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Sample records for optical isomers

  1. 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...

  2. Differential Effect of Amphetamine Optical Isomers on Bender Gestalt Performance of the Minimally Brain Dysfunctioned

    Science.gov (United States)

    Arnold, L. Eugene; And Others

    1978-01-01

    The differential effect of amphetamine optical isomers on Bender Gestalt performance was examined in 31 hyperkinetic minimally brain dysfunctioned children between the ages of 4 and 12 years, using a double-blind Latin-square crossover comparison. (Author)

  3. Portable, Battery Operated Capillary Electrophoresis with Optical Isomer Resolution Integrated with Ionization Source for Mass Spectrometry

    Science.gov (United States)

    Moini, Mehdi; Rollman, Christopher M.

    2016-03-01

    We introduce a battery operated capillary electrophoresis electrospray ionization (CE/ESI) source for mass spectrometry with optical isomer separation capability. The source fits in front of low or high resolution mass spectrometers similar to a nanospray source with about the same weight and size. The source has two high voltage power supplies (±25 kV HVPS) capable of operating in forward or reverse polarity modes and powered by a 12 V rechargeable lithium ion battery with operation time of ~10 h. In ultrafast CE mode, in which short narrow capillaries (≤15 μm i.d., 15-25 cm long) and field gradients ≥1000 V/cm are used, peak widths at the base are <1 s wide. Under these conditions, the source provides high resolution separation, including optical isomer resolution in ~1 min. Using a low resolution mass spectrometer (LTQ Velos) with a scan time of 0.07 s/scan, baseline separation of amino acids and their optical isomers were achieved in ~1 min. Moreover, bovine serum albumin (BSA) was analyzed in ~1 min with 56% coverage using the data-dependent MS/MS. Using a high resolution mass spectrometer (Thermo Orbitrap Elite) with 15,000 resolution, the fastest scan time achieved was 0.15 s, which was adequate for CE-MS analysis when optical isomer separation is not required or when the optical isomers were well separated. Figures of merit including a detection limit of 2 fmol and linear dynamic range of two orders of magnitude were achieved for amino acids.

  4. Lactones 42. Stereoselective enzymatic/microbial synthesis of optically active isomers of whisky lactone.

    Science.gov (United States)

    Boratyński, Filip; Smuga, Małgorzata; Wawrzeńczyk, Czesław

    2013-11-01

    Two different methods, enzyme-mediated reactions and biotrasformations with microorganisms, were applied to obtain optically pure cis- and trans-isomers of whisky lactone 4a and 4b. In the first method, eight alcohol dehydrogenases were investigated as biocatalysts to enantioselective oxidation of racemic erythro- and threo-3-methyloctane-1,4-diols (1a and 1b). Oxidation processes with three of them, alcohol dehydrogenases isolated from horse liver (HLADH) as well as recombinant from Escherichia coli and primary alcohol dehydrogenase (PADH I), were characterized by the highest degree of conversion with moderate enantioselectivity (ee=27-82%) of the reaction. In all enzymatic reactions enantiomerically enriched not naturally occurring isomers of trans-(-)-(4R,5S)-4b or cis-(+)-(4R,5R)-4a were formed preferentially. In the second strategy, based on microbial lactonization of γ-oxoacids, naturally occurring opposite isomers of whisky lactones were obtained. Trans-(+)-(4S,5R)-isomer (ee=99%) of whisky lactone 4b was stereoselectively formed as the only product of biotransformations of 3-methyl-4-oxooctanoic acid (5) catalyzed by Didimospheria igniaria KCH6651, Laetiporus sulphurens AM525, Chaetomium sp.1 KCH6670 and Saccharomyces cerevisiae AM464. Biotransformation of γ-oxoacid 5, in the culture of Beauveria bassiana AM278 and Pycnidiella resinae KCH50 afforded a mixtures of trans-(+)-(4S,5R)-4b with enantiomeric excess ee=99% and cis-(-)-(4S,5S)-4a with enantiomeric excesses ee=77% and ee=45% respectively.

  5. Comparative study on pharmacological effects of DM-phencynonate hydrochloride and its optical isomers

    Institute of Scientific and Technical Information of China (English)

    Li-yun WANG; Jian-quan ZHENG; Yun WANG; Bo-hua ZHONG; Jin-xiu RUAN; Ke-liang LIU

    2005-01-01

    Aim: The 3 -azabicyclo(3,3, 1)nonanyl-9-α-yl-α-cyclopentyl-α-phenyl-α-glycolate (DM-phencynonate hydrochloride, DMCPG) is a demethylated metabolite of 3-methyl-3-azabicyclo(3,3,1)nonanyl-9-α-yl-α-cyclopentyl-α-phenyl-α-glycolate (phencynonate hydrochloride, CPG). (±)DMCPG had one chiral center and two enantiomers [R(-) and S(+)DMCPG]. Here we carried out a comparative study of the pharmacological profiles of these optical isomers. Methods: Affinity and relative efficacy were tested using a radioligand-binding assay with muscarinic acetylcholine receptors from the rat cerebral cortex. Pharmacological activity was assessed in three individual experiments: (1) potentiating the effect of a subthreshold hypnotic dose of sodium pentobarbital; (2) inhibiting oxotremorineinduced salivation; and (3) inhibiting the contractile response to carbachol.Results: In the competitive binding assay, R(-)DMCPG (Ki=763.75 nmol/L) was 4-and 2-fold more potent than (±)DMCPG (Ki=3186 nmol/L) and S(+)DMCPG (Ki= 1699 nmol/L) in inhibiting the binding of [3H]QNB. The R(-) and S (+) configurations showed positive cooperation (nH>1) with the muscarinic receptor, whereas (±)DMCPG had a negative cooperation (nH<1) relationship with the muscarinic receptor in a radio-binding assay. Both the R(-) and S(+) configurations could potentiate the effect of sub-threshold hypnotic dose of sodium pentobarbital in a dose-dependent manner (the ED50 values were 2.53 and 18.65 mg/kg, respectively),but (±)DMCPG did not display significant central depressant effects at doses from 10 to 29.15 mg/kg (P>0.05). (±)DMCPG and its optical isomers suppressed the guinea pig ileum contractile response to carbachol. The IC50 values were 7.78×10-9,1.88×10-7, and 1.03× 10-7 nmol/L, respectively. In the anti-salivation study,(±)DMCPG and its enantiomers depressed oxotremorine- induced salivation in a dose-dependent manner, and the order of potency was R(-)DMCPG (ED50=0.44 mg/kg)>(±)DMCPG (ED50

  6. Stereochemical analysis of menthol and menthylamine isomers using calculated and experimental optical rotation data

    Science.gov (United States)

    Reinscheid, F.; Reinscheid, U. M.

    2016-01-01

    The complete series of menthol isomers and their corresponding amino derivatives (base and protonated/HCl forms), were investigated using experimental and theoretical data. Our study focused on the conformational and configurational analysis, and revealed that experimental data should be used in combination with calculated data. Furthermore, even in the case of the highly studied member, menthol, discrepancies were found among previously published literature values. We show that the correct determination of the population mix is a must for the correct prediction of the absolute configuration (AC) of neoisomenthol. The neoiso forms are of special interest since a number of structural inconsistences can be found in the literature. We present a stringent proof of the AC of neoisomenthol based on literature information. To the best of our knowledge, the AC of neoisomenthylamine is for the first time shown using experimental and calculated optical rotation data. A correction of a series of publications containing an important error in the assignment of (+)-menthylamine (correct: (+)-neomenthylamine) is presented. With 26 data pairs (experimental versus calculated) of optical rotation values a regression is performed. The AC of all 12 compounds, even the most difficult neoiso forms, could be predicted correctly using experimental low-temperature NMR data. Furthermore, if only experimental data with an optical rotation outside the range of -10 +10 are used, all 12 compounds would have been correctly assigned without low-temperature NMR data as restraints.

  7. Pharmacological profiles of an anticholinergic agent, phencynonate hydrochloride, and its optical isomers

    Institute of Scientific and Technical Information of China (English)

    Li-yun WANG; Yun WANG; Jian-quan ZHENG; Bo-hua ZHONG; He LIU; Si-jian DONG; Jin-xiu RUAN; Ke-liang LIU

    2005-01-01

    Aim: To comparatively study the pharmacological profiles of 3-methyl-3-azabicyclo (3,3,1)nonanyl-9-α-yl-α-cyclopentyl-α-phenyl-α-glycolate (phencynonate hydrochloride, CPG), an anticholinergic agent, and its enantiomers [R(-)- and S(+)-CPG]. Methods: The affinity and relative efficacy were tested using radioligand-binding assay with muscarinic acetylcholine receptors from rat cerebral cortex. The pharmacological activities were assessed in three individual experiments: (1) potentiating the effect of subthreshold hypnotic dose of sodium pentobarbital; (2) inhibiting oxotremorine-induced salivation; and (3) inhibiting the contractile response to carbachol. Results: The order of potency of phencynonate hydrochloride and its optical isomers to inhibit the binding of [3H]quinuclidinyl benzilate ([3H] QNB) was R(-)-CPG (Ki=46.49± 1.27 nmol/L)>CPG (Ki=271.37±72.30 nmol/L)>S(+)-CPG (Ki=1263.12±131.64 nmol/L). The results showed that R(-)-CPG had the highest affinity to central muscarinic receptors among the three compounds, but did not show any central depressant effects at dose from 10.00 to 29.15 mg/kg. CPG increased the effects of subthreshold hypnotic dose of sodium pentobarbital induced-sleeping [the ED50±95 % LC value was 21.06±3.04 mg/kg]. CPG and R(-)-CPG displayed nearly equipotent effect in depressing oxotremorineinduced salivation [the ED50±95% LC for R(-) and CPG were 1.10±0.28 and 1.07±0.15 mg/kg, respectively], and the contractile response to carbachol (pA2 values for R(-) and CPG were 6.84 and 6.80, respectively). S(+)-CPG presented the lowest anticholinergic profiles, but could potentate effects of its enantiomers in some manner. Conclusions: These data suggested that R(-)-CPG acted as an eutomer in racemate and a competitive antagonist to acetylcholine muscarinic receptors,but S(+)-CPG was less active in comparison to R(-)-CPG and its racemate. The central depressant effects of R(-)-CPG and S(+)-CPG were lower in comparison to its racemate.

  8. Optimal performance of single-column chromatography and simulated moving bed processes for the separation of optical isomers

    Science.gov (United States)

    Medi, Bijan; Kazi, Monzure-Khoda; Amanullah, Mohammad

    2013-06-01

    Chromatography has been established as the method of choice for the separation and purification of optically pure drugs which has a market size of about 250 billion USD. Single column chromatography (SCC) is commonly used in the development and testing phase of drug development while multi-column Simulated Moving Bed (SMB) chromatography is more suitable for large scale production due to its continuous nature. In this study, optimal performance of SCC and SMB processes for the separation of optical isomers under linear and overloaded separation conditions has been investigated. The performance indicators, namely productivity and desorbent requirement have been compared under geometric similarity for the separation of a mixture of guaifenesin, and Tröger's base enantiomers. SCC process has been analyzed under equilibrium assumption i.e., assuming infinite column efficiency, and zero dispersion, and its optimal performance parameters are compared with the optimal prediction of an SMB process by triangle theory. Simulation results obtained using actual experimental data indicate that SCC may compete with SMB in terms of productivity depending on the molecules to be separated. Besides, insights into the process performances in terms of degree of freedom and relationship between the optimal operating point and solubility limit of the optical isomers have been ascertained. This investigation enables appropriate selection of single or multi-column chromatographic processes based on column packing properties and isotherm parameters.

  9. Optical Isomers of 5-Methyl-1- (1-naphthyl) -1,2,3-triazole in the Crystal Structure

    Institute of Scientific and Technical Information of China (English)

    DONG Heng-Shan; ZHUANG Shan-Xue; LIU Shi-Qian; QUAN Bin; ZHANG Tong-Qiang

    2003-01-01

    @@ ( ± )-5-Methyl-1-( 1-naphthyl )-1,2, 3-triazole by which 5-methyl-1-( 1-naphthyl )-1,2, 3-triazol-4-carboxylic acid was prepared from aromatic amine was reported. The product was investigated with X-ray crystallography. Compound, C13H 11N3, Mr = 209.25, crystallized in the orthorhombic space group Pbca with unit cell parameters a = 1.0373(2) nm, b=1.1691(2) nm, c=1.7579(4) nm, α=90.00°, β=90.00°, γ=90.00°, V=2.1318(7)nm3, Z = 8, Dm = 1. 304 Mg/m3. The optical isomers of 5-methyl-1-(1-naphthyl)-1, 2,3-triazole was investigated in the crystal structure.

  10. Potential antifertility agents. 6. Synthesis and biological activities of optical isomers of 4 beta-(p-methozyphenyl)-2 beta-methylcyclohexane-alpha-carboxylic acid and related compounds.

    Science.gov (United States)

    Crenshaw, R R; Jenks, T A; Luke, G M; Bialy, G

    1974-12-01

    The optical isomers of the title compound were synthesized and the biological potencies of the two enantiomers were compared. There was essentially no difference in their hypocholesterolemic activities, as had been predicted, and little or no difference between their uterotropic potencies. The approximately equal uterotropic activities seen with the enantiomers is explained in terms of stereochemical requirements at the receptor level for an estrogenic response. A working model of an estrogenic receptor is proposed. An accompanying paper provides support for the proposed model.

  11. The effects of the EW dipeptide optical and chemical isomers on the CFU-S population in intact and irradiated mice.

    Science.gov (United States)

    Deigin, V I; Semenets, T N; Zamulaeva, I A; Maliutina, Ya V; Selivanova, E I; Saenko, A S; Semina, O V

    2007-03-01

    The influence of Glu-Trp (EW) synthetic dipeptide isomers on hemopoietic progenitor cells and certain immune response reactions is determined by their optical and chemical properties. Thus, the all L-amino acid containing dipeptides L-Glu-L-Trp and L-gammaGlu-L-Trp have no effect on proliferation of committed and pluripotent CFU-S in intact bone marrow. The optical isomers of the Glu residue are an essential determinant of the EW dipeptide biological activity. The inversion of the amino acid optical form imparts suppressor properties: D-Glu-D-Trp,D--gammaGlu-D-Trp, D-Glu-L-Trp and D-gammaGlu-L-Trp inhibit proliferation of hemopoietic progenitors in intact bone marrow. The type of the peptide bond between L-Glu and Trp is another important factor for the biological activity of the L-Glu-containing peptides. Unlike L-Glu-D-Trp with alpha-peptide bond, the dipeptide L-gammaGlu-D-Trp with gamma-peptide bond stimulates CFU-S-8 proliferation in intact bone marrow. The diverse effects of the EW optical isomers on hemopoietic progenitors underlie the radioprotective properties of the D-Glu-containing dipeptides and the radiotherapeutic ones of the L-Glu dipeptides. In animals, pre-irradiation injection of D-Glu-D-Trp, D-gammaGlu-D-Trp, D-Glu-L-Trp, D-gammaGlu-L-Trp, or post-irradiation injection of L-Glu-L-Trp, L-gammaGlu-L-Trp promoted regeneration of the hemopoietic progenitor population.

  12. Photoinduced dichroism and optical anisotropy in a liquid-crystalline azobenzene side chain polymer caused by anisotropic angular distribution of trans and cis isomers

    Science.gov (United States)

    Blinov, Lev M.; Kozlovsky, Mikhail V.; Ozaki, Masanori; Skarp, Kent; Yoshino, Katsumi

    1998-10-01

    Photochromism has been studied for two comb-like liquid-crystalline copolymers (I) and (II) containing azobenzene chromophores in their side chains. In a smectic glass phase of both copolymers, upon short-time irradiation by UV light, long-living cis isomers are observed. Both copolymers manifest the photoinduced anisotropy, the physical mechanisms of which seem to be quite different. In spin-coated films of polymer (II), the origin of the anisotropy is a strong stable dichroism, which is due to an enrichment and depletion of the chosen angular direction, correspondingly, with trans and cis isomers of the azobenzene chromophores. Polymer (I) manifests no dichroism at all, and its induced optical anisotropy may be accounted for by a rather slow chromophore reorientation. In copolymer (II) a considerable reorientation of the mesogenic groups also occurs as a secondary phenomenon at the stage of the cis isomer formation only. This observation shed more light on the general process of the light-induced molecular reorientation in polymers, liquid crystals, and Langmuir-Blodgett films, which is of great importance for holographic information recording.

  13. In Vivo Differences between Two Optical Isomers of Radioiodinated o-iodo-trans-decalinvesamicol for Use as a Radioligand for the Vesicular Acetylcholine Transporter.

    Directory of Open Access Journals (Sweden)

    Izumi Uno

    Full Text Available To develop a superior VAChT imaging probe for SPECT, radiolabeled (--OIDV and (+-OIDV were isolated and investigated for differences in their binding affinity and selectivity to VAChT, as well as their in vivo activities.Radioiodinated o-iodo-trans-decalinvesamicol ([125I]OIDV has a high binding affinity for vesicular acetylcholine transporter (VAChT both in vitro and in vivo. Racemic [125I]OIDV was separated into its two optical isomers (--[125I]OIDV and (+-[125I]OIDV by HPLC. To investigate VAChT binding affinity (Ki of two OIDV isomers, in vitro binding assays were performed. In vivo biodistribution study of each [125I]OIDV isomer in blood, brain regions and major organs of rats was performed at 2,30 and 60 min post-injection. In vivo blocking study were performed to reveal the binding selectivity of two [125I]OIDV isomers to VAChT in vivo. Ex vivo autoradiography were performed to reveal the regional brain distribution of two [125I]OIDV isomers and (--[123I]OIDV for SPECT at 60 min postinjection.VAChT binding affinity (Ki of (--[125I]OIDV and (+-[125I]OIDV was 22.1 nM and 79.0 nM, respectively. At 2 min post-injection, accumulation of (--[125I]OIDV was the same as that of (+-[125I]OIDV. However, (+-[125I]OIDV clearance from the brain was faster than (--[125I]OIDV. At 30 min post-injection, accumulation of (--[125I]OIDV (0.62 ± 0.10%ID/g was higher than (+-[125I]OIDV (0.46 ± 0.07%ID/g in the cortex. Inhibition of OIDV binding showed that (--[125I]OIDV was selectively accumulated in regions known to express VAChT in the rat brain, and ex vivo autoradiography further confirmed these results showing similar accumulation of (--[125I]OIDV in these regions. Furthermore, (--[123I]OIDV for SPECT showed the same regional brain distribution as (--[125I]OIDV.These results suggest that radioiodinated (--OIDV may be a potentially useful tool for studying presynaptic cholinergic neurons in the brain.

  14. Photoelectron spectroscopy and theoretical study of M(IO3)2(-) (M = H, Li, Na, K): structural evolution, optical isomers, and hyperhalogen behavior.

    Science.gov (United States)

    Hou, Gao-Lei; Wu, Miao Miao; Wen, Hui; Sun, Qiang; Wang, Xue-Bin; Zheng, Wei-Jun

    2013-07-28

    H(IO3)2(-) and M(IO3)2(-) (M = Li, Na, K) anions were successfully produced via electrospray ionization of their corresponding bulk salt solutions, and were characterized by combining negative ion photoelectron spectroscopy and quantum chemical calculations. The experimental vertical detachment energies (VDEs) of M(IO3)2(-) (M = H, Li, Na, K) are 6.25, 6.57, 6.60, and 6.51 eV, respectively, and they are much higher than that of IO3(-) (4.77 eV). The theoretical calculations show that each of these anions has two energetically degenerate optical isomers. It is found that the structure of H(IO3)2(-) can be written as IO3(-)(HIO3), in which the H atom is tightly bound to one of the IO3(-) groups and forms an iodic acid (HIO3) molecule; while the structures of M(IO3)2(-) can be written as (IO3(-))M(+)(IO3(-)), in which the alkali metal atoms interact with the two IO3(-) groups almost equally and bridge the two IO3(-) groups via two O atoms of each IO3(-) with the two MOOI planes nearly perpendicular to each other. In addition, the high VDEs of M(IO3)2(-) (M = Li, Na, K) can be explained by the hyperhalogen behavior of their neutral counterparts.

  15. Photoelectron spectroscopy and theoretical study of M(IO3)2- (M = H, Li, Na, K): Structural evolution, optical isomers, and hyperhalogen behavior

    Science.gov (United States)

    Hou, Gao-Lei; Wu, Miao Miao; Wen, Hui; Sun, Qiang; Wang, Xue-Bin; Zheng, Wei-Jun

    2013-07-01

    H(IO3)2- and M(IO3)2- (M = Li, Na, K) anions were successfully produced via electrospray ionization of their corresponding bulk salt solutions, and were characterized by combining negative ion photoelectron spectroscopy and quantum chemical calculations. The experimental vertical detachment energies (VDEs) of M(IO3)2- (M = H, Li, Na, K) are 6.25, 6.57, 6.60, and 6.51 eV, respectively, and they are much higher than that of IO3- (4.77 eV). The theoretical calculations show that each of these anions has two energetically degenerate optical isomers. It is found that the structure of H(IO3)2- can be written as IO3-(HIO3), in which the H atom is tightly bound to one of the IO3- groups and forms an iodic acid (HIO3) molecule; while the structures of M(IO3)2- can be written as (IO3-)M+(IO3-), in which the alkali metal atoms interact with the two IO3- groups almost equally and bridge the two IO3- groups via two O atoms of each IO3- with the two MOOI planes nearly perpendicular to each other. In addition, the high VDEs of M(IO3)2- (M = Li, Na, K) can be explained by the hyperhalogen behavior of their neutral counterparts.

  16. Photoelectron Spectroscopy and Theoretical Study of M(IO3)2– (M = H, Li, Na, K): Structural Evolution, Optical Isomers and Hyperhalogen Behavior

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Gao-Lei; Wu, Miao Miao; Wen, Hui; Sun, Qiang N.; Wang, Xue B.; Zheng, Weijun

    2013-07-31

    H(IO3)2- and M(IO3)2- (M = Li, Na, K) anions were successfully produced via electrospray ionization of their corresponding bulk salt solutions, and were characterized by combining negative ion photoelectron spectroscopy and quantum chemical calculations. The photoelectron spectra reveal that all these M(IO3)2- species possess very high vertical detachment energies (VDEs), to be 6.25, 6.57, 6.60 and 6.51 eV for H(IO3)2-, Li(IO3)2-, Na(IO3)2- and K(IO3)2-, respectively, which are much higher than that of IO3- (4.77 eV). The theoretical calculations show that each of these anions has two energetically degenerated optical isomers. It is found that the structure of H(IO3)2- can be written as IO3-(HIO3), in which the H atom is tightly bound to one of the IO3- groups and forms an iodic acid (HIO3) molecule; while the structures of M(IO3)2- can be written as (IO3-)M+(IO3-), in which the alkali metal atoms interact with the two IO3- groups almost equally and bridge the two IO3- groups via two O atoms of each IO3- with the two MOOI planes nearly perpendicular to each other. In addition, the high VDEs of M(IO3)2- (M = Li, Na, K) can be explained by the hyperhalogen behavior of their neutral counterparts.

  17. Rewarding effects of the optical isomers of 3,4-methylenedioxy-methylamphetamine ('Ecstasy') and 3,4-methylenedioxy-ethylamphetamine ('Eve') measured by conditioned place preference in rats.

    Science.gov (United States)

    Meyer, Anja; Mayerhofer, Andreas; Kovar, Karl-Artur; Schmidt, Werner J

    2002-09-27

    3,4-methylenedioxy-methylamphetamine (MDMA) ('Ecstasy') and its analogue 3,4-methylenedioxy-methylamphetamine (MDE) ('Eve') are well known illicit street drugs mainly abused by young people. In spite of the actual research going on, the classification of their abuse potential remains unclear. Since secondary reinforcers are the main factors responsible for craving and relapse, the aim of our study was to assess the potency of MDMA and MDE in a second order reinforcement paradigm, i.e. conditioned place preference (CPP). For the general assessment of our study conditions, we compared MDMA with amphetamine. Unexpectedly, no significant CPP for MDMA was found in contrast to amphetamine. Detailed analysis of current literature led us to the working hypothesis that social environment is crucial for the development of CPP. In a subsequent experiment we tested the influence of housing conditions on CPP using MDMA and demonstrated that isolated animals show significant CPP compared to group-housed ones. In order to better understand the rewarding mechanisms of Ecstasy-derivatives, we tested both the racemic drugs and the pure isomers in the CPP paradigm. Both MDMA's optical isomers and racemic MDMA showed significant CPP without notable differences, while MDE and its isomers completely failed to show any significant CPP. In conclusion, the mechanism by which MDMA induces addiction is much more complicated than assumed so far and more pronounced in isolated animals. The fact that both optical isomers of MDMA led to CPP implies that at least two pathways by which MDMA induces craving behaviour exist.

  18. Structural and photophysical characterisation of coordination and optical isomers of mononuclear ruthenium(II) polypyridyl 1,2,4-triazole complexes

    NARCIS (Netherlands)

    Browne, Wesley R.; Hesek, Dusan; Gallagher, John F.; O’Connor, Christine M.; Killeen, J. Scott; Aoki, Fumiko; Ishida, Hitoshi; Inoue, Yoshihisa; Villani, Claudio; Vos, Johannes G.

    2003-01-01

    The X-ray crystal structure of the N2 isomers of the Ru(bipy)2 complexes of Hphpztr (1) and Hpztr (2), (bipy = 2,2'-bipyridine, Hphpztr = 2-(5'-phenyl-4'H-[1,2,4]triazol-3'-yl)pyrazine and Hpztr = 2-(4'H-[1,2,4]triazol-3'-yl)pyrazine) are reported. The molecular structure obtained for 2 demonstrates

  19. Second harmonic generation and electro-optical Pockels effect of 1-and 3-nitro-6-azabenzo[]pyrene N-oxide isomers: A Hartree-Fock and Coulomb-attenuating density functional theory investigation

    Indian Academy of Sciences (India)

    Andrea Alparone

    2014-05-01

    Structural, energetic, spectroscopic, linear and nonlinear optical (NLO) properties of the environmental mutagens 1- and 3-nitro-6-azabenzo[]pyrene -oxides were characterized by means of Hartree-Fock as well as B3LYP and CAM-B3LYP density functional theory computations. The NLO investigations were performed for the second harmonic generation (SHG) and electro-optical Pockels effect (EOPE) at the incident wavelength of 1064 nm. The results show that, the predicted structures, vibrational spectra, nucleus independent chemical shifts, ionization energy, electron affinity as well as electronic polarizabilities are little influenced by the position of the nitro substituent. Differently, the dipole moment () and the first-order hyperpolarizabilities () are significantly dependent on the isomerization. The rather different mutagenic activity of the investigated isomers could be related to their diverse polarity. At the CAM-B3LYP level, when passing from the 1- to the 3-nitro-6-azabenzo[a]pyrene -oxide isomer, the datum increases by about 5 D (a factor of three), whereas the static and dynamic values decrease by ca. 50%. Dipole moment measurement and SHG and EOPE NLO techniques are potentially useful to distinguish these important environmental mutagens.

  20. 高效液相色谱法拆分盐酸舍曲林片的光学异构体%Separation of Four Optical Isomers Determination of Sertraline Hydrochloride Tablets by HPLC

    Institute of Scientific and Technical Information of China (English)

    陈积暖; 冯晓梅

    2012-01-01

    目的 建立测定盐酸舍曲林片光学异构体的高效液相色谱法.方法 采用反相高效液相色谱法,以外标法测定.色谱柱为依利特Hypersil ODS2柱(150mm×4.6mm,5μm),流动相为磷酸二氢钠缓冲液(取磷酸二氢钠12.5g,β-环糊精12.8g,HP-β-环糊精17.3g,加水至1 000 mL)-乙腈-三乙胺[800:200:10,用磷酸调节pH为(2.5±0.5)]为流动相,流速为1.0 mL/min,检测波长为214 nm.结果 所建立的流动相能拆分盐酸舍曲林4个光学异构体,光学异构体之间的分离度均良好.结论 该方法专属性好,准确、灵敏,盐酸舍曲林异构体与主峰分离良好,可作为控制盐酸舍曲林片有关物质检查的方法.%Objective To establish a HPLC method for determining four optical isomers in Sertraline Hydrochloride Tablets. Methods RP - HPLC was adopted with the external standard method for detection. The separation was carried out on the Hypersil ODS2 column (150 mm×4. 6 mm,5 μm) with the mobile phase of sodium dihydrogen phosphate buffer (taking sodium dihydrogen phosphate 12.5 g, beta - cyclodextrin 12.8 g, hydroxypropyl - beta - cyclodextrin 17. 3 g and adding water to 1 000 mL) - acetonitrile - triethylamine (800 : 200 : 10,adjusting to pH 2.5 ±0.5 with phosphoric acid). The flow rate was 1.0 mL/min and the detection wavelength was 214 nm. Results Four optical isomers of sertraline hydrochloride were effectively separated by the established the mobile phase. The degree of separation among isomers was good. Conclusion This method is specific, accurate and sensitive with better separation of isomers from main peak,and can be used as the detection method for controlling the related substances of Sertraline Hydrochloride Tabletso

  1. Corrigendum to "Stereochemical analysis of menthol and menthylamine isomers using calculated and experimental optical rotation data" [J. Mol. Struct. 1103 (2016) 166-176

    Science.gov (United States)

    Reinscheid, F.; Reinscheid, U. M.

    2016-04-01

    The authors regret to inform that a typographical error occurred in the published version of the article. In the last sentence of the abstract and of the conclusion the correct expression with the specific optical rotation should read "-10 < [α] < +10". We would like to apologize for the inconvenience caused.

  2. Isomer Energy System Design Concepts

    Energy Technology Data Exchange (ETDEWEB)

    Vogt, D

    2003-09-01

    Isomer energy supplies offer the potential to increase the output power over time to accommodate varying power needs. Other materials with similar energy density (for example isotopic energy sources such as {sup 238}Pu) do not offer the potential to increase power with time. Often the design life of an energy source is significant when compared to the half-life of the isotope. As a result, the conventional isotopic energy supplies operate with significant excess power at start of life to meet the power needs at end-of-life. For example a {sup 238}Pu radioisotope energy supply with a 35-year design life must account for radioactive decay losses of about 25% of the plutonium present at the start of life. This decay loss is significant if the required output power from the device is constant with time. If the required power output from the device increases with time (such as some space applications), significant increases in power supply weight are required to meet design power requirements. Isomer energy supplies offer the potential to increase the output power over time to meet varying power needs, thereby offering a significant advantage over conventional systems. Isomer energy supplies also offer the possibility of being ''turned on'' based on need at a specific time. These characteristics offer distinct advantages to isomer energy supplies. This report examines the basic engineering characteristics of a hypothetical isomer energy supply in order to gain insight into properties of isomers that will make them potentially useful as energy sources in engineered systems. These isomer properties provide a basis for identification of candidate isomers and provide a basis for an isomer search.

  3. Isomer Spectrum of Small Carbon Clusters

    Institute of Scientific and Technical Information of China (English)

    SHENG Yang; LI Peng; NING Xi-Jing

    2004-01-01

    A theoretical method is developed to find isomers of cluster particles, and the isomer spectrum of carbon clusters Cn (n = 3-44) is obtained. It is found that the isomers of 3-11 atoms are in either mono-ring or line shapes,while the isomers of 12-18 atoms show flat sheet shapes. As cluster size increases, bowl isomers become more (n > 19) until cage isomers dominate the structures (n > 27). Based on the isomer spectrum, results of a previous experiment are interpreted.

  4. Adsorption equilibria of dimethylnaphthalene isomers

    Energy Technology Data Exchange (ETDEWEB)

    Rota, R.; Morbidelli, M. [Politecnico di Milano (Italy). Dipt. di Chimica Fisica Applicata; Rombi, E.; Monaci, R.; Ferino, I.; Solinas, V. [Univ. di Cagliari (Italy). Dipt. di Scienze Chimiche

    1996-01-01

    Commercial sources of DMNs are the aromatic petroleum fraction of the appropriate boiling range and the coal liquefaction products. Adsorption processes for separating mixtures of dimethylnaphthalene (DMN) isomers are of potential interest for the production of 2,6-DMN. In this work, the adsorption equilibria of liquid mixtures of DMN isomers on zeolites have been investigated experimentally. The separation factors between the various isomers have been found to depend strongly on the composition of the fluid phase. A suitable equilibrium model, based on the adsorbed solution theory, has been developed to describe the multicomponent adsorption equilibria in the entire range of interest. Its performance has been tested using binary and ternary equilibrium data.

  5. Definition of "positional isomer" as it pertains to the control of schedule I controlled substances. Final rule.

    Science.gov (United States)

    2007-12-03

    On May 25, 2006, DEA published a Notice of Proposed Rulemaking which proposed the addition of a specific definition for the term "positional isomer" to allow for the systematic determination of which isomers of schedule I substances would be considered to be "positional," and therefore, subject to schedule I control. This rulemaking finalizes that definition. The Controlled Substances Act (CSA) and its implementing regulations specify which hallucinogenic substances are considered schedule I controlled substances. The CSA states that all salts, isomers, and salts of isomers of these substances are also schedule I controlled substances. In non-technical terms, an isomer of a substance is a different compound, but a compound which has the same number and kind of atoms. The terms "optical isomer" and "geometric isomer" are specific scientific terms and it is easy to determine whether one substance is an optical or geometric isomer of another. The term "positional isomer," however, is subject to scientific interpretation. The addition of a definition for the term "positional isomer" will assist legitimate research[ers] and industry in determining the control status of materials that are "positional isomers" of schedule I hallucinogens. While the DEA will remain the authority for ultimately determining the control status of a given material, providing a specific definition for "positional isomer" will ensure consistent criteria are utilized in making these determinations. This rule does not change existing laws, regulations, policies, processes, and procedures regarding the determination of control status for schedule I hallucinogenic substances. This rule merely makes available to the public the longstanding definition of "positional isomer" which DEA has used when making these scheduling determinations. This rule is relevant only to specialized forensic or research chemists. Most of these individuals are existing DEA registrants who are authorized by the DEA to handle

  6. Biological actions of formoterol isomers.

    Science.gov (United States)

    Handley, Dean A; Senanayake, Chris H; Dutczak, William; Benovic, Jeffrey L; Walle, Thomas; Penn, Raymond B; Wilkinson, H Scott; Tanoury, Gerald J; Andersson, Rolf G G; Johansson, Fredrik; Morley, John

    2002-01-01

    Racemic beta(2) agonists, composed of equal amounts of (R)- and (S)-isomers, can display anomalous actions that compromise their effectiveness as asthma therapies. Loss of efficacy during regular use is characteristic of isoprenaline, albuterol and terbutaline and has in part been attributed to the biological effects of the (S)-isomer. This hypothesis was applied to the (R,R)- and (S,S)-isomers of formoterol. (R,R)-formoterol had 1000-times greater affinity (2.9 nm) to the human beta(2) adrenoceptor than (S,S)-formoterol (3100 nm), with receptor binding modulating intracellular cAMP levels. The minimum lethal intravenous (IV) dose was determined to be 100 mg/kg for (R,R)- and 50 mg/kg for (S,S)-formoterol, suggesting that the toxicity of (S,S)-formoterol may not be related to the binding of beta(2) adrenoceptors. In tissues pretreated with (S,S)-formoterol but not with (R,R)- or racemic formoterol contractions to high concentrations of carbachol were exaggerated. In vivo experiments with sensitized guinea pigs demonstrated that (R,R)-formoterol inhibited both histamine and antigen-induced bronchoconstriction with greater potency than (R,R/S,S)-formoterol while (S,S)-formoterol was ineffective. Metabolic radiolabeling experiments of (R,R)-, (S,S)- or (R,R/S,S)-formoterol with crude human liver phenolsulfotransferase (PST) determined the V(max)/K(m) values to be (0.151), (0.74) and (0.143), respectively. The reciprocal plot illustrates a 2-fold reduction in sulfation rate when (R,R)-formoterol is present as a single isomer. The data presented here suggest that (R,R)-formoterol binds to the beta(2) adrenoceptor and inhibits the contraction of bronchial tissues by spasmogens. However, (S,S)-formoterol exhibits properties inconsistent as an asthma therapeutic and may antagonize the actions of (R,R)-formoterol. Copyright 2002 Elsevier Science Ltd.

  7. 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)

  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. Isomer Energy Source for Space Propulsion Systems

    Science.gov (United States)

    2004-03-01

    Nuclear Thermal Rocket PBR Particle-Bed Reactor SNTP Space Nuclear Thermal Propulsion TIC Triggered Isomer Core TIHE Triggered Isomer Heat...energy in a nuclear thermal rocket (NTR) configuration. This includes study of the current state of triggered isomer research, an investigation of 4... thermal rocket this means that heat from the reactive core must be prevented from raising the temperature of the propellant prior to its release from

  10. High spin isomer beam line at RIKEN

    Energy Technology Data Exchange (ETDEWEB)

    Kishida, T.; Ideguchi, E.; Wu, H.Y. [Institute of Physical and Chemical Research, Saitama (Japan)] [and others

    1996-12-31

    Nuclear high spin states have been the subject of extensive experimental and theoretical studies. For the production of high spin states, fusion reactions are usually used. The orbital angular momentum brought in the reaction is changed into the nuclear spin of the compound nucleus. However, the maximum induced angular momentum is limited in this mechanism by the maximum impact parameter of the fusion reaction and by the competition with fission reactions. It is, therefore, difficult to populate very high spin states, and as a result, large {gamma}-detector arrays have been developed in order to detect subtle signals from such very high spin states. The use of high spin isomers in the fusion reactions can break this limitation because the high spin isomers have their intrinsic angular momentum, which can bring the additional angular momentum without increasing the excitation energy. There are two methods to use the high spin isomers for secondary reactions: the use of the high spin isomers as a target and that as a beam. A high spin isomer target has already been developed and used for several experiments. But this method has an inevitable shortcoming that only {open_quotes}long-lived{close_quotes} isomers can be used for a target: {sup 178}Hf{sup m2} (16{sup +}) with a half-life of 31 years in the present case. By developing a high spin isomer beam, the authors can utilize various short-lived isomers with a short half-life around 1 {mu}s. The high spin isomer beam line of RIKEN Accelerator Facility is a unique apparatus in the world which provides a high spin isomer as a secondary beam. The combination of fusion-evaporation reaction and inverse kinematics are used to produce high spin isomer beams; in particular, the adoption of `inverse kinematics` is essential to use short-lived isomers as a beam.

  11. On the calculation of Mossbauer isomer shift

    NARCIS (Netherlands)

    Filatov, Michael

    2007-01-01

    A quantum chemical computational scheme for the calculation of isomer shift in Mossbauer spectroscopy is suggested. Within the described scheme, the isomer shift is treated as a derivative of the total electronic energy with respect to the radius of a finite nucleus. The explicit use of a finite nuc

  12. Spectral identification of fullerene C82 isomers

    Science.gov (United States)

    Gao, Bin; Liu, Lei; Wang, ChunRu; Wu, ZiYu; Luo, Yi

    2007-10-01

    Ultraviolet photoelectron spectra (UPS) of C82 isomers have been calculated using hybrid density functional theory in combination with the Gelius model [Proceedings of the International Conference on Electron spectroscopy, edited by D. A. Shirley (North-Holland, Amsterdam, 1972), p. 311; J. Electron Spectrosc. Relat. Phenom. 5, 985 (1974)]. The calculated UPS spectra are found to be isomer dependent and in good agreement with the experimental counterparts. Near-edge x-ray absorption fine structure (NEXAFS), x-ray photoelectron spectroscopy (XPS), x-ray emission spectroscopy, and the resonant inelastic x-ray scattering (RIXS) spectra of three important isomers [3(C2), 6(Cs), and 9(C2v)] have also been simulated. Strong isomer dependence has also been found for NEXAFS, XPS, and RIXS spectra.

  13. Conjugated linoleic acid isomers and cancer.

    Science.gov (United States)

    Kelley, Nirvair S; Hubbard, Neil E; Erickson, Kent L

    2007-12-01

    We reviewed the literature regarding the effects of conjugated linoleic acid (CLA) preparations enriched in specific isomers, cis9, trans11-CLA (c9, t11-CLA) or trans10, cis12-CLA (t10, c12-CLA), on tumorigenesis in vivo and growth of tumor cell lines in vitro. We also examined the potential mechanisms by which CLA isomers may alter the incidence of cancer. We found no published reports that examined the effects of purified CLA isomers on human cancer in vivo. Incidence of rat mammary tumors induced by methylnitrosourea was decreased by c9, t11-CLA in all studies and by t10, c12-CLA in just a few that included it. Those 2 isomers decreased the incidence of forestomach tumors induced by benzo (a) pyrene in mice. Both isomers reduced breast and forestomach tumorigenesis. The c9, t11-CLA isomer did not affect the development of spontaneous tumors of the intestine or mammary gland, whereas t10, c12-CLA increased development of genetically induced mammary and intestinal tumors. In vitro, t10, c12-CLA inhibited the growth of mammary, colon, colorectal, gastric, prostate, and hepatoma cell lines. These 2 CLA isomers may regulate tumor growth through different mechanisms, because they have markedly different effects on lipid metabolism and regulation of oncogenes. In addition, c9, t11-CLA inhibited the cyclooxygenase-2 pathway and t10, c12-CLA inhibited the lipooxygenase pathway. The t10, c12-CLA isomer induced the expression of apoptotic genes, whereas c9, t11-CLA did not increase apoptosis in most of the studies that assessed it. Several minor isomers including t9, t11-CLA; c11, t13-CLA; c9, c11-CLA; and t7, c11-CLA were more effective than c9, t11-CLA or t10, c12-CLA in inhibiting cell growth in vitro. Additional studies with purified isomers are needed to establish the health benefit and risk ratios of each isomer in humans.

  14. High-harmonic spectroscopy of molecular isomers

    Energy Technology Data Exchange (ETDEWEB)

    Wong, M. C. H.; Brichta, J.-P.; Bhardwaj, V. R. [Department of Physics, University of Ottawa, 150 Louis-Pasteur, Ottawa, Ontario, K1N 6N5 (Canada); Spanner, M.; Patchkovskii, S. [National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario, K1A 0R6 (Canada)

    2011-11-15

    We demonstrate that high-order-harmonic generation (HHG) spectroscopy can be used to probe stereoisomers of randomly oriented 1,2-dichloroethylene (C{sub 2}H{sub 2}Cl{sub 2}) and 2-butene (C{sub 4}H{sub 8}). The high-harmonic spectra of these isomers are distinguishable over a range of laser intensities and wavelengths. Time-dependent numerical calculations of angle-dependent ionization yields for 1,2-dichloroethylene suggest that the harmonic spectra of molecular isomers reflect differences in their strong-field ionization. The subcycle ionization yields for the cis isomer are an order of magnitude higher than those for the trans isomer. The sensitivity in discrimination of the harmonic spectra of cis- and trans- isomers is greater than 8 and 5 for 1,2-dichloroethylene and 2-butene, respectively. We show that HHG spectroscopy cannot differentiate the harmonic spectra of the two enantiomers of the chiral molecule propylene oxide (C{sub 3}H{sub 6}O).

  15. Cis and Trans Isomers of Cycloalkenes

    Science.gov (United States)

    Barrows, Susan E.; Eberlein, Thomas H.

    2005-09-01

    As a rule, a trans disubstituted alkene is more stable than the corresponding cis isomer. For cycloalkenes of fewer than eleven members, cis isomers are more stable than their trans counterparts. Although this exception to the normal rule is occasionally noted in beginning organic chemistry textbooks, it is often done without a careful analysis of the reasons behind it. The purpose of this article is to provide that analysis. In order for a cycloalkene to accommodate a trans double bond one or more of the following nonideal geometries must occur: a twisted π bond; pyramidal sp 2 -carbon atoms; nonideal sp 3 bond angles; or longer than normal C C single and double bonds. This article provides a list of experimentally determined relative energies of the cis and trans isomers within the series cycloheptene cycloundecene, along with computationally derived energies at several levels of theory. It also examines the geometric distortions through which cycloalkenes relieve the strain introduced by a trans double bond.

  16. Analysis of Heme oxygenase isomers in rat

    Institute of Scientific and Technical Information of China (English)

    Yun-ZhuLi; Wen-JunCui; Xue-HongZhang; Qing-XiangShen; JianWang; She

    2002-01-01

    AIM:To purify and identify heme oxygenase(HO) isomers which exist in rat liver,spleen and brain treated with hematin and phenylhydrazine and in untrated rat liver and to investigate the characteristics of HO isomers,to isolate and confirm the rat HO-1 cDNA that actually encodes HO-1 by expressing cDNA in monkey Kidney cells(COS-1 cells),to prepare the rat heme oxygenase-1(HO-1)mutant and to detect inhibition of HO-1 mutated enzyme.

  17. Two Novel Isomers of HPS3 System

    Institute of Scientific and Technical Information of China (English)

    Hai Tao YU; Ming Xia LI; Yu Juan CHI; Fu Long YUANG; Hong Gang FU; Jia Zhong SUN

    2003-01-01

    Two new isomers of HPS3 system, HP(S)S2 and HSSPS, are predicted by means of B3LYP method with 6-311++G(3df,3pd) basis set. The two isomers can isomerize into thermodynamically the most stable species HSPS2, which have been experimentally identified, with relatively higher reaction barriers. In view of their higher thermodynamical and kinetic stability and the experimental observation for HP(O)O2 and HOOPO in previous study, we can reasonably believe that the two species can be spectrosymmetrically characterized in future experiments.

  18. An Assessment of Nuclear Isomers as an Energy Storage Medium

    Energy Technology Data Exchange (ETDEWEB)

    Hartouni, E P

    2008-12-08

    Nuclear Isomers have been suggested as a potential high energy density medium that might be used to store energy. This talk assesses the state of the science supporting key elements of using nuclear isomers in energy storage applications. The focus is on the nuclear isomer {sup 178m2}Hf which has been most widely suggested for energy storage applications. However, the science issues apply to all nuclear isomer. The assessment addresses the production of the nuclear isomer, and inducing the release of the isomer. Also discussed are novel speculations on photon and/or neutron chain reactions, both as a 'pure' material as well as mixed with other materials.

  19. 'Melatonin isomer' in wine is not an isomer of the melatonin but tryptophan-ethylester.

    Science.gov (United States)

    Gardana, Claudio; Iriti, Marcello; Stuknytė, Milda; De Noni, Ivano; Simonetti, Paolo

    2014-11-01

    Melatonin is a neurohormone, chronobiotic, and antioxidant compound found in wine and deriving directly from grapes and/or synthesized by yeast during alcoholic fermentation. In addition, a melatonin isomer has been detected in different foods, wine among them. The special interest for melatonin isomer related to the fact that it was found in greater quantities than melatonin and probably shares some of its biological properties. Despite this, its chemical structure has not yet been defined; although some researchers hypothesize, it could be melatonin with the ethylacetamide group shifted into position N1. Thus, the aim of our study was to identify the structures of the melatonin isomer. For this purpose, melatonin and melatonin isomer in Syrah wine were separated chromatographically by a sub-2 μm particle column and detected by tandem mass spectrometry. The sample was then purified and concentrated by solid-phase extraction, hydrolyzed with alkali or esterase, and substrates and products quantified by UPLC-MS/MS. Moreover, melatonin, melatonin isomer, and their product ions were evaluated by high-resolution mass spectrometry. The amount of melatonin isomer and melatonin in the wine was 84 ± 4 and 3 ± 0 ng/mL, respectively. In the solutions, containing diluted alkali or esterase, melatonin isomer was hydrolyzed in about 8 min. Correspondingly, tryptophan was detected, and its amount increased and reached the maximum concentration in about 8 min. Melatonin concentration was not affected by diluted alkali or esterase. The fragmentation pattern of melatonin isomer was different from that of melatonin but comparable to that of tryptophan-ethylester. Finally, the so-called melatonin isomer identity was verified by cochromatography with authentic standard of tryptophan-ethylester. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  20. Theoretical characterization of four distinct isomer types in hydrated-electron clusters, and proposed assignments for photoelectron spectra of water cluster anions.

    Science.gov (United States)

    Jacobson, Leif D; Herbert, John M

    2011-12-14

    Water cluster anions, (H(2)O)(N)(-), are examined using mixed quantum/classical molecular dynamics based on a one-electron pseudopotential model that incorporates many-body polarization and predicts vertical electron detachment energies (VDEs) with an accuracy of ~0.1 eV. By varying the initial conditions under which the clusters are formed, we are able to identify four distinct isomer types that exhibit different size-dependent VDEs. On the basis of a strong correlation between the electron's radius of gyration and its optical absorption maximum, and extrapolating to the bulk limit (N → ∞), our analysis supports the assignment of the "isomer Ib" data series, observed in photoelectron spectra of very cold clusters, as arising from cavity-bound (H(2)O)(N)(-) cluster isomers. The "isomer I" data reported in warmer experiments are assigned to surface-bound isomers in smaller clusters, transitioning to partially embedded isomers in larger clusters. The partially embedded isomers are characterized by a partially formed solvent cavity at the cluster surface, and they are spectroscopically quite similar to internalized cavity isomers. These assignments are consistent with various experimental data, and our theoretical characterization of these isomers sheds new light on a long-standing assignment problem. © 2011 American Chemical Society

  1. A new isomer in {sup 125}La

    Energy Technology Data Exchange (ETDEWEB)

    Canchel, G. [Lyon-1 Univ., 69 - Villeurbanne (France). Inst. de Physique Nucleaire]|[Department of Physics, Accelerator Laboratory, University of Jyvaeskylae, P.O. Box 35, FIN-40351 Jyvaeskylae (Finland); Beraud, R.; Chabanat, E.; Emsallem, A.; Redon, N. [Lyon-1 Univ., 69 - Villeurbanne (France). Inst. de Physique Nucleaire; Dendooven, P.; Huikari, J.; Jokinen, A.; Kolhinen, V.; Lhersonneau, G.; Oinonen, M.; Nieminen, A.; Penttilae, H.; Peraejaervi, K.; Wang, J.C.; Aeystoe, J. [Department of Physics, Accelerator Laboratory, University of Jyvaeskylae, P.O. Box 35, FIN-40351 Jyvaeskylae (Finland)

    1999-05-01

    Levels in {sup 125}La have been studied via {beta}{sup +}/EC decay of on-line mass-separated {sup 125}Ce using the HIGISOL technique. A new (390{+-}40) ms isomer is definitely attributed to {sup 125}La by conversion electron measurements of the 107 keV E3 isomeric transition. (orig.) With 2 figs., 1 tab., 11 refs.

  2. Organometallic chemistry: Heavyweight isomer brings stability

    Science.gov (United States)

    Scheschkewitz, David

    2016-11-01

    Due to its high reactivity, vinylidene -- the sole 'electron-precise' isomer of acetylene -- is only known to exist in the gas phase. Now, a stable base-free digermanium version of a vinylidene has been isolated by the clever use of suitable substituents.

  3. Modelling Study of Interstellar Ethanimine Isomers

    Science.gov (United States)

    Quan, Donghui; Herbst, Eric; Corby, Joanna F.; Durr, Allison; Hassel, George

    2016-06-01

    Ethanimine (CH3CHNH) , including both the E- and Z- isomers, were detected towards the star-forming region Sgr B2(N) using the GBT PRIMOS data (Loomis et al 2013), and were recently imaged by the ACTA (Corby et al. 2015). These aldimines can serve as precursors of biological molecules such as amino acids thus are considered prebiotic molecules in interstellar medium. In this study, we present chemical simulations of ethanimine with various physical conditions. From models for Sgr B2(N) and environs, calculated ethanimine abundances show reasonable agreement with observed values, while the translucent cloud models yield much lower abundances. These results agree with locations suggested by observations that ethanimine isomers were detected in the foreground of the shells of the hot core.

  4. Phase transition equilibrium of terthiophene isomers

    Energy Technology Data Exchange (ETDEWEB)

    Costa, Jose C.S.; Lima, Carlos F.R.A.C.; Rocha, Marisa A.A. [Centro de Investigacao em Quimica, Departamento de Quimica e Bioquimica, Faculdade de Ciencias da Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal); Gomes, Ligia R. [CIAGEB, Faculdade de Ciencias de Saude Escola Superior de Saude da UFP, Universidade Fernando Pessoa, Rua Carlos da Maia, 296, P-4200-150 Porto (Portugal); REQUIMTE, Departamento de Quimica e Bioquimica, Faculdade de Ciencias, Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal); Santos, Luis M.N.B.F., E-mail: lbsantos@fc.up.p [Centro de Investigacao em Quimica, Departamento de Quimica e Bioquimica, Faculdade de Ciencias da Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal)

    2011-02-15

    The thermodynamic study of the phase transition (fusion and sublimation) of 2,2':5',2''-terthiophene and 3,2':5',3''-terthiophene is presented. The obtained data is used to evaluate the (solid + liquid) and (solid + gas) phase equilibrium, and draw the phase diagrams of the pure compounds near the triple point coordinates. For each compound the vapour pressures at different temperatures were measured by a combined Knudsen effusion method with a vacuum quartz crystal microbalance. Based on the previous results, the standard molar enthalpies, entropies and Gibbs energies of sublimation were derived at T = 298.15 K. For the two terthiophenes and for 3,3'-bithiophene, the temperature, and the molar enthalpies of fusion were measured in a power compensated differential scanning calorimetry. The relationship between structure and energetics is discussed based on the experimental results, ab initio calculations and previous literature data for 2,2'-bithiophene and 3,3'-bithiophene. The 3,2':5',3''-terthiophene shows a higher solid phase stability than the 2,2':5',2''-terthiophene isomer arising from the higher cohesive energy due to positioning of the sulphur atom in the thiophene ring. The higher phase stability of 3,3'-bithiophene relative to 2,2'-bithiophene isomer is also related to its higher absolute entropy in the solid phase associated with the ring positional degeneracy observed in the crystal structure of this isomer. A significant differentiation in the crystal phase stability between isomers was found.

  5. A thirty second isomer in Hf-171

    NARCIS (Netherlands)

    Campbell, P; Billowes, J; Cochrane, ECA; Cooke, JL; Cooper, TG; Dendooven, P; Evans, DE; Grant, IS; Griffith, JAR; Honkanen, A; Huhta, M; Oinonen, M; Pearson, MR; Penttila, H; Persson, B.L.; Richardson, DS; Tungate, G; Wheeler, PD; Zybert, L; Aysto, J

    1997-01-01

    An isomer has been detected in Hf-171 with a half-life of T-1/2 = 29.5(9) s. The state was populated in the Yb-170(alpha,3n)Hf-171m reaction at a beam energy of E-alpha = 50 MeV in an on-line ion guide isotope separator. The isomeric Hf-17lm(+) beam was extracted from the ion guide, mass-analysed an

  6. Conjugated linoleic acid isomers: differences in metabolism and biological effects.

    Science.gov (United States)

    Churruca, Itziar; Fernández-Quintela, Alfredo; Portillo, Maria Puy

    2009-01-01

    The term conjugated linoleic acid (CLA) refers to a mixture of linoleic acid positional and geometric isomers, characterized by having conjugated double bonds, not separated by a methylene group as in linoleic acid. CLA isomers appear as a minor component of the lipid fraction, found mainly in meat and dairy products from cows and sheep. The most abundant isomer is cis-9,trans-11, which represents up to 80% of total CLA in food. These isomers are metabolized in the body through different metabolic pathways, but important differences, that can have physiological consequences, are observed between the two main isomers. The trans-10,cis-12 isomer is more efficiently oxidized than the cis-9,trans-11 isomer, due to the position of its double bounds. Interest in CLA arose in its anticarcinogenic action but there is an increasing amount of specific scientific literature concerning the biological effects and properties of CLA. Numerous biological effects of CLA are due to the separate action of the most studied isomers, cis-9,trans-11 and trans-10,cis-12. It is also likely that some effects are induced and/or enhanced by these isomers acting synergistically. Although the cis-9,trans-11 isomer is mainly responsible for the anticarcinogenic effect, the trans-10,cis-12 isomer reduces body fat and it is referred as the most effective isomer affecting blood lipids. As far as insulin function is concerned, both isomers seem to be responsible for insulin resistance in humans. Finally, with regard to the immune system it is not clear whether individual isomers of CLA could act similarly or differently.

  7. Conformation analysis of isomers of imidoyl halides

    Energy Technology Data Exchange (ETDEWEB)

    Gershikov, A.G.; Vul' fov, A.L.; Savelova, V.A.; Drizhd, L.P.

    1985-09-01

    The possible mechanisms of the intramolecular syn-anti isomerization of imidoyl halides have been analyzed with the aid of nonempirical quantum-chemical calculations. In the liquid phase isomerization can occur after a preliminary step of ionization with the formation of nitrilium cations. The conformational features have been studied by the methods of molecular mechanics, the differences between the energies of the syn and anti isomers of a number of imidoyl halides and closely related azomethines have been calculated, and the relative equilibrium concentrations of the isomeric forms at 298/sup 0/K have been evaluated.

  8. 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

    2016-01-01

    We present the detection of two H2C3O 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 H2C3O 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. PMID:27013768

  9. Nuclear isomers as ultra-high-energy-density materials

    Science.gov (United States)

    Poppe, C. H.; Weiss, M. S.; Anderson, J. D.

    1992-09-01

    A major energy advance could result if the enormous potential of nuclear energy storage could be tapped without the penalty of radioactive by-products. Recent research has uncovered a new method for nuclear energy storage with high energy density and no residual radioactivity. Nuclear isomers are metastable states of atomic nuclei which release their energy in a prompt burst of electromagnetic radiation; in many cases the product remaining after decay of isomer is stable and no activity is produced by the electromagnetic decay. Two kinds of nuclear isomers are known: spin isomers and shape isomers. The former lacks a release mechanism. Theory has predicted the existence of shape isomers in the mass range around mercury and gold where decay by fission is prohibited. Experiments on the existence of fissionless shape isomers have resulted in evidence for 27 different shape isomers in isotopes of mercury, lead, and thallium. Three potential candidates for release mechanisms have been identified to date: neutron catalysis (Hf- 178), laser-electron-nuclear coupling (Th-229), and Stark-shift-induced mixing (speculative). Ways of producing nonfissioning shape isomers are discussed.

  10. Produções de ácido acético, etanol e dos isômeros óticos do ácido lático por linhagens de Lactobacillus isoladas de fermentações alcoólicas industriais Production of acetic acid, ethanol and optical isomers of lactic acid by Lactobacillus strains isolated from industrial ethanol fermentations

    Directory of Open Access Journals (Sweden)

    Vanessa Moreira Costa

    2008-04-01

    mixture of equal amounts of glucose and fructose as the carbon source, and supplemented with yeast extract, mineral nutrients and buffer. Bacterial growth was estimated by absorbance at 600nm and the main end products of bacterial metabolism (lactate, acetate and ethanol were measured by high performance liquid chromatography, while the stereoisomers, D(-- and L(+-lactate, were assayed by an enzymatic methodology using stereospecific lactate-dehydrogenases. According to the results, all the three types of metabolism were found among the bacteria investigated: obligately homofermentative (8 strains, facultative heterofermentative (1 strain and obligately heterofermentative (8 strains. The results have showed a predominance of DL strains regarding the stereoisomers production, but it was also found strains producing a single type of the isomeric form. These findings suggest the possibility to explore the lactobacilli biodiversity in fuel ethanol fermentation plants for lactate production of chemically pure optical isomers. This is the first report on lactic acid isomers formation by Lactobacillus strains isolated from sugar cane based-industrial fermentations.

  11. Structures and Stability of HNS2 Isomers

    Institute of Scientific and Technical Information of China (English)

    CHI,Yu-Juan(池玉娟); YU,Hai-Tao(于海涛); Fu,Hong-Gang(傅宏刚); HUANG,Xu-Ri(黄旭日); LI,Ze-Sheng(李泽生); SUN,Jia-Zhong(孙家钟)

    2002-01-01

    Potential energy surface of HNS2 is investigated by means of second-order Moller-Plesset perturbation theory (MP2) and QCISD(T) (single-point) methods. At final QCISD (T)/6-311++ G(3df,2p)//MP2/6-311++ G(d,p) level with zero-point vibrational energies included, cis-HNSS is found to be global minimum on the potential energy surface, followed by low-lying trans-HNSS, HN(S)S(C2v), cis-HSNS, cis-HSSN,rans-HSNS, trans-HSSN, and HN(S)S(Cs) by 13.46,66.92, 78.25, 80.38, 81.22, 81.38 and 86.40 kJ/mol, respectively. A new high-lying HS(N)S isomer with Cs symmetry is located on the potential energy surface. The kinetic stabilities of all isomers are predicted. Comparisons are made for HNS2 with its analogues, HNO2, HPS2 and HPO2. The causes that lead to the differences between HNS2 and its analogues are hypervalent capacity of phosphorus and distinct electronegativities of hydrogen, nitrogen and phosphorus.

  12. 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

  13. Structures and Stability of NHS2 Isomers

    Institute of Scientific and Technical Information of China (English)

    池玉娟; 于海涛; 等

    2002-01-01

    Potential energy surface of HNS2 is investigated by means of second-order Moller-Plesset Perturbation theory(MP2) and QCISD(T) (single-point)methods,At final QCISD (T)/6-311++G(3df,2p)//MP2/6-311+G(d,p),level with zero-point vibrational energies included,cis-NHSS is found to be global minimum on the potential energy sufrace,followed by low-lying trans-HNSS ,HN(S)S(C2v).cis-HSNS,cis-NSSN,trans-HSNS,trans-NSSN,and HN(S)S(Cs) by 13.46,66.92,78.25,80.38,81.22,81.38 and 86.40 kJ/mol,respectively.A new high-lying HS(N)S isomer with Cs symmetry is located on the potential energy surface ,The kinetic stabilities of all isomers are predicted.Comprisons are made for HNS2 with its analogues,NHO2,HPS2 and HPO2,The causes that lead to the differences between HNS2 and its analogues are hypervalent capacity of phosphorus and distinct electronegativities of hydrogen,nitrogen and phosphorus.

  14. Static and Dynamic Electronic (Hyperpolarizabilities of Dimethylnaphthalene Isomers: Characterization of Spatial Contributions by Density Analysis

    Directory of Open Access Journals (Sweden)

    Andrea Alparone

    2013-01-01

    Full Text Available Static and frequency-dependent electronic (hyperpolarizabilities of the dimethylnaphthalene (DMN isomers were computed in vacuum using the Coulomb-attenuating Density Functional Theory method. The nonlinear optical Second Harmonic Generation (SHG and Electro-Optical Pockels Effect (EOPE were investigated at the characteristic Nd:YAG laser wavelength of 1064 nm. The response electric properties especially the longitudinal polarizability, polarizability anisotropy, and first-order hyperpolarizability are significantly affected by the position of the methyl groups. The SHG and EOPE techniques can be potentially useful to discriminate the ,-DMN isomers (2,6-DMN < 2,7-DMN < 2,3-DMN as well as the ,-DMN isomers (1,5-DMN < 1,4-DMN < 1,8-DMN. The (hyperpolarizability differences among the investigated DMNs were elucidated through density analysis calculations. The predicted polarizabilities exhibit good linear relationships with the experimental first-order biomass-normalized rate coefficient, a physicochemical property connected to the rates of biodegradation processes of polycyclic aromatic hydrocarbons.

  15. 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…

  16. The Structures and Stability of HNOS Isomers

    Institute of Scientific and Technical Information of China (English)

    CHI,Yu-Juan; YU,Hai-Tao; FU,Hong-Gang; XIN,Bai-Fu; LI,Ze-Sheng; SUN,Jia-Zhong

    2003-01-01

    Potential energy surface of HNOS system is investigated by means ofMP2 method with 6-311 ++ G(d, p)basis set. The energyfor each minimum and saddle point on the potential energy surface is corrected at the QCISD(T)/6-311 ++ G(3df, 2p) level of theory with zero-point vibrational energy included. As a result, eighteen isoners are theoretically predicted and cis-HNSO is found to be global minimum on the potential energy surface. Wherein, fourteen isoners are considered as kinetically stable species, and should be experimentally observed. Comparisons are made for HNOS system with its analogues, HNO2 and HNS2. The nature of bonding and isomers' stability of HNOS system are similar to HNS2. The obvious similarities and discrepancies among HNOS, HNO2 and HNS2are attributed to the hypervalent capacity of sulfur, oxygen and nitrogen atoms.

  17. Analysis of Heme oxygenase isomers in rat

    Institute of Scientific and Technical Information of China (English)

    Zhen-Wei Xia; Wen-Jun Cui; Xue-Hong Zhang; Qing-Xiang Shen; Jian Wang; Yun-Zhu Li; Shen-Nian Chen; Shan-Chang Yu

    2002-01-01

    AIM: To purify and identify heme oxygenase (HO) isomers which exist in rat liver, spleen and brain treated with hematin and phenylhydrazine and in untreated rat liver and to investigate the characteristics of HO isomers, to isolate and confirm the rat HO-1 cDNA that actually encodes HO-1 by expressing cDNA in monkey kidney cells (COS-1 cells), to prepare the rat heme oxygenase-1 (HO-1) mutant and to detect inhibition of HO-1 mutated enzyme.METHODS: First, rat liver, spleen and brain microsomal fi-actions were purified by DEAE-Sephacel and hydroxylapatite. The characteristics including activity, immunity and inducibility of two isomers (HO-1 and HO-2), and their apparent molecular weight were measured by detecting enzymatic activities, SDS-polyacrylamide gel electrophoresis (SDS-PAGE) and Western blotting analysis, respectively. Second, plasmid pcDNA3HO1 containing native rat HO-1 cDNA and pcDNA3HO1D25 carrying mutated rat HO-1 cDNA (His25Ala) were constructed by site-directed mutagenesis. COS-1 cells transfected with pcDNA3HO1 and pcDNA3HO1D25 were collected and disrupted by sonication, the microsomes were prepared by ultracentrifugation. Third, the inhibition of rat HO-1 mutant was analyzed.RESULTS: Two isomers were purified and identified in treated rat liver, spleen, brain and untreated rat liver. HO-1 was the predominant form with a ratio of 2.0:1 and 3.2:1 of HO-1 and HO-2 in liver and spleen, respectively, but only the activity of HO-2 in the brain and untreated liver could be detected. The apparent molecular weights of HO-1 and HO-2 were about Mr 30 000 and Mr 36 000 under reducing conditions, respectively. The antiserum against liver HO-2 was employed in Western blotting analysis, the reactivity of HO-1 in the liver was not observed. The plasmid pcDNA3HO1 was highly expressed in endoplasmic reticulum of transfected COS-1 cells. The specific activity was ≈5-fold higher than that of the control. However, the enzyme activity of mutated HO-1 declined. While

  18. Optics

    CERN Document Server

    Fincham, W H A

    2013-01-01

    Optics: Ninth Edition Optics: Ninth Edition covers the work necessary for the specialization in such subjects as ophthalmic optics, optical instruments and lens design. The text includes topics such as the propagation and behavior of light; reflection and refraction - their laws and how different media affect them; lenses - thick and thin, cylindrical and subcylindrical; photometry; dispersion and color; interference; and polarization. Also included are topics such as diffraction and holography; the limitation of beams in optical systems and its effects; and lens systems. The book is recommen

  19. Systematic Investigation of Benzodithiophene-Benzothiadiazole Isomers for Organic Photovoltaics.

    Science.gov (United States)

    Du, Jia; Fortney, Andria; Washington, Katherine E; Bulumulla, Chandima; Huang, Peishen; Dissanayake, Dushanthi; Biewer, Michael C; Kowalewski, Tomasz; Stefan, Mihaela C

    2016-12-07

    Two new donor-acceptor small molecules based on benzo[1,2-b:4,5-b']dithiophene (BDT) and benzo[c][1,2,5]thiadiazole (BT) were designed and synthesized. Small molecules 4,4'-[(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis(2,2'-bithiophene)-5,5'-diyl]bis(benzo[c][1,2,5]thiadiazole) (BDT-TT-BT) and 4,4'-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis[7-(2,2'-bithiophene-5-yl)benzo[c][1,2,5]thiadiazole] (BDT-BT-TT) are structural isomers with the 2,2-bithiophene unit placed either between the BDT and BT units or at the end of the BT units. This work is targeted toward finding the effect of structural variation on optoelectronic properties, morphology, and photovoltaic performance. On the basis of theoretical calculations, the molecular geometry and energy levels are different for these two molecules when the position of the 2,2-bithiophene unit is changed. Optical and electrochemical properties of these two small molecules were characterized using UV-vis and cyclic voltammetry. The results showed that BDT-BT-TT has broader absorption and an elevated HOMO energy level when compared with those of BDT-TT-BT. The performance of these two isomers in solar cell devices was tested by blending with [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM). Power conversion efficiencies as high as 3.22 and 3.71% were obtained in conventional solar cell structures for BDT-TT-BT and BDT-BT-TT, respectively. The morphology was studied using grazing incident wide-angle X-ray scattering and transmission electron microscopy, which revealed different phase separations of these two molecules when blended with PC71BM.

  20. Comparison of the repeated dose toxicity of isomers of dinitrotoluene.

    Science.gov (United States)

    Lent, Emily May; Crouse, Lee C B; Quinn, Michael J; Wallace, Shannon M

    2012-03-01

    Dinitrotoluene (DNT) is a nitroaromatic explosive used in propellant mixtures and in the production of plastics. Isomers of DNT were administered daily via oral gavage to male Sprague-Dawley rats for 14 days to determine the subacute toxicity of individual isomers of DNT. The 3,5-DNT isomer was the most toxic isomer, inducing weight loss and mortality within 3 days. Cyanosis and anemia were observed for all isomers. Exposure to 2,4-, 2,6-, and 3,5-DNT resulted in decreased testes mass and degenerative histopathological changes. Increased splenic mass was observed for 2,4-, 2,6-, and 2,5-DNT. Extramedullary hematopoiesis of the spleen was noted for all isomers, while lymphoid hyperplasia of the spleen was noted for all isomers except 2,5-DNT. Increased liver mass was observed for 2,3-DNT and 3,4-DNT. Hepatocellular lesions were observed for 2,6-DNT and 2,4-DNT. Neurotoxic effects were noted for 3,4-DNT, 2,4-DNT, and 3,5-DNT.

  1. Adsorption and Diffusion of Xylene Isomers on Mesoporous Beta Zeolite

    Directory of Open Access Journals (Sweden)

    Aixia Song

    2015-12-01

    Full Text Available A systematic and detailed analysis of adsorption and diffusion properties of xylene isomers over Beta zeolites with different mesoporosity was conducted. Adsorption isotherms of xylene isomers over microporous and mesoporous Beta zeolites through gravimetric methods were applied to investigate the impact of mesopores inside Beta zeolites on the adsorption properties of xylene isomers in the pressure range of lower 20 mbar. It is seen that the adsorption isotherms of three xylene isomers over microporous and mesoporous Beta zeolites could be successfully described by the single-site Toth model and the dual-site Toth model, respectively. The enhanced adsorption capacities and decreased Henry’s constants (KH and the initial heats of adsorption (Qst for the all xylene isomers are observed after the introduction of mesopores in the zeolites. For three xylene isomers, the order of Henry’s constant is o-xylene > m-xylene > p-xylene, whereas the adsorption capacities of Beta zeolite samples for xylene isomers execute the following order of o-xylene > p-xylene > m-xylene, due to the comprehensive effects from the molecular configuration and electrostatic interaction. At the same time, the diffusion properties of xylene isomers in the mesoporous Beta zeolites were also studied through the desorption curves measured by the zero length column (ZLC method at 333–373 K. It turned out that the effective diffusion time constant (Deff/R2 is a growing trend with the increasing mesoporosity, whereas the tendency of the activation energy is just the reverse, indicating the contribution of mesopores to facilitate molecule diffusion by shortening diffusion paths and reducing diffusion resistances. Moreover, the diffusivities of three xylene isomers in all Beta zeolites follow an order of p-xylene > m-xylene > o-xylene as opposed to KH, conforming the significant effects of adsorbate-adsorbent interaction on the diffusion.

  2. Optics

    CERN Document Server

    Fincham, W H A

    2013-01-01

    Optics: Eighth Edition covers the work necessary for the specialization in such subjects as ophthalmic optics, optical instruments and lens design. The text includes topics such as the propagation and behavior of light; reflection and refraction - their laws and how different media affect them; lenses - thick and thin, cylindrical and subcylindrical; photometry; dispersion and color; interference; and polarization. Also included are topics such as diffraction and holography; the limitation of beams in optical systems and its effects; and lens systems. The book is recommended for engineering st

  3. Separation and identification of indene–C70 bisadduct isomers

    Science.gov (United States)

    Zhang, Bolong; Subbiah, Jegadesan; Jones, David J

    2016-01-01

    Summary Following an initial work on the isolation of a single geometric isomer from an indene–C70 bisadduct (IC70BA) mixture, we report the full fractionation and identification of the bisadduct species in the material. Eleven fractions of IC70BA isomers were separated by high-performance liquid chromatography. A number of fractions contained relatively pure isomer species and their configuration were deduced using a variety of analytical techniques including 1H and 13C NMR and UV–vis spectroscopy. The electrochemical properties and the organic solar cell device performance were investigated for fractions where a reasonable quantity of sample could be isolated. PMID:27340480

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

    CERN Document Server

    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.

  5. Studies of high-K isomers at TRIUMF-ISAC

    Energy Technology Data Exchange (ETDEWEB)

    Smith, M.B. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC (Canada); Walker, P.M. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC (Canada); Department of Physics, University of Surrey, Guildford, Surrey (United Kingdom); Chakrawarthy, R.S. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC (Canada); Austin, R.A.E. [Department of Physics and Astronomy, McMaster University, Hamilton, ON (Canada); Ball, G.C. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC (Canada); Carroll, J.J. [Department of Physics and Astronomy, Youngstown State University, Ohio (United States); Cunningham, E. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC (Canada); Finlay, P. [Department of Physics, University of Guelph, Guelph, ON (Canada); Garrett, P.E. [Lawrence Livermore National Laboratory, Livermore, California (United States); Grinyer, G.F. [Department of Physics, University of Guelph, Guelph, ON (Canada); Hackman, G. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC (Canada); Hyland, B. [Department of Physics, University of Guelph, Guelph, ON (Canada); Koopmans, K. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC (Canada); Department of Physics and Astronomy, McMaster University, Hamilton, ON (Canada); Kulp, W.D. [School of Physics, Georgia Institute of Technology, Atlanta, Georgia (United States); Leslie, J.R. [Physics Department, Queen' s University, Kingston, ON (Canada); Phillips, A.A. [Department of Physics, University of Guelph, Guelph, ON (Canada); Propri, R. [Department of Physics and Astronomy, Youngstown State University, Ohio (United States); Regan, P.H. [Department of Physics, University of Surrey, Guildford, Surrey (United Kingdom); Sarazin, F. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC (Canada); Schumaker, M.A. [Department of Physics, University of Guelph, Guelph, ON (Canada); Scraggs, H.C. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC (Canada)] [and others

    2004-12-27

    The properties of high-K isomers have been investigated by measuring {gamma} rays from a source of the 31-year {sup 178}Hf{sup m2} isomer and from the decay of implanted {sup 178,179}Lu beams. Low-intensity transitions have been identified in the decay of {sup 178}Hf{sup m2}, demonstrating a consistent extension of K-hindrance systematics to higher multipolarities, and elucidating the spin-dependence of the mixing between the two K{sup {pi}} = 8{sup -} bands. A search is underway for new isomers in {sup 178,179}Lu and the preliminary results of the analysis are reported.

  6. 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.

  7. Improvement of ISOM by using filter

    Directory of Open Access Journals (Sweden)

    Imen Chaabouni

    2012-05-01

    Full Text Available Image compression helps in storing the transmitted data in proficient way by decreasing its redundancy. This technique helps in transferring more digital or multimedia data over internet as it increases the storage space. It is important to maintain the image quality even if it is compressed to certain extent. Depend upon this the image compression is classified into two categories : lossy and lossless image compression. There are many lossy digital image compression techniques exists. Among this Incremental Self Organizing Map is a familiar one. The good pictures quality can be retrieved if image denoising technique is used for compression and also provides better compression ratio. Image denoising is an important pre-processing step for many image analysis and computer vision system. It refers to the task of recovering a good estimate of the true image from a degraded observation without altering and changing useful structure in the image such as discontinuities and edges. Many approaches have been proposed to remove the noise effectively while preserving the original image details and features as much as possible. This paper proposes a technique for image compression using Incremental Self Organizing Map (ISOM with Discret Wavelet Transform (DWT by applying filtering techniques which play a crucial role in enhancing the quality of a reconstructed image. The experimental result shows that the proposed technique obtained better compression ratio value.

  8. Carotenoids and their isomers: color pigments in fruits and vegetables.

    Science.gov (United States)

    Khoo, Hock-Eng; Prasad, K Nagendra; Kong, Kin-Weng; Jiang, Yueming; Ismail, Amin

    2011-02-18

    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.

  9. Reelfoot and Lake Isom National Wildlife Refuges : Wildlife Inventory Plan

    Data.gov (United States)

    US Fish and Wildlife Service, Department of the Interior — This wildlife inventory plan for Reelfoot and Lake Isom National Wildlife Refuges includes survey procedure forms that represent cost effective inventory of the...

  10. 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.

  11. Aromaticity of All Possible C26N2 Isomers

    Institute of Scientific and Technical Information of China (English)

    TANG,Ming-Hui; ABLIKIM,Kerim

    2008-01-01

    The aromaticity of all possible heterofullerenes C26N2 and C28 based on Td symmetry has been studied by means of the topological resonance energy and percentage topological resonance energy methods. The relationship between the aromaticity of the C26N2 isomers and the sites where nitrogen atoms dope at the C28 cage has been discussed. The calculation results show that the most stable isomer of C26N2 derivatives is formed by nitrogen atoms doping at the two tetrahedral vertices. C26N2 isomers are more stable than C28, but the C26N2-2 isomers are less stable than C4-28. The effect of nitrogen substitution on C28 stability was investigated by the topological charge stabilization rule.

  12. Separation of amyl alcohol isomers in ZIF-77

    NARCIS (Netherlands)

    Bueno-Perez, R.; Gutiérrez-Sevillano, J.J.; Dubbeldam, D.; Merkling, P.J.; Calero, S.

    2015-01-01

    The separation of pentanol isomer mixtures is shown to be very efficient using the nanoporous adsorbent zeolitic imidazolate framework ZIF-77. Through molecular simulations, we demonstrate that this material achieves a complete separation of linear from monobranchedand these from dibranchedisomers.

  13. Reelfoot/Lake Isom National Wildlife Refuge: Comprehensive Conservation Plan

    Data.gov (United States)

    US Fish and Wildlife Service, Department of the Interior — This Comprehensive Conservation Plan (CCP) was written to guide management on Reelfoot and Lake Isom NWRs for the next 15 years. This plan outlines the refuges'...

  14. Static and dynamic electronic (hyper)polarizabilities of dimethylnaphthalene isomers: characterization of spatial contributions by density analysis.

    Science.gov (United States)

    Alparone, Andrea

    2013-01-01

    Static and frequency-dependent electronic (hyper)polarizabilities of the dimethylnaphthalene (DMN) isomers were computed in vacuum using the Coulomb-attenuating Density Functional Theory method. The nonlinear optical Second Harmonic Generation (SHG) and Electro-Optical Pockels Effect (EOPE) were investigated at the characteristic Nd:YAG laser wavelength of 1064 nm. The response electric properties especially the longitudinal polarizability, polarizability anisotropy, and first-order hyperpolarizability are significantly affected by the position of the methyl groups. The SHG and EOPE techniques can be potentially useful to discriminate the α,α-DMN isomers (2,6-DMN analysis calculations. The predicted polarizabilities exhibit good linear relationships with the experimental first-order biomass-normalized rate coefficient, a physicochemical property connected to the rates of biodegradation processes of polycyclic aromatic hydrocarbons.

  15. Anaerobic biodegradability of phthalic acid isomers and related compounds.

    Science.gov (United States)

    Kleerebezem, R; Pol, L W; Lettinga, G

    1999-02-01

    All three phthalic acid isomers (ortho, meta and para benzene dicarboxylic acid) are produced in massive amounts, and used in the chemical industry as plasticizers or for the production of polyester. Wastestreams generated during the production of phthalate isomers generally contain high concentrations of aromatic acids. To study the potential biodegradability of these primarily anthropogenic compounds in anaerobic bioreactors, biodegradability studies were performed. Compounds tested were benzoate, ortho-phthalate, isophthalate, terephthalate, dimethyl phthalate, dimethyl terephthalate, para-toluate and para-xylene. Seed materials tested were two types of granular sludge and digested sewage sludge. It was found that all phthalate isomers and their corresponding dimethyl-esters, could be completely mineralized by all seed materials studied. Lag phases required for 50% degradation of these compounds, ranged from 17 to 156 days. The observed degradation curves could be explained by growth of an initially small amount of organisms in the inoculum with the specific ability to degrade one phthalate isomer. The observed order in the length of the lag phases for the phthalate isomers is: phthalate terephthalate terephthalate was found to be fermentation of the phthalate isomer. Para-toluate was degraded only by digested sewage sludge after a lag phase of 425 days. The observed degradation rates of this compound were very low. No mineralization of para-xylene was observed. In general, the differences in the lag phases between different seed materials were relatively small. These results indicate that the time needed for the start-up of anaerobic bioreactors treating wastewaters containing phthalic acid isomers, depends little on the microbial composition of the seed material applied, but may take several months.

  16. 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.)

  17. Direct observation of long-lived isomers in $^{212}$Bi

    CERN Document Server

    Chen, L; Geissel, H; Litvinov, Yu A; Beckert, K; Beller, P; Bosch, F; Boutin, D; Caceres, L; Carroll, J J; Cullen, D M; Cullen, I J; Franzke, B; Gerl, J; Górska, M; Jones, G A; Kishada, A; Knöbel, R; Kozhuharov, C; Kurcewicz, J; Litvinov, S A; Liu, Z; Mandal, S; Montes, F; Münzenberg, G; Nolden, F; Ohtsubo, T; Patyk, Z; Plaß, W R; Podolyák, Zs; Rigby, S; Saito, N; Saito, T; Scheidenberger, C; Simpson, E C; Shindo, M; Steck, M; Sun, B; Williams, S J; Weick, H; Winkler, M; Wollersheim, H -J; Yamaguchi, T

    2013-01-01

    Long-lived isomers in 212Bi have been studied following 238U projectile fragmentation at 670 MeV per nucleon. The fragmentation products were injected as highly charged ions into the GSI storage ring, giving access to masses and half-lives. While the excitation energy of the first isomer of 212Bi was confirmed, the second isomer was observed at 1478(30) keV, in contrast to the previously accepted value of >1910 keV. It was also found to have an extended Lorentz-corrected in-ring halflife >30 min, compared to 7.0(3) min for the neutral atom. Both the energy and half-life differences can be understood as being due a substantial, though previously unrecognised, internal decay branch for neutral atoms. Earlier shell-model calculations are now found to give good agreement with the isomer excitation energy. Furthermore, these and new calculations predict the existence of states at slightly higher energy that could facilitate isomer de-excitation studies.

  18. Ab initio search for global minimum structures of neutral and anionic B 4H 5 clusters. Optical isomerism in B 4H 5 and B4H5-

    Science.gov (United States)

    Olson, Jared K.; Boldyrev, Alexander I.

    2011-11-01

    Potential energy surfaces of neutral and anionic B 4H 5 clusters were sampled using the Coalescence Kick method. We found that the neutral B 4H 5 cluster has two optical isomers as either a global minimum structure, or as almost degenerate isomers with the global minimum structure. For the B4H5- anion only the third lowest isomer forms a pair of optical isomers. The chemical bonding patterns revealed by the Adaptive Natural Density Partitioning (AdNDP) analysis can easily explain the geometric structure of even very exotic isomers and global minima. Theoretical vertical electron detachment energies (VDEs) were calculated for comparison with future experimental work.

  19. Isomer-specific analysis of nonylphenols with estrogenic activity and their distribution in aquatic environment in relation to endocrine disrupters

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Y.S.; Katase, T.; Inoue, T. [Nihon Univ., Fujisawa, Kanagawa (Japan). College of Bioresource Sciences; Horii, Y.; Yamashita, N. [National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki (Japan); Makino, M.; Uchiyama, T.; Fujimoto, Y. [Nihon Univ., Chiba (Japan). College of Pharmacy

    2004-09-15

    The effect of estrogen-exposure on levels of a larval storage protein of Balanus amphitrite, cypris major protein (CMP), which is related to barnacle vitellin, has been examined at low concentrations (0.01-1.0 {mu}g/l) of 4-nonylphenol (NP) and 17{beta}-estradiol (E2) (1.0 {mu}g/l) from egg hatching until the nauplius cypris stage. Eventually, the exposure to 0.01 {mu}g/l of NP led to a ca. 50% increase in the optical density of the CMP. There are theoretically ca. 170 kinds of isomers of NP, based on the structure of the nonyl side chain in NP. We fractionated a commercial NP by high performance liquid chromatography (HPLC) to give six fractions (Fr. 1- Fr. 6). Fr. 3 - Fr. 5 were further separated to afford 14 fractions by using gas chromatograph equipped with a preparative fraction collector (GC-PFC) and 11 NP isomers were identified by gas chromatograph equipped with mass spectrometry (GC-MS) and nuclear magnetic resonance spectroscopy (NMR). The chemical structures of 11 isomers (NP1 to NP14) were characterized and estrogenicities of the selected isomers were tested in recombinant yeast screen system. The 4-(1,1-dimethyl-2-ethyl-pentyl)- phenol (NP7) was found to exhibit the highest estrogenic activity corresponding to 1.9 x 10{sup -3} that of E2. The NP4 and 6 were structurally in diastereomer. The individual isomer of NP in aquatic samples taken from Ariake Sea and Tokyo, Japan was analyzed by steam distillation extraction in the present study.

  20. Effects of butanol isomers on dipalmitoylphosphatidylcholine bilayer membranes.

    Science.gov (United States)

    Reeves, Megan D; Schawel, Adam K; Wang, Weidong; Dea, Phoebe

    2007-06-01

    Differential scanning calorimetry and (31)P-NMR were used to study the effects of butanol isomers on the thermotropic phase behavior of dipalmitoylphosphatidylcholine (DPPC) bilayers. The threshold concentration for the onset of interdigitation for each isomer was determined by the disappearance of the pretransition and the onset of a large hysteresis between the heating and cooling scans of the gel-to-liquid main transition. The threshold concentration was found to correlate with increased solubility of the isomers in the aqueous phase, led by tert-butanol. However, as the solution concentration of tert-butanol increased, there was an abrupt shrinking of the hysteresis, initially with well-resolved shoulder peaks indicating mixed phases. The eventual disappearance of the shoulder peaks was correlated with a breakdown of the multilamellar structure identified using (31)P-NMR.

  1. 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.

  2. Isomer and decay studies for the rp process at IGISOL

    Energy Technology Data Exchange (ETDEWEB)

    Kankainen, A.; Elomaa, V.V.; Eronen, T.; Hakala, J.; Jokinen, A.; Karvonen, P.; Reponen, M.; Rissanen, J.; Saastamoinen, A.; Weber, C.; Aeystoe, J. [University of Jyvaeskylae, Department of Physics, Jyvaeskylae (Finland); Novikov, Yu.N.; Batist, L. [Petersburg Nuclear Physics Institute, Gatchina (Russian Federation); Oinonen, M. [University of Helsinki, Dating Laboratory, Helsinki (Finland); Vorobjev, G. [Gesellschaft fuer Schwerionenforschung mbH, Darmstadt (Germany)

    2012-04-15

    This article reviews the decay studies of neutron-deficient nuclei within the mass region A=56-100 performed at the Ion-Guide Isotope Separator On-Line (IGISOL) facility in the University of Jyvaeskylae over last 25 years. Development from He-jet measurements to on-line mass spectrometry, and eventually to atomic mass measurements and post-trap spectroscopy at IGISOL, has yielded studies of around 100 neutron-deficient nuclei over the years. The studies form a solid foundation to astrophysical rp -process path modelling. The focus is on isomers studied either via spectroscopy or via Penning-trap mass measurements. The review is complemented with recent results on the ground and isomeric states of {sup 90}Tc. The excitation energy of the low-spin isomer in {sup 90}Tc has been measured as E{sub x}=144.1(17) keV with JYFLTRAP double Penning trap and the ground state of {sup 90}Tc has been confirmed to be the (8{sup +}) state with a half-life of T{sub 1/2}=49.2(4) s. Finally, the mass-excess results for the spin-gap isomers {sup 53}Co{sup m} and {sup 95}Pd{sup m} and implications from the JYFLTRAP mass measurements for the (21{sup +}) isomer in {sup 94}Ag are discussed. (orig.)

  3. ISOMER-SELECTED DECAY OF THE GDR IN DY-156

    NARCIS (Netherlands)

    VANSCHAGEN, JPS; HARAKEH, MN; HESSELINK, WHA; NOORMAN, RF

    1995-01-01

    The strength distribution of high-energy gamma-rays emitted in the statistical decay of the 156Dy compound nucleus, with E* = 92.5 MeV, has been measured inclusively and for selected decay pathways in which isomers in 149Dy, 151Dy and 152Dy were populated. For both spectra a deformation \\beta\\ = 0.3

  4. 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.

  5. High Spin Isomers and Super Heavy Elements (SHE) Synthesis

    Science.gov (United States)

    Popescu, Domitian G.

    2010-04-01

    To get closer to the SHE-Island the new radioactive beams are proposed for future fusion reaction. We suggest something different : to use the advantage of High Spin Isomer States, by tacking into account the importance of the G (spin-isospin cupling) suggested by Ripka 1.

  6. Identification of position isomers by energy-resolved mass spectrometry.

    Science.gov (United States)

    Menachery, Sunil Paul M; Laprévote, Olivier; Nguyen, Thao P; Aravind, Usha K; Gopinathan, Pramod; Aravindakumar, Charuvila T

    2015-07-01

    This study reports an energy-resolved mass spectrometric (ERMS) strategy for the characterization of position isomers derived from the reaction of hydroxyl radicals ((●)OH) with diphenhydramine (DPH) that are usually hard to differentiate by other methods. The isomer analogues formed by (●)OH attack on the side chain of DPH are identified with the help of a specific fragment ion peak (m/z 88) in the collision-induced dissociation (CID) spectrum of the protonated molecule. In the negative ion mode, the breakdown curves of the deprotonated molecules show an order of stability (supported by density functional theory (DFT) calculations) ortho > meta > para of the positional isomers formed by the hydroxylation of the aromatic ring. The gas phase stability of the deprotonated molecules [M - H](-) towards the benzylic cleavage depends mainly on the formation of intramolecular hydrogen bonds and of the mesomeric effect of the phenol hydroxyl. The [M - H](-) molecules of ortho and meta isomers result a peak at m/z 183 with notably different intensities because of the presence/absence of an intramolecular hydrogen bonding between the OH group and C9 protons. The ERMS approach discussed in this report might be an effective replacement for the conventional methods that requires very costly and time-consuming separation/purification methods along with the use of multi-spectroscopic methods.

  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. Shape Isomer in 236U Populated by Thermal Neutron Capture

    DEFF Research Database (Denmark)

    Andersen, Verner; Christensen, Carl Jørgen; Borggreen, J.

    1976-01-01

    The 116 ns shape isomer in 236U was populated by thermal neutron capture. Conversion electrons and X-rays were detected simultaneously in delayed coincidence with fission. The ratio of delayed to prompt fission was measured with the result, σIIf/σf = (1.0±0.2) × 10−5. A branching of the isomeric...

  9. Thorium isomer for radiative emission of neutrino pair

    CERN Document Server

    Sasao, N; Yoshimi, A; Yoshimura, K; Yoshimura, M

    2013-01-01

    It is proposed to use the isomer ionic ground state $^{229m}$Th$^{4+}$ embedded in transparent crystals for precision determination of unknown neutrino parameters. Isolation from solid environment of the proposed nuclear process, along with available experimental techniques of atomic physics, has a great potentiality for further study.

  10. FY2011 Annual Report for the Actinide Isomer Detection Project

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-10-01

    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 {mu}s. 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

  11. Isomer-specific regulation of metabolism and PPARγ signaling by CLA in human preadipocytes

    OpenAIRE

    Brown, J. Mark; Boysen, Maria Sandberg; Jensen, Søren Skov; Morrison, Ron F.; Storkson, Jayne; Lea-Currie, Renee; Pariza, Michael; Mandrup, Susanne; McIntosh, Michael K.

    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 in primary human adiopcytes in vitro. Here we investigated the mechanism behind the isomer-specific, CLA-mediated reduction in TG accumulation in differentiating human preadipocytes. Trans-10,cis-12 CLA de...

  12. On the decrease in charge radii of multi-quasi particle isomers

    Energy Technology Data Exchange (ETDEWEB)

    Bissell, M.L. [School of Physics and Astronomy, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Flanagan, K.T. [Schuster Laboratory, University of Manchester, Manchester M13 9PL (United Kingdom); Gardner, M.D. [School of Physics and Astronomy, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Avgoulea, M. [Schuster Laboratory, University of Manchester, Manchester M13 9PL (United Kingdom); Billowes, J. [Schuster Laboratory, University of Manchester, Manchester M13 9PL (United Kingdom); Campbell, P. [Schuster Laboratory, University of Manchester, Manchester M13 9PL (United Kingdom); Cheal, B. [Schuster Laboratory, University of Manchester, Manchester M13 9PL (United Kingdom)]. E-mail: bc@mags.ph.man.ac.uk; Eronen, T. [Department of Physics, University of Jyvaeskylae, PB 35 (YFL) FIN-40351 Jyvaeskylae (Finland); Forest, D.H. [School of Physics and Astronomy, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Huikari, J. [Department of Physics, University of Jyvaeskylae, PB 35 (YFL) FIN-40351 Jyvaeskylae (Finland); Jokinen, A. [Department of Physics, University of Jyvaeskylae, PB 35 (YFL) FIN-40351 Jyvaeskylae (Finland); Moore, I.D. [Department of Physics, University of Jyvaeskylae, PB 35 (YFL) FIN-40351 Jyvaeskylae (Finland); Nieminen, A. [Schuster Laboratory, University of Manchester, Manchester M13 9PL (United Kingdom); Penttilae, H. [Department of Physics, University of Jyvaeskylae, PB 35 (YFL) FIN-40351 Jyvaeskylae (Finland); Rinta-Antila, S. [Department of Physics, University of Jyvaeskylae, PB 35 (YFL) FIN-40351 Jyvaeskylae (Finland); Tordoff, B. [Schuster Laboratory, University of Manchester, Manchester M13 9PL (United Kingdom); Tungate, G. [School of Physics and Astronomy, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Aystoe, J. [Department of Physics, University of Jyvaeskylae, PB 35 (YFL) FIN-40351 Jyvaeskylae (Finland)

    2007-02-15

    We report changes in mean-square charge radii, {delta}, magnetic moments and quadrupole moments for three multi-quasi particle isomers; {sup 97m2}Y, {sup 176m}Yb and {sup 178m1}Hf. All the isomers are observed to display a decrease in compared to the lower-lying nuclear state on which the isomer is built. The decreases in occur despite the isomers showing increases in quadrupole moment. Possible mechanisms for the effect, which is now seen for six multi-quasi particle isomers, are discussed.

  13. Population and decay of a Kπ=8- two-quasineutron isomer in 244Pu

    Science.gov (United States)

    Hota, S. S.; Tandel, S. K.; Chowdhury, P.; Ahmad, I.; Carpenter, M. P.; Chiara, C. J.; Greene, J. P.; Hoffman, C. R.; Jackson, E. G.; Janssens, R. V. F.; Kay, B. P.; Khoo, T. L.; Kondev, F. G.; Lakshmi, S.; Lalkovski, S.; Lauritsen, T.; Lister, C. J.; McCutchan, E. A.; Moran, K.; Peterson, D.; Shirwadkar, U.; Seweryniak, D.; Stefanescu, I.; Toh, Y.; Zhu, S.

    2016-08-01

    The decay of a Kπ=8- isomer in 244Pu and the collective band structures populating the isomer were studied using deep inelastic excitations with 47Ti and 208Pb beams, respectively. Precise measurements of M 1 /E 2 branching ratios in the band confirm a 9 /2-[734] ν⊗7 /2+[624] ν configuration assignment for the isomer, validating the systematics of Kπ=8- , two-quasineutron isomers observed in even-Z , N =150 isotones. These isomers around the deformed shell gap at N =152 provide critical benchmarks for theoretical predictions of single-particle energies in this gateway region to superheavy nuclei.

  14. A thirty second isomer in {sup 171}Hf

    Energy Technology Data Exchange (ETDEWEB)

    Campbell, P.; Billowes, J.; Cooper, T.G.; Grant, I.S.; Pearson, M.R.; Wheeler, P.D. [Schuster Laboratory, University of Manchester, M13 9PL (United Kingdom); Cochrane, E.C.A.; Cooke, J.L.; Evans, D.E.; Griffith, J.A.R.; Persson, J.R.; Richardson, D.S.; Tungate, G.; Zybert, L. [School of Physics and Space Research, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Dendooven, P.; Honkanen, A.; Huhta, M.; Oinonen, M.; Penttilae, H.; Aeystoe, J. [Accelerator Laboratory, University of Jyvaeskylae, PL 35 Jyvaeskylae SF-403 51 (Finland)

    1997-09-01

    An isomer has been detected in {sup 171}Hf with a half-life of T{sub 1/2} 29.5(9) s. The state was populated in the {sup 170}Yb({alpha},3n){sup 171m}Hf reaction at a beam energy of E{sub {alpha}} = 50 MeV in an on-line ion guide isotope separator. The isomeric {sup 171m}Hf{sup +} beam was extracted from the ion guide, mass-analysed and implanted in the surface of a microchannel-plate. The half-life of the collected activity was measured from the decay of the microchannel-plate count rate. We associate the isomer with the first excited state in {sup 171}Hf with spin 1/2{sup -} at an excitation energy of 22(2) keV. (author)

  15. Fluorescence characteristics of polychlorinated biphenyl isomers in cyclodextrin media

    Energy Technology Data Exchange (ETDEWEB)

    Femia, R.A.; Scypinski, S.; Love, L.J.C.

    1985-01-01

    The fluorescence characteristics of several polychlorinated biphenyl (PCB) isomers in ..cap alpha..- and ..beta..-cyclodextrin (CD) are discussed and contrasted. The steric hindrance of PCBs imposed by the positions of the chlorine atoms on the rings determines the overall stability of the resulting inclusion complexes with cyclodextrin which is reflected in the fluorescence intensities. Less substituted homologues include into the CD cavity equally well in both cyclodextrins, but very heavily substituted molecules show drastic differences between their fluorescence intensities in the ..cap alpha..- and ..beta..-cyclodextrin solutions. This behavior can be employed as a method for spectral fractionation of PCB isomers. Spectral separation is demonstrated here for two variably substituted molecules, and the photophysical limitations of this approach are discussed.

  16. Spectroscopic Studies of the Several Isomers of UO3

    Energy Technology Data Exchange (ETDEWEB)

    Sweet, Lucas E.; Reilly, Dallas D.; Abrecht, David G.; Buck, Edgar C.; Meier, David E.; Su, Yin-Fong; Brauer, Carolyn S.; Schwantes, Jon M.; Tonkyn, Russell G.; Szecsody, James E.; Blake, Thomas A.; Johnson, Timothy J.

    2013-09-26

    Uranium trioxide is known to adopt seven different structural forms. While these structural forms have been well characterized using x-ray or neutron diffraction techniques, little work has been done to characterize their spectroscopic properties, particularly of the pure phases. Since the structural isomers of UO3 all have similar thermodynamic stabilities and most tend to hydrolyze under open atmospheric conditions, mixtures of UO3 phases and the hydrolysis products are common. Much effort went into isolating pure phases of UO3. Utilizing x-ray diffraction as a sample identification check, UV/Vis/NIR spectroscopic signatures of α-UO3, β-UO3, γ-UO3 and UO2(OH)2 products were obtained. The spectra of the pure phases can now be used to characterize typical samples of UO3, which are often mixtures of isomers.

  17. Observation of the 2$^+$ isomer in $^{52}$Co

    CERN Document Server

    Orrigo, S E A; Gelletly, W; Fujita, Y; Blank, B; Giovinazzo, J; Agramunt, J; Algora, A; Ascher, P; Bilgier, B; Cáceres, L; Cakirli, R B; de France, G; Ganioğlu, E; Gerbaux, M; Grévy, S; Kamalou, O; Kozer, H C; Kucuk, L; Kurtukian-Nieto, T; Molina, F; Popescu, L; Rogers, A M; Susoy, G; Stodel, C; Suzuki, T; Tamii, A; Thomas, J C

    2016-01-01

    We report the first observation of the 2$^+$ isomer in $^{52}$Co, produced in the $\\beta$ decay of the 0$^+$, $^{52}$Ni ground state. We have observed three $\\gamma$-rays at 849, 1910, and 5185 keV characterizing the de-excitation of the isomer. We have measured a half-life of 102(6) ms for the isomeric state. The Fermi and Gamow-Teller transition strengths for the $\\beta$ decay of $^{52m}$Co to $^{52}$Fe have been determined. We also add new information on the $\\beta$ decay of the 6$^+$, $^{52}$Co ground state, for which we have measured a half-life of 112(3) ms.

  18. The structural and dynamical variables of pentane isomers

    Science.gov (United States)

    Patel, Tarika K.; Vaghela, M. V.; Gajjar, P. N.

    2016-05-01

    We derived structural and dynamical properties of pentane isomers: normal pentane, iso-pentane and neo pentane for liquid and gaseous state. We use molecular dynamics simulation to calculate the dynamical properties of pentane isomers for number of particles 729 using the intermolecular potential and force due to Lenard Jones potential. The computations also include mean square displacement and self diffusion co-efficient using Einstein relation. In structural properties, structure factor and phonon frequency are obtaining from P Y Method and Hubbard and Beeby Approach respectively. The Intermolecular potential and self diffusion co-efficient depend on the branching in the structure. The pair correlation function and phonon dispersion curves revels the complex structure of neo-pentane with respect to iso-pentane and n-pentane.

  19. Theoretical characterisation of the SSO, cyclic SOS and SOS isomers

    Science.gov (United States)

    Denis, Pablo A.

    2010-01-01

    The SSO, cyclic SOS and open SOS isomers have been investigated, employing the CCSD(T) methodology and the cc-pV(X + d)Z X = 3, 4, 5, 6 basis sets. The anharmonic force fields have been calculated to predict the fundamental vibrational frequencies, rotational constants, vibration-rotation corrections, anharmonic corrections to zero-point energies, and structural parameters. At the CCSD(T)/CBS limit and including corrections for scalar relativistic effects, complete quadruple excitations, spin-orbit and core-valence correlation effects, the estimated enthalpies of formation are -13.9 ± 1, 32.1 ± 1, and -51.2 ± 1 kcal/mol, for SSO, cyclic-SOS and open-SOS, respectively. Finally, it was found that the asymmetric SO stretch of the open and cyclic SOS isomers are located in a nearly identical position and it is likely that SOS also maybe present in the surface of Io.

  20. Mobilities of Li(+)-attached butanol isomers in He gas.

    Science.gov (United States)

    Takahashi, K; Saito, K; Koizumi, T; Matoba, S; Kojima, T M; Tanuma, H; Shiromaru, H

    2013-08-28

    Mobilities of Li(+)-attached butanol isomers, (n-BuOH)Li(+), (s-BuOH)Li(+), (i-BuOH)Li(+), and (t-BuOH)Li(+), in helium gas were measured over a range of reduced electric fields (E/N = 25-96 Td) at room temperature. Arrival time measurements accurately identified small differences in the measured mobilities of the isomer ions. At low E/N (≤30 Td, corresponding to a mean collision energy ε≤0.05 eV), (n-BuOH)Li(+) showed a mobility about 1.5% greater than that of the other ions, but at high E/N (≥75 Td, ε≥0.1 eV) its mobility was about 1.1% less.

  1. Preparation of Conjugated Linoleic Acid and Identification of Its Isomers

    Institute of Scientific and Technical Information of China (English)

    郭诤; 张根旺; 孙彦

    2003-01-01

    Conjugated linoleic acid(CLA)is a kind of fatty acid with physiological activities and potential appli-cation prospect ,A synthesis method of conjugated linoleic acid and a purification technology were studied .CLA was prepared and purified by urea-complexation and conjugation using safflower oil as raw material,The purity of CLA and total recovery of the product was more than 95% and 48%,respectively,The main isomers produced in alkali-catalyzed conjugation were identified by gas chromatography (GC)linked to mass spectrometry(MS) and Fourier transform infrared spectroscopy(FTIR),The total amount of the two main isomers (9cis,11trans-and 10trans,12cis-CLA) determined by GC was more than 90% of the product.

  2. A simple, rapid method for HPLC analysis of lycopene isomers.

    Science.gov (United States)

    Ishida, B K; Ma, J; Chan, B

    2001-01-01

    A rapid method for the extraction, separation and quantification of the geometric isomers of lycopene and beta-carotene from tomato fruit is described. Carotenoids in tomato were separated and eluted using a reversed-phase HPLC with a C30 column and a mobile phase consisting of methyl-t-butyl ether, methanol and ethyl acetate. The system provided sharp resolution of cis- and trans-isomers of lycopene within approximately 23 min in contrast to the longer and more complex gradient procedures required by previously described methods. Experiments indicate that the stability of extracts of fresh tomato may be improved if stored at -20 degrees C, and that the presence of the antioxidant BHA has no apparent effect on stability.

  3. Condensations of single DNA molecules induced by heptaplatin and its chiral isomer

    Science.gov (United States)

    Zhang, Hong-Yan; Liu, Yu-Ru; Li, Wei; Li, Hui; Dou, Shuo-Xing; Xie, Ping; Wang, Wei-Chi; Wang, Peng-Ye

    2014-08-01

    Heptaplatin is a third-generation platinum antitumor drug. It has a chiral isomer. We studied the interactions between the two isomers and DNA by using magnetic tweezers and atomic force microscopy (AFM) to investigate the effect of chiralities of the isomers on the interactions. We found that the extension curves and average condensation rates of DNA molecules incubated with heptaplatin were nearly the same as those incubated with its chiral isomer. In addition, the structures of DNA molecules incubated with heptaplatin were also similar to those incubated with its chiral isomer. These results indicate the difference in chirality of the two isomers does not induce different interactions of the isomers with DNA. Our study may facilitate the understanding of interactions of platinum complexes with DNA and the design of new antitumor platinum complexes.

  4. Focal point analysis of torsional isomers of acrylic acid

    Science.gov (United States)

    Alev Çiftçioğlu, Gökçen; Trindle, Carl; Yavuz, Ilhan

    2010-10-01

    The thermochemistry of acrylic acid has presented challenges owing to its high reactivity, tendency to dimerize in the gas phase, and the existence of two very nearly equal energy conformational isomers. Well-tested thermochemical schemes including G2, G3, G4, and CBS-QB3 agree in the prediction that the s-cis syn structure is the most stable of the torsional isomers, with the s-cis anti form lying 3 kJ mol-1 or less higher in energy. Microwave spectra suggest a value of 0.63 kJ mol-1. The energy barrier between these forms is in the neighbourhood of 25 kJ mol-1 according to a MP2/cc-pVDZ calculation. We present estimates of the relative energies of all four torsional isomers and the rotational barrier based on a variant of the Focal Point Analysis developed by Császár and co-workers. These calculations, extending to the CCSD(T)/cc-pV5Z level, predict that the s-cis anti torsional isomer is the most stable form, in contrast to prior estimates. The s-cis syn form lies about 2.9 kJ mol-1 higher, while the s-trans syn and anti forms lie at about 21.7 and 23.3 kJ mol-1, respectively. We estimate the rotational barrier between the s-cis trans and s-cis anti structures to be about 23.9 kJ mol-1. Error ranges derived from the fit to extrapolation forms suggest that our estimates have an uncertainty of about 0.1 kJ mol-1.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

    1977-10-17

    Experiments aimed at testing for the existence of yrast traps are reported. A search for delayed ..gamma.. 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 /sup 40/Ar, /sup 50/Ti, and /sup 65/Cu projectiles. An island of high-spin isomers is found to exist in the region 64 < or approx. = Z > or approx. = 71 and N < or approx. = 82.

  6. 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.

  7. Determination of aminocresol isomers by high-speed liquid chromatography.

    Science.gov (United States)

    Sakurai, H; Kito, M

    Aminocresol isomers (4-hydroxy-m-toluidine [II], 3-hydroxy-p-toluidine [II], 2-hydroxy-p-toluidine [III]) and p-aminophenol have been separated and determined by a high-speed liquid Chromatographie method. Since this method is applicable in aqueous media, it was used to investigate the suitability of a haemin-cysteine system as a model for the cytochrome P-450 mono-oxygenase system, by determination of the [I], [II], [III] and p-aminophenol formed.

  8. Flame Propagation of Butanol Isomers/Air Mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Veloo, Peter S.; Egolfopoulos, Fokion N.

    2011-01-01

    An experimental and computational study was conducted on the propagation of flames of saturated butanol isomers. The experiments were performed in the counterflow configuration under atmospheric pressure, unburned mixture temperature of 343 K, and for a wide range of equivalence ratios. The experiments were simulated using a recent kinetic model for the four isomers of butanol. Results indicate that n-butanol/air flames propagate somewhat faster than both sec-butanol/air and iso-butanol/air flames, and that tert-butanol/air flames propagate notably slower compared to the other three isomers. Reaction path analysis of tert-butanol/air flames revealed that iso-butene is a major intermediate, which subsequently reacts to form the resonantly stable iso-butenyl radical retarding thus the overall reactivity of tert-butanol/air flames relatively to the other three isomers. Through sensitivity analysis, it was determined that the mass burning rates of sec-butanol/air and iso-butanol/air flames are sensitive largely to hydrogen, carbon monoxide, and C{sub 1}–C{sub 2} hydrocarbon kinetics and not to fuel-specific reactions similarly to n-butanol/air flames. However, for tert-butanol/air flames notable sensitivity to fuel-specific reactions exists. While the numerical results predicted closely the experimental data for n-butanol/air and sec-butanol/air flames, they overpredicted and underpredicted the laminar flame speeds for iso-butanol/air and tert-butanol/air flames respectively. It was demonstrated further that the underprediction of the laminar flame speeds of tert-butanol/air flames by the model was most likely due to deficiencies of the C{sub 4}-alkene kinetics.

  9. Spectroscopic and computational study of a new isomer of salinomycin

    Science.gov (United States)

    Pankiewicz, Radosław

    2013-09-01

    A new derivative of polyether ionophore salinomycin was obtained as a result of a rearrangement catalysed by sulphuric acid in two-phase medium of water/methylene chloride solution. The new isomer was fully characterized by multinuclear 2D NMR, NOESY and MALDI-TOF. The properties of the new compound were additionally study by semiempirical (PM5) and DFT (B3LYP) methods. A potential mechanism of the rearrangement was also proposed.

  10. Characterization and performance of short cationic antimicrobial peptide isomers.

    Science.gov (United States)

    Juba, Melanie; Porter, Devin; Dean, Scott; Gillmor, Susan; Bishop, Barney

    2013-07-01

    Cationic antimicrobial peptides (CAMPs) represent an ancient defense mechanism against invading bacteria, with peptides such as the cathelicidins being essential elements of vertebrate innate immunity. CAMPs are typically associated with broad-spectrum antimicrobial potency and limited bacterial resistance. The cathelicidin identified from the elapid snake Naja atra (NA-CATH) contains a semi-conserved repeated 11-residue motif (ATRA motif) with a sequence pattern consistent with formation of an amphipathic helical conformation. Short peptide amides (ATRA-1, -1A, -1P, and -2) generated based on the pair of ATRA motifs in NA-CATH exhibited varied antimicrobial potencies. The small size of the ATRA peptides, coupled with their varied antimicrobial performances, make them interesting models to study the impact various physico-chemical properties have on antimicrobial performance in helical CAMPs. Accordingly, the D- and L-enantiomers of the peptide ATRA-1A, which in earlier studies had shown both good antimicrobial performance and strong helical character, were investigated in order to assess the impact peptide stereochemistry has on antimicrobial performance and interaction with chiral membranes. The ATRA-1A isomers exhibit varied potencies against four bacterial strains, and their conformational properties in the presence of mixed zwitterionic/anionic liposomes are influenced by anionic lipid content. These studies reveal subtle differences in the properties of the peptide isomers. Differences are also seen in the abilities of the ATRA-1A isomers to induce liposome fusion/aggregation, bilayer rearrangement and lysing through turbidity studies and fluorescence microscopy. The similarities and differences in the properties of the ATRA-1A isomers could aid in efforts to develop D-peptide-based therapeutics using high-performing L-peptides as templates.

  11. 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...

  12. Isomer-specific biodegradation of methylphenanthrenes by soil bacteria.

    Science.gov (United States)

    Lamberts, Rasmus F; Christensen, Jan H; Mayer, Philipp; Andersen, Ole; Johnsen, Anders R

    2008-07-01

    It is assumed that bacteria generally degrade 2-methylphenanthrene (2MPhe) in preference to 1-methylphenanthrene (1MPhe), and that environmental biodegradation of methylated PAHs therefore can be described qualitatively by changes in relative concentrations of these isomers. Our objective was to investigate whether microbial phenanthrene degraders (Sphingomonas and Mycobacterium) show such isomer-specific PAH degradation. Eleven out of twenty-nine phenanthrene degraders could grow on methylphenanthrene. The mycobacteria grew only on 2MPhe, the sphingomonads grew mostly on 1MPhe, and one sphingomonad could utilize both substrates. Seven strains were tested in a two-phase system where 1MPhe and 2MPhe were supplied in heptamethylnonane. For these strains, a consistent description of biodegradation based on the 2MPhe/1MPhe diagnostic ratio would not be possible because three Mycobacterium and one Sphingomonas degraded 2MPhe faster than 1MPhe, another Sphingomonas degraded 1MPhe and 2MPhe at almost equal rates, and two Sphingomonas degraded 1MPhe faster than 2MPhe. Thus, environmental biodegradation of phenanthrenes may theoretically proceed with only minor changes in 2MPhe/1MPhe ratios if individual members of the degrader community have different isomer preferences. However, two soil microcosms polluted with bunker oil confirmed the general decline in 2MPhe/1MPhe ratio during oil biodegradation.

  13. Diffusion studies of dihydroxybenzene isomers in water-alcohol systems.

    Science.gov (United States)

    Codling, Dale J; Zheng, Gang; Stait-Gardner, Tim; Yang, Shu; Nilsson, Mathias; Price, William S

    2013-03-01

    Nuclear magnetic resonance diffusion studies can be used to identify different compounds in a mixture. However, because the diffusion coefficient is primarily dependent on the effective hydrodynamic radius, it is particularly difficult to resolve compounds with similar size and structure, such as isomers, on the basis of diffusion. Differential solution interactions between species in certain solutions can afford possibilities for separation. In the present study, the self-diffusion of the three isomers of dihydroxybenzene (i.e., (1,2-) catechol, (1,3-) resorcinol, and (1,4-) hydroquinone) was studied in water, aqueous monohydric alcohols (i.e., ethanol, 1-propanol, tert-butanol), and aqueous ethylene glycol. These systems allowed the effects of isomerism and differential solvent interactions on diffusion to be examined. It was found that, while in aqueous solution these isomers had the same diffusion coefficient, in water-monohydric alcohol systems the diffusion coefficient of catechol differed from those of resorcinol and hydroquinone. The separation was found to increase at higher concentrations of monohydric alcohols. The underlying chemical reasons for these differences were investigated.

  14. Borromean halo, Tango halo, and halo isomers in atomic nuclei

    Science.gov (United States)

    Izosimov, Igor

    2016-01-01

    Structure of the ground and excited states in halo-like nuclei is discussed. Both the Borromean and tango halo types can be observed for n-p configurations of atomic nuclei.Structure of the halo may be different for the different levels and resonances in atomic nuclei. Isobar analog, double isobar analog, configuration, and double configuration states can simultaneously have n-n, n-p, and p-p halo components in their wave functions. When the halo structure of the excited state differs from that of the ground state, or the ground state has non-halo structure, the γ-transition from the excited state to the ground state can be essentially hindered, i.e. the formation of a specific type of isomers (halo isomers) becomes possible. B(Mγ) and B(Eγ) values for γ-transitions in 6,7,8Li, 8,9,10Be, 8,10,11B, 10,11,12,13,14C, 13,14,15,16,17N, 15,16,17,19O, and 17F are analyzed. Special attention is given to nuclei which ground state does not exhibit halo structure but the excited state (halo isomer) may have one.

  15. Solvent and temperature induced switching between structural isomers of Rh(I) phosphinoalkyl thioether (PS) complexes.

    Science.gov (United States)

    Wiester, Michael J; Braunschweig, Adam B; Yoo, Hyojong; Mirkin, Chad A

    2010-08-02

    To develop functional systems based on the weak-link approach (WLA), it is important to understand how solvent and ligand binding strength alter the coordination geometry of complexes formed from this method. A series of phosphinoalkyl thioether (PS) hemilabile ligands with varying electron donating abilities were synthesized and incorporated into homoligated Rh(I)(PS)2Cl complexes to help understand the effects of solvent and ligand binding strength on the preferred coordination modes. The switching between closed and semiopen structural isomers of these Rh(I)(PS)2Cl complexes was studied by variable temperature 31P NMR spectroscopy in different solvent mixtures of CH2Cl2 and tetrahydrofuran (THF) to obtain thermodynamic parameters (DeltaG(o), DeltaH(o), TDeltaS(o), and K(eq)). The isomers differ in the position of the chloride counterion. In the closed isomer, the Cl- anion occupies the outer coordination sphere, while in the semiopen isomer, the Cl- has moved inner sphere and displaced one of the Rh-S bonds. The closed isomer is favored in CH2Cl2 and the semiopen isomer is favored in THF. The preference for either isomer at equilibrium depends on the solvent polarity, based upon the E(T)(N) solvent polarity scale, as was determined from 15 different solvents, with more polar solvents favoring the closed isomer. The isomer preference also depends on the electron donating ability of the group attached to the sulfur of the PS ligand, with electron donating groups favoring the closed isomers and electron withdrawing groups favoring the semiopen isomers. The formation of the semiopen isomer from the closed isomer is entropically favored but enthalpically disfavored under all conditions studied. Elucidation of the principles and environments that determine the equilibrium between the two isomers will aid in the design of functional complexes prepared by the WLA.

  16. Distribution of perfluorooctane sulfonate isomers and predicted risk of thyroid hormonal perturbation in drinking water.

    Science.gov (United States)

    Yu, Nanyang; Wang, Xiaoxiang; Zhang, Beibei; Yang, Jingping; Li, Meiying; Li, Jun; Shi, Wei; Wei, Si; Yu, Hongxia

    2015-06-01

    We documented the distribution of seven perfluorooctane sulfonate (PFOS) isomers in drinking water in Jiangsu Province, China. Compared to the 30% proportion of branched PFOS in technical PFOS, the levels of branched PFOS in drinking water increased to 31.8%-44.6% of total PFOS. Because of previous risk assessment without considering the PFOS isomer profile and the toxicity of individual PFOS isomers, here we performed a new health risk assessment of PFOS for thyroid hormonal perturbation in drinking water with the contribution from individual PFOS isomers. The risk quotients (RQs) of individual PFOS isomers indicated that linear PFOS contributed most to the risk among all the target PFOS isomers (83.0%-90.2% of the total PFOS RQ), and that risk from 6m-PFOS (5.2%-11.9% of the total PFOS RQ) was higher than that from other branched PFOS isomers. We found that the risks associated with PFOS in drinking water would be overestimated by 10.0%-91.7% if contributions from individual PFOS isomers were not considered. The results revealed that the PFOS isomer profile and the toxicity of individual PFOS isomers were important factors in health risk assessment of PFOS and should be considered in the future risk assessments. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. Structures and photoelectric properties of five benzotrithiophene isomers-based donor-acceptor copolymers

    Science.gov (United States)

    Cheng, Na; Ma, Yuchen; Liu, Yongjun; Zhang, Changqiao; Liu, Chengbu

    2016-04-01

    In this paper, we have investigated the structures, electronic and optical properties of five conjugated copolymers (BTT1-BTz, BTT2-BTz, BTT3-BTz, BTT4-BTz and BTT5-BTz) featuring benzotrithiophene (BTT) isomers as donor units and benzothiadiazole (BTz) as acceptor units, linked through thiophene spacers, employing many-body perturbation theory (MBPT). We have explored the isomer effects by configuration of the sulfur atoms in BTT units, aimed to get insight into how the structural modifications to the conjugated backbone can influence the molecular structures and electronic properties of conjugated polymers. Using the trimer as the computational model, the calculated low and high energy absorption bands (660 and 413 nm) for BTT1-BTz agree well with the experimental ones (645 and 430 nm) with a small offset of ~ 15 nm. On the basis of our calculations, it is found that the backbones of these polymers display different coplanarities, with the dihedral angles between the two neighboring rings varying from 12.3° to 79.0°. Importantly, both BTT1-BTz and BTT2-BTz exhibit intense adsorption around 660 and 623 nm, indicating their promising application in solar cells, whereas BTT3-BTz and BTT4-BTz display the intense adsorption at 569 and 551 nm, which are also usable in the tandem solar cells. BTT5-BTz has narrow and weak adsorption in the visible and infrared region, implying it is not conducive to the sunlight absorption. The blue shift of about 150 nm from BTT1-BTz to BTT5-BTz is suggested to be originated from the shorter effective conjugation lengths.

  18. Differential adsorption of CHON isomers at interstellar grain surfaces

    Science.gov (United States)

    Lattelais, M.; Pauzat, F.; Ellinger, Y.; Ceccarelli, C.

    2015-06-01

    Context. The CHON generic chemical formula covers different isomers such as isocyanic acid (HNCO), cyanic acid (HOCN), fulminic acid (HCNO), and isofulminic acid (HONC); the first three have been identified in a large variety of environments in the interstellar medium (ISM). Several phenomena could be at the origin of the observed abundances, such as different pathways of formation and destruction involving gas phase reactions with different possible activation barriers and/or surface processes depending on the local temperature and the nature of the support. Aims: The scope of this article is to shed some light on the interaction of the CHON isomers with interstellar grains as a function of the nature of the surface and to determine the corresponding adsorption energies in order to find whether this phenomenon could play a role in the abundances observed in the ISM. Methods: The question was addressed by means of numerical simulations using first principle periodic density functional theory (DFT) to represent the grain support as a solid of infinite dimension. Results: Regardless of the nature of the model surface (water ice, graphene, silica), two different classes of isomers were identified: weakly bound (HNCO and HCNO) and strongly bound (HOCN and HONC), with the adsorption energies of the latter group being about twice those of the former. The range of the adsorption energies is (from highest to lowest) HOCN > HONC > HNCO > HCNO. They are totally disconnected from the relative stabilities, which range from HNCO > HOCN > HCNO > HONC. Conclusions: The possibility of hydrogen bonding is the discriminating factor in the trapping of CHON species on grain surfaces. Whatever the environment, differential adsorption is effective and its contribution to the molecular abundances should not be ignored. The theoretical adsorption energies provided here could be profitably used for a more realistic modeling of molecule-surfaces interactions.

  19. Theoretical Study on Two C16H12O4 Isomers of Derivatives of Pagodane

    Institute of Scientific and Technical Information of China (English)

    LIU Feng-Ling; DU Ai-Ming; WANG Su-Jing

    2006-01-01

    Two C16H12O4 isomers of derivatives of pagodane were firstly reported and studied by using DFT method. Geometries, energies, and vibrational frequencies have been calculated for the two C16H12O4 isomers with pagodane-like structures at the B3LYP/6-31G** level of theory. Symmetries of isomer 1 and 2 are D2h and D2d, respectively. Heats of formation for the two C16H12O4 isomers have been estimated in this paper. According to the heats of formation, the two C16H12O4 isomers are more stable than pagodane. Heats of formation as well as the vibrational analysis indicate that the two C16H12O4 isomers enjoy sufficient stability to allow for the experi- mental preparation.

  20. An Isomer-Specific Approach to Endocrine-Disrupting Nonylphenol in Infant Food.

    Science.gov (United States)

    Günther, Klaus; Räcker, Torsten; Böhme, Roswitha

    2017-02-15

    Nonylphenols (NPs) are persistent endocrine disruptors that are priority hazardous substances of the European Union Water Framework Directive. Their presence in the environment has caused growing concern regarding their impact on human health. Recent studies have shown that nonylphenol is ubiquitous in commercially available foodstuffs and is also present in human blood. The isomer distribution of 4-nonylphenol was analyzed by gas chromatography - mass spectrometry in 44 samples of infant food. Our study shows that the distribution of nonylphenol isomers is dependent on the foodstuff analyzed. Although some isomer groups prevail, different distributions are frequent. Variations are even found in the same food group. Nonylphenol is a complex mixture of isomers, and the estrogenic potentials of each of these isomers are very different. Consequently, to determine the potential toxicological impact of NP in food, an isomer-specific approach is necessary.

  1. Formation of melatonin and its isomer during bread dough fermentation and effect of baking.

    Science.gov (United States)

    Yılmaz, Cemile; Kocadağlı, Tolgahan; Gökmen, Vural

    2014-04-02

    Melatonin is produced mainly by the pineal gland in vertebrates. Also, melatonin and its isomer are found in foods. Investigating the formation of melatonin and its isomer is of importance during bread dough fermentation and its degradation during baking since bread is widely consumed in high amounts. Formation of melatonin was not significant during dough fermentation. The melatonin isomer content of nonfermented dough was found to be 4.02 ng/g and increased up to 16.71 ng/g during fermentation. Lower amounts of isomer in crumb and crust than dough showed that the thermal process caused a remarkable degree of degradation in melatonin isomer. At the end of the 180 min fermentation Trp decreased by 58%. The results revealed for the first time the formation of a melatonin isomer in bread dough during yeast fermentation.

  2. Aromatic Character of All Possible C36H2 Isomers

    Institute of Scientific and Technical Information of China (English)

    Ablikim Kerim

    2006-01-01

    The stability of C36H2 isomers and selection rules for choosing position in addition reactions based on symmetrical C36(D6h and D2d) fullerene have been studied by means of Aihara's topological resonance energy (TRE) and bond resonance energy (BRE) methods. The relation between the addition pattern and BREs is established, showing high antiaromatic bonds are preferred for addition. These results show that TRE and BRE methods can be used to predict and interpret addition sites for these systems.

  3. Stability and electronic spectra of C76N2 isomers

    Institute of Scientific and Technical Information of China (English)

    TENG Qi-wen; WU Shi

    2005-01-01

    Study of geometries of 16 possible isomers for C76N2 based on C78(C2v) by intermediate neglect of differential overlap (INDO) series of methods indicated that the most stable geometry 25,78-C76N2 where two nitrogen atoms substitute two apexes C(25) and C(78) near the shortest X axis and Y axis formed by two hexagons and a pentagon. Electronic structures and spectra of C76N2 were investigated. The reason for the red-shift for absorptions of C76N2 compared with that of C78(C2v) is discussed.

  4. Nuclear states with anomalously large radius (size isomers)

    Energy Technology Data Exchange (ETDEWEB)

    Ogloblin, A. A.; Demyanova, A. S., E-mail: a.s.demyanova@bk.ru; Danilov, A. N. [National Research Center Kurchatov Institute (Russian Federation); Belyaeva, T. L. [Ciudad Universitaria, Universidad Nacional Autónoma de Meéxico (Mexico); Goncharov, S. A. [Moscow State University, Faculty of Physics (Russian Federation); Trzaska, W. [University of Jyvaäskylaä (Finland)

    2016-07-15

    Methods of determination of the nuclear excited state radii are discussed together with the recently obtained data on the states of some light nuclei having abnormally large radii (size isomers). It is shown that such states include excited neutron-halo states in {sup 9}Be, {sup 11}Be, and {sup 13}C and some alpha-cluster states in {sup 12}C, {sup 11}B, and {sup 13}C. Among the latter ones, there is the well-known Hoyle state in {sup 12}C—the structure of this state exhibit rudimentary features of alpha-particle states.

  5. Isomers of broparoestrol and antiestrogen action: comparison with tamoxifen.

    Science.gov (United States)

    Edery, M; Barnova, A; Drosdowsky, M; Guggiari, M; Vives, C; Rudali, G

    1985-01-01

    This study compares the relative biological potencies of a known antiestrogen tamoxifen to two triarylethylene compounds which have been shown previously to be potent inhibitors of rodent mammary tumorigenesis. Based on a) uterotrophic and anti-uterotrophic tests, b) indexes of cellularity, and c) protein content, these studies indicate that the trans, as well as the cis, isomers of bromotriphenylethylene are partial estrogen antagonists with no estrogenic effects in rat uteri and partial agonists in mouse uteri, whereas tamoxifen shows partial antiestrogenic/estrogenic effects in rats and is fully estrogenic in mice.

  6. Correlation of Fe2+ isomer shifts with bond lengths and bond strengths in neso- and sorosilicates

    Institute of Scientific and Technical Information of China (English)

    李哲; E.DeGrave

    1995-01-01

    An evaluation of Mbssbauer isomer shift and quadrupole splitting data of Fe2+ in a number of structurally well characterized neso- and sorosilicates is presented. It is found that the nearly linear correlations exist both between the isomer shift and the bond length and between the isomer shift and the bond strength. These correlations are discussed on the basis of the variation of the s-electron density at the Fe2+ nuclei with the chemical bond characteristics.

  7. 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...... by inserting 18 carbon atoms into an opened C-60. We have shown how the different local arrangements of these 18 carbon atoms are responsible for the significant isomer dependence observed. Our calculated spectra are in excellent agreement with the experimental counterparts....

  8. Chemical Simulations of Prebiotic Molecules: Interstellar Ethanimine Isomers

    Science.gov (United States)

    Quan, Donghui; Herbst, Eric; Corby, Joanna F.; Durr, Allison; Hassel, George

    2016-06-01

    The E- and Z-isomers of ethanimine (CH3CHNH) 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-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.

  9. The prenucleosome, a stable conformational isomer of the nucleosome.

    Science.gov (United States)

    Fei, Jia; Torigoe, Sharon E; Brown, Christopher R; Khuong, Mai T; Kassavetis, George A; Boeger, Hinrich; Kadonaga, James T

    2015-12-15

    Chromatin comprises nucleosomes as well as nonnucleosomal histone-DNA particles. Prenucleosomes are rapidly formed histone-DNA particles that can be converted into canonical nucleosomes by a motor protein such as ACF. Here we show that the prenucleosome is a stable conformational isomer of the nucleosome. It consists of a histone octamer associated with ∼ 80 base pair (bp) of DNA, which is located at a position that corresponds to the central 80 bp of a nucleosome core particle. Monomeric prenucleosomes with free flanking DNA do not spontaneously fold into nucleosomes but can be converted into canonical nucleosomes by an ATP-driven motor protein such as ACF or Chd1. In addition, histone H3K56, which is located at the DNA entry and exit points of a canonical nucleosome, is specifically acetylated by p300 in prenucleosomes relative to nucleosomes. Prenucleosomes assembled in vitro exhibit properties that are strikingly similar to those of nonnucleosomal histone-DNA particles in the upstream region of active promoters in vivo. These findings suggest that the prenucleosome, the only known stable conformational isomer of the nucleosome, is related to nonnucleosomal histone-DNA species in the cell.

  10. A Rapid, Comprehensive Liquid Chromatography-Mass Spectrometry (LC-MS)-based Survey of the Asp Isomers in Crystallins from Human Cataract Lenses*

    Science.gov (United States)

    Fujii, Norihiko; Sakaue, Hiroaki; Sasaki, Hiroshi; Fujii, Noriko

    2012-01-01

    Cataracts are caused by clouding of the eye lens and may lead to partial or total loss of vision. The mechanism of cataract development, however, is not well understood. It is thought that abnormal aggregates of lens proteins form with age, causing loss of lens clarity and development of the cataract. Lens proteins are composed of soluble α-, β-, and γ-crystallins, and as long lived proteins, they undergo post-translational modifications including isomerization, deamidation, and oxidation, which induce insolubilization, aggregation, and loss of function that may lead to cataracts. Therefore, analysis of post-translational modifications of individual amino acid residues in proteins is important. However, detection of the optical isomers of amino acids formed in these proteins is difficult because optical resolution is only achieved using complex methodology. In this study, we describe a new method for the analysis of isomerization of individual Asp residues in proteins using LC-MS and the corresponding synthetic peptides containing the Asp isomers. This makes it possible to analyze isomers of Asp residues in proteins precisely and quickly. We demonstrate that Asp-58, -76, -84, and -151 of αA-crystallin and Asp-62 and -96 of αB-crystallin are highly converted to lβ-, dβ-, and dα-isomers. The amount of isomerization of Asp is greater in the insoluble fraction at all Asp sites in lens proteins, therefore indicating that isomerization of these Asp residues affects the higher order structure of the proteins and contributes to the increase in aggregation, insolubilization, and disruption of function of proteins in the lens, leading to the cataract. PMID:23007399

  11. A rapid, comprehensive liquid chromatography-mass spectrometry (LC-MS)-based survey of the Asp isomers in crystallins from human cataract lenses.

    Science.gov (United States)

    Fujii, Norihiko; Sakaue, Hiroaki; Sasaki, Hiroshi; Fujii, Noriko

    2012-11-16

    Cataracts are caused by clouding of the eye lens and may lead to partial or total loss of vision. The mechanism of cataract development, however, is not well understood. It is thought that abnormal aggregates of lens proteins form with age, causing loss of lens clarity and development of the cataract. Lens proteins are composed of soluble α-, β-, and γ-crystallins, and as long lived proteins, they undergo post-translational modifications including isomerization, deamidation, and oxidation, which induce insolubilization, aggregation, and loss of function that may lead to cataracts. Therefore, analysis of post-translational modifications of individual amino acid residues in proteins is important. However, detection of the optical isomers of amino acids formed in these proteins is difficult because optical resolution is only achieved using complex methodology. In this study, we describe a new method for the analysis of isomerization of individual Asp residues in proteins using LC-MS and the corresponding synthetic peptides containing the Asp isomers. This makes it possible to analyze isomers of Asp residues in proteins precisely and quickly. We demonstrate that Asp-58, -76, -84, and -151 of αA-crystallin and Asp-62 and -96 of αB-crystallin are highly converted to lβ-, dβ-, and dα-isomers. The amount of isomerization of Asp is greater in the insoluble fraction at all Asp sites in lens proteins, therefore indicating that isomerization of these Asp residues affects the higher order structure of the proteins and contributes to the increase in aggregation, insolubilization, and disruption of function of proteins in the lens, leading to the cataract.

  12. 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

  13. Structures and stability of isomers of [Si,N,N,P] system

    Institute of Scientific and Technical Information of China (English)

    KAN Wei; YU Haitao; LI Mingxia; FU Honggang; SUN Jiazhong

    2004-01-01

    Some stationary points on the potential energy surface of [Si, N, N, P] system were located at the B3LYP/6-311G(d) and QCISD(t)/6-311+G(2df)(single-point) levels of theory, while the isomerization, structures, and stability of these obtained isomers were suggested. The computed results indicate that only four-membered ring isomer SiNPN(E1, 2A"), which possesses butterfly-like structure and Si-P cross bonding, is kinetically stable in all optimized isomers. Other isomers may be considered as kinetically unstable towards isomerization or dissociation because of the corresponding smaller reaction barriers. Furthermore, the present paper also proposes electronic and geometric structures, vibrational frequencies and the corresponding vibrational modes, dipole moments, and rotational constants of isomer E1. To make use of the computed results, we can clearly know that the reaction pathway via an intermediate E3 (SiNPN) is the most favorable channel producing isomer E1 from fragments SiN (2∏) and PN (1∑), which have been well characterized in space, and thus, isomer E1 can be considered as a candidate for interstellar observation. The reaction enthalpy of SiN (2∏) + pN(1∑)→E1 and the standard enthalpy of formation of isomer E1 are 215.25 and 457.99 k J/mol, respectively, at 298.15 K.

  14. Quantification of minerals and tocopherols isomers in chestnuts approach chemometrics

    Directory of Open Access Journals (Sweden)

    Nilson Evelazio de Souza

    2014-10-01

    Full Text Available The levels of the ?, ?, and (?+?-tocopherol isomers and the amounts of the minerals Se, Zn, Ca, Fe, K, Mn, Mg, and Cu were analyzed in chestnuts. High contents of Zn (>65% relative to the recommended dietary intake (RDI were found in all chestnuts except macadamia nuts (25% of the RDI. All samples had Se contents higher than the RDI: Brazil nuts > macadamia nuts, cashew nuts > pecans > almonds > pistachio nuts > hazelnuts > European nuts. A greater concentration of ?-tocopherol was found in almonds (30% of RDI. All samples, except for hazelnuts, almonds, and macadamia nuts, had (?+?- tocopherols, with the largest amount found in pistachios. Only pecan nuts and European nuts had ?-tocopherol and only in low amounts. Multivariate analysis allowed for better characterization and distinction of the chestnuts

  15. Synthesis and Applications of Hajos-Parrish Ketone Isomers.

    Science.gov (United States)

    Eagan, James M; Hori, Masahiro; Wu, Jianbin; Kanyiva, Kyalo Stephen; Snyder, Scott A

    2015-06-26

    Numerous natural products possess ring systems and functionality for which Hajos-Parrish ketone isomers with a transposed methyl group (termed "iso-Hajos-Parrish ketones") would be of value. However, such building blocks have not been exploited to the same degree as the more typical Hajos-Parrish hydrindane. An efficient three-step synthesis of such materials was fueled by a simple method for the rapid preparation of highly functionalized cyclopentenones, several of which are new chemical entities that would be challenging to access through other approaches. Furthermore, one iso-Hajos-Parrish ketone was converted into two distinct natural product analogues and one natural product. As one indication of the value of these new building blocks, that latter target was obtained in 10 steps, having previously been accessed in 18 steps using the Hajos-Parrish ketone. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Electronic Single Molecule Identification of Carbohydrate Isomers by Recognition Tunneling

    CERN Document Server

    Im, JongOne; Liu, Hao; Zhao, Yanan; Sen, Suman; Biswas, Sudipta; Ashcroft, Brian; Borges, Chad; Wang, Xu; Lindsay, Stuart; Zhang, Peiming

    2016-01-01

    Glycans play a central role as mediators in most biological processes, but their structures are complicated by isomerism. Epimers and anomers, regioisomers, and branched sequences contribute to a structural variability that dwarfs those of nucleic acids and proteins, challenging even the most sophisticated analytical tools, such as NMR and mass spectrometry. Here, we introduce an electron tunneling technique that is label-free and can identify carbohydrates at the single-molecule level, offering significant benefits over existing technology. It is capable of analyzing sub-picomole quantities of sample, counting the number of individual molecules in each subset in a population of coexisting isomers, and is quantitative over more than four orders of magnitude of concentration. It resolves epimers not well separated by ion-mobility and can be implemented on a silicon chip. It also provides a readout mechanism for direct single-molecule sequencing of linear oligosaccharides.

  17. Separation of C6-Olefin Isomers in Reactive Extractants

    Institute of Scientific and Technical Information of China (English)

    SONG Fengxia; YU Yanmei; CHEN Jian

    2008-01-01

    Chemical complexation,in which certain metal ions (especially Ag+ and Cu+) reversibly and selectively complex olefin isomers,was used to separate 1-hexene from a mixture of intemal hexenes as an attractive alternative to traditional distillation.Several potential reactive extractants were investigated for their selectivity of both 1-hexene to 2-hexene and 1-hexene to 3-hexene.With 3 mol/L AgNO3-N-methyl-pyrrolidone (NMP) solution as extractant,the selectivity of 1-hexene to 3-hexane was increased to about 2.0 and the selectivity of 1-hexene to 2-hexene reached 1.5.Both the raffinate phase and the extracted phase were analyzed using a gas chromatograph equipped with a flame ionization detector and a 50-m capillary column.The experimental results show that the silver nitrate NMP solution has the better selectivity than other reactive extractions.

  18. Energetics of cyclohexane isomers: a density-functional study

    CERN Document Server

    Lee, C Y

    1999-01-01

    The binding energies and the geometric structures of conformational isomers of cyclohexane (C sub 6 H sub 1 sub 2) are determined from the density-functional theory combined with ultrasoft pseudopotentials and gradient-corrected nonlocal exchange-correlation functionals. The ground-state chair conformation is found to have a binding energy of 99.457 eV, and the metastable twist-boat conformation has 99.161 eV. The chair conformation converts to another conformation via a half-chair conformation with an energy barrier of 0.507 eV whereas the twist-boat conformation converts to another twist-boat conformation via a boat conformation with a much smaller energy barrier of 0.015 eV.

  19. Electronic Structure and Stability of C20 Isomers

    Institute of Scientific and Technical Information of China (English)

    曹则贤

    2001-01-01

    The electronic structure of the C20 cluster in monocyclic ring, bowl and fullerene isomers has been calculated using the tight-binding scheme developed by Harrison, starting in particular from the sp2.803-hybrids for the fullerene structure. The study of energetics predicts the fullerene to be the ground state with the bowl and ring lying over 1.32 and 3.35 eV higher in energy. The total energies will be lowered by Peierls or Jahn-Teller distortion, but the energetic ordering remains unchanged. It is also shown that the range of valence electron, the level difference between the highest occupied molecular orbital and the lowest unoccupied molecular orbital as well as the σ - π gap, which are less sensitive to the exact geometry, vary in the ring, bowl and fullerene sequence.

  20. Communication: "Position" does matter: The photofragmentation of the nitroimidazole isomers

    Science.gov (United States)

    Bolognesi, P.; Casavola, A. R.; Cartoni, A.; Richter, R.; Markus, P.; Borocci, S.; Chiarinelli, J.; Tošić, S.; Sa'adeh, H.; Masič, M.; Marinković, B. P.; Prince, K. C.; Avaldi, L.

    2016-11-01

    A combined experimental and theoretical approach has been used to disentangle the fundamental mechanisms of the fragmentation of the three isomers of nitroimidazole induced by vacuum ultra-violet (VUV) radiation, namely, 4-, 5-, and 2-nitroimidazole. The results of mass spectrometry as well as photoelectron-photoion coincidence spectroscopy display striking differences in the radiation-induced decomposition of the different nitroimidazole radical cations. Based on density functional theory (DFT) calculations, a model is proposed which fully explains such differences, and reveals the subtle fragmentation mechanisms leading to the release of neutral species like NO, CO, and HCN. Such species have a profound impact in biological media and may play a fundamental role in radiosensitising mechanisms during radiotherapy.

  1. Metabolic engineering of Saccharomyces cerevisiae for production of butanol isomers.

    Science.gov (United States)

    Generoso, Wesley Cardoso; Schadeweg, Virginia; Oreb, Mislav; Boles, Eckhard

    2015-06-01

    Saccharomyces cerevisiae has decisive advantages in industrial processes due to its tolerance to alcohols and fermentation conditions. Butanol isomers are considered as suitable fuel substitutes and valuable biomass-derived chemical building blocks. Whereas high production was achieved with bacterial systems, metabolic engineering of yeast for butanol production is in the beginning. For isobutanol synthesis, combination of valine biosynthesis and degradation, and complete pathway re-localisation into cytosol or mitochondria gave promising results. However, competing pathways, co-factor imbalances and FeS cluster assembly are still major issues. 1-Butanol production via the Clostridium pathway seems to be limited by cytosolic acetyl-CoA, its central precursor. Endogenous 1-butanol pathways have been discovered via threonine or glycine catabolism. 2-Butanol production was established but was limited by B12-dependence.

  2. Submolecular imaging of chloronitrobenzene isomers on Cu(111)

    Science.gov (United States)

    Niemi, Eeva; Simic-Milosevic, Violeta; Morgenstern, Karina; Korventausta, Antti; Paavilainen, Sami; Nieminen, Jouko

    2006-11-01

    We compare computer simulations to experimental scanning tunneling microscopy (STM) images of chloronitrobenzene molecules on a Cu(111) surface. The experiments show that adsorption induced isomerization of the molecules takes place on the surface. Furthermore, not only the submolecular features can be seen in the STM images, but different isomers can also be recognized. The Todorov-Pendry approach to tunneling produces simulated STM images which are in good accordance with the experiments. Alongside with STM simulations in a tight-binding basis, ab initio calculations are performed in order to analyze the symmetry of relevant molecular orbitals and to consider the nature of tunneling channels. Our calculations show that while the orbitals delocalized to the phenyl ring create a relatively transparent tunneling channel, they also almost isolate the orbitals of the substitute groups at energies which are relevant in STM experiments. These features of the electronic structure are the key ingredients of the accurate submolecular observations.

  3. Enantiomers of a nonylphenol isomer: absolute configurations and estrogenic potencies.

    Science.gov (United States)

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

    2009-02-01

    Enantiomers of 4-(1,1,2-trimethylhexyl)phenol, a chiral isomer of the endocrine disrupting chemical nonylphenol, have been resolved and isolated by preparative chiral HPLC. The absolute configurations of the enantiomers were then determined by an X-ray crystallographic study of the (-)-camphanoyl derivative of the first eluted enantiomer NP(35)E1. The first enantiomer (NP(35)E1) and the second enantiomer (NP(35)E2) eluted were found to have the S and R absolute configurations, respectively. The estrogenic potencies of the S and R enantiomers were tested by the E-screen assay. A slight difference was observed in the relative proliferative effect between the S enantiomer and R enantiomer in the E-screen assay.

  4. Structures and stability of isomers of [C,N,N,P] system

    Institute of Scientific and Technical Information of China (English)

    KAN Wei; ZHONG Hua; YU Haitao; FU Honggang; SUN Jiazhong

    2005-01-01

    Nine isomers, twenty transition states, and some relative dissociation fragments of [C,N,N,P] system were located at the B3LYP/6-311G(d) and QCISD(t)/6-311+G(2df) (single-point) levels of theory, and the isomerization, structures, and stability of these obtained isomers were suggested. The results indicate that four nonlinear chainlike isomers NCNP, NCPN, CNPN, and CNNP with 2A′ electronic state are kinetically stable. Other isomers are kinetically unstable towards isomerization or dissociation because of the corresponding smaller reaction barriers. Furthermore, calculated vibrational frequencies, rotational constants, dipole moments, the first adiabatic ionization energies, and adiabatic electron affinities of the four isomers may provide some theoretical information that is helpful for identifying their existence in future laboratory and interstellar investigations. The results are also compared with [Si,N,N,P] system.

  5. Lipid and Glycolipid Isomer Analyses Using Ultra-High Resolution Ion Mobility Spectrometry Separations

    Energy Technology Data Exchange (ETDEWEB)

    Wojcik, Roza; Webb, Ian; Deng, Liulin; Garimella, Sandilya; Prost, Spencer; Ibrahim, Yehia; Baker, Erin; Smith, Richard

    2017-01-01

    Understanding the biological mechanisms related to lipids and glycolipids is challenging due to the vast number of possible isomers. Mass spectrometry (MS) measurements are currently the dominant approach for studying and providing detailed information on lipid and glycolipid structures. However, difficulties in distinguishing many structural isomers (e.g. distinct acyl chain positions, double bond locations, as well as glycan isomers) inhibit the understanding of their biological roles. Here we utilized ultra-high resolution ion mobility spectrometry (IMS) separations based upon the use of traveling waves in a serpentine long path length multi-pass Structures for Lossless Manipulations (SLIM) to enhance isomer resolution. The multi-pass arrangement allowed separations ranging from ~16 m (1 pass) to ~470 m (32 passes) to be investigated for the distinction of lipids and glycolipids with extremely small structural differences. These ultra-high resolution SLIM IMS-MS analyses provide a foundation for exploring and better understanding isomer specific biological and disease processes.

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

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Suman; Singh, Partapbir [Department of Microbiology, Guru Nanak Dev University, Amritsar 143005, Punjab (India); Raj, Mayil [MTCC, IMTECH, Sector 39-A, Chandigarh 160036 (India); Chadha, Bhupinder Singh [Department of Microbiology, Guru Nanak Dev University, Amritsar 143005, Punjab (India); Saini, Harvinder Singh, E-mail: sainihs@yahoo.com [Department of Microbiology, Guru Nanak Dev University, Amritsar 143005, Punjab (India)

    2009-11-15

    The different isomers of technical-grade hexachlorocyclohexane (t-HCH) including the insecticidal {gamma}-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, {beta}-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.

  7. 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.

  8. Temperature Effects on the Dissociative Electron Attachment to Dichlorobenzene Isomers

    Science.gov (United States)

    Mahmoodi-Darian, M.; Mauracher, A.; Aleem, A.; Denifl, S.; Rittenschober, B.; Bacher, A.; Probst, M.; Märk, T. D.; Scheier, P.

    2009-10-01

    Dissociative electron attachment to all three isomers of dichlorobenzene has been investigated in the electron energy range from 0 to 2 eV and in the gas temperature range from 391 to 696 K using a crossed electron-molecular beam apparatus with a new temperature-regulated effusive molecular beam source. In the case of the dissociative electron attachment channel Cl-/1,2-dichlorobenzene and Cl-/1,4-dichlorobenzene, strong enhancement of the negative ion production with the gas temperature at low electron energies has been observed. The low-energy peak increases dramatically when the gas temperature is raised from 391 to 696 K. Activation energies for dissociative electron attachment of (482 ± 20) meV for 1,2-dichlorobenzene and (59 ± 20) meV for 1,4-dichlorobenzene have been determined. For the resonance at (0.49 ± 0.03) eV in 1,2-dichlorobenzene and (0.32 ± 0.03) eV in 1,4-dichlorobenzene, no dependence of the cross sections on the gas temperature has been observed. In the case of the dissociative electron attachment to Cl-/1,3-dichlorobenzene, the cross section does not depend on the temperature in the electron energy range from 0 to 2 eV. Quantum chemical calculations of the reaction energies and of the potential energy curves involved in the dissociation of Cl- have been performed, together with an analysis of the thermo dynamical accessibility of the relevant vibrational modes. Possible reasons for the different temperature dependences of the isomers are discussed.

  9. 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.

  10. Measuring the Th-229 nuclear isomer transition with U-233 doped crystals

    CERN Document Server

    Stellmer, Simon; Kazakov, Georgy; Sterba, Johannes; Schumm, Thorsten

    2015-01-01

    We propose a simple approach to measure the energy of the few-eV isomeric state in Th-229. To this end, U-229 nuclei are doped into VUV-transparent crystals, where they undergo alpha decay into Th-229, and, with a probability of 2%, populate the isomeric state. These Th-229m nuclei may decay into the nuclear ground state under emission of the sought-after VUV gamma, whose wavelength can be determined with a spectrometer. Based on measurements of the optical transmission of U:CaF2 crystals in the VUV range, we expect a signal at least 2 orders of magnitude larger compared to current schemes using surface-implantation of recoil nuclei. The signal background is dominated by Cherenkov radiation induced by beta decays of the thorium decay chain. We estimate that, even if the isomer undergoes radiative de-excitation with a probability of only 0.1%, the VUV gamma can be detected within a reasonable measurement time.

  11. Analysis and deconvolution of dimethylnaphthalene isomers using gas chromatography vacuum ultraviolet spectroscopy and theoretical computations.

    Science.gov (United States)

    Schenk, Jamie; Mao, James X; Smuts, Jonathan; Walsh, Phillip; Kroll, Peter; Schug, Kevin A

    2016-11-16

    An issue with most gas chromatographic detectors is their inability to deconvolve coeluting isomers. Dimethylnaphthalenes are a class of compounds that can be particularly difficult to speciate by gas chromatography - mass spectrometry analysis, because of their significant coelution and similar mass spectra. As an alternative, a vacuum ultraviolet spectroscopic detector paired with gas chromatography was used to study the systematic deconvolution of mixtures of coeluting isomers of dimethylnaphthalenes. Various ratio combinations of 75:25; 50:50; 25:75; 20:80; 10:90; 5:95; and 1:99 were prepared to test the accuracy, precision, and sensitivity of the detector for distinguishing overlapping isomers that had distinct, but very similar absorption spectra. It was found that, under reasonable injection conditions, all of the pairwise overlapping isomers tested could be deconvoluted up to nearly two orders of magnitude (up to 99:1) in relative abundance. These experimental deconvolution values were in agreement with theoretical covariance calculations performed for two of the dimethylnaphthalene isomers. Covariance calculations estimated high picogram detection limits for a minor isomer coeluting with low to mid-nanogram quantity of a more abundant isomer. Further characterization of the analytes was performed using density functional theory computations to compare theory with experimental measurements. Additionally, gas chromatography - vacuum ultraviolet spectroscopy was shown to be able to speciate dimethylnaphthalenes in jet and diesel fuel samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Physical chemistry and membrane properties of two phosphatidylinositol bisphosphate isomers.

    Science.gov (United States)

    Slochower, David R; Wang, Yu-Hsiu; Radhakrishnan, Ravi; Janmey, Paul A

    2015-05-21

    The most highly charged phospholipids, polyphosphoinositides, are often involved in signaling pathways that originate at cell-cell and cell-matrix contacts, and different isomers of polyphosphoinositides have distinct biological functions that cannot be explained by separate highly specific protein ligand binding sites [Lemmon, Nat. Rev. Mol. Cell Biol., 2008, 9, 99-111]. PtdIns(3,5)P2 is a low abundance phosphoinositide localized to cytoplasmic-facing membrane surfaces, with relatively few known ligands, yet PtdIns(3,5)P2 plays a key role in controlling membrane trafficking events and cellular stress responses that cannot be duplicated by other phosphoinositides [Dove et al., Nature, 1997, 390, 187-192; Michell, FEBS J., 2013, 280, 6281-6294]. Here we show that PtdIns(3,5)P2 is structurally distinct from PtdIns(4,5)P2 and other more common phospholipids, with unique physical chemistry. Using multiscale molecular dynamics techniques on the quantum level, single molecule, and in bilayer settings, we found that the negative charge of PtdIns(3,5)P2 is spread over a larger area, compared to PtdIns(4,5)P2, leading to a decreased ability to bind divalent ions. Additionally, our results match well with experimental data characterizing the cluster forming potential of these isomers in the presence of Ca(2+) [Wang et al., J. Am. Chem. Soc., 2012, 134, 3387-3395; van den Bogaart et al., Nature, 2011, 479, 552-555]. Our results demonstrate that the different cellular roles of PtdIns(4,5)P2 and PtdIns(3,5)P2in vivo are not simply determined by their localization by enzymes that produce or degrade them, but also by their molecular size, ability to chelate ions, and the partial dehydration of those ions, which might affect the ability of PtdIns(3,5)P2 and PtdIns(4,5)P2 to form phosphoinositide-rich clusters in vitro and in vivo.

  13. Isolation and spectral characterization of thermally generated multi-Z-isomers of lycopene and the theoretically preferred pathway to di-Z-isomers.

    Science.gov (United States)

    Honda, Masaki; Kudo, Tatsuya; Kuwa, Takahiro; Higashiura, Takuma; Fukaya, Tetsuya; Inoue, Yoshinori; Kitamura, Chitoshi; Takehara, Munenori

    2017-02-01

    Lycopene has a large number of geometric isomers caused by E/Z isomerization at arbitrary sites within the 11 conjugated double bonds, offering varying characteristics related to features such as antioxidant capacity and bioavailability. However, the geometric structures of only a few lycopene Z-isomers have been thoroughly identified from natural sources. In this study, seven multi-Z-isomers of lycopene, (9Z,13'Z)-, (5Z,13Z,9'Z)-, (9Z,9'Z)-, (5Z,13'Z)-, (5Z,9'Z)-, (5Z,9Z,5'Z)-, and (5Z,9Z)-lycopene, were obtained from tomato samples by thermal isomerization, and then isolated by elaborate chromatography, and fully assigned using proton nuclear magnetic resonance. Moreover, the theoretically preferred pathway from (all-E)-lycopene to di-Z-isomers was examined with a computational approach using a Gaussian program. Fine-tuning of the HPLC separation conditions led to the discovery of novel multi-Z-isomers, and whose formation was supported by advanced theoretical calculations.

  14. Isomer Shift and Magnetic Moment of the Long-Lived 1/2^{+} Isomer in _{30}^{79}Zn_{49}: Signature of Shape Coexistence near ^{78}Ni.

    Science.gov (United States)

    Yang, X F; Wraith, C; 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

    2016-05-01

    Collinear laser spectroscopy is performed on the _{30}^{79}Zn_{49} isotope at ISOLDE-CERN. The existence of a long-lived isomer with a few hundred milliseconds half-life is confirmed, and the nuclear spins and moments of the ground and isomeric states in ^{79}Zn as well as the isomer shift are 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 μ (^{79}Zn)=-1.1866(10)μ_{N}, confirms the spin-parity 9/2^{+} with a νg_{9/2}^{-1} shell-model configuration, in excellent agreement with the prediction from large scale shell-model theories. The magnetic moment μ (^{79m}Zn)=-1.0180(12)μ_{N} supports a positive parity for the isomer, with a wave function dominated by a 2h-1p neutron excitation across the N=50 shell gap. The large isomer shift reveals an increase of the intruder isomer mean square charge radius with respect to that of the ground state, δ⟨r_{c}^{2}⟩^{79,79m}=+0.204(6)  fm^{2}, providing first evidence of shape coexistence.

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

    CERN Document Server

    Staszczak, Andrzej

    2015-01-01

    We review our theoretical knowledge of possible toroidal high-spin isomers in the light mass region in 28$\\le$$A$$\\le$52 obtained previously in cranked Skyrme-Hartree-Fock calculations. We report additional toroidal high-spin isomers in $^{56}$Ni with $I$=114$\\hbar$ and 140$\\hbar$, 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 $^{20}$Ne or $^{28}$Si as an active target in time-projection-chamber (TCP) experiments.

  16. Quantification of Triacylglycerol Positional Isomers in Rat Milk.

    Science.gov (United States)

    Watanabe, Natsuko; Nagai, Toshiharu; Mizobe, Hoyo; Yoshinaga, Kazuaki; Yoshida, Akihiko; Kitamura, Yohei; Shimizu, Takashi; Beppu, Fumiaki; Gotoh, Naohiro

    2016-12-01

    The absolute amount of triacylglycerol (TAG) positional isomers was analyzed in rat milk fat, a representative of non-ruminant milk fat, using a HPLC-UV-atmospheric pressure chemical ionization-MS/MS system equipped with an octacosyl silylation column or polymeric ODS column. TAGs consisting of two oleic acids (O) and one palmitic acid (P) were the most abundant. In particular, β-OPO, a TAG binding P at the β-position (sn-2) and two Os at the α-positions (sn-1/3), was prominent. The β-OPO content decreased over time, while a TAG consisting of two Ps and one capric acid, a medium-chain fatty acid, increased. TAGs consisting of two Ps and one docosahexaenoic acid were present in small amounts and decreased with time. These results indicated that the recombination of fatty acids in TAGs in milk fat occurs in the mother, and is thought to depend on the infant's stage of growth, in response to their nutritional needs. It was also demonstrated that medium-chain fatty acids were mainly located at the α-position (sn-3), while Ps were mainly located at the β-position (sn-2). Therefore, the combination and binding positions of fatty acids of TAG are considered very important in infant nutrition.

  17. Interstellar Isomers: The Importance of Bonding Energy Differences

    CERN Document Server

    Remijan, A J; Lovas, F J; Plusquellic, D F; Jewell, P R; Remijan, Anthony J.

    2005-01-01

    We present strong detections of methyl cyanide, vinyl cyanide, ethyl cyanide and cyanodiacetylene molecules with the Green Bank Telescope (GBT) toward the Sgr B2(N) molecular cloud. Attempts to detect the corresponding isocyanide isomers were only successful in the case of methyl isocyanide for its J(K)=1(0)-0(0) transition, which is the first interstellar report of this line. To determine the spatial distribution of methyl isocyanide, we used archival Berkeley-Illinois-Maryland Association (BIMA) array data for the J(K)=4(K)-3(K) (K=0-3) transitions but no emission was detected. From ab initio calculations, the bonding energy difference between the cyanide and isocyanide molecules is >8500 cm^-1 (>12,000 K). That we detect methyl isocyanide emission with a single antenna (Gaussian beamsize(Omega_B)=1723 arcsec^2) but not with an interferometer (Omega_B=192 arcsec^2), strongly suggests that methyl isocyanide has a widespread spatial distribution toward the Sgr B2(N) region. Thus, large-scale, non-thermal proc...

  18. Isomer spectroscopy of {sup 125,127}Cd

    Energy Technology Data Exchange (ETDEWEB)

    Naqvi, F. [Institut fuer Kernphysik, Universitaet Koeln (Germany); GSI, Helmholtzzentrum fuer Schwerionenforschung, Darmstadt (Germany); Gorska, M.; Grawe, H.; Pietri, S. [GSI, Helmholtzzentrum fuer Schwerionenforschung, Darmstadt (Germany); Caceres, L. [GSI, Helmholtzzentrum fuer Schwerionenforschung, Darmstadt (Germany); Departmento de Fisicia Teorica, Universidad Autonoma de Madrid (Spain); Jungclaus, A. [Departmento de Fisicia Teorica, Universidad Autonoma de Madrid (Spain); Pfuetzner, M. [IEP, Warsaw University, Warsaw (Poland); Regan, P.H; Podolyak, Z. [Department of Physics, University of Surrey, Guildford (United Kingdom); Rudolf, D. [Department of Physics, Lund University (Sweden)

    2010-07-01

    The results of investigations of isomeric decay in odd mass heavy Cd isotopes namely {sup 125,127}Cd are reported. To date information has been obtained on even mass heavy Cd isotopes and the systematics show evolution of single particle energies for them. The experiment was performed at GSI, Darmstadt to investigate the single particle level structure of odd mass heavy Cd isotopes. Nuclei of interest were produced in fragmentation reaction of {sup 136}Xe beam at energy 750MeV/u on a {sup 9}Be target of 4g/cm{sup 2} thickness. Selection of ions from unwanted reaction products and event by event identification was facilitated by FRagment Separator (FRS). Isomers populated in the reaction were implanted in a plastic catcher surrounded by 15 Ge cluster detectors from RISING array to detect gamma radiations. Level schemes based on the intensity balance and life time information were constructed for the first time for these nuclei. Comparison of the experimental results with shell model calculation are discussed.

  19. 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...

  20. Search for superradiant emission states in nuclear isomer crystals

    Energy Technology Data Exchange (ETDEWEB)

    Rundberg, R.S.; Wilhelmy, J.B.; Taylor, R.D.; Solem, J.C.; Fowler, M.M.; Miller, G.G.; Baldwin, G.

    1998-01-01

    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). The objective was to verify the stimulated emission of gamma rays from {sup 125m}Te, as claimed by Russian scientists. The reported cross section for stimulated emission was sufficiently large to allow gain in a single-pass gamma-ray laser. The stimulated emission of gamma rays from a nuclear isomer is expected to result in collinear photons and, therefore, should be observable as a sum peak in the gamma-ray spectrum. Skorobogatov and Dzevitskii reported an increase of an order of magnitude in the sum peak (218.56 keV) when a sample of beryllium telluride containing {sup 125m}Te was cooled from room temperature to near-liquid-helium temperatures. The authors have repeated their experiment and have observed no increase in the sum peak above accidental summing. The upper limit for the stimulated-emission cross section based on the three-standard-deviation statistical error is 6.8 x 10 {sup {minus}21} cm{sup 2}. This result is one order of magnitude lower than the cross section reported by Skorobogatov and Dzevitskii. The cross section would not allow gain in a single-pass gamma-ray laser. Their results support the position of Baldwin and Solem rather than that of Kamenov.

  1. 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.

  2. Theoretical Studies on Structures and Stabilities of C4H2+ Isomers

    Institute of Scientific and Technical Information of China (English)

    ZHAO Ying; WAN Su-qin; LIU Hui-ling; HUANG Xu-ri; SUN Chia-chung

    2013-01-01

    The structures,energies,stabilities and spectroscopies of doublet C4H2+ cations were explored at the DFT/B3LYP/6-311G(d,p),CCSD(T)/6-311+G(2df,2pd)(single-point),and G3B3 levels.Ten minimum isomers including the chainlike,three-member-ring,and four-member-ring structures are interconverted by means of 15 interconversion transition states.The potential energy surface was investigated.At the CCSD(T)/6-311+G(2df,2pd) and G3B3 levels,the global minimum isomer was found to be a linear HCCCCH.The structures of the stable isomer and its relevant transition state are further optimized at the QCISD/6-311G(d,p) level.The bonding nature and structure of isomer HCCCCH were analyzed.

  3. 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.

  4. Toroidal high-spin isomers in light nuclei with N not equal to Z

    CERN Document Server

    Staszczak, Andrzej

    2014-01-01

    The combined considerations of both the bulk liquid-drop-type behavior and the quantized aligned rotation with cranked Skyrme-Hartree-Fock approach revealed previously that even-even, N=Z, toroidal high-spin isomeric states have general occurrences for light nuclei with A between 28 and 52. We find that in this mass region there are in addition N not equal to Z toroidal high-spin isomers when the single-particle shells for neutrons and protons occur at the same cranked frequency $\\hbar \\omega$. Examples of N not equal to Z toroidal high-spin isomers, $^{36}_{16}$S$_{20}$($I$=74$\\hbar$) and $^{40}_{18}$Ar$_{22}$($I$=80,102$\\hbar$), are located and examined. The systematic properties of these N not equal to Z toroidal high-spin isomers fall into the same regular (muti-particle)-(muti-hole) patterns as other N=Z toroidal high-spin isomers.

  5. Synthesis of an isomer of dihydrocolensenone; Sintesis parcial de un isomero de la dihidrocolensenona

    Energy Technology Data Exchange (ETDEWEB)

    Fraga, B.M.; Hernandez, M.G.; Luis, J.G. [Instituto de Productos naturales y Agrobiologia CSIC, Universidad de La Laguna, Tenerife (Spain)

    1994-12-31

    Starting from the diterpene ribenone, a isomer of dihydrocolensenone has been prepared. Its structure was different of dihydrotiganone, showing that the structure previously assigned to tiganone was erroneous. 13 refs.

  6. 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 $\

  7. Structural, Electronic, and Vibrational Properties of Amino-adamantane and Rimantadine Isomers

    CERN Document Server

    Garcia, Joelson Cott; Machado, Wanda V M; Assali, Lucy V C; 10.1021/jp107496b

    2012-01-01

    We performed a first principles total energy investigation on the structural, electronic, and vibrational properties of adamantane molecules, functionalized with amine and ethanamine groups. We computed the vibrational signatures of amantadine and rimantadine isomers with the functional groups bonded to different carbon sites. By comparing our results with recent infrared and Raman spectroscopic data, we discuss the possible presence of different isomers in experimental samples.

  8. Discovery of a 7.6-hour high-spin isomer of einsteinium-256

    CERN Document Server

    Lougheed, R W; Daniels, W R; Hoffman, D C; Jackson, S V; Landrum, J H; Starner, J W; Wilhelmy, J B

    1976-01-01

    A 7.6-hour, beta-emitting isomer of /sup 256/Es has been produced via the (t, p) reaction by bombarding /sup 254g/Es with 16-MeV tritons. No evidence for an alpha branch has been found. A number of gamma rays have been observed, on the basis of which a partial decay scheme is proposed. It is concluded that the isomer has spin 7 or 8. (2 refs).

  9. Theoretical investigation of thermodynamic balance between cluster isomers and statistical model for predicting isomerization rate

    CERN Document Server

    Lin, Zheng-Zhe

    2013-01-01

    By molecular dynamics simulations and free energy calculations based on Monte Carlo method, the detailed balance between Pt cluster isomers was investigated. For clusters of n50. Then, a statistical mechanical model was built to evaluate unimolecular isomerization rate and simplify the prediction of isomer formation probability. This model is simpler than transition state theory and can be easily applied on ab initio calculations to predict the lifetime of nanostructures.

  10. The sim Operon Facilitates the Transport and Metabolism of Sucrose Isomers in Lactobacillus casei ATCC 334

    OpenAIRE

    2008-01-01

    Inspection of the genome sequence of Lactobacillus casei ATCC 334 revealed two operons that might dissimilate the five isomers of sucrose. To test this hypothesis, cells of L. casei ATCC 334 were grown in a defined medium supplemented with various sugars, including each of the five isomeric disaccharides. Extracts prepared from cells grown on the sucrose isomers contained high levels of two polypeptides with Mrs of ~50,000 and ~17,500. Neither protein was present in cells grown on glucose, ma...

  11. On the Relative Stability of Cumulenone and Aldehyde Isomers: when we HEAT345(Q) Things UP

    Science.gov (United States)

    Lee, Kelvin; McCarthy, Michael C.; Stanton, John F.

    2017-06-01

    Isomers of H_2C_{2n+1}O are examples of complex organic molecules that are either known or proposed to exist in the interstellar medium. For the smallest of these chains (H_2C_3O) only two of three isomers are observed in space: propynal (HC(O)CCH) and cyclopropenone (c-C_3H_2O), while evidence for the remaining isomer propadienone (H_2C_3O) is currently lacking. Potentially, this behaviour may be rationalised by a thermodynamic argument: several studies have provided quantum chemical calculations in an effort to determine the relative thermodynamic stability between these three isomers. An early study by Radom, at the SCF/6-31G** level ranked HC(O)CCH as the thermodynamic minimum, followed by H_2C_3O, and c-C_3H_2O. The most recent determination by Karton and Talbi, using W2-F12 theory, places H_2C_3O as the lowest energy isomer; 2.5 kJ mol^{-1} lower than the HC(O)CCH form. In an attempt to resolve this long-standing ambiguity, we were motivated to provide high level calculations based on the HEAT protocol. In this talk, we will discuss the relative stability of H_2C_3O and H_2C_5O isomers, along with their sulfur analogues, as revealed by HEAT345(Q) theory.

  12. Roles of the tyrosine isomers meta-tyrosine and ortho-tyrosine in oxidative stress.

    Science.gov (United States)

    Ipson, Brett R; Fisher, Alfred L

    2016-05-01

    The damage to cellular components by reactive oxygen species, termed oxidative stress, both increases with age and likely contributes to age-related diseases including Alzheimer's disease, atherosclerosis, diabetes, and cataract formation. In the setting of oxidative stress, hydroxyl radicals can oxidize the benzyl ring of the amino acid phenylalanine, which then produces the abnormal tyrosine isomers meta-tyrosine or ortho-tyrosine. While elevations in m-tyrosine and o-tyrosine concentrations have been used as a biological marker of oxidative stress, there is emerging evidence from bacterial, plant, and mammalian studies demonstrating that these isomers, particularly m-tyrosine, directly produce adverse effects to cells and tissues. These new findings suggest that the abnormal tyrosine isomers could in fact represent mediators of the effects of oxidative stress. Consequently the accumulation of m- and o-tyrosine may disrupt cellular homeostasis and contribute to disease pathogenesis, and as result, effective defenses against oxidative stress can encompass not only the elimination of reactive oxygen species but also the metabolism and ultimately the removal of the abnormal tyrosine isomers from the cellular amino acid pool. Future research in this area is needed to clarify the biologic mechanisms by which the tyrosine isomers damage cells and disrupt the function of tissues and organs and to identify the metabolic pathways involved in removing the accumulated isomers after exposure to oxidative stress.

  13. Estrogen equivalent concentration of individual isomer-specific 4-nonylphenol in Ariake sea water, Japan.

    Science.gov (United States)

    Kim, Yun-Seok; Katase, Takao; Horii, Yuichi; Yamashita, Nobuyoshi; Makino, Mitsuko; Uchiyama, Taketo; Fujimoto, Yasuo; Inoue, Tadashi

    2005-01-01

    Concentrations of 4-nonylphenol (NP) were determined by isomer-specific quantification of individual NP isomers based on relative response factor (RRF) quantification with GC-MS in combination with steam distillation extraction. Concentrations of NP in the Ariake Sea decreased with distance from the river mouth (St.A; 49 ng NP/l) to offshore areas (St.C; 11 ng NP/l). Even the least concentration in water from St.C in Ariake Sea was sufficient to have adverse effects on barnacles. The isomers, NP1-NP14 were separated by GC-PFC and identified structurally with NMR. The isomers varied in estrogenic activity with NP7 exhibiting the greatest estrogenic activity with a potency that was approximately 1.9 x 10(-3) that of 17beta-estradiol (E2) in recombinant yeast screen system. The coefficient of variation (CV) of NP isomer's concentrations among three samples at St.A, B and C were 4-75%. This suggests that NP isomers might be independently degraded in aquatic environmental samples. The predicted estrogenic activity of measured concentrations of NP in Ariake Sea was 2.7-3.0-fold greater than the measured estrogen agonist activity.

  14. Surfactant mediated enhanced biodegradation of hexachlorocyclohexane (HCH) isomers by Sphingomonas sp. NM05.

    Science.gov (United States)

    Manickam, Natesan; Bajaj, Abhay; Saini, Harvinder S; Shanker, Rishi

    2012-09-01

    Environmental biodegradation of several chlorinated pesticides is limited by their low solubility and sorption to soil surfaces. To mitigate this problem we quantified the effect of three biosurfactant viz., rhamnolipid, sophorolipid and trehalose-containing lipid on the dissolution, bioavailability, and biodegradation of HCH-isomers in liquid culture and in contaminated soil. The effect of biosurfactants was evaluated through the critical micelle concentration (CMC) value as determined for each isomer. The surfactant increased the solubilization of HCH isomers by 3-9 folds with rhamnolipid and sophorolipid being more effective and showing maximum solubilization of HCH isomers at 40 μg/mL, compared to trehalose-containing lipid showing peak solubilization at 60 μg/mL. The degradation of HCH isomers by Sphingomonas sp. NM05 in surfactant-amended liquid mineral salts medium showed 30% enhancement in 2 days as compared to degradation in 10 days in the absence of surfactant. HCH-spiked soil slurry incubated with surfactant also showed around 30-50% enhanced degradation of HCH which was comparable to the corresponding batch culture experiments. Among the three surfactants, sophorolipid offered highest solubilization and enhanced degradation of HCH isomers both in liquid medium and soil culture. The results of this study suggest the effectiveness of surfactants in improving HCH degradation by increased bioaccessibility.

  15. 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

  16. Vibronic Spectroscopy of a Structural Isomer of Quinoline: -

    Science.gov (United States)

    Mehta-Hurt, Deepali N.; Korn, Joseph A.; Zwier, Timothy S.

    2013-06-01

    This talk will present results of a gas phase, jet-cooled vibronic spectroscopy study of (Z)-phenylvinylnitrile ((Z)-C_6H_5-CH=CH-C=N, (Z)-PVN). With a substituent locked into a cis conformation with respect to the aromatic ring, (Z)-PVN is postulated to be a molecule with an ideal functionality to isomerize to quinoline upon photoexcitation. As such, (Z)-PVN is particularly relevant to Titan's nitrile-containing atmosphere, where much of the chemistry is photochemically driven. As a first step towards such photochemical studies, a fluorescence excitation spectrum of a mixture of (E)- and (Z)-PVN was collected spanning the range 33,300-35,580 cm^{-1} (300.0-281.0 nm). Previous investigations in the Zwier group pertaining to the vibronic spectroscopy of (E)-PVN allowed for the identification of peaks in the (E)- and (Z)-PVN composite spectrum that were solely due to (Z)-PVN, and the S_0-S_1 origin of (Z)-PVN was identified as a dominant band that occurs at 33,706 cm^{-1}. For additional confirmation, ultraviolet depletion spectroscopy (UVD) was used to obtain an isomer specific spectrum of (Z)-PVN as well as search for non-radiative transitions. Dispersed fluorescence spectra that characterize the vibronic activity have also been acquired. A comparison between the vibronic spectroscopy of (Z)-PVN with both (E)-PVN and (Z)-phenylvinylacetylene ((Z)-PVA), the hydrocarbon analog of (Z)-PVN, will be made in this talk.

  17. 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.

  18. Chiral recognition of pinacidil and its 3-pyridyl isomer by canine cardiac and smooth muscle: Antagonism by sulfonylureas

    Energy Technology Data Exchange (ETDEWEB)

    Steinberg, M.I.; Wiest, S.A.; Zimmerman, K.M.; Ertel, P.J.; Bemis, K.G.; Robertson, D.W. (Eli Lilly and Company, Indianapolis, IN (USA))

    1991-01-01

    Pinacidil, a potassium channel opener (PCO), relaxes vascular smooth muscle by increasing potassium ion membrane conductance, thereby causing membrane hyperpolarization. PCOs also act on cardiac muscle to decrease action potential duration (APD) selectively. To examine the enantiomeric selectivity of pinacidil, the stereoisomers of pinacidil (a 4-pyridylcyanoguanidine) and its 3-pyridyl isomer (LY222675) were synthesized and studied in canine Purkinje fibers and cephalic veins. The (-)-enantiomers of both pinacidil and LY222675 were more potent in relaxing phenylephrine-contracted cephalic veins and decreasing APD than were their corresponding (+)-enantiomers. The EC50 values for (-)-pinacidil and (-)-LY222675 in relaxing cephalic veins were 0.44 and 0.09 microM, respectively. In decreasing APD, the EC50 values were 3.2 microM for (-)-pinacidil and 0.43 microM for (-)-LY222675. The eudismic ratio was greater for the 3-pyridyl isomer than for pinacidil in both cardiac (71 vs. 22) and vascular (53 vs. 17) tissues. (-)-LY222675 and (-)-pinacidil (0.1-30 microM) also increased 86Rb efflux from cephalic veins to a greater extent than did their respective optical antipodes. The antidiabetic sulfonylurea, glyburide (1-30 microM), shifted the vascular concentration-response curve of (-)-pinacidil to the right by a similar extent at each inhibitor concentration. Glipizide also antagonized the response to (-)-pinacidil, but was about 1/10 as potent with a maximal shift occurring at 10 and 30 microM. Glyburide antagonized the vascular relaxant effects of 0.3 microM (-)-LY222675 (EC50, 2.3 microM) and reversed the decrease in APD caused by 3 microM (-)-LY222675 (EC50, 1.9 microM). Nitroprusside did not alter 86Rb efflux, and vascular relaxation induced by sodium nitroprusside was unaffected by sulfonylureas.

  19. Pharmacological profile of barnidipine: a single optical isomer dihydropyridine calcium antagonist.

    Science.gov (United States)

    van Zwieten, P A

    1998-01-01

    This article reviews the pharmacological profile of the dihydropyridine calcium antagonist (CaA) barnidipine [(+)-(3'S,4S)-3-(1'-benzyl-3'-pyrrolidinyl)-methyl-2,6-dimethyl-4-(m-nit rophenyl)-1,4dihydropyridine-3,5-dicarboxylate x HCl]. The characteristics and potential advantages of its pharmacological selectivity are also outlined. Barnidipine is an L-type CaA with high affinity for [3H]nitrendipine binding sites (Ki = 0.21 nmol/l). Its pharmacological profile has been studied in a variety of isolated tissues and animal models, such as isolated coronary arteries (pig, dog, rat), aorta (guinea pig) and in hypertensive rats (spontaneously hypertensive, renal hypertensive, desoxycorticosterone acetate [DOCA]-salt). Barnidipine may be characterized as a highly potent drug with vasoselectivity and, accordingly, a lack of negative inotropic activity. The onset of its action in vivo is slow, and it does not elicit reflex tachycardia. Its long duration of action, due to its lipophilicity, means that satisfactory control of elevated blood pressure can be obtained with once-daily dosing. Another interesting feature of barnidipine is its stereoselectivity. As the barnidipine molecule contains two chiral centres, it can have four possible enantiomers. The active component in the capsules used clinically consists of the S,S form, which is the most potent and longest acting of the four enantiomers.

  20. On the intrinsic optical absorptions by tetrathiafulvalene radical cations and isomers

    DEFF Research Database (Denmark)

    Kirketerp, Maj-Britt Suhr; Leal, Leonardo Andrés Espinosa; Varsano, Daniele;

    2011-01-01

    Gas-phase action spectroscopy shows unambiguously that the low-energy absorptions by tetramethylthiotetrathiafulvalene and tetrathianaphthalene cations in solution phase are due to monomers and not π-dimers....

  1. Optical Spectroscopy of an Atomic Nucleus: Progress toward Direct Observation of the 229Th Isomer Transition

    Science.gov (United States)

    2011-09-28

    produce sufficiently high 229mTh-229gTh luminescence rates under excitation with a VUV source such as the ALS. Our preliminary studies find LiCAF to be an...hour per response, including the time for reviewing instructions, ~earchi ng existing data sources , gathering and maintaining the data needed, and...229mTh transition energy can be identified to within 0.1 nm by luminescence excitation and luminescence spectroscopy using the Advanced Light Source

  2. Maternal dietary Alpine butter intake affects human milk: fatty acids and conjugated linoleic acid isomers.

    Science.gov (United States)

    Bertschi, Isabelle; Collomb, Marius; Rist, Lukas; Eberhard, Pius; Sieber, Robert; Bütikofer, Ulrich; Wechsler, Daniel; Folkers, Gerd; von Mandach, Ursula

    2005-06-01

    Consumption of CLA by lactating women affects the composition of their milk, but the pattern of the different CLA isomers is still unknown. We determined the effects of short maternal supplementation with CLA-rich Alpine butter on the occurrence of FA and CLA isomers in human milk. In an open randomized controlled study with a two-period cross-over design, milk FA and CLA isomer concentrations were measured on postpartum days > or = 20 in two parallel groups of lactating women before, during, and after consumption of defined quantities of Alpine butter or margarine with comparable fat content (10 d of butter followed by 10 d of margarine for one group, and vice versa in the other). In the 16 women who completed the study (8/group), Alpine butter supplementation increased the C16 and C18 FA, the sum of saturated FA, the 18:1 trans FA, and the trans FA with CLA. The CLA isomer 18:2 c9,t11 increased by 49.7%. Significant increases were also found for the isomers t9,t11, t7,c9, t11,c13, and t8,c10 18:2. The remaining nine of the total 14 detectable isomers showed no changes, and concentrations were <5 mg/100 g fat. A breastfeeding mother can therefore modulate the FA/CLA supply of her child by consuming Alpine butter. Further studies will show whether human milk containing this FA and CLA isomer pattern acts as a functional food for newborns.

  3. Recent Advances in IR and UV/VIS Spectroscopic Characterization of the C76 and C84 Isomers of D2 Symmetry

    Directory of Open Access Journals (Sweden)

    Tamara Jovanović

    2014-01-01

    Full Text Available The stable isomers of the higher fullerenes C76 and C84 with D2 symmetry as well as the basic fullerenes C60 and C70 were isolated from carbon soot and characterized by the new and advanced methods, techniques, and processes. The validity of several semiempirical, ab initio, and DFT theoretical calculations in predicting the general pattern of IR absorption and the vibrational frequencies, as well as the molecular electronic structure of the C76 and C84 isomers of D2 symmetry, is confirmed, based on recent experimental results. An excellent correlation was found between the previously reported theoretical data and the recently obtained experimental results for these molecules over the relevant spectral range for the identification of fullerenes. These results indicate that there are no errors in the calculations in the significant spectral regions, the assumptions that were based on previous comparisons with partial experimental results. Isolated fullerenes are important for their applications in electronic and optical devices, solar cells, optical limiting, sensors, polymers, nanophotonic materials, diagnostic and therapeutic agents, health and environment protection, and so forth.

  4. Solvation effects on brain uptakes of isomers of 99mTc brain imaging agents

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Analysis of electrostatic hydration free energies of the isomers of the 99mTc-BAT and 99mTc-DADT complexes is carried out using the computer simulation technique. The results show that not only a correlation exists between the logarithm of the brain uptake and the electrostatic hydration free energy for the isomers of 99mTc-brain radiopharmaceuticals, but also a linear relationship exists between the logarithm of the ratio of the brain uptake of the syn isomer to that of the anti one and the difference between the electrostatic hydration free energy of the syn-isomer and that of the anti one. Furthermore, the investigation on the important factors influencing the brain uptakes of 99mTc-radiopharmaceuticals and the reasons of the different biodistribution of the isomers of the 99mTc-complexes is explored at the molecular level. The results may provide a reference for the rational drug design of brain imaging agents.

  5. Experimental and theoretical cross sections for positron scattering from the pentane isomers

    Science.gov (United States)

    Chiari, L.; Zecca, A.; Blanco, F.; García, G.; Brunger, M. J.

    2016-02-01

    Isomerism is ubiquitous in chemistry, physics, and biology. In atomic and molecular physics, in particular, isomer effects are well known in electron-impact phenomena; however, very little is known for positron collisions. Here we report on a set of experimental and theoretical cross sections for low-energy positron scattering from the three structural isomers of pentane: normal-pentane, isopentane, and neopentane. Total cross sections for positron scattering from normal-pentane and isopentane were measured at the University of Trento at incident energies between 0.1 and 50 eV. Calculations of the total cross sections, integral cross sections for elastic scattering, positronium formation, and electronic excitations plus direct ionization, as well as elastic differential cross sections were computed for all three isomers between 1 and 1000 eV using the independent atom model with screening corrected additivity rule. No definitive evidence of a significant isomer effect in positron scattering from the pentane isomers appears to be present.

  6. 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.

  7. Surface behavior of amphiphiles in aqueous solution: a comparison between different pentanol isomers.

    Science.gov (United States)

    Walz, M-M; Caleman, C; Werner, J; Ekholm, V; Lundberg, D; Prisle, N L; Öhrwall, G; Björneholm, O

    2015-06-07

    Position isomerism is ubiquitous in atmospheric oxidation reactions. Therefore, we have compared surface-active oxygenated amphiphilic isomers (1- and 3-pentanol) at the aqueous surface with surface- and chemically sensitive X-ray photoelectron spectroscopy (XPS), which reveals information about the surface structure on a molecular level. The experimental data are complemented with molecular dynamics (MD) simulations. A concentration-dependent orientation and solvation of the amphiphiles at the aqueous surface is observed. At bulk concentrations as low as around 100 mM, a monolayer starts to form for both isomers, with the hydroxyl groups pointing towards the bulk water and the alkyl chains pointing towards the vacuum. The monolayer (ML) packing density of 3-pentanol is approx. 70% of the one observed for 1-pentanol, with a molar surface concentration that is approx. 90 times higher than the bulk concentration for both molecules. The molecular area at ML coverage (≈100 mM) was calculated to be around 32 ± 2 Å(2) per molecule for 1-pentanol and around 46 ± 2 Å(2) per molecule for 3-pentanol, which results in a higher surface concentration (molecules per cm(2)) for the linear isomer. In general we conclude therefore that isomers - with comparable surface activities - that have smaller molecular areas will be more abundant at the interface in comparison to isomers with larger molecular areas, which might be of crucial importance for the understanding of key properties of aerosols, such as evaporation and uptake capabilities as well as their reactivity.

  8. Optics/Optical Diagnostics Laboratory

    Data.gov (United States)

    Federal Laboratory Consortium — The Optics/Optical Diagnostics Laboratory supports graduate instruction in optics, optical and laser diagnostics and electro-optics. The optics laboratory provides...

  9. Discrimination of 1,1-difluoroethylene nuclear spin isomers in the presence of non-adiabatic coupling terms

    Science.gov (United States)

    Gómez, Sandra; Oppel, Markus; González, Leticia

    2017-09-01

    The possibility to discriminate the ortho and para nuclear spin isomers of 1,1-difluoroethylene via their excited state dynamics is studied using wavepacket propagations including non-adiabatic couplings. The two nuclear spin isomers are connected via a torsional motion around the double bond. Photo-excitation induces a different interference pattern, with different torsional periods - a fact that can be exploited to distinguish, and eventually separate the nuclear spin isomers using femtosecond pump-probe experiments. The inclusion of non-adiabatic couplings results in a slowdown of the wavepacket, increasing the torsional periods of the nuclear spin isomers.

  10. In vitro interaction study of retinoic acid isomers with telmisartan and amlodipine by equilibrium dialysis method using UV spectroscopy

    Science.gov (United States)

    Varghese, Susheel John; Johny, Sojimol K.; Paul, David; Ravi, Thengungal Kochupappy

    2011-07-01

    The in vitro protein binding of retinoic acid isomers (isotretinoin and tretinoin) and the antihypertensive drugs (amlodipine and telmisartan) was studied by equilibrium dialysis method. In this study, free fraction of drugs and the % of binding of drugs in the mixture to bovine serum albumin (BSA) were calculated. The influence of retinoic acid isomers on the % of protein binding of telmisartan and amlodipine at physiological pH (7.4) and temperature (37 ± 0.5 °C) was also evaluated. The in vitro displacement interaction study of drugs telmisartan and amlodipine on retinoic acid isomers and also interaction of retinoic acid isomers on telmisartan and amlodipine were carried out.

  11. Isomer discrimination of polycyclic aromatic hydrocarbons in the Murchison meteorite by resonant ionization.

    Science.gov (United States)

    Callahan, Michael P; Abo-Riziq, Ali; Crews, Bridgit; Grace, Louis; de Vries, Mattanjah S

    2008-12-15

    We have used two-color resonant two-photon ionization (2C-R2PI) mass spectrometry to discriminate between isomers of polycyclic aromatic hydrocarbons in the Murchison meteorite. We measured the 2C-R2PI spectra of chrysene and triphenylene seeded in a supersonic jet by laser desorption. Since each isomer differs in its R2PI spectrum, we can distinguish between isomers using wavelength dependent ionization and mass spectrometry. We found both chrysene and triphenylene in sublimates from carbonaceous residue obtained by acid demineralization of the Murchison meteorite. Their R2PI mass spectra show only the molecular ion, even though these samples contain a complex inventory of organic molecules.

  12. Study of the separation method of structural isomer using Magneto-Archimedes method

    Energy Technology Data Exchange (ETDEWEB)

    Mori, T.; Kobayadhi, T.; Mishima, F.; Akiyama, Y.; Nishijima, Shigehiro [Osaka University, Osaka (Japan)

    2016-03-15

    Organic compounds have a problem that the separation of structural isomer in the preparation process requires high energy consumption. This study proposes a new separation method of structural isomer using Magneto- Archimedes method. Firstly, the levitation height of 1, 6-DDA and 1, 10-DDA was respectively calculated by simulation of the forces acting on the particles under magnetic field, and it was indicated that they could be separated by the difference of levitation height. To confirm the phenomenon experimentally, white powders of 1, 6-DDA and 1, 10-DDA were formed into pellets, and were soaked in manganese chloride solution. Then the solution was put on the center of the cryostat of HTS bulk magnet (maximum magnetic flux density is 3T). As a result, it was confirmed that the separation of structural isomer by difference of levitation height could be possible.

  13. [GC-FTIR analysis of structural isomers from hydrogenation products of p-phenylphenol].

    Science.gov (United States)

    Xin, Jun-Na; Xu, Qiang; Zhang, Hua; Yang, Xi-Chuan; Lü, Lian-Hai

    2008-04-01

    The hydrogenation of p-phenylphenol is a consecutive and parallel complex reaction. Owing to the difference in the hydrogenation ability of the two benzene rings in pphenylphenol, the hydrogenation products contained several structural isomers, which can not be identified by normal analytical method. However, the reaction mixture was effectively separated and identified by GC-FTIR technique. According to the characteristic wave numbers of benzene ring substituted at different positions, the main product was confirmed to be p-cyclohexylphenol, and the two typical by-products were p-phenylcyclohexanol and p-cyclohexylcyclohexanol, respectively. Each product has several stereo-isomers. GC-MS, melting point measurement and NMR proved the accuracy of GC-FTIR results, indicating that GC-IR is an useful and rapid method for analyzing structural isomers of organic compounds.

  14. How to avoid mass transfer limitations in ozonation kinetics of phenylphenol isomers?

    Directory of Open Access Journals (Sweden)

    Olak-Kucharczyk Magdalena

    2016-03-01

    Full Text Available Ozonation is a heterogeneous process of chemical absorption often controlled by a gas-liquid mass transfer rate. This paper presents the results of kinetics in a reaction between phenylphenol isomers and ozone. The degradation of phenylphenol isomers during ozonation proceeds quite fast. In order to avoid the influence of mass transfer limitation the kinetics experiments were conducted in a homogenous liquid-liquid system. The second-order rate constants were determined using classical and competition methods, which are especially recommended for fast reactions. The determined rate constants at pH 2 using the two different methods are almost the same. The increase of pH causes an increase of rate constants for the reaction of phenylphenol isomers with ozone.

  15. 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.

  16. Decay of the 67-μs Isomer in 142pm

    Institute of Scientific and Technical Information of China (English)

    柳敏良; 张玉虎; 周小红; 郭应祥; 雷相国; 刘忠; 何建军; 温书贤; 吴晓光; 袁观俊

    2004-01-01

    Excited states in 142pm are investigated via the 128 Te(19F, 5n)142pm reaction at beam energies from 75 to 95 MeV by using techniques of in-beam γ-ray spectroscopy. Measurements of γ-ray excitation function, X-γ and γ-γ-tcoincidences are performed with 10 BGO(AC)HPGe detectors. Decay of the previously known 67-μs isomer in 142Pm is observed and added into the new level scheme. This isomer is definitely placed at the excitation energy of 2828.5 keV. The spin of this isomer is suggested to be 13h according to the measured γ-ray anisotropies.

  17. 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.

    2017-08-01

    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.

  18. Effects of pentanol isomers on the phase behavior of phospholipid bilayer membranes.

    Science.gov (United States)

    Griffin, Kathryn L; Cheng, Chih-Yin; Smith, Eric A; Dea, Phoebe K

    2010-11-01

    Differential scanning calorimetry (DSC) was used to analyze the thermotropic phase behavior of dipalmitoylphosphatidylcholine (DPPC) bilayers in the presence of pentanol isomers. The concentration of each pentanol isomer needed to induce the interdigitated phase was determined by the appearance of a biphasic effect in the main transition temperatures, the onset of a hysteresis associated with the main transition from the gel-to-liquid crystalline phase, and the disappearance of the pretransition. Lower threshold concentrations were found to correlate with isomers of greater alkyl chain length while branching of the alkyl chain was found to increase biphasic behavior. The addition of a methyl group to butanol systems drastically decreased threshold concentrations. However, as demonstrated in the DPPC/neopentanol system, branching of the alkyl chain away from the -OH group lowers the threshold concentration while maintaining a biphasic effect.

  19. Reduction of MTT to Purple Formazan by Vitamin E Isomers in the Absence of Cells.

    Science.gov (United States)

    Lim, Su-Wen; Loh, Hwei-San; Ting, Kang-Nee; Bradshaw, Tracey Dawn; Allaudin, Zeenathul Nazariah

    2015-04-01

    The yellow tetrazolium salt 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide (MTT) is widely used to determine cell viability in cell proliferation and cytotoxic assays. MTT is reduced by metabolically active cells to form an insoluble purple formazan product that is quantifiable by spectrophotometry. It is the most common and direct assay for cell viability. However, in this present study, we demonstrated that the vitamin E isomers α-β-γ-δ-tocotrienols and α-tocopherol were able to reduce MTT into a formazan product, despite the absence of living cells. For comparison, a second method for determining cell viability, which is the neutral red uptake assay, was used in parallel with the MTT assay. The results showed that neutral red did not interact with the vitamin E isomers. Our findings suggest that the MTT assay is not suitable for studying the proliferative effects of vitamin E isomers on cell growth.

  20. New μs isomers in the neutron-rich {sup 210}Hg nucleus

    Energy Technology Data Exchange (ETDEWEB)

    Gottardo, A., E-mail: andrea.gottardo@lnl.infn.it [Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Legnaro, Legnaro, 35020 (Italy); Dipartimento di Fisica dell' Università degli Studi di Padova, Padova, 35131 (Italy); Valiente-Dobón, J.J. [Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Legnaro, Legnaro, 35020 (Italy); Benzoni, G. [Istituto Nazionale di Fisica Nucleare, Sezione di Milano, Milano, 20133 (Italy); Gadea, A. [Instituto de Física Corpuscular, CSIC-Universitat de València, València, E-46980 (Spain); Lunardi, S. [Dipartimento di Fisica dell' Università degli Studi di Padova, Padova, 35131 (Italy); Istituto Nazionale di Fisica Nucleare, Sezione di Padova, Padova, 35131 (Italy); Boutachkov, P. [GSI Helmholtzzentrum für Schwerionenforschung, Darmstadt, D-64291 (Germany); Bruce, A.M. [School of Computing, Engineering and Mathematics, University of Brighton, Brighton, BN2 4GJ (United Kingdom); Górska, M. [GSI Helmholtzzentrum für Schwerionenforschung, Darmstadt, D-64291 (Germany); Grebosz, J. [Niewodniczanski Institute of Nuclear Physics, Polish Academy of Science, Krakow, PL-31-342 (Poland); Pietri, S. [GSI Helmholtzzentrum für Schwerionenforschung, Darmstadt, D-64291 (Germany); Podolyák, Zs. [Department of Physics, University of Surrey, Guildford, GU2 7XH (United Kingdom); Pfützner, M. [Faculty of Physics, University of Warsaw, Warsaw, PL-00681 (Poland); Regan, P.H. [Department of Physics, University of Surrey, Guildford, GU2 7XH (United Kingdom); Weick, H. [GSI Helmholtzzentrum für Schwerionenforschung, Darmstadt, D-64291 (Germany); Alcántara Núñez, J. [Universidade de Santiago de Compostela, Santiago de Compostela, E-175706 (Spain); and others

    2013-10-01

    Neutron-rich nuclei in the lead region, beyond N=126, have been studied at the FRS-RISING setup at GSI, exploiting the fragmentation of a primary uranium beam. Two isomeric states have been identified in {sup 210}Hg: the 8{sup +} isomer expected from the seniority scheme in the νg{sub 9/2} shell and a second one at low spin and low excitation energy. The decay strength of the 8{sup +} isomer confirms the need of effective three-body forces in the case of neutron-rich lead isotopes. The other unexpected low-lying isomer has been tentatively assigned as a 3{sup −} state, although this is in contrast with theoretical expectations.

  1. Experimental investigation of the low temperature oxidation of the five isomers of hexane.

    Science.gov (United States)

    Wang, Zhandong; Herbinet, Olivier; Cheng, Zhanjun; Husson, Benoit; Fournet, René; Qi, Fei; Battin-Leclerc, Frédérique

    2014-07-31

    The low-temperature oxidation of the five hexane isomers (n-hexane, 2-methyl-pentane, 3-methyl-pentane, 2,2-dimethylbutane, and 2,3-dimethylbutane) was studied in a jet-stirred reactor (JSR) at atmospheric pressure under stoichiometric conditions between 550 and 1000 K. The evolution of reactant and product mole fraction profiles were recorded as a function of the temperature using two analytical methods: gas chromatography and synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). Experimental data obtained with both methods were in good agreement for the five fuels. These data were used to compare the reactivity and the nature of the reaction products and their distribution. At low temperature (below 800 K), n-hexane was the most reactive isomer. The two methyl-pentane isomers have about the same reactivity, which was lower than that of n-hexane. 2,2-Dimethylbutane was less reactive than the two methyl-pentane isomers, and 2,3-dimethylbutane was the least reactive isomer. These observations are in good agreement with research octane numbers given in the literature. Cyclic ethers with rings including 3, 4, 5, and 6 atoms have been identified and quantified for the five fuels. While the cyclic ether distribution was notably more detailed than in other literature of JSR studies of branched alkane oxidation, some oxiranes were missing among the cyclic ethers expected from methyl-pentanes. Using SVUV-PIMS, the formation of C2-C3 monocarboxylic acids, ketohydroperoxides, and species with two carbonyl groups have also been observed, supporting their possible formation from branched reactants. This is in line with what was previously experimentally demonstrated from linear fuels. Possible structures and ways of decomposition of the most probable ketohydroperoxides were discussed. Above 800 K, all five isomers have about the same reactivity, with a larger formation from branched alkanes of some unsaturated species, such as allene and propyne, which

  2. Quantitative Analysis of the Distribution of cis-Eicosenoic Acid Positional Isomers in Marine Fishes from the Indian Ocean.

    Science.gov (United States)

    Senarath, Samanthika; Yoshinaga, Kazuaki; Nagai, Toshiharu; Yoshida, Akihiko; Beppu, Fumiaki; Jayasinghe, Chamila; Devadawson, Chandravathany; Gotoh, Naohiro

    2017-02-01

    This study investigated the occurrence and distribution of cis-eicosenoic acid (c-20:1) positional isomers in fishes from the Indian Ocean and compared to those from the Pacific and Atlantic Ocean. Lipids were extracted from the edible part of the fish and then methylated. The eicosenoic acid methyl ester fraction was separated from total fatty acid methyl esters by reversed-phase HPLC and quantitatively analyzed using a GC-FID fitted with the SLB-IL111 highly polar GC column. c14-20:1 was used as an internal standard. The results indicated that the highest levels of c-20:1 positional isomers were found in fishes from the Pacific Ocean (saury, 166.95±12.4 mg/g of oil), followed by the Atlantic Ocean (capelin, 162.7±3.5 mg/g of oil), and lastly in fishes from the Indian Ocean (goatfish, 34.39 mg/g of oil). With only a few exceptions, the most abundant 20:1 positional isomer found in fishes of the Indian and Atlantic Ocean was the c11-20:1 isomer (>50%) followed by the c13-20:1 isomer (<25%). Unusually, the c7-20:1 isomer was predominantly found in a few fishes such as the tooth ponyfish, longface emperor, and commerson's sole. The c9, c5, and c15-20:1 isomers were the least occurring in fishes from the Indian and Atlantic Ocean. In contrast, the c9-20:1 isomer was the principal isomer identified in fishes from the Pacific Ocean. The results revealed that the content and distribution of c-20:1 positional isomers varied among fishes in different oceans. The data presented in the current study are the first to report on the distribution of c-20:1 positional isomers in fishes from the Indian Ocean.

  3. Isomer separation and measurement of nuclear moments with the ISOLDE RILIS

    Energy Technology Data Exchange (ETDEWEB)

    Koester, U.; Catherall, R. [ISOLDE, CERN (Switzerland); Fedoseyev, V.N. [Russian Academy of Sciences, Institute of Spectroscopy (Russian Federation); Franchoo, S. [K.U. Leuven, Instituut voor Kern en Stralingsfysica (Belgium); Georg, U. [ISOLDE, CERN (Switzerland); Huyse, M.; Kruglov, K. [K.U. Leuven, Instituut voor Kern en Stralingsfysica (Belgium); Lettry, J. [ISOLDE, CERN (Switzerland); Mishin, V.I. [Russian Academy of Sciences, Institute of Spectroscopy (Russian Federation); Oinonen, M.; Ravn, H. [ISOLDE, CERN (Switzerland); Seliverstov, M.D. [St. Petersburg Nuclear Physics Institute (Russian Federation); Simon, H. [ISOLDE, CERN (Switzerland); Van Duppen, P.; Van Roosbroeck, J.; Weissman, L. [K.U. Leuven, Instituut voor Kern en Stralingsfysica (Belgium)

    2000-08-15

    Short-lived radioisotopes are element selectively ionized by the resonance ionization laser ion source (RILIS) of the on-line isotope separator ISOLDE (CERN). The relative production of low and high spin isomers can be significantly changed when a narrow-bandwidth laser is used to scan through the atomic hyperfine structure. This allows the assignment of gamma ray transitions to the decay of the individual isomers. Moreover, the measurement of the hyperfine splitting provides a very sensitive method for the determination of magnetic moments of exotic isotopes. The technical developments are discussed for the example of copper.

  4. Solvent effects on reactivity properties of dicarba-closo-dodecarboranes isomers

    Science.gov (United States)

    Junqueira, G. M. A.; Rocha, L. C.; Cotta, V. T.; César, E. T.

    2012-06-01

    In this Letter, a discussion on global reactivity indexes - electronic chemical potential (μ), chemical hardness (η) and electrophilicity (ω) - for dicarba-closo-dodecarboranes isomers, in gas phase and aqueous solution is reported. A sequential Monte Carlo/quantum mechanics methodology (S-MC/QM) was used in simulations. The results obtained showed the solvent must be considered on reactivity properties of the studied compounds. Generally, the solvated isomers become softer (η decreases) and the μ increases comparing to gas phase values, indicating the charge transfer from solvent to the solute.

  5. Tryptophan-Ethylester, the False (Unveiled) Melatonin Isomer in Red Wine

    Science.gov (United States)

    Iriti, Marcello; Vigentini, Ileana

    2015-01-01

    Among the food plants, the presence of melatonin in grapes (Vitis vinifera L.) deserves particular attention because of the production of wine, an alcoholic beverage of economic relevance and with putative healthy effects. Furthermore, melatonin isomers have been detected in wine too. Recently, one of these isomers has been identified as tryptophan-ethylester, a compound with the same molecular weight of melatonin. In this Commentary, we briefly comment the source(s) of tryptophan-ethylester in wine and the putative nutritional role(s). PMID:25922582

  6. Laboratory data base for isomer-specific determination of polychlorinated biphenyls

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, T.R.; Campbell, R.D.; Stalling, D.L.; Little, R.L.; Petty, J.D.; Hogan, J.W.; Kaiser, E.M.

    1984-07-01

    A computer-assisted technique for quantitative determination of polychlorinated biphenyl isomers is described. PCB isomers were identified by use of a retention index system with n-alkyl trichloroacetates as retention index marker compounds. A laboratory data base system was developed to aid in editing and quantitation of data generated from capillary gas chromatographic data. Data base management was provided by computer programs written in DSM-11 (Digital Standard MUMPS) for the PDP-11 family of computers. 13 references, 4 figures, 2 tables.

  7. Laminar burning velocities and flame instabilities of butanol isomers-air mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Gu, Xiaolei; Huang, Zuohua; Wu, Si; Li, Qianqian [State Key Laboratory of Multiphase Flow in Power Engineering, Xi' an Jiaotong University, Xi' an 710049 (China)

    2010-12-15

    Laminar burning velocities and flame instabilities of the butanol-air premixed flames and its isomers are investigated using the spherically expanding flame with central ignition at initial temperature of 428 K and initial pressures of 0.10 MPa, 0.25 MPa, 0.50 MPa and 0.75 MPa. Laminar burning velocities and sensitivity factor of n-butanol-air mixtures are computed using a newly developed kinetic mechanism. Unstretched laminar burning velocity, adiabatic temperature, Lewis number, Markstein length, critical flame radius and Peclet number are obtained over a wide range of equivalence ratios. Effect of molecular structure on laminar burning velocity of the isomers of butanol is analyzed from the aspect of C-H bond dissociation energy. Study indicates that although adiabatic flame temperatures of the isomers of butanol are the same, laminar burning velocities give an obvious difference among the isomers of butanol. This indicates that molecular structure has a large influence on laminar burning velocities of the isomers of butanol. Branching (-CH3) will decrease laminar burning velocity. Hydroxyl functional group (-OH) attaching to the terminal carbon atoms gives higher laminar burning velocity compared to that attaching to the inner carbon atoms. Calculated dissociation bond energies show that terminal C-H bonds have larger bond energies than that of inner C-H bonds. n-Butanol, no branching and with hydroxyl functional group (-OH) attaching to the terminal carbon atom, gives the largest laminar burning velocity. tert-Butanol, with highly branching and hydroxyl functional group (-OH) attaching to the inner carbon atom, gives the lowest laminar burning velocity. Laminar burning velocities of iso-butanol and sec-butanol are between those of n-butanol and tert-butanol. The instant of transition to cellularity is experimentally determined for the isomers of butanol and subsequently interpreted on the basis of hydrodynamic and diffusion-thermal instabilities. Little effect

  8. Observation of a New (25/2+) Isomer in 121Sb

    Science.gov (United States)

    Kownacki, J.; Kisielinski, M.; Kowalczyk, M.; Droste, Ch.; Morek, T.; Ruchowska, E.; Srebrny, J.; Wolinska-Cichocka, M.; Palacz, M.; Korman, A.; Andrzejewski, J.; KrXf3l, A.; Perkowski, J.; Lieder, R.; Mierzejewski, J.; Sankowska, I.

    2008-02-01

    The beam pulse structure of the HIL cyclotron and thick target gamma -gamma coincidence measurements in the in-beam and off-beam modes have been used to search for isomers in the A approx 120 mass region using heavy-ion reactions. The half-life of the 2721 keV, (25/2+) level in 121Sb was determined in the off-beam mode to be 167 pm 19 mu s. Two deexcitation sequences of this isomer are proposed. The isomeric state is considered to be of 3-quasiparticle nature pi (d5/2)nu (h11/22)10+.

  9. Revised structure of a homonojirimycin isomer from Aglaonema treubii: first example of a naturally occurring alpha-homoallonojirimycin.

    Science.gov (United States)

    Martin, O R; Compain, P; Kizu, H; Asano, N

    1999-11-01

    The structure of a homonojirimycin isomer isolated from Aglaonema treublii and originally proposed as alpha-3,4-di-epi-homonojirimycin was revised to alpha-4-epi-homonojirimycin 3 ("alpha-homoallonojirimycin") on the basis of NMR analysis and synthetic studies. Its activity as a glycosidase inhibitor is compared to that of other homonojirimycin isomers.

  10. The interstellar chemistry of C3H and C3H2 isomers

    Science.gov (United States)

    Loison, Jean-Christophe; Agúndez, Marcelino; Wakelam, Valentine; Roueff, Evelyne; Gratier, Pierre; Marcelino, Núria; Reyes, Dianailys Nuñez; Cernicharo, José; Gerin, Maryvonne

    2017-10-01

    We report the detection of linear and cyclic isomers of C3H and C3H2 towards various starless cores and review the corresponding chemical pathways involving neutral (C3Hx with x = 1,2) and ionic (C3Hx+ with x = 1,2,3) isomers. We highlight the role of the branching ratio of electronic dissociative recombination (DR) reactions of C3H2+ and C3H3+ isomers, showing that the statistical treatment of the relaxation of C3H* and C3H2* produced in these DR reactions may explain the relative c,l-C3H and c,l-C3H2 abundances. We have also introduced in the model the third isomer of C3H2 (HCCCH). The observed cyclic-to-linear C3H2 ratio varies from 110 ± 30 for molecular clouds with a total density of about 1 × 104 molecules cm-3 to 30 ± 10 for molecular clouds with a total density of about 4 × 105 molecules cm-3, a trend well reproduced with our updated model. The higher ratio for molecular clouds with low densities is determined mainly by the importance of the H + l-C3H2 → H + c-C3H2 and H + t-C3H2 → H + c-C3H2 isomerization reactions.

  11. Ab Initio Investigations of the C2F4S Isomers and of Their Interconversions

    DEFF Research Database (Denmark)

    Shim, Irene; Vallano-Lorenzo, Sandra; Lisbona-Martin, Pilar

    2003-01-01

    The transition states and the activation energies for the unobserved isomerization reactions between the three possible C2F4S isomers with divalent sulfur, trifluorothioacetyl fluoride 1, tetrafluorothiirane 2, and trifluoroethenesulfenyl fluoride 3, have been determined by ab initio Hartree-Fock...

  12. 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.

  13. 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, 2-methylp

  14. Structures, Vibrational Spectra, and Relative Energetics of CH3COIO3 Isomers

    Institute of Scientific and Technical Information of China (English)

    GE,Mao-Fa; MA,Chun-Ping

    2008-01-01

    The structures,vibrational spectra,relative energetics,and enthalpies of formation of CH3COlO3 isomers have been investigated with B3LYP,B3P86 and B3PW91 methods in conjugation with the 6-31+G(d),6-311+G(d,p)and 6-311++G(3df,3pd) basis sets.The CH3COOIO2 structure was found to be the most stable form among the isomers with an estimated enthalpy of formation of -314.6 kJ·mol-1.The enthalpies of formation for CH3COOOOI,CH3COOOIO and CH3COIO3 are -180.7,-184.9 and -50.6 kJ·mol-1,respectively.The implication of the formation of CH3COIO3 isomers from the atmospheric cross-reactions of the acetylperoxy (CH3COO2) and iodine monoxide (IO) radicals was examined and the possible dissociation products of the most likely CH3COIO3 isomers were determined.

  15. Beta decay of {sup 94}Pd and of the 71s isomer of {sup 94}Rh

    Energy Technology Data Exchange (ETDEWEB)

    Batist, L. [St. Petersburg Nuclear Physics Institute, Gatchina (Russian Federation); Department of Physics of the University ' ' Federico II' ' , Napoli (Italy); Blazhev, A. [Gesellschaft fuer Schwerionenforschung, Darmstadt (Germany); University of Sofia, Sofia (Bulgaria); Doering, J. [University of Sofia, Sofia (Bulgaria); Grawe, H.; Kirchner, R.; Mazzocchi, C.; Plettner, C.; Roeckl, E. [Gesellschaft fuer Schwerionenforschung, Darmstadt (Germany); Kavatsyuk, M.; Kavatsyuk, O. [Gesellschaft fuer Schwerionenforschung, Darmstadt (Germany); National Taras Shevchenko University of Kyiv, Kyiv (Ukraine); La Commara, M.; Romoli, M. [Department of Physics of the University ' ' Federico II' ' , Napoli (Italy); Mukha, I. [Gesellschaft fuer Schwerionenforschung, Darmstadt (Germany); University of Seville, Sevilla (Spain)

    2006-08-15

    The {beta} decay of {sup 94}Pd and of the 71s isomer of {sup 94}Rh was investigated by using total {gamma}-ray absorption techniques. Several levels in {sup 94}Rh are established, including a new low-lying isomer characterized by a half-life of 0.48(3) {mu}s and a de-exciting transition of 55keV. E2 multipolarity is determined for this transition by measuring the intensities of its {gamma}-rays and the characteristic X-rays from its electron conversion. On the basis of the measured reduced {beta}-decay transition rates to known {sup 94}Ru levels and shell model considerations, the spin-parity of the 71s and the 0.48{mu}s isomers of {sup 94}Rh is assigned to be (4{sup +}) and (2{sup +}), respectively. The {beta}-decay strength distributions measured for {sup 94}Pd and the 71s isomer of {sup 94}Rh yield Q{sub EC} values of 6700(320) and 9750(320)keV for these decays and give evidence for the population of those states below and above the magic N=50 gap that belong to both components of the 0g spin-orbit doublet. (orig.)

  16. Lipid and Glycolipid Isomer Analyses Using Ultra-High Resolution Ion Mobility Spectrometry Separations

    Directory of Open Access Journals (Sweden)

    Roza Wojcik

    2017-01-01

    Full Text Available Understanding the biological roles and mechanisms of lipids and glycolipids is challenging due to the vast number of possible isomers that may exist. Mass spectrometry (MS measurements are currently the dominant approach for studying and providing detailed information on lipid and glycolipid presence and changes. However, difficulties in distinguishing the many structural isomers, due to the distinct lipid acyl chain positions, double bond locations or specific glycan types, inhibit the delineation and assignment of their biological roles. Here we utilized ultra-high resolution ion mobility spectrometry (IMS separations by applying traveling waves in a serpentine multi-pass Structures for Lossless Ion Manipulations (SLIM platform to enhance the separation of selected lipid and glycolipid isomers. The multi-pass arrangement allowed the investigation of paths ranging from ~16 m (one pass to ~60 m (four passes for the distinction of lipids and glycolipids with extremely small structural differences. These ultra-high resolution SLIM IMS-MS analyses provide a foundation for exploring and better understanding isomer-specific biological activities and disease processes.

  17. Isomer production ratios and the angular momentum distribution of fission fragments

    Science.gov (United States)

    Stetcu, I.; Talou, P.; Kawano, T.; Jandel, M.

    2013-10-01

    Latest generation fission experiments provide an excellent testing ground for theoretical models. In this contribution we compare the measurements for 235U(nth,f), obtained with the Detector for Advanced Neutron Capture Experiments (DANCE) calorimeter at Los Alamos Neutron Science Center (LANSCE), with our full-scale simulation of the primary fragment de-excitation, using the recently developed cgmf code, based on a Monte Carlo implementation of the Hauser-Feshbach theoretical model. We compute the isomer ratios as a function of the initial angular momentum of the fission fragments, for which no direct information exists. Comparison with the available experimental data allows us to determine the initial spin distribution. We also study the dependence of the isomer ratio on the knowledge of the low-lying discrete spectrum input for nuclear fission reactions, finding a high degree of sensitivity. Finally, in the same Hauser-Feshbach approach, we calculate the isomer production ratio for thermal neutron capture on stable isotopes, where the initial conditions (spin, excitation energy, etc.) are well understood. We find that with the current parameters involved in Hauser-Feshbach calculations, we obtain up to a factor of 2 deviation from the measured isomer ratios.

  18. Microsecond isomers in the odd-odd nucleus [sup 144]Tb

    Energy Technology Data Exchange (ETDEWEB)

    Sferrazza, M.; Bazzacco, D.; Lunardi, S.; Maglione, E. (INFN, Padua (Italy) Dipt. di Fisica, Padua Univ. (Italy)); Cardona, M.A.; Rico, J.; Facco, A. (INFN, Laboratori Nazionali di Legnaro (Italy)); De Angelis, G.; Bizzeti, P.G.; Bizzeti-Sona, A.M. (INFN, Florence (Italy) Dipt. di Fisica, Florence Univ. (Italy))

    1992-11-01

    Two new isomers with half-lives of 0.67(6) [mu]s and 2.8(3) [mu]s have been identified in the odd-odd nucleus [sup 144]Tb. A partial decay scheme is presented. An interpretation in the framework of the shell model is discussed for the low lying energy states. (orig.).

  19. Lack of selective developmental toxicity of three butanol isomers administered by inhalation to rats.

    Science.gov (United States)

    Nelson, B K; Brightwell, W S; Khan, A; Burg, J R; Goad, P T

    1989-04-01

    As part of an ongoing study of the developmental toxicology of industrial alcohols, this report presents the results of the teratology assessments of 1-butanol, 2-butanol, and t-butanol administered by inhalation to rats. Groups of approximately 15 Sprague-Dawley rats were exposed at 8000, 6000, 3500, or 0 ppm 1-butanol, 7000, 5000, 3500, or 0 ppm 2-butanol, or 5000, 3500, 2000, or 0 ppm t-butanol for 7 hr/day on Gestation Days 1-19 (sperm = 0). In each case, the highest concentration was selected to produce maternal toxicity. Dams were sacrificed on Gestation Day 20, and fetuses were individually weighed, tagged, and examined for external malformations. One-half of the fetuses were stained and examined for skeletal abnormalities, and the other half were examined for visceral defects using the Wilson technique. For each butanol isomer examined, the highest concentration (and the intermediate in some cases) was maternally toxic, as manifest by reduced weight gain and feed intake. Even at a maternally toxic dose, and in spite of a dose-dependent reduction in fetal weights for each isomer, the only teratogenicity observed was a slight increase in skeletal malformations (primarily rudimentary cervical ribs), seen with the highest concentration of 1-butanol. Thus, although teratogenicity was observed at 8000 ppm 1-butanol, and developmental toxicity was observed with each of the butyl alcohol isomers studied, concentrations 50 times the current permissible exposure limits for these three butanol isomers do not produce teratogenicity in rats.

  20. Toward the laboratory identification of [O,N,S,S] isomers: Implications for biological NO chemistry

    Science.gov (United States)

    Ayari, Tarek; Jaidane, Nejm-Eddine; Al Mogren, Muneerah Mogren; Francisco, Joseph S.; Hochlaf, Majdi

    2016-06-01

    Benchmark ab initio calculations are performed to investigate the stable isomers of [O,N,S,S]. These computations are carried out using coupled cluster (RCCSD(T)) and explicitly correlated coupled cluster methods (RCCSD(T)-F12). In addition to the already known cis isomer of SSNO, nine other stable forms are predicted. The most stable isomer is cis-OSNS. Nine structures are chain bent-bent with relatively large dipole moments which make them detectable, as cis-SSNO, by infrared, far-infrared, and microwave spectroscopies. We found also a C2v isomer (NS2O). Since these species are strongly suggested to play an important role as intermediates during the bioactive reaction products of the NO/H2S interaction, the rotational and vibrational spectroscopic parameters are presented to help aid the in vivo identification and assignment of these spectra. Results from this work show that [O,N,S,S] may play key roles during nitric oxide transport and deliver in biological media, as well as, provide an explanation for the weak characteristic of disulfide bridges within proteins.

  1. Prospects for measuring the $^{229}$Th isomer energy using a metallic magnetic microcalorimeter

    CERN Document Server

    Kazakov, G A; Sterba, J H; Fleischmann, A; Enss, C; Schumm, T

    2013-01-01

    The Thorium-229 isotope features a nuclear isomer state with extremely low energy. The currently most accepted energy value, $7.8 \\pm 0.5$\\,eV, was obtained from an indirect measurements using a NASA x-ray microcalorimeter with instrumental resolution (FWHM) of 26\\,eV. We study, how state-of-the-art magnetic metallic microcalorimeters with an energy resolution down to a few eV can be used to measure the isomer energy. Resolving the 29.18\\,keV doublet in the $\\gamma$-spectrum following the $\\alpha$-decay of Uranium-233, corresponding to the decay into the ground and isomer state, allows to measure the isomer transition energy without additional theoretical input parameters and increase the energy accuracy. We study the dependence of the attainable precision of this measurement on the signal and background count rates and the instrumental energy resolution. Assuming realistic experimental parameters corresponding to the currently available detector technology, we show that such a measurement is highly feasable.

  2. Infrared spectroscopy of the acetyl cation and its protonated ketene isomer

    Energy Technology Data Exchange (ETDEWEB)

    Mosley, J. D.; Young, J. W.; Duncan, M. A. [Department of Chemistry, University of Georgia, Athens, Georgia 30602 (United States)

    2014-07-14

    [C{sub 2},H{sub 3},O]{sup +} ions are generated with a pulsed discharge in a supersonic expansion containing methyl acetate or acetone. These ions are mass selected and their infrared spectra are recorded via laser photodissociation and the method of argon tagging. Computational chemistry is employed to investigate structural isomers and their spectra. The acetyl cation (CH{sub 3}CO{sup +}) is the global minimum and protonated ketene (CH{sub 2}COH{sup +}) is the next lowest energy isomer (+176.2 kJ/mol). When methyl acetate is employed as the precursor, the infrared spectrum reveals that only the acetyl cation is formed. Partially resolved rotational structure reveals rotation about the C{sub 3} axis. When acetone is used as the precursor, acetyl is still the most abundant cation, but there is also a minor component of protonated ketene. Computations reveal a significant barrier to interconversion between the two isomers (+221 kJ/mol), indicating that protonated ketene must be obtained via kinetic trapping. Both isomers may be present in interstellar environments, and their implications for astrochemistry are discussed.

  3. The sim operon facilitates the transport and metabolism of sucrose isomers in Lactobacillus casei ATCC 334.

    Science.gov (United States)

    Thompson, John; Jakubovics, Nicholas; Abraham, Bindu; Hess, Sonja; Pikis, Andreas

    2008-05-01

    Inspection of the genome sequence of Lactobacillus casei ATCC 334 revealed two operons that might dissimilate the five isomers of sucrose. To test this hypothesis, cells of L. casei ATCC 334 were grown in a defined medium supplemented with various sugars, including each of the five isomeric disaccharides. Extracts prepared from cells grown on the sucrose isomers contained high levels of two polypeptides with M(r)s of approximately 50,000 and approximately 17,500. Neither protein was present in cells grown on glucose, maltose or sucrose. Proteomic, enzymatic, and Western blot analyses identified the approximately 50-kDa protein as an NAD(+)- and metal ion-dependent phospho-alpha-glucosidase. The oligomeric enzyme was purified, and a catalytic mechanism is proposed. The smaller polypeptide represented an EIIA component of the phosphoenolpyruvate-dependent sugar phosphotransferase system. Phospho-alpha-glucosidase and EIIA are encoded by genes at the LSEI_0369 (simA) and LSEI_0374 (simF) loci, respectively, in a block of seven genes comprising the sucrose isomer metabolism (sim) operon. Northern blot analyses provided evidence that three mRNA transcripts were up-regulated during logarithmic growth of L. casei ATCC 334 on sucrose isomers. Internal simA and simF gene probes hybridized to approximately 1.5- and approximately 1.3-kb transcripts, respectively. A 6.8-kb mRNA transcript was detected by both probes, which was indicative of cotranscription of the entire sim operon.

  4. Comparative dielectric study of pentanol isomers with terahertz time-domain spectroscopy

    Science.gov (United States)

    Yomogida, Yoshiki; Sato, Yuki; Yamakawa, Kazuyoshi; Nozaki, Ryusuke; Mishina, Tomobumi; Nakahara, Jun'ichiro

    2010-04-01

    Using terahertz (THz) time-domain spectroscopy, we have measured the complex permittivity of seven pentanol isomers (1-pentanol, 2-pentanol, 3-pentanol, 2-methly-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, and 3-methyl-2-butanol) in the frequency range of 0.2-2.5 THz at temperatures from 253 to 323 K. For all samples, the complex permittivity contains the following three components: (i) a high-frequency side of dielectric relaxation processes, (ii) a broad vibration mode around 1.5 THz, and (iii) a low-frequency side of an intermolecular stretching mode located above 2.5 THz. At low temperatures, the relaxation process moves to a low-frequency range and a peak of the broad vibration mode, which is independent of temperature, is clearly observed around 1.5 THz. Spectra in the THz region change sensitively according to the molecular structure of the pentanol isomers. We have also observed the complex permittivity in the microwave range of 1 MHz-20 GHz. The behavior of the dielectric relaxation processes below GHz region much depend on the isomers. Our experimental data demonstrate that the molecular structures of the pentanol isomers influence all the molecular dynamics ranging from dielectric relaxation phenomena, which are due to reorientational motion of the molecules, to vibration dynamics within the hydrogen-bonded network structure.

  5. 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})

  6. Conformational preferences and synthesis of isomers Z and E of oxazole-dehydrophenylalanine.

    Science.gov (United States)

    Staś, Monika; Bujak, Maciej; Broda, Małgorzata A; Siodłak, Dawid

    2016-05-01

    Dehydrophenylalanine, ΔPhe, is the most commonly studied α,β-dehydroamino acid. In nature, further modifications of the α,β-dehydroamino acids were found, for example, replacement of the C-terminal amide group by oxazole ring. The conformational properties of oxazole-dehydrophenylalanine residue (ΔPhe-Ozl), both isomers Z and E, were investigated. To determine all possible conformations, theoretical calculations were performed using Ac-(Z/E)-ΔPhe-Ozl(4-Me) model compounds at M06-2X/6-31++G(d,p) level of theory. Ac-(Z/E)-ΔPhe-Ozl-4-COOEt compounds were synthesized and the conformational preferences of each isomer, Z and E, were investigated using FTIR and NMR-NOE in solutions of increasing polarity (CHCl3 , DMSO-d6). The solid-state low-temperature structures of Ac-(Z)-ΔPhe-Ozl-4-COOEt and its intermediate analog Ac-(Z)-ΔPhe-Ozn(4-OH)-4-COOEt were also determined. In a weakly polar environment, the ΔPhe-Ozl residue has a tendency to adopt the conformation β2 with the calculated φ and ψ angles of -127° and 0° for the isomer Z and -170° and 26° for the isomer E. The increase of environment polarity favors the helical conformation α and the beta-turn like conformation β, but the conformation β2 seems to be still accessible. The (E)-ΔPhe-Ozl residue can be obtained from the isomer Z in photoisomerization reaction. However, hydroxyl-oxazoline-dehydrophenylalanine ΔPhe-Ozn(4-OH) decomposes in such conditions. Alternatively, (E)-ΔPhe-NH2 can be applied as a substrate in the Hantzsch reaction. © 2016 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 106: 283-294, 2016.

  7. Probing ground and low-lying excited states for HIO2 isomers

    Science.gov (United States)

    de Souza, Gabriel L. C.; Brown, Alex

    2014-12-01

    We present a computational study on HIO2 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 × 10-3).

  8. An experimental and kinetic modeling study of the oxidation of the four isomers of butanol.

    Science.gov (United States)

    Moss, Jeffrey T; Berkowitz, Andrew M; Oehlschlaeger, Matthew A; Biet, Joffrey; Warth, Valérie; Glaude, Pierre-Alexandre; Battin-Leclerc, Frédérique

    2008-10-30

    Butanol, an alcohol which can be produced from biomass sources, has received recent interest as an alternative to gasoline for use in spark ignition engines and as a possible blending compound with fossil diesel or biodiesel. Therefore, the autoignition of the four isomers of butanol (1-butanol, 2-butanol, iso-butanol, and tert-butanol) has been experimentally studied at high temperatures in a shock tube, and a kinetic mechanism for description of their high-temperature oxidation has been developed. Ignition delay times for butanol/oxygen/argon mixtures have been measured behind reflected shock waves at temperatures and pressures ranging from approximately 1200 to 1800 K and 1 to 4 bar. Electronically excited OH emission and pressure measurements were used to determine ignition-delay times. The influence of temperature, pressure, and mixture composition on ignition delay has been characterized. A detailed kinetic mechanism has been developed to describe the oxidation of the butanol isomers and validated by comparison to the shock-tube measurements. Reaction flux and sensitivity analysis illustrates the relative importance of the three competing classes of consumption reactions during the oxidation of the four butanol isomers: dehydration, unimolecular decomposition, and H-atom abstraction. Kinetic modeling indicates that the consumption of 1-butanol and iso-butanol, the most reactive isomers, takes place primarily by H-atom abstraction resulting in the formation of radicals, the decomposition of which yields highly reactive branching agents, H atoms and OH radicals. Conversely, the consumption of tert-butanol and 2-butanol, the least reactive isomers, takes place primarily via dehydration, resulting in the formation of alkenes, which lead to resonance stabilized radicals with very low reactivity. To our knowledge, the ignition-delay measurements and oxidation mechanism presented here for 2-butanol, iso-butanol, and tert-butanol are the first of their kind.

  9. Backbone cyclization of analgesic conotoxin GeXIVA facilitates direct folding of the ribbon isomer.

    Science.gov (United States)

    Wu, Xiaosa; Huang, Yen-Hua; Kaas, Quentin; Harvey, Peta J; Wang, Conan K; Tae, Han-Shen; Adams, David J; Craik, David J

    2017-08-28

    Conotoxin GeXIVA inhibits the α9α10 nicotinic acetylcholine receptor (nAChR) and is analgesic in animal models of pain. α-conotoxins have four cysteines, which can have three possible disulfide connectivities: globular (CysI-CysIII and CysII-CysIV); ribbon (CysI-CysIV and CysII-CysIII) or bead (CysI-CysII and CysIII-CysIV). Native α-conotoxins preferably adopt the globular connectivity, and previous studies of α-conotoxins have focused on the globular isomers as the ribbon and bead isomers typically have lower potency at nAChRs than the globular form. A recent report showed that the bead and ribbon isomers of GeXIVA are more potent than the globular isomer, with low nanomolar half maximal inhibitory concentrations (IC50s). Despite this high potency, the therapeutic potential of GeXIVA is limited because, like most peptides, it is susceptible to proteolytic degradation and is challenging to synthesize in high yield. Here we used backbone cyclization as a strategy to improve the folding yield as well as increase the serum stability of ribbon GeXIVA while preserving activity at the α9α10 nAChR. Specifically, cyclization of ribbon GeXIVA with a two-residue linker maintained the biological activity at the human α9α10 nAChR and improved stability in human serum. Short linkers led to selective formation of the ribbon disulfide isomer without requiring orthogonal protection. Overall, this study highlights the value of backbone cyclization in directing folding, improving yields and stabilizing conotoxins with therapeutic potential. Copyright © 2017, The American Society for Biochemistry and Molecular Biology.

  10. Heroin discriminative stimulus effects of methadone, LAAM and other isomers of acetylmethadol in rats.

    Science.gov (United States)

    Newman, Jennifer L; Vann, Robert E; May, Everette L; Beardsley, Patrick M

    2002-10-01

    LAAM (alpha- l-acetylmethadol) is a derivative of the synthetic mu-opiate agonist methadone and is one of the four isomers of acetylmethadol. Methadone and LAAM have similar pharmacological properties and both are approved medications for the treatment of heroin dependency disorders. Few studies have reported on the pharmacology of acetylmethadol's other isomers and most of these have focused on their potential analgesic activity. The purpose of the present investigation was to examine the discriminative stimulus effects of LAAM, the other isomers of acetylmethadol, and methadone in rats trained to discriminate heroin from water, and to compare the duration of the discriminative stimulus effects of heroin, methadone, and LAAM. Long-Evans rats were trained to discriminate 0.3 mg/kg heroin from water under a fixed ratio 10 (FR10) schedule of food reinforcement. Dose-response functions for heroin, methadone, LAAM, three other isomers of acetylmethadol: alpha- d-acetylmethadol, beta- d-acetylmethadol, beta- l-acetylmethadol, and its precursor, beta- l-methadol were examined. Additionally, the time course effects for heroin, methadone, and LAAM were examined. LAAM and methadone dose-dependently occasioned heroin-like discriminative stimulus effects. Two of acetylmethadol's isomers, alpha- d-acetylmethadol and beta- d-acetylmethadol, were more potent than LAAM in producing heroin-like effects. The beta- l-methadol precursor and beta- l-acetylmethadol did not fully substitute for heroin's discriminative stimulus. LAAM elicited heroin-like discriminative stimulus effects for at least 6 h and generated partial generalization up to 36 h following administration. Methadone, LAAM, beta- d-acetylmethadol and alpha- d-acetylmethadol, but not beta- l-acetylmethadol and beta- l-methadol evoke heroin-like discriminative stimulus effects.

  11. 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 to differentiate under normal MS settings. Keywords: Chlorogenic acids, geometrical isomers, fragmentation, sodium adduct, QTOF- MS, Cone voltage. Rapid Communications in Mass Spectrometry 3 INTRODUCTION Caffeoylquinic acid (CQA) derivatives...-H-162]- was much more intense than that of the sodium adduct at m/z 375.065. [28] Between the cis isomers, the cis-cis isomer was observed to form more of the sodium adduct (m/z 375.065) relative to the deprotonated caffeoylquinic acid fragment (m...

  12. Trolox equivalent antioxidant capacity of different geometrical isomers of alpha-carotene, beta-carotene, lycopene, and zeaxanthin.

    Science.gov (United States)

    Böhm, Volker; Puspitasari-Nienaber, Ni Luh; Ferruzzi, Mario G; Schwartz, Steven J

    2002-01-02

    Isomerization of carotenoids, which is often encountered in food processing under the influence of temperature and light, may play a role in the observed protective effects of this group of secondary plant products. Investigation of in vitro antioxidant activity of prominent carotenoid geometrical isomers was undertaken in light of recent reports illustrating a large percentage of carotenoid (Z)-isomers in biological fluids and tissues. Alpha-carotene, beta-carotene, lycopene, and zeaxanthin were isolated from foods or supplements and subsequently photoisomerized with iodine as a catalyst. Major Z-isomers of each carotenoid were fractionated by semipreparative C(30) HPLC. In vitro antioxidant activity of all isomers collected was measured photometrically using the Trolox equivalent antioxidant capacity (TEAC) assay. TEAC values of 17 geometrical isomers investigated ranged from 0.5 to 3.1 mmol/L. Three unidentified (Z)-isomers of lycopene showed the highest antioxidant activity, being significantly higher than the result for (all-E)-lycopene, which had approximately two times the activity of (all-E)-beta-carotene. On the other hand, (9Z)-zeaxanthin had a more than 80% lower TEAC value compared to that of (all-E)-lycopene. These results allow for the in vivo relevance of (Z)-isomers of carotenoids to be considered.

  13. 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.

  14. Assessment of the in vivo genotoxicity of isomers of dinitrotoluene using the alkaline Comet and peripheral blood micronucleus assays.

    Science.gov (United States)

    Lent, Emily May; Crouse, Lee C B; Quinn, Michael J; Wallace, Shannon M

    2012-02-18

    Dinitrotoluene (DNT) is a nitroaromatic explosive that exists as six isomers; two major isomers (2,4- and 2,6-DNT) and four minor isomers (2,3-, 2,5-, 3,4-, and 3,5-DNT). DNT has been found in soil, surface water, and groundwater near ammunition production plants. The major isomers of DNT are classified as "likely to cause cancer in humans."In vitro studies have provided conflicting data regarding the genotoxicity of the minor isomers. Studies indicate that metabolism in the gut and liver are necessary to convert DNT to genotoxic compounds. As such, in the present study the genotoxicity of isomers of DNT was assessed using two in vivo genotoxicity assays. The Comet assay was used to detect DNA damage in liver cells from male Sprague-Dawley rats following oral exposure (14-day) to individual isomers of DNT. The micronucleus assay was conducted using flow cytometric analysis to detect chromosomal damage in peripheral blood. Treatment with 2,3-, 3,4-, 2,4-, 2,5- and 3,5-DNT did not induce DNA damage in liver cells or increase the frequency of micronucleated reticulocytes (MN-RET) in peripheral blood at the doses tested. Treatment with 2,6-DNT induced DNA damage in liver tissue at all doses tested, but did not increase the frequency of micronucleated reticulocytes (MN-RET) in peripheral blood. Thus, 2,4-DNT and the minor isomers were not genotoxic under these test conditions, while 2,6-DNT was genotoxic in the target tissue, the liver. These results support previous research which indicated that the hepatocarcinogenicity of technical grade DNT (TG-DNT) could be attributed to the 2,6-DNT isomer. Published by Elsevier B.V.

  15. High-K isomers in {sup 176}W and mechanisms of K-violation

    Energy Technology Data Exchange (ETDEWEB)

    Crowell, B.; Janssens, R.V.F.; Blumenthal, D.J. [and others

    1995-08-01

    K-isomers are states in deformed nuclei whose {gamma}-decay is hindered by selection rules involving K, the projection of the angular momentum along the axis of symmetry of the nucleus. Previous work with the Argonne Notre Dame BGO Array delineated the existence of two K-isomers in {sup 176}W, one of which had a very unusual pattern of decay. A short description of this work was published as a letter, and a more complete account is being readied for submission. These results provided evidence that quantum-mechanical fluctuations in the nuclear shape may be responsible for some of the observed K-violating transitions. In addition, hints were present in the data of the existence of another K-isomer with an even higher in. An experiment was performed in September 1994 to observe this isomer, using the reaction {sup 50}Ti({sup 130}Te,4n), and a technique in which recoiling {sup 176}W nuclei were created 17-cm upstream of the center of the array and caught on a Pb catcher foil at the center. Intense ({approximately} 3 pnA) beams of {sup 130}Te were supplied by the ECR source using a new sputtering technique. The recoil-shadow geometry was highly successful at removing the background from non-isomeric decays, allowing the weakly populated K-isomers to be detected cleanly. In addition, the availability of pulsed beams from ATLAS and the timing data from the BGO array provided a second technique for isolating the decays of interest, by selecting events in which a given number of BGO detectors fired between beam pulses. This method was used in the previous experiment, and was also applied in this experiment as a second level of selection. As a result, gamma-ray transitions were detected in the present experiment with intensities as small as {approximately} 0.02 % of the {sup 176}W reaction channel. The existence of the new isomer was confirmed, and a partial level-scheme was constructed.

  16. Optic glioma

    Science.gov (United States)

    Glioma - optic; Optic nerve glioma; Juvenile pilocytic astrocytoma; Brain cancer - optic glioma ... Optic gliomas are rare. The cause of optic gliomas is unknown. Most optic gliomas are slow-growing ...

  17. Isomer and β-decay spectroscopy of Tz=1 isotopes below the N=Z=50 shell gap

    Science.gov (United States)

    Boutachkov, P.; Braun, N.; Brock, T.; Nara Singh, B. S.; Blazhev, A.; Liu, Z.; Wadsworth, R.; Górska, M.; Grawe, H.; Pietri, S.; Domingo-Pardo, C.; Faestermann, T.; Farinon, F.; Grebosz, J.; Kojuharov, I.; Kurz, N.; Nociforo, C.; Podolyák, Zs; Prochazka, A.; Steer, S.; Cáceres, L.; Engert, T.; Gerl, J.; Goel, N.; Hoischen, R.; Schaffner, H.; Weick, H.; Wollersheim, H.-J.; Bettermann, L.; Finke, F.; Geibel, K.; Ilie, G.; Iwasaki, H.; Jolie, J.; Nyberg, J.; Reiter, P.; Scholl, C.; Söderström, P.-A.; Warr, N.; Eppinger, K.; Gottardo, A.; Hinke, C.; Krücken, R.; Pfützner, M.; Regan, P.; Rinta-Antila, S.; Rudolph, D.; Woods, P.; Ataç, A.; Merchán, E.

    2011-09-01

    The RISING setup at the GSI-FRS facility was used to investigate the isomer and beta decays in N~Z~50 Cd, Ag and Pd isotopes. A preliminary analysis of the data has revealed new results on the Tz=1, 94Pd, 96Ag and 98Cd isotopes. In 94Pd a new high-spin isomer was observed, whilst in 96Ag 3 new isomeric states were identified, including core-excited states. In 98Cd a new high-energy isomeric γ-ray transition is observed, thus enabling us to confirm the previous spin assignment for the core-excited 12+ isomer.

  18. Differentiation of flavonoid glycoside isomers by using metal complexation and electrospray ionization mass spectrometry.

    Science.gov (United States)

    Pikulski, Michael; Brodbelt, Jennifer S

    2003-12-01

    The elucidation of flavonoid isomers is accomplished by electrospray ionization tandem mass spectrometry (ESI-MS/MS) via formation and collisional activated dissociation (CAD) of metal/flavonoid complexes containing an auxiliary ligand. Addition of a metal salt and a suitable neutral auxiliary ligand to flavonoids in solution results in the formation of [M(II) (flavonoid-H) ligand]+ complexes by ESI which, upon collisional activated dissociation, often result in more distinctive fragmentation patterns than observed for conventional protonated or deprotonated flavonoids. Previously, 2,2'-bipyridine was used as an auxiliary ligand, and now we compare and explore the use of alternative pyridyl ligands, including 4,7-diphenyl-1,10-phenanthroline. Using this technique, three groups of flavonoid glycoside isomers are differentiated, including glycosides of apigenin, quercetin, and luteolin.

  19. Exclusive accumulation of Z-isomers of monolignols and their glucosides in bark of Fagus grandifolia

    Science.gov (United States)

    Lewis, N. G.; Inciong, E. J.; Ohashi, H.; Towers, G. H.; Yamamoto, E.

    1988-01-01

    In addition to Z-coniferyl and Z-sinapyl alcohols, bark extracts of Fagus grandifolia also contain significant amounts of the glucosides, Z-coniferin, Z-isoconiferin (previously called faguside) and Z-syringin. The corresponding E-isomers of these glucosides do not accumulate to a detectable level. The accumulation of the Z-isomers suggests that either they are not lignin precursors or that they are reservoirs of monolignols for subsequent lignin biosynthesis; it is not possible to distinguish between these alternatives. The co-occurrence of Z-coniferin and Z-isoconiferin demonstrate that glucosylation of monolignols can occur at either the phenolic or the allylic hydroxyl groups.

  20. Decays of the {sup 97}Y isomers to the single neutron nucleus {sup 97}Zr

    Energy Technology Data Exchange (ETDEWEB)

    Lhersonneau, G.; Dendooven, P.; Hankonen, S.; Honkanen, A.; Huhta, M.; Julin, R.; Juutinen, S.; Oinonen, M.; Penttilae, H.; Savelius, A.; Toermaenen, S.; Aeystoe, J. [Department of Physics, University of Jyvaeskylae, Finland, P.O. Box 35, FIN-40351 Jyvaeskylae (Finland); Butler, P.A.; Cocks, J.F.; Jones, P.M.; Smith, J.F. [Oliver Lodge Laboratory, University of Liverpool, P.O. Box 147, Liverpool L69 3BX (United Kingdom)

    1996-09-01

    The decays of the 9/2{sup +} and of the three-quasiparticle high spin isomer in {sup 97}Y have been investigated following on-line mass separation with the ion-guide technique. Spins and parities for several of the lowest-lying levels in the daughter nucleus {sup 97}Zr are revised and configurations are proposed. In particular, the 2264 keV level is identified as the {ital h}{sub 11/2} single-neutron level. The population of a cascade on top of the {ital h}{sub 11/2} level provides evidence for Gamow-Teller {beta} decay of the high-spin {sup 97}Y isomer. Levels and transition rates are qualitatively well reproduced by regarding {sup 97}Zr as a single-neutron nucleus with respect to the doubly closed {sup 96}Zr core. {copyright} {ital 1996 The American Physical Society.}

  1. Adsorptive process design for the separation of hexane isomers using zeolites.

    Science.gov (United States)

    Luna-Triguero, A; Gómez-Álvarez, P; Calero, S

    2017-02-15

    The product of catalytic isomerization is a mixture of linear and branched hydrocarbons that are in thermodynamic equilibrium, and their separation becomes necessary in the petrochemical industry. Zeolite 5A is usually industrially used to sieve alkane isomers, but its pore size allows only the separation of linear alkanes from the monobranched and dibranched alkanes by a kinetic mechanism. A more efficient approach to improve the average research octane number would be to adsorptively separate the di-methyl alkanes as products and recycle both the linear and mono-methyl alkanes to the isomerization reactor. Since the microscopic processes of adsorbates in zeolites are generally difficult or impossible to determine by experiments, especially in the case of mixtures, molecular simulation represents an attractive alternative. In this computational study, we propose a conceptual separation process for hexane isomers consisting of several adsorptive steps. Different zeolite topologies were examined for their ability to conduct this separation based on adsorption equilibrium and kinetics.

  2. Large-scale shell model study of the newly found isomer in 136La

    Science.gov (United States)

    Teruya, E.; Yoshinaga, N.; Higashiyama, K.; Nishibata, H.; Odahara, A.; Shimoda, T.

    2016-07-01

    The doubly-odd nucleus 136La is theoretically studied in terms of a large-scale shell model. The energy spectrum and transition rates are calculated and compared with the most updated experimental data. The isomerism is investigated for the first 14+ state, which was found to be an isomer in the previous study [Phys. Rev. C 91, 054305 (2015), 10.1103/PhysRevC.91.054305]. It is found that the 14+ state becomes an isomer due to a band crossing of two bands with completely different configurations. The yrast band with the (ν h11/2 -1⊗π h11 /2 ) configuration is investigated, revealing a staggering nature in M 1 transition rates.

  3. An experimental and kinetic modelling study of the oxidation of the four isomers of butanol

    CERN Document Server

    Moss, J T; Oehlschlaeger, M A; Biet, Joffrey; Warth, Valérie; Glaude, Pierre-Alexandre; Battin-Leclerc, Frédérique; 10.1021/jp806464p

    2008-01-01

    Butanol, an alcohol which can be produced from biomass sources, has received recent interest as an alternative to gasoline for use in spark ignition engines and as a possible blending compound with fossil diesel or biodiesel. Therefore, the autoignition of the four isomers of butanol (1-butanol, 2-butanol, iso-butanol, and tert-butanol) has been experimentally studied at high temperatures in a shock tube and a kinetic mechanism for description of their high-temperature oxidation has been developed. Ignition delay times for butanol/oxygen/argon mixtures have been measured behind reflected shock waves at temperatures and pressures ranging from approximately 1200 to 1800 K and 1 to 4 bar. Electronically excited OH emission and pressure measurements were used to determine ignition delay times. A detailed kinetic mechanism has been developed to describe the oxidation of the butanol isomers and validated by comparison to the shock tube measurements. Reaction flux and sensitivity analysis indicate that the consumpti...

  4. Spectroscopic quadrupole moments of high-spin isomers in {sup 193}Pb

    Energy Technology Data Exchange (ETDEWEB)

    Balabanski, D.L. [IKS, University of Leuven, Celestijnenlaan 200 D, B-3001, Leuven (Belgium); Faculty of Physics, St. Kliment Ohridski University of Sofia, BG-1164, Sofia (Bulgaria); Ionescu-Bujor, M.; Iordachescu, A.; Bucurescu, D. [National Institute for Physics and Nuclear Engineering, P.O. Box MG-6, Bucharest (Romania); Bazzacco, D.; Brandolini, F.; Menegazzo, R.; Pavan, P.; Rossi Alvarez, C. [Dipartimento di Fisica dell' Universita di Padova and INFN, Sezione di Padova, Padova (Italy); Chmel, S.; Huebel, H. [ISKP, Universitaet Bonn, D-53115, Bonn (Germany); Danchev, M. [Faculty of Physics, St. Kliment Ohridski University of Sofia, BG-1164, Sofia (Bulgaria); De Poli, M. [Laboratori Nazionali di Legnaro, INFN, Legnaro (Italy); Georgiev, G. [Grand Accelerateur National d' Ions Lourds, F-14076, Caen Cedex 5 (France); Haas, H. [Bereich Festkorperphysik, Hahn-Meitner Institut, D-14109, Berlin (Germany); Marginean, N. [National Institute for Physics and Nuclear Engineering, P.O. Box MG-6, Bucharest (Romania); Laboratori Nazionali di Legnaro, INFN, Legnaro (Italy); Neyens, G.; Vyvey, K. [IKS, University of Leuven, Celestijnenlaan 200 D, B-3001, Leuven (Belgium); Rainovski, G. [Faculty of Physics, St. Kliment Ohridski University of Sofia, BG-1164, Sofia (Bulgaria); Department of Physics, University of Liverpool, L69 7ZE, Liverpool (United Kingdom); Ur, C.A. [National Institute for Physics and Nuclear Engineering, P.O. Box MG-6, Bucharest (Romania); Dipartimento di Fisica dell' Universita di Padova and INFN, Sezione di Padova, Padova (Italy); Frauendorf, S.

    2004-04-01

    The quadrupole interaction of high-spin isomers in {sup 193}Pb implanted into solid Hg cooled at a temperature T=170 K has been investigated by the time-differential perturbed {gamma}-ray angular-distribution method. Spectroscopic quadrupole moment values of vertical stroke Q{sub s} vertical stroke =0.22(2) eb and 0.45(4) eb have been deduced for the 21/2{sup -} and 33/2{sup +} three-neutron states, respectively. A much higher value vertical stroke Q{sub s} vertical stroke =2.84(26) eb has been determined for the 29/2{sup -} isomer, the band head of a magnetic rotational band. (orig.)

  5. High-K isomers in $^{176}$W and mechanisms of K-violation

    CERN Document Server

    Crowell, B; Blumenthal, D J; Freeman, S J; Lister, C J; Carpenter, M P; Henry, R G; Janssens, R V F; Khoo, T L; Lauritsen, T; Liang, Y; Soramel, F; Bearden, I G; Crowell, B; Chowdhury, P; Blumenthal, D J; Freeman, S J; Lister, C J; Carpenter, M P; Henry, R G; Janssens, R V F; Khoo, T L; Lauritsen, T; Liang, Y; Soramel, F; Bearden, I G

    1996-01-01

    An isomer, with t1/2 = 35 +- 10 ns and J, Kpi = 14, 14+, has been observed in the nucleus 176W using the reaction 150Nd(30Si,4n) at a beam energy of 133 MeV. The isomer exhibits an unusual pattern of decay in which the _majority_ of the flux proceeds directly to states with =0, bypassing available levels of intermediate K. This severe breakdown of normal K-selection rules in 176W is compared with recent observations of K-violation in neighboring nuclei, within the framework of proposed theoretical approaches. The available data on these K-violating decays seem to have a consistent explanation in models of K-mixing which include large-amplitude fluctuations of the nuclear shape.

  6. 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.

  7. Purification of 2,6-Diisopropylnaphthalene by Static Melt Crystallization from a Mixture Containing Diisopropylnaphthalene Isomers

    Institute of Scientific and Technical Information of China (English)

    TIAN,Zheng-Hua; JIA,Hong-Min; ZHAO,Gui-Li; HU,Wei-Qi

    2007-01-01

    2,6-Diisopropylnaphthalene (2,6-DIPN), as the precursor of important monomer 2,6-naphthalene dicarboxylic acid, could be produced by the shape-selective isopropylation of naphthalene with propene resulting in an isomeric mixture having different alkylation levels. Since the boiling points of DIPNs were very close and the differences of melting points in-between isomers were quite distinctive, the static melt crystallization was applied to separate and purify 2,6-DIPN from its isomers. 2,6-DIPN with purity ≥99% was produced through a process of three stages:crystallization→sweating→melting. The phase diagram of 2,6-DIPN-2,7-DIPN binary system was plotted to optimize the temperature control of crystallization. By repeated crystallization of melts with different concentration levels, the yield of pure 2,6-DIPN could be enhanced to 87%. No solvent was necessary.

  8. Mass measurements and implications for the energy of the high-spin isomer in 94Ag

    CERN Document Server

    Kankainen, A; Batist, L; Eliseev, S; Eronen, T; Hager, U; Hakala, J; Jokinen, A; Moore, I D; Novikov, Yu N; Pentillä, H; Popov, A; Rahaman, S; Rinta-Antila, S; Rissanen, J; Saastamoinen, A; Seliverstov, D M; Sonoda, T; Vorobjev, G; Weber, C; Äystö, J

    2008-01-01

    Nuclides in the vicinity of 94Ag have been studied with the Penning trap mass spectrometer JYFLTRAP at IGISOL. The masses of the two-proton decay daughter 92Rh and the beta-decay daughter 94Pd of the high-spin isomer in 94Ag have been measured and the masses of 93Pd and 94Ag have been deduced. When combined with the data from the one-proton or two-proton decay experiments, the results lead to contradictory mass excess values for the high-spin isomer in 94Ag, -46370(170) keV or -44970(100) keV, corresponding to excitation energies of 6960(400) keV or 8360(370) keV, respectively.

  9. Electronic single-molecule identification of carbohydrate isomers by recognition tunnelling

    Science.gov (United States)

    Im, Jongone; Biswas, Sovan; Liu, Hao; Zhao, Yanan; Sen, Suman; Biswas, Sudipta; Ashcroft, Brian; Borges, Chad; Wang, Xu; Lindsay, Stuart; Zhang, Peiming

    2016-12-01

    Carbohydrates are one of the four main building blocks of life, and are categorized as monosaccharides (sugars), oligosaccharides and polysaccharides. Each sugar can exist in two alternative anomers (in which a hydroxy group at C-1 takes different orientations) and each pair of sugars can form different epimers (isomers around the stereocentres connecting the sugars). This leads to a vast combinatorial complexity, intractable to mass spectrometry and requiring large amounts of sample for NMR characterization. Combining measurements of collision cross section with mass spectrometry (IM-MS) helps, but many isomers are still difficult to separate. Here, we show that recognition tunnelling (RT) can classify many anomers and epimers via the current fluctuations they produce when captured in a tunnel junction functionalized with recognition molecules. Most importantly, RT is a nanoscale technique utilizing sub-picomole quantities of analyte. If integrated into a nanopore, RT would provide a unique approach to sequencing linear polysaccharides.

  10. Characterization of tetra-aryl benzene isomers by using preparative gas chromatography with mass spectrometry, nuclear magnetic resonance spectroscopy, and X-ray crystallographic methods.

    Science.gov (United States)

    Rühle, Christian P G; Niere, Julie; Morrison, Paul D; Jones, Roderick C; Caradoc-Davies, Tom; Canty, Allan J; Gardiner, Michael G; Tolhurst, Vicki-Anne; Marriott, Philip J

    2010-06-01

    The present study describes a preparative gas chromatographic (GC) approach employed to study a series of products arising from reaction of phenylacetylene with para-substituted aryl-iodides under Sonogashira catalysis conditions. GC analysis resolves the isomers from each reaction; however, it cannot provide structural details (their MS data are virtually identical). Since classical liquid chromatography cannot resolve the isomers, preparative-scale GC is the only practical approach to provide further spectroscopic characterization of the isomers. The products are well separated by GC so a single thick-film capillary column is adequate for this case, with operation up to approximately +300 degrees C. By collection of 50+ repeat injections, sufficient material could be isolated for (1)H NMR spectral analysis of the isomers, and for one isomer (isomer I) of a number of analogous related catalytic reaction mixtures, X-ray crystal structure determination enabled complete structural elucidation (absolute configuration) of the substitution pattern of the structure of this isomer. This confirmed isomer I to be the 2-para-aryl-substituted 1,3,5-triphenylbenzene product in all cases. (1)H NMR spectra of isomer I products generally had similar patterns but differed markedly from the second major isomer product (isomer II).

  11. Determination of ortho-cresyl phosphate isomers of tricresyl phosphate used in aircraft turbine engine oils by gas chromatography and mass spectrometry.

    Science.gov (United States)

    De Nola, G; Kibby, J; Mazurek, W

    2008-07-25

    Tricresyl phosphate (TCP) is used as an anti-wear additive in aircraft turbine engine oil. Concerns about its toxicity are largely based on the tri-o-cresyl phosphate isomer content. However, the presence of other and more toxic isomers has been previously suggested. In this work, the structural isomers of TCP have been determined by two methods (experimental and semi-theoretical). First, the TCP isomers were separated by gas chromatography (GC) and identified by mass spectrometry (MS). Second, after base cleavage of TCP, GC was used to quantify the cresol precursors. These results were used to calculate the TCP isomer distribution based on the assumption of a statistical distribution of the TCP isomers. The results from the two determinations showed reasonable agreement for three of the four oils studied. The o-cresyl isomers were found to be present almost exclusively as the more toxic mono-o-cresyl isomers in the concentration range 13-150 mg/L. The ability to analyse for the mono-o-cresyl isomers allows the toxicity of TCP to be based on the latter isomers rather than on the less toxic tri-o-cresyl phosphate isomer.

  12. 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

    in primary human adipocytes in vitro. Here we investigated the mechanism behind the isomer-specific, CLA-mediated reduction in TG accumulation in differentiating human preadipocytes. Trans-10,cis-12 CLA decreased insulin-stimulated glucose uptake and oxidation, and reduced insulin-dependent glucose...... uptake and oxidation and preadipocyte differentiation by altering preadipocyte gene transcription in a manner that appeared to be due, in part, to decreased PPARgamma expression....

  13. Regiospecific formation of cobamide isomers is directed by CobT.

    Science.gov (United States)

    Crofts, Terence S; Hazra, Amrita B; Tran, Jennifer L A; Sokolovskaya, Olga M; Osadchiy, Vadim; Ad, Omer; Pelton, Jeffrey; Bauer, Stefan; Taga, Michiko E

    2014-12-16

    Cobamides, which include vitamin B₁₂ (cobalamin), are a class of modified tetrapyrroles synthesized exclusively by prokaryotes that function as cofactors for diverse biological processes. Cobamides contain a centrally bound cobalt ion that coordinates to upper and lower axial ligands. The lower ligand is covalently linked to a phosphoribosyl moiety through an alpha-glycosidic bond formed by the CobT enzyme. CobT can catalyze the phosphoribosylation of a variety of substrates. We investigated the ability of CobT to act on either of two nitrogen atoms within a single, asymmetric benzimidazole substrate to form two isomeric riboside phosphate products. Reactions containing asymmetric benzimidazoles as substrates for homologues of CobT from different bacteria resulted in the production of distinct ratios of two isomeric products, with some CobT homologues favoring the production of a single isomer and others forming a mixture of products. These preferences were reflected in the production of cobamide isomers with lower ligands attached in different orientations, some of which are novel cobamides that have not been characterized previously. Two isomers of methoxybenzimidazolylcobamide were found to be unequal in their ability to support ethanolamine ammonia-lyase dependent growth in Salmonella enterica, suggesting that CobT's regiospecificity could be biologically important. We also observed differences in pKa, which can influence the reactivity of the cofactor and could contribute to these distinct biological activities. Relaxed regiospecificity was achieved by introducing a single point mutation in an active site residue of CobT. These new cobamide isomers could be used to probe the mechanisms of cobamide-dependent enzymes.

  14. Ignition of Isomers of Pentane: An Experimental and Kinetic Modeling Study

    Science.gov (United States)

    2000-08-04

    diesel engines [26,27], and ignition under homogeneous charge compres- sion ignition ( HCCI ) conditions [26,28]. Kinetic modeling shows that the isomers of...Introduction Hydrocarbon ignition is important in many prac- tical combustion systems, including internal com- bustion engines , detonations, pulse combustors...tem- peratures are similar to those in automotive engines during diesel ignition and end-gas autoignition in spark-ignition engines . The RCM provides

  15. Catalytic Oxidative Dehydration of Butanol Isomers: 1-Butanol, 2-Butanol, and Isobutanol

    Science.gov (United States)

    2011-09-01

    G.; Russo, M. E.; Marzocchella, A.; Salatino, P. Butanol Production by Clostridium Acetobutylicum in a Continuous Packed Bed Reactor. Journal of...industries because it is easily available through fermentation of non-food biomass and wastewater (1–3). Dehydration of butanol isomers (1-butanol, 2... Fermentative Butanol Production by Clostridia. Biotechnology and Bioengineering 2008, 101, 209–228. 3. Zverlov, V. V.; Berezina, O.; Velikodvorskaya, G. A

  16. Analysis of shape isomer yields of 237Pu in the framework of dynamical–statistical model

    Indian Academy of Sciences (India)

    Hadi Eslamizadeh

    2012-02-01

    Data on shape isomer yield for + 235U reaction at $E^{\\text{lab}}$ = 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 well should be less than the results of statistical model calculations.

  17. Efficient algorithms to enumerate isomers and diamutamers with more than one type of substituent

    Science.gov (United States)

    van Almsick M; Dolhaine; Honig

    2000-07-01

    In this paper we describe numeric as well as symbolic algorithms for the enumeration of substitutional isomers with an unlimited number of different achiral substituents. We consider three different scenarios: first, the enumeration of diamutamers with a given set of ligand types and ligand multiplicity, second, the enumeration of diamutamer libraries with a given ligand assortment pattern, and, third, the enumerations of libraries with diamutamers exhibiting a limited number of ligands.

  18. Separation and identification of Taxifolin 3-O-glucoside isomers from Chamaecyparis obtusa (Cupressaceae).

    Science.gov (United States)

    Sakushima, Akiyo; Ohno, Kosei; Coskun, Makusut; Seki, Koh-Ichi; Ohkura, Kazue

    2002-12-01

    Taxifolin 3-O-glucoside isomers, [(2R, 3R)-, (2R, 3S)-, (2S, 3R)- and (2S, 3S)-] were isolated from leaves of Chamaecyparis obtuse (Cupressaceae). Their structures were elucidated on the basis of UV, MS, CD, 1H- and 13C-NMR spectral data, including 2D shift correlation. It was found that the compounds could be distinguished by the use of 1H- and 13C-NMR spectral data.

  19. Investigation of HNCO isomer formation in ice mantles by UV and thermal processing: An experimental approach

    Energy Technology Data Exchange (ETDEWEB)

    Jiménez-Escobar, A.; Giuliano, B. M.; Caro, G. M. Muñoz; Cernicharo, J. [Centro de Astrobiología, INTA-CSIC, Carretera de Ajalvir, km 4, Torrejón de Ardoz, E-28850 Madrid (Spain); Marcelino, N., E-mail: bgiuliano@cab.inta-csic.es [National Radio Astronomy Observatory, 520 Edgemont Road, Charlottesville, VA 22903 (United States)

    2014-06-10

    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{sub 2}O, NH{sub 3}, CO, HCN, CH{sub 3}OH, CH{sub 4}, and N{sub 2} followed by warm-up under astrophysically relevant conditions. Only the H{sub 2}O:NH{sub 3}:CO and H{sub 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{sub 2}O:NH{sub 3}:CO and H{sub 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{sub 2}O:NH{sub 3}:CO and H{sub 2}O:HCN ices lead to the formation of OCN{sup –} 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.

  20. PARTICLE-HOLE NATURE OF THE LIGHT HIGH-SPIN TOROIDAL ISOMERS

    Energy Technology Data Exchange (ETDEWEB)

    Staszczak, A. [Maria Curie-Sklodowska University, Poland; Wong, Cheuk-Yin [ORNL

    2015-01-01

    Nuclei under non-collective rotation with a large angular momentum above some threshold can assume a toroidal shape. In our previous work, we showed by using cranked Skyrme Hartree Fock approach that even even, N = Z, high-K, toroidal isomeric states may have general occurrences for light nuclei with 28 < A < 52. We present here some additional results and systematics on the particle-hole nature of these high-spin toroidal isomers.

  1. Detection of biologically active isomers of conjugated linoleic acid in kaymak

    OpenAIRE

    Ökten, Sevtap; Gönç, Siddik; Tokusoglu, Özlem; Sibel Akalin, A.

    2005-01-01

    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 s...

  2. Trans fatty acid isomers from hydrogenated fats: The controversy about health implications

    OpenAIRE

    Valenzuela, Alfonso; King, Judith; Nieto, Susana

    1995-01-01

    Wherever there is a double bond in a fatty acid, there is also a possibility for isomerization. Under partial hydrogenation triacylglycerols composing oils'double bonds may change from cis to trans configuration, therefore products derived from hydrogenated oils such as margarines, shortenings and other industrial fats show high content of trans fatty acid isomers. The health implications of trans fatty acids in our d...

  3. Low and High Temperature Combustion Chemistry of Butanol Isomers in Premixed Flames and Autoignition Systems

    Energy Technology Data Exchange (ETDEWEB)

    Sarathy, S M; Pitz, W J; Westbrook, C K; Mehl, M; Yasunaga, K; Curran, H J; Tsujimura, T; Osswald, P; Kohse-Hoinghaus, K

    2010-12-12

    Butanol is a fuel that has been proposed as a bio-derived alternative to conventional petroleum derived fuels. The structural isomer in traditional 'bio-butanol' fuel is n-butanol, but newer conversion technologies produce iso-butanol as a fuel. In order to better understand the combustion chemistry of bio-butanol, this study presents a comprehensive chemical kinetic model for all the four isomers of butanol (e.g., 1-, 2-, iso- and tert-butanol). The proposed model includes detailed high temperature and low temperature reaction pathways. In this study, the primary experimental validation target for the model is premixed flat low-pressure flame species profiles obtained using molecular beam mass spectrometry (MBMS). The model is also validated against previously published data for premixed flame velocity and n-butanol rapid compression machine and shock tube ignition delay. The agreement with these data sets is reasonably good. The dominant reaction pathways at the various pressures and temperatures studied are elucidated. At low temperature conditions, we found that the reaction of alphahydroxybutyl with O{sub 2} was important in controlling the reactivity of the system, and for correctly predicting C{sub 4} aldehyde profiles in low pressure premixed flames. Enol-keto isomerization reactions assisted by HO{sub 2} were also found to be important in converting enols to aldehydes and ketones in the low pressure premixed flames. In the paper, we describe how the structural features of the four different butanol isomers lead to differences in the combustion properties of each isomer.

  4. 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 (pcoffee. CGA isomer content was positively correlated (pcoffee to reduce nitric oxide and scavenge Frémy's salt. Indices of browning in roasted coffee were positively correlated (pcoffee 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.

  5. The Immunomodulatory Activity of Jacaric Acid, a Conjugated Linolenic Acid Isomer, on Murine Peritoneal Macrophages.

    Directory of Open Access Journals (Sweden)

    Wai Nam Liu

    Full Text Available This study aims at demonstrating the immunomodulatory property of jacaric acid, a conjugated linolenic acid (CLNA isomer that is present in jacaranda seed oil, on murine peritoneal macrophages. Our results showed that jacaric acid exhibited no significant cytotoxicity on the thioglycollate-elicited murine peritoneal macrophages as revealed by the neutral red uptake assay, but markedly increased their cytostatic activity on the T-cell lymphoma MBL-2 cells as measured by the fluorometric CyQuant® NF Cell Proliferation Assay Kit. Flow cytometric analysis indicated that jacaric acid could enhance the endocytic activity of macrophages and elevated their intracellular production of superoxide anion. Moreover, jacaric acid-treated macrophages showed an increase in the production of nitric oxide which was accompanied by an increase in the expression level of inducible nitric oxide synthase protein. In addition, the secretion of several pro-inflammatory cytokines, including interferon-γ, interleukin-1β and tumor necrosis factor-α, was up-regulated. Collectively, our results indicated that the naturally-occurring CLNA isomer, jacaric acid, could exhibit immunomodulating activity on the murine peritoneal macrophages in vitro, suggesting that this CLNA isomer may act as an immunopotentiator which can be exploited for the treatment of some immunological disorders with minimal toxicity and fewer side effects.

  6. Prospect of triggering the 178m2Hf isomer and the role of resonance conversion

    Science.gov (United States)

    Karpeshin, F. F.; Trzhaskovskaya, M. B.; Zhang, J.

    2009-03-01

    A mechanism of triggering the 12.7keV E3 transition, based on the new decay mode of the 31y isomer via resonance internal conversion and emission of a 1.4keV X-ray quantum, is considered. Actually, this decay mode was observed previously in the decay of 45- and 46-fold ions of 125Te . For the purpose of triggering, the atomic radiative vertex has to be induced by resonance radiation. This mechanism makes triggering by an order of magnitude more efficient than triggering a bare nucleus, and is achieved at a lower combination frequency. An experiment is proposed for the direct observation of the new decay mode. This also offers a new way of resonance scattering of these X-rays. Triggering through higher-lying 2573 and 2805keV states is also considered. The results are extended to the general problem of triggering. The main obstacle for enhancing the efficiency is a high internal conversion rate. For this reason, shape isomers with low multipole order -- E1 , M1 , and with a high enough energy of triggering transition are of interest for triggering. The partial ionization of the outer electrons will also help. The same recommendations hold for triggering isomers in laser-produced plasma.

  7. Control of multiscale systems with constraints. 2. Fractal nuclear isomers and clusters

    CERN Document Server

    Adamenko, S; Novikov, V

    2013-01-01

    We consider the influence of the Fermi statistics of nucleons on the binding energy of a new type of nuclear structures such as fractal nuclear clusters (fractal isomers of nuclei). It is shown that the fractal nuclear isomers possess a wide spectrum of binding energies that exceed, in many cases, the values known at the present time. The transition of the nuclear matter in the form of ordinary nuclei (drops of the nuclear fluid) in the state with the fractal structure or in the form of bubble nuclei opens new sources of energy and has huge perspectives. This transition is based on a new state of matter - collective coherently correlated state. It manifests itself, first of all, in the property of nonlocality of nuclear multiparticle processes. We develop a phenomenological theory of the binding energy of nuclear fractal structures and modify the Bethe - Weizs\\"acker formula for nuclear clusters with the mass number A, charge Z, and fractal dimension D_f. The consideration of fractal nuclear isomers allows on...

  8. Partition function and astronomical observation of interstellar isomers: Is there a link?

    Science.gov (United States)

    Etim, Emmanuel E.; Arunan, Elangannan

    2017-02-01

    The unsuccessful astronomical searches for some important astrophysical and astrobiological molecules have been linked to the large partition function of these molecules. This letter reports an extensive investigation of the relationship between partition function and astronomical observation of interstellar isomers using high level quantum chemical calculations. 120 molecules from 30 different isomeric groups have been considered. Partition function and thermodynamic stabilities are determined for each set of isomeric species. From the results, there is no direct correlation between partition function and astronomical observation of the same isomeric species. Though interstellar formations processes are generally controlled by factors like kinetics, thermodynamics, formation and destruction pathways. However, the observation of the isomers seems to correlate well with thermodynamics. For instance, in all the groups considered, the astronomically detected isomers are the thermodynamically most stable molecules in their respective isomeric groups. The implications of these results in accounting for the limited number of known cyclic interstellar molecules, unsuccessful searches for amino acid and the possible molecules for astronomical observations are discussed.

  9. 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.

  10. 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.

  11. Screening of multicomponent crystals of L-tryptophan with three isomers of pyridinedicarboxylic acids

    Science.gov (United States)

    Das, Babulal

    2016-08-01

    Multicomponent crystallization of L-tryptophan with three different isomers of pyridinedicarboxylic acids, namely, 2,3-pyridinedicarboxylic acid (2,3-PDA), 2,5-pyridinedicarboxylic acid (2,5-PDA) and 2,6-pyridinedicarboxylic acid (2,6-PDA), were screened using conventional solution cocrystallization technique. Whereas the new phases derived from the amino acid with 2,3-PDA or 2,5-PDA were analyzed using powder X-ray diffraction and thermal analysis techniques, the crystalline phase synthesized from 2,6-substituted isomer was further characterized by single crystal X-ray diffraction. Structural analysis revealed that the amino acid exists in the zwitterionic form interacting with the neutral 2,6-PDA by strong intermolecular hydrogen bonding. The components in the co-crystal self-assemble leading to a three dimensional hydrogen bonded closed packed network structure. Isothermal calorimetric titration showed that among the three isomers, 2,6-PDA showed relatively strong binding interaction towards the amino acid in water at 298 K. All the crystals exhibit marginal quenching of fluorescence properties of L-tryptophan in the solid state.

  12. 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

    2015-01-16

    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.

  13. Thermal decomposition of 1-pentanol and its isomers: a theoretical study.

    Science.gov (United States)

    Zhao, Long; Ye, Lili; Zhang, Feng; Zhang, Lidong

    2012-09-20

    Pentanol is one of the promising "next generation" alcohol fuels with high energy density and low hygroscopicity. In the present work, dominant reaction channels of thermal decomposition of three isomers of pentanol: 1-pentanol, 2-methyl-1-butanol, and 3-methyl-1-butanol were investigated by CBS-QB3 calculations. Subsequently, the temperature- and pressure-dependent rate constants for these channels were computed by RRKM/master equation simulations. The difference between the thermal decomposition behavior of pentanol and butanol were discussed, while butanol as another potential alternative alcohol fuel has been extensively studied both experimentally and theoretically. Rate constants of barrierless bond dissociation reactions of pentanol isomers were treated by the variational transition state theory. The comparison between various channels revealed that the entropies of variational transition states significantly impact the rate constants of pentanol decomposition reactions. This work provides sound quality kinetic data for major decomposition channels of three pentanol isomers in the temperature range of 800-2000 K with pressure varying from 7.6 to 7.6 × 10(4) Torr, which might be valuable for developing detailed kinetic models for pentanol combustion.

  14. Reaction dynamics of Cl + butanol isomers by crossed-beam sliced ion imaging.

    Science.gov (United States)

    Estillore, Armando D; Visger-Kiefer, Laura M; Suits, Arthur G

    2012-01-01

    Butanol is now prominent among the prototype renewable biofuels. We have studied oxidation of a variety of butanol isomers under single collision conditions using chlorine atom as the oxidizing agent to gain detailed insight into the energetics and dynamics of these reactions. The interaction of chlorine atom radicals with butanol isomers: n-butanol, iso-butanol, sec-butanol, and tert-butanol have been studied by crossed-beam dc slice ion imaging techniques. The hydroxybutyl radicals generated from the H-abstraction processes were probed by single photon ionization using an F2 excimer laser. After background subtraction and density-to-flux correction of the raw images, translational energy distribution and product angular distributions were generated. At low collision energy, the hydroxyalkyl products are backscattered with respect to the alcohol beam and the scattering shifts to the forward direction as the collision energy is increased. The translational energy distributions are reminiscent to that of Cl + pentane reactions we studied earlier, i.e. a sharp forward peak -80% of the collision energy appears at the high collision energy. Isomer-specific details of the reactions will be discussed.

  15. 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

  16. Anionic fructose-related conformational and positional isomers assigned through PES experiments and DFT calculations.

    Science.gov (United States)

    Zeng, Zhen; Bernstein, Elliot R

    2017-08-30

    Gas phase, isolated fructose anionic species, fructose(-), (fructose-H)(-), (fructose-OH)(-), and (fructose-H2O)(-), are investigated employing anionic photoelectron spectroscopy (PES) combined with density functional theory (DFT) calculations. The PES vertical detachment energies (VDEs) for these anions are determined and, based on these experimental values, their calculated anionic structures are assigned. Generation of these four species through the matrix assisted laser desorption ionization (MALDI) process is sample desorption substrate dependent. The parent anion fructose(-) exists as a single, dominant open chain structure in the gas phase, with substrate dependent specific conformational isomers. (Fructose-H)(-) and (fructose-OH)(-) are mainly produced from the laser ablation process rather than from fragmentation reaction pathways associated with the parent anion species. Both conformational and positional isomers are identified in the gas phase for these latter anions. (Fructose-H2O)(-) has two types of positional isomers, both of which contribute to two different components of the observed PES feature. The fixed positions for losing an OH group and an H atom, in addition to thermodynamic calculations, provide reaction pathways for generating a dehydration product (open chain structures) from the parent anion (open chain and furanose structures), further demonstrating the active nature of fructose upon capturing an extra electron.

  17. Supplementation with CLA: isomer incorporation into serum lipids and effect on body fat of women.

    Science.gov (United States)

    Petridou, Anatoli; Mougios, Vassilis; Sagredos, Angelos

    2003-08-01

    Animal studies have suggested that CLA, a natural component of meat and dairy products, may confer beneficial effects on health. However, human studies using supplementation with CLA have produced contradictory results. The aim of the present study was to further investigate the effect of CLA supplementation on human body fat, serum leptin, and serum lipids, as well as the incorporation of CLA isomers into serum lipids classes. Sixteen young healthy nonobese sedentary women received 2.1 g of CLA (divided equally between the cis,trans-9,11 and trans,cis-10,12 isomers) daily for 45 d and placebo for 45 d in a randomized double-blind crossover design. Body fat was estimated (by measurement of skinfold thickness at 10 sites), and blood was sampled at the beginning, middle, and end of the entire intervention period; an additional blood sample was obtained 2 wk thereafter. No significant differences in energy, carbohydrate, lipid, or protein intake existed between the CLA and placebo intake periods. No significant differences were found in body fat or serum leptin, TAG, total cholesterol, HDL-cholesterol, and alanine aminotransferase between CLA and placebo. The CLA isomer content of serum TAG, phospholipids, and total lipids increased 2-5 times with CLA supplementation (P lipids. These data indicate that supplementation with 2.1 g of CLA daily for 45 d increased its levels in blood but had no effect on body composition or the lipidemic profile of nonobese women.

  18. 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.

  19. Characterization of charge isomers of yeast phosphoglycerate kinase. Evidence for intracellular differences.

    Science.gov (United States)

    Arvidsson, L; Schierbeck, B; Larsson-Raźnikiewicz, M

    1976-01-01

    Three electrophoretic components of phosphoglycerate kinase have been isolated from baker's yeast. The isoionic point of the major component is 7.18 at 10 degrees C. Corresponding values for the minor ones are 6.91 and 7.48, respectively. There is a difference of one charge-unit between the isomers 1 and 2, and between the isomers 2 and 3. The release of component 3 from the yeast cells appears in contrast to the isomers 1 and 2 to be promoted by an organic solvent, thus suggesting this component to be bound to the cell-membrane. The amino-terminal amino acid residue appears to be N-acetylated serine in each of the three cases. The carboxyl-terminal ends seem to be identical also with -(Ala, Leu, Val, Lys)- Ala-Lys as the ultimate sequence. From the circular dichroism spectra the contents of alpha-helix and beta-structure were estimated to 15 and 40-50%, respectively. Factors have been determined for transformation and comparison of the specific activities as determined under the various conditions used at different laboratories.

  20. First principles electron-correlated calculations of optical absorption in magnesium clusters

    CERN Document Server

    Shinde, Ravindra

    2015-01-01

    In this paper we report the calculations of linear optical absorption spectra of various isomers of magnesium clusters Mg$_{n}$ (n=2--5) involving valence transitions, performed using the large-scale all-electron configuration interaction (CI) methodology. First, geometries of several low-lying isomers of each cluster were optimized at the coupled-cluster singles doubles (CCSD) level of theory. These geometries were subsequently employed to perform ground and excited state calculations on these systems using the multi-reference singles-doubles configuration-interaction (MRSDCI) approach, which includes electron correlation effects at a sophisticated level. Resultant CI wave functions were used to compute the optical absorption spectra within the electric-dipole approximation. Our results on magnesium dimer (Mg$_{2}$) isomer are in excellent agreement with the experiments as far as oscillator strengths, and excitation energies are concerned. Owing to a better description of electron-correlation effects, these ...

  1. Conformational gel analysis and graphics: Measurement of side chain rotational isomer populations by NMR and molecular mechanics

    CERN Document Server

    Haydock, Christopher

    2007-01-01

    Conformational gel analysis and graphics systematically identifies and evaluates plausible alternatives to the side chain conformations found by conventional peptide or protein structure determination methods. The proposed analysis determines the populations of side chain rotational isomers and the probability distribution of these populations. The following steps are repeated for each side chain of a peptide or protein: first, extract the local molecular mechanics of side chain rotational isomerization from a single representative global conformation; second, expand the predominant set of rotational isomers to include all probable rotational isomers down to those that constitute just a small percentage of the population; and third, evaluate the constraints vicinal coupling constants and NOESY cross relaxation rates place on rotational isomer populations. In this article we apply conformational gel analysis to the cobalt glycyl-leucine dipeptide and detail the steps necessary to generalize the analysis to oth...

  2. Discrimination of eight chloramphenicol isomers by liquid chromatography tandem mass spectrometry in order to investigate the natural occurence of chloramphenicol

    NARCIS (Netherlands)

    Berendsen, B.J.A.; Zuidema, T.; Jong, de J.; Stolker, A.A.M.; Nielen, M.W.F.

    2011-01-01

    This paper describes the discrimination of eight different isomers of chloramphenicol (CAP), an antibiotic banned for use in food producing animals, by reversed phase and chiral liquid chromatography in combination with tandem mass spectrometric detection. Previously, by liquid chromatography couple

  3. Production of isotopes and isomers with irradiation of Z = 47–50 targets by 23-MeV bremsstrahlung

    Energy Technology Data Exchange (ETDEWEB)

    Karamian, S. A., E-mail: karamian@nrmail.jinr.ru [Joint Institute for Nuclear Research (Russian Federation); Carroll, J. J. [US Army Research Laboratory (United States); Aksenov, N. V.; Albin, Yu. A.; Belov, A. G.; Bozhikov, G. A.; Dmitriev, S. N.; Starodub, G. Ya. [Joint Institute for Nuclear Research (Russian Federation)

    2015-09-15

    The irradiations of Ag to Sn targets by bremsstrahlung generated with 23-MeV electron beams are performed at the MT-25 microtron. Gamma spectra of the induced activities have been measured and the yields of all detected radionuclides and isomers are carefully measured and analyzed. A regular dependence of yields versus changed reaction threshold is confirmed. Many isomers are detected and the suppression of the production probability is observed with growing product spin. Special peculiarities for the isomer-to-ground state ratios were deduced for the {sup 106m}Ag, {sup 108m}Ag, {sup 113m}In, {sup 115m}In, and {sup 123m}Sn isomers. The production of such nuclides as {sup 108m}Ag, {sup 115m}In, {sup 117g}In, and {sup 113m}Cd is of interest for applications, especially when economic methods are available.

  4. Enantioseparation of Dencichine and D-Isomer on L-Cysteine Derivative Phase by Ligand-exchange Chromatography

    Institute of Scientific and Technical Information of China (English)

    Yan Shun MA; Qing Hua MENG; Hong Yu SHI; Yuan De LONG; Tian Bao HUANG

    2006-01-01

    The enantioseparation of dencichine and its D-isomer was achieved on a novel chiral stationary phase via coating N-(2-hydroxyl-3-octoxyl) propyl-S-benzyl-(L)-cysteine on YWG-C18phase by ligand exchange chromatography.

  5. Solvent effect on the stability and properties of platinum-substituted borirene and boryl isomers: The polarizable continuum model

    Science.gov (United States)

    Ghiasi, Reza; Peikari, Ali

    2016-11-01

    The structure and properties of platinum borirene complex trans-[Cl(PMe3)2Pt{μ-BN(SiMe3)2C=C}Ph] and its isomer the platinum boryl complex trans-[Cl(PMe3)2PtBN(SiMe3)2C≡CPh] were investigated theoretically. The solvent effect on the stability, structural parameters, frontier orbital energies, HOMO-LUMO gaps, and hardness of isomers was investigated using the polarizable continuum model (PCM). It was found that borirene isomer is the most stable isomer in the gas phase and solvent. The calculated results show that the presence of solvent reduces the frontier orbital energy of the studied molecules. Geometries obtained from calculations were used to perform NBO analysis.

  6. Ab initio correlated study of the Al13H- anion: Isomers, their kinetic stability and vertical detachment energies

    Science.gov (United States)

    Moc, Jerzy

    2012-01-01

    We report correlated ab initio calculations for the Al13H- cluster anion isomers, their kinetic stability and vertical detachment energies (VDEs). Of the two most energetically favored anion structures involving H atom in terminal and threefold bridged sites of the icosahedral Al13-, the higher energy ‘threefold bridged' isomer is shown to be of low kinetic stability. Our results are consistent with the recent photoelectron spectroscopy (PE) study of Grubisic et al. who observed two distinct Al13H- isomers, one of them identified as ‘metastable'. The VDE energies computed at the CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVDZ level for the ‘terminal' and ‘threefold bridged' Al13H- isomers of 3.21 and 2.32 eV are in good agreement with those determined in the PE study.

  7. 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.

  8. 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

  9. An experimental and kinetic modeling study of combustion of isomers of butanol

    Energy Technology Data Exchange (ETDEWEB)

    Grana, Roberto; Frassoldati, Alessio; Faravelli, Tiziano; Ranzi, Eliseo [Dipartimento di Chimica, Materiali e Ingegneria Chimica, Politecnico di Milano, Milano (Italy); Niemann, Ulrich; Seiser, Reinhard; Cattolica, Robert; Seshadri, Kalyanasundaram [Department of Mechanical and Aerospace Engineering, University of California at San Diego, La Jolla, CA 92093-0411 (United States)

    2010-11-15

    A kinetic model is developed to describe combustion of isomers of butanol - n-butanol (n-C{sub 4}H{sub 9}OH), sec-butanol (sec-C{sub 4}H{sub 9}OH), iso-butanol (iso-C{sub 4}H{sub 9}OH), and tert-butanol (tert-C{sub 4}H{sub 9}OH). A hierarchical approach is employed here. This approach was previously found to be useful for developing detailed and semi-detailed mechanism of oxidation of various hydrocarbon fuels. This method starts from lower molecular weight compounds of a family of species and proceeds to higher molecular weight compounds. The pyrolysis and oxidation mechanisms of butanol isomers are similar to those for hydrocarbon fuels. Here, the development of the complete set of the primary propagation reactions for butanol isomers proceeds from the extension of the kinetic parameters for similar reactions already studied and recently revised for ethanol, n-propanol and iso-propanol. A detailed description leading to evaluation of rate constants for initiation reactions, metathesis reactions, decomposition reactions of alkoxy radicals, isomerization reactions, and four-center molecular dehydration reactions are given. Decomposition and oxidation of primary intermediate products are described using a previously developed semi-detailed kinetic model for hydrocarbon fuels. The kinetic mechanism is made up of more than 7000 reactions among 300 species. The model is validated by comparing predictions made using this kinetic model with previous and new experimental data on counterflow non-premixed flames of n-butanol and iso-butanol. The structures of these flames were measured by removing gas samples from the flame and analyzing them using a gas chromatograph. Temperature profiles were measured using coated thermocouples. The flame structures were measured under similar conditions for both fuels to elucidate the similarities and differences in combustion characteristics of the two isomers. The profiles measured include those of butanol, oxygen, carbon dioxide

  10. Identification of structurally closely related monosaccharide and disaccharide isomers by PMP labeling in conjunction with IM-MS/MS.

    Science.gov (United States)

    Yang, Hongmei; Shi, Lei; Zhuang, Xiaoyu; Su, Rui; Wan, Debin; Song, Fengrui; Li, Jinying; Liu, Shuying

    2016-06-16

    It remains particularly difficult for gaining unambiguous information on anomer, linkage, and position isomers of oligosaccharides using conventional mass spectrometry (MS) methods. In our laboratory, an ion mobility (IM) shift strategy was employed to improve confidence in the identification of structurally closely related disaccharide and monosaccharide isomers using IMMS. Higher separation between structural isomers was achieved using 1-phenyl-3-methyl-5-pyrazolone (PMP) derivatization in comparison with phenylhydrazine (PHN) derivatization. Furthermore, the combination of pre-IM fragmentation of PMP derivatives provided sufficient resolution to separate the isomers not resolved in the IMMS. To chart the structural variation observed in IMMS, the collision cross sections (CCSs) for the corresponding ions were measured. We analyzed nine disaccharide and three monosaccharide isomers that differ in composition, linkages, or configuration. Our data show that coexisting carbohydrate isomers can be identified by the PMP labeling technique in conjunction with ion-mobility separation and tandem mass spectrometry. The practical application of this rapid and effective method that requires only small amounts of sample is demonstrated by the successful analysis of water-soluble ginseng extract. This demonstrated the potential of this method to measure a variety of heterogeneous sample mixtures, which may have an important impact on the field of glycomics.

  11. The antiproliferative effects of biologically active isomers of conjugated linoleic acid on human colorectal and prostatic cancer cells.

    Science.gov (United States)

    Palombo, John D; Ganguly, Aniruddha; Bistrian, Bruce R; Menard, Michael P

    2002-03-28

    The antiproliferative effects of two commercial preparations of conjugated linoleic acid (CLA) and their constituent isomers, cis-9, trans-11 (c9,t11)-CLA, c9,c11-CLA, and t10,c12-CLA, were determined in vitro using human colorectal (HT-29, MIP-101) and prostate (PC-3) carcinoma cells adapted to serum-free medium. The antiproliferative effects of the preparations were dependent upon the type and concentration of CLA isomer present. The t10,c12-CLA isomer exhibited the greatest potency against colorectal cancer proliferation, and the c9,t11 and t10,c12 isomers were moderately effective against prostate cancer. The t10,c12 isomer induced caspase-dependent apoptosis in MIP-101 and PC-3 cells. The results are the first to demonstrate that physiologic levels of two CLA preparations, their constituent isomers, and the c9,t11-CLA elongation product, c11,t13-conjugated eicosadienoic acid, induce dose-dependent inhibitory effects on cancer proliferation in vitro. Novel CLA preparations may prove effective as chemopreventive supplements for individuals at risk of or diagnosed with colorectal or prostate cancer.

  12. Tangerine tomatoes increase total and tetra-cis-lycopene isomer concentrations more than red tomatoes in healthy adult humans.

    Science.gov (United States)

    Burri, Betty Jane Burri; Chapman, Mary H; Neidlinger, Terry R; Seo, Jung S; Ishida, Betty K

    2009-01-01

    Lycopene, or the foods that contain it, may prevent prostate cancer. Studies suggest that some cis-lycopene isomers are more bioavailable than the trans-lycopene isomer. We hypothesized that tangerine tomatoes, which predominantly contain the tetra-cis isomer, should be a good source of bioavailable lycopene. We fed lunches containing 300 g tangerine or red tomato sauce per day to 21 healthy adults in a double-blind crossover design. We collected blood at baseline and after each treatment and washout period. We measured tetra-cis, other cis, and trans lycopene, as well as other carotenoids, by reversed-phase high-performance liquid chromatography. Both tomato sauces increased lycopene concentrations in blood, but the tangerine tomato sauce caused a greater increase of total and tetra-cis-lycopene. The cis isomer(s) may also have facilitated absorption of the trans-lycopene isomer. Indices of oxidative damage decreased as serum lycopene concentrations increased. Our results suggest that total lycopene concentrations can be increased by substituting tetra-cis-lycopene-rich tangerine tomatoes for common red tomatoes in the diet.

  13. Polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) isomer patterns from municipal waste combustion: formation mechanism fingerprints.

    Science.gov (United States)

    Ryu, Jae-Yong; Choi, Kum-Chan; Mulholland, James A

    2006-11-01

    Polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) byproducts can be formed in combustion systems by a variety of mechanisms. While total PCDD/F emissions and, to a lesser extent, homologue distributions from incinerators have been found to vary widely depending on combustion conditions, PCDD/F isomer distributions do not. Formation mechanisms can be grouped into two general categories: condensation of precursors, such as chlorinated phenols, and formation from particulate carbon, termed de novo synthesis. In addition to these mechanisms, chlorination and dechlorination reactions may affect isomer patterns. In this work, isomer patterns from field and laboratory municipal waste combustion samples are compared with computed thermodynamic distributions and those from the following experimental investigations: both gas-phase and metal-catalyzed condensation of chlorinated phenols, chlorination of dibenzo-p-dioxin and dibenzofuran, and dechlorination of octachlorodibenzo-p-dioxin and octachlorodibenzofuran. PCDD/F isomer patterns produced by different formation mechanisms in controlled experiments are distinct and robust, largely unaffected by combustion conditions. PCDD isomer patterns from municipal waste combustion are most similar to those produced by CuCl(2)-catalyzed phenol condensation from 10 chlorinated phenols. PCDF isomer patterns are most similar to those produced by chlorination and dechlorination.

  14. Discrimination of eight chloramphenicol isomers by liquid chromatography tandem mass spectrometry in order to investigate the natural occurrence of chloramphenicol.

    Science.gov (United States)

    Berendsen, Bjorn J A; Zuidema, Tina; de Jong, Jacob; Stolker, Linda A A M; Nielen, Michel W F

    2011-08-26

    This paper describes the discrimination of eight different isomers of chloramphenicol (CAP), an antibiotic banned for use in food producing animals, by reversed phase and chiral liquid chromatography in combination with tandem mass spectrometric detection. Previously, by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) the presence of CAP was confirmed in some grass and herb samples collected on Mongolian pastures up to concentrations of 450 μg kg(-1). It was not possible to establish the cause of CAP residues which has initiated research on the natural occurrence of this drug. CAP occurs in the para-configuration and in the meta-configuration and contains two chiral centers thus eight different isomeric configurations exist, namely four (RR, SS, RS, SR) meta-stereoisomers and four para-stereoisomers. It is known that only RR-p-CAP has antimicrobial properties. To find out if the CAP detected in the plant material samples is the active configuration, a high resolution reversed phase LC-MS/MS system was tested for its ability to separate the different isomers. This system proved to be able to discriminate between some isomers, but not between RR-p-CAP and SS-p-CAP, also called dextramycin. Despite a detailed elucidation of the product ions and the fragmentation patterns of all isomers, MS/MS did not add sufficient specificity for full discrimination of the isomers. Therefore a chiral liquid chromatographic separation with MS/MS detection that is able to distinguish all isomers was developed and finally the isomeric ratio of non-compliant plant material samples and some CAP formulations was determined using this system. This showed that Mongolian grass and herb samples only contain the biological active isomer of CAP as do the obtained formulations. Therefore the CAP present in the plant material might origin from the production by soil organisms or from a manufactured source.

  15. Quantitative trace analysis of eight chloramphenicol isomers in urine by chiral liquid chromatography coupled to tandem mass spectrometry.

    Science.gov (United States)

    Berendsen, Bjorn J A; Essers, Martien L; Stolker, Linda A A M; Nielen, Michel W F

    2011-10-14

    Chloramphenicol is a broad-spectrum antibiotic with, apart from its human medicinal use, veterinary abuse in all major food-producing animals. Chloramphenicol occurs in four stereoisomers (all para-nitro substituted) and furthermore four meta-nitro analogs of chloramphenicol exist. In this paper these are referred to as eight chloramphenicol isomers. According to EU regulations an analytical method should be able to discriminate the analyte from interfering substances that might be present in the sample, including isomers. For the first time a quantitative method for the analysis of trace levels of eight chloramphenicol isomers in urine by chiral liquid chromatography in combination with tandem mass spectrometric detection is reported. The separation of the isomers on the analytical column, the clean-up of urine and the selectivity of the monitored product ions turned out to be critical parameters. To obtain reproducible retention isocratic elution on a chiral AGP column was applied. For urine samples matrix compounds present in the final extract caused decreased retention of the isomers on the chiral stationary phase and a lack of chromatographic resolution. Therefore an extended clean-up procedure that combines solid phase extraction and liquid-liquid extraction had to be developed. The final method was fully validated and showed satisfactory performance for all isomers with decision limits (CCα) ranging from 0.005 to 0.03 μg L(-1) and within-laboratory reproducibility of all isomers below 20% at the minimum required performance limit level of 0.3 μg L(-1).

  16. Inositol pentakisphosphate isomers bind PH domains with varying specificity and inhibit phosphoinositide interactions

    Directory of Open Access Journals (Sweden)

    Schultz Carsten

    2011-02-01

    Full Text Available Abstract Background PH domains represent one of the most common domains in the human proteome. These domains are recognized as important mediators of protein-phosphoinositide and protein-protein interactions. Phosphoinositides are lipid components of the membrane that function as signaling molecules by targeting proteins to their sites of action. Phosphoinositide based signaling pathways govern a diverse range of important cellular processes including membrane remodeling, differentiation, proliferation and survival. Myo-Inositol phosphates are soluble signaling molecules that are structurally similar to the head groups of phosphoinositides. These molecules have been proposed to function, at least in part, by regulating PH domain-phosphoinositide interactions. Given the structural similarity of inositol phosphates we were interested in examining the specificity of PH domains towards the family of myo-inositol pentakisphosphate isomers. Results In work reported here we demonstrate that the C-terminal PH domain of pleckstrin possesses the specificity required to discriminate between different myo-inositol pentakisphosphate isomers. The structural basis for this specificity was determined using high-resolution crystal structures. Moreover, we show that while the PH domain of Grp1 does not possess this high degree of specificity, the PH domain of protein kinase B does. Conclusions These results demonstrate that some PH domains possess enough specificity to discriminate between myo-inositol pentakisphosphate isomers allowing for these molecules to differentially regulate interactions with phosphoinositides. Furthermore, this work contributes to the growing body of evidence supporting myo-inositol phosphates as regulators of important PH domain-phosphoinositide interactions. Finally, in addition to expanding our knowledge of cellular signaling, these results provide a basis for developing tools to probe biological pathways.

  17. 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

    2016-02-03

    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.

  18. Inositol Pentakisphosphate Isomers Bind PH Domains with Varying Specificity and Inhibit Phosphoinositide Interactions

    Energy Technology Data Exchange (ETDEWEB)

    S Jackson; S Al-Saigh; C Schultz; M Junop

    2011-12-31

    PH domains represent one of the most common domains in the human proteome. These domains are recognized as important mediators of protein-phosphoinositide and protein-protein interactions. Phosphoinositides are lipid components of the membrane that function as signaling molecules by targeting proteins to their sites of action. Phosphoinositide based signaling pathways govern a diverse range of important cellular processes including membrane remodeling, differentiation, proliferation and survival. Myo-Inositol phosphates are soluble signaling molecules that are structurally similar to the head groups of phosphoinositides. These molecules have been proposed to function, at least in part, by regulating PH domain-phosphoinositide interactions. Given the structural similarity of inositol phosphates we were interested in examining the specificity of PH domains towards the family of myo-inositol pentakisphosphate isomers. In work reported here we demonstrate that the C-terminal PH domain of pleckstrin possesses the specificity required to discriminate between different myo-inositol pentakisphosphate isomers. The structural basis for this specificity was determined using high-resolution crystal structures. Moreover, we show that while the PH domain of Grp1 does not possess this high degree of specificity, the PH domain of protein kinase B does. These results demonstrate that some PH domains possess enough specificity to discriminate between myo-inositol pentakisphosphate isomers allowing for these molecules to differentially regulate interactions with phosphoinositides. Furthermore, this work contributes to the growing body of evidence supporting myo-inositol phosphates as regulators of important PH domain-phosphoinositide interactions. Finally, in addition to expanding our knowledge of cellular signaling, these results provide a basis for developing tools to probe biological pathway.

  19. Trapping efficiency of 1,3-dichloropropene isomers by XAD-4 sorbent tubes for air sampling

    Science.gov (United States)

    Gao, S.; Pflaum, T.; Qin, R.

    2011-08-01

    Emission monitoring is necessary to evaluate the impact of air pollutants such as soil fumigants on the environment. Quantifying fumigant emissions often involves the use of air sampling tubes filled with sorbents to trap fumigants. 1,3-dichloropropene (1,3-D) and chloropicrin (CP) are being increasingly used in combination in soil fumigation since the phase-out of methyl bromide. Charcoal and XAD-4 resins are used for trapping 1,3-D and CP, respectively. If one sampling tube can trap both chemicals, the number of samples, the amount of work, and associated costs can be significantly reduced. The objective of this research was to determine the efficiency of XAD-4 sorbent tubes for trapping cis- and trans-1,3-D isomers as a function of flow rate (100-1000 ml min -1) and sampling time period (10-360 min). The results showed that XAD-4 could trap both 1,3-D isomers as efficiently as charcoal, but breakthrough occurred depending on the amount of sorbent materials in a tube, fumigant amount, flow rate and sampling time period. No significant breakthrough was observed from either small (120 mg) or large (600 mg) XAD-4 sorbent tubes over short sampling time periods (≤30 min) at any flow rate. Longer sampling period at low flow rates (100 ml min -1) resulted in ≥50% breakthrough from the small tubes during a 3 h sampling period; but no remarkable breakthrough from the large XAD-4 tubes up to 6 h sampling period when 3.0 mg 1,3-D isomers were tested. Field data showed agreement with laboratory tests. At high flow rates (1000 ml min -1), >40% breakthrough was observed from large XAD-4 sorbent tubes during 3 h trapping tests suggesting that short sampling time intervals are necessary to avoid potential breakthrough of fumigants from the sampling tubes.

  20. Quadrupole splitting and isomer shifts in Te oxides investigated using nuclear forward scattering

    Science.gov (United States)

    Klobes, Benedikt; Barrier, Nicolas; Vertruyen, Benedicte; Martin, Christine; Hermann, Raphaël P.

    2014-04-01

    Nuclear forward scattering by 125Te is a viable alternative to conventional 125Te Mössbauer spectroscopy avoiding all source related issues. Using reference compounds with known hyperfine parameters and Te oxides exhibiting stereochemically active lone pairs, we show that nuclear forward scattering by 125Te can be reliably used to extract quadrupole splitting energy and relative isomer shift. The rough correlation between Te-Ocoordination and quadrupole splitting energy as put forward by Takeda and Greenwood (J. Chem. Soc. Dalton, 2207, 1975), is corroborated by the presented results.

  1. E- and Z-Isomers of New Phytoecdysteroid Conjugates from French Polynesian Microsorum membranifolium (Polypodiaceae Fronds

    Directory of Open Access Journals (Sweden)

    René Lafont

    2012-09-01

    Full Text Available Phytochemical investigation of the fronds of Microsorum membranifolium resulted in the isolation of a new phytoecdysteroid, E-2-deoxy-20-hydroxyecdysone 3-[4-(1-b-D-glucopyranosyl]-caffeate (1, together with two known phytoecdysteroids, E-2-deoxy-20-hydroxyecdysone 3-[4-(1-b-D-glucopyranosyl]-ferulate (2, E-2-deoxyecdysone 3-[4-(1-b-D-glucopyranosyl]-ferulate (3. Their respective Z-isomers 4–6 were also observed and identified for the first time. The new structures were elucidated on the basis of extensive spectroscopic data analysis (1D, 2D-NMR and HR-MS techniques.

  2. Simple synthesis and biological evaluation of flocoumafen and its structural isomers

    Indian Academy of Sciences (India)

    Jae-Chul Jung; Soyong Jang; Seikwan Oh; Oee-Sook Park

    2010-11-01

    Simple synthesis and biological properties of flocoumafen 1 and its structural isomers are described. The key synthetic strategies involve Knoevenagel condensation, Grignard reaction, intramolecular ring cyclization and coupling reaction. Flocoumafen 1 was easily separated into cis and trans forms using flash column chromatography. They were then evaluated for suppression of LPS-induced NO generation and anti-excitotoxicity in vitro. It was found that the trans-flocoumafen was potent suppressor of NO generation with the concentration of 10 M in vitro, while no significant effect for neurotoxicity in cultured cortical neurons.

  3. 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...

  4. 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

  5. Gene characterized for membrane desaturase that produces (E)-11 isomers of mono- and diunsaturated fatty acids

    OpenAIRE

    Liu, Weitian; Jiao, Hongmei; Murray, Nancy C.; O'Connor, Marion; Roelofs, Wendell L.

    2002-01-01

    Moth species have evolved integral membrane desaturases that exhibit a wide diversity in substrate specificity, as well as in regiospecificity and stereospecificity of the unsaturated products. We report here the cloning and expression of a single desaturase from the sex pheromone gland of the light brown apple moth, Epiphyas postvittana, that makes E11 isomers of monounsaturated (E11-16 and E11-14) fatty acids and a diunsaturated (E9,E11-14) fatty acid. In the pheromone gland, the monoene pr...

  6. Resonance ionization spectroscopy of thorium isotopes - towards a laser spectroscopic identification of the low-lying 7.6 eV isomer of $^{229}$Th

    CERN Document Server

    Raeder, S; Wendt, K; Sonnenschein, V; Trautmann, N; Rothe, S; Reponen, M; Gottwald, T; 10.1088/0953-4075/44/16/165005

    2011-01-01

    In-source resonance ionization spectroscopy was used to identify an efficient and selective three step excitation/ionization scheme of thorium, suitable for titanium:sapphire (Ti:sa) lasers. The measurements were carried out in preparation of laser spectroscopic investigations for an identification of the low-lying Th-229m isomer predicted at 7.6 +- 0.5 eV above the nuclear ground state. Using a sample of Th-232, a multitude of optical transitions leading to over 20 previously unknown intermediate states of even parity as well as numerous high-lying odd parity auto-ionizing states were identified. Level energies were determined with an accuracy of 0.06 cm-1 for intermediate and 0.15 cm-1 for auto-ionizing states. Using different excitation pathways an assignment of total angular momenta for several energy levels was possible. One particularly efficient ionization scheme of thorium, exhibiting saturation in all three optical transitions, was studied in detail. For all three levels in this scheme, the isotope s...

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

    Directory of Open Access Journals (Sweden)

    Dracoulis G.D.

    2014-03-01

    Full Text Available Recent results on high-spin isomers populated in deep-inelastic reactions in the transitional tungsten-osmium region are outlined with a focus on 190Os, 192Os and 194Os. As well as the characterization of several two-quasinutron isomers, the 12+ and 20+ isomers in 192Os are interpreted as manifestations of maximal rotation alignment within the neutron i13/2 and possibly proton h11/2 shells at oblate deformation.

  8. 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.

  9. The trans-10,cis-12 isomer of conjugated linoleic acid reduces hepatic triacylglycerol content without affecting lipogenic enzymes in hamsters.

    Science.gov (United States)

    Zabala, Amaia; Churruca, Itziar; Macarulla, M Teresa; Rodríguez, Víctor M; Fernández-Quintela, Alfredo; Martínez, J Alfredo; Portillo, María P

    2004-09-01

    Conjugated linoleic acid (CLA) refers to the positional and geometric dienoic isomers of linoleic acid. The dietary intake of CLA has been associated with changes in lipid metabolism. The aim of the present work was to assess the effects of the two main isomers of CLA on sterol regulatory element binding protein (SREBP)-1a and SREBP-1c mRNA levels, as well as on mRNA levels and the activities of several lipogenic enzymes in liver. For this purpose hamsters were fed an atherogenic diet supplemented with 5 g linoleic acid, cis-9,trans-11 or trans-10,cis-12 CLA/kg diet for 6 weeks. The trans-10,cis-12 isomer intake produced significantly greater liver weight, but also significantly decreased liver fat accumulation. No changes in mRNA levels of SREBP-1a, SREBP-1c and lipogenic enzymes, or in the activities of these enzymes, were observed. There was no effect of feeding cis-9,trans-11 CLA. These results suggest that increased fat accumulation in liver does not occur on the basis of liver enlargement produced by feeding the trans-10,cis-12 isomer of CLA in hamsters. The reduction in hepatic triacylglycerol content induced by this isomer was not attributable to changes in lipogenesis.

  10. A theoretical study of porphyrin isomers and their core-modified analogues: cis-trans isomerism, tautomerism and relative stabilities

    Indian Academy of Sciences (India)

    M Punnagai; Saju Joseph; G Narahari Sastry

    2004-08-01

    Semiempirical (AM1 and PM3) and density functional theory (DFT) calculations were performed on about 50 porphyrin isomers with 25 each of 1,2 (syn) and 1,3 (anti) tautomeric forms. The corresponding oxa- and thia-core-modified analogues were also computed. The variations of relative energies and stabilities of the core-modified analogues were compared with parent porphyrin 1 and the corresponding oxa- and thia-analogues. The trends in relative energies are not significantly changed while going from parent system to oxa- and thia-core-modified porphyrins in case of both syn and anti tautomers. Isomers of types [2.2.0.0], [3.0.1.0], [3.1.0.0], and [4.0.0.0] are destabilized due to the absence of methine bridge, which results in angle strain for tetrapyrroles. Isomers having [2.1.1.0], [2.1.0.1], [2.0.2.0] and [2.2.0.0] connectivity, the isomers, are more stable compared to the corresponding isomers in both syn and anti forms of parent and core-modified analogues.

  11. Up- and down-regulation of beta-adrenoreceptors in rat cerebral cortex following exposure to isomers of hexachlorocyclohexane

    Energy Technology Data Exchange (ETDEWEB)

    Stark, L.; Hollinger, M.; Joy, R.

    1986-03-01

    The authors have shown that the gamma (lindane) and beta isomers of hexachlorocyclohexane (HCH) have opposite effects on the kindling model of epilepsy (gamma facilitates, beta retards kindling acquisition). In the present study the authors determined the effects of these two isomers on ..beta..-adrenoreceptors in rat brain using /sup 3/H-dihydroalprenolol as the ligand following 10 days treatment with 10 mg/kg p.o. of isomers or corn oil. Results showed a statistically significant decrease in the number of ..beta..-adrenoreceptors in cortical tissue taken from lindane treated rats. In contrast, there was a significant increase in the number of ..beta..-adreno receptors in cortical tissue taken from beta-HCH treated rats. Neither treatment caused a significant change in Kd. It is concluded that the ..beta..-adrenoreceptor system in rat brain is differentially affected by the isomers of HCH. Since the kindling model of epilepsy is sensitive to modulation in adrenergic function, this system may be involved in the pro- and anticonvulsant effects of these HCH isomers on kindling acquisition.

  12. Bioaccumulation of perfluoroalkyl acids including the isomers of perfluorooctane sulfonate in carp (Cyprinus carpio) in a sediment/water microcosm.

    Science.gov (United States)

    Fang, Shuhong; Zhang, Yifeng; Zhao, Shuyan; Qiang, Liwen; Chen, Meng; Zhu, Lingyan

    2016-12-01

    Carp (Cyprinus carpio) were exposed to perfluoroalkyl acids (PFAAs) including perfluorooctane sulfonate (PFOS) isomers in an artificially contaminated sediment/water microcosm. The uptake constant of PFAAs increased with increasing carbon chain length, whereas the elimination coefficient displayed the opposite trend, suggesting that carbon chain length plays an important role in the bioaccumulation of PFAAs. When the contribution of suspended particulate matter was taken into account, the bioaccumulation factors (BAFs) became lower (3.61-600 L/kg) compared with BAFs derived from only considering the absorption from free PFAAs in water (3.85-97000 L/kg). The results indicate that suspended particulate matter in water constitutes an important source of exposure for aquatic organisms to long-chain PFAAs. Linear (n-)PFOS was preferentially accumulated compared with branched isomers in carp. Among the branched isomers, 1m-PFOS displayed the greatest bioaccumulation, whereas m2 -PFOS had the lowest. Linear PFOS displayed greater partitioning ability from blood to other tissues over branched PFOS (br-PFOS) isomers, leading to a relatively lower n-PFOS proportion in blood. In summary, suspended particulate matter made a contribution to the accumulation of long-chain PFAAs in aquatic organisms, and n-PFOS was preferentially accumulated compared with br-PFOS isomers. Environ Toxicol Chem 2016;35:3005-3013. © 2016 SETAC.

  13. Tautomeric conversion, vibrational spectra, and density functional studies on peripheral sulfur derivatives of benzothiazole and benzothiazoline isomers

    Science.gov (United States)

    Altun, Ahmet; Kuliyev, Eziz; Aghatabay, Naz M.

    2016-01-01

    The room temperature structural (tautomerism, dimerization, conformational preference, geometry parameters) and vibrational spectral (IR and Raman) analyses have been performed on benzothiazoline (benzothiazoline-2-thione, 3-methyl-benzothiazoline-2-thione) and benzothiazole [2-mercaptobenzothiazole, 2-methylthiobenzothiazole, and bis(benzothiazole-2-ylthio)ethane] derivatives at the B3LYP/6-311++G∗∗ level of theory. Although the keto to enol transition barriers are too high over the most stable benzothiazoline isomers, vibrational spectral analyses reveal some major bands of benzothiazole isomers in the present room temperature experimental FT-IR and FT-Raman specta. Therefore, benzothiazole isomers exist at rare amounts in the powdered samples that are mainly composed of benzothiazoline isomers. The benzothiazole isomers have two stable conformations due to the orientation of their SH and SCH3 moieties. The energetic and vibrational spectral analyses suggest that the benzothiazoline-2-thione molecules can be stabilized further through the NH⋯S intermolecular hydrogen bonds in solid phase. All observed fundamental vibrational bands of the molecules have been assigned based on the calculated mode frequencies and IR/Raman intensities. The mode assignments have been expressed in terms of internal coordinates and their percent potential energy distributions. The effects of substitution at the nitrogen and peripheral sulfur atoms have been analyzed for the geometries and vibrational bands of the molecules.

  14. Clomiphene and Its Isomers Block Ebola Virus Particle Entry and Infection with Similar Potency: Potential Therapeutic Implications

    Directory of Open Access Journals (Sweden)

    Elizabeth A. Nelson

    2016-08-01

    Full Text Available The 2014 outbreak of Ebola virus (EBOV in Western Africa highlighted the need for anti-EBOV therapeutics. Clomiphene is a U.S. Food and Drug Administration (FDA-approved drug that blocks EBOV entry and infection in cells and significantly protects EBOV-challenged mice. As provided, clomiphene is, approximately, a 60:40 mixture of two stereoisomers, enclomiphene and zuclomiphene. The pharmacokinetic properties of the two isomers vary, but both accumulate in the eye and male reproductive tract, tissues in which EBOV can persist. Here we compared the ability of clomiphene and its isomers to inhibit EBOV using viral-like particle (VLP entry and transcription/replication-competent VLP (trVLP assays. Clomiphene and its isomers inhibited the entry and infection of VLPs and trVLPs with similar potencies. This was demonstrated with VLPs bearing the glycoproteins from three filoviruses (EBOV Mayinga, EBOV Makona, and Marburg virus and in two cell lines (293T/17 and Vero E6. Visual problems have been noted in EBOV survivors, and viral RNA has been isolated from semen up to nine months post-infection. Since the clomiphene isomers accumulate in these affected tissues, clomiphene or one of its isomers warrants consideration as an anti-EBOV agent, for example, to potentially help ameliorate symptoms in EBOV survivors.

  15. Nuclear spins of the isomers /sup 191m-185m/Hg determined by on-line quantum-beat spectroscopy

    CERN Document Server

    Kremmling, H; Fischer, H G; Kluge, H J; Kühl, T; Schüssler, H A

    1979-01-01

    The nuclear spins of the very neutron-deficient /sup 191m-185m/Hg isomers were measured on line at the mass separator ISOLIDE at CERN using pulsed-laser excitation and observation of the time-resolved quantum beats from selected hyperfine-structure states. The spins of these isomers are with I=13/2 equal to those of the long-lived isomers /sup 199m-193m/Hg already known. The persistence of this spin value for eight isomers is explained by the model of rotation-aligned coupling. (12 refs).

  16. Effects of ingestion of tomatoes, tomato juice and tomato purée on contents of lycopene isomers, tocopherols and ascorbic acid in human plasma as well as on lycopene isomer pattern.

    Science.gov (United States)

    Fröhlich, Kati; Kaufmann, Karin; Bitsch, Roland; Böhm, Volker

    2006-04-01

    Tomatoes are an important part of the diet. Lycopene, the predominant carotenoid in tomatoes, is hypothesised to mainly mediate the health benefits of tomato products. Anticancer activity of tomato products and lycopene has been suggested by numerous studies. The aim of the present study was to investigate the effect of ingestion of three different tomato-based foodstuffs on plasma contents of lycopene, tocopherols and ascorbic acid. Because isomers of lycopene may have different biological activities, a special interest was to look how the lycopene isomer pattern is changed depending on the matrix of tomato products. Following a 2-week depletion phase volunteers ingested 12.5 mg lycopene/d for 4 weeks comprising tomatoes, tomato juice or tomato purée. The basal levels of lycopene in plasma were comparable for all groups and decreased significantly during the 2 weeks of depletion to approximately half of the basal values. Following intervention, plasma lycopene concentration increased significantly. Conversely, supplementation did not significantly affect levels of tocopherols and ascorbic acid in plasma. Regarding isomers of lycopene, the (Z)-lycopene:(all-E)-lycopene plasma isomer ratio was significantly changed during the study for all groups. A remarkable enrichment of the relative contents of (5Z)-lycopene was observed during the depletion period, which supports the hypothesis that lycopene (Z)-isomers are formed within the human body after ingestion of (all-E)-lycopene. After dietary intervention with lycopene-rich products the isomer ratios returned to those observed at the start of the study. Further investigations will clarify the process of isomerisation in more detail.

  17. Lubricating and Waxy Esters. VI. Effect of Symmetry about Ester on Crystallization of Linear Monoester Isomers

    Directory of Open Access Journals (Sweden)

    Laziz Bouzidi

    2014-08-01

    Full Text Available The crystal structure development of jojoba-like esters incorporating either 1-decenoic acid and/or 1-decenol, namely octadec-9-enyl dec-9-enoate (JLE-281, and its isomer dec-9-enyl oleate (JLE-282 was investigated to reveal the effect of symmetry about the ester group on crystallization of aliphatic fatty monoesters. The phase transformation path was investigated with temperature-time resolved X-ray diffraction during stepped isothermal crystallization, and while cooling from the melt at a fixed rate. Startling differences in phase behavior were uncovered between the isomers. When stepped isothermals were used, selective extinctions occurred at a transition temperature for JLE-281 but not for JLE-282. The extinctions, which are due to dramatic changes in the electronic density of certain families of planes, indicate a phase transition attributed to a brusque rearrangement of the oxygen atoms in the crystal subcell. The phase transition did not occur when the JLEs were cooled continuously. The crucial role played by the position of the alkyl chain and its orientation relative to the easy rotation site of the C–O bond in the phase trajectories of the JLEs was particularly highlighted.

  18. Reactivation of immobilized acetylcholinesterase-tabun complex by pralidoxime, its isomers, and homologs.

    Science.gov (United States)

    Hoskovcová, Monika; Halámek, Emil; Kobliha, Zbynek; Tusarová, Ivana

    2010-06-01

    Reactivation efficacy of three homologous and three isomeric series of pralidoxime-type reactivators with aldoxime group in position 2, 3 and 4 of the heterocycle was tested in reactivation of tabun-inhibited AChE. The experiments were performed with immobilized and stabilized porcine brain AChE. The enzyme activity was measured by Ellman method. Reactivation efficacy was determined by measurement of indicator fabric coloration intensity as a measure of AChE activity. Of the studied group of nine reactivators, isomers with the functional group in position 2 were the most effective. The highest value (30 %) for reactivation of inhibited AChE was found for 2PAE after treatment for 15 min at concentration 0.5 mg/cm(3). The efficacy of the isomers decreased in the order ortho > para > meta. No marked effect on the efficacy of the reactivators was observed on prolongation of the reactivation time. The reactivators efficacy decreased with decreasing concentration of their solutions.

  19. Observation of new microsecond isomers among fission products of 345 MeV/nucleon 238U

    CERN Document Server

    Kameda, D; Ohnishi, T; Kusaka, K; Yoshida, A; Yoshida, K; Ohtake, M; Fukuda, N; Takeda, H; Tanaka, K; Inabe, N; Yanagisawa, Y; Gono, Y; Watanabe, H; Otsu, H; Baba, H; Ichihara, T; Yamaguchi, Y; Takechi, M; Nishimura, S; Ueno, H; Yoshimi, A; Sakurai, H; Motobayashi, T; Nakao, T; Mizoi, Y; Matsushita, M; Ieki, K; Kobayashi, N; Tanaka, K; Kawada, Y; Tanaka, N; Deguchi, S; Satou, Y; Kondo, Y; Nakamura, T; Yoshinaga, K; Ishii, C; Yoshii, H; Miyashita, Y; Uematsu, N; Shiraki, Y; Sumikama, T; Chiba, J; Ideguchi, E; Saito, A; Yamaguchi, T; Hachiuma, I; Suzuki, T; Moriguchi, T; Ozawa, A; Ohtsubo, T; Famiano, M A; Geissel, H; Nettleton, A S; Tarasov, O B; Bazin, D; Sherrill, B M; Manikonda, S L; Nolen, J A

    2012-01-01

    A search for isomeric gamma-decays among fission fragments from 345 MeV/nucleon 238U has been performed at the RIKEN Nishina Center RI Beam Factory. Fission fragments were selected and identified using the superconducting in-flight separator BigRIPS and were implanted in an aluminum stopper. Delayed gamma-rays were detected using three clover-type high-purity germanium detectors located at the focal plane within a time window of 20 microseconds following the implantation. We identified a total of 54 microsecond isomers with half-lives of ~0.1 - 10 microseconds, including discovery of 18 new isomers in very neutron-rich nuclei: 59Tim, 90Asm, 92Sem, 93Sem, 94Brm, 95Brm, 96Brm, 97Rbm, 108Nbm, 109Mom, 117Rum, 119Rum, 120Rhm, 122Rhm, 121Pdm, 124Pdm, 124Agm and 126Agm, and obtained a wealth of spectroscopic information such as half-lives, gamma-ray energies, gamma-ray relative intensities and gamma-gamma coincidences over a wide range of neutron-rich exotic nuclei. Proposed level schemes are presented for 59Tim, 82...

  20. Isomers and high-spin structures in the N =81 isotones 135Xe and 137Ba

    Science.gov (United States)

    Vogt, A.; Birkenbach, B.; Reiter, P.; Blazhev, A.; Siciliano, M.; Hadyńska-Klek, K.; Valiente-Dobón, J. J.; Wheldon, C.; Teruya, E.; Yoshinaga, N.; Arnswald, K.; Bazzacco, D.; Bowry, M.; Bracco, A.; Bruyneel, B.; Chakrawarthy, R. S.; Chapman, R.; Cline, D.; Corradi, L.; Crespi, F. C. L.; Cromaz, M.; de Angelis, G.; Eberth, J.; Fallon, P.; Farnea, E.; Fioretto, E.; Freeman, S. J.; Fu, B.; Gadea, A.; Geibel, K.; Gelletly, W.; Gengelbach, A.; Giaz, A.; Görgen, A.; Gottardo, A.; Hayes, A. B.; Hess, H.; Hirsch, R.; Hua, H.; John, P. R.; Jolie, J.; Jungclaus, A.; Kaya, L.; Korten, W.; Lee, I. Y.; Leoni, S.; Lewandowski, L.; Liang, X.; Lunardi, S.; Macchiavelli, A. O.; Menegazzo, R.; Mengoni, D.; Michelagnoli, C.; Mijatović, T.; Montagnoli, G.; Montanari, D.; Müller-Gatermann, C.; Napoli, D.; Pearson, C. J.; Pellegri, L.; Podolyák, Zs.; Pollarolo, G.; Pullia, A.; Queiser, M.; Radeck, F.; Recchia, F.; Regan, P. H.; Rosiak, D.; Saed-Samii, N.; Şahin, E.; Scarlassara, F.; Schneiders, D.; Seidlitz, M.; Siebeck, B.; Sletten, G.; Smith, J. F.; Söderström, P.-A.; Stefanini, A. M.; Steinbach, T.; Stezowski, O.; Szilner, S.; Szpak, B.; Teng, R.; Ur, C.; Vandone, V.; Warner, D. D.; Wiens, A.; Wu, C. Y.; Zell, K. O.

    2017-02-01

    The high-spin structures and isomers of the N =81 isotones 135Xe and 137Ba are investigated after multinucleon-transfer (MNT) and fusion-evaporation reactions. Both nuclei are populated (i) in 136Xe+238U and (ii) 136Xe+208Pb MNT reactions employing the high-resolution Advanced Gamma Tracking Array (AGATA) coupled to the magnetic spectrometer PRISMA, (iii) in the 136Xe+198Pt MNT reaction employing the γ -ray array GAMMASPHERE in combination with the gas-detector array CHICO, and (iv) via a 11B+130Te fusion-evaporation reaction with the HORUS γ -ray array at the University of Cologne. The high-spin level schemesof 135Xe and 137Ba are considerably extended to higher energies. The 2058-keV (19 /2-) state in 135Xe is identified as an isomer, closing a gap in the systematics along the N =81 isotones. Its half-life is measured to be 9.0(9) ns, corresponding to a reduced transition probability of B (E 2 ,19 /2-→15 /2-) =0.52 (6 ) W.u. The experimentally deduced reduced transition probabilities of the isomeric states are compared to shell-model predictions. Latest shell-model calculations reproduce the experimental findings generally well and provide guidance to the interpretation of the new levels.

  1. First-principles structure search for the stable isomers of stoichiometric WS2 nano-clusters

    CERN Document Server

    Hafizi, Roohollah; Alaei, Mojtaba; Jangrouei, MohammadReza; Akbarzadeh, Hadi

    2016-01-01

    In this paper, we employ evolutionary algorithm along with the full-potential density functional theory (DFT) computations to perform a comprehensive search for the stable structures of stoichiometric (WS2)n nano-clusters (n=1-9), within three different exchange-correlation functionals. Our results suggest that n=3, 5, 8 are possible candidates for the low temperature magic sizes of WS2 nano-clusters while at temperatures above 600 Kelvin, n=5 and 7 exhibit higher relative stability among the studied systems. The electronic properties and energy gap of the lowest energy isomers were computed within several schemes, including semilocal PBE and BLYP functionals, hybrid B3LYP functional, many body based DFT+GW approach, and time dependent DFT calculations. Vibrational spectra of the lowest lying isomers, computed by the force constant method, are used to address IR spectra and thermal free energy of the clusters. Time dependent density functional calculation in real time domain is applied to determine the full a...

  2. Investigations on Synperiplanar and Antiperiplanar Isomers of Losartan: Theoretical and Experimental NMR Studies.

    Science.gov (United States)

    Kujawski, Jacek; Czaja, Kornelia; Ratajczak, Tomasz; Jodłowska, Elżbieta; Chmielewski, Marcin K

    2015-06-29

    Losartan inhibits the renin-angiotensin-aldosterone system by blocking the angiotensin II receptor. It is commonly used in cardiovascular diseases, such as hypertension. Several publications applied the ab initio and density functional theory methods to investigate the molecule of losartan. Only in one of them were the nuclear magnetic resonance spectra calculations carried out, and their results were correlated with the experimental values. The authors focused their attention on calculations of the anion form of losartan, taking into consideration both its synperiplanar and antiperiplanar configurations. Coefficients of determination and mean absolute deviation parameters were calculated for the experimental and calculated chemical shifts for every used basis set. They showed a noticeably stronger correlation for the anti-isomers than for the syn-isomers. Moreover, the solvation model increased the value of this parameter. The results of calculations confirmed that an anti-conformation of the analyte seems to be the preferred one, and such an orientation might be most potent within the receptor cavity, which is in agreement with the results of previous studies.

  3. The association of matrix Gla protein isomers with calcification in capsules surrounding silicone breast implants.

    Science.gov (United States)

    Hunter, Larry W; Lieske, John C; Tran, Nho V; Miller, Virginia M

    2011-11-01

    Implanted silicone medical prostheses induce a dynamic sequence of histologic events in adjacent tissue resulting in the formation of a fibrotic peri-prosthetic capsule. In some cases, capsular calcification occurs, requiring surgical intervention. In this study we investigated capsules from silicone gel-filled breast prostheses to test the hypothesis that this calcification might be regulated by the small vitamin K-dependent protein, matrix Gla protein (MGP), a potent inhibitor of arterial calcification, or by Fetuin-A, a hepatocyte-derived glycoprotein also implicated as a regulator of pathologic calcification. Immunolocalization studies of explanted capsular tissue, using conformation-specific antibodies, identified the mineralization-protective γ-carboxylated MGP isomer (cMGP) within cells of uncalcified capsules, whereas the non-functional undercarboxylated isomer (uMGP) was typically absent. Both were upregulated in calcific capsules and co-localized with mineral plaque and adjacent fibers. Synovial-like metaplasia was present in one uncalcified capsule in which MGP species were differentially localized within the pseudosynovium. Fetuin-A was localized to cells within uncalcified capsules and to mineral deposits within calcific capsules. The osteoinductive cytokine bone morphogenic protein-2 localized to collagen fibers in uncalcified capsules. These findings demonstrate that MGP, in its vitamin K-activated conformer, may represent a pharmacological target to sustain the health of the peri-prosthetic tissue which encapsulates silicone breast implants as well as other implanted silicone medical devices.

  4. 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.

  5. Separation of positional CPP isomers by chiral HPLC-DAD of seized tablets.

    Science.gov (United States)

    Schürenkamp, Jennifer; Beike, Justus; Pfeiffer, Heidi; Köhler, Helga

    2011-01-01

    Meta-chlorophenylpiperazine, one of the synthetic piperazine-derived designer drugs, is to date controlled as an illicit substance in five European member states. Depending on the position of the chlorine atom, different positional isomers of CPP (ortho-, meta- and para-) are possible. Therefore, there is a need to develop an analytical method for the separation and identification of the three 1-chlorophenylpiperazines in tablets containing CPP. In this work, the position isomers o-, m- and p-CPP were separated by liquid chromatography (HPLC) on a reversed-phase chiral column. Different mobile phase compositions and pH ranges were systematically studied to find optimum chromatographic conditions. Best results were achieved with isocratic mobile phase of triethyl amine buffer and methanol (V/V = 70/30) at pH 9 with a flow rate of 0.8 ml/min. The method was validated in terms of selectivity, linearity, limit of detection and quantification and precision. At last, the developed method was successfully applied on seized ecstasy tablets.

  6. Tuning zinc coordination architectures by benzenedicarboxylate position isomers and bis(triazole)

    Science.gov (United States)

    Peng, Yan-fen; Li, Ke; Zhao, Shan; Han, Shan-shan; Li, Bao-long; Li, Hai-Yan

    2015-08-01

    Three position isomers 1,2-, 1,3-, 1,4-benzenedicarboxylate and 1,4-bis(1,2,4-triazol-4-yl)benzene were used to assembly zinc(II) coordination polymers {[Zn2(btx)0.5(1,2-bdc)2(H2O)]·H2O}n (1), {[Zn(btx)(1,3-bdc)]·2H2O·(DMF)}n (2) and {[Zn(btx)(1,4-bdc)]·3H2O}n (3). 1 is a (3,4,4,4)-connected two-dimensional network with point symbol (42·6)(44·62)(43·62·8)(42·6·103). 2 shows a two-dimensional (4,4) network. 3 exhibits a 5-fold interpenetrated three-dimensional diamondoid network. The structural versatility shows that the structures of coordination polymers can be tuned by the position isomers ligands. The luminescence and thermal stability were investigated.

  7. 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.

  8. Sequence Analysis of Trimer Isomers Formed by Montmorillonite Catalysis in the Reaction of Binary Monomer Mixtures

    Science.gov (United States)

    Ertem, Gözen; Hazen, Robert M.; Dworkin, Jason P.

    2007-10-01

    Oligonucleotides are structurally similar to short RNA strands. Therefore, their formation via non-enzymatic reactions is highly relevant to Gilbert's RNA world scenario (1986) and the origin of life. In laboratory synthesis of oligonucleotides from monomers, it is necessary to remove the water molecules from the reaction medium to shift the equilibrium in favor of oligonucleotide formation, which would have been impossible for reactions that took place in dilute solutions on the early Earth. Model studies designed to address this problem demonstrate that montmorillonite, a phyllosilicate common on Earth and identified on Mars, efficiently catalyzes phosphodiester-bond formation between activated mononucleotides in dilute solutions and produces RNA-like oligomers. The purpose of this study was to examine the sequences and regiospecificity of trimer isomers formed in the reaction of 5'-phosphorimidazolides of adenosine and uridine. Results demonstrated that regiospecificity and sequence specificity observed in the dimer fractions are conserved in their elongation products. With regard to regiospecificity, 61% of the linkages were found to be RNA-like 3',5'-phosphodiester bonds. With regard to sequence specificity, we found that 88% of the linear trimers were hetero-isomers with 61% A-monomer and 39% U-monomer incorporation. These results lend support to Bernal's hypothesis that minerals may have played a significant role in the chemical processes that led to the origin of life by catalyzing the formation of phosphodiester bonds in RNA-like oligomers.

  9. MALDI mechanism of dihydroxybenzoic acid isomers: desorption of neutral matrix and analyte.

    Science.gov (United States)

    Liang, Chi Wei; Lee, Chih Hao; Lin, Yu-Jiun; Lee, Yuan Tseh; Ni, Chi Kung

    2013-05-01

    Angular resolved velocity distributions of laser desorbed neutral matrices (dihydroxybenzoic acids, DHB) and analytes (tryptophan) embedded in these matrices were investigated at 322 nm by a modified crossed molecular beam apparatus. Desorbed ions generated from MALDI were measured by a time-of-flight mass spectrometer. Desorptions of neutral matrix and analyte from 2,3-DHB, 2,4-DHB, 2,5-DHB, 2,6-DHB, and 3,5--DHB at 322 nm have similar properties, but the ion intensities are in the order 2,3DHB ≅ 2,6-DHB > 2,5-DHB ≅ 2,4-DHB > 3,5-DHB. It indicates that the combination of various parameters related to neutral species, including absorption coefficient, sublimation energy, contact of analyte and matrix in crystal, and plume dynamics of desorbed species are not crucial in the determination of MALDI process for DHB isomers. The difference of matrix activity of DHB isomers at this wavelength must result from the other properties, like the excited state lifetime, proton affinity, gas-phase basicity, acidity, ionization energy, or the other properties related to the primary reactions in ion generation.

  10. Ultrasonic Investigations of Molecular Interaction in Binary Mixtures of Cyclohexanone with Isomers of Butanol

    Directory of Open Access Journals (Sweden)

    Sk. Md Nayeem

    2014-01-01

    Full Text Available Ultrasonic speed, u, and density, ρ, have been measured in binary liquid mixtures of cyclohexanone with the isomers of butanol (n-butanol, sec-butanol, and tert-butanol at 308.15 K over the entire range of composition. Molar volume (Vm, adiabatic compressibility (ks, intermolecular free length (Lf, acoustic impedance (z, and their excess/deviation along with Δu have been calculated from the experimental data. These values have been fitted to Redlich-Kister type polynomial equation. Positive values of VmE, Δks, LfE and negative values of zE, Δu have been observed for all the liquid mixtures indicating the existence of weak interactions between components. Rupture of H-bond or reduction in H-bond strength of isomers of butanol or breaking of the structure of one or both of the components in a solution causes the existence of dispersions in the present investigated binary mixtures. The data obtained from V-m,1, V-m,2, and excess partial molar volumes V-m, 1E, V-m, 2E, reflects the inferences drawn from VmE. Furthermore, FTIR spectra support the conclusions drawn from excess/deviation properties. The measured values of ultrasonic speed for all the investigated mixtures have been compared with the theoretically estimated values using empirical relations such as, Nomoto, Van Dael and Vangeels, Impedance and Rao specific sound speed.

  11. Investigation of HNCO isomers formation in ice mantles by UV and thermal processing: an experimental approach

    CERN Document Server

    Jiménez-Escobar, A; 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 a 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 analogues 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 was simulated using the Interstellar Astrochemistry Chamber (ISAC), 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 (QMS) detected the desorption of the molecules in the gas phase....

  12. Investigations on Synperiplanar and Antiperiplanar Isomers of Losartan: Theoretical and Experimental NMR Studies

    Directory of Open Access Journals (Sweden)

    Jacek Kujawski

    2015-06-01

    Full Text Available Losartan inhibits the renin-angiotensin-aldosterone system by blocking the angiotensin II receptor. It is commonly used in cardiovascular diseases, such as hypertension. Several publications applied the ab initio and density functional theory methods to investigate the molecule of losartan. Only in one of them were the nuclear magnetic resonance spectra calculations carried out, and their results were correlated with the experimental values. The authors focused their attention on calculations of the anion form of losartan, taking into consideration both its synperiplanar and antiperiplanar configurations. Coefficients of determination and mean absolute deviation parameters were calculated for the experimental and calculated chemical shifts for every used basis set. They showed a noticeably stronger correlation for the anti-isomers than for the syn-isomers. Moreover, the solvation model increased the value of this parameter. The results of calculations confirmed that an anti-conformation of the analyte seems to be the preferred one, and such an orientation might be most potent within the receptor cavity, which is in agreement with the results of previous studies.

  13. Determination of the D and L isomers of some protein amino acids present in soils

    Science.gov (United States)

    Pollock, G. E.; Cheng, C.-N.; Cronin, S. E.

    1977-01-01

    The D and L isomers of some protein amino acids present in soils were measured by using a gas chromatographic technique. The results of two processing procedures were compared to determine the better method. Results of the comparison indicated that the determination of D and L percentages requires amino acid purification if one is to obtain accurate data. It was found that very significant amounts of D-alanine, D-aspartic acid, and D-glutamic acid were present in the contemporary soils studied. Valine, isoleucine, leucine, proline, and phenylalanine generally contained only a trace to very small amounts of the D isomer. It is probable that the D-amino acids from the alanine, aspartic, and glutamic acids are contributed to the soil primarily via microorganisms. The finding of very significant quantities of some D-amino acids (about 5-16%) in present-day soils may alert some investigators of geological sediments to a possible problem in using amino acid racemization as an age-dating technique.

  14. Synthesis, Crystal Structure and Theoretically Study of 2-(Dimethylamino)-1,3-dithiocyanatopropane and Its Isomer

    Institute of Scientific and Technical Information of China (English)

    YU Guan-ping; MA Yi; LIU Zhuo; WANG Gang; LI Zheng-ming

    2011-01-01

    2-(Dimethylamino)-1,3-dithiocyanatopropane(1)has been prepared as a key intermediate synthesizing a natural insecticide Cartap by the reaction of 1-dimethylamino-2,3-dichloropropane with sodium thiocyanate.The crystal structures of compound 1 and its isomer 1-(dimethylamino)-2,3-dithiocyanotopropane(2)formed during the reaction were determined by X-ray single-crystal diffraction.Bond lengths in both the compounds are common and fall within normal ranges.There are some weak C-H…N hydrogen bonds in the lattice of compound 1,which makes it form a three-dimensional network,which stabilize the crystal structure.No classic hydrogen bonds were founded in its isomer(2),only van der Waals forces contribute to the stability of the structure.In addition,DFT and MP2 calculations with 6-311+G(d,p)basis set have also been carried out to investigate the thermodynamic properties of compounds 1 and 2.The research will be applied to the further investigation of the tautomerization of compounds 1 and 2.

  15. Characterization of epoxydecenal isomers as potent odorants in black tea (Dimbula) infusion.

    Science.gov (United States)

    Kumazawa, Kenji; Wada, Yoshiyuki; Masuda, Hideki

    2006-06-28

    In a black tea (Dimbula) infusion, the potent "sweet and/or juicy" odorants were identified as the cis- and trans-4,5-epoxy-(E)-2-decenals by comparison of their gas chromatography retention indices, mass spectra, and odor quality to those of the actual synthetic compounds. Of the two odorants, cis-4,5-epoxy-(E)-2-decenal has been identified for the first time in the black tea. On the basis of the aroma extract dilution analysis on the flavor distillate obtained using the solvent-assisted flavor evaporation technique from the black tea infusion, these isomers showed higher flavor dilution (FD) factors. The FD factors and concentrations of these odorants in the black tea infusion were observed to be much higher than those from Japanese green tea. In addition, the model studies showed that these odorants were generated from linoleic acid and its hydroperoxides by heating, but the generated amounts of these odorants from linoleic acid were much less than those of its hydroperoxides. It can be assumed from these results that the withering and fermentation, which are characteristic processes during the manufacturing of the black tea, which includes the enzymatic reaction such as lipoxygenase, is one of the most important factors for the formation of the epoxydecenal isomers.

  16. 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.

  17. Separation of Opiate Isomers Using Electrospray Ionization and Paper Spray Coupled to High-Field Asymmetric Waveform Ion Mobility Spectrometry

    Science.gov (United States)

    Manicke, Nicholas E.; Belford, Michael

    2015-05-01

    One limitation in the growing field of ambient or direct analysis methods is reduced selectivity caused by the elimination of chromatographic separations prior to mass spectrometric analysis. We explored the use of high-field asymmetric waveform ion mobility spectrometry (FAIMS), an ambient pressure ion mobility technique, to separate the closely related opiate isomers of morphine, hydromorphone, and norcodeine. These isomers cannot be distinguished by tandem mass spectrometry. Separation prior to MS analysis is, therefore, required to distinguish these compounds, which are important in clinical chemistry and toxicology. FAIMS was coupled to a triple quadrupole mass spectrometer, and ionization was performed using either a pneumatically assisted heated electrospray ionization source (H-ESI) or paper spray, a direct analysis method that has been applied to the direct analysis of dried blood spots and other complex samples. We found that FAIMS was capable of separating the three opiate structural isomers using both H-ESI and paper spray as the ionization source.

  18. Tailorable PC71 BM Isomers: Using the Most Prevalent Electron Acceptor to Obtain High-Performance Polymer Solar Cells.

    Science.gov (United States)

    Zhan, Xin-Xing; Zhang, Xin; Dai, Si-Min; Li, Shu-Hui; Lu, Xu-Zhai; Deng, Lin-Long; Xie, Su-Yuan; Huang, Rong-Bin; Zheng, Lan-Sun

    2016-12-23

    Despite being widely used as electron acceptor in polymer solar cells, commercially available PC71 BM (phenyl-C71 -butyric acid methyl ester) usually has a "random" composition of mixed regioisomers or stereoisomers. Here PC71 BM has been isolated into three typical isomers, α-, β1 - and β2 -PC71 BM, to establish the isomer-dependent photovoltaic performance on changing the ternary composition of α-, β1 - and β2 -PC71 BM. Mixing the isomers in a ratio of α/β1 /β2 =8:1:1 resulted in the best power conversion efficiency (PCE) of 7.67 % for the polymer solar cells with PTB7:PC71 BM as photoactive layer (PTB7=poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl

  19. Isolation and Metabolic Characterization of a Pseudomonas stutzeri Mutant Able To Grow on the Three Isomers of Xylene

    Science.gov (United States)

    Di, Le; Accarino, M.; Bolognese, F.; Galli, E.; Barbieri, P.

    1997-01-01

    From an o-xylene-degrading Pseudomonas stutzeri strain (OX1), we previously isolated mutant M1, which had acquired the ability to grow on m-xylene and p-xylene but lost the ability to utilize the ortho isomer. From M1 cultures we have now isolated a revertant strain (R1) which grows on o-xylene and retains the ability to grow with the meta and para isomers regardless of the selective pressure applied. In P. stutzeri R1, o-xylene is degraded through two successive monooxygenations of the aromatic ring, while m-xylene and p-xylene catabolism proceeds through the progressive oxidation of a methyl substituent, although unquantifiable amounts of these two substrates are transformed into the corresponding dimethylphenols, which are not utilized for further growth. The two catabolic pathways are inducible by all three xylene isomers. PMID:16535677

  20. 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.

  1. Rapid survey of four Asp isomers in disease-related proteins by LC-MS combined with commercial enzymes.

    Science.gov (United States)

    Maeda, Hiroki; Takata, Takumi; Fujii, Norihiko; Sakaue, Hiroaki; Nirasawa, Satoru; Takahashi, Saori; Sasaki, Hiroshi; Fujii, Noriko

    2015-01-06

    Until relatively recently, it was considered that D-amino acids were excluded from living systems except for the cell wall of microorganisms. However, D-aspartate residues have now been detected in long-lived proteins from various tissues of elderly humans. Formation of D-aspartate in proteins induces aggregation and loss of function, leading to age-related disorders such as cataracts and Alzheimer disease. A recent study used LC-MS to analyze isomers of Asp residues in proteins precisely without complex purification of the proteins. However, to identify the four Asp isomers (Lα, Lβ, Dβ, and Dα) on the chromatogram, it was necessary to synthesize reference peptides containing the four different Asp isomers as standards. Here, we describe a method for rapidly and comprehensively identifying Asp isomers in proteins using a combination of LC-MS and commercial enzymes without synthesizing reference peptides. The protein sample is treated with trypsin, trypsin plus Asp-N, trypsin plus PIMT, trypsin plus paenidase, and the resulting peptides are applied to LC-MS. Because Asp-N hydrolyzes peptide bonds on the N-terminus of only Lα-Asp residues, it differentiates peptides containing Lα-Asp from those containing the other three isomers. Similarly, PIMT recognizes only peptides containing Lβ-Asp residues, and paenidase internally cleaves the C-terminus of Dα-Asp residues. This approach was successfully applied to the analysis of all tryptic peptides in aged lens. The comprehensive quantitative data of Asp isomer formation in age-related proteins obtained via this method might be used as biomarkers of age-related disease.

  2. Insights into gas-phase reaction mechanisms of small carbon radicals using isomer-resolved product detection.

    Science.gov (United States)

    Trevitt, Adam J; Goulay, Fabien

    2016-02-17

    For reactive gas-phase environments, including combustion, extraterrestrials atmospheres and our Earth's atmosphere, the availability of quality chemical data is essential for predictive chemical models. These data include reaction rate coefficients and product branching fractions. This perspective overviews recent isomer-resolved production detection experiments for reactions of two of the most reactive gas phase radicals, the CN and CH radicals, with a suite of small hydrocarbons. A particular focus is given to flow-tube experiments using synchrotron photoionization mass spectrometry. Coupled with computational studies and other experiment techniques, flow tube isomer-resolved product detection have provided significant mechanistic details of these radical + neutral reactions with some general patterns emerging.

  3. Simultaneous determination of nitrophenol isomers at the single-wall carbon nanotube compound conducting polymer film modified electrode

    Institute of Scientific and Technical Information of China (English)

    ZHANG Hui; WANG Zhenhui; ZHOU Shuping

    2005-01-01

    Based on the molecular recognition ability of conductive polymer and the peculiar properties of carbon nanotubes, a novel single wall nanotubes (SWNTs) compound poly(4- aminopyridine) modified electrode (SWNTs/POAPE) is prepared at glass carbon electrode (GCE). The electrochemistry response of nitrophenol isomers is studied at the SWNTs/POAPE. The result indicates that o-, m- and p-nitrophenol are separated entirely at the SWNTs/POAPE interface. The electrode present here can be easily used to determine nitrophenol isomers simultaneously with higher sensitivity.

  4. K-isomers in Hf nuclei at and beyond the neutron-rich edge of beta-stability

    CERN Document Server

    Chowdhury, P; Seabury, E H; Walker, P M; Wheldon, C; Ahmad, I; Carpenter, M P; Hackman, G; Janssens, R V F; Khoo, T L; Nisius, D; Reiter, P

    1999-01-01

    New high-K isomers are populated in sup 1 sup 8 sup 0 sup , sup 1 sup 8 sup 1 sup , sup 1 sup 8 sup 2 Hf nuclei via inelastic excitation and transfer reactions, using pulsed sup 2 sup 3 sup 8 U beams on Hf targets. The new data explore K-hindrances for different multipolarities and the role of residual spin-spin interactions for multi-quasiparticle (qp) configurations at the neutron-rich edge of the beta-stability line. The mapping of 4-qp K-isomers in the A approx 180 region is extended into neutron-rich territory.

  5. Application of the high-spin isomer beams to the secondary fusion reaction and the measurement of g-factor

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, H. [RIKEN - Institute of Physical and Chemical Research, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Asahi, K. [RIKEN - Institute of Physical and Chemical Research, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Kishida, T. [RIKEN - Institute of Physical and Chemical Research, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Ueno, H. [RIKEN - Institute of Physical and Chemical Research, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Sato, W. [RIKEN - Institute of Physical and Chemical Research, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Yoshimi, A. [RIKEN - Institute of Physical and Chemical Research, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Kobayashi, Y. [RIKEN - Institute of Physical and Chemical Research, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Kameda, D. [Department of Physics, Tokyo Institute of Technology, 2-12-1 Oh-okayama, Meguro, Tokyo 152-8551 (Japan); Miyoshi, H. [Department of Physics, Tokyo Institute of Technology, 2-12-1 Oh-okayama, Meguro, Tokyo 152-8551 (Japan); Fukuchi, T. [Department of Physics, Kyushu University, Fukuoka 812-8581 (Japan); Wakabayashi, Y. [Department of Physics, Kyushu University, Fukuoka 812-8581 (Japan); Sasaki, T. [Department of Physics, Kyushu University, Fukuoka 812-8581 (Japan); Kibe, M. [Department of Physics, Kyushu University, Fukuoka 812-8581 (Japan); Hokoiwa, N. [Department of Physics, Kyushu University, Fukuoka 812-8581 (Japan); Odahara, A. [Nishinippon Institute of Technology, Kanda, Fukuoka 800-03 (Japan); Cederwall, B. [Department of Physics, Royal Institute of Technology, Frescativ gen 24, Stockholm 10405 (Sweden); Lagergren, K. [Department of Physics, Royal Institute of Technology, Frescativ gen 24, Stockholm 10405 (Sweden); Podolyak, Zs. [Department of Physics, University of Surrey, Guildford GU2 7XH (United Kingdom); Ishihara, M. [RIKEN - Institute of Physical and Chemical Research, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan)] [and others

    2004-12-27

    A technique for providing high-spin isomers as probes of the fusion reaction and the measurement of g-factor has been worked out at RIKEN. In the study of the fusion reaction {sup 12}C({sup 145m}Sm,xn){sup 157-x}Er, the {gamma} rays emitted from the fusion-evaporation residue {sup 154}Er have been successfully observed. The nuclear g-factor of the T{sub 1/2} = 28 ns high-spin isomer in {sup 149}Dy has been measured with the {gamma}-ray TDPAD method.

  6. K-isomers in Hf nuclei at and beyond the neutron-rich edge of {beta}-stability.

    Energy Technology Data Exchange (ETDEWEB)

    Chowdhury, P.; Alarcao, R. D.; Seabury, E. H.; Walker, P. M.; Wheldon, C.; Ahmad. I.; Carpenter, M. P.; Hackman, G.; Janssens, R. V. F.; Khoo, T. L.; Nisius, D.; Reiter, P.

    1999-03-30

    New high-K isomers are populated in {sup 180,181,182}Hf nuclei via inelastic excitation and transfer reactions, using pulsed {sup 238}U beams on Hf targets. The new data explore K-hindrances for different multipolarities and the role of residual spin-spin interactions for multi-quasiparticle (qp) configurations at the neutron-rich edge of the {beta}-stability line. The mapping of 4-qp K-isomers in the A {approx} 180 region is extended into neutron-rich territory.

  7. Influence of anthraquinone scaffold on E/Z isomer distribution of two thiosemicarbazone derivatives. 2D NMR and DFT studies

    Science.gov (United States)

    Marković, Violeta; Joksović, Milan D.; Marković, Svetlana; Jakovljević, Ivan

    2014-01-01

    A distribution of possible isomeric and tautomeric forms of two tautomerizable anthraquinone-thiosemicarbazones with pronounced cytotoxic potential was investigated using 2D NMR and DFT studies. Conformational analysis of the E and Z isomers of both thiosemicarbazones was performed to find out the most stable conformation for each molecule. It was found that superior stability of E-isomers results from ten-membered intramolecular hydrogen bond between thiosemicarbazone N2H and anthraquinone carbonyl group. This hydrogen bond is stronger than that between thiosemicarbazone N2H and ester oxygen, owing to the large partial negative charge on the anthraquinone oxygen.

  8. The determination of the linear alkylbenzene sulfonate isomers in water samples by gas-chromatography/mass spectrometry.

    Science.gov (United States)

    Moldovan, Zaharie; Avram, Veronica; Marincas, Olivian; Petrov, Plamen; Ternes, Thomas

    2011-01-14

    A number of 20 compounds of linear alkylbenzene sulfonates (LASs) family were identified by electron impact mass spectrometry (EI-MS) in water samples collected from wastewater treatment plants (WWTP). This paper presents the mass spectra of 20 compounds, the proposed mechanism of formation of the diagnostic ions obtained by EI-MS and the distribution of individual isomers in water samples collected from compartments of WWTP. The individual isomers from four homolog series C(10)-, C(11)-, C(12)- and C(13)-LAS were analyzed as methyl derivatives.

  9. 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

  10. Trans fatty acid isomers from hydrogenated fats: The controversy about health implications

    Directory of Open Access Journals (Sweden)

    Valenzuela, Alfonso

    1995-12-01

    Full Text Available Wherever there is a double bond in a fatty acid, there is also a possibility for isomerization. Under partial hydrogenation triacylglycerols composing oils'double bonds may change from cis to trans configuration, therefore products derived from hydrogenated oils such as margarines, shortenings and other industrial fats show high content of trans fatty acid isomers. The health implications of trans fatty acids in our diet is now a concern of controversy, because it has been demonstrated that its metabolic behaviour is as saturated fats. Trans fatty acids increase LDL-cholesterol and simultaneously decrease HDL-cholesterol, being considered both parameters as atherogenics. The oleochemical industry has developed several strategies to reduce the trans fatty acid content of hydrogenated oils, and now margarines and other hydrogenated derived products with low trans fatty acids content can be obtained from the retail market.

    Toda vez que exista un doble enlace en un ácido graso, existe la posibilidad de formación de estructuras isómeras. La hidrogenación parcial de los dobles enlaces de los triglicéridos que forman un aceite puede cambiar la isomería de estos enlaces desde la configuración cisa la configuración trans,por lo cual aquellos productos derivados de la hidrogenación de aceites, tales como las margarinas, las mantecas y otras grasas industriales, presentarán altos contenidos de ácidos grasos con isomería trans.Las implicaciones para la salud derivadas del consumo de ácidos grasos trans en la dieta, son en la actualidad motivo de muchas controversias, ya que se ha demostrado que los ácidos grasostrans se comportan biológicamente como ácidos grasos saturados. Los ácidos grasos transaumentan el colesterol-LDL y disminuyen simultáneamente el colesterol-HDL, siendo consideradas ambas situaciones como aterogénicas. La industria

  11. 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

  12. Effect of Mono- and Di-hydration on the Intramolecular Proton Transfers and Stability of Cyanuric Acid Isomers: A DFT Study

    Indian Academy of Sciences (India)

    YOUNES VALADBEIGI

    2016-08-01

    Structural and thermodynamic properties of 10 isomers of cyanuric acid were studied in aqueous and gas phases, employing B3LYP/6-311++G(d,p) method. The aromaticities of these isomers were evaluated using nucleus-independent chemical shift (NICS) index. The calculations showed that as the number of the ketogroups increases the stability of the isomers increases and the aromaticity decreases. Mono- and di-hydrations of the isomers did not change the stability trend, so that the tri-keto isomer was the most stable isomer amongthe hydrated and non-hydrated isomers. The activation energies (Ea) of the intramolecular proton transfers (tautomerisms) and energy barriers of H-rotations around its C-O axis in enolic isomers were calculated. The energy barriers were smaller than 45 kJ/mol for the H-rotations while the Ea values of the proton transfers were in the range of 130-210 kJ/mol. Effect of micro-hydrations on the transition state structures and the energy barriers of the tautomerisms were investigated. The mono- and di-hydrations lower the activation energies to100-130 kJ/mol and 110-145 kJ/mol, respectively.

  13. LC-H-1 NMR used for determination of the elution order of S-naproxen glucuronide isomers in two isocratic reversed-phase LC-systems

    DEFF Research Database (Denmark)

    Mortensen, R. W.; Corcoran, O.; Cornett, Claus;

    2001-01-01

    .D. Wilson, J.K. Nicholson, J. Chromatogr. B Biomed. Appl. 685 (1996) 113-122]. The alpha -1-O-acyl isomer was found to be present at approximately 3% of the initial S-naproxen-beta -1-O-acyl glucuronide concentration in the glucuronide isomer mixture after 6 h of incubation at pH 7.40 and 37 degrees...

  14. Manifesting Subtle Differences of Neutral Hydrophilic Guest Isomers in a Molecular Container by Phase Transfer.

    Science.gov (United States)

    Lee, Hyun Hee L; Lee, Jong Wha; Jang, Yoonjung; Ko, Young Ho; Kim, Kimoon; Kim, Hugh I

    2016-07-11

    Achieving strong host-guest interactions between synthetic hosts and hydrophilic guests in solution is challenging because solvation effects overwhelm other effects. To resolve this issue, we transferred complexes of cucurbit[7]uril (CB[7]) and monosaccharides to the gas phase and report here their intrinsic host-guest chemistry in the absence of solvation effects. It was observed that effective host-guest interactions in the gas phase mediated by ammonium cations allow the differentiation of the monosaccharide isomers in complex with CB[7] upon vibrational excitation. The potential of the unique observation was extended to a quantitative supramolecular analytical method for the monosaccharide guests. The combination of host-guest chemistry and phase transfer presented in this study is an effective approach to overcome current limitations in supramolecular chemistry.

  15. Isomers and oblate collectivity at high spin in neutron-rich Pt isotopes

    Directory of Open Access Journals (Sweden)

    Tandel S.K.

    2016-01-01

    Full Text Available Isomers and high-spin structures with rotation-aligned oblate configurations have been studied in several Pt isotopes. The 12+ states in the even Pt isotopes from 192–198Pt are found to be metastable, and have (i13/22 neutron character. The progression of E2 transition probabilities from the 12+ to 10+ states across the Pt isotopic chain implies reduction in collectivity, followed by an abrupt decrease at N=120 (198Pt. This behavior is quite distinct from the gradual decrease of B(E2 values near the respective ground states. A large contribution from aligned angular momentum, to the rotational sequences built on the 12+ states, is visible. This is due to the relatively small crossing frequencies for nucleons in low-Ω orbitals at oblate deformation in comparison to higher values for prolate shapes. As a result, oblate rotation is found to be increasingly favored for higher neutron numbers.

  16. Bonding and Moessbauer Isomer Shifts in (Hg,Pb)—1223 Cuprate

    Institute of Scientific and Technical Information of China (English)

    高发明; 田永君; 谌岩; 李东春; 董海峰; 张思远

    2003-01-01

    By using the chemical bond theory of dielectric description,the chemical bond parameters of(Hg,Pb)-1223 were calculated.The results show that the(Ba,Sr)-O and Ca-0 types of bond have higher ionic character,while the Cu-O and(Hg,Pb)-0 types of bond have more covalent character.Moessbauer isomer shifts of 57Fe and 119Sn doped in(Hg,Pb)-1223 were calculated by using the chemical environmental factor,he,defined by covalency and electronic polarizability.Four valence state tin and three valence iron sites were identified in 57Fe and 119Sn doped(Hg,Pb)-1223 superconductor.It can be concluded that all of the Fe atoms substitute the Cu at square planar Cu(1) site,Whereas Sn prefers to substitute the square pyramidal Cu(2) site.

  17. Bonding and M?ssbauer Isomer Shifts in (Tl,Pb) - 1223 Cuprate

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    By using the chemical bond theory of dielectric description,the chemical bond parameters of (Tl,Pb) - 1223 was calculated.The results show that the Sr-O,Tl-O,and Ca-O types of bond have higher ionic character and the Cu-O types of bond have more covalent character.M?ssbauer isomer shifts of 57Fe and 119Sn doped in (Tl,Pb) -1223 were calculated by using the chemical environmental factor,he,defined by covalency and electronic polarizability.Four valence state tin and three valence iron sites were identified in 57Fe,and 119Sn doped (Tl,Pb) -1223 superconductor.We conclude that all of the Fe atoms substitute the Cu at square planar Cu (1) site,whereas Sn prefers to substitute the square pyramidal Cu (2) site.

  18. Antitumor activity of platinum(II) complexes of 1,2-diamino-cyclohexane isomers.

    Science.gov (United States)

    Kidani, Y; Noji, M; Tashiro, T

    1980-10-01

    Dichloro, dibromo, oxalato, malonato, dinitrato, sulfato and mono and bis-(D-glucuronato) platinum(II) complexes of 1,2-diaminocyclohexane (dach) isomers were prepared and tested on L1210 mouse leukemia employing the NCI protocol for evaluation of Pt analogs. A large number of long-term survivors were observed with certain analogs, though the therapeutic indices (optimal dose/minimum effective dose) were not large. Among the analogs tested, the oxalato, malonato, dinitrato and mono-(D-glucuronato) Pt(II) complexes of trans-1,2-diaminocyclohexane were found to be particularly effective. The glucuronato Pt complexes appear to be promising candidates for clinical trial since they have the highest solubility in water.

  19. Large prebiotic molecules in space: photo-physics of acetic acid and its isomers

    CERN Document Server

    Puletti, Fabrizio; Mulas, Giacomo; Cecchi-Pestellini, Cesare

    2009-01-01

    An increasing number of large molecules have been positively identified in space. Many of these molecules are of biological interest and thus provide insight into prebiotic organic chemistry in the protoplanetary nebula. Among these molecules, acetic acid is of particular importance due to its structural proximity to glycine, the simplest amino acid. We compute electronic and vibrational properties of acetic acid and its isomers, methyl formate and glycolaldehyde, using density functional theory. From computed photo-absorption cross-sections, we obtain the corresponding photo-absorption rates for solar radiation at 1 AU and find them in good agreement with previous estimates. We also discuss glycolaldehyde diffuse emission in Sgr B2(N), as opposite to emissions from methyl formate and acetic acid that appear to be concentrate in the compact region Sgr B2(N-LMH).

  20. 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.

  1. Uncovering biologically significant lipid isomers with liquid chromatography, ion mobility spectrometry and mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Kyle, Jennifer E.; Zhang, Xing; Weitz, Karl K.; Monroe, Matthew E.; Ibrahim, Yehia M.; Moore, Ronald J.; Cha, Jeeyeon; Sun, Xiaofei; Lovelace, Erica S.; Wagoner, Jessica; Polyak, Steve; Metz, Thomas O.; Dey, Sudhansu K.; Smith, Richard D.; Burnum-Johnson, Kristin E.; Baker, Erin Shammel

    2016-01-01

    Understanding how biological molecules are generated, metabolized and eliminated in living systems is important for interpreting processes such as immune response and disease pathology. While genomic and proteomic studies have provided vast amounts of information over the last several decades, interest in lipidomics has also grown due to improved analytical technologies revealing altered lipid metabolism in type 2 diabetes, cancer, and lipid storage disease. Liquid chromatography and mass spectrometry (LC-MS) measurements are currently the dominant approach for characterizing the lipidome by providing detailed information on the spatial and temporal composition of lipids. However, interpreting lipids’ biological roles is challenging due to the existence of numerous structural and stereoisomers (i.e. distinct acyl chain and double-bond positions), which are unresolvable using present LC-MS approaches. Here we show that combining structurally-based ion mobility spectrometry (IMS) with LC-MS measurements distinguishes lipid isomers and allows insight into biological and disease processes.

  2. Separation of porphyrin-based photosensitizer isomers by laser-induced fluorescence capillary electrophoresis.

    Science.gov (United States)

    Peng, Xuejun; Sternberg, Ethan; Dolphin, David

    2005-10-01

    Methods for the separation of photosensitizer isomers, such as benzoporphyrin derivative monoacid, benzoporphyrin ethyl monoacid, 2-[1-hexyloxyethyl]-2-devinylpyropheophorbide-a, diethyleneglycol diester benzoporphyrin derivative, tin ethyl etiopurpurin, and phthalocyanine tetrasulfonate, have been systematically developed by CE. Detection was accomplished by UV absorption at 214 nm or by LIF with excitation at 442/488 nm and emission at 690 nm. The effects of three major experimental parameters of buffer types, organic solvents, and surfactant additives are described. The optimized separation conditions were determined so as to provide satisfactory separation efficiency and analysis time. The methods are shown to be suitable for the separation and determination of porphyrin and phthalocyanines regioisomers, diastereoisomers, and enantiomers.

  3. Pharmacological profile of the isomers of the GluR-specific agonist ATPA.

    Science.gov (United States)

    Curry, K; Pajouhesh, H

    1998-06-01

    We have synthesized the (R)- and (S)-isomers of 2-amino-3-(3-hydroxy-5-tert-butylisoxazol-4-yl) propanoate (ATPA) by stereochemically certain routes. Our studies in the rat cortical wedge preparation indicate that (R)-ATPA has no observable excitatory effect, while (S)-ATPA has an apparent K(D) of 16 microM. This excitatory response is unaffected by the specific N-methyl-D-aspartate (NMDA) antagonist, D-2-amino-5-phosphonopentanoic acid (DAP5) but is partially blocked by 6-nitro-sulfamoyl[f]quinoxalinedione (NBQX) at concentrations that attenuate the effects of alpha-amino-3-hydroxy-5-methyl-4-isoxazole-4-propionate (AMPA), the effects are however reduced by the nonspecific antagonist kynurenate (KYN), indicating an interaction with a class of kainate receptor.

  4. NMR characterization of functional groups: 9--isomer ratios of available chloromethylstyrene mixtures

    Science.gov (United States)

    Manatt, S. L.; Khune, G. D.; Khatri, N. A.

    1985-01-01

    From the assignments of the 1H and 13C 11.7 tesla NMR spectra of available mixtures of m- and p-chloromethylstyrene, the proportion of the meta and para compounds are easily determined. For these materials from two common commercial sources, proportions of 72 and 28% and 68 and 32% were found. These concentrations are substantially different from the often assumed 60 and 40% for the meta and para compounds, respectively. The influence of this difference on the desired properties of copolymers made from such mixtures is discussed. An alternative quantitative procedure for determining the chloromethyl group isomer ratios is also described which employs silver trifluoroacetate in acetone displacement of chloride and 19F NMR examination of the resulting ester mixture with a 2.3 tesla spectrometer.

  5. Pairing and Blocking in High-K Isomers: Variation of the Collective Parameter gR

    Directory of Open Access Journals (Sweden)

    Stone N.J.

    2013-12-01

    Full Text Available Using the principle of additivity, the quasi-particle contribution to magnetism in high-K isomers of Lu - Re has been estimated. Based on these estimates band structure branching ratio data is used to explore the behavior of the collective contribution as the number and neutron/proton nature (Np, Nn, of the quasi-particle excitations, change. A striking systematic variation of the collective g-factor gR with the difference, Np – Nn, is revealed. Basic ideas of pairing, its quenching by quasi-particle excitation and the consequent changes to moment of inertia and collective magnetism are discussed. The new found systematic behaviour of gR opens a fresh window on these effects amenable to detailed theoretical investigation.

  6. Confinement effects on the nuclear spin isomer conversion of H$_2$O

    CERN Document Server

    Turgeon, Pierre-Alexandre; Alexandrowicz, Gil; Peperstraete, Yoann; Philippe, Laurent; Fillion, Jean-Hugues; Michaut, Xavier; Ayotte, Patrick

    2016-01-01

    The mechanism for interconversion between the nuclear spin isomers (NSI) of H$_2$O remains shrouded in uncertainties. The temperature dependence displayed by NSI interconversion rates for H$_2$O isolated in an Argon matrix provides evidence that confinement effects are responsible for the dramatic increase in their kinetics with respect to the gas phase, providing new pathways for o-H$_2$O $\\leftrightarrow$ p-H$_2$O conversion in endohedral compounds. This reveals intramolecular aspects of the interconversion mechanism which may improve methodologies for the separation and storage of NSI en route to applications in nuclear magnetic resonance spectroscopy and imaging. It may also improve astronomers' ability to use their relative abundance in the interstellar medium as proxies, thereby providing a valuable "astronomical clock".

  7. Urinary sialyloligosaccharides in adult type sialidosis: occurrence of two positional isomers.

    Science.gov (United States)

    Kuriyama, M; Ariga, T; Ando, S; Suzuki, M; Yamada, T; Miyatake, T

    1981-04-01

    Two positional isomers of sialyloligosaccharides were isolated from the urine of a patient with adult type sialidosis with partial deficiency of beta-galactosidase. From structural studies including sugar analysis, enzyme degradation and methylation analysis, the following structures are deduced; 1. alpha-AcNeu-(2 leads to 3)-beta-Gal-(1 leads to 4)-beta-GlcNAc-(1 leads to 2)-alpha-Man-(1 leads to 3)-beta-Man-(1 leads to 4)-GlcNAc 2. alpha-AcNeu-(2 leads to 3)-beta-Gal-(1 leads to 4)-beta-GlcNAc-(1 leads to 2)-alpha-Man-(1 leads to 6)-beta-Man-(1 leads to 4)-GlcNAc The sialyloligosaccharide 1 has previously been reported to be present in liver and urine of patients with mucolipidosis I, II and variant forms. The sialyloligosaccharide 2 was first demonstrated in human urine.

  8. COLD ELECTRON REACTIONS PRODUCING THE ENERGETIC ISOMER OF HYDROGEN CYANIDE IN INTERSTELLAR CLOUDS

    Energy Technology Data Exchange (ETDEWEB)

    Mendes, Mario B.; Buhr, Henrik; Berg, Max H.; Froese, Michael; Grieser, Manfred; Jordon-Thaden, Brandon; Krantz, Claude; Novotny, Oldrich; Novotny, Steffen; Orlov, Dmitry A.; Petrignani, Annemieke; Repnow, Roland; Schwalm, Dirk; Shornikov, Andrey; Stuetzel, Julia; Wolf, Andreas [Max-Planck-Institut fuer Kernphysik, Saupfercheckweg 1, 69117 Heidelberg (Germany); Heber, Oded; Rappaport, Michael L.; Zajfman, Daniel, E-mail: A.Wolf@mpi-hd.mpg.de [Weizmann Institute of Science, P.O. Box 26, 76100 Rehovot (Israel)

    2012-02-10

    Using event-by-event fragment momentum spectroscopy in a storage-ring merged-beams experiment, we find laboratory evidence that in the dissociative recombination (DR) of HCNH{sup +} with cold electrons the energetic isomer HNC is produced with a high yield, similar to that of HCN. With a newly implemented mass-sensitive fragment imaging detector, we analyze the kinetic energy release of the triatomic fragments DCN/DNC from the DR reaction of the isotopologue DCND{sup +} with cold (near 10 K) electrons. The results show that the internal energy of these fragments is extremely high, far exceeding the isomerization barrier between DNC and DCN. From this laboratory characterization of the DR reaction we conclude that also the triatomic fragment HCN/HNC from the DR of HCNH{sup +} will carry a large amount of ro-vibrational excitation and show that this implies an isomeric production ratio in a narrow range near unity.

  9. Coexisting shape- and high-K isomers in the shape transitional nucleus {sup 188}Pt

    Energy Technology Data Exchange (ETDEWEB)

    Mukhopadhyay, S., E-mail: somm@barc.gov.in [Nuclear Physics Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Biswas, D.C. [Nuclear Physics Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Tandel, S.K. [UM-DAE Centre for Excellence in Basic Sciences, Mumbai 400098 (India); Danu, L.S.; Joshi, B.N.; Prajapati, G.K. [Nuclear Physics Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Nag, Somnath [Dept. of Physics, IIT Kharagpur, Kharagpur 721302 (India); Trivedi, T.; Saha, S.; Sethi, J.; Palit, R. [Dept. of Nuclear and Atomic Physics, TIFR, Mumbai 400005 (India); Joshi, P.K. [Homi Bhabha Centre for Science Education, TIFR, Mumbai 400088 (India)

    2014-12-12

    A high-spin study of the shape transitional nucleus {sup 188}Pt reveals the unusual coexistence of both shape- and K-isomeric states. Reduced B(E2) transition probabilities for decays from these states inferred from the data clearly establish their hindered character. In addition to other excited structures, a rotational band built upon the K isomer is identified, and its configuration has been assigned through an analysis of alignments and branching ratios. The shape evolution with spin in this nucleus has been inferred from both experimental observables and cranking calculations. The yrast positive parity structure appears to evolve from a near-prolate deformed shape through triaxial at intermediate excitation, and eventually to oblate at the highest spins.

  10. Searching for high-K isomers in the proton-rich A ˜ 80 mass region

    Science.gov (United States)

    Bai, Zhi-Jun; Jiao, Chang-Feng; Gao, Yuan; Xu, Fu-Rong

    2016-09-01

    Configuration-constrained potential-energy-surface calculations have been performed to investigate the K isomerism in the proton-rich A ˜ 80 mass region. An abundance of high-K states are predicted. These high-K states arise from two and four-quasi-particle excitations, with Kπ = 8+ and Kπ = 16+, respectively. Their excitation energies are comparatively low, making them good candidates for long-lived isomers. Since most nuclei under study are prolate spheroids in their ground states, the oblate shapes of the predicted high-K states may indicate a combination of K isomerism and shape isomerism. Supported by National Key Basic Research Program of China (2013CB834402) and National Natural Science Foundation of China (11235001, 11320101004 and 11575007)

  11. A Singlet Thiophosphoryl Nitrene and Its Interconversion with Thiazyl and Thionitroso Isomers.

    Science.gov (United States)

    Li, Hongmin; Wu, Zhuang; Li, Dingqing; Zeng, Xiaoqing; Beckers, Helmut; Francisco, Joseph S

    2015-09-02

    Thiophosphoryl nitrenes, R2P(S)N, are thiazirine-like intermediates that have been chemically inferred from trapping products in early solution studies. In this work, photolysis of the simplest thiophosphoryl azide, F2P(S)N3, in solid noble-gas matrices enabled a first-time spectroscopic (IR and UV-vis) identification of the thiophosphoryl nitrene F2P(S)N in its singlet ground state. Upon visible-light irradiation (≥495 nm), it converts into the thionitroso isomer F2P-N═S, which can also be produced in the gas phase from flash vacuum pyrolysis of F2P(S)N3. Further irradiation of F2P-NS with 365 nm UV light leads to the reformation of F2P(S)N and isomerization to the thiazyl species F2P-S≡N.

  12. Cationic iridium(III) complexes with two carbene-based cyclometalating ligands: cis versus trans isomers.

    Science.gov (United States)

    Monti, Filippo; La Placa, Maria Grazia I; Armaroli, Nicola; Scopelliti, Rosario; Grätzel, Michael; Nazeeruddin, Mohammad Khaja; Kessler, Florian

    2015-03-16

    A series of cationic iridium(III) complexes with two carbene-based cyclometalating ligands and five different N^N bipyridine and 1,10-phenanthroline ancillary ligands is presented. For the first time--in the frame of a rarely studied class of bis(heteroleptic) iridium complexes with two carbene-based cyclometalating ligands--a pair of cis and trans isomers has been isolated. All complexes (trans-1-5 and cis-3) were characterized by (1)H NMR, (13)C NMR, (31)P NMR, and HRMS (ESI-TOF); in addition, crystal structures of cis-3 and trans-4 are reported and discussed. Cyclic voltammetric studies show that the whole series exhibits highly reversible oxidation and reduction processes, suggesting promising potential for optoelectronic applications. Ground-state DFT and TD-DFT calculations nicely predict the blue shift experimentally observed in the room-temperature absorption and emission spectra of cis-3, compared to the trans complexes. In CH3CN, cis-3 displays a 4-fold increase in photoluminescence quantum yield (PLQY) with respect to trans-3, as a consequence of drastically slower nonradiative rate constant. By contrast, at 77 K, the emission properties of all the compounds, including the cis isomer, are much more similar, with a pronounced hypsochromic shift for the trans complexes. A similar behavior is found in solid state (1% w/w poly(methyl methacrylate) matrix), with all complexes displaying PLQY of ∼70-80%, comparable emission lifetimes (τ ≈ 1.3 μs), and a remarkable rigidochromic shift. To rationalize the more pronounced nonradiative deactivation (and smaller PLQY) observed for photoexcited trans complexes, comparative temperature-dependent emission studies in the range of 77-450 K for cis-3 and trans-3 were made in propylene glycol, showing that solvation effects are primarily responsible for the observed behavior.

  13. Fixation of the two Tabun isomers in acetylcholinesterase: a QM/MM study.

    Science.gov (United States)

    Kwasnieski, Ophélie; Verdier, Laurent; Malacria, Max; Derat, Etienne

    2009-07-23

    Dysfunction of acetylcholinesterase (AChE) due to inhibition by organophosphorus (OP) compounds is a major threat since AChE is a key enzyme in neurotransmission. To more rigorously design reactivation agents, it is of prime importance to understand the mechanism of inhibition of AChE by OP compounds. Tabun is one of the more potent nerve agents. It is produced as a mixture of two enantiomers, one of them (the levorotatory isomer) being 6.3 times more potent. Could it be that the inhibition mechanism is different for the two enantiomers? To address this critical issue, we used a hybrid quantum mechanics/molecular mechanics (QM/MM) methodology. Calculations were performed using BP86 functional and TZVP basis set. Single points were also done with B3LYP and PBE0 functionals. We studied the four possible attacks of tabun on the oxygen of Ser203 using two crystallographic structures (PDB codes 2C0P and 3DL7): (S) tabun with the cyano group syn to the oxygen of Ser203 and (R) tabun with the cyano group anti, corresponding to the experimental X-ray structure; (S) tabun with the cyano group anti to the oxygen of Ser203 and (R) tabun with the cyano group syn, leading to a different isomer than was experimentally seen. We found that the most active enantiomer is (S) tabun with the cyano group syn to the oxygen of Ser203. Thus it seems that the cyano group does not leave anti to the oxygen of Ser203 due to repulsive polar interactions between cyanide and aromatic residues in the active site.

  14. Androstanediol glucuronide isomers in normal men and women and in men infused with labeled dihydrotestosterone

    Energy Technology Data Exchange (ETDEWEB)

    Rittmaster, R.S.; Thompson, D.L.; Listwak, S.; Loriaux, D.L.

    1988-01-01

    3 alpha-Androstanediol glucuronide (Adiol G) is a major metabolite of dihydrotestosterone (DHT). Adiol G actually represents 2 different compounds, since the glucuronide can be conjugated at the 3-carbon position (Adiol 3-G) or at the 17-carbon position (Adiol 17-G). To determine which glucuronide represents the predominant physiological DHT metabolite and which isomer is the major circulating form, we developed a RIA to directly measure Adiol 3-G in serum extracts. In 10 normal men, mean serum Adiol 3-G and total Adiol G levels were 4.44 +/- 0.49 (+/- SE) nmol/L (208 +/- 23 ng/dL) and 27.9 +/- 2.8 nmol/L (1310 +/- 129 ng/dL), respectively (13.9 +/- 3.0% of Adiol G was Adiol 3-G). In 10 normal women sampled during the early follicular phase, mean serum Adiol 3-G and total Adiol G levels were 2.64 +/- 0.64 nmol/L (124 +/- 30 ng/dL) and 14.9 +/- 1.5 nmol/L (697 +/- 69 ng/dL), respectively (17.4 +/- 3.6% of Adiol G was Adiol 3-G). In 4 normal men infused for 8 h with tritiated DHT, 17.4 +/- 3.4% of the resulting tritiated Adiol G was Adiol 3-G. These results indicate that Adiol 17-G is the predominant circulating form of Adiol G in normal men and women and that it is also the major Adiol G isomer derived from DHT.

  15. Solid-matrix luminescence interactions and analytical aspects of phenylphenol isomers on filter paper

    Energy Technology Data Exchange (ETDEWEB)

    Purdy, B.B.

    1992-01-01

    The solid-matrix luminescence limits of detection, percent relative standard deviation, and linear concentration ranges were obtained for model compounds adsorbed on four different solid-matrices. Filter paper showed the best analytical merit. Several solid-matrix luminescence properties of phenylphenol isomers adsorbed on Whatman filter paper were investigated. In the presence of sodium halide salts, the luminescence intensity, lifetime, quantum yield and modulus data were obtained to study heavy-atom effects, quenching effects by salts and moisture, and photophysical processes and molecular interactions in the solid-matrix. For 4-phenylphenol, 3-phenylphenol, and 2-phenylphenol, heavy-atom effects were observed for the room-temperature luminescence intensities. The room-temperature phosphorescence was sensitive to the structural differences among the isomers. The quenching of room-temperature fluorescence by halides was best described by a modified Perrin quenching model which considered a quenching sphere volume and residual fluorescence. At room temperature, the phosphorescence intensities were quenched by moisture while the phosphorescence lifetimes and fluorescence intensities were slightly affected by moisture for 4-phenylphenol and 2-phenylphenol with sodium halides. It was concluded that the adsorption of moisture on the filter paper matrix decreased the matrix rigidity, and thus the phosphorescence intensities of adsorbed phosphors were diminished. The phosphors were well-protected in the matrix, and water molecules could not diffuse effectively to the phosphor molecules. The photophysical data showed how the absorbed energy was channeled into the various radiative and nonradiative processes. Modulus experiments showed there were no differences in the Young's modulus values of filter paper containing NaCl, NaBr, or NaI. A correlation was found between Young's modulus and phosphorescence intensity as a function of the water content adsorbed on

  16. Virtual libraries of tetrapyrrole macrocycles. Combinatorics, isomers, product distributions, and data mining.

    Science.gov (United States)

    Taniguchi, Masahiko; Du, Hai; Lindsey, Jonathan S

    2011-09-26

    A software program (PorphyrinViLiGe) has been developed to enumerate the type and relative amounts of substituted tetrapyrrole macrocycles in a virtual library formed by one of four different classes of reactions. The classes include (1) 4-fold reaction of n disubstituted heterocycles (e.g., pyrroles or diiminoisoindolines) to form β-substituted porphyrins, β-substituted tetraazaporphyrins, or α- or β-substituted phthalocyanines; (2) combination of m aminoketones and n diones to form m × n pyrroles, which upon 4-fold reaction give β-substituted porphyrins; (3) derivatization of an 8-point tetrapyrrole scaffold with n reagents, and (4) 4-fold reaction of n aldehydes and pyrrole to form meso-substituted porphyrins. The program accommodates variable ratios of reactants, reversible or irreversible reaction (reaction classes 1 and 2), and degenerate modes of formation. Pólya's theorem (for enumeration of cyclic entities) has also been implemented and provides validation for reaction classes 3 and 4. The output includes the number and identity of distinct reaction-accessible substituent combinations, the number and identity of isomers thereof, and the theoretical mass spectrum. Provisions for data mining enable assessment of the number of products having a chosen pattern of substituents. Examples include derivatization of an octa-substituted phthalocyanine with eight reagents to afford a library of 2,099,728 members (yet only 6435 distinct substituent combinations) and reversible reaction of six distinct disubstituted pyrroles to afford 2649 members (yet only 126 distinct substituent combinations). In general, libraries of substituted tetrapyrrole macrocycles occupy a synthetically accessible region of chemical space that is rich in isomers (>99% or 95% for the two examples, respectively).

  17. DDT and HCH, two discontinued organochlorine insecticides in the Great Lakes region: isomer trends and sources.

    Science.gov (United States)

    Venier, Marta; Hites, Ronald A

    2014-08-01

    The uses of the insecticides 1,1'-(2,2,2-trichloroethylidene)bis[4-chlorobenzene] (p,p'-DDT) and γ-hexachlorocyclohexane (γ-HCH) have been discontinued for several years, but they are still consistently detected in air samples collected on the shores of the Great Lakes. Although the agricultural uses of DDT have been restricted in the United States since 1972, DDT continued to be used to manufacture the miticide, dicofol, up until 2011. The use of the technical HCH mixture in North America was restricted in the 1970s, when it was replaced by one of its purified conformers, γ-HCH, also known as lindane. In this study, we have focused on isomer-specific data to gain insights on the temporal trends and possible sources of these compounds. In particular, we calculated ratios of the concentrations of p,p'-DDE+p,p'-DDD versus the sum of the concentrations of the three p,p' isomers. These ratios are about the same at all five of our sampling sites and are about the same as observed globally. We also calculated the ratio of the concentrations of o,p'-DDT versus the sum of concentrations of o,p'-DDT+p,p'-DDT. This ratio has increased significantly at all five sites over the last 15-20 years. We suggest that dicofol, which contained about 11% o,p'-DDT, may now be a significant, additional source of DDT to the Great Lakes. The average ratio of the concentration of γ-HCH (lindane) versus the sum of the concentrations of γ-HCH+α-HCH did not vary significantly with time, but it did show an urban signature, suggesting that cities may be more important sources of these compounds than previously suspected.

  18. Combustion of butanol isomers - A detailed molecular beam mass spectrometry investigation of their flame chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Osswald, Patrick; Gueldenberg, Hanna; Kohse-Hoeinghaus, Katharina [Department of Chemistry, Bielefeld University (Germany); Yang, Bin [National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui (China); Department of Aerospace and Mechanical Engineering, University of Southern California, Los Angeles, CA (United States); Yuan, Tao; Qi, Fei [National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui (China)

    2011-01-15

    The combustion chemistry of the four butanol isomers, 1-, 2-, iso- and tert-butanol was studied in flat, premixed, laminar low-pressure (40 mbar) flames of the respective alcohols. Fuel-rich ({phi} = 1.7) butanol-oxygen-(25%)argon flames were investigated using different molecular beam mass spectrometry (MBMS) techniques. Quantitative mole fraction profiles are reported as a function of burner distance. In total, 57 chemical compounds, including radical and isomeric species, have been unambiguously assigned and detected quantitatively in each flame using a combination of vacuum ultraviolet (VUV) photoionization (PI) and electron ionization (EI) MBMS. Synchrotron-based PI-MBMS allowed to separate isomeric combustion intermediates according to their different ionization thresholds. Complementary measurements in the same flames with a high mass-resolution EI-MBMS system provided the exact elementary composition of the involved species. Resulting mole fraction profiles from both instruments are generally in good quantitative agreement. In these flames of the four butanol isomers, temperature, measured by laser-induced fluorescence (LIF) of seeded nitric oxide, and major species profiles are strikingly similar, indicating seemingly analog global combustion behavior. However, significant variations in the intermediate species pool are observed between the fuels and discussed with respect to fuel-specific destruction pathways. As a consequence, different, fuel-specific pollutant emissions may be expected, by both their chemical nature and concentrations. The results reported here are the first of their kind from premixed isomeric butanol flames and are thought to be valuable for improving existing kinetic combustion models. (author)

  19. Optical processing

    Science.gov (United States)

    Gustafson, S. C.

    1985-12-01

    The technical contributions were as follows: (1) Optical parallel 2-D neighborhood processor and optical processor assessment technique; (2) High accuracy with moderately accurate components and optical fredkin gate architectures; (3) Integrated optical threshold computing, pipelined polynomial processor, and all optical analog/digital converter; (4) Adaptive optical associative memory model with attention; (5) Effectiveness of parallelism and connectivity in optical computers; (6) Optical systolic array processing using an integrated acoustooptic module; (7) Optical threshold elements and networks, holographic threshold processors, adaptive matched spatial filtering, and coherence theory in optical computing; (8) Time-varying optical processing for sub-pixel targets, optical Kalman filtering, and adaptive matched filtering; (9) Optical degrees of freedom, ultra short optical pulses, number representations, content-addressable-memory processors, and integrated optical Givens rotation devices; (10) Optical J-K flip flop analysis and interfacing for optical computers; (11) Matrix multiplication algorithms and limits of incoherent optical computers; (12) Architecture for machine vision with sensor fusion, pattern recognition functions, and neural net implementations; (13) Optical computing algorithms, architectures, and components; and (14) Dynamic optical interconnections, advantages and architectures.

  20. Pulse-fluence-specified optimal control simulation with applications to molecular orientation and spin-isomer-selective molecular alignment

    Energy Technology Data Exchange (ETDEWEB)

    Yoshida, Masataka; Nakashima, Kaoru; Ohtsuki, Yukiyoshi [Department of Chemistry, Graduate School of Science, Tohoku University 6-3 Aza-Aoba, Aramaki, Aoba-ku, Sendai 980-8578 (Japan)

    2015-12-31

    We propose an optimal control simulation with specified pulse fluence and amplitude. The simulation is applied to the orientation control of CO molecules to examine the optimal combination of THz and laser pulses, and to discriminate nuclear-spin isomers of {sup 14}N{sub 2} as spatially anisotropic distributions.

  1. Structure and spectroscopic properties of neutral and cationic tetratomic [C,H,N,Zn] isomers: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Redondo, Pilar; Largo, Antonio; Vega-Vega, Álvaro; Barrientos, Carmen, E-mail: cbb@qf.uva.es [Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47011 Valladolid (Spain)

    2015-05-14

    The structure and spectroscopic parameters of the most relevant [C,H,N,Zn] isomers have been studied employing high-level quantum chemical methods. For each isomer, we provide predictions for their molecular structure, thermodynamic stabilities as well as vibrational and rotational spectroscopic parameters which could eventually help in their experimental detection. In addition, we have carried out a detailed study of the bonding situations by means of a topological analysis of the electron density in the framework of the Bader’s quantum theory of atoms in molecules. The analysis of the relative stabilities and spectroscopic parameters suggests two linear isomers of the neutral [C,H,N,Zn] composition, namely, cyanidehydridezinc HZnCN ({sup 1}Σ) and hydrideisocyanidezinc HZnNC ({sup 1}Σ), as possible candidates for experimental detections. For the cationic [C,H,N,Zn]{sup +} composition, the most stable isomers are the ion-molecule complexes arising from the direct interaction of the zinc cation with either the nitrogen or carbon atom of either hydrogen cyanide or hydrogen isocyanide, namely, HCNZn{sup +} ({sup 2}Σ) and HCNZn{sup +} ({sup 2}Σ)

  2. A QSAR for the Mutagenic Potencies of Twelve 2-Amino-trimethylimidazopyridine Isomers: Structural, Quantum Chemical,and Hydropathic Factors

    Energy Technology Data Exchange (ETDEWEB)

    Knize, M G; Hatch, F T; Tanga, M J; Lau, E V; Colvin, M E

    2005-04-23

    An isomeric series of heterocyclic amines related to one found in heated muscle meats was investigated for properties that predict their measured mutagenic potency. Eleven of the 12 possible 2-amino-trimethylimidazopyridine (TMIP) isomers were tested for mutagenic potency in the Ames/Salmonella test with bacterial strain TA98, and resulted in a 600-fold range in potency. Structural, quantum chemical and hydropathic data were calculated on the parent molecules and the corresponding nitrenium ions of all of the tested isomers to establish models for predicting the potency of the unknown isomer. The regression model accounting for the largest fraction of the total variance in mutagenic potency contains four predictor variables: dipole moment, a measure of the gap between amine LUMO and HOMO energies, percent hydrophilic surface, and energy of amine LUMO. The most important determinants of high mutagenic potency in these amines are: (1) a small dipole moment, (2) the combination of b-face ring fusion and N3-methyl group, and (3) a lower calculated energy of the {pi} electron system. Based on predicted potency from the average of five models, the isomer not yet synthesized and tested is expected to have a mutagenic potency of 0.84 revertants/{micro}g in test strain TA98.

  3. Reverse shape selectivity in the liquid-phase adsorption of xylene isomers in zirconium terephthalate MOF UiO-66.

    Science.gov (United States)

    Moreira, Mariana A; Santos, João C; Ferreira, Alexandre F P; Loureiro, José M; Ragon, Florence; Horcajada, Patricia; Shim, Kyu-E; Hwang, Young-K; Lee, U-Hwang; Chang, Jong-S; Serre, Christian; Rodrigues, Alírio E

    2012-04-03

    Powder, agglomerates, and tablets of the microporous zirconium(IV) terephthalate metal-organic framework UiO-66 were evaluated for the selective adsorption and separation of xylene isomers in the liquid phase using n-heptane as the eluent. Pulse experiments, performed at 313 K in the presence of n-heptane, revealed the o-xylene preference of this material, which was further confirmed by binary and multicomponent breakthrough experiments in the presence of m- and p-xylene, resulting in selectivities at 313 K of 1.8 and 2.4 with regards to m-xylene and p-xylene, respectively. Additionally, because p-xylene is the less retained isomer, UiO-66 presents a selectivity pattern that is reverse of that of the xylenes' molecular dimension with respect to shape selectivity. The shaping of the material as tablets did not significantly change its selectivity toward the o-xylene isomer or toward p-xylene, which was the less retained isomer, despite a loss in capacity. Finally, the selectivity behavior of UiO-66 in the liquid n-heptane phase makes it a suitable material for o-xylene separation in the extract (heavy product) or p-xylene separation in the raffinate (light product) by simulated moving bed technology.

  4. Analysis of 2,4,6-nonatrienal geometrical isomers from male flea beetles, Epitrix hirtipennis and E. fuscula.

    Science.gov (United States)

    Zilkowski, Bruce W; Bartelt, Robert J; Vermillion, Karl

    2008-07-09

    Geometrical isomers of 2,4,6-nonatrienal have been reported from a variety of food- and insect-related sources. It was discovered recently that the eggplant flea beetle, Epitrix fuscula, uses the (2 E,4 E,6 Z) and (2 E,4 E,6 E) isomers as components of its male-produced aggregation pheromone. Here, we learned that the related species, E. hirtipennis, also emits a blend of 2,4,6-nonatrienals, including isomers not previously characterized. Patterns in emission and response suggest a pheromonal function. In an effort to acquire standards to aid in identification, we found that exposing (2 E,4 E,6 E)-2,4,6-nonatrienal (or other available 2,4,6-nonatrienals) to light readily generated a mixture of six geometrical isomers. Configurations of these were determined by NMR, and chromatographic properties (GC and HPLC) were documented. On the basis of chromatographic comparison to these standards, the most abundant, new compound from E. hirtipennis was concluded to be (2 E,4 Z,6 Z)-2,4,6-nonatrienal. Minor components from both E. hirtipennis and E. fuscula were also characterized. The analytical approach given here would also be of use in the food industry, where 2,4,6-nonatrienals are important as aroma compounds.

  5. Improved Resolution of Hydrocarbon Structures and Constitutional Isomers in Complex Mixtures Using Gas Chromatography-Vacuum Ultraviolet-Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Isaacman, Gabriel [Univ. of California, Berkeley, CA (United States); Wilson, Kevin R. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Chan, Arthur W. H. [Univ. of California, Berkeley, CA (United States); Worton, David R. [Univ. of California, Berkeley, CA (United States). Aerosol Dynamics Inc., Berkeley, CA (United States); Kimmel, Joel R. [Aerodyne Research, Inc., Billerica, MA (United States); Univ. of Colorado, Boulder, CO (United States). Tofwerk AG, Thun (Switzerland); Nah, Theodora [Univ. of California, Berkeley, CA (United States); Hohaus, Thorsten [Aerodyne Research, Inc., Billerica, MA (United States); Gonin, Marc [Tofwerk AG, Thun (Switzerland); Kroll, Jesse H. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Worsnop, Douglas R. [Aerodyne Research, Inc., Billerica, MA (United States); Goldstein, Allen H. [Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2012-01-30

    Understanding the composition of complex hydrocarbon mixtures is important for environmental studies in a variety of fields, but many prevalent compounds cannot be confidently identified using traditional gas chromatography/mass spectrometry (GC/MS) techniques. In this study, we use vacuum-ultraviolet (VUV) ionization to elucidate the structures of a traditionally “unresolved complex mixture” by separating components by GC retention time, tR, and mass-to-charge ratio, m/z, which are used to determine carbon number, NC, and the number of rings and double bonds, NDBE. Constitutional isomers are resolved on the basis of tR, enabling the most complete quantitative analysis to date of structural isomers in an environmentally relevant hydrocarbon mixture. Unknown compounds are classified in this work by carbon number, degree of saturation, presence of rings, and degree of branching, providing structural constraints. The capabilities of this analysis are explored using diesel fuel, in which constitutional isomer distribution patterns are shown to be reproducible between carbon numbers and follow predictable rules. Nearly half of the aliphatic hydrocarbon mass is shown to be branched, suggesting branching is more important in diesel fuel than previously shown. Lastly, the classification of unknown hydrocarbons and the resolution of constitutional isomers significantly improves resolution capabilities for any complex hydrocarbon mixture.

  6. Relaciones entre pruebas de velocidad, tests de salto y dinamometría isométrica en velocistas

    Directory of Open Access Journals (Sweden)

    Rafael Sabido Solana

    2010-09-01

    Full Text Available Dentro de las habilidades deportivas, la capacidad de producir fuerza lo más rápidamente posible, o fuerza explosiva, juega el papel más importante en la optimización de dichas habilidades. Zatsiorsky (1995 la define como “la habilidad para desarrollar la máxima fuerza en la menor cantidad de tiempo”. Las correlaciones existentes entre pruebas de velocidad y tests de salto han sido ampliamente observadas. Sin embargo, las correlaciones entre pruebas de velocidad y tests isométricos están menos estudiadas. Una muestra de 24 velocistas de categoría junior fue sometida a pruebas de velocidad específica, tests de salto con contramovimiento y en profundidad, así como a un test isométrico máximo para la musculatura extensora del tobillo. Los resultados muestran fuertes relaciones entre los tests de carrera y los de salto, así como de estos últimos con los de dinamometría. Por otro lado, sólo con el test de 20 metros se obtienen correlaciones con variables del test isométrico, sin que se encuentren correlaciones con la marca en 100 metros lisos. La principal conclusión de nuestros datos es que las variables medidas en un test isométrico van a tener alta relación con la primera fase de la carrera en pruebas de velocidad.

  7. Binding Energy Calculation of Patchouli Alcohol Isomer Cyclooxygenase Complexes Suggested as COX-1/COX-2 Selective Inhibitor

    Directory of Open Access Journals (Sweden)

    Sentot Joko Raharjo

    2014-01-01

    Full Text Available To understand the structural features that dictate the selectivity of the two isoforms of the prostaglandin H2 synthase (PGHS/COX, the three-dimensional (3D structure of COX-1/COX-2 was assessed by means of binding energy calculation of virtual molecular dynamic with using ligand alpha-Patchouli alcohol isomers. Molecular interaction studies with COX-1 and COX-2 were done using the molecular docking tools by Hex 8.0. Interactions were further visualized by using Discovery Studio Client 3.5 software tool. The binding energy of molecular interaction was calculated by AMBER12 and Virtual Molecular Dynamic 1.9.1 software. The analysis of the alpha-Patchouli alcohol isomer compounds showed that all alpha-Patchouli alcohol isomers were suggested as inhibitor of COX-1 and COX-2. Collectively, the scoring binding energy calculation (with PBSA Model Solvent of alpha-Patchouli alcohol isomer compounds (CID442384, CID6432585, CID3080622, CID10955174, and CID56928117 was suggested as candidate for a selective COX-1 inhibitor and CID521903 as nonselective COX-1/COX-2.

  8. Effect of C6-olefin isomers on π-complexation for purification of 1-hexene by reactive extractive distillation

    NARCIS (Netherlands)

    Wentink, A.E.; Kockmann, D.; Kuipers, N.J.M.; Haan, de A.B.; Scholz, J.; Mulder, H.

    2002-01-01

    Separation of α-olefins from other olefin isomers is a difficult and expensive operation because of the low selectivities encountered. A promising alternative is π-complexation in combination with extractive distillation: reactive extractive distillation (RED). In this paper, silver nitrate dissolve

  9. Regiospecific Distribution of trans-Octadecenoic Acid Positional Isomers in Triacylglycerols of Partially Hydrogenated Vegetable Oil and Ruminant Fat.

    Science.gov (United States)

    Yoshinaga, Kazuaki; Kawamura, Yoshinori; Kitayama, Takashi; Nagai, Toshiharu; Mizobe, Hoyo; Kojima, Koichi; Watanabe, Yomi; Sato, Shinichi; Beppu, Fumiaki; Gotoh, Naohiro

    2015-01-01

    It is revealed that binding position of fatty acid in triacylglycerol (TAG) deeply relates to the expression of its function. Therefore, we investigated the binding positions of individual trans-octadecenoic acid (trans-C18:1) positional isomers, known as unhealthy fatty acids, on TAG in partially hydrogenated canola oil (PHCO), milk fat (MF), and beef tallow (BT). The analysis was carried out by the sn-1(3)-selective transesterification of Candida antarctica Lipase B and by using a highly polar ionic liquid capillary column for gas chromatography-flame ionization detection. Trans-9-C18:1, the major trans-C18:1 positional isomer, was selectively located at the sn-2 position of TAG in PHCO, although considerable amounts of trans-9-C18:1 were also esterified at the sn-1(3) position. Meanwhile, trans-11-C18:1, the major isomer in MF and BT, was preferentially located at the sn-1(3) position. These results revealed that the binding position of trans-C18:1 positional isomer varies between various fats and oils.

  10. Effects on thyroid hormone and retinoid metabolism in transthyretin-null mice by polychlorinated biphenyl isomers 118 and 114

    Energy Technology Data Exchange (ETDEWEB)

    Nishimura, N.; Yonemoto, J.; Takeuchi, Y.; Yokoi, C.; Tohyama, C. [National Inst. for Environmental Studies, Tsukuba (Japan)

    2004-09-15

    Some congeners/isomers of polychlorinated biphenyls (PCBs) and their metabolites are known to disturb thyroid and retinoid metabolism in laboratory animals and humans. Among 209 isomers of PCBs, 12 PCB isomers termed as the coplanar PCBs are grouped into dioxin-like chemicals based on their resemblance of toxic effects and mechanism(s) to dioxins. Mechanism(s) of toxicity by the dioxin-like chemicals have been established to be mediated through aryl hydrocarbon receptor (AhR). The toxic potency of each congener/isomer of dioxin-like chemicals has been evaluated by relative potency to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) as the toxic equivalent factor (TEF). Because dioxins in environments are generally distributed as mixtures, the toxic equivalency (TEQ) concept has been adopted to evaluate the health risk of exposure to complex environmental mixtures. TEQ values are calculated by multiplication of the sum of the chemical concentrations by the corresponding TEF values. The present study was undertaken to investigate the effects of two coplanar PCBs, PCB118, highly detected in human tissues and milk (TEF value: 0.0001), and PCB114 (TEF value: 0.0005) on thyroid hormone and retinoid metabolism. Possible involvement of transthyretin (TTR), the principal carrier of thyroid hormone and retinol-binding protein in the rodent, in PCBs-induced disruption of thyroid and retinoid homeostasis was investigated.

  11. Uncommon Synergy between Adsorption and Diffusion of Hexane Isomer Mixtures in MFI Zeolite Induced by Configurational Entropy Effects

    NARCIS (Netherlands)

    Titze, T.; Chmelik, C.; Kärger, J.; van Baten, J.M.; Krishna, R.

    2014-01-01

    While n-hexane (nC6) can adsorb at any location within the MFI zeolite pore network, configurational considerations cause the branched isomer 2-methylpentane (2MP) to locate preferentially at the channel intersections. For adsorption of nC6/2MP mixtures, infrared microscopy (IRM) measurements show t

  12. Structure and spectroscopic properties of neutral and cationic tetratomic [C,H,N,Zn] isomers: A theoretical study.

    Science.gov (United States)

    Redondo, Pilar; Largo, Antonio; Vega-Vega, Álvaro; Barrientos, Carmen

    2015-05-14

    The structure and spectroscopic parameters of the most relevant [C,H,N,Zn] isomers have been studied employing high-level quantum chemical methods. For each isomer, we provide predictions for their molecular structure, thermodynamic stabilities as well as vibrational and rotational spectroscopic parameters which could eventually help in their experimental detection. In addition, we have carried out a detailed study of the bonding situations by means of a topological analysis of the electron density in the framework of the Bader's quantum theory of atoms in molecules. The analysis of the relative stabilities and spectroscopic parameters suggests two linear isomers of the neutral [C,H,N,Zn] composition, namely, cyanidehydridezinc HZnCN ((1)Σ) and hydrideisocyanidezinc HZnNC ((1)Σ), as possible candidates for experimental detections. For the cationic [C,H,N,Zn](+) composition, the most stable isomers are the ion-molecule complexes arising from the direct interaction of the zinc cation with either the nitrogen or carbon atom of either hydrogen cyanide or hydrogen isocyanide, namely, HCNZn(+) ((2)Σ) and HCNZn(+) ((2)Σ).

  13. Separation of cis/trans fatty acid isomers on gas chromatography compared to the Ag-TLC method

    Energy Technology Data Exchange (ETDEWEB)

    Ravi Kiran, C.; Reshma, M. V.; Sundaresan, A.

    2013-05-01

    The present study investigates the separation of the cis/ trans isomers of fatty acids on the 75 m SP2560 column under different gas chromatographic (GC) conditions including an isothermal program and a time-temperature program. The time-temperature program showed improved separation of cis/trans isomers of C{sub 1}4:1, C{sub 1}6:1, C{sub 1}8:1, C{sub 1}8:2 and C{sub 1}8:3 fatty acids along with short chain fatty acids compared to the isothermal program. The separation of trans/trans isomers of C{sub 1}8:1 fatty acids including elaidic acid (C{sub 1}8:1 .9t) and vaccenic acid (C{sub 1}8:1 {Delta}11t) was difficult with the time-temperature program. The thin layer chromatography impregnated with silver nitrate (Ag- TLC) method was performed to separate cis/trans fractions and GC analysis was carried out with the trans fraction. But GC analysis showed a co-elution of trans isomers of C{sub 1}8:1 fatty acid. Thus the study shows that a time-temperature programmed GC method with the highly polar cyanopropyl column is sufficient to resolve trans fatty acids along with short chain fatty acids when a large number of samples has to be analyzed. (Author) 33 refs.

  14. The sim Operon Facilitates the Transport and Metabolism of Sucrose Isomers in Lactobacillus casei ATCC 334▿

    Science.gov (United States)

    Thompson, John; Jakubovics, Nicholas; Abraham, Bindu; Hess, Sonja; Pikis, Andreas

    2008-01-01

    Inspection of the genome sequence of Lactobacillus casei ATCC 334 revealed two operons that might dissimilate the five isomers of sucrose. To test this hypothesis, cells of L. casei ATCC 334 were grown in a defined medium supplemented with various sugars, including each of the five isomeric disaccharides. Extracts prepared from cells grown on the sucrose isomers contained high levels of two polypeptides with Mrs of ∼50,000 and ∼17,500. Neither protein was present in cells grown on glucose, maltose or sucrose. Proteomic, enzymatic, and Western blot analyses identified the ∼50-kDa protein as an NAD+- and metal ion-dependent phospho-α-glucosidase. The oligomeric enzyme was purified, and a catalytic mechanism is proposed. The smaller polypeptide represented an EIIA component of the phosphoenolpyruvate-dependent sugar phosphotransferase system. Phospho-α-glucosidase and EIIA are encoded by genes at the LSEI_0369 (simA) and LSEI_0374 (simF) loci, respectively, in a block of seven genes comprising the sucrose isomer metabolism (sim) operon. Northern blot analyses provided evidence that three mRNA transcripts were up-regulated during logarithmic growth of L. casei ATCC 334 on sucrose isomers. Internal simA and simF gene probes hybridized to ∼1.5- and ∼1.3-kb transcripts, respectively. A 6.8-kb mRNA transcript was detected by both probes, which was indicative of cotranscription of the entire sim operon. PMID:18310337

  15. Nucleosynthesis of 92Nb and the relevance of the low-lying isomer at 135.5 keV

    Science.gov (United States)

    Mohr, Peter

    2016-06-01

    Background: Because of its half-life of about 35 million years, 92Nb is considered as a chronometer for nucleosynthesis events prior to the birth of our sun. The abundance of 92Nb in the early solar system can be derived from meteoritic data. It has to be compared to theoretical estimates for the production of 92Nb to determine the time between the last nucleosynthesis event before the formation of the early solar system. Purpose: The influence of a low-lying short-lived isomer on the nucleosynthesis of 92Nb is analyzed. The thermal coupling between the ground state and the isomer via so-called intermediate states affects the production and survival of 92Nb. Method: The properties of the lowest intermediate state in 92Nb are known from experiment. From the lifetime of the intermediate state and from its decay branchings, the transition rate from the ground state to the isomer and the effective half-life of 92Nb are calculated as functions of the temperature. Results: The coupling between the ground state and the isomer is strong. This leads to thermalization of ground state and isomer in the nucleosynthesis of 92Nb in any explosive production scenario and almost 100% survival of 92Nb in its ground state. However, the strong coupling leads to a temperature-dependent effective half-life of 92Nb which makes the 92Nb survival very sensitive to temperatures as low as about 8 keV, thus turning 92Nb at least partly into a thermometer. Conclusions: The low-lying isomer in 92Nb does not affect the production of 92Nb in explosive scenarios. In retrospect this validates all previous studies where the isomer was not taken into account. However, the dramatic reduction of the effective half-life at temperatures below 10 keV may affect the survival of 92Nb after its synthesis in supernovae, which are the most likely astrophysical sites for the nucleosynthesis of 92Nb.

  16. Levitation effect in zeolites: Quasielastic neutron scattering and molecular dynamics study of pentane isomers in zeolite NaY.

    Science.gov (United States)

    Borah, Bhaskar J; Jobic, H; Yashonath, S

    2010-04-14

    We report the quasielastic neutron scattering (QENS) and molecular dynamics (MD) investigations into diffusion of pentane isomers in zeolite NaY. The molecular cross section perpendicular to the long molecular axis varies for the three isomers while the mass and the isomer-zeolite interaction remains essentially unchanged. Both QENS and MD results show that the branched isomers neopentane and isopentane have higher self-diffusivities as compared with n-pentane at 300 K in NaY zeolite. This result provides direct experimental evidence for the existence of nonmonotonic, anomalous dependence of self-diffusivity on molecular diameter known as the levitation effect. The energetic barrier at the bottleneck derived from MD simulations exists for n-pentane which lies in the linear regime while no such barrier is seen for neopentane which is located clearly in the anomalous regime. Activation energy is in the order E(a)(n-pentane)>E(a)(isopentane)>E(a)(neopentane) consistent with the predictions of the levitation effect. In the liquid phase, it is seen that D(n-pentane)>D(isopentane)>D(neopentane) and E(a)(n-pentane)isomer has a higher diffusivity as compared with the linear analog is at variation from what is normally seen.

  17. Simultaneous Spectrophotometric Determination of Three Tolualdehyde Isomers by Artificial Neural Networks and Its Comparison with Partial Least Squares

    Institute of Scientific and Technical Information of China (English)

    FANG,Huiwen; LI,Hui; LI,Yanwei; ZHAO,Jing; XU,Jian

    2009-01-01

    The simultaneous determination of tolualdehyde isomer mixtures by using a spectrophotometric method is a difficult problem in analytical chemistry,due to spectral interference.By multivariate calibration methods,such as partial least squares(PLS)and artificial neural network(ANN),it is possible to obtain a model adjusted to the con-centration values of the mixtures used in the calibration range.The ANN calibration model of simultaneous deter-mination of tolualdehyde isomers was based on absorption spectra in the 230-304 nm range for 48 different mix-tures of tolualdehyde isomers,and the concentration ranges for O-tolualdehyde,m-tolualdehyde and P-tolualdehyde were 6.0-15.0,7.0-16.0 and 8.0-19.0μg·mL-1, respectively.Other 7 samples were applied to testing me pre-dictive ability of the calibration model.The effect of the three isomers with different concentration ratios in their mixtures on the accuracy of determination results was discussed and the appropriate range of concentration ratio was found.The proposed method Was applied to simultaneous determination of the three isomers in synthetic sam-ples and the recoveries were between 84.00%and 109.60%.The results of determination were compared with the PLS model without significant difference at 0.05 level for o-tolualdehyde and m-tolualdehyde by paired t-test.But a better performance for p-tolualdehyde in their mixtures could be obtained by the ANN calibration model.

  18. Ab initio Calculations of Optical Properties of Clusters

    CERN Document Server

    Shinde, Ravindra

    2016-01-01

    We have performed systematic large-scale all-electron correlated calculations on boron Bn, aluminum Aln and magnesium Mgn clusters (n=2--5), to study their linear optical absorption spectra. Several possible isomers of each cluster were considered, and their geometries were optimized at the coupled-cluster singles doubles (CCSD) level of theory. Using the optimized ground-state geometries, excited states of different clusters were computed using the multi-reference singles-doubles configuration interaction (MRSDCI) approach, which includes electron correlation effects at a sophisticated level. These CI wavefunctions were used to compute the transition dipole matrix elements connecting the ground and various excited states of different clusters, eventually leading to their linear absorption spectra. The convergence of our results with respect to the basis sets, and the size of the CI expansion was carefully examined. Isomers of a given cluster show a distinct signature spectrum, indicating a strong structure p...

  19. The content of conjugated linoleic acid (CLA) isomer groups in milk of two Polish sheep breeds determined by silver ion liquid chromatography (Ag(+)-HPLC).

    Science.gov (United States)

    Rozbicka-Wieczorek, Agnieszka; Radzik-Rant, Aurelia; Rant, Witold; Czauderna, Marian

    2013-01-01

    Sheep milk is rich in CLA isomers which are biologically active components influencing human health. There are four geometric CLA isomer pairs: cis, trans; trans, cis; trans, trans and cis, cis. The aim of the present study was the analysis of CLA isomer groups content by Ag+-HPLC in milk fat of Zelazneńska (ZS) and Wrzosówka (WS) sheep breeds. The ewes of both breeds were kept under the same environmental and nutritional conditions. Milk samples were collected from 60 suckling ewes (30 from each breed), at the age of 3-4 years and in their 4th week of lactation. A higher total amount of all CLA isomer groups was obtained in milk of ZS ewes, however, this result was statistically insignificant. The percentage of the main c9, t11 isomer in total CLA was higher in Wrzosówka milk (68% vs. 74%). The content of the trans, trans isomer group in milk fat of the studied breeds was similar. The percentage of this group in total CLA in milk of WS and ZS constitutes 7.2% and 7.7%, respectively. The amount of cis,cis isomers in milk fat of ZS was higher thanWS (P < or = 0.01).

  20. A honeycomb network based on hybrid lanthanum complexes encircling a [β-Mo8O26]4- isomer: Synthesis, characterization and crystal structure of [La (η2-NO3) (dmso)7]2 [β-Mo8O26

    Science.gov (United States)

    Khélifa, Arbia Ben; Ezzayani, Khaireddine; Belkhiria, Mouhamed Salah

    2016-10-01

    A novel isopolymolybdates functionalized by rare earth complexes namely, [La (η2-NO3) (dmso)7]2 [β-Mo8O26] (1) has been successfully synthesized and characterized by routine methods: IR, X-ray powder diffraction, UV-Visible absorption and single crystal X-ray diffraction. The title compound is crystallized in monoclinic space group P21/n with a = 11.566 (2) Å, b = 28.522 (6) Å, c = 12.644 (3) Å, β = 91.94 (3)°. The structural feature of 1 is that lanthanum complexes form a honeycomb network, in which resides the [β-Mo8O26]4- isomer. The cohesion structure is ensured by non typical hydrogen bonding interactions causes a 3D supramolecular network. Absorption spectrum, optical band gap energies have been investigated.

  1. Conjugated linoleic acids (CLAs) decrease prostate cancer cell proliferation: different molecular mechanisms for cis-9, trans-11 and trans-10, cis-12 isomers.

    Science.gov (United States)

    Ochoa, Julio J; Farquharson, Andrew J; Grant, Ian; Moffat, L E; Heys, Steven D; Wahle, Klaus W J

    2004-07-01

    The aims of this study were to examine the anti-proliferative effects of different concentrations of a commercial preparation of conjugated linoleic acids (CLA) mixture of isomers [cis-9, trans-11 CLA (c9,t11 CLA): trans-10, cis-12 CLA (50:50)] and their constituent isomers on PC-3, a human prostatic carcinoma cell line, and to study their effects on gene expression (mRNA and protein levels) of different enzymes and oncoproteins involved in oncogenesis and progression of prostate cancer. This includes pathways for arachidonic acid metabolism [cyclooxygenase 1 (COX-1), 2 (COX-2) and 5-lipoxygenase (5-LOX)], apoptosis (bcl-2) and cell cycle control (p21(WAF/Cip1)). Our results indicate a significant decrease in PC-3 proliferation elicited by CLA, although with high variability between isomers. The trans-10, cis-12 CLA was the most effective isomer (55% inhibition). This isomer was also able to decrease bcl-2 gene expression and to increase p21(WAF1/Cip1) mRNA levels (60% increase at highest concentration). In contrast, cis-9, trans-11 had no effect on these proteins but had a clear effect on 5-LOX expression and to a lesser degree on COX-2 protein level isomers. In conclusion, the anti-proliferative effects on PC-3 of CLA mixture and their constituent isomers are not equivalent, due to the different pathways involved for individual isomers. Trans-10, cis-12 seems to work preferentially through modulation of apoptosis and cell cycle control, while c9,t11 CLA isomer affects arachidonic acid metabolism.

  2. Sorption of a branched nonylphenol isomer and perfluorooctanoic acid on geosorbents and carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Li, Chengliang

    2011-10-13

    As metabolites of organic surfactants, both nonylphenol (NP) and perfluorooctanoic acid (PFOA) are toxic and ubiquitous in the environment. Their sorption on soils and sediments is of importance for their fate and transport in the environment. Especially in China, there is still a lack of consolidated knowledge on the sorption behavior of NP and PFOA on geosorbents such as Yangtze River sediments. Thus, the present thesis investigates the sorption of a branched NP isomer [4-(1-ethyl-1, 3-dimethylpentyl) phenol] (NP111) and PFOA on Yangtze River sediments and their model components, i.e. a clay mineral (illite), metal oxides (goethite and {delta}-Al{sub 2}O{sub 3}) and organic matter (isolated from Yangtze River sediments and commercial organic matter) by both batch and dialysis techniques. NP111 is the most environmentally relevant NP isomer and its fate in the environment is unknown. Because PFOA is weakly adsorbed on geosorbents, multi-walled carbon nanotubes (MWCNTs) were studied as promising adsorbents. One of the MWCNTs studied contained traces of metal catalyst on the outer surface. Sorption isotherms of NP111 and PFOA on the sediments and their model components were fitted well by the Freundlich model. Sorption of NP111 on the sediments depended largely on their organic carbon content, resulting in organic carbon-normalized sorption coefficient (K{sub OC}) values between 6.3 x 10{sup 3} and 1.1 x 10{sup 4} L kg{sup -1}. The sorption of NP111 on {delta}-Al{sub 2}O{sub 3} and illite was comparable to that on sediments, but significantly lower than that on goethite. In contrast, the sorption of PFOA on the sediments was significantly lower. The affinity of PFOA to goethite and {delta}-Al{sub 2}O{sub 3} was slightly higher than to the sediments, but it was negligible to natural organic matter and illite. The results suggest that the organic carbon content of the sediments plays a dominant role in the sorption of NP111, whereas goethite acts as a potential sink

  3. Anti-neoplastic activity of two flavone isomers derived from Gnaphalium elegans and Achyrocline bogotensis.

    Directory of Open Access Journals (Sweden)

    Christan M Thomas

    Full Text Available Over 4000 flavonoids have been identified so far and among these, many are known to have antitumor activities. The basis of the relationships between chemical structures, type and position of substituent groups and the effects these compounds exert specifically on cancer cells are not completely elucidated. Here we report the differential cytotoxic effects of two flavone isomers on human cancer cells from breast (MCF7, SK-BR-3, colon (Caco-2, HCT116, pancreas (MIA PaCa, Panc 28, and prostate (PC3, LNCaP that vary in differentiation status and tumorigenic potential. These flavones are derived from plants of the family Asteraceae, genera Gnaphalium and Achyrocline reputed to have anti-cancer properties. Our studies indicate that 5,7-dihydroxy-3,6,8-trimethoxy-2-phenyl-4H-chromen-4-one (5,7-dihydroxy-3,6,8-trimethoxy flavone displays potent activity against more differentiated carcinomas of the colon (Caco-2, and pancreas (Panc28, whereas 3,5-dihydroxy-6,7,8-trimethoxy-2-phenyl-4H-chromen-4-one (3,5-dihydroxy-6,7,8-trimethoxy flavone cytototoxic action is observed on poorly differentiated carcinomas of the colon (HCT116, pancreas (Mia PaCa, and breast (SK-BR3. Both flavones induced cell death (>50% as proven by MTT cell viability assay in these cancer cell lines, all of which are regarded as highly tumorigenic. At the concentrations studied (5-80 µM, neither flavone demonstrated activity against the less tumorigenic cell lines, breast cancer MCF-7 cells, androgen-responsive LNCaP human prostate cancer line, and androgen-unresponsive PC3 prostate cancer cells. 5,7-dihydroxy-3,6,8-trimethoxy-2-phenyl-4H-chromen-4-one (5,7-dihydroxy-3,6,8-trimethoxy flavone displays activity against more differentiated carcinomas of the colon and pancreas, but minimal cytotoxicity on poorly differentiated carcinomas of these organs. On the contrary, 3,5-dihydroxy-6,7,8-trimethoxy-2-phenyl-4H-chromen-4-one (3,5-dihydroxy-6,7,8-trimethoxy flavone is highly cytotoxic to

  4. Anti-Neoplastic Activity of Two Flavone Isomers Derived from Gnaphalium elegans and Achyrocline bogotensis

    Science.gov (United States)

    Pendleton, Morgan H.; Torrenegra, Ruben D.; Rodriguez, Oscar E.; Harirforoosh, Sam; Ballester, Maria; Lightner, Janet; Krishnan, Koyamangalath; Ramsauer, Victoria P.

    2012-01-01

    Over 4000 flavonoids have been identified so far and among these, many are known to have antitumor activities. The basis of the relationships between chemical structures, type and position of substituent groups and the effects these compounds exert specifically on cancer cells are not completely elucidated. Here we report the differential cytotoxic effects of two flavone isomers on human cancer cells from breast (MCF7, SK-BR-3), colon (Caco-2, HCT116), pancreas (MIA PaCa, Panc 28), and prostate (PC3, LNCaP) that vary in differentiation status and tumorigenic potential. These flavones are derived from plants of the family Asteraceae, genera Gnaphalium and Achyrocline reputed to have anti-cancer properties. Our studies indicate that 5,7-dihydroxy-3,6,8-trimethoxy-2-phenyl-4H-chromen-4-one (5,7-dihydroxy-3,6,8-trimethoxy flavone) displays potent activity against more differentiated carcinomas of the colon (Caco-2), and pancreas (Panc28), whereas 3,5-dihydroxy-6,7,8-trimethoxy-2-phenyl-4H-chromen-4-one (3,5-dihydroxy-6,7,8-trimethoxy flavone) cytototoxic action is observed on poorly differentiated carcinomas of the colon (HCT116), pancreas (Mia PaCa), and breast (SK-BR3). Both flavones induced cell death (>50%) as proven by MTT cell viability assay in these cancer cell lines, all of which are regarded as highly tumorigenic. At the concentrations studied (5–80 µM), neither flavone demonstrated activity against the less tumorigenic cell lines, breast cancer MCF-7 cells, androgen-responsive LNCaP human prostate cancer line, and androgen-unresponsive PC3 prostate cancer cells. 5,7-dihydroxy-3,6,8-trimethoxy-2-phenyl-4H-chromen-4-one (5,7-dihydroxy-3,6,8-trimethoxy flavone) displays activity against more differentiated carcinomas of the colon and pancreas, but minimal cytotoxicity on poorly differentiated carcinomas of these organs. On the contrary, 3,5-dihydroxy-6,7,8-trimethoxy-2-phenyl-4H-chromen-4-one (3,5-dihydroxy-6,7,8-trimethoxy flavone) is highly cytotoxic to

  5. Analysis of a series of chlorogenic acid isomers using differential ion mobility and tandem mass spectrometry.

    Science.gov (United States)

    Willems, Jamie L; Khamis, Mona M; Mohammed Saeid, Waleed; Purves, Randy W; Katselis, George; Low, Nicholas H; El-Aneed, Anas

    2016-08-24

    Chlorogenic acids are among the most abundant phenolics found in the human diet. Of these, the mono-caffeoylquinic acids are the predominant phenolics found in fruits, such as apples and pears, and products derived from them. In this research, a comprehensive study of the electrospray ionization (ESI) tandem mass spectrometric (MS/MS) dissociation behavior of the three most common mono-caffeoylquinic acids, namely 5-O-caffeoylquinic acid (5-CQA), 3-O-caffeoylquinic acid (3-CQA) and 4-O-caffeoylquinic acid (4-CQA), were determined using both positive and negative ionization. All proposed structures of the observed product ions were confirmed with second-generation MS(3) experiments. Similarities and differences between the dissociation pathways in the positive and negative ion modes are discussed, confirming the proposed structures and the established MS/MS fingerprints. MS/MS dissociation was primarily driven via the cleavage of the ester bond linking the quinic acid moiety to the caffeic acid moiety within tested molecules. Despite being structural isomers with the same m/z values and dissociation behaviors, the MS/MS data in the negative ion mode was able to differentiate the three isomers based on ion intensity for the major product ions, observed at m/z 191, 179 and 173. This differentiation was consistent among various MS instruments. In addition, ESI coupled with high-field asymmetric waveform ion mobility spectrometry-mass spectrometry (ESI-FAIMS-MS) was employed for the separation of these compounds for the first time. By combining MS/MS data and differential ion mobility, a method for the separation and identification of mono-caffeoylquinic in apple/pear juice samples was developed with a run time of less than 1 min. It is envisaged that this methodology could be used to identify pure juices based on their chlorogenic acid profile (i.e., metabolomics), and could also be used to detect juice-to-juice adulteration (e.g., apple juice addition to pear juice).

  6. Development of a RIMMPA-TOFMS. Isomer selective soft ionization of PCDDs/DFs

    Energy Technology Data Exchange (ETDEWEB)

    Kirihara, N.; Haruaki, Y.; Mizuho, T.; Kenji, T.; Norifumi, K.; Yasuo, S. [IDX Corporation, Tokyo (Japan); Toru, S. [JFE Engineering Corporation, Kanagawa (Japan)

    2004-09-15

    Laser mass spectrometry is an excellent technique for analyzing the dioxin discharge that changes continuously in a waste incinerator because of its rapidity and sensitivity. This instrument is being developed by many research groups around the world. A laser has also been proposed that uses a pico-second or femto-second pulse width in order to ionize softly for the polychlorodibenzo-p-dioxins and polychlorodibenzofurans (PCDDs/DFs) because of the short excitation lifetime of their molecules. In contrast, we have developed a new laser mass spectrometer, RIMMPA-TOFMS (Resonance Ionization with Multi-Mirror-System Photon Accumulation coupled with Time of Flight Mass Spectrometry), based on a two-color-two-photon ionization scheme and using a nanosecond pulse laser, which enables isomer selective soft ionization for the PCDDs/DFs, and which has high-sensitivity performance with a minimum limit of detection of 3.7 pptv (signal-to-noise ratio S/N = 3, 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TeCDD)). In particular, a pulse valve has been developed that can operate under a high-temperature condition and produce a supersonic jet under the choke-flow condition, enabling isomer selective soft ionization of the PCDDs/DFs. If the supersonic jet gas ejected from our short pulse valve can not only be cooled to cryogenic temperature, but also be ordered uniformly so that the collisions between particles are minimized and the excitation lifetime of its compounds becomes longer, then the nano-second pulse width laser will also ionize softly. In this paper, we report the experimental results of the following PCDDs/DFs detected by RIMMPA-TOFMS: 2,3,7,8-TeCDD, 1,2,3,7,8-pentachlorodibenzofuran (PnCDF) and 2,3,4,7,8- PnCDF, and the mass and wavelength two-dimensional map database for the 14 kinds of PCDDs/DFs.

  7. Search for X-Ray Induced Acceleration of the Decay of the 31-yr Isomer 178Hf Using Synchrotron Radiation

    Energy Technology Data Exchange (ETDEWEB)

    Ahmad, I; Banar, J C; Becker, J A; Gemmell, D S; Kraemer, A; Mashayekhi, A; McNabb, D P; Miller, G G; Moore, E F; Pangault, L N; Rundberg, R S; Schiffer, J P; Shastri, S D; Wang, T F; Wilhelmy, J B

    2002-05-09

    Releasing the energy stored in an isomeric nuclear state in a controlled way with an atomic or electromagnetic trigger is an attractive speculation: the energy gain may be on the order of the ratio of nuclear/atomic energies - MeV/keV. (Nuclear isomers are loosely defined as excited nuclear states with lifetimes longer than 10{sup -9} s.) Nuclear isomers, therefore, represent an opportunity for a stand-alone energy source if suitable schemes for trigger and control of the energy release can be found. Potential applications include space drive, as well as very bright {gamma}-ray sources. The nucleus {sup 178}Hf has a nuclear isomer with excitation energy E{sub x} = 2.447 MeV. The 2.447-MeV isomeric state decays slowly (t{sub 1/2} = 31 y) to the nearby state at 2.433 MeV. The J{sup {pi}} = 13{sup -} state loses energy in a rapid (t {approx} 10{sup -12} s) {gamma}-ray cascade ending at the 8{sup -} rotational band head which in turn decays via the ground-state rotational band cascade. The {gamma}-ray cascade is delayed at the 8{sup -} state at 1.147 MeV, since the 8{sup -} state is also isomeric, with t{sub 1/2} = 4 s. Very scarce quantities of the 16{sup +}, 31-yr isomer are available for research ({approx} 10{sup 15} atoms). Reports of triggered decay of the {sup 178}Hf isomer induced by x-rays delivered by a dental x-ray machine have been made [2,3]. Enhancements of {approx} 1 - 2% in the isomer decay rate (dN/dt = - (1 + {var_epsilon})N/{tau}) had been reported for various {gamma}-rays in the cascade (distinguished by red and vertical lines in Figure 1). The reported integrated cross section for triggering the decay is cm{sup 2} keV, so large as to demand new physics. We have sought to verify these reports taking advantage of the intense photon flux available at the Advanced Photon Source.

  8. Performance of some DFT functionals with dispersion on modeling of the translational isomers of a solvent-switchable [2]rotaxane

    Science.gov (United States)

    Ivanov, Petko

    2016-03-01

    The balances of interactions were studied by computational methods in the translational isomers of a solvent switchable fullerene-stoppered [2]rotaxane (1) manifesting unexpected behavior, namely that due to favorable dispersion interactions the fullerene stopper becomes the second station upon change of the solvent. For comparison, another system, a pH switchable molecular shuttle (2), was also examined as an example of prevailing electrostatic interactions. Tested for 1 were five global hybrid Generalized Gradient Approximation functionals (B3LYP, B3LYP-D3, B3LYP-D3BJ, PBEh1PBE and APFD), one long-range corrected, range-separated functional with D2 empirical dispersion correction, ωB97XD, the Zhao-Truhlar's hybrid meta-GGA functional M06 with double the amount of nonlocal exchange (2X), and a pure functional, B97, with the Grimme's D3BJ dispersion (B97D3). The molecular mechanics method qualitatively correctly reproduced the behavior of the [2]rotaxanes, whereas the DFT models, except for M06-2X to some extent, failed in the case of significant dispersion interactions with participation of the fulleropyrrolidine stopper (rotaxane 1). Unexpectedly, the benzylic amide macrocycle tends to adopt preferentially 'boat'-like conformation in most of the cases. Four hydrogen bonds interconnect the axle with the wheel for the translational isomer with the macroring at the succinamide station (station II), whereas the number of hydrogen bonds vary for the isomer with the macroring at the fulleropyrrolidine stopper (station I) depending of the computational model used. The B3LYP and the PBEh1PBE results show strong preference of station II in the gas phase and in the model solvent DMSO. After including empirical dispersion correction, the translational isomer with the macroring at station I has the lower energy with B3LYP, both in the gas phase and in DMSO. The same result, but with higher preference of station I, was estimated with APFD, ωB97XD and B97D3. Only M06-2X

  9. Potent inhibitory effect of trans9, trans11 isomer of conjugated linoleic acid on the growth of human colon cancer cells

    OpenAIRE

    Beppu, Fumiaki; Hosokawa, Masashi; Tanaka, Leo; Kohno, Hiroyuki; Tanaka, Takuji; Miyashita, Kazuo

    2006-01-01

    This study compared the growth inhibitory effects of pure conjugated linoleic acid (CLA) isomers [cis(c)9,c11-CLA, c9,trans(t)11-CLA, t9,t11-CLA, and t10,c12-CLA] on human colon cancer cell lines (Caco-2, HT-29 and DLD-1). When Caco-2 cells were incubated up to 72 h with 200 μM, each isomer, even in the presence of 10% fetal bovine serum (FBS), cell proliferation was inhibited by all CLA isomers in a time-dependent manner. The strongest inhibitory effect was shown by t9,t11-CLA, followed by t...

  10. Modern optics

    CERN Document Server

    Guenther, B D

    2015-01-01

    Modern Optics is a fundamental study of the principles of optics using a rigorous physical approach based on Maxwell's Equations. The treatment provides the mathematical foundations needed to understand a number of applications such as laser optics, fiber optics and medical imaging covered in an engineering curriculum as well as the traditional topics covered in a physics based course in optics. In addition to treating the fundamentals in optical science, the student is given an exposure to actual optics engineering problems such as paraxial matrix optics, aberrations with experimental examples, Fourier transform optics (Fresnel-Kirchhoff formulation), Gaussian waves, thin films, photonic crystals, surface plasmons, and fiber optics. Through its many pictures, figures, and diagrams, the text provides a good physical insight into the topics covered. The course content can be modified to reflect the interests of the instructor as well as the student, through the selection of optional material provided in append...

  11. Optic Neuritis

    OpenAIRE

    1989-01-01

    Demyelinating optic neuritis is the most common cause of unilateral painful visual loss in the United States. Although patients presenting with demyelinating optic neuritis have favorable long-term visual prognosis, optic neuritis is the initial clinical manifestation of multiple sclerosis in 20% of patients. The Optic Neuritis Treatment Trial (ONTT) has helped stratify the risk of developing multiple sclerosis after the first episode of optic neuritis based on abnormal findings on brain MRI....

  12. A calculation of all possible oligosaccharide isomers both branched and linear yields 1.05 x 10(12) structures for a reducing hexasaccharide: the Isomer Barrier to development of single-method saccharide sequencing or synthesis systems.

    Science.gov (United States)

    Laine, R A

    1994-12-01

    The number of all possible linear and branched isomers of a hexasaccharide was calculated and found to be > 1.05 x 10(12). This large number defines the Isomer Barrier, a persistent technological barrier to the development of a single analytical method for the absolute characterization of carbohydrates, regardless of sample quantity. Because of this isomer barrier, no single method can be employed to determine complete oligosaccharide structure in 100 nmol amounts with the same assurance that can be achieved for 100 pmol amounts with single-procedure Edman peptide or Sanger DNA sequencing methods. Difficulties in the development of facile synthetic schemes for oligosaccharides are also explained by this large number. No current method of chemical or physical analysis has the resolution necessary to distinguish among 10(12) structures having the same mass. Therefore the 'characterization' of a middle-weight oligosaccharide solely by NMR or mass spectrometry necessarily contains a very large margin of error. Greater uncertainty accompanies results performed solely by sequential enzyme degradation followed by gel-permeation chromatography or electrophoresis, as touted by some commercial advertisements. Much of the literature which uses these single methods to 'characterize' complex carbohydrates is, therefore, in question, and journals should beware of publishing structural characterizations unless the authors reveal all alternate possible structures which could result from their analysis.(ABSTRACT TRUNCATED AT 250 WORDS)

  13. Yeast contribution to melatonin, melatonin isomers and tryptophan ethyl ester during alcoholic fermentation of grape musts.

    Science.gov (United States)

    Vigentini, Ileana; Gardana, Claudio; Fracassetti, Daniela; Gabrielli, Mario; Foschino, Roberto; Simonetti, Paolo; Tirelli, Antonio; Iriti, Marcello

    2015-05-01

    Melatonin (MEL) has been found in some medicinal and food plants, including grapevine, a commodity of particular interest for the production of wine, a beverage of economic relevance. It has also been suggested that MEL in wine may, at least in part, contribute to the health-promoting properties attributed to this beverage and, possibly, to other traditional Mediterranean foodstuffs. After a preliminary screening of 9 yeast strains in laboratory medium, three selected strains (Saccharomyces cerevisiae EC1118, Torulaspora delbrueckii CBS1146(T) and Zygosaccharomyces bailii ATCC36947(T) ) were inoculated in experimental musts obtained from 2 white (Moscato and Chardonnay) and 2 red (Croatina and Merlot) grape varieties. The production of MEL, melatonin isomers (MIs) and tryptophan ethyl ester (TEE) was monitored during the alcoholic fermentation. The screening showed that the three investigated strains produced the highest concentrations of MEL and two MIs in optimal growth conditions. However, MEL and MIs were not produced in oenological conditions, but the three strains synthesized high concentrations of a new MI and TEE in musts.

  14. Monoterpene synthases of loblolly pine (Pinus taeda) produce pinene isomers and enantiomers.

    Science.gov (United States)

    Phillips, M A; Savage, T J; Croteau, R

    1999-12-01

    The turpentine fraction of conifer oleoresin is a complex mixture of monoterpene olefins and plays important roles in defense and in the mediation of chemical communication between conifer hosts and insect predators. The stereochemistry of the turpentine monoterpenes is critical in these interactions, influencing host recognition, toxicity, and potency of derived pheromones, and the stereochemical composition of these compounds lends insight into their biogenetic origin, with implications for the numbers and types of enzymes responsible and their corresponding genes. Analysis of the oleoresin from several tissues of loblolly pine (Pinus taeda) showed the derived turpentine to consist mainly of (+)-(3R:5R)-alpha-pinene and (-)-(3S:5S)-beta-pinene. Cell-free extracts from xylem tissue yielded three monoterpene synthases which together account for the monoterpene isomer and enantiomer content of the turpentine of this tissue. The major products of these enzymes, produced from the universal precursor of monoterpenes, geranyl diphosphate, were shown to be (+)-alpha-pinene, (-)-alpha-pinene, and (-)-beta-pinene, respectively. In most properties (molecular mass of approximately 60 kDa, K(m) for geranyl diphosphate of 3 microM, requirement for monovalent and divalent cations), these enzymes resemble other monoterpene synthases from conifer species.

  15. Unequivocal glycyrrhizin isomer determination and comparative in vitro bioactivities of root extracts in four Glycyrrhiza species

    Directory of Open Access Journals (Sweden)

    Mohamed A. Farag

    2015-01-01

    Full Text Available Glycyrrhiza glabra, commonly known as licorice, is a popular herbal supplement used for the treatment of chronic inflammatory conditions and as sweetener in the food industry. This species contains a myriad of phytochemicals including the major saponin glycoside glycyrrhizin (G of Glycyrrhetinic acid (GA aglycone. In this study, 2D-ROESY NMR technique was successfully applied for distinguishing 18α and 18β glycyrrhetinic acid (GA. ROESY spectra acquired from G. glabra, Glycyrrhiza uralensis and Glycyrrhiza inflata crude extracts revealed the presence of G in its β-form. Anti-inflammatory activity of four Glycyrrhiza species, G, glabra, G. uralensis, G. inflata, and G. echinata roots was assessed against COX-1 inhibition revealing that phenolics rather than glycyrrhizin are biologically active in this assay. G. inflata exhibits a strong cytotoxic effect against PC3 and HT29 cells lines, whereas other species are inactive. This study presents an effective NMR method for G isomer assignment in licorice extracts that does not require any preliminary chromatography or any other purification step.

  16. Evolution of nuclear structure in neutron-rich odd-Zn isotopes and isomers

    Science.gov (United States)

    Wraith, C.; Yang, X. F.; Xie, L.; Babcock, C.; Bieroń, J.; Billowes, J.; Bissell, M. L.; Blaum, K.; Cheal, B.; Filippin, L.; Garcia Ruiz, R. F.; Gins, W.; Grob, L. K.; Gaigalas, G.; Godefroid, M.; Gorges, C.; Heylen, H.; Honma, M.; Jönsson, P.; Kaufmann, S.; Kowalska, M.; Krämer, J.; Malbrunot-Ettenauer, S.; Neugart, R.; Neyens, G.; Nörtershäuser, W.; Nowacki, F.; Otsuka, T.; Papuga, J.; Sánchez, R.; Tsunoda, Y.; Yordanov, D. T.

    2017-08-01

    Collinear laser spectroscopy was performed on Zn (Z = 30) isotopes at ISOLDE, CERN. The study of hyperfine spectra of nuclei across the Zn isotopic chain, N = 33- 49, allowed the measurement of nuclear spins for the ground and isomeric states in odd-A neutron-rich nuclei up to N = 50. Exactly one long-lived (>10 ms) isomeric state has been established in each 69-79Zn isotope. The nuclear magnetic dipole moments and spectroscopic quadrupole moments are well reproduced by large-scale shell-model calculations in the f5pg9 and fpg9d5 model spaces, thus establishing the dominant term in their wave function. The magnetic moment of the intruder Iπ = 1 /2+ isomer in 79Zn is reproduced only if the νs1/2 orbital is added to the valence space, as realized in the recently developed PFSDG-U interaction. The spin and moments of the low-lying isomeric state in 73Zn suggest a strong onset of deformation at N = 43, while the progression towards 79Zn points to the stability of the Z = 28 and N = 50 shell gaps, supporting the magicity of 78Ni.

  17. Bioaccumulation of HCH isomers in selected macroinvertebrates from the Elbe River: sources and environmental implications.

    Science.gov (United States)

    Kolaříková, Kateřina; von Tümpling, Wolf; Bartels, Peter

    2013-05-01

    Sediments of the Elbe River have been extremely polluted by contaminants originating from previous large-scale hexachlorocyclohexane (HCH) production and the application of γ-HCH (lindane) in its catchment in the second half of the twentieth century. In order to gain knowledge on bioaccumulation processes at lower trophic levels, field investigations of HCHs in macroinvertebrates were carried out along the longitudinal profile of the Elbe and tributary. Among the sites studied, concentrations in macroinvertebrates ranged within five orders of magnitude (0.01-100 μg/kg). In general, lower values of HCH isomers were observed at all Czech sites (mostly Elbe catchment, and these concentrations are decreasing over time to a lesser extent than γ-HCH. Higher HCH concentrations in sediments in the springtime are considered to be the result of erosion and transport processes during and after spring floods, and lower concentrations at sites downstream are thought to be caused by the time lapse involved in the transportation of contaminated particles from upstream. In addition, comparison with fish (bream) data from the literature revealed no increase in tissue concentrations between invertebrates and fish.

  18. Membrane Materials and Technology for Xylene Isomers Separation and Isomerization via Pervaporation

    KAUST Repository

    Bilaus, Rakan

    2014-11-01

    P-xylene is one of the highly influential commodities in the petrochemical industry. It is used to make 90% of the world’s third largest plastic production, polyethylene terephthalate (PET). With a continuously increasing demand, the current technology’s high energy intensity has become a growing concern. Membrane separation technology is a potential low-energy alternative. Polymeric membranes were investigated in a pervaporation experiment to separate xylene isomers. Polymers of intrinsic microporosity (PIMs) as well as polyimides (PIM-PI), including thermally cross-linked PIM-1, PIM-6FDA-OH and thermally-rearranged PIM-6FDA-OH were investigated as potential candidates. Although they exhibited extremely high permeability to xylenes, selectivity towards p-xylene was poor. This was attributed to the polymers low chemical resistance which was apparent in their strong tendency to swell in xylenes. Consequently, a perfluoro-polymer, Teflon AF 2400, with a high chemical resistance was tested, which resulted in a slightly improved selectivity. A super acid sulfonated perfluoro-polymer (Nafion-H) was used as reactive membrane for xylenes isomerization. The membrane exhibited high catalytic activity, resulting in 19.5% p-xylene yield at 75ᵒC compared to 20% p-xylene yield at 450ᵒC in commercial fixed bed reactors. Nafion-H membrane outperforms the commercial technology with significant energy savings.

  19. Isomers and conformational barriers of gas phase nicotine, nornicotine and their protonated forms

    Energy Technology Data Exchange (ETDEWEB)

    Yoshida, Tomoki; Farone, William A.; Xantheas, Sotiris S.

    2014-07-17

    We report extensive conformational searches of the neutral nicotine, nornicotine and their protonated analogs that are based on ab-initio second order Møller-Plesset perturbation (MP2) electronic structure calculations. Initial searches were performed with the 6-31G(d,p) and the energetics of the most important structures were further refined from geometry optimizations with the aug-cc-pVTZ basis set. Based on the calculated free energies at T=298 K for the gas phase molecules, neutral nicotine has two dominant trans conformers, whereas neutral nornicotine is a mixture of several conformers. For nicotine, the protonation on both the pyridine and the pyrrolidine sites is energetically competitive, whereas nornicotine prefers protonation on the pyridine nitrogen. The protonated form of nicotine is mainly a mixture of two pyridine-protonated trans conformers and two pyrrolidine-protonated trans conformers, whereas the protonated form of nornicotine is a mixture of four pyridine-protonated trans conformers. Nornicotine is conformationally more flexible than nicotine, however it is less protonated at the biologically important pyrrolidine nitrogen site. The lowest energy isomers for each case were found to interconvert via low (< 6 kcal/mol) rotational barriers around the pyridine-pyrrolidine bond.

  20. Encapsulation of citral isomers in extracted lemongrass oil with cyclodextrins: molecular modeling and physicochemical characterizations.

    Science.gov (United States)

    Rungsardthong Ruktanonchai, Uracha; Srinuanchai, Wanwisa; Saesoo, Somsak; Sramala, Issara; Puttipipatkhachorn, Satit; Soottitantawat, Apinan

    2011-01-01

    The complexation between two isomers of citral in lemongrass oil and varying types of cyclodextrins (CDs), α-CD, β-CD, and HP-β-CD, were studied by molecular modeling and physicochemical characterization. The results obtained revealed that the most favorable complex formation governing between citrals in lemongrass oil and CDs were found at a 1:2 mole ratio for all CDs. Complex formation between E-citral and CD was more favorable than between Z-citral and CD. The thermal stability of the inclusion complex was observed compared to the citral in the lemongrass oil. The release time course of citral from the inclusion complex was the diffusion control, and it correlated well with Avrami's equation. The release rate constants of the E- and Z-citral inclusion complexes at 50 °C, 50% RH were observed at 1.32×10(-2) h(-1) and 1.43×10(-2) h(-1) respectively.

  1. Stability of isoflavone isomers in steamed black soybeans and black soybean koji stored under different conditions.

    Science.gov (United States)

    Huang, Ru-Yue; Chou, Cheng-Chun

    2009-03-11

    Steamed black soybeans and black soybean koji, a potentially functional food additive, were stored at 4 or 25 degrees C with or without deoxidant and desiccant for 120 days. After storage, steamed black soybeans and koji showed various extents of reduction in isoflavone contents dependent on storage temperature, packaging condition, and the kind of isoflavone isomer. Generally, black soybeans and koji showed the highest residual of isoflavone when they were stored at 4 degrees C with deoxidant and desiccant. Under this storage condition, beta-glucosides (daidzin, glycitin, and genistein), acetyl glucosides (acetyldaidzin, acetylglycitin, and acetylgenistin), manlonyl glucosides (malonyldaidzin, malonglycitin, and malonylgenistin), and aglycones (daidzein, glycitein, and genistin) in steamed black soybeans exhibited residuals of 100.1-100.9, 92.0-99.4, 90.0-94.0, and 77.2-78.8%, respectively, of their original contents after 120 days of storage. Meanwhile, the residuals found in black soybean koji were 77.8-90.0, 13.1-88.9, 66.7-85.5, and 76.4-80.6%, respectively.

  2. Calibration of the isomer shift of {sup 133}Cs from internal conversion measurement

    Energy Technology Data Exchange (ETDEWEB)

    Ishii, Hiroko; Tanaka, Eiji; Muramatsu, Hisakazu [Shinshu Univ., Matsumoto, Nagano (Japan)] [and others

    1997-03-01

    In this study, for 81 KeV transition of 133-Cs which is one of Moessbauer nuclides belonged to alkaline element and can be useful probe on study of binding state in a compound with high ionic boundability specific to alkaline element, an experiment to obtain {Delta}R/R was conducted by measurement of Moessbauer isomer shift and of internal conversion intensity of outer shell electron, using an internal conversion method, one of obtaining methods of {Delta} at the most accuracy. 133-Xe was buried at shallow surface of a host metal, reduced energy loss of internal conversion electron to realize high resolution and aimed to separate O-shell from P-shell to reduce injected ionic spaced and prepare a source. In range measurement of various energy to confirm actual speed reduction of ion, transmittance of 133-Xe on Cu layer vapor-deposited 2 to 10 micro g/sq cm thick on an Ni-foil was conducted. As a result, mean ranges of each energy were 5:2.2, 10:3.7, 15:4.8, and 20:5.6 micro g/sq cm, respectively. It was thought to be proved that speed reduction was certainly conducted by facts that the range increased with increase of the incident energy which showed good agreement with calculation results due to TRIM-95 code. (G.K.)

  3. Two positional isomers of sialylheptasaccharides isolated from the urine of a patient with sialidosis.

    Science.gov (United States)

    Kuriyama, M; Ariga, T; Ando, S; Suzuki, M; Yamada, T; Miyatake, T; Igata, A

    1985-10-01

    We describe the structures of two positional isomers of sialylheptasaccharide isolated from the urine of a patient with sialidosis with partial deficiency of beta-galactosidase. Based on structural studies including compositional sugar analysis, exoglycosidase digestion, chemical ionization mass spectrometry, proton nuclear magnetic resonance spectrometry, and methylation analysis, their structures were deduced to be as follows: AcNeu alpha 2----6Gal beta 1----4GlcNac beta 1----2Man alpha 1----3(Man alpha 1----6)Man beta 1----4GlcNac; AcNeu alpha 2----6Gal beta 1----4GlcNac beta 1----2Man alpha 1----6(Man alpha 1----3)Man beta 1----4GlcNac. Sialyloligosaccharide 1 has previously been found in the urine and liver of patients with mucolipidosis I and II and sialidosis, but sialyloligosaccharide 2 has not been found yet in human urine. These two sialyloligosaccharides could not be completely separated by any chromatographic procedures tested. The analytical techniques, including methylation study and NMR spectroscopy, could not clearly detect the differences between them. However, alpha-mannosidase treatment gave important information for the structural analyses of these sialyloligosaccharides.

  4. Evolution of nuclear structure in neutron-rich odd-Zn isotopes and isomers

    Directory of Open Access Journals (Sweden)

    C. Wraith

    2017-08-01

    Full Text Available Collinear laser spectroscopy was performed on Zn (Z=30 isotopes at ISOLDE, CERN. The study of hyperfine spectra of nuclei across the Zn isotopic chain, N=33–49, allowed the measurement of nuclear spins for the ground and isomeric states in odd-A neutron-rich nuclei up to N=50. Exactly one long-lived (>10 ms isomeric state has been established in each 69–79Zn isotope. The nuclear magnetic dipole moments and spectroscopic quadrupole moments are well reproduced by large-scale shell–model calculations in the f5pg9 and fpg9d5 model spaces, thus establishing the dominant term in their wave function. The magnetic moment of the intruder Iπ=1/2+ isomer in 79Zn is reproduced only if the νs1/2 orbital is added to the valence space, as realized in the recently developed PFSDG-U interaction. The spin and moments of the low-lying isomeric state in 73Zn suggest a strong onset of deformation at N=43, while the progression towards 79Zn points to the stability of the Z=28 and N=50 shell gaps, supporting the magicity of 78Ni.

  5. Thermodynamic Analysis of Chemically Reacting Mixtures and Their Kinetics: Example of a Mixture of Three Isomers.

    Science.gov (United States)

    Pekař, Miloslav

    2016-10-18

    Thermodynamics provides consequences of and restrictions on chemically reacting mixtures, particularly their kinetics, which have not been fully explored. Herein, a comprehensive thermodynamic analysis is illustrated for a reacting mixture of three isomers. The rate equation is first derived on the basis of the results of nonequilibrium continuum thermodynamics of linear fluids, and is then subjected to the requirement of consistency with entropic inequality (the second law). This consistency test involves the correct representation of the reaction rate as a function of affinities. It is shown that entropic inequality restricts the signs or values of coefficients in the constitutive equations for reaction rates/rate constants. The use of reverse rate constants and the identification of thermodynamic and kinetic equilibrium constants are not necessary in this approach. Although the presented thermodynamic analysis works only for independent reactions, the rates of dependent reactions are not excluded from having effects on kinetics. It is shown that the rates of dependent reactions are combined from the rates of independent reactions differently than dependent reactions are combined from independent reactions. The results are compared to the classical mass-action rate equations, and new restrictions on the values of the classical rate constants are derived.

  6. Spermicidal Effect of Propranolol and Its Isomers on Human Sperm in vitro

    Institute of Scientific and Technical Information of China (English)

    陆仁康; 袁德祥

    1995-01-01

    Fourty semen samples were collected from healthy volunteers by masturbation. The samples were then divided into four groups according to the quality and quantity of the sperm. The propranolol (D,L-P) and its isomers including the Dextro-propranolol (D-P) and Leco-propranolol (L-P) solution of various concentrations were tested. Spermicidal effect at carious intervals was observed by microscopy, and then compared to the Nonoxynol (NP-9) as a reference spermicide. The results showed that the mean values of lowest effective spermicidal concentration of D,L-P, D-P and L-P within twenty seconds were 1.00±0.63,1.10±0.62 and 0.91±0.54 (mg/ml) respectively, there was no significant difference among them (P>0.05), but they were significantly different from that of NP-9 (P<0.001). It is well known that the D-P has no significant beta-adrenoceptor blocking activity, so the D-P might be a new promising vaginal contraceptive drug.

  7. Exploring Solvent Shape and Function Using - and Isomer-Selective Vibrational Spectroscopy

    Science.gov (United States)

    Johnson, Mark

    2010-06-01

    We illustrate the new types of information than can be obtained through isomer-selective ``hole-burning'' spectroscopy carried out in the vibrational manifolds of Ar-tagged cluster ions. Three examples of increasing complexity will be presented where the changes in a solute ion are correlated with different morphologies of a surrounding solvent cage. In the first, we discuss the weak coupling limit where different hydration morphologies lead to small distortions of a covalent ion. We then introduce the more interesting case of the hydrated electron, where different shapes of the water network lead to dramatic changes in the extent of delocalization in the diffuse excess electron cloud. We then turn to the most complex case involving hydration of the nitrosonium ion, where different arrangements of the same number of water molecules span the range in behavior from simple solvation to actively causing a chemical reaction. The latter results are particularly interesting as they provide a microscopic, molecular-level picture of the ``solvent coordinate'' commonly used to describe solvent mediated processes.

  8. Kinetic crystallization separation process of the inositol isomers by controlling metastable zones

    Science.gov (United States)

    Konuki, Kaname; Hirasawa, Izumi

    2013-06-01

    D-chiro-inositol (DCI) is prepared by the immobilized enzyme reaction which uses myo-inositol (MI) as the substrate and the conversion rate is about 13%. The aim of this study was to develop a separation method for high purity DCI crystals from a reaction solution including low purity DCI only by the crystallization process. We succeeded in separating DCI crystals of 96% purity by water cooling crystallization, but it was presumed that scale-up was difficult. Although we tried anti-solvent crystallization similar to water cooling crystallization, high purity DCI crystals were not obtained. Therefore, we proposed the crystallization separation process by controlling metastable zones. The purity of a desired compound is controlled by this process, because solid-liquid separation is achieved before crystallization of compound in metastable zone. By the crystallization using this method, the DCI crystals of 97% purity were obtained. Although the yield per batch is about 50%, the actual yield is improved as the last mother liquor returns into the process of the following batch. When this process was repeated, the purity and the yield of DCI were reproduced and the robustness of this process was proved. It is expected that scale-up of this process will be successful, and this purification method could be applicable to similar systems such as separation of isomers and analogs.

  9. Anomalously large difference in dipole moment of isomers with nearly identical thermodynamic stability.

    Science.gov (United States)

    Nadykto, Alexey B; Yu, Fangqun

    2008-08-07

    Sulfuric acid is a primary atmospheric nucleation precursor, with the ability to form stable aqueous hydrogen-bonded clusters/complexes. The electrical dipole moment of such clusters/complexes is important for ion-induced nucleation, largely controlled by dipole-charge interaction of airborne ions with vapor monomers and pre-existing clusters. Although experiments typically trace a single lowest energy conformer at low temperatures, the present study shows that the immediate vicinity (dipole moments. The difference in the dipole moment of mono-, di-, and trihydrates of the sulfuric acid exceeds 1.3-1.5 Debyes ( approximately 50-60%), 1.4-2.6 Debyes ( approximately 50-90%), and 3.8-4.2 Debyes ( approximately 370-550%), respectively. Being driven by the temperature dependence of the Boltzmann distribution, the difference between the Boltzmann-Gibbs average dipole moment and the dipole moment of the most stable isomer increases with the ambient temperature, leading to large variations in the dipole-ion interaction strength, which may have important implications for the ion-mediated production of ultrafine aerosol particles associated with various climatic and health impacts.

  10. Accurate High-Temperature Reaction Networks for Alternative Fuels: Butanol Isomers

    Energy Technology Data Exchange (ETDEWEB)

    Van Geem, K. M.; Pyl, S. P.; Marin, G. B.; Harper, M. R.; Green, W. H.

    2010-11-03

    Oxygenated hydrocarbons, particularly alcohol compounds, are being studied extensively as alternatives and additives to conventional fuels due to their propensity of decreasing soot formation and improving the octane number of gasoline. However, oxygenated fuels also increase the production of toxic byproducts, such as formaldehyde. To gain a better understanding of the oxygenated functional group’s influence on combustion properties—e.g., ignition delay at temperatures above the negative temperature coefficient regime, and the rate of benzene production, which is the common precursor to soot formation—a detailed pressure-dependent reaction network for n-butanol, sec-butanol, and tert-butanol consisting of 281 species and 3608 reactions is presented. The reaction network is validated against shock tube ignition delays and doped methane flame concentration profiles reported previously in the literature, in addition to newly acquired pyrolysis data. Good agreement between simulated and experimental data is achieved in all cases. Flux and sensitivity analyses for each set of experiments have been performed, and high-pressure-limit reaction rate coefficients for important pathways, e.g., the dehydration reactions of the butanol isomers, have been computed using statistical mechanics and quantum chemistry. The different alcohol decomposition pathways, i.e., the pathways from primary, secondary, and tertiary alcohols, are discussed. Furthermore, comparisons between ethanol and n-butanol, two primary alcohols, are presented, as they relate to ignition delay.

  11. Beta decay of medium and high spin isomers in sup 9 sup 4 Ag

    CERN Document Server

    La Commara, M; Döring, J; Galanopoulos, S; Grawe, H; Harissopoulos, S V; Hellström, M; Janas, Z; Kirchner, R; Mazzocchi, C; Ostrowski, A N; Plettner, C; Rainovski, G; Roeckl, E; Schmidt, K

    2002-01-01

    The very neutron-deficient isotope sup 9 sup 4 Ag was produced at the GSI on-line mass separator by using the reaction sup 5 sup 8 Ni( sup 4 sup 0 Ca, p3n). The beta-decay properties of sup 9 sup 4 Ag were studied by detecting for the first time beta-delayed gamma rays and beta-gamma-gamma coincidences. Both the population of excited levels in the daughter nucleus sup 9 sup 4 Pd and the beta-decay half-life of sup 9 sup 4 Ag were investigated. The major part of the feeding was assigned to the decay of an I suppi=(7 sup +) isomer with a half-life of (0.36+-0.03) s. A weak beta-decay branch was found to populate high-spin levels in the sup 9 sup 4 Pd daughter with I>=18. It is tentatively assigned to the decay of a high-spin parent state in sup 9 sup 4 Ag with I>=17 and a half-life (0.3+-0.2) s. The measured beta-decay properties as well as the level structure of sup 9 sup 4 Ag and sup 9 sup 4 Pd are discussed in comparison with shell-model predictions.

  12. HPLC-F analysis of melatonin and resveratrol isomers in wine using an SPE procedure.

    Science.gov (United States)

    Mercolini, Laura; Addolorata Saracino, Maria; Bugamelli, Francesca; Ferranti, Anna; Malaguti, Marco; Hrelia, Silvana; Raggi, Maria Augusta

    2008-04-01

    An original analytical method has been developed for the determination of the antioxidants trans-resveratrol (t-RSV) and cis-resveratrol (c-RSV) and of melatonin (MLT) in red and white wine. The method is based on HPLC coupled to fluorescence detection. Separation was obtained by using a RP column (C8, 150 mm x 4.6 mm id, 5 mum) and a mobile phase composed of 79% aqueous phosphate buffer at pH 3.0 and 21% ACN. Fluorescence intensity was monitored at lambda = 386 nm while exciting at lambda = 298 nm, mirtazapine was used as the internal standard. A careful pretreatment of wine samples was developed, using SPE with C18 cartridges (100 mg, 1 mL). The calibration curves were linear over the following concentration ranges: 0.03-5.00 ng/mL for MLT, 3-500 ng/mL for t-RSV and 1-150 ng/mL for c-RSV. The LOD values were 0.01 ng/mL for MLT, 1 ng/mL for t-RSV and 0.3 ng/mL for c-RSV. Precision data, as well as extraction yield and sample purification results, were satisfactory. Thus, the method seems to be suitable for the analysis of MLT and resveratrol isomers in wine samples. Moreover, wine total polyphenol content and antioxidant activity were evaluated.

  13. New isomers in the neutron-rich A approx 190 mass region

    CERN Document Server

    Caamano, M

    2002-01-01

    Previously unobserved isomeric states in sup 1 sup 8 sup 8 Ta, sup 1 sup 9 sup 0 W, sup 1 sup 9 sup 2 Re, sup 1 sup 9 sup 3 Re, sup 1 sup 9 sup 5 Os, sup 1 sup 9 sup 7 Ir, sup 1 sup 9 sup 8 Ir, sup 2 sup 0 sup 0 Pt, sup 2 sup 0 sup 1 Pt, sup 2 sup 0 sup 2 Pt and sup 2 sup 0 sup 3 Au, with half-lives ranging from 10 ns to 290 mu s have been populated and studied using a fragmentation reaction in conjunction with a forward focussing spectrometer. In most cases, this provided the first ever spectroscopic data made available for the nucleus, and sup 2 sup 0 sup 0 Pt presented the first new seniority 4 state, on the basis of gamma-gamma coincidences, following a fragmentation reaction. Half-lives have been measured and tentative level schemes have been drawn for each isomer, spins and parities being consistent with blocked BCS calculations, hindrance factors, systematics and the relative intensities of gamma-rays and X-rays (where possible). Isomeric ratios have been measured, values ranging from 1 % to 64 %. Pote...

  14. Antidepressant versus neuroleptic activities of sulpiride isomers on four animal models of depression.

    Science.gov (United States)

    Vaccheri, A; Dall'Olio, R; Gaggi, R; Gandolfi, O; Montanaro, N

    1984-01-01

    The atypical neuroleptic sulpiride is also prescribed for depression because of its activating effect. However, such an effect does not necessarily imply an action identical to that of classical antidepressants, and a laboratory comparison of the neuroleptic and antidepressant activities of sulpiride may contribute to a better definition of its psychotherapeutic profile. Sulpiride isomers were studied in the rat in four behavioural models of depression which are thought to be influenced by neuroleptics in different ways. Desipramine (imipramine) and haloperidol were employed in each test as a standard antidepressant and neuroleptic, respectively. The four tests were: 1) prevention of apomorphine-induced sedation: 2) antagonism of apomorphine-induced hypothermia; 3) behavioural despair (swim test); 4) learned helplessness ( FR2 lever pressing escape). Desipramine ameliorated behaviour in all tests; haloperidol ameliorated the response to test 1, influenced that to test 2 in a neuroleptic-like way and worsened the responses to tests 3 and 4. (-)-Sulpiride worked in a similar way to haloperidol in all tests. (+)-Sulpiride significantly and dose-dependently ameliorated the responses to test 3 and was inactive in the others. No conclusion was drawn from test 1 owing to its lack of specificity; the results of the remaining tests indicated a neuroleptic profile of (-)-sulpiride and suggested a potential "antidepressant" activity of (+)-sulpiride which merits further investigation.

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

    Institute of Scientific and Technical Information of China (English)

    陈洲; 佟秋男; 张丛丛; 胡湛

    2015-01-01

    Identification of acetone and its two isomers, and the control of their ionization and dissociation processes are per-formed 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. Com-pared 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.

  16. The CH3CHOO `Criegee Intermediate' and its anion: Isomers, Infrared spectra, and W3-F12 energetics

    CERN Document Server

    Kettner, Marcus; McKinley, Allan; Wild, Duncan

    2015-01-01

    For the CH3CHOO Criegee intermediates (ethanal-oxide) and analogous anions, we obtain heats of formations and electron affinities at CCSDT(Q)/CBS level of theory by means of the high-level W3-F12 thermochemical protocol. The electron affinities amount to 0.20 eV and 0.35 eV for the cis and trans isomer, respectively. Neutral cis and trans isomers are separated by 14.1 kJ/mol, the anions are almost isoenergetic (0.4 kJ/mol separation). Harmonic vibrational frequencies are presented at CCSD(T)/aug'-cc-pVTZ level of theory. Since the synthesis of these species in gas-phase experiments might be possible in the near future, we include a predicted photoelectron spectrum.

  17. Preparation and Characterization of (E)- and (Z)-2-(Biphenyl-4-yl)-1-(4-bromophenyl)-1-phenylethene Isomers

    Energy Technology Data Exchange (ETDEWEB)

    Son, Hojun; Lee, Dongwoo; Lee, Taewon; Ok, Kangmin; Park, Kwangyong [Chung-Ang Univ., Seoul (Korea, Republic of)

    2014-06-15

    Stilbene compounds, well known for their biological activities, have been widely investigated as short subunits of poly(p-phenylenevinylene), the first light-emitting polymer, to understand the emission mechanism and relationship between the molecular structure and emitted light. Distyrylarylene derivatives are also well known as blue fluorescent materials and hole-transport materials. As part of our program directed toward the development of novel blue electroluminescent materials with unsymmetrical stilbene or distyrylarylene skeletons, we have prepared various bromostilbene intermediates by the Horner. Wadsworth.Emmons reaction of bromobenzophenone derivatives with benzyl phosphonates. However, great difficulties arise when isolating and identifying pure products from these reactions because of the generation of chromatographically inseparable mixtures of (E)- and (Z)-geometric isomers. Therefore, an efficient process for separating the two isomers is quite necessary for the systematic development of electroluminescent π-conjugated hydrocarbons.

  18. The 75As(n,2n) Cross Sections into the 74As Isomer and Ground State

    Energy Technology Data Exchange (ETDEWEB)

    Younes, W; Garrett, P E; Becker, J A; Bernstein, L A; Ormand, W E; Dietrich, F S; Nelson, R O; Devlin, M; Fotiades, N

    2003-06-30

    The {sup 75}As(n, 2n) cross section for the population of the T{sub 1/2} = 26.8-ns isomer at E{sub x} = 259.3 keV in {sup 74}As has been measured as a function of incident neutron energy, from threshold to E{sub n} = 20 MeV. The cross section was measured using the GEANIE spectrometer at LANSCE/WNR. For convenience, the {sup 75}As(n, 2n) population cross section for the {sup 74}As ground state has been deduced as the difference between the previously-known (n, 2n) reaction cross section and the newly measured {sup 75}As(n, 2n){sup 74}As{sup m} cross section. The (n, 2n) reaction, ground-state, and isomer population cross sections are tabulated in this paper.

  19. Spectrophotometric thermodynamic study of orientational isomers formed by inclusion of methyl orange into β-cyclodextrin nanocavity

    DEFF Research Database (Denmark)

    Kompany Zare, Mohsen; Mokhtari, Zeinab; Abdollahi, Hamid

    2012-01-01

    of methyl orange. This study was performed in basic and acidic media to yield the microconstants and thermodynamic parameters for inclusion complex formation equilibria in each media. The recorded data set at a constant temperature is rank deficient, because there is a linear dependency between...... was also performed, to calculate the microconstants and thermodynamic parameters related to ionization. The interaction of the basic form of methyl orange with β-cyclodextrin in basic medium led to two orientational isomers. In acidic medium methyl orange has two tautomeric forms, called ammonium......Spectrophotometry has been used to investigate the interaction of methyl orange (MO), an azo dye as a guest, with β-cyclodextrin (CD) as the host. Inclusion of methyl orange into β-cyclodextrin nanocavity leads to two orientational isomers, so-called inclumers, because of the asymmetric structure...

  20. Cage Compounds as Potential Energetic Oxidizers: A Theoretical Study of a Cage Isomer of N2O3

    Science.gov (United States)

    2014-07-01

    in Aqueous Alkaline-Solutions – Evidence for the Existence of Molecular Isomers of Dintrogen Tetraoxide and Dintrogen Trioxide, J. [a] R.J... Molecular Volumes, J. Phys. Chem. A 2007, 111, 10874 [21] G. Singh, S. P. Felix, P. Soni, Studies on energetic compounds Part 21. Thermolysis and...25] a) P. Piecuch, M. Wloch, Renormalized coupled- cluster methods exploiting left eigenstates of the similarity-transformed Hamiltonian , J. Chem

  1. Decay of the 16.3 min Decay of the 16.3 min {sup 182}Ta Isomer

    Energy Technology Data Exchange (ETDEWEB)

    Hoejeberg, M. [Inst. of Physics, Univ. of Stockholm, Stockholm (Sweden); Malmskog, S.G. [AB Atomenergi, Nykoeping (Sweden)

    1967-01-15

    Some transitions in the decay of the 16.3 min {sup 182}Ta isomer have been studied with a Ge(Li) detector and a double lens electron coincidence spectrometer. Gamma ray and conversion electron intensities were measured. From a delayed coincidence experiment it was concluded that both of the two lowest excited states in {sup 182}Ta had a half life less than 30 psec.

  2. Dynamic Kinetic Asymmetric Amination of Alcohols: From A Mixture of Four Isomers to Diastereo- and Enantiopure α-Branched Amines.

    Science.gov (United States)

    Rong, Zi-Qiang; Zhang, Yao; Chua, Raymond Hong Bing; Pan, Hui-Jie; Zhao, Yu

    2015-04-22

    The first dynamic kinetic asymmetric amination of alcohols via borrowing hydrogen methodology is presented. Under the cooperative catalysis by an iridium complex and a chiral phosphoric acid, α-branched alcohols that exist as a mixture of four isomers undergo racemization by two orthogonal mechanisms and are converted to diastereo- and enantiopure amines bearing adjacent stereocenters. The preparation of diastereo- and enantiopure 1,2-amino alcohols is also realized using this catalytic system.

  3. Dechlorination of three tetrachlorobenzene isomers by contaminated harbor sludge-derived enrichment cultures follows thermodynamically favorable reactions

    NARCIS (Netherlands)

    Lu, Yue; Ramiro-Garcia, Javier; Vandermeeren, Pieter; Herrmann, Steffi; Cichocka, Danuta; Springael, Dirk; Atashgahi, Siavash; Smidt, Hauke

    2016-01-01

    Dechlorination patterns of three tetrachlorobenzene isomers, 1,2,3,4-, 1,2,3,5-, and 1,2,4,5-TeCB, were studied in anoxic microcosms derived from contaminated harbor sludge. The removal of doubly, singly, and un-flanked chlorine atoms was noted in 1,2,3,4- and 1,2,3,5-TeCB fed microcosms, whereas

  4. Isomer separation and gas-phase configurations of organoruthenium anticancer complexes: ion mobility mass spectrometry and modeling.

    Science.gov (United States)

    Williams, Jonathan P; Bugarcic, Tijana; Habtemariam, Abraha; Giles, Kevin; Campuzano, Iain; Rodger, P Mark; Sadler, Peter J

    2009-06-01

    We have used ion mobility-mass spectrometry combined with molecular modeling for the separation and configurational analysis of three low-molecular-weight isomeric organoruthenium anticancer complexes containing ortho-, meta-, or para-terphenyl arene ligands. The isomers were separated using ion mobility based on traveling-wave technology and the experimentally determined collision cross sections were compared to theoretical calculations. Excellent agreement was observed between the experimentally and theoretically derived measurements.

  5. Test purchase, synthesis, and characterization of 2-methoxydiphenidine (MXP) and differentiation from its meta- and para-substituted isomers.

    Science.gov (United States)

    McLaughlin, Gavin; Morris, Noreen; Kavanagh, Pierce V; Power, John D; O'Brien, John; Talbot, Brian; Elliott, Simon P; Wallach, Jason; Hoang, Khoa; Morris, Hamilton; Brandt, Simon D

    2016-01-01

    The structurally diverse nature of the 1,2-diphenylethylamine template provides access to a range of substances for drug discovery work but some have attracted attention as 'research chemicals'. The most recent examples include diphenidine, i.e. 1-(1,2-diphenylethyl)piperidine and 2-methoxydiphenidine, i.e. 1-[1-(2-methoxyphenyl)-2-phenylethyl]piperidine (MXP, methoxyphenidine, 2-MXP) that have been associated with uncompetitive N-methyl-D-aspartate (NMDA) receptor antagonist activity. Analytical challenges encountered during chemical analysis include the presence of positional isomers. Three powdered samples suspected to contain 2-MXP were obtained from three Internet retailers in the United Kingdom and subjected to analytical characterization by gas chromatography (GC) and high performance liquid chromatography (HPLC) coupled to various forms of mass spectrometry (MS). Nuclear magnetic resonance spectroscopy, infrared spectroscopy and thin layer chromatography were also employed. This was supported by the synthesis of all three isomers (2-, 3- and 4-MXP) by two different synthetic routes. The analytical data obtained for the three purchased samples were consistent with the synthesized 2-MXP standard and the differentiation between the isomers was possible. Distinct stability differences were observed for all three isomers during in-source collision-induced dissociation of the protonated molecule when employing detection under HPLC selected-ion monitoring detection, which added to the ability to differentiate between them. Furthermore, the analysis of a 2-MXP tablet by matrix assisted inlet ionization Orbitrap mass spectrometry confirmed that it was possible to detect the protonated molecule of 2-MXP directly from the tablet surface following addition of 3-nitrobenzonitrile as the matrix.

  6. Solid-vapor sorption of xylenes: prioritized selectivity as a means of separating all three isomers using a single substrate.

    Science.gov (United States)

    Lusi, Matteo; Barbour, Leonard J

    2012-04-16

    A Werner complex is highly selective for o-xylene in a vapor mixture containing all three isomers. However, in the absence of o-xylene, the substrate shows similar selectivity for m-xylene over p-xylene. Kinetic studies show a different trend whereby m-xylene is absorbed most rapidly, implying that thermodynamic factors must be responsible for the selectivity. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. PBPK modeling of the cis- and trans-permethrin isomers and their major urinary metabolites in rats.

    Science.gov (United States)

    Willemin, Marie-Emilie; Desmots, Sophie; Le Grand, Rozenn; Lestremau, François; Zeman, Florence A; Leclerc, Eric; Moesch, Christian; Brochot, Céline

    2016-03-01

    Permethrin, a pyrethroid insecticide, is suspected to induce neuronal and hormonal disturbances in humans. The widespread exposure of the populations has been confirmed by the detection of the urinary metabolites of permethrin in biomonitoring studies. Permethrin is a chiral molecule presenting two forms, the cis and the trans isomers. Because in vitro studies indicated a metabolic interaction between the trans and cis isomers of permethrin, we adapted and calibrated a PBPK model for trans- and cis-permethrin separately in rats. The model also describes the toxicokinetics of three urinary metabolites, cis- and trans-3-(2,2 dichlorovinyl)-2,2-dimethyl-(1-cyclopropane) carboxylic acid (cis- and trans-DCCA), 3-phenoxybenzoic acid (3-PBA) and 4'OH-phenoxybenzoic acid (4'-OH-PBA). In vivo experiments performed in Sprague-Dawley rats were used to calibrate the PBPK model in a Bayesian framework. The model captured well the toxicokinetics of permethrin isomers and their metabolites including the rapid absorption, the accumulation in fat, the extensive metabolism of the parent compounds, and the rapid elimination of metabolites in urine. Average hepatic clearances in rats were estimated to be 2.4 and 5.7 L/h/kg for cis- and trans-permethrin, respectively. High concentrations of the metabolite 4'-OH-PBA were measured in urine compared to cis- and trans-DCCA and 3-PBA. The confidence in the extended PBPK model was then confirmed by good predictions of published experimental data obtained using the isomers mixture. The extended PBPK model could be extrapolated to humans to predict the internal dose of exposure to permethrin from biomonitoring data in urine.

  8. Using torsional forces to explain the gradient temperature Raman spectra of endosulfan isomers and its irreversible isomerization

    Science.gov (United States)

    Schmidt, Walter F.; Hapeman, Cathleen J.; McConnell, Laura L.; Rice, Clifford P.; Broadhurst, C. Leigh; Nguyen, Julie K.; Qin, Jianwei; Chao, Kuanglin; Kim, Moon S.; Shelton, Daniel R.

    2017-07-01

    Since the 1950's, the broad-spectrum, organochlorine insecticide endosulfan (6,7,8, 9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide) has been used on numerous crops. Due to its persistence, bioaccumulation, long-range transport, and adverse effects to human health and ecosystems, it was officially identified as a persistent organic pollutant (POP) in 2011. The last uses in the United States were phased out in 2016. Endosulfan consists of two diastereomers, α-endosulfan and β-endosulfan, and while the α-isomer exists as two asymmetrical, twist-chair enantiomers which interchange, the β-isomer is a symmetrical-chair conformation. In addition, the β-isomer was found to isomerize to the α-isomer. Gradient Temperature Raman Spectroscopy (GTRS) enables identification the molecular sites at which bending vibrational modes becomes twisting or wagging vibrational modes. Previous studies using GTRS and chemical calculations afforded evidence for specific bond movements and the irreversibility of the isomerization mechanism. However, not all of the vibrational modes observed in the spectra could be explained. Thus, new analyses of the GTRS data were conducted to examine the effects of torsional forces on the bond movement, which allowed for the identification of all the peaks. These newly-identified torsional forces provide further confirmation of the isomerization mechanism and its irreversibility. Finally, this isomerization explains why β-endosulfan is rarely detected in the atmosphere.

  9. Preparation of new 2,3-diphenylpropenoic acid esters - good yields even for the more hindered Z isomers.

    Science.gov (United States)

    Boros, László; Felföldi, Károly; Pálinkó, István

    2004-03-31

    The potassium salt of E- and Z-2,3-diphenylpropenoic acids prepared in situ could be esterified efficiently in DMSO with the appropriate alkyl halides at room temperature. In this way 10 previously undescribed esters of these acids were synthesised and characterised. Excellent yields were observed for most of the E isomers and the more hindered Z esters were also obtained in good yields, far better than those obtained applying the classical acid-catalysed esterification reaction.

  10. Gravitational Gamma Spectrometer for Studying the Gamma Resonance of the Long-Lived Isomer 103mRh

    CERN Document Server

    Davydov, A V; Kalantarov, V D; Korotkov, M M; Migachev, V V; Novozhilov, Yu B; Stepanov, A M

    2015-01-01

    The principle of operation and the construction are described of the gravitational gamma spectrometer to study the gamma resonance of the long-lived isomer $^{103m}$Rh. This is a table-top device which measures the form of gamma resonance by the dependence of counting rate of gamma-rays in collimated beams on the angle of their inclination with respect of the horizontal plane. Methods of fabrication of gamma-sources for this device are considered.

  11. Synthesis, analytical characterization and capillary electrophoretic use of the single-isomer heptakis-(6-O-sulfobutyl)-beta-cyclodextrin.

    Science.gov (United States)

    Malanga, Milo; Fejős, Ida; Varga, Erzsébet; Benkovics, Gábor; Darcsi, András; Szemán, Julianna; Béni, Szabolcs

    2017-09-08

    This contribution reports the synthesis, characterization and capillary electrophoretic application of heptakis-(6-O-sulfobutyl-ether)-β-cyclodextrin sodium salt, (6-(SB)7-β-CD). The compound was obtained through a five-steps synthesis and it represents the first example of single-isomer sulfobutylated cyclodextrin that carries the negatively charged functions exclusively on its primary side and it is unmodified on the lower rim. The purity of each intermediate was determined by appropriate liquid chromatographic methods, while the isomeric purity of the final product was established by an ad-hoc developed HPLC method based on a CD-Screen-IEC column. The structural identification of 6-(SB)7-β-CD was carried out by 1D, 2D NMR spectroscopy and ESI-MS. The chiral separation ability of 6-(SB)7-β-CD was studied by chiral capillary electrophoresis using the single-isomer host as a background electrolyte additive to separate the enantiomers of a representative set of pharmacologically significant model compounds such as verapamil, dapoxetine, ondansetron, propranolol, atenolol, metoprolol, carvedilol, terbutaline, amlodipine and tadalafil. The enantiomer migration order and the effects of the selector concentration on the enantiorecognition properties were investigated. NMR spectroscopy was applied to deepen and further confirm the host-guest interactions and in the case of the model compound dapoxetine a potential representation for the supramolecular assembly was developed based on the dataset collected by the extensive 2D NMR analysis. This single-isomer chiral selector offers a new alternative to the widely applied randomly sulfobutylated- and sulfated-beta-cylodextrins as well as to the single-isomer sulfated and carboxymethylated derivatives in chiral separations. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Engineering Optics

    CERN Document Server

    Iizuka, Keigo

    2008-01-01

    Engineering Optics is a book for students who want to apply their knowledge of optics to engineering problems, as well as for engineering students who want to acquire the basic principles of optics. It covers such important topics as optical signal processing, holography, tomography, holographic radars, fiber optical communication, electro- and acousto-optic devices, and integrated optics (including optical bistability). As a basis for understanding these topics, the first few chapters give easy-to-follow explanations of diffraction theory, Fourier transforms, and geometrical optics. Practical examples, such as the video disk, the Fresnel zone plate, and many more, appear throughout the text, together with numerous solved exercises. There is an entirely new section in this updated edition on 3-D imaging.

  13. The role of core excitations in the structure and decay of the 16+ spin-gap isomer in 96Cd

    Directory of Open Access Journals (Sweden)

    P.J. Davies

    2017-04-01

    Full Text Available The first evidence for β-delayed proton emission from the 16+ spin gap isomer in 96Cd is presented. The data were obtained from the Rare Isotope Beam Factory, at the RIKEN Nishina Center, using the BigRIPS spectrometer and the EURICA decay station. βp branching ratios for the ground state and 16+ isomer have been extracted along with more precise lifetimes for these states and the lifetime for the ground state decay of 95Cd. Large scale shell model (LSSM calculations have been performed and WKB estimates made for ℓ=0,2,4 proton emission from three resonance-like states in 96Ag, that are populated by the β decay of the isomer, and the results compared to the new data. The calculations suggest that ℓ=2 proton emission from the resonance states, which reside ∼5 MeV above the proton separation energy, dominates the proton decay. The results highlight the importance of core-excited wavefunction components for the 16+ state.

  14. The impact of technical cashew nut shell liquid on thermally-induced trans isomers in edible oils.

    Science.gov (United States)

    Guo, Qin; Wang, Feng; He, Fan; Ha, Yi-Ming; Li, Qing-Peng; Jin, Jing; Deng, Zhao-Xuan

    2016-03-01

    The effects of technical cashew nut shell liquid (TCNSL) on the trans isomerization of edible oils during heating are investigated. Edible oils were subjected to thermal treatment at various heating times and temperatures. Our results show that the addition of TCNSL to edible oils at the appropriate concentration during heating suppresses trans fatty acid formation and induces formation of conjugated linoleic acid (CLA) isomers. A concentration of 0.2 % TCNSL demonstrates the best ability to inhibit formation of trans-oleic acid, trans-linoleic acid, and trans-linolenic acid isomers as well as increase the formation of 9 t,11 t-CLA and 10 t,12 t-CLA isomers. Our analysis indicates that the presence of 0.2 % TCNSL in corn oil does not significantly reduce the acid value, but may significantly lower the peroxide value. TCNSL is also observed to have better function compared to Vitamin E (VE) and tertiary butylhydroquinone (TBHQ), indicating that it may be considered an effective additive in edible oils.

  15. Enhancing glycan isomer separations with metal ions and positive and negative polarity ion mobility spectrometry-mass spectrometry analyses

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Xueyun; Zhang, Xing; Schocker, Nathaniel S.; Renslow, Ryan S.; Orton, Daniel J.; Khamsi, Jamal; Ashmus, Roger A.; Almeida, Igor C.; Tang, Keqi; Costello, Catherine E.; Smith, Richard D.; Michael, Katja; Baker, Erin S.

    2016-09-07

    Glycomics has become an increasingly important field of research since glycans play critical roles in biology processes ranging from molecular recognition and signaling to cellular communication. Glycans often conjugate with other biomolecules such as proteins and lipids, and alter their properties and functions, so understanding the effect glycans have on cellular systems is essential. However the analysis of glycans is extremely difficult due to their complexity and structural diversity (i.e., the number and identity of monomer units, and configuration of their glycosidic linkages and connectivities). In this work, we coupled ion mobility spectrometry with mass spectrometry (IMS-MS) to characterize glycan standards and biologically important isomers of synthetic αGal-containing O-glycans including glycotopes of the protozoan parasite Trypanosoma cruzi, which is the causative agent of Chagas disease. IMS-MS results showed significant differences for the glycan structural isomers when analyzed in positive and negative polarity and complexed with different metal cations. These results suggest specific metal ions or ion polarities could be used to target and baseline separate glycan isomers of interest with IMS-MS.

  16. HiFSA Fingerprinting Applied to Isomers with Near-Identical NMR Spectra: The Silybin/Isosilybin Case

    Science.gov (United States)

    Napolitano, José G.; Lankin, David C.; Graf, Tyler N.; Friesen, J. Brent; Chen, Shao-Nong; McAlpine, James B.; Oberlies, Nicholas H.; Pauli, Guido F.

    2013-01-01

    This study demonstrates how regio- and diastereo-isomers with near-identical NMR spectra can be distinguished and unambiguously assigned using quantum mechanical driven, 1H iterative Full Spin Analysis (HiFSA). The method is illustrated with four natural products, the flavonolignans silybin A, silybin B, isosilybin A, and isosilybin B, which exhibit extremely similar coupling patterns and chemical shift differences well below the commonly reported level of accuracy of 0.01 ppm. The HiFSA approach generated highly reproducible 1H NMR fingerprints that enable distinction of all four isomers at 1H frequencies from 300 to 900 MHz. Furthermore, it is demonstrated that the underlying numeric 1H NMR profiles, combined with iterative computational analysis, allow parallel quantification of all four isomers, even in difficult to characterize reference materials and mixtures. The results shed new light on the historical challenges to the qualitative and quantitative analysis of these therapeutically relevant flavonolignans and open new opportunities to explore hidden diversity in the chemical space of organic molecules. PMID:23461697

  17. Assigning Peptide Disulfide Linkage Pattern Among Regio-Isomers via Methoxy Addition to Disulfide and Tandem Mass Spectrometry

    Science.gov (United States)

    Durand, Kirt L.; Tan, Lei; Stinson, Craig A.; Love-Nkansah, Chasity B.; Ma, Xiaoxiao; Xia, Yu

    2017-02-01

    Pinpointing disulfide linkage pattern is critical in the characterization of proteins and peptides consisting of multiple disulfide bonds. Herein, we report a method based on coupling online disulfide modification and tandem mass spectrometry (MS/MS) to distinguish peptide disulfide regio-isomers. Such a method relies on a new disulfide bond cleavage reaction in solution, involving methanol as a reactant and 254 nm ultraviolet (UV) irradiation. This reaction leads to selective cleavage of a disulfide bond and formation of sulfenic methyl ester (-SOCH3) at one cysteine residue and a thiol (-SH) at the other. Under low energy collision-induced dissociation (CID), cysteine sulfenic methyl ester motif produces a signature methanol loss (-32 Da), allowing its identification from other possible isomeric structures such as S-hydroxylmethyl (-SCH2OH) and methyl sulfoxide (-S(O)-CH3). Since disulfide bond can be selectively cleaved and modified upon methoxy addition, subsequent MS2 CID of the methoxy addition product provides enhanced sequence coverage as demonstrated by the analysis of bovine insulin. More importantly, this reaction does not induce disulfide scrambling, likely due to the fact that radical intermediates are not involved in the process. An approach based on methoxy addition followed by MS3 CID has been developed for assigning disulfide linkage patterns in peptide disulfide regio-isomers. This methodology was successfully applied to characterizing peptide systems having two disulfide bonds and three disulfide linkage isomers: side-by-side, overlapped, and looped-within-a-loop configurations.

  18. High-spin structures in 132Xe and 133Xe and evidence for isomers along the N =79 isotones

    Science.gov (United States)

    Vogt, A.; Siciliano, M.; Birkenbach, B.; Reiter, P.; Hadyńska-Klek, K.; Wheldon, C.; Valiente-Dobón, J. J.; Teruya, E.; Yoshinaga, N.; Arnswald, K.; Bazzacco, D.; Blazhev, A.; Bracco, A.; Bruyneel, B.; Chakrawarthy, R. S.; Chapman, R.; Cline, D.; Corradi, L.; Crespi, F. C. L.; Cromaz, M.; de Angelis, G.; Eberth, J.; Fallon, P.; Farnea, E.; Fioretto, E.; Fransen, C.; Freeman, S. J.; Fu, B.; Gadea, A.; Gelletly, W.; Giaz, A.; Görgen, A.; Gottardo, A.; Hayes, A. B.; Hess, H.; Hetzenegger, R.; Hirsch, R.; Hua, H.; John, P. R.; Jolie, J.; Jungclaus, A.; Karayonchev, V.; Kaya, L.; Korten, W.; Lee, I. Y.; Leoni, S.; Liang, X.; Lunardi, S.; Macchiavelli, A. O.; Menegazzo, R.; Mengoni, D.; Michelagnoli, C.; Mijatović, T.; Montagnoli, G.; Montanari, D.; Müller-Gatermann, C.; Napoli, D.; Pearson, C. J.; Podolyák, Zs.; Pollarolo, G.; Pullia, A.; Queiser, M.; Recchia, F.; Regan, P. H.; Régis, J.-M.; Saed-Samii, N.; Şahin, E.; Scarlassara, F.; Seidlitz, M.; Siebeck, B.; Sletten, G.; Smith, J. F.; Söderström, P.-A.; Stefanini, A. M.; Stezowski, O.; Szilner, S.; Szpak, B.; Teng, R.; Ur, C.; Warner, D. D.; Wolf, K.; Wu, C. Y.; Zell, K. O.

    2017-08-01

    The transitional nuclei 132Xe and 133Xe are investigated after multinucleon-transfer (MNT) and fusion-evaporation reactions. Both nuclei are populated (i) in 136Xe+208Pb MNT reactions employing the high-resolution Advanced GAmma Tracking Array (AGATA) coupled to the magnetic spectrometer PRISMA, (ii) in the 136Xe+198Pt MNT reaction employing the GAMMASPHERE spectrometer in combination with the gas-detector array CHICO, and (iii) as an evaporation residue after a 130Te(α ,x n )134 -x nXe fusion-evaporation reaction employing the HORUS γ -ray array at the University of Cologne. The high-spin level schemes are considerably extended above the Jπ=(7-) and (10+) isomers in 132Xe and above the 11 /2- isomer in 133Xe. The results are compared to the high-spin systematics of the Z =54 as well as the N =78 and N =79 chains. Furthermore, evidence is found for a long-lived (T1 /2≫1 μ s ) isomer in 133Xe which closes a gap along the N =79 isotones. Shell-model calculations employing the SN100PN and PQM130 effective interactions reproduce the experimental findings and provide guidance to the interpretation of the observed high-spin features.

  19. Assigning Peptide Disulfide Linkage Pattern Among Regio-Isomers via Methoxy Addition to Disulfide and Tandem Mass Spectrometry

    Science.gov (United States)

    Durand, Kirt L.; Tan, Lei; Stinson, Craig A.; Love-Nkansah, Chasity B.; Ma, Xiaoxiao; Xia, Yu

    2017-06-01

    Pinpointing disulfide linkage pattern is critical in the characterization of proteins and peptides consisting of multiple disulfide bonds. Herein, we report a method based on coupling online disulfide modification and tandem mass spectrometry (MS/MS) to distinguish peptide disulfide regio-isomers. Such a method relies on a new disulfide bond cleavage reaction in solution, involving methanol as a reactant and 254 nm ultraviolet (UV) irradiation. This reaction leads to selective cleavage of a disulfide bond and formation of sulfenic methyl ester (-SOCH3) at one cysteine residue and a thiol (-SH) at the other. Under low energy collision-induced dissociation (CID), cysteine sulfenic methyl ester motif produces a signature methanol loss (-32 Da), allowing its identification from other possible isomeric structures such as S-hydroxylmethyl (-SCH2OH) and methyl sulfoxide (-S(O)-CH3). Since disulfide bond can be selectively cleaved and modified upon methoxy addition, subsequent MS2 CID of the methoxy addition product provides enhanced sequence coverage as demonstrated by the analysis of bovine insulin. More importantly, this reaction does not induce disulfide scrambling, likely due to the fact that radical intermediates are not involved in the process. An approach based on methoxy addition followed by MS3 CID has been developed for assigning disulfide linkage patterns in peptide disulfide regio-isomers. This methodology was successfully applied to characterizing peptide systems having two disulfide bonds and three disulfide linkage isomers: side-by-side, overlapped, and looped-within-a-loop configurations. [Figure not available: see fulltext.

  20. Kinetic and sequence-structure-function analysis of known LinA variants with different hexachlorocyclohexane isomers.

    Directory of Open Access Journals (Sweden)

    Pooja Sharma

    Full Text Available BACKGROUND: Here we report specific activities of all seven naturally occurring LinA variants towards three different isomers, α, γ and δ, of a priority persistent pollutant, hexachlorocyclohexane (HCH. Sequence-structure-function differences contributing to the differences in their stereospecificity for α-, γ-, and δ-HCH and enantiospecificity for (+- and (--α -HCH are also discussed. METHODOLOGY/PRINCIPAL FINDINGS: Enzyme kinetic studies were performed with purified LinA variants. Models of LinA2(B90A A110T, A111C, A110T/A111C and LinA1(B90A were constructed using the FoldX computer algorithm. Turnover rates (min(-1 showed that the LinAs exhibited differential substrate affinity amongst the four HCH isomers tested. α-HCH was found to be the most preferred substrate by all LinA's, followed by the γ and then δ isomer. CONCLUSIONS/SIGNIFICANCE: The kinetic observations suggest that LinA-γ1-7 is the best variant for developing an enzyme-based bioremediation technology for HCH. The majority of the sequence variation in the various linA genes that have been isolated is not neutral, but alters the enantio- and stereoselectivity of the encoded proteins.

  1. Crystal structures and electronic properties of BaC2 isomers by theoretical study based on DFT

    Institute of Scientific and Technical Information of China (English)

    FENG Jing; XIAO Bing; CHEN JingChao

    2008-01-01

    Band structures and electronic properties of two BaC2 isomers were calculated by using density functional theory (DFT) properly. The ionic bond features are all typical between cation (Ba) and anion clusters (C2) in both structures of the isomers. However, a much stronger covalent bond exists in anion clusters which can be seen by inspecting the electron distribution contour that has a dull bell like shape between two carbon atoms. The shortest distance between Ba2+ and C22- and the bond length in anion clusters are different in these isomers of BaC2, which are 0.2945 nm and 0.1185 nm for the structure with the 14/mmm space group and 0.2744 and 0.1136 nm with the C2/c type, respectively. Band structures were clarified by combining the DOS to indicate the ionic bonding features more clearly. Population analysis provided further evidence on these ideas. Thermodynamical calculation results reveal that the transition temperature of these two polymorphs of BaC2 locates near 132 K, which is consistent with the recent experimental results.

  2. Crystal structures and electronic properties of BaC2 isomers by theoretical study based on DFT

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Band structures and electronic properties of two BaC2 isomers were calculated by using density func-tional theory(DFT) properly.The ionic bond features are all typical between cation(Ba) and anion clusters(C2) in both structures of the isomers.However,a much stronger covalent bond exists in anion clusters which can be seen by inspecting the electron distribution contour that has a dull bell like shape between two carbon atoms.The shortest distance between Ba2+ and C22? and the bond length in anion clusters are different in these isomers of BaC2,which are 0.2945 nm and 0.1185 nm for the structure with the I4/mmm space group and 0.2744 and 0.1136 nm with the C2/c type,respectively.Band structures were clarified by combining the DOS to indicate the ionic bonding features more clearly.Population analysis provided further evidence on these ideas.Thermodynamical calculation results reveal that the transition temperature of these two polymorphs of BaC2 locates near 132 K,which is consistent with the recent experimental results.

  3. Reveal of small alkanes and isomers using calculated core and valence binding energy spectra and total momentum cross sections

    CERN Document Server

    Yang, Zejin

    2013-01-01

    The present study revealed quantum mechanically that the C1s binding energy spectra of the small alkanes (upto six carbons) provide a clear picture of isomeric chemical shift in linear alkanes and branched isomers, whereas the valence binding energy spectra contain more sensitive information regarding the length of the carbon chains. Total momentum cross sections of the alkanes exhibit the information of the chain length as well as constitutional isomers of the small alkanes. The C1s binding energies of small alkanes (including isomers) are position specific and the terminal carbons have the lowest energies. The length of an alkane chain does not apparently affect the C1s energies so that the terminal carbons (289.11 eV) of pentane are almost the same as those of hexane. The valence binding energy spectra of the alkanes are characterized by inner valence and outer valence regions which are separated by an energy gap at approximately 17 eV. The intensities of the total momentum cross sections of the alkanes ar...

  4. Onset of isomers in Cd125,126,127,128 and weakened neutron-neutron interaction strength

    Science.gov (United States)

    Hoteling, N.; Walters, W. B.; Tomlin, B. E.; Mantica, P. F.; Pereira, J.; Becerril, A.; Fleckenstein, T.; Hecht, A. A.; Lorusso, G.; Quinn, M.; Pinter, J. S.; Stoker, J. B.

    2007-10-01

    The presence of isomeric levels with half-lives in the microsecond range has been identified in Cd125,126,127,128. Neutron-rich Cd isotopes were produced from the fragmentation of a 120 MeV/nucleon Xe136 beam and uniquely identified through their time-of-flight, energy loss, and total kinetic energy. γ rays from these isomeric levels were measured with an array of Ge detectors that were gated for 15 μs by a particle implantation trigger from a stack of Si detectors. The γ rays observed in the decay of Cd126,128 isomers populate low-energy levels previously identified in the β decay of Ag126,128. The γ rays found in the decay of Cd125,127 isomers are consistent with expected yrast structures observed in lighter, odd-mass Cd isotopes. The appearance of these isomers at the point where N/Z exceeds 1.6 is interpreted as an indication of the onset of a weakened neutron-neutron interaction that has been proposed for Sn134, whose N/Z also exceeds 1.6.

  5. Simultaneous spectrophotometric determination of nitroaniline isomers after cloud point extraction by using least-squares support vector machines

    Science.gov (United States)

    Niazi, Ali; Ghasemi, Jahanbakhsh; Yazdanipour, Ateesa

    2007-11-01

    Cloud point extraction has been used for the preconcentration of m-nitroaniline, o-nitroaniline and p-nitroaniline and later simultaneous spectrophotometric determination using polyethylene glycol tert-octylphenyl ether (Triton X-100) as surfactant. The resolution of a ternary mixture of the nitroaniline isomers (after extraction by cloud point) by the application of least-squares support vector machines (LS-SVM) was performed. The chemical parameters affecting the separation phase and detection process were studied and optimized. Under the optimum experimental conditions (i.e. pH 7.0, Triton X-100 = 0.6%, equilibrium time 20 min and cloud point 75 °C), calibration graphs were linear in the range of 0.2-20.0, 0.1-15.0 and 0.1-17.0 μg ml -1 with detection limits of 0.08, 0.05 and 0.06 μg ml -1 for m-nitroaniline, o-nitroaniline and p-nitroaniline, respectively. The experimental calibration matrix was designed with 21 mixtures of these chemicals. The concentrations were varied between calibration graphs concentrations of nitroaniline isomers. The root mean square error of prediction (RMSEP) for m-nitroaniline, o-nitroaniline and p-nitroaniline were 0.0146, 0.0308 and 0.0304, respectively. This procedure allows the simultaneous determination of nitroaniline isomers in synthetic and real matrix samples good reliability of the determination was proved.

  6. Search for X-Ray Induced Acceleration of the Decay of the 31-yr Isomer 178Hf Using Synchrotron Radiation

    CERN Document Server

    Ahmad, I; Becker, J A; Gemmell, D S; Krämer, A; Mashayekhi, A; McNabb, D P; Miller, G G; Moore, E F; Pangault, L N; Rundberg, R S; Schiffer, J P; Shastri, S D; Wang, T F; Wilhelmy, J B

    2002-01-01

    Releasing the energy stored in an isomeric nuclear state in a controlled way with an atomic or electromagnetic trigger is an attractive speculation: the energy gain may be on the order of the ratio of nuclear/atomic energies - MeV/keV. (Nuclear isomers are loosely defined as excited nuclear states with lifetimes longer than 10 sup - sup 9 s.) Nuclear isomers, therefore, represent an opportunity for a stand-alone energy source if suitable schemes for trigger and control of the energy release can be found. Potential applications include space drive, as well as very bright gamma-ray sources. The nucleus sup 1 sup 7 sup 8 Hf has a nuclear isomer with excitation energy E sub x = 2.447 MeV. The 2.447-MeV isomeric state decays slowly (t sub 1 sub / sub 2 = 31 y) to the nearby state at 2.433 MeV. The J suppi = 13 sup - state loses energy in a rapid (t approx 10 sup - sup 1 sup 2 s) gamma-ray cascade ending at the 8 sup - rotational band head which in turn decays via the ground-state rotational band cascade. The gamma...

  7. Search for X-ray induced decay of the 31-yr isomer of 178Hf using synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Ahmad, I; Banar, J C; Becker, J A; Bredeweg, T A; Cooper, J R; Gemmell, D S; Kraemer, A; Mashayekhi, A; McNabb, D P; Miller, G G; Moore, E F; Palmer, P; Pangault, L N; Rundberg, R S; Schiffer, J P; Shastri, S D; Wang, T F; Wilhelmy, J B

    2004-09-13

    Isomeric {sup 178}Hf (t{sub 1/2} = 31 yr, E{sub x} = 2.446 MeV, J{sup {pi}} = 16{sup +}) was bombarded by a white beam of x-rays from the Advanced Photon Source at Argonne National Laboratory. A search was made for x-ray induced decay of the isomer by detecting prompt and delayed {gamma} rays associated with the decay. No induced decay was observed. Upper limits for such a process for x-ray energies between 7-100 keV were set. The limits between 7 and 30 keV are below {approx} 3 x 10{sup -27} cm{sup 2}-keV for induced decay that bypasses the 4-s isomer and {approx} 5 x 10{sup -27} cm{sup 2}-keV for induced decay that is delayed through this isomer, orders of magnitude below values at which induced decay was reported previously. These limits are consistent with what is known about the properties of atomic nuclei.

  8. An UPLC-MS/MS method for separation and accurate quantification of tamoxifen and its metabolites isomers.

    Science.gov (United States)

    Arellano, Cécile; Allal, Ben; Goubaa, Anwar; Roché, Henri; Chatelut, Etienne

    2014-11-01

    A selective and accurate analytical method is needed to quantify tamoxifen and its phase I metabolites in a prospective clinical protocol, for evaluation of pharmacokinetic parameters of tamoxifen and its metabolites in adjuvant treatment of breast cancer. The selectivity of the analytical method is a fundamental criteria to allow the quantification of the main active metabolites (Z)-isomers from (Z)'-isomers. An UPLC-MS/MS method was developed and validated for the quantification of (Z)-tamoxifen, (Z)-endoxifen, (E)-endoxifen, Z'-endoxifen, (Z)'-endoxifen, (Z)-4-hydroxytamoxifen, (Z)-4'-hydroxytamoxifen, N-desmethyl tamoxifen, and tamoxifen-N-oxide. The validation range was set between 0.5ng/mL and 125ng/mL for 4-hydroxytamoxifen and endoxifen isomers, and between 12.5ng/mL and 300ng/mL for tamoxifen, tamoxifen N-desmethyl and tamoxifen-N-oxide. The application to patient plasma samples was performed. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Production of the $^{178m2}$Hf Isomer Using a 4.5-GeV Electron Accelerator

    CERN Document Server

    Karamian, S A; Adam, J; Demekhina, N A

    2004-01-01

    High-productivity methods are required for the accumulation of long-lived isomers in amounts that are sufficient for the creation of experimental targets. A tantalum sample was activated with the Yerevan synchrotron using 4.5-GeV bremsstrahlung and the presence of ^{178m2}Hf was detected with good statistical accuracy by gamma-activity measurements. The integrated and mean cross-section values were deduced from the experiment. The isomer-to-ground-state ratio was then estimated and compared with that known for the p+Ta reaction studied at 660 MeV. In the present experiment, both the converter and the target were relatively thin for better definition of the experimental conditions. However, an assembly designed for high-productivity irradiations should be thick and the converter can also serve as a target sample when irradiated with a high-energy electron beam. The optimization of the isomer production was solved analytically and the largest estimated yield was determined as calibrated to the experimental yiel...

  10. Populations of carbonic acid isomers at 210 K from a fast two-electron reduced-density matrix theory.

    Science.gov (United States)

    Schwerdtfeger, Christine A; Mazziotti, David A

    2011-11-03

    Parametrization of the 2-electron reduced density matrix (2-RDM) rather than the many-electron wave function yields a new family of electronic-structure methods that are faster and more accurate than traditional coupled electron-pair methods including coupled cluster with single and double excitations. Deriving the parametrization from N-representability conditions generates a 2-RDM that captures significant correlation from triple and higher-order excitations at the cost of double excitations. We apply the parametric 2-RDM method to confirm recent experiments determining the relative thermodynamic populations of the cis-cis and cis-trans isomers of carbonic acid. In 2010 Bernard et al. showed by infrared spectroscopy that the populations of cis-cis and cis-trans isomers have a 10:1 ratio at 210 K. By use of the parametric 2-RDM method, we predict a 8:1 ratio at 210 K. Comparable ab initio methods overestimate the stability of the cis-cis isomer with 24:1 and 21:1 ratios. These 2-RDM-based methods promise to have significant applications throughout chemistry.

  11. Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure.

    Science.gov (United States)

    Hu, Pan; Lee, Sangsu; Park, Kyu Hyung; Das, Soumyajit; Herng, Tun Seng; Gonçalves, Théo P; Huang, Kuo-Wei; Ding, Jun; Kim, Dongho; Wu, Jishan

    2016-04-01

    The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl-or pentafluorophenyl-substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability in an ambient environment, while OZI-M has high reactivity and can be easily oxidized to a dioxo product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F, and 15.

  12. Isomer separation of $^{70g}Cu$ and $^{70m}Cu$ with a resonance ionization laser ion source

    CERN Document Server

    Köster, U; Mishin, V I; Weissman, L; Huyse, M; Kruglov, K; Müller, W F; Van Duppen, P; Van Roosbroeck, J; Thirolf, P G; Thomas, H C; Weisshaar, D W; Schulze, W; Borcea, R; La Commara, M; Schatz, H; Schmidt, K; Röttger, S; Huber, G; Sebastian, V; Kratz, K L; Catherall, R; Georg, U; Lettry, Jacques; Oinonen, M; Ravn, H L; Simon, H

    2000-01-01

    Radioactive copper isotopes were ionized with the resonance ionization laser ion source at the on-line isotope separator ISOLDE (CERN). Using the different hyperfine structure in the 3d/sup 10/ 4s /sup 2/S/sub 1/2/-3d/sup 10/ 4p /sup 2/P/sub 1/2//sup 0/ transition the low- and high-spin isomers of /sup 70/Cu were selectively enhanced by tuning the laser wavelength. The light was provided by a narrow-bandwidth dye laser pumped by copper vapor lasers and frequency doubled in a BBO crystal. The ground state to isomeric state intensity ratio could be varied by a factor of 30, allowing to assign gamma transitions unambiguously to the decay of the individual isomers. It is shown that the method can also be used to determine magnetic moments. In a first experiment for the 1/sup +/ ground state of /sup 70/Cu a magnetic moment of (+)1.8(3) mu /sub N/ and for the high-spin isomer of /sup 70/Cu a magnetic moment of (+or-)1.2(3) mu /sub N/ could be deduced. (20 refs).

  13. The Anti-tumour Agent, Cisplatin, and its Clinically Ineffective Isomer, Transplatin, Produce Unique Gene Expression Profiles in Human Cells

    Directory of Open Access Journals (Sweden)

    Anne M. Galea

    2008-01-01

    Full Text Available Cisplatin is a DNA-damaging anti-cancer agent that is widely used to treat a range of tumour types. Despite its clinical success, cisplatin treatment is still associated with a number of dose-limiting toxic side effects. The purpose of this study was to clarify the molecular events that are important in the anti-tumour activity of cisplatin, using gene expression profi ling techniques. Currently, our incomplete understanding of this drug’s mechanism of action hinders the development of more efficient and less harmful cisplatin-based chemotherapeutics. In this study the effect of cisplatin on gene expression in human foreskin fibroblasts has been investigated using human 19K oligonucleotide microarrays. In addition its clinically inactive isomer, transplatin, was also tested. Dual-fluor microarray experiments comparing treated and untreated cells were performed in quadruplicate. Cisplatin treatment was shown to significantly up- or down-regulate a consistent subset of genes. Many of these genes responded similarly to treatment with transplatin, the therapeutically inactive isomer of cisplatin. However, a smaller proportion of these transcripts underwent differential expression changes in response to the two isomers. Some of these genes may constitute part of the DNA damage response induced by cisplatin that is critical for its anti-tumour activity. Ultimately, the identification of gene expression responses unique to clinically active compounds, like cisplatin, could thus greatly benefit the design and development of improved chemotherapeutics.

  14. Biodegradation of endosulfan isomers and its metabolite endosulfate by two biosurfactant producing bacterial strains of Bordetella petrii.

    Science.gov (United States)

    Odukkathil, Greeshma; Vasudevan, Namasivayam

    2015-01-01

    The main objective of the investigation was to study the biodegradation of endosulfan isomers and its major metabolite endosulfate by two biosurfactant producing bacterial strains of Bordetella petrii. The significance of the study is to evaluate the capability of biosurfactant producing bacterial strains in enhancing the bioavailability of endosulfan. Sixty bacterial strains were isolated from the endosulfan degrading bacterial consortium and were screened for endosulfan degradation and biosurfactant production. Among those, two strains Bordetella petrii I GV 34 (Gene bank Accession No KJ02262) and Bordetella petrii II GV 36 (Gene bank Accession No KJ022625) were capable of degrading endosulfan with simultaneous biosurfactant production. Bordetella petrii I degraded 89% of α and 84% of β isomers of endosulfan whereas Bordetella petrii II degraded 82% of both the isomers. Both the strains were able to reduce the surface tension up to 19.6% and 21.4% with a minimum observed surface tension of 45 Dynes/cm and 44 Dynes/cm, respectively. The study revealed that the strains have the potential to enhance the degradation endosulfan residues in contaminated sites and water by biosurfactant production.

  15. Nucleosynthesis of $^{92}$Nb and the relevance of the low-lying isomer at 135.5 keV

    CERN Document Server

    Mohr, Peter

    2016-01-01

    Background: Because of its half-life of about 35 million years, 92Nb is considered as a chronometer for nucleosynthesis events prior to the birth of our sun. The abundance of 92Nb in the early solar system can be derived from meteoritic data. It has to be compared to theoretical estimates for the production of 92Nb to determine the time between the last nucleosynthesis event before the formation of the early solar system. Purpose: The influence of a low-lying short-lived isomer on the nucleosynthesis of 92Nb is analyzed. The thermal coupling between the ground state and the isomer via so-called intermediate states affects the production and survival of 92Nb. Method: The properties of the lowest intermediate state in 92Nb are known from experiment. From the lifetime of the intermediate state and from its decay branchings, the transition rate from the ground state to the isomer and the effective half-life of 92Nb are calculated as a function of the temperature. Results: The coupling between the ground state and...

  16. Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure

    KAUST Repository

    Hu, Pan

    2016-03-11

    The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl or pentafluorophenyl substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability under the ambient environment while OZI-M has high reactivity and can be easily oxidized to a dioxo-product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F and 15.

  17. Synthesis of 5'-bromo-2'-hydroxy-4,4',6'-trimethoxychalcone from Garcinia nervosa and of its isomer 3'-bromo-2'-hydroxy-4,4',6'- trimethoxychalcone

    Digital Repository Service at National Institute of Oceanography (India)

    Parab, S.J.; Kapdi, S.G.; Naik, C.G.; Kamat, S.P.

    The unambiguous syntheses of the naturally occurring 5'-bromo-2'-hydroxy-4,4',6'-trimethoxychalcone 1, a constituent of Garcinia nervosa, and its positional isomer 3'-bromo-2'-hydroxy-4,4',6'-trimethoxychalcone 6 are described...

  18. Synthesis of a new cyclosporine-based stationary phase and separation behaviors toward aromatic positional isomers by high-performance liquid chromatography.

    Science.gov (United States)

    Liu, Wen-na; Fan, Jun; Lin, Chun; Zheng, Sheng-run; Zhang, Wei-guang

    2015-04-01

    A new cyclosporine-bonded stationary phase has been synthesized through the Staudinger reaction between azido cyclosporine A (CsA) and aminopropyl silica gel and applied in separations of six disubstituted aromatic analytes by high-performance liquid chromatography. For dimethyl phthalate, nitroaniline and chloronitrobenzene, their positional isomers were well-separated on this CsA stationary phase, in which the separation factor for m-/o-dimethyl phthalates was the biggest. For nitrotoluene, dichlorobenzene and benzenediol, the m-/o-isomers were co-eluted. Then, effects of chromatographic conditions (such as types and content of alcoholic modifiers) on separation of nitroaniline positional isomers have been investigated. Retention behaviors of nitroaniline isomers on the column exhibited the strengthening trend along with increasing carbon number of alcohols, from ethanol to 1-propanol, and to 1-butanol. A similar phenomenon was observed by lowering the content of alcohol.

  19. An isomer-specific study of solid nitromethane decomposition pathways - Detection of aci-nitromethane (H2CNO(OH)) and nitrosomethanol (HOCH2NO) intermediates

    Science.gov (United States)

    Maksyutenko, Pavlo; Förstel, Marko; Crandall, Parker; Sun, Bing-Jian; Wu, Mei-Hung; Chang, Agnes H. H.; Kaiser, Ralf I.

    2016-08-01

    An isomer specific study of energetic electron exposed nitromethane ices was performed via photoionization - reflectron time of flight mass spectrometry (PI-ReTOF-MS) of the subliming products employing tunable vacuum ultraviolet light for ionization. Supported by electronic structure calculations, nitromethane (CH3NO2) was found to isomerize to methyl nitrite (CH3ONO) and also via hydrogen migration to the hitherto elusive aci-nitromethane isomer (H2CNO(OH)). The latter isomerizes to nitrosomethanol (HOCH2NO) through hydroxyl group (OH) migration, and, probably, ring closure to the cyclic 2-hydroxy-oxaziridine isomer (c-H2CON(OH)) as well. The importance of hydrogen migrations was also verified via the nitrosomethane (CH3NO) - formaldehyde oxime isomer (CH2NOH) pair.

  20. Electron optics

    CERN Document Server

    Grivet, Pierre; Bertein, F; Castaing, R; Gauzit, M; Septier, Albert L

    1972-01-01

    Electron Optics, Second English Edition, Part I: Optics is a 10-chapter book that begins by elucidating the fundamental features and basic techniques of electron optics, as well as the distribution of potential and field in electrostatic lenses. This book then explains the field distribution in magnetic lenses; the optical properties of electrostatic and magnetic lenses; and the similarities and differences between glass optics and electron optics. Subsequent chapters focus on lens defects; some electrostatic lenses and triode guns; and magnetic lens models. The strong focusing lenses and pris

  1. A possible role for triplet H2CN+ isomers in the formation of HCN and HNC in interstellar clouds

    Energy Technology Data Exchange (ETDEWEB)

    Allen, Thomas L. [Univ. of California, Davis, CA (United States); Goddard, John D. [Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Schaefer, III, Henry F. [Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    1980-10-01

    We determine the structures and energies of the lowest triplet states of four isomers of H2CN+ by self-consistent field and configuration interaction calculations. When both hydrogen atoms are attached to the nitrogen atom, H2CN+, the molecule has its lowest triplet state energy, which is 97.2 kcal mol-1 above the energy of the linear singlet ground state. The structure has C2v symmetry, with an HCH bond angle of 116.8°, and bond lengths of 1.009 Å (H–N) and 1.268 Å (N–C). Other isomers investigated include the H2CN+ isomer at 104.7, the c i s-HCNH+ isomer at 105.3, and the t r a n s-HCNH+ isomer at 113.6 kcal mol-1. The H2CN+ isomer has an unusual ’’carbonium nitrene’’ structure, with a C–N bond length of 1.398 Å. It is suggested that the triplet H2CN+ isomer may play a role in determining the relative yields of HCN and HNC from the reaction of C+ and NH3. Specifically, a triplet path is postulated in which C+ and NH3 yield the triplet H2NC+ isomer, which then yields the singlet H2CN+ isomer by phosphorescent emission. Furthermore, because this emission removes a large amount of energy, the singlet H2CN+ isomer may have insufficient energy to isomerize to the linear singlet ground state. Subsequent dissociative recombination would yield the HNC isomer exclusively.

  2. Inclusion of fresh forage in the ration for dairy cows: effects on CLA and trans C18:1 isomers content of milk fat

    Directory of Open Access Journals (Sweden)

    P. Secchiari

    2010-01-01

    Full Text Available Milk fat is the richest natural source of conjugated linoleic acid (CLA isomers. The 9-cis, 11-trans CLA isomer (rumenic acid, RA origins from two pathways: as an intermediate of the rumen biohydrogenation process of linoleic acid or as the product of the activity of mammary Stearoyl Co-A desaturase enzyme (SCD with trans-11, C18:1 (vaccenic acid, VA as the precursor, another intermediate in the biohydrogenation of linoleic and linolenic acid.

  3. The influence of interfaces on properties of thin-film inorganic structural isomers containing SnSe—NbSe₂ Subunits

    Energy Technology Data Exchange (ETDEWEB)

    Alemayehu, Matti B.; Falmbigl, Matthias; Ta, Kim; Johnson, David C. (Oregon)

    2016-06-15

    Inorganic isomers ([SnSe]1+δ)m(NbSe₂)n([SnSe]1+δ)p(NbSe₂)q([SnSe]1+δ)r(NbSe₂)s where m, n, p, q, r, and s are integers and m + p + r = n + q + s = 4 were prepared using the modulated elemental reactant technique. This series of all six possible isomers provides an opportunity to study the influence of interface density on properties while maintaining the same unit cell size and composition. As expected, all six compounds were observed to have the same atomic compositions and an almost c-axis lattice parameter of ≈4.90 (5) nm, with a slight trend in the c-axis lattice parameter correlated with the different number of interfaces in the isomers: two, four and six. The structures of the constituents in the ab-plane were independent of one another, confirming the nonepitaxial relationship between them. The temperature dependent electrical resistivities revealed metallic behavior for all the six compounds. Surprisingly, the electrical resistivity at room temperature decreases with increasing number of interfaces. Hall measurements suggest this results from changes in carrier concentration, which increases with increasing thickness of the thickest SnSe block in the isomer. Carrier mobility scales with the thickness of the thickest NbSe₂ block due to increased interfacial scattering as the NbSe₂ blocks become thinner. The observed behavior suggests that the two constituents serve different purposes with respect to electrical transport. SnSe acts as a charge donor and NbSe₂ acts as the charge transport layer. This separation of function suggests that such heterostructures can be designed to optimize performance through choice of constituent, layer thickness, and layer sequence. A simplistic model, which predicts the properties of the complex isomers from a weighted sum of the

  4. Micellar and sub-micellar ultra-high performance liquid chromatography of hydroxybenzoic acid and phthalic acid positional isomers.

    Science.gov (United States)

    Fasciano, Jennifer M; Danielson, Neil D

    2016-03-18

    Micellar liquid chromatography (MLC) has been used primarily for the separation of neutral analytes of varying polarities, most commonly phenols and polyaromatic hydrocarbons, but does not seem to have been used to study aromatic hydroxy acids in detail. We have studied the separation of hydroxybenzoic acid mixtures, including monohydroxybenzoic and dihydroxybenzoic acid positional isomers by MLC. Sodium dodecylsulfate (SDS) is investigated as the modifying surfactant on a C18 ultra-high performance liquid chromatography (UHPLC) column (100 × 2.1mm, 1.8 μm). The addition of only SDS (no organic solvent) to the mobile phase reduced the influence of hydrophobic interactions while improving the retention times, resolution, and peak shapes, even at concentrations below the critical micellization concentration (CMC). The UHPLC separation of 7 hydroxybenzoic acids, including 6 dihydroxybenzoic acid positional isomers and one trihydroxybenzoic acid, is achieved with high efficiency using 0.1% SDS in 1.84 mM sulfuric acid (pH 2.43) mobile phase, in less than 6 min with a flow rate of 0.3 mL min(-1), and in less than four min with a flow rate of 0.7 mL min(-1). Six monohydroxybenzoic acid isomers are also effectively separated by MLC, using a 0.5% SDS mobile phase modifier, in less than 20 min with a flow rate of 0.3 mL min(-1), and in less than 14 min with a flow rate of 0.7 mL min(-1). The 3 phthalic acid isomers could be separated using a similar mobile phase and flow rates in less than 6 and 4 min. Solute-micelle equilibrium constants and partition coefficients are calculated for 6 monohydroxybenzoic acids based on a plot of MLC retention factor vs. mobile phase micelle concentration. All aromatic acid isomers studied can be classified as binding solutes in the MLC retention mechanism. Less effective separations are observed with shorter chain surfactants, leading to higher retention times and poor peak shapes. It is concluded that increasing chain length led to more

  5. Kinetics and mechanism of the reaction of OH with the trimethylbenzenes--experimental evidence for the formation of adduct isomers.

    Science.gov (United States)

    Bohn, Birger; Zetzsch, Cornelius

    2012-10-28

    The reversible gas-phase addition of OH radicals to the trimethylbenzenes was investigated in pulsed experiments utilizing VUV flash-photolysis resonance-fluorescence of H(2)O in the temperature range of 275-340 K. Triexponential OH decays were observed in the presence of the trimethylbenzenes, indicating the participation of more than one adduct species. Analytical solutions for the system of differential equations with two adduct isomers were derived, and the OH decay curves were evaluated based on this reaction model. This led to significant improvements of fit qualities and notable changes in OH rate constants compared to a previous model with a single adduct species. The detailed analysis was confined to 1,3,5-trimethylbenzene where reversible formation of two OH-aromatic ortho- and ipso-adduct isomers is feasible in accordance with the extended reaction model. Only after inclusion of additional isomerization reactions, consistent thermochemical data were obtained from the fitted rate constants. Reaction enthalpies of -83 ± 7 kJ mol(-1) and -35 ± 22 kJ mol(-1) were derived for the formation of one adduct isomer and the isomerization into the other, respectively. Based on literature data, the more and less stable adducts were assigned to ipso- and ortho-adduct isomers, respectively. The potential isomerization precluded the determination of primary yields of adduct isomers but formation of the ipso-adduct in any case is a minor process. For the rate constants of the OH + 1,3,5-trimethylbenzene reaction an Arrhenius expression k(OH) = 1.32 × 10(-11) cm(3) s(-1) exp(450 ± 50 K/T) was obtained. Based on the same approach, the rate constants of the OH reactions with 1,2,3-trimethylbenzene and 1,2,4-trimethylbenzene were derived as k(OH) = 3.61 × 10(-12) cm(3) s(-1) exp(620 ± 80 K/T) and k(OH) = 2.73 × 10(-12) cm(3) s(-1) exp(730 ± 70 K/T), respectively.

  6. Identification of conjugated linoleic acid (CLA) isomers by silver ion-liquid chromatography/in-line ozonolysis/mass spectrometry (Ag+-LC/O3-MS).

    Science.gov (United States)

    Sun, Chenxing; Black, Brenna A; Zhao, Yuan-Yuan; Gänzle, Michael G; Curtis, Jonathan M

    2013-08-06

    A novel method for the identification of conjugated linoleic acid (CLA) isomers has been developed in which silver ion liquid chromatography is coupled to in-line ozonolysis/mass spectrometry (Ag(+)-LC/O3-MS). The mobile phase containing CLA isomers eluting from the Ag(+)-LC column flows through a length of gas-permeable tubing within an ozone rich environment. Ozone penetrating the tubing wall reacts with the conjugated double bonds forming ozonolysis product aldehydes. These, and their corresponding methanol loss fragment ions formed within the atmospheric pressure photoionization (APPI) source, were detected by in-line MS and used for the direct assignment of double bond positions. Assignment of positional isomers is based entirely on the two pairs of diagnostic ions seen in the in-line O3-MS mass spectra. In this way, de novo identification of CLA positional isomers, i.e. without requiring comparison to CLA standards, was achieved. The Ag(+)-LC/O3-MS method was applied to the analysis of CLA isomers in a commercial CLA supplement, milk fat, and the lipid extract from a Lactobacillus plantarum TMW1460 culture. The results demonstrate how Ag(+)-LC/O3-MS can be used for the direct and fast determination of CLA isomers at low concentrations and in complex lipid mixtures.

  7. Optical Solitons

    Science.gov (United States)

    Taylor, J. R.

    2005-08-01

    1. Optical solitons in fibres: theoretical review A. Hasegawa; 2. Solitons in optical fibres: an experimental account L. F. Mollenauer; 3. All-optical long-distance soliton-based transmission systems K. Smith and L. F. Mollenauer; 4. Nonlinear propagation effects in optical fibres: numerical studies K. J. Blow and N. J. Doran; 5. Soliton-soliton interactions C. Desem and P. L. Chu; 6. Soliton amplification in erbium-doped fibre amplifiers and its application to soliton communication M. Nakazawa; 7. Nonlinear transformation of laser radiation and generation of Raman solitons in optical fibres E. M. Dianov, A. B. Grudinin, A. M. Prokhorov and V. N. Serkin; 8. Generation and compression of femtosecond solitons in optical fibers P. V. Mamyshev; 9. Optical fibre solitons in the presence of higher order dispersion and birefringence C. R. Menyuk and Ping-Kong A. Wai; 10. Dark optical solitons A. M. Weiner; 11. Soliton Raman effects J. R. Taylor; Bibliography; Index.

  8. Alterations of metallothionein isomers in Hg{sup 0}-exposed rat brain

    Energy Technology Data Exchange (ETDEWEB)

    Yasutake, A. [Biochemistry Section, National Institute for Minamata Disease, Minamata, Kumamoto 867-0008 (Japan); Nagano, M. [Morikawa Kenkodo Co., Ltd., 2170 Taguchi, Kosa, Kamimashiki, Kumamoto 861-4616 (Japan); Hirayama, K. [Kumamoto University College of Medical Science, Kuhonji, Kumamoto 862-0976 (Japan)

    2003-01-01

    Previously we found that exposure to mercury vapor effectively induced brain metallothionein (MT) in rats. Here, using FPLC-gel chromatography, we examined time-dependent alterations in the MT isomers, MT-I/II and MT-III, following 3 weeks of exposure. Rats were exposed to mercury vapor at 8.3 mg/m{sup 3} for 15 h in total over 5 consecutive days. Total MT levels in rat cerebrum and cerebellum increased by 65% and 155%, respectively, 24 h after the final exposure. The increased levels in both tissues remained unchanged for at least 2 weeks after termination of exposure. Interestingly, most MT in control rat cerebrum and cerebellum was accounted for by MT-III, with MT-I/II being less than 10%. Through mercury vapor exposure, MT-I/II was quickly induced to a significant extent in both tissues, reaching a level comparable to that of MT-III. The induction rate of MT-I/II in the cerebellum was somewhat higher than in the cerebrum. Chromatograms showed that the MT-I/II thus induced began to decline at an early stage in both tissues. In the cerebrum, the amount of MT-I/II on day 22 was about 30% of the maximum level on day 1. On the other hand, the induction of MT-III was not that dramatic, but it did become evident, at least in the latter stage, when MT-I/II had begun to decrease. Thus, though the induction rate of MT-III was not as high as MT-I/II, it was sustained throughout the experimental period. (orig.)

  9. Dibenzoheptazethrene isomers with different biradical characters: An exercise of clar's aromatic sextet rule in singlet biradicaloids

    KAUST Repository

    Sun, Zhe

    2013-12-04

    Clar\\'s aromatic sextet rule has been widely used for the prediction of the reactivity and stability of polycyclic aromatic hydrocarbons with a closed-shell electronic configuration. Recent advances in open-shell biradicaloids have shown that the number of aromatic sextet rings plays an important role in determination of their ground states. In order to test the validity of this rule in singlet biradicaloids, the two soluble and stable dibenzoheptazethrene isomers DBHZ1 and DBHZ2 were prepared by different synthetic approaches and isolated in crystalline form. These two molecules have different numbers of aromatic sextet rings in their respective biradical resonance forms and thus are expected to exhibit varied singlet biradical character. This assumption was verified by different experimental methods, including nuclear magnetic resonance (NMR), electron spin resonance (ESR), superconducting quantum interference device (SQUID), steady-state and transient absorption spectroscopy (TA), and X-ray crystallographic analysis, assisted by unrestricted symmetry-broken density functional theory (DFT) calculations. DBHZ2, with more aromatic sextet rings in the biradical form, was demonstrated to possess greater biradical character than DBHZ1; as a result, DBHZ2 exhibited an intense one-photon absorption (OPA) in the near-infrared region (λabs max = 804 nm) and a large two-photon absorption (TPA) cross-section (σ(2)max = 2800 GM at 1600 nm). This investigation together with previous studies indicates that Clar\\'s aromatic sextet rule can be further extended to the singlet biradicaloids to predict their ground states and singlet biradical characters. © 2013 American Chemical Society.

  10. 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.

  11. The gamma-ray spectra of 5-carbon alkane isomers in the positron annihilation process

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Xiaoguang, E-mail: hsiaoguangma@188.com; Zhu, Yinghao; Liu, Yang

    2016-05-06

    The gamma-ray spectra of pentane (C{sub 5}H{sub 12}) and its two isomers, i.e., 2-Methylbutane (CH{sub 3}C(CH{sub 3})HC{sub 2}H{sub 5}) and 2,2-Dimethylpropane (C(CH{sub 3}){sub 4}) have been studied theoretically in the present work. The recent experimental gamma-ray spectra of these three molecules show that they have the same Doppler shifts, although their molecular structures are dramatically different. In order to reveal why the gamma-ray spectra of these molecules are less sensitive to the molecular structures, the one-dimensional gamma-ray spectra and spherically averaged momentum (SAM) distributions, the two-dimensional angular correlation of annihilation radiation (ACAR), and the three-dimensional momentum distributions of the positron–electron pair are studied. The one-centered momentum distributions of the electrons are found to play more important role than the multi-centered coordinate distributions. The present theoretical predictions have confirmed the experimental findings for the first time. The dominance of the inner valence electrons in the positron–electron annihilation process has also been suggested in the present work. - Highlights: • The structure effects only play a minor role in the one-dimension gamma-ray spectra. • The present study further confirms the dominance of the inner valence electrons in the positron–electron annihilation process. • The momentum distributions of the electrons play more important role than the coordinate distributions.

  12. Determination of phenylenediamine isomers in hair dyes by coal cinders micro-column extraction and MEKC.

    Science.gov (United States)

    Wu, Yiwei; Jiang, Feng; Chen, Lin; Zheng, Jing; Deng, Zhenli; Tao, Qing; Zhang, Jing; Han, Lijuan; Wei, Xiaoshu; Yu, Aimin; Zhang, Haili

    2011-06-01

    A new micellar electrokinetic chromatography (MEKC) method using beta-cyclodextrins (β-CDs) and 1-butyl-3-methylimidazolium hexafluorophosphates (ionic liquids) as additives was successfully developed for determination of para-, meta-, and ortho-phenylenediamines isomers (p-P, m-P, and o-P) in hair dyes. To improve the sensitivity of the MEKC-UV, a simple and cheap flow injection (FI) technique using a micro-column packed with coal cinders (the by-products from combustion in a boiler) as solid-phase extractant was also investigated. In the presence of 20 mmol L(-1) phosphates at pH 5.5, addition of 12 mmol L(-1) ionic liquids and 8 mmol L(-1) β-CDs greatly improved the separation efficiency. The three analytes could be quantitatively adsorbed by coal cinders, and desorbed readily with 0.15 mL of 0.01 mol L(-1) NaOH. Under the optimum conditions, an enrichment factor (EF) of 33.3 was obtained, and determination limits of p-P, m-P, and o-P were 1.97 × 10(-7), 0.99 × 10(-7), and 0.61 × 10(-7) mol L(-1), respectively. The adsorption capacities of the coal cinders micro-column for p-P, m-P, and o-P were all 1.20 mg g(-1). The presented procedure was successfully applied to the determination of p-P, m-P, and o-P in hair dyes with satisfactory results.

  13. Contraction and expansion of the silicon scaffold of stable Si6R6 isomers.

    Science.gov (United States)

    Abersfelder, Kai; Russell, Adam; Rzepa, Henry S; White, Andrew J P; Haycock, Peter R; Scheschkewitz, David

    2012-09-26

    The reactivity of two stable Si(6)R(6) clusters (4 and 5, R = 2,4,6-(i)Pr(3)C(6)H(2)) with unsymmetrical substitution patterns (including Si, SiR, and SiR(2) vertices) is reported. In order to account for the importance of such clusters as model systems for transient intermediates in the deposition of elemental silicon, we here propose the term "siliconoids" for silicon clusters with unsaturated valencies. With the hexasilaprismane 8a, a saturated-i.e., non-siliconoid-Si(6)R(6) isomer is accessible from a suitable Si(3) precursor. Thermal redistribution of the substituents converts 1,1,2-trichlorocyclotrisilane 6 into the corresponding 1,2,3-derivative 7 prior to the requisite reductive coupling step leading to 8a. On the other hand, a stable expanded Si(11)-siliconoid 9 was isolated as a minor side product of the thermal isomerization of 4 to 5, thus providing a first example of siliconoid cluster expansion in the condensed phase. In the solid-state structure, the two unsubstituted vertices of 9 strongly interact in a staggered propellane-like fashion. Oxidative cluster contraction of a siliconoid scaffold is observed upon treatment of siliconoid 5 with a large excess of iodine in refluxing toluene, thus providing access to a highly functionalized hexaiodocyclopentasilane 11 in high yield. Conversely, chlorination of the isomeric 4 with BiCl(3) as a mild source of Cl(2) results in a complex mixture of products from chlorination of the unsubstituted vertices as well as σ-bonds of the cluster framework of 4. The main product, 1,2-dichlorotricyclo[2.2.0.0(2,5)]hexasilane 12, undergoes thermal cluster contraction to give tricyclo[2.1.0.0(2,5)]pentasilane 14 with an exohedral chlorosilyl group.

  14. 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.

  15. Optical biosensors

    OpenAIRE

    Damborský, Pavel; Švitel, Juraj; Katrlík, Jaroslav

    2016-01-01

    Optical biosensors represent the most common type of biosensor. Here we provide a brief classification, a description of underlying principles of operation and their bioanalytical applications. The main focus is placed on the most widely used optical biosensors which are surface plasmon resonance (SPR)-based biosensors including SPR imaging and localized SPR. In addition, other optical biosensor systems are described, such as evanescent wave fluorescence and bioluminescent optical fibre biose...

  16. Optical keyboard

    Science.gov (United States)

    Veligdan, James T.; Feichtner, John D.; Phillips, Thomas E.

    2001-01-01

    An optical keyboard includes an optical panel having optical waveguides stacked together. First ends of the waveguides define an inlet face, and opposite ends thereof define a screen. A projector transmits a light beam outbound through the waveguides for display on the screen as a keyboard image. A light sensor is optically aligned with the inlet face for sensing an inbound light beam channeled through the waveguides from the screen upon covering one key of the keyboard image.

  17. 3d-4f Metal-Organic Framework with Dual Luminescent Centers That Efficiently Discriminates the Isomer and Homologues of Small Organic Molecules.

    Science.gov (United States)

    Zeng, Guang; Xing, Shanghua; Wang, Xiuru; Yang, Yulin; Ma, Dingxuan; Liang, Hongwei; Gao, Lu; Hua, Jia; Li, Guanghua; Shi, Zhan; Feng, Shouhua

    2016-02-01

    A 3d-4f luminescent metal-organic framework (MOF), [Tb2(Cu8I8)(C12H8NO2)6(H2O)4]·5C4H8O2 (4), and three analogues {[La2(Cu8I8)(C12H8NO2)6(C4H8O2)2(H2O)2]·3C4H8O2·2H2O (1), [Ce2(Cu8I8)(C12H8NO2)6(H2O)4]·5C4H8O2 (2), and [Eu2(Cu8I8)(C12H8NO2)6(H2O)4]·5C4H8O2 (3)}, were self-assembled from copper(I) halide clusters and lanthanide metal ions with an organic linker [3-(pyridin-4-yl)benzoic acid] under solvothermal conditions. Compound 4 with high quantum yield (Φ = 68%) exhibits reversible luminescence behavior, accompanying the removal and recovery of guest molecules (1,4-dioxane). Because of the unique porous structure and dual luminescent centers of compound 4, it can efficiently differentiate benzene series with different sizes and provide readouts in corresponding optical signals. Furthermore, it also can unambiguously discriminate the isomers, homologues, and other small molecules with similar structural motifs from one another. The luminescent color of the MOF sensor in different guest solvents has obvious changes that can be clearly distinguished by the naked eye. This multicolor luminescence originates from emissions of the dual luminescent centers, and the emissions have shifted, enhanced, weakened, or quenched to different degrees.

  18. Theoretical Investigation on the Absorption and Emission Properties of the Three Isomers of Bis(thiocyanato)(2,2'-bipyridyl)platinum(Ⅱ)

    Institute of Scientific and Technical Information of China (English)

    HU,Xiao-Ying; LIU,Xiao-Juan; FENG,Ji-Kang

    2007-01-01

    This paper presents a Density Functional or Time Dependent Density Functional (DFT/TDDFT) study of the molecular and electronic structures, optical absorption and emission spectra of three linkage isomers:bis(isothiocyanato-S)(2,2'-bipyridyl) platinum(Ⅱ) ([Pt(SCN)2(bpy)]), (isothiocyanato-S)(thiocyanato-N)-(2,2'-bipyridyl) platinum(Ⅱ) ([Pt(SCN)(NCS)(bpy)]), and bis(thiocyanato-N)(2,2')-bipyridyl)platinum(Ⅱ) ([Pt(NCS)2(bpy)]),in which different coordination ligands based on the N- and S-coordination of the thiocyanato ligands control the luminescent color. The electronic structures were studied using the B3LYP functional. Optimized geometries were compared to the experimentally observed structures. TDDFT calculation was carried out to investigate the excited singlet and triplet states. Calculations have been performed both in vacuo and in solvents, using a polarized continuum model (PCM) to account for solute-solvent interactions. Inclusion of the solvent led to a significant energy change, and as a consequence, the computed spectrum calculated in the presence of the solvent was in good agreement with the experimental determinations. The first two absorptions were found to originate from mixed platinum-SCN (or NSC) to bipyridyl-π* transitions rather than pure metal-to-ligand-charge-transfer (MLCT) transitions,whereas the higher-energy bands arose from intraligand π→π* transitions. The stretching frequencies of C≡N have been calculated both in the ground and excited states, which are relative to the charge transition during the excitation. In addition, different sizes of basis sets were also discussed in this paper.

  19. Optical interconnects

    CERN Document Server

    Chen, Ray T

    2006-01-01

    This book describes fully embedded board level optical interconnect in detail including the fabrication of the thin-film VCSEL array, its characterization, thermal management, the fabrication of optical interconnection layer, and the integration of devices on a flexible waveguide film. All the optical components are buried within electrical PCB layers in a fully embedded board level optical interconnect. Therefore, we can save foot prints on the top real estate of the PCB and relieve packaging difficulty reduced by separating fabrication processes. To realize fully embedded board level optical

  20. Optical fibres

    CERN Document Server

    Geisler, J; Boutruche, J P

    1986-01-01

    Optical Fibers covers numerous research works on the significant advances in optical fibers, with particular emphasis on their application.This text is composed of three parts encompassing 15 chapters. The first part deals with the manufacture of optical fibers and the materials used in their production. The second part describes optical-fiber connectors, terminals and branches. The third part is concerned with the major optoelectronic components encountered in optical-communication systems.This book will be of value to research scientists, engineers, and patent workers.