A Structure-Activity Study with Aryl Acylamidases

PubMed Central

Villarreal, David T.; Turco, Ronald F.; Konopka, Allan

1994-01-01

We examined the relationship between chemical structure and biodegradability of acylanilide herbicides by using a set of model compounds. Four bacterial isolates (one gram-negative and three gram-positive) that grew on acetanilide were used. These soil isolates cleaved the amide bond of acetanilide via an aryl acylamidase reaction, producing aniline and the organic acid acetate. A series of acetanilide analogs with alkyl substitutions on the nitrogen atom or the aromatic ring were tested for their ability to induce aryl acylamidase activity and act as substrates for the enzyme. The substrate range, in general, was limited to those analogs not disubstituted in the ortho position of the benzene ring or which did not contain an alkyl group on the nitrogen atom. These same N-substituted compounds did not induce enzyme activity either, whereas the ortho-substituted compounds could in some cases. PMID:16349428

Receptor interactrions of imidazolines. VI. Significance of carbon bridge separating phenyl and imidazoline rings of tolazoline-like alpha adrenergic imidazolines.

PubMed

Ruffolo, R R; Yaden, E L; Waddell, J E; Dillard, R D

1980-09-01

The pharmacological significance of the carbon bridge separating the imidazoline and phenyl rings of tolazoline-like alpha adrenergic imidazolines has been investigated. Extending the carbon bridge to two carbon atoms, or deleting the carbon bridge, lowers affinity of the imidazolines for the alpha receptor and markedly decreases or abolishes efficacy (i.e., agonist activity), suggesting that a single carbon atome optimallyu separates the phenyl and imidazoline rings. Although one carbon is optimal for alpha adrenergic activity, this particular atom does not appear to be essential since nitrogen may substitute for carbon with no marked or consistent changes observed in affinity or efficacy. Hydroxylation of the carbon bridge decreases affinity for the receptor approximately 10-fold but does not alter efficacy, whereas a similar substitution made in the norepinephrine-series of phenethylamines markedly increases affinity (Patil et al., 1974). With both the imidazolines and phenethylamines, this carbon atom may stereoselectively influence binding to the receptor. These results suggest that the carbon atom bridging the phenyl and imidazoline rings of tolazoline-like imidazolines serves only to provide optimal separation between these rings and does not contribute directly to the binding process. It is proposed that alpha adrenergic imidazolines interact differently with the alpha adrenergic receptor than the norepinephrine-like phenethylamines.

Retardation effect of nitrogen compounds and condensed aromatics on shale oil catalytic cracking processing and their characterization.

PubMed

Li, Nan; Chen, Chen; Wang, Bin; Li, Shaojie; Yang, Chaohe; Chen, Xiaobo

Untreated shale oil, shale oil treated with HCl aqueous solution and shale oil treated with HCl and furfural were used to do comparative experiments in fixed bed reactors. Nitrogen compounds and condensed aromatics extracted by HCl and furfural were characterized by electrospray ionization Fourier transform cyclotron resonance mass spectrometry and gas chromatography and mass spectrometry, respectively. Compared with untreated shale oil, the conversion and yield of liquid products increased considerably after removing basic nitrogen compounds by HCl extraction. Furthermore, after removing nitrogen compounds and condensed aromatics by both HCl and furfural, the conversion and yield of liquid products further increased. In addition, N 1 class species are predominant in both basic and non-basic nitrogen compounds, and they are probably indole, carbazole, cycloalkyl-carbazole, pyridine and cycloalkyl-pyridine. As for the condensed aromatics, most of them possess aromatic rings with two to three rings and zero to four carbon atom.

Concise copper-catalyzed synthesis of tricyclic biaryl ether-linked aza-heterocyclic ring systems.

PubMed

Mestichelli, Paola; Scott, Matthew J; Galloway, Warren R J D; Selwyn, Jamie; Parker, Jeremy S; Spring, David R

2013-11-01

A new method for the synthesis of tricyclic biaryl ether-linked ring systems incorporating seven-, eight-, and nine-membered ring amines is presented. In the presence of catalytic quantities of copper(I), readily accessible acyclic precursors undergo an intramolecular carbon-oxygen bond-forming reaction facilitated by a "templating" chelating nitrogen atom. The methodology displays a broad substrate scope, is practical, and generates rare and biologically interesting tricyclic heteroaromatic products that are difficult to access by other means.

Stability and molecular properties of the boron-nitrogen alternating analogs of azulene and naphthalene: a computational study.

PubMed

Catão, Anderson José Lopes; López-Castillo, Alejandro

2017-04-01

In this work, the spectroscopic information, stability and aromaticity of the boron-nitrogen azulene and naphthalene molecules are provided by the use of CC2 (geometry optimization, dipole moment, UV-vis spectrum calculations) and DFT (vibrational spectrum and NMR calculations) methodologies. One isomer of the investigated boron-nitrogen naphthalene (boroazanaphthalene) and two isomers of boron-nitrogen azulene, 1,3,4,6,8-pentaaza-2,3a,5,7,8a-pentaboraazulene (BN-azulene) and 2,3a,5,7,8a-pentaaza-1,3,4,6,8- pentaboraazulene (NB-azulene), are stable systems. However, these molecules have different properties, i.e., different stability, dipole moment, and aromaticity based on the NICS approach. BN-naphthalene has a high dipole moment magnitude showing high polar character, while naphthalene is apolar. BN- and NB-azulene are weakly polar, while ordinary azulene is highly polar in character. Also, substitution of C atoms by B and N atoms decreases the aromaticity. In the case of NB-azulene, the seven-membered ring has anti-aromaticity behavior while both rings of BN-azulene exhibit aromaticity. We expect that the new theoretical data provided in this work will be useful in identifying and characterizing experimentally the compounds investigated, and in helping our understanding of the chemistry of boron-nitrogen molecules. Graphical abstract Boron-nitrogen alternating analogs of azulene. Spectral distinction between isomers.

Metal-sulfur type cell having improved positive electrode

DOEpatents

Dejonghe, Lutgard C.; Visco, Steven J.; Mailhe, Catherine C.; Armand, Michel B.

1989-01-01

An novel metal-sulfur type cell operable at a temperature of 200.degree. C. or less with an energy density of 150 Whrs/Kg or better is disclosed characterized by an organo-sulfur cathode formed from an organic-sulfur compound having the general formula, in its charged state, of (R(S).sub.y).sub.n wherein y=1 to 6; n=2 to 20; and R is one or more different aliphatic or aromatic organic moieties having 1 to 20 carbon atoms, which may include one or more oxygen, sulfur, or nitrogen heteroatoms when R comprisises one of more aromatic rings, or one or more oxygen, sulfur, nitrogen, or fluorine atoms associtated with the chain when R comprises an aliphatic chain, wherein the aliphatic group may be linear or branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon.

Metal-sulfur type cell having improved positive electrode

DOEpatents

DeJonghe, L.C.; Visco, S.J.; Mailhe, C.C.; Armand, M.B.

1988-03-31

A novel metal-sulfur type cell operable at a temperature of 200/degree/C or less with an energy density of 150 Whrs/Kg or better is disclosed characterized by an organo-sulfur cathode formed from an organic-sulfur compound having the general formula, in its charged state, of (R(S)/sub y/)n wherein y = 1 to 6; n = 2 to 20; and R is one or more different aliphatic or aromatic organic moieties having 1 to 20 carbon atoms, which may include one or more oxygen, sulfur, or nitrogen heteroatoms when R comprises one or more aromatic rings, or one or more oxygen, sulfur, nitrogen, or fluorine atoms associated with the chain when R comprises an aliphatic chain, wherein the aliphatic group may be linear or branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon. 4 figs.

Influence of C-H···O Hydrogen Bonds on Macroscopic Properties of Supramolecular Assembly.

PubMed

Ji, Wei; Liu, Guofeng; Li, Zijian; Feng, Chuanliang

2016-03-02

For CH···O hydrogen bonds in assembled structures and the applications, one of the critical issues is how molecular spatial structures affect their interaction modes as well as how to translate the different modes into the macroscopic properties of materials. Herein, coumarin-derived isomeric hydrogelators with different spatial structures are synthesized, where only nitrogen atoms locate at the ortho, meso, or para position in the pyridine ring. The gelators can self-assemble into single crystals and nanofibrous networks through CH···O interactions, which are greatly influenced by nitrogen spatial positions in the pyridine ring, leading to the different self-assembly mechanisms, packing modes, and properties of the nanofibrous networks. Typically, different cell proliferation rates are obtained on the different CH···O bonds driving nanofibrous structures, implying that tiny variation of the stereo-position of nitrogen atoms can be sensitively detected by cells. The study paves a novel way to investigate the influence of isomeric molecular assembly on macroscopic properties and functions of materials.

Fast intramolecular electron transfer and dual fluorescence. Configurational change of the amino nitrogen (pyramidal{yields}planar)

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

Haar, Th. von der; Hebecker, A.; Il'Ichev, Yu.

1996-04-01

The fast excited state intramolecular charge transfer (ICT) and dual fluorescence observed with several 4-aminobenzonitriles is discussed. It is shown that the magnitude of the energy gap between the two lowest excited states determines the occurrence or absence of ICT. The photophysical behavior of a series of four 4-aminobenzonitriles in which the amino nitrogen atom is part of a four- to seven-membered heterocyclic ring, P4C to P7C, is studied by using time-resolved fluorescence measurements. The ICT rate constant strongly decreases with decreasing ring size. With P4C in diethyl ether ICT does not occur. This is attributed to the increase ofmore » the amino nitrogen inversion barrier with decreasing ring size. The change of the amino nitrogen from pyramidal to planar is considered to be an important reaction coordinate. The photophysics of the 4-aminobenzonitriles is different from that of other ICT systems such as donor/acceptor-substituted stilbenes and 9,9'-bianthryl, which are governed by the charge distribution and macroscopic Coulombic interaction in their CT states.« less

Fast intramolecular electron transfer and dual fluorescence. Configurational change of the amino nitrogen (pyramidal-->planar)

NASA Astrophysics Data System (ADS)

von der Haar, Th.; Hebecker, A.; Il'Ichev, Yu.; Kühnle, W.; Zachariasse, K. A.

1996-04-01

The fast excited state intramolecular charge transfer (ICT) and dual fluorescence observed with several 4-aminobenzonitriles is discussed. It is shown that the magnitude of the energy gap between the two lowest excited states determines the occurrence or absence of ICT. The photophysical behavior of a series of four 4-aminobenzonitriles in which the amino nitrogen atom is part of a four- to seven-membered heterocyclic ring, P4C to P7C, is studied by using time-resolved fluorescence measurements. The ICT rate constant strongly decreases with decreasing ring size. With P4C in diethyl ether ICT does not occur. This is attributed to the increase of the amino nitrogen inversion barrier with decreasing ring size. The change of the amino nitrogen from pyramidal to planar is considered to be an important reaction coordinate. The photophysics of the 4-aminobenzonitriles is different from that of other ICT systems such as donor/acceptor-substituted stilbenes and 9,9'-bianthryl, which are governed by the charge distribution and macroscopic Coulombic interaction in their CT states.

New Synthetic Approaches to TAT

DTIC Science & Technology

1990-03-30

stabilized externally by resonance stabilization of electron withdrawing substituents placed on all four Nitrogen aL,.ms (T,- N -:, ...7; 4- N -NO2 HMX, etc...or internally by ring carbonyl groups adja- cent to the ring- N -atoms (amide resonance). 1. Cyclization experiments on methylene-bisacetamide (MBA4...more, the high instability of the desired 8-membered [8]ane- N 4 system, and the difficulty to apply proper cond’tion-. what the final products can

Nuclear magnetic and nuclear quadrupole resonance parameters of β-carboline derivatives calculated using density functional theory

NASA Astrophysics Data System (ADS)

Ahmadinejad, Neda; Tari, Mostafa Talebi

2017-04-01

A density functional theory (DFT) calculations using B3LYP/6-311++G( d,p) method were carried out to investigate the relative stability of the molecules of β-carboline derivatives such as harmaline, harmine, harmalol, harmane and norharmane. Calculated nuclear quadrupole resonance (NQR) parameters were used to determine the 14N nuclear quadrupole coupling constant χ, asymmetry parameter η and EFG tensor ( q zz ). For better understanding of the electronic structure of β-carboline derivatives, natural bond orbital (NBO) analysis, isotropic and anisotropic NMR chemical shieldings were calculated for 14N nuclei using GIAO method for the optimized structures. The NBO analysis shows that pyrrole ring nitrogen (N9) atom has greater tendency than pyridine ring nitrogen (N2) atom to participate in resonance interactions and aromaticity development in the all of these structures. The NMR and NQR parameters were studied in order to find the correlations between electronic structure and the structural stability of the studied molecules.

Photophysical Properties on Functional Pi-Electronic Molecular Systems

DTIC Science & Technology

2012-08-01

the aromaticity; i) it is possible to control the number of conjugated π-electrons by changing the number of connected pyrrole rings, ii) by...flexibilities, and facile capture and release of two pyrrolic protons upon two-electron oxidation and reduction, respectively. Scheme 2. (a...nitrogen atoms of pyrrole A, B, C and D, and the ortho-carbon atom of meso-pentafluorophenyl group in a trigonal bipyramidal manner. The 1 H NMR spectrum

In silico design of novel proton-pump inhibitors with reduced adverse effects.

PubMed

Li, Xiaoyi; Kang, Hong; Liu, Wensheng; Singhal, Sarita; Jiao, Na; Wang, Yong; Zhu, Lixin; Zhu, Ruixin

2018-05-30

The development of new proton-pump inhibitors (PPIs) with less adverse effects by lowering the pKa values of nitrogen atoms in pyrimidine rings has been previously suggested by our group. In this work, we proposed that new PPIs should have the following features: (1) number of ring II = number of ring I + 1; (2) preferably five, six, or seven-membered heteroatomic ring for stability; and (3) 1 < pKa1 < 4. Six molecular scaffolds based on the aforementioned criteria were constructed, and R groups were extracted from compounds in extensive data sources. A virtual molecule dataset was established, and the pKa values of specific atoms on the molecules in the dataset were calculated to select the molecules with required pKa values. Drug-likeness screening was further conducted to obtain the candidates that significantly reduced the adverse effects of long-term PPI use. This study provided insights and tools for designing targeted molecules in silico that are suitable for practical applications.

Synthesis, XRD single crystal structure analysis, vibrational spectral analysis, molecular dynamics and molecular docking studies of 2-(3-methoxy-4-hydroxyphenyl) benzothiazole

NASA Astrophysics Data System (ADS)

Sarau Devi, A.; Aswathy, V. V.; Sheena Mary, Y.; Yohannan Panicker, C.; Armaković, Stevan; Armaković, Sanja J.; Ravindran, Reena; Van Alsenoy, C.

2017-11-01

The vibrational spectra and corresponding vibrational assignments of 2-(3-methoxy-4-hydroxyphenyl)benzothiazole is reported. Single crystal XRD data of the title compound is reported and the orientation of methoxy group is cis to nitrogen atom of the thiazole ring. The phenyl ring breathing modes of the title compound are assigned at 1042 and 731 cm-1 theoretically. The charge transfer within the molecule is studied using frontier molecular orbital analysis. The chemical reactivity descriptors are calculated theoretically. The NMR spectral data predicted theoretically are in good agreement with the experimental data. The strong negative region spread over the phenyl rings, nitrogen atom and oxygen atom of the hydroxyl group in the MEP plot is due to the immense conjugative and hyper conjugative resonance charge delocalization of π-electrons. Molecule sites prone to electrophilic attacks have been determined by analysis of ALIE surfaces, while Fukui functions provided further insight into the local reactivity properties of title molecule. Autoxidation properties have been investigated by calculation of bond dissociation energies (BDEs) of hydrogen abstraction, while BDEs of the rest of the single acyclic bonds were valuable for the further investigation of degradation properties. Calculation of radial distribution functions was performed in order to determine which atoms of the title molecule have pronounced interactions with water molecules. The title compound forms a stable complex with aryl hydrocarbon receptor and can be a lead compound for developing new anti-tumor drug. Antimicrobial properties of the title compound was screened against one bacterial culture Escherchia coli and four fungal cultures viz., Aspergillus niger, Pencillum chrysogenum, Saccharomyces cerevisiae and Rhyzopus stolonifer.

Crystal structure of 4,5-dinitro-1 H-imidazole

DOE PAGES

Windler, G. Kenneth; Scott, Brian L.; Tomson, Neil C.; ...

2015-01-01

Here, the title compound, C 3H 2N 4O 4, forms crystals with two molecules in the asymmetric unit which are conformationally similar. With the exception of the O atoms of the nitro groups, the molecules are essentially planar. In the crystal, adjacent molecules are associated by N—H...N hydrogen bonds involving the imidazole N—H donors and N-atom acceptors of the unsaturated nitrogen of neighboring rings, forming layers parallel to (010).

Biosynthesis of oxygen and nitrogen-containing heterocycles in polyketides

PubMed Central

Hemmerling, Franziska

2016-01-01

Summary This review highlights the biosynthesis of heterocycles in polyketide natural products with a focus on oxygen and nitrogen-containing heterocycles with ring sizes between 3 and 6 atoms. Heterocycles are abundant structural elements of natural products from all classes and they often contribute significantly to their biological activity. Progress in recent years has led to a much better understanding of their biosynthesis. In this context, plenty of novel enzymology has been discovered, suggesting that these pathways are an attractive target for future studies. PMID:27559404

Polymeric Cd(II), trinuclear and mononuclear Ni(II) complexes of 5-methyl-4-phenyl-1,2,4-triazole-3-thione: Synthesis, structural characterization, thermal behaviour, fluorescence properties and antibacterial activity

NASA Astrophysics Data System (ADS)

Bharty, M. K.; Paswan, S.; Dani, R. K.; Singh, N. K.; Sharma, V. K.; Kharwar, R. N.; Butcher, R. J.

2017-02-01

Syntheses of a polymeric Cd(II) complex, [Cd(mptt)2]n (1), a trinuclear Ni(II) complex, [Ni3(μ-mptt)4(μ-H2O)2(H2O)2(ttfa)2]·3H2O (2) and a mononuclear Ni(II) complex [Ni(mptt)2(en)2] (3) have been performed using the ligand 5-methyl-4-phenyl-1,2,4-triazole-3-thione (Hmptt) and nickel(II)/cadmium(II) salts {ttfa = thenoyltrifluroacetonate). The ligand and the complexes have been characterized by various physicochemical methods in addition to their single crystal X-ray structure. The Cd centre in complex 1 adopts a distorted tetrahedral geometry with one sulfur atom and two mptt ligands provide three nitrogen atoms from three triazole units. The sulfur atom of the ligand binds covalently and overall the ligand acts as uninigative N,S/N,N bidentate moiety. The polymeric structure of complex 1 results from the N atoms of the neighboring triazole units coordinating with the Cd(II) centre. The three Ni(II) centres in the trinuclear Ni(II) complex 2 form a linear arrangement and all have six coordinated arrangements. The middle Ni(II) binds with four deprotonated triazole ring nitrogens and two water molecules form two bridges. The terminal Ni(II) centres bind through two thenoyl oxygens, two triazole nitrogens and water molecules that formed bridges with the middle Ni centre. In complex 3, the nickel(II) centre is covalently bonded through two deprotonated triazole ring nitrogens from two ligand moieties and other four sites are occupied by four nitrogens from two bidentate en ligands. Thermogravimetric analyses (TGA) of the complexes indicated for NiO as the final residue. The bioefficacy of the ligand and complexes 2 and 3 have been examined against the growth of bacteria to evaluate their anti-microbial potential. Complex 2 showed high antibacterial activity as compared to the ligand and complex 3. Complexes 1, 2 and 3 are fluorescent materials with maximum emissions at 425, 421 and 396 nm at an excitation wavelength of 323, 348 and 322 nm, respectively.

Conformation analysis of 1″,4″-Dispirocyclohexane-6,6'-bis(benzothiazoline): Combined IR, Raman, XRD and DFT approach.

PubMed

P J, Arathi; Gupta, Parth; Babu N, Jagadeesh; C N, Sundaresan; Venkatnarayan, Ramanathan

2016-03-15

The subject of the study is the structure and conformation of 1″,4″-Dispiro-cyclohexane-6,6'-bis(benzothiazoline), a dispiro compound that has a cyclohexyl ring flanked by two benzothiazoline rings on either side. Using single crystal X-ray diffraction measurements, Infra-red absorption, and Raman spectroscopy techniques, it is found that the central cyclohexyl ring assumes the chair conformation and the sulfur, nitrogen atoms in both the benzothiazole rings are in the trans configurations. The experimental findings are further corroborated by geometry optimization and frequency calculations at B3LYP/6-311++G** level of theory using Gaussian 09 suite of program. Copyright © 2015 Elsevier B.V. All rights reserved.

Long-range effect of ion implantation of Raex and Hardox steels

NASA Astrophysics Data System (ADS)

Budzyński, P.; Kamiński, M.; Droździel, A.; Wiertel, M.

2016-09-01

Ion implantation involves introduction of ionized atoms of any element (nitrogen) to metals thanks to the high kinetic energy that they acquired in the electric field. The distribution of nitrogen ions implanted at E = 65 keV energy and D = 1.1017 N+ /cm2 fluence in the steel sample and vacancies produced by them was calculated using the SRIM program. This result was confirmed by RBS measurements. The initial maximum range of the implanted nitrogen ions is ∼⃒0.17 μm. This value is relatively small compared to the influence of nitriding on the thickness surface layer of modified steel piston rings. Measurements of the friction coefficient during the pin-on-disc tribological test were performed under dry friction conditions. The friction coefficient of the implanted sample increased to values characteristic of an unimplanted sample after ca. 1500 measurement cycles. The depth of wear trace is ca. 2.4 μm. This implies that the thickness of the layer modified by the implantation process is ∼⃒2.4 μm and exceeds the initial range of the implanted ions by an order of magnitude. This effect, referred to as a long-range implantation effect, is caused by migration of vacancies and nitrogen atoms into the sample. This phenomenon makes ion implantation a legitimate process of modification of the surface layer in order to enhance the tribological properties of critical components of internal combustion engines such as steel piston rings.

Homologation process making higher alcohols

DOEpatents

Leung, Tak W.; Dombek, Bernard D.

1990-01-01

A liquid phase process for the manufacture of C.sub.2+ alkanols by the reaction of hydrogen with carbon monoxide in the presence of a catalyst containing ruthenium, cobalt, a halide-containing compound, and an aromatic compound substituted in adjacent ring positions by nitrogen atoms. The process embraces the use of rhodium as an additive to the catalyst system.

A 'bottom up', ab initio computational approach to understanding fundamental photophysical processes in nitrogen containing heterocycles, DNA bases and base pairs.

PubMed

Marchetti, Barbara; Karsili, Tolga N V; Ashfold, Michael N R; Domcke, Wolfgang

2016-07-27

The availability of non-radiative decay mechanisms by which photoexcited molecules can revert to their ground electronic state, without experiencing potentially deleterious chemical transformation, is fundamental to molecular photostability. This Perspective Article combines results of new ab initio electronic structure calculations and prior experimental data in an effort to systematise trends in the non-radiative decay following UV excitation of selected families of heterocyclic molecules. We start with the prototypical uni- and bicyclic molecules phenol and indole, and explore the structural and photophysical consequences of incorporating progressively more nitrogen atoms within the respective ring structures en route to the DNA bases thymine, cytosine, adenine and guanine. For each of the latter, we identify low energy non-radiative decay pathways via conical intersections with the ground state potential energy surface accessed by out-of-plane ring deformations. This is followed by summary descriptions and illustrations of selected rival (electron driven H atom transfer) non-radiative excited state decay processes that demand consideration once the nucleobases are merely components in larger biomolecular systems like nucleosides, and both individual and stacked base-pairs.

Understanding the directed ortho lithiation of (R)-Ph₂P(=NCO₂Me)NHCH(Me)Ph. NMR spectroscopic and computational study of the structure of the N-lithiated species.

PubMed

Casimiro, M; García-López, J; Iglesias, M J; López-Ortiz, F

2014-10-14

A multinuclear magnetic resonance ((1)H, (7)Li, (13)C, (15)N, (31)P) and DFT computational study at the M06-2X(SMD,THF)/6-311+G(d,p)//B3LYP/6-31G(d) level of the structure of a N-lithiated phosphinimidic amide (R)-Ph2P(=NCO2Me)NHCH(Me)Ph 13 has been performed. In THF solution it exists as an equilibrium mixture of monomers and dimers. The monomers consist of a six-membered ring formed by coordination of the lithium atom with the deprotonated nitrogen and the oxygen atom of the carbonyl group. This coordination mode is in contrast to the standard N,N-chelation observed in N-lithiated N,N'-bis(trimethylsilyl)phosphinimidic amides. The calculations showed that the metallacycle adopts a twist-boat conformation and that the lithium atom is in a tetrahedral environment involving O,N-chelation by the ligand and coordination to two/one THF molecules in the monomer/dimer. Dimerization takes place through O-Li bridges. For all species two series of isomers have been identified, which originated by restricted rotation of the methoxy group and ring inversion. The twist-boat conformational interconversion seems to be operating for explaining the pattern of signals observed in the (7)Li and (31)P NMR spectra. The structure found for the most stable dimer is analogous to the molecular structure reported for a related C(α)-lithiated phosphazene 20. The structural study revealed that the chiral side-arm of the N-lithiated species is oriented to the outer face of the pro-S P-phenyl ring, which shows one ortho-proton very close to the nitrogen atom of the carbamate moiety. In this conformation, proton abstraction by a base is highly favoured, in agreement with the experimental results.

The π-Electron Delocalization in 2-Oxazolines Revisited: Quantification and Comparison with Its Analogue in Esters

PubMed Central

Fimberger, Martin; Luef, Klaus P.; Payerl, Claudia; Fischer, Roland C.; Stelzer, Franz; Kállay, Mihály; Wiesbrock, Frank

2015-01-01

The single crystal X-ray analysis of the ester-functionalized 2-oxazoline, methyl 3-(4,5-dihydrooxazol-2-yl)propanoate, revealed π-electron delocalization along the N–C–O segment in the 2-oxazoline pentacycle to significant extent, which is comparable to its counterpart along the O–C–O segment in the ester. Quantum chemical calculations based on the experimental X-ray geometry of the molecule supported the conjecture that the N–C–O segment has a delocalized electronic structure similar to an ester group. The calculated bond orders were 1.97 and 1.10 for the N=C and C–O bonds, and the computed partial charges for the nitrogen and oxygen atoms of −0.43 and −0.44 were almost identical. In the ester group, the bond orders were 1.94 and 1.18 for the C–O bonds, while the partial charges of the oxygen atom are −0.49 and −0.41, which demonstrates the similar electronic structure of the N–C–O and O–C–O segments. In 2-oxazolines, despite the higher electronegativity of the oxygen atom (compared to the nitrogen atom), the charges of the hetero atoms oxygen and nitrogen are equalized due to the delocalization, and it also means that a cationic attack on the nitrogen is possible, enabling regioselectivity during the initiation of the cationic ring-opening polymerization of 2-oxazoline monomers, which is a prerequisite for the synthesis of materials with well-defined structures. PMID:28184258

Conformational analysis of polyfunctional amino compounds by molecular mechanics. Part III. 1,3,5-Triazacyclohexanes, 2,5,7,10-tetrazabicyclo[4.4.0]-decanes and 1,3,5,7-tetrazabicyclo[3.3.1]nonanes

NASA Astrophysics Data System (ADS)

Carballeira, Luis; Mosquera, Ricardo A.; Ríos, Miguel A.

1989-04-01

The molecular mechanics program of Allinger, MM2,has been applied to the conformational analysis of various cyclic and bicyclic compounds containing the NCN unit. The results have been compared with the available experimental data and with previous MM2 results for other cyclic amino compounds. It is found that the inclusion of more NCN units in the ring has no effect on the agreement between theory and experiment. Changes in ring geometry due to substitution and to increasing the number of nitrogen atoms have been analysed using Cremer-Pople's ring-puckering coordinates.

Synthesis and crystal structure of new copper(II) metal complex: Noncovalent interactions and electrical conductance properties

NASA Astrophysics Data System (ADS)

Pathak, Sudipta; Chakraborty, Koushik; Ghosh, Surajit; Roy, Kunal; Jana, Barnali; Konar, Saugata

2018-01-01

[Cu(pydc)(apyz)(H2O)2] (1) (where pydcH2 = pyridine-2,6-dicarboxylic acid; apyz = 2- aminopyrazine) has been synthesized and characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction techniques. Crystallographic analysis revealed that complex 1 has distorted octahedral geometry with pydcH2 coordinated as tridentate ligands to metal ion through two oxygen atoms of each carboxylate group, nitrogen atom of the pyridine ring and the auxiliary ligand pyrazine nitrogen atom form basal plane and apical positions are occupied by two oxygen atoms of water molecules. In addition, the coordination compounds are connected by a variety of non covalent interactions like OH … π, lone pair … π, π … π and hydrogen bonds. The evaluation of these noncovalent interactions is useful for rationalizing their influence in the crystal packing. In addition, electrical current measured at room temperature on thin film before and after annealed is in the order of 229 μA and 246 μA respectively with bias voltage 1 V.

Motion of protons in the central opening of porphyrins

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

Zayats, V.Y.; Lobanov, V.V.; Pinchuk, V.M.

1986-09-01

The distribution of the electrostatic potential of the molecule of porphine (P) and the anions formed by the successive elimination of one and two central protons from it has been studied by the SCF-MO-LCAO method in the all-valence-electron CNDO/2 approximation. The electrostatic potential of the potential of the (P-2HO/sup 2 -/ dianion is characterized by the presence of four minima located at a distance of about 1 A from the nitrogen atoms. The potential in them is equal to -991 kJ/mole. The value of the potential at the center of the opening is -978 kJ/mole. The distribution of the electrostaticmore » potential of the (P-H)/sup -/ anion with a fixed position of the proton near one of the nitrogen atoms is characterized by the presence of a deep valley situated at the oppositely lying nitrogen atom perpendicularly to the N-H bond. The potential of the molecule of P in the plane of the ring does not have negative values, attesting to the energetic unfavorability of the planar conformations of the (P+H)/sup +/ cation.« less

Nitrogen Rings and Cages Stabilized by Metallic Atoms

DTIC Science & Technology

2009-12-18

1 UNIVERSIDAD DE GUANAJUATO DEPARTAMENTO DE QUIMICA DIVISION DE CIENCIAS NATURALES Y EXACTAS Dr. Gabriel Merino NORIA ALTA s/n...this collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data...collection of information if it does not display a currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. 1 . REPORT

Biosynthesis of the trehalase inhibitor trehazolin.

PubMed

Sugiyama, Yasumasa; Nagasawa, Hiromichi; Suzuki, Akinori; Sakuda, Shohei

2002-03-01

Trehazolin (1) is a trehalase inhibitor produced by Micromonospora coriacea. Biosynthesis of 1 was studied by feeding experiments with a variety of labeled precursors. Feeding experiments with [1-13C]- and [6-13C]-D-glucose revealed that the carbon skeletons of both a glucose residue and a cyclopentane ring moiety in 1 were each derived from glucose, and that C-C bond formation between C-1 and C-5 of glucose occurred during the cyclopentane ring formation. Furthermore, an experiment with [guanidino-13C, 15N2]-L-arginine revealed that two nitrogen atoms and a quaternary carbon atom involved in the aminooxazoline moiety of 1 originated from an amidino group of arginine. Further feeding experiments with [1-2H]-, [2-2H]-, [4-2H]-, [6,6-2H2]- and [1,2,3,4,5,6,6-2H7]-D-glucose as well as [1-13C]-D-fructose showed that deuteriums on C-1, C-3, C-4 and C-6 of glucose were retained during the formation of the cyclopentane ring moiety of 1.

The low photo-inactivation rate of bacteria in human plasma II. Inhibition of methylene blue bleaching in plasma and effective bacterial destruction by the addition of dilute acetic acid to human plasma.

PubMed

Chen, Jie; Cesario, Thomas C; Li, Runze; Er, Ali O; Rentzepis, Peter M

2015-10-01

Methylene blue (MB) and other photo-sensitizer molecules have been recognized as effective means for the inactivation of bacteria and other pathogens owing to their ability to photo-generate reactive oxygen species (ROS) including singlet oxygen. These reactive species react with the membrane of the bacteria causing their destruction. However, the efficiency of MB to destroy bacteria in plasma is very low because the MB 660 nm absorption band, that is responsible for the ROS generation, is bleached. The bleaching of MB, in plasma, is caused by the attachment of a hydrogen atom to the central ring nitrogen of MB, which destroys the ring conjugation and forms Leuco-MB which does not absorb in the 600 nm region. In this paper we show that addition of dilute acetic acid, ∼10(-4) M, to human plasma, prevents H-atom attachment to MB, allowing MB to absorb at 660 nm, generates singlet oxygen and thus inactivates bacteria. The mechanism proposed, for preventing MB bleaching in plasma, is based on the oxidation of cysteine to cystine, by reaction with added dilute acetic acid, thus eliminating the availability of the thiol hydrogen atom which attaches to the MB nitrogen. It is expected that the addition of acetic acid to plasma will be effective in the sterilization of plasma and killing of bacteria in wounds and burns.

Probes for Narcotic Receptor Mediated Phenomena. 39. Enantiomeric N-Substituted Benzofuro[2,3-c]pyridin-6-ols: Synthesis and Topological Relationship to Oxide-Bridged Phenylmorphans

DTIC Science & Technology

2009-01-01

ray crystallographic analysis of the salt (-)-10 3R-(-)- mandelate (Figure 2). N-Alkylation of the secondary amine 4aR,9aS-9 or 4aS,9aR-10 (Scheme 3... rmsd ) between the heavy atoms of both the dihydrofuran and the piperidine rings. Conformer B1 is epimeric to A and was obtained by nitrogen inversion... rmsd value of the fitting is 0.13, 0.12, and 0.07 Å. The dihydrofuran ring of conformer C overlaps well with that of the para-d isomer that is known to

Analysis of the contributions of ring current and electric field effects to the chemical shifts of RNA bases.

PubMed

Sahakyan, Aleksandr B; Vendruscolo, Michele

2013-02-21

Ring current and electric field effects can considerably influence NMR chemical shifts in biomolecules. Understanding such effects is particularly important for the development of accurate mappings between chemical shifts and the structures of nucleic acids. In this work, we first analyzed the Pople and the Haigh-Mallion models in terms of their ability to describe nitrogen base conjugated ring effects. We then created a database (DiBaseRNA) of three-dimensional arrangements of RNA base pairs from X-ray structures, calculated the corresponding chemical shifts via a hybrid density functional theory approach and used the results to parametrize the ring current and electric field effects in RNA bases. Next, we studied the coupling of the electric field and ring current effects for different inter-ring arrangements found in RNA bases using linear model fitting, with joint electric field and ring current, as well as only electric field and only ring current approximations. Taken together, our results provide a characterization of the interdependence of ring current and electric field geometric factors, which is shown to be especially important for the chemical shifts of non-hydrogen atoms in RNA bases.

Effect of nitrogen plasma afterglow on the surface charge effect resulted during XPS surface analysis of amorphous carbon nitride thin films

NASA Astrophysics Data System (ADS)

Kayed, Kamal

2018-06-01

The aim of this paper is to investigate the relationship between the micro structure and the surface charge effect resulted during XPS surface analysis of amorphous carbon nitride thin films prepared by laser ablation method. The study results show that the charge effect coefficient (E) is not just a correction factor. We found that the changes in this coefficient value due to incorporation of nitrogen atoms into the carbon network are related to the spatial configurations of the sp2 bonded carbon atoms, order degree and sp2 clusters size. In addition, results show that the curve E vs. C(sp3)-N is a characteristic curve of the micro structure. This means that using this curve makes it easy to sorting the samples according to the micro structure (hexagonal rings or chains).

Proton-bound dimers of nitrogen heterocyclic molecules: Substituent effects on the structures and binding energies of homodimers of diazine, triazine, and fluoropyridine

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

Attah, Isaac K.; Platt, Sean P.; Meot-Ner, Michael

2014-03-21

The bonding energies of proton-bound homodimers BH{sup +}B were measured by ion mobility equilibrium studies and calculated at the DFT B3LYP/6-311++G{sup **} level, for a series of nitrogen heterocyclic molecules (B) with electron-withdrawing in-ring N and on-ring F substituents. The binding energies (ΔH°{sub dissoc}) of the proton-bound dimers (BH{sup +}B) vary significantly, from 29.7 to 18.1 kcal/mol, decreasing linearly with decreasing the proton affinity of the monomer (B). This trend differs significantly from the constant binding energies of most homodimers of other organic nitrogen and oxygen bases. The experimentally measured ΔH°{sub dissoc} for (1,3-diazine){sub 2}H{sup +}, i.e., (pyrimidine){sub 2}H{sup +}more » and (3-F-pyridine){sub 2}H{sup +} are 22.7 and 23.0 kcal/mol, respectively. The measured ΔH°{sub dissoc} for the pyrimidine{sup ·+}(3-F-pyridine) radical cation dimer (19.2 kcal/mol) is signifcantly lower than that of the proton-bound homodimers of pyrimidine and 3-F-pyridine, reflecting the stronger interaction in the ionic H-bond of the protonated dimers. The calculated binding energies for (1,2-diazine){sub 2}H{sup +}, (pyridine){sub 2}H{sup +}, (2-F-pyridine){sub 2}H{sup +}, (3-F-pyridine){sub 2}H{sup +}, (2,6-di-F-pyridine){sub 2}H{sup +}, (4-F-pyridine){sub 2}H{sup +}, (1,3-diazine){sub 2}H{sup +}, (1,4-diazine){sub 2}H{sup +}, (1,3,5-triazine){sub 2}H{sup +}, and (pentafluoropyridine){sub 2}H{sup +} are 29.7, 24.9, 24.8, 23.3, 23.2, 23.0, 22.4, 21.9, 19.3, and 18.1 kcal/mol, respectively. The electron-withdrawing substituents form internal dipoles whose electrostatic interactions contribute to both the decreased proton affinities of (B) and the decreased binding energies of the protonated dimers BH{sup +}B. The bonding energies also vary with rotation about the hydrogen bond, and they decrease in rotamers where the internal dipoles of the components are aligned efficiently for inter-ring repulsion. For compounds substituted at the 3 or 4 (meta or para) positions, the lowest energy rotamers are T-shaped with the planes of the two rings rotated by 90° about the hydrogen bond, while the planar rotamers are weakened by repulsion between the ortho hydrogen atoms of the two rings. Conversely, in ortho-substituted (1,2-diazine){sub 2}H{sup +} and (2-F-pyridine){sub 2}H{sup +}, attractive interactions between the ortho (C–H) hydrogen atoms of one ring and the electronegative ortho atoms (N or F) of the other ring are stabilizing, and increase the protonated dimer binding energies by up to 4 kcal/mol. In all of the dimers, rotation about the hydrogen bond can involve a 2–4 kcal/mol barrier due to the relative energies of the rotamers.« less

Submolecular resolution in scanning probe images of Sn-phthalocyanines on Cu(1 0 0) using metal tips

NASA Astrophysics Data System (ADS)

Buchmann, Kristof; Hauptmann, Nadine; Foster, Adam S.; Berndt, Richard

2017-10-01

Single Sn-phthalocyanine (SnPc) molecules adsorb on Cu(1 0 0) with the Sn ion above (Sn-up) or below (Sn-down) the molecular plane. Here we use a combination of atomic force microscopy (AFM), scanning tunnelling microscopy (STM) and first principles calculations to understand the adsorption configuration and origin of observed contrast of molecules in the Sn-down state. AFM with metallic tips images the pyrrole nitrogen atoms in these molecules as attractive features while STM reveals a chirality of the electronic structure of the molecules close to the Fermi level E_F, which is not observed in AFM. Using density functional theory calculations, the origin of the submolecular contrast is analysed and, while the electrostatic forces turn out to be negligible, the van der Waals interaction between the phenyl rings of SnPc and the substrate deform the molecule, push the pyrrole nitrogen atoms away from the substrate and thus induce the observed submolecular contrast. Simulated STM images reproduce the chirality of the electronic structure near E_F.

Complexation of molecular clips containing fragments of diphenylglycoluril and benzocrown ethers with paraquat and its derivatives

PubMed Central

Kikot', Leonid S; Kulygina, Catherine Yu; Lyapunov, Alexander Yu; Shishkina, Svetlana V; Zubatyuk, Roman I; Bogaschenko, Tatiana Yu

2017-01-01

The complexation of molecular clips containing fragments of diphenylglycoluril and benzocrown ethers with paraquat and its derivatives has been studied both in solution and in the solid state. In this paper we studied the influence of the crown ether ring size and the nature of the substituents at the nitrogen atoms of the paraquat derivatives on the composition and stability of these complexes. PMID:29062427

Synthesis and characterization of Ni(II) complex with 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7,14-dienium bromide

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

Yusoff, Latifah M.; Yusoff, Siti Fairus M.; Ismail, Wafiuddin

Nickel(II) complex have been synthesized by treating a 14-membered ring tetraaza macrocyclic compound, 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7,14-dienium, bromide (Me{sub 6}N{sub 4}H{sub 4})Br{sub 2} with nickel acetate in metanol. The complex was characterized using elemental analysis, Fourier Transform Infrared (FTIR), Ultraviolet-Visible (UV-Vis), and single crystal diffraction (X-ray). The nickel atom coordinates through four nitrogen atoms in the ligand. Square planar geometry has been proposed for this complex.

Interactions between 2,4-bis-pteridine-1,5-benzodiazepine and group 12 dihalides: synthesis, spectral and XRD structural studies and theoretical calculations.

PubMed

Illán-Cabeza, Nuria A; Jiménez-Pulido, Sonia B; Hueso-Ureña, Francisco; Peña-Ruiz, Tomás; Quirós-Olozábal, Miguel; Moreno-Carretero, Miguel N

2016-11-28

2,4-Bis(1,3,7-trimethyl-pteridine-2,4(1H,3H)-dione-6-yl)-2,3-dihydro-2-methyl-1H-1,5-benzodiazepine (DLMBZD) has been prepared and its molecular and crystal structures have been determined from spectral and XRD data. The benzodiazepine ligand was reacted with zinc(ii), cadmium(ii) and mercury(ii) chloride, bromide and iodide to give complexes with general formula [M(DLMBZD)X 2 ]. The complexes have been synthesized and characterized by IR, NMR and elemental analysis. The structure of seven complexes has been obtained by single crystal X-ray diffraction. In all the cases, the metal is (2 + 2 + 1)-five-coordinated by two halide ligands, two nitrogen atoms from pyrazine and diazepine rings and a carbonyl oxygen from a pteridine ring. The coordinated-metal environment is a square-based pyramid, with increasing trigonality from Hg(ii) to Zn(ii) complexes. To coordinate the metals, the ligand folds itself, establishing four intramolecular σ-π interactions with the pyrimidine and pyrazine rings. A topological analysis of the electron density using the Quantum Theory of Atoms in Molecules and the complexes stability has been performed.

Synthesis and structural characterization of lithium, sodium and potassium complexes supported by a tridentate amino-bisphenolate ligand

NASA Astrophysics Data System (ADS)

Durango-García, Clara J.; Rufino-Felipe, Ernesto; López-Cardoso, Marcela; Muñoz-Hernández, Miguel-Ángel; Montiel-Palma, Virginia

2018-07-01

Reactions of methylamino-N,N-bis(2-methylene-4,6-di-tert-butylphenol) (1) with one or two equivalents of bulk Li, Na or K metals in THF or DMSO render mono or dialkali metal complexes depending on the stoichiometric ratio of the reactants. The metal-methylamino-N-(2-methylene-4,6-tert-butylphenol)sbnd N-(2-methylene-4,6-tert-butylphenolate) complexes, 2Li, 2Na and 2K, are generated upon the substitution of a single phenol hydrogen of 1. In the solid state, complex 2Na is a dimer due to the establishment of two symmetric hydrogen bonds between two adjacent molecules. The Na center also engages into the formation of a ten-membered metallacycle ring with a butterfly-like structure. Due to dimerization, an intermolecular six-membered core is formed involving two sodium and four oxygen atoms. The weakly coordinated nitrogen atom from the ligand is nearly perpendicular to the hexagonal core. The dimetal-methylamino-N,N‧-bis(2-methylene-4,6-di-tert-butylphenolate) complexes, 3Li, 3Na and 3K result from metal substitution of the two phenol hydrogens from ligand 1. The SC-XRD structures of 3Li and 3Na are discreet, each incorporating two metal atoms in different coordination environments. Ten-membered rings with boat-boat conformations are also observed as are rhombic central M2O2 cores. The molecular structure of 3K in DMSO shows a higher degree of aggregation. It effectively comprises four K atoms, two ligand backbones and seven solvent molecules forming a central four-membered K2O2 ring perpendicular to an eight-membered structure formed also by K and O atoms spanning over the two ligand moieties.

Carbon and nitrogen isotope variations in tree-rings as records of perturbations in regional carbon and nitrogen cycles.

PubMed

Bukata, Andrew R; Kyser, T Kurtis

2007-02-15

Increasing anthropogenic pollution from urban centers and fossil fuel combustion can impact the carbon and nitrogen cycles in forests. To assess the impact of twentieth century anthropogenic pollution on forested system carbon and nitrogen cycles, variations in the carbon and nitrogen isotopic compositions of tree-rings were measured. Individual annual growth rings in trees from six sites across Ontario and one in New Brunswick, Canada were used to develop site chronologies of tree-ring delta 15N and delta 13C values. Tree-ring 615N values were approximately 0.5% per hundred higher and correlated with contemporaneous foliar samples from the same tree, but not with delta 15N values of soil samples. Temporal trends in carbon and nitrogen isotopic compositions of these tree-rings are consistent with increasing anthropogenic influence on both the carbon and nitrogen cycles since 1945. Tree-ring delta 13C values and delta 15N values are correlated at both remote and urban-proximal sites, with delta 15N values decreasing since 1945 and converging on 1% per hundred at urban-proximal sites and decreasing but not converging on a single delta 15N value in remote sites. These results indicate that temporal trends in tree-ring nitrogen and carbon isotopic compositions record the regional extent of pollution.

Tetrabenzoporphyrin and -mono-, -cis-di- and Tetrabenzotriazaporphyrin Derivatives: Electrochemical and Spectroscopic Implications of meso CH Group Replacement with Nitrogen.

PubMed

van As, Adele; Joubert, Chris C; Buitendach, Blenerhassitt E; Erasmus, Elizabeth; Conradie, Jeanet; Cammidge, Andrew N; Chambrier, Isabelle; Cook, Michael J; Swarts, Jannie C

2015-06-01

Nonperipherally hexyl-substituted metal-free tetrabenzoporphyrin (2H-TBP, 1a) tetrabenzomonoazaporphyrin (2H-TBMAP, 2a), tetrabenzo-cis-diazaporphyrin (2H-TBDAP, 3a), tetrabenzotriazaporphyrin (2H-TBTAP, 4a), and phthalocyanine (2H-Pc, 5a), as well as their copper complexes (1b-5b), were synthesized. As the number of meso nitrogen atoms increases from zero to four, λmax of the Q-band absorption peak becomes red-shifted by almost 100 nm, and extinction coefficients increased at least threefold. Simultaneously the blue-shifted Soret (UV) band substantially decreased in intensity. These changes were related to the relative electron-density of each macrocycle expressed as the group electronegativity sum of all meso N and CH atom groups, ∑χR. X-ray photoelectron spectroscopy differentiated between the three different types of macrocyclic nitrogen atoms (the Ninner, (NH)inner, and Nmeso) in the metal-free complexes. Binding energies of the Nmeso and Ninner,Cu atoms in copper chelates could not be resolved. Copper insertion lowered especially the cathodic redox potentials, while all four observed redox processes occurred at larger potentials as the number of meso nitrogens increased. Computational chemical methods using density functional theory confirmed 1b to exhibit a Cu(II) reduction prior to ring-based reductions, while for 2b, Cu(II) reduction is the first reductive step only if the nonperipheral substituents are hydrogen. When they are methyl groups, it is the second reduction process; when they are ethyl, propyl, or hexyl, it becomes the third reductive process. Spectro-electrochemical measurements showed redox processes were associated with a substantial change in intensity of at least two main absorbances (the Q and Soret bands) in the UV spectra of these compounds.

Water-soluble conductive polymers

DOEpatents

Aldissi, Mahmoud

1989-01-01

Polymers which are soluble in water and are electrically conductive. The monomer repeat unit is a thiophene or pyrrole molecule having an alkyl group substituted for the hydrogen atom located in the beta position of the thiophene or pyrrole ring and having a surfactant molecule at the end of the alkyl chain. Polymers of this class having 8 or more carbon atoms in the alkyl chain exhibit liquid crystalline behavior, resulting in high electrical anisotropy. The monomer-to-monomer bonds are located between the carbon atoms which are adjacent to the sulfur or nitrogen atoms. The number of carbon atoms in the alkyl group may vary from 1 to 20 carbon atoms. The surfactant molecule consists of a sulfonate group, or a sulfate group, or a carboxylate group, and hydrogen or an alkali metal. Negative ions from a supporting electrolyte which may be used in the electrochemical synthesis of a polymer may be incorporated into the polymer during the synthesis and serve as a dopant to increase the conductivity.

Water-soluble conductive polymers

DOEpatents

Aldissi, Mahmoud

1990-01-01

Polymers which are soluble in water and are electrically conductive. The monomer repeat unit is a thiophene or pyrrole molecule having an alkyl group substituted for the hydrogen atom located in the beta position of the thiophene or pyrrole ring and having a surfactant molecule at the end of the alkyl chain. Polymers of this class having 8 or more carbon atoms in the alkyl chain exhibit liquid crystalline behavior, resulting in high electrical anisotropy. The monomer-to-monomer bonds are located between the carbon atoms which are adjacent to the sulfur or nitrogen atoms. The number of carbon atoms in the alkyl group may vary from 1 to 20 carbon atoms. The surfactant molecule consists of a sulfonate group, or a sulfate group, or a carboxylate group, and hydrogen or an alkali metal. Negative ions from a supporting electrolyte which may be used in the electrochemical synthesis of a polymer may be incorporated into the polymer during the synthesis and serve as a dopant to increase the conductivity.

Water-soluble conductive polymers

DOEpatents

Aldissi, M.

1988-02-12

Polymers which are soluble in water and are electrically conductive. The monomer repeat unit is a thiophene or pyrrole molecule having an alkyl group substituted for the hydrogen atom located in the beta position of the thiophene or pyrrole ring and having a surfactant molecule at the end of the alkyl chain. Polymers of this class having 8 or more carbon atoms in the alkyl chain exhibit liquid crystalline behavior, resulting in high electrical anisotropy. The monomer-to-monomer bonds are located between the carbon atoms which are adjacent to the sulfur or nitrogen atoms. The number of carbon atoms in the alkyl group may vary from 1 to 20 carbon atoms. The surfactant molecule consists of a sulfonate group, or a sulfate group, or a carboxylate group, and hydrogen or an alkali metal. Negative ions from a supporting electrolyte which may be used in the electrochemical synthesis of a polymer may be incorporated into the polymer during the synthesis and serve as a dopant to increase the conductivity.

Role of hydrogen bonding in ligand interaction with the N-methyl-D-aspartate receptor ion channel

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

Leeson, P.D.; Carling, R.W.; James, K.

1990-05-01

Displacement of (3H)MK-801 (dizocilpine, 1) binding to rat brain membranes has been used to evaluate the affinities of novel dibenzocycloalkenimines related to 1 for the ion channel binding site (also known as the phencyclidine or PCP receptor) on the N-methyl-D-aspartate (NMDA) subtype of excitory amino acid receptor. In common with many other agents having actions in the central nervous system, these compounds contain a hydrophobic aromatic moiety and a basic nitrogen atom. The conformational rigidity of these ligands provides a unique opportunity to evaluate the importance of specific geometrical properties that influence active-site recognition, in particular the role of themore » nitrogen atom in hydrogen-bonding interactions. The relative affinities (IC50s) of hydrocarbon-substituted analogues of 1 and ring homologated cyclooctenimines illustrate the importance of size-limited hydrophobic binding of both aryl rings and of the quaternary C-5 methyl group. Analysis of the binding of a series of the 10 available structurally rigid dibenzoazabicyclo(x.y.z)alkanes, by using molecular modeling techniques, uncovered a highly significant correlation between affinity and a proposed ligand-active site hydrogen bonding vector (r = 0.950, p less than 0.001). These results are used to generate a pharmacophore of the MK-801 recognition site/PCP receptor, which accounts for the binding of all of the known ligands.« less

Magnesium K-Edge NEXAFS Spectroscopy of Chlorophyll a in Solution.

PubMed

Witte, Katharina; Streeck, Cornelia; Mantouvalou, Ioanna; Suchkova, Svetlana A; Lokstein, Heiko; Grötzsch, Daniel; Martyanov, Wjatscheslav; Weser, Jan; Kanngießer, Birgit; Beckhoff, Burkhard; Stiel, Holger

2016-11-17

The interaction of the central magnesium atom of chlorophyll a (Chl a) with the carbon and nitrogen backbone was investigated by magnesium K near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in fluorescence detection mode. A crude extract of Chl a was measured as a 1 × 10 -2 mol/L ethanol solution (which represents an upper limit of concentration without aggregation) and as dried droplets. For the first time, the investigation of Mg bound to Chl a in a liquid environment by means of X-ray absorption spectroscopy is demonstrated. A pre-edge feature in the dissolved as well as in dried Chl a NEXFAS spectra has been identified as a characteristic transition originating from Mg in the Chl a molecule. This result is confirmed by theoretical DFT calculations leading to molecular orbitals (MO) which are mainly situated on the magnesium atom and nitrogen and carbon atoms from the pyrrole rings. The description is the first referring to the MO distribution with respect to the central Mg ion of Chl a and the surrounding atoms. On this basis, new approaches for the investigations of dynamic processes of molecules in solution and structure-function relationships of photosynthetic pigments and pigment-protein complexes in their native environment can be developed.

Prediction of Setschenow constants of N-heteroaromatics in NaCl solutions based on the partial charge on the heterocyclic nitrogen atom.

PubMed

Yang, Bin; Li, Zhongjian; Lei, Lecheng; Sun, Feifei; Zhu, Jingke

2016-02-01

The solubilities of 19 different kinds of N-heteroaromatic compounds in aqueous solutions with different concentrations of NaCl were determined at 298.15 K with a UV-vis spectrophotometry and titration method, respectively. Setschenow constants, Ks, were employed to describe the solubility behavior, and it is found that the higher ring numbers of N-heteroaromatics gave rise to the lower values of Ks. Moreover, Ks showed a good linear relationship with the partial charge on the nitrogen atom (QN) for either QN > 0 or QN < 0 N-heteroaromatics. It further revealed that QN was well-matched in the prediction of salting-out effect for N-heteroaromatics compared to the conventional descriptors such as molar volume (VH) and the octanol-water partition coefficient (Kow). The heterocyclic N in N-heteroaromatics may interact with Na(+) ions in NaCl solution for QN < 0 and with Cl(-) for QN > 0.

Stepwise O-Atom Transfer in Heme-Based Tryptophan Dioxygenase: Role of Substrate Ammonium in Epoxide Ring Opening.

PubMed

Shin, Inchul; Ambler, Brett R; Wherritt, Daniel; Griffith, Wendell P; Maldonado, Amanda C; Altman, Ryan A; Liu, Aimin

2018-03-28

Heme-based tryptophan dioxygenases are established immunosuppressive metalloproteins with significant biomedical interest. Here, we synthesized two mechanistic probes to specifically test if the α-amino group of the substrate directly participates in a critical step of the O atom transfer during catalysis in human tryptophan 2,3-dioxygenase (TDO). Substitution of the nitrogen atom of the substrate to a carbon (probe 1) or oxygen (probe 2) slowed the catalytic step following the first O atom transfer such that transferring the second O atom becomes less likely to occur, although the dioxygenated products were observed with both probes. A monooxygenated product was also produced from probe 2 in a significant quantity. Analysis of this new product by HPLC coupled UV-vis spectroscopy, high-resolution mass spectrometry, 1 H NMR, 13 C NMR, HSQC, HMBC, and infrared (IR) spectroscopies concluded that this monooxygenated product is a furoindoline compound derived from an unstable epoxyindole intermediate. These results prove that small molecules can manipulate the stepwise O atom transfer reaction of TDO and provide a showcase for a tunable mechanism by synthetic compounds. The product analysis results corroborate the presence of a substrate-based epoxyindole intermediate during catalysis and provide the first substantial experimental evidence for the involvement of the substrate α-amino group in the epoxide ring-opening step during catalysis. This combined synthetic, biochemical, and biophysical study establishes the catalytic role of the α-amino group of the substrate during the O atom transfer reactions and thus represents a substantial advance to the mechanistic comprehension of the heme-based tryptophan dioxygenases.

Crystal structures and intermolecular interactions of two novel antioxidant triazolyl-benzimidazole compounds

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

Karayel, A., E-mail: matchlessjimmy@163.com, E-mail: yccaoh@hotmail.com; Özbey, S.; Ayhan-Kılcıgil, G.

2015-12-15

The crystal structures of 5-(2-(p-chlorophenylbenzimidazol-1-yl-methyl)-4-(3-fluorophenyl)-2, 4-dihydro-[1,2,4]-triazole-3-thione (G6C) and 5-(2-(p-chlorophenylbenzimidazol-1-yl-methyl)-4-(2-methylphenyl)-2, 4-dihydro-[1,2,4]-triazole-3-thione (G4C) have been determined by single-crystal X-ray diffraction. Benzimidazole ring systems in both molecules are planar. The triazole part is almost perpendicular to the phenyl and the benzimidazole parts of the molecules in order to avoid steric interactions between the rings. The crystal structures are stabilized by intermolecular hydrogen bonds between the amino group of the triazole and the nitrogen atom of benzimidazole of a neighboring molecule.

Structure-activity relationships of selected phenazines against Mycobacterium leprae in vitro.

PubMed Central

Franzblau, S G; O'Sullivan, J F

1988-01-01

Structure-activity relationships of phenazines against Mycobacterium leprae were investigated by using an in vitro radiorespirometric assay. In general, activity in ascending order was observed in compounds containing no chlorine atoms, a monochlorinated phenazine nucleus, and chlorines in the para positions of both the anilino and phenyl rings. The most active compounds contained a 2,2,6,6-tetramethylpiperidine substitution at the imino nitrogen. Most of these chlorinated phenazines were considerably more active in vitro than clofazimine (B663). PMID:3056241

Calcined polyaniline-iron composite as a high efficient cathodic catalyst in microbial fuel cells.

PubMed

Lai, Bin; Wang, Peng; Li, Haoran; Du, Zhuwei; Wang, Lijuan; Bi, Sichao

2013-03-01

A new type of carbon-nitrogen-metal catalyst, PANI-Fe-C, was synthesized by calcination process. According to the results of FT-IR and XPS analysis, polyaniline chain was broken by calcination. Small nitrogen-contained molecular fragments were gasified during calcination process, while the remaining nitrogen atoms were enchased in the new produced multiple carbon rings by C-N and CN bonds and performed as the catalytic active sites and the covalent centers for soluble iron components. Calculated from the polarization curves, a maximum power density of 10.17W/m(3) for the MFC with the synthetic catalyst was obtained, which was slightly higher than the MFC with Pt/C catalyst of 9.56W/m(3). All the results obtained in this paper proved that the newly synthetic nitrogen-carbon-metal catalyst would be a potential alternative to the expensive Pt/C catalyst in the field of MFC. Copyright © 2012 Elsevier Ltd. All rights reserved.

Energetic factors determining the binding of type I inhibitors to c-Met kinase: experimental studies and quantum mechanical calculations.

PubMed

Yu, Zhe; Ma, Yu-chi; Ai, Jing; Chen, Dan-qi; Zhao, Dong-mei; Wang, Xin; Chen, Yue-lei; Geng, Mei-yu; Xiong, Bing; Cheng, Mao-sheng; Shen, Jing-Kang

2013-11-01

To decipher the molecular interactions between c-Met and its type I inhibitors and to facilitate the design of novel c-Met inhibitors. Based on the prototype model inhibitor 1, four ligands with subtle differences in the fused aromatic rings were synthesized. Quantum chemistry was employed to calculate the binding free energy for each ligand. Symmetry-adapted perturbation theory (SAPT) was used to decompose the binding energy into several fundamental forces to elucidate the determinant factors. Binding free energies calculated from quantum chemistry were correlated well with experimental data. SAPT calculations showed that the predominant driving force for binding was derived from a sandwich π-π interaction with Tyr-1230. Arg-1208 was the differentiating factor, interacting with the 6-position of the fused aromatic ring system through the backbone carbonyl with a force pattern similar to hydrogen bonding. Therefore, a hydrogen atom must be attached at the 6-position, and changing the carbon atom to nitrogen caused unfavorable electrostatic interactions. The theoretical studies have elucidated the determinant factors involved in the binding of type I inhibitors to c-Met.

Electron density reactivity indexes of the tautomeric/ionization forms of thiamin diphosphate.

PubMed

Jaña, Gonzalo A; Delgado, Eduardo J

2013-09-01

The generation of the highly reactive ylide in thiamin diphosphate catalysis is analyzed in terms of the nucleophilicity of key atoms, by means of density functional calculations at X3LYP/6-31++G(d,p) level of theory. The Fukui functions of all tautomeric/ionization forms are calculated in order to assess their reactivity. The results allow to conclude that the highly conserved glutamic residue does not protonate the N1' atom of the pyrimidyl ring, but it participates in a strong hydrogen bonding, stabilizing the eventual negative charge on the nitrogen, in all forms involved in the ylide generation. This condition provides the necessary reactivity on key atoms, N4' and C2, to carry out the formation of the ylide required to initiate the catalytic cycle of ThDP-dependent enzymes. This study represents a new approach for the ylide formation in ThDP catalysis.

Production mechanism of atomic nitrogen in atmospheric pressure pulsed corona discharge measured using two-photon absorption laser-induced fluorescence

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

Teramoto, Yoshiyuki; Ono, Ryo; Oda, Tetsuji

To study the production mechanism of atomic nitrogen, the temporal profile and spatial distribution of atomic nitrogen are measured in atmospheric pressure pulsed positive corona discharge using two-photon absorption laser-induced fluorescence. The absolute atomic nitrogen density in the streamer filaments is estimated from decay rate of atomic nitrogen in N{sub 2} discharge. The results indicate that the absolute atomic nitrogen density is approximately constant against discharge energy. When the discharge voltage is 21.5 kV, production yield of atomic nitrogen produced by an N{sub 2} discharge pulse is estimated to be 2.9 - 9.8 Multiplication-Sign 10{sup 13} atoms and the energymore » efficiency of atomic nitrogen production is estimated to be about 1.8 - 6.1 Multiplication-Sign 10{sup 16} atoms/J. The energy efficiency of atomic nitrogen production in N{sub 2} discharge is constant against the discharge energy, while that in N{sub 2}/O{sub 2} discharge increases with discharge energy. In the N{sub 2}/O{sub 2} discharge, two-step process of N{sub 2} dissociation plays significant role for atomic nitrogen production.« less

Direct detection of pyridine formation by the reaction of CH (CD) with pyrrole: a ring expansion reaction

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

Soorkia, Satchin; Taatjes, Craig A.; Osborn, David L.

The reaction of the ground state methylidyne radical CH (X2Pi) with pyrrole (C4H5N) has been studied in a slow flow tube reactor using Multiplexed Photoionization Mass Spectrometry coupled to quasi-continuous tunable VUV synchrotron radiation at room temperature (295 K) and 90 oC (363 K), at 4 Torr (533 Pa). Laser photolysis of bromoform (CHBr3) at 248 nm (KrF excimer laser) is used to produce CH radicals that are free to react with pyrrole molecules in the gaseous mixture. A signal at m/z = 79 (C5H5N) is identified as the product of the reaction and resolved from 79Br atoms, and themore » result is consistent with CH addition to pyrrole followed by Helimination. The Photoionization Efficiency curve unambiguously identifies m/z = 79 as pyridine. With deuterated methylidyne radicals (CD), the product mass peak is shifted by +1 mass unit, consistent with the formation of C5H4DN and identified as deuterated pyridine (dpyridine). Within detection limits, there is no evidence that the addition intermediate complex undergoes hydrogen scrambling. The results are consistent with a reaction mechanism that proceeds via the direct CH (CD) cycloaddition or insertion into the five-member pyrrole ring, giving rise to ring expansion, followed by H atom elimination from the nitrogen atom in the intermediate to form the resonance stabilized pyridine (d-pyridine) molecule. Implications to interstellar chemistry and planetary atmospheres, in particular Titan, as well as in gas-phase combustion processes, are discussed.« less

The study of azaarene behavior over atmosphere of subtropical city(Keelung)

NASA Astrophysics Data System (ADS)

Liu, Chih Yun

2017-04-01

In this study, we collected the Total Suspended Particulates (TSP) from July 2014 to February 2016 in the subtropical city (Keelung), and researched azaarene behavior over atmosphere. Polycyclic Aromatic Compounds (PAHs) are ubiquitous pollutants in the environment; they have known carcinogens and/or mutagens, mainly produce from incomplete combustion. Azaarenes are polycyclic aromatic hydrocarbon derivative compounds in which a carbon atom in one of the aromatic rings is substituted by a nitrogen atom. Organism exposure to azaarenes occurs through inhalation of polluted air and by ingestion of food and/or water containing combustion products and accumulate in the body. Total azaarene concentration (16 individual compound concentration of the aggregate) is between 0.92 to 3.76 μg/m3, results showed that the concentration of azaarenes have significant seasonal variation, they have higher concentration in the cold month. In molecular weight, the highest proportion is the molecular weight equal to 143(ΣMQ) and then the molecular weight equal to 179(BAP), ΣMQ would rise from 30% 40% to 40% 50% during the cold month and warm months. Compared to ring number, 2-rings are biggest part, the smallest is 4-rings, its ratio has slight variation, but primary species is 2-rings. Emissions from transportation, local housing heating, factories burning fossil fuels and dust from Mainland south air mass are pollutant, their sources and climate conditions can affect concentration and composition of compound. There are highly significant correlation between 3-rings and 4-rings, which suggests that there are similar source strengths and transport mechanisms for these compounds. Correlation between concentration of azaarenes and ambient temperature is negative moderation, with concentration of atmospheric suspended particles is positive moderate correlation. Finally, we establish the relationship between the three parameters to predict concentration of azaarenes over atmosphere of subtropical regions. Key words: azaarenes, atmospheric suspended particles, subtropical city, multiple regression analysis.

Evaluation of Doped Phthalocyanines and a Chemically-Sensitive Field Effect Transistor for Detecting Nitrogen Dioxide

DTIC Science & Technology

1989-12-04

atom (31:708). Also, embedded in the cytochrome-c protein structure, the heme -group is derived from a porphyrin ring system with iron as the centrally...character DEFINT n DIM freqa(401 ),maga(401 ),phasea(401 ),freqg(401 ),magg(401 ),phaseg(401) LET ans$-=n" INPUT ’file with refamp data: ",air$ INPUT...REM and yields envelope of every three points DEFINT n,Ilast, keepers,tposit, po sht DIM frequ(1009),ampu(1009),freqn(1009),ampn(1009) INPUT ’file of

Azetidinones as zinc-binding groups to design selective HDAC8 inhibitors.

PubMed

Galletti, Paola; Quintavalla, Arianna; Ventrici, Caterina; Giannini, Giuseppe; Cabri, Walter; Penco, Sergio; Gallo, Grazia; Vincenti, Silvia; Giacomini, Daria

2009-12-01

2-Azetidinones, commonly known as beta-lactams, are well-known heterocyclic compounds. Herein we described the synthesis and biological evaluation of a series of novel beta-lactams. In vitro inhibition assays against HDAC isoforms showed an interesting isoform-selectivity of these compounds towards HDAC6 and HDAC8. The isoform selectivity changed in response to modification of the azetidinone-ring nitrogen atom substituent. The presence of an N-thiomethyl group is a prerequisite for the activity of these compounds in the micromolar range towards HDAC8.

Generation of photocurrent by visible-light irradiation of conjugated dawson polyoxophosphovanadotungstate-porphyrin copolymers.

PubMed

Azcarate, Iban; Huo, Zhaohui; Farha, Rana; Goldmann, Michel; Xu, Hualong; Hasenknopf, Bernold; Lacôte, Emmanuel; Ruhlmann, Laurent

2015-05-26

Four hybrid polyoxometalate-porphyrin copolymer films were obtained by the electrooxidation of zinc octaethylporphyrin in the presence of four different Dawson-type polyoxometalates bearing two pyridyl groups (POM(py)2) with various spacers. The POM monomers were designed around 1,3,5-trisubstituted benzene rings. Two of the substituents of the benzene ring are linked to the pyridyl groups, and the third is connected to the POM subunit. The four monomers vary in the relative positions of the nitrogen atoms of the pyridine rings or in the distance from the carbonyl group. The monomers were fully characterized by (1)H, (31)P, and (13)C NMR spectroscopy, electrospray mass spectrometry, IR and UV/Vis spectroscopy, and electrochemistry. The copolymers were characterized by UV/Vis spectroscopy, X-ray photoelectron spectroscopy, electrochemistry, and AFM. Their photovoltaic performance under visible light irradiation was investigated by photocurrent transient measurements under visible illumination. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The molecular structure of 4-methylpyridine-N-oxide: Gas-phase electron diffraction and quantum chemical calculations

NASA Astrophysics Data System (ADS)

Belova, Natalya V.; Girichev, Georgiy V.; Kotova, Vitaliya E.; Korolkova, Kseniya A.; Trang, Nguyen Hoang

2018-03-01

The molecular structure of 4-methylpiridine-N-oxide, 4-MePyO, has been studied by gas-phase electron diffraction monitored by mass spectrometry (GED/MS) and quantum chemical (DFT) calculations. Both, quantum chemistry and GED analyses resulted in CS molecular symmetry with the planar pyridine ring. Obtained molecular parameters confirm the hyperconjugation in the pyridine ring and the sp2 hybridization concept of the nitrogen and carbon atoms in the ring. The experimental geometric parameters are in a good agreement with the parameters for non-substituted N-oxide and reproduced very closely by DFT calculations. The presence of the electron-donating CH3 substituent in 4-MePyO leads to a decrease of the ipso-angle and to an increase of r(N→O) in comparison with the non-substituted PyO. Electron density distribution analysis has been performed in terms of natural bond orbitals (NBO) scheme. The nature of the semipolar N→O bond is discussed.

Isoxazole-type derivatives related to combretastatin A-4, synthesis and biological evaluation.

PubMed

Kaffy, Julia; Pontikis, Renée; Carrez, Danièle; Croisy, Alain; Monneret, Claude; Florent, Jean-Claude

2006-06-15

Novel combretastatin analogues bearing various five-membered heterocycles with consecutive oxygen and nitrogen atoms, in place of the olefinic bridge of CA4, have been synthesized (isoxazole, isoxazoline, oxadiazole, etc). These compounds have been evaluated for cytotoxicity and their ability to inhibit the tubulin assembly. On the basis of the relative position of the aromatic A- and B-rings on the heterocyclic moiety, they could be split in two classes, the alpha,gamma- or alpha,beta-diaryl heterocyclic derivatives. In the first series, the 3,5-diaryloxadiazole 9a displayed comparable antitubulin activity to that of CA4, but was devoid of cytotoxic effects. Among the alpha,beta-diaryl heterocyclic derivatives, the 4,5-diarylisoxazole 35 exhibited greater antitubulin activity than that of CA4 (0.75 vs 1.2 microM), but modest antiproliferative activity. These data showed that minor alteration in the chemical structure of the heterocyclic ring and its relative orientation with regard to the two phenyl rings of CA4 could dramatically influence the tubulin binding properties.

Toluene nitration in irradiated nitric acid and nitrite solutions

NASA Astrophysics Data System (ADS)

Elias, Gracy; Mincher, Bruce J.; Mezyk, Stephen P.; Muller, Jim; Martin, Leigh R.

2011-04-01

The kinetics, mechanisms, and stable products produced for the nitration of aryl alkyl mild ortho-para director toluene in irradiated nitric acid and neutral nitrite solutions were investigated using γ and pulse radiolysis. Electron pulse radiolysis was used to determine the bimolecular rate constants for the reaction of toluene with different transient species produced by irradiation. HPLC with UV detection, GC-MS and LC-MS, were used to assess the stable reaction products. Free-radical based nitration reaction products were found in irradiated acidic and neutral media. In 6.0 M HNO3, ring substitution, side chain substitution, and oxidation, produced different nitrated toluene products. For ring substitution, nitrogen oxide radicals were added mainly to cyclohexadienyl radicals, whereas for side chain substitution, these radicals were added to the carbon-centered benzyl radical produced by H-atom abstraction. In neutral nitrite solutions, radiolytically-induced ring nitration products approached a statistically random distribution, suggesting a direct free-radical reaction involving addition of the rad NO2 radical.

Structural Characterization of Am(III)- and Pu(III)-DOTA Complexes.

PubMed

Audras, Matthieu; Berthon, Laurence; Berthon, Claude; Guillaumont, Dominique; Dumas, Thomas; Illy, Marie-Claire; Martin, Nicolas; Zilbermann, Israel; Moiseev, Yulia; Ben-Eliyahu, Yeshayahu; Bettelheim, Armand; Cammelli, Sebastiano; Hennig, Christoph; Moisy, Philippe

2017-10-16

The complexation of 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) ligand with two trivalent actinides (Am 3+ and Pu 3+ ) was investigated by UV-visible spectrophotometry, NMR spectroscopy, and extended X-ray absorption fine structure in conjunction with computational methods. The complexation process of these two cations is similar to what has been previously observed with lanthanides(III) of similar ionic radius. The complexation takes place in different steps and ends with the formation of a (1:1) complex [(An(III)DOTA)(H 2 O)] - , where the cation is bonded to the nitrogen atoms of the ring, the four carboxylate arms, and a water molecule to complete the coordination sphere. The formation of An(III)-DOTA complexes is faster than the Ln(III)-DOTA systems of equivalent ionic radius. Furthermore, it is found that An-N distances are slightly shorter than Ln-N distances. Theoretical calculations showed that the slightly higher affinity of DOTA toward Am over Nd is correlated with slightly enhanced ligand-to-metal charge donation arising from oxygen and nitrogen atoms.

Nature of isomerism of solid isothiourea salts, inhibitors of nitric oxide synthases, as studied by 1H-14N nuclear quadrupole double resonance, X-ray, and density functional theory/quantum theory of atoms in molecules.

PubMed

Latosińska, J N; Latosińska, M; Seliger, J; Žagar, V; Maurin, J K; Kazimierczuk, Z

2012-02-09

Isothioureas, inhibitors of nitric oxide synthases, have been studied experimentally in solid state by nuclear quadrupole double resonance (NQDR) and X-ray methods and theoretically by the quantum theory of atoms in molecules/density functional theory. Resonance frequencies on (14)N have been detected and assigned to particular nitrogen sites in each molecule. The crystal packings of (S)-3,4-dichlorobenzyl-N-methylisothiouronium chloride with the disordered chlorine positions in benzene ring and (S)-butyloisothiouronium bromide have been resolved in X-ray diffraction studies. (14)N NQDR spectra have been found good indicators of isomer type and strength of intra- or intermolecular N-H···X (X = Cl, Br) interactions. From among all salts studied, only for (S)-2,3,4,5,6-pentabromobenzylisothiouronium chloride are both nitrogen sites equivalent, which has been explained by the slow exchange. This unique structural feature can be a key factor in the high biological activity of (S)-2,3,4,5,6-pentabromobenzylisothiouronium salts.

Silver sulfadoxinate: Synthesis, structural and spectroscopic characterizations, and preliminary antibacterial assays in vitro

NASA Astrophysics Data System (ADS)

Zanvettor, Nina T.; Abbehausen, Camilla; Lustri, Wilton R.; Cuin, Alexandre; Masciocchi, Norberto; Corbi, Pedro P.

2015-02-01

The sulfa drug sulfadoxine (SFX) reacted with Ag+ ions in aqueous solution, affording a new silver(I) complex (AgSFX), which was fully characterized by chemical, spectroscopic and structural methods. Elemental, ESI-TOF mass spectrometric and thermal analyses of AgSFX suggested a [Ag(C12H13N4O2S)] empirical formula. Infrared spectroscopic measurements indicated ligand coordination to Ag(I) through the nitrogen atoms of the (deprotonated) sulfonamide group and by the pyrimidine ring, as well as through oxygen atom(s) of the sulfonamide group. These hypotheses were corroborated by 13C and 15N SS-NMR spectroscopy and by an unconventional structural characterization based on X-ray powder diffraction data. The latter showed that AgSFX crystallizes as centrosymmetric dimers with a strong Ag⋯Ag interaction of 2.7435(6) Å, induced by the presence of exo-bidentate N,N‧ bridging ligands and the formation of an eight-membered ring of [AgNCN]2 sequence, nearly planar. Participation of oxygen atoms of the sulfonamide residues generates in the crystal a 1D coordination polymer, likely responsible for its very limited solubility in all common solvents. Besides the analytical, spectroscopic and structural description, the antibacterial properties of AgSFX were assayed using disc diffusion methods against Escherichia coli and Pseudomonas aeruginosa (Gram-negative), and Staphylococcus aureus (Gram-positive) bacterial strains. The AgSFX complex showed to be active against Gram-positive and Gram-negative bacterial strains, being comparable to the activities of silver sulfadiazine.

Inner hydrogen atom transfer in benzo-fused low symmetrical metal-free tetraazaporphyrin and phthalocyanine analogues: density functional theory studies.

PubMed

Qi, Dongdong; Zhang, Yuexing; Cai, Xue; Jiang, Jianzhuang; Bai, Ming

2009-02-01

Density functional theory (DFT) calculations were carried out to study the inner hydrogen atom transfer in low symmetrical metal-free tetrapyrrole analogues ranging from tetraazaporphyrin H(2)TAP (A(0)B(0)C(0)D(0)) to naphthalocyanine H(2)Nc (A(2)B(2)C(2)D(2)) via phthalocyanine H(2)Pc (A(1)B(1)C(1)D(1)). All the transition paths of sixteen different compounds (A(0)B(0)C(0)D(0)-A(2)B(2)C(2)D(2) and A(0)B(0)C(m)D(n), m

Cheminformatic Insight into the Differences between Terrestrial and Marine Originated Natural Products.

PubMed

Shang, Jun; Hu, Ben; Wang, Junmei; Zhu, Feng; Kang, Yu; Li, Dan; Sun, Huiyong; Kong, De-Xin; Hou, Tingjun

2018-06-07

This is a new golden age for drug discovery based on natural products derived from both marine and terrestrial sources. Herein, a straightforward but important question is "what are the major structural differences between marine natural products (MNPs) and terrestrial natural products (TNPs)?" To answer this question, we analyzed the important physicochemical properties, structural features, and drug-likeness of the two types of natural products and discussed their differences from the perspective of evolution. In general, MNPs have lower solubility and are often larger than TNPs. On average, particularly from the perspective of unique fragments and scaffolds, MNPs usually possess more long chains and large rings, especially 8- to 10-membered rings. MNPs also have more nitrogen atoms and halogens, notably bromines, and fewer oxygen atoms, suggesting that MNPs may be synthesized by more diverse biosynthetic pathways than TNPs. Analysis of the frequently occurring Murcko frameworks in MNPs and TNPS also reveals a striking difference between MNPs and TNPs. The scaffolds of the former tend to be longer and often contain ester bonds connected to 10-membered rings, while the scaffolds of the latter tend to be shorter and often bear more stable ring systems and bond types. Besides, the prediction from the naïve Bayesian drug-likeness classification model suggests that most compounds in MNPs and TNPs are drug-like, although MNPs are slightly more drug-like than TNPs. We believe that MNPs and TNPs with novel drug-like scaffolds have great potential to be drug leads or drug candidates in drug discovery campaigns.

Mode selectivity in the intramolecular cyclization of ketenimines bearing N-acylimino units: a computational and experimental study.

PubMed

Alajarín, Mateo; Sánchez-Andrada, Pilar; Vidal, Angel; Tovar, Fulgencio

2005-02-18

[reaction: see text] The mode selectivity in the intramolecular cyclization of a particular class of ketenimines bearing N-acylimino units has been studied by ab initio and DFT calculations. In the model compounds the carbonyl carbon atom and the keteniminic nitrogen atom are linked either by a vinylic or an o-phenylene tether. Two cyclization modes have been analyzed: the [2+2] cycloaddition furnishing compounds with an azeto[2,1-b]pyrimidinone moiety and a 6pi-electrocyclic ring closure leading to compounds enclosing a 1,3-oxazine ring. The [2+2] cycloaddition reaction takes place via a two-step process with formation of a zwitterionic intermediate, which has been characterized as a cross-conjugated mesomeric betaine. The 6pi-electrocyclic ring closure occurs via a transition state whose pseudopericyclic character has been established on the basis of its magnetic properties, geometry, and NBO analysis. The 6pi-electrocyclic ring closure is energetically favored over the [2+2] cycloaddition, although the [2+2] cycloadducts are the thermodynamically controlled products. A quantitative kinetic analysis predicts that 1,3-oxazines would be the kinetically controlled products, but they should transform rapidly and totally into the [2+2] cycloadducts at room temperature. In the experimental study, a number of N-acylimino-ketenimines, in which both reactive functions are supported on an o-phenylene scaffold, have been successfully synthesized in three steps starting from 2-azidobenzoyl chloride. These compounds rapidly convert into azeto[2,1-b]quinazolin-8-ones in moderate to good yields as a result of a formal [2+2] cycloaddition.

Optical ferris wheel for ultracold atoms

NASA Astrophysics Data System (ADS)

Franke-Arnold, S.; Leach, J.; Padgett, M. J.; Lembessis, V. E.; Ellinas, D.; Wright, A. J.; Girkin, J. M.; Ohberg, P.; Arnold, A. S.

2007-07-01

We propose a versatile optical ring lattice suitable for trapping cold and quantum degenerate atomic samples. We demonstrate the realisation of intensity patterns from pairs of Laguerre-Gauss (exp(iℓө) modes with different ℓ indices. These patterns can be rotated by introducing a frequency shift between the modes. We can generate bright ring lattices for trapping atoms in red-detuned light, and dark ring lattices suitable for trapping atoms with minimal heating in the optical vortices of blue-detuned light. The lattice sites can be joined to form a uniform ring trap, making it ideal for studying persistent currents and the Mott insulator transition in a ring geometry.

Synthesis and spectroscopic studies on the new Schiff base derived from the 1:2 condensation of 2,6-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transition metal complexes. Influence on biologically active peptides-regulating aminopeptidases.

PubMed

Hueso-Ureña, Francisco; Illán-Cabeza, Nuria A; Moreno-Carretero, Miguel N; Martínez-Martos, José M; Ramírez-Expósito, María J

2003-04-01

The synthesis, spectroscopic (IR, 1H and 13C NMR, UV-Vis-NIR, EPR), magnetic measurements and biological studies of a number of complexes of Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Au(III) and Hg(II) of the Schiff base derived from the 1:2 condensation of 2,6-diformyl-4-methylphenol and 5-aminouracil, ((5-[[(3-[[(2,4-dioxopyrimidin-5(1H,3H)-yl)imino]methyl]-2-hydroxy-5-methylphenyl)methylene]amino]pyrimidine-2,4(1H,3H)-dione, hereafter denoted as BDF5AU) are reported. In all cases, the complexes appear to be monomeric. The deprotonated ligand in the phenolic oxygen atom shows a tridentate coordination mode through the two azomethine nitrogen atoms and the phenolic oxygen atom. The coordination of the neutral ligand takes place through the phenolic oxygen atom and one azomethine nitrogen atom and the carbonylic oxygen atom in fourth position of one uracil ring. The biological properties of some perchlorate complexes on the activity of some neutral, acid, basic and omega aminopeptidases (AP) are assayed, demonstrating a general inhibitory effect. Neutral and basic AP are mainly inhibited by Cu(II), Ni(II) and Cd(II) complexes, although tyrosyl-AP is activated by Zn(II) complex. Glutamyl-AP but not aspartyl-AP is inhibited by all the complexes assayed excepting Zn(II) complex. Finally, omega AP is inhibited by Ni(II) and Cd(II) complexes. Copyright 2003 Elsevier Science Inc.

Synthesis, crystal structure determination and antiproliferative activity of novel 2-amino-4-aryl-4,10-dihydro[1,3,5]triazino[1,2- a]benzimidazoles

NASA Astrophysics Data System (ADS)

Hranjec, Marijana; Pavlović, Gordana; Karminski-Zamola, Grace

2012-01-01

This manuscript describes the synthesis of novel 2-amino-4-aryl-4,10-dihydro-[1,3,5]triazino[1,2- a]benzimidazoles as hydrochloride salts 4a-n and 5b which were prepared in the reaction of cyclocondensation between 2-guanidinobenzimidazole and versatile heteroaromatic aldehydes. Structures of all prepared compounds have been studied by using 1H and 13C NMR, IR and UV/Vis spectroscopy. The crystal and molecular structure of 4f was determined by X-ray diffraction on single crystals. The molecule of 2-amino-4-(4'-methylphenyl)-4,10-dihydro[1,3,5]triazino[1,2- a]benzimidazole hydrochloride 4f (C 16H 16N 5+·Cl -) exists in the solid state in one of the possible tautomeric forms, being protonated at the one of the nitrogen atoms of the 1,4-dihydrotriazine ring. The molecule is highly delocalized within the 4,10-dihydro[1,3,5]triazino[1,2- a]benzimidazole moiety with the highest deviation from the plane for the methine carbon atom and the protonated nitrogen atom of the 1,4-dihydrotriazine ring. The cations are joined via N-H⋯N hydrogen bonds into R22(8) centrosymmetric dimers. Cation dimers are further connected with Cl - ions via N-H⋯Cl and C-H⋯Cl hydrogen bonds into 2D chains spreading along the b axis. The obtained single-crystal X-ray structure determination unequivocally confirms tautomeric form of the compound present in the solid-state and can represent tantative pattern for other prepared compounds. All prepared compounds were tested on their antiproliferative activity in vitro on several human cancer cell lines. Compound 4m was the most active one (IC 50 ≈ 20 μM), while compounds 4d, 4f, 4k, 4l4m showed moderate, but non-selective, antiproliferative activity with IC 50 25-60 μM.

Conformational landscape, photochemistry, and infrared spectra of sulfanilamide.

PubMed

Borba, Ana; Gómez-Zavaglia, Andrea; Fausto, Rui

2013-01-31

A combined matrix isolation FTIR and theoretical DFT(B3LYP)/6-311++G(3df,3pd) study of sulfanilamide (SA) was performed. The full conformational search on the potential energy surface of the compound allowed the identification of four different minima, all of them bearing the sulfamide nitrogen atom placed in the perpendicular orientation relatively to the aromatic ring and differing from each other in the orientation of the hydrogen atoms connected to the two nitrogen atoms of the molecule. All conformers were predicted to be significantly populated in the gas phase (at 100 °C, their relative populations were estimated as being 1:0.9:0.3:0.2). However, in agreement with the theoretically calculated low-energy barriers for conformational isomerization, in the low-temperature matrices, only the most stable conformer could be observed, with the remaining forms being converted into this form during matrix deposition (conformational cooling). The unimolecular photochemistry of matrix-isolated SA (in both argon and xenon) was also investigated. Upon broadband UV irradiation (λ > 215 nm), two photofragmentation pathways were observed: the prevalent pathway (A), leading to extrusion of sulfur dioxide and simultaneous formation of benzene-1,4-diamine, which then converts to 2,5-cyclohexadiene-1,4-diimine, and the minor pathway (B), conducting an γ-cleavage plus [1,3] H-atom migration from the sulfamide group to the aromatic ring, which leads to formation of iminosulfane dioxide and aniline, the latter undergoing subsequent phototransformation into cyclohexa-2,5-dien-1-imine. Finally, the crystalline polymorph of SA resulting from warming (265 K) the amorphous solid obtained from fast cooling of the vapor of the compound onto the cold (13 K) substrate of the cryostat was identified spectroscopically, and found to be the γ-crystalline phase, the one exhibiting in average longer H-bonds and an infrared spectrum resembling more that of the low temperature SA glass. Full assignment of the infrared spectra of this crystalline variety as well as of those of the β-polymorph room temperature crystalline sample and low temperature amorphous state was undertaken with help of theoretical results obtained for the crystallographically relevant dimer of SA.

Formation of the nitrogen aggregates in annealed diamond by neutron irradiation

NASA Astrophysics Data System (ADS)

Mita, Y.; Nisida, Y.; Okada, M.

2018-02-01

Neutron heavy irradiation was performed on synthetic diamonds contain nitrogen atoms in isolated substitutional form (called "type Ib diamond") and they were annealed under a pressure of 6 GPa. A large number of nitrogen B-aggregate which consists of four substitutional nitrogen atoms symmetrically surrounding a vacancy was formed within 30 m from single nitrogen atoms. Furthermore it is observed that, in these diamonds, single nitrogen atoms coexist with the B-aggregates, which is unexplainable by the simple nitrogen aggregation model.

Energetic factors determining the binding of type I inhibitors to c-Met kinase: experimental studies and quantum mechanical calculations

PubMed Central

Yu, Zhe; Ma, Yu-chi; Ai, Jing; Chen, Dan-qi; Zhao, Dong-mei; Wang, Xin; Chen, Yue-lei; Geng, Mei-yu; Xiong, Bing; Cheng, Mao-sheng; Shen, Jing-kang

2013-01-01

Aim: To decipher the molecular interactions between c-Met and its type I inhibitors and to facilitate the design of novel c-Met inhibitors. Methods: Based on the prototype model inhibitor 1, four ligands with subtle differences in the fused aromatic rings were synthesized. Quantum chemistry was employed to calculate the binding free energy for each ligand. Symmetry-adapted perturbation theory (SAPT) was used to decompose the binding energy into several fundamental forces to elucidate the determinant factors. Results: Binding free energies calculated from quantum chemistry were correlated well with experimental data. SAPT calculations showed that the predominant driving force for binding was derived from a sandwich π–π interaction with Tyr-1230. Arg-1208 was the differentiating factor, interacting with the 6-position of the fused aromatic ring system through the backbone carbonyl with a force pattern similar to hydrogen bonding. Therefore, a hydrogen atom must be attached at the 6-position, and changing the carbon atom to nitrogen caused unfavorable electrostatic interactions. Conclusion: The theoretical studies have elucidated the determinant factors involved in the binding of type I inhibitors to c-Met. PMID:24056705

Synthesis and biological evaluation of new 2-(4,5-dihydro-1H-imidazol-2-yl)-3,4-dihydro-2H-1,4-benzoxazine derivatives.

PubMed

Touzeau, Frédérique; Arrault, Axelle; Guillaumet, Gérald; Scalbert, Elizabeth; Pfeiffer, Bruno; Rettori, Marie-Claire; Renard, Pierre; Mérour, Jean-Yves

2003-05-08

2-(4,5-Dihydro-1H-imidazol-2-yl)-3,4-dihydro-2H-1,4-benzoxazine derivatives and tricyclic analogues with a fused additional ring on the nitrogen atom of the benzoxazine moiety have been prepared and evaluated for their cardiovascular effects as potential antihypertensive agents. The imidazoline ring was generated by reaction of the corresponding ethyl ester with ethylenediamine. Affinities for imidazoline binding sites (IBS) I(1) and I(2) and alpha(1) and alpha(2) adrenergic receptors were evaluated as well as the effects on mean arterial blood pressure (MAP) and heart rate (HR) of spontaneously hypertensive rats. With few exceptions the most active compounds on MAP were those with high affinities for IBS and alpha(2) receptor. Among these, compound 4h was the most interesting and is now, together with its enantiomers, under complementary pharmacological evaluation.

Superfluid qubit systems with ring shaped optical lattices

PubMed Central

Amico, Luigi; Aghamalyan, Davit; Auksztol, Filip; Crepaz, Herbert; Dumke, Rainer; Kwek, Leong Chuan

2014-01-01

We study an experimentally feasible qubit system employing neutral atomic currents. Our system is based on bosonic cold atoms trapped in ring-shaped optical lattice potentials. The lattice makes the system strictly one dimensional and it provides the infrastructure to realize a tunable ring-ring interaction. Our implementation combines the low decoherence rates of neutral cold atoms systems, overcoming single site addressing, with the robustness of topologically protected solid state Josephson flux qubits. Characteristic fluctuations in the magnetic fields affecting Josephson junction based flux qubits are expected to be minimized employing neutral atoms as flux carriers. By breaking the Galilean invariance we demonstrate how atomic currents through the lattice provide an implementation of a qubit. This is realized either by artificially creating a phase slip in a single ring, or by tunnel coupling of two homogeneous ring lattices. The single qubit infrastructure is experimentally investigated with tailored optical potentials. Indeed, we have experimentally realized scaled ring-lattice potentials that could host, in principle, n ~ 10 of such ring-qubits, arranged in a stack configuration, along the laser beam propagation axis. An experimentally viable scheme of the two-ring-qubit is discussed, as well. Based on our analysis, we provide protocols to initialize, address, and read-out the qubit. PMID:24599096

Two-dimensional B-C-O alloys: a promising class of 2D materials for electronic devices.

PubMed

Zhou, Si; Zhao, Jijun

2016-04-28

Graphene, a superior 2D material with high carrier mobility, has limited application in electronic devices due to zero band gap. In this regard, boron and nitrogen atoms have been integrated into the graphene lattice to fabricate 2D semiconducting heterostructures. It is an intriguing question whether oxygen can, as a replacement of nitrogen, enter the sp2 honeycomb lattice and form stable B-C-O monolayer structures. Here we explore the atomic structures, energetic and thermodynamic stability, and electronic properties of various 2D B-C-O alloys using first-principles calculations. Our results show that oxygen can be stably incorporated into the graphene lattice by bonding with boron. The B and O species favor forming alternate patterns into the chain- or ring-like structures embedded in the pristine graphene regions. These B-C-O hybrid sheets can be either metals or semiconductors depending on the B : O ratio. The semiconducting (B2O)nCm and (B6O3)nCm phases exist under the B- and O-rich conditions, and possess a tunable band gap of 1.0-3.8 eV and high carrier mobility, retaining ∼1000 cm2 V(-1) s(-1) even for half coverage of B and O atoms. These B-C-O alloys form a new class of 2D materials that are promising candidates for high-speed electronic devices.

Nitrogen diffusion in hafnia and the impact of nitridation on oxygen and hydrogen diffusion: A first-principles study

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

Sathiyanarayanan, Rajesh, E-mail: rajessat@in.ibm.com, E-mail: rajesh.sathiyanarayanan@gmail.com; Pandey, R. K.; Murali, K. V. R. M.

2015-01-21

Using first-principles simulations, we have computed incorporation energies and diffusion barriers of ammonia, the nitrogen molecule and atomic nitrogen in monoclinic hafnia (m-HfO{sub 2}). Our calculations show that ammonia is likely to dissociate into an NH{sub 2} molecular unit, whereas the nitrogen molecule remains as a molecule either in the interstitial space or at an oxygen lattice site. The lowest energy pathway for the diffusion of atomic nitrogen interstitials consists of the hopping of the nitrogen interstitial between neighboring three-coordinated lattice oxygen atoms that share a single Hf atom, and the barrier for such hops is determined by a switchingmore » mechanism. The substitutional nitrogen atom shows a preference for diffusion through the doubly positive oxygen vacancy-mediated mechanism. Furthermore, we have investigated the impact of nitrogen atoms on the diffusion barriers of oxygen and hydrogen interstitials in m-HfO{sub 2}. Our results show that nitrogen incorporation has a significant impact on the barriers for oxygen and hydrogen diffusion: nitrogen atoms attract oxygen and hydrogen interstitials diffusing in the vicinity, thereby slowing down (reducing) their diffusion (diffusion length)« less

Dual levitated coils for antihydrogen production

NASA Astrophysics Data System (ADS)

Wofford, J. D.; Ordonez, C. A.

2013-04-01

Two coaxial superconducting magnetic coils that carry currents in the same direction and that are simultaneously levitated may serve for antihydrogen plasma confinement. The configuration may be suitable for use by a collaboration at the CERN Antiproton Decelerator facility to test fundamental symmetries between the properties of hydrogen and antihydrogen. Nested Penning traps are currently used to confine recombining antihydrogen plasma. Symmetry studies require the production of sufficiently cold antihydrogen. However, plasma drifts within nested Penning traps can increase the kinetic energy of antiprotons that form antihydrogen atoms. Dual levitated coils may serve to confine relatively large, cold, dense non-drifting recombining antihydrogen plasmas. A minimum-B magnetic field that is produced by the coils could provide for atom trapping. A toroidal plasma is confined between the coils. High density plasmas may be possible, by allowing plasma pressure to balance mechanical pressure to keep the coils apart. Progress is reported on theoretical and experimental efforts. The theoretical effort includes the development of a classical trajectory Monte Carlo simulation of confinement. The experimental effort includes levitation of a NdFeB permanent ring magnet, which produces a magnetic field that is qualitatively similar to the field that would be produced by the two coaxial superconducting magnetic coils. Liquid-nitrogen-cooled Bi-2223 high-temperature-superconducting components, with a critical temperature of 108 K, were used to levitate the ring magnet. An issue concerning keeping the plane of the levitated ring horizontal is discussed.

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.

Soliton Dynamics of an Atomic Spinor Condensate on a Ring Lattice

DTIC Science & Technology

2013-02-22

REPORT Soliton dynamics of an atomic spinor condensate on a Ring Lattice 14. ABSTRACT 16. SECURITY CLASSIFICATION OF: We study the dynamics of...8/98) Prescribed by ANSI Std. Z39.18 - Soliton dynamics of an atomic spinor condensate on a Ring Lattice Report Title ABSTRACT We study the dynamics...Report Number Soliton dynamics of an atomic spinor condensat Block 13: Supplementary Note © 2013 . Published in Physical Review A (accepted), Vol. Ed

Distinct domains within the NITROGEN LIMITATION ADAPTATION protein mediate its subcellular localization and function in the nitrate-dependent phosphate homeostasis pathway

USDA-ARS?s Scientific Manuscript database

The NITROGEN LIMITATION ADAPTATION (NLA) protein is a RING-type E3 ubiquitin ligase that plays an essential role in the regulation of nitrogen and phosphate homeostasis. NLA is localized to two distinct subcellular sites, the plasma membrane and nucleus, and contains four distinct domains: i) a RING...

2-Methyl-2-phenyl-1-(pyrrolidin-1-yl)propan-1-one.

PubMed

Ren, Dong-Mei

2013-05-01

In the title compound, C14H19NO, the dihedral angle between the benzene ring and the plane of the amide group is 80.6 (1)°. In the crystal, mol-ecules are connected via weak C-H⋯O hydrogen bonds, forming chains along the c-axis direction. The conformation of the five-memebred ring is an envelope, with one of the ring C atoms adjacent to the ring N atom as the flap atom.

New multifunctional tungsten nitride with energetic N6 and extreme hardness predicted from first principles

NASA Astrophysics Data System (ADS)

Li, Qian; Sha, Lei; Zhu, Chunye; Yao, Yansun

2017-05-01

We report a new member to the family of tungsten nitrides, WN6, predicted from the structure search. Ground-state convex hull calculation reveals that crystalline WN6 is thermodynamically stable at pressures above 16 GPa, but remains dynamically stable at ambient conditions. The predicted high-pressure WN6 structure contains chaired \\text{cyclo-N}6{6-} rings isoelectronic to cyclo-hexasulfur (S6), which is unprecedented in nitrogen. In the \\text{cyclo-N}6{6-} unit all nitrogen atoms are singly bonded and therefore contain a high energy density. By means of efficiently packing the covalent-bonded species, WN6 is estimated to have extremely high Vickers hardness greater than 40 GPa at ambient conditions, placing it as one of the hardest materials. The present results reveal that WN6 may be used as a superhard material but simultaneously maintaining other desirable properties, which represents an interesting example of multifunctional materials.

Electronic distributions within protein phenylalanine aromatic rings are reflected by the three-dimensional oxygen atom environments.

PubMed Central

Thomas, K A; Smith, G M; Thomas, T B; Feldmann, R J

1982-01-01

The atomic environments of 170 phenylalanine-residue aromatic rings from 28 protein crystal structures are transformed into a common orientation and combined to calculate an average three-dimensional environment. The spatial distribution of atom types in this environment reveals a preferred interaction between oxygen atoms and the edge of the planar aromatic rings. From the difference in frequency of interaction of oxygen atoms with the edge and the top of the ring, an apparent net free energy difference of interaction favoring the edge of the ring is estimated to be about -1 kcal/mol (1 cal = 4.184 J). Ab initio quantum mechanical calculations, performed on a model consisting of benzene and formamide, indicate that the observed geometry is stabilized by a favorable enthalpic interaction. Although benzene rings are considered to be nonpolar, the electron distribution is a complex multipole with no net dipole moment. The observed interaction orientation frequencies demonstrate that these multipolar electron distributions, when occurring at the short distances encountered in densely packed protein molecules, are significant determinants of internal packing geometries. PMID:6956896

Mixing of MnPc electronic states at the MnPc/Au(110) interface

NASA Astrophysics Data System (ADS)

Gargiani, Pierluigi; Lisi, Simone; Avvisati, Giulia; Mondelli, Pierluigi; Fatale, Sara; Betti, Maria Grazia

2017-10-01

Manganese-phthalocyanines form assembled chains with a variety of ordered super-structures, flat lying along the Au(110) reconstructed channels. The chains first give rise to a ×5 symmetry reconstruction, while further deposition of MnPc leads to a ×7 periodicity at the completion of the first single layer. A net polarization with the formation of an interface dipole is mainly due to the molecular π-states located on the macrocycles pyrrole rings, while the central metal ion induces a reduction in the polarization, whose amount is related to the Mn-Au interaction. The adsorption-induced interface polarization is compared to other 3d-metal phthalocyanines, to unravel the role of the central metal atom configuration in the interaction process of the d-states. The MnPc adsorption on Au(110) induces the re-hybridization of the electronic states localized on the central metal atom, promoting a charge redistribution of the molecular orbitals of the MnPc molecules. The molecule-substrate interaction is controlled by a symmetry-determined mixing between the electronic states, involving also the molecular empty orbitals with d character hybridized with the nitrogen atoms of the pyrrole ring, as deduced by photoemission and X-ray absorption spectroscopy exploiting light polarization. The symmetry-determined mixing between the electronic states of the Mn metal center and of the Au substrate induces a density of states close to the Fermi level for the ×5 phase.

Single atom array to form a Rydberg ring

NASA Astrophysics Data System (ADS)

Zhan, Mingsheng; Xu, Peng; He, Xiaodong; Liu, Min; Wang, Jin

2012-02-01

Single atom arrays are ideal quantum systems for studying few-body quantum simulation and quantum computation [1]. Towards realizing a fully controllable array we did a lot of experimental efforts, which include rotating single atoms in a ring optical lattice generated by a spatial light modulator [2], high efficient loading of two atoms into a microscopic optical trap by dynamically reshaping the trap with a spatial light modulator [3], and trapping a single atom in a blue detuned optical bottle beam trap [4]. Recently, we succeeded in trapping up to 6 atoms in a ring optical lattice with one atom in each site. Further laser cooling the array and manipulation of the inner states will provide chance to form Ryberg rings for quantum simulation. [4pt] [1] M. Saffman et al., Rev. Mod. Phys. 82, 2313 (2010)[0pt] [2] X.D. He et al., Opt. Express 17, 21014 (2009)[0pt] [3] X.D. He et al., Opt. Express 18, 13586 (2010)[0pt] [4] P. Xu et al., Opt. Lett. 35, 2164 (2010)

Synthesis and antiproliferative activity of 6-phenylaminopurines.

PubMed

Canela, María-Dolores; Liekens, Sandra; Camarasa, María-José; Priego, Eva María; Pérez-Pérez, María-Jesús

2014-11-24

A series of novel 6-phenylaminopurines have been efficiently synthesized in 3 steps exploring different groups at positions 2, 8 and 9 of the purine ring and at the exocyclic nitrogen atom at position 6. Among the newly described purines, five compounds showed antiproliferative activity with IC50 values below 10 μM, the tetrahydroquinoline derivative at position 6 of phenylaminopurine being the most active of the series in the six cell lines tested. Moreover, the compounds induced G2/M phase arrest in human cervical carcinoma HeLa cells as reported for tubulin depolymerizing agents. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

The structures of cytosolic and plastid-located glutamine synthetases from Medicago truncatula reveal a common and dynamic architecture

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

Torreira, Eva; Seabra, Ana Rita; Marriott, Hazel

The experimental models of dicotyledonous cytoplasmic and plastid-located glutamine synthetases unveil a conserved eukaryotic-type decameric architecture, with subtle structural differences in M. truncatula isoenzymes that account for their distinct herbicide resistance. The first step of nitrogen assimilation in higher plants, the energy-driven incorporation of ammonia into glutamate, is catalyzed by glutamine synthetase. This central process yields the readily metabolizable glutamine, which in turn is at the basis of all subsequent biosynthesis of nitrogenous compounds. The essential role performed by glutamine synthetase makes it a prime target for herbicidal compounds, but also a suitable intervention point for the improvement of cropmore » yields. Although the majority of crop plants are dicotyledonous, little is known about the structural organization of glutamine synthetase in these organisms and about the functional differences between the different isoforms. Here, the structural characterization of two glutamine synthetase isoforms from the model legume Medicago truncatula is reported: the crystallographic structure of cytoplasmic GSII-1a and an electron cryomicroscopy reconstruction of plastid-located GSII-2a. Together, these structural models unveil a decameric organization of dicotyledonous glutamine synthetase, with two pentameric rings weakly connected by inter-ring loops. Moreover, rearrangement of these dynamic loops changes the relative orientation of the rings, suggesting a zipper-like mechanism for their assembly into a decameric enzyme. Finally, the atomic structure of M. truncatula GSII-1a provides important insights into the structural determinants of herbicide resistance in this family of enzymes, opening new avenues for the development of herbicide-resistant plants.« less

Nucleophilic ring opening reactions of aziridines.

PubMed

Akhtar, Rabia; Naqvi, Syed Ali Raza; Zahoor, Ameer Fawad; Saleem, Sameera

2018-05-04

Aziridine ring opening reactions have gained tremendous importance in the synthesis of nitrogen containing biologically active molecules. During recent years, a great effort has been put forward by scientists toward unique bond construction methodologies via ring opening of aziridines. In this regard, a wide range of chiral metal- and organo-catalyzed desymmetrization reactions of aziridines have been reported with carbon, sulfur, oxygen, nitrogen, halogen, and other nucleophiles. In this review, an outline of methodologies adopted by a number of scientists during 2013-2017 for aziridine ring opening reactions as well as their synthetic applications is described.

Lithium/organosulfur redox cell having protective solid electrolyte barrier formed on anode and method of making same

DOEpatents

De Jonghe, Lutgard C.; Visco, Steven J.; Liu, Meilin; Mailhe, Catherine C.

1990-01-01

A lithium/organosulfur redox cell is disclosed which comprises a solid lium anode, a liquid organosulfur cathode, and a barrier layer formed adjacent a surface of the solid lithium anode facing the liquid organosulfur cathode consisting of a reaction product of the lithium anode with the organosulfur cathode. The organosulfur cathode comprises a material having the formula (R(S).sub.y).sub.N where y=1 to 6, n=2 to 20 and R is one or more different aliphatic or aromatic organic moieties having 1 to 20 carbon atoms, which may include one or more oxygen, sulfur, nitrogen, or fluorine atoms associated with the chain when R comprises an aliphatic chain, wherein the linear chain may be linear or branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon.

Chemical reactivity of hydrogen, nitrogen, and oxygen atoms at temperatures below 100 k

NASA Technical Reports Server (NTRS)

Mcgee, H. A., Jr.

1973-01-01

The synthesis of unusual compounds by techniques employing cryogenic cooling to retard their very extreme reactivity was investigated. Examples of such species that were studied are diimide (N2H2), cyclobutadiene (C4H4), cyclopropanone (C3H4O), oxirene (C2H2O), and many others. Special purpose cryogenically cooled inlet arrangements were designed such that the analyses incurred no warm-up of the cold, and frequently explosively unstable, compounds. Controlled energy electron impact techniques were used to measure critical potentials and to develop the molecular energetics and thermodynamics of these molecules and to gain some insight into their kinetic characteristics as well. Three and four carbon strained ring molecules were studied. Several reactions of oxygen and hydrogen atoms with simple molecules of H, N, C, and O in hard quench configurations were studied. And the quench stabilization of BH3 was explored as a model system in cryochemistry.

Synthesis, crystal structure, spectroscopic characterization and nonlinear optical properties of manganese (II) complex of picolinate: A combined experimental and computational study

NASA Astrophysics Data System (ADS)

Tamer, Ömer; Avcı, Davut; Atalay, Yusuf; Çoşut, Bünyemin; Zorlu, Yunus; Erkovan, Mustafa; Yerli, Yusuf

2016-02-01

A novel manganese (II) complex with picolinic acid (pyridine 2-carboxylic acid, Hpic), namely, [Mn(pic)2(H2O)2] was prepared and its crystal structure was fully characterized by using single crystal X-ray diffraction. Picolinate (pic) ligands were coordinated to the central manganese(II) ion as bidentate N,O-donors through the nitrogen atoms of pyridine rings and the oxygen atoms of carboxylate groups forming five-membered chelate rings. The spectroscopic characterization of Mn(II) complex was performed by the applications of FT-IR, Raman, UV-vis and EPR techniques. In order to support these studies, density functional theory (DFT) calculations were carried out by using B3LYP level. IR and Raman spectra were simulated at B3LYP level, and obtained results indicated that DFT calculations generally give compatible results to the experimental ones. The electronic structure of the Mn(II) complex was predicted using time dependent DFT (TD-DFT) method with polarizable continuum model (PCM). Molecular stability, hyperconjugative interactions, intramolecular charge transfer (ICT) and bond strength were investigated by applying natural bond orbital (NBO) analysis. Nonlinear optical properties of Mn(II) complex were investigated by the determining of molecular polarizability (α) and hyperpolarizability (β) parameters.

Interaction of scandium and titanium atoms with a carbon surface containing five- and seven-membered rings

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

Krasnov, P. O., E-mail: kpo1980@gmail.com; Eliseeva, N. S.; Kuzubov, A. A., E-mail: alex_xx@rambler.ru

2012-01-15

The use of carbon nanotubes coated by atoms of transition metals to store molecular hydrogen is associated with the problem of the aggregation of these atoms, which leads to the formation of metal clusters. The quantum-chemical simulation of cluster models of the carbon surface of a graphene type with scandium and titanium atoms has been performed. It has been shown that the presence of five- and seven-membered rings, in addition to six-membered rings, in these structures makes it possible to strongly suppress the processes of the migration of metal atoms over the surface, preventing their clustering.

The generalized anomeric effect in the 1,3-thiazolidines: Evidence for both sulphur and nitrogen as electron donors. Crystal structures of various N-acylthiazolidines including mercury(II) complexes. Possible relevance to penicillin action

NASA Astrophysics Data System (ADS)

Chandrasekhar, Sosale; Chopra, Deepak; Gopalaiah, Kovuru; Guru Row, Tayur N.

2007-06-01

Evidence for the generalized anomeric effect (GAE) in the N-acyl-1,3-thiazolidines, an important structural motif in the penicillins, was sought in the crystal structures of N-(4-nitrobenzoyl)-1,3-thiazolidine and its (2:1) complex with mercuric chloride, N-acetyl-2-phenyl-1,3-thiazolidine, and the (2:1) complex of N-benzoyl-1,3-thiazolidine with mercuric bromide. An inverse relationship was generally observed between the C2- N and C2- S bond lengths of the thiazolidine ring, supporting the existence of the GAE. (Maximal bond length changes were ˜0.04 Å for C2- N3, S1- C2, and ˜0.08 Å for N3- C6.) Comparison with N-acylpyrrolidines and tetrahydrothiophenes indicates that both the nitrogen-to-sulphur and sulphur-to-nitrogen GAE's operate simultaneously in the 1,3-thiazolidines, the former being dominant. (This is analogous to the normal and exo-anomeric effects in pyranoses, and also leads to an interesting application of Baldwin's rules.) The nitrogen-to-sulphur GAE is generally enhanced in the mercury(II) complexes (presumably via coordination at the sulphur); a 'competition' between the GAE and the amide resonance of the N-acyl moiety is apparent. There is evidence for a 'push-pull' charge transfer between the thiazolidine moieties in the mercury(II) complexes, and for a 'back-donation' of charge from the bromine atoms to the thiazolidine moieties in the HgBr 2 complex. (The sulphur atom appears to be sp 2 hybridised in the mercury(II) complexes, possibly for stereoelectronic reasons.) These results are apparently relevant to the mode of action of the penicillins.

Does the number of nitrogen atoms have an influence on the conducting properties of diphenylazines? A DFT insight

NASA Astrophysics Data System (ADS)

Moral, Mónica; Granadino-Roldán, José Manuel; Garzón, Andrés; García, Gregorio; Fernández-Gómez, Manuel

2011-01-01

The present study reports on the variation of some structural and electronic properties related to the electron conductivity for the series of diphenylazines represented by the formula Ph sbnd (C 2+nN 4-nH n) sbnd Ph, n = 0 - 4. Properties such as planarity, aromaticity, HOMO → LUMO excitation energy, electron affinity, LUMO level energy, reorganization energy and electron coupling between neighboring molecules in the crystal were analyzed from a theoretical perspective as a function of the number of nitrogen atoms in the molecular structure. As a result, the planarity, aromaticity and electron affinity increase with the number of N atoms in the central ring while the HOMO → LUMO excitation energy and LUMO levels diminish. It is worth noting that up to n = 3, the frontier orbitals appear delocalized throughout the whole system while for n = 4 the localized character of the LUMO might explain the increase in the reorganization energy and thus the higher difficulty to delocalize the excess of negative charge. Electron coupling between neighboring molecules was also estimated on the basis of the energy splitting in dimer method and the reported crystal structures for some of the studied molecules. Accordingly, the highest | t12| value was obtained for Ph 2T N3 (0.06 eV) while Ph 2Tz should be the most advantageous candidate of the series in terms of electron injection.

Solution structures of chloroquine-ferriheme complexes modeled using MD simulation and investigated by EXAFS spectroscopy.

PubMed

Kuter, David; Streltsov, Victor; Davydova, Natalia; Venter, Gerhard A; Naidoo, Kevin J; Egan, Timothy J

2016-01-01

The interaction of chloroquine (CQ) and the μ-oxo dimer of iron(III) protoporphyrin IX (ferriheme) in aqueous solution was modeled using molecular dynamics (MD) simulations. Two models of the CQ-(μ-oxo ferriheme) complex were investigated, one involving CQ π-stacked with an unligated porphyrin face of μ-oxo ferriheme and the other in which CQ was docked between the two porphyrin rings. The feasibility of both models was tested by fitting computed structures to the experimental extended X-ray absorption fine structure (EXAFS) spectrum of the CQ-(μ-oxo ferriheme) complex in frozen aqueous solution. The docked model produced better agreement with experimental data, suggesting that this is the more likely structure in aqueous solution. The EXAFS fit indicated a longer than expected Fe-O bond of 1.87Å, accounting for the higher than expected magnetic moment of the complex. As a consequence, the asymmetric Fe-O-Fe stretch shifts much lower in frequency and was identified in the precipitated solid at 744cm(-1) with the aid of the O(18) isomer shift. Three important CQ-ferriheme interactions were identified in the docked structure. These were a hydrogen bond between the oxide bridge of μ-oxo ferriheme and the protonated quinolinium nitrogen atom of CQ; π-stacking between the quinoline ring of CQ and the porphyrin rings; and a close contact between the 7-chloro substituent of CQ and the porphyrin methyl hydrogen atoms. These interactions can be used to rationalize previously observed structure-activity relationships for quinoline-ferriheme association. Copyright © 2015 Elsevier Inc. All rights reserved.

Excitation of atomic nitrogen by electron impact

NASA Technical Reports Server (NTRS)

Stone, E. J.; Zipf, E. C.

1972-01-01

Absolute cross sections were measured for the excitation of the N I(1134, 1164, 1168, 1200, 1243, and 1743 A) multiplets by electron impact on atomic nitrogen. The presence of vibrationally excited molecular nitrogen in the discharged gas was confirmed, and its effect on the measurements is discussed. The ratio of the oscillator strengths of the 1200 and 1134 A resonance transitions is presented, as well as the branching ratio for the N I(1311/1164 A) multiplets. Striking differences in the distribution of intensity between the spectra of atomic nitrogen and molecular nitrogen excited by energetic electrons suggest an optical method for measuring the density of atomic nitrogen in the upper atmosphere.

Syntheses, spectroscopic characterization, thermal study, molecular modeling, and biological evaluation of novel Schiff's base benzil bis(5-amino-1,3,4-thiadiazole-2-thiol) with Ni(II), and Cu(II) metal complexes

NASA Astrophysics Data System (ADS)

Chandra, Sulekh; Gautam, Seema; Rajor, Hament Kumar; Bhatia, Rohit

2015-02-01

Novel Schiff's base ligand, benzil bis(5-amino-1,3,4-thiadiazole-2-thiol) was synthesized by the condensation of benzil and 5-amino-1,3,4-thiadiazole-2-thiol in 1:2 ratio. The structure of ligand was determined on the basis of elemental analyses, IR, 1H NMR, mass, and molecular modeling studies. Synthesized ligand behaved as tetradentate and coordinated to metal ion through sulfur atoms of thiol ring and nitrogen atoms of imine group. Ni(II), and Cu(II) complexes were synthesized with this nitrogen-sulfur donor (N2S2) ligand. Metal complexes were characterized by elemental analyses, molar conductance, magnetic susceptibility measurements, IR, electronic spectra, EPR, thermal, and molecular modeling studies. All the complexes showed molar conductance corresponding to non-electrolytic nature, expect [Ni(L)](NO3)2 complex, which was 1:2 electrolyte in nature. [Cu(L)(SO4)] complex may possessed square pyramidal geometry, [Ni(L)](NO3)2 complex tetrahedral and rest of the complexes six coordinated octahedral/tetragonal geometry. Newly synthesized ligand and its metal complexes were examined against the opportunistic pathogens. Results suggested that metal complexes were more biological sensitive than free ligand.

A Computational Study of Structure and Reactivity of N-Substitued-4-Piperidones Curcumin Analogues and Their Radical Anions.

PubMed

Martínez-Cifuentes, Maximiliano; Weiss-López, Boris; Araya-Maturana, Ramiro

2016-12-02

In this work, a computational study of a series of N -substitued-4-piperidones curcumin analogues is presented. The molecular structure of the neutral molecules and their radical anions, as well as their reactivity, are investigated. N -substituents include methyl and benzyl groups, while substituents on the aromatic rings cover electron-donor and electron-acceptor groups. Substitutions at the nitrogen atom do not significantly affect the geometry and frontier molecular orbitals (FMO) energies of these molecules. On the other hand, substituents on the aromatic rings modify the distribution of FMO. In addition, they influence the capability of these molecules to attach an additional electron, which was studied through adiabatic (AEA) and vertical electron affinities (VEA), as well as vertical detachment energy (VDE). To study electrophilic properties of these structures, local reactivity indices, such as Fukui ( f ⁺) and Parr ( P ⁺) functions, were calculated, and show the influence of the aromatic rings substituents on the reactivity of α,β-unsaturated ketones towards nucleophilic attack. This study has potential implications for the design of curcumin analogues based on a 4-piperidone core with desired reactivity.

Weyl Exceptional Rings in a Three-Dimensional Dissipative Cold Atomic Gas (Author’s Manuscript)

DTIC Science & Technology

2017-01-27

Weyl Exceptional Rings in a Three-Dimensional Dissipative Cold Atomic Gas Yong Xu,∗ Sheng-Tao Wang, and L.-M. Duan Department of Physics, University...atomic gas trapped in an optical lattice. Recently, condensed matter systems have proven to be a powerful platform to study low energy gapless...possess a nonzero quantized Chern number. This leads to a natural question of whether there exists a topological ring exhibiting both a quantized Chern

Modeling of recovery mechanism of ozone zero phenomenaby adding small amount of nitrogen in atmospheric pressure oxygen dielectric barrier discharges

NASA Astrophysics Data System (ADS)

Akashi, Haruaki; Yoshinaga, Tomokazu

2013-09-01

Ozone zero phenomena in an atmospheric pressure oxygen dielectric barrier discharges have been one of the major problems during a long time operation of ozone generators. But it is also known that the adding a small amount of nitrogen makes the recover from the ozone zero phenomena. To make clear the mechanism of recovery, authors have been simulated the discharges with using the results of Ref. 3. As a result, the recovery process can be seen and ozone density increased. It is found that the most important species would be nitrogen atoms. The reaction of nitrogen atoms and oxygen molecules makes oxygen atoms which is main precursor species of ozone. This generation of oxygen atoms is effective to increase ozone. The dependence of oxygen atom density (nO) and nitrogen atom density (nN) ratio was examined in this paper. In the condition of low nN/nO ratio case, generation of nitrogen oxide is low, and the quenching of ozone by the nitrogen oxide would be low. But in the high ratio condition, the quenching of ozone by nitrogen oxide would significant. This work was supported by KAKENHI(23560352).

Nitrated metalloporphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1992-01-01

Alkanes are oxidized by contact with oxygen-containing gas in the presence as catalyst of a metalloporphyrin in which hydrogen atoms in the porphyrin ring have been replaced with one or more nitro groups. Hydrogen atoms in the porphyrin ring may also be substituted with halogen atoms.

Cyano- and polycyanometalloporphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1992-01-01

Alkanes are oxidized by contact with oxygen-containing gas in the presence as catalyst of a metalloporphyrin in which hydrogen atoms in the porphyrin ring have been substituted with one or more cyano groups. Hydrogen atoms in the porphyrin ring may also be substituted with halogen atoms.

Structure elucidation of the designer drug N-(1-amino-3,3-dimethyl-1-oxobutan-2-yl)-1-(5-fluoropentyl)-3-(4-fluorophenyl)-pyrazole-5-carboxamide and the relevance of predicted (13) C NMR shifts - a case study.

PubMed

Girreser, Ulrich; Rösner, Peter; Vasilev, Andrej

2016-07-01

The detailed structure elucidation process of the new cannabimimetic designer drug, N-(1-amino-3,3-dimethyl-1-oxobutan-2-yl)-1-(5-fluoropentyl)-3-(4-fluorophenyl)-pyrazole-5-carboxamide, with a highly substituted pyrazole skeleton, using nuclear magnetic resonance (NMR) spectroscopic and mass spectrometric (MS) techniques is described. After a first analysis of the NMR spectra and comparison with 48 possible pyrazole and imidazole structures, a subset of six positional isomeric pyrazoles and six imidazoles remained conceivable. Four substituents of the heterocyclic skeleton were identified: a proton bound to a pyrazole ring carbon atom; a 5-fluoropentyl group; a 4-fluorophenyl substituent; and a carbamoyl group, which is N-substituted with a methyl residue carrying a tert.-butyl and a carbamoyl substituent. The 5-fluoropentyl residue is situated at the nitrogen ring atom. Additional NMR experiments like the (1) H,(13) C HMBC were performed, but due to the small number of signals based on long-range couplings, the comparison of predicted and observed (13) C chemical shifts became necessary. The open access Internet shift prediction programs NMRDB, NMRSHIFTDB2, and CSEARCH were employed for the prediction of (13) C shift values which allowed an efficient and unambiguous structure determination. For the identified N-(1-amino-3,3-dimethyl-1-oxobutan-2-yl)-1-(5-fluoropentyl)-3-(4-fluorophenyl)-pyrazole-5-carboxamide, the best agreement between predicted (13) C shifts and the observed chemical shifts and long-range couplings for the pyrazole ring carbon atoms, with a standard error of about 2 ppm, was found with each of the predictions. For the comparison of measured and predicted chemical shifts model compounds with simple substituents proved helpful. The identified compound is a homologue of AZ-037 which is offered by Internet suppliers. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

Infrared spectroscopy of matrix-isolated neutral polycyclic aromatic nitrogen heterocycles: The acridine series

NASA Astrophysics Data System (ADS)

Mattioda, A. L.; Bauschlicher, C. W.; Ricca, A.; Bregman, J.; Hudgins, D. M.; Allamandola, L. J.

2017-06-01

The matrix-isolated, mid-infrared spectra of seven acridine-based polycyclic aromatic nitrogen heterocycles (PANHs) have been measured and compared to their non-nitrogen containing parent molecule. The acridine species investigated include acridine, benz[a]acridine, benz[c]acridine, dibenz[a,j]acridine, dibenz[c,h]acridine, dibenz[a,h]acridine and dibenz[a,c]acridine. The previously reported results for 1 and 2-azabenz[a]anthracenes are included for comparison. The experimentally determined band frequencies and intensities are compared with their B3LYP/6-31G(d) values. The overall agreement between experimental and theoretical values is good and in line with our previous investigations. Shifts, typically to the blue, are noted for the C-H out-of-plane (CHoop) motions upon insertion of a nitrogen atom. The formation of a bay region upon addition of additional benzene rings to the anthracene/acridine structure splits the solo hydrogen motions into a bay region solo and an external solo hydrogen, with the bay region solo hydrogen coupling to the quartet hydrogen motions and the external solo hydrogen coupling with the duo hydrogen motions resulting in an extreme decrease in intensity for the CHoop solo hydrogen band when the external hydrogen is replaced by a nitrogen atom. The C-C and C-H in-plane region of this acridine series exhibits the characteristic two fold increase in intensity, noted previously for PANHs. The strong ≈1400 cm-1 band, which was identified in the previous PANH study, is noted in several molecular species as well as another strong PANH feature between 1480 and 1515 cm-1 for several molecules. The presence of these strong bands appear to be primarily responsible for the two-fold increase in the C-H in-plane region's (1100-1600 cm-1) intensity. The C-H stretching region can be characterized by contributions from the solo (bay or external), duo and quartet hydrogens, similar to what was observed in the dibenzopolyacene compounds.

Crystal structure of 2-diazo-imidazole-4,5-dicarbo-nitrile.

PubMed

Parrish, Damon A; Kramer, Stephanie; Windler, G Kenneth; Chavez, David E; Leonard, Philip W

2015-07-01

In the title compound, C5N6, all the atoms are approximately coplanar. In the crystal, mol-ecules are packed with short contact distances of 2.885 (2) (between the diazo N atom connected to the ring and a cyano N atom on a neighboring mol-ecule) and 3.012 (2) Å (between the terminal diazo N atom and an N atom of a neighboring imidazole ring).

Precise control of atomic nitrogen production in an electron cyclotron resonance plasma using N2/noble gas mixtures

NASA Astrophysics Data System (ADS)

Fan, Z. Y.; Newman, N.

1998-07-01

The atomic nitrogen flux and impacting ion kinetic energy are two important parameters which influence the quality of deposited nitride films using reactive growth. In this letter, a method is described to control the flux and kinetic energy of atomic and molecular nitrogen ions using an electron cyclotron resonance plasma with N2/Ar and N2/Ne gas mixtures. The results clearly show that the addition of neon to nitrogen plasma can remarkably enhance the production rate of atomic nitrogen due to Penning ionization involving the metastable state of Ne. In contrast, the addition of argon significantly decreases the rate.

Synthesis and spectral studies on metal complexes of s-triazine based ligand and non linear optical properties

NASA Astrophysics Data System (ADS)

Shanmugakala, R.; Tharmaraj, P.; Sheela, C. D.

2014-11-01

A series of transition metal complexes of type [ML] and [ML2]Cl2 (where M = Cu(II), Ni(II), Co(II) have synthesized from 2-phenylamino-4,6-dichloro-s-triazine and 3,5-dimethyl pyrazole; their characteristics have been investigated by means of elemental analyses, magnetic susceptibility, molar conductance, IR, UV-Vis, Mass, NMR and ESR spectra. The electrochemical behavior of copper(II) complexes we have studied, by using cyclic voltammetry. The ESR spectra of copper(II) complexes are recorded at 300 K and 77 K and their salient features are appropriately reported. Spectral datas, we found, show that the ligand acts as a neutral tridentate, and coordinates through the triazine ring nitrogen and pyrazolyl ring nitrogen atoms to the metal ion. Evident from our findings, the metal(II) complexes of [ML] type exhibit square pyramidal geometry, and that of [ML2]Cl2 exhibit octahedral geometry. The in vitro antimicrobial activities of the ligand and its complexes are evaluated against Bacillus subtilis, Micrococcus luteus, Staphylococcus aureus, Staphylococcus epidermidis, Streptococcus mutans, Escherichia coli, Enterobacter aerogenes, Klebsiella pneumoniae, Proteus vulgaris, Cryptococcus neoformans, Pseudomonas aeruginosa, Salmonella typhi, Serratia marcescens, Shigella flexneri, Vibrio cholera, Vibris parahaemolyticus, Aspergillus niger, Candida albicans and Penicillium oxalicum by well-diffusion method. The second harmonic generation efficiency of the ligand and its complexes are determined and compared with urea and KDP.

Activity of alkaloids on peptic ulcer: what's new?

PubMed

do Nascimento, Raphaela Francelino; de Sales, Igor Rafael Praxedes; de Oliveira Formiga, Rodrigo; Barbosa-Filho, José Maria; Sobral, Marianna Vieira; Tavares, Josean Fechine; Diniz, Margareth de Fátima Formiga Melo; Batista, Leônia Maria

2015-01-08

Peptic ulcer is a common disease characterized by lesions that affect the mucosa of the esophagus, stomach and/or duodenum, and may extend into the muscular layer of the mucosa. Natural products have played an important role in the process of development and discovery of new drugs, due to their wide structural diversity and present, mostly specific and selective biological activities. Among natural products the alkaloids, biologically active secondary metabolites, that can be found in plants, animals or microorganisms stand out. The alkaloids are compounds consisting of a basic nitrogen atom that may or may not be part of a heterocyclic ring. This review will describe 15 alkaloids with antiulcer activity in animal models and in vitro studies.

Cold atoms in one-dimensional rings: a Luttinger liquid approach to precision measurement

NASA Astrophysics Data System (ADS)

Ragole, Stephen; Taylor, Jacob

Recent experiments have realized ring shaped traps for ultracold atoms. We consider the one-dimensional limit of these ring systems with a moving weak barrier, such as a blue-detuned laser beam. In this limit, we employ Luttinger liquid theory and find an analogy with the superconducting charge qubit. In particular, we find that strongly-interacting atoms in such a system could be used for precision rotation sensing. We compare the performance of this new sensor to the state of the art non-interacting atom interferometry. Funding provided by the Physics Frontier Center at the JQI and by DARPA QUASAR.

2-Benzylpiperazine: A new scaffold for potent human carbonic anhydrase inhibitors. Synthesis, enzyme inhibition, enantioselectivity, computational and crystallographic studies and in vivo activity for a new class of intraocular pressure lowering agents.

PubMed

Chiaramonte, Niccolò; Bua, Silvia; Ferraroni, Marta; Nocentini, Alessio; Bonardi, Alessandro; Bartolucci, Gianluca; Durante, Mariaconcetta; Lucarini, Laura; Chiapponi, Donata; Dei, Silvia; Manetti, Dina; Teodori, Elisabetta; Gratteri, Paola; Masini, Emanuela; Supuran, Claudiu T; Romanelli, Maria Novella

2018-05-10

Two series of 2-benzylpiperazines have been prepared and tested for the inhibition of physiologically relevant isoforms of human carbonic anhydrases (hCA, EC 4.2.1.1). The new compounds carry on one nitrogen atom of the piperazine ring a sulfamoylbenzamide group as zinc-binding moiety, and different alkyl/acyl/sulfonyl groups on the other nitrogen. Regio- and stero-isomers are described. The majority of these compounds showed Ki values in the low-medium nanomolar range against hCA I, II and IV, but not IX. In many instances interaction with the enzyme was enantioselective. The binding mode has been studied by means of X-ray crystallography and molecular modelling. Two compounds, evaluated in rabbit models of glaucoma, were able to significantly reduce intraocular pressure, making them interesting candidates for further studies. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

High-pressure synthesis of a pentazolate salt [High-pressure synthesis of condensed-phase pentazolate

DOE PAGES

Steele, Brad A.; Stavrou, Elissaios; Crowhurst, Jonathan C.; ...

2016-12-06

The pentazolates, the last all-nitrogen members of the azole series, have been notoriously elusive for the last hundred years despite enormous efforts to make these compounds in either gas or condensed phases. Here, we report a successful synthesis of a solid state compound consisting of isolated pentazolate anions N 5 –, which is achieved by compressing and laser heating cesium azide (CsN 3) mixed with N 2 cryogenic liquid in a diamond anvil cell. The experiment was guided by theory, which predicted the transformation of the mixture at high pressures to a new compound, cesium pentazolate salt (CsN 5). Electronmore » transfer from Cs atoms to N 5 rings enables both aromaticity in the pentazolates as well as ionic bonding in the CsN 5 crystal. As a result, this work provides critical insight into the role of extreme conditions in exploring unusual bonding routes that ultimately lead to the formation of novel high nitrogen content species.« less

New group-V elemental bilayers: A tunable structure model with four-, six-, and eight-atom rings

NASA Astrophysics Data System (ADS)

Kong, Xiangru; Li, Linyang; Leenaerts, Ortwin; Liu, Xiong-Jun; Peeters, François M.

2017-07-01

Two-dimensional group-V elemental materials have attracted widespread attention due to their nonzero band gap while displaying high electron mobility. Using first-principles calculations, we propose a series of new elemental bilayers with group-V elements (Bi, Sb, As). Our study reveals the dynamical stability of four-, six-, and eight-atom ring structures, demonstrating their possible coexistence in such bilayer systems. The proposed structures for Sb and As are large-gap semiconductors that are potentially interesting for applications in future nanodevices. The Bi structures have nontrivial topological properties with a direct nontrivial band gap. The nontrivial gap is shown to arise from a band inversion at the Brillouin zone center due to the strong intrinsic spin-orbit coupling in Bi atoms. Moreover, we demonstrate the possibility of tuning the properties of these materials by enhancing the ratio of six-atom rings to four- and eight-atom rings, which results in wider nontrivial band gaps and lower formation energies.

Stability branching induced by collective atomic recoil in an optomechanical ring cavity

NASA Astrophysics Data System (ADS)

Ian, Hou

2017-02-01

In a ring cavity filled with an atomic condensate, self-bunching of atoms due to the cavity pump mode produce an inversion that re-emits into the cavity probe mode with an exponential gain, forming atomic recoil lasing. An optomechanical ring cavity is formed when one of the reflective mirrors is mounted on a mechanical vibrating beam. In this paper, we extend studies on the stability of linear optomechanical cavities to such ring cavities with two counter-propagating cavity modes, especially when the forward propagating pump mode is taken to its weak coupling limit. We find that when the atomic recoil is in action, stable states of the mechanical mode of the mirror converge into branch cuts, where the gain produced by the recoiling strikes balance with the multiple decay sources, such as cavity leakage in the optomechanical system. This balance is obtained when the propagation delay in the dispersive atomic medium matches in a periodic pattern to the frequencies and linewidths of the cavity mode and the collective bosonic mode of the atoms. We show an input-output hysteresis cycle between the atomic mode and the cavity mode to verify the multi-valuation of the stable states after branching at the weak coupling limit.

Large diameter metal ring seal prevents gas leakage at 5000 psi

NASA Technical Reports Server (NTRS)

Middelkoop, J. H.

1966-01-01

Large metal ring seal prevents gas leakage in hydrogen, helium, or nitrogen storage bottles at pressures up to 5,000 psi. The grooved ring seal which contains elastomer O-rings is installed between the mating faces of the access cover and the storage bottle.

Irreversible insertion of benzonitrile into platinum(II)-nitrogen bonds of nucleobase complexes. Synthesis and structural characterization of stable azametallacycle compounds.

PubMed

Montagner, Diego; Venzo, Alfonso; Zangrando, Ennio; Longato, Bruno

2010-03-01

Deprotonation of 1-methylcytosine (1-MeCy) and 9-methyladenine (9-MeAd) promoted by cis-[L(2)Pt(mu-OH)](2)(NO(3))(2) (L = PPh(3), PMePh(2), (1)/(2)dppe) in PhCN causes the irreversible insertion of a nitrile molecule into the Pt-N4 and Pt-N6 bonds of the cytosinate and adeninate ligands, respectively, to form the stable azametallacycle complexes cis-[L(2)PtNH=C(Ph){1-MeCy(-2H)}]NO(3) (L = PPh(3), 1; PMePh(2), 2; (1)/(2)dppe, 3) and cis-[L(2)PtNH=C(Ph){9-MeAd(-2H)}]NO(3) (L = PPh(3), 4; PMePh(2), 5) containing the deprotonated form of the molecules (Z)-9-N-(1-methyl-2-oxo-2,3-dihydropyrimidin-4(1H)-ylidene)benzimidamide and (Z)-N-(9-methyl-1H-purin-6(9H)-ylidene)benzimidamide. Single-crystal X-ray analyses of 2 and 4 show the metal coordinated to the N3 cytosine site [Pt-N3 = 2.112(7) A] and to the N1 site of adenine [Pt-N1 = 2.116(6) A] and to the nitrogen atom of the inserted benzonitrile [Pt-N2 = 2.043(6) and 2.010(6) A in 2 and 4, respectively], with the exocyclic nucleobase amino nitrogen bound to the carbon atom of the CN group. Complex 2, in solution, undergoes a dynamic process related to a partially restricted rotation around Pt-P bonds, arising from a steric interaction of the oxygen atom of the cytosine with one ring of the phosphine ligands. The reaction of 4 with acetylacetone (Hacac) causes the quantitative protonation of the anionic ligand, affording the acetylacetonate complex cis-[(PPh(3))(2)Pt(acac)]NO(3) and the free benzimidamide NH=C(Ph){9-MeAd(-H)}. In the same experimental conditions, complex 3 reacts with Hacac only partially.

Boroxol rings from diffraction data on vitreous boron trioxide.

PubMed

Soper, Alan K

2011-09-14

There has been a considerable debate about the nature of the short range atomic order in vitreous B(2)O(3). Some authorities state that it is not possible to build a model of glassy boron oxide of the correct density containing a large number of six-membered rings which also fits experimental diffraction data, but recent computer simulations appear to overrule that view. To discover which view is correct I use empirical potential structure refinement (EPSR) on existing neutron and x-ray diffraction data to build two models of vitreous B(2)O(3). One of these consists only of single boron and oxygen atoms arranged in a network to reproduce the diffraction data as closely as possible. This model has less than 10% of boron atoms in boroxol rings. The second model is made up of an equimolar mixture of B(3)O(3) hexagonal ring 'molecules' and BO(3) triangular molecules, with no free boron or oxygen atoms. This second model therefore has 75% of the boron atoms in boroxol rings. It is found that both models give closely similar diffraction patterns, suggesting that the diffraction data in this case are not sensitive to the number of boroxol rings present in the structure. This reinforces recent Raman, ab initio, and NMR claims that the percentage of boroxol rings in this material may be as high as 75%. The findings of this study probably explain why some interpretations based on different simulation techniques only find a small fraction of boroxol rings. The results also highlight the power of EPSR for the extraction of accurate atomistic representations of amorphous structures, provided adequate additional, non-scattering data (such as Raman and NMR in this case) are available.

Atomic Oxygen (AO) and Nitrogen (AN) In-situ Flux Sensor

DTIC Science & Technology

2016-03-10

AFRL-AFOSR-VA-TR-2016-0126 DURIP 09) AN ATOMIC OXYGEN FLUX MONITOR FOR USE IN THE SEARCH FOR NEW AND BETT Malcolm Beasley LELAND STANFORD JUNIOR UNIV...Grant # FA9550-01-1-0433 M. R. Beasley, PI Stanford University Project Title: Atomic Oxygen (AO) and Nitrogen (AN) In-situ Flux Sensor...of actively controlled in-situ sources of atomic oxygen and nitrogen suitable for MBE application. The goal of this DURIP was to work with a

A simple structural hydrazide-based gelator as a fluoride ion colorimetric sensor.

PubMed

Bai, Binglian; Ma, Jie; Wei, Jue; Song, Jianxi; Wang, Haitao; Li, Min

2014-06-07

A 4-nitrobenzohydrazide derivative, N-(3,4,5-octyloxybenzoyl)-N'-(4'-nitrobenzoyl)hydrazine (C8), was synthesized. It could form stable gels in some of the tested organic solvents. The wide-angle X-ray diffraction analysis showed that the xerogels exhibited a layered structure. SEM images revealed that the molecules self-assembled into fibrous aggregates in the xerogels. FT-IR studies confirmed that the intermolecular hydrogen bonding between C=O and N-H groups was the major driving force for the formation of self-assembling gel processes. The gel is utilized for a 'naked eye' detection of fluoride ions, through a reversible gel-sol transition, which is associated with a color change from colorless to red. An extended conjugated system formed through the phenyl group and a five-membered ring based on intramolecular hydrogen bonding between the oxygen atom near the deprotonation nitrogen atom and the other NH, which is responsible for the dramatic color change upon addition of fluoride ions.

Investigations into the synthesis and fluorescence properties of Eu(III), Tb(III), Sm(III) and Gd(III) complexes of a novel bis- β-diketone-type ligand

NASA Astrophysics Data System (ADS)

Luo, Yi-Ming; Chen, Zhe; Tang, Rui-Ren; Xiao, Lin-Xiang; Peng, Hong-Jian

2008-02-01

A novel bis- β-diketon ligand, 1,1'-(2,6-bispyridyl)bis-3-phenyl-1,3-propane-dione (L), was designed and synthesized and its complexes with Eu(III), Tb(III), Sm(III) and Gd(III) ions were successfully prepared. The ligand and the corresponding metal complexes were characterized by elemental analysis, and infrared, mass and proton nuclear magnetic resonance spectroscopy. Analysis of the IR spectra suggested that each of the lanthanide metal ions coordinated to the ligand via the carbonyl oxygen atoms and the nitrogen atom of the pyridine ring. The fluorescence properties of these complexes in solid state were investigated and it was discovered that all of the lanthanide ions could be sensitized by the ligand (L) to some extent. In particular, the Tb(III) complex was an excellent green-emitter and would be a potential candidate material for applications in organic light-emitting devices (OLEDs) and medical diagnosis.

Ultraviolet absorption experiment MA-059

NASA Technical Reports Server (NTRS)

Donahue, T. M.; Hudson, R. D.; Anderson, J.; Kaufman, F.; Mcelroy, M. B.

1976-01-01

The ultraviolet absorption experiment performed during the Apollo Soyuz mission involved sending a beam of atomic oxygen and atomic nitrogen resonance radiation, strong unabsorbable oxygen and nitrogen radiation, and visual radiation, all filling the same 3 deg-wide field of view from the Apollo to the Soyuz. The radiation struck a retroreflector array on the Soyuz and was returned to a spectrometer onboard the Apollo. The density of atomic oxygen and atomic nitrogen between the two spacecraft was measured by observing the amount of resonance radiation absorbed when the line joining Apollo and Soyuz was perpendicular to their velocity with respect to the ambient atmosphere. Information concerning oxygen densities was also obtained by observation of resonantly fluorescent light. The absorption experiments for atomic oxygen and atomic nitrogen were successfully performed at a range of 500 meters, and abundant resonance fluorescence data were obtained.

Adsorption Energies of Carbon, Nitrogen, and Oxygen Atoms on the Low-temperature Amorphous Water Ice: A Systematic Estimation from Quantum Chemistry Calculations

NASA Astrophysics Data System (ADS)

Shimonishi, Takashi; Nakatani, Naoki; Furuya, Kenji; Hama, Tetsuya

2018-03-01

We propose a new simple computational model to estimate the adsorption energies of atoms and molecules to low-temperature amorphous water ice, and we present the adsorption energies of carbon (3 P), nitrogen (4 S), and oxygen (3 P) atoms based on quantum chemistry calculations. The adsorption energies were estimated to be 14,100 ± 420 K for carbon, 400 ± 30 K for nitrogen, and 1440 ± 160 K for oxygen. The adsorption energy of oxygen is consistent with experimentally reported values. We found that the binding of a nitrogen atom is purely physisorption, while that of a carbon atom is chemisorption, in which a chemical bond to an O atom of a water molecule is formed. That of an oxygen atom has a dual character, with both physisorption and chemisorption. The chemisorption of atomic carbon also implies the possibility of further chemical reactions to produce molecules bearing a C–O bond, though this may hinder the formation of methane on water ice via sequential hydrogenation of carbon atoms. These properties would have a large impact on the chemical evolution of carbon species in interstellar environments. We also investigated the effects of newly calculated adsorption energies on the chemical compositions of cold dense molecular clouds with the aid of gas-ice astrochemical simulations. We found that abundances of major nitrogen-bearing molecules, such as N2 and NH3, are significantly altered by applying the calculated adsorption energy, because nitrogen atoms can thermally diffuse on surfaces, even at 10 K.

Bias in bonding behavior among boron, carbon, and nitrogen atoms in ion implanted a-BN, a-BC, and diamond like carbon films

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

Genisel, Mustafa Fatih; Uddin, Md. Nizam; Say, Zafer

2011-10-01

In this study, we implanted N{sup +} and N{sub 2}{sup +} ions into sputter deposited amorphous boron carbide (a-BC) and diamond like carbon (DLC) thin films in an effort to understand the chemical bonding involved and investigate possible phase separation routes in boron carbon nitride (BCN) films. In addition, we investigated the effect of implanted C{sup +} ions in sputter deposited amorphous boron nitride (a-BN) films. Implanted ion energies for all ion species were set at 40 KeV. Implanted films were then analyzed using x-ray photoelectron spectroscopy (XPS). The changes in the chemical composition and bonding chemistry due to ion-implantationmore » were examined at different depths of the films using sequential ion-beam etching and high resolution XPS analysis cycles. A comparative analysis has been made with the results from sputter deposited BCN films suggesting that implanted nitrogen and carbon atoms behaved very similar to nitrogen and carbon atoms in sputter deposited BCN films. We found that implanted nitrogen atoms would prefer bonding to carbon atoms in the films only if there is no boron atom in the vicinity or after all available boron atoms have been saturated with nitrogen. Implanted carbon atoms also preferred to either bond with available boron atoms or, more likely bonded with other implanted carbon atoms. These results were also supported by ab-initio density functional theory calculations which indicated that carbon-carbon bonds were energetically preferable to carbon-boron and carbon-nitrogen bonds.« less

The Kinetics of Nitrogen Atom Recombination

ERIC Educational Resources Information Center

Brown, G. Ronald; Winkler, C. A.

1977-01-01

Describes a study of the kinetics of the recombination of nitrogen atoms in which concentration-time relations are determined directly by utilizing visual observations of emissions to make gas phase titrations of N atoms with NO. (MLH)

Syntheses, spectroscopic characterization, thermal study, molecular modeling, and biological evaluation of novel Schiff's base benzil bis(5-amino-1,3,4-thiadiazole-2-thiol) with Ni(II), and Cu(II) metal complexes.

PubMed

Chandra, Sulekh; Gautam, Seema; Rajor, Hament Kumar; Bhatia, Rohit

2015-02-25

Novel Schiff's base ligand, benzil bis(5-amino-1,3,4-thiadiazole-2-thiol) was synthesized by the condensation of benzil and 5-amino-1,3,4-thiadiazole-2-thiol in 1:2 ratio. The structure of ligand was determined on the basis of elemental analyses, IR, (1)H NMR, mass, and molecular modeling studies. Synthesized ligand behaved as tetradentate and coordinated to metal ion through sulfur atoms of thiol ring and nitrogen atoms of imine group. Ni(II), and Cu(II) complexes were synthesized with this nitrogen-sulfur donor (N2S2) ligand. Metal complexes were characterized by elemental analyses, molar conductance, magnetic susceptibility measurements, IR, electronic spectra, EPR, thermal, and molecular modeling studies. All the complexes showed molar conductance corresponding to non-electrolytic nature, expect [Ni(L)](NO3)2 complex, which was 1:2 electrolyte in nature. [Cu(L)(SO4)] complex may possessed square pyramidal geometry, [Ni(L)](NO3)2 complex tetrahedral and rest of the complexes six coordinated octahedral/tetragonal geometry. Newly synthesized ligand and its metal complexes were examined against the opportunistic pathogens. Results suggested that metal complexes were more biological sensitive than free ligand. Copyright © 2014 Elsevier B.V. All rights reserved.

15N in tree rings as a bio-indicator of changing nitrogen cycling in tropical forests: an evaluation at three sites using two sampling methods

PubMed Central

van der Sleen, Peter; Vlam, Mart; Groenendijk, Peter; Anten, Niels P. R.; Bongers, Frans; Bunyavejchewin, Sarayudh; Hietz, Peter; Pons, Thijs L.; Zuidema, Pieter A.

2015-01-01

Anthropogenic nitrogen deposition is currently causing a more than twofold increase of reactive nitrogen input over large areas in the tropics. Elevated 15N abundance (δ15N) in the growth rings of some tropical trees has been hypothesized to reflect an increased leaching of 15N-depleted nitrate from the soil, following anthropogenic nitrogen deposition over the last decades. To find further evidence for altered nitrogen cycling in tropical forests, we measured long-term δ15N values in trees from Bolivia, Cameroon, and Thailand. We used two different sampling methods. In the first, wood samples were taken in a conventional way: from the pith to the bark across the stem of 28 large trees (the “radial” method). In the second, δ15N values were compared across a fixed diameter (the “fixed-diameter” method). We sampled 400 trees that differed widely in size, but measured δ15N in the stem around the same diameter (20 cm dbh) in all trees. As a result, the growth rings formed around this diameter differed in age and allowed a comparison of δ15N values over time with an explicit control for potential size-effects on δ15N values. We found a significant increase of tree-ring δ15N across the stem radius of large trees from Bolivia and Cameroon, but no change in tree-ring δ15N values over time was found in any of the study sites when controlling for tree size. This suggests that radial trends of δ15N values within trees reflect tree ontogeny (size development). However, for the trees from Cameroon and Thailand, a low statistical power in the fixed-diameter method prevents to conclude this with high certainty. For the trees from Bolivia, statistical power in the fixed-diameter method was high, showing that the temporal trend in tree-ring δ15N values in the radial method is primarily caused by tree ontogeny and unlikely by a change in nitrogen cycling. We therefore stress to account for tree size before tree-ring δ15N values can be properly interpreted. PMID:25914707

(15)N in tree rings as a bio-indicator of changing nitrogen cycling in tropical forests: an evaluation at three sites using two sampling methods.

PubMed

van der Sleen, Peter; Vlam, Mart; Groenendijk, Peter; Anten, Niels P R; Bongers, Frans; Bunyavejchewin, Sarayudh; Hietz, Peter; Pons, Thijs L; Zuidema, Pieter A

2015-01-01

Anthropogenic nitrogen deposition is currently causing a more than twofold increase of reactive nitrogen input over large areas in the tropics. Elevated (15)N abundance (δ(15)N) in the growth rings of some tropical trees has been hypothesized to reflect an increased leaching of (15)N-depleted nitrate from the soil, following anthropogenic nitrogen deposition over the last decades. To find further evidence for altered nitrogen cycling in tropical forests, we measured long-term δ(15)N values in trees from Bolivia, Cameroon, and Thailand. We used two different sampling methods. In the first, wood samples were taken in a conventional way: from the pith to the bark across the stem of 28 large trees (the "radial" method). In the second, δ(15)N values were compared across a fixed diameter (the "fixed-diameter" method). We sampled 400 trees that differed widely in size, but measured δ(15)N in the stem around the same diameter (20 cm dbh) in all trees. As a result, the growth rings formed around this diameter differed in age and allowed a comparison of δ(15)N values over time with an explicit control for potential size-effects on δ(15)N values. We found a significant increase of tree-ring δ(15)N across the stem radius of large trees from Bolivia and Cameroon, but no change in tree-ring δ(15)N values over time was found in any of the study sites when controlling for tree size. This suggests that radial trends of δ(15)N values within trees reflect tree ontogeny (size development). However, for the trees from Cameroon and Thailand, a low statistical power in the fixed-diameter method prevents to conclude this with high certainty. For the trees from Bolivia, statistical power in the fixed-diameter method was high, showing that the temporal trend in tree-ring δ(15)N values in the radial method is primarily caused by tree ontogeny and unlikely by a change in nitrogen cycling. We therefore stress to account for tree size before tree-ring δ(15)N values can be properly interpreted.

INDIUM AND ZINC MEDIATED ONE-ATOM CARBOCYCLE ENLARGEMENT IN WATER. (R822668)

EPA Science Inventory

Abstract

Six-, seven-, eight-membered rings are enlarged by one carbon-atom into seven-, eight- and nine-membered ring derivatives respectively, via indium or zinc mediated reactions in aqueous medium.

The Jumping Ring Experiment

ERIC Educational Resources Information Center

Baylie, M.; Ford, P. J.; Mathlin, G. P.; Palmer, C.

2009-01-01

The jumping ring experiment has become central to liquid nitrogen shows given as part of the outreach and open day activities carried out within the University of Bath. The basic principles of the experiment are described as well as the effect of changing the geometry of the rings and their metallurgical state. In general, aluminium rings are…

DC-Powered Jumping Ring

ERIC Educational Resources Information Center

Jeffery, Rondo N.; Farhang, Amiri

2016-01-01

The classroom jumping ring demonstration is nearly always performed using alternating current (AC), in which the ring jumps or flies off the extended iron core when the switch is closed. The ring jumps higher when cooled with liquid nitrogen (LN2). We have performed experiments using DC to power the solenoid and find similarities and significant…

The earth's ring current - Present situation and future thrusts

NASA Technical Reports Server (NTRS)

Williams, D. J.

1987-01-01

Particle distributions, currents, and the ring current situation prior to the August 1984 launch of the AMPTE Charge Composition Explorer (CCE) are discussed. CCE results which demonstrate the capability of these new measurements to pursue questions of ring current sources, energization, and transport are presented. Consideration is given to various ring current generation mechanisms which have been discussed in the literature, and a two-step generation process which to a certain extent unifies the previous mechanisms is presented. The first in-situ global observations of ring current decay as obtained through the detection of energetic neutral atoms generated by charge exchange interactions between the ring current and hydrogen geocorona are discussed, as well as the possibility of using the detection of energetic neutral atoms to obtain global images of the earth's ring current.

Electronic Properties of Curved and Defective 2-D BN Nanostructures

NASA Astrophysics Data System (ADS)

Beach, Kory; Terrones, Humberto; Raeliarijaona, Aldo; Siegel, Ross; Florio, Fred

Density functional theory (DFT) with local density approximation (LDA) pseudopotentials is used to calculate the band structure and density of states of various novel 2-D BN nanostructures. Three types of systems are studied: Schwarzites, a Haeckelite, and an h-BN monolayer. Schwarzites are negatively curved structures in which the curvature is due to the introduction of octagonal rings of alternating boron and nitrogen atoms. In particular, three families of Schwarzites are analyzed: P, G and IWP. The Haeckelites on the other hand, are flat layers composed of squares and octagons of BN. It is found that all these BN allotropes are metastable in which the band gap is direct and smaller than the most stable system, h-BN. National Science Foundation (EFRI-1433311).

Synthesis and antibacterial activity of sulfonamides. SAR and DFT studies

NASA Astrophysics Data System (ADS)

Boufas, Wahida; Dupont, Nathalie; Berredjem, Malika; Berrezag, Kamel; Becheker, Imène; Berredjem, Hajira; Aouf, Nour-Eddine

2014-09-01

A series of substituted sulfonamide derivatives were synthesized from chlorosulfonyl isocyanate (CSI) in tree steps (carbamoylation, sulfamoylation and deprotection). Antibacterial activity in vitro of some newly formed compounds investigated against clinical strains Gram-positive and Gram-negative: Escherichia coli and Staphylococcus aureus applying the method of dilution and minimal inhibition concentration (MIC) methods. These compounds have significant bacteriostatic activity with totalities of bacterial strains used. DFT calculations with B3LYP/6-31G(d) level have been used to analyze the electronic and geometric characteristics deduced for the stable structure of three compounds presenting conjugation between a nitrogen atom N through its lone pair and an aromatic ring next to it. The principal quantum chemical descriptors have been correlated with the antibacterial activity.

Regio-selective bromination of multiflorine and structures of 3-bromomultiflorine and its molecular complex with succinimide

NASA Astrophysics Data System (ADS)

Borowiak, Teresa; Kubicki, Maciej; Wysocka, Waleria; Przybył, Anna

1998-02-01

The regio-specific bromination of multiflorine, an alkaloid isolated from Lupinus albus is described. The bromomultiflorine and its molecular complex with succinimide have been characterized by IR and NMR spectroscopy, as well as by X-ray diffraction. The conformation in solution and in the solid state has been determined. The molecular complex formation between 3-bromomultiflorine and succinimide molecules is the first case in the class of lupine alkaloids. Both molecules of this complex are held together by an intermolecular hydrogen bond NH⋯N which leads to a conversion of alkaloid nitrogen atom configuration. As a consequence, ring C adopts a chair conformation, whereas it is in a boat form in 3-bromomultiflorine.

Deviation from Normal Boltzmann Distribution of High-lying Energy Levels of Iron Atom Excited by Okamoto-cavity Microwave-induced Plasmas Using Pure Nitrogen and Nitrogen-Oxygen Gases.

PubMed

Wagatsuma, Kazuaki

2015-01-01

This paper describes several interesting excitation phenomena occurring in a microwave-induced plasma (MIP) excited with Okamoto-cavity, especially when a small amount of oxygen was mixed with nitrogen matrix in the composition of the plasma gas. An ion-to-atom ratio of iron, which was estimated from the intensity ratio of ion to atomic lines having almost the same excitation energy, was reduced by adding oxygen gas to the nitrogen MIP, eventually contributing to an enhancement in the emission intensities of the atomic lines. Furthermore, Boltzmann plots for iron atomic lines were observed in a wide range of the excitation energy from 3.4 to 6.9 eV, indicating that plots of the atomic lines having lower excitation energies (3.4 to 4.8 eV) were well fitted on a straight line while those having more than 5.5 eV deviated upwards from the linear relationship. This overpopulation would result from any other excitation process in addition to the thermal excitation that principally determines the Boltzmann distribution. A Penning-type collision with excited species of nitrogen molecules probably explains this additional excitation mechanism, in which the resulting iron ions recombine with captured electrons, followed by cascade de-excitations between closely-spaced excited levels just below the ionization limit. As a result, these high-lying levels might be more populated than the low-lying levels of iron atom. The ionization of iron would be caused less actively in the nitrogen-oxygen plasma than in a pure nitrogen plasma, because excited species of nitrogen molecule, which can provide the ionization energy in a collision with iron atom, are consumed through collisions with oxygen molecules to cause their dissociation. It was also observed that the overpopulation occurred to a lesser extent when oxygen gas was added to the nitrogen plasma. The reason for this was also attributed to decreased number density of the excited nitrogen species due to collisions with oxygen molecule.

Single- and double-photoionization cross sections of atomic nitrogen from threshold to 31 A

NASA Technical Reports Server (NTRS)

Samson, James A. R.; Angel, G. C.

1990-01-01

The relative photoionization cross section of atomic nitrogen for the production of singly and doubly charged ions has been measured from 44.3 to 275 A and from 520 to 852 A. The results have been made absolute by normalization to one-half of the molecular nitrogen cross section at short wavelengths. The smoothed atomic nitrogen cross sections sigma can be accurately represented, at short wavelengths, by the equation sigma(Mb) = 36,700 x (E exp-2.3) as a function of the photon energy E (eV), thereby allowing the cross sections to be extrapolated to the nitrogen K edge at 31 A.

Strategy for designing stable and powerful nitrogen-rich high-energy materials by introducing boron atoms.

PubMed

Wu, Wen-Jie; Chi, Wei-Jie; Li, Quan-Song; Li, Ze-Sheng

2017-06-01

One of the most important aims in the development of high-energy materials is to improve their stability and thus ensure that they are safe to manufacture and transport. In this work, we theoretically investigated open-chain N 4 B 2 isomers using density functional theory in order to find the best way of stabilizing nitrogen-rich molecules. The results show that the boron atoms in these isomers are aligned linearly with their neighboring atoms, which facilitates close packing in the crystals of these materials. Upon comparing the energies of nine N 4 B 2 isomers, we found that the structure with alternating N and B atoms had the lowest energy. Structures with more than one nitrogen atom between two boron atoms had higher energies. The energy of N 4 B 2 increases by about 50 kcal/mol each time it is rearranged to include an extra nitrogen atom between the two boron atoms. More importantly, our results also show that boron atoms stabilize nitrogen-rich molecules more efficiently than carbon atoms do. Also, the combustion of any isomer of N 4 B 2 releases more heat than the corresponding isomer of N 4 C 2 does under well-oxygenated conditions. Our study suggests that the three most stable N 4 B 2 isomers (BN13, BN24, and BN34) are good candidates for high-energy molecules, and it outlines a new strategy for designing stable boron-containing high-energy materials. Graphical abstract The structural characteristics, thermodynamic stabilities, and exothermic properties of nitrogen-rich N 4 B 2 isomers were investigated by means of density functional theory.

Two-photon absorption laser-induced fluorescence measurements of atomic nitrogen in a radio-frequency atmospheric-pressure plasma jet

NASA Astrophysics Data System (ADS)

Wagenaars, E.; Gans, T.; O'Connell, D.; Niemi, K.

2012-08-01

The first direct measurements of atomic nitrogen species in a radio-frequency atmospheric-pressure plasma jet (APPJ) are presented. Atomic nitrogen radicals play a key role in new plasma medicine applications of APPJs. The measurements were performed with a two-photon absorption laser-induced fluorescence diagnostic, using 206.65 nm laser photons for the excitation of ground-state N atoms and observing fluorescence light around 744 nm. The APPJ was run with a helium gas flow of 1 slm and varying small admixtures of molecular nitrogen of 0-0.7 vol%. A maximum in the measured N concentration was observed for an admixture of 0.25 vol% N2.

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

Yuan, Bing; Bernstein, Elliot R., E-mail: erb@Colostate.edu

Unimolecular decomposition of nitrogen-rich energetic salt molecules bis(ammonium)5,5′-bistetrazolate (NH{sub 4}){sub 2}BT and bis(triaminoguanidinium) 5,5′-azotetrazolate TAGzT, has been explored via 283 nm laser excitation. The N{sub 2} molecule, with a cold rotational temperature (<30 K), is observed as an initial decomposition product, subsequent to UV excitation. Initial decomposition mechanisms for the two electronically excited salt molecules are explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(12,8)/6-31G(d) ((NH{sub 4}){sub 2}BT) and ONIOM (CASSCF/6-31G(d):UFF) (TAGzT) levels illustrate that conical intersections play an essential role in the decomposition mechanism as they provide non-adiabatic, ultrafast radiationless internalmore » conversion between upper and lower electronic states. The tetrazole ring opens on the S{sub 1} excited state surface and, through conical intersections (S{sub 1}/S{sub 0}){sub CI}, N{sub 2} product is formed on the ground state potential energy surface without rotational excitation. The tetrazole rings open at the N2—N3 ring bond with the lowest energy barrier: the C—N ring bond opening has a higher energy barrier than that for any of the N—N ring bonds: this is consistent with findings for other nitrogen-rich neutral organic energetic materials. TAGzT can produce N{sub 2} either by the opening of tetrazole ring or from the N=N group linking its two tetrazole rings. Nonetheless, opening of a tetrazole ring has a much lower energy barrier. Vibrational temperatures of N{sub 2} products are hot based on theoretical predictions. Energy barriers for opening of the tetrazole ring for all the nitrogen-rich energetic materials studied thus far, including both neutral organic molecules and salts, are in the range from 0.31 to 2.71 eV. Energy of the final molecular structure of these systems with dissociated N{sub 2} product is in the range from −1.86 to 3.11 eV. The main difference between energetic salts and neutral nitrogen-rich energetic material is that energetic salts usually have lower excitation energy.« less

Process for making ultra-fine ceramic particles

DOEpatents

Stangle, Gregory C.; Venkatachari, Koththavasal R.; Ostrander, Steven P.; Schulze, Walter A.

1995-01-01

A process for producing ultra-fine ceramic particles in which droplets are formed from a ceramic precursor mixture containing a metal cation, a nitrogen-containing fuel, a solvent, and an anion capable of participating in an anionic oxidation-reduction reaction with the nitrogen containing fuel. The nitrogen-containing fuel contains at least three nitrogen atoms, at least one oxygen atom, and at least one carbon atom. The ceramic precursor mixture is dried to remove at least 85 weight percent of the solvent, and the dried mixture is then ignited to form a combusted powder.

Influence of N-Oxide Introduction on the Stability of Nitrogen-Rich Heteroaromatic Rings: A Quantum Chemical Study.

PubMed

Yuan, Jia; Long, Xinping; Zhang, Chaoyang

2016-12-01

N-Oxidization is an important strategy for enhancing the density and energy of energetic materials. Nevertheless, the influence of N + -O - introduction on molecular stability remains relatively unknown. Thus, the present work comprehensively studied 102 basic N-rich ring structures, including azoles, furazans, and azines, as well as their N-oxides by quantum chemical calculations. The introduction of N + -O - weakens molecular stability in most cases because the process elongates chemical bonds, decreases ring aromaticity, narrows the gaps between the highest occupied and lowest unoccupied molecular orbitals, and increases the photochemical reactivity. Besides, the easy H transfer to the neighboring O atom, which forms a N-OH isomer in azoles, renders the stabilization by N-oxide introduction ineffective. However, N-oxide introduction can enhance the molecular stability of 1,2,3,4-tetrazine-1,3-dioxide and tetrazino-tetrazine 1,3,6,8-tetraoxide by promoting σ-π separation and relieving lone-pair repulsion. Moreover, the alternate arrangement of positive and negative charges is another factor stabilizing the 1,2,3,4-tetrazine ring by 1,3-dioxidation. Finally, we assess the accessibility of N-oxidized azoles and azines by regarding N 2 O and H 2 O 2 as oxidizers. We find that all the oxidations were exothermic, thermodynamically spontaneous, and kinetically feasible. After an overall evaluation, we propose 19 N-oxides as basic structures for high-energy materials with considerable stability.

Investigation of the acid-base and electromigration properties of 5-azacytosine derivatives using capillary electrophoresis and density functional theory calculations.

PubMed

Geffertová, Denisa; Ali, Syed Tahir; Šolínová, Veronika; Krečmerová, Marcela; Holý, Antonín; Havlas, Zdeněk; Kašička, Václav

2017-01-06

Capillary electrophoresis (CE) and quantum mechanical density functional theory (DFT) were applied to the investigation of the acid-base and electromigration properties of important compounds: newly synthesized derivatives of 5-azacytosine - analogs of efficient antiviral drug cidofovir. These compounds exhibit a strong antiviral activity and they are considered as potential new antiviral agents. For their characterization and application, it is necessary to know their acid-base properties, particularly the acidity constants (pK a ) of their ionogenic groups (the basic N 3 atom of the triazine ring and the acidic phosphonic acid group in the alkyl chain). First, the mixed acidity constants (pK a mix ) of these ionogenic groups and the ionic mobilities of these compounds were determined by nonlinear regression analysis of the pH dependence of their effective electrophoretic mobilities. Effective mobilities were measured by CE in a series of background electrolytes in a wide pH range (2.0-10.5), at constant ionic strength (25mM) and constant temperature (25°C). Subsequently, the pK a mix values were recalculated to thermodynamic pK a values using the Debye-Hückel theory. The thermodynamic pK a value of the NH + moiety at the N 3 atom of the triazine ring was found to be in the range 2.82-3.30, whereas the pK a of the hydrogenphosphonate group reached values from 7.19 to 7.47, depending on the structure of the analyzed compounds. These experimentally determined pK a values were in good agreement with those calculated by quantum mechanical DFT. In addition, DFT calculations revealed that from the four nitrogen atoms in the 5-azacytosine moiety, the N 3 atom of the triazine ring is preferentially protonated. Effective charges of analyzed compounds ranged from zero or close-to-zero values at pH 2 to -2 elementary charges at pH≥9. Ionic mobilities were in the range (-16.7 to -19.1)×10 -9 m 2 V -1 s -1 for univalent anions and in the interval (-26.9 to -30.3)×10 -9 m 2 V -1 s -1 for divalent anions. Copyright © 2016 Elsevier B.V. All rights reserved.

Efficient electrocatalytic conversion of CO.sub.2 to CO using ligand-protected Au.sub.25 clusters

DOEpatents

Kauffman, Douglas; Matranga, Christopher; Qian, Huifeng; Jin, Rongchao; Alfonso, Dominic R.

2015-09-22

An apparatus and method for CO.sub.2 reduction using an Au.sub.25 electrode. The Au.sub.25 electrode is comprised of ligand-protected Au.sub.25 having a structure comprising an icosahedral core of 13 atoms surrounded by a shell of six semi-ring structures bonded to the core of 13 atoms, where each semi-ring structure is typically --SR--Au--SR--Au--SR or --SeR--Au--SeR--Au--SeR. The 12 semi-ring gold atoms within the six semi-ring structures are stellated on 12 of the 20 faces of the icosahedron of the Au.sub.13 core, and organic ligand --SR or --SeR groups are bonded to the Au.sub.13 core with sulfur or selenium atoms. The Au.sub.25 electrode and a counter-electrode are in contact with an electrolyte comprising CO.sub.2 and H+, and a potential of at least -0.1 volts is applied from the Au.sub.25 electrode to the counter-electrode.

Crystal structure of N′-[(E)-(1S,3R)-(3-isopropyl-1-methyl-2-oxo­cyclo­pent­yl)methyl­idene]-4-methyl­benzene­sulfono­hydrazide

PubMed Central

Tymann, David; Dragon, Dina Christina; Golz, Christopher; Preut, Hans; Strohmann, Carsten; Hiersemann, Martin

2015-01-01

The title compound, C17H24N2O3S, was synthesized in order to determine the relative configuration of the corresponding β-keto aldehyde. In the U-shaped mol­ecule, the five-membered ring approximates an envelope, with the methyl­ene C atom adjacent to the quaternary C atom being the flap, and the methyl and isopropyl substituents lying to the same side of the ring. The dihedral angles between the four nearly coplanar atoms of the five-membered ring and the flap and the aromatic ring are 35.74 (15) and 55.72 (9)°, respectively. The bond angles around the S atom are in the range from 103.26 (12) to 120.65 (14)°. In the crystal, mol­ecules are linked via N—H⋯O hydrogen bonds, forming a chain along the a axis. PMID:26870519

5-Chloro-5''-[4-(di-methyl-amino)-benzyl-idene]-4'-[4-(di-methyl-amino)-phen-yl]-1',1''-di-methyl-dispiro-[indoline-3,2'-pyrrolidine-3',3''-piperidine]-2,4''-dione.

PubMed

Farag, I S Ahmed; Girgis, Adel S; Ramadan, A A; Moustafa, A M; Tiekink, Edward R T

2014-01-01

The title compound, C34H38ClN5O2, has spiro links connecting the pyrrolidine ring and indole residue, as well as the piperidine and pyrrolidine rings. A half-chair conformation is found for the piperidine ring with the C atom connected to the spiro-C atom lying 0.738 (4) Å out of the plane of the remaining five atoms (r.m.s. deviation = 0.0407 Å). The methyl-ene C atom is the flap in the envelope conformation for the pyrrolidine ring. In the crystal, supra-molecular chains are sustained by alternating eight-membered {⋯HNCO}2 and 14-membered {⋯HC5O}2 synthons. Chains are connected into a three-dimensional network by (pyrrolidine-bound phenyl-meth-yl)C-H⋯π(pyrrolidine-bound phen-yl) edge-to-face inter-actions.

The influence of nitrogen ion implantation on the tribological properties of piston rings made of Hardox and Raex steels

NASA Astrophysics Data System (ADS)

Budzyński, P.; Kamiński, M.; Pyszniak, K.

2016-09-01

The implantation of nitrogen, carbon, and oxygen can be used for enhancing the tribological properties of critical components for internal combustion engines. Hardox and Raex steels have very similar strength parameters as for steel used for piston rings in internal combustion engines. An essential criterion when selecting material for the production of piston rings is a low friction factor and a low wear index. The aim of this study was to determine the extent to which these parameters can be enhanced by nitrogen ion implantation. Samples were implanted with nitrogen ions with 65 keV energy and the fluence of implanted ions set to 1.1017 N + /cm2. Friction and wear measurements were performed on a pin-on disc stand. The results demonstrate that implantation with nitrogen ions significantly reduces the friction factor and wear of Hardox 450 and Raex 400 steels. Implantation can and should be used for enhancing the tribological properties of steel used for friction elements in internal combustion engines, particularly when heat treatment is excluded. Final elements can be subjected to implantation, as the process does not change their dimensions.

Theoretical study of NMR, infrared and Raman spectra on triple-decker phthalocyanines

NASA Astrophysics Data System (ADS)

Suzuki, Atsushi; Oku, Takeo

2016-02-01

Electronic structures and magnetic properties of multi-decker phthalocyanines were studied by theoretical calculation. Electronic structures, excited processes at multi-states, isotropic chemical shifts of 13C, 14N and 1H-nuclear magnetic resonance (NMR), principle V-tensor in electronic field gradient (EFG) tensor and asymmetry parameters (η), vibration mode in infrared (IR) and Raman spectra of triple-decker phthalocyanines were calculated by density functional theory (DFT) and time-dependent DFT using B3LYP as basis function. Electron density distribution was delocalized on the phthalocyanine rings with electron static potential. Considerable separation of chemical shifts in 13C, 14N and 1H-NMR was originated from nuclear spin interaction between nitrogen and carbon atoms, nuclear quadrupole interaction based on EFG and η of central metal under crystal field. Calculated optical absorption at multi-excited process was derived from overlapping π-orbital on the phthalocyanine rings. The vibration modes in IR and Raman spectra were based on in-plane deformation and stretching vibrations of metal-ligand coordination bond on the deformed structure.

Complexation of imidazopyridine-based cations with a 24-crown-8 ether host: [2]pseudorotaxane and partially threaded structures.

PubMed

Moreno-Olivares, Surisadai I; Cervantes, Ruy; Tiburcio, Jorge

2013-11-01

A new series of linear molecules derived from 1,2-bis(imidazopyridin-2-yl)ethane can fully or partially penetrate the cavity of the dibenzo-24-crown-8 macrocycle to produce a new family of host-guest complexes. Protonation or alkylation of the nitrogen atoms on the pyridine rings led to an increase in the guest total positive charge up to 4+ and simultaneously generated two new recognition sites (pyridinium motifs) that are in competition with the 1,2-bis(benzimidazole)ethane motif for the crown ether. The relative position of the pyridine ring and the chemical nature of the N-substituent determined the preferred motif and the host-guest complex geometry: (i) for linear guests with relatively bulky groups (i.e., a benzyl substituent), the 1,2-bis(benzimidazole)ethane motif is favored, leading to a fully threaded complex with a [2]pseudorotaxane geometry; (ii) for small substituents, such as -H and -CH3 groups, regardless of the guest shape, the pyridinium motifs are preferred, leading to external partially threaded complexes in a 2:1 host to guest stoichiometry.

Fused-ring structure of decahydroisoquinolin as a novel scaffold for SARS 3CL protease inhibitors.

PubMed

Shimamoto, Yasuhiro; Hattori, Yasunao; Kobayashi, Kazuya; Teruya, Kenta; Sanjoh, Akira; Nakagawa, Atsushi; Yamashita, Eiki; Akaji, Kenichi

2015-02-15

The design and evaluation of a novel decahydroisoquinolin scaffold as an inhibitor for severe acute respiratory syndrome (SARS) chymotrypsin-like protease (3CL(pro)) are described. Focusing on hydrophobic interactions at the S2 site, the decahydroisoquinolin scaffold was designed by connecting the P2 site cyclohexyl group of the substrate-based inhibitor to the main-chain at the α-nitrogen atom of the P2 position via a methylene linker. Starting from a cyclohexene enantiomer obtained by salt resolution, trans-decahydroisoquinolin derivatives were synthesized. All decahydroisoquinolin inhibitors synthesized showed moderate but clear inhibitory activities for SARS 3CL(pro), which confirmed the fused ring structure of the decahydroisoquinolin functions as a novel scaffold for SARS 3CL(pro) inhibitor. X-ray crystallographic analyses of the SARS 3CL(pro) in a complex with the decahydroisoquinolin inhibitor revealed the expected interactions at the S1 and S2 sites, as well as additional interactions at the N-substituent of the inhibitor. Copyright © 2014 Elsevier Ltd. All rights reserved.

Ethylene biosynthesis by 1-aminocyclopropane-1-carboxylic acid oxidase: a DFT study.

PubMed

Bassan, Arianna; Borowski, Tomasz; Schofield, Christopher J; Siegbahn, Per E M

2006-11-24

The reaction catalyzed by the plant enzyme 1-aminocyclopropane-1-carboxylic acid oxidase (ACCO) was investigated by using hybrid density functional theory. ACCO belongs to the non-heme iron(II) enzyme superfamily and carries out the bicarbonate-dependent two-electron oxidation of its substrate ACC (1-aminocyclopropane-1-carboxylic acid) concomitant with the reduction of dioxygen and oxidation of a reducing agent probably ascorbate. The reaction gives ethylene, CO(2), cyanide and two water molecules. A model including the mononuclear iron complex with ACC in the first coordination sphere was used to study the details of O-O bond cleavage and cyclopropane ring opening. Calculations imply that this unusual and complex reaction is triggered by a hydrogen atom abstraction step generating a radical on the amino nitrogen of ACC. Subsequently, cyclopropane ring opening followed by O-O bond heterolysis leads to a very reactive iron(IV)-oxo intermediate, which decomposes to ethylene and cyanoformate with very low energy barriers. The reaction is assisted by bicarbonate located in the second coordination sphere of the metal.

Light and/or atomic beams to detect ultraweak gravitational effects

NASA Astrophysics Data System (ADS)

Tartaglia, Angelo; Belfi, Jacopo; Beverini, Nicolò; Di Virgilio, Angela; Ortolan, Antonello; Porzio, Alberto; Ruggiero, Matteo Luca

2014-06-01

We shall review the opportunities lent by ring lasers and atomic beams interferometry in order to reveal gravitomagnetic effects on Earth. Both techniques are based on the asymmetric propagation of waves in the gravitational field of a rotating mass; actually the times of flight for co- or counter-rotating closed paths turn out to be different. After discussing properties and limitations of the two approaches we shall describe the proposed GINGER experiment which is being developed for the Gran Sasso National Laboratories in Italy. The experimental apparatus will consist of a three-dimensional array of square rings, 6m × 6m, that is planned to reach a sensitivity in the order of 1prad/√Hertz or better. This sensitivity would be one order of magnitude better than the best existing ring, which is the G-ring in Wettzell, Bavaria, and would allow for the terrestrial detection of the Lense-Thirring effect and possibly of deviations from General Relativity. The possibility of using either the ring laser approach or atomic interferometry in a space mission will also be considered. The technology problems are under experimental study using both the German G-ring and the smaller G-Pisa ring, located at the Gran Sasso.

Nucleophilic ring opening of bridging thietanes in open triosmium cluster complexes

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

Adams, R.D.; Belinski, J.A.

1992-07-01

The complexes Os{sub 3}(CO){sub 9}({mu}{sub 3}-S)[{mu}-SCH{sub 2}CMe{sub 2}CMe{sub 2}CH{sub 2}] (1) and Os{sub 3}(CO){sub 9}({mu}{sub 3}-S)[{mu}-SCH{sub 2}CH{sub 2}CH{sub 2}] (2) were obtained from the reactions of Os{sub 3}(CO){sub 10}({mu}{sub 3}-S) with 3,3-dimethylthietane (DMT) and thietane, respectively, at -42 {degree}C in the presence of Me{sub 3}NO. Compound 1 was characterized by a single-crystal X-ray diffraction analysis and was found to contain a DMT group bridging two of the nonbonded metal atoms in the open cluster of three metal atoms by using both lone pairs of electrons on the sulfur atom. Compound 1 reacted with bis(triphenylphosphine)nitrogen(1+) chloride ([PPN]Cl) at 25 {degrees}C tomore » yield the salt [PPN][Os{sub 3}-(CO){sub 9}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}Cl)({mu}{sub 3}-S)] (3; 76%), in which the chloride ion was added to one of the methylene groups of the DMT ring in a process that caused the ring to open by cleavage of one of the carbon-sulfur bonds. A 4-chloro-3,3-dimethylpropanethiolate ligand bridges the open edge of the anionic triosmium cluster. Compound 3 was converted to the neutral complex Os{sub 3}(CO){sub 9}[{mu}-SCH{sub 2}CMe{sub 2}CMe{sub 2}CH{sub 2}Cl]({mu}{sub 3}-S)({mu}-H) (4) by reaction with HCl at 25 {degrees}C. Compound 4 is structurally similar to 3, except that is contains a hydride ligand bridging one of the two metal-metal bonds. Compounds 1 and 2 react with HCl in CH{sub 2}Cl{sub 2} solvent to yield the neutral compounds 4 and Os{sub 3}(CO){sub 9}[{mu}-SCH{sub 2}CH{sub 2}CH{sub 2}Cl]({mu}{sub 3}-S)({mu}-H) (5) in 89% and 90% yields, respectively, in one step. 11 refs., 3 figs., 10 tabs.« less

Ultraviolet absorption: Experiment MA-059. [measurement of atmospheric species concentrations

NASA Technical Reports Server (NTRS)

Donahue, T. M.; Hudson, R. D.; Rawlins, W. T.; Anderson, J.; Kaufman, F.; Mcelroy, M. B.

1977-01-01

A technique devised to permit the measurement of atmospheric species concentrations is described. This technique involves the application of atomic absorption spectroscopy and the quantitative observation of resonance fluorescence in which atomic or molecular species scatter resonance radiation from a light source into a detector. A beam of atomic oxygen and atomic nitrogen resonance radiation, strong unabsorbable oxygen and nitrogen radiation, and visual radiation was sent from Apollo to Soyuz. The density of atomic oxygen and atomic nitrogen between the two spacecraft was measured by observing the amount of resonance radiation absorbed when the line joining Apollo and Soyuz was perpendicular to their velocity with respect to the ambient atmosphere. Results of postflight analysis of the resonance fluorescence data are discussed.

Infrared spectroscopy of matrix-isolated neutral polycyclic aromatic nitrogen heterocycles: The acridine series.

PubMed

Mattioda, A L; Bauschlicher, C W; Ricca, A; Bregman, J; Hudgins, D M; Allamandola, L J

2017-06-15

The matrix-isolated, mid-infrared spectra of seven acridine-based polycyclic aromatic nitrogen heterocycles (PANHs) have been measured and compared to their non-nitrogen containing parent molecule. The acridine species investigated include acridine, benz[a]acridine, benz[c]acridine, dibenz[a,j]acridine, dibenz[c,h]acridine, dibenz[a,h]acridine and dibenz[a,c]acridine. The previously reported results for 1 and 2-azabenz[a]anthracenes are included for comparison. The experimentally determined band frequencies and intensities are compared with their B3LYP/6-31G(d) values. The overall agreement between experimental and theoretical values is good and in line with our previous investigations. Shifts, typically to the blue, are noted for the C-H out-of-plane (CH oop ) motions upon insertion of a nitrogen atom. The formation of a bay region upon addition of additional benzene rings to the anthracene/acridine structure splits the solo hydrogen motions into a bay region solo and an external solo hydrogen, with the bay region solo hydrogen coupling to the quartet hydrogen motions and the external solo hydrogen coupling with the duo hydrogen motions resulting in an extreme decrease in intensity for the CH oop solo hydrogen band when the external hydrogen is replaced by a nitrogen atom. The C-C and C-H in-plane region of this acridine series exhibits the characteristic two fold increase in intensity, noted previously for PANHs. The strong ≈1400cm -1 band, which was identified in the previous PANH study, is noted in several molecular species as well as another strong PANH feature between 1480 and 1515cm -1 for several molecules. The presence of these strong bands appear to be primarily responsible for the two-fold increase in the C-H in-plane region's (1100-1600cm -1 ) intensity. The C-H stretching region can be characterized by contributions from the solo (bay or external), duo and quartet hydrogens, similar to what was observed in the dibenzopolyacene compounds. Published by Elsevier B.V.

Synthesis, structural characterization and DNA interaction of zinc complex from 2,6-diacetylpyridine dihydrazone and {4-[(2E)-2-(hydroxyimino)acetyl]phenoxy} acetic acid.

PubMed

Gup, Ramazan; Gökçe, Cansu; Dilek, Nefise

2015-03-01

A new water soluble zinc complex has been prepared and structurally characterized. The Zn(II) complex was synthesized by the reaction of 2,6-diacetylpyridine dihydrazone (dph) with {4-[(2E)-2-(hydroxyimino)acetyl]phenoxy} acetic acid (H₂L) in the presence of zinc(II) acetate. Single crystal X-ray diffraction study revealed that the zinc ion is situated in distorted trigonal-bipyramidal environment where the equatorial position is occupied by the nitrogen atom of pyridine ring and the oxygen atoms of acetate groups of two oxime ligands (H₂L) whereas the axial positions of the zinc complex are occupied by the imine nitrogen atoms of dph ligand. Characterization of the complex with FTIR, (1)H and (13)C NMR, UV-vis and elemental analysis also confirmed the proposed structure. Interaction of the Zn(II) complex with calf-thymus DNA (CT-DNA) was investigated through UV-vis spectroscopy and viscosity measurements. The results suggest that the complex preferably bind to DNA through the groove binding mode. The zinc complex cleaves plasmid pBR 322 DNA in the presence and absence of an oxidative agent (H₂O₂), possibly through a hydrolytic pathway which is also supported by DNA cleave experiments in the presence of different radical scavengers. The nuclease activity of the zinc complex significantly depends on concentration of the complex and incubation time both in the presence and absence of H₂O₂. DNA cleave activity is inhibited in the presence of methyl green indicating that the zinc complex seems to bind the major groove of DNA. Copyright © 2015 Elsevier B.V. All rights reserved.

Enumeration method for tree-like chemical compounds with benzene rings and naphthalene rings by breadth-first search order.

PubMed

Jindalertudomdee, Jira; Hayashida, Morihiro; Zhao, Yang; Akutsu, Tatsuya

2016-03-01

Drug discovery and design are important research fields in bioinformatics. Enumeration of chemical compounds is essential not only for the purpose, but also for analysis of chemical space and structure elucidation. In our previous study, we developed enumeration methods BfsSimEnum and BfsMulEnum for tree-like chemical compounds using a tree-structure to represent a chemical compound, which is limited to acyclic chemical compounds only. In this paper, we extend the methods, and develop BfsBenNaphEnum that can enumerate tree-like chemical compounds containing benzene rings and naphthalene rings, which include benzene isomers and naphthalene isomers such as ortho, meta, and para, by treating a benzene ring as an atom with valence six, instead of a ring of six carbon atoms, and treating a naphthalene ring as two benzene rings having a special bond. We compare our method with MOLGEN 5.0, which is a well-known general purpose structure generator, to enumerate chemical structures from a set of chemical formulas in terms of the number of enumerated structures and the computational time. The result suggests that our proposed method can reduce the computational time efficiently. We propose the enumeration method BfsBenNaphEnum for tree-like chemical compounds containing benzene rings and naphthalene rings as cyclic structures. BfsBenNaphEnum was from 50 times to 5,000,000 times faster than MOLGEN 5.0 for instances with 8 to 14 carbon atoms in our experiments.

Substituent effects on rates and torquoselectivities of electrocyclic ring-openings of N-substituted 2-azetines.

PubMed

Lopez, Steven A; Houk, K N

2014-07-03

Transition structures for the conrotatory electrocyclic ring-opening reactions of N-substituted 2-azetines were computed with the density functional M06-2X/6-31+G(d,p). A wide range of substituents from π acceptors (e.g., CHO, CN) to π donors (NMe2, OMe) was explored. Acceptor substituents delocalize the nitrogen lone pair and stabilize the reactant state of 2-azetines, while donors destabilize the 2-azetine reactant state. The conrotatory ring-opening is torquoselective, and the transition state for the outward rotation of the N-substituent and inward rotation of the nitrogen lone pair is preferred. This transition structure is stabilized by an interaction between the nitrogen lone pair and the vacant π* orbital. The activation free energies are linearly related to the reaction free energies and the Taft σR(0) parameter.

Crystal structure of 5''-benzyl-idene-1'-methyl-4'-phenyl-tri-spiro-[ace-naphthyl-ene-1,2'-pyrrolidine-3',1''-cyclo-hexane-3'',2'''-[1,3]dioxane]-2,6''-dione.

PubMed

Chandralekha, Kuppan; Gavaskar, Deivasigamani; Sureshbabu, Adukamparai Rajukrishnan; Lakshmi, Srinivasakannan

2016-03-01

In the title compound, C36H31NO4, two spiro links connect the methyl-substituted pyrrolidine ring to the ace-naphthyl-ene and cyclo-hexa-none rings. The cyclo-hexa-none ring is further connected to the dioxalane ring by a third spiro junction. The five-membered ring of the ace-naphthylen-1-one ring system adopts a flattened envelope conformation with the ketonic C atom as flap, whereas the dioxalane and pyrrolidine rings each have a twist conformation. The cyclo-hexa-none ring assumes a boat conformation. Three intra-molecular C-H⋯O hydrogen bonds involving both ketonic O atoms as acceptors are present. In the crystal, C-H⋯O hydrogen bonds connect centrosymmetrically related mol-ecule into chains parallel to the b axis, forming rings of R 2 (2)(10)and R 2 (2)(8) graph-set motifs.

Experimental and theoretical investigation of the inhibitory effect of new pyridazine derivatives for the corrosion of mild steel in 1 M HCl

NASA Astrophysics Data System (ADS)

Mashuga, Motsie E.; Olasunkanmi, Lukman O.; Ebenso, Eno E.

2017-05-01

The effects of four pyridazine derivatives namely, 2-(6-chloropyridazin-3-yl)-2-phenylacetonitrile (P1), 3-(6-chloro-3-pyridazinyl)-1H-indole (P2), 4-(6-chloropyridazin-3-yl)benzoic acid (P3) and 3-(6-chloropyridazin-3-yl)benzoic acid (P4) on electrochemical dissolution of mild steel in 1 M HCl were studied using electrochemical, spectroscopic, and theoretical computational chemistry techniques. The inhibition efficiency increases with increasing concentration of the inhibitors and the shift in corrosion potentials obtained revealed that the compounds are mixed-type inhibitors and steel dissolution was found to be a charge transfer process with the steel/electrolyte interface showed pseudo-capacitive behaviour. P1 and P2 showed the best protection performances for mild steel in the studied medium, attributable to the presence of more nitrogen atoms and unsaturated groups in their molecules compared to P3 and P4. The experimental adsorption data obeyed the Langmuir and Temkin isotherm models and was found to involve both physisorption and chemisorption. Spectroscopic studies revealed that the inhibitor molecules interact chemically with mild steel and the pyridazine ring is actively involved in these interactions. Quantum chemical calculations also showed that pyridazine ring has the tendency of interacting with metallic atoms via both forward and backward donations. Molecular dynamic simulation revealed that the molecules can adsorb strongly onto the surface of iron in a near flat orientation.

Electronic structure of graphene nanoribbons doped with nitrogen atoms: a theoretical insight.

PubMed

Torres, A E; Fomine, S

2015-04-28

The electronic structure of graphene nanoribbons doped with a graphitic type of nitrogen atoms has been studied using B3LYP, B2PLYP and CAS methods. In all but one case the restricted B3LYP solutions were unstable and the CAS calculations provided evidence for the multiconfigurational nature of the ground state with contributions from two dominant configurations. The relative stability of the doped nanoribbons depends mostly on the mutual position of the dopant atoms and notably less on the position of nitrogen atoms within the nanoribbon. N-graphitic doping affects cationic states much more than anionic ones due the participation of the nitrogen atoms in the stabilization of the positive charge, resulting in a drop in ionization energies (IPs) for N-graphitic doped systems. Nitrogen atoms do not participate in the negative charge stabilization of anionic species and, therefore, the doping does not affect the electron affinities (EAs). The unrestricted B3LYP method is the method of choice for the calculation of IPs and EAs. Restricted B3LYP and B2PLYP produces unreliable results for both IPs and EAs while CAS strongly underestimates the electron affinities. This is also true for the reorganization energies where restricted B3LYP produces qualitatively incorrect results. Doping changes the reorganization energy of the nanoribbons; the hole reorganization energy is generally higher than the corresponding electron reorganization energy due to the participation of nitrogen atoms in the stabilization of the positive charge.

Reactivity of amino acid anions with nitrogen and oxygen atoms.

PubMed

Wang, Zhe-Chen; Li, Ya-Ke; He, Sheng-Gui; Bierbaum, Veronica M

2018-02-14

For many decades, astronomers have searched for biological molecules, including amino acids, in the interstellar medium; this endeavor is important for investigating the hypothesis of the origin of life from space. The space environment is complex and atomic species, such as nitrogen and oxygen atoms, are widely distributed. In this work, the reactions of eight typical deprotonated amino acids (glycine, alanine, cysteine, proline, aspartic acid, histidine, tyrosine, and tryptophan) with ground state nitrogen and oxygen atoms are studied by experiment and theory. These amino acid anions do not react with nitrogen atoms. However, the reactions of these ions with oxygen atoms show an intriguing variety of ionic products and the reaction rate constants are of the order of 10 -10 cm 3 s -1 . Density functional calculations provide detailed mechanisms of the reactions, and demonstrate that spin conversion is essential for some processes. Our study provides important data and insights for understanding the kinetic and dynamic behavior of amino acids in space environments.

Bimetallic lanthanide amido complexes as highly active initiators for the ring-opening polymerization of lactides.

PubMed

Sun, Song; Nie, Kun; Tan, Yufang; Zhao, Bei; Zhang, Yong; Shen, Qi; Yao, Yingming

2013-02-28

A series of neutral bimetallic lanthanide amido complexes supported by rigid phenylene bridged bis(β-diketiminate) ligands were synthesized, and their catalytic behavior for the polymerization of L-lactide and rac-lactide was explored. The amine elimination reaction of Ln[N(TMS)(2)](3)(μ-Cl)Li(THF)(3) with PARA-H(2), [PARA-H(2) = 2[2,6-(i)Pr(2)C(6)H(3)NHC(Me)C(H)C(Me)N]-(para-phenylene)] in a 2:1 molar ratio in THF at 25 °C afforded the corresponding bimetallic lanthanide amido complexes PARA-{Ln[N(SiMe(3))(2)](2)}(2) [Ln = Nd(1), Sm(2), Y(3)] in high isolated yields. Similar reaction of Nd[N(TMS)(2)](3)(μ-Cl)Li(THF)(3) with META-H(2), [META-H(2) = 2[2,6-(i)Pr(2)C(6)H(3)NHC(Me)C(H)C(Me)N]-(meta-phenylene)] at 90 °C in toluene for about 48 h gave META-{Nd[N(SiMe(3))(2)](2)}(2) (4). Complexes 1-4 were well characterized by elemental analysis, IR spectroscopy, and their definitive structures were confirmed by an X-ray crystal structure analysis. The coordination environment and coordination geometry around the metal atoms are similar in these complexes. Each of the metal atoms is four-coordinated with two nitrogen atoms from the N,N-chelating β-diketiminate unit, and two nitrogen atoms from two (Me(3)Si)(2)N- groups to form a distorted tetrahedron. These complexes can serve as highly active initiators for L-lactide polymerization in toluene. In addition, they also showed high activity towards rac-lactide polymerization in THF at room temperature, giving heterotactic-enriched polymers (P(r) ≈ 0.70), and complex 4 displays obviously higher activity in comparison with complex 1.

Combined quantum-mechanics/molecular-mechanics dynamics simulation of A-DNA double strands irradiated by ultra-low-energy carbon ions

NASA Astrophysics Data System (ADS)

Ngaojampa, C.; Nimmanpipug, P.; Yu, L. D.; Anuntalabhochai, S.; Lee, V. S.

2011-02-01

In order to promote understanding of the fundamentals of ultra-low-energy ion interaction with DNA, molecular dynamics simulations using combined quantum-mechanics/molecular-mechanics of poly-AT and poly-GC A-DNA double strands irradiated by <200 eV carbon ions were performed to investigate the molecular implications of mutation bias. The simulations were focused on the responses of the DNA backbones and nitrogenous bases to irradiation. Analyses of the root mean square displacements of the backbones and non-hydrogen atoms of base rings of the simulated DNA structure after irradiation revealed a potential preference of DNA double strand separation, dependent on the irradiating energy. The results show that for the backbones, the large difference in the displacement between poly-GC and poly-AT in the initial time period could be the reason for the backbone breakage; for the nitrogenous base pairs, A-T is 30% more sensitive or vulnerable to ion irradiation than G-C, demonstrating a preferential, instead of random, effect of irradiation-induced mutation.

Synthesis, structure, and properties of nickel complexes with nitrilotris(methylenephosphonic acid) [Ni(H{sub 2}O)3N(CH2PO{sub 3}H){sub 3}] and Na{sub 4}[Ni(H{sub 2}O)N(CH{sub 2}PO{sub 3}){sub 3}] ∙ 11H{sub 2}O

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

Somov, N. V., E-mail: somov@phys.unn.ru; Chausov, F. F., E-mail: chaus@yandex.ru; Zakirova, R. M.

2016-03-15

Nitrilotris(methylenephosphonato)triaquanickel and tetrasodium nitrilotris(methylenephosphonato) aquanickelate undecahydrate were synthesized and characterized. The crystal of [Ni(H{sub 2}O){sub 3}N(CH{sub 2}PO{sub 3}H){sub 3}] is composed of linear coordination polymers and belongs to sp. gr. P2{sub 1}/c, Z = 4, a = 9.17120(10) Å, b = 16.05700(10) Å, c = 9.70890(10) Å, β = 115.830(2)°. The Ni atom is in an octahedral coordination formed by two oxygen atoms of one phosphonate ligand, one oxygen atom of another ligand molecule, and three water molecules in a meridional configuration. The crystal of Na{sub 4}[Ni(H{sub 2}O)N(CH{sub 2}PO{sub 3}){sub 3}] ∙ 11H{sub 2}O has an island dimeric chelate structuremore » and belongs to sp. gr. C2/c, Z = 8, a = 18.7152(2) Å, b = 12.05510(10) Å, c = 21.1266(2) Å, β = 104.4960(10)°. The Ni atom has a slightly distorted octahedral coordination involving one nitrogen atom and closes three five-membered N–C–P–O–Ni rings sharing the Ni–N bond.« less

AuNx stabilization with interstitial nitrogen atoms: A Density Functional Theory Study

NASA Astrophysics Data System (ADS)

Quintero, J. H.; Gonzalez-Hernandez, R.; Ospina, R.; Mariño, A.

2017-06-01

Researchers have been studying 4d and 5d Series Transition Metal Nitrides lately as a result of the experimental production of AuN, PtN, CuN. In this paper, we used the Density Functional Theory (DFT) implementing a pseudopotential plane-wave method to study the incorporation of nitrogen atoms in the face-centered cube (fcc) lattice of gold (Au). First, we took the fcc structure of gold, and gradually located the nitrogen atoms in tetrahedral (TH) and octahedral (OH) interstitial sites. AuN stabilized in: 2OH (30%), 4OH and 4TH (50%), 4OH - 2TH (close to the wurtzite structure) and 6TH (60%). This leads us to think that AuN behaves like a Transition Metal Nitride since the nitrogen atoms look for tetrahedral sites.

4-(4-Bromo-phen-yl)-1-(2,6-difluoro-benz-yl)-3-(3,4,5-trimeth-oxy-phen-yl)-1H-1,2,4-triazole-5(4H)-thione.

PubMed

Fun, Hoong-Kun; Ooi, Chin Wei; Chandrakantha, B; Isloor, Arun M; Shetty, Prakash

2012-01-01

In the title compound, C(24)H(20)BrF(2)N(3)O(3)S, the triazole ring (r.m.s. deviation = 0.0107 Å) makes dihedral angles of 28.18 (14), 63.76 (14) and 77.01 (18)°, respectively, with the trimeth-oxy-, bromo-, and difluoro-substituted benzene rings. The C atoms of the meta meth-oxy groups are roughly coplanar with their ring [displacements = -0.289 (4) and 0.083 (7) Å], whereas the C atom of the para group is displaced [1.117 (3) Å]. In the crystal, inversion dimers linked by two pairs of C-H⋯O hydrogen bonds occur. The ring motif of the two hydrogen bonds to their symmetry-generated O-atom acceptors is R(2) (2)(8).

High-energy accelerator for beams of heavy ions

DOEpatents

Martin, Ronald L.; Arnold, Richard C.

1978-01-01

An apparatus for accelerating heavy ions to high energies and directing the accelerated ions at a target comprises a source of singly ionized heavy ions of an element or compound of greater than 100 atomic mass units, means for accelerating the heavy ions, a storage ring for accumulating the accelerated heavy ions and switching means for switching the heavy ions from the storage ring to strike a target substantially simultaneously from a plurality of directions. In a particular embodiment the heavy ion that is accelerated is singly ionized hydrogen iodide. After acceleration, if the beam is of molecular ions, the ions are dissociated to leave an accelerated singly ionized atomic ion in a beam. Extraction of the beam may be accomplished by stripping all the electrons from the atomic ion to switch the beam from the storage ring by bending it in magnetic field of the storage ring.

Determination of As in tree-rings of poplar (Populus alba L.) by U-shaped DC arc.

PubMed

Marković, D M; Novović, I; Vilotić, D; Ignjatović, Lj

2009-04-01

An argon-stabilized U-shaped DC arc with a system for aerosol introduction was used for determination of As in poplar (Populus alba L.) tree-rings. After optimization of the operating parameters and selection of the most appropriate signal integration time (30 s), the limit of detection for As was reduced to 15.0 ng/mL. This detection limit obtained with the optimal integration time was compared with those for other methods: inductively coupled plasma-atomic emission spectrometry (ICP-AES), direct coupled plasma-atomic emission spectrometry (DCP-AES), microwave induced plasma-atomic emission spectrometry (MIP-AES) and improved thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS). Arsenic is toxic trace element which can adversely affect plant, animal and human health. As an indicator of environment pollution we collected poplar tree-rings from two locations. The first area was close to the "Nikola Tesla" (TENT-A) power plant, Obrenovac, while the other was in the urban area of Novi Sad. In all cases elevated average concentrations of As were registered in poplar tree-rings from the Obrenovac location.

THE EFFECTS OF INITIAL ABUNDANCES ON NITROGEN IN PROTOPLANETARY DISKS

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

Schwarz, Kamber R.; Bergin, Edwin A.

2014-12-20

The dominant form of nitrogen provided to most solar system bodies is currently unknown, though available measurements show that the detected nitrogen in solar system rocks and ices is depleted with respect to solar abundances and the interstellar medium. We use a detailed chemical/physical model of the chemical evolution of a protoplanetary disk to explore the evolution and abundance of nitrogen-bearing molecules. Based on this model, we analyze how initial chemical abundances provided as either gas or ice during the early stages of disk formation influence which species become the dominant nitrogen bearers at later stages. We find that amore » disk with the majority of its initial nitrogen in either atomic or molecular nitrogen is later dominated by atomic and molecular nitrogen as well as NH{sub 3} and HCN ices, where the dominant species varies with disk radius. When nitrogen is initially in gaseous ammonia, it later becomes trapped in ammonia ice except in the outer disk where atomic nitrogen dominates. For a disk with the initial nitrogen in the form of ammonia ice, the nitrogen remains trapped in the ice as NH{sub 3} at later stages. The model in which most of the initial nitrogen is placed in atomic N best matches the ammonia abundances observed in comets. Furthermore, the initial state of nitrogen influences the abundance of N{sub 2}H{sup +}, which has been detected in protoplanetary disks. Strong N{sub 2}H{sup +} emission is found to be indicative of an N{sub 2} abundance greater than n{sub N{sub 2}}/n{sub H{sub 2}}>10{sup −6} in addition to tracing the CO snow line. Our models also indicate that NO is potentially detectable, with lower N gas abundances leading to higher NO abundances.« less

Virtual Exploration of the Ring Systems Chemical Universe.

PubMed

Visini, Ricardo; Arús-Pous, Josep; Awale, Mahendra; Reymond, Jean-Louis

2017-11-27

Here, we explore the chemical space of all virtually possible organic molecules focusing on ring systems, which represent the cyclic cores of organic molecules obtained by removing all acyclic bonds and converting all remaining atoms to carbon. This approach circumvents the combinatorial explosion encountered when enumerating the molecules themselves. We report the chemical universe database GDB4c containing 916 130 ring systems up to four saturated or aromatic rings and maximum ring size of 14 atoms and GDB4c3D containing the corresponding 6 555 929 stereoisomers. Almost all (98.6%) of these ring systems are unknown and represent chiral 3D-shaped macrocycles containing small rings and quaternary centers reminiscent of polycyclic natural products. We envision that GDB4c can serve to select new ring systems from which to design analogs of such natural products. The database is available for download at www.gdb.unibe.ch together with interactive visualization and search tools as a resource for molecular design.

Acid-Base Interactions of Polystyrene Sulfonic Acid in Amorphous Solid Dispersions Using a Combined UV/FTIR/XPS/ssNMR Study.

PubMed

Song, Yang; Zemlyanov, Dmitry; Chen, Xin; Nie, Haichen; Su, Ziyang; Fang, Ke; Yang, Xinghao; Smith, Daniel; Byrn, Stephen; Lubach, Joseph W

2016-02-01

This study investigates the potential drug-excipient interactions of polystyrene sulfonic acid (PSSA) and two weakly basic anticancer drugs, lapatinib (LB) and gefitinib (GB), in amorphous solid dispersions. Based on the strong acidity of the sulfonic acid functional group, PSSA was hypothesized to exhibit specific intermolecular acid-base interactions with both model basic drugs. Ultraviolet (UV) spectroscopy identified red shifts, which correlated well with the color change observed in lapatinib-PSSA solutions. Fourier transform infrared (FTIR) spectra suggest the protonation of the quinazoline nitrogen atom in both model compounds, which agrees well with data from the crystalline ditosylate salt of lapatinib. X-ray photoelectron spectroscopy (XPS) detected increases in binding energy of the basic nitrogen atoms in both lapatinib and gefitinib, strongly indicating protonation of these nitrogen atoms. (15)N solid-state NMR spectroscopy provided direct spectroscopic evidence for protonation of the quinazoline nitrogen atoms in both LB and GB, as well as the secondary amine nitrogen atom in LB and the tertiary amine nitrogen atom in GB. The observed chemical shifts in the LB-PSSA (15)N spectrum also agree very well with the lapatinib ditosylate salt where proton transfer is known. Additionally, the dissolution and physical stability behaviors of both amorphous solid dispersions were examined. PSSA was found to significantly improve the dissolution of LB and GB and effectively inhibit the crystallization of LB and GB under accelerated storage conditions due to the beneficial strong intermolecular acid-base interaction between the sulfonic acid groups and basic nitrogen centers.

Thermoluminescence Dynamics During Destructions of Porous Structures Formed by Nitrogen Nanoclusters in Bulk Superfluid Helium

NASA Astrophysics Data System (ADS)

Meraki, Adil; Mao, Shun; McColgan, Patrick T.; Boltnev, Roman E.; Lee, David M.; Khmelenko, Vladimir V.

2016-11-01

We studied the dynamics of thermoluminescence during destruction of porous structures formed by nanoclusters of nitrogen molecules containing high concentrations of stabilized nitrogen atoms. The porous structures were formed in bulk superfluid helium by injection of the products of discharges in nitrogen-helium gas mixtures through the liquid helium surface. Fast recombination of nitrogen atoms during warming-up led to explosive destruction of the porous structures accompanied by bright flashes. Intense emissions from the α -group of nitrogen atoms, the β -group of oxygen atoms and the Vegard-Kaplan bands of N_2 molecules were observed at the beginning of destruction. At the end of destruction the M- and β -bands of NO molecules as well as bands of O_2 molecules were also observed. Observation of the emissions from NO molecules at the end of destruction was explained by processes of accumulation of NO molecules in the system due to the large van der Waals interaction of NO molecules. For the first time, we observed the emission of the O_2 molecules at the end of destruction of the porous nitrogen structures as a result of the (NO)_2 dimer formation in solid nitrogen and subsequent processes leading to the appearance of excited O_2 molecules.

3He NMR studies on helium-pyrrole, helium-indole, and helium-carbazole systems: a new tool for following chemistry of heterocyclic compounds.

PubMed

Radula-Janik, Klaudia; Kupka, Teobald

2015-02-01

The (3)He nuclear magnetic shieldings were calculated for free helium atom and He-pyrrole, He-indole, and He-carbazole complexes. Several levels of theory, including Hartree-Fock (HF), Second-order Møller-Plesset Perturbation Theory (MP2), and Density Functional Theory (DFT) (VSXC, M062X, APFD, BHandHLYP, and mPW1PW91), combined with polarization-consistent pcS-2 and aug-pcS-2 basis sets were employed. Gauge-including atomic orbital (GIAO) calculated (3)He nuclear magnetic shieldings reproduced accurately previously reported theoretical values for helium gas. (3)He nuclear magnetic shieldings and energy changes as result of single helium atom approaching to the five-membered ring of pyrrole, indole, and carbazole were tested. It was observed that (3)He NMR parameters of single helium atom, calculated at various levels of theory (HF, MP2, and DFT) are sensitive to the presence of heteroatomic rings. The helium atom was insensitive to the studied molecules at distances above 5 Å. Our results, obtained with BHandHLYP method, predicted fairly accurately the He-pyrrole plane separation of 3.15 Å (close to 3.24 Å, calculated by MP2) and yielded a sizable (3)He NMR chemical shift (about -1.5 ppm). The changes of calculated nucleus-independent chemical shifts (NICS) with the distance above the rings showed a very similar pattern to helium-3 NMR chemical shift. The ring currents above the five-membered rings were seen by helium magnetic probe to about 5 Å above the ring planes verified by the calculated NICS index. Copyright © 2014 John Wiley & Sons, Ltd.

Mixing of gaseous reactants in chemical generation of atomic iodine for COIL: two-dimensional study

NASA Astrophysics Data System (ADS)

Jirasek, Vit; Spalek, Otomar; Kodymova, Jarmila; Censky, Miroslav

2003-11-01

Two-dimensional CFD model was applied for the study of mixing and reaction between gaseous chlorine dioxide and nitrogen monoxide diluted with nitrogen during atomic iodine generation. The influence of molecular diffusion on the production of atomic chlorine as a precursor of atomic iodine was predominantly studied. The results were compared with one-dimensional modeling of the system.

High-Affinity Accumulation of Chloroquine by Mouse Erythrocytes Infected with Plasmodium berghei

PubMed Central

Fitch, Coy D.; Yunis, Norman G.; Chevli, Rekha; Gonzalez, Yolanda

1974-01-01

Washed erythrocytes infected with chloroquine-susceptible (CS) or with chloroquine-resistant (CR) P. berghei were used in model systems in vitro to study the accumulation of chloroquine with high affinity. The CS model could achieve distribution ratios (chloroquine in cells: chloroquine in medium) of 100 in the absence of substrate. 200—300 in the presence of 10 mM pyruvate or lactate, and over 600 in the presence of 1 mM glucose or glycerol. In comparable studies of the CR model, the distribution ratios were 100 in the absence of substrate and 300 or less in the presence of glucose or glycerol. The presence of lactate stimulated chloroquine accumulation in the CR model, whereas the presence of pyruvate did not. Lactate production from glucose and glycerol was undiminished in the CR model, and ATP concentrations were higher than in the CS model. Cold, iodoacetate, 2,4-dinitrophenol, or decreasing pH inhibited chloroquine accumulation in both models. These findings demonstrate substrate involvement in the accumulation of chloroquine with high affinity. In studies of the CS model, certain compounds competitively inhibited chloroquine accumulation, while others did not. This finding is attributable to a specific receptor that imposes structural constraints on the process of accumulation. For chloroquine analogues, the position and length of the side chain, the terminal nitrogen atom of the side chain, and the nitrogen atom in the quinoline ring are important determinants of binding to this receptor. PMID:4600044

Pd-catalyzed versus uncatalyzed, PhI(OAc)2-mediated cyclization reactions of N6-([1,1'-biaryl]-2-yl)adenine nucleosides.

PubMed

Satishkumar, Sakilam; Poudapally, Suresh; Vuram, Prasanna K; Gurram, Venkateshwarlu; Pottabathini, Narender; Sebastian, Dellamol; Yang, Lijia; Pradhan, Padmanava; Lakshman, Mahesh K

2017-11-09

In this work we have assessed reactions of N 6 -([1,1'-biaryl]-2-yl)adenine nucleosides with Pd(OAc) 2 and PhI(OAc) 2 , via a Pd II /Pd IV redox cycle. The substrates are readily obtained by Pd/Xantphos-catalyzed reaction of adenine nucleosides with 2-bromo-1,1'-biaryls. In PhMe, the N 6 -biarylyl nucleosides gave C6-carbazolyl nucleoside analogues by C-N bond formation with the exocyclic N 6 nitrogen atom. In the solvent screening for the Pd-catalyzed reactions, an uncatalyzed process was found to be operational. It was observed that the carbazolyl products could also be obtained in the absence of a metal catalyst by reaction with PhI(OAc) 2 in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP). Thus, under Pd catalysis and in HFIP, reactions proceed to provide carbazolyl nucleoside analogues, with some differences. If reactions of N 6 -biarylyl nucleoside substrates were conducted in MeCN, formation of aryl benzimidazopurinyl nucleoside derivatives was observed in many cases by C-N bond formation with the N 1 ring nitrogen atom of the purine (carbazole and benzimidazole isomers are readily separated by chromatography). Whereas Pd II /Pd IV redox is responsible for carbazole formation under the metal-catalyzed conditions, in HFIP and MeCN radical cations and/or nitrenium ions can be intermediates. An extensive set of radical inhibition experiments was conducted and the data are presented.

Nucleophilic ring opening of bridging thietane ligands in trirhenium carbonyl cluster complexes

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

Adams, R.D.; Cortopassi, J.E.; Falloon, S.B.

1992-11-01

The reactions of 3,3-dimethylthietane, SCH{sub 2}CMe{sub 2}CH{sub 2} (3,3-DMT), and thietane, SCH{sub 2}CH{sub 2}CH{sub 2}, with Re{sub 3}(CO){sub 10}[{mu}-SCH{sub 2}CH{sub 2}CH{sub 2}]({mu}-H){sub 3}, 2b. Compound 2a was characterized crystallographically and was found to consist of a trirhenium cluster with three bridging hydride ligands and a bridging thietane ligand coordinated through its sulfur atom. 2a and 2b react with halide ions by ring-opening additions to the 3,3-DMT ligand to yield the complex anions [Re{sub 3}(CO){sub 10}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}x)({mu}-h){sub 3}]{sup -} 3A-6A, X = F (71%), Cl(71%), Br(84%), I(87%) and [Re{sub 3}(CO){sub 10}({mu}-SCH{sub 2}CH{sub 2}CH{sub 2}Cl)({mu}-H){sub 3}]{sup -}, 4b (67%). Similarly,more » addition of NMe{sub 3} to 2a and 2b yielded the ring-opened zwitterions Re{sub 3}(CO){sub 10}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}NMe{sub 3})({mu}-H){sub 3}, 7 a crystographically. They are zwitterions positively charged at the nitrogen atoms and negatively charged on the trirhenium clusters. Complex 7b was also obtained in a 48% yield from the reaction of Re{sub 3}(C){sub 12}({mu}-H){sub 3} with Me{sub 3}NO in the presence of thietane, but the corresponding reaction using 3,3-DMT yielded only 2a and Re{sub 3}(CO){sub 11}(SCH{sub 2}CMe{sub 2}CH{sub 2})({mu}-H){sub 3}, 8. Attempts to obtain a ring-opening addition to 2a by reaction with PMe{sub 2}Ph yielded only Re{sub 3}(CO){sub 10}(PMe{sub 2}PH){sub 2}({mu}-H){sub 3} by ligand substitution. Attempts to obtain ring opening addition to 8 by reaction with I{sup -} yielded only [Re{sub 3}(CO){sub 11}I({mu}-H){sub 3}]{sup -} by ligand substitution. 20 refs., 3 figs., 10 tabs.« less

{pi}-{pi} Interactions and magnetic properties in a series of hybrid inorganic-organic crystals

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

Gonzalez, M.; Lemus-Santana, A.A.; Rodriguez-Hernandez, J.

The series of hybrid inorganic-organic solids T(Im){sub 2}[Ni(CN){sub 4}] with T=Fe, Co, Ni and Im=imidazole were prepared by soft chemical routes from aqueous solutions of the involved building units: imidazole, T{sup 2+} metal and the [Ni(CN){sub 4}]{sup 2-} anionic block. The obtained samples were characterized from infrared and UV-vis spectroscopies, and thermogravimetric, X-ray diffraction and magnetic measurements. Anhydrous solids which crystallize with a monoclinic unit cell, in the I2/a space group with four formula units per cell (Z=4) were obtained. Their crystal structure was solved ab initio from the recorded X-ray powder patterns and then refined by the Rietveld method.more » The metal T is found with octahedral coordination to four N ends of CN groups and two imidazole molecules while the inner Ni atom preserves its planar coordination. The system of layers remains stacked in an ordered 3D structure through dipole-dipole and {pi}-{pi} interactions between imidazole rings from neighboring layers. In this way, a pillared structure is achieved without requiring the coordination of both nitrogen atoms from imidazole ring. The recorded magnetic data indicate the occurrence of a predominant ferromagnetic interaction at low temperature for Co and Ni but not for Fe. Such magnetic ordering is more favorable for Ni with transition temperature of 14.67 K, which was ascribed to the relatively high polarizing power for this metal. Within the considered T metals, to nickel the highest electron-withdrawing ability corresponds and this leads to an increase for the metal-ligand electron clouds overlapping and to a stronger {pi}-{pi} attractive interaction, two factors that result into a higher magnetic ordering temperature. - Graphical Abstract: Magnetic ordering through the {pi}-{pi} interaction between the imidazole rings. Highlights: Black-Right-Pointing-Pointer Hybrid inorganic-organic solids. Black-Right-Pointing-Pointer Hybrid inorganic-organic molecular based magnets. Black-Right-Pointing-Pointer Ferromagnetic interaction through {pi}-{pi} stacking of imidazole rings. Black-Right-Pointing-Pointer Organic pillars formed through {pi}-{pi} stacking.« less

Electrochemical CO 2 Reduction with Atomic Iron-Dispersed on Nitrogen-Doped Graphene

DOE PAGES

Zhang, Chenhao; Yang, Shize; Wu, Jingjie; ...

2018-03-25

Electrochemical reduction of CO 2 provides an opportunity to reach a carbon-neutral energy recycling regime, in which CO 2 emissions from fuel use are collected and converted back to fuels. The reduction of CO 2 to CO is the first step toward the synthesis of more complex carbon-based fuels and chemicals. Therefore, understanding this step is crucial for the development of high-performance electrocatalyst for CO 2 conversion to higher order products such as hydrocarbons. In this paper, atomic iron dispersed on nitrogen-doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO 2 reduction to CO. Fe/NG has a lowmore » reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen-confined atomic Fe moieties on the nitrogen-doped graphene layer is confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. Finally, the CO 2 reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N 4) embedded in nitrogen-doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.« less

Electrochemical CO 2 Reduction with Atomic Iron-Dispersed on Nitrogen-Doped Graphene

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

Zhang, Chenhao; Yang, Shize; Wu, Jingjie

Electrochemical reduction of CO 2 provides an opportunity to reach a carbon-neutral energy recycling regime, in which CO 2 emissions from fuel use are collected and converted back to fuels. The reduction of CO 2 to CO is the first step toward the synthesis of more complex carbon-based fuels and chemicals. Therefore, understanding this step is crucial for the development of high-performance electrocatalyst for CO 2 conversion to higher order products such as hydrocarbons. In this paper, atomic iron dispersed on nitrogen-doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO 2 reduction to CO. Fe/NG has a lowmore » reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen-confined atomic Fe moieties on the nitrogen-doped graphene layer is confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. Finally, the CO 2 reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N 4) embedded in nitrogen-doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.« less

Pollution and Climate Effects on Tree-Ring Nitrogen Isotopes

NASA Astrophysics Data System (ADS)

Savard, M. M.; Bégin, C.; Marion, J.; Smirnoff, A.

2009-04-01

BACKGROUND Monitoring of nitrous oxide concentration only started during the last 30 years in North America, but anthropogenic atmospheric nitrogen has been significantly emitted over the last 150 years. Can geochemical characteristics of tree rings be used to infer past changes in the nitrogen cycle of temperate regions? To address this question we use nitrogen stable isotopes in 125 years-long ring series from beech specimens (Fagus grandifolia) of the Georgian Bay Islands National Park (eastern Ontario), and pine (Pinus strobus) and beech trees of the Arboretum Morgan near Montreal (western Quebec). To evaluate the reliability of the N stable isotopes in wood treated for removal of soluble materials, we tested both tree species from the Montreal area. The reproducibility from tree to tree was excellent for both pine and beech trees, the isotopic trends were strongly concordant, and they were not influenced by the heartwood-sapwood transition zone. The coherence of changes of the isotopic series observed for the two species suggests that their tree-ring N isotopic values can serve as environmental indicator. RESULTS AND INTERPRETATION In Montreal and Georgian Bay, the N isotopes show strong and similar parallel agreement (Gleichlaufigkeit test) with the climatic parameters. So in fact, the short-term isotopic fluctuations correlate directly with summer precipitation and inversely with summer and spring temperature. A long-term decreasing isotope trend in Montreal indicates progressive changes in soil chemistry after 1951. A pedochemical change is also inferred for the Georgian Bay site on the basis of a positive N isotopic trend initiated after 1971. At both sites, the long-term ^15N series correlate with a proxy for NOx emissions (Pearson correlation), and carbon-isotope ring series suggest that the same trees have been impacted by phytotoxic pollutants (Savard et al., 2009a). We propose that the contrasted long-term nitrogen-isotope changes of Montreal and Georgian Bay reflect deposition of NOx emissions from cars and coal-power plants, with higher proportions from coal burning in Georgian Bay (Savard et al., 2009b). This interpretation is conceivable because recent monitoring indicates that coal-power plant NOx emissions play an important role in the annual N budget in Ontario, but they are negligible on the Quebec side. CONCLUSION Interpretations of long tree-ring N isotopic series in terms of effects generated by airborne N-species have been previously advocated. Here we further propose that the contrasted isotopic trends obtained for wood samples from two regions reflect different regional anthropogenic N deposition combined with variations of climatic conditions. This research suggests that nitrogen tree-ring series may record both regional climatic conditions and anthropogenic perturbations of the N cycle. REFERENCES Savard, M.M., Bégin,C., Marion, J., Aznar, J.-C., Smirnoff, A., 2009a. Changes of Air Quality in an urban region as inferred from tree-ring width and stable isotopes. Chapter 9 in "Relating Atmospheric Source Apportionment to Vegetation Effects: Establishing Cause Effect Relationships" (A. Legge ed.). Elsevier, Amsterdam; doi: 10.1016/S1474-8177(08)00209x. Savard, M.M., Bégin, C., Smirnoff, A., Marion, J., Rioux-Paquette, E., 2009b. Tree-ring nitrogen isotopes reflect climatic effects and anthropogenic NOx emissions. Env. Sci. Tech (doi: 10.1021/es802437k).

A Six-Coordinate Peroxynitrite Low-Spin Iron(III) Porphyrinate Complex—The Product of the Reaction of Nitrogen Monoxide (·NO (g)) with a Ferric-Superoxide Species

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

Sharma, Savita K.; Schaefer, Andrew W.; Lim, Hyeongtaek

Peroxynitrite ( –OON=O, PN) is a reactive nitrogen species (RNS) which can effect deleterious nitrative or oxidative (bio)chemistry. It may derive from reaction of superoxide anion (O 2 •–) with nitric oxide (·NO) and has been suggested to form an as-yet unobserved bound heme-iron-PN intermediate in the catalytic cycle of nitric oxide dioxygenase (NOD) enzymes, which facilitate a ·NO homeostatic process, i.e., its oxidation to the nitrate anion. Here, a discrete six-coordinate low-spin porphyrinate-Fe III complex [(P Im)Fe III( –OON=O)] (P Im; a porphyrin moiety with a covalently tethered imidazole axial “base” donor ligand) has been identified and characterized bymore » various spectroscopies (UV–vis, NMR, EPR, XAS, resonance Raman) and DFT calculations, following its formation at –80 °C by addition of ·NO (g) to the heme-superoxo species, [(P Im)Fe III(O 2 •–)]. DFT calculations confirm that is a six-coordinate low-spin species with the PN ligand coordinated to iron via its terminal peroxidic anionic O atom with the overall geometry being in a cis-configuration. Complex thermally transforms to its isomeric low-spin nitrato form [(P Im)Fe III(NO 3 –)]. While previous (bio)chemical studies show that phenolic substrates undergo nitration in the presence of PN or PN-metal complexes, in the present system, addition of 2,4-di- tert-butylphenol ( 2,4DTBP) to complex does not lead to nitrated phenol; the nitrate complex still forms. Furthermore, DFT calculations reveal that the phenolic H atom approaches the terminal PN O atom (farthest from the metal center and ring core), effecting O–O cleavage, giving nitrogen dioxide (·NO 2) plus a ferryl compound [(P Im)Fe IV=O] (7); this rebounds to give [(P Im)Fe III(NO 3 –)].The generation and characterization of the long sought after ferriheme peroxynitrite complex has been accomplished.« less

A Six-Coordinate Peroxynitrite Low-Spin Iron(III) Porphyrinate Complex—The Product of the Reaction of Nitrogen Monoxide (·NO (g)) with a Ferric-Superoxide Species

DOE PAGES

Sharma, Savita K.; Schaefer, Andrew W.; Lim, Hyeongtaek; ...

2017-11-01

Peroxynitrite ( –OON=O, PN) is a reactive nitrogen species (RNS) which can effect deleterious nitrative or oxidative (bio)chemistry. It may derive from reaction of superoxide anion (O 2 •–) with nitric oxide (·NO) and has been suggested to form an as-yet unobserved bound heme-iron-PN intermediate in the catalytic cycle of nitric oxide dioxygenase (NOD) enzymes, which facilitate a ·NO homeostatic process, i.e., its oxidation to the nitrate anion. Here, a discrete six-coordinate low-spin porphyrinate-Fe III complex [(P Im)Fe III( –OON=O)] (P Im; a porphyrin moiety with a covalently tethered imidazole axial “base” donor ligand) has been identified and characterized bymore » various spectroscopies (UV–vis, NMR, EPR, XAS, resonance Raman) and DFT calculations, following its formation at –80 °C by addition of ·NO (g) to the heme-superoxo species, [(P Im)Fe III(O 2 •–)]. DFT calculations confirm that is a six-coordinate low-spin species with the PN ligand coordinated to iron via its terminal peroxidic anionic O atom with the overall geometry being in a cis-configuration. Complex thermally transforms to its isomeric low-spin nitrato form [(P Im)Fe III(NO 3 –)]. While previous (bio)chemical studies show that phenolic substrates undergo nitration in the presence of PN or PN-metal complexes, in the present system, addition of 2,4-di- tert-butylphenol ( 2,4DTBP) to complex does not lead to nitrated phenol; the nitrate complex still forms. Furthermore, DFT calculations reveal that the phenolic H atom approaches the terminal PN O atom (farthest from the metal center and ring core), effecting O–O cleavage, giving nitrogen dioxide (·NO 2) plus a ferryl compound [(P Im)Fe IV=O] (7); this rebounds to give [(P Im)Fe III(NO 3 –)].The generation and characterization of the long sought after ferriheme peroxynitrite complex has been accomplished.« less

Natural bond orbital approach to the transmission of substituent effect through the fulvene and benzene ring systems.

PubMed

Oziminski, Wojciech P; Krygowski, Tadeusz M

2011-03-01

Electronic structure of 22 monosubstituted derivatives of benzene and exocyclically substituted fulvene with substituents: B(OH)(2), BH(2), CCH, CF(3), CH(3), CHCH(2), CHO, Cl, CMe(3), CN, COCH(3), CONH(2), COOH, F, NH(2), NMe(2), NO, NO(2), OCH(3), OH, SiH(3), SiMe(3) were studied theoretically by means of Natural Bond Orbital analysis. It is shown, that sum of π-electron population of carbon atoms of the fulvene and benzene rings, pEDA(F) and pEDA(B), respectively correlate well with Hammett substituent constants [Formula in text] and aromaticity index NICS. The substituent effect acting on pi-electron occupation at carbon atoms of the fulvene ring is significantly stronger than in the case of benzene. Electron occupations of ring carbon atoms (except C1) in fulvene plotted against each other give linear regressions with high correlation coefficients. The same is true for ortho- and para-carbon atoms in benzene. Positive slopes of the regressions indicate similar for fulvene and benzene kind of substituent effect - mostly resonance in nature. Only the regressions of occupation at the carbon atom in meta- position of benzene against ortho- and para-positions gives negative slopes and low correlation coefficients.

Crystal structure of (E)-N′-{[(1R,3R)-3-isopropyl-1-methyl-2-oxo­cyclo­pent­yl]methyl­idene}-4-methyl­benzene­sulfono­hydrazide

PubMed Central

Tymann, David; Dragon, Dina Christina; Golz, Christopher; Preut, Hans; Strohmann, Carsten; Hiersemann, Martin

2015-01-01

The title compound, C17H24N2O3S, was synthesized in order to determine the relative configuration of the corresponding β-keto aldehyde. In the U-shaped mol­ecule, the five-membered ring approximates an envelope with the methyl­ene atom adjacent to the quaternary C atom being the flap. The dihedral angles between the four nearly coplanar atoms of the five-membered ring and the flap and the aromatic ring are 38.8 (4) and 22.9 (2)°, respectively. The bond angles around the S atom are in the range 104.11 (16)–119.95 (16)°. In the crystal, mol­ecules are linked via N—H⋯O by hydrogen bonds, forming a chain along the a-axis direction. PMID:25878892

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.

Determination of the line shapes of atomic nitrogen resonance lines by magnetic scans

NASA Technical Reports Server (NTRS)

Lawrence, G. M.; Stone, E. J.; Kley, D.

1976-01-01

A technique is given for calibrating an atomic nitrogen resonance lamp for use in determining column densities of atoms in specific states. A discharge lamp emitting the NI multiplets at 1200 A and 1493 A is studied by obtaining absorption by atoms in a magnetic field (0-2.5 T). This magnetic scanning technique enables the determination of the absorbing atom column density, and an empirical curve of growth is obtained because the atomic f-value is known. Thus, the calibrated lamp can be used in the determination of atomic column densities.

Ethyl 2-{4-[(1,5-dibenzyl-2,4-dioxo-2,3,4,5-tetra-hydro-1H-1,5-benzo-diazepin-3-yl)meth-yl]-1H-1,2,3-triazol-1-yl}acetate.

PubMed

Jabli, Hind; Kandri Rodi, Y; Ladeira, Sonia; Essassi, El Mokhtar; Ng, Seik Weng

2009-12-12

The reaction of 1,5-dibenzyl-3-propargyl-1,5-benzodiazepine-2,4-dione with ethyl azido-acetate in the presence of copper sulfate pentahydrate and sodium ascorbate leads to the formation of the title regioisomer, C(30)H(29)N(5)O(4), which features a phenyl-ene ring fused with a seven-membered diazepinyl ring. The latter ring adopts a boat conformation (with the methyl-triazolylacetate-bearing C atom as the prow and the fused-ring C atoms as the stern). The benzyl groups connected to the diazepinyl ring jprotrude from the sides; the methyl-triazolylacetate substituent occupies an axial position.

Odd nitrogen production by meteoroids

NASA Technical Reports Server (NTRS)

Park, C.; Menees, G. P.

1978-01-01

The process by which odd nitrogen species (atomic nitrogen and nitric oxide) are formed during atmospheric entry of meteoroids is analyzed theoretically. An ablating meteoroid is assumed to be a point source of mass with a continuum regime evolving in its wake. The amounts of odd nitrogen species, produced by high-temperature reactions of air in the continuum wake, are calculated by numerical integration of chemical rate equations. Flow properties are assumed to be uniform across the wake, and 29 reactions involving five neutral species and five singly ionized species are considered, as well as vibrational and electron temperature nonequilibrium phenomena. The results, when they are summed over the observed mass, velocity, and entry-angle distribution of meteoroids, provide odd-nitrogen-species annual global production rates as functions of altitude. The peak production of nitric oxide is found to occur at an altitude of about 85 km; atomic nitrogen production peaks at about 95 km. The total annual rate for nitric oxide is 40 million kg; for atomic nitrogen it is 170 million kg.

Methyl 4-(4-fluoro­phen­yl)-6-isopropyl-2-[N-methyl-N-(methylsulfonyl)amino]­pyrimidine-5-carboxyl­ate

PubMed Central

He, Wei; Yang, Dong-Ling; Cui, Yong-Tao; Xu, Ye-Ming; Guo, Cheng

2008-01-01

In the mol­ecule of the title compound, C17H20FN3O4S, the pyrimidine and benzene rings are oriented at a dihedral angle of 35.59 (3)°. Intra­molecular C—H⋯N and C—H⋯O hydrogen bonds result in the formation of one five- and two six-membered non-planar rings. One of the six-membered rings adopts a chair conformation, while the other six-membered ring and the five-membered ring exhibit envelope conformations with O and N atoms displaced by 0.837 (3) and 0.152 (3) Å, respectively from the planes of the other ring atoms. In the crystal structure, inter­molecular C—H⋯F hydrogen bonds link the mol­ecules into infinite chains. PMID:21202637

Three dimensional atom probe imaging of GaAsSb quantum rings.

PubMed

Beltrán, A M; Marquis, E A; Taboada, A G; Ripalda, J M; García, J M; Molina, S I

2011-07-01

Unambiguous evidence of ring-shaped self-assembled GaSb nanostructures grown by molecular beam epitaxy is presented on the basis of atom-probe tomography reconstructions and dark field transmission electron microscopy imaging. The GaAs capping process causes a strong segregation of Sb out of the center of GaSb quantum dots, leading to the self-assembled GaAs(x)Sb(1-x) quantum rings of 20-30 nm in diameter with x ∼ 0.33. Copyright © 2011 Elsevier B.V. All rights reserved.

1-(2-Chloro­acet­yl)-3-methyl-2,6-bis­(3,4,5-trimethoxy­phen­yl)piperidine-4-one

PubMed Central

Lakshminarayana, B. N.; Shashidhara Prasad, J.; Gnanendra, C. R.; Sridhar, M. A.; Chenne Gowda, D.

2009-01-01

In the crystal structure of the title compound, C26H32ClNO8, the piperidine ring is in a twist-chair conformation, with puckering parameters Q = 0.655 (4) Å, θ = 93.1 (1) and ϕ = 254.4 (3)°. The ortho C atoms of the piperidine ring deviate from the plane defined by the remaining ring atoms by 0.380 (3) and −0.250 (3) Å. PMID:21583104

New Data for Modeling Hypersonic Entry into Earth's Atmosphere: Electron-impact Ionization of Atomic Nitrogen

NASA Astrophysics Data System (ADS)

Savin, Daniel Wolf; Ciccarino, Christopher

2017-06-01

Meteors passing through Earth’s atmosphere and space vehicles returning to Earth from beyond orbit enter the atmosphere at hypersonic velocities (greater than Mach 5). The resulting shock front generates a high temperature reactive plasma around the meteor or vehicle (with temperatures greater than 10,000 K). This intense heat is transferred to the entering object by radiative and convective processes. Modeling the processes a meteor undergoes as it passes through the atmosphere and designing vehicles to withstand these conditions requires an accurate understanding of the underlying non-equilibrium high temperature chemistry. Nitrogen chemistry is particularly important given the abundance of nitrogen in Earth's atmosphere. Line emission by atomic nitrogen is a major source of radiative heating during atomspheric entry. Our ability to accurately calculate this heating is hindered by uncertainties in the electron-impact ionization (EII) rate coefficient for atomic nitrogen.Here we present new EII calculations for atomic nitrogen. The atom is treated as a 69 level system, incorporating Rydberg values up to n=20. Level-specific cross sections are from published B-Spline R-Matrix-with-Pseudostates results for the first three levels and binary-encounter Bethe (BEB) calculations that we have carried out for the remaining 59 levels. These cross section data have been convolved into level-specific rate coefficients and fit with the commonly-used Arrhenius-Kooij formula for ease of use in hypersonic chemical models. The rate coefficient data can be readily scaled by the relevant atomic nitrogen partition function which varies in time and space around the meteor or reentry vehicle. Providing data up to n=20 also enables modelers to account for the density-dependent lowering of the continuum.

Influence of Mechanical Stretching on Adsorption Properties of Nitrogen-Doped Graphene

NASA Astrophysics Data System (ADS)

Dolinskii, I. Yu.; Katin, K. P.; Grishakov, K. S.; Prudkovskii, V. S.; Kargin, N. I.; Maslov, M. M.

2018-04-01

This paper presents the results of quantum chemical modeling of chemisorption of atomic hydrogen and epoxy, carboxyl, and hydroxyl functional groups on nitrogen-doped graphene. It is shown that the substitutional nitrogen atom does not bind to adsorbing groups directly, but significantly increases the adsorption activity of neighboring carbon atoms. Mechanical stretching of doped graphene reduces the adsorption energy of all the aforementioned radicals. This reduction is significantly greater for the epoxy group than for the other functional groups. The results obtained confirm that, upon a sufficient stretching of a nitrogen-doped graphene sheet, the dissociation of molecular hydrogen and oxygen with subsequent precipitation of the resulting radicals onto graphene can be energetically favorable.

Kinetics of Fast Atoms in the Terrestrial Atmosphere

NASA Technical Reports Server (NTRS)

Kharchenko, Vasili A.; Dalgarno, A.; Mellott, Mary (Technical Monitor)

2002-01-01

This report summarizes our investigations performed under NASA Grant NAG5-8058. The three-year research supported by the Geospace Sciences SR&T program (Ionospheric, Thermospheric, and Mesospheric Physics) has been designed to investigate fluxes of energetic oxygen and nitrogen atoms in the terrestrial thermosphere. Fast atoms are produced due to absorption of the solar radiation and due to coupling between the ionosphere and the neutral thermospheric gas. We have investigated the impact of hot oxygen and nitrogen atoms on the thermal balance, chemistry and radiation properties of the terrestrial thermosphere. Our calculations have been focused on the accurate quantitative description of the thermalization of O and N energetic atoms in collisions with atom and molecules of the ambient neutral gas. Upward fluxes of oxygen and nitrogen atoms, the rate of atmospheric heating by hot oxygen atoms, and the energy input into translational and rotational-vibrational degrees of atmospheric molecules have been evaluated. Altitude profiles of hot oxygen and nitrogen atoms have been analyzed and compared with available observational data. Energetic oxygen atoms in the terrestrial atmosphere have been investigated for decades, but insufficient information on the kinetics of fast atmospheric atoms has been a main obstacle for the interpretation of observational data and modeling of the hot geocorona. The recent development of accurate computational methods of the collisional kinetics is seen as an important step in the quantitative description of hot atoms in the thermosphere. Modeling of relaxation processes in the terrestrial atmosphere has incorporated data of recent observations, and theoretical predictions have been tested by new laboratory measurements.

Blue-detuned optical ring trap for Bose-Einstein condensates based on conical refraction.

PubMed

Turpin, A; Polo, J; Loiko, Yu V; Küber, J; Schmaltz, F; Kalkandjiev, T K; Ahufinger, V; Birkl, G; Mompart, J

2015-01-26

We present a novel approach for the optical manipulation of neutral atoms in annular light structures produced by the phenomenon of conical refraction occurring in biaxial optical crystals. For a beam focused to a plane behind the crystal, the focal plane exhibits two concentric bright rings enclosing a ring of null intensity called the Poggendorff ring. We demonstrate both theoretically and experimentally that the Poggendorff dark ring of conical refraction is confined in three dimensions by regions of higher intensity. We derive the positions of the confining intensity maxima and minima and discuss the application of the Poggendorff ring for trapping ultra-cold atoms using the repulsive dipole force of blue-detuned light. We give analytical expressions for the trapping frequencies and potential depths along both the radial and the axial directions. Finally, we present realistic numerical simulations of the dynamics of a ⁸⁷Rb Bose-Einstein condensate trapped inside the Poggendorff ring which are in good agreement with corresponding experimental results.

Super-elite plasma rings and the orbits of planets and satellites isomorphic to the orbits of electrons in the Bohr's model of the hydrogen atom

NASA Astrophysics Data System (ADS)

Rabinovich, B. I.

2007-10-01

This paper continues the series of papers [1 5] and generalizes the previous results to a proto-ring of magnetized plasma whose density decreases in the radial direction. The problem of quantization of the sector and orbital velocities, and of the radii and periods of revolution of elite plasma rings is considered. A new concept of super-elite rings is introduced. Their isomorphism with the orbits of the planets and planetary satellites in the Solar System is proved. This isomorphism also extends to the orbits of electrons in the Bohr’s model of the hydrogen atom.

Total Synthesis of Bryostatins. Development of Methodology for Atom-Economic and Stereoselective Synthesis of the C-ring Subunit

PubMed Central

Trost, Barry M.; Frontier, Alison J.; Thiel, Oliver R.; Yang, Hanbiao; Dong, Guangbin

2012-01-01

Bryostatins, a family of structurally complicated macrolides, exhibit an exceptional range of biological activities. The limited availability and structural complexity of these molecules makes development of an efficient total synthesis particularly important. This article describes our initial efforts towards the total synthesis of bryostatins, in which chemoselective and atom-economical methods for stereoselective assembly of the C-ring subunit were developed. A Pd-catalyzed tandem alkyne-alkyne coupling/6-endo-dig cyclization sequence was explored and successfully pursued in the synthesis of a dihydropyran ring system. Elaboration of this methodology ultimately led to a concise synthesis of the C-ring subunit of bryostatins. PMID:21793057

Ultrafine particles and nitrogen oxides generated by gas and electric cooking.

PubMed

Dennekamp, M; Howarth, S; Dick, C A; Cherrie, J W; Donaldson, K; Seaton, A

2001-08-01

To measure the concentrations of particles less than 100 nm diameter and of oxides of nitrogen generated by cooking with gas and electricity, to comment on possible hazards to health in poorly ventilated kitchens. Experiments with gas and electric rings, grills, and ovens were used to compare different cooking procedures. Nitrogen oxides (NO(x)) were measured by a chemiluminescent ML9841A NO(x) analyser. A TSI 3934 scanning mobility particle sizer was used to measure average number concentration and size distribution of aerosols in the size range 10-500 nm. High concentrations of particles are generated by gas combustion, by frying, and by cooking of fatty foods. Electric rings and grills may also generate particles from their surfaces. In experiments where gas burning was the most important source of particles, most particles were in the size range 15-40 nm. When bacon was fried on the gas or electric rings the particles were of larger diameter, in the size range 50-100 nm. The smaller particles generated during experiments grew in size with time because of coagulation. Substantial concentrations of NO(X) were generated during cooking on gas; four rings for 15 minutes produced 5 minute peaks of about 1000 ppb nitrogen dioxide and about 2000 ppb nitric oxide. Cooking in a poorly ventilated kitchen may give rise to potentially toxic concentrations of numbers of particles. Very high concentrations of oxides of nitrogen may also be generated by gas cooking, and with no extraction and poor ventilation, may reach concentrations at which adverse health effects may be expected. Although respiratory effects of exposure to NO(x) might be anticipated, recent epidemiology suggests that cardiac effects cannot be excluded, and further investigation of this is desirable.

Enhanced nitrogen diffusion induced by atomic attrition

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

Ochoa, E.A.; Figueroa, C.A.; Czerwiec, T.

2006-06-19

The nitrogen diffusion in steel is enhanced by previous atomic attrition with low energy xenon ions. The noble gas bombardment generates nanoscale texture surfaces and stress in the material. The atomic attrition increases nitrogen diffusion at lower temperatures than the ones normally used in standard processes. The stress causes binding energy shifts of the Xe 3d{sub 5/2} electron core level. The heavy ion bombardment control of the texture and stress of the material surfaces may be applied to several plasma processes where diffusing species are involved.

Tracing the atomic nitrogen abundance in star-forming regions with ammonia deuteration

NASA Astrophysics Data System (ADS)

Furuya, Kenji; Persson, Magnus V.

2018-06-01

Partitioning of elemental nitrogen in star-forming regions is not well constrained. Most nitrogen is expected to be partitioned among atomic nitrogen (N I), molecular nitrogen (N_2), and icy N-bearing molecules, such as NH_3 and N_2. N I is not directly observable in the cold gas. In this paper, we propose an indirect way to constrain the amount of N I in the cold gas of star-forming clouds, via deuteration in ammonia ice, the [ND2H/NH2D]/[NH2D/NH3] ratio. Using gas-ice astrochemical simulations, we show that if atomic nitrogen remains as the primary reservoir of nitrogen during cold ice formation stages, the [ND2H/NH2D]/[NH2D/NH3] ratio is close to the statistical value of 1/3 and lower than unity, whereas if atomic nitrogen is largely converted into N-bearing molecules, the ratio should be larger than unity. Observability of ammonia isotopologues in the inner hot regions around low-mass protostars, where ammonia ice has sublimated, is also discussed. We conclude that the [ND2H/NH2D]/[NH2D/NH3] ratio can be quantified using a combination of Very Large Array and Atacama Large Millimeter/submillimeter Array observations with reasonable integration times, at least towards IRAS 16293-2422, where high molecular column densities are expected.

Quantum oscillation and the Aharonov-Bohm effect in a multiply connected normal-conductor loop

NASA Astrophysics Data System (ADS)

Takai, Daisuke; Ohta, Kuniichi

1994-12-01

The magnetostatic and electrostatic Aharonov-Bohm (AB) effects in multiply connected normal-conductor rings are studied. A previously developed model of a single mesoscopic ring is generalized to include an arbitrary number of rings, and the oscillatory behavior of the total transmission coefficients for the serially connected N (N is equal to integer) rings are derived as a function of the magnetic flux threading each ring and as a function of the electrostatic potential applied to the rings. It is shown that quantum oscillation of multiple rings exhibits greater variety of behavior than in periodic superlattices. We investigate the influence of the scattering at a junction and the number of atoms in the ring in both magnetostatic and electrostatic oscillation of multiring systems. For the electrostatic AB effects, when scattering occurs at the junctions between the connecting wire and the ring, the conductance in the AB oscillation is modified to an N-1 peaked shape. It is shown that this oscillatory behavior is greatly influenced by the number of atoms in the ring and is controlled by the electrostatic potential or magnetic flux that is applied to the ring. We discuss the behavior of the quantum oscillations upon varying the number of connected rings and the number of minibands.

Atomic cobalt on nitrogen-doped graphene for hydrogen generation

PubMed Central

Fei, Huilong; Dong, Juncai; Arellano-Jiménez, M. Josefina; Ye, Gonglan; Dong Kim, Nam; Samuel, Errol L.G.; Peng, Zhiwei; Zhu, Zhuan; Qin, Fan; Bao, Jiming; Yacaman, Miguel Jose; Ajayan, Pulickel M.; Chen, Dongliang; Tour, James M.

2015-01-01

Reduction of water to hydrogen through electrocatalysis holds great promise for clean energy, but its large-scale application relies on the development of inexpensive and efficient catalysts to replace precious platinum catalysts. Here we report an electrocatalyst for hydrogen generation based on very small amounts of cobalt dispersed as individual atoms on nitrogen-doped graphene. This catalyst is robust and highly active in aqueous media with very low overpotentials (30 mV). A variety of analytical techniques and electrochemical measurements suggest that the catalytically active sites are associated with the metal centres coordinated to nitrogen. This unusual atomic constitution of supported metals is suggestive of a new approach to preparing extremely efficient single-atom catalysts. PMID:26487368

Ultrafine particles and nitrogen oxides generated by gas and electric cooking

PubMed Central

Dennekamp, M; Howarth, S; Dick, C; Cherrie, J; Donaldson, K; Seaton, A

2001-01-01

OBJECTIVES—To measure the concentrations of particles less than 100 nm diameter and of oxides of nitrogen generated by cooking with gas and electricity, to comment on possible hazards to health in poorly ventilated kitchens.
METHODS—Experiments with gas and electric rings, grills, and ovens were used to compare different cooking procedures. Nitrogen oxides (NOx) were measured by a chemiluminescent ML9841A NOx analyser. A TSI 3934 scanning mobility particle sizer was used to measure average number concentration and size distribution of aerosols in the size range 10-500 nm.
RESULTS—High concentrations of particles are generated by gas combustion, by frying, and by cooking of fatty foods. Electric rings and grills may also generate particles from their surfaces. In experiments where gas burning was the most important source of particles, most particles were in the size range 15-40 nm. When bacon was fried on the gas or electric rings the particles were of larger diameter, in the size range 50-100 nm. The smaller particles generated during experiments grew in size with time because of coagulation. Substantial concentrations of NOX were generated during cooking on gas; four rings for 15 minutes produced 5 minute peaks of about 1000 ppb nitrogen dioxide and about 2000 ppb nitric oxide.
CONCLUSIONS—Cooking in a poorly ventilated kitchen may give rise to potentially toxic concentrations of numbers of particles. Very high concentrations of oxides of nitrogen may also be generated by gas cooking, and with no extraction and poor ventilation, may reach concentrations at which adverse health effects may be expected. Although respiratory effects of exposure to NOx might be anticipated, recent epidemiology suggests that cardiac effects cannot be excluded, and further investigation of this is desirable.


Keywords: cooking fuels; nitrogen oxides; ultrafine particles PMID:11452045

Tris[dimethyl (benzoyl­amido)­phosphato-κ2 O,O′](1,10-phenanthroline-κ2 N,N′)neodymium(III)

PubMed Central

Kariaka, Nataliia S.; Trush, Victor A.; Medviediev, Volodymyr V.; Sliva, Tetyana Yu.; Amirkhanov, Vladimir M.

2013-01-01

In both independent mol­ecules of the title compound, [Nd(C9H11NO4P)3(C12H8N2)], the NdIII atom is coordinated by six O atoms belonging to three phosphoryl ligands and two N atoms of 1,10-phenanthroline in a dodeca­hedral geometry. In the phosphoryl ligands, the benzene rings are twisted with respect to the planes of the sp 2-hybridized C atoms of the chelate rings by 12.1 (1)–24.7 (1)°. PMID:23476491

Design and synthesis of novel HDAC8 inhibitory 2,5-disubstituted-1,3,4-oxadiazoles containing glycine and alanine hybrids with anti cancer activity.

PubMed

Pidugu, Vijaya Rao; Yarla, Nagendra Sastry; Pedada, Srinivasa Rao; Kalle, Arunasree M; Satya, A Krishna

2016-11-01

Oxadiazole is a heterocyclic compound containing an oxygen atom and two nitrogen atoms in a five-membered ring. Of the four oxadiazoles known, 1,3,4-oxadiazole has become an important structural motif for the development of new drugs and the compounds containing 1,3,4-oxadiazole cores have a broad spectrum of biological activity. Herein, we describe the design, synthesis and biological evaluation of a series of novel 2,5-disubstituted 1,3,4-oxadiazoles (10a-10j) as class I histone deacetylase (HDAC) inhibitors. The compounds were designed and evaluated for HDAC8 selectivity using in silico docking software (Glide) and the top 10 compounds with high dock score and obeying Lipinski's rule were synthesized organically. Further the biological HDAC inhibitory and selectivity assays and anti-proliferative assays were carried out. In in silico and in vitro studies, all compounds (10a-10j) showed significant HDAC inhibition and exhibited HDAC8 selectivity. Among all tested compounds, 10b showed substantial HDAC8 inhibitory activity and better anticancer activity which is comparable to the positive control, a FDA approved drug, vorinostat (SAHA). Structural activity relation is discussed with various substitutions in the benzene ring connected on 1,3,4-oxadizole and glycine/alanine. The study warranted further investigations to develop HDAC8-selective inhibitory molecule as a drug for neoplastic diseases. Novel 1,3,4-oxadizole substituted with glycine/alanine showed HDAC8 inhibition. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ion mobility studies of PdC{sub n}{sup +} clusters: Where are the fullerenes?

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

Shelimov, K.B.; Jarrold, M.F.

1995-12-14

Gas-phase ion mobility measurements have been used to study the structures and isomerization of PdC{sub n}{sup +} (n = 10-60) clusters. Non-fullerene isomers of PdC{sub n}{sup +} clusters are similar to those of C{sub n}{sup +} and MC{sub n}{sup +} (M = La and Nb) clusters, and include metal-containing mono- and bicyclic rings and graphite sheets. Neither endohedral nor nonendohedral PdC{sub n} {sup +} fullerene isomers are detected. When collisionally heated, PdC{sub n}{sup +} clusters efficiently convert into fullerenes, but the exothermicity of this process results in the loss of the Pd atom and the formation of a pure carbonmore » cluster cation. PdC{sub n}{sup +} bicyclic rings with an odd number of carbon atoms efficiently isomerize into monocyclic rings, while no evidence is found for this isomerization process for bicyclic rings with an even number of carbon atoms. 18 refs., 4 figs.« less

Tree-ring strontium-90 and cesium-137 as potential indicators of radioactive pollution.

PubMed

Kagawa, Akira; Aoki, Toru; Okada, Naoki; Katayama, Yukio

2002-01-01

To examine whether tree rings can be used to detect or assess local historical 90Sr or 137Cs fallout, such as that resulting from the Hiroshima atomic bomb, radial distribution of 90Sr and 137Cs in trees was examined. We studied a gymnosperm [Japanese cedar, Cryptomeria japonica (L. f.) D. Don] and an angiosperm (Japanese persimmon, Diospyros kaki Thunb.) tree species from the vicinity of the atomic bomb hypocenter, and from other locations in Japan. A significant amount of 137Cs was detected in tree rings formed before 1945, indicating lateral migration of Cs. In contrast, the specific activity of 90Sr in the Hiroshima Japanese cedar showed the highest level in 1945, due to relatively immobile characteristics of Sr compared with Cs. Strontium-90 and Sr analyses in tree rings helped identify and distinguish between residual 90Sr activity from the Hiroshima atomic bomb and the atmospheric nuclear testing. This indicates the possibility of detecting or assessing previous local 90Sr pollution through with treering analysis.

CIT-7, a crystalline, molecular sieve with pores bounded by 8 and 10-membered rings

DOE PAGES

Schmidt, Joel E.; Xie, Dan; Rea, Thomas; ...

2015-01-23

A new crystalline molecular sieve, denoted CIT-7, is synthesized using an imidazolium-based diquaternary organic structure directing agent (OSDA). The framework structure is determined from a combination of rotation electron diffraction and synchrotron X-ray powder diffraction data. The structure has 10 crystallographically unique tetrahedral atoms (T-atoms) in the unit cell, and can be described as an ordered arrangement of the [4 25 46 2] mtw building unit and a previously unreported [4 45 2] building unit. The framework contains a 2-dimensional pore system that is bounded by 10 T-atom rings (10-ring, 5.1 Å × 6.2 Å opening) that are connected withmore » oval 8-rings (2.9 Å × 5.5 Å opening) through medium-sized cavities (~7.9 Å) at the channel intersections. CIT-7 can be synthesized over a broad range of compositions including pure-silica and heteroatom, e.g., aluminosilicate and titanosilicate, containing variants.« less

Electronic conductance of a poly(p-phenylene)-like nanowire in the presence of thermal atomic vibrations

NASA Astrophysics Data System (ADS)

Shariati, Ashrafalsadat; Rabani, Hassan; Mardaani, Mohammad

2017-10-01

We present a theoretical method based on Green’s function technique and tight-binding approach as well as harmonic approximation in order to calculate the coherent electronic conductance of an extended poly(p-phenylene) oligomer in the presence of thermal atomic vibrations. We study two proposed mass-spring models for atomic vibrations: one, including rigid benzene rings connected to each other by vibrating bonds; and in another, the bonds along the oligomer vibrate even in the benzene rings. The electron-phonon (e-ph) interaction influences the electron hopping energies linearly with respect to atomic displacements. The model shows that the conductance spectra exhibit some new energy gaps in the presence of e-ph interaction even at zero temperature. The conductance is more affected by e-ph interaction when the atomic vibrations are supposed to be present in the benzene rings. At the edges of the band energy and central gap, the phonon-assisted phenomena can be observed. Generally, the increasing e-ph interaction strength as well as temperature destroys the electronic conductance especially in the resonance region.

The effect of nitrogen incorporation on the bonding structure of hydrogenated carbon nitride films

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

Camero, M.; Buijnsters, J. G.; Gomez-Aleixandre, C.

2007-03-15

This work describes the composition and bonding structure of hydrogenated carbon nitride (a-CN{sub x}:H) films synthesized by electron cyclotron resonance chemical vapor deposition using as precursor gases argon, methane, and nitrogen. The composition of the films was derived from Rutherford backscattering and elastic recoil detection analysis and the bonding structure was examined by infrared (IR) spectroscopy and x-ray absorption near edge spectroscopy (XANES). By varying the nitrogen to methane ratio in the applied gas mixture, polymeric a-CN{sub x}:H films with N/C contents varying from 0.06 to 0.49 were obtained. Remarkably, the H content of the films ({approx}40 at. %) wasmore » rather unaffected by the nitrogenation process. The different bonding states as detected in the measured XANES C(1s) and N(1s) spectra have been correlated with those of a large number of reference samples. The XANES and IR spectroscopy results indicate that N atoms are efficiently incorporated into the amorphous carbon network and can be found in different bonding environments, such as pyridinelike, graphitelike, nitrilelike, and amino groups. The nitrogenation of the films results in the formation of N-H bonding environments at the cost of C-H structures. Also, the insertion of N induces a higher fraction of double bonds in the structure at the expense of the linear polymerlike chains, hence resulting in a more cross-linked solid. The formation of double bonds takes place through complex C=N structures and not by formation of graphitic aromatic rings. Also, the mechanical and tribological properties (hardness, friction, and wear) of the films have been studied as a function of the nitrogen content. Despite the major modifications in the bonding structure with nitrogen uptake, no significant changes in these properties are observed.« less

[The Emission Spectroscopy of Nitrogen Discharge under Low Voltage at Room Temperature].

PubMed

Shen, Li-hua; Yu, Chun-xia; Yan, Bei; Zhang, Cheng-xiao

2015-03-01

A set of direct current (DC) discharge device of N2 plasma was developed, carbon nanotubes (CNT) modified ITO electrode was used as anode, aluminum plate as cathode, with -80 μm separation between them. Nitrogen emission spectra was observed at room temperature and low DC voltage (less than 150 V), and the emission spectrometry was used to diagnose the active species of the process of nitrogen discharge. Under DC discharge, the strongest energy band N2 (C3π(u)), the weak Gaydon's Green system N2 (H3 -Φ(u)-G3 Δ(g)) and the emission line of nitrogen atoms (4 p-4 p0) at 820 nm were observed. Found that metastable state of nitrogen molecules were the main factors leading to a series of excited state nitrogen atoms and nitrogen ionization. Compared the emission spectra under DC with that under alternating current (AC) (1.1 kV), and it can be seen that under DC the spectra band of nitrogen atoms can be obviously observed, and there was a molecular band in the range of 500 - 800 nm. The effect of oxygen and hydrogen on the emission spectra of nitrogen was investigated. The results showed that the oxygen inhibited the luminescence intensity of nitrogen, but the shape of spectra unchanged. All of the second positive system, Gaydon's Green system and atomic lines of nitrogen can be observed. The second positive system and Gaydon's Green system of nitrogen will be greatly affected when the volume ratio of nitrogen and hydrogen greatly affected is 1 : 1, which was due to the hydrogen. The hydrogen can depresse nitrogen plasma activation, and make the Gaydon's Green System disappeared. CNT modified ITO electrode can reduce the breakdown voltage, and the optical signal generated by the weakly ionized gas can be observed by the photo-multiplier tube at low voltage of 10 V.

Agreement between experimental and theoretical effects of nitrogen gas flowrate on liquid jet atomization

NASA Technical Reports Server (NTRS)

Ingebo, Robert D.

1987-01-01

Two-phase flows were investigated by using high velocity nitrogen gas streams to atomize small-diameter liquid jets. Tests were conducted primarily in the acceleration-wave regime for liquid jet atomization, where it was found that the loss of droplets due to vaporization had a marked effect on drop size measurements. In addition, four identically designed two-fluid atomizers were fabricated and tested for similarity of spray profiles. A scattered-light scanner was used to measure a characteristic drop diameter, which was correlated with nitrogen gas flowrate. The exponent of 1.33 for nitrogen gas flowrate is identical to that predicted by atomization theory for liquid jet breakup in the acceleration-wave regime. This is higher than the value of 1.2 which was previously obtained at a sampling distance of 4.4 cm downstream of the atomizer. The difference is attributed to the fact that drop-size measurements obtained at a 2.2 cm sampling distance are less effected by vaporization and dispersion of small droplets and therefore should give better agreement with atomization theory. Profiles of characteristic drop diameters were also obtained by making at least five line-of-sight measurements across the spray at several horizontal positions above and below the center line of the spray.

Agreement between experimental and theoretical effects of nitrogen gas flowrate on liquid jet atomization

NASA Technical Reports Server (NTRS)

Ingebo, Robert D.

1987-01-01

Two-phase flows were investigated by using high velocity nitrogen gas streams to atomize small-diameter liquid jets. Tests were conducted primarily in the acceleration-wave regime for liquid jet atomization, where it was found that the loss of droplets due to vaporization had a marked effect on drop-size measurements. In addition, four identically designed two-fluid atomizers were fabricated and tested for similarity of spray profiles. A scattered-light scanner was used to measure a characteristic drop diameter, which was correlated with nitrogen gas flowrate. The exponent of 1.33 for nitrogen gas flowrate is identical to that predicted by atomization theory for liquid jet breakup in the acceleration-wave regime. This is higher than the value of 1.2 which was previously obtained at a smapling distance of 4.4 cm downstream of the atomizer. The difference is attributed to the fact that drop-size measurements obtained at a 2.2 cm sampling distance are less affected by vaporization and dispersion of small droplets and therefore should give better agreement with atomization theory. Profiles of characteristic drop diameters were also obtained by making at least five line-of-sight measurements across the spray at several horizontal positions above and below the center line of the spray.

trans-Bis(hexafluoroantimonato)(phthalocyaninato)copper(II).

PubMed

Gardberg, A S; Ibers, J A

2001-05-01

The title compound, trans-bis(hexafluoroantimonato-F)(phthalocyaninato-kappa(4)N(29,30,31,32))copper(II), [Cu(SbF(6))(2)(C(32)H(16)N(8))] or Cu(pc)(SbF(6))(2) (pc is phthalocyaninate), comprises a six-coordinate Cu atom, lying on an inversion center, bonded to four N atoms of a phthalocyanine ring and to F atoms of two trans SbF(6)(-) groups. The compound is presumed to consist of a Cu(II) center and a doubly oxidized phthalocyanine ring, by analogy with Cu(pc)(ReO(4))(2).

Ethyl methyl 1,4-dihydro-4-(3-nitrophenyl)-2, 6-bis(1-piperidylmethyl)pyridine-3,5-dicarboxylate.

PubMed

Duque, J; Novoa De Armas, H; Pomés Hernández, R; Suárez Navarro, M; Ochoa Rodríguez, E; Salfrán, E; Verdecia Reyes, Y; Blaton, N M; Peeters, O M; De Ranter, C J

2000-11-01

In the title compound, C(28)H(38)N(4)O(6), the 4-aryl substituent occupies a pseudo-axial position approximately orthogonal to the plane of the dihydropyridine ring [88.1 (3) degrees ]. The dihydropyridine ring adopts a flattened boat conformation. The H atom on the pyridine N atom is involved in a bifurcated intramolecular hydrogen bond, the acceptors being the N atoms of the two piperidylmethyl groups [N.N 2.629 (4) and 2.695 (4) A].

Direct visualization of atomically precise nitrogen-doped graphene nanoribbons

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

Zhang, Yi; Zhang, Yanfang; Li, Geng

2014-07-14

We have fabricated atomically precise nitrogen-doped chevron-type graphene nanoribbons by using the on-surface synthesis technique combined with the nitrogen substitution of the precursors. Scanning tunneling microscopy and spectroscopy indicate that the well-defined nanoribbons tend to align with the neighbors side-by-side with a band gap of 1.02 eV, which is in good agreement with the density functional theory calculation result. The influence of the high precursor coverage on the quality of the nanoribbons is also studied. We find that graphene nanoribbons with sufficient aspect ratios can only be fabricated at sub-monolayer precursor coverage. This work provides a way to construct atomically precisemore » nitrogen-doped graphene nanoribbons.« less

Paramagnetic Gd IIIFe III heterobimetallic complexes of DTPA-bis-salicylamide

NASA Astrophysics Data System (ADS)

Aime, S.; Botta, M.; Fasano, M.; Terreno, E.

1993-08-01

The reaction between DTPA (diethylenetriaminepenta-acetic acid)-anhydride and p-aminosalicylic acid (PAS) affords a novel ligand, [DTPA(PAS) 2], able to form stable heterobimetallic complexes with Gd 3+ and Fe 3+ ions. The lanthanide ion occupies an internal coordination cage formed by three nitrogen atoms, two carboxylate and two carboxoamido groups of the ligand, whereas the outer salicylic moieties form stable chelate rings with Fe III ions. The stoichiometry of the resulting heterobimetallic complexes, established by measurements of water proton relaxation enhancement, is [(H 2O)-Gd-DTPA(PAS) 2] 2-Fe(H 2O) 2 or [(H 2O)-Gd-DTPA(PAS) 2] 3-Fe depending on the pH of the aqueous solution. The individual contributions to the observed relaxation enhancement from Gd 3+ and Fe 3+ paramagnetic ions have been clearly distinguished and analysed.

(S)-2-(Iodo-meth-yl)-1-tosyl-pyrrolidine.

PubMed

Wang, Ya-Wen; Peng, Yu

2007-12-06

In the title mol-ecule, C(12)H(16)INO(2)S, the pyrrolidine ring is in an envelope conformation. The dihedral angle between the four essentially coplanar atoms of the pyrrolidine ring and the benzene ring is 75.5 (4)°.

Calculation and Specification of the Multiple Chirality Displayed by Sugar Pyranoid Ring Structures.

ERIC Educational Resources Information Center

Shallenberger, Robert S.; And Others

1981-01-01

Describes a method, using simple algebraic notation, for calculating the nature of the salient features of a sugar pyranoid ring, the steric disposition of substituents about the reference, and the anomeric carbon atoms contained within the ring. (CS)

First-principles calculations of K-shell X-ray absorption spectra for warm dense nitrogen

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

Li, Zi; Zhang, Shen; Kang, Wei

2016-05-15

X-ray absorption spectrum is a powerful tool for atomic structure detection on warm dense matter. Here, we perform first-principles molecular dynamics and X-ray absorption spectrum calculations on warm dense nitrogen along a Hugoniot curve. From the molecular dynamics trajectory, the detailed atomic structures are examined for each thermodynamical condition. The K-shell X-ray absorption spectrum is calculated, and its changes with temperature and pressure along the Hugoniot curve are discussed. The warm dense nitrogen systems may contain isolated nitrogen atoms, N{sub 2} molecules, and nitrogen clusters, which show quite different contributions to the total X-ray spectrum due to their different electronmore » density of states. The changes of X-ray spectrum along the Hugoniot curve are caused by the different nitrogen structures induced by the temperature and the pressure. Some clear signatures on X-ray spectrum for different thermodynamical conditions are pointed out, which may provide useful data for future X-ray experiments.« less

Theoretical analysis of the influence of chelate-ring size and vicinal effects on electronic circular dichroism spectra of cobalt(III) EDDA-type complexes.

PubMed

Wang, Ai; Wang, Yuekui; Jia, Jie; Feng, Lixia; Zhang, Chunxia; Liu, Linlin

2013-06-20

To assess the contributions of configurational and vicinal effects as well as chelate-ring size to rotational strengths, the geometries of a series of cobalt(III) complexes [Co(EDDA-type)(L)](±) with the tetradentate EDDA-type ligands, EDDA (ethylenediamine-N,N'-diacetate), DMEDDA (N,N'-dimethylethylenediamine-N,N'-diacetate), DEEDDA (N,N'-diethylethylenediamine-N,N'-diacetate), and a bidentate ancillary ligand L (L = ethylenediamine, oxalate, carbonate, (S)-alanine, and malonate) in aqueous solution have been optimized at the DFT/B3LYP/6-311++G(2d,p) level of theory. Based on the optimized geometries, the excitation energies and oscillator and rotational strengths have been calculated using the time-dependent density functional theory (TDDFT) method with the same functional and basis set. The calculated circular dichroism (CD) curves are in excellent agreement with the observed ones except for some small red or blue shifts in peak wavelengths. For the influence of chelate-ring size of the bidentate ligands on the CD intensities, a qualitative analysis together with the quantitative TDDFT calculation reveal that it depends on the symmetry of the cobalt-EDDA backbone. For the s-cis-isomers, the influence is negligible due to the perturbation is symmetric. For the uns-cis-isomers, the perturbation is unsymmetric. Since a small ring size means a large perturbation, this leads to the integral CD intensities decreasing with increasing the chelate ring size. The vicinal effects of asymmetric nitrogens incorporate both the substitutent effects and conformational relaxation effects, with the former being dominant. By analyzing the contributions of chiral arrays to rotational strengths, we found that the part of contributions dominated by the S-type chiral nitrogens could be considered as a good measure for the vicinal effects of chiral nitrogens. In addition, we found that the twist form (δ/λ) of the backbone ethylenediamine ring (E-ring) of the coordinated EDDA-type ligands is a key factor to understand the properties of these chelates, because it not only dominates the relative stabilities of the s-cis-Λ(SS)-diastereoisomers with the result that λ > δ but also affects the major CD band by changing the order of the first two transitions. Moreover, the twist angle of E-ring is inversely related to the vicinal effect of chiral nitrogens. These findings may help us to understand the chelate ring size as well as vicinal effect related chiroptical phenomenon of the cobalt EDDA-type chelates.

5-Bromo-N-methyl­pyrimidin-2-amine

PubMed Central

Yang, Qi; Xu, Ning; Zhu, Kai; Lv, Xiaoping; Han, Ping-fang

2012-01-01

In the title mol­ecule, C5H6BrN3, the pyrimidine ring is essentially planar, with an r.m.s. deviation of 0.007 Å. The Br and N atoms substituted to the pyrimidine ring are coplanar with the ring [displacements = 0.032 (1) and 0.009 (5) Å, respectively], while the methyl C atom lies 0.100 (15) Å from this plane with a dihedral angle between the pyrimidine ring and the methyl­amine group of 4.5 (3)°. In the crystal, C—H⋯N, C—H⋯Br and N—H⋯N hydrogen bonds link the mol­ecules into a two-dimensional network in the (011) plane. PMID:22259398

AceDRG: a stereochemical description generator for ligands

PubMed Central

Emsley, Paul; Gražulis, Saulius; Merkys, Andrius; Vaitkus, Antanas

2017-01-01

The program AceDRG is designed for the derivation of stereochemical information about small molecules. It uses local chemical and topological environment-based atom typing to derive and organize bond lengths and angles from a small-molecule database: the Crystallography Open Database (COD). Information about the hybridization states of atoms, whether they belong to small rings (up to seven-membered rings), ring aromaticity and nearest-neighbour information is encoded in the atom types. All atoms from the COD have been classified according to the generated atom types. All bonds and angles have also been classified according to the atom types and, in a certain sense, bond types. Derived data are tabulated in a machine-readable form that is freely available from CCP4. AceDRG can also generate stereochemical information, provided that the basic bonding pattern of a ligand is known. The basic bonding pattern is perceived from one of the computational chemistry file formats, including SMILES, mmCIF, SDF MOL and SYBYL MOL2 files. Using the bonding chemistry, atom types, and bond and angle tables generated from the COD, AceDRG derives the ‘ideal’ bond lengths, angles, plane groups, aromatic rings and chirality information, and writes them to an mmCIF file that can be used by the refinement program REFMAC5 and the model-building program Coot. Other refinement and model-building programs such as PHENIX and BUSTER can also use these files. AceDRG also generates one or more coordinate sets corresponding to the most favourable conformation(s) of a given ligand. AceDRG employs RDKit for chemistry perception and for initial conformation generation, as well as for the interpretation of SMILES strings, SDF MOL and SYBYL MOL2 files. PMID:28177307

Photoionization research on atomic radiation. 3: The ionization cross section of atomic nitrogen

NASA Technical Reports Server (NTRS)

Comes, F. J.; Elzer, A.

1982-01-01

The photoionization cross section of atomic nitrogen was measured between the ionization limit and 432 A. The experimental values are well fitted by those from a calculation of HENRY due to the dipole velocity approximation. A Rydberg series converging to the 5S-state of the ion is clearly identified from the ionization measurements and is shown to ionize.

The Effect of n vs. iso Isomerization on the Thermophysical Properties of Aromatic and Non-aromatic Ionic Liquids.

PubMed

Rodrigues, Ana S M C; Almeida, Hugo F D; Freire, Mara G; Lopes-da-Silva, José A; Coutinho, João A P; Santos, Luís M N B F

2016-09-15

This work explores the n vs. iso isomerization effects on the physicochemical properties of different families of ionic liquids (ILs) with variable aromaticity and ring size. This study comprises the experimental measurements, in a wide temperature range, of the ILs' thermal behavior, heat capacities, densities, refractive indices, surface tensions, and viscosities. The results here reported show that the presence of the iso -alkyl group leads to an increase of the temperature of the glass transition, T g . The iso- pyrrolidinium (5 atoms ring cation core) and iso -piperidinium (6 atoms ring cation core) ILs present a strong differentiation in the enthalpy and entropy of melting. Non-aromatic ILs have higher molar heat capacities due to the increase of the atomic contribution, whereas it was not found any significant differentiation between the n and iso -alkyl isomers. A small increase of the surface tension was observed for the non-aromatic ILs, which could be related to their higher cohesive energy of the bulk, while the lower surface entropy observed for the iso isomers indicates a structural resemblance between the IL bulk and surface. The significant differentiation between ILs with a 5 and 6 atoms ring cation in the n -alkyl series (where 5 atoms ring cations have higher surface entropy) is an indication of a more efficient arrangement of the non-polar region at the surface in ILs with smaller cation cores. The ILs constituted by non-aromatic piperidinium cation, and iso -alkyl isomers were found to be the most viscous among the studied ILs due to their higher energy barriers for shear stress.

Crystal structure of 1-(8-meth-oxy-2H-chromen-3-yl)ethanone.

PubMed

Koh, Dongsoo

2014-09-01

In the structure of the title compound, C12H12O3, the di-hydro-pyran ring is fused with the benzene ring. The di-hydro-pyran ring is in a half-chair conformation, with the ring O and methyl-ene C atoms positioned 1.367 (3) and 1.504 (4) Å, respectively, on either side of the mean plane formed by the other four atoms. The meth-oxy group is coplanar with the benzene ring to which it is connected [Cb-Cb-Om-Cm torsion angle = -0.2 (4)°; b = benzene and m = meth-oxy], and similarly the aldehyde is coplanar with respect to the double bond of the di-hydro-pyran ring [Cdh-Cdh-Ca-Oa = -178.1 (3)°; dh = di-hydro-pyran and a = aldehyde]. In the crystal, mol-ecules are linked by weak meth-yl-meth-oxy C-H⋯O hydrogen bonds into supra-molecular chains along the a-axis direction.

Characterization of heterocyclic rings through quantum chemical topology.

PubMed

Griffiths, Mark Z; Popelier, Paul L A

2013-07-22

Five-membered rings are found in a myriad of molecules important in a wide range of areas such as catalysis, nutrition, and drug and agrochemical design. Systematic insight into their largely unexplored chemical space benefits from first principle calculations presented here. This study comprehensively investigates a grand total of 764 different rings, all geometry optimized at the B3LYP/6-311+G(2d,p) level, from the perspective of Quantum Chemical Topology (QCT). For the first time, a 3D space of local topological properties was introduced, in order to characterize rings compactly. This space is called RCP space, after the so-called ring critical point. This space is analogous to BCP space, named after the bond critical point, which compactly and successfully characterizes a chemical bond. The relative positions of the rings in RCP space are determined by the nature of the ring scaffold, such as the heteroatoms within the ring or the number of π-bonds. The summed atomic QCT charges of the five ring atoms revealed five features (number and type of heteroatom, number of π-bonds, substituent and substitution site) that dictate a ring's net charge. Each feature independently contributes toward a ring's net charge. Each substituent has its own distinct and systematic effect on the ring's net charge, irrespective of the ring scaffold. Therefore, this work proves the possibility of designing a ring with specific properties by fine-tuning it through manipulation of these five features.

Global, Energy-Dependent Ring Current Response During Two Large Storms

NASA Astrophysics Data System (ADS)

Goldstein, J.; Angelopoulos, V.; Burch, J. L.; De Pascuale, S.; Fuselier, S. A.; Genestreti, K. J.; Kurth, W. S.; LLera, K.; McComas, D. J.; Reeves, G. D.; Spence, H. E.; Valek, P. W.

2015-12-01

Two recent large (~200 nT) geomagnetic storms occurred during 17--18 March 2015 and 22--23 June 2015. The global, energy-dependent ring current response to these two extreme events is investigated using both global imaging and multi-point in situ observations. Energetic neutral atom (ENA) imaging by the Two Wide-angle Imaging Neutral-atom Spectrometers (TWINS) mission provides a global view of ring current ions. Local measurements are provided by two multi-spacecraft missions. The two Van Allen Probes measure in situ plasma (including ion composition) and fields at ring current and plasmaspheric L values. The recently launched Magnetospheric Multiscale (MMS) comprises four spacecraft that have just begun to measure particles (including ion composition) and fields at outer magnetospheric L-values. We analyze the timing and energetics of the stormtime evolution of ring current ions, both trapped and precipitating, using TWINS ENA images and in situ data by the Van Allen Probes and MMS.

Single-molecule conductance through multiple π-π-stacked benzene rings determined with direct electrode-to-benzene ring connections.

PubMed

Schneebeli, Severin T; Kamenetska, Maria; Cheng, Zhanling; Skouta, Rachid; Friesner, Richard A; Venkataraman, Latha; Breslow, Ronald

2011-02-23

Understanding electron transport across π-π-stacked systems will help to answer fundamental questions about biochemical redox processes and benefit the design of new materials and molecular devices. Herein we employed the STM break-junction technique to measure the single-molecule conductance of multiple π-π-stacked aromatic rings. We studied electron transport through up to four stacked benzene rings held together in an eclipsed fashion via a paracyclophane scaffold. We found that the strained hydrocarbons studied herein couple directly to gold electrodes during the measurements; hence, we did not require any heteroatom binding groups as electrical contacts. Density functional theory-based calculations suggest that the gold atoms of the electrodes bind to two neighboring carbon atoms of the outermost cyclophane benzene rings in η(2) fashion. Our measurements show an exponential decay of the conductance with an increasing number of stacked benzene rings, indicating a nonresonant tunneling mechanism. Furthermore, STM tip-substrate displacement data provide additional evidence that the electrodes bind to the outermost benzene rings of the π-π-stacked molecular wires.

Dichloridobis(phenanthridine-κN)zinc(II).

PubMed

Khoshtarkib, Zeinab; Ebadi, Amin; Alizadeh, Robabeh; Ahmadi, Roya; Amani, Vahid

2009-06-06

In the mol-ecule of the title compound, [ZnCl(2)(C(13)H(9)N)(2)], the Zn(II) atom is four-coordinated in a distorted tetra-hedral configuration by two N atoms from two phenanthridine ligands and by two terminal Cl atoms. The dihedral angle between the planes of the phenanthridine ring systems is 69.92 (3)°. An intra-molecular C-H⋯Cl inter-action results in the formation of a planar five-membered ring, which is oriented at a dihedral angle of 8.32 (3)° with respect to the adjacent phenanthridine ring system. In the crystal structure, π-π contacts between the phenanthridine systems [centroid-centroid distances = 3.839 (2), 3.617 (1) and 3.682 (1) Å] may stabilize the structure. Two weak C-H⋯π inter-actions are also found.

The oxidation degradation of aromatic compounds

NASA Technical Reports Server (NTRS)

Brezinsky, Kenneth; Glassman, Irvin

1987-01-01

A series of experiments were conducted which focused on understanding the role that the O atom addition to aromatic rings plays in the oxidation of benzene and toluene. Flow reactor studies of the oxidation of toluene gave an indication of the amount of O atoms available during an oxidation and the degree to which the O atom adds to the ring. Flow reactor studies of the oxidation of toluene and benzene to which NO2 was added, have shown that NO2 appears to suppress the formation of O atoms and consequently reduce the amount of phenols and cresols formed by O atom addition. A high temperature pyrolysis study of phenol has confirmed that the major decomposition products are carbon monoxide and cyclopentadiene. A preliminary value for the overall decomposition rate constant was also obtained.

Electrode structure of a compact microwave driven capacitively coupled atomic beam source

NASA Astrophysics Data System (ADS)

Shimabukuro, Yuji; Takahashi, Hidenori; Wada, Motoi

2018-01-01

A compact magnetic field free atomic beam source was designed, assembled and tested the performance to produce hydrogen and nitrogen atoms. A forced air-cooled solid-state microwave power supply at 2.45 GHz frequency drives the source up to 100 W through a coaxial transmission cable coupled to a triple stub tuner for realizing a proper matching condition to the discharge load. The discharge structure of the source affected the range of operation pressure, and the pressure was reduced by four orders of magnitude through improving the electrode geometry to enhance the local electric field intensity. Optical emission spectra of the produced plasmas indicate production of hydrogen and nitrogen atoms, while the flux intensity of excited nitrogen atoms monitored by a surface ionization type detector showed the signal level close to a source developed for molecular beam epitaxy applications with 500 W RF power.

Collisional-radiative nonequilibrium in partially ionized atomic nitrogen

NASA Technical Reports Server (NTRS)

Kunc, J. A.; Soon, W. H.

1989-01-01

A nonlinear collisional-radiative model for determination of nonequilibrium production of electrons, excited atoms, and bound-bound, dielectronic and continuum line intensities in stationary partially ionized atomic nitrogen is presented. Populations of 14 atomic levels and line intensities are calculated in plasma with T(e) = 8000-15,000 K and N(t) = 10 to the 12th - 10 to the 18th/cu cm. Transport of radiation is included by coupling the rate equations of production of the electrons and excited atoms with the radiation escape factors, which are not constant but depend on plasma conditions.

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

Chumakov, Yu. M.; Tsapkov, V. I., E-mail: vtsapkov@gmail.com; Antosyak, B. Ya.

Nitrato-4-bromo-2-[(2-hydroxyethylimino)methyl]phenolatoimidazolecopper and nitrato-4-chloro-2-[(2-hydroxyethylimino)methyl]phenolatoimidazolecopper were synthesized and studied by X-ray diffraction. The crystals are isostructural. The coordination polyhedron of the copper atom can be described as a distorted square pyramid whose basal plane is formed by the phenolic and alcoholic oxygen atoms and the nitrogen atom of the monodeprotonated tridentate azomethine molecule and the imidazole nitrogen atom. The apex of the copper polyhedron is occupied by the oxygen atom of the nitrato group. The complexes are linked together by hydrogen bonds with the participation of the nitrato groups to form a three-dimensional framework.

NO.sub.x reduction method

DOEpatents

Sekar, Ramanujam R.; Hoppie, Lyle O.

1996-01-01

A method of reducing oxides of nitrogen (NO.sub.X) in the exhaust of an internal combustion engine includes producing oxygen enriched air and nitrogen enriched air by an oxygen enrichment device. The oxygen enriched air may be provided to the intake of the internal combustion engine for mixing with fuel. In order to reduce the amount of NO.sub.X in the exhaust of the internal combustion engine, the molecular nitrogen in the nitrogen enriched air produced by the oxygen enrichment device is subjected to a corona or arc discharge so as to create a plasma and as a result, atomic nitrogen. The resulting atomic nitrogen then is injected into the exhaust of the internal combustion engine causing the oxides of nitrogen in the exhaust to be reduced into nitrogen and oxygen. In one embodiment of the present invention, the oxygen enrichment device that produces both the oxygen and nitrogen enriched air can include a selectively permeable membrane.

7-Meth­oxy-2-phenyl­chroman-4-one

PubMed Central

Piaskowska, Agata; Hodorowicz, Maciej; Nitek, Wojciech

2013-01-01

In the title compound, C16H14O3, the ring O atom and the two adjacent non-fused C atoms, as well as the attached phenyl ring, exhibit static disorder [occupancy ratio 0.559 (12):0.441 (12)]. The crystal packing features π–π [centroid–centroid distance = 3.912 (1) Å] and C—H⋯π inter­actions. PMID:23424545

Dispersion engineering of thick high-Q silicon nitride ring-resonators via atomic layer deposition.

PubMed

Riemensberger, Johann; Hartinger, Klaus; Herr, Tobias; Brasch, Victor; Holzwarth, Ronald; Kippenberg, Tobias J

2012-12-03

We demonstrate dispersion engineering of integrated silicon nitride based ring resonators through conformal coating with hafnium dioxide deposited on top of the structures via atomic layer deposition. Both, magnitude and bandwidth of anomalous dispersion can be significantly increased. The results are confirmed by high resolution frequency-comb-assisted-diode-laser spectroscopy and are in very good agreement with the simulated modification of the mode spectrum.

Mechanism for Ring-Opening of Aromatic Polymers by Remote Atmospheric Pressure Plasma

NASA Astrophysics Data System (ADS)

Gonzalez, Eleazar; Barankin, Michael; Guschl, Peter; Hicks, Robert

2009-10-01

A low-temperature, atmospheric pressure oxygen and helium plasma was used to treat the surfaces of polyetheretherketone, polyphenylsulfone, polyethersulfone, and polysulfone. These aromatic polymers were exposed to the afterglow of the plasma, which contained oxygen atoms, and to a lesser extent metastable oxygen (^1δg O2) and ozone. After less than 2.5 seconds treatment, the polymers were converted from a hydrophobic state with a water contact angle of 85±5 to a hydrophilic state with a water contact angle of 13±5 . It was found that plasma activation increased the bond strength to adhesives by as much as 4 times. X-ray photoelectron spectroscopy revealed that between 7% and 27% of the aromatic carbon atoms on the polymer surfaces was oxidized and converted into aldehyde and carboxylic acid groups. Analysis of polyethersulfone by internal reflection infrared spectroscopy showed that a fraction of the aromatic carbon atoms were transformed into C=C double bonds, ketones, and carboxylic acids after plasma exposure. It was concluded that the oxygen atoms generated by the atmospheric pressure plasma insert into the double bonds on the aromatic rings, forming a 3-member epoxy ring, which subsequently undergoes ring opening and oxidation to yield an aldehyde and a carboxylic acid group.

Trace elements and nitrogen content in naturally growing moss Hypnum cupressiforme in urban and peri-urban forests of the Municipality of Ljubljana (Slovenia).

PubMed

Berisha, S; Skudnik, M; Vilhar, U; Sabovljević, M; Zavadlav, S; Jeran, Z

2017-02-01

We monitored trace metals and nitrogen using naturally growing moss Hypnum cupressiforme Hedw. in urban and peri-urban forests of the City Municipality of Ljubljana. The aim of this study was to explore the differences in atmospheric deposition of trace metals and nitrogen between urban and peri-urban forests. Samples were collected at a total of 44 sites in urban forests (forests within the motorway ring road) and peri-urban forests (forests outside the motorway ring road). Mosses collected in urban forests showed increased trace metal concentrations compared to samples collected from peri-urban forests. Higher values were significant for As, Cr, Cu, Hg, Mo, Ni, Pb, Sb, Tl and V. Within the motorway ring road, the notable differences in element concentrations between the two urban forests were significant for Cr, Ni and Mo. Factor analysis showed three groups of elements, highlighting the contribution of traffic emissions, individual heating appliances and the resuspension of contaminated soils and dust as the main sources of trace elements in urban forests.

Transnitrosation of alicyclic N-nitrosamines containing a sulfur atom.

PubMed

Inami, Keiko; Kondo, Sonoe; Ono, Yuta; Saso, Chiharu; Mochizuki, Masataka

2013-12-15

Aromatic and aliphatic nitrosamines are known to transfer a nitrosonium ion to another amine. The transnitrosation of alicyclic N-nitroso compounds generates S-nitrosothiols, which are potential nitric oxide donors in vivo. In this study, certain alicyclic N-nitroso compounds based on non-mutagenic N-nitrosoproline or N-nitrosothioproline were synthesised, and the formation of S-nitrosoglutathione (GSNO) was quantified under acidic conditions. We then investigated the effect of a sulfur atom as the substituent and as a ring component on the GSNO formation. In the presence of thiourea under acidic conditions, GSNO was formed from N-nitrosoproline and glutathione, and an N-nitroso compound containing a sulfur atom and glutathione produced GSNO without thiourea. The quantity of GSNO derived from the reaction of the N-nitrosamines containing a sulfur atom and glutathione was higher than that from the N-nitrosoproline and glutathione plus thiourea. Among the analogues that contained a sulfur atom either in the ring or as a substituent, the thiazolidines produced a slightly higher quantity of GSNO than the analogue with a thioamide group. A compound containing sulfur atoms both in the ring and as a substituent exhibited the highest activity for GSNO formation among the alicyclic N-nitrosamines tested. The results indicate that the intramolecular sulfur atom plays an important role in the transnitrosation via alicyclic N-nitroso compounds to form GSNO. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

N2 Dissociation In The Mesosphere Due To Secondary Electrons During A Solar Proton Event: The Effect On Atomic Nitrogen and Nitric Oxide

NASA Astrophysics Data System (ADS)

Verronen, P. T.; Shematovich, V. I.; Bisikalo, D. V.; Turunen, E.; Ulich, Th.

Solar proton events have an effect on the middle atmospheric odd nitrogen chem- istry. During a solar proton event high energy protons enter Earth's middle atmosphere where they ionize ambient gas. Ionization leads to production of atomic nitrogen, and further to production of nitric oxide, through ion chemistry. In addition, ionization processes produce secondary electrons that, if possessing 9.76 eV or more energy, dissociate N2 providing an additional source of atomic nitrogen. We have calculated mesospheric N2 dissociation rate due to secondary electrons dur- ing a solar proton event. Further, we have studied the effect on atomic nitrogen and nitric oxide at altitudes between 50 and 90 km. It was found that N2 is efficiently dis- sociated in the lower mesosphere by secondary electrons, with rates up to 103 cm-3 s-1 at 50 km. Thus, secondary electrons significantly add to odd nitrogen produc- tion. As a result of N2 dissociation, atomic nitrogen is greatly enhanced in both N(4S) and N(2D) states by 259% and 1220% maximum increases at 50 km, respectively. This further leads to a maximum increase of 16.5% in NO concentration at 61 km via chemical reactions. In our study a Monte Carlo model was used to calculate the total ionization rate and secondary electrons flux due to precipitating protons. These where then used as input to a detailed ion and neutral chemistry model and a steady-state solution was calcu- lated for two cases: With and without N2 dissociation due to secondary electrons.

β-Lactam Ring Opening: A Useful Entry to Amino Acids and Relevant Nitrogen-Containing Compounds

NASA Astrophysics Data System (ADS)

Palomo, C.; Oiarbide, M.

The main strategies for the ring opening of β-lactams by chemical means are described. The discovery of each approach is put into context, sometimes in connection to processes occurring in biological systems, and the synthetic opportunities each approach offers are shown. Thus, this β-lactam route affords a number of synthetically relevant building-blocks, including α-amino acids, β-amino acids, their derived peptides, and other nitrogen containing heterocycles and open chain molecules. The content, which encompases references to initial work, further major development, and the most relevant recent literature contributions, is categorized according to the ring bond cleavaged (N 1-C 2, C 2-C 3, C 3 -C 4 , N 1-C 4), to finish with ring opening strategies leading to large heterocyclic compounds. Within each category, distinction has been made according to the type of nucleophilic agent employed, principally O-, N-, and C-nucleophiles. Also, a variety of applications of the strategy to the synthesis of interesting target compounds are shown.

Dark optical lattice of ring traps for cold atoms

NASA Astrophysics Data System (ADS)

Courtade, Emmanuel; Houde, Olivier; Clément, Jean-François; Verkerk, Philippe; Hennequin, Daniel

2006-09-01

We propose an optical lattice for cold atoms made of a one-dimensional stack of dark ring traps. It is obtained through the interference pattern of a standard Gaussian beam with a counterpropagating hollow beam obtained using a setup with two conical lenses. The traps of the resulting lattice are characterized by a high confinement and a filling rate much larger than unity, even if loaded with cold atoms from a magneto-optical trap. We have implemented this system experimentally, and demonstrated its feasibility. Applications in statistical physics, quantum computing, and Bose-Einstein condensate dynamics are conceivable.

Permeability of two-dimensional graphene and hexagonal-boron nitride to hydrogen atom

NASA Astrophysics Data System (ADS)

Gupta, Varun; Kumar, Ankit; Ray, Nirat

2018-05-01

The permeability of atomic hydrogen in monolayer hexagonal Boron Nitride(h-BN) and graphene has been studied using first-principles density functional theory based simulations. For the specific cases of physisorption and chemisoroption, barrier heights are calculated using the nudged elastic band approach. We find that the barrier potential for physisorption through the ring is lower for graphene than h-BN. In the case of chemisorption, where the H atom passes through by making bonds with the atoms in the ring, the barrier potential for the graphene was found to be higher than that of h-BN. We conclude that the penetration of H atom with notable kinetic energy (<3eV) through physiosorption is more probable for graphene as compared to h-BN. Whereas through chemisorption, lower kinetic energy (>3eV) H-atoms have a higher chance to penetrate through h-BN than graphene.

Nitrogen spark denoxer

DOEpatents

Ng, Henry K.; Novick, Vincent J.; Sekar, Ramanujam R.

1997-01-01

A NO.sub.X control system for an internal combustion engine includes an oxygen enrichment device that produces oxygen and nitrogen enriched air. The nitrogen enriched air contains molecular nitrogen that is provided to a spark plug that is mounted in an exhaust outlet of an internal combustion engine. As the nitrogen enriched air is expelled at the spark gap of the spark plug, the nitrogen enriched air is exposed to a pulsating spark that is generated across the spark gap of the spark plug. The spark gap is elongated so that a sufficient amount of atomic nitrogen is produced and is injected into the exhaust of the internal combustion engine. The injection of the atomic nitrogen into the exhaust of the internal combustion engine causes the oxides of nitrogen to be reduced into nitrogen and oxygen such that the emissions from the engine will have acceptable levels of NO.sub.X. The oxygen enrichment device that produces both the oxygen and nitrogen enriched air can include a selectively permeable membrane.

Total synthesis of bryostatins: the development of methodology for the atom-economic and stereoselective synthesis of the ring C subunit.

PubMed

Trost, Barry M; Frontier, Alison J; Thiel, Oliver R; Yang, Hanbiao; Dong, Guangbin

2011-08-22

Bryostatins, a family of structurally complicated macrolides, exhibit an exceptional range of biological activities. The limited availability and structural complexity of these molecules makes development of an efficient total synthesis particularly important. This article describes our initial efforts towards the total synthesis of bryostatins, in which chemoselective and atom-economical methods for the stereoselective assembly of the ring C subunit were developed. A Pd-catalyzed tandem alkyne-alkyne coupling/6-endo-dig cyclization sequence was explored and successfully pursued in the synthesis of a dihydropyran ring system. Elaboration of this methodology ultimately led to a concise synthesis of the ring C subunit of bryostatins. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystal structure of bis-(μ-3-nitro-benzoato)-κ3O,O':O;κ3O:O,O'-bis-[bis-(3-cyano-pyridine-κN1)(3-nitro-benzoato-κ2O,O')cadmium].

PubMed

Hökelek, Tuncer; Akduran, Nurcan; Özen, Azer; Uğurlu, Güventürk; Necefoğlu, Hacali

2017-03-01

The asymmetric unit of the title compound, [Cd 2 (C 7 H 4 NO 4 ) 4 (C 6 H 4 N 2 ) 4 ], contains one Cd II atom, two 3-nitro-benzoate (NB) anions and two 3-cyano-pyridine (CPy) ligands. The two CPy ligands act as monodentate N(pyridine)-bonding ligands, while the two NB anions act as bidentate ligands through the carboxyl-ate O atoms. The centrosymmetric dinuclear complex is generated by application of inversion symmetry, whereby the Cd II atoms are bridged by the carboxyl-ate O atoms of two symmetry-related NB anions, thus completing the distorted N 2 O 5 penta-gonal-bipyramidal coordination sphere of each Cd II atom. The benzene and pyridine rings are oriented at dihedral angles of 10.02 (7) and 5.76 (9)°, respectively. In the crystal, C-H⋯N hydrogen bonds link the mol-ecules, enclosing R 2 2 (26) ring motifs, in which they are further linked via C-H⋯O hydrogen bonds, resulting in a three-dimensional network. In addition, π-π stacking inter-actions between parallel benzene rings and between parallel pyridine rings of adjacent mol-ecules [shortest centroid-to-centroid distances = 3.885 (1) and 3.712 (1) Å, respectively], as well as a weak C-H⋯π inter-action, may further stabilize the crystal structure.

Modeling aerosols formed in the ring - pack of reciprocating piston

NASA Astrophysics Data System (ADS)

Dallstream, Brian Ellis

The hydrocarbon emissions of an internal combustion engine are directly correlated with the engine's oil consumption. This oil consumption is associated with reverse blow-by, a condition in which gases flow past the ring-pack from the crankcase to the combustion chamber. This reverse blow-by breaks down the oil film on the cylinder walls and entrains oil particles in the gas flow during the downstroke of the piston. In this project a numerical model was developed that accurately describes the formation of aerosols in the ring pack by simulating the mechanisms by which oil globules are broken up, atomized, and entrained in a gas flowing through an orifice. The results of this numerical model are in good agreement with experimental values. Thus, this numerical model gives insight into the parameters that govern oil consumption. A discussion is also presented regarding the general applications of atomization and how past researchers have developed and advanced the theories of atomization.Included in this discussion is an introduction to past models of oil consumption and the conditions needed for aerosols to form within the ring-pack of a piston.

Enumerating Substituted Benzene Isomers of Tree-Like Chemical Graphs.

PubMed

Li, Jinghui; Nagamochi, Hiroshi; Akutsu, Tatsuya

2018-01-01

Enumeration of chemical structures is useful for drug design, which is one of the main targets of computational biology and bioinformatics. A chemical graph with no other cycles than benzene rings is called tree-like, and becomes a tree possibly with multiple edges if we contract each benzene ring into a single virtual atom of valence 6. All tree-like chemical graphs with a given tree representation are called the substituted benzene isomers of . When we replace each virtual atom in with a benzene ring to obtain a substituted benzene isomer, distinct isomers of are caused by the difference in arrangements of atom groups around a benzene ring. In this paper, we propose an efficient algorithm that enumerates all substituted benzene isomers of a given tree representation . Our algorithm first counts the number of all the isomers of the tree representation by a dynamic programming method. To enumerate all the isomers, for each , our algorithm then generates the th isomer by backtracking the counting phase of the dynamic programming. We also implemented our algorithm for computational experiments.

A quantum chemical study for exploring the inhibitory effect of nitrogen containing species on the adsorption of polynuclear aromatic hydrocarbons over a Bronsted acid site

NASA Astrophysics Data System (ADS)

Celis-Cornejo, C. M.; Garnica Mantilla, M. M.; Baldovino-Medrano, V. G.; Ramírez-Caballero, G. E.

2016-08-01

The analysis of the inhibitory effect of nitrogenated compounds on the hydroprocessing and hydropurification of oil derived fuels is important to produce cleaner fuels. In this work, density functional theory calculations were performed to investigate the effect of the nitrogen containing molecules on the adsorption of Polynuclear Aromatic Hydrocarbons (PAHs). Mordenite was chosen as a zeolitic structure for simulating a Bronsted acid site. The character of the acid site was confirmed by both a vibrational frequency calculation and a Bader charge analysis. From the adsorption calculations, it was found that the adsorption energy of PAHs increases with the number of aromatic rings in the structure. Also, the nitrogen containing species possibly inhibit more extensively two and three rings PAHs because of their lower adsorption energies. Finally, it was observed that the nitrogen species tend to drag the proton from the mordenite acid site. This explains the inhibitory effect in the adsorption of PAHs and contributes to understanding the dynamics of hydrocarbon hydroprocessing in refineries.

Ring Current Dynamics in Moderate and Strong Storms: Comparative Analysis of TWINS and IMAGE/HENA Data with the Comprehensive Ring Current Model

NASA Technical Reports Server (NTRS)

Buzulukova, N.; Fok, M.-C.; Goldstein, J.; Valek, P.; McComas, D. J.; Brandt, P. C.

2010-01-01

We present a comparative study of ring current dynamics during strong and moderate storms. The ring current during the strong storm is studied with IMAGE/HENA data near the solar cycle maximum in 2000. The ring current during the moderate storm is studied using energetic neutral atom (ENA) data from the Two Wide-Angle Imaging Neutral- Atom Spectrometers (TWINS) mission during the solar minimum in 2008. For both storms, the local time distributions of ENA emissions show signatures of postmidnight enhancement (PME) during the main phases. To model the ring current and ENA emissions, we use the Comprehensive Ring Current Model (CRCM). CRCM results show that the main-phase ring current pressure peaks in the premidnight-dusk sector, while the most intense CRCM-simulated ENA emissions show PME signatures. We analyze two factors to explain this difference: the dependence of charge-exchange cross section on energy and pitch angle distributions of ring current. We find that the IMF By effect (twisting of the convection pattern due to By) is not needed to form the PME. Additionally, the PME is more pronounced for the strong storm, although relative shielding and hence electric field skewing is well developed for both events.

(S)-2-(Iodo­meth­yl)-1-tosyl­pyrrolidine

PubMed Central

Wang, Ya-Wen; Peng, Yu

2008-01-01

In the title mol­ecule, C12H16INO2S, the pyrrolidine ring is in an envelope conformation. The dihedral angle between the four essentially coplanar atoms of the pyrrolidine ring and the benzene ring is 75.5 (4)°. PMID:21200932

Quantitative structure-activity relationship analysis of substituted arylazo pyridone dyes in photocatalytic system: Experimental and theoretical study.

PubMed

Dostanić, J; Lončarević, D; Zlatar, M; Vlahović, F; Jovanović, D M

2016-10-05

A series of arylazo pyridone dyes was synthesized by changing the type of the substituent group in the diazo moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The structural and electronic properties of the investigated dyes was calculated at the M062X/6-31+G(d,p) level of theory. The observed good linear correlations between atomic charges and Hammett σp constants provided a basis to discuss the transmission of electronic substituent effects through a dye framework. The reactivity of synthesized dyes was tested through their decolorization efficiency in TiO2 photocatalytic system (Degussa P-25). Quantitative structure-activity relationship analysis revealed a strong correlation between reactivity of investigated dyes and Hammett substituent constants. The reaction was facilitated by electron-withdrawing groups, and retarded by electron-donating ones. Quantum mechanical calculations was used in order to describe the mechanism of the photocatalytic oxidation reactions of investigated dyes and interpret their reactivities within the framework of the Density Functional Theory (DFT). According to DFT based reactivity descriptors, i.e. Fukui functions and local softness, the active site moves from azo nitrogen atom linked to benzene ring to pyridone carbon atom linked to azo bond, going from dyes with electron-donating groups to dyes with electron-withdrawing groups. Copyright © 2016 Elsevier B.V. All rights reserved.

Optical and Electron Spin Resonance Studies of Destruction of Porous Structures Formed by Nitrogen-Rare Gas Nanoclusters in Bulk Superfluid Helium

NASA Astrophysics Data System (ADS)

McColgan, Patrick T.; Meraki, Adil; Boltnev, Roman E.; Lee, David M.; Khmelenko, Vladimir V.

2017-04-01

We studied optical and electron spin resonance spectra during destruction of porous structures formed by nitrogen-rare gas (RG) nanoclusters in bulk superfluid helium containing high concentrations of stabilized nitrogen atoms. Samples were created by injecting products of a radio frequency discharge of nitrogen-rare gas-helium gas mixtures into bulk superfluid helium. These samples have a high energy density allowing the study of energy release in chemical processes inside of nanocluster aggregates. The rare gases used in the studies were neon, argon, and krypton. We also studied the effects of changing the relative concentrations between nitrogen and rare gas on thermoluminescence spectra during destruction of the samples. At the beginning of the destructions, α -group of nitrogen atoms, Vegard-Kaplan bands of N_2 molecules, and β -group of O atoms were observed. The final destruction of the samples were characterized by a series bright flashes. Spectra obtained during these flashes contain M- and β -bands of NO molecules, the intensities of which depend on the concentration of molecular nitrogen in the gas mixture as well as the type of rare gas present in the gas mixture.

Dietary nitrogen alters codon bias and genome composition in parasitic microorganisms.

PubMed

Seward, Emily A; Kelly, Steven

2016-11-15

Genomes are composed of long strings of nucleotide monomers (A, C, G and T) that are either scavenged from the organism's environment or built from metabolic precursors. The biosynthesis of each nucleotide differs in atomic requirements with different nucleotides requiring different quantities of nitrogen atoms. However, the impact of the relative availability of dietary nitrogen on genome composition and codon bias is poorly understood. Here we show that differential nitrogen availability, due to differences in environment and dietary inputs, is a major determinant of genome nucleotide composition and synonymous codon use in both bacterial and eukaryotic microorganisms. Specifically, low nitrogen availability species use nucleotides that require fewer nitrogen atoms to encode the same genes compared to high nitrogen availability species. Furthermore, we provide a novel selection-mutation framework for the evaluation of the impact of metabolism on gene sequence evolution and show that it is possible to predict the metabolic inputs of related organisms from an analysis of the raw nucleotide sequence of their genes. Taken together, these results reveal a previously hidden relationship between cellular metabolism and genome evolution and provide new insight into how genome sequence evolution can be influenced by adaptation to different diets and environments.

The role of nitrogen ions in the ring current dynamics

NASA Astrophysics Data System (ADS)

Ilie, R.; Liemohn, M. W.; Dandouras, I. S.

2017-12-01

Changes in the ion composition throughout the Earth's magnetosphere can have profound implications on plasma structures and dynamics, since it can modify the temperature and the magnetic field configuration, altering the convection patterns inside the magnetosphere. The ratio of hydrogen to oxygen ions has been shown to be highly dependent of geomagnetic activity, with the O+ content increasing with increasing activity. This suggests that ions of ionospheric origin can become the dominant species in the inner magnetosphere during disturbed times. Therefore, numerous studies have focused on the transport and energization of O+ through the ionosphere-magnetosphere system; however, relatively few have considered the contribution of N+, in addition to that of O+ to the near-Earth plasma dynamics, even though past observations have established that N+ is a significant ion species in the ionosphere and its presence in the magnetosphere is significant. Ring current observations from the Active Magnetospheric Particle Tracer Explorer (AMPTE) spacecraft show that high energy N+ fluxes are comparable to those of O+ during disturbed times, confirming the substantial presence of N+ions in the inner magnetosphere. In spite of only 12% mass difference, N+ and O+ have different ionization potentials, scale heights and charge exchange cross sections. The latter, together with the geocoronal density distribution, plays a key role in the formation of Energetic Neutral Atoms (ENAs), which in turn control the energy budget of the inner magnetosphere and the decay of the ring current. Numerical simulations using the Hot Electron and Ion Drift Integrator (HEIDI) model suggest that the contribution of N+ to the ring current dynamics is significant, as the presence of N+, in addition to that of O+, alters the development and the decay rate of the ring current. These findings suggest that differentiating the N+ transport from that of O+ in the near-Earth environment has a profound impact on global magnetosphere dynamics, as plasma composition affects both the local and the global properties of the plasma.

Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study

DOE PAGES

Chuang, Cheng-Hao; Ray, Sekhar C.; Mazumder, Debarati; ...

2017-02-10

Nitrogen-doped graphene oxides (GO:N x) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH 2) 2 ]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:N x synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in whichmore » each N-atom trigonally bonds to three distinct sp 2 -hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:N x . The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.« less

Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study

NASA Astrophysics Data System (ADS)

Chuang, Cheng-Hao; Ray, Sekhar C.; Mazumder, Debarati; Sharma, Surbhi; Ganguly, Abhijit; Papakonstantinou, Pagona; Chiou, Jau-Wern; Tsai, Huang-Ming; Shiu, Hung-Wei; Chen, Chia-Hao; Lin, Hong-Ji; Guo, Jinghua; Pong, Way-Faung

2017-02-01

Nitrogen-doped graphene oxides (GO:Nx) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH2)2]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:Nx synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in which each N-atom trigonally bonds to three distinct sp2-hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:Nx. The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.

From rotating atomic rings to quantum Hall states.

PubMed

Roncaglia, M; Rizzi, M; Dalibard, J

2011-01-01

Considerable efforts are currently devoted to the preparation of ultracold neutral atoms in the strongly correlated quantum Hall regime. However, the necessary angular momentum is very large and in experiments with rotating traps this means spinning frequencies extremely near to the deconfinement limit; consequently, the required control on parameters turns out to be too stringent. Here we propose instead to follow a dynamic path starting from the gas initially confined in a rotating ring. The large moment of inertia of the ring-shaped fluid facilitates the access to large angular momenta, corresponding to giant vortex states. The trapping potential is then adiabatically transformed into a harmonic confinement, which brings the interacting atomic gas in the desired quantum-Hall regime. We provide numerical evidence that for a broad range of initial angular frequencies, the giant-vortex state is adiabatically connected to the bosonic ν = 1/2 Laughlin state.

Dichloridobis(phenanthridine-κN)zinc(II)

PubMed Central

Khoshtarkib, Zeinab; Ebadi, Amin; Alizadeh, Robabeh; Ahmadi, Roya; Amani, Vahid

2009-01-01

In the mol­ecule of the title compound, [ZnCl2(C13H9N)2], the ZnII atom is four-coordinated in a distorted tetra­hedral configuration by two N atoms from two phenanthridine ligands and by two terminal Cl atoms. The dihedral angle between the planes of the phenanthridine ring systems is 69.92 (3)°. An intra­molecular C—H⋯Cl inter­action results in the formation of a planar five-membered ring, which is oriented at a dihedral angle of 8.32 (3)° with respect to the adjacent phenanthridine ring system. In the crystal structure, π–π contacts between the phenanthridine systems [centroid–centroid distances = 3.839 (2), 3.617 (1) and 3.682 (1) Å] may stabilize the structure. Two weak C—H⋯π inter­actions are also found. PMID:21582680

Effect of solar proton events in 1978 and 1979 on the odd nitrogen abundance in the middle atmosphere

NASA Technical Reports Server (NTRS)

Jackman, Charles H.; Meade, Paul E.

1988-01-01

Daily average solar proton flux data for 1978 and 1979 are used in a proton energy degradation scheme to derive ion pair production rates and atomic nitrogen production rates. The latter are computed in a form suitable for inclusion in an atmopheric, two-dimensional, time-dependent photochemical model. Odd nitrogen distributions are computed from the model, including atomic nitrogen production from solar protons, and are compared with baseline distributions. The comparisons show that the average effect of the solar protons in 1978 and 1979 was to cause changes in odd nitrogen only above 10 mbar and at latitudes only above about 50 deg in both hemispheres. The influence of the solar proton-produced odd nitrogen on the local abundance of odd nitrogen depends primarily on the background odd nitrogen abundance as well as the altitude and season.

Modification of the G-phonon mode of graphene by nitrogen doping

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

Lukashev, Pavel V., E-mail: pavel.lukashev@uni.edu; Hurley, Noah; Zhao, Liuyan

2016-01-25

The effect of nitrogen doping on the phonon spectra of graphene is analyzed. In particular, we employ first-principles calculations and scanning Raman analysis to investigate the dependence of phonon frequencies in graphene on the concentration of nitrogen dopants. We demonstrate that the G phonon frequency shows oscillatory behavior as a function of nitrogen concentration. We analyze different mechanisms which could potentially be responsible for this behavior, such as Friedel charge oscillations around the localized nitrogen impurity atom, the bond length change between nitrogen impurity and its nearest neighbor carbon atoms, and the long-range interactions of the nitrogen point defects. Wemore » show that the bond length change and the long range interaction of point defects are possible mechanisms responsible for the oscillatory behavior of the G frequency as a function of nitrogen concentration. At the same time, Friedel charge oscillations are unlikely to contribute to this behavior.« less

Impact parameter sensitive study of inner-shell atomic processes in the experimental storage ring

NASA Astrophysics Data System (ADS)

Gumberidze, A.; Kozhuharov, C.; Zhang, R. T.; Trotsenko, S.; Kozhedub, Y. S.; DuBois, R. D.; Beyer, H. F.; Blumenhagen, K.-H.; Brandau, C.; Bräuning-Demian, A.; Chen, W.; Forstner, O.; Gao, B.; Gassner, T.; Grisenti, R. E.; Hagmann, S.; Hillenbrand, P.-M.; Indelicato, P.; Kumar, A.; Lestinsky, M.; Litvinov, Yu. A.; Petridis, N.; Schury, D.; Spillmann, U.; Trageser, C.; Trassinelli, M.; Tu, X.; Stöhlker, Th.

2017-10-01

In this work, we present a pilot experiment in the experimental storage ring (ESR) at GSI devoted to impact parameter sensitive studies of inner shell atomic processes for low-energy (heavy-) ion-atom collisions. The experiment was performed with bare and He-like xenon ions (Xe54+, Xe52+) colliding with neutral xenon gas atoms, resulting in a symmetric collision system. This choice of the projectile charge states was made in order to compare the effect of a filled K-shell with the empty one. The projectile and target X-rays have been measured at different observation angles for all impact parameters as well as for the impact parameter range of ∼35-70 fm.

Reporting of nitrogen-isotope abundances (Technical Report)

USGS Publications Warehouse

Coplen, Tyler B.; Krouse, H.R.; Böhlke, John Karl

1992-01-01

To eliminate possible confusion in the reporting of nitrogen-isotope analyses, the Commission on Atomic Weights and Isotopic Abundances recommends that the value 272 be employed for the 14N/15N value of N2 in air for calculating atom percent 15N from measured δ15N values.

NOx reduction by electron beam-produced nitrogen atom injection

DOEpatents

Penetrante, Bernardino M.

2002-01-01

Deactivated atomic nitrogen generated by an electron beam from a gas stream containing more than 99% N.sub.2 is injected at low temperatures into an engine exhaust to reduce NOx emissions. High NOx reduction efficiency is achieved with compact electron beam devices without use of a catalyst.

Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret

NASA Astrophysics Data System (ADS)

Sun, Hongyan; Vaghjiani, Ghanshyam L.

2015-05-01

Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH2 group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C2v symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice-Ramsperger-Kassel-Marcus/multi-well master equation simulations, the results of which reveal the formation of (NO2 + H2O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358-366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.

Ab Initio Kinetics and Thermal Decomposition Mechanism of Mononitrobiuret and 1,5- Dinitrobiuret

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

Sun, Hongyan; Vaghjiani, Ghanshyam G.

2015-05-26

Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was foundmore » that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH2 group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C2v symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice–Ramsperger–Kassel–Marcus/multi-well master equation simulations, the results of which reveal the formation of (NO2 + H2O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358–366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.« less

Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret.

PubMed

Sun, Hongyan; Vaghjiani, Ghanshyam L

2015-05-28

Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH2 group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C2v symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice-Ramsperger-Kassel-Marcus/multi-well master equation simulations, the results of which reveal the formation of (NO2 + H2O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358-366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.

DC-Powered Jumping Ring

NASA Astrophysics Data System (ADS)

Jeffery, Rondo N.; Amiri, Farhang

2016-02-01

The classroom jumping ring demonstration is nearly always performed using alternating current (AC), in which the ring jumps or flies off the extended iron core when the switch is closed. The ring jumps higher when cooled with liquid nitrogen (LN2). We have performed experiments using DC to power the solenoid and find similarities and significant differences from the AC case. In particular, the ring does not fly off the core but rises a short distance and then falls back. If the ring jumps high enough, the rising and the falling motion of the ring does not follow simple vertical motion of a projectile. This indicates that there are additional forces on the ring in each part of its motion. Four possible stages of the motion of the ring with DC are identified, which result from the ring current changing directions during the jump in response to a changing magnetic flux through the moving ring.

Carbon Fibers Conductivity Studies

NASA Technical Reports Server (NTRS)

Yang, C. Y.; Butkus, A. M.

1980-01-01

In an attempt to understand the process of electrical conduction in polyacrylonitrile (PAN)-based carbon fibers, calculations were carried out on cluster models of the fiber consisting of carbon, nitrogen, and hydrogen atoms using the modified intermediate neglect of differential overlap (MINDO) molecular orbital (MO) method. The models were developed based on the assumption that PAN carbon fibers obtained with heat treatment temperatures (HTT) below 1000 C retain nitrogen in a graphite-like lattice. For clusters modeling an edge nitrogen site, analysis of the occupied MO's indicated an electron distribution similar to that of graphite. A similar analysis for the somewhat less stable interior nitrogen site revealed a partially localized II electron distribution around the nitrogen atom. The differences in bonding trends and structural stability between edge and interior nitrogen clusters led to a two-step process proposed for nitrogen evolution with increasing HTT.

Preparation, one- and two-photon properties of carbazole derivatives containing nitrogen heterocyclic ring

NASA Astrophysics Data System (ADS)

Zhang, Yichi; Wang, Ping; Li, Liang; Chen, Zhimin; He, Chunying; Wu, Yiqun

Preparation of recording materials with high two-photon absorption activities is one of the important issues to superhigh- density two-photon absorption (TPA) three-dimensional (3D) optical data storage. In this paper, three new carbazole derivatives containing nitrogen heterocyclic ring with symmetric and asymmetric structures are prepared using ethylene as the π bridge between the carbazole unit and nitrogen heterocyclic ring, namely, 9-butyl-3-(2-(1,8- naphthyridin)vinyl)-carbazole (material 1), 9-butyl-3,6-bis(2-(1,8-naphthyl)vinyl)-carbazole (material 2) and 9-butyl-3,6- bis(2-(quinolin)vinyl)-carbazole (material 3). Their one photon properties including linear absorption spectra, fluorescence emission spectra, and fluorescence quantum yields are studied. The fluorescence excited by 120 fs pulse at 800 nm Ti: sapphire laser operating at 1 kHz repetition rate with different incident powers of 9-butyl-3-(2-(quinolin) vinyl)-carbazole (material 3) was investigated, and two-photon absorption cross-sections has been obtained. It is shown that material 3 containing quinoline rings as electron acceptor with symmetric structure exhibit high two-photon absorption activity. The result implies that material 3 (9-butyl-3-(2-(quinolin) vinyl)-carbazole) is a good candidate as a promising recording material for super-high-density two-photon absorption (TPA) three-dimensional (3D) optical data storage. The influence of chemical structure of the materials on the optical properties is discussed.

[Effects of invasive Cenchrus spinifex on nitrogen pools in sandy grassland].

PubMed

Zhang, Ting; Fu, Wei Dong; Zhang, Rui Hai; Song, Zhen; Bai, Chao; Huang, Cheng Cheng; Zhang, Guo Liang

2017-05-18

Cenchrus spinifex is an invasive plant found in large areas of northern China. In this study, we focused on analysis of the effects of C. spinifex on soil nitrogen and plant nitrogen pools in Horqin sandy grassland. In addition, a pot experiment with 15 N tracing techniques was designed to study the biological nitrogen fixation ability of C. spinifex, compared with two native grasses, Elymus dahuricus and Agropyron cristatum. The total soil nitrogen pool in C. spinifex invaded-area increased significantly by 47.5% and 20.8%, and the soil ammonium nitrogen pool decreased significantly by 25.6% and 25.2%, compared with those in bare and native plant Roegneria kamoji areas, respectively. The plant shoot nitrogen pool decreased significantly by 18.7% in C. spinifex compared with native plant R. kamoji. Atom% 15 N, atom% 15 N excess and atom% 15 N weighting excess of C. spinifex were all significantly lower than those of E. dahuricus and A. cristatum. The nitrogen use efficiencies of C. spinifex and E. dahuricus were 48.5% and 47.0%, respectively, and no significant difference was observed. Ndfa of C. spinifex accounted for 60.2%, when growing together with E. dahuricus. These results suggested that the characteristics on the high efficient use for nitrogen of this invasive weed might an ecological adaptation mechanism, leading to successful colonization and spread in Horqin Steppe.

Electron paramagnetic resonance spectral study of [Mn(acs){sub 2}(2–pic){sub 2}(H{sub 2}O){sub 2}] single crystals

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

Kocakoç, Mehpeyker, E-mail: mkocakoc@cu.edu.tr; Tapramaz, Recep, E-mail: recept@omu.edu.tr

Acesulfame potassium salt is a synthetic and non-caloric sweetener. It is also important chemically for its capability of being ligand in coordination compounds, because it can bind over Nitrogen and Oxygen atoms of carbonyl and sulfonyl groups and ring oxygen. Some acesulfame containing transition metal ion complexes with mixed ligands exhibit solvato and thermo chromic properties and these properties make them physically important. In this work single crystals of Mn{sup +2} ion complex with mixed ligand, [Mn(acs){sub 2}(2-pic){sub 2}(H{sub 2}O){sub 2}], was studied with electron paramagnetic resonance (EPR) spectroscopy. EPR parameters were determined. Zero field splitting parameters indicated that themore » complex was highly symmetric. Variable temperature studies showed no detectable chance in spectra.« less

Selective Inhibitors of Fibroblast Activation Protein (FAP) with a (4-Quinolinoyl)-glycyl-2-cyanopyrrolidine Scaffold.

PubMed

Jansen, Koen; Heirbaut, Leen; Cheng, Jonathan D; Joossens, Jurgen; Ryabtsova, Oxana; Cos, Paul; Maes, Louis; Lambeir, Anne-Marie; De Meester, Ingrid; Augustyns, Koen; Van der Veken, Pieter

2013-05-09

Fibroblast activation protein (FAP) is a serine protease that is generally accepted to play an important role in tumor growth and other diseases involving tissue remodeling. Currently there are no FAP inhibitors with reported selectivity toward both the closely related dipeptidyl peptidases (DPPs) and prolyl oligopeptidase (PREP). We present the discovery of a new class of FAP inhibitors with a N-(4-quinolinoyl)-Gly-(2-cyanopyrrolidine) scaffold. We have explored the effects of substituting the quinoline ring and varying the position of its sp(2) hybridized nitrogen atom. The most promising inhibitors combined low nanomolar FAP inhibition and high selectivity indices (>10(3)) with respect to both the DPPs and PREP. Preliminary experiments on a representative inhibitor demonstrate that plasma stability, kinetic solubility, and log D of this class of compounds can be expected to be satisfactory.

The VOrtex Ring Transit EXperiment (VORTEX) GAS project

NASA Technical Reports Server (NTRS)

Bilen, Sven G.; Langenderfer, Lynn S.; Jardon, Rebecca D.; Cutlip, Hansford H.; Kazerooni, Alexander C.; Thweatt, Amber L.; Lester, Joseph L.; Bernal, Luis P.

1995-01-01

Get Away Special (GAS) payload G-093, also called VORTEX (VOrtex Ring Transit EXperiment), is an investigation of the propagation of a vortex ring through a liquid-gas interface in microgravity. This process results in the formation of one or more liquid droplets similar to earth based liquid atomization systems. In the absence of gravity, surface tension effects dominate the drop formation process. The Shuttle's microgravity environment allows the study of the same fluid atomization processes as using a larger drop size than is possible on Earth. This enables detailed experimental studies of the complex flow processes encountered in liquid atomization systems. With VORTEX, deformations in both the vortex ring and the fluid surface will be measured closely for the first time in a parameters range that accurately resembles liquid atomization. The experimental apparatus will record images of the interactions for analysis after the payload has been returned to earth. The current design of the VORTEX payload consists of a fluid test cell with a vortex ring generator, digital imaging system, laser illumination system, computer based controller, batteries for payload power, and an array of housekeeping and payload monitoring sensors. It is a self-contained experiment and will be flown on board the Space Shuttle in a 5 cubic feet GAS canister. The VORTEX Project is entirely run by students at the University of Michigan but is overseen by a faculty advisor acting as the payload customer and the contact person with NASA. This paper summarizes both the technical and programmatic aspects of the VORTEX Project.

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

Krasnokutski, Serge A., E-mail: skrasnokutskiy@yahoo.com; Huisken, Friedrich, E-mail: friedrich.huisken@uni-jena.de

The reaction of carbon atoms with benzene has been investigated in liquid helium droplets at T = 0.37 K. We found an addition of the carbon atom to form an initial intermediate complex followed by a ring opening and the formation of a seven-membered ring. In contrast to a previous gas phase study, the reaction is frozen after these steps and the loss of hydrogen does not occur. A calorimetric technique was applied to monitor the energy balance of the reaction. It was found that more than 267 kJ mol{sup −1} were released in this reaction. This estimation is inmore » line with quantum chemical calculations of the formation energy of a seven-membered carbon ring. It is suggested that reactions of this kind could be responsible for the low abundance of small polycyclic aromatic hydrocarbon molecules in the interstellar medium. We also found the formation of weakly bonded water-carbon adducts, in which the carbon atom is linked to the oxygen atom of the water molecule with a binding energy of about 33.4 kJ mol{sup −1}.« less

Physiological responses to fertilization recorded in tree rings: isotopic lessons from a long-term fertilization trial - 2008

EPA Science Inventory

Nitrogen fertilizer applications are common land-use management tools, but details on physiological responses to these applications are often lacking, particularly for long-term responses over decades of forest management. We used tree-ring growth patterns and stable isotopes to...

Physiological responses to fertilization recorded in tree rings: Isotopic lessons from a long-term fertilization trial

EPA Science Inventory

Nitrogen fertilizer applications are common land use management tools, but details on physiological responses to these applications are often lacking, particularly for long-term responses over decades of forest management. We used tree ring growth patterns and stable isotopes to ...

Synthesis, structural characterization, and thermal stability studies of heteroleptic cadmium(II) dithiocarbamate with different pyridyl groups

NASA Astrophysics Data System (ADS)

Onwudiwe, Damian C.; Hosten, Eric C.

2018-01-01

The synthesis, characterization and crystal structures of three chloroform solvated adducts of cadmium with mixed ligands of N-alkyl-N-phenyldithiocarbamate and pyridine, 2,2-bipyridine and 1, 10 phenanthroline represented as [CdL1L2 (py)2]·CHCl3(1), [CdL1L2bpy]•CHCl3(2), and [CdL1L2phen]•CHCl3(3) (LI = N-methyl-N-phenyldithiocarbamate, L2 = N-ethyl-N-phenyldithiocarbamate, py = pyridine, bpy = 2,2-bipyridine and phen = 1,10-phenanthroline) respectively are reported. Complex 1, which crystallized in the monoclinic space group P-1, is a centrosymmetric dimeric structure where each Cd center is bonded to two monodentate pyridine, a bidentate terminal dithiocarbamate, and another bidentate bridging dithiocarbamate to form a four-membered ring. Complex 2 crystallized in the monoclinic space group P21/c, with four discrete monomeric molecules in the asymmetric unit. The structure presents a cadmium atom coordinated by two sulphur atoms of a dithiocarbamate ligand and two nitrogen atoms of the 2,2‧-bipyridine to form a CdS4N2 fragment, thus giving the structure around the Cd atom a distorted trigonal prism geometry. Complex 3 contains two discrete monomeric molecules of (phenanthroline) (N, N-methyl phenyl-N, N-ethyl phenyl dithiocarbamato)cadmium (II) per unit cell, and the complex crystallized in the triclinic space group P-1. The structure showed that the Cd atom is bonded to two bidentate dithiocarbamate ligands and to one bidentate phenanthroline ligand in a distorted trigonal prism geometry. All the compounds resulted in CdS as residue upon thermal decomposition process conducted under inert atmosphere.

Clarifying atomic weights: A 2016 four-figure table of standard and conventional atomic weights

USGS Publications Warehouse

Coplen, Tyler B.; Meyers, Fabienne; Holden, Norman E.

2017-01-01

To indicate that atomic weights of many elements are not constants of nature, in 2009 and 2011 the Commission on Isotopic Abundances and Atomic Weights (CIAAW) of the International Union of Pure and Applied Chemistry (IUPAC) replaced single-value standard atomic weight values with atomic weight intervals for 12 elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, magnesium, silicon, sulfur, chlorine, bromine, and thallium); for example, the standard atomic weight of nitrogen became the interval [14.00643, 14.00728]. CIAAW recognized that some users of atomic weight data only need representative values for these 12 elements, such as for trade and commerce. For this purpose, CIAAW provided conventional atomic weight values, such as 14.007 for nitrogen, and these values can serve in education when a single representative value is needed, such as for molecular weight calculations. Because atomic weight values abridged to four figures are preferred by many educational users and are no longer provided by CIAAW as of 2015, we provide a table containing both standard atomic weight values and conventional atomic weight values abridged to four figures for the chemical elements. A retrospective review of changes in four-digit atomic weights since 1961 indicates that changes in these values are due to more accurate measurements over time or to the recognition of the impact of natural isotopic fractionation in normal terrestrial materials upon atomic weight values of many elements. Use of the unit “u” (unified atomic mass unit on the carbon mass scale) with atomic weight is incorrect because the quantity atomic weight is dimensionless, and the unit “amu” (atomic mass unit on the oxygen scale) is an obsolete term: Both should be avoided.

Origin of Quantum Ring Formation During Droplet Epitaxy

NASA Astrophysics Data System (ADS)

Zhou, Z. Y.; Zheng, C. X.; Tang, W. X.; Tersoff, J.; Jesson, D. E.

2013-07-01

Droplet epitaxy of GaAs is studied in real time using in situ surface electron microscopy. The resulting movies motivate a theoretical model for quantum ring formation which can explain the origin of nanoscale features such as double rings observed under a variety of experimental conditions. Inner rings correspond to GaAs deposition at the droplet edge, while outer rings result from the reaction of Ga and As atoms diffusing along the surface. The observed variety of morphologies primarily reflects relative changes in the outer rings with temperature and As flux.

Oxygen ions observed near Saturn's A ring.

PubMed

Waite, J H; Cravens, T E; Ip, W-H; Kasprzak, W T; Luhmann, J G; McNutt, R L; Niemann, H B; Yelle, R V; Mueller-Wodarg, I; Ledvina, S A; Scherer, S

2005-02-25

Ions were detected in the vicinity of Saturn's A ring by the Ion and Neutral Mass Spectrometer (INMS) instrument onboard the Cassini Orbiter during the spacecraft's passage over the rings. The INMS saw signatures of molecular and atomic oxygen ions and of protons, thus demonstrating the existence of an ionosphere associated with the A ring. A likely explanation for these ions is photoionization by solar ultraviolet radiation of neutral O2 molecules associated with a tenuous ring atmosphere. INMS neutral measurements made during the ring encounter are dominated by a background signal.

2-(4-Meth-oxy-phen-yl)-1-pentyl-4,5-di-phenyl-1H-imidazole.

PubMed

Simpson, Jim; Mohamed, Shaaban K; Marzouk, Adel A; Talybov, Avtandil H; Abdelhamid, Antar A

2013-01-01

The title compound, C27H28N2O, is a lophine (2,4,5-triphenyl-1H-imidazole) derivative with an n-pentyl chain on the amine N atom and a 4-meth-oxy substituent on the benzene ring. The two phenyl and meth-oxy-benzene rings are inclined to the imidazole ring at angles of 25.32 (7), 76.79 (5) and 35.42 (7)°, respectively, while the meth-oxy substituent lies close to the plane of its benzene ring, with a maximum deviation of 0.126 (3) Å for the meth-oxy C atom. In the crystal, inversion dimers linked by pairs of C-H⋯O hydrogen bonds generate R2(2)(22) loops. These dimers are stacked along the a-axis direction.

Characterisation of zinc-binding domains of peroxisomal RING finger proteins using size exclusion chromatography/inductively coupled plasma-mass spectrometry.

PubMed

Koellensperger, Gunda; Daubert, Simon; Erdmann, Ralf; Hann, Stephan; Rottensteiner, Hanspeter

2007-11-01

We determined the zinc binding stoichiometry of peroxisomal RING finger proteins by measuring sulfur/metal ratios using inductively coupled plasma-mass spectrometry coupled to size exclusion chromatography, a strategy that provides a fast and quantitative overview on the binding of metals in proteins. As a quality control, liquid chromatography-electrospray ionisation-time of flight-mass spectrometry was used to measure the molar masses of the intact proteins. The RING fingers of Pex2p, Pex10p, and Pex12p showed a stoichiometry of 2.0, 2.1, and 1.2 mol zinc/mol protein, respectively. Thus, Pex2p and Pex10p possess a typical RING domain with two coordinated zinc atoms, whereas that of Pex12p coordinates only a single zinc atom.

N-(4-Meth-oxy-phen-yl)-6-methyl-2-phenyl-5-{[4-(tri-fluoro-meth-yl)anilino]meth-yl}pyrimidin-4-amine.

PubMed

Cieplik, Jerzy; Pluta, Janusz; Bryndal, Iwona; Lis, Tadeusz

2013-11-27

The title compound, C26H23F3N4O, crystallizes with two symmetry-independent mol-ecules in the asymmetric unit, denoted A and B, which differ mainly in the rotation of the meth-oxy-phenyl ring. The -CF3 group of mol-ecule B is disordered by rotation, with the F atoms split over two sets of sites; the occupancy factor for the major component is 0.853 (4). The dihedral angles between the pyrimidine ring and the attached phenyl, meth-oxy-phenyl and tri-fluoro-methyl-phenyl rings are 8.1 (2), 37.5 (2) and 70.7 (2)°, respectively, in mol-ecule A, and 9.3 (2), 5.3 (2) and 79.7 (2)° in mol-ecule B. An intra-molecular N-H⋯N hydrogen bond occurs in each mol-ecule. In the crystal, two crystallographically independent mol-ecules associate into a dimer via a pair of N-H⋯N hydrogen bonds, with a resulting R 2 (2)(12) ring motif and π-π stacking inter-actions [centroid-centroid distance = 3.517 (4) Å] between the pyrimidine rings. For the A mol-ecules, there are inter-molecular C-H⋯O hydrogen bonds between an aryl C atom of meth-oxy-phenyl ring and a meth-oxy O atom of an adjacent mol-ecule. A similar inter-action is lacking in the B mol-ecules.

3D tomographic reconstruction of the terrestrial exosphere and its time-dependent coupling to the magnetospheric ring current

NASA Astrophysics Data System (ADS)

Waldrop, L.; Cucho-Padin, G.; Ilie, R.

2017-12-01

Charge exchange collisions between ring current ions and hydrogen (H) atoms in the outer exosphere serve to dissipate magnetospheric energy, particularly during the slow recovery phase of geomagnetic storms, through the generation of energetic neutral atoms (ENAs) which escape the system. As a result, knowledge of the spatial distribution and temporal variability of exospheric H density is critical for reliable interpretation of ENA flux measurements as well as for accurate modeling of the ring current. Although numerous theoretical, numerical, and empirical H distributions have been used for such analyses, their reliance on ad hoc or unphysical assumptions, together with their inherently static formulations, is a source of significant uncertainty. Our recent development of a robust tomographic technique for the model-independent estimation of global exospheric H density from optical remote sensing data overcomes the limitations of past analysis and enables an unprecedented investigation of global exospheric and ring current dynamics. Here, we present sample results of our 3D, time-dependent reconstructions of exospheric structure, derived from measurements of resonantly scattered solar Lyman-alpha (121.6 nm) photons acquired by the Lyman-alpha detectors (LADs) onboard NASA's Two Wide-angle Imaging Neutral-atom Spectrometers (TWINS) mission. We use the Hot Electron and Ion Drift Integrator (HEIDI) kinetic model of the ring current to investigate the charge exchange interactions between the resulting H density distribution and ring current ions and generate synthetic images of ENA flux for comparison with those measured by TWINS.

Chains of benzenes with lithium-atom adsorption: Vibrations and spontaneous symmetry breaking

NASA Astrophysics Data System (ADS)

Ortiz, Yenni P.; Stegmann, Thomas; Klein, Douglas J.; Seligman, Thomas H.

2017-09-01

We study effects of different configurations of adsorbates on the vibrational modes as well as symmetries of polyacenes and poly-p-phenylenes focusing on lithium atom adsorption. We found that the spectra of the vibrational modes distinguish the different configurations. For more regular adsorption schemes the lowest states are bending and torsion modes of the skeleton, which are essentially followed by the adsorbate. On poly-p-phenylenes we found that lithium adsorption reduces and often eliminates the torsion between rings thus increasing symmetry. There is spontaneous symmetry breaking in poly-p-phenylenes due to double adsorption of lithium atoms on alternating rings.

N′-[(E)-3-Chloro-2-fluoro­benzyl­idene]-6-methyl­nicotinohydrazide monohydrate

PubMed Central

Fun, Hoong-Kun; Quah, Ching Kheng; Shyma, P. C.; Kalluraya, Balakrishna; Vidyashree, J. H. S.

2012-01-01

The title compound, C14H11ClFN3O·H2O, exists in an E conformation with respect to the N=C bond. The pyridine ring forms a dihedral angle of 5.00 (9)° with the benzene ring. In the crystal, the ketone O atom accepts one O—H⋯O and one C—H⋯O hydrogen bond, the water O atom accepts one N—H⋯O and two C—H⋯O hydrogen bonds and the pyridine N atom accepts one O—H⋯N hydrogen bond, forming layers parallel to the ab plane. PMID:22798798

Discovery of Oxygen Kalpha X-ray Emission from the Rings of Saturn

NASA Technical Reports Server (NTRS)

Bhardwaj, Anil; Elsner, Ronald F.; Waite, J. Hunter, Jr.; Gladstone, G Randall; Cravens, Thomas E.; Ford, Peter G.

2005-01-01

Using the Advanced CCD Imaging Spectrometer (ACIS), the Chandra X-ray Observatory (CXO) observed the Saturnian system for one rotation of the planet (approx.37 ks) on 20 January, 2004, and again on 26-27 January, 2004. In this letter we report the detection of X-ray emission from the rings of Saturn. The X-ray spectrum from the rings is dominated by emission in a narrow (approx.130 eV wide) energy band centered on the atomic oxygen Ka fluorescence line at 0.53 keV. The X-ray power emitted from the rings in the 0.49-0.62 keV band is about one-third of that emitted from Saturn disk in the photon energy range 0.24-2.0 keV. Our analysis also finds a clear detection of X-ray emission from the rings in the 0.49-0.62 keV band in an earlier (14-15 April, 2003) Chandra ACIS observation of Saturn. Fluorescent scattering of solar X-rays from oxygen atoms in the H20 icy ring material is the likely source mechanism for ring X-rays, consistent with the scenario of solar photo-production of a tenuous ring oxygen atmosphere and ionosphere recently discovered by Cassini.

The RING 2.0 web server for high quality residue interaction networks.

PubMed

Piovesan, Damiano; Minervini, Giovanni; Tosatto, Silvio C E

2016-07-08

Residue interaction networks (RINs) are an alternative way of representing protein structures where nodes are residues and arcs physico-chemical interactions. RINs have been extensively and successfully used for analysing mutation effects, protein folding, domain-domain communication and catalytic activity. Here we present RING 2.0, a new version of the RING software for the identification of covalent and non-covalent bonds in protein structures, including π-π stacking and π-cation interactions. RING 2.0 is extremely fast and generates both intra and inter-chain interactions including solvent and ligand atoms. The generated networks are very accurate and reliable thanks to a complex empirical re-parameterization of distance thresholds performed on the entire Protein Data Bank. By default, RING output is generated with optimal parameters but the web server provides an exhaustive interface to customize the calculation. The network can be visualized directly in the browser or in Cytoscape. Alternatively, the RING-Viz script for Pymol allows visualizing the interactions at atomic level in the structure. The web server and RING-Viz, together with an extensive help and tutorial, are available from URL: http://protein.bio.unipd.it/ring. © The Author(s) 2016. Published by Oxford University Press on behalf of Nucleic Acids Research.

Spontaneous symmetry breaking by double lithium adsorption in polyacenes

NASA Astrophysics Data System (ADS)

Ortiz, Yenni. P.; Seligman, Thomas H.

2010-12-01

We show that adsorption of one lithium atom to polyacenes, i.e. chains of linearly fused benzene rings, will cause such chains to be slightly deformed. If we adsorb a second identical atom on the opposite side of the same ring, this deformation is dramatically enhanced despite the fact that a symmetric configuration seems possible. We argue, that this may be due to an instability of the Jahn-Teller type possibly indeed to a Peierls instability.

Spontaneous symmetry breaking by double lithium adsorption in polyacenes

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

Ortiz, Yenni. P.; Seligman, Thomas H.; Centro Internacional de Ciencias, Cuernavaca, Morelos

2010-12-23

We show that adsorption of one lithium atom to polyacenes, i.e. chains of linearly fused benzene rings, will cause such chains to be slightly deformed. If we adsorb a second identical atom on the opposite side of the same ring, this deformation is dramatically enhanced despite the fact that a symmetric configuration seems possible. We argue, that this may be due to an instability of the Jahn-Teller type possibly indeed to a Peierls instability.

Discovery of an Inner Disk Component Around HD 141569 A

NASA Technical Reports Server (NTRS)

Konishi, Mihoko; Grady, Carol A.; Schneider, Glenn; Shibai, Hiroshi; McElwain, Michael W.; Nesvold, Erika R.; Kuchner, Marc J.; Carson, Joseph; Debes, John H.; Gaspar, Andras;

(Z)-3-Methyl-4-[1-(4-methyl­anilino)propyl­idene]-1-phenyl-1H-pyrazol-5(4H)-one

PubMed Central

Sharma, Naresh; Vyas, Komal M.; Jadeja, R. N.; Kant, Rajni; Gupta, Vivek K.

2013-01-01

In the title mol­ecule, C20H21N3O, the central pyrazole ring forms dihedral angles of 4.75 (9) and 49.11 (9)°, respectively, with the phenyl and methyl-substituted benzene rings. The dihedral angle between the phenyl and benzene rings is 51.76 (8)°. The amino group and carbonyl O atom are involved in an intra­molecular N—H⋯O hydrogen bond. In the crystal, π–π inter­actions are observed between benzene rings [centroid–centroid seperation = 3.892 (2) Å] and pyrazole rings [centroid–centroid seperation = 3.626 (2) Å], forming chains along [111]. The H atoms of the methyl group on the p-tolyl substituent were refined as disordered over two sets of sites in a 0.60 (4):0.40 (4) ratio. PMID:24109353

Crystal structure and Hirshfield analysis of the 4-(di-methyl-amino)-pyridine adduct of 4-meth-oxy-phenyl-borane.

PubMed

Shooter, Jesse; Allen, Caleb J; Tinsley, Colby W K; Zakharov, Lev N; Abbey, Eric R

2017-11-01

The title compound [systematic name: 4-(di-methyl-amino)-pyridine-4-meth-oxy-phenyl-borane (1/1)], C 14 H 19 BN 2 O, contains two independent mol-ecules in the asymmetric unit. Both molecules exhibit coplanar, mostly sp 2 -hybridized meth-oxy and di-methyl-amino substituents on their respective aromatic rings, consistent with π-donation into the aromatic systems. The B-H groups exhibit an intra-molecular close contact with a C-H group of the pyridine ring, which may be evidence of electrostatic attraction between the hydridic B-H and the electropositive aromatic C-H. There appears to be weak C-H⋯π(arene) inter-actions between two of the H atoms of an amino-methyl group and the meth-oxy-substituted benzene ring of the other independent mol-ecule, and another C-H⋯π (arene) inter-action between one of the pyridine ring H atoms and the same benzene ring.

Fused thiophene-based conjugated polymers and their use in optoelectronic devices

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

Facchetti, Antonio; Marks, Tobin J.; Takai, Atsuro

The present teachings relate to polymeric compounds and their use as organic semiconductors in organic and hybrid optical, optoelectronic, and/or electronic devices such as photovoltaic cells, light emitting diodes, light emitting transistors, and field effect transistors. The disclosed compounds generally include as repeating units at least one annulated thienyl-vinylene-thienyl (TVT) unit and at least one other pi-conjugated unit. The annulated TVT unit can be represented by the formula: ##STR00001## where Cy.sup.1 and Cy.sup.2 can be a five- or six-membered carbocyclic ring. The annulated TVT unit can be optionally substituted at any available ring atom(s), and can be covalently linked tomore » the other pi-conjugated unit via either the thiophene rings or the carbocyclic rings Cy.sup.1 and Cy.sup.2. The other pi-conjugated unit can be a conjugated linear linker including one or more unsaturated bonds, or a conjugated cyclic linker including one or more carbocyclic and/or heterocyclic rings.« less

Vibrational investigation on the copper(II) binding mode of carcinine and its pH dependence

NASA Astrophysics Data System (ADS)

Torreggiani, Armida; Reggiani, Matteo; Manco, Immacolata; Tinti, Anna

2007-05-01

A comparative FT-Raman and FT-IR study of Carcinine (Carc), a natural imidazole dipeptide, and its complexes with Cu(II) ions was performed at different pH's. Both Raman and IR spectra present marker bands useful for the identification of the predominant complexes; in particular, Raman spectroscopy appears useful for identifying the metal-coordination site of the imidazole ring (N π or N τ atoms) of Carc. Free Carc shows a strong network of H-bonds and tautomer I (N τ-H) is the preferred form of the imidazolic ring (bands at 1578, 1292 and 988 cm -1). The presence of Cu(II) does not affect the tautomeric equilibrium at pH 7, whereas the deprotonation of both N-imidazolic nitrogens is strongly induced at higher pH. Under neutral and alkaline conditions the primary amino group takes part to the Cu(II) chelation, whereas all the peptidic moieties are involved in coordination only at pH 7. Thus, Carc acts as a tri-dentate ligand at neutral pH, mainly giving a monomeric complex, [CuLH -1], containing tautomer I, whereas an oligonuclear complex, probably [Cu 4L 4H -8], where metal-imidazolate ions connect different ligand molecules, predominates at alkaline pH.

Synthesis, Characterization and Antifertility Activity of New Unsymmetrical Macrocyclic Complexes of Tin(II)

PubMed Central

Sharma, Kripa; Joshi, S. C.

2000-01-01

A new series of unsymmetrical macrocyclic complexes of tin(ll) has been prepared by the template process using bis(3-oxo-2-butylidene)propane-1,3-diamine as precursor. This affords a method to synthesize these complexes with various ring sizes. The tetradentate macrocyclic precursor [N4mL] reacts with SnCl2 and different diamines in a 1:1:1 molar ratio in refluxing methanol to give complexes of the type [Sn(N4mL)Cl2]. The ring expansion has been achieved by varying the diamine between the two diacetyl amino nitrogen atoms. The macrocyclic precursor and its metal complexes have been characterized on the basis of elemental analysis, molar conductance, molecular weight determinations, IR, 1H NMR,13C NMR, 119Sn NMR and electronic spectral studies. An octahedral geometry around the metal ion is suggested for these complexes. On the basis of molecular weights and conductivity measurements, their monomeric and non-electrolytic nature has been confirmed. The precursor and complexes have been screened in vitro against a number of pathogenic fungi and bacteria to assess their growth inhibiting potential. The testicular sperm density and testicular sperm morphology, sperm motility, density of cauda epididymal spermatozoa and fertility in mating trails and biochemicals parameters of reproductive organs have been examined and discussed. PMID:18475951

Saturn Ring

NASA Image and Video Library

2007-12-12

Like Earth, Saturn has an invisible ring of energetic ions trapped in its magnetic field. This feature is known as a "ring current." This ring current has been imaged with a special camera on Cassini sensitive to energetic neutral atoms. This is a false color map of the intensity of the energetic neutral atoms emitted from the ring current through a processed called charged exchange. In this process a trapped energetic ion steals and electron from cold gas atoms and becomes neutral and escapes the magnetic field. The Cassini Magnetospheric Imaging Instrument's ion and neutral camera records the intensity of the escaping particles, which provides a map of the ring current. In this image, the colors represent the intensity of the neutral emission, which is a reflection of the trapped ions. This "ring" is much farther from Saturn (roughly five times farther) than Saturn's famous icy rings. Red in the image represents the higher intensity of the particles, while blue is less intense. Saturn's ring current had not been mapped before on a global scale, only "snippets" or areas were mapped previously but not in this detail. This instrument allows scientists to produce movies (see PIA10083) that show how this ring changes over time. These movies reveal a dynamic system, which is usually not as uniform as depicted in this image. The ring current is doughnut shaped but in some instances it appears as if someone took a bite out of it. This image was obtained on March 19, 2007, at a latitude of about 54.5 degrees and radial distance 1.5 million kilometres (920,000 miles). Saturn is at the center, and the dotted circles represent the orbits of the moon's Rhea and Titan. The Z axis points parallel to Saturn's spin axis, the X axis points roughly sunward in the sun-spin axis plane, and the Y axis completes the system, pointing roughly toward dusk. The ion and neutral camera's field of view is marked by the white line and accounts for the cut-off of the image on the left. The image is an average of the activity over a (roughly) 3-hour period. http://photojournal.jpl.nasa.gov/catalog/PIA10094

Charge-free method of forming nanostructures on a substrate

DOEpatents

Hoffbauer; Mark , Akhadov; Elshan

2010-07-20

A charge-free method of forming a nanostructure at low temperatures on a substrate. A substrate that is reactive with one of atomic oxygen and nitrogen is provided. A flux of neutral atoms of least one of oxygen and nitrogen is generated within a laser-sustained-discharge plasma source and a collimated beam of energetic neutral atoms and molecules is directed from the plasma source onto a surface of the substrate to form the nanostructure. The energetic neutral atoms and molecules in the beam have an average kinetic energy in a range from about 1 eV to about 5 eV.

Crystal structure of [(2R,3R,4S)-3,4-bis(acet-yloxy)-5-iodo-3,4-di-hydro-2H-pyran-2-yl]methyl acetate.

PubMed

Zukerman-Schpector, Julio; Caracelli, Ignez; Stefani, Hélio A; Shamim, Anwar; Tiekink, Edward R T

2015-01-01

In the title compound, C12H15IO7, the 3,4-di-hydro-2H-pyran ring is in a distorted half-boat conformation with the atom bearing the acet-yloxy group adjacent to the C atom bearing the methyl-acetate group lying 0.633 (6) Å above the plane of the remaining ring atoms (r.m.s. deviation = 0.0907 Å). In the crystal, mol-ecules are linked into a supra-molecular chain along the a axis through two C-H⋯O inter-actions to the same acceptor carbonyl O atom; these chains pack with no specific inter-molecular inter-actions between them.

Electron configuration and hydrogen-bonding pattern in several thymine and uracil analogues studied by 1H-14N NQDR and DFT/QTAIM.

PubMed

Seliger, Janez; Žagar, Veselko; Latosińska, Magdalena; Latosińska, Jolanta Natalia

2012-08-02

Some thio- and aza-derivatives of natural nucleobases uracil and thymine: 2-thiouracil, 4-thiouracil, 6-methyl-2-thiouracil, 6-azauracil, and 6-aza-2-thiothymine have been studied experimentally in solid state by (1)H-(14)N NMR-NQR double resonance (NQDR) and theoretically by the Density Functional Theory (DFT)/Quantum Theory of Atoms in Molecules (QTAIM). The (14)N resonance frequencies have been measured at 173 and 295 K and assigned to particular nitrogen sites (-N═ and -NH-). The temperature factor has been found negligible. The changes in the molecular skeletons, electric charge distribution, intermolecular interactions pattern, and molecular aggregations caused by oxygen replacement with sulfur and carbon replacement with nitrogen are discussed in detail. Correlations between all the principal components of the (14)N quadrupole coupling tensor have been found helpful in the search for the experimental (14)N NQR frequencies, their assignment to a particular nitrogen positions and estimation of the strength of the inter- and intramolecular interactions. The variation in the NQR parameters have been mainly related to the variation in the population of π-electron orbital. For thiouracil derivatives a general trend is that the stronger the hydrogen bond is, the lower is the asymmetry parameter, while for thymine and 6-aza-2-thiotymine, the opposite relation holds. Differences in correlations of the principal components of the (14)N quadrupole coupling tensor at the amino and iminonitrogen positions in heterocyclic rings are discussed. The effect of C→H and C→N substitution at the amino nitrogen position and C→N substitution at the iminonitrogen position on the quadrupole coupling tensor is analyzed. This study also demonstrates the advantages of combining NQR and DFT/QTAIM to predict an unsolved crystalline structure of 4-thiouracil.

Synthesis of nitrogen-containing carbon by solution plasma in aniline with high-repetition frequency discharges

NASA Astrophysics Data System (ADS)

Hyun, Koangyong; Ueno, Tomonaga; Saito, Nagahiro

2016-01-01

Nitrogen-containing carbon nanoparticles were synthesized in aniline by solution plasma with high-repetition frequency discharges. We developed a bipolar pulsed power supply that can apply high-repetition frequencies ranging from 25 to 200 kHz. By utilizing high-repetition frequencies, conductive carbons were directly synthesized. The crystallinity was increased and H/C ratio of carbon was decreased. Furthermore, nitrogen atoms were simultaneously embedded in the carbon matrix. Due to the presence of nitrogen atoms, the conductivity and electrocatalytic activity of the samples were remarkably improved compared to that of a pure carbon matrix synthesized from a benzene precursor.

3-(2-Bromo-4,5-dimethoxy­phen­yl)propiononitrile

PubMed Central

Liu, Yan-Ping; Wang, De-Cai; Chen, Hui; Kang, Si-Shun; Huang, Xin-Ming

2008-01-01

In the mol­ecule of the title compound, C11H12BrNO2, a weak intra­molecular C—H⋯Br hydrogen bond results in the formation of a five-membered ring, which adopts an envelope conformation with the H atom displaced by 0.486 Å from the plane of the other ring atoms. In the crystal structure, inter­molecular C—H⋯O hydrogen bonds link the mol­ecules. PMID:21202583

Rotational Spectra and Nuclear Quadrupole Coupling Constants of Iodoimidazoles

NASA Astrophysics Data System (ADS)

Cooper, Graham A.; Anderson, Cara J.; Medcraft, Chris; Legon, Anthony; Walker, Nick

2017-06-01

The microwave spectra of two isomers of iodoimidazole have been recorded and assigned with resolution of their nuclear quadrupole coupling constants. These constants have been analysed in terms of the conjugation between the lone pairs on the iodine atom and the aromatic π-bonding system, and the effect of this conjugation on the distribution of π-electron density in the ring. A comparison of these properties has been made between iodoimidazole and other 5- and 6-membered aromatic rings bonded to halogen atoms.

4-Meth-oxy-3-(meth-oxy-meth-yl)benzalde-hyde.

PubMed

Zhang, Jing-Chao; Sun, Jun; Zhang, Juan; Liu, Guang-Lin; Guo, Cheng

2013-01-01

In the title compound, C10H12O3, the dihedral angle between the benzene ring and the meth-oxy-methyl side chain is 9.7 (2)°. The O atom of the aldehyde group and the C atom of the meth-oxy group deviate from the plane of the ring by 0.039 (3) and 0.338 (4) Å, respectively. The only inter-molecular inter-actions are very weak C-H⋯π inter-actions.

Storage rings for spin-polarized hydrogen

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

Thompson, D.; Lovelace, R.V.E.; Lee, D.

1989-11-01

A strong-focusing storage ring is proposed for the long-term magnetic confinement of a collisional gas of neutral spin-polarized hydrogen atoms in the Za{l arrow} and Zb{l arrow} hyperfine states. The trap uses the interaction of the magnetic moments of the gas atoms with a static magnetic field. Laser cooling and evaporative cooling can be utilized to enhance the confinement and to offset the influence of viscous heating. An important application of the trap is to the attainment of Bose--Einstein condensation.

Conformational Preference and Donor Atom Interaction Leading to Hexacoordination vs Pentacoordination in Bicyclic Tetraoxyphosphoranes(1).

PubMed

Sherlock, David J.; Chandrasekaran, A.; Prakasha, T. K.; Day, Roberta O.; Holmes, Robert R.

1998-01-12

New bicyclic tetraoxyphosphoranes all containing a six-membered oxaphosphorinane ring, C(6)H(8)(CH(2)O)(2)P(OC(12)H(8))(OXyl) (1), (C(6)H(4)O)(2)P(OC(12)H(8))(OXyl) (2), CH(2)[(t-Bu)(2)C(6)H(2)O](2)P(OC(12)H(8))(OXyl) (3), O(2)S[(t-Bu)MeC(6)H(2)O](2)P(OC(12)H(8))(OXyl) (4), and S[(t-Bu)MeC(6)H(2)O](2)P(OC(12)H(8))(OXyl) (5), were synthesized by the oxidative addition reaction of the cyclic phosphine P(OC(12)H(8))(OXyl) (6) with an appropriate diol in the presence of N-chlorodiisopropylamine. X-ray analysis revealed trigonal bipyramidal (TBP) geometries for 1-4 where the dioxa ring varied in size from six- to eight-membered. With a sulfur donor atom as part of an eight-membered ring in place of a potential oxygen donor atom of a sulfone group as in 4, the X-ray study of 5 showed the formation of a hexacoordinated structure via a P-S interaction. Ring constraints are evaluated to give an order of conformational flexibility associated with the (TBP) tetraoxyphosphoranes 4 > 3 approximately 1 > 2 which parallels the degree of shielding from (31)P NMR chemical shifts: 4 > 3 > 1 > 2. The six- and seven-membered dioxa rings in 1 and 2, respectively, are positioned at axial-equatorial sites, whereas the eight-membered dioxa ring in 3 and 4 occupies diequatorial sites of a TBP. V-T (1)H NMR data give barriers to xylyl group rotation about the C-OXyl bond. The geometry of 5 is located along a coordinate from square pyramidal toward octahedral to the extent of 60.7%. Achieving hexacoordination in bicyclic tetraoxyphosphoranes of reduced electrophilicity relative to bicyclic pentaoxyphosphoranes appears to be dependent on the presence of a sufficiently strong donor atom.

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

PubMed

Nourry, Sendres; Krim, Lahouari

2016-07-21

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

Fluorescence quenching and the "ring-mode" to "red-mode" transition in alkali inductively coupled plasmas

NASA Astrophysics Data System (ADS)

Huang, M.; Bazurto, R.; Camparo, J.

2018-01-01

The ring-mode to red-mode transition in alkali metal inductively coupled plasmas (ICPs) (i.e., rf-discharge lamps) is perhaps the most important physical phenomenon affecting these devices as optical pumping light sources for atomic clocks and magnetometers. It sets the limit on useful ICP operating temperature, thereby setting a limit on ICP light output for atomic-clock/magnetometer signal generation, and it is a temperature region of ICP operation associated with discharge instability. Previous work has suggested that the mechanism driving the ring-mode to red-mode transition is associated with radiation trapping, but definitive experimental evidence validating that hypothesis has been lacking. Based on that hypothesis, one would predict that the introduction of an alkali-fluorescence quenching gas (i.e., N2) into the ICP would increase the ring-mode to red-mode transition temperature. Here, we test that prediction, finding direct evidence supporting the radiation-trapping hypothesis.

Copper Causes Regiospecific Formation of C4F8-Containing Six-Membered Rings and their Defluorination/Aromatization to C4F4-Containing Rings in Triphenylene/1,4-C4F8I2 Reactions

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

Rippy, Kerry C.; Bukovsky, Eric V.; Clikeman, Tyler T.

The presence of Cu in reactions of triphenylene (TRPH) and 1,4-C4F8I2 at 360 °C led to regiospecific substitution of TRPH ortho C(β) atoms to form C4F8-containing rings, completely suppressing substitution on C(α) atoms. In addition, Cu caused selective reductive-defluorination/aromatization (RD/A) to form C4F4- containing aromatic rings. Without Cu, the reactions of TRPH and 1,4- C4F8I2 were not regiospecific and no RD/A was observed. These results, supported by DFT calculations, are the first examples of Cupromoted (i) regiospecific perfluoroannulation, (ii) preparative C–F activation, and (iii) RD/A. HPLC-purified products were characterized by X-ray diffraction, low-temperature PES, and 1H/19F NMR.

Crystal structure of (3S*,4R*)-4-fluoro-3-(4-meth-oxy-phen-yl)-1-oxo-2-phenyl-1,2,3,4-tetra-hydro-iso-quinoline-4-carb-oxy-lic acid.

PubMed

Lehmann, Anna; Lechner, Lisa; Radacki, Krzysztof; Braunschweig, Holger; Holzgrabe, Ulrike

2017-06-01

The title compound, C 23 H 18 FNO 4 , crystallized as a racemate. It exhibits a cis conformation with respect to the F atom and the methine H atom. The piperidine ring has a screw-boat conformation. The meth-oxy-phenyl ring and the phenyl ring are inclined to the mean plane of the iso-quinoline ring system by 89.85 (4) and 46.62 (5)°, respectively, and by 78.15 (5)° to one another. In the crystal, mol-ecules are linked by an O-H⋯O hydrogen bond forming chains propagating along the a -axis direction. The chains are linked by C-H⋯F hydrogen bonds, forming layers lying parallel to the ab plane.

The crystal structure of N-acetyl-L-glutamate synthase from Neisseria gonorrhoeae provides insights into mechanisms of catalysis and regulation.

PubMed

Shi, Dashuang; Sagar, Vatsala; Jin, Zhongmin; Yu, Xiaolin; Caldovic, Ljubica; Morizono, Hiroki; Allewell, Norma M; Tuchman, Mendel

2008-03-14

The crystal structures of N-acetylglutamate synthase (NAGS) in the arginine biosynthetic pathway of Neisseria gonorrhoeae complexed with acetyl-CoA and with CoA plus N-acetylglutamate have been determined at 2.5- and 2.6-A resolution, respectively. The monomer consists of two separately folded domains, an amino acid kinase (AAK) domain and an N-acetyltransferase (NAT) domain connected through a 10-A linker. The monomers assemble into a hexameric ring that consists of a trimer of dimers with 32-point symmetry, inner and outer ring diameters of 20 and 100A, respectively, and a height of 110A(.) Each AAK domain interacts with the cognate domains of two adjacent monomers across two 2-fold symmetry axes and with the NAT domain from a second monomer of the adjacent dimer in the ring. The catalytic sites are located within the NAT domains. Three active site residues, Arg316, Arg425, and Ser427, anchor N-acetylglutamate in a position at the active site to form hydrogen bond interactions to the main chain nitrogen atoms of Cys356 and Leu314, and hydrophobic interactions to the side chains of Leu313 and Leu314. The mode of binding of acetyl-CoA and CoA is similar to other NAT family proteins. The AAK domain, although catalytically inactive, appears to bind arginine. This is the first reported crystal structure of any NAGS, and it provides insights into the catalytic function and arginine regulation of NAGS enzymes.

The Crystal Structure of N-Acetyl-L-glutamate Synthase from Neisseria gonorrhoeae Provides Insights into Mechanisms of Catalysis and Regulation

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

Shi, Dashuang; Sagar, Vatsala; Jin, Zhongmin

2010-01-07

The crystal structures of N-acetylglutamate synthase (NAGS) in the arginine biosynthetic pathway of Neisseria gonorrhoeae complexed with acetyl-CoA and with CoA plus N-acetylglutamate have been determined at 2.5- and 2.6-A resolution, respectively. The monomer consists of two separately folded domains, an amino acid kinase (AAK) domain and an N-acetyltransferase (NAT) domain connected through a 10-A linker. The monomers assemble into a hexameric ring that consists of a trimer of dimers with 32-point symmetry, inner and outer ring diameters of 20 and 100A, respectively, and a height of 110A(.) Each AAK domain interacts with the cognate domains of two adjacent monomersmore » across two 2-fold symmetry axes and with the NAT domain from a second monomer of the adjacent dimer in the ring. The catalytic sites are located within the NAT domains. Three active site residues, Arg316, Arg425, and Ser427, anchor N-acetylglutamate in a position at the active site to form hydrogen bond interactions to the main chain nitrogen atoms of Cys356 and Leu314, and hydrophobic interactions to the side chains of Leu313 and Leu314. The mode of binding of acetyl-CoA and CoA is similar to other NAT family proteins. The AAK domain, although catalytically inactive, appears to bind arginine. This is the first reported crystal structure of any NAGS, and it provides insights into the catalytic function and arginine regulation of NAGS enzymes.« less

Energetic Metastable Oxygen and Nitrogen Atoms in the Terrestrial Atmosphere

NASA Technical Reports Server (NTRS)

Kharchenko, Vasili; Dalgarno, A.

2005-01-01

This report summarizes our research performed under NASA Grant NAG5-11857. The three-year grant have been supported by the Geospace Sciences SR&T program. We have investigated the energetic metastable oxygen and nitrogen atoms in the terrestrial stratosphere, mesosphere and thermosphere. Hot atoms in the atmosphere are produced by solar radiation, the solar wind and various ionic reactions. Nascent hot atoms arise in ground and excited electronic states, and their translational energies are larger by two - three orders of magnitude than the thermal energies of the ambient gas. The relaxation kinetics of hot atoms determines the rate of atmospheric heating, the intensities of aeronomic reactions, and the rate of atom escape from the planet. Modeling of the non-Maxwellian energy distributions of metastable oxygen and nitrogen atoms have been focused on the determination of their impact on the energetics and chemistry of the terrestrial atmosphere between 25 and 250 km . At this altitudes, we have calculated the energy distribution functions of metastable O and N atoms and computed non-equilibrium rates of important aeronomic reactions, such as destruction of the water molecules by O(1D) atoms and production of highly excited nitric oxide molecules. In the upper atmosphere, the metastable O(lD) and N(2D) play important role in formation of the upward atomic fluxes. We have computed the upward fluxes of the metastable and ground state oxygen atoms in the upper atmosphere above 250 km. The accurate distributions of the metastable atoms have been evaluated for the day and night-time conditions.

Reactions of Ground State Nitrogen Atoms N(4S) with Astrochemically-Relevant Molecules on Interstellar Dusts

NASA Astrophysics Data System (ADS)

Krim, Lahouari; Nourry, Sendres

2015-06-01

In the last few years, ambitious programs were launched to probe the interstellar medium always more accurately. One of the major challenges of these missions remains the detection of prebiotic compounds and the understanding of reaction pathways leading to their formation. These complex heterogeneous reactions mainly occur on icy dust grains, and their studies require the coupling of laboratory experiments mimicking the extreme conditions of extreme cold and dilute media. For that purpose, we have developed an original experimental approach that combine the study of heterogeneous reactions (by exposing neutral molecules adsorbed on ice to non-energetic radicals H, OH, N...) and a neon matrix isolation study at very low temperatures, which is of paramount importance to isolate and characterize highly reactive reaction intermediates. Such experimental approach has already provided answers to many questions raised about some astrochemically-relevant reactions occurring in the ground state on the surface of dust grain ices in dense molecular clouds. The aim of this new present work is to show the implication of ground state atomic nitrogen on hydrogen atom abstraction reactions from some astrochemically-relevant species, at very low temperatures (3K-20K), without providing any external energy. Under cryogenic temperatures and with high barrier heights, such reactions involving N(4S) nitrogen atoms should not occur spontaneously and require an initiating energy. However, the detection of some radicals species as byproducts, in our solid samples left in the dark for hours at 10K, proves that hydrogen abstraction reactions involving ground state N(4S) nitrogen atoms may occur in solid phase at cryogenic temperatures. Our results show the efficiency of radical species formation stemming from non-energetic N-atoms and astrochemically-relevant molecules. We will then discuss how such reactions, involving nitrogen atoms in their ground states, might be the first key step towards complex organic molecules production in the interstellar medium.

3-Ethyl-2-methyl-5-methyl­ene-6,7-di­hydroindol-4(5H)-one

PubMed Central

Sonar, Vijayakumar N.; Parkin, Sean; Crooks, Peter A.

2008-01-01

The title compound, C12H15NO, a degradation product of molindone hydro­chloride, was prepared by the reaction of molindone with methyl iodide and subsequent reaction of the resulting quaternary ammonium salt with 2N aqueous sodium hydroxide. The newly formed double bond is exocyclic in nature and the carbonyl group is conjugated with the π-electrons of the pyrrole ring. The six-membered ring is in the half-chair conformation. The H atom attached to the N atom is involved in an inter­molecular hydrogen bond with the O atom of a screw-related mol­ecule, thus forming a continuous chain. PMID:21200723

Conductive atomic force microscopy studies on the transformation of GeSi quantum dots to quantum rings.

PubMed

Zhang, S L; Xue, F; Wu, R; Cui, J; Jiang, Z M; Yang, X J

2009-04-01

Conductive atomic force microscopy has been employed to study the topography and conductance distribution of individual GeSi quantum dots (QDs) and quantum rings (QRs) during the transformation from QDs to QRs by depositing an Si capping layer on QDs. The current distribution changes significantly with the topographic transformation during the Si capping process. Without the capping layer, the QDs are dome-shaped and the conductance is higher at the ring region between the center and boundary than that at the center. After capping with 0.32 nm Si, the shape of the QDs changes to pyramidal and the current is higher at both the center and the arris. When the Si capping layer increases to 2 nm, QRs are formed and the current of individual QRs is higher at the rim than that at the central hole. By comparing the composition distributions obtained by scanning Auger microscopy and atomic force microscopy combined with selective chemical etching, the origin of the current distribution change is discussed.

A physically interpretable quantum-theoretic QSAR for some carbonic anhydrase inhibitors with diverse aromatic rings, obtained by a new QSAR procedure.

PubMed

Clare, Brian W; Supuran, Claudiu T

2005-03-15

A QSAR based almost entirely on quantum theoretically calculated descriptors has been developed for a large and heterogeneous group of aromatic and heteroaromatic carbonic anhydrase inhibitors, using orbital energies, nodal angles, atomic charges, and some other intuitively appealing descriptors. Most calculations have been done at the B3LYP/6-31G* level of theory. For the first time we have treated five-membered rings by the same means that we have used for benzene rings in the past. Our flip regression technique has been expanded to encompass automatic variable selection. The statistical quality of the results, while not equal to those we have had with benzene derivatives, is very good considering the noncongeneric nature of the compounds. The most significant correlation was with charge on the atoms of the sulfonamide group, followed by the nodal orientation and the solvation energy calculated by COSMO and the charge polarization of the molecule calculated as the mean absolute Mulliken charge over all atoms.

Crystal structure of di-μ-chlorido-bis-(chlorido-{N1,N1-diethyl-N4-[(pyridin-2-yl-κN)methyl-idene]benzene-1,4-di-amine-κN4}mercury(II)).

PubMed

Faizi, Md Serajul Haque; Dege, Necmi; Goleva, Kateryna

2017-06-01

The title dinuclear mercury(II) complex, [Hg 2 Cl 4 (C 16 H 19 N 3 ) 2 ], synthesized from the pyridine-derived Schiff base ( E )- N 1 , N 1 -diethyl- N 4 -[(pyridin-2-yl)methyl-idene]benzene-1,4-di-amine (DPMBD), has inversion symmetry. The five-coordinated Hg II atoms have distorted square-pyramidal stereochemistry comprising two N-atom donors from bidentate chelate BPMBD ligands and three Cl-atom donors, two bridging and one monodentate. The dihedral angle between the benzene and the pyridine rings in the BPMBD ligand is 7.55 (4)°. In the crystal, the dinuclear mol-ecules are linked by weak C-H⋯Cl hydrogen bonds, forming zigzag ribbons lying parallel to [001]. Also present in the structure are π-π inter-actions between benzene and pyridine rings [minimum ring-centroid separation = 3.698 (8) Å].

Morphological evolution of Ge/Si(001) quantum dot rings formed at the rim of wet-etched pits.

PubMed

Grydlik, Martyna; Brehm, Moritz; Schäffler, Friedrich

2012-10-30

We demonstrate the formation of Ge quantum dots in ring-like arrangements around predefined {111}-faceted pits in the Si(001) substrate. We report on the complex morphological evolution of the single quantum dots contributing to the rings by means of atomic force microscopy and demonstrate that by careful adjustment of the epitaxial growth parameters, such rings containing densely squeezed islands can be grown with large spatial distances of up to 5 μm without additional nucleation of randomly distributed quantum dots between the rings.

Transformation of self-assembled InAs/InP quantum dots into quantum rings without capping.

PubMed

Sormunen, Jaakko; Riikonen, Juha; Mattila, Marco; Tiilikainen, Jouni; Sopanen, Markku; Lipsanen, Harri

2005-08-01

Transformation of self-assembled InAs quantum dots (QDs) on InP(100) into quantum rings (QRs) is studied. In contrast to the typical approach to III--V semiconductor QR growth, the QDs are not capped to form rings. Atomic force micrographs reveal a drastic change from InAs QDs into rings after a growth interruption in tertiarybutylphosphine ambient. Strain energy relief in the InAs QD is discussed and a mechanism for dot-to-ring transformation by As/P exchange reactions is proposed.

Ethyl 2-(4-meth-oxy-phen-yl)-6-oxa-3-aza-bicyclo[3.1.0]hexane-3-carboxyl-ate: crystal structure and Hirshfeld analysis.

PubMed

Zukerman-Schpector, Julio; Sugiyama, Fabricia H; Garcia, Ariel L L; Correia, Carlos Roque D; Jotani, Mukesh M; Tiekink, Edward R T

2017-07-01

The title compound, C 14 H 17 NO 4 , features an epoxide-O atom fused to a pyrrolidyl ring, the latter having an envelope conformation with the N atom being the flap. The 4-meth-oxy-phenyl group is orthogonal to [dihedral angle = 85.02 (6)°] and lies to the opposite side of the five-membered ring to the epoxide O atom, while the N-bound ethyl ester group (r.m.s. deviation of the five fitted atoms = 0.0187 Å) is twisted with respect to the ring [dihedral angle = 17.23 (9)°]. The most prominent inter-actions in the crystal are of the type methine-C-H⋯O(carbon-yl) and these lead to the formation of linear supra-molecular chains along the c axis; weak benzene-C-H⋯O(epoxide) and methine-C-H⋯O(meth-oxy) inter-actions connect these into a three-dimensional architecture. The analysis of the Hirshfeld surface confirms the presence of C-H⋯O inter-actions in the crystal, but also the dominance of H⋯H dispersion contacts.

Charge-free low-temperature method of forming thin film-based nanoscale materials and structures on a substrate

DOEpatents

Hoffbauer, Mark [Los Alamos, NM; Mueller, Alex [Santa Fe, NM

2008-07-01

A method of forming a nanostructure at low temperatures. A substrate that is reactive with one of atomic oxygen and nitrogen is provided. A flux of neutral atoms of at least one of nitrogen and oxygen is generated within a laser-sustained-discharge plasma source and a collimated beam of energetic neutral atoms and molecules is directed from the plasma source onto a surface of the substrate to form the nanostructure. The energetic neutral atoms and molecules in the plasma have an average kinetic energy in a range from about 1 eV to about 5 eV.

Influence of attrition milling on nano-grain boundaries

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

Rawers, J.; Cook, D.

1999-03-01

Nanostructured materials have a relatively large proportion of their atoms associated with the grain boundary, and the method used to develop the nano-grains has a strong influence on the resulting grain boundary structure. In this study, attrition milling iron powders and blends of iron powders produced micron-size particles composed of nano-size grains. Mechanical cold-working powder resulted in dislocation generation, multiplication, and congealing that produced grain refinement. As the grain size approached nano-dimensions, dislocations were no longer sustained within the grain and once generated, rapidly diffused to the grain boundary. Dislocations on the grain boundary strained the local lattice structure which,more » as the grain size decreased, became the entire grain. Mechanical alloying of substitutional aluminium atoms into iron powder resulted in the aluminium atoms substituting for iron atoms in the grain boundary cells and providing a grain boundary structure similar to that of the iron powder processed in argon. Attrition milling iron powder in nitrogen gas resulted in nitrogen atoms being adsorbed onto the particle surface. Continued mechanical milling infused the nitrogen atoms into interstitial lattice sites on the grain boundary which also contributed to expanding and straining the local lattice.« less

Charge Exchange Contribution to the Decay of the Ring Current, Measured by Energetic Neutral Atoms (ENAs)

NASA Technical Reports Server (NTRS)

Jorgensen, A. M.; Henderson, M. G.; Roelof, E. C.; Reeves, G. D.; Spence, H. E.

2001-01-01

In this paper we calculate the contribution of charge exchange to the decay of the ring current. Past works have suggested that charge exchange of ring current protons is primarily responsible for the decay of the ring current during the late recovery phase, but there is still much debate about the fast decay of the early recovery phase. We use energetic neutral atom (ENA) measurements from Polar to calculate the total ENA energy escape. To get the total ENA escape we apply a forward modeling technique, and to estimate the total ring current energy escape we use the Dessler-Parker-Sckopke relationship. We find that during the late recovery phase of the March 10, 1998 storm ENAs with energies greater than 17.5 keV can account for 75% of the estimated energy loss from the ring current. During the fast recovery the measured ENAs can only account for a small portion of the total energy loss. We also find that the lifetime of the trapped ions is significantly shorter during the fast recovery phase than during the late recovery phase, suggesting that different processes are operating during the two phases.

Building Atoms Shell by Shell.

ERIC Educational Resources Information Center

Sussman, Beverly

1993-01-01

Describes an atom-building activity where students construct three-dimensional models of atoms using a styrofoam ball as the nucleus and pom-poms, gum drops, minimarshmallows, or other small items of two different colors to represent protons and neutrons attached. Rings of various sizes with pom-poms attached represent electron shells and…

Unusual case of desmotropy. Combined spectroscopy (¹H-¹⁴N NQDR) and quantum chemistry (periodic hybrid DFT/QTAIM and Hirshfeld surface-based) study of solid dacarbazine (anti-neoplastic).

PubMed

Latosińska, Jolanta Natalia; Latosińska, Magdalena; Seliger, Janez; Žagar, Veselko; Burchardt, Dorota V; Derwich, Katarzyna

2015-01-01

Antineoplastic chemo-therapeutic drug 5-(3,3-dimethyl-1-triazenyl)imidazole-4-carboxamide (Dacarbazine, DTIC), has been studied experimentally in solid state by ¹H-¹⁴N NQDR double resonance at 295 K and theoretically by the Density Functional Theory (DFT)/Quantum Theory of Atoms in Molecules (QTAIM) and Hirshfeld surfaces analysis. Only one set of eighteen resonance frequencies was found in the experiment. This indicates the presence of six inequivalent nitrogen sites: -N(CH₃), -NH₂, -NH- and three -N= (of which one is a ring, two are from triazene) in the DTIC molecule. This contradicts the X-ray data which revealed the multiplication of nitrogen sites due to unusual desmotropism. The averaging of NQR frequencies caused by the fast in NQR time-scale exchange of protons in a double-well potential combined with the oscillations of twisted supramolecular synthons was proposed as a potential mechanism responsible for this apparent contradiction. An effective improvement in the quality of the spectrum reproduction was achieved when the calculations were performed assuming the periodic boundary conditions, BLYP functional, the DNP basis set and taking the 3×3×3 k-point separation. The ordering of the nitrogen sites according to the increasing quadrupole coupling constant (QCC): N(3)

Supramolecular packing and polymorph screening of N-isonicotinoyl arylketone hydrazones with phenol and amino modifications

NASA Astrophysics Data System (ADS)

Hean, Duane; Michael, Joseph P.; Lemmerer, Andreas

2018-04-01

Thirteen structural variants based on the (E)-N‧-(1-arylethylidene)pyridohydrazide template were prepared, investigated and screened for possible polymorphic behaviour. Four variants showed from Differential Scanning Calorimetry Scans thermal events indicative of new solid-state phases. The thirteen variants included substituents R = sbnd OH or sbnd NH2 placed at ortho, meta and para positions on the phenyl ring; and shifting the pyridyl nitrogen between positions 4-, 3- and 2-. The crystal structures of twelve of the compounds were determined to explore their supramolecular structures. The outcomes of these modifications demonstrated that the pyridyl nitrogen at the 2- position is 'locked' by forming a hydrogen bond with the amide hydrogen; while placing the pyridyl nitrogen at positions 3- and 4- offers a greater opportunity for hydrogen bonding with neighbouring molecules. Such interactions include Osbnd H⋯N, Nsbnd H⋯N, Osbnd H⋯O, Nsbnd H⋯O, Nsbnd H⋯π, π⋯π stacking, as well as other weaker interactions such as Csbnd H⋯N, Csbnd H⋯O, Csbnd H⋯N(pyridyl). When OH or NH2 donors are placed in the ortho position, an intramolecular hydrogen bond is formed between the acceptor hydrazone nitrogen and the respective donor. The meta- and para-positioned donors form an unpredictable array of supramolecular structures by forming hydrogen-bonded chains with the pyridyl nitrogen and carbonyl acceptors respectively. In addition to the intramolecular and chain hydrogen bond formation demonstrated throughout the crystal structures under investigation, larger order hydrogen-bonded rings were also observed in some of the supramolecular aggregations. The extent of the hydrogen-bonded ring formations range from two to six molecular participants depending on the specific crystal structure.

Coherent π-electron dynamics of (P)-2,2'-biphenol induced by ultrashort linearly polarized UV pulses: Angular momentum and ring current

NASA Astrophysics Data System (ADS)

Mineo, H.; Lin, S. H.; Fujimura, Y.

2013-02-01

The results of a theoretical investigation of coherent π-electron dynamics for nonplanar (P)-2,2'-biphenol induced by ultrashort linearly polarized UV pulses are presented. Expressions for the time-dependent coherent angular momentum and ring current are derived by using the density matrix method. The time dependence of these coherences is determined by the off-diagonal density matrix element, which can be obtained by solving the coupled equations of motion of the electronic-state density matrix. Dephasing effects on coherent angular momentum and ring current are taken into account within the Markov approximation. The magnitudes of the electronic angular momentum and current are expressed as the sum of expectation values of the corresponding operators in the two phenol rings (L and R rings). Here, L (R) denotes the phenol ring in the left (right)-hand side of (P)-2,2'-biphenol. We define the bond current between the nearest neighbor carbon atoms Ci and Cj as an electric current through a half plane perpendicular to the Ci-Cj bond. The bond current can be expressed in terms of the inter-atomic bond current. The inter-atomic bond current (bond current) depends on the position of the half plane on the bond and has the maximum value at the center. The coherent ring current in each ring is defined by averaging over the bond currents. Since (P)-2,2'-biphenol is nonplanar, the resultant angular momentum is not one-dimensional. Simulations of the time-dependent coherent angular momentum and ring current of (P)-2,2'-biphenol excited by ultrashort linearly polarized UV pulses are carried out using the molecular parameters obtained by the time-dependent density functional theory (TD-DFT) method. Oscillatory behaviors in the time-dependent angular momentum (ring current), which can be called angular momentum (ring current) quantum beats, are classified by the symmetry of the coherent state, symmetric or antisymmetric. The bond current of the bridge bond linking the L and R rings is zero for the symmetric coherent state, while it is nonzero for the antisymmetric coherent state. The magnitudes of ring current and ring current-induced magnetic field are also evaluated, and their possibility as a control parameter in ultrafast switching devices is discussed. The present results give a detailed description of the theoretical treatment reported in our previous paper [H. Mineo, M. Yamaki, Y. Teranish, M. Hayashi, S. H. Lin, and Y. Fujimura, J. Am. Chem. Soc. 134, 14279 (2012), 10.1021/ja3047848].

Coherent π-electron dynamics of (P)-2,2'-biphenol induced by ultrashort linearly polarized UV pulses: angular momentum and ring current.

PubMed

Mineo, H; Lin, S H; Fujimura, Y

2013-02-21

The results of a theoretical investigation of coherent π-electron dynamics for nonplanar (P)-2,2'-biphenol induced by ultrashort linearly polarized UV pulses are presented. Expressions for the time-dependent coherent angular momentum and ring current are derived by using the density matrix method. The time dependence of these coherences is determined by the off-diagonal density matrix element, which can be obtained by solving the coupled equations of motion of the electronic-state density matrix. Dephasing effects on coherent angular momentum and ring current are taken into account within the Markov approximation. The magnitudes of the electronic angular momentum and current are expressed as the sum of expectation values of the corresponding operators in the two phenol rings (L and R rings). Here, L (R) denotes the phenol ring in the left (right)-hand side of (P)-2,2'-biphenol. We define the bond current between the nearest neighbor carbon atoms Ci and Cj as an electric current through a half plane perpendicular to the Ci-Cj bond. The bond current can be expressed in terms of the inter-atomic bond current. The inter-atomic bond current (bond current) depends on the position of the half plane on the bond and has the maximum value at the center. The coherent ring current in each ring is defined by averaging over the bond currents. Since (P)-2,2'-biphenol is nonplanar, the resultant angular momentum is not one-dimensional. Simulations of the time-dependent coherent angular momentum and ring current of (P)-2,2'-biphenol excited by ultrashort linearly polarized UV pulses are carried out using the molecular parameters obtained by the time-dependent density functional theory (TD-DFT) method. Oscillatory behaviors in the time-dependent angular momentum (ring current), which can be called angular momentum (ring current) quantum beats, are classified by the symmetry of the coherent state, symmetric or antisymmetric. The bond current of the bridge bond linking the L and R rings is zero for the symmetric coherent state, while it is nonzero for the antisymmetric coherent state. The magnitudes of ring current and ring current-induced magnetic field are also evaluated, and their possibility as a control parameter in ultrafast switching devices is discussed. The present results give a detailed description of the theoretical treatment reported in our previous paper [H. Mineo, M. Yamaki, Y. Teranish, M. Hayashi, S. H. Lin, and Y. Fujimura, J. Am. Chem. Soc. 134, 14279 (2012)].

Identification of B-K near edge x-ray absorption fine structure peaks of boron nitride thin films prepared by sputtering deposition

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

Niibe, Masahito; Miyamoto, Kazuyoshi; Mitamura, Tohru

2010-09-15

Four {pi}{sup *} resonance peaks were observed in the B-K near edge x-ray absorption fine structure spectra of boron nitride thin films prepared by magnetron sputtering. In the past, these peaks have been explained as the K-absorption of boron atoms, which are present in environment containing nitrogen vacancies, the number of which is 1-3 corresponding to the three peaks at higher photon energy. However, the authors found that there was a strong correlation between the intensities of these three peaks and that of O-K absorption after wide range scanning and simultaneous measurement of nitrogen and oxygen K-absorptions of the BNmore » films. Therefore, the authors conclude that these three peaks at the higher energy side correspond to boron atoms bound to one-to-three oxygen atoms instead of three nitrogen atoms surrounding the boron atom in the h-BN structure. The result of the first-principles calculation with a simple cluster model supported the validity of this explanation.« less

Platinum clusters with precise numbers of atoms for preparative-scale catalysis.

PubMed

Imaoka, Takane; Akanuma, Yuki; Haruta, Naoki; Tsuchiya, Shogo; Ishihara, Kentaro; Okayasu, Takeshi; Chun, Wang-Jae; Takahashi, Masaki; Yamamoto, Kimihisa

2017-09-25

Subnanometer noble metal clusters have enormous potential, mainly for catalytic applications. Because a difference of only one atom may cause significant changes in their reactivity, a preparation method with atomic-level precision is essential. Although such a precision with enough scalability has been achieved by gas-phase synthesis, large-scale preparation is still at the frontier, hampering practical applications. We now show the atom-precise and fully scalable synthesis of platinum clusters on a milligram scale from tiara-like platinum complexes with various ring numbers (n = 5-13). Low-temperature calcination of the complexes on a carbon support under hydrogen stream affords monodispersed platinum clusters, whose atomicity is equivalent to that of the precursor complex. One of the clusters (Pt 10 ) exhibits high catalytic activity in the hydrogenation of styrene compared to that of the other clusters. This method opens an avenue for the application of these clusters to preparative-scale catalysis.The catalytic activity of a noble metal nanocluster is tied to its atomicity. Here, the authors report an atom-precise, fully scalable synthesis of platinum clusters from molecular ring precursors, and show that a variation of only one atom can dramatically change a cluster's reactivity.

Recent developments in trapping and manipulation of atoms with adiabatic potentials

NASA Astrophysics Data System (ADS)

Garraway, Barry M.; Perrin, Hélène

2016-09-01

A combination of static and oscillating magnetic fields can be used to ‘dress’ atoms with radio-frequency (RF), or microwave, radiation. The spatial variation of these fields can be used to create an enormous variety of traps for ultra-cold atoms and quantum gases. This article reviews the type and character of these adiabatic traps and the applications which include atom interferometry and the study of low-dimensional quantum systems. We introduce the main concepts of magnetic traps leading to adiabatic dressed traps. The concept of adiabaticity is discussed in the context of the Landau-Zener model. The first bubble trap experiment is reviewed together with the method used for loading it. Experiments based on atom chips show the production of double wells and ring traps. Dressed atom traps can be evaporatively cooled with an additional RF field, and a weak RF field can be used to probe the spectroscopy of the adiabatic potentials. Several approaches to ring traps formed from adiabatic potentials are discussed, including those based on atom chips, time-averaged adiabatic potentials and induction methods. Several proposals for adiabatic lattices with dressed atoms are also reviewed.

Ultrafast absorption of intense x rays by nitrogen molecules

NASA Astrophysics Data System (ADS)

Buth, Christian; Liu, Ji-Cai; Chen, Mau Hsiung; Cryan, James P.; Fang, Li; Glownia, James M.; Hoener, Matthias; Coffee, Ryan N.; Berrah, Nora

2012-06-01

We devise a theoretical description for the response of nitrogen molecules (N2) to ultrashort and intense x rays from the free electron laser Linac Coherent Light Source (LCLS). We set out from a rate-equation description for the x-ray absorption by a nitrogen atom. The equations are formulated using all one-x-ray-photon absorption cross sections and the Auger and radiative decay widths of multiply-ionized nitrogen atoms. Cross sections are obtained with a one-electron theory and decay widths are determined from ab initio computations using the Dirac-Hartree-Slater (DHS) method. We also calculate all binding and transition energies of nitrogen atoms in all charge states with the DHS method as the difference of two self-consistent field (SCF) calculations (ΔSCF method). To describe the interaction with N2, a detailed investigation of intense x-ray-induced ionization and molecular fragmentation are carried out. As a figure of merit, we calculate ion yields and the average charge state measured in recent experiments at the LCLS. We use a series of phenomenological models of increasing sophistication to unravel the mechanisms of the interaction of x rays with N2: a single atom, a symmetric-sharing model, and a fragmentation-matrix model are developed. The role of the formation and decay of single and double core holes, the metastable states of N_2^{2+}, and molecular fragmentation are explained.

Exploring the anti-cancer activity of novel thiosemicarbazones generated through the combination of retro-fragments: dissection of critical structure-activity relationships.

PubMed

Serda, Maciej; Kalinowski, Danuta S; Rasko, Nathalie; Potůčková, Eliška; Mrozek-Wilczkiewicz, Anna; Musiol, Robert; Małecki, Jan G; Sajewicz, Mieczysław; Ratuszna, Alicja; Muchowicz, Angelika; Gołąb, Jakub; Simůnek, Tomáš; Richardson, Des R; Polanski, Jaroslaw

2014-01-01

Thiosemicarbazones (TSCs) are an interesting class of ligands that show a diverse range of biological activity, including anti-fungal, anti-viral and anti-cancer effects. Our previous studies have demonstrated the potent in vivo anti-tumor activity of novel TSCs and their ability to overcome resistance to clinically used chemotherapeutics. In the current study, 35 novel TSCs of 6 different classes were designed using a combination of retro-fragments that appear in other TSCs. Additionally, di-substitution at the terminal N4 atom, which was previously identified to be critical for potent anti-cancer activity, was preserved through the incorporation of an N4-based piperazine or morpholine ring. The anti-proliferative activity of the novel TSCs were examined in a variety of cancer and normal cell-types. In particular, compounds 1d and 3c demonstrated the greatest promise as anti-cancer agents with potent and selective anti-proliferative activity. Structure-activity relationship studies revealed that the chelators that utilized "soft" donor atoms, such as nitrogen and sulfur, resulted in potent anti-cancer activity. Indeed, the N,N,S donor atom set was crucial for the formation of redox active iron complexes that were able to mediate the oxidation of ascorbate. This further highlights the important role of reactive oxygen species generation in mediating potent anti-cancer activity. Significantly, this study identified the potent and selective anti-cancer activity of 1d and 3c that warrants further examination.

Using Hyperfine Structure to Quantify the Effects of Substitution on the Electron Distribution Within a Pyridine Ring: a Study of 2-, 3-, and 4-PICOLYLAMINE

NASA Astrophysics Data System (ADS)

McDivitt, Lindsey M.; Himes, Korrina M.; Bailey, Josiah R.; McMahon, Timothy J.; Bird, Ryan G.

2017-06-01

The ground state rotational spectra of the three methylamine substituted pyridines, 2-, 3-, and 4-picolylamine, were collected and analyzed over the frequency range of 7-17.5 GHz using chirped-pulsed Fourier transform microwave spectroscopy. All three molecules show a distinctive quadrupole splitting, which is representative of the local electronic environment around the two different ^{14}N nuclei, with the pyridine nitrogen being particularly sensitive to the pi-electron distribution within the ring. The role that the position of the methylamine group plays on the quadrupole coupling constants on both nitrogens will be discussed and compared to other substituted pyridines.

(7-Chloro-2-oxo-2H-chromen-4-yl)methyl pyrrolidine-1-carbodi­thio­ate

PubMed Central

Kotresh, O.; Devarajegowda, H. C.; Shirahatti, Arunkumar; Kumar, K. Mahesh; Mahabhaleshwaraiah, N. M.

2013-01-01

In the title compound, C15H14ClNO2S2, the 2H-chromene ring system is essentially planar, with a maximum deviation of 0.0133 (10) Å. Three C atoms and their attached H atoms of the pyrrolidine ring are disordered [occupany ratio 0.874 (7):0.126 (7)] with both disorder components adopting a twisted conformation. The dihedral angle between the 2H-chromene ring system and the major occupancy component of the pyrrolidine ring is 89.45 (7)°. In the crystal, inversion dimers linked by pairs of C—H⋯S and C—H⋯O inter­actions generate R 2 2(24) and R 2 2(10) loops, respectively. Further C—H⋯O hydrogen bonds link the dimers into [100] chains. C—H⋯π inter­actions also occur and there is very weak π–π stacking [inter­planar spacing = 3.650 (5) Å; centroid–centroid distance = 4.095 (7) Å] between inversion-related chloro­benzene rings. PMID:24454115

Surface compositional profiles of self-assembled InAs/GaAs quantum rings

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

Magri, Rita; Heun, Stefan; Biasiol, Giorgio

2010-01-04

The surface composition profiles of self-assembled InAs/GaAs quantum rings (QR) are studied both experimentally and theoretically. By using X-ray Photoemission Electron Microscopy (XPEEM) we obtain a 2D composition mapping of unburied rings, which can be directly related to the QR topography measured by Atomic Force Microscopy (AFM). Top-surface composition mapping allows us to obtain information on structures which cannot be directly accessed with cross-sectional studies since overgrowing the QRs with a thick GaAs film alters both their morphology and composition. The 2D surface maps reveal a non-uniform distribution across the rings with an In richer InGaAs alloy in the centralmore » hole regions. Elastic energy calculations via a Valence Force Field (VFF) approach show that, for a given shape of the rings and a fixed total number of Ga and In atoms, an In enrichment of the alloy in the central hole region, together with an In enrichment of the surface layers, leads to a lowering of the total strain energy.« less

Recent advances in transition metal-catalyzed N -atom transfer reactions of azides

PubMed Central

Driver, Tom G.

2011-01-01

Transition metal-catalyzed N-atom transfer reactions of azides provide efficient ways to construct new carbon–nitrogen and sulfur–nitrogen bonds. These reactions are inherently green: no additive besides catalyst is needed to form the nitrenoid reactive intermediate, and the by-product of the reaction is environmentally benign N2 gas. As such, azides can be useful precursors for transition metal-catalyzed N-atom transfer to sulfides, olefins and C–H bonds. These methods offer competitive selectivities and comparable substrate scope as alternative processes to generate metal nitrenoids. PMID:20617243

Revealing the Origin of Activity in Nitrogen-Doped Nanocarbons towards Electrocatalytic Reduction of Carbon Dioxide.

PubMed

Xu, Junyuan; Kan, Yuhe; Huang, Rui; Zhang, Bingsen; Wang, Bolun; Wu, Kuang-Hsu; Lin, Yangming; Sun, Xiaoyan; Li, Qingfeng; Centi, Gabriele; Su, Dangsheng

2016-05-23

Carbon nanotubes (CNTs) are functionalized with nitrogen atoms for reduction of carbon dioxide (CO2 ). The investigation explores the origin of the catalyst's activity and the role of nitrogen chemical states therein. The catalysts show excellent performances, with about 90 % current efficiency for CO formation and stability over 60 hours. The Tafel analyses and density functional theory calculations suggest that the reduction of CO2 proceeds through an initial rate-determining transfer of one electron to CO2 , which leads to the formation of carbon dioxide radical anion (CO2 (.-) ). The initial reduction barrier is too high on pristine CNTs, resulting in a very high overpotentials at which the hydrogen evolution reaction dominates over CO2 reduction. The doped nitrogen atoms stabilize the radical anion, thereby lowering the initial reduction barrier and improving the intrinsic activity. The most efficient nitrogen chemical state for this reaction is quaternary nitrogen, followed by pyridinic and pyrrolic nitrogen. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nitrogen plasma-treated multilayer graphene-based field effect transistor fabrication and electronic characteristics

NASA Astrophysics Data System (ADS)

Su, Wei-Jhih; Chang, Hsuan-Chen; Honda, Shin-ichi; Lin, Pao-Hung; Huang, Ying-Sheng; Lee, Kuei-Yi

2017-08-01

Chemical doping with hetero-atoms is an effective method used to change the characteristics of materials. Nitrogen doping technology plays a critical role in regulating the electronic properties of graphene. Nitrogen plasma treatment was used in this work to dope nitrogen atoms to modulate multilayer graphene electrical properties. The measured I-V multilayer graphene-base field-effect transistor characteristics (GFETs) showed a V-shaped transfer curve with the hole and electron region separated from the measured current-voltage (I-V) minimum. GFETs fabricated with multilayer graphene from chemical vapor deposition (CVD) exhibited p-type behavior because of oxygen adsorption. After using different nitrogen plasma treatment times, the minimum in I-V characteristic shifted into the negative gate voltage region with increased nitrogen concentration and the GFET channel became an n-type semiconductor. GFETs could be easily fabricated using this method with potential for various applications. The GFET transfer characteristics could be tuned precisely by adjusting the nitrogen plasma treatment time.

(Nitrato-κ2 O,O′)bis­(1,10-phenanthroline-κ2 N,N′)copper(II) tricyano­methanide

PubMed Central

Lacková, Katarína; Potočňák, Ivan

2012-01-01

The title compound, [Cu(NO3)(C12H8N2)2][C(CN)3], is formed of discrete [Cu(NO3)(phen)2]+ complex cations (phen is 1,10-phenanthroline) and C(CN)3 − counter-anions. The CuII atom has an asymmetric tetragonal–bipyramidal (4 + 1+1) stereochemistry with a pseudo-C 2 symmetry axis bis­ecting the nitrate ligand and passing through the CuII atom between the two phen ligands. The four N atoms of the phen ligands coordinate to the CuII atom with Cu—N distances in the range 1.974 (2)–2.126 (2) Å, while the two O atoms coordinate at substanti­ally different distances [2.154 (2) and 2.586 (2) Å]. The structure is stabilized by C—H⋯O hydrogen bonds and weak π–π inter­actions between nearly parallel benzene and pyridine rings of two adjacent phen mol­ecules, with centroid–centroid distances of 3.684 (2) and 3.6111 (2) Å, and between π-electrons of the tricyano­methanide anion and the pyridine or benzene rings [N⋯(ring centroid) distances = 3.553 (3)–3.875 (3) Å]. PMID:23468758

Compounds for neutron radiation detectors and systems thereof

DOEpatents

Payne, Stephen A; Stoeffl, Wolfgang; Zaitseva, Natalia P; Cherepy, Nerine J; Carman, M. Leslie

2014-05-27

A material according to one embodiment exhibits an optical response signature for neutrons that is different than an optical response signature for gamma rays, said material exhibiting performance comparable to or superior to stilbene in terms of distinguishing neutrons from gamma rays, wherein the material is not stilbene, the material comprising a molecule selected from a group consisting of: two or more benzene rings, one or more benzene rings with a carboxylic acid group, one or more benzene rings with at least one double bound adjacent to said benzene ring, and one or more benzene rings for which at least one atom in the benzene ring is not carbon.

Single-ring magnetic cusp low gas pressure ion source

DOEpatents

Bacon, Frank M.; Brainard, John P.; O'Hagan, James B.; Walko, Robert J.

1985-01-01

A single-ring magnetic cusp low gas pressure ion source designed for use in a sealed, nonpumped neutron generator utilizes a cathode and an anode, three electrically floating electrodes (a reflector behind the cathode, a heat shield around the anode, and an aperture plate), together with a single ring-cusp magnetic field, to establish and energy-filtering mechanism for producing atomic-hydrogen ions.

Synthesis, characterization, DNA binding and catalytic applications of Ru(III) complexes.

PubMed

Shoair, A F; El-Shobaky, A R; Azab, E A

2015-01-01

A new series of azodye ligands 5-chloro-3-hydroxy-4-(aryldiazenyl)pyridin-2(1H)-one (HLn) were synthesized by coupling of 5-chloro-3-hydroxypyridin-2(1H)-one with aniline and its p-derivatives. These ligands and their Ru(III) complexes of the type trans-[Ru(Ln)2(AsPh3)2]Cl were characterized by elemental analyses, IR, (1)H NMR and UV-Visible spectra as well as magnetic and thermal measurements. The molar conductance measurements proved that all the complexes are electrolytes. IR spectra show that the ligands (HLn) acts as a monobasic bidentate ligand by coordinating via the nitrogen atom of the azo group (NN) and oxygen atom of the deprotonated phenolic OH group, thereby forming a six-membered chelating ring and concomitant formation of an intramolecular hydrogen bond. The molecular and electronic structures of the investigated compounds (HLn) were also studied using quantum chemical calculations. The calf thymus DNA binding activity of the ligands (HLn) and their Ru(III) complexes were studied by absorption spectra and viscosity measurements. The mechanism and the catalytic oxidation of benzyl alcohol by trans-[Ru(Ln)2(AsPh3)2]Cl with hydrogen peroxide as co-oxidant were described. Copyright © 2015 Elsevier B.V. All rights reserved.

Blue Photoluminescence From Silacyclobutene Compounds

NASA Astrophysics Data System (ADS)

Pernisz, Udo

1999-04-01

Organosilicon compounds in which the Si atom is bound to an aromatic moiety such as a phenyl group, exhibit strong blue photoluminescence when excited with UV light (for example at a wavelength of 337 nm). This phenomenon was investigated quantitatively at room temperature and at the temperature of liquid nitrogen (78 K) by measuring the emission and excitation spectra of the total luminescence, and of the phosphorescence, for a silacyclobutene compound in which two phenyl groups are joined across the C=C double bond of the ring. The effect of a series of organic substituents on the Si atom was investigated as well as the time dependence of the phosphorescence intensity decay for this class of materials. A tentative model of the energy levels in this compound is proposed. The observation of visible blue emission -- in contrast to photoluminescence in the UV from the aromatic groups -- is explained by the Si-C bond lowering the energy of the molecular orbitals, an effect that is currently under study for a range of Si-containing compounds. Synthesis of the silacyclobutene compounds was performed at the laboratory of Prof. N. Auner, now at J.W. Goethe Universität, Frankfurt, Germany. His contributions, and those of his collaborators, to the work reported here are gratefully acknowledged.

A complex study of 5-amino-3-methyl-4-[2-(5-amino-1,3,4-oxadiazolo)]-isoxazole monohydrate: A new low-molecular-weight immune response modifier

NASA Astrophysics Data System (ADS)

Ryng, Stanisław; Zimecki, Michał; Jezierska-Mazzarello, Aneta; Panek, Jarosław J.; Mączyński, Marcin; Głowiak, Tadeusz; Sawka-Dobrowolska, Wanda; Koll, Aleksander

2011-07-01

A new potential lead structure with immunological activity, 5-amino-3-methyl-4-[2-(5-amino-1,3,4-oxadiazolo)]-isoxazole monohydrate, was synthesized. A detailed description of synthesis is presented together with X-ray structural analysis. In vitro assays showed that the compound had a potent immunosuppressive activity. Next, Density Functional Theory (DFT) was employed to shed a light on molecular properties of the investigated isoxazole derivative. The molecular modeling part included geometric as well as electronic structure descriptions: (i) the conformational analysis was performed to localize the most appropriate conformation; (ii) the coordination energy and Basis Set Superposition Error (BSSE) were estimated for the complex of the isoxazole derivative interacting with water molecule; (iii) the potential energy distribution was used to assign molecular vibrations, and NBO population analysis served to describe the electronic structure; (iv) the electrostatic potential map was generated to provide the graphical presentation of regions exposed for intermolecular interactions. The contacts between the water molecule and the nitrogen atom of the isoxazole ring edge were present in the solid phase. On the other hand, the theoretical DFT prediction was that the oxygen atom of the edge should form a more stable complex with the water molecule.

Effects of variation in chain length on ternary polymer electrolyte - Ionic liquid mixture - A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Raju, S. G.; Hariharan, Krishnan S.; Park, Da-Hye; Kang, HyoRang; Kolake, Subramanya Mayya

2015-10-01

Molecular dynamics (MD) simulations of ternary polymer electrolyte - ionic liquid mixtures are conducted using an all-atom model. N-alkyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([CnMPy][TFSI], n = 1, 3, 6, 9) and polyethylene oxide (PEO) are used. Microscopic structure, energetics and dynamics of ionic liquid (IL) in these ternary mixtures are studied. Properties of these four pure IL are also calculated and compared to that in ternary mixtures. Interaction between pyrrolidinium cation and TFSI is stronger and there is larger propensity of ion-pair formation in ternary mixtures. Unlike the case in imidazolium IL, near neighbor structural correlation between TFSI reduces with increase in chain length on cation in both pure IL and ternary mixtures. Using spatial density maps, regions where PEO and TFSI interact with pyrrolidinium cation are identified. Oxygens of PEO are above and below the pyrrolidinium ring and away from the bulky alkyl groups whereas TFSI is present close to nitrogen atom of CnMPy. In pure IL, diffusion coefficient (D) of C3MPy is larger than of TFSI but D of C9MPy and C6MPy are larger than that of TFSI. The reasons for alkyl chain dependent phenomena are explored.

Cryogenic and Simulated Fuel Jet Breakup in Argon, Helium and Nitrogen Gas Flows

NASA Technical Reports Server (NTRS)

Ingebo, Robert D.

1995-01-01

Two-phase flow atomization of liquid nitrogen jets was experimentally investigated. They were co-axially injected into high-velocity gas flows of helium, nitrogen and argon, respectively, and atomized internally inside a two-fluid fuel nozzle. Cryogenic sprays with relatively high specific surface areas were produced, i.e., ratios of surface area to volume were fairly high. This was indicated by values of reciprocal Sauter mean diameters, RSMD's, as measured with a scattered- light scanning instrument developed at NASA Lewis Research Center. Correlating expressions were derived for the three atomizing gases over a gas temperature range of 111 to 422 K. Also, the correlation was extended to include waterjet breakup data that had been previously obtained in simulating fuel jet breakup in sonic velocity gas flow. The final correlating expression included a new dimensionless molecular-scale acceleration group. It was needed to correlate RSMD data, for LN2 and H2O sprays, with the fluid properties of the liquid jets and atomizing gases used in this investigation.

Evidence for the Formation of Nitrogen-Rich Platinum and Palladium Nitride Nanoparticles

DOE PAGES

Veith, Gabriel M.; Lupini, Andrew R.; Baggetto, Loïc; ...

2013-12-03

Here, we report evidence for the formation of nitrogen-rich precious metal nanoparticles (Pt, Pd) prepared by reactive sputtering of the pure metal in a N 2 plasma. The composition of the nanoparticles varies as a function of particle size and growth conditions. For the smallest particles the nitrogen content appears to be as high as 6.7 N atoms for each Pd atom or 5.9 N atoms for each Pt atom whereas bulk films have nominal compositions of Pt 7.3N and Pd 2.5N. The nanoparticles are metastable in air and moisture, slowly decomposing over several years. This paper describes the synthesismore » of these materials along with experimental evidence of the composition, oxidation state, and growth modes. Moreover, the catalytic properties of these N-rich nanoparticles were accessed by rotating disk electrode electrochemical studies, the liquid phase oxidation of benzyl alcohol and gas phase CO oxidation and support the experimental evidence for the materials composition.« less

Preferential incorporation of substitutional nitrogen near the atomic step edges in diluted nitride alloys

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

Cornet, C.; Nguyen Thanh, T.; Almosni, S.

We have investigated the influence of the surface roughness on nitrogen incorporation during the molecular beam epitaxy of diluted nitrides, independently of the other growth parameters. GaPN/GaP layers grown simultaneously on surfaces displaying different roughnesses reveal a large difference in nitrogen incorporation despite the same growth temperature and growth rate. The same difference is found on quasi-lattice-matched GaAsPN demonstrating that the phenomenon is not related to any strain-induced mechanisms. The tendency is clearly confirmed when varying the growth conditions. As a direct consequence, the incorporation of substitutional nitrogen near the atomic step edges is found to be 6.7 times moremore » probable than the in-plane nitrogen incorporation. The formation of N-N{sub i} clusters and their stability on the surface is discussed.« less

Synthesis of pyrido[1,2-a]benzimidazoles and other fused imidazole derivatives with a bridgehead nitrogen atom

NASA Astrophysics Data System (ADS)

Begunov, Roman S.; Ryzvanovich, Galina A.

2013-01-01

Main methods for the synthesis of fused imidazole derivatives with a bridgehead nitrogen atom are systematically considered and summarized. The reaction mechanisms that underlie the methods for the synthesis of pyrido[1,2-a]benzimidazoles and related compounds are described. Biological properties and mechanisms of the biological activity of fused azaheterocycles are discussed. The bibliography includes 152 references.

First-principles studies of a photovoltaic material based on silicon heavily codoped with sulfur and nitrogen

NASA Astrophysics Data System (ADS)

Dong, Xiao; Wang, Yongyong; Song, Xiaohui; Yang, Feng

2018-03-01

In silicon co-hyperdoped with nitrogen and sulfur, dopant atoms tend to form dimers in the near-equilibrium process. The dimer that contains substitutional N and S atoms has the lowest formation energy and can form an impurity band that overlaps with the conduction band (CB). When separating the two atoms far apart from each other, the impurity band is clearly isolated from the CB and becomes an intermediate band (IB). The sub-band-gap absorption decreases with the decrease in the substitutional atom distance. The sub-band-gap absorption of the material is the combined effect of the configurations with different N-S distances.

Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret

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

Sun, Hongyan, E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil; Vaghjiani, Ghanshyam L., E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil

2015-05-28

Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was foundmore » that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH{sub 2} group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C{sub 2v} symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice–Ramsperger–Kassel–Marcus/multi-well master equation simulations, the results of which reveal the formation of (NO{sub 2} + H{sub 2}O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358–366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.« less

The Contrasting Alkylations of 4-(Dimethylaminomethyl)pyridine and 4-(Dimethylamino)pyridine: An Organic Chemistry Experiment

ERIC Educational Resources Information Center

Jantzi, Kevin L.; Wiltrakis, Susan; Wolf, Lauren; Weber, Anna; Cardinal, Josh; Krieter, Katie

2011-01-01

A critical factor for the increased nucleophilicity of the pyridine nitrogen in 4-(dimethylamino)pyridine (DMAP) is electron donation via resonance from the amino group into the aromatic ring that increases electron density on the pyridine nitrogen. To explore how important this resonance effect is, 4-(dimethylaminomethyl)pyridine (DMAMP) was…

Redox shuttles for overcharge protection of lithium batteries

DOEpatents

Amine, Khalil; Chen, Zonghai; Wang, Qingzheng

2010-12-14

The present invention is generally related to electrolytes containing novel redox shuttles for overcharge protection of lithium-ion batteries. The redox shuttles are capable of thousands hours of overcharge tolerance and have a redox potential at about 3-5.5 V vs. Li and particularly about 4.4-4.8 V vs. Li. Accordingly, in one aspect the invention provides electrolytes comprising an alkali metal salt; a polar aprotic solvent; and a redox shuttle additive that is an aromatic compound having at least one aromatic ring with four or more electronegative substituents, two or more oxygen atoms bonded to the aromatic ring, and no hydrogen atoms bonded to the aromatic ring; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.

Poly[diaqua­tris­(μ4-1,3-phenyl­enediacetato)­dineodymium(III)

PubMed Central

Gao, Zhu-Qing; Lv, Dong-Yu; Li, Hong-Ji; Gu, Jin-Zhong

2011-01-01

In the title coordination polymer, [Nd2(C10H8O4)3(H2O)2]n, each of the two NdIII ions is nine-coordinated by eight O atoms from six different 2,2′-(m-phenyl­ene)diacetate (pda) bivalent anions and by one O atom from a water mol­ecule, forming a distorted tricapped trigonal–prismatic coordination geometry. Eight NdIII ions and 12 pda ligands form a large [Nd8(pda)12] ring, and four NdIII ions and six pda ligands form a small [Nd4(pda)6] ring. These rings are further connected by the coordination inter­actions of pda ligands and NdIII, generating a three-dimensional supra­molecular framework. PMID:21522305

1-(Prop-2-yn-yl)indoline-2,3-dione.

PubMed

Qachchachi, Fatima-Zahrae; Ouazzani Chahdi, Fouad; Misbahi, Houria; Bodensteiner, Michael; El Ammari, Lahcen

2014-03-01

The structure of the title compound, C11H7NO2, is isotypic to that of its homologue, 1-octylindoline-2,3-dione [Qachchachi et al. (2013 ▶). Acta Cryst. E69, o1801]. The indoline ring and the two carbonyl O atoms are approximately coplanar, the largest deviation from the mean plane being 0.021 (1) Å for one of the O atoms. The mean plane through the fused ring system is nearly perpendicular to the propynyl group, as indicated by the N-C-C-C torsion angle of 77.9 (1)°. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds and π-π inter-actions between benzene rings [inter-centroid distance = 3.5630 (10) Å], forming a three-dimensional structure.

Understanding Am3+/Cm3+ separation with H4TPAEN and its hydrophilic derivatives: a quantum chemical study.

PubMed

Huang, Pin-Wen; Wang, Cong-Zhi; Wu, Qun-Yan; Lan, Jian-Hui; Song, Gang; Chai, Zhi-Fang; Shi, Wei-Qun

2018-05-23

Am3+/Cm3+ separation is an extremely hard but important task in nuclear waste treatment. In this study, Am and Cm complexes formed with a back-extraction agent N,N,N',N'-tetrakis[(6-carboxypyridin-2-yl)methyl]ethylene-diamine (H4TPAEN) and its two derivatives with hydrophilic substituents (methoxy and morpholine groups) were investigated using the density functional theory (DFT). The optimized geometrical structures indicated that the Am3+ cation matched better with the cavities of the three studied ligands than Cm3+, and the Am3+ cations were located deeper in the cavities of the ligands. The bond order and quantum theory of atoms in molecules (QTAIM) analyses suggested that ionic interactions dominated An-N and An-O (An = Cm and Am) bonds. However, weak and different extents of partial covalency could also be found in the Am-N and Cm-N bonds. The O donor atoms in the carboxylate groups preferably coordinated with Cm3+ rather than Am3+, whereas the N atoms preferred Am3+. Therefore, the Am3+/Cm3+ selectivity of H4TPAEN and its two hydrophilic derivatives may be ascribed to the competition between the An-N and An-O interactions and the few dissimilarities in their geometrical structures. Based on our calculations, the methoxy and morpholine groups in the two derivatives can serve as electron-donating groups and enhance the strength of the An-NPY bonds (NPY denotes the nitrogen atom of pyridine ring). When compared with the Am-complex, the Cm-complex exhibited significant strength effect, resulting in the relatively lower Am3+/Cm3+ separation ability of the H4TPAEN's hydrophilic derivatives.

Angular distribution of photoelectrons from atomic oxygen, nitrogen and carbon. [in upper atmosphere

NASA Technical Reports Server (NTRS)

Manson, S. J.; Kennedy, D. J.; Starace, A. F.; Dill, D.

1974-01-01

The angular distributions of photoelectrons from atomic oxygen, nitrogen, and carbon are calculated. Both Hartree-Fock and Hartree-Slater (Herman-Skillman) wave functions are used for oxygen, and the agreement is excellent; thus only Hartree-Slater functions are used for carbon and nitrogen. The pitch-angle distribution of photoelectrons is discussed, and it is shown that previous approximations of energy-independent isotropic or sin squared theta distributions are at odds with the authors' results, which vary with energy. This variation with energy is discussed, as is the reliability of these calculations.

Pseudocapacitive Effects of N-Doped Carbon Nanotube Electrodes in Supercapacitors

PubMed Central

Yun, Young Soo; Park, Hyun Ho; Jin, Hyoung-Joon

2012-01-01

Nitrogen- and micropore-containing carbon nanotubes (NMCNTs) were prepared by carbonization of nitrogen-enriched, polymer-coated carbon nanotubes (CNTs), and the electrochemical performances of the NMCNTs with different heteroatom contents were investigated. NMCNTs-700 containing 9.1 wt% nitrogen atoms had a capacitance of 190.8 F/g, which was much higher than that of pristine CNTs (48.4 F/g), despite the similar surface area of the two CNTs, and was also higher than that of activated CNTs (151.7 F/g) with a surface area of 778 m2/g and a nitrogen atom content of 1.2 wt%. These results showed that pseudocapacitive effects play an important role in the electrochemical performance of supercapacitor electrodes.

Rapid solidification of metallic particulates

NASA Technical Reports Server (NTRS)

Grant, N. J.

1982-01-01

In order to maximize the heat transfer coefficient the most important variable in rapid solidification is the powder particle size. The finer the particle size, the higher the solidification rate. Efforts to decrease the particle size diameter offer the greatest payoff in attained quench rate. The velocity of the liquid droplet in the atmosphere is the second most important variable. Unfortunately the choices of gas atmospheres are sharply limited both because of conductivity and cost. Nitrogen and argon stand out as the preferred gases, nitrogen where reactions are unimportant and argon where reaction with nitrogen may be important. In gas atomization, helium offers up to an order of magnitude increase in solidification rate over argon and nitrogen. By contrast, atomization in vacuum drops the quench rate several orders of magnitude.

Atmospheric Pseudohalogen Chemistry

NASA Technical Reports Server (NTRS)

Lary, David John

2004-01-01

Hydrogen cyanide is not usually considered in atmospheric chemical models. The paper presents three reasons why hydrogen cyanide is likely to be significant for atmospheric chemistry. Firstly, HCN is a product and marker of biomass burning. Secondly, it is also likely that lightning is producing HCN, and as HCN is sparingly soluble it could be a useful long-lived "smoking gun" marker of lightning activity. Thirdly, the chemical decomposition of HCN leads to the production of small amounts of the cyanide (CN) and NCO radicals. The NCO radical can be photolyzed in the visible portion of the spectrum yielding nitrogen atoms (N). The production of nitrogen atoms is significant as it leads to the titration of total nitrogen from the atmosphere via N+N->N2, where N2 is molecular nitrogen.

Crystal structure of 2α-(1,1-di­phenyl­eth­yl)-4-methyl-4α,5α-diphenyl-1,3-dioxolane: the result of a non-acid pinacol rearrangement

PubMed Central

Kirchner, Richard M.; Corfield, Peter W. R.; Annabi, Michelle; Regan, John; Speina, Kevin; DiProperzio, Anthony; Ciaccio, James A.; Capitani, Joseph F.

2015-01-01

The title compound, C30H28O2, was obtained during recrystallization of (±)-1,2-diphenyl-1,2-propane­diol in 1-butanol, from an unexpected non-acid-catalyzed pinacol rearrangement followed by acetal formation of the newly formed aldehyde with the diol. The tri-substituted dioxolane ring has a twist conformation on the C—O bond opposite the methyl-substituted C atom. There is an intra­molecular C—H⋯π inter­action present involving one of the di­phenyl­ethyl rings and an H atom of the phenyl ring in position 4 of the dioxolane ring. In the crystal, mol­ecules are linked by weak C—H⋯O hydrogen bonds, forming chains along [001]. The chains are linked by a second C—H⋯π inter­action, forming sheets parallel to the bc plane. PMID:26594491

Docking model of the nicotinic acetylcholine receptor and nitromethylene neonicotinoid derivatives with a longer chiral substituent and their biological activities.

PubMed

Nagaoka, Hikaru; Nishiwaki, Hisashi; Kubo, Takuya; Akamatsu, Miki; Yamauchi, Satoshi; Shuto, Yoshihiro

2015-02-15

In the present study, nitromethylene neonicotinoid derivatives possessing substituents that contain a sulfur atom, oxygen atom or aromatic ring at position 5 on the imidazolidine ring were synthesized to evaluate their affinity for the nicotinic acetylcholine receptor (nAChR) and their insecticidal activity against adult female houseflies. Comparing the receptor affinity of the alkylated derivative with the receptor affinity of compounds possessing either ether or thioether groups revealed that conversion of the carbon atom to a sulfur atom did not influence the receptor affinity, whereas conversion to an oxygen atom was disadvantageous for the receptor affinity. The receptor affinity of compounds possessing a benzyl or phenyl group was lower than that of the unsubstituted compound. Analysis of the three-dimensional quantitative structure-activity relationship using comparative molecular field analysis demonstrated that steric hindrance of the receptor should exist around the C3 of an n-butyl group attached at position 5 on the imidazolidine ring. A docking study of the nAChR-ligand model suggested that the ligand-binding region expands as the length of the substituent increases by brushing against the amino acids that form the binding region. The insecticidal activity of the compounds was positively correlated with the receptor affinity by considering logP and the number of heteroatoms, including sulfur and oxygen atoms, in the substituents, suggesting that the insecticidal activity is influenced by the receptor affinity, hydrophobicity, and metabolic stability of the compounds. Copyright © 2015 Elsevier Ltd. All rights reserved.

Empirical model of atomic nitrogen in the upper thermosphere

NASA Technical Reports Server (NTRS)

Engebretson, M. J.; Mauersberger, K.; Kayser, D. C.; Potter, W. E.; Nier, A. O.

1977-01-01

Atomic nitrogen number densities in the upper thermosphere measured by the open source neutral mass spectrometer (OSS) on Atmosphere Explorer-C during 1974 and part of 1975 have been used to construct a global empirical model at an altitude of 375 km based on a spherical harmonic expansion. The most evident features of the model are large diurnal and seasonal variations of atomic nitrogen and only a moderate and latitude-dependent density increase during periods of geomagnetic activity. Maximum and minimum N number densities at 375 km for periods of low solar activity are 3.6 x 10 to the 6th/cu cm at 1500 LST (local solar time) and low latitude in the summer hemisphere and 1.5 x 10 to the 5th/cu cm at 0200 LST at mid-latitudes in the winter hemisphere.

Phosphorescence Tuning through Heavy Atom Placement in Unsymmetrical Difluoroboron β-Diketonate Materials.

PubMed

Liu, Tiandong; Zhang, Guoqing; Evans, Ruffin E; Trindle, Carl O; Altun, Zikri; DeRosa, Christopher A; Wang, Fang; Zhuang, Meng; Fraser, Cassandra L

2018-02-06

Difluoroboron β-diketonates (BF 2 bdks) show both fluorescence (F) and room-temperature phosphorescence (RTP) when confined to a rigid matrix, such as poly(lactic acid). These materials have been utilized as optical oxygen sensors (e.g., in tumors, wounds, and cells). Spectral features include charge transfer (CT) from the major aromatic donor to the dioxaborine acceptor. A series of naphthyl-phenyl dyes (BF 2 nbm) (1-6) were prepared to test heavy-atom placement effects. The BF 2 nbm dye (1) was substituted with Br on naphthyl (2), phenyl (3), or both rings (4) to tailor the fluorescence/phosphorescence ratio and RTP lifetime-important features for designing O 2 sensing dyes by means of the heavy atom effect. Computational studies identify the naphthyl ring as the major donor. Thus, Br substitution on the naphthyl ring produced greater effects on the optical properties, such as increased RTP intensity and decreased RTP lifetime compared to phenyl substitution. However, for electron-donating piperidyl-phenyl dyes (5), the phenyl aromatic is the major donor. As a result, Br substitution on the naphthyl ring (6) did not alter the optical properties significantly. Experimental data and computational modeling show the importance of Br position. The S 1 and T 1 states are described by two singly occupied MOs (SOMOs). When both of these SOMOs have substantial amplitude on the heavy atom, passage from S 1 to T 1 and emission from T 1 to S 0 are both favored. This shortens the excited-state lifetimes and enhances phosphorescence. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The antitumour drug 7-ethyl-10-hydroxycamptothecin monohydrate and its solid-state hydrolysis mechanism on heating.

PubMed

Ali, Md Ashraf; Noguchi, Shuji; Watanabe, Miteki; Iwao, Yasunori; Itai, Shigeru

2016-10-01

7-Ethyl-10-hydroxycamptothecin [systematic name: (4S)-4,11-diethyl-4,9-dihydroxy-1H-pyrano[3',4':6,7]indolizino[1,2-b]quinoline-3,14(4H,12H)-dione, SN-38] is an antitumour drug which exerts activity through the inhibition of topoisomerase I. The crystal structure of SN-38 as the monohydrate, C 22 H 20 N 2 O 5 ·H 2 O, reveals that it is a monoclinic crystal, with one SN-38 molecule and one water molecule in the asymmetric unit. When the crystal is heated to 473 K, approximately 30% of SN-38 is hydrolyzed at its lactone ring, resulting in the formation of the inactive carboxylate form. The molecular arrangement around the water molecule and the lactone ring of SN-38 in the crystal structure suggests that SN-38 is hydrolyzed by the water molecule at (x, y, z) nucleophilically attacking the carbonyl C atom of the lactone ring at (x - 1, y, z - 1). Hydrogen bonding around the water molecules and the lactone ring appears to promote this hydrolysis reaction: two carbonyl O atoms, which are hydrogen bonded as hydrogen-bond acceptors to the water molecule at (x, y, z), might enhance the nucleophilicity of this water molecule, while the water molecule at (-x, y + 1/2, -z), which is hydrogen bonded as a hydrogen-bond donor to the carbonyl O atom at (x - 1, y, z - 1), might enhance the electrophilicity of the carbonyl C atom.

Nitrogen-doped carbon monolith for alkaline supercapacitors and understanding nitrogen-induced redox transitions.

PubMed

Wang, Da-Wei; Li, Feng; Yin, Li-Chang; Lu, Xu; Chen, Zhi-Gang; Gentle, Ian R; Lu, Gao Qing; Cheng, Hui-Ming

2012-04-23

A nitrogen-doped porous carbon monolith was synthesized as a pseudo-capacitive electrode for use in alkaline supercapacitors. Ammonia-assisted carbonization was used to dope the surface with nitrogen heteroatoms in a way that replaced carbon atoms but kept the oxygen content constant. Ammonia treatment expanded the micropore size-distributions and increased the specific surface area from 383 m(2) g(-1) to 679 m(2) g(-1). The nitrogen-containing porous carbon material showed a higher capacitance (246 F g(-1)) in comparison with the nitrogen-free one (186 F g(-1)). Ex situ electrochemical spectroscopy was used to investigate the evolution of the nitrogen-containing functional groups on the surface of the N-doped carbon electrodes in a three-electrode cell. In addition, first-principles calculations were explored regarding the electronic structures of different nitrogen groups to determine their relative redox potentials. We proposed possible redox reaction pathways based on the calculated redox affinity of different groups and surface analysis, which involved the reversible attachment/detachment of hydroxy groups between pyridone and pyridine. The oxidation of nitrogen atoms in pyridine was also suggested as a possible reaction pathway. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crown ethers in graphene

DOE PAGES

Guo, Junjie; Lee, Jaekwang; Contescu, Cristian I.; ...

2014-11-13

Crown ethers, introduced by Pedersen1, are at their most basic level neutral rings constructed of oxygen atoms linked by two- or three-carbon chains. They have attracted special attention for their ability to selectively incorporate various atoms2 or molecules within the cavity formed by the ring3-6. This property has led to the use of crown ethers and their compounds in a wide range of chemical and biological applications7,8. However, crown ethers are typically highly flexible, frustrating efforts to rigidify them for many uses that demand higher binding affinity and selectivity9,10. In this Letter, we report atomic-resolution images of the same basicmore » structures of the original crown ethers embedded in graphene. This arrangement constrains the crown ethers to be rigid and planar and thus uniquely suited for the many applications that crown ethers are known for. First-principles calculations show that the close similarity of the structures seen in graphene with those of crown ether molecules also extends to their selectivity towards specific metal cations depending on the ring size. Atoms (or molecules) incorporated within the crown ethers in graphene offer a simple environment that can be easily and systematically probed and modeled. Thus, we expect that this discovery will introduce a new wave of investigations and applications of chemically functionalized graphene.« less

Ab Initio Molecular Dynamics Simulations and GIPAW NMR Calculations of a Lithium Borate Glass Melt.

PubMed

Ohkubo, Takahiro; Tsuchida, Eiji; Takahashi, Takafumi; Iwadate, Yasuhiko

2016-04-14

The atomic structure of a molten 0.3Li2O-0.7B2O3 glass at 1250 K was investigated using ab initio molecular dynamics (AIMD) simulations. The gauge including projector augmented wave (GIPAW) method was then employed for computing the chemical shift and quadrupolar coupling constant of (11)B, (17)O, and (7)Li from 764 AIMD derived structures. The chemical shift and quadrupolar coupling constant distributions were directly estimated from the dynamical structure of the molten glass. (11)B NMR parameters of well-known structural units such as the three-coordinated ring, nonring, and four-coordinated tetrahedron were found to be in good agreement with the experimental results. In this study, more detailed classification of B units was presented based on the number of O species bonded to the B atoms. This highlights the limitations of (11)B NMR sensitivity for resolving (11)B local environment using the experimentally obtained spectra only. The (17)O NMR parameter distributions can theoretically resolve the bridging and nonbridging O atoms with different structural units such as nonring, single boroxol ring, and double boroxol ring. Slight but clear differences in the number of bridging O atoms surrounding Li that have not been reported experimentally were observed in the theoretically obtained (7)Li NMR parameters.

Gaseous toroid around Saturn. [Saturnian ring system for atomic hydrogen trapping in Titan atmospheric model

NASA Technical Reports Server (NTRS)

Mcdonough, T. R.

1974-01-01

The trapping of Titan's escaping atmosphere in the Saturnian system by a toroidal ring is discussed. The radius of the toroid is comparable to Titan's orbit, or about ten times larger than the visible rings. Theoretical atmospheric models are formulated that consider Saturn's gravitational attraction and magnetospheric properties in forming this toroid and in protecting toroid particles from direct ionization by solar wind particles.

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

Wang, Jian-Guo; Lee, Patrick K.-M.; Dong, Yu-Hui

Acetohydroxyacid synthase (AHAS; EC 2.2.1.6) is the first enzyme in the biosynthetic pathway of the branched-chain amino acids. It catalyzes the conversion of two molecules of pyruvate into 2-acetolactate or one molecule of pyruvate and one molecule of 2-ketobutyrate into 2-aceto-2-hydroxybutyrate. AHAS requires the cofactors thiamine diphosphate (ThDP), Mg{sup 2+} and FAD for activity. The herbicides that target this enzyme are effective in protecting a broad range of crops from weed species. However, resistance in the field is now a serious problem worldwide. To address this, two new sulfonylureas, monosulfuron and monosulfuron ester, have been developed as commercial herbicides inmore » China. These molecules differ from the traditional sulfonylureas in that the heterocyclic ring attached to the nitrogen atom of the sulfonylurea bridge is monosubstituted rather than disubstituted. The structures of these compounds in complex with the catalytic subunit of Arabidopsis thaliana AHAS have been determined to 3.0 and 2.8 {angstrom}, respectively. In both complexes, these molecules are bound in the tunnel leading to the active site, such that the sole substituent of the heterocyclic ring is buried deepest and oriented towards the ThDP. Unlike the structures of Arabidopsis thaliana AHAS in complex with the classic disubstituted sulfonylureas, where ThDP is broken, this cofactor is intact and present most likely as the hydroxylethyl intermediate.« less

Identification of BVT.2938 metabolites by LC/MS and LC/MS/MS after in vitro incubations with liver microsomes and hepatocytes.

PubMed

Edlund, Per Olof; Baranczewski, Pawel

2004-03-10

The metabolism of the 5HT2c agonist BVT.2938, 1-(3-[2-[(2-ethoxy-3-pyridinyl)oxy]ethoxy]-2-pyrazinyl)-2(R)-methylpiperazine, was studied in vitro by incubation with rat, monkey and human liver microsomes as well as cryopreserved hepatocytes, followed by liquid chromatography/mass spectrometry (LC/MS) and LC/MS/MS analysis on a quadrupole-time of flight mass spectrometer for structural elucidation. Deuterium exchange on column was used to differentiate between hydroxylation and N-oxidation. Liver microsomes were incubated in two different buffer systems with optimum conditions for cytochrome P450 activity or UDP-glucuronosyltransferase activity. The major phase I metabolites of BVT.2938 originated from O-deethylation of the pyridine ring, O-dealkylation of the ethylene bridge, pyrazine ring hydroxylation, hydroxylation of pyridine ring and piperazine ring N-hydroxylation. When a hydrogen carbonate buffer system was supplemented with UDPGA, the piperazine carbamoyl-glucuronide from the parent compound was identified together with several glucuronides of the phase I metabolites. The metabolite pattern in hepatocytes was similar to microsomes except that the sulphate at the N-position of the piperazine ring of BVT.2938 was identified, while the carbamoyl-glucuronide was missing. Excellent correlation was obtained between radioactivity detection and the chemiluminescent nitrogen detector when the nitrogen content of the analytes was taken into account.

Atomizing-gas temperature effect on cryogenic spray dropsize

NASA Technical Reports Server (NTRS)

Ingebo, Robert D.

1993-01-01

Correlating expressions for two-phase flow breakup of liquid nitrogen, LN2, jets in sonic velocity nitrogen gasflows were obtained for an atomizing-gas temperature range of 111 to 442 K. The correlations were based on characteristic dropsize measurements obtained with a scattered-light scanner. The effect of droplet vaporization on the measurements of the volume-median dropsize was calculated by using previously determined heat and momentum transfer expressions for droplets evaporating in high-velocity gasflow. Finally, the dropsize of the originally unvaporized spray was calculated, normalized with respect to jet diameter and correlated with atomizing-gas flowrate and temperature.

A theoretical investigation into the strength of N-NO2 bonds, ring strain and electrostatic potential upon formation of intermolecular H-bonds between HF and the nitro group in nitrogen heterocyclic rings C n H2n N-NO2 (n = 2-5), RDX and HMX.

PubMed

Wang, Bao-Guo; Ren, Fu-de; Shi, Wen-Jing

2015-11-01

Changes in N-NO2 bond strength, ring strain energy and electrostatic potential upon formation of intermolecular H-bonds between HF and the nitro group in nitrogen heterocyclic rings C n H2n N-NO2 (n = 2-5), RDX and HMX were investigated using DFT-B3LYP and MP2(full) methods with the 6-311++G(2df,2p) and aug-cc-pVTZ basis sets. Analysis of electron density shifts was also carried out. The results indicate that H-bonding energy correlates well with the increment of ring strain energy. Upon complex formation, the strength of the N-NO2 trigger-bond is enhanced, suggesting reduced sensitivity, while judged by the increased ring strain energy, sensitivity is increased. However, some features of the molecular surface electrostatic potential, such as a local maximum above the N-NO2 bond and ring, σ + (2) and electrostatic balance parameter ν, remain essentially unchanged upon complex formation, and only a small change in the impact sensitivity h 50 is suggested. It is not sufficient to determine sensitivity solely on the basis of trigger bond or ring strain; as a global feature of a molecule, the molecular surface electrostatic potential is available to help judge the change of sensitivity in H-bonded complexes. Graphical Abstract The strengthened N-NO2 bond suggests reduced sensitivity, while it is reverse by theincreased ring strain energy upon the complex formation. However, the molecular surfaceelectrostatic potential (V S) shows the little change of h 50. The V S should be taken into accountin the analysis of explosive sensitivity in the H-bonded complex.

Spirocyclic character of ixazomib citrate revealed by comprehensive XRD, NMR and DFT study

NASA Astrophysics Data System (ADS)

Skorepova, Eliska; Čerňa, Igor; Vlasáková, Růžena; Zvoníček, Vít; Tkadlecová, Marcela; Dušek, Michal

2017-11-01

Ixazomib citrate is a very recently approved anti-cancer drug. Until now, to the best of our knowledge, no one has been able to solve any crystal structures of this compound. In this work, we present the crystal structures of two isostructural solvates of ixazomib citrate. In all currently available literature, the molecule is characterized as containing a single optically active carbon atom and a borate cycle formed when ixazomib is reacted with citric acid to form a stabilized ixazomib citrate that can be administered orally. However, the crystal structures revealed that none of the up-to-date presented structural formulas of ixazomib citrate are fully accurate. In addition to the citrate ring, another 5-membered ring is formed. These two rings are connected by the boron atom, making this compound a spirocyclic borate. By spirocyclization, the boron atom becomes tetrahedral and therefore optically active. In the crystal structures, ixazomib citrate was found to be in forms of two RR and RS stereoisomers. The results are supported by solid-state and solution NMR and DFT quantum mechanical calculations.

A Saturnian gas ring and the recycling of Titan's atmosphere

NASA Technical Reports Server (NTRS)

Mcdonough, T. R.; Brice, N. M.

1973-01-01

Atoms which escape Titan's atmosphere are unlikely to possess escape velocity from Saturn and can orbit the planet until lost by ionization or collision with Titan. It is predicted that a toroidal ring of between 1 and 1,000 atoms or molecules per cubic centimeter exists around Saturn at a distance of about 10 times the radius of the visible rings. This torus may be detectable from earth orbit and detection or nondetection of it may provide some information about the presence or absence of a Saturnian magnetic field, and the exospheric temperature and atmospheric escape rate of Titan. It is estimated that, if Titan has a large exosphere, 97% or more of the escaping atoms can be recaptured by Titan, thereby decreasing the effective net atmospheric loss rate by up to two orders of magnitude. It is shown that, if Saturn has a magnetic field comparable to Jupiter's the magnetospheric plasma can supply Titan with hydrogen at a rate comparable to the loss rates in some of the models of Trafton (1972) and Sagan (1973).

Sc20C60: a volleyballene

NASA Astrophysics Data System (ADS)

Wang, Jing; Ma, Hong-Man; Liu, Ying

2016-06-01

An exceptionally stable hollow cage containing 20 scandium atoms and 60 carbon atoms has been identified. This Sc20C60 molecular cluster has a Th point group symmetry and a volleyball-like shape that we refer to below as ``Volleyballene''. Electronic structure analysis shows that the formation of delocalized π bonds between Sc atoms and the neighboring pentagonal rings made of carbon atoms is crucial for stabilizing the cage structure. A relatively large HOMO-LUMO gap (~1.4 eV) was found. The results of vibrational frequency analysis and molecular dynamics simulations both demonstrate that this Volleyballene molecule is exceptionally stable.An exceptionally stable hollow cage containing 20 scandium atoms and 60 carbon atoms has been identified. This Sc20C60 molecular cluster has a Th point group symmetry and a volleyball-like shape that we refer to below as ``Volleyballene''. Electronic structure analysis shows that the formation of delocalized π bonds between Sc atoms and the neighboring pentagonal rings made of carbon atoms is crucial for stabilizing the cage structure. A relatively large HOMO-LUMO gap (~1.4 eV) was found. The results of vibrational frequency analysis and molecular dynamics simulations both demonstrate that this Volleyballene molecule is exceptionally stable. Electronic supplementary information (ESI) available: Sc20C60: a Volleyballene_SI. See DOI: 10.1039/c5nr07784b

Molecular Simulation of Ionic Polyimides and Composites with Ionic Liquids as Gas-Separation Membranes.

PubMed

Abedini, Asghar; Crabtree, Ellis; Bara, Jason E; Turner, C Heath

2017-10-24

Polyimides are at the forefront of advanced membrane materials for CO 2 capture and gas-purification processes. Recently, ionic polyimides (i-PIs) have been reported as a new class of condensation polymers that combine structural components of both ionic liquids (ILs) and polyimides through covalent linkages. In this study, we report CO 2 and CH 4 adsorption and structural analyses of an i-PI and an i-PI + IL composite containing [C 4 mim][Tf 2 N]. The combination of molecular dynamics (MD) and grand canonical Monte Carlo (GCMC) simulations is used to compute the gas solubility and the adsorption performance with respect to the density, fractional free volume (FFV), and surface area of the materials. Our results highlight the polymer relaxation process and its correlation to the gas solubility. In particular, the surface area can provide meaningful guidance with respect to the gas solubility, and it tends to be a more sensitive indicator of the adsorption behavior versus only considering the system density and FFV. For instance, as the polymer continues to relax, the density, FFV, and pore-size distribution remain constant while the surface area can continue to increase, enabling more adsorption. Structural analyses are also conducted to identify the nature of the gas adsorption once the ionic liquid is added to the polymer. The presence of the IL significantly displaces the CO 2 molecules from the ligand nitrogen sites in the neat i-PI to the imidazolium rings in the i-PI + IL composite. However, the CH 4 molecules move from the imidazolium ring sites in the neat i-PI to the ligand nitrogen atoms in the i-PI + IL composite. These molecular details can provide critical information for the experimental design of highly selective i-PI materials as well as provide additional guidance for the interpretation of the simulated adsorption systems.

Nanopores creation in boron and nitrogen doped polycrystalline graphene: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Izadifar, Mohammadreza; Abadi, Rouzbeh; Nezhad Shirazi, Ali Hossein; Alajlan, Naif; Rabczuk, Timon

2018-05-01

In the present paper, molecular dynamic simulations have been conducted to investigate the nanopores creation on 10% of boron and nitrogen doped polycrystalline graphene by silicon and diamond nanoclusters. Two types of nanoclusters based on silicon and diamond are used to investigate their effect for the fabrication of nanopores. Therefore, three different diameter sizes of the clusters with five kinetic energies of 10, 50, 100, 300 and 500 eV/atom at four different locations in boron or nitrogen doped polycrystalline graphene nanosheets have been perused. We also study the effect of 3% and 6% of boron doped polycrystalline graphene with the best outcome from 10% of doping. Our results reveal that the diamond cluster with diameter of 2 and 2.5 nm fabricates the largest nanopore areas on boron and nitrogen doped polycrystalline graphene, respectively. Furthermore, the kinetic energies of 10 and 50 eV/atom can not fabricate nanopores in some cases for silicon and diamond clusters on boron doped polycrystalline graphene nanosheets. On the other hand, silicon and diamond clusters fabricate nanopores for all locations and all tested energies on nitrogen doped polycrystalline graphene. The area sizes of nanopores fabricated by silicon and diamond clusters with diameter of 2 and 2.5 nm are close to the actual area size of the related clusters for the kinetic energy of 300 eV/atom in all locations on boron doped polycrystalline graphene. The maximum area and the average maximum area of nanopores are fabricated by the kinetic energy of 500 eV/atom inside the grain boundary at the center of the nanosheet and in the corner of nanosheet with diameters of 2 and 3 nm for silicon and diamond clusters on boron and nitrogen doped polycrystalline graphene.

The synthesis, structure and properties of N-acetylated derivatives of ethyl 3-amino-1H-pyrazole-4-carboxylate.

PubMed

Kusakiewicz-Dawid, Anna; Masiukiewicz, Elzbieta; Rzeszotarska, Barbara; Dybała, Izabela; Kozioł, Anna Eugenia; Broda, Małgorzata Anna

2007-05-01

Ethyl 3-amino-1H-pyrazole-4-carboxylate (1) was yielded through total synthesis and reacted with acetic anhydride to give the acetylated products 2-6. Compounds 1-6 were studied with HPLC, X-ray, FT-IR, (1)H-NMR, (13)C-NMR and MS. Acetylation was carried out in solvents of various polarity, namely; chloroform; dioxane; DMF; acetic anhydride, at room temperature and at boiling points; and in the presence and absence of DMAP. The acetylated products are mainly nitrogen atoms in the ring. The position of the ring proton in the solution was based on NOESY; multinuclear HMBC, HSQC spectra and calculations. For equivalent amounts (1-1.5 mol) of acetic anhydride at room temperature two products of monoacetylation are produced in the ring: 2 and 3, ca. 2 : 1 and at the same time only small amount of the third product of monoacetylated, 5 in DMF, as well the product diacetylated, 4. The greatest amount of the product 4 is produced during the reaction with chloroform. However, in this solvent and in dioxane no product 5 is produced. Compound 2 is, largely, formed in dimethylformamide, in the presence DMAP, 0.2 eq. In the presence of this catalytic base, for the first hour, there is a mixture 2 and 3 to the ratio ca. 95 : 5. With 8 eq of Ac(2)O at reflux, after another hour, the compounds 3, 4 and 6 appear about equal amounts. After a longer time, the compound, which appears most in this mixture is triacetylated derivative 6. The structural and spectroscopic characteristics of compounds 1-6 have been given and the methods for their preparation have been provided.

Conversion of Exogenous Cholesterol into Glycoalkaloids in Potato Shoots, Using Two Methods for Sterol Solubilisation

PubMed Central

Petersson, Erik V.; Nahar, Nurun; Dahlin, Paul; Broberg, Anders; Tröger, Rikard; Dutta, Paresh C.; Jonsson, Lisbeth; Sitbon, Folke

2013-01-01

Steroidal glycoalkaloids (SGA) are toxic secondary metabolites naturally occurring in the potato, as well as in certain other Solanaceous plant species, such as tomato, eggplant and pepper. To investigate the steroidal origin of SGA biosynthesis, cut potato shoots were fed cholesterol labelled with deuterium (D) in the sterol ring structure (D5- or D6-labelled), or side chain (D7-labelled), and analysed after three or five weeks. The labelled cholesterol and presence of D-labelled SGA were analysed by GC-MS and LC-MS/MS, respectively. When feeding D-labelled cholesterol solubilised in Tween-80, labelled cholesterol in free form became present in both leaves and stems, although the major part was recovered as steryl esters. Minor amounts of D-labelled SGA (α-solanine and α-chaconine) were identified in cholesterol-treated shoots, but not in blank controls, or in shoots fed D6-27-hydroxycholesterol. Solubilising the labelled cholesterol in methyl-β-cyclodextrin instead of Tween-80 increased the levels of labelled SGA up to 100-fold, and about 1 mole% of the labelled cholesterol was recovered as labelled SGA in potato leaves. Both side chain and ring structure D labels were retained in SGA, showing that the entire cholesterol molecule is converted to SGA. However, feeding side chain D7-labelled cholesterol resulted in D5-labelled SGA, indicating that two hydrogen atoms were released during formation of the SGA nitrogen-containing ring system. Feeding with D7-sitosterol did not produce any labelled SGA, indicating that cholesterol is a specific SGA precursor. In conclusion, we have demonstrated a superior performance of methyl-β-cyclodextrin for delivery of cholesterol in plant tissue feeding experiments, and given firm evidence for cholesterol as a specific sterol precursor of SGA in potato. PMID:24349406

Biotransformation and bioactivation reactions of alicyclic amines in drug molecules.

PubMed

Bolleddula, Jayaprakasam; DeMent, Kevin; Driscoll, James P; Worboys, Philip; Brassil, Patrick J; Bourdet, David L

2014-08-01

Aliphatic nitrogen heterocycles such as piperazine, piperidine, pyrrolidine, morpholine, aziridine, azetidine, and azepane are well known building blocks in drug design and important core structures in approved drug therapies. These core units have been targets for metabolic attack by P450s and other drug metabolizing enzymes such as aldehyde oxidase and monoamine oxidase (MAOs). The electron rich nitrogen and/or α-carbons are often major sites of metabolism of alicyclic amines. The most common biotransformations include N-oxidation, N-conjugation, oxidative N-dealkylation, ring oxidation, and ring opening. In some instances, the metabolic pathways generate electrophilic reactive intermediates and cause bioactivation. However, potential bioactivation related adverse events can be attenuated by structural modifications. Hence it is important to understand the biotransformation pathways to design stable drug candidates that are devoid of metabolic liabilities early in the discovery stage. The current review provides a comprehensive summary of biotransformation and bioactivation pathways of aliphatic nitrogen containing heterocycles and strategies to mitigate metabolic liabilities.

Production and characterization of a nitrogen-implanted Fe standard to calibrate PIGE measurements

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

Rodrigues, C. L.; Silva, T. F.; Added, N.

2014-11-11

Three calibration standard was produced by ion implantation of nitrogen in samples of Armco iron (99.7% iron). The samples was irradiated with nitrogen ion beams at several different energies (between 4 keV and 40 keV), and the ion doses were adjusted to obtain an uniform depth profile, using simulations with SRIM code. Two standards, one thick and other a foil (1.62mg/cm{sup 2}), was irradiated at same time with total nominal dose of 6.6×10{sup −16} atoms/cm{sup 2} distributed in a region of 100 nm in depth, with an average concentration of 9.0% nitrogen in iron. The third sample uses the samemore » profile, but with a small dose, 1.1×10{sup −16} atoms/cm{sup 2} and average concentration of 1.5% nitrogen. The characterization of the implanted samples was done using RBS and NRA techniques to quantification of nitrogen.« less

Theoretical studies of the nitrogen containing compounds adsorption behavior on Na(I)Y and rare earth exchanged RE(III)Y zeolites.

PubMed

Geng, Wei; Zhang, Haitao; Zhao, Xuefei; Zan, Wenyan; Gao, Xionghou; Yao, Xiaojun

2015-01-01

In this work, the adsorption behavior of nitrogen containing compounds including NH3, pyridine, quinoline, and carbazole on Na(I)Y and rare earth exchanged La(III)Y, Pr(III)Y, Nd(III)Y zeolites was investigated by density functional theory (DFT) calculations. The calculation results demonstrate that rare earth exchanged zeolites have stronger adsorption ability for nitrogen containing compounds than Na(I)Y. Rare earth exchanged zeolites exhibit strongest interaction with quinoline while weakest with carbazole. Nd(III)Y zeolites are found to have strongest adsorption to all the studied nitrogen containing compounds. The analysis of the electronic total charge density and electron orbital overlaps show that nitrogen containing compounds interact with zeolites by π-electrons of the compounds and the exchanged metal atom. Mulliken charge population analysis also proves that adsorption energies are strongly dependent on the charge transfer between the nitrogen containing molecules and exchanged metal atom in the zeolites.

Experimental and theoretical study on free 5-nitroquinoline, 5-nitroisoquinoline, and their zinc(II) halide complexes

NASA Astrophysics Data System (ADS)

Yurdakul, Şenay; Badoğlu, Serdar; Güleşci, Yeliz

2015-02-01

In this study where the interpretations of the experimental IR and Raman spectra recorded at room temperature for the ligands 5-nitroquinoline (5NQ) and 5-nitroisoquinoline (5NIQ) and also for their Zn(II) halide (halogen: chlorine, bromine, iodine) complexes were first reported, the assignments of the observed fundamental bands were achieved in the light of the vibrational spectral data and total energy distribution (TED) values calculated at B3LYP/6-311++G(d,p) and B3LYP/LANL2DZ levels of theory. The equilibrium geometrical parameters, Natural Bond Orbital (NBO) charges and frontier orbital (HOMO, LUMO) energies of these molecular structures were also calculated at the same level of theory. Comparisons over the corresponding experimental and theoretical data obtained for the title ligands and their complexes revealed that in complex form both ligands bond to Zn(II) ion through their ring nitrogen atoms and NO2 groups at the same time.

Synthesis of tetra- and octa-aurated heteroaryl complexes towards probing aromatic indoliums

PubMed Central

Yuan, Jun; Sun, Tingting; He, Xin; An, Ke; Zhu, Jun; Zhao, Liang

2016-01-01

Polymetalated aromatic compounds are particularly challenging synthetic goals because of the limited thermodynamic stability of polyanionic species arising from strong electrostatic repulsion between adjacent carbanionic sites. Here we describe a facile synthesis of two polyaurated complexes including a tetra-aurated indole and an octa-aurated benzodipyrrole. The imido trinuclear gold(I) moiety exhibits nucleophilicity and undergoes an intramolecular attack on a gold(I)-activated ethynyl to generate polyanionic heteroaryl species. Their computed magnetic properties reveal the aromatic character in the five-membered ring. The incorporation of the aurated substituents at the nitrogen atom can convert non-aromaticity in the parent indolium into aromaticity in the aurated one because of hyperconjugation. Thus, the concept of hyperconjugative aromaticity is extended to heterocycles with transition metal substituents. More importantly, further analysis indicates that the aurated substituents can perform better than traditional main-group substituents. This work highlights the difference in aromaticity between polymetalated aryls and their organic prototypes. PMID:27186982

Spin mixing at level anti-crossings in the rotating frame makes high-field SABRE feasible.

PubMed

Pravdivtsev, Andrey N; Yurkovskaya, Alexandra V; Vieth, Hans-Martin; Ivanov, Konstantin L

2014-12-07

A new technique is proposed to carry out Signal Amplification By Reversible Exchange (SABRE) experiments at high magnetic fields. SABRE is a method, which utilizes spin order transfer from para-hydrogen to the spins of a substrate in transient complexes using suitable catalysts. Such a transfer of spin order is efficient at low magnetic fields, notably, in the Level Anti-Crossing (LAC) regions. Here it is demonstrated that LAC conditions can also be fulfilled at high fields in the rotating reference frame under the action of an RF-field. Spin mixing at LACs allows one to polarize substrates at high fields as well; the achievable NMR enhancements are around 360 for the ortho-protons of partially deuterated pyridine used as a substrate and around 700 for H2 and substrate in the active complex with the catalyst. High-field SABRE effects have also been found for several other molecules containing a nitrogen atom in the aromatic ring.

A highly stretchable autonomous self-healing elastomer

NASA Astrophysics Data System (ADS)

Li, Cheng-Hui; Wang, Chao; Keplinger, Christoph; Zuo, Jing-Lin; Jin, Lihua; Sun, Yang; Zheng, Peng; Cao, Yi; Lissel, Franziska; Linder, Christian; You, Xiao-Zeng; Bao, Zhenan

2016-06-01

It is a challenge to synthesize materials that possess the properties of biological muscles—strong, elastic and capable of self-healing. Herein we report a network of poly(dimethylsiloxane) polymer chains crosslinked by coordination complexes that combines high stretchability, high dielectric strength, autonomous self-healing and mechanical actuation. The healing process can take place at a temperature as low as -20 °C and is not significantly affected by surface ageing and moisture. The crosslinking complexes used consist of 2,6-pyridinedicarboxamide ligands that coordinate to Fe(III) centres through three different interactions: a strong pyridyl-iron one, and two weaker carboxamido-iron ones through both the nitrogen and oxygen atoms of the carboxamide groups. As a result, the iron-ligand bonds can readily break and re-form while the iron centres still remain attached to the ligands through the stronger interaction with the pyridyl ring, which enables reversible unfolding and refolding of the chains. We hypothesize that this behaviour supports the high stretchability and self-healing capability of the material.

Investigating isoindoline, tetrahydroisoquinoline, and tetrahydrobenzazepine scaffolds for their sigma receptor binding properties.

PubMed

Linkens, Kathryn; Schmidt, Hayden R; Sahn, James J; Kruse, Andrew C; Martin, Stephen F

2018-05-10

Substituted norbenzomorphans are known to display high affinity and selectivity for the two sigma receptor (σR) subtypes. In order to study the effects of simplifying the structures of these compounds, a scaffold hopping strategy was used to design several novel sets of substituted isoindolines, tetrahydroisoquinolines and tetrahydro-2-benzazepines. The binding affinities of these new compounds for the sigma 1 (σ1R) and sigma 2 (σ2R) receptors were determined, and some analogs were identified that exhibit high affinity (K i  ≤ 25 nM) and significant selectivity (>10-fold) for σ1R or σ2R. The preferred binding modes of selected compounds for the σ1R are predicted by modeling studies, and the nature of substituents on the aromatic ring and the nitrogen atom of the bicyclic skeleton appears to affect the preferred binding orientation of σ1R-preferring ligands. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Self-assembly 2D zinc-phthalocyanine heterojunction: An ideal platform for high efficiency solar cell

NASA Astrophysics Data System (ADS)

Jiang, Xue; Jiang, Zhou; Zhao, Jijun

2017-12-01

As an alternative to silicon-based solar cells, organic photovoltaic cells emerge for their easy manufacture, low cost, and light weight but are limited by their less stability, low power conversion efficiencies, and low charge carrier mobilities. Here, we design a series of two-dimensional (2D) organic materials incorporating zinc-phthalocyanine (ZnPc) based building blocks which can inherit their excellent intrinsic properties but overcome those shortcomings. Our first-principles calculation shows that such 2D ZnPc-based materials exhibit excellent thermal stabilities, suitable bandgaps, small effective masses, and good absorption properties. The additional benzene rings and nitrogen atoms incorporated between ZnPc molecules are mainly responsible for the modifications of electronic and optical properties. Moreover, some heterojunction solar cells constructed using those 2D ZnPc monolayers as the donor and acceptor have an appropriate absorber gap and interface band alignment. Among them, a power conversion efficiency up to 14.04% is achieved, which is very promising for the next-generation organic solar cells.

2, 4, 6-Trithiol-1, 3, 5-Triazine-Modified Gold Nanoparticles and Its Potential as Formalin Detector

NASA Astrophysics Data System (ADS)

Yulizar, Y.; Ariyanta, H. A.; Rakhmania, L.; Hafizah, M. A. E.

2018-04-01

Stabilized gold nanoparticles (AuNP) have been successfully prepared by a modification of ligand 2, 4, 6-trithiol-1, 3, 5-triazine (TT). TT has three thiol groups and nitrogen atoms on the aromatic ring that can interact and stabilize AuNP. TT modified AuNP (AuNP/TT) was characterized using UV-Vis spectrophotometer, particle size analyzer (PSA) and transmission electron microscopy (TEM). The characterization showed that AuNP/TT stable at a maximum wavelength (λmaks) of 537 nm with the particle diameter of 9.41 nm. The increased acidity (pH) causes the protonated thiol groups of TT marked with a visual change of colloidal AuNP/TT from purple to blue, causing AuNP and TT bonds weakened. In this study, the AuNP/TT was reacted with formalin. This interaction shows that AuNP/TT has a potential as an efficient detector of formalin, marked by changes in the diameter of the particle, colloidal color, and maximum wavelength shift.

Spectroscopic, structural characterizations and antioxidant capacity of the chromium (III) niacinamide compound as a diabetes mellitus drug model

NASA Astrophysics Data System (ADS)

Refat, Moamen S.; El-Megharbel, Samy M.; Hussien, M. A.; Hamza, Reham Z.; Al-Omar, Mohamed A.; Naglah, Ahmed M.; Afifi, Walid M.; Kobeasy, Mohamed I.

2017-02-01

New binuclear chromium (III) niacinamide compound with chemical formula [Cr2(Nic)(Cl)6(H2O)4]·H2O was obtained upon the reaction of chromium (III) chloride with niacinamide (Nic) in methanol solvent at 60 °C. The proposed structure was discussed with the help of microanalytical analyses, conductivity, spectroscopic (FT-IR and UV-vis.), magnetic calculations, thermogravimetric analyses (TG/TGA), and morphological studies (X-ray of solid powder and scan electron microscopy. The infrared spectrum of free niacinamide in comparison with its chromium (III) compound indicated that the chelation mode occurs via both nitrogen atoms of pyridine ring and primary -NH2 group. The efficiency of chromium (III) niacinamide compound in decreasing of glucose level of blood and HbA1c in case of diabetic rats was checked. The ameliorating gluconeogenic enzymes, lipid profile and antioxidant defense capacities are considered as an indicator of the efficiency of new chromium (III) compound as antidiabetic drug model.

Use of UV Sources for Detection and Identification of Explosives

NASA Technical Reports Server (NTRS)

Hug, William; Reid, Ray; Bhartia, Rohit; Lane, Arthur

2009-01-01

Measurement of Raman and native fluorescence emission using ultraviolet (UV) sources (<400 nm) on targeted materials is suitable for both sensitive detection and accurate identification of explosive materials. When the UV emission data are analyzed using a combination of Principal Component Analysis (PCA) and cluster analysis, chemicals and biological samples can be differentiated based on the geometric arrangement of molecules, the number of repeating aromatic rings, associated functional groups (nitrogen, sulfur, hydroxyl, and methyl), microbial life cycles (spores vs. vegetative cells), and the number of conjugated bonds. Explosive materials can be separated from one another as well as from a range of possible background materials, which includes microbes, car doors, motor oil, and fingerprints on car doors, etc. Many explosives are comprised of similar atomic constituents found in potential background samples such as fingerprint oils/skin, motor oil, and soil. This technique is sensitive to chemical bonds between the elements that lead to the discriminating separability between backgrounds and explosive materials.

Crystal structure of methyl 3'-benzamido-4'-(4-meth-oxy-phen-yl)-1'-methyl-spiro-[indeno-[1,2-b]quinoxaline-11,2'-pyrrolidine]-3'-carboxyl-ate.

PubMed

Chandralekha, Kuppan; Sureshbabu, Adukamparai Rajukrishnan; Gavaskar, Deivasigamani; Lakshmi, Srinivasakannan

2016-09-01

In the title compound, C 35 H 30 N 4 O 3 , the spiro C atom connects the five-membered pyrrolidine ring and the indeno-quinoxaline ring system. The pyrrolidine ring adopts a twist conformation. An intra-molecular N-H⋯N inter-action between the amino group and the pyrazine ring is observed. In the crystal, mol-ecules are linked by a pairs of C-H⋯O hydrogen bonds, forming inversion dimers.

Heteroaromatic-based electrolytes for lithium and lithium-ion batteries

DOEpatents

Cheng, Gang; Abraham, Daniel P.

2017-04-18

The present invention provides an electrolyte for lithium and/or lithium-ion batteries comprising a lithium salt in a liquid carrier comprising heteroaromatic compound including a five-membered or six-membered heteroaromatic ring moiety selected from the group consisting of a furan, a pyrazine, a triazine, a pyrrole, and a thiophene, the heteroaromatic ring moiety bearing least one carboxylic ester or carboxylic anhydride substituent bound to at least one carbon atom of the heteroaromatic ring. Preferred heteroaromatic ring moieties include pyridine compounds, pyrazine compounds, pyrrole compounds, furan compounds, and thiophene compounds.

Stacking interactions between nitrogen-containing six-membered heterocyclic aromatic rings and substituted benzene: studies in solution and in the solid state.

PubMed

Gung, Benjamin W; Wekesa, Francis; Barnes, Charles L

2008-03-07

The stacking interactions between an aromatic ring and a pyridine or a pyrimidine ring are studied by using a series of triptycene-derived scaffolds. The indicative ratios of the syn and anti conformers were determined by variable-temperature NMR spectroscopy. The syn conformer aligns the attached aromatic ring and the heterocycle in a parallel-displaced orientation while the anti conformer sets the two rings apart from each other. Comparing to the corresponding control compounds where a benzene ring is in the position of the heterocycle, higher attractive interactions are observed as indicated by the higher syn/anti ratios. In general, the attractive interactions are much less sensitive to the substituent effects than the corresponding nonheterocycles. The greatest attractive interactions were observed between a pyrimidine ring and a N,N-dimethylaminobenzene, consistent with a predominant donor-acceptor interaction. The interactions between a pyridine ring and a substituted benzene ring show that the pyridine is comparable to that of a NO2- or a CN-substituted benzene ring except for the unpredictable substituent effects.

Nitrogen-fixing symbiosis inferred from stable isotope analysis of fossil tree rings from the Oligocene of Ethiopia

Treesearch

Erik L. Gulbranson; Bonnie F. Jacobs; William C. Hockaday; Michael C. Wiemann; Lauren A. Michel; Kaylee Richards; John W. Kappelman

2017-01-01

The acquisition of reduced nitrogen (N) is essential for plant life, and plants have developed numerous strategies and symbioses with soil microorganisms to acquire this form of N. The evolutionary history of specific symbiotic relationships of plants with soil bacteria, however, lacks evidence from the fossil record confirming these mutualistic relationships. Here we...

Role of the pyridine nitrogen in pyridoxal 5'-phosphate catalysis: activity of three classes of PLP enzymes reconstituted with deazapyridoxal 5'-phosphate.

PubMed

Griswold, Wait R; Toney, Michael D

2011-09-21

Pyridoxal 5'-phosphate (PLP; vitamin B(6))-catalyzed reactions have been well studied, both on enzymes and in solution, due to the variety of important reactions this cofactor catalyzes in nitrogen metabolism. Three functional groups are central to PLP catalysis: the C4' aldehyde, the O3' phenol, and the N1 pyridine nitrogen. In the literature, the pyridine nitrogen has traditionally been assumed to be protonated in enzyme active sites, with the protonated pyridine ring providing resonance stabilization of carbanionic intermediates. This assumption is certainly correct for some PLP enzymes, but the structures of other active sites are incompatible with protonation of N1, and, consequently, these enzymes are expected to use PLP in the N1-unprotonated form. For example, aspartate aminotransferase protonates the pyridine nitrogen for catalysis of transamination, while both alanine racemase and O-acetylserine sulfhydrylase are expected to maintain N1 in the unprotonated, formally neutral state for catalysis of racemization and β-elimination. Herein, kinetic results for these three enzymes reconstituted with 1-deazapyridoxal 5'-phosphate, an isosteric analogue of PLP lacking the pyridine nitrogen, are compared to those for the PLP enzyme forms. They demonstrate that the pyridine nitrogen is vital to the 1,3-prototropic shift central to transamination, but not to reactions catalyzed by alanine racemase or O-acetylserine sulfhydrylase. Not all PLP enzymes require the electrophilicity of a protonated pyridine ring to enable formation of carbanionic intermediates. It is proposed that modulation of cofactor electrophilicity plays a central role in controlling reaction specificity in PLP enzymes.

2-Amino-5-chloro-pyrimidin-1-ium hydrogen maleate.

PubMed

Fun, Hoong-Kun; Hemamalini, Madhukar; Rajakannan, Venkatachalam

2012-01-01

In the title salt, C(4)H(5)ClN(3) (+)·C(4)H(3)O(4) (-), the 2-amino-5-chloro-pyrimidinium cation is protonated at one of its pyrimidine N atoms. In the roughly planar (r.m.s. deviation = 0.026 Å) hydrogen malate anion, an intra-molecular O-H⋯O hydrogen bond generates an S(7) ring. In the crystal, the protonated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxyl-ate O atoms of the anion via a pair of N-H⋯O hydrogen bonds, forming an R(2) (2)(8) ring motif. The ion pairs are connected via further N-H⋯O hydrogen bonds and a short C-H⋯O inter-action, forming layers lying parallel to the bc plane.

Di­chlorido­[N-(N,N-di­methyl­carbamimido­yl)-N′,N′,4-tri­methyl­benzohydrazonamide]­platinum(II) nitro­methane hemisolvate

PubMed Central

Bolotin, Dmitrii S.; Bokach, Nadezha A.; Haukka, Matti

2014-01-01

In the title compound, [PtCl2(C13H21N5)]·0.5CH3NO2, the PtII atom is coordinated in a slightly distorted square-planar geometry by two Cl atoms and two N atoms of the bidentate ligand. The (1,3,5-tri­aza­penta­diene)PtII metalla ring is slightly bent and does not conjugate with the aromatic ring. In the crystal, N—H⋯Cl hydrogen bonds link the complex mol­ecules, forming chains along [001]. The nitromethane solvent molecule shows half-occupancy and is disordered over two sets of sites about an inversion centre. PMID:24826095

Two-dimensional network of atomtronic qubits

NASA Astrophysics Data System (ADS)

Safaei, S.; Grémaud, B.; Dumke, R.; Kwek, L.-C.; Amico, L.; Miniatura, C.

2018-04-01

Through a combination of laser beams, we engineer a two-dimensional optical lattice of Mexican hat potentials able to host atoms in its ring-shaped wells. When tunneling can be ignored (at high laser intensities), we show that a well-defined qubit can be associated with the states of the atoms trapped in each of the rings. Each of these two-level systems can be manipulated by a suitable configuration of Raman laser beams imprinting a synthetic flux onto each Mexican hat cell of the lattice. Overall, we believe that the system has the potential to form a scalable architecture for atomtronic flux qubits.

First principles calculations for interaction of tyrosine with (ZnO)3 cluster

NASA Astrophysics Data System (ADS)

Singh, Satvinder; Singh, Gurinder; Kaura, Aman; Tripathi, S. K.

2018-04-01

First Principles Calculations have been performed to study interactions of Phenol ring of Tyrosine (C6H5OH) with (ZnO)3 atomic cluster. All the calculations have been performed under the Density Functional Theory (DFT) framework. Structural and electronic properties of (ZnO)3/C6H5OH have been studied. Gaussian basis set approach has been adopted for the calculations. A ring type most stable (ZnO)3 atomic cluster has been modeled, analyzed and used for the calculations. The compatibility of the results with previous studies has been presented here.

High-resolution 17O double-rotation NMR characterization of ring and non-ring oxygen in vitreous B2O3.

PubMed

Wong, Alan; Howes, Andy P; Parkinson, Ben; Anupõld, Tiit; Samoson, Ago; Holland, Diane; Dupree, Ray

2009-08-28

The application of double rotation (DOR) NMR to crystalline materials (both inorganic and organic) has made tremendous strides in providing site-specific information about materials in recent years. However (17)O DOR has yet to demonstrate its potential in disordered materials such as glasses. In the present study, we have successfully recorded high resolution (17)O DOR spectra of vitreous B(2)O(3) (v-B(2)O(3)), a highly effective glass-forming oxide of considerable technological importance. Two distinct oxygen sites are resolved and a complete set of (17)O NMR parameters were determined from the DOR spectra. These were assigned to oxygen atoms in the planar boroxol ring [B(3)O(6)] and in the non-boroxol [BO(3)] groups which share oxygen with the ring boron atoms. This assignment was based on the similarity of all of their (17)O parameters with those found by DFT calculation for caesium enneaborate, Cs(2)O.9B(2)O(3), which has two boroxol rings in its structure. The boroxol ring oxygens have a more positive chemical shift, a larger shift anisotropy and a smaller electric field gradient than non ring oxygens (O(R): delta(iso) = 100 +/- 1 ppm, span = 180 +/- 20 ppm, skew = -0.4 +/- 0.1, P(q) = 5.0 +/- 0.2 MHz; O(NR): delta(iso) = 86 +/- 1 ppm, span = 100 +/- 20 ppm, skew = 0.1 +/- 0.1, P(q) = 5.7 +/- 0.2 MHz). The relative proportions of the two sites in v-B(2)O(3) are approximately 1 : 1, as expected if all three boron atoms in the boroxol ring are each connected to one oxygen in a linking [BO(3)] group and there are very few [BO(3)]-[BO(3)] linkages. We see no evidence for a third oxygen site such as has been reported in an earlier study of v-B(2)O(3). This work demonstrates the potential of (17)O DOR to provide site-specific information in disordered materials.

Lyman-alpha observations in the vicinity of Saturn with Copernicus

NASA Technical Reports Server (NTRS)

Barker, E.; Cazes, S.; Emerich, C.; Vidal-Madjar, A.; Owen, T.

1980-01-01

For the first time, high-resolution Ly-alpha observations of the Saturn vicinity were completed with the Princeton spectrometer on board the Copernicus satellite. They showed that near a minimum solar activity the emissions related to several sources are 250 + or - 50 rayleighs for the interplanetary medium in a near-downwind direction, less than 100 rayleighs for the rings, 200 + or - 100 rayleighs for a torus linked to the Titan orbit, and 1400 + or - 450 rayleighs for the disk of Saturn. These results induce some constraints through the corresponding theoretical evaluations: the B ring as the primary source of the atoms for the ring emissions; an efficient production mechanism for hydrogen atoms in the Titan torus; and a slightly larger eddy diffusion coefficient in the Saturn atmosphere than in the Jupiter atmosphere near solar minimum.

1-(Prop-2-yn­yl)indoline-2,3-dione

PubMed Central

Qachchachi, Fatima-Zahrae; Ouazzani Chahdi, Fouad; Misbahi, Houria; Bodensteiner, Michael; El Ammari, Lahcen

2014-01-01

The structure of the title compound, C11H7NO2, is isotypic to that of its homologue, 1-octylindoline-2,3-dione [Qachchachi et al. (2013 ▶). Acta Cryst. E69, o1801]. The indoline ring and the two carbonyl O atoms are approximately coplanar, the largest deviation from the mean plane being 0.021 (1) Å for one of the O atoms. The mean plane through the fused ring system is nearly perpendicular to the propynyl group, as indicated by the N—C—C—C torsion angle of 77.9 (1)°. In the crystal, mol­ecules are linked by C—H⋯O hydrogen bonds and π–π inter­actions between benzene rings [inter­centroid distance = 3.5630 (10) Å], forming a three-dimensional structure. PMID:24765046

Organic nitrogen chemistry during low-grade metamorphism

USGS Publications Warehouse

Boudou, J.-P.; Schimmelmann, A.; Ader, M.; Mastalerz, Maria; Sebilo, M.; Gengembre, L.

2008-01-01

Most of the organic nitrogen (Norg) on Earth is disseminated in crustal sediments and rocks in the form of fossil nitrogen-containing organic matter. The chemical speciation of fossil Norg within the overall molecular structure of organic matter changes with time and heating during burial. Progressive thermal evolution of organic matter involves phases of enhanced elimination of Norg and ultimately produces graphite containing only traces of nitrogen. Long-term chemical and thermal instability makes the chemical speciation of Norg a valuable tracer to constrain the history of sub-surface metamorphism and to shed light on the subsurface biogeochemical nitrogen cycle and its participating organic and inorganic nitrogen pools. This study documents the evolutionary path of Norg speciation, transformation and elimination before and during metamorphism and advocates the use of X-ray photoelectron spectroscopy (XPS) to monitor changes in Norg speciation as a diagnostic tool for organic metamorphism. Our multidisciplinary evidence from XPS, stable isotopes, traditional quantitative coal analyses, and other analytical approaches shows that at the metamorphic onset Norg is dominantly present as pyrrolic and pyridinic nitrogen. The relative abundance of nitrogen substituting for carbon in condensed, partially aromatic systems (where N is covalently bonded to three C atoms) increases exponentially with increasing metamorphic grade, at the expense of pyridinic and pyrrolic nitrogen. At the same time, much Norg is eliminated without significant nitrogen isotope fractionation. The apparent absence of Rayleigh-type nitrogen isotopic fractionation suggests that direct thermal loss of nitrogen from an organic matrix does not serve as a major pathway for Norg elimination. Instead, we propose that hot H, O-containing fluids or some of their components gradually penetrate into the carbonaceous matrix and eliminate Norg along a progressing reaction front, without causing nitrogen isotope fractionation in the residual Norg in the unreacted core of the carbonaceous matrix. Before the reaction front can reach the core, an increasing part of core Norg chemically stabilizes in the form of nitrogen atoms substituting for carbon in condensed, partially aromatic systems forming graphite-like structural domains with delocalized ??-electron systems (nitrogen atoms substituting for "graphitic" carbon in natural metamorphic organic matter). Thus, this nitrogen species with a conservative isotopic composition is the dominant form of residual nitrogen at higher metamorphic grade. ?? 2007 Elsevier Ltd. All rights reserved.

Etude des trois molecules H 2P-NH 2, ClHP-NH 2, H 2P-NHCl au moyen d'une methode de pseudopotentiels

NASA Astrophysics Data System (ADS)

Barthelat, M.; Mathis, R.; Mathis, F.

The three molecules H 2P-NH 2, ClHP-NH 2 and H 2P-NHCl have been studied by a pseudo-potential method, with a minimal basis of quality mono-zeta, with 3 d functions on the phosphorus atom. The geometry of each molecule was optimized and the phosphorus-nitrogen rotation barrier calculated. The results of the calculations confirm that the polarity of the phosphorus-nitrogen bond is P +-N -. Three weak interactions appear: a partial coordinative bond between the nitrogen doublet and a 3 d orbital of the phosphorus atom, hyperconjugation between the nitrogen doublet and the P-H bonds, and participation of the 3 d orbital of phosphorus in the P-N bond.

Polymer useful for an ion exchange membrane

DOEpatents

Liang, Siwei; Lynd, Nathaniel A.

2017-03-14

The present invention provides for a polymer formed by reacting a first reactant polymer, or a mixture of first reactant polymers comprising different chemical structures, comprising a substituent comprising two or more nitrogen atoms (or a functional group/sidechain comprising a two or more nitrogen atoms) with a second reactant polymer, or a mixture of second reactant polymers comprising different chemical structures, comprising a halogen substituent (or a functional group/sidechain comprising a halogen).

Ultraviolet electroluminescence from nitrogen-doped ZnO-based heterojuntion light-emitting diodes prepared by remote plasma in situ atomic layer-doping technique.

PubMed

Chien, Jui-Fen; Liao, Hua-Yang; Yu, Sheng-Fu; Lin, Ray-Ming; Shiojiri, Makoto; Shyue, Jing-Jong; Chen, Miin-Jang

2013-01-23

Remote plasma in situ atomic layer doping technique was applied to prepare an n-type nitrogen-doped ZnO (n-ZnO:N) layer upon p-type magnesium-doped GaN (p-GaN:Mg) to fabricate the n-ZnO:N/p-GaN:Mg heterojuntion light-emitting diodes. The room-temperature electroluminescence exhibits a dominant ultraviolet peak at λ ≈ 370 nm from ZnO band-edge emission and suppressed luminescence from GaN, as a result of the decrease in electron concentration in ZnO and reduced electron injection from n-ZnO:N to p-GaN:Mg because of the nitrogen incorporation. The result indicates that the in situ atomic layer doping technique is an effective approach to tailoring the electrical properties of materials in device applications.

The impact of gas-surface reactions on mass spectrometric measurements of atomic nitrogen. [determination of atmosphere ion sources

NASA Technical Reports Server (NTRS)

Engebretson, M. J.; Mauersberger, K.

1979-01-01

The paper presents a simplified model of the ion source chemistry, explains several details of the data reduction method used in obtaining atomic-nitrogen (N) densities from OSS data, and discusses implications of gas-surface reactions for the design of future satellite-borne mass spectrometers. Because of various surface reactions, N appears in three different forms in the ion source, as N, NO, and NO2. Considering the rather small spin modulation of NO and NO2 in the semi-open ionization chamber used in the OSS instrument, it is not surprising that these reaction products have not been previously identified in closed source instruments as a measure of the presence of atomic nitrogen. Warmup and/or outgassing of the ion source are shown to drastically reduce the NO2 concentration, thereby making possible reliable measurement of ambient N densities.

2-tert-Butyl-5-(2-pyridyl)-2H-tetrazole as a chelating ligand in the direct synthesis of novel Cu(II) and heterobimetallic Cu(II)/Mn(II) complexes.

PubMed

Mosalkova, Anastasiya P; Voitekhovich, Sergei V; Lyakhov, Alexander S; Ivashkevich, Ludmila S; Lach, Jochen; Kersting, Berthold; Gaponik, Pavel N; Ivashkevich, Oleg A

2013-02-28

For the first time, a representative of the 2,5-disubstituted tetrazoles, namely, 2-tert-butyl-5-(2-pyridyl)-2H-tetrazole (L), has been found to participate in oxidative dissolution of copper powder in homometalic systems Cu0–L–NH4X–DMSO (X = Cl, SCN, ClO4) and heterobimetallic ones Cu0–Mn(OAc)2–L–NH4OAc–Solv (Solv = DMSO, DMF), providing the formation of molecular homometallic complexes [CuL2Cl2] (1), [CuL2(SCN)2] (2), and [CuL2(H2O)](ClO4)2 (3), heterobimetallic complex [Cu2MnL2(OAc)6] (4) from DMF solution and its mixture with complex [Cu2MnL2(OAc)6]·2DMSO (5) from DMSO solution. Free ligand L and complexes 1–4 were characterized by elemental analysis, IR spectroscopy, thermal and X-ray single crystal analyses, whereas complex 5 was characterized by X-ray analysis only. Compounds 1–3 are mononuclear complexes, with chelating coordination mode of L via the tetrazole ring N4 and pyridine ring N7 atoms. Heterobimetallic complexes 4 and 5 possess trinuclear structures, with a linear Cu–Mn–Cu arrangement of the metal atoms, linked by the acetate anions; each copper(II) atom is decorated by a chelating unit of L via the tetrazole ring N1 and pyridine ring N7 atoms in complex 4, and via the N4, N7 atoms in complex 5. Temperature-dependent magnetic susceptibility measurements of complex 4 revealed a weak antiferromagnetic coupling between the paramagnetic copper(II) and manganese(II) ions (J = −2.5 cm(−1), g(Cu) = 2.25 and g(Mn) = 2.01), with magnetic exchange through the acetato bridges.

Sc-Decorated Porous Graphene for High-Capacity Hydrogen Storage: First-Principles Calculations.

PubMed

Chen, Yuhong; Wang, Jing; Yuan, Lihua; Zhang, Meiling; Zhang, Cairong

2017-08-02

The generalized gradient approximation (GGA) function based on density functional theory is adopted to investigate the optimized geometrical structure, electron structure and hydrogen storage performance of Sc modified porous graphene (PG). It is found that the carbon ring center is the most stable adsorbed position for a single Sc atom on PG, and the maximum number of adsorbed H₂ molecules is four with the average adsorption energy of -0.429 eV/H₂. By adding a second Sc atom on the other side of the system, the hydrogen storage capacity of the system can be improved effectively. Two Sc atoms located on opposite sides of the PG carbon ring center hole is the most suitable hydrogen storage structure, and the hydrogen storage capacity reach a maximum 9.09 wt % at the average adsorption energy of -0.296 eV/H₂. The adsorption of H₂ molecules in the PG system is mainly attributed to orbital hybridization among H, Sc, and C atoms, and Coulomb attraction between negatively charged H₂ molecules and positively charged Sc atoms.

Sc-Decorated Porous Graphene for High-Capacity Hydrogen Storage: First-Principles Calculations

PubMed Central

Chen, Yuhong; Wang, Jing; Yuan, Lihua; Zhang, Meiling

2017-01-01

The generalized gradient approximation (GGA) function based on density functional theory is adopted to investigate the optimized geometrical structure, electron structure and hydrogen storage performance of Sc modified porous graphene (PG). It is found that the carbon ring center is the most stable adsorbed position for a single Sc atom on PG, and the maximum number of adsorbed H2 molecules is four with the average adsorption energy of −0.429 eV/H2. By adding a second Sc atom on the other side of the system, the hydrogen storage capacity of the system can be improved effectively. Two Sc atoms located on opposite sides of the PG carbon ring center hole is the most suitable hydrogen storage structure, and the hydrogen storage capacity reach a maximum 9.09 wt % at the average adsorption energy of −0.296 eV/H2. The adsorption of H2 molecules in the PG system is mainly attributed to orbital hybridization among H, Sc, and C atoms, and Coulomb attraction between negatively charged H2 molecules and positively charged Sc atoms. PMID:28767084

Atomic-level molybdenum oxide nanorings with full-spectrum absorption and photoresponsive properties.

PubMed

Yang, Yong; Yang, Yang; Chen, Shuangming; Lu, Qichen; Song, Li; Wei, Yen; Wang, Xun

2017-11-16

Superthin nanostructures, particularly with atomic-level thicknesses, typically display unique optical properties because of their exceptional light-matter interactions. Here, we report a facile strategy for the synthesis of sulfur-doped molybdenum oxide nanorings with an atomic-level size (thickness of 0.5 nm) and a tunable ring-in-ring architecture. These atomic-level nanorings displayed strong photo-absorption in both the visible and infrared-light ranges and acted as a photothermal agent. Under irradiation with an 808 nm laser with an intensity of 1 W/cm 2 , a composite of the nanorings embedded in polydimethylsiloxane showed an ultrafast photothermal effect, delivering a local temperature of up to 400 °C within 20 s, which to the best of our knowledge is the highest temperature by light irradiation reported to date. Meanwhile, the resulting nanorings were also employed as a photoinitiator to remotely induce a visible-light shape memory response, self-healing, reshaping performance and reversible actuation of dynamic three-dimensional structures. This study demonstrates an advancement towards controlling atomic-level-sized nanostructures and achieving greatly enhanced optical performances for optoelectronics.

Characteristics of microbial community functional structure of a biological coking wastewater treatment system.

PubMed

Joshi, Dev Raj; Zhang, Yu; Zhang, Hong; Gao, Yingxin; Yang, Min

2018-01-01

Nitrogenous heterocyclic compounds are key pollutants in coking wastewater; however, the functional potential of microbial communities for biodegradation of such contaminants during biological treatment is still elusive. Herein, a high throughput functional gene array (GeoChip 5.0) in combination with Illumina HiSeq2500 sequencing was used to compare and characterize the microbial community functional structure in a long run (500days) bench scale bioreactor treating coking wastewater, with a control system treating synthetic wastewater. Despite the inhibitory toxic pollutants, GeoChip 5.0 detected almost all key functional gene (average 61,940 genes) categories in the coking wastewater sludge. With higher abundance, aromatic ring cleavage dioxygenase genes including multi ring1,2diox; one ring2,3diox; catechol represented significant functional potential for degradation of aromatic pollutants which was further confirmed by Illumina HiSeq2500 analysis results. Response ratio analysis revealed that three nitrogenous compound degrading genes- nbzA (nitro-aromatics), tdnB (aniline), and scnABC (thiocyanate) were unique for coking wastewater treatment, which might be strong cause to increase ammonia level during the aerobic process. Additionally, HiSeq2500 elucidated carbozole and isoquinoline degradation genes in the system. These findings expanded our understanding on functional potential of microbial communities to remove organic nitrogenous pollutants; hence it will be useful in optimization strategies for biological treatment of coking wastewater. Copyright © 2017. Published by Elsevier B.V.

Energetic Nitrogen Ions within the Inner Magnetosphere of Saturn

NASA Astrophysics Data System (ADS)

Sittler, E. C.; Johnson, R. E.; Richardson, J. D.; Jurac, S.; Moore, M.; Cooper, J. F.; Mauk, B. H.; Smith, H. T.; Michael, M.; Paranicus, C.; Armstrong, T. P.; Tsurutani, B.; Connerney, J. E. P.

2003-05-01

Titan's interaction with Saturn's magnetosphere will result in the energetic ejection of atomic nitrogen atoms into Saturn's magnetosphere due to dissociation of N2 by electrons, ions, and UV photons. The ejection of N atoms into Saturn's magnetosphere will form a nitrogen torus around Saturn with mean density of about 4 atoms/cm3 with source strength of 4.5x1025 atoms/sec. These nitrogen atoms are ionized by photoionization, electron impact ionization and charge exchange reactions producing an N+ torus of 1-4 keV suprathermal ions centered on Titan's orbital position. We will show Voyager plasma observations that demonstrate presence of a suprathermal ion component within Saturn's outer magnetosphere. The Voyager LECP data also reported the presence of inward diffusing energetic ions from the outer magnetosphere of Saturn, which could have an N+ contribution. If so, when one conserves the first and second adiabatic invariant the N+ ions will have energies in excess of 100 keV at Dione's L shell and greater than 400 keV at Enceladus' L shell. Energetic charged particle radial diffusion coefficients are also used to constrain the model results. But, one must also consider the solar wind as another important source of keV ions, in the form of protons and alpha particles, for Saturn's outer magnetosphere. Initial estimates indicate that a solar wind source could dominate in the outer magnetosphere, but various required parameters for this estimate are highly uncertain and will have to await Cassini results for confirmation. We show that satellite sweeping and charged particle precipitation within the middle and outer magnetosphere will tend to enrich N+ ions relative to protons within Saturn's inner magnetosphere as they diffuse radially inward for radial diffusion coefficients that do not violate observations. Charge exchange reactions within the inner magnetosphere can be an important loss mechanism for O+ ions, but to a lesser degree for N+ ions. Initial LECP results using composition data at energies greater than 200 keV/nucl., showed that heavy ions within Saturn's inner magnetosphere dominated over protons, but that contrary to original suggestions that these ions were O+ , we now argue that they are instead N+ ions. With energetic N+ ions bombarding the icy satellite surfaces chemical reactions can occur at the end of the ion tracks and produce nitrogen oxides or other nitrogen containing molecules such that the radiology within the icy surfaces is driven by the impacting energetic nitrogen ions. These can accumulate over the lifetime of the Saturn system.

Mathematical analysis of compressive/tensile molecular and nuclear structures

NASA Astrophysics Data System (ADS)

Wang, Dayu

Mathematical analysis in chemistry is a fascinating and critical tool to explain experimental observations. In this dissertation, mathematical methods to present chemical bonding and other structures for many-particle systems are discussed at different levels (molecular, atomic, and nuclear). First, the tetrahedral geometry of single, double, or triple carbon-carbon bonds gives an unsatisfying demonstration of bond lengths, compared to experimental trends. To correct this, Platonic solids and Archimedean solids were evaluated as atoms in covalent carbon or nitrogen bond systems in order to find the best solids for geometric fitting. Pentagonal solids, e.g. the dodecahedron and icosidodecahedron, give the best fit with experimental bond lengths; an ideal pyramidal solid which models covalent bonds was also generated. Second, the macroscopic compression/tension architectural approach was applied to forces at the molecular level, considering atomic interactions as compressive (repulsive) and tensile (attractive) forces. Two particle interactions were considered, followed by a model of the dihydrogen molecule (H2; two protons and two electrons). Dihydrogen was evaluated as two different types of compression/tension structures: a coaxial spring model and a ring model. Using similar methods, covalent diatomic molecules (made up of C, N, O, or F) were evaluated. Finally, the compression/tension model was extended to the nuclear level, based on the observation that nuclei with certain numbers of protons/neutrons (magic numbers) have extra stability compared to other nucleon ratios. A hollow spherical model was developed that combines elements of the classic nuclear shell model and liquid drop model. Nuclear structure and the trend of the "island of stability" for the current and extended periodic table were studied.

Structures and anti-inflammatory properties of 4-halogenated -mofebutazones

NASA Astrophysics Data System (ADS)

Reichelt, Hendrik; Paradies, Henrich H.

2018-02-01

The crystal structures of the 4-halogenated (hal: F, Cl, Br)-4-butyl-1-phenyl-1,3-pyrolidine-dione (mofebutazone) are determined, and compared with their solution structures. The racemic 4-halogenated mofebutazone approximants crystallize in a monoclinic space group with four molecules in the unit cell. The 4-hal-mofebutazone molecules reveal strong hydrogen bonding between the hydrogen atom located at the N-2 nitrogen atom and a carbonyl oxygen atom of an adjacent 4-hal-mofebutazone molecule. The hydrogen bond angle for 4-Br-mifebutazone N (2)sbnd H (1)⋯O (1) is 173(3) °, so that the hydrogen bond is essentially linear indicating an infinite chain hydrogen bond network. The 3d and 2d structures are stabilized by π-π and σ-π interactions, short intermolecular distances, and apolar forces between adjacently stacked phenyl rings. Small-angle-X-ray scattering (SAXS) experiments and osmometric measurements reveal the presence of dimers for the 4-hal-mofebutazone molecules. Molecular simulations indicate similar solution structure factors for the 4-hal-mofebutazones solutions, S(Q), and in the solid state. There is a strong indication that the [1,1,0], [1,0,0], and [1,0,0] periodicities of the 4-Brsbnd , 4-Clsbnd and 4-F-mofebutazone in the crystalline solid state were also present in the solution phase. The biochemical and cellular activities of the different 4-hal-mofebutazones were monitored by the magnitude of their inhibition of the PGE2 biosynthesis through the cyclo-oxygenase (COX-1) in macrophages, and on the inhibition of LTD4 (5-lipoxygenase) in polymorphonuclear leukocytes.

Hologram quantitative structure-activity relationship and comparative molecular field analysis studies within a series of tricyclic phthalimide HIV-1 integrase inhibitors.

PubMed

Magalhães, Uiaran de Oliveira; Souza, Alessandra Mendonça Teles de; Albuquerque, Magaly Girão; Brito, Monique Araújo de; Bello, Murilo Lamim; Cabral, Lucio Mendes; Rodrigues, Carlos Rangel

2013-01-01

Acquired immunodeficiency syndrome is a public health problem worldwide caused by the Human immunodeficiency virus (HIV). Treatment with antiretroviral drugs is the best option for viral suppression, reducing morbidity and mortality. However, viral resistance in HIV-1 therapy has been reported. HIV-1 integrase (IN) is an essential enzyme for effective viral replication and an attractive target for the development of new inhibitors. In the study reported here, two- and three-dimensional quantitative structure-activity relationship (2D/3D-QSAR) studies, applying hologram quantitative structure-activity relationship (HQSAR) and comparative molecular field analysis (CoMFA) methods, respectively, were performed on a series of tricyclic phthalimide HIV-1 IN inhibitors. The best HQSAR model (q (2) = 0.802, r (2) = 0.972) was obtained using atoms, bonds, and connectivity as the fragment distinction, a fragment size of 2-5 atoms, hologram length of 61 bins, and six components. The best CoMFA model (q (2) = 0.748, r (2) = 0.974) was obtained with alignment of all atoms of the tricyclic phthalimide moiety (alignment II). The HQSAR contribution map identified that the carbonyl-hydroxy-aromatic nitrogen motif made a positive contribution to the activity of the compounds. Furthermore, CoMFA contour maps suggested that bulky groups in meta and para positions in the phenyl ring would increase the biological activity of this class. The conclusions of this work may lead to a better understanding of HIV-1 IN inhibition and contribute to the design of new and more potent derivatives.

Hologram quantitative structure–activity relationship and comparative molecular field analysis studies within a series of tricyclic phthalimide HIV-1 integrase inhibitors

PubMed Central

de Oliveira Magalhães, Uiaran; de Souza, Alessandra Mendonça Teles; Albuquerque, Magaly Girão; de Brito, Monique Araújo; Bello, Murilo Lamim; Cabral, Lucio Mendes; Rodrigues, Carlos Rangel

2013-01-01

Acquired immunodeficiency syndrome is a public health problem worldwide caused by the Human immunodeficiency virus (HIV). Treatment with antiretroviral drugs is the best option for viral suppression, reducing morbidity and mortality. However, viral resistance in HIV-1 therapy has been reported. HIV-1 integrase (IN) is an essential enzyme for effective viral replication and an attractive target for the development of new inhibitors. In the study reported here, two- and three-dimensional quantitative structure–activity relationship (2D/3D-QSAR) studies, applying hologram quantitative structure–activity relationship (HQSAR) and comparative molecular field analysis (CoMFA) methods, respectively, were performed on a series of tricyclic phthalimide HIV-1 IN inhibitors. The best HQSAR model (q2 = 0.802, r2 = 0.972) was obtained using atoms, bonds, and connectivity as the fragment distinction, a fragment size of 2–5 atoms, hologram length of 61 bins, and six components. The best CoMFA model (q2 = 0.748, r2 = 0.974) was obtained with alignment of all atoms of the tricyclic phthalimide moiety (alignment II). The HQSAR contribution map identified that the carbonyl-hydroxy-aromatic nitrogen motif made a positive contribution to the activity of the compounds. Furthermore, CoMFA contour maps suggested that bulky groups in meta and para positions in the phenyl ring would increase the biological activity of this class. The conclusions of this work may lead to a better understanding of HIV-1 IN inhibition and contribute to the design of new and more potent derivatives. PMID:24039405

Fine tuning of graphene properties by modification with aryl halogens

NASA Astrophysics Data System (ADS)

Bouša, D.; Pumera, M.; Sedmidubský, D.; Šturala, J.; Luxa, J.; Mazánek, V.; Sofer, Z.

2016-01-01

Graphene and its derivatives belong to one of the most intensively studied materials. The radical reaction using halogen derivatives of arene-diazonium salts can be used for effective control of graphene's electronic properties. In our work we investigated the influence of halogen atoms (fluorine, chlorine, bromine and iodine) as well as their position on the benzene ring towards the electronic and electrochemical properties of modified graphenes. The electronegativity as well as the position of the halogen atoms on the benzene ring has crucial influence on graphene's properties due to the inductive and mesomeric effects. The results of resistivity measurement are in good agreement with the theoretical calculations of electron density within chemically modified graphene sheets. Such simple chemical modifications of graphene can be used for controllable and scalable synthesis of graphene with tunable transport properties.Graphene and its derivatives belong to one of the most intensively studied materials. The radical reaction using halogen derivatives of arene-diazonium salts can be used for effective control of graphene's electronic properties. In our work we investigated the influence of halogen atoms (fluorine, chlorine, bromine and iodine) as well as their position on the benzene ring towards the electronic and electrochemical properties of modified graphenes. The electronegativity as well as the position of the halogen atoms on the benzene ring has crucial influence on graphene's properties due to the inductive and mesomeric effects. The results of resistivity measurement are in good agreement with the theoretical calculations of electron density within chemically modified graphene sheets. Such simple chemical modifications of graphene can be used for controllable and scalable synthesis of graphene with tunable transport properties. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06295k

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

PubMed

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

2018-05-10

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

Structure of 6-diazo-5-oxo-norleucine-bound human gamma-glutamyl transpeptidase 1, a novel mechanism of inactivation

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

Terzyan, Simon S.; Cook, Paul F.; Heroux, Annie

Intense efforts are underway to identify inhibitors of the enzyme gamma–glutamyl transpeptidase 1 (GGT1) which cleaves extracellular gamma–glutamyl compounds and contributes to the pathology of asthma, reperfusion injury and cancer. The glutamate analog, 6–diazo–5–oxo–norleucine (DON), inhibits GGT1. DON also inhibits many essential glutamine metabolizing enzymes rendering it too toxic for use in the clinic as a GGT1 inhibitor. We investigated the molecular mechanism of human GGT1 (hGGT1) inhibition by DON to determine possible strategies for increasing its specificity for hGGT1. DON is an irreversible inhibitor of hGGT1. The second order rate constant of inactivation was 0.052 m M –1 minmore » –1 and the K i was 2.7 ± 0.7 m M. The crystal structure of DON–inactivated hGGT1 contained a molecule of DON without the diazo–nitrogen atoms in the active site. The overall structure of the hGGT1–DON complex resembled the structure of the apo–enzyme; however, shifts were detected in the loop forming the oxyanion hole and elements of the main chain that form the entrance to the active site. The structure of hGGT1–DON complex revealed two covalent bonds between the enzyme and inhibitor which were part of a six membered ring. The ring included the OG atom of Thr381, the reactive nucleophile of hGGT1 and the α–amine of Thr381. As a result, the structure of DON–bound hGGT1 has led to the discovery of a new mechanism of inactivation by DON that differs from its inactivation of other glutamine metabolizing enzymes, and insight into the activation of the catalytic nucleophile that initiates the hGGT1 reaction.« less

Structure of 6-diazo-5-oxo-norleucine-bound human gamma-glutamyl transpeptidase 1, a novel mechanism of inactivation.

PubMed

Terzyan, Simon S; Cook, Paul F; Heroux, Annie; Hanigan, Marie H

2017-06-01

Intense efforts are underway to identify inhibitors of the enzyme gamma-glutamyl transpeptidase 1 (GGT1) which cleaves extracellular gamma-glutamyl compounds and contributes to the pathology of asthma, reperfusion injury and cancer. The glutamate analog, 6-diazo-5-oxo-norleucine (DON), inhibits GGT1. DON also inhibits many essential glutamine metabolizing enzymes rendering it too toxic for use in the clinic as a GGT1 inhibitor. We investigated the molecular mechanism of human GGT1 (hGGT1) inhibition by DON to determine possible strategies for increasing its specificity for hGGT1. DON is an irreversible inhibitor of hGGT1. The second order rate constant of inactivation was 0.052 mM -1 min -1 and the K i was 2.7 ± 0.7 mM. The crystal structure of DON-inactivated hGGT1 contained a molecule of DON without the diazo-nitrogen atoms in the active site. The overall structure of the hGGT1-DON complex resembled the structure of the apo-enzyme; however, shifts were detected in the loop forming the oxyanion hole and elements of the main chain that form the entrance to the active site. The structure of hGGT1-DON complex revealed two covalent bonds between the enzyme and inhibitor which were part of a six membered ring. The ring included the OG atom of Thr381, the reactive nucleophile of hGGT1 and the α-amine of Thr381. The structure of DON-bound hGGT1 has led to the discovery of a new mechanism of inactivation by DON that differs from its inactivation of other glutamine metabolizing enzymes, and insight into the activation of the catalytic nucleophile that initiates the hGGT1 reaction. © 2017 The Protein Society.

Structure of 6-diazo-5-oxo-norleucine-bound human gamma-glutamyl transpeptidase 1, a novel mechanism of inactivation

DOE PAGES

Terzyan, Simon S.; Cook, Paul F.; Heroux, Annie; ...

2017-04-05

Intense efforts are underway to identify inhibitors of the enzyme gamma–glutamyl transpeptidase 1 (GGT1) which cleaves extracellular gamma–glutamyl compounds and contributes to the pathology of asthma, reperfusion injury and cancer. The glutamate analog, 6–diazo–5–oxo–norleucine (DON), inhibits GGT1. DON also inhibits many essential glutamine metabolizing enzymes rendering it too toxic for use in the clinic as a GGT1 inhibitor. We investigated the molecular mechanism of human GGT1 (hGGT1) inhibition by DON to determine possible strategies for increasing its specificity for hGGT1. DON is an irreversible inhibitor of hGGT1. The second order rate constant of inactivation was 0.052 m M –1 minmore » –1 and the K i was 2.7 ± 0.7 m M. The crystal structure of DON–inactivated hGGT1 contained a molecule of DON without the diazo–nitrogen atoms in the active site. The overall structure of the hGGT1–DON complex resembled the structure of the apo–enzyme; however, shifts were detected in the loop forming the oxyanion hole and elements of the main chain that form the entrance to the active site. The structure of hGGT1–DON complex revealed two covalent bonds between the enzyme and inhibitor which were part of a six membered ring. The ring included the OG atom of Thr381, the reactive nucleophile of hGGT1 and the α–amine of Thr381. As a result, the structure of DON–bound hGGT1 has led to the discovery of a new mechanism of inactivation by DON that differs from its inactivation of other glutamine metabolizing enzymes, and insight into the activation of the catalytic nucleophile that initiates the hGGT1 reaction.« less

Direct asymmetric N-specific reaction of nitrosobenzene with aldehydes catalyzed by a chiral primary amine-based organocatalyst.

PubMed

Qin, Long; Li, Lei; Yi, Lei; Da, Chao-Shan; Zhou, Yi-Feng

2011-08-01

Nitroso compounds have two reactive nitrogen and oxygen atoms. It is interesting and important to perform a nitrogen or oxygen selective reaction with interesting substrates. These atom specific reactions are crucial to specifically synthesis of specific compounds. An enantioselective N-specific reaction of nitrosobenzene with unmodified aldehydes was successfully achieved catalyzed first by a variety of primary amine-based organocatalysts with higher yield and enantioselectivity. The bulkier substituted groups of the organocatalyst and two hydrogen bonds from the organocatalyst and the oxygen atom of nitrosobenzene make the reaction preferentially N-specific and predominantly afford R products. Copyright © 2011 Wiley-Liss, Inc.

Synthesis and structural characterization of two half-sandwich nickel(II) complexes with the scorpionate ligands

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

Wang, G.-F., E-mail: wgf1979@126.com, E-mail: s-shuwen@163.com; Zhang, X., E-mail: zhangx@hit.edu.cn; Sun, S.-W.

The synthesis and characterization of two new halfsandwich mononuclear nickel(II) complexes with the scorpionate ligands, [k{sup 3}-N, N',N''-Tp{sup t-Bu}, {sup Me}NiI] (1) and [k{sup 3}-N,N',N''-Tp{sup t-Bu}, {sup Me}NiNO{sub 3}] (2), are reported. These complexes have been fully characterized by elemental analyses and infrared spectra. Their molecular structures were determined by single crystal X-ray diffraction. The nickel(II) ion of complex 1 is in a four-coordinate environment, in which the donor atoms are provided by three nitrogen atoms of a hydrotris(pyrazolyl) borate ligand and one iodide atom, while that of complex 2 is in a five-coordinate environment with three nitrogen atoms frommore » a hydrotris(pyrazolyl)borate ligand and two oxygen atoms from a nitrate ion.« less

Ab Initio Path Integral Molecular Dynamics Study of the Nuclear Quantum Effect on Out-of-Plane Ring Deformation of Hydrogen Maleate Anion.

PubMed

Kawashima, Yukio; Tachikawa, Masanori

2014-01-14

Ab initio path integral molecular dynamics (PIMD) simulation was performed to understand the nuclear quantum effect on the out-of-plane ring deformation of hydrogen maleate anion and investigate the existence of a stable structure with ring deformation, which was suggested in experimental observation (Fillaux et al., Chem. Phys. 1999, 120, 387-403). The isotope effect and the temperature effect are studied as well. We first investigated the nuclear quantum effect on the proton transfer. In static calculation and classical ab initio molecular dynamics simulations, the proton in the hydrogen bond is localized to either oxygen atom. On the other hand, the proton is located at the center of two oxygen atoms in quantum ab initio PIMD simulations. The nuclear quantum effect washes out the barrier of proton transfer. We next examined the nuclear quantum effect on the motion of hydrogen maleate anion. Principal component analysis revealed that the out-of-plane ring bending modes have dominant contribution to the entire molecular motion. In quantum ab initio PIMD simulations, structures with ring deformation were the global minimum for the deuterated isotope at 300 K. We analyzed the out-of-plane ring bending mode further and found that there are three minima along a ring distortion mode. We successfully found a stable structure with ring deformation of hydrogen maleate for the first time, to our knowledge, using theoretical calculation. The structures with ring deformation found in quantum simulation of the deuterated isotope allowed the proton transfer to occur more frequently than the planar structure. Static ab initio electronic structure calculation found that the structures with ring deformation have very small proton transfer barrier compared to the planar structure. We suggest that the "proton transfer driven" mechanism is the origin of stabilization for the structure with out-of-plane ring deformation.

A new storage-ring light source

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

Chao, Alex

2015-06-01

A recently proposed technique in storage ring accelerators is applied to provide potential high-power sources of photon radiation. The technique is based on the steady-state microbunching (SSMB) mechanism. As examples of this application, one may consider a high-power DUV photon source for research in atomic and molecular physics or a high-power EUV radiation source for industrial lithography. A less challenging proof-of-principle test to produce IR radiation using an existing storage ring is also considered.

The Discovery of Crown Ethers

NASA Astrophysics Data System (ADS)

Pedersen, Charles J.

1988-07-01

The discovery of the crown ethers stemmed from efforts to control the catalytic activity of vanadium and copper by complexation with multidentate ligands. The first crown ether, 2,3,11,12-dibenzo-1,4,7,10,13,16-hexaoxacyclo-octadeca-2,11-diene, was obtained in 0.4% yield during an attempt to prepare a phenolic ligand from catechol and bis(2-chloroethyl)ether. This compound, which complexed with the sodium cation, was the first compound known to display such activity and became known as dibenzo-18-crown-6, an 18-atom heterocycle containing 6 oxygen atoms. Some 60 related compounds were made involving heterocyclic rings containing 12 to 60 atoms including 4 and 10 oxygen atoms. There are optimum polyether ring sizes for the different alkali metal cations: 15 to 18 for sodium, 18 for potassium, and 18 to 21 for cesium. Complexes having polyether to cation ratios of 1:1, 3:2, and 2:1 were prepared. Solubilization of inorganic salts in aprotic solvents, especially by saturated crown ethers, was demonstrated.

Macroevolutionary trends of atomic composition and related functional group proportion in eukaryotic and prokaryotic proteins.

PubMed

Zhang, Yu-Juan; Yang, Chun-Lin; Hao, You-Jin; Li, Ying; Chen, Bin; Wen, Jian-Fan

2014-01-25

To fully explore the trends of atomic composition during the macroevolution from prokaryote to eukaryote, five atoms (oxygen, sulfur, nitrogen, carbon, hydrogen) and related functional groups in prokaryotic and eukaryotic proteins were surveyed and compared. Genome-wide analysis showed that eukaryotic proteins have more oxygen, sulfur and nitrogen atoms than prokaryotes do. Clusters of Orthologous Groups (COG) analysis revealed that oxygen, sulfur, carbon and hydrogen frequencies are higher in eukaryotic proteins than in their prokaryotic orthologs. Furthermore, functional group analysis demonstrated that eukaryotic proteins tend to have higher proportions of sulfhydryl, hydroxyl and acylamino, but lower of sulfide and carboxyl. Taken together, an apparent trend of increase was observed for oxygen and sulfur atoms in the macroevolution; the variation of oxygen and sulfur compositions and their related functional groups in macroevolution made eukaryotic proteins carry more useful functional groups. These results will be helpful for better understanding the functional significances of atomic composition evolution. Copyright © 2013 Elsevier B.V. All rights reserved.

Curare-Like Activity of Mono-Quaternary Salts Containing Adamantyl Residue at the Nitrogen Atom

DTIC Science & Technology

As shown in previous works, mono-quaternary salts of alkamine esters of benzoic and cinnamic acids types and exhibit a pronounced curare like action...A series of methiodides of alkamine esters of benzoic and cinnamic acids were synthesized, containing at the quaternary nitrogen atom a 1-adamantyl...adamantyl causes a change of the substance’s mechanism of action, this applying both to the benzoic acid derivatives and to the cinnamic acid derivatives

Two molecular wheels 12-MC-6 complexes: Synthesis, structure and magnetic property of [Co(μ{sub 2}-SEt){sub 2}]{sub 6} and [Fe(μ{sub 2}-SEt){sub 2}]{sub 6}

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

Wang, Jing; Jian, Fangfang, E-mail: ffj2003@163169.net; Huang, Baoxin

2013-08-15

The syntheses and structures of two ethyl mercaptan molecular wheels complexes, [M(μ{sub 2}-SCH{sub 2}CH{sub 3}){sub 2}]{sub 6} (M=Fe, Co), have been reported. Each metal atom is surrounded by four S atoms of the μ{sub 2}-SCH{sub 2}CH{sub 3} ligands in a distorted square plane fashion. The edge-sharing S{sub 4} square planes connect with each other to form a ring. Six metal atoms are located at the vertices of an almost hexagon, with M···M separations in the range of 2.903(1)∼2.936(2) Å for Fe and 2.889(2)∼2.962(2) Å for Co. The diameter of the ring, defined as the average distance between two opposing metalmore » atoms, is 5.850(1) Å for Fe and 5.780(1) Å for Co, respectively. The magnetic property behaves of cobalt(II) cluster complex is studied. Highlights: • Two new ethyl mercaptan cyclic hexanuclear complexes were reported. • The crystal structures shown center formation of M{sub 6}S{sub 12} molecular wheels. • The Co{sub 6} ring cluster complex represents as weak ferromagnet.« less

Characterization of non-classical Csbnd Br⋯π interactions in (E)-1,3-dibromo-5-(2-(ferrocenyl)vinyl)benzene and related derivatives of ferrocene

NASA Astrophysics Data System (ADS)

Shukla, Rahul; Panini, Piyush; McAdam, C. John; Robinson, Brian H.; Simpson, Jim; Tagg, Tei; Chopra, Deepak

2017-03-01

Amongst the halogens, the involvement of bromine atoms in various types of intermolecular interactions is comparatively the least studied. In this manuscript, we report the formation of Csbnd Br⋯π interactions, with the π-rings being the cyclopentadienyl (Cp) rings of a ferrocene molecule in a newly synthesized compound (E)-1,3-dibromo-5-(2-(ferrocenyl)vinyl)benzene. We have also performed a detailed quantitative analysis on Csbnd Br⋯π interactions observed in the synthesized molecule and in several related molecules found in the Cambridge Structure Database (CSD) showing the presence of these interactions. A topological analysis based upon QTAIM theory and electrostatic potential ESP mapped on the Hirshfeld surface of these molecules confirm that these interactions are better described as "halogen bonds" wherein the electropositive region (σ-hole) on the Br-atom interacts with the electronegative region over the Cp-ring of the ferrocene. Further, the electronegative region on the bromine atom (perpendicular to the Csbnd Br bond) was observed to be involved in the formation of highly directional Csbnd H⋯Br interactions with the ∠Csbnd Br⋯H close to 90°. Thus the bromine atom is acting as both a "halogen bond donor" and "hydrogen bond acceptor" in the crystal packing with the two interactions being mutually orthogonal.

N-H.N hydrogen bonding in 4,6-diphenyl-2-pyrimidinylamine isolated from the plant Justicia secunda (Acanthaceae).

PubMed

Gallagher, John F; Goswami, Shyamaprosad; Chatterjee, Baidyanath; Jana, Subrata; Dutta, Kalyani

2004-04-01

The title compound, C(16)H(13)N(3), isolated from Justicia secunda (Acanthaceae), comprises two molecules (which differ slightly in conformation) in the asymmetric unit of space group P-1. Intermolecular N(amino)-H.N(pyrm) interactions (N(pyrm) is a pyrimidine ring N atom) involve only one of the two donor amino H atoms and pyrimidine N atoms per molecule, forming dimeric units via R(2)(2)(8) rings, with N.N distances of 3.058 (2) and 3.106 (3) A, and N-H.N angles of 172.7 (18) and 175.8 (17) degrees. The dimers are linked by C-H.pi(arene) contacts, with an H.centroid distance of 2.77 A and a C-H.centroid angle of 141 degrees.

Study of nitrogen flowing afterglow with mercury vapor injection

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

Mazánková, V., E-mail: mazankova@fch.vutbr.cz; Krčma, F.; Trunec, D.

2014-10-21

The reaction kinetics in nitrogen flowing afterglow with mercury vapor addition was studied by optical emission spectroscopy. The DC flowing post-discharge in pure nitrogen was created in a quartz tube at the total gas pressure of 1000 Pa and discharge power of 130 W. The mercury vapors were added into the afterglow at the distance of 30 cm behind the active discharge. The optical emission spectra were measured along the flow tube. Three nitrogen spectral systems – the first positive, the second positive, and the first negative, and after the mercury vapor addition also the mercury resonance line at 254more » nm in the spectrum of the second order were identified. The measurement of the spatial dependence of mercury line intensity showed very slow decay of its intensity and the decay rate did not depend on the mercury concentration. In order to explain this behavior, a kinetic model for the reaction in afterglow was developed. This model showed that the state Hg(6 {sup 3}P{sub 1}), which is the upper state of mercury UV resonance line at 254 nm, is produced by the excitation transfer from nitrogen N{sub 2}(A{sup 3}Σ{sup +}{sub u}) metastables to mercury atoms. However, the N{sub 2}(A{sup 3}Σ{sup +}{sub u}) metastables are also produced by the reactions following the N atom recombination, and this limits the decay of N{sub 2}(A{sup 3}Σ{sup +}{sub u}) metastable concentration and results in very slow decay of mercury resonance line intensity. It was found that N atoms are the most important particles in this late nitrogen afterglow, their volume recombination starts a chain of reactions which produce excited states of molecular nitrogen. In order to explain the decrease of N atom concentration, it was also necessary to include the surface recombination of N atoms to the model. The surface recombination was considered as a first order reaction and wall recombination probability γ = (1.35 ± 0.04) × 10{sup −6} was determined from the experimental data. Also sensitivity analysis was applied for the analysis of kinetic model in order to reveal the main control parameters in the model.« less

Mg2+ ions: do they bind to nucleobase nitrogens?

PubMed Central

Leonarski, Filip; D'Ascenzo, Luigi; Auffinger, Pascal

2017-01-01

Given the many roles proposed for Mg2+ in nucleic acids, it is essential to accurately determine their binding modes. Here, we surveyed the PDB to classify Mg2+ inner-sphere binding patterns to nucleobase imine N1/N3/N7 atoms. Among those, purine N7 atoms are considered to be the best nucleobase binding sites for divalent metals. Further, Mg2+ coordination to N7 has been implied in several ribozyme catalytic mechanisms. We report that Mg2+ assigned near imine nitrogens derive mostly from poor interpretations of electron density patterns and are most often misidentified Na+, K+, NH4+ ions, water molecules or spurious density peaks. Consequently, apart from few documented exceptions, Mg2+ ions do not bind to N7 atoms. Without much of a surprise, Mn2+, Zn2+ and Cd2+, which have a higher affinity for nitrogens, may contact N7 atoms when present in crystallization buffers. In this respect, we describe for the first time a potential Zn2+ ribosomal binding site involving two purine N7 atoms. Further, we provide a set of guidelines to help in the assignment of Mg2+ in crystallographic, cryo-EM, NMR and model building practices and discuss implications of our findings related to ion substitution experiments. PMID:27923930

Nitrogen vacancy, self-interstitial diffusion, and Frenkel-pair formation/dissociation in B 1 TiN studied by ab initio and classical molecular dynamics with optimized potentials

NASA Astrophysics Data System (ADS)

Sangiovanni, D. G.; Alling, B.; Steneteg, P.; Hultman, L.; Abrikosov, I. A.

2015-02-01

We use ab initio and classical molecular dynamics (AIMD and CMD) based on the modified embedded-atom method (MEAM) potential to simulate diffusion of N vacancy and N self-interstitial point defects in B 1 TiN. TiN MEAM parameters are optimized to obtain CMD nitrogen point-defect jump rates in agreement with AIMD predictions, as well as an excellent description of Ti Nx(˜0.7

Crystal structure of di-bromo-meth-oxy-seselin (DBMS), a photobiologically active pyran-ocoumarin.

PubMed

Bauri, A K; Foro, Sabine; Rahman, A F M M

2017-05-01

The title compound, C 15 H 14 Br 2 O 4 [systematic name: rac -(9 S ,10 R )-3,9-dibromo-10-methoxy-8,8-dimethyl-9,10-dihydropyrano[2,3- h ]chromen-2(8 H )-one], is a pyran-ocoumarin derivative formed by the bromination of seselin, which is a naturally occurring angular pyran-ocoumarin isolated from the Indian herb Trachyspermum stictocarpum . In the mol-ecule, the benzo-pyran ring system is essentially planar, with a maximum deviation of 0.044 (2) Å for the O atom. The di-hydro-pyran ring is in a half-chair conformation and the four essentially planar atoms of this ring form a dihedral angle of 4.6 (2)° with the benzo-pyran ring system. In the crystal, mol-ecules are linked by weak C-H⋯O hydrogen bonds, forming chains propagating along [010]. In addition, π-π stacking inter-actions, with centroid-centroid distances of 3.902 (2) and 3.908 (2) Å, link the hydrogen-bonded chains into layers parallel to (001).

The surface of 1-euro coins studied by X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Gou, F.; Gleeson, M. A.; Villette, J.; Kleyn, S. E. F.; Kleyn, A. W.

2004-03-01

The two alloy surfaces (pill and ring) that are present on 1-euro coins have been studied by X-ray photoelectron spectroscopy (XPS). Comparison is made between coins from general circulation and coin surfaces that have been subjected to a variety of cleaning and oxidation treatments. The concentrations and possible oxidation states of the metals (nickel, copper and zinc) at the surface were derived from analysis of the 2p 3/2 core levels. The surface atomic ratios measured for the pill and the ring parts of the euro coins were compared to the official bulk ratios. This study shows a clear nickel enrichment of both pill and ring surfaces. Nickel at surface seems to be present mainly in hydroxide form although the chloride form cannot be excluded. A small concentration of zinc was present on the surface of the pill, even though it is not present in the bulk alloy. Evidence of both nickel and zinc surface enrichment is observed for the ring. No surface enrichment is observed for the atomically clean or oxidized alloy surfaces over a 60-h time scale.

Influence of ring size on the cognition-enhancing activity of DM235 and MN19, two potent nootropic drugs.

PubMed

Guandalini, L; Martini, E; Di Cesare Mannelli, L; Dei, S; Manetti, D; Scapecchi, S; Teodori, E; Ghelardini, C; Romanelli, M N

2012-03-01

A series of analogs of DM235 and MN19, characterized by rings with different size, have been prepared and evaluated for their nootropic activity in the mouse passive-avoidance test. It was found that the optimal ring size for the analogs of DM235, showing endocyclic both amidic groups, is 6 or 7 atoms. For the compounds structurally related to MN19, carrying an exocyclic amide group, the piperidine ring is the moiety which gives the most interesting compounds. Copyright © 2012 Elsevier Ltd. All rights reserved.

(2-{[2-(1H-Benzimidazol-2-yl-κN 3)phen­yl]imino­methyl-κN}-5-methyl­phenolato-κO)chloridozinc(II)

PubMed Central

Eltayeb, Naser Eltaher; Teoh, Siang Guan; Chantrapromma, Suchada; Fun, Hoong-Kun

2011-01-01

In the title mononuclear complex, [Zn(C21H16N3O)Cl], the ZnII ion is coordinated in a distorted tetra­hedral geometry by two benzimidazole N atoms and one phenolate O atom from the tridentate Schiff base ligand and a chloride ligand. The benzimidazole ring system forms dihedral angles of 26.68 (9) and 56.16 (9)° with the adjacent benzene ring and the methyl­phenolate group benzene ring, respectively. In the crystal, mol­ecules are linked by N—H⋯Cl hydrogen bonds into chains along [100]. Furthermore, weak C—H⋯O and C—H⋯π inter­actions, in addition to π–π inter­actions with centroid–centroid distances in the range 3.5826 (13)–3.9681 (13) Å, are also observed. PMID:22065469

Kinetic Simulation and Energetic Neutral Atom Imaging of the Magnetosphere

NASA Technical Reports Server (NTRS)

Fok, Mei-Ching H.

2011-01-01

Advanced simulation tools and measurement techniques have been developed to study the dynamic magnetosphere and its response to drivers in the solar wind. The Comprehensive Ring Current Model (CRCM) is a kinetic code that solves the 3D distribution in space, energy and pitch-angle information of energetic ions and electrons. Energetic Neutral Atom (ENA) imagers have been carried in past and current satellite missions. Global morphology of energetic ions were revealed by the observed ENA images. We have combined simulation and ENA analysis techniques to study the development of ring current ions during magnetic storms and substorms. We identify the timing and location of particle injection and loss. We examine the evolution of ion energy and pitch-angle distribution during different phases of a storm. In this talk we will discuss the findings from our ring current studies and how our simulation and ENA analysis tools can be applied to the upcoming TRIO-CINAMA mission.

Crystal structure of 5''-(4-chloro-benzyl-idene)-4'-(4-chloro-phen-yl)-1'-methyltri-spiro[acenapthylene-1,2'-pyrrolidine-3',1''-cyclo-hexane-3'',2'''-[1,3]dioxane]-2(1H),6''-dione.

PubMed

Chandralekha, Kuppan; Gavaskar, Deivasigamani; Sureshbabu, Adukamparai Rajukrishnan; Lakshmi, Srinivasakannan

2015-11-01

In the title compound, C36H29Cl2NO4, two spiro links connect the methyl-substituted pyrrolidine ring to the ace-naphthyl-ene and cyclo-hexa-none rings. The cyclo-hexa-none ring is further connected to the dioxalane ring by a third spiro junction. The five-membered ring of the ace-naphthylen-1-one ring system adopts a flattened envelope conformation, with the ketonic C atom as the flap, whereas the dioxalane and pyrrolidine rings each have a twist conformation. The cyclo-hexenone ring assumes a boat conformation. An intra-molecular C-H⋯O hydrogen-bond inter-action is present. In the crystal, mol-ecules are linked by non-classical C-H⋯O hydrogen bonds, forming chains extending parallel to the a axis.

Ocean plankton. Environmental characteristics of Agulhas rings affect interocean plankton transport.

PubMed

Villar, Emilie; Farrant, Gregory K; Follows, Michael; Garczarek, Laurence; Speich, Sabrina; Audic, Stéphane; Bittner, Lucie; Blanke, Bruno; Brum, Jennifer R; Brunet, Christophe; Casotti, Raffaella; Chase, Alison; Dolan, John R; d'Ortenzio, Fabrizio; Gattuso, Jean-Pierre; Grima, Nicolas; Guidi, Lionel; Hill, Christopher N; Jahn, Oliver; Jamet, Jean-Louis; Le Goff, Hervé; Lepoivre, Cyrille; Malviya, Shruti; Pelletier, Eric; Romagnan, Jean-Baptiste; Roux, Simon; Santini, Sébastien; Scalco, Eleonora; Schwenck, Sarah M; Tanaka, Atsuko; Testor, Pierre; Vannier, Thomas; Vincent, Flora; Zingone, Adriana; Dimier, Céline; Picheral, Marc; Searson, Sarah; Kandels-Lewis, Stefanie; Acinas, Silvia G; Bork, Peer; Boss, Emmanuel; de Vargas, Colomban; Gorsky, Gabriel; Ogata, Hiroyuki; Pesant, Stéphane; Sullivan, Matthew B; Sunagawa, Shinichi; Wincker, Patrick; Karsenti, Eric; Bowler, Chris; Not, Fabrice; Hingamp, Pascal; Iudicone, Daniele

2015-05-22

Agulhas rings provide the principal route for ocean waters to circulate from the Indo-Pacific to the Atlantic basin. Their influence on global ocean circulation is well known, but their role in plankton transport is largely unexplored. We show that, although the coarse taxonomic structure of plankton communities is continuous across the Agulhas choke point, South Atlantic plankton diversity is altered compared with Indian Ocean source populations. Modeling and in situ sampling of a young Agulhas ring indicate that strong vertical mixing drives complex nitrogen cycling, shaping community metabolism and biogeochemical signatures as the ring and associated plankton transit westward. The peculiar local environment inside Agulhas rings may provide a selective mechanism contributing to the limited dispersal of Indian Ocean plankton populations into the Atlantic. Copyright © 2015, American Association for the Advancement of Science.

Photo-excitation of electrons in cytochrome c oxidase as a theory of the mechanism of the increase of ATP production in mitochondria by laser therapy

NASA Astrophysics Data System (ADS)

Zielke, Andrzej

2014-02-01

The hypothesis explains the molecular basis for restoring mitochondrial function by laser therapy. It also explains how laser therapy reverses both excessive oxidation (lack of NADH/FADH2) and excessive reduction (lack of O2) states of cytochrome c oxidase complex. It is proposed that photons interact with heme molecules of cytochrome c oxidase. A molecule of heme contains a porphyrin ring and an atom of iron in the center. The iron atom (Fe) can switch oxidation states back and forth between ferrous (Fe2+) and ferric (Fe3+) by accepting or releasing an electron. The porphyrin ring is a complex aromatic molecule that has 26 pi electrons which are "delocalized", spinning in the carbon rings creating a resonating electromagnetic cloud. Photons with similar wavelengths are absorbed by the cloud increasing its energy. The energy is then passed on to the centrally located atom of iron existing in a reduced state (Fe2+). The electrons on the orbits of the iron atom accept this electromagnetic energy, and change orbitals to a higher energetic level. If the energy is sufficient, electrons leave the atom entirely. If this occurs, Fe2+ become oxidized to Fe3+ releasing electrons, thus restoring electron flow and the production of ATP. At the same time, electrons freed from complex IV may have sufficient energy to be picked by NAD+/FADH and re-enter the chain at the complex I or II amplifying the flow of electrons.

Hydrogen atom transfer reactions in thiophenol: photogeneration of two new thione isomers.

PubMed

Reva, Igor; Nowak, Maciej J; Lapinski, Leszek; Fausto, Rui

2015-02-21

Photoisomerization reactions of monomeric thiophenol have been investigated for the compound isolated in low-temperature argon matrices. The initial thiophenol population consists exclusively of the thermodynamically most stable thiol form. Phototransformations were induced by irradiation of the matrices with narrowband tunable UV light. Irradiation at λ > 290 nm did not induce any changes in isolated thiophenol molecules. Upon irradiation at 290-285 nm, the initial thiol form of thiophenol converted into its thione isomer, cyclohexa-2,4-diene-1-thione. This conversion occurs by transfer of an H atom from the SH group to a carbon atom at the ortho position of the ring. Subsequent irradiation at longer wavelengths (300-427 nm) demonstrated that this UV-induced hydrogen-atom transfer is photoreversible. Moreover, upon irradiation at 400-425 nm, the cyclohexa-2,4-diene-1-thione product converts, by transfer of a hydrogen atom from the ortho to para position, into another thione isomer, cyclohexa-2,5-diene-1-thione. The latter thione isomer is also photoreactive and is consumed if irradiated at λ < 332 nm. The obtained results clearly show that H-atom-transfer isomerization reactions dominate the unimolecular photochemistry of thiophenol confined in a solid argon matrix. A set of low-intensity infrared bands, observed in the spectra of UV irradiated thiophenol, indicates the presence of a phenylthiyl radical with an H- atom detached from the SH group. Alongside the H-atom-transfer and H-atom-detachment processes, the ring-opening photoreaction occurred in cyclohexa-2,4-diene-1-thione by the cleavage of the C-C bond at the alpha position with respect to the thiocarbonyl C[double bond, length as m-dash]S group. The resulting open-ring conjugated thioketene adopts several isomeric forms, differing by orientations around single and double bonds. The species photogenerated upon UV irradiation of thiophenol were identified by comparison of their experimental infrared spectra with the spectra theoretically calculated for the candidate structures at the B3LYP/aug-cc-pVTZ level.

Palladium complexes with simple iminopyridines as catalysts for polyketone synthesis.

PubMed

Rosar, V; Dedeic, D; Nobile, T; Fini, F; Balducci, G; Alessio, E; Carfagna, C; Milani, B

2016-10-07

Four iminopyridines (N-N') differing in the nature of the substituents on the iminic carbon and on the ortho positions of the aryl ring (H or CH3) on the iminic nitrogen were used for the synthesis of neutral and monocationic palladium(ii) complexes of general formulae [Pd(CH3)Cl(N-N')] and [Pd(CH3)(NCCH3)(N-N')][PF6]. The detailed NMR characterization in solution highlighted that: (i) for both series of complexes, the Pd-CH3 signal is progressively shifted to a lower frequency on increasing the number of methyl groups on the ligand skeleton; (ii) for the neutral derivatives, the chemical shift of the (15)N NMR signals, determined through {(1)H,(15)N}-HMBC spectra, is significantly affected by the coordination to palladium; (iii) the coordination induced shift (CIS) of the nitrogen atom trans to the CH3 ligand is smaller than the other. The structure in the solid state for the neutral derivatives with all the four ligands was solved, pointing out that: (iv) the Pd-C bond distance increases with the basicity of the nitrogen-donor ligand; (v) the Pd-N bond distance correlates well with the CIS value. The combining of the solution and solid state structural features allows stating that: (vi) the Pd-CH3 singlet is a good probe for the electron donor capability of the ligand; (vii) the CIS value might be used as a probe for the strength of the Pd-N bond. All monocationic complexes generated active catalysts for the CO/vinyl arene copolymerization, leading to prevailingly syndiotactic polyketones. The catalyst performances, both in terms of catalyst productivity and polymer molecular weight, correlate well with the precatalyst structural features.

Structure and reactivity of the distonic and aromatic radical cations of tryptophan.

PubMed

Piatkivskyi, Andrii; Osburn, Sandra; Jaderberg, Kendall; Grzetic, Josipa; Steill, Jeffrey D; Oomens, Jos; Zhao, Junfang; Lau, Justin Kai-Chi; Verkerk, Udo H; Hopkinson, Alan C; Siu, K W Michael; Ryzhov, Victor

2013-04-01

In this work, we regiospecifically generate and compare the gas-phase properties of two isomeric forms of tryptophan radical cations-a distonic indolyl N-radical (H3N(+) - TrpN(•)) and a canonical aromatic π (Trp(•+)) radical cation. The distonic radical cation was generated by nitrosylating the indole nitrogen of tryptophan in solution followed by collision-induced dissociation (CID) of the resulting protonated N-nitroso tryptophan. The π-radical cation was produced via CID of the ternary [Cu(II)(terpy)(Trp)](•2+) complex. CID spectra of the two isomeric species were found to be very different, suggesting no interconversion between the isomers. In gas-phase ion-molecule reactions, the distonic radical cation was unreactive towards n-propylsulfide, whereas the π radical cation reacted by hydrogen atom abstraction. DFT calculations revealed that the distonic indolyl radical cation is about 82 kJ/mol higher in energy than the π radical cation of tryptophan. The low reactivity of the distonic nitrogen radical cation was explained by spin delocalization of the radical over the aromatic ring and the remote, localized charge (at the amino nitrogen). The lack of interconversion between the isomers under both trapping and CID conditions was explained by the high rearrangement barrier of ca.137 kJ/mol. Finally, the two isomers were characterized by infrared multiple-photon dissociation (IRMPD) spectroscopy in the ~1000-1800 cm(-1) region. It was found that some of the main experimental IR features overlap between the two species, making their distinction by IRMPD spectroscopy in this region problematic. In addition, DFT theoretical calculations showed that the IR spectra are strongly conformation-dependent.

A large atomic chlorine source inferred from mid-continental reactive nitrogen chemistry.

PubMed

Thornton, Joel A; Kercher, James P; Riedel, Theran P; Wagner, Nicholas L; Cozic, Julie; Holloway, John S; Dubé, William P; Wolfe, Glenn M; Quinn, Patricia K; Middlebrook, Ann M; Alexander, Becky; Brown, Steven S

2010-03-11

Halogen atoms and oxides are highly reactive and can profoundly affect atmospheric composition. Chlorine atoms can decrease the lifetimes of gaseous elemental mercury and hydrocarbons such as the greenhouse gas methane. Chlorine atoms also influence cycles that catalytically destroy or produce tropospheric ozone, a greenhouse gas potentially toxic to plant and animal life. Conversion of inorganic chloride into gaseous chlorine atom precursors within the troposphere is generally considered a coastal or marine air phenomenon. Here we report mid-continental observations of the chlorine atom precursor nitryl chloride at a distance of 1,400 km from the nearest coastline. We observe persistent and significant nitryl chloride production relative to the consumption of its nitrogen oxide precursors. Comparison of these findings to model predictions based on aerosol and precipitation composition data from long-term monitoring networks suggests nitryl chloride production in the contiguous USA alone is at a level similar to previous global estimates for coastal and marine regions. We also suggest that a significant fraction of tropospheric chlorine atoms may arise directly from anthropogenic pollutants.

1-Do-decyl-indoline-2,3-dione.

PubMed

Qachchachi, Fatima-Zahrae; Ouazzani Chahdi, Fouad; Misbahi, Houria; Bodensteiner, Michael; El Ammari, Lahcen

2014-02-01

The structure of the title compound, C20H29NO2, is isotypic to that of its homologue 1-octylindoline-2,3-dione. The indoline ring and the two carbonyl-group O atoms are approximately coplanar, the largest deviation from the mean plane being 0.0760 (10) Å. The mean plane through the fused-ring system is nearly perpendicular to the mean plane passing through the 1-dodecyl chain [dihedral angle = 77.69 (5)°]. All C atoms of the dodecyl group are in an anti-periplanar arrangement. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds, forming a three-dimensional network.

CIT-7, a crystalline, molecular sieve with pores bounded by 8 and 10-membered rings† †Electronic supplementary information (ESI) available: Details of the synthesis and characterization of all materials as well as details on the synchrotron and RED data collection and structure determination, including the cif file. See DOI: 10.1039/c4sc03935a Click here for additional data file.

PubMed Central

Schmidt, Joel E.; Xie, Dan; Rea, Thomas

2015-01-01

A new crystalline molecular sieve, denoted CIT-7, is synthesized using an imidazolium-based diquaternary organic structure directing agent (OSDA). The framework structure is determined from a combination of rotation electron diffraction and synchrotron X-ray powder diffraction data. The structure has 10 crystallographically unique tetrahedral atoms (T-atoms) in the unit cell, and can be described as an ordered arrangement of the [425462] mtw building unit and a previously unreported [4452] building unit. The framework contains a 2-dimensional pore system that is bounded by 10 T-atom rings (10-ring, 5.1 Å × 6.2 Å opening) that are connected with oval 8-rings (2.9 Å × 5.5 Å opening) through medium-sized cavities (∼7.9 Å) at the channel intersections. CIT-7 can be synthesized over a broad range of compositions including pure-silica and heteroatom, e.g., aluminosilicate and titanosilicate, containing variants. PMID:29163872

Configuring pnicogen rings in skutterudites for low phonon conductivity

NASA Astrophysics Data System (ADS)

Uher, Ctirad

2013-03-01

During the past dozen or so years, skutterudites have attracted much interest as prospective thermoelectric materials for power-generation applications in the temperature range 500K - 850K. Primary interest was focused on filled forms of skutterudites where loosely-bonded filler species resonantly scatter normal phonon modes of the structure thus reducing the lattice thermal conductivity. Using this approach with multiple fillers and incorporating various forms of nanoinclusions, impressive figures of merit ZT = 1.5-1.7 have been reported with n-type filled skutterudites. Since the dominant heat-carrying modes in skutterudites are associated with vibrations of the pnicogen rings, disruptions of the ring structure by substitutional alloying should be a similarly effective approach of lowering the lattice thermal conductivity. In this talk I discuss our recent work exploring alloying configurations of pnicogen rings that yield particularly low values of the thermal conductivity. We found that compensated double-substitution (replacing two Sb atoms with one atom each from the column IV and column VI elements) is a very effective approach. Our ab initio calculations, in combination with a cluster expansion, have allowed us to identify stable alloy configurations on the Sb rings. Subsequent molecular and lattice dynamics simulations on low energy configurations established the range of atomic displacement parameters and values of the thermal conductivity. Theoretical results turned out to be in good agreement with our experimental thermal conductivity values. Combining both approaches of compensated double-substitution and filling of structural cages should be an effective way of further improving the thermoelectric figure of merit of skutterudites. Work supported by the Center for Solar and Thermal Energy Conversion, and Enegy Frontier Research Center funded by the Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0000957

Toward a detailed description of the pathways of allosteric communication in the GroEL chaperonin through atomistic simulation.

PubMed

Piggot, Thomas J; Sessions, Richard B; Burston, Steven G

2012-02-28

GroEL, along with its coprotein GroES, is essential for ensuring the correct folding of unfolded or newly synthesized proteins in bacteria. GroEL is a complex, allosteric molecule, composed of two heptameric rings stacked back to back, that undergoes large structural changes during its reaction cycle. These structural changes are driven by the cooperative binding and subsequent hydrolysis of ATP, by GroEL. Despite numerous previous studies, the precise mechanisms of allosteric communication and the associated structural changes remain elusive. In this paper, we describe a series of all-atom, unbiased, molecular dynamics simulations over relatively long (50-100 ns) time scales of a single, isolated GroEL subunit and also a heptameric GroEL ring, in the presence and absence of ATP. Combined with results from a distance restraint-biased simulation of the single ring, the atomistic details of the earliest stages of ATP-driven structural changes within this complex molecule are illuminated. Our results are in broad agreement with previous modeling studies of isolated subunits and with a coarse-grained, forcing simulation of the single ring. These are the first reported all-atom simulations of the GroEL single-ring complex and provide a unique insight into the role of charged residues K80, K277, R284, R285, and E388 at the subunit interface in transmission of the allosteric signal. These simulations also demonstrate the feasibility of performing all-atom simulations of very large systems on sufficiently long time scales on typical high performance computing facilities to show the origins of the earliest events in biologically relevant processes.

Synthetic Heme/Copper Assemblies: Toward an Understanding of Cytochrome c Oxidase Interactions with Dioxygen and Nitrogen Oxides

PubMed Central

Hematian, Shabnam; Garcia-Bosch, Isaac; Karlin, Kenneth D.

2016-01-01

Conspectus Our long-time niche in synthetic biological inorganic chemistry has been to design ligands and generate coordination complexes of copper and/or iron ions, those reacting with dioxygen (O2) and/or nitrogen oxides (e.g., nitric oxide (NO(g)) and nitrite (NO2−)). As inspiration for this work, we turn to mitochondrial cytochrome c oxidase which is responsible for dioxygen consumption and is also the predominant target for NO(g) and nitrite within mitochondria. In this Account, we highlight recent advances in studying synthetic heme/Cu complexes in two respects. First, there is the design, synthesis and characterization of new O2-adducts whose further study will add insights into O2-reductive cleavage chemistry. Second, we describe how related heme/Cu constructs reduce nitrite ion to NO(g) or the reverse, oxidize NO(g) to nitrite. The reactions of nitrogen oxides occur as part of CcO’s function, which is intimately tied to cellular O2-balance. We had first discovered that reduced heme/Cu compounds react with O2 giving μ-oxo heme-FeIII-O-CuII(L) products; their properties are discussed. The O-atom is derived from dioxygen and interrogations of these systems led to the construction and characterization of three distinctive classes of heme-peroxo-complexes, two high-spin and one low-spin species. Recent investigations include a new approach to the synthesis of low-spin heme-peroxo-Cu complexes, employing a “naked” synthon, where the copper ligand denticity and geometric types can be varied. The result is a collection of such complexes; spectroscopic and structural features (by DFT calculations) are described. Some of these compounds are reactive toward reductants/protons effecting subsequent O-O cleavage. This points to how subtle improvements in ligand environment lead to a desired local structure and resulting optimized reactivity, as known to occur at enzyme active-sites. The other sector of research is focused on heme/Cu assemblies mediating the redox interplay between nitrite and NO(g). In the nitrite reductase chemistry, the cupric center serves as a Lewis acid while the heme is the redox active center providing the electron. The orientation of nitrite in approaching the ferrous heme center and N-atom binding are important. Also, detailed spectroscopic and kinetic studies of the NO(g) oxidase chemistry, in excellent agreement with theoretical calculations, reveal the intermediates and key mechanistic steps. Thus, we suggest that both chemical and biochemical heme/Cu mediated nitrite reductase and NO(g) oxidase chemistry require N-atom binding to a ferrous heme along with cupric ion O-atom coordination, proceeding via a three-membered O-Fe-N chelate ring transition state. These important mechanistic features of heme/Cu systems interconverting NO(g) and nitrite are discussed for the first time. PMID:26244814

Inhibitors of human immunodeficiency virus type 1 (HIV-1) attachment. 5. An evolution from indole to azaindoles leading to the discovery of 1-(4-benzoylpiperazin-1-yl)-2-(4,7-dimethoxy-1H-pyrrolo[2,3-c]pyridin-3-yl)ethane-1,2-dione (BMS-488043), a drug candidate that demonstrates antiviral activity in HIV-1-infected subjects.

PubMed

Wang, Tao; Yin, Zhiwei; Zhang, Zhongxing; Bender, John A; Yang, Zhong; Johnson, Graham; Yang, Zheng; Zadjura, Lisa M; D'Arienzo, Celia J; DiGiugno Parker, Dawn; Gesenberg, Christophe; Yamanaka, Gregory A; Gong, Yi-Fei; Ho, Hsu-Tso; Fang, Hua; Zhou, Nannan; McAuliffe, Brian V; Eggers, Betsy J; Fan, Li; Nowicka-Sans, Beata; Dicker, Ira B; Gao, Qi; Colonno, Richard J; Lin, Pin-Fang; Meanwell, Nicholas A; Kadow, John F

2009-12-10

Azaindole derivatives derived from the screening lead 1-(4-benzoylpiperazin-1-yl)-2-(1H-indol-3-yl)ethane-1,2-dione (1) were prepared and characterized to assess their potential as inhibitors of HIV-1 attachment. Systematic replacement of each of the unfused carbon atoms in the phenyl ring of the indole moiety by a nitrogen atom provided four different azaindole derivatives that displayed a clear SAR for antiviral activity and all of which displayed marked improvements in pharmaceutical properties. Optimization of these azaindole leads resulted in the identification of two compounds that were advanced to clinical studies: (R)-1-(4-benzoyl-2-methylpiperazin-1-yl)-2-(4-methoxy-1H-pyrrolo[2,3-b]pyridin-3-yl)ethane-1,2-dione (BMS-377806, 3) and 1-(4-benzoylpiperazin-1-yl)-2-(4,7-dimethoxy-1H-pyrrolo[2,3-c]pyridin-3-yl)ethane-1,2-dione (BMS-488043, 4). In a preliminary clinical study, 4 administered as monotherapy for 8 days, reduced viremia in HIV-1-infected subjects, providing proof of concept for this mechanistic class.

An experimental and theoretical study of a hydrogen-bonded complex: O-phenylenediamine with 2,6-pyridinedicarboxylic acid

NASA Astrophysics Data System (ADS)

Ghasemi, Khaled; Rezvani, Ali Reza; Habibi-Khorassani, Sayyed Mostafa; Shahraki, Mehdi; Shokrollahi, Ardeshir; Moghimi, Abolghasem; Tamandani, Halimeh Kord; Gavahi, Sara

2015-11-01

The hydrogen-bonded complex, [(OPDH)+(dipicH)-.H2O], between o-phenylenediamine (OPD) and 2,6-pyridinedicarboxylic acid (dipicH2) has been characterized in water by the 1H, 13C NMR and IR spectroscopies. The crystal structure showed that the edge to face C-H⋯π and C-O⋯π stacking interactions between the dipicH2 and OPD rings play an extra significant role in the formation of the hydrogen-bonded complex and supported the H-bonding interactions. The proton transfer also investigated theoretically in gas phase and thermodynamic parameters such as ΔH‡, ΔG‡, ΔS‡ were calculated for this process. Moreover, intramolecular hydrogen-bonding interaction has been recognized by calculating the electron density ρ(r) and Laplacian ∇2ρ(r) at the bond critical point (BCP) using Atoms-In-Molecule (AIM) method and also the interaction between electron acceptor (σ*) of OH with the lone pair of the nitrogen atom as an electron donor using Natural Bond Orbital (NBO) analysis. In addition, the protonation constants of dipicH2 and OPD and the equilibrium constants for the dipic-OPD (1:1) proton transfer system were obtained by the potentiometric pH titration method using the Hyperquad 2008 program. The stoichiometry of the proton transfer species in the solution confirmed the solid state result.

Molecular structure and interactions in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

PubMed

Dhumal, Nilesh R; Noack, Kristina; Kiefer, Johannes; Kim, Hyung J

2014-04-03

Electronic structure theory (density functional and Møller-Plesset perturbation theory) and vibrational spectroscopy (FT-IR and Raman) are employed to study molecular interactions in the room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Different conformers of a cation-anion pair based on their molecular interactions are simulated in the gas phase and in a dielectric continuum solvent environment. Although the ordering of conformers in energy varies with theoretical methods, their predictions for three lowest energy conformers in the gas phase are similar. Strong C-H---N interactions between the acidic hydrogen atom of the cation imidazole ring and the nitrogen atom of the anion are predicted for either the lowest or second lowest energy conformer. In a continuum solvent, different theoretical methods yield the same ion-pair conformation for the lowest energy state. In both phases, the density functional method predicts that the anion is in a trans conformation in the lowest energy ion pair state. The theoretical results are compared with experimental observations from Raman scattering and IR absorption spectroscopies and manifestations of the molecular interactions in the vibrational spectra are discussed. The directions of the frequency shifts of the characteristic vibrations relative to the free anion and cation are explained by calculating the difference electron density coupled with electron density topography.

Spectroscopic studies of the intramolecular hydrogen bonding in o-hydroxy Schiff bases, derived from diaminomaleonitrile, and their deprotonation reaction products

NASA Astrophysics Data System (ADS)

Szady-Chełmieniecka, Anna; Kołodziej, Beata; Morawiak, Maja; Kamieński, Bohdan; Schilf, Wojciech

2018-01-01

The structural study of five Schiff bases derived from diaminomaleonitrile (DAMN) and 2-hydroxy carbonyl compounds was performed using 1H, 13C and 15N NMR methods in solution and in the solid state as well. ATR-FTIR and X-Ray spectroscopies were used for confirmation of the results obtained by NMR method. The imine obtained from DAMN and benzaldehyde was synthesized as a model compound which lacks intramolecular hydrogen bond. Deprotonation of all synthesized compounds was done by treating with tetramethylguanidine (TMG). NMR data revealed that salicylidene Schiff bases in DMSO solution exist as OH forms without intramolecular hydrogen bonds and independent on the substituents in aromatic ring. In the case of 2-hydroxy naphthyl derivative, the OH proton is engaged into weak intramolecular hydrogen bond. Two of imines (salDAMN and 5-BrsalDAMN) exist in DMSO solution as equilibrium mixtures of two isomers (A and B). The structures of equilibrium mixture in the solid state have been studied by NMR, ATR-FTIR and X-Ray methods. The deprotonation of three studied compounds (salDAMN, 5-BrsalDAMN, and 5-CH3salDAMN) proceeded in two different ways: deprotonation of oxygen atom (X form) or of nitrogen atom of free primary amine group of DAMN moiety (Y form). For 5-NO2salDAMN and naphDAMN only one form (X) was observed.

Genotoxicity risk assessment of diversely substituted quinolines using the SOS chromotest.

PubMed

Duran, Leidy Tatiana Díaz; Rincón, Nathalia Olivar; Galvis, Carlos Eduardo Puerto; Kouznetsov, Vladimir V; Lorenzo, Jorge Luis Fuentes

2015-03-01

Quinolines are aromatic nitrogen compounds with wide therapeutic potential to treat parasitic and microbial diseases. In this study, the genotoxicity of quinoline, 4-methylquinoline, 4-nitroquinoline-1-oxide (4-NQO), and diversely functionalized quinoline derivatives and the influence of the substituents (functional groups and/or atoms) on their genotoxicity were tested using the SOS chromotest. Quinoline derivatives that induce genotoxicity by the formation of an enamine epoxide structure did not induce the SOS response in Escherichia coli PQ37 cells, with the exception of 4-methylquinoline that was weakly genotoxic. The chemical nature of the substitution (C-5 to C-8: hydroxyl, nitro, methyl, isopropyl, chlorine, fluorine, and iodine atoms; C-2: phenyl and 3,4-methylenedioxyphenyl rings) of quinoline skeleton did not significantly modify compound genotoxicities; however, C-2 substitution with α-, β-, or γ-pyridinyl groups removed 4-methylquinoline genotoxicity. On the other hand, 4-NQO derivatives whose genotoxic mechanism involves reduction of the C-4 nitro group were strong inducers of the SOS response. Methyl and nitrophenyl substituents at C-2 of 4-NQO core affected the genotoxic potency of this molecule. The relevance of these results is discussed in relation to the potential use of the substituted quinolines. The work showed the sensitivity of SOS chromotest for studying structure-genotoxicity relationships and bioassay-guided quinoline synthesis. © 2013 Wiley Periodicals, Inc.

Supramolecular interactions in carboxylate and sulfonate salts of 2,6-diamino-4-chloropyrimidinium.

PubMed

Mohana, Marimuthu; Thomas Muthiah, Packianathan; Butcher, Ray J

2017-07-01

Two new salts, namely 2,6-diamino-4-chloropyrimidinium 2-carboxy-3-nitrobenzoate, C 4 H 6 ClN 4 + ·C 8 H 4 NO 6 - , (I), and 2,6-diamino-4-chloropyrimidinium p-toluenesulfonate monohydrate, C 4 H 6 ClN 4 + ·C 7 H 7 O 3 S - ·H 2 O, (II), have been synthesized and characterized by single-crystal X-ray diffraction. In both crystal structures, the N atom in the 1-position of the pyrimidine ring is protonated. In salt (I), the protonated N atom and the amino group of the pyrimidinium cation interact with the carboxylate group of the anion through N-H...O hydrogen bonds to form a heterosynthon with an R 2 2 (8) ring motif. In hydrated salt (II), the presence of the water molecule prevents the formation of the familiar R 2 2 (8) ring motif. Instead, an expanded ring [i.e. R 3 2 (8)] is formed involving the sulfonate group, the pyrimidinium cation and the water molecule. Both salts form a supramolecular homosynthon [R 2 2 (8) ring motif] through N-H...N hydrogen bonds. The molecular structures are further stabilized by π-π stacking, and C=O...π, C-H...O and C-H...Cl interactions.

Lattice Gas Model Based Optimization of Plasma-Surface Processes for GaN-Based Compound Growth

NASA Astrophysics Data System (ADS)

Nonokawa, Kiyohide; Suzuki, Takuma; Kitamori, Kazutaka; Sawada, Takayuki

2001-10-01

Progress of the epitaxial growth technique for GaN-based compounds makes these materials attractive for applications in high temperature/high-power electronic devices as well as in short-wavelength optoelectronic devices. For MBE growth of GaN epilayer, atomic nitrogen is usually supplied from ECR-plasma while atomic Ga is supplied from conventional K-cell. To grow high-quality epilayer, fundamental knowledge of the detailed atomic process, such as adsorption, surface migration, incorporation, desorption and so forth, is required. We have studied the influence of growth conditions on the flatness of the growth front surface and the growth rate using Monte Carlo simulation based on the lattice gas model. Under the fixed Ga flux condition, the lower the nitrogen flux and/or the higher the growth temperature, the better the flatness of the front surface at the sacrifice of the growth rate of the epilayer. When the nitrogen flux is increased, the growth rate reaches saturation value determined from the Ga flux. At a fixed growth temperature, increasing of nitrogen to Ga flux ratio results in rough surface owing to 3-dimensional island formation. Other characteristics of MBE-GaN growth using ECR-plasma can be well reproduced.

Molecular characterization of nitrogen and sulfur containing compounds in night-time SOA

NASA Astrophysics Data System (ADS)

Iinuma, Yoshiteru; Mutzel, Anke; Rodigast, Maria; Böge, Olaf; Herrmann, Hartmut

2014-05-01

The oxidation of volatile organic compounds (VOCs) leads to the formation of low volatile organic compounds that can form secondary organic aerosol (SOA). Studies in the past showed that laboratory generated and ambient SOA are made of polar molecules with O/C ratios generally greater than 0.5. More recent studies have shown that SOA compounds can contain heteroatoms mainly sulfur and nitrogen atoms. Offline chemical analysis with high-resolution mass spectrometers and fragmentation experiments has shown that sulphur containing compounds are mainly organosulfates and nitrogen containing species are aromatic heterocyclic compounds such as imidazole and nitrated aromatic compounds such as nitrophenols. In addition to these, SOA compounds containing both sulfur and nitrogen have been reported from the analysis of ambient organic aerosol, rainwater, fog and cloud samples. Based on the mass spectrometric evidence these compounds are attributed to nitrooxy-organosulfates originating from isoprene and monoterpenes. Although these compounds are ubiquitously detected in the ambient samples, reports about their detection in laboratory generated SOA are scares and their formation mechanisms are not well understood. In the present study, we investigated the formation of sulfur and nitrogen containing SOA species in the oxidation of biogenic VOCs. Photooxidation and night-time oxidation experiments were performed in a smog chamber to produce SOA samples. The laboratory generated SOA samples were analysed with UPLC-IMS-TOFMS (Ultra Performance Liquid Chromatography coupled to Ion Mobility Spectrometry and Time of Flight Mass Spectrometry). The presence of highly acidic sulphate seed particles (pH0) did not promote the formation of compounds with chemical formula of C10H17NO7S- and m/z value of 294.0653, indicating that the formation mechanisms of these compounds unlikely involve the ring opening reactions of epoxides and subsequent sulfation reactions. On the other hand, their formation was significantly enhanced when the night-time oxidation was performed in the presence of both neutral seed particle and gas-phase SO2, suggesting that the presence of gas-phase SO2 is a key for their formation.

Synthesis, Properties, Calculations and Applications of Small Molecular Host Materials Containing Oxadiazole Units with Different Nitrogen and Oxygen Atom Orientations for Solution-Processable Blue Phosphorescent OLEDs

NASA Astrophysics Data System (ADS)

Ye, Hua; Wu, Hongyu; Chen, Liangyuan; Ma, Songhua; Zhou, Kaifeng; Yan, Guobing; Shen, Jiazhong; Chen, Dongcheng; Su, Shi-Jian

2018-03-01

A series of new small molecules based on symmetric electron-acceptor of 1,3,4-oxadiazole moiety or its asymmetric isomer of 1,2,4-oxadiazole unit were successfully synthesized and applied to solution-processable blue phosphorescent organic light-emitting diodes for the first time, and their thermal, photophysical, electrochemical properties and density functional theory calculations were studied thoroughly. Due to the high triplet energy levels ( E T, 2.82-2.85 eV), the energy from phosphorescent emitter of iridium(III) bis[(4,6-difluorophenyl)-pyridinate- N,C2']picolinate (FIrpic) transfer to the host molecules could be effectively suppressed and thus assuring the emission of devices was all from FIrpic. In comparison with the para-mode conjugation in substitution of five-membered 1,3,4-oxadiazole in 134OXD, the meta-linkages of 1,2,4-isomer appending with two phenyl rings cause the worse conjugation degree and the electron delocalization as well as the lower electron-withdrawing ability for the other 1,2,4-oxadiazole-based materials. Noting that the solution-processed device based on 134OXD containing 1,3,4-oxadiazole units without extra vacuum thermal-deposited hole/exciton-blocking layer and electron-transporting layer showed the highest maximum current efficiency (CEmax) of 8.75 cd/A due to the excellent charge transporting ability of 134OXD, which far surpassed the similar devices based on other host materials containing 1,2,4-oxadiazole units. Moreover, the device based on 134OXD presented small efficiency roll-off with current efficiency (CE) of 6.26 cd/A at high brightness up to 100 cd/m2. This work demonstrates different nitrogen and oxygen atom orientations of the oxadiazole-based host materials produce major impact on the optoelectronic characteristics of the solution-processable devices.

The impact of exospheric neutral dynamics on ring current decay

NASA Astrophysics Data System (ADS)

Ilie, R.; Liemohn, M. W.; Skoug, R. M.; Funsten, H. O.; Gruntman, M.; Bailey, J. J.; Toth, G.

2015-12-01

The geocorona plays an important role in the energy budget of the Earth's inner magnetosphere since charge exchange of energetic ions with exospheric neutrals makes the exosphere act as an energy sink for ring current particles. Long-term ring current decay following a magnetic storm is mainly due to these electron transfer reactions, leading to the formation energetic neutral atoms (ENAs) that leave the ring current system on ballistic trajectories. The number of ENAs emitted from a given region of space depends on several factors, such as the energy and species of the energetic ion population in that region and the density of the neutral gas with which the ions undergo charge exchange. However, the density and structure of the exosphere are strongly dependent on changes in atmospheric temperature and density as well as charge exchange with the ions of plasmaspheric origin, which depletes the geocorona (by having a neutral removed from the system). Moreover, the radiation pressure exerted by solar far-ultraviolet photons pushes the geocoronal hydrogen away from the Earth in an anti-sunward direction to form a tail of neutral hydrogen. TWINS ENA images provide a direct measurement of these ENA losses and therefore insight into the dynamics of the ring current decay through interactions with the geocorona. We assess the influence of geocoronal neutrals on ring current formation and decay by analysis of the predicted ENA emissions using 6 different geocoronal models and simulations from the HEIDI ring current model during storm time. Comparison with TWINS ENA images shows that the location of the peak ENA enhancements is highly dependent on the distribution of geocoronal hydrogen density. We show that the neutral dynamics has a strong influence on the time evolution of the ring current populations as well as on the formation of energetic neutral atoms.

THE IBEX RIBBON AND THE PICKUP ION RING STABILITY IN THE OUTER HELIOSHEATH. II. MONTE-CARLO AND PARTICLE-IN-CELL MODEL RESULTS

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

Niemiec, J.; Florinski, V.; Heerikhuisen, J.

2016-08-01

The nearly circular ribbon of energetic neutral atom (ENA) emission discovered by NASA’s Interplanetary Boundary EXplorer satellite ( IBEX ), is most commonly attributed to the effect of charge exchange of secondary pickup ions (PUIs) gyrating about the magnetic field in the outer heliosheath (OHS) and the interstellar space beyond. The first paper in the series (Paper I) presented a theoretical analysis of the pickup process in the OHS and hybrid-kinetic simulations, revealing that the kinetic properties of freshly injected proton rings depend sensitively on the details of their velocity distribution. It was demonstrated that only rings that are notmore » too narrow (parallel thermal spread above a few km s{sup −1}) and not too wide (parallel temperature smaller than the core plasma temperature) could remain stable for a period of time long enough to generate ribbon ENAs. This paper investigates the role of electron dynamics and the extra spatial degree of freedom in the ring ion scattering process with the help of two-dimensional full particle-in-cell (PIC) kinetic simulations. A good agreement is observed between ring evolution under unstable conditions in hybrid and PIC models, and the dominant modes are found to propagate parallel to the magnetic field. We also present more realistic ribbon PUI distributions generated using Monte Carlo simulations of atomic hydrogen in the global heliosphere and examine the effect of both the cold ring-like and the hot “halo” PUIs produced from heliosheath ENAs on the ring stability. It is shown that the second PUI population enhances the fluctuation growth rate, leading to faster isotropization of the solar-wind-derived ring ions.« less

The IBEX Ribbon and the Pickup Ion Ring Stability in the Outer Heliosheath II. Monte-Carlo and Particle-in-cell Model Results

NASA Astrophysics Data System (ADS)

Niemiec, J.; Florinski, V.; Heerikhuisen, J.; Nishikawa, K.-I.

2016-08-01

The nearly circular ribbon of energetic neutral atom (ENA) emission discovered by NASA’s Interplanetary Boundary EXplorer satellite (IBEX), is most commonly attributed to the effect of charge exchange of secondary pickup ions (PUIs) gyrating about the magnetic field in the outer heliosheath (OHS) and the interstellar space beyond. The first paper in the series (Paper I) presented a theoretical analysis of the pickup process in the OHS and hybrid-kinetic simulations, revealing that the kinetic properties of freshly injected proton rings depend sensitively on the details of their velocity distribution. It was demonstrated that only rings that are not too narrow (parallel thermal spread above a few km s-1) and not too wide (parallel temperature smaller than the core plasma temperature) could remain stable for a period of time long enough to generate ribbon ENAs. This paper investigates the role of electron dynamics and the extra spatial degree of freedom in the ring ion scattering process with the help of two-dimensional full particle-in-cell (PIC) kinetic simulations. A good agreement is observed between ring evolution under unstable conditions in hybrid and PIC models, and the dominant modes are found to propagate parallel to the magnetic field. We also present more realistic ribbon PUI distributions generated using Monte Carlo simulations of atomic hydrogen in the global heliosphere and examine the effect of both the cold ring-like and the hot “halo” PUIs produced from heliosheath ENAs on the ring stability. It is shown that the second PUI population enhances the fluctuation growth rate, leading to faster isotropization of the solar-wind-derived ring ions.

Spatial Concentrations of Silicon Atoms in RF Discharges of Silane.

DTIC Science & Technology

1985-02-18

regions. These profiles were much more sensitive to plasma chemistry changes than profiles obtained from plasma emission. Experiments with nitrogen...addition demonstrated significant changes in the silicon atom profiles near the sheath boundary. Originator supplied keywords include: rf discharge, silane, plasma chemistry , silicon atom, laser-induced fluorescence.

Adsorption of O_{2} on Ag(111): Evidence of Local Oxide Formation.

PubMed

Andryushechkin, B V; Shevlyuga, V M; Pavlova, T V; Zhidomirov, G M; Eltsov, K N

2016-07-29

The atomic structure of the disordered phase formed by oxygen on Ag(111) at low coverage is determined by a combination of low-temperature scanning tunneling microscopy and density functional theory. We demonstrate that the previous assignment of the dark objects in STM to chemisorbed oxygen atoms is incorrect and incompatible with trefoil-like structures observed in atomic-resolution images in current work. In our model, each object is an oxidelike ring formed by six oxygen atoms around the vacancy in Ag(111).

Biosynthesis of Costunolide, Dihydrocostunolide, and Leucodin. Demonstration of Cytochrome P450-Catalyzed Formation of the Lactone Ring Present in Sesquiterpene Lactones of Chicory

PubMed Central

de Kraker, Jan-Willem; Franssen, Maurice C.R.; Joerink, Maaike; de Groot, Aede; Bouwmeester, Harro J.

2002-01-01

Chicory (Cichorium intybus) is known to contain guaianolides, eudesmanolides, and germacranolides. These sesquiterpene lactones are postulated to originate from a common germacranolide, namely (+)-costunolide. Whereas a pathway for the formation of germacra-1(10),4,11(13)-trien-12-oic acid from farnesyl diphosphate had previously been established, we now report the isolation of an enzyme activity from chicory roots that converts the germacrene acid into (+)-costunolide. This (+)-costunolide synthase catalyzes the last step in the formation of the lactone ring present in sesquiterpene lactones and is dependent on NADPH and molecular oxygen. Incubation of the germacrene acid in the presence of 18O2 resulted in the incorporation of one atom of 18O into (+)-costunolide. The label was situated at the ring oxygen atom. Hence, formation of the lactone ring most likely occurs via C6-hydroxylation of the germacrene acid and subsequent attack of this hydroxyl group at the C12-atom of the carboxyl group. Blue light-reversible CO inhibition and experiments with cytochrome P450 inhibitors demonstrated that the (+)-costunolide synthase is a cytochrome P450 enzyme. In addition, enzymatic conversion of (+)-costunolide into 11(S),13-dihydrocostunolide and leucodin, a guaianolide, was detected. The first-mentioned reaction involves an enoate reductase, whereas the formation of leucodin from (+)-costunolide probably involves more than one enzyme, including a cytochrome P450 enzyme. PMID:12011356

Biosynthesis of costunolide, dihydrocostunolide, and leucodin. Demonstration of cytochrome p450-catalyzed formation of the lactone ring present in sesquiterpene lactones of chicory.

PubMed

de Kraker, Jan-Willem; Franssen, Maurice C R; Joerink, Maaike; de Groot, Aede; Bouwmeester, Harro J

2002-05-01

Chicory (Cichorium intybus) is known to contain guaianolides, eudesmanolides, and germacranolides. These sesquiterpene lactones are postulated to originate from a common germacranolide, namely (+)-costunolide. Whereas a pathway for the formation of germacra-1(10),4,11(13)-trien-12-oic acid from farnesyl diphosphate had previously been established, we now report the isolation of an enzyme activity from chicory roots that converts the germacrene acid into (+)-costunolide. This (+)-costunolide synthase catalyzes the last step in the formation of the lactone ring present in sesquiterpene lactones and is dependent on NADPH and molecular oxygen. Incubation of the germacrene acid in the presence of 18O2 resulted in the incorporation of one atom of 18O into (+)-costunolide. The label was situated at the ring oxygen atom. Hence, formation of the lactone ring most likely occurs via C6-hydroxylation of the germacrene acid and subsequent attack of this hydroxyl group at the C12-atom of the carboxyl group. Blue light-reversible CO inhibition and experiments with cytochrome P450 inhibitors demonstrated that the (+)-costunolide synthase is a cytochrome P450 enzyme. In addition, enzymatic conversion of (+)-costunolide into 11(S),13-dihydrocostunolide and leucodin, a guaianolide, was detected. The first-mentioned reaction involves an enoate reductase, whereas the formation of leucodin from (+)-costunolide probably involves more than one enzyme, including a cytochrome P450 enzyme.

Modeling the near-Earth interaction between ring current ions and exospheric neutrals: escape through energetic neutral atoms (ENAs)

NASA Astrophysics Data System (ADS)

LLera, K.; Goldstein, J.; McComas, D. J.; Valek, P. W.

2016-12-01

The two major loss processes for ring current decay are precipitation and energetic neutral atoms (ENAs). Since the exospheric neutral density increases with decreasing altitudes, precipitating ring current ions (reaching down to 200 - 800 km in altitude) also produce low-altitude ENA signatures that can be stronger than the ring current emission at equatorial distances ( 2 - 9 Re). The higher density results in multiple collisions between the ring current ions and exospheric oxygen. The affect on hydrogen ions is the focus of this study. Since the H particle sustains energy loss ( 36 eV) at each neutralizing or re-ionizing interaction, the escaped ENAs do not directly reflect the ring current properties. We model the energy loss due to multiple charge exchange and electron stripping interactions of 1 - 100 keV precipitating ring current ions undergo before emerging as low-altitude ENAs. The H particle is either an ion or an ENA throughout the simulation. Their lifetime is analytically determined by the length of one mean free path. We track the ion state with Lorentz motion while the ENA travels ballistically across the geomagnetic field. Our simulations show the energy loss is greater than 20% for hydrogen ring current ions below 30 keV (60 keV for the simulations that wander equatorward). This is the first quantification of the energy loss associated with the creation of low-altitude ENAs. Our model (currently constrained in the meridional plane) has revealed characteristics on how precipitation is affected by the near-Earth neutral exosphere. This ion-neutral interaction removes particles from the loss cone but promotes loss through ENA generation. These findings should be implemented in models predicting the ring current decay and used as an analysis tool to reconstruct the ring current population from observed low-altitude ENAs.

Diversity and distribution of actinobacterial aromatic ring oxygenase genes across contrasting soil properties.

PubMed

Weidow, Christopher A; Bae, Hee-Sung; Chauhan, Ashvini; Ogram, Andrew

2015-04-01

The diversity of a gene family encoding Actinobacterial aromatic ring oxygenases (AAROs) was detected by the PCR-cloning approach using a newly designed PCR primer set. The distribution of AAROs was investigated in 11 soils representing different land management and vegetation zones and was correlated with several geochemical parameters including pH, organic matter (OM), total Kjeldahl nitrogen (TKN), and nitrogen oxides (NO(x)-N: mostly NO3(-)-N). The distribution of individual clades encoding enzymes with potentially different substrates were correlated with different environmental factors, suggesting differential environmental controls on the distribution of specific enzymes as well as sequence diversity. For example, individual clades associated with phthalate dioxygenases were either strongly negatively correlated with pH, or not correlated with pH but showed strong positive correlation with organic carbon content. A large number of clones clustering in a clade related to PAH oxygenases were positively correlated with pH and nitrogen, but not with organic matter. This analysis may yield insight into the ecological forces driving the distribution of these catabolic genes.

Theoretical study of the alkaline hydrolysis of an aza-β-lactam derivative of clavulanic acid

NASA Astrophysics Data System (ADS)

Garcías, Rafael C.; Coll, Miguel; Donoso, Josefa; Muñoz, Francisco

2003-04-01

DFT calculations based on the hybrid functional B3LYP/6-31+G * were used to study the alkaline hydrolysis of an aza-clavulanic acid, which results from the substitution of the carbon atom at position 6 in clavulanic acid by a nitrogen atom. The presence of the nitrogen atom endows the compound with special properties; in fact, once formed, the tetrahedral intermediate can evolve with cleavage of the N 4-C 7 or N 6-C 7 bond, which obviously leads to different reaction products. These differential bond cleavages may play a central role in the inactivation of β-lactamases, so the compound may be a powerful inactivator of these enzymes.

Point defect weakened thermal contraction in monolayer graphene

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

Zha, Xian-Hu; Department of Physics, University of Science and Technology of China, Hefei; USTC-CityU Joint Advanced Research Centre, Suzhou 215123

We investigate the thermal expansion behaviors of monolayer graphene and three configurations of graphene with point defects, namely the replacement of one carbon atom with a boron or nitrogen atom, or of two neighboring carbon atoms by boron-nitrogen atoms, based on calculations using first-principles density functional theory. It is found that the thermal contraction of monolayer graphene is significantly decreased by point defects. Moreover, the corresponding temperature for negative linear thermal expansion coefficient with the maximum absolute value is reduced. The cause is determined to be point defects that enhance the mechanical strength of graphene and then reduce the amplitudemore » and phonon frequency of the out-of-plane acoustic vibration mode. Such defect weakening of graphene thermal contraction will be useful in nanotechnology to diminish the mismatching or strain between the graphene and its substrate.« less