 2 tabs.

1-(Benzofuran-2-yl)-2-(3,3,3-trifluoropropyl)aminopentane HCl, 3-F-BPAP, antagonizes the enhancer effect of (-)-BPAP in the shuttle box and leaves the effect of (-)-deprenyl unchanged.

Science.gov (United States)

Knoll, Joseph; Miklya, Ildikó; Knoll, Berta; Yasusa, Takuya; Shimazu, Seiichiro; Yoneda, Fumio

2002-09-13

The subcutaneous administration of 1 mg/kg tetrabenazine, once daily for 5 days, which depletes the catecholamine stores in the brain, significantly inhibits in rats the acquisition of a two-way conditioned avoidance reflex in the shuttle box. Enhancer substances, the tryptamine-derived selective and highly potent enhancer, R-(-)-1-(benzofuran-2-yl)-2-propylaminopentane HCl [(-)-BPAP] (0.05-10 mg/kg), the beta-phenylethylamine (PEA)-derived enhancer, (-)-deprenyl (1-5 mg/kg) and the (-)-deprenyl analogue, free of MAO-B inhibitory potency, (-)-1-phenyl-2-propylaminopentane HCl [(-)-PPAP], (1-5 mg/kg), antagonize in a dose-dependent manner the inhibition of learning caused by tetrabenazine. 1-(Benzofuran 2 yl)-2-(3,3,3-trifluoropropyl)aminopentane HCl [3 F BPAP], a newly synthetized analogue of (-)-BPAP with low specific activity, significantly antagonized the enhancer effect of (-)-BPAP but left the effect of (-)-deprenyl and (-)-PPAP unchanged. This is the first proof for a difference in the mechanism of action between a PEA-derived enhancer substance and its tryptamine-derived peer.

Tunable far infrared laser spectroscopy of van der Waals bonds: Ar-NH sub 3

Energy Technology Data Exchange (ETDEWEB)

Gwo, Dz-Hung (Lawrence Berkeley Lab., CA (USA) California Univ., Berkeley, CA (USA). Dept. of Chemistry)

1989-11-01

Hyperfine resolved vibration-rotation-tunneling spectra of Ar--NH{sub 3} and (NH{sub 3}){sub 2}, generated in a planar supersonic jet, have been measured with the Berkeley tunable far infrared laser spectrometer. Among the seven rotationally assigned bands, one band belongs to Ar--NH{sub 3}, and the other six belong to (NH{sub 3}){sub 2}. To facilitate the intermolecular vibrational assignment for Ar--NH{sub 3}, a dynamics study aided by a permutation-inversion group theoretical treatment is performed on the rovibrational levels. The rovibrational quantum number correlation between the free internal rotor limit and the semi-rigid limit is established to provide a basic physical picture of the evolution of intermolecular vibrational component states. An anomalous vibronically allowed unique Q branch vibrational band structure is predicted to exist for a near prolate binary complex containing an inverting subunit. According to the model developed in this work, the observed band of Ar--NH{sub 3} centered at 26.470633(17) cm{sup {minus}1} can correlate only to either the fundamental dimeric stretching band for the A{sub 2} states with the NH{sub 3} inversional quantum number v{sub i} = 1, or the K{sub a} = 0 {l arrow} 0 subband of the lowest internal-rotation-inversion difference band. Although the estimated nuclear quadrupole coupling constant favors a tentative assignment in terms of the first possibility, a definitive assignment will require far infrared data and a dynamical model incorporating a potential surface.

In situ attenuated total reflection infrared (ATR-IR) study of the adsorption of NO2-, NH2OH, and NH4+ on Pd/Al2O3 and Pt/Al2O3.

NARCIS (Netherlands)

Ebbesen, S.D.; Mojet, Barbara; Lefferts, Leonardus

2008-01-01

In relation to the heterogeneous hydrogenation of nitrite, adsorption of NO2-, NH4+, and NH2OH from the aqueous phase was examined on Pt/Al2O3, Pd/Al2O3, and Al2O3. None of the investigated inorganic nitrogen compounds adsorb on alumina at conditions presented in this study. NO2-(aq) and NH4+(aq) on

Meteorite impacts on ancient oceans opened up multiple NH3 production pathways.

Science.gov (United States)

Shimamura, Kohei; Shimojo, Fuyuki; Nakano, Aiichiro; Tanaka, Shigenori

2017-05-10

A recent series of shock experiments by Nakazawa et al. starting in 2005 (e.g. [Nakazawa et al., Earth Planet. Sci. Lett., 2005, 235, 356]) suggested that meteorite impacts on ancient oceans would have yielded a considerable amount of NH 3 to the early Earth from atmospheric N 2 and oceanic H 2 O through reduction by meteoritic iron. To clarify the mechanisms, we imitated the impact events by performing multi-scale shock technique-based ab initio molecular dynamics in the framework of density functional theory in combination with multi-scale shock technique (MSST) simulations. Our previous simulations with impact energies close to that of the experiments revealed picosecond-order rapid NH 3 production during shock compression [Shimamura et al., Sci. Rep., 2016, 6, 38952]. It was also shown that the reduction of N 2 took place with an associative mechanism as seen in the catalysis of nitrogenase enzymes. In this study, we performed an MSST-AIMD simulation to investigate the production by meteorite impacts with higher energies, which are closer to the expected values on the early Earth. It was found that the amount of NH 3 produced further increased. We also found that the increased NH 3 production is due to the emergence of multiple reaction mechanisms at increased impact energies. We elucidated that the reduction of N 2 was not only attributed to the associative mechanism but also to a dissociative mechanism as seen in the Haber-Bosch process and to a mechanism through a hydrazinium ion. The emergence of these multiple production mechanisms capable of providing a large amount of NH 3 would support the suggestions from recent experiments much more strongly than was previously believed, i.e., shock-induced NH 3 production played a key role in the origin of life on Earth.

NH (X 3 summation -, v=1--3) formation and vibrational relaxation in electron-irradiated Ar/N2/H2 mixtures

International Nuclear Information System (INIS)

Dodd, J.A.; Lipson, S.J.; Flanagan, D.J.; Blumberg, W.A.M.; Person, J.C.; Green, B.D.

1991-01-01

Measurements of the dynamics of NH(X 3 summation - , v =1--3), created in electron-irradiated N 2 /H 2 and Ar/N 2 /H 2 mixtures, have been performed. Time-resolved Fourier spectroscopy was used to observe NH(v→v--1) vibrational fundamental band emission. Time-dependent populations were then determined by spectral fitting. Subsequent kinetic fitting of these populations using a single-quantum relaxation model and a power-law dependence of k v on v yielded the following NH(v =1--3) relaxation rate constants (units of 10 -14 cm 3 s -1 ): k v=1 (N 2 )=1.2±0.5, k v=2 (N 2 )=3.8±1.5, k v=3 (N 2 )=7.5±2.5; k v=1 (Ar)=0.2±0.1, k v=2 (Ar)=0.5±0.2, k v=3 (Ar)=0.8±0.3; k v=1 (H 2 )≤50, k v=2 (H 2 )≤100, k v=3 (H 2 )≤150. In addition, the N 2 /H 2 data provided a measurement of the nascent excited vibrational state distribution resulting from the reaction N( 2 D)+H 2 →NH(X,v)+H. The ratio NH(1):NH(2):NH(3) was found to be 1.0:0.97:0.81 (±0.28 in each value). Comparison of the observed nascent distribution with that of a statistical model suggests that the ratio NH(0):NH(1)=0.47. Using this derived distribution, we find the average product level left-angle v right-angle =1.6, and the fraction of the available product energy in vibration left-angle f v right-angle =0.44

Infrared aircraft measurements of stratospheric composition over Antarctica during September 1987

International Nuclear Information System (INIS)

Toon, G.C.; Farmer, C.B.; Lowes, L.L.; Schaper, P.W.; Blavier, J.F.; Norton, R.H.

1989-01-01

The Jet Propulsion Laboratory Mark IV interferometer recorded high-resolution, infrared solar spectra from the NASA DC-8 aircraft during flights over Antarctica in September 1987. The atmospheric absorption features in these spectra have been analyzed to determine the burdens of O 3 , NO, NO 2 , HNO 3 , ClNO 3 , HCl, HF, CO 2 , CH 4 , N 2 O, HCN, CO, H 2 O, CFCl 3 , and CF 2 Cl 2 . The results show a collar of high HNO 3 and ClNO 3 surrounding a core in which the burdens of these and of HCl and NO 2 are very low. Clear increases in the burdens of HF and HNO 3 were observed during the course of September in the Vortex core. HCl and NO 2 exhibited smaller, less significant increases. The burdens of the tropospheric source gases, N 2 O, CH 4 , HCN, CFCl 3 , CF 2 Cl 2 , CO, and H 2 O, were observed to be much smaller over Antarctica than at mid-latitudes. This, together with the fact that HF over Antarctica was more than double its mid-latitude value, suggests that downwelling had occurred

The role of char and tar in determining the gas-phase partitioning of nitrogen during biomass gasification

International Nuclear Information System (INIS)

Broer, Karl M.; Brown, Robert C.

2015-01-01

Highlights: • Switchgrass was gasified at an equivalence ratio of zero and 650–850 °C. • Short residence times were employed to minimize secondary reactions. • Char- and tar-bound nitrogen, NH_3, HCN, and N_2 were all significant products. • Increasing temperature leads to increased release of gaseous nitrogen compounds. • Kinetic models of gasification should include nitrogen release from char and tar. - Abstract: Gasification is an attractive option for converting biomass into fuels and chemicals. Most biomass contains significant amounts of fuel-bound nitrogen (FBN), which partially converts into ammonia (NH_3) and hydrogen cyanide (HCN) during gasification. These nitrogen compounds are problematic as they can lead to NO_X emissions or catalyst poisoning in downstream applications of syngas. FBN can convert to other products as well, including diatomic nitrogen (N_2), char-bound nitrogen (char-N), and tar-bound nitrogen (tar-N). Efforts to predict concentrations of NH_3 and HCN have been hindered by a lack of accurate, comprehensive measurements of nitrogen partitioning among gasification products. The present study gasified switchgrass under allothermal, short residence time conditions and measured NH_3, HCN, char-N, and tar-N as a function of temperature in the range of 650–850 °C with diatomic nitrogen determined by difference. It was found that a major portion of FBN was retained in the char and tar products. As temperature was increased, char and tar were consumed, releasing nitrogen as gaseous NH_3 and HCN. This increase in undesirable nitrogen compounds is contrary to the predictions of most gasification models, which overlook the presence of significant nitrogen in char and tar even if they include tar cracking and char gasification reactions. The results of this study demonstrate that gas-phase reactions alone are not sufficient to predict the fate of nitrogen during gasification. In order for modeling efforts to obtain more accurate

HERSCHEL/HIFI DISCOVERY OF HCL+ IN THE INTERSTELLAR MEDIUM

International Nuclear Information System (INIS)

De Luca, M.; Gerin, M.; Falgarone, E.; Gupta, H.; Drouin, B. J.; Pearson, J. C.; Neufeld, D.; Teyssier, D.; Lis, D. C.; Monje, R.; Phillips, T. G.; Goicoechea, J. R.; Godard, B.; Bell, T. A.; Coutens, A.

2012-01-01

The radical ion HCl + , a key intermediate in the chlorine chemistry of the interstellar gas, has been identified for the first time in the interstellar medium with the Herschel Space Observatory's Heterodyne Instrument for the Far-Infrared. The ground-state rotational transition of H 35 Cl + , 2 Π 3/2 J = 5/2-3/2, showing Λ-doubling and hyperfine structure, is detected in absorption toward the Galactic star-forming regions W31C (G10.6-0.4) and W49N. The complex interstellar absorption features are modeled by convolving in velocity space the opacity profiles of other molecular tracers toward the same sources with the fine and hyperfine structure of HCl + . This structure is derived from a combined analysis of optical data from the literature and new laboratory measurements of pure rotational transitions, reported in the accompanying Letter by Gupta et al. The models reproduce well the interstellar absorption, and the frequencies inferred from the astronomical observations are in exact agreement with those calculated using spectroscopic constants derived from the laboratory data. The detection of H 37 Cl + toward W31C, with a column density consistent with the expected 35 Cl/ 37 Cl isotopic ratio, provides additional evidence for the identification. A comparison with the chemically related molecules HCl and H 2 Cl + yields an abundance ratio of unity with both species (HCl + : H 2 Cl + : HCl ∼ 1). These observations also yield the unexpected result that HCl + accounts for 3%-5% of the gas-phase chlorine toward W49N and W31C, values several times larger than the maximum fraction (∼1%) predicted by chemical models.

Electron paramagnetic resonance of gamma irradiated (CH3)3NHClO4 and CH3NH3ClO4 single crystals

International Nuclear Information System (INIS)

Yavuz, Metin; Koeksal, Fevzi

1999-01-01

Gamma irradiation damage centers in (CH 3 ) 3 NHClO 4 and CH 3 NH 3 ClO 4 single crystals have been investigated at room temperature by the electron paramagnetic resonance (EPR) technique. It has been found that γ-irradiation produces the (CH 3 ) 3 N + radical in the first, and NH + 3 and ClO 3 radicals in the second compound. The EPR parameters of the observed radicals have been determined and discussed

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

Science.gov (United States)

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

2017-04-05

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

Improvement of CH3NH3PbI3 thin film using the additive 1,8-diiodooctane for planar heterojunction perovskite cells

Science.gov (United States)

Abdulrahman, Solh; Wang, Chunhua; Cao, Chenghao; Zhang, Chujun; Yang, Junliang; Jiang, Li

2017-10-01

The thin-film quality is critical for obtaining high-performance perovskite solar cells (PSCs). The additive 1,8-diiodooctane (DIO) was used to control the morphology and structure of CH3NH3PbI3 perovskite thin films, and planar heterojunction (PHJ) PSCs with an architecture of ITO/PEDOT: PSS/CH3NH3PbI3/PCBM/Al was fabricated. It was found that the DIO played an important role on CH3NH3PbI3 thin-film quality and the performance of PHJ-PSCs. With the optimal volume ratio of 2%, the compact and uniform high-quality CH3NH3PbI3 thin films with enhanced crystallinity and less roughness were achieved, resulting in the great improvement of power conversion efficiency (PCE) from about 4.5% to over 9.0%. The research results indicate that the additive DIO is a simple and effective method to produce high-quality perovskite thin film and accordingly develop high-performance PHJ-PSCs.

Reactions of 11C recoil atoms in the systems H2O-NH3, H2O-CH4 and NH3-CH4

International Nuclear Information System (INIS)

Nebeling, B.

1988-11-01

In this study the chemical reactions of recoil carbon 11 in the binary gas mixtures H 2 O-NH 3 , H 2 O-CH 4 and NH 3 -CH 4 in different mixing ratios as well as in solid H 2 O and in a solid H 2 O-NH 3 mixture were analyzed in dependence of the dose. The analyses were to serve e.g. the simulation of chemical processes caused by solar wind, solar radiation and cosmic radiation in the coma and core of comets. They were to give further information about the role of the most important biogeneous element carbon, i.e. carbon, in the chemical evolution of the solar system. Besides the actual high energy processes resulting in the so-called primary products, also the radiation-chemical changes of the primary products were also observed in a wide range of dosing. The generation of the energetic 11 C atoms took place according to the target composition by the nuclear reactions 14 N(p,α) 11 C, 12 C( 3 He,α) 11 C or the 16 O(p,αpn) 11 C reaction. The identification of the products marked with 11 C was carried out by means of radio gas chromatography or radio liquid chromatography (HPLC). (orig./RB) [de

Ir Spectroscopic Studies on Microsolvation of HCl by Water

Science.gov (United States)

Mani, Devendra; Schwan, Raffael; Fischer, Theo; Dey, Arghya; Kaufmann, Matin; Redlich, Britta; van der Meer, Lex; Schwaab, Gerhard; Havenith, Martina

2016-06-01

Acid dissociation reactions are at the heart of chemistry. These reactions are well understood at the macroscopic level. However, a microscopic level understanding is still in the early stages of development. Questions such as 'how many H_2O molecules are needed to dissociate one HCl molecule?' have been posed and explored both theoretically and experimentally.1-5 Most of the theoretical calculations predict that four H_2O molecules are sufficient to dissociate one HCl molecule, resulting in the formation of a solvent separated H_3O+(H_2O)3Cl- cluster.1-3 IR spectroscopy in helium nanodroplets has earlier been used to study this dissociation process.3-5 However, these studies were carried out in the region of O-H and H-Cl stretch, which is dominated by the spectral features of undissociated (HCl)m-(H_2O)n clusters. This contributed to the ambiguity in assigning the spectral features arising from the dissociated cluster.4,5 Recent predictions from Bowman's group, suggest the presence of a broad spectral feature (1300-1360 wn) for the H_3O+(H_2O)3Cl- cluster, corresponding to the umbrella motion of H_3O+ moiety.6 This region is expected to be free from the spectral features due to the undissociated clusters. In conjunction with the FELIX laboratory, we have performed experiments on the (HCl)m(H_2O)n (m=1-2, n≥4) clusters, aggregated in helium nanodroplets, in the 900-1700 wn region. Mass selective measurements on these clusters revealed the presence of a weak-broad feature which spans between 1000-1450 wn and depends on both HCl as well as H_2O concentration. Measurements are in progress for the different deuterated species. The details will be presented in the talk. References: 1) C.T. Lee et al., J. Chem. Phys., 104, 7081 (1996). 2) H. Forbert et al., J. Am. Chem. Soc., 133, 4062 (2011). 3) A. Gutberlet et al., Science, 324, 1545 (2009). 4) S. D. Flynn et al., J. Phys. Chem. Lett., 1, 2233 (2010). 5) M. Letzner et al., J. Chem. Phys., 139, 154304 (2013). 6) J. M

First principles investigation of half-metallicity and spin gapless semiconductor in CH3NH3Cr x Pb1- x I3 mixed perovskites

Science.gov (United States)

Huang, H. M.; Zhu, Z. W.; Zhang, C. K.; He, Z. D.; Luo, S. J.

2018-04-01

The structural, electronic and magnetic properties of organic-inorganic hybrid mixed perovskites CH3NH3Cr x Pb1- x I3 ( x = 0.25, 0.50, 0.75, 1.00) in cubic, tetragonal and orthorhombic phases have been investigated by first-principles calculation. The results indicate that the tetragonal CH3NH3Cr0.75Pb0.25I3 is a spin gapless semiconductor with Curie temperature of 663 K estimated using mean field approximation. All other CH3NH3Cr x Pb1- x I3 mixed perovskites are half-metallic ferromagnets together with 100% spin polarization, and their total magnetic moment are 4.00, 8.00, 12.00 and 16.00 µB per unit cell for x = 0.25, 0.50, 0.75 and 1.00, respectively. The effect of , and orientation of organic cation CH3NH3 + on the electronic properties of CH3NH3Cr0.50Pb0.50I3 was investigated. The results show that the CH3NH3 + in different orientations have a slight effect on the lattice constants, the energy gap in minority-spin states, half-metallic gap, local magnetic moment, and Curie temperature.

Orthorhombic fulleride (CH3NH2)K3C60 close to Mott-Hubbard instability: Ab initio study

Science.gov (United States)

Potočnik, Anton; Manini, Nicola; Komelj, Matej; Tosatti, Erio; Arčon, Denis

2012-08-01

We study the electronic structure and magnetic interactions in methylamine-intercalated orthorhombic alkali-doped fullerene (CH3NH2)K3C60 within the density functional theory. As in the simpler ammonia intercalated compound (NH3)K3C60, the orthorhombic crystal-field anisotropy Δ lifts the t1u triple degeneracy at the Γ point and drives the system deep into the Mott-insulating phase. However, the computed Δ and conduction electron bandwidth W cannot alone account for the abnormally low experimental Néel temperature, TN=11 K, of the methylamine compound, compared to the much higher value TN=40 K of the ammonia one. Significant interactions between CH3NH2 and C603- are responsible for the stabilization of particular fullerene-cage distortions and the ensuing low-spin S=1/2 state. These interactions also seem to affect the magnetic properties, as interfullerene exchange interactions depend on the relative orientation of deformations of neighboring C603- molecules. For the ferro-orientational order of CH3NH2-K+ groups we find an apparent reduced dimensionality in magnetic exchange interactions, which may explain the suppressed Néel temperature. The disorder in exchange interactions caused by orientational disorder of CH3NH2-K+ groups could further contribute to this suppression.

Near room temperature approaches for the preparation of air-stable and crystalline CH{sub 3}NH{sub 3}PbI{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Gujarathi, Yogini D.; Haram, Santosh K., E-mail: haram@chem.unipune.ac.in

2016-04-15

This work demonstrates an exotic role of CH{sub 2}Cl{sub 2} in a formation of stable phase of highly crystalline CH{sub 3}NH{sub 3}PbI{sub 3} perovskite, on a bulk scale. In the first method, a partially-reacted product obtained after co-grinding of precursors viz. CH{sub 3}NH{sub 3}I and PbI{sub 2}was sonicated in CH{sub 2}Cl{sub 2} to form pure phase of CH{sub 3}NH{sub 3}PbI{sub 3}. In second method, the precursors in γ-Butyrolactone were treated with CH{sub 2}Cl{sub 2} to form crystalline and phase-pure CH{sub 3}NH{sub 3}PbI{sub 3}. X-ray Diffraction analysis confirmed the formation of stable and highly crystalline tetragonal phase of CH{sub 3}NH{sub 3}PbI{sub 3} perovskite having space group I4cm. Well-defined rhombo-hexagonal dodecahedron crystals were seen in SEM and TEM images. Exceptional air stability of CH{sub 3}NH{sub 3}PbI{sub 3} so forms are attributed to adsorption of CH{sub 2}Cl{sub 2}. Optical band gaps obtained from the diffused reflectance spectra (Kubelka–Munk analysis), matched very well with the one estimated from Cyclic Voltammetry (CV). Valence band and conduction band edge positions estimated from the CV analysis are in good agreement with the one reported from UV photoelectron spectroscopy. Both the samples gave steady state fluorescence at ca. 750 nm with quantum yields in the range 15–35.5%. - Highlights: • A role of CH{sub 2}Cl{sub 2} is brought out in formation of stable CH{sub 3}NH{sub 3}PbI{sub 3} perovskite. • Cyclic voltammetry has been used to estimate the band edge positions. • Excellent fluorescence quantum yield, underlines the minimal structural defects.

Investigation of Structural and Electronic Properties of CH3NH3PbI3 Stabilized by Varying Concentrations of Poly(Methyl Methacrylate (PMMA

Directory of Open Access Journals (Sweden)

Celline Awino

2017-08-01

Full Text Available Studies have shown that perovskites have a high potential of outdoing silicon based solar cells in terms of solar energy conversion, but their rate of degradation is also high. This study reports on improvement on the stability of CH3NH3PbI3 by passivating it with polymethylmethacrylate (PMMA. Structural and electronic properties of CH3NH3PbI3 stabilized by polymethylmethacrylate (PMMA were investigated by varying concentrations of PMMA in the polymer solutions. Stability tests were performed over a period of time using modulated surface photovoltage (SPV spectroscopy, X-ray diffraction (XRD, and photoluminescence (PL measurements. The XRD patterns confirm the tetragonal structure of the deposited CH3NH3PbI3 for every concentration of PMMA. Furthermore, CH3NH3PbI3 coated with 40 mg/mL of PMMA did not show any impurity phase even after storage in air for 43 days. The Tauc gap (ETauc determined on the basis of the in-phase SPV spectra was found in the range from 1.585 to 1.62 eV for the samples stored during initial days, but shifted towards lower energies as the storage time increased. This can be proposed to be due to different chemical reactions between CH3NH3PbI3/PMMA interfaces and air. PL intensity increased with increasing concentration of PMMA except for the perovskite coated with 40 mg/mL of PMMA. PL quenching in the perovskite coated with 40 mg/mL of PMMA can be interpreted as fast electron transfer towards the substrate in the sample. This study shows that, with an optimum concentration of PMMA coating on CH3NH3PbI3, the lifetime and hence stability on electrical and structural behavior of CH3NH3PbI3 is improved.

THE VARIABILITY OF HCN IN TITAN’S UPPER ATMOSPHERE AS IMPLIED BY THE CASSINI ION-NEUTRAL MASS SPECTROMETER MEASUREMENTS

Energy Technology Data Exchange (ETDEWEB)

Cui, J.; Cao, Y.-T. [National Astronomical Observatories, Chinese Academy of Sciences, Beijing 100012 (China); Lavvas, P. P. [Groupe de Spectroscopie Moleculaire et Atmospherique, Universite de Reims, Champagne-Ardenne, CNRS UMR F-7331 (France); Koskinen, T. T. [Lunar and Planetary Laboratory, University of Arizona, Tucson, AZ 85721 (United States)

2016-07-20

HCN is an important constituent in Titan’s upper atmosphere, serving as the main coolant in the local energy budget. In this study, we derive the HCN abundance at the altitude range of 960–1400 km, combining the Ion-Neutral Mass Spectrometer data acquired during a large number of Cassini flybys with Titan. Typically, the HCN abundance declines modestly with increasing altitude and flattens to a near constant level above 1200 km. The data reveal a tendency for dayside depletion of HCN, which is clearly visible below 1000 km but weakens with increasing altitude. Despite the absence of convincing anti-correlation between HCN volume mixing ratio and neutral temperature, we argue that the variability in HCN abundance makes an important contribution to the large temperature variability observed in Titan’s upper atmosphere.

Plasma chemistry in an atmospheric pressure Ar/NH3 dielectric barrier discharge

DEFF Research Database (Denmark)

Fateev, A.; Leipold, F.; Kusano, Y.

2005-01-01

An atmospheric pressure dielectric barrier discharge (DBD) in Ar/NH3 (0.1 - 10%) mixtures with a parallel plate electrode geometry was studied. The plasma was investigated by emission and absorption spectroscopy in the UV spectral range. Discharge current and voltage were measured as well. UV...... of an atmospheric pressure Ar/NH3 DBD are H-2, N-2 and N2H4. The hydrazine (N2H4) concentration in the plasma and in the exhaust gases at various ammonia concentrations and different discharge powers was measured. Thermal N2H4 decomposition into NH2 radicals may be used for NOx reduction processes....

Characterizing the influence of highways on springtime NO2 and NH3 concentrations in regional forest monitoring plots

International Nuclear Information System (INIS)

Watmough, Shaun A.; McDonough, Andrew M.; Raney, Shanel M.

2014-01-01

Highways are major sources of nitrogen dioxide (NO 2 ) and ammonia (NH 3 ). In this study, springtime NO 2 and NH 3 concentrations were measured at 17 Ontario Forest Biomonitoring Network (OFBN) plots using passive samplers. Average springtime NO 2 concentrations were between 1.3 μg m −3 and 27 μg m −3 , and NH 3 concentrations were between 0.2 μg m −3 and 1.7 μg m −3 , although concentrations measured in May (before leaf out) were typically twice as high as values recorded in June. Average NO 2 concentrations, and to a lesser extent NH 3 , could be predicted by road density at all radii (around the plot) tested (500 m, 1000 m, 1500 m). Springtime NO 2 concentrations were predicted for a further 50 OFBN sites. Normalized plant/lichen N concentrations were positively correlated with estimated springtime NO 2 and NH 3 concentrations. Epiphytic foliose lichen richness decreased with increasing NO 2 and NH 3 , but vascular plant richness was positively related to estimated springtime NO 2 and NH 3 . - Highlights: • Springtime concentrations of NO 2 and NH 3 in Ontario forest plots vary greatly. • Concentrations of NO 2 and NH 3 can be predicted by surrounding road density. • Plant and lichen N concentrations are positively related to predicted NO 2 and NH 3 . • Epiphytic lichen richness in negatively related to NO 2 and NH 3 . • Vascular plant richness is positively related to NO 2 and NH 3 . - “Springtime concentrations of NO 2 and NH 3 at Ontario forest monitoring plots vary greatly and can be predicted by road density surrounding the plot”