Single-ion anisotropy and exchange interactions in the cyano-bridged trimers MnIII2MIII(CN)6 (MIII = Co, Cr, Fe) species incorporating [Mn(5-Brsalen)]+ units: an inelastic neutron scattering and magnetic susceptibility study

DEFF Research Database (Denmark)

Tregenna-Piggott, Philip L W; Sheptyakov, Denis; Keller, Lukas

2009-01-01

expectations based on the unquenched orbital angular momentum of the [Fe(CN)(6)](3-) anion, giving rise to an M(s) approximately +/-9/2 ground state, isolated by approximately 11.5 cm(-1) from the higher-lying levels. The reported INS and magnetic data should now serve as a benchmark against which theoretical...... interactions that define the low-lying states of the Mn-M(III)-Mn trimeric units. Despite the presence of an antiferromagnetic intertrimer interaction, the experimental evidence supports the classification of both the Cr(III) and Fe(III) compounds as single-molecule magnets. The value of 17(2) cm(-1...

On the Adjacent Strong Equitable Edge Coloring of Pn ∨ Pn, Pn ∨ Cn and Cn ∨ Cn

OpenAIRE

Liu Jun; Zhao Chuan Cheng; Yao Shu Xia; Guo Ren Zhi; Yue Qiu Ju

2016-01-01

A proper edge coloring of graph G is called equitable adjacent strong edge coloring if colored sets from every two adjacent vertices incident edge are different,and the number of edges in any two color classes differ by at most one,which the required minimum number of colors is called the adjacent strong equitable edge chromatic number. In this paper, we discuss the adjacent strong equitable edge coloring of join-graphs about Pn ∨ Pn, Pn ∨ Cn and Cn ∨ Cn.

General synthesis of (salen)ruthenium(III) complexes via N...N coupling of (salen)ruthenium(VI) nitrides.

Science.gov (United States)

Man, Wai-Lun; Kwong, Hoi-Ki; Lam, William W Y; Xiang, Jing; Wong, Tsz-Wing; Lam, Wing-Hong; Wong, Wing-Tak; Peng, Shie-Ming; Lau, Tai-Chu

2008-07-07

Reaction of [Ru (VI)(N)(L (1))(MeOH)] (+) (L (1) = N, N'-bis(salicylidene)- o-cyclohexylenediamine dianion) with excess pyridine in CH 3CN produces [Ru (III)(L (1))(py) 2] (+) and N 2. The proposed mechanism involves initial equilibrium formation of [Ru (VI)(N)(L (1))(py)] (+), which undergoes rapid N...N coupling to produce [(py)(L (1))Ru (III) N N-Ru (III)(L (1))(py)] (2+); this is followed by pyridine substituion to give the final product. This ligand-induced N...N coupling of Ru (VI)N is utilized in the preparation of a series of new ruthenium(III) salen complexes, [Ru (III)(L)(X) 2] (+/-) (L = salen ligand; X = H 2O, 1-MeIm, py, Me 2SO, PhNH 2, ( t )BuNH 2, Cl (-) or CN (-)). The structures of [Ru (III)(L (1))(NH 2Ph) 2](PF 6) ( 6), K[Ru (III)(L (1))(CN) 2] ( 9), [Ru (III)(L (2))(NCCH 3) 2][Au (I)(CN) 2] ( 11) (L (2) = N, N'-bis(salicylidene)- o-phenylenediamine dianion) and [N ( n )Bu 4][Ru (III)(L (3))Cl 2] ( 12) (L (3) = N, N'-bis(salicylidene)ethylenediamine dianion) have been determined by X-ray crystallography.

Synthesis, Structural and Antibacterial Studies of New Dithiocarbamate Complexes of Sb (III) And Bi (III)

International Nuclear Information System (INIS)

Nur Amirah Jamaluddin; Ibrahim Baba; Nazlina Ibrahim

2014-01-01

Six new dithiocarbamate complexes from three different amines, for example N-ethyl ethanol-, N-butylethyl- and N-benzylmethylamine were successfully prepared using in situ method. All complexes were characterized by elemental analysis, IR, UV-Vis, 13 C and 1 H NMR. Elemental analysis data (C, H, N and S) showed an agreement with the general formula of MCl(S 2 CNR ' R '' ) 2 , (M = Sb (III), Bi (III); R ' = ethyl, butyl and benzyl; R '' = ethanol, ethyl and methyl). The complexes had been characterized by infrared spectroscopy that showed a thioureido bands, v(C-N) in the region of 1427 - 1490 cm -1 followed by v(C-S) bands that can be seen in the region of 935 - 1060 cm -1 and v(M-S) bands existed in the region of 350 - 392 cm -1 . Maximum wavelength absorption for ultraviolet-visible spectroscopy for N-C-S group was at 254 nm which indicates π → π * transition. Data from 13 C NMR showed a signal in the region of 198.39 - 199.44 ppm that corresponded to the NCS 2 group. The crystal structure of bis(N,N ' utylethyldithiocarbamato)chloride antimony (III), SbCl (S 2 CN(C 4 H 9 )(C 2 H 5 )) 2 demonstrated a five-coordination geometry, triclinic system, space group P1 with a = 10.0141(8) Armstrong, b = 10.1394(7) Am strong, c = 11.8665(9) Armstrong, α = 67.960(2) degree, β = 87.616(2) degree and γ = 80.172(2) degree. Minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) tests were done using five dithiocarbamate complexes which are Bi Cl[S 2 CN(C 2 H 5 )(C 2 H 4 OH)) 2 , SbCl[S 2 CN(C 2 H 5 )(C 2 H 4 OH)) 2 , Bi Cl(S 2 CN(C 4 H 9 )(C 2 H 5 )) 2 , SbCl(S 2 CN(C 4 H 9 )(C 2 H 5 )) 2 , Bi Cl(S 2 CN(C 7 H 7 )(CH 3 )) 2 towards S. aureus, S. epidermidis, E. aerogenes and E. coli. It was found that all four complexes were active against S. aureus except SbCl(S 2 CN(C 2 H 5 )(C 2 H 4 OH)) 2 while Bi Cl(S 2 CN(C 7 H 7 )(CH 3 )) 2 and Bi Cl(S 2 CN(CH 3 )(C 6 H 11 )) 2 complexes were active against S. epidermidis with MIC value of 5.0 mg/ m

SCS-CN parameter determination using rainfall-runoff data in heterogeneous watersheds. The two-CN system approach

Science.gov (United States)

Soulis, K. X.; Valiantzas, J. D.

2011-10-01

The Soil Conservation Service Curve Number (SCS-CN) approach is widely used as a simple method for predicting direct runoff volume for a given rainfall event. The CN values can be estimated by being selected from tables. However, it is more accurate to estimate the CN value from measured rainfall-runoff data (assumed available) in a watershed. Previous researchers indicated that the CN values calculated from measured rainfall-runoff data vary systematically with the rainfall depth. They suggested the determination of a single asymptotic CN value observed for very high rainfall depths to characterize the watersheds' runoff response. In this paper, the novel hypothesis that the observed correlation between the calculated CN value and the rainfall depth in a watershed reflects the effect of the inevitable presence of soil-cover complex spatial variability along watersheds is being tested. Based on this hypothesis, the simplified concept of a two-CN heterogeneous system is introduced to model the observed CN-rainfall variation by reducing the CN spatial variability into two classes. The behavior of the CN-rainfall function produced by the proposed two-CN system concept is approached theoretically, it is analyzed systematically, and it is found to be similar to the variation observed in natural watersheds. Synthetic data tests, natural watersheds examples, and detailed study of two natural experimental watersheds with known spatial heterogeneity characteristics were used to evaluate the method. The results indicate that the determination of CN values from rainfall runoff data using the proposed two-CN system approach provides reasonable accuracy and it over performs the previous original method based on the determination of a single asymptotic CN value. Although the suggested method increases the number of unknown parameters to three (instead of one), a clear physical reasoning for them is presented.

SCS-CN parameter determination using rainfall-runoff data in heterogeneous watersheds - the two-CN system approach

Science.gov (United States)

Soulis, K. X.; Valiantzas, J. D.

2012-03-01

The Soil Conservation Service Curve Number (SCS-CN) approach is widely used as a simple method for predicting direct runoff volume for a given rainfall event. The CN parameter values corresponding to various soil, land cover, and land management conditions can be selected from tables, but it is preferable to estimate the CN value from measured rainfall-runoff data if available. However, previous researchers indicated that the CN values calculated from measured rainfall-runoff data vary systematically with the rainfall depth. Hence, they suggested the determination of a single asymptotic CN value observed for very high rainfall depths to characterize the watersheds' runoff response. In this paper, the hypothesis that the observed correlation between the calculated CN value and the rainfall depth in a watershed reflects the effect of soils and land cover spatial variability on its hydrologic response is being tested. Based on this hypothesis, the simplified concept of a two-CN heterogeneous system is introduced to model the observed CN-rainfall variation by reducing the CN spatial variability into two classes. The behaviour of the CN-rainfall function produced by the simplified two-CN system is approached theoretically, it is analysed systematically, and it is found to be similar to the variation observed in natural watersheds. Synthetic data tests, natural watersheds examples, and detailed study of two natural experimental watersheds with known spatial heterogeneity characteristics were used to evaluate the method. The results indicate that the determination of CN values from rainfall runoff data using the proposed two-CN system approach provides reasonable accuracy and it over performs the previous methods based on the determination of a single asymptotic CN value. Although the suggested method increases the number of unknown parameters to three (instead of one), a clear physical reasoning for them is presented.

CN radical in diffuse interstellar clouds

International Nuclear Information System (INIS)

Federman, S.R.; Danks, A.C.; Lambert, D.L.

1984-01-01

A survey of 15 lines of sight for the CN B 2 Σ + --X 2 Σ + interstellar absorption lines shows that the CN column density in diffuse interstellar clouds follows the relation log N(CN)proportionalm log N(H 2 ), where mroughly-equal3. This result is reproduced by a reaction network in which CN is produced primarily from C 2 by the neutral-neutral reaction C 2 +N → CN+C, and photodissociation is the main destruction pathway for the neutral molecules CH, C 2 , and CN. The CN radical is the first molecular species observed in diffuse clouds that requires a neutral-neutral reaction for its formation in the gas phase. The network also reproduces the observed ratio N(CN)/N(H 2 )

CN in dark clouds

International Nuclear Information System (INIS)

Churchwell, E.; Bieging, J.H.

1983-01-01

We have detected CN (N = 1--0) emission toward six locations in the Taurus dark cloud complex, but not toward L183 or B227. The two hyperfine components, F = 3/2--1/2 and F = 5/2--3/2 (of J = 3/2--1/2), have intensity ratios near unity toward four locations in Taurus, consistent with large line optical depths. CN column densities are found to be > or approx. =6 x 10 13 cm -2 in those directions where the hyperfine ratios are near unity. By comparing CN with NH 3 and C 18 O column densities, we find that the relative abundance of CN in the Taurus cloudlets is at least a factor of 10 greater than in L183. In this respect, CN fits the pattern of enhanced abundances of carbon-bearing molecules (in partricular the cyanopolyynes) in the Taurus cloudlets relative to similar dark clouds outside Taurus

Strong and anisotropic superexchange in the single-molecule magnet (SMM) [MnIII(6)OsIII]3+: promoting SMM behavior through 3d-5d transition metal substitution.

Science.gov (United States)

Hoeke, Veronika; Stammler, Anja; Bögge, Hartmut; Schnack, Jürgen; Glaser, Thorsten

2014-01-06

The reaction of the in situ generated trinuclear triplesalen complex [(talent-Bu2)MnIII3(solv)n]3+ with (Ph4P)3[OsIII(CN)6] and NaClO4·H2O affords [MnIII6OsIII](ClO4)3 (= [{(talent-Bu2)MnIII3}2{OsIII(CN)6}](ClO4)3) in the presence of the oxidizing agent [(tacn)2NiIII](ClO4)3 (tacn =1,4,7-triazacyclononane), while the reaction of [(talent-Bu2)MnIII3(solv)n]3+ with K4[OsII(CN)6] and NaClO4·H2O yields [MnIII6OsII](ClO4)2 under an argon atmosphere. The molecular structure of [MnIII6OsIII]3+ as determined by single-crystal X-ray diffraction is closely related to the already published [MnIII6Mc]3+ complexes (Mc = CrIII, FeIII, CoIII, MnIII). The half-wave potential of the OsIII/OsII couple is E1/2 = 0.07 V vs Fc+/Fc. The FT-IR and electronic absorption spectra of [MnIII6OsII]2+ and [MnIII6OsIII]3+ exhibit distinct features of dicationic and tricationic [MnIII6Mc]n+ complexes, respectively. The dc magnetic data (μeff vs T, M vs B, and VTVH) of [MnIII6OsII]2+ are successfully simulated by a full-matrix diagonalization of a spin-Hamiltonian including isotropic exchange, zero-field splitting with full consideration of the relative orientation of the D-tensors, and Zeeman interaction, indicating antiferromagnetic MnIII–MnIII interactions within the trinuclear triplesalen subunits (JMn–Mn(1) = −(0.53 ± 0.01) cm–1, Ĥex = −2∑iSMM [MnIII6OsIII]3+ compared to the 3d analogue [MnIII6FeIII]3+ due to the stronger and anisotropic Mc–MnIII exchange interaction.

SCS-CN parameter determination using rainfall-runoff data in heterogeneous watersheds – the two-CN system approach

Directory of Open Access Journals (Sweden)

J. D. Valiantzas

2012-03-01

Full Text Available The Soil Conservation Service Curve Number (SCS-CN approach is widely used as a simple method for predicting direct runoff volume for a given rainfall event. The CN parameter values corresponding to various soil, land cover, and land management conditions can be selected from tables, but it is preferable to estimate the CN value from measured rainfall-runoff data if available. However, previous researchers indicated that the CN values calculated from measured rainfall-runoff data vary systematically with the rainfall depth. Hence, they suggested the determination of a single asymptotic CN value observed for very high rainfall depths to characterize the watersheds' runoff response. In this paper, the hypothesis that the observed correlation between the calculated CN value and the rainfall depth in a watershed reflects the effect of soils and land cover spatial variability on its hydrologic response is being tested. Based on this hypothesis, the simplified concept of a two-CN heterogeneous system is introduced to model the observed CN-rainfall variation by reducing the CN spatial variability into two classes. The behaviour of the CN-rainfall function produced by the simplified two-CN system is approached theoretically, it is analysed systematically, and it is found to be similar to the variation observed in natural watersheds. Synthetic data tests, natural watersheds examples, and detailed study of two natural experimental watersheds with known spatial heterogeneity characteristics were used to evaluate the method. The results indicate that the determination of CN values from rainfall runoff data using the proposed two-CN system approach provides reasonable accuracy and it over performs the previous methods based on the determination of a single asymptotic CN value. Although the suggested method increases the number of unknown parameters to three (instead of one, a clear physical reasoning for them is presented.

Nitrile hydration by thiolate- and alkoxide-ligated Co-NHase analogues. Isolation of Co(III)-amidate and Co(III)-iminol intermediates.

Science.gov (United States)

Swartz, Rodney D; Coggins, Michael K; Kaminsky, Werner; Kovacs, Julie A

2011-03-23

Nitrile hydratases (NHases) are thiolate-ligated Fe(III)- or Co(III)-containing enzymes, which convert nitriles to the corresponding amide under mild conditions. Proposed NHase mechanisms involve M(III)-NCR, M(III)-OH, M(III)-iminol, and M(III)-amide intermediates. There have been no reported crystallographically characterized examples of these key intermediates. Spectroscopic and kinetic data support the involvement of a M(III)-NCR intermediate. A H-bonding network facilitates this enzymatic reaction. Herein we describe two biomimetic Co(III)-NHase analogues that hydrate MeCN, and four crystallographically characterized NHase intermediate analogues, [Co(III)(S(Me2)N(4)(tren))(MeCN)](2+) (1), [Co(III)(S(Me2)N(4)(tren))(OH)](+) (3), [Co(III)(S(Me2)N(4)(tren))(NHC(O)CH(3))](+) (2), and [Co(III)(O(Me2)N(4)(tren))(NHC(OH)CH(3))](2+) (5). Iminol-bound 5 represents the first example of a Co(III)-iminol compound in any ligand environment. Kinetic parameters (k(1)(298 K) = 2.98(5) M(-1) s(-1), ΔH(‡) = 12.65(3) kcal/mol, ΔS(‡) = -14(7) e.u.) for nitrile hydration by 1 are reported, and the activation energy E(a) = 13.2 kcal/mol is compared with that (E(a) = 5.5 kcal/mol) of the NHase enzyme. A mechanism involving initial exchange of the bound MeCN for OH- is ruled out by the fact that nitrile exchange from 1 (k(ex)(300 K) = 7.3(1) × 10(-3) s(-1)) is 2 orders of magnitude slower than nitrile hydration, and that hydroxide bound 3 does not promote nitrile hydration. Reactivity of an analogue that incorporates an alkoxide as a mimic of the highly conserved NHase serine residue shows that this moiety facilitates nitrile hydration under milder conditions. Hydrogen-bonding to the alkoxide stabilizes a Co(III)-iminol intermediate. Comparison of the thiolate versus alkoxide intermediate structures shows that C≡N bond activation and C═O bond formation proceed further along the reaction coordinate when a thiolate is incorporated into the coordination sphere.

Nanomechanical properties of TiCN and TiCN/Ti coatings on Ti prepared by Filtered Arc Deposition

International Nuclear Information System (INIS)

Sun, Yong; Lu, Cheng; Yu, Hailiang; Kiet Tieu, A.; Su, Lihong; Zhao, Yue; Zhu, Hongtao; Kong, Charlie

2015-01-01

Monolayer TiCN and multilayer TiCN/Ti coatings were deposited on the surface of Ti using the Filtered Arc Deposition System (FADS). Nanoindentation tests were performed on both coatings. The multilayer TiCN/Ti coating exhibited better ductility than the monolayer TiCN coating. The lattice constants of the coatings were characterized by X-ray diffraction. Transmission Electron Microscopy (TEM) was used to investigate the fracture behavior of the coatings. Inter-columnar, inclined and lateral cracks were found to be the dominant crack modes in the monolayer TiCN coatings while small bending crack and radial crack were the dominant crack modes in the multilayer TiCN/Ti coatings. The Finite Element Method (FEM) was used to simulate the indentation process. It was found that the Ti interlayer in the multilayer TiCN/Ti coating could efficiently suppress the fracture, which is responsible for the improved ductility of the multilayer TiCN/Ti coating

Nitrile Hydration by Thiolate–and Alkoxide–Ligated Co-NHase Analogues. Isolation of Co(III)-Amidate and Co(III)–Iminol Intermediates

Science.gov (United States)

Swartz, Rodney D.; Coggins, Michael K.; Kaminsky, Werner; Kovacs, Julie A.

2011-01-01

Nitrile hydratases (NHases) are thiolate–ligated Fe(III)- or Co(III)-containing enzymes, which convert nitriles to the corresponding amide under mild conditions. Proposed NHase mechanisms involve M(III)–NCR, M(III)–OH, M(III)–iminol and M(III)–amide intermediates. Spectroscopic and kinetic data support the involvement of a M(III)–NCR intermediate. A H–bonding network facilitates this enzymatic reaction. There have been no reported crystallographically characterized examples of these key intermediates. Herein we describe two biomimetic Co(III)–NHase analogues that hydrate MeCN. Four key crystallographically characterized NHase intermediate anaologues, [CoIII(SMe2N4(tren))(MeCN)]2+ (1), [CoIII(SMe2N4(tren))(OH)]+ (3), [CoIII(SMe2N4(tren))(NHC(O)CH3)]+ (2), and [CoIII(OMe2N4(tren))(NHC(OH)CH3)]2+ (5) are described. Iminol–bound 5 represents the first example of a Co(III)-iminol compound in any ligand environment. Kinetic parameters (k1(298 K)= 2.98(5) M−1s−1, ΔH‡ = 12.65(3) kcal/mol, ΔS‡ = −14(7) e.u.) for nitrile hydration by 1 are reported, and the activation energy Ea= 13.2 kcal/mol is compared with that (Ea= 5.5 kcal/mol) of the NHase enzyme. A mechanism involving initial exchange of the bound MeCN for OH− is ruled out by the fact that nitrile exchange from 1 (kex(300 K)= 7.3(1) x10−3 s−1) is two orders of magnitude slower than nitrile hydration, and that hydroxide bound 3 does not promote nitrile hydration. Reactivity of an analogue that incorporates an alkoxide as a mimic of the highly conserved NHase serine residue shows that this moiety facilitates nitrile hydration under milder conditions. Hydrogen-bonding to the alkoxide stabilizes a Co(III)-iminol intermediate. Comparison of the thiolate versus alkoxide intermediate structures shows that C≡N bond activation and C=O bond formation proceed further along the reaction coordinate when a thiolate is incorporated into the coordination sphere. PMID:21351789

Clues to NaCN formation

Science.gov (United States)

Quintana-Lacaci, G.; Cernicharo, J.; Velilla Prieto, L.; Agúndez, M.; Castro-Carrizo, A.; Fonfría, J. P.; Massalkhi, S.; Pardo, J. R.

2017-11-01

Context. ALMA is providing us essential information on where certain molecules form. Observing where these molecules emission arises from, the physical conditions of the gas, and how this relates with the presence of other species allows us to understand the formation of many species, and to significantly improve our knowledge of the chemistry that occurs in the space. Aims: We studied the molecular distribution of NaCN around IRC +10216, a molecule detected previously, but whose origin is not clear. High angular resolution maps allow us to model the abundance distribution of this molecule and check suggested formation paths. Methods: We modeled the emission of NaCN assuming local thermal equilibrium (LTE) conditions. These profiles were fitted to azimuthal averaged intensity profiles to obtain an abundance distribution of NaCN. Results: We found that the presence of NaCN seems compatible with the presence of CN, probably as a result of the photodissociation of HCN, in the inner layers of the ejecta of IRC +10216. However, similar as for CH3CN, current photochemical models fail to reproduce this CN reservoir. We also found that the abundance peak of NaCN appears at a radius of 3 × 1015 cm, approximately where the abundance of NaCl, suggested to be the parent species, starts to decay. However, the abundance ratio shows that the NaCl abundance is lower than that obtained for NaCN. We expect that the LTE assumption might result in NaCN abundances higher than the real ones. Updated photochemical models, collisional rates, and reaction rates are essential to determine the possible paths of the NaCN formation. Based on observations carried out with ALMA and the IRAM 30 m Telescope. ALMA is a partnership of ESO (representing its member states), NSF (USA) and NINS (Japan), together with NRC (Canada) and NSC and ASIAA (Taiwan), in cooperation with the Republic of Chile. The Joint ALMA Observatory is operated by ESO, AUI/NRAO and NAOJ. IRAM is supported by INSU/CNRS (France

Thermophysical properties of the ionic liquids [EMIM][B(CN)4] and [HMIM][B(CN)4].

Science.gov (United States)

Koller, Thomas M; Rausch, Michael H; Ramos, Javier; Schulz, Peter S; Wasserscheid, Peter; Economou, Ioannis G; Fröba, Andreas P

2013-07-18

In the present study, the thermophysical properties of the tetracyanoborate-based ionic liquids (ILs) 1-ethyl-3-methylimidazolium tetracyanoborate ([EMIM][B(CN)4]) and 1-hexyl-3-methylimidazolium tetracyanoborate ([HMIM][B(CN)4]) obtained by both experimental methods and molecular dynamics (MD) simulations are presented. Conventional experimental techniques were applied for the determination of refractive index, density, interfacial tension, and self-diffusion coefficients for [HMIM][B(CN)4] at atmospheric pressure in the temperature range from 283.15 to 363.15 K. In addition, surface light scattering (SLS) experiments provided accurate viscosity and interfacial tension data. As no complete molecular parametrization was available for the MD simulations of [HMIM][B(CN)4], our recently developed united-atom force field for [EMIM][B(CN)4] was partially transferred to the homologous IL [HMIM][B(CN)4]. Deviations between our simulated and experimental data for the equilibrium properties are less than ±0.3% in the case of density and less than ±8% in the case of interfacial tension for both ILs. Furthermore, the calculated and measured data for the transport properties viscosity and self-diffusion coefficient are in good agreement, with deviations of less than ±30% over the whole temperature range. In addition to a comparison with the literature, the influence of varying cation chain length on thermophysical properties of [EMIM][B(CN)4] and [HMIM][B(CN)4] is discussed.

Analysis of gold(I/III)-complexes by HPLC-ICP-MS demonstrates gold(III) stability in surface waters.

Science.gov (United States)

Ta, Christine; Reith, Frank; Brugger, Joël; Pring, Allan; Lenehan, Claire E

2014-05-20

Understanding the form in which gold is transported in surface- and groundwaters underpins our understanding of gold dispersion and (bio)geochemical cycling. Yet, to date, there are no direct techniques capable of identifying the oxidation state and complexation of gold in natural waters. We present a reversed phase ion-pairing HPLC-ICP-MS method for the separation and determination of aqueous gold(III)-chloro-hydroxyl, gold(III)-bromo-hydroxyl, gold(I)-thiosulfate, and gold(I)-cyanide complexes. Detection limits for the gold species range from 0.05 to 0.30 μg L(-1). The [Au(CN)2](-) gold cyanide complex was detected in five of six waters from tailings and adjacent monitoring bores of working gold mines. Contrary to thermodynamic predictions, evidence was obtained for the existence of Au(III)-complexes in circumneutral, hypersaline waters of a natural lake overlying a gold deposit in Western Australia. This first direct evidence for the existence and stability of Au(III)-complexes in natural surface waters suggests that Au(III)-complexes may be important for the transport and biogeochemical cycling of gold in surface environments. Overall, these results show that near-μg L(-1) enrichments of Au in environmental waters result from metastable ligands (e.g., CN(-)) as well as kinetically controlled redox processes leading to the stability of highly soluble Au(III)-complexes.

Heterobimetallic [NiFe] Complexes Containing Mixed CO/CN- Ligands: Analogs of the Active Site of the [NiFe] Hydrogenases.

Science.gov (United States)

Perotto, Carlo U; Sodipo, Charlene L; Jones, Graham J; Tidey, Jeremiah P; Blake, Alexander J; Lewis, William; Davies, E Stephen; McMaster, Jonathan; Schröder, Martin

2018-03-05

The development of synthetic analogs of the active sites of [NiFe] hydrogenases remains challenging, and, in spite of the number of complexes featuring a [NiFe] center, those featuring CO and CN - ligands at the Fe center are under-represented. We report herein the synthesis of three bimetallic [NiFe] complexes [Ni( N 2 S 2 )Fe(CO) 2 (CN) 2 ], [Ni( S 4 )Fe(CO) 2 (CN) 2 ], and [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] that each contain a Ni center that bridges through two thiolato S donors to a {Fe(CO) 2 (CN) 2 } unit. X-ray crystallographic studies on [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ], supported by DFT calculations, are consistent with a solid-state structure containing distinct molecules in the singlet ( S = 0) and triplet ( S = 1) states. Each cluster exhibits irreversible reduction processes between -1.45 and -1.67 V vs Fc + /Fc and [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] possesses a reversible oxidation process at 0.17 V vs Fc + /Fc. Spectroelectrochemical infrared (IR) and electron paramagnetic resonance (EPR) studies, supported by density functional theory (DFT) calculations, are consistent with a Ni III Fe II formulation for [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] + . The singly occupied molecular orbital (SOMO) in [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] + is based on Ni 3d z 2 and 3p S with the S contributions deriving principally from the apical S-donor. The nature of the SOMO corresponds to that proposed for the Ni-C state of the [NiFe] hydrogenases for which a Ni III Fe II formulation has also been proposed. A comparison of the experimental structures, and the electrochemical and spectroscopic properties of [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] and its [Ni( N 2 S 3 )] precursor, together with calculations on the oxidized [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] + and [Ni( N 2 S 3 )] + forms suggests that the binding of the {Fe(CO)(CN) 2 } unit to the {Ni(CysS) 4 } center at the active site of the [NiFe] hydrogenases suppresses thiolate-based oxidative chemistry involving the bridging thiolate S donors

SCS-CN parameter determination using rainfall-runoff data in heterogeneous watersheds. The two-CN system approach

OpenAIRE

K. X. Soulis; J. D. Valiantzas

2011-01-01

The Soil Conservation Service Curve Number (SCS-CN) approach is widely used as a simple method for predicting direct runoff volume for a given rainfall event. The CN values can be estimated by being selected from tables. However, it is more accurate to estimate the CN value from measured rainfall-runoff data (assumed available) in a watershed. Previous researchers indicated that the CN values calculated from measured rainfall-runoff data vary systematically with the rainfall depth. The...

Solid solution cermet: (Ti,Nb)(CN)-Ni cermet.

Science.gov (United States)

Kwon, Hanjung; Jung, Sun-A

2014-11-01

Solid solution powders without W, (Ti,Nb)(CN) powders with a B1 structure (NaCl like), were synthesized by high energy milling and carbothermal reduction in nitrogen. The range of molar ratios of Ti/Nb for forming complete (Ti,Nb)(CN) phase was broader than that of Ti/W for the (Ti,W)(CN) phase because carbide or carbonitride of Nb had a B1 crystal structure identical to Ti(CN) while WC had a hexagonal crystal structure. The results revealed that the hardness of (Ti,Nb)(CN)-Ni cermets was higher than that of (Ti,W)(CN)-Ni cermets. The lower density of the (Ti,Nb)(CN) powder contributed to the higher hardness compared to (Ti,W)(CN) because the volumetric ratio of (Ti,Nb)(CN) in the (Ti,Nb)(CN)-Ni cermets was higher than that of (Ti,Nb)(CN) in the (Ti,W)(CN)-Ni cermets at the same weight ratio of Ni. Additionally, it was assumed that intrinsic the properties of (Ti,Nb)(CN) could also be the cause for the high hardness of the (Ti,Nb)(CN)-Ni cermets.

Observation of the long-lived triplet excited state of perylenebisimide (PBI) in C^N cyclometalated Ir(III) complexes and application in photocatalytic oxidation.

Science.gov (United States)

Sun, Jifu; Zhong, Fangfang; Zhao, Jianzhang

2013-07-14

Perylenebisimide (PBI) was used to prepare C^N cyclometalated Ir(III) complexes that show strong absorption of visible light and it is the first time the long-lived triplet excited state of PBI chromophore was observed in a transition metal complex (τT = 22.3 μs). Previously, the lifetime of the triplet state of PBI in transition metal complexes was usually shorter than 1.0 μs. Long-lived triplet excited states are useful for applications in photocatalysis or other photophysical processes concerning triplet-triplet-energy-transfer. PBI and amino-PBI were used for preparation of cyclometalated Ir(III) complexes (Ir-2 and Ir-3), in which the PBI chromophore was connected to the coordination center via C≡C π-conjugation bond. The new complexes show strong absorption in visible region (ε = 34,200 M(-1) cm(-1) at 541 nm for Ir-2, and ε = 19,000 at 669 nm for Ir-3), compared to the model complex Ir(ppy)(bpy)[PF6] Ir-1 (ε PBI-localized long-lived (3)IL states were populated for Ir-2 and Ir-3 upon photoexcitation. The complexes were used as triplet photosensitizers for (1)O2-mediated photooxidation of 1,5-dihydronaphthalene to produce juglone, an important intermediate for preparation of anti-cancer compounds. (1)O2 quantum yields (Φ(Δ)) up to 91% were observed for the new Ir(III) complexes and the overall photosensitizing ability is much higher than the conventional Ir(III) complex Ir-1, which shows the typical weak visible light absorption in visible region. Our results are useful for preparation of transition metal complexes that show strong absorption of visible light and long-lived triplet excited state and for the application of these complexes in photocatalysis.

On the ortho-positronium quenching reactions promoted by Fe(II), Fe(III), Co(III), Ni(II), Zn(II) and Cd(II) cyanocomplexes

Science.gov (United States)

Fantola Lazzarini, Anna L.; Lazzarini, Ennio

The o-Ps quenching reactions promoted in aqueous solutions by the following six cyanocomplexes: [Fe(CN) 6] 4-; [Co(CN) 6] 3-; [Zn(CN) 4] 2-; [Cd(CN) 6] 2-; [Fe(CN) 6] 3-; [Ni(CN) 4] 2- were investigated. The first four reactions probably consist in o-Ps addition across the CN bond, their rate constants at room temperature, Tr, being ⩽(0.04±0.02) × 10 9 M -1 s -1, i.e. almost at the limit of experimental errors. The rate constant of the fifth reaction, in o-Ps oxydation, at Tr is (20.3±0.4) × 10 9 M -1 s -1. The [Ni(CN) 4] 2-k value at Tr, is (0.27±0.01) × 10 9 M -1 s -1, i.e. 100 times less than the rate constants of o-Ps oxydation, but 10 times larger than those of the o-Ps addition across the CN bond. The [Ni(CN) 4] 2- reaction probably results in formation of the following positronido complex: [Ni(CN) 4Ps] 2-. However, it is worth noting that the existence of such a complex is only indirectly deduced. In fact it arises from comparison of the [Ni(CN) 4] 2- rate constant with those of the Fe(II), Zn(II), Cd(II), and Co(III) cyanocomplexes, which, like the Ni(II) cyanocomplex, do not promote o-Ps oxydation or spin exchange reactions.

H12CN and H13CN excitation analysis in the circumstellar outflow of R Sculptoris

Science.gov (United States)

Saberi, M.; Maercker, M.; De Beck, E.; Vlemmings, W. H. T.; Olofsson, H.; Danilovich, T.

2017-03-01

Context. The 12CO/13CO isotopologue ratio in the circumstellar envelope (CSE) of asymptotic giant branch (AGB) stars has been extensively used as the tracer of the photospheric 12C/13C ratio. However, spatially-resolved ALMA observations of R Scl, a carbon rich AGB star, have shown that the 12CO/13CO ratio is not consistent over the entire CSE. Hence, it can not necessarily be used as a tracer of the 12C/13C ratio. The most likely hypothesis to explain the observed discrepancy between the 12CO/13CO and 12C/13C ratios is CO isotopologue selective photodissociation by UV radiation. Unlike the CO isotopologue ratio, the HCN isotopologue ratio is not affected by UV radiation. Therefore, HCN isotopologue ratios can be used as the tracer of the atomic C ratio in UV irradiated regions. Aims: We aim to present ALMA observations of H13CN(4-3) and APEX observations of H12CN(2-1), H13CN(2-1, 3-2) towards R Scl. These new data, combined with previously published observations, are used to determine abundances, ratio, and the sizes of line-emitting regions of the aforementioned HCN isotopologues. Methods: We have performed a detailed non-LTE excitation analysis of circumstellar H12CN(J = 1-0, 2-1, 3-2, 4-3) and H13CN(J = 2-1, 3-2, 4-3) line emission around R Scl using a radiative transfer code based on the accelerated lambda iteration (ALI) method. The spatial extent of the molecular distribution for both isotopologues is constrained based on the spatially resolved H13CN(4-3) ALMA observations. Results: We find fractional abundances of H12CN/H2 = (5.0 ± 2.0) × 10-5 and H13CN/H2 = (1.9 ± 0.4) × 10-6 in the inner wind (r ≤ (2.0 ± 0.25) ×1015 cm) of R Scl. The derived circumstellar isotopologue ratio of H12CN/H13CN = 26.3 ± 11.9 is consistent with the photospheric ratio of 12C/13C 19 ± 6. Conclusions: We show that the circumstellar H12CN/H13CN ratio traces the photospheric 12C/13C ratio. Hence, contrary to the 12CO/13CO ratio, the H12CN/H13CN ratio is not affected by UV

AD Leonis: Radial Velocity Signal of Stellar Rotation or Spin–Orbit Resonance?

Science.gov (United States)

Tuomi, Mikko; Jones, Hugh R. A.; Barnes, John R.; Anglada-Escudé, Guillem; Butler, R. Paul; Kiraga, Marcin; Vogt, Steven S.

2018-05-01

AD Leonis is a nearby magnetically active M dwarf. We find Doppler variability with a period of 2.23 days, as well as photometric signals: (1) a short-period signal, which is similar to the radial velocity signal, albeit with considerable variability; and (2) a long-term activity cycle of 4070 ± 120 days. We examine the short-term photometric signal in the available All-Sky Automated Survey and Microvariability and Oscillations of STars (MOST) photometry and find that the signal is not consistently present and varies considerably as a function of time. This signal undergoes a phase change of roughly 0.8 rad when considering the first and second halves of the MOST data set, which are separated in median time by 3.38 days. In contrast, the Doppler signal is stable in the combined High-Accuracy Radial velocity Planet Searcher and High Resolution Echelle Spectrometer radial velocities for over 4700 days and does not appear to vary in time in amplitude, phase, period, or as a function of extracted wavelength. We consider a variety of starspot scenarios and find it challenging to simultaneously explain the rapidly varying photometric signal and the stable radial velocity signal as being caused by starspots corotating on the stellar surface. This suggests that the origin of the Doppler periodicity might be the gravitational tug of a planet orbiting the star in spin–orbit resonance. For such a scenario and no spin–orbit misalignment, the measured v\\sin i indicates an inclination angle of 15.°5 ± 2.°5 and a planetary companion mass of 0.237 ± 0.047 M Jup.

SORPTION OF Au(III BY Saccharomyces cerevisiae BIOMASS

Directory of Open Access Journals (Sweden)

Amaria Amaria

2010-07-01

Full Text Available Au(III sorption by S. cerevisiae biomass extracted from beer waste industry was investigated. Experimentally, the sorption was conducted in batch method. This research involved five steps: 1 identification the functional groups present in the S. cerevisiae biomass by infrared spectroscopic technique, 2 determination of optimum pH, 3 determination of the sorption capacity and energy, 4 determination of the sorption type by conducting desorption of sorbed Au(III using specific eluents having different desorption capacity such as H2O (van der Waals, KNO3 (ion exchange, HNO3 (hydrogen bond, and tiourea (coordination bond, 5 determination of effective eluents in Au(III desorption by partial desorption of sorbed Au(III using thiourea, NaCN and KI. The remaining Au(III concentrations in filtrate were analyzed using Atomic Absorption Spectrophotometer. The results showed that: 1 Functional groups of S. cerevisiae biomass that involved in the sorption processes were hydroxyl (-OH, carboxylate (-COO- and amine (-NH2, 2 maximum sorption was occurred at pH 4, equal to 98.19% of total sorption, 3 The sorption capacity of biomass was 133.33 mg/g (6.7682E-04 mol/g and was involved sorption energy 23.03 kJ mol-1, 4 Sorption type was dominated by coordination bond, 5 NaCN was effective eluent to strip Au(III close to 100%.   Keywords: sorption, desorption, S. cerevisiae biomass, Au(III

Simultaneous speciation of arsenic (As(III), MMA, DMA, and As(V)) and selenium (Se(IV), Se(VI), and SeCN{sup -}) in petroleum refinery aqueous streams

Energy Technology Data Exchange (ETDEWEB)

Tonietto, Gisele B.; Godoy, Jose M.; Oliveira, Ana Cristina [Pontificia Universidade Catolica do Rio de Janeiro, Rio de Janeiro, RJ (Brazil); Souza, Marcia V. de [Petrobras/Cenpes, Research and Development Center, Rio de Janeiro (Brazil)

2010-07-15

High-performance liquid chromatography (HPLC) coupled to an ICP-MS with an octapole reaction system (ORS) has been used to carry out quantitative speciation of selenium (Se) and arsenic (As) in the stream waters of a refining process. The argon dimers interfering with the {sup 78}Se and {sup 80}Se isotopes were suppressed by pressurizing the octapole chamber with 3.1 mL min{sup -1} H{sub 2} and 0.5 mL min{sup -1} He. Four arsenic species arsenite - As(III), arsenate (As(V)), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) - and three inorganic Se species - selenite Se(IV), selenate Se(VI), and selenocyanate (SeCN{sup -}) - were separated in a single run by ion chromatography (IC) using gradient elution with 100 mmol L{sup -1} NH{sub 4}NO{sub 3}, pH 8.5, adjusted by addition of NH{sub 3}, as eluent. Repeatabilities of peak position and of peak area evaluation were better than 1% and about 3%, respectively. Detection limits (as 3{sigma} of the baseline noise) were 81, 56, and 75 ng L{sup -1} for Se(IV), Se(VI), and SeCN{sup -}, respectively, and 22, 19, 25, and 16 ng L{sup -1} for As(III), As(V), MMA, and DMA, respectively. Calibration curve R {sup 2} values ranged between 0.996 and 0.999 for the arsenic and selenium species. Column recovery for ion chromatography was calculated to be 97 {+-} 6% for combined arsenic species and 98 {+-} 3% for combined selenium species. Because certified reference materials for As and Se speciation studies are still not commercially available, in order to check accuracy and precision the method was applied to certified reference materials, BCR 714, BCR 1714, and BCR 715 and to two different refinery samples - inlet and outlet wastewater. The method was successfully used to study the quantitative speciation of selenium and arsenic in petroleum refinery wastewaters. (orig.)

Tetraethylammonium dicyanido(5,10,15,20-tetraphenylporphyrinatoferrate(III dichloromethane monosolvate

Directory of Open Access Journals (Sweden)

Michael Shatruk

2013-08-01

Full Text Available The title compound, (C8H20N[Fe(C44H28N4(CN2]·CH2Cl2 or (Et4N[Fe(TPP(CN2], was recrystallized from dichloromethane–diethyl ether. The compound crystallizes with the two unique halves of the FeIII porphyrinato complex, one tetraethylammonium cation and one interstitial dichloromethane molecule within the asymmetric unit. Both anionic FeIII complexes exhibit inversion symmetry. Both the cation and the solvent molecules show positional disorder. The cation is disordered over two sets of sites with an occupancy ratio of 0.710 (3:0.290 (3; the solvent molecule is disordered over three positions with a 0.584 (6:0.208 (3:0.202 (5 ratio. The crystal packing features columns of [Fe(TPP(CN2]− anions that propagate along [001]. The columns further pack into layers that are parallel to (011 and also include the Et4N+ cations. The interstitial CH2Cl2 molecules appear in the interlayer space. This complex may serve as a useful precursor for the assembly of multinuclear and extended CN-bridged complexes for the design of single-molecule and single-chain magnets, respectively.

Synthesis, characterisation and modelling of a ferromagnetically coupled chromium(III) Dimer

DEFF Research Database (Denmark)

Morsing, Thorbjørn Juul; Weihe, Høgni; Bendix, Jesper

2014-01-01

A rare example of a ferromagnetically coupled dinuclear chromium(III) complex, the di-μ-hydroxobis[tetrakis(isothiocyanato)chromate(III)] anion, is reported. This complex has been synthesised from the oxo-bridged acetonitrile complex [(CH3CN)5CrOCr(NCCH3)5](BF4)4 and isolated as the solvated...

Is interstellar detection of higher members of the linear radicals CnCH and CnN feasible?

Science.gov (United States)

Pauzat, F.; Ellinger, Y.; Mclean, A. D.

1991-01-01

Rotational constants and dipole moments for linear-chain radicals CnCH and CnN are estimated using a combinatiaon of ab initio molecular orbital calculations and observed data on the starting members of the series. CnCH with n = 0-5 have been observed by radioastronomy in carbon-rich interstellar clouds; higher members of the series have 2Pi ground states with large dipole moments and are strong candidates for observation. CN and C3N have also been observed by radioastronomy; higher members of the series, with the possible exception of C5N, have 2Pi ground states with near-zero dipole moments making their interstellar detection hopeless under present observational conditions. C5N can be a strong candidate only if it has a 2Sigma ground state, and best computations so far indicate that this is not the case.

Is interstellar detection of higher members of the linear radicals CnCH and CnN feasible?

International Nuclear Information System (INIS)

Pauzat, F.; Ellinger, Y.; Mclean, A.D.

1991-01-01

Rotational constants and dipole moments for linear-chain radicals CnCH and CnN are estimated using a combinatiaon of ab initio molecular orbital calculations and observed data on the starting members of the series. CnCH with n = 0-5 have been observed by radioastronomy in carbon-rich interstellar clouds; higher members of the series have 2Pi ground states with large dipole moments and are strong candidates for observation. CN and C3N have also been observed by radioastronomy; higher members of the series, with the possible exception of C5N, have 2Pi ground states with near-zero dipole moments making their interstellar detection hopeless under present observational conditions. C5N can be a strong candidate only if it has a 2Sigma ground state, and best computations so far indicate that this is not the case. 20 refs

Evidence of significant covalent bonding in Au(CN)(2)(-).

Science.gov (United States)

Wang, Xue-Bin; Wang, Yi-Lei; Yang, Jie; Xing, Xiao-Peng; Li, Jun; Wang, Lai-Sheng

2009-11-18

The Au(CN)(2)(-) ion is the most stable Au compound known for centuries, yet a detailed understanding of its chemical bonding is still lacking. Here we report direct experimental evidence of significant covalent bonding character in the Au-C bonds in Au(CN)(2)(-) using photoelectron spectroscopy and comparisons with its lighter congeners, Ag(CN)(2)(-) and Cu(CN)(2)(-). Vibrational progressions in the Au-C stretching mode were observed for all detachment transitions for Au(CN)(2)(-), in contrast to the atomic-like transitions for Cu(CN)(2)(-), revealing the Au-C covalent bonding character. In addition, rich electronic structural information was obtained for Au(CN)(2)(-) by employing 118 nm detachment photons. Density functional theory and high-level ab initio calculations were carried out to understand the photoelectron spectra and obtain insight into the nature of the chemical bonding in the M(CN)(2)(-) complexes. Significant covalent character in the Au-C bonding due to the strong relativistic effects was revealed in Au(CN)(2)(-), consistent with its high stability.

Behaviour of Au(I,III) cyanides on anion exchangers in the presence of Pd compounds

International Nuclear Information System (INIS)

Knothe, M.

1985-01-01

The behaviour of low concentrations of [Au(I)(CN) 2 ] - and [Au(III)(CN) 4 ] - in the presence of [Pd(NH 3 ) 4 ](NO 3 ) 2 when adsorbed by anionites has been studied with the aid of labelled Au compounds. The adsorption rate of Au decreased with increasing ageing of the feed solution, which was due to the conversion of gold cyanides into species not capable of being adsorbed. This conversion proceeded at a considerably lower rate when the cyanides of gold had been fixed on the ionite. Au(I) cyanides were always converted at a higher rate than Au(III) cyanides. Thus, an effective separation of Au cyanides by anionites is possible only in the Au(III) system. (author)

Thermal decomposition of [Co(en)3][Fe(CN)6]∙ 2H2O: Topotactic dehydration process, valence and spin exchange mechanism elucidation.

Science.gov (United States)

Trávníček, Zdeněk; Zbořil, Radek; Matiková-Maľarová, Miroslava; Drahoš, Bohuslav; Cernák, Juraj

2013-01-01

The Prussian blue analogues represent well-known and extensively studied group of coordination species which has many remarkable applications due to their ion-exchange, electron transfer or magnetic properties. Among them, Co-Fe Prussian blue analogues have been extensively studied due to the photoinduced magnetization. Surprisingly, their suitability as precursors for solid-state synthesis of magnetic nanoparticles is almost unexplored. In this paper, the mechanism of thermal decomposition of [Co(en)3][Fe(CN)6] ∙∙ 2H2O (1a) is elucidated, including the topotactic dehydration, valence and spins exchange mechanisms suggestion and the formation of a mixture of CoFe2O4-Co3O4 (3:1) as final products of thermal degradation. The course of thermal decomposition of 1a in air atmosphere up to 600°C was monitored by TG/DSC techniques, (57)Fe Mössbauer and IR spectroscopy. As first, the topotactic dehydration of 1a to the hemihydrate [Co(en)3][Fe(CN)6] ∙∙ 1/2H2O (1b) occurred with preserving the single-crystal character as was confirmed by the X-ray diffraction analysis. The consequent thermal decomposition proceeded in further four stages including intermediates varying in valence and spin states of both transition metal ions in their structures, i.e. [Fe(II)(en)2(μ-NC)Co(III)(CN)4], Fe(III)(NH2CH2CH3)2(μ-NC)2Co(II)(CN)3] and Fe(III)[Co(II)(CN)5], which were suggested mainly from (57)Fe Mössbauer, IR spectral and elemental analyses data. Thermal decomposition was completed at 400°C when superparamagnetic phases of CoFe2O4 and Co3O4 in the molar ratio of 3:1 were formed. During further temperature increase (450 and 600°C), the ongoing crystallization process gave a new ferromagnetic phase attributed to the CoFe2O4-Co3O4 nanocomposite particles. Their formation was confirmed by XRD and TEM analyses. In-field (5 K / 5 T) Mössbauer spectrum revealed canting of Fe(III) spin in almost fully inverse spinel structure of CoFe2O4. It has been found that the thermal

Variation of the solvation number of Eu(III) in mixed system of methanol and water

International Nuclear Information System (INIS)

Suganuma, H.; Arisaka, M.; Omori, T.; Satoh, I.; Choppin, G.R.

1999-01-01

The stability constants (β 1 ) of the monofluoride complex of Eu(III) have been determined in mixed solvents of methanol and water at a 0.10 M ionic strength using a solvent extraction technique. The values of ln β 1 increase as the mole fraction of methanol in the mixed solvent system increases. The variation in the stability constants can be correlated with both the large effect due to the solvation of F and the small effect due to both (1) the solvation of cations in connection with complexation and (2) the electrostatic attraction between Eu 3+ and F - . Based on the variation in the sum of (1) and (2) in water and the mixed solvent solutions, it was determined that the coordination number (CN) of Eu(III) varied from a mixture of CN = 9 and 8 to CN = 8 at about a 0.03 mole fraction of methanol in the mixed solvent. (orig.)

Magnetic anisotropy of [Mo(CN)7]4- anions and fragments of cyano-bridged magnetic networks.

Science.gov (United States)

Chibotaru, Liviu F; Hendrickx, Marc F A; Clima, Sergiu; Larionova, Joulia; Ceulemans, Arnout

2005-08-18

Quantum chemistry calculations of CASSCF/CASPT2 level together with ligand field analysis are used for the investigation of magnetic anisotropy of [Mo(CN)7]4- complexes. We have considered three types of heptacyano environments: two ideal geometries, a pentagonal bipyramid and a capped trigonal prism, and the heptacyanomolybdate fragment of the cyano-bridged magnetic network K2[Mn(H2O)2]3[Mo(CN)7]2.6H2O. At all geometries the first excited Kramers doublet is found remarkably close to the ground one due to a small orbital energy gap in the ligand field spectrum, which ranges between a maximal value in the capped trigonal prism (800 cm(-1)) and zero in the pentagonal bipyramid. The small value of this gap explains (i) the axial form of the g tensor and (ii) the strong magnetic anisotropy even in strongly distorted complexes. Comparison with available experimental data for the g tensor of the mononuclear precursors reveals good agreement with the present calculations for the capped trigonal prismatic complex and a significant discrepancy for the pentagonal bipyramidal one. The calculations for the heptacyanomolybdate fragment of K2[Mn(H2O)2]3[Mo(CN)7]2.6H2O give g(perpendicular)/g(parallel) approximately 0.5 and the orientation of the local anisotropy axis close to the symmetry axis of an idealized pentagonal bipyramid. These findings are expected to be important for the understanding of the magnetism of anisotropic Mo(III)-Mn(II) cyano-bridged networks based on the [Mo(CN)7]4- building block.

The new carbodiimide Li_2Gd_2Sr(CN_2)_5 having a crystal structure related to that of Gd_2(CN_2)_3

International Nuclear Information System (INIS)

Unverfehrt, Leonid; Stroebele, Markus; Meyer, H. Juergen

2013-01-01

The new carbodiimide compounds Li_2RE_2Sr(CN_2)_5 (RE = Sm, Gd, Eu, Tb) were prepared by a straight forward solid state metathesis reaction of REF_3, SrF_2, and Li_2(CN_2) at around 600 C. The crystal structure of Li_2Gd_2Sr(CN_2)_5 was solved based on X-ray single-crystal diffraction data. Corresponding Li_2RE_2Sr(CN_2)_5 compounds were analyzed by isotypic indexing of their powder patterns. The crystal structure of Li_2Gd_2Sr(CN_2)_5 can be well related to that of Gd_2(CN_2)_3, because both structures are based on layered structures composed of close packed layers of [N=C=N]"2"- sticks, alternating with layers of metal ions. The crystal structure of Li_2Gd_2Sr(CN_2)_5 can be considered to contain an ABC layer sequence of [N = C=N]"2"- layers with the interlayer voids being occupied by (three) distinct types of cations. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Synthesis, Crystal Structures, Magnetic Properties, and Theoretical Investigation of a New Series of NiII-LnIII-WV Heterotrimetallics: Understanding the SMM Behavior of Mixed Polynuclear Complexes.

Science.gov (United States)

Vieru, Veacheslav; Pasatoiu, Traian D; Ungur, Liviu; Suturina, Elizaveta; Madalan, Augustin M; Duhayon, Carine; Sutter, Jean-Pascal; Andruh, Marius; Chibotaru, Liviu F

2016-12-05

The polynuclear compounds containing anisotropic metal ions often exhibit efficient barriers for blocking of magnetization at fairly arbitrary geometries. However, at variance with mononuclear complexes, which usually become single-molecule magnets (SMM) under the sole requirement of a highly axial crystal field at the metal ion, the factors influencing the SMM behavior in polynuclear complexes, especially, with weakly axial magnetic ions, still remain largely unrevealed. As an attempt to clarify these conditions, we present here the synthesis, crystal structures, magnetic behavior, and ab initio calculations for a new series of Ni II -Ln III -W V trimetallics, [(CN) 7 W(CN)Ni(H 2 O)(valpn)Ln(H 2 O) 4 ]·H 2 O (Ln = Y 1, Eu 2, Gd 3, Tb 4, Dy 5, Lu 6). The surprising finding is the absence of the magnetic blockage even for compounds involving strongly anisotropic Dy III and Tb III metal ions. This is well explained by ab initio calculations showing relatively large transversal components of the g-tensor in the ground exchange Kramers doublets of 1 and 4 and large intrinsic tunneling gaps in the ground exchange doublets of 3 and 5. In order to get more insight into this behavior, another series of earlier reported compounds with the same trinuclear [W V Ni II Ln III ] core structure, [(CN) 7 W(CN)Ni(dmf)(valdmpn)Ln(dmf) 4 ]·H 2 O (Ln = Gd III 7, Tb III 8a, Dy III 9, Ho III 10), [(CN) 7 W(CN)Ni(H 2 O)(valdmpn)Tb(dmf) 2.5 (H 2 O) 1.5 ]·H 2 O·0.5dmf 8b, and [(CN) 7 W(CN)Ni(H 2 O)(valdmpn)Er(dmf) 3 (H 2 O) 1 ]·H 2 O·0.5dmf 11, has been also investigated theoretically. In this series, only 8b exhibits SMM behavior which is confirmed by the present ab initio calculations. An important feature for the entire series is the strong ferromagnetic coupling between Ni(II) and W(V), which is due to an almost perfect trigonal dodecahedron geometry of the octacyano wolframate fragment. The reason why only 8b is an SMM is explained by positive zero-field splitting on the nickel

NbCN Josephson junctions with AlN barriers

International Nuclear Information System (INIS)

Thomasson, S.L.; Murduck, J.M.; Chan, H.

1991-01-01

This paper reports on niobium carbonitride (NbCN) Josephson circuits which operate over a wider temperature range than either niobium or niobium nitride circuits. Higher operating temperature places NbCN technology more comfortably within the range of closed cycle refrigerators, a key factor in aerospace applications. We have fabricated tunnel junctions from NbCN films with transition temperatures up to 18 Kelvin. High quality NbCN tunnel junction fabrication generally requires low stress films with roughness less than the barrier thickness (∼20 Angstrom). We have developed scanning tunneling microscopy as a tool for measuring and optimizing film smoothness. Junctions formed in situ with AIN tunneling barriers show reproducible I-V characteristics

Interaction between gold (III) chloride and potassium hexacyanoferrate (II/III)-Does it lead to gold analogue of Prussian blue?

Energy Technology Data Exchange (ETDEWEB)

Harish, S. [Electrodics and Electrocatalysis Division, CSIR-Central Electrochemical Research Institute, Karaikudi 630006, Tamilnadu (India); Joseph, James, E-mail: jameskavlam@yahoo.com [Electrodics and Electrocatalysis Division, CSIR-Central Electrochemical Research Institute, Karaikudi 630006, Tamilnadu (India); Phani, K.L.N. [Electrodics and Electrocatalysis Division, CSIR-Central Electrochemical Research Institute, Karaikudi 630006, Tamilnadu (India)

2011-06-30

Highlights: > In group IB, Cu and Ag form Prussian blue analogues but similar formation of gold hexacyanoferrate was not found in the literature and non-existence of gold hexacyanoferrate remains a mystery. > Potential cycling of gold chloride and potassium ferro/ferri cyanide was resulted in the formation of Au-PB nano-composite. > Redox reaction between gold chloride and potassium ferrocyanide ion is spontaneous but no reaction occurs when gold chloride and potassium ferricyanide is mixed. > We are proposing the formation of a compound with general formula 'KFe{sub x}[Au(CN){sub 2}]{sub y}' and discussing the formation of gold hexacyanoferrate is not feasible by simple chemical or electrochemical reaction in contrast to other PB analogues. - Abstract: Prussian blue analogues are a class of compounds formed by the reaction between metal salt and potassium hexacyanoferrate (II/III). In our earlier report, the formation of Au-Prussian blue nano-composite was noticed on potential cycling the glassy carbon electrode in a medium containing gold (III) chloride and potassium hexacyanoferrate (III). Hence in this work, the formation of gold hexacyanoferrate was attempted by a simple chemical reaction. The reaction of gold (III) chloride with potassium hexacyanoferrate (II/III) was examined by UV-Vis spectroscopy and found that there is no redox reaction between gold (III) chloride and potassium hexacyanoferrate (III). However, the redox reaction occurs between gold (III) chloride and potassium hexacyanoferrate (II) leading to the formation of charge transfer band and the conversion of hexacyanoferrate (II) to hexacyanoferrate (III) was evidenced by the emergence of new absorption peaks in UV-Vis spectra. The oxidation state of gold in Au-Fe complex was found to be +1 from X-ray photoelectron spectroscopy. The stability of the Au-Fe complex was also studied by cyclic voltammetry. Cyclic voltammetric results indicated the presence of high spin iron in Au

Interaction between gold (III) chloride and potassium hexacyanoferrate (II/III)-Does it lead to gold analogue of Prussian blue?

International Nuclear Information System (INIS)

Harish, S.; Joseph, James; Phani, K.L.N.

2011-01-01

Highlights: → In group IB, Cu and Ag form Prussian blue analogues but similar formation of gold hexacyanoferrate was not found in the literature and non-existence of gold hexacyanoferrate remains a mystery. → Potential cycling of gold chloride and potassium ferro/ferri cyanide was resulted in the formation of Au-PB nano-composite. → Redox reaction between gold chloride and potassium ferrocyanide ion is spontaneous but no reaction occurs when gold chloride and potassium ferricyanide is mixed. → We are proposing the formation of a compound with general formula 'KFe x [Au(CN) 2 ] y ' and discussing the formation of gold hexacyanoferrate is not feasible by simple chemical or electrochemical reaction in contrast to other PB analogues. - Abstract: Prussian blue analogues are a class of compounds formed by the reaction between metal salt and potassium hexacyanoferrate (II/III). In our earlier report, the formation of Au-Prussian blue nano-composite was noticed on potential cycling the glassy carbon electrode in a medium containing gold (III) chloride and potassium hexacyanoferrate (III). Hence in this work, the formation of gold hexacyanoferrate was attempted by a simple chemical reaction. The reaction of gold (III) chloride with potassium hexacyanoferrate (II/III) was examined by UV-Vis spectroscopy and found that there is no redox reaction between gold (III) chloride and potassium hexacyanoferrate (III). However, the redox reaction occurs between gold (III) chloride and potassium hexacyanoferrate (II) leading to the formation of charge transfer band and the conversion of hexacyanoferrate (II) to hexacyanoferrate (III) was evidenced by the emergence of new absorption peaks in UV-Vis spectra. The oxidation state of gold in Au-Fe complex was found to be +1 from X-ray photoelectron spectroscopy. The stability of the Au-Fe complex was also studied by cyclic voltammetry. Cyclic voltammetric results indicated the presence of high spin iron in Au-Fe complex. Hence 'as

Estimation of CN Parameter for Small Agricultural Watersheds Using Asymptotic Functions

Directory of Open Access Journals (Sweden)

Tomasz Kowalik

2015-03-01

Full Text Available This paper investigates a possibility of using asymptotic functions to determine the value of curve number (CN parameter as a function of rainfall in small agricultural watersheds. It also compares the actually calculated CN with its values provided in the Soil Conservation Service (SCS National Engineering Handbook Section 4: Hydrology (NEH-4 and Technical Release 20 (TR-20. The analysis showed that empirical CN values presented in the National Engineering Handbook tables differed from the actually observed values. Calculations revealed a strong correlation between the observed CN and precipitation (P. In three of the analyzed watersheds, a typical pattern of the observed CN stabilization during abundant precipitation was perceived. It was found that Model 2, based on a kinetics equation, most effectively described the P-CN relationship. In most cases, the observed CN in the investigated watersheds was similar to the empirical CN, corresponding to average moisture conditions set out by NEH-4. Model 2 also provided the greatest stability of CN at 90% sampled event rainfall.

From Point Cloud to Digital Fabrication: a Tangible Reconstruction of Ca' Venier Dei Leoni, the Guggenheim Museum in Venice

Science.gov (United States)

Balletti, C.; D'Agnano, F.; Guerra, F.; Vernier, P.

2016-06-01

The paper describes how new digital methodologies can be used within the field of Cultural Heritage, not only with the aim of documenting the actual state of an architecture but to review the past transformations it has undergone, conserving and representing these histories as well. The premise to conservation and enhancement of our Heritage is a deep study in terms of position, shape, colour, and also of the historical and artistic features. Survey methods have acquired data acquisition techniques in line with technological progress: today's electronic and IT technologies, that are the tools of modern Geomatics, allow the effective survey and representation of 3D objects, from architectural structures to sculptures or archaeological finds. Over the last few years, the methodologies of acquisition and integrated representation for 3D patrimony documentation have developed and consolidated considerably: the possibilities of the digital realm can augment the understanding and the valorisation of a monument. The specific case offered in the present paper, Ca' Venier dei Leoni, the palace where is the Guggenheim Museum in Venice, is a significant example. It suggests not only the theme of the "no longer existing", or better never built, but also the opportunity to formulate hypotheses regarding its implementation and the impact that the palace would have had in the Venetian contest.

Reduction reactions of water soluble cyano-cobalt(III)-porphyrins: Metal versus ligand centered processes

International Nuclear Information System (INIS)

Mosseri, S.; Neta, P.; Harriman, A.; Hambright, P.

1990-01-01

Reduction reactions of dicyano-cobalt(III)-porphyrins [potential in vivo cyanide scavenger drugs] were studied by radiolytic and electrochemical methods using the water soluble tetrakis(4-sulfonatophenyl)porphyrin (TPPS) and tetrakis(N-methyl-4-pyridyl)porphyrin (TMPyP). For [(CN)2CoIIITPPS]-, reduction occurs stepwise to the CoII, CoI, and finally to the phlorin anion. This behavior is similar to that of the cobalt porphyrins in the absence of cyanide, except that the cyanide ligand shifts the reduction potentials to much more negative values. On the other hand, under radiolytic conditions, [(CN)2CoIIITMPyP]- is reduced on the porphyrin macrocycle by one electron to give the CoIII pi-radical anion, which disproportionates into the initial complex and the two-electron ring reduced CoIII phlorin. The radical anion is also formed by intramolecular electron transfer subsequent to the reaction of CoIITMPyP and cyanide. The results are compared with the chemistry of Vitamin B-12

Potassium tetracyanidoaurate(III monohydrate: a redetermination

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Nobuyuki Matsushita

2017-03-01

Full Text Available The structure of the title metal complex salt, K[Au(CN4]·H2O, has been redetermined using X-ray diffraction data at 173 K in order to improve the precision. The previous determination was based on neutron diffraction data [Bertinotti & Bertinotti (1970. Acta Cryst. B26, 422–428]. The title compound crystallizes in the space group P212121 with one potassium cation, one [Au(CN4]− anion and one water molecule in the asymmetric unit. The AuIII atom lies on a general position and has an almost square-planar coordination sphere defined by four cyanide ligands. Interactions between the potassium cation and N atoms of the complex anion, as well as O—H...N hydrogen bonds, lead to the formation of a three-dimensional framework structure.

cn.MOPS: mixture of Poissons for discovering copy number variations in next-generation sequencing data with a low false discovery rate.

Science.gov (United States)

Klambauer, Günter; Schwarzbauer, Karin; Mayr, Andreas; Clevert, Djork-Arné; Mitterecker, Andreas; Bodenhofer, Ulrich; Hochreiter, Sepp

2012-05-01

Quantitative analyses of next-generation sequencing (NGS) data, such as the detection of copy number variations (CNVs), remain challenging. Current methods detect CNVs as changes in the depth of coverage along chromosomes. Technological or genomic variations in the depth of coverage thus lead to a high false discovery rate (FDR), even upon correction for GC content. In the context of association studies between CNVs and disease, a high FDR means many false CNVs, thereby decreasing the discovery power of the study after correction for multiple testing. We propose 'Copy Number estimation by a Mixture Of PoissonS' (cn.MOPS), a data processing pipeline for CNV detection in NGS data. In contrast to previous approaches, cn.MOPS incorporates modeling of depths of coverage across samples at each genomic position. Therefore, cn.MOPS is not affected by read count variations along chromosomes. Using a Bayesian approach, cn.MOPS decomposes variations in the depth of coverage across samples into integer copy numbers and noise by means of its mixture components and Poisson distributions, respectively. The noise estimate allows for reducing the FDR by filtering out detections having high noise that are likely to be false detections. We compared cn.MOPS with the five most popular methods for CNV detection in NGS data using four benchmark datasets: (i) simulated data, (ii) NGS data from a male HapMap individual with implanted CNVs from the X chromosome, (iii) data from HapMap individuals with known CNVs, (iv) high coverage data from the 1000 Genomes Project. cn.MOPS outperformed its five competitors in terms of precision (1-FDR) and recall for both gains and losses in all benchmark data sets. The software cn.MOPS is publicly available as an R package at http://www.bioinf.jku.at/software/cnmops/ and at Bioconductor.

CN in the Sgr A* environment - first results

International Nuclear Information System (INIS)

Stankovic, M; Seaquist, E R; Muehle, S

2006-01-01

The radical CN, through the CN/HCN ratio, has proven to be an exceptionally good tool to study the photodissociation regions (PDRs) dominated by FUV radiation. Our region of interest, the circumnuclear disk (CND) surrounding Sgr A*, is exposed to the strong UV radiation field originating from the central stellar cluster. It contains potentially star forming cores recently elucidated by interferometric HCN observations with OVRO by Christopher et al. (2005). We present the results of preliminary observations of CN (N = 2-l) transitions with the IRAM 30-m telescope and report, for the first time, detection of CN emission in the GC region indicative of PDR, activity. This work motivates the further investigation of the role of PDRs in the clumpy medium of the Galactic center (GC) environment in global photodissociation and in promoting or inhibiting star formation in the CND

Technetium cyanide chemistry: synthesis and characterization of technetium(III) and -(V) cyanide complexes

International Nuclear Information System (INIS)

Trop, H.S.; Jones, A.G.; Davison, A.

1980-01-01

Several new technetium cyanide complexes have been prepared and characterized. The reaction of ammonium hexaiodotechnetate(IV) with potassium cyanide in refluxing aqueous methanol under nitrogen yields potassium heptacyanotechnetate(III) dihydrate, K 4 Tc(CN) 7 .2H 2 O (1). Infrared and Raman measurements indicate that 1 has a pentagonal bipyramidal structure (D/sub 5h/) in both solid and solution. Aqueous solutions of 1 are air sensitive, decomposing to potassium oxopentacyanotechnetate(V) tetrahydrate, K 2 TcO(CN) 5 .4H 2 O (2). This species can also be prepared from the reaction of TcO 2 .xH 2 O with hot aqueous potassium cyanide solutions. Hydrolysis of 2 in water yields potassium trans-dioxo-tetracyanotechnetate(V), K 3 TcO 2 (CN) 4 (3). Preparation of 3 can also be achieved from the treatment of [TcO 2 (Py) 4 ]ClO 4 .2H 2 O with aqueous potassium cyanide. Infrared and Raman measurements on 3 are consistent with the proposed trans-dioxo (D/sub 4h/) structure. Reaction of the oxotetrachlorotechnetate(V) anion, TcOCl 4 , with potassium cyanide in methanol produces trans-oxomethoxytetracyanotechnetate(V). [TcO(OMe)(CN) 4 ] (4). The full details of the synthesis and characterization of these interesting technetium(III) and -(V) complexes, as well as observations on the infrared and Raman spectra of trans-dioxo metal complexes and the hydrolysis of species 2, are presented

Ion beam analysis, corrosion resistance and nanomechanical properties of TiAlCN/CN{sub x} multilayer grown by reactive magnetron sputtering

Energy Technology Data Exchange (ETDEWEB)

Alemón, B.; Flores, M. [Departamento de Ingeniería de Proyectos, CUCEI, Universidad de Guadalajara, J. Guadalupe Zuno 48, Los Belenes, Zapopan, Jal. 45101 (Mexico); Canto, C. [Instituto de Física, UNAM, Avenida de la Investigación S/N, Coyoacán, Mexico, DF 04510 (Mexico); Andrade, E., E-mail: andrade@fisica.unam.mx [Instituto de Física, UNAM, Avenida de la Investigación S/N, Coyoacán, Mexico, DF 04510 (Mexico); Lucio, O.G. de [Instituto de Física, UNAM, Avenida de la Investigación S/N, Coyoacán, Mexico, DF 04510 (Mexico); Rocha, M.F. [ESIME-Z, Instituto Politécnico Nacional, ALM Zacatenco, Mexico, DF 07738 (Mexico); Broitman, E. [Thin Films Physics Division, IFM, Linköping University, SE-58183 Linköping (Sweden)

2014-07-15

A novel TiAlCN/CN{sub x} multilayer coating, consisting of nine TiAlCN/CN{sub x} periods with a top layer 0.5 μm of CN{sub x}, was designed to enhance the corrosion resistance of CoCrMo biomedical alloy. The multilayers were deposited by dc and RF reactive magnetron sputtering from Ti{sub 0.5}Al{sub 0.5} and C targets respectively in a N{sub 2}/Ar plasma. The corrosion resistance and mechanical properties of the multilayer coatings were analyzed and compared to CoCrMo bulk alloy. Ion beam analysis (IBA) and X-ray diffraction tests were used to measure the element composition profiles and crystalline structure of the films. Corrosion resistance was evaluated by means of potentiodynamic polarization measurements using simulated body fluid (SBF) at typical body temperature and the nanomechanical properties of the multilayer evaluated by nanoindentation tests were analyzed and compared to CoCrMo bulk alloy. It was found that the multilayer hardness and the elastic recovery are higher than the substrate of CoCrMo. Furthermore the coated substrate shows a better general corrosion resistance than that of the CoCrMo alloy alone with no observation of pitting corrosion.

Phonon dispersion curves for CsCN

International Nuclear Information System (INIS)

Gaur, N.K.; Singh, Preeti; Rini, E.G.; Galgale, Jyostna; Singh, R.K.

2004-01-01

The motivation for the present work was gained from the recent publication on phonon dispersion curves (PDCs) of CsCN from the neutron scattering technique. We have applied the extended three-body force shell model (ETSM) by incorporating the effect of coupling between the translation modes and the orientation of cyanide molecules for the description of phonon dispersion curves of CsCN between the temperatures 195 and 295 K. Our results on PDCs in symmetric direction are in good agreement with the experimental data measured with inelastic neutron scattering technique. (author)

Metalloporphyrin Co(III)TMPyP ameliorates acute, sublethal cyanide toxicity in mice.

Science.gov (United States)

Benz, Oscar S; Yuan, Quan; Amoscato, Andrew A; Pearce, Linda L; Peterson, Jim

2012-12-17

The formation of Co(III)TMPyP(CN)(2) at pH 7.4 has been shown to be completely cooperative (α(H) = 2) with an association constant of 2.1 (±0.2) × 10(11). The kinetics were investigated by stopped-flow spectrophotometry and revealed a complicated net reaction exhibiting 4 phases at pH 7.4 under conditions where cyanide was in excess. The data suggest molecular HCN (rather than CN(-)) to be the attacking nucleophile around neutrality. The two slower phases do not seem to be present when cyanide is not in excess, and the other two phases have rates comparable to that observed for cobalamin, a known effective cyanide scavenger. Addition of bovine serum albumin (BSA) did not affect the cooperativity of cyanide binding to Co(III)TMPyP, only lowered the equilibrium constant slightly to 1.2 (±0.2) × 10(11) and had an insignificant effect on the observed rate. A sublethal mouse model was used to assess the effectiveness of Co(III)TMPyP as a potential cyanide antidote. The administration of Co(III)TMPyP to sodium cyanide intoxicated mice resulted in the time required for the surviving mice to right themselves from a supine position being significantly decreased (9 ± 2 min) compared to that of the controls (33 ± 2 min). All observations were consistent with the demonstrated antidotal activity of Co(III)TMPyP operating through a cyanide-binding (i.e., scavenging) mechanism.

Lanthanide(III) complexes of bis-semicarbazone and bis-imine-substituted phenanthroline ligands: solid-state structures, photophysical properties, and anion sensing.

Science.gov (United States)

Nadella, Sandeep; Selvakumar, Paulraj M; Suresh, Eringathodi; Subramanian, Palani S; Albrecht, Markus; Giese, Michael; Fröhlich, Roland

2012-12-21

Phenanthroline-based hexadentate ligands L(1) and L(2) bearing two achiral semicarbazone or two chiral imine moieties as well as the respective mononuclear complexes incorporating various lanthanide ions, such as La(III), Eu(III), Tb(III), Lu(III), and Y(III) metal ions, were synthesized, and the crystal structures of [ML(1)Cl(3)] (M=La(III), Eu(III), Tb(III), Lu(III), or Y(III)) complexes were determined. Solvent or water molecules act as coligands for the rare-earth metals in addition to halide anions. The big Ln(III) ion exhibits a coordination number (CN) of 10, whereas the corresponding Eu(III), Tb(III), Lu(III), and Y(III) centers with smaller ionic radii show CN=9. Complexes of L(2), namely [ML(2)Cl(3)] (M=Eu(III), Tb(III), Lu(III), or Y(III)) ions could also be prepared. Only the complex of Eu(III) showed red luminescence, whereas all the others were nonluminescent. The emission properties of the Eu derivative can be applied as a photophysical signal for sensing various anions. The addition of phosphate anions leads to a unique change in the luminescence behavior. As a case study, the quenching behavior of adenosine-5'-triphosphate (ATP) was investigated at physiological pH value in an aqueous solvent. A specificity of the sensor for ATP relative to adenosine-5'-diphosphate (ADP) and adenosine-5'-monophosphate (AMP) was found. (31)P NMR spectroscopic studies revealed the formation of a [EuL(2)(ATP)] coordination species. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

7 CFR Appendix C to Part 226 - Child Nutrition (CN) Labeling Program

Science.gov (United States)

2010-01-01

...). EC17SE91.009 (c) The CN label statement includes the following: (1) The product identification number... 7 Agriculture 4 2010-01-01 2010-01-01 false Child Nutrition (CN) Labeling Program C Appendix C to.... C Appendix C to Part 226—Child Nutrition (CN) Labeling Program 1. The Child Nutrition (CN) Labeling...

7 CFR Appendix C to Part 225 - Child Nutrition (CN) Labeling Program

Science.gov (United States)

2010-01-01

...). EC17SE91.006 (c) The CN label statement includes the following: (1) The product identification number... 7 Agriculture 4 2010-01-01 2010-01-01 false Child Nutrition (CN) Labeling Program C Appendix C to... Appendix C to Part 225—Child Nutrition (CN) Labeling Program 1. The Child Nutrition (CN) Labeling Program...

A serials of sandwich-like trinuclear and one-dimensional chain cyanide-bridged iron(III)-copper(II) complexes: Syntheses, crystal structures and magnetic properties

Science.gov (United States)

Shi, Jingwen; Lan, Wenlong; Ren, Yanjie; Liu, Qingyun; Liu, Hui; Dong, Yunhui; Zhang, Daopeng

2018-04-01

Four pyridinecarboxamide trans-dicyanideiron(III) building blocks and one macrocyclic copper(II) compound have been employed to assemble cyanide-bridged heterometallic complexes, resulting in a serials of cyanide-bridged FeIII-CuII complexes with different structure types. The series of complexes can be formulated as: {[Cu(Cyclam)][Fe(bpb)(CN)2]2}·4H2O (1), {{[Cu(Cyclam)][Fe(bpb)(CN)2]}ClO4}n·nH2O (2), and {[Cu(Cyclam)][Fe(bpmb)(CN)2]2}·4H2O (3), {[Cu(Cyclam)][Fe(bpClb)(CN)2]2}·4H2O (4) and {{[Cu(Cyclam)][Fe(bpdmb)(CN)2]}ClO4}n·2nCH3OH (5) (bpb2- = 1,2-bis(pyridine-2-carboxamido)benzenate, bpmb2- = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate, bpClb2- = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate, bpdmb2- = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate, Cyclam = 1,4,8,11-tetraazacyclotetradecane). All the complexes have been characterized by elemental analysis, IR spectra and structural determination. Single X-ray diffraction analysis shows the similar neutral sandwich-like structures for complexes 1, 3 and 4, in which the two cyano precursors acting as monodentate ligand through one of their two cyanide groups were coordinated face to face to central Cu(II) ion. The complexes 2 and 5 can be structurally characterized as one-dimensional cationic single chain consisting of alternating units of [Cu(Cyclam)]2+ and [Fe(bpb/bpdmb)(CN)2]- with free ClO4- as balanced anion. Investigation over magnetic properties of the whole serials of complexes reveals the antiferromagnetic magnetic coupling between the neighboring cyanide-bridged Fe(III) and Cu(II) ions in complexes 3 and 4 and the ferromagnetic interaction in complexes 1, 2 and 5, respectively.

Synthesis and electrical, spectroscopic and nonlinear optical properties of cobalt molecular materials obtained from PcCo(CN)L (L = ethylenediamine, 1,4-diaminebutane, 1,12-diaminododecane and 2,6-diamineanthraquinone)

International Nuclear Information System (INIS)

Morales-Saavedra, O.G.; Sanchez-Vergara, M.E.; Rodriguez-Rosales, A.A.; Ortega-Martinez, R.; Ortiz-Rebollo, A.; Frontana-Uribe, B.A.; Garcia-Montalvo, V.

2010-01-01

Novel PcCo(CN)L monomeric complexes were synthesized from [PcCoCN] n compounds and bidentate axial ligands (L) such as ethylenediamine, 1,4-diaminebutane, 1,12-diaminedodecane and 2,6-diamineanthraquinone. These complexes were implemented to fabricate pellets and thin films by the vacuum thermal evaporation technique. The obtained compounds and deposited thin films were characterized by different spectroscopic techniques. Measurements of the electrical conductivity and the electrical current as a function of temperature were also carried out. IR-spectroscopy studies showed that the ligand attaches to the [PcCoCN] n unit. The C=N vibrational band is found in the PcCo(et)CN and PcCo(bu)CN molecular solids, although it is displaced with respect to other reported values. Compounds PcCo(do) 2 and PcCo(an) 2 do not show C=N vibrational bands. This fact suggests a double bond between the ligand and the macrocycle and a coordination at the fifth and sixth position on the Co(III) atom. UV-vis spectra of the thin films exhibited higher conjugation degree for the CN-based samples. Electrical conductivity for the PcCo(an) 2 complex was consistently low for all temperature ranges under measurement, whereas the other synthesized compounds showed a semiconductor-like dependence of electric current with temperature. Additionally, cubic nonlinear optical (NLO) characterizations of the film samples were performed with the Z-Scan and third harmonic generation (THG) techniques, all samples exhibit outstandingly high nonlinear activity.

Prediction of the Iron-Based Polynuclear Magnetic Superhalogens with Pseudohalogen CN as Ligands.

Science.gov (United States)

Ding, Li-Ping; Shao, Peng; Lu, Cheng; Zhang, Fang-Hui; Liu, Yun; Mu, Qiang

2017-07-17

To explore stable polynuclear magnetic superhalogens, we perform an unbiased structure search for polynuclear iron-based systems based on pseudohalogen ligand CN using the CALYPSO method in conjunction with density functional theory. The superhalogen properties, magnetic properties, and thermodynamic stabilities of neutral and anionic Fe 2 (CN) 5 and Fe 3 (CN) 7 clusters are investigated. The results show that both of the clusters have superhalogen properties due to their electron affinities (EAs) and that vertical detachment energies (VDEs) are significantly larger than those of the chlorine element and their ligand CN. The distribution of the extra electron analysis indicates that the extra electron is aggregated mainly into pseudohalogen ligand CN units in Fe 2 (CN) 5 ¯ and Fe 3 (CN) 7 ¯ cluster. These features contribute significantly to their high EA and VDE. Besides superhalogen properties, these two anionic clusters carry a large magnetic moment just like the Fe 2 F 5 ¯ cluster. Additionally, the thermodynamic stabilities are also discussed by calculating the energy required to fragment the cluster into various smaller stable clusters. It is found that Fe(CN) 2 is the most favorable fragmentation product for anionic Fe 2 (CN) 5 ¯ and Fe 3 (CN) 7 ¯ clusters, and both of the anions are less stable against ejection of Fe atoms than Fe(CN) n-x .

The effect of Ti(CN/TiNb(CN coating on erosion–corrosion resistance

Directory of Open Access Journals (Sweden)

William Aperador Chaparro

2012-05-01

Full Text Available The goal of this work was to study electrochemical behaviour in corrosion-erosion conditions for Ti(CN/TiNb(CN multilayer coatings having 1, 50, 100, 150 and 200 bilayer periods on AISI 4140 steel substrates by using a multi-target magnetron reactive sputtering device, with an r.f. source (13.56 MHz, two cylindrical magnetron cathodes and two stoichiometric TiC and Nb targets. The multi-layers were evaluated by comparing them to corrosion, erosion and erosion corrosion for a 30º impact angle in a solution of 0.5 M NaCl and silica, analysing the effect of impact angle and the number of bilayers on these coatings’ corrosion resistance. The electrochemical characterisation was performed using electrochemical impedance spectroscopy for analysing corrosion surface; surface morphology was characterised by using a high-resolution scanning electron microscope (SEM. The results showed a de-creased corrosion rate for multilayer systems tested at 30°.

A theoretical study of spectroscopy and metastability of the CN2+ dication

Czech Academy of Sciences Publication Activity Database

Fišer, J.; Polák, Rudolf

2012-01-01

Roč. 392, č. 1 (2012), s. 55-62 ISSN 0301-0104 Institutional research plan: CEZ:AV0Z40400503 Keywords : CN * CN+ * CN2+ Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.957, year: 2012

Seismotectonic models and CN algorithm: The case of Italy

International Nuclear Information System (INIS)

Costa, G.; Orozova Stanishkova, I.; Panza, G.F.; Rotwain, I.M.

1995-07-01

The CN algorithm is here utilized both for the intermediate term earthquake prediction and to validate the seismotectonic model of the Italian territory. Using the results of the analysis, made through the CN algorithm and taking into account the seismotectonic model, three areas, one for Northern Italy, one for Central Italy and one for Southern Italy, are defined. Two transition areas, between the three main areas are delineated. The earthquakes which occurred in these two areas contribute to the precursor phenomena identified by the CN algorithm in each main area. (author). 26 refs, 6 figs, 2 tabs

Insight into the Extraction Mechanism of Americium(III) over Europium(III) with Pyridylpyrazole: A Relativistic Quantum Chemistry Study.

Science.gov (United States)

Kong, Xiang-He; Wu, Qun-Yan; Wang, Cong-Zhi; Lan, Jian-Hui; Chai, Zhi-Fang; Nie, Chang-Ming; Shi, Wei-Qun

2018-05-10

Separation of trivalent actinides (An(III)) and lanthanides (Ln(III)) is one of the most important steps in spent nuclear fuel reprocessing. However, it is very difficult and challenging to separate them due to their similar chemical properties. Recently the pyridylpyrazole ligand (PypzH) has been identified to show good separation ability toward Am(III) over Eu(III). In this work, to explore the Am(III)/Eu(III) separation mechanism of PypzH at the molecular level, the geometrical structures, bonding nature, and thermodynamic behaviors of the Am(III) and Eu(III) complexes with PypzH ligands modified by alkyl chains (Cn-PypzH, n = 2, 4, 8) have been systematically investigated using scalar relativistic density functional theory (DFT). According to the NBO (natural bonding orbital) and QTAIM (quantum theory of atoms in molecules) analyses, the M-N bonds exhibit a certain degree of covalent character, and more covalency appears in Am-N bonds compared to Eu-N bonds. Thermodynamic analyses suggest that the 1:1 extraction reaction, [M(NO 3 )(H 2 O) 6 ] 2+ + PypzH + 2NO 3 - → M(PypzH)(NO 3 ) 3 (H 2 O) + 5H 2 O, is the most suitable for Am(III)/Eu(III) separation. Furthermore, the extraction ability and the Am(III)/Eu(III) selectivity of the ligand PypzH is indeed enhanced by adding alkyl-substituted chains in agreement with experimental observations. Besides this, the nitrogen atom of pyrazole ring plays a more significant role in the extraction reactions related to Am(III)/Eu(III) separation compared to that of pyridine ring. This work could identify the mechanism of the Am(III)/Eu(III) selectivity of the ligand PypzH and provide valuable theoretical information for achieving an efficient Am(III)/Eu(III) separation process for spent nuclear fuel reprocessing.

Synthesis and electrical, spectroscopic and nonlinear optical properties of cobalt molecular materials obtained from PcCo(CN)L (L = ethylenediamine, 1,4-diaminebutane, 1,12-diaminododecane and 2,6-diamineanthraquinone)

Energy Technology Data Exchange (ETDEWEB)

Morales-Saavedra, O.G., E-mail: omar.morales@ccadet.unam.mx [Lab. of Nonlinear Optics, Centro de Ciencias Aplicadas y Desarrollo Tecnologico, Universidad Nacional Autonoma de Mexico, CCADET-UNAM, Apdo, Postal 70-186, C.P. 04510 Coyoacan, Cd. Universitaria, Mexico D. F. (Mexico); Sanchez-Vergara, M.E. [Coordinacion de Ingenieria Mecatronica, Facultad de Ingenieria, Universidad Anahuac del Norte, Avenida Universidad Anahuac 46, Col. Lomas Anahuac, 52786 Huixquilucan, Estado de Mexico (Mexico); Rodriguez-Rosales, A.A.; Ortega-Martinez, R. [Lab. of Nonlinear Optics, Centro de Ciencias Aplicadas y Desarrollo Tecnologico, Universidad Nacional Autonoma de Mexico, CCADET-UNAM, Apdo, Postal 70-186, C.P. 04510 Coyoacan, Cd. Universitaria, Mexico D. F. (Mexico); Ortiz-Rebollo, A. [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, IIM-UNAM, A.P. 70-360 Coyoacan, 04510 Mexico D. F. (Mexico); Frontana-Uribe, B.A. [Centro Conjunto de Investigacion en Quimica Sustentable UAEM-UNAM Km. 14.5, Carretera Toluca-Atlacomulco, C.P. 50200 Toluca, Estado de Mexico (Mexico); Garcia-Montalvo, V. [Instituto de Quimica, Universidad Nacional Autonoma de Mexico, Circuito Exterior, Ciudad Universitaria, Mexico D. F. 04510 (Mexico)

2010-10-01

Novel PcCo(CN)L monomeric complexes were synthesized from [PcCoCN]{sub n} compounds and bidentate axial ligands (L) such as ethylenediamine, 1,4-diaminebutane, 1,12-diaminedodecane and 2,6-diamineanthraquinone. These complexes were implemented to fabricate pellets and thin films by the vacuum thermal evaporation technique. The obtained compounds and deposited thin films were characterized by different spectroscopic techniques. Measurements of the electrical conductivity and the electrical current as a function of temperature were also carried out. IR-spectroscopy studies showed that the ligand attaches to the [PcCoCN]{sub n} unit. The C=N vibrational band is found in the PcCo(et)CN and PcCo(bu)CN molecular solids, although it is displaced with respect to other reported values. Compounds PcCo(do){sub 2} and PcCo(an){sub 2} do not show C=N vibrational bands. This fact suggests a double bond between the ligand and the macrocycle and a coordination at the fifth and sixth position on the Co(III) atom. UV-vis spectra of the thin films exhibited higher conjugation degree for the CN-based samples. Electrical conductivity for the PcCo(an){sub 2} complex was consistently low for all temperature ranges under measurement, whereas the other synthesized compounds showed a semiconductor-like dependence of electric current with temperature. Additionally, cubic nonlinear optical (NLO) characterizations of the film samples were performed with the Z-Scan and third harmonic generation (THG) techniques, all samples exhibit outstandingly high nonlinear activity.

High pressure effects on a trimetallic Mn(II/III) SMM.

Science.gov (United States)

Prescimone, Alessandro; Sanchez-Benitez, Javier; Kamenev, Konstantin V; Moggach, Stephen A; Lennie, Alistair R; Warren, John E; Murrie, Mark; Parsons, Simon; Brechin, Euan K

2009-09-28

A combined study of the high pressure crystallography and high pressure magnetism of the complex [Mn3(Hcht)2(bpy)4](ClO4)3.Et2O.2MeCN (1.Et2O.2MeCN) (H3cht is cis,cis-1,3,5-cyclohexanetriol) is presented in an attempt to observe and correlate pressure induced changes in its structural and physical properties. At 0.16 GPa the complex 1.Et2O.2MeCN loses all associated solvent in the crystal lattice, becoming 1. At higher pressures structural distortions occur changing the distances between the metal centres and the bridging oxygen atoms making the magnetic exchange between the manganese ions weaker. No significant variations are observed in the Jahn-Teller axis of the only Mn(III) present in the structure. High pressure dc chiMT plots display a gradual decrease in both the low temperature value and slope. Simulations show a decrease in J with increasing pressure although the ground state is preserved. Magnetisation data do not show any change in |D|.

Facile and reversible formation of iron(III)-oxo-cerium(IV) adducts from nonheme oxoiron(IV) complexes and cerium(III)

Energy Technology Data Exchange (ETDEWEB)

Draksharapu, Apparao; Rasheed, Waqas; Klein, Johannes E.M.N.; Que, Lawrence Jr. [Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN (United States)

2017-07-24

Ceric ammonium nitrate (CAN) or Ce{sup IV}(NH{sub 4}){sub 2}(NO{sub 3}){sub 6} is often used in artificial water oxidation and generally considered to be an outer-sphere oxidant. Herein we report the spectroscopic and crystallographic characterization of [(N4Py)Fe{sup III}-O-Ce{sup IV}(OH{sub 2})(NO{sub 3}){sub 4}]{sup +} (3), a complex obtained from the reaction of [(N4Py)Fe{sup II}(NCMe)]{sup 2+} with 2 equiv CAN or [(N4Py)Fe{sup IV}=O]{sup 2+} (2) with Ce{sup III}(NO{sub 3}){sub 3} in MeCN. Surprisingly, the formation of 3 is reversible, the position of the equilibrium being dependent on the MeCN/water ratio of the solvent. These results suggest that the Fe{sup IV} and Ce{sup IV} centers have comparable reduction potentials. Moreover, the equilibrium entails a change in iron spin state, from S=1 Fe{sup IV} in 2 to S=5/2 in 3, which is found to be facile despite the formal spin-forbidden nature of this process. This observation suggests that Fe{sup IV}=O complexes may avail of reaction pathways involving multiple spin states having little or no barrier. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Enantiomeric separation of iridium (III) complexes using HPLC chiral stationary phases based on amylose derivatives

International Nuclear Information System (INIS)

Kim, Hee Eun; Seo, Na Hyeon; Hyun, Myung Ho

2016-01-01

Cyclometalated iridium (III) complexes formed with three identical cyclometalating (C-N) ligands (homoleptic) or formed with two cyclometalating (C-N) ligands and one ancillary (LX) ligand (heteroleptic) have been known as highly phosphorescent materials and, thus, they have been utilized as efficient phosphorescent dopants in organic light emitting diodes (OLEDs) 1–3 or as effective phosphorescent chemosensors. 4–7 Cylometalated iridium (III) complexes are chiral compounds consisting of lambda (Λ, left-handed) and delta (Δ, right-handed) isomers. Racemic cyclometa- lated iridium (III) complexes emit light with no net polarization, but optically active cyclometalated iridium (III) complexes emit circularly polarized light. 8,9 Circularly polarized light can be used in various fields including highly efficient three dimensional electronic devices, photo nic devices for optical data storage, biological assays, and others. 8,9 In order to obtain optically active cylometalated iridium (III) complexes and to determine the enantiomeric composition of optically active cylometalated iridium (III) complexes, liquid chromatogr aphic enantiomer separation method on chiral stationary phases (CSPs) has been used. For example, Okamoto and coworkers first reported the high performance liquid chromatographic (HPLC) direct enantiomeric separation of two homoleptic cylometalated iridium (III) complexes on immobilized amylose tris(3,5- dimethylphenylcarbamate) (Chiralpak IA), coated cellulose tris(3,5-dimethylphenylcarbamate) (Chiralc el OD), and coated cellulose tris(4-methylbenzoate) (Chiralce l OJ). 10 Supercritical fluid chromatography (SFC) was also used by Bernhard and coworkers for the enantiomeric separation of cylometalated iridium (III) complexes on coated amylose tris(3,5-dimethylphenylcarbamate) (Chiralpak AD-H). 8 However, the general use of the HPLC method for the direct enantiomeric separation of homoleptic

Enantiomeric separation of iridium (III) complexes using HPLC chiral stationary phases based on amylose derivatives

Energy Technology Data Exchange (ETDEWEB)

Kim, Hee Eun; Seo, Na Hyeon; Hyun, Myung Ho [Dept. of Chemistry and Chemistry Institute for Functional Materials, Pusan National University, Busan (Korea, Republic of)

2016-12-15

Cyclometalated iridium (III) complexes formed with three identical cyclometalating (C-N) ligands (homoleptic) or formed with two cyclometalating (C-N) ligands and one ancillary (LX) ligand (heteroleptic) have been known as highly phosphorescent materials and, thus, they have been utilized as efficient phosphorescent dopants in organic light emitting diodes (OLEDs) 1–3 or as effective phosphorescent chemosensors. 4–7 Cylometalated iridium (III) complexes are chiral compounds consisting of lambda (Λ, left-handed) and delta (Δ, right-handed) isomers. Racemic cyclometa- lated iridium (III) complexes emit light with no net polarization, but optically active cyclometalated iridium (III) complexes emit circularly polarized light. 8,9 Circularly polarized light can be used in various fields including highly efficient three dimensional electronic devices, photo nic devices for optical data storage, biological assays, and others. 8,9 In order to obtain optically active cylometalated iridium (III) complexes and to determine the enantiomeric composition of optically active cylometalated iridium (III) complexes, liquid chromatogr aphic enantiomer separation method on chiral stationary phases (CSPs) has been used. For example, Okamoto and coworkers first reported the high performance liquid chromatographic (HPLC) direct enantiomeric separation of two homoleptic cylometalated iridium (III) complexes on immobilized amylose tris(3,5- dimethylphenylcarbamate) (Chiralpak IA), coated cellulose tris(3,5-dimethylphenylcarbamate) (Chiralc el OD), and coated cellulose tris(4-methylbenzoate) (Chiralce l OJ). 10 Supercritical fluid chromatography (SFC) was also used by Bernhard and coworkers for the enantiomeric separation of cylometalated iridium (III) complexes on coated amylose tris(3,5-dimethylphenylcarbamate) (Chiralpak AD-H). 8 However, the general use of the HPLC method for the direct enantiomeric separation of homoleptic.

Colorimetric and luminescent bifunctional iridium(III) complexes for the sensitive recognition of cyanide ions

Science.gov (United States)

Chen, Xiudan; Wang, Huili; Li, Jing; Hu, Wenqin; Li, Mei-Jin

2017-02-01

Two new cyclometalated iridium(III) complexes [(ppy)2Irppz]Cl (1) and [(ppy)2Irbppz]Cl (2) (where ppy = 2-phenylpyridine, ppz = 4,7-phenanthrolino-5,6:5,6-pyrazine, bppz = 2.3-di-2-pyridylpyrazine), were designed and synthesized. The structure of [(ppy)2Irppz]Cl was determined by single crystal X-ray diffraction. Their photophysical properties were also studied. This kind of complexes could coordinate with Cu2 +, the photoluminescence (PL) of the complex was quenched, and the color changed from orange-red to green. The forming M-Cu (M: complexes 1 and 2) ensemble could be further utilized as a colorimetric and emission ;turn-on; bifunctional detection for CN-, especially for complex 1-Cu2 + showed a high sensitivity toward CN- with a limit of diction is 97 nM. Importantly, this kind of iridium(III) complexes shows a unique recognition of cyanide ions over other anions which makes it an eligible sensing probe for cyanide ions.

Structure and bonding of ScCN and ScNC: Ground and low-lying states

International Nuclear Information System (INIS)

Kalemos, Apostolos; Metropoulos, Aristophanes; Mavridis, Aristides

2012-01-01

Graphical abstract: The experimentally unknown systems ScCN and ScNC have been studied through single reference CISD and CCSD(T) methods. A total of 20 = 10 (ScCN) + 10 (ScNC) states were examined. All states are quite ionic whereas ScNC(X ∼3 Δ) is stabler than ScCN(X ∼3 Δ) by ∼5 kcal/mol. Display Omitted Highlights: ► We have studied through ab initio methods the polytopic system Sc[CN]. ► A series of low lying states for both isomeric forms have been examined. ► Around equilibrium the system displays a pronounced Sc + [CN] − ionic character. - Abstract: We have studied the experimentally unknown Sc[CN] molecular system in both its isomeric forms, scandium cyanide (ScCN) and isocyanide (ScNC), through ab initio computations. We report energetics, geometries, harmonic frequencies, and dipole moments for the first 20 Sc[CN] states correlating diabatically to Sc + ( 3 D, 1 D, 3 F) + CN − (X 1 Σ + ). Both isomers have a pronounced ionic character around equilibrium due to the high electron affinity of the CN group and the low ionization energy of the Sc atom. According to our calculations the ScNC isomer (X ∼3 Δ) is stabler than the ScCN(X ∼3 Δ) by ∼5 kcal/mol.

Ordered perovskites with cationic vacancies. 9. Compounds of the type Sr/sub 2/Srsub(1/4)Bsub(1/2)sup(III)vacantsub(1/4)WO/sub 6/ equivalent to Sr/sub 8/SrB/sub 2/sup(III)vacantW/sub 4/O/sub 24/ (Bsup(III) = La, Pr, Nd, Sm - Tm, Y)

Energy Technology Data Exchange (ETDEWEB)

Kemmler-Sack, S; Ehmann, A [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1981-08-01

The compounds Sr/sub 2/Srsub(1/4)Bsub(1/2)sup(III)vacantsub(1/4)WO/sub 6/ equivalent to Sr/sub 8/SrB/sub 2/sup(III)vacantW/sub 4/O/sub 24/ belong to the group of perovskites with octahedral cationic vacancies (cation/vacancy ratio (CN 6) = 7:1). For the larger Bsup(III) ions (La, Pr, Nd, Sm-Dy) different ordering effects are observed. The perovskites with Bsup(III) = Sm, Eu, Gd are polymorphic too (HT modification: higher ordered cubic perovskite (Bsup(III) = Gd: a = 2 x 8.23/sub 4/ A); LT modification: hexagonal perovskite stacking polytype (Bsup(III) = Gd: a = 9.95/sub 4/ A; c = 19.0/sub 4/ A)). With the smaller Bsup(III) ions (Ho, Er, Tm and Y) a cubic, 1:1 ordered perovskite type is observed.

Polarization due to dust scattering in the planetary nebula Cn1-1

International Nuclear Information System (INIS)

Bhatt, H.C.

1989-01-01

The peculiar emission-line object Cn1-1 (=HDE330036=PK330+4 degrees 1), classified both as a symbiotic star and as a planetary nebula, was detected by the Infrared Astronomical Satellite (IRAS) as a strong source of far-infrared dust in the system. Bhatt and Mallik (1986) discussed the nature of the dust in Cn1-1 and argued that the object is a Type I protoplanetary nebula in a binary system. The argument presented here is that the polarization is intrinsic to Cn1-1 and is due to scattering by large (compared to interstellar) dust grains in the protoplanetary nebula that are asymmetrically distributed around the central star. The large degree of polarization (approximately 3 percent for the Cn1-1 distance of approximately 450 pc) with a large lambda(sub max) is naturally explained if it is caused by scattering by large dust grains in the Cn1-1 nebula. Since the H(sub alpha) line is also polarized at the same level and position angle as the continuum, the dust must be asymmetrically distributed around the central star. The morphology of the protoplanetary nebula in Cn1-1 may be bipolar. Thus, the polarization observations support the suggestion that Cn1-1 is a bipolar Type I planetary nebula

New approach to neurorehabilitation: cranial nerve noninvasive neuromodulation (CN-NINM) technology

Science.gov (United States)

Danilov, Yuri P.; Tyler, Mitchel E.; Kaczmarek, Kurt A.; Skinner, Kimberley L.

2014-06-01

Cranial Nerve NonInvasive NeuroModulation (CN-NINM) is a primary and complementary multi-targeted rehabilitation therapy that appears to initiate the recovery of multiple damaged or suppressed brain functions affected by neurological disorders. It is deployable as a simple, home-based device (portable neuromodulation stimulator, or PoNSTM) and training regimen following initial patient training in an outpatient clinic. It may be easily combined with many existing rehabilitation therapies, and may reduce or eliminate the need for more aggressive invasive procedures or possibly decrease total medication intake. CN-NINM uses sequenced patterns of electrical stimulation on the tongue. Our hypothesis is that CN-NINM induces neuroplasticity by noninvasive stimulation of two major cranial nerves: trigeminal (CN-V), and facial (CN-VII). This stimulation excites a natural flow of neural impulses to the brainstem (pons varolli and medulla), and cerebellum, to effect changes in the function of these targeted brain structures, extending to corresponding nuclei of the brainstem. CN-NINM represents a synthesis of a new noninvasive brain stimulation technique with applications in physical medicine, cognitive, and affective neurosciences. Our new stimulation method appears promising for treatment of a full spectrum of movement disorders, and for both attention and memory dysfunction associated with traumatic brain injury.

Estimation of CN Parameter for Small Agricultural Watersheds Using Asymptotic Functions

OpenAIRE

Tomasz Kowalik; Andrzej Walega

2015-01-01

This paper investigates a possibility of using asymptotic functions to determine the value of curve number (CN) parameter as a function of rainfall in small agricultural watersheds. It also compares the actually calculated CN with its values provided in the Soil Conservation Service (SCS) National Engineering Handbook Section 4: Hydrology (NEH-4) and Technical Release 20 (TR-20). The analysis showed that empirical CN values presented in the National Engineering Handbook tables differed from t...

7 CFR Appendix C to Part 220 - Child Nutrition (CN) Labeling Program

Science.gov (United States)

2010-01-01

... product label that contains a CN label statement and CN logo as defined in paragraph 3 (b) and (c) below... statement” as defined in paragraph 3(c). EC17SE91.003 (c) The “CN label statement” includes the following... alternate product toward the meat/meat alternate, bread/bread alternate, and/or vegetable/fruit component of...

InterProScan Result: CN211485 [KAIKOcDNA[Archive

Lifescience Database Archive (English)

Full Text Available CN211485 CN211485_2_ORF1 AA5126E0BA1C15EC PRINTS PR00385 P450 3.6e-08 T IPR001128 Cytochrome P450 Molecular... Function: monooxygenase activity (GO:0004497)|Molecular Function: iron ion binding (GO:0005506)|Molecular... Function: electron carrier activity (GO:0009055)|Molecular Function: heme binding (GO:0020037) ...

A Novel Cyanide-Bridged Thulium-Nickel Heterobimetallic Polymeric Complex (H2O)2(DMF)10Tm2[Ni(CN)4]2[Ni(CN)4] including O-H···N Hydrogen Bond

International Nuclear Information System (INIS)

Chung, Janghoon; Park, Daeyoung; Song, Mina; Ha, Sungin; Kang, Ansoo; Moon, Sangbong; Ryu, Cheolhwi

2012-01-01

The experimental section lists the observed infrared absorption frequencies for the complex. Typically bridging CN ligands have higher stretching frequencies than the terminal CN ligands. Accordingly, cyanide stretching bands (2170, 2156, 2139 cm -1 . at higher frequencies than the stretching band (2127 cm -1 ) of K 2 [Ni(CN) 4 ] are assigned to bridging cyanide ligands. The band at 2128 cm -1 is assigned to terminal cyanide ligands because their location in the cyanide stretching region compares with the absorption observed for the nonbridging cyanide ligands in K 2 [Ni(CN) 4 ]. Array (H 2 O) 2 (DMF) 10 Tm 2 [Ni(CN) 4 ] 2 [Ni(CN) 4 ] and other lanthanide metal-Ni systems display similar CN stretching patterns in their spectra. A broad absorption band at 2950-3550 cm -1 was observed in the spectrum. This supports the presence of O-H···N intermolecular hydrogen bond interactions between the polymers

First detection of cyanamide (NH2CN) towards solar-type protostars

Science.gov (United States)

Coutens, A.; Willis, E. R.; Garrod, R. T.; Müller, H. S. P.; Bourke, T. L.; Calcutt, H.; Drozdovskaya, M. N.; Jørgensen, J. K.; Ligterink, N. F. W.; Persson, M. V.; Stéphan, G.; van der Wiel, M. H. D.; van Dishoeck, E. F.; Wampfler, S. F.

2018-05-01

Searches for the prebiotically relevant cyanamide (NH2CN) towards solar-type protostars have not been reported in the literature. We present here the first detection of this species in the warm gas surrounding two solar-type protostars, using data from the Atacama Large Millimeter/Submillimeter Array Protostellar Interferometric Line Survey (PILS) of IRAS 16293-2422 B and observations from the IRAM Plateau de Bure Interferometer of NGC 1333 IRAS2A. We also detected the deuterated and 13C isotopologs of NH2CN towards IRAS 16293-2422 B. This is the first detection of NHDCN in the interstellar medium. Based on a local thermodynamic equilibrium analysis, we find that the deuteration of cyanamide ( 1.7%) is similar to that of formamide (NH2CHO), which may suggest that these two molecules share NH2 as a common precursor. The NH2CN/NH2CHO abundance ratio is about 0.2 for IRAS 16293-2422 B and 0.02 for IRAS2A, which is comparable to the range of values found for Sgr B2. We explored the possible formation of NH2CN on grains through the NH2 + CN reaction using the chemical model MAGICKAL. Grain-surface chemistry appears capable of reproducing the gas-phase abundance of NH2CN with the correct choice of physical parameters.

Study on re-sputtering during CN{sub x} film deposition through spectroscopic diagnostics of plasma

Energy Technology Data Exchange (ETDEWEB)

Liang, Peipei; Yang, Xu; Li, Hui; Cai, Hua [Department of Optical Science and Engineering, Fudan University, Shanghai 200433 (China); Sun, Jian; Xu, Ning [Department of Optical Science and Engineering, Fudan University, Shanghai 200433 (China); Shanghai Engineering Research Center of Ultra-Precision Optical Manufacturing, Fudan University, Shanghai 200433 (China); Wu, Jiada, E-mail: jdwu@fudan.edu.cn [Department of Optical Science and Engineering, Fudan University, Shanghai 200433 (China); Shanghai Engineering Research Center of Ultra-Precision Optical Manufacturing, Fudan University, Shanghai 200433 (China); Engineering Research Center of Advanced Lighting Technology, Ministry of Education, Fudan University, Shanghai 200433 (China)

2015-10-15

A nitrogen-carbon plasma was generated during the deposition of carbon nitride (CN{sub x}) thin films by pulsed laser ablation of a graphite target in a discharge nitrogen plasma, and the optical emission of the generated nitrogen-carbon plasma was measured for the diagnostics of the plasma and the characterization of the process of CN{sub x} film deposition. The nitrogen-carbon plasma was recognized to contain various species including nitrogen molecules and molecular ions excited in the ambient N{sub 2} gas, carbon atoms and atomic ions ablated from the graphite target and CN radicals. The temporal evolution and spatial distribution of the CN emission and their dependence on the substrate bias voltage show two groups of CN radicals flying in opposite directions. One represents the CN radicals formed as the products of the reactions occurring in the nitrogen-carbon plasma, revealing the reactive deposition of CN{sub x} film due to the reactive expansion of the ablation carbon plasma in the discharge nitrogen plasma and the effective formation of gaseous CN radicals as precursors for CN{sub x} film growth. The other one represents the CN radicals re-sputtered from the growing CN{sub x} film by energetic plasma species, evidencing the re-sputtering of the growing film accompanying film growth. And, the re-sputtering presents ion-induced sputtering features.

SCS-CN based time-distributed sediment yield model

Science.gov (United States)

Tyagi, J. V.; Mishra, S. K.; Singh, Ranvir; Singh, V. P.

2008-05-01

SummaryA sediment yield model is developed to estimate the temporal rates of sediment yield from rainfall events on natural watersheds. The model utilizes the SCS-CN based infiltration model for computation of rainfall-excess rate, and the SCS-CN-inspired proportionality concept for computation of sediment-excess. For computation of sedimentographs, the sediment-excess is routed to the watershed outlet using a single linear reservoir technique. Analytical development of the model shows the ratio of the potential maximum erosion (A) to the potential maximum retention (S) of the SCS-CN method is constant for a watershed. The model is calibrated and validated on a number of events using the data of seven watersheds from India and the USA. Representative values of the A/S ratio computed for the watersheds from calibration are used for the validation of the model. The encouraging results of the proposed simple four parameter model exhibit its potential in field application.

Pressure-induced polymerization of P(CN){sub 3}

Energy Technology Data Exchange (ETDEWEB)

Gou, Huiyang, E-mail: hgou@ciw.edu, E-mail: tstrobel@ciw.edu; Kim, Duck Young; Strobel, Timothy A., E-mail: hgou@ciw.edu, E-mail: tstrobel@ciw.edu [Geophysical Laboratory, Carnegie Institution of Washington, 5251 Broad Branch Road, NW, Washington, DC 20015 (United States); Yonke, Brendan L. [NRC Postdoctoral Associate, Naval Research Laboratory, 4555 Overlook Ave., SW, Washington, DC 20375 (United States); Epshteyn, Albert [Naval Research Laboratory, 4555 Overlook Ave., SW, Washington, DC 20375 (United States); Smith, Jesse S. [High Pressure Collaborative Access Team, Geophysical Laboratory, Carnegie Institution of Washington, Argonne, Illinois 60439 (United States)

2015-05-21

Motivated to explore the formation of novel extended carbon-nitrogen solids via well-defined molecular precursor pathways, we studied the chemical reactivity of highly pure phosphorous tricyanide, P(CN){sub 3}, under conditions of high pressure at room temperature. Raman and infrared (IR) spectroscopic measurements reveal a series of phase transformations below 10 GPa, and several low-frequency vibrational modes are reported for the first time. Synchrotron powder X-ray diffraction measurements taken during compression show that molecular P(CN){sub 3} is highly compressible, with a bulk modulus of 10.0 ± 0.3 GPa, and polymerizes into an amorphous solid above ∼10.0 GPa. Raman and IR spectra, together with first-principles molecular-dynamics simulations, show that the amorphization transition is associated with polymerization of the cyanide groups into CN bonds with predominantly sp{sup 2} character, similar to known carbon nitrides, resulting in a novel phosphorous carbon nitride (PCN) polymeric phase, which is recoverable to ambient pressure.

Tetraethylammonium (2,2′-bipyridinetetracyanidocobaltate(III sesquihydrate acetonitrile solvate

Directory of Open Access Journals (Sweden)

Ganna Lyubartseva

2010-04-01

Full Text Available The title complex, (C8H20N[Co(CN4(C10H8N2]·CH3CN·1.5H2O, consists of tetraethyl ammonium cations, mononuclear [CoIIIbpy(CN4]− anions and uncoordinated water and acetonitrile molecules. The CoIII atom is six-coordinated by two 2,2′-bipyridine (bpy N atoms and four cyanide C atoms in a distorted octahedral geometry. The acute bite angle of the chelating bpy [82.28 (8°] is the main factor accounting for this distortion. In addition, the tetraethylammonium cation is significantly disordered [occupancy ratio 0.611 (3:0.389 (3]. The presence of water molecules, one of which is disordered over two positions about an inversion center, results in the formation of a network of O—H...N hydrogen bonds involving the cyanide N atoms.

THE SPATIAL DISTRIBUTION OF OH AND CN RADICALS IN THE COMA OF COMET ENCKE

International Nuclear Information System (INIS)

Ihalawela, Chandrasiri A.; Pierce, Donna M.; Dorman, Garrett R.; Cochran, Anita L.

2011-01-01

Multiple potential parent species have been proposed to explain CN abundances in comet comae, but the parent has not been definitively identified for all comets. This study examines the spatial distribution of CN radicals in the coma of comet Encke and determines the likelihood that CN is a photodissociative daughter of HCN in the coma. Comet Encke is the shortest orbital period (3.3 years) comet known and also has a low dust-to-gas ratio based on optical observations. Observations of CN were obtained from 2003 October 22 to 24, using the 2.7 m telescope at McDonald Observatory. To determine the parent of CN, the classical vectorial model was modified by using a cone shape in order to reproduce Encke's highly aspherical and asymmetric coma. To test the robustness of the modified model, the spatial distribution of OH was also modeled. This also allowed us to obtain CN/OH ratios in the coma. Overall, we find the CN/OH ratio to be 0.009 ± 0.004. The results are consistent with HCN being the photodissociative parent of CN, but we cannot completely rule out other possible parents such as CH 3 CN and HC 3 N. We also found that the fan-like feature spans ∼90°, consistent with the results of Woodney et al..

CN rings in full protoplanetary disks around young stars as probes of disk structure

Science.gov (United States)

Cazzoletti, P.; van Dishoeck, E. F.; Visser, R.; Facchini, S.; Bruderer, S.

2018-01-01

Aims: Bright ring-like structure emission of the CN molecule has been observed in protoplanetary disks. We investigate whether such structures are due to the morphology of the disk itself or if they are instead an intrinsic feature of CN emission. With the intention of using CN as a diagnostic, we also address to which physical and chemical parameters CN is most sensitive. Methods: A set of disk models were run for different stellar spectra, masses, and physical structures via the 2D thermochemical code DALI. An updated chemical network that accounts for the most relevant CN reactions was adopted. Results: Ring-shaped emission is found to be a common feature of all adopted models; the highest abundance is found in the upper outer regions of the disk, and the column density peaks at 30-100 AU for T Tauri stars with standard accretion rates. Higher mass disks generally show brighter CN. Higher UV fields, such as those appropriate for T Tauri stars with high accretion rates or for Herbig Ae stars or for higher disk flaring, generally result in brighter and larger rings. These trends are due to the main formation paths of CN, which all start with vibrationally excited H_2^* molecules, that are produced through far ultraviolet (FUV) pumping of H2. The model results compare well with observed disk-integrated CN fluxes and the observed location of the CN ring for the TW Hya disk. Conclusions: CN rings are produced naturally in protoplanetary disks and do not require a specific underlying disk structure such as a dust cavity or gap. The strong link between FUV flux and CN emission can provide critical information regarding the vertical structure of the disk and the distribution of dust grains which affects the UV penetration, and could help to break some degeneracies in the SED fitting. In contrast with C2H or c-C3H2, the CN flux is not very sensitive to carbon and oxygen depletion.

Rhodium(III)-Catalyzed Amidation of Unactivated C(sp(3) )-H Bonds.

Science.gov (United States)

Wang, He; Tang, Guodong; Li, Xingwei

2015-10-26

Nitrogenation by direct functionalization of C-H bonds represents an important strategy for constructing C-N bonds. Rhodium(III)-catalyzed direct amidation of unactivated C(sp(3) )-H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp(3) )-H bonds are amidated under rhodium catalysis in high efficiency using 3-substituted 1,4,2-dioxazol-5-ones as the amide source. The protocol broadens the scope of rhodium(III)-catalyzed C(sp(3) )-H activation chemistry, and is applicable to the late-stage functionalization of natural products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Regional Calibration of SCS-CN L-THIA Model: Application for Ungauged Basins

OpenAIRE

Jeon, Ji-Hong; Lim, Kyoung; Engel, Bernard

2014-01-01

Estimating surface runoff for ungauged watershed is an important issue. The Soil Conservation Service Curve Number (SCS-CN) method developed from long-term experimental data is widely used to estimate surface runoff from gaged or ungauged watersheds. Many modelers have used the documented SCS-CN parameters without calibration, sometimes resulting in significant errors in estimating surface runoff. Several methods for regionalization of SCS-CN parameters were evaluated. The regionalization met...

Synthesis of Diazonium Tetrachloroaurate(III Precursors for Surface Grafting

Directory of Open Access Journals (Sweden)

Sabine N. Neal

2013-12-01

Full Text Available The synthesis of diazonium tetrachloroaurate(III complexes [R-4-C6H4N≡N]AuCl4 involves protonation of anilines CN-4-C6H4NH2, C8F17-4-C6H4NH2, and C6H13-4-C6H4NH2 with tetrachloroauric acid H[AuCl4] 3H2O in acetonitrile followed by one-electron oxidation using [NO]PF6. FT-IR shows the diazonium stretching frequency at 2277 cm−1 (CN, 2305 cm−1 (C8F17, and 2253 cm−1 (C6H13. Thermogravimetric Analysis (TGA shows the high stabilities of the electron-withdrawing substituents C8F17 and CN compared with the electron-donating substituent C6H13. Residual Gas Analysis (RGA shows the release of molecular nitrogen as the main gas residue among other small molecular weight chlorinated hydrocarbons and chlorobenzene. Temperature-Dependent X-Ray Powder Diffraction (TD-XRD shows the thermal decomposition in C6H13 diffraction patterns at low temperature of 80 °C which supports the TGA and RGA (TGA-MS conclusions. X-ray structure shows N≡N bond distance of approximately 1.10 Å and N≡N-C bond angle of 178°.

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.

Structure of MoCN films deposited by cathodic arc evaporation

Energy Technology Data Exchange (ETDEWEB)

Gilewicz, A., E-mail: adam.gilewicz@tu.koszalin.pl [Koszalin University of Technology, Faculty of Technology and Education, Sniadeckich 2, 75-453 Koszalin (Poland); Jedrzejewski, R.; Kochmanska, A.E. [West Pomeranian University of Technology Szczecin, Faculty of Mechanical Engineering and Mechatronics, 19 Piastów Ave., 70-313 Szczecin (Poland); Warcholinski, B. [Koszalin University of Technology, Faculty of Technology and Education, Sniadeckich 2, 75-453 Koszalin (Poland)

2015-02-27

Molybdenum carbonitride (MoCN) coatings were deposited onto HS6-5-2 steel substrate using pure Mo targets in mixed acetylene and nitrogen atmosphere by cathodic arc evaporation. The structural properties of MoCN coatings with different carbon contents (as an effect of the C{sub 2}H{sub 2} flow rate) were investigated systematically. Phase and chemical composition evolution of the coatings were characterized both by the glancing angle of X-ray diffraction (XRD) and wavelength dispersive spectrometry, respectively. These analyses have been supplemented by estimates of grain sizes and stress in the coatings. The XRD results show that the increase in acetylene flow rate causes the formation of molybdenum carbide (MoC) hexagonal phase in the coatings, a reduction of grain size and an increase in internal stress. - Highlights: • MoN and MoCN coatings were deposited by cathodic arc evaporation in nitrogen atmosphere. • MoCN coatings were formed using different acetylene flow rates. • Phase composition evolution was observed. • Crystallite size and stress were calculated.

Magnetic interactions in oxide-bridged dichromium(III) complexes. Computational determination of the importance of non-bridging ligands

DEFF Research Database (Denmark)

Morsing, Thorbjørn Juul; Sauer, Stephan P. A.; Weihe, Høgni

2013-01-01

The magnetic susceptibility of the dinuclear chromium(III) complex [(CH3CN)5CrOCr(NCCH3)5](BF4)4 · 2 CH3CN has been measured and analyzed. With a fitted value of the triplet energy J = 650 cm-1, the antiferromagnetic coupling is the strongest hitherto determined for an unsupported linear oxide-br...... relative errors typically of less than 10 % ranging from the strongest coupled systems to systems with moderately strong couplings. A significant influence (>20%) of the chemical nature of the peripheral, non-bridging ligands on the exchange coupling was found and rationalized....

Magneto-paper electrophoresis in the separation of inorganic ions

International Nuclear Information System (INIS)

Mukherjee, H.G.; Datta, S.K.

1983-01-01

A comparative study of the separation of lanthanide ions by paper electrophoresis and magneto-paper electrophoresis is reported. The separation of La(III)-Gd(III), La(III)-Dy(III), Lu(III)-Gd(III), Lu(III)-Ho(III) etc. was achieved by magneto paper electrophoresis using 0.1M KCl as carrier electrolyte. Separation of different oxidation states of the same element like Cu(I)-Cu(II), Ce(III)-Ce(IV), Mn(CN) 6 3 - -Mn(CN) 6 4 - , Co(C 2 O 4 ) 2 2 - -Co(C 2 O 4 ) 3 3 - , V(CN) 6 3 - -VO(CN) 5 3 - , W(CN) 8 4 - -W(CN) 8 3 - and Ru(CN) 6 3 - Ru(CN) 6 4 - was also achieved by magneto paper electrophoretic technique using different carrier electrolytes. (Author)

Dissociation mechanisms and dynamics of doubly charged CD3CN observed by PEPIPICO spectroscopy

International Nuclear Information System (INIS)

Harada, C.; Tada, S.; Yamamoto, K.; Senba, Y.; Yoshida, H.; Hiraya, A.; Wada, S.; Tanaka, K.; Tabayashi, K.

2006-01-01

Dissociation of free acetonitrile-d 3 molecule, CD 3 CN induced by core level excitation was studied near the nitrogen K-edge by time-of-flight fragment mass spectroscopy. A variety of atomic and molecular fragment cations such as D + , CD n + , C 2 D n + , and CD n CN + were detected using the effusive CD 3 CN beam. Photoelectron-photoion-photoion coincidence technique was applied to analyse the dissociation mechanisms and dynamics of doubly charged CD 3 CN 2+ following the N(1s-π * ) excitation. The charge separation mechanisms of core-excited CD 3 CN were discussed in connection with Auger final state distributions

ESR studies of electron irradiated K3Ir(CN)6 in KCl single crystals

International Nuclear Information System (INIS)

Vugman, N.V.; Pinhal, N.M.

1983-01-01

ESR studies of KCl single crystals doped with small amounts of K 3 Ir(CN) 6 and submitted to a prolongued 2 MeV electron irradiation at room temperature reveal the presence of the [IR(CN) 5 Cl] 4- and [Ir(CN) 4 Cl 2 ] 4- new molecular species. Ligand spin densities and ligand field parameters are calculated from the experimental hyperfine and superhyperfine interactions and compared to previous data on the [Ir(CN) 5 ] 4- species. (Author) [pt

Tree species is the major factor explaining C:N ratios in European forest soils

DEFF Research Database (Denmark)

Cools, Nathalie; Vesterdal, Lars; De Vos, Bruno

2014-01-01

The C:N ratio is considered as an indicator of nitrate leaching in response to high atmospheric nitrogen (N) deposition. However, the C:N ratio is influenced by a multitude of other site-related factors. This study aimed to unravel the factors determining C:N ratios of forest floor, mineral soil...... mineral soil layers it was the humus type. Deposition and climatic variables were of minor importance at the European scale. Further analysis for eight main forest tree species individually, showed that the influence of environmental variables on C:N ratios was tree species dependent. For Aleppo pine...... and peat top soils in more than 4000 plots of the ICP Forests large-scale monitoring network. The first objective was to quantify forest floor, mineral and peat soil C:N ratios across European forests. Secondly we determined the main factors explaining this C:N ratio using a boosted regression tree...

CN molecule vibrational spectra excitation in several LTE plasma sources conditions

International Nuclear Information System (INIS)

Iova, I.; Iova, Floriana; Ionita, I.; Bazavan, M.; Ilie, Gh.; Stanescu, G.

2001-01-01

Our interest in CN plasma study steams of the facilities to obtain the CN radicals in a free atmosphere electric discharge where the C of the coal electrodes can to combine in the enough high temperature plasma with the atmospheric nitrogen. Also of much interest is the very important phenomena in which the CN vibrational spectra can be implied and used as a diagnostic tool (plasma chemistry, astrophysics and so on). A peculiar importance presents the CN vibrational spectra in the transient plasmas. It is the reason why we have investigated here some internal processes of a continued and interrupted arc of various pulse lengths. To these purposes we present with enough accuracy the behaviour of the relative band head intensities of the sequences Δ v = +1 and Δ v = 0 belonging to the CN electronic transition (B 2 Σ - X 2 Σ), as a function of the pulse length (50 - 200 ms) as well as a function of the cathode to anode separation. These behaviours give us indications on the vibrational levels of the electronic state populations in several regions of the arc plasma as well on the efficiency of these levels excitation for several plasma pulse lengths. (authors)

Intercalation of hydrotalcites with hexacyanoferrate(II) and (III)-a thermoRaman spectroscopic study

International Nuclear Information System (INIS)

Frost, Ray L.; Musumeci, Anthony W.; Bouzaid, Jocelyn; Adebajo, Moses O.; Martens, Wayde N.; Theo Kloprogge, J.

2005-01-01

Raman spectroscopy using a hot stage indicates that the intercalation of hexacyanoferrate(II) and (III) in the interlayer space of a Mg, Al hydrotalcites leads to layered solids where the intercalated species is both hexacyanoferrate(II) and (III). Raman spectroscopy shows that depending on the oxidation state of the initial hexacyanoferrate partial oxidation and reduction takes place upon intercalation. For the hexacyanoferrate(III) some partial reduction occurs during synthesis. The symmetry of the hexacyanoferrate decreases from O h existing for the free anions to D 3d in the hexacyanoferrate interlayered hydrotalcite complexes. Hot stage Raman spectroscopy reveals the oxidation of the hexacyanoferrate(II) to hexacyanoferrate(III) in the hydrotalcite interlayer with the removal of the cyanide anions above 250 deg. C. Thermal treatment causes the loss of CN ions through the observation of a band at 2080cm -1 . The hexacyanoferrate (III) interlayered Mg, Al hydrotalcites decomposes above 150 deg. C

Determination of lead by hydride generation inductively coupled plasma mass spectrometry (HG-ICP-MS): On-line generation of plumbane using potassium hexacyanomanganate(III)

Energy Technology Data Exchange (ETDEWEB)

Yilmaz, Vedat [Jackson State University, Department of Chemistry and Biochemistry, Jackson, MS 39217 (United States); Erciyes University, Faculty of Pharmacy, Department of Analytical Chemistry, 38039 Kayseri (Turkey); Arslan, Zikri, E-mail: zikri.arslan@jsums.edu [Jackson State University, Department of Chemistry and Biochemistry, Jackson, MS 39217 (United States); Rose, LaKeysha [Jackson State University, Department of Chemistry and Biochemistry, Jackson, MS 39217 (United States)

2013-01-25

Highlights: Black-Right-Pointing-Pointer Potassium hexacyanomanganate(III), (K{sub 3}Mn(CN){sub 6}, was utilized first time for hydride generation (HG). Black-Right-Pointing-Pointer Hexacyanomanganate(III) promoted generation of lead hydride (PbH{sub 4}) remarkably. Black-Right-Pointing-Pointer The HG method using K{sub 3}Mn(CN){sub 6} enhanced sensitivity by at least 40-fold. Black-Right-Pointing-Pointer The method detection limits for Pb were as low as 8 ng L{sup -1} by ICP-MS. Black-Right-Pointing-Pointer The method is highly suitable for quantitative determination of Pb in various samples and salt matrices by ICP-MS. - Abstract: A hydride generation (HG) procedure has been described for determination of Pb by ICP-MS using potassium hexacyanomanganate(III), K{sub 3}Mn(CN){sub 6}, as an additive to facilitate the generation of plumbane (PbH{sub 4}). Potassium hexacyanomanganate(III) was prepared in acidic medium as it was unstable in water. The stability of hexacyanomanganate(III) was examined in dilute solutions of HCl, HNO{sub 3} and H{sub 2}SO{sub 4}. The solutions prepared in 1% v/v H{sub 2}SO{sub 4} were found to be stable for over a period of 24 h. The least suitable medium was 1% v/v HNO{sub 3}. For generation of plumbane, acidic hexacyanomanganate(III) and sample solutions were mixed on-line along a 5-cm long tygon tubing (1.14 mm i.d.) and then reacted with 2% m/v sodium borohydride (NaBH{sub 4}). A concentration of 0.5% m/v K{sub 3}Mn(CN){sub 6} facilitated the generation of PbH{sub 4} remarkably. In comparison to H{sub 2}SO{sub 4}, HCl provided broader working range for which optimum concentration was 1% v/v. No significant interferences were noted from transition metals and hydride forming elements, up to 0.5 {mu}g mL{sup -1} levels, except Cu which depressed the signals severely. The depressive effects in the presence of 0.1 {mu}g mL{sup -1} Cu were alleviated by increasing the concentration of K{sub 3}Mn(CN){sub 6} to 2% m/v. Under these conditions

NMR spectroscopic and X-ray crystallographic study of methylcobalt(III) compounds with saturated amine ligands

DEFF Research Database (Denmark)

Kofod, Pauli; Harris, Pernille

2004-01-01

The C-13 chemical shifts of methylcobalt(III) compounds with saturated amine ligands in cis positions to the methyl group and a monodentate ligand, L = CN-, NH3, NO2, N-3(-), H2O, or OH-, in the trans position are reported. The amine ligands used, 1,2-ethanediamine (en), 1,3-propanediamine (tn), N...

Preparation of mesoporous carbon nitride structure by the dealloying of Ni/a-CN nanocomposite films

Science.gov (United States)

Zhou, Han; Shen, Yongqing; Huang, Jie; Liao, Bin; Wu, Xianying; Zhang, Xu

2018-05-01

The preparation of mesoporous carbon nitride (p-CN) structure by the selective dealloying process of Ni/a-CN nanocomposite films is investigated. The composition and structure of the Ni/a-CN nanocomposite films and porous carbon nitride (p-CN) films are determined by scan electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Phase separated structure including nickel carbide phase and the surrounding amorphous carbon nitride (a-CN) matrix are detected for the as-deposited films. Though the bulk diffusion is introduced in the film during the annealing process, the grain sizes for the post-annealed films are around 10 nm and change little comparing with the ones of the as-deposited films, which is associated with the thermostability of the CN surrounding in the film. The p-CN skeleton with its pore size around 12.5 nm is formed by etching the post-annealed films, indicative of the stability of the phase separated structure during the annealing process.

Application of GIS-based SCS-CN method in West Bank catchments, Palestine

Directory of Open Access Journals (Sweden)

Sameer Shadeed

2010-03-01

Full Text Available Among the most basic challenges of hydrology are the prediction and quantification of catchment surface runoff. The runoff curve number (CN is a key factor in determining runoff in the SCS (Soil Conservation Service based hydrologic modeling method. The traditional SCS-CN method for calculating the composite curve number is very tedious and consumes a major portion of the hydrologic modeling time. Therefore, geographic information systems (GIS are now being used in combination with the SCS-CN method. This paper assesses the modeling of flow in West Bank catchments using the GIS-based SCS-CN method. The West Bank, Palestine, is characterized as an arid to semi-arid region with annual rainfall depths ranging between 100 mm in the vicinity of the Jordan River to 700 mm in the mountains extending across the central parts of the region. The estimated composite curve number for the entire West Bank is about 50 assuming dry conditions. This paper clearly demonstrates that the integration of GIS with the SCS-CN method provides a powerful tool for estimating runoff volumes in West Bank catchments, representing arid to semi-arid catchments of Palestine.

Two different one-dimensional structural motifs in [catena-{Cu(tacn)}2Pd(CN)4]Br2.[catena-Cu(tacn)Pd(CN)4]2.H2O (tacn is 1,4,7-triazacyclononane).

Science.gov (United States)

Kuchár, Juraj; Cernák, Juraj

2009-07-01

The title compound, catena-poly[[bis[(triazacyclononane-kappa(3)N,N',N'')copper(II)]-di-mu-cyanido-kappa(4)N:C-palladate(II)-di-mu-cyanido-kappa(4)C:N] dibromide bis[[(triazacyclononane-kappa(3)N,N',N'')copper(II)]-mu-cyanido-kappa(2)N:C-[dicyanidopalladate(II)]-mu-cyanido-kappa(2)C:N] monohydrate], {[Cu(2)Pd(CN)(4)(C(6)H(15)N(3))(2)]Br(2).[Cu(2)Pd(2)(CN)(8)(C(6)H(15)N(3))(2)].H(2)O}(n), (I), was isolated from an aqueous solution containing tacn.3HBr (tacn is 1,4,7-triazacyclononane), Cu(2+) and tetracyanidopalladate(2-) anions. The crystal structure of (I) is essentially ionic and built up of 2,2-electroneutral chains, viz. [Cu(tacn)(NC)-Pd(CN)(2)-(CN)-], positively charged 2,4-ribbons exhibiting the composition {[Cu(tacn)(NC)(2)-Pd(CN)(2)-Cu(tacn)](2n+)}(n), bromide anions and one disordered water molecule of crystallization. The O atom of the water molecule occupies two unique crystallographic positions, one on a centre of symmetry, which is half occupied, and the other in a general position with one-quarter occupancy. One of the tacn ligands also exhibits disorder. The formation of two different types of one-dimensional structural motif within the same structure is a unique feature of this compound.

Moessbauer spectroscopic studies of alkylammonium iron(III) complexes

International Nuclear Information System (INIS)

Katada, M.; Kozawa, S.; Nakajima, Y.

2006-01-01

Alkylammonium iron(III) complexes, [(n-C n H 2n+1 )mNH 4-m ] 3 [Fe(CN) 6 ] were prepared and studied by Moessbauer spectroscopy, XRD, and DSC. In the complexes with m=2, the temperature dependences of the area intensity of Moessbauer are correlated to the motion of alkyl chains. The temperature dependence of the complex with n=4 was linear and smaller than that of other complexes. Especially in the complex with n=6, the deviation from the linear was the largest in the complexes observed. This result is attributed to the structural difference of the complex. The complexes with n≥8 consist of two-dimensional layer structure. The temperature dependence of the area intensity was similar to each other. This means that the motion of alkyl chain in these complexes are almost the same. The values of quadrupole splitting for the complexes were larger those that of the complexes (m=1). This indicates that the form of [Fe(CN) 6 ] 3- ion is affected by the differences of the number of alkyl groups. (author)

Highly efficient alkane oxidation catalyzed by [Mn(V)(N)(CN)4](2-). Evidence for [Mn(VII)(N)(O)(CN)4](2-) as an active intermediate.

Science.gov (United States)

Ma, Li; Pan, Yi; Man, Wai-Lun; Kwong, Hoi-Ki; Lam, William W Y; Chen, Gui; Lau, Kai-Chung; Lau, Tai-Chu

2014-05-28

The oxidation of various alkanes catalyzed by [Mn(V)(N)(CN)4](2-) using various terminal oxidants at room temperature has been investigated. Excellent yields of alcohols and ketones (>95%) are obtained using H2O2 as oxidant and CF3CH2OH as solvent. Good yields (>80%) are also obtained using (NH4)2[Ce(NO3)6] in CF3CH2OH/H2O. Kinetic isotope effects (KIEs) are determined by using an equimolar mixture of cyclohexane (c-C6H12) and cyclohexane-d12 (c-C6D12) as substrate. The KIEs are 3.1 ± 0.3 and 3.6 ± 0.2 for oxidation by H2O2 and Ce(IV), respectively. On the other hand, the rate constants for the formation of products using c-C6H12 or c-C6D12 as single substrate are the same. These results are consistent with initial rate-limiting formation of an active intermediate between [Mn(N)(CN)4](2-) and H2O2 or Ce(IV), followed by H-atom abstraction from cyclohexane by the active intermediate. When PhCH2C(CH3)2OOH (MPPH) is used as oxidant for the oxidation of c-C6H12, the major products are c-C6H11OH, c-C6H10O, and PhCH2C(CH3)2OH (MPPOH), suggesting heterolytic cleavage of MPPH to generate a Mn═O intermediate. In the reaction of H2O2 with [Mn(N)(CN)4](2-) in CF3CH2OH, a peak at m/z 628.1 was observed in the electrospray ionization mass spectrometry, which is assigned to the solvated manganese nitrido oxo species, (PPh4)[Mn(N)(O)(CN)4](-)·CF3CH2OH. On the basis of the experimental results the proposed mechanism for catalytic alkane oxidation by [Mn(V)(N)(CN)4](2-)/ROOH involves initial rate-limiting O-atom transfer from ROOH to [Mn(N)(CN)4](2-) to generate a manganese(VII) nitrido oxo active species, [Mn(VII)(N)(O)(CN)4](2-), which then oxidizes alkanes (R'H) via a H-atom abstraction/O-rebound mechanism. The proposed mechanism is also supported by density functional theory calculations.

Cubic mesoporous Ag@CN: a high performance humidity sensor.

Science.gov (United States)

Tomer, Vijay K; Thangaraj, Nishanthi; Gahlot, Sweta; Kailasam, Kamalakannan

2016-12-01

The fabrication of highly responsive, rapid response/recovery and durable relative humidity (%RH) sensors that can precisely monitor humidity levels still remains a considerable challenge for realizing the next generation humidity sensing applications. Herein, we report a remarkably sensitive and rapid %RH sensor having a reversible response using a nanocasting route for synthesizing mesoporous g-CN (commonly known as g-C 3 N 4 ). The 3D replicated cubic mesostructure provides a high surface area thereby increasing the adsorption, transmission of charge carriers and desorption of water molecules across the sensor surfaces. Owing to its unique structure, the mesoporous g-CN functionalized with well dispersed catalytic Ag nanoparticles exhibits excellent sensitivity in the 11-98% RH range while retaining high stability, negligible hysteresis and superior real time %RH detection performances. Compared to conventional resistive sensors based on metal oxides, a rapid response time (3 s) and recovery time (1.4 s) were observed in the 11-98% RH range. Such impressive features originate from the planar morphology of g-CN as well as unique physical affinity and favourable electronic band positions of this material that facilitate water adsorption and charge transportation. Mesoporous g-CN with Ag nanoparticles is demonstrated to provide an effective strategy in designing high performance %RH sensors and show great promise for utilization of mesoporous 2D layered materials in the Internet of Things and next generation humidity sensing applications.

Synthesis, spectroscopic, thermal and structural properties of [M(3-aminopyridine)2Ni(μ-CN)2(CN)2]n (M(II) = Co and Cu) heteropolynuclear cyano-bridged complexes

Science.gov (United States)

Kartal, Zeki

2016-01-01

Two novel cyano-bridged heteropolynuclear complexes, [Co(3-aminopyridine)2Ni(μ-CN)2(CN)2]n and [Cu(3-aminopyridine)2Ni(μ-CN)2(CN)2]n have been synthesized and characterized by elemental, thermal, FT-IR and FT-Raman spectroscopies. The structures of complexes have been determined by X-ray powder diffraction. The FT-IR and FT-Raman spectra of complexes have been recorded in the region of 3500-400 cm-1 and 3500-100 cm-1, respectively. General information was acquired about structural properties of these complexes from FT-IR and FT-Raman spectra by considering changes at characteristic peaks of the cyano group and 3AP. The splitting of the ν(Ctbnd N) stretching bands in the FT-IR spectra for complexes indicates the presence of terminal and bridging cyanides. The thermal behaviors of these complexes have been also investigated in the range of 25-950 °C using TG and DTG methods. Magnetic susceptibility measurements were made at room temperature using Gouy-balance.

Evaluation of SCS-CN method using a fully distributed physically based coupled surface-subsurface flow model

Science.gov (United States)

Shokri, Ali

2017-04-01

The hydrological cycle contains a wide range of linked surface and subsurface flow processes. In spite of natural connections between surface water and groundwater, historically, these processes have been studied separately. The current trend in hydrological distributed physically based model development is to combine distributed surface water models with distributed subsurface flow models. This combination results in a better estimation of the temporal and spatial variability of the interaction between surface and subsurface flow. On the other hand, simple lumped models such as the Soil Conservation Service Curve Number (SCS-CN) are still quite common because of their simplicity. In spite of the popularity of the SCS-CN method, there have always been concerns about the ambiguity of the SCS-CN method in explaining physical mechanism of rainfall-runoff processes. The aim of this study is to minimize these ambiguity by establishing a method to find an equivalence of the SCS-CN solution to the DrainFlow model, which is a fully distributed physically based coupled surface-subsurface flow model. In this paper, two hypothetical v-catchment tests are designed and the direct runoff from a storm event are calculated by both SCS-CN and DrainFlow models. To find a comparable solution to runoff prediction through the SCS-CN and DrainFlow, the variance between runoff predictions by the two models are minimized by changing Curve Number (CN) and initial abstraction (Ia) values. Results of this study have led to a set of lumped model parameters (CN and Ia) for each catchment that is comparable to a set of physically based parameters including hydraulic conductivity, Manning roughness coefficient, ground surface slope, and specific storage. Considering the lack of physical interpretation in CN and Ia is often argued as a weakness of SCS-CN method, the novel method in this paper gives a physical explanation to CN and Ia.

After-Effects of the Cobalt-57-Iron-57 Electron-Capture Reaction in Hexacyanocobaltate (III) Complexes

DEFF Research Database (Denmark)

Fenger, Jørgen Folkvard; Siekierska, K.E.; Olsen, J.

1973-01-01

Isomorphous hexacyanocobaltate(III) complexes with the bivalent metal cations Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, and Cd2+ have been labelled with 57Co and used as Mössbauer sources. Whilst the spectrum of the complex Fe3[57Co(CN)6]2 can be resolved into a single line corresponding to the ion Fe II...

Structural phase transitions in Zn(CN)2 under high pressures

International Nuclear Information System (INIS)

Poswal, H.K.; Tyagi, A.K.; Lausi, Andrea; Deb, S.K.; Sharma, Surinder M.

2009-01-01

High pressure behavior of zinc cyanide (Zn(CN) 2 ) has been investigated with the help of synchrotron-based X-ray diffraction measurements. Our studies reveal that under pressure this compound undergoes phase transformations and the structures of the new phases depend on whether the pressure is hydrostatic or not. Under hydrostatic conditions, Zn(CN) 2 transforms from cubic to orthorhombic to cubic-II to amorphous phases. In contrast, the non-hydrostatic pressure conditions drive the ambient cubic phase to a partially disordered crystalline phase, which eventually evolves to a substantially disordered phase. The final disordered phase in the latter case is distinct from the amorphous phase observed under the hydrostatic pressures. - Graphical abstract: High pressure X-ray diffraction investigations on Zn(CN) 2 show three phase transformations i.e., cubic→orthorhombic→cubic-II→amorphous. However, the results strongly depend upon the nature of stress

Hybrid molecular materials based upon organic pi-electron donors and inorganic metal complexes. Conducting salts of bis(ethylenediseleno)tetrathiafulvalene (BEST) with the octahedral anions hexacyanoferrate(III) and nitroprusside

CERN Document Server

Clemente-Leon, M; Galan-Mascaros, J R; Giménez-Saiz, C; Gómez-García, C J; Fabre, J M; Mousdis, G A; Papavassiliou, G C

2002-01-01

The synthesis, structure and physical characterization of three new radical salts formed by the organic donor bis(ethylenediseleno)tetrathiafulvalene (BEDS-TTF or BEST) and the paramagnetic hexacyanoferrate(III) anion [Fe(CN) sub 6] sup 3 sup - or the photochromic nitroprusside anion [Fe(CN) sub 5 NO] sup 2 sup - are reported: (BEST) sub 4 [Fe(CN) sub 6] (1), (BEST) sub 3 [Fe(CN) sub 6] sub 2 centre dot H sub 2 O (2) and (BEST) sub 2 [Fe(CN) sub 5 NO] (3). Salts 1 and 3 show a layered structure with alternating organic (beta-type packing) and inorganic slabs. Salt 2 shows an original interpenetrated structure probably due to the unprecedented presence of (BEST) sup 2 sup + dications. The three salts are semiconductors although salt 1 exhibits a high room temperature conductivity and a semiconducting-semiconducting transition at ca. 150 K which has been attributed to a dimerization in the organic sublattice.

WebCN: A web-based computation tool for in situ-produced cosmogenic nuclides

Energy Technology Data Exchange (ETDEWEB)

Ma Xiuzeng [Department of Physics, Purdue University, West Lafayette, IN 47907 (United States)]. E-mail: hongju@purdue.edu; Li Yingkui [Department of Geography, University of Missouri-Columbia, Columbia, MO 65211 (United States); Bourgeois, Mike [Department of Physics, Purdue University, West Lafayette, IN 47907 (United States); Caffee, Marc [Department of Physics, Purdue University, West Lafayette, IN 47907 (United States); Elmore, David [Department of Physics, Purdue University, West Lafayette, IN 47907 (United States); Granger, Darryl [Department of Earth and Atmospheric Sciences, Purdue University, West Lafayette, IN 47907 (United States); Muzikar, Paul [Department of Physics, Purdue University, West Lafayette, IN 47907 (United States); Smith, Preston [Department of Physics, Purdue University, West Lafayette, IN 47907 (United States)

2007-06-15

Cosmogenic nuclide techniques are increasingly being utilized in geoscience research. For this it is critical to establish an effective, easily accessible and well defined tool for cosmogenic nuclide computations. We have been developing a web-based tool (WebCN) to calculate surface exposure ages and erosion rates based on the nuclide concentrations measured by the accelerator mass spectrometry. WebCN for {sup 10}Be and {sup 26}Al has been finished and published at http://www.physics.purdue.edu/primelab/for{sub u}sers/rockage.html. WebCN for {sup 36}Cl is under construction. WebCN is designed as a three-tier client/server model and uses the open source PostgreSQL for the database management and PHP for the interface design and calculations. On the client side, an internet browser and Microsoft Access are used as application interfaces to access the system. Open Database Connectivity is used to link PostgreSQL and Microsoft Access. WebCN accounts for both spatial and temporal distributions of the cosmic ray flux to calculate the production rates of in situ-produced cosmogenic nuclides at the Earth's surface.

A syntactical comparison between pair sentential calculus PSC and Gupta's definitional calculus Cn

OpenAIRE

石井,忠夫

2016-01-01

In this paper we will compare two logical systems PSC and Cn with a syntactical point of view. Because both notions of the pair-sentence with stage number in PSC and Gupta's sentence-definition with revision stage number in Cn are very similar, and both can deal with paradoxical sentences like a simple Liar sentence. His system was defined as a predicate calculus, but here we will introduce the propositional version of Cn for the comparison, and we had the following results: (1) C0 is a sublo...

Synthesis and molecular structure of [Cu(NH3)4][Ni(CN)4]: A missing piece in the [Cu(NH3)n][Ni(CN)4] story

Science.gov (United States)

Solanki, Dina; Hogarth, Graeme

2015-11-01

Reaction of CuCl2·2H2O and K2[Ni(CN)4]·2H2O in aqueous ammonia gave blue rod-like crystals of [Cu(NH3)4][Ni(CN)4]. An X-ray crystallographic reveals that square-planar anions and cations are weakly associated through coordination of a cis pair of cyanide ligands to copper, with one short and one long contact and thus the copper centre is best described as a square-based pyramid. Crystals lose ammonia readily upon removal from the solvent and this has been probed by TGA and DSC measurements. For comparison we have also re-determined the structure of the related ethylenediamine (en) complex [Cu(en)2][Ni(CN)4] at 150 K. This consists of a 1D chain in which a trans pair of cyanide ligands bind to copper such that the latter has an overall tetragonally distorted octahedral coordination geometry.

Rh(III)-catalyzed oxidative olefination of N-(1-naphthyl)sulfonamides using activated and unactivated alkenes.

Science.gov (United States)

Li, Xuting; Gong, Xue; Zhao, Miao; Song, Guoyong; Deng, Jian; Li, Xingwei

2011-11-04

Rhodium(III)-catalyzed oxidative olefination of N-(1-naphthyl)sulfonamides has been achieved at the peri position. Three categories of olefins have been successfully applied. Activated olefins reacted to afford five-membered azacycles as a result of oxidative olefination-hydroamination. Unactivated olefins reacted to give the olefination product. 2-fold oxidative C-C and C-N coupling was achieved for allylbenzenes. © 2011 American Chemical Society

Efficient adsorption of Au(CN)2- from gold cyanidation with graphene oxide-polyethylenimine hydrogel as adsorbent

Science.gov (United States)

Yang, Lang; Jia, Feifei; Yang, Bingqiao; Song, Shaoxian

The adsorption of gold cyanide complex ion (Au(CN)2-) on graphene oxide-polyethylenimine hydrogel (GO/PEI hydrogel) from gold cyanidation has been studied to explore the possibility of the application of GO/PEI hydrogel in gold cyanidation process for extracting gold from ores. The adsorption was carried out in artificial Au(CN)2- aqueous solution with GO/PEI hydrogel as adsorbent. The experimental results, as well as IR, XPS and SEM-EDS, have shown that GO/PEI hydrogel exhibited a high adsorption capacity and a fast adsorption rate of Au(CN)2-, suggesting that GO/PEI hydrogel might be a good adsorbent for the recovery of Au(CN)2-. The adsorption of Au(CN)2- on GO/PEI hydrogel obeyed the Langmuir isotherm model and fitted well with the pseudo second order model. The good recovery of Au(CN)2- was largely related to the porous structure, large specific surface area, as well as the oxygenous functional groups on the surface of GO/PEI hydrogel.

EDF-1 downregulates the CaM/Cn/NFAT signaling pathway during adipogenesis

International Nuclear Information System (INIS)

López-Victorio, Carlos J.; Velez-delValle, Cristina; Beltrán-Langarica, Alicia; Kuri-Harcuch, Walid

2013-01-01

Highlights: ► EDF-1 participates early adipogenesis in 3T3F442A cells induced with Staurosporine/Dexamethasone. ► EDF-1 associates with CaM and Cn, most likely inactivating Cn. ► EDF-1/CaM complex seems to prevent NFATc1 activation by Cn. ► EDF-1 regulates the Cn/CaM/NFATc1 pathway during adipogenesis. ► EDF-1 may regulate the activation of Cn through a complex formation with CaM. - Abstract: The endothelial differentiation factor-1 (EDF-1) is a calmodulin binding protein that regulates calmodulin-dependent enzymes. In endothelial cells, this factor can form a protein complex with calmodulin. We analyzed the relationship between this factor and the members of calmodulin/calcineurin/nuclear factor of activated T-cells (NFAT) signaling pathway during adipogenesis of 3T3-F442A cells. We found that the expression of edf1 is upregulated during early adipogenesis, whereas that of calcineurin gene is lowered, suggesting that this pathway should be downregulated to allow for adipogenesis to occur. We also found that EDF-1 associates with calmodulin and calcineurin, most likely inactivating calcineurin. Our results showed that EDF-1 inactivates the calmodulin/calcineurin/NFAT pathway via sequestration of calmodulin, during early adipogenesis, and we propose a mechanism that negatively regulates the activation of calcineurin through a complex formation between EDF-1 and calmodulin. This finding raises the possibility that modulating this pathway might offer some alternatives to regulate adipose biology

EDF-1 downregulates the CaM/Cn/NFAT signaling pathway during adipogenesis

Energy Technology Data Exchange (ETDEWEB)

López-Victorio, Carlos J.; Velez-delValle, Cristina; Beltrán-Langarica, Alicia [Department of Cell Biology, Center for Research and Advanced Studies-IPN, Apdo. Postal 14-740, México City 07000 (Mexico); Kuri-Harcuch, Walid, E-mail: walidkuri@gmail.com [Department of Cell Biology, Center for Research and Advanced Studies-IPN, Apdo. Postal 14-740, México City 07000 (Mexico)

2013-03-01

Highlights: ► EDF-1 participates early adipogenesis in 3T3F442A cells induced with Staurosporine/Dexamethasone. ► EDF-1 associates with CaM and Cn, most likely inactivating Cn. ► EDF-1/CaM complex seems to prevent NFATc1 activation by Cn. ► EDF-1 regulates the Cn/CaM/NFATc1 pathway during adipogenesis. ► EDF-1 may regulate the activation of Cn through a complex formation with CaM. - Abstract: The endothelial differentiation factor-1 (EDF-1) is a calmodulin binding protein that regulates calmodulin-dependent enzymes. In endothelial cells, this factor can form a protein complex with calmodulin. We analyzed the relationship between this factor and the members of calmodulin/calcineurin/nuclear factor of activated T-cells (NFAT) signaling pathway during adipogenesis of 3T3-F442A cells. We found that the expression of edf1 is upregulated during early adipogenesis, whereas that of calcineurin gene is lowered, suggesting that this pathway should be downregulated to allow for adipogenesis to occur. We also found that EDF-1 associates with calmodulin and calcineurin, most likely inactivating calcineurin. Our results showed that EDF-1 inactivates the calmodulin/calcineurin/NFAT pathway via sequestration of calmodulin, during early adipogenesis, and we propose a mechanism that negatively regulates the activation of calcineurin through a complex formation between EDF-1 and calmodulin. This finding raises the possibility that modulating this pathway might offer some alternatives to regulate adipose biology.

Hydrothermal syntheses, structural, Raman, and luminescence studies of Cm[M(CN)2]3.3H2O and Pr[M(CN)2]3.3H2O (M=Ag, Au)

International Nuclear Information System (INIS)

Assefa, Zerihun; Haire, Richard G.; Sykora, Richard E.

2008-01-01

We have prepared Cm[Au(CN) 2 ] 3 .3H 2 O and Cm[Ag(CN) 2 ] 3 .3H 2 O as a part of our continuing investigations into the chemistry of the 5f-elements' dicyanometallates. Single crystals of Cm[Au(CN) 2 ] 3 .3H 2 O were obtained from the reaction of CmCl 3 and KAu(CN) 2 under mild hydrothermal conditions. Due to similarities in size, the related praseodymium compounds were also synthesized and characterized for comparison with the actinide systems. The compounds crystallize in the hexagonal space group P6 3 /mcm, where the curium and the transition metals interconnect through cyanide bridging. Crystallographic data (Mo Kα, λ=0.71073 A): Cm[Au(CN) 2 ] 3 .3H 2 O (1), a=6.6614(5) A, c=18.3135(13) A, V=703.77(9), Z=2; Pr[Au(CN) 2 ] 3 .3H 2 O (3), a=6.6662(8) A, c=18.497(3) A, V=711.83(17), Z=2; Pr[Ag(CN) 2 ] 3 .3H 2 O (4), a=6.7186(8) A, c=18.678(2) A, V=730.18(14), Z=2. The Cm 3+ and/or Pr 3+ ions are coordinated to six N-bound CN - groups resulting in a trigonal prismatic arrangement. Three oxygen atoms of coordinated water molecules tricap the trigonal prismatic arrangement providing a coordination number of nine for the f-elements. The curium ions in both compounds exhibit a strong red emission corresponding to the 6 D 7/2 → 8 S 7/2 transition. This transition is observed at 16,780 cm -1 , with shoulders at 17,080 and 16,840 cm -1 for the Ag complex, while the emission is red shifted by ∼100 cm -1 in the corresponding gold complex. The Pr systems also provide well-resolved emissions upon f-f excitation. - Graphical abstract: Coordination polymeric compounds between a trans-plutonium element, curium and transition metal ions, gold(I) and silver(I), were prepared using the hydrothermal synthetic procedure. The curium ion and the transition metals are interconnected through cyanide bridging. The Cm ion has a tricapped trigonal prismatic coordination environment with coordination number of nine. Detail photoluminescence studies of the complexes are also reported

Review IPEEE C.N. external event Vandellos II; Revision del IPEEE de otros sucesos externos de C.N. Vandellos II

Energy Technology Data Exchange (ETDEWEB)

Hernandez, H.; Gasca, C.; Beltran, F.; Salvat, M.; Pifarre, D.; Canadell, F.; Aleman, A.

2010-07-01

Within the process of maintaining and updating the risk analysis of CN Vandellos II, results from the review of the study of vulnerability of the plant against severe accidents caused by external events (Individual Plant Examination on Extornal Events, IPEEE).

Investigation of the kinetics of hydrolysis of mixed cyanothiocyanatochromates(III) by high voltage ionophoresis

International Nuclear Information System (INIS)

Blasius, E.; Augustin, H.; Ehrhardt, T.

1975-01-01

The hydrolysis of the mixed cyanothiocyanatochromates(III) is studied with respect to the influence of the light and of the darkness upon the reaction rate. As representatives the labelled complexes [Cr(N 14 CS) 6 ] 3- , [Cr( 14 CN)(NCS) 5 ] 3- and trans-[Cr( 14 CN) 2 (NCS) 4 ] 3- , being easy preparated, are used. After the high voltage ionophoresis, their zones on the pherogramms are located by means of the activity distribution curves. The activities of the stamped zones of the complexes are taken into account for the concentrations, in measuring the concentration-time dependence at various pH values and temperatures. The reaction rates, the half-times and the Arrhenius energy of activation are reported. The rate of hydrolysis is dependent on the structure of the complexes and 50-fold in the light

μ-Peroxido-bis[acetonitrilebis(ethylenediaminecobalt(III] tetrakis(perchlorate

Directory of Open Access Journals (Sweden)

Valentina A. Kalibabchuk

2010-12-01

Full Text Available The title compound, [Co2(O2(CH3CN2(C2H8N24](ClO44, consists of centrosymmetric binuclear cations and perchlorate anions. Two CoIII atoms, which have a slightly distorted octahedral coordination, are connected through a peroxido bridge; the O—O distance is 1.476 (3 Å. Both acetonitrile ligands are situated in a trans position with respect to the O—O bridge. In the crystal, the complex cations are connected by N—H...O hydrogen bonds between ethylendiamine NH groups and O atoms from the perchlorate anions and peroxide O atoms.

Routine production of H11CN and :11C:-1-aminocyclopentanecarboxylic acid

International Nuclear Information System (INIS)

Sambre, J.; Vandecasteele, C.; Geothals, P.; Rabi, N.A.; Haver, D. van; Slegers, G.

1985-01-01

The production of H 11 CN using the 14 N(p,α) 11 C reaction, was studied. The yield is 140 mCi/μA at saturation (EOB). From 1.8 Ci of H 11 CN 140 mCi of [ 11 C]ACPC are produced routinely and under remote-control. Chemical and pharmaceutical controls showed that the product is suitable for injection. (author)

[Hydrogen production and enzyme activity of acidophilic strain X-29 at different C/N ratio].

Science.gov (United States)

Li, Qiu-bo; Xing, De-feng; Ren, Nan-qi; Zhao, Li-hua; Song, Ye-ying

2006-04-01

Some fermentative bacteria can produce hydrogen by utilizing carbohydrate and other kinds of organic compounds as substrates. Hydrogen production was also determined by both the limiting of growth and related enzyme activity in energy metabolism. Carbon and nitrogen are needed for the growth and metabolism of microorganisms. In addition, the carbon/nitrogen (C/N) ratio can influence the material metabolized and the energy produced. In order to improve the hydrogen production efficiency of the bacteria, we analyzed the effect of different C/N ratios on hydrogen production and the related enzyme activities in the acidophilic strain X-29 using batch test. The results indicate that the differences in the metabolism level and enzyme activity are obvious at different C/N ratios. Although the difference in liquid fermentative products produced per unit of biomass is not obvious, hydrogen production is enhanced at a specifically determined ratio. At a C/N ratio of 14 the accumulative hydrogen yield of strain X-29 reaches the maximum, 2210.9 mL/g. At different C/N ratios, the expression of hydrogenase activity vary; the activity of hydrogenase decrease quickly after reaching a maximum along with the fermentation process, but the time of expression is short. The activity of alcohol dehydrogenase (ADH) tend to stabilize after reaching a peak along with the fermentation process, the difference in expression activity is little, and the expression period is long at different C/N ratios. At a C/N ratio of 14 hydrogenase and ADH reach the maximum 2.88 micromol x (min x mg)(-1) and 33.2 micromol x (min x mg)(-1), respectively. It is shown that the C/N ratio has an important effect on enhancing hydrogen production and enzyme activity.

Low energy electron attachment to cyanamide (NH{sub 2}CN)

Energy Technology Data Exchange (ETDEWEB)

Tanzer, Katrin; Denifl, Stephan, E-mail: Andrzej.Pelc@poczta.umcs.lublin.pl, E-mail: Stephan.Denifl@uibk.ac.at [Institut für Ionenphysik und Angewandte Physik, Leopold Franzens Universität Innsbruck, Technikerstr. 25, 6020 Innsbruck (Austria); Pelc, Andrzej, E-mail: Andrzej.Pelc@poczta.umcs.lublin.pl, E-mail: Stephan.Denifl@uibk.ac.at [Mass Spectrometry Department, Institute of Physics, Marie Curie-Sklodowska University, Pl. M. C.-Sklodowskiej 1, 20-031 Lublin (Poland); Huber, Stefan E. [Institut für Ionenphysik und Angewandte Physik, Leopold Franzens Universität Innsbruck, Technikerstr. 25, 6020 Innsbruck (Austria); Lehrstuhl für Theoretische Chemie, Technische Universität München, Lichtenbergstr. 4, 85747 Garching (Germany); Czupyt, Z. [Ion Microprobe Facility Micro-area Analysis Laboratory, Polish Geological Institute–National Research Institute, Rakowiecka 4, 00-975 Warszawa (Poland)

2015-01-21

Cyanamide (NH{sub 2}CN) is a molecule relevant for interstellar chemistry and the chemical evolution of life. In the present investigation, dissociative electron attachment to NH{sub 2}CN has been studied in a crossed electron–molecular beams experiment in the electron energy range from about 0 eV to 14 eV. The following anionic species were detected: NHCN{sup −}, NCN{sup −}, CN{sup −}, NH{sub 2}{sup −}, NH{sup −}, and CH{sub 2}{sup −}. The anion formation proceeds within two broad electron energy regions, one between about 0.5 and 4.5 eV and a second between 4.5 and 12 eV. A discussion of possible reaction channels for all measured negative ions is provided. The experimental results are compared with calculations of the thermochemical thresholds of the anions observed. For the dehydrogenated parent anion, we explain the deviation between the experimental appearance energy of the anion with the calculated corresponding reaction threshold by electron attachment to the isomeric form of NH{sub 2}CN—carbodiimide.

Multiple stellar populations of globular clusters from homogeneous Ca-Cn photometry. II. M5 (NGC 5904) and a new filter system

OpenAIRE

Lee, Jae-Woo

2017-01-01

Using our ingeniously designed new filter systems, we investigate the multiple stellar populations of the RGB and AGB in the GC M5. Our results are the following. (1) Our cn_jwl index accurately traces the nitrogen abundances in M5, while other color indices fail to do so. (2) We find bimodal CN distributions both in the RGB and the AGB sequences, with the number ratios between the CN-weak (CN-w) and the CN-strong (CN-s) of n(CN-w):n(CN-s) = 29:71(+/- 2) and 21:79(+/- 7), respectively. (3) We...

Applications of Palladium-Catalyzed C-N Cross-Coupling Reactions.

Science.gov (United States)

Ruiz-Castillo, Paula; Buchwald, Stephen L

2016-10-12

Pd-catalyzed cross-coupling reactions that form C-N bonds have become useful methods to synthesize anilines and aniline derivatives, an important class of compounds throughout chemical research. A key factor in the widespread adoption of these methods has been the continued development of reliable and versatile catalysts that function under operationally simple, user-friendly conditions. This review provides an overview of Pd-catalyzed N-arylation reactions found in both basic and applied chemical research from 2008 to the present. Selected examples of C-N cross-coupling reactions between nine classes of nitrogen-based coupling partners and (pseudo)aryl halides are described for the synthesis of heterocycles, medicinally relevant compounds, natural products, organic materials, and catalysts.

EST Table: CN379387 [KAIKOcDNA[Archive

Lifescience Database Archive (English)

Full Text Available CN379387 rzhswbb0_004120 10/09/28 99 %/113 aa gb|ADB13006.1| elongation factor-1 alpha [Colias pelidne skinn...eri] 10/09/01 95 %/113 aa FBpp0257399|DyakGE12389-PA 10/08/28 77 %/113 aa R03G5.1d#

Synthesis of SiCN@TiO2 core-shell ceramic microspheres via PDCs method

Science.gov (United States)

Liu, Hongli; Wei, Ning; Li, Jing; Zhang, Haiyuan; Chu, Peng

2018-02-01

A facile and effective polymer-derived ceramics (PDCs) emulsification-crosslinking-pyrolysis method was developed to fabricate SiCN@TiO2 core-shell ceramic microspheres with polyvinylsilazane (PVSZ) and tetrabutyl titanate (TBT) as precursors. The TBT: PVSZ mass ratios, emulsifier concentrations and the pyrolysis temperature were examined as control parameters to tune the size and morphology of microspheres. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) confirmed the synthesized SiCN@TiO2 microspheres to be comprised of SiCN core coated with TiO2 crystals, with an average size of 0.88 μm when pyrolyzed at 1400 °C. The analysis of Fourier transform infrared spectroscopy (FT-IR), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) ensured that SiCN@TiO2 core-shell ceramic microspheres composed of rutile TiO2, β-SiC and Si3N4 crystalline phases, The thermal properties were characterized by thermogravimetric analysis (TGA). The obtained SiCN@TiO2 core-shell ceramic microspheres were the promising candidate of the infrared opacifier in silica aerogels and this technique can be extended to other preceramic polymers.

Synergy between erosion-corrosion of steel AISI 4140 covered by a multilayer TiCN / TiNbCN, at an impact angle of 90°

Directory of Open Access Journals (Sweden)

Willian Aperador Chaparro

2013-01-01

Full Text Available El propósito de este trabajo es estudiar el efecto de la erosión corrosión en el desgaste de los recubrimientos en forma de multicapas de [TiCN / TiNbCN] n depositadas sobre sustratos de acero AISI 4140. El crecimiento de las multicapas de [TiCN / TiNbCN] n se realizó mediante un sistema magnetrón sputtering con RF reactivo en el que se varió sistemáticamente el período bicapa (Λ, y el número bicapa (n, manteniendo constante el espesor total de las capas (~ 3 micras. Las multicapas se evaluaron comparando la corrosión, erosión y erosión – corrosión a un ángulo de impacto de 90 º en una solución de 0,5 M de NaCl y de sílice, analizando el número de bicapas sobre en la resistencia a la corrosión de estos recubrimientos. Las curvas de polarización se realizaron en el potencial de reposo. Posteriormente de la realización de los experimentos de las curvas de polarización las muestras se analizaron por microscopía electrónica de barrido. Los resultados muestran que el buen rendimiento de los sistemas multicapa en sistemas dinámicos de corrosión y corrosión por erosión y la mejora de desgaste es debido al hecho de que las curvas de polarización se mueven hacia las zonas donde las densidades de corriente disminuyen al aumentar el número de bicapas.

Synthesis of polypyrrole within the cell wall of yeast by redox-cycling of [Fe(CN)6](3-)/[Fe(CN)6](4-).

Science.gov (United States)

Ramanavicius, Arunas; Andriukonis, Eivydas; Stirke, Arunas; Mikoliunaite, Lina; Balevicius, Zigmas; Ramanaviciene, Almira

2016-02-01

Yeast cells are often used as a model system in various experiments. Moreover, due to their high metabolic activity, yeast cells have a potential to be applied as elements in the design of biofuel cells and biosensors. However a wider application of yeast cells in electrochemical systems is limited due to high electric resistance of their cell wall. In order to reduce this problem we have polymerized conducting polymer polypyrrole (Ppy) directly in the cell wall and/or within periplasmic membrane. In this research the formation of Ppy was induced by [Fe(CN)6](3-)ions, which were generated from K4[Fe(CN)6], which was initially added to polymerization solution. The redox process was catalyzed by oxido-reductases, which are present in the plasma membrane of yeast cells. The formation of Ppy was confirmed by spectrophotometry and atomic force microscopy. It was confirmed that the conducting polymer polypyrrole was formed within periplasmic space and/or within the cell wall of yeast cells, which were incubated in solution containing pyrrole, glucose and [Fe(CN)6](4-). After 24h drying at room temperature we have observed that Ppy-modified yeast cell walls retained their initial spherical form. In contrast to Ppy-modified cells, the walls of unmodified yeast have wrinkled after 24h drying. The viability of yeast cells in the presence of different pyrrole concentrations has been evaluated. Copyright © 2015 Elsevier Inc. All rights reserved.

Review IPEEE C.N. external event Vandellos II

International Nuclear Information System (INIS)

Hernandez, H.; Gasca, C.; Beltran, F.; Salvat, M.; Pifarre, D.; Canadell, F.; Aleman, A.

2010-01-01

Within the process of maintaining and updating the risk analysis of CN Vandellos II, results from the review of the study of vulnerability of the plant against severe accidents caused by external events (Individual Plant Examination on Extornal Events, IPEEE).

Gas-phase infrared spectrum of phosphorus (III) oxycyanide, OPCN: experimental and theoretical investigations

Science.gov (United States)

Allaf, Abdul. W.; Kassem, M.; Alibrahim, M.; Boustani, Ihsan

1999-03-01

An attempt was made to observe the gas-phase infrared spectrum of Phosphorus (III) oxycyanide, OPCN for the first time. This molecule was produced by an on-line process using phosphorus (III) oxychloride, OPCl as precursor passed over heated AgCN. The products were characterised by the infrared spectra of their vapours. The low resolution gas-phase Fourier transform infrared spectrum shows two bands centered at 2165 and 1385 cm -1. These bands are assigned to, ν1 (CN stretch) and ν2 (OP stretch), respectively. Ab initio self-consistent-field (SCF) molecular orbital (MO) and Møller-Plesset second order perturbation theory (MP2) calculations were performed to determine the geometry, total energy and vibrational frequencies of OPCN.

Multiple Stellar Populations of Globular Clusters from Homogeneous Ca-CN Photometry. II. M5 (NGC 5904) and a New Filter System

Science.gov (United States)

Lee, Jae-Woo

2017-07-01

Using our ingeniously designed new filter systems, we investigate multiple stellar populations of the red giant branch (RGB) and the asymptotic giant branch (AGB) in the globular cluster (GC) M5. Our results are the following. (1) Our {{cn}}{JWL} index accurately traces nitrogen abundances in M5, while other color indices fail to do so. (2) We find bimodal CN distributions in both RGB and AGB sequences, with number ratios between CN-weak (CN-w) and CN-strong (CN-s) of n(CN-w):n(CN-s) = 29:71 (±2) and 21:79 (±7), respectively. (3) We also find a bimodal photometric [N/Fe] distribution for M5 RGB stars. (4) Our {{cn}}{JWL}-[O/Fe] and {{cn}}{JWL}-[Na/Fe] relations show clear discontinuities between the two RGB populations. (5) Although small, the RGB bump of CN-s is slightly brighter, {{Δ }}{V}{bump} = 0.07 ± 0.04 mag. If real, the difference in the helium abundance becomes {{Δ }}Y = 0.028 ± 0.016, in the sense that CN-s is more helium enhanced. (6) Very similar radial but different spatial distributions with comparable center positions are found for the two RGB populations. The CN-s RGB and AGB stars are more elongated along the NW-SE direction. (7) The CN-s population shows a substantial net projected rotation, while that of the CN-w population is nil. (8) Our results confirm the deficiency of CN-w AGB stars previously noted by others. We show that it is most likely due to stochastic truncation in the outer part of the cluster. Finally, we discuss the formation scenario of M5. Based on observations made with the Cerro Tololo Inter-American Observatory (CTIO) 1 m telescope, which is operated by the SMARTS consortium.

Usefulness of intraoperative electromyographic monitoring of oculomotor and abducens nerves during skull base surgery.

Science.gov (United States)

Li, Zi-Yi; Li, Ming-Chu; Liang, Jian-Tao; Bao, Yu-Hai; Chen, Ge; Guo, Hong-Chuan; Ling, Feng

2017-10-01

Intraoperative neurophysiologic monitoring of the extraocular cranial nerve (EOCN) is not commonly performed because of technical difficulty and risk, reliability of the result and predictability of the postoperative function of the EOCN. We performed oculomotor nerve (CN III) and abducens nerve (CN VI) intraoperative monitoring in patients with skull base surgery by recording the spontaneous muscle activity (SMA) and compound muscle action potential (CMAP). Two types of needle electrodes of different length were percutaneously inserted into the extraocular muscles with the free-hand technique. We studied the relationships between the SMA and CMAP and postoperative function of CN III and CN VI. A total of 23 patients were included. Nineteen oculomotor nerves and 22 abducens nerves were monitored during surgery, respectively. Neurotonic discharge had a positive predictive value of less than 50% and negative predictive value of more than 80% for postoperative CN III and CN VI dysfunction. The latency of patients with postoperative CN III dysfunction was 2.79 ± 0.13 ms, longer than that with intact CN III function (1.73 ± 0.11 ms). One patient had transient CN VI dysfunction, whose CMAP latency (2.54 ms) was longer than that of intact CN VI function (2.11 ± 0.38 ms). There was no statistically significant difference between patients with paresis and with intact function. The method of intraoperative monitoring of EOCNs described here is safe and useful to record responses of SMA and CMAP. Neurotonic discharge seems to have limited value in predicting the postoperative function of CN III and CN VI. The onset latency of CMAP longer than 2.5 ms after tumor removal is probably relevant to postoperative CN III and CN VI dysfunction. However, a definite quantitative relationship has not been found between the amplitude and stimulation intensity of CMAP and the postoperative outcome of CN III and CN VI.

Thioether-ligated iron(ii) and iron(iii)-hydroperoxo/alkylperoxo complexes with an H-bond donor in the second coordination sphere†

OpenAIRE

Widger, Leland R.; Jiang, Yunbo; McQuilken, Alison C.; Yang, Tzuhsiung; Siegler, Maxime A.; Matsumura, Hirotoshi; Moënne-Loccoz, Pierre; Kumar, Devesh; de Visser, Sam P.; Goldberg, David P.

2014-01-01

The non-heme iron complexes, [FeII(N3PySR)(CH3CN)](BF4)2 (1) and [FeII(N3PyamideSR)](BF4)2 (2), afford rare examples of metastable Fe(iii)-OOH and Fe(iii)-OOtBu complexes containing equatorial thioether ligands and a single H-bond donor in the second coordination sphere. These peroxo complexes were characterized by a range of spectroscopic methods and density functional theory studies. The influence of a thioether ligand and of one H-bond donor on the stability and spectroscopic properties of...

Soil microbial C:N ratio is a robust indicator of soil productivity for paddy fields

Science.gov (United States)

Li, Yong; Wu, Jinshui; Shen, Jianlin; Liu, Shoulong; Wang, Cong; Chen, Dan; Huang, Tieping; Zhang, Jiabao

2016-10-01

Maintaining good soil productivity in rice paddies is important for global food security. Numerous methods have been developed to evaluate paddy soil productivity (PSP), most based on soil physiochemical properties and relatively few on biological indices. Here, we used a long-term dataset from experiments on paddy fields at eight county sites and a short-term dataset from a single field experiment in southern China, and aimed at quantifying relationships between PSP and the ratios of carbon (C) to nutrients (N and P) in soil microbial biomass (SMB). In the long-term dataset, SMB variables generally showed stronger correlations with the relative PSP (rPSP) compared to soil chemical properties. Both correlation and variation partitioning analyses suggested that SMB N, P and C:N ratio were good predictors of rPSP. In the short-term dataset, we found a significant, negative correlation of annual rice yield with SMB C:N (r = -0.99), confirming SMB C:N as a robust indicator for PSP. In treatments of the short-term experiment, soil amendment with biochar lowered SMB C:N and improved PSP, while incorporation of rice straw increased SMB C:N and reduced PSP. We conclude that SMB C:N ratio does not only indicate PSP but also helps to identify management practices that improve PSP.

Vibrational emission analysis of the CN molecules in laser-induced breakdown spectroscopy of organic compounds

Energy Technology Data Exchange (ETDEWEB)

Fernández-Bravo, Ángel; Delgado, Tomás; Lucena, Patricia; Laserna, J. Javier, E-mail: laserna@uma.es

2013-11-01

Laser-induced breakdown spectroscopy (LIBS) of organic materials is based on the analysis of atomic and ionic emission lines and on a few molecular bands, the most important being the CN violet system and the C{sub 2} Swan system. This paper is focused in molecular emission of LIBS plasmas based on the CN (B{sup 2}Σ–X{sup 2}Σ) band, one of the strongest emissions appearing in all carbon materials when analyzed in air atmosphere. An analysis of this band with sufficient spectral resolution provides a great deal of information on the molecule, which has revealed that valuable information can be obtained from the plume chemistry and dynamics affecting the excitation mechanisms of the molecules. The vibrational emission of this molecular band has been investigated to establish the dependence of this emission on the molecular structure of the materials. The paper shows that excitation/emission phenomena of molecular species observed in the plume depend strongly on the time interval selected and on the irradiance deposited on the sample surface. Precise time resolved LIBS measurements are needed for the observation of distinctive CN emission. For the organic compounds studied, larger differences in the behavior of the vibrational emission occur at early stages after plasma ignition. Since molecular emission is generally more complex than that involving atomic emission, local plasma conditions as well as plume chemistry may induce changes in vibrational emission of molecules. As a consequence, alterations in the distribution of the emissions occur in terms of relative intensities, being sensitive to the molecular structure of every single material. - Highlights: • Vibrational emission of CN species in laser-induced plasmas has been investigated. • Distribution of vibrational emission of CN has been found to be time dependent. • Laser irradiance affects the vibrational distribution of the CN molecules. • Plume chemistry controls the excitation mechanisms of CN

Chemical Complexity in Local Diffuse and Translucent Clouds: Ubiquitous Linear C3H and CH3CN, a Detection of HC3N and an Upper Limit on the Abundance of CH2CN

Science.gov (United States)

Liszt, Harvey; Gerin, Maryvonne; Beasley, Anthony; Pety, Jerome

2018-04-01

We present Jansky Very Large Array observations of 20–37 GHz absorption lines from nearby Galactic diffuse molecular gas seen against four cosmologically distant compact radio continuum sources. The main new observational results are that l-C3H and CH3CN are ubiqitous in the local diffuse molecular interstellar medium at {\\text{}}{A}{{V}} ≲ 1, while HC3N was seen only toward B0415 at {\\text{}}{A}{{V}} > 4 mag. The linear/cyclic ratio is much larger in C3H than in C3H2 and the ratio CH3CN/HCN is enhanced compared to TMC-1, although not as much as toward the Horsehead Nebula. More consequentially, this work completes a long-term program assessing the abundances of small hydrocarbons (CH, C2H, linear and cyclic C3H and C3 {{{H}}}2, and C4H and C4H‑) and the CN-bearing species (CN, HCN, HNC, HC3N, HC5N, and CH3CN): their systematics in diffuse molecular gas are presented in detail here. We also observed but did not strongly constrain the abundances of a few oxygen-bearing species, most prominently HNCO. We set limits on the column density of CH2CN, such that the anion CH2CN‑ is only viable as a carrier of diffuse interstellar bands if the N(CH2CN)/N(CH2CN‑) abundance ratio is much smaller in this species than in any others for which the anion has been observed. We argue that complex organic molecules (COMS) are not present in clouds meeting a reasonable definition of diffuse molecular gas, i.e., {\\text{}}{A}{{V}} ≲ 1 mag. Based on observations obtained with the NRAO Jansky Very Large Array (VLA).

Multisensor system for determination of iron(II), iron(III) and uranium(VI) in complex solutions

International Nuclear Information System (INIS)

Legin, A.V.; Seleznev, B.L.; Rudnitskaya, A.M.; Vlasov, Yu.G.

1998-01-01

The aim of the present paper is the development and analytical evaluation of a multisensor system for determination of low content of iron(II), iron(III) and uranium(VI) in complex aqueous media. Sensor array included sensors on the basis of chalcogenide vitreous materials with redox and ionic cross-sensitivities, crystalline silver sulphide electrode, noble metal electrodes Pt, Au, Ag and redox sensor on the basis of oxide glass. Potentiometric measurements have been taken in a conventional electrochemical cell vs. a standard Ag/AgCl reference electrode. All measurements have been taken at room temperature. Calibration solutions contained UO 2 (NO 3 ) 2 in concentration range 10 -6 -1,610 -5 mol/L, K 3 Fe(CN) 6 and K 4 Fe(CN) 6 or FeSO 4 (NH 4 ) 2 SO 4 and FeCl 3 , with the ratio of Fe(II)/Fe(III) concentration from 100:1 to 1:100, the total concentration of Fe was 10 -4 and 10 -5 mol/L. All solutions have been made on the background electrolyte of calcium and magnesium chlorides and sulphates with the fixed content of 5-27 mmol/L of each component which is a typical one for groundwater or mining water. Sensor potentials have been processed by a back-propagation artificial neural net. Average error of determination of Fe(II) and Fe(III) is about 20 %, of uranium(VI) - 40 %. It was found that sensitivity of the sensor array to iron and uranium is irrespective of the chemical form of these species

Kinetic study of the substitution of pyridine by cyanide in the bis(pyridine)cobalt(III)hematoporphyrin-IX: distinguishing between Isub(d) and D mechanism

International Nuclear Information System (INIS)

Birush, M.; Pribanicj, M.

1977-01-01

''Mass-law (rate) retardation'' effect shows that the reaction between the cyanide ion and bis(pyridine)cobalt(III)hematoporphyrin-IX complex to give (CN) 2 cobalt(III)hematoporphyrin-IX occurs by a purely dissociative (D but not Isub(d)) mechanism in chloroform. Limiting rate constant at the excess of cyanide ion concentration at 25 deg C was found to be 2.5x10 -3 S -1 and the competition ratio of pyridine (ksub(-) 1 ) and the cyanide ion (k 2 ) for a five coordinate intermediate (pyridin) cobalt(III)hematoporphyrin-IX complex was obtained as ksub(-) 1 /k 2 =0.35. (author)

Gas-phase infrared spectrum of phosphorus (III) oxycyanide, OPCN: Experimental and theoretical and theoretical investigations

International Nuclear Information System (INIS)

Allaf, A.W.; Kassem, M.; Alibrahim, M.

1999-01-01

An attempt was made to observe the gas-phase infrared spectrum of phosphorus (III) oxycyanide, OPCN for the first time. This molecule was produced by on-line process using phosphorus (III) oxychloride, OPCI as precursor passed over heated Ag CN. The products were characterised by the infrared spectra of their vapours. The low resolution gas-phase Fourier transform infrared spectrum shows two bands at 2165 and 1385 cm -1 . These bands are assigned to ν 1 (C≡N stretch) and ν 2 (O=P stretch), respectively. Ab initio self-consistent-field (SCF) molecular orbital (MO) and Moeller - Plesset second order perturbation theory (MP2) calculations were performed to determine the geometry, total energy and vibrational frequencies of OPCN. (authors)

On A Recent Theory of 'Legal Obligation'

Directory of Open Access Journals (Sweden)

Bruno Leoni

2009-02-01

Full Text Available This paper, by the late Bruno Leoni, was originally published in the Italian journal Il Politico in 1966. In the article, Leoni reviews H.L.A. Hart’s The Concept of Law (1961. Hart first analyzes the concept of law by resorting to the classical concept of “obligation.” But he later tries a “fresh start” by resorting to the concept of “secondary rules.” In his review, Leoni argues that the former attempt is confronted with serious difficulties, and that the latter attempt (to which professor Hart possibly resorts in view of overcoming some of said difficulties is ultimately inconsistent with the former

Iodine capture by Hofmann-type clathrate Ni(II)(pz)[Ni(II)(CN)_4

International Nuclear Information System (INIS)

Massasso, Giovanni; Long, Jerome; Haines, Julien; Devautour-Vinot, Sabine; Maurin, Guillaume; Larionova, Joulia; Guerin, Christian; Guari, Yannick; Grandjean, Agnes; Onida, Barbara; Donnadieu, Bruno

2014-01-01

The thermally stable Hofmann-type clathrate framework Ni(II)(pz)[Ni(II)(CN)_4] (pz = pyrazine) was investigated for the efficient and reversible sorption of iodine (I_2) in the gaseous phase and in solution with a maximum adsorption capacity of 1 mol of I_2 per 1 mol of Ni(II)pz)[Ni(II)(CN)_4] in solution. (authors)

2D water layer enclathrated between Mn(II)-Ni(CN)4 coordination frameworks

International Nuclear Information System (INIS)

Ray, Ambarish; Bhowmick, Indrani; Sheldrick, William S.; Jana, Atish Dipankar; Ali, Mahammed

2009-01-01

A [Ni(CN) 4 ] 2- based two-dimensional Mn(II) coordination polymer {Mn(H 2 O) 2 [NiCN] 4 .4H 2 O}, in which the coordination layers are stacked on top of each other sandwiching 2D water layer of boat-shaped hexagonal water clusters has been synthesized. The complex exhibits high thermal decomposition temperature and reversible water absorption, which were clearly demonstrated by thermal and PXRD studies on the parent and rehydrated complex after dehydration. - Abstract: A coordination polymer, {Mn(H 2 O) 2 [NiCN] 4 .4H 2 O} n , showed that the coordination layers are stacked on top of each other sandwiching 2D ice layer of boat-shaped hexagonal water clusters . Display Omitted

A critical quantum chemical and experimental study of the potentiality of direct labeling of the CN group with [99mTc(CO)3]+ or [186/188Re(CO)3]+ in CN containing biomolecules

International Nuclear Information System (INIS)

Safi, Benasser; Mertens, John; Kersemans, Ken; Geerlings, Paul

2008-01-01

Introduction: It was determined recently that [ 99m Tc(OH 2 ) 2 (X - )(CO 3 ) 3 ] could strongly bind to the CN group, allowing direct labeling of CN in vitamin B 12 despite the presence of a benzimidazole group. The aim of this paper was to perform a critical study of this potentiality, coupling quantum chemical calculations to experimental evidence. Methods: Computational methods: Within the density functional theory calculations, the 6-31+G** basis set (C, H, O, N atoms) and the LANL2DZ basis set (Tc,Re) were used. Stability calculations of the [RCNM(CO) 3 ] + ) (M=Tc,Re) complexes were performed with the Gaussian 03 suite of programs, while for the evaluation of relative stability substitution reactions were used. Radiochemistry: Vitamin B 12 , 4-hydroxy-benzylcyanide and 4-methoxy-benzonitrile were labeled at 100 deg. C during 30 min. High-performance liquid chromatography analysis was performed using radioactive and UV detection. Results: Computational methods: The influence of different ligands on the stability yielded a sequence: imidazole>tBuCN>NH 3 ∼CH 3 CN>HCN (mimicking the best CoCN)>H 2 O. The transmetalation reaction indicates that all ligands prefer Re to Tc. The preference for the nitrogen atom of imidazole to the cyanide nitrogen atom for complex formation with [Tc(CO) 3 (H 2 O) 3 ] + is interpreted in terms of the hard and soft acid and base properties principle. Radiochemistry: 4-Hydroxy-benzylcyanide and 4-methoxy-benzonitrile did not show any labeling. An excess of acetonitrile did not inhibit the labeling of vitamin B 12 as expected if the CN group should be involved, indicating that the labeling occurs on a stronger complexing group present like benzimidazole. Conclusion: Both theory and experiments prove that [CN-Tc(CO) 3 (H 2 O) (2-x) L x ] + complexes are weak and that in vitamin B 12 most probably the benzimidazole group is involved

Reactions of the CN Radical with Benzene and Toluene: Product Detection and Low-Temperature Kinetics

Energy Technology Data Exchange (ETDEWEB)

Trevitt, Adam J.; Goulay, Fabien; Taatjes, Craig A.; Osborn, David L.; Leone, Stephen R.

2009-12-23

Low temperature rate coefficients are measured for the CN + benzene and CN + toluene reactions using the pulsed Laval nozzle expansion technique coupled with laser-induced fluorescence detection. The CN + benzene reaction rate coefficient at 105, 165 and 295 K is found to be relatively constant over this temperature range, 3.9 - 4.9 x 10-10 cm3 molecule-1 s-1. These rapid kinetics, along with the observed negligible temperature dependence, are consistent with a barrierless reaction entrance channel and reaction efficiencies approaching unity. The CN + toluene reaction is measured to have a slower rate coefficient of 1.3 x 10-10 cm3 molecule-1 s-1 at 105 K. At room temperature, non-exponential decay profiles are observed for this reaction that may suggest significant back-dissociation of intermediate complexes. In separate experiments, the products of these reactions are probed at room temperature using synchrotron VUV photoionization mass spectrometry. For CN + benzene, cyanobenzene (C6H5CN) is the only product recorded with no detectable evidence for a C6H5 + HCN product channel. In the case of CN + toluene, cyanotoluene (NCC6H4CH3) constitutes the only detected product. It is not possible to differentiate among the ortho, meta and para isomers of cyanotoluene because of their similar ionization energies and the ~;; 40 meV photon energy resolution of the experiment. There is no significant detection of benzyl radicals (C6H5CH2) that would suggest a H-abstraction or a HCN elimination channel is prominent at these conditions. As both reactions are measured to be rapid at 105 K, appearing to have barrierless entrance channels, it follows that they will proceed efficiently at the temperatures of Saturn?s moon Titan (~;;100 K) and are also likely to proceed at the temperature of interstellar clouds (10-20 K).

Influence of trimethylsilane flow on the microstructure, mechanical and tribological properties of CrSiCN coatings in water lubrication

International Nuclear Information System (INIS)

Wu, Zhiwei; Zhou, Fei; Wang, Qianzhi; Zhou, Zhifeng; Yan, Jiwang; Li, Lawrence Kwok-Yan

2015-01-01

Highlights: • CrSiCN coatings with different Si and C contents were deposited. • CrSiCN coatings consisted of Cr(C,N) nanocrystallites and amorphous phases such as a-Si_3N_4(SiC, SiCN) and a-C(a-CN_x). • CrSiCN coatings exhibited the highest hardness of 21.3 GPa at the TMS flow of 10 sccm. • CrSiCN coatings deposited at the TMS flow of 10 sccm possessed the excellent tribological properties in water. • The wear mechanism changed from tribochemical wear to mechanical wear when the TMS flow increased. - Abstract: CrSiCN coatings with different silicon and carbon contents were deposited on silicon wafers and 316L stainless steels using unbalanced magnetron sputtering via adjusting trimethylsilane (TMS) flow, and their microstructure and mechanical properties were characterized by X-ray diffraction (XRD), scanning electron microscopy(SEM), X-ray photoelectrons spectroscopy(XPS) and nano-indenter, respectively. The tribological properties of CrSiCN coatings sliding against SiC balls in water were investigated using ball-on-disk tribometer. The results showed that the CrSiCN coatings had fine composite microstructure consisting of nanocrystallites of Cr(C, N) crystal and amorphous phases such as a-Si_3N_4 and a-C(a-CN_x). The typical columnar structures changed from fine cluster to coarse ones when the Si content was beyond 3.4 at.%. With an increase in the TMS flow, the hardness and Young's modulus of Corsican coatings all first increased, and then rapidly decreased, but the compressive stress in the coatings varied in the range of 2.8–4.8 GPa. When the TMS flow was 10 sccm, the CrSiCN coatings exhibited the highest hardness of 21.3 GPa and the lowest friction coefficient (0.11) and wear rate (8.4 × 10"−"8 mm"3/N m). But when the TMS flow was beyond 15 sccm, the tribological properties of CrSiCN coatings in water became poor.

Polymer-derived Ceramic SiCN-MoS2 Nanosheet Composite for Lithium Ion Battery Anodes

Science.gov (United States)

Bhandavat, Romil; Singh, Gurpreet

2012-02-01

We demonstrate synthesis of a novel SiCN-MoS2 nanosheet composite for use as Li-ion battery anode for high power applications. The nanosheet composite was prepared by thermal decomposition of polysilazane (SiCN precursor) on exfoliated MoS2 surfaces. The morphology and chemical structure was studied using a range of spectroscopy techniques that revealed a sidewall functionalization of exfoliated MoS2 by the polymeric precursor. The thermodynamic stability of SiCN-MoS2 nanosheets was also confirmed by thermo-gravimetric analysis (1000 degree C). Batteries assembled using MoS2-SiCN nanosheets as active anode material showed that lithium can be reversibly intercalated in the voltage range of 0-2.5 V with first cycle discharge capacity of 620 mAh/g at a current density of 100 mA/g.

Application of GIS-based SCS-CN method in West Bank catchments, Palestine

OpenAIRE

Sameer Shadeed; Mohammad Almasri

2010-01-01

Among the most basic challenges of hydrology are the prediction and quantification of catchment surface runoff. The runoff curve number (CN) is a key factor in determining runoff in the SCS (Soil Conservation Service) based hydrologic modeling method. The traditional SCS-CN method for calculating the composite curve number is very tedious and consumes a major portion of the hydrologic modeling time. Therefore, geographic information systems (GIS) are now being used in combination with the SCS...

Friction and wear of TiCN coatings deposited by filtered arc

International Nuclear Information System (INIS)

Huang, S.W.; Ng, K.; Samandi, M.

1998-01-01

A series of macroparticle-free TiN, TiCN and TiC coatings were deposited on 316 austenitic stainless steel using a titanium target in a filtered arc deposition system and reactive mixtures of CH4 and N2 gases. The microhardness of the coatings were measured by using an Ultra Microhardness Indentation System (UMIS-2000). The wear and friction of the coatings were assessed under controlled test conditions in a pin-on-disc tribometer. The results show a significant increase in microhardness and wear resistance as the CH4 :N2 gas flow rate ratio is increased. At lower load (14N), all coatings exhibited low friction and wear. At higher load (25N), the higher carbon content TiCN and TiC coatings showed a much lower friction and wear compared to TiN and low carbon TiCN. The topographical examination of coatings and worn surfaces established that the self-lubricating effect of the carbonaceous particles condensed from the plasma during the deposition was primarily responsible for the low friction and wear regime. (authors)

Growth feature of ionic nitrogen doped CN_x bilayer films with Ti and TiN interlayer by pulse cathode arc discharge

International Nuclear Information System (INIS)

Zhou, Bing; Liu, Zhubo; Piliptsou, D.G.; Rogachev, A.V.; Yu, Shengwang; Wu, Yanxia; Tang, Bin; Rudenkov, A.S.

2016-01-01

Graphical abstract: - Highlights: • Ti/ and TiN/CN_x (N"+) bilayers are prepared at various frequencies by pulse cathode arc. • Ti interlayer facilitates the introduction of N atoms into the CN_x (N"+) films. • The most N-sp"2C bonds (mainly graphite-like N) present in the TiN/CN_x (N"+, 3 Hz) film. • Ti/CN_x (N"+, 3 Hz) bilayer possesses small size and disordering of Csp"2 clusters. • The higher hardness and the lower stress presents in the TiN/CN_x (N"+, 10 Hz) bilayer. - Abstract: Using nano-scaled Ti and TiN as interlayer, ionic nitrogen doped carbon (CN_x (N"+)) bilayer films were prepared at various pulse frequencies by cathode arc technique. Elemental distribution at the interface, bonding compositions, microstructure, and mechanical properties of CN_x (N"+) bilayer films were investigated in dependence of interlayer and pulse frequency by Auger electron spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, nanoindentation, and surface profilometer. The results showed that the diffusion extent of C atoms at the interface of CN_x (N"+) bilayers is higher than for the α-C and CN_x (N_2) bilayers with the same interlayer. Nitrogen atoms could diffuse throughout the pre-deposited Ti and TiN layers into the Si substrate for all CN_x (N"+) bilayers. Ti interlayer facilitates the introduction of N atoms into the CN_x (N"+) films and exhibits a certain catalytic effect on the coordination of N atoms with sp"2- and sp"3-C binding. More nitrogenated and intense CN bonding configurations (mainly graphite-like N) form in the TiN/CN_x (N"+) bilayer. Ti/CN_x (N"+) bilayer prepared at low frequency possesses small size and disordering of Csp"2 clusters but TiN interlayer weakens the formation of Csp"2 bonding and increases the disordering of Csp"2 clusters in the films. The residual stress in the bilayer is lower than for CN_x (N"+) monolayer. The higher hardness and the lower residual stress are present in the TiN/CN_x (N"+, 10 Hz) bilayer.

CN emission spectroscopy study of carbon plasma in nitrogen environment

International Nuclear Information System (INIS)

Abdelli-Messaci, S.; Kerdja, T.; Bendib, A.; Malek, S.

2005-01-01

Spectroscopic emission diagnostics of a carbon plasma created by an excimer KrF laser pulse at three laser fluences (12, 25 and 32 J/cm 2 ) is performed under nitrogen ambient at pressures of 0.5 and 1 mbar. By following the time evolution of the radical CN spectral emission profiles, we notice, at a certain distance from the target surface, the existence of twin peaks for the time of flight distribution. This double structure depends on laser fluence and gas pressure parameters. The first peak moves forward in relation with the plasma expansion whereas the second peak moves backward and it is attributed to CN species undergoing oscillations or reflected shocks

Fe4 cluster and a buckled macrocycle complex from the reduction of [(dmgBF2)2Fe(L)2] (L = MeCN, (t)Bu(i)NC).

Science.gov (United States)

Rose, Michael J; Winkler, Jay R; Gray, Harry B

2012-02-20

We report the syntheses, X-ray structures, and reductive electrochemistry of the Fe(II) complexes [(dmgBF(2))(2)Fe(MeCN)(2)] (1; dmg = dimethylglyoxime, MeCN = acetonitrile) and [(dmgBF(2))Fe((t)Bu(i)NC)(2)] (2; (t)Bu(i)NC = tert-butylisocyanide). The reaction of 1 with Na/Hg amalgam led to isolation and the X-ray structure of [(dmgBF(2))(2)Fe(glyIm)] (3; glyIm = glyimine), wherein the (dmgBF(2))(2) macrocyclic frame is bent to accommodate the binding of a bidentate apical ligand. We also report the X-ray structure of a rare mixed-valence Fe(4) cluster with supporting dmg-type ligands. In the structure of [(dmg(2)BF(2))(3)Fe(3)((1)/(2)dmg)(3)Fe(O)(6)] (4), the (dmgBF(2))(2) macrocycle has been cleaved, eliminating BF(2) groups. Density functional theory calculations and electron paramagnetic resonance data are in accordance with a central Fe(III) ion surrounded by three formally Fe(II)dmg(2)BF(2) units.

Fine-structure resolved rotational transitions and database for CN+H2 collisions

Science.gov (United States)

Burton, Hannah; Mysliwiec, Ryan; Forrey, Robert C.; Yang, B. H.; Stancil, P. C.; Balakrishnan, N.

2018-06-01

Cross sections and rate coefficients for CN+H2 collisions are calculated using the coupled states (CS) approximation. The calculations are benchmarked against more accurate close-coupling (CC) calculations for transitions between low-lying rotational states. Comparisons are made between the two formulations for collision energies greater than 10 cm-1. The CS approximation is used to construct a database which includes highly excited rotational states that are beyond the practical limitations of the CC method. The database includes fine-structure resolved rotational quenching transitions for v = 0 and j ≤ 40, where v and j are the vibrational and rotational quantum numbers of the initial state of the CN molecule. Rate coefficients are computed for both para-H2 and ortho-H2 colliders. The results are shown to be in good agreement with previous calculations, however, the rates are substantially different from mass-scaled CN+He rates that are often used in astrophysical models.

Supramolecular architecture based on [Fe(CN)6]3- metallotectons and melaminium synthons

Science.gov (United States)

Krichen, Firas; Walha, Siwar; Lhoste, Jérôme; Bulou, Alain; Kabadou, Ahlem; Goutenoire, François

2017-10-01

Assembly involving [Fe(CN)6]3- metallotectons as building units and melaminium organic cation has been envisioned in order to elaborate a hybrid supramolecular based on ionic H-bonds with formula {(H-mel)4[Fe(CN)6]Cl} (H-mel+: melaminium cation). The compound has been prepared by diffusion method and characterized by single-crystal X-ray diffraction, EDX analysis, and Raman-IR spectroscopies with assignment from ab initio calculations. The melaminium exhibit self cationic coupling with cyclic hydrogen bonds to give a one dimensional {[H-mel]+}∝ synthon. Therefore, these cationic ribbons are inter-linked via hydrogen bonds by the anionic tectons [Fe(CN)6]3- and chlorine anion resulting on a 3D network. Molecular hirshfeld surfaces revealed that the crystal structure has been supported mainly by Nsbnd H⋯N and Nsbnd H⋯Cl intermolecular Hydrogen bonds and by favoured C⋯C and C⋯N weak interactions.

Feasibility of diffuse reflectance infrared Fourier spectroscopy (DRIFTS) to quantify iron-cyanide (Fe-CN) complexes in soil

Science.gov (United States)

Sut-Lohmann, Magdalena; Raab, Thomas

2017-04-01

Contaminated sites create a significant risk to human health, by poisoning drinking water, soil, air and as a consequence food. Continuous release of persistent iron-cyanide (Fe-CN) complexes from various industrial sources poses a high hazard to the environment and indicates the necessity to analyze considerable amount of samples. At the present time quantitative determination of Fe-CN concentration in soil usually requires a time consuming two step process: digestion of the sample (e.g., micro distillation system) and its analytical detection performed, e.g., by automated spectrophotometrical flow injection analysis (FIA). In order to determine the feasibility of diffuse reflectance infrared Fourier spectroscopy (DRIFTS) to quantify the Fe-CN complexes in soil matrix, 42 soil samples were collected (8 to 12.520 mg kg-1CN) indicating single symmetrical CN band in the range 2092 - 2084 cm-1. Partial least squares (PLS) calibration-validation model revealed IR response to CNtot exceeding 1268 mg kg-1 (limit of detection, LOD). Subsequently, leave-one-out cross-validation (LOO-CV) was performed on soil samples containing low CNtot (900 mg kg-1 resulted in LOD equal to 3494 mg kg-1. Our results indicate that spectroscopic data in combination with PLS statistics can efficiently be used to predict Fe-CN concentrations in soil. We conclude that the protocol applied in this study can strongly reduce the time and costs essential for the spatial and vertical screening of the site affected by complexed Fe-CN.

Phonons and colossal thermal expansion behavior of Ag3Co(CN)6 and Ag3Fe(CN)6.

Science.gov (United States)

Mittal, R; Zbiri, M; Schober, H; Achary, S N; Tyagi, A K; Chaplot, S L

2012-12-19

Recently colossal volume thermal expansion has been observed in the framework compounds Ag(3)Co(CN)(6) and Ag(3)Fe(CN)(6). We have measured phonon spectra using neutron time-of-flight spectroscopy as a function of temperature and pressure. Ab initio calculations were carried out for the sake of analysis and interpretation. Bonding is found to be very similar in the two compounds. At ambient pressure, modes in the intermediate frequency part of the vibrational spectra in the Co compound are shifted slightly to higher energies as compared to the Fe compound. The temperature dependence of the phonon spectra gives evidence for a large explicit anharmonic contribution to the total anharmonicity for low-energy modes below 5 meV. We have found that modes are mainly affected by the change in size of the unit cell, which in turn changes the bond lengths and vibrational frequencies. Thermal expansion has been calculated via the volume dependence of phonon spectra. Our analysis indicates that Ag phonon modes within the energy range 2-5 meV are strongly anharmonic and major contributors to thermal expansion in both systems. The application of pressure hardens the low-energy part of the phonon spectra involving Ag vibrations and confirms the highly anharmonic nature of these modes.

Density functional study of electronic, magnetic and hyperfine properties of [M(CN)5 NO]2- (M=Fe, Ru) and reduction products

International Nuclear Information System (INIS)

Gomez, J.A.; Guenzburger, Diana

1999-06-01

The Discrete Variational method (DVM) in density functional theory was employed to investigate the electronic structure of the complexes [Fe(CN) 5 NO] 2- (Nitroprusside), [Fe(CN) 5 NO] 3- , [Fe(CN) 4 NO] 2- , [Ru(CN) 5 NO] 2- and [Ru(CN) 5 NO] 3- . Total energy calculations revealed that in pentacyano nitrosyl ferrate (I) and pentacyano nitrosyl ruthenate (I), which are paramagnetic ions containing one unpaired electron, the M-N-O angle is bent, having values of 152.5 deg and 144 deg, respectively. From self-consistent spin-polarized calculations, the distribution of unpaired electron in the paramagnetic complexes [Fe(CN) 5 NO] 3, [Fe(CN) 4 NO] 2- and [Ru(CN) 5 NO] 3- was obtained as well as spin-density maps. A long-standing controversy regarding the configuration of [Fe(CN) 5 NO] 3- was elucidated, and it was found that the unpaired electron in this complex is in an orbital primarily localized on π * (NO). Moessbauer quadrupole splittings on Fe and Ru were derived from calculations of the electric-field gradients. Magnetic hyperfine coupling constants on No of the NO ligand were also obtained for the paramagnetic complexes. (author)

Synthesis of Ruthenium(III Phthalocyanine with Di-axial Bromo Ligands - A Promising Molecular Conductor with Giant Negative Magnetoresistance

Directory of Open Access Journals (Sweden)

Mario A.V. Gamboa

2015-01-01

Full Text Available The electron transport of Phthalocyanines (Pc with central metal and di-axial ligands (such as FeIII(PcL2; where L = CN, Cl, Br originates from its intermolecular Pc π-π orbital overlap while its giant negative magnetoresistance (GNMR arises from its intramolecular Pc-π(HOMO and Fe-d (s=1/2 interaction. However, the π-d interaction tends to localize itinerant electrons resulting in the decrease in the conductivity of the FeIII(PcL2 series compared to the non-magnetic CoIII(PcL2 where π-d interaction is absent. More so, the axial ligand field energy of the FeIII(PcL2 system is found to have the ability to proportionally modulate the π-d interaction. In reference thereof, theoretical calculations point that isostructural RuIII(PcBr2 would provide the best balance of π-d orbital energy interplay. That is, RuIII(PcBr2 is expected to be a molecule with high electrical conductivity and GNMR which would make it an ideal magnetic molecular conductor. This paper reports on the synthesis of RuIII(PcBr2.

Crystallization and preliminary crystallographic study of carnosinase CN2 from mice

Energy Technology Data Exchange (ETDEWEB)

Yamashita, Tetsuo; Unno, Hideaki; Ujita, Sayuri; Otani, Hiroto; Okumura, Nobuaki; Hashida-Okumura, Akiko; Nagai, Katsuya; Kusunoki, Masami, E-mail: kusunoki@protein.osaka-u.ac.jp [Institute for Protein Research, Osaka University, 3-2 Yamada-oka, Suita, Osaka 565-0871 (Japan)

2006-10-01

Mouse carnosinase was crystallized in complex with Zn{sup 2+} or Mn{sup 2+} and the complexes are undergoing structure determination by the MAD method. Mammalian tissues contain several histidine-containing dipeptides, of which l-carnosine is the best characterized and is found in various tissues including the brain and skeletal muscles. However, the mechanism for its biosynthesis and degradation have not yet been fully elucidated. Crystallographic study of carnosinase CN2 from mouse has been undertaken in order to understand its enzymatic mechanism from a structural viewpoint. CN2 was crystallized by the hanging-drop vapour-diffusion technique using PEG 3350 as a precipitant. Crystals were obtained in complex with either Mn{sup 2+} or Zn{sup 2+}. Both crystals of CN2 belong to the monoclinic space group P2{sub 1} and have almost identical unit-cell parameters (a = 54.41, b = 199.77, c = 55.49 Å, β = 118.52° for the Zn{sup 2+} complex crystals). Diffraction data were collected to 1.7 and 2.3 Å for Zn{sup 2+} and Mn{sup 2+} complex crystals, respectively, using synchrotron radiation. Structure determination is ongoing using the multiple-wavelength anomalous diffraction (MAD) method.

Crystallization and preliminary crystallographic study of carnosinase CN2 from mice

International Nuclear Information System (INIS)

Yamashita, Tetsuo; Unno, Hideaki; Ujita, Sayuri; Otani, Hiroto; Okumura, Nobuaki; Hashida-Okumura, Akiko; Nagai, Katsuya; Kusunoki, Masami

2006-01-01

Mouse carnosinase was crystallized in complex with Zn 2+ or Mn 2+ and the complexes are undergoing structure determination by the MAD method. Mammalian tissues contain several histidine-containing dipeptides, of which l-carnosine is the best characterized and is found in various tissues including the brain and skeletal muscles. However, the mechanism for its biosynthesis and degradation have not yet been fully elucidated. Crystallographic study of carnosinase CN2 from mouse has been undertaken in order to understand its enzymatic mechanism from a structural viewpoint. CN2 was crystallized by the hanging-drop vapour-diffusion technique using PEG 3350 as a precipitant. Crystals were obtained in complex with either Mn 2+ or Zn 2+ . Both crystals of CN2 belong to the monoclinic space group P2 1 and have almost identical unit-cell parameters (a = 54.41, b = 199.77, c = 55.49 Å, β = 118.52° for the Zn 2+ complex crystals). Diffraction data were collected to 1.7 and 2.3 Å for Zn 2+ and Mn 2+ complex crystals, respectively, using synchrotron radiation. Structure determination is ongoing using the multiple-wavelength anomalous diffraction (MAD) method

SFG experiment and ab initio study of the chemisorption of CN - on low-index platinum surfaces

Science.gov (United States)

Tadjeddine, M.; Flament, J.-P.; Le Rille, A.; Tadjeddine, A.

2006-05-01

A dual analysis is proposed in order to have a better understanding of the adsorption of the cyanide ions on a platinum electrode. The SFG (Sum Frequency Generation) spectroscopy allows the in situ vibrational study and the SFG spectra of the CN - species adsorbed on single crystal Pt electrode allow a systematic study of the low-index platinum surfaces. This experimental work is supported by ab initio calculations using density functional theory and cluster models. For each surface orientation and each geometry, a cluster model of 20-30 Pt atoms has been built in order to interpret the chemisorption of the CN - ions through four kinds of adsorption geometry: on-top or bridge site, bonding via C or N atoms. Geometries have been optimized and adsorption energies, electronic properties and vibrational frequencies have been computed. From the electronic properties, we can propose an analysis of the bonding mechanism for each studied kind of adsorption. The SFG spectra of the CN -/Pt(1 1 1) system present an unique resonance owing to the top C adsorption. It is mainly the same for the CN -/Pt(1 0 0) system. It is also the case for the SFG spectra of the CN -/Pt(1 1 0) system recorded at negative electrochemical voltage; at more positive voltage, a second resonance appears at a lower frequency, owing to the top N adsorption. Experimental and theoretical values of the C-N stretching frequencies are in excellent agreement.

Estimating Composite Curve Number Using an Improved SCS-CN Method with Remotely Sensed Variables in Guangzhou, China

Directory of Open Access Journals (Sweden)

Qihao Weng

2013-03-01

Full Text Available The rainfall and runoff relationship becomes an intriguing issue as urbanization continues to evolve worldwide. In this paper, we developed a simulation model based on the soil conservation service curve number (SCS-CN method to analyze the rainfall-runoff relationship in Guangzhou, a rapid growing metropolitan area in southern China. The SCS-CN method was initially developed by the Natural Resources Conservation Service (NRCS of the United States Department of Agriculture (USDA, and is one of the most enduring methods for estimating direct runoff volume in ungauged catchments. In this model, the curve number (CN is a key variable which is usually obtained by the look-up table of TR-55. Due to the limitations of TR-55 in characterizing complex urban environments and in classifying land use/cover types, the SCS-CN model cannot provide more detailed runoff information. Thus, this paper develops a method to calculate CN by using remote sensing variables, including vegetation, impervious surface, and soil (V-I-S. The specific objectives of this paper are: (1 To extract the V-I-S fraction images using Linear Spectral Mixture Analysis; (2 To obtain composite CN by incorporating vegetation types, soil types, and V-I-S fraction images; and (3 To simulate direct runoff under the scenarios with precipitation of 57mm (occurred once every five years by average and 81mm (occurred once every ten years. Our experiment shows that the proposed method is easy to use and can derive composite CN effectively.

K4 Fe(CN)6 as a spectrophotometric agent for uranium analysis

International Nuclear Information System (INIS)

Soedyartomo; Tarwita.

1976-01-01

The properties of K 4 Fe(CN) 6 as a spectrophotometric agent for Uranium analysis was observed by putting some experiment into practice. The experiment covers the observation of expanding colour stability, the optimization of operating condition (p,H. and wavelength), the effect of K 4 Fe(CN) 6 concentration and the preparation of its standard curves (transmitansion vs uranium concentration) and the observation of the interfering metal spectra s (Cu ++ , Fe ++ ) either of its mixtures or themselves alone, has been carried out. The result and discussion on it are given. (author)

Wireless passive polymer-derived SiCN ceramic sensor with integrated resonator/antenna

Science.gov (United States)

Li, Yan; Yu, Yuxi; San, Haisheng; Wang, Yansong; An, Linan

2013-10-01

This paper presents a passive wireless polymer-derived silicon carbonitride (SiCN) ceramic sensor based on cavity radio frequency resonator together with integrated slot antenna. The effect of the cavity sensor dimensions on the Q-factor and resonant frequency is investigated by numerical simulation. A sensor with optimal dimensions is designed and fabricated. It is demonstrated that the sensor signal can be wirelessly detected at distances up to 20 mm. Given the high-temperature stability of the SiCN, the sensor is very promising for high-temperature wireless sensing applications.

Probing the mer- to fac-isomerization of tris-cyclometallated homo- and heteroleptic (C,N)3 Iridium(III) complexes

NARCIS (Netherlands)

McDonald, A.R.; Lutz, M.; von Chrzanowski, L.S.; van Klink, G.P.M.; Spek, A.L.; van Koten, G.

2008-01-01

We have developed techniques which allow for covalent tethering, via a “hetero” cyclometallating ligand, of heteroleptic tris-cyclometallated iridium(III) complexes to polymeric supports (for application in light-emitting diode technologies). This involved the selective synthesis and thorough

Selective hydrogenation of phenol to cyclohexanone over Pd@CN (N-doped porous carbon): Role of catalyst reduction method

Science.gov (United States)

Hu, Shuo; Yang, Guangxin; Jiang, Hong; Liu, Yefei; Chen, Rizhi

2018-03-01

Selective phenol hydrogenation is a green and sustainable technology to produce cyclohexanone. The work focused on investigating the role of catalyst reduction method in the liquid-phase phenol hydrogenation to cyclohexanone over Pd@CN (N-doped porous carbon). A series of reduction methods including flowing hydrogen reduction, in-situ reaction reduction and liquid-phase reduction were designed and performed. The results highlighted that the reduction method significantly affected the catalytic performance of Pd@CN in the liquid-phase hydrogenation of phenol to cyclohexanone, and the liquid-phase reduction with the addition of appropriate amount of phenol was highly efficient to improve the catalytic activity of Pd@CN. The influence mechanism was explored by a series of characterizations. The results of TEM, XPS and CO chemisorption confirmed that the reduction method mainly affected the size, surface composition and dispersion of Pd in the CN material. The addition of phenol during the liquid-phase reduction could inhibit the aggregation of Pd NPs and promote the reduction of Pd (2+), and then improved the catalytic activity of Pd@CN. The work would aid the development of high-performance Pd@CN catalysts for selective phenol hydrogenation.

Co-composting of green waste and food waste at low C/N ratio

International Nuclear Information System (INIS)

Kumar, Mathava; Ou, Y.-L.; Lin, J.-G.

2010-01-01

In this study, co-composting of food waste and green waste at low initial carbon to nitrogen (C/N) ratios was investigated using an in-vessel lab-scale composting reactor. The central composite design (CCD) and response surface method (RSM) were applied to obtain the optimal operating conditions over a range of preselected moisture contents (45-75%) and C/N ratios (13.9-19.6). The results indicate that the optimal moisture content for co-composting of food waste and green waste is 60%, and the substrate at a C/N ratio of 19.6 can be decomposed effectively to reduce 33% of total volatile solids (TVS) in 12 days. The TVS reduction can be modeled by using a second-order equation with a good fit. In addition, the compost passes the standard germination index of white radish seed indicating that it can be used as soil amendment.

Gold nano-particle formation from crystalline AuCN: Comparison of thermal, plasma- and ion-beam activated decomposition

Energy Technology Data Exchange (ETDEWEB)

Beck, Mihály T.; Bertóti, Imre, E-mail: bertoti.imre@ttk.mta.hu; Mohai, Miklós; Németh, Péter; Jakab, Emma; Szabó, László; Szépvölgyi, János

2017-02-15

In this work, in addition to the conventional thermal process, two non-conventional ways, the plasma and ion beam activations are described for preparing gold nanoparticles from microcrystalline AuCN precursor. The phase formation at plasma and ion beam treatments was compared with that at thermal treatments and the products and transformations were characterized by thermogravimetry-mass-spectrometry (TG-MS), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). TG-MS measurements in Ar atmosphere revealed that AuCN decomposition starts at 400 °C and completes at ≈700 °C with evolution of gaseous (CN){sub 2}. XPS and TEM show that in heat treatment at 450 °C for 1 h in Ar, loss of nitrogen and carbon occurs and small, 5–30 nm gold particles forms. Heating at 450 °C for 10 h in sealed ampoule, much larger, 60–200 nm size and well faceted Au particles develop together with a fibrous (CN){sub n} polymer phase, and the Au crystallites are covered by a 3–5 nm thick polymer shell. Low pressure Ar plasma treatment at 300 eV energy results in 4–20 nm size Au particles and removes most of the nitrogen and part of carbon. During Ar{sup +} ion bombardment with 2500 eV energy, 5–30 nm size Au crystallites form already in 10 min, with preferential loss of nitrogen and with increased amount of carbon residue. The results suggest that plasma and ion beam activation, acting similarly to thermal treatment, may be used to prepare Au nanoparticles from AuCN on selected surface areas either by depositing AuCN precursors on selected regions or by focusing the applied ionized radiation. Thus they may offer alternative ways for preparing tailor-made catalysts, electronic devices and sensors for different applications. - Graphical abstract: Proposed scheme of the decomposition mechanism of AuCN samples: heat treatment in Ar flow (a) and in sealed ampoule (b); Ar{sup +} ion treatment at 300 eV (c) and at 2500 eV (d). Cross section sketches

Structural transition induced by charge-transfer in RbMn[Fe(CN) sub 6]. Investigation by synchrotron-radiation X-ray powder analysis

CERN Document Server

Moritomo, Y; Sakata, M; Kato, K; Kuriki, A; Tokoro, H; Ohkoshi, S I; Hashimoto, K

2002-01-01

Temperature dependence of atomic coordinates is determined for RbMn[Fe(CN) sub 6] by means of synchrotron-radiation (SR) X-ray powder structural analysis. We observed a structural transition from the cubic (F4-bar3m; Z=4) to the tetragonal (I4-barm2; Z=2) phase at approx. =210K in the cooling run and at approx. =300K in the warming run. In the low-temperature tetragonal phase, we found Jahn-Tellar type distortion of the MnN sub 6 octahedra and compression of the averaged Fe-C bond distance. These structural data suggest that the structural transition is triggered by the inter-metallic charge-transfer from the Mn(II) site to the Fe(III) site.

Crystal structure of tri­chlorido­(4'-ferrocenyl-2,2':6',2''-terpyridine-[kappa]3N,N',N'')iridium(III) aceto­nitrile disolvate

KAUST Repository

Davaasuren, Bambar; Padhy, Harihara; Rothenberger, Alexander

2015-01-01

In the title compound, [FeIr(C5H5)(C20H14N3)Cl3]·2CH3CN, the central IrIII atom is sixfold coordinated by three chloride ligands and three terpyridine N atoms in a slightly distorted octa­hedral fashion. The terpyridine ligand is functionalized

Blue phosphorescent mono-cyclometalated iridium(III) complexes

International Nuclear Information System (INIS)

Ham, Ho Wan; Yang, Yoon A; Kim, Young Sik

2010-01-01

New deep blue phosphorescent iridium(III) complexes comprised of one cyclometalate, two phosphines trans to each other and two cis-ancillary ligands, such as Ir(F 2 Meppy)(PPh 2 Me) 2 (H)(Cl), Ir(F 2 Meppy)(PPh 2 Me) 2 (H)(NCMe) + , and Ir(F 2 Meppy)(PPh 2 Me) 2 (H)(CN), [F 2 Meppy = 2-(2', 4'- difluorophenyl)-4-methyl-pyridine] were synthesized and studied to tune the phosphorescence wavelength to the deep blue region and to enhance the luminescence efficiencies. We investigated the strong field effects of ancillary ligands to gain insight into the factors responsible for the emission color change and the different luminescence efficiency. Reducing the molecular weight of the phosphine ligand with PPh 2 Me leads to more efficient deep-blue organic light-emitting devices (OLED) by thermal processing instead of through solution processing. The electron-withdrawing difluoro group substituted on the phenyl ring, the electron-donating methyl group on the pyridyl ring, and the cyano strong field ancillary ligand increased the HOMO-LUMO gap and achieved a hypsochromic shift in the emission color. As a result, the maximum emission spectra of Ir(F 2 Meppy)-(PPh 2 Me) 2 (H)(Cl), Ir(F 2 Meppy)(PPh 2 Me) 2 (H)(NCMe) + , and Ir(F 2 Meppy)(PPh 2 Me) 2- (H)(CN) were in the ranges of 440.5, 437, 436 nm, respectively.

A Survey of CH3CN and HC3N in Protoplanetary Disks

Science.gov (United States)

Bergner, Jennifer B.; Guzmán, Viviana G.; Öberg, Karin I.; Loomis, Ryan A.; Pegues, Jamila

2018-04-01

The organic content of protoplanetary disks sets the initial compositions of planets and comets, thereby influencing subsequent chemistry that is possible in nascent planetary systems. We present observations of the complex nitrile-bearing species CH3CN and HC3N toward the disks around the T Tauri stars AS 209, IM Lup, LkCa 15, and V4046 Sgr as well as the Herbig Ae stars MWC 480 and HD 163296. HC3N is detected toward all disks except IM Lup, and CH3CN is detected toward V4046 Sgr, MWC 480, and HD 163296. Rotational temperatures derived for disks with multiple detected lines range from 29 to 73 K, indicating emission from the temperate molecular layer of the disk. V4046 Sgr and MWC 480 radial abundance profiles are constrained using a parametric model; the gas-phase CH3CN and HC3N abundances with respect to HCN are a few to tens of percent in the inner 100 au of the disk, signifying a rich nitrile chemistry at planet- and comet-forming disk radii. We find consistent relative abundances of CH3CN, HC3N, and HCN between our disk sample, protostellar envelopes, and solar system comets; this is suggestive of a robust nitrile chemistry with similar outcomes under a wide range of physical conditions.

Regional Calibration of SCS-CN L-THIA Model: Application for Ungauged Basins

Directory of Open Access Journals (Sweden)

Ji-Hong Jeon

2014-05-01

Full Text Available Estimating surface runoff for ungauged watershed is an important issue. The Soil Conservation Service Curve Number (SCS-CN method developed from long-term experimental data is widely used to estimate surface runoff from gaged or ungauged watersheds. Many modelers have used the documented SCS-CN parameters without calibration, sometimes resulting in significant errors in estimating surface runoff. Several methods for regionalization of SCS-CN parameters were evaluated. The regionalization methods include: (1 average; (2 land use area weighted average; (3 hydrologic soil group area weighted average; (4 area combined land use and hydrologic soil group weighted average; (5 spatial nearest neighbor; (6 inverse distance weighted average; and (7 global calibration method, and model performance for each method was evaluated with application to 14 watersheds located in Indiana. Eight watersheds were used for calibration and six watersheds for validation. For the validation results, the spatial nearest neighbor method provided the highest average Nash-Sutcliffe (NS value at 0.58 for six watersheds but it included the lowest NS value and variance of NS values of this method was the highest. The global calibration method provided the second highest average NS value at 0.56 with low variation of NS values. Although the spatial nearest neighbor method provided the highest average NS value, this method was not statistically different than other methods. However, the global calibration method was significantly different than other methods except the spatial nearest neighbor method. Therefore, we conclude that the global calibration method is appropriate to regionalize SCS-CN parameters for ungauged watersheds.

Validity and extension of the SCS-CN method for computing infiltration and rainfall-excess rates

Science.gov (United States)

Mishra, Surendra Kumar; Singh, Vijay P.

2004-12-01

A criterion is developed for determining the validity of the Soil Conservation Service curve number (SCS-CN) method. According to this criterion, the existing SCS-CN method is found to be applicable when the potential maximum retention, S, is less than or equal to twice the total rainfall amount. The criterion is tested using published data of two watersheds. Separating the steady infiltration from capillary infiltration, the method is extended for predicting infiltration and rainfall-excess rates. The extended SCS-CN method is tested using 55 sets of laboratory infiltration data on soils varying from Plainfield sand to Yolo light clay, and the computed and observed infiltration and rainfall-excess rates are found to be in good agreement.

Antibacterial activity and cell compatibility of TiZrN, TiZrCN, and TiZr-amorphous carbon coatings

Energy Technology Data Exchange (ETDEWEB)

Huang, Heng-Li [School of Dentistry, China Medical University, Taichung 404, Taiwan (China); Department of Bioinformatics and Medical Engineering, Asia University, Taichung 41354, Taiwan (China); Chang, Yin-Yu, E-mail: yinyu@nfu.edu.tw [Department of Mechanical and Computer-aided Engineering, National Formosa University, Yunlin 632, Taiwan (China); Liu, Jia-Xu [Department of Mechanical and Computer-aided Engineering, National Formosa University, Yunlin 632, Taiwan (China); Tsai, Ming-Tzu [Department of Biomedical Engineering, Hungkuang University, Taichung 433, Taiwan (China); Lai, Chih-Ho [Department of Microbiology and Immunology, Graduate Institute of Biomedical Sciences, Chang Gung University, Taoyuan, Taiwan (China)

2015-12-01

A cathodic-arc evaporation system with plasma-enhanced duct equipment was used to deposit TiZrN, TiZrCN, and TiZr/a-C coatings. Reactive gases (N{sub 2} and C{sub 2}H{sub 2}) activated by the Ti and Zr plasma in the evaporation process was used to deposit the TiZrCN and TiZr/a-C coatings with different C and nitrogen contents. The crystalline structures and bonding states of coatings were analyzed by X-ray diffraction and X-ray photoelectron spectroscopy. The microbial activity of the coatings was evaluated against Staphylococcus aureus (Gram-positive bacteria) and Actinobacillus actinomycetemcomitans (Gram-negative bacteria) by in vitro antibacterial analysis using a fluorescence staining method employing SYTO9 and a bacterial-viability test on an agar plate. The cell compatibility and morphology related to CCD-966SK cell-line human skin fibroblast cells on the coated samples were also determined using the 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide assay, reverse-transcriptase-polymerase chain reaction, and scanning electron microscopy. The results suggest that the TiZrCN coatings not only possess better antibacterial performance than TiZrN and TiZr/a-C coatings but also maintain good compatibility with human skin fibroblast cells. - Highlights: • TiZrN, TiZrCN, and TiZr/a-C coatings were deposited using cathodic arc evaporation. • The TiZrCN showed a composite structure containing TiN, ZrN, and a-C. • The TiZrCN-coated Ti showed the least hydrophobicity among the samples. • The TiZrCN-coated Ti showed good human skin fibroblast cell viability. • The TiZrCN-coated Ti exhibited good antibacterial performance.

Improvement of the Surface Hardness of Stainless Steel with the TitaniumCarbonitride Ti(CN) Thin Films

International Nuclear Information System (INIS)

Agus-Purwadi; Tri-Mardji Atmono; Widdi-Usada; Lely-Susita; Yunanto

2000-01-01

Fabrication of the T i (CN) thin films with methods of implantation and RFsputtering for improving the surfaces hardness of stainless steel (SS) hasbeen done. Some kinds of T i C thin films which made individually by varyingof RF sputtering power from 0 up to 160 watt are implanted by the nitrogenion beams on the doses and energy ion optimum of 6.107 x 10 17 ion/cm 2 and100 keV, also fabrication of T i (CN) thin films use RF sputtering method withT i target and reaction gases as argon, silene and nitrogen on the optimum ofsputtering parameter condition. The thin films yields are characterized byusing Microhardness Tester MX 170, obtained SS hardness which layered T i (CN)as 402.5 KHN from its initial of 215.54 KHN and 371.74 KHN (layered T i C), itmeans that the SS surface hardness improve 1.867 times cumulatively. From theX-Ray Diffraction (XRD) analysis yield showed that the microstructure ofT i (CN) films on the SS substrates are dominated by characteristic cubiccrystal structure with Miller plane orientation (111) on the scattering angleof 2 θ = 44 o . Morphology visualization of T i (CN) thin films crosssection on the SS substrate is realized by Spectroscopy Electron Microscope(SEM). (author)

Mechanistic study on the fluorination of K[B(CN)4] with ClF enabling the high yield and large scale synthesis of K[B(CF3)4] and K[(CF3)3BCN].

Science.gov (United States)

Bernhardt, Eduard; Finze, Maik; Willner, Helge

2011-10-17

The fluorination of K[B(CN)(4)] with ClF is studied by millimolar test reactions in aHF and CH(2)Cl(2) solution and by subsequent identification of intermediates such as B-CF═NCl, B-CF(2)-NCl(2), and B-CF(3) species as well as NCl(3) by (19)F, (11)B NMR, and Raman spectroscopy, respectively. At first one cyano group of K[B(CN)(4)] is converted fast into a CF(3) group, and with increasing fluorination the reaction becomes slower and several intermediates could be observed. On the basis of these results, a synthesis was developed for K[B(CF(3))(4)] on a 0.2 molar scale by treatment of K[B(CN)(4)] diluted in aHF with ClF. The course of the reactions was followed by (i) monitoring the vapor pressure inside the reactor, (ii) observing the heat dissipation during ClF uptake, and (iii) measuring the volume of the released nitrogen gas. Since the fluorination of the last cyano group proceeds very slowly, the selective synthesis of K[(CF(3))(3)BCN] on a 0.2 molar scale is possible, as well. The analysis of the mechanisms, thermodynamics, and kinetics of the fluorination reactions is supported by density functional theory (DFT) calculations.

Post-transition state dynamics and product energy partitioning following thermal excitation of the F⋯HCH2CN transition state: Disagreement with experiment

Science.gov (United States)

Pratihar, Subha; Ma, Xinyou; Xie, Jing; Scott, Rebecca; Gao, Eric; Ruscic, Branko; Aquino, Adelia J. A.; Setser, Donald W.; Hase, William L.

2017-10-01

Born-Oppenheimer direct dynamics simulations were performed to study atomistic details of the F + CH3CN → HF + CH2CN H-atom abstraction reaction. The simulation trajectories were calculated with a combined M06-2X/MP2 algorithm utilizing the 6-311++G** basis set. The experiments were performed at 300 K, and assuming the accuracy of transition state theory (TST), the trajectories were initiated at the F⋯HCH2CN abstraction TS with a 300 K Boltzmann distribution of energy and directed towards products. Recrossing of the TS was negligible, confirming the accuracy of TST. HF formation was rapid, occurring within 0.014 ps of the trajectory initiation. The intrinsic reaction coordinate (IRC) for reaction involves rotation of HF about CH2CN and then trapping in the CH2CN⋯HF post-reaction potential energy well of ˜10 kcal/mol with respect to the HF + CH2CN products. In contrast to this IRC, five different trajectory types were observed: the majority proceeded by direct H-atom transfer and only 11% approximately following the IRC. The HF vibrational and rotational quantum numbers, n and J, were calculated when HF was initially formed and they increase as potential energy is released in forming the HF + CH2CN products. The population of the HF product vibrational states is only in qualitative agreement with experiment, with the simulations showing depressed and enhanced populations of the n = 1 and 2 states as compared to experiment. Simulations with an anharmonic zero-point energy constraint gave product distributions for relative translation, HF rotation, HF vibration, CH2CN rotation, and CH2CN vibration as 5%, 11%, 60%, 7%, and 16%, respectively. In contrast, the experimental energy partitioning percentages to HF rotation and vibration are 6% and 41%. Comparisons are made between the current simulation and those for other F + H-atom abstraction reactions. The simulation product energy partitioning and HF vibrational population for F + CH3CN → HF + CH2CN

Characterization of thick and thin film SiCN for pressure sensing at high temperatures.

Science.gov (United States)

Leo, Alfin; Andronenko, Sergey; Stiharu, Ion; Bhat, Rama B

2010-01-01

Pressure measurement in high temperature environments is important in many applications to provide valuable information for performance studies. Information on pressure patterns is highly desirable for improving performance, condition monitoring and accurate prediction of the remaining life of systems that operate in extremely high temperature environments, such as gas turbine engines. A number of technologies have been recently investigated, however these technologies target specific applications and they are limited by the maximum operating temperature. Thick and thin films of SiCN can withstand high temperatures. SiCN is a polymer-derived ceramic with liquid phase polymer as its starting material. This provides the advantage that it can be molded to any shape. CERASET™ also yields itself for photolithography, with the addition of photo initiator 2, 2-Dimethoxy-2-phenyl-acetophenone (DMPA), thereby enabling photolithographical patterning of the pre-ceramic polymer using UV lithography. SiCN fabrication includes thermosetting, crosslinking and pyrolysis. The technology is still under investigation for stability and improved performance. This work presents the preparation of SiCN films to be used as the body of a sensor for pressure measurements in high temperature environments. The sensor employs the phenomenon of drag effect. The pressure sensor consists of a slender sensitive element and a thick blocking element. The dimensions and thickness of the films depend on the intended application of the sensors. Fabrication methods of SiCN ceramics both as thin (about 40-60 μm) and thick (about 2-3 mm) films for high temperature applications are discussed. In addition, the influence of thermosetting and annealing processes on mechanical properties is investigated.

Characterization of Thick and Thin Film SiCN for Pressure Sensing at High Temperatures

Directory of Open Access Journals (Sweden)

Rama B. Bhat

2010-02-01

Full Text Available Pressure measurement in high temperature environments is important in many applications to provide valuable information for performance studies. Information on pressure patterns is highly desirable for improving performance, condition monitoring and accurate prediction of the remaining life of systems that operate in extremely high temperature environments, such as gas turbine engines. A number of technologies have been recently investigated, however these technologies target specific applications and they are limited by the maximum operating temperature. Thick and thin films of SiCN can withstand high temperatures. SiCN is a polymer-derived ceramic with liquid phase polymer as its starting material. This provides the advantage that it can be molded to any shape. CERASET™ also yields itself for photolithography, with the addition of photo initiator 2, 2-Dimethoxy-2-phenyl-acetophenone (DMPA, thereby enabling photolithographical patterning of the pre-ceramic polymer using UV lithography. SiCN fabrication includes thermosetting, crosslinking and pyrolysis. The technology is still under investigation for stability and improved performance. This work presents the preparation of SiCN films to be used as the body of a sensor for pressure measurements in high temperature environments. The sensor employs the phenomenon of drag effect. The pressure sensor consists of a slender sensitive element and a thick blocking element. The dimensions and thickness of the films depend on the intended application of the sensors. Fabrication methods of SiCN ceramics both as thin (about 40–60 µm and thick (about 2–3 mm films for high temperature applications are discussed. In addition, the influence of thermosetting and annealing processes on mechanical properties is investigated.

Cloning, Expression Profiling and Functional Analysis of CnHMGS, a Gene Encoding 3-hydroxy-3-Methylglutaryl Coenzyme A Synthase from Chamaemelum nobile

Directory of Open Access Journals (Sweden)

Shuiyuan Cheng

2016-03-01

Full Text Available Roman chamomile (Chamaemelum nobile L. is renowned for its production of essential oils, which major components are sesquiterpenoids. As the important enzyme in the sesquiterpenoid biosynthesis pathway, 3-hydroxy-3-methylglutaryl coenzyme A synthase (HMGS catalyze the crucial step in the mevalonate pathway in plants. To isolate and identify the functional genes involved in the sesquiterpene biosynthesis of C. nobile L., a HMGS gene designated as CnHMGS (GenBank Accession No. KU529969 was cloned from C. nobile. The cDNA sequence of CnHMGS contained a 1377 bp open reading frame encoding a 458-amino-acid protein. The sequence of the CnHMGS protein was highly homologous to those of HMGS proteins from other plant species. Phylogenetic tree analysis revealed that CnHMGS clustered with the HMGS of Asteraceae in the dicotyledon clade. Further functional complementation of CnHMGS in the mutant yeast strain YSC6274 lacking HMGS activity demonstrated that the cloned CnHMGS cDNA encodes a functional HMGS. Transcript profile analysis indicated that CnHMGS was preferentially expressed in flowers and roots of C. nobile. The expression of CnHMGS could be upregulated by exogenous elicitors, including methyl jasmonate and salicylic acid, suggesting that CnHMGS was elicitor-responsive. The characterization and expression analysis of CnHMGS is helpful to understand the biosynthesis of sesquiterpenoid in C. nobile at the molecular level and also provides molecular wealth for the biotechnological improvement of this important medicinal plant.

Cloning, Expression Profiling and Functional Analysis of CnHMGS, a Gene Encoding 3-hydroxy-3-Methylglutaryl Coenzyme A Synthase from Chamaemelum nobile.

Science.gov (United States)

Cheng, Shuiyuan; Wang, Xiaohui; Xu, Feng; Chen, Qiangwen; Tao, Tingting; Lei, Jing; Zhang, Weiwei; Liao, Yongling; Chang, Jie; Li, Xingxiang

2016-03-08

Roman chamomile (Chamaemelum nobile L.) is renowned for its production of essential oils, which major components are sesquiterpenoids. As the important enzyme in the sesquiterpenoid biosynthesis pathway, 3-hydroxy-3-methylglutaryl coenzyme A synthase (HMGS) catalyze the crucial step in the mevalonate pathway in plants. To isolate and identify the functional genes involved in the sesquiterpene biosynthesis of C. nobile L., a HMGS gene designated as CnHMGS (GenBank Accession No. KU529969) was cloned from C. nobile. The cDNA sequence of CnHMGS contained a 1377 bp open reading frame encoding a 458-amino-acid protein. The sequence of the CnHMGS protein was highly homologous to those of HMGS proteins from other plant species. Phylogenetic tree analysis revealed that CnHMGS clustered with the HMGS of Asteraceae in the dicotyledon clade. Further functional complementation of CnHMGS in the mutant yeast strain YSC6274 lacking HMGS activity demonstrated that the cloned CnHMGS cDNA encodes a functional HMGS. Transcript profile analysis indicated that CnHMGS was preferentially expressed in flowers and roots of C. nobile. The expression of CnHMGS could be upregulated by exogenous elicitors, including methyl jasmonate and salicylic acid, suggesting that CnHMGS was elicitor-responsive. The characterization and expression analysis of CnHMGS is helpful to understand the biosynthesis of sesquiterpenoid in C. nobile at the molecular level and also provides molecular wealth for the biotechnological improvement of this important medicinal plant.

Post-transition state dynamics and product energy partitioning following thermal excitation of the F⋯HCH2CN transition state: Disagreement with experiment.

Science.gov (United States)

Pratihar, Subha; Ma, Xinyou; Xie, Jing; Scott, Rebecca; Gao, Eric; Ruscic, Branko; Aquino, Adelia J A; Setser, Donald W; Hase, William L

2017-10-14

Born-Oppenheimer direct dynamics simulations were performed to study atomistic details of the F + CH 3 CN → HF + CH 2 CN H-atom abstraction reaction. The simulation trajectories were calculated with a combined M06-2X/MP2 algorithm utilizing the 6-311++G** basis set. The experiments were performed at 300 K, and assuming the accuracy of transition state theory (TST), the trajectories were initiated at the F⋯HCH 2 CN abstraction TS with a 300 K Boltzmann distribution of energy and directed towards products. Recrossing of the TS was negligible, confirming the accuracy of TST. HF formation was rapid, occurring within 0.014 ps of the trajectory initiation. The intrinsic reaction coordinate (IRC) for reaction involves rotation of HF about CH 2 CN and then trapping in the CH 2 CN⋯HF post-reaction potential energy well of ∼10 kcal/mol with respect to the HF + CH 2 CN products. In contrast to this IRC, five different trajectory types were observed: the majority proceeded by direct H-atom transfer and only 11% approximately following the IRC. The HF vibrational and rotational quantum numbers, n and J, were calculated when HF was initially formed and they increase as potential energy is released in forming the HF + CH 2 CN products. The population of the HF product vibrational states is only in qualitative agreement with experiment, with the simulations showing depressed and enhanced populations of the n = 1 and 2 states as compared to experiment. Simulations with an anharmonic zero-point energy constraint gave product distributions for relative translation, HF rotation, HF vibration, CH 2 CN rotation, and CH 2 CN vibration as 5%, 11%, 60%, 7%, and 16%, respectively. In contrast, the experimental energy partitioning percentages to HF rotation and vibration are 6% and 41%. Comparisons are made between the current simulation and those for other F + H-atom abstraction reactions. The simulation product energy partitioning and HF vibrational population for F + CH 3 CN �

Magnetic structure of molecular magnet Fe[Fe(CN) 6

Indian Academy of Sciences (India)

We have studied the magnetic structure of Fe[Fe(CN)6]·4H2O, prepared by precipitation method, using neutron diffraction technique. Temperature dependent DC magnetization study down to 4.2 K shows that the compound undergoes from a high temperature disordered (paramagnetic) to an ordered magnetic phase ...

New Insights into Understanding Irreversible and Reversible Lithium Storage within SiOC and SiCN Ceramics.

Science.gov (United States)

Graczyk-Zajac, Magdalena; Reinold, Lukas Mirko; Kaspar, Jan; Sasikumar, Pradeep Vallachira Warriam; Soraru, Gian-Domenico; Riedel, Ralf

2015-02-24

Within this work we define structural properties of the silicon carbonitride (SiCN) and silicon oxycarbide (SiOC) ceramics which determine the reversible and irreversible lithium storage capacities, long cycling stability and define the major differences in the lithium storage in SiCN and SiOC. For both ceramics, we correlate the first cycle lithiation or delithiation capacity and cycling stability with the amount of SiCN/SiOC matrix or free carbon phase, respectively. The first cycle lithiation and delithiation capacities of SiOC materials do not depend on the amount of free carbon, while for SiCN the capacity increases with the amount of carbon to reach a threshold value at ~50% of carbon phase. Replacing oxygen with nitrogen renders the mixed bond Si-tetrahedra unable to sequester lithium. Lithium is more attracted by oxygen in the SiOC network due to the more ionic character of Si-O bonds. This brings about very high initial lithiation capacities, even at low carbon content. If oxygen is replaced by nitrogen, the ceramic network becomes less attractive for lithium ions due to the more covalent character of Si-N bonds and lower electron density on the nitrogen atom. This explains the significant difference in electrochemical behavior which is observed for carbon-poor SiCN and SiOC materials.

Structural, Mechanical and Tribological Properties of NbCN-Ag Nanocomposite Films Deposited by Reactive Magnetron Sputtering

Directory of Open Access Journals (Sweden)

Fanjing Wu

2018-01-01

Full Text Available In this study, reactive magnetron sputtering was applied for preparing NbCN-Ag films with different Ag additions. Ag contents in the as-deposited NbCN-Ag films were achieved by adjusting Ag target power. The composition, microstructure, mechanical properties, and tribological properties were characterized using energy-dispersive X-ray spectroscopy (EDS, X-ray diffraction (XRD, field emission scanning electron microscope (FE-SEM, high resolution transmission electron microscopy (HRTEM, Raman spectrometry, nano-indentation, and high-temperature sliding wear tests. Results indicated that face-centered cubic (fcc NbN, hexagonal close-packed (hcp NbN and fcc Ag, amorphous C and amorphous CNx phase co-existed in the as-deposited NbCN-Ag films. After doping with 2.0 at.% Ag, the hardness and elastic modulus reached a maximum value of 33 GPa and 340 GPa, respectively. Tribological properties were enhanced by adding Ag in NbCN-Ag films at room temperature. When the test temperature rose from 300 to 500 °C, the addition of Ag was found beneficial for the friction properties, showing a lowest friction coefficient of ~0.35 for NbCN-12.9 at.% Ag films at 500 °C. This was mainly attributed to the existence of AgOx, NbOx, and AgNbOx lubrication phases that acted as solid lubricants to modify the wear mechanism.

New Insights into Understanding Irreversible and Reversible Lithium Storage within SiOC and SiCN Ceramics

Directory of Open Access Journals (Sweden)

Magdalena Graczyk-Zajac

2015-02-01

Full Text Available Within this work we define structural properties of the silicon carbonitride (SiCN and silicon oxycarbide (SiOC ceramics which determine the reversible and irreversible lithium storage capacities, long cycling stability and define the major differences in the lithium storage in SiCN and SiOC. For both ceramics, we correlate the first cycle lithiation or delithiation capacity and cycling stability with the amount of SiCN/SiOC matrix or free carbon phase, respectively. The first cycle lithiation and delithiation capacities of SiOC materials do not depend on the amount of free carbon, while for SiCN the capacity increases with the amount of carbon to reach a threshold value at ~50% of carbon phase. Replacing oxygen with nitrogen renders the mixed bond Si-tetrahedra unable to sequester lithium. Lithium is more attracted by oxygen in the SiOC network due to the more ionic character of Si-O bonds. This brings about very high initial lithiation capacities, even at low carbon content. If oxygen is replaced by nitrogen, the ceramic network becomes less attractive for lithium ions due to the more covalent character of Si-N bonds and lower electron density on the nitrogen atom. This explains the significant difference in electrochemical behavior which is observed for carbon-poor SiCN and SiOC materials.

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.

76 FR 28727 - Child Nutrition (CN) Labeling Program; Request for Extension and Revision of a Currently Approved...

Science.gov (United States)

2011-05-18

... (CN) Labeling Program; Request for Extension and Revision of a Currently Approved Information... INFORMATION: Title: Child Nutrition Labeling Program. OMB Number: 0581-0261 . Expiration Date of Approval: 3... collection. Abstract: The Child Nutrition (CN) Labeling Program is a voluntary technical assistance service...

Analysis of the Runoff for Watershed Using SCS-CN Method and Geographic Information Systems

OpenAIRE

P.Sundar Kumar; Dr.M.J.Ratna Kanth Babu,; Dr. T.V.Praveen; Venkata kumar.vagolu

2010-01-01

The Soil Conservation Service Curve Number (SCS-CN) method is widely used for predicting direct runoff volume for a given rainfall event. The applicability of the SCS-CN method and the runoff generation mechanism were thoroughly analyzed in a Mediterranean experimental watershed in Hyderabad. The region is characterized by a Mediterranean semi-arid climate. A detailed land cover and soil survey using remote sensing and GIS techniques, showed that the watershed is dominated by coarse soils wit...

Quantitative effects of composting state variables on C/N ratio through GA-aided multivariate analysis

International Nuclear Information System (INIS)

Sun Wei; Huang, Guo H.; Zeng Guangming; Qin Xiaosheng; Yu Hui

2011-01-01

It is widely known that variation of the C/N ratio is dependent on many state variables during composting processes. This study attempted to develop a genetic algorithm aided stepwise cluster analysis (GASCA) method to describe the nonlinear relationships between the selected state variables and the C/N ratio in food waste composting. The experimental data from six bench-scale composting reactors were used to demonstrate the applicability of GASCA. Within the GASCA framework, GA searched optimal sets of both specified state variables and SCA's internal parameters; SCA established statistical nonlinear relationships between state variables and the C/N ratio; to avoid unnecessary and time-consuming calculation, a proxy table was introduced to save around 70% computational efforts. The obtained GASCA cluster trees had smaller sizes and higher prediction accuracy than the conventional SCA trees. Based on the optimal GASCA tree, the effects of the GA-selected state variables on the C/N ratio were ranged in a descending order as: NH 4 + -N concentration > Moisture content > Ash Content > Mean Temperature > Mesophilic bacteria biomass. Such a rank implied that the variation of ammonium nitrogen concentration, the associated temperature and the moisture conditions, the total loss of both organic matters and available mineral constituents, and the mesophilic bacteria activity, were critical factors affecting the C/N ratio during the investigated food waste composting. This first application of GASCA to composting modelling indicated that more direct search algorithms could be coupled with SCA or other multivariate analysis methods to analyze complicated relationships during composting and many other environmental processes. - Research Highlights: → A genetic algorithm aided stepwise cluster analysis method in food waste composting. → Nonlinear relationships between the selected state variables and the C/N ratio. → Introduced proxy tables save around 70% computational

Quantitative effects of composting state variables on C/N ratio through GA-aided multivariate analysis

Energy Technology Data Exchange (ETDEWEB)

Sun Wei [Faculty of Engineering and Applied Science, University of Regina, Regina, Saskatchewan, S4S 0A2 (Canada); Huang, Guo H., E-mail: huangg@iseis.org [Faculty of Engineering and Applied Science, University of Regina, Regina, Saskatchewan, S4S 0A2 (Canada); MOE Key Laboratory of Regional Energy Systems Optimization, Sino-Canada Energy and Environmental Research Academy, North China Electric Power University, Beijing, 102206 (China); Zeng Guangming [MOE Key Laboratory of Environmental Biology and Pollution Control, College of Environmental Science and Engineering, Hunan University, Changsha, Hunan, 410082 (China); Qin Xiaosheng [School of Civil and Environmental Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Yu Hui [Faculty of Engineering and Applied Science, University of Regina, Regina, Saskatchewan, S4S 0A2 (Canada)

2011-03-01

It is widely known that variation of the C/N ratio is dependent on many state variables during composting processes. This study attempted to develop a genetic algorithm aided stepwise cluster analysis (GASCA) method to describe the nonlinear relationships between the selected state variables and the C/N ratio in food waste composting. The experimental data from six bench-scale composting reactors were used to demonstrate the applicability of GASCA. Within the GASCA framework, GA searched optimal sets of both specified state variables and SCA's internal parameters; SCA established statistical nonlinear relationships between state variables and the C/N ratio; to avoid unnecessary and time-consuming calculation, a proxy table was introduced to save around 70% computational efforts. The obtained GASCA cluster trees had smaller sizes and higher prediction accuracy than the conventional SCA trees. Based on the optimal GASCA tree, the effects of the GA-selected state variables on the C/N ratio were ranged in a descending order as: NH{sub 4}{sup +}-N concentration > Moisture content > Ash Content > Mean Temperature > Mesophilic bacteria biomass. Such a rank implied that the variation of ammonium nitrogen concentration, the associated temperature and the moisture conditions, the total loss of both organic matters and available mineral constituents, and the mesophilic bacteria activity, were critical factors affecting the C/N ratio during the investigated food waste composting. This first application of GASCA to composting modelling indicated that more direct search algorithms could be coupled with SCA or other multivariate analysis methods to analyze complicated relationships during composting and many other environmental processes. - Research Highlights: {yields} A genetic algorithm aided stepwise cluster analysis method in food waste composting. {yields} Nonlinear relationships between the selected state variables and the C/N ratio. {yields} Introduced proxy tables

Complete Genome Sequence of Bacillus velezensis CN026 Exhibiting Antagonistic Activity against Gram-Negative Foodborne Pathogens

OpenAIRE

Nannan, Catherine; Gillis, Annika; Caulier, Simon; Mahillon, Jacques

2018-01-01

ABSTRACT We report here the complete genome sequence of Bacillus velezensis strain CN026, a member of the B. subtilis group, which is known for its many industrial applications. The genome contains 3,995,812 bp and displays six gene clusters potentially involved in strain CN026’s activity against Gram-negative foodborne pathogens.

iCN718, an Updated and Improved Genome-Scale Metabolic Network Reconstruction of Acinetobacter baumannii AYE.

Science.gov (United States)

Norsigian, Charles J; Kavvas, Erol; Seif, Yara; Palsson, Bernhard O; Monk, Jonathan M

2018-01-01

Acinetobacter baumannii has become an urgent clinical threat due to the recent emergence of multi-drug resistant strains. There is thus a significant need to discover new therapeutic targets in this organism. One means for doing so is through the use of high-quality genome-scale reconstructions. Well-curated and accurate genome-scale models (GEMs) of A. baumannii would be useful for improving treatment options. We present an updated and improved genome-scale reconstruction of A. baumannii AYE, named iCN718, that improves and standardizes previous A. baumannii AYE reconstructions. iCN718 has 80% accuracy for predicting gene essentiality data and additionally can predict large-scale phenotypic data with as much as 89% accuracy, a new capability for an A. baumannii reconstruction. We further demonstrate that iCN718 can be used to analyze conserved metabolic functions in the A. baumannii core genome and to build strain-specific GEMs of 74 other A. baumannii strains from genome sequence alone. iCN718 will serve as a resource to integrate and synthesize new experimental data being generated for this urgent threat pathogen.

Synthesis, crystal structure, and vibrational spectra of the anhydrous lithium dicyanamide Li[N(CN){sub 2}

Energy Technology Data Exchange (ETDEWEB)

Reckeweg, Olaf [Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853-1301 (United States); Institut fuer Anorganische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany); DiSalvo, Francis J. [Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853-1301 (United States); Schulz, Armin [Max-Planck-Institut fuer Festkoerperforschung, Heisenbergstrasse 1, 70569 Stuttgart (Germany); Blaschkowski, Bjoern; Schleid, Thomas [Institut fuer Anorganische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany); Jagiella, Stefan [Institut fuer Physikalische und Theoretische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany)

2014-04-15

Crystals of Li[N(CN){sub 2}] were synthesized from a metathesis reaction of stoichiometric amounts of aqueous solutions of Na[N(CN){sub 2}] and Li{sub 2}[SO{sub 4}] followed by subsequent treatment with ethanol and evaporation of the filtered-off solution at 80 C under normal atmospheric conditions. The single crystals of the title compound are transparent, colorless, and extremly hygroscopic. X-ray structure analysis showed that Li[N(CN){sub 2}] crystallizes in the monoclinic space group P2/c with the cell parameters a = 530.79(8) pm, b = 524.89(9) pm, c = 1149.77(17) pm, β = 101.551(7) , and Z = 4. The crystal structure contains Li{sup +} cations in both tetrahedral and octahedral nitrogen coordination of the boomerang-shaped [N≡C-N-C≡N]{sup -} anions. The vibrational spectra of Li[N(CN){sub 2}] are reported as well, together with ab initio calculations for geometry and harmonic frequencies of the free dicyanamide anion. (Copyright copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Quantitative and sensitive analysis of CN molecules using laser induced low pressure He plasma

Energy Technology Data Exchange (ETDEWEB)

Pardede, Marincan [Department of Electrical Engineering, University of Pelita Harapan, 1100 M.H. Thamrin Boulevard, Lippo Village, Tangerang 15811 (Indonesia); Hedwig, Rinda [Department of Computer Engineering, Bina Nusantara University, 9 K.H. Syahdan, Jakarta 14810 (Indonesia); Abdulmadjid, Syahrun Nur; Lahna, Kurnia; Idris, Nasrullah; Ramli, Muliadi [Department of Physics, Faculty of Mathematics and Natural Sciences, Syiah Kuala University, Darussalam, Banda Aceh 23111, NAD (Indonesia); Jobiliong, Eric [Department of Industrial Engineering, University of Pelita Harapan, 1100 M.H. Thamrin Boulevard, Lippo Village, Tangerang 15811 (Indonesia); Suyanto, Hery [Department of Physics, Faculty of Mathematics and Natural Sciences, Udayana University, Kampus Bukit Jimbaran, Denpasar 80361, Bali (Indonesia); Marpaung, Alion Mangasi [Department of Physics, Faculty of Mathematics and Natural Sciences, Jakarta State University, 10 Rawamangun, Jakarta 13220 (Indonesia); Suliyanti, Maria Margaretha [Research Center for Physics, Indonesia Institute of Sciences, Kawasan Puspiptek, Serpong, Tangerang Selatan, 15314 Banten (Indonesia); Tjia, May On [Physics of Magnetism and Photonics Group, Faculty of Mathematics and Natural Sciences, Bandung Institute of Technology, 10 Ganesha, Bandung 40132 (Indonesia); Research Center of Maju Makmur Mandiri Foundation, 40/80 Srengseng Raya, Jakarta 11630 (Indonesia); Lie, Tjung Jie; Lie, Zener Sukra; Kurniawan, Davy Putra; Kurniawan, Koo Hendrik, E-mail: kurnia18@cbn.net.id [Research Center of Maju Makmur Mandiri Foundation, 40/80 Srengseng Raya, Jakarta 11630 (Indonesia); Kagawa, Kiichiro [Research Center of Maju Makmur Mandiri Foundation, 40/80 Srengseng Raya, Jakarta 11630 (Indonesia); Fukui Science Education Academy, Takagi Chuou 2 choume, Fukui 910-0804 (Japan)

2015-03-21

We report the results of experimental study on CN 388.3 nm and C I 247.8 nm emission characteristics using 40 mJ laser irradiation with He and N{sub 2} ambient gases. The results obtained with N{sub 2} ambient gas show undesirable interference effect between the native CN emission and the emission of CN molecules arising from the recombination of native C ablated from the sample with the N dissociated from the ambient gas. This problem is overcome by the use of He ambient gas at low pressure of 2 kPa, which also offers the additional advantages of cleaner and stronger emission lines. The result of applying this favorable experimental condition to emission spectrochemical measurement of milk sample having various protein concentrations is shown to yield a close to linear calibration curve with near zero extrapolated intercept. Additionally, a low detection limit of 5 μg/g is found in this experiment, making it potentially applicable for quantitative and sensitive CN analysis. The visibility of laser induced breakdown spectroscopy with low pressure He gas is also demonstrated by the result of its application to spectrochemical analysis of fossil samples. Furthermore, with the use of CO{sub 2} ambient gas at 600 Pa mimicking the Mars atmosphere, this technique also shows promising applications to exploration in Mars.

Formation of Nitriles in the Interstellar Medium via Reactions of Cyano Radicals, CN(X2Σ+), with Unsaturated Hydrocarbons

Science.gov (United States)

Balucani, N.; Asvany, O.; Huang, L. C. L.; Lee, Y. T.; Kaiser, R. I.; Osamura, Y.; Bettinger, H. F.

2000-12-01

Crossed molecular beam experiments of cyano radicals, CN(X2Σ+, ν=0), in their electronic and vibrational ground state reacting with unsaturated hydrocarbons acetylene, C2H2(X1Σ+g), ethylene, C2H4(X1Ag), methylacetylene, CH3CCH(X1A1), allene, H2CCCH2(X1A1), dimethylacetylene, CH3CCCH3(X1A1'), and benzene, C6H6 (X1A1g), were performed at relative collision energies between 13.3 and 36.4 kJ mol-1 to unravel the formation of unsaturated nitriles in the outflows of late-type AGB carbon stars and molecular clouds. In all reactions, the CN radical was found to attack the π electron density of the hydrocarbon molecule with the radical center located at the carbon atom; the formation of an initial addition complex is a prevalent pathway on all the involved potential energy surfaces. A subsequent carbon-hydrogen bond rupture yields the nitriles cyanoacetylene, HCCCN (X1Σ+), vinylcyanide, C2H3CN (X1A'), 1-methylcyanoacetylene, CH3CCCN (X1A1), cyanoallene, H2CCCH(CN) (X1A'), 3-methylcyanoacetylene, HCCCH2CN(X1A'), 1,1-cyanomethylallene, H2CCC(CN)(CH3) (X1A'), and cyanobenzene, C6H5CN (X1A1). In case of acetylene and ethylene, a second reaction channel involves a [1, 2]-H atom shift in the initial HCCHCN and H2CCH2CN collision complexes prior to a hydrogen atom release to form cyanoacetylene, HCCCN (X1Σ+), and vinylcyanide, C2H3CN (X1A'). Since all these radical-neutral reactions show no entrance barriers, have exit barriers well below the energy of the reactant molecules, and are exothermic, the explicit identification of this CN versus H atom exchange pathway under single collision conditions makes this reaction class a compelling candidate to synthesize unsaturated nitriles in interstellar environments holding temperatures as low as 10 K. This general concept makes it even feasible to predict the formation of nitriles once the corresponding unsaturated hydrocarbons are identified in the interstellar medium. Here HCCCN, C2H3CN, and CH3CCCN have been already observed

Complete Genome Sequence of Bacillus velezensis CN026 Exhibiting Antagonistic Activity against Gram-Negative Foodborne Pathogens.

Science.gov (United States)

Nannan, Catherine; Gillis, Annika; Caulier, Simon; Mahillon, Jacques

2018-01-25

We report here the complete genome sequence of Bacillus velezensis strain CN026, a member of the B. subtilis group, which is known for its many industrial applications. The genome contains 3,995,812 bp and displays six gene clusters potentially involved in strain CN026's activity against Gram-negative foodborne pathogens. Copyright © 2018 Nannan et al.

Cellular uptake of exogenous calcineurin B is dependent on TLR4/MD2/CD14 complexes, and CnB is an endogenous ligand of TLR4.

Science.gov (United States)

Yang, Jinju; Qin, Nannan; Zhang, Hongwei; Yang, Rui; Xiang, Benqiong; Wei, Qun

2016-04-19

Our previous research showed that recombinant calcineurin B (rhCnB) stimulates cytokine secretion by immune cells, probably through TLR4. Exogenous CnB can be incorporated into many different tumour cells in vitro, but the mode of uptake and receptors required remain unknown. Here, we report that exogenous CnB is taken up by cells in a time- and concentration-dependent manner via clathrin-dependent receptor-mediated internalization. Our findings further confirm that uptake is mediated by the TLR4/MD2 complex together with the co-receptor CD14. The MST results revealed a high affinity between CnB and the TLR4 receptor complex. No binding was detected between CnB and LPS. CnB inhibited the uptake of LPS, and LPS also inhibited the uptake of CnB. These results indicate that the uptake of exogenous CnB did not occur through LPS and that CnB was not a chaperone of LPS. Thus, we conclude that TLR4 receptor complexes were required for the recognition and internalization of exogenous CnB. CnB could be a potential endogenous ligand of TLR4 and function as an agonist of TLR4. These properties of CnB support its potential for development as an anti-cancer drug.

Blue phosphorescent mono-cyclometalated iridium(III) complexes

Energy Technology Data Exchange (ETDEWEB)

Ham, Ho Wan; Yang, Yoon A; Kim, Young Sik [Hongik University, Seoul (Korea, Republic of)

2010-12-15

New deep blue phosphorescent iridium(III) complexes comprised of one cyclometalate, two phosphines trans to each other and two cis-ancillary ligands, such as Ir(F{sub 2}Meppy)(PPh{sub 2}Me){sub 2}(H)(Cl), Ir(F{sub 2}Meppy)(PPh{sub 2}Me){sub 2}(H)(NCMe){sup +}, and Ir(F{sub 2}Meppy)(PPh{sub 2}Me){sub 2}(H)(CN), [F{sub 2}Meppy = 2-(2', 4'- difluorophenyl)-4-methyl-pyridine] were synthesized and studied to tune the phosphorescence wavelength to the deep blue region and to enhance the luminescence efficiencies. We investigated the strong field effects of ancillary ligands to gain insight into the factors responsible for the emission color change and the different luminescence efficiency. Reducing the molecular weight of the phosphine ligand with PPh{sub 2}Me leads to more efficient deep-blue organic light-emitting devices (OLED) by thermal processing instead of through solution processing. The electron-withdrawing difluoro group substituted on the phenyl ring, the electron-donating methyl group on the pyridyl ring, and the cyano strong field ancillary ligand increased the HOMO-LUMO gap and achieved a hypsochromic shift in the emission color. As a result, the maximum emission spectra of Ir(F{sub 2}Meppy)-(PPh{sub 2}Me){sub 2}(H)(Cl), Ir(F{sub 2}Meppy)(PPh{sub 2}Me){sub 2}(H)(NCMe){sup +}, and Ir(F{sub 2}Meppy)(PPh{sub 2}Me){sub 2-}(H)(CN) were in the ranges of 440.5, 437, 436 nm, respectively.

Optimal C:N ratio for the production of red pigments by Monascus ruber.

Science.gov (United States)

Said, Farhan M; Brooks, John; Chisti, Yusuf

2014-09-01

The carbon-to-nitrogen (C:N) ratio in the biomass of microfungi tends to be quite different (e.g. 10-15) compared with the C:N ratio in the red pigments (e.g. >20) of the fungus Monascus ruber. Therefore, determining an optimal C:N ratio in the culture medium for maximizing the production of the pigments is important. A culture medium composition is established for maximizing the production of the red pigment by the fungus M. ruber ICMP 15220 in submerged culture. The highest volumetric productivity of the red pigment was 0.023 AU L(-1) h(-1) in a batch culture (30 °C, initial pH of 6.5) with a defined medium of the following composition (g L(-1)): glucose (10), monosodium glutamate (MSG) (10), MgSO4·7H2O (0.5), KH2PO4 (5), K2HPO4 (5), ZnSO4·7H2O (0.01), FeSO4·7H2O (0.01), CaCl2 (0.1), MnSO4·H2O (0.03). This medium formulation had a C:N mole ratio of 9:1. Under these conditions, the specific growth rate of the fungus was 0.043 h(-1) and the peak biomass concentration was 6.7 g L(-1) in a 7-day culture. The biomass specific productivity of the red pigment was 1.06 AU g(-1) h(-1). The best nitrogen source proved to be MSG although four other inorganic nitrogen sources were evaluated.

Polarized Neutron Diffraction to Probe Local Magnetic Anisotropy of a Low-Spin Fe(III) Complex.

Science.gov (United States)

Ridier, Karl; Mondal, Abhishake; Boilleau, Corentin; Cador, Olivier; Gillon, Béatrice; Chaboussant, Grégory; Le Guennic, Boris; Costuas, Karine; Lescouëzec, Rodrigue

2016-03-14

We have determined by polarized neutron diffraction (PND) the low-temperature molecular magnetic susceptibility tensor of the anisotropic low-spin complex PPh4 [Fe(III) (Tp)(CN)3]⋅H2O. We found the existence of a pronounced molecular easy magnetization axis, almost parallel to the C3 pseudo-axis of the molecule, which also corresponds to a trigonal elongation direction of the octahedral coordination sphere of the Fe(III) ion. The PND results are coherent with electron paramagnetic resonance (EPR) spectroscopy, magnetometry, and ab initio investigations. Through this particular example, we demonstrate the capabilities of PND to provide a unique, direct, and straightforward picture of the magnetic anisotropy and susceptibility tensors, offering a clear-cut way to establish magneto-structural correlations in paramagnetic molecular complexes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A single optical sensor with high sensitivity for detection of Fe{sup 3+} and CN{sup −} ions

Energy Technology Data Exchange (ETDEWEB)

Afshani, Jafar [School of Chemistry, College of Science, University of Tehran, Tehran (Iran, Islamic Republic of); Badiei, Alireza, E-mail: abadiei@khayam.ut.ac.ir [School of Chemistry, College of Science, University of Tehran, Tehran (Iran, Islamic Republic of); Nanobiomedicine Center of Excellence, Nanoscience and Nanotechnology Research Center, University of Tehran, Tehran (Iran, Islamic Republic of); Jafari, Maryam; Shayesteh, Alireza; Karimi, Mehdi; Lashgari, Negar [School of Chemistry, College of Science, University of Tehran, Tehran (Iran, Islamic Republic of); Mohammadi Ziarani, Ghodsi [Department of Chemistry, Alzahra University, Tehran (Iran, Islamic Republic of)

2016-11-15

1,2-Bis(2-hydroxymethylphenoxy)ethane was synthesized and characterized by FT-IR and {sup 1}H NMR spectroscopy, and single crystal X-ray diffraction method. The sensing ability of the sensor was studied in the presence of different cations and anions. Following the excitation wavelengths at 275 nm in EtOH/H{sub 2}O (1:9, v/v) and 310 nm in MeCN/H{sub 2}O (1:9, v/v), two distinct emissions at 305 and 356 nm were obtained, respectively. Fe{sup 3+} and CN{sup −} ions were successfully detected in EtOH/H{sub 2}O and MeCN/H{sub 2}O mixtures, respectively. While the fluorescence intensity of the sensor quenched considerably in the presence of Fe{sup 3+} cation at 305 nm, it enhanced in the presence of CN{sup −} anion at 356 nm. Selectivity of the sensor toward these ions was verified in the presence of a variety of common interfering ions. The detection limits of Fe{sup 3+} and CN{sup −} were calculated as 5.4 × 10{sup −9} mol L{sup −1} and 1.9 × 10{sup −8} mol L{sup −1}, respectively which shows the high sensitivity of the sensor toward the target ions. Finally, the interaction of the sensor and CN{sup −} anion was determined by computational studies.

Preliminary verification of structure design for CN HCCB TBM with 1 × 4 configuration

Energy Technology Data Exchange (ETDEWEB)

Zhao, Zhou, E-mail: zhaozhou@swip.ac.cn; Zhou, Bing; Wang, Qijie; Cao, Qixiang; Feng, Kaiming; Wang, Xiaoyu; Zhang, Guoshu

2016-02-15

Highlights: • A new and simplification structural design scheme with 1 × 4 configuration is proposed for CN HCCB TBM. • The detail conceptual structural design for 1 × 4 TBM is completed. • The preliminary hydraulic analysis, thermo-hydraulic analysis and structural analysis for 1 × 4 TBM had been carried out. - Abstract: Based on the conceptual design of CN HCCB TBM with 1 × 4 configuration, the preliminary hydraulic analysis, thermo-hydraulic analysis and structural analysis had been carried out for it. Hydraulic and thermo-hydraulic analyses show that the coolant manifold system could meet the fluid design requirement preliminarily and the temperature of RAFMs structural parts, Be and Li{sub 4}SiO{sub 4} pebble beds are within the allowable range, and no zone shows a stress higher than the allowable limit in the preliminary structural analysis. These results indicate the design for CN HCCB TBM with 1 × 4 configuration is preliminary reasonable.

Preliminary verification of structure design for CN HCCB TBM with 1 × 4 configuration

International Nuclear Information System (INIS)

Zhao, Zhou; Zhou, Bing; Wang, Qijie; Cao, Qixiang; Feng, Kaiming; Wang, Xiaoyu; Zhang, Guoshu

2016-01-01

Highlights: • A new and simplification structural design scheme with 1 × 4 configuration is proposed for CN HCCB TBM. • The detail conceptual structural design for 1 × 4 TBM is completed. • The preliminary hydraulic analysis, thermo-hydraulic analysis and structural analysis for 1 × 4 TBM had been carried out. - Abstract: Based on the conceptual design of CN HCCB TBM with 1 × 4 configuration, the preliminary hydraulic analysis, thermo-hydraulic analysis and structural analysis had been carried out for it. Hydraulic and thermo-hydraulic analyses show that the coolant manifold system could meet the fluid design requirement preliminarily and the temperature of RAFMs structural parts, Be and Li_4SiO_4 pebble beds are within the allowable range, and no zone shows a stress higher than the allowable limit in the preliminary structural analysis. These results indicate the design for CN HCCB TBM with 1 × 4 configuration is preliminary reasonable.

Mechanical Properties And Microstructure Of AlN/SiCN Nanocomposite Coatings Prepared By R.F.-Reactive Sputtering Method

Directory of Open Access Journals (Sweden)

Nakafushi Y.

2015-06-01

Full Text Available FIn this work, AlN/SiCN composite coatings were deposited by r.f.-reactive sputtering method using a facing target-type sputtering (FTS apparatus with composite targets consisting of Al plate and SiC chips in a gaseous mixture of Ar and N2, and investigated their mechanical properties and microstructure. The indentation hardness (HIT of AlN/SiCN coatings prepared from composite targets consisting of 8 ~32 chips of SiC and Al plate showed the maximum value of about 29~32 GPa at a proper nitrogen gas flow rate. X-ray diffraction (XRD patterns for the AlN/SiCN composite coatings indicated the presence of the only peeks of hexagonal (B4 structured AlN phase. AlN coatings clarified the columnar structure of the cross sectional view TEM observation. On the other hand, microstructure of AlN/SiCN composite coatings changed from columnar to equiaxed structure with increasing SiCN content. HR-TEM observation clarified that the composite coatings consisted of very fine equiaxial grains of B4 structured AlN phase and amorphous phase.

Quantitative effects of composting state variables on C/N ratio through GA-aided multivariate analysis.

Science.gov (United States)

Sun, Wei; Huang, Guo H; Zeng, Guangming; Qin, Xiaosheng; Yu, Hui

2011-03-01

It is widely known that variation of the C/N ratio is dependent on many state variables during composting processes. This study attempted to develop a genetic algorithm aided stepwise cluster analysis (GASCA) method to describe the nonlinear relationships between the selected state variables and the C/N ratio in food waste composting. The experimental data from six bench-scale composting reactors were used to demonstrate the applicability of GASCA. Within the GASCA framework, GA searched optimal sets of both specified state variables and SCA's internal parameters; SCA established statistical nonlinear relationships between state variables and the C/N ratio; to avoid unnecessary and time-consuming calculation, a proxy table was introduced to save around 70% computational efforts. The obtained GASCA cluster trees had smaller sizes and higher prediction accuracy than the conventional SCA trees. Based on the optimal GASCA tree, the effects of the GA-selected state variables on the C/N ratio were ranged in a descending order as: NH₄+-N concentration>Moisture content>Ash Content>Mean Temperature>Mesophilic bacteria biomass. Such a rank implied that the variation of ammonium nitrogen concentration, the associated temperature and the moisture conditions, the total loss of both organic matters and available mineral constituents, and the mesophilic bacteria activity, were critical factors affecting the C/N ratio during the investigated food waste composting. This first application of GASCA to composting modelling indicated that more direct search algorithms could be coupled with SCA or other multivariate analysis methods to analyze complicated relationships during composting and many other environmental processes. Copyright © 2010 Elsevier B.V. All rights reserved.

Isolation and partial characterization of antimicrobial compounds from a new strain Streptomyces sp. CN207

International Nuclear Information System (INIS)

Slama, Nedra; Lazim, Hadeer; Barkallah, Insaf; Limam, Ferid

2008-01-01

A distinct streptomyces strains were isolated from Tunisian soil. the isolate designed CN207, was assigned to the genus streptomyces on the basis of morphological and chemotaxonomic criteria. A 16S rDNA sequence of the isolate was determined. Streptomyces sp CN207 secreted large amount antibiotic against gram positive bacteria, gram negative bacteria, yeast and fungi on his barley (HB) medium. (HB) medium was found to be suitable substrate of the medium for CN207 production. Maximum yield of CN207 product (700 mg/ml) after optimize fermentation process. Bioactive molecules from strain CN207 were extracted with ethyl acetate and analyzed by PTLC using silica gel plates.The separated compounds were visualiszed under UV at 254 nm and the active spots were detected by bioautography on silica gel plates using salmonella thyphimurium NRRL B4420 and Staphylococcus aureus CDC 103 as indicator microorganisms. The crude extract (8.36 g) was fractionated on Sep-pack column (C18 cartridge) and elution was performed using a discontinue gradient of methanol-water. Two active fractions eluted by 20% and 40% of methanol were obtained. The bioactive compounds were separated by preparative high performance liquid chromatography (HPLC) on a C18 reversed phase column and eluted with a linear gradient of acetonitrile -water in presence of 0.1% formic acid. The peaks were collected separately, concentrated and bioassayed against the routine indicator microorganisms. The absorption spectrum of the active molecules was determined with a shimadzu UV-160 a spectrophotometer. Determination of the chemical structure of these compounds on the basis on their IR, COSY and H 1: C13 is in progress

Te(II)/Te(IV) Mediated C-N Bond Formation on 2,5-Diphenyltellurophene and a Reassignment of the Product from the Reaction of PhI(OAc)2 with 2 TMS-OTf.

Science.gov (United States)

Aprile, Antonino; Iversen, Kalon J; Wilson, David J D; Dutton, Jason L

2015-05-18

We report a novel C-H to C-N bond metathesis at the 3-position of 1,2-diphenyltellurophene via oxidation of the Te(II) center to Te(IV) using the I(III) oxidant [PhI(4-DMAP)2](2+). Spontaneous reduction of a transient Te(IV) coordination compound to Te(II) generates an electrophilic equivalent of 4-DMAP that substitutes at a C-H bond at the 3-position of the tellurophene. Theoretical and synthetic reaction pathway studies confirm that a Te(IV) coordination complex with 4-DMAP is an intermediate. In the course of these pathway studies, it was also found that the identity of the I(III) oxidant generated from PhI(OAc)2 and 2 TMS-OTf is PhI(OAc)(OTf) and not PhI(OTf)2, as had been previously thought.

Serendipitous preparation of fac-(acetonitrile-κNtrichlorido[(1,2,5,6-η-cycloocta-1,5-diene]iridium(III

Directory of Open Access Journals (Sweden)

David M. Morris

2015-04-01

Full Text Available A reaction between [(CODIrCl]2 (COD is cycloocta-1,5-diene, HCl and indene failed to provide the hoped for chloridoindenyliridium dimer, but instead produced the title compound, [IrCl3(CH3CN(C8H12], which is an octahedral complex of iridium(III with a chelating cycloocta-1,5-diene ligand, three chloride ligands in a fac arrangement, and one acetonitrile ligand. Attempts to devise a rational synthesis for the title compound were unsuccessful.

Study on optoelectronic properties of Spiro-CN for developing an efficient OLED

Science.gov (United States)

Mishra, Ashok Kumar

2018-05-01

There are a class of organic molecules and polymers which exhibit semiconductor behavior because of nearly free conjugate π-electrons. Hopping of these electrons in molecules forms different excited singlet and triplet states named as excitons. Some of these organic molecules can be set to emit photons by triplet-singlet excitonic transition via a process called Thermally Activated Delayed Fluorescence (TADF) which is exploited for designing the Organic Light Emitting diode (OLED.) Spiro-CN (spirobifluorene skeletons) Spiro is one of these reported noble metal-free TADF molecules which offers unique optical and electronic properties arising from the efficient transition and reverse intersystem crossing between the lowest singlet (S) and triplet (T) excited states. Its ability to harvest triplet excitons for fluorescence through facilitated reverse intersystem crossing (T→S) could directly impact their properties and performances, which is attractive for a wide variety of low-cost optoelectronic device. In the present study, the Spiro-CN compounds have been taken up for the investigation of various optoelectronic properties including the thermally activated delayed fluorescence (TADF) by using the Koopmans Method and Density Functional Theory. The present study discusses the utility of the Spiro-CN organic semiconductor as a suitable TADF material essential for developing an efficient Organic Light Emitting Diode (OLED).

Anomalous cosmic ray carbon and oxygen tracks in CN-Kodak.

Science.gov (United States)

Kondratyeva, M A; Tretyakova, C A; Tretyakova, S P; Zhuravlev, D A

2001-06-01

For observation of low energy cosmic ray particles we used CN-Kodak nuclear track detectors on Cosmos satellites. In solar quiet periods during solar minima conditions the detectors registered anomalous cosmic rays (ACRs). The ACRs are characterized by flux enhancements of several elements and it is known that the carbon enhancement is small compared with that of oxygen. In all of our quiet-time exposures the relation between carbon and oxygen was extremely small (C/O ~ 0.03). But in two quiet-time periods of 14.03.96-11.06.96 and of 15.12.97-14.04.98 we have identified many tracks as carbon in a L-R diagram. As a result the observed C/O ratio appears to be more than 0.5, whereas other experiments show no evidence of enhanced flux of carbon during these periods. The reason for the unexpected response of CN-Kodak is discussed. c2001 Elsevier Science Ltd. All rights reserved.

The influence of the pyrolysis temperature on the electrochemical behavior of carbon-rich SiCN polymer-derived ceramics as anode materials in lithium-ion batteries

Science.gov (United States)

Reinold, Lukas Mirko; Yamada, Yuto; Graczyk-Zajac, Magdalena; Munakata, Hirokazu; Kanamura, Kiyoshi; Riedel, Ralf

2015-05-01

Within this study we report on the impact of the pyrolysis temperature on the structural and electrochemical properties of the poly(phenylvinylsilylcarbodiimide) derived silicon carbonitride (SiCN) ceramic. Materials pyrolysed at 800 °C and 1300 °C, SiCN 800 and SiCN 1300, are found amorphous. Raman spectroscopy measurements indicate the increase in ordering of the free carbon phase with increasing pyrolysis temperature which leads to lower capacity recovered by SiCN 1300. Significant hysteresis is found for materials pyrolysed at 800 °C during electrochemical lithium insertion/extraction. This feature is attributed to much higher hydrogen content in SiCN 800 sample. An aging of SiCN 800 reflected by a change of elemental composition upon contact to air and a strong film formation are attenuated at a higher pyrolysis temperature. Single particle microelectrode investigation on SiCN 800 and SiCN 1300 clarify different electrochemical behavior of the materials. Much lower charge transfer resistance of SiCN 1300 in comparison to SiCN 800 explains better high currents electrochemical performance. Lithium ions diffusion coefficient Dmin ranges from 3.2 10-9 cm2s-1 to 6.4 10-11 cm2s-1 and is independent on the potential.

A family of acetato-diphenoxo triply bridged dimetallic Zn(II)Ln(III) complexes: SMM behavior and luminescent properties.

Science.gov (United States)

Oyarzabal, Itziar; Artetxe, Beñat; Rodríguez-Diéguez, Antonio; García, JoséÁngel; Seco, José Manuel; Colacio, Enrique

2016-06-21

Eleven dimetallic Zn(II)-Ln(III) complexes of the general formula [Zn(µ-L)(µ-OAc)Ln(NO3)2]·CH3CN (Ln(III) = Pr (1), Nd (2), Sm (3), Eu (4), Gd (5), Tb (6), Dy (7), Ho (8), Er (9), Tm (10), Yb (11)) have been prepared in a one-pot reaction from the compartmental ligand N,N'-dimethyl-N,N'-bis(2-hydroxy-3-formyl-5-bromo-benzyl)ethylenediamine (H2L). In all these complexes, the Zn(II) ions occupy the internal N2O2 site whereas the Ln(III) ions show preference for the O4 external site. Both metallic ions are bridged by an acetate bridge, giving rise to triple mixed diphenoxido/acetate bridged Zn(II)Ln(III) compounds. The Nd, Dy, Er and Yb complexes exhibit field induced single-ion magnet (SIM) behaviour, with Ueff values ranging from 14.12 to 41.55 K. The Er complex shows two relaxation processes, but only the second relaxation process with an energy barrier of 21.0 K has been characterized. The chromophoric L(2-) ligand is able to act as an "antenna" group, sensitizing the near-infrared (NIR) Nd(III) and Yb(III)-based luminescence in complexes 2 and 11 and therefore, both compounds can be considered as magneto-luminescent materials. In addition, the Sm(III), Eu(III) and Tb(III) derivatives exhibit characteristic emissions in the visible region.

The Cn method applied to problems with an anisotropic diffusion law

International Nuclear Information System (INIS)

Grandjean, P.M.

A 2-dimensional Cn calculation has been applied to homogeneous media subjected to the Rayleigh impact law. Results obtained with collision probabilities and Chandrasekhar calculations are compared to those from Cn method. Introducing in the expression of the transport equation, an expansion truncated on a polynomial basis for the outgoing angular flux (or possibly entrance flux) gives two Cn systems of algebraic linear equations for the expansion coefficients. The matrix elements of these equations are the moments of the Green function in infinite medium. The search for the Green function is effected through the Fourier transformation of the integrodifferential equation and its moments are derived from their Fourier transforms through a numerical integration in the complex plane. The method has been used for calculating the albedo in semi-infinite media, the extrapolation length of the Milne problem, and the albedo and transmission factor of a slab (a concise study of convergence is presented). A system of integro-differential equations bearing on the moments of the angular flux inside the medium has been derived, for the collision probability method. It is numerically solved with approximately the bulk flux by step functions. The albedo in semi-infinite medium has also been computed through the semi-analytical Chandrasekhar method. In the latter, the outgoing flux is expressed as a function of the entrance flux by means of a integral whose kernel is numerically derived [fr

Rainfall - CN (Curve Number relationships in a tropical rainforest microbasin within the Panamá Canal watershed

Directory of Open Access Journals (Sweden)

José R. Fábrega D

2012-01-01

Full Text Available Relaciones de Precipitación (P y Número de Curva (CN para diferentesrangos de flujo base obtenidas dentro de la cuenca alta del Río Chagres fueron aplicadas a una microcuenca de 6.5 Ha localizada dentro de la cuenca del Canal de Panamá. Estas relaciones estiman valores de CN a partir de los datos de P empleando una ecuación establecida por Calvo et al (10. Esta ecuación usa k y CN∞ como parámetros de ajuste. Datos de precipitación/escorrentía de la microcuenca, colectados en un período de 6 meses fueron analizados. Estos análisis mostraron que los valores de CN en la microcuenca son más cercanos a los valores de CN predichos por la ecuación correspondiente al rango más bajo de los flujos base (14-42 m3/s de la cuenca alta del Río Chagres. Estos resultados se explican si consideramos no los valores absolutos del flujo base Qbase, sino los valores relativos de este parámetro con respecto al área de la cuenca bajo estudio.

GTLine – Gasoline as a potential CN suppressant for GTL

KAUST Repository

Reijnders, Jos; Boot, Michael; Johansson, Bengt; de Goey, Philip

2018-01-01

The main driver to investigate low temperature combustion concepts, such as partially premixed combustion (PPC), is the promise of low particulate matter (PM) and nitric oxide (NOx) emissions. A critical prerequisite for PPC is to temporally isolate the fuel injection and combustion events. In practice, exhaust gas recirculation (EGR) is applied in order to sufficiently extend the ignition delay to that effect. Hereby, in general, higher EGR rates are necessary for fuels with higher cetane numbers (CN). Against this background, the objective of this paper is to investigate the efficacy, with respect to PM-NOx emissions and engine efficiency, of gasoline as a potential gas-to-liquid (GTL) CN suppressant in various dosages. The performance of the resulting GTLine blend will be evaluated under PPC operating conditions in a heavy-duty direct-injected diesel engine. Setting aside for a moment any potential practical issues (e.g., flash point, vapor pressure) that fall outside the scope of this study, our data suggest that blending gasoline to otherwise high CN GTL appears to be a promising route to improve not only the efficiency, but also PM and NOx emissions, particularly when operating in PPC mode. Interestingly, this benefit is notwithstanding the high aromaticity of the gasoline compared to GTL. Given the ongoing dieselization trend and associated surplus of gasoline in many regions, notably Europe, along with the fact that the cost price of gasoline is significantly lower than that of GTL, the proposed GTLine approach promises to be a cost effective way to accommodate GTL in a world wherein low temperature combustion concepts, such as PPC, appear to be really taking off.

GTLine – Gasoline as a potential CN suppressant for GTL

KAUST Repository

Reijnders, Jos

2018-03-23

The main driver to investigate low temperature combustion concepts, such as partially premixed combustion (PPC), is the promise of low particulate matter (PM) and nitric oxide (NOx) emissions. A critical prerequisite for PPC is to temporally isolate the fuel injection and combustion events. In practice, exhaust gas recirculation (EGR) is applied in order to sufficiently extend the ignition delay to that effect. Hereby, in general, higher EGR rates are necessary for fuels with higher cetane numbers (CN). Against this background, the objective of this paper is to investigate the efficacy, with respect to PM-NOx emissions and engine efficiency, of gasoline as a potential gas-to-liquid (GTL) CN suppressant in various dosages. The performance of the resulting GTLine blend will be evaluated under PPC operating conditions in a heavy-duty direct-injected diesel engine. Setting aside for a moment any potential practical issues (e.g., flash point, vapor pressure) that fall outside the scope of this study, our data suggest that blending gasoline to otherwise high CN GTL appears to be a promising route to improve not only the efficiency, but also PM and NOx emissions, particularly when operating in PPC mode. Interestingly, this benefit is notwithstanding the high aromaticity of the gasoline compared to GTL. Given the ongoing dieselization trend and associated surplus of gasoline in many regions, notably Europe, along with the fact that the cost price of gasoline is significantly lower than that of GTL, the proposed GTLine approach promises to be a cost effective way to accommodate GTL in a world wherein low temperature combustion concepts, such as PPC, appear to be really taking off.

Characterization of a tricationic trigonal bipyramidal iron(IV) cyanide complex, with a very high reduction potential, and its iron(II) and iron(III) congeners.

Science.gov (United States)

England, Jason; Farquhar, Erik R; Guo, Yisong; Cranswick, Matthew A; Ray, Kallol; Münck, Eckard; Que, Lawrence

2011-04-04

Currently, there are only a handful of synthetic S = 2 oxoiron(IV) complexes. These serve as models for the high-spin (S = 2) oxoiron(IV) species that have been postulated, and confirmed in several cases, as key intermediates in the catalytic cycles of a variety of nonheme oxygen activating enzymes. The trigonal bipyramidal complex [Fe(IV)(O)(TMG(3)tren)](2+) (1) was both the first S = 2 oxoiron(IV) model complex to be generated in high yield and the first to be crystallographically characterized. In this study, we demonstrate that the TMG(3)tren ligand is also capable of supporting a tricationic cyanoiron(IV) unit, [Fe(IV)(CN)(TMG(3)tren)](3+) (4). This complex was generated by electrolytic oxidation of the high-spin (S = 2) iron(II) complex [Fe(II)(CN)(TMG(3)tren)](+) (2), via the S = 5/2 complex [Fe(III)(CN)(TMG(3)tren)](2+) (3), the progress of which was conveniently monitored by using UV-vis spectroscopy to follow the growth of bathochromically shifting ligand-to-metal charge transfer (LMCT) bands. A combination of X-ray absorption spectroscopy (XAS), Mössbauer and NMR spectroscopies was used to establish that 4 has a S = 0 iron(IV) center. Consistent with its diamagnetic iron(IV) ground state, extended X-ray absorption fine structure (EXAFS) analysis of 4 indicated a significant contraction of the iron-donor atom bond lengths, relative to those of the crystallographically characterized complexes 2 and 3. Notably, 4 has an Fe(IV/III) reduction potential of ∼1.4 V vs Fc(+/o), the highest value yet observed for a monoiron complex. The relatively high stability of 4 (t(1/2) in CD(3)CN solution containing 0.1 M KPF(6) at 25 °C ≈ 15 min), as reflected by its high-yield accumulation via slow bulk electrolysis and amenability to (13)C NMR at -40 °C, highlights the ability of the sterically protecting, highly basic peralkylguanidyl donors of the TMG(3)tren ligand to support highly charged high-valent complexes.

Effects of C/N ratio on nitrate removal and floc morphology of autohydrogenotrophic bacteria in a nitrate-containing wastewater treatment process.

Science.gov (United States)

Nguyen, Tran Ngoc Phu; Chao, Shu-Ju; Chen, Pei-Chung; Huang, Chihpin

2018-07-01

The effects of C/N ratio of a nitrate-containing wastewater on nitrate removal performed by autohydrogenotrophic bacteria as well as on the morphological parameters of floc such as floc morphology, floc number distribution, mean particle size (MPS), aspect ratio and transparency were examined in this study. The results showed that the nitrate reduction rate increased with increasing C/N ratio from 0.5 to 10 and that the nitrogen removal of up to 95% was found at the C/N ratios of higher than 5 (between 0.5-10). Besides, high C/N ratio values reflected a corresponding high nitrite accumulation after 12-hr operation, and a fast decreasing rate of nitrite in the rest of operational time. The final pH values increased with the C/N ratio increasing from 0.5 to 2.5, but decreased with the C/N ratio increasing from 2.5 to 10. There were no significant changes in floc morphology with the MPSs ranging from 35 to 40μm. Small and medium-sized flocs were dominant in the sludge suspension, and the number of flocs increased with the increasing C/N ratios. Furthermore, the highest apparent frequency of 10% was observed at aspect ratios of 0.5 and 0.6, while the transparency of flocs changed from 0.1 to 0.7. Copyright © 2017. Published by Elsevier B.V.

PREDICTION OF THE SPECTROSCOPIC PARAMETERS OF NEW IRON COMPOUNDS: HYDRIDE OF IRON CYANIDE/ISOCYANIDE, HFeCN/HFeNC

Energy Technology Data Exchange (ETDEWEB)

Redondo, Pilar; Barrientos, Carmen; Largo, Antonio, E-mail: predondo@qf.uva.es [Departamento de Química Física y Química Inorgánica Facultad de Ciencias, Universidad de Valladolid Campus Miguel Delibes Paseo de Belén 7, E-47011, Valladolid (Spain)

2016-09-01

Iron is the most abundant transition metal in space. Its abundance is similar to that of magnesium, and until today only, FeO and FeCN have been detected. However, magnesium-bearing compounds such as MgCN, MgNC, and HMgNC are found in IRC+10216. It seems that the hydrides of iron cyanide/isocyanide could be good candidates to be present in space. In the present work we carried out a characterization of the different minima on the quintet and triplet [C, Fe, H, N] potential energy surfaces, employing several theoretical approaches. The most stable isomers are predicted to be hydride of iron cyanide HFeCN, and isocyanide HFeNC, in their {sup 5}Δ states. Both isomers are found to be quasi-isoenergetics. The HFeNC isomer is predicted to lie about 0.5 kcal/mol below HFeCN. The barrier for the interconversion process is estimated to be around 6.0 kcal/mol, making this process unfeasible under low temperature conditions, such as those in the interstellar medium. Therefore, both HFeCN and HFeNC could be candidates for their detection. We report geometrical parameters, vibrational frequencies, and rotational constants that could help with their experimental characterization.

PREDICTION OF THE SPECTROSCOPIC PARAMETERS OF NEW IRON COMPOUNDS: HYDRIDE OF IRON CYANIDE/ISOCYANIDE, HFeCN/HFeNC

International Nuclear Information System (INIS)

Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

2016-01-01

Iron is the most abundant transition metal in space. Its abundance is similar to that of magnesium, and until today only, FeO and FeCN have been detected. However, magnesium-bearing compounds such as MgCN, MgNC, and HMgNC are found in IRC+10216. It seems that the hydrides of iron cyanide/isocyanide could be good candidates to be present in space. In the present work we carried out a characterization of the different minima on the quintet and triplet [C, Fe, H, N] potential energy surfaces, employing several theoretical approaches. The most stable isomers are predicted to be hydride of iron cyanide HFeCN, and isocyanide HFeNC, in their 5 Δ states. Both isomers are found to be quasi-isoenergetics. The HFeNC isomer is predicted to lie about 0.5 kcal/mol below HFeCN. The barrier for the interconversion process is estimated to be around 6.0 kcal/mol, making this process unfeasible under low temperature conditions, such as those in the interstellar medium. Therefore, both HFeCN and HFeNC could be candidates for their detection. We report geometrical parameters, vibrational frequencies, and rotational constants that could help with their experimental characterization.

Effective Biological Nitrogen Removal Treatment Processes for Domestic Wastewaters with Low C/N Ratios: A Review

DEFF Research Database (Denmark)

Sun, Sheng-Peng; Pellicer i Nàcher, Carles; Merkey, Brian

2010-01-01

with high efficiency and relative low costs. However, the removal of nitrogen from domestic wastewater with a low carbon/nitrogen (C/N) ratio can often be limited in municipal wastewater plants (WWTPs) because organic carbon is a limiting factor for denitrification. The present work reviews innovative....... They can effectively be used for nitrogen removal from low C/N domestic wastewater without external carbon addition. In addition, conventional and alternative carbon sources for enhanced biological nitrogen removal were also reviewed. We conclude that alternative carbon sources such as wine distillery...... at large scale for nitrogen removal from low C/N domestic wastewater, (2) further method logic are explored to introduce the Anammox pathway into domestic wastewater treatment, and (3) alternative carbon sources are explored and optimized for supporting the denitrification. With these efforts, cost...

Monitoring of the future strong Vrancea events by using the CN formal earthquake prediction algorithm

International Nuclear Information System (INIS)

Moldoveanu, C.L.; Novikova, O.V.; Panza, G.F.; Radulian, M.

2003-06-01

The preparation process of the strong subcrustal events originating in Vrancea region, Romania, is monitored using an intermediate-term medium-range earthquake prediction method - the CN algorithm (Keilis-Borok and Rotwain, 1990). We present the results of the monitoring of the preparation of future strong earthquakes for the time interval from January 1, 1994 (1994.1.1), to January 1, 2003 (2003.1.1) using the updated catalogue of the Romanian local network. The database considered for the CN monitoring of the preparation of future strong earthquakes in Vrancea covers the period from 1966.3.1 to 2003.1.1 and the geographical rectangle 44.8 deg - 48.4 deg N, 25.0 deg - 28.0 deg E. The algorithm correctly identifies, by retrospective prediction, the TJPs for all the three strong earthquakes (Mo=6.4) that occurred in Vrancea during this period. The cumulated duration of the TIPs represents 26.5% of the total period of time considered (1966.3.1-2003.1.1). The monitoring of current seismicity using the algorithm CN has been carried out since 1994. No strong earthquakes occurred from 1994.1.1 to 2003.1.1 but the CN declared an extended false alarm from 1999.5.1 to 2000.11.1. No alarm has currently been declared in the region (on January 1, 2003), as can be seen from the TJPs diagram shown. (author)

Determination of ionization energies of CnN (n=4-12): Vacuum-ultraviolet (VUV) photoionization experiments and theoretical calculations

International Nuclear Information System (INIS)

Kostko, Oleg; Zhou, Jia; Sun, Bian Jian; Lie, Jie Shiuan; Chang, Agnes H.H.; Kaiser, Ralf I.; Ahmed, Musahid

2010-01-01

Results from single photon vacuum ultraviolet photoionization of astrophysically relevant CnN clusters, n = 4 - 12, in the photon energy range of 8.0 eV to 12.8 eV are presented. The experimental photoionization efficiency curves, combined with electronic structure calculations, provide improved ionization energies of the CnN species. A search through numerous nitrogen-terminated CnN isomers for n=4-9 indicates that the linear isomer has the lowest energy, and therefore should be the most abundant isomer in the molecular beam. Comparison with calculated results also shed light on the energetics of the linear CnN clusters, particularly in the trends of the even-carbon and the odd-carbon series. These results can help guide the search of potential astronomical observations of these neutral molecules together with their cations in highly ionized regions or regions with a high UV/VUV photon flux (ranging from the visible to VUV with flux maxima in the Lyman-a region) in the interstellar medium.

Enhanced Photocatalytic Degradation of Methyl Orange Dye under the Daylight Irradiation over CN-TiO₂ Modified with OMS-2.

Science.gov (United States)

Hassan, Mohamed Elfatih; Chen, Jing; Liu, Guanglong; Zhu, Duanwei; Cai, Jianbo

2014-12-12

In this study, CN-TiO₂ was modified with cryptomelane octahedral molecular sieves (OMS-2) by the sol-gel method based on the self-assembly technique to enhance its photocatalytic activity under the daylight irradiation. The synthesized samples were characterized by X-ray diffraction (XRD), UV-vis spectroscopy, Fourier transform infrared spectroscopy (FT-IR) and porosimeter analysis. The results showed that the addition of OMS-2 in the sol lead to higher Brunauer-Emmett-Teller (BET) surface area, pore volume, porosity of particle after heat treatment and the specific surface area, porosity, crystallite size and pore size distribution could be controlled by adjusting the calcination temperature. Compared to the CN-TiO₂-400 sample, CN-TiO₂/OMS-2-400 exhibited greater red shift in absorption edge of samples in visible region due to the OMS-2 coated. The enhancement of photocatalytic activity of CN-TiO₂/OMS-2 composite photocatalyst was subsequently evaluated for the degradation of the methyl orange dye under the daylight irradiation in water. The results showed that the methyl orange dye degradation rate reach to 37.8% for the CN-TiO₂/OMS-2-400 sample under the daylight irradiation for 5 h, which was higher than that of reference sample. The enhancement in daylight photocatalytic activities of the CN-TiO₂/OMS samples could be attributed to the synergistic effects of OMS-2 coated, larger surface area and red shift in adsorption edge of the prepared sample.

Synthesis and photophysical studies of blue phosphorescent Ir(III) complexes with dimethylphenylphospine.

Science.gov (United States)

Ham, Ho-Wan; Jung, Kyung-Yoon; Kim, Young-Sik

2012-02-01

New blue emitting mixed ligand iridium(III) complexes comprising one cyclometalating, two phosphines trans to each other such as Ir{(CF3)2Meppy}(PPhMe3)2(H)(L) [L = CI, NCMe, CN] [(CF3)2Meppy = 2-(3', 5'-bis-trifluoromethylphenyl)-4-methylpyridine] were synthesized and studied to tune the phosphorescence wavelength to the deep blue region and to enhance the luminescence efficiencies. To achieve deep blue emission, the trifluoromethyl group substituted on the phenyl ring and the methyl group substituted on the pyridyl ring increased HOMO-LUMO gap and achieved the hypsochromic shift. To gain insight into the factors responsible for the emission color change and the different luminescence efficiency, we investigate the electron-withdrawing capabilities of ancillary ligands using the DFT and TD-DFT calculations on the ground and excited states of the complexes. From these results, we discuss how the ancillary ligand influences the emission peak as well as the metal to ligand charge transfer (MLCT) transition efficiency. The maximum emission spectra of Ir{(CF3)2Meppy}(PPhMe3)2(H)(Cl), [Ir{(CF3),Meppy)(PPhMe3),(H)(NCMe)]+ and Ir{(CF3)2Meppy}(PPhMe3)2(H)(CN) were in the ranges of 441, 435, 434 nm, respectively.

Behavior of Am in acidic and basic solutions of potassium ferri/ferrocyanide

International Nuclear Information System (INIS)

Kulyako, Yu.M.; Trofimov, T.I.; Malikov, D.A.; Lebedev, I.A.; Myasoedov, B.F.

1994-01-01

The behavior of Am in acidic and basic solutions containing the Fe(CN) 3- 6 /Fe(CN) 4- 6 redox system is studied. In mineral acids, K 3 Fe(CN) 6 and Am(III) form the poorly soluble compound AmFe(CN) 6 , which with time undergoes a change owing to radiolytic reduction of Fe(CN) 3- 6 to Fe(CN) 4- 6 . In basic solutions of K 3 Fe(CN) 6 , Am(III) is oxidized to AmO + 2 , forming the soluble complex (AmO 2 ) 3 Fe(CN) 6 , which gradually decomposes to produce the solid double hydroxide Na 2 AmO 2 (OH) 3 ·nH 2 O. An Am(IV) hydroxide is formed if [Am] and [K 3 Fe(CN) 6 ] are equal

Influence of high temperature annealing on the structure, hardness and tribological properties of diamond-like carbon and TiAlSiCN nanocomposite coatings

International Nuclear Information System (INIS)

Xie, Z.W.; Wang, L.P.; Wang, X.F.; Huang, L.; Lu, Y.; Yan, J.C.

2011-01-01

Diamond-like carbon (DLC) and TiAlSiCN nanocomposite coatings were synthesized and annealed at different temperatures in a vacuum environment. The microstructure, hardness and tribological properties of as-deposited and annealed DLC-TiAlSiCN nanocomposite coatings were characterized by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Raman spectroscopy, nano-indentation and friction tests. The TEM results reveal that the as-deposited DLC-TiAlSiCN coating has a unique nanocomposite structure consisting of TiCN nanocrystals embedded in an amorphous matrix consisting of a-Si 3 N 4 , a-SiC, a-CN and DLC, and the structure changed little after annealing at 800 °C. However, XPS and Raman results show that an obvious graphitization of the DLC phase occurred during the annealing process and it worsened with annealing temperature. Because of the graphitization, the hardness of the DLC-TiAlSiCN coating after annealing at 800 °C decreased from 45 to 36 GPa. In addition, the DLC-TiAlSiCN coating after annealing at 800 °C has a similar friction coefficient to the as-deposited coating.

Beyond the SCS-CN method: A theoretical framework for spatially lumped rainfall-runoff response

Science.gov (United States)

Bartlett, M. S.; Parolari, A. J.; McDonnell, J. J.; Porporato, A.

2016-06-01

Since its introduction in 1954, the Soil Conservation Service curve number (SCS-CN) method has become the standard tool, in practice, for estimating an event-based rainfall-runoff response. However, because of its empirical origins, the SCS-CN method is restricted to certain geographic regions and land use types. Moreover, it does not describe the spatial variability of runoff. To move beyond these limitations, we present a new theoretical framework for spatially lumped, event-based rainfall-runoff modeling. In this framework, we describe the spatially lumped runoff model as a point description of runoff that is upscaled to a watershed area based on probability distributions that are representative of watershed heterogeneities. The framework accommodates different runoff concepts and distributions of heterogeneities, and in doing so, it provides an implicit spatial description of runoff variability. Heterogeneity in storage capacity and soil moisture are the basis for upscaling a point runoff response and linking ecohydrological processes to runoff modeling. For the framework, we consider two different runoff responses for fractions of the watershed area: "prethreshold" and "threshold-excess" runoff. These occur before and after infiltration exceeds a storage capacity threshold. Our application of the framework results in a new model (called SCS-CNx) that extends the SCS-CN method with the prethreshold and threshold-excess runoff mechanisms and an implicit spatial description of runoff. We show proof of concept in four forested watersheds and further that the resulting model may better represent geographic regions and site types that previously have been beyond the scope of the traditional SCS-CN method.

The CN/C15N isotopic ratio towards dark clouds

Science.gov (United States)

Hily-Blant, P.; Pineau des Forêts, G.; Faure, A.; Le Gal, R.; Padovani, M.

2013-09-01

Understanding the origin of the composition of solar system cosmomaterials is a central question, not only in the cosmochemistry and astrochemistry fields, and requires various approaches to be combined. Measurements of isotopic ratios in cometary materials provide strong constraints on the content of the protosolar nebula. Their relation with the composition of the parental dark clouds is, however, still very elusive. In this paper, we bring new constraints based on the isotopic composition of nitrogen in dark clouds, with the aim of understanding the chemical processes that are responsible for the observed isotopic ratios. We have observed and detected the fundamental rotational transition of C15N towards two starless dark clouds, L1544 and L1498. We were able to derive the column density ratio of C15N over 13CN towards the same clouds and obtain the CN/C15N isotopic ratios, which were found to be 500 ± 75 for both L1544 and L1498. These values are therefore marginally consistent with the protosolar value of 441. Moreover, this ratio is larger than the isotopic ratio of nitrogen measured in HCN. In addition, we present model calculations of the chemical fractionation of nitrogen in dark clouds, which make it possible to understand how CN can be deprived of 15N and HCN can simultaneously be enriched in heavy nitrogen. The non-fractionation of N2H+, however, remains an open issue, and we propose some chemical way of alleviating the discrepancy between model predictions and the observed ratios. Appendices are available in electronic form at http://www.aanda.orgThe reduced spectra (in FITS format) are available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/557/A65

Histone fractionation by high-performance liquid chromatography on cyanoalkylsilane (CN) reverse-phase columns

International Nuclear Information System (INIS)

Gurley, L.R.; Prentice, D.A.; Valdez, J.G.; Spall, W.D.

1983-01-01

Previous work described conditions for the rapid fractionation of histones by high-performance liquid chromatography (HPLC) using a reverse-phase μBondapak C 18 column. That procedure resolved the major classes of histones with one exception: the more hydrophobic H2A variant, (MHP)H2A, was not resolved from the H4 histone class. This report extends that work describing experiments using a μBondapak CN column which better resolves the classes of histones from each other including the resolution of (MHP)H2A from the H4. In addition, the less hydrophobic H2A variant, (LHP)H2A, is partially resolved from the (MHP)H2A, and the less hydrophobic H3 variant, (LHP)H3, is resolved from the more hydrophobic H3 variant, (MHP)H3. Lower trifluoroacetic acid (TFA) concentrations (0.1%) in the eluting water/acetonitrile solvent were used with the CN column than were used with the C 18 column which increased the sensitivity of histone detection by ultraviolet absorption at 206 nm. Greater than 95% of the total [ 3 H]lysine-labeled protein applied to the CN column was eluted from the column. Contaminating nonhistone proteins were found to chromatograph in the region of histone elution. These were greatly reduced by isolating nuclei prior to histone preparation. The fractionation of the histones appears to be based on the hydrophobic properties of the proteins. The histone fractions (identified by their electrophoretic mobilities) were eluted from the CN column in the following order: H1, H2B, (LHP)H2A, (MHP)H2A, H4, (LHP)H3, and (MHP)H3. Phosphorylated and acetylated histone species were not resolved from their unmodified parental species

Catchment area-based evaluation of the AMC-dependent SCS-CN-based rainfall-runoff models

Science.gov (United States)

Mishra, S. K.; Jain, M. K.; Pandey, R. P.; Singh, V. P.

2005-09-01

Using a large set of rainfall-runoff data from 234 watersheds in the USA, a catchment area-based evaluation of the modified version of the Mishra and Singh (2002a) model was performed. The model is based on the Soil Conservation Service Curve Number (SCS-CN) methodology and incorporates the antecedent moisture in computation of direct surface runoff. Comparison with the existing SCS-CN method showed that the modified version performed better than did the existing one on the data of all seven area-based groups of watersheds ranging from 0.01 to 310.3 km2.

The effects of sunlight exposure on the neutron response of CN-85 track detector

International Nuclear Information System (INIS)

Ahmad, N.; Mirza, N.M.; Mirza, S.K.; Tufail, M.

1996-01-01

The effect of sunlight exposure on the neutron response of CN-85 track detectors has been studied. It has been observed that the response during the first 28 days of sunlight exposure is slightly enhanced (10%) and then deceases continuously with increase in the sunlight exposure. After 84 days of sunlight exposure the response of the exposed detector relative to an unexposed detector is only 22%. It is also observed that the response can not be maintained by wrapping the CN-85 etch track detectors in typewriter black carbon papers if they are exposed to sunlight. (author)

Electronic Switch in the Carbon-Centered [Re12CS17(CN6] n−Nanocluster

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Gabuda SP

2009-01-01

Full Text Available Abstract An abrupt change in internuclear Re–Re distances between {Re6} subunits in the carbon-centered [Re12μ6-CS17(CN6] n−complexes caused by the change of the oxidation state (n = 6, 8 is first theoretically shown to be possibly controlled by an external electric field.13C NMR signal is shown to change over ~400 ppm (~37G for μ6-C atom together withn. Thereby, the metal cluster [Re12μ6-CS17(CN6] n−can be considered as a perspective model of a molecular switch.

Cm3+-F- interaction in a mixed system of methanol and water

International Nuclear Information System (INIS)

Satoh, I.; Watanabe, T.; Ishii, Y.; Kawasaki, M.; Suganuma, H.

2003-01-01

The stability constants (β 1 ) of the monofluoro complex of Cm(III) have been determined in mixed solvents of methanol and water using the solvent extraction technique. The values of Inβ 1 increase as the molar fraction of methanol (X s ) in the mixed solvent increases. The variation in the stability constants mainly depends on the solvation of F - and slightly depends on both (1) the solvation of cations in connection with the complexation of CmF 2+ and (2) the electrostatic attraction of Cm 3+ -F - . The variation in Inβ 1 for Cm(III) due to the effect of both (1) and (2) is similar to that for Sm(III). By variation of Inβ 1 the coordination number in the primary hydration sphere (CN) of Cm(III) decreased from a value between CN = 9 and CN = 8 to CN = 8, at about X s = 0.02. The X s value of the inflection point of the CN for Cm is slightly lower than X s = 0.06 for Sm(III) and X s = 0.03 for Eu(III), previously obtained. (author)

Bifunctional Zn(II)Ln(III) dinuclear complexes combining field induced SMM behavior and luminescence: enhanced NIR lanthanide emission by 9-anthracene carboxylate bridging ligands.

Science.gov (United States)

Palacios, María A; Titos-Padilla, Silvia; Ruiz, José; Herrera, Juan Manuel; Pope, Simon J A; Brechin, Euan K; Colacio, Enrique

2014-02-03

There were new dinuclear Zn(II)-Ln(III) complexes of general formulas [Zn(μ-L)(μ-OAc)Ln(NO3)2] (Ln(III) = Tb (1), Dy (2), Er (3), and Yb (4)), [Zn(μ-L)(μ-NO3)Er(NO3)2] (5), [Zn(H2O)(μ-L)Nd(NO3)3]·2CH3OH (6), [Zn(μ-L)(μ-9-An)Ln(NO3)2]·2CH3CN (Ln(III) = Tb (7), Dy (8), Er (9), Yb(10)), [Zn(μ-L)(μ-9-An)Yb(9-An)(NO3)3]·3CH3CN (11), [Zn(μ-L)(μ-9-An)Nd(9-An)(NO3)3]·2CH3CN·3H2O (12), and [Zn(μ-L)(μ-9-An)Nd(CH3OH)2(NO3)]ClO4·2CH3OH (13) prepared from the reaction of the compartmental ligand N,N',N″-trimethyl-N,N″-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine (H2L), with ZnX2·nH2O (X = NO3(-) or OAc(-)) salts, Ln(NO3)3·nH2O, and, in some instances, 9-anthracenecarboxylate anion (9-An). In all these complexes, the Zn(II) ions invariably occupy the internal N3O2 site whereas the Ln(III) ions show preference for the O4 external site, giving rise to a Zn(μ-diphenoxo)Ln bridging fragment. Depending on the Zn(II) salt and solvent used in the reaction, a third bridge can connect the Zn(II) and Ln(III) metal ions, giving rise to triple-bridged diphenoxoacetate in complexes 1-4, diphenoxonitrate in complex 5, and diphenoxo(9-anthracenecarboxylate) in complexes 8-13. Dy(III) and Er(III) complexes 2, 8 and 3, 5, respectively, exhibit field induced single molecule magnet (SMM) behavior, with Ueff values ranging from 11.7 (3) to 41(2) K. Additionally, the solid-state photophysical properties of these complexes are presented showing that ligand L(2-) is able to sensitize Tb(III)- and Dy(III)-based luminescence in the visible region through an energy transfer process (antenna effect). The efficiency of this process is much lower when NIR emitters such as Er(III), Nd(III), and Yb(III) are considered. When the luminophore 9-anthracene carboxylate is incorporated into these complexes, the NIR luminescence is enhanced which proves the efficiency of this bridging ligand to act as antenna group. Complexes 2, 3, 5, and 8 can be considered as dual materials

Li dynamics in carbon-rich polymer-derived SiCN ceramics probed by NMR

Science.gov (United States)

Baek, Seung-Ho; Reinold, Lukas; Graczyk-Zajac, Magdalena; Riedel, Ralf; Hammerath, Franziska; Buechner, Bernd; Grafe, Hajo

2014-03-01

We report 7Li, 29Si, and 13C NMR studies of two different carbon-rich SiCN ceramics SiCN-1 and SiCN-3 derived from the preceramic polymers polyphenylvinylsilylcarbodiimide and polyphenylvinylsilazane, respectively. From the spectral analysis of the three nuclei at room temperature, we find that only the 13C spectrum is strongly influenced by Li insertion/extraction, suggesting that carbon phases are the major electrochemically active sites for Li storage. Temperature and Larmor frequency (ωL) dependences of the 7Li linewidth and spin-lattice relaxation rates T1-1 are described by an activated law with the activation energy EA of 0.31 eV and the correlation time τ0 in the high temperature limit of 1.3 ps. The 3 / 2 power law dependence of T1-1 on ωL which deviates from the standard Bloembergen, Purcell, and Pound (BPP) model implies that the Li motion on the μs timescale is governed by continuum diffusion mechanism rather than jump diffusion. On the other hand, the rotating frame relaxation rate T1ρ-1 results suggest that the slow motion of Li on the ms timescale may be affected by complex diffusion and/or non-diffusion processes.

Synthesis of (Cr,V){sub 2}(C,N) solid solution powders by thermal processing precursors

Energy Technology Data Exchange (ETDEWEB)

Liu, Anrui [School of Materials Science & Engineering, Sichuan University, Chengdu, 610065 (China); Liu, Ying [School of Materials Science & Engineering, Sichuan University, Chengdu, 610065 (China); Key Laboratory of Advanced Special Material & Technology, Ministry of Education, Chengdu, 610065 (China); Ma, Shiqing; Qiu, Yuchong; Rong, Pengcheng; Ye, Jinwen [School of Materials Science & Engineering, Sichuan University, Chengdu, 610065 (China)

2017-06-01

The single-phase (Cr,V){sub 2}(C,N) solid solution powders were fabricated via carbothermal reduction-nitridation (CRN) processing technique. The effects of heat treatment temperature, nitrogen pressure and carbon proportion were experimentally studied in detail by X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM) and thermal analysis. The chemical transformations of vanadium and chromium compounds were as follows: precursors → V{sub 2}O{sub 3}, Cr{sub 2}O{sub 3} → Cr{sub 3}C{sub 2}, Cr{sub 2}O{sub 3}, (Cr,V){sub 2}(C,N) → (Cr,V){sub 2}(C,N). When the heat-treated temperature was below 1200 °C, chromium oxides didn’t completely react. However, higher temperature ∼1300 °C could not only lead to the segregation of some nitrides and carbon black, but also to the occurrence of fiber-bridged particles. The system nitrogen pressure over 0.03 MPa would cause a subtle transformation of (Cr,V){sub 2}(C,N) to VCrN{sub 2}. When the carbon proportion was below 15 wt%, the oxides could not be completely reduced, while when the carbon proportion was above 15.5 wt%, some undesired carbides, like Cr{sub 23}C{sub 6} and Cr{sub 3}C{sub 2}, would form. Ultimately, the homogeneously distributed pure-phase (Cr,V){sub 2}(C,N) spherical particles with the average size of ∼1.5 μm were obtained at the optimal conditions of the treatment of precursors at 1200 °C for 1 h with the nitrogen pressure of 0.03 MPa and carbon content of 15.5 wt%. The chemical composition of the solid solution with the optimal process could be drawn as (Cr{sub 0.85}V{sub 0.15}){sub 2}(C{sub 0.57}N{sub 0.43}). Thermal processing precursors method shows the advantages of lower synthesis temperature, shorter period and finer particles when comparing with the conventional preparations. - Highlights: • Single phase of (Cr,V){sub 2}(C,N) powders were synthesized for the first time. • Precursors were used to prepared the powders by carbothermal

Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S2CN(iPr)CH2CH2OH]2

International Nuclear Information System (INIS)

Tan, Yee Seng; Halim, Siti Nadiah Abdul; Tiekink, Edward R.T.; Sunway Univ., Bandar Sunway

2016-01-01

Crystallization of Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 from ethanol yields the coordination polymer [{Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 }.EtOH] ∞ (1) within 3 h. When the solution is allowed to stand for another hour, the needles begin to dissolve and prisms emerge of the supramolecular isomer (SI), binuclear {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 .2EtOH (2). These have been fully characterized spectroscopically and by X-ray crystallography. Polymeric 1 has 2-fold symmetry and features dithiocarbamate ligands coordinating two octahedral Cd atoms in a μ 2 κ 2 -tridentate mode. Binuclear 2 is centrosymmetric with two ligands being μ 2 κ 2 -tridentate as for 1 but the other two being κ 2 -chelating leading to square pyramidal geometries. The conversion of the kinetic crystallization product, 1, to thermodynamic 2 is irreversible but transformations mediated by recrystallization (ethanol and acetonitrile) to related literature SI species, namely coordination polymer [{Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 3 .MeCN] ∞ and binuclear {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 .2H 2 O.2MeCN, are demonstrated, some of which are reversible. Three other crystallization outcomes are described whereby crystal structures were obtained for the 1:2 co-crystal {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 :2[3-(propan-2-yl)-1,3-oxazolidine-2-thione] (3), the salt co-crystal [iPrNH 2 (CH 2 CH 2 OH)] 4 [SO 4 ] 2 {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 (4) and the salt [iPrNH 2 (CH 2 CH 2 OH)]{Cd[S 2 CN(iPr)CH 2 CH 2 OH] 3 } (5). These arise as a result of decomposition/oxidation of the dithiocarbamate ligands. In each of 3 and 4 the binuclear {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 SI, as in 2, is observed strongly suggesting a thermodynamic preference for this form.

Spectrophotometric determination of dopamine hydrochloride in pharmaceutical, banana, urine and serum samples by potassium ferricyanide-Fe(III).

Science.gov (United States)

Guo, Li; Zhang, Yan; Li, Quanmin

2009-12-01

In the present work, we developed a simple, sensitive and inexpensive method to determine dopamine hydrochloride using potassium ferricyanide-Fe(III) by spectrophotometry. The results show that Fe(III) is deoxidized to Fe(II) by dopamine hydrochloride at pH 4.0, and then Fe(II) reacts with potassium ferricyanide to form a soluble prussian blue (KFe(III)[Fe(II)(CN)6]). The absorbance of this product was monitored over time using a spectrophotometer at an absorption maximum of 735 nm, and the amount of dopamine hydrochloride could be calculated based on the absorbance. A good linear relationship of the concentration of dopamine hydrochloride versus absorbance was observed, and a linear regression equation of A = 0.022 + 0.16921C (microg mL(-1)) was obtained. Moreover, the apparent molar absorption coefficient for the indirect determination of dopamine hydrochloride was 3.2 x 10(4) L mol(-1) cm(-1). This described method has been used to determine dopamine hydrochloride in pharmaceutical, banana, urine and serum samples with satisfactory results.

Application and comparison of the SCS-CN-based rainfall-runoff model in meso-scale watershed and field scale

Science.gov (United States)

Luo, L.; Wang, Z.

2010-12-01

Soil Conservation Service Curve Number (SCS-CN) based hydrologic model, has widely been used for agricultural watersheds in recent years. However, there will be relative error when applying it due to differentiation of geographical and climatological conditions. This paper introduces a more adaptable and propagable model based on the modified SCS-CN method, which specializes into two different scale cases of research regions. Combining the typical conditions of the Zhanghe irrigation district in southern part of China, such as hydrometeorologic conditions and surface conditions, SCS-CN based models were established. The Xinbu-Qiao River basin (area =1207 km2) and the Tuanlin runoff test area (area =2.87 km2)were taken as the study areas of basin scale and field scale in Zhanghe irrigation district. Applications were extended from ordinary meso-scale watershed to field scale in Zhanghe paddy field-dominated irrigated . Based on actual measurement data of land use, soil classification, hydrology and meteorology, quantitative evaluation and modifications for two coefficients, i.e. preceding loss and runoff curve, were proposed with corresponding models, table of CN values for different landuse and AMC(antecedent moisture condition) grading standard fitting for research cases were proposed. The simulation precision was increased by putting forward a 12h unit hydrograph of the field area, and 12h unit hydrograph were simplified. Comparison between different scales show that it’s more effectively to use SCS-CN model on field scale after parameters calibrated in basin scale These results can help discovering the rainfall-runoff rule in the district. Differences of established SCS-CN model's parameters between the two study regions are also considered. Varied forms of landuse and impacts of human activities were the important factors which can impact the rainfall-runoff relations in Zhanghe irrigation district.

A CN-Based Ensembled Hydrological Model for Enhanced Watershed Runoff Prediction

Directory of Open Access Journals (Sweden)

Muhammad Ajmal

2016-01-01

Full Text Available A major structural inconsistency of the traditional curve number (CN model is its dependence on an unstable fixed initial abstraction, which normally results in sudden jumps in runoff estimation. Likewise, the lack of pre-storm soil moisture accounting (PSMA procedure is another inherent limitation of the model. To circumvent those problems, we used a variable initial abstraction after ensembling the traditional CN model and a French four-parameter (GR4J model to better quantify direct runoff from ungauged watersheds. To mimic the natural rainfall-runoff transformation at the watershed scale, our new parameterization designates intrinsic parameters and uses a simple structure. It exhibited more accurate and consistent results than earlier methods in evaluating data from 39 forest-dominated watersheds, both for small and large watersheds. In addition, based on different performance evaluation indicators, the runoff reproduction results show that the proposed model produced more consistent results for dry, normal, and wet watershed conditions than the other models used in this study.

Development of the dyed-track method for Kodak CN-85 detector

International Nuclear Information System (INIS)

Somogyi, G.; Toth-Szilagyi, M.; Varga, Z.; Monnin, M.; Lferde, M.

1984-01-01

The dyed-track method has been successfully developed for cellulose derivatives. The track parameters (width, colouration deepness, contrast, registration sensitivity), however, proved to be very dependent on the detector material and on the track processing conditions. In our previous works optimum conditions were presented mostly for cellulose acetate sheets. In the present work we have studied the influence of track processing parameters on the dyed-track formation in Kodak cellulose nitrate detector called CN-85. It is found that in this material optimum dyed-tracks can be produced with using no swelling but with a thermal annealing at 100 deg C for 1 hour after particle irradiation. For sensitization a treatment with 15% HCl at 22 deg C for 20 hours and for dyeing 0.3 wt% Rhodamine-B at 100 deg C for 1 hour proved to be the best. For better understanding the track dyeing phenomenon we have studied the colouration behaviour of electron-irradiated CN-85 detectors. (author)

Development of the dyed-track method for Kodak CN-85 detector

Energy Technology Data Exchange (ETDEWEB)

Somogyi, G.; Toth-Szilagyi, M.; Varga, Z. (Magyar Tudomanyos Akademia, Debrecen. Atommag Kutato Intezete); Monnin, M.; Lferde, M. (Clermont-Ferrand-2 Univ., 63 - Aubiere (France). Lab. de Physique Corpusculaire)

1984-01-01

The dyed-track method has been successfully developed for cellulose derivatives. The track parameters (width, colouration deepness, contrast, registration sensitivity), however, proved to be very dependent on the detector material and on the track processing conditions. In our previous works optimum conditions were presented mostly for cellulose acetate sheets. In the present work we have studied the influence of track processing parameters on the dyed-track formation in Kodak cellulose nitrate detector called CN-85. It is found that in this material optimum dyed-tracks can be produced with using no swelling but with a thermal annealing at 100 deg C for 1 hour after particle irradiation. For sensitization a treatment with 15% HCl at 22 deg C for 20 hours and for dyeing 0.3 wt% Rhodamine-B at 100 deg C for 1 hour proved to be the best. For better understanding the track dyeing phenomenon we have studied the colouration behaviour of electron-irradiated CN-85 detectors.

Local Structure in Americium and Californium Hexa-cyanoferrates - Comparison with Their Lanthanide Analogues

International Nuclear Information System (INIS)

Dupouy, G.; Bonhoure, I.; Dumas, Th.; Moisy, Ph.; Petit, S.; Den Auwer, Ch.; Conradson, St.D.; Hennig, Ch.; Scheinost, A.C.; Le Naour, C.; Simoni, E.

2011-01-01

Metal hexa-cyanoferrates are well known molecular solids for a large variety of cations, although very little has been described for actinide adducts. Two new members of actinide(III) hexa-cyanoferrates were synthesized with the cations americium and californium. They were structurally characterized by infrared and X-ray absorption spectroscopy. Combined EXAFS data at the iron K edge and actinide L 3 edge provide evidence for a three-dimensional model for these two new compounds. Structural data in terms of bond lengths were compared to those reported for the parent lanthanide(III) compounds, neodymium and gadolinium hexa-cyanoferrates, respectively: the americium compound with (KNd(III)Fe(II)-Fe-III(CN) 6 .4H 2 O and the californium compound with (KGd(III)Fe(II)(CN) . 3.5H 2 O and (KGd(III)Fe(II)(CN) 6 .3H 2 O. This comparison between actinide and lanthanide homologues has been carried out on the basis of ionic radii considerations. The americium and neodymium environments appear to be very similar and are arranged in a tri-capped trigonal prism polyhedron of coordination number 9 (CN: 9), in which the americium atom is bonded to six nitrogen atoms and to three water molecules. For the californium adduct, a similar comparison and bond length and angle values derived from EXAFS studies suggest that the californium cation sits in a bi-capped trigonal prism (CN: 8) as in (KGd(III)Fe(II)(CN) 6 . 3H 2 O. This arrangement differs from that in the structure of (KGd(III)Fe(II)(CN) 6 .3.5H 2 O, in which the gadolinium atom is surrounded by 9 atoms. This is one of the rare pieces of information revealed by EXAFS spectroscopy for americium and californium in comparison to lanthanide atoms in molecular solid compounds. A discussion on the decrease in bond length and coordination number from americium to californium is also provided, on the basis of crystallographic results reported in the literature for actinide(III) and lanthanide(III) hydrate series. (authors)

Exact estimation of biodiesel cetane number (CN) from its fatty acid methyl esters (FAMEs) profile using partial least square (PLS) adapted by artificial neural network (ANN)

International Nuclear Information System (INIS)

Hosseinpour, Soleiman; Aghbashlo, Mortaza; Tabatabaei, Meisam; Khalife, Esmail

2016-01-01

Highlights: • Estimating the biodiesel CN from its FAMEs profile using ANN-based PLS approach. • Comparing the capability of ANN-adapted PLS approach with the standard PLS model. • Exact prediction of biodiesel CN from it FAMEs profile using ANN-based PLS method. • Developing an easy-to-use software using ANN-PLS model for computing the biodiesel CN. - Abstract: Cetane number (CN) is among the most important properties of biodiesel because it quantifies combustion speed or in better words, ignition quality. Experimental measurement of biodiesel CN is rather laborious and expensive. However, the high proportionality of biodiesel fatty acid methyl esters (FAMEs) profile with its CN is very appealing to develop straightforward and inexpensive computerized tools for biodiesel CN estimation. Unfortunately, correlating the chemical structure of biodiesel to its CN using conventional statistical and mathematical approaches is very difficult. To solve this issue, partial least square (PLS) adapted by artificial neural network (ANN) was introduced and examined herein as an innovative approach for the exact estimation of biodiesel CN from its FAMEs profile. In the proposed approach, ANN paradigm was used for modeling the inner relation between the input and the output PLS score vectors. In addition, the capability of the developed method in predicting the biodiesel CN was compared with the basal PLS method. The accuracy of the developed approaches for computing the biodiesel CN was assessed using three statistical criteria, i.e., coefficient of determination (R"2), mean-squared error (MSE), and percentage error (PE). The ANN-adapted PLS method predicted the biodiesel CN with an R"2 value higher than 0.99 demonstrating the fidelity of the developed model over the classical PLS method with a markedly lower R"2 value of about 0.85. In order to facilitate the use of the proposed model, an easy-to-use computer program was also developed on the basis of ANN-adapted PLS

Nitrato-complexes of Y(III), La(III), Ce(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III), Dy(III) and Ho(III) with 2-(2'-pyridyl) benzimidazole

Energy Technology Data Exchange (ETDEWEB)

Mishra, A; Singh, M P; Singh, V K

1982-05-01

The nitrato-complexes, (Y(PyBzH)/sub 2/(NO/sub 3/)/sub 2/)NO/sub 3/.H/sub 2/O and Nd, Sm, Gd, Tb, Dy, Ho ; n=1-3, m=0-0.5 ; PyBzh=2-(2 -pyridyl)benzimidazole) are formed on interaction of the ligand with metal nitrates in ethanol. The electrical conductance values (116-129 ohm/sup -1/cm/sup 2/mol/sup -1/) suggest 1:1 electrolyte-nature of the complexes. Magnetic moment values of Ce(2.53 B.M.), Pr(3.62 B.M.), Nd(3.52 B.M.), Sm(1.70 B.M.), Gd(8.06 B.M.), Tb(9.44 B.M.), Dy(10.56 B.M.) and Ho(10.51 B.M.) in the complexes confirm the positive state of the metals. Infrared evidences are obtained for the existance of both coordinated (C/sub 2/v) and uncoordinated (D/sub 3/h) nitrate groups. Electronic absorption spectra of Pr(III)-, Nd(III)-, Sm(III)-, Tb(III)-, Dy(III)- and Ho(III)-complexes have been analysed in the light of LSJ terms.

Nitrato-complexes of Y(III), La(III), Ce(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III), Dy(III) and Ho(III) with 2-(2'-pyridyl) benzimidazole

International Nuclear Information System (INIS)

Mishra, A.; Singh, M.P.; Singh, V.K.

1982-01-01

The nitrato-complexes, [Y(PyBzH) 2 (NO 3 ) 2 ]NO 3 .H 2 O and Nd, Sm, Gd, Tb, Dy, Ho ; n=1-3, m=0-0.5 ; PyBzh=2-(2 -pyridyl)benzimidazole] are formed on interaction of the ligand with metal nitrates in ethanol. The electrical conductance values (116-129 ohm -1 cm 2 mol -1 ) suggest 1:1 electrolyte-nature of the complexes. Magnetic moment values of Ce(2.53 B.M.), Pr(3.62 B.M.), Nd(3.52 B.M.), Sm(1.70 B.M.), Gd(8.06 B.M.), Tb(9.44 B.M.), Dy(10.56 B.M.) and Ho(10.51 B.M.) in the complexes confirm the terpositive state of the metals. Infrared evidences are obtained for the existance of both coordinated (C 2 v) and uncoordinated (D 3 h) nitrate groups. Electronic absorption spectra of Pr(III)-, Nd(III)-, Sm(III)-, Tb(III)-, Dy(III)- and Ho(III)-complexes have been analysed in the light of LSJ terms. (author)

Effect of nano-CeO 2 on microstructure properties of TiC/TiN+TiCN ...

Indian Academy of Sciences (India)

TiC/TiN+TiCN-reinforced composite coatings were fabricated on Ti–6Al–4V alloy by laser cladding, which improved surface performance of the substrate. ... X-ray diffraction results indicated that Al3Ti+TiC/TiN+nano-CeO2 laser-cladded coating consisted of Ti3Al, TiC, TiN, Ti2Al20Ce, TiC0.3N0.7, Ce(CN)3 and CeO2, this ...

Determination of stability constants for thallium(III) cyanide complexes in aqueous solution by means of 13C and 205Ti NMR

International Nuclear Information System (INIS)

Blixt, J.; Gyori, B.; Glaser, J.

1989-01-01

In contrast to what is usually assumed, we have found and proved that thallium(III) forms very strong cyanide complexes in aqueous solution. The authors have investigated this system using 205 Tl, 13 C, and 14 N NMR and potentiometry and established the existence of four thallium(III)-cyanide complexes of the composition Tl(CN) n 3-n , n = 1-4. We have measured their chemical shifts and spin-spin coupling constants and determined their formation constants at 25 degree C in dilute (0.05 M) aqueous solution in the ionic medium ([Na + ] = 1 M, [Li + ] + [H + ] = 3 M, [ClO 4 - ] = 4 M). We have also determined the stability constant for HCN in the same ionic medium, log K a = 10.11 (5)

A highly selective fluorescent chemosensor for CN- based on a novel bis(salamo)-type tetraoxime ligand

Science.gov (United States)

Wang, Fei; Gao, Lei; Zhao, Qing; Zhang, Yang; Dong, Wen-Kui; Ding, Yu-Jie

2018-02-01

The optical properties of a novel chemosensor for cyanide anions based on a symmetric bis(salamo)-type ligand (H3L) were investigated by UV-Vis and fluorescence spectroscopy in MeOH/H2O (1:1 v/v) solution. Sensor H3L can selectively sense CN- based on prominent color changes among other anions. The chemosensor exhibits an apparent fluorescence enhancement at 482 nm to CN- which because cyanide ions interact with Cdbnd N bonds. Combining the corrected Benesi-Hildebrand formula, the binding constant of the formed host-guest complex was calculated as 2.42 × 105 M- 1. Meanwhile, the detection limit of the sensor toward CN- was 8.91 × 10- 7 M. It is worth noting that the designed sensor can be used for rapid detection of cyanide anions in basic pH range, and has great practical value.

Comparative studies of neodymium (III)-selective PVC membrane sensors

Energy Technology Data Exchange (ETDEWEB)

Gupta, Vinod K., E-mail: vinodfcy@iitr.ernet.in [Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247 667 (India); Goyal, Rajendra N.; Sharma, Ram A. [Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247 667 (India)

2009-08-04

Sensors based on two neutral ionophores, N,N'-bis((1H-pyrrol-2-yl)methylene)cyclohexane-1,2-diamine (L{sub 1}) and 3,3'-(cyclohexane-1,2-diylbis(azan-1-yl-1-ylidene) bis(methan-1-yl-1-ylidene)bis(5-hydroxymethyl)pyridine-2-ol) (L{sub 2}) are described for quantification of neodymium (III). Effect of various plasticizers; 2-nitrophenyloctylether (o-NPOE), dibutyl butylphosphonate (DBBP), tri-n-butyl phosphates (TBP), dioctylpthalate (DOP) and chloronapthalen (CN) and anion excluder, sodiumtetraphenylborate (NaTPB) has been studied. The membrane composition of PVC:o-NPOE:ionophore (L{sub 1}):NaTPB (w/w; mg) of 150:300:5:5 exhibited best performance. The sensor with ionophore (L{sub 1}) exhibits significantly enhanced selectivity towards neodymium (III) in the concentration range 5.0 x 10{sup -7} to 1.0 x 10{sup -2} M with a detection limit of 1.0 x 10{sup -7} M and a Nernstian compliance (19.8 {+-} 0.3 mV decade{sup -1} of activity) within pH range 4.0-8.0. The response time of sensor was found as 10 s. The influence of the membrane composition and possible interfering ions has also been investigated on the response properties of the electrode. The fast and stable response, good reproducibility and long-term stability of the sensor are observed. The sensor has been found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of methanol, ethanol or acetonitrile and could be used for a period of 3 months. The selectivity coefficients determined by using fixed interference method (FIM) indicate high selectivity for neodymium. The proposed electrode shows fairly good discrimination of neodymium (III) from other cations. The application of prepared sensor has been demonstrated in the determination of neodymium (III) in spiked water samples.

TiCN thin films grown by reactive crossed beam pulsed laser deposition

Science.gov (United States)

Escobar-Alarcón, L.; Camps, E.; Romero, S.; Muhl, S.; Camps, I.; Haro-Poniatowski, E.

2010-12-01

In this work, we used a crossed plasma configuration where the ablation of two different targets in a reactive atmosphere was performed to prepare nanocrystalline thin films of ternary compounds. In order to assess this alternative deposition configuration, titanium carbonitride (TiCN) thin films were deposited. Two crossed plasmas were produced by simultaneously ablating titanium and graphite targets in an Ar/N2 atmosphere. Films were deposited at room temperature onto Si (100) and AISI 4140 steel substrates whilst keeping the ablation conditions of the Ti target constant. By varying the laser fluence on the carbon target it was possible to study the effect of the carbon plasma on the characteristics of the deposited TiCN films. The structure and composition of the films were analyzed by X-ray Diffraction, Raman Spectroscopy and non-Rutherford Backscattering Spectroscopy. The hardness and elastic modulus of the films was also measured by nanoindentation. In general, the experimental results showed that the TiCN thin films were highly oriented in the (111) crystallographic direction with crystallite sizes as small as 6.0 nm. It was found that the hardness increased as the laser fluence was increased, reaching a maximum value of about 33 GPa and an elastic modulus of 244 GPa. With the proposed configuration, the carbon content could be easily varied from 42 to 5 at.% by changing the laser fluence on the carbon target.

Thermochemistry of the reactions between CN+ and H2O in the gas phase

Science.gov (United States)

Ijjaali, Fatima; Alcami, Manuel; Mo, Otilia; Yanez, Manuel

The [H2, C, N, O]+ potential energy surface (PES) has been explored by means of high-level ab initio calculations, carried out in the framework of the G2 theory. From this survey we concluded that the predominant products of the CN+ +H2O reaction are the result of the dissociation of HNCOH+ species and to a much lesser extent of the CNHOH+ cation to yield CNH+ +OH. According to our results HCN+ should not be a product of this reaction because all pathways leading to its formation are unfavourable with regards to other competitive processes. Other reactive channels lead to the formation of the H2ONC+ structure which dissociates into CN + H2O+. The loss of NH(3Σ) and O(3P) seems to take place following spin-forbidden reaction paths through an intersystem crossing between the singlet and the triplet PESs. The global minimum of the PES, H2NCO+ is easily accessible and should lead to the loss of carbon monoxide which has not been experimentally observed in CN+ + H2O reactions. We cannot oOEer a clear explanation for this disagreement between theory and experiment.

Extraction of benzene and cyclohexane using [BMIM][N(CN)2] and their equilibrium modeling

Science.gov (United States)

Ismail, Marhaina; Bustam, M. Azmi; Man, Zakaria

2017-12-01

The separation of aromatic compound from aliphatic mixture is one of the essential industrial processes for an economically green process. In order to determine the separation efficiency of ionic liquid (IL) as a solvent in the separation, the ternary diagram of liquid-liquid extraction (LLE) 1-butyl-3-methylimidazolium dicyanamide [BMIM][N(CN)2] with benzene and cyclohexane was studied at T=298.15 K and atmospheric pressure. The solute distribution coefficient and solvent selectivity derived from the equilibrium data were used to evaluate if the selected ionic liquid can be considered as potential solvent for the separation of benzene from cyclohexane. The experimental tie line data was correlated using non-random two liquid model (NRTL) and Margules model. It was found that the solute distribution coefficient is (0.4430-0.0776) and selectivity of [BMIM][N(CN)2] for benzene is (53.6-13.9). The ternary diagram showed that the selected IL can perform the separation of benzene and cyclohexane as it has extractive capacity and selectivity. Therefore, [BMIM][N(CN)2] can be considered as a potential extracting solvent for the LLE of benzene and cyclohexane.

Computational investigation of the electronic and structural properties of CN radical on the pristine and Al-doped (6, 0) BN nanotubes

International Nuclear Information System (INIS)

Soltani, Alireza; Moradi, Ali Varasteh; Bahari, Mahsa; Masoodi, Anis; Shojaee, Shamim

2013-01-01

We have performed first-principle calculations to investigate the adsorption behavior of the CN radical (CåN) on the external surface of H-capped Al-doped (6, 0) zigzag single-walled BN nanotubes (BNNT). We calculated the bond length, gap energies, dipole moments, and electronic properties of the · CN on the exterior surface of SWBNNT. Binding energy corresponding to the most stable configuration of CN radical on Al N -doped BNNT is found to be −471.73 kJ mol −1 . The calculated density of states (DOS) reveals that there is a significant orbital hybridization between · CN and Al-doping species in the adsorption process being evidence of an exothermic process. The results indicate that BNNT could be a suitable sensor

Structural variety in solvated lanthanoid (III) halide complexes

International Nuclear Information System (INIS)

Deacon, G.B; Feng, T.; Scott, N.M.; Junk, P.C.; James Cook University, Townsville, QLD; Meyer, G.; Skelton, B.W.; White, A.H.

2000-01-01

Treatment of lanthanum metal with CH 2 Br 2 or CH 2 I 2 in tetrahydrofuran (thf) under ultrasound conditions yields the corresponding [LaX 3 (thf) 4 ] (X Br, I) complexes in good yield. Recrystallization of [LaBr 3 (thf) 4 ] from 1,2-dimethoxyethane (dme) or bis(2-methoxyethyl) ether (dig-lyme) generates [LaBr 2 (μ-Br)(dme) 2 ] 2 and [LaBr 2 (dig-lyme) 2 ][LaBr 4 (diglyme)]. Treatment of lanthanoid metals with hexachloroethane in dme yields [LnCl 3 (dme) 2 ] (Ln = La, Nd, Er or Yb) and in acetonitrile [YbCl 2 (MeCN) 5 ] 2 [YbCl 3 (MeCN)(-Cl) 2 YbCl 3 (MeCN)]. The reaction of Yb metal pieces with 1,2-dibromoethane in thf and dme gave single crystals of [YbBr 3 (thf) 3 ] and [YbBr 3 (dme) 2 ], respectively. The X-ray determined structure of [LaBr 3 (thf) 4 ] shows a seven-coordinate monomer with pentagonal-bipyramidal stereochemistry and apical bromide ligands. For [YbBr 3 (thf) 3 ], a monomeric structure with mer-octahedral stereochemistry is observed. In [LaBr 2 (μ-Br)(dme) 2 ] 2 , two eight-coordinate La centres are linked by two bridging bromides. The dme ligands have a trans relationship to each other, and cis terminal bromides are transoid to the bridging bromides with dodecahedral stereochemistry for La. By contrast, the 1: 1.5 diglyme adduct is found to be ionic [LaBr 2 (diglyme) 2 ][LaBr 4 (diglyme)], with an eight-coordinate bicapped trigonal-prismatic lanthanum cation and a seven-coordinate pentagonal-bipyramidal lanthanum anion. In the cation, the bromide ligands are cis to each other, and in the anion, two bromides are equatorial and two are axial. In [YbBr 3 (dme) 2 ], [YbCl 3 (dme) 2 ] and [ErCl 3 (dme) 2 ], a seven-coordinate pentagonal-bipyramidal arrangement exists with apical halogen ligands. Far-infrared data, and in particular the absence of absorptions attributable to I(La-Cl ter ), suggest that [LaCl 3 (dme)] is polymeric with six bridging chlorides per lanthanum. For [YbCl 2 (MeCN) 5 ] 2 [YbCl 3 (MeCN)(-Cl) 2 YbCl 3 -(MeCN)], a remarkable

A density functional study of structures and stability of SinCN clusters

International Nuclear Information System (INIS)

Gai Zhigang; Yang Li; Zhao Jie; Chu Shibo

2011-01-01

In this paper, density functional theory (DFT) B3LYP method with 6-311G * basis set has been used to investigate geometric configurations, vibrational frequencies and ground state energies of Si n CN (n = 2 ∼ 6) clusters. The energies and spin multiplicities of ground states and substable states have been discussed, respectively. Harmonic frequencies and infrared spectra intensity for these clusters are given in order to aid in the characterization of the stable structures. The results show that the zero point energy (ZPE), thermocapacity and entropies are nearly in proportion to increased n, whose average enhancement are 0.80 kcal/mol, 5.20 cal/mol · K and 12.72 cal/ mol · K, respectively. The stability of Si n CN (n = 2 ∼ 6) clusters with even n are greater than that with odd n. (authors)

The Possible Interstellar Anion CH2CN-: Spectroscopic Constants, Vibrational Frequencies, and Other Considerations

Science.gov (United States)

Fortenberry, Ryan C.; Crawford, T. Daniel; Lee, Timothy J.

2013-01-01

The A\\ ^1B_1 \\leftarrow \\tilde{X}\\ ^1A^{\\prime } excitation into the dipole-bound state of the cyanomethyl anion (CH2CN-) has been hypothesized as the carrier for one diffuse interstellar band. However, this particular molecular system has not been detected in the interstellar medium even though the related cyanomethyl radical and the isoelectronic ketenimine molecule have been found. In this study, we are employing the use of proven quartic force fields and second-order vibrational perturbation theory to compute accurate spectroscopic constants and fundamental vibrational frequencies for \\tilde{X}\\ ^1A^{\\prime } CH2CN- in order to assist in laboratory studies and astronomical observations.

Post-transition state dynamics and product energy partitioning following thermal excitation of the F∙∙∙HCH₂ CN transition state: Disagreement with experiment

Energy Technology Data Exchange (ETDEWEB)

Pratihar, Subha [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA; Ma, Xinyou [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA; Xie, Jing [Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA; Scott, Rebecca [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA; Gao, Eric [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA; Ruscic, Branko [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA and Computation Institute, University of Chicago, Chicago, Illinois 60637, USA; Aquino, Adelia J. A. [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA; School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, People’s Republic of China; Institute for Soil Research University of Natural Resources and Life Sciences Vienna, Peter-Jordan-Strasse 82, A-1190 Vienna, Austria; Setser, Donald W. [Institute for Soil Research University of Natural Resources and Life Sciences Vienna, Peter-Jordan-Strasse 82, A-1190 Vienna, Austria; Hase, William L. [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA

2017-10-14

Born-Oppenheimer direct dynamics simulations were performed to study atomistic details of the F + CH₃CN → HF + CH₂CN H-atom abstraction reaction. The simulation trajectories were calculated with a combined M06-2X/MP2 algorithm utilizing the 6-311++G** basis set. In accord with experiment and assuming the accuracy of transition state theory (TST), the trajectories were initiated at the F-HCH₂CN abstraction TS with a 300 K Boltzmann distribution of energy and directed towards products. Recrossing of the TS was negligible, confirming the accuracy of TST for the simulation. HF formation was rapid, occurring within 0.014 ps of the trajectory initiation. The intrinsic reaction coordinate (IRC) for reaction involves rotation of HF about CH₂CN and then trapping in the CH₂CN-HF post-reaction potential energy well of ~10 kcal/mol with respect to the HF + CH₂CN products. In contrast to this IRC, five different trajectory types were observed, with the majority involving direct dissociation and only 11% approximately following the IRC. The HF vibrational and rotational quantum numbers, n and J, were calculated when HF was initially formed and they increase as potential energy is released in forming the HF + CH₂CN products. The population of the HF product vibrational states is only in qualitative agreement with experiment, with the simulations showing depressed and enhanced populations of the n = 1 and 2 states as compared to experiment. From the simulations and with an anharmonic zero-point energy constraint, the percentage partitioning of the product energy to relative translation, HF rotation, HF vibration, CH₂CN rotation and CH₂CN vibration is 5, 11, 60, 7, and 16%, respectively. In contrast the experimental energy partitioning percentages to HF rotation and vibration are 6 and 41%. Comparisons are made between the current simulation and those for other F + H

Co-intercalation of Mg(2+) and Na(+) in Na(0.69)Fe2(CN)6 as a High-Voltage Cathode for Magnesium Batteries.

Science.gov (United States)

Kim, Dong-Min; Kim, Youngjin; Arumugam, Durairaj; Woo, Sang Won; Jo, Yong Nam; Park, Min-Sik; Kim, Young-Jun; Choi, Nam-Soon; Lee, Kyu Tae

2016-04-06

Thanks to the advantages of low cost and good safety, magnesium metal batteries get the limelight as substituent for lithium ion batteries. However, the energy density of state-of-the-art magnesium batteries is not high enough because of their low operating potential; thus, it is necessary to improve the energy density by developing new high-voltage cathode materials. In this study, nanosized Berlin green Fe2(CN)6 and Prussian blue Na(0.69)Fe2(CN)6 are compared as high-voltage cathode materials for magnesium batteries. Interestingly, while Mg(2+) ions cannot be intercalated in Fe2(CN)6, Na(0.69)Fe2(CN)6 shows reversible intercalation and deintercalation of Mg(2+) ions, although they have the same crystal structure except for the presence of Na(+) ions. This phenomenon is attributed to the fact that Mg(2+) ions are more stable in Na(+)-containing Na(0.69)Fe2(CN)6 than in Na(+)-free Fe2(CN)6, indicating Na(+) ions in Na(0.69)Fe2(CN)6 plays a crucial role in stabilizing Mg(2+) ions. Na(0.69)Fe2(CN)6 delivers reversible capacity of approximately 70 mA h g(-1) at 3.0 V vs Mg/Mg(2+) and shows stable cycle performance over 35 cycles. Therefore, Prussian blue analogues are promising structures for high-voltage cathode materials in Mg batteries. Furthermore, this co-intercalation effect suggests new avenues for the development of cathode materials in hybrid magnesium batteries that use both Mg(2+) and Na(+) ions as charge carriers.

The Beckman-Quarles theorem for continuous mappings from R^n to C^n

OpenAIRE

Tyszka, Apoloniusz

2002-01-01

Let \\phi((x_1,...,x_n),(y_1,...,y_n))=(x_1-y_1)^2+...+(x_n-y_n)^2. We say that f:R^n -> C^n preserves distance d>=0 if for each x,y \\in R^n \\phi(x,y)=d^2 implies \\phi(f(x),f(y))=d^2. We prove that if x,y \\in R^n (n>=3) and |x-y|=(\\sqrt{2+2/n})^k \\cdot (2/n)^l (k,l are non-negative integers) then there exists a finite set {x,y} \\subseteq S(x,y) \\subseteq R^n such that each unit-distance preserving mapping from S(x,y) to C^n preserves the distance between x and y. It implies that each continuou...

Collision energy-resolved study of the emission cross-section and the Penning ionization cross-section in the reaction of BrCN with He*(2 3S)

Science.gov (United States)

Kanda, Kazuhiro; Yamakita, Yoshihiro; Ohno, Koichi

2001-12-01

The dissociative excitation of BrCN producing CN(B 2Σ +) fragment by the collision of He *(2 3S) was investigated by the collision energy-resolved electron and emission spectroscopy using time-of-flight method with a high-intensity He * beam. The Penning electrons ejected from BrCN and the subsequent CN ( B2Σ +- X2Σ +) emission were measured as a function of collision energy in the range of 90-180 meV. The formation of CN ( B2Σ +) is concluded to proceed dominantly via the promotion of an electron from Π-character orbital, by comparison between the collision energy dependence of the partial Penning ionization cross-sections and the CN ( B2Σ +- X2Σ +) emission cross-section.

Effects of C/N ratio on nitrous oxide production from nitrification in a laboratory-scale biological aerated filter reactor.

Science.gov (United States)

He, Qiang; Zhu, Yinying; Fan, Leilei; Ai, Hainan; Huangfu, Xiaoliu; Chen, Mei

2017-03-01

Emission of nitrous oxide (N 2 O) during biological wastewater treatment is of growing concern. This paper reports findings of the effects of carbon/nitrogen (C/N) ratio on N 2 O production rates in a laboratory-scale biological aerated filter (BAF) reactor, focusing on the biofilm during nitrification. Polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) and microelectrode technology were utilized to evaluate the mechanisms associated with N 2 O production during wastewater treatment using BAF. Results indicated that the ability of N 2 O emission in biofilm at C/N ratio of 2 was much stronger than at C/N ratios of 5 and 8. PCR-DGGE analysis showed that the microbial community structures differed completely after the acclimatization at tested C/N ratios (i.e., 2, 5, and 8). Measurements of critical parameters including dissolved oxygen, oxidation reduction potential, NH 4 + -N, NO 3 - -N, and NO 2 - -N also demonstrated that the internal micro-environment of the biofilm benefit N 2 O production. DNA analysis showed that Proteobacteria comprised the majority of the bacteria, which might mainly result in N 2 O emission. Based on these results, C/N ratio is one of the parameters that play an important role in the N 2 O emission from the BAF reactors during nitrification.

Computational investigation of the electronic and structural properties of CN radical on the pristine and Al-doped (6, 0) BN nanotubes

Energy Technology Data Exchange (ETDEWEB)

Soltani, Alireza, E-mail: alireza.soltani46@yahoo.com [Young Researchers and Elite Club, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of); Moradi, Ali Varasteh [Department of Chemistry, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of); Bahari, Mahsa [Young Researchers and Elite Club, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of); Masoodi, Anis [Department of Chemistry, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of); Shojaee, Shamim [Young Researchers and Elite Club, Gorgan Branch, Islamic Azad University, Gorgan (Iran, Islamic Republic of)

2013-12-01

We have performed first-principle calculations to investigate the adsorption behavior of the CN radical (CåN) on the external surface of H-capped Al-doped (6, 0) zigzag single-walled BN nanotubes (BNNT). We calculated the bond length, gap energies, dipole moments, and electronic properties of the {sup ·}CN on the exterior surface of SWBNNT. Binding energy corresponding to the most stable configuration of CN radical on Al{sub N}-doped BNNT is found to be −471.73 kJ mol{sup −1}. The calculated density of states (DOS) reveals that there is a significant orbital hybridization between {sup ·}CN and Al-doping species in the adsorption process being evidence of an exothermic process. The results indicate that BNNT could be a suitable sensor.

Valence shell threshold photoelectron spectroscopy of the CHxCN (x = 0-2) and CNC radicals.

Science.gov (United States)

Garcia, Gustavo A; Krüger, Julia; Gans, Bérenger; Falvo, Cyril; Coudert, Laurent H; Loison, Jean-Christophe

2017-07-07

We present the photoelectron spectroscopy of four radical species, CH x CN (x = 0-2) and CNC, formed in a microwave discharge flow-tube reactor by consecutive H abstractions from CH 3 CN (CH x CN + F → CH x-1 CN + HF (x = 1-3)). The spectra were obtained combining tunable vacuum ultraviolet synchrotron radiation with double imaging electron/ion coincidence techniques, which yielded mass-selected threshold photoelectron spectra. The results obtained for H 2 CCN complement existing ones while for the other radicals the data represent the first observation of their (single-photon) ionizing transitions. In the case of H 2 CCN, Franck-Condon calculations have been performed in order to assign the vibrational structure of the X + 1 A 1 ←X 2 B 1 ionizing transition. A similar treatment for the HCCN, CCN, and CNC radicals appeared to be more complicated mainly because a Renner-Teller effect strongly affects the vibrational levels of the ground electronic state of the HCCN + , CCN, and CNC species. Nevertheless, the first adiabatic ionization energies of these radicals are reported and compared to our ab initio calculated values, leading to new values for enthalpies of formation (Δ f H 298 0 (HCCN + (X 2 A ' ))=1517±12kJmol -1 ,Δ f H 298 0 (CCN(X 2 Π))=682±13kJmol -1 , and Δ f H 298 0 (CNC(X 2 Πg))=676±12kJmol -1 ), which are of fundamental importance for astrochemistry.

Estimating Composite Curve Number Using an Improved SCS-CN Method with Remotely Sensed Variables in Guangzhou, China

OpenAIRE

Fan, Fenglei; Deng, Yingbin; Hu, Xuefei; Weng, Qihao

2013-01-01

The rainfall and runoff relationship becomes an intriguing issue as urbanization continues to evolve worldwide. In this paper, we developed a simulation model based on the soil conservation service curve number (SCS-CN) method to analyze the rainfall-runoff relationship in Guangzhou, a rapid growing metropolitan area in southern China. The SCS-CN method was initially developed by the Natural Resources Conservation Service (NRCS) of the United States Department of Agriculture (USDA), and is on...

Structure, tribological and electrochemical properties of low friction TiAlSiCN/MoSeC coatings

International Nuclear Information System (INIS)

Bondarev, A.V.; Kiryukhantsev-Korneev, Ph.V.; Sheveyko, A.N.; Shtansky, D.V.

2015-01-01

Highlights: • TiAlSiCN/MoSeC coatings for tribological applications. • Doping with MoSeC reduces friction coefficient in humid air from 0.8–0.9 to 0.05. • Doping with MoSeC increases wear resistance by one-two orders of magnitude. • TiAlSiCN/MoSeC coatings demonstrated low friction coefficient in distilled water. • TiAlSiCN/MoSeC coatings showed superior tribological properties at moderate temperatures. - Abstract: The present paper is focused on the development of hard tribological coatings with low friction coefficient (CoF) in different environments (humid air, distilled water) and at elevated temperatures. TiAlSiCN/MoSeC coatings were deposited by magnetron sputtering of four-segment targets consisting of quarter circle TiAlSiCN segments, obtained by self-propagating high-temperature synthesis, and one or two cold pressed segments made of MoSe 2 and C powders in a ratio 1:1 wt%. The structure and phase composition of coatings were investigated by means of X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. The coatings were characterized in terms of their hardness, elastic modulus, and elastic recovery. The tribological properties of coatings were investigated first at room temperature against Al 2 O 3 and WC–Co balls, after which studied in distilled water and during continuous heating in air in the temperature range of 25–400 °C against Al 2 O 3 counterpart material. To evaluate their electrochemical characteristics, the coatings were tested in 1 N H 2 SO 4 solution. The obtained results show that the coating hardness depends on the amount of MoSeC additives and decreased from 40 to 28 (one MoSeC segment) and 12 GPa (two MoSeC segments). Doping with MoSeC resulted in a significant reduction of CoF values measured in humid air (RH 60 ± 5%) from 0.8–0.9 to 0.05 and an increase of wear resistance by one or two orders of magnitude depending on counterpart material. This was attributed

Structure, tribological and electrochemical properties of low friction TiAlSiCN/MoSeC coatings

Energy Technology Data Exchange (ETDEWEB)

Bondarev, A.V.; Kiryukhantsev-Korneev, Ph.V.; Sheveyko, A.N.; Shtansky, D.V., E-mail: shtansky@shs.misis.ru

2015-02-01

Highlights: • TiAlSiCN/MoSeC coatings for tribological applications. • Doping with MoSeC reduces friction coefficient in humid air from 0.8–0.9 to 0.05. • Doping with MoSeC increases wear resistance by one-two orders of magnitude. • TiAlSiCN/MoSeC coatings demonstrated low friction coefficient in distilled water. • TiAlSiCN/MoSeC coatings showed superior tribological properties at moderate temperatures. - Abstract: The present paper is focused on the development of hard tribological coatings with low friction coefficient (CoF) in different environments (humid air, distilled water) and at elevated temperatures. TiAlSiCN/MoSeC coatings were deposited by magnetron sputtering of four-segment targets consisting of quarter circle TiAlSiCN segments, obtained by self-propagating high-temperature synthesis, and one or two cold pressed segments made of MoSe{sub 2} and C powders in a ratio 1:1 wt%. The structure and phase composition of coatings were investigated by means of X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. The coatings were characterized in terms of their hardness, elastic modulus, and elastic recovery. The tribological properties of coatings were investigated first at room temperature against Al{sub 2}O{sub 3} and WC–Co balls, after which studied in distilled water and during continuous heating in air in the temperature range of 25–400 °C against Al{sub 2}O{sub 3} counterpart material. To evaluate their electrochemical characteristics, the coatings were tested in 1 N H{sub 2}SO{sub 4} solution. The obtained results show that the coating hardness depends on the amount of MoSeC additives and decreased from 40 to 28 (one MoSeC segment) and 12 GPa (two MoSeC segments). Doping with MoSeC resulted in a significant reduction of CoF values measured in humid air (RH 60 ± 5%) from 0.8–0.9 to 0.05 and an increase of wear resistance by one or two orders of magnitude depending on

Effect of ryegrass (Lolium perenne L.) roots inoculation using different arbuscular mycorrhizal fungi (AMF) species on sorption of iron-cyanide (Fe-CN) complexes

Science.gov (United States)

Sut, Magdalena; Boldt-Burisch, Katja; Raab, Thomas

2016-04-01

Soils and groundwater on sites of the former Manufactured Gas Plants (MGPs) are contaminated with various complex iron-cyanides (Fe-CN). Phytoremediation is a promising tool in stabilization and remediation of Fe-CN affected soils, however, it can be a challenging task due to extreme adverse and toxic conditions. Phytoremediation may be enhanced via rhizosphere microbial activity, which can cooperate on the degradation, transformation and uptake of the contaminants. Recently, increasing number of scientist reports improved plants performance in the removal of toxic compounds with the support of arbuscular mycorrhizae fungi (AMF). Series of batch experiments using potassium hexacyanoferrate (II) solutions, in varying concentrations, were used to study the effect of ryegrass roots (Lolium perenne L.) inoculation with Rhizophagus irregularis and a mixture of Rhizophagus irregularis, Funneliformis mosseae, Rhizophagus aggregatus, and Claroideoglomus etunicatum on Fe-CN sorption. Results indicated significantly higher colonization of R. irregularis than for the mixture of AMF species on ryegrass roots. Sorption experiments revealed significantly higher reduction of total CN and free CN content in the mycorrhizal roots, indicating greater cyanide decrease in the treatment inoculated with R. irregularis. Our study indicates contribution of AM fungi in phytoremediation of Fe-CN contaminated soil.

Cooperative redox-active additives of anthraquinone-2,7-disulphonate and K4Fe(CN)6 for enhanced performance of active carbon-based capacitors

Science.gov (United States)

Tian, Ying; Liu, Ming; Che, Ruxing; Xue, Rong; Huang, Liping

2016-08-01

Two redox additives of anthraquinone-2,7-disulphonate (AQDS) and K4Fe(CN)6 are introduced into the neutral medium of KNO3 for enhanced performance of active carbon-based (AC) capacitor. The Faradaic redox reactions of AQ/H2AQ and Fe(CN)63-/Fe(CN)64- are diffusion-controlled and occurred on the negative electrode and the positive electrode respectively and simultaneously, resulting in the enhancement of specific capacitance, power density and energy density of 240 F g-1, 527 W kg-1 and 26.3 Wh kg-1, respectively at a current density of 1.0 A g-1 for a symmetric AC capacitor in the electrolyte of 1 M KNO3-0.017 M K4Fe(CN)6-0.017 M AQDS. These values are much higher than those in the controls of either 1 M KNO3-0.017 M K4Fe(CN)6 or 1 M KNO3-0.017 M AQDS with only one pair of redox additives. These results demonstrate the cooperative K4Fe(CN)6 and AQDS for enhanced performance of AC capacitor, and thus provide an alternative approach for efficient capacitors.

Effects of styrene unit on molecular conformation and spectral properties of CNsbnd PhCHdbnd NPhCHdbnd CHPhsbnd CN

Science.gov (United States)

Fang, Zhengjun; Wu, Feng; Jiao, Yingchun; Wang, Nanfang; Au, Chaktong; Cao, Chenzhong; Yi, Bing

2018-05-01

Compound CN-PhCH=NPhCH=CHPh-CN with both stilbene and benzylidene aniline units was synthesized, and studied from the viewpoint of molecular conformation and spectroscopic property by a combined use of experimental and computational methods. The maximum UV absorption wavelength (λmax) of the compound in ethanol, acetonitrile, chloroform and cyclohexane solvents were measured, and the 13C NMR chemical shift value δC(Cdbnd N) in chloroform-d was determined. The crystal structure of the compound was determined by X-ray diffraction. The frontier molecular orbital was calculated by density functional theory method. The results show that the UV absorption spectrum of the titled compound is similar to those of Schiff bases, while there is a larger red shift of λmax comparing to that of CN-PhCH=NPh-CN. Moreover, the molecular configuration of the titled compound relative to Cdbnd N is anti-form, having a more obvious twisted structure. The spectral and structural behaviors are further supported by the results of frontier molecular orbital analyses, NBO, electrostatic potentials and TD-DFT calculations. The study provides deeper insights into the molecular conformation of Schiff bases.

Scaling analysis of [Fe(pyrazole)4]2[Nb(CN)8] molecular magnet

International Nuclear Information System (INIS)

Konieczny, P.; Pełka, R.; Zieliński, P.M.; Pratt, F.L.; Pinkowicz, D.; Sieklucka, B.; Wasiutyński, T.

2013-01-01

The critical behaviour of the three dimensional (3D) molecular magnet {[Fe II (pirazol) 4 ] 2 [Nb IV (CN) 8 ]·4H 2 O} n has been studied with the use of experimental techniques such as ac magnetometry and zero field μSR spectroscopy. The sample orders magnetically below T c =7.8 K. The measurements allowed to determine static exponents β, γ, and the dynamic exponent w. The resulting exponent values indicate that the studied system belongs to the universality class of the 3D Heisenberg model. - Highlights: • The critical behaviour of {[Fe II (pirazol) 4 ] 2 [Nb IV (CN) 8 ]∙4H 2 O} n has been studied. • Critical exponents β, γ, and w were obtained from ac magnetometry and ZF µSR data. • All obtained values of critical exponents are close to the 3D Heisenberg model

Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2′-bipyridine2(CN2

Directory of Open Access Journals (Sweden)

Kasper S. Kjær

2017-07-01

Full Text Available We have used femtosecond resolution UV-visible and Kβ x-ray emission spectroscopy to characterize the electronic excited state dynamics of [Fe(bpy2(CN2], where bpy=2,2′-bipyridine, initiated by metal-to-ligand charge transfer (MLCT excitation. The excited-state absorption in the transient UV-visible spectra, associated with the 2,2′-bipyridine radical anion, provides a robust marker for the MLCT excited state, while the transient Kβ x-ray emission spectra provide a clear measure of intermediate and high spin metal-centered excited states. From these measurements, we conclude that the MLCT state of [Fe(bpy2(CN2] undergoes ultrafast spin crossover to a metal-centered quintet excited state through a short lived metal-centered triplet transient species. These measurements of [Fe(bpy2(CN2] complement prior measurement performed on [Fe(bpy3]2+ and [Fe(bpy(CN4]2− in dimethylsulfoxide solution and help complete the chemical series [Fe(bpyN(CN6–2N]2N-4, where N = 1–3. The measurements confirm that simple ligand modifications can significantly change the relaxation pathways and excited state lifetimes and support the further investigation of light harvesting and photocatalytic applications of 3d transition metal complexes.

Electric dipole ordering in alkali-cyanides: NaCN and KCN

International Nuclear Information System (INIS)

Koiller, B.; Davidovich, M.A.; Carmo, L.C.S. do; Luety, F.

1983-01-01

A simple model for the low temperature electrically ordered state of NaCN and KCN is presented. The model takes into account electric dipole dressing effects which include cationic displacements determined experimentally. The ground state structure and the calculated values for the local electric fields are in fair agreement with experimental results. A parametrization for the elastic potencial confirms the plausibility of these model. (Author) [pt

Enhanced Rate Capability of Polymer-Derived SiCN Anode Material for Electrochemical Storage of Lithium with 3-D Carbon Nanotube Network Dispersed in Nanoscale.

Science.gov (United States)

Zhang, Junwei; Xu, Caihong; Liu, Zhaoping; Wang, Wei; Xin, Xing; Shen, Lu; Zhou, Xiaobing; Zhou, Jie; Huang, Qing

2015-04-01

Electrochemical performances of multi-walled carbon nanotubes (CNT)-SiCN composite have been investigated. The sample was synthesized by a simple ultrasonication assisted method combined with high-temperature pyrolysis and characterized by Fourier transform infrared spectra, Raman spectra, X-ray diffraction, field emission scanning electron microscopy and transmission electronic microscopy. In this composite, CNT were uniformly distributed in the SiCN ceramic matrix, it retained the structural integrity during the polymer-ceramic conversion and had a relatively strong bonding with the SiCN ceramic matrix. When tested as anode in the half cell, the obtained composite exhibited enhanced rate capability and cyclic capacity than that of pristine SiCN powder, CNT and graphite, it could supply a capacity of 222.7 mA h/g when charged at 2000 mA/g, while the SiCN anode showed nearly no capacity even at the low current density of 200 mA/g. It is expected that the CNT-SiCN composite, perhaps the series of CNT-PDC composites, may be prospective candidate for high power applications.

Progressive Transformation between Two Magnetic Ground States for One Crystal Structure of a Chiral Molecular Magnet.

Science.gov (United States)

Li, Li; Nishihara, Sadafumi; Inoue, Katsuya; Kurmoo, Mohamedally

2016-03-21

We report the exceptional observation of two different magnetic ground states (MGS), spin glass (SG, T(B) = 7 K) and ferrimagnet (FI, T(C) = 18 K), for one crystal structure of [{Mn(II)(D/L-NH2ala)}3{Mn(III)(CN)6}]·3H2O obtained from [Mn(CN)6](3-) and D/L-aminoalanine, in contrast to one MGS for [{Mn(II)(L-NH2ala)}3{Cr(III)(CN)6}]·3H2O. They consist of three Mn(NH2ala) helical chains bridged by M(III)(CN)6 to give the framework with disordered water molecules in channels and between the M(III)(CN)6. Both MGS are characterized by a negative Weiss constant, bifurcation in ZFC-FC magnetizations, blocking of the moments, both components of the ac susceptibilities, and hysteresis. They differ in the critical temperatures, absolute magnetization for 5 Oe FC (lack of spontaneous magnetization for the SG), and the shapes of the hysteresis and coercive fields. While isotropic pressure increases both T(crit) and the magnetizations linearly and reversibly in each case, dehydration progressively transforms the FI into the SG as followed by concerted in situ magnetic measurements and single-crystal diffraction. The relative strengths of the two moderate Mn(III)-CN-Mn(II) antiferromagnetic (J1 and J2), the weak Mn(II)-OCO-Mn(II) (J3), and Dzyaloshinkii-Moriya antisymmetric (DM) interactions generate the two sets of characters. Examination of the bond lengths and angles for several crystals and their corresponding magnetic properties reveals a correlation between the distortion of Mn(III)(CN)6 and the MGS. SG is favored by higher magnetic anisotropy by less distorted Mn(III)(CN)6 in good accordance with the Mn-Cr system. This conclusion is also born out of the magnetization measurements on orientated single crystals with fields parallel and perpendicular to the unique c axis of the hexagonal space group.

Sorghum phytochrome B inhibits flowering in long days by activating expression of SbPRR37 and SbGHD7, repressors of SbEHD1, SbCN8 and SbCN12.

Directory of Open Access Journals (Sweden)

Shanshan Yang

Full Text Available Light signaling by phytochrome B in long days inhibits flowering in sorghum by increasing expression of the long day floral repressors PSEUDORESPONSE REGULATOR PROTEIN (SbPRR37, Ma1 and GRAIN NUMBER, PLANT HEIGHT AND HEADING DATE 7 (SbGHD7, Ma6. SbPRR37 and SbGHD7 RNA abundance peaks in the morning and in the evening of long days through coordinate regulation by light and output from the circadian clock. 58 M, a phytochrome B deficient (phyB-1, ma3R genotype, flowered ∼60 days earlier than 100 M (PHYB, Ma3 in long days and ∼11 days earlier in short days. Populations derived from 58 M (Ma1, ma3R, Ma5, ma6 and R.07007 (Ma1, Ma3, ma5, Ma6 varied in flowering time due to QTL aligned to PHYB/phyB-1 (Ma3, Ma5, and GHD7/ghd7-1 (Ma6. PHYC was proposed as a candidate gene for Ma5 based on alignment and allelic variation. PHYB and Ma5 (PHYC were epistatic to Ma1 and Ma6 and progeny recessive for either gene flowered early in long days. Light signaling mediated by PhyB was required for high expression of the floral repressors SbPRR37 and SbGHD7 during the evening of long days. In 100 M (PHYB the floral activators SbEHD1, SbCN8 and SbCN12 were repressed in long days and de-repressed in short days. In 58 M (phyB-1 these genes were highly expressed in long and short days. Furthermore, SbCN15, the ortholog of rice Hd3a (FT, is expressed at low levels in 100 M but at high levels in 58 M (phyB-1 regardless of day length, indicating that PhyB regulation of SbCN15 expression may modify flowering time in a photoperiod-insensitive manner.

Copper (I) Selenocyanate (CuSeCN) as a Novel Hole-Transport Layer for Transistors, Organic Solar Cells, and Light-Emitting Diodes

KAUST Repository

Wijeyasinghe, Nilushi; Tsetseris, Leonidas; Regoutz, Anna; Sit, Wai-Yu; Fei, Zhuping; Du, Tian; Wang, Xuhua; McLachlan, Martyn A.; Vourlias, George; Patsalas, Panos A.; Payne, David J.; Heeney, Martin; Anthopoulos, Thomas D.

2018-01-01

The synthesis and characterization of copper (I) selenocyanate (CuSeCN) and its application as a solution-processable hole-transport layer (HTL) material in transistors, organic light-emitting diodes, and solar cells are reported. Density-functional theory calculations combined with X-ray photoelectron spectroscopy are used to elucidate the electronic band structure, density of states, and microstructure of CuSeCN. Solution-processed layers are found to be nanocrystalline and optically transparent (>94%), due to the large bandgap of ≥3.1 eV, with a valence band maximum located at −5.1 eV. Hole-transport analysis performed using field-effect measurements confirms the p-type character of CuSeCN yielding a hole mobility of 0.002 cm2 V−1 s−1. When CuSeCN is incorporated as the HTL material in organic light-emitting diodes and organic solar cells, the resulting devices exhibit comparable or improved performance to control devices based on commercially available poly(3,4-ethylenedioxythiophene):polystyrene sulfonate as the HTL. This is the first report on the semiconducting character of CuSeCN and it highlights the tremendous potential for further developments in the area of metal pseudohalides.

Copper (I) Selenocyanate (CuSeCN) as a Novel Hole-Transport Layer for Transistors, Organic Solar Cells, and Light-Emitting Diodes

KAUST Repository

Wijeyasinghe, Nilushi

2018-02-01

The synthesis and characterization of copper (I) selenocyanate (CuSeCN) and its application as a solution-processable hole-transport layer (HTL) material in transistors, organic light-emitting diodes, and solar cells are reported. Density-functional theory calculations combined with X-ray photoelectron spectroscopy are used to elucidate the electronic band structure, density of states, and microstructure of CuSeCN. Solution-processed layers are found to be nanocrystalline and optically transparent (>94%), due to the large bandgap of ≥3.1 eV, with a valence band maximum located at −5.1 eV. Hole-transport analysis performed using field-effect measurements confirms the p-type character of CuSeCN yielding a hole mobility of 0.002 cm2 V−1 s−1. When CuSeCN is incorporated as the HTL material in organic light-emitting diodes and organic solar cells, the resulting devices exhibit comparable or improved performance to control devices based on commercially available poly(3,4-ethylenedioxythiophene):polystyrene sulfonate as the HTL. This is the first report on the semiconducting character of CuSeCN and it highlights the tremendous potential for further developments in the area of metal pseudohalides.

Value of Free-Run Electromyographic Monitoring of Extraocular Cranial Nerves during Expanded Endonasal Surgery (EES) of the Skull Base.

Science.gov (United States)

Thirumala, Parthasarathy D; Mohanraj, Santhosh Kumar; Habeych, Miguel; Wichman, Kelley; Chang, Yue-Fang; Gardner, Paul; Snyderman, Carl; Crammond, Donald J; Balzer, Jeffrey

2013-06-01

Objective To evaluate the value of free-run electromyography (f-EMG) monitoring of extraocular cranial nerves (EOCN) III, IV, and VI during expanded endonasal surgery (EES) of the skull base in reducing iatrogenic cranial nerve (CN) deficits. Design We retrospectively identified 200 patients out of 990 who had at least one EOCN monitored during EES. We further separated patients into groups according to the specific CN monitored. In each CN group, we classified patients who had significant (SG) f-EMG activity as Group I and those who did not as Group II. Results A total of 696 EOCNs were monitored. The number of muscles supplied by EOCNs that had SG f-EMG activity was 88, including CN III = 46, CN IV = 21, and CN VI = 21. There were two deficits involving CN VI in patients who had SG f-EMG activity during surgery. There were 14 deficits observed, including CN III = 3, CN IV = 2, and CN VI = 9 in patients who did not have SG f-EMG activity during surgery. Conclusions f-EMG monitoring of EOCN during EES can be useful in identifying the location of the nerve. It seems to have limited value in predicting postoperative neurological deficits. Future studies to evaluate the EMG of EOCN during EES need to be done with both f-EMG and triggered EMG.

Rapid synthesis of graphitic carbon nitride powders by metathesis reaction between CaCN2 and C2Cl6

International Nuclear Information System (INIS)

Pang Linlin; Bi Jianqiang; Bai Yujun; Qi Yongxin; Zhu Huiling; Wang Chengguo; Wu Jiwei; Lu Chengwei

2008-01-01

Carbon nitride powders were rapidly synthesized at low temperature via the chemical metathesis reaction between CaCN 2 and C 2 Cl 6 . X-ray diffraction results confirm the formation of crystalline graphitic carbon nitride. Besides the dominant morphology of nanoparticles, flakes, nanorods, hollow and solid spheres can be observed by transmission electron microscopy. The absorption peaks of C-N, C=N and s-triazine rings, as well as the absence of C≡N peak in the infrared spectra, further verify the formation of graphite-like sp 2 -bonded structure with planar networks. Elemental analysis gives an atomic ratio of N/C around 0.3. X-ray photoelectron spectra exhibit the existence of chemical bonding between C and N

Engine Performance Test of the 1975 Chrysler - Nissan Model CN633 Diesel Engine

Science.gov (United States)

1975-09-01

An engine test of the Chrysler-Nissan Model CN633 diesel engine was performed to determine its steady-state fuel consumption and emissions (HC, CO, NOx) maps. The data acquired are summarized in this report.

On the development of a coupled regional climate-vegetation model RCM-CLM-CN-DV and its validation in Tropical Africa

Science.gov (United States)

Wang, Guiling; Yu, Miao; Pal, Jeremy S.; Mei, Rui; Bonan, Gordon B.; Levis, Samuel; Thornton, Peter E.

2016-01-01

This paper presents a regional climate system model RCM-CLM-CN-DV and its validation over Tropical Africa. The model development involves the initial coupling between the ICTP regional climate model RegCM4.3.4 (RCM) and the Community Land Model version 4 (CLM4) including models of carbon-nitrogen dynamics (CN) and vegetation dynamics (DV), and further improvements of the models. Model improvements derive from the new parameterization from CLM4.5 that addresses the well documented overestimation of gross primary production (GPP), a refinement of stress deciduous phenology scheme in CN that addresses a spurious LAI fluctuation for drought-deciduous plants, and the incorporation of a survival rule into the DV model to prevent tropical broadleaf evergreens trees from growing in areas with a prolonged drought season. The impact of the modifications on model results is documented based on numerical experiments using various subcomponents of the model. The performance of the coupled model is then validated against observational data based on three configurations with increasing capacity: RCM-CLM with prescribed leaf area index and fractional coverage of different plant functional types (PFTs); RCM-CLM-CN with prescribed PFTs coverage but prognostic plant phenology; RCM-CLM-CN-DV in which both the plant phenology and PFTs coverage are simulated by the model. Results from these three models are compared against the FLUXNET up-scaled GPP and ET data, LAI and PFT coverages from remote sensing data including MODIS and GIMMS, University of Delaware precipitation and temperature data, and surface radiation data from MVIRI and SRB. Our results indicate that the models perform well in reproducing the physical climate and surface radiative budgets in the domain of interest. However, PFTs coverage is significantly underestimated by the model over arid and semi-arid regions of Tropical Africa, caused by an underestimation of LAI in these regions by the CN model that gets exacerbated

Three-Dimensional Cadmium(II Cyanide Coordination Polymers with Ethoxy-, Butoxy- and Hexyloxy-ethanol

Directory of Open Access Journals (Sweden)

Takeshi Kawasaki

2016-08-01

Full Text Available The three novel cadmium(II cyanide coordination polymers with alkoxyethanols, [Cd(CN2(C2H5OCH2CH2OH]n (I, [{Cd(CN2(C4H9OCH2CH2OH}3{Cd(CN2}]n (II and [{Cd(CN2(H2O2}{Cd(CN2}3·2(C6H13OCH2CH2OH]n (III, were synthesized and charcterized by structural determination. Three complexes have three-dimensional Cd(CN2 frameworks; I has distorted tridymite-like structure, and, II and III have zeolite-like structures. The cavities of Cd(CN2 frameworks of the complexes are occupied by the alkoxyethanol molecules. In I and II, hydroxyl oxygen atoms of alkoxyethanol molecules coordinate to the Cd(II ions, and the Cd(II ions exhibit slightly distort trigonal-bipyramidal coordination geometry. In II, there is also tetrahedral Cd(II ion which is coordinated by only the four cyanides. The hydroxyl oxygen atoms of alkoxyethanol connects etheric oxygen atoms of the neighboring alkoxyethanol by hydrogen bond in I and II. In III, hexyloxyethanol molecules do not coordinate to the Cd(II ions, and two water molecules coordnate to the octahedral Cd(II ions. The framework in III contains octahedral Cd(II and tetrahedral Cd(II in a 1:3 ratio. The Cd(CN2 framework structures depended on the difference of alkyl chain for alkoxyethanol molecules.

Biogas Improvement by Adding Australian Zeolite During the Anaerobic Digestion of C:N Ratio Adjusted Swine Manure

DEFF Research Database (Denmark)

Wijesinghe, D. Thushari N.; Dassanayake, Kithsiri B.; Sommer, Sven G.

2018-01-01

Abstract: Maintenance of the ideal carbon: nitrogen (C:N) ratio with a minimum level of TAN is a key challenge for achieving maximum potential CH4 production through the anaerobic digestion process of agricultural waste such as swine manure. Biogas production can be enhanced by adding zeolite...... into the anaerobic digestion medium. However, the effects of zeolite addition to C:N ratio adjusted feedstock, on the digester performance is unknown. The objectives of this study were to investigate the effect of Australian zeolite on anaerobic digestion of swine manure with a C:N ratio adjusted to 30...... and to determine the optimal zeolite application rate to achieve the best performance. The Australian zeolite significantly enhanced CH4 production and reduced the lag phase of anaerobic digestion in batch production. The optimal addition rate of zeolite was appeared to be around 40 g/L. The better digester...

Nursery Culture Performance of Litopenaeus vannamei with Probiotics Addition and Different C/N Ratio Under Laboratory Condition

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WIDANARNI

2010-09-01

Full Text Available Application of bioflocs technology and probiotics has improved water quality and production of Pacific white shrimp (Litopenaeus vannamei culture. This experiment was to verify the effect of probiotic bacteria addition and different carbon:nitrogen (C:N ratio on water quality and performance of Pacific white shrimp nursery culture. Nursery culture was carried out for 25 days in an aquarium under laboratory condition with stock density of one Post-Larvae (PL (poslarval per liter (24 PL/aquarium of PL16 shrimp. Different C:N ratio resulted a significant difference on shrimp production performance. Treatment of 10 C:N ratio demonstrated the best shrimp growth (20.37 + 0.48% per day in weight and 6.05 + 0.41% per day in length, harvesting yield (1180 + 62 g/m3 and feed efficiency (121 + 6%. There was however no significant difference observed between treatments in water quality.

Nursery Culture Performance of Litopenaeus vannamei with Probiotics Addition and Different C/N Ratio Under Laboratory Condition

Directory of Open Access Journals (Sweden)

WIDANARNI

2010-09-01

Full Text Available Application of bioflocs technology and probiotics has improved water quality and production of Pacific white shrimp (Litopenaeus vannamei culture. This experiment was to verify the effect of probiotic bacteria addition and different carbon:nitrogen (C:N ratio on water quality and performance of Pacific white shrimp nursery culture. Nursery culture was carried out for 25 days in an aquarium under laboratory condition with stock density of one Post-Larvae (PL (poslarval per liter (24 PL/aquarium of PL16 shrimp. Different C:N ratio resulted a significant difference on shrimp production performance. Treatment of 10 C:N ratio demonstrated the best shrimp growth (20.37 ± 0.48% per day in weight and 6.05 ± 0.41% per day in length, harvesting yield (1180 ± 62 g/m3 and feed efficiency (121 ± 6%. There was however no significant difference observed between treatments in water quality.

Influence of trimethylsilane flow on the microstructure, mechanical and tribological properties of CrSiCN coatings in water lubrication

Science.gov (United States)

Wu, Zhiwei; Zhou, Fei; Wang, Qianzhi; Zhou, Zhifeng; Yan, Jiwang; Li, Lawrence Kwok-Yan

2015-11-01

CrSiCN coatings with different silicon and carbon contents were deposited on silicon wafers and 316L stainless steels using unbalanced magnetron sputtering via adjusting trimethylsilane (TMS) flow, and their microstructure and mechanical properties were characterized by X-ray diffraction (XRD), scanning electron microscopy(SEM), X-ray photoelectrons spectroscopy(XPS) and nano-indenter, respectively. The tribological properties of CrSiCN coatings sliding against SiC balls in water were investigated using ball-on-disk tribometer. The results showed that the CrSiCN coatings had fine composite microstructure consisting of nanocrystallites of Cr(C, N) crystal and amorphous phases such as a-Si3N4 and a-C(a-CNx). The typical columnar structures changed from fine cluster to coarse ones when the Si content was beyond 3.4 at.%. With an increase in the TMS flow, the hardness and Young's modulus of Corsican coatings all first increased, and then rapidly decreased, but the compressive stress in the coatings varied in the range of 2.8-4.8 GPa. When the TMS flow was 10 sccm, the CrSiCN coatings exhibited the highest hardness of 21.3 GPa and the lowest friction coefficient (0.11) and wear rate (8.4 × 10-8 mm3/N m). But when the TMS flow was beyond 15 sccm, the tribological properties of CrSiCN coatings in water became poor.

Elucidation of C{sub 2} and CN formation mechanisms in laser-induced plasmas through correlation analysis of carbon isotopic ratio

Energy Technology Data Exchange (ETDEWEB)

Dong, Meirong [School of Electric Power, South China University of Technology, Guangzhou, Guangdong 510640 (China); Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Chan, George C.-Y.; Mao, Xianglei; Gonzalez, Jhanis J. [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Lu, Jidong [School of Electric Power, South China University of Technology, Guangzhou, Guangdong 510640 (China); Russo, Richard E., E-mail: RERusso@lbl.gov [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States)

2014-10-01

Laser ablation molecular isotopic spectrometry (LAMIS) was recently reported for rapid isotopic analysis by measuring molecular emission from laser-induced plasmas at atmospheric pressure. With {sup 13}C-labeled benzoic acid as a model sample, this research utilized the LAMIS approach to clarify the formation mechanisms of C{sub 2} and CN molecules during laser ablation of organic materials. Because the isotopic ratios in the molecular bands could deviate from statistical distribution depending on their formation pathways, the dominant mechanism can be identified through a comparison of the experimental observed isotopic patterns in the molecular emission with the theoretical statistical pattern. For C{sub 2} formation, the experimental {sup 12}C{sup 12}C/{sup 13}C{sup 12}C ratios not only support a recombination mechanism through atomic carbon at early delay time but also indicate the presence of other operating mechanisms as the plasma evolves; it is proposed that some of the C{sub 2} molecules are released directly from the aromatic ring of the sample as molecular fragments. In contrast, the temporal profiles in the {sup 12}C/{sup 13}C ratios derived from CN emission exhibited opposite behavior with those derived from C{sub 2} emission, which unambiguously refutes mechanisms that require C{sub 2} as a precursor for CN formation; CN formation likely involves atomic carbon or species with a single carbon atom. - Highlights: • C{sub 2} and CN formation mechanisms during laser ablation of organic material studied • Some C{sub 2} molecules are directly desorbed from the organic compound. • C{sub 2} molecules are not important precursor for CN-radical formation.

Dissociative adsorption of environment-friendly insulating medium C3F7CN on Cu(111) and Al(111) surface: A theoretical evaluation

Science.gov (United States)

Zhang, Xiaoxing; Li, Yi; Chen, Dachang; Xiao, Song; Tian, Shuangshuang; Tang, Ju; Wang, Dibo

2018-03-01

SF6 is extensively used in electrical applications because of its excellent insulation and arc extinguishing performance, but its strong greenhouse effect has negative impact on the atmosphere. The excellent performance of C3F7CN in greenhouse effect, insulation ability, safety, and thermal stability has been demonstrated, indicating that this compound can replace SF6 in electrical applications. However, little information is available on the compatibility of C3F7CN with metals, such as copper and aluminum, in devices. Material compatibility between new gas mixtures and materials used in Gas Insulated Switchgear (GIS) should be investigated to determine the long-term behavior of materials. In this paper, dissociative adsorption of C3F7CN on Cu (1 1 1) and Al (1 1 1) surfaces were analyzed based on density functional theory. Adsorption energy, charge transfer, density of states, and electron density difference of interaction between C3F7CN and two metals were analyzed. It was found that the adsorption energy of C3F7CN adsorbed on Cu (1 1 1) and Al (1 1 1) is both below 0.8 eV. This value indicates that the interaction between them is not very strong. In addition, the dissociation reaction path of gas molecules after adsorption requires certain activation energy. Therefore, C3F7CN and copper or aluminum have certain compatibility and the compatibility of C3F7CN with aluminum is better than that of copper. Related results provide a reference for predicting the aging mechanism of equipment and the selection or modification of major materials for equipment.

New solar carbon abundance based on non-LTE CN molecular spectra

International Nuclear Information System (INIS)

Mount, G.H.; Linsky, J.L.

1975-01-01

A detailed non-LTE analysis of solar CN spectra strongly suggests a revised carbon abundance for the Sun. A value of log A/subc/=8.35plus-or-minus0.15 which is significantly lower than the presently accepted value of log A/subc/=8.55 is suggested. This revision may have important consequences in astrophysics

Ash content, carbon and C/N ratio in paricá in function of NPK fertilization

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CRISTIANE R. VIEIRA

2018-02-01

Full Text Available ABSTRACT Fertilization in areas of forest plantations is needed to supplement plants´ nutritional needs until harvest. An experiment was performed to check the influence of fertilization on levels of ash, carbon and C/N relation in Schizolobium amazonicum. Soil liming was performed and fertilization occurred after 15 days of incubation. S. amazonicum seedlings were produced and submitted to fertilization with N, P and K: N = 0, 40, 80 and 120 kg ha-1; P2O5 = 0, 50, 100 and 200 kg ha-1; K2O = 0, 50, 100 and 200 kg ha-1. The plants were measured after 180 days. The seedlings of 20 treatments with the highest increase in height and diameter were transplanted to the field. Soil was fertilized and limestone was spread; seedlings were distributed into randomized blocks, with six replications. After 12 months, the plants were removed to determine ash, organic carbon, C/N relation contents. The ashes were submitted to digestion to determine nutrient concentrations. Fertilization influenced the levels of ash and organic carbon and C/N relation in S. amazonicum. Results indicate that the species has a potential for energy production.

Ash content, carbon and C/N ratio in paricá in function of NPK fertilization.

Science.gov (United States)

Vieira, Cristiane R; Weber, Oscarlina L S; Scaramuzza, José Fernando

2018-01-01

Fertilization in areas of forest plantations is needed to supplement plants´ nutritional needs until harvest. An experiment was performed to check the influence of fertilization on levels of ash, carbon and C/N relation in Schizolobium amazonicum. Soil liming was performed and fertilization occurred after 15 days of incubation. S. amazonicum seedlings were produced and submitted to fertilization with N, P and K: N = 0, 40, 80 and 120 kg ha-1; P2O5 = 0, 50, 100 and 200 kg ha-1; K2O = 0, 50, 100 and 200 kg ha-1. The plants were measured after 180 days. The seedlings of 20 treatments with the highest increase in height and diameter were transplanted to the field. Soil was fertilized and limestone was spread; seedlings were distributed into randomized blocks, with six replications. After 12 months, the plants were removed to determine ash, organic carbon, C/N relation contents. The ashes were submitted to digestion to determine nutrient concentrations. Fertilization influenced the levels of ash and organic carbon and C/N relation in S. amazonicum. Results indicate that the species has a potential for energy production.

Isolation and Molecular Structure of Hexacyanoruthenate(III)

DEFF Research Database (Denmark)

Bendix, J; Steenberg, P; Søtofte, Inger

2003-01-01

The [Ru(CN)(6)](3-) ion is synthesized in aqueous solution and isolated as [Ph(4)AS](3)[Ru(CN)(6)].2H(2)O (1). Compound 1 crystallizes as orange needles in the monoclinic space group P2(1)/n with cell parameters a = 11.346(2) Angstrom, b = 23.107(5) Angstrom, c = 25.015(5) Angstrom, beta = 99...

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

Science.gov (United States)

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

2009-03-21

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

Multimodel simulations of forest harvesting effects on long‐term productivity and CN cycling in aspen forests.

Science.gov (United States)

Wang, Fugui; Mladenoff, David J; Forrester, Jodi A; Blanco, Juan A; Schelle, Robert M; Peckham, Scott D; Keough, Cindy; Lucash, Melissa S; Gower, Stith T

The effects of forest management on soil carbon (C) and nitrogen (N) dynamics vary by harvest type and species. We simulated long-term effects of bole-only harvesting of aspen (Populus tremuloides) on stand productivity and interaction of CN cycles with a multiple model approach. Five models, Biome-BGC, CENTURY, FORECAST, LANDIS-II with Century-based soil dynamics, and PnET-CN, were run for 350 yr with seven harvesting events on nutrient-poor, sandy soils representing northwestern Wisconsin, United States. Twenty CN state and flux variables were summarized from the models' outputs and statistically analyzed using ordination and variance analysis methods. The multiple models' averages suggest that bole-only harvest would not significantly affect long-term site productivity of aspen, though declines in soil organic matter and soil N were significant. Along with direct N removal by harvesting, extensive leaching after harvesting before canopy closure was another major cause of N depletion. These five models were notably different in output values of the 20 variables examined, although there were some similarities for certain variables. PnET-CN produced unique results for every variable, and CENTURY showed fewer outliers and similar temporal patterns to the mean of all models. In general, we demonstrated that when there are no site-specific data for fine-scale calibration and evaluation of a single model, the multiple model approach may be a more robust approach for long-term simulations. In addition, multimodeling may also improve the calibration and evaluation of an individual model.

Effects of C/N controlled periphyton based organic farming of freshwater prawn on water quality parameters and biotic factors

Directory of Open Access Journals (Sweden)

Md. Rezoanul Haque

2014-08-01

Full Text Available The effects of C:N controlled periphyton based organic farming of freshwater prawn on water quality parameters and biotic factors were investigated. The experiment had two treatments: T1 and T2 each with three replications. Stocking density was maintained at 20,000 juveniles ha-1. In T1, only commercially available prawn feed was applied and in T2, a locally formulated and prepared feed containing 24% crude protein with C:N ratio close to 20 was used, and maize flour and bamboo side shoots were provided for maintaining C:N ratio 20.Mean values of water quality parameters did not vary significantly (P>0.05 between treatments. Periphytic biomass in terms of dry matter, ash free dry matter (AFDM and chlorophyll a showed significant difference (P<0.05 among different sampling months. Individual harvesting weight, individual weight gain, specific growth rates, gross and net yields of prawn were significantly higher (P<0.05 in T2 than T1. Therefore, it was concluded that freshwater prawn might consume periphyton biomass in C:N controlled periphyton based organic farming practices resulted a significantly (P<0.05 higher production of freshwater prawn than traditional farming.

Structural Properties and UV-Visible Absorption Spectroscopy of Retinal-pyridyl-CN Re(I) Carbonyl Bipyridine Complex: A Theoretical Study.

Science.gov (United States)

Eng, Julien; Daniel, Chantal

2015-10-29

The structural, electronic, and optical properties of the all-trans and five cis conformers of [Re(CO)3(bpy)(ret-pyr-CN)](+) (bpy = 2,2'-bipyridine; ret-pyr-CN = pyridyl-CN-3,7-dimethyl-9-(2,6,6-trimethylcyclohex-2-n)-none-(2,4,6,8-tetraen) were studied in solvent by means of density functional theory (DFT) and time-dependent DFT. The isolated retinal-like chromophore ret-pyr-CN was investigated as well for comparison. By coordination to the complex the two lowest intraligand (IL) states localized on the retinal group are slightly red-shifted from 627 to 690 nm and from 415 to 450 nm, respectively. Several isomerization pathways are open upon irradiation of the Re(I) complex by visible light (400-450 nm), especially to two cis conformers corresponding to the isomerization of the two double bonds of the retinal-like ligand close to the pyridyl group linked to the Re(I) fragment. The metal-to-ligand charge transfer states localized either on the retinal group or on the bpy ligand should play a minor role in the isomerization process itself but could improve its efficiency via ultra-fast intersystem crossing.

Cyclometalated N-heterocyclic carbene iridium(iii) complexes with naphthalimide chromophores: a novel class of phosphorescent heteroleptic compounds.

Science.gov (United States)

Lanoë, Pierre-Henri; Chan, Jonny; Groué, Antoine; Gontard, Geoffrey; Jutand, Anny; Rager, Marie-Noelle; Armaroli, Nicola; Monti, Filippo; Barbieri, Andrea; Amouri, Hani

2018-03-06

A series of cyclometalated N-heterocyclic carbene complexes of the general formula [Ir(C^N) 2 (C^C:)] has been prepared. Two sets of compounds were designed, those where (C^C:) represents a bidentate naphthalimide-substituted imidazolylidene ligand and (C^N) = ppy (3a), F2ppy (4a), bzq (5a) and those where (C^C:) represents a naphthalimide-substituted benzimidazolylidene ligand and (C^N) = ppy (3b), F2ppy (4b), bzq (5b). The naphthalimide-imidazole and naphthalimide-benzimidazole ligands 1a,b and the related imidazolium and benzimidazolium salts 2a,b were also prepared and fully characterized. The N-heterocyclic carbene Ir(iii) complexes have been characterized by NMR spectroscopy, cyclic voltammetry and elemental analysis. Moreover, the molecular structures of one imidazolium salt and four Ir(iii) complexes were determined by single-crystal X-ray diffraction. The structures provide us with valuable information, most notably the orientation of the naphthalimide chromophore with respect to the N-heterocyclic carbene moiety. All compounds are luminescent at room temperature and in a frozen solvent at 77 K, exhibiting a broad emission band that extends beyond 700 nm. The presence of the naphthalimide moiety changes the character of the lowest excited state from 3 MLCT to 3 LC, as corroborated by DFT and TD-DFT calculations. Remarkably, replacing imidazole with a benzimidazole unit improves the quantum yields of these compounds by decreasing the k nr values which is an important feature for optimized emission performance. These studies provide valuable insights about a novel class of N-heterocyclic carbene-based luminescent complexes containing organic chromophores and affording metal complexes emitting across the red-NIR range.

Cyanide metallocenes of trivalent f-elements

International Nuclear Information System (INIS)

Maynadie, J.; Berthet, J.C.; Thuery, P.; Ephritikhine, M.

2007-01-01

Addition of N n Bu 4 CN to (C 5 Me 5 ) 2 UI(py), (C 5 Me 5 ) 2 CeI, or (C 5 Me 5 ) 2 M(OTf) (M = U, Ce) in acetonitrile led to the precipitation of the neutral mono-cyanide species [(C 5 Me 5 ) 2 M(μ-CN)] n [M = U (1), Ce (2)], which likely have an oligomeric structure, as shown by the tri-meric cyanide-bridged complex [(C 5 Me 5 ) 2 Ce(μ-CN)(CN t Bu)] 3 (3) obtained by addition of excess t BuNC into a suspension of 2 in acetonitrile. The structure of the U(III,IV) mixed valence compound [{(C 5 Me 5 ) 2 U} 2 (μ-CN){(μ-CN) 2 Na(thf)} 2 ] ∞ (4), which crystallized from a thf solution of (C 5 Me 5 ) 2 UI(py) in the presence of excess NaCN, reveals a unique example of an f-element-(μ-CN)-M interaction (M = main group or d transition metal). The anionic poly-cyanides [(C 5 Me 5 ) 2 M(CN) 3 ][N n Bu 4 ] 2 [M = U (5), Ce (6)] were synthesized by treatment of 1 and 2 with 2 equiv or an excess of N n Bu 4 CN in acetonitrile; they were also prepared in a one-pot procedure by stepwise addition of 1 equiv of KCN and 2 equiv of N n Bu 4 CN to the parent iodides in acetonitrile. The bent metallocenes 5 and 6 are unique low-valent molecular poly-cyanide compounds of an f-element that have been structurally identified, while 5 is the first fully characterized actinide(III) cyanide. Comparison of the crystal structures of 5 and 6 shows that the M-C(C 5 Me 5 ) and M-C(CN) distances are 0.02-0.03 Angstroms shorter for M = U than for M Ce, while the ionic radius of uranium(III) is 0.02 Angstroms larger than that of cerium(III). (authors)

Electrocatalytic oxidation of K₄[Fe(CN)₆] by metal-reducing bacteriumShewanella oneidensis MR-1

DEFF Research Database (Denmark)

Zheng, Zhiyong; Xiao, Yong; Wu, Ranran

2017-01-01

of an inorganic redox compound K4[Fe(CN)6]. A pair of symmetric peak in the cyclic voltammetry (CV) of K4[Fe(CN)6] were found on bare glassy carbon electrode (GCE). Surprisingly, when the GCE is coated MR-1, the anodic peak almost sustained at the same level; while the cathodic peak apparently shrunk. We...

Fabrication of nano-scaled polymer-derived SiAlCN ceramic components using focused ion beam

Science.gov (United States)

Tian, Ye; Shao, Gang; Wang, Xingwei; An, Linan

2013-09-01

Fully dense polymer-derived amorphous silicoaluminum carbonitride (SiAlCN) ceramics were synthesized from polysilazane as preceramic precursors followed by a thermal decomposition process. The nanofabrication of amorphous SiAlCN ceramics was implemented with a focused ion beam (FIB). FIB conditions such as the milling rate, the beam current, and the number of passes were considered. It was found that nanopatterns with a feature size of less than 100 nm could be fabricated onto polymer-derived ceramics (PDCs) precisely and quickly. Specific nanostructures of thin walls, nozzle, and gear have been fabricated as demonstrations, indicating that the FIB technique was a promising method to realize nanostructures on PDCs, especially for microelectromechanical system and micro/nano-sensor applications.

Fabrication of nano-scaled polymer-derived SiAlCN ceramic components using focused ion beam

International Nuclear Information System (INIS)

Tian, Ye; Wang, Xingwei; Shao, Gang; An, Linan

2013-01-01

Fully dense polymer-derived amorphous silicoaluminum carbonitride (SiAlCN) ceramics were synthesized from polysilazane as preceramic precursors followed by a thermal decomposition process. The nanofabrication of amorphous SiAlCN ceramics was implemented with a focused ion beam (FIB). FIB conditions such as the milling rate, the beam current, and the number of passes were considered. It was found that nanopatterns with a feature size of less than 100 nm could be fabricated onto polymer-derived ceramics (PDCs) precisely and quickly. Specific nanostructures of thin walls, nozzle, and gear have been fabricated as demonstrations, indicating that the FIB technique was a promising method to realize nanostructures on PDCs, especially for microelectromechanical system and micro/nano-sensor applications. (paper)

Soft X-ray emission spectroscopy used for the characterization of a-C and CN{sub x} thin films

Energy Technology Data Exchange (ETDEWEB)

Nepijko, S.A., E-mail: nepijko@uni-mainz.de [Institute of Physics, University of Mainz, Staudingerweg 7, 55128 Mainz (Germany); Chernenkaya, A. [Institute of Physics, University of Mainz, Staudingerweg 7, 55128 Mainz (Germany); Graduate School Materials Science in Mainz, Staudingerweg 9, 55128 Mainz (Germany); Medjanik, K.; Chernov, S.V. [Institute of Physics, University of Mainz, Staudingerweg 7, 55128 Mainz (Germany); Klimenkov, M. [Institute for Applied Materials, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Vlasenko, O.V. [Sumy State University, Rimsky-Korsakov str. 2, 40007 Sumy (Ukraine); Petrovskaya, S.S. [Frantsevich Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, Krzhizhanovsky str. 3, 03142 Kiev (Ukraine); Odnodvorets, L.V. [Sumy State University, Rimsky-Korsakov str. 2, 40007 Sumy (Ukraine); Zaulichnyy, Ya.V. [National Technical University of Ukraine (KPI), Pobedy Av. 37, 03056 Kiev (Ukraine); Schönhense, G. [Institute of Physics, University of Mainz, Staudingerweg 7, 55128 Mainz (Germany)

2015-02-27

We present the results of a soft X-ray emission spectroscopy study of a-C and CN{sub x} films on a Si(100) substrate. Also for the characterization of the homogeneity in depth of these films electron energy loss spectroscopy measurements with localization better than 4 nm were carried out. In case of CN{sub x} films the highest diamond-like modification occurs in the region close to the Si(100) substrate. The film density decreases with increasing distance from the substrate and becomes almost constant in range of thicknesses more than ~ 2 nm. - Highlights: • CN{sub x} and a-C film densities decrease with the increase of thickness. • Density increases with the decrease of Si(100) substrate temperature at preparation. • Highest concentration of the diamond-like structure is in the substrate vicinity. • It reduces further from the substrate and stabilizes at thickness ≥ 2 nm.

Near-infrared Spectroscopic Observations of Comet C/2013 R1 (Lovejoy) by WINERED: CN Red-system Band Emission

Energy Technology Data Exchange (ETDEWEB)

Shinnaka, Yoshiharu; Yasui, Chikako; Izumi, Natsuko [National Astronomical Observatory of Japan, 2-21-1 Osawa, Mitaka, Tokyo 181-8588 (Japan); Kawakita, Hideyo; Kondo, Sohei; Ikeda, Yuji; Kobayashi, Naoto; Hamano, Satoshi; Sameshima, Hiroaki; Fukue, Kei; Matsunaga, Noriyuki; Otsubo, Shogo; Takenaka, Keiichi; Watase, Ayaka; Kawanishi, Takafumi; Nakanishi, Kenshi; Nakaoka, Tetsuya [Laboratory of Infrared High-resolution Spectroscopy, Koyama Astronomical Observatory, Kyoto Sangyo University, Motoyama, Kamigamo, Kita-ku, Kyoto 603-8555 (Japan); Mizumoto, Misaki, E-mail: yoshiharu.shinnaka@nao.ac.jp, E-mail: kawakthd@cc.kyoto-su.ac.jp [Department of Astronomy, School of Science, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan)

2017-08-01

Although high-resolution spectra of the CN red-system band are considered useful in cometary sciences, e.g., in the study of isotopic ratios of carbon and nitrogen in cometary volatiles, there have been few reports to date due to the lack of high-resolution ( R  ≡  λ /Δ λ  > 20,000) spectrographs in the near-infrared region around ∼1 μ m. Here, we present the high-resolution emission spectrum of the CN red-system band in comet C/2013 R1 (Lovejoy), acquired by the near-infrared high-resolution spectrograph WINERED mounted on the 1.3 m Araki telescope at the Koyama Astronomical Observatory, Kyoto, Japan. We applied our fluorescence excitation models for CN, based on modern spectroscopic studies, to the observed spectrum of comet C/2013 R1 (Lovejoy) to search for CN isotopologues ({sup 13}C{sup 14}N and {sup 12}C{sup 15}N). We used a CN fluorescence excitation model involving both a “pure” fluorescence excitation model for the outer coma and a “fully collisional” fluorescence excitation model for the inner coma region. Our emission model could reproduce the observed {sup 12}C{sup 14}N red-system band of comet C/2013 R1 (Lovejoy). The derived mixing ratio between the two excitation models was 0.94(+0.02/−0.03):0.06(+0.03/−0.02), corresponding to the radius of the collision-dominant region of ∼800–1600 km from the nucleus. No isotopologues were detected. The observed spectrum is consistent, within error, with previous estimates in comets of {sup 12}C/{sup 13}C (∼90) and {sup 14}N/{sup 15}N (∼150).

Electrochemical performance of DVB-modified SiOC and SiCN polymer-derived negative electrodes for lithium-ion batteries

International Nuclear Information System (INIS)

Liu, Guanwei; Kaspar, Jan; Reinold, Lukas Mirko; Graczyk-Zajac, Magdalena; Riedel, Ralf

2013-01-01

Highlights: • Polymer-derived SiCN and SiOC ceramics are studied as anode for Li-ion batteries. • Ceramic precursors are modified in order to increase the carbon content. • Ceramic matrix stabilizes free carbon phase. • Stabilizing role is lost once the amount of carbon exceeds a threshold value. -- Abstract: Chemical modification of commercially available polyorganosilazane (HTT1800) and polyorganosiloxane (Polyramic RD-684a) with divinylbenzene (DVB) is accomplished via hydrosilylation reaction. The incorporation of DVB leads to an increase of the free carbon amount after pyrolysis within the corresponding SiCN and SiOC ceramics. The modification is carried out with lower, equal and higher stoichiometric ratios of the Si-H to C=C groups present in the Si-based polymer and DVB. FTIR results indicate a complete consumption of the Si-H bonds in the case of the stoichiometric amount of DVB and polymer RD-684a, while for HTT1800 neither the stoichiometric ratio nor DVB excess leads to a complete consumption of the Si-H groups. For both SiCN and SiOC ceramics the carbon content is found to increase with the amount of DVB. However, the most significant increase in free carbon content is registered for SiCN samples, namely of ca. 40%. The carbon content changed from 9.9 wt.% in the pure HTT1800-derived material up to 49.3 wt.% for the SiCN ceramic obtained with the highest amount of DVB addition. Accordingly, Li-ion storage and therefore charge storage capacity are simultaneously increased, for the first cycle from 136 to 574 mAh g −1 , while columbic efficiency is raised by 10% up to 60.4%

Lithium dynamics in carbon-rich polymer-derived SiCN ceramics probed by nuclear magnetic resonance

Science.gov (United States)

Baek, Seung-Ho; Reinold, Lukas Mirko; Graczyk-Zajac, Magdalena; Riedel, Ralf; Hammerath, Franziska; Büchner, Bernd; Grafe, Hans-Joachim

2014-05-01

We report 7Li, 29Si, and 13C NMR studies of two different carbon-rich SiCN ceramics SiCN-1 and SiCN-3 derived from the preceramic polymers polyphenylvinylsilylcarbodiimide and polyphenylvinylsilazane, respectively. From the spectral analysis of the three nuclei, we find that only the 13C spectrum is strongly influenced by Li insertion/extraction, suggesting that carbon phases are the major electrochemically active sites for Li storage. Temperature (T) and Larmor frequency (ωL) dependences of the 7Li linewidth and spin-lattice relaxation rates T1-1 are described by an activated law with the activation energy EA of 0.31 eV and the correlation time τ0 in the high temperature limit of 1.3 ps. The 3 / 2 power law dependence of T1-1 on ωL which deviates from the standard Bloembergen, Purcell, and Pound (BPP) model implies that the Li motion on the μs timescale is governed by continuum diffusion mechanism rather than jump diffusion. On the other hand, the rotating frame relaxation rate T1ρ-1 results suggest that the slow motion of Li on the ms timescale may be affected by complex diffusion and/or non-diffusion processes.

Cavernous malformations isolated from cranial nerves: Unexpected diagnosis?

Science.gov (United States)

Rotondo, Michele; Natale, Massimo; D'Avanzo, Raffaele; Pascale, Michela; Scuotto, Assunta

2014-11-01

Cranial nerves (CN) cavernous malformations (CMs) are lesions that are isolated from the CNs. The authors present three cases of CN CMs, for which MR was demonstrated to be critical for management, and surgical resection produced good outcomes for the patients. Surgical removal is the recommended course of action to restore or preserve neurological function and to eliminate the risk of future haemorrhage. However, the anatomical location and the complexity of nearby neural structures can make these lesions difficult to access and remove. In this study, the authors review the literature of reported cases of CN CMs to analyse the clinical and radiographic presentations, surgical approaches and neurological outcomes. A MEDLINE/Pub Med search was performed and revealed 86 cases of CN CMs. The authors report three additional cases in this study for a total of 89 cases. CMs affecting the optic nerve (CN II), oculomotor nerve (CN III), facial/vestibule-cochlear nerves (CN VII, CN VIII) have been described. The records of three patients were reviewed with respect to the lesion locations, symptoms, surgical approaches and therapeutic considerations. Clinical and radiological follow-up results are reported. Three patients (2 females, 1 male; age range 21-37 year) presented with three CN lesions. One lesion involved CN III, one lesion involved CN VII-CN VIII, and one involved CN II. The patient with the CN III lesion had a one-month history of mild right ptosis and diplopia. The patient with the CN VII-CN VIII lesion exhibited acute hearing loss and on the left and left facial paresis. The patient with the opticchiasmatic lesion presented with acute visual deterioration on the right and a left temporal field deficit in the left eye. Pterional and orbitozygomatic craniotomies were performed for the CN III lesion and the CN II lesion, and retrosigmoid craniotomy was performed for the cerebello-pontine angle lesion. All patients experienced symptom improvement after surgery. On

Synthesis and single-crystal structure of the pseudo-ternary compounds LiA[N(CN){sub 2}]{sub 2} (A = K or Rb)

Energy Technology Data Exchange (ETDEWEB)

Reckeweg, Olaf; DiSalvo, Francis J. [Cornell Univ., Ithaca, NY (United States). Baker Lab.

2016-04-01

Crystals of LiA[N(CN){sub 2}]{sub 2} were obtained from the reaction of LiCl and ACl (A = K or Rb) with Ag[N(CN){sub 2}] in water and subsequent evaporation of the filtered solution at 80 C under normal atmospheric conditions. Crystals of the title compound form thin rectangular plates that are transparent, colorless, and very fragile. Single-crystal structure analyses have shown that both compounds are isotypic and adopt the tetragonal space group I4/mcm (no. 140, Z = 4) with the cell parameters a = 701.53(12) and c = 1413.7(5) pm for LiK[N(CN){sub 2}]{sub 2} and a = 730.34(10) and c = 1414.4(4) pm for LiRb[N(CN){sub 2}]{sub 2}. The crystal structure is described and compared to that of the pseudo-binary alkali metal dicyanamides.

Strong quadrupole interaction in electron paramagnetic resonance. Study of the indium hexacyanide (III) in KCl irradiated with electrons

International Nuclear Information System (INIS)

Vugman, N.V.

1973-08-01

The radiation effects in ]Ir III (CN) 6 ] 3- diamagnetic complexe inserted in the KCl lattice and irradiated with electrons of 2MeV by electron spin resonance (ESR) are analysed. Formulas for g and A tensors in the ligand field approximation, are derivated to calculate non coupling electron density in the metal. The X polarization field of inner shells is positive, indicating a 6s function mixture in the non coupling electron molecular orbital. The observed hyperfine structure is assigned to 4 equivalent nitrogen and one non equivalent nitrogen. This hypothesis is verified by experience of isotope substitution with 15 N. The s and p spin density in ligands are calculated and discussed in terms of molecular obitals. The effects of strong quadrupole interaction into the EPR spectra of ]Ir II (CN) 5 ] 3- complex are analysed by MAGNSPEC computer program to diagonalize the Spin Hamiltonian of the system. Empiric rules for EPR espectrum interpretation with strong quadrupole interaction. A review of EPR technique and a review of main concepts of crystal-field and ligand field theories, are also presented. (M.C.K.) [pt

Electrochemical studies on Li /K ion exchange behaviour in K4Fe(CN)

Indian Academy of Sciences (India)

based,24 sol-gel,17–21 and solid-state16 meth- ods. There are a .... Double potential step chronoamper- ometry was ... removal of moisture as well as water of crystallisa- tion and the .... active material, K4Fe(CN)6, carbon black and graphite.

Particle Aggregation During Fe(III) Bioreduction in Nontronite

Science.gov (United States)

Jaisi, D. P.; Dong, H.; Hi, Z.; Kim, J.

2005-12-01

This study was performed to evaluate the rate and mechanism of particle aggregation during bacterial Fe (III) reduction in different size fractions of nontronite and to investigate the role of different factors contributing to particle aggregation. To achieve this goal, microbial Fe(III) reduction experiments were performed with lactate as an electron donor, Fe(III) in nontronite as an electron acceptor, and AQDS as an electron shuttle in bicarbonate buffer using Shewanella putrefaceins CN32. These experiments were performed with and without Na- pyrophosphate as a dispersant in four size fractions of nontronite (0.12-0.22, 0.41-0.69, 0.73-0.96 and 1.42-1.8 mm). The rate of nontronite aggregation during the Fe(III) bioreduction was measured by analyzing particle size distribution using photon correlation spectroscopy (PCS) and SEM images analysis. Similarly, the changes in particle morphology during particle aggregation were determined by analyses of SEM images. Changes in particle surface charge were measured with electrophoretic mobility analyzer. The protein and carbohydrate fraction of EPS produced by cells during Fe(III) bioreduction was measured using Bradford and phenol-sulfuric acid extraction method, respectively. In the presence of the dispersant, the extent of Fe(III) bioreduction was 11.5-12.2% within the first 56 hours of the experiment. There was no measurable particle aggregation in control experiments. The PCS measurements showed that the increase in the effective diameter (95% percentile) was by a factor of 3.1 and 1.9 for particle size of 0.12-0.22 mm and 1.42-1.80 mm, respectively. The SEM image analyses also gave the similar magnitude of increase in particle size. In the absence of the dispersant, the extent of Fe(III) bioreduction was 13.4-14.5% in 56 hours of the experiment. The rate of aggregation was higher than that in the presence of the dispersant. The increase in the effective diameter (95% percentile) was by a factor of 13.6 and 4.1 for

Organometallic Gold(III) Complexes Similar to Tetrahydroisoquinoline Induce ER-Stress-Mediated Apoptosis and Pro-Death Autophagy in A549 Cancer Cells.

Science.gov (United States)

Huang, Ke-Bin; Wang, Feng-Yang; Tang, Xiao-Ming; Feng, Hai-Wen; Chen, Zhen-Feng; Liu, Yan-Cheng; Liu, You-Nian; Liang, Hong

2018-04-26

Agents inducing both apoptosis and autophagic death can be effective chemotherapeutic drugs. In our present work, we synthesized two organometallic gold(III) complexes harboring C^N ligands that structurally resemble tetrahydroisoquinoline (THIQ): Cyc-Au-1 (AuL 1 Cl 2 , L 1 = 3,4-dimethoxyphenethylamine) and Cyc-Au-2 (AuL 2 Cl 2 , L 2 = methylenedioxyphenethylamine). In screening their in vitro activity, we found both gold complexes exhibited lower toxicity, lower resistance factors, and better anticancer activity than those of cisplatin. The organometallic gold(III) complexes accumulate in mitochondria and induce elevated ROS and an ER stress response through mitochondrial dysfunction. These effects ultimately result in simultaneous apoptosis and autophagy. Importantly, compared to cisplatin, Cyc-Au-2 exhibits lower toxicity and better anticancer activity in a murine tumor model. To the best of our knowledge, Cyc-Au-2 is the first organometallic Au(III) compound that induces apoptosis and autophagic death. On the basis of our results, we believe Cyc-Au-2 to be a promising anticancer agent or lead compound for further anticancer drug development.

The Use of Asymptotic Functions for Determining Empirical Values of CN Parameter in Selected Catchments of Variable Land Cover

Science.gov (United States)

Wałęga, Andrzej; Młyński, Dariusz; Wachulec, Katarzyna

2017-12-01

The aim of the study was to assess the applicability of asymptotic functions for determining the value of CN parameter as a function of precipitation depth in mountain and upland catchments. The analyses were carried out in two catchments: the Rudawa, left tributary of the Vistula, and the Kamienica, right tributary of the Dunajec. The input material included data on precipitation and flows for a multi-year period 1980-2012, obtained from IMGW PIB in Warsaw. Two models were used to determine empirical values of CNobs parameter as a function of precipitation depth: standard Hawkins model and 2-CN model allowing for a heterogeneous nature of a catchment area. The study analyses confirmed that asymptotic functions properly described P-CNobs relationship for the entire range of precipitation variability. In the case of high rainfalls, CNobs remained above or below the commonly accepted average antecedent moisture conditions AMCII. The study calculations indicated that the runoff amount calculated according to the original SCS-CN method might be underestimated, and this could adversely affect the values of design flows required for the design of hydraulic engineering projects. In catchments with heterogeneous land cover, the results of CNobs were more accurate when 2-CN model was used instead of the standard Hawkins model. 2-CN model is more precise in accounting for differences in runoff formation depending on retention capacity of the substrate. It was also demonstrated that the commonly accepted initial abstraction coefficient λ = 0.20 yielded too big initial loss of precipitation in the analyzed catchments and, therefore, the computed direct runoff was underestimated. The best results were obtained for λ = 0.05.

Magnetic field effects on electric behavior of [Fe(CN6]3− at bare and membrane-coated electrodes

Directory of Open Access Journals (Sweden)

Govindachetty Saravanan, Katsuhiko Fujio and Sumio Ozeki

2008-01-01

Full Text Available The cyclic voltammetric behavior of [Fe(CN6]3− was investigated under homogeneous magnetic fields perpendicular to the electrode surface in order to determine the effects of magnetic fields on the distribution of an Fe2+/Fe3+ redox couple. The cathodic current was enhanced much more than the anodic current by a homogeneous magnetic field, suggesting that the concentration gradient of paramagnetic [Fe(CN6]3− and diamagnetic [Fe(CN6]4− formed at an electrode surface may also contribute to the asymmetric current. The apparent diffusion coefficient of the redox couple increased by over 30% in both cathodic and anodic processes upon applying a magnetic field. For a gold electrode coated with dioctadecyldimethylammonium, the application of a magnetic field perpendicular to the surface increased the peak-to-peak separation, and enhanced the asymmetric current. It is inferred that the application of a magnetic field promotes the electron-tunneling process by tilting chain molecules in the barrier membrane.

Temperaturedependent After-Effects of the Cobalt-57-Iron-57 Electron-Capture Reaction in Cd3[57Co(CN)6]2,12H2O

DEFF Research Database (Denmark)

Fenger, Jes; Olsen, Jørgen

1974-01-01

The Mössbauer emission spectrum of Cd3[57Co(CN)6]2,12H2O was measured at temperatures between 78 and 323 K. Above 200 K the spectra can be resolved into two doublets; one is ascribed to 57Fe(CN)63– and one to 57Fe(CN)52–; it is suggested that the pentacyanide is formed by a Coulomb explosion...... following an Auger process associated with the 57Co(EC)57Fe-decay. Below 200 K a third species is detected; it may be Fe2+ formed by cyanide linkage isomerism. Measurements of the total intensity of the spectrum and the relative intensities of the individual doublets as a function of temperature permit...... in principle a determination of the f-factors for the species formed. It is estimated that the 57Fe(CN)52– has a formal Debye temperature of 170 K; at room temperature it is detected with a probability of only 50% of that of the 57Fe(CN)63–....

cn.FARMS: a latent variable model to detect copy number variations in microarray data with a low false discovery rate.

Science.gov (United States)

Clevert, Djork-Arné; Mitterecker, Andreas; Mayr, Andreas; Klambauer, Günter; Tuefferd, Marianne; De Bondt, An; Talloen, Willem; Göhlmann, Hinrich; Hochreiter, Sepp

2011-07-01

Cost-effective oligonucleotide genotyping arrays like the Affymetrix SNP 6.0 are still the predominant technique to measure DNA copy number variations (CNVs). However, CNV detection methods for microarrays overestimate both the number and the size of CNV regions and, consequently, suffer from a high false discovery rate (FDR). A high FDR means that many CNVs are wrongly detected and therefore not associated with a disease in a clinical study, though correction for multiple testing takes them into account and thereby decreases the study's discovery power. For controlling the FDR, we propose a probabilistic latent variable model, 'cn.FARMS', which is optimized by a Bayesian maximum a posteriori approach. cn.FARMS controls the FDR through the information gain of the posterior over the prior. The prior represents the null hypothesis of copy number 2 for all samples from which the posterior can only deviate by strong and consistent signals in the data. On HapMap data, cn.FARMS clearly outperformed the two most prevalent methods with respect to sensitivity and FDR. The software cn.FARMS is publicly available as a R package at http://www.bioinf.jku.at/software/cnfarms/cnfarms.html.

Heat production in growing pigs calculated according to the RQ and CN methods

DEFF Research Database (Denmark)

Christensen, K; Chwalibog, André; Henckel, S

1988-01-01

1. Heat production, calculated according to the respiratory quotient methods, HE(RQ), and the carbon nitrogen balance method, HE(CN), was compared using the results from a total of 326 balance trials with 56 castrated male pigs fed different dietary composition and variable feed levels during...

Isothiocyanato complexes of Gd(III), Tb(III), Dy(III) and Ho(III) with 2-(2'-pyridyl)benzimidazole

Energy Technology Data Exchange (ETDEWEB)

Mishra, A; Singh, V K

1982-01-01

Six-coordinated complexes of the type (Ln(PyBzH)/sub 2/NCS.H/sub 2/O) (NCS)/sub 2/.nH/sub 2/O/mC/sub 2/H/sub 5/OH (Ln = Gd(III), Tb(III), Dy(III) and Ho(III), n=1-2; m=1) have been prepared from Ln(NCS)/sub 6//sup 3 -/. The room temperature magnetic moment values confirm the terpositive state of the lanthanide ions. Infrared spectra suggest the N-coordination of thiocyanate group. Electronic spectral studies of Tb(III), Dy(III) and Ho(III) complexes have been made in terms of LSJ term energies. 13 refs.

Raster-based derivation of a flood runoff susceptibility map using the revised runoff curve number (CN) for the Kuantan watershed, Malaysia

DEFF Research Database (Denmark)

Akbari, Abolghasem; Samah, Azizan Abu; Daryabor, Farshid

2016-01-01

This study aims to develop a methodology for generating a flood runoff susceptibility (FRS) map using a revised curve number (CN) method. The study area is in the Kuantan watershed (KW), Malaysia, which was seriously affected by floods in December 2013 and December 2014. A revised runoff CN map w......, the finding of this research provides a road map for government agencies to effectively implement flood mitigation projects in the study area.......This study aims to develop a methodology for generating a flood runoff susceptibility (FRS) map using a revised curve number (CN) method. The study area is in the Kuantan watershed (KW), Malaysia, which was seriously affected by floods in December 2013 and December 2014. A revised runoff CN map....... Approximately 5% of the study area was identified as a very high-risk zone and 13% as high-risk zone. However, the spatial extent of a high-risk zone in the downstream end and lowland areas of the KW could be considered to be the main cause of flood damage in recent years. From practical point of view...

TEGS-CN: A Statistical Method for Pathway Analysis of Genome-wide Copy Number Profile.

Science.gov (United States)

Huang, Yen-Tsung; Hsu, Thomas; Christiani, David C

2014-01-01

The effects of copy number alterations make up a significant part of the tumor genome profile, but pathway analyses of these alterations are still not well established. We proposed a novel method to analyze multiple copy numbers of genes within a pathway, termed Test for the Effect of a Gene Set with Copy Number data (TEGS-CN). TEGS-CN was adapted from TEGS, a method that we previously developed for gene expression data using a variance component score test. With additional development, we extend the method to analyze DNA copy number data, accounting for different sizes and thus various numbers of copy number probes in genes. The test statistic follows a mixture of X (2) distributions that can be obtained using permutation with scaled X (2) approximation. We conducted simulation studies to evaluate the size and the power of TEGS-CN and to compare its performance with TEGS. We analyzed a genome-wide copy number data from 264 patients of non-small-cell lung cancer. With the Molecular Signatures Database (MSigDB) pathway database, the genome-wide copy number data can be classified into 1814 biological pathways or gene sets. We investigated associations of the copy number profile of the 1814 gene sets with pack-years of cigarette smoking. Our analysis revealed five pathways with significant P values after Bonferroni adjustment (number data, and causal mechanisms of the five pathways require further study.

Numerical analysis of heat treatment of TiCN coated AA7075 aluminium alloy

Science.gov (United States)

Srinath, M. K.; Prasad, M. S. Ganesha

2018-04-01

The Numerical analysis of heat treatments of TiCN coated AA7075 aluminium alloys is presented in this paper. The Convection-Diffusion-Reaction (CDR) equation with solutions in the Streamlined-Upward Petrov-Galerkin (SUPG) method for different parameters is provided for the understanding of the process. An experimental process to improve the surface properties of AA-7075 aluminium alloy was attempted through the coatings of TiCN and subsequent heat treatments. From the experimental process, optimized temperature and time was obtained which gave the maximum surface hardness and corrosion resistance. The paper gives an understanding and use of the CDR equation for application of the process. Expression to determine convection, diffusion and reaction parameters are provided which is used to obtain the overall expression of the heat treatment process. With the substitution of the optimized temperature and time, the governing equation may be obtained. Additionally, the total energy consumed during the heat treatment process is also developed to give a mathematical formulation of the energy consumed.

Very high laser-damage threshold of polymer-derived Si(B)CN-carbon nanotube composite coatings.

Science.gov (United States)

Bhandavat, R; Feldman, A; Cromer, C; Lehman, J; Singh, G

2013-04-10

We study the laser irradiance behavior and resulting structural evolution of polymer-derived silicon-boron-carbonitride (Si(B)CN) functionalized multiwall carbon nanotube (MWCNT) composite spray coatings on copper substrate. We report a damage threshold value of 15 kWcm(-2) and an optical absorbance of 0.97 after irradiation. This is an order of magnitude improvement over MWCNT (1.4 kWcm(-2), 0.76), SWCNT (0.8 kWcm(-2), 0.65) and carbon paint (0.1 kWcm(-2), 0.87) coatings previously tested at 10.6 μm (2.5 kW CO2 laser) exposure. Electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy suggests partial oxidation of Si(B)CN forming a stable protective SiO2 phase upon irradiation.

Sheet-like of Mo –Sm assembly containing [Mo (CN)8 ] and Sm ions ...

Indian Academy of Sciences (India)

Administrator

421–427. © Indian Academy of Sciences. 421 ... Department of Chemistry, Nankai University, Tianjin, 300071, PR China e-mail: ... [Mo(CN)8]3– building blocks, this paper details the ..... 20601014), and National Basic Research Program of.

μ-Peroxido-bis­[acetonitrile­bis­(ethyl­enediamine)­cobalt(III)] tetrakis(per­chlorate)

Science.gov (United States)

Regeta, Khrystyna O.; Odarich, Iryna; Pavlova, Svetlana V.; Kalibabchuk, Valentina A.; Haukka, Matti

2010-01-01

The title compound, [Co2(O2)(CH3CN)2(C2H8N2)4](ClO4)4, consists of centrosymmetric binuclear cations and perchlorate anions. Two CoIII atoms, which have a slightly distorted octa­hedral coordination, are connected through a peroxido bridge; the O—O distance is 1.476 (3) Å. Both acetonitrile ligands are situated in a trans position with respect to the O—O bridge. In the crystal, the complex cations are connected by N—H⋯O hydrogen bonds between ethyl­endiamine NH groups and O atoms from the perchlorate anions and peroxide O atoms. PMID:21589305

Encapsulation of ferro- and ferricyanide complexes inside ZSM-5 zeolite synthesized from rice straw: Implications for synthesis of Prussian blue pigment

International Nuclear Information System (INIS)

Ali, Ibraheem O.; Salama, Tarek M.; Thabet, Mohamed S.; El-Nasser, Karam S.; Hassan, Ali M.

2013-01-01

Encapsulation of [Fe(CN) 6 ] 4− and [Fe(CN) 6 ] 3− complexes in the intracrystalline pores of ZSM-5 zeolite, Fe II L/Z and Fe III L/Z respectively, by the zeolite synthesis method was reported. The modified zeolites were characterized by powder XRD, FT-IR and UV–vis spectroscopy. The nitrogen adsorption isotherms allow for the evaluation of pore structure of the complex-modified zeolites, whereas the thermal analysis (TGA/DTA) measurements provide insight into the decomposition products of the immobilized complexes. The modified zeolites exhibited smaller pore volumes and surface areas as compared with those of unpromoted ZSM-5, suggesting the inclusion of iron cyanides inside the interconnecting channels of ZSM-5. While the ferricyanide complex enhanced the formation of highly crystalline zeolite, the ferrocyanide one resulted in a lesser effect. The electronic spectra of the colloidal species developed when Fe III L/Z brought in contact with an aqueous solution of [Fe(CN) 6 ] 3− exhibit absorptions attributed to CN − → iron charge-transfer. New bands at 294 and 319 nm due to d–d transitions of Fe III tetrahedral monomeric moieties were emitted concurrently under successive adsorption of [Fe(CN) 6 ] aq 3− over Fe III L/Z, along with a broad band at 555 nm assigned to polymeric [Fe II –C–N–Fe III ] of Prussian blue (PB). The FT-IR spectra of Fe III/II L/Z devoted to the adsorption of an aqueous solution of [Fe(CN) 6 ] 3− showed a band at 2092 cm −1 assigned to the C–N stretch in the Fe II –CN–Fe III linkages. The vibrations attributable to Fe–O–Si bonding along with hydrocarbon and nitroprusside appeared only in the spectrum of Fe III L/Z, thus was found to be strong evidence for the mutual interaction between [Fe(CN) 6 ] 3− and the latter sample. - Highlights: • We synthesized ferrous and ferric cyanide complexes inside ZSM-5 zeolite. • The decomposition of the encapsulated complexes occurred at high temperatures. �

Molecular and electronic structure of actinide hexa-cyanoferrates; Structure moleculaire et electronique des hexacyanoferrates d'actinides

Energy Technology Data Exchange (ETDEWEB)

Bonhoure, I

2001-07-01

The goal of this work is to improve our knowledge on the actinide-ligand bond properties. To this end, the hexacyanoferrate entities have been used as pre-organized ligand. We have synthesized, using mild chemistry, the following series of complexes: An{sup IV}[Fe{sup II}(CN){sub 6}].xH{sub 2}O (An = Th, U, Np, Pu); Am{sup III}[Fe{sup III}(CN){sub 6}].xH{sub 2}O; Pu {sup III}[Co{sup III}(CN){sub 6}].xH{sub 2}O and K(H?)An{sup III}[Fe{sup II}(CN){sub 6}].xH{sub 2}O (An = Pu, Am). The metal oxidation states have been obtained thanks to the {nu}{sub CN}, stretching vibration and to the actinide L{sub III} absorption edge studies. As Prussian Blue, the An{sup IV}[Fe{sup II}(CN){sub 6}].xH{sub 2}O (An = Np, Pu) are class II of Robin and Day compounds. X-ray Diffraction has shown besides that these complexes crystallize in the P6{sub 3}/m space group, as the isomorphic LaKFe(CN){sub 6}.4H{sub 2}O complex used as structural model. The EXAFS oscillations at the iron K edge and at the An L{sub III} edge allowed to determine the An-N, An-O, Fe-C and Fe-N distances. The display of the multiple scattering paths for both edges explains the actinide contribution absence at the iron edge, whereas the iron signature is present at the actinide edge. We have shown that the actinide coordination sphere in actinides hexa-cyanoferrates is comparable to the one of lanthanides. However, the actinides typical behavior towards the lanthanides is brought to the fore by the An{sup IV} versus Ln{sup III} ions presence in this family of complexes. Contrarily to the 4f electrons, the 5f electrons influence the electronic properties of the compounds of this family. However, the gap between the An-N and Ln-N distances towards the corresponding metals ionic radii do not show any covalence bond evolution between the actinide and lanthanide series. (author)

Iodide Ion Pairing with Highly Charged Ruthenium Polypyridyl Cations in CH3CN.

Science.gov (United States)

Swords, Wesley B; Li, Guocan; Meyer, Gerald J

2015-05-04

A series of three highly charged cationic ruthenium(II) polypyridyl complexes of the general formula [Ru(deeb)3-x(tmam)x](PF6)2x+2, where deeb is 4,4'-diethyl ester-2,2'-bipyridine and tmam is 4,4'-bis[(trimethylamino)methyl]-2,2'-bipyridine, were synthesized and characterized and are referred to as 1, 2, or 3 based on the number of tmam ligands. Crystals suitable for X-ray crystallography were obtained for the homoleptic complex 3, which was found to possess D3 symmetry over the entire ruthenium complex. The complexes displayed visible absorption spectra typical of metal-to-ligand charge-transfer (MLCT) transitions. In acetonitrile, quasi-reversible waves were assigned to Ru(III/II) electron transfer, with formal reduction potentials that shifted negative as the number of tmam ligands was increased. Room temperature photoluminescence was observed in acetonitrile with quantum yields of ϕ ∼ 0.1 and lifetimes of τ ∼ 2 μs. The spectroscopic and electrochemical data were most consistent with excited-state localization on the deeb ligand for 1 and 2 and on the tmam ligand for 3. The addition of tetrabutylammonium iodide to the complexes dissolved in a CH3CN solution led to changes in the UV-vis absorption spectra consistent with ion pairing. A Benesi-Hildebrand-type analysis of these data revealed equilibrium constants that increased with the cationic charge 1 10(8) s(-1). The possible relevance of this work to solar energy conversion and dye-sensitized solar cells is discussed.

Reply to comment by Fred L. Ogden et al. on "Beyond the SCS-CN method: A theoretical framework for spatially lumped rainfall-runoff response"

Science.gov (United States)

Bartlett, M. S.; Parolari, A. J.; McDonnell, J. J.; Porporato, A.

2017-07-01

Though Ogden et al. list several shortcomings of the original SCS-CN method, fit for purpose is a key consideration in hydrological modelling, as shown by the adoption of SCS-CN method in many design standards. The theoretical framework of Bartlett et al. [2016a] reveals a family of semidistributed models, of which the SCS-CN method is just one member. Other members include event-based versions of the Variable Infiltration Capacity (VIC) model and TOPMODEL. This general model allows us to move beyond the limitations of the original SCS-CN method under different rainfall-runoff mechanisms and distributions for soil and rainfall variability. Future research should link this general model approach to different hydrogeographic settings, in line with the call for action proposed by Ogden et al.

A structural phase transition coupled to the Fe{sup 3+} spin-state crossover in anhydrous RbMn[Fe(CN){sub 6}

Energy Technology Data Exchange (ETDEWEB)

Rykov, A. I., E-mail: rykov3@yahoo.com; Wang, J., E-mail: wangjh@dicp.ac.cn; Zhang, T. [Chinese Academy of Sciences, Moessbauer Effect Data Center, Dalian Institute of Chemical Physics (China); Nomura, K. [University of Tokyo, Graduate School of Engineering (Japan)

2013-04-15

Linkage isomerism is the coexistence of iso-compositional molecules or solids differing by connectivity of the metal to a ligand. In a crystalline solid state, the rotation is possible for asymmetric ligands, e.g., for cyanide ligand. Here we report on our observation of a phase transition in anhydrous RbMn[Fe(CN){sub 6}] (nearly stoichiometric) and on the effect of linkage isomerism ensuing our interpretation of the results of Moessbauer study in which we observe the iron spin state crossover among two phases involved into this transition. The anhydrous RbMn[Fe(CN){sub 6}] can be prepared via prolonged thermal treatment (1 week at at 80 Degree-Sign C) of the as-synthesized hydrated RbMn[Fe(CN){sub 6}]{center_dot}H{sub 2}O. The latter compound famous for its charge-transfer phase transition is a precursor in our case. As the temperature is raising above 80 Degree-Sign C (remaining below 100 Degree-Sign C) we observe RbMn[Fe(CN){sub 6}] that inherited its F-43 m symmetry from RbMn[Fe(CN){sub 6}]{center_dot}H{sub 2}O transforming to a phase of the Fm-3 m symmetry. In the latter, more than half of Fe{sup 3 + } ions are in high-spin state. We suggest a plausible way to explain the spin-crossover that is to allow the linkage isomerism by rotation of the cyanide ligands.

Complexation of trivalent actinides and lanthanides with hydrophilic N-donor ligands for Am(III)/Cm(III) and An(III)/Ln(III) separation; Komplexierung von trivalenten Actiniden und Lanthaniden mit hydrophilen N-Donorliganden zur Am(III)/Cm(III)- bzw. An(III)/Ln(III)-Trennung

Energy Technology Data Exchange (ETDEWEB)

Wagner, Christoph

2017-07-24

The implementation of actinide recycling processes is considered in several countries, aiming at the reduction of long-term radiotoxicity and heat load of used nuclear fuel. This requires the separation of the actinides from the fission and corrosion products. The separation of the trivalent actinides (An(III)) Am(III) and Cm(III), however, is complicated by the presence of the chemically similar fission lanthanides (Ln(III)). Hydrophilic N-donor ligands are employed as An(III) or Am(III) selective complexing agents in solvent extraction to strip An(III) or Am(III) from an organic phase loaded with An(III) and Ln(III). Though they exhibit excellent selectivity, the complexation chemistry of these ligands and the complexes formed during solvent extraction are not sufficiently characterized. In the present thesis the complexation of An(III) and Ln(III) with hydrophilic N-donor ligands is studied by time resolved laser fluorescence spectroscopy (TRLFS), UV/Vis, vibronic sideband spectroscopy and solvent extraction. TRLFS studies on the complexation of Cm(III) and Eu(III) with the Am(III) selective complexing agent SO{sub 3}-Ph-BTBP (tetrasodium 3,3{sup '},3'',3{sup '''}-([2,2{sup '}-bipyridine]-6,6{sup '}-diylbis(1,2,4-triazine-3,5,6-triyl)) tetrabenzenesulfonate) revealed the formation of [M(SO{sub 3}-Ph-BTBP){sub n}]{sup (4n-3)-} complexes (M = Cm(III), Eu(III); n = 1, 2). The conditional stability constants were determined in different media yielding two orders of magnitude larger β{sub 2}-values for the Cm(III) complexes, independently from the applied medium. A strong impact of ionic strength on the stability and stoichiometry of the formed complexes was identified, resulting from the stabilization of the pentaanionic [M(SO{sub 3}-Ph-BTBP){sub 2}]{sup 5-} complex with increasing ionic strength. Thermodynamic studies of Cm(III)-SO{sub 3}-Ph-BTBP complexation showed that the proton concentration of the applied medium impacts

Static Recrystallization Behavior of Z12CN13 Martensite Stainless Steel

Science.gov (United States)

Luo, Min; Zhou, Bing; Li, Rong-bin; Xu, Chun; Guo, Yan-hui

2017-09-01

In order to increase the hot workability and provide proper hot forming parameters of forging Z12CN13 martensite stainless steel for the simulation and production, the static recrystallization behavior has been studied by double-pass hot compression tests. The effects of deformation temperature, strain rate and inter-pass time on the static recrystallization fraction by the 2% offset method are extensively studied. The results indicate that increasing the inter-pass time and the deformation temperature as well as strain rate appropriately can increase the fraction of static recrystallization. At the temperature of 1050-1150 °C, inter-pass time of 30-100 s and strain rate of 0.1-5 s-1, the static recrystallization behavior is obvious. In addition, the kinetics of static recrystallization behavior of Z12CN13 steel has been established and the activation energy of static recrystallization is 173.030 kJ/mol. The substructure and precipitates have been studied by TEM. The results reveal that the nucleation mode is bulging at grain boundary. Undissolved precipitates such as MoNi3 and Fe3C have a retarding effect on the recrystallization kinetics. The effect is weaker than the accelerating effect of deformation temperature.

Radiological Protection Service of CN Asco; Servicio de ProteccionRadiologica de C. N. Asco

Energy Technology Data Exchange (ETDEWEB)

NONE

2015-07-01

Briefly explains the structure of Radiation Protection Service (SPR) of CN Asco to address these performances, as well as a short description of the main activities that have been reinforced or have been incorporated into the routine activities of the SPR. (Author)

Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S{sub 2}CN(iPr)CH{sub 2}CH{sub 2}OH]{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Tan, Yee Seng; Halim, Siti Nadiah Abdul [Malaya Univ., Kuala Lumpur (Malaysia). Dept. of Chemistry; Tiekink, Edward R.T. [Malaya Univ., Kuala Lumpur (Malaysia). Dept. of Chemistry; Sunway Univ., Bandar Sunway (Malaysia). Centre for Chemical Crystallography

2016-04-01

Crystallization of Cd[S{sub 2}CN(iPr)CH{sub 2}CH{sub 2}OH]{sub 2} from ethanol yields the coordination polymer [{Cd[S_2CN(iPr)CH_2CH_2OH]_2}.EtOH]{sub ∞} (1) within 3 h. When the solution is allowed to stand for another hour, the needles begin to dissolve and prisms emerge of the supramolecular isomer (SI), binuclear {Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 2}.2EtOH (2). These have been fully characterized spectroscopically and by X-ray crystallography. Polymeric 1 has 2-fold symmetry and features dithiocarbamate ligands coordinating two octahedral Cd atoms in a μ{sub 2}κ{sup 2}-tridentate mode. Binuclear 2 is centrosymmetric with two ligands being μ{sub 2}κ{sup 2}-tridentate as for 1 but the other two being κ{sup 2}-chelating leading to square pyramidal geometries. The conversion of the kinetic crystallization product, 1, to thermodynamic 2 is irreversible but transformations mediated by recrystallization (ethanol and acetonitrile) to related literature SI species, namely coordination polymer [{Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 3}.MeCN]{sub ∞} and binuclear {Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 2}.2H{sub 2}O.2MeCN, are demonstrated, some of which are reversible. Three other crystallization outcomes are described whereby crystal structures were obtained for the 1:2 co-crystal {Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 2}:2[3-(propan-2-yl)-1,3-oxazolidine-2-thione] (3), the salt co-crystal [iPrNH{sub 2}(CH{sub 2}CH{sub 2}OH)]{sub 4}[SO{sub 4}]{sub 2}{Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 2} (4) and the salt [iPrNH{sub 2}(CH{sub 2}CH{sub 2}OH)]{Cd[S_2CN(iPr)CH_2CH_2OH]_3} (5). These arise as a result of decomposition/oxidation of the dithiocarbamate ligands. In each of 3 and 4 the binuclear {Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 2} SI, as in 2, is observed strongly suggesting a thermodynamic preference for this form.

Structure and property relationships of amorphous CN sub x a joint experimental and theoretical study

CERN Document Server

Santos, M C D

2000-01-01

Amorphous CN sub x and CN sub x :H have been prepared by the ion beam assisted deposition technique. Samples were characterized through X-ray and UV photoemission, IR absorption and Raman spectroscopies. These spectra have been interpreted with the aid of quantum chemical calculations based upon the Hartree-Fock theory on several molecular models. The understanding of the electronic and structural properties of the amorphous alloy as a function of nitrogen content could help in the task of synthesizing the metastable silicon-nitride like-phase beta-C sub 3 N sub 4 , a solid which has been predicted to be as hard as diamond. The physical picture emerging from the present study helps to clarify the difficulties in obtaining the crystalline phase of the material, suggesting new experimental directions for syntheses.

Complexes of 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III)

International Nuclear Information System (INIS)

Ferenc, W.; Bernat, M; Gluchowska, H.W.; Sarzynski, J.

2010-01-01

The complexes of 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III) have been synthesized as polycrystalline hydrated solids, and characterized by elemental analysis, spectroscopy, magnetic studies and also by X-ray diffraction and thermogravimetric measurements. The analysed complexes have the following colours: violet for Nd(III), white for Gd(III) and cream for Ho(III) compounds. The carboxylate groups bind as bidentate chelating (Ho) or bridging ligands (Nd, Gd). On heating to 1173K in air the complexes decompose in several steps. At first, they dehydrate in one step to form anhydrous salts, that next decompose to the oxides of respective metals. The gaseous products of their thermal decomposition in nitrogen were also determined and the magnetic susceptibilities were measured over the temperature range of 76-303K and the magnetic moments were calculated. The results show that 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III) are high-spin complexes with weak ligand fields. The solubility value in water at 293K for analysed 4-chlorophenoxyacetates is in the order of 10 -4 mol/dm 3 . (author)

Evidence of amino acid precursors: C-N bond coupling in simulated interstellar CO2/NH3 ices

Science.gov (United States)

Esmaili, Sasan

2015-08-01

Low energy secondary electrons are abundantly produced in astrophysical or planetary ices by the numerous ionizing radiation fields typically encountered in space environments and may thus play a role in the radiation processing of such ices [1]. One approach to determine their chemical effect is to irradiate nanometer thick molecular solids of simple molecular constituents, with energy selected electron beams and to monitor changes in film chemistry with the surface analytical techniques [2].Of particular interest is the formation of HCN, which is a signature of dense gases in interstellar clouds, and is ubiquitous in the ISM. Moreover, the chemistry of HCN radiolysis products such as CN- may be essential to understand of the formation of amino acids [3] and purine DNA bases. Here we present new results on the irradiation of multilayer films of CO2 and NH3 with 70 eV electrons, leading to CN bond formations. The electron stimulated desorption (ESD) yields of cations and anions are recorded as a function of electron fluence. The prompt desorption of cationic reaction/scattering products [4], is observed at low fluence (~4x1013 electrons/cm2). Detected ions include C2+, C2O2+, C2O+, CO3+, C2O3+ or CO4+ from pure CO2, and N+, NH+, NH2+, NH3+, NH4+, N2+, N2H+ from pure NH3, and NO+, NOH+ from CO2/NH3 mixtures. Most saliently, increasing signals of negative ion products desorbing during prolonged irradiation of CO2/NH3 films included C2-, C2H-, C2H2-, as well as CN-, HCN- and H2CN-. The identification of particular product ions was accomplished by using 13CO2 and 15NH3 isotopes. The chemistry induced by electrons in pure films of CO2 and NH3 and mixtures with composition ratios (3:1), (1:1), and (1:3), was also studied by X-ray photoelectron spectroscopy (XPS). Irradiation of CO2/NH3 mixed films at 22 K produces species containing the following bonds/functional groups identified by XPS: C=O, O-H, C-C, C-O, C=N and N=O. (This work has been funded by NSERC).

Elimination Reactions of (E)-2,4,6-Trinitrobenzaldehyde O-benzoyloximes Promoted by R2NH in MeCN. Change of Reaction Mechanism

International Nuclear Information System (INIS)

Cho, Bong Rae; Pyun, Sang Yong

2010-01-01

We have studied the nitrile-forming elimination reactions from 1 promoted by R 2 NH in MeCN. The reaction proceeded by (E1cb) irr mechanism. Change of the β-aryl group from 2,4-dinitrophenyl to a more strongly electron-withdrawing 2,4,6-trinitrophenyl increased the reaction rate by 470-fold, shifted the transition state toward more reactant-like, and changed the reaction mechanism from E2 to (E1cb) irr . To the best of our knowledge, this is the first example of nitrile-forming elimination reaction that proceeds by the (E1cb) irr mechanism in MeCN. Noteworthy is the carbanion stabilizing ability of the 2,4,6-trinitrophenyl group in aprotic solvent. Nitrile-forming elimination reactions of (E)-benzaldoxime derivatives have been extensively investigated under various conditions. The reactions proceeded by the E2 mechanism in MeCN despite the fact that the reactants have syn stereochemistry, poor leaving, and sp 2 hybridized β-carbon atom, all of which favor E1cb- or E1cb-like transition state. Moreover, the transition state structures were relatively insensitive to the variation of the reactant structures. The results have been attributed to the poor anion solvating ability of MeCN, which favors E2 transition state with maximum charge dispersal. For eliminations from strongly activated (E)-2,4-(NO 2 ) 2 C 6 H 3 CH=NOC(O)C 6 H 4 X, a change in the reaction mechanism from E2 to (E1cb) irr was observed as the base-solvent was changed from R 2 NH in MeCN to R 2 NH/R 2 NH 2 + in 70 mol % MeCN(aq). A combination of a strong electron-withdrawing β-aryl group and anion-solvating protic solvent was required for the mechanistic change

(Acetonitrile-κNchloridobis[2-(pyridin-2-ylphenyl-κ2C1,N]iridium(III

Directory of Open Access Journals (Sweden)

Florian Blasberg

2011-12-01

Full Text Available The IrIII atom of the title compound, [Ir(C11H8N2Cl(CH3CN], displays a distorted octahedral coordination. The pyridyl groups are in trans positions [N—Ir—N = 173.07 (10°], while the phenyl groups are trans with respect to the acetonitrile and chloride groups [C—Ir—N = 178.13 (11 and C—Ir—Cl = 176.22 (9°]. The pyridylphenyl groups only show a small deviation from planarity, with the dihedral angle between the planes of the two six-membered rings in each pyridylphenyl group being 5.6 (2 and 5.8 (1°. The crystal packing shows intermolecular C—H...Cl, C—H...π(acetonitrile and C—H...π(pyridylphenyl contacts.

Satellite-derived land covers for runoff estimation using SCS-CN method in Chen-You-Lan Watershed, Taiwan

Science.gov (United States)

Zhang, Wen-Yan; Lin, Chao-Yuan

2017-04-01

The Soil Conservation Service Curve Number (SCS-CN) method, which was originally developed by the USDA Natural Resources Conservation Service, is widely used to estimate direct runoff volume from rainfall. The runoff Curve Number (CN) parameter is based on the hydrologic soil group and land use factors. In Taiwan, the national land use maps were interpreted from aerial photos in 1995 and 2008. Rapid updating of post-disaster land use map is limited due to the high cost of production, so the classification of satellite images is the alternative method to obtain the land use map. In this study, Normalized Difference Vegetation Index (NDVI) in Chen-You-Lan Watershed was derived from dry and wet season of Landsat imageries during 2003 - 2008. Land covers were interpreted from mean value and standard deviation of NDVI and were categorized into 4 groups i.e. forest, grassland, agriculture and bare land. Then, the runoff volume of typhoon events during 2005 - 2009 were estimated using SCS-CN method and verified with the measured runoff data. The result showed that the model efficiency coefficient is 90.77%. Therefore, estimating runoff by using the land cover map classified from satellite images is practicable.

Nitrogen removal and nitrous oxide emission in surface flow constructed wetlands for treating sewage treatment plant effluent: Effect of C/N ratios.

Science.gov (United States)

Li, Ming; Wu, Haiming; Zhang, Jian; Ngo, Huu Hao; Guo, Wenshan; Kong, Qiang

2017-09-01

In order to design treatment wetlands with maximal nitrogen removal and minimal nitrous oxide (N 2 O) emission, the effect of influent C/N ratios on nitrogen removal and N 2 O emission in surface flow constructed wetlands (SF CWs) for sewage treatment plant effluent treatment was investigated in this study. The results showed that nitrogen removal and N 2 O emission in CWs were significantly affected by C/N ratio of influent. Much higher removal efficiency of NH 4 + -N (98%) and TN (90%) was obtained simultaneously in SF CWs at C/N ratios of 12:1, and low N 2 O emission (8.2mg/m 2 /d) and the percentage of N 2 O-N emission in TN removal (1.44%) were also observed. These results obtained in this study would be utilized to determine how N 2 O fluxes respond to variations in C/N ratios and to improve the sustainability of CWs for wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2 '-bipyridine)(CN)4]2-

DEFF Research Database (Denmark)

Kjær, Kasper Skov; Kunnus, Kristjan; Harlang, Tobias C. B.

2018-01-01

The excited state dynamics of solvated [Fe(bpy)(CN)4]2-, where bpy = 2,2'-bipyridine, show significant sensitivity to the solvent Lewis acidity. Using a combination of optical absorption and X-ray emission transient spectroscopies, we have previously shown that the metal to ligand charge transfer...... the MLCT excited state relaxation dynamics of [Fe(bpy)(CN)4]2- in water, a strong Lewis acid solvent. The charge-transfer excited state is now found to decay in less than 100 femtoseconds, forming a quasi-stable metal centered excited state with a 13 picosecond lifetime. We find that this MC excited state...... developed for solar applications....

Electron paramagnetic resonance of K3Rh(CN)6 irradiated with electrons in KCl

International Nuclear Information System (INIS)

Vugman, N.V.

1970-07-01

Using a simple theory, it was estimated the electronic density of the diamagnetic complex Rh (CN) 3- 6 in a KCl lattice. The g// and g1 values were determined by EPR, and the experimental results fit the theoretical calculations. (M.W.O.) [pt

Nano-galvanic coupling for enhanced Ag+ release in ZrCN-Ag films : Antibacterial application

NARCIS (Netherlands)

Calderon, S.; Ferreri, I.; Henriques, M.; De Hosson, J. T. M.; Cavaleiro, A.; Carvalho, S.

2016-01-01

The antibacterial properties of materials developed for medical devices with embedded silver nanoparticles are enhanced by controlling the release of silver ions. In this study, a simple experimental procedure for the augmentation of the silver ion release from ZrCN-Ag coatings is described. The

The effects of phase transformation on the structure and mechanical properties of TiSiCN nanocomposite coatings deposited by PECVD method

Science.gov (United States)

Abedi, Mohammad; Abdollah-zadeh, Amir; Bestetti, Massimiliano; Vicenzo, Antonello; Serafini, Andrea; Movassagh-Alanagh, Farid

2018-06-01

In the present study, the effects of phase transformations on the structure and mechanical properties of TiSiCN coatings were investigated. TiSiCN nanocomposite coatings were deposited on AISI H13 hot-work tool steel by a pulsed direct current plasma-enhanced chemical vapor deposition process at 350 or 500 °C, using TiCl4 and SiCl4 as the precursors of Ti and Si, respectively, in a CH4/N2/H2/Ar plasma as the source of carbon and nitrogen and reducing environment. Some samples deposited at 350 °C were subsequently annealed at 500 °C under Ar atmosphere. Super hard self-lubricant TiSiCN coatings, having nanocomposite structure consisting of TiCN nanocrystals and amorphous carbon particles embedded in an amorphous SiCNx matrix, formed through spinodal decomposition in the specimens deposited or annealed at 500 °C. In addition, it was revealed that either uncomplete or relatively coarse phase segregation of titanium compounds was achieved during deposition at 350 °C and 500 °C, respectively. On the contrary, by deposition at 350 °C followed by annealing at 500 °C, a finer structure was obtained with a sensible improvement of the mechanical properties of coatings. Accordingly, the main finding of this work is that significant enhancement in key properties of TiSiCN coatings, such as hardness, adhesion and friction coefficient, can be obtained by deposition at low temperature and subsequent annealing at higher temperature, thanks to the formation of a fine grained nanocomposite structure.

Strong ligand field effects of blue phosphorescent mono-cyclometalated iridium(III) complexes

International Nuclear Information System (INIS)

Ham, Ho Wan; Jung, Kyung Yoon; Kim, Young Sik

2010-01-01

A series of mono-cyclometalated blue phosphorescent iridium(III) complexes with two phosphines trans to each other and two cis-ancillary ligands, such as Ir(F 2 Meppy)(PPhMe 2 ) 2 (H)(Cl), [Ir(F 2 Meppy)(PPhMe 2 ) 2 (H)(NCMe)] + and Ir(F 2 Meppy)(PPhMe 2 ) 2 -(H)(CN), [F 2 Meppy = 2-(2',4'-difluorophenyl)-4-methyl-pyridine] were synthesized and studied to tune the phosphorescence wavelength to the deep blue region and to enhance the luminescence efficiencies. We investigate the electron-withdrawing capabilities of ancillary ligands using the DFT and TD-DFT calculations on the ground and excited states of the three complexes to gain insight into the factors responsible for the emission color change and the different luminescence efficiency. Reducing the molecular weight of phosphine ligand with PPhMe 2 leads to a strategy of the efficient deep blue organic light-emitting devices (OLED) by thermal processing instead of the solution processing. The electron-withdrawing difluoro group substituted on the phenyl ring and the cyano strong field ancillary ligand in the trans position to the carbon atom of phenyl ring increased HOMO-LUMO gap and achieved the hypsochromic shift in emission color. As a result, the maximum emission spectra of Ir(F 2 Meppy)(PPhMe 2 ) 2 (H)(Cl), [Ir(F 2 Meppy)(PPhMe 2 ) 2 (H)-(NCMe)] + and Ir(F 2 Meppy)(PPh-Me 2 ) 2 (H)(CN) were in the ranges of 446, 440, 439 nm, respectively.

Comment on "Beyond the SCS-CN method: A theoretical framework for spatially lumped rainfall-runoff response" by M. S. Bartlett et al.

Science.gov (United States)

Ogden, Fred L.; Hawkins, Richard Pete; Walter, M. Todd; Goodrich, David C.

2017-07-01

Bartlett et al. (2016) performed a re-interpretation and modification of the space-time lumped USDA NRCS (formerly SCS) Curve Number (CN) method to extend its applicability to forested watersheds. We believe that the well documented limitations of the CN method severely constrains the applicability of the modifications proposed by Bartlett et al. (2016). This forward-looking comment urges the research communities in hydrologic science and engineering to consider the CN method as a stepping stone that has outlived its usefulness in research. The CN method fills a narrow niche in certain settings as a parsimonious method having utility as an empirical equation to estimate runoff from a given amount of rainfall, which originated as a static functional form that fits rainfall-runoff data sets. Sixty five years of use and multiple reinterpretations have not resulted in improved hydrological predictability using the method. We suggest that the research community should move forward by (1) identifying appropriate dynamic hydrological model formulations for different hydro-geographic settings, (2) specifying needed model capabilities for solving different classes of problems (e.g., flooding, erosion/sedimentation, nutrient transport, water management, etc.) in different hydro-geographic settings, and (3) expanding data collection and research programs to help ameliorate the so-called "overparameterization" problem in contemporary modeling. Many decades of advances in geo-spatial data and processing, computation, and understanding are being squandered on continued focus on the static CN regression method. It is time to truly "move beyond" the Curve Number method.

Further Insight into the Lability of MeCN Ligands of Cytotoxic Cycloruthenated Compounds: Evidence for the Antisymbiotic Effect Trans to the Carbon Atom at the Ru Center.

Science.gov (United States)

Barbosa, Ana Soraya Lima; Werlé, Christophe; Colunga, Claudia Olivia Oliva; Rodríguez, Cecilia Franco; Toscano, Ruben Alfredo; Le Lagadec, Ronan; Pfeffer, Michel

2015-08-03

The two MeCN ligands in [Ru(2-C6H4-2'-Py-κC,N)(Phen, trans-C)(MeCN)2]PF6 (1), both trans to a sp(2) hybridized N atom, cannot be substituted by any other ligand. In contrast, the isomerized derivative [Ru(2-C6H4-2'-Py-κC,N)(Phen, cis-C)(MeCN)2]PF6 (2), in which one MeCN ligand is now trans to the C atom of the phenyl ring orthometalated to Ru, leads to fast and quantitative substitution reactions with several monodentate ligands. With PPh3, 2 affords [Ru(2-C6H4-2'-Py-κC,N)(Phen, cis-C)(PPh3)(MeCN)]PF6 (3), in which PPh3 is trans to the C σ bound to Ru. Compound 3 is not kinetically stable, because, under thermodynamic control, it leads to 4, in which the PPh3 is trans to a N atom of the Phen ligand. Dimethylsulfoxide (DMSO) can also substitute a MeCN ligand in 2, leading to 5, in which DMSO is coordinated to Ru via its S atom trans to the N atom of the Phen ligand, the isomer under thermodynamic control being the only compound observed. We also found evidence for the fast to very fast substitution of MeCN in 2 by water or a chloride anion by studying the electronic spectra of 2 in the presence of water or NBu4Cl, respectively. An isomerization related to that observed between 3 and 4 is also found for the known monophosphine derivative [Ru(2-C6H4-2'-Py-κC,N)(PPh3, trans-C)(MeCN)3]PF6 (10), in which the PPh3 is located trans to the C of the cyclometalated 2-phenylpyridine, since, upon treatment by refluxing MeCN, it leads to its isomer 11, [Ru(2-C6H4-2'-Py-κC,N)(PPh3, cis-C)(MeCN)3]PF6. Further substitutions are also observed on 11, whereby N^N chelates (N^N = 2,2'-bipyridine and phenanthroline) substitute two MeCN ligands, affording [Ru(2-C6H4-2'-Py-κC,N)(PPh3, cis-C)(N^N)(MeCN)]PF6 (12a and 12b). Altogether, the behavior of the obtained complexes by ligand substitution reactions can be rationalized by an antisymbiotic effect on the Ru center, trans to the C atom of the cyclometalated unit, leading to compounds having the least nucleophilic ligand trans to C

Preparation and Characterization of SiO2/SiCN Core-shell Ceramic Microspheres

Directory of Open Access Journals (Sweden)

ZHANG Hai-yuan

2017-05-01

Full Text Available The SiO2/PSN core-shell microspheres were prepared via an emulsion reaction combined with the polymer-derived ceramics (PDCs method using polysilazane (PSN in situ polymerization on the surface of SiO2 modified by silane coupling agents MPS, followed by pyrolysis process to obtain SiO2/SiCN core-shell ceramic microspheres. The effects of raw mass ratio, curing time and pyrolysis temperature on the formation and the morphology of core-shell microspheres were studied. The morphology, chemical composition and phase transformation were characterized by SEM, EDS, TEM, FT-IR and XRD. The results show that after reaction for 4h at 200℃, SiO2 completely coated PSN forms a core-shell microsphere with rough surface when the mass ratio of SiO2 and PSN is 1:4; when pyrolysis temperature is at 800-1200℃, amorphous SiO2/SiCN core-shell ceramic microspheres are prepared; at 1400℃, the amorphous phase partially crystallizes to produce SiO2, SiC and Si3N4 phase.

Surface modification of an aluminum alloy by electron beam introducing TiCN nanoparticles

Science.gov (United States)

Kolev, M.; Dimitrova, R.; Parshorov, St.; Valkov, St.; Lazarova, R.; Petrov, P.

2018-03-01

TiCN nanopowder deposited in an appropriate way on the surface of an AlSi12Cu2NiMg substrate was incorporated in the matrix using an electron beam technology. The samples were studied by means of light microscopy, SEM, and EDX; their microhardness was also determined. The formation was found of a uniform and dense coating with a thickness of 7 – 10 μgm with a good adherence to the substrate. A modified zone appeared under the coating with a thickness of 100 – 150 μgm containing dendrites of an α-solid solution and a fine eutectic between them, as well as primary silicon crystals. The microhardness of this modified zone was up to 2.4 times higher than that of the matrix. The results of SEM and EDX studies revealed unambiguously the presence of titanium in the coating and in the zones below it. Obviously, the electron beam treatment resulted in the TiCN nanoparticles penetrating into the coating and the substrate immediately below the coating.

THE POSSIBLE INTERSTELLAR ANION CH{sub 2}CN{sup -}: SPECTROSCOPIC CONSTANTS, VIBRATIONAL FREQUENCIES, AND OTHER CONSIDERATIONS

Energy Technology Data Exchange (ETDEWEB)

Fortenberry, Ryan C.; Lee, Timothy J. [NASA Ames Research Center, Moffett Field, CA 94035-1000 (United States); Crawford, T. Daniel, E-mail: Ryan.C.Fortenberry@nasa.gov, E-mail: Timothy.J.Lee@nasa.gov [Department of Chemistry, Virginia Tech, Blacksburg, VA 24061 (United States)

2013-01-10

The A {sup 1}B{sub 1} Leftwards-Open-Headed-Arrow X-tilde{sup 1}A' excitation into the dipole-bound state of the cyanomethyl anion (CH{sub 2}CN{sup -}) has been hypothesized as the carrier for one diffuse interstellar band. However, this particular molecular system has not been detected in the interstellar medium even though the related cyanomethyl radical and the isoelectronic ketenimine molecule have been found. In this study, we are employing the use of proven quartic force fields and second-order vibrational perturbation theory to compute accurate spectroscopic constants and fundamental vibrational frequencies for X-tilde{sup 1} A' CH{sub 2}CN{sup -} in order to assist in laboratory studies and astronomical observations.

Formation constants of Sm(III), Dy(III), Gd(III), Pr(III) and Nd(III) complexes of tridentate schiff base, 2-[(1H-benzimidazol-2-yl-methylene) amino] phenol

International Nuclear Information System (INIS)

Omprakash, K.L.; Chandra Pal, A.V.; Reddy, M.L.N.

1982-01-01

A new tridentate schiff base, 2- (1H-benzimidazol-2-yl-methylene)amino phenol derived from benzimididazole-2-carbo-xaldehyde and 2-aminophenol has been synthesised and characterised by spectral and analytical data. Proton-ligand formation constants of the schiff base and metal-ligand formation constants of its complexes with Sm(III), Dy(III), Gd(III), Nd(III) and Pr(III) have been determined potentiometrically in 50% (v/v) aqueous dioxane at an ionic strength of 0.1M (NaClO 4 ) and at 25deg C using the Irving-Rossotti titration technique. The order of stability constants (logβ 2 ) is found to be Sm(III)>Dy(III)>Gd(III)>Pr(III)>Nd(III). (author)

Formation constants of Sm(III), Dy(III), Gd(III), Pr(III) and Nd(III) complexes of tridentate schiff base, 2-((1H-benzimidazol-2-yl-methylene) amino) phenol

Energy Technology Data Exchange (ETDEWEB)

Omprakash, K L; Chandra Pal, A V; Reddy, M L.N. [Osmania Univ., Hyderabad (India). Dept. of Chemistry

1982-03-01

A new tridentate schiff base, 2- (1H-benzimidazol-2-yl-methylene)amino phenol derived from benzimididazole-2-carbo-xaldehyde and 2-aminophenol has been synthesised and characterised by spectral and analytical data. Proton-ligand formation constants of the schiff base and metal-ligand formation constants of its complexes with Sm(III), Dy(III), Gd(III), Nd(III) and Pr(III) have been determined potentiometrically in 50% (v/v) aqueous dioxane at an ionic strength of 0.1M (NaClO/sub 4/) and at 25deg C using the Irving-Rossotti titration technique. The order of stability constants (log..beta../sub 2/) is found to be Sm(III)>Dy(III)>Gd(III)>Pr(III)>Nd(III).

Development of the dyed-track method for Kodak CN-85 detector. No. E/3

International Nuclear Information System (INIS)

Somogyi, G.; Toth-Szilagyi, M.; Varga, Zs.; Monnin, M.; Lferde, M.

1983-01-01

The dyed-track method has been successfully developed for cellulose derivatives. The track parameters (width, coloration deepness, contrast, registration sensitivity), however, proved to be very dependent on the detector material and on the track processing conditions. In the authors' previous works optimum conditions were presented mostly for cellulose acetate sheets. In the present work the influence of track processing parameters on the dyed-track formation was studied in Kodak cellulose nitrate detector called CN-85. It is found that in this material optimum dyed-tracks can be produced with using no swelling but with a thermal annealing at 100 deg C for 1 hour after particles irradiation. For sensitization a treatment with 15% HCL at 22 deg C for 20 hours and for dyeing 0.3 wt% Rhodamine-B at 100 deg C for 1 hour proved to be best. For understanding the track dyeing phenomenon the coloration behaviour of electron-irradiated CN-85 detectors was studied. (author)

Low-dimensional compounds containing cyano groups. XVII. Crystal structure, spectroscopic, thermal and magnetic properties of [Cu(bmen)2][Pt(CN)4] (bmen=N,N'-dimethylethylenediamine)

International Nuclear Information System (INIS)

Potocnak, Ivan; Vavra, Martin; Cizmar, Erik; Kajnakova, Marcela; Radvakova, Alena; Steinborn, Dirk; Zvyagin, Sergei A.; Wosnitza, Jochen; Feher, Alexander

2009-01-01

The synthesis, structural analysis, spectroscopic studies, susceptibility and specific-heat measurements of {[Cu(bmen) 2 ][Pt(CN) 4 ]} n (bmen=N,N'-dimethylethylenediamine) are presented. X-ray crystal-structure analysis revealed that the [Pt(CN) 4 ] 2- building blocks are combined with [Cu(bmen) 2 ] 2+ units to form a chain-like structure along the a axis. The Cu(II) atoms are hexacoordinated by four nitrogen atoms in the equatorial plane belonging to two molecules of bidentate bmen ligands with average Cu-N distance of 2.043(18) A. The axial positions are occupied by two nitrogen atoms from bridging [Pt(CN) 4 ] 2- anions at a longer axial Cu-N distance of 2.490(4) A. The compound is characterized by the presence of a weak antiferromagnetic exchange coupling J/k B =0.6 K. Despite the one-dimensional (1D) character of the structure, the analysis of the magnetic properties and specific heat at very low temperatures shows that [Cu(bmen) 2 ][Pt(CN) 4 ] behaves as a two-dimensional (2D) square-lattice Heisenberg magnet with weak interlayer coupling. - Graphical abstract: The synthesis, structural analysis, spectroscopic studies, susceptibility and specific-heat measurements of {[Cu(bmen) 2 ][Pt(CN) 4 ]} n (bmen=N,N'-dimethylethylenediamine) are presented. X-ray crystal-structure analysis revealed that the [Pt(CN) 4 ] 2- building blocks are combined with [Cu(bmen) 2 ] 2+ units to form a chain-like structure. The compound is characterized by the presence of a weak antiferromagnetic exchange coupling J/k B =-0.6 K. Despite the one-dimensional character of the structure, the analysis of the magnetic properties and specific heat at very low temperatures shows that [Cu(bmen) 2 ][Pt(CN) 4 ] behaves as a two-dimensional square-lattice Heisenberg magnet with weak interlayer coupling

Spectrophotometric and pH-Metric Studies of Ce(III, Dy(III, Gd(III,Yb(III and Pr(III Metal Complexes with Rifampicin

Directory of Open Access Journals (Sweden)

A. N. Sonar

2011-01-01

Full Text Available The metal-ligand and proton-ligand stability constant of Ce(III, Dy(III, Gd(III,Yb(III and Pr(III metals with substituted heterocyclic drug (Rifampicin were determined at various ionic strength by pH metric titration. NaClO4 was used to maintain ionic strength of solution. The results obtained were extrapolated to the zero ionic strength using an equation with one individual parameter. The thermodynamic stability constant of the complexes were also calculated. The formation of complexes has been studied by Job’s method. The results obtained were of stability constants by pH metric method is confirmed by Job’s method.

Rapid synthesis of graphitic carbon nitride powders by metathesis reaction between CaCN{sub 2} and C{sub 2}Cl{sub 6}

Energy Technology Data Exchange (ETDEWEB)

Pang Linlin [Key Laboratory of Liquid Structure and Heredity of Materials, Ministry of Education, Shandong University, Jinan, 250061 (China); Carbon Fiber Engineering Research Center of Shandong Province, Shandong University, Jinan 250061 (China); Bi Jianqiang [Key Laboratory of Liquid Structure and Heredity of Materials, Ministry of Education, Shandong University, Jinan, 250061 (China); Bai Yujun [Key Laboratory of Liquid Structure and Heredity of Materials, Ministry of Education, Shandong University, Jinan, 250061 (China) and Carbon Fiber Engineering Research Center of Shandong Province, Shandong University, Jinan 250061 (China)], E-mail: byj97@126.com; Qi Yongxin [Carbon Fiber Engineering Research Center of Shandong Province, Shandong University, Jinan 250061 (China); Zhu Huiling [Key Laboratory of Liquid Structure and Heredity of Materials, Ministry of Education, Shandong University, Jinan, 250061 (China); Carbon Fiber Engineering Research Center of Shandong Province, Shandong University, Jinan 250061 (China); Wang Chengguo; Wu Jiwei [Carbon Fiber Engineering Research Center of Shandong Province, Shandong University, Jinan 250061 (China); Lu Chengwei [Department of Equipment, Shandong University of Science and Technology, Jinan 250031 (China)

2008-12-20

Carbon nitride powders were rapidly synthesized at low temperature via the chemical metathesis reaction between CaCN{sub 2} and C{sub 2}Cl{sub 6}. X-ray diffraction results confirm the formation of crystalline graphitic carbon nitride. Besides the dominant morphology of nanoparticles, flakes, nanorods, hollow and solid spheres can be observed by transmission electron microscopy. The absorption peaks of C-N, C=N and s-triazine rings, as well as the absence of C{identical_to}N peak in the infrared spectra, further verify the formation of graphite-like sp{sup 2}-bonded structure with planar networks. Elemental analysis gives an atomic ratio of N/C around 0.3. X-ray photoelectron spectra exhibit the existence of chemical bonding between C and N.

Alkyl hydrogen atom abstraction reactions of the CN radical with ethanol

Science.gov (United States)

Athokpam, Bijyalaxmi; Ramesh, Sai G.

2018-04-01

We present a study of the abstraction of alkyl hydrogen atoms from the β and α positions of ethanol by the CN radical in solution using the Empirical Valence Bond (EVB) method. We have built separate 2 × 2 EVB models for the Hβ and Hα reactions, where the atom transfer is parameterized using ab initio calculations. The intra- and intermolecular potentials of the reactant and product molecules were modelled with the General AMBER Force Field, with some modifications. We have carried out the dynamics in water and chloroform, which are solvents of contrasting polarity. We have computed the potential of mean force for both abstractions in each of the solvents. They are found to have a small and early barrier along the reaction coordinate with a large energy release. Analyzing the solvent structure around the reaction system, we have found two solvents to have little effect on either reaction. Simulating the dynamics from the transition state, we also study the fate of the energies in the HCN vibrational modes. The HCN molecule is born vibrationally hot in the CH stretch in both reactions and additionally in the HCN bends for the Hα abstraction reaction. In the early stage of the dynamics, we find that the CN stretch mode gains energy at the expense of the energy in CH stretch mode.

Complexes of lanthanum(III), cerium(III), samarium(III) and dysprosium(III) with substituted piperidines

Energy Technology Data Exchange (ETDEWEB)

Manhas, B S; Trikha, A K; Singh, H; Chander, M

1983-11-01

Complexes of the general formulae M/sub 2/Cl/sub 6/(L)/sub 3/.C/sub 2/H/sub 5/OH and M/sub 2/(NO/sub 3/)/sub 6/(L)/sub 2/.CH/sub 3/OH have been synthesised by the reactions of chlorides and nitrates of La(III), Ce(III), Sm(III) and Dy(III) with 2-methylpiperidine, 3-methylpiperidine and 4-methylpiperidine. These complexes have been characterised on the basis of their elemental analysis, and IR and electronic reflectance spectra. IR spectral data indicate the presence of coordinated ethanol and methanol molecules and bidentate nitrate groups. Coordination numbers of the metal ions vary from 5 to 8. 19 refs.

Encapsulation of ferro- and ferricyanide complexes inside ZSM-5 zeolite synthesized from rice straw: Implications for synthesis of Prussian blue pigment

Energy Technology Data Exchange (ETDEWEB)

Ali, Ibraheem O.; Salama, Tarek M., E-mail: tm_salama@yahoo.com; Thabet, Mohamed S.; El-Nasser, Karam S.; Hassan, Ali M.

2013-06-15

Encapsulation of [Fe(CN){sub 6}]{sup 4−} and [Fe(CN){sub 6}]{sup 3−} complexes in the intracrystalline pores of ZSM-5 zeolite, Fe{sup II}L/Z and Fe{sup III}L/Z respectively, by the zeolite synthesis method was reported. The modified zeolites were characterized by powder XRD, FT-IR and UV–vis spectroscopy. The nitrogen adsorption isotherms allow for the evaluation of pore structure of the complex-modified zeolites, whereas the thermal analysis (TGA/DTA) measurements provide insight into the decomposition products of the immobilized complexes. The modified zeolites exhibited smaller pore volumes and surface areas as compared with those of unpromoted ZSM-5, suggesting the inclusion of iron cyanides inside the interconnecting channels of ZSM-5. While the ferricyanide complex enhanced the formation of highly crystalline zeolite, the ferrocyanide one resulted in a lesser effect. The electronic spectra of the colloidal species developed when Fe{sup III}L/Z brought in contact with an aqueous solution of [Fe(CN){sub 6}]{sup 3−} exhibit absorptions attributed to CN{sup −} → iron charge-transfer. New bands at 294 and 319 nm due to d–d transitions of Fe{sup III} tetrahedral monomeric moieties were emitted concurrently under successive adsorption of [Fe(CN){sub 6}]{sub aq}{sup 3−} over Fe{sup III}L/Z, along with a broad band at 555 nm assigned to polymeric [Fe{sup II}–C–N–Fe{sup III}] of Prussian blue (PB). The FT-IR spectra of Fe{sup III/II}L/Z devoted to the adsorption of an aqueous solution of [Fe(CN){sub 6}]{sup 3−} showed a band at 2092 cm{sup −1} assigned to the C–N stretch in the Fe{sup II}–CN–Fe{sup III} linkages. The vibrations attributable to Fe–O–Si bonding along with hydrocarbon and nitroprusside appeared only in the spectrum of Fe{sup III}L/Z, thus was found to be strong evidence for the mutual interaction between [Fe(CN){sub 6}]{sup 3−} and the latter sample. - Highlights: • We synthesized ferrous and ferric cyanide

Spatial distributions of H, CN, and C2 in a diamond growing oxyacetylene flame

NARCIS (Netherlands)

Klein-Douwel, R.J.H.; Meulen, ter J.J.

1998-01-01

Two-dimensional laser-induced fluorescence (2D-LIF) measurements are applied to the chemical vapor deposition (CVD) of diamond by an oxyacetylene flame to visualize the distributions of atomic hydrogen, C2, and CN in the gas phase during diamond growth. Experiments are carried out in laminar flames

Analysis of the runoff generation mechanism for the investigation of the SCS-CN method applicability to a partial area experimental watershed

Science.gov (United States)

Soulis, K. X.; Valiantzas, J. D.; Dercas, N.; Londra, P. A.

2009-01-01

The Soil Conservation Service Curve Number (SCS-CN) method is widely used for predicting direct runoff volume for a given rainfall event. The applicability of the SCS-CN method and the runoff generation mechanism were thoroughly analysed in a Mediterranean experimental watershed in Greece. The region is characterized by a Mediterranean semi-arid climate. A detailed land cover and soil survey using remote sensing and GIS techniques, showed that the watershed is dominated by coarse soils with high hydraulic conductivities, whereas a smaller part is covered with medium textured soils and impervious surfaces. The analysis indicated that the SCS-CN method fails to predict runoff for the storm events studied, and that there is a strong correlation between the CN values obtained from measured runoff and the rainfall depth. The hypothesis that this correlation could be attributed to the existence of an impermeable part in a very permeable watershed was examined in depth, by developing a numerical simulation water flow model for predicting surface runoff generated from each of the three soil types of the watershed. Numerical runs were performed using the HYDRUS-1D code. The results support the validity of this hypothesis for most of the events examined where the linear runoff formula provides better results than the SCS-CN method. The runoff coefficient of this formula can be taken equal to the percentage of the impervious area. However, the linear formula should be applied with caution in case of extreme events with very high rainfall intensities. In this case, the medium textured soils may significantly contribute to the total runoff and the linear formula may significantly underestimate the runoff produced.

Phase transitions of doped carbon in CrCN coatings with modified mechanical and tribological properties via filtered cathodic vacuum arc deposition

International Nuclear Information System (INIS)

Guan, J.J.; Wang, H.Q.; Qin, L.Z.; Liao, B.; Liang, H.; Li, B.

2017-01-01

The CrCN coatings were fabricated onto Si (1 1 1) wafers and SUS304 stainless steel plates using filtered cathodic vacuum arc deposition (FCVAD) technique under different flow ratios of N_2/C_2H_2 gas mixture. The morphology, crystalline structure and chemical composition of the coatings were characterized. It was found that the grain size reduce with increasing carbon content, which makes the CrCN coatings refined and smooth. The quasi-one-dimensional carbolite phase was also found in CrN host lattice with C_2H_2 content ranging from 5% to 20%, and it will be evolved into amorphous carbon and amorphous CN_x phases as C_2H_2 content exceeds 20%. Moreover, we examined the mechanical and tribological properties of the CrCN coatings, and the experimental results confirmed that the friction coefficient of the coatings descend to the lowest value as 0.39 with 30% C_2H_2 content, due to the graphite (sp"2 C−C) phase embed in CrN host lattice; while the chromium carbon (Cr_3C_2) and diamond (sp"3 C−C) phases may give rise to the increase of the coating hardness with the highest value at 23.97 GPa under 20% C_2H_2 content.

Organic carbon source and C/N ratio affect inorganic nitrogen profile in the biofloc-based culture media of Pacific white shrimp (Litopenaeus vannamei

Directory of Open Access Journals (Sweden)

Muhammad Hanif Azhar

2016-03-01

Full Text Available Organic carbon source and C/N ratio play an important role in aquaculture system with biofloc technology application. Nitrogen control by adding carbohydrates to the water to stimulate heterotrophic bacterial growth by converting nitrogen into bacterial biomass. The study investigated the effect molasses, tapioca, tapioca by product and rice bran as carbon sources in a biofloc media at three different C/N ratios i.e. 10, 15, and 20 on total ammonia reduction in biofloc media. Five liters of biofloc media in a conical tank was prepared for each replicate, which consisted of 500 mL of biofloc suspension collected from a shrimp culture unit with biofloc technology application and 4.5 L seawater. Pacific white shrimp culture was performed in 40L glass aquaria at a shrimp density of 30/aquarium. There was a significant interaction between carbon source and the C/N ratio applied (P<0.05. The use of molasses resulted in the highest reduction rate irrespective to the C/N ratio. Keywords: molasses, tapioca, tapioca by product, rice bran, biofloc, total ammonia nitrogen

Tribological behavior and self-healing functionality of TiNbCN-Ag coatings in wide temperature range

Energy Technology Data Exchange (ETDEWEB)

Bondarev, A.V., E-mail: abondarev88@gmail.com; Kiryukhantsev-Korneev, Ph.V.; Levashov, E.A.; Shtansky, D.V., E-mail: shtansky@shs.misis.ru

2017-02-28

Highlights: • TiNbCN–Ag coatings for wide temperature range tribological applications. • Alloying with Nb and Ag improve tribological properties and oxidation resistance. • Ag-rich TiNbCN coatings show friction coefficient below 0.45 in range of 25–700 °C. • Ag-doped coatings show active oxidation protection and self-healing functionality. - Abstract: Ag- and Nb-doped TiCN coatings with about 2 at.% of Nb and Ag contents varied between 4.0 and 15.1 at.% were designed as promising materials for tribological applications in a wide temperature range. We report on the structure, mechanical, and tribological properties of TiNbCN-Ag coatings fabricated by simultaneous co-sputtering of TiC{sub 0.5} + 10%Nb{sub 2}C and Ag targets in comparison with those of Ag-free coating. The tribological characteristics were evaluated during constant-temperature tests both at room temperature and 300 °C, as well as during dynamic temperature ramp tests in the range of 25–700 °C. The coating structure and elemental composition were studied by means of X-ray diffraction, scanning and transmission electron microscopy, and glow discharge optical emission spectroscopy. The coating microstructures and elemental compositions inside wear tracks, as well as the wear products, were examined by scanning electron microscopy, energy-dispersive spectroscopy, and Raman spectroscopy. We demonstrate that simultaneous alloying with Nb and Ag permits to overcome the main drawbacks of TiCN coatings such as their relatively high values of friction coefficient at elevated temperatures and low oxidation resistance. It is shown that a relatively high amount of Ag (15 at.%) is required to provide enhanced tribological behavior in a wide temperature range of 25–700 °C. In addition, the prepared Ag-doped coatings demonstrated active oxidation protection and self-healing functionality due to the segregation of Ag metallic particles in damage areas such as cracks, pin-holes, or oxidation sites.

Inner-sphere and outer-sphere complexes of yttrium(III), lanthanum (III), neodymium(III), terbium(III) and thulium(III) with halide ions in N,N-dimethylformamide

International Nuclear Information System (INIS)

Takahashi, Ryouta; Ishiguro, Shin-ichi

1991-01-01

The formation of chloro, bromo and iodo complexes of yttrium(III), and bromo and iodo complexes of lanthanum(III), neodymium(III), terbium(III) and thulium(III) has been studied by precise titration calorimetry in N,N-dimethylformamide (DMF) at 25 o C. The formation of [YCl] 2+ , [YCl 2 ] + , [YCl 3 ] and [YCl 4 ] - , and [MBr] 2+ and [MBr 2 ] + (M = Y, La, Nd, Tb, Tm) was revealed, and their formation constants, enthalpies and entropies were determined. It is found that the formation enthalpies change in the sequence ΔH o (Cl) > ΔH o (l), which is unusual for hard metal (III) ions. This implies that, unlike the chloride ion, the bromide ion forms outer-sphere complexes with the lanthanide(III) and yttrium(III) ions in DMF. Evidence for either an inner- or outer-sphere complex was obtained from 89 Y NMR spectra for Y(ClO 4 ) 3 , YCl 3 and YBr 3 DMF solutions at room temperature. (author)

A sediment graph model based on SCS-CN method

Science.gov (United States)

Singh, P. K.; Bhunya, P. K.; Mishra, S. K.; Chaube, U. C.

2008-01-01

SummaryThis paper proposes new conceptual sediment graph models based on coupling of popular and extensively used methods, viz., Nash model based instantaneous unit sediment graph (IUSG), soil conservation service curve number (SCS-CN) method, and Power law. These models vary in their complexity and this paper tests their performance using data of the Nagwan watershed (area = 92.46 km 2) (India). The sensitivity of total sediment yield and peak sediment flow rate computations to model parameterisation is analysed. The exponent of the Power law, β, is more sensitive than other model parameters. The models are found to have substantial potential for computing sediment graphs (temporal sediment flow rate distribution) as well as total sediment yield.

Monomers, dimers, and trimers of [Au(CN2]− in a Ba(diaza-18-crown-62+ coordination polymer

Directory of Open Access Journals (Sweden)

2009-03-01

Full Text Available The structure of the title compound, poly[triaquatetra-μ-cyanido-tetracyanidobis(1,4,10,13-tetraoxa-7,16-diazacyclooctadecanedibarium(IItetragold(I], [Au4Ba2(CN8(C12H26N2O42(H2O3]n, displays O—H...N hydrogen bonding between water molecules and cyano ligands and an unusual pattern of aurophilic interactions that yields a monomer, dimer, and trimer of [Au(CN2]− within the same crystal structure. In two of the five Au positions, the atom resides on a center of inversion. The overall arrangement is that of a coordination polymer assisted by aurophilic and hydrogen-bonded interactions.

Tris(8-hydroxyquinoline)aluminum (III) (Alq3) nanowires templated from an eggshell membrane

Energy Technology Data Exchange (ETDEWEB)

Lee, Tu, E-mail: tulee@cc.ncu.edu.t [Department of Chemical and Materials Engineering, National Central University, 300 Jhong-Da Rd, Jhong-Li City 320, Taiwan (China); Chang, Shih Chia; Peng, Jen Fan [Department of Chemical and Materials Engineering, National Central University, 300 Jhong-Da Rd, Jhong-Li City 320, Taiwan (China)

2010-07-30

One to 2-{mu}m long, {<=} 400-nm wide amorphous tris(8-hydroxyquinoline)aluminum (III) (Alq3) nanowires (NWs) grown from the 15-min boiled outer shell membrane (OSM) of the hen's egg and from the OSM solution cast film via thermal evaporation with a source temperature of 260 {sup o}C and a substrate temperature of 138 {sup o}C under 6.7 x 10{sup -2} Pa gave about 1.4 to 1.7 times more photoluminescence emission than the control Alq3 sample did, which was grown from the plain glass surface. The characteristic bonding energies of C 1s X-ray photoelectron signal at 282 eV, O 1s signal at 529 eV and N 1s signal at 397 eV suggested that the relatively high NW density for the 15-min boiled OSM and the OSM solution cast film, was mainly caused by the formation of the O=C-O-C=O anhydride moiety and the C=N group in the proteinaceous OSM at high temperature of 90 {sup o}C to 100 {sup o}C. Therefore, we proposed that the 15-min boiled OSM and the OSM solution cast film apparently served as good templates by providing nano-regions of high concentration of the O=C-O-C=O anhydride groups and the C=N groups for nesting the Alq3 gas molecules to form nano-conical Alq3 nuclei for the growth of long and narrow NWs.

Effect of C/N ratio, aeration rate and moisture content on ammonia and greenhouse gas emission during the composting.

Science.gov (United States)

Jiang, Tao; Schuchardt, Frank; Li, Guoxue; Guo, Rui; Zhao, Yuanqiu

2011-01-01

Gaseous emission (N2O, CH4 and NH3) from composting can be an important source of anthropogenic greenhouse gas and air pollution. A laboratory scale orthogonal experiment was conducted to estimate the effects of C/N ratio, aeration rate and initial moisture content on gaseous emission during the composting of pig faeces from Chinese Ganqinfen system. The results showed that about 23.9% to 45.6% of total organic carbon (TOC) was lost in the form of CO2 and 0.8% to 7.5% of TOC emitted as CH4. Most of the nitrogen was lost in the form of NH3, which account for 9.6% to 32.4% of initial nitrogen. N2O was also an important way of nitrogen losses and 1.5% to 7.3% of initial total nitrogen was lost as it. Statistic analysis showed that the aeration rate is the most important factor which could affect the NH3 (p = 0.0189), CH4 (p = 0.0113) and N2O (p = 0.0493) emissions significantly. Higher aeration rates reduce the CH4 emission but increase the NH3 and N2O losses. C/N ratio could affect the NH3 (p = 0.0442) and CH4 (p = 0.0246) emissions significantly, but not the N2O. Lower C/N ratio caused higher NH3 and CH4 emissions. The initial moisture content can not influence the gaseous emission significantly. Most treatments were matured after 37 days, except a trial with high moisture content and a low C/N ratio.

Reaction of cyanide with cytochrome ba3 from Thermus thermophilus: spectroscopic characterization of the Fe(II)a3-CN.Cu(II)B-CN complex suggests four 14N atoms are coordinated to CuB.

Science.gov (United States)

Surerus, K K; Oertling, W A; Fan, C; Gurbiel, R J; Einarsdóttir, O; Antholine, W E; Dyer, R B; Hoffman, B M; Woodruff, W H; Fee, J A

1992-01-01

Cytochrome ba3 from Thermus thermophilus reacts slowly with excess HCN at pH 7.4 to create a form of the enzyme in which CuA, cytochrome b, and CuB remain oxidized, while cytochrome a3 is reduced by one electron, presumably with the formation of cyanogen. We have examined this form of the enzyme by UV-visible, resonance Raman, EPR, and electron nuclear double resonance spectroscopies in conjunction with permutations of 13C- and 15N-labeled cyanide. The results support a model in which one CN- binds through the carbon atom to ferrous a3, supporting a low-spin (S = 0) configuration on the Fe; bridging by this cyanide to the CuB is weak or absent. Four 14N atoms, presumably donated by histidine residues of the protein, provide a strong equatorial ligand field about CuB; a second CN- is coordinated through the carbon atom to CuB in an axial position. PMID:1314380

Triosmium cluster compounds containing isocyanide and hydride ligands. Crystal and molecular structures of (μ-H)(H)Os3(CO)10(CN-t-C4H9) and (μ-H)2Os3(CO)9(CN-t-C4H9)

International Nuclear Information System (INIS)

Adams, R.D.; Golembski, N.M.

1979-01-01

The structures of the compounds (μ-H)(H)Os 3 (CO) 10 (CN-t-C 4 H 9 ) and (μ-H) 2 Os 3 (CO) 9 (CN-t-C 4 H 9 ) have been revealed by x-ray crystallographic techniques. For (μ-H)(H)Os 3 (CO) 10 (CN-t-C 4 H 9 ): a = 9.064 (3), b = 12.225 (3), c = 20.364 (4) A; β = 98.73 (3) 0 ; space group P2 1 /c[C/sub 2h/ 5 ], No. 14; Z = 4; d/sub calcd/ = 2.79 g cm -3 . This compound contains a triangular cluster of three osmium atoms; Os(1)--Os(2) = 2.930 (1) A, Os(1)--Os(3) = 2.876 (1) A, and Os(2)--Os(3) = 3.000 (1) A. There are ten linear terminal carbonyl groups and one linear terminal isocyanide ligand which occupies an axial coordination site. The hydrogen atoms were not observed crystallographically, but their positions are strongly inferred from considerations of molecular geometry. For (μ-H) 2 Os 3 (CO) 9 (CN-t-C 4 H 9 ): a = 15.220 (8), b = 12.093 (6), c = 23.454 (5) A; space group Pbcn [D/sub 2h/ 14 ], No. 60; Z = 8; d/sub calcd/ = 2.79 g cm -3 . The compound is analogous to the parent carbonyl (μ-H) 2 Os 3 (CO) 10 and has two normal and one short osmium--osmium bonds: Os(1)--Os(2) = 2.827 (1) A, Os(1)--Os(3) = 2.828 (1) A, Os(2)--Os(3) = 2.691 (1) A. The isocyanide ligand resides in an equatorial coordination site on osmium Os(2). The hydrogen atoms were not observed but are believed to occupy bridging positions as in the parent carbonyl complex. 2 figures, 7 tables

Identification of the c(10×6)-CN/Cu(001) surface structure

KAUST Repository

Shuttleworth, I.G.

2014-01-01

© 2014 Elsevier B.V. All rights reserved. A systematic survey of all possible c(10 x 6)-CN/Cu(0 0 1) structures has been performed using density functional theory (DFT). A group of four preferred structures is presented with one of the structures identified as optimal. An analysis of the bonding within the optimal structure has shown that a significant localisation of the surface Cu 4s bonds occurs in the saturated system.

Identification of the c(10×6)-CN/Cu(001) surface structure

KAUST Repository

Shuttleworth, I.G.

2014-12-01

© 2014 Elsevier B.V. All rights reserved. A systematic survey of all possible c(10 x 6)-CN/Cu(0 0 1) structures has been performed using density functional theory (DFT). A group of four preferred structures is presented with one of the structures identified as optimal. An analysis of the bonding within the optimal structure has shown that a significant localisation of the surface Cu 4s bonds occurs in the saturated system.

Pressure-induced structural change of liquid InAs and the systematics of liquid III-V compounds

International Nuclear Information System (INIS)

Hattori, T.; Tsuji, K.; Miyata, Y.; Sugahara, T.; Shimojo, F.

2007-01-01

To understand the pressure-induced structural changes of liquid III-V compounds systematically, the pressure dependence of l-InAs was investigated using the synchrotron x-ray diffraction and an ab initio molecular-dynamics simulation (AIMD). The x-ray diffraction experiments revealed that the liquid changes its compression behavior from a nearly uniform type to a nonuniform one around 9 GPa. Corresponding to this change, the coordination number (China), which is maintained up to 9 GPa, markedly increases from 6.0 to 7.5. The AIMD simulation revealed that this change is related to the change in the pressure dependence of all three pair correlations. In particular, a marked change is observed in the As-As correlation; in the low-pressure region, the position of the first peak in g AsAs (r), r AsAs , increases while maintaining the CN AsAs , but in the high-pressure region, the r AsAs stops increasing and the CN AsAs begins to increase. The AIMD simulation also revealed that each partial structure of l-InAs is similar to that for the pure-element liquid with the same valence electron number. Upon compression, each partial structure approaches the respective one for a heavier element in the same group. These findings suggest that the structures of liquid compounds are locally controlled by the number of the valence electrons in each ion pair and that the change in each partial structure obeys the empirical rule that the high-pressure state resembles the ambient state of a heavier element in the same group. Comparing the pressure-induced structural change of l-InAs to those of other liquid III-V compounds (GaSb and InSb) has revealed that, although the high-pressure behaviors of these three liquids are apparently different, their structural changes are systematically understood by a common structural sequence. This systematics originates from the same effect on each partial structure between increasing the atomic number and the pressurization

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)

Fitomassa e relação C/N em consórcios de sorgo e milho com espécies de cobertura Biomass and C/N ratio in intercrops of sorghum and maize with cover crops

Directory of Open Access Journals (Sweden)

Paulo Claudeir Gomes da Silva

2009-11-01

Full Text Available O objetivo deste trabalho foi quantificar a produtividade de fitomassa, o teor e acúmulo de nitrogênio (N, e a relação carbono/nitrogênio (C/N de monocultivos de sorgo (Sorghum bicolor e milho (Zea mays e de seus consórcios com guandu-anão (Cajanus cajan, crotalária (Crotalaria juncea, tremoço branco (Lupinus albus, girassol (Helianthus annuus e nabo-forrageiro (Raphanus sativus, manejados em diferentes estádios. O experimento foi conduzido de março a julho de 2008, em Argissolo Vermelho distroférrico de textura média, no sistema plantio direto. O delineamento experimental foi o de blocos completos ao acaso, com quatro repetições, e parcelas subdivididas, constituído pelos tratamentos: monocultivos de sorgo e milho e seus respectivos consórcios com guandu-anão, crotalária, girassol, nabo-forrageiro e tremoço branco, nas parcelas; e épocas de corte, aos 60, 90 e 120 dias após a semeadura nas subparcelas. Consórcios de sorgo e milho com outras espécies superaram expressivamente a produtividade de fitomassa de seus monocultivos que ainda acumularam menos N e apresentaram maiores relações C/N na fitomassa. Para aumentar a produtividade de fitomassa, a melhor época de corte é aos 120 dias após a semeadura das culturas de cobertura. O corte aos 90 dias após a semeadura propicia o maior acúmulo de N e as menores relações C/N.The objective of this work was to quantify the biomass production, the content and accumulation of nitrogen (N and the carbon/nitrogen (C/N relation in monocultures of sorghum (Sorghum bicolor and corn (Zea mays, and intercrops with pigeon pea (Cajanus cajan, sun hemp (Crotalaria juncea, white lupine (Lupinus albus, sunflower (Helianthus annuus and turnip forage (Raphanus sativus, managed in different stages. The experiment was carried out from March to July 2008, in a Haplic Acrisol, medium texture, under no-tillage. A randomized complete block design, with four replicates and split plots with the

Phase transitions of doped carbon in CrCN coatings with modified mechanical and tribological properties via filtered cathodic vacuum arc deposition

Energy Technology Data Exchange (ETDEWEB)

Guan, J.J. [Faculty of Materials and Energy, Southwest University, Chongqing 400715 (China); Wang, H.Q. [College of Nuclear Science and Technology, Beijing Normal University, Beijing 100875 (China); Qin, L.Z., E-mail: qin8394@163.com [Faculty of Materials and Energy, Southwest University, Chongqing 400715 (China); Liao, B.; Liang, H. [College of Nuclear Science and Technology, Beijing Normal University, Beijing 100875 (China); Li, B. [Faculty of Materials and Energy, Southwest University, Chongqing 400715 (China)

2017-04-15

The CrCN coatings were fabricated onto Si (1 1 1) wafers and SUS304 stainless steel plates using filtered cathodic vacuum arc deposition (FCVAD) technique under different flow ratios of N{sub 2}/C{sub 2}H{sub 2} gas mixture. The morphology, crystalline structure and chemical composition of the coatings were characterized. It was found that the grain size reduce with increasing carbon content, which makes the CrCN coatings refined and smooth. The quasi-one-dimensional carbolite phase was also found in CrN host lattice with C{sub 2}H{sub 2} content ranging from 5% to 20%, and it will be evolved into amorphous carbon and amorphous CN{sub x} phases as C{sub 2}H{sub 2} content exceeds 20%. Moreover, we examined the mechanical and tribological properties of the CrCN coatings, and the experimental results confirmed that the friction coefficient of the coatings descend to the lowest value as 0.39 with 30% C{sub 2}H{sub 2} content, due to the graphite (sp{sup 2} C−C) phase embed in CrN host lattice; while the chromium carbon (Cr{sub 3}C{sub 2}) and diamond (sp{sup 3} C−C) phases may give rise to the increase of the coating hardness with the highest value at 23.97 GPa under 20% C{sub 2}H{sub 2} content.

Searching for Stable SinCn Clusters: Combination of Stochastic Potential Surface Search and Pseudopotential Plane-Wave Car-Parinello Simulated Annealing Simulations

Directory of Open Access Journals (Sweden)

Larry W. Burggraf

2013-07-01

Full Text Available To find low energy SinCn structures out of hundreds to thousands of isomers we have developed a general method to search for stable isomeric structures that combines Stochastic Potential Surface Search and Pseudopotential Plane-Wave Density Functional Theory Car-Parinello Molecular Dynamics simulated annealing (PSPW-CPMD-SA. We enhanced the Sunders stochastic search method to generate random cluster structures used as seed structures for PSPW-CPMD-SA simulations. This method ensures that each SA simulation samples a different potential surface region to find the regional minimum structure. By iterations of this automated, parallel process on a high performance computer we located hundreds to more than a thousand stable isomers for each SinCn cluster. Among these, five to 10 of the lowest energy isomers were further optimized using B3LYP/cc-pVTZ method. We applied this method to SinCn (n = 4–12 clusters and found the lowest energy structures, most not previously reported. By analyzing the bonding patterns of low energy structures of each SinCn cluster, we observed that carbon segregations tend to form condensed conjugated rings while Si connects to unsaturated bonds at the periphery of the carbon segregation as single atoms or clusters when n is small and when n is large a silicon network spans over the carbon segregation region.

Investigation of the direct runoff generation mechanism for the analysis of the SCS-CN method applicability to a partial area experimental watershed

Science.gov (United States)

Soulis, K. X.; Valiantzas, J. D.; Dercas, N.; Londra, P. A.

2009-05-01

The Soil Conservation Service Curve Number (SCS-CN) method is widely used for predicting direct runoff volume for a given rainfall event. The applicability of the SCS-CN method and the direct runoff generation mechanism were thoroughly analysed in a Mediterranean experimental watershed in Greece. The region is characterized by a Mediterranean semi-arid climate. A detailed land cover and soil survey using remote sensing and GIS techniques, showed that the watershed is dominated by coarse soils with high hydraulic conductivities, whereas a smaller part is covered with medium textured soils and impervious surfaces. The analysis indicated that the SCS-CN method fails to predict runoff for the storm events studied, and that there is a strong correlation between the CN values obtained from measured runoff and the rainfall depth. The hypothesis that this correlation could be attributed to the existence of an impermeable part in a very permeable watershed was examined in depth, by developing a numerical simulation water flow model for predicting surface runoff generated from each of the three soil types of the watershed. Numerical runs were performed using the HYDRUS-1D code. The results support the validity of this hypothesis for most of the events examined where the linear runoff formula provides better results than the SCS-CN method. The runoff coefficient of this formula can be taken equal to the percentage of the impervious area. However, the linear formula should be applied with caution in case of extreme events with very high rainfall intensities. In this case, the medium textured soils may significantly contribute to the total runoff and the linear formula may significantly underestimate the runoff produced.

Investigation of the direct runoff generation mechanism for the analysis of the SCS-CN method applicability to a partial area experimental watershed

Directory of Open Access Journals (Sweden)

K. X. Soulis

2009-05-01

Full Text Available The Soil Conservation Service Curve Number (SCS-CN method is widely used for predicting direct runoff volume for a given rainfall event. The applicability of the SCS-CN method and the direct runoff generation mechanism were thoroughly analysed in a Mediterranean experimental watershed in Greece. The region is characterized by a Mediterranean semi-arid climate. A detailed land cover and soil survey using remote sensing and GIS techniques, showed that the watershed is dominated by coarse soils with high hydraulic conductivities, whereas a smaller part is covered with medium textured soils and impervious surfaces. The analysis indicated that the SCS-CN method fails to predict runoff for the storm events studied, and that there is a strong correlation between the CN values obtained from measured runoff and the rainfall depth. The hypothesis that this correlation could be attributed to the existence of an impermeable part in a very permeable watershed was examined in depth, by developing a numerical simulation water flow model for predicting surface runoff generated from each of the three soil types of the watershed. Numerical runs were performed using the HYDRUS-1D code. The results support the validity of this hypothesis for most of the events examined where the linear runoff formula provides better results than the SCS-CN method. The runoff coefficient of this formula can be taken equal to the percentage of the impervious area. However, the linear formula should be applied with caution in case of extreme events with very high rainfall intensities. In this case, the medium textured soils may significantly contribute to the total runoff and the linear formula may significantly underestimate the runoff produced.

Vibrational frequencies and structural investigation of (M(CN)4)2- (M Cd, Hg and Zn) ions

International Nuclear Information System (INIS)

Gurkan, Keshan; Tomas, Polivka; Cemal, Parlak; Mustafa, Shenyel

2011-01-01

The normal mode frequencies and corresponding vibrational assignments of tetracyanometallate (II) ions ([M(CN) 4 ] 2 -, M = Cd, Hg and Zn) have been theoretically examined by means of standard quantum chemical techniques. All normalmodes have been successfully assigned to one of six types of motion utilizing the T d symmetry of M(CN) 4 2 -. Calculations have been performed at the Becke-3-Lee-Yang-Parr (B3LYP) density functional method using the Lanl2dz effective core basis set. Furthermore, reliable vibrational assignments have been made on the basis of potential energy distribution (PED) calculated and the thermodynamics functions, highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) of the title ions have been predicted together with their infrared intensities and Raman activities. Theoretical results have been successfully compared against available experimental data

Solvent extraction of anionic chelate complexes of lanthanum(III), europium(III), lutetium(III), scandium(III), and indium(III) with 2-thenoyltrifluoroacetone as ion-pairs with tetrabutylammonium ions

International Nuclear Information System (INIS)

Noro, Junji; Sekine, Tatsuya.

1992-01-01

The solvent extraction of lanthanum(III), europium(III), lutetium(III), scandium(III), and indium(III) in 0.1 mol dm -3 sodium nitrate solutions with 2-thenoyltrifluoroacetone (Htta) in the absence and presence of tetrabutylammonium ions (tba + ) into carbon tetrachloride was measured. The extraction of lanthanum(III), europium(III), and lutetium(III) was greatly enhanced by the addition of tba + ; this could be explained in terms of the extraction of a ternary complex, M(tta) 4 - tba + . However, the extractions of scandium(III) and indium(III) were nearly the same when tba + was added. The data were treated on the basis of the formation equilibrium of the ternary complex from the neutral chelate, M(tta) 3 , with the extracted ion-pairs of the reagents, tta - tba + , in the organic phase. It was concluded that the degree of association of M(tta) 3 with the ion-pair, tta - tba + , is greater in the order La(tta) 3 ≅ Eu(tta) 3 > Lu(tta) 3 , or that the stability of the ternary complex in the organic phase is higher in the order La(tta) 4 - tba + ≅ Eu(tta) 4 - tba + > Lu(tta) 4 - tba + . This is similar to those of adduct metal chelates of Htta with tributylphosphate (TBP) in synergistic extraction systems. (author)

Strong ligand field effects of blue phosphorescent mono-cyclometalated iridium(III) complexes

Energy Technology Data Exchange (ETDEWEB)

Ham, Ho Wan [Department of Information Display, Hongik University, Seoul, 121-791 (Korea, Republic of); Jung, Kyung Yoon [International Design School for Advanced Studies, Hongik University, Seoul 121-791 (Korea, Republic of); Kim, Young Sik, E-mail: youngkim@hongik.ac.k [Department of Information Display, Hongik University, Seoul, 121-791 (Korea, Republic of)

2010-09-01

A series of mono-cyclometalated blue phosphorescent iridium(III) complexes with two phosphines trans to each other and two cis-ancillary ligands, such as Ir(F{sub 2}Meppy)(PPhMe{sub 2}){sub 2}(H)(Cl), [Ir(F{sub 2}Meppy)(PPhMe{sub 2}){sub 2}(H)(NCMe)]{sup +} and Ir(F{sub 2}Meppy)(PPhMe{sub 2}){sub 2}-(H)(CN), [F{sub 2}Meppy = 2-(2',4'-difluorophenyl)-4-methyl-pyridine] were synthesized and studied to tune the phosphorescence wavelength to the deep blue region and to enhance the luminescence efficiencies. We investigate the electron-withdrawing capabilities of ancillary ligands using the DFT and TD-DFT calculations on the ground and excited states of the three complexes to gain insight into the factors responsible for the emission color change and the different luminescence efficiency. Reducing the molecular weight of phosphine ligand with PPhMe{sub 2} leads to a strategy of the efficient deep blue organic light-emitting devices (OLED) by thermal processing instead of the solution processing. The electron-withdrawing difluoro group substituted on the phenyl ring and the cyano strong field ancillary ligand in the trans position to the carbon atom of phenyl ring increased HOMO-LUMO gap and achieved the hypsochromic shift in emission color. As a result, the maximum emission spectra of Ir(F{sub 2}Meppy)(PPhMe{sub 2}){sub 2}(H)(Cl), [Ir(F{sub 2}Meppy)(PPhMe{sub 2}){sub 2}(H)-(NCMe)]{sup +} and Ir(F{sub 2}Meppy)(PPh-Me{sub 2}){sub 2} (H)(CN) were in the ranges of 446, 440, 439 nm, respectively.

Scaling analysis of [Fe(pyrazole){sub 4}]{sub 2}[Nb(CN){sub 8}] molecular magnet

Energy Technology Data Exchange (ETDEWEB)

Konieczny, P., E-mail: piotr.konieczny@ifj.edu.pl [Institute of Nuclear Physics, Polish Academy of Sciences, Radzikowskiego 152, 31-342 Kraków (Poland); Pełka, R.; Zieliński, P.M. [Institute of Nuclear Physics, Polish Academy of Sciences, Radzikowskiego 152, 31-342 Kraków (Poland); Pratt, F.L. [ISIS Facility, Rutherford Appleton Laboratory, Chilton, Oxfordshire OX11 0QX (United Kingdom); Pinkowicz, D.; Sieklucka, B. [Department of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow (Poland); Wasiutyński, T. [Institute of Nuclear Physics, Polish Academy of Sciences, Radzikowskiego 152, 31-342 Kraków (Poland)

2013-10-15

The critical behaviour of the three dimensional (3D) molecular magnet {[Fe"I"I(pirazol)_4]_2[Nb"I"V(CN)_8]·4H_2O}{sub n} has been studied with the use of experimental techniques such as ac magnetometry and zero field μSR spectroscopy. The sample orders magnetically below T{sub c}=7.8 K. The measurements allowed to determine static exponents β, γ, and the dynamic exponent w. The resulting exponent values indicate that the studied system belongs to the universality class of the 3D Heisenberg model. - Highlights: • The critical behaviour of {[Fe"I"I(pirazol)_4]_2[Nb"I"V(CN)_8]∙4H_2O}{sub n} has been studied. • Critical exponents β, γ, and w were obtained from ac magnetometry and ZF µSR data. • All obtained values of critical exponents are close to the 3D Heisenberg model.

Synthesis and characterization of a multifunctional inorganic-organic hybrid mixed-valence copper(I/II) coordination polymer: {[CuCN][Cu(isonic)2]}n

Science.gov (United States)

Liu, Dong-Sheng; Chen, Wen-Tong; Ye, Guang-Ming; Zhang, Jing; Sui, Yan

2017-12-01

A new multifunctional mixed-valence copper(I/II) coordination polymer, {[CuCN][Cu(isonic)2]}n(1) (Hisonic = isonicotinic acid), was synthesized by treating isonicotinic acid and 5-amino-tetrazolate (Hatz = 5-amino-tetrazolate) with copper(II) salts under hydrothermal conditions, and characterized by elemental analysis, infrared spectroscopy, and single crystal X-ray diffraction, respectively. The X-ray diffraction analysis reveals that compound exhibit noncentrosymmetric polar packing arrangement. It is three-dimensional (3D) framework with (3,5)-connected 'seh-3' topological network constructed from metal organic framework {[Cu(isonic)2]}n and the inorganic linear chain{Cu(CN)}n subunits. A remarkable feature of 1 is the rhombic open channels that are occupied by a linear chain of {Cu(CN)}n. Impressively compound 1 displays not only a second harmonic generation (SHG) response, but also a ferroelectric behavior and magnetic properties.

Superconductivity at 2.8 K and 1.5 kbar in κ-(BEDT-TTF)2Cu2(CN)3: The first organic superconductor containing a polymeric copper cyanide anion

International Nuclear Information System (INIS)

Geiser, Urs; Wang Hau, H.; Carlson, K.D.; Williams, J.M.; Charlier, H.A. Jr.; Heindl, J.E.; Yaconi, G.A.; Love, B.J.; Lathrop, M.W.; Schirber, J.E.; Overmyer, D.L.; Ren, Jingquing; Whangbo, Myung-Hwan

1991-01-01

Attempts to synthesize new k-phase superconductors have concentrated on ET salts with complex anions composed of Cu(I) or Ag(I) metal ions and pseudohalide anions. The 'targeted anion approach', by use of a preformed anion found in KCu 2 (CN) 3 .H 2 O and the presence of trace amounts of water, led to the discovery of the first copper-cyanide containing superconductor, K-(ET) 2 Cu 2 (CN) 3 . The crystal structure, superconducting properties, and band electronic structure are described in this article. The complex k-(ET) 2 Cu 2 (CN) 3 is in many ways similar to the superconductor K-(ET) 2 Cu[N(CN) 2 ]Cl, the superconductor with the highest T c reported to date. 28 refs., 3 figs

Development of LIFE4-CN: a combined code for steady-state and transient analyses of advanced LMFBR fuels

International Nuclear Information System (INIS)

Liu, Y.Y.; Zawadzki, S.; Billone, M.C.; Nayak, U.P.; Roth, T.

1979-01-01

The methodology used to develop the LMFBR carbide/nitride fuels code, LIFE4-CN, is described in detail along with some subtleties encountered in code development. Fuel primary and steady-state thermal creep have been used as an example to illustrate the need for physical modeling and the need to recognize the importance of the materials characteristics. A self-consistent strategy for LIFE4-CN verification against irradiation data has been outlined with emphasis on the establishment of the gross uncertainty bands. These gross uncertainty bands can be used as an objective measure to gauge the overall success of the code predictions. Preliminary code predictions for sample steady-state and transient cases are given

Sparkle/PM3 for the modeling of europium(III), gadolinium(III), and terbium(III) complexes

International Nuclear Information System (INIS)

Freire, Ricardo O.; Rocha, Gerd B.; Simas, Alfredo M.

2009-01-01

The Sparkle/PM3 model is extended to europium(III), gadolinium(III), and terbium(III) complexes. The validation procedure was carried out using only high quality crystallographic structures, for a total of ninety-six Eu(III) complexes, seventy Gd(III) complexes, and forty-two Tb(III) complexes. The Sparkle/PM3 unsigned mean error, for all interatomic distances between the trivalent lanthanide ion and the ligand atoms of the first sphere of coordination, is: 0.080 A for Eu(III); 0.063 A for Gd(III); and 0.070 A for Tb(III). These figures are similar to the Sparkle/AM1 ones of 0.082 A, 0.061 A, and 0.068 A respectively, indicating they are all comparable parameterizations. Moreover, their accuracy is similar to what can be obtained by present-day ab initio effective core potential full geometry optimization calculations on such lanthanide complexes. Finally, we report a preliminary attempt to show that Sparkle/PM3 geometry predictions are reliable. For one of the Eu(III) complexes, BAFZEO, we created hundreds of different input geometries by randomly varying the distances and angles of the ligands to the central Eu(III) ion, which were all subsequently fully optimized. A significant trend was unveiled, indicating that more accurate local minima geometries cluster at lower total energies, thus reinforcing the validity of sparkle model calculations. (author)

Animated Dreamsi peaauhind läks Tšiili

Index Scriptorium Estoniae

2009-01-01

Pimedate Ööde 13. filmifestivali teise alafestivali Animated Dreams auhinnasaajad : võitis Cristobal Leoni, Niles Atallah' ja Joaquin Cocina "Lucia", Anoba nominatsiooni sai Kaspar Jancise "Krokodill"

Interrelationship of Cn2 & Eddy Dissipation rate based on Scintillometer and Doppler Lidar observations in complex terrain during the Perdigao Campaign 2017

Science.gov (United States)

Creegan, E. D.; Krishnamurthy, R.; Hocut, C. M.; Pattantyus, A.; Leo, L. S.; Wang, Y.; Fernando, H. J.; Bariteau, L.

2017-12-01

The Perdigao campaign is a joint EU/US science project designed to provide information on flow field(s) over complex terrain and through wind turbines at unprecedented high spatial and temporal resolution. The goal is to improve wind energy physics and overcome the current deficiencies of wind resource models. Topographically the Perdigao location is an expansion of the "double hill in crossflow", consisting of two parallel ridges along the NW-SE direction. The site was heavily instrumented with an array of towers (with multiple transects along the valley and across two ridges) and a large suite of ground based and aerial remote sensing platforms. On the outflow side of the NW ridge a scintillometer was emplaced with the line-of-sight (LOS) running adjacent to the towers comprising the NE transect from the ridgetop down to the base. Scanning lidars were placed at both ends of this LOS. Other instruments included a tethered lifting system (TLS), sodar, microwave radiometer, an energy budget flux tower and radiosonde releases. Scintillomoter data provides a quantitative measure of the intensity of optical turbulence, through the refractive index structure parameter, Cn2, where averaged Cn2 is often determined as a function of local differences in temperature, moisture, and wind velocity at discrete points. The refractive index structure parameter is also a function of the inner (dissipation) and outer (energy producing) turbulent scales. The scintillometer directly gives path averaged Cn2 and Eddy Dissipation rate along the LOS. Coplanar scans along the same path were synchronized using two scanning coherent Doppler lidars. Algorithms have been developed to estimate both eddy dissipation rate and Cn2 from Doppler lidar data effectively creating a new lidar data product. Additionally, from TLS measurements, Cn2 and dissipation rate are calculated using the high frequency spectra of the hot-wire sensor. In this work, measurements of Cn2 and Eddy Dissipation rate

C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex.

Science.gov (United States)

Man, Wai-Lun; Xie, Jianhui; Pan, Yi; Lam, William W Y; Kwong, Hoi-Ki; Ip, Kwok-Wa; Yiu, Shek-Man; Lau, Kai-Chung; Lau, Tai-Chu

2013-04-17

We report experimental and computational studies of the facile oxidative C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex. We provide evidence that the initial step involves nucleophilic attack of aniline at the nitrido ligand of the ruthenium complex, which is followed by proton and electron transfer to afford a (salen)ruthenium(II) diazonium intermediate. This intermediate then undergoes unimolecular decomposition to generate benzene and N2.

Desulfurization of organic sulfur from a subbituminous coal by electron-transfer process with K{sub 4}(Fe(CN){sub 6})

Energy Technology Data Exchange (ETDEWEB)

Dipu Borah [Pragjyotika J College, Titabar (India). Department of Chemistry

2006-02-01

The desulfurization reaction involving direct electron transfer from potassium ferrocyanide, K{sub 4}(Fe(CN){sub 6}), successfully removed organic sulfur from a subbituminous coal. The temperature variation of desulfurization revealed that increase of temperature enhanced the level of sulfur removal. Moreover, the desulfurization reaction was found to be dependent on the concentration of K{sub 4}(Fe(CN){sub 6}). Gradual increase in the concentration of K{sub 4}(Fe(CN){sub 6}) raised the magnitude of desulfurization, but at higher concentration the variation was not significant. The removal of organic sulfur from unoxidized coal slightly increased with reduced particle size. Desulfurization from oxidized coals (prepared by aerial oxidation) revealed a higher level of sulfur removal in comparison to unoxidized coal. Highest desulfurization of 36.4 wt % was obtained at 90{sup o}C and 0.1 M concentration of K{sub 4}(Fe(CN){sub 6}) in the 100-mesh size oxidized coal prepared at 200{sup o}C. Model sulfur compound study revealed that aliphatic types of sulfur compounds are primarily responsible for desulfurization. Because of higher stability, thiophene and condensed thiophene-type of compounds perhaps remained unaffected by the electron-transfer agent. Infrared study revealed the formation of oxidized sulfur compounds (sulfoxide, sulfone, sulfonic acid, etc.) in the oxidized coals. The desulfurization reaction in different systems is well-represented by the pseudo-first-order kinetic model. Application of the transition state theory indicated that the desulfurization reaction proceeds with the absorption of heat (endothermic reaction) and is nonspontaneous in nature. 53 refs., 6 figs., 3 tabs.

Investigation of the direct runoff generation mechanism for the analysis of the SCS-CN method applicability to a partial area experimental watershed

OpenAIRE

Soulis, K. X.; Valiantzas, J. D.; Dercas, N.; Londra, P. A.

2009-01-01

The Soil Conservation Service Curve Number (SCS-CN) method is widely used for predicting direct runoff volume for a given rainfall event. The applicability of the SCS-CN method and the direct runoff generation mechanism were thoroughly analysed in a Mediterranean experimental watershed in Greece. The region is characterized by a Mediterranean semi-arid climate. A detailed land cover and soil survey using remote sensing and GIS techniques, showed that the watershed is dominated by coarse soils...

A novel cyanide-selective colorimetric and fluorescent chemosensor: First molecular security keypad lock based on phosphotungstic acid and CN{sup −} inputs

Energy Technology Data Exchange (ETDEWEB)

Tavallali, Hossein, E-mail: Tavallali@pnu.ac.ir; Deilamy-Rad, Gohar; Parhami, Abolfath; Hasanli, Nahid

2014-02-15

Highlights: • Our probe is commercially available with good photo stability and high quantum yield. • Both color and fluorescence change with long emission wavelength in aqueous media. • Characteristics of an ON–OFF–ON fluorescence switch. • The simple receptor for CN{sup -} detection with low detection limit (≪WHO). • Mimic the function of a security keypad lock on sequential addition of PTA and CN{sup −}. -- Abstract: Rhodamine B (Rh{sub B}) an available dye has been developed as novel and efficient colorimetric and fluorometric chemosensor for cyanide ions in an absolutely aqueous media. The UV–vis absorption and fluorescent emission titrations experiments have been employed to study the sensing process. Rh{sub B} could act as an efficient “ON–OFF” fluorescent response for phosphotungstic acid (H{sub 3}PW{sub 12}O{sub 40} or PTA) based on an ion associate process. Also (Rh{sub B}{sup +}){sub 3}·PTA{sup 3−} could operate as an “OFF–ON” fluorescent sensor for cyanide anions based on a ligand substitution process. It has been identified as highly sensitive probe for CN{sup −} which responds at 0.3 and 0.04 μmol L{sup −1} concentration levels by absorption and fluorescent method respectively. Depending upon the sequence of addition of PTA and CN{sup −} ions into the solution, Rh{sub B} could be as a molecular security keypad lock with PTA and CN{sup −} inputs. The ionic inputs to new fluorophore have been mimicked as a superimposed electronic molecular keypad lock. The results were compared successfully (>96%) with the data of a spectrophotometry approved method (EPA 9014-1) for cyanide ions.

Cis-[RuCl(BzCN)(N-N)(P-P)]PF6 complexes: Synthesis and in vitro antitumor activity: (BzCN=benzonitrile; N-N=2,2'-bipyridine; 1,10-phenanthroline; P-P=1,4-bis(diphenylphosphino) butane, 1,2-bis(diphenylphosphino)ethane, or 1,1'-(diphenylphosphino)ferrocene).

Science.gov (United States)

Pereira, Flávia de C; Lima, Benedicto A V; de Lima, Aliny P; Pires, Wanessa C; Monteiro, Thallita; Magalhães, Lorena F; Costa, Wanderson; Graminha, Angélica E; Batista, Alzir A; Ellena, Javier; Siveira-Lacerda, Elisângela de P

2015-08-01

The motivation to use ruthenium complexes in cancer treatment has led our research group to synthesize complexes with this metal and test them against several types of tumor cells, yielding promising results. In this paper the results of biological tests, assessed by the MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay, were carried out on the complexes cis-[RuCl(BzCN)(bipy)(dppe)]PF6 (1), cis-[RuCl(BzCN)(bipy)(dppb)]PF6 (2), cis-[RuCl(BzCN)(bipy)(dppf)]PF6 (3) and cis-[RuCl(BzCN)(phen)(dppb)]PF6 (4) which are described [BzCN = b enzonitrile; bipy = 2,2'-bipyridine; phen = 1,10-phenanthroline; dppe = 1,2-bis(diphenylphosphino) ethane; dppb = 1,4-bis-(diphenylphosphino)butane; dppf = 1,1'-bis(diphenylphosphino)ferrocene]. The present study is focused on the cytotoxic activity of complexes (1)-(4) against four tumor cell lines and on the apoptosis and changes in the cell cycle and gene expression observed in the sarcoma 180 (S180) tumor cell line treated with complex (1). The results demonstrated that this complex inhibits S180 cell growth, with an IC50 of 17.02 ± 8.21 μM, while exhibiting lower cytotoxicity (IC50 = 53.73 ± 5.71 μM) towards lymphocytes (normal cells). Flow cytometry revealed that the complex inhibits the growth of tumor cells by inducing apoptosis as evidenced by an increase in the proportion of cells positive for annexin V staining and G0/G1 phase cell-cycle arrest. Further investigation showed that complex (1) induces a drop in the mitochondrial membrane potential and provokes a decrease in Bcl-2 protein expression and increase in caspase 3 activation, while the increased activation of caspase 8 caused a decrease in the gene expression in caspases 3 and 9. Increases in Tp53 and Bax expressions were also observed. Copyright © 2015 Elsevier Inc. All rights reserved.

Uranium (III)-Plutonium (III) co-precipitation in molten chloride

Science.gov (United States)

Vigier, Jean-François; Laplace, Annabelle; Renard, Catherine; Miguirditchian, Manuel; Abraham, Francis

2018-02-01

Co-management of the actinides in an integrated closed fuel cycle by a pyrochemical process is studied at the laboratory scale in France in the CEA-ATALANTE facility. In this context the co-precipitation of U(III) and Pu(III) by wet argon sparging in LiCl-CaCl2 (30-70 mol%) molten salt at 705 °C is studied. Pu(III) is prepared in situ in the molten salt by carbochlorination of PuO2 and U(III) is then introduced as UCl3 after chlorine purge by argon to avoid any oxidation of uranium up to U(VI) by Cl2. The oxide conversion yield through wet argon sparging is quantitative. However, the preferential oxidation of U(III) in comparison to Pu(III) is responsible for a successive conversion of the two actinides, giving a mixture of UO2 and PuO2 oxides. Surprisingly, the conversion of sole Pu(III) in the same conditions leads to a mixture of PuO2 and PuOCl, characteristic of a partial oxidation of Pu(III) to Pu(IV). This is in contrast with coconversion of U(III)-Pu(III) mixtures but in agreement with the conversion of Ce(III).

Uniaxial Negative Thermal Expansion, Negative Linear Compressibility, and Negative Poisson's Ratio Induced by Specific Topology in Zn[Au(CN)2]2.

Science.gov (United States)

Wang, Lei; Luo, Hubin; Deng, Shenghua; Sun, Ying; Wang, Cong

2017-12-18

The well-known idea of "structure determines properties" can be understood profoundly in the case of hexagonal zinc dicyanometalate. Using density functional theory (DFT) calculations, we show the uniaxial negative thermal expansion (NTE) and negative linear compressibility (NLC) properties of Zn[Au(CN) 2 ] 2 . The temperature dependence of phonon frequencies within the quasi-harmonic approximation (QHA) is investigated. The abnormal phonon hardening (frequency increase on heating) is detected in the ranges of 0-225, 320-345, and 410-430 cm -1 , which can be indicative of the unusual physical properties of Zn[Au(CN) 2 ] 2 . Due to the significance of low-energy phonon frequencies in Zn[Au(CN) 2 ] 2 , in this work, the corresponding vibrational mode of the lowest-frequency optical phonon at the zone center is analyzed. The specific topology of a springlike framework that will produce the effects of a compressed spring on heating and an extended spring under hydrostatic pressure is identified and leads to the coexistence of uniaxial-NTE and NLC behaviors in Zn[Au(CN) 2 ] 2 . The distinguishing phonon group velocity along the a axis and c axis facilitates different responses for both the axes under temperature and hydrostatic pressure field. Through an analysis and visualization of the spatial dependence of elastic tensors, it is found that a negative Poisson's ratio (NPR) is presented in all projection planes due to the specific topology.

Tribological behavior and self-healing functionality of TiNbCN-Ag coatings in wide temperature range

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Bondarev, A. V.; Kiryukhantsev-Korneev, Ph. V.; Levashov, E. A.; Shtansky, D. V.

2017-02-01

Ag- and Nb-doped TiCN coatings with about 2 at.% of Nb and Ag contents varied between 4.0 and 15.1 at.% were designed as promising materials for tribological applications in a wide temperature range. We report on the structure, mechanical, and tribological properties of TiNbCN-Ag coatings fabricated by simultaneous co-sputtering of TiC0.5 + 10%Nb2C and Ag targets in comparison with those of Ag-free coating. The tribological characteristics were evaluated during constant-temperature tests both at room temperature and 300 °C, as well as during dynamic temperature ramp tests in the range of 25-700 °C. The coating structure and elemental composition were studied by means of X-ray diffraction, scanning and transmission electron microscopy, and glow discharge optical emission spectroscopy. The coating microstructures and elemental compositions inside wear tracks, as well as the wear products, were examined by scanning electron microscopy, energy-dispersive spectroscopy, and Raman spectroscopy. We demonstrate that simultaneous alloying with Nb and Ag permits to overcome the main drawbacks of TiCN coatings such as their relatively high values of friction coefficient at elevated temperatures and low oxidation resistance. It is shown that a relatively high amount of Ag (15 at.%) is required to provide enhanced tribological behavior in a wide temperature range of 25-700 °C. In addition, the prepared Ag-doped coatings demonstrated active oxidation protection and self-healing functionality due to the segregation of Ag metallic particles in damage areas such as cracks, pin-holes, or oxidation sites.

8-12 GHz Radio Observations of Flare Activity On M dwarf CN Leo

Science.gov (United States)

Wofford, Alia; Villadsen, Jackie; Quintana, Elisa; Barclay, Thomas; Thackeray, Beverly

2018-01-01

Red dwarfs are cool stars that make up 70% of all stars. Red dwarfs can be utilized to detect potentially habitable planets but they have particularly strong magnetic activity that can be detrimental to orbiting planets’ atmospheres and habitability. A coronal mass ejection (CME) is an eruption of magnetized plasma from the star that is ejected into the interplanetary medium which can erode a planet’s atmosphere daily. Based on the sun CMEs are expected to produce very bright radio bursts along with optical flares. We are using M dwarf CN Leo, a well studied flare star that was in the K2 campaign field in summer 2017, as a template to understand the relationship between radio and optical flares and the space weather conditions impacting M dwarf planets. Using radio frequencies ranging from 0.22 GHz-12 GHz we search for simultaneous radio bursts and optical flares to infer if CMEs, flares or aurorae are occurring on the star. I will present the 8-12 GHz radio data from eight 1.5-hour observations with simultaneous optical data. CN Leo produced a bright non-thermal radio flare that lasted approximately for a day during two consecutive observations, with a gyrosynchrotron emission mechanism.

Synthesis and characterization of polyureasilazane derived SiCN ceramics

International Nuclear Information System (INIS)

Andronenko, Sergey I.; Stiharu, Ion; Misra, Sushil K.

2006-01-01

Samples of SiCN ceramics were synthesized by thermal treatment of commercially available CERASET TM polyureasilazane, used as liquid-polymer precursor, at pyrolysis temperatures of 1000, 1050, 1100, 1150, and 1200 deg. C. Electron paramagnetic resonance (EPR) signals due to sp 2 -hybridized carbon-related dangling bonds were recorded over the 4-300 K temperature range at X band (9.6 GHz), and the spectra showed the presence of an intense EPR line with g=2.0027 at room temperature for all samples; at liquid helium temperature an additional line was seen present as a shoulder to main line. These two signals are due to carbon-related dangling bonds present as (i) defects on the free-carbon phase and (ii) within the bulk of SiCN ceramic network. The value of the antiferromagnetic exchange constant between dangling bonds in the various samples, not hitherto available in the literature, was estimated from the temperature variation of the EPR linewidth to be anywhere from J=-12 to J=-15 K in the samples synthesized at 1000, 1100, and 1150 deg. C. The EPR linewidth of the samples decreased with increasing pyrolysis temperature of a sample, being 0.07 mT at X band at room temperature for the samples synthesized at 1150 and 1200 deg. C, which can be used potentially as stable g markers, due to their very narrow linewidth. The W-band (95 GHz) room-temperature spectrum of the sample pyrolyzed at 1100 deg. C exhibited only one line consistent with the X-band spectrum. At higher frequency of G band (170 GHz) the EPR spectra are better resolved, clearly showing the presence of a strong (g=2.0027) and a weak (g=2.0032) EPR line at room temperature, and the latter corresponds to the line present at X band as shoulder at liquid-helium temperature. In addition, nuclear magnetic resonance measurements were carried out to confirm the existence of free-carbon phase and oxygen atoms in the samples

Characterization by FTIR and nuclear analytical techniques of CN{sub x} films elaborated by laser ablation; Caracterizacion por FTIR y tecnicas analiticas nucleares de peliculas de CN{sub x} elaboradas por ablacion laser

Energy Technology Data Exchange (ETDEWEB)

Olea M, O.F

2003-07-01

At the present time the technique of deposit of laser ablation is used to produce different types of thin films. At the moment in the National Institute of Nuclear Research (ININ) it is carried out an investigation on the thermoluminescent response of thin films of CN{sub x} with possible application in dosimetry of electromagnetic radiation. Under this context, the present work is part of this investigation and has as objective to characterize thin films of CN{sub x} by means of Infrared spectrometry and nuclear analytical techniques. The deposits were elaborated by laser ablation under different such experimental conditions as: pressure of Nitrogen in the system (3 x 10{sup -3} and 7.5 X 10{sup -2} Torr), Distance target-substrate (3 and 5 cm) and density of incident energy in the target (from 17.5 up to 23.8 J/cm{sup 2}). Graphite of high purity was used like target and the deposits were made on their substrates of intrinsic silicon (100). By means of infrared spectrometry by Fourier Transform (Ftir) the type of bonds which are in the structure of the films of CN{sub x} were determined. The spectra of this type of samples present in general four characteristic bands related with different types of bonds among the elements C, O, H, N such as: C-C, C-N, C-H, N-H, O-H, C=N, C{identical_to}N, among others. It was carried out a semi quantitative study of the samples isolating each band of the total infrared spectra and making a comparison between their intensities and forms. This study allowed to observe that there is a dependence of the structure of the films with regard to the time, since mainly bonds of the type Sp{sup 3} between Hydrogen and Carbon (C-H) they presented a remarkable variation in intensity, increasing as it lapsed the time until reaching to a stabilization where the bonds already not varying. This increase probably is due to the absorption of water of the atmosphere, although one has seen in the literature that the incorporation of this compound in

The mechanism of transition-metal (Cu or Pd)-catalyzed synthesis of benzimidazoles from amidines: theoretical investigation.

Science.gov (United States)

Li, Juan; Gu, Honghong; Wu, Caihong; Du, Lijuan

2014-11-28

In this study, the Cu(OAc)2- and [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines were theoretically investigated using density functional theory calculations. For the Cu-catalyzed system, our calculations supported a four-step-pathway involving C-H activation of an arene with Cu(II) via concerted metalation-deprotonation (CMD), followed by oxidation of the Cu(II) intermediate and deprotonation of the imino group by Cu(III), and finally reductive elimination from Cu(III). In our calculations, the barriers for the CMD step and the oxidation step are the same. The results are different from the ones reported by Fu et al. in which the whole reaction mechanism includes three steps and the CMD step is rate determining. On the basis of the calculation results for the [PdCl2(PhCN)2]-catalyzed system, C-H bond breaking by CMD occurs first, followed by the rate-determining C-N bond formation and N-H deprotonation. Pd(III) species is not involved in the [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines.

(2-Benzoyl-1-phenylethenolato-κ2O,O′bis[2-(1-phenyl-1H-benzimidazol-2-ylphenyl-κC1]iridium(III dichloromethane disolvate

Directory of Open Access Journals (Sweden)

Stanislav I. Bezzubov

2016-12-01

Full Text Available We present here synthesis and crystal structure of a neutral IrIII complex, [Ir(C19H13N22(C15H11O2]·2CH2Cl2 or [Ir(C^N2O^O]·2CH2Cl2, where C^N is 1,2-diphenyl-1H-benzimidazole and O^O is 2-benzoyl-1-phenylethenolate. The coordination sphere of the IrIII atom, located on a twofold rotation axis, is that of a slighlty distorted C2N2O2 octahedron, with the N atoms in a trans configuration. In the crystal, complex molecules assemble through weak C—H...π interactions in the range 2.699 (3–2.892 (3 Å. The solvent CH2Cl2 molecules reside in channels aligned along the a axis and are connected to the complex molecules by C—H...O interactions.

Phonon-electron coupling and tunneling effect on charge transport in organic semi-conductor crystals of Cn-BTBT

Science.gov (United States)

Zhou, Yecheng; Deng, Wei-Qiao; Zhang, Hao-Li

2016-09-01

Cn-[1]benzothieno[3,2-b][1]-benzothiophene (BTBT) crystals show very high hole mobilities in experiments. These high mobilities are beyond existing theory prediction. Here, we employed different quantum chemistry methods to investigate charge transfer in Cn-BTBT crystals and tried to find out the reasons for the underestimation in the theory. It was found that the hopping rate estimated by the Fermi Golden Rule is higher than that of the Marcus theory due to the high temperature approximation and failure at the classic limit. More importantly, molecular dynamics simulations revealed that the phonon induced fluctuation of electronic transfer integral is much larger than the average of the electronic transfer integral itself. Mobilities become higher if simulations implement the phonon-electron coupling. This conclusion indicates that the phonon-electron coupling promotes charge transfer in organic semi-conductors at room temperature.

The Use of Asymptotic Functions for Determining Empirical Values of CN Parameter in Selected Catchments of Variable Land Cover

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Wałęga Andrzej

2017-12-01

Full Text Available The aim of the study was to assess the applicability of asymptotic functions for determining the value of CN parameter as a function of precipitation depth in mountain and upland catchments. The analyses were carried out in two catchments: the Rudawa, left tributary of the Vistula, and the Kamienica, right tributary of the Dunajec. The input material included data on precipitation and flows for a multi-year period 1980–2012, obtained from IMGW PIB in Warsaw. Two models were used to determine empirical values of CNobs parameter as a function of precipitation depth: standard Hawkins model and 2-CN model allowing for a heterogeneous nature of a catchment area.

Decitabine improves progression-free survival in older high-risk MDS patients with multiple autosomal monosomies: results of a subgroup analysis of the randomized phase III study 06011 of the EORTC Leukemia Cooperative Group and German MDS Study Group.

Science.gov (United States)

Lübbert, Michael; Suciu, Stefan; Hagemeijer, Anne; Rüter, Björn; Platzbecker, Uwe; Giagounidis, Aristoteles; Selleslag, Dominik; Labar, Boris; Germing, Ulrich; Salih, Helmut R; Muus, Petra; Pflüger, Karl-Heinz; Schaefer, Hans-Eckart; Bogatyreva, Lioudmila; Aul, Carlo; de Witte, Theo; Ganser, Arnold; Becker, Heiko; Huls, Gerwin; van der Helm, Lieke; Vellenga, Edo; Baron, Frédéric; Marie, Jean-Pierre; Wijermans, Pierre W

2016-01-01

In a study of elderly AML patients treated with the hypomethylating agent decitabine (DAC), we noted a surprisingly favorable outcome in the (usually very unfavorable) subgroup with two or more autosomal monosomies (MK2+) within a complex karyotype (Lübbert et al., Haematologica 97:393-401, 2012). We now analyzed 206 myelodysplastic syndrome (MDS) patients (88 % of 233 patients randomized in the EORTC/GMDSSG phase III trial 06011, 61 of them with RAEBt, i.e. AML by WHO) with cytogenetics informative for MK status.. Endpoints are the following: complete/partial (CR/PR) and overall response rate (ORR) and progression-free (PFS) and overall survival (OS). Cytogenetic subgroups are the following: 63 cytogenetically normal (CN) patients, 143 with cytogenetic abnormalities, 73 of them MK-negative (MK-), and 70 MK-positive (MK+). These MK+ patients could be divided into 17 with a single autosomal monosomy (MK1) and 53 with at least two monosomies (MK2+). ORR with DAC in CN patients: 36.1 %, in MK- patients: 16.7 %, in MK+ patients: 43.6 % (MK1: 44.4 %, MK2+ 43.3 %). PFS was prolonged by DAC compared to best supportive care (BSC) in the CN (hazard ratio (HR) 0.55, 99 % confidence interval (CI), 0.26; 1.15, p = 0.03) and MK2+ (HR 0.50; 99 % CI, 0.23; 1.06, p = 0.016) but not in the MK-, MK+, and MK1 subgroups. OS was not improved by DAC in any subgroup. In conclusion, we demonstrate for the first time in a randomized phase III trial that high-risk MDS patients with complex karyotypes harboring two or more autosomal monosomies attain encouraging responses and have improved PFS with DAC treatment compared to BSC.

FTIR spectroscopic study on the Hofmann -Td- type clathrates: Ni(benzoic acid)2M(CN)4.aniline (M=Zn, Cd, Hg)

International Nuclear Information System (INIS)

Kesan, G.; Kartal, Z.

2010-01-01

The Hofmann-Td-type clathrates formulated as Ni(L) 2 M(CN) 4 .nG where L is a bidentate or a pair of unidentate ligand molecule, M is Zn, Cd or Hg, G is a guest molecule and n is the number of guest molecule. The host lattice of the Hofmann-Td-type clathrates is formed from endless chains of -Ni-L-L-Ni-L-L-Ni- and M(CN) 4 ions arranged between the consecutive crossing -Ni-L-L-Ni-L-L-Ni- chains with the O-ends bound to the Ni metal atoms. These polymeric layers are held in parallel by Van der Walls interaction between ligand molecules. This structure provides α-type cavity. In this study, Ni(Benzoic Acid ) 2M(CN) 4 .Aniline (M = Zn, Cd, Hg) is obtained for the first time by means of chemical methods in powder form and their infrared spectra are reported in range of (4000-400) cm - 1. The spectral data suggest that the new clathrates are similar in structure to the Hofmann-type clathrates.

DFT Simulation of Structural and Optical Properties of 9-Aminoacridine Half-Sandwich Ru(II), Rh(III), and Ir(III) Antitumoral Complexes and Their Interaction with DNA.

Science.gov (United States)

Cerón-Carrasco, José Pedro; Ruiz, José; Vicente, Consuelo; de Haro, Concepción; Bautista, Delia; Zúñiga, José; Requena, Alberto

2017-08-08

In this work, we use DFT-based methods to simulate the chemical structures, optical properties, and interaction with DNA of a recently synthesized chelated C^N 9-aminoacridine arene Ru(II) anticancer agent and two new closely related Rh(III) and Ir(III) complexes using DFT-based methods. Four chemical models and a number of theoretical approaches, which representatively include the PBE0, B97D, ωB97X, ωB97X-D, M06, and M06-L density functionals and the LANL2DZ, def2-SVP, and def2-TZVP basis sets, are tested. The best overall accuracy/cost performance for the optimization process is reached at the ωB97X-D/def2-SVP and M06/def2-SVP levels of theory. Inclusion of explicit solvent molecules (CHCl 3 ) further refines the geometry, while taking into account the crystal network gives no significant improvements of the computed bond distances and angles. The analysis of the excited states reveals that the M06 level matches better the experimental absorption spectra, compared to ωB97X-D. The use of the M06/def2-SVP approach is therefore a well-balanced method to study theoretically the bioactivity of this type of antitumoral complexes, so we couple this TD-DFT approach to molecular dynamics simulations in order to assess their reactivity with DNA. The reported results demonstrate that these drugs could be used to inject electrons into DNA, which might broaden their applications in photoactivated chemotherapy and as new materials for DNA-based electrochemical nanodevices.

Toward structural dynamics: protein motions viewed by chemical shift modulations and direct detection of C'N multiple-quantum relaxation.

Science.gov (United States)

Mori, Mirko; Kateb, Fatiha; Bodenhausen, Geoffrey; Piccioli, Mario; Abergel, Daniel

2010-03-17

Multiple quantum relaxation in proteins reveals unexpected relationships between correlated or anti-correlated conformational backbone dynamics in alpha-helices or beta-sheets. The contributions of conformational exchange to the relaxation rates of C'N coherences (i.e., double- and zero-quantum coherences involving backbone carbonyl (13)C' and neighboring amide (15)N nuclei) depend on the kinetics of slow exchange processes, as well as on the populations of the conformations and chemical shift differences of (13)C' and (15)N nuclei. The relaxation rates of C'N coherences, which reflect concerted fluctuations due to slow chemical shift modulations (CSMs), were determined by direct (13)C detection in diamagnetic and paramagnetic proteins. In well-folded proteins such as lanthanide-substituted calbindin (CaLnCb), copper,zinc superoxide dismutase (Cu,Zn SOD), and matrix metalloproteinase (MMP12), slow conformational exchange occurs along the entire backbone. Our observations demonstrate that relaxation rates of C'N coherences arising from slow backbone dynamics have positive signs (characteristic of correlated fluctuations) in beta-sheets and negative signs (characteristic of anti-correlated fluctuations) in alpha-helices. This extends the prospects of structure-dynamics relationships to slow time scales that are relevant for protein function and enzymatic activity.

The Glory of a Nearby Star

Science.gov (United States)

2001-08-01

Optical Light from a Hot Stellar Corona Detected with the VLT Summary The solar corona is a beautiful sight during total solar eclipses . It is the uppermost region of the extended solar atmosphere and consists of a very hot (over 1 million degrees), tenuous plasma of highly ionised elements that emit strong X-ray radiation. There is also a much weaker coronal emission in the optical part of the spectrum . The Sun is a normal star and X-ray observations from rockets and orbiting X-ray telescopes have shown that many other stars also possess coronae . But due to observational limits of the telescopes available so far, the much fainter optical emission from stellar coronae had never been detected. Now, however, an optical coronal line from iron ions that have lost 12 electrons (Fe XIII) has for the first time been observed in a star other than the Sun . The object, a cool star named CN Leonis , is located at a distance of 8 light-years. This impressive observational feat was performed with the UV-Visual Echelle Spectrograph (UVES) on the VLT 8.2-m KUEYEN telescope at the ESO Paranal Observatory , within a programme by German astronomer Jürgen Schmitt and his collaborators at the University of Hamburg Observatory. The possibility to observe stellar coronae with ground-based telescopes opens up new and exciting research opportunities, including the detailed study of stellar cycles , similar to the 11-year solar period. PR Photo 24a/01 : The solar corona during the August 11, 1999, solar eclipse. PR Photo 24b/01 : The nearby star CN Leonis . PR Photo 24c/01 : Ultraviolet spectrum of CN Leonis , obtained with UVES at VLT KUEYEN. PR Photo 24d/01 : The coronal Fe XIII emission line at 3388 Ångstrom in CN Leonis . The 'coronium' mystery ESO PR Photo 24a/01 ESO PR Photo 24a/01 [Preview - JPEG: 450 x 400 pix - 26k] [Normal - JPEG: 899 x 800 pix - 328k] [HiRes - JPEG: 3000 x 2669 pix - 3.1Mk] Caption : Photo of the solar corona, obtained by Philippe Duhoux (ESO) on August 11

Franklin Medal and Bower prize awarded to C.N. Yang. On the Yang-Mills gauge field theory

International Nuclear Information System (INIS)

Ma Zhongqi

1995-01-01

C.N. Yang was awarded the Benjamin Franklin Medal and 1995 Bower Prize mainly for his fundamental work on nonabelian gauge field theory. A brief introduction to this theory and its important role in the development of physics is given

K3[Fe(CN)6].3H2O supported on silica gel: An efficient and selective ...

Indian Academy of Sciences (India)

Department of Chemistry, Payame Noor University, 19395-4697 Tehran, I. R. of IRAN e-mail: ... K3[Fe(CN)6].3H2O, Silica gel; oxime; aldehyde; ketone. 1. Introduction .... ysis, hydrogenation, etc., using organic and inorganic reagents. Besides ...

A [4Fe-4S]-Fe(CO)(CN)-l-cysteine intermediate is the first organometallic precursor in [FeFe] hydrogenase H-cluster bioassembly

Science.gov (United States)

Rao, Guodong; Tao, Lizhi; Suess, Daniel L. M.; Britt, R. David

2018-05-01

Biosynthesis of the [FeFe] hydrogenase active site (the 'H-cluster') requires the interplay of multiple proteins and small molecules. Among them, the radical S-adenosylmethionine enzyme HydG, a tyrosine lyase, has been proposed to generate a complex that contains an Fe(CO)2(CN) moiety that is eventually incorporated into the H-cluster. Here we describe the characterization of an intermediate in the HydG reaction: a [4Fe-4S][(Cys)Fe(CO)(CN)] species, 'Complex A', in which a CO, a CN- and a cysteine (Cys) molecule bind to the unique 'dangler' Fe site of the auxiliary [5Fe-4S] cluster of HydG. The identification of this intermediate—the first organometallic precursor to the H-cluster—validates the previously hypothesized HydG reaction cycle and provides a basis for elucidating the biosynthetic origin of other moieties of the H-cluster.

FITOCENOSIS EN LOS MOGOTES DE LA GRAN MESETA DE GUANTÁNAMO, CUBA ORIENTAL

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Reyes Orlando

2013-07-01

Full Text Available Los mogotes de la Gran Meseta de Guantánamo están constituidos por calizas durasde la Formación Charco Redondo. La temperatura del aire varía entre 22 y 240C yllueve de 1 200 a 1 400 mm al año. Mediante la metodología de la Escuela Zurich- Montpellier se describe un nuevo orden, Coccothrinaci leonis - Guapiretaliarufescentis, con su alianza Coccothrinaci leonis - Guapirion rufescentis y tresasociaciones. Bactrio cubensis - Podocarpodetum ekmanii y Phyllantho epiphyllanthi- Tabebuietum myrtifoliae que se establecen en la parte superior de los mogotes y laasociación Pileo fruticulosae - Thelypteridetum alatae en fragmentos verticales, lasdos primeras tienen una bien desarrollada estera radical donde se produce el reciclajede nutrientes de este ecosistema

A localized surface plasmon resonance (LSPR) immunosensor for CRP detection using 4-chloro-1-naphtol (4-CN) precipitation

Science.gov (United States)

Ha, Su-Ji; Park, Jin-Ho; Byun, Ju-Young; Ahn, Young-Deok; Kim, Min-Gon

2017-07-01

In this study, C-reactive protein (CRP) was detected by monitoring of LSPR shift promoted by precipitation of 4-chloro-1-naphthol (4-CN). The precipitation occurred by horseradish peroxide (HRP) catalyst which is modified at CRP-detection antibody utilized in sandwich enzyme-linked immunosorbent assay (ELISA) on gold nano bipyramid (GNBP) substrate. Due to 4-CN precipitates which are located nearby the surface of GNBP, local refractive index (RI) and molecular density were greatly increased. This phenomenon eventually induced strong spectral red-shift of absorption band of GNBP. An excellent linear relationship (R2=0.9895) between the LSPR shift and CRP concentration was obtained in the range from 100 pg/mL to 100 ng/mL and limit of detection (LOD) was reached to 87 pg/mL.

Thermal expansion in 3d-metal Prussian Blue Analogs-A survey study

International Nuclear Information System (INIS)

Adak, Sourav; Daemen, Luke L.; Hartl, Monika; Williams, Darrick; Summerhill, Jennifer; Nakotte, Heinz

2011-01-01

We present a comprehensive study of the structural properties and the thermal expansion behavior of 17 different Prussian Blue Analogs (PBAs) with compositions M II 3 [(M') III (CN) 6 ] 2 .nH 2 O and M II 2 [Fe II (CN) 6 ].nH 2 O, where M II =Mn, Fe, Co, Ni, Cu and Zn, (M') III =Co, Fe and n is the number of water molecules, which range from 5 to 18 for these compounds. The PBAs were synthesized via standard chemical precipitation methods, and temperature-dependent X-ray diffraction studies were performed in the temperature range between -150 deg. C (123 K) and room-temperature. The vast majority of the studied PBAs were found to crystallize in cubic structures of space groups Fm3-bar m, F4-bar 3m and Pm3-bar m. The temperature dependence of the lattice parameters was taken to compute an average coefficient of linear thermal expansion in the studied temperature range. Of the 17 compounds, 9 display negative values for the average coefficient of linear thermal expansion, which can be as large as 39.7x 1 0 -6 K -1 for Co 3 [Co(CN) 6 ] 2 .12H 2 O. All of the M II 3 [Co III (CN) 6 ] 2 .nH 2 O compounds show negative thermal expansion behavior, which correlates with the Irving-Williams series for metal complex stability. The thermal expansion behavior for the PBAs of the M II 3 [Fe III (CN) 6 ] 2 .nH 2 O family are found to switch between positive (for M=Mn, Co, Ni) and negative (M=Cu, Zn) behavior, depending on the choice of the metal cation (M). On the other hand, all of the M II 2 [Fe II (CN) 6 ].nH 2 O compounds show positive thermal expansion behavior. - Graphical Abstract: The structure of Prussian Blue analogs (PBAs) consists of two types of metal centered octahedral units connected by cyanide ligand. Lattice and interstitial water molecules are present in these framework structures. All the PBAs of the M 3 [Co(CN) 6 ] 2 .nH 2 O family show negative thermal expansion (NTE) behavior. The lattice parameters and magnitude of NTE correlates inversely with the Irving

Framework for event-based semidistributed modeling that unifies the SCS-CN method, VIC, PDM, and TOPMODEL

Science.gov (United States)

Bartlett, M. S.; Parolari, A. J.; McDonnell, J. J.; Porporato, A.

2016-09-01

Hydrologists and engineers may choose from a range of semidistributed rainfall-runoff models such as VIC, PDM, and TOPMODEL, all of which predict runoff from a distribution of watershed properties. However, these models are not easily compared to event-based data and are missing ready-to-use analytical expressions that are analogous to the SCS-CN method. The SCS-CN method is an event-based model that describes the runoff response with a rainfall-runoff curve that is a function of the cumulative storm rainfall and antecedent wetness condition. Here we develop an event-based probabilistic storage framework and distill semidistributed models into analytical, event-based expressions for describing the rainfall-runoff response. The event-based versions called VICx, PDMx, and TOPMODELx also are extended with a spatial description of the runoff concept of "prethreshold" and "threshold-excess" runoff, which occur, respectively, before and after infiltration exceeds a storage capacity threshold. For total storm rainfall and antecedent wetness conditions, the resulting ready-to-use analytical expressions define the source areas (fraction of the watershed) that produce runoff by each mechanism. They also define the probability density function (PDF) representing the spatial variability of runoff depths that are cumulative values for the storm duration, and the average unit area runoff, which describes the so-called runoff curve. These new event-based semidistributed models and the traditional SCS-CN method are unified by the same general expression for the runoff curve. Since the general runoff curve may incorporate different model distributions, it may ease the way for relating such distributions to land use, climate, topography, ecology, geology, and other characteristics.

Hallucinogen-like effects of 2-([2-(4-cyano-2,5-dimethoxyphenyl) ethylamino]methyl)phenol (25CN-NBOH), a novel N-benzylphenethylamine with 100-fold selectivity for 5-HT2A receptors, in mice

DEFF Research Database (Denmark)

Fantegrossi, William E; Gray, Bradley W; Bailey, Jessica M

2015-01-01

RATIONALE: 2-([2-(4-cyano-2,5-dimethoxyphenyl)ethylamino]methyl)phenol (25CN-NBOH) is structurally similar to N-benzyl substituted phenethylamine hallucinogens currently emerging as drugs of abuse. 25CN-NBOH exhibits dramatic selectivity for 5-HT2A receptors in vitro, but has not been behaviorally...... an intermediate degree of generalization (55 %) for the DOI training dose, and these interoceptive effects were attenuated by M100907. Finally, 25CN-NBOH did not generalize to M100907 at any dose, but ketanserin fully substituted in these animals. CONCLUSIONS: 25CN-NBOH was behaviorally active, but less effective...

Physical Properties of (NH4)2Pt(CN)4[Clo.42].3H2O: A new Quasi-One-Dimensional Conductor

DEFF Research Database (Denmark)

Carneiro, Kim; Petersen, A. S.; Underhill, A. E.

1979-01-01

The quasi-one-dimensional conductor (NH4)2[Pt(CN)4]Cl0.42·3H2O, ACP(Cl), has been studied experimentally by means of electrical conduction measurements, x-ray diffuse scattering, and neutron inelastic scattering. This allows the determination of all the physical parameters of interest for the the......The quasi-one-dimensional conductor (NH4)2[Pt(CN)4]Cl0.42·3H2O, ACP(Cl), has been studied experimentally by means of electrical conduction measurements, x-ray diffuse scattering, and neutron inelastic scattering. This allows the determination of all the physical parameters of interest...

Scaling analysis of [Fe(pyrazole)4]2[Nb(CN)8] molecular magnet

Science.gov (United States)

Konieczny, P.; Pełka, R.; Zieliński, P. M.; Pratt, F. L.; Pinkowicz, D.; Sieklucka, B.; Wasiutyński, T.

2013-10-01

The critical behaviour of the three dimensional (3D) molecular magnet {[FeII(pirazol)4]2[NbIV(CN)8]·4H2O}n has been studied with the use of experimental techniques such as ac magnetometry and zero field μSR spectroscopy. The sample orders magnetically below Tc=7.8 K. The measurements allowed to determine static exponents β, γ, and the dynamic exponent w. The resulting exponent values indicate that the studied system belongs to the universality class of the 3D Heisenberg model.

Effects of carbohydrate source for maintaining a high C:N ratio and fish driven re-suspension on pond ecology and production in periphyton-based freshwater prawn culture systems

NARCIS (Netherlands)

Asaduzzaman, M.; Wahab, M.A.; Verdegem, M.C.J.; Adhikary, R.K.; Rahman, S.M.S.; Azim, M.E.; Verreth, J.A.J.

2010-01-01

The present research investigated the effect of carbohydrate (CH) source for maintaining a high C:N ratio, and tilapia driven bioturbation on pond ecology, production and economical performances in C/N controlled periphyton-based (C/N-CP) freshwater prawn ponds. Two carbohydrate sources (high-cost

Thermodecomposition of lanthanides (III) and ytrium (III) glucoheptonates

International Nuclear Information System (INIS)

Giolito, J.

1987-01-01

The lanthanides (III) and yttrium (III) glucoheptonates as well the D-glucoheptono 1-4 lactone were studied using common analytical methods, elemental microanalysis of carbon and hydrogen, thermogravimetry and differential scanning calorimetry. These compounds were prepared from the reaction between the lanthanides (III) and yttrium (III) hydroxides and glucoheptonic acid aqueous solution obtained by means of the delta lactone hydrolysis of this acid. After stoichiometric reaction the compounds were precipitated by the addition of absolute ethanol, washed with the same solvent and dried in desiccator. Thermogravimetric the (TG) curves of the lanthanides glucoheptonates of the ceric group present thermal profiles with enough differences permitting an easy caracterization of each compound and the yttrium (III) glucoheptonate TG curve showed a great similarity with the erbium (III) compound TG curve. The differential scanning calometry (DSC) curves showed endothermic and exothermic peaks by their shape, height and position (temperature) permit an easy and rapid identification of each compound specially if DSC and TG curves were examined simultaneously. (author) [pt

The Moessbauer effect in Fe(III) HEDTA, Fe(III) EDTA, and Fe(III) CDTA compounds

International Nuclear Information System (INIS)

Prado, F.R.

1989-01-01

The dependence of Moessbauer spectra with pH value of Fe(III)HEDTA and Fe(III)CDTA compounds is studied. Informations on formation processes of LFe-O-FeL (L=ligand) type dimers by the relation of titration curves of Fe(III)EDTA, Fe(III)HEDTA and Fe(III)CDTA compounds with the series of Moessbauer spectra, are obtained. Some informations on Fe-O-Fe bond structure are also obtained. Comparing the titration curves with the series of Moessbauer spectra, it is concluded that the dimerization process begins when a specie of the form FeXOH α (X = EDTA, HEDTA, CDTA; α = -1, -2) arises. (M.C.K.) [pt

Reciprocal polyhedra and the Euler relationship: cage hydrocarbons, CnHn and closo-boranes [BxHx]2−

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Henning Hopf

2011-02-01

Full Text Available The closo-boranes BxHx+2, or their corresponding anions [BxHx]2− (where x = 5 through 12 and polycycloalkanes CnHn (where n represents even numbers from 6 through 20 exhibit a complementary relationship whereby the structures of the corresponding molecules, e.g., [B6H6]2− and C8H8 (cubane, are based on reciprocal polyhedra. The vertices in the closo-boranes correspond to faces in its polycyclic hydrocarbon counterpart and vice versa. The different bonding patterns in the two series are described. Several of these hydrocarbons (cubane, pentagonal dodecahedrane and the trigonal and pentagonal prismanes are known while others still remain elusive. Synthetic routes to the currently known CnHn highly symmetrical polyhedral species are briefly summarized and potential routes to those currently unknown are discussed. Finally, the syntheses of the heavier element analogues of cubane and the prismanes are described.

Synthesis of novel '4+1' Tc(III)/Re(III) mixed-ligand complexes with dendritically modified ligands

International Nuclear Information System (INIS)

Gniazdowska, E.; Kuenstler, J.U.; Stephan, H.; Pietzsch, H.J.

2006-01-01

Coordination chemistry of technetium and rhenium attracts a considerable interest due to the nuclear medicine applications of their radionuclides. Inert, so-called '3+1' or '4+1' technetium/rhenium mixed-ligand complexes open a new way to application of 99 mTc/ 188 Re labeled compounds in tumor diagnosis and therapy. In the presented paper, authors describe the synthesis and study of novel 99 mTc/ 188 Re complexes with dendritically functionalized tetradentate (tripodal chelator 2,2',2''-nitrilotris(ethanethiol), NS 3 and carboxyl group-bearing ligand, NS 3 (COOH) 3 ) and monodentate (dendritically modified isocyanide, CN-R(COOMe) 3 and isocyanide-modified peptide, CN-GGY) ligands. To verify the identity of the prepared n.c.a. complexes, non-radioactive analogous '4+1' Re compounds were synthesized. The experimental data show that a dendritic modification of the tetradentate/monodentate ligands changes the complex lipophilicity and does not influence its stability

Crystallographic and infrared spectroscopic study of bond distances in Ln[Fe(CN)6].4H2O (Ln=lanthanide)

International Nuclear Information System (INIS)

Zhou Xianju; Wong, W.-T.; Faucher, Michele D.; Tanner, Peter A.

2008-01-01

Along with crystallographic data of Ln[Fe(CN) 6 ].4H 2 O (Ln=lanthanide), the infrared spectra are reassigned to examine bond length trends across the series of Ln. The changes in mean Ln-O, Ln-N, C≡N and Fe-C distances are discussed and the bond natures of Ln-N and Ln-O are studied by bond length linear or quadratic fitting and comparisons with relevant ionic radii. The two different C≡N bond distances have been simulated by the covalo-electrostatic model. - Graphical abstract: Crystallographic and FTIR data for Ln[Fe(CN) 6 ].4H 2 O enable the changes in Ln-O, Ln-N, C≡N and Fe-C distances to be determined and modeled across the lanthanide series

Distinct features of C/N balance regulation in Prochlorococcus sp. strain MIT9313.

Science.gov (United States)

Domínguez-Martín, María Agustina; López-Lozano, Antonio; Rangel-Zúñiga, Oriol Alberto; Díez, Jesús; García-Fernández, José Manuel

2018-02-01

The abundance and significant contribution to global primary production of the marine cyanobacterium Prochlorococcus have made it one of the main models in marine ecology. Several conditions known to cause strong effects on the regulation of N-related enzymes in other cyanobacteria lacked such effect in Prochlorococcus. Prochlorococcus sp. strain MIT9313 is one of the most early-branching strains among the members of this genus. In order to further understand the C/N control system in this cyanobacterium, we studied the effect of the absence of three key elements in the ocean, namely N, P and Fe, as well as the effect of inhibitors of the N assimilation or photosynthesis on the N metabolism of this strain. Furthermore, we focused our work in the effect of ageing, as the age of cultures has clear effects on the regulation of some enzymes in Prochlorococcus. To reach this goal, expression of the main three regulators involved in N assimilation in cyanobacteria, namely ntcA, glnB and pipX, as well as that of icd (encoding for isocitrate dehydrogenase) were analysed. Our results show that the control of the main proteins involved in the C/N balance in strain MIT9313 differs from other model Prochlorococcus strains. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Light fragment preformation in cold fission of {sup 282}Cn

Energy Technology Data Exchange (ETDEWEB)

Poenaru, D.N.; Gherghescu, R.A. [Horia Hulubei National Institute of Physics and Nuclear Engineering (IFIN-HH), P.O. Box MG-6, Bucharest-Magurele (Romania); Johann Wolfgang Goethe University, Frankfurt Institute for Advanced Studies (FIAS), Frankfurt am Main (Germany)

2016-11-15

In a previous article, published in Phys. Rev. C 94, 014309 (2016), we have shown for the first time that the best dynamical trajectory during the deformation toward fission of the superheavy nucleus {sup 286}Fl is a linearly increasing radius of the light fragment, R{sub 2}. This macroscopic-microscopic result reminds us about the α or cluster preformation at the nuclear surface, assumed already in 1928, and proved microscopically many times. This time we give more detailed arguments for the nucleus {sup 282}Cn. Also similar figures are presented for heavy nuclei {sup 240}Pu and {sup 252} Cf. The deep minimum of the total deformation energy near the surface is shown for the first time as a strong argument for cluster preformation. (orig.)

Superconductivity of k-(BEDT-TTF) sub 2 Cu[N(CN) sub 2]I under pressure

CERN Document Server

Kushch, N D; Yagubskii, E B; Ishiguro, T

2001-01-01

The insulating state of k-(BEDT-TTF) sub 2 Cu[N(CN) sub 2]I salt appearing at ambient pressure at low temperatures is suppressed by hydrostatic pressure. The resistive measurement showed that in high-quality crystals the emerging metallic state reveals superconductivity. The superconducting state with the transition temperature of about 8 K is stable at pressures higher than 0.1 GPa

Sorption of trace amounts of gallium (III) on iron (III) oxide

International Nuclear Information System (INIS)

Music, S.; Gessner, M.; Wolf, R.H.H.

1979-01-01

The sorption of trace amounts of gallium(III) on iron(III) oxide has been studied as a function of pH. Optimum conditions have been found for the preconcentration of traces of gallium(III) by iron(III) oxide. The influence of surface active substances and of complexing agents on the sorption of trace amounts of gallium(III) on iron(III) oxide has been also studied. (orig.) [de

Sorption of trace amounts of gallium (III) on iron (III) oxide

Energy Technology Data Exchange (ETDEWEB)

Music, S; Gessner, M; Wolf, R H.H. [Institut Rudjer Boskovic, Zagreb (Yugoslavia)

1979-01-01

The sorption of trace amounts of gallium(III) on iron(III) oxide has been studied as a function of pH. Optimum conditions have been found for the preconcentration of traces of gallium(III) by iron(III) oxide. The influence of surface active substances and of complexing agents on the sorption of trace amounts of gallium(III) on iron(III) oxide has been also studied.

Capturing inhomogeneous broadening of the -CN stretch vibration in a Langmuir monolayer with high-resolution spectra and ultrafast vibrational dynamics in sum-frequency generation vibrational spectroscopy (SFG-VS)

Science.gov (United States)

Velarde, Luis; Wang, Hong-fei

2013-08-01

While in principle the frequency-domain and time-domain spectroscopic measurements should generate identical information for a given molecular system, the inhomogeneous character of surface vibrations in sum-frequency generation vibrational spectroscopy (SFG-VS) studies has only been studied with time-domain SFG-VS by mapping the decay of the vibrational polarization using ultrafast lasers, this due to the lack of SFG vibrational spectra with high enough spectral resolution and accurate enough lineshape. Here, with the recently developed high-resolution broadband SFG-VS (HR-BB-SFG-VS) technique, we show that the inhomogeneous lineshape can be obtained in the frequency-domain for the anchoring CN stretch of the 4-n-octyl-4'-cyanobiphenyl (8CB) Langmuir monolayer at the air-water interface, and that an excellent agreement with the time-domain SFG free-induction-decay can be established. We found that the 8CB CN stretch spectrum consists of a single peak centered at 2234.00 ± 0.01 cm-1 with a total linewidth of 10.9 ± 0.3 cm-1 at half maximum. The Lorentzian contribution accounts only for 4.7 ± 0.4 cm-1 to this width and the Gaussian (inhomogeneous) broadening for as much as 8.1 ± 0.2 cm-1. Polarization analysis of the -CN spectra showed that the -CN group is tilted 57° ± 2° from the surface normal. The large heterogeneity in the -CN spectrum is tentatively attributed to the -CN group interactions with the interfacial water molecules penetrated/accommodated into the 8CB monolayer, a unique phenomenon for the nCB Langmuir monolayers reported previously.

Branching fractions of the CN + C3H6 reaction using synchrotron photoionization mass spectrometry: evidence for the 3-cyanopropene product.

Science.gov (United States)

Trevitt, Adam J; Soorkia, Satchin; Savee, John D; Selby, Talitha S; Osborn, David L; Taatjes, Craig A; Leone, Stephen R

2011-11-24

The gas-phase CN + propene reaction is investigated using synchrotron photoionization mass spectrometry (SPIMS) over the 9.8-11.5 eV photon energy range. Experiments are conducted at room temperature in 4 Torr of He buffer gas. The CN + propene addition reaction produces two distinct product mass channels, C(3)H(3)N and C(4)H(5)N, corresponding to CH(3) and H elimination, respectively. The CH(3) and H elimination channels are measured to have branching fractions of 0.59 ± 0.15 and 0.41 ± 0.10, respectively. The absolute photoionization cross sections between 9.8 and 11.5 eV are measured for the three considered H-elimination coproducts: 1-, 2-, and 3-cyanopropene. Based on fits using the experimentally measured photoionization spectra for the C(4)H(5)N mass channel and contrary to the previous study (Int. J. Mass. Spectrom.2009, 280, 113-118), where it was concluded that 3-cyanopropene was not a significant product, the new data suggests 3-cyanopropene is produced in significant quantity along with 1-cyanopropene, with isomer branching fractions from this mass channel of 0.50 ± 0.12 and 0.50 ± 0.24, respectively. However, similarities between the 1-, 2-, and 3-cyanopropene photoionization spectra make an unequivocal assignment difficult based solely on photoionization spectra. The CN + CH(2)CHCD(3) reaction is studied and shows, in addition to the H-elimination product signal, a D-elimination product channel (m/z 69, consistent with CH(2)CHCD(2)CN), providing further evidence for the formation of the 3-cyanopropene reaction product.

WISC-III e WAIS-III na avaliação da inteligência de cegos WISC-III/WAIS-III en ciegos WISC-III and WAIS-III in intellectual assessment of blind people

Directory of Open Access Journals (Sweden)

Elizabeth do Nascimento

2007-12-01

Full Text Available Diante da escassez de pesquisas nacionais e de testes psicológicos destinados a avaliar pessoas cegas, desenvolveu-se um estudo psicométrico com as escalas verbais dos testes WISC-III e WAIS-III. Após as adaptações de alguns estímulos e das instruções, os testes foram aplicados em crianças (N = 120 e adultos (N = 52 residentes em Belo Horizonte. Os resultados indicaram que as escalas verbais modificadas apresentam uma boa consistência interna (alfa> 0,80. Além disso, a investigação da validade fatorial identifica a presença clara de apenas um componente. Este componente explica 81% e 64% para o WISC-III e WAIS-III, respectivamente. Conclui-se que as adaptações a que se procedeu não afetaram a estrutura fatorial das escalas. Deste modo, os profissionais poderão utilizar as escalas modificadas para avaliar a inteligência de pessoas cegas.Frente a la escasez de investigaciones nacionales asi como la ausencia de tests psicológicos que evaluen personas ciegas, se ha desarrollado un estudio psicometrico com la escalas verbales del WISC-III y WAIS-III. Posteriormente a las adaptaciones de algunos estímulos y de las instrucciones, las escalas fueron aplicadas a una muestra de niños (n=120 y de adultos (n=52 residentes en la ciudad de Belo Horizonte-Brasil. Los resultados indican que las escalas verbales modificadas presentan una alta fiabilidad (alpha >0,80 asi como la presencia clara de un unico componente responsable por 81% y 64% de la variancia del WIC-III e WAIS-III respectivamente. Se ha concluido que las modificaciones efectuadas no han comprometido la estructura factorial de las escalas verbales. Por tanto, los profesionales psicólogos pueden utilizar las escalas modificadas para la evaluación de la inteligencia de personas portadoras de ceguera.Owing to the almost lack of a national research on psychological testing for the evaluation of blind people, a psychometric study has been developed with the WISC-III and WAIS-III

Crystal structure of trichlorido(4′-ferrocenyl-2,2′:6′,2′′-terpyridine-κ3N,N′,N′′iridium(III acetonitrile disolvate

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Bambar Davaasuren

2015-03-01

Full Text Available In the title compound, [FeIr(C5H5(C20H14N3Cl3]·2CH3CN, the central IrIII atom is sixfold coordinated by three chloride ligands and three terpyridine N atoms in a slightly distorted octahedral fashion. The terpyridine ligand is functionalized at the 4′-position with a ferrocenyl group, the latter being in an eclipsed conformation. In the crystal, molecules are stacked in rows parallel to [001], with the acetonitrile solvent molecules situated between the rows. An extensive network of intra- and intermolecular C—H...Cl interactions is present, stabilizing the three-dimensional structure.

Animated Dreamsi grand prix läks Tšiilisse / Kristiina Davidjants

Index Scriptorium Estoniae

Davidjants, Kristiina, 1974-

2009-01-01

Pimedate Ööde 13. filmifestivali teise alafestivali Animated Dreams auhinnasaajad: võitis Cristobal Leoni, Niles Atallah' ja Joaquin Cocina "Lucia", ANOBA nominatsiooni sai Kaspar Jancise "Krokodill". Lisatud nimekiri "Animated Dreamsi võitjad"

Alterações da relação C/N de um Latossolo Vermelho-Amarelo sob diferentes coberturas vegetais em Brasnorte – MT. Changes in C/N relation of a Red-Yellow Latosol under different plant cultivations in Brasnorte – MT.

Directory of Open Access Journals (Sweden)

Cristiane Ramos VIEIRA

2014-12-01

Full Text Available Este estudo objetivou analisar as alterações nos teores de carbono e de nitrogênio e na relação C/N em solos sob diferentes coberturas. Os sistemas avaliados foram: Floresta Secundária, pastagem, e plantios de teca (Tectona grandis com 8, 13, 16 e 19 anos, utilizando o delineamento inteiramente casualizado para a coleta do solo nas profundidades 0 a 5, 5 a 10 e 10 a 20 cm. Nas áreas dos plantios de T. grandis as amostras de solo foram coletadas na projeção da copa e nas entrelinhas, e nas áreas de pastagem e de Floresta Secundária a coleta foi aleatória. Verificou-se que os teores de carbono orgânico total – COT foram mais elevados nas primeiras camadas de solo, diminuindo conforme a profundidade. A manutenção dos teores de C e de N, semelhantes aos da Floresta Secundária, permitem caracterizar o solo dos sistemas pastagem e de cultivo de T. grandis como quimicamente não degradados, sendo que os valores de relação C/N indicam que o processo dominante em todos os sistemas foi a mineralização. This study aimed to analyze the changes in the levels of carbon and nitrogen and C/N relation in different soil covers. The systems evaluated were: Secondary Forest, pasture, and plantations of teak at 8, 13, 16 and 19 years old, using a completely randomized design in split plot to collect soil in three depths (0-5, 5-10 and 10-20 cm. In the area of teak plantations samples of soil were collected on the projection of the tree crown and between lines, in the pasture and Secondary Forest they were collected randomly. It was found that the concentration of total organic carbon – TOC was higher in the first depth, decreasing as the depth. The maintenance of the levels of C and N similar to Secondary Forest can characterize the soil of grass pastures systems and cultivation of teak as chemical not degraded and C/N relation indicates that the dominant process on all systems was the mineralization.

Fate of nutrient enrichment on continental shelves as indicated by the C/N content of bottom sediments

Energy Technology Data Exchange (ETDEWEB)

Walsh, J.J.; Premuzic, E.T.; Whitledge, T.E.

1980-01-01

The trajectory and fate of particulate matter are poorly understood processes in a spatially heterogeneous coastal ocean. Parameterization of appropriate hydrodynamics for a quantitative description of these loss processes must thus await definition of the important biological time and space scales. Since the bottom sands tend to record the history of the water column, we have selected the C/N content of shelf sediments as a possible tracer of (1) sites of nutrient introduction to the shelf by various physical mechanisms, of (2) areas of subsequent downstream utilization by the phytoplankton, and of (3) where loss of particulate matter might occur from the water column. An analysis is made of the C/N patterns of bottom surface sediments in relation to the nitrogen sources from upwelling, river runoff, and tidal mixing on the Peruvian, west African, Amazonian, Gulf of Mexico, eastern US, Bering, and North Sea shelves in an initial attempt to proscribe the particle trajectories of organic matter on the continental shelf.

Fate of nutrient enrichment on continental shelves as indicated by the C/N content of bottom sediments

International Nuclear Information System (INIS)

Walsh, J.J.; Premuzic, E.T.; Whitledge, T.E.

1980-01-01

The trajectory and fate of particulate matter are poorly understood processes in a spatially heterogeneous coastal ocean. Parameterization of appropriate hydrodynamics for a quantitative description of these loss processes must thus await definition of the important biological time and space scales. Since the bottom sands tend to record the history of the water column, we have selected the C/N content of shelf sediments as a possible tracer of (1) sites of nutrient introduction to the shelf by various physical mechanisms, of (2) areas of subsequent downstream utilization by the phytoplankton, and of (3) where loss of particulate matter might occur from the water column. An analysis is made of the C/N patterns of bottom surface sediments in relation to the nitrogen sources from upwelling, river runoff, and tidal mixing on the Peruvian, west African, Amazonian, Gulf of Mexico, eastern US, Bering, and North Sea shelves in an initial attempt to proscribe the particle trajectories of organic matter on the continental shelf

Statistical optimization of fermentative hydrogen production from xylose by newly isolated Enterobacter sp. CN1

Energy Technology Data Exchange (ETDEWEB)

Long, Chuannan; Cui, Jingjing; Liu, Zuotao; Liu, Yuntao; Hu, Zhong [Department of Biology, Shantou University, Shantou 515063 (China); Long, Minnan [The School of Energy Research, Xiamen University, Xiamen 361005 (China)

2010-07-15

Statistical experimental designs were applied for the optimization of medium constituents for hydrogen production from xylose by newly isolated Enterobacter sp. CN1. Using Plackett-Burman design, xylose, FeSO{sub 4} and peptone were identified as significant variables which highly influenced hydrogen production. The path of steepest ascent was undertaken to approach the optimal region of the three significant factors. These variables were subsequently optimized using Box-Behnken design of response surface methodology (RSM). The optimum conditions were found to be xylose 16.15 g/L, FeSO{sub 4} 250.17 mg/L, peptone 2.54 g/L. Hydrogen production at these optimum conditions was 1149.9 {+-} 65 ml H{sub 2}/L medium. Under different carbon sources condition, the cumulative hydrogen volume were 1217 ml H{sub 2}/L xylose medium, 1102 ml H{sub 2}/L glucose medium and 977 ml H{sub 2}/L sucrose medium; the maximum hydrogen yield were 2.0 {+-} 0.05 mol H{sub 2}/mol xylose, 0.64 mol H{sub 2}/mol glucose. Fermentative hydrogen production from xylose by Enterobacter sp. CN1 was superior to glucose and sucrose. (author)

The Effects of Fiddler Crabs (Uca sp on C/N Ratio and Redox Potential of Soil in Mangrove Ecosystems

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Mulyanto Mulyanto

2017-08-01

Full Text Available Research has been done in Ketapang mangrove area of  Probolinggo city in months of September-November 2015. The objectives are to observe the fiddler crab community stucture and to analyze the effects of fiddler crabs on C/N ratio and redox potential of soil in mangrove ecosystems. The samples of fiddler crabs were taken during the low tides at 4 station (20 transects with sizes of 1 m2. Data of the fiddler crabs were measured from the soil digging insides the transect. The soil samples were taken from these crab holes wall (at the surface and at the depth of 20 cm, under the holes at the depth of 40 cm as well as from the locations that undwells by these animals at the same depth. The fiddler crab identified are U. Triangularis between 2 – 6 ind/m2, U paradussumieri 1 – 3 ind/m2, U perplexa 14 – 32 ind/m2, U dussumieri 12 – 27 ind/m2 and U. Tetragonon 3 – 6 ind/m2. The diversity is moderate (H = 1.7 and the dominance index was low (C = 0.37. C/N ratio soil were inhabited by fiddler crab between 6 – 14, the undwelled area were 14 – 20. Soil C/N ratio was inhabited by the fiddler crab at the surface and depth of 20 cm in average of 9 cm while at 40 cm in avergae of 12. The low of C/N ratio at surface and depth of 20 cm causing the organic matter turnover faster because the high nitorgen content. Soil potential redox (Eh the undwelled areas was found –0.647 mV, meanwhile the soil Eh in the dwelled areas was positive (0.68 till 0.87 mV. This mean, the decpmposition was occured during aerobic condition and will produce untoxic subtances.