Viscosity, Conductivity, and Electrochemical Property of Dicyanamide Ionic Liquids

PubMed Central

Yuan, Wen-Li; Yang, Xiao; He, Ling; Xue, Ying; Qin, Song; Tao, Guo-Hong

2018-01-01

The instructive structure-property relationships of ionic liquids (ILs) can be put to task-specific design of new functionalized ILs. The dicyanamide (DCA) ILs are typical CHN type ILs which are halogen free, chemical stable, low-viscous, and fuel-rich. The transport properties of DCA ionic liquids are significant for their applications as solvents, electrolytes, and hypergolic propellants. This work systematically investigates several important transport properties of four DCA ILs ([C4mim][N(CN)2], [C4m2im][N(CN)2], N4442[N(CN)2], and N8444[N(CN)2]) including viscosity, conductivity, and electrochemical property at different temperatures. The melting points, temperature-dependent viscosities and conductivities reveal the structure-activity relationship of four DCA ILs. From the Walden plots, the imidazolium cations exhibit stronger cation–anion attraction than the ammonium cations. DCA ILs have relatively high values of electrochemical windows (EWs), which indicates that the DCA ILs are potential candidates for electrolytes in electrochemical applications. The cyclic voltammograms of Eu(III) in these DCA ILs at GC working electrode at various temperatures 303–333 K consists of quasi-reversible waves. The electrochemical properties of the DCA ILs are also dominated by the cationic structures. The current intensity (ip), the diffusion coefficients (Do), the charge transfer rate constants (ks) of Eu(III) in DCA ILs all increased with the molar conductivities increased. The cationic structure-transport property relationships of DCA ILs were constructed for designing novel functionalized ILs to fulfill specific demands. PMID:29600245

Laboratory Detection of HSiCN and HSiNC

NASA Astrophysics Data System (ADS)

Sanz, M. Eugenia; McCarthy, Michael C.; Thaddeus, Patrick

2002-09-01

Two new silicon-bearing molecules, the closed-shell asymmetric tops cyanosilylene HSiCN and its isomer HSiNC, have been detected in a laboratory discharge by molecular beam Fourier transform microwave spectroscopy. The rotational spectra of the normal and deuterated isotopic species of both molecules have been analyzed to derive precise spectroscopic constants, which allow the astronomically most interesting transitions up to 120 GHz to be calculated to an accuracy better than 1 km s-1 in equivalent radial velocity. Both molecules are good candidates for astronomical detection, closely related in structure and composition to known astronomical molecules, and they are highly polar, with estimated dipole moments of 3.5 D for HSiCN and 2.5 D for HSiNC.

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

PubMed

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.

Structure of sodium cyanide by molecular beam electric resonance spectroscopy

NASA Astrophysics Data System (ADS)

van Vaals, J. J.; Meerts, W. Leo; Dymanus, A.

1982-11-01

The results of the first successful observations of the microwave spectrum of sodium cyanide are presented. Twenty rotational transitions between 9.5 and 40 GHz were used to determine the rotational constants and the effective structure of the free molecule in the ground vibrational state. The structure was found to be T-shaped and the results (in Å) are: rCN=1.169(6), rNaC=2.366(29), and rNaN=2.243(27). (AIP)

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

NASA Technical Reports Server (NTRS)

Hoobler, Ray J.; Leone, Stephen R.

1997-01-01

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

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

NASA Astrophysics Data System (ADS)

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.

Structural and spectroscopic characterization of various isotopologues of 2-hydroxyacetonitrile using highly correlated ab initio methods

NASA Astrophysics Data System (ADS)

Dalbouha, Samira; Domínguez-Gómez, Rosa M.; Senent, Maria Luisa

2017-06-01

Various isotopologues of 2-hydroxyacetonitrile (OHCH2CN), a detectable astrophysical molecule, are characterized using explicitly correlated coupled cluster theory (CCSD(T)-F12/AVTZ-F12). Rovibrational parameters and far infrared transitions are computed to help the interpretation of the rotational spectra and radioastronomical observations. OHCH2CN displays non-rigid properties. The OH internal rotation intertransforms two conformers, gauche and trans, whose energy separation reaches 1.41 kcal/mol. The process is restricted by energy barriers of V t = 645 cm-1 and V g → g = 425 cm-1. Isotopic effects on the rotational constants and on the torsional energy levels are evaluated for isotopic varieties containing the most abundant cosmological isotopes (13C, 18C, 15N and D). Effects are relevant for ODCH2CN where the ground vibrational state splits in two components separated by 0.51 cm-1. This gap has been evaluated to be 3.20 cm-1 for the main isotopologue.

Vapochromic Behaviour of M[Au(CN)2]2-Based Coordination Polymers (M = Co, Ni)

PubMed Central

Lefebvre, Julie; Korčok, Jasmine L.; Katz, Michael J.; Leznoff, Daniel B.

2012-01-01

A series of M[Au(CN)2]2(analyte)x coordination polymers (M = Co, Ni; analyte = dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), pyridine; x = 2 or 4) was prepared and characterized. Addition of analyte vapours to solid M(μ-OH2)[Au(CN)2]2 yielded visible vapochromic responses for M = Co but not M = Ni; the IR νCN spectral region changed in every case. A single crystal structure of Zn[Au(CN)2]2(DMSO)2 revealed a corrugated 2-D layer structure with cis-DMSO units. Reacting a Ni(II) salt and K[Au(CN)2] in DMSO yielded the isostructural Ni[Au(CN)2]2(DMSO)2 product. Co[Au(CN)2]2(DMSO)2 and M[Au(CN)2]2(DMF)2 (M = Co, Ni) complexes have flat 2-D square-grid layer structures with trans-bound DMSO or DMF units; they are formed via vapour absorption by solid M(μ-OH2)[Au(CN)2]2 and from DMSO or DMF solution synthesis. Co[Au(CN)2]2(pyridine)4 is generated via vapour absorption by Co(μ-OH2)[Au(CN)2]2; the analogous Ni complex is synthesized by immersion of Ni(μ-OH2)[Au(CN)2]2 in 4% aqueous pyridine. Similar immersion of Co(μ-OH2)[Au(CN)2]2 yielded Co[Au(CN)2]2(pyridine)2, which has a flat 2-D square-grid structure with trans-pyridine units. Absorption of pyridine vapour by solid Ni(μ-OH2)[Au(CN)2]2 was incomplete, generating a mixture of pyridine-bound complexes. Analyte-free Co[Au(CN)2]2 was prepared by dehydration of Co(μ-OH2)[Au(CN)2]2 at 145 °C; it has a 3-D diamondoid-type structure and absorbs DMSO, DMF and pyridine to give the same materials as by vapour absorption from the hydrate. PMID:22737031

Atmospheric turbulent structures and their correlative factor leading to the thunderstorm events at the NE region of India

NASA Astrophysics Data System (ADS)

Zahan, Y.; Devi, M.; Barbara, A. K.; Pathak, K.; Ray, K. P.

2017-08-01

Starting with the seasonal occurrence characteristics of thunderstorm (TS) over North Eastern (NE) part of India, the paper addresses hydrodynamic factors leading to TS. Further, atmospheric structure constant (Cn2) and Reynolds number (Re) the two turbulence parameters are analysed in association with TS, on the background that these two variabilities and TS events are associated with atmospheric temperature and humidity. The analysis result shows that during the growth and development processes of TS, the correlation coefficient between Cn2 and Re is enhanced by 50% compared to non-thunderstorm days. These observations are explained in terms of eddies and vortices generated in a moving fluid system of an atmosphere as represented by Cn2 and Re. The vortices are the turbulent pockets of fluid that move randomly within the medium and ultimately dissipate their kinetic energy in the form of heat. This process leads to the transfer of energy between atmospheric layers by changing the buoyancy that may cause dry, wet or storm conditions of the weather. Such kind of energy transfer processes may be widespread or localized. The active movement of the fluid during localized condition produces rapid changes in Cn2 and Re which in turn may provide storm conditions. In this background, the paper examines the role of these parameters in the growth and development of TS over NE region.

CN radical reactions with hydrogen cyanide and cyanogen - Comparison of theory and experiment

NASA Technical Reports Server (NTRS)

Yang, D. L.; Yu, T.; Lin, M. C.; Melius, C. F.

1992-01-01

The method of laser photolysis/laser-induced fluorescence is used to obtain absolute rate constants for CN radical reactions with HCN and C2N2. The rate constants were found to be temperature-dependent in the range 300-740 K and pressure independent in the range 100-600 Torr. Rice-Remsperger-Kassel-Marcus theory for both reactions employing the transition state parameters obtained by the BAC-MP4 method are made. These calculations yielded reasonable results for the CN + HCN reaction, predicting both the temperature dependence and pressure independence. No pressure effect was observed in the pressure range 100-1000 Torr at temperatures below 900 K, confirming the experimental results.

Progesterone binding nano-carriers based on hydrophobically modified hyperbranched polyglycerols

NASA Astrophysics Data System (ADS)

Alizadeh Noghani, M.; Brooks, D. E.

2016-02-01

Progesterone (Pro) is a potent neurosteroid and promotes recovery from moderate Traumatic Brain Injury but its clinical application is severely impeded by its poor water solubility. Here we demonstrate that reversibly binding Pro within hydrophobically modified hyperbranched polyglycerol (HPG-Cn-MPEG) enhances its solubility, stability and bioavailability. Synthesis, characterization and Pro loading into HPG-Cn-MPEG is described. The release kinetics are correlated with structural properties and the results of Differential Scanning Calorimetry studies of a family of HPG-Cn-MPEGs of varying molecular weight and alkylation. While the maximum amount of Pro bound correlates well with the amount of alkyl carbon per molecule contributing to its hydrophobicity, the dominant first order rate constant for Pro release correlates strongly with the amount of structured or bound water in the dendritic domain of the polymer. The results provide evidence to justify more detailed studies of interactions with biological systems, both single cells and in animal models.Progesterone (Pro) is a potent neurosteroid and promotes recovery from moderate Traumatic Brain Injury but its clinical application is severely impeded by its poor water solubility. Here we demonstrate that reversibly binding Pro within hydrophobically modified hyperbranched polyglycerol (HPG-Cn-MPEG) enhances its solubility, stability and bioavailability. Synthesis, characterization and Pro loading into HPG-Cn-MPEG is described. The release kinetics are correlated with structural properties and the results of Differential Scanning Calorimetry studies of a family of HPG-Cn-MPEGs of varying molecular weight and alkylation. While the maximum amount of Pro bound correlates well with the amount of alkyl carbon per molecule contributing to its hydrophobicity, the dominant first order rate constant for Pro release correlates strongly with the amount of structured or bound water in the dendritic domain of the polymer. The results provide evidence to justify more detailed studies of interactions with biological systems, both single cells and in animal models. Electronic supplementary information (ESI) available: Fig. S-1: chemical structure of progesterone (Pro). Fig. S-2: 1H NMR spectrum of HPG-C8-MPEG. Fig. S-3: GPC chromatogram of HPG-C8-MPEG. Fig. S-4: 1H NMR spectrum of HPG-C12-MPEG. Fig. S-5: GPC chromatogram of HPG-C8-MPEG. Fig. S-6: FTIR spectrum of HPG-C8-MPEG. Fig. S-7: inverse-gated 13C NMR spectrum of HPG-C8-MPEG in methanol-d4. Fig. S-8: semi-log plot to determine initial rapid release kinetics for HPG-C8-MPEG/Pro in PBS. Fig. S-9: semi-log plot to determine secondary slow release kinetics for HPG-C8-MPEG/Pro in PBS. Fig. S-10: semi-log plot illustrating the kinetics of Pro release from HPG-C8-MPEG/Pro in plasma. Fig. S-11: dependence of k1 and Vp - Va. Fig. S-12: correlation between the maximum binding capacity of HPG-Cn-MPEG polymeric systems for binding Pro and their total mass of alkyl carbon external to the oxygen (R2 = 0.77 and p < 0.025). Table S-1: effect of loaded Pro on HPG-Cn-MPEG size. Fig. S-13. DLS size determination of HPG-C10-MPEG at 2 mg ml-1 (on the left) and HPG-C10-MPEG/Pro at 2 mg ml-1 of polymer and 25 μg ml-1 of Pro (on the right). The minor population of larger particles was reduced in diameter by Pro binding, illustrated above, consistent with an earlier report.11 See DOI: 10.1039/c5nr08175k

Applications of ZVMo NMR spectroscopy. 17. ZVMo and UN relaxation time measurements confirming that (Mo(CN)8)U is dodecahedral in aqueous solution

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

Brownlee, R.T.; Shehan, B.P.; Wedd, A.G.

1987-07-01

Variable-temperature NMR line width measurements of ZVMo and UN in aqueous solutions of K4(Mo(CN)8) x 2H2O indicate that the stereochemistry of the (Mo(CN)8)U ion in solution is dodecahedral. A value for the ZVMo quadrupole coupling constant of 3.61 MHz is obtained. 27 references, 1 figure, 1 table.

Synthesis of new structurally related cyanamide compounds LiM(CN{sub 2}){sub 2} where M is Al{sup 3+}, In{sup 3+} or Yb{sup 3+}

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

Kubus, Mariusz, E-mail: mariusz.kubus@anorg.uni-tuebingen.de; Heinicke, Robert; Ströbele, Markus

2015-02-15

Highlights: • New cyanamide compounds LiM(CN{sub 2}){sub 2} where M is Al{sup 3+}, In{sup 3+} or Yb{sup 3+}. • New luminescent material LiIn(CN{sub 2}){sub 2}:Tb{sup 3+}. • Reduction in efficiency of luminescence with temperature increase. - Abstract: New ternary cyanamide compounds isostructural to LiY(CN{sub 2}){sub 2} were obtained by solid state metathesis reaction. The crystal structure of LiAl(CN{sub 2}){sub 2} was determined by single crystal X-ray diffraction, the structures of LiIn(CN{sub 2}){sub 2} and LiYb(CN{sub 2}){sub 2} were solved from X-ray powder diffraction data. Photoluminescence properties of Tb{sup 3+}-doped LiIn(CN{sub 2}){sub 2} are reported too.

Experimental and numerical study of underwater beam propagation in a Rayleigh-Bénard turbulence tank.

PubMed

Nootz, Gero; Matt, Silvia; Kanaev, Andrey; Judd, Kyle P; Hou, Weilin

2017-08-01

The propagation of a laser beam through Rayleigh-Bénard (RB) turbulence is investigated experimentally and by way of numerical simulation. For the experimental part, a focused laser beam transversed a 5  m×0.5  m×0.5  m water filled tank lengthwise. The tank is heated from the bottom and cooled from the top to produce convective RB turbulence. The effect of the turbulence on the beam is recorded on the exit of the beam from the tank. From the centroid motion of the beam, the index of refraction structure constant Cn2 is determined. For the numerical efforts RB turbulence is simulated for a tank of the same geometry. The simulated temperature fields are converted to the index of refraction distributions, and Cn2 is extracted from the index of refraction structure functions, as well as from the simulated beam wander. To model the effect on beam propagation, the simulated index of refraction fields are converted to discrete index of refraction phase screens. These phase screens are then used in a split-step beam propagation method to investigate the effect of the turbulence on a laser beam. The beam wander as well as the index of refraction structure parameter Cn2 determined from the experiment and simulation are compared and found to be in good agreement.

Effect of RF power and annealing on chemical bonding and morphology of a-CN{sub x} thin films as humidity sensor

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

Aziz, N. F. H; Hussain, N. S. Mohamed; Awang, R.

2013-11-27

Amorphous carbon nitride (a-CN{sub x}) thin films were deposited using radio frequency plasma enhanced chemical vapor deposition (rf-PECVD) technique. A set of a-CN{sub x} thin films were prepared using pure methane (CH{sub 4}) gas diluted with nitrogen (N{sub 2}) gas. The rf power was varied at 50, 60, 70, 80, 90 and 100 W. These films were then annealed at 400 °C in a quartz tube furnace in argon (Ar) gas. The effects of rf power and thermal annealing on the chemical bonding and morphology of these samples were studied. Surface profilometer was used to measure film thickness. Fourier transformmore » infra-red spectroscopy (FTIR) and Field emission scanning electron microscopy (FESEM) measurements were used to determine their chemical bonding and morphology respectively. The deposition rate of the films increased constantly with increasing rf power up to 80W, before decreasing with further increase in rf power. Fourier transform infra-red spectroscopy (FTIR) studies showed a systematic change in the spectra and revealed three main peaks included C-N, C=N, C=C and C≡N triple bond. C=N and C≡N bonds decreased with increased C-N bonds after thermal annealing process. The FESEM images showed that the structure is porous for as-deposited and covered by granule-like grain structure after thermal annealing process was done. The resistance of the a-CN{sub x} thin film changed from 23.765 kΩ to 5.845 kΩ in the relative humidity range of 5 to 92 % and the film shows a good response and repeatability as a humidity sensing materials. This work showed that rf power and thermal annealing has significant effects on the chemical bonding and surface morphology of the a-CN{sub x} films and but yield films which are potential candidate as humidity sensor device.« less

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

NASA Technical Reports Server (NTRS)

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?

PubMed

Pauzat, F; Ellinger, Y; McLean, A D

1991-03-01

Rotational constants and dipole moments for linear-chain radicals CnCH and CnN are estimated using a combination 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 2 pi 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 2 pi 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 2 sigma ground state, and our 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

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

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

1991-03-01

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 presentmore » 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.« less

Lead Barium Potassium Sodium Niobate Ceramics for Piezoelectric Applications

NASA Astrophysics Data System (ADS)

Sambasiva Rao, K.; Vallisnath, N.; Prasad, T. N. V. K. V.; Ch. Varada Rajulu, K.; Tilak, B.; Lee, Joon Hyung

This paper reports a systematic study of tungsten bronze morphotropic phase boundary (MPB) system Pb2-2X-3Y/2Ba2xREyK1-xNaxNb5O15, where, x = 0.20, 0.25, 0.30, RE = Pr and Bi and y = 0.05 and their structure, microstructure, hysteresis, dielectric, piezoelectric, and Pyroelectric properties. Enhanced piezoelectric constants kp, kt, k31, d31, d33, g31, g33, S11 E as 30.8%, 47.6%, 18.9%, 57 × 10-12 C/N, 159 × 10-12 C/N, 6.89 × 10-3 mV/N, 19.23 × 10-3 mV/N, and 13.88 × 10-12 m2/N respectively are observed in the composition for which y = 0, and x = 0.30, which is above MPB. Also, a change in thickness, 0.0159 μm has been developed for a thickness of the sample 1.2 mm, d33 = 159 × 10-12 C/N and for an applied voltage of 100 V. The same material produces a length extension, 0.0475 μm for d31 = 57 × 10-12 C/N, l = 10 mm, t = 1.2 mm, for an applied voltage of 100 V. Thus the material may be useful for a piezoelectric transducer. Enhanced piezoelectric coefficients, d31 = 96 × 10-12 C/N and g33 = 12.95 × 10-3 mV/N are also observed in the composition for which RE = Pr and x = 0.25.

Enantioselective excited-state quenching of racemic Tb (III) and Eu (III) Tris (pyridine-2,6-dicarboxylate) by vitamin B 12 derivatives

NASA Astrophysics Data System (ADS)

Meskers, Stefan C. J.; Dekkers, Harry P. J. M.

1999-08-01

Enantioselectivity in the dynamic quenching of the luminescence of the Δ and Λ enantiomers of racemic Tb(III)(pyridine-2,6-dicarboxylate=DPA) 33- and Eu(DPA) 33- by a series of corrinoids is demonstrated by time resolved luminescence and circular-polarization-of-luminescence (CPL) spectroscopy. Studied are cyanocobalamin (vitamin B 12), aquacobalamin (B 12a) and its conjugated base hydroxocobalamin (HOCbl), dicyanocobinamide ((CN) 2Cbi) and the heptamethyl ester of dicyanocobyrinic acid ((CN) 2Cby(OMe) 7). For this set of quenchers (Q), the diastereomeric quenching rate constants ( kqΔ and kqΛ) are reported together with the degree of enantioselectivity Eq=( kqΔ- kqΛ)/( kqΔ+ kqΛ). In the systems with Tb, values of the average rate constant kqavg(=( kqΔ+ kqΛ)/2) are 1.0, 2.9 and 0.53 10 8 M -1 s -1 for CNCbl, (CN) 2Cbi, (CN) 2Cby(OMe) 7 with Eq=-0.24, -0.20, +0.01 (standard error of Eq is 0.01). The quenching by B 12a is strongly dependent on pH and ionic strength ( I); when I=12 mM we find kqavg=5.3, Eq=-0.23 at pH 6.7 and kqavg=1.3, Eq=-0.27 at pH 8.9. Corresponding rates for Eu are 0.41, 27, 3.4 10 7 M -1 s -1 and for B 12a, 7.3 and 1.2 10 7 M -1 s -1, corresponding values for Eq -0.27, -0.29, +0.02, -0.21 and -0.29. The quenching reaction is modeled as a pre-equilibrium involving the formation of an encounter complex (association constant K) followed by the actual electronic energy transfer step (rate ket). By relating the quenching data with molecular structure it is argued that the binding in the encounter complex involves two hydrogen bonds between the uncoordinated carboxylate oxygen atom of two DPA ligands of Ln(DPA) 33- and two amide groups of the corrinoid, presumably involving the a and g, the a and b, or the b and g side chains. For some corrinoid/Ln(DPA) 33- complexes the association constants and enantioselectivities in the ground state are known (Spectrochimica Acta 55A (1999) 1837-1855), which allows for an estimate of the average rate of energy transfer, ketavg (i.e. ( ketΔ+ ketΛ)/2). The enantioselectivity in the quenching reaction is lower than in the ground state association which is interpreted in terms of different values of ket in the two diastereomeric Ln-corrinoid complexes; for both Tb and Eu we find ketΔ/ ketΛ˜0.3 with CNCbl, B 12a at pH 6.7 and (CN) 2Cbi. These data imply that the chiral discrimination in the energy transfer is considerable and counteracts that in the binding but does not dominate it.

Investigation of the redox states of (Ru(bpy) sub 2 CN) sub 2 CN sup + : Evidence for valence delocalization of the singly oxidized complex

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

Cooper, J.B.; Vess, T.M.; Kalsbeck, W.A.

1991-05-15

A spectroelectrochemical study of both the oxidized and reduced forms of (Ru(bpy){sub 2}CN){sub 2}CN{sup +} is reported. The uv-vis spectra of the parent and reduced species indicate the complex consists of two identical chromophores, which are nearly identical with the Ru(bpy){sub 2}(CN){sub 2} chromophore, even though one ruthenium is bound to the carbon of the bridging CN while the other is nitrogen bound. Only the shift in the bridging CN stretching frequency wit reduction offers any distinction between the two following observations: (1) only two CN stretches are observed in the oxidized form, (2) the shift to higher energy ofmore » the terminal CN stretches for the bimetallic species is half of that observed upon oxidation of the monometallic complex, (3) the sharpness and solvent independence of the near-IR band is not consistent with Hush predictions for the IVT band, and (4) the separation of the oxidation waves implies a comproportionation constant for the bimetallic species of 1.38 {times} 10{sup 10} (assuming no difference in metal centers) comparable in magnitude to other delocalized systems. 40 refs., 8 figs., 2 tabs.« less

Free-space optical communication link performance enhancement via modified receiver geometric characteristics

NASA Astrophysics Data System (ADS)

Prasad, Narasimha S.; Kratovil, Patrick T.; Tucker, Sara C.; Vallestero, Neil J.; Khusid, Mark

2004-01-01

A free-space, line-of-sight, ground-based optical link at 1.5 microns is attractive for tactical communications because it would provide eye-safety, covertness and jam-proof operation. However, the effects of atmospheric turbulence have to be appropriately mitigated for achieving acceptable bit-error-rate (BER) for reliable dissemination of information. Models to predict achievable BER at 1.5 microns for several beam propagation schemes that include beam scanning have been developed for various turbulence conditions. In this paper, we report performance characterization of free-space, high-data (>1Gb/s) rate beam propagation parameters at 1.5 microns for achieving BER reduction under the presence of turbulence. For standard free-space optical links, the mean SNR limits the achievable BER to lesser than 10-6 for Cn2 (structure constant of refractive index fluctuations) around 10-12 m-2/3. To validate these models, simultaneous measurements of structure constant of refractive index fluctuations, Cn2, and coherence diameter over tactical ranges have been carried out and analyzed. The effect of input beam conditioning to reduce BER levels have been explored. Furthermore, single and multiple transmit beams in conjunction with single and multiple detector arrangements have been examined. Based on these measurements, it is shown that the advantages of input beam conditioning coupled with modified receiver geometric characteristics would provide a path for BER reduction and hence, appreciable enhancements in data link reliability.

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

Gil, D.M.; Osiry, H.; Pomiro, F.

The hydrogen bond and π-π stacking are two non-covalent interactions able to support cooperative magnetic ordering between paramagnetic centers. This contribution reports the crystal structure and related magnetic properties for VO[Fe(CN){sub 5}NO]·2H{sub 2}O, which has a layered structure. This solid crystallizes with an orthorhombic unit cell, in the Pna2{sub 1} space group, with cell parameters a=14.1804(2), b=10.4935(1), c=7.1722(8) Å and four molecules per unit cell (Z=4). Its crystal structure was solved and refined from powder X-ray diffraction data. Neighboring layers remain linked through a network of hydrogen bonds involving a water molecule coordinated to the axial position for the Vmore » atom and the unbridged axial NO and CN ligands. An uncoordinated water molecule is found forming a triple bridge between these last two ligands and the coordinated water molecule. The magnetic measurements, recorded down to 2 K, shows a ferromagnetic interaction between V atoms located at neighboring layers, with a Curie-Weiss constant of 3.14 K. Such ferromagnetic behavior was interpreted as resulting from a superexchange interaction through the network of strong OH····O{sub H2O}, OH····N{sub CN}, and OH····O{sub NO} hydrogen bonds that connects neighboring layers. The interaction within the layer must be of antiferromagnetic nature and it was detected close to 2 K. - Graphical abstract: Coordination environment for the metals in vanadyl (II) nitroprusside dihydrate. Display Omitted - Highlights: • Crystal structure of vanadyl nitroprusside dehydrate. • Network of hydrogen bonds. • Magnetic interactions through a network of hydrogen bonds. • Layered transition metal nitroprussides.« less

VizieR Online Data Catalog: Cyanomethyl anion and its deuterated derivatives (Liton+, 2014)

NASA Astrophysics Data System (ADS)

Liton, M.; Das., A.; Chakrabarti, S. K.

2013-11-01

We performed detailed quantum chemical simulations to present the spectral properties (infrared, electronic, and rotational) of various forms of the cyanomethyl radical. Moller-Plesset perturbation theory along with the triple-zeta, correlation-consistent basis set is used to obtain different spectroscopic constants of CH2CN-, CHDCN-, and CD2CN- in the gas phase. (4 data files).

VizieR Online Data Catalog: Cyanomethyl anion and its deuterated derivatives (Majumdar+, 2014)

NASA Astrophysics Data System (ADS)

Majumdar, L.; Das., A.; Chakrabarti, S. K.

2013-11-01

We performed detailed quantum chemical simulations to present the spectral properties (infrared, electronic, and rotational) of various forms of the cyanomethyl radical. Moller-Plesset perturbation theory along with the triple-zeta, correlation-consistent basis set is used to obtain different spectroscopic constants of CH2CN-, CHDCN-, and CD2CN- in the gas phase. (4 data files).

Quantification of optical turbulence in the ocean and its effects on beam propagation.

PubMed

Nootz, Gero; Jarosz, Ewa; Dalgleish, Fraser R; Hou, Weilin

2016-11-01

The influence of optically active turbulence on the propagation of laser beams is investigated in clear ocean water over a path length of 8.75 m. The measurement apparatus is described and the effects of optical turbulence on the laser beam are presented. The index of refraction structure constant is extracted from the beam deflection and the results are compared to independently made measures of the turbulence strength (Cn2) by a vertical microstructure profiler. Here we present values of Cn2 taken from aboard the R/V Walton Smith during the Bahamas optical turbulence exercise (BOTEX) in the Tongue of the Ocean between June 30 and July 12, 2011, spanning a range from 10^-14 to 10^-10  m^-2/3. To the best of our knowledge, this is the first time such measurements are reported for the ocean.

Iron(II) catalysis in oxidation of hydrocarbons with ozone in acetonitrile

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

Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

Oxidation of alcohols, ethers, and sulfoxides by ozone in acetonitrile is catalyzed by submillimolar concentrations of Fe(CH 3CN) 6 2+. The catalyst provides both rate acceleration and greater selectivity toward the less oxidized products. For example, Fe(CH 3CN) 6 2+-catalyzed oxidation of benzyl alcohol yields benzaldehyde almost exclusively (>95%), whereas the uncatalyzed reaction generates a 1:1 mixture of benzaldehyde and benzoic acid. Similarly, aliphatic alcohols are oxidized to aldehydes/ketones, cyclobutanol to cyclobutanone, and diethyl ether to a 1:1 mixture of ethanol and acetaldehyde. The kinetics of oxidation of alcohols and diethyl ether are first-order in [Fe(CH 3CN) 6 2+] andmore » [O 3] and independent of [substrate] at concentrations greater than ~5 mM. In this regime, the rate constant for all of the alcohols is approximately the same, k cat = (8 ± 1) × 10 4 M –1 s –1, and that for (C 2H 5) 2O is (5 ± 0.5) × 10 4 M –1 s –1. In the absence of substrate, Fe(CH 3CN) 6 2+ reacts with O 3 with k Fe = (9.3 ± 0.3) × 10 4 M –1 s –1. The similarity between the rate constants k Fe and k cat strongly argues for Fe(CH 3CN) 6 2+/O 3 reaction as rate-determining in catalytic oxidation. The active oxidant produced in Fe(CH 3CN) 6 2+/O 3 reaction is suggested to be an Fe(IV) species in analogy with a related intermediate in aqueous solutions. As a result, this assignment is supported by the similarity in kinetic isotope effects and relative reactivities of the two species toward substrates.« less

Iron(II) catalysis in oxidation of hydrocarbons with ozone in acetonitrile

DOE PAGES

Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

2015-02-11

Oxidation of alcohols, ethers, and sulfoxides by ozone in acetonitrile is catalyzed by submillimolar concentrations of Fe(CH 3CN) 6 2+. The catalyst provides both rate acceleration and greater selectivity toward the less oxidized products. For example, Fe(CH 3CN) 6 2+-catalyzed oxidation of benzyl alcohol yields benzaldehyde almost exclusively (>95%), whereas the uncatalyzed reaction generates a 1:1 mixture of benzaldehyde and benzoic acid. Similarly, aliphatic alcohols are oxidized to aldehydes/ketones, cyclobutanol to cyclobutanone, and diethyl ether to a 1:1 mixture of ethanol and acetaldehyde. The kinetics of oxidation of alcohols and diethyl ether are first-order in [Fe(CH 3CN) 6 2+] andmore » [O 3] and independent of [substrate] at concentrations greater than ~5 mM. In this regime, the rate constant for all of the alcohols is approximately the same, k cat = (8 ± 1) × 10 4 M –1 s –1, and that for (C 2H 5) 2O is (5 ± 0.5) × 10 4 M –1 s –1. In the absence of substrate, Fe(CH 3CN) 6 2+ reacts with O 3 with k Fe = (9.3 ± 0.3) × 10 4 M –1 s –1. The similarity between the rate constants k Fe and k cat strongly argues for Fe(CH 3CN) 6 2+/O 3 reaction as rate-determining in catalytic oxidation. The active oxidant produced in Fe(CH 3CN) 6 2+/O 3 reaction is suggested to be an Fe(IV) species in analogy with a related intermediate in aqueous solutions. As a result, this assignment is supported by the similarity in kinetic isotope effects and relative reactivities of the two species toward substrates.« less

Epitope characterization of a supramolecular protein assembly with a collection of monoclonal antibodies: the case of casein micelle.

PubMed

Johansson, Annette; Lugand, Damien; Rolet-Répécaud, Odile; Mollé, Daniel; Delage, Marie-Madeleine; Peltre, Gabriel; Marchesseau, Sylvie; Léonil, Joëlle; Dupont, Didier

2009-03-01

In milk, kappa-, beta-, alphas(1)- and alphas(2)-casein (CN) are associated into a supramolecular assembly, the micelle. In this work, CN micelles contained in fresh skim milk were used to produce over 100 monoclonal antibodies. The specificity of these probes was determined using libraries of synthetic peptides and peptides fractionated from tryptic hydrolysis of purified CNs. Although kappa-CN and alphas(2)-CN are minor proteins in the micelle (ratio 1:1:4:4 for kappa, alphas(2), alphas(1), beta) a proportionally high number of clones were produced towards these two proteins (32 for each), compared to 9 and 29 for alphas(1)-CN and beta-CN, respectively. Most of the beta-CN and kappa-CN epitopes were identified, while about 50% of alphas(1)-CN and alphas(2)-CN antibodies were suspected to react to conformational linear or discontinuous epitopes, since no peptide binding could be identified. Antibody binding to the phosphoserine rich regions of the three calcium sensitive CNs was weak or non-existing, suggesting them to be hidden in the micelle structure together with alphas(1)-CN. The C-terminal glycomacropeptide of kappa-CN and the C-terminal moiety of beta-CN were well exposed generating the majority of the antibodies specific for these two proteins. The two major antigenic sites of alphas(2) were alphas(2)-CN (f96-114) and (f16-35). Cross-reaction between alphas(2)-CN specific antibodies with alphas(1)-CN illustrated the tangled structure between the two proteins. Immuno-dominant epitopes identified in the present study totally differ from those known for the purified caseins suggesting they were specific for the micelle supramolecular structure.

High-resolution spectroscopy of the C-N stretching band of methylamine

NASA Astrophysics Data System (ADS)

Lees, Ronald M.; Sun, Zhen-Dong; Billinghurst, B. E.

2011-09-01

The C-N stretching infrared fundamental of CH3NH2 has been investigated by high-resolution laser sideband and Fourier transform synchrotron spectroscopy to explore the energy level structure and to look for possible interactions with high-lying torsional levels of the ground state and other vibrational modes. The spectrum is complicated by two coupled large-amplitude motions in the molecule, the CH3 torsion and the NH2 inversion, which lead to rich spectral structure with a wide range of energy level splittings and relative line intensities. Numerous sub-bands have been assigned for K values ranging up to 12 for the stronger a inversion species for the vt = 0 torsional state, along with many of the weaker sub-bands of the s species. The C-N stretching sub-state origins have been determined by fitting the upper-state term values to J(J + 1) power-series expansions. For comparison with the ground-state behaviour, both ground and C-N stretch origins have been fitted to a phenomenological Fourier series model that produces an interesting pattern with the differing periodicities of the torsional and inversion energies. The amplitude of the torsional energy oscillation increases substantially for the C-N stretch, while the amplitude of the inversion energy oscillation is relatively unchanged. Independent inertial scale factors ρ were fitted for the torsion and the inversion and differ significantly in the upper state. The C-N stretching vibrational energy is determined to be 1044.817 cm-1, while the effective upper state B-value is 0.7318 cm-1. Several anharmonic resonances with vt = 4 ground-state levels have been observed and partially characterized. A variety of J-localized level-crossing resonances have also been seen, five of which display forbidden transitions arising from intensity borrowing that allow determination of the interaction coupling constants.

A two force-constant model for complexes B⋯M-X (B is a Lewis base and MX is any diatomic molecule): Intermolecular stretching force constants from centrifugal distortion constants D(J) or Δ(J).

PubMed

Bittner, Dror M; Walker, Nicholas R; Legon, Anthony C

2016-02-21

A two force-constant model is proposed for complexes of the type B⋯MX, in which B is a simple Lewis base of at least C2v symmetry and MX is any diatomic molecule lying along a Cn axis (n ≥ 2) of B. The model assumes a rigid subunit B and that force constants beyond quadratic are negligible. It leads to expressions that allow, in principle, the determination of three quadratic force constants F11, F12, and F22 associated with the r(B⋯M) = r2 and r(M-X) = r1 internal coordinates from the equilibrium centrifugal distortion constants DJ (e) or ΔJ (e), the equilibrium principal axis coordinates a1 and a2, and equilibrium principal moments of inertia. The model can be applied generally to complexes containing different types of intermolecular bond. For example, the intermolecular bond of B⋯MX can be a hydrogen bond if MX is a hydrogen halide, a halogen-bond if MX is a dihalogen molecule, or a stronger, coinage-metal bond if MX is a coinage metal halide. The equations were tested for BrCN, for which accurate equilibrium spectroscopic constants and a complete force field are available. In practice, equilibrium values of DJ (e) or ΔJ (e) for B⋯MX are not available and zero-point quantities must be used instead. The effect of doing so has been tested for BrCN. The zero-point centrifugal distortion constants DJ (0) or ΔJ (0) for all B⋯MX investigated so far are of insufficient accuracy to allow F11 and F22 to be determined simultaneously, even under the assumption F12 = 0 which is shown to be reasonable for BrCN. The calculation of F22 at a series of fixed values of F11 reveals, however, that in cases for which F11 is sufficiently larger than F22, a good approximation to F22 is obtained. Plots of F22 versus F11 have been provided for Kr⋯CuCl, Xe⋯CuCl, OC⋯CuCl, and C2H2⋯AgCl as examples. Even in cases where F22 ∼ F11 (e.g., OC⋯CuCl), such plots will yield either F22 or F11 if the other becomes available.

A two force-constant model for complexes B⋯M-X (B is a Lewis base and MX is any diatomic molecule): Intermolecular stretching force constants from centrifugal distortion constants DJ or ΔJ

NASA Astrophysics Data System (ADS)

Bittner, Dror M.; Walker, Nicholas R.; Legon, Anthony C.

2016-02-01

A two force-constant model is proposed for complexes of the type B⋯MX, in which B is a simple Lewis base of at least C2v symmetry and MX is any diatomic molecule lying along a Cn axis (n ≥ 2) of B. The model assumes a rigid subunit B and that force constants beyond quadratic are negligible. It leads to expressions that allow, in principle, the determination of three quadratic force constants F11, F12, and F22 associated with the r(B⋯M) = r2 and r(M-X) = r1 internal coordinates from the equilibrium centrifugal distortion constants DJ e or ΔJ e , the equilibrium principal axis coordinates a1 and a2, and equilibrium principal moments of inertia. The model can be applied generally to complexes containing different types of intermolecular bond. For example, the intermolecular bond of B⋯MX can be a hydrogen bond if MX is a hydrogen halide, a halogen-bond if MX is a dihalogen molecule, or a stronger, coinage-metal bond if MX is a coinage metal halide. The equations were tested for BrCN, for which accurate equilibrium spectroscopic constants and a complete force field are available. In practice, equilibrium values of DJ e or ΔJ e for B⋯MX are not available and zero-point quantities must be used instead. The effect of doing so has been tested for BrCN. The zero-point centrifugal distortion constants DJ 0 or ΔJ 0 for all B⋯MX investigated so far are of insufficient accuracy to allow F11 and F22 to be determined simultaneously, even under the assumption F12 = 0 which is shown to be reasonable for BrCN. The calculation of F22 at a series of fixed values of F11 reveals, however, that in cases for which F11 is sufficiently larger than F22, a good approximation to F22 is obtained. Plots of F22 versus F11 have been provided for Kr⋯CuCl, Xe⋯CuCl, OC⋯CuCl, and C2H2⋯AgCl as examples. Even in cases where F22 ˜ F11 (e.g., OC⋯CuCl), such plots will yield either F22 or F11 if the other becomes available.

Substitution structure of cyanogen, NCCN, from high-resolution far infrared spectra

NASA Astrophysics Data System (ADS)

Grecu, John C.; Winnewisser, Brenda P.; Winnewisser, Manfred

2003-04-01

The lowest lying vibrational bands of the gas-phase spectra of cyanogen, NCCN, and four of its isotopomers, 15NCCN, N13CCN, 15NCC15N, and N13C13CN, were recorded with a Fourier transform interferometer. The resolution was limited by the maximum optical path difference (MOPD) attainable with the interferometer to FWHM=0.0012 cm-1. Rovibrational transitions of the ν5 ( ≈230 cm-1) and also the ν2- ν5 ( ≈610 cm-1) band systems were assigned for all five isotopomers. The use of an effective Hamiltonian for linear molecules to fit the data yielded precise spectroscopic vibrational and rotational constants for the vibrational states ( v1v2v3v4v5) or ( v4v5)=(00), (01), (02), (03), and (01000). These data include the first rotationally resolved transitions involving (01000). Complete substitution ( rs) structures of cyanogen, based on both single and double isotopic substitution of the parent species, were calculated. The derived structure is rCC=138.48(17) pm and rCN=115.66(13) pm. The two rs structures coincide within the errors due to remaining contributions of zero-point vibrations.

Binuclear Pt-Tl bonded complex with square pyramidal coordination around Pt: a combined multinuclear NMR, EXAFS, UV-Vis, and DFT/TDDFT study in dimethylsulfoxide solution.

PubMed

Purgel, Mihály; Maliarik, Mikhail; Glaser, Julius; Platas-Iglesias, Carlos; Persson, Ingmar; Tóth, Imre

2011-07-04

The structure and bonding of a new Pt-Tl bonded complex formed in dimethylsulfoxide (dmso), (CN)(4)Pt-Tl(dmso)(5)(+), have been studied by multinuclear NMR and UV-vis spectroscopies, and EXAFS measurements in combination with density functional theory (DFT) and time dependent density functional theory (TDDFT) calculations. This complex is formed following the equilibrium reaction Pt(CN)(4)(2-) + Tl(dmso)(6)(3+) ⇆ (CN)(4)Pt-Tl(dmso)(5)(+) + dmso. The stability constant of the Pt-Tl bonded species, as determined using (13)C NMR spectroscopy, amounts to log K = 2.9 ± 0.2. The (NC)(4)Pt-Tl(dmso)(5)(+) species constitutes the first example of a Pt-Tl bonded cyanide complex in which the sixth coordination position around Pt (in trans with respect to the Tl atom) is not occupied. The spectral parameters confirm the formation of the metal-metal bond, but differ substantially from those measured earlier in aqueous solution for complexes (CN)(5)Pt-Tl(CN)(n)(H(2)O)(x)(n-) (n = 0-3). The (205) Tl NMR chemical shift, δ = 75 ppm, is at extraordinary high field, while spin-spin coupling constant, (1)J(Pt-Tl) = 93 kHz, is the largest measured to date for a Pt-Tl bond in the absence of supporting bridging ligands. The absorption spectrum is dominated by two strong absorption bands in the UV region that are assigned to MMCT (Pt → Tl) and LMCT (dmso → Tl) bands, respectively, on the basis of MO and TDDFT calculations. The solution of the complex has a bright yellow color as a result of a shoulder present on the low energy side of the band at 355 nm. The geometry of the (CN)(4)Pt-Tl core can be elucidated from NMR data, but the particular stoichiometry and structure involving the dmso ligands are established by using Tl and Pt L(III)-edge EXAFS measurements. The Pt-Tl bond distance is 2.67(1) Å, the Tl-O bond distance is 2.282(6) Å, and the Pt-C-N entity is linear with Pt-C and Pt···N distances amounting to 1.969(6) and 3.096(6) Å, respectively. Geometry optimizations on the (CN)(4)Pt-Tl(dmso)(5)(+) system by using DFT calculations (B3LYP model) provide bond distances in excellent agreement with the EXAFS data. The four cyanide ligands are located in a square around the Pt atom, while the Tl atom is coordinated in a distorted octahedral fashion with the metal being located 0.40 Å above the equatorial plane described by four oxygen atoms of dmso ligands. The four equatorial Tl-O bonds and the four cyano ligands around the Pt atom are arranged in an alternate geometry. The coordination environment around Pt may be considered as being square pyramidal, where the apical position is occupied by the Tl atom. The optimized geometry of (CN)(4)Pt-Tl(dmso)(5)(+) is asymmetrical (C(1) point group). This low symmetry might be responsible for the unusually large NMR linewidths observed due to intramolecular chemical exchange processes. The nature of the Pt-Tl bond has been studied by MO analysis. The metal-metal bond formation in (CN)(4)Pt-Tl(dmso)(5)(+) can be simply interpreted as the result of a Pt(5d(z(2)))(2) → Tl(6s)(0) donation. This bonding scheme may rationalize the smaller thermodynamic stability of this adduct compared to the related complexes with (CN)(5)Pt-Tl entity, where the linear C-Pt-Tl unit constitutes a very stable bonding system. © 2011 American Chemical Society

Metal dioxides as analogue of SiO2 under strong compression studied by synchrotron XRD and simulations

NASA Astrophysics Data System (ADS)

Liu, H.; Liu, L. L.

2017-12-01

The phase transition sequence of SiO2 inducing by high pressure was theoretically predicted as coordination number (CN=6) structures (rutile, pyrite), CN=8 (Pnma) and CN=9 (P-62m) structures, but only the phases up to pyrite structure in SiO2 were observed experimentally up to now. The CN8 phase and CN9 phases of SiO2 were predicted to be stable at least 650 GPa, which is challenging to achieve in the static DAC experiment at present. In other metal dioxide systems, such as TiO2, the ambient rutile and anatase phases first transform to pyrite (CN6), then to the baddeleyite (CN7) phase, to a Pnma (CN8) phase and P-62m(CN9) phase. In this report, under strong compression at room temperature, several metal dioxides were studied experimentally and theoretically, to verify whether this theoretical predicted trend is common transition path under strong compression. This work was supported by Natural Science Foundation of China (11374075), Heilongjiang Province Science Fund for Distinguished Young Scholars (JC201005), Longjiang Scholar, the Fundamental Research Funds for the Central Universities (HIT. BRET1.2010002, HIT. IBRSEM.A.201403).

TRAPPIST monitoring of comet C/2012 F6 (Lemmon)

NASA Astrophysics Data System (ADS)

Opitom, C.; Jehin, E.; Manfroid, J.; Hutsemékers, D.; Gillon, M.; Magain, P.

2015-02-01

We report the results of the long-term narrowband photometry and imaging monitoring of comet C/2012 F6 (Lemmon) with the robotic TRAPPIST telescope (La Silla Observatory). Observations covered 52 nights pre- and post-perihelion between December 11, 2012, and June 11, 2013 (perihelion: 24 March, 2013). We followed the evolution of the OH, NH, CN, C3, and C2 production rates computed with the Haser model as well as the evolution of the A(θ)fρ parameter as a proxy for the dust production. All five gas species display similar slopes for the heliocentric dependence. An asymmetry about perihelion is observed, the rate of brightening being steeper than the rate of fading. The chemical composition of the comet's coma changes slightly along the orbit: the relative abundance of C2 to CN increases with the heliocentric distance (r) below -1.4 au and decreases with r beyond 1.4 au while the C3-to-CN ratio is constant during our observations. The behavior of the dust is different from that of the gas, the slope of the heliocentric dependence becoming steeper in early February, correlated to a change in the visual lightcurve slope. However, the dust color does not vary during the observations. The application of several enhancement techniques on the images revealed structures in the CN, C3, and C2 images. These features imply the existence of one or several active zone(s) on the comet nucleus. The shape of the structures is similar in these three filters and changes from a roughly hourglass shape in December and January to a corkscrew shape in February and March. The structures in the continuum filters (sampling the dust) are not correlated to those observed for the gas. During several full nights in February, we observed changes in the CN and C2 structures that repeated periodically because of the nucleus rotation, our derived rotational period being of 9.52 ± 0.05 h. Full Tables 2, 4, 6 are only 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/574/A38

Titania/CnTAB Nanoskeleton as adsorbent and photocatalyst for removal of alkylphenols dissolved in water.

PubMed

Sakai, Toshio; Da Loves, Albar; Okada, Tomohiko; Mishima, Shozi

2013-03-15

We report here on the removal of alkylphenols (phenol, 4-n-propylphenol, 4-n-heptylphenol and 4-nonylphenol) dissolved in water using the composite particles of nanocrystalline titania and alkyltrimethylammonium bromide (CnH2n+1N(CH3)3Br, CnTAB; n=12, 14, 16 and 18) (named as TiO2/CnTAB Nanoskeleton) as adsorbents and photocatalysts. In particular, the adsorption of alkylphenols onto TiO2/CnTAB Nanoskeleton in water was investigated in terms of hydrophobic interaction between alkylphenols and CnTAB, surface area, pore structure and crystal size of TiO2/CnTAB Nanoskeleton. We revealed that CnTAB incorporated in the TiO2/CnTAB Nanoskeleton promotes the adsorption of alkylphenols onto TiO2/CnTAB Nanoskeleton due to the hydrophobic interaction between alkylphenols and CnTAB. On the other hand, the surface area, pore structure and crystal size of TiO2/CnTAB Nanoskeleton did not affect the adsorption of alkylphenols onto TiO2/CnTAB Nanoskeleton. We also found that the alkylphenols dissolved in water were completely removed by the combination of adsorption and photocatalytic degradation by the TiO2/CnTAB Nanoskeleton under UV irradiation. These results prove that the TiO2/CnTAB Nanoskeleton acts as in tandem an adsorbent and a photocatalyst for removal of alkylphenols dissolved in water. Copyright © 2013 Elsevier B.V. All rights reserved.

Coherent assembly of heterostructures in ternary and quaternary carbonitrides

NASA Astrophysics Data System (ADS)

Caicedo, J. C.; Aperador, W.; Saldarriaga, W.

2018-05-01

In this study, ternary and quaternary carbonitride heterostructure systems were grown on silicon (100) substrates in order to investigate coherent assembly in TiCN/TiNbCN. The heterostructure films were grown using the reactive r. f. magnetron sputtering technique by systematically varying the bilayer period (Λ) and the bilayer number (n), while maintaining a constant total coating thickness (∼3 μm). The heterostructures were characterized by high angle X-ray diffraction (HA-XRD) and low angle X-ray diffraction, while the TiCN and TiNbCN layers were analyzed by X-ray photoelectron spectroscopy and transmission electron microscopy. The HA-XRD results indicated preferential growth in the face-centered cubic (111) crystal structure for the [TiCN/TiNbCN]n heterostructures. The maximum coherent assembly was observed with the presence of satellite peaks. Thus, ternary and quaternary carbonitride films were designed and deposited on Si (100) substrates with bilayer periods (Λ) in a broad range from nanometers to hundreds of nanometers in order to study the structural evolution and coherent assembly progress as the bilayer thickness decreased. We determined physical properties comprising the critical angle (θc) (0.362°), electronic density (ρe) (0.521 × 1033 el/m3), dispersion coefficient (δ) (0.554 el/m3), and refractive index (n) (0.999944) as functions of the number of bilayers (n).

An Integrated approach (thermodynamic, structural, and computational) to the study of complexation of alkali-metal cations by a lower-rim calix[4]arene amide derivative in acetonitrile.

PubMed

Horvat, Gordan; Stilinović, Vladimir; Hrenar, Tomica; Kaitner, Branko; Frkanec, Leo; Tomišić, Vladislav

2012-06-04

The calix[4]arene secondary-amide derivative L was synthesized, and its complexation with alkali-metal cations in acetonitrile (MeCN) was studied by means of spectrophotometric, NMR, conductometric, and microcalorimetric titrations at 25 °C. The stability constants of the 1:1 (metal/ligand) complexes determined by different methods were in excellent agreement. For the complexation of M(+) (M = Li, Na, K) with L, both enthalpic and entropic contributions were favorable, with their values and mutual relations being quite strongly dependent on the cation. The enthalpic and overall stability was the largest in the case of the sodium complex. Molecular and crystal structures of free L, its methanol and MeCN solvates, the sodium complex, and its MeCN solvate were determined by single-crystal X-ray diffraction. The inclusion of a MeCN molecule in the calixarene hydrophobic cavity was observed both in solution and in the solid state. This specific interaction was found to be stronger in the case of metal complexes compared to the free ligand because of the better preorganization of the hydrophobic cone to accept the solvent molecule. Density functional theory calculations showed that the flattened cone conformation (C(2) point group) of L was generally more favorable than the square cone conformation (C(4) point group). In the complex with Na(+), L was in square cone conformation, whereas in its adduct with MeCN, the conformation was slightly distorted from the full symmetry. These conformations were in agreement with those observed in the solid state. The classical molecular dynamics simulations indicated that the MeCN molecule enters the L hydrophobic cavity of both the free ligand and its alkali-metal complexes. The inclusion of MeCN in the cone of free L was accompanied by the conformational change from C(2) to C(4) symmetry. As in solution studies, in the case of ML(+) complexes, an allosteric effect was observed: the ligand was already in the appropriate square cone conformation to bind the solvent molecule, allowing it to more easily and faster enter the calixarene cavity.

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

NASA Astrophysics Data System (ADS)

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.

Tribological behavior and self-healing functionality of TiNbCN-Ag coatings in wide temperature range

NASA Astrophysics Data System (ADS)

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.

Ordered bimetallic ferromagnets of chromium(III): [Cr(NH 3) 6][Cr(CN) 6], [Cr(H 2O)(NH 3) 5][Cr(CN) 6], and trans-[Cr(en) 2(H 2O) 2]trans-[Cr(en) 2(OH)F] 2(CIO 4) 5·2H 2O

NASA Astrophysics Data System (ADS)

Burriel, Ramón; Casabó, Jaime; Pons, Josefina; Carnegie, David W.; Carlin, Richard L.

1985-07-01

The magnetic bahavior of the isomorphous compounds [Cr(NH 3) 6][Cr(CN) 6] and [Cr(H 2O)(NH 3) 5][Cr(CN) 6] has been studied by means of zero-field susceptibility measurements. The materials order ferromagnetically at 0.60 and 0.38K, respectively. The compounds behave as examples of the ferromagnetic ( S=3/2) Heisenberg body-center-cubic lattice. The susceptibilities have been analyzed and compared to the Padé approximants of the high-temperature series expansion for this model, a remarkably good fit being obtained with exchange constants 0.042 and 0.022 K, respectively. Another bimetallic substance, trans-[Cr(en) 2(H 2O) 2] trans-[Cr(en) 2(OH)F] 2(CIO 4) 5·2H 2O, with a dominant Heisenberg ferromagnetic interaction J/ kB=0.122 K in one dimension, orders antiferromagnetically at 0.14 K due to a weaker interchain interaction with exchange constant z‧ J‧/ kB=-0.019 K. The three sets of measurements have been carried out on powdered samples for which demagnetization effects are important. The exchange interactions are remarkably weak for such concentrated magnetic materials, yet they are stronger than those found in a number of other such Cr/Cr compounds.

Structure of cyano-anion ionic liquids: X-ray scattering and simulations

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

Dhungana, Kamal B.; Faria, Luiz F. O.; Wu, Boning

2016-07-14

Ionic liquids with cyano anions have long been used because of their unique combination of low-melting temperatures, reduced viscosities, and increased conductivities. Recently we have shown that cyano anions in ionic liquids are particularly interesting for their potential use as electron donors to excited state photo-acceptors [B. Wu et al., J. Phys. Chem. B 119, 14790–14799 (2015)]. Here we report on bulk structural and quantum mechanical results for a series of ionic liquids based on the 1-ethyl-3-methylimidazolium cation, paired with the following five cyano anions: SeCN-, SCN-, N(CN)-2N(CN)2-, C(CN)-3C(CN)3-, and B(CN)-4B(CN)4-. By combining molecular dynamics simulations, high-energy X-ray scattering measurements,more » and periodic boundary condition DFT calculations, we are able to obtain a comprehensive description of the liquid landscape as well as the nature of the HOMO-LUMO states for these ionic liquids in the condensed phase. Features in the structure functions for these ionic liquids are somewhat different than the commonly observed adjacency, charge-charge, and polarity peaks, especially for the bulkiest B(CN)-4B(CN)4- anion. While the other four cyano-anion ionic liquids present an anionic HOMO, the one for Im+2,1Im2,1+/B(CN)-4B(CN)4- is cationic.« less

Iodide-free ionic liquid with dual redox couples for dye-sensitized solar cells with high open-circuit voltage.

PubMed

Li, Chun-Ting; Lee, Chuan-Pei; Lee, Chi-Ta; Li, Sie-Rong; Sun, Shih-Sheng; Ho, Kuo-Chuan

2015-04-13

A novel ionic-liquid mediator, 1-butyl-3-{2-oxo-2-[(2,2,6,6-tetramethylpiperidin-4-yl)amino]ethyl}-1H-imidazol-3-ium selenocyanate (ITSeCN), has been successfully synthesized for dye-sensitized solar cells (DSSCs). ITSeCN possesses dual redox channels, imidazolium-functionalized 2,2,6,6-tetramethylpiperidine N-oxyl (TEMPO) and selenocyanate, which can serve as the cationic redox mediator and the anionic redox mediator, respectively. Therefore, ITSeCN has a favorable redox nature, which results in a more positive standard potential, larger diffusivity, and better kinetic heterogeneous rate constant than those of iodide. The DSSC with the ITSeCN electrolyte shows an efficiency of 8.38 % with a high open-current voltage (VOC ) of 854.3 mV, and this VOC value is about 150 mV higher than that for the iodide-based DSSC. Moreover, different electrocatalytic materials were employed to trigger the redox reaction of ITSeCN. The ITSeCN-based DSSC with the CoSe counter electrode achieved the best performance of 9.01 %, which suggested that transition-metal compound-type materials would be suitable for our newly synthesized ITSeCN mediator. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical study on the potential energy surfaces of CaNC and CaCN

NASA Astrophysics Data System (ADS)

Ishii, Keisaku; Taketsugu, Tetsuya; Hirano, Tsuneo

2003-06-01

The potential energy surfaces of CaNC ( overlineX2Σ+) and CaCN ( overlineX2Σ+) have been investigated by the highly correlated ab initio molecular orbital methods. The bending potential for CaNC is shallow, and shows quite anharmonic and anomalous character, which can explain why the centrifugal distortion constants up to the tenth order were required for the analysis of its rotational spectrum. The reaction path for the isomerization reaction of CaNC and CaCN was also determined: The activation barrier is 2111 cm -1 from the CaNC side, and 602 cm -1 from the CaCN side. Core-core and core-valence correlation contributions of Ca M-shell electrons make the Ca-N (for CaNC) and Ca-C (for CaCN) bond lengths shorter by 0.05 and 0.04 Å, respectively, which indicates the significance of these core-correlation effects.

Structural and magnetic properties of Prussian blue analogue molecular magnet Fe1.5[Cr(CN)6].mH2O

NASA Astrophysics Data System (ADS)

Bhatt, Pramod; Meena, S. S.; Mukadam, M. D.; Yusuf, S. M.

2016-05-01

Molecular magnets, based on Prussian blue analogues, Fe1.5[Cr(CN)6].mH2O have been synthesized in the bulk as well as nanoparticle forms using a co-precipitation method, and their structural and magnetic properties have been investigated using x-ray diffraction (XRD) Mössbauer spectroscopy and dc magnetization. The XRD study confirms the single phase crystalline and nanoparticle nature of the compounds with a face centered cubic (fcc) structure of space group Fm3m. The values of lattice constant are found to be ~10.18(5) Å and ~9.98(9)Å, for the bulk and nanoparticle samples, respectively. The dc magnetization shows a Curie temperature (TC) of ~17 K and ~5 K for the bulk and nanopartcile samples, respectively. The Mossouber spectroscopy reveal that the compound shows spin flipping from the high spin (HS) Fe (CrIII-C≡N-FeII) to low spin (LS) FeII ions (CrIII-N≡C-FeII). Moreover, the TC and the HS state of the Fe ions decreases (converts to its LS states) with time as well as in the nanoparticle form compared to bulk.

Synchrotron microtomographic quantification of geometrical soil pore characteristics affected by compaction

NASA Astrophysics Data System (ADS)

Udawatta, Ranjith P.; Gantzer, Clark J.; Anderson, Stephen H.; Assouline, Shmuel

2016-05-01

Soil compaction degrades soil structure and affects water, heat, and gas exchange as well as root penetration and crop production. The objective of this study was to use X-ray computed microtomography (CMT) techniques to compare differences in geometrical soil pore parameters as influenced by compaction of two different aggregate size classes. Sieved (diameter < 2 mm and < 0.5 mm) and repacked (1.51 and 1.72 Mg m-3) Hamra soil cores of 5 by 5 mm (average porosities were 0.44 and 0.35) were imaged at 9.6 μm resolution at the Argonne Advanced Photon Source (synchrotron facility) using X-ray CMT. Images of 58.9 mm3 volume were analyzed using 3-Dimensional Medial Axis (3-DMA) software. Geometrical characteristics of the spatial distributions of pore structures (pore radii, volume, connectivity, path length, and tortuosity) were numerically investigated. Results show that the coordination number (CN) distribution and path length (PL) measured from the medial axis were reasonably fit by exponential relationships P(CN) = 10-CN/Co and P(PL) = 10-PL/PLo, respectively, where Co and PLo are the corresponding characteristic constants. Compaction reduced porosity, average pore size, number of pores, and characteristic constants. The average pore radii (63.7 and 61 µm; p < 0.04), largest pore volume (1.58 and 0.58 mm3; p = 0.06), number of pores (55 and 50; p = 0.09), and characteristic coordination number (3.74 and 3.94; p = 0.02) were significantly different between the low-density than the high-density treatment. Aggregate size also influenced measured geometrical pore parameters. This analytical technique provides a tool for assessing changes in soil pores that affect hydraulic properties and thereby provides information to assist in assessment of soil management systems.

Vibrational Spectra of Tetrahedral Fullerenes.

PubMed

Cheng; Li; Tang

1999-01-01

From the topological structures of the following classes of tetrahedral fullerenes-(1) Cn(h, h; -i, i), Cn(h, 0; -i, 2i), Cn(2h + i, -h + i; i, i), Cn(h - i, h + 2i; -i, 2i), and Cn(h, i; 0, i) for Td symmetry; (2) Cn(h, k; k, h), Cn(h, k; -h - k, k), and Cn(h, k; -h, h + k) for Th symmetry; (3) Cn(h, k; i, j) for T symmetry-we have obtained theoretically the formulas for the numbers of their IR and Raman active modes for all of the tetrahedral fullerenes through the decomposition of their nuclear motions into irreducible representations by means of group theory. Copyright 1999 Academic Press.

Rotational Spectrum, Conformational Composition, and Quantum Chemical Calculations of Cyanomethyl Formate (HC(O)OCH2C≡N), a Compound of Potential Astrochemical Interest.

PubMed

Samdal, Svein; Møllendal, Harald; Carles, Sophie

2015-08-27

The rotational spectrum of cyanomethyl formate (HC(O)OCH2C≡N) has been recorded in the 12–123 GHz spectral range. The spectra of two conformers were assigned. The rotamer denoted I has a symmetry plane and two out-of plane hydrogen atoms belonging to the cyanomethyl (CH2CN) moiety. In the conformer called II, the cyanomethyl group is rotated 80.3° out of this plane. Conformer I has an energy that is 1.4(6) kJ/mol lower than the energy of II according to relative intensity measurements. A large number of rotational transitions have been assigned for the ground and vibrationally excited states of the two conformers and accurate spectroscopic constants have been obtained. These constants should predict frequencies of transitions outside the investigated spectral range with a very high degree of precision. It is suggested that cyanomethyl formate is a potential interstellar compound. This suggestion is based on the fact that its congener methyl formate (HC(O)OCH3) exists across a large variety of interstellar environments and the fact that cyanides are very prevalent in the Universe. The experimental work has been augmented by high-level quantum chemical calculations. The CCSD/cc-pVQZ calculations are found to predict structures of the two forms that are very close to the Born–Oppenheimer equilibrium structures. MP2/cc-pVTZ predictions of several vibration–rotation interaction constants were generally found to be rather inaccurate. A gas-phase reaction between methyl formate and the cyanomethyl radical CH2CN to produce a hydrogen atom and cyanomethyl formate was mimicked using MP2/cc-pVTZ calculations. It was found that this reaction is not favored thermodynamically. It is also conjectured that the possible formation of cyanomethyl formate might be catalyzed and take place on interstellar particles.

Diffusion tensor imaging for anatomical localization of cranial nerves and cranial nerve nuclei in pontine lesions: initial experiences with 3T-MRI.

PubMed

Ulrich, Nils H; Ahmadli, Uzeyir; Woernle, Christoph M; Alzarhani, Yahea A; Bertalanffy, Helmut; Kollias, Spyros S

2014-11-01

With continuous refinement of neurosurgical techniques and higher resolution in neuroimaging, the management of pontine lesions is constantly improving. Among pontine structures with vital functions that are at risk of being damaged by surgical manipulation, cranial nerves (CN) and cranial nerve nuclei (CNN) such as CN V, VI, and VII are critical. Pre-operative localization of the intrapontine course of CN and CNN should be beneficial for surgical outcomes. Our objective was to accurately localize CN and CNN in patients with intra-axial lesions in the pons using diffusion tensor imaging (DTI) and estimate its input in surgical planning for avoiding unintended loss of their function during surgery. DTI of the pons obtained pre-operatively on a 3Tesla MR scanner was analyzed prospectively for the accurate localization of CN and CNN V, VI and VII in seven patients with intra-axial lesions in the pons. Anatomical sections in the pons were used to estimate abnormalities on color-coded fractional anisotropy maps. Imaging abnormalities were correlated with CN symptoms before and after surgery. The course of CN and the area of CNN were identified using DTI pre- and post-operatively. Clinical associations between post-operative improvements and the corresponding CN area of the pons were demonstrated. Our results suggest that pre- and post-operative DTI allows identification of key anatomical structures in the pons and enables estimation of their involvement by pathology. It may predict clinical outcome and help us to better understand the involvement of the intrinsic anatomy by pathological processes. Copyright © 2014 Elsevier Ltd. All rights reserved.

Synthesis, PtS-type structure, and anomalous mechanics of the Cd(CN)2 precursor Cd(NH3)2[Cd(CN)4].

PubMed

Coates, Chloe S; Makepeace, Joshua W; Seel, Andrew G; Baise, Mia; Slater, Ben; Goodwin, Andrew L

2018-05-15

We report the nonaqueous synthesis of Cd(CN)2 by oxidation of cadmium metal with Hg(CN)2 in liquid ammonia. The reaction proceeds via an intermediate of composition Cd(NH3)2[Cd(CN)4], which converts to Cd(CN)2 on prolonged heating. Powder X-ray diffraction measurements allow us to determine the crystal structure of the previously-unreported Cd(NH3)2[Cd(CN)4], which we find to adopt a twofold interpenetrating PtS topology. We discuss the effect of partial oxidation on the Cd/Hg composition of this intermediate, as well as its implications for the reconstructive nature of the deammination process. Variable-temperature X-ray diffraction measurements allow us to characterise the anisotropic negative thermal expansion (NTE) behaviour of Cd(NH3)2[Cd(CN)4] together with the effect of Cd/Hg substitution; ab initio density functional theory (DFT) calculations reveal a similarly anomalous mechanical response in the form of both negative linear compressibility (NLC) and negative Poisson's ratios.

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

NASA Astrophysics Data System (ADS)

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.

Analysis of the Photomagnetic Properties of Cyano-Bridged Heterobimetallic Complexes by X-Ray Diffraction

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

Svendsen, Helle; Jørgensen, Mads Ry Vogel; Overgaard, Jacob

2012-10-11

Single crystal synchrotron X-ray diffraction measurements have been carried out on [Nd(DMF){sub 4}(H{sub 2}O){sub 3}({mu}-CN)Fe(CN){sub 5}] {center_dot} H{sub 2}O (DMF = dimethyl-formamide), 1; [Y(DMF){sub 4}(H{sub 2}O){sub 3}({mu}-CN)Fe(CN){sub 5}] {center_dot} H{sub 2}O, 2; [Ce(DMF){sub 4}(H{sub 2}O){sub 3}({mu}-CN)Fe(CN){sub 5}] {center_dot} H{sub 2}O, 3; [Sm(DMF){sub 4}(H{sub 2}O){sub 3}({mu}-CN)Fe(CN){sub 5}] {center_dot} H{sub 2}O, 4; [Tb(DMF){sub 4}(H{sub 2}O)3({mu}-CN)Fe(CN){sub 5}] {center_dot} H{sub 2}O, 5; [Yb(DMF){sub 4}(H{sub 2}O){sub 3}({mu}-CN)Fe(CN){sub 5}] {center_dot} H{sub 2}O, 6; and [Nd(DMF){sub 4}(H{sub 2}O){sub 3}({mu}-CN)Co(CN){sub 5}] {center_dot} H{sub 2}O, 7, at 15(2) K with and without UV illumination of the crystals. Significant changes in unit cell parameters are observed for all of themore » iron-containing complexes, while compound 7 shows no response to UV illumination. These results are consistent with previous results and are furthermore reproduced by powder synchrotron X-ray diffraction for compounds 1 and 7. Photoexcited crystal structures have been determined for 1-6 from refinements of two-conformer models, and excited state occupancies in the range 80-94% are found. Significant bond length changes are observed for the Fe-ligand bonds (up to 0.06 {angstrom}), the cyano bonds (up to 0.02 {angstrom}), and the lanthanide-ligand bonds (up to 0.1 {angstrom}). On the contrary, powder X-ray diffraction on the simple compound K{sub 3}Fe(CN)6, 8, upon UV illumination does not show any structural changes, suggesting that the photomagnetic effect requires the presence of both the transition metal and the lanthanide ion. Photomagnetic measurements show an increase in magnetization of the excited state of 1 of up to 3%, which is much diminished compared with previously published values of 45%. Furthermore, they show that the isostructural complex [La(DMF){sub 4}(H{sub 2}O){sub 3}({mu}-CN)Fe(CN){sub 5}] {center_dot} H{sub 2}O, 9, exhibits identical magnetic responses in the UV-induced excited crystal structure.« less

Synthesis, crystal structure, theoretical calculations and antimicrobial properties of [Pt(tetramethylthiourea)4] [Pt(CN)4]·4H2O

NASA Astrophysics Data System (ADS)

Sadaf, Haseeba; Isab, Anvarhusein A.; Ahmad, Saeed; Espinosa, Arturo; Mas-Montoya, Míriam; Khan, Islam Ullah; Ejaz; Rehman, Seerat-ur; Ali, Muhammad Akhtar Javed; Saleem, Muhammad; Ruiz, José; Janiak, Christoph

2015-04-01

A new platinum(II) complex, [Pt(Tmtu)4][Pt(CN)4]·4H2O (1) was synthesized by reaction of K2[PtCl4], KCN and tetramethylthiourea (Tmtu). Its structure was determined by X-ray crystallography. The [Pt(CN)4]2- anion shows regular square planar geometry at platinum, while in the [Pt(Tmtu)4]2+ cation the geometry at platinum is somewhat distorted. Hydrogen bonding between water molecules and the cyanide nitrogen of [Pt(CN)4]2- ions stabilizes the structure and leads to a supramolecular 2D network. DFT calculations support the experimentally found dinuclear (homocoordinated) ion-pair structure 1 as the most stable in comparison to noncovalent dimer [Pt(CN)2(Tmtu)2]222 that could, in turn, be involved in the formation sequence of 1. Antimicrobial activities of the complex were evaluated by minimum inhibitory concentration and the results showed that the complex exhibited moderate activities against gram-negative bacteria (Escherichiacoli, Pseudomonas aeruginosa) and molds (Aspergillus niger,Penicilliumcitrinum).

Investigating vibrational anharmonic couplings in cyanide-bridged transition metal mixed valence complexes using two-dimensional infrared spectroscopy.

PubMed

Slenkamp, Karla M; Lynch, Michael S; Van Kuiken, Benjamin E; Brookes, Jennifer F; Bannan, Caitlin C; Daifuku, Stephanie L; Khalil, Munira

2014-02-28

Using polarization-selective two-dimensional infrared (2D IR) spectroscopy, we measure anharmonic couplings and angles between the transition dipole moments of the four cyanide stretching (νCN) vibrations found in [(NH3)5Ru(III)NCFe(II)(CN)5](-) (FeRu) dissolved in D2O and formamide and [(NC)5Fe(II)CNPt(IV)(NH3)4NCFe(II)(CN)5](4-) (FePtFe) dissolved in D2O. These cyanide-bridged transition metal complexes serve as model systems for studying the role of high frequency vibrational modes in ultrafast photoinduced charge transfer reactions. Here, we focus on the spectroscopy of the νCN modes in the electronic ground state. The FTIR spectra of the νCN modes of the bimetallic and trimetallic systems are strikingly different in terms of frequencies, amplitudes, and lineshapes. The experimental 2D IR spectra of FeRu and FePtFe and their fits reveal a set of weakly coupled anharmonic νCN modes. The vibrational mode anharmonicities of the individual νCN modes range from 14 to 28 cm(-1). The mixed-mode anharmonicities range from 2 to 14 cm(-1). In general, the bridging νCN mode is most weakly coupled to the radial νCN mode, which involves the terminal CN ligands. Measurement of the relative transition dipole moments of the four νCN modes reveal that the FeRu molecule is almost linear in solution when dissolved in formamide, but it assumes a bent geometry when dissolved in D2O. The νCN modes are modelled as bilinearly coupled anharmonic oscillators with an average coupling constant of 6 cm(-1). This study elucidates the role of the solvent in modulating the molecular geometry and the anharmonic vibrational couplings between the νCN modes in cyanide-bridged transition metal mixed valence complexes.

German cooperation-network 'equity in health'-health promotion in settings.

PubMed

Mielck, Andreas; Kilian, Holger; Lehmann, Frank; Richter-Kornweitz, Antje; Kaba-Schönstein, Lotte

2018-04-01

In 2003, the German Federal Centre for Health Education (BZgA) initiated the national Cooperation-Network (CN) 'Equity in Health'. The CN is constantly increasing in size and scope, supporting setting approaches aimed at reducing health inequalities. A detailed description of the CN has not yet been available in English. The CN comprises a total of 66 institutional cooperation partners. Information concerning the structure and activities can be found on a special website. Coordination Centres (CC) have been established in the 16 federal states, for the coordination of all state-specific activities. Funding for the CN and CC is provided by the BZgA, the German statutory sickness funds and by the state-specific ministries of health. These partners also support the continuous quality improvement, which is based on the good-practice criteria developed by the Advisory Committee of the CN. In 2011, the 'Municipal Partner Process (MPP)' has been launched, specifically supporting local partners and integrated life-course approaches focussing on children. In 2015, the focus has been widened to include all age-groups. In July 2015, a new national health law concerning health promotion and prevention has been ratified by the federal Parliament, with a focus on reducing health inequalities. Currently, the details of its implementation are discussed on a nationwide basis. The CN has long advocated for such a law, and today the CN is a well-accepted partner providing concepts, methods and a strong and long-standing network. The article closes with future challenges faced by the CN.

Benchmark analysis of native and artificial NAD+-dependent enzymes generated by a sequence based design method with or without phylogenetic data.

PubMed

Nakano, Shogo; Motoyama, Tomoharu; Miyashita, Yurina; Ishizuka, Yuki; Matsuo, Naoya; Tokiwa, Hiroaki; Shinoda, Suguru; Asano, Yasuhisa; Ito, Sohei

2018-05-22

The expansion of protein sequence databases has enabled us to design artificial proteins by sequence-based design methods, such as full consensus design (FCD) and ancestral sequence reconstruction (ASR). Artificial proteins with enhanced activity levels compared with native ones can potentially be generated by such methods, but successful design is rare because preparing a sequence library by curating the database and selecting a method is difficult. Utilizing a curated library prepared by reducing conservation energies, we successfully designed two artificial L-threonine 3-dehydrogenase (SDR-TDH) with higher activity levels than native SDR-TDH, FcTDH-N1 and AncTDH, using FCD and ASR, respectively. The artificial SDR-TDHs had excellent thermal stability and NAD+ recognition compared to native SDR-TDH from Cupriavidus necator (CnTDH): the melting temperatures of FcTDH-N1 and AncTDH were about 10 and 5°C higher than CnTDH, respectively, and the dissociation constants toward NAD+ of FcTDH-N1 and AncTDH were two- and seven-fold lower than that of CnTDH, respectively. Enzymatic efficiency of the artificial SDR-TDHs were comparable to that of CnTDH. Crystal structures of FcTDH-N1 and AncTDH were determined at 2.8 and 2.1 Å resolution, respectively. Structural and MD simulation analysis of the SDR-TDHs indicated that only the flexibility at specific regions was changed, suggesting that multiple mutations introduced in the artificial SDR-TDHs altered their flexibility and thereby affected their enzymatic properties. Benchmark analysis of the SDR-TDHs indicated that both FCD and ASR can generate highly functional proteins if a curated library is prepared appropriately.

Structural and energetic properties of acetonitrile-Group IV (A & B) halide complexes.

PubMed

Helminiak, Heather M; Knauf, Robin R; Danforth, Samuel J; Phillips, James A

2014-06-19

We have conducted an extensive computational study of the structural and energetic properties of select acetonitrile-Group IV (A & B) tetrahalide complexes, both CH3CN-MX4 and (CH3CN)2-MX4 (M = Si, Ge, Ti; X = F, Cl). We have also examined the reactivity of CH3CN with SiF4, SiCl4, GeCl4, and TiCl4, and measured low-temperature IR spectra of thin films containing CH3CN with SiF4, GeCl4, or TiCl4. The six 1:1 complexes fall into two general structural classes. CH3CN-TiCl4, CH3CN-TiF4, and CH3CN-GeF4, exhibit relatively short M-N bonds (~2.3 Å), an intermediate degree of distortion in the MX4 subunit, and binding energies ranging from 11.0 to 13.0 kcal/mol. Conversely, CH3CN-GeCl4, CH3CN-SiF4, and CH3CN-SiCl4, are weakly bonded systems, with long M-N distances (>3.0 Å), little distortion in the MX4 subunit, and binding energies ranging from 3.0 to 4.4 kcal/mol. The structural features of analogous 2:1 systems resemble those of their 1:1 counterparts, whereas the binding energies (relative to three isolated fragments) are roughly twice as large. Calculated M-N potential curves in the gas phase and bulk, dielectric media are reported for all 1:1 complexes, and for two systems, CH3CN-GeF4 and CH3CN-SiF4, these data predict significant condensed-phase structural changes. The effect on the CH3CN-SiF4 potential is extreme; the curve becomes quite flat over a broad range in dielectric media, and at higher ε values, the global minimum shifts inward by about 1.0 Å. In bulk reactivity experiments, no reaction was observed between CH3CN and SiF4, SiCl4, or GeCl4, whereas CH3CN and TiCl4 were found to react immediately upon contact. Also, thin-film IR spectra indicate a strong interaction between CH3CN and TiCl4, yet only weak interactions between CH3CN and GeCl4 or SiF4 in the solid state.

Ab initio molecular orbital calculations on the associated complexes of lithium cyanide with ammonia

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

Mohandas, P.; Shivaglal, M.C.; Chandrasekhar, J.

Ab initio molecular orbital (MO) calculations with the 3-21G and 6-31G basis sets are carried out on a series of complexes of NH{sub 3} with Li{sup +}, C{triple_bond}N{sup -}, LiCN, and its isomer LiNC. The BSSE-corrected interaction energies, geometrical parameters, internal force constants, and harmonic vibrational frequencies are evaluated for 15 species. Complexes with trifurcated (C{sub 3v}) structures are calculated to be saddle points on the potential energy surfaces and have one imaginary frequency each. Calculated energies, geometrical parameters, internal force constants, and harmonic vibrational frequencies of the various species considered are discussed in terms of the nature of associationmore » of LiCN with ammonia. The vibrational frequencies of the relevant complexed species are compared with the experimental frequencies reported earlier for solutions of lithium cyanide in liquid ammonia. 40 refs., 1 fig., 4 tabs.« less

Identification of a potential superhard compound ReCN

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

Fan, Xiaofeng; Li, M. M.; Singh, David J.

2015-01-24

Here, we identify a new ternary compound, ReCN and characterize its properties including structural stability and indicators of hardness using first principles calculations. Furthermore, we find that there are two stable structures with space groups P63mc (HI) and P3m1 (HII), in which there are no C–C and N–N bonds. Both structures, H1 and III are elastically and dynamically stable. The electronic structures show that ReCN is a semiconductor, although the parent compounds, ReC 2 and ReN 2 are both metallic. ReCN is found to possess the outstanding mechanical properties with the large bulk modulus, shear modulus and excellent ideal strengths.more » Additionally, ReCN may perhaps be synthesized relatively easily because it becomes thermodynamic stable with respect to decomposition at very low pressures.« less

Microstructure and Corrosion Behavior of CrN and CrSiCN Coatings

NASA Astrophysics Data System (ADS)

Cai, Feng; Yang, Qi; Huang, Xiao; Wei, Ronghua

2010-07-01

Three CrN-based coatings were deposited on 17-4PH stainless steel substrate using plasma enhanced magnetron sputtering (PEMS) technique. The microstructure and corrosion resistance were evaluated to examine the effect of Si and C in the coatings. The three coating compositions were CrN(Cr0.69N0.31), CrSiCN-1 (Cr0.55Si0.014C0.14N0.3), and CrSiCN-2 (Cr0.43Si0.037C0.24N0.3). The testing results indicated that with the increase of Si concentration, the coating microstructure transformed from B1 structure to B1 + Si3N4 structure. All the three coating systems were subjected to electrochemical tests in 3.5% NaCl solution at room temperature. Potentiodynamic polarization results revealed that the CrSiCN-2 coating had a higher anodic current density and a lower corrosion potential when compared to the CrN and CrSiCN-1 coatings. Extended exposure in 3.5% NaCl caused several localized corrosion to the CrSiCN-2 coating due to the porous coating structure. Electrochemical impedance spectroscopic measurements demonstrated that the CrSiCN-1 has better corrosion resistance than CrN and CrSiCN-2.

The microwave spectrum of a triplet carbene: HCCN in the X 3Sigma - state

NASA Astrophysics Data System (ADS)

Saito, Shuji; Endo, Yasuki; Hirota, Eizi

1984-02-01

A simple carbene, the HCCN radical, has been identified in the gas phase using a microwave spectroscopic method. The HCCN molecule was generated in a free space absorption cell by the reaction of CH3CN with the microwave discharge products of CF4. Five rotational transitions, each split into three fine structure components, were observed in the region of 110 to 198 GHz. No hyperfine structure was resolved, although some of the observed lines showed broadening. The rotational constant, the centrifugal distortion constant, the spin-spin coupling constant, and the spin-rotation coupling constant were determined with good precision. The observed spectrum is completely consistent with that expected for a linear molecule in a 3Σ state, in agreement with an earlier matrix EPR study of Bernheim et al. [J. Chem. Phys. 43, 196 (1965)].

[CrIII(NCMe)6]3+--a labile CrIII source enabling formation of Cr[M(CN)6] (M=V, Cr, Mn, Fe) Prussian blue-type magnetic materials.

PubMed

Nelson, Kendric J; Daniels, Matthew C; Reiff, William M; Troff, Shayla A; Miller, Joel S

2007-11-26

The kinetic inertness of the hexaaquachromium(III) (kH2O=2.4x10(-6) s(-1)) has led to challenges with respect to incorporating CrIII ions into Prussian blue-type materials; however, hexakis(acetonitrile)chromium(III) was shown to be substantially more labile (approximately 10(4) times) and enables a new synthetic route for the synthesis of these materials via nonaqueous solvents. The synthesis, spectroscopic, and physical properties of Cr[M(CN)6] (M=V, Cr, Mn, Fe) Prussian blue analogues synthesized from [CrIII(NCMe)6]3+ and the corresponding [MIII(CN)6]3- are described. All these compounds {(NEt4)0.02CrIII[VIII(CN)6]0.98(BF4)(0.08).0.10MeCN (1), CrIII[CrIII(CN)6].0.16MeCN (2), CrIII[MnIII(CN)6].0.10MeCN (3), and (NEt4)0.04CrIII0.64CrIV0.40[FeII(CN)6]0.40[FeIII(CN)6]0.60(BF4)(0.16).1.02MeCN (4)} are ferrimagnets exhibiting cluster-glass behavior. Strong antiferromagnetic coupling was observed for M=V, Cr, and Mn with Weiss constants (theta) ranging from -132 to -524 K; and in 2, where the strongest coupling is observed (theta=-524 K), the highest Tc (110 K) value was observed. Weak antiferromagnetic coupling was observed for M=Fe (theta=-12 K) leading to the lowest Tc (3 K) value in this series. Weak coupling and the low Tc value observed in 4 were additionally contributed by the presence of both [FeII(CN)6]4- and [FeIII(CN)6]3- as confirmed by 57Fe-Mössbauer spectroscopy.

Synthesis and characterization of T[Ni(CN){sub 4}].2pyz with T=Fe, Ni; pyz=pyrazine: Formation of T-pyz-Ni bridges

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

Lemus-Santana, A.A.; Rodriguez-Hernandez, J.; Institute of Materials Science and Technology, University of Havana

2011-08-15

The formation of T-pyz-Ni bridges (pyz=pyrazine) in the T[Ni(CN){sub 4}].2pyz series is known for T=Mn, Zn, Cd and Co but not with T=Fe, Ni. In this contribution the existence of such bridges also for T=Fe, Ni is discussed. The obtained pillared solids, T[Ni(CN){sub 4}].2pyz, were characterized from XRD, TG, UV-Vis, IR, Raman, Moessbauer and magnetic data. Their crystal structures were refined in the orthorhombic Pmna space group from XRD powder patterns. The structural behavior of these solids on cooling down to 77 K was also studied. In the 180-200 K temperature range the occurrence of a structural transition to amore » monoclinic structure (P2{sub 1}/c space group) was observed. No temperature induced spin transition was observed for Fe[Ni(CN){sub 4}].2pyz. The iron (II) was found to be in high spin electronic state and this configuration is preserved on cooling down to 2 K. The magnetic data indicate the occurrence of a low temperature weak anti-ferromagnetic interaction between T metal centers within the T[Ni(CN){sub 4}] layer. In the paramagnetic region for Ni[Ni(CN){sub 4}].2pyz, a reversible temperature induced spin transition for the inner Ni atom was detected. - Graphical abstract: Rippled sheets structure for the pillared solids T[Ni(CN){sub 4}].2pyz. The pyrazine molecule is found forming T-pyz-Ni bridges between neighboring layers. Highlights: > Pillared 2D solids. > Inorganic-organic solids. > Assembling of molecular blocks. > From 1D and 2D building blocks to 3D solids.« less

Effect of pH on dissociation of casein micelles in yak skim milk.

PubMed

Yang, M; Zhang, G D; Yang, J T; Sun, D; Wen, P C; Zhang, W B

2018-04-01

The dissociation of yak casein (CN) micelles was evaluated by scanning electron microscopy, particle size, fluorescence properties, and soluble mineral and CN molecule content at pH 4.6 to 8.2. The results showed that the size of CN micelles remained constant with decreasing pH from 8.2 to 5.8 but sharply increased at pH ≤5.4. Casein micelles began to aggregate at pH 5.4, and the serum magnesium, potassium, iron, zinc, copper, and manganese levels had their minimum values at this pH level. During acidification, colloidal calcium phosphate dramatically disassociated from yak CN micelles, but the soluble CN monomer content decreased slightly. During alkalization, the soluble calcium and phosphorus content decreased below pH 6.8 but increased with pH increases from 6.8 to 8.2. However, the soluble CN content increased markedly during alkalization. The emission wavelength of 8-anilino-1-naphthalenesulfonic acid sodium salt fluorescence decreased during both acidification and alkalization from pH 6.6, whereas the opposite was found for intrinsic fluorescence. Copyright © 2018 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Fourier transform spectroscopy of the Swan (d(sup 3)pi(sub g) - a(sup 3)pi(sub u)) system of the jet-cooled C2 molecule

NASA Technical Reports Server (NTRS)

Prasad, C. V. V.; Bernath, P. F.

1994-01-01

The Swan (d(sup 3)pi(sub g) - a(sup 3)pi(sub u)) system of the C2 molecule was produced in a jet-cooled corona excited supersonic expansion of helium using diazoacetonitrile as a percursor molecule. This spectrum was recorded using the McMath Fourier transform spectrometer of the National Solar Observatory at Kitt Peak. A total of nine bands with v prime = 0 to 3 and v prime prime = 0 to 4 in the range 16,570-22,760/cm were observed and rotationally analyzed. The C2 molecules in this source had a rotational temperature of only 90 K so that only the low-J lines were present in the spectrum. In some sense the low temperatures in the jet source simulate conditions in the interstellar medium. The Swan system of C2 was also produced in a composite wall hollow cathode made Al4C3/Cu, and the rotational structure of the 1-0, 2-1, 3-2, 0-0, and 1-1 bands were analyzed. The data obtained from both these spectra were fitted together along with some recently published line positions. The rotational constants, lambda doubling parameters and the vibrational constants were estimated from this global fit. Our work on jet-cooled C2 follows similar work on the violet and red systems of CN. A summary of this CN work is also presented. also presented.

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

PubMed

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.

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

Osiry, H.; Cano, A.; Reguera, L.

The pentacyanonitrosylferrate complex anion, [Fe(CN){sub 5}NO]{sup 2−}, forms an insoluble solid with Hg(I) ion, of formula unit Hg{sub 2}[Fe(CN){sub 5}NO]·2H{sub 2}O, whose crystal structure and related properties are unknown. This contribution reports the preparation of that compound by the precipitation method and its structural study from X-ray powder patterns complemented with spectroscopic information from IR, Raman, and UV–vis techniques. The crystal structure was solved ab initio and then refined using the Rietveld method. The solid crystallizes with a triclinic unit cell, in the P−1 space group, with cell parameters a=10.1202(12), b=10.1000(13), c=7.4704(11) Å; α=110.664(10), β=110.114(10), γ=104.724(8) °. Within the unitmore » cell, two formula units are accommodated (Z=2). It adopts a layered structure related with the coordination of the equatorial CN groups at their N end to the Hg atoms while the axial CN ligand remains unlinked. Within the layers neighboring Hg{sub 2}[Fe(CN){sub 5}NO] building units remain linked through four relatively strong Hg–Hg interactions, with an interatomic distance of 2.549(3) Å. The charge donation from the equatorial CN groups through their 5σ orbitals results into an increase for the electron density on the Hg atoms, which strengths the Hg–Hg bond. In the Raman spectrum, that metal–metal bond is detected as a stretching vibration band at 167 cm{sup −1}. The available free volume between neighboring layers accommodates two water molecules, which are stabilized within the framework through hydrogen bonds with the N end of the unlinked axial CN group. The removal of these weakly bonded water molecules results in structural disorder for the material 3D framework. - Graphical abstract: Assembling of Hg{sub 2}[Fe(CN){sub 5}NO] units through Hg–Hg interactions. - Highlights: • Homometallic Hg–Hg interactions in metal nitroprusside. • 2D structure supported on metal–metal interactions. • Crystal structure and related properties for mercury (I) nitroprusside. • IR and UV–vis spectral features for mercury (I) nitroprusside.« less

Syntheses, structures, and magnetic properties of three new MnII-[MoIII(CN)7]4- molecular magnets.

PubMed

Wei, Xiao-Qin; Pi, Qian; Shen, Fu-Xing; Shao, Dong; Wei, Hai-Yan; Wang, Xin-Yi

2018-05-22

By reaction of K4[MoIII(CN)7]·2H2O, Mn(ClO4)2·6H2O and bidentate chelating ligands, three new cyano-bridged compounds, namely Mn2(3-pypz)(H2O)(CH3CN)[Mo(CN)7] (1), Mn2(1-pypz)(H2O)(CH3CN)[Mo(CN)7] (2) and Mn2(pyim)(H2O)(CH3CN)[Mo(CN)7] (3) (3-pypz = 2-(1H-pyrazol-3-yl)pyridine, 1-pypz = 2-(1H-pyrazol-1-yl)pyridine, pyim = 2-(1H-imidazol-2-yl)pyridine), have been synthesized and characterized structurally and magnetically. Single crystal X-ray analyses revealed that although the chelating ligands are different, compounds 1 to 3 are isomorphous and crystallize in the same monoclinic space group C2/m. Connected by the bridging cyano groups, one crystallographically unique [Mo(CN)7]4- unit and three crystallographically unique MnII ions of different coordination environments form similar three-dimensional frameworks, which have a four-nodal 3,4,4,7-connecting topological net with a vertex symbol of {43}{44·62}2{410·611}. Magnetic measurements revealed that compounds 1-3 display long-range magnetic ordering with critical temperatures of 64, 66 and 62 K, respectively. These compounds are rare examples of a small number of chelating co-ligand coordinated [Mo(CN)7]4--based magnetic materials. Specifically, the bidentate chelating ligands were successfully introduced into the heptacyanomolybdate system for the first time.

Photomagnetic switching of heterometallic complexes [M(dmf)4(H2O)3(mu-CN)Fe(CN)5].H2O (M=Nd, La, Gd, Y) analyzed by single-crystal X-ray diffraction and ab initio theory.

PubMed

Svendsen, Helle; Overgaard, Jacob; Chevallier, Marie A; Collet, Eric; Chen, Yu-Sheng; Jensen, Frank; Iversen, Bo B

2010-06-25

Single-crystal X-ray diffraction measurements have been carried out on [Nd(dmf)(4)(H(2)O)(3)(mu-CN)Fe(CN)(5)].H(2)O (1; dmf=dimethylformamide), [Nd(dmf)(4)(H(2)O)(3)(mu-CN)Co(CN)(5)].H(2)O (2), [La(dmf)(4)(H(2)O)(3)(mu-CN)Fe(CN)(5)].H(2)O (3), [Gd(dmf)(4)(H(2)O)(3)(mu-CN)Fe(CN)(5)].H(2)O (4), and [Y(dmf)(4)(H(2)O)(3)(mu-CN)Fe(CN)(5)].H(2)O (5), at 15(2) K with and without UV illumination of the crystals. Significant changes in unit-cell parameters were observed for all the iron-containing complexes, whereas 2 showed no response to UV illumination. Photoexcited crystal structures have been determined for 1, 3, and 4 based on refinements of two-conformer models, and excited-state occupancies of 78.6(1), 84(6), and 86.6(7)% were reached, respectively. Significant bond-length changes were observed for the Fe-ligand bonds (up to 0.19 A), the cyano bonds (up to 0.09 A), and the lanthanide-ligand bonds (up to 0.10 A). Ab initio theoretical calculations were carried out for the experimental ground-state geometry of 1 to understand the electronic structure changes upon UV illumination. The calculations suggest that UV illumination gives a charge transfer from the cyano groups on the iron atom to the lanthanide ion moiety, {Nd(dmf)(4)(H(2)O)(3)}, with a distance of approximately 6 A from the iron atom. The charge transfer is accompanied by a reorganization of the spin state on the {Fe(CN)(6)} complex, and a change in geometry that produces a metastable charge-transfer state with an increased number of unpaired electrons, thus accounting for the observed photomagnetic effect.

Cyanide-bridged Fe(III)-Mn(III) bimetallic complexes with dimeric and chain structures constructed from a newly made mer-Fe tricyanide: structures and magnetic properties.

PubMed

Kim, Jae Il; Kwak, Hyun Young; Yoon, Jung Hee; Ryu, Dae Won; Yoo, In Young; Yang, Namgeun; Cho, Beong Ki; Park, Je-Geun; Lee, Hyosug; Hong, Chang Seop

2009-04-06

Four cyanide-linked Fe(III)-Mn(III) complexes were prepared by reacting Mn Schiff bases with a new molecular precursor (PPh(4))[Fe(qcq)(CN)(3)] [1; qcq = 8-(2-quinolinecarboxamido)quinoline anion]. They include a dimeric molecule, [Fe(qcq)(CN)(3)][Mn(3-MeOsalen)(H(2)O)] x 2 H(2)O [2 x 2 H(2)O; 3-MeOsalen = N,N'-ethylenebis(3-methoxysalicylideneiminato) dianion], and three 1D zigzag chains, [Fe(qcq)(CN)(3)][Mn(5-Clsalen)] x 3 H(2)O [3 x 2 MeOH; 5-Clsalen = N,N'-ethylenebis(5-chlorosalicylideneiminato) dianion], [Fe(qcq)(CN)(3)][Mn(5-Brsalen)] x 2 MeOH [4 x 2 MeOH; 5-Brsalen = N,N'-ethylenebis(5-bromosalicylideneiminato) dianion], and Fe(qcq)(CN)(3)][Mn(salen)].MeCN x H(2)O [5 x MeCN; salen = N,N'-ethylenebis(salicylideneiminato) dianion]. The complexes consist of extensive hydrogen bonding and pi-pi stacking interactions, generating multidimensional structures. Magnetic studies demonstrate that antiferromagnetic couplings are operative between Fe(III) and Mn(III) centers bridged by cyanide ligands. On the basis of an infinite chain model, magnetic coupling parameters of 2-5 range from -9.3 to -14.1 cm(-1). A long-range order is observed at 2.3 K for 3 and 2.2 K for 4, while compound 5 shows spin glass behavior possibly coupled with magnetic ordering.

Sorption Mechanisms of Cesium on Cu II2Fe II(CN) 6and Cu II3[Fe III(CN) 6] 2Hexacyanoferrates and Their Relation to the Crystalline Structure

NASA Astrophysics Data System (ADS)

Ayrault, S.; Jimenez, B.; Garnier, E.; Fedoroff, M.; Jones, D. J.; Loos-Neskovic, C.

1998-12-01

CuII2FeII(CN)6·xH2O and CuII3[FeIII(CN)6]2·xH2O can be prepared with reproducible chemical compositions and structures after careful washing. They have cubicFmoverline3mstructures with iron vacancies. In CuII2FeII(CN)6, copper occupies two different sites: Cu1 in position 4blinked to Fe through the CN groups, and Cu2 not linked to the CN groups and partially occupying the interstitial 24epositions. The second type of site is not present in CuII3[FeIII(CN)6]2. Sorption kinetics and isotherms were determined for cesium on both hexacyanoferrates by batch experiments. On CuII3[FeIII(CN)6]2, the maximum uptake is only 0.073 Cs/Fe (at./at.). On CuII2FeII(CN)6, the uptake reaches 1.5 Cs/Fe. The sorption kinetics include at least two steps: at1/2variation until approximately 72 h and then a slow evolution studied up to 6 months. The sorption mechanism is complex. The main process seems to be diffusion of ion pairs, followed by a reorganization of the solid, resulting in one or more new solid phases. The presence of the Cu2 site seems to play a favorable role in the sorption. Owing to its good midterm stability and the first rapid step of exchange, CuII2FeII(CN)6·xH2O seems to be one of the most promising compounds for the recovery of cesium from nuclear liquid wastes.

Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

NASA Astrophysics Data System (ADS)

Peresypkina, Eugenia V.; Samsonenko, Denis G.; Vostrikova, Kira E.

2015-04-01

The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [{Mn(acacen)}2Ru(NO)(CN)5]n and two complexes composed of different cyanorhenates, [Ni(cyclam)]2[ReO(OH)(CN)4](ClO4)2(H2O)1.25 and [Cu(cyclam)]2[Re(CN)7](H2O)12, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]3[Re(CN)7]2 (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]3[Re(CN)7]2 complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN)n]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu4N)2[Ru(NO)(CN)5], soluble in organic media.

Electric dipole moment of diatomic molecules by configuration interaction. V - Two states of /2/Sigma/+/ symmetry in CN.

NASA Technical Reports Server (NTRS)

Green, S.

1972-01-01

Previous accurate dipole moment calculation techniques are modified to be applicable to higher excited states of symmetry. The self-consistent fields and configuration interactions are calculated for the X(2)Sigma(+) and B(2)Sigma(+) states of CN. Spin hyperfine constants and spin density at the nucleus are considered in the context of one-electron operator properties. The values of the self-consistent field and configuration interaction for the spin density are compared with experimental values for several diatomic molecules.

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

NASA Astrophysics Data System (ADS)

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.

Cyanide bridged hetero-metallic polymeric complexes: Syntheses, vibrational spectra, thermal analyses and crystal structures of complexes [M(1,2-dmi)2Ni(μ-CN)4]n (M = Zn(II) and Cd(II))

NASA Astrophysics Data System (ADS)

Kürkçüoğlu, Güneş Süheyla; Sayın, Elvan; Şahin, Onur

2015-12-01

Two cyanide bridged hetero-metallic complexes of general formula, [M(1,2-dmi)2Ni(μ-CN)4]n (1,2-dmi = 1,2-dimethylimidazole and M = Zn(II) or Cd(II)) have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal analyses and elemental analyses. The crystallographic analyses reveal that the complexes, [Zn(1,2-dmi)2Ni(μ-CN)4] (1) and [Cd(1,2-dmi)2Ni(μ-CN)4] (2), have polymeric 2D networks. In the complexes, four cyanide groups of [Ni(CN)4]2- coordinated to the adjacent M(II) ions and distorted octahedral geometries of complexes are completed by two nitrogen atoms of trans 1,2-dmi ligands. The structures of 1 and 2 are similar and linked via intermolecular hydrogen bonding, C-H⋯Ni interactions to give rise to 3D networks. Vibration assignments are given for all the observed bands and the spectral features also supported to the crystal structures of heteronuclear complexes. The FT-IR and Raman spectra of the complexes are very much consistent with the structural data presented.

Infrared Spectra and Optical Constants of Nitrile Ices Relevant to Titan's Atmosphere

NASA Technical Reports Server (NTRS)

Anderson, Carrie; Ferrante, Robert F.; Moore, W. James; Hudson, Reggie; Moore, Marla H.

2011-01-01

Spectra and optical constants of nitrile ices known or suspected to be in Titan?s atmosphere have been determined from 2.0 to 333.3 microns (approx.5000 to 30/cm). These results are relevant to the ongoing modeling of Cassini CIRS observations of Titan?s winter pole. Ices studied were: HCN, hydrogen cyanide; C2N2, cyanogen; CH3CN, acetonitrile; C2H5CN, propionitrile; and HC3N, cyanoacetylene. Optical constants were calculated, using Kramers-Kronig analysis, for each nitrile ice?s spectrum measured at a variety of temperatures, in both the amorphous- and crystalline phases. Spectra were also measured for many of the nitriles after quenching at the annealing temperature and compared with those of annealed ices. For each of these molecules we also measured the real component, n, of the refractive index for amorphous and crystalline phases at 670 nm. Several examples of the information contained in these new data sets and their usefulness in modeling Titan?s observed features will be presented (e.g., the broad emission feature at 160/cm; Anderson and Samuelson, 2011).

Efficiencies of state and velocity-changing collisions of superthermal CN A(2)Pi with He, Ar, N(2) and O(2).

PubMed

Alagappan, Azhagammai; Ballingall, Iain; Costen, Matthew L; McKendrick, Kenneth G; Paterson, Grant

2007-02-14

Polarized laser photolysis of ICN is combined with saturated optical pumping to prepare state-selected CN Alpha(2)Pi (nu' = 4, J = 0.5, F(2), f) with a well-defined anisotropic superthermal speed distribution. The collisional evolution of the prepared state is observed by Doppler-resolved Frequency Modulated (FM) spectroscopy via stimulated emission on the CN Alpha(2)Pi-Chi(2)Sigma(+) (4,2) band. The phenomenological rate constants for removal of the prepared state in collisions with He, Ar, N(2) and O(2) are reported. The observed collision cross-sections are consistent with attractive forces contributing significantly for all the colliders with the exception of He. The collisional evolution of the prepared velocity distribution demonstrates that no significant back-transfer into the prepared level occurs, and that any elastic scattering is strongly in the forward hemisphere.

Reaction of singlet-excited 2,3-diazabicyclo[2.2.2]oct-2-ene and tert-butoxyl radicals with aryl-substituted benzofuranones.

PubMed

Lundgren, Cecilia Vannesjö; Koner, Apurba L; Tinkl, Michael; Pischel, Uwe; Nau, Werner M

2006-03-03

5,7-Di-tert-butyl-3-aryl-3H-benzofuran-2-ones are lactones with potential antioxidant activity, owing to their abstractable benzylic C-H hydrogens. The fluorescence quenching of the azoalkane 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO), an established probe for the hydrogen-donor propensity of chain-breaking antioxidants, was investigated for 16 aryl-substituted benzofuranone derivatives [m,m-(CF3)2, p-CN, m-CN, p-CF3, p-COOCH3, m-CF3, p-Cl, p-F, H, m-CH3, p-CH3, m,p-(CH3)2, p-OCH3, o-CH3, o-CF3, o,m-(CH3)2]. Analysis of the rate data in terms of a linear free energy relationship yielded a reaction constant of rho = +0.35. This implies that n,pi*-excited DBO acts as nucleophilic species. In contrast, hydrogen abstraction of tert-butoxyl radicals from the benzofuranones was accelerated by electron-donating substituents (rho = -0.23), in conformity with the electrophilic character of oxygen-centered alkoxyl radicals. Possible implications for the optimization of the hydrogen-donor propensity of antioxidants through structural variation are discussed.

Early-lanthanide(III) acetonitrile–solvento adducts with iodide and noncoordinating anions

DOE PAGES

Brown, Jessie L.; Davis, Benjamin L.; Scott, Brian L.; ...

2015-12-25

Dissolution of LnI 3 (Ln = La, Ce) in acetonitrile (MeCN) results in the highly soluble solvates LnI 3(MeCN) 5 [Ln = La (1), Ce (2)] in good yield. The ionic complex [La(MeCN) 9][LaI 6] (4), containing a rare homoleptic La 3+ cation and anion, was also isolated as a minor product. Extending this chemistry to NdI 3 results in the consistent formation of the complex ionic structure [Nd(MeCN) 9] 2[NdI 5(MeCN)][NdI 6][I] (3), which contains an unprecedented pentaiodide lanthanoid anion. Also described is the synthesis, isolation, and structural characterization of several homoleptic early-lanthanide MeCN solvates with noncoordinating anions, namely,more » [Ln(MeCN) 9][AlCl 4] 3 [Ln = La (5), Ce (6), Nd (7)]. Notably, complex 6 is the first homoleptic cerium MeCN solvate reported to date. All reported complexes were structurally characterized by X-ray crystallography, as well as by IR spectroscopy and CHN elemental analysis. Furthermore, complexes 1–3 were also characterized by thermogravimetric analysis coupled with mass spectrometry to further elucidate their bulk composition in the solid-state.« less

TiCN thin films grown by reactive crossed beam pulsed laser deposition

NASA Astrophysics Data System (ADS)

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.

Syntheses, crystal structures, and magnetic properties of four new cyano-bridged bimetallic complexes based on the mer-[Fe(III)(qcq)(CN)3]- building block.

PubMed

Shen, Xiaoping; Zhou, Hongbo; Yan, Jiahao; Li, Yanfeng; Zhou, Hu

2014-01-06

Four new cyano-bridged bimetallic complexes, [{Mn(III)(salen)}2{Fe(III)(qcq)(CN)3}2]n·3nCH3CN·nH2O (1) [salen = N,N'-ethylenebis(salicylideneiminato) dianion; qcq(-) = 8-(2-quinoline-2-carboxamido)quinoline anion], [{Mn(III)(salpn)}2{Fe(III)(qcq)(CN)3}2]n·4nH2O (2) [salpn = N,N'-1,2-propylenebis(salicylideneiminato)dianion], [{Mn(II)(bipy)(CH3OH)}{Fe(III)(qcq)(CN)3}2]2·2H2O·2CH3OH (3) (bipy = 2,2'-bipyridine), and [{Mn(II)(phen)2}{Fe(III)(qcq)(CN)3}2]·CH3CN·2H2O (4) (phen = 1,10-phenanthroline) have been synthesized and characterized both structurally and magnetically. The structures of 1 and 2 are both unique 1-D linear branch chains with additional structural units of {Mn(III)(salen/salpn)}{Fe(III)(qcq)(CN)3} dangling on the sides. In contrast, 3 and 4 are cyano-bridged bimetallic hexanuclear and trinuclear clusters, respectively. The intermolecular short contacts such as π-π interactions and hydrogen bonds extend 1-4 into high dimensional supermolecular networks. Magnetic investigation reveals the dominant intramolecular antiferromagnetic interactions in 1, 3, and 4, while ferromagnetic and antiferromagnetic interactions coexist in 2. Alternating current measurement at low temperature indicates the existence of slow magnetic relaxation in 1 and 2, which should be due to the single ion anisotropy of Mn(III).

Application of Vorob'ev's asymptotic solution to retrieval of the structural characteristics Cn2 from BSA-lidar data

NASA Astrophysics Data System (ADS)

Razenkov, I. A.

2017-11-01

Micro pulse lasers have allowed solution of some technical problems and design of a specialized aerosol lidar capable of recording backscattering amplification (BSA) in a turbulent atmosphere (2014) by now. The BSA-lidar has two receiving channels, one of which is affected by a turbulence. The measurement result is the ratio of echo signals, i.e., the coefficient of backscattering amplification. The problem of lidar data inversion and retrieval of "optical" turbulence parameters was recently solved by V.V. Vorob'ev theoretically (2016). A lidar experiment was organized for testing the solution, and the asymptotic solution was applied to echo signals, which allowed estimating the daily behavior of the structural characteristics Cn 2 along a horizontal 2-km path. The experiment was accompanied by parallel independent measurements of Cn 2 by an image jitter sensor along the same path. It was shown experimentally that the Vorob'ev solution is applicable to Cn 2 retrieval from BSA-lidar data if β0 2<=3 for β0 2>3, the saturation of the amplification effect and a decrease in the experimental data with respect to calculation results are observed. The coefficient of correlation between the retrieved structural characteristics Cn 2 of the lidar and jitter sensor is 0.8-0.9. The Cn 2 values retrieved from lidar signals turned out to be 20-40% lower than the Cn 2 values of the image jitter sensor.

Photochemical Construction of Carbonitride Structures for Red-Light Redox Catalysis.

PubMed

Yang, Pengju; Wang, Ruirui; Zhou, Min; Wang, Xinchen

2018-05-22

Metal-free carbonitride(CN) semiconductors are appealing light-transducers for photocatalytic redox reactions owing to the unique band gap and stability. To harness solar energy efficiently, CN catalysts that are active over a wider range of the visible spectrum are desired. Now a photochemical approach has been used to prepare a new-type triazine-based CN structure. The obtained CN shows extraordinary light-harvesting characteristics, with suitable semiconductor-redox potentials. The light absorption edge of the CN reaches up to 735 nm, which is significantly longer than that of the conventional CN semiconductor at about 460 nm. As expected, the CN can efficiently catalyze oxidation of alcohols and reduction of CO 2 with visible light, even under red-light irradiation. The results represent an important step toward the development of red-light-responsive triazine-based structures for solar applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigating vibrational anharmonic couplings in cyanide-bridged transition metal mixed valence complexes using two-dimensional infrared spectroscopy

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

Slenkamp, Karla M.; Lynch, Michael S.; Van Kuiken, Benjamin E.

2014-02-28

Using polarization-selective two-dimensional infrared (2D IR) spectroscopy, we measure anharmonic couplings and angles between the transition dipole moments of the four cyanide stretching (ν{sub CN}) vibrations found in [(NH{sub 3}){sub 5}Ru{sup III}NCFe{sup II}(CN){sub 5}]{sup −} (FeRu) dissolved in D{sub 2}O and formamide and [(NC){sub 5}Fe{sup II}CNPt{sup IV}(NH{sub 3}){sub 4}NCFe{sup II}(CN){sub 5}]{sup 4−} (FePtFe) dissolved in D{sub 2}O. These cyanide-bridged transition metal complexes serve as model systems for studying the role of high frequency vibrational modes in ultrafast photoinduced charge transfer reactions. Here, we focus on the spectroscopy of the ν{sub CN} modes in the electronic ground state. The FTIR spectramore » of the ν{sub CN} modes of the bimetallic and trimetallic systems are strikingly different in terms of frequencies, amplitudes, and lineshapes. The experimental 2D IR spectra of FeRu and FePtFe and their fits reveal a set of weakly coupled anharmonic ν{sub CN} modes. The vibrational mode anharmonicities of the individual ν{sub CN} modes range from 14 to 28 cm{sup −1}. The mixed-mode anharmonicities range from 2 to 14 cm{sup −1}. In general, the bridging ν{sub CN} mode is most weakly coupled to the radial ν{sub CN} mode, which involves the terminal CN ligands. Measurement of the relative transition dipole moments of the four ν{sub CN} modes reveal that the FeRu molecule is almost linear in solution when dissolved in formamide, but it assumes a bent geometry when dissolved in D{sub 2}O. The ν{sub CN} modes are modelled as bilinearly coupled anharmonic oscillators with an average coupling constant of 6 cm{sup −1}. This study elucidates the role of the solvent in modulating the molecular geometry and the anharmonic vibrational couplings between the ν{sub CN} modes in cyanide-bridged transition metal mixed valence complexes.« less

Can the tricyanomethanide anion improve CO2 absorption by acetate-based ionic liquids?

PubMed

Lepre, L F; Szala-Bilnik, J; Pison, L; Traïkia, M; Pádua, A A H; Ando, R A; Costa Gomes, M F

2017-05-17

Carbon dioxide absorption by mixtures of two ionic liquids with a common cation-1-butyl-3-methylimidazolium acetate, [C 4 C 1 Im][OAc], and 1-butyl-3-methylimidazolium tricyanomethanide, [C 4 C 1 Im][C(CN) 3 ]-was determined experimentally at pressures below atmospheric pressure as a function of temperature between 303 K and 343 K, and at 303 K as a function of pressure up to 10 bar. It is observed that the absorption of carbon dioxide decreases with increasing tricyanomethanide anion concentration and with increasing temperature, showing a maximum of 0.4 mole fraction of carbon dioxide in pure [C 4 C 1 Im][OAc] at 303 K. At this temperature, the CO 2 absorption in the mixtures [C 4 C 1 Im][OAc] (1-x) [C(CN) 3 ] x is approximately the mole-fraction average of that in the pure ionic liquids. By applying an appropriate thermodynamic treatment, after identification of the species in solution, it was possible to calculate both the equilibrium constant, K eq , and Henry's law constant, K H , in the different mixtures studied thus obtaining an insight into the relative contribution of chemical and physical absorption of the gas. It is shown that chemical sorption proceeds through a 1 : 2 stoichiometry between CO 2 and acetate-based ionic liquid. The presence of the C(CN) 3 - anion does not significantly affect the chemical reaction of the gas with the solvent (K eq = 75 ± 2 at 303 K) but leads to lower Henry's law constants (from K H = 77.8 ± 0.6 bar to K H = 49.5 ± 0.5 bar at 303 K), thus pointing towards larger physical absorption of the gas. The tricyanomethanide anion considerably improves the mass transfer by increasing the fluidity of the absorbent as proven by the larger diffusivities of all the ions when the concentration of the C(CN) 3 - anion increases in the mixtures.

Nitroxyl Radical plus Hydroxylamine Pseudo Self-Exchange Reactions: Tunneling in Hydrogen Atom Transfer

PubMed Central

Wu, Adam; Mader, Elizabeth A.; Datta, Ayan; Hrovat, David A.; Borden, Weston Thatcher; Mayer, James M.

2009-01-01

Bimolecular rate constants have been measured for reactions that involve hydrogen atom transfer (HAT) from hydroxylamines to nitroxyl radicals, using the stable radicals TEMPO• (2,2,6,6-tetramethylpiperidine-1-oxyl radical), 4-oxo-TEMPO• (2,2,6,6-tetramethyl-4-oxo-piperidine-1-oxyl radical), di-tert-butylnitroxyl (tBu2NO•), and the hydroxylamines TEMPO-H, 4-oxo-TEMPO-H, 4-MeO-TEMPO-H (2,2,6,6-tetramethyl-N-hydroxy-4-methoxy-piperidine), and tBu2NOH. The reactions have been monitored by UV-vis stopped-flow methods, using the different optical spectra of nitroxyl radicals. The HAT reactions all have |ΔGo| ≤ 1.4 kcal mol−1 and therefore are close to self-exchange reactions. The reaction of 4-oxo-TEMPO• + TEMPO-H → 4-oxo-TEMPO-H + TEMPO• occurs with k2H,MeCN = 10 ± 1 M−1 s−1 in MeCN at 298 K (K2H,MeCN = 4.5 ± 1.8). Surprisingly, the rate constant for the analogous deuterium atom transfer reaction is much slower: k2D,MeCN = 0.44 ± 0.05 M−1 s−1 with k2H,MeCN/k2D,MeCN = 23 ± 3 at 298 K. The same large kinetic isotope effect (KIE) is found in CH2Cl2, 23 ± 4, suggesting that the large KIE is not caused by solvent dynamics or hydrogen bonding to solvent. The related reaction of 4-oxo-TEMPO• with 4-MeO-TEMPO-H(D) also has a large KIE, k3H/k3D = 21 ± 3 in MeCN. For these three reactions, the EaD – EaH values, between 0.3 ± 0.6 and 1.3 ± 0.6 kcal mol−1, and the log(AH/AD) values, between 0.5 ± 0.7 and 1.1 ± 0.6, indicate that hydrogen tunneling plays an important role. The related reaction of tBu2NO• + TEMPO-H(D) in MeCN has a large KIE, 16 ± 3 in MeCN, and very unusual isotopic activation parameters, EaD – EaH = −2.6 ± 0.4 and log(AH/AD) = 3.1 ± 0.6. Computational studies, using POLYRATE, also indicate substantial tunneling in the (CH3)2NO• + (CH3)2NOH model reaction for the experimental self-exchange processes. Additional calculations on TEMPO(•/H), tBu2NO(•/H), and Ph2NO(•/H) self-exchange reactions reveal why the phenyl groups make the last of these reactions several orders of magnitude faster than the first two. By inference, the calculations also suggest why tunneling appears to be more important in the self-exchange reactions of dialkylhydroxylamines than of arylhydroxylamines. PMID:19618933

Tuning of chain chirality by interchain stacking forces and the structure-property relationship in coordination systems constructed by meridional FeIII cyanide and MnIII Schiff bases.

PubMed

Sohn, Ah Ram; Lim, Kwang Soo; Kang, Dong Won; Song, Jeong Hwa; Koh, Eui Kwan; Moon, Dohyun; Hong, Chang Seop

2016-12-06

We synthesized six Fe(iii)-Mn(iii) bimetallic compounds by self-assembling the newly developed mer-Fe cyanide PPh 4 [Fe(Clqpa)(CN) 3 ]·H 2 O (1) and PPh 4 [Fe(Brqpa)(CN) 3 ]·H 2 O (2) with Mn Schiff base Mn(5-Xsalen) + cations. These compounds include [Fe(Xqpa)(CN) 3 ][Mn(5-Ysalen)]·pMeOH·qH 2 O [qpaH 2 = N-(quinolin-8-yl)picolinamide; salen = N,N'-ethylenebis(salicylideneiminato) dianion; X = Cl, Y = H (3); X = Cl, Y = Br (4); X = Br, Y = H (5); X = Br, Y = F (6); X = Br, Y = Cl (7); X = Br, Y = Br (8)]. When precursor 1 was used, compounds 3 and 4 were isolated to give a dinuclear entity and a linear chain structure, respectively. The reaction of precursor 2 with the Schiff bases afforded four linear Fe(iii)-Mn(iii) chain complexes. Chain chirality with P- and M-helicity emerges in 4, 7, and 8, while 5 exhibits chain helicity opposite to the previous chain complexes and 6 presents no chain helicity. Such a structural feature is heavily dependent on the interchain π-π contacts and the Fe precursor bridging unit. Chiral induction from a local ethylenediamine link of Y-salen is propagated over the chain via noncovalent π-π interactions. All the bimetallic compounds show antiferromagnetic interactions transmitted by the cyanide linkage. A field-induced metamagnetic transition is involved in 4, 7, and 8, while a field-induced two-step transition is evident in 6. From a magnetostructural viewpoint, the coupling constant is primarily governed by the Mn-N ax -C ax angle (ax = axial) in the bimetallic chain complexes composed of mer-Fe(iii) tricyanides, although the torsion angle plays a role.

Probing the Surface Tension of Ionic Liquids Using the Langmuir Principle

PubMed Central

2018-01-01

At 298 K, the surface tension of ionic liquids (ILs) of the 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide series, [CnC1Im][NTf2], ranges from around 35 mN·m–1 for [C2C1Im][NTf2] to just below 30 mN·m–1 for [C12C1Im][NTf2]. However, the decrease rate along the series is not constant: a large decrease from [C2C1Im][NTf2] to [C8C1Im][NTf2] is followed by almost constant values from [C8C1Im][NTf2] to [C12C1Im][NTf2]. Such behavior is hard to interpret from a molecular point of view without suitable information about the free-surface structure of the different ILs. In this work, we have successfully used the Langmuir principle in combination with structural data obtained from angle-resolved X-ray photoelectron spectroscopy experiments and molecular dynamics simulations, to predict the correct surface tension trend along the IL series. The concepts unveiled for this particular homologous IL family can be easily extended to other systems. PMID:29485882

Biodegradation of high concentrations of hexadecane by Aspergillus niger in a solid-state system: kinetic analysis.

PubMed

Volke-Sepúlveda, Tania; Gutiérrez-Rojas, Mariano; Favela-Torres, Ernesto

2006-09-01

Solid-state microcosms were used to assess the influence of constant and variable C/N ratios on the biodegradation efficiency by Aspergillus niger at high hexadecane (HXD) concentrations (180-717 mg g-1). With a constant C/N ratio, 100% biodegradation (33-44% mineralization) was achieved after 15 days, at rates increasing as the HXD concentration increased. Biomass yields (YX/S) remained almost independent (approximately 0.77) of the carbon-source amount, while the specific growth rates (mu) decreased with increasing concentrations of HXD. With C/N ratios ranging from 29 to 115, complete degradation was only attained at 180 mg g-1, corresponding to 46% mineralization. YX/S diminished (approximately 0.50 units) as the C/N ratio increased. The highest values of mu (1.08 day-1) were obtained at low C/N values. Our results demonstrate that, under balanced nutritional conditions, high HXD concentrations can be completely degraded in solid-state microcosms, with a negligible (<10%) formation of by-products.

A new family of metal borohydride guanidinate complexes: Synthesis, structures and hydrogen-storage properties

NASA Astrophysics Data System (ADS)

Wu, Hui; Zhou, Xiuquan; Rodriguez, Efrain E.; Zhou, Wei; Udovic, Terrence J.; Yildirim, Taner; Rush, John J.

2016-10-01

We report on a new class of complex hydrides: borohydride guanidinate complexes (MBH4·nCN3H5, M=Li, Mg, and Ca). They can be prepared via facile solid-state synthesis routes. Their crystal structures were successfully determined using a combination of X-ray diffraction, first-principles calculations and neutron vibrational spectroscopy. Among these compounds, Mg(BH4)2·6CN3H5 is composed of large complex Mg[CN3H5]62+ cations and surrounding BH4- ions, while Ca(BH4)2·2CN3H5 possesses layers of corner-sharing Ca[BH4]4(CN3H5)2 octahedra. Our dehydrogenation results show that ≈10 wt% hydrogen can be released from MBH4·nCN3H5 (M=Li, Mg, and Ca) at moderate temperatures with minimal ammonia and diborane contamination thanks to the synergistic effect of C-N bonds from guanidine and hydridic H from borohydrides leading to a weakening of the N-H bonds, thus impeding ammonia gas liberation. Further tuning the dehydrogenation with different cation species indicates that Mg(BH4)2·nCN3H5 can exhibit the optimum properties with nearly thermally neutral dehydrogenation and very high purity hydrogen release.

A new family of metal borohydride guanidinate complexes: Synthesis, structures and hydrogen-storage properties

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

Wu, Hui, E-mail: huiwu@nist.gov; Zhou, Xiuquan; Rodriguez, Efrain E.

We report on a new class of complex hydrides: borohydride guanidinate complexes (MBH{sub 4}·nCN{sub 3}H{sub 5}, M=Li, Mg, and Ca). They can be prepared via facile solid-state synthesis routes. Their crystal structures were successfully determined using a combination of X-ray diffraction, first-principles calculations and neutron vibrational spectroscopy. Among these compounds, Mg(BH{sub 4}){sub 2}·6CN{sub 3}H{sub 5} is composed of large complex Mg[CN{sub 3}H{sub 5}]{sub 6}{sup 2+} cations and surrounding BH{sub 4}{sup -} ions, while Ca(BH{sub 4}){sub 2}·2CN{sub 3}H{sub 5} possesses layers of corner-sharing Ca[BH{sub 4}]{sub 4}(CN{sub 3}H{sub 5}){sub 2} octahedra. Our dehydrogenation results show that ≈10 wt% hydrogen can be releasedmore » from MBH{sub 4}·nCN{sub 3}H{sub 5} (M=Li, Mg, and Ca) at moderate temperatures with minimal ammonia and diborane contamination thanks to the synergistic effect of C-N bonds from guanidine and hydridic H from borohydrides leading to a weakening of the N-H bonds, thus impeding ammonia gas liberation. Further tuning the dehydrogenation with different cation species indicates that Mg(BH{sub 4}){sub 2}·nCN{sub 3}H{sub 5} can exhibit the optimum properties with nearly thermally neutral dehydrogenation and very high purity hydrogen release. - Graphical abstract: A new family of complex hydrides: borohydride guanidinates, was developed with diverse crystal structures and remarkable hydrogen storage properties. - Highlights: • A new family of complex hydrides, borohydride guanidinate complexes, are synthesized. • Their diverse crystal structures are determined using combined characterizations. • These compounds can release ~10 wt% pure H{sub 2} at moderate temperatures. • Dehydrogenation thermodynamics and H{sub 2} purity can be tuned by varying cation species.« less

Synchrotron Microtomographic Quantification of Geometrical Soil Pore Characteristics Affected by Compaction

NASA Astrophysics Data System (ADS)

Udawatta, Ranjith; Gantzer, Clark; Anderson, Stephen; Assouline, Shmuel

2015-04-01

Soil compaction degrades soil structure and affects water, heat, and gas exchange as well as root penetration and crop production. The objective of this study was to use X-ray computed microtomography (CMT) techniques to compare differences in geometrical soil pore parameters as influenced by compaction of two different aggregate size classes. Sieved (diam. < 2mm and < 0.5mm) and repacked (1.51 and 1.72 Mg m-3) Hamra soil cores of 5- by 5-mm (average porosities were 0.44 and 0.35) were imaged at 9.6-micrometer resolution at the Argonne Advanced Photon Source (synchrotron facility) using X-ray computed microtomography. Images of 58.9 mm3 volume were analyzed using 3-Dimensional Medial Axis (3DMA) software. Geometrical characteristics of the spatial distributions of pore structures (pore radii, volume, connectivity, path length, and tortuosity) were numerically investigated. Results show that the coordination number (CN) distribution and path length (PL) measured from the medial axis were reasonably fit by exponential relationships P(CN)=10-CN/Co and P(PL)=10-PL/PLo, respectively, where Co and PLo are the corresponding characteristic constants. Compaction reduced porosity, average pore size, number of pores, and characteristic constants. The average pore radii (64 and 61 μm; p<0.04), largest pore volume (1.6 and 0.6 mm3; p=0.06), number of pores (55 and 50; p=0.09), characteristic coordination number (6.3 and 6.0; p=0.09), and characteristic path length number (116 and 105; p=0.001) were significantly greater in the low density than the high density treatment. Aggregate size also influenced measured geometrical pore parameters. This analytical technique provides a tool for assessing changes in soil pores that affect hydraulic properties and thereby provides information to assist in assessment of soil management systems.

Synchrotron microtomographic quantification of geometrical soil pore characteristics affected by compaction

NASA Astrophysics Data System (ADS)

Udawatta, R. P.; Gantzer, C. J.; Anderson, S. H.; Assouline, S.

2015-07-01

Soil compaction degrades soil structure and affects water, heat, and gas exchange as well as root penetration and crop production. The objective of this study was to use X-ray computed microtomography (CMT) techniques to compare differences in geometrical soil pore parameters as influenced by compaction of two different aggregate size classes. Sieved (diam. < 2 mm and < 0.5 mm) and repacked (1.51 and 1.72 Mg m-3) Hamra soil cores of 5- by 5 mm (average porosities were 0.44 and 0.35) were imaged at 9.6-micrometer resolution at the Argonne Advanced Photon Source (synchrotron facility) using X-ray computed microtomography. Images of 58.9 mm3 volume were analyzed using 3-Dimensional Medial Axis (3DMA) software. Geometrical characteristics of the spatial distributions of pore structures (pore radii, volume, connectivity, path length, and tortuosity) were numerically investigated. Results show that the coordination number (CN) distribution and path length (PL) measured from the medial axis were reasonably fit by exponential relationships P(CN) = 10-CN/Co and P(PL) = 10-PL/PLo, respectively, where Co and PLo are the corresponding characteristic constants. Compaction reduced porosity, average pore size, number of pores, and characteristic constants. The average pore radii (63.7 and 61 μm; p < 0.04), largest pore volume (1.58 and 0.58 mm3; p = 0.06), number of pores (55 and 50; p = 0.09), characteristic coordination number (6.32 and 5.94; p = 0.09), and characteristic path length number (116 and 105; p = 0.001) were significantly greater in the low density than the high density treatment. Aggregate size also influenced measured geometrical pore parameters. This analytical technique provides a tool for assessing changes in soil pores that affect hydraulic properties and thereby provides information to assist in assessment of soil management systems.

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

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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.

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

NASA Astrophysics Data System (ADS)

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.

A theoretical study of OH radical-initiated atmospheric oxidation of 1-chloronaphthalene

NASA Astrophysics Data System (ADS)

Cui, Yang; Ding, Zhezheng; Sun, Yanhui; Yi, Yayi; Xu, Fei; Zhang, Qingzhu; Wang, Wenxing

2018-05-01

OH-initiated atmospheric oxidation mechanism of 1-chloronaphthalene (1-CN) was investigated using density functional theory (DFT) calculations. The oxidation is predicted to be initiated by OH addition to the α-positions, and the additions to C4 and C5 are more favorable. 1-CN-OH adducts tend to react with ambient O2 to produce peroxy intermediates, followed by intramolecular H-shifts producing C10H7OCl and diketone or unimolecular ring closure forming methyl glyoxal and Cl-substituted phthalaldialdehyde. Despite that the rate constants are influenced by the tunneling factors, intramolecular H-shift reactions are suggested to be more favorable. The OH-determined lifetime of 1-CN is 0.62 days.

Electronic structure calculations on multiply charged anions containing M bond S bonds (M = Cr, Mo, W) and their heterobimetallic cluster complexes

NASA Astrophysics Data System (ADS)

Gili, Pedro; Tsipis, Athanassios C.

Molecular and electronic structures of multiply charged mononuclear [CrS4]2-/3-, [MoOxS4-x]2-/3- (x = 0-4) and [WS4]2-/3- anionic species, and their heterobimetallic dinuclear and trinuclear clusters formulated as [MoOS3(CuCl)]2-, [WOS3(CuCl)]2-, [MoS4{Cu(CN)}]2-, [(CN)Cu(?-CrS4)Cu(CN)]2-, [(CN)Cu(?-MoS4)Cu(CN)]2-, [ClCu(?-MoS4)CuCl]2-, [Cl2Fe(?-MoS4)CuCl2]2-, and [(CN)Cu(?-WS4)Cu(CN)]2- have been investigated using electronic structure calculation (HF, MP4SDQ and DFT) methods. For the discrete mononuclear anions HF/lanl2dz(M)?6-31+G*(S,O) method provided the best description of their molecular structures, while for the heterobimetallic dinuclear and trinuclear clusters the B3LYP/lanl2dz(M)?6-31+G* method gave equilibrium geometries closely resembling the experimental ones. Electronic and spectroscopic (IR, UV-Vis) properties of the thiometalates are discussed in relation to their structures, while the bonding mechanism was analyzed in the framework of the natural bond orbital (NBO) approach. The nature of the highest occupied molecular orbitals (HOMOs) of all thiometalates indicated their ability to act as ligands coordinated with metal centers and forming clusters of higher nuclearity. The lowest-lying vertical one-electron detachment processes from the ground state of the [CrS4]2/3-, [MoOxS4-x]2/3- (x = 0-4) and [WS4]2/3- anions have been calculated using the outer valence Green's function (OVGF) method. Interestingly, in the heterobimetallic dinuclear and trinuclear clusters intemetallic M?M? interactions exist corresponding to d10 ? d0 dative bonding. Finally, the complete energetic and geometric profile of the successive acid-catalyzed formation reactions:and the reverse hydrolysis reactions have been delineated and details of the mechanism have been furnished.

Structural differences between bovine A(1) and A(2) β-casein alter micelle self-assembly and influence molecular chaperone activity.

PubMed

Raynes, J K; Day, L; Augustin, M A; Carver, J A

2015-04-01

Within each milk protein there are many individual protein variants and marked alterations to milk functionality can occur depending on the genetic variants of each protein present. Bovine A(1) and A(2) β-casein (β-CN) are 2 variants that contribute to differences in the gelation performance of milk. The A(1) and A(2) β-CN variants differ by a single AA, the substitution of histidine for proline at position 67. β-Casein not only participates in formation of the casein micelle but also forms an oligomeric micelle itself and functions as a molecular chaperone to prevent the aggregation of a wide range of proteins, including the other caseins. Micelle assembly of A(1) and A(2) β-CN was investigated using dynamic light scattering and small-angle X-ray scattering, whereas protein functionality was assessed using fluorescence techniques and molecular chaperone assays. The A(2) β-CN variant formed smaller micelles than A(1) β-CN, with the monomer-micelle equilibrium of A(2) β-CN being shifted toward the monomer. This shift most likely arose from structural differences between the 2 β-CN variants associated with the adoption of greater polyproline-II helix in A(2) β-CN and most likely led to enhanced chaperone activity of A(2) β-CN compared with A(1) β-CN. The difference in micelle assembly, and hence chaperone activity, may provide explain differences in the functionality of homozygous A(1) and A(2) milk. The results of this study highlight that substitution of even a single AA can significantly alter the properties of an intrinsically unstructured protein such as β-CN and, in this case, may have an effect on the functionality of milk. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

The Submillimeter Wave Spectrum of Isotopic Methyl Cyanide

NASA Technical Reports Server (NTRS)

Pearson, J. C.; Mueller, H. S. P.

1996-01-01

The laboratory submillimeter wave rotational spectrum of the 13CH3CN, CH3C13CN, and CH3C15N isotopomers of methyl cyanide has been observed in natural abundance in the 294 to 607 GHz region. The maximum J and K values are 34 and 14, respectively. Fifteen additional CH3CN transitions up to K = 21 were also measured. The transitions of all four species are fitted to a symmetric top Hamiltonian, and the rotation and distortion constants are determined. The 14N quadrupole and spin rotation coupling constants are also calculated and presented. Suggested values for many other parameters, which could not be directly determined from the isotope spectra, are calculated from the normal species values and isotope relationships. The determined and calculated constants should predict the spectrum of the three isotopomers to well over 1 THz accurately enough for astronomical assignments.

Periodic density functional theory study of spin crossover in the cesium iron hexacyanochromate prussian blue analog

NASA Astrophysics Data System (ADS)

Wojdeł, Jacek C.; Moreira, Ibério de P. R.; Illas, Francesc

2009-01-01

This paper presents a detailed theoretical analysis of the electronic structure of the CsFe[Cr(CN)6] prussian blue analog with emphasis on the structural origin of the experimentally observed spin crossover transition in this material. Periodic density functional calculations using generalized gradient approximation (GGA)+U and nonlocal hybrid exchange-correlation potentials show that, for the experimental low temperature crystal structure, the t2g6eg0 low spin configuration of FeII is the most stable and CrIII (S =3/2, t2g3eg0) remains the same in all cases. This is also found to be the case for the low spin GGA+U fully relaxed structure with the optimized unit cell. A completely different situation emerges when calculations are carried out using the experimental high temperature structure. Here, GGA+U and hybrid density functional theory calculations consistently predict that the t2g4eg2 FeII high spin configuration is the ground state. However, the two spin configurations appear to be nearly degenerate when calculations are carried out for the geometries arising from a GGA+U full relaxation of the atomic structure carried out at experimental high temperature lattice constant. A detailed analysis of the energy difference between the two spin configurations as a function of the lattice constant strongly suggests that the observed spin crossover transition has a structural origin with non-negligible entropic contributions of the high spin state.

Structural and magnetic properties of Prussian blue analogue molecular magnet Fe{sub 1.5}[Cr(CN){sub 6}]·mH{sub 2}O

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

Bhatt, Pramod, E-mail: prabhatt@barc.gov.in; Meena, S. S.; Mukadam, M. D.

2016-05-23

Molecular magnets, based on Prussian blue analogues, Fe{sub 1.5}[Cr(CN){sub 6}]·mH{sub 2}O have been synthesized in the bulk as well as nanoparticle forms using a co-precipitation method, and their structural and magnetic properties have been investigated using x-ray diffraction (XRD) Mössbauer spectroscopy and dc magnetization. The XRD study confirms the single phase crystalline and nanoparticle nature of the compounds with a face centered cubic (fcc) structure of space group Fm3m. The values of lattice constant are found to be ~10.18(5) Å and ~9.98(9)Å, for the bulk and nanoparticle samples, respectively. The dc magnetization shows a Curie temperature (T{sub C}) of ~17more » K and ~5 K for the bulk and nanopartcile samples, respectively. The Mossouber spectroscopy reveal that the compound shows spin flipping from the high spin (HS) Fe (Cr{sup III}–C≡N–Fe{sup II}) to low spin (LS) Fe{sup II} ions (Cr{sup III}–N≡C–Fe{sup II}). Moreover, the T{sub C} and the HS state of the Fe ions decreases (converts to its LS states) with time as well as in the nanoparticle form compared to bulk.« less

Effect of Scintillometer Height on Structure Parameter of the Refractive Index of Air Measurements

NASA Astrophysics Data System (ADS)

Gowda, P. H.; Howell, T. A.; Hartogensis, O.; Basu, S.; Scanlon, B. R.

2009-12-01

Scintillometers measure amount of scintillations by emitting a beam of light over a horizontal path and expresses as the atmospheric turbulence structure parameter as the refractive index of air (Cn2). Cn2 represents the turbulent strength of the atmosphere and describes the ability of the atmosphere to transport heat and humidity. The main objective of this study was to evaluate the effect of scintillometer height on Cn2 measurements and on the estimation of latent heat fluxes. The study was conducted during the 2009 summer growing season in the USDA-ARS Conservation and Production Research Laboratory (CPRL) at Bushland [350 11' N, 1020 06' W; 1,170 m elevation MSL], Texas. Field experiment consisted of two steps: (1) cross-calibration of scintillometers and (2) measurement of Cn2 at different heights. In the first step, three large aperture scintillometers (LAS) were deployed across two large lysimeter fields with bare soil surfaces. During the 3-week cross-calibration period, all three scintillometers were installed at a 2-m height with a path length of 420 m. Cn2 was monitored at a 1-min interval and averaged for 15-min periods. Cn2 measurements were synchronized with weather station and weighing lysimeter measurements. After the cross-calibration period, scintillometers were installed at 2-, 2.5- and 3-m heights, and Cn2 measurements were continued for another 3-week period. In addition to the Cn2 measurements, net radiation (Rn) and soil heat fluxes (G) were measured in both lysimeter fields. Cn2 values were corrected for inner scale dependence before cross calibration and estimation of sensible heat fluxes. Measurements of wind speed, air temperature, and relative humidity were used with Cn2 data to derive sensible heat fluxes. Latent heat fluxes were estimated as a residual from the energy balance and compared with lysimeter data. Results of cross calibration and effects of scintillometer height on the estimation of latent heat fluxes were reported and discussed.

Synthesis and synchrotron X-ray characterization of two 2D Hoffman related compounds [Ni(p-Xylylenediamine)nNi(CN)4] and [Ni(p-tetrafluoroxylylenediamine)nNi(CN)4

NASA Astrophysics Data System (ADS)

Wong-Ng, W.; Culp, J. T.; Siderius, D. W.; Chen, Y. S.

2018-07-01

Synchrotron X-ray single crystal structure determination of two 2D Hofmann-related compounds, [Ni(p-Xylyenediamine)n-tetracyanonickelate] (abbreviated as Ni-pXdam) and [Ni(tetrafluoro-p-Xylyenediamine)n-tetracyanonickelate] (abbreviated as Ni-pXdamF4), have been conducted. Both the pXdam and pXdamF4 ligands contain two short chains of -CH2NH2 at the para-positions of a phenyl ring. These flexible chains link the 6-fold coordinated Ni2 sites throughout the network. In Ni-pXdam, the closed-2D network of [Ni-(CN-Ni1/4-)4]∞ is broken into 1D chains, leaving the C≡N groups at the trans-positions of the Ni(CN)4 moiety unbridged. The resulting 1D chains [(trans-)-NC-Ni(CN)2-CN-Ni-]∞ runs along the [010] direction of the unit cell. The pXdam ligands bridge in pair between the Ni atoms of the adjacent chains. The catenation structure of [Ni{(pXdam)}]∞ could be referred to as double -1D. In Ni-pXdamF4, the -CH2NH2 ligands connect the neighboring chains via the 6-fold Ni2 site. Surrounding the 4-fold Ni1 site, the two trans terminal C≡N groups were replaced by the Lewis base NH3 during the synthesis process, therefore preventing the propagation of the 2D net to form a 3D network. Computed pore volume of both compounds indicated that there is not sufficient space in the structure to accommodate gas molecules. In both compounds, hydrogen bonds were found, and solvent of crystallization was absent due to the limited free space in the structure.

Electrochemistry and speciation of Au(+) in a deep eutectic solvent: growth and morphology of galvanic immersion coatings.

PubMed

Ballantyne, Andrew D; Forrest, Gregory C H; Frisch, Gero; Hartley, Jennifer M; Ryder, Karl S

2015-11-11

In this study we compare the electrochemical and structural properties of three gold salts AuCl, AuCN and KAu(CN)2 in a Deep Eutectic Solvent (DES) electrolyte (Ethaline 200) in order to elucidate factors affecting the galvanic deposition of gold coatings on nickel substrates. A chemically reversible diffusion limited response was observed for AuCl, whereas AuCN and KAu(CN)2 showed much more complicated, kinetically limited responses. Galvanic exchange reactions were performed on nickel substrates from DES solutions of the three gold salts; the AuCN gave a bright gold coating, the KAu(CN)2 solution give a visibly thin coating, whilst the coating from AuCl was dull, friable and poorly adhesive. This behaviour was rationalised by the differing speciation for each of these compounds, as evidenced by EXAFS methods. Analysis of EXAFS data shows that AuCl forms the chlorido-complex [AuCl2](-), AuCN forms a mixed [AuCl(CN)](-) species, whereas KAu(CN)2 maintains its [Au(CN)2](-) structure. The more labile Cl(-) enables easier reduction of Au when compared to the tightly bound cyanide species, hence leading to slower kinetics of deposition and differing electrochemical behaviour. We conclude that metal speciation in DESs is a function of the initial metal salt and that this has a strong influence on the mechanism and rate of growth, as well as on the morphology of the metal deposit obtained. In addition, these coatings are also extremely promising from a technological perspective as Electroless Nickel Immersion Gold (ENIG) finishes in the printed circuit board (PCB) industry, where the elimination of acid in gold plating formulation could potentially lead to more reliable coatings. Consequently, these results are both significant and timely.

On P2 ⋄ Pn -supermagic labeling of edge corona product of cycle and path graph

NASA Astrophysics Data System (ADS)

Yulianto, R.; Martini, Titin S.

2018-04-01

A simple graph G = (V, E) admits a H-covering, where H is subgraph of G, if every edge in E belongs to a subgraph of G isomorphic to H. Graph G is H-magic if there is a total labeling f:V(G)\\cup E(G)\\to 1,2,\\ldots,|V(G)|+|E(G)|, such that each subgraph {H}{\\prime }=({V}{\\prime },{E}{\\prime }) of G isomorphic to H and satisfying f{({H}{\\prime })}=def{\\sum }\\upsilon \\in {V{\\prime }}f(\\upsilon )+{\\sum }e\\in {E{\\prime }}f(e)=m(f) where m(f) is a constant magic sum. Additionaly, G admits H-supermagic if f(V)=1,2,\\ldots,|V|. The edge corona {C}n \\diamond {P}n of Cn and Pn is defined as the graph obtained by taking one copy of Cn and n copies of Pn , and then joining two end-vertices of the i-th edge of Cn to every vertex in the i-th copy of Pn . This research aim is to find H-supermagic covering on an edge corona product of cycle and path graph {C}n \\diamond {P}n where H is {P}2 \\diamond {P}n. We use k-balanced multiset to solve our reserarch. Here, we find that an edge corona product of cycle and path graph {C}n \\diamond {P}n is {P}2 \\diamond {P}n supermagic for n > 3.

Pristine Basal- and Edge-Plane-Oriented Molybdenite MoS2 Exhibiting Highly Anisotropic Properties.

PubMed

Tan, Shu Min; Ambrosi, Adriano; Sofer, Zdenĕk; Huber, Štěpán; Sedmidubský, David; Pumera, Martin

2015-05-04

The layered structure of molybdenum disulfide (MoS2 ) is structurally similar to that of graphite, with individual sheets strongly covalently bonded within but held together through weak van der Waals interactions. This results in two distinct surfaces of MoS2 : basal and edge planes. The edge plane was theoretically predicted to be more electroactive than the basal plane, but evidence from direct experimental comparison is elusive. Herein, the first study comparing the two surfaces of MoS2 by using macroscopic crystals is presented. A careful investigation of the electrochemical properties of macroscopic MoS2 pristine crystals with precise control over the exposure of one plane surface, that is, basal plane or edge plane, was performed. These crystals were characterized thoroughly by AFM, Raman spectroscopy, X-ray photoelectron spectroscopy, voltammetry, digital simulation, and DFT calculations. In the Raman spectra, the basal and edge planes show anisotropy in the preferred excitation of E2g and A1g phonon modes, respectively. The edge plane exhibits a much larger heterogeneous electron transfer rate constant k(0) of 4.96×10(-5) and 1.1×10(-3)  cm s(-1) for [Fe(CN)6 ](3-/4-) and [Ru(NH3 )6 ](3+/2+) redox probes, respectively, compared to the basal plane, which yielded k(0) tending towards zero for [Fe(CN)6 ](3-/4-) and about 9.3×10(-4)  cm s(-1) for [Ru(NH3 )6 ](3+/2+) . The industrially important hydrogen evolution reaction follows the trend observed for [Fe(CN)6 ](3-/4-) in that the basal plane is basically inactive. The experimental comparison of the edge and basal planes of MoS2 crystals is supported by DFT calculations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ion mass spectrometry investigations of the discharge during reactive high power pulsed and direct current magnetron sputtering of carbon in Ar and Ar/N{sub 2}

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

Schmidt, S.; Greczynski, G.; Jensen, J.

2012-07-01

Ion mass spectrometry was used to investigate discharges formed during high power impulse magnetron sputtering (HiPIMS) and direct current magnetron sputtering (DCMS) of a graphite target in Ar and Ar/N{sub 2} ambient. Ion energy distribution functions (IEDFs) were recorded in time-averaged and time-resolved mode for Ar{sup +}, C{sup +}, N{sub 2}{sup +}, N{sup +}, and C{sub x}N{sub y}{sup +} ions. An increase of N{sub 2} in the sputter gas (keeping the deposition pressure, pulse width, pulse frequency, and pulse energy constant) results for the HiPIMS discharge in a significant increase in C{sup +}, N{sup +}, and CN{sup +} ion energies.more » Ar{sup +}, N{sub 2}{sup +}, and C{sub 2}N{sup +} ion energies, in turn, did not considerably vary with the changes in working gas composition. The HiPIMS process showed higher ion energies and fluxes, particularly for C{sup +} ions, compared to DCMS. The time evolution of the plasma species was analyzed for HiPIMS and revealed the sequential arrival of working gas ions, ions ejected from the target, and later during the pulse-on time molecular ions, in particular CN{sup +} and C{sub 2}N{sup +}. The formation of fullerene-like structured CN{sub x} thin films for both modes of magnetron sputtering is explained by ion mass-spectrometry results and demonstrated by transmission electron microscopy as well as diffraction.« less

On Modeling Biomolecular-Surface Nonbonded Interactions: Application to Nucleobase Adsorption on Single-Wall Carbon Nanotube Surfaces

DTIC Science & Technology

2012-01-01

expressed in terms of the Hamaker constants Cn, i.e. 1E(R) = − ∑ ∞ n=6 Cn Rn , where R is their separation. The first term (C6) for two molecules A and B...the Hamaker constant is given by C = 1 4π ∫ ∞ 0 duα(iu)( ε(iu)−1 ε(iu)+1 ) [14], where ε(iu) is the frequency- dependent dielectric function at the

Optical and thermal charge-transfer processes occurring in a series of three-centered, cyanide-bridged intervalent charge-transfer complexes

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

Pfennig, B.W.; Bocarsly, A.B.

1992-01-09

The mixed-valent compound (Pt(NH{sub 3}){sub 4}){sub 2}((NC){sub 5}Fe-CN-Pt(NH{sub 3}){sub 4}-NC-Fe(CN){sub 5} was used as the starting point for the synthesis and characterization of two series of trinuclear {open_quotes}M-Pt-M{close_quotes} compounds. The first group of complexes have the general formula Na{sub 2}(L(NC){sub 4}Fe-CN-Pt(NH{sub 3}){sub 4}-NC-Fe(CN){sub 4}L) (where the sixth coordination site on the terminal iron units has been varied using six different substituted pyridine or pyrazine ligands, L), and the secondary group of compounds have the general formula (Pt(NH){sub 3}){sub 4}){sub 2}((NC){sub 5}M-CN-Pt(NH{sub 3}){sub 4}-NC-M(CN){sub 5}) (where M = Fe, Ru, and Os). All of the compounds yielded an absorption spectrum containingmore » an intervalent charge-transfer (IT) band in the visible. Both series of complexes were modeled using Marcus-Hush theory to estimate the reorganization energies for the optical electron-transfer processes, electron-transfer rate constants, thermal-activation barriers, and the degrees of delocalization of these species. In addition, the kinetics of formation, photochemical decomposition, and a novel solvent-gated charge-transfer process are discussed. 26 refs., 10 figs., 4 tabs.« less

Distorted Carbon Nitride Structure with Substituted Benzene Moieties for Enhanced Visible Light Photocatalytic Activities.

PubMed

Kim, Hyejin; Gim, Suji; Jeon, Tae Hwa; Kim, Hyungjun; Choi, Wonyong

2017-11-22

Carbon nitride (CN) is being intensively investigated as a low-cost visible light active photocatalyst, but its practical applications are limited because of the fast charge pair recombination and low visible light absorption. Here, we introduce a new strategy for enhancing its visible light photocatalytic activity by designing the CN structure in which the nitrogen of tertiary amine is substituted with a benzene molecule connected by three heptazine rings. The intramolecular benzene doping induced the structural changes from planar symmetric structure to distorted geometry, which could be predicted by density functional theory calculation. This structural distortion facilitated the spatial separation of photogenerated charge pairs and retarded charge recombination via exciton dissociation. Such unique properties of the benzene-incorporated CN were confirmed by the photoluminescence (PL) and photoelectrochemical analyses. The optimal loading of benzene doping reduced the PL of the conjugated ring system (π → π* transition) but enhanced the PL of the forbidden n → π* transition at the nitrogen atoms with lone pair electrons due to the distortion from the planar geometry. The photoelectrode of benzene-doped CN exhibited higher photocurrent and lower charge transfer resistance than bare CN electrode, indicating that the photogenerated charge pairs are more efficiently separated. As a result, the benzene-doped CN markedly increased the photocatalytic activity for the degradation of various organic pollutants and that for H 2 O 2 production (via O 2 reduction). This study proposes a simple strategy for chemical structural modification of carbon nitride to boost the visible light photocatalytic activity.

Self-assembled 3D heterometallic Cu(II)/Fe(II) coordination polymers with octahedral net skeletons: structural features, molecular magnetism, thermal and oxidation catalytic properties.

PubMed

Karabach, Yauhen Y; Guedes da Silva, M Fátima C; Kopylovich, Maximilian N; Gil-Hernández, Beatriz; Sanchiz, Joaquin; Kirillov, Alexander M; Pombeiro, Armando J L

2010-12-06

The new three-dimensional (3D) heterometallic Cu(II)/Fe(II) coordination polymers [Cu(6)(H(2)tea)(6)Fe(CN)(6)](n)(NO(3))(2n)·6nH(2)O (1) and [Cu(6)(Hmdea)(6)Fe(CN)(6)](n)(NO(3))(2n)·7nH(2)O (2) have been easily generated by aqueous-medium self-assembly reactions of copper(II) nitrate with triethanolamine or N-methyldiethanolamine (H(3)tea or H(2)mdea, respectively), in the presence of potassium ferricyanide and sodium hydroxide. They have been isolated as air-stable crystalline solids and fully characterized including by single-crystal X-ray diffraction analyses. The latter reveal the formation of 3D metal-organic frameworks that are constructed from the [Cu(2)(μ-H(2)tea)(2)](2+) or [Cu(2)(μ-Hmdea)(2)](2+) nodes and the octahedral [Fe(CN)(6)](4-) linkers, featuring regular (1) or distorted (2) octahedral net skeletons. Upon dehydration, both compounds show reversible escape and binding processes toward water or methanol molecules. Magnetic susceptibility measurements of 1 and 2 reveal strong antiferromagnetic [J = -199(1) cm(-1)] or strong ferromagnetic [J = +153(1) cm(-1)] couplings between the copper(II) ions through the μ-O-alkoxo atoms in 1 or 2, respectively. The differences in magnetic behavior are explained in terms of the dependence of the magnetic coupling constant on the Cu-O-Cu bridging angle. Compounds 1 and 2 also act as efficient catalyst precursors for the mild oxidation of cyclohexane by aqueous hydrogen peroxide to cyclohexanol and cyclohexanone (homogeneous catalytic system), leading to maximum total yields (based on cyclohexane) and turnover numbers (TONs) up to about 22% and 470, respectively.

Millimeter/submillimeter Spectroscopy of PH2CN ({\\tilde{X}} 1A') and CH3PH2 ({\\tilde{X}} 1A'): Probing the Complexity of Interstellar Phosphorus Chemistry

NASA Astrophysics Data System (ADS)

Halfen, D. T.; Clouthier, D. J.; Ziurys, L. M.

2014-11-01

Millimeter/submillimeter spectra of PH2CN ({\\tilde{X}} 1A') and CH3PH2 ({\\tilde{X}} 1A') have been recorded for the first time using direct absorption techniques. This work extends previous measurements of both molecules beyond the 10-50 GHz range. Both species were created in the presence of an AC discharge by the reaction of phosphorus vapor and either cyanogen and hydrogen (PH2CN) or methane (CH3PH2). Twelve rotational transitions of PH2CN were recorded over the region 305-422 GHz for asymmetry components Ka = 0 through 8. For CH3PH2, eight rotational transitions were measured from 210-470 GHz with Ka = 0 through 16; these spectra exhibited greater complexity due to the presence of internal rotation, which splits the Ka = 1, 2, and 3 asymmetry components into A and E states. Combined analyses of the millimeter/submillimeter and previous microwave data were performed for both molecules. For PH2CN, the spectra were fit with a Watson S-reduced asymmetric top Hamiltonian, resulting in more accurate rotational and centrifugal distortion constants. In the case of CH3PH2, an asymmetric top internal-rotation Hamiltonian was employed in the analysis, significantly improving the rotational and torsional parameters over previous microwave estimates. Searches for both molecules were subsequently conducted toward Sgr B2(N), using the 12 m telescope of the Arizona Radio Observatory (ARO). Neither species was identified, with abundance upper limits, relative to H2, of f (PH2CN/H2) < 7.0 × 10-12 and f (CH3PH2/H2) < 8.4 × 10-12. The nitrogen analogs NH2CN and CH3NH2 are therefore more abundant in Sgr B2(N) by factors of >2 and >200, respectively.

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

PubMed

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. This is in addition to the role of the Fe center in modulating the redox potential and geometry and supporting a bridging hydride species between the Ni and Fe centers in the Ni-C state.

Influence of Samarium Substitution on Impedance Dielectric and Electromechanical Properties of Pb(1-x)K2xNb2O6

NASA Astrophysics Data System (ADS)

Sambasiva Rao, K.; Murali Krishna, P.; Madhava Prasad, D.; Lee, Joon Hyung

Ferroelectric, hysteresis, impedance spectroscopy parameters, AC conductivity, and piezoelectric properties in the ceramics of Pb0.74K0.52Nb2O6 and Pb0.74K0.13Sm0.13Nb2O6 have been studied. X-ray diffraction study reveals single phase with the orthorhombic structure. The samples were characterized for ferroelectric and impedance spectroscopy properties from room temperature to 600°C. Cole-Cole plots (Z″ versus Z‧) are drawn at different temperatures. The results obtained are analyzed to understand the conductivity mechanism in both the samples. The piezoelectric constant d33 has been found to be 96 × 10-12 C/N in PKN.

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

NASA Astrophysics Data System (ADS)

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.

New 2D Carbon Nitride Organic Materials Synthesis with Huge-Application Prospects in CN Photocatalyst.

PubMed

Zhao, Gang; Cheng, Yanling; Wu, Yongzhong; Xu, Xijin; Hao, Xiaopeng

2018-04-01

In recent years, 2D materials are attracting increased attention because of their excellent properties. In this paper, new 2D carbon nitride (CN) organic materials are successfully prepared on the basis of the organic synthesis theory, and the thickness is about 1.5 nm. This new 2D CN organic material further strengthens the 2D materials family. Meanwhile, their synthetic mechanism is theoretically speculated. Then CN photocatalysts of several structures are obtained by roasting 2D CN organic materials. Through the photocatalytic hydrogen production experiments, the results exhibit that these kinds of photocatalysts have good photocatalytic effects compared to common g-C 3 N 4 . © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnetic relaxation of 1D coordination polymers (X)₂[Mn(acacen)Fe(CN)₆], X = Ph₄P⁺, Et₄N⁺.

PubMed

Rams, Michał; Peresypkina, Eugenia V; Mironov, Vladimir S; Wernsdorfer, Wolfgang; Vostrikova, Kira E

2014-10-06

Substitution of the organic cation X in the 1D polymer, (X)2[Mn(acacen)Fe(CN)6], leads to an essential change in magnetic behavior. Due to the presence of more voluminous Ph4P(+) cations, the polyanion has a more geometrically distorted chain skeleton and, as a consequence, enhanced single chain magnet (SCM) characteristics compared to those for Et4N(+). The Arrhenius relaxation energy barriers, the exchange interaction constant and the zero-field splitting anisotropy of Mn(III) are determined from the analysis of magnetic measurements. The discussion is supported with ligand field calculations for [Fe(CN)6](3-) that unveils the significant anisotropy of Fe magnetic moments.

Enhanced selective photocatalytic reduction of CO2 to CH4 over plasmonic Au modified g-C3N4 photocatalyst under UV-vis light irradiation

NASA Astrophysics Data System (ADS)

Li, Hailong; Gao, Yan; Xiong, Zhuo; Liao, Chen; Shih, Kaimin

2018-05-01

A series of Au-g-C3N4 (Au-CN) catalysts were prepared through a NaBH4-reduction method using g-C3N4 (CN) from pyrolysis of urea as precursor. The catalysts' surface area, crystal structure, surface morphology, chemical state, functional group composition and optical properties were characterized by X-ray diffraction, transmission electron microscope, X-ray photoelectron spectroscopy, ultraviolet visible (UV-vis) diffuse reflectance spectra, fourier transform infrared, photoluminescence and transient photocurrent analysis. The carbon dioxide (CO2) photoreduction activities under ultraviolet visible (UV-vis) light irradiation were significantly enhanced when gold (Au) was loaded on the surface of CN. 2Au-CN catalyst with Au to CN mole ratio of 2% showed the best catalytic activity. After 2 h UV-vis light irradiation, the methane (CH4) yield over the 2Au-CN catalyst was 9.1 times higher than that over the pure CN. The CH4 selectivity also greatly improved for the 2Au-CN compared to the CN. The deposited Au nanoparticles facilitated the separation of electron-hole pairs on the CN surface. Moreover, the surface plasmon resonance effect of Au further promoted the generation of hot electrons and visible light absorption. Therefore, Au loading significantly improved CO2 photoreduction performance of CN under UV-vis light irradiation.

Quenching of p-Cyanophenylalanine Fluorescence by Various Anions.

PubMed

Pazos, Ileana M; Roesch, Rachel M; Gai, Feng

2013-03-20

To expand the spectroscopic utility of the non-natural amino acid p -cyanophenylalanine (Phe CN ), we examine the quenching efficiencies of a series of commonly encountered anions toward its fluorescence. We find that iodide exhibits an unusually large Stern-Volmer quenching constant, making it a convenient choice in Phe CN fluorescence quenching studies. Indeed, using the villin headpiece subdomain as a testbed we demonstrate that iodide quenching of Phe CN fluorescence offers a convenient means to reveal protein conformational heterogeneity. Furthermore, we show that the amino group of Phe CN strongly quenches its fluorescence, suggesting that Phe CN could be used as a local pH sensor.

Crystal structures and magnetic properties of chiral heterobimetallic chains based on the dicyanoruthenate building block.

PubMed

Ru, Jing; Gao, Feng; Yao, Min-Xia; Wu, Tao; Zuo, Jing-Lin

2014-12-28

By the reaction of chiral Mn(III) Schiff-base complexes with the dicyanoruthenate building block, [Ru(salen)(CN)2](-) (salen(2-) = N,N'-ethylenebis(salicylideneimine) dianion), two couples of enantiomerically pure chiral cyano-bridged heterobimetallic one-dimensional (1D) chain complexes, [Mn((R,R)-salcy)Ru(salen)(CN)2]n (1-(RR)) and [Mn((S,S)-salcy)Ru(salen)(CN)2]n (1-(SS)) (Salcy = N,N'-(1,2-cyclohexanediylethylene)bis(salicylideneiminato) dianion), [Mn((R,R)-salphen)Ru(salen)(CN)2]n (2-(RR)) and [Mn((S,S)-salphen)Ru(salen)(CN)2]n (2-(SS)) (salphen = N,N'-(1,2-diphenylethylene)bis(salicylideneiminato) dianion), were synthesized and structurally characterized. Circular dichroism (CD) and vibrational circular dichroism (VCD) spectra confirm the enantiomeric nature of the optically active complexes. Structural analyses reveal the formation of neutral cyano-bridged zigzag single chains in 1-(RR) and 1-(SS), and double chains in 2-(RR) and 2-(SS). Magnetic studies show that antiferromagnetic coupling is operative between Ru(III) and Mn(III) centers bridged by cyanide. Compounds 1-(RR) and 1-(SS) show metamagnetic behavior with a critical field of about 7.2 kOe at 1.9 K resulting from the intermolecular π∙∙∙π interactions. Additionally, magnetostructural correlation for some typical cyano-bridged heterobimetallic Ru(III)-Mn(III) compounds is discussed.

Synthesis, structural elucidation, solvatochromism and spectroscopic properties of some azo dyes derived from 6-chloro-4-hydroxyquinoline-2(1H)-one

NASA Astrophysics Data System (ADS)

Rufchahi, E. O. Moradi; Gilani, A. Ghanadzadeh; Taghvaei, V.; Karimi, R.; Ramezanzade, N.

2016-03-01

Malondianilide (I) derived from p-chloroaniline was cyclized to 6-chloro-4-hydroxyquinoline-2(1H)-one (II) in moderately good yield using polyphosphoric acid as catalyst. This compound was then coupled with some diazotized aromatic amines to give the corresponding azo disperse dyes 1-12. A systematic study of the effect of solvent, acid, base and pH upon the electronic absorption spectra of the dyes 1-12 was carried out. In DMSO, DMF, CH3CN, CHCl3, EtOH and acidic media (CH3COOH, acidified EtOH) these dyes that theoretically may be involved in azo-hydrazone tautomerism have been detected only as hydrazone tautomers T1 and T2. The acidic dissociation constants of the dyes were measured in 80 vol% ethanol-water solution at room temperature and ionic strength of 0.1. The results were correlated by the Hammett-type equation using the substituent constants σx.

AB Initio Characterization of MgCCH, MgCCH(+), and MgC2, and Pathways to their Formation in the Interstellar Medium

NASA Technical Reports Server (NTRS)

Woon, David E.

1996-01-01

A study of Mg-bearing compounds has been performed in order to determine molecular properties which are critical for planning new astronomical searches and laboratory studies. The primary focus of the work is on MgCCH, MgCCH(+), and the isomers of MgC2. Only MgCCH has been identified in laboratory studies. Additional calculations have been carried out on MgH, MgNC, MgCN, and their cations in an effort to evaluate pathways to the formation of MgCCH and MgCCH(+) in the InterStellar Medium (ISM) or in circumstellar envelopes. Correlated ab initio methods and correlation-consistent basis sets have been employed. Properties including structures, rotational constants, dipole moments, and harmonic frequencies are reported. A transition state between linear MgCC and cyclic MgC2 has been characterized and was found to yield a minimal barrier (approx. 0.5 kcal/mole), indicating easy interconversion to the cyclic form. Direct reactions in the ISM between Mg or Mg(+) and HCCH are precluded by energetic considerations, but a number of ion- molecule or neutral-neutral exchange reactions between CCH and various Mg-containing species offer plausible pathways to MgCCH or MgCCH(+). Weakly bound MgH may react with CCH to form MgCCH, but MgH has not been detected. Both MgNC and MgCN have been observed, but reactions with CCH are slightly endothermic by 1-3 kcal/mole. Although MgH(+), MgNC(+), and MgCN(+) have not been detected, their reactions with CCH to form MgCCH(+) are all exothermic. With only a small barrier separating linear MgCC and cyclic MgC2, the dissociative recombination of MgCCH(+) with an electron is expected to yield cyclic MgC2, and regenerate Mg and CCH. New astronomical searches for MgCCH, MgCCH(+), cyclic MgC2, MgNC(+), and MgCN(+) will provide further insight into organo-magnesium astrochemistry.

Effect of scintillometer height on structure parameter of the refractive index of air measurements

USDA-ARS?s Scientific Manuscript database

Scintillometers measure amount of scintillations by emitting a beam of light over a horizontal path and expresses as the atmospheric turbulence structure parameter as the refractive index of air (Cn**2). Cn**2 represents the turbulent strength of the atmosphere and describes the ability of the atmos...

Structure of cyano-anion ionic liquids: X-ray scattering and simulations.

PubMed

Dhungana, Kamal B; Faria, Luiz F O; Wu, Boning; Liang, Min; Ribeiro, Mauro C C; Margulis, Claudio J; Castner, Edward W

2016-07-14

Ionic liquids with cyano anions have long been used because of their unique combination of low-melting temperatures, reduced viscosities, and increased conductivities. Recently we have shown that cyano anions in ionic liquids are particularly interesting for their potential use as electron donors to excited state photo-acceptors [B. Wu et al., J. Phys. Chem. B 119, 14790-14799 (2015)]. Here we report on bulk structural and quantum mechanical results for a series of ionic liquids based on the 1-ethyl-3-methylimidazolium cation, paired with the following five cyano anions: SeCN(-), SCN(-), N(CN)2 (-), C(CN)3 (-), and B(CN)4 (-). By combining molecular dynamics simulations, high-energy X-ray scattering measurements, and periodic boundary condition DFT calculations, we are able to obtain a comprehensive description of the liquid landscape as well as the nature of the HOMO-LUMO states for these ionic liquids in the condensed phase. Features in the structure functions for these ionic liquids are somewhat different than the commonly observed adjacency, charge-charge, and polarity peaks, especially for the bulkiest B(CN)4 (-) anion. While the other four cyano-anion ionic liquids present an anionic HOMO, the one for Im2,1 (+)/B(CN)4 (-) is cationic.

1D cyanide complexes with 2-pyridinemethanol: Synthesis, crystal structures and spectroscopic properties

NASA Astrophysics Data System (ADS)

Sayın, Elvan; Kürkçüoğlu, Güneş Süheyla; Yeşilel, Okan Zafer; Hökelek, Tuncer

2015-12-01

Two new one-dimensional coordination polymers, [Cu(hmpH)2Pd(μ-CN)2(CN)2]n (1) and [Cu(hmpH)2Pt(μ-CN)2(CN)2]n (2), (hmpH = 2-pyridinemethanol), have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal and elemental analyses techniques. Single crystal X-ray diffraction analysis indicates that complexes 1 and 2 are isomorphous and isostructural, and crystallize in the triclinic system and P-1 space group. The Pd(II) or Pt(II) ions are four coordinated with four cyanide-carbon atoms in a square planar geometry. Cu(II) ion displays a distorted octahedral coordination by two N-atoms and two O-atoms of hmpH ligands, two bridging cyanide groups. In one dimensional structure of the complexes, [M(CN)4]2- (M = Pd(II) or Pt(II)) anions and [Cu(hmpH)2]2+ cations are linked via bridging cyanide ligands. In the complexes, the presence of intramolecular C-H⋯M (M = Pd(II) or Pt(II)) interactions with distance values of 3.00-2.95 Å are established, respectively.

First Observation of Photoinduced Magnetization for the Cyano-Bridged 3d 4f Heterobimetallic Assembly Nd(DMF)4(H2O)3(μ-CN)Fe(CN)5ṡH2O (DMF=N,N-Dimethylformamide)

NASA Astrophysics Data System (ADS)

Li, Guangming; Akitsu, Takashiro; Sato, Osamu; Einaga, Yasuaki

2004-12-01

Photoinduced magnetization of the cyano-bridged 3d 4f hetero-bimetallic assembly Nd (DMF)4(H2O)3(μ-CN)Fe(CN)5ṡH2O (1) (DMF=N,N-dimethylformamide) is described in this paper. The χM T values are enhanced by about 45% after UV light illumination in the temperature range of 5 50 K. We propose that UV light illumination induces a structural distortion in 1. This small structural change is propagated by molecular interactions in the inorganic network. Furthermore, the cooperativity resulting from the molecular interaction functions to increase the activation energy of the relaxation processes, which makes observation of the photoexcited state possible. The flexible network structure through the hydrogen bonds in 1 plays an essential role for the photoinduced phenomenon. This finding may open up a new domain for developing molecule-based magnetic materials.

Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

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

Peresypkina, Eugenia V.; Samsonenko, Denis G.; Novosibirsk State University, Novosibirsk 630090

The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [(Mn(acacen)){sub 2}Ru(NO)(CN){sub 5}]{sub n} and two complexes composed of different cyanorhenates, [Ni(cyclam)]{sub 2}[ReO(OH)(CN){sub 4}](ClO{sub 4}){sub 2}(H{sub 2}O){sub 1.25} and [Cu(cyclam)]{sub 2}[Re(CN){sub 7}](H{sub 2}O){sub 12}, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds.more » However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN){sub n}]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu{sub 4}N){sub 2}[Ru(NO)(CN){sub 5}], soluble in organic media. - Graphical abstract: The very first results in the design of 2D coordination polymers based on penta- and heptacyanometallates of 4d and5d transitions metals are presented. - Highlights: • Design of coordination polymers based on penta- and heptacyanometallates. • New Ru and Re cyanide based heterobimetallic coordination complexes. • Hydrolysis and ox/red processes involving [Re(CN){sub 7}]{sup 3+} during crystallization. • High magnetic anisotropy of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2}(H{sub 2}O){sub n}, M=Cu, Ni, complexes.« less

Experimental study on the atlanto-axial joint and related structures with regional anatomy and medical imaging.

PubMed

Lv, S; He, H; Yang, L; Lin, Q; Duan, S

2011-10-01

To evaluate the anatomy and medical imaging characteristics in a study observing the atlanto-axial joint (AAJ) and related structures. Eight cadaveric specimens of the AAJ segment were studied with both anatomical and imaging methods. The vertebral arteries of the AAJ segment (VA-A), the first and second cervical nerves (CN1, CN2) and synovial fold (SF) of the AAJ were observed and measured. After extending from the vertebral canal, the CN1 goes between the posterior arch of the atlas and VA-A, and the CN2 passes between the posterior arch of the atlas and axis, and is posterior to VA-A. Among the eight cases, six were found in the SF in the central anterior AAJ and five in lateral. The vertebral arteries of the AAJ segment go along the AAJ with four curves, of which the second and fourth are away from the bone structure of the AAJ. The distance from CN1, CN2 to VA-A and that from the second, fourth curve of VA-A to AAJ is 0.0-2.2 mm, 0.0-3.6 mm and 0.0-4.8 mm, 2.0-7.9 mm respectively. There is no significant difference between the measurements made anatomically and those by the imaging method (p > 0.05). The anatomical method has advantages in observing the CN and SF, while the imaging method shows clearly and directly the VA-A and AAJ. Both are mutually complementary with consistent measurements. The combined use of the two provides a new way to study the complicated anatomy in this region.

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

PubMed

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 .

Dynamics of a Room Temperature Ionic Liquid in Supported Ionic Liquid Membranes vs the Bulk Liquid: 2D IR and Polarized IR Pump-Probe Experiments.

PubMed

Shin, Jae Yoon; Yamada, Steven A; Fayer, Michael D

2017-01-11

Supported ionic liquid membranes (SILMs) are membranes that have ionic liquids impregnated in their pores. SILMs have been proposed for advanced carbon capture materials. Two-dimensional infrared (2D IR) and polarization selective IR pump-probe (PSPP) techniques were used to investigate the dynamics of reorientation and spectral diffusion of the linear triatomic anion, SeCN - , in poly(ether sulfone) (PES) membranes and room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimNTf 2 ). The dynamics in the bulk EmimNTf 2 were compared to its dynamics in the SILM samples. Two PES membranes, PES200 and PES30, have pores with average sizes, ∼300 nm and ∼100 nm, respectively. Despite the relatively large pore sizes, the measurements reveal that the reorientation of SeCN - and the RTIL structural fluctuations are substantially slower in the SILMs than in the bulk liquid. The complete orientational randomization, slows from 136 ps in the bulk to 513 ps in the PES30. 2D IR measurements yield three time scales for structural spectral diffusion (SSD), that is, the time evolution of the liquid structure. The slowest decay constant increases from 140 ps in the bulk to 504 ps in the PES200 and increases further to 1660 ps in the PES30. The results suggest that changes at the interface propagate out and influence the RTIL structural dynamics even more than a hundred nanometers from the polymer surface. The differences between the IL dynamics in the bulk and in the membranes suggest that studies of bulk RTIL properties may be poor guides to their use in SILMs in carbon capture applications.

Structure Characterization and Properties of K-Containing Copper Hexacyanoferrate

DOE PAGES

Ojwang, Dickson O.; Grins, Jekabs; Wardecki, Dariusz; ...

2016-06-03

Copper hexacyanoferrate, Cu II[Fe III(CN) 6] 2/3 nH 2O, was synthesized, and varied amounts of K + ions were inserted via reduction by K 2S 2O 3 (aq). Ideally, the reaction can be written as Cu II[Fe III(CN) 6] 2/3∙ nH 2O + 2x/3K + + 2x/3e⁻ ↔K 2x/3Cu II[Fe II xFe III 1- x(CN) 6] 2/3 nH 2O. Infrared, Raman, and Mössbauer spectroscopy studies show that Fe III is continuously reduced to Fe II with increasing x, accompanied by a decrease of the a-axis of the cubic Fmore » $$m\\bar{3}$$m unit cell. Elemental analysis of K by inductively coupled plasma shows that the insertion only begins when a significant fraction, ~20% of the Fe III, has already been reduced. Thermogravimetric analysis shows a fast exchange of water with ambient atmosphere and a total weight loss of ~26 wt % upon heating to 180 °C, above which the structure starts to decompose. The crystal structures of Cu II[Fe III(CN) 6] 2/3∙ nH 2O and K 2/3Cu[Fe(CN) 6] 2/3∙ nH 2O were refined using synchrotron X-ray powder diffraction data. In both, one-third of the Fe(CN) 6 groups are vacant, and the octahedron around Cu II is completed by water molecules. In the two structures, difference Fourier maps reveal three additional zeolitic water sites (8c, 32f, and 48g) in the center of the cavities formed by the Cu N C Fe framework. In conclusion, the K-containing compound shows an increased electron density at two of these sites (32f and 48g), indicating them to be the preferred positions for the K + ions.« less

Multifractal characteristics of optical turbulence measured through a single beam holographic process.

PubMed

Pérez, Darío G; Barillé, Regis; Morille, Yohann; Zielińska, Sonia; Ortyl, Ewelina

2014-08-11

We have previously shown that azopolymer thin films exposed to coherent light that has travelled through a turbulent medium produces a surface relief grating containing information about the intensity of the turbulence; for instance, a relation between the refractive index structure constant C(n)2 as a function of the surface parameters was obtained. In this work, we show that these films capture much more information about the turbulence dynamics. Multifractal detrended fluctuation and fractal dimension analysis from images of the surface roughness produced by the light on the azopolymer reveals scaling properties related to those of the optical turbulence.

The Distribution and Excitation of CH3CN in a Solar Nebula Analog

NASA Astrophysics Data System (ADS)

Loomis, Ryan A.; Cleeves, L. Ilsedore; Öberg, Karin I.; Aikawa, Yuri; Bergner, Jennifer; Furuya, Kenji; Guzman, V. V.; Walsh, Catherine

2018-06-01

Cometary studies suggest that the organic composition of the early Solar Nebula was rich in complex nitrile species such CH3CN. Recent ALMA detections in protoplanetary disks suggest that these species may be common during planet and comet formation, but connecting gas-phase measurements to cometary abundances first requires constraints on formation chemistry and distributions of these species. We present here the detection of seven spatially resolved transitions of CH3CN in the protoplanetary disk around the T-Tauri star TW Hya. Using a rotational diagram analysis, we find a disk-averaged column density of {N}T={1.45}-0.15+0.19× {10}12 cm‑2 and a rotational temperature of {T}rot}={32.7}-3.4+3.9 K. A radially resolved rotational diagram shows the rotational temperature to be constant across the disk, suggesting that the CH3CN emission originates from a layer at z/r ∼ 0.3. Through comparison of the observations with predictions from a disk chemistry model, we find that grain-surface reactions likely dominate CH3CN formation and that in situ disk chemistry is sufficient to explain the observed CH3CN column density profile without invoking inheritance from the protostellar phase. However, the same model fails to reproduce a solar system cometary abundance of CH3CN relative to H2O in the midplane, suggesting that either vigorous vertical mixing or some degree of inheritance from interstellar ices occurred in the Solar Nebula.

A novel µ-conopeptide, CnIIIC, exerts potent and preferential inhibition of NaV1.2/1.4 channels and blocks neuronal nicotinic acetylcholine receptors

PubMed Central

Favreau, Philippe; Benoit, Evelyne; Hocking, Henry G; Carlier, Ludovic; D' hoedt, Dieter; Leipold, Enrico; Markgraf, René; Schlumberger, Sébastien; Córdova, Marco A; Gaertner, Hubert; Paolini-Bertrand, Marianne; Hartley, Oliver; Tytgat, Jan; Heinemann, Stefan H; Bertrand, Daniel; Boelens, Rolf; Stöcklin, Reto; Molgó, Jordi

2012-01-01

BACKGROUND AND PURPOSE The µ-conopeptide family is defined by its ability to block voltage-gated sodium channels (VGSCs), a property that can be used for the development of myorelaxants and analgesics. We characterized the pharmacology of a new µ-conopeptide (µ-CnIIIC) on a range of preparations and molecular targets to assess its potential as a myorelaxant. EXPERIMENTAL APPROACH µ-CnIIIC was sequenced, synthesized and characterized by its direct block of elicited twitch tension in mouse skeletal muscle and action potentials in mouse sciatic and pike olfactory nerves. µ-CnIIIC was also studied on HEK-293 cells expressing various rodent VGSCs and also on voltage-gated potassium channels and nicotinic acetylcholine receptors (nAChRs) to assess cross-interactions. Nuclear magnetic resonance (NMR) experiments were carried out for structural data. KEY RESULTS Synthetic µ-CnIIIC decreased twitch tension in mouse hemidiaphragms (IC50= 150 nM), and displayed a higher blocking effect in mouse extensor digitorum longus muscles (IC = 46 nM), compared with µ-SIIIA, µ-SmIIIA and µ-PIIIA. µ-CnIIIC blocked NaV1.4 (IC50= 1.3 nM) and NaV1.2 channels in a long-lasting manner. Cardiac NaV1.5 and DRG-specific NaV1.8 channels were not blocked at 1 µM. µ-CnIIIC also blocked the α3β2 nAChR subtype (IC50= 450 nM) and, to a lesser extent, on the α7 and α4β2 subtypes. Structure determination of µ-CnIIIC revealed some similarities to α-conotoxins acting on nAChRs. CONCLUSION AND IMPLICATIONS µ-CnIIIC potently blocked VGSCs in skeletal muscle and nerve, and hence is applicable to myorelaxation. Its atypical pharmacological profile suggests some common structural features between VGSCs and nAChR channels. PMID:22229737

Excitation and emission wavelength ratiometric cyanide-sensitive probes for physiological sensing.

PubMed

Badugu, Ramachandram; Lakowicz, Joseph R; Geddes, Chris D

2004-04-01

We characterize three new fluorescent probes that show both spectral shifts and intensity changes in the presence of aqueous cyanide, allowing for both excitation and fluorescence emission wavelength ratiometric and colorimetric sensing. The relatively high binding constants of the probes for cyanide enables a distinct colorimetric change to be visually observed with as little as 10 microM cyanide. The response of the new probes is based on the ability of the boronic acid group to interact with the CN(-) anion, changing from the neutral form of the boronic acid group R-B(OH)(2) to the anionic R-B(-)(OH)3 form, which is an electron-donating group. The presence of an electron-deficient quaternary heterocyclic nitrogen center and a strong electron-donating amino group in the 6 position on the quinolinium backbone provides for the spectral changes observed upon CN(-) complexation. We have determined the binding constants for the ortho-, meta-, and para-boronic acid probes to be 0.12, 0.17, and 0.14 microM(-3). In addition we have synthesized a control compound that does not contain the boronic acid moiety, allowing for structural comparisons and a rationale for the sensing mechanism to be made. Finally we show that the affinity for monosaccharides, such as glucose or fructose, is relatively low as compared to that for cyanide, enabling the potential detection of cyanide in physiologies up to lethal levels.

Function of CN group in organic sensitizers: The first principle study.

PubMed

Liu, Yun; Shao, Di; Bai, Xiaohui; Yang, Zhenqing; Lin, Chundan; Shao, Changjin

2017-05-15

The cyano group (CN) of the acceptor in organic sensitizers plays an important role for highly efficient dye-sensitized solar cells. In this paper, three 5, 6-difluoro-2,1,3-benzothiadiazole (DFBTD) organic molecules with different number of CN units, named ME15, ME16 and ME17, were investigated by the density functional theory (DFT) and time-dependent DFT (TDDFT). We analyzed the CNs effects on the electronic structures, optical properties, adsorption modes and electron transfer and injection. The result shows that ME17 has the largest maximum absorption wavelength (λ max ) among these new designed dyes due to the strong electron withdrawing ability of two CNs. In addition, CN greatly influence the adsorption modes of dye/TiO 2 and electron injection mechanism. ME16 with one CN also has good optical absorption properties and its acceptor has the strongest coupling strength with the TiO 2 semiconductor which is favorable for electron transfer and injection. Thus, we believe that the number of CN groups in acceptor should be moderate and one CN in D-A-π-A structure dyes may be the more appropriate focusing on the light harvesting ability, electron transfer and electron injection. Copyright © 2017 Elsevier B.V. All rights reserved.

Surface Chemistry Interactions of Cationorm with Films by Human Meibum and Tear Film Compounds

PubMed Central

Georgiev, Georgi As.; Yokoi, Norihiko; Nencheva, Yana; Peev, Nikola; Daull, Philippe

2017-01-01

Cationorm® (CN) cationic nanoemulsion was demonstrated to enhance tear film (TF) stability in vivo possibly via effects on tear film lipid layer (TFLL). Therefore the interactions of CN with human meibum (MGS) and TFLL in vitro and in vivo deserve special study. MGS and CN were spread at the air/water interface of a Langmuir surface balance to ensure a range of MGS/CN oil phase ratios: 20/1, 10/1, 5/1, 3/1, 2/1 and 1/1. The films capability to reorganize during dynamic area changes was evaluated via the surface pressure-area compression isotherms and step/relaxation dilatational rheology studies. Films structure was monitored with Brewster angle microscopy. CN/TFLL interactions at the ocular surface were monitored with non-contact specular microscopy. The in vitro studies of MGS/CN layers showed that (i) CN inclusion (at fixed MGS content) increased film elasticity and thickness and that (ii) CN can compensate for moderate meibum deficiency in MGS/CN films. In vivo CN mixed with TFLL in a manner similar to CN/MGS interactions in vitro, and resulted in enhanced thickness of TFLL. In vitro and in vivo data complement each other and facilitated the study of the composition-structure-function relationship that determines the impact of cationic nanoemulsions on TF. PMID:28718823

H2CN+ and H2CNH+: New insight into the structure and dynamics from mass-selected threshold photoelectron spectra

NASA Astrophysics Data System (ADS)

Holzmeier, Fabian; Lang, Melanie; Hader, Kilian; Hemberger, Patrick; Fischer, Ingo

2013-06-01

In this paper, we reinvestigate the photoionization of nitrogen containing reactive intermediates of the composition H2CN and H2CNH, molecules of importance in astrochemistry and biofuel combustion. In particular, H2CN is also of considerable interest to theory, because of its complicated potential energy surface. The species were generated by flash pyrolysis, ionized with vacuum ultraviolet synchrotron radiation, and studied by mass-selected threshold photoelectron (TPE) spectroscopy. In the mass-selected TPE-spectrum of m/z = 28, contributions of all four isomers of H2CN were identified. The excitation energy to the triplet cation of the methylene amidogen radical H2CN was determined to be 12.32 eV. Considerable activity in the C-N mode of the cation is visible. Furthermore, we derived values for excitation into the triplet cations of 11.72 eV for cis-HCNH, 12.65 eV for trans-HCNH, and 11.21 eV for H2NC. The latter values are probably accurate to within one vibrational quantum. The spectrum features an additional peak at 10.43 eV that corresponds to excitation into the C2v-symmetric H2CN+. As this structure constitutes a saddle point, the peak is assigned to an activated complex on the singlet potential energy surface of the cation, corresponding to a hydrogen atom migration. For methanimine, H2CNH, the adiabatic ionization energy IEad was determined to be 9.99 eV and the vibrational structure of the spectrum was analyzed in detail. The uncertainty of earlier values that simply assigned the signal onset to the IEad is thus considerably reduced. The spectrum is dominated by the H-N-C bending mode ν1+ and the rocking mode ν3+. All experimental data were supported by calculations and Franck-Condon simulations.

[In-vitro evaluation of cinnarizine as a competing agent to beta-cyclodextrin inclusion complexes: effect of cinnarizine on the membrane permeation rate of progesterone from its beta-cyclodextrin inclusion complex].

PubMed

Muraoka, Atsushi; Tokumura, Tadakazu; Machida, Yoshiharu

2008-01-01

The use of competing agents is considered a powerful tool for the development of a drug-delivery system with drug/cyclodextrin inclusion complexes. However, there are very few studies examining this issue. To explain this phenomenon, it was thought that a competing agent with a sufficiently high stability constant had not yet been reported. In this study, cinnarizine (CN), which has a high stability constant with beta-cyclodextrin (beta-CD) and unique solubility characteristics, was selected, and its ability as a competing agent was examined in a membrane permeability study. The permeability study showed that the permeation rates of the drugs flurbiprofen, progesterone, and spironolactone decreased with their stability constants with the addition of beta-CD. In one of the drugs, progesterone (Pro), the decrease was restored by the addition of CN. The amount of CN added was a 1:1 molar ratio to the amount of Pro. However, no similar action was induced with the addition of DL-phenylalanine (Phe) in the permeation study at the 1:5 (Pro:Phe) molar ratio. These finding indicate that CN acts as a competing agent, and its action is much stronger than that of Phe.

Formation of negative ions in the interstellar medium by dissociative electron attachment to the H2CN molecule

NASA Astrophysics Data System (ADS)

Kokoouline, Viatcheslav; Fonseca Dos Santos, Samantha; Douguet, Nicolas; Orel, Ann

2013-05-01

The methylene amidogen radical (H2CN) was first discovered, in 1962 by Cochran et al ., and since then it has received considerable attention from both experimentalists and theoreticians. It is considered an important intermediate in the combustion of nitramine propellants and proposed to play a role in extraterrestrial atmospheres. It was detected in interstellar clouds in 1994, and its dissociative electron attachment (DEA) process may be responsible for the formation of the CN- and the H- negative ions: e-+H2CN --> CN- + H2; e-+H2CN --> H- + HCN. We report here the results of our ab initio quantum chemical studies of the geometrical and electronic structure of the methylene amidogen and and its negative ion H2CN- in the theoretical of DEA in H2CN. The scattering calculations are carried out using the complex Kohn variational method. The nuclear dynamics, including dissociation, will later be treated using the MCTDH code with a three-dimensional potential energy surface, in which the distance of CN is kept frozen. This work is supported by the DOE Office of Basic Energy Science and the National Science Foundation, Grant No's PHY-11-60611 and PHY-10-68785.

Octacyanoniobate(IV)-based molecular magnets revealing 3D long-range order

NASA Astrophysics Data System (ADS)

Pełka, R.; Pinkowicz, D.; Drath, O.; Bałanda, M.; Rams, M.; Majcher, A.; Nitek, W.; Sieklucka, B.

2011-07-01

Isostructural series of chemical formula {[MII(pirazol)4]2[NbIV(CN)8]· 4H2O}n (MII = Mn (1), Fe (2), Co (3), Ni (4)) has been obtained by the self-assembly technique. Its unique crystallographic structure consists in the formation of a 3D extended network of magnetic centers braced by geometrically identical cyanido bridges. Magnetic measurements reveal the transitions to the 3D order at temperatures 23.7, 8.3, 5.9, 13.4 K for 1, 2, 3, and 4, respectively. The character of order is demonstrated to be ferrimagnetic for 1 and 2 and ferromagnetic for 3 and 4. The mean-field approach is used to determine the corresponding exchange coupling constants. The observed interactions are discussed within the magnetic orbital model.

Structure cristalline du composé intermétallique Ni18Ge12

PubMed Central

Kars, Mohammed; Herrero, Adrian Gómez; Roisnel, Thierry; Rebbah, Allaoua; Otero-Diáz, L. Carlos

2015-01-01

Single crystals of octa­deca­nickel dodeca­germanide were grown by chemical transport reaction. The inter­metallic compound crystallizes in a superstructure of the hexa­gonal NiAs type (B8 type). All atoms in the asymmetric unit lie on special positions except one Ni atom (two Ni atoms have site symmetry -6.. and another one has site symmetry .2. while the Ge atoms have site symmetries 32., m.. and 3..). In the structure, the Ni atoms are arranged in 11- or 13-vertex polyhedra (CN = 11–13). The coordination polyhedra of the Ge atoms are bicapped square anti­prisms (CN = 10) or 11-vertex polyhedra (CN = 11). The structure exhibits strong Ge⋯Ni inter­actions, but no close Ge⋯Ge contacts are observed. The Ni atoms with CN = 13 form infinite chains along [001] with an Ni—Ni distance of 2.491 (2) Å. PMID:25844198

Carbon Nanotubes/Nanofibers by Plasma Enhanced Chemical Vapour Deposition

NASA Technical Reports Server (NTRS)

Teo, K. B. K.; Hash, D. B.; Bell, M. S.; Chhowalla, M.; Cruden, B. A.; Amaratunga, G. A. J.; Meyyappan, M.; Milne, W. I.

2005-01-01

Plasma enhanced chemical vapour deposition (PECVD) has been recently used for the production of vertically aligned carbon nanotubedfibers (CN) directly on substrates. These structures are potentially important technologically as electron field emitters (e.g. microguns, microwave amplifiers, displays), nanoelectrodes for sensors, filter media, superhydrophobic surfaces and thermal interface materials for microelectronics. A parametric study on the growth of CN grown by glow discharge dc-PECVD is presented. In this technique, a substrate containing thin film Ni catalyst is exposed to C2H2 and NH3 gases at 700 C. Without plasma, this process is essentially thermal CVD which produces curly spaghetti-like CN as seen in Fig. 1 (a). With the plasma generated by biasing the substrate at -6OOV, we observed that the CN align vertically during growth as shown in Fig. l(b), and that the magnitude of the applied substrate bias affects the degree of alignment. The thickness of the thin film Ni catalyst was found to determine the average diameter and inversely the length of the CN. The yield and density of the CN were controlled by the use of different diffusion barrier materials under the Ni catalyst. Patterned CN growth [Fig. l(c)], with la variation in CN diameter of 4.1% and 6.3% respectively, is achieved by lithographically defining the Ni thin film prior to growth. The shape of the structures could be varied from very straight nanotube-like to conical tip-like nanofibers by increasing the ratio of C2H2 in the gas flow. Due to the plasma decomposition of C2H2, amorphous carbon (a-C) is an undesirable byproduct which could coat the substrate during CN growth. Using a combination of depth profiled Auger electron spectroscopy to study the substrate and in-situ mass spectroscopy to examine gas phase neutrals and ions, the optimal conditions for a-C free growth of CN is determined.

Dependence of atmospheric refractive index structure parameter (Cn2) on the residence time and vertical distribution of aerosols.

PubMed

Anand, N; Satheesh, S K; Krishna Moorthy, K

2017-07-15

Effects of absorbing atmospheric aerosols in modulating the tropospheric refractive index structure parameter (Cn2) are estimated using high resolution radiosonde and multi-satellite data along with a radiative transfer model. We report the influence of variations in residence time and vertical distribution of aerosols in modulating Cn2 and why the aerosol induced atmospheric heating needs to be considered while estimating a free space optical communication link budget. The results show that performance of the link is seriously affected if large concentrations of absorbing aerosols reside for a long time in the atmospheric path.

Crystal structures of two mixed-valence copper cyanide complexes with N-methyl­ethylenedi­amine

PubMed Central

Sabatino, Alexander

2017-01-01

The crystal structures of two mixed-valence copper cyanide compounds involving N-methyl­ethylenedi­amine (meen), are described. In compound (I), poly[bis(μ3-cyanido-κ3 C:C:N)tris(μ2-cyanido-κ2 C:N)bis(N-methylethane-1,2-di­amine-κ2 N,N′)tricopper(I)copper(II)], [Cu4(CN)5(C3H10N2)2] or Cu4(CN)5meen2, cyanide groups link CuI atoms into a three-dimensional network containing open channels parallel to the b axis. In the network, two tetra­hedrally bound CuI atoms are bonded by the C atoms of two end-on bridging CN groups to form Cu2(CN)6 moieties with the Cu atoms in close contact at 2.560 (1) Å. Other trigonally bound CuI atoms link these units together to form the network. The CuII atoms, coordinated by two meen units, are covalently linked to the network via a cyanide bridge, and project into the open network channels. In the mol­ecular compound (II), [(N-methylethylenediamine-κ2 N,N′)copper(II)]-μ2-cyanido-κ2 C:N-[bis(cyanido-κC)copper(I)] monohydrate, [Cu2(CN)3(C3H10N2)2]·H2O or Cu2(CN)3meen2·H2O, a CN group connects a CuII atom coordinated by two meen groups with a trigonal–planar CuI atom coordinated by CN groups. The mol­ecules are linked into centrosymmetric dimers via hydrogen bonds to two water mol­ecules. In both compounds, the bridging cyanide between the CuII and CuI atoms has the N atom bonded to CuII and the C atom bonded to CuI, and the CuII atoms are in a square-pyramidal coordination. PMID:28217329

Post-activation of in situ Bsbnd F codoped g-C3N4 for enhanced photocatalytic H2 evolution

NASA Astrophysics Data System (ADS)

Cui, Yanjuan; Wang, Hao; Yang, Chuanfeng; Li, Ming; Zhao, Yimeng; Chen, Fangyan

2018-05-01

Porous graphitic carbon nitride polymer (p-CN-BF) with enhanced photoproduction of H2 from water was prepared by a two-step treatment process including in-situ Boron and fluorine codoping using [Emim]BF4 as dopants followed by post-calcination in air. Several techniques were employed to characterize the modified structure and elucidate the doping state of B and F. It was shown that in-situ doping method is necessary for efficient doping of heteroatoms into the molecular composition of CN. The difference of doping state of B and F was that B doping primary existing in the inside skeleton of CN, but F doping merely presents in the surface layer. The inside doped B made for the enhanced visible light absorption and the production of uniform porous structure during post-sintering process. By the synergistic effect of Bsbnd F codoping and post-activation, p-CN-BF showed much enhanced photoelectron generation, transmission and separation, therefore, it performs high photocatalytic activity for H2 evolution (351 μmol h-1), which was 13 and 5 times higher than samples only modified by Bsbnd F codoping (CN-BF) or post-annealing (P-CN).

Chemical transitions for interstellar C2 and CN in cloud envelopes

NASA Technical Reports Server (NTRS)

Federman, S. R.; Strom, C. J.; Lambert, D. L.; Cardelli, Jason A.; Smith, V. V.; Joseph, C. L.

1994-01-01

Observations were made of absorption from CH, C2, and CN toward moderately reddened stars in Sco, OB2, Ceo OB3, and Taurus/Auriga. For these directions, most of the reddening is associated with a single cloud complex, for example, the rho Ophiuchus molecular cloud, and as a result, the observations probe moderately dense material. When combined with avaliable data for nearby directions, the survey provides the basis for a comprehensive analysis of the chemistry for these species. The chemical transitions affecting C2 and CN in cloud envelopes were analyzed. The depth into a cloud at which a transition takes place was characterized by tau(sub uv), the grain optical depth at 1000 A. One transition at tau(sub uv) approx. = 2, which arises from, the conversion of C(+) into CO, affects the chemistries for both molecules because of the key role this ion plays. A second one involving production terms in the CN chemistry occurs at tau(sub uv) of approx. = 3; neutral reactions which C2 and CH is more important at larger values for tau(sub uv). The transition from photodissociation to chemical destruction takes place at tau(sub uv) approx. = 4.5 for C2 and CN. The observational data for stars in Sco OB2, Cep OB3, and Taurus/Auriga were studied with chemical rate equations containing the most important production and destruction mechanisms. Because the sample of stars in Sco OB2 includes sight lines with A(sub v) ranging from 1-4 mag, sight lines dominated by photochemistry could be analyzed separately from those controlled by gas-phase destruction. The analysis yielded values for two poorly known rate constants for reactions involved in the production of CN; the reactions are C2 + N yields CN + C and C(+) + NH yields all products. The other directions were analyzed with the inferred values. The predicted column densities for C2 and CN agree with the observed values to better than 50%, and in most instances 20%. When combining the estimates for density and temperature derived from chemical modeling and molecular excitation for a specific cloud, such as the rho Ophiuchus molecular cloud, the portion of the cloud envelope probed by C2 and CN absorption was found to be in pressure equilibrium.

Infrared Spectra, Index of Refraction, and Optical Constants of Nitrile Ices Relevant to Titan's Atmosphere

NASA Technical Reports Server (NTRS)

Moore, Marla; Ferrante, Robert; Moore, William; Hudson, Reggie

2010-01-01

Spectra and optical constants of nitrite ices known or suspected to be in Titan's atmosphere are presented from 2.5 to 200 microns (4000 to 50 per cm ). These results are relevant to the ongoing modeling of Cassini CIRS observations of Titan's winter pole. Ices studied include: HCN, hydrogen cyanide; C2N2, cyanogen; CH3CN, acetonitrile; C 2H5CN, propionitrile; and HC3N, cyanoacetylene. For each of these molecules we report new measurements of the index of refraction, n, determined in both the amorphous- and crystallinephase at 670 nm. Spectra were measured and optical constants were calculated for each nitrite at a variety of temperatures including 20, 35, 50, 75, 95, and 110 K, in the amorphous- and crystalline-phase. This laboratory effort uses a dedicated FTIR spectrometer to record transmission spectra of thin-film ice samples. Laser interference is used to measure film thickness during condensation onto a transparent cold window attached to the tail section of a closed-cycle helium cryostat. Optical constants, real (n) and imaginary (k) refractive indices, are determined using Kramers-Kronig (K-K) analysis. Our calculation reproduces the complete spectrum, including all interference effects. Index of refraction measurements are made in a separate dedicated FTIR spectrometer where interference deposit fringes are measured using two 670 nm lasers at different angles to the ice substrate. A survey of these new measurements will be presented along with a discussion of their validation, errors, and application to Titan data.

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

PubMed

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 Pure Rotational Spectra of SiCCN by Fourier-Transform Microwave Spectroscopy

NASA Astrophysics Data System (ADS)

Umeki, Hiroya; Nakajima, Masakazu; Endo, Yasuki

2014-06-01

Pure rotational spectra of SiCCN ( ˜{X} 2Π3/2) have been observed using Fourier-transform microwave (FTMW) spectroscopy in the frequency region 13 to 35 GHz. The SiCCN radical was produced in a supersonic jet by discharging a mixture gas, 0.2% SiCl4 and 0.2% CH3CN diluted in Ar. The effective rotational constant Beff,3/2, the centrifugal distortion constant D, and the hyperfine coupling constants, a + (b + c)/2 and eQq0, were determined with a standard deviation of the fit to be 6 kHz. Determined B and eQq0 are consistent with those derived from ab initio calculations. Λ-type doublings were not resolved for the observed spectra.

Orientation control of barium titanate films using metal oxide nanosheet layer

NASA Astrophysics Data System (ADS)

Uchida, Hiroshi; Oi, Tomotake; Noguchi, Keito; Moki, Shota; Kim, Jin Woon; Shima, Hiromi; Nishida, Ken; Kiguchi, Takanori; Akama, Akihiko; Konno, Toyohiko J.; Funakubo, Hiroshi

2016-10-01

In the present work, we aim to achieve the preferred crystal orientation of chemical solution deposition (CSD)-derived BaTiO3 films on ubiquitous Si wafers with the assistance of Ca2Nb3O10 nanosheet (ns-CN) template layers. The ns-CN on platinized Si (Pt/Si) substrates aligned the BaTiO3(100) plane to the substrate surface, because of the favorable lattice matching of the ns-CN (001) plane. The CSD process in air required a high crystallization temperature of 900 °C for the preferred crystal orientation of BaTiO3(100) because of the BaCO3 byproduct generated during the combustion reaction of the precursor gel. The processing in vacuum to remove CO2 species enhanced the crystal orientation even at the crystallization temperature of 800 °C, although it can generate oxygen vacancies (\\text{V}\\text{O}{} \\bullet \\bullet ) that cause distorted polarization behavior under an applied field higher than approximately 150 kV/cm. The relative dielectric constant (εr) of the (100)-oriented BaTiO3 film on the ns-CN-supported Pt/Si substrate (ns-CN/Pt/Si) was generally larger than that of the randomly oriented film on Pt/Si, depending on the degree of crystal orientation.

Polymeric carbon nitride nanomesh as an efficient and durable metal-free catalyst for oxidative desulfurization.

PubMed

Shen, Lijuan; Lei, Ganchang; Fang, Yuanxing; Cao, Yanning; Wang, Xinchen; Jiang, Lilong

2018-03-06

We report the first use of polymeric carbon nitride (CN) for the catalytic selective oxidation of H 2 S. The as-prepared CN with unique ultrathin "nanomeshes" structure exhibits excellent H 2 S conversion and high S selectivity. In particular, the CN nanomesh also displays better durability in the desulfurization reaction than traditional catalysts, such as carbon- and iron-based materials.

Explaining global surface aerosol number concentrations in terms of primary emissions and particle formation

NASA Astrophysics Data System (ADS)

Spracklen, D. V.; Carslaw, K. S.; Merikanto, J.; Mann, G. W.; Reddington, C. L.; Pickering, S.; Ogren, J. A.; Andrews, E.; Baltensperger, U.; Weingartner, E.; Boy, M.; Kulmala, M.; Laakso, L.; Lihavainen, H.; Kivekäs, N.; Komppula, M.; Mihalopoulos, N.; Kouvarakis, G.; Jennings, S. G.; O'Dowd, C.; Birmili, W.; Wiedensohler, A.; Weller, R.; Gras, J.; Laj, P.; Sellegri, K.; Bonn, B.; Krejci, R.; Laaksonen, A.; Hamed, A.; Minikin, A.; Harrison, R. M.; Talbot, R.; Sun, J.

2010-05-01

We synthesised observations of total particle number (CN) concentration from 36 sites around the world. We found that annual mean CN concentrations are typically 300-2000 cm-3 in the marine boundary layer and free troposphere (FT) and 1000-10 000 cm-3 in the continental boundary layer (BL). Many sites exhibit pronounced seasonality with summer time concentrations a factor of 2-10 greater than wintertime concentrations. We used these CN observations to evaluate primary and secondary sources of particle number in a global aerosol microphysics model. We found that emissions of primary particles can reasonably reproduce the spatial pattern of observed CN concentration (R2=0.46) but fail to explain the observed seasonal cycle (R2=0.1). The modeled CN concentration in the FT was biased low (normalised mean bias, NMB=-88%) unless a secondary source of particles was included, for example from binary homogeneous nucleation of sulfuric acid and water (NMB=-25%). Simulated CN concentrations in the continental BL were also biased low (NMB=-74%) unless the number emission of anthropogenic primary particles was increased or a mechanism that results in particle formation in the BL was included. We ran a number of simulations where we included an empirical BL nucleation mechanism either using the activation-type mechanism (nucleation rate, J, proportional to gas-phase sulfuric acid concentration to the power one) or kinetic-type mechanism (J proportional to sulfuric acid to the power two) with a range of nucleation coefficients. We found that the seasonal CN cycle observed at continental BL sites was better simulated by BL particle formation (R2=0.3) than by increasing the number emission from primary anthropogenic sources (R2=0.18). The nucleation constants that resulted in best overall match between model and observed CN concentrations were consistent with values derived in previous studies from detailed case studies at individual sites. In our model, kinetic and activation-type nucleation parameterizations gave similar agreement with observed monthly mean CN concentrations.

Mapping Vinyl Cyanide and Other Nitriles in Titan’s Atmosphere Using ALMA

NASA Astrophysics Data System (ADS)

Lai, J. C.-Y.; Cordiner, M. A.; Nixon, C. A.; Achterberg, R. K.; Molter, E. M.; Teanby, N. A.; Palmer, M. Y.; Charnley, S. B.; Lindberg, J. E.; Kisiel, Z.; Mumma, M. J.; Irwin, P. G. J.

2017-11-01

Vinyl cyanide (C2H3CN) is theorized to form in Titan’s atmosphere via high-altitude photochemistry and is of interest regarding the astrobiology of cold planetary surfaces due to its predicted ability to form cell membrane-like structures (azotosomes) in liquid methane. In this work, we follow up on the initial spectroscopic detection of C2H3CN on Titan by Palmer et al. with the detection of three new C2H3CN rotational emission lines at submillimeter frequencies. These new, high-resolution detections have allowed for the first spatial distribution mapping of C2H3CN on Titan. We present simultaneous observations of C2H5CN, HC3N, and CH3CN emission, and obtain the first (tentative) detection of C3H8 (propane) at radio wavelengths. We present disk-averaged vertical abundance profiles, two-dimensional spatial maps, and latitudinal flux profiles for the observed nitriles. Similarly to HC3N and C2H5CN, which are theorized to be short-lived in Titan’s atmosphere, C2H3CN is most abundant over the southern (winter) pole, whereas the longer-lived CH3CN is more concentrated in the north. This abundance pattern is consistent with the combined effects of high-altitude photochemical production, poleward advection, and the subsequent reversal of Titan’s atmospheric circulation system following the recent transition from northern to southern winter. We confirm that C2H3CN and C2H5CN are most abundant at altitudes above 200 km. Using a 300 km step model, the average abundance of C2H3CN is found to be 3.03 ± 0.29 ppb, with a C2H5CN/C2H3CN abundance ratio of 2.43 ± 0.26. Our HC3N and CH3CN spectra can be accurately modeled using abundance gradients above the tropopause, with fractional scale-heights of 2.05 ± 0.16 and 1.63 ± 0.02, respectively.

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

Halfen, D. T.; Ziurys, L. M.; Clouthier, D. J., E-mail: halfendt@as.arizona.edu

Millimeter/submillimeter spectra of PH{sub 2}CN ( X-tilde {sup 1}A') and CH{sub 3}PH{sub 2} ( X-tilde {sup 1}A') have been recorded for the first time using direct absorption techniques. This work extends previous measurements of both molecules beyond the 10-50 GHz range. Both species were created in the presence of an AC discharge by the reaction of phosphorus vapor and either cyanogen and hydrogen (PH{sub 2}CN) or methane (CH{sub 3}PH{sub 2}). Twelve rotational transitions of PH{sub 2}CN were recorded over the region 305-422 GHz for asymmetry components K{sub a} = 0 through 8. For CH{sub 3}PH{sub 2}, eight rotational transitions weremore » measured from 210-470 GHz with K{sub a} = 0 through 16; these spectra exhibited greater complexity due to the presence of internal rotation, which splits the K{sub a} = 1, 2, and 3 asymmetry components into A and E states. Combined analyses of the millimeter/submillimeter and previous microwave data were performed for both molecules. For PH{sub 2}CN, the spectra were fit with a Watson S-reduced asymmetric top Hamiltonian, resulting in more accurate rotational and centrifugal distortion constants. In the case of CH{sub 3}PH{sub 2}, an asymmetric top internal-rotation Hamiltonian was employed in the analysis, significantly improving the rotational and torsional parameters over previous microwave estimates. Searches for both molecules were subsequently conducted toward Sgr B2(N), using the 12 m telescope of the Arizona Radio Observatory (ARO). Neither species was identified, with abundance upper limits, relative to H{sub 2}, of f (PH{sub 2}CN/H{sub 2}) < 7.0 × 10{sup –12} and f (CH{sub 3}PH{sub 2}/H{sub 2}) < 8.4 × 10{sup –12}. The nitrogen analogs NH{sub 2}CN and CH{sub 3}NH{sub 2} are therefore more abundant in Sgr B2(N) by factors of >2 and >200, respectively.« less

Crystal Structure and Energy Transfer in Double-Complex Salts Composed of Tris(2,2'-bipyridine)ruthenium(II) or Tris(2,2'-bipyridine)osmium(II) and Hexacyanochromate(III).

PubMed

Otsuka, Takuhiro; Takahashi, Naoto; Fujigasaki, Naoki; Sekine, Akiko; Ohashi, Yuji; Kaizu, Youkoh

1999-03-22

In crystals of double-complex salts [M(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O (M(2+) = Ru(2+), Os(2+); bpy = 2,2'-bipyridine), luminescence from (3)CT state of [M(bpy)(3)](2+) is partially quenched by [Cr(CN)(6)](3)(-) at 77 K and room temperature (RT). This quenching is attributed to intermolecular excitation energy transfer from the (3)CT state of [M(bpy)(3)](2+) to the (2)E(g) state of [Cr(CN)(6)](3)(-). Crystal structure and crystal parameters of [Os(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O: monoclinic, C2, a = 22.384(4) Å, b = 13.827(4) Å, c = 22.186(3) Å, beta = 90.70(2) degrees, V = 6866(2) Å(3), Z = 4, R = 0.0789, R(w) = 0.1932: are almost the same as those of [Ru(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O: monoclinic, C2, a = 22.414(2) Å, b = 13.7686(15) Å, c = 22.207(2) Å, beta = 90.713(8) degrees, V = 6852.9(12) Å(3), Z = 4, R = 0.0554, R(w) = 0.1679. Moreover, these double complex salts have the same distance and relative orientation between donor and acceptor. The rate of intermolecular energy transfer from [M(bpy)(3)](2+) to [Cr(CN)(6)](3)(-) was evaluated by the decay time of luminescence from (3)CT state of [M(bpy)(3)](2+) in single- and double-complex salts. The rate of energy transfer in [Os(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O (4.9 x 10(7) s(-)(1)) is about eight times larger than that in [Ru(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O (6.0 x 10(6) s(-)(1)) at 77 K. The difference of energy transfer rate is brought about by only the spectral overlap between the normalized luminescence spectrum from the (3)CT state of donor ([M(bpy)(3)](2+)) and the normalized excitation spectrum of the (2)E(g) state of acceptor ([Cr(CN)(6)](3)(-)) in the salts. Decay rates of the (3)CT state in [M(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O were measured as a function of temperature. A large enhancement of a decay rate from the (3)CT state was obtained for [Ru(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O as the temperature was increased. This result implies that an additional path from the (3)CT state of [Ru(bpy)(3)](2+) to the (2)T(2g) state of [Cr(CN)(6)](3)(-) would be opened for energy transfer with a rise in temperature in [Ru(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O.

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.

PubMed

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.

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

PubMed Central

Gray, Bradley W.; Bailey, Jessica M.; Smith, Douglas; Hansen, Martin; Kristensen, Jesper L.

2014-01-01

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 characterized. Objective 25CN-NBOH was compared to the traditional phenethylamine hallucinogen R(−)-2,5-dimethoxy-4-iodoamphetamine (DOI) using mouse models of drug-elicited head twitch behavior and drug discrimination. Methods Drug-elicited head twitches were quantified for 10 min following administration of various doses of either DOI or 25CN-NBOH, with and without pretreatments of 0.01 mg/kg 5-HT2A antagonist M100907 or 3.0 mg/kg 5-HT2C antagonist RS102221. The capacity of 25CN-NBOH to attenuate DOI-elicited head twitch was also investigated. Mice were trained to discriminate DOI or M100907 from saline, and 25CN-NBOH was tested for generalization. Results 25CN-NBOH induced a head twitch response in the mouse that was lower in magnitude than that of DOI, blocked by M100907, but not altered by RS102221. DOI-elicited head twitch was dose-dependently attenuated by 25CN-NBOH pretreatment. 25CN-NBOH produced 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 than DOI in two mouse models of hallucinogenic effects. The effectiveness with which M100907 antagonized the behavioral actions of 25CN-NBOH strongly suggests that the 5-HT2A receptor is an important site of agonist action for this compound in vivo. PMID:25224567

Fabrication and characterization of PbO2 electrode modified with [Fe(CN)6](3-) and its application on electrochemical degradation of alkali lignin.

PubMed

Hao, Xu; Quansheng, Yuan; Dan, Shao; Honghui, Yang; Jidong, Liang; Jiangtao, Feng; Wei, Yan

2015-04-09

PbO2 electrode modified by [Fe(CN)6](3-) (marked as FeCN-PbO2) was prepared by electro-deposition method and used for the electrochemical degradation of alkali lignin (AL). The surface morphology and the structure of the electrodes were characterized by scanning electronic microscopy (SEM) and X-ray diffraction (XRD), respectively. The stability and electrochemical activity of FeCN-PbO2 electrode were characterized by accelerated life test, linear sweep voltammetry, electrochemical impedance spectrum (EIS) and AL degradation. The results showed that [Fe(CN)6](3-) increased the average grain size of PbO2 and formed a compact surface coating. The service lifetime of FeCN-PbO2 electrode was 287.25 h, which was longer than that of the unmodified PbO2 electrode (100.5h). The FeCN-PbO2 electrode showed higher active surface area and higher oxygen evolution potential than that of the unmodified PbO2 electrode. In electrochemical degradation tests, the apparent kinetics coefficient of FeCN-PbO2 electrode was 0.00609 min(-1), which was higher than that of unmodified PbO2 electrode (0.00419 min(-1)). The effects of experimental parameters, such as applied current density, initial AL concentration, initial pH value and solution temperature, on electrochemical degradation of AL by FeCN-PbO2 electrode were evaluated. Copyright © 2015 Elsevier B.V. All rights reserved.

The effects of phase transformation on the structure and mechanical properties of TiSiCN nanocomposite coatings deposited by PECVD method

NASA Astrophysics Data System (ADS)

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.

Lesions of the amygdala central nucleus abolish lipoprivic-enhanced responding during oil-predicting conditioned stimuli.

PubMed

Benoit, S C; Morell, J R; Davidson, T L

1999-12-01

T. L. Davidson, A. M. Altizer, S. C. Benoit, E. K. Walls, and T. L. Powley (1997) reported that rats show facilitated responding to conditioned stimuli (CSs) that predict oil, after administration of the lipoprivic agent, Na-2-mercaptoacetate (MA). This facilitation was blocked by vagal deafferentation. The present article extends that investigation to another structure, the amygdala central nucleus (CN). The CN receives inputs from dorsal vagal nuclei, and neurotoxic lesions of this nucleus are reported to abolish feeding in response to lipoprivic challenges. In Experiment 1, rats with ibotenic acid (IBO) lesions of the CN failed to show enhanced appetitive responding during oil-predicting CSs after administration of MA. Experiment 2 used a conditioned taste-aversion procedure to establish that rats with IBO lesions of the CN were able to discriminate the tastes of sucrose and peanut oil and had intact CS-US representations. It is concluded that the amygdala CN is a necessary structure for the detection of lipoprivic challenges.

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

PubMed

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.

Magnetic ordering and spin-glass behavior in first-row transition metal hexacyanomanganate(IV) Prussian blue analogues.

PubMed

Buschmann, W E; Miller, J S

2000-05-29

Magnetically ordered Prussian blue analogues with the general formulation of M[Mn(CN)6] (M = V, Cr, Mn, Co, Ni) were made in aprotic media utilizing [MnIV(CN)6]2-. These analogs are valence-ambiguous, as they can be formulated as MII[MnIV(CN)6] or MIII[MnIII(CN)6]. The X-ray powder diffraction of each member of this family can be indexed to the face-centered cubic (fcc) Prussian blue structure type, with atypically reduced unit cell parameters (a approximately 9.25 +/- 0.25 A) with respect to hydrated Prussian blue structured materials (a > or = 10.1 A). The reduced a-values are attributed to a contraction of the lattice in the absence of water or coordinating solvent molecule (i.e., MeCN) that is necessary to help stabilize the structure during lattice formation. Based on vCN IR absorptions, X-ray photoelectron spectra, and magnetic data, the following oxidation state assignments are made: MII[MnIV(CN)6] (M = Co, Ni) and MIII[MnIII(CN)6] (M = V, Cr, Mn). Formation of MnIII[MnIII(CN)6] is in contrast to MnII[MnIV(CN)6] prepared from aqueous media. Above 250 K, the magnetic susceptibilities of M[Mn(CN)6] (M = V, Cr, Mn, Co, Ni) can be fit to the Curie-Weiss equation with theta = -370, -140, -105, -55, and -120 K, respectively, suggesting strong antiferromagnetic coupling. The room temperature effective moments, respectively, are 3.71, 4.62, 5.66, 4.54, and 4.91 microB, consistent with the above oxidation state assignments. All compounds do not exhibit magnetic saturation at 50 kOe, and exhibit frequency-dependent chi'(T) and chi"(T) responses characteristic of spin-glass-like behavior. M[Mn(CN)6] order as ferrimagnets, with Tc's taken from the peak in the 10 Hz chi'(T) data, of 19, 16, 27.1, < 1.75, and 4.8 K for M = V, Cr, Mn, Co, and Ni, respectively. The structural and magnetic disorder prevents NiII[MnIV(CN)6] from ordering as a ferromagnet as anticipated, and structural inhomogeneities allow CoII[MnIV(CN)6] and VIII[MnIII(CN)6] to unexpectedly order as ferrimagnets. Also, MnIII[MnIII(CN)6] behaves as a reentrant spin glass showing two transitions at 20 and 27.1 K, and similar behavior is evident for CrIII[MnIII(CN)6]. Hysteresis with coercive fields of 340, 130, 8, 9, and 220 Oe and remanent magnetizations of 40, 80, 1500, 4, and 250 emuOe/mol are observed for M = V, Cr, Mn, Co, and Ni, respectively.

N-Functionalized MXenes: ultrahigh carrier mobility and multifunctional properties.

PubMed

Shao, Yangfan; Zhang, Fang; Shi, Xingqiang; Pan, Hui

2017-11-01

Two dimensional (2D) nanomaterials have demonstrated huge potential in wide applications from nanodevices to energy harvesting/storage. In this work, we propose a new class of 2D monolayers, nitrogen-functionalized MXenes (Nb 2 CN 2 and Ta 2 CN 2 ), based on density-functional theory (DFT). We find that these monolayers are direct semiconductors with near linear energy dispersions at the Γ point. M 2 CN 2 monolayers have significant small effective mass and show an ultra-high mobility of up to 10 6 cm 2 V -1 s -1 . We show that the electronic structures of the M 2 CN 2 monolayers can be easily controlled by biaxial and uniaxial strains. Importantly, the carrier mobility and direct band gap can be dramatically increased within a certain range of strain. A direct-indirect band gap transition can be triggered and the band gap can be tuned under strain. The tunable electronic properties are attributed to the structural changes and charge redistribution under stain. Our findings demonstrate that N-functionalized MXenes are promising materials for nanodevices with high speed and low power.

Dispersed fluorescence spectroscopy of the SiCN A ˜ 2 Δ - X ˜ 2 Π system: Observation of some vibrational levels with chaotic characteristics

NASA Astrophysics Data System (ADS)

Fukushima, Masaru; Ishiwata, Takashi

2016-12-01

The laser induced fluorescence (LIF) spectrum of the A ˜ 2Δ - X ˜ 2Π transition was obtained for SiCN generated by laser ablation under supersonic free jet expansion. The vibrational structures of the dispersed fluorescence (DF) spectra from single vibronic levels (SVL's) were analyzed with consideration of the Renner-Teller (R-T) interaction. Analysis of the pure bending (ν2) structure by a perturbation approach including R-T, anharmonicity, spin-orbit (SO), and Herzberg-Teller (H-T) interactions indicated considerably different spin splitting for the μ and κ levels of the X ˜ 2Π state of SiCN, in contrast to identical spin splitting for general species derived from the perturbation approach, where μ and κ specify the lower and upper levels, respectively, separated by R-T. Further analysis of the vibrational structure including R-T, anharmonicity, SO, H-T, Fermi, and Sears interactions was carried out via a direct diagonalization procedure, where Sears resonance is a second-order interaction combined from SO and H-T interactions with Δ K = ± 1, ΔΣ = ∓1, and Δ P = 0, and where P is a quantum number, P = K + Σ. The later numerical analysis reproduced the observed structure, not only the pure ν2 structure but also the combination structure of the ν2 and the Si-CN stretching (ν3) modes. As an example, the analysis demonstrates Sears resonance between vibronic levels, (0110) κ Σ(+) and ( 0 2 0 0 ) μ Π /1 2 , with Δ K = ± 1 and Δ P = 0. On the basis of coefficients of their eigen vectors derived from the numerical analysis, it is interpreted as an almost one-to-one mixing between the two levels. The mixing coefficients of the two vibronic levels agree with those obtained from computational studies. The numerical analysis also indicates that some of the vibronic levels show chaotic characteristics in view of the two-dimensional harmonic oscillator (2D-HO) basis which is used as the basis function in the present numerical analysis; i.e., the eigen vectors for some of the observed levels have several components of the basis, and we have not been able to give precise vibronic assignments for the levels, but just vibronically labeled, referring the largest component in their vectors. (To emphasize this situation, we do not use the word "assignment," but prefer to use "label" as the meaning of just "label," but not "assign," throughout this paper.) The latter shows that the vibronic labels of the levels are meaningless, and the P quantum number and the order of their eigen states in the P matrix block derived in the numerical analysis only characterize the vibronic levels. Comparing the constants obtained for all of the interactions with those of species showing Sears resonance and studied previously, it is found that none of them are strong, but are moderate. It is thus concluded that the chaotic appearance is not derived by any strong interaction, but is induced by complex and accidental proximities of the vibronic levels caused by the moderate interactions.

The ν 1Band System of H-CC-CN (Cyanoacetylene)

NASA Astrophysics Data System (ADS)

Winther, F.; Klee, S.; Mellau, G.; Naı̈m, S.; Mbosei, L.; Fayt, A.

1996-02-01

The ν1band system of cyanoacetylene (H-CC-CN) has been observed with an effective resolution of 0.006 cm-1. ν1= 3327.37085(3) cm-1,B1= 0.15149762(2) cm-1,D1= 1.8065(3) × 10-8cm-1. Several hot bands from the statesv5= 1,v6= 1,v7= 1, 2 (l= 0 and 2), 3 (l= 1 and 3), and 4 (l= 0 and 2),v6=v7= 1 (l= 0 and 2), andv6= 1 andv7= 2 (l= 3) have also been observed and analyzed. Many bands show strong local perturbations due to interactions with states which are combinations of the modes 4, 5, 6, and 7. These perturbing states are also described quantitatively, and rovibrational constants are given.

[Fe(III)(dmbpy)(CN)4]-: a new building block for designing single-chain magnets.

PubMed

Toma, Luminita Marilena; Pasán, Jorge; Ruiz-Pérez, Catalina; Lloret, Francesc; Julve, Miguel

2012-11-28

We herein present the synthesis and magneto-structural study of a new family of heterobimetallic chains of general formula {[Fe(III)(dmbpy)(CN)(4)](2)M(II)(H(2)O)(2)}(n)·pnH(2)O [dmbpy = 4,4'-dimethyl-2,2'-bipyridine; M = Mn (2), Cu (3), Ni (4) and Co (5) with p = 4 (2), 3 (3), 9 (4) and 3.5 (5)] which were prepared by using the mononuclear PPh(4)[Fe(III)(dmbpy)(CN)(4)]·3H(2)O (1) building block (PPh(4)(+) = tetraphenylphosphonium) as a ligand toward fully solvated M(II) ions. The structure of 1 consists of discrete [Fe(III)(dmbpy)(CN)(4)](-) anions, tetraphenylphosphonium cations and noncoordinated water molecules. Complexes 2-5 are isostructural compounds whose structure consists of neutral 4,2-wave like heterobimetallic chains of formula {[Fe(III)(dmbpy)(CN)(4)](2)M(II)(H(2)O)(2)}(n) where the [Fe(III)(dmbpy)(CN)(4)](-) entity adopts a bis-monodentate coordination mode toward trans-[M(II)(H(2)O)(2)] units through two of its four cyanide groups in cis positions. 1 exhibits the magnetic behaviour of magnetically isolated six-coordinate low-spin Fe(III) complexes with an important orbital contribution. 2 behaves as ferrimagnetic Fe(III)(2)Mn(II) chains, whereas 3-5 exhibit intrachain ferromagnetic couplings between the low-spin Fe(III) and either Cu(II) (3), Ni (4) or Co(II) (5) as well as frequency-dependence of the out-of-phase ac susceptibility signals below 3.0 (3), 5.5 (4) and 5.0 K (5). The relaxation time and the energy to reverse the magnetization of 3-5 are related to the anisotropy of the M(II) center and to the intra- and interchain magnetic interactions. Unprecedentedly in the world of cyanide-bearing complexes, 5 exhibits a double slow relaxation of the magnetization.

Increasing the hydrolysis constant of the reactive site upon introduction of an engineered Cys¹⁴-Cys³⁹ bond into the ovomucoid third domain from silver pheasant.

PubMed

Hemmi, Hikaru; Kumazaki, Takashi; Kojima, Shuichi; Yoshida, Takuya; Ohkubo, Tadayasu; Yokosawa, Hideyoshi; Miura, Kin-Ichiro; Kobayashi, Yuji

2011-08-01

P14C/N39C is the disulfide variant of the ovomucoid third domain from silver pheasant (OMSVP3) introducing an engineered Cys¹⁴-Cys³⁹ bond near the reactive site on the basis of the sequence homology between OMSVP3 and ascidian trypsin inhibitor. This variant exhibits a narrower inhibitory specificity. We have examined the effects of introducing a Cys¹⁴-Cys³⁹ bond into the flexible N-terminal loop of OMSVP3 on the thermodynamics of the reactive site peptide bond hydrolysis, as well as the thermal stability of reactive site intact inhibitors. P14C/N39C can be selectively cleaved by Streptomyces griseus protease B at the reactive site of OMSVP3 to form a reactive site modified inhibitor. The conversion rate of intact to modified P14C/N39C is much faster than that for wild type under any pH condition. The pH-independent hydrolysis constant (K(hyd) °) is estimated to be approximately 5.5 for P14C/N39C, which is higher than the value of 1.6 for natural OMSVP3. The reactive site modified form of P14C/N39C is thermodynamically more stable than the intact one. Thermal denaturation experiments using intact inhibitors show that the temperature at the midpoint of unfolding at pH 2.0 is 59 °C for P14C/N39C and 58 °C for wild type. There have been no examples, except P14C/N39C, where introducing an engineered disulfide causes a significant increase in K(hyd) °, but has no effect on the thermal stability. The site-specific disulfide introduction into the flexible N-terminal loop of natural Kazal-type inhibitors would be useful to further characterize the thermodynamics of the reactive site peptide bond hydrolysis. Copyright © 2011 European Peptide Society and John Wiley & Sons, Ltd.

In vitro activation of dibromoacetonitrile to cyanide by myeloperoxidase.

PubMed

Al-Abbasi, Fahad A

2016-08-01

Dibromoacetonitrile (DBAN) is a disinfection by-product classified as a potential human and animal carcinogen. This study aimed at investigating the ability of myeloperoxidase (MPO) to oxidize DBAN to cyanide (CN - ) in vitro Detection of CN - served as a marker for the possible generation of free radical intermediates implicated in DBAN-induced toxicity. Optimum conditions for the oxidation of DBAN to CN - were characterized with respect to pH, temperature, and time of incubation as well as DBAN, MPO, potassium chloride, and hydrogen peroxide (H 2 O 2 ) concentrations in incubation mixtures. Maximum reaction velocity and Michaelis-Menten constant were assessed. Addition of sodium hypochlorite to the reaction mixtures significantly enhanced the rate of the reaction. Addition of the MPO inhibitors, sodium azide, 4-amino benzoic acid hydrazine, or indomethacin to the reaction mixtures significantly decreased the rate of DBAN oxidation. Inclusion of the antioxidant enzyme superoxide dismutase in the incubation mixtures significantly decreased the rate of reaction. Inclusion of the sulfhydryl compounds as reduced glutathione, N-acetylcysteine, d-penicillamine, or l-cysteine enhanced the rate of DBAN oxidation. These results demonstrate the ability of MPO/H 2 O 2 /chloride ion system to oxidize DBAN to CN - and provide insight for the elucidation of DBAN chronic toxicity. © The Author(s) 2015.

Metal-free spin and spin-gapless semiconducting heterobilayers: monolayer boron carbonitrides on hexagonal boron nitride.

PubMed

Pan, Hongzhe; Zhang, Hongyu; Sun, Yuanyuan; Ding, Yingchun; Chen, Jie; Du, Youwei; Tang, Nujiang

2017-06-07

The interfaces between monolayer boron carbonitrides and hexagonal boron nitride (h-BN) play an important role in their practical applications. Herein, we respectively investigate the structural and electronic properties of two metal-free heterobilayers constructed by vertically stacking two-dimensional (2D) spintronic materials (B 4 CN 3 and B 3 CN 4 ) on a h-BN monolayer from the viewpoints of lattice match and lattice mismatch models using density functional calculations. It is found that both B 4 CN 3 and B 3 CN 4 monolayers can be stably adsorbed on the h-BN monolayer due to the van der Waals interactions. Intriguingly, we demonstrate that the bipolar magnetic semiconductor (BMS) behavior of the B 4 CN 3 layer and the spin gapless semiconductor (SGS) property of the B 3 CN 4 layer can be well preserved in the B 4 CN 3 /BN and B 3 CN 4 /BN heterobilayers, respectively. The magnetic moments and spintronic properties of the two systems originate mainly from the 2p z electrons of the carbon atoms in the B 4 CN 3 and B 3 CN 4 layers. Furthermore, the BMS behavior of the B 4 CN 3 /BN bilayer is very robust while the electronic property of the B 3 CN 4 /BN bilayer is sensitive to interlayer couplings. These theoretical results are helpful both in understanding the interlayer coupling between B 4 CN 3 or B 3 CN 4 and h-BN monolayers and in providing a possibility of fabricating 2D composite B 4 CN 3 /BN and B 3 CN 4 /BN metal-free spintronic materials theoretically.

Synthesis, spectroscopic, thermal and structural properties of 4-(2-aminoethyl)pyridinium tetracyanometallate(II) complexes

NASA Astrophysics Data System (ADS)

Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla; Şenyel, Mustafa; Şahin, Onur

2017-05-01

In this study, three new complexes (4aepyH)2[Ni(CN)4] (1), (4aepyH)2[Pd(CN)4] (2) and (4aepyH)2[Pt(CN)4] (3) [4aepy = 4-(2-aminoethyl)pyridine] have been synthesized and characterized by elemental, thermal, vibrational (FT-IR and Raman) and single-crystal X-ray diffraction techniques. The crystallographic analyses reveal that the complexes crystallize in the monoclinic system, space group C2/c. The asymmetric units of the complexes contain one M(II) ion, two cyanide ligands and one non-coordinated the 4aepy ligand. Each M(II) ion is four coordinated with four cyanide-carbon atoms in a square planar geometry and the [M(CN)4]2- anions act as a counter ion. The 4aepyH cations in the complexes compose of the protonation of the 4aepy. The vibrational spectral data also supported to the crystal structures of the complexes. Thermal stabilities and decomposition products of the complexes were investigated in the temperature range 40-700 °C in the static air atmosphere.

Synthesis and Structural Characterization of Tris(dimethyldithicarbamate)Indium(III), In[S2CN(CH3)2]3

NASA Technical Reports Server (NTRS)

Clark, Eric B.; Breen, Marc L.; Fanwick, Phillip E.; Hepp, Aloysius F.; Duraj, Stan A.

1998-01-01

The synthesis and structure of the indium dithiocarbamate, In[S2CN(CH3)2]30 central dot 1/2 4- mepy (4-mepy = 4-methylpyridine), is described. Indium metal was oxidized by tetramethylthiuramdisulfide in 4-methylpyridine at 25 C to form a new, homoleptic indium(III) dithiocarbamate in yields exceeding 60%. In[S2CN(CH3)2]3 exists as a discrete molecule with a distorted-octahedral geometry. The compound crystallizes in the P 1-bar (No. 2) space group with a = 9.282(l) A, b = 10.081 (1) A, c, c = 12.502 A, alpha = 73.91 (1)(sup 0), beta = 70.21(1)(sup 0), gamma = 85.84(1)(sup 0), Z = 2, V (A(sup 3) = 1057.3(3), R = 0.046, and R(sub w) = 0.061.

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

NASA Astrophysics Data System (ADS)

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.

Improving the hydrogen storage properties of metal-organic framework by functionalization.

PubMed

Xia, Liangzhi; Liu, Qing; Wang, Fengling; Lu, Jinming

2016-10-01

Based on the structure of MOF-808, different substituents were introduced to replace hydrogen atom on the phenyl ring of MOF-808. The GCMC method was used to study the effect of functional groups on the hydrogen storage properties of MOF-808-X (X = -OH, -NO 2 , -CH 3 , -CN, -I). The H 2 uptakes and isosteric heat of adsorption were simulated at 77 K. The results indicate that all these substituents have favorable impact on the hydrogen storage capacity, and -CN is found to be the most promising substituent to improve H 2 uptake. These results may be helpful for the design of MOFs with higher hydrogen storage capacity. Graphical abstract Atomistic structures of MOFs. (a) The structures of MOF-808-X. (b) Model of organic linker. Atom color scheme: C, gray; H, white; O, red; X, palegreen (X = -OH, -NO 2 , -CH 3 , -CN, -I).

Nuclearity controlled cyanide-bridged bimetallic CrIII-MnII compounds: synthesis, crystal structures, magnetic properties and theoretical calculations.

PubMed

Toma, Luminita; Lescouëzec, Rodrigue; Vaissermann, Jacqueline; Delgado, Fernando S; Ruiz-Pérez, Catalina; Carrasco, Rosa; Cano, Juan; Lloret, Francesc; Julve, Miguel

2004-11-19

The preparation, X-ray crystallography and magnetic investigation of the compounds PPh4[Cr(bipy)(CN)4].2 CH3CN.H2O (1) (mononuclear), [[Cr(bipy)(CN)4]2Mn-(H2O)4].4H2O (2) (trinuclear), [[Cr(bipy)(CN)4]2Mn(H2O)2] (3) (chain) and [[Cr(bipy)(CN)4]2Mn(H2O)].H2O.CH3CN (4) (double chain) [bipy=2,2'-bipyridine; PPh4 (+)=tetraphenylphosphonium] are described herein. The [Cr(bipy)(CN)4]- unit act either as a monodentate (2) or bis-monodentate (3) ligand toward the manganese atom through one (2) or two (3) of its four cyanide groups. The manganese atom is six-coordinate with two (2) or four (3) cyanide nitrogens and four (2) or two (3) water molecules building a distorted octahedral environment. In 4, two chains of 3 are pillared through interchain Mn-N-C-Cr links which replace one of the two trans-coordinated water molecules at the manganese atom to afford a double chain structure where bis- and tris-monodenate coordination modes of [Cr(bipy)(CN)4]- coexist. The magnetic properties of 1-4 were investigated in the temperature range 1.9-300 K. A Curie law behaviour for a magnetically isolated spin quartet is observed for 1. A significant antiferromagnetic interaction between CrIII and MnII through the single cyanide bridge [J=-6.2 cm(-1), the Hamiltonian being defined as H=-J(SCr1.SMn+SCr2.SMn] occurs in 2 leading to a low-lying spin doublet which is fully populated at T <5 K. A metamagnetic behaviour is observed for 3 and 4 [the values of the critical field Hc being ca. 3000 (3) and 1500 Oe (4)] which is associated to the occurrence of weak interchain antiferromagnetic interactions between ferrimagnetic Cr2III MnII chains. The analysis of the exchange pathways in 2-4 through DFT type calculations together with the magnetic bevaviour simulation using the quantum Monte Carlo methodology provided a good understanding of their magnetic properties.

Ammonium boranes for the selective complexation of cyanide or fluoride ions in water.

PubMed

Hudnall, Todd W; Gabbaï, François P

2007-10-03

With the recognition of aqueous fluoride and cyanide ions as an objective, we have investigated the anion binding properties of two isomeric ammonium boranes, namely [p-(Mes2B)C6H4(NMe3)]+ ([1]+) and [o-(Mes2B)C6H4(NMe3)]+ ([2]+). These cationic boranes, which could be obtained by reaction of the known 4- and 2-dimesitylboryl-N,N-dimethylaniline with MeOTf, have been investigated both experimentally and computationally. They both react with fluoride and cyanide ions in organic solvents to afford the corresponding fluoroborate/ or cyanoborate/ammonium zwitterions 1F, 1CN, 2F, and 2CN. In aqueous solution, however, these cationic boranes behave as remarkably selective receptors. Indeed, [1]+ only complexes cyanide ions while [2]+ only complexes fluoride ions. In H2O/DMSO 60:40 vol (HEPES 6 mM, pH 7), the cyanide binding constant of [1]+ and the fluoride binding constant of [2]+ are respectively equal to 3.9 (+/-0.1) x 108 and 910 (+/-50) M-1. Structural and computational studies indicate that both steric and electronic effects contribute to the unusual selectivity displayed by these cationic boranes. Owing to favorable Coulombic effects, the para-derivative [1]+ has a very high affinity for cyanide; yet these effects are not sufficiently intense to allow complexation of the more efficiently hydrated and less basic fluoride anion. In the case of the ortho-derivative [2]+, the proximity of the ammonium moiety leads to an increase in the Lewis acidity of the boron center thus making fluoride binding possible. However, steric effects prevent cyanide coordination to the boron center of [2]+. Finally, cation [1]+ and [2]+ bind their dedicated anions reversibly and show a negligible response in the presence of other common anions including Cl-, Br-, I-, NO3-, OAc-, H2PO4-, and HSO4-.

Mapping Vinyl Cyanide and Other Nitriles in Titan’s Atmosphere Using ALMA

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

Lai, J. C.-Y.; Cordiner, M. A.; Nixon, C. A.

Vinyl cyanide (C{sub 2}H{sub 3}CN) is theorized to form in Titan’s atmosphere via high-altitude photochemistry and is of interest regarding the astrobiology of cold planetary surfaces due to its predicted ability to form cell membrane-like structures (azotosomes) in liquid methane. In this work, we follow up on the initial spectroscopic detection of C{sub 2}H{sub 3}CN on Titan by Palmer et al. with the detection of three new C{sub 2}H{sub 3}CN rotational emission lines at submillimeter frequencies. These new, high-resolution detections have allowed for the first spatial distribution mapping of C{sub 2}H{sub 3}CN on Titan. We present simultaneous observations of C{submore » 2}H{sub 5}CN, HC{sub 3}N, and CH{sub 3}CN emission, and obtain the first (tentative) detection of C{sub 3}H{sub 8} (propane) at radio wavelengths. We present disk-averaged vertical abundance profiles, two-dimensional spatial maps, and latitudinal flux profiles for the observed nitriles. Similarly to HC{sub 3}N and C{sub 2}H{sub 5}CN, which are theorized to be short-lived in Titan’s atmosphere, C{sub 2}H{sub 3}CN is most abundant over the southern (winter) pole, whereas the longer-lived CH{sub 3}CN is more concentrated in the north. This abundance pattern is consistent with the combined effects of high-altitude photochemical production, poleward advection, and the subsequent reversal of Titan’s atmospheric circulation system following the recent transition from northern to southern winter. We confirm that C{sub 2}H{sub 3}CN and C{sub 2}H{sub 5}CN are most abundant at altitudes above 200 km. Using a 300 km step model, the average abundance of C{sub 2}H{sub 3}CN is found to be 3.03 ± 0.29 ppb, with a C{sub 2}H{sub 5}CN/C{sub 2}H{sub 3}CN abundance ratio of 2.43 ± 0.26. Our HC{sub 3}N and CH{sub 3}CN spectra can be accurately modeled using abundance gradients above the tropopause, with fractional scale-heights of 2.05 ± 0.16 and 1.63 ± 0.02, respectively.« less

Magnetically separable Prussian blue analogue Mn₃[Co(CN)₆]₂·nH₂O porous nanocubes as excellent absorbents for heavy metal ions.

PubMed

Hu, Lin; Mei, Ji-Yang; Chen, Qian-Wang; Zhang, Ping; Yan, Nan

2011-10-05

The application of Prussian blue analogue (PBA) Mn(3)[Co(CN)(6)](2)·nH(2)O porous nanocubes as absorbents for heavy metal ions has been demonstrated. The result indicates that Mn(3)[Co(CN)(6)](2)·nH(2)O porous nanocubes with average diameter of 240 nm possess excellent adsorption efficiency for Pb(2+) ions (94.21% at initial Pb(2+) concentration of 10 mg L(-1)). Moreover, Mn(3)[Co(CN)(6)](2)·nH(2)O porous nanocubes can also show high adsorption efficiency on heavy metal ions even in a strong acidic solution due to its chemical stability. Notably, an external magnet could be used to accelerate the separation of Mn(3)[Co(CN)(6)](2)·nH(2)O from the treated solution. It is suggested that the high adsorption efficiency may derive from the large surface area, M(3)(II)[M(III)(CN)(6)](2)·nH(2)O porous framework structure and affinity between polarizable π-electron clouds of the cyanide bridges and heavy metals ions.

Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

NASA Astrophysics Data System (ADS)

Li, Jin-Feng; Sun, Yin-Yin; Bai, Hongcun; Li, Miao-Miao; Li, Jian-Li; Yin, Bing

2015-06-01

The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M2(CN)5]-1 (M = Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca2(CN)5]-1 which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green's function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.

Structure of thallium(III) chloride, bromide, and cyanide complexes in aqueous solution

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

Blixt, J.; Glaser, J.; Sandstroem, M.

1995-05-10

The structures of the hydrated thallium(III) halide and pseudohalide complexes, [TlX{sub n}(OH{sub 2}){sub m}]{sup (3-d)+}, X = Cl, Br, CN, in aqueous solution have been studied by a combination of X-ray absorption fine structure spectroscopy (XAFS), large-angle X-ray scattering (LAXS), and vibrational spectroscopic (Raman and IR) techniques including far-infrared studies of aqueous solutions and some solid phases with known structures. The vibrational Tl-X frequencies of all complexes are reported, force constants are calculated using normal coordinate analysis, and assignments are given. The structural results are consistent with octahedral six-coordination for the cationic complexes Tl(OH{sub 2}){sub 6}{sup 3$PLU}, TlX(OH{sub 2}){sub 5}{supmore » 2+}, and trans-TlX{sub 2}(OH{sub 2}){sub 4}{sup +}. The coordination geometry changes to trigonal bipyramidal for the neutral TlBr{sub 3}(OH{sub 2}){sub 2} complex and possibly also for TlCl{sub 3}(OH{sub 2}){sub 2}. The TlX{sub 4}{sup -} complexes are all tetrahedral. Higher chloride complexes, TlCl{sub 5}(OH{sub 2}){sup 2-} and TlCl{sub 6}{sup 3-}, are formed and have again octahedral coordination geometry. 65 refs., 7 figs., 5 tabs.« less

PHOTOCHEMICAL REACTION OF NITRO-POLYCYCLIC AROMATIC HYDROCARBONS: EFFECT BY SOLVENT AND STRUCTURE

PubMed Central

Stewart, Gernerique; Smith, Keonia; Chornes, Ashley; Harris, Tracy; Honeysucker, Tiffany; Dasary, Suman Raj; Yu, Hongtao

2010-01-01

Photochemical degradation of 1-nitropyrene, 2-nitrofluorene, 2,7-dinitrofluorene, 6-nitrochrysene, 3-nitrofluoranthene, 5-nitroacenaphthene, and 9-nitroanthracene were examined in CHCl3, CH2Cl2, DMF, DMF/H2O (80/20), CH3CN, or CH3CN/H2O (80/20). The degradation follows mostly the 1st order kinetics; but a few follow 2nd order kinetics or undergo self-catalysis. The photodegradation rates follow the order: CHCl3 > CH2Cl2 > DMF > DMF/H2O > CH3CN > CH3CN/H2O. DMF is an exceptional solvent because 3 of the 7 compounds undergo self-catalytic reaction. 9-Nitroanthracene, which has a perpendicular nitro group, is the fastest, while the more compact 1-nitropyrene and 3-nitrofluoranthene, are the slowest degrading compounds. PMID:21170286

Removal of cyanide by woody plants.

PubMed

Larsen, Morten; Trapp, Stefan; Pirandello, Alessandro

2004-01-01

Hydrogen cyanide is a high volume production chemical that causes severe environmental problems. The toxicity of potassium cyanide (KCN) to basket willow trees (Salix viminalis) was tested. In aqueous solution, 2 mg CN l(-1) as KCN depressed the transpiration after 72 h about 50%. Trees exposed to 0.4 mg CN l(-1) in aqueous solution showed initially a depression of transpiration, but recovered. Doses of 8 and 20 mg CN l(-1) in aqueous solution were quickly mortal to the trees. At the end of the test, almost all cyanide had disappeared from the solutions. Levels of cyanide in plants were related to the toxicity, with no elevated levels of cyanide in plants exposed to 0.4 mg CN l(-1). Willows grown in sand survived 423.5 h irrigation with 20 mg CN l(-1). Willows grown in sand irrigated with 50 mg CN l(-1) died within a few days. The roots of the surviving willows were able to consume about 10 mg CN kg fresh weight(-1)h(-1). Vascular plants possess the enzymes beta-cyanoalanine synthase and beta-cyanoalanine hydrolase, which convert free cyanide to the amino acid asparagine. The in vivo capacity of woody plants (willow, poplar, elder, rose, birch) to remove cyanide was evaluated. Tests were performed with detached leaves and roots in KCN solutions of different concentrations. The highest removal capacity was obtained for basket willow hybrids (Salix viminalis x schwerinii). The Michaelis-Menten kinetics was determined. Realistic values of the half-saturation constant, K(M), were between 0.6 and 1.7 mg CN l(-1); the maximum metabolic capacity, v(max), was around 9.3 mg CN kg fresh weight(-1)h(-1). The removal of cyanide by plants might be useful in phytoremediation and treatment of wastewater from gold mining.

[Cu(aq)]2+ is structurally plastic and the axially elongated octahedron goes missing

NASA Astrophysics Data System (ADS)

Frank, Patrick; Benfatto, Maurizio; Qayyum, Munzarin

2018-05-01

High resolution (k = 18 Å-1 or k = 17 Å-1) copper K-edge EXAFS and MXAN (Minuit X-ray Absorption Near Edge) analyses have been used to investigate the structure of dissolved [Cu(aq)]2+ in 1,3-propanediol (1,3-P) or 1,5-pentanediol (1,5-P) aqueous frozen glasses. EXAFS analysis invariably found a single axially asymmetric 6-coordinate (CN6) site, with 4×Oeq = 1.97 Å, Oax1 = 2.22 Å, and Oax2 = 2.34 Å, plus a second-shell of 4×Owater = 3.6 Å. However, MXAN analysis revealed that [Cu(aq)]2+ occupies both square pyramidal (CN5) and axially asymmetric CN6 structures. The square pyramid included 4×H2O = 1.95 Å and 1×H2O = 2.23 Å. The CN6 sites included either a capped, near perfect, square pyramid with 5×H2O = 1.94 ± 0.04 Å and H2Oax = 2.22 Å (in 1,3-P) or a split axial configuration with 4×H2O = 1.94, H2Oax1 = 2.14 Å, and H2Oax2 = 2.28 Å (in 1,5-P). The CN6 sites also included an 8-H2O second-shell near 3.7 Å, which was undetectable about the strictly pyramidal sites. Equatorial angles averaging 94° ± 5° indicated significant departures from tetragonal planarity. MXAN assessment of the solution structure of [Cu(aq)]2+ in 1,5-P prior to freezing revealed the same structures as previously found in aqueous 1M HClO4, which have become axially compressed in the frozen glasses. [Cu(aq)]2+ in liquid and frozen solutions is dominated by a 5-coordinate square pyramid, but with split axial CN6 appearing in the frozen glasses. Among these phases, the Cu-O axial distances vary across 1 Å, and the equatorial angles depart significantly from the square plane. Although all these structures remove the dx2-y2, dz2 degeneracy, no structure can be described as a Jahn-Teller (JT) axially elongated octahedron. The JT-octahedral description for dissolved [Cu(aq)]2+ should thus be abandoned in favor of square pyramidal [Cu(H2O)5]2+. The revised ligand environments have bearing on questions of the Cu(i)/Cu(ii) self-exchange rate and on the mechanism for ligand exchange with bulk water. The plasticity of dissolved Cu(ii) complex ions falsifies the foundational assumption of the rack-induced bonding theory of blue copper proteins and obviates any need for a thermodynamically implausible protein constraint.

New Vanadium Compounds in Venezuela Heavy Crude Oil Detected by Positive-ion Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

PubMed Central

Zhao, Xu; Shi, Quan; Gray, Murray R.; Xu, Chunming

2014-01-01

Metalloporphyrins are ubiquitous in nature, particularly iron porphyrins (hemes) and magnesium dihydroporphyrins or chlorophylls. Oxovanadium (IV) complexes of alkyl porphyrins are widely distributed in petroleum, oil shales and maturing sedimentary bitumen. Here we identify new vanadium compounds in Venezuela Orinoco heavy crude oil detected by Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS). These compounds likely have the main structure of porphyrin, with the addition of more aromatic rings, thiophene and amino functional groups, corresponding to molecular series of CnH2n-40N4V1O1 (36 ≤ n ≤ 58),CnH2n-42N4V1O1 (37 ≤ n ≤ 57),CnH2n-44N4V1O1 (38 ≤ n ≤ 59),CnH2n-46N4V1O1 (43 ≤ n ≤ 54),CnH2n-48N4V1O1 (45 ≤ n ≤ 55),CnH2n-38N4V1S1O1 (36 ≤ n ≤ 41),CnH2n-40N4V1S1O1 (35 ≤ n ≤ 51),CnH2n-42N4V1S1O1 (36 ≤ n ≤ 54),CnH2n-44N4V1S1O1 (41 ≤ n ≤ 55),CnH2n-46N4V1S1O1 (39 ≤ n ≤ 55),CnH2n-27N5V1O1 (29 ≤ n ≤ 40),CnH2n-29N5V1O1 (34 ≤ n ≤ 42),CnH2n-33N5V1O1 (31 ≤ n ≤ 38),CnH2n-35N5V1O1 (32 ≤ n ≤ 41),CnH2n-27N5V1O2 (32 ≤ n ≤ 41) and CnH2n-29N5V1O2 (33 ≤ n ≤ 42). These findings are significant for the understanding of the existing form of vanadium species in nature, and are helpful for enhancing the amount of information on palaeoenvironments and improving the level of applied basic theory for the processing technologies of heavy oils. PMID:24948028

A fluorophosphate-based inverse Keggin structure

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

Fielden, John; Quasdorf, Kyle; Cronin, Leroy

An unusual PFO(3)(2-)-templated "inverse Keggin" polyanion, [Mo(12)O(46)(PF)(4)](4-), has been isolated from the degradation reaction of an {Mo(132)}-type Keplerate to [PMo(12)O(40)](3-) by [Cu(MeCN)(4)](PF(6)) in acetonitrile. (31)P-NMR studies suggest a structure-directing role for [Cu(MeCN)(4)](+) in the formation of the highly unusual all-inorganic inverse Keggin structure.

A fluorophosphate-based inverse Keggin structure.

PubMed

Fielden, John; Quasdorf, Kyle; Cronin, Leroy; Kögerler, Paul

2012-09-07

An unusual PFO(3)(2-)-templated "inverse Keggin" polyanion, [Mo(12)O(46)(PF)(4)](4-), has been isolated from the degradation reaction of an {Mo(132)}-type Keplerate to [PMo(12)O(40)](3-) by [Cu(MeCN)(4)](PF(6)) in acetonitrile. (31)P-NMR studies suggest a structure-directing role for [Cu(MeCN)(4)](+) in the formation of the highly unusual all-inorganic inverse Keggin structure.

Kinetic study of acetaminophen degradation by visible light photocatalysis.

PubMed

Gotostos, Mary Jane N; Su, Chia-Chi; De Luna, Mark Daniel G; Lu, Ming-Chun

2014-01-01

In this work, a novel photocatalyst K3[Fe(CN)6]/TiO2 synthesized via a simple sol-gel method was utilized to degrade acetaminophen (ACT) under visible light with the use of blue and green LED lights. Parameters (medium pH, initial concentration of reactant, catalyst concentration, temperature, and number of blue LED lights) affecting photocatalytic degradation of ACT were also investigated. The experimental result showed that compared to commercially available Degussa P-25 (DP-25) photocatalyst, K3[Fe(CN)6]/TiO2 gave higher degradation efficiency and rate constant (kapp) of ACT. The degradation efficiency or kapp decreased with increasing initial ACT concentration and temperature, but increased with increased number of blue LED lamps. Additionally, kapp increased as initial pH was increased from 5.6 to 6.9, but decreased at a high alkaline condition (pH 8.3). Furthermore, the degradation efficiency and kapp of ACT increased as K3[Fe(CN)6]/TiO2 loading was increased to 1 g L(-1) but decreased and eventually leveled off at photocatalyst loading above this value. Photocatalytic degradation of ACT in K3[Fe(CN)6]/TiO2 catalyst system follows a pseudo-first-order kinetics. The Langmuir-Hinshelwood equation was also satisfactorily used to model the degradation of ACT in K3[Fe(CN)6]/TiO2 catalyst system indicated by a satisfactory linear correlation between 1/kapp and Co, with kini = 6.54 × 10(-4) mM/min and KACT = 17.27 mM(-1).

Structural-electrochemical relations in the aqueous copper hexacyanoferrate-zinc system examined by synchrotron X-ray diffraction

NASA Astrophysics Data System (ADS)

Renman, Viktor; Ojwang, Dickson O.; Valvo, Mario; Gómez, Cesar Pay; Gustafsson, Torbjörn; Svensson, Gunnar

2017-11-01

The storage process of Zn2+ in the Prussian blue analogue (PBA) copper hexacyanoferrate (Cu[Fe(CN)6]2/3·nH2O - CuHCF) framework structure in a context of rechargeable aqueous batteries is examined by means of in operando synchrotron X-ray diffraction. Via sequential unit-cell parameter refinements of time-resolved diffraction data, it is revealed that the step-profile of the cell output voltage curves during repeated electrochemical insertion and removal of Zn2+ in the CuHCF host structure is associated with a non-linear contraction and expansion of the unit-cell in the range 0.36 < x < 1.32 for Znx/3Cu[Fe(CN)6]2/3·nH2O. For a high insertion cation content there is no apparent change in the unit-cell contraction. Furthermore, a structural analysis with respect to the occupancies of possible Zn2+ sites suggests that the Fe(CN)6 vacancies within the CuHCF framework play an important role in the structural-electrochemical behavior of this particular system. More specifically, it is observed that Zn2+ swaps position during electrochemical cycling, hopping between cavity sites to vacant ferricyanide sites.

Second-derivative synchronous fluorescence spectroscopy for the simultaneous determination of cinnarizine and nicergoline in pharmaceutical preparations.

PubMed

Walash, Mohamed I; Belal, Fathalla; El-Enany, Nahed; Abdelal, Amina

2008-01-01

A rapid, simple, and highly sensitive second-derivative synchronous fluorometric method has been developed for the simultaneous analysis of binary mixtures of cinnarizine (CN) and nicergoline (NIC). The method is based upon measurement of the native fluorescence of these drugs at constant wavelength difference (Deltalambda) = 80 nm in aqueous methanol (50%, v/v). The different experimental parameters affecting the native fluorescence of the studied drugs were carefully studied and optimized. The fluorescence-concentration plots were rectilinear over the range of 0.025-1.5 and 0.25-5.5 microg/mL for CN and NIC, respectively, with lower detection limits of 0.58 and 0.82 ng/mL and quantitation limits of 1.93 and 2.73 ng/mL for CN and NIC, respectively. The proposed method was successfully applied for the determination of the studied compounds in synthetic mixtures and in commercial tablets. The results obtained were in good agreement with those obtained with reference methods. The high sensitivity attained by the proposed method allowed the determination of CN in real and spiked human plasma. The mean recovery in the case of spiked human plasma [number of trials (n) = 3] was 102.82 +/- 2.17%, while that in real human plasma (n = 3) was 105.25 +/- 2.05.

Simulating the Refractive Index Structure Constant ({C}_{n}^{2}) in the Surface Layer at Antarctica with a Mesoscale Model

NASA Astrophysics Data System (ADS)

Qing, Chun; Wu, Xiaoqing; Li, Xuebin; Tian, Qiguo; Liu, Dong; Rao, Ruizhong; Zhu, Wenyue

2018-01-01

In this paper, we introduce an approach wherein the Weather Research and Forecasting (WRF) model is coupled with the bulk aerodynamic method to estimate the surface layer refractive index structure constant (C n 2) above Taishan Station in Antarctica. First, we use the measured meteorological parameters to estimate C n 2 using the bulk aerodynamic method, and second, we use the WRF model output parameters to estimate C n 2 using the bulk aerodynamic method. Finally, the corresponding C n 2 values from the micro-thermometer are compared with the C n 2 values estimated using the WRF model coupled with the bulk aerodynamic method. We analyzed the statistical operators—the bias, root mean square error (RMSE), bias-corrected RMSE (σ), and correlation coefficient (R xy )—in a 20 day data set to assess how this approach performs. In addition, we employ contingency tables to investigate the estimation quality of this approach, which provides complementary key information with respect to the bias, RMSE, σ, and R xy . The quantitative results are encouraging and permit us to confirm the fine performance of this approach. The main conclusions of this study tell us that this approach provides a positive impact on optimizing the observing time in astronomical applications and provides complementary key information for potential astronomical sites.

Thermal Decomposition Mechanism of CL-20 at Different Temperatures by ReaxFF Reactive Molecular Dynamics Simulations.

PubMed

Wang, Fuping; Chen, Lang; Geng, Deshen; Wu, Junying; Lu, Jianying; Wang, Chen

2018-04-26

Hexanitrohexaazaisowurtzitane (CL-20) has a high detonation velocity and pressure, but its sensitivity is also high, which somewhat limits its applications. Therefore, it is important to understand the mechanism and characteristics of thermal decomposition of CL-20. In this study, a ε-CL-20 supercell was constructed and ReaxFF-lg reactive molecular dynamics simulations were performed to investigate thermal decomposition of ε-CL-20 at various temperatures (2000, 2500, 2750, 3000, 3250, and 3500 K). The mechanism of thermal decomposition of CL-20 was analyzed from the aspects of potential energy evolution, the primary reactions, and the intermediate and final product species. The effect of temperature on thermal decomposition of CL-20 is also discussed. The initial reaction path of thermal decomposition of CL-20 is N-NO 2 cleavage to form NO 2 , followed by C-N cleavage, leading to the destruction of the cage structure. A small number of clusters appear in the early reactions and disappear at the end of the reactions. The initial reaction path of CL-20 decomposition is the same at different temperatures. However, as the temperature increases, the decomposition rate of CL-20 increases and the cage structure is destroyed earlier. The temperature greatly affects the rate constants of H 2 O and N 2 , but it has little effect on the rate constants of CO 2 and H 2 .

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

NASA Astrophysics Data System (ADS)

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.

Somatosensory Projections to Cochlear Nucleus are Up-regulated after Unilateral Deafness

PubMed Central

Zeng, Chunhua; Yang, Ziheng; Shreve, Lauren; Bledsoe, Sanford; Shore, Susan

2012-01-01

The cochlear nucleus (CN) receives innervation from auditory and somatosensory structures, which can be identified using vesicular glutamate transporters, VGLUT1 and VGLUT2. VGLUT1 is highly expressed in the magnocellular ventral CN (VCN), which receives auditory nerve inputs. VGLUT2 is predominantly expressed in the granule cell domain (GCD), which receives non-auditory inputs from somatosensory nuclei, including spinal trigeminal nucleus (Sp5) and cuneate nucleus (Cu). Two weeks after unilateral deafening VGLUT1 is significantly decreased in ipsilateral VCN while VGLUT2 is significantly increased in the ipsilateral GCD (Zeng et al., 2009), putatively reflecting decreased inputs from auditory nerve and increased inputs from non-auditory structures in guinea pigs. Here we wished to determine whether the upregulation of VGLUT2 represents increases in the number of somatosensory projections to the CN that are maintained for longer periods of time. Thus we examined concurrent changes in VGLUT levels and somatosensory projections in the CN using immunohistochemistry combined with anterograde tract tracing three and six weeks following unilateral deafening. The data reveal that unilateral deafness leads to increased numbers of VGLUT2-colabeled Sp5 and Cu projections to the ventral and dorsal CN. These findings suggest that Sp5 and Cu play significant and unique roles in cross-modal compensation and that, unlike after shorter term deafness, neurons in the magnocelluar regions also participate in the compensation. The enhanced glutamatergic somatosensory projections to the CN may play a role in neural spontaneous hyperactivity associated with tinnitus. PMID:23136418

The trend of production rates with heliocentric distance for comet P/Halley

NASA Technical Reports Server (NTRS)

Fink, Uwe

1994-01-01

Comet P/Halley was observed spectroscopically in the wavelength range 5200-10,400 A during 10 observing runs, roughly a month apart from 1985 August 28 to 1986 June 6. The observations span a heliocentric distance from 0.73 to 2.52 AU. This data set is analyzed to determine the course of the production rate with heliocentric distance for C2, NH2, CN, and the continuum. The effect of changing the Haser scale lengths and their heliocentric distance dependence is examined. The production rate ratios to water change only in a minor way, but the absolute values of the production rates are more severely affected. Fluorescent efficiencies, or g-factors for the CN red system are calculated, and band intensity ratios for NH2 and CN are presented. Using presently available fluorescence efficiencies and Haser scale lengths, mixing ratios for the parents of C2, CN, and NH2 with respect to water are: 0.34 +/- 0.07%, 0.15 +/- 0.04%, and 0.13 +/- 0.05%. It is found that these mixing ratios are essentially constant over the heliocentric distance range of the observations, implying a rather uniform nucleus and uniform outgassing characteristics, although there are indications of smaller scale day-to-day variations. The results provide strong observational confirmation that water evaporation controls the activity of the comet over the distance range studied. Continuum values Af rho are determined, and their ratios to QH2O are found to have a clear dependence with heliocentric distance approximately r(exp -1.0) with a post-perihelion enhancement. No correlation of the production rate ratios with light curve of P/Halley were found, nor was there any correlation of the C2 or CN production with the dust.

Effect of the porous structure of activated carbon on the adsorption kinetics of gold(I) cyanide complex

NASA Astrophysics Data System (ADS)

Ibragimova, P. I.; Grebennikov, S. F.; Gur'yanov, V. V.; Fedyukevich, V. A.; Vorob'ev-Desyatovskii, N. V.

2014-06-01

The effect the porous structure of activated carbons obtained from furfural and coconut shells has on the kinetics of [Au(CN)2]- ion adsorption is studied. Effective diffusion coefficients for [Au(CN)2]- anions in transport and adsorbing pores and mass transfer coefficients in a transport system of the pores and in microporous zones are calculated using the statistical moments of the kinetic curve.

Conformational stability, structural parameters and vibrational assignment from variable temperature infrared spectra of krypton solutions and ab initio calculations of ethylisothiocyanate.

PubMed

Durig, James R; Zheng, Chao

2007-11-01

Variable temperature (-105 to -150 degrees C) studies of the infrared spectra (3500-400 cm(-1)) of ethylisothiocyanate, CH(3)CH(2)NCS, dissolved in liquid krypton have been recorded. Additionally the infrared spectra of the gas and solid have been re-investigated. These spectroscopic data indicate a single conformer in all physical states with a large number of molecules in the gas phase at ambient temperature in excited states of the CN torsional mode which has a very low barrier to conformational interchange. To aid in the analyses of the vibrational and rotational spectra, ab initio calculations have been carried out by the perturbation method to the second order (MP2) with valence and core electron correlation using a variety of basis sets up to 6-311+G(2df,2pd). With the smaller basis sets up to 6-311+G(d,p) and cc-PVDZ, the cis conformer is indicated as a transition state with all larger basis sets the cis conformer is the only stable form. The predicted energy difference from these calculations between the cis form and the higher energy trans conformer is about 125 cm(-1) which represents essentially the barrier to internal rotation of the NCS group (rotation around NC axis). Density functional theory calculation by the B3LYP method with the same basis sets predicts this barrier to be about 25 cm(-1). By utilizing the previously reported microwave rotational constants with the structural parameters predicted by the ab initio MP2(full)/6-311+G(d,p) calculations, adjusted r(0) structural parameters have been obtained for the cis form. The determined heavy atom parameters are: r(NC)=1.196(5), r(CS)=1.579(5), r(CN)=1.439(5), r(CC)=1.519(5)A for the distances and angles of angleCCN=112.1(5), angleCNC=146.2(5), angleNCS=174.0(5) degrees . The centrifugal distortion constants, dipole moments, conformational stability, vibrational frequencies, infrared intensities and Raman activities have been predicted from ab initio calculations and compared to experimental quantities when available. These results are compared to the corresponding quantities of some similar molecules.

Syntheses, structural characterization and spectroscopic studies of cadmium(II)-metal(II) cyanide complexes with 4-(2-aminoethyl)pyridine

NASA Astrophysics Data System (ADS)

Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla; Şenyel, Mustafa; Hökelek, Tuncer

2017-02-01

Three new cadmium(II)-metal(II) cyanide complexes, [Cd(4aepy)2(H2O)2][Ni(CN)4] (1), [Cd(4aepy)2(H2O)2][Pd(CN)4] (2) and [Cd(4aepy)2(H2O)2][Pt(CN)4] (3) [4aepy = 4-(2-aminoethyl)pyridine], have been synthesized and characterized by elemental, thermal, FT-IR and Raman spectral analyses. The crystal structures of 1 and 2 have been determined by single crystal X-ray diffraction technique, in which they crystallize in the monoclinic system and C2/c space group. The M(II) [M(II) = Ni(II), Pd(II) and Pt(II)] ions are coordinated with the carbon atoms of the four cyanide groups in the square planar geometries and the [M(CN)4]2- ions act as counter ions. The Cd(II) ions display an N4O2 coordination sphere with a distorted octahedral geometry, the nitrogen donors belonging to four molecules of the organic 4aepy that act as unidentate ligands and two oxygen atoms from aqua ligands. 3D supramolecular structures of 1 and 2 were occurred by M⋯π and hydrogen bonding (Nsbnd H⋯N and Osbnd H⋯N) interactions. Vibrational assignments of all the observed bands were given and the spectral properties were also supported the crystal structures of the complexes. A possible decompositions of the complexes were investigated in the temperature range 30-800 °C in the static atmosphere.

Self-organization of dendritic supermolecules, based on isocyanide-gold(I), -copper(I), -palladium(II), and -platinum(II) complexes, into micellar cubic mesophases.

PubMed

Coco, Silverio; Cordovilla, Carlos; Donnio, Bertrand; Espinet, Pablo; García-Casas, María Jesús; Guillon, Daniel

2008-01-01

First- and second-generation dendrimers with an isocyanide group as the focal functional point (CN-G(n); n: 1,2) and their corresponding organometallic complexes [MCl(CN-G(n))] (M: Au, Cu), [{CuCl(CN-G(n))2}2], and trans-[MI2(CN-G(n))2] (M: Pd, Pt) have been synthesized. The free ligands and the first-generation complexes do not show mesogenic behavior, but all of the second-generation complexes display a thermotropic micellar cubic mesophase, over a large temperature range, and some of them directly at room temperature. The structure of the mesophase consists of the packing of two, discrete polyhedral micellar aggregates in a three-dimensional cubic Im$\\bar 3$m lattice.

Structural Basis of Neutralization of the Major Toxic Component from the Scorpion Centruroides noxius Hoffmann by a Human-derived Single-chain Antibody Fragment

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

Canul-Tec, Juan Carlos; Riaño-Umbarila, Lidia; Rudiño-Piñera, Enrique

2011-08-09

It has previously been reported that several single-chain antibody fragments of human origin (scFv) neutralize the effects of two different scorpion venoms through interactions with the primary toxins of Centruroides noxius Hoffmann (Cn2) and Centruroides suffusus suffusus (Css2). Here we present the crystal structure of the complex formed between one scFv (9004G) and the Cn2 toxin, determined in two crystal forms at 2.5 and 1.9 {angstrom} resolution. A 15-residue span of the toxin is recognized by the antibody through a cleft formed by residues from five of the complementarity-determining regions of the scFv. Analysis of the interface of the complexmore » reveals three features. First, the epitope of toxin Cn2 overlaps with essential residues for the binding of {beta}-toxins to its Na+ channel receptor site. Second, the putative recognition of Css2 involves mainly residues that are present in both Cn2 and Css2 toxins. Finally, the effect on the increase of affinity of previously reported key residues during the maturation process of different scFvs can be inferred from the structure. Taken together, these results provide the structural basis that explain the mechanism of the 9004G neutralizing activity and give insight into the process of directed evolution that gave rise to this family of neutralizing scFvs.« less

Local Order-Disorder Transition Driving by Structural Heterogeneity in a Benzyl Functionalized Ionic Liquid.

PubMed

Faria, Luiz F O; Paschoal, Vitor H; Lima, Thamires A; Ferreira, Fabio F; Freitas, Rafael S; Ribeiro, Mauro C C

2017-10-26

A local order-disorder transition has been disclosed in the thermophysical behavior of the ionic liquid 1-benzyl-3-methylimidazolium dicyanamide, [Bzmim][N(CN) 2 ], and its microscopic nature revealed by spectroscopic techniques. Differential scanning calorimetry and specific heat measurements show a thermal event of small enthalpy variation taking place in the range 250-260 K, which is not due to crystallization or melting. Molecular dynamic simulations and X-ray diffraction measurements have been used to discuss the segregation of domains in the liquid structure of [Bzmim][N(CN) 2 ]. Raman and NMR spectroscopy measurements as a function of temperature indicate that the microscopic origin of the event observed in the calorimetric measurements comes from structural rearrangement involving the benzyl group. The results indicate that the characteristic structural heterogeneity allow for rearrangements within local domains implying the good glass-forming ability for the low viscosity ionic liquid [Bzmim][N(CN) 2 ]. This work sheds light on our understanding of the microscopic origin behind complex thermal behavior of ionic liquids.

In vivo determination of triglyceride (TG) secretion in rats fed different dietary saturated fats using (2- sup 3 H)-glycerol

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

Lai, H.C.; Yang, H.; Lasekan, J.

1990-02-26

Male, Sprague-Dawley rats (154{plus minus}1 g) were fed diets containing 2% corn oil (CO) + 14% butterfat (BF), beef tallow (BT), olive oil (OO) or coconut oil (CN) vs a 16% CO control diet for 5 weeks. Changes in plasma TG specific activity (dpm/mg TG) were determined in individual unanesthetized rats after injection of 100 {mu}Ci (2-{sup 3}H)-glycerol via a carotid cannula. Fractional rate constants were obtained using a 2-compartment model and nonlinear regression analysis. Results demonstrated no difference in the fractional rate constants among dietary groups; but, differences in the rates of hepatic TG secretion were noted. Rats fedmore » BT showed a higher rate of hepatic TG secretion than rats fed CO. Rats fed BF, OO or CN showed somewhat higher rates of hepatic TG secretion than CO. VLDL TG, phospholipid, and apolipoprotein B and E levels were higher with saturated fats vs CO. The data suggest that the higher plasma TG levels noted in response to feeding saturated fats vs corn oil can be explained, in part, by an increased flux of hepatic TG secretion.« less

From synthetic coiled coils to functional proteins: automated design of a receptor for the calmodulin-binding domain of calcineurin.

PubMed

Ghirlanda, G; Lear, J D; Lombardi, A; DeGrado, W F

1998-08-14

A series of synthetic receptors capable of binding to the calmodulin-binding domain of calcineurin (CN393-414) was designed, synthesized and characterized. The design was accomplished by docking CN393-414 against a two-helix receptor, using an idealized three-stranded coiled coil as a starting geometry. The sequence of the receptor was chosen using a side-chain re-packing program, which employed a genetic algorithm to select potential binders from a total of 7.5x10(6) possible sequences. A total of 25 receptors were prepared, representing 13 sequences predicted by the algorithm as well as 12 related sequences that were not predicted. The receptors were characterized by CD spectroscopy, analytical ultracentrifugation, and binding assays. The receptors predicted by the algorithm bound CN393-414 with apparent dissociation constants ranging from 0.2 microM to >50 microM. Many of the receptors that were not predicted by the algorithm also bound to CN393-414. Methods to circumvent this problem and to improve the automated design of functional proteins are discussed. Copyright 1998 Academic Press

The coordination chemistry of nitrosyl in cyanoferrates. An exhibit of bioinorganic relevant reactions.

PubMed

Olabe, José A

2008-07-28

Sodium nitroprusside (SNP, Na(2)[Fe(CN)(5)(NO)].2H(2)O) is a widely used NO-donor hypotensive agent, containing the formally described nitrosonium (NO(+)) ligand, which may be redox-interconverted to the corresponding one-electron (NO) and two-electron (NO(-)/HNO) reduced bound species. Thus, the chemistry of the three nitrosyl ligands may be explored with adequate, biologically relevant substrates. The nitrosonium complex, [Fe(CN)(5)(NO)](2-), is formed through a reductive nitrosylation reaction of [Fe(III)(CN)(5)(H(2)O)](2-) with NO, or, alternatively, through the coordination of NO(2)(-) to [Fe(II)(CN)(5)(H(2)O)](3-) and further proton-assisted dehydration. It is extremely inert toward NO(+)-dissociation, and behaves as an electrophile toward different bases: OH(-), amines, thiolates, etc. Also, SNP releases NO upon UV-vis photo-activation, with formation of [Fe(III)(CN)(5)(H(2)O)](2-). The more electron rich [Fe(CN)(5)(NO)](3-) may be prepared from [Fe(II)(CN)(5)(H(2)O)](3-) and NO, and is also highly inert toward the dissociation of NO (k = 1.6 x 10(-5) s(-1), 25.0 degrees C, pH 10.2). It reacts with O(2) leading to SNP, with the intermediacy of a peroxynitrite adduct. The [Fe(CN)(5)(NO)](3-) ion is labile toward the release of trans-cyanide, forming the [Fe(CN)(4)(NO)](2-) ion. Both complexes exist in a pH-dependent equilibrium, and decompose thermally in the hours time scale, releasing cyanides and NO. The latter may further bind to [Fe(CN)(4)(NO)](2-) with formation of a singlet dinitrosyl species, [Fe(CN)(4)(NO)(2)](2-), which in turn is unstable toward disproportionation into SNP and N(2)O, and toward the parallel formation of a tetrahedral paramagnetic dinitrosyl compound, [Fe(CN)(2)(NO)(2)]. Emerging studies with the putative nitroxyl complex, [Fe(CN)(5)(HNO)](3-), should allow for a complete picture of the three nitrosyl ligands in the same pentacyano fragment. The present Perspective, based on an adequate characterization of structural and spectroscopic properties, will focus on the kinetic and mechanistic description of the above mentioned reactions, which display a versatile scenario, fundamentally related to the biologically relevant processes associated with NO reactivity.

Cooperative autoinhibition and multi-level activation mechanisms of calcineurin

PubMed Central

Li, Sheng-Jie; Wang, Jue; Ma, Lei; Lu, Chang; Wang, Jie; Wu, Jia-Wei; Wang, Zhi-Xin

2016-01-01

The Ca2+/calmodulin-dependent protein phosphatase calcineurin (CN), a heterodimer composed of a catalytic subunit A and an essential regulatory subunit B, plays critical functions in various cellular processes such as cardiac hypertrophy and T cell activation. It is the target of the most widely used immunosuppressants for transplantation, tacrolimus (FK506) and cyclosporin A. However, the structure of a large part of the CNA regulatory region remains to be determined, and there has been considerable debate concerning the regulation of CN activity. Here, we report the crystal structure of full-length CN (β isoform), which revealed a novel autoinhibitory segment (AIS) in addition to the well-known autoinhibitory domain (AID). The AIS nestles in a hydrophobic intersubunit groove, which overlaps the recognition site for substrates and immunosuppressant-immunophilin complexes. Indeed, disruption of this AIS interaction results in partial stimulation of CN activity. More importantly, our biochemical studies demonstrate that calmodulin does not remove AID from the active site, but only regulates the orientation of AID with respect to the catalytic core, causing incomplete activation of CN. Our findings challenge the current model for CN activation, and provide a better understanding of molecular mechanisms of CN activity regulation. PMID:26794871

Neutral six-coordinate bis(dithiocarbamato)silicon(iv) complexes with an SiCl2S4 skeleton.

PubMed

Baus, Johannes A; Tacke, Reinhold

2017-07-11

Treatment of SiCl 4 with lithium dithiocarbamates of the formula type Li[R 2 NCS 2 ] (R = Ph, iPr) in a molar ratio of 1 : 2 afforded the respective six-coordinate silicon(iv) complexes [Ph 2 NCS 2 ] 2 SiCl 2 (3) and [iPr 2 NCS 2 ] 2 SiCl 2 (4), which were isolated as the solvates 3·MeCN and 4·MeCN. Compounds 3·MeCN and 4·MeCN were structurally characterised by single-crystal X-ray diffraction and multinuclear NMR spectroscopic studies in the solid state and in solution. In this study, dithiocarbamato ligands were implemented in silicon coordination chemistry for the first time. Compounds 3 and 4 represent the first six-coordinate silicon(iv) complexes with an SiCl 2 S 4 skeleton.

Interrelationship of Cn2 & Eddy Dissipation rate based on Scintillometer and Doppler Lidar observations in complex terrain during the Perdigao Campaign 2017

NASA Astrophysics Data System (ADS)

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 between multiple Doppler lidars, scintillometer and TLS are compared and the relationship between refractive index structure parameter and turbulence is explored. The effect of optical turbulence under various atmospheric conditions in complex terrain will be investigated.

Shells in the C2 coma of Comet P/Halley

NASA Technical Reports Server (NTRS)

Schulz, Rita; A'Hearn, Michael F.

1995-01-01

We reanalyzed the CN images of Comet P/Halley, in which jets have been discovered for the first time, in search of shell structures. Shells were actually detected at the outer edges of the frames on those dates for which shells with radii small enough to be covered by the limited field of view of the CCD were predicted. The C2 images of the same data set were subjected to an analogous investigation which led to the discovery of shell structures in C2 as well. The morphology of the CN and the C2 shells is essentially equal on the same observational date. They have the same radii and show almost identical asymmetries which suggests that CN and C2 in the shells originate from the same general source. The comparison of the jets in both species before and after a two-dimensional continuum subtraction supports this supposition. The similar morphology of the jets indicates that both species are produced from the same bulk of precursor material which has been ejected in the form of jets from the same active area. However, similarly located and oriented jets in CN and C2 do not show similar relative intensities in most cases. These differences in the intensity distribution imply that the production rates of CN and C2 follow different laws.

The primary structure of rat liver ribosomal protein L37. Homology with yeast and bacterial ribosomal proteins.

PubMed

Lin, A; McNally, J; Wool, I G

1983-09-10

The covalent structure of the rat liver 60 S ribosomal subunit protein L37 was determined. Twenty-four tryptic peptides were purified and the sequence of each was established; they accounted for all 111 residues of L37. The sequence of the first 30 residues of L37, obtained previously by automated Edman degradation of the intact protein, provided the alignment of the first 9 tryptic peptides. Three peptides (CN1, CN2, and CN3) were produced by cleavage of protein L37 with cyanogen bromide. The sequence of CN1 (65 residues) was established from the sequence of secondary peptides resulting from cleavage with trypsin and chymotrypsin. The sequence of CN1 in turn served to order tryptic peptides 1 through 14. The sequence of CN2 (15 residues) was determined entirely by a micromanual procedure and allowed the alignment of tryptic peptides 14 through 18. The sequence of the NH2-terminal 28 amino acids of CN3 (31 residues) was determined; in addition the complete sequences of the secondary tryptic and chymotryptic peptides were done. The sequence of CN3 provided the order of tryptic peptides 18 through 24. Thus the sequence of the three cyanogen bromide peptides also accounted for the 111 residues of protein L37. The carboxyl-terminal amino acids were identified after carboxypeptidase A treatment. There is a disulfide bridge between half-cystinyl residues at positions 40 and 69. Rat liver ribosomal protein L37 is homologous with yeast YP55 and with Escherichia coli L34. Moreover, there is a segment of 17 residues in rat L37 that occurs, albeit with modifications, in yeast YP55 and in E. coli S4, L20, and L34.

Thermal Gradient During Vacuum-Deposition Dramatically Enhances Charge Transport in Organic Semiconductors: Toward High-Performance N-Type Organic Field-Effect Transistors.

PubMed

Kim, Joo-Hyun; Han, Singu; Jeong, Heejeong; Jang, Hayeong; Baek, Seolhee; Hu, Junbeom; Lee, Myungkyun; Choi, Byungwoo; Lee, Hwa Sung

2017-03-22

A thermal gradient distribution was applied to a substrate during the growth of a vacuum-deposited n-type organic semiconductor (OSC) film prepared from N,N'-bis(2-ethylhexyl)-1,7-dicyanoperylene-3,4:9,10-bis(dicarboxyimide) (PDI-CN2), and the electrical performances of the films deployed in organic field-effect transistors (OFETs) were characterized. The temperature gradient at the surface was controlled by tilting the substrate, which varied the temperature one-dimensionally between the heated bottom substrate and the cooled upper substrate. The vacuum-deposited OSC molecules diffused and rearranged on the surface according to the substrate temperature gradient, producing directional crystalline and grain structures in the PDI-CN2 film. The morphological and crystalline structures of the PDI-CN2 thin films grown under a vertical temperature gradient were dramatically enhanced, comparing with the structures obtained from either uniformly heated films or films prepared under a horizontally applied temperature gradient. The field effect mobilities of the PDI-CN2-FETs prepared using the vertically applied temperature gradient were as high as 0.59 cm 2 V -1 s -1 , more than a factor of 2 higher than the mobility of 0.25 cm 2 V -1 s -1 submitted to conventional thermal annealing and the mobility of 0.29 cm 2 V -1 s -1 from the horizontally applied temperature gradient.

Photocatalytic degradation of perfluorooctanoic acid with beta-Ga2O3 in anoxic aqueous solution.

PubMed

Zhao, Baoxiu; Lv, Mou; Zhou, Li

2012-01-01

Perfluorooctanoic acid (PFOA) is a new-found hazardous persistent organic pollutant, and it is resistant to decomposition by hydroxyl radical (HO*) due to its stable chemical structure and the high electronegativity of fluorine. Photocatalytic reduction of PFOA with beta-Ga2O3 in anoxic aqueous solution was investigated for the first time, and the results showed that the photoinduced electron (e(cb-)) coming from the beta-Ga2O3 conduction band was the major degradation substance for PFOA, and shorter-chain perfluorinated carboxylic acids (PFCAs, CnF2n+i1COOH, 1 < or = n < or = 6) were the dominant products. Furthermore, the concentration of F- was measured by the IC technique and defluorination efficiency was calculated. After 3 hr, the photocatalytic degradation efficiency was 98.8% and defluorination efficiency was 31.6% in the presence of thiosulfate and bubbling N2. The degradation reaction followed first-order kinetics (k = 0.0239 min(-1), t1/2 = 0.48 hr). PFCAs (CnF2n+1COOH, 1 < or = n < or = 7) were detected and measured by LC-MS and LC-MS/MS methods. It was deduced that the probable photocatalytic degradation mechanism involves e(cb-) attacking the carboxyl of CnF2n+1COOH, resulting in decarboxylation and the generation of CnF2n+1*. The produced CnF2n+1* reacted with H2O, forming CnF2n+1OH, then CnF2n+1OH underwent HF loss and hydrolysis to form CnF2n+1COOH.

Improved synthesis and crystal structure of the flexible pillared layer porous coordination polymer: Ni(1,2-bis(4-pyridyl)ethylene)[Ni(CN) 4

DOE PAGES

Wong-Ng, W.; Culp, J. T.; Chen, Y. S.; ...

2013-01-01

This paper reports our synthesis of flexible coordination polymer, Ni(L)[Ni(CN) 4], (L = 1,2-bis(4-pyridyl)ethylene (nicknamed bpene)), and its structural characterization using synchrotron single crystal X-ray diffraction. The structure of the purplish crystals has been determined to be monoclinic, space group P2 1/m, a = 13.5941(12) Å, b = 14.3621(12) Å, c = 14.2561(12) Å, β = 96.141(2)°, V = 2767.4(4) Å 3, Z = 4, D c = 1.46 g cm -1. Ni(bpene)[Ni(CN) 4] assumes a pillared layer structure with layers defined by Ni[Ni(CN) 4] n nets and bpene ligands acting as pillars. With the present crystallization technique which involvesmore » the use of concentrated ammonium hydroxide solution and dimethyl sulfoxide (DMSO), disordered free bpene ligands and solvents of crystallization (DMSO and water molecules) occupy the pores, resulting in a formula of Ni(bpene)[Ni(CN) 4](1/2)bpene∙DMSO 2H 2O, or Ni 2N 7C 24H 25SO 3. Without the inclusion of free bpene ligands and solvent molecules, the free volume is approximately 61% of the total volume; this free volume fraction is reduced to 50% with the free ligands present. Pores without the free ligands were found to have a local diameter of 5.7 Å and a main aperture of 3.5 Å. Based on the successful crystal synthesis, we also devised a new bulk synthetic technique which yielded a polycrystalline material with a significantly improved CO 2 uptake as compared to the originally reported powder material. The improved synthetic technique yielded a polycrystalline material with 40% higher CO 2 uptake compared to the previously reported powder material. An estimated 14.4 molecules of CO 2 per unit cell was obtained.« less

Water-Free Rare Earth-Prussian Blue Type Analogues: Synthesis, Structure, Computational Analysis, and Magnetic Data of {Ln[superscript III](DMF)[subscript 6]Fe[superscript III](CN)[subcsript 6]}[subscript infinity] (Ln = Rare Earths Excluding Pm)

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

Wilson, Duane C.; Liu, Shengming; Chen, Xuenian

2009-11-04

Water-free rare earth(III) hexacyanoferrate(III) complexes, {l_brace}Ln(DMF){sub 6}({mu}-CN){sub 2}Fe(CN){sub 4}{r_brace}{sub {infinity}} (DMF = N,N-dimethylformamide; Ln = Sm, 1; Eu, 2; Gd, 3; Tb, 4; Dy, 5; Ho, 6; Er, 7; Tm, 8; Yb, 9; Lu, 10; Y, 11; La, 12; Ce, 13; Pr, 14; Nd, 15), were synthesized in dry DMF through the metathesis reactions of [(18-crown-6)K]{sub 3}Fe(CN){sub 6} with LnX{sub 3}(DMF){sub n} (X = Cl or NO{sub 3}). Anhydrous DMF solutions of LnX{sub 3}(DMF){sub n} were prepared at room temperature from LnCl{sub 3} or LnX{sub 3} {center_dot} nH{sub 2}O under a dynamic vacuum. All compounds were characterized by IR, X-raymore » powder diffraction (except for 10), and single crystal X-ray diffraction (except for 2, 7, 10). Infrared spectra reveal that a monotonic, linear relationship exists between the ionic radius of the lanthanide and the {nu}{sub {mu}-CN} stretching frequency of 1-10, 12-15 while 11 deviates slightly from the ionic radius relationship. X-ray powder diffraction data are in agreement with powder patterns calculated from single crystal X-ray diffraction results, a useful alternative for bulk sample confirmation when elemental analysis data are difficult to obtain. Eight-coordinate Ln(III) metal centers are observed for all structures. trans-cyanide units of [Fe(CN){sub 6}]{sup 3-} formed isocyanide linkages to Ln(III) resulting in one-dimensional polymeric chains. Structures of compounds 1-9 and 11 are isomorphous, crystallizing in the space group C2/c. Structures of compounds 12-15 are also isomorphous, crystallizing in the space group P2/n. One unique polymeric chain exists in the structures of 1-9 and 11 while two unique polymeric chains exist in structures of 12-15. One of the polymeric chains of 12-15 is similar to that observed for 1-9, 11 while the other is more distorted and has a shorter Ln-Fe distance. Magnetic susceptibility measurements for compounds 3-6, 8, 11 were performed on polycrystalline samples of the compounds.« less

Laboratory Rotational Spectra of Silyl Isocyanide

NASA Astrophysics Data System (ADS)

Lee, K. L. K.; Gottlieb, C. A.; McCarthy, M. C.

2018-06-01

The rotational spectrum of silyl isocyanide (SiH3NC), an isomer of the well-studied silyl cyanide (SiH3CN), has been detected in the laboratory in a supersonic molecular beam, and the identification was confirmed by observations of the corresponding rotational transitions in the rare isotopic species {SiH}}3}15{NC} and SiH3N13C. Spectroscopic constants derived from 19 transitions between 11 and 35 GHz in the three lowest harmonically related rotational transitions in the K = 0 and 1 ladders of the normal isotopic species including the nitrogen nuclear quadrupole hyperfine constant allow the principal astronomical transitions of SiH3NC to be calculated to an uncertainty of about 4 km s‑1 in equivalent radial velocity, or within the FWHM of narrow spectral features in the inner region of IRC+10216 near 200 GHz. The concentration of SiH3NC in our molecular beam is three times less than SiH3CN, or about the same as the corresponding ratio of the isomeric pair SiNC and SiCN produced under similar conditions. Silyl isocyanide is an excellent candidate for astronomical detection, because the spectroscopic and chemical properties are very similar to SiH3CN, which was recently identified in the circumstellar envelope of IRC+10216 by Cernicharo et al. and of SiNC and SiCN in the same source.

Unravelling the spin-state of solvated [Fe(bpp)2]2+ spin-crossover complexes: structure-function relationship.

PubMed

Giménez-López, Maria Del Carmen; Clemente-León, Miguel; Giménez-Saiz, Carlos

2018-05-23

This paper reports firstly the syntheses, crystal structures, and thermal and magnetic properties of spin crossover salts of formulae [Fe(bpp)2]3[Cr(CN)6]2·13H2O (1) and [Fe(bpp)2][N(CN)2]2·H2O (2) (bpp = 2,6-bis(pyrazol-3-yl)pyridine) exhibiting hydrogen-bonded networks of low-spin [Fe(bpp)2]2+ complexes and [Cr(CN)6]3- or [N(CN)2]- anions, with solvent molecules located in the voids. Desolvation of 1 is accompanied by a complete low-spin (LS) to a high-spin (HS) transformation that becomes reversible after rehydration by exposing the sample to the humidity of air. The influence of the lattice water on the magnetic properties of spin-crossover [Fe(bpp)2]X2 complex salts has been documented. In most cases, it stabilises the LS state over the HS one. In other cases, it is rather the contrary. The second part of this paper is devoted to unravelling the reasons why the lattice solvent stabilises one form over the other through magneto-structural correlations of [Fe(bpp)2]2+ salts bearing anions with different charge/size ratios (Xn-). The [Fe(bpp)2]2+ stacking explaining these two different behaviours is correlated here with the composition of the second coordination sphere of the Fe centers and the ability of these anions to form hydrogen bonds and/or π-π stacking interactions between them or the bpp ligand.

Volumetric Properties of the Ionic Liquid, 1-Butyl-3-methylimidazolium Tetrafluoroborate, in Organic Solvents at T = 298.15K

NASA Astrophysics Data System (ADS)

Shekaari, Hemayat; Zafarani-Moattar, Mohammed Taghi

2008-04-01

Apparent molar volumes, V_φ , and compressibilities, kappa _φ , of 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) have been determined from precise density and speed-of-sound measurements in organic solvents, methanol (MeOH), acetonitrile (MeCN), tetrahydrofuran (THF), N, N-dimethylacetamide (DMA), and dimethylsulfoxide (DMSO) in the dilute region of the ionic liquid. Corresponding values at infinite dilution are estimated by the Redlich-Mayer and Pitzer equations. The results have been interpreted by the interaction of the [BMIm][BF4] in the organic solvents. Results show that the structure and dielectric constant of the organic solvents play an important role for the ion-solvent interactions in these mixtures. It was found that the strength of interaction between [BMIm][BF4] with the studied organic solvents has the order DMSO > DMA > MeOH > MeCN > THF.

Anion-π aromatic neutral tweezers complexes: are they stable in polar solvents?

PubMed

Sánchez-Lozano, Marta; Otero, Nicolás; Hermida-Ramón, Jose M; Estévez, Carlos M; Mandado, Marcos

2011-03-17

The impact of the solvent environment on the stabilization of the complexes formed by fluorine (T-F) and cyanide (T-CN) substituted tweezers with halide anions has been investigated theoretically. The study was carried out using computational methodologies based on density functional theory (DFT) and symmetry adapted perturbation theory (SAPT). Interaction energies were obtained at the M05-2X/6-31+G* level. The obtained results show a large stability of the complexes in solvents with large dielectric constant and prove the suitability of these molecular tweezers as potential hosts for anion recognition in solution. A detailed analysis of the effects of the solvent on the electron withdrawing ability of the substituents and its influence on the complex stability has been performed. In particular, the interaction energy in solution was split up into intermonomer and solvent-complex terms. In turn, the intermonomer interaction energy was partitioned into electrostatic, exchange, and polarization terms. Polar resonance structures in T-CN complexes are favored by polar solvents, giving rise to a stabilization of the intermonomer interaction, the opposite is found for T-F complexes. The solvent-complex energy increases with the polarity of the solvent in T-CN complexes, nonetheless the energy reaches a maximum and then decreases slowly in T-F complexes. An electron density analysis was also performed before and after complexation, providing an explanation to the trends followed by the interaction energies and their different components in solution.

Fine-structure-resolution for Rovibrational Excitation of CN Due to H2

NASA Astrophysics Data System (ADS)

Byrd, Nat; Yang, Benhui H.; Stancil, Phillip C.

2018-06-01

Diatomic molecules can be readily excited in interstellar environments exposed to intense UV radiation, such as the inner rim of a protoplanetary disk. Non-thermal populations of excited rovibrational levels can result, for example, following decay from electronically excited states to the electronic ground state. Competition between radiative decay and collisional processes, mostly due to H2, determine the resulting rovibrational emission spectrum. For CN, and other open-shell molecules, the resulting spectrum will be complicated due to fine-structure splitting of the rotational levels. In some cases, fine-structure resolution has been previously computed for rotational transitions in atom- or diatom-diatom collisional processes. Here we present the first fine-structure resolution for vibrational deexcitation for CN colliding with H2. The collisional cross sections were computed using a 6D potential energy surface with a full close-coupling approach. Fine-structure resolution is obtained by adopting an angular momentum recoupling scheme to transform the scattering matrices to a recoupled basis. Here we present low-energy calculations for the v=1 to 0 transition.This work was supported by NASA Grant NNX16AF09G.

Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

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

Li, Jin-Feng; Sun, Yin-Yin; Li, Miao-Miao

2015-06-15

The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M{sub 2}(CN){sub 5}]{sup −1} (M =  Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca{sub 2}(CN){sub 5}]{sup −1} which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green’s function (OVGF) method either overestimatesmore » or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.« less

Syntheses and multi-NMR study of fac- and mer-OsO(3)F(2)(NCCH(3)) and the X-ray crystal structure (n = 2) and Raman spectrum (n = 0) of fac-OsO(3)F(2)(NCCH(3)).nCH(3)CN.

PubMed

Hughes, Michael J; Gerken, Michael; Mercier, Hélène P A; Schrobilgen, Gary J

2010-06-07

Dissolution of the infinite chain polymer, (OsO(3)F(2))(infinity), in CH(3)CN solvent at -40 degrees C followed by solvent removal under vacuum at -40 degrees C yielded fac-OsO(3)F(2)(NCCH(3)).nCH(3)CN (n >/= 2). Continued pumping at -40 degrees C with removal of uncoordinated CH(3)CN yielded fac-OsO(3)F(2)(NCCH(3)). Both fac-OsO(3)F(2)(NCCH(3)).nCH(3)CN and fac-OsO(3)F(2)(NCCH(3)) are yellow-brown solids and were characterized by low-temperature (-150 degrees C) Raman spectroscopy. The crystal structure (-173 degrees C) of fac-OsO(3)F(2)(NCCH(3)).2CH(3)CN consists of two co-crystallized CH(3)CN molecules and a pseudo-octahedral OsO(3)F(2).NCCH(3) molecule in which three oxygen atoms are in a facial arrangement and CH(3)CN is coordinated trans to an oxygen atom in an end-on fashion. The Os---N bond length (2.205(3) A) is among the shortest M---N adduct bonds observed for a d(0) transition metal oxide fluoride. The (19)F NMR spectrum of (OsO(3)F(2))(infinity) in CH(3)CN solvent (-40 degrees C) is a singlet (-99.6 ppm) corresponding to fac-OsO(3)F(2)(NCCH(3)). The (1)H, (15)N, (13)C, and (19)F NMR spectra of (15)N-enriched OsO(3)F(2)(NCCH(3)) were recorded in SO(2)ClF solvent (-84 degrees C). Nitrogen-15 enrichment resulted in splitting of the (19)F resonance of fac-OsO(3)F(2)((15)NCCH(3)) into a doublet ((2)J((15)N-(19)F), 21 Hz). In addition, a doublet of doublets ((2)J((19)F(ax)-(19)F(eq)), 134 Hz; (2)J((15)N-(19)F(eq)), 18 Hz) and a doublet ((2)J((19)F(ax)-(19)F(eq)), 134 Hz) were observed in the (19)F NMR spectrum that have been assigned to mer-OsO(3)F(2)((15)NCCH(3)); however, coupling of (15)N to the axial fluorine-on-osmium environment could not be resolved. The nitrogen atom of CH(3)CN is coordinated trans to a fluorine ligand in the mer-isomer. Quantum-chemical calculations at the SVWN and B3LYP levels of theory were used to calculate the energy-minimized gas-phase geometries, vibrational frequencies of fac- and mer-OsO(3)F(2)(NCCH(3)) and of CH(3)CN. The relative stabilities of the mer- and fac-isomers have been determined and are in accordance with the solution NMR assignments.

Innovative scheme for high-repetition-rate imaging of CN radical.

PubMed

Satija, Aman; Ruesch, Morgan D; Powell, Michael S; Son, Steven F; Lucht, Robert P

2018-02-01

We have employed, to the best of our knowledge, a novel excitation scheme to perform the first high-repetition-rate planar laser-induced fluorescence (PLIF) measurements of a CN radical in combustion. The third harmonic of a Nd:YVO 4 laser at 355 nm due to its relatively large linewidth overlaps with several R branch transitions in a CN ground electronic state. Therefore, the 355 nm beam was employed to directly excite the CN transitions with good efficiency. The CN measurements were performed in premixed CH 4 -N 2 O flames with varying equivalence ratios. A detailed characterization of the high-speed CN PLIF imaging system is presented via its ability to capture statistical and dynamical information in these premixed flames. Single-shot CN PLIF images obtained over a HMX pellet undergoing self-supported deflagration are presented as an example of the imaging system being applied towards characterizing the flame structure of energetic materials.

[Chemistry of alpha-aminonitriles. Aziridine-2-carbonitrile: photochemical formation from 2-aminopropenenitrile

NASA Technical Reports Server (NTRS)

Drenkard, S.; Ferris, J.; Eschenmoser, A.

1990-01-01

2-Aminopropenenitrile in solvents such as MeCN, MeOH, or H2O is photoisomerized by UV light to racemic aziridine-2-carbonitrile (rac-2); the larger part of the starting material, however, fragments to HCN and MeCN. The observed photocyclization constitutes a structural connection within an ensemble of C3H4N2 compounds considered to be potentially relevant to prebiotic chemistry.

Hexanuclear Fe(III) wheels functionalized by amino-acetonitrile derivatives

NASA Astrophysics Data System (ADS)

Kravtsov, Victor Ch.; Malaestean, Iurie; Stingach, Eugenia P.; Duca, Gheorghe G.; Macaev, Fliur Z.; van Leusen, Jan; Kögerler, Paul; Hauser, Jürg; Krämer, Karl; Decurtins, Silvio; Liu, Shi-Xia; Ghosh, Ashta C.; Garcia, Yann; Baca, Svetlana G.

2018-04-01

Three new hexanuclear Fe(III) coordination wheels [Fe6Cl6(L1)6]·5(MeCN) (1), [Na0.5Fe6Cl6(L1)6](N3)0.5·4.5(MeCN) (2), and [Fe6Cl6(L2)6]·2(MeCN) (3) have been synthesized with new prepared amino-acetonitrile derivatives 2-[bis(2-hydroxyethyl)amino]acetonitrile hydrochloride (H2L1) and 3-[bis(2-hydroxyethyl)amino]propanenitrile hydrochloride (H2L2). They were structurally characterized by single-crystal X-ray diffraction. Mößbauer spectroscopy and magnetic susceptibility measurements indicate dominant antiferromagnetic behavior between the Fe(III) centers.

Conductive bridge random access memory characteristics of SiCN based transparent device due to indium diffusion

NASA Astrophysics Data System (ADS)

Kumar, Dayanand; Aluguri, Rakesh; Chand, Umesh; Tseng, Tseung-Yuen

2018-03-01

In this work, the transparent bipolar resistive switching characteristics of a SiCN-based ITO/SiCN/AZO structure due to In diffusion from ITO is studied. The SiCN based device is found to be 80% transparent in the visible wavelength region. This device, with AZO as both top and bottom electrodes, does not show any RRAM property due to deposition of the high quality O2-free SiCN film. Replacing the AZO top electrode with ITO in this device results in good resistive switching (RS) characteristics with a high on/off ratio and long retention. Replacing the SiCN film with ZrO2 also results in excellent RS characteristics due to the formation of an oxygen vacancies filament inside the ZrO2 film. A resistance ratio of on/off is found to be higher in the SiCN based device compared to that of the ZrO2 device. Diffusion of In from ITO into the SiCN film on application of high positive voltage during forming can be attributed to the occurrence of RS in the device, which is confirmed by the analyses of energy dispersive spectroscopy and secondary-ion mass spectrometry. This study shows a pathway for the fabrication of CBRAM based transparent devices for non-volatile memory application.

Automated Carrier Landing of an Unmanned Combat Aerial Vehicle Using Dynamic Inversion

DTIC Science & Technology

2007-06-01

17 CN normal force coefficient . . . . . . . . . . . . . . . . . . . . 17 CA axial force coefficient...slug·ft2 Ixzb 0 slug·ft2 The aircraft has a single engine inlet for a single, centerline mounted turbofan engine. For purposes of this research, the...assumed to remain constant for each simulation run and were based on an assumed 10% fuel load with full weapons [2]. The rest of these values were

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

PubMed

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|.

Spectra, Index of Refraction, and Optical Constants of Nitrile Ices Relevant to Titan's Atmosphere

NASA Astrophysics Data System (ADS)

Moore, Marla; Hudson, Reggie; Ferrante, Robert; Moore, William

Spectra and optical constants of nitrile ices known or suspected to be in Titan's atmosphere are presented from 2.5 to 200 microns (4000 to 50 cm-1 ). These results are relevant to the ongoing modeling of Cassini CIRS observations of Titan's winter pole. Ices studied include: HCN, hydrogen cyanide; C2 N2 , cyanogen; CH3 CN, acetonitrile; C2 H5 CN, propionitrile; and HC3 N, cyanoacetylene. For each of these molecules we report new measurements of the index of refraction, n, determined in both the amorphous-and crystalline-phase at 670 nm. Spectra were measured and optical constants were calculated for each nitrile at a variety of temperatures including 20, 35, 50, 75, 95, and 110 K, in the amorphous-and crystalline-phase. This laboratory effort uses a dedicated FTIR spectrometer to record transmission spectra of thin-film ice samples. Laser interference is used to measure film thickness during condensation onto a transparent cold window attached to the tail section of a closed-cycle helium cryo-stat. Optical constants, real (n) and imaginary (k) refractive indices, are determined using Kramers-Kronig (K-K) analysis. Our calculation reproduces the complete spectrum, including all interference effects. Index of refraction measurements are made in a separate dedicated FTIR spectrometer where interference deposit fringes are measured using two 670 nm lasers at different angles to the ice substrate. A survey of these new measurements will be presented along with a discussion of their validation, errors, and application to Titan data. We acknowledge Mark Loeffler who recently joined in our refractive index measurements. The authors also acknowledge support from the Cassini Data Analysis Program. RLH and MHM acknowledge additional funding from NASA's PGG and Outer Planets Programs, and the Goddard Center for Astrobiology.

Water-assisted production of honeycomb-like g-C3N4 with ultralong carrier lifetime and outstanding photocatalytic activity

NASA Astrophysics Data System (ADS)

Wang, Zhenyu; Guan, Wei; Sun, Yanjuan; Dong, Fan; Zhou, Ying; Ho, Wing-Kei

2015-01-01

Graphitic carbon nitride (g-C3N4) is a visible light photocatalyst, limited by low activity mainly caused by rapid recombination of charge carriers. In the present work, honeycomb-like g-C3N4 was synthesized via thermal condensation of urea with addition of water at 450 °C for 1 h. Prolonging the condensation time caused the morphology of g-C3N4 to change from a porous honeycomb structure to a velvet-like nanoarchitecture. Unlike in previous studies, the photocatalytic activity of g-C3N4 decreased with increasing surface area. The honeycomb-like g-C3N4 with a relatively low surface area showed highly enhanced photocatalytic activity with an NO removal ratio of 48%. The evolution of NO2 intermediate was dramatically inhibited over the honeycomb-like g-C3N4. The short and long lifetimes of the charge carriers for honeycomb-like g-C3N4 were unprecedentedly prolonged to 22.3 and 165.4 ns, respectively. As a result, the honeycomb-like g-C3N4 was highly efficient and stable in activity and could be used repeatedly. Addition of water had the following multiple positive effects on g-C3N4: (1) formation of the honeycomb structure, (2) promotion of charge separation and migration, (3) enlargement of the band gap, (4) increase in production yield, and (5) decrease in energy cost. These advantages make the present preparation method for highly efficient g-C3N4 extremely appealing for large-scale applications. The active species produced from g-C3N4 under illumination were confirmed using DMPO-ESR spin-trapping, the reaction intermediate was monitored, and the reaction mechanism of photocatalytic NO oxidation by g-C3N4 was revealed. This work could provide an attractive alternative method for mass-production of highly active g-C3N4-based photocatalysts for environmental and energetic applications.Graphitic carbon nitride (g-C3N4) is a visible light photocatalyst, limited by low activity mainly caused by rapid recombination of charge carriers. In the present work, honeycomb-like g-C3N4 was synthesized via thermal condensation of urea with addition of water at 450 °C for 1 h. Prolonging the condensation time caused the morphology of g-C3N4 to change from a porous honeycomb structure to a velvet-like nanoarchitecture. Unlike in previous studies, the photocatalytic activity of g-C3N4 decreased with increasing surface area. The honeycomb-like g-C3N4 with a relatively low surface area showed highly enhanced photocatalytic activity with an NO removal ratio of 48%. The evolution of NO2 intermediate was dramatically inhibited over the honeycomb-like g-C3N4. The short and long lifetimes of the charge carriers for honeycomb-like g-C3N4 were unprecedentedly prolonged to 22.3 and 165.4 ns, respectively. As a result, the honeycomb-like g-C3N4 was highly efficient and stable in activity and could be used repeatedly. Addition of water had the following multiple positive effects on g-C3N4: (1) formation of the honeycomb structure, (2) promotion of charge separation and migration, (3) enlargement of the band gap, (4) increase in production yield, and (5) decrease in energy cost. These advantages make the present preparation method for highly efficient g-C3N4 extremely appealing for large-scale applications. The active species produced from g-C3N4 under illumination were confirmed using DMPO-ESR spin-trapping, the reaction intermediate was monitored, and the reaction mechanism of photocatalytic NO oxidation by g-C3N4 was revealed. This work could provide an attractive alternative method for mass-production of highly active g-C3N4-based photocatalysts for environmental and energetic applications. Electronic supplementary information (ESI) available: XRD patterns of CN-1-10, CN-1-20 and CN-1-30 samples. FT-IR spectra of CN-1, CN-3, and CN-5. SEM images of CN-1, CN-3 and CN-5. TEM images of CN-1-10 and CN-1-30. The N2 adsorption-desorption isotherms and corresponding pore-size distribution curves of CN-1, CN-3, CN-5, CN-1-10, CN-1-20 and CN-1-30. Enlarged view of the pore-size distribution curve of the CN-1 sample. UV-vis DRS of CN-1-10, CN-1-20 and CN-1-30. Visible light photocatalytic activities of the CN-1-10, CN-1-20, CN-1-30 for removal of NO in air. See DOI: 10.1039/c4nr05732e

Rotation-stimulated structures in the CN and C3 comae of comet 103P/Hartley 2 close to the EPOXI encounter

NASA Astrophysics Data System (ADS)

Waniak, W.; Borisov, G.; Drahus, M.; Bonev, T.

2012-07-01

Context. In late 2010, a Jupiter family comet 103P/Hartley 2 was the subject of an intensive world-wide investigation. On UT October 20.7, the comet approached the Earth within only 0.12 AU, and on UT November 4.6 it was visited by the NASA EPOXI spacecraft. Aims: We joined this international effort and organized a ground-based observing campaign with three key goals to: (1) measure the parameters of the nucleus rotation in a time series of CN; (2) investigate the compositional structure of the coma by comparing the CN images with nightly snapshots of C3; and (3) investigate the photochemical relation of CN to HCN, using the HCN data collected nearly simultaneously with our images. Methods: The images were obtained through narrowband filters using the two-meter telescope of the Rozhen National Astronomical Observatory. They were taken over four nights about the moment of the EPOXI encounter. Image processing methods and periodicity analysis techniques were used to identify transient coma structures and investigate their repeatability and kinematics. Results: We observe shells, arc-, jet- and spiral-like patterns that are very similar for the CN and C3 comae. The CN features expanded outwards with the sky-plane projected velocities of between 0.1 to 0.3 km s-1. A corkscrew structure, observed on November 6, evolved with a much higher velocity of 0.66 km s-1. The photometry of the inner coma of CN shows variability with a period of 18.32 ± 0.30 h (valid for the middle moment of our run, UT 2010 Nov 5.0835), which we attribute to the nucleus rotation. This result is fully consistent with independent determinations around the same time by other teams. The pattern of repeatability is, however, imperfect, which is understendable given the suggested excitation of the rotation state, and the variability detected in CN correlates well with the cyclic changes in HCN, but only in the active phases. The identified coma structures, along with the snapshot of the nucleus orientation obtained by EPOXI, enable us to estimate the spin axis orientation. We obtain RA = 122°, Dec = +16° (epoch J2000.0), neglecting at this point the rotational excitation. Based on data collected with two-meter RCC telescope at Rozhen National Astronomical Observatory.Appendix A and movies are available in electronic form at http://www.aanda.org

Ionic liquid-assisted synthesis of Br-modified g-C3N4 semiconductors with high surface area and highly porous structure for photoredox water splitting

NASA Astrophysics Data System (ADS)

Zhao, Shuo; Zhang, Yiwei; Wang, Yanyun; Zhou, Yuming; Qiu, Kaibo; Zhang, Chao; Fang, Jiasheng; Sheng, Xiaoli

2017-12-01

Coping with the gradually increasing worldwide energy and environmental issues, it is urgent to develop efficient, cheap and visible-light-driven photocatalysts for hydrogen production. Here, we present a facile way to synthesize bromine doped graphitic carbon nitride (CN-BrX) with highly porous structure by using ionic liquid (1-butyl-3-vinylimidazolium bromide) as the Br source and soft-template for the first time, which applied in hydrogen evolution under visible light irradiation. A systematic study is conducted on the optimization in the doping amount. The results find that the as-fabricated CN-BrX photocatalysts possess a uniform porous network with thin walls due to the release of volatile domains and decomposition of ionic liquids. The highly porous structure with the large surface area (≤150 m2/g) benefits the exposure of active sites. Moreover, the bromine modification and porous structure can narrow the band gap, enhance the transportation capability of photogenerated electrons, improve the optical and conductive properties of CN, thus contribute to an outstanding H2 evolution rate under visible light irradiation (120 μmol h-1), which is about 3.6 times higher than pure CN. This work provides a new insight for designing the novel g-C3N4 based photocatalysts for hydrogen production, CO2 conversion and environmental remediation.

Noninertial Multirelativity

NASA Astrophysics Data System (ADS)

Smarandache, Florentin

2012-10-01

We firstly propose an extension of Einstein's thought experiment with atomic clocks of the Special Theory of Relativity: considering non-constant accelerations and arbitrary 3D-curves for both a particle's speed and trajectory inside the rocket and respectively the rocket's speed and trajectory. And secondly we propose as research multiple reference frames F1, F2, , Fn moving on respectively arbitrary 3D-curves C1, C2, , Cn with respectively arbitrary non-constant accelerations a1, a2, , an and respectively initial velocities v1, v2, , vn. The reference frame Fi is moving with a nonconstant acceleration ai and initial velocity vi on a 3D-curve Ci with respect to another reference frame Fi+1 (where 1 <= i <= n-1).

Effect of Hydrofluoroether Cosolvent Addition on Li Solvation in Acetonitrile-Based Solvate Electrolytes and Its Influence on S Reduction in a Li–S Battery

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

See, Kimberly A.; Wu, Heng -Liang; Lau, Kah Chun

Li-S batteries are a promising next-generation battery technology. Due to the formation of soluble polysulfides during cell operation, the electrolyte composition of the cell plays an active role in directing the formation and speciation of the soluble lithium polysulfides. Recently, new classes of electrolytes termed "solvates" that contain stoichiometric quantities of salt and solvent and form a liquid at room temperature have been explored due to their sparingly solvating properties with respect to polysulfides. The viscosity of the solvate electrolytes is understandably high limiting their viability; however, hydrofluoroether cosolvents, thought to be inert to the solvate structure itself, can bemore » introduced to reduce viscosity and enhance diffusion. Nazar and co-workers previously reported that addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) to the LiTFSI in acetonitrile solvate, (MeCN) 2-LiTFSI, results in enhanced capacity retention compared to the neat solvate. Here, we evaluate the effect of TTE addition on both the electrochemical behavior of the Li-S cell and the solvation structure of the (MeCN) 2-LiTFSI electrolyte. Contrary to previous suggestions, Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that TTE coordinates to Li + at the expense of MeCN coordination, thereby producing a higher content of free MeCN, a good polysulfide solvent, in the electrolyte. Furthermore, the electrolytes containing a higher free MeCN content facilitate faster polysulfide formation kinetics during the electrochemical reduction of S in a Li-S cell likely as a result of the solvation power of the free MeCN.« less

Effect of Hydrofluoroether Cosolvent Addition on Li Solvation in Acetonitrile-Based Solvate Electrolytes and Its Influence on S Reduction in a Li–S Battery

DOE PAGES

See, Kimberly A.; Wu, Heng -Liang; Lau, Kah Chun; ...

2016-11-16

Li-S batteries are a promising next-generation battery technology. Due to the formation of soluble polysulfides during cell operation, the electrolyte composition of the cell plays an active role in directing the formation and speciation of the soluble lithium polysulfides. Recently, new classes of electrolytes termed "solvates" that contain stoichiometric quantities of salt and solvent and form a liquid at room temperature have been explored due to their sparingly solvating properties with respect to polysulfides. The viscosity of the solvate electrolytes is understandably high limiting their viability; however, hydrofluoroether cosolvents, thought to be inert to the solvate structure itself, can bemore » introduced to reduce viscosity and enhance diffusion. Nazar and co-workers previously reported that addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) to the LiTFSI in acetonitrile solvate, (MeCN) 2-LiTFSI, results in enhanced capacity retention compared to the neat solvate. Here, we evaluate the effect of TTE addition on both the electrochemical behavior of the Li-S cell and the solvation structure of the (MeCN) 2-LiTFSI electrolyte. Contrary to previous suggestions, Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that TTE coordinates to Li + at the expense of MeCN coordination, thereby producing a higher content of free MeCN, a good polysulfide solvent, in the electrolyte. Furthermore, the electrolytes containing a higher free MeCN content facilitate faster polysulfide formation kinetics during the electrochemical reduction of S in a Li-S cell likely as a result of the solvation power of the free MeCN.« less

Effect of Hydrofluoroether Cosolvent Addition on Li Solvation in Acetonitrile-Based Solvate Electrolytes and Its Influence on S Reduction in a Li-S Battery.

PubMed

See, Kimberly A; Wu, Heng-Liang; Lau, Kah Chun; Shin, Minjeong; Cheng, Lei; Balasubramanian, Mahalingam; Gallagher, Kevin G; Curtiss, Larry A; Gewirth, Andrew A

2016-12-21

Li-S batteries are a promising next-generation battery technology. Due to the formation of soluble polysulfides during cell operation, the electrolyte composition of the cell plays an active role in directing the formation and speciation of the soluble lithium polysulfides. Recently, new classes of electrolytes termed "solvates" that contain stoichiometric quantities of salt and solvent and form a liquid at room temperature have been explored due to their sparingly solvating properties with respect to polysulfides. The viscosity of the solvate electrolytes is understandably high limiting their viability; however, hydrofluoroether cosolvents, thought to be inert to the solvate structure itself, can be introduced to reduce viscosity and enhance diffusion. Nazar and co-workers previously reported that addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) to the LiTFSI in acetonitrile solvate, (MeCN) 2 -LiTFSI, results in enhanced capacity retention compared to the neat solvate. Here, we evaluate the effect of TTE addition on both the electrochemical behavior of the Li-S cell and the solvation structure of the (MeCN) 2 -LiTFSI electrolyte. Contrary to previous suggestions, Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that TTE coordinates to Li + at the expense of MeCN coordination, thereby producing a higher content of free MeCN, a good polysulfide solvent, in the electrolyte. The electrolytes containing a higher free MeCN content facilitate faster polysulfide formation kinetics during the electrochemical reduction of S in a Li-S cell likely as a result of the solvation power of the free MeCN.

Two solvent and temperature dependent copper(II) compounds formed by a flexible ligand: syntheses, structures and SC-SC transformation.

PubMed

Sun, Haixia; Xie, Wenli; Lv, Shenghong; Xu, Yan; Wu, Yong; Zhou, Yaoming; Ma, Zhenmao; Fang, Min; Liu, Hong-Ke

2012-07-07

A nonporous neutral framework [CuCl(2)(m-bttmb)(2)](n) (1) was changed into a porous ionic {[Cu(m-bttmb)(2)(H(2)O)Cl]Cl(CH(3)CN)(0.5)(H(2)O)(2.75)}(n) (2) by simply increasing the amount of CH(3)CN in the mixed solvent (CH(3)CN and H(2)O) or temperature in the reactions of CuCl(2)·2H(2)O with 1,3-bis(triazol-1-ylmethyl)-2,4,6-trimethylbenzene (m-bttmb). 1 undergoes transformation into 2 when treated with CH(3)CN. Both 1 and 2 have 2D 4-connected (4,4) network architectures but in different packing arrangements. These compounds have been characterized by single-crystal X-ray diffraction analysis, elemental analysis, IR spectra and thermogravimetric analysis. This work may provide a way to control the formation of neutral or ionic frameworks, as well as porosities by adjusting the polarity and components of the solvents.

Ultrafast intramolecular charge transfer with N-(4-cyanophenyl)carbazole. Evidence for a LE precursor and dual LE + ICT fluorescence.

PubMed

Galievsky, Victor A; Druzhinin, Sergey I; Demeter, Attila; Mayer, Peter; Kovalenko, Sergey A; Senyushkina, Tamara A; Zachariasse, Klaas A

2010-12-09

The photophysics of N-(4-cyanophenyl)carbazole (NP4CN) was investigated by using absorption and fluorescence spectra, picosecond fluorescence decays, and femtosecond transient absorption. In the nonpolar n-hexane as well as in the polar solvent acetonitrile (MeCN), a locally excited (LE) state is detected, as a precursor for the intramolecular charge transfer (ICT) state. A LE → ICT reaction time τ(2) at 22 °C of 0.95 ps in ethyl cyanide (EtCN) and 0.32 ps in MeCN is determined from the decay of the LE excited state absorption (ESA) maximum around 620 nm. In the ESA spectrum of NP4CN in n-hexane at a pump-probe delay time of 100 ps, an important contribution of the LE band remains alongside the ICT band, in contrast to what is observed in EtCN and MeCN. This shows that a LE ⇄ ICT equilibrium is established in this solvent and the ICT reaction time of 0.5 ps is equal to the reciprocal of the sum of the forward and backward ICT rate constants 1/(k(a) + k(d)). In the photostationary S(0) → S(n) absorption spectrum of NP4CN in n-hexane and MeCN, an additional CT absorption band appears, absent in the sum of the spectra of its electron donor (D) and acceptor (A) subgroups carbazole and benzonitrile. This CT band is located at an energy of ∼4000 cm(-1) lower than for N-phenylcarbazole (NPC), due to the larger electron affinity of the benzonitrile moiety of NP4CN than the phenyl subunit of NPC. The fluorescence spectrum of NP4CN in n-hexane at 25 °C mainly consists of a structured LE emission, with a small ICT admixture, indicating that a LE → ICT reaction just starts to occur under these conditions. In di-n-pentyl ether (DPeE) and di-n-butyl ether (DBE), a LE emission is found upon cooling at the high-energy edge of the ICT fluorescence band, caused by the onset of dielectric solvent relaxation. This is not the case in more polar solvents, such as diethyl ether (DEE) and MeCN, in which a structureless ICT emission band fully overlaps the strongly quenched LE fluorescence. For the series of D/A molecules NPC, N-(4-fluorophenyl)carbazole (NP4F), N-[4-(trifluoromethyl)phenyl]carbazole (NP4CF), and NP4CN, with increasing electron affinity of their phenyl subgroup, an ICT emission in n-hexane 25 °C only is present for NP4CN, whereas in MeCN an ICT fluorescence is observed with NP4CF and NP4CN. The ICT fluorescence appears when for the energies E(ICT) of the ICT state and E(S(1)) of the lowest excited singlet state the condition E(ICT) ≤ E(S(1)) holds. E(ICT) is calculated from the difference E(D/D(+)) - E(A(-)/A) of the redox potentials of the D and A subgroups of the N-phenylcarbazoles. From solvatochromic measurements with NP4CN an ICT dipole moment μ(e)(ICT) = 19 D is obtained, somewhat larger than the literature values of 10-16 D, because of a different Onsager radius ρ. The carbazole/phenyl twist angle θ = 45° of NP4CN in the S(0) ground state, determined from X-ray crystal analysis, has become smaller for its ICT state, in analogy with similar conclusions for related N-phenylcarbazoles and other D/A molecules in the literature.

X-ray structure of the metcyano form of dehaloperoxidase from Amphitrite ornata: evidence for photoreductive dissociation of the iron-cyanide bond

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

de Serrano, V.S.; Davis, M.F.; Gaff, J.F.

X-ray crystal structures of the metcyano form of dehaloperoxidase-hemoglobin (DHP A) from Amphitrite ornata (DHPCN) and the C73S mutant of DHP A (C73SCN) were determined using synchrotron radiation in order to further investigate the geometry of diatomic ligands coordinated to the heme iron. The DHPCN structure was also determined using a rotating-anode source. The structures show evidence of photoreduction of the iron accompanied by dissociation of bound cyanide ion (CN{sup -}) that depend on the intensity of the X-ray radiation and the exposure time. The electron density is consistent with diatomic molecules located in two sites in the distal pocketmore » of DHPCN. However, the identities of the diatomic ligands at these two sites are not uniquely determined by the electron-density map. Consequently, density functional theory calculations were conducted in order to determine whether the bond lengths, angles and dissociation energies are consistent with bound CN{sup -} or O{sub 2} in the iron-bound site. In addition, molecular-dynamics simulations were carried out in order to determine whether the dynamics are consistent with trapped CN{sup -} or O{sub 2} in the second site of the distal pocket. Based on these calculations and comparison with a previously determined X-ray crystal structure of the C73S-O{sub 2} form of DHP [de Serrano et al. (2007), Acta Cryst. D63, 1094-1101], it is concluded that CN{sup -} is gradually replaced by O{sub 2} as crystalline DHP is photoreduced at 100 K. The ease of photoreduction of DHP A is consistent with the reduction potential, but suggests an alternative activation mechanism for DHP A compared with other peroxidases, which typically have reduction potentials that are 0.5 V more negative. The lability of CN{sup -} at 100 K suggests that the distal pocket of DHP A has greater flexibility than most other hemoglobins.« less

Correlation between bonding structure and microstructure in fullerenelike carbon nitride thin films

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

Gago, R.; Abendroth, B.; Moeller, W.

2005-03-15

The bonding structure of highly ordered fullerenelike (FL) carbon nitride (CN{sub x}) thin films has been assessed by x-ray absorption near-edge spectroscopy (XANES). Samples with different degrees of FL character have been analyzed to discern spectral signatures related to the FL microstructure. The XANES spectra of FL-CN{sub x} films resemble that of graphitic CN{sub x}, evidencing the sp{sup 2} hybridization of both C and N atoms. The FL structure is achieved with the promotion of N in threefold positions over pyridinelike and cyanidelike bonding environments. In addition, the relative {pi}{sup *}/{sigma}* XANES intensity ratio at the C(1s) edge is independentmore » of the FL character, while it decreases {approx}40% at the N(1s) edge with the formation of FL arrangements. This result indicates that there is no appreciable introduction of C-sp{sup 3} hybrids with the development of FL structures and, additionally, that a different spatial localization of {pi} electrons at C and N sites takes place in curved graphitic structures. The latter has implications for the elastic properties of graphene sheets and could, as such, explain the outstanding elastic properties of FL-CN{sub x}.« less

Slow magnetic relaxation and luminescence properties in lanthanide(iii)/anil complexes.

PubMed

Maniaki, Diamantoula; Mylonas-Margaritis, Ioannis; Mayans, Julia; Savvidou, Aikaterini; Raptopoulou, Catherine P; Bekiari, Vlasoula; Psycharis, Vassilis; Escuer, Albert; Perlepes, Spyros P

2018-05-22

The initial use of anils, i.e. bidentate Schiff bases derived from the condensation of anilines with salicylaldehyde or its derivatives, in 4f-metal chemistry is described. The 1 : 1 reactions between Ln(NO3)3·xH2O (Ln = lanthanide) or Y(NO3)3·6H2O and N-(5-bromosalicylidene)aniline (5BrsalanH) in MeCN has provided access to complexes [Ln(NO3)3(5BrsalanH)2(H2O)]·MeCN (Ln = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) and [Y(NO3)3(5BrsalanH)2(H2O)]·MeCN, respectively, in good yields. The structures of the isomorphous complexes with Ln = Pr(1·MeCN), Sm(3·MeCN), Gd(5·MeCN), Dy(7·MeCN) and Er(9·MeCN) have been determined by single-crystal X-ray crystallography. The other complexes were proven to be isostructural with the fully structurally characterized compounds based on elemental analyses, IR spectra, unit cell determinations and powder X-ray patterns. The 9-coordinate LnIII centre in the [Ln(NO3)3(5BrsalanH)2(H2O)] molecules is bound to six oxygen atoms from the three bidentate chelating nitrato groups, two oxygen atoms that belong to the organic ligands and one oxygen atom from the aquo ligand. The 5BrsalanH molecules behave as monodentate O-donors; the acidic H atom is clearly located on the imino N atom and thus the formally neutral ligands adopt an extremely rare coordination mode participating in the zwitterionic form. The coordination polyhedra defined by the nine donor atoms around the LnIII centres are best described as spherical capped square antiprisms. Various intermolecular interactions build the crystal structures and Hirshfeld surface analysis was applied to evaluate the magnitude of interactions between the molecules. Solid-state IR and UV/VIS data are discussed in terms of structural features. 1H NMR data prove that the diamagnetic [Y(NO3)3(5BrsalanH)2(H2O)] complex decomposes in DMSO. Combined dc and ac magnetic susceptibility, as well as magnetization data for 7 suggest that this complex shows field-induced slow magnetic relaxation. Two magnetization relaxation processes are evident. The fit to the Arrhenius law has been performed using the 6.5-8.5 K ac data, affording an effective barrier for the magnetization reversal of 27 cm-1. Cole-Cole plot analysis in the temperature range in which the Orbach relaxation process is assumed, reveals a narrow distribution of relaxation times. The solid Dy(iii) complex 7 emits green light at 338 nm, the emission being ligand-centered. The perspectives of the present, first results in the lanthanide(iii)-anil chemistry are critically discussed.

A new modification of an old framework: Hofmann layers with unusual tetracyanidometallate groups

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

Keene, Tony D.; Murphy, Michael J.; Price, Jason R.

2012-05-10

Cyanidometallate complexes are highly versatile building units for the generation of functional porous materials. Here we report five new pillared Hofmann layer compounds incorporating the tetracyanidometallates [MoO(CN){sub 4}]{sup 2-} and [MnN(CN){sub 4}]{sup 2-}. These metalloligands, which are new to this class of materials, have been combined with divalent 1st-row transition metals to produce Hofmann layers that are linked into three-dimensional frameworks by ditopic bridging dipyridyls. We report the structures and anomalous thermal expansion properties of five new materials: [Mn(H{sub 2}O)(bpy){sub 1/2}{l_brace}MoO(CN){sub 4}(bpy){sub 1/2}{r_brace}] {center_dot} 2H{sub 2}O (1), [Mn(H{sub 2}O)(bpy){sub 1/2}{l_brace}MnN(CN){sub 4}(bpy){sub 1/2}{r_brace}] {center_dot} 2H{sub 2}O (2), [Fe(H{sub 2}O)(bpy){sub 1/2}{l_brace}MnN(CN){sub 4}(bpy){submore » 1/2}{r_brace}] {center_dot} 2H{sub 2}O (3), [Co(H{sub 2}O)(bpy){sub 1/2}{l_brace}MnN(CN){sub 4}(bpy){sub 1/2}{r_brace}] {center_dot} 2H{sub 2}O (4) and [{l_brace}Mn(H{sub 2}O){sub 2}{r_brace}{sub 1/2}{l_brace}Mn(bpa){sub 2}{r_brace}{sub 1/2}{l_brace}MoO(CN){sub 4}(bpa){sub 1/2}{r_brace}] {center_dot} MeOH (5), (where bpy = 4,4'-bipyridine and bpa = 4,4'-bipyridylacetylene).« less

The structure of carbodiimide, HNCNH

NASA Astrophysics Data System (ADS)

Jabs, Wolfgang; Winnewisser, Manfred; Belov, Sergei P.; Lewen, Frank; Maiwald, Frank; Winnewisser, Gisbert

An experimentally determined rs -type structure of HNCNH is reported: rNH = 1.0074 A, rCN = 1.2242 A, /HNC = 118.63, /NCN = 170.63, /HN NH = 88.99 . The number of digits quoted allow for errors with two significant figures. In order to obtain these values we recorded rotational-torsional spectra of HN13CNH, H15NC15NH and DNCND, by using isotopically enriched cyanamide. A chemical equilibrium exists between carbodiimide, HNCNH, and the more stable isomer cyanamide, H2NCN, which strongly favours cyanamide (approximately 1:115 at 110 oC). The expensive C- and N-substituted isotopomers could only be investigated in the millimetre wave region, while for DNCND the far infrared spectrum between 10-350 cm-1 was also recorded. Rotational constants of the three isotopomers, as well as of the parent species, were determined by fitting the assigned spectral transitions to the Watson Hamiltonian in S reduction. Using fitting programs written by Schwendeman and Rudolph, r0, rs and rrho m structures of HNCNH were derived. The experimentally determined structural parameters are compared with an ab initio re structure.

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

PubMed

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.

Spectroscopic properties of morin in various CH3OH-H2O and CH3CN-H2O mixed solvents.

PubMed

Park, Hyoung-Ryun; Im, Seo-Eun; Seo, Jung-Ja; Kim, Bong-Gon; Yoon, Jin Ah; Bark, Ki-Min

2015-01-01

The specific fluorescence properties of morin (3,2',4',5,7-pentahydroxyflavone) were studied in various CH3OH-H2O and CH3CN-H2O mixed solvents. Although the dihedral angle is large in the S0 state, morin has an almost planar molecular structure in the S1 state owing to the very low rotational energy barrier around the interring bond between B and the A, C ring. The excited state intramolecular proton transfer (ESIPT) at the S1 state cannot occur immediately after excitation, S1 → S0 fluorescence can be observed. Two conformers, Morin A and B have been known. At the CH3OH-H2O, Morin B will be the principal species but at the CH3CN-H2O, Morin A is the principal species. At the CH3OH-H2O, owing to the large Franck-Condon (FC) factor for S2 → S1 internal convernal (IC) and flexible molecular structure, only S1 → S0 fluorescence was exhibited. At the CH3CN-H2O, as the FC factor for S2 → S1 IC is small and molecular structure is rigid, S2 → S0 and S1 → S0 dual fluorescence was observed. This abnormal fluorescence property was further supported by the small pK1 value, effective delocalization of the lone pair electrons of C(2')-OH to the A, C ring, and a theoretical calculation. © 2014 The American Society of Photobiology.

General calibration methodology for a combined Horton-SCS infiltration scheme in flash flood modeling

NASA Astrophysics Data System (ADS)

Gabellani, S.; Silvestro, F.; Rudari, R.; Boni, G.

2008-12-01

Flood forecasting undergoes a constant evolution, becoming more and more demanding about the models used for hydrologic simulations. The advantages of developing distributed or semi-distributed models have currently been made clear. Now the importance of using continuous distributed modeling emerges. A proper schematization of the infiltration process is vital to these types of models. Many popular infiltration schemes, reliable and easy to implement, are too simplistic for the development of continuous hydrologic models. On the other hand, the unavailability of detailed and descriptive information on soil properties often limits the implementation of complete infiltration schemes. In this work, a combination between the Soil Conservation Service Curve Number method (SCS-CN) and a method derived from Horton equation is proposed in order to overcome the inherent limits of the two schemes. The SCS-CN method is easily applicable on large areas, but has structural limitations. The Horton-like methods present parameters that, though measurable to a point, are difficult to achieve a reliable estimate at catchment scale. The objective of this work is to overcome these limits by proposing a calibration procedure which maintains the large applicability of the SCS-CN method as well as the continuous description of the infiltration process given by the Horton's equation suitably modified. The estimation of the parameters of the modified Horton method is carried out using a formal analogy with the SCS-CN method under specific conditions. Some applications, at catchment scale within a distributed model, are presented.

Visual stimulation synchronizes or desynchronizes the activity of neuron pairs between the caudate nucleus and the posterior thalamus.

PubMed

Rokszin, Alice; Gombköto, Péter; Berényi, Antal; Márkus, Zita; Braunitzer, Gábor; Benedek, György; Nagy, Attila

2011-10-18

Recent morphological and physiological studies have suggested a strong relationship between the suprageniculate nucleus (Sg) of the posterior thalamus and the input structure of the basal ganglia, the caudate nucleus (CN) of the feline brain. Accordingly, to clarify if there is a real functional relationship between Sg and CN during visual information processing, we investigated the temporal relations of simultaneously recorded neuronal spike trains of these two structures, looking for any significant cross-correlation between the spiking of the simultaneously recorded neurons. For the purposes of statistical analysis, we used the shuffle and jittering resampling methods. Of the recorded 288 Sg-CN neuron pairs, 26 (9.2%) showed significantly correlated spontaneous activity. Nineteen pairs (6.7%) showed correlated activity during stationary visual stimulation, while 21 (7.4%) pairs during stimulus movement. There was no overlap between the neuron pairs that showed cross-correlated spontaneous activity and the pairs that synchronized their activity during visual stimulation. Thus visual stimulation seems to have been able to synchronize, and also, by other neuron pairs, desynchronize the activity of CN and Sg. In about half of the cases, the activation of Sg preceded the activation of CN by a few milliseconds, while in the other half, CN was activated earlier. Our results provide the first piece of evidence for the existence of a functional cooperation between Sg and CN. We argue that either a monosynaptic bidirectional direct connection should exist between these structures, or a common input comprising of parallel pathways synchronizing them. Copyright © 2011 Elsevier B.V. All rights reserved.

Processing, Structure and High Temperature Oxidation Properties of Polymer-Derived and Hafnium Oxide Based Ceramic Systems

NASA Astrophysics Data System (ADS)

Terauds, Kalvis

Demands for hypersonic aircraft are driving the development of ultra-high temperature structural materials. These aircraft, envisioned to sustain Mach 5+, are expected to experience continuous temperatures of 1200--1800°C on the aircraft surface and temperatures as high as 2800°C in combustion zones. Breakthroughs in the development of fiber based ceramic matrix composites (CMCs) are opening the door to a new class of high-tech UHT structures for aerospace applications. One limitation with current carbon fiber or silicon carbide fiber based CMC technology is the inherent problem of material oxidation, requiring new approaches for protective environmental barrier coatings (EBC) in extreme environments. This thesis focuses on the development and characterization of SiCN-HfO2 based ceramic composite EBC systems to be used as a protective layer for silicon carbide fiber based CMCs. The presented work covers three main architectures for protection (i) multilayer films, (ii) polymer-derived HfSiCNO, and (iii) composite SiCN-HfO 2 infiltration. The scope of this thesis covers processing development, material characterization, and high temperature oxidation behavior of these three SiCN-HfO2 based systems. This work shows that the SiCN-HfO 2 composite materials react upon oxidation to form HfSiO4, offering a stable EBC in streaming air and water vapor at 1600°C.

Linear trichromium complexes with the anion of 2,6-di(phenylimino)piperidine.

PubMed

Clérac, R; Cotton, F A; Daniels, L M; Dunbar, K R; Murillo, C A; Zhou, H C

2000-07-24

The anion of 2,6-di(phenylimino)piperidine (DPhIP) has been found to support linear chains of three metal atoms. Three new compounds, [Cr3(DPhIP)4Cl]Cl.(1).5CH2Cl2.0.5H2O (1.1.5CH2Cl2.0.5H2O), [Cr3(DPhIP)4(CH3CN)]- (PF6)2.H2O.4CH3CN (2.H2O.4CH3CN), and [Cr3(DPhIP)4(F)(CH3CN)](BF4)2.5CH3CN (3.5CH3CN), have been synthesized and characterized by X-ray crystallography. Compound 1 has a linear chain of three chromium atoms arranged in an unsymmetrical fashion, with two of them forming a quadruply bonded unit (Cr-Cr distance 1.932(2) A) and the third being a non-metal-metal-bound 5-coordinate unit (Cr...Cr distance 2.659(2) A). The fifth coordination site is occupied by a chloride ion, and another chloride ion is located in the interstices of the crystal. The trimetal unit in compound 2 is structurally similar to that in compound 1 except that the axial ligand in 2 is a CH3CN molecule. Compound 3 is an oxidation product prepared by reaction of 1 with AgBF4. Here, a square pyramidal CrIII unit, FCrN4, and a Cr-Cr quadruply bonded (Cr-Cr distance 1.968(2) A) unit, with an axially coordinated acetonitrile molecule, form the trichromium chain. The CrIII...CrII separation of 2.594(2) A in 3 is too long to be considered a bonding interaction.

Effect of diblock copolymer properties on the photophysical properties of dendrimer silicon phthalocyanine nanoconjugates

NASA Astrophysics Data System (ADS)

Chen, Kuizhi; Pan, Sujuan; Zhuang, Xuemei; Lv, Hafei; Que, Shoulin; Xie, Shusen; Yang, Hongqin; Peng, Yiru

2016-07-01

1-2 generation poly(benzyl aryl ether) dendrimer silicon phthalocyanines with axially disubstituted cyano terminal functionalities (G n -DSiPc(CN)4 n , (G n = n-generation dendrimer, n = 1-2)) were synthesized. Their structures were characterized by elemental analysis, IR, 1H NMR, and ESI-MS. Polymeric nanoparticles (G n -DSiPc(CN)4 n /m) were formed through encapsulating G n -DSiPc(CN)4 n into three monomethoxyl poly(ethylene glycol)-poly(ɛ-caprolactone) diblock copolymers (MPEG-PCL) with different hydrophilic/hydrophobic proportion, respectively. The effect of dendritic generation and the hydrophilic/hydrophobic proportion of diblock copolymers on the UV/Vis and fluorescence spectra of G n -DSiPc(CN)4 n and G n -DSiPc(CN)4 n /m were studied. The photophysical properties of polymeric nanoparticles exhibited dendritic generation and hydrophilic/hydrophobic proportion dependence. The fluorescence intensities and lifetimes of G n -DSiPc(CN)4 n /m were lower than the corresponding free dendrimer phthalocyanines. G n -DSiPc(CN)4 n encapsulated into MPEG-PCL with hydrophilic/hydrophobic molecular weight ratio 2000:4000 exhibited excellent photophysical property. The mean diameter of MPEG2000-PCL2000 micelles was about 70 nm, which decreased when loaded with G n -DSiPc(CN)4 n .

The relative availability of inorganic carbon and inorganic nitrogen influences the response of the dinoflagellate Protoceratium reticulatum to elevated CO2.

PubMed

Pierangelini, Mattia; Raven, John A; Giordano, Mario

2017-04-01

This work originates from three facts: (i) changes in CO 2 availability influence metabolic processes in algal cells; (ii) Spatial and temporal variations of nitrogen availability cause repercussions on phytoplankton physiology; (iii) Growth and cell composition are dependent on the stoichiometry of nutritional resources. In this study, we assess whether the impact of rising pCO 2 is influenced by N availability, through the impact that it would have on the C/N stoichiometry, in conditions of N sufficiency. Our experiments used the dinoflagellate Protoceratium reticulatum, which we cultured under three CO 2 regimes (400, 1,000, and 5,000 ppmv, pH of 8.1) and either variable (the NO 3 - concentration was always 2.5 mmol · L -1 ) or constant (NO 3 - concentration varied to maintain the same C i /NO 3 - ratio at all pCO 2 ) C i /NO 3 - ratio. Regardless of N availability, cells had higher specific growth rates, but lower cell dry weight and C and N quotas, at elevated CO 2 . The carbohydrate pool size and the C/N was unaltered in all treatments. The lipid content only decreased at high pCO 2 at constant C i /NO 3 - ratio. In the variable C i /NO 3 - conditions, the relative abundance of Rubisco (and other proteins) also changed; this did not occur at constant C i /NO 3 - . Thus, the biomass quality of P. reticulatum for grazers was affected by the C i /NO 3 - ratio in the environment and not only by the pCO 2 , both with respect to the size of the main organic pools and the composition of the expressed proteome. © 2016 Phycological Society of America.

Confinement induced ordering in dewetting of ultra-thin polymer bilayers on nanopatterned substrates.

PubMed

Bhandaru, Nandini; Das, Anuja; Mukherjee, Rabibrata

2016-01-14

We report the dewetting of a thin bilayer of polystyrene (PS) and poly(methylmethacrylate) (PMMA) on a topographically patterned nonwettable substrate comprising an array of pillars, arranged in a square lattice. With a gradual increase in the concentration of the PMMA solution (Cn-PMMA), the morphology of the bottom layer changes to: (1) an aligned array of spin dewetted droplets arranged along substrate grooves at very low Cn-PMMA; (2) an interconnected network of threads surrounding each pillar at intermediate Cn-PMMA; and (3) a continuous bottom layer at higher Cn-PMMA. On the other hand the morphology of the PS top layer depends largely on the nature of the pre-existing bottom layer, in addition to Cn-PS. An ordered array of PMMA core-PS shell droplets forms right after spin coating when both Cn-PMMA and Cn-PS are very low. Bilayers with all other initial configurations evolve during thermal annealing, resulting in a variety of ordered structures. Unique morphologies realized include laterally coexisting structures of the two polymers confined within the substrate grooves due to initial rupture of the bottom layer on the substrate followed by a squeezing flow of the top layer; an array of core-shell and single polymer droplets arranged in an alternating order etc., to highlight a few. Such structures cannot be fabricated by any stand-alone lithography technique. On the other hand, in some cases the partially dewetted bottom layer imparts stability to an intact top PS layer against dewetting. Apart from ordering, under certain specific conditions significant miniaturization and downsizing of dewetted feature periodicity and dimension as compared to dewetting of a single layer on a flat substrate is observed. With the help of a morphology phase diagram we show that ordering is achieved over a wide combination of Cn-PMMA and Cn-PS, though the morphology and dewetting pathway differs significantly with variation in the thickness of the individual layers.

Myochrysine Solution Structure and Reactivity

PubMed Central

Jones, William B.; Zhao, Zheng; Dorsey, John G.; Tepperman, Katherine

1994-01-01

We have determined the framework structure of Myochrysine (disodium gold(I)thiomalate) in the solid state and extremely concentrated aqueous solution, previously. It consists of an open chain polymer with linear gold coordination to two thiolates from the thiomalic acid moieties which bridge between pairs of gold atoms providing an Au-S-Au angle of 95°. The question remained: was this structure relevant to the dilute solutions of drugs administered and the still lower concentrations of gold found in the bodies of patients (typically 1 ppm Au in blood and urine or 5 μM in Au). We have provided an answer to that question using extended X-ray absorption spectroscopy (EXAFS) and capillary zone electrophoresis (CZE). EXAFS studies confirm that the polymeric structure with two sulfur atoms per gold atom persists from molar concentrations down to millimolar concentrations. CZE is able to separate and detect Myochrysine at millimolar levels. More importantly, at micromolar levels Myochrysine solutions exhibit identical CZE behavior to that measured at millimolar levels. Thus, aqueous solutions of the drug remain oligomeric at concentrations commensurate with those found in patient blood and urine. The reactivity of Myochrysine with cyanide, a species especially prevalent in smoking patients, was explored using CZE. Cyanide freely replaces thiomalic acid to form [Au(CN)2]- and thiomalic acid via a mixed ligand intermediate. The overall apparent equilibrium constant (Kapp) for the reaction is 6×10-4M-1. Further reaction of [Au(CN)2]- with a large excess of L, where L is cysteine, N-acetylcysteine, or glutathione, shows that these amino acids readily replace cyanide to form [AuL2]-. These species are thus potential metabolites and could possibly be active forms of gold in vivo. That all of these species are readily separated and quantified using CZE demonstrates that capillary electrophoresis is an accessible and powerful tool to add to those used for the study of gold-based antiarthritis drugs. PMID:18476256

Microstructures, mechanical behavior and strengthening mechanism of TiSiCN nanocomposite films

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

Li, Wei; Liu, Ping; Xue, Zenghui

Recently, the arguments have existed in the strengthening mechanism and microstructural model of the nanocomposite film due to lack of the convincible experimental evidences. In this investigation, the quarternary TiSiCN nanocomposite films with the different C and Si contents are synthesized by the reactive-magnetron-sputtering technique. The TiSiCN film is characterized as the nanocomposite structure with the TiN nanocrystallites surrounded by the (Si 3N 4 + C + CN x) interface phase. When the C/Si content ratio is 2:2, the TiSiCN nanocomposite film is remarkably strengthened with the maximal hardness and elastic modulus of 46.1 GPa and 425 GPa, respectively. Meanwhile,more » the (Si 3N 4 + C + CN x) interfaces exhibit as a crystallized form, which can coordinate the growth misorientations and maintain the coherently epitaxial growth between the TiN nanocrystallites and interfaces. Through the high-resolution transmission electron microscopy (HRTEM) observations, this investigation firstly provides the direct experimental evidence for the crystallized feature of the interfaces when the TiSiCN nanocomposite film is strengthened, suggesting that the strengthening effect of the TiSiCN nanocomposite film can be attributed to the coherent-interface strengthening mechanism, which is expressed as the “nc-TiN/c-Si 3N 4/c-C/c-CN x” model.« less

Microstructures, mechanical behavior and strengthening mechanism of TiSiCN nanocomposite films

DOE PAGES

Li, Wei; Liu, Ping; Xue, Zenghui; ...

2017-05-18

Recently, the arguments have existed in the strengthening mechanism and microstructural model of the nanocomposite film due to lack of the convincible experimental evidences. In this investigation, the quarternary TiSiCN nanocomposite films with the different C and Si contents are synthesized by the reactive-magnetron-sputtering technique. The TiSiCN film is characterized as the nanocomposite structure with the TiN nanocrystallites surrounded by the (Si 3N 4 + C + CN x) interface phase. When the C/Si content ratio is 2:2, the TiSiCN nanocomposite film is remarkably strengthened with the maximal hardness and elastic modulus of 46.1 GPa and 425 GPa, respectively. Meanwhile,more » the (Si 3N 4 + C + CN x) interfaces exhibit as a crystallized form, which can coordinate the growth misorientations and maintain the coherently epitaxial growth between the TiN nanocrystallites and interfaces. Through the high-resolution transmission electron microscopy (HRTEM) observations, this investigation firstly provides the direct experimental evidence for the crystallized feature of the interfaces when the TiSiCN nanocomposite film is strengthened, suggesting that the strengthening effect of the TiSiCN nanocomposite film can be attributed to the coherent-interface strengthening mechanism, which is expressed as the “nc-TiN/c-Si 3N 4/c-C/c-CN x” model.« less

Necessary and sufficient conditions for discrete wavelet frames in CN

NASA Astrophysics Data System (ADS)

Deepshikha; Vashisht, Lalit K.

2017-07-01

We present necessary and sufficient conditions with explicit frame bounds for a discrete wavelet system of the form {DaTk ϕ } a ∈ U(N) , k ∈IN to be a frame for the unitary space CN. It is shown that the canonical dual of a discrete wavelet frame for CN has the same structure. This is not true (well known) for canonical dual of a wavelet frame for L2(R) . Several numerical examples are given to illustrate the results.

Does Metal Ion Complexation Make Radical Clocks Run Fast? An Experimental Perspective.

PubMed

Abdel Latif, Marwa K; Spencer, Jared N; Paradzinsky, Mark; Tanko, James M

2017-12-28

The rate constant for the β-scission of the cumyloxyl radical (k β ) was measured in the presence of various added electrolytes in acetonitrile and DMSO solvent. The results show that in CH 3 CN, k β increases in the presence of added electrolyte, roughly paralleling the size of the cation: Li + > Mg 2+ ≈ Na + > n Bu 4 N + > no added electrolyte. As suggested by Bietti et al. earlier, this effect is attributable to stabilizing ion-dipole interactions in the transition state of the developing carbonyl group, a conclusion further amplified by MO calculations (gas phase) reported herein. Compared to the gas phase predictions, however, this effect is seriously attenuated in solution because complexation of the cation to the electrophilic alkoxyl radical (relative to the solvent, CH 3 CN) is very weak. Because the interaction of Li + and Na + is much stronger with DMSO than with CH 3 CN, addition of these ions has no effect on the rate of β-scission.

Understanding temperature and magnetic-field actuated magnetization polarity reversal in the Prussian blue analogue Cu 0.73 Mn 0.77 [Fe(CN) 6 ]. z H 2 O, using XMCD

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

Lahiri, Debdutta; Choi, Yongseong; Yusuf, S. M.

2016-02-23

We have investigated the microscopic origin of temperature and magnetic-field actuated magnetization reversal in Cu0.73Mn0.77[Fe(CN)(6)]center dot zH(2)O, using XMCD. Our results show a fair deviation from the mean-field-theory in the form of different ordering temperatures of Fe and Mn sublattices. A preferential sign reversal of Mn spin under magnetic field and different spin cant angles for the two sublattices have also been observed. An antiferromagnetic coupling between the Fe and Mn sublattices along with different ordering temperatures (sublattice decoupling) for these sublattices explain the temperature-dependent magnetization reversal. Whereas, Mn spin reversal alone (under external magnetic field) is responsible for themore » observed field-dependent magnetization reversal. The dissimilar magnetic behavior of Fe and Mn sublattices in this cubic 3d-orbital system has been understood by invoking disparity and competition among inter-sublattice magnetic control parameters, viz. magnetic Zeeman energy, exchange coupling constant and magnetic anisotropy constant. Our results have significant design implications for future magnetic switches, by optimizing the competition among these magnetic control parameters.« less

Persistent inflammation with pedal osteolysis 1 Year after Charcot neuropathic osteoarthropathy

PubMed Central

Sinacore, David R.; Bohnert, Kathryn L.; Smith, Kirk E.; Hastings, Mary K.; Commean, Paul K.; Gutekunst, David J.; Johnson, Jeffrey E.; Prior, Fred W.

2017-01-01

Structured Abstract Aims To determine local and systemic markers of inflammation and bone mineral density (BMD) in the foot and central sites in participants with diabetes mellitus and peripheral neuropathy (DMPN) with and without acute Charcot neuropathic osteoarthropathy (CN). Methods Eighteen participants with DMPN and CN and 19 participants without CN had foot temperature assessments, serum markers of inflammation [C-reactive protein, (CRP) and erythrocyte sedimentation rate, (ESR)] and BMD of the foot, hip and lumbar spine at baseline and 1 year follow-up. Results CN foot temperature difference was higher compared to DMPN controls at baseline (4.2 ± 1.9 °F vs. 1.2 ± 0.9 °F, P < 0.01) and after 1 year (2.9 ± 3.2 °F vs. 0.9 ± 1.1 °F, P < 0.01). Serum inflammatory markers in the CN group were greater at baseline and remained elevated 1 year later compared to DMPN controls (CRP, P =0.02, ESR, P = 0.03). All pedal bones’ BMD decreased an average of 3% in the CN foot with no changes in hip or lumbar spine. DMPN controls’ foot, hip and lumbar spine BMD remained unchanged. Conclusions Local and systemic inflammation persists1 year after CN with an accompanying pedal osteolysis that may contribute to mid foot deformity which is the hallmark of the chronic Charcot foot. PMID:28254346

Dynamics in a Water Interfacial Boundary Layer Investigated with IR Polarization-Selective Pump-Probe Experiments.

PubMed

Yuan, Rongfeng; Yan, Chang; Nishida, Jun; Fayer, Michael D

2017-05-04

The dynamics of water molecules near the surfactant interface in large Aerosol-OT reverse micelles (RMs) (w 0 = 16-25) was investigated with IR polarization-selective pump-probe experiments using the SeCN - anion as a vibrational probe. Linear absorption spectra of RMs (w 0 = 25-2) can be decomposed into the weighted sum of the SeCN - spectra in bulk water and the spectrum of the SeCN - anion interacting with the interfacial sulfonate head groups (w 0 = 1). The spectra of the large RMs, w 0 ≥ 16, are overwhelmingly dominated by the bulk water component. Anisotropy decays (orientational relaxation) of the anion for w 0 ≥ 16 displayed bulk water relaxation (1.4 and 4.5 ps) plus an additional slow decay with a time constant of ∼13 ps. The amplitude of the slow decay was too large to be associated with SeCN - in contact with the interface on the basis of the linear spectrum decomposition. The results indicate that the observed slow components arise from SeCN - in a water boundary layer, in which water molecules are perturbed by the interface but are not directly associated with it. This layer is the transition between water in direct contact with the interface and bulk water in the large RM cores. In the boundary layer, the water dynamics is slow compared to that in bulk water.

Pressure–Temperature Phase Diagram Reveals Spin–Lattice Interactions in Co[N(CN) 2 ] 2

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

Musfeldt, J. L.; O’Neal, K. R.; Brinzari, T. V.

2017-04-07

Diamond anvil cell techniques, synchrotron-based infrared and Raman spectroscopies, and lattice dynamics calculations are combined with prior magnetic property work to reveal the pressure–temperature phase diagram of Co[N(CN)2]2. The second-order structural boundaries converge on key areas of activity involving the spin state exposing how the pressure-induced local lattice distortions trigger the ferromagnetic → antiferromagnetic transition in this quantum material.

Self-standing paper based anodes prepared from siliconcarbonitride-MoS2 composite for Li-ion battery applications

NASA Astrophysics Data System (ADS)

David, Lamuel; Singh, Gurpreet

2013-03-01

We study synthesis of free-standing polymer derived SiCN/ MoS2 composite paper anode for Li-ion battery application. This was achieved following a two-step approach: First, polysilazane was interfaced with exfoliated MoS2 nanosheets which upon pyrolysis resulted in SiCN/MoS2 composite. Second, dispersion of SiCN/MoS2 in isopropanol was vacuum filtered resulting in formation of a self-standing composite paper. Physical and chemical characterization of the composite was carried out by use of electron microscopy, Fourier transform infrared spectroscopy (FT-IR) and Thermo-gravimetric analysis (TGA). FT-IR data indicated complete conversion of polysilazane precursor to SiCN ceramic, while electron microscopy confirmed layered structure of the paper. Thermo-gravimetric analysis showed enhanced thermodynamic stability of the composite paper up to 800 °C. Electrochemical analysis of SiCN/MoS2 composite paper anodes showed that Li-ion can reversible intercalate in the voltage range of 0-2.5 V with a first cycle discharge capacity of 770 mAh/g at a current density of 100 mA/g.

Laboratory detection and millimeter spectrum of the MgCCH radical

NASA Technical Reports Server (NTRS)

Anderson, M. A.; Ziurys, L. M.

1995-01-01

The pure rotational spectrum of the magnesium monoacetylide radical, MgCCH, has been recorded in the laboratory using millimeter/sub-mm direct absorption spectroscopy. These measurements constitute the first time this molecule has been observed in the laboratory by any spectroscopic method. Seventeen rotational transitions were observed in the frequency range 210-370 GHz for MgCCH, which appears to be a linear molecule with a (sup 2)Sigma ground electronic state. Rotational and fine structure constants were determined for this radical from a nonlinear least squares fit to the data. The rotational rest frequencies measured here will enable astronomical observations to be carried out for MgCCH towards IRC +10216, where the magnesium compounds MgCN and MgNC, as well as many acetylide species, are present.

Solvation of Cr 3+ cation in water-acetonitrile mixture studied by IR spectroscopy: molecular penetration into the solvation shells

NASA Astrophysics Data System (ADS)

Jamróz, Dorota; Wójcik, Marek; Lindgren, Jan

2000-09-01

Infrared spectra of mixtures of water and deuteroacetonitrile containing the Cr 3+ cation have been studied as a function of concentration, time and temperature. The CN stretching vibration of CD 3CN molecules has been used as a probe of the structural environments. The CN band in the spectra of the solutions is a superposition of four subbands, which may be attributed to CD 3CN bound in the first, second, and third solvation shells of the cation and to non-bound CD 3CN. The character of changes of the integral intensities of the subbands with time for various H 2O:Cr 3+ molar ratios are explained by suggesting mechanisms of molecular replacement within the solvation shells of Cr 3+.

Terrestrial C sequestration at elevated CO2 and temperature: the role of dissolved organic N loss

USGS Publications Warehouse

Rastetter, Edward B.; Perakis, Steven S.; Shaver, Gaius R.; Agren, Goran I.

2005-01-01

We used a simple model of carbon–nitrogen (C–N) interactions in terrestrial ecosystems to examine the responses to elevated CO2 and to elevated CO2 plus warming in ecosystems that had the same total nitrogen loss but that differed in the ratio of dissolved organic nitrogen (DON) to dissolved inorganic nitrogen (DIN) loss. We postulate that DIN losses can be curtailed by higher N demand in response to elevated CO2, but that DON losses cannot. We also examined simulations in which DON losses were held constant, were proportional to the amount of soil organic matter, were proportional to the soil C:N ratio, or were proportional to the rate of decomposition. We found that the mode of N loss made little difference to the short‐term (<60 years) rate of carbon sequestration by the ecosystem, but high DON losses resulted in much lower carbon sequestration in the long term than did low DON losses. In the short term, C sequestration was fueled by an internal redistribution of N from soils to vegetation and by increases in the C:N ratio of soils and vegetation. This sequestration was about three times larger with elevated CO2 and warming than with elevated CO2 alone. After year 60, C sequestration was fueled by a net accumulation of N in the ecosystem, and the rate of sequestration was about the same with elevated CO2 and warming as with elevated CO2alone. With high DON losses, the ecosystem either sequestered C slowly after year 60 (when DON losses were constant or proportional to soil organic matter) or lost C (when DON losses were proportional to the soil C:N ratio or to decomposition). We conclude that changes in long‐term C sequestration depend not only on the magnitude of N losses, but also on the form of those losses.

Synthesis, characterization, structural and biological aspects of copper(II) dithiocarbamate complexes - Part II, [Cu{S2CN(Me)(R1)}2], [Cu{S2CN(Me)(R2)}2] and [Cu{S2CN(R3)(R4)}2] {R1 = CH2CH(OMe)2, R2 = 2-methyl-1,3-dioxolane, R3 = CH2(CH2)2NCHPhOCH2Ph and R4 = CH2CH2OH}

NASA Astrophysics Data System (ADS)

Ferreira, Isabella P.; de Lima, Geraldo M.; Paniago, Eucler B.; Takahashi, Jacqueline A.; Krambrock, Klaus; Pinheiro, Carlos B.; Wardell, James L.; Visentin, Lorenzo C.

2013-09-01

Three new copper(II) dithiocarbamates (DTC), [Cu{S2CN(Me)(R1)}2] (1), [Cu{S2CN(Me)(R2)}2] (2) and [Cu{S2CN(R3)(R4)}2] (3) with R1 = CH2CH(OMe)2, R2 = 2-methyl-1,3-dioxolane, R3 = CH2(CH2)2NCHPhOCH2Ph and R4 = CH2CH2OH, have been synthesized and characterized by different spectroscopic techniques. Complexes (1) and (2) display typical EPR spectra for separated Cu(II) centers, and the spectrum of (3) is characteristic of two magnetically coupled Cu(II) ions with S = 1. The X-ray crystallographic determination has shown that complexes (1) and (2) crystallise in the triclinic and monoclinic systems. In addition both complexes are monomers in which the geometry at each Cu(II) is square planar. The in vitro antimicrobial activity of the sodium salts of ligands, and of the Cu(II)-DTC complexes have been screened against Aspergillus flavus, Aspergillus niger, Aspergillus parasiticus, Penicillium citrinum and Curvularia senegalensis, as well as Gram positive and Gram negative bacteria. Finally, the toxic effects of complexes (1)-(3) were performed using Chlorella vulgaris.

Porous framework of T{sub 2}[Fe(CN){sub 6}].xH{sub 2}O with T=Co, Ni, Cu, Zn, and H{sub 2} storage

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

Avila, M.; Reguera, L.; Rodriguez-Hernandez, J.

2008-11-15

The materials under study were prepared from aqueous solutions of ferrocyanic acid and salts of the involved transition metals and their crystal structure solved and refined from X-ray powder diffraction data. Complementary information from thermogravimetric, infrared and Moessbauer data was also used for the structural study. Three different crystal structures were found: hexagonal (P-3) for Zn with the zinc atom coordinated to three N ends of CN groups plus a water molecule, cubic (Pm-3m) for Ni and Cu, and monoclinic (P2{sub 1}/m) for Co. For Ni and Cu the obtained solids have an open channel framework related to 50% ofmore » vacancies for the building unit, [Fe(CN){sub 6}]. In the as-synthesized material the framework free volume is occupied by coordinated and hydrogen-bonded water molecules. These of hexacyanoferrates (II) have received certain attention as prototype of materials for the hydrogen storage. In the anhydrous phase of Ni and Cu, 50% of the metal (T) coordination sites, located at the cavities surface, will be available to interact with the hydrogen molecule. However, when the crystal waters are removed the porous frameworks collapse as it is suggested by H{sub 2} and CO{sub 2} adsorption data. For Co, a structure of stacked layers was found where the cobalt atoms have both tetrahedral and octahedral coordination. The layers remain together through a network of hydrogen-bonding interactions between coordinated and weakly bonded water molecules. No H{sub 2} adsorption was observed in the anhydrous phase of Co. For Zn, the porous framework remains stable on the water removal but with a system of narrow channels and a small available volume, also inaccessible to H{sub 2}. - Graphical abstract: Structure of stacked layers for CO{sub 2}[Fe(CN){sub 6}].xH{sub 2}O.« less

Unique coordination of pyrazine in T[Ni(CN){sub 4}].2pyz with T=Mn, Zn, Cd

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

Lemus-Santana, A.A.; Rodriguez-Hernandez, J.; Castillo, L.F. del, E-mail: lfelipe@servidor.unam.m

2009-04-15

The materials under study, T[Ni(CN){sub 4}].2pyz with T=Mn, Zn, Cd, were prepared by separation of T[Ni(CN){sub 4}] layers in citrate aqueous solution to allow the intercalation of the pyrazine molecules. The obtained solids were characterized from chemical analyses, X-ray diffraction, infrared, Raman, thermogravimetry, UV-Vis, magnetic and adsorption data. Their crystal structure was solved from ab initio using direct methods and then refined by the Rietveld method. A unique coordination for pyrazine to metal centers at neighboring layers was observed. The pyrazine molecule is found forming a bridge between Ni and T atoms, quite different from the proposed structures for T=Fe,more » Ni where it remains coordinated to two T atoms to form a vertical pillar between neighboring layers. The coordination of pyrazine to both Ni and T atoms minimizes the material free volume and leads to form a hydrophobic framework. On heating the solids remain stable up to 140 deg. C. No CO{sub 2} and H{sub 2} adsorption was observed in the small free spaces of their frameworks. - Graphical abstract: Framework for T[Ni(CN){sub 4}].2pyz with T=Mn, Zn, Cd.« less

Cationic copper (I) complexes with bulky 1,4-diaza-1,3-butadiene ligands - Synthesis, solid state structure and catalysis

NASA Astrophysics Data System (ADS)

Anga, Srinivas; Kottalanka, Ravi K.; Pal, Tigmansu; Panda, Tarun K.

2013-05-01

We report the full characterization of two glyoxal-based ligands N,N bis(diphenylmethyl)-1,4-diaza-1,3-butadiene ligand (DADPh2, 1) and more bulky N,N bis(triphenylmethyl)-1,4-diaza-1,3-butadiene ligand (DADPh3, 2) by the condensation reaction of glyoxal and diphenylmethanamine and triphenyl-methanamine respectively. The copper (I) complex of composition [Cu(DADPh2)2]PF6 (3) having two neutral bidentate N,N bis(diphenyl-methyl)-1,4-diaza-1,3-butadiene ligand was prepared by the reaction of [Cu(CH3CN)4]PF6 and 1 in 1:2 ratio in dichloromethane. In a similar reaction with N,N bis(triphenylmethyl)-1,4-diaza-1,3-butadiene ligand (2) and [Cu(CH3CN)4]PF6 in dichloromethane yielded corresponding heteroleptic copper (I) complex [Cu(DADPh3)(CH3CN)2]PF6 (4). Another copper (I) complex [Cu(DADPh2)(PPh3)]PF6 (5) can also be obtained by the one pot reaction involving ligand 1, [Cu(CH3CN)4]PF6 and triphenylphosphine. Solid state structures of all the five compounds were established by single crystal X-ray diffraction analysis. The solid state structures of the copper complexes 3-5 reveal a distorted tetrahedral geometry around the copper (I) centers. The copper complexes 3-5 were tested as catalysts for the coupling reaction of o-iodophenol and phenyl acetylene and it was observed that complex 4 exhibits the highest catalytic activity.

Kinetics and Mechanism of the Reaction of Hydoxyl Radicals with Acetonitrile under Atmospheric Conditions

NASA Technical Reports Server (NTRS)

Hynes, A. J.; Wine, P. H.

1997-01-01

The pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to determine absolute rate coefficients for the reaction OH + CH3CN (1) and its isotopic variants, OH + CD3CN (2), OD + CH3CN (3), and OD + CD3CN (4). Reactions 1 and 2 were studied as a function of pressure and temperature in N2, N2/O2, and He buffer gases. In the absence of O2 all four reactions displayed well-behaved kinetics with exponential OH decays and pseudo-first rate constants which were proportional to substrate concentration. Data obtained in N2 over the range 50-700 Torr at 298 K are consistent with k(sub 1), showing a small pressure dependence. The Arrhenius expression obtained by averaging data at all pressures in k(sub 1)(T) = (1.1(sup +0.5)/(sub -0.3)) x 10(exp -12) exp[(-1130 +/- 90)/T] cu cm /(molecule s). The kinetics of reaction 2 are found to be pressure dependent with k(sub 2) (298 K) increasing from (1.21 +/- 0.12) x 10(exp -14) to (2.16 +/- 0.11) x 10(exp -14) cm(exp 3)/ (molecule s) over the pressure range 50-700 Torr of N2 at 298 K. Data at pressures greater than 600 Torr give k(sub 2)(T) = (9.4((sup +13.4)(sub -5.0))) x 10(exp -13) exp[(-1180 +/- 250)/T] cu cm/(molecule s). The rates of reactions 3 and 4 are found to be independent of pressure over the range 50-700 Torr of N2 with 298 K rate coefficient given by k(sub 3) =(3.18 +/- 0.40) x 10(exp -14) cu cm/(molecule s) and k(sub 4) = (2.25 +/-0.28) x 10(exp -14) cu cm/(molecule s). In the presence of O2 each reaction shows complex (non-pseudo-first-order) kinetic behavior and/or an apparent decrease in the observed rate constant with increasing [O2], indicating the presence of significant OH or OD regeneration. Observation of regeneration of OH in (2) and OD in (3) is indicative of a reaction channel which proceeds via addition followed by reaction of the adduct, or one of its decomposition products, with O2. The observed OH and OD decay profiles have been modeled by using a simple mechanistic scheme to extract kinetic information about the adduct reations with O2 and branching ratios for OH regeneration. A plausible mechanism for OH regeneration in (2) involves OH addition to the nitrogen atom followed by O2 addition to the cyano carbon atom, isomeriazation and decomposition to D2CO + DOCN + OH. Our results suggest that the OH + CH3CN reaction occurs via a complex mechanism involving both bimolecular and termolecular pathways, analogous to the mechanisms for the the important atmospheric reactions of OH with CO and HNO3.

A spirooxazine derivative as a highly sensitive cyanide sensor by means of UV-visible difference spectroscopy.

PubMed

Zhu, Shaoyin; Li, Minjie; Sheng, Lan; Chen, Peng; Zhang, Yumo; Zhang, Sean Xiao-An

2012-12-07

A spirooxazine derivative 2-nitro-5a-(2-(4-dimethylaminophenyl)-ethylene)-6,6-dimethyl-5a,6-dihydro-12H-indolo[2,1-b][1,3]benzooxazine (P1) was explored as a sensitive cyanide probe. Different from conventional spiropyrans, P1 avoided locating the 3H-indolium cation and the 4-nitrophenolate anion in the same conjugated structure, which enhanced the positive charge of 3H-indolium cation so that the sensitivity and reaction speed were improved highly. UV-visible difference spectroscopy using P1 detection solution as a timely reference improved the measurement accuracy, prevented the error caused by the inherent absorption change of P1 solution with time. This enabled the "positive-negative alternative absorption peaks" in difference spectrum to be used as a finger-print to distinguish whether the spectral change was caused by cyanide. Benefiting from the special design of the molecular structure and the strategy of difference spectroscopy, P1 showed high selectivity and sensitivity for CN(-). A detection limit of 0.4 μM and a rate constant of 1.1 s(-1) were achieved.

The millimeter and sub-millimeter rotational spectrum of triple 13C-substituted ethyl cyanide

NASA Astrophysics Data System (ADS)

Pienkina, A. O.; Margulès, L.; Motiyenko, R. A.; Müller, H. S. P.; Guillemin, J.-C.

2017-05-01

Context. A recently published astronomical detection of all three doubly 13C-substituted ethyl cyanides toward Sgr B2(N2) motivated us to investigate triple 13C isotopic species that are expected to be also present in the ISM. Aims: We aim to present an experimental study of the rotational spectrum of triple 13C-substituted ethyl cyanide, 13CH313CH213CN, in the frequency range 150-990 GHz. We want to use the determined spectroscopic parameters for searching for 13CH313CH213CN in ALMA data. The main objective of this work is to provide accurate frequency predictions to search for this molecule in the Galactic center source Sagittarius B2(N) and to facilitate its detection in space. Methods: The laboratory rotational spectrum of 13CH313CH213CN has been recorded with the Lille's fast DDS solid-state spectrometer between 150 GHz and 990 GHz. Results: More than 4000 rotational transitions were identified in the laboratory. The quantum numbers reach J = 115 and Ka = 39. Watson's Hamiltonian in the A and S reductions were used to analyze the spectra. Accurate spectroscopic parameters were determined. The rotational spectra of the 13C containing species CH3CH2CN have been assigned, thus allowing the determination of the rotational and centrifugal distortion constants Full Table 3 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/601/A2

Ligand-Mediated Ring → Cube Transformation in a Catalytic Subnanocluster: Co4O4(MeCN)n with n = 1-6.

PubMed

Luo, Sijie; Dibble, Collin J; Duncan, Michael A; Truhlar, Donald G

2014-08-07

We studied the Co4O4 subnanocluster and its MeCN-coated species using density functional theory, and we found that the Co4O4 core presents distinctive structures in bare and ligand-coated species. We propose a possible ligand-mediated ring → cube transformation mechanism during the ligand-coating process of the Co4O4 core due to the stronger binding energies of the MeCN ligands to the 3D distorted cube structure than to the 2D ring and ladder structures; theory indicates that three ligands are sufficient to stabilize the cube structure. Both ring and cube structures are ferromagnetic. Our finding is potentially useful for understanding the catalysis mechanism of Co4O4 species, which have important applications in solar energy conversion and water splitting; these catalysis reactions usually involve frequent addition and subtraction of various ligands and thus possibly involve core rearrangement processes similar to our findings.

Optimal Server Scheduling to Maintain Constant Customer Waiting Times

DTIC Science & Technology

1988-12-01

I I• I I I I I LCn CN OPTIMAL SERVER SCHEDUUNG TO MAINTAIN CONSTANT CUSTOMER WAITING TIMES THESIS Thomas J. Frey Captain UISAF AFIT/GOR/ENS/88D-7...hw bees appsewlf in ple rtan. cd = , ’ S 087 AFIT/GORMENS/8D-7 OPTIMAL SERVER SCHEDUUNG TO MAINTAIN~ CONSTANT CUSTOMER WAITING TIMES THESIS Thomas j...CONSTANT CUSTOMER WAITING TIMES THESIS Presented to the Faculty of the School of Engineering of the Air Force Institute of Technology Air University In

The application of chiroptical spectroscopy (circular dichroism) in quantifying binding events in lanthanide directed synthesis of chiral luminescent self-assembly structures† †Electronic supplementary information (ESI) available. CCDC 999267–999270 and 1026036. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc02474e Click here for additional data file. Click here for additional data file.

PubMed Central

Blasco, Salvador; Twamley, Brendan; O'Brien, John; Peacock, Robert D.; Kitchen, Jonathan A.; Martínez-Calvo, Miguel

2015-01-01

The binding of asymmetrical and optically pure tridentate ligands (L = 1(S) and 1(R)) containing one carboxylic group and 2-naphthyl as an antenna to lanthanide ions (M = La(iii) and Eu(iii)) was studied in CH3CN, showing the successive formation of M:L, M:L2 and M:L3 stoichiometric species in solution. The europium complexes EuL3 were also synthesised, structurally characterised and their photophysical properties probed in CH3OH and CH3CN. The changes in the chiroptical properties of both 1(S) and 1(R) were used (by circular dichroism (CD) spectroscopy) to monitor the formation of these chiral self-assemblies in solution. While circularly polarised luminescence (CPL) showed the formation of Eu(1(S))3 and Eu(1(R))3 as enantiomers, with high luminescence dissymmetry factors (g lum), fitting the CD changes allowed for binding constants to be determined that were comparable to those seen in the analyses of absorbance and luminescence changes. PMID:28936303

Very high laser-damage threshold of polymer-derived Si(B)CN-carbon nanotube composite coatings.

PubMed

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.

Variability in the fractionation of stable isotopes during degradation of two intertidal red algae

NASA Astrophysics Data System (ADS)

Hill, Jaclyn M.; McQuaid, Christopher D.

2009-04-01

Macroalgae contribute to intertidal food webs primarily as detritus, with unclear implications for food web studies using stable isotope analysis. We examined differences in the thallus parts of two South African rhodophytes ( Gelidium pristoides and Hypnea spicifera) and changes in overall δ13C, δ15N signatures and C:N ratios during degradation in both the field and laboratory. We hypothesized that both degrading macroalgal tissue and macroalgal-derived suspended particulate material (SPM) would show negligible changes in δ13C, but enriched δ15N signatures and lower C:N ratios relative to healthy plants. Only C:N laboratory ratios conformed to predictions, with both species of macroalgae showing decomposition related changes in δ13C and significant depletions in δ15N in both the field and laboratory. In the laboratory, algal tissue and SPM from each species behaved similarly (though some effects were non-significant) but with differing strengths. Gelidium pristoides δ13C increased and C:N ratios decreased over time in tissue and SPM; δ15N became depleted only in SPM. Hypnea spicifera, δ13C, δ15N and C:N ratios all decreased during degradation in both SPM and algae. Over 60 days in the field, δ13C was depleted in both species (1-2‰) and in naturally senescent Gelidium pristoides fronds. δ15N was depleted in Hypnea spicifera (approx. 1‰), while C:N ratios of both species were unaffected. The two species differed in δ13C, δ15N and C:N after degradation, but only in C:N beforehand. We suggest isotope changes in the laboratory mainly reflect microbial effects, while in the field these are combined with leaching due to constant water replenishment and agitation. Differences between these two species in the isotope responses to degradation highlight the difficulty of linking the signature of SPM to its multiple sources.

[Tl(III)(dota)](-): An Extraordinarily Robust Macrocyclic Complex.

PubMed

Fodor, Tamás; Bányai, István; Bényei, Attila; Platas-Iglesias, Carlos; Purgel, Mihály; Horváth, Gábor L; Zékány, László; Tircsó, Gyula; Tóth, Imre

2015-06-01

The X-ray structure of {C(NH2)3}[Tl(dota)]·H2O shows that the Tl(3+) ion is deeply buried in the macrocyclic cavity of the dota(4-) ligand (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate) with average Tl-N and Tl-O distances of 2.464 and 2.365 Å, respectively. The metal ion is directly coordinated to the eight donor atoms of the ligand, which results in a twisted square antiprismatic (TSAP') coordination around Tl(3+). A multinuclear (1)H, (13)C, and (205)Tl NMR study combined with DFT calculations confirmed the TSAP' structure of the complex in aqueous solution, which exists as the Λ(λλλλ)/Δ(δδδδ) enantiomeric pair. (205)Tl NMR spectroscopy allowed the protonation constant associated with the protonation of the complex according to [Tl(dota)](-) + H(+) ⇆ [Tl(Hdota)] to be determined, which turned out to be pK(H)Tl(dota) = 1.4 ± 0.1. [Tl(dota)](-) does not react with Br(-), even when using an excess of the anion, but it forms a weak mixed complex with cyanide, [Tl(dota)](-) + CN(-) ⇆ [Tl(dota)(CN)](2-), with an equilibrium constant of Kmix = 6.0 ± 0.8. The dissociation of the [Tl(dota)](-) complex was determined by UV-vis spectrophotometry under acidic conditions using a large excess of Br(-), and it was found to follow proton-assisted kinetics and to take place very slowly (∼10 days), even in 1 M HClO4, with the estimated half-life of the process being in the 10(9) h range at neutral pH. The solution dynamics of [Tl(dota)](-) were investigated using (13)C NMR spectroscopy and DFT calculations. The (13)C NMR spectra recorded at low temperature (272 K) point to C4 symmetry of the complex in solution, which averages to C4v as the temperature increases. This dynamic behavior was attributed to the Λ(λλλλ) ↔ Δ(δδδδ) enantiomerization process, which involves both the inversion of the macrocyclic unit and the rotation of the pendant arms. According to our calculations, the arm-rotation process limits the Λ(λλλλ) ↔ Δ(δδδδ) interconversion.

[Effect of stimulation of GABA-ergic structures of the substantia nigra and caudate nucleus on food-getting behavior in the cat].

PubMed

Shugalev, N P

1983-01-01

A study was made of the functional significance of GABA-ergic structures of the substantia nigra (SN) and the caudate nucleus (CN) and their role in food-procuring behaviour of cats. Analysis was made of behavioral and EEG-effects of local GABA and the GABA antagonist, picrotoxin, microinjections into the studied brain structures. Stimulation of the GABA-ergic structures of the SN produced a sedative effect and depression of the cat food-procuring behaviour. Effects of stimulation of the CN GABA-ergic structures were to a great degree reverse. The conclusion has been made that GABA-ergic structures of the SN and the CN play different roles in controlling the CN inhibitory influence upon food-procuring behaviour.

An extended source for CN jets in Comet P/Halley

NASA Technical Reports Server (NTRS)

Klavetter, James Jay; A'Hearn, Michael F.

1994-01-01

We examined radial intensity profiles of CN jets in comparison with the diffuse, isotropic component of the CN coma of Comet P/Halley. All images were bias-subtracted, flat-fielded, and continuum-subtracted. We calculated the diffuse profiles by finding the azimuthal mean of the coma least contaminated by jets yielding profiles similar to those of vectorial and Haser models of simple photodissociation. We found the jet profiles by calculating a mean around a Gaussian-fitted center in r-theta space. There is an unmistakable difference between the profiles of the CN jets and the profiles of the diffuse CN. Spatial derivatives of these profiles, corrected for geometrical expansion, show that the diffuse component is consistent with a simple photodissociation process, but the jet component is not. The peak production of the jet profile occurs 6000 km from the nucleus at a heliocentric distance of 1.4 AU. Modeling of both components of the coma indicate results that are consistent with the diffuse CN photochemically produced, but the CN jets need an additional extended source. We found that about one-half of the CN in the coma of Comet P/Halley originated from the jets, the rest from the diffuse component. These features, along with the width of the jet being approximately constant, are consistent with a CHON grain origin for the jets.

Structural and magnetic diversity in cyano-bridged bi- and trimetallic complexes assembled from cyanometalates and [M(rac-CTH)]n+ building blocks (CTH = d,l-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane).

PubMed

Rodríguez-Diéguez, Antonio; Kivekäs, Raikko; Sillanpää, Reijo; Cano, Joan; Lloret, Francesc; McKee, Vickie; Stoeckli-Evans, Helen; Colacio, Enrique

2006-12-25

Seven new cyano-bridged heterometallic systems have been prepared by assembling [M'(rac-CTH)]n+ complexes (M' = CrIII, NiII, CuII), which have two cis available coordination positions, and [M(CN)6]3- (M = FeIII, CrIII) and [Fe(CN)2(bpy)2]+ cyanometalate building blocks. The assembled systems, which have been characterized by X-ray crystallography and magnetic investigations, are the molecular squares (meso-CTH-H2)[{Ni(rac-CTH)}2{Fe(CN)6)}2].5H2O (2) and [{Ni(rac-CTH)}2{Fe(CN)2(bpy)2}2](ClO4)4.H2O (5), the bimetallic chain [{Ni(rac-CTH)}2{Cr(CN)6)}2Ni(meso-CTH)].4H2O (3), the trimetallic chain [{Ni(rac-CTH)}2{Fe(CN)6)}2Cu(cyclam)]6H2O (4), the pentanuclear complexes [{Cu(rac-CTH}3{Fe(CN)6}2].2H2O (6) and [{Cu(rac-CTH)}3{Cr(CN)6)}2].2H2O (7), and the dinuclear complex [Cr(rac-CTH)(H2O)Fe(CN)6].2H2O (8). With the exception of 5, all compounds exhibit ferromagnetic interaction between the metal ions (JFeNi = 12.8(2) cm-1 for 2; J1FeCu= 13.8(2) cm-1 and J2FeCu= 3.9(4) cm-1 for 6; J1CrCu= 6.95(3) cm-1 and J2CrCu= 1.9(2)cm-1 for 7; JCrFe = 28.87(3) cm-1 for 8). Compound 5 exhibits the end of a transition from the high-spin to the low-spin state of the octahedral FeII ions. The bimetallic chain 3 behaves as a metamagnet with a critical field Hc = 300 G, which is associated with the occurrence of week antiferromagnetic interactions between the chains. Although the trimetallic chain 4 shows some degree of spin correlation along the chain, magnetic ordering does not occur. The sign and magnitude of the magnetic exchange interaction between CrIII and FeIII in compound 8 have been justified by DFT type calculations.

Copper(II) cyanido-bridged bimetallic nitroprusside-based complexes: Syntheses, X-ray structures, magnetic properties, {sup 57}Fe Moessbauer spectroscopy and thermal studies

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

Travnicek, Zdenek, E-mail: zdenek.travnicek@upol.c; Herchel, Radovan; Mikulik, Jiri

2010-05-15

Three heterobimetallic cyanido-bridged copper(II) nitroprusside-based complexes of the compositions [Cu(tet)Fe(CN){sub 5}NO].H{sub 2}O (1), where tet=N,N'-bis(3-aminopropyl)ethylenediamine, [Cu(hto)Fe(CN){sub 5}NO].2H{sub 2}O (2), where hto=1,3,6,9,11,14-hexaazatricyclo[12.2.1.1{sup 6,9}]octadecane and [Cu(nme){sub 2}Fe(CN){sub 5}NO].H{sub 2}O (3), where nme=N-methylethylenediamine, were synthesized and characterized by elemental analyses, {sup 57}Fe Moessbauer and FTIR spectroscopies, thermal analysis, magnetic measurements and single-crystal X-ray analysis. The products of thermal degradation processes of 2 and 3 were studied by XRD, {sup 57}Fe Moessbauer spectroscopy, SEM and EDS, and they were identified as mixtures of CuFe{sub 2}O{sub 4} and CuO. - Three heterobimetallic cyano-bridged copper(II) nitroprusside-based complexes of the general compositions of [Cu(L)Fe(CN){sub 5}NO].xH{sub 2}O, wheremore » L=N,N'-bis(3-aminopropyl)ethylenediamine (complex 1), 1,3,6,9,11,14-hexaazatricyclo[12.2.1.1{sup 6,9}]-octadecane (complex 2) and N-methylethylenediamine (complex 3), were synthesized, and fully structurally and magnetically characterized. SEM, EDS, XRD and {sup 57}Fe Moessbauer experiments were used for characterization of thermal decomposition products of complexes 2 and 3.« less

Two-State Intramolecular Charge Transfer (ICT) with 3,5-Dimethyl-4-(dimethylamino)benzonitrile (MMD) and Its Meta-Isomer mMMD. Ground State Amino Twist Not Essential for ICT.

PubMed

Druzhinin, Sergey I; Galievsky, Victor A; Demeter, Attila; Kovalenko, Sergey A; Senyushkina, Tamara; Dubbaka, Srinivas R; Knochel, Paul; Mayer, Peter; Grosse, Christian; Stalke, Dietmar; Zachariasse, Klaas A

2015-12-10

From X-ray structure analysis, amino twist angles of 90.0° for 2,4-dimethyl-3-(dimethylamino)benzonitrile (mMMD), 82.7° for 4-(di-tert-butylamino)benzonitrile (DTABN), and 88.7° for 6-cyanobenzoquinuclidine (CBQ) are determined, all considerably larger than the 57.4° of 3,5-dimethyl-4-(dimethylamino)benzonitrile (MMD). This large twist leads to lengthening of the amino-phenyl bond, 143.5 pm (mMMD), 144.1 pm (DTABN), 144.6 pm (CBQ), and 141.4 pm (MMD), as compared with 136.5 pm for the planar 4-(dimethylamino)benzonitrile (DMABN). As a consequence, the electronic coupling between the amino and phenyl subgroups in mMMD, DTABN, CBQ, and MMD is much weaker than in DMABN, as seen from the strongly reduced molar absorption coefficients. The fluorescence spectrum of MMD in n-hexane at 25 °C consists of two emissions, from a locally excited (LE) and an intramolecular charge transfer (ICT) state, with a fluorescence quantum yield ratio Φ'(ICT)/Φ(LE) of 12.8. In MeCN, a single ICT emission is found. With mMMD in n-hexane, in contrast, only LE fluorescence is observed, whereas the spectrum in MeCN originates from the ICT state. These differences are also seen from the half-widths of the overall fluorescence bands, which in n-hexane are larger for MMD than for mMMD, decreasing with solvent polarity for MMD and increasing for mMMD, reflecting the disappearance of LE and the onset of ICT in the overall spectra, respectively. From solvatochromic measurements the dipole moments μe(ICT) of MMD (16 D) and mMMD (15 D) are obtained. Femtosecond excited state absorption (ESA) spectra at 22 °C, together with the dual (LE + ICT) fluorescence, reveal that MMD in n-hexane undergoes a reversible LE ⇄ ICT reaction, with LE as the precursor, with a forward rate constant ka = 5.6 × 10(12) s(-1) and a back-reaction kd ∼ 0.05 × 10(12) s(-1). With MMD in the strongly polar solvent MeCN, ICT is faster: ka = 10 × 10(12) s(-1). In the case of mMMD in n-hexane, the ESA spectra show that ICT does not take place, contrary to MeCN, in which ka = 2.5 × 10(12) s(-1). The ICT reactions with MMD and mMMD are much faster than that of the parent compound DMABN in MeCN, with ka = 0.24 × 10(12) s(-1). Because of the very short ICT reaction times of 180 fs (MMD, n-hexane), 100 fs (MMD, MeCN), and 400 fs (mMMD, MeCN), it is clear that the picosecond fluorescence decays of these systems appear to be single exponential, due to the insufficient time resolution of 3 ps. It is concluded that the faster LE → ICT reaction of MMD as compared with DMABN (ka = 0.24 × 10(12) s(-1) in MeCN) is caused by a smaller energy gap ΔE(S1,S2) between the lowest singlet excited states and not by the large amino twist angle. Similarly, the larger ΔE(S1,S2) of mMMD as compared with MMD is held responsible for its smaller ICT efficiency (no reaction in n-hexane).

Boltzmann transport properties of ultra thin-layer of h-CX monolayers

NASA Astrophysics Data System (ADS)

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

2018-04-01

Structural, electronic and thermoelectric properties of monolayer h-CX (X= Al, As, B, Bi, Ga, In, P, N, Sb and Tl) have been computed using density functional theory (DFT). The structural, electronic band structure, phonon dispersion curves and thermoelectric properties have been investigated. h-CGa and h-CTl show the periodically lattice vibrations and h-CB and h-CIn show small imaginary ZA frequencies. Thermoelectric properties are obtained using BoltzTrap code with the constant relaxation time (τ) approximation such as electronic, thermal and electrical conductivity calculated for various temperatures. The results indicate that h-CGa, h-CIn, h-CTl and h-CAl have direct band gaps with minimum electronic thermal and electrical conductivity while h-CB and h-CN show the high electronic thermal and electrical conductivity with highest cohesive energy.

Synthesis and characterization of high quantum yield and oscillator strength 6-chloro-2-(4-cynophenyl)-4-phenyl quinoline (cl-CN-DPQ) organic phosphor for solid-state lighting.

PubMed

Ghate, Minakshi; Dahule, H K; Thejo Kalyani, N; Dhoble, S J

2018-03-01

A novel blue luminescent 6-chloro-2-(4-cynophenyl) substituted diphenyl quinoline (Cl-CN DPQ) organic phosphor has been synthesized by the acid-catalyzed Friedlander reaction and then characterized to confirm structural, optical and thermal properties. Structural properties of Cl-CN-DPQ were analyzed by Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction technique (XRD) and scanning electron microscopy (SEM) and energy dispersive analysis of X-ray (EDAX) spectroscopy. FTIR spectra confirmed the presence of different functional groups and bond stretching. 1 H-NMR and 13 C-NMR confirmed the formation of an organic Cl-CN-DPQ compound. X-ray diffraction study provided its crystalline nature. The surface morphology of Cl-CN-DPQ was analyzed by SEM, while EDAX spectroscopy revealed the elemental analysis. Differential thermal analysis (TGA/DTA) disclosed its thermal stability up to 250°C. The optical properties of Cl-CN-DPQ were investigated by UV-vis absorption and photoluminescence (PL) measurements. Cl-CN-DPQ exhibits intense blue emission at 434 nm in a solid-state crystalline powder with CIE co-ordinates (0.157, 0.027), when excited at 373 nm. Cl-CN-DPQ shows remarkable Stokes shift in the range 14800-5100 cm -1 , which is the characteristic feature of intense light emission. A narrow full width at half-maximum (FWHM) value of PL spectra in the range 42-48 nm was observed. Oscillator strength, energy band gap, quantum yield, and fluorescence energy yield were also examined using UV-vis absorption and photoluminescence spectra. These results prove its applications towards developing organic luminescence devices and displays, organic phosphor-based solar cells and displays, organic lasers, chemical sensors and many more. Copyright © 2017 John Wiley & Sons, Ltd.

SCS-CN based time-distributed sediment yield model

NASA Astrophysics Data System (ADS)

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.

Self powered sensing by combining novel sensor architectures with energy harvesting

NASA Astrophysics Data System (ADS)

Bedekar, Vishwas Narayan

The sensing techniques investigated in this thesis utilize piezoelectric materials, piezoresistive materials, and magnetoelectric composites. Prior studies on structural health monitoring have demonstrated the use and promise of piezoelectric sensors. In this research, impedance spectroscopy based sensing technique was investigated with respect to two parameters (i) effect of the piezoelectric vibration mode on damage index metric, and (ii) selection of frequency band through manipulation of the electrode size and shape. These results were then used to determine sensor geometry and dimensions for detecting surface defects, fatigue and corrosion. Based upon these results, power requirement for structural health monitoring sensors was determined. Next, piezoelectric materials were coupled with magnetostrictive material for novel magnetic field gradient sensing. The ceramic -- ceramic (CC) gradiometer resembles in functionality a magnetoelectric transformer. It measures the magnetic field gradient and sensitivity with respect to a reference value. The CC gradiometer designed in this study was based upon the magnetoelectric (ME) composites and utilizes the ring-dot piezoelectric transformer structure working near resonance as the basis. This study investigated the gradiometer design and characterized the performance of gradiometer based upon Terfenol--D -- PZT composites. Based upon these results, next a metal -- ceramic gradiometer consisting of PZT and nickel was designed and characterized. In this thesis, two different designs of gradiometer with nickel and PZT laminate composites were fabricated. Nickel was chosen over other materials considering its co-firing ability with PZT. It can give a better control over dimensional parameters of the gradiometer sample and further size reduction is possible with tape casting technique. Detailed theoretical analysis was conducted in order to understand the experimental results. In order to significantly reduce the power consumption of health monitoring and magnetic field sensors, bottom -- up design of structural health monitoring and magnetic field sensors was investigated. A MWCNT/SiCN nanotube template was developed that exhibits piezoresistive effect. Next, a novel nanotube morphology "nanoNecklace" was synthesized that consists of BaTiO 3 (BTO) nanoparticles decorated along the surface of SiCN. Monolayer coating of SiCN on MWCNT serves two purposes: (i) modifies the surface wetting characteristics, and (ii) enhances the piezoresistive effect. Investigation of the mechanisms that provide periodic arrangement of BTO on nanotube surface was conducted using HRTEM and contact angle measurements. Next, we tried to modify the surface wetting characteristics of MWCNTs in order to get a full coating of BTO nanoparticles. The SiCN/MWCNT approach was further extended to fabricate magnetoelectric nanowire based sensors designs. In this approach a SiCN-NT template was coated with BTO and CoFe2O4 (CFO) nanoparticles. Microstructural studies indicated the presence of piezoelectric (BTO) as well as magnetic (CFO) material on the nanotube surface. In order to power the sensors from mechanical vibrations, we investigated two different techniques, (i) piezoelectric and (ii) inductive. An analytical model for energy harvesting from bimorph transducer was developed which was confirmed by experimental measurements. The results show that power density of bimorph transducer can be enhanced by increasing the magnitude of product (d.g), where d is the piezoelectric strain constant and g is the piezoelectric voltage constant. Under inductive energy harvesting, we designed and fabricated a small scale harvester that was integrated inside a pen commonly carried by humans to harvest vibration energy. Inductive energy harvesting was selected in order to achieve high power at lower frequencies. The prototype cylindrical harvester was found to generate 3mW at 5 Hz and 1mW at 3.5 Hz operating under displacement amplitude of 16mm (corresponding to an acceleration of approximately 1.14 grms at 5Hz and 0.56 grms at 3.5 Hz, respectively). (Abstract shortened by UMI.)

Microstructural, textural, and sensory characteristics of probiotic yogurts fortified with sodium calcium caseinate or whey protein concentrate.

PubMed

Akalın, A S; Unal, G; Dinkci, N; Hayaloglu, A A

2012-07-01

The influence of milk protein-based ingredients on the textural characteristics, sensory properties, and microstructure of probiotic yogurt during a refrigerated storage period of 28 d was studied. Milk was fortified with 2% (wt/vol) skim milk powder as control, 2% (wt/vol) sodium calcium caseinate (SCaCN), 2% (wt/vol) whey protein concentrate (WPC) or a blend of 1% (wt/vol) SCaCN and 1% (wt/vol) WPC. A commercial yogurt starter culture and Bifidobacterium lactis Bb12 as probiotic bacteria were used for the production. The fortification with SCaCN improved the firmness and adhesiveness. Higher values of viscosity were also obtained in probiotic yogurts with SCaCN during storage. However, WPC enhanced water-holding capacity more than the caseinate. Addition of SCaCN resulted in a coarse, smooth, and more compact protein network; however, WPC gave finer and bunched structures in the scanning electron microscopy micrographs. The use of SCaCN decreased texture scores in probiotic yogurt; probably due to the lower water-holding capacity and higher syneresis values in the caseinate-added yogurt sample. Therefore, the textural characteristics of probiotic yogurts improved depending on the ingredient variety. Copyright © 2012 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Group 1 and group 2 metal complexes supported by a bidentate bulky iminopyrrolyl ligand: synthesis, structural diversity, and ε-caprolactone polymerization study.

PubMed

Kottalanka, Ravi K; Harinath, A; Rej, Supriya; Panda, Tarun K

2015-12-14

We report here a series of alkali and alkaline earth metal complexes, each with a bulky iminopyrrolyl ligand [2-(Ph3CN=CH)C4H3NH] (1-H) moiety in their coordination sphere, synthesized using either alkane elimination or silylamine elimination methods or the salt metathesis route. The lithium salt of molecular composition [Li(2-(Ph3CN=CH)C4H3N)(THF)2] (2) was prepared using the alkane elimination method, and the silylamine elimination method was used to synthesize the dimeric sodium and tetra-nuclear potassium salts of composition [(2-(Ph3CN=CH)C4H3N)Na(THF)]2 (3) and [(2-(Ph3CN=CH)C4H3N)K(THF)0.5]4 (4) respectively. The magnesium complex of composition [(THF)2Mg(CH2Ph){2-(Ph3CN=CH)C4H3N}] (5) was synthesized through the alkane elimination method, in which [Mg(CH2Ph)2(OEt2)2] was treated with the bulky iminopyrrole ligand 1-H in 1 : 1 molar ratio, whereas the bis(iminopyrrolyl)magnesium complex [(THF)2Mg{2-(Ph3CN=CH)C4H3N}2] (6) was isolated using the salt metathesis route. The heavier alkaline earth metal complexes of the general formula {(THF)nM(2-(Ph3CN=CH)C4H3N)2} [M = Ca (7), Sr (8), and n = 2; M = Ba (9), n = 3] were prepared in pure form using two synthetic methods: in the first method, the bulky iminopyrrole ligand 1-H was directly treated with the alkaline earth metal precursor [M{N(SiMe3)2}2(THF)n] (where M = Ca, Sr and Ba) in 2 : 1 molar ratio in THF solvent at ambient temperature. The complexes 7-9 were also obtained using the salt metathesis reaction, which involves the treatment of the potassium salt (4) with the corresponding metal diiodides MI2 (M = Ca, Sr and Ba) in 2 : 1 molar ratio in THF solvent. The molecular structures of all the metal complexes (1-H, 2-9) in the solid state were established through single-crystal X-ray diffraction analysis. The complexes 5-9 were tested as catalysts for the ring-opening polymerization of ε-caprolactone. High activity was observed in the heavier alkaline earth metal complexes 7-9, with a very narrow polydispersity index in comparison to that of magnesium complexes 5 and 6.

Effect of the metal environment on the ferromagnetic interaction in the Co-NC-W pairs of octacyanotungstate(V)-Cobalt(II) three-dimensional networks.

PubMed

Clima, Sergiu; Hendrickx, Marc F A; Chibotaru, Liviu F; Soncini, Alessandro; Mironov, Vladimir; Ceulemans, Arnout

2007-04-02

State of the art CASSCF and CASPT2 calculations have been performed to elucidate the nature of ferromagnetism of CoII-NC-WV pairs in the three-dimensional compound [[WV(CN)2]2[(micro-CN)4CoII(H2O)2]3.4H2O]n, which has been recently synthesized and investigated by a number of experimental techniques (Herrera, J. M.; Bleuzen, A.; Dromzée, Y.; Julve, M.; Lloret, F.; Verdaguer, M. Inorg. Chem. 2003, 42, 7052-7059). In this network, the Co ions are in the high-spin (S = 3/2) state, while the single unpaired electron on the W centers occupies the lowest orbital of the dz2 type of the 5d shell. In agreement with the suggestion made by Herrera et al., we find that the ferromagnetism is due to a certain occupation scheme of the orbitals from the parent octahedral t2g shell on CoII sites, in which the orbital accommodating the unpaired electron is orthogonal to the dz2 orbitals of the surrounding W ions. We investigate the stabilization of such an orbital configuration on the Co sites and find that it cannot be achieved in the ground state of isolated mononuclear fragments [CoII(NC)4(OH2)2]2- for any conformations of the coordinated water molecules and Co-N-C bond angles. On the other hand, it is stabilized by the interaction of the complex with neighboring W ions, which are simulated here by effective potentials. The calculated exchange coupling constants for the CoII-NC-WV binuclear fragments are in reasonable agreement with the measured Curie-Weiss constant for this compound. As additional evidence for the inferred electronic configuration on the Co sites, the ligand-field transitions, the temperature-dependent magnetic susceptibility, and the field-dependent low-temperature magnetization, simulated ab initio for the mononuclear Co fragments, are in agreement with the available data for another compound [WIV[(micro-CN)4-CoII(H2O)2]2.4H2O]n containing diamagnetic W and high-spin Co ions in an isostructural environment.

Cross-linked g-C3 N4 /rGO nanocomposites with tunable band structure and enhanced visible light photocatalytic activity.

PubMed

Li, Yibing; Zhang, Haimin; Liu, Porun; Wang, Dan; Li, Ying; Zhao, Huijun

2013-10-11

Cross-linked rather than non-covalently bonded graphitic carbon nitride (g-C3 N4 )/reduced graphene oxide (rGO) nanocomposites with tunable band structures have been successfully fabricated by thermal treatment of a mixture of cyanamide and graphene oxide with different weight ratios. The experimental results indicate that compared to pure g-C3 N4 , the fabricated CN/rGO nanocomposites show narrowed bandgaps with an increased in the rGO ratio. Furthermore, the band structure of the CN/rGO nanocomposites can be readily tuned by simply controlling the weight ratio of the rGO. It is found that an appropriate rGO ratio in nanocomposite leads to a noticeable positively shifted valence band edge potential, meaning an increased oxidation power. The tunable band structure of the CN/rGO nanocomposites can be ascribed to the formation of C-O-C covalent bonding between the rGO and g-C3 N4 layers, which is experimentally confirmed by Fourier transform infrared (FT-IR) and X-ray photoelectron (XPS) data. The resulting nanocomposites are evaluated as photocatalysts by photocatalytic degradation of rhodamine B (RhB) and 4-nitrophenol under visible light irradiation (λ > 400 nm). The results demonstrate that the photocatalytic activities of the CN/rGO nanocomposites are strongly influenced by rGO ratio. With a rGO ratio of 2.5%, the CN/rGO-2.5% nanocomposite exhibits the highest photocatalytic efficiency, which is almost 3.0 and 2.7 times that of pure g-C3 N4 toward photocatalytic degradation of RhB and 4-nitrophenol, respectively. This improved photocatalytic activity could be attributed to the improved visible light utilization, oxidation power, and electron transport property, due to the significantly narrowed bandgap, positively shifted valence band-edge potential, and enhanced electronic conductivity. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation of hydroxyl radicals and kinetic study of 2-chlorophenol photocatalytic oxidation using C-doped TiO2, N-doped TiO2, and C,N Co-doped TiO2 under visible light.

PubMed

Ananpattarachai, Jirapat; Seraphin, Supapan; Kajitvichyanukul, Puangrat

2016-02-01

This work reports on synthesis, characterization, adsorption ability, formation rate of hydroxyl radicals (OH(•)), photocatalytic oxidation kinetics, and mineralization ability of C-doped titanium dioxide (TiO2), N-doped TiO2, and C,N co-doped TiO2 prepared by the sol-gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy were used to analyze the titania. The rate of formation of OH(•) for each type of titania was determined, and the OH-index was calculated. The kinetics of as-synthesized TiO2 catalysts in photocatalytic oxidation of 2-chlorophenol (2-CP) under visible light irradiation were evaluated. Results revealed that nitrogen was incorporated into the lattice of titania with the structure of O-Ti-N linkages in N-doped TiO2 and C,N co-doped TiO2. Carbon was joined to the Ti-O-C bond in the C-doped TiO2 and C,N co-doped TiO2. The 2-CP adsorption ability of C,N co-doped TiO2 and C-doped TiO2 originated from a layer composed of a complex carbonaceous mixture at the surface of TiO2. C,N co-doped TiO2 had highest formation rate of OH(•) and photocatalytic activity due to a synergistic effect of carbon and nitrogen co-doping. The order of photocatalytic activity per unit surface area was the same as that of the formation rate of OH(•) unit surface area in the following order: C,N co-doped TiO2 > C-doped TiO2 > N-doped TiO2 > undoped TiO2.

[Analysis on the impact of composting with different proportions of corn stalks and pig manure on humic acid fractions and IR spectral feature].

PubMed

Sun, Xiang-Ping; Li, Guo-Xue; Xiao, Ai-Ping; Shi, Hong; Wang, Yi-Ming; Li, Yang-Yang

2014-09-01

Using pig manure and corn straw as raw materials for high-temperature composting, setting three different treat- ments: C/N 15, C/N 25, and C/N 35. Composting period is 120 days, which contains 30 days for ventilation cycle by forced continuous ventilation. Sampled on 0, 22, 30, 60, 90, 120th days, they were analyzed by elemental analysis and IR spectroscopy to study effect of different lignin content on compost humic acid (HA) composition and molecular structure. The results showed that the change in composting humic acid C focused on the first 30 days, while after composting, the O/C of compost HA increased, H/C decreased, and N content increased. Low C/N (15) and higher C/N ratio (35) had higher degree of oxidation than the C/N 25 in compost HA. FTIR indicated that the infrared spectrum shapes with different lignin content treatment are similar during the composting process, but the peak intensity is obviously different. Research results proved that the composting stage is more conducive to enhanced aromatic in compost HA. After composting, C/N 15 had less polysaccharide and fat ingredients and more aromatic structural components in compost HA, compared with C/N 25 and 35. In addition, compost HA of C/N 15 had higher degree of humification and its structure was more stable.

Soft x-ray absorption spectroscopy study of the electronic structures of the MnFe Prussian blue analogs (RbxBay) Mn[3 -(x +2 y )]/2[Fe (CN) 6] H2O

NASA Astrophysics Data System (ADS)

Lee, Eunsook; Seong, Seungho; Kim, Hyun Woo; Kim, D. H.; Thakur, Nidhi; Yusuf, S. M.; Kim, Bongjae; Min, B. I.; Kim, Younghak; Kim, J.-Y.; de Groot, F. M. F.; Kang, J.-S.

2017-11-01

The electronic structures of Prussian blue analog (RbxBay) Mn[3 -(x +2 y )]/2[Fe (CN) 6] cyanides have been investigated by employing soft x-ray absorption spectroscopy (XAS) and magnetic circular dichroism (XMCD) at the Fe and Mn L (2 p ) edges. The measured XAS spectra have been analyzed with the configuration-interaction (CI) cluster model calculations. The valence states of the Fe and Mn ions are found to be Fe2 +-Fe3 + mixed valent, with an average valency of v (Fe )˜2.8 and nearly divalent (Mn2 +), respectively. Our Mn/Fe 2 p XMCD study supports that Mn2 + ions are in the high-spin states while Fe2 +-Fe3 + ions are in the low-spin states. The Fe and Mn 2 p XAS spectra are found to be essentially the same for 80 ≤T ≤ 300 K, suggesting that a simple charge transfer upon cooling from Fe3 +-CN -Mn2 + to Fe2 +-CN -Mn3 + does not occur in (RbxBay) Mn[3 -(x +2 y )]/2[Fe (CN) 6] . According to the CI cluster model analysis, it is necessary to take into account both the ligand-to-metal charge transfer and the metal-to-ligand charge transfer in describing Fe 2 p XAS, while the effect of charge transfer is negligible in describing Mn 2 p XAS. The CI cluster model analysis also shows that the trivalent Fe3 + ions have a strong covalent bonding with the C ≡N ligands and are under a large crystal-field energy of 10 D q ˜3 eV, in contrast to the weak covalency effect and a small 10 D q ˜0.6 eV for the divalent Mn2 + ions.

K 3 Fe(CN) 6 under External Pressure: Dimerization of CN – Coupled with Electron Transfer to Fe(III)

DOE PAGES

Li, Kuo; Zheng, Haiyan; Wang, Lijuan; ...

2015-09-14

The addition polymerization of charged monomers like C≡C 2– and C≡N– is scarcely seen at ambient conditions but can progress under external pressure with their conductivity significantly enhanced, which expands the research field of polymer science to inorganic salts. Moreover, the reaction pressures of transition metal cyanides like Prussian blue and K 3Fe(CN) 6 are much lower than that of alkali cyanides. To figure out the effect of the transition metal on the reaction, the crystal structure and electronic structure of K 3Fe(CN) 6 under external pressure are investigated by in situ neutron diffraction, in situ X-ray absorption fine structuremore » (XAFS), and neutron pair distribution functions (PDF) up to ~15 GPa. The cyanide anions react following a sequence of approaching–bonding–stabilizing. The Fe(III) brings the cyanides closer which makes the bonding progress at a low pressure (2–4 GPa). At ~8 GPa, an electron transfers from the CN to Fe(III), reduces the charge density on cyanide ions, and stabilizes the reaction product of cyanide. Finally, from this study we can conclude that bringing the monomers closer and reducing their charge density are two effective routes to decrease the reaction pressure, which is important for designing novel pressure induced conductor and excellent electrode materials.« less

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

PubMed

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.

Polymer-Derived Ceramic Functionalized MoS2 Composite Paper as a Stable Lithium-Ion Battery Electrode

NASA Astrophysics Data System (ADS)

David, L.; Bhandavat, R.; Barrera, U.; Singh, G.

2015-04-01

A facile process is demonstrated for the synthesis of layered SiCN-MoS2 structure via pyrolysis of polysilazane functionalized MoS2 flakes. The layered morphology and polymer to ceramic transformation on MoS2 surfaces was confirmed by use of electron microscopy and spectroscopic techniques. Tested as thick film electrode in a Li-ion battery half-cell, SiCN-MoS2 showed the classical three-stage reaction with improved cycling stability and capacity retention than neat MoS2. Contribution of conversion reaction of Li/MoS2 system on overall capacity was marginally affected by the presence of SiCN while Li-irreversibility arising from electrolyte decomposition was greatly suppressed. This is understood as one of the reasons for decreased first cycle loss and increased capacity retention. SiCN-MoS2 in the form of self-supporting paper electrode (at 6 mg.cm-2) exhibited even better performance, regaining initial charge capacity of approximately 530 mAh.g-1 when the current density returned to 100 mA.g-1 after continuous cycling at 2400 mA.g-1 (192 mAh.g-1). MoS2 cycled electrode showed mud-cracks and film delamination whereas SiCN-MoS2 electrodes were intact and covered with a uniform solid electrolyte interphase coating. Taken together, our results suggest that molecular level interfacing with precursor-derived SiCN is an effective strategy for suppressing the metal-sulfide/electrolyte degradation reaction at low discharge potentials.

Synthesis, characterization, DFT calculations and antibacterial activity of palladium(II) cyanide complexes with thioamides

NASA Astrophysics Data System (ADS)

Ahmad, Saeed; Nadeem, Shafqat; Anwar, Aneela; Hameed, Abdul; Tirmizi, Syed Ahmed; Zierkiewicz, Wiktor; Abbas, Azhar; Isab, Anvarhusein A.; Alotaibi, Mshari A.

2017-08-01

Palladium(II) cyanide complexes of thioamides (or thiones) having the general formula PdL2(CN)2, where L = Thiourea (Tu), Methylthiourea (Metu), N,N‧-Dimethylthiourea (Dmtu), Tetramethylthiourea (Tmtu), 2-Mercaptopyridine (Mpy) and 2-Mercaptopyrimidine (Mpm) were prepared by reacting K2[PdCl4] with potassium cyanide and thioamides in the molar ratio of 1:2:2. The complexes were characterized by elemental analysis, thermal and spectroscopic methods (IR, 1H and 13C NMR). The structures of three of the complexes were predicted by DFT calculations. The appearance of a band around 2100 cm-1 in IR and resonances around 120-130 ppm in the 13C NMR spectra indicated the coordination of cyanide to palladium(II). More than one resonances were observed for CN- carbon atoms in 13C NMR indicating the existence of equilibrium between different species in solution. DFT calculations revealed that in the case of the palladium(II) complex of Tmtu, the ionic dinuclear [Pd(Tmtu)4][Pd(CN)4] form was more stable than the dimer of mononuclear complex [Pd(Tmtu)2(CN)2] by 0.91 kcal mol-1, while for the complexes of Tu or Mpy ligands, the nonionic [Pd(L)2(CN)2] forms were more stable than the corresponding [Pd(L)4][Pd(CN)4] complexes by 1.26 and 6.49 kcal mol-1 for L = Tu and Mpy, respectively. The complexes were screened for antibacterial effects and some of them showed significant activities against both gram positive as well as gram negative bacteria.

Gaussian versus flat-top spatial beam profiles for optical stimulation of the prostate nerves

NASA Astrophysics Data System (ADS)

Tozburun, Serhat; Lagoda, Gwen A.; Burnett, Arthur L.; Fried, Nathaniel M.

2010-02-01

The cavernous nerves (CN) course along the prostate surface and are responsible for erectile function. Improved identification and preservation of the CN's is critical to maintaining sexual potency after prostate cancer surgery. Noncontact optical nerve stimulation (ONS) of the CN's was recently demonstrated in a rat model, in vivo, as a potential alternative to electrical nerve stimulation (ENS) for identification of the CN's during prostate surgery. However, the therapeutic window for ONS is narrow, so optimal design of the fiber optic delivery system is critical for safe, reproducible stimulation. This study describes modeling, assembly, and testing of an ONS probe for delivering a small, collimated, flat-top laser beam for uniform CN stimulation. A direct comparison of the magnitude and response time of the intracavernosal pressure (ICP) for both Gaussian and flat-top spatial beam profiles was performed. Thulium fiber laser radiation (λ=1870 nm) was delivered through a 200-μm fiber, with distal fiber tip chemically etched to convert a Gaussian to flat-top beam profile. The laser beam was collimated to a 1-mm-diameter spot using an aspheric lens. Computer simulations of light propagation were used to optimize the probe design. The 10-Fr (3.4-mm-OD) laparoscopic probe provided a constant radiant exposure at the CN surface. The probe was tested in four rats, in vivo. ONS of the CN's was performed with a 1-mm-diameter spot, 5-ms pulse duration, and pulse rate of 20 Hz for a duration of 15-30 s. The flat-top laser beam profile consistently produced a faster and higher ICP response at a lower radiant exposure than the Gaussian beam profile due, in part, to easier alignment of the more uniform beam with nerve. The threshold for ONS was approximately 0.14 J/cm2, corresponding to a temperature increase of 6-8°C at the CN surface after a stimulation time of 15 s. With further development, ONS may be used as a diagnostic tool for identification of CN's during prostate cancer surgery.

Pentacoordinate and Hexacoordinate Mn(III) Complexes of Tetradentate Schiff-Base Ligands Containing Tetracyanidoplatinate(II) Bridges and Revealing Uniaxial Magnetic Anisotropy.

PubMed

Nemec, Ivan; Herchel, Radovan; Trávníček, Zdeněk

2016-12-08

Crystal structures and magnetic properties of polymeric and trinuclear heterobimetallic Mn III ···Pt II ···Mn III coordination compounds, prepared from the Ba[Pt(CN)₄] and [Mn(L4A/B)(Cl)] ( 1a / b ) precursor complexes, are reported. The polymeric complex [{Mn(L4A)}₂{μ⁴-Pt(CN)₄}] n ( 2a ), where H₂L4A = N , N '-ethylene-bis(salicylideneiminate), comprises the {Mn(L4A)} moieties covalently connected through the [Pt(CN)₄] 2- bridges, thus forming a square-grid polymeric structure with the hexacoordinate Mn III atoms. The trinuclear complex [{Mn(L4B)}₂{μ-Pt(CN)₄}] ( 2b ), where H₂L4B = N , N '-benzene-bis(4-aminodiethylene-salicylideneiminate), consists of two [{Mn(L4B)} moieties, involving pentacoordinate Mn III atoms, bridged through the tetracyanidoplatinate (II) bridges to which they are coordinated in a trans fashion. Both complexes possess uniaxial type of magnetic anisotropy, with D (the axial parameter of zero-field splitting) = -3.7(1) in 2a and -2.2(1) cm -1 in 2b . Furthermore, the parameters of magnetic anisotropy 2a and 2b were also thoroughly studied by theoretical complete active space self-consistent field (CASSCF) methods, which revealed that the former is much more sensitive to the ligand field strength of the axial ligands.

The structure and energetics of the HCN → HNC transition state

NASA Astrophysics Data System (ADS)

Lee, Timothy J.; Rendell, Alistair P.

1991-03-01

The optimum geometries and quadratic force constants of HCN, HNC and the transition state connecting them have been determined at the single and double excitation coupled-cluster (CCSD) and CCSD(T) levels of theory. Energy differences were evaluated using the CCSD and CCSD(T) methods in conjunction with large atomic natural orbital basis sets containing g-type basis functions on the heavy atoms and f-type functions on hydrogen. The most reliable structure obtained for the transition state has bond distances of 1.194, 1.188 and 1.389 Å for rCN, rCH and rNH, respectively. Including a correction for zero-point vibrational energies, the transition state is predicted to be 44.6 ± 1.0 kcal/mol above the HCN isomer, while HNC is predicted to be 14.4 ± 1.0 kcal/mol above HCN. The latter value is in excellent agreement with the most recent experimental determination (14.8 ± 2.0 kcal/mol).

A high level Ab initio study of the anionic hydrogen-bonded complexes FH-CN-, FH-NC-, H2O-CN- and H2O-NC-

NASA Technical Reports Server (NTRS)

Lee, Timothy J.

1989-01-01

HF, H2O, CN- and their hydrogen-bonded complexes were studied using state-of-the-art ab initio quantum mechanical methods. A large Gaussian one particle basis set consisting of triple zeta plus double polarization plus diffuse s and p functions (TZ2P + diffuse) was used. The theoretical methods employed include self consistent field, second order Moller-Plesset perturbation theory, singles and doubles configuration interaction theory and the singles and doubles coupled cluster approach. The FH-CN- and FH-NC- and H2O-CN-, H2O-NC- pairs of complexes are found to be essentially isoenergetic. The first pair of complexes are predicted to be bound by approx. 24 kcal/mole and the latter pair bound by approximately 15 kcal/mole. The ab initio binding energies are in good agreement with the experimental values. The two being shorter than the analogous C-N hydrogen bond. The infrared (IR) spectra of the two pairs of complexes are also very similar, though a severe perturbation of the potential energy surface by proton exchange means that the accurate prediction of the band center of the most intense IR mode requires a high level of electronic structure theory as well as a complete treatment of anharmonic effects. The bonding of anionic hydrogen-bonded complexes is discussed and contrasted with that of neutral hydrogen-bonded complexes.

Ab initio investigation of Ti2Al(C,N) solid solutions

NASA Astrophysics Data System (ADS)

Arróyave, Raymundo; Radovic, Miladin

2011-10-01

Mn+1AXn phases (M: early transition metal, A: IIIA- or IVA-group element, X: carbon or nitrogen) are layered ternary compounds that possess both metal- and ceramic-like properties with numerous potential applications in bulk and thin film forms, particularly under high-temperature conditions. In this work, we use the cluster expansion formalism to investigate the energetics of C-N interactions across the entire Ti2AlC-Ti2AlN composition range. It is shown that there is a definite tendency for ordering in the C,N sublattice. However, the molar volume and bulk modulus of the ordered structures found along the Ti2AlC-Ti2AlN composition range show small deviations from the (linear) rule of mixing, indicating that despite the ordering tendencies, the C-N interactions are not strong and the solution becomes disordered at relatively low temperatures. Random solid solutions of Ti2AlC1-xNx are simulated using special quasirandom structures (SQS) with x=0.25, 0.50, and 0.75. The thermodynamic properties of these structures are compared to those of the structures found to belong to the ground state through the cluster expansion approach. It is found that the structural properties of these approximations to random alloys do not deviate significantly from Vegard's law. The trend in the structural parameters of these SQS are found to agree well with available experimental data and the predictions of the bulk modulus suggest a very weak alloying effect—with respect to Vegard's law—on the elastic properties of Ti2AlC1-xNx.

Synthesis, Structure, Characterization, and Decomposition of Nickel Dithiocarbamates: Effect of Precursor Structure and Processing Conditions on Solid-State Products

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Kulis, Michael J.; McNatt, Jeremiah S.; Duffy, Norman V.; Hoops, Michael D.; Gorse, Elizabeth; Fanwick, Philip E.; Masnovi, John; Cowen, Jonathan E.; Dominey, Raymond N.

2016-01-01

Single-crystal X-ray structures of four nickel dithiocarbamate complexes, the homoleptic mixed-organic bis-dithiocarbamates Ni[S2CN(isopropyl)(benzyl)]2, Ni[S2CN(ethyl)(n-butyl)]2, and Ni[S2CN(phenyl)(benzyl)]2, as well as the heteroleptic mixed-ligand complex NiCl[P(phenyl)3][(S2CN(phenyl)(benzyl)], were determined. Synthetic, spectroscopic, structural, thermal, and sulfide materials studies are discussed in light of prior literature. The spectroscopic results are routine. A slightly distorted square-planar nickel coordination environment was observed for all four complexes. The organic residues adopt conformations to minimize steric interactions. Steric effects also may determine puckering, if any, about the nickel and nitrogen atoms, both of which are planar or nearly so. A trans-influence affects the Ni-S bond distances. Nitrogen atoms interact with the CS2 carbons with a bond order of about 1.5, and the other substituents on nitrogen display transoid conformations. There are no strong intermolecular interactions, consistent with prior observations of the volatility of nickel dithiocarbamate complexes. Thermogravimetric analysis of the homoleptic species under inert atmosphere is consistent with production of 1:1 nickel sulfide phases. Thermolysis of nickel dithiocarbamates under flowing nitrogen produced hexagonal or -NiS as the major phase; thermolysis under flowing forming gas produced millerite (-NiS) at 300 C, godlevskite (Ni9S8) at 325 and 350 C, and heazlewoodite (Ni3S2) at 400 and 450 C. Failure to exclude oxygen results in production of nickel oxide. Nickel sulfide phases produced seem to be primarily influenced by processing conditions, in agreement with prior literature. Nickel dithiocarbamate complexes demonstrate significant promise to serve as single-source precursors to nickel sulfides, a quite interesting family of materials with numerous potential applications.

Exploring structural properties of small carbon clusters Cn (n = 1, 2, 3) using molecular mechanics and energy minimization

NASA Astrophysics Data System (ADS)

Miswan, M. A.; Gopir, G.; Anas, M. M.

2016-11-01

Geometry optimization is one of the most widely used methods to study in carbon cluster Cn to understand its structural properties. The total energy for each of the structures was calculated using Octopus software with conjugate gradient Broyden-Fletcher-Goldfarb-Shanno (CG-BFGS). Our calculation and other studies indicate that the linear forms are the most stable structures. However, the C3 isomers have equal probability to form, as the differences in our calculation of total energy are statistically insignificant. Despite there are two cohort of total energy, the calculations are acceptable due to the energy ratio between C3 to C2 and C2 to C1 are comparable to others work. Meanwhile, the bond properties of the C2 and C3 bonds also gives significant difference between our work and previous study.

Photomagnetic Switching of the Complex [Nd(dmf)[subscript 4](H[subscript 2]O)[subscript 3]([mu]-CN)Fe(CN)[subscript 5

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

Svendsen, Helle; Overgaard, Jacob; Chevallier, Marie

2009-10-21

Single-crystal XRD experiments (see picture) reveal the excited-state structure of the photomagnetic heterobimetallic title complex. The system shows a decrease in all the iron-ligand bond lengths, suggesting that photoexcitation involves a ligand-to-metal charge transfer or a change in the superexchange coupling between the metal centers.

Probabilistic properties of the Curve Number

NASA Astrophysics Data System (ADS)

Rutkowska, Agnieszka; Banasik, Kazimierz; Kohnova, Silvia; Karabova, Beata

2013-04-01

The determination of the Curve Number (CN) is fundamental for the hydrological rainfall-runoff SCS-CN method which assesses the runoff volume in small catchments. The CN depends on geomorphologic and physiographic properties of the catchment and traditionally it is assumed to be constant for each catchment. Many practitioners and researchers observe, however, that the parameter is characterized by a variability. This sometimes causes inconsistency in the river discharge prediction using the SCS-CN model. Hence probabilistic and statistical methods are advisable to investigate the CN as a random variable and to complement and improve the deterministic model. The results that will be presented contain determination of the probabilistic properties of the CNs for various Slovakian and Polish catchments using statistical methods. The detailed study concerns the description of empirical distributions (characteristics, QQ-plots and coefficients of goodness of fit, histograms), testing of the statistical hypotheses about some theoretical distributions (Kolmogorov-Smirnow, Anderson-Darling, Cramer-von Mises, χ2, Shapiro-Wilk), construction of confidence intervals and comparisons among catchments. The relationship between confidence intervals and the ARC soil classification will also be performed. The comparison between the border values of the confidence intervals and the ARC I and ARC III conditions is crucial for further modeling. The study of the response of the catchment to the stormy rainfall depth when the variability of the CN arises is also of special interest. ACKNOWLEDGMENTS The investigation described in the contribution has been initiated by first Author research visit to Technical University of Bratislava in 2012 within a STSM of the COST Action ES0901. Data used here have been provided by research project no. N N305 396238 founded by PL-Ministry of Science and Higher Education. The support provided by the organizations is gratefully acknowledged.

Surface-attached and suspended bacterial community structure as affected by C/N ratios: relationship between bacteria and fish production.

PubMed

Yu, Ermeng; Xie, Jun; Wang, Jinlin; Ako, Harry; Wang, Guangjun; Chen, Zhanghe; Liu, Yongfeng

2016-07-01

Bacteria play crucial roles in the combined system of substrate addition and C/N control, which has been demonstrated to improve aquaculture production. However, the complexity of surface-attached bacteria on substrates and suspended bacteria in the water column hamper further application of this system. This study firstly applied this combined system into the culture of grass carp, and then explored the relationship between microbial complexes from surface-attached and suspended bacteria in this system and the production of grass carp. In addition, this study investigated bacterial community structures as affected by four C/N ratios using Illumina sequencing technology. The results demonstrated that the weight gain rate and specific growth rate of grass carp in the CN20 group (C/N ratio 20:1) were the highest (P < 0.05), and dietary supplementation of the microbial complex had positive effects on the growth of grass carp (P < 0.05). Sequencing data revealed that, (1) the proportions of Verrucomicrobiae and Rhodobacter (surface-attached), sediminibacterium (suspended), and emticicia (surface-attached and suspended) were much higher in the CN20 group compared with those in the other groups (P < 0.05); (2) Rhodobacter, Flavobacterium, Acinetobacter, Pseudomonas, Planctomyces, and Cloacibacterium might be important for the microbial colonization on substrates; (3) as the C/N ratio increased, proportions of Hydrogenophaga (surface-attached and suspended), Zoogloea, and Flectobacillus (suspended) increased, but proportions of Bacillus, Clavibacter, and Cellvibro (surface-attached and suspended) decreased. In summary, a combined system of substrate addition and C/N control increased the production of grass carp, and Verrucomicrobiae and Rhodobacter in the surface-attached bacterial community were potential probiotic bacteria that contributed to the enhanced growth of grass carp.

Magnetism of cyano-bridged hetero-one-dimensional Ln3+-M3+ complexes (Ln3+ = Sm, Gd, Yb; M3+ = FeLS, Co).

PubMed

Figuerola, Albert; Diaz, Carmen; Ribas, Joan; Tangoulis, Vassilis; Sangregorio, Claudio; Gatteschi, Dante; Maestro, Miguel; Mahía, José

2003-08-25

The reaction of Ln(NO(3))(3).aq with K(3)[Fe(CN)(6)] or K(3)[Co(CN)(6)] and 2,2'-bipyridine in water led to five one-dimensional complexes: trans-[M(CN)(4)(mu-CN)(2)Ln(H(2)O)(4) (bpy)](n)().XnH(2)O.1.5nbpy (M = Fe(3+) or Co(3+); Ln = Sm(3+), Gd(3+), or Yb(3+); X = 4 or 5). The structures for [Fe(3)(+)-Sm(3+)] (1), [Fe(3)(+)-Gd(3+)] (2), [Fe(3)(+)-Yb(3+)] (3), [Co(3)(+)-Gd(3+)] (4), and [Co(3)(+)-Yb(3+)] (5) have been solved; they crystallize in the triclinic space P1 and are isomorphous. The [Fe(3+)-Sm(3+)] complex is a ferrimagnet, its magnetic studies suggesting the onset of weak ferromagnetic 3-D ordering at 3.5 K. The [Fe(3+)-Gd(3+)] interaction is weakly antiferromagnetic. The isotropic nature of Gd(3+) allowed us to evaluate the exchange interaction (J = 0.77 cm(-)(1)).

Assembly of bicyclic or monocyclic clusters from [(η5-C5Me5)2Mo2(μ3-S)4(CuMeCN)2]2+ with tetraphosphine or N,P mixed ligands: syntheses, structures and enhanced third-order NLO performances.

PubMed

Ren, Zhi-Gang; Sun, Sha; Dai, Min; Wang, Hui-Fang; Lü, Chun-Ning; Lang, Jian-Ping; Sun, Zhen-Rong

2011-09-07

Reactions of the preformed cluster [(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)(MeCN)(2)](ClO(4))(2) (1) with two tetraphosphine ligands, 1,4-N,N,N',N'-tetra(diphenylphosphanylmethyl)benzene diamine (dpppda) and N,N,N',N'-tetra(diphenylphosphanylmethyl)ethylene diamine (dppeda), produced two bicyclic clusters {[(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)](2)(L)}(ClO(4))(4) (3: L = dpppda; 4: L = dppeda). Analogous reactions of 1 or [(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)(MeCN)(2)](PF(6))(2) (2) with two N,P mixed ligands, N,N-bi(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) and N-diphenylphosphanylmethyl-4-aminopyridine (dppmapy), afforded two monocyclic clusters {[(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)](2)(L)(2)}X(4) (5: L = bdppmapy, X = ClO(4); 6: L = dppmapy, X = PF(6)). Compounds 3-6 were fully characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H and (31)P{(1)H} NMR spectra, ESI-MS and single-crystal X-ray crystallography. In the tetracations of 3-6, two cubane-like [Mo(2)(μ(3)-S)(4)Cu(2)] cores are linked either by one dpppda or dppeda bridge to form a bicyclic structure or by a pair of bdppmapy or dppmapy bridges to afford a monocyclic structure. The third-order nonlinear optical (NLO) properties of 1 and 3-6 in MeCN were also investigated by femtosecond degenerate four-wave mixing (DFWM) technique with a 50 fs pulse width at 800 nm. Compounds 3-6 exhibited enhanced third-order NLO performances relative to that of 1. This journal is © The Royal Society of Chemistry 2011

Self-exchange reaction of [Ni(mnt)2](1-,2-) in nonaqueous solutions.

PubMed

Kowert, Bruce A; Fehr, Michael J; Sheaff, Pamela J

2008-07-07

The rate constant, k, for the homogeneous electron transfer (self-exchange) reaction between the diamagnetic bis(maleonitriledithiolato)nickel dianion, [Ni(mnt) 2] (2-), and the paramagnetic monoanion, [Ni(mnt) 2] (1-), has been determined in acetone and nitromethane (CH 3NO 2) using (13)C NMR line widths at 22 degrees C (mnt = 1,2-S 2C 2(CN) 2). The values of k (2.91 x 10 (6) M (-1) s (-1) in acetone, 5.78 x 10 (6) M (-1) s (-1) in CH 3NO 2) are faster than those for the electron transfer reactions of other Ni(III,II) couples; the structures of [Ni(mnt) 2] (1-) and [Ni(mnt) 2] (2-) allow for a favorable overlap that lowers the free energy of activation. The values of k are consistent with the predictions of Marcus theory. In addition to k, the spin-lattice relaxation time, T 1e, of [Ni(mnt) 2] (1-) is obtained from the NMR line width analysis; the values are consistent with those predicted by spin relaxation theory.

Theoretical study of the magnetic exchange coupling behavior substituting Cr(III) with Mo(III) in cyano-bridged transition metal complexes

NASA Astrophysics Data System (ADS)

Zhang, Yi-Quan; Luo, Cheng-Lin

Molecular magnetism in a series of cyano-bridged first and second transition metal complexes has been investigated using density functional theory (DFT) combined with the broken-symmetry (BS) approach. Several exchange-correlation (XC) functionals in the ADF package were used to investigate complexes I [-(Me3tacn)2(cyclam)NiMo2(CN)6]2+, II [-(Me3tacn)2(cyclam)Ni-Cr2(CN)6]2+, III [(Me3tacn)6MnMo6(CN)18]2+, and IV [(Me3tacn)6MnCr6(CN)18]2+ (Me3tacn = N,N?,N‴-trimethyl-1,4,7-triazacyclononane). For models A (the molded structure of complex I) and B (the modeled structure of complex II), all the XCs given qualitatively reasonable results and predict ferromagnetic coupling character between M (M = MoIII for A or CrIII for B) and NiII in coincidence with the experimental results (see Tables and ). The calculated using Operdew, OPBE, O3LYP, and B3LYP functionals and experimental J values show that substituting CrIII with MoIII will enhance the ferromagnetic exchange coupling interactions. But VWN, PW91, PBE, VSXC, and tau-HCTH functionals have no way to differentiate the relative strength of the intramolecular magnetic exchange coupling interactions of A and B correctly. For models C (the modeled structure of complex III) and D (the modeled structure of complex IV), all the XCs in ADF and B3LYP in Gaussian 03 with several basis sets show that substituting CrIII with MoIII will enhance the antiferromagnetic exchange coupling interactions. From the above calculations, the substitution of CrIII by MoIII will enhance the magnetic coupling interactions, whether the magnetic coupling interactions are ferro- or antiferromagnetic. Moreover, Kahn's model was applied to investigate the above facts.

The Impact of Operating Room Layout on Circulating Nurse's Work Patterns and Flow Disruptions: A Behavioral Mapping Study.

PubMed

Bayramzadeh, Sara; Joseph, Anjali; San, Dee; Khoshkenar, Amin; Taaffe, Kevin; Jafarifiroozabadi, Roxana; Neyens, David M

2018-01-01

To assess how the adjacencies of functionally different areas within operating rooms (ORs) can influence the circulating nurse's (CN) workflow patterns and disruptions. The CN plays a significant role in promoting patient safety during surgical procedures by observing, monitoring, and managing potential threats at and around the surgical field. Their work requires constant movement to different parts of the OR to support team members. The layout of the OR and crowded and cluttered environment might impact the CN's workflow and cause disruptions during the surgery. A convenience sample of 25 surgeries were video recorded and thematically coded for CN's activities, locations, and flow disruptions. The OR layout was categorized into transitional zones and functional zones (workstations, supply zones, support zones, and sterile areas around the surgical table). CN's activities were classified into patient-, equipment-, material-, and information-related activities. Flow disruptions included those related to environmental hazards and layout. The CN traveled through multiple zones during 91% of the activities. The CN's workstation acted as a main hub from which the CN made frequent trips to both sides of the surgical table, the foot of the OR table, supply zones, and support zones. Transitional zones accounted for 58.3% of all flow disruption that the CN was involved in whereas 28% occurred in areas surrounding the OR bed. The similarity of the movement and flow disruption patterns, despite variations in OR layout, highlighted the adjacencies required between major zones that CNs regularly visit. These optimum adjacencies should be considered while designing ORs such that they are more efficient and safer.

Redetermination of the crystal structure of the 2D heterometallic framework prepared from [Ni(cyclam)]2+ and [Re(CN)7]3-

NASA Astrophysics Data System (ADS)

Sukhikh, Taisiya S.; Vostrikova, Kira E.

2018-02-01

A new XRD experiment and crystal structure refinement was performed for the earlier published compound in the paper "Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates" by Peresypkina et al. (2015) [1]. A choice of a crystal cell taking in consideration the superstructural reflections allowed to obtain more reliable data about the symmetry and bond distances in the heterometallic 2D framework {[Ni(cyclam)]2[ReO(OH)0.5(MeOH)0.5(CN)4]}2.5+. Additionally, doubling of the parameter c permitted to get more details about interlayer space. As a result, disordered perchlorate anions and solvate molecules were located.

Filtered pulsed cathodic arc deposition of fullerene-like carbon and carbon nitride films

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

Tucker, Mark D., E-mail: martu@ifm.liu.se; Broitman, Esteban; Näslund, Lars-Åke

Carbon and carbon nitride films (CN{sub x}, 0 ≤ x ≤ 0.26) were deposited by filtered pulsed cathodic arc and were investigated using transmission electron microscopy and X-ray photoelectron spectroscopy. A “fullerene-like” (FL) structure of ordered graphitic planes, similar to that of magnetron sputtered FL-CN{sub x} films, was observed in films deposited at 175 °C and above, with N{sub 2} pressures of 0 and 0.5 mTorr. Higher substrate temperatures and significant nitrogen incorporation are required to produce similar FL structure by sputtering, which may, at least in part, be explained by the high ion charge states and ion energies characteristic of arc deposition. A gradualmore » transition from majority sp{sup 3}-hybridized films to sp{sup 2} films was observed with increasing substrate temperature. High elastic recovery, an attractive characteristic mechanical property of FL-CN{sub x} films, is evident in arc-deposited films both with and without nitrogen content, and both with and without FL structure.« less

Copper(II) cyanido-bridged bimetallic nitroprusside-based complexes: Syntheses, X-ray structures, magnetic properties, 57Fe Mössbauer spectroscopy and thermal studies

NASA Astrophysics Data System (ADS)

Trávníček, Zdeněk; Herchel, Radovan; Mikulík, Jiří; Zbořil, Radek

2010-05-01

Three heterobimetallic cyanido-bridged copper(II) nitroprusside-based complexes of the compositions [Cu(tet)Fe(CN) 5NO]·H 2O ( 1), where tet= N,N' -bis(3-aminopropyl)ethylenediamine, [Cu(hto)Fe(CN) 5NO]·2H 2O ( 2), where hto=1,3,6,9,11,14-hexaazatricyclo[12.2.1.1 6,9]octadecane and [Cu(nme) 2Fe(CN) 5NO]·H 2O ( 3), where nme= N-methylethylenediamine, were synthesized and characterized by elemental analyses, 57Fe Mössbauer and FTIR spectroscopies, thermal analysis, magnetic measurements and single-crystal X-ray analysis. The products of thermal degradation processes of 2 and 3 were studied by XRD, 57Fe Mössbauer spectroscopy, SEM and EDS, and they were identified as mixtures of CuFe 2O 4 and CuO.

Uptake, accumulation and metabolic response of ferricyanide in weeping willows.

PubMed

Yu, Xiao-Zhang; Gu, Ji-Dong

2009-01-01

The remediation potential and metabolic responses of plants to ferricyanide were investigated using pre-rooted weeping willows (Salix babylonica L.) grown hydroponically in growth chambers and treated with potassium ferricyanide. Positive responses were observed for the plants exposed to

Syntheses, crystal structures and spectroscopic properties of copper(II)-tetracyanometallate(II) complexes with nicotinamide and isonicotinamide ligands

NASA Astrophysics Data System (ADS)

Sayın, Elvan; Kürkçüoğlu, Güneş Süheyla; Yeşilel, Okan Zafer; Hökelek, Tuncer

2015-09-01

Four new one dimensional (1D) cyanide complexes, namely {[Cu(NH3)4(μ-na)][M‧(CN)4]}n and {[Cu(NH3)2(ina)2M‧(μ-CN)2(CN)2]}n (M‧(II) = Pd (1 and 3) or Pt (2 and 4), na:nicotinamide and ina:isonicotinamide) have been synthesized and characterized by elemental, spectral (FT-IR and Raman), and thermal (TG, DTG and DTA) analyses. The crystal structures of complexes 1-3 have been determined by single crystal X-ray diffraction technique. In complexes 1 and 2, na ligand is coordinated to the adjacent Cu(II) ions as a bridging ligand, giving rise to 1D linear cationic chain and the [M‧(CN)4]2- anionic complex acts as a counter ion. Complexes 3 and 4 are also 1D linear chain in which two cyanide ligands bridged neighboring M‧(II) and Cu(II) ions, while ina ligand is coordinated Cu(II) ion through nitrogen atom of pyridine ring. In the complexes, the Cu(II) ions adopt distorted octahedral geometries, while M‧(II) ions are four coordinated with four carbon atoms from cyanide ligands in square-planar geometries. The adjacent chains are further stacked through intermolecular hydrogen bond, Nsbnd Hṡṡṡπ, Csbnd H⋯M‧ and M‧⋯π interactions to form 3D supramolecular networks. Vibration assignments are given for all the observed bands. In addition, thermal stabilities of the compounds are also discussed.

The molecular structures and conformation of o-selenobenzyl fluoride derivatives, ArSeX (Ar=C 6H 4CH 2F; X=CN, Cl, Me): ab initio and DFT calculations

NASA Astrophysics Data System (ADS)

Jeong, Myongho; Kwon, Younghi

2000-10-01

Ab initio and density functional theory methods are applied to investigate the molecular structures, intramolecular orbital interactions, and 19F and 77Se NMR chemical shifts of o-selenobenzyl fluoride derivatives, ArSeX ( Ar= C6H4CH2F; X= CN, Cl, Me) , at both RHF and B3LYP levels with the basis sets 6-311G ∗∗ and 6-311+G ∗∗. There are two stable rotational conformers for ArSeX. The energy differences between both conformers for each compound are small (within 2 kcal/mol) at various levels.

Magneto-structural correlation in a series of bimetallic alternating chain complexes of [CrIIIL(CN)4]n[MnIII(salpn)]n.nsolvents (L=2,2'-bipy or 9,10-phen, salpn=substituted salicyldehyde, solvents=water and methanol).

PubMed

Pan, Feng; Wang, Zhe-Ming; Gao, Song

2007-11-26

Five chain compounds based on the building block of [Cr(L)(CN)4]- (L=2,2'-bipy, 1-4; L=9,10-phen, 5) and [Mn(salpn)]+ (salpn=substituted salicyldehyde-type Schiff base in Scheme 1) have been prepared and characterized structurally and magnetically. The four compounds (1-4) consisting of [Cr(bipy)(CN)4]- units possess straight bimetallic chains as the [Cr(bpy)(CN)4]- unit links the two neighbor [Mn(salpn)]+ units with the two trans-cyanide ligands, while in 5 the chain is zigzag because the [Cr(phen)(CN)4]- unit connects the [Mn(salpn)]+ units with its two cis-cyanide ligands. The bond angles of Mn-N-C-Cr are adjusted by different coligands of salpn and bipy/phen. The chains are stacking via mainly the aromatic pi-pi-type interactions. All compounds show 3D antiferromagnetic ordering with Néel temperatures ranging from 3.7 to 8.1 K, and they are metamagnets displaying antiferromagnetic to ferrimagnetic transition at critical fields of 4.0-13.1 kOe at 1.9 K. This is due to weak interchain antiferromagnetic interactions between the ferrimagnetic bimetallic chains in the materials. The intrachain couplings (J, in cm(-1)) in the materials, between cyanide-bridged CrIII and MnIII ions, from -1.84 to -5.35 cm(-1), follow a linear relationship (J=-33+0.18alpha) to the Mn-N-C angles (alpha, in deg). In addition, the weak interchain antiferromagnetic interactions and critical fields for antiferromagnetic-ferrimagnetic transition are closely related to some of their structural factors, which were studied very superficially only referring to the separations of nearest chains in each material.

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.

PubMed

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 site, precluding magnetization blocking in complexes with fewer axial Ln ions. Further analysis has shown that, in the absence of ZFS on Ni ion, all compounds in the two series (except those containing Y and Gd) would be SMMs. The same situation arises for perfectly axial ZFS on Ni(II) with the main anisotropy axis parallel to the main magnetic axis of Ln(III) ions. In all other cases the ZFS on Ni(II) will worsen the SMM properties. The general conclusion is that the design of efficient SMMs on the basis of such complexes should involve isotropic or weekly anisotropic metal ions, such as Mn(II), Fe(III), etc., along with strongly axial lanthanides.

Structural investigations of transition metal (II) tetracyanonickelate complexes of 3-chloropyridine using Fourier transform-infrared and laser Raman spectroscopy

NASA Astrophysics Data System (ADS)

Akyüz, Sevim; Akyüz, Tanil; Eric, J.; Davies, D.

1992-01-01

The FT-IR and laser-Raman spectra of five new complexes of the formula ML 2Ni(CN) 4 (where MMn, Fe, Ni, Zn or Cd; L3-chloropyridine) are reported. The complexes are shown to have a structure consisting of two dimensional polymeric layers formed with Ni(CN) 4 ions bridged by ML 2 cations. For a given series of isomorphous complexes, the effects of metal ligand bond formation on the ligand vibrational modes are examined and the metal-sensitivity sequence of the ligand frequencies is found to be Mn≈Cd

Structure of zirconocene complexes relevant for olefin catalysis: infrared fingerprint of the Zr(C(5)H(5))(2)(OH)(CH(3)CN)(+) cation in the gas phase.

PubMed

Lagutschenkov, Anita; Springer, Andreas; Lorenz, Ulrich Joseph; Maitre, Philippe; Dopfer, Otto

2010-02-11

Cationic zirconocene complexes are active species in Ziegler-Natta catalysis for olefin polymerization. Their structure and metal-ligand bond strength strongly influence their activity. In the present work, the infrared multiphoton dissociation (IRMPD) spectrum of mass selected Zr(C(5)H(5))(2)(OH)(CH(3)CN)(+) cations was obtained in the 300-1500 cm(-1) fingerprint range by coupling a Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometer equipped with an electrospray ionization (ESI) source and the infrared free electron laser (IR-FEL) at the Centre Laser Infrarouge d'Orsay (CLIO). The experimental efforts are complemented by quantum chemical calculations at the MP2 and B3LYP levels using the 6-311G* basis set. Vibrational assignments of transitions observed in the IRMPD spectra to modes of the Zr-O-H, C(5)H(5), and CH(3)CN moieties are based on comparison to calculated linear absorption spectra. Both the experimental data and the calculations provide unprecedented information about structure, metal-ligand bonding, charge distribution, and binding energy of the complex.

Thermochemical and kinetic analysis of the thermal decomposition of monomethylhydrazine: an elementary reaction mechanism.

PubMed

Sun, Hongyan; Law, Chung K

2007-05-17

The reaction kinetics for the thermal decomposition of monomethylhydrazine (MMH) was studied with quantum Rice-Ramsperger-Kassel (QRRK) theory and a master equation analysis for pressure falloff. Thermochemical properties were determined by ab initio and density functional calculations. The entropies, S degrees (298.15 K), and heat capacities, Cp degrees (T) (0 < or = T/K < or = 1500), from vibrational, translational, and external rotational contributions were calculated using statistical mechanics based on the vibrational frequencies and structures obtained from the density functional study. Potential barriers for internal rotations were calculated at the B3LYP/6-311G(d,p) level, and hindered rotational contributions to S degrees (298.15 K) and Cp degrees (T) were calculated by solving the Schrödinger equation with free rotor wave functions, and the partition coefficients were treated by direct integration over energy levels of the internal rotation potentials. Enthalpies of formation, DeltafH degrees (298.15 K), for the parent MMH (CH3NHNH2) and its corresponding radicals CH3N*NH2, CH3NHN*H, and C*H2NHNH2 were determined to be 21.6, 48.5, 51.1, and 62.8 kcal mol(-1) by use of isodesmic reaction analysis and various ab initio methods. The kinetic analysis of the thermal decomposition, abstraction, and substitution reactions of MMH was performed at the CBS-QB3 level, with those of N-N and C-N bond scissions determined by high level CCSD(T)/6-311++G(3df,2p)//MPWB1K/6-31+G(d,p) calculations. Rate constants of thermally activated MMH to dissociation products were calculated as functions of pressure and temperature. An elementary reaction mechanism based on the calculated rate constants, thermochemical properties, and literature data was developed to model the experimental data on the overall MMH thermal decomposition rate. The reactions of N-N and C-N bond scission were found to be the major reaction paths for the modeling of MMH homogeneous decomposition at atmospheric conditions.

Electromagnetic field radiation model for lightning strokes to tall structures

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

Motoyama, H.; Janischewskyj, W.; Hussein, A.M.

1996-07-01

This paper describes observation and analysis of electromagnetic field radiation from lightning strokes to tall structures. Electromagnetic field waveforms and current waveforms of lightning strokes to the CN Tower have been simultaneously measured since 1991. A new calculation model of electromagnetic field radiation is proposed. The proposed model consists of the lightning current propagation and distribution model and the electromagnetic field radiation model. Electromagnetic fields calculated by the proposed model, based on the observed lightning current at the CN Tower, agree well with the observed fields at 2km north of the tower.

Characterization of casein gene complex and genetic diversity analysis in Indian goats.

PubMed

Rout, P K; Kumar, A; Mandal, A; Laloe, D; Singh, S K; Roy, R

2010-04-01

Milk protein polymorphism plays an important role in genetic diversity analysis, phylogenetic studies, establishing geographical diversity, conservation decision, and improving breeding goals. Milk protein polymorphism in Indian goat breeds has not been well studied; therefore, an investigation was carried out to analyze the genetic structure of the casein gene and milk protein diversity at six milk protein loci in nine Indian goat breeds/genetic groups from varied agro-climatic zones. Milk protein genotyping was carried out in 1098 individual milk samples by SDS-PAGE at alphaS1-CN (CSN1S1), beta-CN (CSN2), alphaS2-CN (CSN1S2), kappa-CN (CSN3), beta-LG, and alpha-LA loci. Indian goats exhibited alphaS1-casein A allele in higher frequency in the majority of breeds except Ganjam and local goats. The alphaS1-casein A allele frequencies varied from 0.45 to 0.77. A total of 16 casein haplotypes were observed in seven breeds and breed specific haplotypes were observed with respect to geographic region. The average number of alleles was lowest in Ganjam (1.66 +/- 0.81) and highest in Sirohi goats (2.50 +/- 1.05). Expected heterozygosity at six different loci demonstrated genetic diversity and breed fragmentation. Neighbor-Joining tree was built basing on Nei's distance. There was about 16.95% variability due to differences between breeds, indicating a strong subdivision. Principal component analysis was carried out to highlight the relationship among breeds. The variability among goat breeds was contributed by alphaS2-CN, beta-LG and alphaS1-CN. The Indian goats exhibited alphaS1-CN (CSN1S1) A allele in higher frequency in all the breeds indicating the higher casein yield in their milk.

Spectroscopic detection and mapping of vinyl cyanide on Titan

NASA Astrophysics Data System (ADS)

Cordiner, Martin; Yukiko Palmer, Maureen; Lai, James; Nixon, Conor A.; Teanby, Nicholas; Charnley, Steven B.; Vuitton, Veronique; Kisiel, Zbigniew; Irwin, Patrick; Molter, Ned; Mumma, Michael J.

2017-10-01

The first spectroscopic detection of vinyl cyanide (otherwise known as acrylonitrile; C2H3CN) on Titan was obtained by Palmer et al. (2017), based on three rotational emission lines observed with ALMA at millimeter wavelengths (in receiver band 6). The astrobiological significance of this detection was highlighted due to the theorized ability of C2H3CN molecules to combine into cell membrane-like structures under the cold conditions found in Titan's hydrocarbon lakes. Here we report the detection of three additional C2H3CN transitions at higher frequencies (from ALMA band 7 flux calibration data). We present the first emission maps for this gas on Titan, and compare the molecular distribution with that of other nitriles observed with ALMA including HC3N, CH3CN, C2H5CN and HNC. The molecular abundance patterns are interpreted based on our understanding of Titan's high-altitude photochemistry and time-variable global circulation. Similar to the short-lived HC3N molecule, vinyl cyanide is found to be most abundant in the vicinity of the southern (winter) pole, whereas the longer-lived CH3CN is more concentrated in the north. The vertical abundance profile of C2H3CN (from radiative transfer modeling), as well as its latitudinal distribution, are consistent with a short photochemical lifetime for this species. Complementary results from our more recent (2017) nitrile mapping studies at higher spatial resolution will also be discussed.REFERENCES:Palmer, M. Y., Cordiner, M. A., Nixon, C. A. et al. "ALMA detection and astrobiological potential of vinyl cyanide on Titan", Sci. Adv. 2017, 3, e1700022

Redox-switched complexation/decomplexation of K(+) and Cs(+) by molecular cyanometalate boxes.

PubMed

Boyer, Julie L; Ramesh, Maya; Yao, Haijun; Rauchfuss, Thomas B; Wilson, Scott R

2007-02-21

The reaction of [N(PPh(3))(2)][CpCo(CN)(3)] and [Cb*Co(NCMe)(3)]PF(6) (Cb* = C(4)Me(4)) in the presence of K(+) afforded {K subset[CpCo(CN)(3)](4)[Cb*Co](4)}PF(6), [KCo(8)]PF(6). IR, NMR, ESI-MS indicate that [KCo(8)]PF(6) is a high-symmetry molecular box containing a potassium ion at its interior. The analogous heterometallic cage {K subset[Cp*Rh(CN)(3)](4)[Cb*Co](4)}PF(6) ([KRh(4)Co(4)]PF(6)) was prepared similarly via the condensation of K[Cp*Rh(CN)(3)] and [Cb*Co(NCMe)(3)]PF(6). Crystallographic analysis confirmed the structure of [KCo(8)]PF(6). The cyanide ligands are ordered, implying that no Co-CN bonds are broken upon cage formation and ion complexation. Eight Co-CN-Co edges of the box bow inward toward the encapsulated K(+), and the remaining four mu-CN ligands bow outward. MeCN solutions of [KCo(8)](+) and [KRh(4)Co(4)](+) were found to undergo ion exchange with Cs(+) to give [CsCo(8)](+) and [CsRh(4)Co(4)](+), both in quantitative yields. Labeling experiments involving [(MeC5H4)Co(CN)(3)]- demonstrated that Cs(+)-for-K(+) ion exchange is accompanied by significant fragmentation. Ion exchange of NH(4+) with [KCo(8)](+) proceeds to completion in THF solution, but in MeCN solution, the exclusive products were [Cb*Co(NCMe)(3)]PF(6) and the poorly soluble salt NH(4)CpCo(CN)(3). The lability of the NH(4+)-containing cage was also indicated by the rapid exchange of the acidic protons in [NH(4)Co(8)](+). Oxidation of [MCo(8)](+) with 4 equiv of FcPF(6) produced paramagnetic (S = 4/2) [Co(8)](4+), releasing Cs(+) or K(+). The oxidation-induced dissociation of M(+) from the cages is chemically reversed by treatment of [Co(8)](4+) and CsOTf with 4 equiv of Cp(2)Co. Cation recognition by [Co(8)] and [Rh(4)Co(4)] cages was investigated. Electrochemical measurements indicated that E(1/2)(Cs(+))--E(1/2)(K(+)) approximately 0.08 V for [MCo(8)](+).

Iron monocyanide (FeCN): Spin-orbit and vibronic interactions in low-lying electronic states

NASA Astrophysics Data System (ADS)

Jerosimić, Stanka V.; Milovanović, Milan Z.

2018-04-01

The spin-orbit eigenvalues of low-energy quartet and sextet spatially degenerate electronic states of FeCN are reported, together with the combined effect of vibronic and spin-orbit interaction in the lowest-lying 14Δ and 16Δ states of FeCN, by using perturbational and variational method. Spin-orbit constants (ASO) have been calculated in the basis of: (a) two components of each degenerate state, (b) four components of 14Δ and 14Π (16Δ and 16Π) states, and (c) ten components of 16Δ, 16Π, 16Σ+, 14Δ, 14Π, and 14Σ+ states. The present calculations predict the values of ASO= -77 cm-1 for 16Δ and ASO= -108 cm-1 for 14Δ state in the lowest-energy spin-orbit manifolds of each state. The major perturbing state for the 14Δ state is the 14Π state (16Π for the sextet 16Δ). As expected, based on extremely small splitting and shallowness of the bending potential energy curves for the lowest-lying 4,6Δ states, the present study indicate that the vibronic coupling does not create significant splitting of the bending levels, but the influence of anharmonicity in the bending mode is more pronounced. However, the spin-orbit fine structure dominantly influences the spectra of this species.

Ab initio evaluation of the thermodynamic and electrochemical properties of alkyl halides and radicals and their mechanistic implications for atom transfer radical polymerization.

PubMed

Lin, Ching Yeh; Coote, Michelle L; Gennaro, Armando; Matyjaszewski, Krzysztof

2008-09-24

High-level ab initio molecular orbital calculations are used to study the thermodynamics and electrochemistry relevant to the mechanism of atom transfer radical polymerization (ATRP). Homolytic bond dissociation energies (BDEs) and standard reduction potentials (SRPs) are reported for a series of alkyl halides (R-X; R = CH 2CN, CH(CH 3)CN, C(CH 3) 2CN, CH 2COOC 2H 5, CH(CH 3)COOCH 3, C(CH 3) 2COOCH 3, C(CH 3) 2COOC 2H 5, CH 2Ph, CH(CH 3)Ph, CH(CH 3)Cl, CH(CH 3)OCOCH 3, CH(Ph)COOCH 3, SO 2Ph, Ph; X = Cl, Br, I) both in the gas phase and in two common organic solvents, acetonitrile and dimethylformamide. The SRPs of the corresponding alkyl radicals, R (*), are also examined. The computational results are in a very good agreement with the experimental data. For all alkyl halides examined, it is found that, in the solution phase, one-electron reduction results in the fragmentation of the R-X bond to the corresponding alkyl radical and halide anion; hence it may be concluded that a hypothetical outer-sphere electron transfer (OSET) in ATRP should occur via concerted dissociative electron transfer rather than a two-step process with radical anion intermediates. Both the homolytic and heterolytic reactions are favored by electron-withdrawing substituents and/or those that stabilize the product alkyl radical, which explains why monomers such as acrylonitrile and styrene require less active ATRP catalysts than vinyl chloride and vinyl acetate. The rate constant of the hypothetical OSET reaction between bromoacetonitrile and Cu (I)/TPMA complex was estimated using Marcus theory for the electron-transfer processes. The estimated rate constant k OSET = approximately 10 (-11) M (-1) s (-1) is significantly smaller than the experimentally measured activation rate constant ( k ISET = approximately 82 M (-1) s (-1) at 25 degrees C in acetonitrile) for the concerted atom transfer mechanism (inner-sphere electron transfer, ISET), implying that the ISET mechanism is preferred. For monomers bearing electron-withdrawing groups, the one-electron reduction of the propagating alkyl radical to the carbanion is thermodynamically and kinetically favored over the one-electron reduction of the corresponding alkyl halide unless the monomer bears strong radical-stabilizing groups. Thus, for monomers such as acrylates, catalysts favoring ISET over OSET are required in order to avoid chain-breaking side reactions.

Synthesis and Structural Characterization of Tris(dimethyldithiocarbamate)Indium(III), In[S2CN(CH3)2]3

NASA Technical Reports Server (NTRS)

Clark, Eric B.; Breen, Marc L.; Fanwick, Phillip E.; Hepp, Aloysius F.; Duraj, Stan A.

1998-01-01

The synthesis and structure of the indium dithiocarbamate, In[SCN(CH3)2]3*1/2 4-mepy (4-mepy = 4-methylpyridine), is described. Indium metal was oxidized by tetramethylthiuramdisulfide in 4-methylpyridine at 25C to form a new, homoleptic indium(HI) dithiocarbamate in yields exceeding 60%. In[S2CN(CH3)213 exists as a discrete molecule with a distorted-octahedral geometry. The compound crystallizes in the P 1-bar (No. 2) space group with a = 9.282(l)A, b = 10.081(1)A, c = 12.502 A, alpha= 73.91 (1) degrees, beta = 70.21(1) degrees, gamma = 85.84(1) degrees, Z = 2,v(A(exp 3)) =1057.3(3), R = 0.046, and R(sub w) = 0.061.

Low temperature structural transformation in T[Ni(CN){sub 4}].xpyz with x=1,2; T=Mn,Co,Ni,Zn,Cd; pyz=pyrazine

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

Rodriguez-Hernandez, J.; Instituto de Ciencia y Tecnologia de Materiales, Universidad de La Habana; Lemus-Santana, A.A.

2010-01-15

The materials under study are pillared solids T[Ni(CN){sub 4}].xpyz with one and two (x=1,2) pyrazine (pyz) molecules and where T=Mn, Co, Ni, Zn, Cd. Stimulated by their structural features and potential role as prototype of porous solids for hydrogen storage, the structural stability under cryogenic conditions for this series of pillared solids was studied. At low temperature, in the 100-200 K range, the occurrence of a reversible structural transformation was found. For T=Mn, Co, Zn, Cd, with x=2, the structural transformation was observed to occur around 185 K, and the low temperature phase crystallizes with a monoclinic unit cell (spacemore » group Pc). This structure change results from certain charge redistribution on cooling within the involved ligands. For T=Ni with x=1, both the low and high temperature phases crystallize with unit cells of tetragonal symmetry, within the same space group but with a different unit cell volume. In this case the structure change is observed around 120 K. Above that temperature the rotational states for the pyrazine molecule are thermally excited and all the pyrazine molecules in the structure become equivalent. Under this condition the material structure is described using a smaller structural unit. The structural study using X-ray powder diffraction data was complemented with calorimetric and Raman spectroscopy measurements. For the low temperature phases the crystal structures were solved from Patterson methods and then refined using the Rietveld method. - Graphical abstract: Low temperature ordered structure for pyrazine in T[Ni(CN){sub 4}].pyz.« less

Silacyanogen

NASA Astrophysics Data System (ADS)

Ignatyev, Igor S.; Schaefer, Henry F., III

1997-10-01

Structures of all possible linear isomers of the Si-substituted cyanogen were optimized at the SCF, B3LYP, MP2, and CCSD levels of theory. At all levels of theory the most stable isomer was found to be SiNCN, while for cyanogen the most stable structure is well known to be NCCN. The theoretical ordering of the stability of the acyclic structures is SiNCN>SiNNO>NSiCN>NSiNC. The difference in the order of stability of silacyanogen and cyanogen isomers is rationalized, taking into account the position of the unpaired electron on carbon in the CN radical and that on nitrogen in the SiN radical.

Kinetic spectrophotometric method for trace determination of thiocyanate based on its inhibitory effect

NASA Astrophysics Data System (ADS)

Naik, Radhey M.; Kumar, Basant; Asthana, Abhas

2010-03-01

A kinetic spectrophotometric method for the determination of thiocyanate, based on its inhibitory effect on silver(I) catalyzed substitution of cyanide ion, by phenylhydrazine in hexacyanoferrate(II) is described. Thiocyanate ions form strong complexes with silver(I) catalyst which is used as the basis for its determination at trace level. The progress of reaction was monitored, spectrophotometrically, at 488 nm ( λmax of [Fe(CN) 5PhNHNH 2] 3-, complex) under the optimum reaction conditions at: 2.5 × 10 -3 M [Fe(CN) 6] 4-, 1.0 × 10 -3 M [PhNHNH 2], 8.0 × 10 -7 M [Ag +], pH 2.8 ± 0.02, ionic strength ( μ) 0.02 M (KNO 3) and temperature 30 ± 0.1 °C. A linear relationship obtained between absorbance (measured at 488 nm at different times) and inhibitor concentration, under specified conditions, has been used for the determination of [thiocyanate] in the range of 0.8-8.0 × 10 -8 M with a detection limit of 2 × 10 -9 M. The standard deviation and percentage error have been calculated and reported with each datum. A most plausible mechanistic scheme has been proposed for the reaction. The values of equilibrium constants for complex formation between catalyst-inhibitor ( KCI), catalyst-substrate ( Ks) and Michaelis-Menten constant ( Km) have been computed from the kinetic data. The influence of possible interference by major cations and anions on the determination of thiocyanate and their limits has been investigated.

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

NASA Technical Reports Server (NTRS)

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

1995-01-01

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

Ferrate(VI) oxidation of zinc-cyanide complex.

PubMed

Yngard, Ria; Damrongsiri, Seelawut; Osathaphan, Khemarath; Sharma, Virender K

2007-10-01

Zinc-cyanide complexes are found in gold mining effluents and in metal finishing rinse water. The effect of Zn(II) on the oxidation of cyanide by ferrate(VI) (Fe(VI)O(4)(2-), Fe(VI)) was thus investigated by studying the kinetics of the reaction of Fe(VI) with cyanide present in a potassium salt of a zinc cyanide complex (K(2)Zn(CN)(4)) and in a mixture of Zn(II) and cyanide solutions as a function of pH (9.0-11.0). The rate-law for the oxidation of Zn(CN)(4)(2-) by Fe(VI) was found to be -d[Fe(VI)]/dt=k[Fe(VI)][Zn(CN)(4)(2-)](0.5). The rate constant, k, decreased with an increase in pH. The effect of temperature (15-45 degrees C) on the oxidation was studied at pH 9.0, which gave an activation energy of 45.7+/-1.5kJmol(-1). The cyanide oxidation rate decreased in the presence of the Zn(II) ions. However, Zn(II) ions had no effect on the cyanide removal efficiency by Fe(VI) and the stoichiometry of Fe(VI) to cyanide was approximately 1:1; similar to the stoichiometry in absence of Zn(II) ions. The destruction of cyanide by Fe(VI) resulted in cyanate. The experiments on removal of cyanide from rinse water using Fe(VI) demonstrated complete conversion of cyanide to cyanate.

(13)C NMR substituent-induced chemical shifts in 4-(substituted phenyl)-3-phenyl-1,2,4-oxadiazol-5(4H)-ones (thiones).

PubMed

Kara, Yesim Saniye

2015-01-01

In the present, study mostly novel ten 4-(substituted phenyl)-3-phenyl-1,2,4-oxadiazol-5(4H)-ones and ten 4-(substituted phenyl)-3-phenyl-1,2,4-oxadiazol-5(4H)-thiones were synthesized. These oxadiazole derivatives were characterized by IR, (1)H NMR, (13)C NMR and elemental analyses. Their (13)C NMR spectra were measured in Deuterochloroform (CDCl3). The correlation analysis for the substituent-induced chemical shift (SCS) with Hammett substituent constants (σ), Brown Okamoto substituent constants (σ(+), σ(-)), inductive substituent constants (σI) and different of resonance substituent constants (σR, σR(o)) were performed using SSP (single substituent parameter), DSP (dual substituent parameter) and DSP-NLR (dual substituent parameter-non-linear resonance) methods, as well as single and multiple regression analysis. Negative ρ values were found for all correlations (reverse substituent effect). The results of all statistical analyses, (13)C NMR chemical shift of CN, CO and CS carbon of oxadiazole rings have shown satisfactory correlation. Copyright © 2015 Elsevier B.V. All rights reserved.

Crystal structure of poly[N,N-diethyl-2-hy-droxy-ethan-1-aminium [μ3-cyanido-κ(3) C:C:N-di-μ-cyanido-κ(4) C:N-dicuprate(I)

PubMed

Corfield, Peter W R; Cleary, Emma; Michalski, Joseph F

2016-07-01

In the title compound, {(C6H16NO)[Cu2(CN)3]} n , the cyanide groups link the Cu(I) atoms into an open three-dimensional anionic network, with the mol-ecular formula Cu2(CN)3 (-). One Cu(I) atom is tetra-hedrally bound to four CN groups, and the other Cu(I) atom is bonded to three CN groups in an approximate trigonal-planar coordination. The tetra-hedrally coordinated Cu(I) atoms are linked into centrosymmetric dimers by the C atoms of two end-on bridging CN groups which bring the Cu(I) atoms into close contact at 2.5171 (7) Å. Two of the cyanide groups bonded to the Cu(I) atoms with trigonal-planar surrounding link the dimeric units into columns along the a axis, and the third links the columns together to form the network. The N,N-di-ethyl-ethano-lamine mol-ecules used in the synthesis have become protonated at the N atoms and are situated in cavities in the network, providing charge neutrality, with no covalent inter-actions between the cations and the anionic network.

Manganese-Chromium-Cyanide Clusters: Molecular MnCr 6(CN) 18 and Mn 3Cr 6(CN) 18 Species and a Related MnCr 3(CN) 9 Chain Compound

NASA Astrophysics Data System (ADS)

Heinrich, Julie L.; Sokol, Jennifer J.; Hee, Allan G.; Long, Jeffrey R.

2001-07-01

As part of an ongoing effort to design new single-molecule magnets, we are exploring synthetic routes to high-nuclearity metal-cyanide clusters. Here, we report the results of solution assembly reactions between [(Me3tacn)Cr(CN)3] (Me3tacn= N,N‧,N″-trimethyl-1,4,7-triazacyclononane) and selected manganese(II) salts. Reaction with the perchlorate salt in the presence of AClO4 (A=Na, K) gives A[(Me3tacn)6MnCr6(CN)18] (ClO4)3, featuring a heptanuclear cluster in which six [(Me3tacn)Cr(CN)3] units surround a central MnII ion. The Mn coordination geometry closely approaches a trigonal prism, with triangular faces twisted away from a fully eclipsed position by an angle of 12.8° and 11.3° for A=Na and K, respectively. The magnetic behavior of both compounds indicates weak antiferromagnetic coupling between neighboring MnII and CrIII centers (J=-3.0 and -3.1 cm-1, respectively) to give an S={13}/{2}; ground state. Alternatively, addition of sodium tetraphenylborate to the reaction solution yields [(Me3tacn)6(H2O)6Mn3Cr6(CN)18] (BPh4)6·12H2O, in which attachment of two MnII ions to the preceding cluster generates a new species with two trigonal bipyramids sharing a common vertex. This compound displays magnetic behavior consistent with weak antiferromagnetic coupling and an S={3}/{2} ground state. Finally, a reaction employing manganese(II) triflate is found to produce the one-dimensional solid [(Me3tacn)3MnCr3(CN)9](CF3SO3)2, exhibiting a closely related chain structure, and, again, weak antiferromagnetic coupling.

Screening Hofmann Compounds as CO 2 Sorbents: Nontraditional Synthetic Route to Over 40 Different Pore-Functionalized and Flexible Pillared Cyanonickelates

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

Culp, Jeffrey T.; Madden, Catherine; Kauffman, Kristi

2013-04-15

A simple reaction scheme based on the heterogeneous intercalation of pillaring ligands (HIPLs) provides a convenient method for systematically tuning pore size, pore functionality, and network flexibility in an extended series of pillared cyanonickelates (PICNICs), commonly referred to as Hofmann compounds. The versatility of the approach is demonstrated through the preparation of over 40 different PICNICs containing pillar ligands ranging from 4 to 15 Å in length and modified with a wide range of functional groups, including fluoro, aldehyde, alkylamine, alkyl, aryl, trifluoromethyl, ester, nitro, ether, and nonmetalated 4,4'-bipyrimidine. The HIPL method involves reaction of a suspension of preformed polymericmore » sheets of powdered anhydrous nickel cyanide with an appropriate pillar ligand in refluxing organic solvent, resulting in the conversion of the planar [Ni{sub 2}(CN){sub 4}]{sub n} networks into polycrystalline three-dimensional porous frameworks containing the organic pillar ligand. Preliminary investigations indicate that the HIPL reaction is also amenable to forming Co(L)Ni(CN){sub 4}, Fe(L)Ni(CN){sub 4}, and Fe(L)Pd(CN){sub 4} networks. The materials show variable adsorption behavior for CO{sub 2} depending on the pillar length and pillar functionalization. Several compounds show structurally flexible behavior during the adsorption and desorption of CO{sub 2}. Interestingly, the newly discovered flexible compounds include two flexible Fe(L)Ni(CN){sub 4} derivatives that are structurally related to previously reported porous spin-crossover compounds. The preparations of 20 pillar ligands based on ring-functionalized 4,4'-dipyridyls, 1,4-bis(4-pyridyl)benzenes, and N-(4-pyridyl)isonicotinamides are also described.« less

Screening Hofmann Compounds as CO 2 Sorbents: Nontraditional Synthetic Route to Over 40 Different Pore-Functionalized and Flexible Pillared Cyanonickelates

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

Culp, Jeffrey T.; Madden, Catherine; Kauffman, Kristi

2013-04-15

A simple reaction scheme based on the heterogeneous intercalation of pillaring ligands (HIPLs) provides a convenient method for systematically tuning pore size, pore functionality, and network flexibility in an extended series of pillared cyanonickelates (PICNICs), commonly referred to as Hofmann compounds. The versatility of the approach is demonstrated through the preparation of over 40 different PICNICs containing pillar ligands ranging from ~4 to ~15 Å in length and modified with a wide range of functional groups, including fluoro, aldehyde, alkylamine, alkyl, aryl, trifluoromethyl, ester, nitro, ether, and nonmetalated 4,4'-bipyrimidine. The HIPL method involves reaction of a suspension of preformed polymericmore » sheets of powdered anhydrous nickel cyanide with an appropriate pillar ligand in refluxing organic solvent, resulting in the conversion of the planar [Ni{sub 2}(CN){sub 4}]{sub n} networks into polycrystalline three-dimensional porous frameworks containing the organic pillar ligand. Preliminary investigations indicate that the HIPL reaction is also amenable to forming Co(L)Ni(CN){sub 4}, Fe(L)Ni(CN){sub 4}, and Fe(L)Pd(CN){sub 4} networks. The materials show variable adsorption behavior for CO{sub 2} depending on the pillar length and pillar functionalization. Several compounds show structurally flexible behavior during the adsorption and desorption of CO{sub 2}. Interestingly, the newly discovered flexible compounds include two flexible Fe(L)Ni(CN){sub 4} derivatives that are structurally related to previously reported porous spin-crossover compounds. The preparations of 20 pillar ligands based on ring-functionalized 4,4'-dipyridyls, 1,4-bis(4- pyridyl)benzenes, and N-(4-pyridyl)isonicotinamides are also described.« less

[Effects of different application rates of calcium cyanamide on soil microbial biomass and enzyme activity in cucumber continuous cropping].

PubMed

Zhang, Xue-peng; Ning, Tang-yuan; Yang, Yan; Sun, Tao; Zhang, Shu-min; Wang, Bin

2015-10-01

A 2-year field experiment was conducted to study the effects of CaCN2 combined with cucumber straw retention on soil microbial biomass carbon (SMBC) , soil microbial biomass nitrogen (SMBN) and soil enzyme activities under cucumber continuous cropping system. Four treatments were used in this study as follows: CK (null CaCN2), CaCN2-90 (1350 kg CaCN2 . hm-2) CaCN2-60 (900 kg CaCN2 . hm-2), CaCN2-30 (450 kg CaCN2 . hm-2). The results indicated that, compared with the other treatments, CaCN2-90 treatment significantly decreased SMBC in 0-10 cm soil layer at seedling stage, but increased SMBC in 0-20 cm soil layer after early-fruit stage. Compared with CK, CaCN2 increased SMBC in 0-20 cm soil layer at late-fruit stage, and increased SMBN in 0-10 cm soil layer at mid- and late-fruit stages, however there was no significant trend among CaCN2 treatments in the first year (2012), while in the second year (2013) SMBN increased with the increasing CaCN2 amount after mid-fruit stage. CaCN2 increased straw decaying and nutrients releasing, and also increased soil organic matter. Furthermore, the CaCN2-90 could accelerate straw decomposition. Compared with CK, CaCN2 effectively increased soil urease, catalase and polyphenol oxidase activity. The soil urease activity increased while the polyphenol oxidase activity decreased with the increase of CaCN2, and CaCN2-60 could significantly improve catalase activity. Soil organic matter, urease activity and catalase activity had significant positive correlations with SMBC and SMBN. However, polyphenol oxidase activity was negatively correlated to SMBC and SMBN. Our findings indicated that CaCN2 application at 900 kg . hm-2 combined with cucumber straw retention could effectively improve soil environment, alleviating the soil obstacles under the cucumber continuous cropping system.

Rogue periodic waves of the modified KdV equation

NASA Astrophysics Data System (ADS)

Chen, Jinbing; Pelinovsky, Dmitry E.

2018-05-01

Rogue periodic waves stand for rogue waves on a periodic background. Two families of travelling periodic waves of the modified Korteweg–de Vries (mKdV) equation in the focusing case are expressed by the Jacobian elliptic functions dn and cn. By using one-fold and two-fold Darboux transformations of the travelling periodic waves, we construct new explicit solutions for the mKdV equation. Since the dn-periodic wave is modulationally stable with respect to long-wave perturbations, the new solution constructed from the dn-periodic wave is a nonlinear superposition of an algebraically decaying soliton and the dn-periodic wave. On the other hand, since the cn-periodic wave is modulationally unstable with respect to long-wave perturbations, the new solution constructed from the cn-periodic wave is a rogue wave on the cn-periodic background, which generalizes the classical rogue wave (the so-called Peregrine’s breather) of the nonlinear Schrödinger equation. We compute the magnification factor for the rogue cn-periodic wave of the mKdV equation and show that it remains constant for all amplitudes. As a by-product of our work, we find explicit expressions for the periodic eigenfunctions of the spectral problem associated with the dn and cn periodic waves of the mKdV equation.

Crystal structure refinement of the electron-transfer-active potassium manganese hexacyanoferrates and isomorphous potassium manganese hexacyanocobaltates

NASA Astrophysics Data System (ADS)

Rykov, Alexandre I.; Li, Xuning; Wang, Junhu

2015-07-01

We report on the crystal structure refinements in the novel electron-transfer-active Prussian Blue analogs (PBA) KMn4II [Co1-xIII FexIII (CN)6 ]3 · nH2 O (n ≃ 12). The series of novel PBA with the end members of KMn4[ Co(CN)6]3 · 11.8H2 O and KMn4[ Fe(CN)6 ]3 · 10.5H2 O have been synthesized for the first time, all showing a number of extra-reflections incompatible with ordinary face-centered cell of the Fm-3m symmetry group. We have analyzed the Rietveld patterns for x = 0 , 0.53 , 1 and found that the extra-reflections could be well fitted using several primitive (P) cell symmetries. The best fitting quality was obtained using the noncentrosymmetric space group (S.G.) P 4 bar 3 m (Z=1) with the origin of coordinate system shifted into a zeolitic site. In this structure model, the Co-CN-Mn entities are bent owing to the charge introduced by the K+ insertion that induces also the electron transfer between Mn and Fe. Using Mössbauer spectroscopy the electron transfer activity is identified with the appearance of unsplit resonance at the isomer shift of typically -0.15 mm/s evidencing the low-spin state for Fe3+ and Fe2+ species. In the same P 4 bar 3 m phases doped with 2+57Fe into the Mn site, a sequence of discrete values of quadrupole splitting (0 mm/s, 0.9 mm/s, 1.8 mm/s) is observed and attributed to different conformations of the polyhedra, in which the ground states are orbital triplet, doublet and singlet, respectively.

Graphite carbon nitride/boron-doped graphene hybrid for efficient hydrogen generation reaction.

PubMed

Yang, Liang; Wang, Xin; Wang, Juan; Cui, Guomin; Liu, Daoping

2018-08-24

Metal-free carbon materials, with tuned surface chemical and electronic properties, hold great potential for the hydrogen evolution reaction (HER). We designed and synthesized a CN/BG hybrid electrocatalytic system with a porous and active graphite carbon nitride (CN) layer on boron-doped graphene (BG). A porous CN layer on graphene could provide exposed defects and edges that act as active sites for proton adsorption and reduction. The composition, structure, surface electronics, and chemical properties of this CN/BG hybrid system were tuned to obtain excellent HER activity and stability. Detailed surface chemical, morphological, and structural analyses demonstrated the synergetic effect arising from the electronic interaction between CN and BG, which contributed to the enhanced electrocatalytic performances.

Tuning the reactivity of Fe(V)(O) toward C-H bonds at room temperature: effect of water.

PubMed

Singh, Kundan K; Tiwari, Mrityunjay k; Ghosh, Munmun; Panda, Chakadola; Weitz, Andrew; Hendrich, Michael P; Dhar, Basab B; Vanka, Kumar; Sen Gupta, Sayam

2015-02-16

The presence of an Fe(V)(O) species has been postulated as the active intermediate for the oxidation of both C-H and C═C bonds in the Rieske dioxygenase family of enzymes. Understanding the reactivity of these high valent iron-oxo intermediates, especially in an aqueous medium, would provide a better understanding of these enzymatic reaction mechanisms. The formation of an Fe(V)(O) complex at room temperature in an aqueous CH3CN mixture that contains up to 90% water using NaOCl as the oxidant is reported here. The stability of Fe(V)(O) decreases with increasing water concentration. We show that the reactivity of Fe(V)(O) toward the oxidation of C-H bonds, such as those in toluene, can be tuned by varying the amount of water in the H2O/CH3CN mixture. Rate acceleration of up to 60 times is observed for the oxidation of toluene upon increasing the water concentration. The role of water in accelerating the rate of the reaction has been studied using kinetic measurements, isotope labeling experiments, and density functional theory (DFT) calculations. A kinetic isotope effect of ∼13 was observed for the oxidation of toluene and d8-toluene showing that C-H abstraction was involved in the rate-determining step. Activation parameters determined for toluene oxidation in H2O/CH3CN mixtures on the basis of Eyring plots for the rate constants show a gain in enthalpy with a concomitant loss in entropy. This points to the formation of a more-ordered transition state involving water molecules. To further understand the role of water, we performed a careful DFT study, concentrating mostly on the rate-determining hydrogen abstraction step. The DFT-optimized structure of the starting Fe(V)(O) and the transition state indicates that the rate enhancement is due to the transition state's favored stabilization over the reactant due to enhanced hydrogen bonding with water.

[Fe(bpb)(CN)2]- as a versatile building block for the design of novel low-dimensional heterobimetallic systems: synthesis, crystal structures, and magnetic properties of cyano-bridged Fe(III)-Ni(II) complexes [(bpb)(2-) = 1,2-bis(pyridine-2-carboxamido)benzenate].

PubMed

Ni, Zhong-Hai; Kou, Hui-Zhong; Zhao, Yi-Hua; Zheng, Lei; Wang, Ru-Ji; Cui, Ai-Li; Sato, Osamu

2005-03-21

A dicyano-containing [Fe(bpb)(CN)2]- building block has been employed for the synthesis of cyano-bridged heterometallic Ni(II)-Fe(III) complexes. The presence of steric bpb(2-) ligand around the iron ion results in the formation of low-dimensional species: five are neutral NiFe2 trimers and three are one-dimensional (1D). The structure of the 1D complexes consists of alternating [NiL]2+ and [Fe(bpb)(CN)2]- generating a cyano-bridged cationic polymeric chain and the perchlorate as the counteranion. In all complexes, the coordination geometry of the nickel ions is approximately octahedral with the cyano nitrogen atoms at the trans positions. Magnetic studies of seven complexes show the presence of ferromagnetic interaction between the metal ions through the cyano bridges. Variable temperature magnetic susceptibility investigations of the trimeric complexes yield the following J(NiFe) values (based on the spin exchange Hamiltonian H = -2J(NiFe) S(Ni) (S(Fe(1)) + S(Fe(2))): J(NiFe) = 6.40(5), 7.8(1), 8.9(2), and 6.03(4) cm(-1), respectively. The study of the magneto-structural correlation reveals that the cyanide-bridging bond angle is related to the strength of magnetic exchange coupling: the larger the Ni-N[triple bond]C bond angle, the stronger the Ni- - -Fe magnetic interaction. One 1D complex exhibits long-range antiferromagnetic ordering with T(N) = 3.5 K. Below T(N) (1.82 K), a metamagnetic behavior was observed with the critical field of approximately 6 kOe. The present research shows that the [Fe(bpb)(CN)2]- building block is a good candidate for the construction of low-dimensional magnetic materials.

Blue photoluminescent carbon nanodots from limeade.

PubMed

Suvarnaphaet, Phitsini; Tiwary, Chandra Sekhar; Wetcharungsri, Jutaphet; Porntheeraphat, Supanit; Hoonsawat, Rassmidara; Ajayan, Pulickel Madhavapanicker; Tang, I-Ming; Asanithi, Piyapong

2016-12-01

Carbon-based photoluminescent nanodot has currently been one of the promising materials for various applications. The remaining challenges are the carbon sources and the simple synthetic processes that enhance the quantum yield, photostability and biocompatibility of the nanodots. In this work, the synthesis of blue photoluminescent carbon nanodots from limeade via a single-step hydrothermal carbonization process is presented. Lime carbon nanodot (L-CnD), whose the quantum yield exceeding 50% for the 490nm emission in gram-scale amounts, has the structure of graphene core functionalized with the oxygen functional groups. The micron-sized flake of the as-prepared L-CnD powder exhibits multicolor emission depending on an excitation wavelength. The L-CnDs are demonstrated for rapidly ferric-ion (Fe(3+)) detection in water compared to Fe(2+), Cu(2+), Co(2+), Zn(2+), Mn(2+) and Ni(2+) ions. The photoluminescence quenching of L-CnD solution under UV light is used to distinguish the Fe(3+) ions from others by naked eyes as low concentration as 100μM. Additionally, L-CnDs provide exceptional photostability and biocompatibility for imaging yeast cell morphology. Changes in morphology of living yeast cells, i.e. cell shape variation, and budding, can be observed in a minute-period until more than an hour without the photoluminescent intensity loss. Copyright © 2016 Elsevier B.V. All rights reserved.

Nickel-Catalyzed Highly Regioselective Hydrocyanation of Terminal Alkynes with Zn(CN)2 Using Water as the Hydrogen Source.

PubMed

Zhang, Xingjie; Xie, Xin; Liu, Yuanhong

2018-06-08

The first efficient and general nickel-catalyzed hydrocyanation of terminal alkynes with Zn(CN) 2 in the presence of water has been developed. The reaction provides a regioselective protocol for the synthesis of functionalized vinyl nitriles with a range of structural diversity under mild reaction conditions while obviating use of the volatile and hazardous reagent of HCN. Deuterium-labeling experiments confirmed the role of water as the hydrogen source in this hydrocyanation reaction.

Studies of a series of [Ni(P(R)2N(Ph)2)2(CH3CN)]2+ complexes as electrocatalysts for H2 production: substituent variation at the phosphorus atom of the P2N2 ligand.

PubMed

Kilgore, Uriah J; Stewart, Michael P; Helm, Monte L; Dougherty, William G; Kassel, W Scott; DuBois, Mary Rakowski; DuBois, Daniel L; Bullock, R Morris

2011-11-07

A series of [Ni(P(R)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2) complexes containing the cyclic diphosphine ligands [P(R)(2)N(Ph)(2) = 1,5-diaza-3,7-diphosphacyclooctane; R = benzyl (Bn), n-butyl (n-Bu), 2-phenylethyl (PE), 2,4,4-trimethylpentyl (TP), and cyclohexyl (Cy)] have been synthesized and characterized. X-ray diffraction studies reveal that the cations of [Ni(P(Bn)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2) and [Ni(P(n-Bu)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2) have distorted trigonal bipyramidal geometries. The Ni(0) complex [Ni(P(Bn)(2)N(Ph)(2))(2)] was also synthesized and characterized by X-ray diffraction studies and shown to have a distorted tetrahedral structure. These complexes, with the exception of [Ni(P(Cy)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2), all exhibit reversible electron transfer processes for both the Ni(II/I) and Ni(I/0) couples and are electrocatalysts for the production of H(2) in acidic acetonitrile solutions. The heterolytic cleavage of H(2) by [Ni(P(R)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2) complexes in the presence of p-anisidine or p-bromoaniline was used to determine the hydride donor abilities of the corresponding [HNi(P(R)(2)N(Ph)(2))(2)](BF(4)) complexes. However, for the catalysts with the most bulky R groups, the turnover frequencies do not parallel the driving force for elimination of H(2), suggesting that steric interactions between the alkyl substituents on phosphorus and the nitrogen atom of the pendant amines play an important role in determining the overall catalytic rate. © 2011 American Chemical Society

Long-term stable water vapor permeation barrier properties of SiN/SiCN/SiN nanolaminated multilayers grown by plasma-enhanced chemical vapor deposition at extremely low pressures

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

Choi, Bum Ho, E-mail: bhchoi@kitech.re.kr; Lee, Jong Ho

2014-08-04

We investigated the water vapor permeation barrier properties of 30-nm-thick SiN/SiCN/SiN nanolaminated multilayer structures grown by plasma enhanced chemical vapor deposition at 7 mTorr. The derived water vapor transmission rate was 1.12 × 10{sup −6} g/(m{sup 2} day) at 85 °C and 85% relative humidity, and this value was maintained up to 15 000 h of aging time. The X-ray diffraction patterns revealed that the nanolaminated film was composed of an amorphous phase. A mixed phase was observed upon performing high resolution transmission electron microscope analysis, which indicated that a thermodynamically stable structure was formed. It was revealed amorphous SiN/SiCN/SiN multilayer structures that are freemore » from intermixed interface defects effectively block water vapor permeation into active layer.« less

Understanding the influence of external perturbation on aziridinium ion formation

NASA Astrophysics Data System (ADS)

Sinha, Sourab; Bhattacharyya, Pradip Kr

2018-01-01

A density functional theory study is performed to understand the effect of discrete water molecules during Az+ ion formation in nitrogen mustards. A comparative study in gas phase, and implicit and explicit solvation models of three drug molecules (mustine, chlorambucil and melphalan) is reported. Noteworthy changes in the structure and C-N stretching frequencies of the transition states have been observed in the presence of explicit water molecules. Presence of explicit water molecules reduces the positive charge around the tricyclic Az+ ring, and hence stabilising it. Both activation energy and rate constants are seen to be significantly affected in the presence of discrete water molecules.

Structure of polyhydroxyalkanoate (PHA) synthase PhaC from Chromobacterium sp. USM2, producing biodegradable plastics.

PubMed

Chek, Min Fey; Kim, Sun-Yong; Mori, Tomoyuki; Arsad, Hasni; Samian, Mohammed Razip; Sudesh, Kumar; Hakoshima, Toshio

2017-07-13

Polyhydroxyalkanoate (PHA) is a promising candidate for use as an alternative bioplastic to replace petroleum-based plastics. Our understanding of PHA synthase PhaC is poor due to the paucity of available three-dimensional structural information. Here we present a high-resolution crystal structure of the catalytic domain of PhaC from Chromobacterium sp. USM2, PhaC Cs -CAT. The structure shows that PhaC Cs -CAT forms an α/β hydrolase fold comprising α/β core and CAP subdomains. The active site containing Cys291, Asp447 and His477 is located at the bottom of the cavity, which is filled with water molecules and is covered by the partly disordered CAP subdomain. We designated our structure as the closed form, which is distinct from the recently reported catalytic domain from Cupriavidus necator (PhaC Cn -CAT). Structural comparison showed PhaC Cn -CAT adopting a partially open form maintaining a narrow substrate access channel to the active site, but no product egress. PhaC Cs -CAT forms a face-to-face dimer mediated by the CAP subdomains. This arrangement of the dimer is also distinct from that of the PhaC Cn -CAT dimer. These findings suggest that the CAP subdomain should undergo a conformational change during catalytic activity that involves rearrangement of the dimer to facilitate substrate entry and product formation and egress from the active site.

Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands

NASA Astrophysics Data System (ADS)

Yin, Bing; Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li; Wen, Zhen-Yi; Jiang, Zhen-Yi

2014-03-01

The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg2(CN)5]- clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN-1 were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties.

Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands.

PubMed

Yin, Bing; Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li; Wen, Zhen-Yi; Jiang, Zhen-Yi

2014-03-07

The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg2(CN)5](-) clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN(-1) were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties.

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

PubMed

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.

Influence of proximal side mutations on the molecular and electronic structure of cyanomet myoglobin: an 1H NMR study.

PubMed

Wu, Y; Chien, E Y; Sligar, S G; La Mar, G N

1998-05-12

A series of proximal side mutants of sperm whale metmyoglobin (metMb) that involves residues which provide hydrogen bonds to the axial His and heme have been prepared, and the CO binding and solution molecular and electronic structure has been investigated by 1H NMR. These include Ser92(F7), whose O gamma serves as a hydrogen-bond acceptor to the axial His ring NdeltaH and whose O gamma H serves as hydrogen-bond donor to the 7-propionate carboxylate, and His97(FG3) whose ring provides the other hydrogen-bond donor to the 7-propionate carboxylate. 2D NMR data on the S92A-metMbCN, S92P-metMbCN and H97F-metMbCN show that the distal structure is completely conserved and that proximal side structural changes are highly localized. For the S92A-metMbCN, altered dipolar contacts to the F-helix backbone show that the axial His imidazole has rotated clockwise by approximately 10 degrees relative to a stationary heme, while in H97F-metMbCN, the altered heme-E helix backbone contacts reveal that the heme has rotated counterclockwise by approximately 3 degrees relative to a conserved axial His. The pattern of axial His rotation was qualitatively predicted by energy minimization calculations. The assignments and conserved structural elements allow the determination of a set of magnetic axes whose major magnetic axis is unchanged with respect to WT and confirms that local distal, and not proximal, interactions control the orientation of the major magnetic axis and, by inference, the degree and direction of tilt of the Fe-CN from the heme normal. The rhombic magnetic axes in S92A-metMbCN are rotated approximately 10 degrees in the opposite direction from the established approximately 10 degrees rotation for the axial His ring as expected. It is shown, moreover, that the pairwise alpha-, gamma-meso vs beta-, delta-meso-H hyperfine shift differences are well predicted by the change in the location of the rhombic magnetic axes. Carbon monoxide ligation rates experience minor but systematic perturbation for the S92A substitutions which confirms an influence (albeit very small) for axial His orientation on ligand affinity.

Technetium and rhenium pentacarbonyl complexes with C₂ and C₁₁ ω-isocyanocarboxylic acid esters.

PubMed

Miroslavov, Alexander E; Polotskii, Yuriy S; Gurzhiy, Vladislav V; Ivanov, Alexander Yu; Lumpov, Alexander A; Tyupina, Margarita Yu; Sidorenko, Georgy V; Tolstoy, Peter M; Maltsev, Daniil A; Suglobov, Dmitry N

2014-08-04

Technetium(I) and rhenium(I) pentacarbonyl complexes with ethyl 2-isocyanoacetate and methyl 11-isocyanoundecanoate, [M(CO)5(CNCH2COOEt)]ClO4 (M = Tc (1) and Re (2)) and [M(CO)5(CN(CH2)10COOMe)]ClO4 (M = Tc (3) and Re (4)), were prepared and characterized by IR, (1)H NMR, and (13)C{(1)H} NMR spectroscopy. The crystal structures of 1 and 2 were determined using single-crystal X-ray diffraction. The kinetics of thermal decarbonylation of technetium complexes 1 and 3 in ethylene glycol was studied by IR spectroscopy. The rate constants and activation parameters of this reaction were determined and compared with those for [Tc(CO)6](+). It was found that rhenium complexes 2 and 4 were stable with respect to thermal decarbonylation. Histidine challenge reaction of complexes 1 and 2 in phosphate buffer was examined by IR spectroscopy. In the presence of histidine, the rhenium pentacarbonyl isocyanide complex partially decomposes to form an unidentified yellow precipitate. Technetium analogue 1 is more stable under these conditions.

A Ta/W mixed addenda heteropolyacid with excellent acid catalytic activity and proton-conducting property

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

Li, Shujun; Peng, Qingpo; Chen, Xuenian, E-mail: xnchen@htu.edu.cn

A new HPAs H{sub 20}[P{sub 8}W{sub 60}Ta{sub 12}(H{sub 2}O){sub 4}(OH){sub 8}O{sub 236}]·125H{sub 2}O (H-1) which comprises a Ta/W mixed addenda heteropolyanion, 20 protons, and 125 crystalline water molecules has been prepared through ion-exchange method. The structure and properties of H-1 have been explored in detail. AC impedance measurements indicate that H-1 is a good solid state proton conducting material at room temperature with a conductivity value of 7.2×10{sup −3} S cm{sup −1} (25 °C, 30% RH). Cyclic voltammograms of H-1 indicate the electrocatalytic activity towards the reduction of nitrite. Hammett acidity constant H{sub 0} of H-1 in CH{sub 3}CN ismore » −2.91, which is the strongest among the present known HPAs. Relatively, H-1 exhibits excellent catalytic activities toward acetal reaction. - Highlights: • A Ta/W mixed addenda Heteropolyacid (H-1) was isolated. • Hammett acidity constant H{sub 0} of H-1 is the strongest among the present known HPAs. • H-1 exhibits excellent catalytic activities toward acetal reaction. • H-1 is a good solid state proton conducting material at room temperature.« less

A comprehensive study of the complexation of alkali metal cations by lower rim calix[4]arene amide derivatives.

PubMed

Horvat, Gordan; Frkanec, Leo; Cindro, Nikola; Tomišić, Vladislav

2017-09-13

The complexation of alkali metal cations by lower rim N,N-dihexylacetamide (L1) and newly synthesized N-hexyl-N-methylacetamide (L2) calix[4]arene tertiary-amide derivatives was thoroughly studied at 25 °C in acetonitrile (MeCN), benzonitrile (PhCN), and methanol (MeOH) by means of direct and competitive microcalorimetric titrations, and UV and 1 H NMR spectroscopies. In addition, by measuring the ligands' solubilities, the solution (transfer) Gibbs energies of the ligands and their alkali metal complexes were obtained. The inclusion of solvent molecules in the free and complexed calixarene hydrophobic cavities was also investigated. Computational (classical molecular dynamics) investigations of the studied systems were also carried out. The obtained results were compared with those previously obtained by studying the complexation ability of an N-hexylacetamidecalix[4]arene secondary-amide derivative (L3). The stability constants of 1 : 1 complexes were determined in all solvents used (the values obtained by different methods being in excellent agreement), as were the corresponding complexation enthalpies and entropies. Almost all of the examined reactions were enthalpically controlled. The most striking exceptions were reactions of Li + with both ligands in methanol, for which the entropic contribution to the reaction Gibbs energy was substantial due the entropically favourable desolvation of the smallest lithium cation. The thermodynamic stabilities of the complexes were quite solvent dependent (the stability decreased in the solvent order: MeCN > PhCN ≫ MeOH), which could be accounted for by considering the differences in the solvation of the ligand and free and complexed alkali metal cations in the solvents used. Comparison of the stability constants of the ligand L1 and L2 complexes clearly revealed that the higher electron-donating ability of the hexyl with respect to the methyl group is of considerable importance in determining the equilibria of the complexation reactions. Additionally, the quite strong influence of intramolecular hydrogen bond formation in compound L3 (not present in ligands L1 and L2) and that of the inclusion of solvent molecules in the calixarene hydrophobic cone were shown to be of great importance in determining the thermodynamic stability of the calixarene-cation complexes. The experimental results were fully supported by those obtained by MD simulations.

Ruthenium(II) carbonyl complexes bearing CCC-pincer bis-(carbene) ligands: synthesis, structures and activities toward recycle transfer hydrogenation reactions.

PubMed

Naziruddin, Abbas Raja; Huang, Zhao-Jiunn; Lai, Wei-Chih; Lin, Wan-Jung; Hwang, Wen-Shu

2013-09-28

A new series of ruthenium(II) carbonyl complexes with benzene-based CCC-pincer bis-(carbene) ligands, [((R)CCC(R))Ru(CO)2(X)](0/+) and [((R)CCC(R))Ru(CO)(NN)](+) ((R)CCC(R) = 2,6-bis-(1-alkylimidazolylidene)benzene, R = Me or (n)Bu; X = I, Br, CH3CN, or 6-(aminomethyl)pyridine (ampy); NN = 2·CH3CN, or chelating ampy or bipyridine), was synthesized and fully characterized. X-Ray structure determinations revealed that these eight complexes have pseudo-octahedral configurations around the ruthenium center with the pincer ligand occupying three meridional sites. These complexes prove to be efficient precatalysts demonstrating very good activity and reusability for the transfer hydrogenation of ketones.

Synthesis, structure, and magnetic characterization of a C3-symmetric Mn(III)3Cr(III) assembly: molecular recognition between a trinuclear Mn(III) triplesalen complex and a fac-triscyano Cr(III) complex.

PubMed

Freiherr von Richthofen, Carl-Georg; Stammler, Anja; Bögge, Hartmut; DeGroot, Marty W; Long, Jeffrey R; Glaser, Thorsten

2009-11-02

The reaction of the tris(tetradentate) triplesalen ligand H(6)talen(t-Bu(2)), which provides three salen-like coordination environments bridged in a meta-phenylene arrangement by a phloroglucinol backbone, with Mn(II) salts under aerobic conditions, affords, in situ, the trinuclear Mn(III) triplesalen complex [(talen(t-Bu(2))){Mn(III)(solv)(n)}(3)](3+). This species then reacts with [(Me(3)tacn)Cr(CN)(3)] to form the tetranuclear complex [{(talen(t-Bu(2)))Mn(III)(3)}{(Me(3)tacn)Cr(CN)(3)}](3+) ([Mn(III)(3)Cr(III)](3+)). The regular ligand folding observed in the trinuclear triplesalen complex preorganizes the three metal ions for the reaction with three facially coordinated nitrogen atoms of [(Me(3)tacn)Cr(CN)(3)]. [{(talen(t-Bu(2)))(Mn(III)(MeOH))(3)}{(Me(3)tacn)Cr(CN)(3)}](ClO(4))(3) (1) was characterized by infrared spectroscopy, elemental analysis, mass spectrometry, electron absorption spectroscopy, and magnetic measurements. The molecular structure was established for the acetate-substituted derivative [{(talen(t-Bu(2)))(Mn(III)(MeOH))(2)(Mn(III)(OAc))}{(Me(3)tacn)Cr(CN)(3)}](ClO(4))(2) (2) by single-crystal X-ray diffraction. Variable-temperature-variable-field and mu(eff) versus T magnetic data have been analyzed in detail by full-matrix diagonalization of the appropriate spin-Hamiltonian, consisting of isotropic exchange, zero-field splitting, and Zeeman interaction components. Satisfactory reproduction of the experimental data has been obtained for the parameters J(Mn-Cr) = -0.12 +/- 0.04 cm(-1), J(Mn-Mn) = -0.70 +/- 0.03 cm(-1), and D(Mn) = -3.0 +/- 0.4 cm(-1). These generate a triply degenerate pseudo S(t) = 7/2 spin manifold, which cannot be appropriately described by a giant spin model and which exhibits a weak easy-axis magnetic anisotropy. This is corroborated by the onset of a frequency-dependent chi'' signal at low temperatures, demonstrating a slow relaxation of the magnetization indicative of 1 being a single-molecule magnet. Comparing the properties to those of the heptanuclear analogue [{(talen(t-Bu(2)))Mn(III)(3)}(2){Cr(III)(CN)(6)}](3+) ([Mn(III)(6)Cr(III)](3+)) formed by the reaction of 2 equiv of [(talen(t-Bu(2))){Mn(III)(solv)(n)}(3)](3+) with 1 equiv of [Cr(CN)(6)](3-) [Glaser, T.; Heidemeier, M.; Weyhermüller, T.; Hoffmann, R.-D.; Rupp, H.; Müller, P. Angew. Chem. Int. Ed., 2006, 45, 6033-6037] demonstrates a lower driving force for formation, a strongly reduced J(Mn-Cr) exchange, a slightly reduced J(Mn-Mn) exchange, and a significantly longer Mn-N(N[triple bond]C) bond length in [Mn(III)(3)Cr(III)](3+). Taking into account magneto-structural correlations establishes a supramolecular interaction between the two [(talen(t-Bu(2)))Mn(III)(3)](3+) subunits in [Mn(III)(6)Cr(III)](3+) responsible for the structural distortion and the short Mn-N(N[triple bond]C) distance which results in a strong J(Mn-Cr) exchange and thus [Mn(III)(6)Cr(III)](3+) being a single-molecule magnet with a relatively high effective anisotropy barrier of 25.4 K.

Metabolic Engineering to Develop a Pathway for the Selective Cleavage of Carbon-Nitrogen Bonds

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

John J. Kilbane II

The objective of the project is to develop a biochemical pathway for the selective cleavage of C-N bonds in molecules found in petroleum. Specifically a novel biochemical pathway will be developed for the selective cleavage of C-N bonds in carbazole. The cleavage of the first C-N bond in carbazole is accomplished by the enzyme carbazole dioxygenase, that catalyzes the conversion of carbazole to 2-aminobiphenyl-2,3-diol. The genes encoding carbazole dioxygenase were cloned from Sphingomonas sp. GTIN11 and from Pseudomonas resinovorans CA10. The selective cleavage of the second C-N bond has been challenging, and efforts to overcome that challenge have been themore » focus of recent research in this project. Enrichment culture experiments succeeded in isolating bacterial cultures that can metabolize 2-aminobiphenyl, but no enzyme capable of selectively cleaving the C-N bond in 2-aminobiphenyl has been identified. Aniline is very similar to the structure of 2-aminobiphenyl and aniline dioxygenase catalyzes the conversion of aniline to catechol and ammonia. For the remainder of the project the emphasis of research will be to simultaneously express the genes for carbazole dioxygenase and for aniline dioxygenase in the same bacterial host and then to select for derivative cultures capable of using carbazole as the sole source of nitrogen.« less

Probing the Gaseous Disk of T Tau N with CN 5-4 Lines

NASA Technical Reports Server (NTRS)

Podio, L.; Kamp, I.; Codella, C.; Nisini, B.; Aresu, G.; Brittain, S.; Cabrit, S.; Dougados, C.; Grady, C.; Meijerink, R.;

Ab initio and density functional force field studies on the IR spectra and structure of diazonium dicyanomethylide (diazodicyanomethane)

NASA Astrophysics Data System (ADS)

Georgieva, Miglena K.

2004-03-01

The structure of diazonium dicyanomethylide (diazodicyanomethane) +N 2-C(CN) 2-↔N 2C(CN) 2 has been studied on the basis of ab initio HF, MP2 and DFT BLYP force field calculations, as well as of literature IR spectra and X-ray diffraction structural data. The results have been compared with those obtained for a series of chemical relatives of the title compound, i.e. molecules, push-pull molecules, anions and zwitterions, containing α-dicyano or diazo fragments, and especially substituted ammonium dicyanomethylides and diazomethane +N 2-CH 2-↔N 2CH 2. It has been found on the basis of spectral, bond length, bond order and electric charge analyses that the diazonium (or carbanionic, left) canonical form is much more important for the title zwitterion, than the corresponding one for diazomethane. So, the title compound can be named (and considered as) both diazonium dicyanomethylide and dicyanodiazomethane.

Balance the Carrier Mobility To Achieve High Performance Exciplex OLED Using a Triazine-Based Acceptor.

PubMed

Hung, Wen-Yi; Chiang, Pin-Yi; Lin, Shih-Wei; Tang, Wei-Chieh; Chen, Yi-Ting; Liu, Shih-Hung; Chou, Pi-Tai; Hung, Yi-Tzu; Wong, Ken-Tsung

2016-02-01

A star-shaped 1,3,5-triazine/cyano hybrid molecule CN-T2T was designed and synthesized as a new electron acceptor for efficient exciplex-based OLED emitter by mixing with a suitable electron donor (Tris-PCz). The CN-T2T/Tris-PCz exciplex emission shows a high ΦPL of 0.53 and a small ΔET-S = -0.59 kcal/mol, affording intrinsically efficient fluorescence and highly efficient exciton up-conversion. The large energy level offsets between Tris-PCz and CN-T2T and the balanced hole and electron mobility of Tris-PCz and CN-T2T, respectively, ensuring sufficient carrier density accumulated in the interface for efficient generation of exciplex excitons. Employing a facile device structure composed as ITO/4% ReO3:Tris-PCz (60 nm)/Tris-PCz (15 nm)/Tris-PCz:CN-T2T(1:1) (25 nm)/CN-T2T (50 nm)/Liq (0.5 nm)/Al (100 nm), in which the electron-hole capture is efficient without additional carrier injection barrier from donor (or acceptor) molecule and carriers mobilities are balanced in the emitting layer, leads to a highly efficient green exciplex OLED with external quantum efficiency (EQE) of 11.9%. The obtained EQE is 18% higher than that of a comparison device using an exciplex exhibiting a comparable ΦPL (0.50), in which TCTA shows similar energy levels but higher hole mobility as compared with Tris-PCz. Our results clearly indicate the significance of mobility balance in governing the efficiency of exciplex-based OLED. Exploiting the Tris-PCz:CN-T2T exciplex as the host, we further demonstrated highly efficient yellow and red fluorescent OLEDs by doping 1 wt % Rubrene and DCJTB as emitter, achieving high EQE of 6.9 and 9.7%, respectively.

The phase diagram and hardness of carbon nitrides

DOE PAGES

Dong, Huafeng; Oganov, Artem R.; Zhu, Qiang; ...

2015-05-06

Novel superhard materials, especially those with superior thermal and chemical stability, are needed to replace diamond. Carbon nitrides (C-N), which are likely to possess these characteristics and have even been expected to be harder than diamond, are excellent candidates. Here we report three new superhard and thermodynamically stable carbon nitride phases. Based on a systematic evolutionary structure searches, we report a complete phase diagram of the C-N system at 0–300 GPa and analyze the hardest metastable structures. Surprisingly, we find that at zero pressure, the earlier proposed graphitic-C 3N 4 structure (P6-bar m2) is dynamically unstable, and we find themore » lowest-energy structure based on s-triazine unit and s-heptazine unit.« less

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

Redondo, Pilar; Barrientos, Carmen; Largo, Antonio, E-mail: predondo@qf.uva.es

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, andmore » 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.« less

Development of TRPN dendrimer-modified disordered mesoporous silica for CO{sub 2} capture

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

Zhang, Xiaoyun; Zhang, Sisi; Qin, Hongyan

2014-08-15

Highlights: • A novel series of TRPN dendrimers are synthesized. • Structurally disordered mesoporous silica was used to develop the CO{sub 2} adsorbent. • The CO{sub 2} adsorption capacity is relatively high. • The sorbent exhibits a high stability after 12 cycling runs. • The sorbent achieves complete desorption at low temperature (60 °C). - Abstract: A novel series of tri(3-aminopropyl) amine (TRPN) dendrimers were synthesized and impregnated on structurally disordered mesoporous silica (DMS) to generate CO{sub 2} adsorbents (TS). The physicochemical and adsorption properties of the adsorbents before and after dendrimer modification were characterized by X-ray diffraction (XRD), thermogravimetricmore » analysis (TGA), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and N{sub 2} adsorption–desorption (N{sub 2}-BET) techniques. CO{sub 2} adsorption–desorption tests indicated that the sorbent demonstrates high CO{sub 2} adsorption capacity (138.1 mg g{sup −1} for G1 sample TS-G1-3CN-50 and 91.7 mg g{sup −1} for G2 sample TS-G2-6CN-50), and can completely desorb CO{sub 2} under vacuum at 60 °C. Its CO{sub 2} adsorption capacity at 25 °C increases with the amine loading, achieving the highest adsorption capacity (140.6 mg g{sup −1} for TS-G1-3CN) at 60%. The developed TS materials exhibited excellent cycling stability. After 12 consecutive adsorption–desorption runs, TS-G1-3CN-50 shows an adsorption capacity of 136.0 mg g{sup −1}, retaining 98.5% of its original value.« less

Synthesis, crystal structure and spectroscopic and electrochemical properties of bridged trisbenzoato copper-zinc heterobinuclear complex of 2,2‧-bipyridine

NASA Astrophysics Data System (ADS)

Koch, Angira; Kumar, Arvind; Singh, Suryabhan; Borthakur, Rosmita; Basumatary, Debajani; Lal, Ram A.; Shangpung, Sankey

2015-03-01

The synthesis of the heterobinuclear copper-zinc complex [CuZn(bz)3(bpy)2]ClO4 (bz = benzoate) from benzoic acid and bipyridine is described. Single crystal X-ray diffraction studies of the heterobinuclear complex reveals the geometry of the benzoato bridged Cu(II)-Zn(II) centre. The copper or zinc atom is pentacoordinate, with two oxygen atoms from bridging benzoato groups and two nitrogen atoms from one bipyridine forming an approximate plane and a bridging oxygen atom from a monodentate benzoate group. The Cu-Zn distance is 3.345 Å. The complex is normal paramagnetic having μeff value equal to 1.75 BM, ruling out the possibility of Cu-Cu interaction in the structural unit. The ESR spectrum of the complex in CH3CN at RT exhibit an isotropic four line spectrum centred at g = 2.142 and hyperfine coupling constants Aav = 63 × 10-4 cm-1, characteristic of a mononuclear square-pyramidal copper(II) complexes. At LNT, the complex shows an isotropic spectrum with g|| = 2.254 and g⊥ = 2.071 and A|| = 160 × 10-4 cm-1. The Hamiltonian parameters are characteristic of distorted square pyramidal geometry. Cyclic voltammetric studies of the complex have indicated quasi-reversible behaviour in acetonitrile solution.

Alkali metal-templated assembly of cyanometalate ``boxes'' (NEt{sub 4}){sub 3}{l{underscore}brace}M[Cp*Rh(CN){sub 3}]{sub 4}[Mo(CO){sub 3}]{sub 4}{r{underscore}brace} (M = K, Cs). Selective binding of Cs{sup +}

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

Klausmeyer, K.K.; Wilson, S.R.; Rauchfuss, T.B.

1999-03-31

The box-like cages {l{underscore}brace}M[Cp*Rh(CN){sub 3}]{sub 4}[Mo(CO){sub 3}]{sub 4}{r{underscore}brace}{sup 3{minus}} form as the sole metal-containing products of the reaction of [Cp*Rh(CN){sub 3}]{sup {minus}} and ({eta}{sup 6}-C{sub 6}H{sub 3}Me{sub 3})Mo(CO){sub 3} in the presence of K{sup +} and Cs{sup +}. Well-defined species could not be identified in solutions of Cp*Rh(CN){sub 3}{sup {minus}} ({eta}{sup 6}-C{sub 6}H{sub 3}Me{sub 3})Mo(CO){sub 3} in the absence of alkali metal cations. The new cages were isolated as their Et{sub 4}N{sup +} salts, M = K{sup +} (1), Cs{sup +} (2). Crystallographic characterization of 1 and 2 reveals box-like M{sub 8}({micro}-CN){sub 12} cages containing alkali metal cations. The cagesmore » feature 12 external CO and 4 external C{sub 5}Me{sub 5} ligands. In 1, the K{sup +} is disordered over two off-center positions, whereas in the case of 2, the Cs{sup +} is centered in the cage with a formal coordination number of 24. Otherwise, the structures of the two compounds are virtually indistinguishable. The persistence of the solid-state structures in solution was established through {sup 13}C NMR spectroscopy and electrospray mass spectrometric measurements. {sup 133}Cs NMR spectroscopy, which readily distinguishes free from included Cs{sup +}, shows that the boxes preferentially bind Cs{sup +} relative to K{sup +}.« less

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

Eisenhart, Reed J.; Carlson, Rebecca K.; Clouston, Laura J.

Heterobimetallic complexes that pair cobalt and copper were synthesized and characterized by a suite of physical methods, including X-ray diffraction, X-ray anomalous scattering, cyclic voltammetry, magnetometry, electronic absorption spectroscopy, electron paramagnetic resonance, and quantum chemical methods. Both Cu(II) and Cu(I) reagents were independently added to a Co(II) metalloligand to provide (py3tren)CoCuCl (1-Cl) and (py3tren)CoCu(CH3CN) (2-CH3CN), respectively, where py3tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. Complex 2-CH3CN can lose the acetonitrile ligand to generate a coordination polymer consistent with the formula “(py3tren)CoCu” (2). One-electron chemical oxidation of 2-CH3CN with AgOTf generated (py3tren)CoCuOTf (1-OTf). The Cu(II)/Cu(I) redox couple for 1-OTf andmore » 2-CH3CN is reversible at -0.56 and -0.33 V vs Fc+/Fc, respectively. The copper oxidation state impacts the electronic structure of the heterobimetallic core, as well as the nature of the Co–Cu interaction. Quantum chemical calculations showed modest electron delocalization in the (CoCu)+4 state via a Co–Cu σ bond that is weakened by partial population of the Co–Cu σ antibonding orbital. By contrast, no covalent Co–Cu bonding is predicted for the (CoCu)+3 analogue, and the d-electrons are fully localized at individual metals.« less

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

Eisenhart, Reed J.; Carlson, Rebecca K.; Clouston, Laura J.

Heterobimetallic complexes that pair cobalt and copper were synthesized and characterized by a suite of physical methods, including X-ray diffraction, X-ray anomalous scattering, cyclic voltammetry, magnetometry, electronic absorption spectroscopy, electron paramagnetic resonance, and quantum chemical methods. Both Cu(II) and Cu(I) reagents were independently added to a Co(II) metalloligand to provide (py 3tren)CoCuCl (1-Cl) and (py 3tren)CoCu(CH 3CN) (2-CH 3CN), respectively, where py3tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. Complex 2-CH 3CN can lose the acetonitrile ligand to generate a coordination polymer consistent with the formula “(py3tren)CoCu” (2). One-electron chemical oxidation of 2-CH 3CN with AgOTf generated (py 3tren)CoCuOTf (1-OTf).more » The Cu(II)/Cu(I) redox couple for 1-OTf and 2-CH 3CN is reversible at -0.56 and -0.33 V vs Fc +/Fc, respectively. The copper oxidation state impacts the electronic structure of the heterobimetallic core, as well as the nature of the Co–Cu interaction. Quantum chemical calculations showed modest electron delocalization in the (CoCu) +4 state via a Co–Cu σ bond that is weakened by partial population of the Co–Cu σ antibonding orbital. By contrast, no covalent Co–Cu bonding is predicted for the (CoCu) +3 analogue, and the d-electrons are fully localized at individual metals.« less

Structural insights into Cn-AMP1, a short disulfide-free multifunctional peptide from green coconut water.

PubMed

Santana, Mábio J; de Oliveira, Aline L; Queiroz Júnior, Luiz H K; Mandal, Santi M; Matos, Carolina O; Dias, Renata de O; Franco, Octavio L; Lião, Luciano M

2015-02-27

Multifunctional and promiscuous antimicrobial peptides (AMPs) can be used as an efficient strategy to control pathogens. However, little is known about the structural properties of plant promiscuous AMPs without disulfide bonds. CD and NMR were used to elucidate the structure of the promiscuous peptide Cn-AMP1, a disulfide-free peptide isolated from green coconut water. Data here reported shows that peptide structure is transitory and could be different according to the micro-environment. In this regard, Cn-AMP1 showed a random coil in a water environment and an α-helical structure in the presence of SDS-d25 micelles. Moreover, deuterium exchange experiments showed that Gly4, Arg5 and Met9 residues are less accessible to solvent, suggesting that flexibility and cationic charges seem to be essential for Cn-AMP1 multiple activities. Copyright © 2015 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

Carbon and nitrogen inputs affect soil microbial community structure and function

NASA Astrophysics Data System (ADS)

Liu, X. J. A.; Mau, R. L.; Hayer, M.; Finley, B. K.; Schwartz, E.; Dijkstra, P.; Hungate, B. A.

2016-12-01

Climate change has been projected to increase energy and nutrient inputs to soils, affecting soil organic matter (SOM) decomposition (priming effect) and microbial communities. However, many important questions remain: how do labile C and/or N inputs affect priming and microbial communities? What is the relationship between them? To address these questions, we applied N (NH4NO3 ; 100 µg N g-1 wk-1), C (13C glucose; 1000 µg C g-1 wk-1), C+N to four different soils for five weeks. We found: 1) N showed no effect, whereas C induced the greatest priming, and C+N had significantly lower priming than C. 2) C and C+N additions increased the relative abundance of actinobacteria, proteobacteria, and firmicutes, but reduced relative abundance of acidobacteria, chloroflexi, verrucomicrobia, planctomycetes, and gemmatimonadetes. 3) Actinobacteria and proteobacteria increased relative abundance over time, but most others decreased over time. 4) substrate additions (N, C, C+N) significantly reduced microbial alpha diversity, which also decreased over time. 5) For beta diversity, C and C+N formed significantly different communities compare to the control and N treatments. Overtime, microbial community structure significantly altered. Four soils have drastically different community structures. These results indicate amounts of substrate C were determinant factors in modulating the rate of SOM decomposition and microbial communities. Variable responses of different microbial communities to labile C and N inputs indicate that complex relationships between priming and microbial functions. In general, we demonstrate that energy inputs can quickly accelerate SOM decomposition whereas extra N input can slow this process, though both had similar microbial community responses.

Enantiomeric resolution and X-ray optical activity of a tricobalt extended metal atom chain.

PubMed

Srinivasan, Anandi; Cortijo, Miguel; Bulicanu, Vladimir; Naim, Ahmad; Clérac, Rodolphe; Sainctavit, Philippe; Rogalev, Andrei; Wilhelm, Fabrice; Rosa, Patrick; Hillard, Elizabeth A

2018-02-07

A simple procedure based on anion exchange was employed for the enantiomeric resolution of the extended metal atom chain (EMAC) [Co 3 (dpa) 4 (MeCN) 2 ] 2+ . Use of the chiral salt (NBu 4 ) 2 [As 2 (tartrate) 2 ], (Λ- 1 or Δ- 1 ), resulted in the selective crystallization of the EMAC enantiomers as [Δ-Co 3 (dpa) 4 (MeCN) 2 ](NBu 4 ) 2 [Λ-As 2 (tartarte) 2 ] 2 , (Δ- 2 ) and [Λ-Co 3 (dpa) 4 (MeCN) 2 ](NBu 4 ) 2 [Δ-As 2 (tartrate) 2 ] 2 (Λ- 2 ), respectively, in the P 42 1 2 space group, whereas a racemic mixture of 1 yielded [Co 3 (dpa) 4 (MeCN) 2 ][As 2 (tartrate) 2 ]·2MeCN ( rac - 3 ), which crystallized in the C 2/ c space group. The local electronic and magnetic structure of the EMAC enantiomers was studied, exploiting a variety of dichroisms in single crystals. A strong linear dichroism at the Co K-edge was observed in the orthoaxial configuration, whereas it vanished in the axial orientation, thus spectroscopically confirming the D 4 crystal symmetry. Compounds Δ- 2 and Λ- 2 are shown to be enantiopure materials as evidenced by mirror-image natural circular dichroism spectra in the UV/vis in solution and in the X-ray range at the Co K-edge in single crystals. The surprising absence of detectable X-ray magnetic circular dichroism or X-ray magnetochiral dichroism signals at the Co K-edge, even at low temperature (3 K) and a high magnetic field (17 T), is ascribed to a strongly delocalized spin density on the tricobalt core.

Half-metallicity in the ferrimagnet [MnII(enH)(H2O)][CrIII(CN)6]·H2O: Ab initio study

NASA Astrophysics Data System (ADS)

Li, N.; Yao, K. L.; Zhong, G. H.; Ching, W. Y.

2013-03-01

The density-functional theory (DFT) within the full potential linearized augmented plane wave (FPLAPW) method is applied to study the two-dimensional achiral soft ferrimagnet [MnII(enH)(H2O)][CrIII(CN)6]·H2O. The phase stability, electronic structure, magnetic and conducting properties are investigated. Our results reveal that the compound has a stable ferrimagnetic ground state in good agreement with the experiment. From the spin density distribution, the spin magnetic moment of the compound is mainly from Cr3+ and Mn2+ ions with small contributions from the oxygen, nitrogen and carbon ions. The calculated electronic band structure predicts the compound to be a half-metal with the spin magnetic moment of 1.000 μB per molecule.

A Schiff-based colorimetric fluorescent sensor with the potential for detection of fluoride ions.

PubMed

Huang, Cheng-Yin; Wan, Chin-Feng; Chir, Jiun-Ly; Wu, An-Tai

2013-11-01

A simple Schiff-based colorimetric fluorescent receptor 1 was prepared. It exhibits a "turn-on-type" mode with high sensitivity in the presence of F(-). The change in color is very easily observed by the naked eye in the presence of F(-), whereas other anions do not induce such a change. Job plot indicated a 1:2 complexation stoichiometry between receptor 1 and F(-). The association constant for 1-F(-) in CH3CN was determined as 1.32*10(5) M(-2) by a Hill plot.

Syntheses, structures and luminescence of three copper(I) cyanide coordination polymers based on trigonal 1,3,5-tris(1H-imidazol-1-yl)benzene ligand

NASA Astrophysics Data System (ADS)

Shao, Min; Li, Ming-Xing; Lu, Li-Ruo; Zhang, Heng-Hua

2016-09-01

Three Cu(I)-cyanide coordination polymers based on trigonal 1,3,5-tris(1H-imidazol-1-yl)benzene (tib) ligand, namely [Cu3(CN)3(tib)]n (1), [Cu4(CN)4(tib)]n (2), and [Cu2(CN)2(tib)]n (3), have been prepared and characterized by elemental analysis, IR, PXRD, thermogravimetry and single-crystal X-ray diffraction analysis. Complex 1 displays a 3D metal-organic framework with nanosized pores. Complex 2 is a 3D coordination polymer assembled by three μ2-cyanides and a μ3-cyanide with a very short Cu(I)···Cu(I) metal bond(2.5206 Å). Complex 3 is a 2D coordination polymer constructing from 1D Cu(I)-cyanide zigzag chain and bidentate tib spacer. Three Cu(I) complexes are thermally stable up to 250-350 °C. Complexes 1-3 show similar orange emission band at 602 nm originating from LMCT mechanism.

Conformational and Structural Studies of Isopropylamine from Temperature Dependent Raman Spectra of Xenon Solutions and {AB INITIO} Calculations

NASA Astrophysics Data System (ADS)

Klaassen, Joshua J.; Darkhalil, Ikhlas D.; Durig, James R.

2012-06-01

The Raman and infrared spectra (4000 to 50 cm-1) of the gas, liquid or solution, and solid have been recorded of isopropylamine, (CH3)2CHNH2. Variable temperature (-50 to -100oC) studies of the Raman spectra (3500 to 100 cm-1) dissolved in liquid xenon have been carried out. From these data, both the {trans} and {gauche} conformers have been identified and their relative stability obtained. The enthalpy difference has been determined from 20 band pairs at 6 temperatures to be 113 +/- 11 cm-1 (1.35 +/- 0.13 kJ mol-1) with the {trans} conformer the more stable form. The percentage of the {gauche} conformer is estimated to be 54 +/- 1 percent at ambient temperature. The conformational stabilities have been predicted from {ab initio} calculations utilizing several different basis sets up to aug-cc-pVTZ from both MP2(full) and density functional theory calculations by the B3LYP method. By utilizing previously reported microwave rotational constants along with {ab initio} MP2(full)/6-311+G(d,p) predicted structural values, adjusted r0 parameters have been obtained for the {trans} conformer. The determined heavy atom and NH2 distances in angstroms are C-C = 1.530(3), C-N = 1.465(3), N-H = 1.019(3) and angles in degrees NCC = 108.9(5), CCC = 111.0(5), HNC = 110.3(5). The structural parameters for the {gauche} conformer were estimated by using the same adjustment differences to the {gauche} form as those obtained for the corresponding {trans} parameters. Vibrational assignments have been provided for the observed bands for both conformers which are supported by MP2(full)/6-31G(d) {ab initio} calculations to predict harmonic force constants, wavenumbers, infrared intensities, Raman activities and depolarization ratios for both conformers. The results are discussed and compared to the corresponding properties of some related molecules.

In-Situ Measurements of HCN and CH3CN in the Pacific Troposphere: Sources, Sinks, and Comparisons with Spectroscopic Observations

NASA Technical Reports Server (NTRS)

Singh, Hanwant B.; Salas, L.; Herlth, D.; Czech, E.; Viezee, W.; Li, Q.; Jacob, D. J.; Blake, D.; Sachse, G.; Harward, C. N.;

The effect of specific solvent-solute interactions on complexation of alkali-metal cations by a lower-rim calix[4]arene amide derivative.

PubMed

Horvat, Gordan; Stilinović, Vladimir; Kaitner, Branko; Frkanec, Leo; Tomišić, Vladislav

2013-11-04

Complexation of alkali-metal cations with calix[4]arene secondary-amide derivative, 5,11,17,23-tetra(tert-butyl)-25,26,27,28-tetra(N-hexylcarbamoylmethoxy)calix[4]arene (L), in benzonitrile (PhCN) and methanol (MeOH) was studied by means of microcalorimetry, UV and NMR spectroscopies, and in the solid state by X-ray crystallography. The inclusion of solvent molecules (including acetonitrile, MeCN) in the calixarene hydrophobic cavity was also investigated. The classical molecular dynamics (MD) simulations of the systems studied were carried out. By combining the results obtained using the mentioned experimental and computational techniques, an attempt was made to get an as detailed insight into the complexation reactions as possible. The thermodynamic parameters, that is, equilibrium constants, reaction Gibbs energies, enthalpies, and entropies, of the investigated processes were determined and discussed. The stability constants of the 1:1 (metal:ligand) complexes measured by different methods were in very good agreement. Solution Gibbs energies of the ligand and its complexes with Na(+) and K(+) in methanol and acetonitrile were determined. It was established that from the thermodynamic point of view, apart from cation solvation, the most important reason for the huge difference in the stability of these complexes in the two solvents lay in the fact that the transfer of complex species from MeOH to MeCN was quite favorable. That could be at least partly explained by a more exergonic inclusion of the solvent molecule in the complexed calixarene cone in MeCN as compared to MeOH, which was supported by MD simulations. Molecular and crystal structures of the lithium cation complex of L with the benzonitrile molecule bound in the hydrophobic calixarene cavity were determined by single-crystal X-ray diffraction. As far as we are aware, for the first time the alkali-metal cation was found to be coordinated by the solvent nitrile group in a calixarene adduct. According to the results of MD simulations, the probability of such orientation of the benzonitrile molecule included in the ligand cone was by far the largest in the case of LiL(+) complex. Because of the favorable PhCN-Li(+) interaction, L was proven to have the highest affinity toward the lithium ion in benzonitrile, which was not the case in the other solvents examined (in acetonitrile, sodium complex was the most stable, whereas in methanol, complexation of lithium was not even observed). That could serve as a remarkable example showing the importance of specific solvent-solute interactions in determining the equilibrium in solution.

Aqueous solvation of Mg(ii) and Ca(ii): A Born-Oppenheimer molecular dynamics study of microhydrated gas phase clusters

NASA Astrophysics Data System (ADS)

León-Pimentel, C. I.; Amaro-Estrada, J. I.; Hernández-Cobos, J.; Saint-Martin, H.; Ramírez-Solís, A.

2018-04-01

The hydration features of [Mg(H2O)n ] 2 + and [Ca(H2O)n ] 2 + clusters with n = 3-6, 8, 18, and 27 were studied by means of Born-Oppenheimer molecular dynamics simulations at the B3LYP/6-31+G** level of theory. For both ions, it is energetically more favorable to have all water molecules in the first hydration shell when n ≤ 6, but stable lower coordination average structures with one water molecule not directly interacting with the ion were found for Mg2+ at room temperature, showing signatures of proton transfer events for the smaller cation but not for the larger one. A more rigid octahedral-type structure for Mg2+ than for Ca2+ was observed in all simulations, with no exchange of water molecules to the second hydration shell. Significant thermal effects on the average structure of clusters were found: while static optimizations lead to compact, spherically symmetric hydration geometries, the effects introduced by finite-temperature dynamics yield more prolate configurations. The calculated vibrational spectra are in agreement with infrared spectroscopy results. Previous studies proposed an increase in the coordination number (CN) from six to eight water molecules for [Ca(H2O)n ] 2 + clusters when n ≥ 12; however, in agreement with recent measurements of binding energies, no transition to a larger CN was found when n > 8. Moreover, the excellent agreement found between the calculated extended X-ray absorption fine structure spectroscopy spectra for the larger cluster and the experimental data of the aqueous solution supports a CN of six for Ca2+.

Fabrication and characterization of thick-film piezoelectric lead zirconate titanate ceramic resonators by tape-casting.

PubMed

Qin, Lifeng; Sun, Yingying; Wang, Qing-Ming; Zhong, Youliang; Ou, Ming; Jiang, Zhishui; Tian, Wei

2012-12-01

In this paper, thick-film piezoelectric lead zirconate titanate (PZT) ceramic resonators with thicknesses down to tens of micrometers have been fabricated by tape-casting processing. PZT ceramic resonators with composition near the morphotropic phase boundary and with different dopants added were prepared for piezoelectric transducer applications. Material property characterization for these thick-film PZT resonators is essential for device design and applications. For the property characterization, a recently developed normalized electrical impedance spectrum method was used to determine the electromechanical coefficient and the complex piezoelectric, elastic, and dielectric coefficients from the electrical measurement of resonators using thick films. In this work, nine PZT thick-film resonators have been fabricated and characterized, and two different types of resonators, namely thickness longitudinal and transverse modes, were used for material property characterization. The results were compared with those determined by the IEEE standard method, and they agreed well. It was found that depending on the PZT formulation and dopants, the relative permittivities ε(T)(33)/ε(0) measured at 2 kHz for these thick-films are in the range of 1527 to 4829, piezoelectric stress constants (e(33) in the range of 15 to 26 C/m(2), piezoelectric strain constants (d(31)) in the range of -169 × 10(-12) C/N to -314 × 10(-12) C/N, electromechanical coupling coefficients (k(t)) in the range of 0.48 to 0.53, and k(31) in the range of 0.35 to 0.38. The characterization results shows tape-casting processing can be used to fabricate high-quality PZT thick-film resonators, and the extracted material constants can be used to for device design and application.

Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2'-bipyridine)(CN) 4] 2-

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

Kjær, Kasper S.; Kunnus, Kristjan; Harlang, Tobias C. B.

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 (MLCT) excited state of [Fe(bpy)(CN) 4] 2- has a 19 picosecond lifetime and no discernable contribution from metal centered (MC) states in weak Lewis acid solvents, such as dimethyl sulfoxide and acetonitrile. Here, in the present work, we use the same combination of spectroscopic techniques to measure the MLCT excited state relaxation dynamics of [Fe(bpy)(CN) 4] 2-more » 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 has triplet ( 3MC) character, unlike other reported six-coordinate Fe(II)-centered coordination compounds, which form MC quintet ( 5MC) states. The solvent dependent changes in excited state non-radiative relaxation for [Fe(bpy)(CN) 4] 2- allows us to infer the influence of the solvent on the electronic structure of the complex. Lastly, the robust characterization of the dynamics and optical spectral signatures of the isolated 3MC intermediate provides a strong foundation for identifying 3MC intermediates in the electronic excited state relaxation mechanisms of similar Fe-centered systems being developed for solar applications.« less

Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2'-bipyridine)(CN) 4] 2-

DOE PAGES

Kjær, Kasper S.; Kunnus, Kristjan; Harlang, Tobias C. B.; ...

2018-01-19

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 (MLCT) excited state of [Fe(bpy)(CN) 4] 2- has a 19 picosecond lifetime and no discernable contribution from metal centered (MC) states in weak Lewis acid solvents, such as dimethyl sulfoxide and acetonitrile. Here, in the present work, we use the same combination of spectroscopic techniques to measure the MLCT excited state relaxation dynamics of [Fe(bpy)(CN) 4] 2-more » 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 has triplet ( 3MC) character, unlike other reported six-coordinate Fe(II)-centered coordination compounds, which form MC quintet ( 5MC) states. The solvent dependent changes in excited state non-radiative relaxation for [Fe(bpy)(CN) 4] 2- allows us to infer the influence of the solvent on the electronic structure of the complex. Lastly, the robust characterization of the dynamics and optical spectral signatures of the isolated 3MC intermediate provides a strong foundation for identifying 3MC intermediates in the electronic excited state relaxation mechanisms of similar Fe-centered systems being developed for solar applications.« less

Effect of solvent on the electronic absorption spectral properties of some mixed β-octasubstituted Zn(II)-tetraphenylporphyrins

NASA Astrophysics Data System (ADS)

Bhyrappa, P.; Sankar, M.

2018-01-01

A series of mixed β-octasubstituted Zn(II)-porphyrins, 2,3,12,13-tetra(chloro/cyano/methyl)-5,7,8,10,15,17,18,20-octaphenylporphinato zinc(II), ZnTPP(Ph)4X4 (X = CN, Cl and CH3) have been examined by electronic absorption spectroscopy in various solvents. These Zn(II)-porphyrins exhibited varying degree of red-shift of absorption bands as high as 20-30 nm in 'B' band and 50-60 nm in longest wavelength band, 'Q(0,0)' band in polar solvents relative to that found in nonpolar solvents. The red-shift of B and Q(0,0) bands showed an unusual trend, ZnTPP(Ph)4(CN)4 > ZnTPP(Ph)4(CH3)4 > ZnTPP(Ph)4Cl4 but fails to follow an anticipated anodic shift in first porphyrin ring oxidation (vs Ag/AgCl) potential: ZnTPP(Ph)4(CN)4 (1.02 V) > ZnTPP(Ph)4Cl4 (0.74 V) > ZnTPP(Ph)4(CH3)4 (0.38 V). Such a trend suggests the combined effect of non-planarity of the macrocycle and electronic effect of the peripheral substituents. The equilibrium constants for the binding of nitrogenous bases with the Zn(II)-porphyrins showed as high as twenty fold increase for ZnTPP(Ph)4X4 (X = Br and CN) relative to ZnTPP(Ph)4(CH3)4 and follow the order: ZnTPP(Ph)4(CN)4 > ZnTPP(Ph)4Br4 > ZnTPP(Ph)4(CH3)4 ≤ ZnTPP which is approximately in line with an increase in anodic shift of their first ring redox potentials (ZnTPP(Ph)4(CN)4 (1.02 V) > ZnTPP(Ph)4Br4 (0.72 V) > ZnTPP (0.84 V) > ZnTPP(Ph)4(CH3)4) (0.38 V).

Cavernous malformations isolated from cranial nerves: Unexpected diagnosis?

PubMed

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 MR follow-up, recurrence was excluded in all patients. CN CMs present with specific symptoms and require complex surgical techniques for resection. These lesions are frequently symptomatic, because of the complexity of the origin tissue. Symptomatic CN CMs should be resected microsurgically and completely when possible to prevent further losses of nerve function, improve function, avoid recurrence, and to eliminate the risk of future haemorrhages. The authors discuss the therapeutic options and the radiological features of these infrequent localisation of CMs. Specifically, the authors focus on the role of magnetic resonance imaging in the identification of these rare lesions. Copyright © 2014 Elsevier B.V. All rights reserved.

Studies of Cobalt-Mediated Electrocatalytic CO2 Reduction Using a Redox-Active Ligand

PubMed Central

2015-01-01

The cobalt complex [CoIIIN4H(Br)2]+ (N4H = 2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene) was used for electrocatalytic CO2 reduction in wet MeCN with a glassy carbon working electrode. When water was employed as the proton source (10 M in MeCN), CO was produced (fCO= 45% ± 6.4) near the CoI/0 redox couple for [CoIIIN4H(Br)2]+ (E1/2 = −1.88 V FeCp2+/0) with simultaneous H2 evolution (fH2= 30% ± 7.8). Moreover, we successfully demonstrated that the catalytically active species is homogeneous through the use of control experiments and XPS studies of the working glassy-carbon electrodes. As determined by cyclic voltammetry, CO2 catalysis occurred near the formal CoI/0redox couple, and attempts were made to isolate the triply reduced compound (“[Co0N4H]”). Instead, the doubly reduced (“CoI”) compounds [CoN4] and [CoN4H(MeCN)]+ were isolated and characterized by X-ray crystallography. Their molecular structures prompted DFT studies to illuminate details regarding their electronic structure. The results indicate that reducing equivalents are stored on the ligand, implicating redox noninnocence in the ligands for H2 evolution and CO2 reduction electrocatalysis. PMID:24773584

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

Wong-Ng, Winnie; Culp, Jeffrey T.; Chen, Yu-S.

The chartreuse monoclinic Ni-dpbz (Ni(L)[Ni(CN) 4], (L = 1,4-Bis(4-pyridyl)benzene, or dpbz) crystal assumes a pillared structure with layers defined by 2-D Ni[Ni(CN) 4] n nets and dpbz ligands as pillars, linking between coordinated Ni sites. In addition to the hysteretic adsorption/desorption feature of Ni-dpbz, in half of the parallelepiped-shape space enclosed by the pillars and nets, an additional dpbz ligand was found to link between the open ends of two four-fold Ni sites. This arrangement results in an unusual 5-fold pseudo square-pyramid environment for Ni and a significantly long Ni–N distance of 2.369(4) Å. The presence of disordered dimethyl sulfoxidemore » (DMSO) solvent molecules give rise to the formula of Ni(dpbz)[Ni(CN) 4]·½dpbz·0.44DMSO. Sorption isotherms showed flexible behavior during the adsorption and desorption of CO 2.« less

Structural distortions upon oxidation in heteroleptic [Cp(2)W(dmit)] tungsten dithiolene complex: combined structural, spectroscopic, and magnetic studies.

PubMed

Reinheimer, Eric W; Olejniczak, Iwona; Łapiński, Andrzej; Swietlik, Roman; Jeannin, Olivier; Fourmigué, Marc

2010-11-01

Four different cation radical salts are obtained upon electrocrystallization of [Cp(2)W(dmit)] (dmit = 1,3-dithiole-2-thione-4,5-dithiolato) in the presence of the BF(4)(-), PF(6)(-), Br(-), and [Au(CN)(2)](-) anions. In these formally d(1) cations, the WS(2)C(2) metallacycle is folded along the S···S hinge to different extents in the four salts, an illustration of the noninnocent character of the dithiolate ligand. Structural characteristics and the charge distribution on atoms, for neutral and ionized complexes with various folding angles, were calculated using DFT methods, together with the normal vibrational modes and theoretical Raman spectra. Raman spectra of neutral complex [Cp(2)W(dmit)] and its salts formed with BF(4)(-), AsF(6)(-), PF(6)(-), Br(-), and [Au(CN)(2)](-) anions were measured using the red excitation (λ = 632.8 nm). A correlation between the folding angle of the metallacycle and the Raman spectroscopic properties is analyzed. The bands attributed to the C═C and C-S stretching modes shift toward higher and lower frequencies by about 0.3-0.4 cm(-1) deg(-1), respectively. The solid state structural and magnetic properties of the three salts are analyzed and compared with those of the corresponding molybdenum complexes. Temperature dependence of the magnetic susceptibility shows the presence of one-dimensional antiferromagnetic interactions in the BF(4)(-), PF(6)(-), and [Au(CN)(2)](-) salts, while an antiferromagnetic ground state is identified in the Br(-) salt below T(Néel) = 7 K. Interactions are systematically weaker in the tungsten salts than in the isostructural molybdenum analogs, a consequence of the decreased spin density on the dithiolene ligand in the tungsten complexes.

Fabrication and Structural Characterization of an Ultrathin Film of a Two-Dimensional-Layered Metal-Organic Framework, {Fe(py)2[Ni(CN)4]} (py = pyridine).

PubMed

Sakaida, Shun; Haraguchi, Tomoyuki; Otsubo, Kazuya; Sakata, Osami; Fujiwara, Akihiko; Kitagawa, Hiroshi

2017-07-17

We report the fabrication and characterization of the first example of a tetracyanonickelate-based two-dimensional-layered metal-organic framework, {Fe(py) 2 Ni(CN) 4 } (py = pyridine), thin film. To fabricate a nanometer-sized thin film, we utilized the layer-by-layer method, whereby a substrate was alternately soaked in solutions of the structural components. Surface X-ray studies revealed that the fabricated film was crystalline with well-controlled growth directions both parallel and perpendicular to the substrate. In addition, lattice parameter analysis indicated that the crystal system is found to be close to higher symmetry by being downsized to a thin film.

Interferon induction by two 2'-modified double-helical RNAs, poly(2'-fluoro-2'-deoxyinosinic acid) x poly(cytidylic acid) and poly(2'-chloro-2'-deoxyinosinic acid) x poly(cytidylic acid).

PubMed

De Clercq, E; Stollar, B D; Hobbs, J; Fukui, T; Kakiuchi, N; Ikehara, M

1980-01-01

In addition to the 2'-azido analogue of (I)n x (C)n, (dIn3)n x (C)n, we have found two other (I)n x (C)n analogues, (dIfl)n x (C)n and (dIcl)n x (C)n, in which the 2'-hydroxyls of the (I)n strand are replaced by either fluorine or chlorine, to be highly effective in inducing interferon. This contrasted with the lack of interferon-inducing activity noted for various other 2'-halogeno analogues of (I)n x (C)n and (A)n x (U)n, i.e. (I)n x (dCcl)n, (dAfl)n x (U)n, (dAcl)n x (U)n, (A)n x (dUfl)n and (A)n x (dUcl)n. In most assay systems, viz. primary rabbit kidney cells, human diploid fibroblasts, HeLa cells, interferon-primed mouse L-929 cells, and intact rabbits, (dIfl)n x (C)n and (dIcl)n x (C)n induced interferon levels that were comparable to those induced by (I)n x (C)n. There was one particular system (L-929 cells treated with DEAE-dextran), however, in which (dIfl)n x (C)n and (dIcl)n x (C)n, unlike (I)n x (C)n, failed to stimulate interferon production. As monitored by both radiochemical and biological means, (dIfl)n x (C)n and, to a lesser extent, (dIcl)n x (C)n were more resistant to degradation by ribonuclease A, T1 and human serum nucleases than was (I)n x (C)n. In their reactivity towards antibodies to double-stranded RNA (dIfl)n x (C)n and (dIcl)n x (C)n conformed more closely to (I)n x (C)n than did other 2'-substituted (e.g. 2'-O-methyl or 2'-O-ethyl) analogues of (I)n x (C)n. The high interferon-inducing potency of (dIfl)n x (C)n and (dIcl)n x (C)n has both theoretical and practical implications. While our findings suggest that (dIfl)n x (C)n and (dIcl)n x (C)n should be further explored for their therapeutic potentials, they also strengthen the notion that the interferon-inducing capacity, and possibly other biological functions of double-stranded RNAs is dependent on the recognition of the overall conformation of the polynucleotide rather than on the binding of specific functional groups such as the 2'-hydroxyl group.

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

PubMed

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.

The Molybdenum(V) and Tungsten(VI) Oxoazides [MoO(N3 )3 ], [MoO(N3 )3 ⋅2 CH3 CN], [(bipy)MoO(N3 )3 ], [MoO(N3 )5 ](2-) , [WO(N3 )4 ], and [WO(N3 )4 ⋅CH3 CN].

PubMed

Haiges, Ralf; Skotnitzki, Juri; Fang, Zongtang; Dixon, David A; Christe, Karl O

2015-12-14

A series of novel molybdenum(V) and tungsten(VI) oxoazides was prepared starting from [MOF4 ] (M=Mo, W) and Me3 SiN3 . While [WO(N3 )4 ] was formed through fluoride-azide exchange in the reaction of Me3 SiN3 with WOF4 in SO2 solution, the reaction with MoOF4 resulted in a reduction of Mo(VI) to Mo(V) and formation of [MoO(N3 )3 ]. Carried out in acetonitrile solution, these reactions resulted in the isolation of the corresponding adducts [MoO(N3 )3 ⋅2 CH3 CN] and [WO(N3 )4 ⋅CH3 CN]. Subsequent reactions of [MoO(N3 )3 ] with 2,2'-bipyridine and [PPh4 ][N3 ] resulted in the formation and isolation of [(bipy)MoO(N3 )3 ] and [PPh4 ]2 [MoO(N3 )5 ], respectively. Most molybdenum(V) and tungsten(VI) oxoazides were fully characterized by their vibrational spectra, impact, friction and thermal sensitivity data and, in the case of [WO(N3 )4 ⋅CH3 CN], [(bipy)MoO(N3 )3 ], and [PPh4 ]2 [MoO(N3 )5 ], by their X-ray crystal structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The interactions between the sterically demanding trimesitylphosphine oxide and trimesityphosphine with scandium and selected lanthanide ions

NASA Astrophysics Data System (ADS)

Platt, Andrew W. G.; Singh, Kuldip

2016-05-01

The reactions between lanthanide nitrates, Ln(NO3)3 and scandium and lanthanide trifluoromethane sulfonates, Ln(Tf)3 with trimesitylphosphine oxide, Mes3PO show that coordination to the metal ions does not lead to crystalline complexes. Investigation of the reactions by 31-P NMR spectroscopy shows that weak complexes are formed in solution. The crystal structures of Mes3PO·0.5CH3CN (1) and [Mes3PO]3H3O·2CH3CN·Tf (2), formed in the reaction between ScTf3 and Mes3PO, are reported. Trimesitylphosphine, Mes3P, is protonated by scandium and lanthanide trifluoromethane sulfonates and lanthanide nitrates in CD3CN and the structure of [Mes3PH]Cl·HCl·2H2O (3) is reported.

Phase transitions of doped carbon in CrCN coatings with modified mechanical and tribological properties via filtered cathodic vacuum arc deposition

NASA Astrophysics Data System (ADS)

Guan, J. J.; Wang, H. Q.; Qin, L. Z.; Liao, B.; Liang, H.; Li, B.

2017-04-01

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 N2/C2H2 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 C2H2 content ranging from 5% to 20%, and it will be evolved into amorphous carbon and amorphous CNx phases as C2H2 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% C2H2 content, due to the graphite (sp2 Csbnd C) phase embed in CrN host lattice; while the chromium carbon (Cr3C2) and diamond (sp3 Csbnd C) phases may give rise to the increase of the coating hardness with the highest value at 23.97 GPa under 20% C2H2 content.

Experimental and Computational Studies of Binding of Dinitrogen, Nitriles, Azides, Diazoalkanes, Pyridine and Pyrazines to M(PR3)2(CO)3 (M=Mo, W; R=Me, iPr)

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

Hoff, C.D.; Muckerman, J.; Achord, P.

2009-08-17

The enthalpies of binding of a number of N-donor ligands to the complex Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3} in toluene have been determined by solution calorimetry and equilibrium measurements. The measured binding enthalpies span a range of {approx}10 kcal mol{sup -1}: {Delta}H{sub binding} = -8.8 {+-} 1.2 (N{sub 2}-Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}); -10.3 {+-} 0.8 (N{sub 2}); -11.2 {+-} 0.4 (AdN{sub 3} (Ad = 1-adamantyl)); -13.8 {+-} 0.5 (N{sub 2}CHSiMe{sub 3}); -14.9 {+-} 0.9 (pyrazine = pz); -14.8 {+-} 0.6 (2,6-Me{sub 2}pz); -15.5 {+-} 1.8 (Me{sub 2}NCN); -16.6 {+-} 0.4 (CH{sub 3}CN); -17.0 {+-} 0.4 (pyridine); -17.5 {+-} 0.8more » ([4-CH{sub 3}pz][PF{sub 6}] (in tetrahydrofuran)); -17.6 {+-} 0.4 (C{sub 6}H{sub 5}CN); -18.6 {+-} 1.8 (N{sub 2}CHC(=O)OEt); and -19.3 {+-} 2.5 kcal mol{sup -1} (pz)Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}). The value for the isonitrile AdNC (-29.0 {+-} 0.3) is 12.3 kcal mol{sup -1} more exothermic than that of the nitrile AdCN (-16.7 {+-} 0.6 kcal mol{sup -1}). The enthalpies of binding of a range of arene nitrile ligands were also studied, and remarkably, most nitrile complexes were clustered within a 1 kcal mol{sup -1} range despite dramatic color changes and variation of v{sub CN}. Computed structural and spectroscopic parameters for the complexes Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}L are in good agreement with experimental data. Computed binding enthalpies for Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}L exhibit considerable scatter and are generally smaller compared to the experimental values, but relative agreement is reasonable. Computed enthalpies of binding using a larger basis set for Mo(PMe{sub 3}){sub 2}(CO){sub 3}L show a better fit to experimental data than that for Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}L using a smaller basis set. Crystal structures of Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(AdCN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(Me{sub 2}NCN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(2,6-F{sub 2}C{sub 6}H{sub 3}CN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(2,4,6-Me{sub 3}C{sub 6}H{sub 2}CN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(2,6-Me{sub 2}pz), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(AdCN), Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(AdNC), and W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(AdNC) are reported.« less

Supramolecular architectures with π-acidic 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine cavities: role of anion-π interactions in the remarkable stability of Fe(II) metallacycles in solution.

PubMed

Chifotides, Helen T; Giles, Ian D; Dunbar, Kim R

2013-02-27

The comprehensive investigation reported herein provides compelling evidence that anion-π interactions are the main driving force in the formation of self-assembled Fe(II)-templated metallacycles with bptz [3,6-bis(2-pyridyl)-1,2,4,5-tetrazine] in high yields. It was demonstrated by X-ray crystallography, (1)H NMR, solution and solid-state MAS (19)F NMR spectroscopies, CV and MS studies that the anions [X](-) = [BF(4)](-), [ClO(4)](-) and the anions [Y](-) = [SbF(6)](-), [AsF(6)](-), [PF(6)](-) template molecular squares [Fe(4)(bptz)(4)(CH(3)CN)(8)][X](8) and pentagons [Fe(5)(bptz)(5)(CH(3)CN)(10)][Y](10), respectively. The X-ray structures of [{Fe(4)(bptz)(4)(CH(3)CN)(8)}⊂BF(4)][BF(4)](7) and [{Fe(5)(bptz)(5)(CH(3)CN)(10)}⊂2SbF(6)][SbF(6)](8) revealed that the [BF(4)](-) and [SbF(6)](-) anions occupy the π-acidic cavities, establishing close directional F···C(tetrazine) contacts with the tetrazine rings that are by ~0.4 Å shorter than the sum of the F···C van der Waals radii (ΣR(vdW) F···C = 3.17 Å). The number and strength of F···C(tetrazine) contacts are maximized; the F···C(tetrazine) distances and anion positioning versus the polygon opposing tetrazine rings are in agreement with DFT calculations for C(2)N(4)R(2)···[X](-)···C(2)N(4)R(2) (R = F, CN; [X](-) = [BF(4)](-), [PF(6)](-)). In unprecedented solid-state (19)F MAS NMR studies, the templating anions, engaged in anion-π interactions in the solid state, exhibit downfield chemical shifts Δδ((19)F) ≈ 3.5-4.0 ppm versus peripheral anions. NMR, CV, and MS studies also establish that the Fe(II) metallacycles remain intact in solution. Additionally, interconversion studies between the Fe(II) metallacycles in solution, monitored by (1)H NMR spectroscopy, underscore the remarkable stability of the metallapentacycles [Fe(5)(bptz)(5)(CH(3)CN)(10)][PF(6)](10) ≪ [Fe(5)(bptz)(5)(CH(3)CN)(10)][SbF(6)](10) < [Fe(5)(bptz)(5)(CH(3)CN)(10)][AsF(6)](10) versus [Fe(4)(bptz)(4)(CH(3)CN)(8)][BF(4)](8), given the inherent angle strain in five-membered rings. Finally, the low anion activation energies of encapsulation (ΔG(‡) ≈ 50 kJ/mol), determined from variable-temperature (19)F NMR studies for [Fe(5)(bptz)(5)(CH(3)CN)(10)][PF(6)](10) and [Zn(4)(bptz)(4)(CH(3)CN)(8)][BF(4)](8), confirm anion encapsulation in the π-acidic cavities by anion-π contacts (~20-70 kJ/mol).

A thermochromic silver nanocluster exhibiting dual emission character

NASA Astrophysics Data System (ADS)

Xu, Qing-Qing; Dong, Xi-Yan; Huang, Ren-Wu; Li, Bo; Zang, Shuang-Quan; Mak, Thomas C. W.

2015-01-01

A Ag12(SCH2C10H7)6(CF3CO2)6(CH3CN)6 (1) nanocluster modified using naphthalen-2-yl-methanethiol was synthesized and structurally characterized by single crystal X-ray analysis. The targeted luminescent nanocluster displays dual emission with the property of reversible thermochromism spanning from red to bright yellow.A Ag12(SCH2C10H7)6(CF3CO2)6(CH3CN)6 (1) nanocluster modified using naphthalen-2-yl-methanethiol was synthesized and structurally characterized by single crystal X-ray analysis. The targeted luminescent nanocluster displays dual emission with the property of reversible thermochromism spanning from red to bright yellow. Electronic supplementary information (ESI) available: Experimental section and supporting Fig. S1-S6. CCDC 1004246. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4nr05122j

Effect of the Hydrofluoroether Cosolvent Structure in Acetonitrile-Based Solvate Electrolytes on the Li+ Solvation Structure and Li-S Battery Performance.

PubMed

Shin, Minjeong; Wu, Heng-Liang; Narayanan, Badri; See, Kimberly A; Assary, Rajeev S; Zhu, Lingyang; Haasch, Richard T; Zhang, Shuo; Zhang, Zhengcheng; Curtiss, Larry A; Gewirth, Andrew A

2017-11-15

We evaluate hydrofluoroether (HFE) cosolvents with varying degrees of fluorination in the acetonitrile-based solvate electrolyte to determine the effect of the HFE structure on the electrochemical performance of the Li-S battery. Solvates or sparingly solvating electrolytes are an interesting electrolyte choice for the Li-S battery due to their low polysulfide solubility. The solvate electrolyte with a stoichiometric ratio of LiTFSI salt in acetonitrile, (MeCN) 2 -LiTFSI, exhibits limited polysulfide solubility due to the high concentration of LiTFSI. We demonstrate that the addition of highly fluorinated HFEs to the solvate yields better capacity retention compared to that of less fluorinated HFE cosolvents. Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that HFEs exhibiting a higher degree of fluorination coordinate to Li + at the expense of MeCN coordination, resulting in higher free MeCN content in solution. However, the polysulfide solubility remains low, and no crossover of polysulfides from the S cathode to the Li anode is observed.

Effect of the Hydrofluoroether Cosolvent Structure in Acetonitrile-Based Solvate Electrolytes on the Li+ Solvation Structure and Li-S Battery Performance.

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

Shin, Minjeong; Wu, Heng-Liang; Narayanan, Badri

We evaluate hydrofluoroether (HFE) cosolvents with varying degrees of fluorination in the acetonitrile-based solvate electrolyte to determine the effect of the HFE structure on the electrochemical performance of the Li-S battery. Solvates or sparingly solvating electrolytes are an interesting electrolyte choice for the Li-S battery due to their low polysulfide solubility. The solvate electrolyte with a stoichiometric ratio of LiTFSI salt in acetonitrile, (MeCN)(2)-LiTFSI, exhibits limited polysulfide solubility due to the high concentration of LiTFSI. We demonstrate that the addition of highly fluorinated HFEs to the solvate yields better capacity retention compared to that of less fluorinated HFE cosolvents. Ramanmore » and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that HFEs exhibiting a higher degree of fluorination coordinate to Li+ at the expense of MeCN coordination, resulting in higher free MeCN content in solution. However, the polysulfide solubility remains low, and no crossover of polysulfides from the S cathode to the Li anode is observed.« less

Hydrothermal recrystallization of transition metal nitroprussides. Formation of the most stable phases

NASA Astrophysics Data System (ADS)

Echevarría, F.; Reguera, L.; González M, M.; Galicia, J.; Ávila, M.; Reguera, E.

2018-02-01

Hydrothermal recrystallization appears to be an appropriate treatment to explore the structural diversity of porous coordination polymers. In this contribution, such a post-synthesis treatment is applied to divalent transition metal nitroprussides, T[Fe(CN)5NO]•xH2O with T =Mn, Fe, Co, Ni, Cu, Zn, Cd. This family of compounds forms an interesting series of nanoporous coordination polymers with a wide structural diversity, related to the synthesis route used and the solid hydration degree (x). The effect of a hydrothermal recrystallization of previously prepared fine powders using the precipitation method, on their crystal structure and related properties is herein discussed. In this series of coordination polymers, for Fe, Co, Ni the precipitated powders are obtained as cubic phase, with a high porosity related to presence of systematic vacancies for building unit [Fe(CN)5NO]. For Fe and Co a structural transition, from cubic to orthorhombic, was observed, which is associated to formation of a most compact structure. The crystal structure for the new orthorhombic phases was refined from the collected powder HR-XRD patterns. For Ni, the cubic phase remains stable even for large heating time, which is ascribed to the high polarizing power of this metal. The high porosity for the cubic phase allows an easy accommodation for the local deformations around the Ni atom coordination sphere. The structural information from XRD was complemented with CO2 and H2 adsorption and TG data, IR and UV-vis spectra, and magnetic measurements. The magnetic data, through the presence of spin-orbit coupling for Fe and Co in the two phases, provide fine details on the coordination environment for the metal linked at the N ends of the CN group.

N-benzoylimido complexes of palladium. Synthesis, structural characterisation and structure-reactivity relationship.

PubMed

Besenyei, Gábor; Párkányi, László; Szalontai, Gábor; Holly, Sándor; Pápai, Imre; Keresztury, Gábor; Nagy, Andrea

2004-07-07

Benzoyl azides, ArC(O)N3, 2, (Ar = phenyl or substituted phenyl), react with [Pd2Cl2(dppm)2], 1, [dppm = bis(diphenylphosphino)methane] with the formation of novel [Pd2Cl2(mu-NC(O)Ar)(dppm)2], 3, benzoylnitrene complexes that were structurally characterised by multinuclear magnetic resonance and IR spectroscopy and, in several instances, by single crystal X-ray diffraction. As shown by crystallographic studies, the C2P4Pd2 rings adopt extended twist-boat conformations with methylene groups bending towards the bridging benzoylimido moieties. X-ray diffraction studies have revealed the chiral nature of the imido complexes, the chiral element being the propeller-like C2P4Pd2 ring. Structural data accumulated on complexes 3 such as short C-N distances (1.32 A), elongated C=O bonds (1.30 A) as well as the outstandingly high barrier to internal rotation around the N-C(O) linkage (88.3 kJ mol(-1)) are in line with extensive ppi-ppi interaction between the bridging nitrogen and the carbonyl carbon atoms. Theoretical calculations indicate an electron shift from the dimer towards the apical nitrogen atom, which, in turn, facilitates the donation of electrons towards the carbonyl moiety. To elucidate the structure-reactivity relationship of benzoyl azides towards 1, crystallographic and solution IR spectroscopic studies were carried out on a series of para-substituted benzoyl azides. The reaction obeys the Hammett equation. The large positive value of the reaction constant indicates that the azides act as electrophiles in the reaction studied. The enhanced reactivity of 2-nitrobenzoyl azide has been attributed to a decreased conjugation of the phenyl and carbonyl moieties in this reagent.

Single-crystal-to-single-crystal transformation and solvochromic luminescence of a dinuclear gold(I)-(aza-[18]crown-6)dithiocarbamate compound.

PubMed

Tzeng, Biing-Chiau; Chao, An

2015-01-26

The treatment of [AuCl(SMe2 )] with an equimolar amount of NaO5 NCS2 (O5 NCS2 =(aza-[18]crown-6)dithiocarbamate) in CH3 CN gave [Au2 (O5 NCS2 )2 ]⋅2 CH3 CN (2⋅2 CH3 CN), and its crystal structure displays a dinuclear gold(I)-azacrown ether ring and an intermolecular gold(I)⋅⋅⋅gold(I) contact of 2.8355(3) Å in crystal lattices. It is noted that two other single crystals of 2⋅tert-butylbenzene⋅H2 O and 2⋅0.5 m-xylene can be successfully obtained from a single-crystal-to-single-crystal (SCSC) transformation process by immersing single crystals of 2⋅2 CH3 CN in the respective solvents, and both also show intermolecular gold(I)⋅⋅⋅gold(I) contacts of 2.9420(5) and 2.890(2)-2.902(2) Å, respectively. Significantly, the emissions of all three 2⋅solvates are well correlated with their respective intermolecular gold(I)⋅⋅⋅gold(I) contacts, where such contacts increase with 2⋅2 CH3 CN (2.8355(3) Å)<2⋅0.5 m-xylene (2.890(2)-2.902(2) Å)<2⋅tert-butylbenzene⋅H2 O (2.9420(5) Å), and their emission energies increase with 2⋅2 CH3 CN (602 nm)<2⋅0.5 m-xylene (583 nm)<2⋅tert-butylbenzene⋅H2 O (546 nm) as well. In this regard, we further examine the solvochromic luminescence for some other aromatics, and finally their emissions are within 546-602 nm. Obviously, the above results are mostly ascribed to the occurrence of intermolecular gold(I)⋅⋅⋅gold(I) contacts in 2⋅solvates, which are induced by the presence of various solvates in the solid state, as a key role to be responsible for their solvochromic luminescence. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnetic field, frequency and temperature dependence of complex conductance of ultrathin La 1.65Sr 0.45CuO 4/La 2CuO 4 films and the organic superconductors κ-(BEDT-TTF) 2Cu[N(CN) 2]Br

DOE PAGES

V. A. Gasparov; Bozovic, I.; He, Xi; ...

2015-09-01

In this study, we used atomic-layer molecular beam epitaxy (ALL-MBE) to synthesize bilayer films of a cuprate metal (La 1.65Sr 0.45CuO 4) and a cuprate insulator (La 2CuO 4), in which interface superconductivity occurs in a layer that is just one-half unit cell thick. We have studied the magnetic field and temperature dependence of the complex sheet conductance, σ(ω), of these films, and compared them to κκ-(BEDT-TTF) 2Cu[N(CN) 2]Br single crystals. The magnetic field H was applied both parallel and perpendicular to the 2D conducting layers. Experiments have been carried out at frequencies between 23 kHz and 50 MHz usingmore » either two-coil mutual inductance technique, or the LC resonators with spiral or rectangular coils. The real and the imaginary parts of the mutual-inductance M(T,ω) between the coil and the sample were measured and converted to complex conductivity. For H perpendicular to the conducting layers, we observed almost identical behavior in both films and κ-Br single crystals: (i) the transition onset in the inductive response, L k –1(T) occurs at a temperature lower by 2 K than in Re σ(T), (ii) this shift is almost constant with magnetic field up to 8 T; (iii) the vortex diffusion constant D(T) is exponential due to pinning of vortex cores. These results can be described by the extended dynamic theory of the Berezinski–Kosterlitz–Thouless (BKT) transition and dynamics of bound vortex–antivortex pairs with short separation lengths.« less

Anionic Hosts for the Incorporation of Cationic Guests

PubMed Central

Peresypkina, Eugenia; Heindl, Claudia; Virovets, Alexander; Brake, Helena; Mädl, Eric

2018-01-01

Abstract Pentaphosphaferrocene [Cp*Fe(η5‐P5)] (1 a) represents an excellent building block for the template‐directed synthesis of spherical supramolecules. Here, the self‐assembly of 1 a with CuI and CuII halides in the presence of the template complexes [FeCp2][PF6], [CoCp2][PF6] and [CoCp2] is reported, testifying to the redox behavior of the formed supramolecules. The oxidation or reduction capacity of these reactive complexes does not inhibit their template impact and, for the first time, the cationic metallocene [CoCp2]+ is enclosed in unprecedented anionic organometallic hosts. Furthermore, the large variety of structural motifs, as icosahedral, trigonal antiprismatic, cuboidal and tetragonal antiprismatic arrangements of 1 a units are realized in the supramolecules [FeCp2]@[{1 a}12(CuBr)17.3] (3), [CoCp2]+ 3{[CoCp2]+@[{1 a}8Cu24.25Br28.25(CH3CN)6]4−} (4), {[Cp2Co]+@[{1 a}8(CuI)28 (CH3CN)9.8]}{[Cp2Co]+@[{1 a)}8Cu24.4I26.4(CH3CN)8]2−} (5), and [{1 a}3{(1 a)2NH}3Cu16I10(CH3CN)7] (6), respectively. PMID:29236336

Properties of an αs-casein-rich casein fraction: influence of dialysis on surface properties, miscibility, and micelle formation.

PubMed

Kessler, Anne; Menéndez-Aguirre, Orquidéa; Hinrichs, Jörg; Stubenrauch, Cosima; Weiss, Jochen

2013-09-01

In this study, the surface tension, miscibility, and particle size distribution of a solution containing an αs-casein (CN)-rich CN fraction (54 wt % αs-CN, 32 wt % β-CN, and 15 wt % κ-CN) were determined at pH 6.6. The nondialyzed CN fraction was compared with a dialyzed one. In the nondialyzed sample, every charge on the protein was compensated by 0.3 charges coming from counterions, whereas in the dialyzed sample, only 0.2 charges could be assigned to each charge on the protein. This relation was determined by calculating the charges at the proteins, taking the measured mineral content into account. The surface tension was measured as a function of the protein concentration by the du Noüy ring method at room temperature. Results indicated alterations in the surface properties after reduction of counterions. The equilibrium surface tension above the critical micelle concentration increased from 40.1×10(-3) to 45×10(-3) N/m, the critical micelle concentration increased from 0.9×10(-4) to 2×10(-3) mol/L, and the minimal area occupied per molecule at the surface increased from 2.4×10(-18) to 4.6×10(-18) m(2). Cloud points were determined by measuring the absorbance of CN solutions as a function of the temperature. The cloud points were found to be concentration dependent and had a minimum at 0.2 wt % at 34°C for nondialyzed CN and at 0.25 wt % at 28°C for dialyzed CN, again demonstrating the influence of counterion reduction. Below the cloud point, a micellar phase was found to exist. The hydrodynamic diameter of the micelles were characterized by dynamic light scattering in both auto- and cross-correlation mode. However, no influence of reduction in counterions could be observed, possibly due to the fact that dynamic light scattering is not a suitable method for this type of system. The presence of self-assembled structures was verified by freeze-fracture electron microscopy. The observed differences between dialyzed and nondialyzed samples were explained by changes in the counterion cloud surrounding the proteins. Consequently, the electrostatic interactions between as well as within the CN are altered by dialysis, which, in turn, affects the behavior at the surface as well as the properties in the solution. Copyright © 2013 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Experimental and Theoretical Evidences of p-Type Conductivity in Nickel Carbodiimide Nanoparticles with a Delafossite Structure Type.

PubMed

Jiang, Tengfei; Polteau, Baptiste; Farré, Yoann; Cario, Laurent; Latouche, Camille; Pellegrin, Yann; Boujtita, Mohammed; Odobel, Fabrice; Tessier, Franck; Cheviré, François; Jobic, Stéphane

2017-07-17

Nickel carbodiimide (NiCN 2 ) was synthesized using a two-step precipitation-decomposition route leading to a brown powder with gypsum-flower-like morphology and a large specific surface area (75 m 2 /g). This layered material crystallizes in the 2H structure type of delafossite (space group P6 3 /mmc), which is built upon infinite 2 / ∞ [NiN 2 ] layers connected by linear carbodiimide ([N═C═N] 2- ) bridges. An X-ray diffraction Rietveld refinement and thermal analyses pointed out some nickel deficiencies in the material, and band structure calculations carried out on the defect compound predicted p-type conductivity in relation to a slight amount of N 2- . This p-type conductivity was demonstrated by electrochemical impedance spectroscopy measurements, and a flat band potential of 0.90 V vs SCE at pH 9.4 was measured. This value, which is more positive than those of CuGaO 2 and CuCrO 2 delafossite oxides and NiO, prompted us to test NiCN 2 nanoparticles as a photocathode in p-type dye-sensitized solar cells.

Oxidation Study of an Ultra High Temperature Ceramic Coatings Based on HfSiCN

NASA Technical Reports Server (NTRS)

Sacksteder, Dagny; Waters, Deborah L.; Zhu, Dongming

2018-01-01

High temperature fiber-reinforced ceramic matrix composites (CMCs) are important for aerospace applications because of their low density, high strength, and significantly higher-temperature capabilities compared to conventional metallic systems. The use of the SiCf/SiC and Cf/SiC CMCs allows the design of lighter-weight, more fuel efficient aircraft engines and also more advanced spacecraft airframe thermal protection systems. However, CMCs have to be protected with advanced environmental barrier coatings when they are incorporated into components for the harsh environments such as in aircraft engine or spacecraft applications. In this study, high temperature oxidation kinetics of an advanced HfSiCN coating on Cf/SiC CMC substrates were investigated at 1300 C, 1400 C, and 1500 C by using thermogravimetric analysis (TGA). The coating oxidation reaction parabolic rate constant and activation energy were estimated from the experimental results. The oxidation reaction studies showed that the coatings formed the most stable, predominant HfSiO4-HfO2 scales at 1400 C. A peroxidation test at 1400 C then followed by subsequent oxidation tests at various temperatures also showed more adherent scales and slower scale growth because of reduced the initial transient oxidation stage and increased HfSiO4-HfO2 content in the scales formed on the HfSiCN coatings.

The effect of cavernous nerve traction on erectile function in rats

PubMed Central

Chen, Liping; Wang, Tao; Wang, Shaogang; Liu, Jihong

2017-01-01

We performed this study to evaluate the effect of cavernous nerve (CN) traction on erectile function in rats. Thirty-two 8- week-old Sprague–Dawley rats were divided into four groups: control, 1-minute CN traction, 2-minute CN traction, and 2-minute CN crush. CN traction was performed using a glass hook with a tensile force of 0.2 Newton. One month later, the mean arterial pressure (MAP) and intracavernosal pressure (ICP) in response to CN stimulation were measured to assess erectile function. The penis and major pelvic ganglion (MPG) were harvested to explore the expression of neuronal nitric oxide synthase (nNOS) and neurofilament, fibrosis and apoptosis. The ICP/MAP ratio was reduced in the 2-minute CN traction group compared with the control group (P < 0.05). The ICP/MAP ratio in the CN crush group was lower than in the other three groups (P < 0.05, for each). Expression of nNOS in both MPG and dorsal penile nerve was lower in the CN traction group than in the control group, but was higher than in the CN crush group (P < 0.05). Nerve fiber number in the dorsal penile nerve was reduced by 2-minute CN traction (P < 0.05). The ratios of collagen to smooth muscle content and the apoptosis were both increased the in 2-minute CN traction group compared with the control group (P < 0.05). The findings indicate that CN traction is an effective CN injury model and the injury it caused is relatively mild compared with the CN crush model. PMID:28982169

The au-scale structure in diffuse molecular gas towards ζ Persei

NASA Astrophysics Data System (ADS)

Boissé, P.; Federman, S. R.; Pineau des Forêts, G.; Ritchey, A. M.

2013-11-01

Context. Spatial structure in molecular material has a strong impact on its physical and chemical evolution and is still poorly known, especially on very small scales. Aims: To better characterize the small-scale structure in diffuse molecular gas and in particular to investigate the CH+ production mechanism, we study the spatial distribution of CH+, CH, and CN towards the bright star ζ Per on scales in the range 1-20 AU. Methods: We use ζ Per's proper motion and the implied drift of the line of sight through the foreground gas at a rate of about 2 AU yr-1 to probe absorption line variations between adjacent lines of sight. The good S/N, high or intermediate resolution spectra of ζ Per, obtained in the interval 2003-2011, allow us to search for low column-density and line width variations for CH+, CH, and CN. Results: CH and CN lines appear remarkably stable in time, implying an upper limit δN/N ≤ 6% for CH and CN (3σ limit). The weak CH+λ4232 line shows a possible increase of 11% during the interval 2004-2007, which appears to be correlated with a comparable increase in the CH+ velocity dispersion over the same period. Conclusions: The excellent stability of CH and CN lines implies that these species are distributed uniformly to good accuracy within the cloud. The small size implied for the regions associated with the CH+ excess is consistent with scenarios in which this species is produced in very small (a few AU) localized active regions, possibly weakly magnetized shocks or turbulent vortices. Based on observations made at McDonald Observatory (USA) and Observatoire de Haute-Provence (France).

Synthesis of Ultra-incompressible sp 3 -Hybridized Carbon Nitride with 1:1 Stoichiometry

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

Stavrou, Elissaios; Lobanov, Sergey; Dong, Huafeng

Search of materials with C-N composition hold a great promise in creating materials which would rival diamond hardness due to the very strong and relatively low-ionic C-N bond. Early experimental and theoretical works on C-N compounds were based on structural similarity with binary A 3B 4 structural types; however, the synthesis of C 3N 4 remains elusive. Here we explored an unbiased synthesis from the elemental materials at high pressures and temperatures. Using in situ synchrotron X-ray diffraction and Raman spectroscopy we demonstrate the synthesis of highly incompressible Pnnm CN compound with sp 3 hybridized carbon above 55 GPa andmore » 7000 K. This result is supported by first principles evolutionary search, which finds that Pnnm CN is the most stable compound above 10.9 GPa. On pressure release below 6 GPa the synthesized CN compound amorphizes reattaining its 1:1 stoichiometry as confirmed by Energy-Dispersive X-ray Spectroscopy. Here, this work underscores the importance of understanding of novel high-pressure chemistry rules and it opens a new route for synthesis of superhard materials.« less

Synthesis of Ultra-incompressible sp 3 -Hybridized Carbon Nitride with 1:1 Stoichiometry

DOE PAGES

Stavrou, Elissaios; Lobanov, Sergey; Dong, Huafeng; ...

2016-10-11

Search of materials with C-N composition hold a great promise in creating materials which would rival diamond hardness due to the very strong and relatively low-ionic C-N bond. Early experimental and theoretical works on C-N compounds were based on structural similarity with binary A 3B 4 structural types; however, the synthesis of C 3N 4 remains elusive. Here we explored an unbiased synthesis from the elemental materials at high pressures and temperatures. Using in situ synchrotron X-ray diffraction and Raman spectroscopy we demonstrate the synthesis of highly incompressible Pnnm CN compound with sp 3 hybridized carbon above 55 GPa andmore » 7000 K. This result is supported by first principles evolutionary search, which finds that Pnnm CN is the most stable compound above 10.9 GPa. On pressure release below 6 GPa the synthesized CN compound amorphizes reattaining its 1:1 stoichiometry as confirmed by Energy-Dispersive X-ray Spectroscopy. Here, this work underscores the importance of understanding of novel high-pressure chemistry rules and it opens a new route for synthesis of superhard materials.« less

Evolution of the SCS curve number method and its applications to continuous runoff simulation

USDA-ARS?s Scientific Manuscript database

The Natural Resources Conservation Service (NRCS) [previously Soil Conservation Service (SCS)] developed the SCS runoff curve-number (CN) method for estimating direct runoff from storm rainfall. The NRCS uses the CN method for designing structures and for evaluating their effectiveness. Structural...

Theoretical study of the decomposition mechanism of environmentally friendly insulating medium C3F7CN in the presence of H2O in a discharge

NASA Astrophysics Data System (ADS)

Zhang, Xiaoxing; Li, Yi; Xiao, Song; Tian, Shuangshuang; Deng, Zaitao; Tang, Ju

2017-08-01

C3F7CN has been the focus of the alternative gas research field over the past two years because of its excellent insulation properties and environmental characteristics. Experimental studies on its insulation performance have made many achievements. However, few studies on the formation mechanism of the decomposition components exist. A discussion of the decomposition characteristics of insulating media will provide guidance for scientific experimental research and the work that must be completed before further engineering application. In this study, the decomposition mechanism of C3F7CN in the presence of trace H2O under discharge was calculated based on the density functional theory and transition state theory. The reaction heat, Gibbs free energy, and activation energy of different decomposition pathways were investigated. The ionization parameters and toxicity of C3F7CN and various decomposition products were analyzed from the molecular structure perspective. The formation mechanism of the C3F7CN discharge decomposition components and the influence of trace water were evaluated. This paper confirms that C3F7CN has excellent decomposition characteristics, which provide theoretical support for later experiments and related engineering applications. However, the existence of trace water has a negative impact on C3F7CN’s insulation performance. Thus, strict trace water content standards should be developed to ensure dielectric insulation and the safety of maintenance personnel.

Hydrological modelling in sandstone rocks watershed

NASA Astrophysics Data System (ADS)

Ponížilová, Iva; Unucka, Jan

2015-04-01

The contribution is focused on the modelling of surface and subsurface runoff in the Ploučnice basin. The used rainfall-runoff model is HEC-HMS comprising of the method of SCS CN curves and a recession method. The geological subsurface consisting of sandstone is characterised by reduced surface runoff and, on the contrary, it contributes to subsurface runoff. The aim of this paper is comparison of the rate of influence of sandstone on reducing surface runoff. The recession method for subsurface runoff was used to determine the subsurface runoff. The HEC-HMS model allows semi- and fully distributed approaches to schematisation of the watershed and rainfall situations. To determine the volume of runoff the method of SCS CN curves is used, which results depend on hydrological conditions of the soils. The rainfall-runoff model assuming selection of so-called methods of event of the SCS-CN type is used to determine the hydrograph and peak flow rate based on simulation of surface runoff in precipitation exceeding the infiltration capacity of the soil. The recession method is used to solve the baseflow (subsurface) runoff. The method is based on the separation of hydrograph to direct runoff and subsurface or baseflow runoff. The study area for the simulation of runoff using the method of SCS CN curves to determine the hydrological transformation is the Ploučnice basin. The Ploučnice is a hydrologically significant river in the northern part of the Czech Republic, it is a right tributary of the Elbe river with a total basin area of 1.194 km2. The average value of CN curves for the Ploučnice basin is 72. The geological structure of the Ploučnice basin is predominantly formed by Mesozoic sandstone. Despite significant initial loss of rainfall the basin response to the causal rainfall was demonstrated by a rapid rise of the surface runoff from the watershed and reached culmination flow. Basically, only surface runoff occures in the catchment during the initial phase of this extreme event. The increase of the baseflow runoff is slower and remains constant after reaching a certain level. The rise of the baseflow runoff is showed in a descending part of the hydrograph. The recession method in this case shows almost 20 hours delay. Results from the HEC-HMS prove availability of both methods for the runoff modeling in this type of catchment. When simulating extreme short-term rainfall-runoff episodes, the influence of geological subsurface is not significant, but it is manifested. Using more relevant rainfall events would bring more satisfactory results.

A conifer ABI3-interacting protein plays important roles during key transitions of the plant life cycle.

PubMed

Zeng, Ying; Zhao, Tiehan; Kermode, Allison R

2013-01-01

ABI3 (for ABSCISIC ACID INSENSITIVE3), a transcription factor of the abscisic acid signal transduction pathway, plays a major role during seed development, dormancy inception, and dormancy maintenance. This protein appears to also function in meristematic and vegetative plant tissues and under certain stress conditions. We have isolated the ABI3 gene ortholog (CnABI3) from yellow cedar (Callitropsis nootkatensis) and found that it was functionally similar to other ABI3 genes of angiosperms. Here, we report that using a yeast (Saccharomyces cerevisiae) two-hybrid approach, we have identified another protein of yellow cedar (CnAIP2; for CnABI3 INTERACTING PROTEIN2) that physically interacts with CnABI3. Functional analyses revealed that CnAIP2 plays important roles during key transitions in the plant life cycle: (1) CnAIP2 impaired seed development and reduced seed dormancy; (2) CnAIP2 promoted root development, particularly the initiation of lateral roots, and the CnAIP2 gene promoter was exquisitely auxin sensitive; and (3) CnAIP2 promoted the transition from vegetative growth to reproductive initiation (i.e. flowering). The nature of the effects of CnAIP2 on these processes and other evidence place CnAIP2 in the category of a "global" regulator, whose actions are antagonistic to those of ABI3.

Noncollinear spin structure in SmxTb1-x[Cr(CN)6]•4H2O having orthogonal single-ion anisotropies

NASA Astrophysics Data System (ADS)

Hozumi, Toshiya; Hashimoto, Kazuhito; Ohkoshi, Shin-Ichi

2006-03-01

A series of SmxIIITb1-xIII[CrIII(CN)6]•4H2O magnets, in which SmIII and TbIII have different magnetic single-ion anisotropies, was prepared. Magnetic ordering temperatures (Tc) decreased from 12.0K (x=0) to 7.4K (x=0.55) and then increased to 10.2K (x=1) with increasing x . The magnetization (Ms) values at 5K gradually decreased from 3.0μB (x=0) to 1.6μB (x=1) . These trends of experimental Tc and Ms values suggest that the present series takes a noncollinear spin structure, in which the directions of the SmIII and TbIII sublattice magnetizations are perpendicular, from the analysis of the molecular-field model.

Ab initio SCF calculations on the potential energy surface of potassium cyanide (KCN)

NASA Astrophysics Data System (ADS)

Wormer, Paul E. S.; Tennyson, Jonathan

1981-08-01

The potential energy surface of KCN has been generated by ab initio SCF calculations in the region of equilibrium bond distances. An analytic representation of the surface is presented. The calculations show that the bonding between K and CN is ionic, and that the structure of KCN is triangular, which confirms recent experimental findings. The computed geometry is &KCN = 62.4°, rCK = 5.492a0, and rCN = 2.186a0.

LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Study of the subpicosecond rotational molecular dynamics in liquids

NASA Astrophysics Data System (ADS)

Nikiforov, V. G.; Lobkov, Vladimir S.

2006-10-01

The parameters of the femtosecond vibration—rotation molecular dynamics of liquid acetonitrile CH3CN, trimethylacetonitrile (CH3)3CCN, propionitrile CH3CH2CN, fluoroform CHF3, and chloroform CHCl3 are found by analysing the ultrafast optical Kerr effect. The influence of the molecular structure on the features of rotational (diffusion and libration) motions is studied. It is shown that the distribution of libration frequencies is described by the Maxwell distribution.

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

NASA Astrophysics Data System (ADS)

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 resemble those for other reactions. A detailed discussion is given of possible origins of the difference between the simulation and experimental energy partitioning dynamics for F + CH3CN → HF + CH2CN. The F + CH3CN reaction also forms the CH3C(F)N intermediate, in which the F-atom adds to the C≡N bond. However, this intermediate and F⋯CH3CN and CH3CN⋯F van der Waals complexes are not expected to affect the F + CH3CN → HF + CH2CN product energy partitioning.

Post-transition state dynamics and product energy partitioning following thermal excitation of the F∙∙∙HCH 2 CN transition state: Disagreement with experiment

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

Pratihar, Subha; Ma, Xinyou; Xie, Jing

Born-Oppenheimer direct dynamics simulations were performed to study atomistic details of the F + CH 3CN → HF + CH 2CN 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-HCH 2CN 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.more » The intrinsic reaction coordinate (IRC) for reaction involves rotation of HF about CH 2CN and then trapping in the CH 2CN-HF post-reaction potential energy well of ~10 kcal/mol with respect to the HF + CH 2CN 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 + CH 2CN 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, CH 2CN rotation and CH 2CN 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-atom abstraction reactions. The simulation product energy partitioning and HF vibrational population for F + CH 3CN → HF + CH 2CN are similar to those for these other reactions. A detailed discussion is given of possible origins of the difference between the simulation and experimental energy partitioning dynamics for the F + CH 3CN → HF + CH 2CN reaction. The F + CH 3CN reaction also forms the CH 3C(F)N intermediate, in which the F-atom adds to the C≡N bond. However, this intermediate and the F---CH 3CN and CH 3CN-F van der Waals complexes are not expected to affect the F + CH 3CN → HF + CH 2CN product energy partitioning.« less

Magneto-structural correlations in a family of Fe(II)Re(IV)(CN)2 single-chain magnets: density functional theory and ab initio calculations.

PubMed

Zhang, Yi-Quan; Luo, Cheng-Lin; Wu, Xin-Bao; Wang, Bing-Wu; Gao, Song

2014-04-07

Until now, the expressions of the anisotropic energy barriers Δξ and ΔA, using the uniaxial magnetic anisotropy D, the intrachain coupling strength J, and the high-spin ground state S for single-chain magnets (SCMs) in the intermediate region between the Ising and the Heisenberg limits, were unknown. To explore this relationship, we used density functional theory and ab initio methods to obtain expressions of Δξ and ΔA in terms of D, J, and S of six R4Fe(II)-Re(IV)Cl4(CN)2 (R = diethylformamide (1), dibutylformamide (2), dimethylformamide (3), dimethylbutyramide (4), dimethylpropionamide (5), and diethylacetamide (6)) SCMs in the intermediate region. The ΔA value for compounds 1-3 was very similar to the magnetic anisotropic energy of a single Fe(II), while the value of Δξ was predicted using the exchange interaction of Fe(II) with the neighboring Re(IV), which could be expressed as 2JSReSFe. Similar to compounds 1-3, the anisotropy energy barrier ΔA of compounds 4 and 5 was also equal to (Di - Ei)SFe(2), but the correlation energy Δξ was closely equal to 2JSReSFe(cos 98.4 - cos 180) due to the reversal of the spins on the opposite Fe(II). For compound 6, one unit cell of Re(IV)Fe(II) was regarded as a domain wall since it had two different Re(IV)-Fe(II) couplings. Thus, the Δξ of compound 6 was expressed as 4J″SRe1Fe1SRe2Fe2, where J″ was the coupling constant of the neighboring unit cells of Re1Fe1 and Re2Fe2, and ΔA was equal to the anisotropic energy barrier of one domain wall given by DRe1Fe1(S(2)Re1Fe1 - 1/4).

Developing descriptors to predict mechanical properties of nanotubes.

PubMed

Borders, Tammie L; Fonseca, Alexandre F; Zhang, Hengji; Cho, Kyeongjae; Rusinko, Andrew

2013-04-22

Descriptors and quantitative structure property relationships (QSPR) were investigated for mechanical property prediction of carbon nanotubes (CNTs). 78 molecular dynamics (MD) simulations were carried out, and 20 descriptors were calculated to build quantitative structure property relationships (QSPRs) for Young's modulus and Poisson's ratio in two separate analyses: vacancy only and vacancy plus methyl functionalization. In the first analysis, C(N2)/C(T) (number of non-sp2 hybridized carbons per the total carbons) and chiral angle were identified as critical descriptors for both Young's modulus and Poisson's ratio. Further analysis and literature findings indicate the effect of chiral angle is negligible at larger CNT radii for both properties. Raman spectroscopy can be used to measure C(N2)/C(T), providing a direct link between experimental and computational results. Poisson's ratio approaches two different limiting values as CNT radii increases: 0.23-0.25 for chiral and armchair CNTs and 0.10 for zigzag CNTs (surface defects <3%). In the second analysis, the critical descriptors were C(N2)/C(T), chiral angle, and M(N)/C(T) (number of methyl groups per total carbons). These results imply new types of defects can be represented as a new descriptor in QSPR models. Finally, results are qualified and quantified against experimental data.

Identifcation of a Novel Mutation p.I240T in the FRMD7 gene in a Family with Congenital Nystagmus

NASA Astrophysics Data System (ADS)

Zhu, Yihua; Zhuang, Jianfu; Ge, Xianglian; Zhang, Xiao; Wang, Zheng; Sun, Ji; Yang, Juhua; Gu, Feng

2013-10-01

Congenital Nystagmus (CN) is a genetically heterogeneous ocular disease, which causes a significant proportion of childhood visual impairment. To identify the underlying genetic defect of a CN family, twenty-two members were recruited. Genotype analysis showed that affected individuals shared a common haplotype with markers flanking FRMD7 locus. Sequencing FRMD7 revealed a T > C transition in exon 8, causing a conservative substitution of Isoleucine to Tyrosine at codon 240. By protein structural modeling, we found the mutation may disrupt the hydrophobic core and destabilize the protein structure. We reviewed the literature and found that exons 2, 8, and 9 (11.4% of the sequence of FRMD7 mRNA) represent the majority (55.3%) of the reported FRMD7 mutations. In summary, we identified a novel mutation in FRMD7, showed its molecular consequence, and revealed the mutation-rich exons of the FRMD7 gene. Collectively, this provides molecular insights for future CN clinical genetic diagnosis and treatment.

Identifcation of a novel mutation p.I240T in the FRMD7 gene in a family with congenital nystagmus.

PubMed

Zhu, Yihua; Zhuang, Jianfu; Ge, Xianglian; Zhang, Xiao; Wang, Zheng; Sun, Ji; Yang, Juhua; Gu, Feng

2013-10-30

Congenital Nystagmus (CN) is a genetically heterogeneous ocular disease, which causes a significant proportion of childhood visual impairment. To identify the underlying genetic defect of a CN family, twenty-two members were recruited. Genotype analysis showed that affected individuals shared a common haplotype with markers flanking FRMD7 locus. Sequencing FRMD7 revealed a T > C transition in exon 8, causing a conservative substitution of Isoleucine to Tyrosine at codon 240. By protein structural modeling, we found the mutation may disrupt the hydrophobic core and destabilize the protein structure. We reviewed the literature and found that exons 2, 8, and 9 (11.4% of the sequence of FRMD7 mRNA) represent the majority (55.3%) of the reported FRMD7 mutations. In summary, we identified a novel mutation in FRMD7, showed its molecular consequence, and revealed the mutation-rich exons of the FRMD7 gene. Collectively, this provides molecular insights for future CN clinical genetic diagnosis and treatment.

Identifcation of a Novel Mutation p.I240T in the FRMD7 gene in a Family with Congenital Nystagmus

PubMed Central

Zhu, Yihua; Zhuang, Jianfu; Ge, Xianglian; Zhang, Xiao; Wang, Zheng; Sun, Ji; Yang, Juhua; Gu, Feng

2013-01-01

Congenital Nystagmus (CN) is a genetically heterogeneous ocular disease, which causes a significant proportion of childhood visual impairment. To identify the underlying genetic defect of a CN family, twenty-two members were recruited. Genotype analysis showed that affected individuals shared a common haplotype with markers flanking FRMD7 locus. Sequencing FRMD7 revealed a T > C transition in exon 8, causing a conservative substitution of Isoleucine to Tyrosine at codon 240. By protein structural modeling, we found the mutation may disrupt the hydrophobic core and destabilize the protein structure. We reviewed the literature and found that exons 2, 8, and 9 (11.4% of the sequence of FRMD7 mRNA) represent the majority (55.3%) of the reported FRMD7 mutations. In summary, we identified a novel mutation in FRMD7, showed its molecular consequence, and revealed the mutation-rich exons of the FRMD7 gene. Collectively, this provides molecular insights for future CN clinical genetic diagnosis and treatment. PMID:24169426

Experimental access to elastic and thermodynamic properties of RbMnFe(CN)6

NASA Astrophysics Data System (ADS)

Boukheddaden, K.; Loutete-Dangui, E. D.; Codjovi, E.; Castro, M.; Rodriguéz-Velamazán, J. A.; Ohkoshi, S.; Tokoro, H.; Koubaa, M.; Abid, Y.; Varret, F.

2011-01-01

We use spectroscopic ellipsometry to study the elastic and thermodynamic properties of the structural first-order transition of the cooperative Jahn-Teller solid, RbMn[Fe(CN)6]. While the analysis of the thermal dependence of the dielectric constant revealed a remarkable energy shift in the metal-to-ligand charge transfer band, that of the refractive index allowed to evaluate the volumetric thermal expansion coefficient in the two phases through the Gladstone-Dale relation. The access to the elastic properties of the solid is obtained with the reflectivity under pressure measurements, from which we estimated the bulk modulus values in the low- and high-temperature phases as BLT=30(±3) GPa and BHT=23(±2) GPa, respectively. Assuming the system is isotropic, the corresponding Debye temperature values have been found to be θDLT(SE)≃360(±25) K and θDHT(SE)≃290(±20) K, in good agreement with those derived from independent Mössbauer spectrometry investigations which led to θDLT(Moss)≃332(±7) K and θDHT(Moss)≃280(±11) K. Moreover, we have been able to extract from the SE data, the entropy change at the transition, ΔS ≈64 J K-1 mol-1, which has been also found in good agreement with the value, ΔS ≈60±5 J K-1 mol-1, derived from calorimetric experiments performed in this work.

Characterization and dioxygen reactivity of a new series of coordinatively unsaturated thiolate-ligated manganese(II) complexes.

PubMed

Coggins, Michael K; Toledo, Santiago; Shaffer, Erika; Kaminsky, Werner; Shearer, Jason; Kovacs, Julie A

2012-06-18

The synthesis, structural, and spectroscopic characterization of four new coordinatively unsaturated mononuclear thiolate-ligated manganese(II) complexes ([Mn(II)(S(Me2)N(4)(6-Me-DPEN))](BF(4)) (1), [Mn(II)(S(Me2)N(4)(6-Me-DPPN))](BPh(4))·MeCN (3), [Mn(II)(S(Me2)N(4)(2-QuinoPN))](PF(6))·MeCN·Et(2)O (4), and [Mn(II)(S(Me2)N(4)(6-H-DPEN)(MeOH)](BPh(4)) (5)) is described, along with their magnetic, redox, and reactivity properties. These complexes are structurally related to recently reported [Mn(II)(S(Me2)N(4)(2-QuinoEN))](PF(6)) (2) (Coggins, M. K.; Kovacs, J. A. J. Am. Chem. Soc.2011, 133, 12470). Dioxygen addition to complexes 1-5 is shown to result in the formation of five new rare examples of Mn(III) dimers containing a single, unsupported oxo bridge: [Mn(III)(S(Me2)N(4)(6-Me-DPEN)](2)-(μ-O)(BF(4))(2)·2MeOH (6), [Mn(III)(S(Me2)N(4)(QuinoEN)](2)-(μ-O)(PF(6))(2)·Et(2)O (7), [Mn(III)(S(Me2)N(4)(6-Me-DPPN)](2)-(μ-O)(BPh(4))(2) (8), [Mn(III)(S(Me2)N(4)(QuinoPN)](2)-(μ-O)(BPh(4))(2) (9), and [Mn(III)(S(Me2)N(4)(6-H-DPEN)](2)-(μ-O)(PF(6))(2)·2MeCN (10). Labeling studies show that the oxo atom is derived from (18)O(2). Ligand modifications, involving either the insertion of a methylene into the backbone or the placement of an ortho substituent on the N-heterocyclic amine, are shown to noticeably modulate the magnetic and reactivity properties. Fits to solid-state magnetic susceptibility data show that the Mn(III) ions of μ-oxo dimers 6-10 are moderately antiferromagnetically coupled, with coupling constants (2J) that fall within the expected range. Metastable intermediates, which ultimately convert to μ-oxo bridged 6 and 7, are observed in low-temperature reactions between 1 and 2 and dioxygen. Complexes 3-5, on the other hand, do not form observable intermediates, thus illustrating the effect that relatively minor ligand modifications have upon the stability of metastable dioxygen-derived species.

Materials Data on K2CN2 (SG:12) by Materials Project

DOE Data Explorer

Kristin Persson

2014-11-02

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

Cation symmetry effect on the volatility of ionic liquids.

PubMed

Rocha, Marisa A A; Coutinho, João A P; Santos, Luís M N B F

2012-09-06

This work reports the first data for the vapor pressures at several temperatures of the ionic liquids, [C(N/2)C(N/2)im][NTf(2)] (N = 4, 6, 8, 10, 12) measured using a Knudsen effusion apparatus combined with a quartz crystal microbalance. The morphology and the thermodynamic parameters of vaporization derived from the vapor pressures, are compared with those for the 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide series, [C(N-1)C(1)im][NTf(2)] (N = 3 - 9, 11, and 13). It was found that the volatility of [C(N/2)C(N/2)im][NTf(2)] series is significantly higher than the asymmetric cation ILs with the same total number of carbons in the alkyl side chains, [C(N-1)C(1)im][NTf(2)]. The observed higher volatility is related with the lower enthalpy of vaporization. The symmetric cation, [C(N/2)C(N/2)im][NTf(2)], presents lower entropies of vaporization compared with the asymmetric [C(N-1)C(1)im][NTf(2)], indicating an increase of the absolute liquid entropy in the symmetric cation ILs, being a reflection of a change of the ion dynamics in the IL liquid phase. Moreover both the enthalpy and entropy of vaporization of the [C(N/2)C(N/2)im][NTf(2)] ILs, present a clear odd-even effect with higher enthalpies/entropies of vaporization for the odd number of carbons in each alkyl chain ([C(3)C(3)im][NTf(2)] and [C(5)C(5)im][NTf(2)]).

A combined crossed molecular beams and theoretical study of the reaction CN + C2H4

NASA Astrophysics Data System (ADS)

Balucani, Nadia; Leonori, Francesca; Petrucci, Raffaele; Wang, Xingan; Casavecchia, Piergiorgio; Skouteris, Dimitrios; Albernaz, Alessandra F.; Gargano, Ricardo

2015-03-01

The CN + C2H4 reaction has been investigated experimentally, in crossed molecular beam (CMB) experiments at the collision energy of 33.4 kJ/mol, and theoretically, by electronic structure calculations of the relevant potential energy surface and Rice-Ramsperger-Kassel-Marcus (RRKM) estimates of the product branching ratio. Differently from previous CMB experiments at lower collision energies, but similarly to a high energy study, we have some indication that a second reaction channel is open at this collision energy, the characteristics of which are consistent with the channel leading to CH2CHNC + H. The RRKM estimates using M06L electronic structure calculations qualitatively support the experimental observation of C2H3NC formation at this and at the higher collision energy of 42.7 kJ/mol of previous experiments.

On the nature of the reversibility of hydration-dehydration on the crystal structure and magnetism of the ferrimagnet [MnII(enH)(H2O)][CrIII(CN)6].H2O.

PubMed

Yoshida, Yusuke; Inoue, Katsuya; Kurmoo, Mohamedally

2009-01-05

We report the synthesis, crystal structure, and thermal and magnetic properties of the two-dimensional achiral soft ferrimagnet [Mn(II)(enH)(H(2)O)][Cr(III)(CN)(6)].H(2)O (1), en = 1,2-diaminoethane, as well as the recyclability of the dehydration and rehydration and their influence on the crystal structure and its magnetic properties. Unlike [Mn(S-pnH)(H(2)O)][Cr(CN)(6)].H(2)O (2S, pn = 1,2-diaminopropane), which is a chiral (P2(1)2(1)2(1)) enantiopure ferrimagnet (T(C) = 38 K), 1 crystallizes in the achiral orthorhombic Pcmn space group, having a similar two-dimensional square network of Mn-Cr with bridging cyanide, and 1 behaves also as a soft ferrimagnet (T(C) = 42 K). X-ray diffraction experiments on a single crystal of 1 indicate a transformation from a single crystal to an amorphous phase upon dehydrataion and partial recovery of its crystallinity upon rehydration. The dehydrated phase 1-DP exhibits long-range ordering at 75 K to a ferrimagnetic state and coercive field at 2 K of 100 Oe, which are a higher critical temperature and coercive field than for the virgin sample (H(C) = 60 Oe). Thermogravimetric analyses indicate that the crystallinity deteriorates upon hydration-dehydration cycling, with persistence toward the amorphous phase, as also seen by magnetization measurements. This effect is associated with an increase of statistical disorder inherent in the dehydration-rehydration process. X-ray powder diffraction suggests that 1-DP may retain order within the layers but loses coherence in the stacking of the layers.

Construction of halide-bridged tungsten-copper-sulfide double cubanelike clusters from a new precursor [(Tp*WS2)2(μ-S2)].

PubMed

Wei, Li-Pei; Ren, Zhi-Gang; Zhu, Lian-Wen; Yan, Wen-Yan; Sun, Sha; Wang, Hui-Fang; Lang, Jian-Ping; Sun, Zhen-Rong

2011-05-16

Treatment of [Et(4)N][Tp*WS(3)] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 2 equiv of AgSCN in MeCN afforded a novel neutral compound [(Tp*WS(2))(2)(μ-S(2))] (2). Reactions of 2 with excess CuX (X = Cl, Br, I) in MeCN and CH(2)Cl(2) or CHCl(3) formed three neutral W/Cu/S clusters [{Tp*W(μ(3)-S)(3)Cu(3)(μ-Cl)}(2)Cu(μ-Cl)(2)(μ(7)-Cl)(MeCN)](2) (3), [{Tp*W(μ(3)-S)(3)Cu(3)}(2)Br(μ-Br)(2)(μ(4)-Br)(MeCN)] (4), and [{Tp*W(μ(3)-S)(3)Cu(3)}(2){Cu(2)(μ-I)(4)(μ(3)-I)(2)}] (5), respectively. On the other hand, treatment of 2 with CuX (X = Cl, Br) in the presence of Et(4)NX (X = Cl, Br) produced two anionic W/Cu/S clusters [Et(4)N][{Tp*W(μ(3)-S)(3)Cu(3)X}(2)(μ-X)(2)(μ(4)-X)] (6: X = Cl; 7 X = Br). Compounds 2-7 were characterized by elemental analysis, IR, UV-vis, (1)H NMR, electrospray ionization (ESI) mass spectra, and single-crystal X-ray crystallography. The dimeric structure of 2 can be viewed as two [Tp*WS(2)] fragments in which two W atoms are connected by one S(2)(2-) dianion. Compounds 3-7 all possess unique halide-bridged double cubanelike frameworks. For 3, two [Tp*W(μ(3)-S)(3)Cu(3)](2+) dications are linked via a μ(7)-Cl(-) bridge, two μ-Cl(-) bridges, and a [Cu(MeCN)(μ-Cl)(2)](+) bridge. For 4, one [Tp*W(μ(3)-S)(3)Cu(3)(MeCN)](2+) dication and one [Tp*W(μ(3)-S)(3)Cu(3)Br](+) cation are linked via a μ(4)-Br(-) and two μ-Br(-) bridges. For 5, the two [Tp*W(μ(3)-S)(3)Cu(3)](2+) dications are bridged by a linear [(μ-I)(2)Cu(μ(3)-I)(2)Cu(μ-I)(2)](4+) species. For 6 and 7, two [Tp*W(μ(3)-S)(3)Cu(3)X](+) cations are linked by a μ(4)-X(-) and two μ-X(-) bridges (X = Cl, Br). In addition, the third-order nonlinear optical (NLO) properties of 2-7 in MeCN/CH(2)Cl(2) were investigated by using femtosecond degenerate four-wave mixing (DFWM) technique.

Fate of zinc in an electroplating sludge during electrokinetic treatments.

PubMed

Liu, Shou-Heng; Wang, H Paul

2008-08-01

Chemical structure of zinc in the electrokinetic treatments of an electroplating sludge has been studied by in situ extended X-ray absorption fine structural (EXAFS) and X-ray absorption near edge structural (XANES) spectroscopies in the present work. The least-square fitted XANES spectra indicate that the main zinc compounds in the sludge were ZnCO(3) (75%), ZnOSiO(2) (17%) and Zn(OH)(2) (7%). Zinc in the sludge possessed a Zn-O bond distance of 2.07 A with a coordination number (CN) of 5. In the second shells, the bond distance of Zn-(O)-Si was 3.05 A (CN=2). An increase of Zn-(O)-Si (0.05 A) with a decrease of its CN (from 5 to <1) was found in the early stage of the electrokinetic treatment. Prolong the electrokinetic treatment time to 180 min, about 34% of Zn(II) was dissolved into the aqueous phase and about 68% of Zn(II) in the sludge (or 23% of total zinc) was migrated to the cathode under the electric field (5 V cm(-1)). The dissolution and electromigration rates of Zn(II) in the sludge were 1.0 and 0.6 mmol h(-1)g(-1) sludge, respectively during the electrokinetic treatment. This work also exemplifies the utilization of in situ EXAFS and XANES for revealing speciation and possible reaction pathways during the course of zinc recycling from the sludge by electrokinetic treatments.

Simple Quaternary Ammonium Ions R4N + ( R= nPr, nBu, nPen) as Versatile Structure Directors for the Synthesis of Zeolite-Like, Heterobimetallic Cyanide Frameworks

NASA Astrophysics Data System (ADS)

Poll, Eyck-Michael; Samba, Sabine; Dieter Fischer, R.; Olbrich, Falk; Davies, Nicola A.; Avalle, Paolo; Apperley, David C.; Harris, Robin K.

2000-06-01

The preparation of three new examples of water insoluble host/guest assemblies of the general composition: [(R4N)(Me3Sn)2M(CN)6·zH2O] (R=n-propyl or n-pentyl, M=Fe or Co, 0≤z≤2) from likewise polymeric super-Prussian-blue derivatives [(Me3Sn)3M(CN)6] and aqueous (R4N)X solutions are reported. According to combined single-crystal X-ray (3a and 3a*: R=nPr, M=Co, z=2; 5b: R=nPen, M=Fe, z=0.5), powder X-ray diffraction (XRD), and multinuclear (13C, 15N, 59Co, 119Sn) CPMAS solid-state magnetic resonance studies, 3a and 3a* contain cis- and trans-isomeric [Co(CN)4(CNSnMe3OH2)2]- building blocks, respectively, which are held together exclusively by Sn←OH2···NC-Co hydrogen bonds. In striking contrast, the building blocks of 5b and 5a are infinite [M-CN-Sn-NC] chains. In all these assemblies, also significant C-H···NC hydrogen bonds between the encapsulated R4N+ guest ion and exclusively terminal cyanide ligands of the host seem to play a notable auxiliary role.

High-Performance Phototransistors Based on PDIF-CN2 Solution-Processed Single Fiber and Multifiber Assembly.

PubMed

Rekab, Wassima; Stoeckel, Marc-Antoine; El Gemayel, Mirella; Gobbi, Marco; Orgiu, Emanuele; Samorì, Paolo

2016-04-20

Here we describe the fabrication of organic phototransistors based on either single or multifibers integrated in three-terminal devices. These self-assembled fibers have been produced by solvent-induced precipitation of an air stable and solution-processable perylene di-imide derivative, i.e., PDIF-CN2. The optoelectronic properties of these devices were compared to devices incorporating more disordered spin-coated PDIF-CN2 thin-films. The single-fiber devices revealed significantly higher field-effect mobilities, compared to multifiber and thin-films, exceeding 2 cm(2) V(-1) s(-1). Such an efficient charge transport is the result of strong intermolecular coupling between closely packed PDIF-CN2 molecules and of a low density of structural defects. The improved crystallinity allows efficient collection of photogenerated Frenkel excitons, which results in the highest reported responsivity (R) for single-fiber PDI-based phototransistors, and photosensitivity (P) exceeding 2 × 10(3) AW(-1), and 5 × 10(3), respectively. These findings provide unambiguous evidence for the key role played by the high degree of order at the supramolecular level to leverage the material's properties toward the fabrication of light-sensitive organic field-effect transistors combining a good operational stability, high responsivity and photosensitivity. Our results show also that the air-stability performances are superior in devices where highly crystalline supramolecularly engineered architectures serve as the active layer.

Using the small alignment index chaos indicator to characterize the vibrational dynamics of a molecular system: LiNC-LiCN.

PubMed

Benitez, P; Losada, J C; Benito, R M; Borondo, F

2015-10-01

A study of the dynamical characteristics of the phase space corresponding to the vibrations of the LiNC-LiCN molecule using an analysis based on the small alignment index (SALI) is presented. SALI is a good indicator of chaos that can easily determine whether a given trajectory is regular or chaotic regardless of the dimensionality of the system, and can also provide a wealth of dynamical information when conveniently implemented. In two-dimensional (2D) systems SALI maps are computed as 2D phase space representations, where the SALI asymptotic values are represented in color scale. We show here how these maps provide full information on the dynamical phase space structure of the LiNC-LiCN system, even quantifying numerically the volume of the different zones of chaos and regularity as a function of the molecule excitation energy.

Physicochemical characterization of mineral (iron/zinc) bound caseinate and their mineral uptake in Caco-2 cells.

PubMed

Shilpashree, B G; Arora, Sumit; Kapila, Suman; Sharma, Vivek

2018-08-15

Milk proteins (especially caseins) are widely accepted as good vehicle for the delivery of various bioactive compounds including minerals. Succinylation is one of the most acceptable chemical modification techniques to enhance the mineral binding ability of caseins. Addition of minerals to succinylated proteins may alter their physicochemical and biochemical properties. Physicochemical characteristics of succinylated sodium caseinate (S.NaCN)-mineral (iron/zinc) complexes were elucidated. Chromatographic behaviour and fluorescence intensity confirmed the structural modification of S.NaCN upon binding with minerals. The bound mineral from protein complexes showed significantly higher (P < 0.05) in vitro bioavailability (mineral uptake) than mineral salts in Caco-2 cells. Also, iron bound S.NaCN showed higher cellular ferritin formation than iron in its free form. These mineral bound protein complexes with improved bioavailability could safely replace inorganic fortificants in various functional food formulations. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

Cano, A.; Osiry, H.; Reguera, L.

The titled compound was prepared by the precipitation method from diluted aqueous solution of sodium nitroprusside and mercury(II) nitrate. The orange solid formed, with formula unit Hg[Fe(CN){sub 5}NO], crystallizes with an orthorhombic unit cell in the Pmna space group with cell parameters: a=11.2788(3), b=6.1965(3), and c=12.3786(6) Å. The unit cell accommodates four formula of the compound (Z=4). Its crystal structure was solved from X-ray powder patterns and then refined by the Rietveld method. The material framework is formed by tetrahedral coordination of Hg atoms at the N end of the equatorial CN groups of the [Fe(CN){sub 5}NO] building block. Thatmore » framework results from the interpenetration of two identical sub-frameworks with a relative shift of (a/2, b/2, c/2). The sub-framework has two types of cavities, ellipsoidal and rhombohedral, with transversal section of ca. 4.5×9.2 Å and ca. 8.5 Å transversal section, respectively. That system of cavities results eclipsed by the relative shift of neighboring sub-frameworks. No transport of H{sub 2} and N{sub 2} molecules through the material framework was observed. The thermal decomposition also reveals limitation for the decomposition products diffusion through the practically compact structure. The structural study was complemented with TG, IR, UV–vis and N{sub 2} and H{sub 2} adsorption data. Neighboring Hg atoms are distant 4.54(3) Å, a relatively large distance to suppose the existence of metal–metal interaction. No previous study on the crystal structure and related properties of mercury(II) nitroprusside has been reported. - Graphical abstract: Mercury(II) nitroprusside framework formed by two identical interpenetrated porous subframeworks where neighboring cavities appear eclipsed. - Highlights: • Interpenetrated frameworks in metal nitroprusside. • Eclipsed porous framework in metal nitroprusside. • Structure and related properties for mercury(II) nitroprusside. • Spectral features for mercury(II) nitroprusside.« less

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

NASA Astrophysics Data System (ADS)

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.

Wavy carbon: A new series of carbon structures explored by quantum chemical calculations

NASA Astrophysics Data System (ADS)

Ohno, Koichi; Satoh, Hiroko; Iwamoto, Takeaki; Tokoyama, Hiroaki; Yamakado, Hideo

2015-10-01

A new carbon family adopting wavy structures has been found by quantum chemical calculations. The key motif of this family is a condensed four-membered ring. Periodically wavy-carbon sheets (wavy-Cn sheets, n = 2, 6, and 8) as well as wavy-C36 tube were found to be very similar to the previously reported prism-Cn carbon tubes (n = 5, 6, and 8) in several respects, including the relative energies per one carbon atom with respect to graphene, CC bond lengths, and CCC bond angles. Because of very high relative energies with respect to graphene (206-253 kJ mol-1), the wavy-carbons may behave as energy reserving materials.

Phytosterols isolated from Clinacanthus nutans induce immunosuppressive activity in murine cells.

PubMed

Le, Cheng-Foh; Kailaivasan, Thina Hareesh; Chow, Sek-Chuen; Abdullah, Zunoliza; Ling, Sui-Kiong; Fang, Chee-Mun

2017-03-01

Clinacanthus nutans (Burm. f.) Lindau is a traditional medicinal plant belonging to the Acanthaceae family. Its therapeutic potentials have been increasingly documented particularly the antiviral activity against Herpes Simplex Virus (HSV), anti-cancer, anti-oxidant, anti-inflammatory and immunomodulatory activities. However, majority of these studies used crude or fractionated extracts and not much is known about individual compounds from these extracts and their biological activities. In the present study, we have isolated four compounds (CN1, CN2, CN3 and CN4) from the hexane fractions of C. nutans leaves. Using NMR spectroscopic analysis, these compounds were identified to be shaftoside (CN1), stigmasterol (CN2), β-sitosterol (CN3) and a triterpenoid lupeol (CN4). To determine the immunosuppressive potential of these compounds, their effects on mitogens induced T and B lymphocyte proliferation and the secretion of helper T cell cytokines were examined. Among the four compounds, stigmasterol (CN2) and β-sitosterol (CN3) were shown to readily inhibit T cell proliferation mediated by Concanavalin A (ConA). However, only β-sitosterol (CN3) and not stigmasterol (CN2) blocks the secretion of T helper 2 (Th2) cytokines (IL-4 and IL-10). Both compounds have no effect on the secretion of Th1 cytokines (IL-2 and IFN-γ), suggesting that β-sitosterol treatment selectively suppresses Th2 activity and promotes a Th1 bias. CN3 was also found to significantly reduce the proliferation of both T helper cells (CD4 + CD25 + ) and cytotoxic T cells (CD8 + CD25 + ) following T cell activation induced by ConA. These results suggested that phytosterols isolated from C. nutans possess immunomodulatory effects with potential development as immunotherapeutics. Copyright © 2017 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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.

The photochemistry of some possible cometary CN parent species

NASA Technical Reports Server (NTRS)

Halpern, Joshua B.

1987-01-01

Laboratory work on the photochemistry of HC3N, C4N2, and CH3CN in relation to their possible role as CN parent molecules in comets is discussed. Photodissociation of HC3N, photolysis of C4N2, and quantum yields of excited CN(B) and CN(A) radicals from the VUV photolysis of CH3CN are considered.

Facile synthesis, microstructure and photophysical properties of core-shell nanostructured (SiCN)/BN nanocomposites

PubMed Central

Zhang, Qian; Jia, Dechang; Yang, Zhihua; Cai, Delong; Laine, Richard M.; Li, Qian; Zhou, Yu

2017-01-01

Increasing structural complexity at nanoscale can permit superior control over photophysical properties in the precursor-derived semiconductors. We demonstrate here the synthesis of silicon carbonitride (SiCN)/boron nitride (BN) nanocomposites via a polymer precursor route wherein the cobalt polyamine complexes used as the catalyst, exhibiting novel composite structures and photophysical properties. High Resolution Transmission Electron Microscopy (HRTEM) analysis shows that the diameters of SiCN−BN core−shell nanocomposites and BN shells are 50‒400 nm and 5‒25 nm, respectively. BN nanosheets (BNNSs) are also observed with an average sheet size of 5‒15 nm. The photophysical properties of these nanocomposites are characterized using the UV-Vis and photoluminescence (PL) analyses. The as-produced composites have emission behavior including an emission lifetime of 2.5 ns (±20 ps) longer observed in BN doped SiCN than that seen for SiC nanoparticles. Our results suggest that the SiCN/BN nanocomposites act as semiconductor displaying superior width photoluminescence at wavelengths spanning the visible to near-infrared (NIR) spectral range (400‒700 nm), owing to the heterojunction of the interface between the SiC(N) nanowire core and the BN nanosheet shell. PMID:28084300

Low-temperature glasslike properties in (NaCl)1-x(NaCN)x

NASA Astrophysics Data System (ADS)

Watson, Susan K.; Pohl, R. O.

1995-04-01

Thermal conductivity, internal friction, transverse sound velocity (60 mK to 300 K), and specific-heat data (100 mK to 40 K) for (NaCl)1-x(NaCN)x (x=0, 0.025, 0.05, 0.1, 0.76, 1) show a progression from crystalline to glasslike behavior as the CN- concentration is increased from 0 to 76 %. The evolution of glasslike properties is compared to that in other crystals in which glasslike properties evolve with increasing disorder, e.g., (KBr)1-x(KCN)x and Ba1-xLaxF2-x. For (KBr)1-x(KCN)x, Sethna and Chow have shown that as the concentration of the almost freely rotating CN- ions is increased the average potential barrier for CN- reorientation also increases through elastic quadrupolar interactions. For x~0.5, only a small density of low-energy states is left, which equals that observed in structural glasses. In Ba1-xLaxF2-x, on the other hand, the crystal field for small doping x is so large that no atomic motion occurs at low temperatures. (NaCl)1-x(NaCN)x is shown to represent an intermediate case, in that the crystal field is non-negligible at small x, yet glasslike low-energy excitations indicative of very small potential barrier heights evolve with increasing x. It is argued that random internal strains cause a decrease of the barrier heights in these crystals, which lead to the low-energy excitations. It is proposed that random strains have a similar effect in other disordered crystals as in Ba1-xLaxF2-x, which for small x show no low-energy mobile states, yet which for large x become glasslike.

Role of higher-multipole deformations and noncoplanarity in the decay of the compound nucleus *220Th within the dynamical cluster-decay model

NASA Astrophysics Data System (ADS)

Hemdeep, Chopra, Sahila; Kaur, Arshdeep; Kaushal, Pooja; Gupta, Raj K.

2018-04-01

Background: The formation and decay of the *220Th compound nucleus (CN) formed via some entrance channels (16O+204Pb,40Ar+180Hf,48Ca+172Yb,82Se+138Ba ) at near barrier energies has been studied within the dynamical cluster-decay model (DCM) [Hemdeep et al. Phys. Rev. C 95, 014609 (2017), 10.1103/PhysRevC.95.044603], for quadrupole deformations (β2 i) and "optimum" orientations (θopt) of the two nuclei or decay fragments lying in the same plane (coplanar nuclei, Φ =0∘ ). Purpose: We aim to investigate the role of higher-multipole deformations, the octupole (β3 i) and hexadecupole (β4 i), and "compact" orientations (θc i) together with the noncoplanarity degree of freedom (Φc) in the noncompound nucleus (nCN) cross section, already observed in the above mentioned study with quadrupole deformations (β2 i) alone, the Φ =0∘ case. Methods: The dynamical cluster-decay model (DCM), based on the quantum mechanical fragmentation theory (QMFT), is used to analyze the decay channel cross sections σx n for various experimentally studied entrance channels. The parameter Ra (equivalently, the neck length Δ R in Ra=R1+R2+Δ R ), which fixes both the preformation and penetration paths, is used to best fit both unobserved (1 n ,2 n ) and observed (3 n -5 n ) decay channel cross sections, keeping the root-mean-square (r.m.s) deviation to the minimum, which allows us to predict the nCN effects, if any, and fusion-fission (ff) cross sections in various reactions at different CN excitation energies E*. Results: For the decay of CN *220Th, the mass fragmentation potential V (Ai ) and preformation yields P0( Ai ) show an asymmetric fission mass distribution, in agreement with one observed in experiments, independent of adding or not adding (β3 i,β4 i ), and irrespective of large changes (by 36° and 34°), respectively, in "compact" orientations θc i and noncoplanarity Φc, and also in the potential energy surface V (Ai ) in light mass (1 n -5 n ) decays. Whereas the 3 n - and 5 n -decay channels fit nearly exactly, i.e., they are always the pure CN decays, the 4 n -decay channel shows the presence of large (˜95 % ) nCN content whose magnitude in every case remains the same within <1 % and hence does not get modified, in contrast to our earlier studies of other CN. Also, the near constancy of best fitted Ra(≡Δ R ) with E*, and with an upper limiting value for reactions with magic nuclei as reaction partner(s), independent of the entrance channel nuclei, allows us to predict the decay channel cross sections σx n,x =3 -5 for 16O+204Pb reaction, whose sum (=∑35σx n ) fits the observed σER data nicely. Also, the variations of CN fusion/formation probability PC N and survival probability Psurv follow the required systematic behavior, giving credence to our DCM analysis. Conclusions: With the inclusion of higher-multipole deformations and "compact" noncoplanarity degree of freedom (Φc≠0 ), the results of our above-mentioned earlier study, using quadrupole deformation (β2 i) alone for coplanar (Φc=0 ) nuclei, remain the same; i.e., of the measured 3 n -5 n decay channels of CN *220Th, the 3 n and 5 n decays are always pure CN decays and the 4 n decay is mainly of nCN content σn CN, whose magnitude also remains constant (within <1 % ) under all approximations. Furthermore, the upper limiting value of the linear dependence of first turning point Ra on E* is shown to be a better choice for predicting the decay channel cross sections σx n for reactions like 16O+204Pb using magic nuclei, whose experimental determination will be a good test of our model.

Isolation and structural analysis of antihypertensive peptides that exist naturally in Gouda cheese.

PubMed

Saito, T; Nakamura, T; Kitazawa, H; Kawai, Y; Itoh, T

2000-07-01

Seven kinds of ripened cheeses (8-mo-aged and 24-mo-aged Gouda, Emmental, Blue, Camembert, Edam, and Havarti) were homogenized with distilled water, and water-soluble peptides were prepared by C-18 hydrophobic chromatography. The inhibitory activity to angiotensin I-converting enzyme and decrease in the systolic blood pressure in spontaneously hypertensive rats were measured before and after oral administration of each peptide sample. The strongest depressive effect in the systolic blood pressure (-24.7 mm Hg) and intensive inhibitory activity to angiotensin I-converting enzyme (75.7%) were detected in the peptides from 8-mo-aged Gouda cheese. Four peptides were isolated by HPLC with reverse-phase and gel filtration modes. Their chemical structures and origins, clarified by combination analyses of protein sequencing, amino acid composition, and mass spectrometry, were as follows: peptide A, Arg-Pro-Lys-His-Pro-Ile-Lys-His-Gln [alpha(s1)-casein (CN), B-8P; f 1-9]; peptide B, Arg-Pro-Lys-His-Pro-Ile-Lys-His-Gln-Gly-Leu-Pro-Gln (alpha(s1)-CN, B-8P; f 1-13); peptide F, Tyr-Pro-Phe-Pro-Gly-Pro-Ile-Pro-Asn (beta-CN, A2-5P; f 60-68); and peptide G, Met-Pro-Phe-Pro-Lys-Tyr-Pro-Val-Gln-Pro-Phe (beta-CN, A2-5P; f 109-119). Peptides A and F, which were chemically synthesized, showed potent angiotensin I-converting enzyme inhibitory activity with little antihypertensive effects.

Theoretical mechanistic study on the ion-molecule reaction of SiCN+/SiNC+ with H2O.

PubMed

Wang, Jian; Ding, Yi-hong; Sun, Chia-chung

2005-02-15

The gas-phase ion-molecule reactions play very important roles in interstellar and in plasma chemistry. Motivated by recent astrophysical detection of the SiCN/SiNC radicals and laboratory characterization of some SiCN-containing species, we carried out a detailed potential energy survey on the SiCN+/SiNC(+) + H2O reaction at the Becke's three-parameter Lee-Yang-Parr-B3LYP/6-311G(d,p) and coupled cluster with single, double, and triple excitations-CCSD(T)/6-311 + G(2df,p) (single-point) levels as an attempt towards understanding the SiCN+/SiNC+ reaction mechanisms. In contrast to the carbene-featured analogous CCN+/CNC(+) + H2X (X=O,S) reactions, the title reaction SiCN+/SiNC(+) + H2O are not associated with any competitive silylene-insertion characters. Moreover, the -CN <--> -NC interconversion has a low barrier and plays an important role in determining the final product distributions. This is also in marked difference from the CCN+/CNC+ reaction. It is shown that the isomeric sila-cations SiCN+ and SiNC+ can both react with H2O to barrierlessly generate the major product P1 HOSi(+) + HCN and the minor one P3 HOSi(+) + HNC, whereas other low-lying products such as P2 SiNCO(+) + H2, and P(0) H2NSi(+) + CO are kinetically unfeasible. The high efficiency of the SiCN+/SiNC+ reaction towards H2O and the potential importance of SiCN+/SiNC+ ion chemistry in interstellar and SiCN-based microelectric and photoelectric processes strongly appeals for future laboratory investigations on the SiCN+/SiNC+ chemical reactivity.

Dramatic influence of an anionic donor on the oxygen-atom transfer reactivity of a Mn(V) -oxo complex.

PubMed

Neu, Heather M; Quesne, Matthew G; Yang, Tzuhsiung; Prokop-Prigge, Katharine A; Lancaster, Kyle M; Donohoe, James; DeBeer, Serena; de Visser, Sam P; Goldberg, David P

2014-11-03

Addition of an anionic donor to an Mn(V) (O) porphyrinoid complex causes a dramatic increase in 2-electron oxygen-atom-transfer (OAT) chemistry. The 6-coordinate [Mn(V) (O)(TBP8 Cz)(CN)](-) was generated from addition of Bu4 N(+) CN(-) to the 5-coordinate Mn(V) (O) precursor. The cyanide-ligated complex was characterized for the first time by Mn K-edge X-ray absorption spectroscopy (XAS) and gives MnO=1.53 Å, MnCN=2.21 Å. In combination with computational studies these distances were shown to correlate with a singlet ground state. Reaction of the CN(-) complex with thioethers results in OAT to give the corresponding sulfoxide and a 2e(-) -reduced Mn(III) (CN)(-) complex. Kinetic measurements reveal a dramatic rate enhancement for OAT of approximately 24 000-fold versus the same reaction for the parent 5-coordinate complex. An Eyring analysis gives ΔH(≠) =14 kcal mol(-1) , ΔS(≠) =-10 cal mol(-1)  K(-1) . Computational studies fully support the structures, spin states, and relative reactivity of the 5- and 6-coordinate Mn(V) (O) complexes. © 2014 The Authors. Published by Wiley-VCHVerlag GmbH & Co. KGaA. This is an open access article under the terms ofthe Creative Commons Attribution License, which permits use, distribution andreproduction in any medium, provided the original work is properly cited.

Placing the Deep Impact Mission into context: Two decades of observations of 9P/Tempel 1 from McDonald Observatory

NASA Astrophysics Data System (ADS)

Cochran, A. L.; Barker, E. S.; Caballero, M. D.; Györgey-Ries, J.

2009-01-01

We report on low-spectral resolution observations of Comet 9P/Tempel 1 from 1983, 1989, 1994 and 2005 using the 2.7 m Harlan J. Smith telescope of McDonald Observatory. This comet was the target of NASA's Deep Impact mission and our observations allowed us to characterize the comet prior to the impact. We found that the comet showed a decrease in gas production from 1983 to 2005, with the decrease being different factors for different species. OH decreased by a factor 2.7, NH by 1.7, CN by 1.6, C 3 by 1.8, CH by 1.4 and C 2 by 1.3. Despite the decrease in overall gas production and these slightly different decrease factors, we find that the gas production rates of OH, NH, C 3, CH and C 2 ratioed to that of CN were constant over all of the apparitions. We saw no change in the production rate ratios after the impact. We found that the peak gas production occurred about two months prior to perihelion. Comet Tempel 1 is a "normal" comet.

Mcdonald Observatory 9P/TEMPEL 1 Data V1.0

NASA Astrophysics Data System (ADS)

Cochran, A. L.; Barker, E. S.; Caballero, M. D.; Gyorgey-Ries, J.

2010-01-01

We report on low-spectral resolution observations of comet 9P/Tempel 1 from 1983, 1989, 1994 and 2005 using the 2.7m Harlan J. Smith telescope of McDonald Observatory. This comet was the target of NASA's Deep Impact mission and our observations allowed us to characterize the comet prior to the impact. In the published paper, we showed that the comet decreased in gas production from 1983 to 2005, with the decrease being different factors for different species. OH decreased by a factor 2.7, NH by 1.7, CN by 1.6, C3 by 1.8, CH by 1.4 and C2 by 1.3. Despite the decrease in overall gas production and these slightly different decrease factors, we found that the ratios of the gas production rates of OH, NH, C3, CH and C2 that of CN were constant over all of the apparitions. We saw no change in the production rate ratios after the impact. We found that the peak gas production occurred about two months prior to perihelion. This data set represents the integrated fluxes and column densities, mentioned in the published paper, which were used to derive the production rates in the paper.

The effects of linear assembly of two carbazole groups on acid-base and DNA-binding properties of a ruthenium(II) complex.

PubMed

Chen, Xi; Xue, Long-Xin; Ju, Chun-Chuan; Wang, Ke-Zhi

2013-07-01

A novel Ru(II) complex of [Ru(bpy)2(Hbcpip)](ClO4)2 {where bpy=2,2-bipyridine, Hbcpip=2-(4-(9H-3,9'-bicarbazol-9-yl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline} is synthesized and characterized. Calf-thymus DNA-binding properties of the complex were studied by UV-vis absorption and luminescence titrations, steady-state emission quenching by [Fe(CN)6](4-), DNA competitive binding with ethidium bromide, thermal denaturation and DNA viscosity measurements. The results indicate that the complex partially intercalated into the DNA with a binding constant of (5.5±1.4)×10(5) M(-1) in buffered 50 mM NaCl. The acid-base properties of the complex were also studied by UV-visible and luminescence spectrophotometric pH titrations, and ground- and excited-state acidity ionization constant values were derived. Copyright © 2013 Elsevier B.V. All rights reserved.

Simultaneous observations of structure function parameter of refractive index using a high-resolution radar and the DataHawk small airborne measurement system

NASA Astrophysics Data System (ADS)

Scipión, Danny E.; Lawrence, Dale A.; Milla, Marco A.; Woodman, Ronald F.; Lume, Diego A.; Balsley, Ben B.

2016-09-01

The SOUSY (SOUnding SYstem) radar was relocated to the Jicamarca Radio Observatory (JRO) near Lima, Peru, in 2000, where the radar controller and acquisition system were upgraded with state-of-the-art parts to take full advantage of its potential for high-resolution atmospheric sounding. Due to its broad bandwidth (4 MHz), it is able to characterize clear-air backscattering with high range resolution (37.5 m). A campaign conducted at JRO in July 2014 aimed to characterize the lower troposphere with a high temporal resolution (8.1 Hz) using the DataHawk (DH) small unmanned aircraft system, which provides in situ atmospheric measurements at scales as small as 1 m in the lower troposphere and can be GPS-guided to obtain measurements within the beam of the radar. This was a unique opportunity to make coincident observations by both systems and to directly compare their in situ and remotely sensed parameters. Because SOUSY only points vertically, it is only possible to retrieve vertical radar profiles caused by changes in the refractive index within the resolution volume. Turbulent variations due to scattering are described by the structure function parameter of refractive index Cn2. Profiles of Cn2 from the DH are obtained by combining pressure, temperature, and relative humidity measurements along the helical trajectory and integrated at the same scale as the radar range resolution. Excellent agreement is observed between the Cn2 estimates obtained from the DH and SOUSY in the overlapping measurement regime from 1200 m up to 4200 m above sea level, and this correspondence provides the first accurate calibration of the SOUSY radar for measuring Cn2.

Rapid chromatographic determination of caseins in milk with photometric and fluorimetric detection using a hydrophobic monolithic column.

PubMed

Ramírez-Palomino, P; Fernández-Romero, J M; Gómez-Hens, A

2014-01-01

Reverse-phase liquid chromatographic methods using a hydrophobic C18 monolithic column and on-line photometric and fluorimetric detection for the determination of the major casein (CN) proteins in milk are presented. The separation of αs1-CN, αs2-CN, β-CN and κ-CN was achieved in only five minutes. Fluorimetric detection enabled better analytical results than photometric detection. Thus, the dynamic ranges of the calibration graphs and detection limits obtained using fluorimetric detection were (mgmL(-)(1)): αs1-CN (0.74-10.0, 0.22), αs2-CN (0.15-10.0, 0.045), β-CN (0.68-10.0, 0.20) and κ-CN (0.21-10.0, 0.06). The analytical features of the photometric method, which does not allow the quantification of β-casein, were (mgmL(-)(1)): αs1-CN (1.5-9.0, 0.45), αs2-CN (1.4-10.0, 0.43) and κ-CN (0.4-9.0, 0.12). Precision data, expressed as relative standard deviation, ranged between 0.6% and 5.3% for the fluorimetric method and between 2.4% and 6.2% for the photometric method. Both methods were applied to the analysis of three different milk samples, obtaining recoveries in the ranges of 86.6-103.2% and 92.0-106.5% using fluorimetric and photometric detection, respectively. Copyright © 2013 Elsevier Ltd. All rights reserved.

Ultimate turbulence experiment: simultaneous measurements of Cn2 near the ground using six devices and eight methods

NASA Astrophysics Data System (ADS)

Yatcheva, Lydia; Barros, Rui; Segel, Max; Sprung, Detlev; Sucher, Erik; Eisele, Christian; Gladysz, Szymon

2015-10-01

We have performed a series of experiments in order to simultaneously validate several devices and methods for measurement of the path-averaged refractive index structure constant ( 𝐶𝑛 2). The experiments were carried out along a horizontal urban path near the ground. Measuring turbulence in this layer is particularly important because of the prospect of using adaptive optics for free-space optical communications in an urban environment. On one hand, several commercial sensors were used: SLS20, a laser scintillometer from Scintec AG, BLS900, a largeaperture scintillometer, also from Scintec, and a 3D sonic anemometer from Thies GmbH. On the other hand, we measured turbulence strength with new approaches and devices developed in-house. Firstly, an LED array combined with a high-speed camera allowed for measurement of 𝐶𝑛 2 from raw- and differential image motion, and secondly a two-part system comprising a laser source, a Shack-Hartmann sensor and a PSF camera recoded turbulent modulation transfer functions, Zernike variances and angle-of-arrival structure functions, yielding three independent estimates of 𝐶𝑛 2. We compare the measured values yielded simultaneously by commercial and in-house developed devices and show very good agreement between 𝐶𝑛 2 values for all the methods. Limitations of each experimental method are also discussed.

Characterizing executive functioning in older special populations: from cognitively elite to cognitively impaired.

PubMed

de Frias, Cindy M; Dixon, Roger A; Strauss, Esther

2009-11-01

The authors examined the structure and invariance of executive functions (EF) across (a) a continuum of cognitive status in 3 groups of older adults (cognitively elite [CE], cognitively normal [CN], and cognitively impaired [CI]) and (b) a 3-year longitudinal interval. Using latent variable analyses (LISREL 8.80), the authors tested 3-factor models ("Inhibition": Hayling [Burgess & Shallice, 1997], Stroop [Regard, 1981]; "Shifting": Brixton [Burgess & Shallice, 1997], Color Trails [D'Elia et al., 1996]; and "Updating": Reading and Computational Span [Salthouse & Babcock, 1991]) and 1-factor models within each group. Participants (initial N = 570; 53-90 years) were from the Victoria Longitudinal Study (Sample 3, Waves 1 and 2). Cross-sectionally, the authors observed a 3-factor EF structure especially for the CE group and 1-factor solutions for all 3 groups. Longitudinally, temporal invariance was supported for the 3-factor model (CE and CN groups) and the 1-factor model (CI and CN groups). Subgroups with higher cognitive status and greater 3-year stability performed better on EF factors than corresponding groups with lower cognitive status and less stability. Studies of EF structure, performance, dedifferentiation, and dysfunction will benefit from considering initial cognitive status and longitudinal stability.

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

PubMed

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 → HF + CH 2 CN resemble those for other reactions. A detailed discussion is given of possible origins of the difference between the simulation and experimental energy partitioning dynamics for F + CH 3 CN → HF + CH 2 CN. The F + CH 3 CN reaction also forms the CH 3 C(F)N intermediate, in which the F-atom adds to the C≡N bond. However, this intermediate and F⋯CH 3 CN and CH 3 CN⋯F van der Waals complexes are not expected to affect the F + CH 3 CN → HF + CH 2 CN product energy partitioning.

Path Profiles of Cn2 Derived from Radiometer Temperature Measurements and Geometrical Ray Tracing

NASA Technical Reports Server (NTRS)

Vyhnalek, Brian E.

2017-01-01

Atmospheric turbulence has significant impairments on the operation of Free-Space Optical (FSO) communication systems, in particular temporal and spatial intensity fluctuations at the receiving aperture resulting in power surges and fades, changes in angle of arrival, spatial coherence degradation, etc. The refractive index structure parameter Cn2 is a statistical measure of the strength of turbulence in the atmosphere and is highly dependent upon vertical height. Therefore to understand atmospheric turbulence effects on vertical FSO communication links such as space-to-ground links, it is necessary to specify Cn2 profiles along the atmospheric propagation path. To avoid the limitations on the applicability of classical approaches, propagation simulation through geometrical ray tracing is applied. This is achieved by considering the atmosphere along the optical propagation path as a spatial distribution of spherical bubbles with varying relative refractive index deviations representing turbulent eddies. The relative deviations of the refractive index are statistically determined from altitude-dependent and time-varying temperature fluctuations, as measured by a microwave profiling radiometer. For each representative atmosphere ray paths are analyzed using geometrical optics, which is particularly advantageous in situations of strong turbulence where there is severe wavefront distortion and discontinuity. The refractive index structure parameter is then determined as a function of height and time.

The Structure and Bonding State for Fullerene-Like Carbon Nitride Films with High Hardness Formed by Electron Cyclotron Resonance Plasma Sputtering

NASA Astrophysics Data System (ADS)

Kamata, Tomoyuki; Niwa, Osamu; Umemura, Shigeru; Hirono, Shigeru

2012-12-01

We studied pure carbon films and carbon nitride (CN) films by using electron cyclotron resonance (ECR) sputtering. The main feature of this method is high density ion irradiation during deposition, which enables the pure carbon films to have fullerene-like (FL) structures without nitrogen incorporation. Furthermore, without substrate heating, the ECR sputtered CN films exhibited an enhanced FL microstructure and hardness comparable to that of diamond at intermediate nitrogen concentration. This microstructure consisted of bent and cross-linked graphene sheets where layered areas remarkably decreased due to increased sp3 bonding. Under high nitrogen concentration conditions, the CN films demonstrated extremely low hardness because nitrile bonding not only decreased the covalent-bonded two-dimensional hexagonal network but also annihilated the bonding there. By evaluating lattice images obtained by transmission electron microscopy and the bonding state measured by X-ray photoelectron spectroscopy, we classified the ECR sputtered CN films and offered phase diagram and structure zone diagram.

Laser-excited luminescence and absorption study of mixed valence for K 2Pt(CN) 4—K 2Pt(CN) 6 crystals

NASA Astrophysics Data System (ADS)

Kasi Viswanath, A.; Smith, Wayne L.; Patterson, H.

1982-04-01

Crystals of K 2Pt(CN) 6 doped with Pt(CN) 2-4 show an absorption band at 337 nm which is assigned as a mixed-valence (MV) transition from Pt (II) to Pt(IV). From a Hush model analysis, the absorption band is interpreted to be class II in the Day—Robin scheme. When the MV band is laser excited at 337 nm, emmision is observed from Pt(CN) 2-4 clusters.

Di-μ-cyanido-1:2κC:N,2:3κN:C-hexa-cyanido-1κC,3κC-tetra-kis(1,10-phenanthroline)-1κN,N';2κN,N';3κN,N'-1,3-dicobalt(III)-2-iron(II) tetra-hydrate.

PubMed

Zhang, Ying; Yuan, Ai-Hua; Zhou, Hu; Guo, Ji-Xi; Liu, Lang

2009-08-08

The hydro-thermal reaction of CoCl(2)·6H(2)O, 1,10-phenanthroline (phen) and K(3)[Fe(CN)(6)] in deionized water yielded the title cyanide-bridged trinuclear cluster, [Co(2)Fe(CN)(8)(C(12)H(8)N(2))(4)]·4H(2)O or [{Co(III)(phen)(CN)(4)}(2){Fe(II)(phen)(2)}]·4H(2)O, which contains two Co(III) centers and one Fe(II) center linked by cyanide bridges. The combination of coordinative bonds, O-H⋯N and O-H⋯O hydrogen bonds and π-π stacking inter-actions [centroid-centroid distance = 3.630 (2) Å] results in the stabilization of a supra-molecular structure. All uncoordinated water molecules are disordered. Thermogravimetric analysis reveals that the title complex loses the four crystal water mol-ecules at about 333 K, then the anhydrous phase loses no further mass up to about 573 K, above which decomposition occurs.

Concentration dependence of Li+/Na+ diffusion in manganese hexacyanoferrates

NASA Astrophysics Data System (ADS)

Takachi, Masamitsu; Fukuzumi, Yuya; Moritomo, Yutaka

2016-06-01

Manganese hexacyanoferrates (Mn-HCFs) with a jungle-gym-type structure are promising cathode materials for Li+/Na+ secondary batteries (LIBs/SIBs). Here, we investigated the diffusion constants D Li/D Na of Li+/Na+ against the Li+/Na+ concentration x Na/x Li and temperature (T) of A 1.32Mn[Fe(CN)6]0.833.6H2O (A = Li and Na). We evaluated the activation energy E\\text{a}\\text{Li}/E\\text{a}\\text{Na} of D Li/D Na against x Na/x Li. We found that E\\text{a}\\text{Na} steeply increases with x Na from 0.41 eV at x Na = 0.69 to 0.7 eV at 1.1. The increase in E\\text{a}\\text{Na} is ascribed to the occupancy effect of the Na+ site. The increase in E\\text{a}\\text{Li} is suppressed, probably because the number of Li+ sites is three times that of Na+ sites.

On the formation of metal cyanides and related compounds in the circumstellar envelope of IRC+10216

NASA Astrophysics Data System (ADS)

Petrie, Simon

1996-10-01

Various pathways to the metal cyanides Na(CN), Mg(CN) and Al(CN) - some of which have been detected in the circumstellar envelope IRC+10216 - are critically assessed. Calculations of rate coefficients for radiative association processes of the types M^++HCN, M^++HNC and M+CN, which are supported by ab initio calculations of the relevant bond strengths, molecular geometries and vibrational frequencies, allow us to conclude that none of these previously proposed pathways to M(CN) can account for the observed abundances of T-Na(CN), MgCN and MgNC within IRC+10216. We propose that the observed sodium and magnesium cyanides are best accounted for by a mechanism involving radiative association of Na^+ and Mg^+ with cyanopolyynes such as HC_5N and HC_7N, and discuss prospects for the formation of Al(CN) by an analogous mechanism. We also estimate the abundance ratios n(NaCN):n(T-Na(CN)) and n(AlCN):n(AlNC), assuming an ion/molecule source for these species and based on calculated themochemical and spectroscopic properties for these isomers; the results suggest that virtually all Na(CN) and Al(CN) should be in the form of T-Na(CN) and linear AlNC respectively, with poor prospects for the detection of the higher energy isomers NaCN and AlCN. Larger homologues of the metal cyanides, such as MNC_2n-1 (M=Na, Mg, Al; n=1,2,3,4...), may also arise in the dissociative recombination of MNC_2n+1H^+ ions. We assess the prospects for formation of the species MgC_2 and MgCCH, and propose also that the metal amides MNH_2 (M=Na, Mg, Al) constitute another class of compound whose formation in IRC+10216 via an ion/molecule mechanism, namely the reaction of M^+ with NH_3, appears highly likely.

Structures of Cryptococcus neoformans Protein Farnesyltransferase Reveal Strategies for Developing Inhibitors That Target Fungal Pathogens

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

Hast, Michael A.; Nichols, Connie B.; Armstrong, Stephanie M.

Cryptococcus neoformans is a fungal pathogen that causes life-threatening infections in immunocompromised individuals, including AIDS patients and transplant recipients. Few antifungals can treat C. neoformans infections, and drug resistance is increasing. Protein farnesyltransferase (FTase) catalyzes post-translational lipidation of key signal transduction proteins and is essential in C. neoformans. We present a multidisciplinary study validating C. neoformans FTase (CnFTase) as a drug target, showing that several anticancer FTase inhibitors with disparate scaffolds can inhibit C. neoformans and suggesting structure-based strategies for further optimization of these leads. Structural studies are an essential element for species-specific inhibitor development strategies by revealing similarities andmore » differences between pathogen and host orthologs that can be exploited. We, therefore, present eight crystal structures of CnFTase that define the enzymatic reaction cycle, basis of ligand selection, and structurally divergent regions of the active site. Crystal structures of clinically important anticancer FTase inhibitors in complex with CnFTase reveal opportunities for optimization of selectivity for the fungal enzyme by modifying functional groups that interact with structurally diverse regions. A substrate-induced conformational change in CnFTase is observed as part of the reaction cycle, a feature that is mechanistically distinct from human FTase. Our combined structural and functional studies provide a framework for developing FTase inhibitors to treat invasive fungal infections.« less

SEC14 is a specific requirement for secretion of phospholipase B1 and pathogenicity of Cryptococcus neoformans

PubMed Central

Chayakulkeeree, Methee; Johnston, Simon Andrew; Oei, Johanes Bijosono; Lev, Sophie; Williamson, Peter Richard; Wilson, Christabel Frewen; Zuo, Xiaoming; Leal, Ana Lusia; Vainstein, Marilene Henning; Meyer, Wieland; Sorrell, Tania Christine; May, Robin Charles; Djordjevic, Julianne Teresa

2011-01-01

Summary Secreted phospholipase B1 (CnPlb1) is essential for dissemination of Cryptococcus neoformans to the central nervous system (CNS) yet essential components of its secretion machinery remain to be elucidated. Using gene deletion analysis we demonstrate that CnPlb1 secretion is dependent on the CnSEC14 product, CnSec14-1p. CnSec14-1p is a homologue of the phosphatidylinositol transfer protein (PITP) ScSec14p, which is essential for secretion and viability in Saccharomyces cerevisiae. In contrast to CnPlb1, neither laccase 1 (Lac1)-induced melanization within the cell wall nor capsule induction were negatively impacted in CnSEC14-1 deletion mutants (CnΔsec14-1 and CnΔsec14-1CnΔsfh5). Similar to the CnPLB1 deletion mutant (CnΔplb1), CnΔsec14-1 was hypo-virulent in mice and did not disseminate to the CNS by day 14 post infection. Furthermore, macrophage expulsion of live CnΔsec14-1 and CnΔplb1 (vomocytosis) was reduced. Individual deletion of CnSEC14-2, a closely-related CnSEC14-1 homologue, and CnSFH5, a distantly-related SEC fourteen-like homologue, did not abrogate CnPlb1 secretion or virulence. However, reconstitution of CnΔsec14-1 with CnSEC14-1 or CnSEC14-2 restored both phenotypes, consistent with functional genetic redundancy. We conclude that CnPlb1 secretion is SEC14-dependent and that C. neoformans preferentially exports virulence determinants to the cell periphery via distinct pathways. We also demonstrate that CnPlb1 secretion is essential for vomocytosis. PMID:21453402

Materials Data on H8CN2(ClO5)2 (SG:60) by Materials Project

DOE Data Explorer

Kristin Persson

2014-11-02

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

Silver(I) coordination polymers assembled from flexible cyclotriphosphazene ligand: structures, topologies and investigation of the counteranion effects.

PubMed

Davarcı, Derya; Gür, Rüştü; Beşli, Serap; Şenkuytu, Elif; Zorlu, Yunus

2016-06-01

The reactions of a flexible ligand hexakis(3-pyridyloxy)cyclotriphosphazene (HPCP) with a variety of silver(I) salts (AgX; X = NO3(-), PF6(-), ClO4(-), CH3PhSO3(-), BF4(-) and CF3SO3(-)) afforded six silver(I) coordination polymers, namely {[Ag2(HPCP)]·(NO3)2·H2O}n (1), {[Ag2(HPCP)(CH3CN)]·(PF6)2}n (2), {[Ag2(HPCP)(CH3CN)]·(ClO4)2}n (3), [Ag3(HPCP)(CH3PhSO3)3]n (4), [Ag2(HPCP)(CH3CN)(BF4)2]n (5) and {[Ag(HPCP)]·(CF3SO3)}n (6). All of the isolated crystalline compounds were structurally determined by X-ray crystallography. Changing the counteranions in the reactions, which were conducted under similar conditions of M/L ratio (1:1), temperature and solvent, resulted in structures with different types of topologies. In complexes (1)-(6), the ligand HPCP shows different coordination modes with Ag(I) ions giving two-dimensional layered structures and three-dimensional frameworks with different topologies. Complex (1) displays a new three-dimensional framework adopting a (3,3,6)-connected 3-nodal net with point symbol {4.6(2)}2{4(2).6(10).8(3)}. Complexes (2) and (3) are isomorphous and have a two-dimensional layered structure showing the same 3,6L60 topology with point symbol {4.2(6)}2{4(8).6(6).8}. Complex (4) is a two-dimensional structure incorporating short Ag...Ag argentophilic interactions and has a uninodal 4-connected sql/Shubnikov tetragonal plane net with {4(4).6(2)} topology. Complex (5) exhibits a novel three-dimensional framework and more suprisingly contains twofold interpenetrated honeycomb-like networks, in which the single net has a trinodal (2,3,5)-connected 3-nodal net with point symbol {6(3).8(6).12}{6(3)}{8}. Complex (6) crystallizes in a trigonal crystal system with the space group R\\bar 3 and possesses a three-dimensional polymeric structure showing a binodal (4,6)-connected fsh net with the point symbol (4(3).6(3))2.(4(6).6(6).8(3)). The effect of the counteranions on the formation of coordination polymers is discussed in this study.

One dimensional coordination polymers: Synthesis, crystal structures and spectroscopic properties

NASA Astrophysics Data System (ADS)

Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla; Şenyel, Mustafa; Şahin, Onur

2016-11-01

Two new one dimensional (1D) cyanide complexes, namely [M(4-aepy)2(H2O)2][Pt(CN)4], (4-aepy = 4-(2-aminoethyl)pyridine M = Cu(II) (1) or Zn(II) (2)), have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal and elemental analyses techniques. The crystallographic analyses reveal that 1 and 2 are isomorphous and isostructural, and crystallize in the monoclinic system and C2 space group. The Pt(II) ions are coordinated by four cyanide-carbon atoms in the square-planar geometry and the [Pt(CN)4]2- ions act as a counter ion. The M(II) ions display an N4O2 coordination sphere with a distorted octahedral geometry, the nitrogen donors belonging to four molecules of the organic 4-aepy that act as unidentate ligands and two oxygen atoms from aqua ligands. The crystal structures of 1 and 2 are similar each other and linked via intermolecular hydrogen bonding, Pt⋯π interactions to form 3D supramolecular network. Vibration assignments of all the observed bands are given and the spectral features also supported to the crystal structures of the complexes.

Functional analogue reaction systems of the DMSO reductase isoenzyme family: probable mechanism of S-oxide reduction in oxo transfer reactions mediated by bis(dithiolene)-tungsten(IV,VI) complexes.

PubMed

Sung, Kie-Moon; Holm, R H

2002-04-24

The recent development of structural and functional analogues of the DMSO reductase family of isoenzymes allows mechanistic examination of the minimal oxygen atom transfer paradigm M(IV) + QO M(VI) O + Q with the biological metals M = Mo and W. Systematic variation of the electronic environment at the WIV center of desoxo bis(dithiolene) complexes is enabled by introduction of para-substituted phenyl groups in the equatorial (eq) dithiolene ligand and the axial (ax) phenolate ligand. The compounds [W(CO)2(S2C2(C6H4-p-X)2)2] (54-60%) have been prepared by ligand transfer from [Ni(S2C2(C6H4-p-X)2)2] to [W(CO)3(MeCN)3]. A series of 25 complexes [W(IV)(OC6H4-p-X')(S2C2(C6H4-p-X)2)2]1- ([X4,X'], X = Br, F, H, Me, OMe; X' = CN, Br, H, Me, NH2; 41-53%) has been obtained by ligand substitution of five dicarbonyl complexes with five phenolate ligands. Linear free energy relationships between E1/2 and Hammett constant p for the electron-transfer series [Ni(S2C2(C6H4-p-X)2)2]0,1-,2- and [W(CO)2(S2C2(C6H4-p-X)2)2]0,1-,2- demonstrate a substituent influence on electron density distribution at the metal center. The reactions [WIV(OC6H4-p-X')(S2C2(C6H4-p-X)2)2]1- + (CH2)4SO [W(VI)O(OC6H4-p-X')(S2C2(C6H4-p-X)2)2]1- + (CH2)4S with constant substrate are second order with large negative activation entropies indicative of an associative transition state. Rate constants at 298 K adhere to the Hammett equations log(k([X4,X']/k[X4,H]) = rho(ax)sigma(p) and log(k[X4,X']/k([H4,X']) = 4rho(eq)sigma(p). Electron-withdrawing groups (EWG) and electron-donating groups (EDG) have opposite effects on the rate such that k(EWG) > k(EDG). The effects of X' on reactivity are found to be approximately 5 times greater than that of X (rho(ax) = 2.1, rho(eq) = 0.44) in the Hammett equation. Using these and other findings, a stepwise oxo transfer reaction pathway is proposed in which an early transition state, of primary W(IV)-O(substrate) bond-making character, is rate-limiting. This is followed by a six-coordinate substrate complex and a second transition state proposed to involve atom and electron transfer leading to the development of the W(VI)=O group. This work is the most detailed mechanistic investigation of oxo transfer mediated by a biological metal.

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

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

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

Solvent effects on the oxidation (electron transfer) reaction of [Fe(CN) 6] 4- by [Co(NH 3) 5pz] 3+

NASA Astrophysics Data System (ADS)

Muriel, F.; Jiménez, R.; López, M.; Prado-Gotor, R.; Sánchez, F.

2004-03-01

Solvent effects on the title reaction were studied in different reaction media constituted by water and organic cosolvents (methanol, tert-butyl alcohol, ethyleneglycol and glucose) at 298.2 K. The results are considered in light of the Marcus-Hush approach for electron transfer reactions. Variations of the electron transfer rate constant are shown to be mainly due to changes in the reaction free energy. On the other hand the energies of the MMCT band, corresponding to the optical electron transfer within the ion pair [Fe(CN) 6] 4-/[Co(NH 3) 5pz] 3+, in the different reaction media, have been obtained. The activation free energies of the thermal electron transfer process have been calculated from the band ( Eop) data, and compared with those obtained from the kinetic study. Quantitative agreement is found between the two series of data. This shows the possibility of estimating activation free energies for electron transfer reactions from static (optical) measurements.

Ligand Field Strength Mediates Electron Delocalization in Octahedral [((H)L)2Fe6(L')m](n+) Clusters.

PubMed

Hernández Sánchez, Raúl; Zheng, Shao-Liang; Betley, Theodore A

2015-09-02

To assess the impact of terminal ligand binding on a variety of cluster properties (redox delocalization, ground-state stabilization, and breadth of redox state accessibility), we prepared three electron-transfer series based on the hexanuclear iron cluster [((H)L)2Fe6(L')m](n+) in which the terminal ligand field strength was modulated from weak to strong (L' = DMF, MeCN, CN). The extent of intracore M-M interactions is gauged by M-M distances, spin ground state persistence, and preference for mixed-valence states as determined by electrochemical comproportionation constants. Coordination of DMF to the [((H)L)2Fe6] core leads to weaker Fe-Fe interactions, as manifested by the observation of ground states populated only at lower temperatures (<100 K) and by the greater evidence of valence trapping within the mixed-valence states. Comproportionation constants determined electrochemically (Kc = 10(4)-10(8)) indicate that the redox series exhibits electronic delocalization (class II-III), yet no intervalence charge transfer (IVCT) bands are observable in the near-IR spectra. Ligation of the stronger σ donor acetonitrile results in stabilization of spin ground states to higher temperatures (∼300 K) and a high degree of valence delocalization (Kc = 10(2)-10(8)) with observable IVCT bands. Finally, the anionic cyanide-bound series reveals the highest degree of valence delocalization with the most intense IVCT bands (Kc = 10(12)-10(20)) and spin ground state population beyond room temperature. Across the series, at a given formal oxidation level, the capping ligand on the hexairon cluster dictates the overall properties of the aggregate, modulating the redox delocalization and the persistence of the intracore coupling of the metal sites.

Differential effects of Phe19 and Phe20 on fibril formation by amyloidogenic peptide A beta 16-22 (Ac-KLVFFAE-NH2).

PubMed

Inouye, Hideyo; Gleason, Katherine A; Zhang, Dong; Decatur, Sean M; Kirschner, Daniel A

2010-08-01

The sequence KLVFFAE (A beta 16-22) in Alzheimer's beta-amyloid is thought to be a core beta-structure that could act as a template for folding other parts of the polypeptide or molecules into fibrillar assemblies rich in beta-sheet. To elucidate the mechanism of the initial folding process, we undertook combined X-ray fiber/powder diffraction and infrared (IR) spectroscopy to analyze lyophilized A beta 16-22 and solubilized/dried peptide containing nitrile probes at F19 and/or F20. Solubilized/dried wild-type (WT) A beta 16-22 and the peptide containing cyanophenylalanine at F19 (19CN) or at F20 (20CN) gave fiber patterns consistent with slab-like beta-crystallites that were cylindrically averaged around the axis parallel to the polypeptide chain direction. The WT and 19CN assemblies showed 30-A period arrays arising from the stacking of the slabs along the peptide chain direction, whereas the 20CN assemblies lacked any such stacking. The electron density projection along the peptide chain direction indicated similar side-chain dispositions for WT and 20CN, but not for 19CN. These X-ray results and modeling imply that in the assembly of WT A beta 16-22 the F19 side chain is localized within the intersheet space and is involved in hydrophobic contact with amino acids across the intersheet space, whereas the F20 side chain localized near the slab surface is less important for the intersheet interaction, but involved in slab stacking. IR observations for the same peptides in dilute solution showed a greater degree of hydrogen bonding for the nitrile groups in 20CN than in 19CN, supporting this interpretation. (c) 2010 Wiley-Liss, Inc.

Tracking the photodissociation dynamics of liquid nitromethane at 266 nm by femtosecond time-resolved broadband transient grating spectroscopy

NASA Astrophysics Data System (ADS)

Wu, Honglin; Song, Yunfei; Yu, Guoyang; Wang, Yang; Wang, Chang; Yang, Yanqiang

2016-05-01

Femtosecond time-resolved transient grating (TG) technique was employed to get insight into the photodissociation mechanism of liquid nitromethane (NM). Broadband white-light continuum was introduced as the probe to observe the evolution of electronic excited states of NM molecules and the formation of photodissociation products simultaneously. The reaction channel of liquid NM under 266 nm excitation was obtained that NM molecules in excited state S2 relax through two channels: about 73% relax to low lying S1 state through S2/S1 internal conversion with a time constant of 0.24 ps and then go back to the ground state through S1/S0 internal conversion; the other 27% will dissociate with a time constant of 2.56 ps. NO2 was found to be one of the products from the experimental TG spectra, which confirmed that C-N bond rupture was the primary dissociation channel of liquid NM.

Very highly excited vibrational states of LiCN using a discrete variable representation

NASA Astrophysics Data System (ADS)

Henderson, James R.; Tennyson, Jonathan

Calculations are presented for the lowest 900 vibrational (J = 0) states of the LiCN floppy system for a two dimensional potential energy surface (rCN frozen). Most of these states lie well above the barrier separating the two linear isomers of the molecule and the point where the classical dynamics of the system becomes chaotic. Analysis of the wavefunctions of individual states in the high energy region shows that while most have an irregular nodal structure, a significant number of states appear regular - corresponding to solutions of standard, 'mode localized' hamiltonians. Motions corresponding in zero-order to Li-CN and Li-NC normal modes as well as free rotor states are identified. The distribution of level spacings is also studied and yields results in good agreement with those obtained by analysing nodal structures.

A simple approach for estimating the refractive index structure parameter (Cn²) profile in the atmosphere.

PubMed

Basu, Sukanta

2015-09-01

Utilizing the so-called Thorpe scale as a measure of the turbulence outer scale, we propose a physically-based approach for the estimation of Cn2 profiles in the lower atmosphere. This approach only requires coarse-resolution temperature profiles (a.k.a., soundings) as input, yet it has the intrinsic ability to capture layers of high optical turbulence. The prowess of this computationally inexpensive approach is demonstrated by validations against observational data from a field campaign over Mauna Kea, Hawaii.

Tris(acetonitrile)chloropalladium tetrafluoroborate synthesis, application and structural analysis

NASA Astrophysics Data System (ADS)

Dybała, Izabela; Demchuk, Oleg M.

2016-10-01

Results of the single crystal X-ray diffraction analysis of tris(acetonitrile)chloropalladium tetrafluoroborate [PdCl(CH3CN)3]BF4 are presented in details. It was found that the title compound crystallises in the monoclinic system, in the space group C2/c. The role of charge-assisted C-HṡṡṡF-B interactions in crystal architecture was investigated. Due to its untypical properties the prepared [PdCl(CH3CN)3]BF4 has proved to be an excellent palladium source in the synthesis of phosphine-palladium complexes.

High-pressure investigations of yttrium(III) oxoarsenate(V): Crystal structure and luminescence properties of Eu3+-doped scheelite-type Y[AsO4] from xenotime-type precursors

NASA Astrophysics Data System (ADS)

Ledderboge, Florian; Nowak, Jan; Massonne, Hans-Joachim; Förg, Katharina; Höppe, Henning A.; Schleid, Thomas

2018-07-01

Colourless, water- and air-stable single crystals of yttrium(III) oxoarsenate(V) Y[AsO4] in the xenotime-type crystal structure were prepared by the reaction of yttrium sesquioxide (Y2O3) dissolved in aqueous nitric acid (13%) with a solution of arsenic(V) oxide hydrate (As2O5·3H2O) and subsequent neutralization with 1 M caustic soda. Y[AsO4] crystallizes tetragonally in the space group I41/amd with the lattice parameters a = 704.63(6) and c = 628.94(5) pm for Z = 4 and is isotypic to the minerals xenotime RE[PO4] (RE: mainly Y and Yb) and chernovite RE[AsO4] (RE: mainly Y and Ce). This xenotime-type yttrium compound was used as precursor in a high-pressure experiment (20 kbar) at 700 °C to create a new tetragonal modification of Y[AsO4]. It shows the scheelite-type structure (space group: I41/a) with the lattice parameters a = 498.23(4) and c = 1120.71(9) pm for Z = 4, named after the mineral scheelite (Ca[WO4]). Both tetragonal structures are characterized by only one crystallographically unique position for each of the Y3+, As5+ and O2- ions with distances of d(Y-O) = 232 and 241 pm (C.N. = 8) as well as d(As-O) = 169 pm (C.N. = 4) in the case of the scheelite-type structure. The xenotime-type compound shows an unexpected slight decrease in average bond lengths for the yttrium to oxygen (d(Y-O) = 230 and 241 pm, C.N. = 8) as well as for the arsenic to oxygen distances (d(As-O) = 168 pm, C.N. = 4), accompanied by a drastic density increase from Dx = 4.85 (xenotime type) to Dx = 5.44 g • cm-3 (scheelite type). Luminescence spectroscopic measurements of the Eu3+-doped Y[AsO4] samples, obtained in experiments at similar conditions as for the pure compounds, show a bright, reddish lighting for the scheelite type, which does not occur for the xenotime type of yttrium(III) oxoarsenate(V).