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Sample records for single isomer anionic

  1. Chiral separation of tedizolid using charge single isomer derivatives of cyclodextrins by capillary electrokinetic chromatography.

    Science.gov (United States)

    Michalska, Katarzyna; Gruba, Ewa; Cielecka-Piontek, Judyta; Bednarek, Elżbieta

    2016-02-20

    A method to enantioseparate tedizolid (TED), the second analogue after linezolid (LIN) in a truly new class of antibacterial agents, the oxazolidinones, was developed based on capillary electrokinetic chromatography using cyclodextrin as chiral pseudophase (CD-cEKC). The single isomer R-tedizolid possesses one chiral centre at C5 of the oxazolidinone ring, which is associated with the antibacterial activity of the drug. Tedizolid enantiomers are non-charged and therefore require the use of charged cyclodextrins (CCDs) as carrier hosts to achieve a velocity difference during migration. During method development, hydrophilic anionic single-isomer and moderately hydrophobic and hydrophobic cyclodextrins were tested, including heptakis-(2,3-dihydroxy-6-sulfo)-β-cyclodextrin (HS-β-CD), heptakis-(2,3-diacetyl-6-sulfo)-β-cyclodextrin (HDAS-β-CD), oktakis-(2,3-diacetyl-6-sulfo)-γ-cyclodextrin (ODAS-γ-CD) and heptakis-(2,3-dimethyl-6-sulfo)-β-cyclodextrin (HDMS-β-CD). Only CDs that have acetyl groups at the C2 and C3 positions with seven (HDAS-β-CD) or eight (ODAS-γ-CD) residues of glucopyranose units provided baseline separation of the tedizolid enantiomers with the addition of organic solvent. During the experiments, different organic solvents were tested, such as methanol, acetonitrile, tetrahydrofuran, which varied in their abilities to donate or accept protons. The best enantiomer separation results were obtained using the CD-cEKC method with 37.5mM HDAS-β-CD dissolved in 50mM formic buffer (pH 4.0) with the addition of acetonitrile (81.4:18.6, v/v) at 27ºC, normal polarity, and 12kV. Finally, the apparent binding constants for each enantiomer-HDAS-β-CD pair were calculated. Moreover, in order to evaluate the behaviour of TED and LIN enantiomers relative to chiral selector, enantioselective interactions towards the precursors of TED and LIN isomers were also investigated. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Toward the laboratory identification of the not-so-simple NS2 neutral and anion isomers

    Science.gov (United States)

    Fortenberry, Ryan C.; Thackston, Russell; Francisco, Joseph S.; Lee, Timothy J.

    2017-08-01

    The NS2 radical is a simple arrangement of atoms with a complex electronic structure. This molecule was first reported by Hassanzadeh and Andrew's group [J. Am. Chem. Soc. 114, 83 (1992)] through Ar matrix isolation experiments. In the quarter century since this seminal work was published, almost nothing has been reported about nitrogen disulfide even though NS2 is isovalent with the common NO2. The present study aims to shed new insight into possible challenges with the characterization of this radical. No less than three potential energy surfaces all intersect in the C2v region of the SNS radical isomer. A type-C Renner-Teller molecule is present for the linear 2Πu state where the potential energy surface is fully contained within the 2.05 kcal/mol lower energy X ˜ 2A1 state. A C2v, 1 2B1 state is present in this same region, but a double excitation is required to access this state from the X ˜ 2A1 state of SNS. Additionally, a 1 2A' NSS isomer is also present but with notable differences in the geometry from the global minimum. Consequently, the rovibronic spectrum of these NS2 isomers is quite complicated. While the present theory and previous Ar matrix experiments agree well on isotopic shifts, they differ notably for the absolute fundamental vibrational frequency transitions. These differences are likely a combination of matrix shifts and issues associated with the neglect of non-adiabatic coupling in the computations. In either case, it is clear that high-resolution gas phase experimental observations will be complicated to sort. The present computations should aid in their analysis.

  3. Toward the laboratory identification of the not-so-simple NS2 neutral and anion isomers.

    Science.gov (United States)

    Fortenberry, Ryan C; Thackston, Russell; Francisco, Joseph S; Lee, Timothy J

    2017-08-21

    The NS 2 radical is a simple arrangement of atoms with a complex electronic structure. This molecule was first reported by Hassanzadeh and Andrew's group [J. Am. Chem. Soc. 114, 83 (1992)] through Ar matrix isolation experiments. In the quarter century since this seminal work was published, almost nothing has been reported about nitrogen disulfide even though NS 2 is isovalent with the common NO 2 . The present study aims to shed new insight into possible challenges with the characterization of this radical. No less than three potential energy surfaces all intersect in the C 2 v region of the SNS radical isomer. A type-C Renner-Teller molecule is present for the linear 2 Π u state where the potential energy surface is fully contained within the 2.05 kcal/mol lower energy X̃  2 A 1 state. A C 2 v , 1  2 B 1 state is present in this same region, but a double excitation is required to access this state from the X̃  2 A 1 state of SNS. Additionally, a 1  2 A ' NSS isomer is also present but with notable differences in the geometry from the global minimum. Consequently, the rovibronic spectrum of these NS 2 isomers is quite complicated. While the present theory and previous Ar matrix experiments agree well on isotopic shifts, they differ notably for the absolute fundamental vibrational frequency transitions. These differences are likely a combination of matrix shifts and issues associated with the neglect of non-adiabatic coupling in the computations. In either case, it is clear that high-resolution gas phase experimental observations will be complicated to sort. The present computations should aid in their analysis.

  4. Mechanism for odd-electron anion generation of dihydroxybenzoic acid isomers in matrix-assisted laser desorption/ionization mass spectrometry with density functional theory calculations.

    Science.gov (United States)

    Yamagaki, Tohru; Takeuchi, Michika; Watanabe, Takehiro; Sugahara, Kohtaro; Takeuchi, Takae

    2016-12-30

    Proton and radical are transferred between matrices and matrix and analyte in matrix-assisted laser desorption/ionization (MALDI) and these transfers drive ionization of analytes. The odd-electron anion [M-2H] •- was generated in dihydroxybenzoic acids (DHBs) and the ion abundance of the 2,5-DHB was the highest among six DHB isomers. We were interested in the mechanism of the ion generation of the odd-electron anion. The observed [M-2H] •- and [M-3H] - ions, which were generated with the hydrogen radical removed from the phenolic hydroxyl groups (OH) in DHB isomers, were analyzed using negative-ion MALDI-MS. The enthalpy for ion generation and their stable structures were calculated using the density functional theory (DFT) calculation program Gaussian 09 with the B3LYP functional and the 6-31+G(d) basis set. The number of observed [M-2H] •- and [M-3H] - ions of the DHB isomers was dependent on the positions of the phenolic OH groups in the DHB isomers because the carboxy group interacts with the ortho OH group due to neighboring group participation, as confirmed from the stable structures of the [M-2H] •- anions calculated with the Gaussian 09 program. The DHB isomers were placed into three categories according to the number of the ions. Odd-electron anions ([M-2H] •- ) and [M-2H • -H] - ([M-3H] - ) ions were generated from DHB isomers due to removal of the hydrogen radical from the phenolic groups. The enthalpy for ion generation revealed that ion formation proceeds via a two-step pathway through the [M-M] - ion as an intermediate. © 2016 The Authors. Rapid Communications in Mass Spectrometry Published by John Wiley & Sons Ltd. © 2016 The Authors. Rapid Communications in Mass Spectrometry Published by John Wiley & Sons Ltd.

  5. Self-Organization of +-Crown Ether Derivatives into Double-Columnar Arrays Controlled by Supramolecular Isomers of Hydrogen-Bonded Anionic Biimidazolate Ni Complexes

    Directory of Open Access Journals (Sweden)

    Makoto Tadokoro

    2012-01-01

    Full Text Available Anionic tris (biimidazolate nickelate (II ([Ni(Hbim3]−, which is a hydrogen-bonding (H-bonding molecular building block, undergoes self-organization into honeycomb-sheet superstructures connected by complementary intermolecular H-bonds. The crystal obtained from the stacking of these sheets is assembled into channel frameworks, approximately 2 nm wide, that clathrate two cationic K+-crown ether derivatives organised into one-dimensional (1D double-columnar arrays. In this study, we have shown that all five cationic guest-included crystals form nanochannel structures that clathrate the 1-D double-columnar arrays of one of the four types of K+-crown ether derivatives, one of which induces a polymorph. This is accomplished by adaptably fitting two types of anionic [Ni(Hbim3]− host arrays. One is a ΔΛ−ΔΛ−ΔΛ⋯ network with H-bonded linkages alternating between the two different optical isomers of the Δ and Λ types with flexible H-bonded [Ni(Hbim3]−. The other is a ΔΔΔ−ΛΛΛ⋯ network of a racemate with 1-D H-bonded arrays of the same optical isomer for each type. Thus, [Ni(Hbim3]− can assemble large cations such as K+ crown-ether derivatives into double-columnar arrays by highly recognizing flexible H-bonding arrangements with two host networks of ΔΛ−ΔΛ−ΔΛ⋯ and ΔΔΔ−ΛΛΛ⋯.

  6. Single-molecule imaging reveals topological isomer-dependent diffusion by 4-armed star and dicyclic 8-shaped polymers

    KAUST Repository

    Habuchi, Satoshi

    2015-04-21

    Diffusion dynamics of topological isomers of polymer molecules was investigated at the single-molecule level in a melt state by employing the fluorophore-incorporated 4-armed star and the corresponding doubly-cyclized, 8-shaped poly(THF) chains. While the single-molecule fluorescence imaging experiment revealed that the diffusion of the 4-armed star polymer was described by a single Gaussian distribution, the diffusion of the 8-shaped polymer exhibited a double Gaussian distribution behaviour. We reasoned that the two 8-shaped polymeric isomers have distinct diffusion modes in the melt state, although ensemble-averaged experimental methods cannot detect differences in overall conformational state of the isomers. The single-molecule experiments suggested that one of the 8-shaped polymeric isomer, having the horizontally oriented form, causes an efficient threading with the linear matrix chains which leads to the slower diffusion compared with the corresponding 4-armed star polymer, while the other 8-shaped polymeric isomer, having the vertically oriented form, displayed faster diffusion by the suppression of effective threading with the linear matrix chains due to its contracted chain conformation.

  7. Structures, stabilities, aromaticity, and electronic properties of C66 fullerene isomers, anions (C662-, C664-, C666-), and metallofullerenes (Sc2-C66)

    International Nuclear Information System (INIS)

    Cui Yanhong; Tian, Wei Quan; Feng Jikang; Chen Deli

    2010-01-01

    Among all the 4478 classical isomers of C 66 , C 66 (C s :0060) with the lowest number of pentagon-pentagon fusions was predicted to be the most stable isomer, followed by isomers C 66 (C 2v :0011) and C 66 (C 2 :0083). The infrared spectra and aromaticity of the most stable isomers were predicted. The relative stabilities of C 66 isomers change with charges or doping of metals. The structures and relative stabilities of the most stable metallofullerenes were delineated and compared with experiment. Sc 2 -C 66 (C 2 :0083) was predicted to be the most stable metallofullerene, although Sc 2 -C 66 (C 2v :0011) was observed. Charge-transfer from Sc 2 to the fused pentagons and the bonding between these two moieties significantly decrease the strain energies caused by the pair of fused pentagons thereby stabilizing the fullerene cage.

  8. High-performance liquid chromatography separation of cis-trans anthocyanin isomers from wild Lycium ruthenicum Murr. employing a mixed-mode reversed-phase/strong anion-exchange stationary phase.

    Science.gov (United States)

    Jin, Hongli; Liu, Yanfang; Guo, Zhimou; Yang, Fan; Wang, Jixia; Li, Xiaolong; Peng, Xiaojun; Liang, Xinmiao

    2015-01-21

    The cis-trans isomerism is a common phenomenon for acylated anthocyanins. Nevertheless, few studies reported effective methods for the preparation of isomeric anthocyanins from natural products. In this work, a high-performance liquid chromatography (HPLC) method was developed to efficiently purify anthocyanin isomers from Lycium ruthenicum Murr. based on a mixed-mode reversed-phase/strong anion-exchange column (named XCharge C8SAX). Four commercially available columns were evaluated with a pair of isomeric anthocyanins, and the results demonstrated that the XCharge C8SAX column exhibited improved selectivity and column efficiency for the isomers. The chromatographic parameters, including pH, organic content, and ionic strength, were investigated. Optimal separation quality for the anthocyanin isomers was achieved on the XCharge C8SAX column. Six pure anthocyanins, including two pairs of cis-trans isomeric anthocyanins with one new anthocyanin, were purified from L. ruthenicum and identified. All of the results indicated that this method is an effective way to separate anthocyanins, especially for cis-trans isomers.

  9. Selective arc-discharge synthesis of Dy2S-clusterfullerenes and their isomer-dependent single molecule magnetism.

    Science.gov (United States)

    Chen, Chia-Hsiang; Krylov, Denis S; Avdoshenko, Stanislav M; Liu, Fupin; Spree, Lukas; Yadav, Ravi; Alvertis, Antonis; Hozoi, Liviu; Nenkov, Konstantin; Kostanyan, Aram; Greber, Thomas; Wolter, Anja U B; Popov, Alexey A

    2017-09-01

    A method for the selective synthesis of sulfide clusterfullerenes Dy 2 S@C 2 n is developed. Addition of methane to the reactive atmosphere reduces the formation of empty fullerenes in the arc-discharge synthesis, whereas the use of Dy 2 S 3 as a source of metal and sulfur affords sulfide clusterfullerenes as the main fullerene products along with smaller amounts of carbide clusterfullerenes. Two isomers of Dy 2 S@C 82 with C s (6) and C 3v (8) cage symmetry, Dy 2 S@C 72 - C s (10528), and a carbide clusterfullerene Dy 2 C 2 @C 82 - C s (6) were isolated. The molecular structure of both Dy 2 S@C 82 isomers was elucidated by single-crystal X-ray diffraction. SQUID magnetometry demonstrates that all of these clusterfullerenes exhibit hysteresis of magnetization, with Dy 2 S@C 82 - C 3v (8) being the strongest single molecule magnet in the series. DC- and AC-susceptibility measurements were used to determine magnetization relaxation times in the temperature range from 1.6 K to 70 K. Unprecedented magnetization relaxation dynamics with three consequent Orbach processes and energy barriers of 10.5, 48, and 1232 K are determined for Dy 2 S@C 82 - C 3v (8). Dy 2 S@C 82 - C s (6) exhibits faster relaxation of magnetization with two barriers of 15.2 and 523 K. Ab initio calculations were used to interpret experimental data and compare the Dy-sulfide clusterfullerenes to other Dy-clusterfullerenes. The smallest and largest barriers are ascribed to the exchange/dipolar barrier and relaxation via crystal-field states, respectively, whereas an intermediate energy barrier of 48 K in Dy 2 S@C 82 - C 3v (8) is assigned to the local phonon mode, corresponding to the librational motion of the Dy 2 S cluster inside the carbon cage.

  10. Ketoprofen pharmacokinetics of R- and S-isomers in juvenile loggerhead sea turtles (Caretta caretta) after single intravenous and single- and multidose intramuscular administration.

    Science.gov (United States)

    Thompson, K A; Papich, M G; Higgins, B; Flanagan, J; Christiansen, E F; Harms, C A

    2018-04-01

    Ketoprofen is a nonsteroidal anti-inflammatory and analgesic agent that nonselectively inhibits cyclooxygenase, with both COX-1 and COX-2 inhibition. Recent studies on COX receptor expression in reptiles suggest that nonselective COX inhibitors may be more appropriate than more selective inhibitors in some reptiles, but few pharmacokinetic studies are available. The goal of this study was to determine single- and multidose (three consecutive days) pharmacokinetics of racemic ketoprofen administered intravenously and intramuscularly at 2 mg/kg in healthy juvenile loggerhead turtles (Caretta caretta). The S-isomer is the predominant isomer in loggerhead sea turtles, similar to most mammals, despite administration of a 50:50 racemic mixture. Multidose ketoprofen administration demonstrated no bioaccumulation; therefore, once-daily dosing will not require dose adjustment over time. S-isomer pharmacokinetic parameters determined in this study were C max of 10.1 μg/ml by IM injection, C 0 of 13.4 μg/ml by IV injection, AUC of 44.7 or 69.4 μg*hr/ml by IM or IV injection, respectively, and T½ of 2.8 or 3.6 hr by IM or IV injection, respectively. Total ketoprofen plasma concentrations were maintained for at least 12 hr above concentrations determined to be effective for rats and humans. A dose of 2 mg/kg either IM or IV every 24 hr is likely appropriate for loggerhead turtles. © 2017 John Wiley & Sons Ltd.

  11. Analysis of trace inorganic anions in weak acid salts by single pump cycling-column-switching ion chromatography.

    Science.gov (United States)

    Huang, Zhongping; Ni, Chengzhu; Zhu, Zhuyi; Pan, Zaifa; Wang, Lili; Zhu, Yan

    2015-05-01

    The application of ion chromatography with the single pump cycling-column-switching technique was described for the analysis of trace inorganic anions in weak acid salts within a single run. Due to the hydrogen ions provided by an anion suppressor electrolyzing water, weak acid anions could be transformed into weak acids, existing as molecules, after passing through the suppressor. Therefore, an anion suppressor and ion-exclusion column were adopted to achieve on-line matrix elimination of weak acid anions with high concentration for the analysis of trace inorganic anions in weak acid salts. A series of standard solutions consisting of target anions of various concentrations from 0.005 to 10 mg/L were analyzed, with correlation coefficients r ≥ 0.9990. The limits of detection were in the range of 0.67 to 1.51 μg/L, based on the signal-to-noise ratio of 3 and a 25 μL injection volume. Relative standard deviations for retention time, peak area, and peak height were all less than 2.01%. A spiking study was performed with satisfactory recoveries between 90.3 and 104.4% for all anions. The chromatographic system was successfully applied to the analysis of trace inorganic anions in five weak acid salts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Concentration and separation of trace metals from seawater using a single anion exchange bead

    International Nuclear Information System (INIS)

    Koide, M.; Lee, D.S.; Stallard, M.O.

    1984-01-01

    A technique has been developed for the quantitative adsorption of trace metals onto a single anion exchange bead. The application to the assay of trace metals in seawater was explored with the following radionuclides: 109 Cd, 103 Pd, 192 Ir, 195 Au, 237 Pu, and /sup 99m/Tc. The major ions, Na + , K + , Mg 2+ , and Ca 2+ exist primarily as positively charged species in seawater under nearly all conditions and did not interfere in the adsorption of anionic forms of trace metals onto the single bead. Three types of applications of the technique were investigated: (A) determination of metals in seawater by the direct adsorption onto a single bead without prior concentration, with or without a subsequent desorption from the bead (e.g., Cd, Zn); (B) determination of metals in seawater by the adsorption onto a single bead after a preconcentration step from several liters of seawater (e.g., Pd, Au, Ir), and (C) increasing the yield of Pu and Tc onto a single bead for improved sensitivity in mass spectrometric analyses

  13. On the structure and dynamics of water associated with single-supported zwitterionic and anionic membranes

    DEFF Research Database (Denmark)

    Miskowiec, A.; Buck, Z. N.; Hansen, Flemming Yssing

    2017-01-01

    We have used high-resolution quasielastic neutron scattering (QENS) to investigate the dynamics of water molecules (time scale of motion similar to ∼10-11- 10-9 s) in proximity to single-supported bilayers of the zwitterionic lipid DMPC (1,2-dimyristoyl-sn-glycero-3-phosphorylcholine......) and the anionic lipid DMPG (1,2-dimyristoyl-sn-glycero-3-phosphoglycerol) in the temperature range 160-295 K. For both membranes, the temperature dependence of the intensity of neutrons scattered elastically and incoherently from these samples indicates a series of freezing/melting transitions...... present at temperatures below the freezing point of bulk-like water. We then go on to determine the temperature dependence of the translational diffusion coefficient of the water associated with single-supported DMPG membranes containing two different amounts of water as we have previously done for DMPC...

  14. Determination of trace inorganic anions in weak acids by single-pump column-switching ion chromatography.

    Science.gov (United States)

    Zhu, Haibao; Chen, Huadong; Zhong, Yingying; Ren, Dandan; Qian, Yaling; Tang, Hongfang; Zhu, Yan

    2010-08-01

    Ion chromatography has been proposed for the determination of three common inorganic anions (chloride, nitrate, and sulfate) in nine weak acids (tartaric acid, citric acid, formic acid, acetic acid, metacetonic acid, butyric acid, butanedioic acid, hexafluorophosphoric acid, and salicylic acid) using a single pump, two valves, a single eluent, and a single conductivity detector. The present system uses ion exclusion, concentrator, and anion-exchange columns connected in series via 6-port and 10-port valves in a Dionex ICS-2100 ion chromatograph. The valves were switched for the determination of three inorganic anions from weak acids in a single chromatographic run. Sample matrices of weak acids with a series of concentrations can be investigated. Complete separations of the previously mentioned anions are demonstrated within 40 min. Under the optimum conditions, the relative standard deviation values ranged from 1.3 to 3.8%. The detection limits of the three inorganic anions (S/N = 3) were in the range of 0.3-1.7 microg/L. The recoveries were in the range of 75.2-117.6%. With this system, automation for routine analysis, short analysis time, and low cost can be achieved.

  15. Intercalation of single-strand oligonucleotides between nucleolipid anionic membranes: a neutron diffraction study.

    Science.gov (United States)

    Milani, Silvia; Berti, Debora; Dante, Silvia; Hauss, Thomas; Baglioni, Piero

    2009-04-07

    This contribution presents a neutron diffraction investigation of anionic lamellar phases composed of mixtures of 1-palmitoyl, 2-oleoyl phosphatidyl-nucleosides (POPN, where N is either adenosine or uridine), and POPC (1-palmitoyl,2-oleoyl-phosphatidyl-choline). Their behavior is studied for two different mole ratios and in the presence of nucleic acids. The samples are formed by the evaporation of liposomal dispersions prepared in water or in solutions containing single-strand oligonucleotides. Previous small angle X-ray scattering (SAXS) experiments on the system POPA/polyU (polyuridylic acid, high degree of polymerization, synthetic ribonucleic acid) proved that the insertion and ordering of the biopolymer in the phospholipid lamellae were driven by molecular recognition. In the present study, we extend the previous investigation to single-strand monodisperse oligonucleotides (50-mers). Structural details of the membranes were obtained from the analysis of the neutron diffraction scattering length density profiles. The evidence of direct and specific interactions, driven by molecular recognition between the nucleic polar heads of the nucleolipid and the single-strand nucleic acid, is strengthened by the comparison with identically charged bilayers formed by POPG/POPC. These results contribute to the understanding of the parameters governing the interactions between nucleolipid membranes and oligonucleotides, providing a novel strategy for the design of lipid-based vehicles for nucleic acids.

  16. On the freezing behavior and diffusion of water in proximity to single-supported zwitterionic and anionic bilayer lipid membranes

    DEFF Research Database (Denmark)

    Miskowiec, A.; Buck, Z. N.; Brown, M. C.

    2014-01-01

    We compare the freezing/melting behavior of water hydrating single-supported bilayers of a zwitterionic lipid DMPC with that of an anionic lipid DMPG. For both membranes, the temperature dependence of the elastically scattered neutron intensity indicates distinct water types undergoing...

  17. On the structure and dynamics of water associated with single-supported zwitterionic and anionic membranes

    Science.gov (United States)

    Miskowiec, A.; Buck, Z. N.; Hansen, F. Y.; Kaiser, H.; Taub, H.; Tyagi, M.; Diallo, S. O.; Mamontov, E.; Herwig, K. W.

    2017-03-01

    We have used high-resolution quasielastic neutron scattering (QENS) to investigate the dynamics of water molecules (time scale of motion ˜10-11-10-9 s) in proximity to single-supported bilayers of the zwitterionic lipid DMPC (1,2-dimyristoyl-sn-glycero-3-phosphorylcholine) and the anionic lipid DMPG (1,2-dimyristoyl-sn-glycero-3-phosphoglycerol) in the temperature range 160-295 K. For both membranes, the temperature dependence of the intensity of neutrons scattered elastically and incoherently from these samples indicates a series of freezing/melting transitions of the membrane-associated water, which have not been observed in previous studies of multilayer membranes. We interpret these successive phase transitions as evidence of different types of water that are common to the two membranes and which are defined by their local environment: bulk-like water located furthest from the membrane and two types of confined water in closer proximity to the lipids. Specifically, we propose a water type termed "confined 2" located within and just above the lipid head groups of the membrane and confined 1 water that lies between the bulk-like and confined 2 water. Confined 1 water is only present at temperatures below the freezing point of bulk-like water. We then go on to determine the temperature dependence of the translational diffusion coefficient of the water associated with single-supported DMPG membranes containing two different amounts of water as we have previously done for DMPC. To our knowledge, there have been no previous studies comparing the dynamics of water in proximity to zwitterionic and anionic membranes. Our analysis of the water dynamics of the DMPG and DMPC membranes supports the classification of water types that we have inferred from their freezing/melting behavior. However, just as we observe large differences in the freezing/melting behavior between these model membranes for the same water type, our measurements demonstrate variation between these

  18. EPR and photoluminescence study of irradiated anion-defective alumina single crystals

    Science.gov (United States)

    Kortov, V. S.; Ananchenko, D. V.; Konev, S. F.; Pustovarov, V. A.

    2017-09-01

    Electron paramagnetic resonance (EPR) and photoluminescence (PL) spectra of anion-defective alumina single crystals were measured. Exposure to a dose 10 Gy-1 kGy causes isotropic EPR signal of a complex form, this signal contains narrow and broad components. At the same time, in the PL spectrum alongside with a band of F+-centers (3.8 eV) an additional emission band with the maximum of 2.25 eV is registered. This band corresponds to aggregate F22+-centers which were create under irradiation. By comparing measurements in EPR and PL spectra with further stepped annealing in the temperature range of 773-1473 K of the samples exposed to the same doses, we were able to conclude that a narrow component of isotropic EPR signal is associated with the formation of paramagnetic F22+-centers under irradiation. A wide component can be caused by deep hole traps which are created by a complex defect (VAl2- - F+) with a localized hole.

  19. Single-Crystal-to-Single-Crystal Anion Exchange in a Gadolinium MOF: Incorporation of POMs and [AuCl4]−

    Directory of Open Access Journals (Sweden)

    Javier López-Cabrelles

    2016-04-01

    Full Text Available The encapsulation of functional molecules inside porous coordination polymers (also known as metal-organic frameworks, MOFs has become of great interest in recent years at the field of multifunctional materials. In this article, we present a study of the effects of size and charge in the anion exchange process of a Gd based MOF, involving molecular species like polyoxometalates (POMs, and [AuCl4]−. This post-synthetic modification has been characterized by IR, EDAX, and single crystal diffraction, which have provided unequivocal evidence of the location of the anion molecules in the framework.

  20. Bis-picolinamide Ruthenium(III) Dihalide Complexes: Dichloride-to-Diiodide Exchange Generates Single trans Isomers with High Potency and Cancer Cell Selectivity.

    Science.gov (United States)

    Basri, Aida M; Lord, Rianne M; Allison, Simon J; Rodríguez-Bárzano, Andrea; Lucas, Stephanie J; Janeway, Felix D; Shepherd, Helena J; Pask, Christopher M; Phillips, Roger M; McGowan, Patrick C

    2017-05-05

    A library of new bis-picolinamide ruthenium(III) dihalide complexes of the type [RuX 2 L 2 ] (X=Cl or I, L=picolinamide) have been synthesised and characterised. The complexes exhibit different picolinamide ligand binding modes, whereby one ligand is bound (N,N) and the other bound (N,O). Structural studies revealed a mixture of cis and trans isomers for the [RuCl 2 L 2 ] complexes but upon a halide exchange reaction to yield [RuI 2 L 2 ], only single trans isomers were detected. High cytotoxic activity against human cancer cell lines was observed, with the potencies of some complexes similar to or better than cisplatin. The conversion to [RuI 2 L 2 ] substantially increased the activity towards cancer cell lines by more than twelvefold. The [RuI 2 L 2 ] complexes displayed potent activity against the A2780cis (cisplatin-resistant human ovarian cancer) cell line, with a more than fourfold higher potency than cisplatin. Equitoxic activity was observed against normoxic and hypoxic cancer cells, which indicates the potential to eradicate both the hypoxic and aerobic fractions of solid tumours with similar efficiency. The activity of selected complexes against non-cancer ARPE-19 cells was also tested. The [RuI 2 L 2 ] complexes were found to be more potent than the [RuCl 2 L 2 ] analogues and also more selective towards cancer cells with a selectivity factor in excess of sevenfold. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Temporary Anion States of Ethene Interacting with Single Molecules of Methane, Ethane, and Water.

    Science.gov (United States)

    Sommerfeld, Thomas; Melugin, Joshua B; Ehara, Masahiro

    2018-03-08

    When an excess electron is added into the π* orbital of ethene, the resulting anion decays by electron autodetachment; that is, it represents an electronic state referred to as a temporary anion or resonance state. Here, the influence of a cluster environment on the energy and lifetime of this state is investigated. The clusters considered are ethene···CH 4 , ethene···C 2 H 6 , and ethene···H 2 O. Most of these clusters are systematically constructed so that the solvent interacts with the π system in a specific way, and are thus by construction not minima with respect to all intermolecular degrees of freedom. However, for water, in addition, a minimal energy structure is examined. Systematic variation of the solvent and solvation geometry allows us to identify trends regarding effects due to polarizability, excluded volume, and polarity of the solvent molecules. The resonance parameters of ethene and all temporary cluster anions are computed with the symmetry-adapted cluster-configuration interaction electronic structure method in combination with a complex absorbing potential. This method is well-established for small to intermediate sized molecules. In addition to the study of the solvation effects themselves, the question of how many basis functions are needed on the closed-shell solvating unit is examined.

  2. Negative Ion MALDI Mass Spectrometry of Polyoxometalates (POMs): Mechanism of Singly Charged Anion Formation and Chemical Properties Evaluation

    Science.gov (United States)

    Boulicault, Jean E.; Alves, Sandra; Cole, Richard B.

    2016-08-01

    MALDI-MS has been developed for the negative ion mode analysis of polyoxometalates (POMs). Matrix optimization was performed using a variety of matrix compounds. A first group of matrixes offers MALDI mass spectra containing abundant intact singly charged anionic adduct ions, as well as abundant in-source fragmentations at elevated laser powers. A relative ranking of the ability to induce POM fragmentation is found to be: DAN > CHCA > CNA > DIT> HABA > DCTB > IAA. Matrixes of a second group provide poorer quality MALDI mass spectra without observable fragments. Sample preparation, including the testing of salt additives, was performed to optimize signals for a model POM, POMc12, the core structure of which bears four negative charges. The matrix 9-cyanoanthracene (CNA) provided the best signals corresponding to singly charged intact POMc12 anions. Decompositions of these intact anionic species were examined in detail, and it was concluded that hydrogen radical-induced mechanisms were not prevalent, but rather that the observed prompt fragments originate from transferred energy derived from initial electronic excitation of the CNA matrix. Moreover, in obtained MALDI mass spectra, clear evidence of electron transfer to analyte POM species was found: a manifestation of the POMs ability to readily capture electrons. The affinity of polyanionic POMc12 toward a variety of cations was evaluated and the following affinity ranking was established: Fe3+ > Al3+ > Li+ > Ga3+ > Co2+ > Cr3+ > Cu2+ > [Mn2+, Mg2+] > [Na+, K+]. Thus, from the available cationic species, specific adducts are preferentially formed, and evidence is given that these higher affinity POM complexes are formed in the gas phase during the early stages of plume expansion.

  3. Capillary electrophoretic enantioseparation of basic drugs using a new single-isomer cyclodextrin derivative and theoretical study of the chiral recognition mechanism.

    Science.gov (United States)

    Liu, Yongjing; Deng, Miaoduo; Yu, Jia; Jiang, Zhen; Guo, Xingjie

    2016-05-01

    A novel single-isomer cyclodextrin derivative, heptakis {2,6-di-O-[3-(1,3-dicarboxyl propylamino)-2-hydroxypropyl]}-β-cyclodextrin (glutamic acid-β-cyclodextrin) was synthesized and used as a chiral selector in capillary electrophoresis for the enantioseparation of 12 basic drugs, including terbutaline, clorprenaline, tulobuterol, clenbuterol, procaterol, carvedilol, econazole, miconazole, homatropine methyl bromide, brompheniramine, chlorpheniramine and pheniramine. The primary factors affecting separation efficiency, which include the background electrolyte pH, the concentration of glutamic acid-β-cyclodextrin and phosphate buffer concentration, were investigated. Satisfactory enantioseparations were obtained using an uncoated fused-silica capillary of 50 cm (effective length 40 cm) × 50 μm id with 120 mM phosphate buffer (pH 2.5-4.0) containing 0.5-4.5 mM glutamic acid-β-cyclodextrin as background electrolyte. A voltage of 20 kV was applied and the capillary temperature was kept at 20°C. The results proved that glutamic acid-β-cyclodextrin was an effective chiral selector for studied 12 basic drugs. Moreover, the possible chiral recognition mechanism of brompheniramine, chlorpheniramine and pheniramine on glutamic acid-β-cyclodextrin was investigated using the semi-empirical Parametric Method 3. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. A Single-Molecule Propyne Trap: Highly Efficient Removal of Propyne from Propylene with Anion-Pillared Ultramicroporous Materials.

    Science.gov (United States)

    Yang, Lifeng; Cui, Xili; Yang, Qiwei; Qian, Siheng; Wu, Hui; Bao, Zongbi; Zhang, Zhiguo; Ren, Qilong; Zhou, Wei; Chen, Banglin; Xing, Huabin

    2018-03-01

    Propyne/propylene (C 3 H 4 /C 3 H 6 ) separation is a critical process for the production of polymer-grade C 3 H 6 . However, optimization of the structure of porous materials for the highly efficient removal of C 3 H 4 from C 3 H 6 remains challenging due to their similar structures and ultralow C 3 H 4 concentration. Here, it is first reported that hybrid ultramicroporous materials with pillared inorganic anions (SiF 6 2- = SIFSIX, NbOF 5 2- = NbOFFIVE) can serve as highly selective C 3 H 4 traps for the removal of trace C 3 H 4 from C 3 H 6 . Especially, it is revealed that the pyrazine-based ultramicroporous material with square grid structure for which the pore shape and functional site disposition can be varied in 0.1-0.5 Å scale to match both the shape and interacting sites of guest molecule is an interesting single-molecule trap for C 3 H 4 molecule. The pyrazine-based single-molecule trap enables extremely high C 3 H 4 uptake under ultralow concentration (2.65 mmol g -1 at 3000 ppm, one C 3 H 4 per unit cell) and record selectivity over C 3 H 6 at 298 K (>250). The single-molecule binding mode for C 3 H 4 within ultramicroporous material is validated by X-ray diffraction experiments and modeling studies. The breakthrough experiments confirm that anion-pillared ultramicroporous materials set new benchmarks for the removal of ultralow concentration C 3 H 4 (1000 ppm on SIFSIX-3-Ni, and 10 000 ppm on SIFSIX-2-Cu-i) from C 3 H 6 . © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Benzene and its Isomers

    Indian Academy of Sciences (India)

    Benzene and its Isomers atomic weights and availability of improved analytical methods. At this time the .... geometry. Forcing them in cyclic structures would lead to signifi- cant strain. Bicyclic structures do not easily accommodate double bonds at bridgehead positions (Bredt's rule). Many of the polycy- clic isomers clearly ...

  6. High-throughput investigation of single and binary protein adsorption isotherms in anion exchange chromatography employing multivariate analysis.

    Science.gov (United States)

    Field, Nicholas; Konstantinidis, Spyridon; Velayudhan, Ajoy

    2017-08-11

    The combination of multi-well plates and automated liquid handling is well suited to the rapid measurement of the adsorption isotherms of proteins. Here, single and binary adsorption isotherms are reported for BSA, ovalbumin and conalbumin on a strong anion exchanger over a range of pH and salt levels. The impact of the main experimental factors at play on the accuracy and precision of the adsorbed protein concentrations is quantified theoretically and experimentally. In addition to the standard measurement of liquid concentrations before and after adsorption, the amounts eluted from the wells are measured directly. This additional measurement corroborates the calculation based on liquid concentration data, and improves precision especially under conditions of weak or moderate interaction strength. The traditional measurement of multicomponent isotherms is limited by the speed of HPLC analysis; this analytical bottleneck is alleviated by careful multivariate analysis of UV spectra. Copyright © 2017. Published by Elsevier B.V.

  7. Single, binary and multi-component adsorption of some anions and heavy metals on environmentally friendly Carpobrotus edulis plant.

    Science.gov (United States)

    Chiban, Mohamed; Soudani, Amina; Sinan, Fouad; Persin, Michel

    2011-02-01

    A low-cost adsorbent and environmentally friendly adsorbent from Carpobrotus edulis plant was used for the removal of NO(3)(-), H(2)PO(4)(-), Pb(2+) and Cd(2+) ions from single, binary and multi-component systems. The efficiency of the adsorbent was studied using batch adsorption technique under different experimental conditions by varying parameters such as pH, initial concentration and contact time. In single component systems, the dried C. edulis has the highest affinity for Pb(2+), followed by NO(3)(-), Cd(2+) and H(2)PO(4)(-), with adsorption capacities of 175mg/g, 125mg/g, 28mg/g and 26mg/g, respectively. These results showed that the adsorption of NO(3)(-) and H(2)PO(4)(-) ions from single and binary component systems can be successfully described by Langmuir and Freundlich isotherms. Freundlich adsorption model, showed the best fit to the single and binary experimental adsorption data. These results also indicated that the adsorption yield of Pb(2+) ion was reduced by the presence of Cd(2+) ion in binary metal mixture. The competitive adsorption of NO(3)(-), H(2)PO(4)(-), Pb(2+) and Cd(2+) ions on dried C. edulis plant shows that NO(3)(-) and H(2)PO(4)(-) anions are able to adsorb on different free binding sites and Pb(2+) and Cd(2+) cations are able to adsorb on the same active sites of C. edulis particles. The dried C. edulis was found to be efficient in removing nitrate, phosphate, cadmium and lead from aqueous solution as compared to other adsorbents already used for the removal of these ions. Copyright © 2010 Elsevier B.V. All rights reserved.

  8. Seniority isomers in nuclei

    International Nuclear Information System (INIS)

    Van Isacker, P

    2011-01-01

    Seniority isomers are nuclear states with an electromagnetic decay that is hindered by selection rules related to the seniority quantum number. A simple analysis is presented of their possible formation with reference to the nickel isotopes 70–76 Ni and the N = 50 isotones from molybdenum to cadmium. It is shown that the existence of seniority isomers in a j = 9/2 shell is predominantly governed by the quadrupole pairing matrix element of the nucleon-nucleon interaction. The analysis is generalized to shells with larger j.

  9. Benzene and its Isomers

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 6; Issue 5. Benzene and its Isomers - How many Structures can we Draw for C6H6? Gopalpur Nagendrappa. General Article Volume 6 Issue 5 May 2001 pp 74-78. Fulltext. Click here to view fulltext PDF. Permanent link:

  10. Absorption spectrum of the firefly luciferin anion isolated in vacuo.

    Science.gov (United States)

    Støchkel, Kristian; Milne, Bruce F; Brøndsted Nielsen, Steen

    2011-03-24

    The excited-state physics of the firefly luciferin anion depends on its chemical environment, and it is therefore important to establish the intrinsic behavior of the bare ion. Here we report electronic absorption spectra of the anion isolated in vacuo obtained at an electrostatic ion storage ring and an accelerator mass spectrometer where ionic dissociation is monitored on a long time scale (from 33 μs and up to 3 ms) and on a short time scale (0-3 μs), respectively. In the ring experiment the yield of all neutrals (mainly CO(2)) as a function of wavelength was measured whereas in the single pass experiment, the abundance of daughter ions formed after loss of CO(2) was recorded to provide action spectra. We find maxima at 535 and 265 nm, and that the band shape is largely determined by the sampling time interval, which is due to the kinetics of the dissociation process. Calculations at the TD-B3LYP/TZVPP++ level predict maximum absorption at 533 and 275 nm for the carboxylate isomer in excellent agreement with the experimental findings. The phenolate isomer lies higher in energy by 0.22 eV, and also its absorption maximum is calculated to be at 463 nm, which is far away from the experimental value. Our data serve to benchmark future theoretical models for bioluminescence from fireflies.

  11. Single crystal structures and theoretical calculations of uranium endohedral metallofullerenes (U@C2n , 2n = 74, 82) show cage isomer dependent oxidation states for U.

    Science.gov (United States)

    Cai, Wenting; Morales-Martínez, Roser; Zhang, Xingxing; Najera, Daniel; Romero, Elkin L; Metta-Magaña, Alejandro; Rodríguez-Fortea, Antonio; Fortier, Skye; Chen, Ning; Poblet, Josep M; Echegoyen, Luis

    2017-08-01

    Charge transfer is a general phenomenon observed for all endohedral mono-metallofullerenes. Since the detection of the first endohedral metallofullerene (EMF), La@C 82 , in 1991, it has always been observed that the oxidation state of a given encapsulated metal is always the same, regardless of the cage size. No crystallographic data exist for any early actinide endohedrals and little is known about the oxidation states for the few compounds that have been reported. Here we report the X-ray structures of three uranium metallofullerenes, U@ D 3h -C 74 , U@ C 2 (5)-C 82 and U@ C 2v (9)-C 82 , and provide theoretical evidence for cage isomer dependent charge transfer states for U. Results from DFT calculations show that U@ D 3h -C 74 and U@ C 2 (5)-C 82 have tetravalent electronic configurations corresponding to U 4+ @ D 3h -C 74 4- and U 4+ @ C 2 (5)-C 82 4- . Surprisingly, the isomeric U@ C 2v (9)-C 82 has a trivalent electronic configuration corresponding to U 3+ @ C 2v (9)-C 82 3- . These are the first X-ray crystallographic structures of uranium EMFs and this is first observation of metal oxidation state dependence on carbon cage isomerism for mono-EMFs.

  12. Substitution effects on the absorption spectra of nitrophenolate isomers.

    Science.gov (United States)

    Wanko, Marius; Houmøller, Jørgen; Støchkel, Kristian; Suhr Kirketerp, Maj-Britt; Petersen, Michael Åxman; Nielsen, Mogens Brøndsted; Nielsen, Steen Brøndsted; Rubio, Angel

    2012-10-05

    Charge-transfer excitations highly depend on the electronic coupling between the donor and acceptor groups. Nitrophenolates are simple examples of charge-transfer systems where the degree of coupling differs between ortho, meta and para isomers. Here we report the absorption spectra of the isolated anions in vacuo to avoid the complications of solvent effects. Gas-phase action spectroscopy was done with two different setups, an electrostatic ion storage ring and an accelerator mass spectrometer. The results are interpreted on the basis of CC2 quantum chemical calculations. We identified absorption maxima at 393, 532, and 399 nm for the para, meta, and ortho isomer, respectively, with the charge-transfer transition into the lowest excited singlet state. In the meta isomer, this π-π* transition is strongly redshifted and its oscillator strength reduced, which is related to the pronounced charge-transfer character, as a consequence of the topology of the conjugated π-system. Each isomer's different charge distribution in the ground state leads to a very different solvent shift, which in acetonitrile is bathochromic for the para and ortho, but hypsochromic for the meta isomer.

  13. Radical anion structure of β-halogen-substituted acetamides in X-ray-irradiated single crystals: an INDO and EPR study

    International Nuclear Information System (INIS)

    Samskog, P.O.; Kispert, L.D.

    1984-01-01

    The anion radicals of bromodifluoroacetamide and chlorodifluoroacetamide are investigated by using the INDO method and EPR spectroscopy. INDO calculations for the anions give a spin density distribution in agreement with that suggested from experiment. Results of the analyses show that the unpaired electron occupies the sigma* orbital composed of the rho orbitals, along the C/sub β/-X bond, on the carbon and the unique halogen atoms. The results are compared to the radical anion in trifluoroacetamide. The electronic structure of SCF 2 CONH 2 - radical anions is a π-radical anion when X = F and a sigma*-radical anion when X = Cl and Br. 2 figures, 4 tables

  14. Isomer effect on the near-infrared electrochromism of anthraquinone imides

    International Nuclear Information System (INIS)

    Yao, Bin; Chen, Fengkun; Jiang, Hong; Zhang, Jie; Wan, Xinhua

    2015-01-01

    Graphical abstract: Display Omitted - Highlights: • Two pairs of unsubstituted isomers (Ia and Ib) and nitro-substituted isomers (IIa and IIb) of anthraquinone imides (AQIs), which are a unique type of cathodically-colouring NIR electrochromic materials bearing both quinone and imide moieties, were synthesized. • Isomer effect on the NIR electrochromism of n-type optoelectric materials was first approached. • A meaningful reference to design cathodically active NIR EC materials, in which the molecular planarity and the orientation of polar groups are two key elements must to be carefully considered, is provided. - Abstract: To deeply explore the interplay between molecular structure and near-infrared electrochromism of anthraquinone imides, two pairs of unsubstituted isomers (Ia and Ib) and nitro-substituted isomers (IIa and IIb) of anthraquinone imides were synthesized, in which the molecules Ia and IIa took more linear shapes than Ib and IIb. Cyclic voltammetry and spectroelectrochemistry were combined to investigate their electrochemical properties. Cyclic voltammetry showed that Ib and IIb revealed decreased first reduction potentials and low cyclic stability compared to their isomers, indicating that the isomerization weakened the stabilization effect. Upon one-electron reduction, both the absorption wavelengths and absorption intensities of radical anions were greatly dependent on the structures of isomers. The radical anions of Ia, IIa, and IIb illustrated NIR absorptions peaked at 820, 1260, and 1380 nm, respectively, but that of Ib exhibited only weak absorption in the visible region centered at 660 nm. Gaussian calculations suggested that the electrons were delocalized over the whole molecular skeletons of Ia and IIa radical anions, but the effective conjugation length was interrupted on the imide section in both Ib and IIb. The isomer effects on the effective conjugation length and electron density distribution were considered to rationalize the

  15. ANIONS FUNCTIONS IN TRANSITION METALS COORDINATION COMPOUNDS

    Directory of Open Access Journals (Sweden)

    T. V. Koksharova

    2016-04-01

    Full Text Available The effect of anions on the structure and properties of coordination compounds of transition metals has been discussed. The examples of changes in the composition of the formed complexes by replacement of the anion are given: metal ratio to a neutral ligand, the composition of the inner sphere, the direction of template synthesis. Anions can determine the presence of isomers in complexes with different ligands. Examples of conformational, ionization isomerism, inner sphere bond isomerization are given. The nature of the coordination polyhedron is highly sensitive to the replacement of the anion too. Examples of coordination compounds where the anion change causes a change in coordination capacity of neutral ligands and the strength of their bonds with the metal, coordination number and geometry of the inner sphere, the organization of molecular structures (the structure of the hydrogen bond networks and the degree of polymerization, crystal packing. The anions significantly affect the binding of the solvent molecules, complexes magnetic and luminescent properties, they can change the compound color, the mechanisms of thermolysis. Anions make a very noticeable influence on possible redox processes following the complexation in some cases. Anions in the coordination sphere can change catalytic and biochemical processes as well as the ways of interaction of metal ions with drugs.

  16. Adsorption behavior of modified Iron stick yam skin with Polyethyleneimine as a potential biosorbent for the removal of anionic dyes in single and ternary systems at low temperature.

    Science.gov (United States)

    Zhang, Yan-Zhuo; Li, Jun; Zhao, Jing; Bian, Wei; Li, Yun; Wang, Xiu-Jie

    2016-12-01

    The skin of Iron stick yam (ISY) was modified with Polyethyleneimine (ISY@PEI) and evaluated for use as a potential biosorbent to remove the anionic dyes Sunset yellow (SY), Lemon yellow (LY), and Carmine (CM) from wastewater under low temperature conditions (5-15°C) in single and ternary dye systems. Both in the single and ternary systems, experimental data showed that adsorption capacity reached the highest value at 5°C, and adsorption capacity decreased when the temperature increased (10-50°C). The equilibrium data fitted very well to the Langmuir model and the extended Langmuir isotherm, for the single and ternary systems, respectively. The maximum adsorption capability was 138.92, 476.31, and 500.13mg/g for LY, SY, and CM, respectively, in a single system and 36.63, 303.31, and 294.12mg/g for LY, SY, and CM, respectively, in a ternary system. The adsorption followed pseudo-second-order kinetics. The thermodynamic parameters indicated that it was a spontaneous and exothermic process. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Projected shell model description for nuclear isomers

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Y. [Department of Physics, Shanghai Jiao Tong University, Shanghai 200240, Popular Republic (China)

    2008-12-15

    The study of nuclear isomer properties is a current research focus. To describe isomers, we present a method based on the Projected Shell Model. Two kinds of isomers, {kappa}-isomers and shape isomers, are discussed. For the {kappa}-isomer treatment, {kappa}-mixing is properly implemented in the model. It is found however that in order to describe the strong {kappa}-violation more efficiently, it may be necessary to further introduce triaxiality into the shell model basis. To treat shape isomers, a scheme is outlined which allows mixing those configurations belonging to different shapes. (Author)

  18. Single turnover of substrate-bound ferric cysteine dioxygenase with superoxide anion: enzymatic reactivation, product formation, and a transient intermediate.

    Science.gov (United States)

    Crawford, Joshua A; Li, Wei; Pierce, Brad S

    2011-11-29

    Cysteine dioxygenase (CDO) is a non-heme mononuclear iron enzyme that catalyzes the O(2)-dependent oxidation of L-cysteine (Cys) to produce cysteine sulfinic acid (CSA). In this study we demonstrate that the catalytic cycle of CDO can be "primed" by one electron through chemical oxidation to produce CDO with ferric iron in the active site (Fe(III)-CDO, termed 2). While catalytically inactive, the substrate-bound form of Fe(III)-CDO (2a) is more amenable to interrogation by UV-vis and EPR spectroscopy than the 'as-isolated' Fe(II)-CDO enzyme (1). Chemical-rescue experiments were performed in which superoxide (O(2)(•-)) anions were introduced to 2a to explore the possibility that a Fe(III)-superoxide species represents the first intermediate within the catalytic pathway of CDO. In principle, O(2)(•-) can serve as a suitable acceptor for the remaining 3-electrons necessary for CSA formation and regeneration of the active Fe(II)-CDO enzyme (1). Indeed, addition of O(2)(•-) to 2a resulted in the rapid formation of a transient species (termed 3a) observable at 565 nm by UV-vis spectroscopy. The subsequent decay of 3a is kinetically matched to CSA formation. Moreover, a signal attributed to 3a was also identified using parallel mode X-band EPR spectroscopy (g ~ 11). Spectroscopic simulations, observed temperature dependence, and the microwave power saturation behavior of 3a are consistent with a ground state S = 3 from a ferromagnetically coupled (J ~ -8 cm(-1)) high-spin ferric iron (S(A) = 5/2) with a bound radical (S(B) = 1/2), presumably O(2)(•-). Following treatment with O(2)(•-), the specific activity of recovered CDO increased to ~60% relative to untreated enzyme.

  19. Initiation and growth of a single pit on 316L stainless steel: Influence of SO42- and ClO4- anions

    International Nuclear Information System (INIS)

    Aouina, N.; Huet, F.; Joiret, S.; Perrot, H.; Vivier, V.; Balbaud-Celerier, F.; Rouillard, F.

    2013-01-01

    In this paper, an ion micro dispenser (IMD) was used to initiate a single pit by generating chloride anions above a 316L stainless steel electrode in either H 2 SO 4 or HClO 4 electrolyte. The current variations with respect to time provided an unambiguous characterization of the single pit evolution. Different pit shapes were observed depending on both the nature of the electrolyte and potential applied to the electrode. Substituting SO 4 2- for ClO 4 - gave smaller (in diameter) but deeper pits at the early stage of pitting. However, when using a different setup that allows the sustaining of the pit propagation with a continuous supply of Cl - , the deeper pits were observed in HClO 4 rather than H 2 SO 4 . The formation of an iron sulphate salt film at the bottom of the pit by precipitation of dissolution products in H 2 SO 4 slowed down the corrosion rate. At high potentials, the repassivation mechanism outweighed the metal dissolution in the ClO 4 - containing solution. (authors)

  20. Constitutional Isomers of Pentahydroxy-Functionalized Pillar[5]arenes: Synthesis, Characterization, and Crystal Structures.

    Science.gov (United States)

    Al-Azemi, Talal F; Vinodh, Mickey; Alipour, Fatemeh H; Mohamod, Abdirahman A

    2017-10-20

    We herein report the preparation of constitutional isomers of pentahydroxy-functionalized pillar[5]arenes via the deprotection of their benzylated derivatives by catalytic hydrogenation. The structures of the obtained isomers were then established using single crystal X-ray diffraction. We also found that the yield distribution of the different constitutional isomers was dependent on the nature of the substitution, as revealed by HPLC analysis of the crude mixture. Finally, further characterization of the separated constitutional isomers indicated that they possess different melting points, NMR spectra, crystal structures, and stacking patterns in the solid state.

  1. Total synthesis of ascididemin via anionic cascade ring closure

    DEFF Research Database (Denmark)

    Petersen, Ida Nymann; Crestey, François; Kristensen, Jesper Langgaard

    2012-01-01

    A new and convergent synthesis of ascididemin is presented. Using an anionic cascade ring closure as the key step, this natural product is obtained in 45% overall yield in just 6 steps starting from 2'-fluoroacetophenone. This new approach was extended to the synthesis of a new isomer...

  2. Ultrahigh performance liquid chromatography-triple quadrupole mass spectrometry inhibitors fishing assay: a novel method for simultaneously screening of xanthine oxidase inhibitor and superoxide anion scavenger in a single analysis.

    Science.gov (United States)

    Liu, Shu; Xing, Junpeng; Zheng, Zhong; Song, Fengrui; Liu, Zhiqiang; Liu, Shuying

    2012-02-17

    Xanthine oxidase (XOD) inhibitors and superoxide anion scavengers play an important role in the treatment of gout and the inhibition of many diseases related to superoxide anion. The respective quantitation of uric acid and superoxide anion by traditional spectroscopic methods is routine in XOD inhibitors and superoxide anion scavengers screening at laboratories worldwide. In the present study, we established an ultrahigh performance liquid chromatography and triple quadrupole mass spectrometry (UHPLC-TQ-MS) method of higher accuracy and speed that combines screening of superoxide anion scavenger and XOD inhibitor in a single analysis by adding WST-1 (2-(4-iodophenyl)-3-(4-nitrophenyl)-5-(2,4-disulfophenyl)-2H-tetrazolium sodium salt) to the enzymatic reaction. We applied the established method to determine the XOD inhibitory activities and superoxide scavenging activities of some herbal extracts and compounds from natural products, which could be classified into six groups based on the results of the assay. Our innovative protocol is fast, accurate and robust. Moreover, it can eliminate false positive and false negative results which may occur in the traditional spectroscopic methods. Copyright © 2011 Elsevier B.V. All rights reserved.

  3. Can voltammetry distinguish glycan isomers?

    Czech Academy of Sciences Publication Activity Database

    Trefulka, Mojmír; Paleček, Emil

    2015-01-01

    Roč. 69, č. 1 (2015), s. 241-244 ISSN 0366-6352 R&D Projects: GA ČR(CZ) GAP301/11/2055 Institutional support: RVO:68081707 Keywords : oligosaccharide isomers * Os(VI) complexes * chemical modification Subject RIV: BO - Biophysics Impact factor: 1.326, year: 2015

  4. Single particle electron microscopy analysis of the bovine anion exchanger 1 reveals a flexible linker connecting the cytoplasmic and membrane domains.

    Directory of Open Access Journals (Sweden)

    Jiansen Jiang

    Full Text Available Anion exchanger 1 (AE1 is the major erythrocyte membrane protein that mediates chloride/bicarbonate exchange across the erythrocyte membrane facilitating CO₂ transport by the blood, and anchors the plasma membrane to the spectrin-based cytoskeleton. This multi-protein cytoskeletal complex plays an important role in erythrocyte elasticity and membrane stability. An in-frame AE1 deletion of nine amino acids in the cytoplasmic domain in a proximity to the membrane domain results in a marked increase in membrane rigidity and ovalocytic red cells in the disease Southeast Asian Ovalocytosis (SAO. We hypothesized that AE1 has a flexible region connecting the cytoplasmic and membrane domains, which is partially deleted in SAO, thus causing the loss of erythrocyte elasticity. To explore this hypothesis, we developed a new non-denaturing method of AE1 purification from bovine erythrocyte membranes. A three-dimensional (3D structure of bovine AE1 at 2.4 nm resolution was obtained by negative staining electron microscopy, orthogonal tilt reconstruction and single particle analysis. The cytoplasmic and membrane domains are connected by two parallel linkers. Image classification demonstrated substantial flexibility in the linker region. We propose a mechanism whereby flexibility of the linker region plays a critical role in regulating red cell elasticity.

  5. Anion-exchange and anthracene-encapsulation within copper(II) and manganese(II)-triazole metal-organic confined space in a single crystal-to-single crystal transformation fashion.

    Science.gov (United States)

    Liu, Ju-Yan; Wang, Qian; Zhang, Li-Jun; Yuan, Bin; Xu, Yao-Yao; Zhang, Xin; Zhao, Cong-Ying; Wang, Dan; Yuan, Yue; Wang, Ying; Ding, Bin; Zhao, Xiao-Jun; Yue, Min Min

    2014-06-16

    A new multidentate ligand 1-(9-(1H-1,2,4-triazol-1-yl)anthracen-10-yl)-1H-1,2,4-triazole (tatrz) was designed and synthesized. Using tatrz as a building block, three novel coordination frameworks, namely, {[Cu(tatrz)2(NO3)2]·(CH3OH)·4H2O}n (1), {[Cu(tatrz)2(H2O)2](BF4)2}n (2), and [Mn(tatrz)2(SCN)2(CH3OH)]·2H2O (3) can be isolated. Anion-exchange experiment indicates that NO3(-) anions in the two-dimensional (2D) copper framework of 1 can be completely exchanged by ClO4(-) in an irreversible single crystal-to-single crystal (SC-SC) transformation fashion, as evidenced by the anion-exchange products of {[Cu(tatrz)2(H2O)2](ClO4)2·4CH3OH} (1a). Further, if 1a was employed as a precursor in N,N-dimethylformamide (DMF), an isomorphic solvate of {[Cu(tatrz)2(DMF)2](ClO4)2·2H2O}n (1b) can be generated during the reversible dynamic transformation process. When 1 was immersed in CH3OH, a distinct 2D layer {[Cu(tatrz)2(NO3)2]·4.4CH3OH·0.6H2O}n (1c) was isolated. Interestingly, the solvent-exchange conversion is also invertible between 1 and 1c, which exhibits spongelike dynamic behavior with retention of crystalline integrity. If the 2-fold interpenetrating three-dimensional (3D) framework 2 is selected, it can be transformed into another 2-fold interpenetrating 3D framework {[Cu(tatrz)2(H2O)2](ClO4)2·5.56H2O}n (2a) in a reversible SC-SC transformation fashion. However, when the light yellow crystals of mononuclear complex 3 were exposed to trichloromethane containing aromatic organic anthracene (atan), through our careful observation, the crystals of 3 were dissolved and reassembled into dark brown crystals of 2D crystalline coordination framework {[Mn(tatrz)2(SCN)2]·(atan)}n (3a). X-ray diffraction revealed that in 3a, atan acting as an organic template was encapsulated in the confined space of the 2D grid. Luminescent measurements illustrate that 3a is the first report of multidimensional polymers based on triazole derivatives as luminescent probes of Mg(2+).

  6. Treatment of isomers in nucleosynthesis codes

    Science.gov (United States)

    Reifarth, René; Fiebiger, Stefan; Göbel, Kathrin; Heftrich, Tanja; Kausch, Tanja; Köppchen, Christoph; Kurtulgil, Deniz; Langer, Christoph; Thomas, Benedikt; Weigand, Mario

    2018-03-01

    The decay properties of long-lived excited states (isomers) can have a significant impact on the destruction channels of isotopes under stellar conditions. In sufficiently hot environments, the population of isomers can be altered via thermal excitation or de-excitation. If the corresponding lifetimes are of the same order of magnitude as the typical time scales of the environment, the isomers have to be treated explicitly. We present a general approach to the treatment of isomers in stellar nucleosynthesis codes and discuss a few illustrative examples. The corresponding code is available online at http://exp-astro.de/isomers/.

  7. Generalized seniority states and isomers in tin isotopes

    Science.gov (United States)

    Jain, Ashok Kumar; Maheshwari, Bhoomika

    2017-07-01

    Isomeric studies in neutron-rich nuclei are a powerful tool for exploring structure at the nuclear extremes. In this paper we discuss the systematic features of the excitation energies and transition probabilities of Sn isotopes in the region N = 50-82 and present their basic understanding in terms of generalized seniority. We further use generalized seniority as a probe to explore the neutron-rich {6}+ seniority isomers in 134-138Sn, and to validate the neutron single-particle energies beyond N = 82. We show that these isomers behave as generalized seniority isomers, where the so-called anomalous {{B}}(E2) behavior of the {6}+ isomer in 136Sn may be naturally explained. We support these results by shell model calculations, where the latest neutron single-particle energies of the N = 82-126 region have been used, and the i13/2 neutron single-particle energy has been suitably modified in the renormalized charge-dependent Bonn interaction. This entails a possible new subshell closure at N = 112 due to the suggested higher location of the i13/2 neutron orbital, also consistent with the choice of orbitals in the generalized seniority scheme. However, a small reduction in the f7/2 two-body matrix elements is still required in the shell model calculations to consistently reproduce the experimental level energies as well as the transition probabilities in 134-138Sn isotopes.

  8. Isomers chart; Table des isomeres

    Energy Technology Data Exchange (ETDEWEB)

    Dupont-Gautier, P.; Chantelot, S.; Moisson, N. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1967-07-01

    The nuclear isomers are nuclides offering the same mass number and the same atomic number, but different energy levels. In the following chart the zero energy ground states are omitted and the metastable isomers, i.e. of non-zero energy, known and of measurable lifetime, are listed. The lower limit of this lifetime was set here to 0.1 x 10{sup -6} s. The various isomers were classified in increasing lifetimes. (authors) [French] Les isomeres nucleaires sont des nucleides presentant le meme nombre de masse et le meme numero atomique, mais des niveaux energetiques differents. Dans la table suivante, on a neglige les etats fondamentaux d'energie nulle et on a recense les isomeres metastables, c'est-a-dire d'energie non nulle, connus et de periode mesurable. La limite inferieure de cette periode a ete fixee ici a 0,1 x 10{sup -6} s. Les differents isomeres ont ete classes par periodes croissantes. (auteurs)

  9. Short-lived isomers in 94Rb

    International Nuclear Information System (INIS)

    Tsekhanovich, I.; Dare, J. A.; Smith, A. G.; Varley, B. J.; Simpson, G. S.; Urban, W.; Soldner, T.; Jolie, J.; Linnemann, A.; Orlandi, R.; Smith, J. F.; Scherillo, A.; Rzaca-Urban, T.; Zlomaniec, A.; Dorvaux, O.; Gall, B. J. P.; Roux, B.

    2008-01-01

    The medium-spin structure of the neutron-rich, odd-odd nucleus 94 Rb was studied by means of γ-ray spectroscopy. Excited levels were populated in the neutron-induced fission of 235 U and in the spontaneous fission of 252 Cf and 248 Cm. Two isomeric states were found at 1485.2 and 2074.8 keV with half-lives of 18 and 107 ns, respectively. The probable structures of the two isomers involve the fully aligned, proton-neutron configurations [π(g 9/2 ) x ν(g 7/2 )] 8 + and [π(g 9/2 ) x ν(h 11/2 )] 10 - , respectively. These new data give information on the single-particle energies in the region

  10. Atlas of nuclear isomers and their systematics

    International Nuclear Information System (INIS)

    Jain, Ashok Kumar; Maheshwari, Bhoomika

    2015-01-01

    Isomers can be viewed as a separate class of nuclei and offer interesting possibilities to study the behavior of nuclei under varied conditions of excitation energy, spin, life-time and particle configuration. We have completed a horizontal evaluation of nuclear isomers and the resulting data set contains a wealth of information which offers new insights in the nuclear structure of a wide range of configurations, nuclei approaching the drip lines etc. We now have reliable data on approximately 2460 isomers having a half-life ≥ 10 ns. A few of the systematics of the properties of nuclear isomers like excitation energy, half-life, spin, abundance etc. will be presented. The data set of semi-magic isomers strongly supports the existence of seniority isomers originating from the higher spin orbitals. (author)

  11. Optical absorption spectra of Ag-11 isomers

    DEFF Research Database (Denmark)

    Martinez, Jose Ignacio; Fernandez, E. M.

    2009-01-01

    The optical absorption spectra of the three most; stable structural isomers of the Ag-11 cluster were calculated using the time-dependent, density functional theory within the Casida formalism. The slightly different, spectra, of the isomers may permit the identification of the ground-stale confi......The optical absorption spectra of the three most; stable structural isomers of the Ag-11 cluster were calculated using the time-dependent, density functional theory within the Casida formalism. The slightly different, spectra, of the isomers may permit the identification of the ground...

  12. Anion-tunable control of thermal Z→E isomerisation in basic azobenzene receptors.

    Science.gov (United States)

    Dąbrowa, Kajetan; Niedbała, Patryk; Jurczak, Janusz

    2014-12-25

    Herein, we report that thermal Z→E isomerisation of simple azobenzene urea derivatives is selectively and predictably controlled by anion binding. The rate of this process depends strictly on the anion concentration and its binding affinity to the Z-isomer of the azobenzene host, i.e. increased rate constants are observed for higher anion concentration as well as for more strongly bound guests. The origin of this phenomenon is attributed to the electron density transfer from the anion to the host π-system, resulting in increased repulsion between the lone electron pairs in the N=N bond.

  13. Comparative aerobic soil metabolism of fenvalerate isomers

    International Nuclear Information System (INIS)

    Lee, P.W.; Powell, W.R.; Stearns, S.M.; McConnell, O.J.

    1987-01-01

    An aerobic soil metabolism study was conducted to determine the degradation rate of individual isomer of fenvalerate and to assess the potential influence of the RS, SR, and RR isomers to the metabolism of the most insecticidally active SS isomer. Individual [phenoxyphenyl- 14 C]fenvalerate isomers degraded at different rates. The calculated half-lives for the SR, RS, SS, and RR isomers in fenvalerate (racemic mixture) were 155, 89, 108, and 178 days, respectively. The resolved SS isomer degraded at a faster rate with a calculated half-life of 74 days. Racemization of the resolved SS isomer did not occur. A qualitative difference in the chemical nature of soil metabolites between fenvalerate and the resolved SS isomer was not observed. Soil degradation products, phenoxybenzoic acid, 3-(4-hydroxyphenoxy)benzoic acid, and 4'-OH- and CONH 2 -fenvalerate, each accounted for less than 2% of the applied radioactivity. Extensive degradation of these soil metabolites was evident since approximately 50% of the applied radioactivity was recovered as 14 C 2 and as unextractable bound residues

  14. The Gamma Resonance Problem of Long-Lived Nuclear Isomers

    Science.gov (United States)

    Davydov, Andrey V.

    2001-07-01

    A review is given of the studies relating to the problem of γ-resonant (Mössbauer) excitation of long-lived nuclear isomers. The theoretical estimates of possible γ-line broadening are presented. Earlier experiments are described with 107mAg and 109mAg isomers using polycrystalline samples of pure Ag and Ag-Pd alloys. The results of these experiments did not contradict the theoretical predictions. The series of papers using Ag single-crystal γ-sources is reviewed. Their results were interpreted as indications of a rather small 109mAg γ-line broadening, which cannot be explained by modern theory. The results of the last experiments by ITEP group with 109mAg are also presented. These data may be coordinated with results of other research, if one takes into account the Zeeman splitting of the γ-spectra by Earth's magnetic field.

  15. Hydrogen in anion vacancies of semiconductors

    Science.gov (United States)

    Du, Mao-Hua; Singh, David

    2009-03-01

    Hydrogen typically terminates the dangling bonds around vacancies in semiconductors, thereby, partially or completely passivating the vacancies. However, it has been shown recently that hydrogen in anion vacancies of many semiconductors, such as ZnO, MgO, InN, SnO2, and GaN, takes multi-coordinated structures and acts as shallow donors, providing n-type conductivity to the materials. We study the hydrogen in the anion vacancies of a series of II-VI and III-V semiconductors using density functional calculations. The results on these materials show that, in the anion vacancies of polar II-VI semiconductors, the hydrogen is usually anionic and is coordinated with more than one cation atoms as a result of the relatively high ionicity of the host materials. The hydrogen coordination number depends on the host anion size. On the other hand, in more covalent semiconductors such as some III-V semiconductors, the single cation-H bonding configuration may become most stable. In the anion vacancies of ZnX and CdX where X represents anions, hydrogen is typically amphoteric except for oxides, in which the small anion size prohibits the formation of the cation-cation bond that is required for the acceptor configuration.

  16. Investigating carbohydrate isomers by IMS-CID-IMS-MS: precursor and fragment ion cross-sections.

    Science.gov (United States)

    Gaye, M M; Kurulugama, R; Clemmer, D E

    2015-10-21

    Ion mobility spectrometry techniques (IMS and IMS-IMS) combined with collision-induced dissociation (CID) and mass spectrometry (MS) are used to investigate the structures of singly-lithiated carbohydrate isomers. With the exception of some favorable cases, IMS-MS analyses of underivatized carbohydrates reveal that most isobaric precursor ions have similar collision cross sections (ccs). In contrast, ccs values for isomeric fragment ions obtained by IMS-CID-IMS-MS analysis are often different, and thus appear to be useful as a means of distinguishing the isomeric precursors. We report values of ccs (in He) for precursor- and associated-fragment ions for three monosaccharide isomers (glucose, galactose and fructose), ten disaccharide isomers (sucrose, leucrose, palatinose, trehalose, cellobiose, β-gentiobiose, isomaltose, maltose, lactose and melibiose), and three trisaccharide isomers (raffinose, melezitose and maltotriose). These values are discussed as a means of differentiating precursor carbohydrates.

  17. Identification of mixed bromidochloridotellurate anions in disordered crystal structures of (bdmim)2[TeX2Y4] (X, Y=Br, Cl; bdmim=1-butyl-2,3-dimethylimidazolium) by combined application of Raman spectroscopy and solid-state DFT calculations.

    Science.gov (United States)

    Närhi, Sari M; Kutuniva, Johanna; Lajunen, Marja K; Lahtinen, Manu K; Tuononen, Heikki M; Karttunen, Antti J; Oilunkaniemi, Raija; Laitinen, Risto S

    2014-01-03

    The discrete mixed [TeBrxCl6-x](2-) anions in their disordered crystal structures have been identified by using the phases prepared by the reaction of 1-butyl-2,3-dimethylimidazolium halogenides (bdmim)X with tellurium tetrahalogenides TeX4 (X=Cl, Br) as examples. Homoleptic (bdmim)2[TeX6] [X=Cl (1), Br (2)] and mixed (bdmim)2[TeBr2Cl4] (3), and (bdmim)2[TeBr4Cl2] (4) are formed depending on the choice of the reagents, and their crystal structures have been determined by single-crystal X-ray diffraction. The coordination environments of tellurium in all hexahalogenidotellurates are almost octahedral. Because of the crystallographic disorder, the mixed [TeBr2Cl4](2-) and [TeBr4Cl2](2-) anions in 3 and 4 cannot be identified in their crystal structures. Pawley refinement of the X-ray powder diffraction patterns of 1-4 indicates the presence of single phases in all four products. The solid state Raman spectra of 1-4 were assigned with help of DFT calculations that were performed both for the discrete anions in vacuum and for the complete crystal structures employing periodic boundary conditions. The fundamental vibrations of the homoleptic [TeX6](2-) (X=Cl, Br) anions could be well reproduced by the solid-state DFT computations and enabled a complete assignment of the Raman spectra. While the presence of cis-isomers in both [TeBr2Cl4](2-) and [TeBr4Cl2](2-) could be inferred by the computed fundamental vibrations, that of trans-isomers among the reaction products is, however, also possible. The pathway of the formation of [TeX4Y2](2-) isomers from TeX4 and Y(-) (X, Y=Cl, Br) was also explored by DFT calculations both in vacuum and in solution and indicated that both reactions afforded 80 mol% of cis-isomers and 20 mol% of trans-isomers. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. K isomers as probes of nuclear structure

    Science.gov (United States)

    Tandel, S. K.

    2014-08-01

    K isomers are studied in Pu and Cm isotopes, and also in Hf and W nuclei. Many high-K states, several of which are isomeric, are identified. Lifetime measurements spanning the ns-s range have been performed, and decay paths of isomers established. Rotational bands built on high-K states are also identified in many cases. Isomer decays are considerably hindered in many instances, both in the A≈180 and 250 regions indicating that K is an approximately conserved quantum number. High-K states become the favored excitation mode at high spins in the A≈180 region. The energies of the 2-quasiparticle high-K states in Cm isotopes suggest the presence of a deformed subshell gap at N=152.

  19. K isomers as probes of nuclear structure

    Energy Technology Data Exchange (ETDEWEB)

    Tandel, S. K., E-mail: sujit.tandel@cbs.ac.in [UM-DAE Centre for Excellence in Basic Sciences, Mumbai 400098 (India)

    2014-08-14

    K isomers are studied in Pu and Cm isotopes, and also in Hf and W nuclei. Many high-K states, several of which are isomeric, are identified. Lifetime measurements spanning the ns-s range have been performed, and decay paths of isomers established. Rotational bands built on high-K states are also identified in many cases. Isomer decays are considerably hindered in many instances, both in the A≈180 and 250 regions indicating that K is an approximately conserved quantum number. High-K states become the favored excitation mode at high spins in the A≈180 region. The energies of the 2-quasiparticle high-K states in Cm isotopes suggest the presence of a deformed subshell gap at N=152.

  20. Crystal field contribution to Moessbauer isomer shift

    International Nuclear Information System (INIS)

    Singh, Avtar; Shrivastava, K.N.

    1975-01-01

    A new temperature dependent contribution to isomer shift in Fe 3+ (ed 5 ) is proposed. The static crystal field gives rise to a new second-order correction to Mossbauer resonance line and crystal field hamiltonian Hc=B 2 0 Y 2 0 +B 2 2 (Y 22 ) usually used in the study of electronspin resonance is employed. The electron charge density at the nuclear site, responsible for the isomer shift is affected by the crystal field through excitation of an electron from 3d to 4s subshell. Further, temperature dependence is analysed by the variation of crystal field parameters with temperature which occurs as a square in the final result. The importance of the sign of the field parameter (KD) is also realised in the isomer shift studies. Although the proposed new second-order contribution to Moessbauer isomer shift is static in nature, yet it is expected to have important implications in the study of temperature depedence of centre shift of a Moessbauer line. Numerical estimates of the shift are also presented. (author)

  1. [Effect of Cr (VI) anions on the Cu (II) adsorption behavior of two kinds of clay minerals in single and binary solution].

    Science.gov (United States)

    Liu, Juan-Juan; Liang, Dong-Li; Wu, Xiao-Long; Qu, Guang-Zhou; Qian, Xun

    2014-01-01

    The adsorption of Cu (II) on kaolinite and montmorillonite was investigated through batch adsorption experiment. Several adsorption models were employed to describe the adsorption of Cu (II) on the two clay minerals in single Cu (II) and Cu(II)-Cr (VI) binary solutions, and the impact of solution with various pH values on the adsorption of Cu (II) on the two target mineral clays was investigated in order to explain the environmental chemical behavior of heavy metals in soil and to provide theoretical basis in remediation of multi-element contaminated soil. The results indicated that the adsorption process of Cu (II) on kaolinite and montmorillonite in both single and binary solutions was fast at the beginning and then slowed down. Adsorption equilibrium was observed within 120 min. In both single and binary solutions, pseudo-second-order model (R2 > 0.983) showed the highest agreement with the adsorption of Cu (II) on the two mineral clays, followed by the intra-particle diffusion model and pseudo-first-order model. Both Intra-particle diffusion model and Boyd model illustrated that the film diffusion process was the rate-limiting step, which mainly occurred at the edge and surface of mineral clays. Copper adsorption on kaolinite was well fitted with the Freundlich equation (R2 > 0.971), which could be attributed to the heterogeneity of kaolinite surface with adsorption sites that have different energies of adsorption. Langmuir equation was best fitted with the isotherm for montmorillonite (R2 > 0.983), which indicated that the adsorption was on a single molecular layer or chemisorptions. In both single and binary solutions, the adsorption of Cu (II ) on the two clay minerals first increased and then decreased with the rising of pH values. The maximum adsorption amount was found at pH = 5.0, and was in the order of Qmon. > Qkao. and Q(Single-Cu) > Q(Cu-Cr binary). Cr (VI) in the solution reduced the adsorption of Cu (II), and the minimal influence of Cr (VI) on Cu

  2. Potentiometric response and mechanism of anionic recognition of heterocalixarene-based ion selective electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Shishkanova, T.V. [Department of Analytical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic)]. E-mail: tatiana.shishkanova@vscht.cz; Sykora, D. [Department of Analytical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic); Sessler, J.L. [Department of Chemistry and Biochemistry, Institute for Cellular and Molecular Biology, University of Texas, Austin, TX 78712-0615 (United States); Kral, V. [Department of Analytical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic)

    2007-03-28

    The ion selective electrode (ISE)-based potentiometric approach is shown to be an effective means of characterizing the anion recognition sites in the molecular receptor calix[2]pyridino[2]pyrrole (CPP). In particular, potentiometric pH-measurements involving the use of experimental PVC-membranes based on CPP revealed the existence of both mono- and diprotonated forms of the receptor under readily accessible conditions. Based on these analyses, apparent surface protonation constants for this heterocalixarene were found to lie between 8.5-8.9 (pK {sub B1}) and 3.3-3.8 (pK {sub B2}). CPP was found to interact with targeted anionic analytes based on both coulombic and hydrogen bond interactions, as inferred from varying the kinds of ionic sites present within the membrane phase. Potentiometric selectivity studies revealed that CPP preferred 'Y-shaped' anions (e.g. acetate, lactate, benzoate) over spherical anions (e.g. fluoride and chloride), fluoride over chloride within the set of spherical anions, and the ortho-isomer over the corresponding meta- and para-isomers in the case of hydroxybenzoate (salicylate and congeners). In the context of this study, the advantages of potentiometric determinations of acetylsalicylic acid using optimized PVC-membranes based on CPP relative to more conventional PVC-membrane ISEs based on traditional anion exchanger were also demonstrated.

  3. Anion-π catalysis.

    Science.gov (United States)

    Zhao, Yingjie; Beuchat, César; Domoto, Yuya; Gajewy, Jadwiga; Wilson, Adam; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2014-02-05

    The introduction of new noncovalent interactions to build functional systems is of fundamental importance. We here report experimental and theoretical evidence that anion-π interactions can contribute to catalysis. The Kemp elimination is used as a classical tool to discover conceptually innovative catalysts for reactions with anionic transition states. For anion-π catalysis, a carboxylate base and a solubilizer are covalently attached to the π-acidic surface of naphthalenediimides. On these π-acidic surfaces, transition-state stabilizations up to ΔΔGTS = 31.8 ± 0.4 kJ mol(-1) are found. This value corresponds to a transition-state recognition of KTS = 2.7 ± 0.5 μM and a catalytic proficiency of 3.8 × 10(5) M(-1). Significantly increasing transition-state stabilization with increasing π-acidity of the catalyst, observed for two separate series, demonstrates the existence of "anion-π catalysis." In sharp contrast, increasing π-acidity of the best naphthalenediimide catalysts does not influence the more than 12 000-times weaker substrate recognition (KM = 34.5 ± 1.6 μM). Together with the disappearance of Michaelis-Menten kinetics on the expanded π-surfaces of perylenediimides, this finding supports that contributions from π-π interactions are not very important for anion-π catalysis. The linker between the π-acidic surface and the carboxylate base strongly influences activity. Insufficient length and flexibility cause incompatibility with saturation kinetics. Moreover, preorganizing linkers do not improve catalysis much, suggesting that the ideal positioning of the carboxylate base on the π-acidic surface is achieved by intramolecular anion-π interactions rather than by an optimized structure of the linker. Computational simulations are in excellent agreement with experimental results. They confirm, inter alia, that the stabilization of the anionic transition states (but not the neutral ground states) increases with the π-acidity of the

  4. phthalocyanine Positional Isomers for Non-linear O

    African Journals Online (AJOL)

    not observed for all isomers as the localization of these chemical shifts are also highly influenced by aggregation. 3.2. Electronic Absorption Spectroscopy, Magnetic Circular. Dichroism ... oxygen atom for the four regio isomers. When comparing the optimized energies of the isomers, no significant difference was observed.

  5. Electronic structures and water reactivity of mixed metal sulfide cluster anions.

    Science.gov (United States)

    Saha, Arjun; Raghavachari, Krishnan

    2014-08-21

    The electronic structures and chemical reactivity of the mixed metal sulfide cluster anion (MoWS4(-)) have been investigated with density functional theory. Our study reveals the presence of two almost isoenergetic structural isomers, both containing two bridging sulfur atoms in a quartet state. However, the arrangement of the terminal sulfur atoms is different in the two isomers. In one isomer, the two metals are in the same oxidation state (each attached to one terminal S). In the second isomer, the two metals are in different oxidation states (with W in the higher oxidation state attached to both terminal S). The reactivity of water with the two lowest energy isomers has also been studied, with an emphasis on pathways leading to H2 release. The reactive behavior of the two isomers is different though the overall barriers in both systems are small. The origin of the differences are analyzed and discussed. The reaction pathways and barriers are compared with the corresponding behavior of monometallic sulfides (Mo2S4(-) and W2S4(-)) as well as mixed metal oxides (MoWO4(-)).

  6. 241Am (n,gamma) isomer ratio measurement

    Energy Technology Data Exchange (ETDEWEB)

    Bond, Evelyn M [Los Alamos National Laboratory; Vieira, David J [Los Alamos National Laboratory; Moody, Walter A [Los Alamos National Laboratory; Slemmons, Alice K [Los Alamos National Laboratory

    2011-01-05

    The objective of this project is to improve the accuracy of the {sup 242}Cm/{sup 241}Am radiochemistry ratio. We have performed an activation experiment to measure the {sup 241}Am(n,{gamma}) cross section leading to either the ground state of {sup 242g}Am (t{sub 1/2} = 16 hr) which decays to {sup 242}Cm (t{sub 1/2} = 163 d) or the long-lived isomer {sup 242m}Am (t{sub 1/2} = 141 yr). This experiment will develop a new set of americium cross section evaluations that can be used with a measured {sup 242}Cm/{sup 241}Am radiochemical measurement for nuclear forensic purposes. This measurement is necessary to interpret the {sup 242}Cm/{sup 241}Am ratio because a good measurement of this neutron capture isomer ratio for {sup 241}Am does not exist. The targets were prepared in 2007 from {sup 241}Am purified from LANL stocks. Gold was added to the purified {sup 241}Am as an internal neutron fluence monitor. These targets were placed into a holder, packaged, and shipped to Forschungszentrum Karlsruhe, where they were irradiated at their Van de Graff facility in February 2008. One target was irradiated with {approx}25 keV quasimonoenergetic neutrons produced by the {sup 7}Li(p,n) reaction for 3 days and a second target was also irradiated for 3 days with {approx}500 keV neutrons. Because it will be necessary to separate the {sup 242}Cm from the {sup 241}Am in order to measure the amount of {sup 242}Cm by alpha spectrometry, research into methods for americium/curium separations were conducted concurrently. We found that anion exchange chromatography in methanol/nitric acid solutions produced good separations that could be completed in one day resulting in a sample with no residue. The samples were returned from Germany in July 2009 and were counted by gamma spectrometry. Chemical separations have commenced on the blank sample. Each sample will be spiked with {sup 244}Cm, dissolved and digested in nitric acid solutions. One third of each sample will be processed at a time

  7. Potentiometric anion selective sensors

    NARCIS (Netherlands)

    Antonisse, M.M.G.; Reinhoudt, David

    1999-01-01

    In comparison with selective receptors (and sensors) for cationic species, work on the selective complexation and detection of anions is of more recent date. There are three important components for a sensor, a transducer element, a membrane material that separates the transducer element and the

  8. Combined single-crystal X-ray and neutron diffraction analysis of the structure of the (Zr6CI18H5)3- poly-anion

    International Nuclear Information System (INIS)

    Cotton, F.A.; Chen, L.; Schultz, A.J.

    1996-01-01

    The octahedral hexa zirconium compound (Ph 4 P) 3 [Zr 6 Cl 18 H 5 ] has been structurally characterized by a combined analysis of single-crystal X-ray and time-of-flight (TOF) neutron diffraction data. The space group is tetragonal, I4 1 /a, Z = 8, with lattice constants at 123 K of a = 32.957(8), c 15.001(3) Angstrom, V = 16,294(6) Angstrom 3 . Difference Fourier maps based on the neutron data exhibited negative troughs on the triangular faces of the hexa zirconium octahedron which were introduced into the structure as hydrogen atoms. Refinement of the atomic positional and occupancy parameters for the hydrogen atoms resulted in about 0.7 H atoms on each triangular face for a total of 5.47(15) hydrogen atoms atoms per hexa zirconium cluster, in good accord with the 1 H NMR measurement (5.0) and the theoretical expectation of 5. The Zr - (μ 3 H) distances range from 1.8 to 2.1 Angstrom. (authors)

  9. Electric quadruple moments of high-spin isomers in 209Po

    International Nuclear Information System (INIS)

    Ivanov, E.A.; Nicolescu, G.; Plostinaru, D.

    1998-01-01

    The electric quadrupole interaction of the 209 Po (17/2) - and (13/2) - isomers in a Bi single-crystal was measured. The results for the quadrupole moments are connected with studies of isomers in Po isotopes. A two level analysis procedure was employed for the combined data of (17/2) - and (13/2) - isomers. The quadrupole moments of the Po isotopes are of special interest for testing nuclear models because of supposed simple nuclear structure with two protons outside a closed magic number shell. While the g-factors are significant for the predominant few-particle structures often present at high spins, the quadrupole moments are sensitive to additional contributions arising from core deformation effects. A systematic study of quadrupole moments of 12 + isomers in Pb isotopes has indeed demonstrated that the valence neutron effective charge increases as more particle pairs are removed from the 208 Pb core. In the present work, quadrupole coupling constants were measured for the isomers by the time-differential perturbed angular distribution (TDPAD) technique, in the presence of quadrupole interactions from the internal electric field gradient (EFG) in Bi crystal. The experiments were performed using a pulsed deuteron-beam of 13 MeV. The (17/2) - isomer state (T 1/2 = 88 ns) and the (13/2) - isomer state (T 1/2 = 24 ns) were populated and aligned by the 209 Bi(d,2n) reaction. The repetition time of the pulse was 10 μs and the width was around 5 ns (FWHM). The rather low bombardment energy was chosen to reduce population of higher spin isomers and to optimize the population of 209 Po((17/2) - ) and 209 Po((13/2) - ). The 209 Po single crystal target was held at a temperature of 470 K in order to reduce possible radiation damage effects. The experiments have been performed with the c axis of the single crystal at 45 angle and 90 angle to the beam direction. We chose to use a calibration based on isomers with well-understood nuclear structure allowing a reliable

  10. The Effect of Single, Binary and Ternary Anions of Chloride, Carbonate and Phosphate on the Release of 2,4-Dichlorophenoxyacetate Intercalated into the Zn-Al-layered Double Hydroxide Nanohybrid.

    Science.gov (United States)

    Hussein, Mohd Zobir; Jaafar, Adila Mohamad; Yahaya, Asmah Hj; Zainal, Zulkarnain

    2009-08-04

    Intercalation of beneficial anion into inorganic host has lead to an opportunity to synthesize various combinations of new organic-inorganic nanohybrids with various potential applications; especially, for the controlled release formulation and storage purposes. Investigation on the release behavior of 2,4-dichlorophenoxyacetate (2,4-D) intercalated into the interlayer of Zn-Al-layered double hydroxide (ZAN) have been carried out using single, binary and ternary aqueous systems of chloride, carbonate and phosphate. The release behavior of the active agent 2,4-D from its double-layered hydroxide nanohybrid ZANDI was found to be of controlled manner governed by pseudo-second order kinetics. It was found that carbonate medium yielded the highest accumulated release of 2,4-D, while phosphate in combination with carbonate and/or nitrate speeds up the release rate of 2,4-D. These results indicate that it is possible to design and develop new delivery system of latex stimulant compound with controlled release property based on 2,4-D that is known as a substance to increase latex production of rubber tree, Hevea brasiliensis.

  11. The Effect of Single, Binary and Ternary Anions of Chloride, Carbonate and Phosphate on the Release of 2,4-Dichlorophenoxyacetate Intercalated into the Zn–Al-layered Double Hydroxide Nanohybrid

    Directory of Open Access Journals (Sweden)

    Zainal Zulkarnain

    2009-01-01

    Full Text Available Abstract Intercalation of beneficial anion into inorganic host has lead to an opportunity to synthesize various combinations of new organic–inorganic nanohybrids with various potential applications; especially, for the controlled release formulation and storage purposes. Investigation on the release behavior of 2,4-dichlorophenoxyacetate (2,4-D intercalated into the interlayer of Zn–Al-layered double hydroxide (ZAN have been carried out using single, binary and ternary aqueous systems of chloride, carbonate and phosphate. The release behavior of the active agent 2,4-D from its double-layered hydroxide nanohybrid ZANDI was found to be of controlled manner governed by pseudo-second order kinetics. It was found that carbonate medium yielded the highest accumulated release of 2,4-D, while phosphate in combination with carbonate and/or nitrate speeds up the release rate of 2,4-D. These results indicate that it is possible to design and develop new delivery system of latex stimulant compound with controlled release property based on 2,4-D that is known as a substance to increase latex production of rubber tree,Hevea brasiliensis.

  12. Isomer Energy Source for Space Propulsion Systems

    Science.gov (United States)

    2004-03-01

    absorbed during formation is reradiated, but in rare situations, such as with this hafnium isomer, “large differences between the spins of the isomeric...The ROVER & NERVA program generated a proven reactor design that was actually slated for a mission to Mars after the U.S. successfully landed on the...1.380 Sm Lanthanide 7.353 1,345 0.133 Hf Transition Metal 13.31 2,506 0.230 HfC Ceramic 12.2 4,173 ? Ta Transition Metal 16.65 3,290 0.575 TaC

  13. Multicomponent adsorption of hexane isomers in MOFs

    OpenAIRE

    Bárcia, Patrick da Silva; Silva, José A.C.; Rodrigues, A.E.

    2010-01-01

    We have performed a set of screening studies for quaternary mixtures of hexane isomers n-hexane (nHEX), 3-methylpentane (3MP), 2,3-dimethylbutane (23DMB) and 2,2-dimethylbutane (22DMB) in two porous rigid MOFs (figure 1). First, the chromium trimesate MIL-100(Cr),1 which possesses mesoporous cages accessible through 5-9 Å microporous windows, and secondly the zirconium terephthalate UiO-66,2 which exhibits a 3D microporous (5-10 Å) pore system. The temperature range 323-423 K and partial pres...

  14. The interstellar chemistry of H2C3O isomers.

    Science.gov (United States)

    Loison, Jean-Christophe; Agúndez, Marcelino; Marcelino, Núria; Wakelam, Valentine; Hickson, Kevin M; Cernicharo, José; Gerin, Maryvonne; Roueff, Evelyne; Guélin, Michel

    2016-03-11

    We present the detection of two H 2 C 3 O isomers, propynal and cyclopropenone, toward various starless cores and molecular clouds, together with upper limits for the third isomer propadienone. We review the processes controlling the abundances of H 2 C 3 O isomers in interstellar media showing that the reactions involved are gas-phase ones. We show that the abundances of these species are controlled by kinetic rather than thermodynamic effects.

  15. Isomer-specific degradation of branched and linear 4-nonylphenol isomers in an oxic soil.

    Science.gov (United States)

    Shan, Jun; Jiang, Bingqi; Yu, Bin; Li, Chengliang; Sun, Yuanyuan; Guo, Hongyan; Wu, Jichun; Klumpp, Erwin; Schäffer, Andreas; Ji, Rong

    2011-10-01

    Using (14)C- and (13)C-ring-labeling, degradation of five p-nonylphenol (4-NP) isomers including four branched (4-NP(38), 4-NP(65), 4-NP(111), and 4-NP(112)) and one linear (4-NP(1)) isomers in a rice paddy soil was studied under oxic conditions. Degradation followed an availability-adjusted first-order kinetics with the decreasing order of half-life 4-NP(111) (10.3 days) > 4-NP(112) (8.4 days) > 4-NP(65) (5.8 days) > 4-NP(38) (2.1 days) > 4-NP(1) (1.4 days), which is in agreement with the order of their reported estrogenicities. One metabolite of 4-NP(111) with less polarity than the parent compound occurred rapidly and remained stable in the soil. At the end of incubation (58 days), bound residues of 4-NP(111) amounted to 54% of the initially applied radioactivity and resided almost exclusively in the humin fraction of soil organic matter, in which chemically humin-bound residues increased over incubation. Our results indicate an increase of specific estrogenicity of the remaining 4-NPs in soil as a result of the isomer-specific degradation and therefore underline the importance of understanding the individual fate (including degradation, metabolism, and bound-residue formation) of isomers for risk assessment of 4-NPs in soil. 4-NP(1) should not be used as a representative of 4-NPs for studies on their environmental behavior.

  16. Probing ground and low-lying excited states for HIO{sub 2} isomers

    Energy Technology Data Exchange (ETDEWEB)

    Souza, Gabriel L. C. de [Departamento de Química, Universidade Federal de Mato Grosso, Cuiabá, Mato Grosso 78060-900 (Brazil); Instituto de Ciências Exatas e Tecnologia, Universidade Federal do Amazonas, Itacoatiara, Amazonas 69100-000 (Brazil); Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2 (Canada); Brown, Alex, E-mail: alex.brown@ualberta.ca [Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2 (Canada)

    2014-12-21

    We present a computational study on HIO{sub 2} molecules. Ground state properties such as equilibrium structures, relative energetics, vibrational frequencies, and infrared intensities were obtained for all the isomers at the coupled-cluster with single and double excitations as well as perturbative inclusion of triples (CCSD(T)) level of theory with the aug-cc-pVTZ-PP basis set and ECP-28-PP effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. The HOIO structure is confirmed as the lowest energy isomer. The relative energies are shown to be HOIO < HOOI < HI(O)O. The HO(O)I isomer is only stable at the density functional theory (DFT) level of theory. The transition states determined show interconversion of the isomers is possible. In order to facilitate future experimental identification, vibrational frequencies are also determined for all corresponding deuterated species. Vertical excitation energies for the three lowest-lying singlet and triplet excited states were determined using the configuration interaction singles, time-dependent density functional theory (TD-DFT)/B3LYP, TD-DFT/G96PW91, and equation of motion-CCSD approaches with the LANL2DZ basis set plus effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. It is shown that HOIO and HOOI isomers have excited states accessible at solar wavelengths (<4.0 eV) but these states have very small oscillator strengths (<2 × 10{sup −3})

  17. Patchouli alkohol isomers pogostemon herba predicted virtually

    Directory of Open Access Journals (Sweden)

    Sentot Joko Raharjo

    2014-02-01

    Full Text Available The aim of our research is predicting the alpha-patchouli alcohol isomer Pogostemon Herba as inhibitors cyclooxygenase (COX-1 and COX-2 isoenzymes. The data for the alpha-patchouli alcohol isomer (CD521903, CD442384, and/or CD6432585 Pogostemon Herba were explored from the pubchem database. Molecular interaction studies with COX-1 and COX-2 from mouse were done using the molecular docking tools Hex 6.12 and LeadIT2 Bisolve. The analysis of the alpha-patchouli alcohol compounds of patchouli oil showed that alpha-Patchouli alcohol (CD521903 binds to COX-1 at active sites including: LEU223B, ASP228B, LEU237B, ARG 332B, TRP 138A, GLU 139A, SER 142A, ASN 143A, and the interaction to COX-2 at active site including: GLN 289B, GLU 290B, ARG 222B, LYS 211B, THR 212B, HIS 214B, ASN 382B, HEM682B, GLN 454B, HIS 386B, TRP 387B, HIS 388B, VAL 274B, GLN 203B, VAL 291B, VAL 295B. The interaction hydrogen bond energy between alpha-patchouli alcohol: (CD521903-COX-1 complexes (-4 kJ/mol and CD521903-COX-2 complexes (-8 kJ/ mol by LeadIT2 Biosolve. This suggests alpha-patchouli alcohol CD521903 as candidate for a selective COX-2 inhibitor. These in silico data need further analyses of biological function activity

  18. Isomers in neutron-rich A ∼ 190 nuclides from 208Pb fragmentation

    International Nuclear Information System (INIS)

    Rykaczewski, Krzysztof Piotr; Caamano, M.; Banu, A.; Walker, P.M.; Morton, N.H.; Regan, P. H.; Regan, Patrick H; Pfutzner, M.; Podolyak, Zs.; Gerl, J.; Hellstrom, M.; Mayet, P.; Miernik, K.; Mineva, M.N.; Aprahamian, A.; Benlliure, J.; Bruce, A.M.; Butler, P.A.; Cortina Gil, D.; Cullen, D.M.; Doring, J.; Enqvist, T.; Fox, C.; Garces Narro, J.; Geissel, H.; Gelletly, W.; Giovinazzo, J.; Gorska, M.; Grawe, H.; Grzywacz, R.; Kleinbohl, A.; Korten, W.; Lewitowicz, M.; Lucas, R.; Mach, H.; O'Leary, C.D.; De Oliveira, F.; Pearson, C.J.; Rejmund, F.

    2004-01-01

    Relativistic projectile fragmentation of 208 Pb has been used to produce isomers in neutron-rich, A ∼ 190 nuclides. A forward-focusing spectrometer provided ion-by-ion mass and charge identification. The detection of gamma-rays emitted by stopped ions has led to the assignment of isomers in 188 Ta, 190 W, 192 Re, 193 Re, 195 Os, 197 Ir, 198 Ir, 200 Pt, 201 Pt, 202 Pt and 203 Au, with half-lives ranging from approximately 10 ns to 1 ms. Tentative isomer information has been found also for 174 Er, 175 Er, 185 Hf, 191 Re, 194 Re and 199 Ir. In most cases, time-correlated, singles gamma-ray events provided the first spectroscopic data on excited states for each nuclide. In 200 Pt and 201 Pt, the assignments are supported by gamma-gamma coincidences. Isomeric ratios provide additional information, such as half-life and transition energy constraints in particular cases. The level structures of the platinum isotopes are discussed, and comparisons are made with isomer systematics

  19. Reaction between peroxynitrite and triphenylphosphonium-substituted arylboronic acid isomers: identification of diagnostic marker products and biological implications.

    Science.gov (United States)

    Sikora, Adam; Zielonka, Jacek; Adamus, Jan; Debski, Dawid; Dybala-Defratyka, Agnieszka; Michalowski, Bartosz; Joseph, Joy; Hartley, Richard C; Murphy, Michael P; Kalyanaraman, Balaraman

    2013-06-17

    Aromatic boronic acids react rapidly with peroxynitrite (ONOO(-)) to yield phenols as major products. This reaction was used to monitor ONOO(-) formation in cellular systems. Previously, we proposed that the reaction between ONOO(-) and arylboronates (PhB(OH)2) yields a phenolic product (major pathway) and a radical pair PhB(OH)2O(•-)···(•)NO2 (minor pathway). [Sikora, A. et al. (2011) Chem. Res. Toxicol. 24, 687-697]. In this study, we investigated the influence of a bulky triphenylphosphonium (TPP) group on the reaction between ONOO(-) and mitochondria-targeted arylboronate isomers (o-, m-, and p-MitoPhB(OH)2). Results from the electron paramagnetic resonance (EPR) spin-trapping experiments unequivocally showed the presence of a phenyl radical intermediate from meta and para isomers, and not from the ortho isomer. The yield of o-MitoPhNO2 formed from the reaction between o-MitoPhB(OH)2 and ONOO(-) was not diminished by phenyl radical scavengers, suggesting a rapid fragmentation of the o-MitoPhB(OH)2O(•-) radical anion with subsequent reaction of the resulting phenyl radical with (•)NO2 in the solvent cage. The DFT quantum mechanical calculations showed that the energy barrier for the dissociation of the o-MitoPhB(OH)2O(•-) radical anion is significantly lower than that of m-MitoPhB(OH)2O(•-) and p-MitoPhB(OH)2O(•-) radical anions. The nitrated product, o-MitoPhNO2, is not formed by the nitrogen dioxide radical generated by myeloperoxidase in the presence of the nitrite anion and hydrogen peroxide, indicating that this specific nitrated product may be used as a diagnostic marker product for ONOO(-). Incubation of o-MitoPhB(OH)2 with RAW 264.7 macrophages activated to produce ONOO(-) yielded the corresponding phenol o-MitoPhOH as well as the diagnostic nitrated product, o-MitoPhNO2. We conclude that the ortho isomer probe reported here is most suitable for specific detection of ONOO(-) in biological systems.

  20. Ion-selective electrode and anion gap range: What should the anion gap be?

    Science.gov (United States)

    Sadjadi, Seyed-Ali; Manalo, Rendell; Jaipaul, Navin; McMillan, James

    2013-01-01

    Using flame photometry technique in the 1970s, the normal value of anion gap (AG) was determined to be 12 ± 4 meq/L. However, with introduction of the autoanalyzers using an ion-selective electrode (ISE), the anion gap value has fallen to lower levels. A retrospective study of US veterans from a single medical center was performed to determine the value of the anion gap in subjects with normal renal function and normal serum albumin and in patients with lactic acidosis and end-stage renal disease on dialysis. In 409 patients with an estimated glomerular filtration rate ≥60 mL/min/1.73 m(2) body surface area and serum albumin ≥4 g/dL, the mean AG was 7.2 ± 2 (range 3-11) meq/L. In 299 patients with lactic acidosis (lactate level ≥4 meq/L) and 68 patients with endstage renal disease on dialysis, the mean AG was 12.5 meq/L and 12.4 meq/L, respectively. A value anion gap and a possible clue to drug intoxication and paraproteinemic disorders. With the advent of ISE for measurement of analytes, the value of the anion gap has fallen. Physicians need to be aware of the normal AG value in their respective institutions, and laboratories need to have an established value for AG based on the type of instrument they are using.

  1. Search for isomers in nuclei near N = 50

    International Nuclear Information System (INIS)

    Taras, P.; Haas, B.; Merdinger, J.C.; Styczen, J.

    1979-01-01

    Targets of sup (58, 60, 61, 62, 64) Ni, Co, and Cu have been bombarded with 42 MeV 16 O beams. Several isomers were produced but no new isomer was found, in particular in 74 Kr which is expected to be a good candidate for yrast traps in the N = 50 region. (author)

  2. Stereospecific Synthesis of the Geometrical Isomers of a Natural Product

    Science.gov (United States)

    Grove, T.; DiLella, D.; Volker, E.

    2006-01-01

    Stereospecific synthesis of a geometrical isomer is not a common topic for the introductory organic chemistry laboratory. We have developed and tested an experiment for the synthesis of (Z) and (E) isomers that has been performed successfully by undergraduate students. The experiment is presented to the students as a puzzle in which they must…

  3. Simultaneous Determination of Two Isomers of Asarone in Piper ...

    African Journals Online (AJOL)

    Purpose: To develop a rapid and reliable reverse phase high performance liquid chromatography (RP-. HPLC) method to quantify the two isomers of asarones in P. sarmentosum extracts using two different columns under similar analytical conditions. Methods: Two isomers, α- and β-asarone, were analyzed using two types ...

  4. Anaerobic Degradation of Lindane and Other HCH Isomers

    NARCIS (Netherlands)

    Mehboob, F.; Langenhoff, A.A.M.; Schraa, G.; Stams, A.J.M.

    2013-01-01

    Lindane (¿-HCH) is a pesticide that has mainly been used in agriculture. Lindane and the other HCH isomers are highly chlorinated hydrocarbons. The presence of a large number of electron withdrawing chlorine groups makes some of the HCH isomers rather recalcitrant in oxic environments. Especially

  5. Complete Hexose Isomer Identification with Mass Spectrometry

    Science.gov (United States)

    Nagy, Gabe; Pohl, Nicola L. B.

    2015-04-01

    The first analytical method is presented for the identification and absolute configuration determination of all 24 aldohexose and 2-ketohexose isomers, including the D and L enantiomers for allose, altrose, galactose, glucose, gulose, idose, mannose, talose, fructose, psicose, sorbose, and tagatose. Two unique fixed ligand kinetic method combinations were discovered to create significant enough energetic differences to achieve chiral discrimination among all 24 hexoses. Each of these 24 hexoses yields unique ratios of a specific pair of fragment ions that allows for simultaneous determination of identification and absolute configuration. This mass spectrometric-based methodology can be readily employed for accurate identification of any isolated monosaccharide from an unknown biological source. This work provides a key step towards the goal of complete de novo carbohydrate analysis.

  6. Optimization of C20 isomers structure

    International Nuclear Information System (INIS)

    Ndjaka, J.M.B.; Charlier, J.C.

    2001-07-01

    We have performed geometry optimization of various possible planar and three-dimensional C 20 geometries. The planar structures considered include a linear chain, a monoclinic ring, and a bicyclic bow tie; while the three-dimensional geometric; consisted of a bowl or corranulene structure and a fullerene cage. In agreement with Wang et al MP2's calculations, our results predict the corranulene bowl to be the lowest energy structure. From the ground state geometry to the highest energy, considered C 20 structures, listed in increasing energy, are bowl, cage, bow tie, ring and chain. For the ring and bow tie isomers, the shape of the optimized structure deviates from that of the initial configuration; while the shape of the optimised bowl, cage and chain remain unchanged. (author)

  7. Identification of isomers of organometallic compounds

    International Nuclear Information System (INIS)

    Mbue, Sona Peter; Cho, Kwang Hwi

    2015-01-01

    The yaChI is a newly suggested chemical naming system. However, yaChI is a derivative of the IUPAC InChI with a modified algorithm that includes additional layers of chemical structure information. Consequently, yaChI string contains more structure details while preserving the original structure file information and can distinctively identify very closely related compounds reducing the chances of ambiguity in chemical compound databases as opposed to the general SMILES, InChI, and InChIKey. This study examines the relative performances of yaChI, SMILES, InChI, and InChIKey in duplication check for isomers. For simplicity, a small data set of 28 organometallic compounds (structural isomers of Rh-containing compounds) subdivided into three major groups (A, B, and C) based on the number and the type of ligands attached to the center atom was used to study the performances of each encoding scheme in describing chemical structures. SMILES, InChI, and InChIKey were generated using Openbabel and RDkit, whereas yaChI strings were generated with in-house program. Strings generated from SMILES, InChI, and InChIKey though different, resulted to only three unique chemical identifiers, with each belonging to one group indicating the presence of only three unique compounds in the study data. However, yaChI results depicted that all structures in each group are indeed unique and differ among themselves as well as those from other groups, mapping each structure with a unique identifier given a total number of 28 unique structures in the study data. This high perception of yaChI probe justifies its accuracy and reliability in duplication check among closely related compounds especially structures exhibiting stereo properties

  8. The many ways of making anionic clays

    Indian Academy of Sciences (India)

    Unknown

    trivalent metal hydroxides and their hydroxy salts are actually anionic clays consisting of positively charged hydroxide layers with anions intercalated in the interlayer region. The anionic clays exhibit anion sorption, anion diffusion and exchange properties together with surface basicity making them materials of importance ...

  9. The many ways of making anionic clays

    Indian Academy of Sciences (India)

    Together with hydrotalcite-like layered double hydroxides, bivalent and trivalent metal hydroxides and their hydroxy salts are actually anionic clays consisting of positively charged hydroxide layers with anions intercalated in the interlayer region. The anionic clays exhibit anion sorption, anion diffusion and exchange ...

  10. Expanding frontiers in materials chemistry and physics with multiple anions.

    Science.gov (United States)

    Kageyama, Hiroshi; Hayashi, Katsuro; Maeda, Kazuhiko; Attfield, J Paul; Hiroi, Zenji; Rondinelli, James M; Poeppelmeier, Kenneth R

    2018-02-22

    During the last century, inorganic oxide compounds laid foundations for materials synthesis, characterization, and technology translation by adding new functions into devices previously dominated by main-group element semiconductor compounds. Today, compounds with multiple anions beyond the single-oxide ion, such as oxyhalides and oxyhydrides, offer a new materials platform from which superior functionality may arise. Here we review the recent progress, status, and future prospects and challenges facing the development and deployment of mixed-anion compounds, focusing mainly on oxide-derived materials. We devote attention to the crucial roles that multiple anions play during synthesis, characterization, and in the physical properties of these materials. We discuss the opportunities enabled by recent advances in synthetic approaches for design of both local and overall structure, state-of-the-art characterization techniques to distinguish unique structural and chemical states, and chemical/physical properties emerging from the synergy of multiple anions for catalysis, energy conversion, and electronic materials.

  11. Properties of neutron-rich hafnium high-spin isomers

    CERN Multimedia

    Tungate, G; Walker, P M; Neyens, G; Billowes, J; Flanagan, K; Koester, U H; Litvinov, Y

    It is proposed to study highly-excited multi-quasiparticle isomers in neutron-rich hafnium (Z=72) isotopes. Long half-lives have already been measured for such isomers in the storage ring at GSI, ensuring their accessibility with ISOL production. The present proposal focuses on:\\\\ (i) an on-line experiment to measure isomer properties in $^{183}$Hf and $^{184}$Hf, and\\\\ (ii) an off-line molecular breakup test using REXTRAP, to provide Hf$^{+}$ beams for future laser spectroscopy and greater sensitivity for the future study of more neutron-rich isotopes.

  12. Detection of Actinides via Nuclear Isomer De-Excitation

    Energy Technology Data Exchange (ETDEWEB)

    Francy, Christopher J. [Oregon State Univ., Corvallis, OR (United States)

    2009-07-01

    This dissertation discusses a data collection experiment within the Actinide Isomer Identification project (AID). The AID project is the investigation of an active interrogation technique that utilizes nuclear isomer production, with the goal of assisting in the interdiction of illicit nuclear materials. In an attempt to find and characterize isomers belonging to 235U and its fission fragments, a 232Th target was bombarded with a monoenergetic 6Li ion beam, operating at 45 MeV.

  13. a Theoretical and Experimental Study of the Conformation of Peroxynitrite Anion (onoo(minus)) and its Stability.

    Science.gov (United States)

    Tsai, Jyh-Hsin Michael

    Peroxynitrite anion (ONOO^-), the reaction product of superoxide (O_2 {cdot}^-) and nitric oxide (cdotNO), is a strong and relatively long-lived oxidant produced by activated macrophages and neutrophils. At physiological pH, peroxynitrous acid forms a hydroxyl radical-like species and has been implicated in pulmonary edema, myocardial ischemia and stroke. Peroxynitrite is remarkably stable in both an alkaline solution and a crystalline state, which appears to be related to the molecule being locked in the cis conformation. To study the conformation of peroxynitrite, Raman spectra with different isotopic substitutions (O^{14}NOO ^-, O^{15} NOO^-, and ^ {18}O^{15}NOO ^-) in alkaline aqueous solutions were recorded in the 200-1800 cm^{ -1} region. The Raman spectra revealed only a single isomer with peaks observed at 375, 642, 791, 931 and 1564 cm^{-1} for O ^{14}NOO^ -. A sixth band was most likely hidden beneath a strong nitrate band centered at 1047 cm^ {-1} or too weak to be observed. The solid state Raman spectra of alkali peroxynitrites are similar to the aqueous solution spectra and consistent with only one isomer being present. A new peak which corresponded to the missing band in aqueous spectra was observed at around 1000 cm^{-1} in the Raman spectra of alkali peroxynitrites. Furthermore, the ^{15}N-NMR spectrum of peroxynitrite revealed only one peak at 178.0 ppm down -field from nitrate, also suggesting the presence of only one stable conformation. Ab initio quantum chemical calculations predicted that the cis conformation is more stable than the trans conformation by 3-4 kcal/mol. The vibrational frequency predictions from the cis conformation are in better agreement with the observed spectra than those from the trans conformation. The Raman torsional band of aqueous peroxynitrite was exceptionally broad, which suggests that peroxynitrite has strong solvent interactions with water molecules. The Raman spectra of peroxynitrite diluted in methanol were also

  14. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng

    2014-01-01

    In the recent surge of metal-free polymerization techniques, phosphazene bases have shown their remarkable potential as organic promoters/catalysts for the anionic polymerization of various types of monomers. By complexation with the counterion (e.g. proton or lithium cation), phosphazene base significantly improve the nucleophilicity of the initiator/chain-end resulting in rapid and usually controlled anionic/quasi-anionic polymerization. In this review, we will introduce the general mechanism, i.e. in situ activation (of initiating sites) and polymerization, and summarize the applications of such a mechanism on macromolecular engineering toward functionalized polymers, block copolymers and complex macromolecular architectures.

  15. Fac and mer isomers of Ru(II) tris(pyrazolyl-pyridine) complexes as models for the vertices of coordination cages: structural characterisation and hydrogen-bonding characteristics.

    Science.gov (United States)

    Metherell, Alexander J; Cullen, William; Stephenson, Andrew; Hunter, Christopher A; Ward, Michael D

    2014-01-07

    We have prepared a series of mononuclear fac and mer isomers of Ru(II) complexes containing chelating pyrazolyl-pyridine ligands, to examine their differing ability to act as hydrogen-bond donors in MeCN. This was prompted by our earlier observation that octanuclear cube-like coordination cages that contain these types of metal vertex can bind guests such as isoquinoline-N-oxide (K = 2100 M(-1) in MeCN), with a significant contribution to binding being a hydrogen-bonding interaction between the electron-rich atom of the guest and a hydrogen-bond donor site on the internal surface of the cage formed by a convergent set of CH2 protons close to a 2+ metal centre. Starting with [Ru(L(H))3](2+) [L(H) = 3-(2-pyridyl)-1H-pyrazole] the geometric isomers were separated by virtue of the fact that the fac isomer forms a Cu(I) adduct which the mer isomer does not. Alkylation of the pyrazolyl NH group with methyl iodide or benzyl bromide afforded [Ru(L(Me))3](2+) and [Ru(L(bz))3](2+) respectively, each as their fac and mer isomers; all were structurally characterised. In the fac isomers the convergent group of pendant -CH2R or -CH3 protons defines a hydrogen-bond donor pocket; in the mer isomer these protons do not converge and any hydrogen-bonding involving these protons is expected to be weaker. For both [Ru(L(Me))3](2+) and [Ru(L(bz))3](2+), NMR titrations with isoquinoline-N-oxide in MeCN revealed weak 1 : 1 binding (K ≈ 1 M(-1)) between the guest and the fac isomer of the complex that was absent with the mer isomer, confirming a difference in the hydrogen-bond donor capabilities of these complexes associated with their differing geometries. The weak binding compared to the cage however occurs because of competition from the anions, which are free to form ion-pairs with the mononuclear complex cations in a way that does not happen in the cage complexes. We conclude that (i) the presence of fac tris-chelate sites in the cage to act as hydrogen-bond donors, and (ii

  16. Carotenoids and Their Isomers: Color Pigments in Fruits and Vegetables

    Directory of Open Access Journals (Sweden)

    Yueming Jiang

    2011-02-01

    Full Text Available Fruits and vegetables are colorful pigment-containing food sources. Owing to their nutritional benefits and phytochemicals, they are considered as ‘functional food ingredients’. Carotenoids are some of the most vital colored phytochemicals, occurring as all-trans and cis-isomers, and accounting for the brilliant colors of a variety of fruits and vegetables. Carotenoids extensively studied in this regard include β-carotene, lycopene, lutein and zeaxanthin. Coloration of fruits and vegetables depends on their growth maturity, concentration of carotenoid isomers, and food processing methods. This article focuses more on several carotenoids and their isomers present in different fruits and vegetables along with their concentrations. Carotenoids and their geometric isomers also play an important role in protecting cells from oxidation and cellular damages.

  17. Simultaneous Determination of Two Isomers of Asarone in Piper ...

    African Journals Online (AJOL)

    Simultaneous Determination of Two Isomers of Asarone in Piper sarmentosum Roxburgh (Piperaceae) Extracts using Different Chromatographic Columns. Mohd Shahrul Ridzuan Hamil, Abdul Hakeem Memon, Amin Malik Shah Abdul Majid, Zhari Ismail ...

  18. Pentaarylfullerenes as noncoordinating cyclopentadienyl anions

    NARCIS (Netherlands)

    Bouwkamp, Marco W.; Meetsma, Auke

    2009-01-01

    The first example of an early-transition-metal complex involving a pentaarylfullerene was prepared. Instead of half-sandwich complexes, solvent separated ion pairs were obtained in which the pentaarylfullerene moiety acts as noncoordinating cyclopentadienyl anion.

  19. Inmersiones isométricas en variedades riemannianas

    Directory of Open Access Journals (Sweden)

    Carlos Alberto Marín Arango

    2011-01-01

    Full Text Available Este trabajo recapitula la teoría básica de conexiones en fibrados principales y fibrados vectoriales con el fin de aplicar tales teorías al estudio de inmersiones isométricas en variedades riemannianas; por medio de una versión apropiada del teorema de Frobenius mostramos un resultado que generaliza el teorema fundamental de las inmersiones isométricas.

  20. Production of isomers in compound and transfer reactions with 4He ions

    International Nuclear Information System (INIS)

    Karamyan, S.A.; Aksenov, N.V.; Albin, Yu.A.; Bozhikov, G.A.; Dmitriev, S.N.; Starodub, G.Ya.; Vostokin, G.K.; Carroll, J.J.

    2011-01-01

    A well-known island of nuclear isomerism appears near A = 175-180 due to the deformation alignment of single-particle orbits at high angular momentum. This sometimes results in the formation of multi-quasiparticle states with record spin that are long-lived because of 'K-hindrance', i.e., symmetry rearrangement. Production methods and spectroscopic studies of these isomers remain a challenge for modern nuclear reaction and nuclear structure physics. Activities were produced by irradiation of 176 Yb(97.6%) enriched and nat Lu targets with 35-MeV 4 He ions from the internal beam of the U200 cyclotron. Induced activities were analyzed applying methods of radiochemistry and gamma spectroscopy. Yields of compound and nucleon-transfer reactions were measured and the isomer-to-ground state ratios were deduced. Calculated results were obtained using standard procedures to reproduce the (α, xn) cross sections, and the systematic behavior of the nucleon-transfer yields was established. The isomer-to-ground state ratios for direct reactions with 4 He ions were examined, resulting in a new characterization of the reaction mechanism

  1. Nonadiabatic dynamics simulation of photoisomerization mechanism of the second stablest isomer of N-salicilydenemethylfurylamine

    Science.gov (United States)

    Gao, Aihua; Li, Jianpeng; Wang, Dehua; Ma, Xiaoguang; Wang, Meishan

    2018-02-01

    The photoisomerization processes of the second stablest isomer in the aromatic Schiff base, N-salicilydenemethylfurylamine, in the gas phase have been studied by static electronic structure calculations and surface-hopping dynamics simulations based on the Zhu-Nakamura theory. Various stable structures are obtained in the optimization because of different orientations of methyl-furyl part with respect to the salicylaldimine part and different orientations of hydroxy group with respect to the benzene ring. Upon photoexcitation into the first excited state, bond isomerization in the salicylaldimine part is completely suppressed until the strong excited-state hydrogen bond is broken. The decay pathway involves two excited-state minima, one in cis-enol form and the other in cis-keto form. After the excited-state proton transfer, twists of bonds lead to a conical intersection between the ground and excited states. After internal conversion around a conical intersection, the molecule is stabilized in cis- or trans-keto form. If the reverse hydrogen transfer process occurs in the ground state, the molecule will finally end up in the cis-enol region. The cis-keto and trans-keto isomers are observed as photoproducts. According to our full-dimensional nonadiabatic dynamics simulations, we find the excited-state intramolecular proton transfer and torsions of three single bonds in the chain to be responsible for photoisomerization of the second stablest isomer of N-salicilydenemethylfurylamine.

  2. Evidence for two interconverting protein isomers in the methotrexate complex of dihydrofolate reductase from Escherichia coli

    Energy Technology Data Exchange (ETDEWEB)

    Falzone, C.J.; Benkovic, S.J. (Pennsylvania State Univ., University Park (United States)); Wright, P.E. (Research Inst. of Scripps Clinic, La Jolla, CA (United States))

    1991-02-26

    Two-dimensional {sup 1}H NMR methods and a knowledge of the X-ray crystal structure have been used to make resonance assignments for the amino acid side chains of dihydrofolate reductase from Escherichia coli complexed with methotrexate. The H7 proton on the pteridine ring of methotrexate was found to have NOEs to the methyl protons of Leu-28 which were assigned by using the L28F mutant. These NOEs indicated that the orientation of the methotrexate pteridine ring is similar in both solution and crystal structures. During the initial assignment process, it became evident that many of the resonances in this complex, unlike those of the folate complex, are severally broadened or doubled. The observation of two distinct sets of resonances in a ratio of approximately 2:1 was attributed to the presence of two protein isomers. Many of the side chains with clearly doubled resonances were located in the {beta}-sheet and the active site. Preliminary studies on the apoprotein also revealed doubled resonances in the absence of the inhibitor, indicating the existence of the protein isomers prior to methotrexate binding. In contrast to the methotrexate complex, the binary complex with folate and the ternary MTX-NADPH-DHFR complex presented a single enzyme form. These results are proposed to reflect the ability of folate and NADPH to bind predominantly to one protein isomer.

  3. Adsorption of butane isomers and SF6 on Kureha activated carbon: 1. Equilibrium.

    Science.gov (United States)

    Zhu, Weidong; Groen, Johan C; Kapteijn, Freek; Moulijn, Jacob A

    2004-06-22

    Adsorption equilibria of butane isomers and SF6 on Kureha activated carbon were investigated using the volumetric method and the tapered element oscillating microbalance (TEOM) technique. The isotherm data of the butane isomers measured by the TEOM technique are in good agreement with those determined by the volumetric method. Single-component adsorption isotherms are reported at temperatures in the range from 298 to 393 K and at pressures up to 120 kPa. SF6 molecules are mainly adsorbed in the larger micropores, resulting in a lower adsorption capacity. The amount adsorbed for n-butane is slightly higher than that for isobutane in the whole range investigated. This is attributed to the fact that the linear n-butane molecule can adsorb in the smaller micropores. The T6th model appropriately describes the equilibrium data of the butane isomers, while the isotherm data of SF6 can be fitted by the Langmuir model. The isosteric heats associated with adsorption for these three adsorptives show different loading dependences. The present study indicates that the activated carbon can be well characterized by the probe molecules having different molecular sizes.

  4. New K isomers in the neutron-rich N =100 isotones 162Sm, 163Eu, and 164Gd

    Science.gov (United States)

    Yokoyama, R.; Go, S.; Kameda, D.; Kubo, T.; Inabe, N.; Fukuda, N.; Takeda, H.; Suzuki, H.; Yoshida, K.; Kusaka, K.; Tanaka, K.; Yanagisawa, Y.; Ohtake, M.; Sato, H.; Shimizu, Y.; Baba, H.; Kurokawa, M.; Nishimura, D.; Ohnishi, T.; Iwasa, N.; Chiba, A.; Yamada, T.; Ideguchi, E.; Fujii, T.; Nishibata, H.; Ieki, K.; Murai, D.; Momota, S.; Sato, Y.; Hwang, J. W.; Kim, S.; Tarasov, O. B.; Morrissey, D. J.; Sherrill, B. M.; Simpson, G.; Praharaj, C. R.

    2017-03-01

    Very neutron-rich Z ˜60 isotopes produced by in-flight fission of a 345 MeV/nucleon 238U beam at the RI Beam Factory, RIKEN Nishina Center, have been studied by delayed γ -ray spectroscopy. New isomers were discovered in the neutron-rich N =100 isotones 162Sm, 163Eu, and 164Gd. Half-lives, γ -ray energies, and relative intensities of these isomers were obtained. Level schemes were proposed for these nuclei and the first 2+ and 4+ states were assigned for the even-even nuclei. The first 2+ and 4+ state energies decrease as the proton numbers get smaller. The energies and the half-lives of the new isomers are very similar to those of 4- isomers known in less neutron-rich N =100 isotones 168Er and 170Yb. A deformed Hartree-Fock with angular momentum projection model suggests Kπ=4- two-quasiparticle states with ν 7 /2 [633 ]⊗ν 1 /2 [521 ] configurations with similar excitation energy. The results suggest that neutron-rich N =100 nuclei are well deformed and the deformation gets larger as Z decreases to 62. The onset of K isomers with the same configuration at almost the same energy in N =100 isotones indicates that the neutron single-particle structures of neutron-rich isotones down to Z =62 do not change significantly from those of the Z =70 stable nuclei. Systematics of the excitation energies of new isomers can be explained without the predicted N =100 shell gap.

  5. Multiple Stimuli Responses of Stereo-Isomers of AIE-Active Ethynylene-Bridged and Pyridyl-Modified Tetraphenylethene.

    Science.gov (United States)

    Wang, Zhaoyang; Cheng, Xiao; Qin, Anjun; Zhang, Haoke; Sun, Jing Zhi; Tang, Ben Zhong

    2018-02-22

    Luminescent molecules with aggregation-induced emission (AIE) property or AIE-active luminogens (AIE-gens) are typical stimuli-responsive materials. Many AIE-gens have shown luminescent responses to mechano-, thermo-, electro-, vapo-, and/or solvato-stimulus, but the detailed structure-property relationship has been addressed for only a few of them. Here, we report a tetraphenylethene (TPE) derivative with pyridyl modifiers and ethynylene bridges. The (Z)- and (E)-isomers are clearly purified, and both of them are AIE-active and demonstrate multiple luminescent responses to external stimuli. Distinct from other reported TPE derivatives, the two isomers show negative solvatochromism due to the large dipole in the ground electronic state. By correlating with the single crystal structures, the subtle differences in quantum efficiency and emission peak wavelength of the solids of the (Z)- and (E)-isomers are rationally explained. Moreover, the ground powder of the (E)-isomer can recover its emission color from green to blue in the air at room temperature but the (Z)-isomer cannot. This difference is interpreted by a mechanism of water-triggered conformational variation, which depends on the hydrogen bond formation between pyridyl moieties and water molecules in the air. In addition to the reversible emission color changes by cyclic grinding-fuming treatments, both of the isomers exhibit a reversible luminescent response to acid-base treatments by switching the emission color between green (basic) and yellow (acid), owing to the incorporation of pyridyl units into the molecule. The unprecedented multiple stimuli-responsive behaviors and clear mechanism explanations allow this kind of AIE-gens to be promising smart materials.

  6. Bound anionic states of adenine

    Energy Technology Data Exchange (ETDEWEB)

    Haranczyk, Maciej; Gutowski, Maciej S; Li, Xiang; Bowen, Kit H

    2007-03-20

    Anionic states of nucleic acid bases are involved in DNA damage by low-energy electrons and in charge transfer through DNA. Previous gas phase studies of free, unsolvated nucleic acid base parent anions probed only dipole-bound states, which are not present in condensed phase environments, but did not observe valence anionic states, which for purine bases, are thought to be adiabatically unbound. Contrary to this expectation, we have demonstrated that some thus far ignored tautomers of adenine, which result from enamine-imine transformations, support valence anionic states with electron vertical detachment energies as large as 2.2 eV, and at least one of these anionic tautomers is adiabatically bound. Moreover, we predict that the new anionic tautomers should also dominate in solutions and should be characterized by larger values of electron vertical detachment energy than the canonical valence anion. All of the new-found anionic tautomers might be formed in the course of dissociative electron attachment followed by a hydrogen atom attachment to a carbon atom, and they might affect the structure and properties of DNA and RNA exposed to low-energy electrons. The discovery of these valence anionic states of adenine was facilitated by the development of: (i) a new experimental method for preparing parent anions of nucleic acid bases for photoelectron experiments, and (ii) a new combinatorial/ quantum chemical approach for identification of the most stable tautomers of organic molecules. The computational portion of this work was supported by the: (i) Polish State Committee for Scientific Research (KBN) Grants: DS/8000-4-0140-7 (M.G.) and N204 127 31/2963 (M.H.), (ii) European Social Funds (EFS) ZPORR/2.22/II/2.6/ARP/U/2/05 (M.H.), and (iii) US DOE Office of Biological and Environmental Research, Low Dose Radiation Research Program (M.G.). M.H. holds the Foundation for Polish Science (FNP) award for young scientists. The calculations were performed at the Academic

  7. Ion-selective electrode and anion gap range: What should the anion gap be?

    Directory of Open Access Journals (Sweden)

    Sadjadi SA

    2013-06-01

    Full Text Available Seyed-Ali Sadjadi, Rendell Manalo, Navin Jaipaul, James McMillan Jerry L Pettis Memorial Veterans Medical Center, Loma Linda University School of Medicine, Loma Linda, CA, USA Background: Using flame photometry technique in the 1970s, the normal value of anion gap (AG was determined to be 12 ± 4 meq/L. However, with introduction of the autoanalyzers using an ion-selective electrode (ISE, the anion gap value has fallen to lower levels. Methods: A retrospective study of US veterans from a single medical center was performed to determine the value of the anion gap in subjects with normal renal function and normal serum albumin and in patients with lactic acidosis and end-stage renal disease on dialysis. Results: In 409 patients with an estimated glomerular filtration rate ≥60 mL/min/1.73 m2 body surface area and serum albumin ≥4 g/dL, the mean AG was 7.2 ± 2 (range 3–11 meq/L. In 299 patients with lactic acidosis (lactate level ≥4 meq/L and 68 patients with end-stage renal disease on dialysis, the mean AG was 12.5 meq/L and 12.4 meq/L, respectively. A value <2 meq/L should be considered a low anion gap and a possible clue to drug intoxication and paraproteinemic disorders. Conclusion: With the advent of ISE for measurement of analytes, the value of the anion gap has fallen. Physicians need to be aware of the normal AG value in their respective institutions, and laboratories need to have an established value for AG based on the type of instrument they are using. Keywords: acidosis, electrolytes, ESRD

  8. Photoelectron Spectroscopy and Theoretical Studies of Anion-pi Interactions: Binding Strength and Anion Specificity

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jian; Zhou, Bin; Sun, Zhenrong; Wang, Xue B.

    2015-01-01

    Proposed in theory and confirmed to exist, anion–π interactions have been recognized as new and important non-covalent binding forces. Despite extensive theoretical studies, numerous crystal structural identifications, and a plethora of solution phase investigations, intrinsic anion–π interaction strengths that are free from complications of condensed phases’ environments, have not been directly measured in the gas phase. Herein we present a joint photoelectron spectroscopic and theoretical study on this subject, in which tetraoxacalix[2]arene[2]triazine 1, an electron-deficient and cavity self-tunable macrocyclic was used as a charge-neutral molecular host to probe its interactions with a series of anions with distinctly different shapes and charge states (spherical halides Cl⁻, Br⁻, I⁻, linear thiocyanate SCN⁻, trigonal planar nitrate NO₃⁻, pyramidic iodate IO₃⁻, and tetrahedral sulfate SO₄²⁻). The binding energies of the resultant gaseous 1:1 complexes (1•Cl⁻,1•Br⁻, 1•I⁻, 1•SCN⁻, 1•NO₃⁻, 1•IO₃⁻ and 1•SO₄²⁻) were directly measured experimentally, exhibiting substantial non-covalent interactions with pronounced anion specific effects. The binding strengths of Cl⁻, NO₃⁻, IO₃⁻ with 1 are found to be strongest among all singly charged anions, amounting to ca. 30 kcal/mol, but only about 40% of that between 1 and SO₄²⁻. Quantum chemical calculations reveal that all anions reside in the center of the cavity of 1 with anion–π binding motif in the complexes’ optimized structures, where 1 is seen to be able to self-regulate its cavity structure to accommodate anions of different geometries and three-dimensional shapes. Electron density surface and natural bond orbital charge distribution analysis further support anion–π binding formation. The calculated binding energies of the anions and 1 nicely reproduce the experimentally estimated electron binding energy increase. This work

  9. g-factor of the Kπ = 14+ isomer in 176 W

    International Nuclear Information System (INIS)

    Ionescu-Bujor, M.; Iordachescu, A.; Marginean, N.; Brandolini, F.; Pavan, P.; Lenzi, S.M.; De Poli, M.; Gadea, A.; Martinez, T.; Medina, N.H.; Ribas, R.V.; Podolyak, Zs.

    2000-01-01

    to the beam direction, respectively, were used. The target was placed in an external magnetic field of 27.2(6) kG whose direction was periodically reversed. The time spectra of the 240, 351, 440 and 558 keV transitions in the ground-state band of 176 W, which collects most of the isomer decay were analysed according to the TDPAD procedures. The modulation ratio corresponding to the total accumulated statistics is presented together with the least-squares fit. For the g-factor of the 14 + isomeric state in 176 W the value g = +0.475(15) has been determined. The sensitivity of the magnetic moment to the nature of the involved quasiparticles allowed a definite configuration assignment for the 14 + isomer. We estimated the g-factors for all four-quasiparticle configurations with J π = K π = 14 + by using g Ω values deduced from experimental g-factors of the deformed single-particle states in odd-mass neighbouring nuclei. The π7/2 + [404] x π 9/2 - [514] x ν7/2 + [633] x ν5/2 - [512] pure configuration has been assigned to the 14 + isomeric state based on the excellent agreement between the calculated g-factor g cal = +0.47 and the measured value. We note that this assignment is in accordance with Woods-Saxon calculations for multi-quasiparticle states in 176 W. Information concerning the isomer shape will be obtained from a static quadrupole moment measurement which is in progress. (authors)

  10. In vivo metabolism and organ distribution of a branched {sup 14}C-nonylphenol isomer in pond snails, Lymnaea stagnalis L

    Energy Technology Data Exchange (ETDEWEB)

    Lalah, J.O.; Schramm, K.-W.; Severin, G.F.; Lenoir, D; Henkelmann, B.; Behechti, A.; Guenther, K.; Kettrup, A

    2003-02-26

    The branched isomers of p-nonylphenol (NP) are perceived to be more resistant to biodegradation in aquatic environments as well as to have more estrogen-like toxicity than the straight chain isomers. By use of GC-MS, some of them have been identified and found to exist in higher concentrations in the isomeric compound mixture than the straight chain isomers. The investigations of the distribution and metabolism of these branched isomers in aquatic organisms are therefore considered to be important in understanding the mechanisms of toxicity of NP. A single tertiary isomer of NP, 4(3'-,6'-dimethyl-3'-heptyl)-phenol, was synthesized in the laboratory and used in in vivo studies of its organ distribution and metabolism in Lymnaea stagnalis L., following a constant exposure of the organisms to {sup 14}C-NP isomer in water over a period of 8 days at an average exposure concentration of 105 ppb (range: 93-116 ppb). The results obtained clearly showed the distribution and bioconcentration of the isomer residues in various internal organs of Lymnaea after uptake in water and food. Analysis of the extracts of the organ tissues and faeces by HPLC and GC-MS after digestion with Pankreatin/{beta}-glucuronidase and nitric acid, respectively, showed that the isomer was metabolized by conjugation to glucuronic acid and hydroxylation to a catechol. The findings from these studies and their implications in the biotransformation and estrogenicity of NP in Lymnaea stagnalis L. are further discussed in detail in this paper.

  11. Spectral modulation through controlling anions in nanocaged phosphors

    NARCIS (Netherlands)

    Bian, H.; Liu, Y.; Yan, D.; Zhu, H.; Liu, C.; Xu, C.S.; Liu, Y.; Zhang, H.; Wang, X.

    2013-01-01

    A new approach has been proposed and validated to modulate the emission spectra of europium-doped 12CaO center dot 7Al(2)O(3) phosphors by tuning the nonradiative and radiative transition rates, realized by controlling the sort and amount of the encaged anions. A single wavelength at 255 nm can

  12. A new high-spin isomer in 195Bi

    International Nuclear Information System (INIS)

    Roy, T.; Mukherjee, G.; Rana, T.K.; Bhattacharya, Soumik; Asgar, Md.A.; Bhattacharya, C.; Bhattacharya, S.; Bhattacharyya, S.; Pai, H.; Madhavan, N.; Bala, I.; Gehlot, J.; Gurjar, R.K.; Jhingan, A.; Kumar, R.; Muralithar, S.; Nath, S.; Singh, R.P.; Varughese, T.; Basu, K.; Bhattacharjee, S.S.; Ghugre, S.S.; Raut, R.; Sinha, A.K.; Palit, R.

    2015-01-01

    A new high-spin isomer has been identified in 195 Bi at the focal plane of the HYbrid Recoil mass Analyser (HYRA) used in the gas-filled mode. The fusion evaporation reactions 169 Tm ( 30 Si, x n) 193, 195 Bi were used with the beam energies on targets of 168 and 146MeV for 6n and 4n channels, respectively. The evaporation residues, separated from the fission fragments, and their decays were detected at the focal plane of HYRA using MWPC, Si-Pad and clover HPGe detectors. The half-life of the new isomer in 195 Bi has been measured to be 1.6(1) μs. The configuration of the new isomer has been proposed and compared with the other isomers in this region. The Total Routhian Surface (TRS) calculations for the three-quasiparticle configurations corresponding to the new isomer suggest an oblate deformation for this isomeric state. The same calculations for different configurations in 195 Bi and for the even-even 194 Pb core indicate that the proton i 13/2 orbital has a large shape driving effect towards oblate shape in these nuclei. (orig.)

  13. A new high-spin isomer in {sup 195}Bi

    Energy Technology Data Exchange (ETDEWEB)

    Roy, T.; Mukherjee, G.; Rana, T.K.; Bhattacharya, Soumik; Asgar, Md.A.; Bhattacharya, C.; Bhattacharya, S.; Bhattacharyya, S.; Pai, H. [Variable Energy Cyclotron Centre, Kolkata (India); Madhavan, N.; Bala, I.; Gehlot, J.; Gurjar, R.K.; Jhingan, A.; Kumar, R.; Muralithar, S.; Nath, S.; Singh, R.P.; Varughese, T. [Inter University Acclerator Centre, New Delhi (India); Basu, K.; Bhattacharjee, S.S.; Ghugre, S.S.; Raut, R.; Sinha, A.K. [UGC-DAE-CSR Kolkata Centre, Kolkata (India); Palit, R. [Tata Institute of Fundamental Research, Department of Nuclear and Atomic Physics, Mumbai (India)

    2015-11-15

    A new high-spin isomer has been identified in {sup 195}Bi at the focal plane of the HYbrid Recoil mass Analyser (HYRA) used in the gas-filled mode. The fusion evaporation reactions {sup 169}Tm ({sup 30}Si, x n) {sup 193,} {sup 195}Bi were used with the beam energies on targets of 168 and 146MeV for 6n and 4n channels, respectively. The evaporation residues, separated from the fission fragments, and their decays were detected at the focal plane of HYRA using MWPC, Si-Pad and clover HPGe detectors. The half-life of the new isomer in {sup 195}Bi has been measured to be 1.6(1) μs. The configuration of the new isomer has been proposed and compared with the other isomers in this region. The Total Routhian Surface (TRS) calculations for the three-quasiparticle configurations corresponding to the new isomer suggest an oblate deformation for this isomeric state. The same calculations for different configurations in {sup 195}Bi and for the even-even {sup 194}Pb core indicate that the proton i{sub 13/2} orbital has a large shape driving effect towards oblate shape in these nuclei. (orig.)

  14. Kinetic Modeling using the Single-Event Methodology: Application to the Isomerization of Light Paraffins Modélisation cinétique basée sur la méthodologie des événements constitutifs : application à l’isomérisation des paraffines légères

    Directory of Open Access Journals (Sweden)

    Surla K.

    2011-08-01

    Full Text Available The construction of kinetic models is an important step in the development of refining processes. Indeed, these models can be used to predict the performances of the process, to optimize the operation of a unit and to optimally design a reactor and the associated process (choice of the reactor configuration, determination of optimal operating conditions, use of recycles, etc.. The current demand for models is particularly focused towards the development of detailed predictive models that are able to account for significant changes in process operation. Hence, they need to allow for the extrapolation to considerably different operating conditions or to very diverse feedstocks. Kinetic modeling based on the single-event theory meets these requirements, since it allows detailed prediction of the composition, and hence the yield structure from the reactors. The single-event theory was initially developed for the radical chemistry occurring during thermal cracking [Clymans et Froment (1984 Comput. Chem. Eng. 8, 2, 137-142; Hillewaert et al. (1988 AIChE J. 34, 1, 17-24; Willems et Froment (1988a Ind. Eng. Chem. Res. 27, 11, 1959-1966; Willems et Froment (1988b Ind. Eng. Chem. Res. 27, 11, 1966-1971], later extended to acid catalysis [Baltanas et Froment (1985 Comput. Chem. Eng. 9, 1, 71-81; Baltanas et al. (1989 Ind. Eng. Chem. Res. 28, 899-910; Vynckier et Froment (1991 Modeling of the kinetics of complex processes upon elementary steps, in Kinetic and thermodynamic lumping of multicomponent mixtures, Astarita G., Sandler S.I. (eds, Elsevier Science Publishers BV, Amsterdam, pp. 131-161], and recently adapted to metal catalyzed processes [Lozano-Blanco et al. (2006 Oil Gas Sci. Technol. 61, 4, 489-496; Lozano- Blanco et al. (2008 Ind. Eng. Chem. Res. 47, 16, 5879-5891]. This methodology developed in the “Laboratorium voor Petrochemische Techniek” at Ghent University consists in constructing a reaction network which, although exhaustive, is

  15. Microscopical study of K isomers in the nuclear region A ∼ 180

    International Nuclear Information System (INIS)

    Libert, J.; Quentin, P.; Pillet, N.; Ponsa, A.

    1997-01-01

    At present the K isomers are the best candidates for high density energy storage, although one of the major problems resides in the availability of simple and fast storage mechanisms. To respond to this question it is necessary to know thoroughly the structure of the concerned isomers and low energy modes of excitation. Particularly, proper to this type of studies is the region of A ∼ 180, where a large number of K isomers are known at present ( 178 Hf, 179 Hf and 180 Ta). Microscopic calculations using Skyrme SIII plus a simple pairing interaction lead to a good reproduction of certain single particle and collective spectroscopic properties of 178 Hf. In this region the spectroscopic properties are governed by three single proton states (5/2 - , 7/2 - and 9/2 + ) and by two single neutron states (7/2 + , 9/2 - ). The computed quasi-particle spectrum reproduces within 100 keV the energies of the isomeric states 16 + , 14 - , 25/2 - and 9 - . Based on this agreement one can predict a band spectroscopy rich in high K values due to a plenty of possible single particle combinations which have themselves high K value. Particularly, one have to stress the quasi-degeneracy of a K π = 15 + with the 16 + configuration in 178 Hf. Should this prediction experimentally be confirmed interesting consequences have to be expected on the spectroscopy above the 16 + isomer of 178 Hf as well as on the states implied in the decay of this storage state. Actually, 1 MeV above the 16 + state one can note isolated states reachable by parity breaking (or not breaking) transitions which could be mixture of K = 15, 14, 13, etc structures due to Coriolis interaction. The calculation reported are although simple (the approximation of the free quasi-particles on the BCS vacuum of 178 Hf). Under current study are the quantitative consequences of the Coriolis coupling, the decrease of pairing gaps with increasing quasi-particle number, the Hartree-Fock polarization (even and odd under time

  16. The spectroscopy and photochemistry of quinioline structural isomers: (E)- and (Z)-phenylvinylnitrile

    Energy Technology Data Exchange (ETDEWEB)

    Mehta-Hurt, Deepali N.; Korn, Joseph A.; Navotnaya, Polina; Parobek, Alexander P.; Clayton, Rachel M.; Zwier, Timothy S., E-mail: zwier@purdue.edu [Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907-2084 (United States)

    2015-08-21

    In Titan’s atmosphere, photochemical pathways that lead to nitrogen heteroaromatics may incorporate photoisomerization of their structural isomers as a final step. (E)- and (Z)-phenylvinylnitrile ((E)- and (Z)-PVN, C{sub 6}H{sub 5} —CH=CHCN) are structural isomers of quinoline that themselves possess extensive absorptions in the ultraviolet, and thus may engage in such photoisomerization pathways. The present study explores the vibronic spectroscopy and photo-induced isomerization of gas-phase (E)- and (Z)-PVN in the 33,600-35,850 cm{sup −1} region under jet-cooled conditions. The S{sub 0}-S{sub 1} origins for (E)- and (Z)-PVN have been identified at 33 827 cm{sup −1} and 33 707 cm{sup −1}, respectively. Isomer-specific UV-UV hole-burning and UV depletion spectra reveal sharp vibronic structure that extends over almost 2000 cm{sup −1}, with thresholds for fast non-radiative decay identified by a comparison between hole-burning and UV depletion spectra. Dispersed fluorescence spectra of the two isomers enable the assignment of many low frequency transitions in both molecules, aided by harmonic frequency calculations (B3LYP/6-311++G(d,p)) and a comparison with the established spectroscopy of phenylvinylacetylene, the ethynyl counterpart to PVN. Both isomers are proven to be planar in both the S{sub 0} ground and S{sub 1} electronic excited states. (E)-PVN exhibits extensive Duschinsky mixing involving out-of-plane modes whose frequencies and character change significantly in the ππ{sup ∗} transition, which modulates the degree of single- and double-bond character along the vinylnitrile substituent. This same mixing is much less evident in (Z)-PVN. The spectroscopic characterization of (E)- and (Z)-PVN served as the basis for photoisomerization experiments using ultraviolet hole-filling spectroscopy carried out in a reaction tube affixed to the pulsed valve. Successful interconversion between (E) and (Z)-PVN was demonstrated via ultraviolet hole

  17. Gas phase vibrational spectroscopy of the protonated water pentamer: the role of isomers and nuclear quantum effects.

    Science.gov (United States)

    Fagiani, Matias R; Knorke, Harald; Esser, Tim K; Heine, Nadja; Wolke, Conrad T; Gewinner, Sandy; Schöllkopf, Wieland; Gaigeot, Marie-Pierre; Spezia, Riccardo; Johnson, Mark A; Asmis, Knut R

    2016-09-29

    We use cryogenic ion trap vibrational spectroscopy to study the structure of the protonated water pentamer, H + (H 2 O) 5 , and its fully deuterated isotopologue, D + (D 2 O) 5 , over nearly the complete infrared spectral range (220-4000 cm -1 ) in combination with harmonic and anharmonic electronic structure calculations as well as RRKM modelling. Isomer-selective IR-IR double-resonance measurements on the H + (H 2 O) 5 isotopologue establish that the spectrum is due to a single constitutional isomer, thus discounting the recent analysis of the band pattern in the context of two isomers based on AIMD simulations 〈W. Kulig and N. Agmon, Phys. Chem. Chem. Phys., 2014, 16, 4933-4941〉. The evolution of the persistent bands in the D + (D 2 O) 5 cluster allows the assignment of the fundamentals in the spectra of both isotopologues, and the simpler pattern displayed by the heavier isotopologue is consistent with the calculated spectrum for the branched, Eigen-based structure originally proposed 〈J.-C. Jiang, et al., J. Am. Chem. Soc., 2000, 122, 1398-1410〉. This pattern persists in the vibrational spectra of H + (H 2 O) 5 in the temperature range from 13 K up to 250 K. The present study also underscores the importance of considering nuclear quantum effects in predicting the kinetic stability of these isomers at low temperatures.

  18. Anion exchange separation and purification of neodymium from fission products

    International Nuclear Information System (INIS)

    Ramkumar, K.L.; Raman, V.A.; Khodade, P.S.; Jain, H.C.

    1979-01-01

    Neodymium-148, the stable fission product has been proved to be one of the best monitors for the determination of nuclear fuel burn-up using triple spike isotope dilution mass spectrometry. For the precise and accurate determination of neodymium it is essential to separate it from bulk of other materials and purify from cerium and samarium which would otherwise cause isobaric interferences. A single stage anion exchange procedure for the separation and purification of neodymium from fission products has been developed. This method supercedes the lengthy and time consuming two stage anion exchange procedure normally used and ensures good chemical yield. (author)

  19. A study of model systems in anionic exchange

    International Nuclear Information System (INIS)

    Haegele, R.; Boeyens, J.C.A.

    1977-01-01

    Preliminary experiments are reported on the preparation and characterization of anionic sulphate and chloride complexes of UO 2+ 2 and iron(III), benzyl-trimethylammonium cation being used as a model substance for the simulation of positive sites in an anionic-exchange resin. The structure of (BTMA) 4 [UO 2 CL 3 -O 2 -CL 3 UO 2 ], a binuclear uranyl-peroxocomplex that has not been reported in the literature, was elucidated by single-crystal x-ray examination, and is described and discussed [af

  20. A Quick Reference on Anion Gap and Strong Ion Gap.

    Science.gov (United States)

    Torrente Artero, Carlos

    2017-03-01

    Metabolic acid-base disorders are common in emergency and critically ill patients. Clinicians may have difficulty recognizing their presence when multiple acid-base derangements are present in a single patient simultaneously. The anion gap and the strong ion gap concepts are useful calculations to identify the components of complex metabolic acid-base associated to the presence of unmeasured anions. This article presents their definition, normal values, indications, limitations, and guidelines for interpretation of changes in the clinical setting. Copyright © 2016 Elsevier Inc. All rights reserved.

  1. Preferential polymerization and adsorption of L-optical isomers of amino acids relative to D-optical isomers on kaolinite templates.

    Science.gov (United States)

    Jackson, T. A.

    1971-01-01

    Experiments on the polymerization of the L- and D-optical isomers of aspartic acid and serine using kaolinite as a catalyst showed that the L-optical isomers were polymerized at a much higher rate than the D-optical isomers; racemic (DL-) mixtures were polymerized at an intermediate rate. The peptides formed from the L-monomers were preferentially adsorbed by the clay. In the absence of kaolinite, no significant or consistent difference in the behavior of the L- and D-optical isomers was observed. In experiments on the adsorption of L- and D-phenylalanine by kaolinite, the L-optical isomer was preferentially adsorbed.

  2. Laser isotope and isomer separations: History and trends

    International Nuclear Information System (INIS)

    Paper will review history and principles of laser isotope and nuclear isomer separation: laser multistep photoionization of isotopic and isomeric atoms, laser IR-UV two-step photodissociation of molecules, laser IR multiphoton photodissociation of polyatomic molecules. The comparison and areas of applications of these methods will be considered. Paper will discuss a present state of art of technology of these methods in practical scale in various countries. In conclusion the trends of research in this field including applications of laser-separated isotopes and isomers will be considered

  3. Theoretical Study of the Diastereofacial Isomers of Aldrin and Dieldrin

    Directory of Open Access Journals (Sweden)

    Zoran Zdravkovski

    2006-02-01

    Full Text Available The Diels-Alder reaction of hexachlorocyclopentadiene with norbornadiene givesaldrin but theoretically three other diastereofacial isomers are possible. On oxidation theseisomers can generate eight adducts one of which is known as dieldrin. All these, as well asthe corresponding reactions with hexafluorocyclopenadiene were studied by semiempirical(AM1 and PM3 and hybrid density functional (B3LYP methods. Besides the energy levels,the transition states were calculated for the reactions leading to the diastereofacial isomers ofaldrin, which indicate that aldrin is the favored product of the reaction both fromthermodynamic and kinetic point of view.

  4. Calcium-tolerant anionic surfactants

    NARCIS (Netherlands)

    Kooreman, Alexander

    1995-01-01

    One of the problems of applying anionic surfactants in, for example, laundry detergents is the precipitation of calcium salts. Much effort has been directed towards avoiding precipitation. There are at least three ways for tackling the problem. The first involves the use of a large quantity of

  5. Quantum mechanics of toroidal anions

    International Nuclear Information System (INIS)

    Afanas'ev, G.N.

    1990-01-01

    We consider a toroidal solenoid with an electric charge attached to it. It turns out that statistical properties of the wave function describing interacting toroidal anions depend on both their relative position and orientation. The influence of the particular gauge choice on the exchange properties of the wave function is studied. 30 refs.; 6 figs

  6. Pu Anion Exchange Process Intensification

    Energy Technology Data Exchange (ETDEWEB)

    Taylor-Pashow, Kathryn M. L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2017-10-06

    This research is focused on improving the efficiency of the anion exchange process for purifying plutonium. While initially focused on plutonium, the technology could also be applied to other ion-exchange processes. Work in FY17 focused on the improvement and optimization of porous foam columns that were initially developed in FY16. These foam columns were surface functionalized with poly(4-vinylpyridine) (PVP) to provide the Pu specific anion-exchange sites. Two different polymerization methods were explored for maximizing the surface functionalization with the PVP. The open-celled polymeric foams have large open pores and large surface areas available for sorption. The fluid passes through the large open pores of this material, allowing convection to be the dominant mechanism by which mass transport takes place. These materials generally have very low densities, open-celled structures with high cell interconnectivity, small cell sizes, uniform cell size distributions, and high structural integrity. These porous foam columns provide advantages over the typical porous resin beads by eliminating the slow diffusion through resin beads, making the anion-exchange sites easily accessible on the foam surfaces. The best performing samples exceeded the Pu capacity of the commercially available resin, and also offered the advantage of sharper elution profiles, resulting in a more concentrated product, with less loss of material to the dilute heads and tails cuts. An alternate approach to improving the efficiency of this process was also explored through the development of a microchannel array system for performing the anion exchange.

  7. Anion binding in biological systems

    Energy Technology Data Exchange (ETDEWEB)

    Feiters, Martin C [Department of Organic Chemistry, Institute for Molecules and Materials, Faculty of Science, Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen (Netherlands); Meyer-Klaucke, Wolfram [EMBL Hamburg Outstation at DESY, Notkestrasse 85, D-22607 Hamburg (Germany); Kostenko, Alexander V; Soldatov, Alexander V [Faculty of Physics, Southern Federal University, Sorge 5, Rostov-na-Donu, 344090 (Russian Federation); Leblanc, Catherine; Michel, Gurvan; Potin, Philippe [Centre National de la Recherche Scientifique and Universite Pierre et Marie Curie Paris-VI, Station Biologique de Roscoff, Place Georges Teissier, BP 74, F-29682 Roscoff cedex, Bretagne (France); Kuepper, Frithjof C [Scottish Association for Marine Science, Dunstaffnage Marine Laboratory, Oban, Argyll PA37 1QA, Scotland (United Kingdom); Hollenstein, Kaspar; Locher, Kaspar P [Institute of Molecular Biology and Biophysics, ETH Zuerich, Schafmattstrasse 20, Zuerich, 8093 (Switzerland); Bevers, Loes E; Hagedoorn, Peter-Leon; Hagen, Wilfred R, E-mail: m.feiters@science.ru.n [Department of Biotechnology, Delft University of Technology, Julianalaan 67, 2628 BC Delft (Netherlands)

    2009-11-15

    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L{sub 3} (2p{sub 3/2}) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  8. Anion binding in biological systems

    International Nuclear Information System (INIS)

    Feiters, Martin C; Meyer-Klaucke, Wolfram; Kostenko, Alexander V; Soldatov, Alexander V; Leblanc, Catherine; Michel, Gurvan; Potin, Philippe; Kuepper, Frithjof C; Hollenstein, Kaspar; Locher, Kaspar P; Bevers, Loes E; Hagedoorn, Peter-Leon; Hagen, Wilfred R

    2009-01-01

    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L 3 (2p 3/2 ) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  9. Anion binding in biological systems

    Science.gov (United States)

    Feiters, Martin C.; Meyer-Klaucke, Wolfram; Kostenko, Alexander V.; Soldatov, Alexander V.; Leblanc, Catherine; Michel, Gurvan; Potin, Philippe; Küpper, Frithjof C.; Hollenstein, Kaspar; Locher, Kaspar P.; Bevers, Loes E.; Hagedoorn, Peter-Leon; Hagen, Wilfred R.

    2009-11-01

    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L3 (2p3/2) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  10. Methods and systems for measuring anions

    KAUST Repository

    Masih, Dilshad

    2016-08-18

    Embodiments of the present disclosure provide for methods for detecting the presence and/or concentration of anions in a solution, systems for detecting the presence and/or concentration of anions in a solution, anion sensor systems, and the like.

  11. The molecular properties of nitrobenzanthrone isomers and their mutagenic activities.

    Science.gov (United States)

    Ostojić, Bojana D; Stanković, Branislav; Ðorđević, Dragana S

    2014-06-01

    The mutagenic activity of five mono-substituted nitrobenzanthrones (NBA) has been determined in the Ames assay (Takamura-Enya et al., 2006). In the present study, a theoretical investigation of the electronic properties of all mono-substituted NBA isomers and their relation to mutagenic activity are presented. Equilibrium geometries, vertical ionization potentials (VIP), vertical electron affinities (VEA), relative energies, dipole moments and electronic dipole polarizabilities, and the IR and Raman spectra of NBA isomers calculated by Density Functional Theory (DFT) methods are presented. The position of the nitro group affects the spectral features of the IR and Raman spectra of the NBA isomers. The results show that a good linear relationship exists between the summation of Raman activities (∑ARaman) over all the 3N-6 vibrational modes and the mutagenic activity of the NBA isomers in Salmonella typhimurium strains. The spectroscopic results suggest that the unknown mutagenic activities of 4-NBA, 5-NBA, 6-NBA, 8-NBA and 10-NBA are predicted to follow the order 4-NBA>10-NBA>5-NBA>8-NBA>6-NBA. Copyright © 2013 Elsevier Ltd. All rights reserved.

  12. Determination of the excitation energy of high spin isomers

    International Nuclear Information System (INIS)

    Bjoernholm, S.; Borggreen, J.; Christensen, O.; Del Zoppo, A.; Herskind, B.; Pedersen, J.; Sletten, G.

    1979-01-01

    The sum spectrometer technique to study delayed radiation is discussed. Results on half-lives and isomer excitation energies are presented for 144 Gd, 147 Gd, 148 Tb, 151 Dy, 152 Dy, 149-153 Ho, 151 Er, 152 Er, 153 Er, and 154 Er. 2 figures, 1 table

  13. Heme isomers substantially affect heme's electronic structure and function

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2017-01-01

    Inspection of heme protein structures in the protein data bank reveals four isomers of heme characterized by different relative orientations of the vinyl side chains; remarkably, all these have been reported in multiple protein structures. Density functional theory computations explain this as due...

  14. Pregnanolone isomers, pregnenolone and their polar conjugates around parturition

    Czech Academy of Sciences Publication Activity Database

    Klak, J.; Hill, M.; Pařízek, A.; Havlíková, H.; Bičíková, M.; Hampl, R.; Fait, T.; Šulcová, J.; Pouzar, Vladimír; Kancheva, R.; Stárka, L.

    2003-01-01

    Roč. 52, - (2003), s. 211-221 ISSN 0862-8408 R&D Projects: GA ČR GA303/00/1559 Institutional research plan: CEZ:AV0Z4055905 Keywords : pregnanolone isomers * pregnanolone * maternal plasma Subject RIV: CC - Organic Chemistry Impact factor: 0.939, year: 2003

  15. "Star" morphologies of charged nanodrops comprised of conformational isomers

    Science.gov (United States)

    In Oh, Myong; Paliy, Maxim; Consta, Styliani

    2018-01-01

    We study the spatial distribution of conformational isomers surrounding a central macroion in a charged droplet with linear dimensions in the nanometer range. Dimethyl carbonate and formic acid are selected as typical solvents that undergo isomerization and a charged buckyball (C60) is selected as a representative example of a macroion. The study is performed by atomistic molecular dynamics simulations. We find that when the charge of the buckyball is above a threshold value, it induces the formation of concentric shells of different conformational isomers surrounding the macroion. The presence of layers with different dielectric properties necessitates the use of different state equations for the solvent polarization in each layer. We find that at a high charge state of the buckyball, the nearest layer to the macroion comprises the conformers with the highest dipole moment. The interface of the outer layers of conformers is characterized by "ray"-forming structures of the higher dielectric constant isomers penetrating into the layer of the lowest dielectric constant isomers. For high values of the solvent dielectric constant, the charged droplet acquires a "star"-like global shape. We demonstrate that these distinct droplet structures are a manifestation of charge-induced instability. We describe this simulation-based phenomenology by an analytical theory that supports this conclusion. The findings suggest new experimental research venues that may explore the reactivity and assembly of molecules within regions of different dielectric properties in droplets.

  16. FY2011 Annual Report for the Actinide Isomer Detection Project

    International Nuclear Information System (INIS)

    Warren, Glen A.; Francy, Christopher J.; Ressler, Jennifer J.; Erikson, Luke E.; Tatishvili, Gocha; Hatarik, R.

    2011-01-01

    This project seeks to identify a new signature for actinide element detection in active interrogation. This technique works by exciting and identifying long-lived nuclear excited states (isomers) in the actinide isotopes and/or primary fission products. Observation of isomers in the fission products will provide a signature for fissile material. For the actinide isomers, the decay time and energy of the isomeric state is unique to a particular isotope, providing an unambiguous signature for SNM. This project entails isomer identification and characterization and neutron population studies. This document summarizes activities from its third year - completion of the isomer identification characterization experiments and initialization of the neutron population experiments. The population and decay of the isomeric state in 235U remain elusive, although a number of candidate gamma rays have been identified. In the course of the experiments, a number of fission fragment isomers were populated and measured (Ressler 2010). The decays from these isomers may also provide a suitable signature for the presence of fissile material. Several measurements were conducted throughout this project. This report focuses on the results of an experiment conducted collaboratively by PNNL, LLNL and LBNL in December 2010 at LBNL. The measurement involved measuring the gamma-rays emitted from an HEU target when bombarded with 11 MeV neutrons. This report discussed the analysis and resulting conclusions from those measurements. There was one strong candidate, at 1204 keV, of an isomeric signature of 235U. The half-life of the state is estimated to be 9.3 μs. The measured time dependence fits the decay time structure very well. Other possible explanations for the 1204-keV state were investigated, but they could not explain the gamma ray. Unfortunately, the relatively limited statistics of the measurement limit, and the lack of understanding of some of the systematic of the experiment, limit

  17. The anion-binding polyanion: a molecular cobalt vanadium oxide with anion-sensitive visual response.

    Science.gov (United States)

    Seliverstov, Andrey; Forster, Johannes; Heiland, Magdalena; Unfried, Johannes; Streb, Carsten

    2014-07-25

    An anionic molecular cobalt vanadium oxide cluster, (n-Bu4N)3[Co(AcO)V4O12] and its use as anion binding site is reported. Cluster formation is controlled by an anion-dependent dynamic solution equilibrium. Reversible anion binding in solution leads to significant spectral changes, allowing the ratiometric optical detection of the anion concentration in situ, even under harsh thermal conditions (T = 90 °C). Comparative studies showed that the spectral response is dependent on the type of anion so that carboxylates, weakly coordinating anions and halides can be distinguished.

  18. Fuel properties of heptadecene isomers prepared via tandem isomerization-decarboxylation of oleic acid

    Science.gov (United States)

    Heptadecene isomers were prepared via tandem isomerization-decarboxylation of oleic acid using catalytic triruthenium dodecacarbonyl [Ru3(CO)12]. Chromatographic and spectroscopic characterization of the isolated heptadecene mixture indicated that it consisted of 96% internal isomers and 4% aromatic...

  19. Foundations of Isomer Physics for Energy Applications

    Science.gov (United States)

    2008-10-16

    14, 1393 (2004) 7. Roman Kolesov, Yuri Rostovstev, Olga Kocharovskaya.: Opt. Commun. 179, 537 (2000) 8. Hasan, Z., Biyikli, L., Macfarlane, PL...75 ps beam-off period, during which the data acquisition system was triggered by single y-ray events, time stamped using an external 10 MHz...AFOSR under Contract F49620-02-1-0187; the AWE (U.K.); and the EPSRC (U.K.). 047303-3 BRICK REPORTS PHYSICAL REVIEW C 76, 047303 (2007) [I] P. H

  20. Laser cooling of molecular anions.

    Science.gov (United States)

    Yzombard, Pauline; Hamamda, Mehdi; Gerber, Sebastian; Doser, Michael; Comparat, Daniel

    2015-05-29

    We propose a scheme for laser cooling of negatively charged molecules. We briefly summarize the requirements for such laser cooling and we identify a number of potential candidates. A detailed computation study with C_{2}^{-}, the most studied molecular anion, is carried out. Simulations of 3D laser cooling in a gas phase show that this molecule could be cooled down to below 1 mK in only a few tens of milliseconds, using standard lasers. Sisyphus cooling, where no photodetachment process is present, as well as Doppler laser cooling of trapped C_{2}^{-}, are also simulated. This cooling scheme has an impact on the study of cold molecules, molecular anions, charged particle sources, and antimatter physics.

  1. Laser Cooling of Molecular Anions

    CERN Document Server

    Yzombard, Pauline; Gerber, Sebastian; Doser, Michael; Comparat, Daniel

    2015-01-01

    We propose a scheme for laser cooling of negatively charged molecules. We briefly summarise the requirements for such laser cooling and we identify a number of potential candidates. A detailed computation study with C$\\_2^-$, the most studied molecular anion, is carried out. Simulations of 3D laser cooling in a gas phase show that this molecule could be cooled down to below 1 mK in only a few tens of milliseconds, using standard lasers. Sisyphus cooling, where no photo-detachment process is present, as well as Doppler laser cooling of trapped C$\\_2^-$, are also simulated. This cooling scheme has an impact on the study of cold molecules, molecular anions, charged particle sources and antimatter physics.

  2. Cationic metal complex, carbonatobis(1,10-phenanthroline)cobalt(III) as anion receptor: Synthesis, characterization, single crystal X-ray structure and packing analysis of [Co(phen) 2CO 3](3,5-dinitrobenzoate)·5H 2O

    Science.gov (United States)

    Sharma, Raj Pal; Singh, Ajnesh; Brandão, Paula; Felix, Vitor; Venugopalan, Paloth

    2009-03-01

    To explore the potential of [Co(phen) 2CO 3] + as anion receptor, red coloured single crystals of [Co(phen) 2CO 3](dnb)·5H 2O (dnb = 3,5-dinitrobenzoate) were obtained by recrystallizing the red microcrystalline product synthesised by the reaction of carbonatobis (1,10-phenanthroline)cobalt(III)chloride with sodium salt of 3,5-dinitrobenzoic acid in aqueous medium (1:1 molar ratio). The newly synthesized complex salt has been characterized by elemental analysis, spectroscopic studies (IR, UV/visible, 1H and 13C NMR), solubility and conductance measurements. The complex salt crystallizes in the triclinic crystal system with space group P1¯, having the cell dimensions a = 10.3140(8), b = 12.2885(11), c = 12.8747(13), α = 82.095(4), β = 85.617(4), γ = 79.221(4)°, V = 1585.6(2) Å 3, Z = 2. Single crystal X-ray structure determination revealed ionic structure consisting of cationic carbonatobis(1,10-phenanthroline)cobalt(III), dnb anion and five lattice water molecule. In the complex cation [Co(phen) 2CO 3] +, the cobalt(III) is bonded to four nitrogen atoms, originating from two phenanthroline ligands and two oxygen atoms from the bidentate carbonato group showing an octahedral geometry around cobalt(III) center. Supramolecular networks between ionic groups [ CHphen+⋯Xanion-] by second sphere coordination i.e. C sbnd H⋯O (benzoate), C sbnd H⋯O (nitro), C sbnd H⋯O (water) besides electrostatic forces of attraction alongwith π-π interactions stabilize the crystal lattice.

  3. New Insights in Catalytic Sites: Characterization of Spectroscopy and Reactivity of Metal Oxide Clusters with Anion Slow Electron Velocity-Map Imaging

    Science.gov (United States)

    2016-06-08

    sites in catalysis . These species present significant spectroscopic challenges, including multiple low-lying structural isomers, a dense manifold of...the very strong hydrogen -bonding in a binary complex of an anion and its conjugate acid is affected by solvation and hydration. Our experiments on...bisulfate is involved in hydrogen -bonding starting at n=1, and the water-water hydrogen bonds are present for n2. We have also begun investigating

  4. Identifying isomers of C-78 by means of x-ray spectroscopy

    DEFF Research Database (Denmark)

    Bassan, Arianna; Nyberg, Mats; Luo, Yi

    2002-01-01

    X-ray photoelectron and absorption spectra of C-78 isomers have been generated using density functional theory with inclusion of the full core-hole potentials. Strong isomer dependence has been found in absorption, but not in the photoelectron spectra. C-78 isomers can be thought to be formed...

  5. Identification of isomers and control of ionization and dissociation processes using dual-mass-spectrometer scheme and genetic algorithm optimization

    International Nuclear Information System (INIS)

    Chen Zhou; Qiu-Nan Tong; Zhang Cong-Cong; Hu Zhan

    2015-01-01

    Identification of acetone and its two isomers, and the control of their ionization and dissociation processes are performed using a dual-mass-spectrometer scheme. The scheme employs two sets of time of flight mass spectrometers to simultaneously acquire the mass spectra of two different molecules under the irradiation of identically shaped femtosecond laser pulses. The optimal laser pulses are found using closed-loop learning method based on a genetic algorithm. Compared with the mass spectra of the two isomers that are obtained with the transform limited pulse, those obtained under the irradiation of the optimal laser pulse show large differences and the various reaction pathways of the two molecules are selectively controlled. The experimental results demonstrate that the scheme is quite effective and useful in studies of two molecules having common mass peaks, which makes a traditional single mass spectrometer unfeasible. (paper)

  6. Cyanoform and Its Isomers. Relative Stabilities, Spectroscopic Features, and Rearrangements by Coupled Cluster and MCSCF-Based Methods.

    Science.gov (United States)

    Szczepaniak, Marek; Moc, Jerzy

    2017-02-16

    Although an isolation of elusive tricyanomethane HC(CN) 3 was recently reported, the existence of other HC 4 N 3 species has yet to be confirmed. In this work, the relative stabilities, spectroscopic features, and rearrangements of tricyanomethane and its four isomers are examined using single- (CCSD(T), CCSD(T)-F12) and multireference (MCSCF, MRPT2) methods. Tricyanomethane and dicyanoketenimine (NC) 2 CCNH, which are found to be the two most stable HC 4 N 3 isomers lying within 9 kcal/mol, can be discriminated by their spectroscopic parameters. The predicted stepwise interconversion path relating HC(CN) 3 and (NC) 2 CCNH features the HC 4 N 3 species comprising the C-C-N ring moiety, with the largest barrier being associated with the initial H migration to one of the CN carbons. Adding a water molecule reduces the H migration barrier strongly and makes it possible to interconvert tricyanomethane to dicyanoketenimine in a "concerted" way.

  7. A series of POM-based entangled frameworks with the rigid ligand 1,4-bis(1-imidazolyl)benzene and different isomers of octamolybdate

    International Nuclear Information System (INIS)

    Zang, Hong-Ying; Du, Dong-Ying; Li, Shun-Li; Lan, Ya-Qian; Yang, Guang-Sheng; Yan, Li-Kai; Shao, Kui-Zhan; Su, Zhong-Min

    2011-01-01

    With BIMB ligand, we have successfully obtained and characterized three novel entangled inorganic-organic hybrid compounds by choosing different metal ions, that is, [Ni(BIMB) 2 (γ-Mo 8 O 26 ) 0.5 ].3H 2 O (1), [Zn(BIMB) 2 (γ-Mo 8 O 26 ) 0.5 ] (2), and [Cu 3 (BIMB) 4 (H 2 O)(δ-Mo 8 O 26 )Cl 2 ].3H 2 O (3) (where BIMB=1,4-bis(1-imidazolyl)benzene). Compound 1 is a 2-fold interpenetration 4-connected 3D framework with the short Schlaefli symbol of (4x6 4 x8) 2 (4 2 x6 2 x8 2 ), in which octamolybdate anion shows γ-isomer; 2 exhibits a (5,6)-connected 3D self-penetrating topological motif with the short Schlaefli symbol of (4x5 7 x6 2 ) 2 (4 2 x5 11 x7 2 ), and 3 shows a (4,6)-connected self-penetrating 3D framework with the short Schlaefli symbol of (4 2 .5 2 .6.7) (4 4 .5.6 9 .8) (5 4 .6 2 ) whose octamolybdate has δ-isomer. In addition, the optical band gaps of these three compounds have been measured, which are 2.98 eV for 1, 3.42 eV for 2, and 2.88 eV for 3. Moreover, 2 has photoluminescent property, which can be attributed to ligand-to-metal charge-transfer (LMCT) band. -- Graphical abstract: With BIMB ligand, we have obtained and characterized three novel POM-based entangled hybrid compounds. Compound 1 is a 2-fold interpenetration 3D framework; 2 and 3 exhibit self-penetrating 3D polycatenated frameworks. Display Omitted Highlights: → Three novel octamolybdate-based entanglement frameworks successfully obtained by choosing the rigid ligand 1,4-bis(1-imidazolyl)benzene and different metal ions. Compound 1 is a 2-fold interpenetration 4-connected 3D framework; 2 exhibits a (5,6)-connected 3D self-penetrating topological net, and 3 shows a (4,6)-connected self-penetrating 3D framework. → In compounds 1 and 2, the octamolybdate anions show the γ-isomer, while in 3 the octamolybdate anion is a δ-isomer. → Optical band gap of these three compounds have been investigated and the results show that they are all wide gap semiconductors, which are 2.98 e

  8. Anion

    Directory of Open Access Journals (Sweden)

    A. Vadivel Murugan

    2003-01-01

    . Its characterization is investigated by Fourier Transform Infrared Spectroscopy (FT-IR and Scanning Electron Microscopy (SEM. The hybrid material presents predominantly high electronic conductivities of around 2.0 and 7.0 S cm-1 at 300 and 400K respectively.

  9. The Search for High Spin State Isomers in the Atomic Mass Region 178-192

    International Nuclear Information System (INIS)

    Ellahrah, M.S.; Arfa, N.S.

    2007-01-01

    Isomers for elements far a way from line of stability are a new field for research to produce artificial isomers that can store considerable amount of energy in small amount of mass without the dangerous hazards on life and environment. These isomers could have very short life time or very long one 10th and 100th of years. It will be possible to get the stored energy by stimulated emission . The purpose of this work to use a theorical model based on Bcs method to find out the possible isomers in the mass reg on 178-192 even -even isotopes so that experimentalists can concentrate their research on these predicted isomers.

  10. Quadrupole moment of the 8/sup -/ isomer in /sup 112/Sb

    Energy Technology Data Exchange (ETDEWEB)

    Mahnke, H.; Dafni, E.; Rafailovich, M.H.; Sprouse, G.D.; Vapirev, E.

    1982-08-01

    The quadrupole interaction of the 8/sup -/ isomeric state (T/sub 1/2/ = 536 ns) in /sup 112/Sb has been measured using the time differential perturbed angular distribution method. The linear momentum transfer from the /sup 103/Rh(/sup 12/C, 3n) reaction recoiled the isomeric nuclei into single crystals of Sb and Sn and a polycrystalline In foil. From the quadrupole coupling constant for the 8/sup -/ state of /sup 112/Sb in Sb, the quadrupole moment was obtained relative to the moment of the stable ground state of /sup 121/Sb: Vertical BarQ(/sup 112/Sb,8/sup -/)/Q(/sup 121/Sb,(5/2)/sup +/)Vertical Bar = 1.958(10). The value is in accordance with the description of the isomer as an odd proton coupled to a neutron-excited Sn core. In addition, the measured coupling constants in Sn and In allow the determination of the quadrupole moments of isomers in /sup 120,122/Sb and /sup 115/Sb.

  11. Decreased anion gap in polyclonal hypergammaglobulinemia.

    Science.gov (United States)

    Qujeq, Durdi; Mohiti, Javad

    2002-02-01

    The anion gap has proved a valuable tool in the diagnosis of various forms of acid-base disorders, although the importance of slight rises in the anion gap remains unclear. The concept of the anion gap is often misunderstood and misapplied. The relationship between gammaglobulins and the serum anion gap has not received much attention except for reports of a narrowing of the gap associated with certain monoclonal immunoglobulin G gammopathies. We present patients with polyclonal gammopathy, the magnitude of which correlated strongly and negatively with the anion gap. The anion gap can be readily calculated from routine laboratory data, and anion gap was calculated as ([Na] +[K])- ([Cl] + [HCO3]). Serum anion gaps were determined in 206 patients with polyclonal hypergammaglobulinemia and 63 healthy subjects. Serum sodium and potassium ions concentration were determined by flame photometry. Serum bicarbonate level was measured as total carbon dioxide content. Serum chloride level was determined by chlorimetric titration with silver ions. All patients with polyclonal hypergammaglobulinemia had a statistically significant reduction in their mean serum anion gaps (6.4 +/- 1.2 mmol/L) when compared with normal control volunteers (15.3 +/- 2.4 mmol/L), p anion gap and gammaglobulins concentration.

  12. Specificity of anion-binding in the substrate-pocket ofbacteriorhodopsin

    Energy Technology Data Exchange (ETDEWEB)

    Facciotti, Marc T.; Cheung, Vincent S.; Lunde, Christopher S.; Rouhani, Shahab; Baliga, Nitin S.; Glaeser, Robert M.

    2003-08-30

    The structure of the D85S mutant of bacteriorhodopsin with a nitrate anion bound in the Schiff-base binding site, and the structure of the anion-free protein have been obtained in the same crystal form. Together with the previously solved structures of this anion pump, in both the anion-free state and bromide-bound state, these new structures provide insight into how this mutant of bacteriorhodopsin is able to bind a variety of different anions in the same binding pocket. The structural analysis reveals that the main structural change that accommodates different anions is the repositioning of the polar side-chain of S85. On the basis of these x-ray crystal structures, the prediction is then made that the D85S/D212N double mutant might bind similar anions and do so over a broader pH range than does the single mutant. Experimental comparison of the dissociation constants, K{sub d}, for a variety of anions confirms this prediction and demonstrates, in addition, that the binding affinity is dramatically improved by the D212N substitution.

  13. Isomer-specific consumption of galactooligosaccharides by bifidobacterial species

    Science.gov (United States)

    Tsui, Man Ki; Mills, David A.; Lebrilla, Carlito B.

    2014-01-01

    Prebiotics are non-digestible substrates that stimulate the growth of beneficial microbes in the human intestine. Galactooligosaccharides (GOS) are food ingredients that possess prebiotic properties, in particular, promoting the growth of bifidobacteria in situ. However precise mechanistic details of GOS consumption by bifidobacteria remains poorly understood. Because GOS are mixtures of polymers of different lengths and linkages, there is interest to determine which specific structures provide prebiotic effects in order to potentially create better supplements. We here present a method comprising porous graphitic carbon separation, isotopic labeling and mass spectrometry analysis for the structure specific analysis of GOS isomers and their bacterial consumption rate. Using this strategy, the differential bacterial consumption of GOS by the bifidobacteria species B. longum subsp. infantis, B. animalis subsp. lactis and B. adolescentis was determined, indicating that the use of specific GOS isomers in infant formula may provide enrichment of distinct species. PMID:24313277

  14. Inmersiones isométricas en variedades riemannianas

    Directory of Open Access Journals (Sweden)

    Carlos Alberto Marín Arango

    2011-06-01

    Full Text Available Este trabajo recapitula la teoría básica de conexiones en fibrados principales y fibrados vectoriales con el fin de aplicar tales teorías al estudio de inmersiones isométricas en variedades riemannianas; por medio de una versión apropiada del teorema de Frobenius mostramos un resultado que generaliza el teorema fundamental de las inmersiones isométricas. Abstract. This paper summarizes the basic theory of connections in principal bundles and vector bundles in order to apply these theories to the study of isometric immersions in Riemannian manifolds; by an appropriate version of the Frobenius theorem we show a result that generalizes the Fundamental Theorem of isometric immersions.

  15. One-of-A-Kind: A Microporous Metal-Organic Framework Capable of Adsorptive Separation of Linear, Mono- and Di-branched Alkane Isomers via Temperature- and Adsorbate-Dependent Molecular Sieving

    KAUST Repository

    Wang, Hao

    2018-03-29

    Separation of alkane isomers represents a crucial process in the petrochemical industry in order to achieve high octane rating of gasoline. Herein, we report the first example of complete separation of linear, monobranched and dibranched alkane isomers by a single adsorbent. A calcium-based robust microporous metal-organic framework, Ca(H2tcpb) (tcpb = 1,2,4,5-tetrakis(4-carboxyphenyl)-benzene) exhibits unique molecular exclusion behavior which enables full separation of binary or ternary mixtures of alkane isomers into pure form of each isomerate. The successful separation of monobranched and dibranched hexane isomers will not only lead to the production of higher quality gasoline with maximum possible octane numbers but also fill the gap in the current separation technology. Exploration of separation mechanism indicates that structural flexibility and adsorbate-dependent structure change of the porous framework plays a vital role for the observed temperature-dependent molecular sieving property of the adsorbent.

  16. High spin states and Yrast isomers in 211Rn

    International Nuclear Information System (INIS)

    Poletti, A.R.; Dracoulis, G.D.; Fahlander, C.; Morrison, I.

    1981-01-01

    Excited states in 211 Rn with spins up to 53/2 have been identified using (HI,xn) reactions and γ-ray techniques. A shell model calculation can reproduce the ordering of the yrast sequence up to spin 41/2 - . Several yrast isomers have been identified. Enhanced E3 transitions are observed and their systematic occurrence in this region discussed. The influence of the neutron hole, and possible core excitations on the effective moment of inertia are also pointed out

  17. Island of high-spin isomers near N = 82

    International Nuclear Information System (INIS)

    Pedersen, J.; Back, B.B.; Bernthal, F.M.; Bjornholm, S.; Borggreen, J.; Christensen, O.; Folkmann, F.; Herskind, B.; Khoo, T.L.; Neiman, M.; Puehlhofer, F.; Sletten, G.

    1977-01-01

    Experiments aimed at testing for the existence of yrast traps are reported. A search for delayed γ radiation of lifetimes longer than approx. 10 ns and of high multiplicity has been performed by producing more than 100 compound nuclei between Ba and Pb in bombardments with 40 Ar, 50 Ti, and 65 Cu projectiles. An island of high-spin isomers is found to exist in the region 64 or approx. = 71 and N < or approx. = 82

  18. High spin states and yrast isomers in 211Rn

    International Nuclear Information System (INIS)

    Poletti, A.R.; Dracoulis, G.D.; Fahlander, C.; Morrison, I.

    1980-12-01

    Excited states in 211 Rn with spins up to 53/2 have been identified using (HI,xn) reactions and γ-ray techniques. A shell model calculation can reproduce the ordering of the yrast sequence up to spin 41/2. Several yrast isomers have been identified. Enhanced E3 transitions are observed and their systematic occurrence in this region discussed. The influence of the neutron hole, and possible core excitations on the effective moment of inertia are also pointed out

  19. Observation of the new isomer 32mAl

    International Nuclear Information System (INIS)

    Robinson, M.; Halse, P.; Lewitowicz, M.; Saint-Laurent, M.G.

    1995-01-01

    A new isomer in the neutron-rich isotope 32 Al has been identified among the fragmentation products of a 40 Ar 16+ beam using the LISE spectrometer at GANIL. The population of the isomeric state was inferred from the detection of γ-radiation following its decay in coincidence with its respective heavy-ion implantation signal. The half-life of 32m Al was determined to be 240 ± 30 ns. (author)

  20. Butane isomer separation with composite zeolite MFI mebranes

    Czech Academy of Sciences Publication Activity Database

    Hrabánek, Pavel; Zikánová, Arlette; Bernauer, B.; Fíla, V.; Kočiřík, Milan

    2009-01-01

    Roč. 245, 1-3 (2009), s. 437-443 ISSN 0011-9164 R&D Projects: GA ČR GA203/07/1443; GA AV ČR KAN400720701; GA AV ČR(CZ) 1QS401250509 Institutional research plan: CEZ:AV0Z40400503 Keywords : zeolite MFI * membranes * separation * butane isomers Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.034, year: 2009

  1. Characteristics of Butanol Isomers Oxidation in a Micro Flow Reactor

    KAUST Repository

    Bin Hamzah, Muhamad Firdaus

    2017-05-01

    Ignition and combustion characteristics of n-butanol/air, 2-butanol.air and isobutanol/air mixtures at stoichiometric (ϕ = 1) and lean (ϕ = 0.5) conditions were investigated in a micro flow reactor with a controlled temperature profile from 323 K to 1313 K, under atmospheric pressure. Sole distinctive weak flame was observed for each mixture, with inlet fuel/air mixture velocity set low at 2 cm/s. One-dimensional computation with comprehensive chemistry and transport was conducted. At low mixture velocities, one-stage oxidation was confirmed from heat release rate profiles, which was broadly in agreement with the experimental results. The weak flame positions were congruent with literature describing reactivity of the butanol isomers. These weak flame responses were also found to mirror the trend in Anti-Knock Indexes of the butanol isomers. Flux and sensitivity analyses were performed to investigate the fuel oxidation pathways at low and high temperatures. Further computational investigations on oxidation of butanol isomers at higher pressure of 5 atm indicated two-stage oxidation through the heat release rate profiles. Low temperature chemistry is accentuated in the region near the first weak cool flame for oxidation under higher pressure, and its impact on key species – such as hydroxyl radical, hydrogen peroxide and carbon monoxide – were considered. Both experimental and computational findings demonstrate the advantage of employing the micro flow reactor in investigating oxidation processes in the temperature region of interest along the reactor channel. By varying physical conditions such as pressure, the micro flow reactor system is proven to be highly beneficial in elucidating oxidation behavior of butanol isomers in conditions in engines such as those that mirror HCCI operations.

  2. Comparison of the Weisskopf estimates in spin and K-isomers

    International Nuclear Information System (INIS)

    Garg, Swati; Maheshwari, B.; Rajput, Rohit; Srivastava, P.C.; Jain, A.K.

    2014-01-01

    Nuclear isomers are the excited metastable states, which exist due to the hindrance on their decay. Study of isomers has recently become very popular due to advances in the experimental techniques and also the arrival of radioactive beams. Large amount of new experimental data is becoming available. The very first 'Atlas of nuclear isomers' lists more than 2460 nuclear isomers with the half-life cut off at 10 ns. Spin isomers mostly exist due to the difficulty in meeting the spin selection rules and cluster around the semi-magic regions. The isomers far from the magic-numbers, which lie in the well-deformed region, mostly exist due to the goodness of the K-quantum number and large K-difference between the decaying states. They are known as K-isomers

  3. Environmental behavior of inorganic anions

    International Nuclear Information System (INIS)

    Garland, T.R.; Cataldo, D.A.; Fellows, R.J.; Wildung, R.E.

    1987-01-01

    Recent efforts have addressed two aspects of anion behavior in the soil/plant system. The first involves evaluation of the gaseous component of the terrestrial iodine cycle in soils and plants. Field analyses of 129 I in soils and vegetation adjacent to a fuels reprocessing facility, which was idle for 10 years prior to the study, indicated that there may be a significant gaseous component to the terrestrial iodine cycle. Soil substrates, including a silt-sand, organic forest soil, quartz sand, and a sterilized soil, were amended with radioiodide, and the rates and quality of the volatile components evaluated

  4. Nuclear structure via isomer tagging of fission fragments

    Science.gov (United States)

    Wu, C. Y.; Cline, D.; Simon, M. W.; Stoyer, M. A.

    1997-10-01

    The high efficiency for detecting high-fold γ rays by large Ge arrays makes it possible to study the detailed spectroscopy of many neutron-rich nuclei produced by fission. Major progress has been made using sealed spontaneous fission sources. Considerable improvement in selectivity is provided, with an open source, both by gating on isomers and by detection of both fission fragments in coincidence with the deexcitation γ rays (see the preceding contribution). The reconstructed kinematics allows a measure of fragment mass and the Doppler shift correction of γ rays. In a recent experiment, fission fragments were detected using half of the CHICO array and an annular PPAC in coincidence with deexcitation γ rays detected by the Rochester array of eight Compton-suppressed Ge detectors. The annular PPAC was located only 1.0" from a 3.7 μCi ^252Cf source for efficient isomer tagging. The correlation was studied between delayed, within a time window between 150 ns and 10 μs after a fission occurring, and prompt γ rays. Several prominent feeding patterns to isomers in the mass region around 100 and 130 are identified by such correlation study. Experimental details and results will be presented.

  5. Nuclear Structure Studies of Microsecond Isomers Near A=100

    Science.gov (United States)

    Simpson, G.; Genevey, J.; Pinston, J. A.; Urban, W.; Zlomaniec, A.; Orlandi, R.; Scherillo, A.; Tsekhanovich, I.; Smith, A. G.; Thallon, A.; Varley, B. J.; Jolie, J.; Warr, N.

    2007-04-01

    A large variety of shapes may be observed in Sr and Zr nuclei of the A = 100 region when the number of neutrons increases from N = 58 to N = 64. The lighter isotopes are rather spherical. It is also well established that three shapes co-exist in the transitional odd-A, N = 59, Sr and Zr nuclei. For N > 59, strongly deformed axially symmetric bands are observed. Recently, a new isomer of half-life 1.4(2) mu s was observed in 95Kr, the odd-odd 96Rb has been reinvestigated and a new high-spin isomer observed in the even-even 98Zr. These nuclei were studied by means of prompt gamma -ray spectroscopy of the spontaneous fission of 248Cm using the EUROGAM 2 Ge array and/or measurements of mu s isomers produced by fission of 239,241Pu with thermal neutrons at the ILL (Grenoble). To allow spectroscopic studies of isomeric states with lifetimes around 100 ns, across a broad range of medium-heavy neutron-rich nuclei, an experiment was performed at a neutron guide of the ILL using thermal-neutron-induced fission. Fission fragments were identified using a small spectrometer consisting of a section to measure time-of-flight and an ionization chamber. Isomeric gamma rays emitted from complementary fragments were detected in an array of Ge detectors.

  6. Isomer probes of nuclear structure following deep inelastic collisions

    CERN Document Server

    Al-Garni, S A; Walker, P

    2002-01-01

    Deep-inelastic collisions of sup 1 sup 3 sup 6 Xe ions with tantalum, tungsten and rhenium targets have been used to study beta-decays and high-spin isomers in neutron-rich A approx 180 nuclei at the GSI on-line mass separator. In particular, gamma rays -associated with the decay of the previously identified K suppi = 37/2 sup - , T sub 1 sub / sub 2 = 51 min isomer in sup 1 sup 7 sup 7 Hf have been observed, but with an unexpectedly high yield considering the release efficiency for short-lived hafnium isotopes from a thermal ion source. These results may be interpreted as possible evidence for a hitherto unrecognised, high-spin beta-decaying isomer in sup 1 sup 7 sup 7 Lu. A two-component half-life analysis of the sup 1 sup 7 sup 7 Hf gamma-ray intensities gives an upper-lying component of 6 + 3 - 2 min, when the lower-lying component half-life is fixed at 51 min. Nilsson multi-quasiparticle calculations with BCS pairing predict a favoured K suppi = 39/2 sup - state in sup 1 sup 7 sup 7 Lu, which is a candid...

  7. Ternary fission of spontaneously fissile uranium isomers excited by neutrons

    International Nuclear Information System (INIS)

    Makarenko, V.E.; Molchanov, Y.D.; Otroshchenko, G.A.; Yan'kov, G.B.

    1989-01-01

    Spontaneously fissile isomers (SFI) of uranium were excited in the reactions 236,238 U(n,n') at an average neutron energy 4.5 MeV. A pulsed electrostatic accelerator and time analysis of the fission events were used. Fission fragments were detected by the scintillation method, and long-range particles from fission were detected by an ionization method. The relative probability of fission of nuclei through a spontaneously fissile isomeric state was measured: (1.30±0.01)·10 -4 ( 236 U) and (1.48±0.02)·10 -4 ( 238 U). Half-lives of the isomers were determined: 121±2 nsec (the SFI 236 U) and 267±13 nsec (the SFI 238 U). In study of the ternary fission of spontaneously fissile isotopes of uranium it was established that the probability of the process amounts to one ternary fission per 163±44 binary fissions of the SFI 236 U and one ternary fission per 49±14 binary fissions of the SFI 238 U. The substantial increase of the probability of ternary fission of SFI of uranium in comparison with the case of ternary fission of nuclei which are not in an isomeric state may be related to a special nucleon configuration of the fissile isomers of uranium

  8. Interstellar Anions: The Role of Quantum Chemistry.

    Science.gov (United States)

    Fortenberry, Ryan C

    2015-10-01

    Six anions have been conclusively detected in the interstellar medium (ISM). They all arrived within a five-year window ending five years ago. Why have no new anions been detected? It is likely a lack of laboratory data for novel anions. This work reviews the role that valence and dipole-bound excited states may play in the formation, detection, and lifetime of anions that may yet be observed in the ISM and how quantum chemistry enhances this understanding. The list of interstellar anions has certainly not been exhausted by any means, but electronic, spectroscopic, and structural data must be provided to aid in any future detections. Quantum chemistry has the flexibility and completeness to provide a full picture of these systems and has shown exceptional accuracies of late. The work reviewed herein gives an overview of what quantum chemical computations have produced and will continue to provide related to anions and how this will enhance both laboratory experiment and astronomical observation.

  9. Clinical usefulness of the serum anion gap.

    Science.gov (United States)

    Lee, Sik; Kang, Kyung Pyo; Kang, Sung Kyew

    2006-03-01

    The anion gap in the serum is useful in the interpretation of acid-base disorders and in the diagnosis of other conditions. In the early 1980s, ion-selective electrodes for specific ionic species were introduced for the measurement of serum electrolytes. This new method has caused a shift of the anion gap from 12±4 mEq/L down 6±3 mEq/L. It is worthy for clinicians to understand the range of normal anion gap and the measuring methods for serum sodium and chloride in the laboratories that support their practice. While an increase in the anion gap is almost always caused by retained unmeasured anions, a decrease in the anion gap can be generated by multiple mechanisms.

  10. Schlenk Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar

    2015-09-01

    Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands for time and skilled technical personnel, HVTs are currently used in only a few research laboratories worldwide. Instead, most researchers in this filed are attracted to more facile Schlenk techniques. The basic principle of this technique followed in all laboratories is substantially the same, i.e. the use of alternate vacuum and inert gas atmosphere in glass apparatus for the purification/charging of monomer, solvents, additives, and for the manipulation of air-sensitive compounds such as alkyl metal initiators, organometallic or organic catalysts. However, it is executed quite differently in each research group in terms of the structure of Schlenk apparatus (manifolds, connections, purification/storage flasks, reactors, etc.), the use of small supplementary devices (soft tubing, cannulas, stopcocks, etc.) and experimental procedures. The operational methods are partly purpose-oriented while also featured by a high flexibility, which makes it impossible to describe in detail each specific one. In this chapter we will briefly exemplify the application of Schlenk techniques for anionic polymerization by describing the performance of a few experiments from our own work.

  11. Isolation by crystallization of translational isomers of a bistable donor-acceptor [2]catenane

    Science.gov (United States)

    Wang, Cheng; Olson, Mark A.; Fang, Lei; Benítez, Diego; Tkatchouk, Ekaterina; Basu, Subhadeep; Basuray, Ashish N.; Zhang, Deqing; Zhu, Daoben; Goddard, William A.; Stoddart, J. Fraser

    2010-01-01

    The template-directed synthesis of a bistable donor-acceptor [2]catenane wherein both translational isomers—one in which a tetrathiafulvalene unit in a mechanically interlocked crown ether occupies the cavity of a cyclobis(paraquat-p-phenylene) ring and the other in which a 1,5-dioxynaphthalene unit in the crown ether resides inside the cavity of the tetracationic cyclophane—exist in equilibrium in solution, has led to the isolation and separation by hand picking of single crystals colored red and green, respectively. These two crystalline co-conformations have been characterized separately at both the molecular and supramolecular levels, and also by dynamic NMR spectroscopy in solution where there is compelling evidence that the mechanically interlocked molecules are present as a complex mixture of translational, configurational, and conformational isomers wherein the isomerization is best described as being a highly dynamic and adaptable phenomenon. PMID:20663950

  12. The Multiplexed Chemical Kinetic Photoionization Mass Spectrometer: A New Approach To Isomer-resolved Chemical Kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Osborne, David L.; Zou, Peng; Johnsen, Howard; Hayden, Carl C.; Taatjes, Craig A.; Knyazev, Vadim D.; North, Simon W.; Peterka, Darcy S.; Ahmed, Musahid; Leone, Stephen R.

    2008-08-28

    We have developed a multiplexed time- and photon-energy?resolved photoionizationmass spectrometer for the study of the kinetics and isomeric product branching of gasphase, neutral chemical reactions. The instrument utilizes a side-sampled flow tubereactor, continuously tunable synchrotron radiation for photoionization, a multi-massdouble-focusing mass spectrometer with 100percent duty cycle, and a time- and positionsensitive detector for single ion counting. This approach enables multiplexed, universal detection of molecules with high sensitivity and selectivity. In addition to measurement of rate coefficients as a function of temperature and pressure, different structural isomers can be distinguished based on their photoionization efficiency curves, providing a more detailed probe of reaction mechanisms. The multiplexed 3-dimensional data structure (intensity as a function of molecular mass, reaction time, and photoionization energy) provides insights that might not be available in serial acquisition, as well as additional constraints on data interpretation.

  13. The many ways of making anionic clays

    Indian Academy of Sciences (India)

    Unknown

    Indian Academy of Sciences. 671. The many ways of making anionic ... In all these cases, the negative charge is compensated for by the inclusion of positive ions in the interlayer region, by virtue ..... as anionic clays. Acknowledgements. The authors thank the Department of Science and Technology, New Delhi for financial.

  14. Test procedure for anion exchange chromatography

    International Nuclear Information System (INIS)

    Cooper, T.D.

    1994-01-01

    Plutonium from stored nitrate solutions will be sorbed onto anion exchange resins and converted to storable plutonium dioxide. Useful information will be simultaneously gained on the thermal stability and ion exchange capacity of four commercially available anion exchange resins over several years and under severe degradative conditions. This information will prove useful in predicting the safe and efficient lifetimes of these resins

  15. Simultaneous anion and cation mobility in polypyrrole

    DEFF Research Database (Denmark)

    Skaarup, Steen; Bay, Lasse; Vidanapathirana, K.

    2003-01-01

    Polypyrrole (PPy) polymer films permanently doped with large, immobile anion dodecyl benzene sulfonate (DBS) have been characterized by cyclic voltammetry in order to clarify the roles of cations and anions in the aqueous electrolyte as mobile ions in the film. Aqueous solutions of 0.05-0.1 M...

  16. Fungal growth on anion surfactant medium.

    Science.gov (United States)

    Hamada, Nobuo; Abe, Niichiro

    2009-12-01

    Before the present study, no fungi using anion surfactant as a nutrient had been identified, although some fungi were known to use nonion surfactant. Washing water collected from 63 washing machines was inoculated onto 0.1% LAS (Sodium dodecyl benzenesulfonate) anion surfactant media to identify fungi that can feed on anion-surfactant. Small dark colonies of fungi were found on several of the Petri-dishes from 12 days after inoculation. These were identified as Cladophialophora boppii and Exophiala spinifera using morphological features and rDNA data. A number of the isolates of C. boppii specifically were recognized as using anion surfactant as a nutrient. The growth characteristics of the two fungal species were examined on surfactant media of three kinds. Apart from anion surfactant, the fungi were also able to grow on nonion surfactant and on soap. The application of these fungi for environmental cleansing after detergent pollution is also discussed.

  17. Creating molecular macrocycles for anion recognition

    Directory of Open Access Journals (Sweden)

    Amar H. Flood

    2016-03-01

    Full Text Available The creation and functionality of new classes of macrocycles that are shape persistent and can bind anions is described. The genesis of triazolophane macrocycles emerges out of activity surrounding 1,2,3-triazoles made using click chemistry; and the same triazoles are responsible for anion capture. Mistakes made and lessons learnt in anion recognition provide deeper understanding that, together with theory, now provides for computer-aided receptor design. The lessons are acted upon in the creation of two new macrocycles. First, cyanostars are larger and like to capture large anions. Second is tricarb, which also favors large anions but shows a propensity to self-assemble in an orderly and stable manner, laying a foundation for future designs of hierarchical nanostructures.

  18. Closing the gap on unmeasured anions

    Science.gov (United States)

    Kellum, John A

    2003-01-01

    Many critically ill and injured patients, especially those with metabolic acidosis, have abnormally high levels of unmeasured anions in their blood. At the same time, such patients are prone to hypoalbuminemia, which makes the traditional anion gap calculation inaccurate. Thus, little is known about the epidemiology and clinical consequences of an excess in unmeasured anions in the blood. Indeed, even the etiology of these "missing ions" is often unclear. Unfortunately, more precise means of quantifying unmeasured anions, such as the strong ion gap (SIG), are cumbersome to use clinically. However, a simple means of correcting the anion gap can be used to estimate SIG and may provide additional insight into this common clinical problem. PMID:12793870

  19. Shape isomer excitation by mu-minus capture

    International Nuclear Information System (INIS)

    Kaplan, S.N.; Monard, J.A.; Nagamiya, S.

    1975-06-01

    In a search for back-decay gamma rays from the shape isomer in 238 U following mu-minus capture, no candidates have been found with yields greater than 2 percent of the muon stoppings. The intensities of the gamma rays are insufficient to permit definitive lifetime measurements of individual peaks; however, for 500-keV energy ranges of gamma ray pulses, lifetimes have been determined that give results consistent with recent electron lifetime measurements. (6 figures, 2 tables) (U.S.)

  20. Three minor valepotriate isomers from Valeriana jatamansi and their cytotoxicity.

    Science.gov (United States)

    Lin, Sheng; Fu, Peng; Chen, Tao; Ye, Ji; Yang, Xian-Wen; Zhang, Wei-Dong

    2017-01-01

    Three new minor valepotriate isomers, jatamanvaltrates Z1 (1), Z2 (2), and Z3 (3), have been isolated from the whole plants of Valeriana jatamansi (syn. Valeriana wallichii.). Their structures were elucidated by extensive spectroscopic analysis, especially 2D NMR and ESI-MS/MS n . All isolated compounds displayed moderate cytotoxicity against the lung adenocarcinoma (A549), metastatic prostate cancer (PC-3 M), colon cancer (HCT-8), and hepatoma (Bel7402) cell lines with IC 50 values of 2.8-8.3 μM.

  1. Spins, Electromagnetic Moments, and Isomers of 107-129Cd

    CERN Document Server

    Yordanov, D T; Bieron, J; Bissell, M L; Blaum, K; Budincevic, I; Fritzsche, S; Frommgen, N; Georgiev, G; Geppert, Ch; Hammen, M; Kowalska, M; Kreim, K; Krieger, A; Neugart, R; Nortershauser, W; Papuga, J; Schmidt, S

    2013-01-01

    The neutron-rich isotopes of cadmium up to the N=82 shell closure have been investigated by high-resolution laser spectroscopy. Deep-UV excitation at 214.5 nm and radioactive-beam bunching provided the required experimental sensitivity. Long-lived isomers are observed in 127Cd and 129Cd for the first time. One essential feature of the spherical shell model is unambiguously confirmed by a linear increase of the 11/2- quadrupole moments. Remarkably, this mechanism is found to act well beyond the h11/2 shell.

  2. Decays of 116Sb isomers to levels in 116Sn

    International Nuclear Information System (INIS)

    Gacsi, Z.; Raman, S.

    1994-01-01

    The excited states of 116 Sn were studied by means of the decays of the 15.8-min, 3 + 116 Sb ground state, and the 60.3-min, 8 - 116 Sb isomer. Over 50 γ rays were observed; these were incorporated into a level scheme consisting of 32 excited states. Except for one new level proposed at 3.986 MeV, the current study fully supports an exhaustive study of levels in 116 Sn reported earlier. The previous study was an attempt to develop a nearly ''complete'' level scheme of 116 Sn up to an excitation energy of 4.3 MeV

  3. Anion Gap Blood Test: MedlinePlus Lab Test Information

    Science.gov (United States)

    ... https://medlineplus.gov/labtests/aniongapbloodtest.html Anion Gap Blood Test To use the sharing features on this page, please enable JavaScript. What is an Anion Gap Blood Test? An anion gap blood test is a way ...

  4. Hydrogen atom transfer reactions in thiophenol: photogeneration of two new thione isomers.

    Science.gov (United States)

    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 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

  5. Calculations of long-lived isomer production in neutron reactions

    International Nuclear Information System (INIS)

    Chadwick, M.B.; Young, P.G.

    1992-01-01

    We present theoretical calculations for the production of the long-lived isomers 93m Nb (1/2-, 16 yr), 121m Sn (11/2-, 55 yr), 166m Ho (7-, 1200 yr), 184m Re (8+, 165 d), 186m Re (8+, 2x10 5 yr), 178 Hf (16+, 31 yr), 179m Hf (25/2-, 25 d), and 192m Ir (9+, 241 yr), all of which pose potential radiation activation problems in nuclear fusion reactors if produced in 14-MeV neutron-induced reactions. We consider (n,2n), (n,n'), and (n,γ) production modes and compare our results both with experimental data (where available) and systematics. We also investigate the dependence of the isomeric cross section ratio on incident neutron energy for the isomers under consideration. The statistical Hauser-Feshbach plus preequilibrium code GNASH was used for the calculations. Where discrete state experimental information was lacking, rotational band members above the isomeric state, which can be justified theoretically but have not been experimentally resolved, were reconstructed. (author). 16 refs, 10 figs, 4 tabs

  6. CHEMICAL SIMULATIONS OF PREBIOTIC MOLECULES: INTERSTELLAR ETHANIMINE ISOMERS

    Energy Technology Data Exchange (ETDEWEB)

    Quan, Donghui; Durr, Allison [Department of Chemistry, Eastern Kentucky University, Richmond, KY 40475 (United States); Herbst, Eric [Departments of Chemistry and Astronomy, University of Virginia, Charlottesville, VA 22904 (United States); Corby, Joanna F. [Department of Astronomy, University of Virginia, Charlottesville, VA 22904 (United States); Hassel, George [Physics and Astronomy Department, Siena College, Loudonville, NY 12211 (United States)

    2016-06-20

    The E- and Z- isomers of ethanimine (CH{sub 3}CHNH) were recently detected toward the star-forming region Sagittarius (Sgr) B2(N) using the Green Bank Telescope PRIMOS cm-wave spectral data, and imaged by the Australia Telescope Compact Array. Ethanimine is not reported in the hot cores of Sgr B2, but only in gas that absorbs at +64 and +82 km s{sup −1} in the foreground of continuum emission generated by H ii regions. The ethanimine isomers can serve as precursors of the amino acid alanine and may play important roles in forming biological molecules in the interstellar medium. Here we present a study of the chemistry of ethanimine using a gas-grain simulation based on rate equations, with both isothermal and warm-up conditions. In addition, the density, kinetic temperature, and cosmic ray ionization rate have been varied. For a variety of physical conditions in the warm-up models for Sgr B2(N) and environs, the simulations show reasonable agreement with observationally obtained abundances. Isothermal models of translucent clouds along the same line of sight yield much lower abundances, so that ethanimine would be much more difficult to detect in these sources despite the fact that other complex molecules have been detected there.

  7. Degradation of a chiral nonylphenol isomer in two agricultural soils

    International Nuclear Information System (INIS)

    Zhang Haifeng; Spiteller, Michael; Guenther, Klaus; Boehmler, Gabriele; Zuehlke, Sebastian

    2009-01-01

    The degradation of a chiral nonylphenol isomer, 4-(1-ethyl-1,4-dimethylpentyl)phenol (NP 112 ), in two agricultural soils from Monheim and Dortmund, Germany has been studied. The degradation of NP 112 and the formation of a nitro-nonylphenol metabolite were determined by means of GC-MS analysis. The degradation followed bi-exponential order kinetics, with half-life of less than 5 days in both soils. The nitro-metabolite was found at different concentration levels in the two soils. The nitro-metabolite of NP 112 was more persistent than its parent compound. After 150 days about 13% of the initially applied NP 112 remained in the Monheim soil as its nitro-metabolite. Results of the E-screen assay revealed that the nitro-NP 112 has oestrogenic potency of 85% of that of NP 112 . Furthermore, the results of chiral GC-MS analysis revealed that no chiral degradation of NP 112 occurred in this study. - The degradation of a chiral nonylphenol isomer in agricultural soils followed bi-exponential order kinetics resulting in a more persistent nitro-metabolite.

  8. Structural and Mechanistic Analysis through Electronic Spectra: Aqueous Hyponitrite Radical (N2O2-) and Nitrosyl Hyponitrite Anion (N3O3-)

    Energy Technology Data Exchange (ETDEWEB)

    Valiev, Marat; Lymar, Sergei V.

    2011-11-03

    Aqueous hyponitrite radical (N{sub 2}O{sub 2}{sup -}) and nitrosyl hyponitrite anion (N{sub 3}O{sub 3}{sup -}) species are important intermediates in the reductive chemistry of NO. The structures and absorption spectra of various hydrated isomers of these compounds were investigated in this work using high-level quantum mechanical calculations combined with the explicit classical description of the aqueous environment. For N{sub 2}O{sub 2}{sup -}, comparison of the calculated spectra and energetics with the experimental data reveals that: (1) upon the one-electron oxidation of trans-hyponitrite (ON=NO{sub 2}{sup -}), the trans configuration of the resulting ON=NO{sup -} radical is preserved; (2) although cis- and trans-ON=NO{sup -} are energetically nearly equivalent, the barrier for the trans-cis isomerization is prohibitively high due to the partial double character of the NN bond; (3) the UV spectrum of ON=NO{sup -} was misinterpreted in the earlier pulse radiolysis work and its more recent revision has been justified. For the N{sub 3}O{sub 3}{sup -} ion, the symmetric isomer is the dominant observable species, and the asymmetric isomer contributes little to the experimental spectrum. Coherent analysis of the calculated and experimental data suggests a re-interpretation of the N{sub 2}O{sub 2}{sup -} + NO reaction mechanism, according to which the reaction evenly bifurcates to yield both the symmetric and asymmetric isomers of N{sub 3}O{sub 3}{sup -}. While the latter isomer rapidly decomposes to the final NO{sub 2}{sup -} + N{sub 2}O products, the former isomer is stable toward this decomposition but its formation is reversible with the homolysis equilibrium constant Khom = 2.2 - 10{sup -7} M. Collectively, these results demonstrate that advanced theoretical modeling can be of significant benefit in structural and mechanistic analysis of UV spectra.

  9. Clinical Usefulness of the Serum Anion Gap

    OpenAIRE

    Lee, Sik; Kang, Kyung Pyo; Kang, Sung Kyew

    2006-01-01

    The anion gap in the serum is useful in the interpretation of acid-base disorders and in the diagnosis of other conditions. In the early 1980s, ion-selective electrodes for specific ionic species were introduced for the measurement of serum electrolytes. This new method has caused a shift of the anion gap from 12±4 mEq/L down 6±3 mEq/L. It is worthy for clinicians to understand the range of normal anion gap and the measuring methods for serum sodium and chloride in the laboratories that suppo...

  10. MODERN TECHNOLOGY OF ANIONIC POLYMERIZATION MONOMERS

    Directory of Open Access Journals (Sweden)

    A. V. Tkachev

    2013-01-01

    Full Text Available The preconditions of use in the manufacture of automobile tyres of vulcanizates-based mortar butadienestyrene rubber with a high content of 1.2 links butadiene and statistical distribution of styrene are formulated. Set out scientific researches in the field of anionic co-polymerization of diene and vinyl aromatic monomers. Formulation of catalytic systems applied in processes of anionic copolymerization of monomers are given. The reasons of formation of gel in the process of anionic polymerization of monomers and terms of their elimination are considered.

  11. Anion conductance of the human red cell is carried by a maxi-anion channel

    DEFF Research Database (Denmark)

    Glogowska, Edyta; Dyrda, Agnieszka; Cueff, Anne

    2010-01-01

    Historically, the anion transport through the human red cell membrane has been perceived to be mediated by Band 3, in the two-component concept with the large electroneutral anion exchange accompanied by the conductance proper, which dominated the total membrane conductance. The status of anion...... that the diversity of anionic channel activities recorded in human erythrocytes corresponds to different kinetic modalities of a unique type of maxi-anion channel with multiple conductance levels and probably multiple gating properties and pharmacology, depending on conditions. It demonstrates the role of activator...... played by serum in the recruitment of multiple new conductance levels showing very complex kinetics and gating properties upon serum addition. These channels, which seem to be dormant under normal physiological conditions, are potentially activable and could confer a far higher anion conductance...

  12. Nano-Second Isomers in Neutron-Rich Ni Region Produced by Deep-Inelastic Collisions

    International Nuclear Information System (INIS)

    Ishii, T.; Asai, M.; Matsuda, M.; Ichikawa, S.; Makishima, A.; Hossain, I.; Kleinheinz, P.; Ogawa, M.

    2001-01-01

    Nuclear structure of the doubly magic 68 Ni and its neighbors has been studied by spectroscopic techniques. Developing a new instrument isomer-scope, we have measured γ rays from nano-second isomers produced in heavy-ion deep-inelastic collisions with great sensitivity. (author)

  13. A new isomer in 195Bi identified at the focal plane of HYRA

    International Nuclear Information System (INIS)

    Roy, T.; Mukherjee, G.; Asgar, Md. A.

    2014-01-01

    Due to the presence of high-j (h 9/2 and i 13/2 ) orbitals near the proton and neutron Fermi levels, high spin isomers are expected to occur for neutron deficient Bismuth nuclei (Z = 83) in A = 190 region. A 750 ns isomer has been known for a long time in 195 Bi whose excitation energy and decay path have been reported recently. A rotational band has been reported in this nucleus based on 13/2 + isomer, originated from the deformation driving i 13/2 orbital. This band reported to have prompt feeding through a 457 keV γ-ray apart from a strong feeding from the 750 ns isomer. In 193 Bi, the 29/2 - state is a 3μs isomer, another isomer with half-life >10μs is also known in this nucleus but its excitation energy, spin and parity are not known. Similar isomer has not yet been observed in 195 Bi. The aim of the present work was to find isomers and their decays in 193,195 Bi

  14. The behaviour of EDDHA isomers in soils as influenced by soil properties.

    NARCIS (Netherlands)

    Schenkeveld, W.D.C.; Reichwein, A.M.; Temminghoff, E.J.M.; Riemsdijk, van W.H.

    2007-01-01

    FeEDDHA products are applied to correct iron chlorosis in plants and consist of a mixture of EDDHA isomers chelated to iron. In this study such mixtures have been divided into four (groups of) isomers: racemic o,o-EDDHA, meso o,o-EDDHA, o,p-EDDHA and rest-EDDHA. The physical and chemical properties

  15. Lutein and Zeaxanthin Isomers in Eye Health and Disease.

    Science.gov (United States)

    Mares, Julie

    2016-07-17

    Current evidence suggests lutein and its isomers play important roles in ocular development in utero and throughout the life span, in vision performance in young and later adulthood, and in lowering risk for the development of common age-related eye diseases in older age. These xanthophyll (oxygen-containing) carotenoids are found in a wide variety of vegetables and fruits, and they are present in especially high concentrations in leafy green vegetables. Additionally, egg yolks and human milk appear to be bioavailable sources. The prevalence of lutein, zeaxanthin, and meso-zeaxanthin in supplements is increasing. Setting optimal and safe ranges of intake requires additional research, particularly in pregnant and lactating women. Accumulating evidence about variable interindividual response to dietary intake of these carotenoids, based on genetic or metabolic influences, suggests that there may be subgroups that benefit from higher levels of intake and/or alternate strategies to improve lutein and zeaxanthin status.

  16. Table of superdeformed nuclear bands and fission isomers

    Energy Technology Data Exchange (ETDEWEB)

    Firestone, R.B. [Lawrence Berkeley Lab., CA (United States); Singh, B. [McMaster Univ., Hamilton, ON (Canada)

    1994-06-01

    A minimum in the second potential well of deformed nuclei was predicted and the associated shell gaps are illustrated in the harmonic oscillator potential shell energy surface calculations shown in this report. A strong superdeformed minimum in {sup 152}Dy was predicted for {beta}{sub 2}-0.65. Subsequently, a discrete set of {gamma}-ray transitions in {sup 152}DY was observed and, assigned to the predicted superdeformed band. Extensive research at several laboratories has since focused on searching for other mass regions of large deformation. A new generation of {gamma}-ray detector arrays is already producing a wealth of information about the mechanisms for feeding and deexciting superdeformed bands. These bands have been found in three distinct regions near A=l30, 150, and 190. This research extends upon previous work in the actinide region near A=240 where fission isomers were identified and also associated with the second potential well. Quadrupole moment measurements for selected cases in each mass region are consistent with assigning the bands to excitations in the second local minimum. As part of our committment to maintain nuclear structure data as current as possible in the Evaluated Nuclear Structure Reference File (ENSDF) and the Table of Isotopes, we have updated the information on superdeformed nuclear bands. As of April 1994, we have complied data from 86 superdeformed bands and 46 fission isomers identified in 73 nuclides for this report. For each nuclide there is a complete level table listing both normal and superdeformed band assignments; level energy, spin, parity, half-life, magneto moments, decay branchings; and the energies, final levels, relative intensities, multipolarities, and mixing ratios for transitions deexciting each level. Mass excess, decay energies, and proton and neutron separation energies are also provided from the evaluation of Audi and Wapstra.

  17. Comparative Autoignition Trends in Butanol Isomers at Elevated Pressure

    KAUST Repository

    Weber, Bryan W.

    2013-03-21

    Autoignition experiments of stoichiometric mixtures of s-, t-, and i-butanol in air have been performed using a heated rapid compression machine (RCM). At compressed pressures of 15 and 30 bar and for compressed temperatures in the range 715-910 K, no evidence of a negative temperature coefficient region in terms of ignition delay response is found. The present experimental results are also compared with previously reported RCM data of n-butanol in air. The order of reactivity of the butanols is n-butanol > s-butanol ≈ i-butanol > t-butanol at the lower pressure but changes to n-butanol > t-butanol > s-butanol > i-butanol at higher pressure. In addition, t-butanol shows preignition heat release behavior, which is especially evident at higher pressures. To help identify the controlling chemistry leading to this preignition heat release, off-stoichiometric experiments are further performed at 30 bar compressed pressure, for t-butanol at φ = 0.5 and φ = 2.0 in air. For these experiments, higher fuel loading (i.e., φ = 2.0) causes greater preignition heat release (as indicated by greater pressure rise) than the stoichiometric or φ = 0.5 cases. Comparison of the experimental ignition delays with the simulated results using two literature kinetic mechanisms shows generally good agreement, and one mechanism is further used to explore and compare the fuel decomposition pathways of butanol isomers. Using this mechanism, the importance of peroxy chemistry in the autoignition of the butanol isomers is highlighted and discussed. © 2013 American Chemical Society.

  18. Table of superdeformed nuclear bands and fission isomers

    International Nuclear Information System (INIS)

    Firestone, R.B.; Singh, B.

    1994-06-01

    A minimum in the second potential well of deformed nuclei was predicted and the associated shell gaps are illustrated in the harmonic oscillator potential shell energy surface calculations shown in this report. A strong superdeformed minimum in 152 Dy was predicted for β 2 -0.65. Subsequently, a discrete set of γ-ray transitions in 152 DY was observed and, assigned to the predicted superdeformed band. Extensive research at several laboratories has since focused on searching for other mass regions of large deformation. A new generation of γ-ray detector arrays is already producing a wealth of information about the mechanisms for feeding and deexciting superdeformed bands. These bands have been found in three distinct regions near A=l30, 150, and 190. This research extends upon previous work in the actinide region near A=240 where fission isomers were identified and also associated with the second potential well. Quadrupole moment measurements for selected cases in each mass region are consistent with assigning the bands to excitations in the second local minimum. As part of our committment to maintain nuclear structure data as current as possible in the Evaluated Nuclear Structure Reference File (ENSDF) and the Table of Isotopes, we have updated the information on superdeformed nuclear bands. As of April 1994, we have complied data from 86 superdeformed bands and 46 fission isomers identified in 73 nuclides for this report. For each nuclide there is a complete level table listing both normal and superdeformed band assignments; level energy, spin, parity, half-life, magneto moments, decay branchings; and the energies, final levels, relative intensities, multipolarities, and mixing ratios for transitions deexciting each level. Mass excess, decay energies, and proton and neutron separation energies are also provided from the evaluation of Audi and Wapstra

  19. K-Isomers as a Probe of Nuclear Structure and Advanced Applications

    Science.gov (United States)

    Kondev, F. G.

    2005-05-01

    Nuclear K-isomers play a pivotal role in understanding the structure of deformed, axially symmetric nuclei. Examples are presented of recent studies of exotic multi-quasiparticle isomers in the A˜180 rare-earth region at the extreme of angular momentum and neutron number. A specific band-mixing scenario is invoked to explain the unusual decay path of the Kπ=57/2- isomer (T1/2=22 ns) in 175Hf, the highest spin K-isomer known in nature. The discovery of a suite of high-K isomers, above the previously known Kπ=23/2- (T1/2=160 d) state in 177Lu, using deep-inelastic and multi-nucleon transfer reactions is discussed.

  20. K-Isomers as a Probe of Nuclear Structure and Advanced Applications

    International Nuclear Information System (INIS)

    Kondev, F.G.

    2005-01-01

    Nuclear K-isomers play a pivotal role in understanding the structure of deformed, axially symmetric nuclei. Examples are presented of recent studies of exotic multi-quasiparticle isomers in the A∼180 rare-earth region at the extreme of angular momentum and neutron number. A specific band-mixing scenario is invoked to explain the unusual decay path of the Kπ=57/2- isomer (T1/2=22 ns) in 175Hf, the highest spin K-isomer known in nature. The discovery of a suite of high-K isomers, above the previously known Kπ=23/2- (T1/2=160 d) state in 177Lu, using deep-inelastic and multi-nucleon transfer reactions is discussed

  1. Aqueous phase partitioning of hexachlorocyclohexane (HCH) isomers by biosurfactant produced by Pseudomonas aeruginosa WH-2

    International Nuclear Information System (INIS)

    Sharma, Suman; Singh, Partapbir; Raj, Mayil; Chadha, Bhupinder Singh; Saini, Harvinder Singh

    2009-01-01

    The different isomers of technical-grade hexachlorocyclohexane (t-HCH) including the insecticidal γ-isomer, commonly known as lindane, have been reported to be toxic, carcinogenic and endocrine disrupters. The spatial arrangements of the chlorine atoms on different isomers and low aqueous phase solubility contribute to their persistence in environment, β-HCH being the most resistance to transformation. The biosurfactant preparation of Pseudomonas aeruginosa isolate WH-2 was evaluated for its ability to improve the aqueous phase partitioning of different isomers of HCH-muck. Further, the ability of biosurfactant preparation to emulsify HCH and n-hexadecane was checked under different conditions, usually characteristic of sites contaminated with pollutants viz. wide range of pH, temperature, and salinity. The data obtained from this study will be helpful in designing suitable bioremediation strategies for huge stock piles of HCH-muck and sites polluted by reckless use/disposal of HCH-isomers.

  2. Cation–Anion Interactions within the Nucleic Acid Ion Atmosphere Revealed by Ion Counting

    Science.gov (United States)

    Gebala, Magdalena; Giambasu, George M.; Lipfert, Jan; Bisaria, Namita; Bonilla, Steve; Li, Guangchao; York, Darrin M.; Herschlag, Daniel

    2016-01-01

    The ion atmosphere is a critical structural, dynamic, and energetic component of nucleic acids that profoundly affects their interactions with proteins and ligands. Experimental methods that “count” the number of ions thermodynamically associated with the ion atmosphere allow dissection of energetic properties of the ion atmosphere, and thus provide direct comparison to theoretical results. Previous experiments have focused primarily on the cations that are attracted to nucleic acid polyanions, but have also showed that anions are excluded from the ion atmosphere. Herein, we have systematically explored the properties of anion exclusion, testing the zeroth-order model that anions of different identity are equally excluded due to electrostatic repulsion. Using a series of monovalent salts, we find, surprisingly, that the extent of anion exclusion and cation inclusion significantly depends on salt identity. The differences are prominent at higher concentrations and mirror trends in mean activity coefficients of the electrolyte solutions. Salts with lower activity coefficients exhibit greater accumulation of both cations and anions within the ion atmosphere, strongly suggesting that cation–anion correlation effects are present in the ion atmosphere and need to be accounted for to understand electrostatic interactions of nucleic acids. To test whether the effects of cation–anion correlations extend to nucleic acid kinetics and thermodynamics, we followed the folding of P4–P6, a domain of the Tetrahymena group I ribozyme, via single-molecule fluorescence resonance energy transfer in solutions with different salts. Solutions of identical concentration but lower activity gave slower and less favorable folding. Our results reveal hitherto unknown properties of the ion atmosphere and suggest possible roles of oriented ion pairs or anion-bridged cations in the ion atmosphere for electrolyte solutions of salts with reduced activity. Consideration of these new

  3. Cationic cobaltammines as anion receptors: Synthesis and characterization of [Co(NH 3) 6](4-np) 3.4H 2O, [Co(NH 3) 6](2,4-dnp) 3 and [Co(NH 3) 6](2,4,6-tnp) 3 (where np=nitrophenolate, dnp=dinitrophenolate, tnp, trinitrophenolate), single crystal X-ray structure and packing of [Co(NH 3) 6](4-np) 3.4H 2O

    Science.gov (United States)

    Sharma, Raj Pal; Bala, Ritu; Sharma, Rajni; Venugopalan, Paloth

    2005-10-01

    In an effort to utilize [Co(NH 3) 6] 3+ cation as a new host for mono-, di- and tri-substituted nitrophenolate anions, yellow solids of composition [Co(NH 3) 6](4-np) 3.4H 2O, [Co(NH 3) 6](2,4-dnp) 3, and [Co(NH 3) 6](2,4,6-tnp) 3 were obtained in high yields by reacting sodium salts of 4-np, 2,4-dnp and 2,4,6-tnp (where np=nitrophenolate, dnp=dinitrophenolate and tnp=trinitrophenolate,) with [Co(NH 3) 6]Cl 3 respectively in 3:1 molar ratio in hot aqueous medium. These cobalt(III) complex salts have been characterized by elemental analyses and spectroscopic techniques (UV/Visible, IR and NMR). Single crystal X-ray structure determination of [Co(NH 3) 6](4-np) 3.4H 2O revealed the presence of discrete ions, [Co(NH 3) 6] 3+ and C 6H 4NO 3- in addition to four lattice water molecules in the solid state. A strong network of hydrogen bond interactions (N-H⋯O (phenolate), N-H⋯O (nitro), O-H⋯O (water) stabilize the crystal lattice. The formation of these salts and measurement of solubility products suggests that [Co(NH 3) 6] 3+ present in [Co(NH 3) 6]Cl 3 may be used as anion receptor for the nitrophenolate ions.

  4. Enhanced E3 transitions and mixed configurations for core excited isomers in 210At and 211At

    International Nuclear Information System (INIS)

    Dracoulis, G.D.; Steed, C.A.; Byrne, A.P.; Poletti, S.J.; Stuchbery, A.E.; Bark, R.A.

    1986-09-01

    The lifetime and branching ratio of the 19 + isomer in 210 At have been measured. Its enhanced E3 decay and g-factor, and those of the related 39/2 - isomer in 211 At are compared with the results of a semi-empirical shell model calculation which includes couplings to the 3 - octupole vibration, resulting in mixed configurations. Lifetimes were also obtained for the 15 - isomer in 210 At, and he 29/2 + isomer in 209 At

  5. Temperature-Dependent Photoelectron Spectroscopy of Methyl-Benzoate Anions: Observation of Steric Effect in Ortho-Methyl-Benzoate

    Energy Technology Data Exchange (ETDEWEB)

    Woo, Hin-koon; Wang, Xue B.; Kiran, Boggavarapu; Wang, Lai S.

    2005-12-22

    Temperature-dependent photoelectron spectra of benzoate anion (C6H5CO2-) and its three methyl-substituted isomers (o-, m-, p-CH3C6H4CO2-) have been obtained using a newly developed low-temperature photoelectron spectroscopy apparatus that features an electrospray source and a cryogenically controlled ion trap. Detachment channels due to removing electrons from the carboxylate group and benzene ring electrons were distinctly observed. Well-resolved vibrational structures were obtained in the lower binding energy region due to the OCO bending modes, except for o-CH3C6H4CO2-, which yielded broad spectra even at the lowest ion trap temperature (18 K). Theoretical calculations revealed a large geometry change in the OCO angles between the anion and neutral ground states, consistent with the broad ground state bands observed for all species. A strong steric effect was observed between the carboxylate and the methyl group in o-CH3C6H4CO2-, such that the -CO2- group is pushed out of the plane of the benzene ring by {approx}25 degrees and its internal rotational barrier is significantly reduced. The low rotational barrier in o-CH3C6H4CO2-, which makes it very difficult to be cooled vibrationally, and the strong coupling between the OCO bending and CO2 torsional modes yielded the broad PES spectra for this isomer. It is shown that there is no C-H?O hydrogen bond in o-CH3C6H4CO2- and the interaction between the carboxylate and methyl groups in this anion is found to be repulsive in nature.

  6. Spectrally Undiscerned Isomers Might Lead to Erroneous Determination of Water Exchange Rates of paraCEST Eu(III) Agents.

    Science.gov (United States)

    Cakić, Nevenka; Tickner, Ben; Zaiss, Moritz; Esteban-Gómez, David; Platas-Iglesias, Carlos; Angelovski, Goran

    2017-07-17

    We report a detailed study of the solution structure and water exchange rate of a Eu(III) complex with the cyclen-based ligand L 1 , containing (S)-2-(2-acetamido)-3-(4-(trifluoromethyl)phenyl)propanoate pendant arms at positions 1 and 7 of the cyclen ring and acetylglycinate pendants at positions 4 and 10. The EuL 1 complex was characterized by a combination of NMR and luminescence spectroscopy and density functional theory (DFT) calculations. The chemical exchange saturation transfer (CEST) spectra obtained at different temperatures and saturation powers present a CEST signal attributed to the coordinated water molecule. However, the spectra recorded at low temperatures (10 °C) and low saturation powers revealed the presence of two different species with coordinated water molecules having very similar chemical shifts. Determination of the water exchange rates of the coordinated water molecules was carried out by using the Bloch four-pool model that accounts for the presence of these isomers, and this model was compared to conventional methods for CEST quantification, namely the Omega plot and QUESP (quantification of exchange rate as a function of saturation power), which assume the presence of a single CEST active species. The results indicated that only the four-pool Bloch equations provide reasonable water exchange rates and activation parameters. Solution NMR studies and DFT calculations indicated that the two isomers present in solution correspond to the SS-Δ(λλλλ) and SS-Λ(δδδδ) isomers, which present capped square-antiprismatic (SAP) coordination environments. Additional NMR studies on the EuL 2 and EuL 3 complexes, which present four (S)-2-(2-acetamido)-3-(4-(trifluoromethyl)phenyl)propanoate or acetylglycinate pendant arms, respectively, confirm the results obtained for EuL 1 .

  7. Capillary electrophoresis separation of neutral organic compounds, pharmaceutical drugs, proteins and peptides, enantiomers, and anions

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Wei -Liang [Iowa State Univ., Ames, IA (United States)

    1999-02-12

    Addition of a novel anionic surfactant, namely lauryl polyoxyethylene sulfate, to an aqueous-acetonitrile electrolyte makes it possible to separate nonionic organic compounds by capillary electrophoresis. Separation is based on differences in the association between analytes and the surfactant. Highly hydrophobic compounds such as polyaromatic hydrocarbons are well separated by this new surfactant. Migration times of analytes can be readily changed over an unusually large range by varying the additive concentration and the proportion of acetonitrile in the electrolyte. Several examples are given, including the separation of four methylbenz[a]anthracene isomers and the separation of normal and deuterated acetophenone. The effect of adding this new surfactant to the acidic electrolyte was also investigated. Incorporation of cetyltrimethylammonium bromide in the electrolyte is shown to dynamically coat the capillary and reverse electroosmotic flow. Chiral recognition mechanism is studied using novel synthetic surfactants as chiral selectors, which are made from amino acids reacting with alkyl chloroformates. A satisfactory separation of both inorganic and organic anions is obtained using electrolyte solutions as high as 5 M sodium chloride using direct photometric detection. The effect of various salts on electrophoretic and electroosmotic mobility is further discussed. Several examples are given under high-salt conditions.

  8. Assessing the impact of anion-π effects on phenylalanine ion structures using IRMPD spectroscopy.

    Science.gov (United States)

    Burt, Michael; Wilson, Kathleen; Marta, Rick; Hasan, Moaraj; Scott Hopkins, W; McMahon, Terry

    2014-11-28

    The gas-phase structures of two halide-bound phenylalanine anions (PheX(-), X = Cl(-) or Br(-)) and five fluorinated derivatives have been identified using infrared multiple photon dissociation (IRMPD) spectroscopy. The addition of electron-withdrawing groups to the aromatic ring creates a π-acidic system that additionally stabilizes the halide above the ring face. Detailed ion structures were determined by comparing the IRMPD spectra with harmonic and anharmonic infrared spectra computed using B3LYP/6-311++G(d,p) as well as with 298 K enthalpies and Gibbs energies determined by the MP2(full)/6-311++G(2d,2p)//B3LYP/6-311++G(d,p) and MP2(full)/aug-cc-pVTZ//B3LYP/6-311++G(d,p) methods. PheX(-) structures were found to be dependent on both the nature of the anion and the extent of ring fluorination. Canonical isomers were established to be the dominant structures in every case, but halide addition significantly narrowed the energy gap with zwitterionic potential energy surfaces. This enabled zwitterions to appear as minor contributors to the gas-phase populations of Phe35F2Cl(-) and PheF5Br(-).

  9. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    International Nuclear Information System (INIS)

    Bowman-James, K.; Wilson, G.; Moyer, B. A.

    2004-01-01

    This project involves the design and synthesis of receptors for oxoanions of environmental importance, including emphasis on high level and low activity waste. Target anions have included primarily oxoanions and a study of the basic concepts behind selective binding of target anions. A primary target has been sulfate because of its deleterious influence on the vitrification of tank wastes

  10. Correction of the anion gap for albumin in order to detect occult tissue anions in shock.

    Science.gov (United States)

    Hatherill, M; Waggie, Z; Purves, L; Reynolds, L; Argent, A

    2002-12-01

    It is believed that hypoalbuminaemia confounds interpretation of the anion gap (AG) unless corrected for serum albumin in critically ill children with shock. To compare the ability of the AG and the albumin corrected anion gap (CAG) to detect the presence of occult tissue anions. Prospective observational study in children with shock in a 22 bed multidisciplinary paediatric intensive care unit of a university childrenrsquo;s hospital. Blood was sampled at admission and at 24 hours, for acid-base parameters, serum albumin, and electrolytes. Occult tissue anions (lactate + truly "unmeasured" anions) were calculated from the strong ion gap. The anion gap ((Na + K) - (Cl + bicarbonate)) was corrected for serum albumin using the equation of Figge: AG + (0.25 x (44 - albumin)). Occult tissue anions (TA) predicted by the anion gap were calculated by (anion gap - 15 mEq/l). Optimal cut off values of anion gap were compared by means of receiver operating characteristic (ROC) curves. Ninety three sets of data from 55 children (median age 7 months, median weight 4.9 kg) were analysed. Data are expressed as mean (SD), and mean bias (limits of agreement). The incidence of hypoalbuminaemia was 76% (n = 42/55). Mean serum albumin was 25 g/l (SD 8). Mean AG was 15.0 mEq/l (SD 6.1), compared to the CAG of 19.9 mEq/l (SD 6.6). Mean TA was 10.2 mmol/l (SD 6.3). The AG underestimated TA with mean bias 10.2 mmol/l (4.1-16.1), compared to the CAG, mean bias 5.3 mmol/l (0.4-10.2). A clinically significant increase of TA >5 mmol/l was present in 83% (n = 77/93) of samples, of which the AG detected 48% (n = 36/77), and the CAG 87% (n = 67/77). Post hoc ROC analysis revealed optimal cut off values for detection of TA >5 mmol/l to be AG >10 mEq/l, and CAG >15.5 mEq/l. Hypoalbuminaemia is common in critically ill children with shock, and is associated with a low observed anion gap that may fail to detect clinically significant amounts of lactate and other occult tissue anions. We suggest that

  11. Structural-based differences in ecotoxicity of benzoquinoline isomers to the zebra mussel (Dreissena polymorpha)

    Energy Technology Data Exchange (ETDEWEB)

    Kraak, M.H.S.; Wijnands, P.; Govers, H.A.J.; Admiraal, W.; Voogt, P. de [Univ. of Amsterdam (Netherlands)

    1997-10-01

    Effects of four benzoquinoline isomers on the filtration rate of the zebra mussel (Dreissena polymorpha) were analyzed, to study the effect of minor differences in chemical structure on adverse biological effects. Filtration rates were measured after 48 h of exposure to different concentrations of acridine, phenanthridine, benzo[f]quinoline, and benzo[h]quinoline in the water. The 50% effective concentration (EC50) values for filtration rate of the four isomers differed significantly. Effects increased in the order benzo[f], -[h], -[b], and -[c]quinoline, and the difference between the most toxic isomer and the least toxic isomer amounted to a factor of 30. Attempts were made to relate these differences in toxicity to the structure of the isomers. Size- or topology-related molecular descriptors provided insufficient resolution to distinguish between the benzoquinoline isomers, and none of the electronic descriptors separately provided a significant correlation with the observed effects. In an alternative approach, molecular shape, accessibility, and minimum agent-macromolecule distance were used to represent repulsive and attractive forces between the benzoquinoline isomers and biological membranes. This approach could tentatively explain the observed effects and is supported by a high correlation between the EC50 data and the reversed-phase C18-HPLC behavior of the benzoquinolines (k{sub 0}), which is likely to be governed by similar processes.

  12. Toroidal high-spin isomers in the nucleus 304120

    Science.gov (United States)

    Staszczak, A.; Wong, Cheuk-Yin; Kosior, A.

    2017-05-01

    Background: Strongly deformed oblate superheavy nuclei form an intriguing region where the toroidal nuclear structures may bifurcate from the oblate spheroidal shape. The bifurcation may be facilitated when the nucleus is endowed with a large angular moment about the symmetry axis with I =Iz . The toroidal high-K isomeric states at their local energy minima can be theoretically predicted using the cranked self-consistent Skyrme-Hartree-Fock method. Purpose: We use the cranked Skyrme-Hartree-Fock method to predict the properties of the toroidal high-spin isomers in the superheavy nucleus 120304184. Method: Our method consists of three steps: First, we use the deformation-constrained Skyrme-Hartree-Fock-Bogoliubov approach to search for the nuclear density distributions with toroidal shapes. Next, using these toroidal distributions as starting configurations, we apply an additional cranking constraint of a large angular momentum I =Iz about the symmetry z axis and search for the energy minima of the system as a function of the deformation. In the last step, if a local energy minimum with I =Iz is found, we perform at this point the cranked symmetry- and deformation-unconstrained Skyrme-Hartree-Fock calculations to locate a stable toroidal high-spin isomeric state in free convergence. Results: We have theoretically located two toroidal high-spin isomeric states of 120304184 with an angular momentum I =Iz=81 ℏ (proton 2p-2h, neutron 4p-4h excitation) and I =Iz=208 ℏ (proton 5p-5h, neutron 8p-8h) at the quadrupole moment deformations Q20=-297.7 b and Q20=-300.8 b with energies 79.2 and 101.6 MeV above the spherical ground state, respectively. The nuclear density distributions of the toroidal high-spin isomers 120304184(Iz=81 ℏ and 208 ℏ ) have the maximum density close to the nuclear matter density, 0.16 fm-3, and a torus major to minor radius aspect ratio R /d =3.25 . Conclusions: We demonstrate that aligned angular momenta of Iz=81 ℏ and 208 ℏ arising from

  13. New borohydride anion B6H7-

    International Nuclear Information System (INIS)

    Kuznetsov, I.Yu.; Vinitskij, D.M.; Solntsev, K.A.

    1985-01-01

    The [Ni(Bipy) 3 ] (B 6 H 7 ) 2 , (Ph 4 P)B 6 H 7 , [Ni(Phen) 3 ](B 6 H 7 ) 2 crystals (where Bipy = bipyridine, Phen = phenathroline, Ph = phenyl) are obtained via the exchange reaction with a subsequent recrystallization from aqua-acetonic and acetonic solutions. The structure is studied of a new borohydride anion B 6 H 7 - possessing a four-valence bond unique for polyhedral borohydride anions. A triangular face of boride skeleton coordinating a hydrogen atom is considerably larger than other faces, and the electron density on this hydrogen atom is evidently much higher than at the end hydride hydrogen atoms. The trend of B 6 H 7 - anion to form statistically disordered structurs testifies to a rather slight effect of the seventh hydrogen atom position on the structure pattern of the ionic crystal lattice

  14. Photoemission from tin and lead cluster anions

    International Nuclear Information System (INIS)

    Gantefoer, G.; Gausa, M.; Meiwes-Broer, K.H.; Lutz, H.O.

    1989-01-01

    Photoelectrons from mass-identified jet-cooled tin and lead cluster anions (Sn n - , Pb n - ) are detached by ultraviolet laser light (hν=3.68 eV). The photoelectron energy spectra give the detachment energies of ground state cluster anions (electron affinities) as well as excitation energies of neutral clusters in the geometry of the anions. The energy spectra for Sn n - are dominated by flat thresholds with an n-dependence similar to that of other group IV clusters. In contrast, for Pb n - we find pronounced narrow lines close to threshold, generally followed by a 0.3-1.4 eV gap which indicates closed-shell behaviour of Pb n - for nearly all n. (orig.)

  15. Theoretical studies of possible toroidal high-spin isomers in the light-mass region

    Directory of Open Access Journals (Sweden)

    Staszczak Andrzej

    2016-01-01

    Full Text Available We review our theoretical knowledge of possible toroidal high-spin isomers in the light mass region in 28≤A≤52 obtained previously in cranked Skyrme-Hartree-Fock calculations. We report additional toroidal high-spin isomers in 56Ni with I=114ħ and 140ħ, which follow the same (multi-particle–(multi-hole systematics as other toroidal high-spin isomers. We examine the production of these exotic nuclei by fusion of various projectiles on 20Ne or 28Si as an active target in time-projection-chamber (TPC experiments.

  16. Effects of high-order deformation on high-K isomers in superheavy nuclei

    International Nuclear Information System (INIS)

    Liu, H. L.; Bertulani, C. A.; Xu, F. R.; Walker, P. M.

    2011-01-01

    Using, for the first time, configuration-constrained potential-energy-surface calculations with the inclusion of β 6 deformation, we find remarkable effects of the high-order deformation on the high-K isomers in 254 No, the focus of recent spectroscopy experiments on superheavy nuclei. For shapes with multipolarity six, the isomers are more tightly bound and, microscopically, have enhanced deformed shell gaps at N=152 and Z=100. The inclusion of β 6 deformation significantly improves the description of the very heavy high-K isomers.

  17. Solvation effect on isomer stability and electronic structures of protonated serotonin

    Science.gov (United States)

    Omidyan, Reza; Amanollahi, Zohreh; Azimi, Gholamhassan

    2017-07-01

    Microsolvation effect on geometry and transition energies of protonated serotonin has been investigated by MP2 and CC2 quantum chemical methods. Also, conductor-like screening model, implemented recently in the MP2 and ADC(2) methods, was examined to address the bulk water environment's effect on the isomer stability and electronic transition energies of protonated serotonin. It has been predicted that the dipole moment of gas phase isomers plays the main role on the isomer stabilization in water solution and electronic transition shifts. Also, both red- and blue-shift effects have been predicted to take place on electronic transition energies, upon hydration.

  18. Identification of a new isomer from a reversible isomerization of ceftriaxone in aqueous solution.

    Science.gov (United States)

    Tian, Ye; Lu, Li; Chang, Yan; Zhang, Dou-sheng; Li, Jin; Feng, Yan-Chun; Hu, Chang-Qin

    2015-01-01

    A reversible isomerization of ceftriaxone in aqueous solution was observed, and the structure of the isomer was determined by mass spectrometry and various 1D and 2D NMR techniques. The mechanism of isomerization was also discussed. Finally, molecular docking simulations were performed and the antimicrobial activities of the isomers were measured. This showed that the biological activity of ceftriaxone was stronger than that of its isomer. The results reported in this article may be important to quality control requirements and to the stability of ceftriaxone products. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Isomer-specific regulation of metabolism and PPARgamma signaling by CLA in human preadipocytes

    DEFF Research Database (Denmark)

    Brown, J Mark; Boysen, Maria Sandberg; Jensen, Søren Skov

    2003-01-01

    Trans-10,cis-12 conjugated linoleic acid (CLA) has previously been shown to be the CLA isomer responsible for CLA-induced reductions in body fat in animal models, and we have shown that this isomer, but not the cis-9,trans-11 CLA isomer, specifically decreased triglyceride (TG) accumulation...... transporter 4 gene expression. Furthermore, trans-10,cis-12 CLA reduced oleic acid uptake and oxidation when compared with all other treatments. In parallel to CLA's effects on metabolism, trans-10,cis-12 CLA decreased, whereas cis-9,trans-11 CLA increased, the expression of peroxisome proliferator...

  20. Reactions of isoprene and sulphoxy radical-anions - a possible source of atmospheric organosulphites and organosulphates

    Science.gov (United States)

    Rudziński, K. J.; Gmachowski, L.; Kuznietsova, I.

    2009-03-01

    Transformation of isoprene coupled with auto-oxidation of SIV in aqueous solutions was studied experimentally and by chemical-kinetic modelling over a broad range of solution acidities (pH=3-9) to complement the research on aqueous-phase and heterogeneous transformation of isoprene reported recently by many laboratories. Isoprene significantly slowed down the auto-oxidation in acidic and basic solutions, and accelerated it slightly in neutral solutions. Simultaneously, production of sulphate ions and formation of solution acidity were significantly reduced. Formation of sulphite and sulphate derivatives of isoprene - sulphurous acid mono-(2-methyl-4-oxo-but-2-enyl) ester (m/z=163), sulphurous acid mono-(4-hydroxy-2-methyl-but-2-enyl) ester (m/z=165), sulphuric acid mono-(2-methyl-4-oxo-but-2-enyl) ester (m/z=179), sulphuric acid mono-(4-hydroxy-2-methyl-but-2-enyl) ester (m/z=181), and possible structural isomers of these species - was indicated by electrospray ionisation mass spectrometric analysis of post-reaction mixtures. The experimental results were explained by changes in a subtle quantitative balance of three superimposed processes whose rates depended in different manner on the acidity of reacting solutions - the scavenging of sulphoxy radical-anions by isoprene, the formation of sulphoxy radical-anions during further reactions of isoprene radicals, and the auto-oxidation of SIV itself. A chemical mechanism based on this idea was explored numerically to show good agreement with experimental data. In basic and neutral solutions, the model overestimated the consumption of isoprene, probably because reactions of primary sulphite and sulphate derivatives of isoprene with sulphoxy radical-anions were not included. Interaction of isoprene with sulphur(IV) species and oxygen can possibly result in formation of new organosulphate and organosulphite components of atmospheric aerosols and waters, and influence the distribution of reactive sulphur and oxygen species

  1. Clinical acid-base pathophysiology: disorders of plasma anion gap.

    Science.gov (United States)

    Moe, Orson W; Fuster, Daniel

    2003-12-01

    The plasma anion gap is a frequently used parameter in the clinical diagnosis of a variety of conditions. The commonest application of the anion gap is to classify cases of metabolic acidosis into those that do and those that do not leave unmeasured anions in the plasma. While this algorithm is useful in streamlining the diagnostic process, it should not be used solely in this fashion. The anion gap measures the difference between the unmeasured anions and unmeasured cations and thus conveys much more information to the clinician than just quantifying anions of strong acids. In this chapter, the significance of the anion gap is emphasized and several examples are given to illustrate a more analytic approach to using the clinical anion gap; these include disorders of low anion gap, respiratory alkalosis and pyroglutamic acidosis.

  2. Microsolvation for the Dicyanamide Anion: [N(CN)2-](H2O)n (n=0-12)

    Energy Technology Data Exchange (ETDEWEB)

    Jagoda-Cwiklik, Barbra; Wang, Xue B.; Woo, Hin-Koon; Yang, Jie; Wang, Guanjun; Zhou, Mingfei; Jungwirth, Pavel; Wang, Lai S.

    2007-08-16

    Photoelectron spectroscopy is combined with ab initio calculations to study the microsolvation of the dicyanamide anion, N(CN)2 -. Photoelectron spectra of [N(CN)2-] (H2O)n (n = 0-12) have been measured at room temperature and also at low temperature for n= 0-4. Vibrationally resolved photoelectron spectra are obtained for N(CN)2-, allowing the electron affinity of the N(CN)2 radical to be determined accurately as 4.135 ±0.010 eV. The electron binding energies and the spectral width of the hydrated clusters are observed to increase with the number of water molecules. The first five waters are observed to provide significant stabilization to the solute, whereas the stabilization becomes weaker for n > 5. The spectral width, which carries information about the solvent reorganization upon electron detachment in [N(CN)2-](H2O)n, levels off for n > 6. Theoretical calculations reveal several close-lying isomers for n= 1 and 2 due to the fact that the N(CN)2- anion possesses three almost equivalent hydration sites. In all the hydrated clusters, the most stable structures consist of a water cluster solvating one end of the N(CN)2- anion.

  3. High Vacuum Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar

    2015-09-01

    Anionic polymerization high vacuum techniques (HVTs) are the most suitable for the preparation of polymer samples with well-defined complex macromolecular architectures. Though HVTs require glassblowing skill for designing and making polymerization reactor, it is the best way to avoid any termination of living polymers during the number of steps for the synthesis of polymers with complex structure. In this chapter, we describe the different polymerization reactors and HVTs for the purification of monomers, solvents, and other reagents for anionic polymerization as well as few model reactions for the synthesis of polymers with simple to complex structure.

  4. Organic superconductors with an incommensurate anion structure

    OpenAIRE

    Kawamoto, Tadashi; Takimiya, Kazuo

    2009-01-01

    Superconducting incommensurate organic composite crystals based on the methylenedithio-tetraselenafulvalene (MDT-TSF) series donors, where the energy band filling deviates from the usual 3/4-filled, are reviewed. The incommensurate anion potential reconstructs the Fermi surface for both (MDT-TSF)(AuI2)0.436 and (MDT-ST)(I3)0.417 neither by the fundamental anion periodicity q nor by 2q, but by 3q, where MDT-ST is 5H-2-(1,3-dithiol-2-ylidene)-1,3-diselena-4,6-dithiapentalene, and q is the recip...

  5. Recognition, Sensing and Separation of Anions

    Indian Academy of Sciences (India)

    Dr Pradyut Ghosh

    2016-11-05

    Nov 5, 2016 ... Arsenate Recognition in Aqueous Medium. Anion log K log Ka log Kb. HAsO4. 2-. 4.42. 4.35. -. H2PO4. -. 3.62. 3.62. 5.52. SO4. 2-. 3.48. 3.36. 4.73. CO3. 2-. 2.68. -. 4.04. Table 1. Association constant value of L in DMSO-d6/D2O (9:1, v/v) with different anion in DMSO-d6/D2O (1.1:1, v/v) at 298 K a: log K ...

  6. ANION GAP NO SANGUE VENOSO EM EQUINOS

    Directory of Open Access Journals (Sweden)

    Luís Carlos Ribeiro Fan

    1994-01-01

    Full Text Available RESUMO A influência do sangue venoso na determinação do anion gap foi estudada em 50 equinos adultos clinicamente sadios no município de Santa Maria, RS. Os resultados obtidos em mEq/1 foram: sódio 140 ± 2,0; potássio 4,2 ± 0,5; cloreto 102 ± 12 e bicarbonato 26,9 ± 2,0. Conclui-se que o sangue venoso pode substituir o arterial na determinação do anion gap em equinos.

  7. Dysregulatory effects of retinoic acid isomers in late zebrafish embryos.

    Science.gov (United States)

    Navarro-Martín, Laia; Oliveira, Eva; Casado, Marta; Barata, Carlos; Piña, Benjamin

    2018-02-01

    All-trans retinoic acid (atRA) and 9-cis retinoic acid (9cRA) are two natural derivatives of vitamin A that contribute to the normal vertebrate development by affecting gene expression through the retinoic acid signalling pathway. We show transcriptomic effects of the ectopic addition of atRA or 9cRA to zebrafish embryos at the posthatching embryonic stage. Exposure for 24 or 72 h to sublethal concentrations of both isomers resulted in characteristic transcriptome changes, in which many proliferation and development-related genes became underexpressed, whereas genes related to retinoid metabolism and some metabolic functions became overrepresented. While short and long exposures elicit essentially the same set of genes, atRA specifically induced expression of a specific subset of proteases, likely acting at the extracellular level, and of elements of the response to xenobiotics. These results reflect the well-known antiproliferative activity of retinoids, and they suggest a dysregulation of the developmental process at final stages of embryogenesis. They also indicate a potential role of endopeptidases as markers of developmental alterations, as well as their possible control by the retinoic signalling pathway. We propose to monitor mRNA levels of cyp16a, cyp16b, and cyp16c in zebrafish embryos as a bioassay for retinoid disruption.

  8. Isomers of fluoroamphetamines detected in forensic cases in Denmark

    DEFF Research Database (Denmark)

    Johansen, Sys Stybe; Hansen, Tina Maria

    2012-01-01

    A study was performed on the detection, separation and quantification of isomers from the new designer drugs named fluoroamphetamines (FAs) in forensic cases in eastern Denmark. The drugs were detected in whole blood extracts by ultraperformance liquid chromatography with time of flight mass...... by the retention time, multiple reaction monitoring (MRM) traces [154¿>¿109 (quantifier); 154¿>¿137], and ion ratio of the two transitions. For all FAs, LOQ was 0.002 mg/kg with linear ranges from 0.002 to 1.0 mg/kg whole blood. Since 2008, a total of 15 forensic investigations, mainly driving under the influence...... of drugs (DUID) cases, involving 4-fluoroamphetamine (4-FA) have been observed with whole blood concentrations ranging from 0.006 to 0.58 mg/kg. One autopsy case involved 4-FA; however, it was determined to be a combined intoxication. In 2010, ortho-fluoroamphetamine (2-FA) was discovered in forensic...

  9. Communication: Remarkable electrophilicity of the oxalic acid monomer: An anion photoelectron spectroscopy and theoretical study

    International Nuclear Information System (INIS)

    Buonaugurio, Angela; Graham, Jacob; Buytendyk, Allyson; Bowen, Kit H.; Ryder, Matthew R.; Gutowski, Maciej; Keolopile, Zibo G.; Haranczyk, Maciej

    2014-01-01

    Our experimental and computational results demonstrate an unusual electrophilicity of oxalic acid, the simplest dicarboxylic acid. The monomer is characterized by an adiabatic electron affinity and electron vertical detachment energy of 0.72 and 1.08 eV (±0.05 eV), respectively. The electrophilicity results primarily from the bonding carbon-carbon interaction in the singly occupied molecular orbital of the anion, but it is further enhanced by intramolecular hydrogen bonds. The well-resolved structure in the photoelectron spectrum is reproduced theoretically, based on Franck-Condon factors for the vibronic anion → neutral transitions

  10. Theoretical study of the geometric and electronic structure of neutral and anionic doped silver clusters, Ag5X0,- with X = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni

    International Nuclear Information System (INIS)

    Hou Xinjuan; Janssens, Ewald; Lievens, Peter; Minh Tho Nguyen

    2006-01-01

    Density functional theory (DFT) has been applied to investigate the low-lying electronic states of neutral and anionic transition metal doped silver clusters Ag 5 X 0,- with X = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni using the B3LYP functional with the Stuttgart SDD basis sets. The structural features, frontier orbital energy gaps (HOMO and LUMO), vertical detachment energies, and vertical and adiabatic electronic affinities are evaluated. For all doped silver clusters, both in neutral and anionic states, two-dimensional and three-dimensional low-energy isomers are found to coexist. For neutral clusters, dopant Sc, Ti, V, and Mn atoms largely decrease the frontier orbital energy gaps, while they are markedly increased by Sc and Fe atoms in the anionic clusters. A completely quenched dopant magnetic moment is found in Ag 5 Sc, while high spin magnetic moments are located on the other dopant atoms in Ag 5 X 0,-

  11. Identifying Tm-C82 isomers with density functional theory calculations

    International Nuclear Information System (INIS)

    Zheng Limin; He Hongqing; Yang Minghui; Zeng Qun; Yang Mingli

    2010-01-01

    Density functional theory calculations have been performed to study the geometrical and electronic properties of endohedral metallofullerene Tm-C 82 isomers. Three energetically favorable isomers (with C s , C 2 and C 2v symmetry, respectively) are identified which are consistent with the nuclear magnetic resonance (NMR) observations. The simulated ultraviolet photoelectron spectra (UPS) based on the three structures agree well with the measurements. Particularly, the parent cage of the experimentally observed Tm-C 82 isomer with C s symmetry is newly assigned, which matches the experiments better than early assignments. In addition, strong interaction between an endohedral Tm atom and the C 82 cage is discussed and is thought to be responsible for the dramatic change in the relative stability of C 82 isomers when Tm is encapsulated.

  12. G-factor for the K-6, Jsup(π) = 6+ isomer in 178Hf

    International Nuclear Information System (INIS)

    Faestermann, T.; Haeusser, O.; Ward, D.; Andrews, H.R.; Alexander, T.K.; Horn, D.

    1978-01-01

    High-K isomers are prevalent towards the end of the rare-earth region of deformed nuclei where the valence particles fill high Ω orbitals. Very little is known about the g-factors for these isomers mainly because in the half-life range encountered, 50 ns-50 μs, quadrupole and paramagnetic relaxation effects can destroy the nuclear alignment very rapidly. In 178 Hf a Isub(π)K=6 + 6 isomer with a half-life of 78 ns has recently been found. It decays predominantly to the ground band (K=O) 6 + and 4 + levels with gamma rays of 921.8 keV and 1247.3 keV respectively. The authors have measured the g-factor of this isomer with the method of perturbed angular distributions. (Auth.)

  13. Mannose7 Glycan Isomer Characterization by IMS-MS/MS Analysis

    Science.gov (United States)

    Zhu, Feifei; Lee, Sunyoung; Valentine, Stephen J.; Reilly, James P.; Clemmer, David E.

    2012-12-01

    The isomers of the Man7GlcNAc2 glycan obtained from bovine ribonuclease B have been characterized by ion mobility spectrometry-tandem mass spectrometry (IMS-MS/MS). In these experiments, [Man7 + 2Na]2+ precursors having different mobilities are selected by ion mobility spectrometry and analyzed by MS/MS techniques in an ion trap. The fragmentation spectra obtained for various precursor ions are specific, suggesting the isolation or enrichment of different glycan isomers. One fragment ion with a mass-to-charge ratio ( m/z) of 903.8 is found to correspond to the loss of an internal mannose residue of a specific isomer. Extracted fragment ion drift time distributions (XFIDTDs) yield distinctive precursor ion drift time profiles indicating the existence of four separate isomers as proposed previously.

  14. The Creation and Destruction of Hf-178m2 Isomer by Neutron Interaction

    Energy Technology Data Exchange (ETDEWEB)

    Hsu, Hsiao-Hua [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); TechSource, Inc. Los Alamos, NM (United States); Talbert, Willard L. [TechSource, Inc. Los Alamos, NM (United States); Ward, Tom [TechSource, Inc. Los Alamos, NM (United States)

    2017-03-06

    The property of the isomer state in 178m2Hf was an interesting topic in nuclear structure studies during the time period 1970 to 1980. The state at 2.446 MeV with spin and parity Kπ = 16+, has a half-life of 31 years. The isomer is described as a four-quasi-particle state. The K forbidden deexcitatiion by gamma emission is the reason for long half-life. During 1980, the isomer became a troublesome issue for radiation safety workers, because this isomer can also be produced in the first wall of a fussion reactor containing tungsten and also in a tungsten beam stop of a high-energy accelerator.

  15. Study on Separation of Structural Isomer with Magneto-Archimedes method

    Science.gov (United States)

    Kobayashi, T.; Mori, T.; Akiyama, Y.; Mishima, F.; Nishijima, S.

    2017-09-01

    Organic compounds are refined by separating their structural isomers, however each separation method has some problems. For example, distillation consumes large energy. In order to solve these problems, new separation method is needed. Considering organic compounds are diamagnetic, we focused on magneto-Archimedes method. With this method, particle mixture dispersed in a paramagnetic medium can be separated in a magnetic field due to the difference of the density and magnetic susceptibility of the particles. In this study, we succeeded in separating isomers of phthalic acid as an example of structural isomer using MnCl2 solution as the paramagnetic medium. In order to use magneto-Archimedes method for separating materials for food or medicine, we proposed harmless medium using oxygen and fluorocarbon instead of MnCl2 aqueous solution. As a result, the possibility of separating every structural isomer was shown.

  16. Gamma spectroscopy within the island of high-spin isomers near N = 82

    International Nuclear Information System (INIS)

    Borggreen, J.; Bjoernholm, S.; Christensen, O.; Del Zoppo, A.; Herskind, B.; Pedersen, J.; Sletten, G.

    1980-01-01

    A NaI sum-spectrometer combined with Ge-counters has been used to characterize the members of the island of high spin isomers near N = 82. On the basis of half lives, total γ-decay energies and discrete γ-lines, assignments of 22 isomers are given or confirmed. The isomers are localized to the region 82 <= N <= 86 and Z <= 68, and the excitation energies vary from 3 MeV to 12.2 MeV. An empirical relation between spin and excitation energy is presented and on this basis isomeric spin values up to (33 +- 2)h are deduced. The isomers are thought to be due to strong alignment of 2 to 8 shellmodel particles in a spherical or possibly weakly oblate potential. (orig.) 891 FKS/orig. 892 HIS

  17. Detection of trans-isomers of hydrocarbon residues of lipid molecules by IR absorption

    Science.gov (United States)

    Mikhalovsky, I. S.; Samoylov, M. V.; Wileishikova, N. P.

    2009-01-01

    IR spectroscopy is used for a comparative analysis of the trans-isomerization of double bonds in hydrocarbon residuals of lactic and hydrogenated lipids. The maximum of the absorption band of the trans-isomers for all the lipid samples is found to lie at 965 cm-1. An absorption band at 970 cm-1 is discovered in the spectra of the lactic lipids near the analytic band of the trans-isomers at 965 cm-1. Based on a gaussian approximation for their absorption spectral bands, the trans-isomer content in the lactic lipid samples is 10-11%. The absorption by lipid molecules at 970 cm-1 has to be taken into account when determining the trans-isomer content of fat and oil products.

  18. Isomer shift and magnetic moment of the long-lived 1/2$^{+}$ isomer in $^{79}_{30}$Zn$_{49}$: signature of shape coexistence near $^{78}$Ni

    CERN Document Server

    Yang, X.F.; Xie, L.; Babcock, C.; Billowes, J.; Bissell, M.L.; Blaum, K.; Cheal, B.; Flanagan, K.T.; Garcia Ruiz, R. F.; Gins, W.; Gorges, C.; Grob, L.K.; Heylen, H.; Kaufmann, S.; Kowalska, M.; Kraemer, J.; Malbrunot-Ettenauer, S.; Neugart, R.; Neyens, G.; Nörtershäuser, W.; Papuga, J.; Sánchez, R.; Yordanov, D.T.

    2016-01-01

    Collinear laser spectroscopy has been performed on the $^{79}_{30}$Zn$_{49}$ isotope at ISOLDE-CERN. The existence of a long-lived isomer with a few hundred milliseconds half-life was confirmed, and the nuclear spins and moments of the ground and isomeric states in $^{79}$Zn as well as the isomer shift were measured. From the observed hyperfine structures, spins $I = 9/2$ and $I = 1/2$ are firmly assigned to the ground and isomeric states. The magnetic moment $\\mu$ ($^{79}$Zn) = $-$1.1866(10) $\\mu_{\\rm{N}}$, confirms the spin-parity $9/2^{+}$ with a $\

  19. Altered stereoselectivity of cocaine and bupivacaine isomers in normal and batrachotoxin-modified Na+ channels

    Science.gov (United States)

    1992-01-01

    The inhibitory effects of local anesthetics (LAs) of cocaine and bupivacaine optical isomers on Na+ currents were studied in clonal GH3 cells under whole-cell patch clamp conditions. At holding potential of - 100 mV, all four isomers inhibited peak Na+ currents when the cell was stimulated infrequently. The dose-response curves of this tonic block of peak Na+ currents by (-)/(+) cocaine and (-)/(+) bupivacaine were well fitted by the Langmuir isotherm, suggesting that one LA isomer blocked one Na+ channel. Each pair of isomers showed no greater than a twofold difference in stereoselectivity toward Na+ channels. Additional block of Na+ currents occurred when the cell was stimulated at 2 Hz. This use-dependent block was also observed in all four isomers, which again displayed little stereoselectivity. The voltage dependence of the use-dependent block produced by cocaine isomers did not overlap with the activation of Na+ channels but did overlap with the steady-state inactivation (h infinity), indicating that cocaine can bind directly to the inactivated state of Na+ channels before channel opening. In comparison, the peak batrachotoxin (BTX)-modified Na+ currents were little inhibited by cocaine and bupivacaine isomers. However, the maintained BTX-modified Na+ currents were highly sensitive toward the (- ) form of cocaine and bupivacaine isomers during a prolonged depolarization. As a result, a profound time-dependent block of BTX- modified Na+ currents was evident in the presence of these LA isomers. The estimated values of the equilibrium dissociation constant (KD in micromolar) at +50 mV were 35.8, 661, 7.0, and 222 for (-)/(+) cocaine and (-)/(+) bupivacaine, respectively. Although chloramine-T (CT) also modified the fast inactivation of Na+ channels and gave rise to a maintained Na+ current during a prolonged depolarization, LA isomers showed no greater stereoselectivity in blocking this maintained current than in blocking the normal transient Na+ current. We

  20. Synthesis of azaphenanthridines via anionic ring closure

    DEFF Research Database (Denmark)

    Hansen, Henriette Møller; Lysén, M.; Begtrup, M.

    2005-01-01

    A new and convergent synthesis of azaphenanthridines via an anionic ring closure is reported. Ortho-lithiation/in situ borylation of cyanopyridines produces the corresponding cyanopyridylboronic esters, which undergo a Suzuki-Miyaura cross-coupling to give the key intermediates. Addition of lithium...

  1. Interstellar dehydrogenated PAH anions: vibrational spectra

    Science.gov (United States)

    Buragohain, Mridusmita; Pathak, Amit; Sarre, Peter; Gour, Nand Kishor

    2018-03-01

    Interstellar polycyclic aromatic hydrocarbon (PAH) molecules exist in diverse forms depending on the local physical environment. Formation of ionized PAHs (anions and cations) is favourable in the extreme conditions of the interstellar medium (ISM). Besides in their pure form, PAHs are also likely to exist in substituted forms; for example, PAHs with functional groups, dehydrogenated PAHs etc. A dehydrogenated PAH molecule might subsequently form fullerenes in the ISM as a result of ongoing chemical processes. This work presents a density functional theory (DFT) calculation on dehydrogenated PAH anions to explore the infrared emission spectra of these molecules and discuss any possible contribution towards observed IR features in the ISM. The results suggest that dehydrogenated PAH anions might be significantly contributing to the 3.3 μm region. Spectroscopic features unique to dehydrogenated PAH anions are highlighted that may be used for their possible identification in the ISM. A comparison has also been made to see the size effect on spectra of these PAHs.

  2. 11-nor-9-carboxy-Δ9-tetrahydrocannabinol glucuronide exhibits acyl-migration isomers.

    Science.gov (United States)

    Hanisch, Stephanie; Paulke, Alexander; Toennes, Stefan W

    2017-11-30

    11-nor-Δ 9 -Tetrahydrocannabinol-9-carboxylic acid glucuronide (THCCOOH-glucuronide) is an 1-β-O-acyl glucuronide which degrades not only to 11-nor-9-carboxy-Δ 9 -THC (THCCOOH) but, additionally, to an isomer with a currently unknown structure. The present study was carried out to examine whether acyl glucuronide isomers are formed by acyl migration and if they are involved in formation of this isomer. THCCOOH-glucuronide was incubated in phosphate buffer (pH 7.4, 37°C, 7days) and a variety of glucuronide cleavage procedures were performed. Samples of the incubation mixture and of different biological specimens from cannabis users were analyzed using liquid chromatography-mass spectrometry (LC-MS/MS). A total of six chromatographically separated isomeric acyl glucuronides were detected during incubation of THCCOOH-glucuronide reference substance. In biological specimens of cannabis users, two additional isomers were found. However, the main glucuronide present in human specimens was different from that of a commercially available reference substance. Both, the commercial and the authentic glucuronide were cleaved by β-glucuronidases, the other formed isomers by alkaline hydrolysis only. Mass spectrometric investigations (i.e. product ion, precursor ion and neutral loss scans) confirmed identity. The THCCOOH isomer was detected in all authentic samples, but not in those after buffer incubation. By analyzing THCCOOH-glucuronide in authentic samples, it has to be taken into account that the authentic glucuronide is different from that of the commercial reference standard. THCCOOH-glucuronide undergoes acyl migration and some isomers occur to minor extents in biological specimens. Acyl migration does not lead to the formation of the THCCOOH isomer. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Conversion electron spectrum of the (1/2)+ isomer of 235U

    International Nuclear Information System (INIS)

    Zhudov, V.I.; Zelenkov, A.G.; Kulakov, V.M.; Mostovoj, V.I.; Odinov, B.V.

    1979-01-01

    The differential conversion electron spectrum of the (1/2) + isomer of 235 U was measured. Three lines were detected in the spectrum which correspond to conversion by the (6psub(1/2)) 2 , (6psub(3/2)) 4 and 6d electron shells of a uranium atom. The excitation energy of the isomer was determined as (76+-2) eV. (author)

  4. Modelling the transport of carbonic acid anions through anion-exchange membranes

    International Nuclear Information System (INIS)

    Nikonenko, V.; Lebedev, K.; Manzanares, J.A.; Pourcelly, G.

    2003-01-01

    Electrodiffusion of carbonate and bicarbonate anions through anion-exchange membranes (AEM) is described on the basis of the Nernst-Planck equations taking into account coupled hydrolysis reactions in the external diffusion boundary layers (DBLs) and internal pore solution. The model supposes local electroneutrality as well as chemical and thermodynamic equilibrium. The transport is considered in three layers being an anion exchange membrane and two adjoining diffusion layers. A mechanism of competitive transport of HCO 3 - and CO 3 2- anions through the membrane which takes into account Donnan exclusion of H + ions is proposed. It is predicted that the pH of the depleting solution decreases and that of the concentrating solution increases during electrodialysis (ED). Eventual deviations from local electroneutrality and local chemical equilibrium are discussed

  5. Quantification of Structural Isomers via Mode-Selective Irmpd

    Science.gov (United States)

    Polfer, Nicolas C.

    2016-06-01

    Mixtures of structural isomers can pose a challenge for vibrational ion spectroscopy. In cases where particular structures display diagnostic vibrations, these structures can be selectively "burned away". In ion traps, the ion population can be subjected to multiple laser shots, in order to fully deplete a particular structure, in effect allowing a quantification of this structure. Protonated para-amino benzoic acid (PABA) serves as an illustrative example. PABA is known to preferentially exist in the N-protonated (N-prot) form in solution, but in the gas phase it is energetically favorable in the O-protonated (O-prot) form. As shown in Figure 1, the N-prot structure can be kinetically trapped in the gas phase when sprayed from non-protic solvent, whereas the O-prot structure is obtained when sprayed from protic solvents, analogous to results by others [1,2]. y parking the light source on the diagnostic 3440 wn mode, the percentage of the O-prot structure can be determined, and by default the remainder is assumed to adopt the N-prot structure. It will be shown that the relative percentages of O-prot vs N-prot are highly dependent on the solvent mixture, going from close to 0% O-prot in non-protic solvents, to 99% in protic solvents. Surprisingly, water behaves much more like a non-protic solvent than methanol. It is observed that the capillary temperature, which aids droplet desolvation by black-body radiation in the ESI source, is critical to promote the appearance of O-prot structures. These results are consistent with the picture that a protic bridge mechanism is at play to facilitate proton transfer, and thus allow conversion from N-prot to O-prot, but that this mechanism is subject to appreciable kinetic barriers on the timescale of solvent evaporation. 1. J. Phys. Chem. A 2011, 115, 7625. 2. Anal. Chem. 2012, 84, 7857.

  6. Experimental Detection of the Pentazole Anion, N5(-)

    National Research Council Canada - National Science Library

    Vij, Ashwani

    2002-01-01

    .... Whereas at low collision voltages the para-phenoxypentazole anion undergoes stepwise N2 elimination generating the corresponding azide and nitrene, at high collision voltages the N5(-) anion is formed...

  7. Advances in anion supramolecular chemistry: from recognition to chemical applications.

    Science.gov (United States)

    Evans, Nicholas H; Beer, Paul D

    2014-10-27

    Since the start of this millennium, remarkable progress in the binding and sensing of anions has been taking place, driven in part by discoveries in the use of hydrogen bonding, as well as the previously under-exploited anion-π interactions and halogen bonding. However, anion supramolecular chemistry has developed substantially beyond anion recognition, and now encompasses a diverse range of disciplines. Dramatic advance has been made in the anion-templated synthesis of macrocycles and interlocked molecular architectures, while the study of transmembrane anion transporters has flourished from almost nothing into a rapidly maturing field of research. The supramolecular chemistry of anions has also found real practical use in a variety of applications such as catalysis, ion extraction, and the use of anions as stimuli for responsive chemical systems. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Enhanced DOC removal using anion and cation ion exchange resins.

    Science.gov (United States)

    Arias-Paic, Miguel; Cawley, Kaelin M; Byg, Steve; Rosario-Ortiz, Fernando L

    2016-01-01

    Hardness and DOC removal in a single ion exchange unit operation allows for less infrastructure, is advantageous for process operation and depending on the water source, could enhance anion exchange resin removal of dissolved organic carbon (DOC). Simultaneous application of cationic (Plus) and anionic (MIEX) ion exchange resin in a single contact vessel was tested at pilot and bench scales, under multiple regeneration cycles. Hardness removal correlated with theoretical predictions; where measured hardness was between 88 and 98% of the predicted value. Comparing bench scale DOC removal of solely treating water with MIEX compared to Plus and MIEX treated water showed an enhanced DOC removal, where removal was increased from 0.5 to 1.25 mg/L for the simultaneous resin application compared to solely applying MIEX resin. A full scale MIEX treatment plant (14.5 MGD) reduced raw water DOC from 13.7 mg/L to 4.90 mg/L in the treated effluent at a bed volume (BV) treatment rate of 800, where a parallel operation of a simultaneous MIEX and Plus resin pilot (10 gpm) measured effluent DOC concentrations of no greater than 3.4 mg/L, even at bed volumes of treatment 37.5% greater than the full scale plant. MIEX effluent compared to simultaneous Plus and MIEX effluent resulted in differences in fluorescence intensity that correlated to decreases in DOC concentration. The simultaneous treatment of Plus and MIEX resin produced water with predominantly microbial character, indicating the enhanced DOC removal was principally due to increased removal of terrestrially derived organic matter. The addition of Plus resin to a process train with MIEX resin allows for one treatment process to remove both DOC and hardness, where a single brine waste stream can be sent to sewer at a full-scale plant, completely removing lime chemical addition and sludge waste disposal for precipitative softening processes. Published by Elsevier Ltd.

  9. Quadrupole moment of the 7/21- isomer state in 43S. Shell model study of sulfur isotopes around N=28

    International Nuclear Information System (INIS)

    Chevrier, Raphael

    2013-01-01

    The goal of this work consists in providing new insights in the shape coexistence expected in neutron-rich nuclei around the N=28 shell closure. In 43 S, recent experimental data as well as their interpretation in the shell model framework were used to predict the coexistence between a J π =3/2 1 - prolate deformed ground state and a 7/2 1 - rather spherical isomer state. We report on the quadrupole moment measurement Q s of the 7/2 1 - isomer state [E*=320.5(5) keV, T 1/2 =415(3) ns] in 43 S. The TDPAD method was applied on 43 S nuclei produced by the fragmentation of a 48 Ca primary beam at 345 A.MeV, and selected in-flight through the BigRIPS spectrometer at RIKEN (Japan). The measured value, |Q s |=23(3) efm 2 , is in remarkable agreement with that calculated in the shell model framework, although it is significantly larger than that expected for a single-particle state. In order to understand the nature of the correlations responsible for the departure of the isomer state from a pure spherical shape, we report on the results of a shell model study using the modern SDPF-U interaction of the neighbors sulfur isotopes 42,44,46 S. Those calculations allowed to identify a slight triaxial degree of freedom in the structure of these nuclei, although the latter happens to be highly hindered at N=28 in 44 S. Spectroscopic factor calculations show that this slight triaxial degree of freedom also impacts the low-lying structure in 43 S. It allows to better understand the deviation of the spectroscopic quadrupole moment value of the isomer state from the limit case of a pure spherical state. (author) [fr

  10. Low-lying level structure of the neutron-rich nucleus {sup 109}Nb: A possible oblate-shape isomer

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, H., E-mail: hiroshi@ribf.riken.j [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Sumikama, T. [Department of Physics, Faculty of Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba (Japan); Nishimura, S. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Yoshinaga, K. [Department of Physics, Faculty of Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba (Japan); Li, Z. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Miyashita, Y. [Department of Physics, Faculty of Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba (Japan); Yamaguchi, K. [Department of Physics, Osaka University, Machikaneyama-machi 1-1, Osaka 560-0043 Toyonaka (Japan); Baba, H. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Berryman, J.S. [Nuclear Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Blasi, N. [INFN, Sezione di Milano, via Celoria 16, I-20133 Milano (Italy); Bracco, A.; Camera, F. [INFN, Sezione di Milano, via Celoria 16, I-20133 Milano (Italy); Dipartimento di Fisica, Universita di Milano, via Celoria 16, I-20133 Milano (Italy); Chiba, J. [Department of Physics, Faculty of Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba (Japan); Doornenbal, P. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Go, S.; Hashimoto, T.; Hayakawa, S. [Center for Nuclear Study, University of Tokyo, Hirosawa 2-1, Wako, Saitama 351-0198 (Japan); Hinke, C. [Physik Department, Technische Universitaet Muenchen, D-85748 Garching (Germany); Ideguchi, E. [Center for Nuclear Study, University of Tokyo, Hirosawa 2-1, Wako, Saitama 351-0198 (Japan); Isobe, T. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan)

    2011-01-31

    The neutron-rich nuclei {sup 109}Nb and {sup 109}Zr have been populated using in-flight fission of a {sup 238}U beam at 345 MeV/nucleon at the RIBF facility. A T{sub 1/2}=150(30) ns isomer at 313 keV has been identified in {sup 109}Nb for the first time. The low-lying levels in {sup 109}Nb have been also populated following the {beta}-decay of {sup 109}Zr. Based on the difference in feeding pattern between the isomeric and {beta} decays, the decay scheme from the isomeric state in {sup 109}Nb was established. The observed hindrances of the electromagnetic transitions deexciting the isomeric state are discussed in terms of possible shape coexistence. Potential energy surface calculations for single-proton configurations predict the presence of low-lying oblate-deformed states in {sup 109}Nb.

  11. Synthesis of Framework Isomer MOFs Containing Zinc and 4-Tetrazolyl Benzenecarboxylic Acid via a Structure Directing Solvothermal Approach

    Directory of Open Access Journals (Sweden)

    Carlos Ordonez

    2015-04-01

    Full Text Available The solvothermal synthesis of framework isomers was carried out using the hybrid carboxylate and tetrazolate functional ligand, 4-tetrazolyl benzenecarboxylic acid (H2TBC, TBC = 4-tetrazolyl benzenecarboxylate and zinc. H2TBC was also synthesized with the solvothermal approach, and is referred herein as structure 1. Using single-crystal X-ray diffraction, we found that the tetrazolate groups of TBC show an unusual “opposite-on” coordination mode with zinc. Three previously characterized metal-organic frameworks (MOFs were obtained by systematically changing the solvents of the H2TBC-Zn reaction, (1 ZnTBC, 2, which has a non-porous structure; (2 Zn2(TBC2(H2O, 3, which has an amphiphilic pore structure and (3 Zn2(TBC2{guest}, 4, which is porous and has channels containing uncoordinated N heteroatoms. Fluorescence spectra of 4 reveal a strong blue emission mainly from the TBC ligands.

  12. Lanthanum-mediated dehydrogenation of butenes: Spectroscopy and formation of La(C4H6) isomers.

    Science.gov (United States)

    Cao, Wenjin; Hewage, Dilrukshi; Yang, Dong-Sheng

    2018-01-28

    La atom reactions with 1-butene, 2-butene, and isobutene are carried out in a laser-vaporization molecular beam source. The three reactions yield the same La-hydrocarbon products from the dehydrogenation and carbon-carbon bond cleavage and coupling of the butenes. The dehydrogenated species La(C 4 H 6 ) is the major product, which is characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectrum of La(C 4 H 6 ) produced from the La+1-butene reaction exhibits two band systems, whereas the MATI spectra produced from the La+2-butene and isobutene reactions display only a single band system. Each of these spectra shows a strong origin band and several vibrational progressions. The two band systems from the spectrum of the 1-butene reaction are assigned to the ionization of two isomers: La[C(CH 2 ) 3 ] (Iso A) and La(CH 2 CHCHCH 2 ) (Iso B), and the single band system from the spectra of the 2-butene and isobutene reactions is attributed to Iso B and Iso A, respectively. The ground electronic states are 2 A 1 (C 3v ) for Iso A and 2 A' (C s ) for Iso B. The ionization of the doublet state of each isomer removes a La 6s-based electron and leads to the 1 A 1 ion of Iso A and the 1 A' ion of Iso B. The formation of both isomers consists of La addition to the C=C double bond, La insertion into two C(sp 3 )-H bonds, and H 2 elimination. In addition to these steps, the formation of Iso A from the La+1-butene reaction may involve the isomerization of 1-butene to isobutene prior to the C-H bond activation, whereas the formation of Iso B from the La+trans-2-butene reaction may include the trans- to cis-butene isomerization after the C-H bond activation.

  13. Lanthanum-mediated dehydrogenation of butenes: Spectroscopy and formation of La(C4H6) isomers

    Science.gov (United States)

    Cao, Wenjin; Hewage, Dilrukshi; Yang, Dong-Sheng

    2018-01-01

    La atom reactions with 1-butene, 2-butene, and isobutene are carried out in a laser-vaporization molecular beam source. The three reactions yield the same La-hydrocarbon products from the dehydrogenation and carbon-carbon bond cleavage and coupling of the butenes. The dehydrogenated species La(C4H6) is the major product, which is characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectrum of La(C4H6) produced from the La+1-butene reaction exhibits two band systems, whereas the MATI spectra produced from the La+2-butene and isobutene reactions display only a single band system. Each of these spectra shows a strong origin band and several vibrational progressions. The two band systems from the spectrum of the 1-butene reaction are assigned to the ionization of two isomers: La[C(CH2)3] (Iso A) and La(CH2CHCHCH2) (Iso B), and the single band system from the spectra of the 2-butene and isobutene reactions is attributed to Iso B and Iso A, respectively. The ground electronic states are 2A1 (C3v) for Iso A and 2A' (Cs) for Iso B. The ionization of the doublet state of each isomer removes a La 6s-based electron and leads to the 1A1 ion of Iso A and the 1A' ion of Iso B. The formation of both isomers consists of La addition to the C=C double bond, La insertion into two C(sp3)—H bonds, and H2 elimination. In addition to these steps, the formation of Iso A from the La+1-butene reaction may involve the isomerization of 1-butene to isobutene prior to the C—H bond activation, whereas the formation of Iso B from the La+trans-2-butene reaction may include the trans- to cis-butene isomerization after the C—H bond activation.

  14. Ultrafast time-resolved absorption spectroscopy of geometric isomers of carotenoids

    International Nuclear Information System (INIS)

    Niedzwiedzki, Dariusz M.; Sandberg, Daniel J.; Cong, Hong; Sandberg, Megan N.; Gibson, George N.; Birge, Robert R.; Frank, Harry A.

    2009-01-01

    The structures of a number of stereoisomers of carotenoids have been revealed in three-dimensional X-ray crystallographic investigations of pigment-protein complexes from photosynthetic organisms. Despite these structural elucidations, the reason for the presence of stereoisomers in these systems is not well understood. An important unresolved issue is whether the natural selection of geometric isomers of carotenoids in photosynthetic pigment-protein complexes is determined by the structure of the protein binding site or by the need for the organism to accomplish a specific physiological task. The association of cis isomers of a carotenoid with reaction centers and trans isomers of the same carotenoid with light-harvesting pigment-protein complexes has led to the hypothesis that the stereoisomers play distinctly different physiological roles. A systematic investigation of the photophysics and photochemistry of purified, stable geometric isomers of carotenoids is needed to understand if a relationship between stereochemistry and biological function exists. In this work we present a comparative study of the spectroscopy and excited state dynamics of cis and trans isomers of three different open-chain carotenoids in solution. The molecules are neurosporene (n = 9), spheroidene (n = 10), and spirilloxanthin (n = 13), where n is the number of conjugated π-electron double bonds. The spectroscopic experiments were carried out on geometric isomers of the carotenoids purified by high performance liquid chromatography (HPLC) and then frozen to 77 K to inhibit isomerization. The spectral data taken at 77 K provide a high resolution view of the spectroscopic differences between geometric isomers. The kinetic data reveal that the lifetime of the lowest excited singlet state of a cis-isomer is consistently shorter than that of its corresponding all-trans counterpart despite the fact that the excited state energy of the cis molecule is typically higher than that of the trans

  15. Nuclear Magnetic Resonance Spectroscopy Investigations of Naphthalene-Based 1,2,3-Triazole Systems for Anion Sensing

    Directory of Open Access Journals (Sweden)

    Karelle Aiken

    2018-02-01

    Full Text Available Detailed Nuclear Magnetic Resonance (NMR spectroscopy investigations on a novel naphthalene-substituted 1,2,3-triazole-based fluorescence sensor provided evidence for the “turn-on” detection of anions. The one-step, facile synthesis of the sensors was implemented using the “Click chemistry” approach in good yield. When investigated for selectivity and sensitivity against a series of anions (F−, Cl−, Br−, I−, H2PO4−, ClO4−, OAc−, and BF4−, the sensor displayed the strongest fluorometric response for the fluoride anion. NMR and fluorescence spectroscopic studies validate a 1:1 binding stoichiometry between the sensor and the fluoride anion. Single crystal X-ray diffraction evidence revealed the structure of the sensor in the solid state.

  16. Modelling the Effects of Competing Anions on Fluoride Removal by ...

    African Journals Online (AJOL)

    NICOLAAS

    ... the physico-chemical properties of anions and their interaction with the adsorbent surface.16. Properties of anions such as the solubility, ionic radius, hydration energy and bulk diffusion coefficient are of great importance for the selective adsorption of anions.17 In our earlier study the equilibrium and thermodynamics of ...

  17. Cationic and Anionic Disorder in CZTSSe Kesterite Compounds: A Chemical Crystallography Study.

    Science.gov (United States)

    Bais, Pierre; Caldes, Maria Teresa; Paris, Michaël; Guillot-Deudon, Catherine; Fertey, Pierre; Domengès, Bernadette; Lafond, Alain

    2017-10-02

    The cationic and anionic disorder in the Cu 2 ZnSnSe 4 -Cu 2 ZnSnS 4 (CZTSe-CZTS) system has been investigated through a chemical crystallography approach including X-ray diffraction (in conventional and resonant setup), 119 Sn and 77 Se NMR spectroscopy, and high-resolution transmission electron microscopy (HRTEM) techniques. Single-crystal XRD analysis demonstrates that the studied compounds behave as a solid solution with the kesterite crystal structure in the whole S/(S + Se) composition range. As previously reported for pure sulfide and pure selenide compounds, the 119 Sn NMR spectroscopy study gives clear evidence that the level of Cu/Zn disorder in mixed S/Se compounds depends on the thermal history of the samples (slow cooled or quenched). This conclusion is also supported by the investigation of the 77 Se NMR spectra. The resonant single-crystal XRD technique shows that regardless of the duration of annealing step below the order-disorder critical temperature the ordering is not a long-range phenomenon. Finally, for the very first time, HREM images of pure selenide and mixed S/Se crystals clearly show that these compounds have different microstructures. Indeed, only the mixed S/Se compound exhibits a mosaic-type contrast which could be the sign of short-range anionic order. Calculated images corroborate that HRTEM contrast is highly dependent on the nature of the anion as well as on the local anionic order.

  18. Interactions between anions and soil constituents

    International Nuclear Information System (INIS)

    Bolt, G.H.; Haan, F.A.M. de

    1965-01-01

    Clay mineral crystals are characterized by a non-isotropic structure, in which a pattern is recognized. It is known that the planar sides are negatively charged (as a result of the isomorphic replacement of Si 4+ by Al 3+ and/or Al 3+ by Mg 2+ ). Under certain conditions the exposed alumina groups at the edges are charged positively. The different types of interaction between ions and clay crystals may be listed as follows: (a) Cations: positive adsorption on planar side (electrostatic interaction modified by -- non-electrostatic -- specific factors); and possibly negative adsorption at positively charged edges (electrostatic effect). (b) Anions: negative adsorption (exclusion) on planar side (electrostatic effect); and positive adsorption on the edges -- in part electrostatic, if edge positively charged; furthermore chemisorption of certain anions, as e.g. PO 4 , SiO 4

  19. An intracellular anion channel critical for pigmentation.

    Science.gov (United States)

    Bellono, Nicholas W; Escobar, Iliana E; Lefkovith, Ariel J; Marks, Michael S; Oancea, Elena

    2014-12-16

    Intracellular ion channels are essential regulators of organellar and cellular function, yet the molecular identity and physiological role of many of these channels remains elusive. In particular, no ion channel has been characterized in melanosomes, organelles that produce and store the major mammalian pigment melanin. Defects in melanosome function cause albinism, characterized by vision and pigmentation deficits, impaired retinal development, and increased susceptibility to skin and eye cancers. The most common form of albinism is caused by mutations in oculocutaneous albinism II (OCA2), a melanosome-specific transmembrane protein with unknown function. Here we used direct patch-clamp of skin and eye melanosomes to identify a novel chloride-selective anion conductance mediated by OCA2 and required for melanin production. Expression of OCA2 increases organelle pH, suggesting that the chloride channel might regulate melanin synthesis by modulating melanosome pH. Thus, a melanosomal anion channel that requires OCA2 is essential for skin and eye pigmentation.

  20. Politseiuuringud kooskõlastamisele / Liivia Anion

    Index Scriptorium Estoniae

    Anion, Liivia

    2003-01-01

    1. aprillil 2003. a. moodustatud uurimistööde kooskõlastamise komisjoni tegevuse eesmärk on saada ülevaade kõrgkoolides õppivate töötajate poolt politseis korraldatavatest uurimustest, kasutada saadud infot politsei kasuks ja vältida teenistujate tööd segavate uurimuste tegemist. Komisjoni liige Liivia Anion teeb ülevaate komisjoni otsustuspädevuse valdkondadest ja töökorraldusest

  1. Sequence anatomy of mitochondrial anion carriers

    Czech Academy of Sciences Publication Activity Database

    Ježek, Petr; Ježek, Jan

    2003-01-01

    Roč. 534, 1-3 (2003), s. 15-25 ISSN 0014-5793 R&D Projects: GA AV ČR IAA5011106; GA ČR GA301/02/1215; GA MŠk ME 389 Institutional research plan: CEZ:AV0Z5011922 Keywords : mitochondrial anion carriers * carrier genomics * bioinformatics Subject RIV: CE - Biochemistry Impact factor: 3.609, year: 2003

  2. Molecular basis of claudin-17 anion selectivity.

    Science.gov (United States)

    Conrad, Marcel P; Piontek, Jörg; Günzel, Dorothee; Fromm, Michael; Krug, Susanne M

    2016-01-01

    Claudin-17 is a paracellular channel-forming tight junction protein. Unlike the cation channels claudin-2 and -15, claudin-17 forms a distinct anion-selective channel. Aim of this study was to determine the molecular basis of channel formation and charge selectivity of this protein. To achieve this, residues located in the extracellular loops (ECL) 1 and 2 of claudin-17 were substituted, preferably those whose charges differed in claudin-17 and in claudin-2 or -15. The respective mutants were stably expressed in MDCK C7 cells and their ability to form charge-selective channels was analyzed by measuring ion permeabilities and transepithelial electrical resistance. The functional data were combined with homology modeling of the claudin-17 protomer using the structure of claudin-15 as template. In ECL1, K65, R31, E48, and E44 were found to be stronger involved in Cldn17 channel function than the clustered R45, R56, R59, and R61. For K65, not only charge but also stereochemical properties were crucial for formation of the anion-selective channel. In ECL2, both Y149 and H154 were found to contribute to constitution of the anion channel in a distinct manner. In conclusion, we provide insight into the molecular mechanism of the formation of charge- and size-selective paracellular ion channels. In detail, we propose a hydrophilic furrow in the claudin-17 protomer spanning from a gap between the ends of TM2 and TM3 along R31, E48, and Y67 to a gap between K65 and S68 lining the anion channel.

  3. Revisiting the Anionic Polymerization of Methyl Ethacrylate

    Energy Technology Data Exchange (ETDEWEB)

    Kennemur, Justin G. [Department of Chemistry and Biochemistry, Florida State University, Tallahassee FL 32306-4390 USA; Bates, Frank S. [Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis MN 55455-0431 USA; Hillmyer, Marc A. [Department of Chemistry, University of Minnesota, Minneapolis MN 55455-0431 USA

    2017-09-26

    Synthesis of poly(methyl ethacrylate), (PMEA), in tetrahydrofuran at -78 °C using anionic polymerization techniques results in high molar mass (>30 kg mol-1), low dispersity (1.3), and high conversion (>81%). The molar masses of a series of samples are consistent with values anticipated by the monomer-to-initiator ratio and conversion. These results represent a significant improvement to earlier reported attempts to prepare PMEA using anionic methods. Successful diblock polymerization of polystyrene-block-PMEA, (PS-PMEA), and poly(4-tert-butylstyrene)-block-PMEA, (PtBS-PMEA), is achieved through sequential anionic polymerization techniques with dispersities as low as 1.06 and segment molar fractions close to those targeted. Broad principal scattering peaks observed by small-angle X-ray scattering (SAXS) for symmetric PS-PMEA at relatively high molar mass (39 kg mol-1) suggests an effective interaction parameter (χeff) that is smaller than for PS-block-poly(methyl methacrylate). On the other hand, PtBS-PMEA block polymers form a well-ordered morphology based on SAXS measurements and is attributable to the more hydrophobic PtBS segment. These results confirm the viability of PMEA as a new constituent in the expanding suite of polymers suitable for preparing nanostructured block polymers.

  4. Deep inelastic reactions and isomers in neutron-rich nuclei across the perimeter of the A = 180 - 190 deformed region

    International Nuclear Information System (INIS)

    Dracoulis, G.D.; Lane, G.J.; Byrne, A.P.; Watanabe, H.; Hughes, R.O.; Kondev, F.G.; Carpenter, M.P.; Janssens, R.V.F.; Lauritsen, T.; Lister, C.J.; Seweryniak, D.; Zhu, S.; Chowdhury, P.; Shi, Y.; Xu, F.R.

    2014-01-01

    Recent results on high-spin isomers populated in deep-inelastic reactions in the transitional tungsten-osmium region are outlined with a focus on 190 Os, 192 Os and 194 Os. As well as the characterization of several two-quasineutron isomers, the 12 + and 20 + isomers in 192 Os are interpreted as manifestations of maximal rotation alignment within the neutron i(13/2) and possibly proton h(11/2) shells at oblate deformation. (authors)

  5. Thermodynamics and Kinetics of Guest-Induced Switching between “Basket Handle” Porphyrin Isomers

    Directory of Open Access Journals (Sweden)

    Alexander B. C. Deutman

    2014-04-01

    Full Text Available The synthesis and switching properties of two “basket handle” porphyrin isomers is described. The cis-oriented meso-phenyl groups of these porphyrins are linked at their ortho-positons via benzocrown-ether-based spacers, which as a result of slow atropisomerization are located either on the same side of the porphyrin plane (cis, or on opposite sides (trans. In solution, the cis-linked isomer slowly isomerizes in the direction of the thermodynamically more stable trans-isomer. In the presence of viologen (N,N'-dialkyl-4,4'-bipyridinium derivatives, which have different affinities for the two isomers, the isomerization equilibrium could be significantly influenced. In addition, the presence of these guests was found to enhance the rate of the switching process, which was suggested to be caused by favorable interactions between the positively charged guest and the crown ethers of the receptor, stabilizing the transition state energies of the isomerization reaction between the two isomers.

  6. Natural and bioremediated selective degradation of polycyclic aromatic alkyl isomers in oil-contaminated soils

    International Nuclear Information System (INIS)

    Sauer, T.C.; McCarthy, K.; Uhler, A.; Porta, A.

    1995-01-01

    In studies where 2- to 6-ring polycyclic aromatic hydrocarbons (PAHs) are determined as part of characterizing released oil constituents in environmental samples, the changes in composition of PAHs from weathering (e.g., evaporation, dissolution) and biodegradation are most often represented by PAH alkyl homologue distributions. Concentrations of PAH alkyl groups are the sum of individual PAH isomers of similar carbon number; such as for C2-naphthalenes, the C2 alkyl group consists of dimethyl and ethyl substitutions on the parent naphthalene. In weathering and degradation studies, the changes in relative concentration of the individual isomers within an alkyl group are rarely reported. In a field study of oiled soils, the authors looked at the selective losses, for a period of a year, of individual PAH alkyl isomers that occur both naturally by weathering processes and through the use of bioremediation technology. Results showed that decreases in alkyl group concentrations were not always represented by similar losses of each isomer in the alkyl group, but were often due to the preferential or selective loss of certain isomers in the group

  7. Three-quasiparticle isomer in 173Ta and the excitation energy dependence of K -forbidden transition rates

    OpenAIRE

    Wood, RT; Walker, PM; Lane, G J; Carroll, R. J.; Cullen, David; Dracoulis, G D; Hota, S. S.; Kibédi, T.; Palalani, N; Podolyak, Zs.; Reed, MW; Schiffl, K; Wright, A.M

    2017-01-01

    Using the 168Er(10B,5n) reaction at a beam energy of 68 MeV, new data have been obtained for the population and decay of a T1/2=148ns, Kπ=21/2− three-quasiparticle isomer at 1717 keV in 173Ta. Revised decay energies and intensities have been determined, together with newly observed members of a rotational band associated with the isomer. By comparison with other isomers in the A≈180 deformed region, the 173Ta isomer properties help to specify the key degrees of freedom that determine K-forbid...

  8. Linear and branched perfluorooctane sulfonate (PFOS) isomer patterns differ among several tissues and blood of polar bears.

    Science.gov (United States)

    Greaves, Alana K; Letcher, Robert J

    2013-09-01

    Perfluorooctane sulfonate (PFOS) is a globally distributed persistent organic pollutant that has been found to bioaccumulate and biomagnify in aquatic food webs. Although principally in its linear isomeric configuration, 21-35% of the PFOS manufactured via electrochemical fluorination is produced as a branched structural isomer. PFOS isomer patterns were investigated in multiple tissues of polar bears (Ursus maritimus) from East Greenland. The liver (n = 9), blood (n = 19), brain (n = 16), muscle (n = 5), and adipose (n = 5) were analyzed for linear PFOS (n-PFOS), as well as multiple mono- and di-trifluoromethyl-substituted branched isomers. n-PFOS accounted for 93.0 ± 0.5% of Σ-PFOS isomer concentrations in the liver, whereas the proportion was significantly lower (pblood (85.4 ± 0.5%). Branched isomers were quantifiable in the liver and blood, but not in the brain, muscle, or adipose. In both the liver and blood, 6-perfluoromethylheptane sulfonate (P6MHpS) was the dominant branched isomer (2.61 ± 0.10%, and 3.26 ± 0.13% of Σ-PFOS concentrations, respectively). No di-trifluoromethyl-substituted isomers were detectable in any of the tissues analyzed. These tissue-specific isomer patterns suggest isomer-specific pharmacokinetics, perhaps due to differences in protein affinities, and thus differences in protein interactions, as well transport, absorption, and/or metabolism in the body. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

  9. Statistical model calculation of fission isomer excitation functions in (n,n') and (n,γ) reactions

    International Nuclear Information System (INIS)

    Chatterjee, A.; Athougies, A.L.; Mehta, M.K.

    1977-01-01

    A statistical model developed by Britt and others (1971, 1973) to analyze isomer excitation functions in spallation type reactions like (α,2n) has been adopted in fission isomer calculations for (n,n') and (n,γ) reactions. Calculations done for 235 U(n,n')sup(238m)U and 235 U(n,γ)sup(236m)U reactions have been compared with experimental measurements. A listing of the computer program ISOMER using FORTRAN IV to calculate the isomer to prompt ratios is given. (M.G.B.)

  10. Probing the early stages of salt nucleation—Experimental and theoretical investigations of sodium/potassium thiocyanate cluster anions

    Energy Technology Data Exchange (ETDEWEB)

    Deng, S. H. M.; Kong, Xiang-Yu; Wang, Xue-Bin, E-mail: xuebin.wang@pnnl.gov [Physical Sciences Division, Pacific Northwest National Laboratory, 902 Battelle Boulevard, P. O. Box 999, MS K8-88, Richland, Washington 99352 (United States)

    2015-01-14

    Due to the fast solvent evaporation in electrospray ionization (ESI), the concentration of initially dilute electrolyte solutions rapidly increases to afford the formation of supersaturated droplets and generation of various pristine anhydrous salt clusters in the gas phase. The size, composition, and charge distributions of these clusters, in principle, witness the nucleation evolution in solutions. Herein, we report a microscopic study on the initial stage of nucleation and crystallization of sodium/potassium thiocyanate salt solutions simulated in the ESI process. Singly charged M{sub x}(SCN){sub x+1}{sup −}, doubly charged M{sub y}(SCN){sub y+2}{sup 2−} (M = Na, K), and triply charged K{sub z}(SCN){sub z+3}{sup 3−} anion clusters (x, y, and z stand for the number of alkali atoms in the singly, doubly, and triply charged clusters, respectively) were produced via electrospray of the corresponding salt solutions and were characterized by negative ion photoelectron spectroscopy (NIPES). The vertical detachment energies (VDEs) of these sodium/potassium thiocyanate cluster anions were obtained, and theoretical calculations were carried out for the sodium thiocyanate clusters in assisting spectral identification. The measured VDEs of singly charged anions M{sub x}(SCN){sub x+1}{sup −} (M = Na and K) demonstrate that they are superhalogen anions. The existence of doubly charged anions M{sub y}(SCN){sub y+2}{sup 2−} (y = 2x, x ≥ 4 and 3 for M = Na and K, respectively) and triply charged anions K{sub z}(SCN){sub z+3}{sup 3−} (z = 3x, x ≥ 6) was initially discovered from the photoelectron spectra for those singly charged anions of M{sub x}(SCN){sub x+1}{sup −} with the same mass-to-charge ratio (m/z), and later independently confirmed by the observation of their distinct mass spectral distributions and by taking their NIPE spectra for those pure multiply charged anions with their m/z different from the singly charged species. For large clusters, multiply

  11. Probing the early stages of salt nucleation—Experimental and theoretical investigations of sodium/potassium thiocyanate cluster anions

    Science.gov (United States)

    Deng, S. H. M.; Kong, Xiang-Yu; Wang, Xue-Bin

    2015-01-01

    Due to the fast solvent evaporation in electrospray ionization (ESI), the concentration of initially dilute electrolyte solutions rapidly increases to afford the formation of supersaturated droplets and generation of various pristine anhydrous salt clusters in the gas phase. The size, composition, and charge distributions of these clusters, in principle, witness the nucleation evolution in solutions. Herein, we report a microscopic study on the initial stage of nucleation and crystallization of sodium/potassium thiocyanate salt solutions simulated in the ESI process. Singly charged M x (SCN)x + 1 - , doubly charged M y (SCN)y + 2 2 - (M = Na, K), and triply charged K z (SCN)z + 3 3 - anion clusters (x, y, and z stand for the number of alkali atoms in the singly, doubly, and triply charged clusters, respectively) were produced via electrospray of the corresponding salt solutions and were characterized by negative ion photoelectron spectroscopy (NIPES). The vertical detachment energies (VDEs) of these sodium/potassium thiocyanate cluster anions were obtained, and theoretical calculations were carried out for the sodium thiocyanate clusters in assisting spectral identification. The measured VDEs of singly charged anions M x (SCN)x + 1 - (M = Na and K) demonstrate that they are superhalogen anions. The existence of doubly charged anions M y (SCN)y + 2 2 - (y = 2x, x ≥ 4 and 3 for M = Na and K, respectively) and triply charged anions K z (SCN)z + 3 3 - (z = 3x, x ≥ 6) was initially discovered from the photoelectron spectra for those singly charged anions of M x (SCN)x + 1 - with the same mass-to-charge ratio (m/z), and later independently confirmed by the observation of their distinct mass spectral distributions and by taking their NIPE spectra for those pure multiply charged anions with their m/z different from the singly charged species. For large clusters, multiply charged clusters were found to become preferred, but at higher temperatures, those multiply charged

  12. N-Protonated Isomers and Coulombic Barriers to Dissociation of Doubly Protonated Ala8Arg

    Science.gov (United States)

    Haeffner, Fredrik; Irikura, Karl K.

    2017-10-01

    Collision-induced dissociation (or tandem mass spectrometry, MS/MS) of a protonated peptide results in a spectrum of fragment ions that is useful for inferring amino acid sequence. This is now commonplace and a foundation of proteomics. The underlying chemical and physical processes are believed to be those familiar from physical organic chemistry and chemical kinetics. However, first-principles predictions remain intractable because of the conflicting necessities for high accuracy (to achieve qualitatively correct kinetics) and computational speed (to compensate for the high cost of reliable calculations on such large molecules). To make progress, shortcuts are needed. Inspired by the popular mobile proton model, we have previously proposed a simplified theoretical model in which the gas-phase fragmentation pattern of protonated peptides reflects the relative stabilities of N-protonated isomers, thus avoiding the need for transition-state information. For singly protonated Ala n ( n = 3-11), the resulting predictions were in qualitative agreement with the results from low-energy MS/MS experiments. Here, the comparison is extended to a model tryptic peptide, doubly protonated Ala8Arg. This is of interest because doubly protonated tryptic peptides are the most important in proteomics. In comparison with experimental results, our model seriously overpredicts the degree of backbone fragmentation at N9. We offer an improved model that corrects this deficiency. The principal change is to include Coulombic barriers, which hinder the separation of the product cations from each other. Coulombic barriers may be equally important in MS/MS of all multiply charged peptide ions. [Figure not available: see fulltext.

  13. Exploring rearrangements along the fragmentation pathways of diuron anion: A combined experimental and computational investigation

    Science.gov (United States)

    Kanawati, Basem; Harir, Mourad; Schmitt-Kopplin, Philippe

    2009-12-01

    Diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea), a common herbicide from phenyl urea class, was investigated by studying the formation of several negative ions [M-H]- in the gas phase and the fragmentation behaviour of the thermodynamically most probably formed isomeric anions upon linear ion acceleration/collision experiments. The collision induced dissociation experiments (CID) were carried out in a hexapole-quadrupole-hexapole hybrid system coupled to 12 T magnet with infinity ICR cell for high resolution measurements. Two distinctive main pathways were observed in the MS/MS spectrum. Sustained off-resonance irradiation (SORI) experiments inside the ICR cell reinforce the fragmentation channels obtained from linear ion acceleration experiments. The fragmentation pathways were also completely investigated by the use of B3LYP/6-311+G(2d,p)//B3LYP/6-31+G(d) level of theory. Elimination of dimethylamine takes place in a two-step process, by which two successive 1,3 proton shifts occur. The second 1,3 proton shift is concerted with the departure of dimethylamine. The driving force for the (CH3)2NH elimination is the formation of isocyanate group. The formed primary product ion can further decompose to release HCl through a new transition state. A stable new aromatic product ion is formed with 10[pi] electrons. Loss of C3H5NO neutral from another anionic isomer of the precursor ion was also observed and is characteristic for the amide terminal of the diamide functional group. A concerted mechanism is proposed, by which N-C bond breakage and cyclization of the eliminated neutral fragment C3H5NO takes place simultaneously to form 1-methyl-aziridin-2-one.

  14. A combined experimental and computational study of the molecular interactions between anionic ibuprofen and water

    International Nuclear Information System (INIS)

    Zapata-Escobar, Andy; Manrique-Moreno, Marcela; Guerra, Doris; Hadad, C. Z.; Restrepo, Albeiro

    2014-01-01

    In this work, we report a detailed study of the microsolvation of anionic ibuprofen, Ibu − . Stochastic explorations of the configurational spaces for the interactions of Ibu − with up to three water molecules at the DFT level lead to very rich and complex potential energy surfaces. Our results suggest that instead of only one preponderant structure, a collection of isomers with very similar energies would have significant contributions to the properties of the solvated drug. One of these properties is the shift on the vibrational frequencies of the asymmetric stretching band of the carboxylate group in hydrated Ibu − with respect to the anhydrous drug, whose experimental values are nicely reproduced using the weighted contribution of the structures. We found at least three types of stabilizing interactions, including conventional CO 2 − ⋯H 2 O, H 2 O⋯H 2 O charge assisted hydrogen bonds (HBs), and less common H 2 O⋯H–C and H 2 O⋯π interactions. Biological water molecules, those in direct contact with Ibu − , prefer to cluster around the carboxylate oxygen atoms via cyclic or bridged charge assisted hydrogen bonds. Many of those interactions are strongly affected by the formal carboxylate charge, resulting in “enhanced” HBs with increased strengths and degree of covalency. We found striking similarities between this case and the microsolvation of dymethylphosphate, which lead us to hypothesize that since microsolvation of phosphatidylcholine depends mainly on the formal charge of its ionic PO 2 − group in the polar head, then microsolvation of anionic ibuprofen and interactions of water molecules with eukaryotic cell membranes are governed by the same types of physical interactions

  15. A combined experimental and computational study of the molecular interactions between anionic ibuprofen and water

    Energy Technology Data Exchange (ETDEWEB)

    Zapata-Escobar, Andy; Manrique-Moreno, Marcela; Guerra, Doris; Hadad, C. Z.; Restrepo, Albeiro, E-mail: albeiro@exactas.udea.edu.co [Instituto de Química, Universidad de Antioquia UdeA, Calle 70 No. 52–21, Medellín (Colombia)

    2014-05-14

    In this work, we report a detailed study of the microsolvation of anionic ibuprofen, Ibu{sup −}. Stochastic explorations of the configurational spaces for the interactions of Ibu{sup −} with up to three water molecules at the DFT level lead to very rich and complex potential energy surfaces. Our results suggest that instead of only one preponderant structure, a collection of isomers with very similar energies would have significant contributions to the properties of the solvated drug. One of these properties is the shift on the vibrational frequencies of the asymmetric stretching band of the carboxylate group in hydrated Ibu{sup −} with respect to the anhydrous drug, whose experimental values are nicely reproduced using the weighted contribution of the structures. We found at least three types of stabilizing interactions, including conventional CO {sub 2}{sup −}⋯H{sub 2}O, H{sub 2}O⋯H{sub 2}O charge assisted hydrogen bonds (HBs), and less common H{sub 2}O⋯H–C and H{sub 2}O⋯π interactions. Biological water molecules, those in direct contact with Ibu{sup −}, prefer to cluster around the carboxylate oxygen atoms via cyclic or bridged charge assisted hydrogen bonds. Many of those interactions are strongly affected by the formal carboxylate charge, resulting in “enhanced” HBs with increased strengths and degree of covalency. We found striking similarities between this case and the microsolvation of dymethylphosphate, which lead us to hypothesize that since microsolvation of phosphatidylcholine depends mainly on the formal charge of its ionic PO {sub 2}{sup −} group in the polar head, then microsolvation of anionic ibuprofen and interactions of water molecules with eukaryotic cell membranes are governed by the same types of physical interactions.

  16. Uterotropic activity of cis and trans isomers of zearalenone and zearalenol.

    Science.gov (United States)

    Mirocha, C J; Pathre, S V; Behrens, J; Schauerhamer, B

    1978-01-01

    The cis and trans isomers of zearalenone [2,4-dihyroxy-6-(10-hydroxy-6-oxo-1-undecenyl)-benzoic acid mu-lactone] and zearalenol [2,4-dihydroxy-6-(6,10-dihydroxy-1-undecenyl)-benzoic acid mu-lactone] were tested for uterotropic activity in the white rat. The metabolites were administered through the oral route (per os) and by topical application to the freshly shaven skin on the back. cis-Zearalenone was significantly more active than trans when fed orally to the rats in the diet or when applied topically by skin application. However, the cis isomer of zearalenol was not significantly different than its trans isomer. trans-Zearalenone was less active than trans-zearalenol. PMID:655715

  17. High-spin isomers in 212Rn in the region of triple neutron core-excitations

    Science.gov (United States)

    Dracoulis, G. D.; Lane, G. J.; Byrne, A. P.; Davidson, P. M.; Kibédi, T.; Nieminen, P.; Watanabe, H.; Wilson, A. N.

    2008-04-01

    The level scheme of 212Rn has been extended to spins of ∼ 38 ℏ and excitation energies of about 13 MeV using the 204Hg(13C, 5n)212Rn reaction and γ-ray spectroscopy. Time correlated techniques have been used to obtain sensitivity to weak transitions and channel selectivity. The excitation energy of the 22+ core-excited isomer has been established at 6174 keV. Two isomers with τ = 25 (2) ns and τ = 12 (2) ns are identified at 12211 and 12548 keV, respectively. These are the highest-spin nuclear isomers now known, and are attributed to configurations involving triple neutron core-excitations coupled to the aligned valence protons. Semi-empirical shell-model calculations can account for most states observed, but with significant energy discrepancies for some configurations.

  18. High-spin isomers in 212Rn in the region of triple neutron core-excitations

    International Nuclear Information System (INIS)

    Dracoulis, G.D.; Lane, G.J.; Byrne, A.P.; Davidson, P.M.; Kibedi, T.; Nieminen, P.; Watanabe, H.; Wilson, A.N.

    2008-01-01

    The level scheme of 212 Rn has been extended to spins of ∼38h and excitation energies of about 13 MeV using the 204 Hg( 13 C, 5n) 212 Rn reaction and γ-ray spectroscopy. Time correlated techniques have been used to obtain sensitivity to weak transitions and channel selectivity. The excitation energy of the 22 + core-excited isomer has been established at 6174 keV. Two isomers with τ=25(2) ns and τ=12(2) ns are identified at 12211 and 12548 keV, respectively. These are the highest-spin nuclear isomers now known, and are attributed to configurations involving triple neutron core-excitations coupled to the aligned valence protons. Semi-empirical shell-model calculations can account for most states observed, but with significant energy discrepancies for some configurations

  19. Activation of Reactive MALDI Adduct Ions Enables Differentiation of Dihydroxylated Vitamin D Isomers

    Science.gov (United States)

    Qi, Yulin; Müller, Miriam J.; Volmer, Dietrich A.

    2017-12-01

    Vitamin D compounds are secosteroids, which are best known for their role in bone health. More recent studies have shown that vitamin D metabolites and catabolites such as dihydroxylated species (e.g., 1,25- and 24,25-dihydroxyvitamin D3) play key roles in the pathologies of various diseases. Identification of these isomers by mass spectrometry is challenging and currently relies on liquid chromatography, as the isomers exhibit virtually identical product ion spectra under collision induced dissociation conditions. Here, we developed a simple MALDI-CID method that utilizes ion activation of reactive analyte/matrix adducts to distinguish isomeric dihydroxyvitamin D3 species, without the need for chromatography separation or chemical derivatization techniques. Specifically, reactive 1,5-diaminonaphthalene adducts of dihydroxyvitamin D3 compounds formed during MADI were activated and specific cleavages in the secosteroid's backbone structure were achieved that produced isomer-diagnostic fragment ions. [Figure not available: see fulltext.

  20. Decomposition Patterns of Three C20 Isomer Clusters: Tight-binding Molecular Dynamics Simulation

    International Nuclear Information System (INIS)

    Lee, Changhoon; Lee, Kee Hag

    2016-01-01

    We investigated the decomposition pattern of three C 20 carbon isomer clusters using molecular dynamics simulations combined with the empirical tight-binding total energy calculation method. Here, the thermodynamic behaviors show up for 2 ps. Dynamic behavior is researched by considering the change in assembly energy, bond distance distribution, total energy, and potential energy as a function of temperature. The bonds start breaking around 3300, 4500, and 5100 K for cage, bowl, and ring isomers, respectively. Once a bond is broken, strain accumulates on the neighbors of that atom, and bond cleavage is further accelerated at the neighboring atoms. Based on the snapshots of decomposition, we suggest a C 20 formation scenario from linear carbon clusters to ring, bowl, or cage isomers.

  1. Effect of isomers of hydroxybenzoic acid on the growth and metabolism of Chlorella vulgaris Beijerinck (Chlorophyceae

    Directory of Open Access Journals (Sweden)

    Andrzej Bajguz

    2014-01-01

    Full Text Available The isomers o-, m-, and p- of hydroxybenzoic acid (HBA in the concentration range 10-1-10-4 M in the unicellular green alga Chlorella vulgaris (Chlorophyceae display marked biological activity. The o-HBA isomer, commonly known as salicylic acid, in a concentration of 10-4 M exerted the most stimulating effect on the parameters analysed (the number of cells, dry mass, the content of chlorophylls a and h, carotenoids, soluble proteins and their secretion, monosaccharides, DNA and RNA whereas p-HBA had weak stimulating properties. On the other hand, m-HBA had a weak inhibitory effect on the growth of C. vulgaris and all the biochemical parameters analysed in comparison with the control culture of algae devoid of HBA isomers.

  2. Ion-selective electrode and anion gap range: What should the anion gap be?

    OpenAIRE

    Sadjadi,; Manalo,Rendell; Jaipaul,Navin; McMillan,James

    2013-01-01

    Seyed-Ali Sadjadi, Rendell Manalo, Navin Jaipaul, James McMillan Jerry L Pettis Memorial Veterans Medical Center, Loma Linda University School of Medicine, Loma Linda, CA, USA Background: Using flame photometry technique in the 1970s, the normal value of anion gap (AG) was determined to be 12 ± 4 meq/L. However, with introduction of the autoanalyzers using an ion-selective electrode (ISE), the anion gap value has fallen to lower levels. Methods: A retrospective study of US veteran...

  3. Investigation of nuclei near N = 82 and Z = 64 VIA radioactive decay of high-spin isomers

    International Nuclear Information System (INIS)

    Toth, K.S.

    1979-01-01

    An island of very high spin isomers was found recently in neutron-deficient Gd-Lu nuclei near the N = 82 closed shell in (H.I.,xn) measurements. This exciting discovery has led to a large number of experiments trying to identify the structures of these isomers and the nuclei in which they occur. These attempts have been helped in many instances by available spectroscopic information at low excitation energies. A systematic investigation of the low-lying structure of nuclei near N = 82 and Z greater than or equal to 64 was carried out. Heavy-ion beams were used to produce proton-rich isotopes which were then transported, with the use of gas-jet systems, to shielded areas where singles and coincidence γ-ray measurements could be made. Earlier investigations dealt with the decay of terbium ( 146-149 Tb) and dysprosium ( 147-152 Dy) nuclei. During the past two years the research program was extended to holmium nuclides (A less than or equal to 152) produced in 10 B bombardments of samarium. Two new isotopes, 149 Ho and 148 Ho, were identified. The decay data of 21-s 149 Ho supplement in-beam results and locate the hg/ 2 neutron state in 149 Dy to be at 1091 keV. The most intense γ-ray associated with 9-s 148 Ho has an energy of 1688 keV. It is possibly the first-excited to ground-state transition in 148 Dy. Recent in-beam measurements have shown that the first-excited state in 146 Gd is, unespectedly, 3 - in contrast to doubly evenN = 82 nuclei below gadolinium where it is 2 + . It would be interesting to determine whether the 1688-keV level in 148 Dy, the next nucleus in this isotonic series, is 2reverse arrow or 3 - in character. 12 references

  4. Graphene-coated polymeric anion exchangers for ion chromatography

    International Nuclear Information System (INIS)

    Zhang, Kai; Cao, Minyi; Lou, Chaoyan; Wu, Shuchao; Zhang, Peimin; Zhi, Mingyu; Zhu, Yan

    2017-01-01

    Carbonaceous stationary phases have gained much attention for their peculiar selectivity and robustness. Herein we report the fabrication and application of a graphene-coated polymeric stationary phase for anion exchange chromatography. The graphene-coated particles were fabricated by a facile evaporation-reduction method. These hydrophilic particles were proven appropriate substrates for grafting of hyperbranched condensation polymers (HBCPs) to make pellicular anion exchangers. The new phase was characterized by zeta potentials, Fourier transform infrared spectroscopy, thermogravimetry and scanning electron microscope. Frontal displacement chromatography showed that the capacities of the anion exchangers were tuned by both graphene amount and HBCPs layer count. The chromatographic performance of graphene-coated anion exchangers was demonstrated with separation of inorganic anions, organic acids, carbohydrates and amino acids. Good reproducibility was obtained by consecutive injections, indicating high chemical stability of the coating. - Highlights: • Graphene-coated polymeric particles were fabricated by a facile method. • Hyperbranched condensation polymers (HBCPs) were grafted from graphene-coated particles to make anion exchangers. • Graphene amount and HBCPs layer count had significant effects on the anion exchange capacities. • Separation of diverse anionic analytes on the anion exchangers was demonstrated. • The prepared anion exchangers exhibited high stability.

  5. Graphene-coated polymeric anion exchangers for ion chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Kai; Cao, Minyi; Lou, Chaoyan [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China); Wu, Shuchao, E-mail: wushch2002@163.com [Zhejiang Institute of Geology and Mineral Resources, Hangzhou 310007 (China); Zhang, Peimin [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China); Zhi, Mingyu [Hangzhou Vocational & Technical College, Hangzhou, 310018 (China); Zhu, Yan, E-mail: zhuyan@zju.edu.cn [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China)

    2017-06-01

    Carbonaceous stationary phases have gained much attention for their peculiar selectivity and robustness. Herein we report the fabrication and application of a graphene-coated polymeric stationary phase for anion exchange chromatography. The graphene-coated particles were fabricated by a facile evaporation-reduction method. These hydrophilic particles were proven appropriate substrates for grafting of hyperbranched condensation polymers (HBCPs) to make pellicular anion exchangers. The new phase was characterized by zeta potentials, Fourier transform infrared spectroscopy, thermogravimetry and scanning electron microscope. Frontal displacement chromatography showed that the capacities of the anion exchangers were tuned by both graphene amount and HBCPs layer count. The chromatographic performance of graphene-coated anion exchangers was demonstrated with separation of inorganic anions, organic acids, carbohydrates and amino acids. Good reproducibility was obtained by consecutive injections, indicating high chemical stability of the coating. - Highlights: • Graphene-coated polymeric particles were fabricated by a facile method. • Hyperbranched condensation polymers (HBCPs) were grafted from graphene-coated particles to make anion exchangers. • Graphene amount and HBCPs layer count had significant effects on the anion exchange capacities. • Separation of diverse anionic analytes on the anion exchangers was demonstrated. • The prepared anion exchangers exhibited high stability.

  6. Geometrical E/Z isomers of (6R)- and (6S)-neoxanthin and biological implications.

    Science.gov (United States)

    Strand; Kvernberg; M Karlsen A; Liaaen-Jensen

    2000-06-01

    9'Z-(3S,5R,6R,3'S,5'R,6'S)-Neoxanthin reisolated from spinach (Spinacea oleracea) and characterized by HPLC, VIS, MS, and 2D (1)H NMR, has been submitted to photoinduced stereomutation in the presence of iodine or diphenyl diselenide at conditions not involving isomerization of the allenic bond. The six individual geometrical isomers, all-E,9Z,9'Z,13Z,13'Z,15Z and three minor di-Z-isomers, presumably 9,9'-di-Z,9',13-di-Z and 9',13'-di-Z, present in the equilibrium mixture have been characterized by HPLC, VIS data, 1H NMR and reversibility tests. Judged by the quantitative composition of the equilibrium mixture the naturally occurring 9'Z-isomer is thermodynamically less stable than the all-E-isomer. The availability of these isomers facilitates future search in natural sources. 9'Z-(6R90% of total neoxanthin in spinach and broccoli (Brassica oleracea var. italica), consistent with previous findings of its abundance in chloroplasts. all-E90% of total violaxanthin in the same sources. It is postulated that a neoxanthin Delta9'-isomerase is present and involved in the biosynthesis of abscisic acid in higher plants. Allenic S-isomers are of interest as postulated biosynthetic precursors of R-allenes. All-E-(6S)- and 9'Z-(6S)-neoxanthin were available as semi-synthetic model compounds. The allenic (6S)-diastereomers could not be detected in spinach or broccoli.

  7. New isomers and medium-spin structure of the 95Y nucleus

    International Nuclear Information System (INIS)

    Urban, W.; Sieja, K.; Simpson, G. S.; Faust, H.; Rzaca-Urban, T.; Zlomaniec, A.; Lukasiewicz, M.; Smith, A. G.; Durell, J. L.; Smith, J. F.; Varley, B. J.; Nowacki, F.; Ahmad, I.

    2009-01-01

    Excited states in 95 Y, populated following the spontaneous fission of 248 Cm and 252 Cf and following fission of 235 U induced by thermal neutrons, were studied by means of γ spectroscopy using the EUROGAM2 and GAMMASPHERE multidetector Ge arrays and the LOHENGRIN fission-fragment separator, respectively. We have found a new (17/2 - ) isomer in 95 Y at 3142.2 keV with a half-life of T 1/2 =14.9(5) ns. Another isomer was identified in 95 Y at 5022.1 keV and it was assigned a spin-parity (27/2 - ). For this isomer a half-life of T 1/2 =65(4) ns was determined and four decay branches were found, including an E3 decay. A new E3 decay branch was also found for the known, 1087.5-keV isomer in 95 Y, for which we measured a half-life of 51.2(9) μs. The B(E3) and B(E1) transition rates, of 2.0 and 3.8x10 -7 W.u., respectively, observed in 95 Y are significantly lower than in the neighboring 96 Zr core, suggesting that octupole correlations in this region are mainly due to the coupling of proton Δj=3 orbitals. Shell-model calculations indicate that the (27/2 - ) isomer in 95 Y corresponds to the πg 9/2 ν(g 7/2 h 11/2 ) maximally aligned configuration and that all three isomers in 95 Y decay, primarily, by M2 transitions between proton g 9/2 and f 5/2 orbitals.

  8. Resolution and Assignment of Differential Ion Mobility Spectra of Sarcosine and Isomers

    Science.gov (United States)

    Berthias, Francis; Maatoug, Belkis; Glish, Gary L.; Moussa, Fathi; Maitre, Philippe

    2018-02-01

    Due to their central role in biochemical processes, fast separation and identification of amino acids (AA) is of importance in many areas of the biomedical field including the diagnosis and monitoring of inborn errors of metabolism and biomarker discovery. Due to the large number of AA together with their isomers and isobars, common methods of AA analysis are tedious and time-consuming because they include a chromatographic separation step requiring pre- or post-column derivatization. Here, we propose a rapid method of separation and identification of sarcosine, a biomarker candidate of prostate cancer, from isomers using differential ion mobility spectrometry (DIMS) interfaced with a tandem mass spectrometer (MS/MS) instrument. Baseline separation of protonated sarcosine from α- and β-alanine isomers can be easily achieved. Identification of DIMS peak is performed using an isomer-specific activation mode where DIMS- and mass-selected ions are irradiated at selected wavenumbers allowing for the specific fragmentation via an infrared multiple photon dissociation (IRMPD) process. Two orthogonal methods to MS/MS are thus added, where the MS/MS(IRMPD) is nothing but an isomer-specific multiple reaction monitoring (MRM) method. The identification relies on the comparison of DIMS-MS/MS(IRMPD) chromatograms recorded at different wavenumbers. Based on the comparison of IR spectra of the three isomers, it is shown that specific depletion of the two protonated α- and β-alanine can be achieved, thus allowing for clear identification of the sarcosine peak. It is also demonstrated that DIMS-MS/MS(IRMPD) spectra in the carboxylic C=O stretching region allow for the resolution of overlapping DIMS peaks. [Figure not available: see fulltext.

  9. Accumulation of D- vs. L-isomers of alanine and leucine in rat prostatic adenocarcinoma

    International Nuclear Information System (INIS)

    Conti, P.S.; Schmall, B.; Bigler, R.E.; Zanzonico, P.B.; Kleinert, E.; Whitmore, W.F. Jr.

    1985-01-01

    It has been reported that tumor tissue may accumulate some D-amino acids preferentially over the L-isomers. In order to investigate the potential use of carbon-11 labeled amino acid isomers for in vivo tumor studies with positron emission tomography in patients, the tissue distributions of alanine and leucine, substrates for the A-type and L-type amino acid transport systems, respectively, were studied in Copenhagen rates bearing the Dunning R3327G prostatic adenocarcinoma. The authors have previously reported differences in the accumulation of A-type vs. L-type amino acids in rat prostatic adenocarcinoma and normal tissues. All compounds were labeled with C-14 in the carboxyl position with specific activities of 30.0-56.6 mCi/mmol. Higher levels of C-14 activity (Relative Concentration (RC)=dpm found per gm tissue + dpm inject per gm animal mass) were observed in tumor tissue using D-alanine (0.71) compared to L- (0.21) or DL-alanine (0.27) at 45 min post-injection. While tumor/prostate and tumor/liver ratios were above 2 for all three substrates, tumor/blood and tumor/muscle were above one for only the D-isomer. Comparisons made with D-, L-, and DL-leucine also demonstrated a higher level of RC in tumor tissue with the D-isomer (0.84) vs. the L-(0.66) and DL-leucine (0.63). In this case, however, tumor/blood, tumor/prostate, and tumor/muscle ratios were above one for all three substrates, while tumor/liver ratios were below one. These results support the observation of a preferential accumulation of D-amino acids in tumor tissue over the natural L-isomers. Observed differences in the accumulation of the isomers in normal tissues are discussed

  10. Source Attribution of Cyanides using Anionic Impurity Profiling, Stable Isotope Ratios, Trace Elemental Analysis and Chemometrics

    Energy Technology Data Exchange (ETDEWEB)

    Mirjankar, Nikhil S.; Fraga, Carlos G.; Carman, April J.; Moran, James J.

    2016-01-08

    Chemical attribution signatures (CAS) for chemical threat agents (CTAs) are being investigated to provide an evidentiary link between CTAs and specific sources to support criminal investigations and prosecutions. In a previous study, anionic impurity profiles developed using high performance ion chromatography (HPIC) were demonstrated as CAS for matching samples from eight potassium cyanide (KCN) stocks to their reported countries of origin. Herein, a larger number of solid KCN stocks (n = 13) and, for the first time, solid sodium cyanide (NaCN) stocks (n = 15) were examined to determine what additional sourcing information can be obtained through anion, carbon stable isotope, and elemental analyses of cyanide stocks by HPIC, isotope ratio mass spectrometry (IRMS), and inductively coupled plasma optical emission spectroscopy (ICP-OES), respectively. The HPIC anion data was evaluated using the variable selection methods of Fisher-ratio (F-ratio), interval partial least squares (iPLS), and genetic algorithm-based partial least squares (GAPLS) and the classification methods of partial least squares discriminate analysis (PLSDA), K nearest neighbors (KNN), and support vector machines discriminate analysis (SVMDA). In summary, hierarchical cluster analysis (HCA) of anion impurity profiles from multiple cyanide stocks from six reported country of origins resulted in cyanide samples clustering into three groups: Czech Republic, Germany, and United States, independent of the associated alkali metal (K or Na). The three country groups were independently corroborated by HCA of cyanide elemental profiles and corresponded to countries with known solid cyanide factories. Both the anion and elemental CAS are believed to originate from the aqueous alkali hydroxides used in cyanide manufacture. Carbon stable isotope measurements resulted in two clusters: Germany and United States (the single Czech stock grouped with United States stocks). The carbon isotope CAS is believed to

  11. Probing the early stages of salt nucleation—experimental and theoretical investigations of sodium/potassium thiocyanate cluster anions

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Shihu; Kong, Xiangyu; Wang, Xue B.

    2015-01-14

    Due to fast solvent evaporation in electrospray ionization (ESI), the concentration of initially dilute electrolyte solutions rapidly increases to afford formation of supersaturated droplets and generating various pristine anhydrous salt clusters in the gas phase. The size, composition, and charge distributions of these clusters, in principle witness the nucleation evolution in solutions. Herein, we report a microscopic study on the initial stage of nucleation and crystallization of sodium/potassium thiocyanate salt solutions simulated in the ESI process. Singly charged Mx(SCN)⁻x+1, doubly charged My(SCN)²⁻y+2 (M = Na, K), and triply charged Kz(SCN)³⁻z+3 anion clusters were produced via electrospray of the corresponding salt solutions, and were characterized by negative ion photoelectron spectroscopy (NIPES). The vertical detachment energies (VDEs) of these sodium/potassium thiocyanate cluster anions were obtained, and theoretical calculations were carried out for sodium thiocyanate clusters in assisting spectral identification. The measured VDEs of singly charged anions Mx(SCN)⁻x+1 (M = Na and K) demonstrate they are superhalogen anions. The existence of doubly charged anions My (SCN)²⁻y+2 (y = 2x, x ≥ 4 and 3 for M = Na and K, respectively) and triply charged anions Kz(SCN)³⁻z+3 (z = 3x, x ≥ 6) were initially discovered from the photoelectron spectra for those singly charged anions of Msub>x(SCN)⁻x+1 with the same mass-to-charge ratio (m/z), and later independently confirmed by observation of their distinct mass spectral distributions and by taking their NIPE spectra for those pure multiply charged anions with their m/z different from the singly charged species. For large clusters, multiply charged clusters are found to become preferred, but at higher temperatures those multiply charged clusters

  12. Conversion-electron experiment to characterize the decay of the 237Np shape isomer

    International Nuclear Information System (INIS)

    Henry, E.A.; Becker, J.A.; Bauer, R.W.; Gardner, D.G.; Decman, D.J.; Meyer, R.A.; Roy, N.; Sale, K.E.

    1987-01-01

    Conversion electrons from the decay of low-lying levels of 237 Np have been measured to detect the population of these levels by gamma-ray decay of the 237 Np shape isomer. Analysis of the 208-keV transition L conversion-electron peak gives an upper limit of about 17 μb for the population of the 3/2 - 267-keV level in 237 Np from the shape isomer decay. Model calculations are compared with the measured limit. Improvements are suggested for this experiment. 9 refs., 4 figs

  13. Nanosized silver?anionic clay matrix as nanostructured ensembles with antimicrobial activity

    OpenAIRE

    2009-01-01

    Abstract Nanostructured ensembles of silver nanoparticles/zinc-substituted anionic clay matrix (Ag/ZnLDH) were obtained by a simple synthetic route in which reconstruction of the layered clay, synthesis of the silver nanoparticles and their organisation on the clay surface took place in a single step at room temperature. The morphology, composition and phase structure of the prepared powders were characterised by X-ray diffraction, infrared spectroscopy, transmission electron micro...

  14. Probes for anionic cell surface detection

    Science.gov (United States)

    Smith, Bradley D.

    2013-03-05

    Embodiments of the present invention are generally directed to compositions comprising a class of molecular probes for detecting the presence of anionic cell surfaces. Embodiments include compositions that are enriched for these compositions and preparations, particularly preparations suitable for use as laboratory/clinical reagents and diagnostic indicators, either alone or as part of a kit. An embodiment of the invention provides for a highly selective agent useful in the discernment and identification of dead or dying cells, such as apoptotic cells, in a relatively calcium-free environment. An embodiment of the invention provides a selective agent for the identification of bacteria in a mixed population of bacterial cells and nonbacterial cells.

  15. Recognition and sensing of fluoride anion.

    Science.gov (United States)

    Cametti, Massimo; Rissanen, Kari

    2009-05-28

    Fluoride anion recognition is attracting a mounting interest in the scientific community due to its duplicitous nature. It is a useful chemical for many industrial applications, and it has been used in human diet, but, recently it has been accused for several human pathologies. Here we describe the ample panorama of different approaches the chemists world-wide have employed to face the challenge of fluoride binding, and we outline some of the research which in our view can contribute to the development of this field, especially when fluoride binding has to be achieved in highly competitive protic solvents and water.

  16. Diagnosing metabolic acidosis in the critically ill: bridging the anion gap, Stewart, and base excess methods.

    Science.gov (United States)

    Fidkowski, Christina; Helstrom, James

    2009-03-01

    Metabolic acid-base disorders are common in critically ill patients. Clinicians may have difficulty recognizing their presence when multiple metabolic acid-base derangements are present in a single patient. Clinicians should be able to identify the components of complex metabolic acid-base disorders since metabolic acidoses due to unmeasured anions are associated with increased mortality in critically ill patients. This review presents the derivation of three commonly used methods of acid-base analysis, which include the anion gap, Stewart physiochemical, and modified base excess. Clinical examples are also provided to demonstrate the subtleties of the different methods and to demonstrate their application to real patient data. A comparison of these methods shows that each one is equally adept at identifying a metabolic acidosis due to unmeasured anions; however, the Stewart physiochemical and the modified base excess methods better evaluate complex metabolic acid-base disorders. While all three methods correctly identify metabolic acidosis due to unmeasured anions, which is a predictor of mortality, it remains unclear if further delineation of complex metabolic acid-base disorders using the Stewart physiochemical or the modified base excess methods is clinically beneficial.

  17. Adsorption of model perfumes at the air-solution interface by coadsorption with an anionic surfactant.

    Science.gov (United States)

    Bradbury, Robert; Penfold, Jeffrey; Thomas, Robert K; Tucker, Ian M; Petkov, Jordan T; Jones, Craig

    2013-03-12

    The adsorption of the model perfumes phenyl ethanol, PE, and linalool, LL, at the air-solution interface by coadsorption with the anionic surfactant sodium dodecyl 6-benezene sulfonate, LAS-6, has been studied primarily by neutron reflectivity, NR. The variation in the mixed surface adsorption with solution composition is highly nonideal, and the more hydrophobic LL is more surface active. At a LAS-6 concentration of 0.5 mM the adsorption of PE and LL is broadly similar but with the LL systematically more surface active, and at 2 mM the LL completes more effectively for the surface than the PE. The variation in surface composition with solution composition and concentration reflect the greater hydrophobicity and hence surface activity of LL, and the greater solubility of PE in aqueous solution. Changing the geometry of the LAS isomer, from the symmetrical LAS-6 geometry to the more asymmetrical LAS-4, results in the LL competing more effectively for the surface due to changes in the packing constraints associated with the hydrophobic region. The results provide insights into the factors that affect coadsorption that can be more broadly applied to the surface delivery of a wide range of molecules other than perfumes.

  18. Permeation of hair dye ingredients, p-phenylenediamine and aminophenol isomers, through protective gloves.

    Science.gov (United States)

    Lee, Hsiao-Shu; Lin, Yu-Wen

    2009-04-01

    Skin irritation and contact allergies are skin disorders common to hairdressers. The predominant oxidative hair dye components, such as p-phenylenediamine (PPD) and aminophenol isomers, can cause contact dermatitis. Use of protective gloves can prevent dermal contact with skin irritants. This study investigates the permeation behaviors of p-aminophenol (PAP), m-aminophenol (MAP), o-aminophenol (OAP) and PPD in single and mixed challenge solutions with disposable natural rubber latex (NRL) gloves, disposable polyvinylchloride (PVC) gloves and neoprene (NP) gloves. The challenge solutions were 4% PPD (w/v), 3% OAP (w/v), 2% PAP (w/v) and 2% MAP (w/v) in ethanol or 12% hydrogen peroxide solutions. The cocktail solutions of the four chemicals were also tested. An American Society for Testing and Materials type permeation cell, ethanol liquid collection and gas chromatography-flame ionization detection of samples taken from the collection medium every 10 min facilitated determination of breakthrough times (BTs), cumulative permeated masses and steady-state permeation rates (SSPRs). Experiments were 4 h long for the NRL and PVC gloves and 8 h for NP gloves. No chemicals tested broke through the NP gloves when exposed for 8 h. In the ethanol solution, PPD and OAP started breaking through the PVC gloves at 40 min. The SSPRs of PVC gloves were higher than those for NRL gloves in all challenge conditions for both single chemicals and mixtures. No tested chemicals in hydrogen peroxide solutions permeated the gloves during the 4-h tests. The chemical composition of the challenge solution was a main effecter of BTs and SSPRs for the NRL glove. For disposable PVC gloves, the main factors of BTs were molecular size [molar volume (MV)] and polarity (logK(ow)), and the primary factors of SSPRs were concentration, MV and logK(ow). In conclusion, disposable NRL gloves and disposable PVC gloves should not be used repeatedly for handling the hair dye products. Hydrogen peroxide did not

  19. Isomeric and high-spin states of 94Tc and the search for yrast isomers near Napprox.50

    International Nuclear Information System (INIS)

    Lee, I.Y.; Johnson, N.R.; McGowan, F.K.; Young, G.R.; Guidry, M.W.; Yates, S.W.

    1981-01-01

    A search for isomers in the Napprox.50 region has produced no evidence of high-spin yrast isomerism. A new 4.5-ns low-multiplicity isomer has been identified and assigned to 94 Tc, while the yrast sequence of 94 Tc has been established to more than 5 MeV in excitation energy

  20. The quantum structure of anionic hydrogen clusters

    Science.gov (United States)

    Calvo, F.; Yurtsever, E.

    2018-03-01

    A flexible and polarizable interatomic potential has been developed to model hydrogen clusters interacting with one hydrogen anion, (H2)nH-, in a broad range of sizes n = 1-54 and parametrized against coupled cluster quantum chemical calculations. Using path-integral molecular dynamics simulations at 1 K initiated from the putative classical global minima, the equilibrium structures are found to generally rely on icosahedral shells with the hydrogen molecules pointing toward the anion, producing geometric magic numbers at sizes n = 12, 32, and 44 that are in agreement with recent mass spectrometry measurements. The energetic stability of the clusters is also connected with the extent of vibrational delocalization, measured here by the fluctuations among inherent structures hidden in the vibrational wave function. As the clusters grow, the outer molecules become increasingly free to rotate, and strong finite size effects are also found between magic numbers, associated with more prominent vibrational delocalization. The effective icosahedral structure of the 44-molecule cluster is found to originate from quantum nuclear effects as well, the classical structure showing no particular symmetry.

  1. An intracellular anion channel critical for pigmentation

    Science.gov (United States)

    Bellono, Nicholas W; Escobar, Iliana E; Lefkovith, Ariel J; Marks, Michael S; Oancea, Elena

    2014-01-01

    Intracellular ion channels are essential regulators of organellar and cellular function, yet the molecular identity and physiological role of many of these channels remains elusive. In particular, no ion channel has been characterized in melanosomes, organelles that produce and store the major mammalian pigment melanin. Defects in melanosome function cause albinism, characterized by vision and pigmentation deficits, impaired retinal development, and increased susceptibility to skin and eye cancers. The most common form of albinism is caused by mutations in oculocutaneous albinism II (OCA2), a melanosome-specific transmembrane protein with unknown function. Here we used direct patch-clamp of skin and eye melanosomes to identify a novel chloride-selective anion conductance mediated by OCA2 and required for melanin production. Expression of OCA2 increases organelle pH, suggesting that the chloride channel might regulate melanin synthesis by modulating melanosome pH. Thus, a melanosomal anion channel that requires OCA2 is essential for skin and eye pigmentation. DOI: http://dx.doi.org/10.7554/eLife.04543.001 PMID:25513726

  2. Isobar Separator for Anions: Current status

    International Nuclear Information System (INIS)

    Alary, Jean-François; Javahery, Gholamreza; Kieser, William; Zhao, Xiao-Lei; Litherland, Albert; Cousins, Lisa; Charles, Christopher

    2015-01-01

    The Isobar Separator for Anions (ISA) is an emerging separation technique of isobars applied first to the selective removal of 36 S from 36 Cl, achieving a relative suppression ratio of 6 orders of magnitude. Using a radio-frequency quadrupole (RFQ) column incorporating low energy gas cells, this innovative technique enables the use of a wide range of low energy ion–molecule reactions and collisional-induced dissociation processes for suppressing specific atomic of molecular anions with a high degree of selectivity. Other elemental pairs (analyte/isobar) successfully separated at AMS level include Ca/K, Sr/(Y, Zr), Cs/Ba, Hf/W and Pu/U. In view of these initial successes, an effort to develop a version of the ISA that can be used as a robust technique for routine AMS analysis has been undertaken. We will discuss the detailed layout of a practical ISA and the functional requirements that a combined ISA/AMS should meet. These concepts are currently being integrated in a pre-commercial ISA system that will be installed soon at the newly established A.E. Lalonde Laboratory in Ottawa, Canada.

  3. Isobar Separator for Anions: Current status

    Energy Technology Data Exchange (ETDEWEB)

    Alary, Jean-François, E-mail: alaryjf@isobarex.ca [Isobarex Corp., 32 Nixon Road Unit #1, Bolton, ON L7E 1W2 (Canada); Javahery, Gholamreza [IONICS Mass Spectrometry, 32 Nixon Road Unit #1, Bolton, ON L7E 1W2 (Canada); Kieser, William; Zhao, Xiao-Lei [Andre E. Lalonde Accelerator Mass Spectrometry Laboratory, Advanced Research Complex, University of Ottawa, 25 Templeton Street, Ottawa, ON K1N 6N5 (Canada); Litherland, Albert [IsoTrace Laboratory, Department of Physics, University of Toronto, 60 St. George Street, Toronto, ON M5S 3B1 (Canada); Cousins, Lisa [IONICS Mass Spectrometry, 32 Nixon Road Unit #1, Bolton, ON L7E 1W2 (Canada); Charles, Christopher [Andre E. Lalonde Accelerator Mass Spectrometry Laboratory, Advanced Research Complex, University of Ottawa, 25 Templeton Street, Ottawa, ON K1N 6N5 (Canada)

    2015-10-15

    The Isobar Separator for Anions (ISA) is an emerging separation technique of isobars applied first to the selective removal of {sup 36}S from {sup 36}Cl, achieving a relative suppression ratio of 6 orders of magnitude. Using a radio-frequency quadrupole (RFQ) column incorporating low energy gas cells, this innovative technique enables the use of a wide range of low energy ion–molecule reactions and collisional-induced dissociation processes for suppressing specific atomic of molecular anions with a high degree of selectivity. Other elemental pairs (analyte/isobar) successfully separated at AMS level include Ca/K, Sr/(Y, Zr), Cs/Ba, Hf/W and Pu/U. In view of these initial successes, an effort to develop a version of the ISA that can be used as a robust technique for routine AMS analysis has been undertaken. We will discuss the detailed layout of a practical ISA and the functional requirements that a combined ISA/AMS should meet. These concepts are currently being integrated in a pre-commercial ISA system that will be installed soon at the newly established A.E. Lalonde Laboratory in Ottawa, Canada.

  4. Anion photoelectron spectroscopy of radicals and clusters

    Energy Technology Data Exchange (ETDEWEB)

    Travis, Taylor R. [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying 2Σ and 2π states of C2nH (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C2H and C4H. Other radicals studied include NCN and I3. The author was able to observe the low-lying singlet and triplet states of NCN for the first time. Measurement of the electron affinity of I3 revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.

  5. Predictive coupled-cluster isomer orderings for some SinCm (m, n ≤ 12) clusters: A pragmatic comparison between DFT and complete basis limit coupled-cluster benchmarks

    International Nuclear Information System (INIS)

    Byrd, Jason N.; Lutz, Jesse J.; Jin, Yifan; Ranasinghe, Duminda S.; Perera, Ajith; Bartlett, Rodney J.; Montgomery, John A.; Duan, Xiaofeng F.; Burggraf, Larry W.; Sanders, Beverly A.

    2016-01-01

    The accurate determination of the preferred Si 12 C 12 isomer is important to guide experimental efforts directed towards synthesizing SiC nano-wires and related polymer structures which are anticipated to be highly efficient exciton materials for the opto-electronic devices. In order to definitively identify preferred isomeric structures for silicon carbon nano-clusters, highly accurate geometries, energies, and harmonic zero point energies have been computed using coupled-cluster theory with systematic extrapolation to the complete basis limit for set of silicon carbon clusters ranging in size from SiC 3 to Si 12 C 12 . It is found that post-MBPT(2) correlation energy plays a significant role in obtaining converged relative isomer energies, suggesting that predictions using low rung density functional methods will not have adequate accuracy. Utilizing the best composite coupled-cluster energy that is still computationally feasible, entailing a 3-4 SCF and coupled-cluster theory with singles and doubles extrapolation with triple-ζ (T) correlation, the closo Si 12 C 12 isomer is identified to be the preferred isomer in the support of previous calculations [X. F. Duan and L. W. Burggraf, J. Chem. Phys. 142, 034303 (2015)]. Additionally we have investigated more pragmatic approaches to obtaining accurate silicon carbide isomer energies, including the use of frozen natural orbital coupled-cluster theory and several rungs of standard and double-hybrid density functional theory. Frozen natural orbitals as a way to compute post-MBPT(2) correlation energy are found to be an excellent balance between efficiency and accuracy.

  6. Inhibition of nuclear waste solutions containing multiple aggressive anions

    International Nuclear Information System (INIS)

    Congdon, J.W.

    1987-01-01

    The inhibition of localized corrosion of carbon steel in caustic, high-level radioactive waste solutions was studied using cyclic potentiodynamic polarization scans, supplemented by partially immersed coupon tests. The electrochemical tests provided a rapid and accurate means of determining the relationship between the minimum inhibitor requirements and the concentration of the aggressive anions in this system. Nitrate, sulfate, chloride, and fluoride were identified as aggressive anions, however, no synergistic effects were observed between these anions. This observation may have important theoretical implications because it tends to contradict the behavior of aggressive anions as predicted by existing theories for localized corrosion. 10 refs., 5 figs., 2 tabs

  7. Photoinduced Dynamics of Neutral, Cationic, and Anionic Species

    DEFF Research Database (Denmark)

    Stephansen, Anne Boutrup

    electrons and subsequently transition from dipole to valence-bound anions in different energy regimes. The investigations indicate that dipole-bound anion formation depends strongly on the magnitude of the molecular dipole moment, while the formation and stability of valence-bound anions depends on ring....... Nucleobase anions are posited to be involved in DNA damage, where the molecular dipole moment of a nucleobase acts as electron-antenna and gateway for low-energy electrons to access the valence system of DNA. The investigations presented herein explore the abilities of adenine, thymine, and uracil to capture...

  8. Photoelectron Spectroscopy of 4-Bromochlorobenzene Dimer and Trimer Anions

    International Nuclear Information System (INIS)

    Kim, Namdoo

    2013-01-01

    I investigated the electron attachment to 4-BCB dimer and trimer anions using anion photoelectron spectroscopy and theoretical calculations. I found that an excess electron can be delocalized to these clusters through extended π-network. However, the nature of the ion core is different for the dimer and trimer. For the heterodimer anions, the geometry is determined by the differences in electronegativity of the molecules. Dimer anions with a large electronegativity difference have T-shaped geometries and those with a small electronegativity difference have PD geometries

  9. Determination of activation level energy of nuclear isomers by calibration of microspectra of radioactive sources

    International Nuclear Information System (INIS)

    Veres, A.; Pavlicsek, I.

    1980-01-01

    Nuclear isomers with unknown activation level were irradiated by calibrated radioactive sources. The integral cross sections were calculated for different energies of the sources. The activation energy was given by values coinciding with each other within the limits of error. The method made the determination of the unknown level of 1180+-10 keV of 195 Pt nucleus possible. (author)

  10. Response of Dendroctonus mexicanus (Hopkins) to two optical isomers of verbenone

    Science.gov (United States)

    Vicente Diaz-Nunez; Guillermo Sanchez-Martinez; Nancy E. Gillette

    2006-01-01

    Given the need for diminishing the use of pesticides in natural environments, in this research we investigated the efficacy of two optical isomers of verbenone (4, 6, 6-trimethylbicyclo[3.1.1] hepto-3-en-e-1) as controls of the attack of Dendroctonus mexicanus (Hopkins) (Coleoptera: Curculionidae: Scolytinae).Two experiments were established in the...

  11. Differentiation of 2- and 6-isomers of (2-dimethylaminopropylbenzofuran by tandem mass spectrometry

    Directory of Open Access Journals (Sweden)

    V. A. Shevyrin

    2016-07-01

    Full Text Available Reliable identification of new psychoactive substances of 2-(2-methylaminopropylbenzofuran and 6-(2-methylaminopropylbenzofuran is problematic when analyzing by gas chromatography–mass spectrometry method. It found that these two isomers can be reliably differentiated by MS/MS spectra obtained by collision-induced dissociation of their protonated molecules.

  12. Calibration of the isomer shift for iodine resonant transition by ab initio calculations

    Czech Academy of Sciences Publication Activity Database

    Wdowik, U. D.; Legut, Dominik; Ruebenbauer, K.

    2010-01-01

    Roč. 114, č. 26 (2010), s. 7146-7152 ISSN 1089-5639 Institutional research plan: CEZ:AV0Z20410507 Keywords : ab initio * isomer shift of iodine * calibration * I127 * I129 Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.732, year: 2010

  13. High-spin isomer in 211Rn, and the shape of the yrast line

    International Nuclear Information System (INIS)

    Dracoulis, G.D.; Fahlander, C.; Poletti, A.R.

    1981-08-01

    High spin yrast states in 211 Rn have been identified. A 61/2 - , 380 ns isomer found at 8856 keV is characterised as a core-excited configuration. The average shape of the yrast line shows a smooth behaviour with spin, in contrast to its neighbour 212 Rn. This difference is attributed to the presence of the neutron hole

  14. Observation of a new high-spin isomer in 94Pd

    International Nuclear Information System (INIS)

    Brock, T. S.; Nara Singh, B. S.; Wadsworth, R.; Boutachkov, P.; Gorska, M.; Grawe, H.; Pietri, S.; Domingo-Pardo, C.; Caceres, L.; Engert, T.; Farinon, F.; Gerl, J.; Goel, N.; Kojuharov, I.; Kurz, N.; Nociforo, C.; Prochazka, A.; Schaffner, H.; Weick, H.; Braun, N.

    2010-01-01

    A second γ-decaying high-spin isomeric state, with a half-life of 197(22)ns, has been identified in the N=Z+2 nuclide 94 Pd as part of a stopped-beam Rare Isotope Spectroscopic INvestigation at GSI (RISING) experiment. Weisskopf estimates were used to establish a tentative spin/parity of 19 - , corresponding to the maximum possible spin of a negative parity state in the restricted (p 1/2 , g 9/2 ) model space of empirical shell model calculations. The reproduction of the E3 decay properties of the isomer required an extension of the model space to include the f 5/2 and p 3/2 orbitals using the CD-Bonn potential. This is the first time that such an extension has been required for a high-spin isomer in the vicinity of 100 Sn and reveals the importance of such orbits for understanding the decay properties of high-spin isomers in this region. However, despite the need for the extended model space for the E3 decay, the dominant configuration for the 19 - state remains (πp 1/2 -1 g 9/2 -3 ) 11 x (νg 9/2 -2 ) 8 . The half-life of the known, 14 + , isomer was remeasured and yielded a value of 499(13) ns.

  15. Mixed diphosphine/diamine ruthenium (II) isomers: Synthesis, structural characterization and catalytic hydrogenation of ketones

    Science.gov (United States)

    Nascimento, Rebecca D.; Silva, Andressa K.; Lião, Luciano M.; Deflon, Victor M.; Ueno, Leonardo T.; Dinelli, Luis R.; Bogado, André L.

    2018-01-01

    The complexes trans-[RuCl2(dppb)(cydn)] (1), trans-[RuCl2(dppb)(opda)] (2) and cis-[RuCl2(dppb)(cydn)] (3) were synthesized from [{RuCl2(dppb)}2-μ-(dppb)] {where: dppb = 1,4-bis(diphenylphosphino)butane; cydn = cis and trans (±) 1,2-diaminocyclohexane, and opda = o-phenylenediamine}. The complexes were characterized by nuclear magnetic resonance of phosphorus (31P{1H} NMR), cyclic voltammetry (CV), infrared and ultraviolet/visible spectra (IR and UV/vis) as well as elemental analyses (CHN). The X-ray structures of (1) and (3) were determined and they are presented here. DFT calculations and experimental data showed that the trans isomers are obtained as thermodynamic products while the cis isomers are kinetic products. This behavior is different than described in the literature for similar complexes, where the cis isomer is obtained from the trans isomer. Additionally, the catalytic activity of the complexes (1), (2) and (3) was investigated, as pre-catalysts, in the reduction of the acetophenone and 4-methylacetophenone by transfer-hydrogenation.

  16. {sup 57}Fe quadrupole splitting and isomer shift in various oxyhemoglobins: study using Moessbauer spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Oshtrakh, M. I., E-mail: oshtrakh@mail.utnet.ru [Ural Federal University (The former Ural State Technical University-UPI), Faculty of Physical Techniques and Devices for Quality Control (Russian Federation); Berkovsky, A. L. [Hematological Scientific Center of the Russian Academy of Sciences (Russian Federation); Kumar, A.; Kundu, S., E-mail: sumankundu@south.du.ac.in [University of Delhi South Campus, Department of Biochemistry (India); Vinogradov, A. V.; Konstantinova, T. S. [Ural State Medical Academy, Faculty of Internal Diseases Propedeutics (Russian Federation); Semionkin, V. A. [Ural Federal University (The former Ural State Technical University-UPI), Faculty of Physical Techniques and Devices for Quality Control (Russian Federation)

    2010-04-15

    A comparative study of normal human, rabbit and pig oxyhemoglobins and oxyhemoglobin from patients with chronic myeloleukemia and multiple myeloma using Moessbauer spectroscopy with a high velocity resolution demonstrated small variations of the {sup 57}Fe quadrupole splitting and isomer shift. These variations may be a result of small structural differences in the heme iron stereochemistry of various hemoglobins.

  17. Effects of retinoic acid isomers on proteomic pattern in human breast cancer MCF-7 cell line

    Czech Academy of Sciences Publication Activity Database

    Flodrová, Dana; Benkovská, Dagmar; Macejová, D.; Bialešová, L.; Bobálová, Janette; Brtko, J.

    2013-01-01

    Roč. 47, č. 4 (2013), s. 205-209 ISSN 1210-0668 R&D Projects: GA MŠk(CZ) 7AMB12SK151 Institutional support: RVO:68081715 Keywords : retinoic acid isomers * retinoid * breast cancer * malignant cells * proteomic analysis Subject RIV: CB - Analytical Chemistry, Separation

  18. Serum profiles of free and conjugated neuroactive pregnanolone isomers in nonpregnant women of fertile age

    Czech Academy of Sciences Publication Activity Database

    Havlíková, H.; Hill, M.; Kancheva, L.; Vrbíková, J.; Pouzar, Vladimír; Černý, Ivan; Kancheva, R.; Stárka, L.

    2006-01-01

    Roč. 91, č. 8 (2006), s. 3092-3099 ISSN 0021-972X R&D Projects: GA MZd(CZ) NR7768 Institutional research plan: CEZ:AV0Z40550506 Keywords : pregnanolone isomers * GABAA * steroids Subject RIV: CC - Organic Chemistry Impact factor: 5.799, year: 2006

  19. The Influence of Water on Butanol Isomers Pervaporation Transport through Polyethylene Membrane..

    Czech Academy of Sciences Publication Activity Database

    Petričkovič, Roman; Setničková, Kateřina; Uchytil, Petr

    2013-01-01

    Roč. 107, APR 2 (2013), s. 85-90 ISSN 1383-5866 R&D Projects: GA ČR GA104/09/1165 Institutional support: RVO:67985858 Keywords : pervaporation * binary mixtures butanol isomers-water * polyethylene membranes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.065, year: 2013

  20. Analysis of shape isomer yields of Pu in the framework of dynamical ...

    Indian Academy of Sciences (India)

    February 2012 physics pp. 231–236. Analysis of shape isomer yields of ... the depth of the second potential well should be less than the results of statistical model calculations. Keywords. Fission; fission barrier ... (2) population of the second potential well and cooling via particle or γ emission (this event is interpreted as the ...

  1. Proline isomer-specific antibodies reveal the early pathogenic tau conformation in Alzheimer's disease.

    Science.gov (United States)

    Nakamura, Kazuhiro; Greenwood, Alex; Binder, Lester; Bigio, Eileen H; Denial, Sarah; Nicholson, Linda; Zhou, Xiao Zhen; Lu, Kun Ping

    2012-03-30

    cis-trans isomerization of proteins phosphorylated by proline-directed kinases is proposed to control numerous signaling molecules and is implicated in the pathogenesis of Alzheimer's and other diseases. However, there is no direct evidence for the existence of cis-trans protein isomers in vivo or for their conformation-specific function or regulation. Here we develop peptide chemistries that allow the generation of cis- and trans-specific antibodies and use them to raise antibodies specific for isomers of phosphorylated tau. cis, but not trans, p-tau appears early in the brains of humans with mild cognitive impairment, accumulates exclusively in degenerated neurons, and localizes to dystrophic neurites during Alzheimer's progression. Unlike trans p-tau, the cis isomer cannot promote microtubule assembly, is more resistant to dephosphorylation and degradation, and is more prone to aggregation. Pin1 converts cis to trans p-tau to prevent Alzheimer's tau pathology. Isomer-specific antibodies and vaccines may therefore have value for the early diagnosis and treatment of Alzheimer's disease. Copyright © 2012 Elsevier Inc. All rights reserved.

  2. New Isomers in the Neutron-Rich Region Beyond 208Pb

    Directory of Open Access Journals (Sweden)

    Gottardo A.

    2014-03-01

    Full Text Available The region of neutron-rich nuclei beyond 208Pb has been very difficult to explore due to its high mass and exoticity. However, recent experimental improvements allowed one to perform a quite extended isomer decay spectroscopy of these nuclei.

  3. Analysis of shape isomer yields of 237 Pu in the framework of ...

    Indian Academy of Sciences (India)

    Data on shape isomer yield for + 235U reaction at E lab = 20–29 MeV are analysed in the framework of a combined dynamical–statistical model. From this analysis, information on the double humped fission barrier parameters for some Pu isotopes has been obtained and it is shown that the depth of the second potential ...

  4. Influence of Si/Al ratio on hexane isomers adsorption equilibria

    NARCIS (Netherlands)

    Ferreira, A.F.P.; Mittelmeijer-Hazeleger, M.C.; Bliek, A.; Moulijn, J.A.

    2008-01-01

    In this work we aim to have a better knowledge of the influence of silica/alumina ratio (SAR) on the adsorption equilibrium of hexane isomers on MFI zeolites. With a manometric set-up coupled with a micro-calorimeter we did address adsorption properties and heats of adsorption of n-hexane,

  5. Adsorption of hexane isomers on MFI type zeolites at ambient temperature: Understanding the aluminium content effect

    NARCIS (Netherlands)

    Ferreira, A.F.P.; Mittelmeijer-Hazeleger, M.C.; v.d. Bergh, J.; Aguado, S.; Jansen, J.C.; Rothenberg, G.; Rodrigues, A.E.; Kapteijn, F.

    2013-01-01

    We investigate the influence of the aluminium content on the adsorption of hexane isomers at 293 K on MFI type zeolites (Si/Al ratios - SAR of 25, 100 and infinity). Adsorption isotherms were assessed with a home-made volumetric system. Temporal up-take curves were recorded using a manometric set-up

  6. Direct sampling tandem mass spectrometry (MS/MS) and multiway calibration for isomer quantitation

    NARCIS (Netherlands)

    Zampronio, Cleidiane G.; Gurden, Stephen P.; Moraes, Luis Alberto B.; Eberlin, Marcos N.; Smilde, Age K.; Poppi, Ronei J.

    2002-01-01

    Direct sampling tandem mass spectrometry (MS/MS) was used for the quantitation of mixtures of the isomers 2-, 3- and 4-ethyl pyridine. The similarity between the analytes and the second-order nature of MS/MS data require the use of multivariate calibration techniques capable of handling multiway

  7. The difference between critical care initiation anion gap and prehospital admission anion gap is predictive of mortality in critical illness.

    Science.gov (United States)

    Lipnick, Michael S; Braun, Andrea B; Cheung, Joyce Ting-Wai; Gibbons, Fiona K; Christopher, Kenneth B

    2013-01-01

    We hypothesized that the delta anion gap defined as difference between critical care initiation standard anion gap and prehospital admission standard anion gap is associated with all cause mortality in the critically ill. Observational cohort study. Two hundred nine medical and surgical intensive care beds in two hospitals in Boston, MA. Eighteen thousand nine hundred eighty-five patients, age ≥18 yrs, who received critical care between 1997 and 2007. The exposure of interest was delta anion gap and categorized a priori as 10 mEq/L. Logistic regression examined death by days 30, 90, and 365 postcritical care initiation and in-hospital mortality. Adjusted odds ratios were estimated by multivariable logistic regression models. The discrimination of delta anion gap for 30-day mortality was evaluated using receiver operator characteristic curves performed for a subset of patients with all laboratory data required to analyze the data via physical chemical principles (n = 664). None. Delta anion gap was a particularly strong predictor of 30-day mortality with a significant risk gradient across delta anion gap quartiles following multivariable adjustment: delta anion gap anion gap 5-10 mEq/L odds ratio 1.56 (95% confidence interval 1.35-1.81; p anion gap >10 mEq/L odds ratio 2.18 (95% confidence interval 1.76-2.71; p anion gap 0-5 mEq/L. Similar significant robust associations post multivariable adjustments are seen with death by days 90 and 365 as well as in-hospital mortality. Correcting for albumin or limiting the cohort to patients with standard anion gap at critical care initiation of 10-18 mEq/L did not materially change the delta anion gap-mortality association. Delta anion gap has similarly moderate discriminative ability for 30-day mortality in comparison to standard base excess and strong ion gap. An increase in standard anion gap at critical care initiation relative to prehospital admission standard anion gap is a predictor of the risk of all cause patient

  8. CYANOMETHANIMINE ISOMERS IN COLD INTERSTELLAR CLOUDS: INSIGHTS FROM ELECTRONIC STRUCTURE AND KINETIC CALCULATIONS

    Energy Technology Data Exchange (ETDEWEB)

    Vazart, Fanny; Latouche, Camille; Skouteris, Dimitrios; Barone, Vincenzo [Scuola Normale Superiore, Piazza dei Cavalieri 7, I-56125 Pisa (Italy); Balucani, Nadia [Dipartimento di Chimica, Biologia e Biotecnologie, Universitá degli Studi di Perugia, Via Elce di Sotto 8, I-06123 Perugia (Italy)

    2015-09-10

    New insights into the formation of interstellar cyanomethanimine, a species of great relevance in prebiotic chemistry, are provided by electronic structure and kinetic calculations for the reaction CN + CH{sub 2} = NH. This reaction is a facile formation route of Z,E-C-cyanomethanimine, even under the extreme conditions of density and temperature typical of cold interstellar clouds. E-C-cyanomethanimine has been recently identified in Sgr B2(N) in the Green Bank Telescope (GBT) PRIMOS survey by P. Zaleski et al. and no efficient formation routes have been envisaged so far. The rate coefficient expression for the reaction channel leading to the observed isomer E-C-cyanomethanimine is 3.15 × 10-10 × (T/300){sup 0.152} × e{sup (−0.0948/T)}. According to the present study, the more stable Z-C-cyanomethanimine isomer is formed with a slightly larger yield (4.59 × 10{sup −10} × (T/300){sup 0.153} × e{sup (−0.0871/T)}. As the detection of E-isomer is favored due to its larger dipole moment, the missing detection of the Z-isomer can be due to the sensitivity limit of the GBT PRIMOS survey and the detection of the Z-isomer should be attempted with more sensitive instrumentation. The CN + CH{sub 2} = NH reaction can also play a role in the chemistry of the upper atmosphere of Titan where the cyanomethanimine products can contribute to the buildup of the observed nitrogen-rich organic aerosols that cover the moon.

  9. Providing theoretical data for detection of four formamidic acid isomers in astrophysical media

    Science.gov (United States)

    Vichietti, R. M.; da Silva, A. B. F.; Haiduke, R. L. A.

    2018-03-01

    We present a theoretical study, so that molecular data (geometrical parameters, vibrational frequencies, infrared intensities, electronic energies, enthalpies, and Gibbs energies) of four formamidic acid (FA) isomers (labeled here as FA1, FA2, FA3, and FA4) and formamide (HCONH2) are obtained from CCSD/cc-pVTZ, CCSD/aug-cc-pVTZ, CCSD/cc-pVQZ, and CCSD(T)/cc-pVTZ calculations. Furthermore, on the basis of insufficient or even lacking theoretical and experimental results in the literature, we employed the aforementioned theory levels to determine benchmark values of dipole moments and rotational constants for these four FA isomers in order to contribute for their detection in astrophysical environments. Besides, we provide for the first time data about forward and reverse rate constants (200-4000 K) and Arrhenius' parameters for each interconversion reaction between pairs of FA isomers as well as for the tautomeric process involving FA4 and formamide, which were calculated from a Complete Basis Set (CBS) extrapolation equation obtained at CCSD/cc-pVTZ optimized geometries. Our kinetic analysis indicated a faster interconversion between the FA structures in comparison with the FA4 ↔ HCONH2 process, suggesting that these isomers could co-exist in astrophysical media. Finally, we estimated that these isomers may be detected with relative abundances, [FAx]/[HCONH2] (x = 1, 2, 3, and 4), between ∼0.01 and ∼0.1% in astrophysical sources at chemical equilibrium conditions and temperatures around 1000 K. However, these ratios can become as high as ∼1, ∼3, and ∼5%, respectively, in hotter regions with temperatures around 2000, 3000, and 4000 K (expected, for example, in massive star-forming regions).

  10. Differential developmental toxicity of naphthoic acid isomers in medaka (Oryzias latipes) embryos

    Science.gov (United States)

    Carney, Michael W.; Erwin, Kyle; Hardman, Ron; Yuen, Bonny; Volz, David C.; Hinton, David E.; Kullman, Seth W.

    2013-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are widespread persistent pollutants that readily undergo biotic and abiotic conversion to numerous transformation products in rivers, lakes and estuarine sediments. Here we characterize the developmental toxicity of four PAH transformation products each structural isomers of hydroxynaphthoic acid: 1H2NA, 2H1NA, 2H3NA, and 6H2NA. Medaka fish (Oryzias latipes) embryos and eleutheroembryos were used to determine toxicity. A 96-well micro-plate format was used to establish a robust, statistically significant platform for assessment of early life stages. Individual naphthoic acid isomers demonstrated a rank order of toxicity with 1H2NA > 2H1NA > 2H3NA > 6H2NA being more toxic. Abnormalities of circulatory system were most pronounced including pericardial edema and tube heart. To determine if HNA isomers were AhR ligands, spatial-temporal expression and activity of CYP1A was measured via in vivo EROD assessments. qPCR measurement of CYP1A induction proved different between isomers dosed at respective concentrations affecting 50% of exposed individuals (EC50s). In vitro, all ANH isomers transactivated mouse AhR using a medaka CYP1A promoter specific reporter assay. Circulatory abnormalities followed P450 induction and response was consistent with PAH toxicity. A 96-well micro-plates proved suitable as exposure chambers and provided statistically sound evaluations as well as efficient toxicity screens. Our results demonstrate the use of medaka embryos for toxicity analysis thereby achieving REACH objectives for the reduction of adult animal testing in toxicity evaluations. PMID:18433798

  11. Once upon Anion: A Tale of Photodetachment

    Science.gov (United States)

    Lineberger, W. Carl

    2013-04-01

    This contribution is very much a personal history of a journey through the wonderful world of anion chemistry, and a tale of how advances in laser technologies, theoretical methods, and computational capabilities continuously enabled advances in our understanding. It is a story of the excitement and joy that come from the opportunity to add to the fabric of science, and to do so by working as a group of excited explorers with common goals. The participants in this journey include me, my students and postdoctoral associates, my collaborators, and our many generous colleagues. It all happened, in the words of the Beatles, “with a little help from my friends.” Actually, it was so much more than a little help!

  12. Structural evolution of small ruthenium cluster anions

    Energy Technology Data Exchange (ETDEWEB)

    Waldt, Eugen [Institut für Nanotechnologie, Karlsruher Institut für Technologie, Postfach 3640, 76021 Karlsruhe (Germany); Hehn, Anna-Sophia; Ahlrichs, Reinhart [Institute für Physikalische Chemie, Karlsruher Institut für Technologie, Kaiserstrasse 12, 76128 Karlsruhe (Germany); Kappes, Manfred M.; Schooss, Detlef, E-mail: detlef.schooss@kit.edu [Institut für Nanotechnologie, Karlsruher Institut für Technologie, Postfach 3640, 76021 Karlsruhe (Germany); Institute für Physikalische Chemie, Karlsruher Institut für Technologie, Kaiserstrasse 12, 76128 Karlsruhe (Germany)

    2015-01-14

    The structures of ruthenium cluster anions have been investigated using a combination of trapped ion electron diffraction and density functional theory computations in the size range from eight to twenty atoms. In this size range, three different structural motifs are found: Ru{sub 8}{sup −}–Ru{sub 12}{sup −} have simple cubic structures, Ru{sub 13}{sup −}–Ru{sub 16}{sup −} form double layered hexagonal structures, and larger clusters form close packed motifs. For Ru{sub 17}{sup −}, we find hexagonal close packed stacking, whereas octahedral structures occur for Ru{sub 18}{sup −}–Ru{sub 20}{sup −}. Our calculations also predict simple cubic structures for the smaller clusters Ru{sub 4}{sup −}–Ru{sub 7}{sup −}, which were not accessible to electron diffraction measurements.

  13. Adsorption of an anionic dispersant on lignite

    Energy Technology Data Exchange (ETDEWEB)

    Yavuz, R.; Kucukbayrak, S. [Istanbul Technical University, Istanbul (Turkey). Dept. of Chemical Engineering, Chemical & Metallurgical Engineering Faculty

    2001-12-01

    Since coal is not a homogeneous substance but a mixture of carbonaceous materials and mineral matter, it has a variety of surface properties. Therefore, it is not easy to control the properties of coal suspensions by simply adjusting variables, such as pH and/or electrolyte. A chemical agent needs to be added to control the properties of the coal suspensions. The adsorption behavior of an anionic dispersant in the presence of a wetting agent using some Turkish lignite samples was investigated. The effects of dispersant concentration, temperature and pH on the dispersant adsorption were studied systematically, and the experimental results are presented. Pellupur B69 as a dispersant, commercial mixture of formaldehyde condensate sodium salt of naphthalene sulphonic acid, and Texapon N{sub 2}5 as a wetting agent, a sodium lauryl ether sulfate, have been used.

  14. Structures and properties of anionic clay minerals

    International Nuclear Information System (INIS)

    Koch, Chr. Bender

    1998-01-01

    The Moessbauer spectra of pyroaurite-sjoegrenite-type compounds (PTC) (layered anion exchangers) are discussed with reference to the crystal structure, cation order, and crystallite morphology. It is shown that cation-ordered layers are produced in the synthesis of carbonate and sulphate types of green rust. In contrast, synthetic and natural pyroaurite only occurs as disordered types. The redox chemistry of Fe(III) within the metal hydroxide layer is illustrated with examples of electrochemical oxidation and reversible reduction by boiling glycerol. The chemistry of iron in the interlayer is exemplified by the intercalation of Fe-cyanide complexes in hydrotalcite. This reaction may be used as a probe for the charge distribution in the interlayer

  15. Anion permselective membrane. [For redox fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, S.S.; Hodgdon, R.B.

    1978-01-01

    Experimental anion permeselective membranes were improved and characterized for use as separators in a chemical redox, power storage cell being developed at the NASA Lewis Research Center. The goal of minimal Fe/sup +3/ ion transfer was achieved for each candidate membrane system. Minimal membrane resistivity was demonstrated by reduction of film thickness using synthetic backing materials but usefulness of thin membranes was limited by the scarcity of compatible fabrics. The most durable and useful backing fabrics were modacrylics. One membrane, a copolymer of 4 vinylpyridine and vinyl benzylchloride was outstanding in overall electrochemical and physical properties. Long term (1000 hrs) membrane chemical and thermal durability in redox environment was shown by three candidate polymers and two membranes. The remainder had good durability at ambient temperature. Manufacturing capability was demonstrated for large scale production of membrane sheets 5.5 ft/sup 2/ in area for two candidate systems.

  16. Anion vacancies in II-VI chalcogenides: Review and critical analysis

    Science.gov (United States)

    Babentsov, V.; James, R. B.

    2013-09-01

    We performed critical analysis and comparison of all EPR, photo-EPR, photosensitive optical absorption, photoluminescence, and photoconductivity data taken on various Zn- and Cd-related II-VI chalcogenides compounds, such as ZnO, ZnS, ZnSe, and ZnTe, and CdS, CdSe, and CdTe. We developed a scheme for the electronic transitions and recombination associated with anion vacancies that is common for all these materials. This scheme explains all known facts obtained to date on quenching and excitation of the EPR signal, optical absorption, photoluminescence and photoconductivity. Based on these data we determined that the location of the energy level of the singly charged anion vacancy, VA+, is nearly equal for Zn-related II-VI materials (EC-1.0 eV) and EC+0.8 eV for Cd-related materials. For Cd-related chalcogenides most of the data were derived only from photoluminescence- and photoconductivity-spectra, so based on the available data, the position of the energy level of a singly charged anion vacancy in these materials was determined not so convincingly. Nonetheless, these materials have attracted much interest for decades because of their industrial applications as luminescent devices, laser filters and other optical elements, infrared, visible- and (X) γ-ray-detectors, solar cells, and the like.

  17. Diffuse neutron scattering from anion-excess strontium chloride

    DEFF Research Database (Denmark)

    Goff, J.P.; Clausen, K.N.; Fåk, B.

    1992-01-01

    The defect structure and diffusional processes have been studied in the anion-excess fluorite (Sr, Y)Cl2.03 by diffuse neutron scattering techniques. Static cuboctahedral clusters found at ambient temperature break up at temperatures below 1050 K, where the anion disorder is highly dynamic. The a...

  18. Anion gap in hyperproteinaemia: With reference to tuberculosis ...

    African Journals Online (AJOL)

    Objectives: (1)To determine the level of electrolyte in TB patients (2) To see if these are significantly different from those of control-match for age and sex (3) To calculate the anion gap levels in TB patient and (4) to see if the anion gap levels could be used in the management of patient with tuberculosis. Patient and Methods: ...

  19. based anion exchange membrane for alkaline polymer electrolyte

    Indian Academy of Sciences (India)

    Administrator

    Alkaline polymer electrolyte fuel cell; anion exchange membrane; PPO; homogeneous quaterni- zation. 1. Introduction. Presently, alkaline polymer electrolyte fuel cells (APEFCs) using anion exchange membranes have received an immense interest among researchers (Varcoe and Slade. 2005). The advantages of ...

  20. Anion binding by biotin[6]uril in water

    DEFF Research Database (Denmark)

    Lisbjerg, Micke; Nielsen, Bjarne Enrico; Milhøj, Birgitte Olai

    2015-01-01

    In this contribution we show that the newly discovered 6 + 6 biotin-formaldehyde macrocycle Biotin[6]uril binds a variety of anionic guest molecules in water. We discuss how and why the anions are bound based on data obtained using NMR spectroscopy, mass spectrometry, isothermal titration...

  1. Protonation Reaction of Benzonitrile Radical Anion and Absorption of Product

    DEFF Research Database (Denmark)

    Holcman, Jerzy; Sehested, Knud

    1975-01-01

    The rate constant for the protonation of benzonitrile radical anions formed in pulse radiolysis of aqueous benzonitrile solutions is (3.5 ± 0.5)× 1010 dm3 mol–1 s–1. A new 270 nm absorption band is attributed to the protonated benzonitrile anion. The pK of the protonation reaction is determined t...

  2. Decreased anion gap associated with monoclonal and pseudomonoclonal gammopathy.

    Science.gov (United States)

    Frohlich, J.; Adam, W.; Golbey, M. J.; Bernstein, M.

    1976-01-01

    Nine patients with monoclonal and one with pseudomonoclonal gammopathy were found to have a decreased anion gap. Eight of the patients had multiple myeloma, one has plasma cell leukemia and one had chronic active hepatitis. In all of the the decreased anion gap was associated with an increased concentration of IgG greater than 5 g/dl. PMID:1032353

  3. Methamphetamine and amphetamine isomer concentrations in human urine following controlled Vicks VapoInhaler administration.

    Science.gov (United States)

    Smith, Michael L; Nichols, Daniel C; Underwood, Paula; Fuller, Zachary; Moser, Matthew A; Flegel, Ron; Gorelick, David A; Newmeyer, Matthew N; Concheiro, Marta; Huestis, Marilyn A

    2014-10-01

    Legitimate use of legal intranasal decongestants containing l-methamphetamine may complicate interpretation of urine drug tests positive for amphetamines. Our study hypotheses were that commonly used immunoassays would produce no false-positive results and a recently developed enantiomer-specific gas chromatography-mass spectrometry (GC-MS) procedure would find no d-amphetamine or d-methamphetamine in urine following controlled Vicks VapoInhaler administration at manufacturer's recommended doses. To evaluate these hypotheses, 22 healthy adults were each administered one dose (two inhalations in each nostril) of a Vicks VapoInhaler every 2 h for 10 h on Day 1 (six doses), followed by a single dose on Day 2. Every urine specimen was collected as an individual void for 32 h after the first dose and assayed for d- and l-amphetamines specific isomers with a GC-MS method with >99% purity of R-(-)-α-methoxy-α-(trifluoromethyl)phenylacetyl derivatives and 10 µg/L lower limits of quantification. No d-methamphetamine or d-amphetamine was detected in any urine specimen by GC-MS. The median l-methamphetamine maximum concentration was 62.8 µg/L (range: 11.0-1,440). Only two subjects had detectable l-amphetamine, with maximum concentrations coinciding with l-methamphetamine peak levels, and always ≤ 4% of the parent's maximum. Three commercial immunoassays for amphetamines EMIT(®) II Plus, KIMS(®) II and DRI(®) had sensitivities, specificities and efficiencies of 100, 97.8, 97.8; 100, 99.6, 99.6 and 100, 100, 100%, respectively. The immunoassays had high efficiencies, but our first hypothesis was not affirmed. The EMIT(®) II Plus assay produced 2.2% false-positive results, requiring an enantiomer-specific confirmation. Published by Oxford University Press 2014. This work is written by (a) US Government employee(s) and is in the public domain in the US.

  4. Extraction of monoclonal antibodies (IgG1) using anionic and anionic/nonionic reverse micelles.

    Science.gov (United States)

    George, Daliya A; Stuckey, David C

    2010-01-01

    Purification schemes for antibody production based on affinity chromatography are trying to keep pace with increases in cell culture expression levels and many current research initiatives are focused on finding alternatives to chromatography for the purification of Monoclonal antibodies (MAbs). In this article, we have investigated an alternative separation technique based on liquid-liquid extraction called the reverse micellar extraction. We extracted MAb (IgG1) using reverse micelles of an anionic surfactant, sodium bis 2-ethyl-hexyl sulfosuccinate (AOT) and a combination of anionic (AOT) and nonionic surfactants (Brij-30, Tween-85, Span-85) using isooctane as the solvent system. The extraction efficiency of IgG1 was studied by varying parameters, such as pH of the aqueous phase, cation concentration, and type and surfactant concentration. Using the AOT/Isooctane reverse micellar system, we could achieve good overall extraction of IgG1 (between 80 and 90%), but only 30% of the bioactivity of IgG1 could be recovered at the end of the extraction by using its binding to affinity chromatography columns as a surrogate measure of activity. As anionic surfactants were suspected as being one of the reasons for the reduced activity, we decided to combine a nonionic surfactant with an anionic surfactant and then study its effect on the extraction efficiency and bioactivity. The best results were obtained using an AOT/Brij-30/Isooctane reverse micellar system, which gave an overall extraction above 90 and 59% overall activity recovery. An AOT/Tween-85/Isooctane reverse micellar system gave an overall extraction of between 75 and 80% and overall activity recovery of around 40-45%. The results showed that the activity recovery of IgG1 can be significantly enhanced using different surfactant combination systems, and if the recovery of IgG1 can be further enhanced, the technique shows considerable promise for the downstream purification of MAbs. © 2010 American Institute of

  5. Anionic magnetite nanoparticle conjugated with pyrrolidinyl peptide nucleic acid for DNA base discrimination

    Energy Technology Data Exchange (ETDEWEB)

    Khadsai, Sudarat; Rutnakornpituk, Boonjira [Naresuan University, Department of Chemistry and Center of Excellence in Biomaterials, Faculty of Science (Thailand); Vilaivan, Tirayut [Chulalongkorn University, Department of Chemistry, Organic Synthesis Research Unit, Faculty of Science (Thailand); Nakkuntod, Maliwan [Naresuan University, Department of Biology, Faculty of Science (Thailand); Rutnakornpituk, Metha, E-mail: methar@nu.ac.th [Naresuan University, Department of Chemistry and Center of Excellence in Biomaterials, Faculty of Science (Thailand)

    2016-09-15

    Magnetite nanoparticles (MNPs) were surface modified with anionic poly(N-acryloyl glycine) (PNAG) and streptavidin for specific interaction with biotin-conjugated pyrrolidinyl peptide nucleic acid (PNA). Hydrodynamic size (D{sub h}) of PNAG-grafted MNPs varied from 334 to 496 nm depending on the loading ratio of the MNP to NAG in the reaction. UV–visible and fluorescence spectrophotometries were used to confirm the successful immobilization of streptavidin and PNA on the MNPs. About 291 pmol of the PNA/mg MNP was immobilized on the particle surface. The PNA-functionalized MNPs were effectively used as solid supports to differentiate between fully complementary and non-complementary/single-base mismatch DNA using the PNA probe. These novel anionic MNPs can be efficiently applicable for use as a magnetically guidable support for DNA base discrimination.Graphical Abstract.

  6. Anionic magnetite nanoparticle conjugated with pyrrolidinyl peptide nucleic acid for DNA base discrimination

    Science.gov (United States)

    Khadsai, Sudarat; Rutnakornpituk, Boonjira; Vilaivan, Tirayut; Nakkuntod, Maliwan; Rutnakornpituk, Metha

    2016-09-01

    Magnetite nanoparticles (MNPs) were surface modified with anionic poly( N-acryloyl glycine) (PNAG) and streptavidin for specific interaction with biotin-conjugated pyrrolidinyl peptide nucleic acid (PNA). Hydrodynamic size ( D h) of PNAG-grafted MNPs varied from 334 to 496 nm depending on the loading ratio of the MNP to NAG in the reaction. UV-visible and fluorescence spectrophotometries were used to confirm the successful immobilization of streptavidin and PNA on the MNPs. About 291 pmol of the PNA/mg MNP was immobilized on the particle surface. The PNA-functionalized MNPs were effectively used as solid supports to differentiate between fully complementary and non-complementary/single-base mismatch DNA using the PNA probe. These novel anionic MNPs can be efficiently applicable for use as a magnetically guidable support for DNA base discrimination.

  7. Substituent Effects in CH Hydrogen Bond Interactions: Linear Free Energy Relationships and Influence of Anions.

    Science.gov (United States)

    Tresca, Blakely W; Hansen, Ryan J; Chau, Calvin V; Hay, Benjamin P; Zakharov, Lev N; Haley, Michael M; Johnson, Darren W

    2015-12-02

    Aryl CH hydrogen bonds (HBs) are now commonly recognized as important factors in a number of fields, including molecular biology, stereoselective catalysis, and anion supramolecular chemistry. As the utility of CH HBs has grown, so to has the need to understand the structure-activity relationship for tuning both their strength and selectivity. Although there has been significant computational effort in this area, an experimental study of the substituent effects on CH HBs has not been previously undertaken. Herein we disclose a systematic study of a single CH HB by using traditional urea donors as directing groups in a supramolecular binding cavity. Experimentally determined association constants are examined by a combination of computational (electrostatic potential) and empirical (σm and σp) values for substituent effects. The dominance of electrostatic parameters, as observed in a computational DFT study, is consistent with current CH HB theory; however, a novel anion dependence of the substituent effects is revealed in solution.

  8. Anionic magnetite nanoparticle conjugated with pyrrolidinyl peptide nucleic acid for DNA base discrimination

    International Nuclear Information System (INIS)

    Khadsai, Sudarat; Rutnakornpituk, Boonjira; Vilaivan, Tirayut; Nakkuntod, Maliwan; Rutnakornpituk, Metha

    2016-01-01

    Magnetite nanoparticles (MNPs) were surface modified with anionic poly(N-acryloyl glycine) (PNAG) and streptavidin for specific interaction with biotin-conjugated pyrrolidinyl peptide nucleic acid (PNA). Hydrodynamic size (D h ) of PNAG-grafted MNPs varied from 334 to 496 nm depending on the loading ratio of the MNP to NAG in the reaction. UV–visible and fluorescence spectrophotometries were used to confirm the successful immobilization of streptavidin and PNA on the MNPs. About 291 pmol of the PNA/mg MNP was immobilized on the particle surface. The PNA-functionalized MNPs were effectively used as solid supports to differentiate between fully complementary and non-complementary/single-base mismatch DNA using the PNA probe. These novel anionic MNPs can be efficiently applicable for use as a magnetically guidable support for DNA base discrimination.Graphical Abstract

  9. Coumarin amide derivatives as fluorescence chemosensors for cyanide anions

    International Nuclear Information System (INIS)

    Wu, Qianqian; Liu, Zhiqiang; Cao, Duxia; Guan, Ruifang; Wang, Kangnan; Shan, Yanyan; Xu, Yongxiao; Ma, Lin

    2015-01-01

    Four coumarin amide derivatives with 4-methyl coumarin or pyrene as terminal group have been synthesized. Their photophysical properties and recognition properties for cyanide anions have been examined. The results indicate that the compounds can recognize cyanide anions with obvious absorption and fluorescence spectra change, at the same time, obvious color and fluorescence change can be observed by naked eye. The in situ hydrogen nuclear magnetic resonance spectra and photophysical properties change confirm that Michael additions between the chemosensors and cyanide anions take place at the 4-position of coumarin. - Highlights: • Four coumarin amide derivatives with 4-methyl coumarin or pyrene as terminal group were synthesized. • The compounds can recognize cyanide anions with obvious absorption and fluorescence spectra change. • Michael additions between the chemosensors and cyanide anions take place at the 4-position of coumarin

  10. Toward Molecular Magnets of Organic Origin via Anion-π Interaction Involving m-Aminyl Diradical: A Theoretical Study

    DEFF Research Database (Denmark)

    Bhattacharya, Debojit; Shil, Suranjan; Misra, Anirban

    2016-01-01

    Here we study a set of novel magnetic organic molecular species with different halide ions (fluoride, chloride, bromide) absorbed ∼2 Å above or below the center of an aromatic π-ring in an m-aminyl diradical. Focus is on the nature of anion-π interaction and its impact on magnetic properties......, specifically on magnetic anisotropy and on intramolecular magnetic exchange coupling. In the development of single molecule magnets, magnetic anisotropy is considered to be the most influential factor. A new insight regarding the magnetic anisotropy that determines the barrier height for relaxation...... of magnetization of m-aminyl diradical-derived anionic complexes is obtained from calculations of the axial zero-field-splitting (ZFS) parameter D. The noncovalent anion-π interaction strongly influences magnetic anisotropy in m-aminyl-halide diradical complexes. In particular, the change of D values from positive...

  11. Structure of two-, four-, and six-quasiparticle isomers in 174Yb and K-forbidden decays

    Science.gov (United States)

    Dracoulis, G. D.; Lane, G. J.; Kondev, F. G.; Byrne, A. P.; Kibédi, T.; Watanabe, H.; Ahmad, I.; Carpenter, M. P.; Freeman, S. J.; Janssens, R. V.; Hammond, N. J.; Lauritsen, T.; Lister, C. J.; Mukherjee, G.; Seweryniak, D.; Chowdhury, P.; Tandel, S. K.

    2005-04-01

    The stable nucleus 174Yb has been studied using deep-inelastic reactions and time-correlated γ-ray spectroscopy. New intrinsic states assigned include a 370-ns isomer at 1765 keV, which we associate with a predicted Kπ=7- two-quasineutron configuration. Analysis of the alignment and in-band properties of its rotational band, identified using time-correlated coincidences, allows characterization of the configuration. The properties of a newly identified rotational band built on the known 830-μs isomer at 1518 keV support the 6+, 2-quasineutron configuration assignment proposed previously. The 6+ band is fed by a four-quasiparticle, Kπ=14+ isomer at 3699 keV and several higher multiquasiparticle states, including a six-quasiparticle isomer at 6147 keV with K=(22,23). The results are discussed in terms of the states predicted on the basis of multiquasiparticle calculations. The anomalously fast K-forbidden transition strengths from the 14+ isomer are attributed to either K mixing in the neutron configuration or to random mixing in the high-level-density region. The 7- isomer decays are not abnormal, whereas the very hindered E2 transition from the 6+ isomer to the ground-state band remains unexplained.

  12. Fixed-bed adsorption separation of xylene isomers over sio2/silicallite-1 core-shell adsorbents

    KAUST Repository

    Khan, Easir A.

    2013-12-29

    SiO2/Silicalite-1 core-shell material has been demonstrated as potential shape selective adsorbent in gas phase separation of p-xylene from a mixture of p/o-xylene isomers. The core-shell composite comprised of large silica core and thin polycrystalline silicalite-1 shell which was synthesized via a self-assembly of silicalite-1 nanocrystals on core silica surface followed by a secondary seeded growth method. The core materials, SiO2 used in this study has mesoporosity with an average pore diameter of 60Å and hence offers no shape selectivity for xylene isomers. However, the shell, silicalite-1 contains rigid pore structures and preferentially adsorbs p-xylene from their isomers mixtures. A series of adsorption fixed bed breakthrough adsorption/desorption experiment was performed to obtain the equilibrium isotherms and adsorption isotherm parameters of xylene isomers. The equilibrium isotherms of xylene isomers follow the Langmuir\\'s model. A chromatographic adsorption model has been used to describe the fixed-bed breakthrough profiles of xylene isomers. The model has successfully predicted the responses of the binary mixtures of p/o-xylene isomers. The SiO2/silicalite-1 core-shell adsorbents have shown para-selectivity as high as 15. © Bangladesh Uni. of Engg. & Tech.

  13. Second sphere coordination in anion binding: Synthesis, characterization of [Co(phen) 2CO 3]X· nH 2O where X = o-nitrophenolate(onp), p-nitrophenolate(pnp), 2,4-dinitrophenolate(dnp), 2,4,6-trinitrophenolate(tnp) and single crystal X-ray structures of [Co(phen) 2CO 3](onp)·2H 2O and [Co(phen) 2CO 3](dnp)·4.5H 2O

    Science.gov (United States)

    Singh, Ajnesh; Sharma, Raj Pal; Brandão, Paula; Félix, Vitor; Venugopalan, Paloth

    2008-12-01

    In an effort to utilize [Co(phen) 2CO 3] + cation as a new host for mono-, di- and tri-substituted nitrophenolate anions, red coloured crystals of composition [Co(phen) 2CO 3](onp)·2H 2O, [Co(phen) 2CO 3](pnp), orange coloured precipitated product of [Co(phen) 2CO 3](dnp)·4.5H 2O (which gave red coloured crystals from acetone-water mixture) and orange-yellow coloured precipitated product of [Co(phen) 2CO 3](tnp) were obtained in good yields by reacting sodium salts of o-nitrophenol, p-nitrophenol 2,4-dinitrophenol and 2,4,6-trinitrophenol with [Co(phen) 2CO 3]Cl·5H 2O, respectively in 1:1 molar ratio in aqueous medium. These cobalt(III) complex salts have been characterized by elemental analyses, spectroscopic techniques (UV/Visible, IR and NMR) and conductance measurements. Single crystal X-ray structure determination of [Co(phen) 2CO 3](onp)·2H 2O and [Co(phen) 2CO 3](dnp)·4.5H 2O revealed the presence of discrete ions and lattice water molecules in the solid state. A strong network of hydrogen bond interactions through the weak second sphere coordination (C sbnd H…O (phenolate), C sbnd H…O (nitro), and strong interactions of type O sbnd H…O (water) besides the electrostatic interactions play a very important role in stabilizing the crystal lattice. The studies indicated that complex cation, [Co(phen) 2CO 3] + may preferentially bind nitrophenolate ions in the aqueous medium.

  14. External anion effect on the synthesis of new MOFs based on formate and a twisted divergent ligands

    Energy Technology Data Exchange (ETDEWEB)

    Lago, Ana Belén, E-mail: ablago@uvigo.es [Departamento de Química Inorgánica/Facultade de Química, Instituto de Investigación Biomédica (IBI), Universidade de Vigo, E-36310 Vigo, Galicia (Spain); Carballo, Rosa [Departamento de Química Inorgánica/Facultade de Química, Instituto de Investigación Biomédica (IBI), Universidade de Vigo, E-36310 Vigo, Galicia (Spain); Lezama, Luis [BCMaterials & Departamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Apartado 644, 48080 Bilbao (Spain); Vázquez-López, Ezequiel M. [Departamento de Química Inorgánica/Facultade de Química, Instituto de Investigación Biomédica (IBI), Universidade de Vigo, E-36310 Vigo, Galicia (Spain)

    2015-11-15

    New copper(II) metal–organic compounds with the formulae [Cu{sub 3}Cl(HCO{sub 2}){sub 5}(SCS){sub 3}(H{sub 2}O){sub 2}]·8H{sub 2}O·EtOH (1) and [Cu{sub 3}(HCO{sub 2}){sub 4}(SCS){sub 4}(H{sub 2}O){sub 2}](NO{sub 3}){sub 2}·9H{sub 2}O (2) (SCS=bis(4-pyridylthio)methane) have been synthesized after a careful study of the reaction of the SCS ligand with copper(II) formate. The compounds were obtained in the presence of sodium chloride and nitrate salts under microwave irradiation. The influence of the anion at different metal/anion ratios on the final architecture has been studied. The new chloride-MOF 1 has been characterized by electron paramagnetic resonance (EPR), magnetic properties and single crystal X-ray diffraction studies. The thermal stability and topological analysis have also been investigated. - Highlights: • Microwave synthesis of coordination polymers. • Anion-derived structural changes. • Influence of anions at different metal/anion ratios on the final architectures. • EPR and magnetic characterization of a MOF compound.

  15. Structural Characterization of de Novo Designed L5K5W Model Peptide Isomers with Potent Antimicrobial and Varied Hemolytic Activities

    Directory of Open Access Journals (Sweden)

    Sung-Jean Park

    2013-01-01

    Full Text Available In an effort to develop short antimicrobial peptides with simple amino acid compositions, we generated a series of undecapeptide isomers having the L5K5W formula. Amino acid sequences were designed to be perfectly amphipathic when folded into a helical conformation by converging leucines onto one side and lysines onto the other side of the helical axis. The single tryptophans, whose positions were varied in the primary structures, were located commonly at the critical amphipathic interface in the helical wheel projection. Helical conformations and the tryptophanyl environments of the 11 L5K5W peptides were confirmed and characterized by circular dichroism, fluorescence and nuclear magnetic resonance spectroscopy. All of the isomers exhibited a potent, broad-spectrum of antibacterial activity with just a slight variance in individual potency, whereas their hemolytic activities against human erythrocytes were significantly diversified. Interestingly, helical dispositions and fluorescence blue shifts of the peptides in aqueous trifluoroethanol solutions, rather than in detergent micelles, showed a marked linear correlation with their hemolytic potency. These results demonstrate that our de novo design strategy for amphipathic helical model peptides is effective for developing novel antimicrobial peptides and their hemolytic activities can be estimated in correlation with structural parameters.

  16. Structural characterization of de novo designed L5K5W model peptide isomers with potent antimicrobial and varied hemolytic activities.

    Science.gov (United States)

    Kim, Seo-Jin; Kim, Jae-Seok; Lee, Yoo-Sup; Sim, Dae-Won; Lee, Sung-Hee; Bahk, Young-Yil; Lee, Kwang-Ho; Kim, Eun-Hee; Park, Sung-Jean; Lee, Bong-Jin; Won, Hyung-Sik

    2013-01-11

    In an effort to develop short antimicrobial peptides with simple amino acid compositions, we generated a series of undecapeptide isomers having the L(5)K(5)W formula. Amino acid sequences were designed to be perfectly amphipathic when folded into a helical conformation by converging leucines onto one side and lysines onto the other side of the helical axis. The single tryptophans, whose positions were varied in the primary structures, were located commonly at the critical amphipathic interface in the helical wheel projection. Helical conformations and the tryptophanyl environments of the 11 L(5)K(5)W peptides were confirmed and characterized by circular dichroism, fluorescence and nuclear magnetic resonance spectroscopy. All of the isomers exhibited a potent, broad-spectrum of antibacterial activity with just a slight variance in individual potency, whereas their hemolytic activities against human erythrocytes were significantly diversified. Interestingly, helical dispositions and fluorescence blue shifts of the peptides in aqueous trifluoroethanol solutions, rather than in detergent micelles, showed a marked linear correlation with their hemolytic potency. These results demonstrate that our de novo design strategy for amphipathic helical model peptides is effective for developing novel antimicrobial peptides and their hemolytic activities can be estimated in correlation with structural parameters.

  17. Isomer spectroscopy of neutron-rich 168 Tb 103

    Energy Technology Data Exchange (ETDEWEB)

    Gurgi, L. A.; Regan, P. H.; Söderström, P. -A.; Watanabe, H.; Walker, P. M.; Podolyák, Zs.; Nishimura, S.; Berry, T. A.; Doornenbal, P.; Lorusso, G.; Isobe, T.; Baba, H.; Xu, Z. Y.; Sakurai, H.; Sumikama, T.; Catford, W. N.; Bruce, A. M.; Browne, F.; Lane, G. J.; Kondev, F. G.; Odahara, A.; Wu, J.; Liu, H. L.; Xu, F. R.; Korkulu, Z.; Lee, P.; Liu, J. J.; Phong, V. H.; Yag, A.; Zhang, G. X.; Alharbi, T.; Carroll, R. J.; Chae, K. Y.; Dombradi, Zs.; Estrade, A.; Fukuda, N.; Griffin, C.; Ideguchi, E.; Inabe, N.; Kanaoka, H.; Kojouharov, I.; Kubo, T.; Kubono, S.; Kurz, N.; Kuti, I.; Lalkovski, S.; Lee, E. J.; Lee, C. S.; Lotay, G.; Moon, C. -B.; Nishizuka, I.; Nita, C. R.; Patel, Z.; Roberts, O. J.; Schaffner, H.; Shand, C. M.; Suzuki, H.; Takeda, H.; Terashima, S.; Vajta, Zs.; Yoshida, S.; Valiente-Dòbon, J. J.

    2017-11-01

    In-flight fission of a 345 MeV per nucleon 238U primary beam on a 2 mm thick 9Be target has been used to produce and study the decays of a range of neutron-rich nuclei centred around the doubly mid-shell nucleus 170Dy at the RIBF Facility, RIKEN, Japan. The produced secondary fragments of interest were identified event-by-event using the BigRIPS separator. The fragments were implanted into the WAS3ABI position sensitive silicon active stopper which allowed pixelated correlations between implants and their subsequent β-decay. Discrete γ-ray transitions emitted following decays from either metastable states or excited states populated following beta decay were identified using the 84 coaxial high-purity germanium (HPGe) detectors of the EURICA spectrometer, which was complemented by 18 additional cerium-doped lanthanum bromide (LaBr3) fast-timing scintillation detectors from the FATIMA collaboration. This paper presents the internal decay of a metastable isomeric excited state in the odd-odd nucleus 168Tb, which corresponds to a single proton-neutron hole configuration in the valence maximum nucleus 170Dy. These data represent the first information on excited states in this nucleus, which is the most neutron-rich odd-odd isotope of terbium (Z=65) studied to date. Nilsson configurations associated with an axially symmetric, prolate-deformed nucleus are proposed for the 168Tb ground state the observed isomeric state by comparison with Blocked BCS-Nilsson calculations.

  18. Isomer spectroscopy of neutron-rich 168Tb103

    Science.gov (United States)

    Gurgi, L. A.; Regan, P. H.; Söderström, P.-A.; Watanabe, H.; Walker, P. M.; Podolyák, Zs.; Nishimura, S.; Berry, T. A.; Doornenbal, P.; Lorusso, G.; Isobe, T.; Baba, H.; Xu, Z. Y.; Sakurai, H.; Sumikama, T.; Catford, W. N.; Bruce, A. M.; Browne, F.; Lane, G. J.; Kondev, F. G.; Odahara, A.; Wu, J.; Liu, H. L.; Xu, F. R.; Korkulu, Z.; Lee, P.; Liu, J. J.; Phong, V. H.; Yag, A.; Zhang, G. X.; Alharbi, T.; Carroll, R. J.; Chae, K. Y.; Dombradi, Zs.; Estrade, A.; Fukuda, N.; Griffin, C.; Ideguchi, E.; Inabe, N.; Kanaoka, H.; Kojouharov, I.; Kubo, T.; Kubono, S.; Kurz, N.; Kuti, I.; Lalkovski, S.; Lee, E. J.; Lee, C. S.; Lotay, G.; Moon, C.-B.; Nishizuka, I.; Nita, C. R.; Patel, Z.; Roberts, O. J.; Schaffner, H.; Shand, C. M.; Suzuki, H.; Takeda, H.; Terashima, S.; Vajta, Zs.; Yoshida, S.; Valiente-Dòbon, J. J.

    2017-11-01

    In-flight fission of a 345 MeV per nucleon 238U primary beam on a 2 mm thick 9Be target has been used to produce and study the decays of a range of neutron-rich nuclei centred around the doubly mid-shell nucleus 170Dy at the RIBF Facility, RIKEN, Japan. The produced secondary fragments of interest were identified event-by-event using the BigRIPS separator. The fragments were implanted into the WAS3ABI position sensitive silicon active stopper which allowed pixelated correlations between implants and their subsequent β-decay. Discrete γ-ray transitions emitted following decays from either metastable states or excited states populated following beta decay were identified using the 84 coaxial high-purity germanium (HPGe) detectors of the EURICA spectrometer, which was complemented by 18 additional cerium-doped lanthanum bromide (LaBr3) fast-timing scintillation detectors from the FATIMA collaboration. This paper presents the internal decay of a metastable isomeric excited state in the odd-odd nucleus 168Tb, which corresponds to a single proton-neutron hole configuration in the valence maximum nucleus 170Dy. These data represent the first information on excited states in this nucleus, which is the most neutron-rich odd-odd isotope of terbium (Z=65) studied to date. Nilsson configurations associated with an axially symmetric, prolate-deformed nucleus are proposed for the 168Tb ground state the observed isomeric state by comparison with Blocked BCS-Nilsson calculations.

  19. Gallium based low-interaction anions

    Science.gov (United States)

    King, Wayne A.; Kubas, Gregory J.

    2000-01-01

    The present invention provides: a composition of the formula M.sup.+x (Ga(Y).sub.4.sup.-).sub.x where M is a metal selected from the group consisting of lithium, sodium, potassium, cesium, calcium, strontium, thallium, and silver, x is an integer selected from the group consisting of 1 or 2, each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide; a composition of the formula (R).sub.x Q.sup.+ Ga(Y).sub.4.sup.- where Q is selected from the group consisting of carbon, nitrogen, sulfur, phosphorus and oxygen, each R is a ligand selected from the group consisting of alkyl, aryl, and hydrogen, x is an integer selected from the group consisting of 3 and 4 depending upon Q, and each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide; an ionic polymerization catalyst composition including an active cationic portion and a gallium based weakly coordinating anion; and bridged anion species of the formula M.sup.+x.sub.y [X(Ga(Y.sub.3).sub.z ].sup.-y.sub.x where M is a metal selected from the group consisting of lithium, sodium, potassium, magnesium, cesium, calcium, strontium, thallium, and silver, x is an integer selected from the group consisting of 1 or 2, X is a bridging group between two gallium atoms, y is an integer selected from the group consisting 1 and 2, z is an integer of at least 2, each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide.

  20. Resolution of the 179W isomer anomaly: exposure of a fermi aligned s-band

    International Nuclear Information System (INIS)

    Walker, P.M.; Surrey Univ., Guildford; Dracoulis, G.D.; Byrne, A.P.; Fabricius, B.; Kibedi, T.; Stuchbery, A.E.

    1991-06-01

    The K Π = 35/2 - , five quasiparticle isomer in 179 W is shown to decay into the region of a backbend in the 7/2 - [514] band, allowing for the first time the identification of a full set of aligned-band states. Destructive interference results from level-mixing in the band-crossing region. The deduced γ-ray branching ratios are used to establish the mixing matrix elements and to show that the aligned band has a high value of the K-quantum number. The properties of well-defined alignment and yet also high-K, provided the first clear example of a Fermi Aligned s-band. The anomalous decay of the isomer itself is now explained. 11 refs., 1 tab., 3 figs

  1. Supramolecular isomers, water clusters and solvent-mediated transformations in a series of lanthanide MOFs

    Science.gov (United States)

    Michaelides, Adonis; Skoulika, Stavroula

    2017-09-01

    A series of Lanthanide MOFs of hydromuconic acid (H2hymuc) with cations of different size (La3+, Ce3+, Gd3+, Y3+) were generated at room temperature, pH = 5.5-5.8, using water as solvent. Two microporous genuine supramolecular isomers were found for the larger cations (La3+, Ce3+) sustained either by discrete (H2O)18 clusters or by infinite water tapes, consisting of fused tetramers, pentamers and hexamers. The smaller cations (Gd3+, Y3+) produced a 2D phase, considered as catenane isomer of previously published lanthanide MOFs with adipic acid. MOFs obtained with Ce3+, Gd3+and Y3+ undergo irreversible solvent-mediated transformation, yielding isomorphous 3D two-fold interpenetrated MOFs. The close structural similarity between the 2D phase and the 3D interpenetrated one indicated a possible mechanism for this transformation.

  2. Interactions between major chlorogenic acid isomers and chemical changes in coffee brew that affect antioxidant activities.

    Science.gov (United States)

    Liang, Ningjian; Xue, Wei; Kennepohl, Pierre; Kitts, David D

    2016-12-15

    Coffee bean source and roasting conditions significantly (p<0.05) affected the content of chlorogenic acid (CGA) isomers, several indices of browning and subsequent antioxidant values. Principal component analysis was used to interpret the correlations between physiochemical and antioxidant parameters of coffee. CGA isomer content was positively correlated (p<0.001) to capacity of coffee to reduce nitric oxide and scavenge Frémy's salt. Indices of browning in roasted coffee were positively correlated (p<0.001) to ABTS and TEMPO radical scavenging capacity, respectively. Only the CGA content of coffee corresponded to intracellular antioxidant capacity measured in Caco-2 intestinal cells. This study concluded that the intracellular antioxidant capacity that best describes potential health benefits of coffee positively corresponds best with CGA content. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

  3. Effect of food processing on degradation of hexachlorocyclohexane and its isomers in milk.

    Science.gov (United States)

    Singh, Sujatha; Nelapati, Krishnaiah

    2017-03-01

    To study the effect of different food processing techniques on the degradation of organochlorine compounds (α, β, ɣ and δ hexachlorocyclohexane isomers (HCH)) residues in both natural and fortified samples of milk. Raw milk samples are collected from the local areas of Hyderabad, India. Naturally and fortified milk samples (HCH) were subjected to various food processing techniques, pasteurization (63ºC for ½ h), sterilization (121ºC for 15 min) and boiling for 5 min and analyzed by gas chromatography with electron capture detector using quick, easy, cheap, effective, rugged and safe method for multiresidue analysis of pesticides in milk with slight modification. The final mean residual concentration of pesticide in milk after heat processing and percentage of degradation were calculated with respective treatments. Heat treatments are highly effective on reduction of mean residual concentration of HCH in milk. In which Sterilization and boiling proved to be more effective in degradation of HCH isomers.

  4. Resolution of the 179W-isomer anomaly: Exposure of a Fermi-aligned s band

    International Nuclear Information System (INIS)

    Walker, P.M.; Dracoulis, G.D.; Byrne, A.P.; Fabricius, B.; Kibedi, T.; Stuchbery, A.E.; Department of Physics, University of Surrey, Guildford, GU2 5XH United Kingdom)

    1991-01-01

    The K π =35/2 - , five-quasiparticle isomer in 179 W is shown to decay into the region of a backbend in the 7/2 - [514] band, allowing for the first time the identification of a full set of aligned-band states. Destructive interference results from level mixing in the band-crossing region. The deduced γ-ray branching ratios are used to establish the mixing matrix elements and to show that the aligned band has a high value of the K quantum number. The properties of well-defined alignment and yet also high K provide the first clear example of a Fermi-aligned s band. The anomalous decay of the isomer itself is now explained

  5. Energy of the 4(+) isomer and new bands in the odd-odd nucleus 74Br

    International Nuclear Information System (INIS)

    Doering, J.; Holcomb, J.W.; Johnson, T.D.; Riley, M.A.; Tabor, S.L.; Womble, P.C.; Winter, G.

    1993-01-01

    High-spin states of the odd-odd nucleus 74 Br were investigated via the reactions 58 Ni ( 19 F,2pn) 74 Br and 65 Cu( 12 C,3n) 74 Br at beam energies of 62 and 50 MeV, respectively. On the basis of coincidence data new levels have been introduced and partly grouped into rotational bands. Some of these new states decay to known levels of negative-parity bands built on both the ground state and the long-lived 4 (+) isomer. Thus, an excitation energy of 13.8 keV has been deduced for the long-lived isomer in 74 Br. The level sequences observed are interpreted in terms of Nilsson configurations in conjunction with collective excitations

  6. Early anion gap metabolic acidosis in acetaminophen overdose.

    Science.gov (United States)

    Zein, Joe G; Wallace, David J; Kinasewitz, Gary; Toubia, Nagib; Kakoulas, Christine

    2010-09-01

    The study aimed to determine the incidence and clinical significance of early high (>15 mEq/L) anion gap metabolic acidosis in acetaminophen (APAP) overdose. A retrospective review of a cohort of 74 patients presenting within 24 hours of APAP overdose was conducted. Early high anion gap metabolic acidosis was present in 41% of patients on admission and persisted for 1.5 ± 0.1 days. The anion gap was associated with an elevated lactate level (4.5 ± 1 mmol/L) (r(2) = 0.66, P anion gap had a higher incidence of confusion (48% vs 3%; P anion gap metabolic acidosis was found in the absence of shock or liver failure. All patients were treated with N-acetylcysteine and, despite the early high anion gap metabolic acidosis, none developed hepatic failure or hypoglycemia. Early high anion gap metabolic acidosis in patients with APAP overdose is self-limited and does not predict clinical or laboratory outcomes. Persistent or late metabolic acidosis in the absence of liver failure is not likely due to APAP and should prompt a search for other causes of metabolic acidosis. Finally, APAP overdose should be considered in patients presenting to the emergency department with altered mental status, as this is a treatable condition when detected early. Copyright © 2010 Elsevier Inc. All rights reserved.

  7. A comparative study of the metal binding behavior of alanine based bis-thiourea isomers

    OpenAIRE

    Fakhar, Imran; Yamin, Bohari M.; Hasbullah, Siti Aishah

    2017-01-01

    Two new symmetrical bis-thiourea, 2,2?-[{(terephthaloylbis(azanediyl)bis(carbonothioyl) bis(azanediyl)}dipropanoic acid] (1A) and 3,3?-[{(terephthaloylbis(azanediyl)bis (carbonothioyl)bis(azanediyl)} dipropanoic acid] (1B) were synthesized by the reaction of terephthaloyl chloride with ?- and ?-alanine in good yields. Their binding properties were investigated with various metal cations using UV?Vis titration experiments. Both isomers exhibited effective binding with Ag+, Cu2+, Hg2+, Pb2+, Fe...

  8. Investigation of HNCO isomer formation in ice mantles by UV and thermal processing: An experimental approach

    International Nuclear Information System (INIS)

    Jiménez-Escobar, A.; Giuliano, B. M.; Caro, G. M. Muñoz; Cernicharo, J.; Marcelino, N.

    2014-01-01

    Current gas-phase models do not account for the abundances of HNCO isomers detected in various environments, suggesting their formation in icy grain mantles. We attempted to study a formation channel of HNCO and its possible isomers by vacuum-UV photoprocessing of interstellar ice analogs containing H 2 O, NH 3 , CO, HCN, CH 3 OH, CH 4 , and N 2 followed by warm-up under astrophysically relevant conditions. Only the H 2 O:NH 3 :CO and H 2 O:HCN ice mixtures led to the production of HNCO species. The possible isomerization of HNCO to its higher energy tautomers following irradiation or due to ice warm-up has been scrutinized. The photochemistry and thermal chemistry of H 2 O:NH 3 :CO and H 2 O:HCN ices were simulated using the Interstellar Astrochemistry Chamber, a state-of-the-art ultra-high-vacuum setup. The ice was monitored in situ by Fourier transform mid-infrared spectroscopy in transmittance. A quadrupole mass spectrometer detected the desorption of the molecules in the gas phase. UV photoprocessing of H 2 O:NH 3 :CO and H 2 O:HCN ices lead to the formation of OCN – as a main product in the solid state and a minor amount of HNCO. The second isomer HOCN has been tentatively identified. Despite its low efficiency, the formation of HNCO and the HOCN isomers by UV photoprocessing of realistic simulated ice mantles might explain the observed abundances of these species in photodissociation regions, hot cores, and dark clouds.

  9. Effect of food processing on degradation of hexachlorocyclohexane and its isomers in milk

    OpenAIRE

    Singh, Sujatha; Nelapati, Krishnaiah

    2017-01-01

    Aim: To study the effect of different food processing techniques on the degradation of organochlorine compounds (α, β, ɣ and δ hexachlorocyclohexane isomers (HCH)) residues in both natural and fortified samples of milk. Materials and Methods: Raw milk samples are collected from the local areas of Hyderabad, India. Naturally and fortified milk samples (HCH) were subjected to various food processing techniques, pasteurization (63ºC for ½ h), sterilization (121ºC for 15 min) and boiling for 5...

  10. Dependence of electrical properties of polypropylene isomers on morphology and chain conformation

    Energy Technology Data Exchange (ETDEWEB)

    Guadagno, Liberata; Raimondo, Marialuigia; Vittoria, Vittoria [Dipartimento di Ingegneria Chimica e Alimentare, Universita di Salerno, Via Ponte Don Melillo, 84084 Fisciano (Italy); Bartolomeo, Antonio Di [Dipartimento di Fisica ' E Caianiello' , Via S Allende, 84081 Baronissi (Italy); De Vivo, Biagio; Lamberti, Patrizia; Tucci, Vincenzo, E-mail: lguadagno@unisa.i [Dipartimento di Ingegneria dell' Informazione e Ingegneria Elettrica Universita di Salerno, Via Ponte Don Melillo, 84084 Fisciano (Saudi Arabia) (Italy)

    2009-07-07

    The electrical properties of polypropylene isomers were correlated with the morphology and chain conformation of differently obtained isotactic (iPP) and syndiotactic (sPP) samples. In the case of iPP, a crystallized and a smectic sample were prepared, whereas for sPP two crystalline helical samples and a mesophase with the chains in trans-planar conformation were considered. The phase composition was obtained for all the samples comparing x-ray diffractograms and transport properties of vapours, which give the crystallinity and the amorphous fraction, respectively. The fraction of mesophase was obtained by the difference of the previous values. The study of the morphology evidenced similarities and differences among the samples, which were discussed and correlated with the phase composition. The electrical conductivity was measured for all the samples, and the syndiotactic isomer showed the lowest value as well as a dependence on the structure. In contrast, the isotactic isomer showed the same behaviour for either polymorph. Based on the structural and electrical results, a phenomenological explanation of the conduction mechanisms taking place in the different forms has been proposed. In particular, the current in the iPP seems to be controlled by Schottky emission, i.e. by field-assisted thermo-ionic injection of carriers from the electrode into the polymer, whereas for the sPP more than one mechanism is likely to be effective, although the ionic transport appears as the predominant one. The experimental data confirm a different behaviour of the ionic conduction properties for the different polymorphs, highlighting the greater insulating characteristics of the mesomorphic structure of the syndiotactic isomer.

  11. Proline Isomer-Specific Antibodies Reveal the Early Pathogenic Tau Conformation in Alzheimer's Disease

    OpenAIRE

    Nakamura, Kazuhiro; Greenwood, Alex; Binder, Lester; Bigio, Eileen H.; Denial, Sarah; Nicholson, Linda; Zhou, Xiao Zhen; Lu, Kun Ping

    2012-01-01

    Cis-trans isomerization of proteins phosphorylated by proline-directed kinases is proposed to control numerous signaling molecules, and is implicated in the pathogenesis of Alzheimer’s and other diseases. However, there is no direct evidence for the existence of cis-trans protein isomers in vivo, or for their conformation-specific function or regulation. Here we develop peptide chemistries that allow the generation of cis and trans-specific antibodies, and use them to raise antibodies specifi...

  12. Phototransformations of dinitropyrene isomers on models of the atmospheric particulate matter.

    Science.gov (United States)

    Arce, Rafael; Morel, María

    2013-08-01

    The 1,6 and 1,8-dinitropyrenes (DNP) isomers are strong mutagens and carcinogens encountered in diesel exhaust and airborne particles. Relative photodegradation rates were determined and some products were characterized when these isomers were irradiated adsorbed onto models of the atmospheric matter. These are compared to their photochemical behavior in a polar nonprotic solvent. The 1,8-DNP isomer is three times more reactive than the 1,6-DNP when irradiated adsorbed onto silica gel surfaces, while the reverse order is observed in solution, demonstrating the influence of structural differences and environmental effects on the photoreactivity. Oxygen is a key factor in the formation of pyrenediones from 1,8-DNP in solution and on silica gel which is not the case for 1,6-DNP. The average pore diameter (2.5 versus 6.0 nm) of the silica surfaces induces a significant change in the product distribution and relative yields of 1,8-DNP because pyrenediones or 8-hydroxy-1-nitropyrene are not produced in the smaller pore silica. A 6-hydroxy-1-nitropyrene product is observed both in acidic alumina and silica (6.0 nm) surfaces. On acidic alumina the rates of phototransformation of the isomers are equal, a significant increase in the relative yield of the hydroxynitropyrene product is observed compared to the silica and unidentified products in which the absence of NO 2 and pyrene absorption bands were observed, demonstrating the surface effect on the photodegradation. Overall, the presence of some products indicates the occurrence of a nitro-nitrite rearrangement on the surface with the participation of a pyrenoxy radical as their precursor.

  13. Discrimination of nuclear spin isomers exploiting the excited state dynamics of a quinodimethane derivative

    Energy Technology Data Exchange (ETDEWEB)

    Obaid, Rana [Institut für Theoretische Chemie, Universität Wien, Währinger Str. 17, 1090 Wien (Austria); Faculty of Pharmacy, Al-Quds University, Abu Dis, Palestine (Country Unknown); Kinzel, Daniel; Oppel, Markus, E-mail: markus.oppel@univie.ac.at; González, Leticia [Institut für Theoretische Chemie, Universität Wien, Währinger Str. 17, 1090 Wien (Austria)

    2014-10-28

    Despite the concept of nuclear spin isomers (NSIs) exists since the early days of quantum mechanics, only few approaches have been suggested to separate different NSIs. Here, a method is proposed to discriminate different NSIs of a quinodimethane derivative using its electronic excited state dynamics. After electronic excitation by a laser field with femtosecond time duration, a difference in the behavior of several quantum mechanical operators can be observed. A pump-probe experimental approach for separating these different NSIs is then proposed.

  14. New decay modes of the high-spin isomer of {sup 124}Cs

    Energy Technology Data Exchange (ETDEWEB)

    Radich, A.J.; Garrett, P.E.; Bianco, L.; Bildstein, V.; Chagnon-Lessard, S.; Demand, G.A.; Diaz Varela, A.; Dunlop, R.; Finlay, P.; Hadinia, B.; Jigmeddorj, B.; Laffoley, A.T.; Leach, K.G.; McGee, E.; Michetti-Wilson, J.; Rand, E.T.; Svensson, C.E.; Wong, J. [University of Guelph, Department of Physics, Guelph, ON (Canada); Andreoiu, C.; Cross, D.S.; Starosta, K. [Simon Fraser University, Department of Chemistry, Burnaby, BC (Canada); Ball, G.C.; Garnsworthy, A.B.; Hackman, G.; Rajabali, M.M. [TRIUMF, Vancouver, BC (Canada); Orce, J.N. [TRIUMF, Vancouver, BC (Canada); University of the Western Cape, Department of Physics, Bellville (South Africa); Sumithrarachchi, C.S. [University of Guelph, Department of Physics, Guelph, ON (Canada); Michigan State University, National Superconducting Cyclotron Laboratory, East Lansing, MI (United States); Triambak, S. [TRIUMF, Vancouver, BC (Canada); University of the Western Cape, Department of Physics, Bellville (South Africa); iThemba LABS, Somerset West (South Africa); Wang, Z.M. [Simon Fraser University, Department of Chemistry, Burnaby, BC (Canada); TRIUMF, Vancouver, BC (Canada); Williams, S.J. [TRIUMF, Vancouver, BC (Canada); Michigan State University, National Superconducting Cyclotron Laboratory, East Lansing, MI (United States); Wood, J.L. [Georgia Institute of Technology, School of Physics, Atlanta, GA (United States); Yates, S.W. [University of Kentucky, Departments of Chemistry and Physics and Astronomy, Lexington, KY (United States)

    2017-09-15

    A new β{sup +}/EC branch of 0.11 ± 0.02 % from the (7){sup +} isomer of {sup 124}Cs was identified in a measurement of the decay of {sup 124}Cs using the 8 π spectrometer at TRIUMF. Combinations of γ-γ, γ-e{sup -}, and e{sup -}-e{sup -} coincidence data were used to further investigate the isomeric decay. Six new transitions were observed and their branching ratios were measured. (orig.)

  15. Constitutional Isomers of Dendrimer-like Star Polymers: Design, Synthesis and Conformational and Structural Properties

    Energy Technology Data Exchange (ETDEWEB)

    Pople, John A

    2001-03-22

    The design, synthesis and solution properties of six constitutional isomers of dendrimer-like star polymers is described. Each of the polymers have comparable molecular weights ({approx} 80,000 g/mol), narrow polydispersities (< 1.19) and an identical number of branching junctures (45) and surface hydroxyl functionalities (48). The only difference in the six isomers is the placement of the branching junctures. The polymers are constructed from high molecular weight poly(e-caprolactone) with branching junctures derived from 2,2'-bis(hydroxylmethyl) propionic acid (bis-MPA) emanating from a central core. The use of various generations of dendritic initiators and dendrons coupled with the ring opening polymerization of e-caprolactones allowed a modular approach to the dendrimer-like star polymer isomers. The most pronounced effects on the physical properties/morphology and hydrodynamic volume was for those polymers in which the branching was distributed throughout the sample in a dendrimer-like fashion. The versatility of this approach has provided the possibility of understanding the relationship between architecture and physical properties. Dynamic light scattering and small angle X-ray scattering techniques were used to determine the hydrodynamic radius Rh and radius of gyration Rg respectively. The relationship between Rg and molecular weight was indicative of a compact star-like structure, and did not show advanced bias towards either the dense core or dense shell models. The radial density distribution of the isomers was therefore modeled according to a many arm star polymer, and good agreement was found with experimental measures of Rh/Rg.

  16. Identification of the naturally occurring isomer of zearalenol produced by Fusarium roseum 'Gibbosum' in rice culture.

    Science.gov (United States)

    Hagler, W M; Mirocha, C J; Pathre, S V; Behrens, J C

    1979-01-01

    One diastereomer of trans-zearalenol [2,4-dihydroxy-6-(6,10-dihydroxy-trans-1-undecenyl)-benzoic acid-mu-lactone] was isolated from cultures of Fusarium roseum 'Gibbosum.' This strongly estrogenic metabolite was identified by analysis of its mass spectrum and its behavior in thin-layer, high-pressure liquid and gas-liquid chromatographic systems. The concentration of zearalenol in cultures was 563 mu g/g, or 7% of the 8,000-mu g/g zearalenone content, while the two diastereomers of 8'-hydroxyzearalenone each occurred at 3% of the zearalenone level. Of the two possible diastereomers of zearalenol, the one occurring in cultures was identical to the low-melting-point (171 degrees C) isomer (alpha) obtained by synthesis. In the rat uterus bioassay, the alpha zearalenol isomer was three times more estrogenic than zearalenone while the beta isomer was equal in activity in zearalenone. The two diastereomers of zearalenol can be distinguished from each other by the intensity of the m/e+ 302 fragment of the mass spectrum of the pure underivatized compound. PMID:485136

  17. Profiling of the Molecular Weight and Structural Isomer Abundance of Macroalgae-Derived Phlorotannins

    Science.gov (United States)

    Heffernan, Natalie; Brunton, Nigel P.; FitzGerald, Richard J.; Smyth, Thomas J.

    2015-01-01

    Phlorotannins are a group of complex polymers of phloroglucinol (1,3,5-trihydroxybenzene) unique to macroalgae. These phenolic compounds are integral structural components of the cell wall in brown algae, but also play many secondary ecological roles such as protection from UV radiation and defense against grazing. This study employed Ultra Performance Liquid Chromatography (UPLC) with tandem mass spectrometry to investigate isomeric complexity and observed differences in phlorotannins derived from macroalgae harvested off the Irish coast (Fucus serratus, Fucus vesiculosus, Himanthalia elongata and Cystoseira nodicaulis). Antioxidant activity and total phenolic content assays were used as an index for producing phlorotannin fractions, enriched using molecular weight cut-off dialysis with subsequent flash chromatography to profile phlorotannin isomers in these macroalgae. These fractions were profiled using UPLC-MS with multiple reaction monitoring (MRM) and the level of isomerization for specific molecular weight phlorotannins between 3 and 16 monomers were determined. The majority of the low molecular weight (LMW) phlorotannins were found to have a molecular weight range equivalent to 4–12 monomers of phloroglucinol. The level of isomerization within the individual macroalgal species differed, resulting in substantially different numbers of phlorotannin isomers for particular molecular weights. F. vesiculosus had the highest number of isomers of 61 at one specific molecular mass, corresponding to 12 phloroglucinol units (PGUs). These results highlight the complex nature of these extracts and emphasize the challenges involved in structural elucidation of these compounds. PMID:25603345

  18. Profiling of the Molecular Weight and Structural Isomer Abundance of Macroalgae-Derived Phlorotannins

    Directory of Open Access Journals (Sweden)

    Natalie Heffernan

    2015-01-01

    Full Text Available Phlorotannins are a group of complex polymers of phloroglucinol (1,3,5-trihydroxybenzene unique to macroalgae. These phenolic compounds are integral structural components of the cell wall in brown algae, but also play many secondary ecological roles such as protection from UV radiation and defense against grazing. This study employed Ultra Performance Liquid Chromatography (UPLC with tandem mass spectrometry to investigate isomeric complexity and observed differences in phlorotannins derived from macroalgae harvested off the Irish coast (Fucus serratus, Fucus vesiculosus, Himanthalia elongata and Cystoseira nodicaulis. Antioxidant activity and total phenolic content assays were used as an index for producing phlorotannin fractions, enriched using molecular weight cut-off dialysis with subsequent flash chromatography to profile phlorotannin isomers in these macroalgae. These fractions were profiled using UPLC-MS with multiple reaction monitoring (MRM and the level of isomerization for specific molecular weight phlorotannins between 3 and 16 monomers were determined. The majority of the low molecular weight (LMW phlorotannins were found to have a molecular weight range equivalent to 4–12 monomers of phloroglucinol. The level of isomerization within the individual macroalgal species differed, resulting in substantially different numbers of phlorotannin isomers for particular molecular weights. F. vesiculosus had the highest number of isomers of 61 at one specific molecular mass, corresponding to 12 phloroglucinol units (PGUs. These results highlight the complex nature of these extracts and emphasize the challenges involved in structural elucidation of these compounds.

  19. Experimental determination of the energy difference between competing isomers of deposited, size-selected gold nanoclusters.

    Science.gov (United States)

    Foster, D M; Ferrando, R; Palmer, R E

    2018-04-03

    The equilibrium structures and dynamics of a nanoscale system are regulated by a complex potential energy surface (PES). This is a key target of theoretical calculations but experimentally elusive. We report the measurement of a key PES parameter for a model nanosystem: size-selected Au nanoclusters, soft-landed on amorphous silicon nitride supports. We obtain the energy difference between the most abundant structural isomers of magic number Au 561 clusters, the decahedron and face-centred-cubic (fcc) structures, from the equilibrium proportions of the isomers. These are measured by atomic-resolution scanning transmission electron microscopy, with an ultra-stable heating stage, as a function of temperature (125-500 °C). At lower temperatures (20-125 °C) the behaviour is kinetic, exhibiting down conversion of metastable decahedra into fcc structures; the higher state is repopulated at higher temperatures in equilibrium. We find the decahedron is 0.040 ± 0.020 eV higher in energy than the fcc isomer, providing a benchmark for the theoretical treatment of nanoparticles.

  20. Elucidation of structural isomers from the homogeneous rhodium-catalyzed isomerization of vegetable oils.

    Science.gov (United States)

    Andjelkovic, Dejan D; Min, Byungrok; Ahn, Dong; Larock, Richard C

    2006-12-13

    The structural isomers formed by the homogeneous rhodium-catalyzed isomerization of several vegetable oils have been elucidated. A detailed study of the isomerization of the model compound methyl linoleate has been performed to correlate the distribution of conjugated isomers, the reaction kinetics, and the mechanism of the reaction. It has been shown that [RhCl(C8H8)2]2 is a highly efficient and selective isomerization catalyst for the production of highly conjugated vegetable oils with a high conjugated linoleic acid (CLA) content, which is highly desirable in the food industry. The combined fraction of the two major CLA isomers [(9Z,11E)-CLA and (10E,12Z)-CLA] in the overall CLA mixture is in the range from 76.2% to 93.4%. The high efficiency and selectivity of this isomerization method along with the straightforward purification process render this approach highly promising for the preparation of conjugated oils and CLA. Proposed improvements in catalyst recovery and reusability will only make this method more appealing to the food, paint, coating, and polymer industries in the future.

  1. Infrared Spectroscopy of Two Isomers of the OCS-CS_{2} Complex

    Science.gov (United States)

    Oliaee, J. N.; Dehghany, M.; Afshari, Mahin; Moazzen-Ahmadi, N.; McKellar, A. R. W.

    2009-06-01

    A second isomer of OCS-CS_{2} complex, with a nonplanar cross-shaped structure, has been studied for the first time by analysing an infrared band in the region of the OCS stretching vibration (2062 cm^{-1}). This isomer has C_{s} symmetry and the observed band consists of purely c-type rotational transitions. The ground state rotational parameters are found to be A=0.07306 cm^{-1}, B=0.03325 cm^{-1} and C=0.02879 cm^{-1}, in good agreement with a previous semi-empirical calculation. In addition, a hybrid band with a- and b-type rotational transitions has been assigned to be due to the known planar form of OCS-CS_{2}, as previously studied by microwave spectroscopy. The spectra were recorded using a rapid-scan tunable diode laser spectrometer to probe a pulsed supersonic jet expansion. Calculations indicate that the planar isomer of OCS-CS_{2} is the lowest in energy, in contrast to CO_{2}-CS_{2} where the crossed form is believed to be the lowest. J. J. Newby, M. M. Serafin, R. A. Peebles and S. A. Peebles, Phys. Chem. Chem. Phys. 7, 487 (2005). C. C. Dutton, D. A. Dows, R. Eikey, S. Evans and R. A. Beaudet, J. Phys. Chem. A 102, 6904 (1998).

  2. Decay spectroscopy of 160Sm: The lightest four-quasiparticle K isomer

    Directory of Open Access Journals (Sweden)

    Z. Patel

    2016-02-01

    Full Text Available The decay of a new four-quasiparticle isomeric state in 160Sm has been observed using γ-ray spectroscopy at the RIBF, RIKEN. The four-quasiparticle state is assigned a 2π⊗2ν π52−[532], π52+[413], ν52−[523], ν72+[633] configuration. The half-life of this (11+ state is measured to be 1.8(4 μs. The (11+ isomer decays into a rotational band structure, based on a (6− ν52−[523]⊗ν72+[633] bandhead, consistent with the gK−gR values. This decays to a (5− two-proton quasiparticle state, which in turn decays to the ground state band. Potential energy surface and blocked-BCS calculations were performed in the deformed midshell region around 160Sm. They reveal a significant influence from β6 deformation and that 160Sm is the best candidate for the lightest four-quasiparticle K isomer to exist in this region. The relationship between reduced hindrance and isomer excitation energy for E1 transitions from multiquasiparticle states is considered with the new data from 160Sm. The E1 data are found to agree with the existing relationship for E2 transitions.

  3. Isomer Information from Ion Mobility Separation of High-Mannose Glycan Fragments.

    Science.gov (United States)

    Harvey, David J; Seabright, Gemma E; Vasiljevic, Snezana; Crispin, Max; Struwe, Weston B

    2018-03-05

    Extracted arrival time distributions of negative ion CID-derived fragments produced prior to traveling-wave ion mobility separation were evaluated for their ability to provide structural information on N-linked glycans. Fragmentation of high-mannose glycans released from several glycoproteins, including those from viral sources, provided over 50 fragments, many of which gave unique collisional cross-sections and provided additional information used to assign structural isomers. For example, cross-ring fragments arising from cleavage of the reducing terminal GlcNAc residue on Man 8 GlcNAc 2 isomers have unique collision cross-sections enabling isomers to be differentiated in mixtures. Specific fragment collision cross-sections enabled identification of glycans, the antennae of which terminated in the antigenic α-galactose residue, and ions defining the composition of the 6-antenna of several of the glycans were also found to have different cross-sections from isomeric ions produced in the same spectra. Potential mechanisms for the formation of the various ions are discussed and the estimated collisional cross-sections are tabulated. Graphical Abstract ᅟ.

  4. Serum Metabolic Fingerprinting Identified Putatively Annotated Sphinganine Isomer as a Biomarker of Wolfram Syndrome.

    Science.gov (United States)

    Zmyslowska, Agnieszka; Ciborowski, Michal; Borowiec, Maciej; Fendler, Wojciech; Pietrowska, Karolina; Parfieniuk, Ewa; Antosik, Karolina; Pyziak, Aleksandra; Waszczykowska, Arleta; Kretowski, Adam; Mlynarski, Wojciech

    2017-11-03

    Wolfram syndrome (WFS) is an example of a rare neurodegenerative disease with coexisting endocrine symptoms including diabetes mellitus as the first clinical symptom. Treatment of WFS is still only symptomatic and associated with poor prognosis. Potential markers of disease progression that could be useful for possible intervention trials are not available. Metabolomics has potential to identify such markers. In the present study, serum fingerprinting by LC-QTOF-MS was performed in patients with WFS (n = 13) and in patients with T1D (n = 27). On the basis of the obtained results, aminoheptadecanediol (17:0 sphinganine isomer) (+50%, p = 0.02), as the most discriminatory metabolite, was selected for validation. The 17:0 sphinganine isomer level was determined using the LC-QQQ method in the samples from WFS patients at two time points and compared with samples obtained from patients with T1D (n = 24) and healthy controls (n = 24). Validation analysis showed higher 17:0 sphinganine isomer level in patients with WFS compared to patients with T1D (p = 0.0097) and control group (p < 0.0001) with progressive reduction of its level after two-year follow-up period. Patients with WFS show a unique serum metabolic fingerprint, differentiating them from patients with T1D. Sphinganine derivate seems to be a marker of the ongoing process of neurodegeneration in WFS patients.

  5. Infrared spectroscopy of the methanol cation and its methylene-oxonium isomer

    Science.gov (United States)

    Mosley, J. D.; Young, J. W.; Huang, M.; McCoy, A. B.; Duncan, M. A.

    2015-03-01

    The carbenium ion with nominal formula [C,H4,O]+ is produced from methanol or ethylene glycol in a pulsed-discharge supersonic expansion source. The ion is mass selected, and its infrared spectrum is measured from 2000 to 4000 cm-1 using laser photodissociation spectroscopy and the method of rare gas atom tagging. Computational chemistry predicts two isomers, the methanol and methylene-oxonium cations. Predicted vibrational spectra based on scaled harmonic and reduced dimensional treatments are compared to the experimental spectra. The methanol cation is the only isomer produced when methanol is used as a precursor. When ethylene glycol is used as the precursor, methylene-oxonium is produced in addition to the methanol cation. Theoretical results at the CCSD(T)/cc-pVTZ level show that methylene-oxonium is lower in energy than methanol cation by 6.4 kcal/mol, and is in fact the global minimum isomer on the [C,H4,O]+ potential surface. Methanol cation is trapped behind an isomerization barrier in our source, providing a convenient method to produce and characterize this transient species. Analysis of the spectrum of the methanol cation provides evidence for strong CH stretch vibration/torsion coupling in this molecular ion.

  6. Selectivity of Brij-35 in Micellar Liquid Chromatographic Separation of Positional Isomers

    Directory of Open Access Journals (Sweden)

    Najma Memon

    2012-01-01

    Full Text Available Implementation of Brij-35, a nonionic surfactant, as a mobile phase for separation of positional isomers is investigated. Chromolith C-18 SpeedROD is used as a stationary phase. The effect of surfactant and organic modifier (propanol concentration on the separation of some selected isomers is studied and evaluated in terms of linear solvation energy relationship (LSER. Shape selectivity is assessed by α value of sorbic and benzoic acid, which is found to be 1.339 by using mobile phase composed of 0.5% aqueous solutions of Brij-35 and propanol in 9 : 1. Isomers of parabens, nitroanilines, nitrophenols, and quinolinols are successfully separated using mobile phases composed of various percentages of surfactant and propanol. System constants for nonionic MLC using LSER analysis show that hydrogen bond basicity and dipolarity may be major contributors to selectivity, while excess molar refraction helps fine-tuning the separation which also imparts unique selectivity to nonionic surfactants as compared to ionic ones.

  7. Ionic Block Copolymers for Anion Exchange Membranes

    Science.gov (United States)

    Tsai, Tsung-Han; Herbst, Dan; Giffin, Guinevere A.; di Noto, Vito; Witten, Tom; Coughlin, E. Bryan

    2013-03-01

    Anion exchange membrane (AEM) fuel cells have regained interest because it allows the use of non-noble metal catalysts. Until now, most of the studies on AEM were based on random polyelectrolytes. In this work, Poly(vinylbenzyltrimethylammonium bromide)-b- (methylbutylene) ([PVBTMA][Br]-b-PMB) was studied by SAXS, TEM and dielectric spectroscopy to understand the fundamental structure-conductivity relationship of ion transport mechanisms within well-ordered block copolymers. The ionic conductivity and the formation of order structure were dependent on the casting solvent. Higher ion exchange capacity (IEC) of the membranes showed higher conductivity at as IEC values below 1.8mmol/g, as above this, the ionic conductivity decreases due to more water uptake leading to dilution of charge density. The humidity dependence of morphology exhibited the shifting of d-spacing to higher value and the alteration in higher characteristic peak of SAXS plot as the humidity increase from the dry to wet state. This phenomenon can be further explained by a newly developed polymer brush theory. Three ionic conduction pathways with different conduction mechanism within the membranes can be confirmed by broadband electric spectroscopy. US Army MURI (W911NF1010520)

  8. Radiosensitization of microorganisms by radical anions

    International Nuclear Information System (INIS)

    Schubert, J.; Stegeman, H.; Swildens, M.

    1981-01-01

    Irradiation of Streptococcus faecalis in a neutral, N 2 O/Br - system leads to practically complete killing with extraordinarily low doses of irradiation, namely a D 10 of 13 Gy compared to 470 Gy in N 2 , 250 Gy in N 2 O and 160 Gy in O 2 . However, irradiation and chemical investigations demonstrated that the apparent radiosensitization in neutral, N 2 O/Br - is due mainly to bromine, Br 2 and HOBr rather than B 3 - or the radical anion, Br 2 - . For example, addition of unirradiated bacteria to a previously irradiated neutral solution of N 2 O/Br - reduces survival. The medium effects are eliminated by radiation chemical and/or chemical reactions which destroy bromine, such as occur in basic solutions, in N 2 /Br - or O 2 /Br - systems because of back reactions of Br 2 with e - sub(aq) in the former and of Br 2 with H 2 O 2 and O 2 - in the latter. Neither are medium effects produced in N 2 O/Br - systems at pH > 9. However, in N 2 /Br - the D 10 = 82 Gy compared to 160 Gy in O 2 which indicates that for S. faecalis Br 2 - is intrinsically a more effective radiosensitizing agent than oxygen. (author)

  9. Globins Scavenge Sulfur Trioxide Anion Radical*

    Science.gov (United States)

    Gardner, Paul R.; Gardner, Daniel P.; Gardner, Alexander P.

    2015-01-01

    Ferrous myoglobin was oxidized by sulfur trioxide anion radical (STAR) during the free radical chain oxidation of sulfite. Oxidation was inhibited by the STAR scavenger GSH and by the heme ligand CO. Bimolecular rate constants for the reaction of STAR with several ferrous globins and biomolecules were determined by kinetic competition. Reaction rate constants for myoglobin, hemoglobin, neuroglobin, and flavohemoglobin are large at 38, 120, 2,600, and ≥ 7,500 × 106 m−1 s−1, respectively, and correlate with redox potentials. Measured rate constants for O2, GSH, ascorbate, and NAD(P)H are also large at ∼100, 10, 130, and 30 × 106 m−1 s−1, respectively, but nevertheless allow for favorable competition by globins and a capacity for STAR scavenging in vivo. Saccharomyces cerevisiae lacking sulfite oxidase and deleted of flavohemoglobin showed an O2-dependent growth impairment with nonfermentable substrates that was exacerbated by sulfide, a precursor to mitochondrial sulfite formation. Higher O2 exposures inactivated the superoxide-sensitive mitochondrial aconitase in cells, and hypoxia elicited both aconitase and NADP+-isocitrate dehydrogenase activity losses. Roles for STAR-derived peroxysulfate radical, superoxide radical, and sulfo-NAD(P) in the mechanism of STAR toxicity and flavohemoglobin protection in yeast are suggested. PMID:26381408

  10. Simultaneous determination of inorganic and organic anions by ion chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Park, Yang Soon; Joe, Ki Soo; Han, Sun Ho; Park, Soon Dal; Choi, Kwang Soon

    1999-06-01

    Four methods were investigated for the simultaneous determination of several inorganic and organic anions in aqueous solution by ion chromatography. The first is two columns coupled system. The second is the gradient elution system with an anion exchange column. The third is the system with a mixed-mode stationary phase. The fourth is the system with an anion exchange column and the eluant of low conductivity without ion suppressor. The advantages and disadvantages of individual systems were discussed. The suitable methods were proposed for the application to the samples of the nuclear power industry and the environment. (author)

  11. A Quick Reference on High Anion Gap Metabolic Acidosis.

    Science.gov (United States)

    Funes, Silvia; de Morais, Helio Autran

    2017-03-01

    High anion gap (AG) metabolic acidoses can be identified by a decrease in pH, decrease in HCO 3 - or base excess, and an increased AG. The AG represents the difference between unmeasured cations and unmeasured anions; it increases secondary to the accumulation of anions other than bicarbonate and chloride. The most common causes of high AG acidosis are renal failure, diabetic ketoacidosis, and lactic acidosis. Severe increases in concentration of phosphorus can cause hyperphosphatemic acidosis. Copyright © 2016 Elsevier Inc. All rights reserved.

  12. Isomer-Specific IR Spectroscopy of BENZENE-(WATER)N Clusters with N=1-8: New Insights from the Water Bend Fundamentals and Isotopically Substituted Clusters

    Science.gov (United States)

    Kusaka, Ryoji; Walsh, Patrick S.; Zwier, Timothy S.

    2014-06-01

    This talk will focus on the isomer-specific IR spectra of benzene-(water)n (BWn) clusters with n = 1-8, returning to a topic studied by our group some 20 years ago, but now with higher resolution (OH stretch region), with inclusion of data from isotopically substituted clusters, and with extension into the HOH bending mode region. Spectra are recorded using resonant ion-dip infrared spectroscopy, an IR-UV double resonance method. Isomer-specific IR spectra in the regions of OH, OD stretches and HOH, HOD bend of benzene-H_2O, -D_2O, -HOD, -(H_2O)_2, -(D_2O)_2, -HOD-DOD were recorded in order to investigate in greater detail the intermolecular potential energy surface between water and benzene. These spectra show strong combination bands in addition to the OH/OD stretch fundamentals arising from large-amplitude "tumbling" and tunneling along internal rotation and torsion coordinates of water(s) on the surface of benzene. Interestingly, the number of extra bands and spectral patterns change dramatically depending on cluster size, the kind of deuterated isomer, and the spectral region probed. In larger clusters with n=3-8, the water HOH bending region is explored for the first time. The prominent bending mode transitions in BW1-8 are spread over a relatively small range (1610-1660 wn), and shift with cluster size in a way that reflects the known structural changes that accompany the increase in size. By comparison of experiment with calculation, it is possible to assign the experimentally observed 1614 wn transition of BW1 and 1615 wn of BW2 bands to the π-bound water molecule. The 1620-1660 wn bands of BW3-8 are due to water molecules that can be categorized as single-acceptor, single-donor (AD) hydrogen-bonded waters. In the case of single-acceptor, double-donor (ADD) water molecules, which are expected to be seen from BW6,a they show higher-frequency bending vibrations and weaker IR intensity, which would correspond to very weakly observed bands in 1660-1750 wn for

  13. Tonoplast anion channel activity modulation by pH in Chara corallina.

    Science.gov (United States)

    Berecki, G; Eijken, M; Van Iren, F; Van Duijn, B

    2001-11-15

    The patch-clamp technique was used to investigate regulation of anion channel activity in the tonoplast of Chara corallina in response to changing proton and calcium concentrations on both sides of the membrane. These channels are known to be Ca2+-dependent, with conductances in the range of 37 to 48 pS at pH 7.4. By using low pH at the vacuolar side (either pH(vac) 5.3 or 6.0) and a cytosolic pH (pH(cyt)) varying in a range of 4.3 to 9.0, anion channel activity and single-channel conductance could be reversibly modulated. In addition, Ca2+-sensitivity of the channels was markedly influenced by pH changes. At pH(cyt) values of 7.2 and 7.4 the half-maximal concentration (EC50) for calcium activation was 100-200 microm, whereas an EC(50) of about 5 microm was found at a pH(cyt) of 6.0. This suggests an improved binding of Ca2+ ions to the channel protein at more acidic cytoplasm. At low pH(cyt), anion channel activity and mean open times were voltage-dependent. At pipette potentials (V(p)) of +100 mV, channel activity was approximately 15-fold higher than activity at negative pipette potentials and the mean open time of the channel increased. In contrast, at pH(cyt) 7.2, anion channel activity and the opening behavior seemed to be independent of the applied V(p). The kinetics of the channel could be further controlled by the Ca2+ concentration at the cytosolic membrane side: the mean open time significantly increased in the presence of a high cytosolic Ca2+ concentration. These results show that tonoplast anion channels are maintained in a highly active state in a narrow pH range, below the resting pH(cyt). A putative physiological role of the pH-dependent modulation of these anion channels is discussed.

  14. Sulfate anion stabilization of native ribonuclease A both by anion binding and by the Hofmeister effect.

    Science.gov (United States)

    Ramos, Carlos H I; Baldwin, Robert L

    2002-07-01

    Data are reported for T(m), the temperature midpoint of the thermal unfolding curve, of ribonuclease A, versus pH (range 2-9) and salt concentration (range 0-1 M) for two salts, Na(2)SO(4) and NaCl. The results show stabilization by sulfate via anion-specific binding in the concentration range 0-0.1 M and via the Hofmeister effect in the concentration range 0.1-1.0 M. The increase in T(m) caused by anion binding at 0.1 M sulfate is 20 degrees at pH 2 but only 1 degree at pH 9, where the net proton charge on the protein is near 0. The 10 degrees increase in T(m) between 0.1 and 1.0 M Na(2)SO(4), caused by the Hofmeister effect, is independent of pH. A striking property of the NaCl results is the absence of any significant stabilization by 0.1 M NaCl, which indicates that any Debye screening is small. pH-dependent stabilization is produced by 1 M NaCl: the increase in T(m) between 0 and 1.0 M is 14 degrees at pH 2 but only 1 degree at pH 9. The 14 degree increase at pH 2 may result from anion binding or from both binding and Debye screening. Taken together, the results for Na(2)SO(4) and NaCl show that native ribonuclease A is stabilized at low pH in the same manner as molten globule forms of cytochrome c and apomyoglobin, which are stabilized at low pH by low concentrations of sulfate but only by high concentrations of chloride.

  15. Fundamental Issues Related to the Origin of Melatonin and Melatonin Isomers during Evolution: Relation to Their Biological Functions

    Directory of Open Access Journals (Sweden)

    Dun-Xian Tan

    2014-09-01

    Full Text Available Melatonin and melatonin isomers exist and/or coexist in living organisms including yeasts, bacteria and plants. The levels of melatonin isomers are significantly higher than that of melatonin in some plants and in several fermented products such as in wine and bread. Currently, there are no reports documenting the presence of melatonin isomers in vertebrates. From an evolutionary point of view, it is unlikely that melatonin isomers do not exist in vertebrates. On the other hand, large quantities of the microbial flora exist in the gut of the vertebrates. These microorganisms frequently exchange materials with the host. Melatonin isomers, which are produced by these organisms inevitably enter the host’s system. The origins of melatonin and its isomers can be traced back to photosynthetic bacteria and other primitive unicellular organisms. Since some of these bacteria are believed to be the precursors of mitochondria and chloroplasts these cellular organelles may be the primary sites of melatonin production in animals or in plants, respectively. Phylogenic analysis based on its rate-limiting synthetic enzyme, serotonin N-acetyltransferase (SNAT, indicates its multiple origins during evolution. Therefore, it is likely that melatonin and its isomer are also present in the domain of archaea, which perhaps require these molecules to protect them against hostile environments including extremely high or low temperature. Evidence indicates that the initial and primary function of melatonin and its isomers was to serve as the first-line of defence against oxidative stress and all other functions were acquired during evolution either by the process of adoption or by the extension of its antioxidative capacity.

  16. Fundamental Issues Related to the Origin of Melatonin and Melatonin Isomers during Evolution: Relation to Their Biological Functions

    Science.gov (United States)

    Tan, Dun-Xian; Zheng, Xiaodong; Kong, Jin; Manchester, Lucien C.; Hardeland, Ruediger; Kim, Seok Joong; Xu, Xiaoying; Reiter, Russel J.

    2014-01-01

    Melatonin and melatonin isomers exist and/or coexist in living organisms including yeasts, bacteria and plants. The levels of melatonin isomers are significantly higher than that of melatonin in some plants and in several fermented products such as in wine and bread. Currently, there are no reports documenting the presence of melatonin isomers in vertebrates. From an evolutionary point of view, it is unlikely that melatonin isomers do not exist in vertebrates. On the other hand, large quantities of the microbial flora exist in the gut of the vertebrates. These microorganisms frequently exchange materials with the host. Melatonin isomers, which are produced by these organisms inevitably enter the host’s system. The origins of melatonin and its isomers can be traced back to photosynthetic bacteria and other primitive unicellular organisms. Since some of these bacteria are believed to be the precursors of mitochondria and chloroplasts these cellular organelles may be the primary sites of melatonin production in animals or in plants, respectively. Phylogenic analysis based on its rate-limiting synthetic enzyme, serotonin N-acetyltransferase (SNAT), indicates its multiple origins during evolution. Therefore, it is likely that melatonin and its isomer are also present in the domain of archaea, which perhaps require these molecules to protect them against hostile environments including extremely high or low temperature. Evidence indicates that the initial and primary function of melatonin and its isomers was to serve as the first-line of defence against oxidative stress and all other functions were acquired during evolution either by the process of adoption or by the extension of its antioxidative capacity. PMID:25207599

  17. Lifetime and g-factor of a new isomer in 130 La

    International Nuclear Information System (INIS)

    Ionescu-Bujor, M.; Iordachescu, A.; Brandolini, F.; Pavan, P.; Rossi Alvarez, C.; De Poli, M.; Medina, N.H.; Rao, M.N.

    1999-01-01

    Pulsed-beam measurements have been recently performed at the XTU-tandem of the National Laboratory of Legnaro with the aim to investigate short-lived isomeric states in neutron-deficient nuclei of the A∼130 region. Isotopically enriched tin targets were irradiated with a 70 MeV 16 O beam (pulse width of 3 ns at a repetition rate of 800 ns) and the γ-ray angular distributions perturbed in magnetic or electric interaction were observed time-differentially. Static electromagnetic moments were thus determined for several known short-lived isomers in 129,130,131 Ce and 129 Ba. In these experiments a new isomeric decay has been also identified and its properties are reported in the present work. The isomer has been observed on a target containing 116 Sn (87%), 117 Sn (8%) and 118 Sn (5%). The tin target of 0.6 mg/cm 2 thickness evaporated on a Pb foil was placed in an external magnetic field of 32 kG whose orientation was periodically reversed. Two planar HPGe detectors positioned at ±135 deg. with respect to the beam direction were used for the γ-ray detection. In the delayed spectra a γ-ray of 105.2 keV has been observed and a half-life of 32(5)ns has been determined for it. The experimental and calculated R(t) modulation ratios of the 105.2 keV γ-ray in the external magnetic field are given. From the derived Larmor frequency a value g = + 0.48(3) has been determined for the isomeric state g-factor. A dipole character has been established for the delayed 105.2 keV γ-transition based on the determined negative A 2 coefficient. The new isomer was tentatively assigned to the odd-odd 130 La populated in the 116,117,118 Sn ( 16 O,pxn) reaction. In this nucleus a state at (150.3 + x) keV de-excited by a 105.2 keV transition is known and it was identified with the isomer. Further experiments are in progress for the definite assignment and the elucidation of the isomer configuration. (authors)

  18. Electrochemistry and electrogenerated chemiluminescence of dithienylbenzothiadiazole derivative. Differential reactivity of donor and acceptor groups and simulations of radical cation-anion and dication-radical anion annihilations.

    Science.gov (United States)

    Shen, Mei; Rodríguez-López, Joaquín; Huang, Ju; Liu, Quan; Zhu, Xu-Hui; Bard, Allen J

    2010-09-29

    We report here the electrochemistry and electrogenerated chemiluminescence (ECL) of a red-emitting dithienylbenzothiadiazole-based molecular fluorophore (4,7-bis(4-(4-sec-butoxyphenyl)-5-(3,5-di(1-naphthyl)phenyl)thiophen-2-yl)-2,1,3-benzothiadiazole, 1b). 1b contains two substituted thiophene groups as strong electron donors at the ends connected directly to a strong electron acceptor, 2,1,3-benzothiadiazole, in the center. Each thiophene moiety is substituted in position 2 by 3,5-di(1-naphthyl)phenyl and in position 3 by 4-sec-butoxyphenyl. Cyclic voltammetry of 1b, with scan rate ranging from 0.05 to 0.75 V/s, shows a single one-electron reduction wave (E°(red) = -1.18 V vs SCE) and two nernstian one-electron oxidation waves (E°(1,ox) = 1.01 V, E°(2,ox) = 1.24 V vs SCE). Reduction of the unsubstituted 2,1,3-benzothiadiazole center shows nernstian behavior with E°(red) = -1.56 V vs SCE. By comparison to a digital simulation, the heterogeneous electron-transfer rate constant for reduction, k(r)° = 1.5 × 10(-3) cm/s, is significantly smaller than those for the oxidations, k(o)° > 0.1 cm/s, possibly indicating that the two substituted end groups have a blocking effect on the reduction of the benzothiadiazole center. The ECL spectrum, produced by electron-transfer annihilation of the reduced and oxidized forms, consists of a single peak with maximum emission at about 635 nm, consistent with the fluorescence of the parent molecule. Relative ECL intensities with respect to 9,10-diphenylanthracene are 330% and 470% for the radical anion-cation and radical anion-dication annihilation, respectively. Radical anion (A(-•))-cation (A(+•)) annihilation produced by potential steps shows symmetric ECL transients during anodic and cathodic pulses, while for anion (A(-•))-dication (A(2+•)) annihilation, transient ECL shows asymmetry in which the anodic pulse is narrower than the cathodic pulse. Digital simulation of the transient ECL experiments showed that the

  19. New anion-exchange polymers for improved separations

    International Nuclear Information System (INIS)

    Jarvinen, G.D.; Barr, M.E.; Marsh, S.F.

    1997-01-01

    Objective is to improve the understanding of how the structure of a new class of anion-exchange polymers controls the binding of anionic actinide complexes from solution. This is needed to develop practical separation systems that will reduce the cost of actinide processing operations within the DOE complex. In addition anion exchange is widely used in industry. Several new series of bifunctional anion- exchange polymers have been designed, synthesized, and tested for removing Pu(IV), Am(III), and U(VI) from nitric acid. The polymers contain a pyridinium site derived from the host poly(4-vinylpyridine) and a second cationic site attached through a chain of 2 to 6 methylene groups. The new polymers removed Pu four to ten times more efficiently than the best commercial materials

  20. An anion channel in Arabidopsis hypocotyls activated by blue light

    Science.gov (United States)

    Cho, M. H.; Spalding, E. P.; Evans, M. L. (Principal Investigator)

    1996-01-01

    A rapid, transient depolarization of the plasma membrane in seedling stems is one of the earliest effects of blue light detected in plants. It appears to play a role in transducing blue light into inhibition of hypocotyl (stem) elongation, and perhaps other responses. The possibility that activation of a Cl- conductance is part of the depolarization mechanism was raised previously and addressed here. By patch clamping hypocotyl cells isolated from dark-grown (etiolated) Arabidopsis seedlings, blue light was found to activate an anion channel residing at the plasma membrane. An anion-channel blocker commonly known as NPPB 15-nitro-2-(3-phenylpropylamino)-benzoic acid] potently and reversibly blocked this anion channel. NPPB also blocked the blue-light-induced depolarization in vivo and decreased the inhibitory effect of blue light on hypocotyl elongation. These results indicate that activation of this anion channel plays a role in transducing blue light into growth inhibition.

  1. Anions for Near-Infrared Selective Organic Salt Photovoltaics.

    Science.gov (United States)

    Traverse, Christopher J; Young, Margaret; Suddard-Bangsund, John; Patrick, Tyler; Bates, Matthew; Chen, Pei; Wingate, Brian; Lunt, Sophia Y; Anctil, Annick; Lunt, Richard R

    2017-11-27

    Organic molecular salts are an emerging and highly tunable class of materials for organic and transparent photovoltaics. In this work, we demonstrate novel phenyl borate and carborane-based anions paired with a near-infrared (NIR)-selective heptamethine cation. We further explore the effects of anion structures and functional groups on both device performance and physical properties. Changing the functional groups on the anion significantly alters the open circuit voltage and yields a clear dependence on electron withdrawing groups. Anion exchange is also shown to selectively alter the solubility and film surface energy of the resulting molecular salt, enabling the potential fabrication of solution-deposited cascade or multi-junction devices from orthogonal solvents. This study further expands the catalog and properties of organic salts for inexpensive, and stable NIR-selective molecular salt photovoltaics.

  2. Adsorption of inorganic anionic contaminants on surfactant modified minerals

    Directory of Open Access Journals (Sweden)

    MAGDALENA TOMASEVIC-CANOVIC

    2003-11-01

    Full Text Available Organo-mineral complexes were obtained by treatment of aluminosilicate minerals (zeolite, bentonite and diatomaceous earth with a primary amine (oleylamine and an alkyl ammonium salt (stearyldimethylbenzyl ammonium chloride. The modification of the zeolite surface was carried out in two steps. The first step was treatment of the zeolite with 2 M HCl. This acid treatment of the zeolite increased its affinity for neutral molecules such as surface-active amines. The second step of the modification was the adsorption of oleylamine on the acid treated zeolite. Four types of organo-mineral complexes were prepared and their anion adsorption properties were compared to those of organo-zeolite. The adsorption of sulphate, bichromate and dihydrogenphosphate anions on the organo-mineral complexes was investigated. The anion adsorption measurements showed that the most efficient adsorbent for anion water pollutants was the primary amine modified H+-form zeolite.

  3. Two independent anion transport systems in rabbit mandibular salivary glands

    DEFF Research Database (Denmark)

    Novak, I; Young, J A

    1986-01-01

    Cholinergically stimulated Cl and HCO3 transport in perfused rabbit mandibular glands has been studied with extracellular anion substitution and administration of transport inhibitors. In glands perfused with HCO3-free solutions, replacement of Cl with other anions supported secretion in the foll......Cholinergically stimulated Cl and HCO3 transport in perfused rabbit mandibular glands has been studied with extracellular anion substitution and administration of transport inhibitors. In glands perfused with HCO3-free solutions, replacement of Cl with other anions supported secretion...... stimulated secretion by about 30%, but when infused in addition to furosemide (0.1 mmol/l), it inhibited by about 20%. Amiloride (1.0 mmol/l) caused no inhibition. The results suggest that there are at least three distinct carriers in the rabbit mandibular gland. One is a furosemide-sensitive Na-coupled Cl...

  4. Unmeasured anions and mortality in critically ill patients in 2016.

    Science.gov (United States)

    Kotake, Yoshifumi

    2016-01-01

    The presence of acid-base disturbances, especially metabolic acidosis may negatively affect the outcome of critically ill patients. Lactic acidosis is the most frequent etiology and has largest impact on the prognosis. Since lactate measurement might not have always been available at bedside, it had been regarded as one of the unmeasured anions. Therefore, anion gap and strong ion gap has been used to as a surrogate of lactate concentration. From this perspective, the relationship between either anion gap or strong ion gap and mortality has been explored. Then, lactate became routinely measurable at bedside and the direct comparison between directly measured lactate and these surrogate parameters can be possible. Currently available evidence suggests that directly measured lactate has larger prognostic ability for mortality than albumin-corrected anion gap and strong ion gap without lactate. In this commentary, the rationale and possible clinical implications of these findings are discussed.

  5. Approach to the Patient With a Negative Anion Gap.

    Science.gov (United States)

    Emmett, Michael

    2016-01-01

    When anion gap calculation generates a very small or negative number, an explanation must be sought. Sporadic (nonreproducible) measurement errors and systematic (reproducible) laboratory errors must be considered. If an error is ruled out, 2 general possibilities exist. A true anion gap reduction can be generated by either reduced concentrations of unmeasured anions such as albumin or increased concentrations of unmeasured cations such as magnesium, calcium, or lithium. This teaching case describes a patient with aspirin (salicylate) poisoning whose anion gap was markedly reduced (-47 mEq/L). The discussion systematically reviews the possibilities and provides the explanation for this unusual laboratory result. Copyright © 2016 National Kidney Foundation, Inc. Published by Elsevier Inc. All rights reserved.

  6. Radiosensitization of microorganisms by radical anions

    International Nuclear Information System (INIS)

    Schubert, J.; Stegeman, H.; Groneman, A.

    1981-01-01

    The inactivation of Streptococcus faecalis by radiolytically generated selective inorganic radical anions was investigated. The Br 2 - radical, but not (CNS) 2 - , had a pronounced radiosensitizing action. In gamma-irradiated solutions at pH7.0, the radiosensitization of a variety of scavenging systems was studied. Among these the D 10 for N 2 /Br - was 0.082 kGy while N 2 O/CNS - = 0.35 kGy, N 2 O = 0.25 kGy, N 2 = 0.47, and O 2 = 0.16 kGy. As shown previously, inactivation in N 2 O/Br - systems is due mainly to Br 2 and HOBr. From the variation of the inactivation with pH by Br 2 - and (CNS) 2 - it was deduced that tyrosine is crucial for the survival of S. faecalis via inactivation of enzymes with essential tyrosine residues such as aldolase and lipoyl dehydrogenase which are presumably needed to make energy available for DNA repair. Studies with a variety of scavengers also revealed that the t-butanol radical produced some radiosensitization of S. faecalis while the damaging effect of e - sub(aq) was much less than OH as shown by the D 10 at pH 7.0; N 2 /t-butanol = 0.32 and N 2 /ethanol = 0.71. The radiosensitizing action of Br 2 - in a natural environment containing sewage sludge was also determined, using the faecal streptococcal group as test organisms. (author)

  7. (100) faceted anion voids in electron irradiated fluorite

    International Nuclear Information System (INIS)

    Johnson, E.

    1979-01-01

    High fluence electron irradiation of fluorite crystals in the temperature range 150 to 320 K results in formation of a simple cubic anion void superlattice. Above 320 K the damage structure changes to a random distribution of large [001] faceted anion voids. This voidage behaviour, similar to that observed in a range of irradiated metals, is discussed in terms points defect rather than conventional colour centre terminology. (Auth.)

  8. GAS-GRAIN MODELS FOR INTERSTELLAR ANION CHEMISTRY

    International Nuclear Information System (INIS)

    Cordiner, M. A.; Charnley, S. B.

    2012-01-01

    Long-chain hydrocarbon anions C n H – (n = 4, 6, 8) have recently been found to be abundant in a variety of interstellar clouds. In order to explain their large abundances in the denser (prestellar/protostellar) environments, new chemical models are constructed that include gas-grain interactions. Models including accretion of gas-phase species onto dust grains and cosmic-ray-induced desorption of atoms are able to reproduce the observed anion-to-neutral ratios, as well as the absolute abundances of anionic and neutral carbon chains, with a reasonable degree of accuracy. Due to their destructive effects, the depletion of oxygen atoms onto dust results in substantially greater polyyne and anion abundances in high-density gas (with n H 2 ∼>10 5 cm –3 ). The large abundances of carbon-chain-bearing species observed in the envelopes of protostars such as L1527 can thus be explained without the need for warm carbon-chain chemistry. The C 6 H – anion-to-neutral ratio is found to be most sensitive to the atomic O and H abundances and the electron density. Therefore, as a core evolves, falling atomic abundances and rising electron densities are found to result in increasing anion-to-neutral ratios. Inclusion of cosmic-ray desorption of atoms in high-density models delays freeze-out, which results in a more temporally stable anion-to-neutral ratio, in better agreement with observations. Our models include reactions between oxygen atoms and carbon-chain anions to produce carbon-chain-oxide species C 6 O, C 7 O, HC 6 O, and HC 7 O, the abundances of which depend on the assumed branching ratios for associative electron detachment.

  9. Gas-Grain Models for Interstellar Anion Chemistry

    Science.gov (United States)

    Cordiner, M. A.; Charnely, S. B.

    2012-01-01

    Long-chain hydrocarbon anions C(sub n) H(-) (n = 4, 6, 8) have recently been found to be abundant in a variety of interstellar clouds. In order to explain their large abundances in the denser (prestellar/protostellar) environments, new chemical models are constructed that include gas-grain interactions. Models including accretion of gas-phase species onto dust grains and cosmic-ray-induced desorption of atoms are able to reproduce the observed anion-to-neutral ratios, as well as the absolute abundances of anionic and neutral carbon chains, with a reasonable degree of accuracy. Due to their destructive effects, the depletion of oxygen atoms onto dust results in substantially greater polyyne and anion abundances in high-density gas (with n(sub H2) approx > / cubic cm). The large abundances of carbon-chain-bearing species observed in the envelopes of protostars such as L1527 can thus be explained without the need for warm carbon-chain chemistry. The C6H(-) anion-to-neutral ratio is found to be most sensitive to the atomic O and H abundances and the electron density. Therefore, as a core evolves, falling atomic abundances and rising electron densities are found to result in increasing anion-to-neutral ratios. Inclusion of cosmic-ray desorption of atoms in high-density models delays freeze-out, which results in a more temporally stable anion-to-neutral ratio, in better agreement with observations. Our models include reactions between oxygen atoms and carbon-chain anions to produce carbon-chain-oxide species C6O, C7O, HC6O, and HC7O, the abundances of which depend on the assumed branching ratios for associative electron detachment

  10. Photoelectron spectroscopic study of carbon aluminum hydride cluster anions

    Science.gov (United States)

    Zhang, Xinxing; Wang, Haopeng; Ganteför, Gerd; Eichhorn, Bryan W.; Kiran, Boggavarapu; Bowen, Kit H.

    2016-10-01

    Numerous previously unknown carbon aluminum hydride cluster anions were generated in the gas phase, identified by time-of-flight mass spectrometry and characterized by anion photoelectron spectroscopy, revealing their electronic structure. Density functional theory calculations on the CAl5-9H- and CAl5-7H2- found that several of them possess unusually high carbon atom coordination numbers. These cluster compositions have potential as the basis for new energetic materials.

  11. Synthesis of Pyridoacridines through Anionic Cascade Ring Closure

    DEFF Research Database (Denmark)

    Petersen, I.N.; Kristensen, Jesper Langgaard

    2014-01-01

    A new synthesis of 13-deazaascididemin (AK-37) based on a recently developed anionic cascade ring closure is presented. Although the isolated yields are modest, the approach provides ready access to new substituted derivatives of 13-deazaascididemin.......A new synthesis of 13-deazaascididemin (AK-37) based on a recently developed anionic cascade ring closure is presented. Although the isolated yields are modest, the approach provides ready access to new substituted derivatives of 13-deazaascididemin....

  12. The gecko visual pigment: the anion hypsochromic effect.

    Science.gov (United States)

    Crescitelli, F; Karvaly, B

    1991-01-01

    The 521-pigment in the retina of the Tokay gecko (Gekko gekko) readily responds to particular physical and chemical changes in its environment. When solubilized in chloride deficient state the addition of Class I anions (Cl-, Br-) induces a bathochromic shift of the absorption spectrum. Class II anions (NO3-, IO3-, N3-, OCN-, SCN-, SeCN-, N(CN)2-), which exhibit ambidental properties, cause an hypsochromic shift. Class III anions (F-, I-, NO2-, CN-, AsO3-, SO2(4-), S2O2(3-) have no spectral effect on the 521-pigment. Cations appear to have no influence on the pigment absorption and Class I anions prevent or reverse the hypsochromic shift caused by Class II anions. It is suggested that the spectral displacements reflect specific changes in the opsin conformation, which alter the immediate (dipolar) environment of the retinal chromophore. The protein conformation seems to promote excited-state processes most in the native 521-pigment state and least in the presence of Class II anions. This in turn suggests that the photosensitivity of the 521-pigment is controlled by the excited rather than by the ground-state properties of the pigment.

  13. Delta- and gamma-tocotrienol isomers are potent in inhibiting inflammation and endothelial activation in stimulated human endothelial cells

    Directory of Open Access Journals (Sweden)

    Suhaila Muid

    2016-07-01

    Full Text Available Background: Tocotrienols (TCTs are more potent antioxidants than α-tocopherol (TOC. However, the effectiveness and mechanism of the action of TCT isomers as anti-atherosclerotic agents in stimulated human endothelial cells under inflammatory conditions are not well established. Aims: 1 To compare the effects of different TCT isomers on inflammation, endothelial activation, and endothelial nitric oxide synthase (eNOS. 2 To identify the two most potent TCT isomers in stimulated human endothelial cells. 3 To investigate the effects of TCT isomers on NFκB activation, and protein and gene expression levels in stimulated human endothelial cells. Methods: Human umbilical vein endothelial cells were incubated with various concentrations of TCT isomers or α-TOC (0.3–10 µM, together with lipopolysaccharides for 16 h. Supernatant cells were collected and measured for protein and gene expression of cytokines (interleukin-6, or IL-6; tumor necrosis factor-alpha, or TNF-α, adhesion molecules (intercellular cell adhesion molecule-1, or ICAM-1; vascular cell adhesion molecule-1, or VCAM-1; and e-selectin, eNOS, and NFκB. Results: δ-TCT is the most potent TCT isomer in the inhibition of IL-6, ICAM-1, VCAM-1, and NFκB, and it is the second potent in inhibiting e-selectin and eNOS. γ-TCT isomer is the most potent isomer in inhibiting e-selectin and eNOS, and it is the second most potent in inhibiting is IL-6, VCAM-1, and NFκB. For ICAM-1 protein expression, the most potent is δ-TCT followed by α-TCT. α- and β-TCT inhibit IL-6 at the highest concentration (10 µM but enhance IL-6 at lower concentrations. γ-TCT markedly increases eNOS expression by 8–11-fold at higher concentrations (5–10 µM but exhibits neutral effects at lower concentrations. Conclusion: δ- and γ-TCT are the two most potent TCT isomers in terms of the inhibition of inflammation and endothelial activation whilst enhancing eNOS, possibly mediated via the NFκB pathway. Hence

  14. Site-specific binding of a water molecule to the sulfa drugs sulfamethoxazole and sulfisoxazole: a laser-desorption isomer-specific UV and IR study.

    Science.gov (United States)

    Uhlemann, Thomas; Seidel, Sebastian; Müller, Christian W

    2018-02-20

    To determine the preferred water molecule binding sites of the polybasic sulfa drugs sulfamethoxazole (SMX) and sulfisoxazole (SIX), we have studied their monomers and monohydrated complexes through laser-desorption conformer-specific UV and IR spectroscopy. Both the SMX and SIX monomer adopt a single conformer in the molecular beam. On the basis of their conformer-specific IR spectra in the NH stretch region, these conformers were assigned to the SMX and SIX global minimum structures, both exhibiting a staggered sulfonamide group and an intramolecular C-HO[double bond, length as m-dash]S hydrogen bond. The SMX-H 2 O and SIX-H 2 O complexes each adopt a single isomer in the molecular beam. Their isomeric structures were determined based on their isomer-specific IR spectra in the NH/OH stretch region. Quantum Theory of Atoms in Molecules analysis of the calculated electron densities revealed that in the SMX-H 2 O complex the water molecule donates an O-HN hydrogen bond to the heterocycle nitrogen atom and accepts an N-HO hydrogen bond from the sulfonamide NH group. In the SIX-H 2 O complex, however, the water molecule does not bind to the heterocycle but instead donates an O-HO[double bond, length as m-dash]S hydrogen bond to the sulfonamide group and accepts an N-HO hydrogen bond from the sulfonamide NH group. Both water complexes are additionally stabilized by a C ph -HOH 2 hydrogen bond. Interacting Quantum Atoms analysis suggests that all intermolecular hydrogen bonds are dominated by the short-range exchange-correlation contribution.

  15. Estimating unmeasured anions in critically ill patients: anion-gap, base-deficit, and strong-ion-gap.

    Science.gov (United States)

    Story, D A; Poustie, S; Bellomo, R

    2002-11-01

    We used 100 routine blood samples from critically ill patients to establish whether correcting the anion-gap and base-deficit for decreased plasma albumin improves agreement with the strong-ion-gap for estimating unmeasured anions and whether the modifications increase the proportion of samples with levels of anion-gap or base-deficit above the reference ranges. We used Bland-Altman analyses to compare the methods of estimating unmeasured ions. Compared with the strong-ion-gap, modification reduced the limits of agreement for both the anion-gap and the base-deficit. The bias for the base-deficit was also reduced but the bias for the anion-gap was increased. The proportion of samples with an anion-gap > 22 meq.l(-1) increased from 4 to 29% (p 5 meq.l(-1) increased from 8 to 42% (p < 0.001). Consequently, metabolic acidosis from unmeasured ions in critically ill patients maybe more frequent than often recognised.

  16. Tamoxifen Isomers and Metabolites Exhibit Distinct Affinity and Activity at Cannabinoid Receptors: Potential Scaffold for Drug Development.

    Science.gov (United States)

    Ford, Benjamin M; Franks, Lirit N; Radominska-Pandya, Anna; Prather, Paul L

    2016-01-01

    Tamoxifen (Tam) is a selective estrogen receptor (ER) modulator (SERM) that is an essential drug to treat ER-positive breast cancer. Aside from known actions at ERs, recent studies have suggested that some SERMs like Tam also exhibit novel activity at cannabinoid subtype 1 and 2 receptors (CB1R and CB2Rs). Interestingly, cis- (E-Tam) and trans- (Z-Tam) isomers of Tam exhibit over a 100-fold difference in affinity for ERs. Therefore, the current study assessed individual isomers of Tam and subsequent cytochrome P450 metabolic products, 4-hydroxytamoxifen (4OHT) and 4-hydroxy-N-desmethyl tamoxifen (End) for affinity and activity at CBRs. Results showed that Z-4OHT, but not Z-Tam or Z-End, exhibits higher affinity for both CB1 and CB2Rs relative to the E-isomer. Furthermore, Z- and E-isomers of Tam and 4OHT show slightly higher affinity for CB2Rs, while both End isomers are relatively CB1R-selective. When functional activity was assessed by G-protein activation and regulation of the downstream effector adenylyl cyclase, all isomers examined act as full CB1 and CB2R inverse agonists. Interestingly, Z-Tam appears to be more efficacious than the full inverse agonist AM630 at CB2Rs, while both Z-Tam and Z-End exhibit characteristics of insurmountable antagonism at CB1 and CB2Rs, respectively. Collectively, these results suggest that the SERMs Tam, 4OHT and End elicit ER-independent actions via CBRs in an isomer-specific manner. As such, this novel structural scaffold might be used to develop therapeutically useful drugs for treatment of a variety of diseases mediated via CBRs.

  17. Tamoxifen Isomers and Metabolites Exhibit Distinct Affinity and Activity at Cannabinoid Receptors: Potential Scaffold for Drug Development.

    Directory of Open Access Journals (Sweden)

    Benjamin M Ford

    Full Text Available Tamoxifen (Tam is a selective estrogen receptor (ER modulator (SERM that is an essential drug to treat ER-positive breast cancer. Aside from known actions at ERs, recent studies have suggested that some SERMs like Tam also exhibit novel activity at cannabinoid subtype 1 and 2 receptors (CB1R and CB2Rs. Interestingly, cis- (E-Tam and trans- (Z-Tam isomers of Tam exhibit over a 100-fold difference in affinity for ERs. Therefore, the current study assessed individual isomers of Tam and subsequent cytochrome P450 metabolic products, 4-hydroxytamoxifen (4OHT and 4-hydroxy-N-desmethyl tamoxifen (End for affinity and activity at CBRs. Results showed that Z-4OHT, but not Z-Tam or Z-End, exhibits higher affinity for both CB1 and CB2Rs relative to the E-isomer. Furthermore, Z- and E-isomers of Tam and 4OHT show slightly higher affinity for CB2Rs, while both End isomers are relatively CB1R-selective. When functional activity was assessed by G-protein activation and regulation of the downstream effector adenylyl cyclase, all isomers examined act as full CB1 and CB2R inverse agonists. Interestingly, Z-Tam appears to be more efficacious than the full inverse agonist AM630 at CB2Rs, while both Z-Tam and Z-End exhibit characteristics of insurmountable antagonism at CB1 and CB2Rs, respectively. Collectively, these results suggest that the SERMs Tam, 4OHT and End elicit ER-independent actions via CBRs in an isomer-specific manner. As such, this novel structural scaffold might be used to develop therapeutically useful drugs for treatment of a variety of diseases mediated via CBRs.

  18. Occurrence, fluxes and sources of perfluoroalkyl substances with isomer analysis in the snow of northern China

    Energy Technology Data Exchange (ETDEWEB)

    Shan, Guoqiang; Chen, Xinwei; Zhu, Lingyan, E-mail: zhuly@nankai.edu.cn

    2015-12-15

    Highlights: • Relatively high levels of PFASs were present in the snow in northern China in 2013. • Particulate bound PFASs contributed 21.5–56.2% to the total PFASs in snow. • Particulate matters are vital for PFASs transport and deposition in urban atmosphere. • Partitioning of PFASs between particulate and dissolved phase was related to carbon chain length. • Isomer profiles in snow suggested that airborne PFASs were mainly from direct release. - Abstract: In this study, perfluoroalkyl substances (PFASs) and the isomers of perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) were analyzed in fresh snow samples collected from 19 cities in northern China, 2013. The levels of total PFASs in the snow samples were 33.5–229 ng/L, suggesting heavy atmospheric pollution of PFASs in northern China. PFOA (9.08–107 ng/L), PFOS (3.52–54.3 ng/L), perfluoroheptanoate (PFHpA) (3.66–44.8 ng/L), and perfluorohexanoate (PFHxA) (3.21–23.6 ng/L) were predominant with a summed contribution of 82% to the total PFASs. The particulate matters (PMs) associated PFASs contributed 21.5–56.2% to the total PFASs in the snow, suggesting PMs are vital for the transport and deposition of airborne PFASs. Partitioning of PFASs between PM and dissolved phases was dependent on the carbon chain length and end functional groups. Isomer profiles of PFOA and PFOS in the snow were in agreement with the signature of the historical 3 M electrochemical fluorination (ECF) products, suggesting that the ECF products were still produced and used in China. Further source analysis showed that the airborne PFASs in urban area were mainly due to direct release rather than degradation of their precursors.

  19. Feeding of the 1 1/2- isomers in stable Ir and Au isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Fotiadis, Nikolaos [Los Alamos National Laboratory; Nelson, Ronald O [Los Alamos National Laboratory; Devlin, Matthew [Los Alamos National Laboratory; Holloway, Shannon T [Los Alamos National Laboratory; Kawano, Toshihiko [Los Alamos National Laboratory; Talou, Patrick [Los Alamos National Laboratory; Chadwick, Mark B [Los Alamos National Laboratory; Becker, John A [LLNL; Garrett, Paul E [U GUELPH, CANADA

    2008-01-01

    Excited states were studied and absolute partial {gamma}-ray cross sections were measured using the ({eta}, {eta}'{gamma}) reaction in {sup 191}Ir, {sup 193}Ir and {sup 197}Au. A Compton-suppressed germanium-detector array (GEANIE) for {gamma}-ray spectroscopy and the broad-spectrum pulsed neutron source of the Los Alamos Neutron Science Center's WNR facility were used for the measurement. The energy of the incident neutrons was determined using the time-of-flight technique. Absolute partial {gamma}-ray cross sections were measured up to incident neutron energy of 20 MeV for several transitions feeding directly the 1 1/2- isomers and ground states in {sup 191}Ir, {sup 193}Ir and {sup 197}Au. The feeding of the 1 1/2- isomers, which originate from the odd proton occupying the h{sub 1 1/2} orbital, was found for the three targets to be very similar and increasing relative to the feeding of the corresponding ground state with increasing neutron energy up to E{sub n} {approx} 10 MeV. Above this neutron energy the opening of the (n, 2{sub n}) reaction channel strongly affects the population of the isomers and leads to a decrease of their relative population compared to the population of the ground states. The experimental results are compared with theoretical predictions from the GNASH reaction model calculation implementing a version of the spin distribution for the pre-equilibrium reaction piece with either a compound nucleus spin distribution (CN-GNASH) or a Feshbach-Kerman-Koonin (FKK-GNASH) quantum mechanical spin distribution. The effects of the spin cutoff parameter values on the population of states are examined. Evidence is presented that FKK-GNASH provides a description of the experimental data that mitigates the need for adjustment of the level density parameter to fit the data.

  20. In vitro neurotoxic hazard characterization of different tricresyl phosphate (TCP) isomers and mixtures.

    Science.gov (United States)

    Duarte, Daniel J; Rutten, Joost M M; van den Berg, Martin; Westerink, Remco H S

    2017-03-01

    Exposure to tricresyl phosphates (TCPs), via for example contaminated cabin air, has been associated with health effects including the so-called aerotoxic syndrome. While TCP neurotoxicity is mainly attributed to ortho-isomers like tri-ortho-cresyl phosphate (ToCP), recent exposure and risk assessments indicate that ToCP levels in cabin air are very low. However, the neurotoxic potential of non-ortho TCP isomers and TCP mixtures is largely unknown. We therefore measured effects of exposure (up to 48h) to different TCP isomers, mixtures and the metabolite of ToCP (CBDP: cresyl saligenin phosphate) on cell viability and mitochondrial activity, spontaneous neuronal electrical activity, and neurite outgrowth in primary rat cortical neurons. The results demonstrate that exposure to TCPs (24-48h, up to 10μM) increases mitochondrial activity, without affecting cell viability. Effects of acute TCP exposure (30min) on neuronal electrical activity are limited. However, electrical activity is markedly decreased for the majority of TCPs (10μM) following 48h exposure. Additional preliminary data indicate that exposure to TCPs (48h, 10μM) did not affect the number of neurites per cell or average neurite length, except for TmCP and the analytical TCP mixture (Sigma) that induced a reduction of average neurite length. The combined neurotoxicity data demonstrate that the different TCPs, including ToCP, are roughly equipotent and a clear structure-activity relation is not apparent for the studied endpoints. The no-observed-effect-concentrations (1μM) are well above current exposure levels indicating limited neurotoxic health risk, although exposures may have been higher in the past. Moreover, prolonged and/or repeated exposure to TCPs may exacerbate the observed neurotoxic effects, which argues for additional research. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Occurrence, fluxes and sources of perfluoroalkyl substances with isomer analysis in the snow of northern China

    International Nuclear Information System (INIS)

    Shan, Guoqiang; Chen, Xinwei; Zhu, Lingyan

    2015-01-01

    Highlights: • Relatively high levels of PFASs were present in the snow in northern China in 2013. • Particulate bound PFASs contributed 21.5–56.2% to the total PFASs in snow. • Particulate matters are vital for PFASs transport and deposition in urban atmosphere. • Partitioning of PFASs between particulate and dissolved phase was related to carbon chain length. • Isomer profiles in snow suggested that airborne PFASs were mainly from direct release. - Abstract: In this study, perfluoroalkyl substances (PFASs) and the isomers of perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) were analyzed in fresh snow samples collected from 19 cities in northern China, 2013. The levels of total PFASs in the snow samples were 33.5–229 ng/L, suggesting heavy atmospheric pollution of PFASs in northern China. PFOA (9.08–107 ng/L), PFOS (3.52–54.3 ng/L), perfluoroheptanoate (PFHpA) (3.66–44.8 ng/L), and perfluorohexanoate (PFHxA) (3.21–23.6 ng/L) were predominant with a summed contribution of 82% to the total PFASs. The particulate matters (PMs) associated PFASs contributed 21.5–56.2% to the total PFASs in the snow, suggesting PMs are vital for the transport and deposition of airborne PFASs. Partitioning of PFASs between PM and dissolved phases was dependent on the carbon chain length and end functional groups. Isomer profiles of PFOA and PFOS in the snow were in agreement with the signature of the historical 3 M electrochemical fluorination (ECF) products, suggesting that the ECF products were still produced and used in China. Further source analysis showed that the airborne PFASs in urban area were mainly due to direct release rather than degradation of their precursors.

  2. Anion gap, anion gap corrected for albumin, and base deficit fail to accurately diagnose clinically significant hyperlactatemia in critically ill patients.

    Science.gov (United States)

    Chawla, Lakhmir S; Jagasia, Dhiraj; Abell, Lynn M; Seneff, Michael G; Egan, Melinda; Danino, Natale; Nguyen, Aline; Ally, Mazer; Kimmel, Paul L; Junker, Christopher

    2008-01-01

    Anion gap, anion gap corrected for serum albumin, and base deficit are often used as surrogates for measuring serum lactate. None of these surrogates is postulated to predict hyperlactatemia in the critically ill. We prospectively collected data from September 2004 through August 2005 for 1381 consecutive admissions. Patients with renal disease, ketoacidosis, or toxic ingestion were excluded. Anion gap, anion gap corrected for albumin, and base deficit were calculated for all patients. We identified 286 patients who met our inclusion or exclusion criteria. The receiver-operating characteristic area under the curve for the prediction of hyperlactatemia for anion gap, anion gap corrected for albumin, and base deficit were 0.55, 0.57, and 0.64, respectively. Anion gap, anion gap corrected for albumin, and base deficit do not predict the presence or absence of clinically significant hyperlactatemia. Serum lactate should be measured in all critically ill adults in whom hypoperfusion is suspected.

  3. Discovery of Interstellar Anions in Cepheus and Auriga

    Science.gov (United States)

    Cordiner, M. A.; Charnely, S. B.; Buckle, J. V.; Walsh, C.

    2011-01-01

    We report the detection of microwave emission lines from the hydrocarbon anion C6H(-) and its parent neutral C6H in the star-forming region LI251 A (in Cepheus), and the pre-stellar core LI512 (in Auriga). The carbon chain-bearing species C4H, HC3N, HC5N, HC7N, and C3S are also detected in large abundances. The observations of L1251A constitute the first detections of anions and long-chain polyynes and cyanopolyynes (with more than five carbon atoms) in the Cepheus Flare star-forming region, and the first detection of anions in the vicinity of a protostar outside of the Taurus molecular cloud complex, indicating a possible wider importance for anions in the chemistry of star formation. Rotational excitation temperatures have been derived from the HC3N hyperfine structure lines and are found to be 6.2 K for L1251A and 8.7 K for LI5l2. The anion-to-neutral ratios are 3.6% and 4.1%, respectively, which are within the range of values previously observed in the interstellar medium, and suggest a relative uniformity in the processes governing anion abundances in different dense interstellar clouds. This research contributes toward the growing body of evidence that carbon chain anions are relatively abundant in interstellar clouds throughout the Galaxy, but especially in the regions of relatively high density and high depletion surrounding pre-stellar cores and young, embedded protostars.

  4. Anion gap among patients of multiple myeloma and normal individuals.

    Science.gov (United States)

    Mansoor, Shireen; Siddiqui, Imran; Adil, Salman; Nabi Kakepoto, Ghulam; Fatmi, Zafar; Ghani, Farooq

    2007-02-01

    To compare the Anion gap between patients of multiple myeloma and normal individuals presenting at a tertiary care hospital. This is a matched case-control study conducted at Aga Khan University Hospital, Karachi, from July 10, 2004 to April 30, 2006. The anion gap (AG) from the medical records of the 82 diagnosed cases of multiple myeloma (MM) and 104 controls were compared. Immunoglobulins (IgG and IgA) were measured by array nephelometric assay. Staging for MM patients were performed based on Salmon-Durie method. AGs were compared by independent sample t-test. Pearson coefficient of correlation was used to correlate paraprotein IgG concentration and anion gap. : Of the 186 study subjects (82 cases and 104 controls), 70% were males and 30% were females. The mean ages of MM and controls were 59.68+/-11.94 and 60+/-9.2 years respectively. There was a significant difference in mean AG, 11.2+/-1.7 mmol/L in control group (panion gap of 8.7+/-1.7 in stage I, 7.93+/-0.47 in stage II and 5.65+/-0.31 in stage III. A significant correlation was found in IgG myeloma when anion gap was expressed as a function of the serum monoclonal protein concentration. The anion gap is significantly lower in multiple myeloma patients compared to controls. Lowered anion gap is more specific feature of the IgG type MM. We suggest that correlation of AG with the disease severity and with paraproteins concentration could potentially be useful in monitoring patients for disease progression. However, longitudinal studies are required to confirm the utility of anion gap in monitoring patients with MM.

  5. Uncertainty budget for determinations of mean isomer shift from Mössbauer spectra

    DEFF Research Database (Denmark)

    Fock, Jeppe; Bogart, Lara Katrina; Posth, Oliver

    2016-01-01

    The magnetite/maghemite content within iron oxide nanoparticles can be determined using the mean isomer shift (δ¯¯). However, accurate characterisation of the composition is limited by the uncertainty associated with δ¯¯. We have identified four independent sources of uncertainty and developed...... a quantitative expression for the uncertainty budget. Sources of uncertainty are categorised as follows: that from the fitting of the Mössbauer spectrum (σ fit), that of the calibration of the α-Fe reference spectrum (σ cal), thermal corrections to the spectrum due to second order Doppler shift (SODS) (σ Δδ...

  6. Radioactive isotope and isomer separation with using light induced drift effect

    International Nuclear Information System (INIS)

    Hradecny, C.; Slovak, J.; Tethal, T.; Ermolaev, I.M.; Shalagin, A.M.

    1991-01-01

    The isotope separation with using light induced drift (LID) is discussed. The basic theoretical characteristics of the method are deduced: separation simultaneously with an arbitrary high enrichment and without significant losses; separation productivity up to 100 μg/h. These characteristics are sufficient and very convenient for separation of expensive radioactive isotopes and isomers which are applied in medicine and science. The first experimental separation of the radioactive isotopes ( 22,24 Na) by using the LID effect is reported. 13 refs.; 5 figs

  7. Contemplation on some cyclic N8 isomers-A DFT treatment

    Directory of Open Access Journals (Sweden)

    Lemi Türker

    2018-02-01

    Full Text Available Various cyclic N8 isomers are considered at the levels of B3LYP/6–311++G(d,p and B3LYP/cPVTZ. Some energies and molecular orbital properties are obtained. The structures are found to be stable in the singlet state but mostly unstable in the triplet. The heats of formation values calculated by means of T1 recipe reveals that they are highly endothermic. NICS(0 values have been calculated and aromaticity/antiaromaticity of the rings are discussed. Additionally, theoretical IR,UV-VIS spectra and the calculated impulse values have been obtained.

  8. Structure of high-spin isomers in trans-lead nuclei

    International Nuclear Information System (INIS)

    Dracoulis, G.D.

    1990-01-01

    The structure of core-excited high-spin isomers in the N ≤ 126 isotopes of At, Rn and Fr is reviewed. New results for high-spin states in 211 Rn and 212 Rn, approaching the limit of the available angular momentum from the valence particles, are presented. The recurring experimental feature is decay by very enhanced E3 transitions. These, and other properties are explained in a natural way by inclusion of particle-octupole vibration coupling, in a semi-empirical shell model. The deformed independent particle model is not successful in explaining these features. 40 refs., 4 tabs., 11 figs

  9. Cyclic Versus Linear Isomers Produced by Reaction of the Methylidyne Radical (CH) with Small Unsaturated Hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Goulay, Fabien; Trevitt, Adam J.; Meloni, Giovanni; Selby, Talitha M.; Osborn, David L.; Taatjes, Craig A.; Vereecken, Luc; Leone, Stephen R.

    2008-12-05

    The reactions of the methylidyne radical (CH) with ethylene, acetylene, allene, and methylacetylene are studied at room temperature using tunable vacuum ultraviolet (VUV) photoionization and time-resolved mass spectrometry. The CH radicals are prepared by 248 nm multiphoton photolysis of CHBr3 at 298 K and react with the selected hydrocarbon in a helium gas flow. Analysis of photoionization efficiency versus VUV photon wavelength permits isomer-specific detection of the reaction products and allows estimation of the reaction product branching ratios. The reactions proceed by either CH insertion or addition followed by H atom elimination from the intermediate adduct. In the CH + C2H4 reaction the C3H5 intermediate decays by H atom loss to yield 70(+-8)percent allene, 30(+-8)percent methylacetylene and less than 10percent cyclopropene, in agreement with previous RRKM results. In the CH + acetylene reaction, detection of mainly the cyclic C3H2 isomer is contrary to a previous RRKM calculation that predicted linear triplet propargylene to be 90percent of the total H-atom co-products. High-level CBS-APNO quantum calculations and RRKM calculation for the CH + C2H2 reaction presented in this manuscript predict a higher contribution of the cyclic C3H2 (27.0percent) versus triplet propargylene (63.5percent) than these earlier predictions. Extensive calculations on the C3H3 and C3H2D system combined with experimental isotope ratios for the CD + C2H2 reaction indicate that H-atom assisted isomerization in the present experiments is responsible for the discrepancy between the RRKM calculations and the experimental results. Cyclic isomers are also found to represent 30(+-6)percent of the detected products in the case of CH + methylacetylene, together with 33(+-6)percent 1,2,3-butatriene and 37(+-6)percent vinylacetylene. The CH + allene reaction gives 23(+-5)percent 1,2,3-butatriene and 77(+-5)percent vinylacetylene, whereas cyclic isomers are produced below the detection limit

  10. Efectos del entrenamiento de fuerza isométrica sobre la presión arterial

    OpenAIRE

    Velázquez Díaz, Daniel

    2015-01-01

    La hipertensión arterial es un problema de salud pública, que afecta a un número muy elevado de personas en todo el mundo. Por ello creo de interés social investigaciones en esta enfermedad para mejorar el control, conocimiento y tratamiento de la misma. En esta revisión se han analizado numerosas publicaciones con el objetivo de estudiar los efectos del entrenamiento de fuerza isométrica (FI) sobre la presión arterial (PA) y para comprobar si es seguro trabajar este tipo de ejercicio físico ...

  11. Proton radioactivity: the case for 53m Co proton-emitter isomer

    International Nuclear Information System (INIS)

    Tavares, O.A.P.; Medeiros, E.L.

    2010-01-01

    The partial proton emission half-life for 53m Co unstable isomer is re-examined in the framework of a semiempirical model based on tunneling through a Coulomb-plus centrifugal- plus-overlapping potential barrier within the spherical nucleus approximation. It is shown that the known measured half-life value of 17 s is compatible with a large prolate shape for 53m Co proton emitter and a high angular momentum ι = 11 assigned to the proton transition to the ground-state of 52 Fe. (author)

  12. Quadrupole moments of the 12+ isomers in 188Hg and 190Hg

    International Nuclear Information System (INIS)

    Dracoulis, G.D.; Lonnroth, T.; Vajda, S.; Dafni, E.; Schatz, G.

    1984-01-01

    The electric quadrupole interaction of the 12 + isomers in 188 Hg and 190 Hg has been measured in solid Hg. The quadrupole moments deduced, vertical strokeQ[ 188 Hg(12 + )]vertical stroke = 91(11) e fm 2 and vertical strokeQ[ 190 Hg(12 + )]vertical stroke = 117(14) e fm 2 suggest a possible change in γ-deformation due to the rotation alignment of the isub(13/2) quasi-neutrons. The temperature dependence of the electric field gradient tensor in Hg was also determined. (orig.)

  13. Simultaneous Analysis of Monovalent Anions and Cations with a Sub-Microliter Dead-Volume Flow-Through Potentiometric Detector for Ion Chromatography

    Science.gov (United States)

    Dumanli, Rukiye; Attar, Azade; Erci, Vildan; Isildak, Ibrahim

    2016-01-01

    A microliter dead-volume flow-through cell as a potentiometric detector is described in this article for sensitive, selective and simultaneous detection of common monovalent anions and cations in single column ion chromatography for the first time. The detection cell consisted of less selective anion- and cation-selective composite membrane electrodes together with a solid-state composite matrix reference electrode. The simultaneous separation and sensitive detection of sodium (Na+), potassium (K+), ammonium (NH4+), chloride (Cl−) and nitrate (NO3−) in a single run was achieved by using 98% 1.5 mM MgSO4 and 2% acetonitrile eluent with a mixed-bed ion-exchange separation column without suppressor column system. The separation and simultaneous detection of the anions and cations were completed in 6 min at the eluent flow-rate of 0.8 mL/min. Detection limits, at S/N = 3, were ranged from 0.2 to 1.0 µM for the anions and 0.3 to 3.0 µM for the cations, respectively. The developed method was successfully applied to the simultaneous determination of monovalent anions and cations in several environmental and biological samples. PMID:26786906

  14. Opposite effects of different hexachlorocyclohexane (lindane) isomers on cerebellar cyclic GMP: relation of cyclic GMP accumulation to seizure activity

    International Nuclear Information System (INIS)

    Fishman, B.E.; Gianutsos, G.

    1987-01-01

    A number of different depressant and convulsant agents have been shown to alter accumulation of cerebellar cyclic GMP. Since the different hexachlorocyclohexane (HCH) isomers elicit different pharmacological responses in mammals, the authors examined their effects on the accumulation of cerebellar cyclic GMP. Mice received one of the HCH isomers and were sacrificed for determination of cyclic GMP concentrations one hour later. Gamma-HCH increased cyclic GMP while alpha and delta -HCH decreased it. In addition, alpha and delta -HCH prevented the increase in cyclic GMP due to the gamma isomer. Picrotoxin increased cyclic GMP in a manner similar to that of gamma-HCH while strychnine produced only a small increase. All three HCH isomers inhibited the binding of 3 H-TBOB (a ligand for the GABA-A-receptor linked chloride channel) in mouse cerebellum. It is concluded the different HCH isomers can have different effects on cerebellar cyclic GMP accumulation and that these effects may mediated through actions at the GABA-A receptor linked chloride channel. 15 references, 1 figure, 3 tables

  15. Revising Reverse-Phase Chromatographic Behavior for Efficient Differentiation of Both Positional and Geometrical Isomers of Dicaffeoylquinic Acids

    Directory of Open Access Journals (Sweden)

    Keabetswe Masike

    2018-01-01

    Full Text Available Dicaffeoylquinic acids (diCQAs are plant metabolites and undergo trans-cis-isomerization when exposed to UV irradiation. As such, diCQAs exist in both trans- and cis-configurations and amplify the already complex plant metabolome. However, analytical differentiation of these geometrical isomers using mass spectrometry (MS approaches has proven to be extremely challenging. Exploring the chromatographic space to develop possible conditions that would aid in differentially separating and determining the elution order of these isomers is therefore imperative. In this study, simple chromatographic parameters, such as column chemistry (phenyl versus alkyl, mobile phase composition (methanol or acetonitrile, and column temperature, were investigated to aid in the separation of diCQA geometrical isomers. The high-performance liquid chromatography photodiode array (HPLC-PDA chromatograms revealed four isomers post UV irradiation of diCQA authentic standards. The elution profile/order was seen to vary on different reverse-phase column chemistries (phenyl versus alkyl using different mobile phase composition. Here, the elution profile/order on the phenyl-derived column matrices (with methanol as the mobile phase composition was observed to be relatively reproducible as compared to the alkyl (C18 columns. Chromatographic resolution of diCQA geometrical isomers can be enhanced with an increase in column temperature. Lastly, the study highlights that chromatographic elution order/profile cannot be relied upon to fathom the complexity of isomeric plant metabolites.

  16. Identification and quantitation of lipid C=C location isomers: A shotgun lipidomics approach enabled by photochemical reaction.

    Science.gov (United States)

    Ma, Xiaoxiao; Chong, Leelyn; Tian, Ran; Shi, Riyi; Hu, Tony Y; Ouyang, Zheng; Xia, Yu

    2016-03-08

    The field of lipidomics has been significantly advanced by mass spectrometric analysis. The distinction and quantitation of the unsaturated lipid isomers, however, remain a long-standing challenge. In this study, we have developed an analytical tool for both identification and quantitation of lipid C=C location isomers from complex mixtures using online Paternò-Büchi reaction coupled with tandem mass spectrometry (MS/MS). The potential of this method has been demonstrated with an implementation into shotgun lipid analysis of animal tissues. Among 96 of the unsaturated fatty acids and glycerophospholipids identified from rat brain tissue, 50% of them were found as mixtures of C=C location isomers; for the first time, to our knowledge, the quantitative information of lipid C=C isomers from a broad range of classes was obtained. This method also enabled facile cross-tissue examinations, which revealed significant changes in C=C location isomer compositions of a series of fatty acids and glycerophospholipid (GP) species between the normal and cancerous tissues.

  17. Metal-Oxide Film Conversions Involving Large Anions

    International Nuclear Information System (INIS)

    Pretty, S.; Zhang, X.; Shoesmith, D.W.; Wren, J.C.

    2008-01-01

    The main objective of my research is to establish the mechanism and kinetics of metal-oxide film conversions involving large anions (I - , Br - , S 2- ). Within a given group, the anions will provide insight on the effect of anion size on the film conversion, while comparison of Group 6 and Group 7 anions will provide insight on the effect of anion charge. This research has a range of industrial applications, for example, hazardous radioiodine can be immobilized by reaction with Ag to yield AgI. From the perspective of public safety, radioiodine is one of the most important fission products from the uranium fuel because of its large fuel inventory, high volatility, and radiological hazard. Additionally, because of its mobility, the gaseous iodine concentration is a critical parameter for safety assessment and post-accident management. A full kinetic analysis using electrochemical techniques has been performed on the conversion of Ag 2 O to (1) AgI and (2) AgBr. (authors)

  18. Anion analysis in uranium more concentrates by ion chromatography

    International Nuclear Information System (INIS)

    Badaut, V.

    2009-01-01

    In the present exploratory study, the applicability of anionic impurities or attributing nuclear material to a certain chemical process or origin has been investigated. Anions (e.g., nitrate, sulphate, fluoride, chloride) originate from acids or salt solutions that are used for processing of solutions containing uranium or plutonium. The study focuses on uranium ore concentrates ('yellow cakes') originating from different mines. Uranium is mined from different types of ore body and depending on the type of rock, different chemical processes for leaching, dissolving and precipitating the uranium need to be applied. Consequently, the anionic patterns observed in he products of these processes (the 'ore concentrates') are different. The concentrations of different anionic species were measured by ion chromatography using conductivity detection. The results show clear differences of anion concentrations and patterns between samples from different uranium mines. Besides this, differences between sampling campaigns n a same mine were also observed indicating that the uranium ore is not homogeneous in a mine. These within-mine variations, however, were smaller than the between-mine variations. (author)

  19. Identification of inorganic anions by gas chromatography/mass spectrometry.

    Science.gov (United States)

    Sakayanagi, Masataka; Yamada, Yaeko; Sakabe, Chikako; Watanabe, Kunio; Harigaya, Yoshihiro

    2006-03-10

    Inorganic anions were identified by using gas chromatography/mass spectrometry (GC/MS). Derivatization of the anions was achieved with pentafluorobenzyl p-toluenesulphonate (PFB-Tos) as the reaction reagent and a crown ether as a phase transfer catalyst. When PFB-Br was used as the reaction reagent, the retention time of it was close to those of the derivatized inorganic anions and interfered with the analysis. In contrast, the retention time of PFB-Tos differed greatly from the PFB derivatives of the inorganic anions and the compounds of interest could be detected without interference. Although the PFB derivatives of SO4, S2O3, CO3, ClO4, and ClO3 could not be detected, the derivatives of F, Cl, Br, I, CN, OCN, SCN, N3, NO3, and NO2 were detected using PFB-Tos as the derivatizing reagent. The inorganic anions were detectable within 30 ng approximately, which is of sufficient sensitivity for use in forensic chemistry. Accurate mass number was measured for each PFB derivative by high-resolution mass spectrometry (HRMS) within a measurement error of 2 millimass units (mmu), which allowed determination of the compositional formula from the mass number. In addition, actual analysis was performed successively by our method using trial samples of matrix.

  20. REACTIVITY OF ANIONS IN INTERSTELLAR MEDIA: DETECTABILITY AND APPLICATIONS

    Energy Technology Data Exchange (ETDEWEB)

    Senent, M. L. [Departamento de Quimica y Fisica Teoricas, Instituto de Estructura de la Materia, IEM-C.S.I.C., Serrano 121, Madrid E-28006 (Spain); Hochlaf, M., E-mail: senent@iem.cfmac.csic.es, E-mail: hochlaf@univ-mlv.fr [Laboratoire de Modelisation et Simulation Multi Echelle, Universite Paris-Est, MSME UMR 8208 CNRS, 5 boulevard Descartes, F-77454 Marne-la-Vallee (France)

    2013-05-01

    We propose a general rule to distinguish between detectable and undetectable astronomical anions. We believe that only few anions live long enough in the interstellar medium and thus can be detected. Our method is based on quantum mechanical calculations capable of describing accurately the evolution of electronic states during chemical processes. The still not fully understood reactivity at low temperatures is discussed considering non-adiabatic effects. The role of excited states has usually been neglected in previous works which basically focused on the ground electronic state for interpretations of experimental observations. Here, we deal with unsaturated carbon chains (e.g., C{sub n} H{sup -}), which show a high density of electronic states close to their corresponding ground electronic states, complex molecular dynamics, and non-adiabatic phenomena. Our general rule shows that it is not sufficient that anions exist in the gas phase (in the laboratory) to be present in media such as astrophysical media, since formation and decomposition reactions of these anions may allow the population of anionic electronic states to autodetach, forming neutrals. For C{sub n} H, reactivity depends strongly on n, where long and short chains behave differently. Formation of linear chains is relevant.

  1. Treatment of acute non-anion gap metabolic acidosis.

    Science.gov (United States)

    Kraut, Jeffrey A; Kurtz, Ira

    2015-02-01

    Acute non-anion gap metabolic acidosis, also termed hyperchloremic acidosis, is frequently detected in seriously ill patients. The most common mechanisms leading to this acid-base disorder include loss of large quantities of base secondary to diarrhea and administration of large quantities of chloride-containing solutions in the treatment of hypovolemia and various shock states. The resultant acidic milieu can cause cellular dysfunction and contribute to poor clinical outcomes. The associated change in the chloride concentration in the distal tubule lumen might also play a role in reducing the glomerular filtration rate. Administration of base is often recommended for the treatment of acute non-anion gap acidosis. Importantly, the blood pH and/or serum bicarbonate concentration to guide the initiation of treatment has not been established for this type of metabolic acidosis; and most clinicians use guidelines derived from studies of high anion gap metabolic acidosis. Therapeutic complications resulting from base administration such as volume overload, exacerbation of hypertension and reduction in ionized calcium are likely to be as common as with high anion gap metabolic acidosis. On the other hand, exacerbation of intracellular acidosis due to the excessive generation of carbon dioxide might be less frequent than in high anion gap metabolic acidosis because of better tissue perfusion and the ability to eliminate carbon dioxide. Further basic and clinical research is needed to facilitate development of evidence-based guidelines for therapy of this important and increasingly common acid-base disorder.

  2. The single electron chemistry of coals

    Energy Technology Data Exchange (ETDEWEB)

    Larsen, J.W.; Flowers, R.A. II.

    1991-04-22

    The simplest explanation for these shifts in the infrared spectra is there exists in coal single electron donors which are capable of transferring an electron to TCNQ in the ground state. All of the TCNQ placed in the coal appears to be converted to the radical anion as displayed in the IR spectrum for all of the coals except for the 100% loading.

  3. Alpha-tocotrienol is the most abundant tocotrienol isomer circulated in plasma and lipoproteins after postprandial tocotrienol-rich vitamin E supplementation

    Directory of Open Access Journals (Sweden)

    Fairus Syed

    2012-01-01

    Full Text Available Abstract Background Tocotrienols (T3 and tocopherols (T, both members of the natural vitamin E family have unique biological functions in humans. T3 are detected in circulating human plasma and lipoproteins, although at concentrations significantly lower than α-tocopherol (α-T. T3, especially α-T3 is known to be neuropotective at nanomolar concentrations and this study evaluated the postprandial fate of T3 and α-T in plasma and lipoproteins. Methods Ten healthy volunteers (5 males and 5 females were administered a single dose of vitamin E [526 mg palm tocotrienol-rich fraction (TRF or 537 mg α-T] after 7-d pre-conditioning on a T3-free diet. Blood was sampled at baseline (fasted and 2, 4, 5, 6, 8, and 24 h after supplementation. Concentrations of T and T3 isomers in plasma, triacylglycerol-rich particles (TRP, LDL, and HDL were measured at each postprandial interval. Results After TRF supplementation, plasma α-T3 and γ-T3 peaked at 5 h (α-T3: 4.74 ± 1.69 μM; γ-T3: 2.73 ± 1.27 μM. δ-T3 peaked earlier at 4 h (0.53 ± 0.25 μM. In contrast, α-T peaked at 6 h (30.13 ± 2.91 μM and 8 h (37.80 ± 3.59 μM following supplementation with TRF and α-T, respectively. α-T was the major vitamin E isomer detected in plasma, TRP, LDL, and HDL even after supplementation with TRF (composed of 70% T3. No T3 were detected during fasted states. T3 are detected postprandially only after TRF supplementation and concentrations were significantly lower than α-T. Conclusions Bio-discrimination between vitamin E isomers in humans reduces the rate of T3 absorption and affects their incorporation into lipoproteins. Although low absorption of T3 into circulation may impact some of their physiological functions in humans, T3 have biological functions well below concentration noted in this study.

  4. A Supramolecular Sensing Platform for Phosphate Anions and an Anthrax Biomarker in a Microfluidic Device

    Directory of Open Access Journals (Sweden)

    Jurriaan Huskens

    2011-10-01

    Full Text Available A supramolecular platform based on self-assembled monolayers (SAMs has been implemented in a microfluidic device. The system has been applied for the sensing of two different analyte types: biologically relevant phosphate anions and aromatic carboxylic acids, which are important for anthrax detection. A Eu(III-EDTA complex was bound to β-cyclodextrin monolayers via orthogonal supramolecular host-guest interactions. The self-assembly of the Eu(III-EDTA conjugate and naphthalene β-diketone as an antenna resulted in the formation of a highly luminescent lanthanide complex on the microchannel surface. Detection of different phosphate anions and aromatic carboxylic acids was demonstrated by monitoring the decrease in red emission following displacement of the antenna by the analyte. Among these analytes, adenosine triphosphate (ATP and pyrophosphate, as well as dipicolinic acid (DPA which is a biomarker for anthrax, showed a strong response. Parallel fabrication of five sensing SAMs in a single multichannel chip was performed, as a first demonstration of phosphate and carboxylic acid screening in a multiplexed format that allows a general detection platform for both analyte systems in a single test run with µM and nM detection sensitivity for ATP and DPA, respectively.

  5. Inverse H/D isotope effects in benzene activation by cationic and anionic cobalt clusters.

    Science.gov (United States)

    Tombers, Matthias; Barzen, Lars; Niedner-Schatteburg, Gereon

    2013-02-14

    Reactions under single collision conditions with benzene C(6)H(6) and with benzene-d(6) C(6)D(6) of size selected cationic cobalt clusters Co(n)(+) and of anionic cobalt clusters Co(n)(-) in the cluster size range n = 3-28 revealed that dehydrogenation by cationic clusters is sparse, whereas it is ubiquitous in reactions by anionic clusters. Kinetic isotope effects (KIE) in total reaction rates are inverse and, in part, large. Dehydrogenation isotope effects (DIE) are normal. A multistep model of adsorption and stepwise dehydrogenation from the precursor adsorbate unravels a possible origin of the inverse KIE: Single step C-H bond activation is swift (no KIE in forward direction) and largely reversible (normal KIE backward) whereas H/D tunneling is likely to contribute (backward). DFT calculations of the structures and energetics along the reaction path in [Co(13)C(6)H(6)](+) lend support to the proposed multistep model. The observed effects on rates and KIEs of cluster charges and of cluster sizes are noted to elucidate further.

  6. Reactions of isoprene and sulphoxy radical-anions – a possible source of atmospheric organosulphites and organosulphates

    Directory of Open Access Journals (Sweden)

    K. J. Rudziński

    2009-03-01

    Full Text Available Transformation of isoprene coupled with auto-oxidation of SIV in aqueous solutions was studied experimentally and by chemical-kinetic modelling over a broad range of solution acidities (pH=3–9 to complement the research on aqueous-phase and heterogeneous transformation of isoprene reported recently by many laboratories. Isoprene significantly slowed down the auto-oxidation in acidic and basic solutions, and accelerated it slightly in neutral solutions. Simultaneously, production of sulphate ions and formation of solution acidity were significantly reduced. Formation of sulphite and sulphate derivatives of isoprene - sulphurous acid mono-(2-methyl-4-oxo-but-2-enyl ester (m/z=163, sulphurous acid mono-(4-hydroxy-2-methyl-but-2-enyl ester (m/z=165, sulphuric acid mono-(2-methyl-4-oxo-but-2-enyl ester (m/z=179, sulphuric acid mono-(4-hydroxy-2-methyl-but-2-enyl ester (m/z=181, and possible structural isomers of these species – was indicated by electrospray ionisation mass spectrometric analysis of post-reaction mixtures. The experimental results were explained by changes in a subtle quantitative balance of three superimposed processes whose rates depended in different manner on the acidity of reacting solutions – the scavenging of sulphoxy radical-anions by isoprene, the formation of sulphoxy radical-anions during further reactions of isoprene radicals, and the auto-oxidation of SIV itself. A chemical mechanism based on this idea was explored numerically to show good agreement with experimental data. In basic and neutral solutions, the model overestimated the consumption of isoprene, probably because reactions of primary sulphite and sulphate derivatives of isoprene with sulphoxy radical-anions were not included. Interaction of isoprene with sulphur(IV species and oxygen can possibly result in formation of new organosulphate and organosulphite components of atmospheric aerosols and waters, and

  7. Anti-Leishmania and cytotoxic activities of perillaldehyde epoxide synthetic positional isomers.

    Science.gov (United States)

    Keesen, Tatjana Souza Lima; da Silva, Larisse Virgolino; da Câmara Rocha, Juliana; Andrade, Luciana Nalone; Lima, Tamires Cardoso; de Sousa, Damião Pergentino

    2018-03-13

    Leishmaniasis belongs to a complex of zoonotic disease caused by protozoa of the genus Leishmania and is considered a major public health problem. Several essential oil chemical components have inhibitory effect against protozoa, including Leishmania donovani. Thus, the aim of this study was to evaluate for the first time the anti-Leishmania activity of two p-menthane monoterpene isomers (EPER-1: perillaldehyde 1,2-epoxide and EPER-2: perillaldehyde 8,9-epoxide) against L. donovani promastigotes as well as evaluating cytotoxic effect on mononuclear peripheral blood cells. Results of anti-Leishmania assay revealed that EPER-2 (IC 50  = 3.8 μg.mL -1 ) was 16-fold more potent than its isomer EPER-1 (IC 50  = 64.6 μg.mL -1 ). In contrast to PBMC cells, EPER-2 was not cytotoxic (IC 50  > 400 μg.mL -1 ) when compared to positive control. These data suggest that the disposition of epoxide group into the p-menthane skeleton affects the anti-Leishmania activity, being that the presence of the exocyclic epoxide group considerably increased potency. Thus, it was possible to observe that the location of the epoxide group into the p-menthane skeleton resulted in different potencies.

  8. Brain metabolites of lindane and related isomers: identification by negative ion mass spectrometry.

    Science.gov (United States)

    Artigas, F; Martínez, E; Camón, L; Gelpí, E; Rodríguez-Farré, E

    1988-04-01

    The application of a new method of gas chromatography-mass spectrometry (GC-MS) to the study of some aspects of the metabolism of hexachlorocyclohexanes is presented. Instead of the classical mode of ionization (Electron Impact, EI), this method uses chemical ionization, recording only the negative ions produced. This enables a tremendous enhancement of the signal when chlorinated compounds elute from the chromatographic column. The mass spectra obtained consist generally in the ions corresponding to the molecular weight of the compound analyzed. The sensitivity of the method is higher than any other GC method described: the limit of detection of several organochlorine compounds can be as low as 60 femtograms. Using this method we have been able to identify several Lindane metabolites (tetra-, penta- and hexachlorocyclohexenes, tetra- and pentachlorobenzene) in rat brain homogenates without any purification step. Using this method, a quantitative study of the main metabolites found in brain after treatment with 4 different HCH isomers has been performed. This study reveals that the HCH isomers are cleared from the brain via different metabolic pathways, with a rate of production of metabolites which is inversely correlated to their half lives in brain.

  9. Conformational inversion-topomerization mechanism of ethylcyclohexyl isomers and its role in combustion kinetics

    KAUST Repository

    Bian, Huiting

    2016-07-26

    With the "strain-free" cyclic structure, cyclohexane and alkyl cyclohexanes (and their radicals) have various conformers (e.g. chair, boat, and twist etc.) by pseudorotation of the alkyl ring. Noting that different conformers will undergo different types of H-migration reactions, the mechanism of conformational change may impact the distribution of cyclohexyl and the branched cyclohexyl radical isomers during cyclohexane and alkyl cyclohexanes combustion. Consequently, it will influence the formation of subsequent decomposition products. In this work, the conformational inversion-topomerization mechanism and H-migration reactions for six ethylcyclohexyl radical isomers were systematically studied by ab initio calculations and the transition state theory. The updated sub-mechanism of these conformational changes is incorporated into an ethylcyclohexane pyrolysis model. By comparing the simulated results of the "complete" model including the sub-mechanism of conformational changes and the simplified model ignoring these processes, the effect of inversion-topomerization mechanism on the relative concentrations of various ethylcyclohexyl radicals and the formation of subsequent decomposition products were revealed. © 2016.

  10. Isomer beam elastic scattering: 26mAl(p, p) for astrophysics

    Science.gov (United States)

    Kahl, D.; Shimizu, H.; Yamaguchi, H.; Abe, K.; Beliuskina, O.; Cha, S. M.; Chae, K. Y.; Chen, A. A.; Ge, Z.; Hayakawa, S.; Imai, N.; Iwasa, N.; Kim, A.; Kim, D. H.; Kim, M. J.; Kubono, S.; Kwag, M. S.; Liang, J.; Moon, J. Y.; Nishimura, S.; Oka, S.; Park, S. Y.; Psaltis, A.; Teranishi, T.; Ueno, Y.; Yang, L.

    2018-01-01

    The advent of radioactive ground-state beams some three decades ago ultimately sparked a revolution in our understanding of nuclear physics. However, studies with radioactive isomer beams are sparse and have often required sophisticated apparatuses coupled with the technologies of ground-state beams due to typical mass differences on the order of hundreds of keV and vastly different lifetimes for isomers. We present an application of a isomeric beam of 26mAl to one of the most famous observables in nuclear astrophysics: galactic 26Al. The characteristic decay of 26Al in the Galaxy was the first such specific radioactivity to be observed originating from outside the Earth some four decades ago. We present a newly-developed, novel technique to probe the structure of low-spin states in 27Si. Using the Center for Nuclear Study low-energy radioisotope beam separator (CRIB), we report on the measurement of 26mAl proton resonant elastic scattering conducted with a thick target in inverse kinematics. The preliminary results of this on-going study are presented.

  11. Effects of isomers of apomorphines on dopamine receptors in striatal and limbic tissue of rat brain

    Energy Technology Data Exchange (ETDEWEB)

    Kula, N.S.; Baldessarini, R.J.; Bromley, S.; Neumeyer, J.L.

    1985-09-16

    The optical isomers of apomorphine (APO) and N-propylnorapomorphine (NPA) were interacted with three biochemical indices of dopamine (Da) receptors in extrapyramidal and limbic preparations of rat brain tissues. There were consistent isomeric preferences for the R(-) configuration of both DA analogs in stimulation adenylate cyclase (D-1 sites) and in competing for high affinity binding of /sup 3/H-spiroperidol (D-2 sites) and of /sup 3/H-ADTN (DA agonist binding sites) in striatal tissue, with lesser isomeric differences in the limbic tissue. The S(+) apomorphines did not inhibit stimulation of adenylate cyclase by DA. The tendency for greater activity of higher apparent affinity of R(-) apomorphines in striatum may reflect the evidently greater abundance of receptor sites in that region. There were only small regional differences in interactions of the apomorphine isomers with all three receptor sites, except for a strong preference of (-)NPA for striatal D-2 sites. These results do not parallel our recent observations indicating potent and selective antidopaminergic actions of S(+) apomorphines in the rat limbic system. They suggest caution in assuming close parallels between current biochemical functional, especially behavioral, methods of evaluating dopamine receptors of mammalian brain.

  12. Effect of food processing on degradation of hexachlorocyclohexane and its isomers in milk

    Directory of Open Access Journals (Sweden)

    Sujatha Singh

    2017-03-01

    Full Text Available Aim: To study the effect of different food processing techniques on the degradation of organochlorine compounds (α, β, ɣ and δ hexachlorocyclohexane isomers (HCH residues in both natural and fortified samples of milk. Materials and Methods: Raw milk samples are collected from the local areas of Hyderabad, India. Naturally and fortified milk samples (HCH were subjected to various food processing techniques, pasteurization (63ºC for ½ h, sterilization (121ºC for 15 min and boiling for 5 min and analyzed by gas chromatography with electron capture detector using quick, easy, cheap, effective, rugged and safe method for multiresidue analysis of pesticides in milk with slight modification. Results: The final mean residual concentration of pesticide in milk after heat processing and percentage of degradation were calculated with respective treatments. Conclusion: Heat treatments are highly effective on reduction of mean residual concentration of HCH in milk. In which Sterilization and boiling proved to be more effective in degradation of HCH isomers.

  13. Isomer pattern and elimination of dioxins in workers exposed at a municipal waste incineration plant

    Science.gov (United States)

    YAMAMOTO, Kenya; KUDO, Mitsuhiro; ARITO, Heihachiro; OGAWA, Yasutaka; TAKATA, Tsutomu

    2015-01-01

    The aim of this study was to clarify patterns of serum concentrations of dioxins in the employees of a waste incineration plant and to estimate elimination rates and half-lives of serum dioxin isomers, and the maximum serum concentrations of dioxin isomers at the time of plant shutdown. Sixteen subjects participating 3 times or more in annual health examinations during an 8-yr period from 2000 to 2007 were recruited for this study. Serum concentrations of dioxins expressed as TEQ/g lipid decreased gradually after plant shutdown with the highest decrease observed in polychlorinated dibenzofurans (PCDFs) followed by polychlorinated deibenzo-p-dioxins (PCDDs) and then coplanar PCBs. The serum toxic equivalency (TEQ) concentrations of PCDF and PCDD congeners in the employees were higher than those in the general population survey by the Ministry of the Environment, Japan, whereas the serum concentrations of coplanar PCBs were similar to those in the general population. The estimated half-lives and elimination rates of PCDDs and PCDFs in the highly exposed workers increased compared with the moderately exposed workers. The estimated geometric mean serum concentrations of PCDDs, PCDFs and total dioxins at the time of plant shutdown were 35, 53 and 107 pg TEQ/g lipid, respectively. PMID:26118856

  14. Determination of melatonin and its isomer in foods by liquid chromatography tandem mass spectrometry.

    Science.gov (United States)

    Kocadağlı, Tolgahan; Yılmaz, Cemile; Gökmen, Vural

    2014-06-15

    This study aimed to develop a reliable analytical method for the determination of melatonin and its isomers in various food products. The method entails ethanol extraction of solid samples (or dilution of liquid samples) prior to liquid chromatography coupled to triple quadruple mass spectrometry (LC-MS/MS) analysis of target analytes. The method was in-house validated and successfully applied to various food matrices. Recovery of melatonin from different matrices were found to be 86.0 ± 3.6%, 76.9 ± 5.4%, 98.6 ± 6.4%, and 67.0 ± 4.5% for beer, walnut, tomato and sour cherry samples, respectively. No melatonin could be detected in black and green tea, sour cherry, sour cherry concentrate, kefir (a fermented milk drink) and red wine while the highest amount of melatonin (341.7 ± 29.3 pg/g) was detected in crumb. The highest amounts of melatonin isomer were detected in yeast-fermented foods such as 170.7 ± 29.9 ng/ml in red wine, 14.3 ± 0.48 ng/ml in beer, and 15.7 ± 1.4 ng/g in bread crumb. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. Selective bioaccumulation, biomagnification, and dissipation of hexachlorocyclohexane isomers in a freshwater food chain.

    Science.gov (United States)

    Di, Shanshan; Liu, Ruiquan; Chen, Li; Diao, Jinling; Zhou, Zhiqiang

    2018-04-30

    Hexachlorocyclohexane isomers (HCHs) are persistent organic pollutants (POPs), having potential risks to humans and ecosystem. This work evaluated the propensity of organisms to accumulate, eliminate, and transfer HCHs along the food chain (Tubifex tubifex and common carp (Cyprinus carpio)). The accumulation of HCHs from water by worms and carp was observed, and the concentrations increased with exposure time. After 8 days, the HCH concentrations in organisms remained stable. The accumulation factor (AF) values of HCHs in T. tubifex were higher than those in carp, indicating that the bioaccumulation abilities of HCHs in T. tubifex were higher than those in carp. The contaminated worms as a dietary source in the food chain led to significantly higher bioaccumulation in carp. The biomagnification factor (BMF) values of HCH isomers were all greater than 1. In the dissipation experiments, the elimination was fast and the half-lives were shorter than 2.5 days. The enantioselective accumulation and dissipation of α-HCH enantiomers were observed in worms and carp (food chain), and the enantiomeric differences should be taken into consideration in the study of contaminants risk assessment. The results on trophic transfer of HCHs in a freshwater food chain should be helpful for better understanding the fate, transport, and transfer of HCHs in freshwater environments.

  16. Unambiguous identification of three $\\beta$-decaying Isomers in $^{70}$Cu

    CERN Document Server

    Van Roosbroeck, J; Audi, G; Beck, D; Blaum, K; Bollen, G; Cederkäll, J; Delahaye, P; De Maesschalck, A; De Witte, H; Fedorov, D; Fedosseev, V; Franchoo, S; Fynbo, H O U; Górska, M; Herfurth, F; Heyde, Kris L G; Huyse, M; Kellerbauer, A G; Kluge, H J; Köster, U; Kruglov, K; Lunney, M D; Mishin, V I; Müller, W F; Nagy, S; Schwarz, S; Schweikhard, L; Smirnova, N A; Van de Vel, K; Van Duppen, P; Van Dyck, A; Walters, W B; Weissman, L; Yazidjian, C

    2004-01-01

    Using resonant laser ionization, $\\beta$-decay studies and for the first time mass measurements, three $\\beta$-decaying states have been unambiguously identified in $^{70}$Cu. A mass excess of -62976.1(1.6) keV and a half-life of 44.5(2) s for the (6$^{-}$) ground state have been determined. The level energies of the (3$^{−}$) isomer at 101.1(3) keV with $T_{1/2}=33(2)$   s and the $1^{+}$ isomer at 242.4(3) keV with $T_{1/2}=6.6(2)$   s are confirmed by high-precision mass measurements. The low-lying levels of $^{70}$Cu populated in the decay of $^{70}$Ni and in transfer reactions compare well with large-scale shell-model calculations, and the wave functions appear to be dominated by one proton–one neutron configurations outside the closed Z=28 shell and N=40 subshell. This does not apply to the $1^{+}$ state at 1980 keV which exhibits a particular feeding and deexcitation pattern not reproduced by the shell-model calculations.

  17. Quantification of the ratio of positional isomer dilinoleoyl-oleoyl glycerols in vegetable oils.

    Science.gov (United States)

    Jakab, A; Jablonkai, I; Forgács, E

    2003-01-01

    The distribution of fatty acids in a triacylglycerol is of great importance from nutritional, biochemical, quality and technological points of view. The ratio of triacylglycerol positional isomers containing two linoleic acid (18:2) and one oleic acid (18:1) moieties--namely, 1(3),2-dilinoleoyl-3(1)-oleoyl glycerol (LLO) and 1,3-dilinoleoyl-2-oleoyl glycerol (LOL)--were quantified in grape seed, olive, pumpkin seed, soybean, sunflower and wheat germ oils by high-performance liquid chromatography/atmospheric pressure chemical ionization mass spectrometry (HPLC/APCI-MS) in selected ion monitoring (SIM) mode. Relative LOL contents (LOL/(LLO+LOL)) of the oils were calculated from the mass abundances of the [LL]+ and [LO]+ diacylglycerol fragment ions ([M+H-RCOOH]+) using a calibration curve. The calibration curve of the relative diacylglycerol mass abundances was measured in SIM mode. The relative LOL contents were found to be relatively consistent for each oil variety. The relative LOL content in grape seed, sunflower, pumpkin seed, soybean and wheat germ oils accounted for 44.2 +/- 2.6, 26.8 +/- 3.2, 16.7 +/- 4.6, 15.9 +/- 2.9 and 13.9 +/- 4.3%, respectively. Only olive oils contained practically 100% of the LLO isomer. These results indicate that the unsaturated fatty acids such as linoleic and oleic acids have 'non-random' distribution patterns in various oils. Copyright 2003 John Wiley & Sons, Ltd.

  18. [Formation of protodioscin and deltoside isomers in suspension cultures of Nepal yam (Dioscorea deltoidea Wall.) cells].

    Science.gov (United States)

    Khandy, M T; Titova, M V; Konstantinova, S V; Kochkin, D V; Ivanov, I M; Nosov, A M

    2016-01-01

    Changes in the content of the furostanol glycosides protodioscin and deltoside, particularly that of the (25S)-isomers of the glycosides, during suspension cultivation of different lines of Nepal yam (Dioscorea deltoidea Wall.) cells of the strain IFR-DM-0.5 has been investigated. The composition of furostanol glycosides has been characterized, and the dynamics of the accumulation of individual glycosides during lengthy subcultivation of cells maintained in flasks or in a barbotage bioreactor has been analyzed. A positive correlation between the growth and accumulation of substances that belonged to the class of furostanol glycosides has been demonstrated for cultured dioscorea cells, whereas the content of some of the individual glycosides varied considerably between the lines of the strain, cultures maintained under different conditions, and even between cells in different phases of the growth cycle. The increased content of (25R)-forms of the glycosides (protodioscin and deltoside) was correlated with a decrease in the cellular growth rate, whereas an increase in culture growth intensity occurred concomitantly to an increase of the amount of (25S)-isomers. This may be indicative of the specific stimulatory effect of (25S)-glycosides, but not the (25R)-forms, on cell proliferation in vitro. Thus, the concentration of (25S)-forms may increase due to the autoselection of cells capable of intensive division during prolonged cultivation.

  19. Occurrence, fluxes and sources of perfluoroalkyl substances with isomer analysis in the snow of northern China.

    Science.gov (United States)

    Shan, Guoqiang; Chen, Xinwei; Zhu, Lingyan

    2015-12-15

    In this study, perfluoroalkyl substances (PFASs) and the isomers of perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) were analyzed in fresh snow samples collected from 19 cities in northern China, 2013. The levels of total PFASs in the snow samples were 33.5-229 ng/L, suggesting heavy atmospheric pollution of PFASs in northern China. PFOA (9.08-107 ng/L), PFOS (3.52-54.3 ng/L), perfluoroheptanoate (PFHpA) (3.66-44.8 ng/L), and perfluorohexanoate (PFHxA) (3.21-23.6 ng/L) were predominant with a summed contribution of 82% to the total PFASs. The particulate matters (PMs) associated PFASs contributed 21.5-56.2% to the total PFASs in the snow, suggesting PMs are vital for the transport and deposition of airborne PFASs. Partitioning of PFASs between PM and dissolved phases was dependent on the carbon chain length and end functional groups. Isomer profiles of PFOA and PFOS in the snow were in agreement with the signature of the historical 3M electrochemical fluorination (ECF) products, suggesting that the ECF products were still produced and used in China. Further source analysis showed that the airborne PFASs in urban area were mainly due to direct release rather than degradation of their precursors. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. New information on the T1/2=47 s isomer in the 136I nucleus

    International Nuclear Information System (INIS)

    Urban, W.; Rzaca-Urban, T.; Saha Sarkar, M.; Sarkar, S.; Durell, J.L.; Smith, A.G.; Genevey, J.A.; Pinston, J.A.; Simpson, G.S.; Ahmad, I.

    2006-01-01

    The 136 I nucleus, populated in the spontaneous fission of 248 Cm, was studied by means of prompt γ-ray spectroscopy using the EUROGAM2 array. The observation in this work of the 42.6 keV prompt-γ, M1+E2 transition de-exciting the 7 - level in 136 I indicates that this level, interpreted as the (πg 7/2 3 νf 7/2 ) 7- configuration, does not correspond to the T=47 s, β-decaying isomer in 136 I. The isomer is placed 42.6 keV below the 7 - level. It has spin 6 - and is interpreted as the (πg 7/2 2 d 5/2 νf 7/2 ) 6- configuration. This and other members of both multiplets can be reproduced properly only if one assumes that the πd 5/2 orbital in 136 I is located 400keV lower than in 133 Sb. Possible mechanisms causing this effect are discussed. (orig.)

  1. Static quadrupole moment of the Kπ = 14+ isomer in 176W

    International Nuclear Information System (INIS)

    Ionescu-Bujor, M.; Iordachescu, A.; Bucurescu, D.; Brandolini, F.; Lenzi, S. M.; Pavan, P.; Rossi Alvarez, C.; Marginean, N.; Medina, N.H.; Ribas, R.V.; De Poli, M.; Napoli, D. R.; Podolyak, Zs.; Ur, C. A.

    2001-01-01

    The investigation of high-K isomeric states in the deformed nuclei of the A∼180 region has found renewed interest in recent years. Much experimental and theoretical work was devoted to understand the mechanisms which govern their decay to lower-lying states, particularly the anomalous strong decays to low-K states. Other questions of great importance are the quenching of the pairing correlations and the shape polarization effects in the high-seniority multi-quasiparticle excitations. Our interest focused on the 41 ns K π =14 + 3746 keV isomeric state with anomalous decay in 176 W. On the basis of a precise g-factor measurement we assigned to this isomer a pure four-quasiparticle configuration, composed by two protons in the 7/2 + [404] and 9/2 - [514] orbitals and two neutrons in the 7/2 + [633] and 5/2 - [512] orbitals. In the present work the measurement of its static quadrupole moment has been performed. Prior to our experiment, static quadrupole moments have been measured only for three high-K isomeric states of seniority ≥ 4 in the A∼180 region: 16 + in 178 Hf, 35/2 - in 179 W and 25 + in 182 Os. A deformation very similar to that of the ground state has been deduced for the 16 + isomer in 178 Hf, while for the high-K isomers in 179 W and 182 Os significantly smaller deformations were reported. The quadrupole interaction of the 14 + isomeric state in 176 W has been investigated in the electric field gradient (EFG) of the polycrystalline lattice of metallic Tl by applying the time-differential perturbed angular distribution method. For W impurities in Tl host the EFG strength and its temperature dependence have been recently reported. The isomer was populated in the 164 Dy( 16 O,4n) 176 W reaction using a 83 MeV 16 O pulsed beam (pulse width 1.5 ns, repetition period 800 ns) delivered by the XTU-Tandem of Laboratori Nazionali di Legnaro. The target consisted of 0.5 mg/cm 2 metallic 164 Dy on thick Tl backing in which both the recoiling 176 W nuclei and

  2. Cell wall bound anionic peroxidases from asparagus byproducts.

    Science.gov (United States)

    Jaramillo-Carmona, Sara; López, Sergio; Vazquez-Castilla, Sara; Jimenez-Araujo, Ana; Rodriguez-Arcos, Rocio; Guillen-Bejarano, Rafael

    2014-10-08

    Asparagus byproducts are a good source of cationic soluble peroxidases (CAP) useful for the bioremediation of phenol-contaminated wastewaters. In this study, cell wall bound peroxidases (POD) from the same byproducts have been purified and characterized. The covalent forms of POD represent >90% of the total cell wall bound POD. Isoelectric focusing showed that whereas the covalent fraction is constituted primarily by anionic isoenzymes, the ionic fraction is a mixture of anionic, neutral, and cationic isoenzymes. Covalently bound peroxidases were purified by means of ion exchange chromatography and affinity chromatography. In vitro detoxification studies showed that although CAP are more effective for the removal of 4-CP and 2,4-DCP, anionic asparagus peroxidase (AAP) is a better option for the removal of hydroxytyrosol (HT), the main phenol present in olive mill wastewaters.

  3. Synthesis and anion binding properties of porphyrins and related compounds

    KAUST Repository

    Figueira, Flávio

    2016-12-02

    Over the last two decades the preparation of pyrrole-based receptors for anion recognition has attracted considerable attention. In this regard porphyrins, phthalocyanines and expanded porphyrins have been used as strong and selective receptors while the combination of those with different techniques and materials can boost their applicability in different applications as chemosensors and extracting systems. Improvements in the field, including the synthesis of this kind of compounds, can contribute to the development of efficient, cheap, and easy-to-prepare anion receptors. Extensive efforts have been made to improve the affinity and selectivity of these compounds and the continuous expansion of related research makes this chemistry even more promising. In this review, we summarize the most recent developments in anion binding studies while outlining the strategies that may be used to synthesize and functionalize these type of macrocycles. © 2016 World Scientific Publishing Company.

  4. Characterization and reactivity of the weakly bound complexes of the [H, N, S]{sup −} anionic system with astrophysical and biological implications

    Energy Technology Data Exchange (ETDEWEB)

    Trabelsi, T.; Ajili, Y.; Ben Yaghlane, S.; Jaidane, N.-E. [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications–LSAMA, Université de Tunis El Manar, Tunis (Tunisia); Mogren Al-Mogren, M. [Chemistry Department, Faculty of Science, King Saud University, P.O. Box 2455, Riyadh 11451 (Saudi Arabia); Francisco, J. S. [Department of Chemistry and Department of Earth and Atmospheric Sciences, Purdue University, West Lafayette, Indiana 47906 (United States); Hochlaf, M., E-mail: hochlaf@univ-mlv.fr [Laboratoire Modélisation et Simulation Multi Echelle, Université Paris-Est, MSME UMR 8208 CNRS, 5 Blvd. Descartes, 77454 Marne-la-Vallée (France)

    2015-07-21

    We investigate the lowest electronic states of doublet and quartet spin multiplicity states of HNS{sup −} and HSN{sup −} together with their parent neutral triatomic molecules. Computations were performed using highly accurate ab initio methods with a large basis set. One-dimensional cuts of the full-dimensional potential energy surfaces (PESs) along the interatomic distances and bending angle are presented for each isomer. Results show that the ground anionic states are stable with respect to the electron detachment process and that the long range parts of the PESs correlating to the SH{sup −} + N, SN{sup −} + H, SN + H{sup −}, NH + S{sup −}, and NH{sup −} + S are bound. In addition, we predict the existence of long-lived weakly bound anionic complexes that can be formed after cold collisions between SN{sup −} and H or SH{sup −} and N. The implications for the reactivity of these species are discussed; specifically, it is shown that the reactions involving SH{sup −}, SN{sup −}, and NH{sup −} lead either to the formation of HNS{sup −} or HSN{sup −} in their electronic ground states or to autodetachment processes. Thus, providing an explanation for why the anions, SH{sup −}, SN{sup −}, and NH{sup −}, have limiting detectability in astrophysical media despite the observation of their corresponding neutral species. In a biological context, we suggest that HSN{sup −} and HNS{sup −} should be incorporated into H{sub 2}S-assisted heme-catalyzed reduction mechanism of nitrites in vivo.

  5. HPLC analysis of geometrical isomers of lutein epoxide isolated from dandelion (Taraxacum officinale F. Weber ex Wiggers).

    Science.gov (United States)

    Meléndez-Martínez, Antonio J; Britton, George; Vicario, Isabel M; Heredia, Francisco J

    2006-04-01

    Lutein epoxide has been isolated from petals of dandelion (Taraxacum officinale F. Weber ex Wiggers) by thin-layer chromatography (TLC) on silica to be used for the accurate identification of this carotenoid in other sources. The extract was analyzed by high-performance liquid chromatography (HPLC) using a C(30) column, as a result of which six geometrical isomers were separated. The identification of these isomers was performed on the basis of their UV/vis spectroscopic features in the mobile phase. In quantitative terms, it was observed that all-E-lutein epoxide was the major carotenoid and that there were also high amounts of the (9Z)- and (9'Z)-isomers, although the latter may be an artifact.

  6. Isomeric and high-spin states of 94Tc and the search for yrast isomers near N~50

    Science.gov (United States)

    Lee, I. Y.; Johnson, N. R.; McGowan, F. K.; Young, G. R.; Guidry, M. W.; Yates, S. W.

    1981-07-01

    A search for isomers in the N~50 region has produced no evidence of high-spin yrast isomerism. A new 4.5-ns low-multiplicity isomer has been identified and assigned to 94Tc, while the yrast sequence of 94Tc has been established to more than 5 MeV in excitation energy. [NUCLEAR REACTIONS 76Ge, 78Se(20Ne,xnypγ), E=80.9 MeV, 89Y, 93Nb(10B,xnypγ), E=52.0,58.4,62.8 MeV; measured Eγ, Iγ, γ-γ prompt and delayed coin, γ-X coin; deduced levels, t12 of 94Tc isomer, yrast states.

  7. Measurements of quadrupole interaction frequencies of long-lived isomers with the level mixing spectroscopy (LEMS) method

    International Nuclear Information System (INIS)

    Neyens, G.; Nouwen, R.; S'heeren, G.; Bergh, M. van den; Coussement, R.

    1993-01-01

    The level mixing spectroscopy (LEMS) method has proven to be a very useful method to determine the quadrupole interaction frequency of an isomer in a solid host. Especially in the 'difficult' cases, e.g. when the isomeric lifetime is very long or its spin is very high, the method yields valuable information which is not accessible with other methods (such as TDPAD). Since the development of the method some years ago, many experiments have been performed on high spin isomers in the lead region. The static quadrupole moment of isomers with lifetimes ranging from 20 ns up to 13 ms and spins up to 65/2h have been determined in neutron deficient isotopes of Bi, At, Fr and Ra. (orig.)

  8. Trans fatty acids: chemical synthesis of eicosapentaenoic acid isomers and detection in rats fed a deodorized fish oil diet.

    Science.gov (United States)

    Ferreri, Carla; Grabovskiy, Stanislav A; Aoun, Manar; Melchiorre, Michele; Kabal'nova, Natalia; Feillet-Coudray, Christine; Fouret, Gilles; Coudray, Charles; Chatgilialoglu, Chryssostomos

    2012-03-19

    Eicosapentaenoic acid (EPA) is a polyunsaturated fatty acid present in fish oils used for omega-3 enriched diets. The natural cis double bond geometry can be transformed to the trans configuration during the deodorization process utilized in the food industry. The analytical discrimination of the possible five monotrans regioisomers represents a limiting step for the recognition and structure-activity relationship in connection with the harmful effects of trans fatty acids in health. We carried out a dual synthetic strategy, providing new access to monotrans EPA isomers and valuable information on GC and NMR characteristics for further applications in metabolomics and lipidomics. This small library was used as an analytical reference for isomer determination in deodorized fish oils and the follow-up of rats fed fish oil diets, evidencing for the first time that monotrans EPA isomers are incorporated in liver mitochondrial membranes after dietary intake. © 2012 American Chemical Society

  9. Polarity-Dependent Isomerization of an Unsymmetrical Overcrowded Ethylene Promoted by Zwitterionic Contribution in the Twisted Isomer.

    Science.gov (United States)

    Hirao, Yasukazu; Nagamachi, Nobuhiro; Hosoi, Katsuma; Kubo, Takashi

    2018-03-02

    The twisted form of bianthrone is known as a metastable state provided by a photo-induced or thermal-induced isomerization of the folded form, and thus prevents the isolation and the detailed analysis of its electronic structure. In this study, an unsymmetrical bianthrone (2), consisting of the electron-withdrawing anthrone and electron-donating acridane, have been synthesized and shown to exhibit a solvent-polarity-dependent isomerization reaction between the folded and twisted isomers. With increasing the polarity of the solvent, 2 showed an isomerization reaction from the folded form to the twisted form. The stabilization of the twisted isomer in polar solvents can be interpreted as proof of its relatively large zwitterionic character. The DMF solution of 2 displayed paramagnetically-broadened NMR signals from the thermally populated triplet state resulting from rotation of the weakened ethylenic double bond of the twisted isomer. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Even-odd alternation of the formation of dimer isomers in irradiated polycrystalline alkanes: evidence from product analysis

    International Nuclear Information System (INIS)

    Baudson, T.; Tilquin, B.

    1984-01-01

    Recent ESR studies on n-alkanes from n-C 11 to n-C 25 have shown that a prominent chain end (-CH 2 -CH 2 ) alkyl radical is formed in odd members of the series. In this preliminary discussion of our study, we shall report the capillary chromatogram in the dimer isomers range for n-alkanes ranging from n-C 11 to n-C 17 irradiated at 80 kGy. Dimer isomers, produced in part by the combination of chain end radicals, are eluted at the end chromatogram. The combination of two chain end radicals gives the dimer (D 11 ) isomer eluted at the last place. It is shown that dimers produced by the combination of chain end alkyl radicals are more important for the odd members of the series than for the even members. (author)

  11. Study of the odd-${A}$, high-spin isomers in neutron-deficient trans-lead nuclei with ISOLTRAP

    CERN Multimedia

    Herfurth, F; Blaum, K; Beck, D; Kowalska, M; Schwarz, S; Stanja, J; Huyse, M L; Wienholtz, F

    We propose to measure the excitation energy of the $\\frac{13^{+}}{2}$ isomers in the neutron-deficient isotopes $^{193,195,197}$Po with the ISOLTRAP mass spectrometer. The assignment of the low- and high-spin isomers will be made by measuring the energy of the $\\alpha$- particles emitted in the decay of purified beams implanted in a windmill system. Using $\\alpha$-decay information, it is then also possible to determine the excitation energy of the similar isomers in the $\\alpha$-daughter nuclei $^{189,191,193}$Pb, $\\alpha$-parent nuclei $^{197,199,201}$Rn, and $\\alpha$-grand-parent nuclei $^{201,203,205}$Ra. The polonium beams are produced with a UC$_{\\textrm{x}}$ target and using the RILIS.

  12. Anion effect on the retention of recoil atom of coordination crystalline compounds

    International Nuclear Information System (INIS)

    Dimotakis, P.N.; Papadopoulos, B.P.

    1980-01-01

    The anion effect of various cobaltic crystalline compounds - having the same cation and differing in anion -on the retention of neutron activated central cobalt atom has been studied. The cation was trans-dichloro(bis)ethylenediamine cobalt(III) and the anions were simple spherical anions (Cl - , Br - , I - ), planar anions (NO 3 - ), trigonal pyramidal anions (ClO 3 - , BrO 3 - ), tetrahedral anions (SO 4 2- , CrO 4 2- , MnO 4 - ) and linear anions (SCN - ). The cobalt-60 activity after reactor irradiation either in simple Co 2+ cation or in cobaltic complex cation determined the retention values. In all irradiations at ordinary temperature and at liquid nitrogen temperature the results showed an effect of the different anions, depending on the geometry, volume and charge, on the recombination of the recoil cobalt with the ligands in the coordination sphere. (author)

  13. Anionic solid lipid nanoparticles supported on protamine/DNA complexes

    International Nuclear Information System (INIS)

    Ye Jiesheng; Liu Chunxi; Chen Zhijin; Zhang Na; Wang Aihua

    2008-01-01

    The objective of this study was to design novel anionic ternary nanoparticles for gene delivery. These ternary nanoparticles were equipped with protamine/DNA binary complexes (150-200 nm) as the support, and the anionic formation was achieved by absorption of anionic solid lipid nanoparticles (≤20 nm) onto the surface of the binary complexes. The small solid lipid nanoparticles (SLNs) were prepared by a modified film dispersion-ultrasonication method, and adsorption of the anionic SLNs onto the binary complexes was typically carried out in water via electrostatic interaction. The formulated ternary nanoparticles were found to be relatively uniform in size (257.7 ± 10.6 nm) with a 'bumpy' surface, and the surface charge inversion from 19.28 ± 1.14 mV to -17.16 ± 1.92 mV could be considered as evidence of the formation of the ternary nanoparticles. The fluorescence intensity measurements from three batches of the ternary nanoparticles gave a mean adsorption efficiency of 96.75 ± 1.13%. Circular dichroism spectra analysis showed that the protamine/DNA complexes had been coated by small SLNs, and that the anionic ternary nanoparticles formed did not disturb the construction of the binary complexes. SYBR Green I analysis suggested that the ternary nanoparticles could protect the DNA from nuclease degradation, and cell viability assay results showed that they exhibit lower cytotoxicity to A549 cells compared with the binary complexes and lipofectamine. The transfection efficiency of the ternary nanoparticles was better than that of naked DNA and the binary complexes, and almost equal to that of lipofectamine/DNA complexes, as revealed by inversion fluorescence microscope observation. These results indicated that the anionic ternary nanoparticles could facilitate gene transfer in cultured cells, and might alleviate the drawbacks of the conventional cationic vector/DNA complexes for gene delivery in vivo

  14. High-Throughput Analysis of Methylmalonic Acid in Serum, Plasma, and Urine by LC-MS/MS. Method for Analyzing Isomers Without Chromatographic Separation.

    Science.gov (United States)

    Kushnir, Mark M; Nelson, Gordon J; Frank, Elizabeth L; Rockwood, Alan L

    2016-01-01

    Measurement of methylmalonic acid (MMA) plays an important role in the diagnosis of vitamin B12 deficiency. Vitamin B12 is an essential cofactor for the enzymatic carbon rearrangement of methylmalonyl-CoA (MMA-CoA) to succinyl-CoA (SA-CoA), and the lack of vitamin B12 leads to elevated concentrations of MMA. Presence of succinic acid (SA) complicates the analysis because mass spectra of MMA and SA are indistinguishable, when analyzed in negative ion mode and the peaks are difficult to resolve chromatographically. We developed a method for the selective analysis of MMA that exploits the significant difference in fragmentation patterns of di-butyl derivatives of the isomers MMA and SA in a tandem mass spectrometer when analyzed in positive ion mode. Tandem mass spectra of di-butyl derivatives of MMA and SA are very distinct; this allows selective analysis of MMA in the presence of SA. The instrumental analysis is performed using liquid chromatography-tandem mass spectrometry (LC-MS/MS) in positive ion mode, which is, in combination with selective extraction of acidic compounds, is highly selective for organic acids with multiple carboxyl groups (dicarboxylic, tricarboxylic, etc.). In this method organic acids with a single carboxyl group are virtually undetectable in the mass spectrometer; the only organic acid, other than MMA, that is detected by this method is its isomer, SA. Quantitative measurement of MMA in this method is performed using a deconvolution algorithm, which mathematically resolves the signal corresponding to MMA and does not require chromatographic resolution of the MMA and SA peaks. Because of its high selectivity, the method utilizes isocratic chromatographic separation; reconditioning and re-equilibration of the chromatographic column between injections is unnecessary. The above features of the method allow high-throughput analysis of MMA with analysis cycle time of 1 min.

  15. Estimation of ΔR/R values by benchmark study of the Mössbauer Isomer shifts for Ru, Os complexes using relativistic DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Kaneko, Masashi [Japan Atomic Energy Agency, Nuclear Science and Engineering Center (Japan); Yasuhara, Hiroki; Miyashita, Sunao; Nakashima, Satoru, E-mail: snaka@hiroshima-u.ac.jp [Hiroshima University, Graduate School of Science (Japan)

    2017-11-15

    The present study applies all-electron relativistic DFT calculation with Douglas-Kroll-Hess (DKH) Hamiltonian to each ten sets of Ru and Os compounds. We perform the benchmark investigation of three density functionals (BP86, B3LYP and B2PLYP) using segmented all-electron relativistically contracted (SARC) basis set with the experimental Mössbauer isomer shifts for {sup 99}Ru and {sup 189}Os nuclides. Geometry optimizations at BP86 theory of level locate the structure in a local minimum. We calculate the contact density to the wavefunction obtained by a single point calculation. All functionals show the good linear correlation with experimental isomer shifts for both {sup 99}Ru and {sup 189}Os. Especially, B3LYP functional gives a stronger correlation compared to BP86 and B2PLYP functionals. The comparison of contact density between SARC and well-tempered basis set (WTBS) indicated that the numerical convergence of contact density cannot be obtained, but the reproducibility is less sensitive to the choice of basis set. We also estimate the values of ΔR/R, which is an important nuclear constant, for {sup 99}Ru and {sup 189}Os nuclides by using the benchmark results. The sign of the calculated ΔR/R values is consistent with the predicted data for {sup 99}Ru and {sup 189}Os. We obtain computationally the ΔR/R values of {sup 99}Ru and {sup 189}Os (36.2 keV) as 2.35×10{sup −4} and −0.20×10{sup −4}, respectively, at B3LYP level for SARC basis set.

  16. Direct infrared observation of hydrogen chloride anions in solid argon.

    Science.gov (United States)

    Huang, Tzu-Ping; Chen, Hui-Fen; Liu, Meng-Chen; Chin, Chih-Hao; Durrant, Marcus C; Lee, Yin-Yu; Wu, Yu-Jong

    2017-09-21

    To facilitate direct spectroscopic observation of hydrogen chloride anions (HCl - ), electron bombardment of CH 3 Cl diluted in excess Ar during matrix deposition was used to generate this anion. Subsequent characterization were performed by IR spectroscopy and quantum chemical calculations. Moreover the band intensity of HCl - decays slowly when the matrix sample is maintained in the dark for a prolonged time. High-level ab inito calculation suggested that HCl - is only weakly bound. Atom-in-molecule charge analysis indicated that both atoms of HCl - are negatively charged and the Cl atom is hypervalent.

  17. Derivatives of Dodecahalo-Closo-Dodecaborate Di-Anion

    OpenAIRE

    Avelar, Amy Cindy

    2009-01-01

    ABSTRACT OF THE DISSERTATIONDerivatives of the Dodecahalo-Closo-Dodecaborate Di-AnionbyAmy AvelarDoctor of Philosophy, Graduate Program in ChemistryUniversity of California, Riverside, December 2009Dr. Christopher A. Reed, ChairpersonThe di-anion, dodecahalo-closo-dodecaborate, B12X122-, where the X = Cl or Br, has been determined to be a useful weakly coordinating anion, WCA. Despite the di- negative charge, several elusive and reactive cationic species were stabilized with B12X122- as the c...

  18. Photoelectron spectroscopy of boron aluminum hydride cluster anions

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Haopeng; Zhang, Xinxing; Ko, Yeon Jae; Gantefoer, Gerd; Bowen, Kit H., E-mail: kbowen@jhu.edu, E-mail: kiran@mcneese.edu [Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Li, Xiang [Center for Space Science and Technology, University of Maryland–Baltimore County, Baltimore, Maryland 21250 (United States); Kiran, Boggavarapu, E-mail: kbowen@jhu.edu, E-mail: kiran@mcneese.edu [Department of Chemistry and Physics, McNeese State University, Lake Charles, Louisiana 70609 (United States); Kandalam, Anil K. [Department of Physics, West Chester University, West Chester, Pennsylvania 19383 (United States)

    2014-04-28

    Boron aluminum hydride clusters are studied through a synergetic combination of anion photoelectron spectroscopy and density functional theory based calculations. Boron aluminum hydride cluster anions, B{sub x}Al{sub y}H{sub z}{sup −}, were generated in a pulsed arc cluster ionization source and identified by time-of-flight mass spectrometry. After mass selection, their photoelectron spectra were measured by a magnetic bottle-type electron energy analyzer. The resultant photoelectron spectra as well as calculations on a selected series of stoichiometries reveal significant geometrical changes upon substitution of aluminum atoms by boron atoms.

  19. Photoelectron spectroscopy of boron aluminum hydride cluster anions.

    Science.gov (United States)

    Wang, Haopeng; Zhang, Xinxing; Ko, Yeon Jae; Gantefoer, Gerd; Bowen, Kit H; Li, Xiang; Kiran, Boggavarapu; Kandalam, Anil K

    2014-04-28

    Boron aluminum hydride clusters are studied through a synergetic combination of anion photoelectron spectroscopy and density functional theory based calculations. Boron aluminum hydride cluster anions, BxAlyHz(-), were generated in a pulsed arc cluster ionization source and identified by time-of-flight mass spectrometry. After mass selection, their photoelectron spectra were measured by a magnetic bottle-type electron energy analyzer. The resultant photoelectron spectra as well as calculations on a selected series of stoichiometries reveal significant geometrical changes upon substitution of aluminum atoms by boron atoms.

  20. Electrokinetic remediation of anionic contaminants from unsaturated soils

    International Nuclear Information System (INIS)

    Lindgren, E.R.; Kozak, M.W.; Mattson, E.D.

    1992-01-01

    Heavy-metal contamination of soil and groundwater is a widespread problem in the DOE weapons complex, and for the nation as a whole. Electrokinetic remediation is one possible technique for in situ removal of such contaminants from unsaturated soils. In previous studies at Sandia National Laboratories, the electromigration of chromate ions and anionic dye ions have been demonstrated. This paper reports on a series of experiments that were conducted to study the effect of moisture content on the electromigration rate of anionic contaminants in unsaturated soil and determine the limiting moisture content for which electromigration occurs

  1. Uranium extraction from sulfuric acid solution using anion exchange resin

    International Nuclear Information System (INIS)

    Sheta, M. E.; Abdel Aal, M. M.; Kandil, A. T.

    2012-12-01

    Uranium is currently recovered from sulfuric acid leach liquor using anion exchange resin as Amberlite IRA 402 (CT). This technology is based on fact that, uranium exists as anionic complexes. This takes place by controlling the pH of the solution, agitation time, temperature and resin to solution ratio (R/S). In this work, batch stirrer tank used for uranium extraction from sulfate medium and after extraction, elution process was done using 1M NaCl solution. After extraction and elution process, the resin was separated from the system and uranium was determined in the solution. (Author)

  2. Photodetachment and Doppler laser cooling of anionic molecules

    Science.gov (United States)

    Gerber, Sebastian; Fesel, Julian; Doser, Michael; Comparat, Daniel

    2018-02-01

    We propose to extend laser-cooling techniques, so far only achieved for neutral molecules, to molecular anions. A detailed computational study is performed for {{{C}}}2- molecules stored in Penning traps using GPU based Monte Carlo simulations. Two cooling schemes—Doppler laser cooling and photodetachment cooling—are investigated. The sympathetic cooling of antiprotons is studied for the Doppler cooling scheme, where it is shown that cooling of antiprotons to subKelvin temperatures could becomes feasible, with impacts on the field of antimatter physics. The presented cooling schemes also have applications for the generation of cold, negatively charged particle sources and for the sympathetic cooling of other molecular anions.

  3. Preparation of Cationic MOFs with Mobile Anions by Anion Stripping to Remove 2,4-D from Water

    Directory of Open Access Journals (Sweden)

    Tao Chen

    2017-07-01

    Full Text Available A cationic porous framework with mobile anions (MIL-101(Cr-Cl was easily and successfully synthesized by utilizing the stronger affinity of F− to Al3+ than Cr3+ in the charge-balanced framework of MIL-101(Cr. The structure, morphology and porosity of MIL-101(Cr-Cl were characterized. The obtained new materials retain the high surface area, good thermostability, and structure topology of MIL-101(Cr. With the mobile Cl− anion, MIL-101(Cr-Cl can be used as an ion-exchange material for anionic organic pollutions. In this work, 2,4-dichlorophenoxyacetic acid (2,4-D was used as a model to test the absorption performance of this new material. This new material exhibited improved adsorbability compared to that of the original metal-organic frameworks (MOFs. At the same time, this material also shows high anti-interference performance with changing solution pH.

  4. Equilibrium and Thermodynamic Studies of Anionic Dyes Removal by an Anionic Clay-Layered Double Hydroxide

    International Nuclear Information System (INIS)

    Kantasamy, N.; Siti Mariam Sumari

    2016-01-01

    Adsorption isotherm describes the interaction of adsorbates with adsorbent in equilibrium. Equilibrium data was examined using Langmuir and Freundlich isotherm models. Thermodynamic studies were used to evaluate the thermodynamic parameters; heat of enthalpy change (ΔH degree), Gibbs free energy change (ΔG degree) and heat of entropy change (ΔSdegree) in order to gain information regarding the nature of adsorption (exothermic or endothermic). Four reactive dyes of anionic type, Acid Blue 29 (AB29), Reactive Black 5 (RB5), Reactive Orange 16 (RO16) and Reactive Red 120 (RR120) were used to obtain equilibrium isotherms at 25, 35, 45 and 55 degree Celsius. Based on Giles' classification, the isotherm produced were of L2-type, indicating strong dye affinity towards the adsorbent, and with weak competition with the solvent molecules for active adsorption sites. Equilibrium data fitted both Langmuir and Freundlich isotherm models with high correlation coefficient (R 2 > 0.91) indicating the possibility of both homogeneity and heterogeneous nature of adsorption. The negative values of ΔGdegree indicate the adsorption processes were spontaneous and feasible. The negative values of ΔHdegree lie between -20 to -75 kJ/ mol, suggesting these processes were exothermic and physical in nature. The negative values of ΔSdegree are indication of decreased disorder and randomness of spontaneous adsorption of reactive dyes on layered double hydroxide as adsorbent. (author)

  5. Detection of biologically active isomers of conjugated linoleic acid in kaymak

    Directory of Open Access Journals (Sweden)

    Ökten, Sevtap

    2005-12-01

    Full Text Available Numerous physiological effects are attributed to conjugated linoleic acids (CLA. Biologically active isomers of CLA ( cis -9, trans -11 (C18:2 and trans- 10, cis- 12 (C18:2 have been reported to have anticarcinogenic, antioxidative and antiatherosclerotic properties. Relatively rich sources of CLA include milk fat-containing foods such as kaymak. Kaymak is a kind of concentrated cream which is traditionally manufactured from buffalo or cow's milk mainly in Turkey . The objective of this study was to determine CLA concentrations during kaymak production. Kaymak was manufactured from cow's milk which was enriched with unfermented cream. Biologically active isomers of CLA in raw milk, cream and kaymak were analyzed using gas chromatography. The method was quick, repeatable and sensitive for the CLA determination of samples. Significant differences were found among the concentrations of both isomer and total CLA during the production process (pNumerosos efectos fisiológicos se atribuyen a los ácidos linoleico conjugados (CLA. Así los isómeros biológicamente activos ( cis -9, trans -11 (C18:2 y trans- 10, cis del ácido linoleico han sido descritos con propiedades anticarcinogénicas, antioxidantes y antiarterioscleróticas. Fuentes relativamente ricas de CLA incluyen alimentos con grasas lácteas tales como el kaymak. El kaymak es una crema concentrada elaborada de leche de búfalo o vaca principalmente en Turquía. El objetivo de este estudio fue la determinación de la concentración de CLA durante la producción de kaymak. El kaymak objeto de estudio fue elaborado a partir de leche de vaca que fue enriquecida con crema no fermentada. Los isómeros biológicamente activos del CLA fueron analizados por cromatografía gaseosa en leche cruda, crema y kaymak. El método empleado fue rápido, reproducible y sensible. Se encontraron diferencias significativas en las concentraciones de ambos isómeros y de CLA total durante el proceso de producci

  6. Trans fatty acid isomers and the trans-9/trans-11 index in fat containing foods

    Science.gov (United States)

    Kuhnt, Katrin; Baehr, Melanie; Rohrer, Carsten; Jahreis, Gerhard

    2011-01-01

    To determine trans fatty acid (TFA) distribution of contemporary foods, especially regarding individual trans octadecenoic acids (trans C18:1), 339 German foods of six categories (semi-solid fats, deep-fried potato products, bakery products, confectioneries, instant products and butter) were analysed using two GC methods. Results showed a high variation of TFA content between and within the categories containing between 0 and 40.5% of FAME except in butter, which is a source of natural TFA. The mean TFA values were below 2.0% of FAME, however, bakery products contained 4.5% and butter fat 3.2%, respectively. In addition, the distribution of individual trans C18:1 differed. In samples containing ruminant fat (butter and various confectioneries), vaccenic acid (t11-C18:1, t11) predominated, while in foods containing industrially hydrogenated fats, elaidic acid (trans-9, t9-) and t10-C18:1 were the major trans isomers.. This was reflected by a low t9/t11 index of 0.3 and 0.5 in butter and ruminant fat containing confectioneries, respectively, whilst the highest index was observed in shortenings and deep-fried potato products at 5.2 and 6.8, respectively. In conclusion, the TFA content of foods available on the German market is generally declining, but substantial variations are present. The t9/t11 index could be used as an indicator to determine ruminant fat. Practical applications: A number of studies provide evidence that a high TFA intake, particularly of industrial origin, adversely affects human health. The TFA content of foods could be reduced due to the introduction of several mandatory regulations and modifications regarding the hydrogenation process of oils. The most abundant dietary TFA are the isomers of trans C18:1. Unfortunately, the differentiation of these isomers is not yet very common, though the trans C18:1 profile differs depending on its origin (bacterial hydrogenation in the rumen or industrial hydrogenation). To date, data for TFA content

  7. Carborane-stilbene dyads: the influence of substituents and cluster isomers on photoluminescence properties.

    Science.gov (United States)

    Ferrer-Ugalde, A; Cabrera-González, J; Juárez-Pérez, E J; Teixidor, F; Pérez-Inestrosa, E; Montenegro, J M; Sillanpää, R; Haukka, M; Núñez, R

    2017-02-14

    Two novel styrene-containing meta-carborane derivatives substituted at the second carbon cluster atom (C c ) with either a methyl (Me) or a phenyl (Ph) group are introduced herein along with a new set of stilbene-containing ortho- (o-) and meta- (m-) carborane dyads. The latter set of compounds have been prepared from styrene-containing carborane derivatives via a Heck coupling reaction. High regioselectivity has been achieved for these compounds by using a combination of palladium complexes [Pd 2 (dba) 3 ]/[Pd(t-Bu 3 P) 2 ] as a catalytic system, yielding exclusively E isomers. All compounds have been fully characterised and the crystal structures of seven of them were analysed by X-ray diffraction. The absorption spectra of these compounds are similar to those of their respective fluorophore groups (styrene or stilbene), showing a very small influence of the substituent (Me or Ph) linked to the second C c atom or the cluster isomer (o- or m-). On the other hand, fluorescence spectroscopy revealed high emission intensities for Me-o-carborane derivatives, whereas their Ph-o-carborane analogues evidenced an almost total lack of fluorescence, confirming the significant role of the substituent bound to the adjacent C c in o-carboranes. In contrast, all the m-carborane derivatives display similar photoluminescence (PL) behavior regardless of the substituent attached to the second C c , demonstrating its small influence on emission properties. Additionally, m-carborane derivatives are significantly more fluorescent than their o-counterparts, reaching quantum yield values as high as 30.2%. Regarding solid state emission, only stilbene-containing Ph-o-carborane derivatives, which showed very low fluorescence in solution, exhibited notable PL emission in films attributed to aggregation-induced emission. DFT calculations were performed to successfully complement the photoluminescence studies, supporting the experimentally observed photophysical behavior of the styrene and

  8. Anion and cation diffusion in barium titanate and strontium titanate

    International Nuclear Information System (INIS)

    Kessel, Markus Franz

    2012-01-01

    Perovskite oxides show various interesting properties providing several technical applications. In many cases the defect chemistry is the key to understand and influence the material's properties. In this work the defect chemistry of barium titanate and strontium titanate is analysed by anion and cation diffusion experiments and subsequent time-of-flight secondary ion mass spectrometry (ToF-SIMS). The reoxidation equation for barium titanate used in multi-layer ceramic capacitors (MLCCs) is found out by a combination of different isotope exchange experiments and the analysis of the resulting tracer diffusion profiles. It is shown that the incorporation of oxygen from water vapour is faster by orders of magnitude than from molecular oxygen. Chemical analysis shows the samples contain various dopants leading to a complex defect chemistry. Dysprosium is the most important dopant, acting partially as a donor and partially as an acceptor in this effectively acceptor-doped material. TEM and EELS analysis show the inhomogeneous distribution of Dy in a core-shell microstructure. The oxygen partial pressure and temperature dependence of the oxygen tracer diffusion coefficients is analysed and explained by the complex defect chemistry of Dy-doped barium titanate. Additional fast diffusion profiles are attributed to fast diffusion along grain boundaries. In addition to the barium titanate ceramics from an important technical application, oxygen diffusion in cubic, nominally undoped BaTiO 3 single crystals has been studied by means of 18 O 2 / 16 O 2 isotope exchange annealing and subsequent determination of the isotope profiles in the solid by ToF-SIMS. It is shown that a correct description of the diffusion profiles requires the analysis of the diffusion through the surface space-charge into the material's bulk. Surface exchange coefficients, space-charge potentials and bulk diffusion coefficients are analysed as a function of oxygen partial pressure and temperature. The

  9. Preferential alkali metal adduct formation by cis geometrical isomers of dicaffeoylquinic acids allows for efficient discrimination from their trans isomers during ultra-high-performance liquid chromatography/quadrupole time-of-flight mass spectrometry

    CSIR Research Space (South Africa)

    Makola, MM

    2016-03-01

    Full Text Available discrimination of the geometrical isomers of these molecules has proven to be an elusive task. UV-irradiated methanolic solutions of diCQA were analyzed using an ultra-high-performance liquid chromatography/quadrupole time-of-flight mass spectrometry (UHPLC...

  10. Dietary cation anion difference: Impact on productive and ...

    African Journals Online (AJOL)

    Various nutritional tools have been used to improve the productive and reproductive performance of animals, among which difference between certain minerals, called dietary cation anion difference (DCAD) plays a pivotal role. Low or negative DCAD diets reduce blood pH and HCO3- and animal becomes acidotic.

  11. The effect of membrane diffusion potential change on anionic drugs ...

    African Journals Online (AJOL)

    The effect of membrane potential change on anionic drugs Indomethacin and barbitone induced human erythrocyte shape change and red cell uptake of drug has been studied using microscopy and spectrophotometry techniques respectively. The membrane potential was changed by reducing the extracellular chloride ...

  12. Core-modified octaphyrins: Syntheses and anion-binding properties

    Indian Academy of Sciences (India)

    Unknown

    proton of the inverted ring of selenophene from the biselenophene unit forms a secondary interaction. (non-electrostatic) with oxygen of the TFA. Apart from the oxygen, the fluorine of the triflate anion also forms secondary interaction with the proton of the methyl group of the mesityl ring. Tetraoxaoctaphyrin 9 also binds two ...

  13. Beneficiation of Nigerian Clay with Poly Anionic Cellulose-Regular ...

    African Journals Online (AJOL)

    ... concentrations and the effect of different concentration of Poly Anionic Cellulose-Regular (PAC-R) on the Emede clay was investigated. The experiment centred on the determination of its suitability for use in drilling mud formulation. Preliminary investigation suggests that Emede clay has a good potential for use in drilling ...

  14. Contribution of attendant anions on cadmium toxicity to soil enzymes.

    Science.gov (United States)

    Tian, Haixia; Kong, Long; Megharaj, Mallavarapu; He, Wenxiang

    2017-11-01

    Sorption and desorption are critical processes to control the mobility and biotoxicity of cadmium (Cd) in soils. It is known that attendant anion species of heavy metals could affect metal adsorption on soils and might further alter their biotoxicity. However, for Cd, the influence of attendant anions on its sorption in soils and subsequent toxicity on soil enzymes are still unknown. In this work, four Cd compounds with different salt anions (SO 4 2- , NO 3 - , Cl - , and Ac - ) were selected to investigate their impact of on the sorption, soil dehydrogenase activity (DHA) and alkaline phosphatase activity (ALP). Thus, a series of simulated Cd pollution batch experiments including measuring adsorption-desorption behavior of Cd on soils and soil enzyme activities were carried out. Results showed that CdSO 4 exhibited highest sorption capacity among the tested soils except in Hunan soil. The Cd sorption with NO 3 - displayed a similar behavior with Cl - on all tested soils. Compared with soil properties, all four kinds of anions on Cd sorption played a more significant role affecting Cd ecological toxicity to soil DHA and ALP. Cd in acetate or nitrate form appears more sensitive towards DHA than sulphate and chloride, while the later pair is more toxic towards ALP than the former. These results have important implications for evaluation of Cd contamination using soil enzyme as bioindicator. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. The anionic biosurfactant rhamnolipid does not denature industrial enzymes

    Directory of Open Access Journals (Sweden)

    Jens Kvist Madsen

    2015-04-01

    Full Text Available Biosurfactants (BS are surface-active molecules produced by microorganisms. Their combination of useful properties and sustainable production make them promising industrial alternatives to petrochemical and oleochemical surfactants. Here we compare the impact of the anionic BS rhamnolipid (RL and the conventional/synthetic anionic surfactant sodium dodecyl sulfate (SDS on the structure and stability of three different commercially used enzymes, namely the cellulase Carezyme® (CZ, the phospholipase Lecitase Ultra® (LT and the α-amylase Stainzyme® (SZ. Our data reveal a fundamental difference in their mode of interaction. SDS shows great diversity of interaction towards the different enzymes. It efficiently unfolds both LT and CZ, but LT is unfolded by SDS through formation of SDS clusters on the protein well below the cmc, while CZ is only unfolded by bulk micelles and on average binds significantly less SDS than LT. SDS binds with even lower stoichiometry to SZ and leads to an increase in thermal stability. In contrast, RL does not affect the tertiary or secondary structure of any enzyme at room temperature, has little impact on thermal stability and only binds detectably (but at low stoichiometries to SZ. Furthermore all enzymes maintain activity at both monomeric and micellar concentrations of RL. We conclude that RL, despite its anionic charge, is a surfactant that does not compromise the structural integrity of industrially relevant proteins. This makes RL a promising alternative to current synthetic anionic surfactants in a wide range of commercial applications.

  16. A carbohydrate-anion recognition system in aprotic solvents.

    Science.gov (United States)

    Ren, Bo; Dong, Hai; Ramström, Olof

    2014-05-01

    A carbohydrate-anion recognition system in nonpolar solvents is reported, in which complexes form at the B-faces of β-D-pyranosides with H1-, H3-, and H5-cis patterns similar to carbohydrate-π interactions. The complexation effect was evaluated for a range of carbohydrate structures; it resulted in either 1:1 carbohydrate-anion complexes, or 1:2 complex formation depending on the protection pattern of the carbohydrate. The interaction was also evaluated with different anions and solvents. In both cases it resulted in significant binding differences. The results indicate that complexation originates from van der Waals interactions or weak CH⋅⋅⋅A(-) hydrogen bonds between the binding partners and is related to electron-withdrawing groups of the carbohydrates as well as increased hydrogen-bond-accepting capability of the anions. © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

  17. Electronic spectra of anions intercalated in layered double hydroxides

    Indian Academy of Sciences (India)

    Transition metal complexes intercalated in layered double hydroxides have a different electronic structure as compared to their free state owing to their confinement within the interlayer gallery. UV–Vis absorptions of the intercalated complex anions show a significant shift as compared to their free state. The ligand to metal ...

  18. Measurement of carbon disulfide anion diffusion in a TPC

    International Nuclear Information System (INIS)

    Ohnuki, Tohru; Snowden-Ifft, D.P.Daniel P.; Martoff, C.J.C. Jeff

    2001-01-01

    A Negative Ion Time Projection Chamber was used to measure the field dependence of lateral and longitudinal diffusion for CS 2 anions drifting in mixtures of CS 2 and Ar at 40 Torr. Ion drift velocities and limits on the capture distance for electrons as a function of field and gas mixture are also reported

  19. Changes in plasma osmolality and anion gap: potential predictors of ...

    African Journals Online (AJOL)

    These changes may be related to mortality in patients on haemodialysis. Objective: To determine the relationship of mortality to plasma osmolality and anion gap inpatients on haemodialysis. Methods: Fifty consecutive dialysis naive stable stage 5 chronic kidney disease subjects aged between 18 and 70 years, attending a ...

  20. The Determination of Anionic Surfactants in Natural and Waste Waters.

    Science.gov (United States)

    Crisp, P. T.; And Others

    1983-01-01

    Background information, procedures, and results of an experiment suitable for measuring subpart per million concentrations of anionic surfactants in natural waters and waste effluents are provided. The experiment required only a spectrophotometer or filter photometer and has been successfully performed by students in an undergraduate environmental…